Classifications

• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B27/00—Layered products comprising a layer of synthetic resin
  • B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
  • B32B27/08—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B15/00—Layered products comprising a layer of metal
  • B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
  • B32B15/08—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B15/00—Layered products comprising a layer of metal
  • B32B15/04—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
  • B32B15/08—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
  • B32B15/09—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 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
  • B32B15/00—Layered products comprising a layer of metal
  • B32B15/20—Layered products comprising a layer of metal comprising aluminium or copper
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B27/00—Layered products comprising a layer of synthetic resin
  • B32B27/28—Layered products comprising a layer of synthetic resin comprising synthetic resins not wholly covered by any one of the sub-groups B32B27/30 - B32B27/42
  • B32B27/281—Layered products comprising a layer of synthetic resin comprising synthetic resins not wholly covered by any one of the sub-groups B32B27/30 - B32B27/42 comprising polyimides
• • 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
  • B32B27/28—Layered products comprising a layer of synthetic resin comprising synthetic resins not wholly covered by any one of the sub-groups B32B27/30 - B32B27/42
  • B32B27/285—Layered products comprising a layer of synthetic resin comprising synthetic resins not wholly covered by any one of the sub-groups B32B27/30 - B32B27/42 comprising polyethers
• • 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
  • B32B7/022—Mechanical properties
• • 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
• • 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
  • B32B2250/00—Layers arrangement
  • B32B2250/40—Symmetrical or sandwich layers, e.g. ABA, ABCBA, ABCCBA
• • 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
  • B32B2255/00—Coating on the layer surface
  • B32B2255/10—Coating on the layer surface on synthetic resin layer or on natural or synthetic rubber layer
• • 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
  • B32B2255/00—Coating on the layer surface
  • B32B2255/20—Inorganic coating
  • B32B2255/205—Metallic coating
• • 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
  • B32B2270/00—Resin or rubber layer containing a blend of at least two different polymers
• • 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
  • B32B2307/204—Di-electric
• • 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
  • B32B2307/206—Insulating
• • 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
  • B32B2307/54—Yield strength; Tensile strength
• • 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
  • B32B2307/70—Other properties
  • B32B2307/732—Dimensional properties
• • 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
  • B32B2307/70—Other properties
  • B32B2307/732—Dimensional properties
  • B32B2307/737—Dimensions, e.g. volume or area
  • B32B2307/7375—Linear, e.g. length, distance or width
  • B32B2307/7376—Thickness

Definitions

• the present disclosure relates to films and laminates.
• JP 2019-199612 A discloses a resin composition containing a styrene polymer, an inorganic filler, and a curing agent, wherein the styrenic 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 parts by mass based on 100 parts by mass of the styrenic polymer.
• a resin composition is described that satisfies specific formulas (A) and (B) in the form of a film having a thickness of 25 ⁇ m.
• a film having a low dielectric loss tangent and excellent suitability for laser processing is provided. Further, according to another embodiment of the present invention, a laminate using the above film is provided.
• the present disclosure includes the following aspects.
• ⁇ 1> As two virtual planes perpendicular to the thickness direction, there is an A side made of composition A and a B side made of composition B, and from A side to B side, composition A The content of at least one component A contained in the composition B decreases, and the content of at least one component B contained in the composition B decreases from the B side toward the A side, and the dielectric loss tangent is 0.010 or less.
• ⁇ 3> The film according to ⁇ 2>, wherein the average thickness of the mixed layer is 1.0% or more with respect to the thickness of the film.
• ⁇ 4> The film according to ⁇ 2> or ⁇ 3>, wherein at least one of layer A and layer B has an average thickness of 0.1 ⁇ m or more.
• ⁇ 5> The value LA obtained by subtracting the weight residual rate at 900°C from the weight residual rate at 440°C of layer A is the value L B obtained by subtracting the weight residual rate at 900°C from the weight residual rate at 440°C of layer B.
• ⁇ 6> The film according to any one of ⁇ 2> to ⁇ 5>, wherein the ratio of the elastic modulus at 160° C. of layer A to the elastic modulus at 160° C. of layer B is 1.2 or more.
• ⁇ 7> The film according to any one of ⁇ 2> to ⁇ 6>, wherein the elastic modulus of layer B at 160° C. is 100 MPa or less.
• ⁇ 8> The film according to any one of ⁇ 2> to ⁇ 7>, wherein layer B contains a thermoplastic resin containing a structural unit derived from a monomer having an aromatic hydrocarbon group.
• ⁇ 9> The film according to any one of ⁇ 2> to ⁇ 8>, wherein layer B contains a liquid crystal polymer.
• ⁇ 10> The film according to any one of ⁇ 2> to ⁇ 9>, wherein layer B contains aromatic polyesteramide.
• layer B contains aromatic polyesteramide.
• layer B contains crosslinked resin particles.
• ⁇ 12> The film according to any one of ⁇ 2> to ⁇ 11>, wherein the layer A contains a liquid crystal polymer.
• ⁇ 13> The film according to any one of ⁇ 2> to ⁇ 12>, wherein layer A contains aromatic polyesteramide.
• ⁇ 14> A laminate comprising the film according to any one of ⁇ 1> to ⁇ 13> and a metal layer or metal wiring disposed on at least one surface of the film.
• a film having a low dielectric loss tangent and excellent suitability for laser processing is provided. Further, according to another embodiment of the present invention, a laminate using the above film is provided.
• ⁇ indicating a numerical range is used to include the numerical values written before and after it as a lower limit value and an upper limit value.
• the upper limit or lower limit described in one numerical range may be replaced with the upper limit or lower limit of another numerical range described step by step.
• the upper limit or lower limit of the numerical range may be replaced with the values shown in the Examples.
• 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. be.
• the term "process” in the present disclosure is not limited to an independent process, but even if it cannot be clearly distinguished from other processes, it is included in this term if the intended purpose of the process is achieved. .
• “mass %” and “weight %” have the same meaning, and “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).
• the film according to the present disclosure has two imaginary planes perpendicular to the thickness direction, an A side made of composition A and a B side made of composition B, and from the A side to the B side. , the content of at least one component A contained in the composition A decreases, the content of at least one component B contained in the composition B decreases from the B side toward the A side, and the dielectric loss tangent is 0. It is .010 or less.
• laser processing suitability in the present disclosure refers to a property that can reduce excessive cutting by a laser when performing laser cutting, especially through-hole processing. It can be said that it has excellent workability into a desired shape.
• the content of at least one component A contained in the composition A decreases from the A side toward the B side
• the content of at least one component A contained in the composition B decreases from the B side toward the A side. Since the content of one component B is reduced, the composition change within the film is gradual, and it is considered that the film has excellent suitability for laser processing.
• the film according to the present disclosure has an A side made of composition A and a B side made of composition B as two virtual planes perpendicular to the thickness direction.
• "Two virtual planes perpendicular to the thickness direction” may be the surfaces (two main surfaces) of the film, or a cross section obtained when cutting in a direction perpendicular to the thickness direction. Good too.
• the composition of the components contained in the A-plane and the B-plane can be confirmed by ATR-IR (total reflection infrared spectroscopy) or TOF-SIMS (time-of-flight secondary ion mass spectrometry).
• the content of at least one component A contained in the composition A decreases from the A side toward the B side
• the content of at least one component A contained in the composition B decreases from the B side toward the A side.
• the content of one component B is reduced. Note that both the direction from the A side to the B side and the direction from the B side to the A side are the thickness directions.
• Examples of embodiments in which the content of at least one component A contained in the composition A decreases from the A side toward the B side include an embodiment in which the content of the component A continuously decreases; An example is an embodiment in which the content decreases in stages.
• an embodiment in which the content of at least one component B contained in the composition B decreases from the B side toward the A side includes, for example, an embodiment in which the content of the component B continuously decreases; An example is an embodiment in which the content of component B is reduced in stages.
