Classifications

• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B15/00—Layered products comprising a layer of metal
  • B32B15/04—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
  • B32B27/00—Layered products comprising a layer of synthetic resin
  • B32B27/32—Layered products comprising a layer of synthetic resin comprising polyolefins
  • B32B27/322—Layered products comprising a layer of synthetic resin comprising polyolefins comprising halogenated polyolefins, e.g. PTFE
• • 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
  • B32B27/06—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
  • B32B27/00—Layered products comprising a layer of synthetic resin
  • B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
• • 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
  • B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
  • B32B27/20—Layered products comprising a layer of synthetic resin characterised by the use of special additives using fillers, pigments, thixotroping agents
• • 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
  • B32B27/32—Layered products comprising a layer of synthetic resin comprising polyolefins
  • B32B27/325—Layered products comprising a layer of synthetic resin comprising polyolefins comprising polycycloolefins
• • 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
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
  • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
  • C08J5/18—Manufacture of films or sheets
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L101/00—Compositions of unspecified macromolecular compounds
  • C08L101/12—Compositions of unspecified macromolecular compounds characterised by physical features, e.g. anisotropy, viscosity or electrical conductivity
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L27/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers
  • C08L27/02—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment
  • C08L27/12—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment containing fluorine atoms
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
• • G—PHYSICS
  • G02—OPTICS
  • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
  • G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
  • G02B1/02—Optical elements characterised by the material of which they are made; Optical coatings for optical elements made of crystals, e.g. rock-salt, semi-conductors
• • H—ELECTRICITY
  • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
  • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
  • H05K1/00—Printed circuits
  • H05K1/02—Details
• • H—ELECTRICITY
  • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
  • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
  • H05K1/00—Printed circuits
  • H05K1/02—Details
  • H05K1/03—Use of materials for the substrate
• • H—ELECTRICITY
  • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
  • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
  • H05K1/00—Printed circuits
  • H05K1/16—Printed circuits incorporating printed electric components, e.g. printed resistors, capacitors or inductors
• • H—ELECTRICITY
  • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
  • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
  • H05K3/00—Apparatus or processes for manufacturing printed circuits
  • H05K3/22—Secondary treatment of printed circuits
  • H05K3/28—Applying non-metallic protective coatings
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B2307/00—Properties of the layers or laminate
  • B32B2307/20—Properties of the layers or laminate having particular electrical or magnetic properties, e.g. piezoelectric
  • B32B2307/202—Conductive
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B2307/00—Properties of the layers or laminate
  • B32B2307/20—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
  • B32B2307/30—Properties of the layers or laminate having particular thermal 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
  • B32B2307/50—Properties of the layers or laminate having particular mechanical properties
  • B32B2307/538—Roughness
• • 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
  • B32B2307/724—Permeability to gases, adsorption
• • 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
  • B32B2307/724—Permeability to gases, adsorption
  • B32B2307/7242—Non-permeable
  • B32B2307/7246—Water vapor barrier
• • 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 a metamaterial base material, a metamaterial, and a laminate.
• a metamaterial comprising a base material and a pattern provided on the surface of the base material, which is composed of a conductive material or the like, has been used as an electromagnetic wave with a frequency of 0.1 THz to 10 THz (wavelength of 30 ⁇ m to 3000 ⁇ m) It is also described as an electromagnetic wave.) is being studied to apply to an optical element for.
• Japanese Patent Application Laid-Open No. 2021-114647 discloses a metamaterial including a metasurface substrate and a pattern of a metal film provided on the surface of the metasurface substrate.
• the pattern provided by the metamaterial functions as a resonator for electromagnetic waves in the terahertz band. Since the part that functions as a resonator for electromagnetic waves in the terahertz band is limited to a part about 0.5 ⁇ m from the surface of the pattern, it is possible to reduce the thickness of the pattern in terms of cost reduction in future development. is assumed.
• a pattern with a small thickness is likely to be formed on the surface of a base material by a method such as sputtering or vapor deposition, and depending on the smoothness of the base material surface, the smoothness of the pattern surface is reduced.
• the smoothness of the pattern surface decreases, the path through which the current flows becomes substantially longer, which tends to increase the possible transmission loss.
• high-frequency electromagnetic waves such as electromagnetic waves in the terahertz band
• a cyclic olefin resin (hereinafter also referred to as COP) film has been used as a base material.
• the surface may be roughened and the smoothness of the formed pattern may be impaired.
• An object to be solved by an embodiment of the present disclosure is to provide a metamaterial base material, a metamaterial, and a laminate that have excellent heat resistance and smoothness and can improve the smoothness of the formed pattern. is.
• ⁇ 4> A metamaterial substrate according to any one of the above ⁇ 1> to ⁇ 3>, and a pattern on a surface of the metamaterial substrate having a surface roughness Ra of 300 nm or less, and a metamaterial, wherein the pattern is composed of at least one of a conductive material and a material that changes from a nonconductor to a conductor.
• ⁇ 5> The metamaterial according to ⁇ 5> above, wherein the pattern has a thickness of less than 5 ⁇ m.
• ⁇ 6> The metamaterial according to ⁇ 4> or ⁇ 5> above, wherein the pattern includes a plurality of structures, and the structures are split ring resonators.
• ⁇ 7> The metamaterial according to any one of ⁇ 4> to ⁇ 6>, wherein the pattern is made of the conductive material, and the conductive material contains a metal.
• ⁇ 8> The metamaterial according to any one of ⁇ 4> to ⁇ 7>above; and an organic film provided on the pattern-side surface of the metamaterial.
• ⁇ 9> The laminate according to ⁇ 8> above, wherein the organic film has a moisture permeability of 3000 g/(m 2 ⁇ 24 hours) or less under an environment of a temperature of 40°C and a relative humidity of 90%.
• the organic film contains an ultraviolet absorber.
• a metamaterial base material a metamaterial, and a laminate that have excellent heat resistance and smoothness and can improve the smoothness of the formed pattern.
• FIG. 1 is a perspective view showing one embodiment of the metamaterial of the present disclosure.
• the numerical range indicated using "-" includes the numerical values before and after "-" as the minimum and maximum values, respectively.
• the upper limit or lower limit of one numerical range may be replaced with the upper or lower limit of another numerical range described step by step.
• the upper or lower limits of the numerical ranges may be replaced with the values shown in the examples.
• each component may contain multiple types of applicable substances.
• layer or film refers to the case where the layer or film is formed in the entire region when observing the region where the layer or film is present, and only a part of the region. It also includes the case where it is formed.
• process includes not only an independent process but also a process that cannot be clearly distinguished from other processes as long as the intended purpose of the process is achieved.
• the term “metamaterial” refers to a member made of a conductive material or the like and having a pattern that functions as a resonator for electromagnetic waves.
• the metamaterial preferably has a pattern that serves as a resonator for electromagnetic waves with frequencies of 0.01 THz to 10 THz (wavelengths of 30 ⁇ m to 30000 ⁇ m), and resonates with electromagnetic waves with frequencies of 0.1 THz to 10 THz (wavelengths of 30 ⁇ m to 3000 ⁇ m). It is more preferable to have a pattern that serves as a vessel.
• measurement of moisture permeability is carried out under the conditions of a temperature of 40°C, a relative humidity of 90%, and standing for 24 hours in accordance with the method described in JIS Z 0208 (1976).
• GPC gel permeation chromatography
• (meth)acrylic is a concept that includes both acrylic and methacrylic.
• solid content means a component that forms a layer formed using a composition or the like, and when the composition or the like contains a solvent (organic solvent, water, etc.), all means a component of In addition, as long as it is a layer-forming component, a liquid component is also regarded as a solid content.
