Classifications

• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
  • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
  • C09D7/20—Diluents or solvents
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B27/00—Layered products comprising a layer of synthetic resin
  • B32B27/34—Layered products comprising a layer 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
  • B32B27/00—Layered products comprising a layer of synthetic resin
  • B32B27/36—Layered products comprising a layer of synthetic resin comprising polyesters
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
  • B32B7/02—Physical, chemical or physicochemical properties
  • B32B7/025—Electric or magnetic properties
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
  • C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
  • C08G63/60—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from the reaction of a mixture of hydroxy carboxylic acids, polycarboxylic acids and polyhydroxy compounds
  • C08G63/605—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from the reaction of a mixture of hydroxy carboxylic acids, polycarboxylic acids and polyhydroxy compounds the hydroxy and carboxylic groups being bound to aromatic rings
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
  • C08G63/78—Preparation processes
  • C08G63/80—Solid-state polycondensation
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
  • C08G63/78—Preparation processes
  • C08G63/82—Preparation processes characterised by the catalyst used
  • C08G63/83—Alkali metals, alkaline earth metals, beryllium, magnesium, copper, silver, gold, zinc, cadmium, mercury, manganese, or compounds thereof
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
  • C08G69/44—Polyester-amides
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
  • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
  • C08J5/18—Manufacture of films or sheets
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K5/00—Use of organic ingredients
  • C08K5/16—Nitrogen-containing compounds
  • C08K5/34—Heterocyclic compounds having nitrogen in the ring
  • C08K5/3412—Heterocyclic compounds having nitrogen in the ring having one nitrogen atom in the ring
  • C08K5/3415—Five-membered rings
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L101/00—Compositions of unspecified macromolecular compounds
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
  • C08L77/12—Polyester-amides
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L9/00—Compositions of homopolymers or copolymers of conjugated diene hydrocarbons
  • C08L9/06—Copolymers with styrene
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
  • C09D153/00—Coating compositions based on block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Coating compositions based on derivatives of such polymers
  • C09D153/005—Modified block copolymers
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
  • C09D177/00—Coating compositions based on polyamides obtained by reactions forming a carboxylic amide link in the main chain; Coating compositions based on derivatives of such polymers
  • C09D177/12—Polyester-amides
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
  • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
  • C09D7/40—Additives
  • C09D7/65—Additives macromolecular
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
  • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
  • C09D7/40—Additives
  • C09D7/66—Additives characterised by particle size
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L2203/00—Applications
  • C08L2203/16—Applications used for films
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L2203/00—Applications
  • C08L2203/20—Applications use in electrical or conductive gadgets
  • C08L2203/206—Applications use in electrical or conductive gadgets use in coating or encapsulating of electronic parts
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L2205/00—Polymer mixtures characterised by other features
  • C08L2205/22—Mixtures comprising a continuous polymer matrix in which are dispersed crosslinked particles of another polymer

Definitions

• the present disclosure relates to compositions and films.
• JP 2019-199612A discloses a resin composition containing a styrene polymer, an inorganic filler, and a curing agent.
• the styrene polymer is an acid-modified styrene polymer having a carboxyl group
• the inorganic filler is silica and/or aluminum hydroxide
• the particle size of the inorganic filler is 1 ⁇ m or less
• the content of is 20 to 80 parts by mass based on 100 parts by mass of the styrenic polymer
• the resin composition has the following formulas (A) and (B) in the form of a film having a thickness of 25 ⁇ m.
• a resin composition that satisfies the requirements is described.
• X 50...(A) Y ⁇ 40...(B)
• X represents the absorption rate (unit: %) of light with a wavelength of 355 nm
• Y represents the haze value (unit: %).
• JP-A No. 2022-17947 discloses a thermosetting adhesive sheet containing a binder resin and a curing agent, in which a cured product obtained by heating the thermosetting adhesive sheet at 180° C. for 1 hour is (i) A thermosetting adhesive sheet that satisfies (iv) is described.
• a thermosetting adhesive sheet that satisfies (iv) is described.
• the dielectric constant is 1.5 to 3.0 at a frequency of 10 GHz and 23°C.
• the dielectric loss tangent is 0.0001 to 0.01 at a frequency of 10 GHz and 23°C.
• the linear expansion coefficient ⁇ 1 at 0°C to glass transition temperature is 100 to 500 ppm/°C.
• the problem to be solved by the embodiments of the present disclosure is to provide a composition that can produce a film that has excellent step followability and excellent suitability for laser processing. Further, another problem to be solved by the other embodiments of the present disclosure is to provide a film that has excellent step followability and excellent suitability for laser processing.
• Means for solving the above problems include the following aspects.
• ⁇ 1> A composition comprising thermoplastic particles having an average particle diameter of 100 ⁇ m or less, an aromatic polyester resin, and a solvent.
• ⁇ 2> A composition comprising thermoplastic particles, an aromatic polyester resin, and a solvent, wherein the content of the thermoplastic particles is 50% by mass or more based on the total mass of solids contained in the composition.
• ⁇ 3> The composition according to ⁇ 2> above, wherein the ratio of the average particle diameter of the thermoplastic particles to the thickness of the layer formed by the following layer formation method is 1.5 or less.
• Method for forming a layer A layer is formed by applying the composition to the surface of a copper base material in an amount of 0.015 g/cm 2 and heating in an environment of 180° C.
• thermoplastic particles are elastomer particles.
• thermoplastic particles described in ⁇ 1> to ⁇ 4> above include at least one of a resin having a constitutional unit having an aromatic hydrocarbon group and an elastomer having a constitutional unit having an aromatic hydrocarbon group.
• ⁇ 6> The composition according to any one of ⁇ 1> to ⁇ 5> above, wherein the aromatic polyester resin contains an aromatic polyester amide.
• solvent contains N-methylpyrrolidone.
• ⁇ 8> having a layer A and a layer B on at least one surface of the layer A,
• the layer B includes particles containing at least one of a resin having a constitutional unit having an aromatic hydrocarbon group and an elastomer having a constitutional unit having an aromatic hydrocarbon group, and an aromatic polyester resin,
• the minimum area ratio of the particles in the thickness direction cross section of the layer B is 50% or more, film.
• ⁇ 9> The film according to ⁇ 8> above, having a dielectric loss tangent of 0.01 or less at 28 GHz.
• ⁇ 10> The film according to ⁇ 8> or ⁇ 9> above, wherein the ratio of the elastic modulus at 160° C. of the layer A to the elastic modulus at 160° C. of the layer B is 1.2 or more.
• ⁇ 11> The film according to any one of ⁇ 8> to ⁇ 10> above, wherein the layer B has an elastic modulus at 160° C. of 10 MPa or less.
• ⁇ 12> The film according to any one of ⁇ 8> to ⁇ 11> above, wherein the layer A has a dielectric loss tangent of 0.01 or less at 28 GHz.
• ⁇ 13> The film according to any one of ⁇ 8> to ⁇ 12> above, wherein the layer A contains a liquid crystal polymer.
• ⁇ 14> The film according to any one of ⁇ 8> to ⁇ 13> above, wherein the layer A contains an aromatic polyesteramide.
• ⁇ 15> The film according to any one of ⁇ 8> to ⁇ 14> above, wherein the layer B has a dielectric loss tangent of 0.01 or less at 28 GHz.
• ⁇ 16> The film according to any one of ⁇ 8> to ⁇ 15> above, wherein the layer B contains a liquid crystal polymer.