• Whether the content of at least one component A contained in composition A decreases from side A to side B can be confirmed using the following method. Further, it can be confirmed in a similar manner whether the content of at least one component B contained in the composition B decreases from the B side toward the A side.
• the film according to the present disclosure has a dielectric loss tangent of 0.010 or less, preferably 0.005 or less, and more preferably more than 0 and 0.002 or less.
• the dielectric loss tangent shall be measured by the following method.
• the measurement of the dielectric loss tangent is carried out using a resonance perturbation method at a frequency of 10 GHz.
• a 10 GHz cavity resonator (Kanto Electronics Application Development Co., Ltd. CP531) was connected to a network analyzer (Agilent Technology "E8363B"), and a measurement sample (width: 2.0 mm x length: 80 mm) was placed in the cavity resonator.
• the dielectric loss tangent of the measurement sample is measured from the change in resonance frequency before and after insertion for 96 hours under an environment of temperature 25° C. and humidity 60% RH.
• a preferred embodiment of the film according to the present disclosure is a layer A made of a composition A and including the A side, a layer B made of the composition B and including the B side, and a layer B located between the layer A and the layer B,
• This is a film that includes, in the thickness direction, a mixed layer containing components included in Product A and Composition B.
• Examples of methods for detecting or determining the layer structure in the film and the thickness of each layer include the following methods.
• 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
• Layer A consists of composition A and includes an A side. Layer A is a uniform layer with a composition of composition A.
• composition A constituting layer A are not particularly limited as long as the dielectric loss tangent of the film can be 0.010 or less.
• Layer A preferably contains a polymer having a dielectric loss tangent of 0.010 or less.
• composition usually means containing a plurality of components, but in the present disclosure, composition A may contain only one component, or may contain two or more components. .
• the type of polymer having a dielectric loss tangent of 0.010 or less is not particularly limited, and known polymers can be used.
• Examples of the polymer contained in layer A include liquid crystal polymers, fluororesins, polymers of compounds having a cycloaliphatic hydrocarbon group and a group having an ethylenically unsaturated bond, polyether ether ketone, polyolefin, polyamide, and polyester. , polyphenylene sulfide, polyether ketone, polycarbonate, polyether sulfone, polyphenylene ether and its modified products, thermoplastic resins such as polyetherimide; elastomers such as copolymers of glycidyl methacrylate and polyethylene; phenolic resins, epoxy resins, polyimides and thermosetting resins such as cyanate resins.
• layer A is made of a liquid crystal polymer, a fluororesin, a polymer of a compound having a cycloaliphatic hydrocarbon group and a group having an ethylenically unsaturated bond, and polyphenylene ether. It is preferable that at least one polymer selected from the group consisting of a liquid crystal polymer and a fluororesin is included, and it is more preferable that at least one polymer selected from the group consisting of a liquid crystal polymer and a fluororesin is included. It is particularly preferable to contain a polymer, and from the viewpoint of dielectric loss tangent, it is particularly preferable to contain a fluororesin.
• liquid crystal polymer The type of liquid crystal polymer is not particularly limited, and any known liquid crystal polymer can be used. Further, the liquid crystal polymer may be a thermotropic liquid crystal polymer that exhibits liquid crystallinity in a molten state, or may be a lyotropic liquid crystal polymer that exhibits liquid crystallinity in a solution state. Further, in the case of thermotropic liquid crystal, it is preferable that the liquid crystal melts at a temperature of 450° C. or lower.
• liquid crystal polymers examples include liquid crystal polyester, liquid crystal polyester amide in which an amide bond is introduced into a liquid crystal polyester, liquid crystal polyester ether in which an ether bond is introduced into a liquid crystal polyester, and liquid crystal polyester carbonate in which a carbonate bond is introduced into a liquid crystal polyester. can be mentioned.
• the liquid crystal polymer is preferably a polymer having an aromatic ring, and more preferably an aromatic polyester or an aromatic polyester amide.
• liquid crystal polymer may be a polymer in which isocyanate-derived bonds such as imide bonds, carbodiimide bonds, and isocyanurate bonds are further introduced into aromatic polyester or aromatic polyester amide.
• liquid crystal polymer is preferably a wholly aromatic liquid crystal polymer using only aromatic compounds as raw material monomers.
• liquid crystal polymer examples include the following liquid crystal polymers. 1) (i) aromatic hydroxycarboxylic acid, (ii) aromatic dicarboxylic acid, and (iii) at least one compound selected from the group consisting of aromatic diol, aromatic hydroxyamine, and aromatic diamine; Something made by polycondensation. 2) A product obtained by polycondensing multiple types of aromatic hydroxycarboxylic acids. 3) A product obtained by polycondensing (i) an aromatic dicarboxylic acid and (ii) at least one compound selected from the group consisting of an aromatic diol, an aromatic hydroxyamine, and an aromatic diamine.
• a product obtained by polycondensing (i) a polyester such as polyethylene terephthalate and (ii) an aromatic hydroxycarboxylic acid.
• a polyester such as polyethylene terephthalate
• an aromatic hydroxycarboxylic acid the aromatic hydroxycarboxylic acid, aromatic dicarboxylic acid, aromatic diol, aromatic hydroxyamine, and aromatic diamine may each be independently replaced with a polycondensable derivative.
• aromatic hydroxycarboxylic acids and aromatic dicarboxylic acids can be replaced with aromatic hydroxycarboxylic acid esters and aromatic dicarboxylic acid esters.
• aromatic hydroxycarboxylic acids and aromatic dicarboxylic acids can be replaced with aromatic hydroxycarboxylic acid halides and aromatic dicarboxylic acid halides.
• aromatic hydroxycarboxylic acids and aromatic dicarboxylic acids can be replaced with aromatic hydroxycarboxylic acid anhydrides and aromatic dicarboxylic acid anhydrides.
• polymerizable derivatives of compounds having hydroxy groups such as aromatic hydroxycarboxylic acids, aromatic diols, and aromatic hydroxyamines include those obtained by acylating a hydroxy group to convert it into an acyloxy group (acylated products) can be mentioned.
• aromatic hydroxycarboxylic acids, aromatic diols, and aromatic hydroxyamines can each be replaced with acylated products.
• polymerizable derivatives of compounds having an amino group such as aromatic hydroxyamines and aromatic diamines include those obtained by acylating an amino group to convert it into an acylamino group (acylated product). For example, by acylating an amino group to convert it into an acylamino group, aromatic hydroxyamine and aromatic diamine can each be replaced with an acylated product.
• the liquid crystal polymer preferably has crystallinity (for example, aromatic polyesteramide described below). When the liquid crystal polymer has crystallinity, the dielectric loss tangent decreases further.
• the melting point of the liquid crystal polymer is preferably 250°C or higher, more preferably 250°C to 350°C, and even more preferably 260°C to 330°C.
• the weight average molecular weight of the liquid crystal polymer is preferably 1,000,000 or less, more preferably 3,000 to 300,000, even more preferably 5,000 to 100,000, 5. 000 to 30,000 is particularly preferred.
• the liquid crystal polymer preferably contains aromatic polyesteramide from the viewpoint of further lowering the dielectric loss tangent.
• Aromatic polyester amide is a resin that has at least one aromatic ring and also has an ester bond and an amide bond.
• the aromatic polyesteramide contained in the resin layer is preferably a wholly aromatic polyesteramide.
• the aromatic polyester amide includes a structural unit represented by the following formula 1, a structural unit represented by the following formula 2, and a structural unit represented by the following formula 3.
• Ar 1 , Ar 2 and Ar 3 each independently represent a phenylene group, a naphthylene group or a biphenylylene group.
• the structural unit etc. represented by Formula 1 will also be referred to as "unit 1" etc.
