Classifications

• • G—PHYSICS
  • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
  • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
  • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
  • G03F7/004—Photosensitive materials
  • G03F7/09—Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers
  • G03F7/092—Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers characterised by backside coating or layers, by lubricating-slip layers or means, by oxygen barrier layers or by stripping-release layers or means
• • G—PHYSICS
  • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
  • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
  • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
  • G03F7/004—Photosensitive materials
  • G03F7/0042—Photosensitive materials with inorganic or organometallic light-sensitive compounds not otherwise provided for, e.g. inorganic resists
  • G03F7/0043—Chalcogenides; Silicon, germanium, arsenic or derivatives thereof; Metals, oxides or alloys thereof
• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01P—WAVEGUIDES; RESONATORS, LINES, OR OTHER DEVICES OF THE WAVEGUIDE TYPE
  • H01P1/00—Auxiliary devices

Definitions

• the present disclosure relates to metamaterials and laminates.
• 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 to 10 THz (wavelength of 30 to 3000 ⁇ m) (hereinafter referred to as the terahertz band 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 included in the metamaterial described in JP-A-2021-114647 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 about 0.5 ⁇ m in the thickness direction from the surface of the pattern, in future development, from the viewpoint of cost reduction, etc., the thickness of the pattern will be reduced. It is assumed to be small.
• the present inventors have found that when the thickness of the pattern is reduced, the rigidity of the pattern decreases, and internal stress is generated due to deformation of the base material due to changes in temperature and humidity, and cracks may occur in the pattern. Obtained.
• the present disclosure has been made based on the above findings, and the problem to be solved by one embodiment of the present disclosure is that the occurrence of cracks can be suppressed (hereinafter also referred to as crack suppression), meta It is to provide materials and laminates.
• ⁇ 4> The above ⁇ 1> to ⁇ 3, wherein the ratio of the product of the thickness of the pattern and the storage elastic modulus at 25° C. to the product of the thickness of the substrate and the storage elastic modulus at 25° C. is less than 10.
• ⁇ 5> The metamaterial according to any one of ⁇ 1> to ⁇ 4>, wherein the pattern includes a plurality of structures, and the structures are split ring resonators.
• ⁇ 6> The metamaterial according to any one of ⁇ 1> to ⁇ 5>, wherein the pattern is made of the conductive material, and the conductive material contains a metal.
• ⁇ 7> The metamaterial according to any one of ⁇ 1> to ⁇ 6>, wherein the substrate contains at least one selected from the group consisting of fluoropolymers and liquid crystal polymers.
• ⁇ 8> The metamaterial according to any one of ⁇ 1> 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.
• 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 container.
• the storage modulus of the base material at 25°C is measured according to the method described in JIS K 7127 (1999) under conditions of a temperature of 25°C and a relative humidity of 50%.
• a test piece having a size of 10 mm ⁇ 150 mm is prepared and the storage elastic modulus of the test piece is measured.
• the pattern formed on the surface of the substrate is cut into a size of 5 mm ⁇ 5 mm, a test piece is prepared, and a scanning probe microscope is used at a temperature of 25 ° C. and a relative humidity of 50%.
• the storage elastic modulus of the test piece is measured under the conditions of
• 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 metamaterial of the present disclosure includes a base material and a pattern provided on the surface of the base material, the pattern is composed of at least one of a conductive material and a material that changes from a nonconductor to a conductor, and the base material A coefficient of thermal expansion is 80 ppm/K or less.
• the metamaterial of the present disclosure has excellent crack suppression properties.
• the reason why the above effect is exhibited is presumed as follows, but is not limited thereto.
• the substrate included in the metamaterial of the present disclosure has a thermal expansion coefficient of 80 ppm/K or less, which is smaller than that of a conventional metamaterial substrate, and the difference in thermal expansion coefficient from the pattern formed on the surface. becomes smaller. It is presumed that the internal stress generated in the pattern can be reduced by reducing the difference in thermal expansion coefficient between the base material and the pattern, and the occurrence of cracks in the pattern can be suppressed.
