Classifications

• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B27/00—Layered products comprising a layer of synthetic resin
  • B32B27/36—Layered products comprising a layer of synthetic resin comprising polyesters
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B15/00—Layered products comprising a layer of metal
  • B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
  • B32B15/08—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
  • B32B15/09—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin comprising polyesters
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B15/00—Layered products comprising a layer of metal
  • B32B15/20—Layered products comprising a layer of metal comprising aluminium or copper
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B27/00—Layered products comprising a layer of synthetic resin
  • B32B27/06—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
  • 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
• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01P—WAVEGUIDES; RESONATORS, LINES, OR OTHER DEVICES OF THE WAVEGUIDE TYPE
  • H01P1/00—Auxiliary devices
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B2255/00—Coating on the layer surface
  • B32B2255/10—Coating on the layer surface on synthetic resin layer or on natural or synthetic rubber layer
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B2255/00—Coating on the layer surface
  • B32B2255/20—Inorganic coating
  • B32B2255/205—Metallic coating
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • 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
  • B32B2307/50—Properties of the layers or laminate having particular mechanical properties
  • B32B2307/51—Elastic
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B2307/00—Properties of the layers or laminate
  • B32B2307/70—Other properties
  • B32B2307/748—Releasability
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B2457/00—Electrical equipment

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 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 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 disclosure has been made based on the above findings, and the problem to be solved by one embodiment of the present disclosure is to provide a metamaterial and a laminate that have excellent adhesion between a substrate and a pattern. .
• a substrate comprising at least an elastic layer having an elastic recovery rate of 80% or less at 25°C; and a pattern provided on the surface of the elastic layer, The pattern is composed of at least one of a conductive material and a material that changes from a nonconductor to a conductor, metamaterial.
• the elastic layer has a thickness of 7 ⁇ m to 15 ⁇ m.
• the elastic layer contains a thermoplastic elastomer having a glass transition temperature of -70°C to 25°C.
• ⁇ 4> The metamaterial according to any one of ⁇ 1> to ⁇ 3> above, wherein the base material has a dielectric loss tangent of 0.01 or less.
• ⁇ 5> The metamaterial according to any one of ⁇ 1> to ⁇ 4>, wherein the pattern has a thickness of less than 5 ⁇ m.
• ⁇ 6> The above ⁇ 1> to ⁇ 5, 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.
• ⁇ 7> The metamaterial according to any one of ⁇ 1> to ⁇ 6>, wherein the pattern includes a plurality of structures, and the structures are split ring resonators.
• ⁇ 8> The metamaterial according to any one of ⁇ 1> to ⁇ 7>, wherein the pattern is made of the conductive material, and the conductive material contains a metal.
• the elastic layer contains at least one selected from the group consisting of fluoropolymers and liquid crystal polymers.
• ⁇ 10> The metamaterial according to any one of ⁇ 1> to ⁇ 9>above; and an organic film provided on the pattern-side surface of the metamaterial.
• ⁇ 11> The laminate according to ⁇ 10> 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%.
• ⁇ 12> The laminate according to ⁇ 10> or ⁇ 11> above, wherein the organic film contains an ultraviolet absorber.
• FIG. 1 is a perspective view showing one embodiment of the metamaterial of the present disclosure.
• FIG. 2 is a cross-sectional view of the metamaterial of FIG. 1 along line AA.
• FIG. 3 is a cross-sectional view of one embodiment of a metamaterial of the present disclosure.
• 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 elastic recovery rate of the elastic layer is measured by the following nanoindentation method.
• a cross-sectional sample of the substrate is cut out using a microtome.
• the elastic layer of the cross-sectional sample is subjected to a load by pressing the indenter from the side, and then the indenter is returned to remove the load, thereby obtaining a load-displacement curve.
• the elastic recovery rate is obtained from the ratio (V2/V1 ⁇ 100) between the maximum displacement amount V1 of the obtained curve and the difference V2 of the displacement amount at which the load becomes 0 when the indenter is returned from the maximum displacement amount.
• the measurement mode is single indentation measurement
• the measurement temperature is 25 ° C.
• the indenter used is a Berkovich (triangular pyramid) type diamond indenter
• the indentation depth of the indenter with respect to the cross-sectional sample is 300 nm
• the indentation of the indenter is The speed is 10 nm/sec
• the drawing speed of the indenter from the cross-sectional sample is 10 nm/sec.