• the aromatic polyester resin contains an aromatic polyester amide.
• compositions that can produce a film that has excellent step followability and excellent suitability for laser processing it is possible to provide a film that has excellent step followability and excellent suitability for laser processing.
• the amount of each component contained in the composition means the total amount of the plurality of substances.
• groups (atomic groups) in this specification descriptions that do not indicate substituted or unsubstituted include those having no substituent as well as those having a substituent.
• 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 with a concept that includes both acrylic and methacrylic.
• 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.
• solids refers to components excluding solvent.
• laser processing suitability refers to a property that can reduce excessive laser cutting when performing laser cutting, especially through-hole processing. It can be said that it has excellent workability into a desired shape.
• dielectric loss tangent shall be measured by the following method.
• the measurement of the dielectric loss tangent is carried out by the resonance perturbation method at a frequency of 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.
• an unnecessary layer may be scraped off with a razor or the like, and an evaluation sample containing only the desired layer may be prepared and used as the measurement target.
• the layer to be measured may be scraped off with a razor, etc., and the resulting powdered sample may be used as the object of measurement for the dielectric loss tangent. .
• the measurement of the dielectric loss tangent of a polymer in the present disclosure is performed by identifying or isolating the chemical structure of the polymer constituting each layer, and using a powdered sample of the polymer to be measured, according to the method for measuring the dielectric loss tangent described above. do.
• GPC gel permeation chromatography
• composition according to the first aspect includes thermoplastic particles having an average particle diameter of 100 ⁇ m or less, an aromatic polyester resin, and a solvent.
• the viscosity of the first composition is preferably 50 mPa ⁇ s to 2000 mPa ⁇ s, more preferably 100 mPa ⁇ s to 1000 mPa ⁇ s, and 200 mPa ⁇ s. More preferably, it is from s to 400 mPa ⁇ s.
• the viscosity is measured by keeping the temperature of the composition at 25° C. and using a rheometer (eg, HAAKE MARS, II manufactured by Thermo Scientific) at a rotational speed of 1000 (1/s).
• the average particle diameter of the thermoplastic particles is preferably 1 ⁇ m to 100 ⁇ m, more preferably 1 ⁇ m to 60 ⁇ m, and 5 ⁇ m to 50 ⁇ m. It is more preferably 10 ⁇ m to 30 ⁇ m, most preferably 10 ⁇ m to 20 ⁇ m.
• the average particle diameter of the thermoplastic particles is intended to be a 50% volume cumulative diameter (D50). The average particle diameter is measured using a particle size analyzer (for example, "FPER-1000" manufactured by Otsuka Electronics Co., Ltd.).
• the thermoplastic particles may be thermoplastic resin particles or elastomer particles.
• the thermoplastic particles are preferably elastomer particles from the viewpoint of the dielectric loss tangent of the film, the suitability for laser processing, and the ability to follow steps.
• elastomer refers to a compound that exhibits elastic deformation. In other words, it is defined as a compound that instantly deforms in response to an external force when applied to it, and recovers its original shape in a short period of time when the external force is removed.
• Elastomers have the property of being able to deform up to 200% with a small external force at room temperature (20°C), and return to 110% or less in a short time when the external force is removed, assuming the original size is 100%. It is preferable to have.
• the weight average molecular weight of the elastomer constituting the elastomer particles or the thermoplastic resin constituting the thermoplastic resin particles should be 1,000,000 or less. It is preferably from 3,000 to 300,000, even more preferably from 5,000 to 100,000, particularly preferably from 5,000 to 30,000.
• the elastomer constituting the elastomer particles is not particularly limited, and examples include elastomers containing repeating units derived from styrene (i.e., polystyrene elastomers), polyester elastomers, polyolefin elastomers, polyurethane elastomers, polyamide elastomers, Examples include acrylic elastomers, silicone elastomers, polyimide elastomers, and the like. Note that the thermoplastic elastomer may be a hydrogenated product.
• polystyrene-based elastomers examples include styrene-butadiene-styrene block copolymer (SBS), styrene-isoprene-styrene block copolymer (SIS), polystyrene-poly(ethylene-propylene) diblock copolymer (SEP), and polystyrene.
• SBS styrene-butadiene-styrene block copolymer
• SIS styrene-isoprene-styrene block copolymer
• SEP polystyrene-poly(ethylene-propylene) diblock copolymer
• polystyrene-based elastomers examples include styrene-butadiene-styrene block copolymer (SBS), styrene-isoprene-styrene block copolymer (SIS), polystyren
• SEPS Poly(ethylene-propylene)-polystyrene triblock copolymer
• SEBS styrene-ethylene-butylene-styrene block copolymer
• SEEPS polystyrene-poly(ethylene/ethylene-propylene)-polystyrene triblock copolymer
• SEEPS polystyrene-poly(ethylene/ethylene-propylene)-polystyrene triblock copolymer
• thermoplastic resins constituting the thermoplastic resin particles include polyurethane resin, polyester resin, (meth)acrylic resin, polystyrene resin, fluororesin, polyimide resin, fluorinated polyimide resin, polyamide resin, polyamideimide resin, and polyetherimide resin.
• cellulose acylate resin for example, polyethylene resin, polypropylene resin, resin consisting of a cyclic olefin copolymer, alicyclic polyolefin resin), polyarylate resin, polyether sulfone
• polysulfone resins include resins, polysulfone resins, fluorene ring-modified polycarbonate resins, alicyclic-modified polycarbonate resins, fluorene ring-modified polyester resins, and the like.
• the thermoplastic particles are made of a resin having a structural unit having an aromatic hydrocarbon group and an elastomer having a constitutional unit having an aromatic hydrocarbon group. It is preferable to include at least one of them.
• the structural unit having an aromatic hydrocarbon group include a phenylethylene group and a butylene terephthalate group.
• the thermoplastic particles preferably contain a polystyrene elastomer, more preferably a hydrogenated polystyrene elastomer, and hydrogenated styrene-ethylene.
• -Butylene-styrene block copolymer is more preferably included.
• the content of thermoplastic particles based on the total mass of solids contained in the first composition is preferably 50% by mass or more, and 50% by mass or more. It is more preferably from 60% to 85% by weight, and even more preferably from 60% to 85% by weight.
• the first composition may contain only one type of thermoplastic particles, or may contain two or more types of thermoplastic particles.
• the first composition includes a liquid crystal polymer.
• the aromatic polyester resin is preferably a polymer exhibiting liquid crystallinity (liquid crystal polymer).
• the liquid crystal aromatic polyester resin may be a thermotropic liquid crystal polymer or a lyotropic liquid crystal polymer. Further, in the case of a thermotropic liquid crystal polymer, it is preferably a liquid crystal polymer that melts at a temperature of 450° C. or lower.
• Aromatic polyester resins include aromatic polyester, aromatic polyesteramide in which amide bonds are introduced into aromatic polyester, aromatic polyester ethers in which ether bonds are introduced into aromatic polyester, and aromatic polyester resins in which carbonate bonds are introduced into aromatic polyester. It is preferable to contain one or more types selected from aromatic polyester carbonates, and it is more preferable to contain aromatic polyesteramide.
• the aromatic polyester resin contains an aromatic polyester amide, from the viewpoint of product flexibility, the content of the aromatic polyester amide based on the total mass of the aromatic polyester resin is preferably 50% by mass or more, and 70% by mass or more. It is more preferably at least 90% by mass, even more preferably at least 95% by mass, most preferably 100% by mass.
