CROSS-REFERENCE TO RELATED APPLICATIONS

This application is a continuation application of International Application No. PCT/JP2023/003882, filed Feb. 6, 2023, the disclosure of which is incorporated herein by reference in its entirety. Further, this application claims priority from Japanese Patent Application No. 2022-030214, filed Feb. 28, 2022, the disclosure of which is incorporated herein by reference in its entirety.

BACKGROUND OF THE INVENTION
1. Field of the Invention

The present disclosure relates to a base material for a metamaterial, a metamaterial, a laminate, and a manufacturing method of a metamaterial.

2. Description of the Related Art

In recent years, it has been studied to apply a metamaterial including a base material and a pattern which is composed of a conductive material or the like and is provided on a surface of the base material to an optical element for electromagnetic waves having a frequency of 0.1 to 10 THz (wavelength: 30 to 3,000 μm) (hereinafter, also referred to as electromagnetic waves in a terahertz band).

For example, JP2021-114647A discloses a metamaterial including a metasurface base material and a pattern of a metal film, provided on a surface of the metasurface base material.

SUMMARY OF THE INVENTION

Here, the above-described pattern included in the metamaterial disclosed in JP2021-114647A functions as a resonator with respect to the electromagnetic waves in a terahertz band. Since a portion that functions as the resonator with respect to the electromagnetic waves in a terahertz band is left up to a portion of approximately 0.5 μm in a thickness direction from a surface of the pattern, it is assumed that the thickness of the pattern is to be reduced from the viewpoint of cost reduction and the like in the future development.

The present inventor has found that, in a case where the thickness of the pattern is reduced, rigidity of the pattern is lowered, an internal stress is generated due to deformation of the base material caused by a change in temperature and humidity, and there is a risk of cracks occurring in the pattern.

The present disclosure has been made based on the above-described findings, and an object to be achieved by an embodiment of the present disclosure is to provide a base material for a metamaterial, a metamaterial, a laminate, and a manufacturing method of a metamaterial, in which occurrence of cracks can be suppressed (hereinafter, also referred to as crack suppressibility).

Specific methods for achieving the object are as follows.

<1> A base material for a metamaterial,

- in which a thermal dimensional change rate in a case of being allowed to stand in an environment of 90° C. for 24 hours is-0.01% or less.

<2> The base material for a metamaterial according to <1>,

- in which the thermal dimensional change rate is more than −10%.

<3> The base material for a metamaterial according to <1> or <2>,

- in which a dielectric loss tangent is 0.01 or less.

<4> The base material for a metamaterial according to any one of <1> to <3>,

- in which the base material for a metamaterial contains at least one selected from the group consisting of a fluorine-based polymer and a liquid crystal polymer.

<5> A metamaterial comprising:

- the base material for a metamaterial according to any one of <1> to <4>; and
- a pattern provided on a surface of the base material for a metamaterial, in which the pattern is composed of at least one of a conductive material or a material which transits from an insulator to a conductor.

<6> The metamaterial according to <5>,

- in which a thickness of the pattern is less than 5 μm.

<7> The metamaterial according to <5> or <6>,

- in which the pattern includes a plurality of structural bodies, and the structural bodies are a split-ring resonator.

<8> The metamaterial according to any one of <5> to <7>,

- in which the pattern is composed of the conductive material, and the conductive material includes a metal.

<9> The metamaterial according to any one of <5> to <8>,

- in which a ratio of a product of a thickness of the pattern and a storage elastic modulus of the pattern at 25° C. to a product of a thickness of the base material for a metamaterial and a storage elastic modulus of the base material for a metamaterial at 25° C. is less than 10.

<10> A laminate comprising:

- the metamaterial according to any one of <5> to <9>; and
- an organic film provided on a surface of the metamaterial on a pattern side.

<11> The laminate according to <10>,

- in which a moisture permeability of the organic film in an environment of a temperature of 40° C. and a relative humidity of 90% is 3,000 g/(m²·24 hours) or less.

<12> The laminate according to <10> or <11>,

- in which the organic film contains an ultraviolet absorber.