• Unit 1 can be introduced, for example, by using an aromatic hydroxycarboxylic acid as a raw material.
• Unit 2 can be introduced, for example, by using an aromatic dicarboxylic acid as a raw material.
• Unit 3 can be introduced, for example, by using aromatic hydroxylamine as a raw material.
• aromatic hydroxycarboxylic acid, aromatic dicarboxylic acid, aromatic diol, and aromatic hydroxylamine may each be independently replaced with a polycondensable derivative.
• aromatic hydroxycarboxylic acids and aromatic dicarboxylic acids can be replaced with aromatic hydroxycarboxylic acid esters and aromatic dicarboxylic acid esters.
• aromatic hydroxycarboxylic acids and aromatic dicarboxylic acids can be replaced with aromatic hydroxycarboxylic acid halides and aromatic dicarboxylic acid halides.
• aromatic hydroxycarboxylic acids and aromatic dicarboxylic acids can be replaced with aromatic hydroxycarboxylic acid anhydrides and aromatic dicarboxylic acid anhydrides.
• polycondensable derivatives of compounds having hydroxy groups such as aromatic hydroxycarboxylic acids and aromatic hydroxyamines include derivatives obtained by acylating a hydroxy group to convert it into an acyloxy group (acylated products). .
• aromatic hydroxycarboxylic acid and aromatic hydroxylamine can each be replaced with an acylated product.
• polycondensable derivatives of aromatic hydroxylamine include those obtained by acylating an amino group to convert it into an acylamino group (acylated product).
• acylated product an aromatic hydroxyamine can be replaced with an acylated product by acylating an amino group to convert it into an acylamino group.
• Ar 1 is preferably a p-phenylene group, a 2,6-naphthylene group, or a 4,4′-biphenylylene group, and more preferably a 2,6-naphthylene group.
• unit 1 is, for example, a structural unit derived from p-hydroxybenzoic acid.
• unit 1 is, for example, a structural unit derived from 6-hydroxy-2-naphthoic acid.
• Ar 1 is a 4,4'-biphenylylene group
• unit 1 is, for example, a structural unit derived from 4'-hydroxy-4-biphenylcarboxylic acid.
• Ar 2 is preferably a p-phenylene group, m-phenylene group, or 2,6-naphthylene group, and more preferably an m-phenylene group.
• unit 2 is, for example, a structural unit derived from terephthalic acid.
• unit 2 is, for example, a structural unit derived from isophthalic acid.
• Ar 2 is a 2,6-naphthylene group
• unit 2 is, for example, a structural unit derived from 2,6-naphthalene dicarboxylic acid.
• Ar 3 is preferably a p-phenylene group or a 4,4'-biphenylylene group, more preferably a p-phenylene group.
• the unit 3 is, for example, a structural unit derived from p-aminophenol.
• unit 3 is, for example, a structural unit derived from 4-amino-4'-hydroxybiphenyl.
• the content of unit 1 is preferably 30 mol% or more, and the content of unit 2 is preferably 35 mol% or less.
• the content of unit 3 is preferably 35 mol% or less.
• the content of unit 1 is more preferably 30 mol% to 80 mol%, more preferably 30 mol% to 60 mol%, based on the total content of unit 1, unit 2, and unit 3. It is preferably 30 mol% to 40 mol%.
• the content of unit 2 is preferably 10 mol% to 35 mol%, more preferably 20 mol% to 35 mol%, based on the total content of unit 1, unit 2, and unit 3. , 30 mol% to 35 mol% is particularly preferred.
• the content of unit 3 is preferably 10 mol% to 35 mol%, more preferably 20 mol% to 35 mol%, based on the total content of unit 1, unit 2, and unit 3. , 30 mol% to 35 mol% is particularly preferred.
• the total content of each structural unit is the value which totaled the substance amount (mol) of each structural unit.
• the amount of substance of each structural unit is calculated by dividing the mass of each structural unit constituting the aromatic polyesteramide by the formula weight of each structural unit.
• the ratio between the content of unit 2 and the content of unit 3 is preferably 0.9/1 to 0.9/1 when expressed as [content of unit 2]/[content of unit 3] (mol/mol).
• the ratio is 1/0.9, more preferably 0.95/1 to 1/0.95, even more preferably 0.98/1 to 1/0.98.
• the aromatic polyester amide may have two or more types of units 1 to 3, each independently. Further, the aromatic polyester amide may have other structural units other than units 1 to 3. The content of other structural units is preferably 10 mol% or less, more preferably 5 mol% or less, based on the total content of all structural units.
• the aromatic polyester amide is preferably produced by melt polymerizing raw material monomers corresponding to the structural units constituting the aromatic polyester amide.
• Layer A may contain only one type of aromatic polyester amide, or may contain two or more types.
• the content of aromatic polyesteramide is preferably 50% by mass or more, more preferably 70% by mass or more, and even more preferably 90% by mass or more, based on the total amount of layer A.
• the upper limit of the aromatic polyesteramide content is not particularly limited, and may be 100% by mass.
• the liquid crystal polymer is preferably produced by melt polymerizing raw material monomers corresponding to the structural units constituting it. Melt polymerization may be carried out in the presence of a catalyst, examples of which include metal compounds such as magnesium acetate, stannous acetate, tetrabutyl titanate, lead acetate, sodium acetate, potassium acetate, antimony trioxide, Examples include nitrogen-containing heterocyclic compounds such as 4-(dimethylamino)pyridine and 1-methylimidazole, and nitrogen-containing heterocyclic compounds are preferably used. Note that the melt polymerization may be further carried out by solid phase polymerization, if necessary.
• the liquid crystal polymer has a flow start temperature of preferably 250°C or higher, more preferably 250°C or higher and 350°C or lower, and even more preferably 260°C or higher and 330°C or lower.
• a flow start temperature of the liquid crystal polymer is within the above range, the solubility, heat resistance, strength and rigidity are excellent, and the viscosity of the solution is appropriate.
• the flow start temperature is also called the flow temperature or flow temperature
• the liquid crystal polymer is melted using a capillary rheometer while increasing the temperature at a rate of 4°C/min under a load of 9.8 MPa (100 kg/cm 2 ).
• This is the temperature at which liquid crystal polymers exhibit a viscosity of 4,800 Pa ⁇ s (48,000 poise) when extruded through a nozzle with an inner diameter of 1 mm and a length of 10 mm, which is a guideline for the molecular weight of liquid crystal polymers (edited by Naoyuki Koide). , "Liquid Crystal Polymers - Synthesis, Molding, and Applications," CMC Co., Ltd., June 5, 1987, p. 95).
• the type of fluororesin is not particularly limited, and any known fluororesin can be used.
• the fluororesin examples include fluorinated ⁇ -olefin monomers, that is, homopolymers and copolymers containing structural units derived from ⁇ -olefin monomers containing at least one fluorine atom.
• the fluororesin is a copolymer containing a structural unit derived from a fluorinated ⁇ -olefin monomer and a structural unit derived from a non-fluorinated ethylenically unsaturated monomer reactive with the fluorinated ⁇ -olefin monomer. can be mentioned.
• vinyl ethers eg, perfluoromethyl vinyl ether, perfluoropropyl vinyl ether, and perfluorooctyl vinyl ether.
• Non-fluorinated ethylenically unsaturated monomers include ethylene, propylene, butene, ethylenically unsaturated aromatic monomers (eg, styrene and ⁇ -methylstyrene), and the like.
• the fluorinated ⁇ -olefin monomers may be used alone or in combination of two or more. Further, the non-fluorinated ethylenically unsaturated monomers may be used alone or in combination of two or more.
• fluororesin examples include polychlorotrifluoroethylene (PCTFE), poly(chlorotrifluoroethylene-propylene), poly(ethylene-tetrafluoroethylene) (ETFE), and poly(ethylene-chlorotrifluoroethylene) (ECTFE).