• a Triboindenter manufactured by Hysitron or a similar device can be used as a nanoindenter.
• thermoplastic elastomer means a polymer with a glass transition temperature of 25°C or lower.
• the glass transition temperature of the thermoplastic elastomer is determined from a DSC curve obtained by differential scanning calorimetry (DSC), and more specifically, JIS K 7121 (1987) "Method for measuring transition temperature of plastics It is determined by the "extrapolation glass transition start temperature” described in "How to determine the glass transition temperature”.
• 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 comprises a substrate comprising at least an elastic layer having an elastic recovery rate of 80% or less at 25°C, and a pattern provided on the surface of the elastic layer, wherein the pattern comprises a conductive material, and at least one of a material that changes from a nonconductor to a conductor.
• the metamaterial of the present disclosure has excellent adhesion between the substrate and the pattern. Although the mechanism by which the above effect is exhibited is not clear, it is speculated as follows.
• the pattern is provided on the surface of the elastic layer having an elastic recovery rate of 80% or less at 25°C, the internal stress generated in the pattern is relaxed, and the adhesion between the metamaterial substrate and the pattern is improved. Guess it will improve.
• the base material included in the metamaterial of the present disclosure includes at least an elastic layer having an elastic recovery rate of 80% or less at 25°C. From the viewpoint of adhesion between the substrate and the pattern and suppression of cracks in the pattern, the elastic recovery rate of the elastic layer is preferably 0.1% to 60%, more preferably 1% to 50%. is more preferred.
• the substrate may have a single layer structure or a multilayer structure. When the base material has a multilayer structure, the elastic layer is provided on the outermost surface of the base material, which can be in contact with the pattern. Also, the substrate may have two or more elastic layers.
• the material constituting the elastic layer is not particularly limited as long as it satisfies the above elastic recovery rate.
• the elastic layer preferably contains a thermoplastic elastomer from the viewpoint of adhesion between the substrate and the pattern and suppression of cracks in the pattern. From the viewpoint of the adhesion between the substrate and the pattern and the suppression of cracks in the pattern, the glass transition temperature of the thermoplastic elastomer is preferably -150°C to 25°C, more preferably -150°C to 5°C. is more preferably -125 ° C. to 0 ° C.
• thermoplastic elastomer is not particularly limited, and examples thereof include polystyrene-based elastomers, olefin-based elastomers, polyvinyl chloride-based elastomers, polyurethane-based elastomers, polyester-based elastomers, polyamide-based elastomers, and the like.
• the thermoplastic elastomer is preferably a styrene-based elastomer or an olefin-based elastomer, more preferably a styrene-based elastomer, from the viewpoint of the adhesion between the substrate and the pattern and the suppression of cracks in the pattern. more preferred.
• the styrene-based elastomer is not particularly limited as long as it contains structural units derived from a styrene compound, and conventionally known ones can be used.
• Styrene-based elastomers include styrene-isobutylene-styrene copolymers, styrene-ethylene-butylene-styrene copolymers, styrene-propylene-styrene copolymers, methyl methacrylate-butadiene-styrene copolymers, and the like.
• at least part of the double bonds of the conjugated diene component of these styrene-based elastomers may be hydrogenated.
• the olefin-based elastomer is not particularly limited as long as it contains structural units derived from an olefin compound, and conventionally known elastomers can be used.
• elastomers copolymers of ⁇ -olefins having 2 to 20 carbon atoms such as ethylene, propylene, 1-butene, 1-hexene, 4-methyl-pentene are preferable, and ethylene-propylene copolymers, ethylene- A propylene-diene copolymer and the like can be mentioned.
• the olefinic elastomer may also be a copolymer of a non-conjugated diene having 2 to 20 carbon atoms such as dicyclopentadiene, 1,4-hexadiene, butadiene and isoprene, and an ⁇ -olefin.
• the weight average molecular weight of the thermoplastic elastomer is not particularly limited, but is preferably 5,000 to 500,000, more preferably 10,000 to 300,000, more preferably 50,000 to 200, 000 is more preferred.
• the content of the thermoplastic elastomer with respect to the total mass of the elastic layer is preferably 30% by mass or more, and preferably 50% by mass or more, from the viewpoint of adhesion between the substrate and the pattern and suppression of cracks in the pattern. more preferably 60% by mass or more, particularly preferably 70% by mass or more, and most preferably 80% by mass or more.