<13> A manufacturing method of a metamaterial, comprising:

- a step of disposing at least one of a conductive material or a material which transits from an insulator to a conductor on a surface of the base material for a metamaterial according to any one of <1> to <4>; and
- a step of patterning the conductive material or the material which transits from an insulator to a conductor, which is disposed on the surface of the base material for a metamaterial, to form a pattern.

According to the embodiment of the present disclosure, it is possible to provide a base material for a metamaterial, a metamaterial, a laminate, and a manufacturing method of a metamaterial, in which crack suppressibility is excellent.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 is a perspective view showing an embodiment of a metamaterial according to the present disclosure.

DESCRIPTION OF THE PREFERRED EMBODIMENTS

In the present disclosure, the numerical ranges shown using “to” include the numerical values described before and after “to” as the minimum value and the maximum value.

In a numerical range described in a stepwise manner in the present disclosure, an upper limit or a lower limit described in one numerical range may be replaced with an upper limit or a lower limit in another numerical range described in a stepwise manner. Further, in a numerical range described in the present disclosure, an upper limit or a lower limit described in the numerical range may be replaced with a value described in an example.

In the present disclosure, each component may contain a plurality of types of corresponding substances.

In the present disclosure, a term “layer” or “film” includes not only a case where the layer or the film is formed over the entire region but also a case where the layer or the film is formed only in part of the region.

In the present disclosure, the term “step” includes not only an independent step but also a step that cannot be clearly distinguished from other steps, as long as the intended purpose of the step is achieved.

In the present disclosure, the term “metamaterial” refers to a member which is composed of a conductive material or the like and has a pattern that functions as a resonator with respect to electromagnetic waves.

The metamaterial preferably has a pattern serving as a resonator with respect to electromagnetic waves having a frequency of 0.01 THz to 10 THz (wavelength: 30 μm to 30,000 μm), and more preferably has a pattern serving as a resonator with respect to electromagnetic waves having a frequency of 0.1 THz to 10 THz (wavelength: 30 μm to 3,000 μm).

In the present disclosure, a measurement of a storage elastic modulus of the base material at 25° C. is carried out under conditions of a temperature of 25° C. and a relative humidity of 50%, in conformity with the method described in JIS K 7127 (1999).

In a case of measuring the storage elastic modulus of the base material, a test piece having a size of 10 mm×150 mm is produced, and the storage elastic modulus of the test piece is measured.

In a case of measuring the storage elastic modulus of the pattern, the pattern formed on the surface of the base material is cut out to have a size of 5 mm×5 mm to produce a test piece, and the storage elastic modulus of the test piece is measured under the conditions of a temperature of 25° C. and a relative humidity of 50% using a scanning probe microscope.

In the present disclosure, a measurement of a moisture permeability is carried out under conditions of a temperature of 40° C., a relative humidity of 90%, and 24 hours of standing, in conformity with the method described in JIS Z 0208 (1976).

In the present disclosure, a weight-average molecular weight (Mw) is a molecular weight converted using polystyrene as a standard substance by performing detection with a gel permeation chromatography (GPC) analysis apparatus using TSKgel SuperHM-H (trade name, manufactured by Tosoh Corporation) column, a solvent of pentafluorophenol (PFP) and chloroform at a mass ratio of 1:2, and a differential refractometer, unless otherwise specified.

In the present disclosure, “(meth)acrylic” is a concept including both acrylic and methacrylic.

In the present disclosure, “solid content” means components forming a layer formed of a composition or the like, and in a case where the composition or the like contains a solvent (an organic solvent, water, or the like), it means all components excluding the solvent. In addition, a liquid component is also regarded as the solid content in a case where the component is a component which forms the layer.

In the present disclosure, in a case where an embodiment is described with reference to the drawing, the configuration of the embodiment is not limited to the configuration shown in the drawing. In addition, sizes of members in each drawing are conceptual, and a relative relationship between the sizes of the members is not limited thereto.

[Base Material for Metamaterial]

In the base material for a metamaterial according to the present disclosure, a thermal dimensional change rate in a case of being allowed to stand in an environment of 90° C. for 24 hours is-0.01% or less.