• the base material for metamaterials of the present disclosure (hereinafter also referred to as base material) has a glass transition temperature of 160° C. or higher and a surface roughness Ra of at least one surface of 300 nm or lower.
• the glass transition temperature of the substrate is preferably 165°C to 300°C, more preferably 170°C to 250°C, even more preferably 175°C to 230°C.
• the glass transition temperature of the base material can be adjusted by changing the materials contained in the base material.
• the glass transition temperature of the substrate is measured as follows. A piece of base material is enclosed in a measurement pan, and a thermogram obtained by raising the temperature at a rate of 20 ° C./min using a differential scanning calorimeter is used. Obtained as the glass transition temperature. As the differential scanning calorimeter, DSC6200 manufactured by Seiko Instruments Inc. or a similar device can be used. When the substrate has two or more glass transition temperatures, if the smaller glass transition temperature is 160° C. or higher, the condition “the substrate has a glass transition temperature of 160° C. or higher” is satisfied.
• the surface roughness Ra of the metamaterial substrate is preferably 250 nm or less, more preferably 100 nm or less, and 50 nm or less. It is more preferably 30 nm or less, particularly preferably 10 nm or less, and most preferably 10 nm or less.
• the lower limit of the surface roughness Ra is not particularly limited, and may be 0 nm.
• the surface roughness Ra of the base material can be adjusted by changing the material contained in the base material, the manufacturing method of the base material, and the like. As a method for forming a film of the base material, a composition containing the above resin etc.
• a method of dissolving or dispersing in a solvent, forming a film by casting or coating, and drying in order to improve the smoothness of the support surface side, it is preferable to use a chill roll or a casting or coating support having high smoothness. Moreover, from the viewpoint of improving smoothness, it is preferable to employ a film forming method in which a solution is cast or applied. Furthermore, in order to improve the smoothness of the surface forming the metamaterial, it is also effective to use a reverse gravure coater or the like to coat and dry the surface of the melt-cast or solution-cast film. . In addition, in order to improve the smoothness, it is also effective to stretch the formed film or to adjust the tension applied to the film in the drying or heat treatment process.
• the surface roughness Ra of the substrate is obtained as follows. First, a cross-sectional sample of the substrate is cut using a microtome. A curve of the interface shape of the cut cross-sectional sample and an average line of the curve of the interface shape are created, and the surface roughness Ra is determined from these. When the base material is included in a metamaterial, laminate, or the like, which will be described later, a cross-sectional sample of the metamaterial or the like is used. For the measurement of the surface roughness Ra, a non-contact surface/layer profile measuring system VertScan (Mitsubishi Chemical Systems Co., Ltd.) or a similar device can be used.
• VertScan Mitsubishi Chemical Systems Co., Ltd.
• the dielectric loss tangent of the substrate is preferably 0.01 or less, more preferably 0.0005 to 0.007, even more preferably 0.001 to 0.006. , 0.001 to 0.005.
• the dielectric loss tangent of the base material can be adjusted by changing the material contained in the base material.
• the dielectric loss tangent of the substrate is measured by the following terahertz time domain spectroscopy (THz-TDS).
• THz-TDS terahertz time domain spectroscopy
• a substrate is cut into a test piece of 100 mm ⁇ 100 mm.
• an optical system for transmission type terahertz spectroscopy was prepared, and the dielectric loss tangent of the test piece was measured from the change in the time waveform of the optical electric field (frequency 1 THz) before and after the test piece was inserted in an environment of 25°C and 10% RH. do.
• the dielectric loss tangent is measured using a base material etched with a solution such as iron chloride.
• the material constituting the base material is not particularly limited, and resin is preferable from the viewpoint of handleability and the like.
• resins that can be contained in the substrate 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 ketones, polyolefins, polyamides, and polyesters.
• thermoplastic resins such as polyetherimide; elastomers such as copolymers of glycidyl methacrylate and polyethylene; phenolic resins , epoxy resins, polyimide resins, and cyanate resins.
• liquid crystal polymers from the viewpoint of dielectric loss tangent, adhesion to patterns, and heat resistance, liquid crystal polymers, fluorine-based polymers, polymers of compounds having a cyclic aliphatic hydrocarbon group and a group having an ethylenically unsaturated bond , polyphenylene ethers and aromatic polyether ketones, and epoxy resins, and more preferably at least one selected from the group consisting of liquid crystal polymers and fluoropolymers. . From the viewpoint of adhesion to the pattern and mechanical strength, it is preferably a liquid crystal polymer, and from the viewpoint of heat resistance and dielectric loss tangent, a group having a cyclic aliphatic hydrocarbon group and an ethylenically unsaturated bond. Polymers of compounds having and, polyarylates, polyethersulfones, and fluoropolymers are preferred.
• the liquid crystal polymer may be a thermotropic liquid crystal polymer that exhibits liquid crystallinity in a molten state, or a lyotropic liquid crystal polymer that exhibits liquid crystallinity in a solution state.
• the liquid crystal polymer is a thermotropic liquid crystal polymer, it is preferably a liquid crystal polymer that melts at a temperature of 450° C. or less.
• liquid crystal polymers include liquid crystal polyesters, liquid crystal polyester amides in which amide bonds are introduced into liquid crystal polyesters, liquid crystal polyester ethers in which ether bonds are introduced into liquid crystal polyesters, and liquid crystal polyester carbonates in which carbonate bonds are introduced into liquid crystal polyesters. can be done.
• the liquid crystal polymer is preferably a polymer having an aromatic ring, more preferably an aromatic polyester or an aromatic polyesteramide.
• the liquid crystal polymer may be a polymer obtained by introducing an isocyanate-derived bond such as an imide bond, a carbodiimide bond, or an isocyanurate bond into an aromatic polyester or an aromatic polyesteramide.
• the liquid crystal polymer is preferably a wholly aromatic liquid crystal polymer using only aromatic compounds as raw material monomers.
• liquid crystal polymers include, for example, the following liquid crystal polymers. 1) (i) an aromatic hydroxycarboxylic acid, (ii) an aromatic dicarboxylic acid, and (iii) at least one compound selected from the group consisting of an aromatic diol, an aromatic hydroxylamine and an aromatic diamine; A product obtained by polycondensation. 2) Those obtained by polycondensing a plurality of types of aromatic hydroxycarboxylic acids. 3) Polycondensation of (i) an aromatic dicarboxylic acid and (ii) at least one compound selected from the group consisting of aromatic diols, aromatic hydroxylamines and aromatic diamines.
• aromatic hydroxycarboxylic acids aromatic dicarboxylic acids, aromatic diols, aromatic hydroxyamines and aromatic diamines may each independently be replaced with polycondensable derivatives.
• aromatic hydroxycarboxylic acids and aromatic dicarboxylic acids can be replaced with aromatic hydroxycarboxylic acid esters and aromatic dicarboxylic acid esters by converting a carboxy group to an alkoxycarbonyl group or an aryloxycarbonyl group.
• Aromatic hydroxycarboxylic acids and aromatic dicarboxylic acids can be replaced with aromatic hydroxycarboxylic acid halides and aromatic dicarboxylic acid halides by converting the carboxy group to a haloformyl group.
• Aromatic hydroxycarboxylic acids and aromatic dicarboxylic acids can be replaced with aromatic hydroxycarboxylic acid anhydrides and aromatic dicarboxylic acid anhydrides by converting carboxy groups to acyloxycarbonyl groups.
• polymerizable derivatives of compounds having a hydroxy group such as aromatic hydroxycarboxylic acids, aromatic diols and aromatic hydroxyamines include those obtained by acylating the hydroxy group to convert it to an acyloxy group (acylated product).
• aromatic hydroxycarboxylic acids, aromatic diols, and aromatic hydroxyamines can each be replaced with an acylate by acylating the hydroxy group to convert it to an acyloxy group.