• aromatic polyester resins include the following liquid crystal polymers. 1) (i) aromatic hydroxycarboxylic acid, (ii) aromatic dicarboxylic acid, and (iii) at least one compound selected from the group consisting of aromatic diol, aromatic hydroxyamine, and aromatic diamine; Something made by polycondensation. 2) A product obtained by polycondensing multiple types of aromatic hydroxycarboxylic acids. 3) A product obtained by polycondensing (i) an aromatic dicarboxylic acid and (ii) at least one compound selected from the group consisting of an aromatic diol, an aromatic hydroxyamine, and an aromatic diamine.
• a product obtained by polycondensing (i) a polyester such as polyethylene terephthalate and (ii) an aromatic hydroxycarboxylic acid.
• a polyester such as polyethylene terephthalate
• an aromatic hydroxycarboxylic acid the aromatic hydroxycarboxylic acid, aromatic dicarboxylic acid, aromatic diol, aromatic hydroxyamine, and aromatic diamine may each be independently replaced with a polycondensable derivative.
• aromatic hydroxycarboxylic acids and aromatic dicarboxylic acids can be replaced with aromatic hydroxycarboxylic acid esters and aromatic dicarboxylic acid esters.
• aromatic hydroxycarboxylic acids and aromatic dicarboxylic acids can be replaced with aromatic hydroxycarboxylic acid halides and aromatic dicarboxylic acid halides.
• aromatic hydroxycarboxylic acids and aromatic dicarboxylic acids can be replaced with aromatic hydroxycarboxylic acid anhydrides and aromatic dicarboxylic acid anhydrides.
• polymerizable derivatives of compounds having hydroxy groups such as aromatic hydroxycarboxylic acids, aromatic diols, and aromatic hydroxyamines include those obtained by acylating a hydroxy group to convert it into an acyloxy group (acylated products) can be mentioned.
• aromatic hydroxycarboxylic acids, aromatic diols, and aromatic hydroxyamines can each be replaced with acylated products.
• polymerizable derivatives of compounds having an amino group such as aromatic hydroxyamines and aromatic diamines include those obtained by acylating an amino group to convert it into an acylamino group (acylated product). For example, by acylating an amino group to convert it into an acylamino group, aromatic hydroxyamine and aromatic diamine can each be replaced with an acylated product.
• the aromatic polyester resin is a structural unit represented by any of the following formulas (1) to (3) (hereinafter, formula (1)). ) is sometimes referred to as the structural unit (1) etc.), it is more preferable to have the structural unit represented by the following formula (1), and the structural unit represented by the following formula (1) etc. is preferable. ), a structural unit represented by the following formula (2), and a structural unit represented by the following formula (3) are particularly preferable.
• Ar 1 represents a phenylene group, a naphthylene group, or a biphenylylene group
• Ar 2 and Ar 3 each independently represent a phenylene group, a naphthylene group, a biphenylylene group
• the following formula (4) represents a group represented by, X and Y each independently represent an oxygen atom or an imino group, and the hydrogen atoms in Ar 1 to Ar 3 are each independently substituted with a halogen atom, an alkyl group, or an aryl group. It's okay.
• Ar 4 and Ar 5 each independently represent a phenylene group or a naphthylene group, and Z represents an oxygen atom, a sulfur atom, a carbonyl group, a sulfonyl group, or an alkylene group.
• halogen atom examples include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.
• alkyl groups include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, s-butyl group, t-butyl group, n-hexyl group, 2-ethylhexyl group, Examples include n-octyl group and n-decyl group.
• the number of carbon atoms in the alkyl group is preferably 1 to 10.
• aryl group examples include phenyl group, o-tolyl group, m-tolyl group, p-tolyl group, 1-naphthyl group and 2-naphthyl group.
• the number of carbon atoms in the aryl group is preferably 6 to 20.
• the number of substitutions in Ar 1 , Ar 2 or Ar 3 is preferably 2 or less, more preferably 1, each independently.
• alkylene group examples include a methylene group, a 1,1-ethanediyl group, a 1-methyl-1,1-ethanediyl group, a 1,1-butanediyl group, and a 2-ethyl-1,1-hexanediyl group.
• the alkylene group preferably has 1 to 10 carbon atoms.
• Structural unit (1) is a structural unit derived from aromatic hydroxycarboxylic acid.
• the structural unit (1) includes an embodiment in which Ar 1 is a p-phenylene group (a structural unit derived from p-hydroxybenzoic acid), and an embodiment in which Ar 1 is a 2,6-naphthylene group (6-hydroxy- A structural unit derived from 2-naphthoic acid) or a 4,4'-biphenylylene group (a structural unit derived from 4'-hydroxy-4-biphenylcarboxylic acid) is preferred.
• the structural unit (2) is a structural unit derived from an aromatic dicarboxylic acid.
• the structural unit (2) includes an embodiment in which Ar 2 is a p-phenylene group (a structural unit derived from terephthalic acid), an embodiment in which Ar 2 is a m-phenylene group (a structural unit derived from isophthalic acid), and an embodiment in which Ar 2 is a m-phenylene group (a structural unit derived from isophthalic acid).
• Ar 2 is a diphenyl ether-4,4'-diyl group (diphenyl ether-4,4'- structural units derived from dicarboxylic acids) are preferred.
• the structural unit (3) is a structural unit derived from aromatic diol, aromatic hydroxylamine, or aromatic diamine.
• the structural unit (3) includes an embodiment in which Ar 3 is a p-phenylene group (a structural unit derived from hydroquinone, p-aminophenol, or p-phenylenediamine), and an embodiment in which Ar 3 is a m-phenylene group (isophthalic acid). ), or an embodiment in which Ar 3 is a 4,4'-biphenylylene group (derived from 4,4'-dihydroxybiphenyl, 4-amino-4'-hydroxybiphenyl or 4,4'-diaminobiphenyl) structural units) are preferred.
• the content of the structural unit (1) is the total amount of all structural units [i.e., the mass of each structural unit (also referred to as "monomer unit") constituting the aromatic polyester resin divided by the formula weight of each structural unit.
• the substance amount equivalent (mol) of each structural unit is calculated, and the sum of these amounts is preferably 30 mol% or more, more preferably 30 mol% to 80 mol%, and even more preferably 30 mol%. % to 60 mol%, particularly preferably 30 mol% to 40 mol%.
• the content of the structural unit (2) is preferably 35 mol% or less, more preferably 10 mol% to 35 mol%, 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 content of the structural unit (1) increases, the heat resistance, strength, and rigidity of the aromatic polyester resin tend to improve, but if the content is too large, the solubility in the solvent tends to decrease.
• 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 aromatic polyester resin may each independently have two or more types of structural units (1) to (3). Further, the aromatic polyester resin may have structural units other than structural units (1) to (3), but the content thereof is preferably 10 mol% or less with respect to the total amount of all structural units. , more preferably 5 mol% or less.
• the aromatic polyester resin has a structural unit (3) in which at least one of X and Y is an imino group, that is, as a structural unit (3), It is preferable to have at least one of a structural unit derived from an aromatic 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 aromatic polyester resin is preferably produced by melt polymerizing raw material monomers corresponding to the structural units constituting the aromatic polyester resin. 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 4-(dimethylamino)pyridine and 1-methylimidazole.