• the ratio of the product of the thickness of the pattern and the storage modulus at 25 ° C. to the product of the thickness of the substrate and the storage modulus at 25 ° C. is preferably less than 10, more preferably 0.005 to 1.0, and 0.005 to 1.0. It is more preferably 01 to 0.5.
• the thermal expansion coefficient of the substrate is more preferably -20 ppm/K to 65 ppm/K, further preferably 0 ppm/K to 55 ppm/K, and 5 ppm/K to 40 ppm/K. K is particularly preferred.
• the coefficient of thermal expansion of the base material can be adjusted by changing the material contained in the base material.
• the coefficient of thermal expansion is measured by the following method. First, a substrate is cut into a test piece of 5 mm ⁇ 20 mm. Then, using a thermomechanical analyzer (TMA), a tensile load of 1 g was applied to both ends of the test piece in the longitudinal direction, and the temperature was raised from 25 ° C. to 150 ° C. at a rate of 5 ° C./min, and then cooled to 25 ° C. The coefficient of thermal expansion is calculated from the slope of the TMA curve between 125 and 50°C.
• TMA thermomechanical analyzer
• 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 as long as it satisfies the conditions of the coefficient of thermal expansion, 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 has at least one of a structural unit derived from hydroxylamine and a structural unit derived from an aromatic diamine, and more preferably has only a structural unit (3) in which at least one of X and Y is an imino group.
• the liquid crystal polymer is preferably produced by melt-polymerizing raw material monomers corresponding to the structural units 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 more preferably have a group, and more preferably have 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 pattern on the surface of a substrate that is composed of at least one of a conductive material and a material that changes from a nonconductor to a conductor.
• the pattern preferably serves as a resonator for electromagnetic waves with a frequency of 0.1 THz to 10 THz (wavelength of 30 ⁇ m to 3000 ⁇ m).
• 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 crack suppression properties.
• 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 viewpoint of easily controlling the temperature and voltage for changing from a nonconductor to a conductor, and from the viewpoint of crack suppression properties.
• 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 crack suppression. 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 hydroxyl group.
• the pattern preferably has functional groups such as amino groups, hydroxyl 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
• a pattern forming method is not particularly limited. For example, by sputtering, a sputtered film is formed on the surface of the substrate, a resist pattern is then formed on the surface of the sputtered film, the sputtered film not covered with the resist pattern is removed by etching, and then the resist pattern is removed. A pattern can be formed by this. Also, instead of the sputtered film, a copper-clad laminate in which a copper foil is laminated on a base material can be used. In this case, in order to adjust the thickness of the copper foil, a desired thickness of copper foil can be used for lamination with the base material. After the plate is produced, the copper foil can be thinned by a known method such as etching. It can also be peeled off and made into a thin film. 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 15 ⁇ 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 15 ⁇ 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.
• the coefficient of thermal expansion of the base material produced as described above was measured by the following method and found to be 42 ppm/K.
• the substrate was cut into test pieces of 5 mm ⁇ 20 mm.
• TMA thermomechanical analyzer
• a tensile load of 1 g was applied to both ends of the test piece in the longitudinal direction, and the temperature was raised from 25 ° C. to 150 ° C. at a rate of 5 ° C./min, and then cooled to 25 ° C.
• the coefficient of thermal expansion was calculated from the slope of the TMA curve between 125 and 50°C.
• the substrate was cut into test specimens with a size of 10 mm x 150 mm.
• the storage modulus of the test piece was measured in accordance with the method described in JIS K 7127 (1999) under the conditions of a distance between chucks of 100 mm, a temperature of 25° C. and a relative humidity of 50%, and was 4.2 GPa. Ta.
• a sputtered copper film having a thickness of 0.5 ⁇ m was formed on the surface of the first layer of the base material. forming a resist pattern on the surface of the sputtered film, etching away the sputtered film not covered by the resist pattern, and then removing the resist pattern to form a pattern including a plurality of C-type split ring resonators; 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.