• polymerizable derivatives of compounds having an amino group such as aromatic hydroxylamines and aromatic diamines include those obtained by acylating the amino group to convert it to an acylamino group (acylated product).
• an acylate can replace an aromatic hydroxyamine and an aromatic diamine, respectively, by acylating the amino group to convert it to an acylamino group.
• the liquid crystal polymer is a structural unit represented by any of the following formulas (1) to (3) (hereinafter, represented by formula (1) may be referred to as a structural unit (1), etc.), more preferably a structural unit represented by the following formula (1), 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 represents a phenylene group, naphthylene group or biphenylylene group
• Ar 2 and Ar 3 each independently represent a phenylene group, naphthylene group, biphenylylene group or the following formula (4) and each of X and Y independently represents an oxygen atom or an imino group
• the hydrogen atoms in Ar 1 to Ar 3 are each independently substituted with a halogen atom, an alkyl group or an aryl group.
• 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.
• the halogen atoms include fluorine, chlorine, bromine and iodine atoms.
• 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, n-octyl and n-decyl groups are included.
• the number of carbon atoms in the alkyl group is preferably 1-10.
• the aryl group includes phenyl group, o-tolyl group, m-tolyl group, p-tolyl group, 1-naphthyl group and 2-naphthyl group.
• the aryl group preferably has 6 to 20 carbon atoms.
• 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, 1,1-ethanediyl group, 1-methyl-1,1-ethanediyl group, 1,1-butanediyl group and 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 an aromatic hydroxycarboxylic acid.
• Ar 1 is a p-phenylene group (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.
• Structural unit (2) is a structural unit derived from an aromatic dicarboxylic acid.
• the structural unit (2) include an embodiment in which Ar 2 is a p-phenylene group (structural unit derived from terephthalic acid), an embodiment in which Ar 2 is an m-phenylene group (structural unit derived from isophthalic acid), and Ar 2 is a 2,6-naphthylene group (structural unit derived from 2,6-naphthalene dicarboxylic acid), or an embodiment in which Ar 2 is a diphenyl ether-4,4'-diyl group (diphenyl ether-4,4'- Structural units derived from dicarboxylic acids) are preferred.
• Structural unit (3) is a structural unit derived from an aromatic diol, aromatic hydroxylamine or aromatic diamine.
• Ar 3 is a p-phenylene group (structural unit derived from hydroquinone, p-aminophenol or p-phenylenediamine)
• Ar 3 is an 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 unit) is preferred.
• the content of the structural unit (1) is obtained by dividing the total amount of all structural units (the mass of each structural unit constituting the liquid crystal polymer (also referred to as "monomer unit") by the formula weight of each structural unit. It is preferably 30 mol% or more, more preferably 30 mol% to 80 mol%, still more preferably 30 mol% to 60 mol, based on the sum of the amounts (moles) equivalent to the amount of substances of the structural units. %, 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%, still more preferably 20 mol% to 35 mol%, particularly It is preferably 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%, still more preferably 20 mol% to 35 mol%, particularly It is preferably 30 mol % to 35 mol %.
• the higher the content of the structural unit (1) the more likely the heat resistance, strength and rigidity are to be improved.
• the ratio between the content of the structural unit (2) and the content of the structural unit (3) is expressed as [content of the structural unit (2)]/[content of the structural unit (3)] (mol/mol). , preferably 0.9/1 to 1/0.9, more preferably 0.95/1 to 1/0.95, still more preferably 0.98/1 to 1/0.98.
• the liquid crystal polymer may have two or more types of structural units (1) to (3) each independently.
• the liquid crystal polymer may have structural units other than the structural units (1) to (3), but the content thereof is preferably 10 mol% or less, more than Preferably, it is 5 mol % or less.
• the liquid crystal polymer has a structural unit (3) in which at least one of X and Y is an imino group, that is, the structural unit (3) is an aromatic It preferably contains at least one of a structural unit derived from hydroxylamine and a structural unit derived from an aromatic diamine, and more preferably contains only the structural unit (3) in which at least one of X and Y is an imino group.
• the liquid crystal polymer is preferably produced by melt-polymerizing raw material monomers corresponding to the structural units that constitute the liquid crystal polymer. Melt polymerization may be carried out in the presence of a catalyst.
• catalysts include metal compounds such as magnesium acetate, stannous acetate, tetrabutyl titanate, lead acetate, sodium acetate, potassium acetate, antimony trioxide, 4-(dimethylamino)pyridine, 1-methylimidazole and the like.
• examples include nitrogen heterocyclic compounds, and nitrogen-containing heterocyclic compounds are preferred.
• the melt polymerization may be further subjected to solid phase polymerization, if necessary.
• 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 are particularly preferred.
• the substrate is excellent in thermal conductivity, heat resistance, strength and rigidity in the thickness direction.
• fluorine-based polymers include polytetrafluoroethylene, polychlorotrifluoroethylene, polyvinylidene fluoride, polyvinyl fluoride, perfluoroalkoxy fluororesin, ethylene tetrafluoride/propylene hexafluoride copolymer, ethylene/tetrafluoride
• fluorine-based polymers include polytetrafluoroethylene, polychlorotrifluoroethylene, polyvinylidene fluoride, polyvinyl fluoride, perfluoroalkoxy fluororesin, ethylene tetrafluoride/propylene hexafluoride copolymer, ethylene/tetrafluoride
• Examples include ethylene copolymers, ethylene/chlorotrifluoroethylene copolymers, and the like. Among them, polytetrafluoroethylene is preferred.
• Fluoropolymers also include fluorinated ⁇ -olefin monomers, i.e. ⁇ -olefin monomers containing at least one fluorine atom, and optionally non-fluorinated ethylene reactive with the fluorinated ⁇ -olefin monomers. Homopolymers and copolymers containing constitutional units derived from polyunsaturated monomers are included.
• vinyl ether eg, perfluoromethyl vinyl ether, perfluoropropyl vinyl ether, perfluorooctyl vinyl ether
• Non-fluorinated monoethylenically unsaturated monomers include ethylene, propylene, butene, ethylenically unsaturated aromatic monomers (eg, styrene and ⁇ -methylstyrene), and the like.
• the fluorinated ⁇ -olefin monomers may be used singly or in combination of two or more.
• the non-fluorinated ethylenically unsaturated monomers may be used singly or in combination of two or more.
• fluorine-based polymers examples include poly(chlorotrifluoroethylene) (PCTFE), poly(chlorotrifluoroethylene-propylene), poly(ethylene-tetrafluoroethylene) (ETFE), poly(ethylene-chlorotrifluoroethylene) (ECTFE).
• PCTFE poly(chlorotrifluoroethylene)
• ETFE poly(ethylene-tetrafluoroethylene)
• ECTFE poly(ethylene-chlorotrifluoroethylene)
• PTFE poly(tetrafluoroethylene)
• FEP fluorinated ethylene-propylene copolymer
• FEP fluoroelastomer
• poly(tetrafluoroethylene-perfluoropropylene vinyl ether) poly(tetrafluoroethylene main chain and fully fluorinated alkoxy side chains.
• copolymer also called perfluoroalkoxy polymer poly(tetrafluoroethylene-perfluoroalkyl vinyl ether) (PFA)) (e.g., poly(tetrafluoroethylene-perfluoropropylene propyl vinyl ether))), polyvinyl fluoride (PVF),
• PVDF polyvinylidene fluoride
• PVDF poly(vinylidene fluoride-chlorotrifluoroethylene
• perfluoropolyether perfluorosulfonic acid
• the fluorine-based polymer may be used singly or in combination of two or more.