• nitrogen-containing heterocyclic compounds and nitrogen-containing heterocyclic compounds are preferred.
• you may further implement solid phase polymerization with respect to the polymer obtained by melt polymerization as needed.
• the lower limit of the flow start temperature of the aromatic polyester resin 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 preferred, and even more preferably 310°C.
• the solubility, heat resistance, strength and rigidity are excellent, and the viscosity of the solution is appropriate.
• the flow start temperature is also called the flow temperature or flow temperature
• the liquid crystal polymer is melted using a capillary rheometer while increasing the temperature at a rate of 4°C/min under a load of 9.8 MPa (100 kg/cm 2 ).
• This is the temperature at which liquid crystal polymers exhibit a viscosity of 4,800 Pa ⁇ s (48,000 poise) when extruded through a nozzle with an inner diameter of 1 mm and a length of 10 mm, which is a guideline for the molecular weight of liquid crystal polymers (edited by Naoyuki Koide). , "Liquid Crystal Polymers - Synthesis, Molding, and Applications," CMC Co., Ltd., June 5, 1987, p. 95).
• the weight average molecular weight of the aromatic polyester resin is preferably 1,000,000 or less, more preferably 3,000 to 300,000, and even more preferably 5,000 to 100,000. It is preferably 5,000 to 30,000, particularly preferably 5,000 to 30,000. When the weight average molecular weight of the aromatic polyester resin is within the above range, the film after heat treatment has excellent thermal conductivity, heat resistance, strength and rigidity in the thickness direction.
• the aromatic polyester resin is preferably a polymer soluble in a specific organic solvent (hereinafter also referred to as "soluble polymer").
• the soluble polymers include N-methylpyrrolidone, N-ethylpyrrolidone, dichloromethane, dichloroethane, chloroform, N,N-dimethylacetamide, ⁇ -butyrolactone, dimethylformamide, ethylene glycol monobutyl ether, and ethylene glycol at 25°C.
• 0.1 g or more is dissolved in 100 g of at least one solvent selected from the group consisting of monoethyl ether, preferably N-methylpyrrolidone (that is, the solubility in the solvent is 0.1% by mass or more); It is more preferable that 5 g or more is dissolved (solubility in the sieve is 0.5% by mass or more), and even more preferably 1.0 g or more is dissolved (solubility in the sieve is 1% by mass or more).
• the content of the aromatic polyester resin based on the total mass of solids contained in the first composition is preferably less than 50% by mass, It is more preferably 5% by mass to 50% by mass, and even more preferably 15% by mass to 40% by mass.
• the first composition may contain only one type of aromatic polyester resin, or may contain two or more types of aromatic polyester resin.
• solvent contained in the first composition examples include dichloromethane, chloroform, 1,1-dichloroethane, 1,2-dichloroethane, 1,1,2,2-tetrachloroethane, 1-chlorobutane, chlorobenzene, o-dichlorobenzene.
• halogenated hydrocarbons such as p-chlorophenol, pentachlorophenol, pentafluorophenol; ethers such as diethyl ether, tetrahydrofuran, 1,4-dioxane; ketones such as acetone, cyclohexanone; ethyl acetate, ⁇ - Esters such as butyrolactone; carbonates such as ethylene carbonate and propylene carbonate; amines such as triethylamine; nitrogen-containing heteroaromatic compounds such as pyridine; nitriles such as acetonitrile and succinonitrile; N,N-dimethylformamide, N,N - Amides such as dimethylacetamide and N-methylpyrrolidone; urea compounds such as tetramethylurea; nitro compounds such as nitromethane and nitrobenzene; sulfur compounds such as dimethylsulfoxide and sulfolane; hexamethylphosphoric acid
• the above-mentioned solvent preferably contains an aprotic compound (particularly preferably an aprotic compound having no 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, more preferably N,N-dimethylformamide, N,N-dimethylacetamide, or N-methylpyrrolidone, and even more preferably 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 it is preferable to include a compound having a boiling point of 220° C. or less at 1 atmosphere, since it can be easily removed if necessary.
• the proportion of the compound having a boiling point of 220°C or less at 1 atm in the entire solvent contained in the first composition is preferably 50% by mass to 100% by mass, more preferably 70% by mass to 100% by mass, particularly preferably It is 90% by mass to 100% by mass.
• the aprotic compound it is preferable to use a compound whose boiling point at 1 atmosphere is 220° C. or less.
• the content of the solvent with respect to the total mass of the first composition is preferably 50% by mass to 95% by mass, and 70% by mass to 90% by mass. It is more preferable that there be.
• the first composition may contain only one type of solvent, or may contain two or more types of solvent.
• the first composition may or may not contain components other than those described above (other additives).
• Other components include organic fillers (described later), inorganic fillers (described later), surfactants, matting agents, hardening agents, leveling agents, antifoaming agents, antioxidants, ultraviolet absorbers, flame retardants, colorants, etc.
• the first composition may or may not contain resins other than the aromatic polyester resin (other resins).
• resins conventionally known resins can be used, and examples thereof include non-aromatic polyester resins, fluorine resins, polyolefin resins, polyamide resins, polyimide resins, and phenol resins.
• composition according to second aspect includes thermoplastic particles, an aromatic polyester resin, and a solvent, and the above-mentioned composition is based on the total mass of solids contained in the composition.
• the content of thermoplastic particles is 50% by mass or more.
• the content of the thermoplastic particles with respect to the total mass of solids contained in the second composition is preferably 50% by mass to 95% by mass. It is preferably 60% by mass to 85% by mass.
• the average particle diameter of the thermoplastic particles contained in the second composition with respect to the thickness of the layer formed by the following method using the second composition.
• the ratio (average particle diameter of thermoplastic particles/layer thickness) is preferably 1.5 or less, more preferably 1.5 to 0.1, and preferably 1 to 0.1. More preferably, it is 0.7 to 0.1.
• Method for forming a layer The second composition is applied to the surface of the copper base material in a coating amount of 0.015 g/cm 2 and heated in an environment of 180° C. for 300 minutes to form a layer.
• the viscosity of the second composition is preferably 50 mPa ⁇ s to 2000 mPa ⁇ s, more preferably 100 mPa ⁇ s to 1000 mPa ⁇ s, and 200 mPa ⁇ s. More preferably, it is from s to 400 mPa ⁇ s.
• the average particle diameter of the thermoplastic particles is preferably 100 ⁇ m or less, more preferably 1 ⁇ m to 100 ⁇ m, and 1 ⁇ m to 60 ⁇ m. It is more preferably 5 ⁇ m to 50 ⁇ m, most preferably 10 ⁇ m to 30 ⁇ m, and may be 10 ⁇ m to 20 ⁇ m.
• thermoplastic particles Preferred embodiments of the thermoplastic particles, aromatic polyester resin, and solvent are the same as those of the first composition, so descriptions thereof will be omitted here.
• the second composition may or may not contain other resins and other additives. Since these are the same as those in the first composition, their description will be omitted here.
• the second composition may contain only one kind of each component, or may contain two or more kinds of each component.
• the film of the present disclosure has a layer A and a layer B on at least one surface of the layer A,
• the layer B includes particles (hereinafter also referred to as specific particles) containing at least one of a resin having a constitutional unit having an aromatic hydrocarbon group and an elastomer having a constitutional unit having an aromatic hydrocarbon group; Contains polyester resin,
• the minimum area ratio of the specific particles in the thickness direction cross section of the layer B is 50% or more.