The base material for a metamaterial according to the present disclosure has excellent crack suppressibility. The mechanism by which the above-described effect is exhibited is not clear, but is presumed as follows. In a case where a pattern is provided on the surface of the base material for a metamaterial according to the embodiment of the present invention, the laminate is used as a metamaterial, and the base material for a metamaterial is stretched and contracted due to a change in temperature or the like, an internal stress is generated in the pattern. In particular, in a case where the internal stress in a tensile direction exceeds a fracture stress of the pattern, cracks occur in the pattern. Since the base material for a metamaterial according to the present disclosure has a specific thermal dimensional change rate, and thus shrinks due to an external stimulus such as a temperature, the amount of deformation on the compression side is added to the pattern, and the amount of deformation in the tensile direction described above is relaxed. As a result, it is presumed that the occurrence of cracks is suppressed because the internal stress generated in the pattern is reduced.

From the viewpoint of crack suppressibility, the thermal dimensional change rate of the base material for a metamaterial is preferably −0.05% or less, more preferably −0.1% or less, still more preferably −0.3% or less, and particularly preferably −0.5% or less.

From the viewpoint of suppressing occurrence of wrinkles in the pattern (hereinafter, also referred to as wrinkle suppressibility), the thermal dimensional change rate of the base material for a metamaterial is preferably more than −10%, more preferably −8% or more, still more preferably −5% or more, and particularly preferably −3% or more.

From the viewpoint of crack suppressibility and wrinkle suppressibility, the thermal dimensional change rate of the base material for a metamaterial is preferably −0.05% or less and more than −10%, more preferably −8% to −0.1%, still more preferably −5% to −0.3%, and particularly preferably −3% to −0.5%.

The thermal dimensional change rate of the base material for a metamaterial can be adjusted by changing a material to be contained in the base material for a metamaterial, changing the conditions of the stretching treatment in a case of manufacturing the base material for a metamaterial, or the like.

In the present disclosure, the thermal dimensional change rate of the base material for a metamaterial is measured by the following method.

First, the base material for a metamaterial is cut into a size of 30 mm×120 mm to produce a test piece.

Markings are put on the test piece at intervals of 10 cm, and the test piece is allowed to stand in an environment of 25° C. and a relative humidity of 60% for 24 hours to be humidity-adjusted, and then the intervals of the markings are measured (the measured value is denoted as L0).

Next, the test piece is allowed to stand in a hot air dryer at 90° C. for 24 hours, and then allowed to stand in an environment of 25° C. and a relative humidity of 60% for 24 hours to be humidity-adjusted, and the intervals of the markings are measured (the measured value is denoted as L1). The thermal dimensional change rate is obtained by the following expression, and means that the film has contracted in a case of a negative value and has expanded in a case of a positive value.

L0 and L1 are substituted into the following expression to calculate the thermal dimensional change rate.

Thermal dimensional change rate [%]=((L1-L0)/L0)×100

From the viewpoint of electrical characteristics, a dielectric loss tangent of the base material for a metamaterial is preferably 0.01 or less, more preferably 0.0005 to 0.007, still more preferably 0.001 to 0.006, and particularly preferably 0.001 to 0.005.

The dielectric loss tangent of the base material for a metamaterial can be adjusted by changing the material to be contained in the base material for a metamaterial, or the like.

In the present disclosure, the dielectric loss tangent of the base material for a metamaterial is measured by the following terahertz time-domain spectroscopy (THz-TDS).

First, the base material is cut into a test piece having a size of 100 mm×100 mm.

Next, an optical system for transmission-type terahertz spectroscopy is produced, and a dielectric loss tangent of the test piece is measured from a change in time waveform of the electric field (frequency: 1 THz) before and after insertion of the test piece in an environment of a temperature of 25° C. and a humidity of 10% RH.

In a case where the pattern described later is formed on the surface of the base material for a metamaterial, the above-described measurement of the dielectric loss tangent is carried out using a base material for a metamaterial, which has been etched with a solution such as iron chloride.