• PCTFE polychlorotrifluoroethylene
• ETFE poly(chlorotrifluoroethylene-propylene)
• ETFE poly(ethylene-tetrafluoroethylene)
• ECTFE poly(ethylene-chlorotrifluoroethylene)
• PTFE poly(tetrafluoroethylene)
• FEP
• the fluororesin may have a structural unit derived from fluorinated ethylene or fluorinated propylene.
• the fluororesin may be used alone or in combination of two or more.
• the fluororesin is preferably FEP, PFA, ETFE, or PTFE.
• FEP is available from DuPont under the trade name TEFLON FEP or from Daikin Industries, Ltd. under the trade name NEOFLON FEP.
• PFA is the product name NEOFLON PFA from Daikin Industries, Ltd., the product name TEFLON (registered trademark) PFA from DuPont, or Solvay Solexis. It is available from Solexis under the trade name HYFLON PFA.
• the fluororesin contains PTFE.
• the PTFE may be a PTFE homopolymer, a partially modified PTFE homopolymer, or a combination including one or both of these.
• the partially modified PTFE homopolymer contains less than 1% by weight of constitutional units derived from comonomers other than tetrafluoroethylene, based on the total weight of the polymer.
• the fluororesin may be a crosslinkable fluoropolymer having a crosslinkable group.
• the crosslinkable fluoropolymer can be crosslinked by conventionally known crosslinking methods.
• One representative crosslinkable fluoropolymer is a fluoropolymer with (meth)acryloyloxy.
• R may be a fluorine-based oligomer chain containing a structural unit derived from tetrafluoroethylene.
• Forming a crosslinked fluoropolymer network by exposing a fluoropolymer with (meth)acryloyloxy groups to a free radical source to initiate a radical crosslinking reaction via the (meth)acryloyloxy groups on the fluororesin be able to.
• the free radical source is not particularly limited, but suitable examples include photoradical polymerization initiators and organic peroxides. Suitable photoradical polymerization initiators and organic peroxides are well known in the art.
• Crosslinkable fluoropolymers are commercially available, such as Viton B manufactured by DuPont.
• Polymers of a compound having a cycloaliphatic hydrocarbon group and a group having an ethylenically unsaturated bond examples include thermoplastic resins having structural units derived from cyclic olefin monomers such as norbornene or polycyclic norbornene monomers. can be mentioned.
• Polymers of compounds having a cycloaliphatic hydrocarbon group and a group having an ethylenically unsaturated bond can be obtained by hydrogenation of a ring-opening polymer of the above-mentioned cyclic olefin or a ring-opening copolymer using two or more types of cyclic olefins. It may be an addition polymer of a cyclic olefin and a chain olefin or an aromatic compound having an ethylenically unsaturated bond such as a vinyl group. Further, a polar group may be introduced into the polymer of the compound having a cycloaliphatic hydrocarbon group and a group having an ethylenically unsaturated bond. The polymer of a compound having a cycloaliphatic hydrocarbon group and a group having an ethylenically unsaturated bond may be used alone or in combination of two or more.
• the ring structure of the cyclic aliphatic hydrocarbon group may be a single ring, a condensed ring of two or more rings, or a bridged ring.
• Examples of the ring structure of the cyclic aliphatic hydrocarbon group include a cyclopentane ring, a cyclohexane ring, a cyclooctane ring, an isoborone ring, a norbornane ring, and a dicyclopentane ring.
• the compound having a cycloaliphatic hydrocarbon group and a group having an ethylenically unsaturated bond is not particularly limited, and includes (meth)acrylate compounds having a cycloaliphatic hydrocarbon group, (meth)acrylate compounds having a cycloaliphatic hydrocarbon group, Examples include meth)acrylamide compounds, vinyl compounds having a cyclic aliphatic hydrocarbon group, and the like. Among these, (meth)acrylate compounds having a cyclic aliphatic hydrocarbon group are preferred.
• the compound having a cycloaliphatic hydrocarbon group and a group having an ethylenically unsaturated bond may be a monofunctional ethylenically unsaturated compound or a polyfunctional ethylenically unsaturated compound.
• the number of cyclic aliphatic hydrocarbon groups in the compound having a cyclic aliphatic hydrocarbon group and a group having an ethylenically unsaturated bond may be one or more, and may have two or more.
• the polymer of a compound having a cycloaliphatic hydrocarbon group and a group having an ethylenically unsaturated bond is obtained by polymerizing a compound having at least one kind of cycloaliphatic hydrocarbon group and a group having an ethylenically unsaturated bond. It may be a polymer of compounds having two or more types of cycloaliphatic hydrocarbon groups and a group having an ethylenically unsaturated bond, or it may be a polymer having no cycloaliphatic hydrocarbon groups. It may also be a copolymer with other ethylenically unsaturated compounds. Further, the polymer of a compound having a cycloaliphatic hydrocarbon group and a group having an ethylenically unsaturated bond is preferably a cycloolefin polymer.
• the average number of phenolic hydroxyl groups per molecule at the end of the molecule is preferably 1 to 5, and 1.5 from the viewpoint of dielectric loss tangent and heat resistance. It is more preferable that the number is 3 to 3.
• the number of terminal hydroxyl groups of polyphenylene ether can be determined, for example, from the specification value of polyphenylene ether products. Further, the number of terminal hydroxyl groups is expressed, for example, as the average number of phenolic hydroxyl groups per molecule of all polyphenylene ethers present in 1 mole of polyphenylene ether.
• One type of polyphenylene ether may be used alone, or two or more types may be used in combination.
• polyphenylene ether examples include polyphenylene ether consisting of 2,6-dimethylphenol and at least one of bifunctional phenol and trifunctional phenol, and poly(2,6-dimethyl-1,4-phenylene oxide). Can be mentioned. More specifically, the polyphenylene ether is preferably a compound having a structure represented by the formula (PPE).
• X represents an alkylene group having 1 to 3 carbon atoms or a single bond
• m represents an integer of 0 to 20
• n represents an integer of 0 to 20
• m and n represent The sum represents an integer from 1 to 30.
• Examples of the alkylene group in the above X include a dimethylmethylene group.
• the weight average molecular weight (Mw) of polyphenylene ether is preferably from 500 to 5,000, preferably from 500 to 3,000, from the viewpoint of heat resistance and film forming properties when it is thermally cured after film formation. It is 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 aromatic polyetherketone is not particularly limited, and any known aromatic polyetherketone can be used.
• the aromatic polyetherketone is a polyetheretherketone.
• Polyetheretherketone is a type of aromatic polyetherketone, and is a polymer in which bonds are arranged in the order of ether bonds, ether bonds, and carbonyl bonds. It is preferable that each bond is connected by a divalent aromatic group.
• One type of aromatic polyetherketone may be used alone, or two or more types may be used in combination.
• aromatic polyetherketones examples include polyetheretherketone (PEEK) having a chemical structure represented by the following formula (P1), and polyetherketone (PEK) having a chemical structure represented by the following formula (P2). , polyetherketoneketone (PEKK) having a chemical structure represented by the following formula (P3), polyetheretherketoneketone (PEEKK) having a chemical structure represented by the following formula (P4), and the following formula (P5) Examples include polyetherketoneetherketoneketone (PEKEKK) having the chemical structure represented by:
• n in each of formulas (P1) to (P5) is preferably 10 or more, and more preferably 20 or more.
• n is preferably 5,000 or less, more preferably 1,000 or less. That is, n is preferably 10 to 5,000, more preferably 20 to 1,000.
• layer A preferably includes at least one polymer having a dielectric loss tangent of 0.010 or less.
• the content of the polymer having a dielectric loss tangent of 0.010 or less is determined from the viewpoint of the dielectric loss tangent of the film and the adhesion with the metal layer. Based on the total mass of It is particularly preferred that the amount is 50% by mass.