• the film of the present disclosure has excellent step followability and excellent suitability for laser processing. Although the reason for the above effect is not clear, it is presumed as follows.
• Layer B included in the film of the present disclosure has a minimum area ratio of the specific particles in the thickness direction cross section of 50% or more, and the dispersibility of the specific particles in layer B is high. As a result, the elastic modulus of layer B is uniformly lowered during hot pressing, and it follows the copper wiring pattern, so it is presumed that the step followability is improved.
• the specific particles have high dispersibility, there are no or very few areas where specific particles are locally present in layer B, and over-cutting during laser processing due to uneven distribution of specific particles is suppressed. It is assumed that this improves suitability for laser processing.
• the minimum area ratio of specific particles in the thickness direction cross section of layer B is preferably 50% to 90%, more preferably 60% to 85%, and even more preferably 70% to 80%.
• the minimum area ratio is measured as follows. First, a cross section of the film is observed with an optical microscope to obtain an optical microscope image. Next, the optical microscope image is subjected to a binarization process to visualize the distribution of the aromatic polyester resin and specific particles contained in layer B.
• the area ratio of the specific particles to a unit area (for example, when the thickness of layer B is 30 ⁇ m, 400 ⁇ m 2 (20 ⁇ m x 20 ⁇ m)) with one side being 2/3 of the film thickness, Measurements are taken at 10 locations at 10 ⁇ m intervals from the center of layer B. Among the 10 locations, the one with the minimum area ratio of specific particles is defined as the above-mentioned minimum area ratio.
• the particles contained in layer B are particles containing a resin having a constitutional unit having an aromatic hydrocarbon group or an elastomer having a constitutional unit having an aromatic hydrocarbon group can be determined by SEM-EDX (scanning). Judgment is made by elemental analysis using Scanning Electron Microscope-Energy Dispersive X-ray Spectroscopy.
• the elastic modulus of layer A at 160° C. in the film of the present disclosure is preferably 100 MPa to 2,500 MPa, more preferably 200 MPa to 2,000 MPa, from the viewpoint of laser processing suitability and step tracking ability. , more preferably from 300 MPa to 1,500 MPa, particularly preferably from 500 MPa to 1,000 MPa.
• the elastic modulus of layer B at 160° C. in the film of the present disclosure is preferably 100 MPa or less, more preferably 10 MPa or less, and 0.001 MPa to 10 MPa, from the viewpoint of laser processing suitability and step followability. More preferably, it is 0.5 MPa to 5 MPa.
• the ratio of the elastic modulus MD A at 160° C. of layer A to the elastic modulus MD B at 160° C. of layer B in the film of the present disclosure is determined from the viewpoint of laser processing suitability and level difference followability. , is preferably 1.2 or more, more preferably 5 to 1,000, even more preferably 10 to 500, and particularly preferably 100 to 400.
• 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 is measured as an indentation elastic modulus using a nanoindentation method. The indentation modulus was measured using a microhardness meter (for example, product name "DUH-W201", manufactured by Shimadzu Corporation) at 160°C, applying a load with a Vickers indenter at a loading rate of 0.28 mN/sec, and measuring the maximum load.
• a microhardness meter for example, product name "DUH-W201", manufactured by Shimadzu Corporation
• the measurement is performed by unloading at a loading rate of 0.28 mN/second.
• the elastic modulus of layers other than layer A and layer B is similarly measured.
• unnecessary layers may be scraped off with a razor or the like, and a sample for evaluation of only the desired layer may be prepared and used as a measurement sample.
• the layer to be measured may be scraped off with a razor, etc., and the resulting powder form may be used as a sample for measuring the elastic modulus. .
• the film of 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 at 28 GHz is preferably 0.01 or less, more preferably 0.005 or less, and preferably 0.004 or less, from the viewpoints of the film's dielectric loss tangent, laser processing suitability, and step followability. More preferably, it is particularly preferably 0.003 or less.
• the lower limit value is not particularly set, but may be, for example, greater than 0.
• Layer A in the film of the present disclosure preferably contains a liquid crystal polymer from the viewpoints of dielectric loss tangent, laser processing suitability, and step tracking ability of the film.
• the liquid crystal polymer is preferably a polymer having an aromatic ring, and more preferably an aromatic polyester resin, from the viewpoints of the dielectric loss tangent, liquid crystallinity, and coefficient of thermal expansion of the film.
• the aromatic polyester resin is as described in the first composition, and the aromatic polyester resin preferably contains an aromatic polyester amide.
• the liquid crystal polymer is preferably a polymer that is soluble in a specific organic solvent (soluble polymer).
• soluble polymer include N-methylpyrrolidone, N-ethylpyrrolidone, dichloromethane, dichloroethane, chloroform, N,N-dimethylacetamide, ⁇ -butyrolactone, dimethylformamide, ethylene glycol monobutyl ether at 25°C.
• solubility in the solvent is 0.1% by mass or more
• solubility in the solvent is 0.1% by mass or more
• 0.5 g or more is dissolved (solubility in the solvent is 0.5% by mass or more)
• 1.0g or more is dissolved (solubility in the solvent is 1% by mass or more).
• Layer A may contain only one type of liquid crystal polymer, or may contain two or more types.
• the content of the liquid crystal polymer relative to the total mass of layer A is preferably 10% by mass to 100% by mass, and preferably 15% to 70% by mass from the viewpoint of the dielectric loss tangent of the film and the adhesion with metal. It is more preferably 20% by mass to 50% by mass, and particularly preferably 25% by mass to 40% by mass.
• Layer A may contain a filler from the viewpoint of thermal expansion coefficient and adhesion to metal.
• the filler may be particulate or fibrous, and may be an inorganic filler or an organic filler.
• the filler is preferably an organic filler from the viewpoint of the dielectric loss tangent of the film, suitability for laser processing, and step followability.
• 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 the air or the substrate), and the range of 3 ⁇ m from the most surface in the depth direction, or 10% of the total thickness of the film from the most surface.
• the smaller of the following ranges is defined as the "surface”.
• the inside of the film refers to parts other than the surface of the film, that is, the inner surface of the film (the surface that does not contact the air or the substrate), and includes, but is not limited to, the area within ⁇ 1.5 ⁇ m from the center of the film in the thickness direction.
• the smaller value of the range or the range of ⁇ 5% of the total thickness from the center in the thickness direction of the film is defined as "inside".
• organic filler known organic fillers can be used.
• the material of the organic filler include polyethylene, polystyrene, urea-formalin resin, polyester, cellulose, acrylic resin, fluorine resin, hardened epoxy resin, crosslinked benzoguanamine resin, crosslinked acrylic resin, liquid crystal polymer, and two or more of these.
• materials include:
• the organic filler may be a fibrous filler such as nanofibers, or may be a hollow resin particle.
• fluororesin particles, polyester resin particles, polyethylene particles, liquid crystal polymer particles, or cellulose resin nanofibers are used as the organic filler.
• the liquid crystal polymer particles refer to, but are not limited to, those obtained by polymerizing a liquid crystal polymer and pulverizing it with a pulverizer or the like to obtain a powdered liquid crystal.
• the average particle size of the liquid crystal polymer particles as the organic filler is preferably smaller than the thickness of each layer.
• the average particle size of the organic filler is preferably from 5 nm to 20 ⁇ m, more preferably from 100 nm to 10 ⁇ m, from the viewpoint of dielectric loss tangent of the film, suitability for laser processing, and ability to follow steps.