• the fluoropolymer is preferably at least one of FEP, PFA, ETFE, or PTFE. They may be fibril-forming or non-fibril-forming.
• 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 trade name of NEOFLON PFA from Daikin Industries, Ltd., the trade name of Teflon (registered trademark) PFA (TEFLON (registered trademark) PFA) from DuPont, or Solvay Solexis. Solexis) under the trade name of HYFLON PFA.
• the fluoropolymer preferably contains PTFE.
• the PTFE can comprise PTFE homopolymer, partially modified PTFE homopolymer, or a combination comprising either or both of these.
• the partially modified PTFE homopolymer preferably contains less than 1% by weight of units derived from comonomers other than tetrafluoroethylene, based on the total weight of the polymer.
• the fluoropolymer may be a crosslinkable fluoropolymer having crosslinkable groups.
• the crosslinkable fluoropolymer can be crosslinked by conventionally known crosslinking methods.
• One representative crosslinkable fluoropolymer is a fluoropolymer having (meth)acryloxy groups.
• R is a fluorine-based oligomer chain having two or more structural units derived from a fluorinated ⁇ -olefin monomer or a non-fluorinated monoethylenically unsaturated monomer
• R ' is H or - CH 3 and n is 1-4.
• R may be a fluorine-based oligomer chain containing constitutional units derived from tetrafluoroethylene.
• Forming a crosslinked fluoropolymer network by exposing a fluoropolymer having (meth)acryloxy groups to a free radical source to initiate a radical crosslinking reaction through the (meth)acryloxy groups on the fluoropolymer.
• the free radical source is not particularly limited, but preferably includes a photoradical polymerization initiator or an organic peroxide. Suitable radical photoinitiators and organic peroxides are well known in the art.
• Crosslinkable fluoropolymers are commercially available, for example, Viton B manufactured by DuPont.
• polymers of compounds having a cyclic aliphatic hydrocarbon group and a group having an ethylenically unsaturated bond include, for example, structural units formed from monomers composed of cyclic olefins such as norbornene or polycyclic norbornene-based monomers and is also called a thermoplastic cyclic olefin resin.
• a polymer of a compound having a cyclic aliphatic hydrocarbon group and a group having an ethylenically unsaturated bond is a ring-opening polymer of the above cyclic olefin or a ring-opening copolymer using two or more cyclic olefins and hydrogenated.
• 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.
• a polar group may be introduced into the polymer of the compound having a cyclic aliphatic hydrocarbon group and a group having an ethylenically unsaturated bond.
• Polymers of compounds having a cyclic aliphatic hydrocarbon group and a group having an ethylenically unsaturated bond may be used singly or in combination of two or more.
• the ring structure of the cycloaliphatic hydrocarbon group may be a monocyclic ring, a condensed ring in which two or more rings are condensed, or a bridged ring.
• the ring structure of the cycloaliphatic hydrocarbon group includes a cyclopentane ring, cyclohexane ring, cyclooctane ring, isoboron ring, norbornane ring, dicyclopentane ring and the like.
• a 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 cycloaliphatic hydrocarbon groups in a compound having a cycloaliphatic hydrocarbon group and a group having an ethylenically unsaturated bond may be 1 or more, and may be 2 or more.
• a polymerized product of a compound having a cyclic aliphatic hydrocarbon group and a group having an ethylenically unsaturated bond is obtained by polymerizing a compound having at least one cyclic aliphatic hydrocarbon group and a group having an ethylenically unsaturated bond.
• It may be a polymer of a compound having two or more cyclic aliphatic hydrocarbon groups and a group having an ethylenically unsaturated bond, or it may be a polymer having no cyclic aliphatic hydrocarbon group. It may be a copolymer with other ethylenically unsaturated compounds.
• the polymer of the compound having a cyclic aliphatic hydrocarbon group and a group having an ethylenically unsaturated bond is preferably a cycloolefin polymer.
• the average number of phenolic hydroxyl groups at the ends of the molecules per molecule is preferably 1 to 5 from the viewpoint of dielectric loss tangent and heat resistance, and 1.5. It is more preferable that the number is from 1 to 3.
• the number of hydroxyl groups or phenolic hydroxyl groups of polyphenylene ether can be known, for example, from the standard values of polyphenylene ether products. Further, the number of terminal hydroxyl groups or the number of terminal phenolic hydroxyl groups includes, for example, a numerical value representing the average value of hydroxyl groups or phenolic hydroxyl groups per molecule of all polyphenylene ethers present in 1 mol 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 composed of 2,6-dimethylphenol and at least one of difunctional phenol and trifunctional phenol, poly(2,6-dimethyl-1,4-phenylene oxide), and the like. and polyphenylene ether as main components. More specifically, for example, it is preferably a compound having a structure represented by 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
• Sum represents an integer from 1-30.
• alkylene group for X include a dimethylmethylene group.
• the aromatic polyether ketone is not particularly limited, and known aromatic polyether ketones can be used.
• the aromatic polyetherketone is preferably polyetheretherketone.
• Polyether ether ketone is a type of aromatic polyether ketone, and is a polymer in which bonds are arranged in the order of ether bond, ether bond, and carbonyl bond (ketone). Each bond is preferably connected by a divalent aromatic group.
• Aromatic polyether ketones may be used singly or in combination of two or more.
• aromatic polyether ketone examples include polyether ether ketone (PEEK) having a chemical structure represented by the following formula (P1) and polyether ketone (PEK) having a chemical structure represented by the following formula (P2). , a polyether ketone ketone (PEKK) having a chemical structure represented by the following formula (P3), a polyether ether ketone ketone (PEEKK) having a chemical structure represented by the following formula (P4), and the following formula (P5) Polyether ketone ether ketone ketone (PEKEKK) having the chemical structure depicted.
• n in each of formulas (P1) to (P5) is preferably 10 or more, more preferably 20 or more.
• n is preferably 5,000 or less, more preferably 1,000 or less, from the viewpoint of easy production of aromatic polyetherketone. That is, n is preferably 10 to 5,000, more preferably 20 to 1,000.
• the content of the resin with respect to the total mass of the substrate is not particularly limited, and is preferably 50% by mass or more, more preferably 70% by mass or more, and further preferably 90% by mass or more. preferable.
• the upper limit of the resin content is not particularly limited, and may be 100% by mass.
• the substrate may contain compounds having functional groups.
• the functional group includes at least one of a conductive material constituting the pattern and a material that changes from a nonconductor to a conductor, a group capable of covalent bonding, a group capable of ionically bonding, and hydrogen. It is preferably at least one group selected from the group consisting of a group capable of bonding, a group capable of dipole interaction, and a group capable of curing reaction.
• the compound having a functional group can also form the above-mentioned bond or the like with the material constituting the base material.
• a compound having a functional group may be a low-molecular-weight compound or a high-molecular-weight compound.
• the compound having a functional group is preferably a low-molecular-weight compound from the viewpoint of the dielectric loss tangent of the substrate, and is preferably a high-molecular compound from the viewpoint of the heat resistance and mechanical strength of the substrate.
• the number of functional groups in the compound having a functional group may be 1 or more, and may be 2 or more, but is preferably 2 or more. From the viewpoint of reducing the dielectric loss tangent, it is preferably 10 or less.
• the compound having a functional group may have only one type of functional group, or may have two or more types of functional groups.
• the low-molecular-weight compound used as the compound having a functional group preferably has a molecular weight of 50 or more and less than 2,000, more preferably 100 or more and less than 1,000, from the viewpoint of adhesion to the pattern. Particularly preferably, the molecular weight is 200 or more and less than 1,000.
• the polymer compound used as the compound having a functional group is preferably a polymer having a weight average molecular weight of 1,000 or more from the viewpoint of adhesion to the pattern, and a polymer having a weight average molecular weight of 2,000 or more.