• -Filler- Layer A may contain at least one filler from the viewpoint of thermal expansion coefficient and adhesion with the metal layer.
• the filler may be particulate or fibrous.
• the filler may be an inorganic filler or an organic filler. From the viewpoint of the dielectric loss tangent of the film and the ability to follow steps, the filler is preferably an organic filler.
• organic filler known organic fillers can be used.
• organic filler material include polyethylene, polystyrene, urea-formalin filler, polyester, cellulose, acrylic resin, fluororesin, hardened epoxy resin, crosslinked benzoguanamine resin, crosslinked acrylic resin, liquid crystal polymer, and two or more of these.
• materials include:
• the organic filler may be in the form of fibers such as nanofibers, or may be hollow resin particles.
• the organic filler is preferably fluororesin particles, polyester resin particles, polyethylene particles, liquid crystal polymer particles, or cellulose resin nanofibers, from the viewpoint of dielectric loss tangent of the film and step tracking ability.
• Polytetrafluoroethylene particles, polyethylene particles, or liquid crystal polymer particles are more preferable, and liquid crystal polymer particles are particularly preferable.
• the liquid crystal polymer particles refer to, but are not limited to, those obtained by polymerizing a liquid crystal polymer and pulverizing it with a pulverizer or the like to obtain a powdered liquid crystal.
• the liquid crystal polymer particles are preferably smaller than the thickness of each layer.
• the average particle size 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 followability.
• 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 with the metal layer. Particular preference is given to particles or glass fibers.
• the average particle size of the inorganic filler is preferably about 20% to about 40% of the thickness of layer A, and may be selected to be, for example, 25%, 30% or 35% of the thickness of layer A. . When the particles or fibers are flat, the length in the short side direction is shown.
• the average particle size of the inorganic filler is preferably 5 nm to 20 ⁇ m, more preferably 10 nm to 10 ⁇ m, and 20 nm to 1 ⁇ m from the viewpoint of thermal expansion coefficient and adhesion with the metal layer. It is more preferably 25 nm to 500 nm.
• -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 B consists of composition B and includes the B side.
• Layer B is a uniform layer with a composition of composition B.
• Composition B constituting Layer B are not particularly limited as long as the dielectric loss tangent of the film can be 0.010 or less.
• layer B comprises at least one polymer.
• Layer B preferably contains a thermoplastic resin from the viewpoints of the film's dielectric loss tangent, laser processing suitability, and level difference followability.
• the thermoplastic resin may be a thermoplastic elastomer.
• the elastomer refers to a polymer compound that exhibits elastic deformation. That is, a polymer compound that has the property of deforming in response to an external force when an external force is applied, and recovering its original shape in a short time when the external force is removed.
• Thermoplastic resins include polyurethane resin, polyester resin, (meth)acrylic resin, polystyrene resin, fluororesin, polyimide resin, fluorinated polyimide resin, polyamide resin, polyamideimide resin, polyetherimide resin, cellulose acylate resin, and polyurethane.
• Resin polyetheretherketone resin, polycarbonate resin, polyolefin resin (for example, polyethylene resin, polypropylene resin, resin consisting of cyclic olefin copolymer, alicyclic polyolefin resin), polyarylate resin, polyethersulfone resin, polysulfone resin, fluorene ring
• polyolefin resin for example, polyethylene resin, polypropylene resin, resin consisting of cyclic olefin copolymer, alicyclic polyolefin resin
• polyarylate resin polyethersulfone resin, polysulfone resin, fluorene ring
• modified polycarbonate resins alicyclic modified polycarbonate resins, and fluorene ring modified polyester resins.
• Thermoplastic elastomers are not particularly limited, and include, for example, elastomers containing repeating units derived from styrene (polystyrene elastomers), polyester elastomers, polyolefin elastomers, polyurethane elastomers, polyamide elastomers, polyacrylic elastomers, and silicones. elastomers, polyimide elastomers, and the like. Note that the thermoplastic elastomer may be a hydrogenated product.
• polystyrene-based elastomers examples include styrene-butadiene-styrene block copolymer (SBS), styrene-isoprene-styrene block copolymer (SIS), polystyrene-poly(ethylene-propylene) diblock copolymer (SEP), and polystyrene.
• SBS styrene-butadiene-styrene block copolymer
• SIS styrene-isoprene-styrene block copolymer
• SEP polystyrene-poly(ethylene-propylene) diblock copolymer
• polystyrene-based elastomers examples include styrene-butadiene-styrene block copolymer (SBS), styrene-isoprene-styrene block copolymer (SIS), polystyren
• SEPS Poly(ethylene-propylene)-polystyrene triblock copolymer
• SEBS styrene-ethylene-butylene-styrene block copolymer
• SEEPS polystyrene-poly(ethylene/ethylene-propylene)-polystyrene triblock copolymer
• SEEPS polystyrene-poly(ethylene/ethylene-propylene)-polystyrene triblock copolymer
• layer B preferably contains a thermoplastic resin containing a structural unit derived from a monomer having an aromatic hydrocarbon group, from the viewpoint of the film's dielectric loss tangent, laser processing suitability, and level difference followability. It is more preferable to contain an elastomer, and it is particularly preferable to contain a hydrogenated styrene-ethylene-butylene-styrene block copolymer. Moreover, from the viewpoints of the dielectric loss tangent of the film, suitability for laser processing, and ability to follow steps, it is preferable that layer B contains a hydrogenated polystyrene elastomer.
• the content of the thermoplastic resin is not particularly limited, but from the viewpoint of the dielectric loss tangent of the film, suitability for laser processing, and adhesion with the metal layer, the content of the thermoplastic resin is 50% by mass to 100% by mass based on the total mass of layer B. It is preferably from 60% by mass to 90% by mass.
• the layer B contains a polymer having a dielectric loss tangent of 0.010 or less.
• a preferred embodiment of the polymer having a dielectric loss tangent of 0.010 or less is the same as a preferred embodiment of the polymer having a dielectric loss tangent of 0.010 or less, which may be included in layer A.
• layer B preferably contains a liquid crystal polymer, and more preferably contains an aromatic polyesteramide.
• layer B contains a polymer having a dielectric loss tangent of 0.010 or less
• the content of the polymer having a dielectric loss tangent of 0.010 or less is not particularly limited, but it depends on the dielectric loss tangent of the film, the suitability for laser processing, and the metal layer. From the viewpoint of adhesion, it is preferably 10% by mass to 100% by mass, more preferably 10% by mass to 70% by mass, and 10% by mass to 60% by mass, based on the total mass of layer B. It is particularly preferable that there be.
• Layer B more preferably contains a filler from the viewpoints of the dielectric loss tangent of the film, suitability for laser processing, adhesion to the metal layer, and step followability.
• Preferred embodiments of the filler used in layer B are the same as those of the filler that may be included in layer A, except as described below.
• the filler used in layer B the above-mentioned thermoplastic resin particles are also preferably mentioned.
• at least one of the polymer and filler contained in layer B is preferably a polymer having a dielectric loss tangent of 0.01 or less. , more preferably a liquid crystal polymer.
• layer B contains crosslinked resin particles as a filler.
• the crosslinked resin in the crosslinked resin particles is not particularly limited, and any known crosslinked resin can be used.
• it may be a crosslinked resin using a crosslinking agent during polymerization, or it may be a crosslinked resin in which a crosslinking agent is reacted with the resin.
• thermoplastic elastomer particles from the viewpoint of the dielectric loss tangent of the film, laser processing suitability, and level difference followability, the above-mentioned thermoplastic elastomer particles are preferable, polystyrene-based elastomer particles are more preferable, and hydrogenated polystyrene-based elastomers are particularly preferable. .
• 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 10% by mass to 90% by mass, and preferably 20% by mass to 90% by mass, based on the total mass of layer B, from the viewpoint of suitability for laser processing and adhesion with the metal layer. 80% by mass is more preferred.