The base material for a metamaterial may have a monolayer structure or a multilayer structure.

(Resin)

The material constituting the base material for a metamaterial is not particularly limited, but from the viewpoint of handleability and the like, a resin is preferable.

Examples of the resin which can be contained in the base material for a metamaterial include thermoplastic resins such as a liquid crystal polymer, a fluorine-based polymer, a polymerized substance of a compound which has a cyclic aliphatic hydrocarbon group and a group having an ethylenically unsaturated bond, polyether ether ketone, polyolefin, polyamide, polyester, polyphenylene sulfide, aromatic polyether ketone, polycarbonate, polyarylate, polyethersulfone, polyphenylene ether and a modified product thereof, and polyetherimide; elastomers such as a copolymer of glycidyl methacrylate and polyethylene; and thermosetting resins such as a phenol resin, an epoxy resin, a polyimide resin, and a cyanate resin.

Among these, from the viewpoint of crack suppressibility, dielectric loss tangent, adhesiveness with the pattern, and heat resistance, at least one selected from the group consisting of a liquid crystal polymer, a fluorine-based polymer, a polymerized substance of a compound which has a cyclic aliphatic hydrocarbon group and a group having an ethylenically unsaturated bond, polyphenylene ether, aromatic polyether ketone, and an epoxy resin is preferable, and at least one selected from the group consisting of a liquid crystal polymer and a fluorine-based polymer is more preferable.

From the viewpoint of adhesiveness with the pattern and mechanical strength, a liquid crystal polymer is preferable, and from the viewpoint of heat resistance and dielectric loss tangent, a polymerized substance of a compound which has a cyclic aliphatic hydrocarbon group and a group having an ethylenically unsaturated bond, a polyarylate, a polyethersulfone, or a fluorine-based polymer is preferable.

The liquid crystal polymer may be a thermotropic liquid crystal polymer which exhibits liquid crystallinity in a molten state, or may be a lyotropic liquid crystal polymer which exhibits liquid crystallinity in a solution state. Further, in a case where the liquid crystal polymer is a thermotropic liquid crystal polymer, the liquid crystal polymer is preferably a liquid crystal polymer which is molten at a temperature of 450° C. or lower.

Examples of the liquid crystal polymer include a liquid crystal polyester, a liquid crystal polyester amide in which an amide bond is introduced into the liquid crystal polyester, a liquid crystal polyester ether in which an ether bond is introduced into the liquid crystal polyester, and a liquid crystal polyester carbonate in which a carbonate bond is introduced into the liquid crystal polyester.

In addition, as the liquid crystal polymer, from the viewpoint of liquid crystallinity and thermal expansion coefficient, a polymer having an aromatic ring is preferable, and an aromatic polyester or an aromatic polyester amide is more preferable.

Further, the liquid crystal polymer may be a polymer in which an imide bond, a carbodiimide bond, a bond derived from an isocyanate, such as an isocyanurate bond, or the like is further introduced into the aromatic polyester or the aromatic polyester amide.

Further, it is preferable that the liquid crystal polymer is a wholly aromatic liquid crystal polymer formed of only an aromatic compound as a raw material monomer.

Examples of the liquid crystal polymer include the following liquid crystal polymers.

1) a liquid crystal polymer obtained by polycondensing (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 hydroxyamine, and an aromatic diamine;

2) a liquid crystal polymer obtained by polycondensing a plurality of types of aromatic hydroxycarboxylic acids;

3) a liquid crystal polymer obtained by polycondensing (i) an aromatic dicarboxylic acid and (ii) at least one compound selected from the group consisting of an aromatic diol, an aromatic hydroxyamine, and an aromatic diamine;

4) a liquid crystal polymer obtained by polycondensing (i) polyester such as polyethylene terephthalate and (ii) an aromatic hydroxycarboxylic acid.

Here, the aromatic hydroxycarboxylic acid, the aromatic dicarboxylic acid, the aromatic diol, the aromatic hydroxyamine, and the aromatic diamine may be each independently replaced with a polycondensable derivative.