• a polymer more preferably a polymer having a weight average molecular weight of 3,000 or more and 1,000,000 or less, and particularly a polymer having a weight average molecular weight of 5,000 or more and 200,000 or less. preferable.
• the resin and the compound having a functional group are compatible with each other.
• being compatible means that no phase separation is confirmed inside the base material.
• the difference between the SP value of the resin by the Hoy method and the SP value of the compound having a functional group by the Hoy method is 5 MPa 0.5 or less from the viewpoint of compatibility, dielectric loss tangent of the substrate, and adhesion to the pattern.
• a lower limit is 0 MPa 0.5 .
• the SP value (solubility parameter value) by the Hoy method is calculated from the molecular structure of the resin by the method described in the Polymer Handbook fourth edition. Also, when the resin is a mixture of a plurality of resins, the SP value is calculated for each structural unit.
• the group capable of covalent bonding is not particularly limited as long as it is a group capable of forming a covalent bond with a conductive material or the like.
• Ester group, glyoxal group, imide ester group, halogenated alkyl group, thiol group, hydroxy group, carboxy group, amino group, amide group, isocyanate group, aldehyde group, sulfonic acid group and the like can be mentioned.
• At least one selected from the group consisting of an epoxy group, an oxetanyl group, an N-hydroxyester group, an isocyanate group, an imidoester group, a halogenated alkyl group, and a thiol group, from the viewpoint of adhesion to the pattern. is preferred, and an epoxy group is particularly preferred.
• a cationic group, an anionic group, etc. are mentioned as an electroconductive material etc. and a group which can be ion-bonded.
• the cationic group is preferably an onium group.
• onium groups include ammonium groups, pyridinium groups, phosphonium groups, oxonium groups, sulfonium groups, selenonium groups, iodonium groups, and the like. Among them, from the viewpoint of adhesion to a pattern, an ammonium group, a pyridinium group, a phosphonium group, or a sulfonium group is preferred, an ammonium group or a phosphonium group is more preferred, and an ammonium group is particularly preferred.
• the anionic group is not particularly limited, and examples thereof include phenolic hydroxyl group, carboxy group, -SO 3 H, -OSO 3 H, -PO 3 H, -OPO 3 H 2 , -CONHSO 2 -, and -SO 2 NHSO. 2 - and the like.
• a phosphoric acid group, a phosphonic acid group, a phosphinic acid group, a sulfuric acid group, a sulfonic acid group, a sulfinic acid group or a carboxy group is preferred, and a phosphoric acid group or a carboxy group is more preferred.
• a carboxy group is more preferred.
• the group capable of forming a hydrogen bond with a conductive material or the like includes a group having a hydrogen bond donating site and a group having a hydrogen bond accepting site.
• the hydrogen bond donating site may have a structure having an active hydrogen atom capable of hydrogen bonding, but preferably has a structure represented by XH.
• X represents a heteroatom, preferably a nitrogen atom or an oxygen atom.
• the hydrogen bond donating site includes a hydroxy group, a carboxyl group, a primary amide group, a secondary amide group, a primary amino group, a secondary amino group, a primary It is preferably at least one structure selected from the group consisting of a primary sulfonamide group, a secondary sulfonamide group, an imide group, a urea bond, and a urethane bond, and a hydroxy group, a carboxyl group, and a primary amide group.
• a secondary amide group, a primary sulfonamide group, a secondary sulfonamide group, a maleimide group, a urea bond and at least one structure selected from the group consisting of a urethane bond, more preferably a hydroxy at least one structure selected from the group consisting of a group, a carboxyl group, a primary amide group, a secondary amide group, a primary sulfonamide group, a secondary sulfonamide group, and a maleimide group More preferably, at least one structure selected from the group consisting of a hydroxy group and a secondary amide group is particularly preferred.
• the hydrogen bond-accepting site preferably has a structure containing an atom having a lone pair, preferably a structure containing an oxygen atom having a lone pair, and a carbonyl group (carboxy group, amide group, imide group , including carbonyl structures such as urea bonds and urethane bonds), and sulfonyl groups (including sulfonyl structures such as sulfonamide groups). More preferably, at least one structure selected from the group consisting of A carbonyl group (including carbonyl structures such as a carboxy group, an amide group, an imide group, a urea bond, and a urethane bond) is particularly preferred.
• the group capable of hydrogen bonding is preferably a group having both a hydrogen bond donating site and a hydrogen bond accepting site, such as a carboxy group, an amide group, an imide group, a urea bond, a urethane bond, or a sulfonamide It preferably has a group, and more preferably has a carboxy group, an amide group, an imide group, or a sulfonamide group.
• a structure other than the structure represented by XH (X represents a hetero atom, a nitrogen atom or an oxygen atom) in the group capable of hydrogen bonding
• X represents a hetero atom, a nitrogen atom or an oxygen atom
• Any group may be used as long as it has a structure, and preferred examples thereof include groups in which atoms having different electronegativities are bonded.
• the combination of atoms with different electronegativities is preferably a combination of at least one atom selected from the group consisting of an oxygen atom, a nitrogen atom, a sulfur atom, and a halogen atom and a carbon atom.
• a combination of at least one atom selected from the group consisting of sulfur atoms and a carbon atom is more preferred.
• a combination of a nitrogen atom and a carbon atom, and a combination of a carbon atom, a nitrogen atom, an oxygen atom and a sulfur atom are preferable from the viewpoint of adhesion to a pattern, and specifically, a cyano group and a cyanuric group. , a sulfonic acid amide group is more preferred.
• a curable compound is a compound that is cured by irradiation with heat or light (eg, visible light, ultraviolet light, near-infrared rays, far-infrared rays, electron beams, etc.).
• curable compounds include epoxy compounds, cyanate ester compounds, vinyl compounds, silicone compounds, oxazine compounds, maleimide compounds, allyl compounds, acrylic compounds, methacrylic compounds, and urethane compounds. These may be used individually by 1 type, and 2 or more types may be used together.
• epoxy compounds from the viewpoint of properties such as compatibility with resins and heat resistance, it is selected from the group consisting of epoxy compounds, cyanate ester compounds, vinyl compounds, silicone compounds, oxazine compounds, maleimide compounds, and allyl compounds. At least one compound is preferred, and at least one compound selected from the group consisting of epoxy compounds, cyanate ester compounds, vinyl compounds, allyl compounds, and silicone compounds is more preferred.
• the content of the compound having a functional group with respect to the total mass of the substrate is preferably 0.01% by mass to 10% by mass, and 0.03% by mass to 5% by mass. more preferably 0.05% by mass to 3% by mass.
• the substrate may contain at least one filler.
• the filler may be an organic filler or an inorganic filler.
• organic fillers include particles of liquid crystal polymers, polyolefins, fluorine-based polymers, and the like.
• Inorganic fillers include particles of silica, alumina, titania, zirconia, kaolin, calcined kaolin, talc, mica, sodium carbonate, calcium carbonate, aluminum hydroxide, magnesium hydroxide, zinc oxide, and the like. From the viewpoint of reducing the coefficient of thermal expansion, it is preferable that the base material contains silica particles among those mentioned above.
• the filler is preferably contained in a layer other than the layer having the surface on which the pattern is formed, from the viewpoint of improving the smoothness of the pattern formed on the surface of the substrate.
• the substrate has a three-layer structure of a first layer, a second layer and a third layer, and a pattern is formed in the first layer, the second layer or the third layer It is preferable to contain a filler.
• the average particle size of the filler is preferably 5 nm to 20 ⁇ m, more preferably 10 nm to 10 ⁇ m, even more preferably 20 nm to 1 ⁇ m, from the viewpoints of thermal expansion coefficient and adhesion to the pattern. , between 25 nm and 500 nm.