• 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 fibers are particularly preferred.
• the average particle size of the inorganic filler is preferably about 20% to about 40% of the thickness of layer A.
• the inorganic filler may be selected to have an average particle size of 25%, 30% or 35% of the thickness of layer A, for example.
• the average particle diameter is a value measured based on the length in the short side direction.
• the average particle size of the inorganic filler is preferably 5 nm to 20 ⁇ m, more preferably 10 nm to 10 ⁇ m, and 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. Further, the content of the filler relative to the total mass of layer A is preferably 5% to 90% by mass, and 30% to 85% by mass from the viewpoint of suitability for laser processing and adhesion to metal. It is more preferably 50% to 80% by weight, particularly preferably 60% to 75% by weight.
• Layer A may contain other additives. Since the other additives are the same as those in the first composition, their description is omitted here.
• 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 adhesiveness with metal.
• the value of T A /T B which is the ratio of the average thickness T A of layer A to the average thickness T B of layer B, is 0.8 to 10 from the viewpoint of the dielectric loss tangent of the film and the adhesion with metal. It is preferably from 1 to 5, even more preferably from more than 1 to 3 or less, and particularly preferably from more than 1 to 2 or less.
• the average thickness of layer A is not particularly limited, but from the viewpoint of dielectric loss tangent of the film and adhesion to 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 film of 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 at least three points on each section, and use the average value as the average thickness.
• the film of the present disclosure has layer B on at least one surface of layer A.
• the dielectric loss tangent of layer B at 28 GHz is preferably 0.01 or less, more preferably 0.005 or less, and preferably 0.004 or less, from the viewpoints of the film's dielectric loss tangent, laser processing suitability, and step followability. More preferably, it is particularly preferably 0.003 or less. Any lower limit value is not particularly set, but may be, for example, greater than 0.
• Layer B contains one or more types of specific particles.
• the specific particles include at least one of a resin having a constitutional unit having an aromatic hydrocarbon group, and an elastomer having a constitutional unit having an aromatic hydrocarbon group. Since the aromatic hydrocarbon group is as explained in the first composition, its description is omitted here. From the viewpoints of dielectric loss tangent, laser processing suitability, and level difference followability of the film, it is preferable that the specific particles include an elastomer having a structural unit having an aromatic hydrocarbon group.
• the content of the elastomer having a structural unit having an aromatic hydrocarbon group relative to the total mass of the specific particle may be 50% by mass or more. It is preferably 70% by mass or more, more preferably 90% by mass or more, particularly preferably 95% by mass or more, and most preferably 100% by mass.
• the resin having a structural unit having an aromatic hydrocarbon group may be a thermoplastic resin.
• the thermoplastic resin is not limited as long as it has a structural unit having an aromatic hydrocarbon group, and includes the thermoplastic resins described in the first composition.
• the elastomer having a structural unit having an aromatic hydrocarbon group is not limited as long as it has a structural unit having an aromatic hydrocarbon group, and examples thereof include the elastomers described in the first composition.
• the elastomer having a structural unit having an aromatic hydrocarbon group is more preferably a polystyrene-based elastomer, and preferably a hydrogenated polystyrene-based elastomer. is more preferred, and hydrogenated styrene-ethylene-butylene-styrene block copolymer is even more preferred.
• the content of the specific particles relative to the total mass of layer B is preferably 50% by mass or more, and 50% by mass to 95% by mass.
• the content is more preferably 60% by mass to 85% by mass.
• layer B includes a liquid crystal polymer.
• Layer B contains one or more aromatic polyester resins. Since the aromatic polyester resin is the same as that of the first composition, its description is omitted here.
• the content of the aromatic polyester resin based on the total mass of layer B is preferably less than 50% by mass, and 5% by mass to 50% by mass. It is more preferable that the amount is 15% by mass to 40% by mass.
• Layer B may or may not contain other additives and other resins. Other additives and other resins that may be included in layer B are the same as those in the first composition, so their descriptions are omitted here.
• 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 film of the present disclosure provides a film that has excellent adhesion to metals.
• layer A has a filler
• layer B is preferably a surface layer (outermost layer).
• the film is used as a laminate (a laminate with a metal layer) having a layer configuration of metal layer/layer A/layer B, another metal layer or a laminate with a metal layer is further placed on the layer B side. There are things to do.
• the polymer contained in layer B contains a polymer having higher breaking strength (toughness) than the polymer contained in layer A.
• the breaking strength shall be measured by the following method. A sample made of the polymer to be measured was prepared, and the stress against elongation was measured using a universal tensile tester "STM T50BP" manufactured by Toyo Baldwin Co., Ltd. at a tensile rate of 10%/min at 25°C and 60% RH, and Find the breaking strength.
• the film of 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 A, the layer C, and the layer B in this order.
• Layer C is preferably an adhesive layer. Further, when a metal layer is present apart from the above-mentioned layers, layer C is preferably a surface layer (outermost layer).
• Layer C preferably contains a polymer having a dielectric loss tangent of 0.01 or less at 28 GHz, from the viewpoint of the dielectric loss tangent of the film and suitability for laser processing.
• 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.
• the polymer having a dielectric loss tangent of 0.01 or less may be a liquid crystal polymer.
• the liquid crystal polymer is preferably a polymer having an aromatic ring, and more preferably an aromatic polyester resin, from the viewpoints of dielectric loss tangent, liquid crystallinity, and coefficient of thermal expansion of the film.
• the content of the polymer having a dielectric loss tangent of 0.01 or less with respect to the total mass of the layer C is preferably 10% by mass to 99% by mass, from the viewpoint of the dielectric loss tangent of the film and the adhesion with metal. It is more preferably 20% by mass to 95% by mass, even more preferably 30% by mass to 90% by mass, and particularly preferably 40% by mass 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.
• layer C preferably contains an epoxy resin in order to bond the metal layer and the resin layer (for example, layer A).
• 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 may or may not contain other additives.
• Other additives that may be included in layer C are the same as those in the first composition, so descriptions thereof will be omitted here.
• 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. , more 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 film of the present disclosure is preferably 6 ⁇ m to 200 ⁇ m, more preferably 12 ⁇ m to 100 ⁇ m, from the viewpoint of strength and electrical properties (characteristic impedance) when formed into a laminate with a metal layer.
• the thickness is preferably from 20 ⁇ m to 80 ⁇ m.
• the dielectric loss tangent of the film of the present disclosure at 28 GHz is preferably 0.008 or less, more preferably 0.005 or less, even more preferably 0.004 or less, and 0. It is especially preferable that it exceeds 0.003 or less.
• the method for producing the film of the present disclosure is not particularly limited, and known methods can be referred to. Suitable methods for producing the film of the present disclosure include, for example, a co-casting method, a multilayer coating method, a co-extrusion method, and the like. Among these, the co-casting method is particularly preferable for forming a relatively thin film, and the co-extrusion method is particularly preferable for forming a thick film.
• components of each layer are dissolved or dispersed in a solvent as a composition for forming layer A, a composition for forming layer B, a composition for forming layer C, etc., and co-casting. It is preferable to use a coating method or a multilayer coating method.