For example, the aromatic hydroxycarboxylic acid and the aromatic dicarboxylic acid can be replaced with aromatic hydroxycarboxylic acid ester and aromatic dicarboxylic acid ester, by converting a carboxy group into an alkoxycarbonyl group or an aryloxycarbonyl group.

The aromatic hydroxycarboxylic acid and the aromatic dicarboxylic acid can be replaced with aromatic hydroxycarboxylic acid halide and aromatic dicarboxylic acid halide, by converting a carboxy group into a haloformyl group.

The aromatic hydroxycarboxylic acid and the aromatic dicarboxylic acid can be replaced with aromatic hydroxycarboxylic acid anhydride and aromatic dicarboxylic acid anhydride, by converting a carboxy group into an acyloxycarbonyl group.

Examples of a polymerizable derivative of a compound having a hydroxy group, such as an aromatic hydroxycarboxylic acid, an aromatic diol, and an aromatic hydroxyamine, include a derivative (acylated product) obtained by acylating a hydroxy group and converting the acylated group into an acyloxy group.

For example, the aromatic hydroxycarboxylic acid, the aromatic diol, and the aromatic hydroxyamine can be each replaced with an acylated product by acylating a hydroxy group and converting the acylated group into an acyloxy group.

Examples of a polymerizable derivative of a compound having an amino group, such as an aromatic hydroxyamine or an aromatic diamine, include a derivative (acylated product) obtained by acylating an amino group and converting the acylated group to an acylamino group.

For example, the aromatic hydroxyamine and the aromatic diamine can be each replaced with an acylated product by acylating an amino group and converting the acylated group into an acylamino group.

From the viewpoint of liquid crystallinity, dielectric loss tangent, and adhesiveness with the pattern, the liquid crystal polymer preferably has a constitutional unit represented by any of Formulae (1) to (3) (hereinafter, a constitutional unit represented by Formula (1) or the like may be referred to as a constitutional unit (1) or the like), more preferably has a constitutional unit represented by Formula (1), and particularly preferably has a constitutional unit represented by Formula (1), a constitutional unit represented by Formula (2), and a constitutional unit represented by Formula (3).

—O—Ar¹—CO— Formula (1)

—CO—Ar²—CO— Formula (2)

—X—Ar³—Y— Formula (3)

in Formulae (1) to (3), Ar¹represents a phenylene group, a naphthylene group, or a biphenylylene group, Ar²and Ar³each independently represent a phenylene group, a naphthylene group, a biphenylylene group, or a group represented by Formula (4), X and Y each independently represent an oxygen atom or an imino group, and hydrogen atoms in Ar¹to Ar³may be each independently substituted with a halogen atom, an alkyl group, or an aryl group,

—Ar⁴—Z—Ar⁵— Formula (4)

in Formula (4), Ar⁴and Ar⁵each 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.

Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.

Examples of the alkyl group include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, an s-butyl group, a t-butyl group, an n-hexyl group, a 2-ethylhexyl group, an n-octyl group, and an n-decyl group. The number of carbon atoms in the alkyl group is preferably 1 to 10.

Examples of the aryl group include a phenyl group, an o-tolyl group, an m-tolyl group, a p-tolyl group, a 1-naphthyl group, and a 2-naphthyl group. The number of carbon atoms in the aryl group is preferably 6 to 20.

In a case where the hydrogen atom is substituted with any of these groups, the number of each of substitutions in Ar¹, Ar², and Ar³independently is preferably 2 or less and more preferably 1.

Examples of the alkylene group include a methylene group, a 1,1-ethanediyl group, a 1-methyl-1,1-ethanediyl group, a 1,1-butanediyl group, and a 2-ethyl-1,1-hexanediyl group. The number of carbon atoms in the alkylene group is preferably 1 to 10.

The constitutional unit (1) is a constitutional unit derived from an aromatic hydroxycarboxylic acid.

As the constitutional unit (1), an aspect in which Ar¹represents a p-phenylene group (constitutional unit derived from p-hydroxybenzoic acid), an aspect in which Ar¹represents a 2,6-naphthylene group (constitutional unit derived from 6-hydroxy-2-naphthoic acid), or an aspect in which Ar¹represents a 4,4′-biphenylylene group (constitutional unit derived from 4′-hydroxy-4-biphenylcarboxylic acid) is preferable.