• the average particle size of the filler is determined by arithmetically averaging the particle sizes of 50 particles randomly selected from the scanning electron microscope (SEM) image.
• the content of the filler relative to the total mass of the substrate is preferably 10% to 40% by mass, and 15% to 35% by mass. and more preferably 20% by mass to 30% by mass.
• the content of the filler relative to the total mass of the layer containing the filler is preferably 20% to 70% by mass, and 30% to 65% by mass, from the viewpoint of reducing the coefficient of thermal expansion. %, more preferably 40% by mass to 60% by mass.
• the substrate may contain various additives, including polymerization initiators, dispersants, surfactants, cross-linking agents, antioxidants, and the like.
• a woven fabric such as a glass cloth or a non-woven fabric impregnated with the above resin may be used.
• a material such as the above-described resin may be used to form a layer on at least one surface of a glass cloth or the like impregnated with the above-described resin to form a multi-layered structure, which may be used as the base material.
• the thickness of the substrate is not particularly limited, and from the viewpoint of handleability, it is preferably 5 ⁇ m to 200 ⁇ m, more preferably 10 ⁇ m to 180 ⁇ m, and even more preferably 15 ⁇ m to 150 ⁇ m.
• the base material may be prepared by a conventionally known method, or may be commercially available. A method for producing the base material is illustrated in Examples.
• the metamaterial of the present disclosure includes a metamaterial substrate and a pattern on a surface of the metamaterial substrate having a surface roughness Ra of 300 nm or less, and the pattern comprises a conductive material and a non-conductive material. It is composed of at least one of materials that change from conductor to conductor. Since the base material for metamaterials has been described above, the description thereof is omitted here.
• the pattern is composed of at least one of a conductive material and a material that changes from a nonconductor to a conductor.
• the conductive material preferably contains metal, more preferably one or more selected from the group consisting of gold, silver, platinum, copper and aluminum. Among these, at least one of gold and copper is particularly preferable from the viewpoint of pattern smoothness, crack suppression, and the like.
• the content of the metal with respect to the total mass of the conductive material is not particularly limited, and may be 80% by mass or more, 90% by mass or more, or 100% by mass.
• a material that changes from a nonconductor to a conductor a material that changes from a nonconductor to a conductor by heating, light irradiation, or voltage application can be used.
• the material that changes from a nonconductor to a conductor is preferably one or more selected from the group consisting of phase change materials, semiconductors, conductive oxides and carbon materials.
• a phase change material means a material that undergoes a phase change between an amorphous phase and a crystalline phase due to Joule heating due to electrical pulses.
• Phase change materials include vanadium oxide, antimony tellurium (SbTe) alloys, germanium tellurium (GeTe) alloys, germanium antimony tellurium (GeSbTe) alloys, indium antimony telluride (InSbTe) alloys, silver indium antimony tellurium (AgInSbTe) alloys, and the like. be done.
• vanadium oxide or a GeSbTe alloy is preferable from the viewpoints of easy control of temperature and voltage at which nonconductors are changed to conductors, smoothness of patterns, crack suppression, and the like.
• Semiconductors include p-type ⁇ -conjugated polymers, condensed polycyclic compounds, triarylamine compounds, five-membered heterocyclic compounds, phthalocyanine compounds, porphyrin compounds, and the like.
• Examples of conductive oxides include indium tin oxide (ITO), indium zinc oxide (IZO), zinc oxide (ZnO), and indium gallium zinc oxide (IGZO). Tin Oxide) and the like.
• Examples of carbon materials include carbon nanotubes and graphene.
• a pattern can include multiple structures.
• a pattern may include two or more types of structures having different shapes, sizes, and the like.
• the shape of the structure is not particularly limited. When an electromagnetic wave in the terahertz band is incident on the metamaterial, electric charges are generated within the structure or between adjacent structures due to interaction with the electric field and magnetic field of the incident electromagnetic wave. A shape that can generate bias, current, etc., and induce a dielectric or magnetic response change is preferred.
• the shape of the structure is not particularly limited. Shapes, such as circular shape and cross shape, are mentioned.
• the structure is composed of a conductive material or a material that changes from a nonconductor to a conductor.
• the structure is a split ring resonator.
• a split ring resonator refers to a structure having a C-shaped or U-shaped configuration, with a gap indicated by G in FIG.
• the size of the structure is not particularly limited, and is preferably equal to or smaller than the wavelength size of the incident electromagnetic wave in the terahertz band.
• the maximum length of the structure means the longest length when a straight line is drawn from one end to the other end of the structure in the in-plane direction of the substrate.
• the width of the structure is preferably 3 ⁇ m to 25 ⁇ m.
• the gap is preferably 1 ⁇ m to 15 ⁇ m from the viewpoint of pattern smoothness. It is preferable that the distance between the structures is appropriately changed according to the shape, size, etc. of the structures, and can be, for example, 30 ⁇ m to 400 ⁇ m.
• the arrangement position of the structure on the substrate surface is not particularly limited, and the arrangement is preferably such that it resonates with electromagnetic waves in the terahertz band.
• the structures are arranged on the substrate surface so as to form a periodic structure in which the amount of phase shift of the terahertz band electromagnetic wave continuously increases or decreases from the center of the substrate surface toward the outer region.
• the periodic structure is a structure in which structures having different diameters are arranged concentrically.
• the variation width of the diameter of the concentrically arranged structures can be 10 ⁇ m to 200 ⁇ m.
• the pattern preferably has a functional group such as an amino group or a hydroxy group.
• the pattern preferably has functional groups such as amino groups, hydroxy groups, epoxy groups, oxetanyl groups, N-hydroxyester groups, imidoester groups, and the like.
• the compound having a functional group has a group capable of ion bonding
• the pattern preferably has a functional group such as a carboxy group, a sulfo group, a phosphoric acid group, a tertiary amino group, a pyridyl group, or a piperidyl group.
• the pattern preferably has a group having a hydrogen bond donating site or a group having a hydrogen bond accepting site.
• the pattern preferably has groups capable of dipole interaction.
• the above functional groups may be introduced by subjecting the surface of the substrate contacting side to a chemical treatment or the like.
• the thickness of the pattern is preferably less than 5 ⁇ m, more preferably 0.05 ⁇ m to 4 ⁇ m, even more preferably 0.1 ⁇ m to 3 ⁇ m, even more preferably 0.3 ⁇ m to 1 ⁇ m. It is particularly preferred to have
• the method of forming the pattern is not particularly limited.
• a sputtering method is used to form a sputtered film on the substrate surface, then a resist pattern is formed on the surface of the sputtered film, and the resist pattern is covered.
• a pattern can be formed by etching away the sputtered film that is not present and then removing the resist pattern.
• the method of forming the pattern is not limited to the above method, and instead of the sputtering method, a vapor deposition method may be used to form the vapor deposition film.
• the metamaterial 10 includes a base material 11 and a pattern 12 provided on the surface of the base material 11 .
• pattern 12 includes a plurality of structures 12a.
• the maximum length of the structure 12a is indicated by L
• the width of the structure 12a is indicated by W
• the gap of the structure 12a is indicated by G
• the distance between the structures is indicated by X.
• Applications of the metamaterial of the present disclosure are not particularly limited, and include flat lenses, diffraction gratings, wavelength filters, polarizers, sensors, reflectors, flat prisms, and the like. Also, the use environment is not particularly limited, and it may be mounted in an electronic device or the like, or may be installed outdoors as a wavelength filter.
• a laminate of the present disclosure includes the metamaterial described above and an organic film provided on the pattern-side surface of the metamaterial.
• the organic film may have a single layer structure or a multilayer structure.