• a support may be used when the film is produced by the above-mentioned co-casting method, multilayer coating method, co-extrusion method, or the like. Furthermore, when a metal layer (metal foil) or the like used in a laminate described later is used as a support, it may be used as it is without being peeled off. Examples of the support include a metal drum, metal band, glass plate, resin film, or metal foil. Among these, metal drums, metal bands, and resin films are preferred.
• Examples of the resin film include polyimide (PI) films, and examples of commercially available products include U-Pyrex S and U-Pyrex R manufactured by Ube Industries, Ltd., Kapton manufactured by DuPont Toray Co., Ltd., and Examples include IF30, IF70, and LV300 manufactured by SKC Kolon PI.
• a surface treatment layer may be formed on the surface of the support so that it can be easily peeled off.
• hard chrome plating, fluororesin, etc. can be used.
• the average thickness of the support is not particularly limited, but is preferably 25 ⁇ m or more and 75 ⁇ m or less, more preferably 50 ⁇ m or more and 75 ⁇ m or less.
• the method for removing at least a portion of the solvent from the cast or applied film-like composition is not particularly limited, and any known drying method may be used. .
• the film of the present disclosure can be stretched as appropriate from the viewpoint of controlling molecular orientation and adjusting linear expansion coefficient and mechanical properties.
• the stretching method is not particularly limited, and known methods can be referred to, and stretching may be carried out in a state containing a solvent or in a dry film state. Stretching in a state containing a solvent may be carried out by gripping and stretching the film, or may be carried out by utilizing self-shrinkage due to drying without stretching. Stretching is particularly effective for improving elongation at break and strength at break when film brittleness is reduced by addition of inorganic fillers or the like.
• the method for producing a film of the present disclosure may include a step of polymerizing with light or heat, as necessary.
• the light irradiation means and heat application means are not particularly limited, and known light irradiation means such as a metal halide lamp, and known heat application means such as a heater can be used.
• the light irradiation conditions and the heat application conditions are not particularly limited, and can be performed at a desired temperature and time and in a known atmosphere.
• the method for producing a film of the present disclosure preferably includes a step of heat-treating (annealing) the film.
• the heat treatment temperature in the above heat treatment step is preferably 260°C to 370°C, more preferably 280°C to 360°C, and 300°C to 350°C from the viewpoint of dielectric loss tangent and peel strength. It is more preferable that The heat treatment time is preferably 15 minutes to 10 hours, more preferably 30 minutes to 5 hours.
• the method for producing a film of the present disclosure may include other known steps as necessary.
• the film of the present disclosure can be used for various purposes, among which it can be suitably used as a film for electronic components such as printed wiring boards, and can be suitably used for flexible printed circuit boards.
• the film of the present disclosure can be used by being attached to a conductive pattern or circuit wiring.
• the laminate according to the present disclosure may be one in which the films of the present disclosure are laminated, but the laminate includes the film of the present disclosure and a metal layer or metal wiring disposed on at least one surface of the film. It is preferable that Further, the laminate according to the present disclosure includes layer A, layer B, and a metal layer or metal wiring in this order, and layer B includes a resin having a structural unit having an aromatic hydrocarbon group, and an aromatic Particles containing at least one of elastomers having a structural unit having a group hydrocarbon group (hereinafter also referred to as specific particles), and an aromatic polyester resin, It is preferable that the minimum area ratio of the specific particles in the thickness direction cross section of the layer B is 50% or more.
• the laminate according to the present disclosure preferably includes the film of the present disclosure and a metal layer disposed on the layer B side surface of the film, and it is more preferable that the metal layer is a copper layer.
• the metal layer disposed on the layer B side surface is preferably a metal layer disposed on the surface of the layer B.
• the laminate according to the present disclosure includes a film of the present disclosure having layer B, layer A, and layer C in this order, a metal layer disposed on the layer B side surface of the film, and It is preferable to have a metal layer disposed on the surface of the film on the layer C side, and it is more preferable that all the metal layers are copper layers.
• the metal layer disposed on the layer C side surface is preferably a metal layer disposed on the surface of the layer C, and the metal layer disposed on the layer B side surface is preferably a metal layer disposed on the layer B side surface. It is more preferable that the metal layer disposed on the surface of the layer C is the metal layer disposed on the surface of the layer C. Furthermore, even if the metal layer disposed on the layer B side surface and the metal layer disposed on the layer C side surface have the same material, thickness, and shape, they may be made of different materials and have different thicknesses. and shaped metal layers.
• the metal layer disposed on the surface on the layer B side and the metal layer disposed on the surface on the layer C side may be metal layers of different materials and thicknesses.
• a metal layer may be laminated only on one side of layer B or layer C.
• an embodiment in which a metal layer is laminated on one side of layer B or layer C and another film is laminated on the other side is also preferably mentioned.
• the peel strength between the film and the copper layer is preferably 0.5 kN/m or more, more preferably 0.7 kN/m or more, It is more preferably .7 kN/m to 2.0 kN/m, and particularly preferably 0.9 kN/m to 1.5 kN/m.
• the peel strength between a film and a metal layer shall be measured by the following method.
• a 1.0 cm wide peel test piece was prepared from the laminate of the film and the metal layer, the film was fixed to a flat plate with double-sided adhesive tape, and the film was peeled at 50 mm/min by the 180° method according to JIS C 5016 (1994).
• the strength (kN/m) is measured when the film is peeled from the metal layer at a speed of .
• the surface roughness Rz of the metal layer on the side in contact with the film is preferably less than 1 ⁇ m, more preferably 0.5 ⁇ m or less, particularly preferably 0.3 ⁇ m or less, from the viewpoint of reducing transmission loss of high-frequency signals. Note that the lower the surface roughness Rz of the metal layer is, the better, so the lower limit is not particularly set, but for example, 0 or more can be mentioned.
• surface roughness Rz refers to a value expressed in micrometers of the sum of the maximum height of the peak and the maximum value of the depth of the valley observed in the roughness curve at the reference length. means.
• the surface roughness Rz of a metal layer shall be measured by the following method. Using VertScan (manufactured by Ryoka System Co., Ltd.), a non-contact surface/layer cross-sectional shape measurement system, a square area of 465.48 ⁇ m in length and 620.64 ⁇ m in width was measured to determine the roughness curve on the surface of the object to be measured (metal layer) and the above. Create an average line for the roughness curve.
• the metal layer is preferably a copper layer.
• the copper layer is a rolled copper foil formed by a rolling method, an electrolytic copper foil formed by an electrolytic method, a copper foil formed by a sputtering method, or a copper foil formed by a vapor deposition method. It is preferable.
• the average thickness of the metal layer, preferably the copper layer, 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 metal layer is provided with a known surface treatment layer (for example, a chemical treatment layer) on the surface in contact with the film to ensure adhesive strength with the resin. It is preferable to have.
• the above-mentioned interacting group is preferably a group corresponding to a functional group of a compound having a functional group contained in the above-mentioned film, such as an amino group and an epoxy group, or a hydroxy group and an epoxy group. Examples of the group capable of interacting include the groups listed above for the functional group in the compound having the functional group. Among these, from the viewpoints of adhesion and ease of processing, a group capable of covalent bonding is preferred, an amino group or a hydroxy group is more preferred, and an amino group is particularly preferred.
• the metal layer in the laminate according to the present disclosure may be a metal layer having a circuit pattern. It is also preferable to process the metal layer in the laminate according to the present disclosure into a desired circuit pattern by etching, for example, to form a flexible printed circuit board.
• the etching method is not particularly limited, and any known etching method can be used.