• 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.
• Layer B is preferably a surface layer (outermost layer).
• a laminate laminate with metal layer
• another metal layer or a laminate with metal layer may be further disposed on the layer B side. . In this case, interface destruction between layer B and another metal layer in the laminate is suppressed, and adhesion with the metal layer is improved.
• the average thickness of at least one of layer A and layer B is preferably 0.1 ⁇ m or more.
• 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 dielectric loss tangent of the film and adhesion to metal. It is preferably from 1 to 5, even more preferably from more than 1 to 3 or less, and particularly preferably from more than 1 to 2 or less.
• the average thickness of layer A is not particularly limited, but from the viewpoint of the dielectric loss tangent of the film and the adhesion with the metal layer, it is preferably 0.1 ⁇ m or more, more preferably 5 ⁇ m to 90 ⁇ m, It is more preferably 10 ⁇ m to 70 ⁇ m, particularly preferably 15 ⁇ m to 60 ⁇ m.
• 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 step followability, it is preferably 0.1 ⁇ m or more, and more preferably 1 ⁇ m to 90 ⁇ m. , more preferably 5 ⁇ m to 60 ⁇ m, particularly preferably 10 ⁇ m to 40 ⁇ m.
• the method for measuring the average thickness of each layer in the film according to the present disclosure is as follows. Cut the film with a microtome, observe the cross section with an optical microscope, and evaluate the thickness of each layer. Cut out the cross-sectional sample at three or more locations, measure the thickness at at least three points on each section, and use the average value as the average thickness.
• the value LA obtained by subtracting the weight residual rate at 900°C from the weight residual rate at 440°C of the layer A is: It is preferable that it is larger than the value L B obtained by subtracting the weight residual rate at 900° C. from the weight residual rate at 440° C. of the layer B.
• the value obtained by subtracting LB from LA (LA - LB ) is not particularly limited, but from the viewpoint of laser processing suitability and step tracking ability, it is preferably less than 100%, and 95%. It is more preferably below, even more preferably 10% to 90%, particularly preferably 10% to 85%.
• L A is preferably 80% or more, more preferably 85% or more, and 90% to 100% from the viewpoint of the dielectric loss tangent of the film, laser processing suitability, and step tracking ability. Particularly preferred. From the viewpoint of the dielectric loss tangent of the film, suitability for laser processing, and step tracking ability, L B is preferably 5% or more, more preferably 8% to 80%, and 10% to 60%. It is particularly preferable.
• the elastic modulus of layer A at 160° C. is preferably larger than the elastic modulus of layer B at 160° C. from the viewpoint of dielectric loss tangent, laser processing suitability, and step tracking ability of the film.
• the ratio of the elastic modulus of layer A at 160° C. to the elastic modulus of layer B at 160° C. is preferably 1.2 or more, and 5 to 1,000 from the viewpoint of laser processing suitability and step followability. It is more preferably 100 to 500.
• the elastic modulus of layer A at 160° C. is preferably 100 MPa to 2,500 MPa, preferably 200 MPa to 2,000 MPa, and 300 MPa to 1,500 MPa, from the viewpoint of laser processing suitability and step followability. More preferably, it is 500 MPa to 1,000 MPa.
• the elastic modulus of layer B at 160° C. is preferably 100 MPa or less, more preferably 10 MPa or less, and more preferably 0.001 MPa to 10 MPa, from the viewpoint of laser processing suitability and step followability. It is preferably 0.5 MPa to 5 MPa, particularly preferably 0.5 MPa to 5 MPa.
• the elastic modulus shall be measured by the following method. First, a cross section of the film is cut using a microtome or the like, and layer A or layer B is identified using an optical microscope. Next, the elastic modulus of the specified layer A or layer B is measured as an indentation elastic modulus using a nanoindentation method. The indentation modulus was measured using a microhardness tester (product name "DUH-W201", manufactured by Shimadzu Corporation) at 160°C with a Vickers indenter at a loading rate of 0.28 mN/sec, with a maximum load of 10 mN. 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
• the mixed layer contains components included in composition A and composition B.
• the mixed layer preferably contains at least one component included in composition A and at least one component included in composition B.
• the composition changes more slowly in the thickness direction of the film, improving suitability for laser processing.
• the mixed layer only needs to contain the components contained in composition A and composition B, and may be a layer with a uniform composition or a layer with a non-uniform composition.
• the average thickness of the mixed layer is preferably 1.0% or more, more preferably 3.0% or more of the film thickness, from the viewpoints of laser processing suitability and interlayer adhesion.
• the upper limit of the average thickness of the mixed layer is not particularly limited, and is, for example, 95%.
• the film according to the present disclosure preferably further has a layer C, and from the viewpoint of adhesion with the metal layer, the film has the layer B, the mixed layer, the layer A, and the layer C in this order. It is more preferable.
• Layer C is preferably an adhesive layer. Further, layer C is preferably a surface layer (outermost layer).
• Layer C preferably contains a polymer from the viewpoint of the dielectric loss tangent of the film and suitability for laser processing. Preferred embodiments of the polymer used for layer C are the same as the preferred embodiments of the polymer used for layer A, which has a dielectric loss tangent of 0.010 or less, except as described below.
• the polymer contained in layer C may be the same as or different from the polymer contained in layer A or layer B, but from the viewpoint of adhesion between layer A and layer C, It is preferable that the polymer contains the same polymer.
• layer C preferably contains a polymer having an aromatic ring, and is a polymer having an aromatic ring and having an ester bond and an amide bond. It is more preferable to include. Further, layer C preferably contains an epoxy resin in order to bond the metal layer and layer A together.
• 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.
• 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 the metal layer, the content of filler in layer A Preferably less than.
• 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, should be greater than 1 from the viewpoint of the dielectric loss tangent of the film and the adhesion with the metal layer. is preferable, 2 to 100 is more preferable, 2.5 to 20 is even more preferable, and 3 to 10 is particularly preferable.
• T B /T C which is the ratio of the average thickness T B of layer B to the average thickness T C of layer C, is greater than 1 from the viewpoint of the dielectric loss tangent of the film and the adhesion with the metal layer. is preferable, 2 to 100 is more preferable, 2.5 to 20 is even more preferable, and 3 to 10 is particularly preferable.
• the average thickness of layer C is preferably 0.1 ⁇ m to 20 ⁇ m, more preferably 0.5 ⁇ m to 15 ⁇ m, and 1 ⁇ m from the viewpoint of dielectric loss tangent of the film and adhesion with the metal layer. It is more preferably 10 ⁇ m to 10 ⁇ m, particularly preferably 2 ⁇ m to 8 ⁇ m.
• the average thickness of the film according to the present disclosure is preferably 6 ⁇ m to 200 ⁇ m, and preferably 12 ⁇ m to 100 ⁇ m, from the viewpoint of strength and electrical properties (characteristic impedance) when formed into a laminate with a metal layer.
• the thickness is more preferably 20 ⁇ m to 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 producing the film according to the present disclosure is not particularly limited, and known methods can be referred to.
• Preferred methods for producing the film according to the present disclosure include, for example, a co-casting method, a sequential casting method, a multilayer coating method, a sequential coating method, a co-extrusion method, etc. Combinations thereof include, for example, co-extrusion A combination of a coating method and a coating method may also be mentioned.
• the co-casting method or the multilayer coating method is particularly preferable for forming a relatively thin film
• 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 method for forming the mixed layer will be described later.