• the content of the thermoplastic elastomer relative to the total mass of the elastic layer is preferably 98% by mass or less, more preferably 95% by mass or less, more preferably 90% by mass, from the viewpoint of suppressing the occurrence of cracks in the pattern. More preferably:
• the elastic layer may contain resin.
• resin does not include the thermoplastic elastomer.
• Resins that can be contained in the elastic layer include liquid crystal polymers, fluoropolymers, polymers of compounds having a cycloaliphatic hydrocarbon group and a group having an ethylenically unsaturated bond, polyetheretherketones, polyolefins, polyamides, and polyesters. , polyphenylene sulfide, aromatic polyether ketone, polycarbonate, polyarylate, polyether sulfone, polyphenylene ether and its modified products, thermoplastic resins such as polyetherimide; thermosetting resins such as phenol resin, epoxy resin, polyimide resin, cyanate resin and flexible 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 resin content relative to the total mass of the elastic layer is not particularly limited, and is preferably 3% by mass to 60% by mass, more preferably 5% by mass to 50% by mass, and 10% by mass. It is more preferably to 40% by mass, and particularly preferably 15% to 30% by mass.
• the elastic layer 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 elastic layer contains silica particles among those mentioned above.
• 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 elastic layer may contain various additives such as polymerization initiators, dispersants, surfactants, cross-linking agents and antioxidants.
• the thickness of the elastic layer is preferably 1 ⁇ m to 20 ⁇ m, more preferably 2 ⁇ m to 19 ⁇ m, more preferably 3 ⁇ m to 18 ⁇ m, from the viewpoint of adhesion between the substrate and the pattern and suppression of cracks in the pattern. more preferably 5 ⁇ m to 17 ⁇ m, most preferably 7 ⁇ m to 15 ⁇ m.
• the substrate may have layers other than the elastic layer.
• Layers other than the elastic layer can contain the above resin.
• the resin is a liquid crystal polymer, a fluorine-based polymer, a polymer of a compound having a cyclic aliphatic hydrocarbon group and a group having an ethylenically unsaturated bond, It is preferably at least one selected from the group consisting of 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.
• a liquid crystal polymer is preferred from the viewpoint of adhesion to a pattern and mechanical strength, and a fluoropolymer is preferred from the viewpoint of heat resistance and dielectric loss tangent.
• the content of the resin with respect to the total mass of the layers other than the elastic layer is not particularly limited, and is preferably 30% by mass to 100% by mass, more preferably 35% by mass to 100% by mass. It is more preferably 40% by mass to 100% by mass, particularly preferably 45% by mass to 100% by mass.
• Layers other than the elastic layer can contain the filler.
• the content of the filler with respect to the total mass of the layers other than the elastic layer is preferably 10% by mass to 70% by mass, more preferably 15% by mass to 70% by mass. It is more preferably 65% by mass, still more preferably 20% to 60% by mass, and particularly preferably 35% to 55% by mass.
• 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 coefficient of thermal expansion of the substrate is more preferably -20 ppm/K to 65 ppm/K, still more preferably 0 ppm/K to 55 ppm/K, and 5 ppm/K to 45 ppm/K, from the viewpoint of crack suppression properties. 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 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 0.01 to 1.0, and 0.01 to 1.0. It is more preferably 03 to 0.5.
• the thickness of the substrate is not particularly limited, and from the viewpoint of handleability, it is preferably 30 ⁇ m to 200 ⁇ m, more preferably 40 ⁇ m to 180 ⁇ m, and even more preferably 40 ⁇ m to 150 ⁇ m.
• the base material may be prepared by a conventionally known method, or may be commercially available.
• a woven fabric such as a glass cloth or a non-woven fabric impregnated with the 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.
• a method for producing the base material is illustrated in Examples.
• 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, adhesion to the substrate, 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 for changing from a nonconductor to a conductor, smoothness of a pattern, adhesion to a substrate, 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 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 .
• the base material 11 includes an elastic layer 11a and layers 11b and 11c other than the elastic layer.
• 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.
• FIG. 2 is a cross-sectional view of the metamaterial in FIG. 1 taken along line AA. As shown in FIG.
• the elastic layer 11a may be provided on the entire surface of the layer 11b other than the elastic layer, or may be provided on a part of the surface.