• the moisture permeability of the organic film in an environment with a temperature of 40 ° C. and a relative humidity of 90% is preferably 3000 g / (m 2 ⁇ 24 hours) or less, 2000 g / (m 2 ⁇ 24 hours) or less, more preferably 1500 g/(m 2 ⁇ 24 hours) or less, and particularly preferably 1000 g/(m 2 ⁇ 24 hours) or less.
• the organic film can contain resin.
• the resin is as described above, and the description is omitted here.
• the resin content relative to the total mass of the organic film is not particularly limited, but is preferably 10% by mass to 90% by mass, more preferably 20% by mass to 80% by mass, and 30% by mass. More preferably, it is up to 70% by mass.
• the organic film may contain an ultraviolet absorber.
• an ultraviolet absorber examples include conjugated diene compounds, aminodiene compounds, salicylate compounds, benzophenone compounds, benzotriazole compounds, acrylonitrile compounds, hydroxyphenyltriazine compounds, indole compounds, and triazine compounds.
• the organic film when the organic film has a multilayer structure, the organic film preferably includes a layer containing an ultraviolet absorber.
• the content of the ultraviolet absorbent with respect to the total mass of the organic film is preferably 0.01% by mass to 30% by mass, and 0.1% by mass to 10% by mass. more preferably 0.5% by mass to 5% by mass.
• the organic film may contain the above additives.
• the thickness of the organic film is not particularly limited, and is preferably 20 ⁇ m or less, more preferably 10 ⁇ m or less, and even more preferably 5 ⁇ m or less in terms of not impairing electromagnetic wave transmission characteristics. Although the lower limit is not particularly limited, it is often 0.5 ⁇ m or more.
• the method of manufacturing the laminate is not particularly limited, and the above-described resin or the like is added to a solvent as necessary to form a composition, and the composition is applied to the surface of the metamaterial and dried. You may Alternatively, the composition is applied to a temporary support and dried to form an organic film, a transfer sheet is produced, and the organic film is transferred from the transfer sheet to the surface of the metamaterial, thereby forming a laminate. may be manufactured.
• the temperature was raised and refluxed at 143° C. for 1 hour. Next, the temperature was raised from 150° C. to 300° C. over 5 hours while distilling off the by-product acetic acid and unreacted acetic anhydride, and the temperature was maintained at 300° C. for 30 minutes. cooled. The resulting solid was pulverized with a pulverizer to obtain powdery liquid crystal polyester A1.
• the liquid crystalline polyester A1 obtained above was heated from room temperature to 160° C. over 2 hours and 20 minutes in a nitrogen atmosphere, then heated from 160° C. to 180° C. over 3 hours and 20 minutes, and then heated to 180° C. for 5 hours. After solid-phase polymerization was carried out by holding, the mixture was cooled and then pulverized with a pulverizer to obtain powdery liquid crystalline polyester A2.
• Liquid crystalline polyester A2 is heated from room temperature (23° C.) to 180° C. over 1 hour and 20 minutes in a nitrogen atmosphere, then heated from 180° C. to 240° C. over 5 hours, and held at 240° C. for 5 hours. Thus, after solid phase polymerization, the mixture was cooled to obtain a powdery liquid crystal polyester LC-A.
• the liquid crystal polyester C1 was held at 290°C for 3 hours in a nitrogen atmosphere for solid phase polymerization, cooled, and then pulverized with a pulverizer to obtain a powdery liquid crystal polyester LC-C.
• a jet mill (KJ-200, manufactured by Kurimoto Iron Works Co., Ltd.) was used to pulverize liquid crystal polyester LC-B to obtain filler F-1.
• the average particle size of filler F-1 was 9 ⁇ m.
• Example 1 The liquid crystalline polyester shown in Table 1 is added to N-methylpyrrolidone, stirred under a nitrogen atmosphere at 140° C. for 4 hours to form a solution, passed through a sintered fiber metal filter with a nominal pore size of 10 ⁇ m, and then Composition A was obtained by passing through a 10 ⁇ m sintered fiber metal filter followed by addition of fillers according to Table 1.
• the liquid crystalline polyester shown in Table 1 was added to N-methylpyrrolidone, stirred at 140° C. for 4 hours under a nitrogen atmosphere, dissolved, and then passed through a sintered fiber metal filter with a nominal pore size of 10 ⁇ m.
• composition B was obtained by passing through a sintered fiber metal filter with a pore size of 10 ⁇ m.
• the contents of liquid crystalline polyesters and fillers in composition A and composition B were as shown in Table 1.
• the composition A and the composition B had a liquid crystal polyester solid content concentration of 10% by mass.
• Composition A and composition B were sent to a casting die equipped with a multi-manifold adjusted for co-casting, and cast on an aluminum foil having a thickness of 50 ⁇ m as a support to form a composition having a thickness of 25 ⁇ m.
• a layer made of the product B (referred to as the first layer in Table 1), a layer made of the composition A having a thickness of 30 ⁇ m (referred to as the second layer in Table 1), and a layer of 5 ⁇ m
• a base material having a three-layer structure of a layer made of Composition B (referred to as the third layer in Table 1) was produced.
• a third layer is in contact with the aluminum foil.
• the solvent was removed from the substrate by drying the substrate at 40°C for 4 hours, and the temperature was raised from room temperature (25°C) to 290°C at a rate of 1°C/min under a nitrogen atmosphere. After cooling to room temperature, the aluminum foil was removed and further heated at 200° C. for 1 minute.
• the dielectric loss tangent of the base material produced as described above was measured by the following terahertz time domain spectroscopy (THz-TDS) and found to be 0.003.
• THz-TDS terahertz time domain spectroscopy
• the substrate was cut into test pieces of 100 mm ⁇ 100 mm.
• an optical system for transmission type terahertz spectroscopy was prepared, and the dielectric loss tangent of the test piece was measured from the change in the time waveform of the optical electric field (frequency 1 THz) before and after the test piece was inserted in an environment of 25°C and 10% RH. did.
• a piece of substrate is enclosed in a measurement pan, and a differential scanning calorimeter (DSC6200) manufactured by Seiko Instruments Inc. is used. From the thermogram obtained by raising the temperature at a rate of 20 ° C./min, the baseline and the variation The temperature at the point of intersection with the tangent line at the bending point was determined as the glass transition temperature and found to be 184°C.
• DSC6200 differential scanning calorimeter
• a sputtered copper film having a thickness of 0.5 ⁇ m was formed on the surface of the first layer of the base material.
• a pattern including a plurality of C-type split ring resonators is formed by forming a resist pattern on the surface of the sputtered film, removing the sputtered film not covered by the resist pattern by etching, and then removing the resist pattern. , obtained a metamaterial.
• the split-ring resonators had a width of 15 ⁇ m, a maximum length of 92 ⁇ m, a C shape when viewed from the normal direction of the substrate, a gap of 10 ⁇ m, and a distance between the split-ring resonators of 200 ⁇ m.
• a cross-sectional sample of the laminate prepared as described above was cut out using a microtome, and the curve of the interface shape of the substrate for metamaterial, the pattern and the organic film and the average line of the interface shape curve were created.
• the surface roughness Ra was obtained from the pattern side (first layer side) interface profile curve and average line of the metamaterial substrate, it was 3 nm.
• the surface roughness Ra was measured in a square area of 465.48 ⁇ m in length and 620.64 ⁇ m in width using a non-contact surface/layer profile measurement system VertScan (manufactured by Mitsubishi Chemical Systems Co., Ltd.).
• Example 2 A metamaterial and a laminate were produced in the same manner as in Example 1, except that filler F-1 was changed to filler F-2.
• the details of the filler F-2 are as follows.
• the glass transition temperature of the substrate was measured by the same method as in Example 1, it was 184°C.