• solvents include halogenated hydrocarbons such as dichloromethane, chloroform, 1,1-dichloroethane, 1,2-dichloroethane, 1,1,2,2-tetrachloroethane, 1-chlorobutane, chlorobenzene, and o-dichlorobenzene; Halogenated phenols such as p-chlorophenol, pentachlorophenol and pentafluorophenol; Ethers such as diethyl ether, tetrahydrofuran and 1,4-dioxane; Ketones such as acetone and cyclohexanone; Esters such as ethyl acetate and ⁇ -butyrolactone; ethylene Carbonates such as carbonate and propylene carbonate; Amines such as triethylamine; Nitrogen-containing heterocyclic aromatic compounds such as pyridine; Nitriles such as acetonitrile and succinonitrile; N,N-dimethylformamide,
• the solvent preferably contains an aprotic compound (particularly preferably an aprotic compound without a halogen atom) because it has low corrosivity and is easy to handle.
• the proportion of the aprotic compound in the entire solvent is preferably 50% to 100% by weight, more preferably 70% to 100% by weight, particularly preferably 90% to 100% by weight.
• amides such as N,N-dimethylformamide, N,N-dimethylacetamide, tetramethylurea, N-methylpyrrolidone, etc. or ⁇ -butyrolactone etc. It preferably contains an ester, and more preferably N,N-dimethylformamide, N,N-dimethylacetamide, or N-methylpyrrolidone.
• the solvent preferably contains a compound having a dipole moment of 3 to 5 because it easily dissolves the above-mentioned polymers such as liquid crystal polymers.
• the proportion of the compound having a dipole moment of 3 to 5 in the entire solvent is preferably 50% to 100% by mass, more preferably 70% to 100% by mass, particularly preferably 90% to 100% by mass. be.
• a compound having a dipole moment of 3 to 5 is preferably used as the aprotic compound.
• the solvent preferably contains a compound having a boiling point of 220° C. or less at 1 atm, since it is easy to remove.
• the proportion of the compound having a boiling point of 220° C. or lower at 1 atm in the entire solvent is preferably 50% by mass to 100% by mass, more preferably 70% by mass to 100% by mass, particularly preferably 90% by mass to 100% by mass. It is.
• the aprotic compound it is preferable to use a compound whose boiling point at 1 atmosphere is 220° C. or less.
• a support may be used when producing the film by the above co-casting method, multilayer coating method, coextrusion method, or the like. Furthermore, when a metal layer (metal foil) or the like used in a laminate described later is used as a support, it may be used as it is without being peeled off. Examples of the support include a metal drum, metal band, glass plate, resin film, or metal foil. Among these, metal drums, metal bands, and resin films are preferred.
• Examples of the resin film include polyimide (PI) films, and examples of commercially available products include U-Pyrex S and U-Pyrex R manufactured by Ube Industries, Ltd., Kapton manufactured by DuPont Toray Co., Ltd., and Examples include IF30, IF70, and LV300 manufactured by SKC Kolon PI.
• a surface treatment layer may be formed on the surface of the support so that it can be easily peeled off.
• hard chrome plating, fluororesin, etc. can be used.
• the average thickness of the support is not particularly limited, but is preferably 25 ⁇ m or more and 75 ⁇ m or less, more preferably 50 ⁇ m or more and 75 ⁇ m or less.
• the method for removing at least a portion of the solvent from the cast or applied film-like composition is not particularly limited, and any known drying method may be used. .
• the film according to the present disclosure can be stretched in combination as appropriate from the viewpoint of controlling molecular orientation and adjusting linear expansion coefficient and mechanical properties.
• the stretching method is not particularly limited, and known methods can be referred to, and stretching may be carried out in a state containing a solvent or in a dry film state. Stretching in a state containing a solvent may be carried out by gripping and stretching the film, or may be carried out by utilizing self-shrinkage due to drying without stretching. Stretching is particularly effective for improving elongation at break and strength at break when film brittleness is reduced by addition of inorganic fillers or the like.
• the method for producing a film according to the present disclosure may include a step of polymerizing with light or heat, as necessary.
• the light irradiation means and heat application means are not particularly limited, and known light irradiation means such as a metal halide lamp, and known heat application means such as a heater can be used.
• the light irradiation conditions and the heat application conditions are not particularly limited, and can be performed at a desired temperature and time and in a known atmosphere.
• the method for manufacturing a film according to the present disclosure preferably includes a step of heat-treating (annealing) the film.
• the heat treatment temperature in the above heat treatment step is preferably 260°C to 370°C, more preferably 280°C to 360°C, and 300°C to 350°C from the viewpoint of dielectric loss tangent and peel strength. It is more preferable that The heat treatment time is preferably 15 minutes to 10 hours, more preferably 30 minutes to 5 hours.
• the method for manufacturing a film according to the present disclosure may include other known steps as necessary.
• the method for forming the mixed layer is not particularly limited, but for example, a method in which each layer is laminated in a fluid state containing a solvent and dried; another layer is laminated in a state containing a residual solvent and dried.
• Particularly preferred is a method using a solvent.
• Also effective are a method of adjusting the SP value of the material of each layer, and a method of adding a common material to each layer to promote mixing.
• the film according to the present disclosure can be used for various purposes, and among them, can be suitably used as a film for electronic components such as printed wiring boards, and can be suitably used for flexible printed circuit boards. Further, the film according to the present disclosure can be suitably used as a metal adhesive film.
• the laminate according to the present disclosure may be a laminate of the films according to the present disclosure, and includes the film according to the present disclosure and a metal layer or metal wiring arranged on at least one surface of the film.
• a laminate is preferred.
• the laminate according to the present disclosure preferably includes the film according to the present disclosure and a metal layer disposed on the layer B side surface of the film, and the metal layer is preferably a copper layer. More preferred.
• 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 according to the present disclosure having a layer B, a layer A, and a layer C in this order in the thickness direction, and a metal disposed on the surface of the layer B side of the film. It is preferable to have a metal layer arranged on the surface of the film on the side of the layer C, and it is more preferable that both 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.
• the metal layer disposed on the layer B side surface and the metal layer disposed on the layer C side surface may be made of different materials and have different thicknesses. and shaped metal layers.
• the metal layer arranged on the surface on the layer B side and the metal layer arranged on the surface on the layer C side may be metal layers of different materials and thicknesses, A metal layer may be laminated only on one side of layer B or layer C.
• an embodiment in which a metal layer is laminated on one side of layer B or layer C and another film is laminated on the other side is also preferably mentioned.
• the 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 preferably a rolled copper foil formed by a rolling method or an electrolytic copper foil formed by an electrolytic method.
• the average thickness of the metal layer, preferably the copper layer, is not particularly limited, but is preferably 2 ⁇ m to 30 ⁇ m, more preferably 3 ⁇ m to 20 ⁇ m, and even more preferably 5 ⁇ 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 10 ⁇ m to 100 ⁇ m, more preferably 18 ⁇ m to 50 ⁇ m.
• the metal layer is provided with a known surface treatment layer (for example, a chemical treatment layer) on the surface in contact with the film to ensure adhesive strength with the resin.
• a known surface treatment layer for example, a chemical treatment layer
• 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.
• 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 viewpoint 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.
• P2 Product name "Tuftec M1913", manufactured by Asahi Kasei Chemicals Co., Ltd., hydrogenated styrene-ethylene-butylene-styrene block copolymer
• PP-1 Liquid crystal polymer particles produced according to the manufacturing method below
• PP-2 Product name "Tuftec M1913, manufactured by Asahi Kasei Chemicals Co., Ltd., freeze-pulverized product of hydrogenated styrene-ethylene-butylene-styrene block copolymer (average particle size 5.0 ⁇ m (D50))
• 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 the aromatic polyesteramide P1 was 302°C.
• 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, and a melting point of 334°C.
• Example 1 Preparation of composition for forming layer C- 8 parts of aromatic polyesteramide P1 were added to 92 parts of N-methylpyrrolidone and stirred for 4 hours at 140°C under a nitrogen atmosphere to obtain an aromatic polyesteramide solution (solid content concentration 8% by mass).