• FIG. 3 shows a cross-sectional view of a metamaterial in which an elastic layer 21a is provided on part of the surface of a layer 21b other than the elastic layer. From the viewpoint of adhesion between the substrate and the pattern and suppression of cracks in the pattern, the elastic layer 21a is preferably provided at least in the region where the structure 22a is provided.
• 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.
• 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 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 10 ⁇ m, and then passed through a sintered fiber metal filter with a nominal pore size of 10 ⁇ m. was passed through a sintered fiber metal filter to obtain composition A.
• composition A powder obtained by freezing and pulverizing thermoplastic elastomer A-1 (Tafmer (registered trademark) MH7020, maleic anhydride-modified polyolefin, Tg ⁇ 65° C., manufactured by Mitsui Chemicals, Inc.) shown in Table 1 was added, After stirring for 30 minutes at 25°C, composition B was obtained. In addition, filler F-1 shown in Table 1 was added to composition A, and the mixture was stirred at 25° C. for 30 minutes to obtain composition C. The contents of the liquid crystalline polyester, thermoplastic elastomer and filler in Compositions A to C were as shown in Table 1. In Compositions A to C, the liquid crystal polyester had a solid content concentration of 10% by mass.
• Compositions A to C are 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 10 ⁇ m.
• a layer made of the product B (described as the first layer in Table 1), a layer made of the composition C having a thickness of 35 ⁇ m (described as the second layer in Table 1), and a layer of 5 ⁇ m
• a substrate having a three-layer structure of a layer made of Composition A (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 elastic recovery rate of the first layer (elastic layer) included in the base material produced as described above was measured by the following nanoindentation method and found to be less than 80%.
• a cross-sectional sample of the substrate was cut using a microtome.
• a nanoindenter trade name “Triboindenter”, manufactured by Hysitron
• the elastic layer of the cross-sectional sample is pushed in from the lateral direction to apply a load, and then the indenter is returned to remove the load.
• a displacement curve was obtained.
• the elastic recovery rate was obtained from the ratio (V2/V1 ⁇ 100) between the maximum displacement amount V1 of the obtained curve and the difference V2 in the displacement amount at which the load becomes 0 when the indenter is returned from the maximum displacement amount.
• the measurement mode is single indentation measurement
• the measurement temperature is 25 ° C.
• the indenter used is a Berkovich (triangular pyramid) type diamond indenter
• the indentation depth of the indenter with respect to the cross-sectional sample is 300 nm
• the indentation of the indenter is The speed was set to 10 nm/sec, and the drawing speed of the indenter from the cross-sectional sample was set to 10 nm/sec.
• the substrate was cut into test specimens with a size of 10 mm x 150 mm.
• the storage elastic modulus of the test piece was measured according to 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 3.4 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.
• 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.
• 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 A metamaterial and a laminate were produced in the same manner as in Example 1, except that the contents of the liquid crystalline polyester and thermoplastic elastomer A-1 in the first layer were changed to the numerical values shown in Table 1.
• 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 base material was measured in the same manner as in Example 1 and found to be 42 ppm/K.
• the elastic recovery rate of the elastic layer included in the substrate was measured by the same method as in Example 1, it was less than 80%.
• the storage elastic moduli of the substrate and the pattern were measured at 25° C. by the same method as in Example 1, they were 3.1 GPa and 30 GPa, respectively.
• Example 3 Filler F-1 is replaced with filler F-2 (polytetrafluoroethylene and perfluoroalkoxyethylene copolymer (PFA) particles, melting point 280 ° C., average particle size 0.2 ⁇ m to 0.5 ⁇ m, dielectric loss tangent 0.001 ), a metamaterial and a laminate were produced in the same manner as in Example 2, except for changing to ).
• PFA polytetrafluoroethylene and perfluoroalkoxyethylene copolymer
• Example 4 A metamaterial and a laminate were produced in the same manner as in Example 2, except that the thicknesses of the first layer and the second layer were changed to the numerical values shown in Table 1.
• 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 base material was measured in the same manner as in Example 1 and found to be 42 ppm/K.
• the elastic recovery rate of the elastic layer included in the substrate was measured by the same method as in Example 1, it was less than 80%.
• the storage elastic moduli of the substrate and the pattern were measured at 25° C. by the same method as in Example 1, they were 3.3 GPa and 30 GPa, respectively.