• a cross section of the film was cut using a microtome or the like, and layer A or layer B was identified using an optical microscope.
• the elastic modulus of the specified layer A or layer B was measured as an indentation elastic modulus using a nanoindentation method.
• the indentation modulus was measured using a microhardness tester (product name "DUH-W201", manufactured by Shimadzu Corporation) at 160°C with a Vickers indenter at a loading rate of 0.28 mN/sec, with a maximum load of 10 mN. After holding for 10 seconds, the measurement was performed by unloading at a loading rate of 0.28 mN/sec.
• A-1 Aromatic polyester amide (liquid crystalline aromatic polyester resin) produced according to the following production method
• 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 After solid phase polymerization, the mixture was cooled. Next, it was ground with a grinder to obtain powdered aromatic polyesteramide A1b.
• the flow initiation temperature of 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 After solid phase polymerization, the mixture was cooled to obtain powdery aromatic polyesteramide A-1.
• the flow initiation temperature of aromatic polyesteramide A-1 was 302°C. Further, the melting point of the aromatic polyesteramide A-1 was measured using a differential scanning calorimeter and was found to be 311°C.
• the solubility of aromatic polyesteramide A-1 in N-methylpyrrolidone at 140° C. was 1% by mass or more.
• a-1 Liquid crystal polymer particles (filler) produced according to the following manufacturing method
• 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.
• Filler a-1 had a median diameter (D50) of 7 ⁇ m, a dielectric loss tangent of 0.0007, and a melting point of 334°C.
• thermoplastic resin b-1 and thermoplastic particles b-2 to b-5 and c-1- b-1 Tuftec M1913, Asahi Kasei Chemicals Co., Ltd., hydrogenated styrene-ethylene-butylene-styrene block copolymer b-2: Tuftec M1913, Asahi Kasei Chemicals Co., Ltd., pulverized product (average particle size 10. 0 ⁇ m (D50), thermoplastic particles, elastomer particles containing a structural unit having an aromatic hydrocarbon group) b-3: Pulverized product of Tuftec M1913, manufactured by Asahi Kasei Chemicals Co., Ltd.
• thermoplastic particles listed in Table 1 55 parts of 1 mm ⁇ Zr beads, and 38 parts of A-1 solution with a solid content concentration of 4.8% by mass, and add the prepared liquid.
• a dispersion liquid was prepared by operating a low frequency resonance acoustic mixer (Resodyn) at an acceleration of 95 G for 24 minutes. The obtained dispersion liquid was filtered through a PET mesh to remove 1 mm ⁇ Zr beads to obtain a layer B coating liquid.
• toluene was added to thermoplastic resin b-1 to adjust the solid content concentration to 20% by mass to obtain a coating liquid for layer B.
• undercoat layer coating liquid, coating liquid for layer A, and coating liquid for layer B are sent to a slot die coater equipped with a slide coater and coated with copper foil (product name: CF-T9DA-SV-18).
• CF-T9DA-SV-18 copper foil
• an average thickness of 18 ⁇ m, manufactured by Fukuda Metal Foil and Powder Industries Co., Ltd. was coated on the treated surface with a three-layer structure (undercoat layer/layer A/layer B) by adjusting the flow rate so that the film thickness was as shown in Table 1.
• the solvent was removed from the coating film by drying at 90°C for 4 hours. Further, a heat treatment was performed in which the temperature was raised from room temperature to 300° C.
• the dielectric loss tangent was measured using a resonance perturbation method at a frequency of 10 GHz.
• a 10 GHz cavity resonator (CP531, manufactured by Kanto Electronics Applied Development Co., Ltd.) was connected to a network analyzer (“E8363B” manufactured by Agilent Technology), 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.
• thermoplastic particles in the thickness direction cross section of layer B The produced single-sided copper-clad laminate was cut along the thickness direction using a cross-section polisher (manufactured by JEOL Ltd.), and the cross section was observed using an optical microscope. The obtained optical microscope image was binarized to visualize the distribution of polymer A-1 and thermoplastic particles.
• the area ratio of thermoplastic particles to a unit area for example, 20 ⁇ m x 20 ⁇ m in Example 1 where one side is 2/3 of the film thickness is determined at 10 ⁇ m intervals from the center of layer B. I found 10 locations. Among the 10 locations, the one with the smallest area ratio of thermoplastic particles is summarized in Table 1 as the minimum area ratio.
• Step tracking ability (wiring tracking ability)]
• a sample - Preparation of base material A with wiring pattern - Copper foil product name ⁇ CF-T9DA-SV-18'', average thickness 18 ⁇ m, manufactured by Fukuda Metal Foil & Powder Industries Co., Ltd.
• a liquid crystal polymer film product name ⁇ CTQ-50'', average thickness 50 ⁇ m, (manufactured by Kuraray Co., Ltd.) was prepared.
• the copper foil, the base material, and the copper foil were stacked in this order so that the treated surface of the copper foil was in contact with the base material.
• 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 heated at 300°C and 4.5 MPa for 10 minutes.
• a double-sided copper-clad laminate was produced by thermocompression bonding for a minute.
• the surfaces of the copper foils on both sides of the double-sided copper-clad laminate were roughened, and a dry film resist was laminated thereon.
• a dry film resist was laminated thereon.
• a wiring pattern with a line/space of 100 ⁇ m/100 ⁇ m including a ground line and 3 pairs of signal lines on both sides of the base material A base material was prepared.
• the length of the signal line was 50 mm, and the width was set so that the characteristic impedance was 50 ⁇ .
• a laminator product name "Vacuum Laminator V-130", manufactured by Nikko Materials Co., Ltd.
• lamination processing was performed for 1 minute at 140°C and a lamination pressure of 0.4 MPa to form a single-sided copper-clad laminate.
• the precursor of was obtained.
• thermocompression bonding machine product name "MP-SNL”, manufactured by Toyo Seiki Seisakusho Co., Ltd.
• the obtained precursor of the single-sided copper-clad laminate was heated at 300° C. and 4.5 MPa for 10 minutes.
• a single-sided copper-clad laminate was produced by thermocompression bonding for a minute.
• the base material of the single-sided copper-clad laminate and the carrier copper foil on the opposite side were peeled off, the surface of the exposed copper foil of 1.5 ⁇ m was roughened, and a dry film resist was laminated.
• a wiring pattern was exposed and developed through a dry film resist, and the areas where the resist pattern was not placed were plated. Furthermore, the dry film resist was peeled off, and the copper exposed by the peeling process was removed by flash etching, thereby producing a base material with a wiring pattern having a line/space of 20 ⁇ m/20 ⁇ m.
• the substrate with the wiring pattern prepared above was superimposed on the layer B side of the single-sided copper-clad laminate prepared above, and a wiring board was obtained by hot pressing at 160° C. and 4 MPa for 1 hour.
• the resulting wiring board has a wiring pattern (ground line and signal line) buried therein, and the thickness of the wiring pattern is 18 ⁇ m when base material A with a wiring pattern is used, and the thickness of the wiring pattern is 18 ⁇ m when base material B with a wiring pattern is used.
• the thickness of the wiring pattern was 12 ⁇ m.
• the films of Examples 1 to 6, which are films of the present disclosure have better step followability and laser processing suitability than the films of Comparative Examples 1 and 2. Furthermore, from the results shown in Table 1, the films of Examples 1 to 6, which are films of the present disclosure, have low dielectric loss tangents.

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