• An aminophenol-type epoxy resin (“jER630" manufactured by Mitsubishi Chemical Corporation, 0.04 parts) was mixed with an aromatic polyesteramide solution (10.0 parts by mass) to prepare a composition for forming layer C. .
• composition for forming layer A Polymer P1 and polymer PP-1 were mixed at a mass ratio of 30:70, and N-methylpyrrolidone was added to adjust the solid content concentration to 22% by mass to obtain composition A1 for forming layer A.
• composition for forming layer B- N-methylpyrrolidone was added to PP-2 to adjust the solid content concentration to 20% by mass to obtain composition B1 for forming layer B.
• composition for forming layer C, composition A1 for forming layer A, and composition B1 for forming layer B were sent to a slot die coater equipped with a slide coater.
• Co., Ltd. CF-T4X-SV-18, thickness 18 ⁇ m, surface roughness Rz of the pasting surface (treated surface) 0.85 ⁇ m).
• the flow rate was applied to the treated surface to achieve the film thickness listed in Table 1. It was adjusted and coated in a three layer configuration (Layer C/Layer A/Layer B). At this time, the layer C was placed on the copper foil side.
• each composition was adjusted so that the thickness of layer C was 4 ⁇ m, and the thicknesses of layers A and B were as shown in Table 1.
• the solvent was removed from the coating film and a mixed layer was formed by drying at 40°C for 4 hours with dry air containing 8% by volume of N-methylpyrrolidone vapor, and then the coating was further dried for 1 hour from room temperature to 300°C under a nitrogen atmosphere.
• a heat treatment was performed in which the temperature was raised at a rate of °C/min and held at that temperature for 2 hours to obtain a film (single-sided copper-clad laminate) having a copper layer.
• Example 2 Example 1 was carried out in the same manner as in Example 1, except that the drying temperature was changed from 40°C to 70°C.
• Example 3 A film having a copper layer (single-sided copper-clad laminate) was obtained in the same manner as in Example 1, except that the manufacturing process of the single-sided copper-clad laminate in Example 1 was changed to the process shown below.
• composition for forming layer C, composition A1 for forming layer A, and composition B1 for forming layer B are fed to a slot die coater equipped with a feed block, and interlayer mixing is performed during feeding.
• CF-T4X-SV-18 thickness 18 ⁇ m, surface roughness Rz of the pasting surface (treated surface) Rz 0.85 ⁇ m
• Table 1 was applied on the treated surface of copper foil (manufactured by Fukuda Metal Foil & Powder Co., Ltd., CF-T4X-SV-18, thickness 18 ⁇ m, surface roughness Rz of the pasting surface (treated surface) Rz 0.85 ⁇ m). Table 1 was applied. The flow rate was adjusted to obtain the film thickness described in , and coating was performed in a three-layer structure (layer C/layer A/layer B). At this time, the layer C was placed on the copper foil side.
• each composition was adjusted so that the thickness of layer C was 4 ⁇ m, and the thicknesses of layers A and B were as shown in Table 1.
• the solvent is removed from the coating film and a mixed layer is formed, and then the temperature is raised from room temperature to 300°C at a rate of 1°C/min under a nitrogen atmosphere, and maintained at that temperature for 2 hours.
• a film having a copper layer (single-sided copper-clad laminate) was obtained.
• Example 1 A film having a copper layer (single-sided copper-clad laminate) was obtained in the same manner as in Example 1, except that the manufacturing process of the single-sided copper-clad laminate in Example 1 was changed to the process shown below.
• the obtained layer C was placed on the treated surface of copper foil (manufactured by Fukuda Metal Foil and Powder Co., Ltd., CF-T4X-SV-18, thickness 18 ⁇ m, surface roughness Rz of the pasting surface (treated surface) Rz 0.85 ⁇ m).
• the forming composition was applied and dried at 150°C for 1 hour.
• the obtained composition A1 for forming layer A was applied and dried at 40° C. for 4 hours.
• the obtained composition B1 for forming layer B was applied and dried at 40° C. for 4 hours.
• the resulting laminate having a three-layer structure (layer C/layer A/layer B) was further heated in a nitrogen atmosphere from room temperature to 300°C at a rate of 1°C/min, and then heat-treated by holding it at that temperature for 2 hours.
• a film (single-sided copper-clad laminate) having a copper layer was obtained.
• Example 2 A film having a copper layer (single-sided copper-clad laminate) was obtained in the same manner as in Example 1, except that the manufacturing process of the single-sided copper-clad laminate in Example 1 was changed to the process shown below.
• composition for forming layer A Polymer P1 and polymer PP-1 were mixed at a mass ratio of 30:70, and N-methylpyrrolidone was added to adjust the solid content concentration to 25% by mass to obtain composition A2 for forming layer A.
• composition for forming layer B- N-methylpyrrolidone was added to polymer P2, and the solid content concentration was adjusted to 20% by mass to obtain composition B2 for forming layer B.
• composition for forming layer C, composition A2 for forming layer A, and composition B2 for forming layer B were fed to a slot die coater equipped with a slide coater, and Co., Ltd., CF-T4X-SV-18, thickness 18 ⁇ m, surface roughness of the pasting surface (treated surface) Rz 0.85 ⁇ m) Adjust the flow rate so that the film thickness listed in Table 1 is obtained. and coated in a two-layer configuration (layer A/layer B). At this time, the layer A was placed on the copper foil side.
• the solvent was removed from the coating film by drying it at 40°C for 4 hours, and then heat treatment was performed in which the temperature was raised from room temperature to 300°C at a rate of 1°C/min in a nitrogen atmosphere and maintained at that temperature for 2 hours.
• a film having layers single-sided copper-clad laminate was obtained.
• the dielectric loss tangent, the elastic modulus at 160° C. of layer A and layer B, and the weight residual ratios L A and L B of layer A and layer B were measured.
• suitability for laser processing and step followability were evaluated.
• the measurement results and evaluation results are shown in Table 1.
• the "40% position” means the 40% position relative to the thickness of the film from the layer B side surface in the thickness direction.
• the composition at this 40% position was expressed as a mass ratio of composition A and composition B.
• the "60% position” means a position at 60% of the thickness of the film from the surface on the layer B side in the thickness direction.
• the composition at this 60% position was expressed as a mass ratio of composition A and composition B.
• Comparative Example 1 and Comparative Example 2 since there was no mixed layer, "-" was written in the column of mixed layer.
• 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.
• Step tracking ability (wiring tracking ability)] (1) Preparation of sample - Preparation of base material with wiring pattern - Copper foil (product name "CF-T9DA-SV-18", average thickness 18 ⁇ m, manufactured by Fukuda Metal Foil & Powder Industries Co., Ltd.) and a liquid crystal polymer film (product name "CTQ-50", average thickness 50 ⁇ m, manufactured by Kuraray Co., Ltd.) as a base material. 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.
• thermocompression bonding machine product name "MP-SNL", manufactured by Toyo Seiki Seisakusho
• the obtained double-sided copper-clad laminate precursor was thermocompression bonded for 10 minutes at 300°C and 4.5MPa. By doing so, a double-sided copper-clad laminate was produced.
• 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 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 had a wiring pattern (ground line and signal line) buried therein, and the thickness of the wiring pattern was 18 ⁇ m.
• the two virtual planes perpendicular to the thickness direction are A side made of composition A and B side made of composition B.
• the content of at least one component A contained in the composition A decreases from the A side toward the B side
• the content of at least one component B contained in the composition B decreases from the B side toward the A side. It was found that the dielectric loss tangent was 0.010 or less, so the suitability for laser processing was excellent.
• the compositions of layer A and layer B are constant, and the content of at least one component A contained in composition A does not decrease from side A to side B. It was found that the content of at least one component B contained in the composition B did not decrease from the B side toward the A side, so that the suitability for laser processing was poor.

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