• the pattern was cut into a size of 5 mm ⁇ 5 mm to prepare a test piece.
• the storage modulus of the test piece was measured using a scanning probe microscope (SPA400, manufactured by SII Nanotechnology Co., Ltd.) in VE-AFM mode at a temperature of 25 ° C. and a relative humidity of 50%. Met.
• Example 2 and Example 3 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 or filler F-3.
• the details of filler F-2 and filler F-3 are as follows.
• the dielectric loss tangent of the substrate was measured by the same method as in Example 1, both were 0.002.
• the thermal expansion coefficients of the substrates were measured by the same method as in Example 1, they were 42 ppm/K and 30 ppm/K, respectively.
• the storage modulus of the base material was measured by the same method as in Example 1, it was 4.0 GPa and 5.5 GPa, respectively.
• the storage elastic modulus of the pattern was 30 GPa.
• 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)
• Filler F-3 Silica particles with an average particle size of 0.5 ⁇ m, manufactured by Admatechs Co., Ltd., SO-C2
• Example 4 (Preparation of base material) Compound M-1 having a functional group was added to composition B of Example 1, and the mixture was stirred at 25° C. for 30 minutes to obtain composition X.
• the contents of liquid crystal polyester LC-A and compound M-1 having a functional group in composition X were as shown in Table 1.
• a composition Y was obtained.
• composition B, composition X and composition Y are sent to a casting die equipped with a multi-manifold adjusted for co-casting, and a 18 ⁇ m thick copper foil (Fukuda Metal Foil & Powder Co., Ltd.) is used as a support.
• a layer made of composition X with a thickness of 15 ⁇ m (referred to as the first layer in Table 1), a thickness of 30 ⁇ m
• a layer made of composition Y (referred to as the second layer in Table 1) and a layer made of composition B having a thickness of 15 ⁇ m (referred to as the third layer in Table 1)
• a substrate having a three-layer structure was produced. Note that the first layer is in contact with the copper foil.
• the solvent is removed from the substrate, and the temperature is raised from room temperature (25 ° C.) to 290 ° C. at 1 ° C./min in a nitrogen atmosphere, Heat treatment was carried out by holding at that temperature for 2 hours, and then cooled to room temperature. Furthermore, the copper foil was half-etched and thinned to a thickness of 5 ⁇ m to obtain a copper-clad laminate comprising the substrate and the copper foil.
• Example 2 In the same manner as in Example 1, the surface of the copper foil of the copper-clad laminate was subjected to resist pattern formation, etching, and removal of the resist pattern to form a pattern including a plurality of C-type split ring resonators. got the material.
• the dielectric loss tangent of the base material was measured by the same method as in Example 1, it was 0.002.
• the thermal expansion coefficient of the substrate was measured by the same method as in Example 1, it was 58 ppm/K.
• the storage elastic modulus of the substrate was measured by the same method as in Example 1, it was 4.2 GPa.
• the storage elastic modulus of the pattern was 30 GPa.
• Example 5 (Preparation of base material)
• the composition B prepared in Example 1 and the composition Y prepared in Example 5 were sent to a casting die equipped with a multi-manifold adjusted for co-casting, and a support having a thickness of 5 ⁇ m was used.
• Cast on a copper foil manufactured by Mitsui Mining & Smelting Co., Ltd., MT18SD-H-T5
• a layer made of composition B with a thickness of 15 ⁇ m (referred to as the first layer in Table 1), 30 ⁇ m
• a layer of composition Y having a thickness of 15 ⁇ m (referred to as the second layer in Table 1) and a layer of composition B having a thickness of 15 ⁇ m (referred to as the third layer in Table 1).
• the first layer is in contact with the copper foil.
• the solvent is removed from the substrate, and the temperature is raised from room temperature (25 ° C.) to 290 ° C. at 1 ° C./min in a nitrogen atmosphere, A heat treatment was performed at that temperature for 2 hours, and the laminate was cooled to room temperature to obtain a copper-clad laminate.