• Example 5 A metamaterial and a laminate were prepared in the same manner as in Example 4, except that filler F-1 was changed to filler F-3 (silica particles having an average particle diameter of 0.5 ⁇ m, manufactured by Admatechs Co., Ltd., SO-C2). manufactured the body.
• filler F-1 was changed to filler F-3 (silica particles having an average particle diameter of 0.5 ⁇ m, manufactured by Admatechs Co., Ltd., SO-C2). manufactured the body.
• 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 base material was measured in the same manner as in Example 1 and found to be 30 ppm/K.
• the elastic recovery rate of the elastic layer included in the substrate was measured by the same method as in Example 1, it was less than 80%.
• the storage elastic moduli of the substrate and the pattern were measured at 25° C. by the same method as in Example 1, they were 6.6 GPa and 30 GPa, respectively.
• Example 6 Metamaterials and laminates were prepared in the same manner as in Example 2, except that thermoplastic elastomer A-1 was changed to thermoplastic elastomer A-2 (manufactured by Nippon Zeon Co., Ltd., Quintac (registered trademark) 3520). manufactured the body.
• thermoplastic elastomer A-1 was changed to thermoplastic elastomer A-2 (manufactured by Nippon Zeon Co., Ltd., Quintac (registered trademark) 3520). manufactured the body.
• 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 base material was measured in the same manner as in Example 1 and found to be 42 ppm/K.
• the elastic recovery rate of the elastic layer included in the substrate was measured by the same method as in Example 1, it was less than 80%.
• the storage elastic moduli of the substrate and the pattern were measured at 25° C. by the same method as in Example 1, they were
• Example 7 Thermoplastic elastomer A-1 was added to dichloromethane and stirred at 60° C. for 30 minutes to form a solution, which was then passed through a sintered fiber metal filter with a nominal pore size of 10 ⁇ m and then through a sintered fiber metal filter with a nominal pore size of 10 ⁇ m. to obtain composition C.
• 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 D.
• composition C and composition D are fed 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 C having a thickness of 5 ⁇ 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 D having a thickness of 45 ⁇ 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 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 base material was measured in the same manner as in Example 1 and found to be 74 pm/K.
• the elastic recovery rate of the elastic layer included in the substrate was measured by the same method as in Example 1, it was less than 80%.
• the storage elastic moduli of the substrate and the pattern were measured at 25° C. by the same method as in Example 1, they were 2.1 GPa and 30 GPa, respectively.
• Example 8 As the second layer, a 100 ⁇ m-thick cycloolefin polymer film (Zeonor (registered trademark) ZF-14, manufactured by Nippon Zeon Co., Ltd., referred to as PF-1 in Table 1) was prepared. One surface of the second layer was corona treated. The above composition B was applied to the corona-treated surface of the second layer using a reverse gravure coater, and the temperature was gradually raised from room temperature (25°C) to 270°C under a nitrogen atmosphere. was performed for 2 hours to form a first layer having a thickness of 10 ⁇ m, thereby obtaining a substrate.
• Zeonor registered trademark
• ZF-14 manufactured by Nippon Zeon Co., Ltd.
• 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 dielectric loss tangent of the substrate was measured by the same method as in Example 1, it was 0.001.
• the coefficient of thermal expansion of the base material was measured in the same manner as in Example 1 and found to be 82 pm/K.
• the elastic recovery rate of the elastic layer included in the substrate was measured by the same method as in Example 1, it was less than 80%.
• the storage elastic moduli of the substrate and the pattern were measured at 25° C. by the same method as in Example 1, they were 2.1 GPa and 30 GPa, respectively.
• Example 1 A metamaterial and a laminate were produced in the same manner as in Example 1, except that composition A was used to form the first layer.
• composition A was used to form the first layer.
• the coefficient of thermal expansion of the base material was measured in the same manner as in Example 1 and found to be 42 pm/K.
• the elastic recovery rate of the elastic layer included in the substrate was measured by the same method as in Example 1, it was over 80%.
• the storage elastic moduli of the substrate and the pattern were measured at 25° C. by the same method as in Example 1, they were 1.9 GPa and 30 GPa, respectively.
• the test piece was allowed to stand still for 72 hours in an environment of 85° C. and 85% relative humidity for humidity conditioning. After conditioning the humidity, 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.
• ⁇ 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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