• the surface roughness Ra of the substrate was measured by the same method as in Example 1, it was 1 nm.
• the dielectric loss tangent of the substrate was measured by the same method as in Example 1, it was 0.002.
• Filler F-2 Copolymer (PFA) particles of tetrafluoroethylene and perfluoroalkoxyethylene (melting point 280° C., average particle diameter 0.2 ⁇ m to 0.5 ⁇ m, dielectric loss tangent 0.001)
• Example 3 The liquid crystalline polyester shown in Table 1 was added to N-methylpyrrolidone, stirred at 140° C. for 4 hours under a nitrogen atmosphere to form a solution, passed through a sintered fiber metal filter with a nominal pore size of 5 ⁇ m, and then passed through a sintered fiber metal filter with a nominal pore size of 5 ⁇ m. of sintered fiber metal filters.
• Compound M-1 aminophenol type epoxy resin, jER630LSD, manufactured by Mitsubishi Chemical Corporation, capable of covalently bonding with the liquid crystal polyester and hydrogen bonding with the glass cloth having a functional group on the liquid crystal polyester after passing through the filter ) was added and stirred at 25°C for 30 minutes to obtain composition D.
• liquid crystalline polyester shown in Table 1 was added to N-methylpyrrolidone, stirred under a nitrogen atmosphere at 140°C for 4 hours, passed through a sintered fiber metal filter with a nominal pore size of 5 ⁇ m, and then sintered with a nominal pore size of 5 ⁇ m.
• Composition E was obtained after passing through a fiber metal filter.
• the contents of the liquid crystalline polyester and the compound M-1 having a functional group in Compositions D and E were as shown in Table 1.
• composition D and composition E were adjusted in solid concentration so that the solution viscosity at room temperature (23° C.) was 0.3 Pa ⁇ s.
• composition E was applied to one surface of the glass cloth substrate using a reverse gravure coater and dried at 160°C. Furthermore, a heat treatment was performed in which the temperature was raised from room temperature to 290° C. at a rate of 1° C./min under a nitrogen atmosphere and held at that temperature for 2 hours to obtain a base material.
• the thickness of the first layer made of composition E was 20 ⁇ m.
• a metamaterial and a laminate were produced in the same manner as in Example 1, except that the base material was changed to the base material produced by the above method and a pattern was formed on the surface of the layer composed of Composition E.
• the glass transition temperature of the substrate was measured by the same method as in Example 1, it was 210°C.
• the surface roughness Ra of the substrate was measured by the same method as in Example 1, it was 6 nm.
• the dielectric loss tangent of the substrate was measured by the same method as in Example 1, it was 0.005.
• Liquid crystalline polyester LC-D manufactured by Polyplastics Co., Ltd., Vectra (registered trademark) A950 was pelletized using a twin-screw extruder under a nitrogen atmosphere.
• the obtained pellets were supplied into a cylinder from the same supply port of a twin-screw extruder with a screw diameter of 50 mm, and heated and kneaded at 340° C. to 350° C. to obtain a kneaded product. Subsequently, the kneaded material was fed to a T-die, and a melted film-like kneaded material was discharged and solidified on a chill roll.
• the obtained film was peeled off from the chill roll and tenter-stretched to adjust the anisotropy of the storage modulus (MD/TD) to 2 or less to obtain a film having a thickness of 55 ⁇ m.
• the composition B is applied using a reverse gravure coater, the temperature is gradually raised from room temperature (25 ° C.) to 270 ° C. in a nitrogen atmosphere, and heat treatment is performed at that temperature for 2 hours.
• a substrate was obtained.
• the base material includes a layer of composition B having a thickness of 15 ⁇ m (referred to as the first layer in Table 1) and a layer of the kneaded product having a thickness of 55 ⁇ m (the second layer in Table 1). ) and a layer made of composition B having a thickness of 5 ⁇ m (referred to as the third layer in Table 1).
• a metamaterial and a laminate were produced in the same manner as in Example 1, except that the base material was changed to the base material produced by the above method.
• the glass transition temperature of the substrate was measured by the same method as in Example 1, it was 184°C and 210°C.
• the surface roughness Ra of the substrate was measured by the same method as in Example 1, it was 1 nm.
• the dielectric loss tangent of the substrate was measured by the same method as in Example 1, it was 0.002.
• Cycloolefin polymer P-1 (manufactured by JSR Corporation, Arton (registered trademark) F3500) was added to dichloromethane, stirred at 60°C for 30 minutes to form a solution, and then passed through a sintered fiber metal filter with a nominal pore size of 10 ⁇ m. Then, it was also passed through a sintered fiber metal filter having a nominal pore size of 10 ⁇ m to obtain Composition F. Compound M-1 having a functional group was added to composition F, and the mixture was stirred at 25° C. for 30 minutes to obtain composition G. The contents of the cycloolefin polymer P-1 and the functional group-containing compound M-1 in Composition F and Composition G were as shown in Table 1.
• composition F and composition G are sent to a casting die equipped with a multi-manifold adjusted for co-casting, cast on a stainless steel band as a support, and composed of composition F with a thickness of 60 ⁇ m.
• a substrate having a two-layer structure of a layer (referred to as the first layer in Table 1) and a layer composed of composition G having a thickness of 60 ⁇ m (referred to as the second layer in Table 1). material was produced.
• a second layer is in contact with the stainless steel band.
• the substrate is dried with hot air and the amount of residual solvent reaches 10% by mass, it is peeled off from the support while applying a 3% draw in the MD direction, held at both ends with tenter clips and dried at 170 ° C. for 3 minutes. While stretching, the film was stretched by 5% in the TD direction.
• a metamaterial and a laminate were produced in the same manner as in Example 1, except that the base material was changed to the base material produced by the above method and a pattern was formed on the surface of the first layer.
• the glass transition temperature of the substrate was measured by the same method as in Example 1, it was 165°C.
• the surface roughness Ra of the substrate was measured by the same method as in Example 1, it was 1 nm.
• the dielectric loss tangent of the substrate was measured by the same method as in Example 1, it was 0.002.
• the glass transition temperature of the substrate was measured by the same method as in Example 1, it was 136°C.
• the surface roughness Ra of the substrate was measured by the same method as in Example 1, it was 20 nm.
• the dielectric loss tangent of the substrate was measured by the same method as in Example 1, it was less than 0.001.
• Example 2 The procedure was the same as in Example 1, except that the substrate was changed to a 50 ⁇ m thick liquid crystal polymer film (manufactured by Kuraray Co., Ltd., Vextor (registered trademark) CTQ, referred to as PF-2 in Table 1). , metamaterials and laminates were manufactured.
• the glass transition temperature of the substrate was measured by the same method as in Example 1, it was 214°C.
• the surface roughness Ra of the substrate was measured by the same method as in Example 1, it was 304 nm.
• the dielectric loss tangent of the substrate was measured by the same method as in Example 1, it was 0.002.
• ⁇ Pattern smoothness evaluation>> Cross-sectional samples of the laminates produced in Examples and Comparative Examples were cut out using a microtome, and the curve of the interface shape of the pattern and the average line of the curve of the interface shape were created.
• the surface roughness Ra was determined from the interface profile curve and average line on the side opposite to the metamaterial substrate side of the pattern, and is shown in Table 2.
• the surface roughness Ra was measured in a square area of 465.48 ⁇ m in length and 620.64 ⁇ m in width using a non-contact surface/layer profile measurement system VertScan (manufactured by Mitsubishi Chemical Systems Co., Ltd.).
• the metamaterials and laminates obtained in Examples have superior heat resistance and smoothness compared to the metamaterials and laminates obtained in Comparative Examples. It can be seen that it is superior in quality.

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