• Example 2 In the same manner as in Example 1, the surface of the copper foil of the copper-clad laminate was subjected to resist pattern formation, etching, and removal of the resist pattern to form a pattern including a plurality of C-type split ring resonators. got the material.
• the dielectric loss tangent of the base material was measured by the same method as in Example 1, it was 0.002.
• the thermal expansion coefficient of the substrate was measured by the same method as in Example 1, it was 58 ppm/K.
• the storage elastic modulus of the substrate was measured by the same method as in Example 1, it was 4.2 GPa.
• the storage elastic modulus of the pattern was 30 GPa.
• Example 6> (Preparation of base material) Composition A and composition B used in Example 1 were fed to a casting die equipped with a multi-manifold adjusted for co-casting, and a carrier copper foil having a thickness of 18 ⁇ m was laminated as a support.
• a layer made of composition B with a thickness of 15 ⁇ m (referred to as the first layer in Table 1), 30 ⁇ m
• a layer of composition A having a thickness of 15 ⁇ m referred to as the second layer in Table 1) and a layer of composition B having a thickness of 15 ⁇ m (referred to as the third layer in Table 1).
• the first layer is in contact with the copper foil.
• the solvent is removed from the substrate, and the temperature is raised from room temperature (25 ° C.) to 290 ° C. at 1 ° C./min in a nitrogen atmosphere, Heat treatment was carried out by holding at that temperature for 2 hours, and then cooled to room temperature. Further, the carrier copper foil was peeled off to obtain a copper-clad laminate.
• Example 2 In the same manner as in Example 1, the surface of the copper foil of the copper-clad laminate was subjected to resist pattern formation, etching, and removal of the resist pattern to form a pattern including a plurality of C-type split ring resonators. got the material.
• the dielectric loss tangent of the base material was measured by the same method as in Example 1, it was 0.003.
• the coefficient of thermal expansion of the substrate was measured by the same method as in Example 1, it was 42 ppm/K.
• the storage elastic modulus of the substrate was measured by the same method as in Example 1, it was 4.2 GPa.
• the storage elastic modulus of the pattern was 30 GPa.
• Example 7 In the production of the base material of Example 6, a 1.5 ⁇ m thick copper foil laminated with a 18 ⁇ m thick carrier copper foil was used instead of the 3 ⁇ m thick copper foil laminated with a 18 ⁇ m thick carrier copper foil. (manufactured by Mitsui Mining & Smelting Co., Ltd., MT18FL) was used in the same manner as in Example 6 to prepare a metamaterial and a laminate.
• the dielectric loss tangent of the base material was measured by the same method as in Example 1, it was 0.003.
• the coefficient of thermal expansion of the substrate was measured by the same method as in Example 1, it was 42 ppm/K.
• the storage elastic modulus of the substrate was measured by the same method as in Example 1, it was 4.2 GPa.
• the storage elastic modulus of the pattern was 30 GPa.
• Example 8> 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.
• composition E was passed through a sintered fiber metal filter with a nominal pore size of 5 ⁇ m and then through a sintered fiber metal filter also with a nominal pore size of 5 ⁇ m.
• 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.
• a glass cloth with low dielectric properties (NE glass, manufactured by Nittobo Co., Ltd.) was impregnated with the composition D, and the solvent was evaporated at 160° C. to obtain a glass cloth substrate having a thickness of 65 ⁇ m.
• 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 layer made of composition E was 15 ⁇ m.
• the dielectric loss tangent of the substrate was measured by the same method as in Example 1, it was 0.005.
• the thermal expansion coefficient of the substrate was measured by the same method as in Example 1, it was 14 ppm/K.
• 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. Moreover, when the storage elastic moduli of the substrate and the pattern were measured by the same method as in Example 1, they were 27 GPa and 30 GPa, respectively.
• Example 9 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, each of the kneaded materials was fed to a T-die having a multi-manifold structure, and a melted film-like kneaded material was discharged and solidified on a chill roll.
• Vectra registered trademark
• the obtained film was peeled off from the chill roll and tenter-stretched to adjust the anisotropy of the storage elastic modulus (MD/TD) to 2 or less to obtain a substrate having a thickness of 80 ⁇ m.
• MD/TD storage elastic modulus
• the dielectric loss tangent of the substrate was measured by the same method as in Example 1, it was 0.002.
• the thermal expansion coefficient of the substrate was measured by the same method as in Example 1, it was 17 ppm/K.
• 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. Moreover, when the storage elastic moduli of the base material and the pattern were measured by the same method as in Example 1, they were 3.6 GPa and 30 GPa, respectively.
• 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.
• a compound M-1 having a functional group was added to the cycloolefin polymer P-1 after passing through the filter, and the mixture was stirred at 25° C. for 30 minutes to obtain a 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 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 2 ⁇ m.
• Two layers a layer made of the substance F (referred to as the first layer in Table 1) and a layer made of the composition G having a thickness of 58 ⁇ m (referred to as the second layer in Table 1)
• a substrate having a structure was produced. When 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.
• the film was stretched by 5% in the TD direction.
• the dielectric loss tangent of the substrate was measured by the same method as in Example 1, it was 0.002.
• the coefficient of thermal expansion of the substrate was measured by the same method as in Example 1, it was 70 ppm/K.
• 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. Moreover, when the storage elastic moduli of the substrate and the pattern were measured by the same method as in Example 1, they were 2.2 GPa and 30 GPa, respectively.
• 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 5 ⁇ m. It was then passed through a sintered fiber metal filter, also with a nominal pore size of 5 ⁇ m.
• Compound M-1 having a functional group was added to cycloolefin polymer P-1 after passing through the filter, and the mixture was stirred at 25° C. for 30 minutes to obtain composition H.
• the contents of the cycloolefin polymer P-1 and the compound M-1 having a functional group in the composition H were as shown in Table 1.
• a glass cloth with low dielectric properties (NE glass, manufactured by Nittobo Co., Ltd.) was impregnated with the composition H, dried at 100 ° C., and then dried at 160 ° C. to remove the solvent, resulting in a thickness of 65 ⁇ m.
• a glass cloth substrate was obtained.
• composition F prepared in Example 10 was applied to one surface of the glass cloth substrate using a reverse gravure coater, dried at 100°C, and then dried at 230°C for 3 minutes. , the solvent was removed to obtain a base material.
• the thickness of the layer made of composition F was 15 ⁇ m.
• the dielectric loss tangent of the substrate was measured by the same method as in Example 1, it was 0.002.
• the thermal expansion coefficient of the substrate was measured by the same method as in Example 1, it was 22 ppm/K.
• 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 F. Moreover, when the storage elastic moduli of the substrate and the pattern were measured by the same method as in Example 1, they were 26 GPa and 30 GPa, respectively.
• the dielectric loss tangent of the base material was measured by the same method as in Example 1, it was less than 0.001.
• the thermal expansion coefficient of the substrate was measured by the same method as in Example 1, it was 82 ppm/K.
• the storage elastic moduli of the substrate and the pattern were measured by the same method as in Example 1, they were 2.1 GPa and 30 GPa, respectively.
• ⁇ Crack suppression evaluation>> The metamaterials produced in the examples and comparative examples, before forming the organic film and forming the laminate, were cut into a size containing 100 split ring resonators to obtain a test piece.
• the test piece was placed in a heat shock tester (TSA series for thermal shock test, manufactured by Espec Co., Ltd.). After leaving the test piece at ⁇ 65° C. for 30 minutes, the temperature was switched to 125° C., left for 30 minutes, and then switched to ⁇ 65° C. This cycle was repeated 150 times, and the temperature was returned to 25° C. and relative humidity of 55%. .
• TSA series for thermal shock test manufactured by Espec Co., Ltd.

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