The constitutional unit (2) is a constitutional unit derived from an aromatic dicarboxylic acid.

As the constitutional unit (2), an aspect in which Ar²represents a p-phenylene group (constitutional unit derived from terephthalic acid), an aspect in which Ar²represents an m-phenylene group (constitutional unit derived from isophthalic acid), an aspect in which Ar²represents a 2,6-naphthylene group (constitutional unit derived from 2,6-naphthalenedicarboxylic acid), or an aspect in which Ar²represents a diphenylether-4,4′-diyl group (constitutional unit derived from diphenylether-4,4′-dicarboxylic acid) is preferable.

The constitutional unit (3) is a constitutional unit derived from an aromatic diol, an aromatic hydroxyamine, or an aromatic diamine.

As the constitutional unit (3), an aspect in which Ar³represents a p-phenylene group (constitutional unit derived from hydroquinone, p-aminophenol, or p-phenylenediamine), an aspect in which Ar³represents an m-phenylene group (constitutional unit derived from isophthalic acid), or an aspect in which Ar³represents a 4,4′-biphenylylene group (constitutional unit derived from 4,4′-dihydroxybiphenyl, 4-amino-4′-hydroxybiphenyl, or 4,4′-diaminobiphenyl) is preferable.

A content of the constitutional unit (1) is preferably 30% by mole or more, more preferably 30% to 80% by mole, still more preferably 30% to 60% by mole, and particularly preferably 30% to 40% by mole with respect to the total amount of all constitutional units (a value obtained by dividing the mass of each constitutional unit (also referred to as “monomer unit”) constituting the liquid crystal polymer by the formula weight of each constitutional unit to calculate an amount (mole) equivalent to the substance amount of each constitutional unit and adding up the amounts).

A content of the constitutional unit (2) is preferably 35% by mole or less, more preferably 10% by mole to 35% by mole, still more preferably 20% by mole to 35% by mole, and particularly preferably 30% by mole to 35% by mole with respect to the total amount of all constitutional units.

A content of the constitutional unit (3) is preferably 35% by mole or less, more preferably 10% by mole to 35% by mole, still more preferably 20% by mole to 35% by mole, and particularly preferably 30% by mole to 35% by mole with respect to the total amount of all constitutional units.

The heat resistance, the strength, and the rigidity are likely to be improved as the content of the constitutional unit (1) increases, but the solubility in a solvent is likely to be decreased in a case where the content thereof is extremely large.

A proportion of the content of the constitutional unit (2) to the content of the constitutional unit (3) is expressed as [content of constitutional unit (2)]/[content of constitutional unit (3)] (mol/mol), and is preferably 0.9/1 to 1/0.9, more preferably 0.95/1 to 1/0.95, and still more preferably 0.98/1 to 1/0.98.

The liquid crystal polymer may have two or more kinds of each of the constitutional units (1) to (3) independently. In addition, the liquid crystal polymer may have a constitutional unit other than the constitutional units (1) to (3), but the content thereof is preferably 10% by mole or less and more preferably 5% by mole or less with respect to the total amount of all the constitutional units.

From the viewpoint of solubility in a solvent, the liquid crystal polymer preferably has, as the constitutional unit (3), a constitutional unit (3) in which at least one of X or Y is an imino group, that is, preferably has as the constitutional unit (3), at least one of a constitutional unit derived from an aromatic hydroxyamine or a constitutional unit derived from an aromatic diamine, and it is more preferable to have only a constitutional unit (3) in which at least one of X or Y is an imino group.

It is preferable that the liquid crystal polymer is produced by melt-polymerizing raw material monomers corresponding to the constitutional units constituting the liquid crystal polymer. The melt polymerization may be carried out in the presence of a catalyst. Examples of the catalyst include metal compounds such as magnesium acetate, stannous acetate, tetrabutyl titanate, lead acetate, sodium acetate, potassium acetate, and antimony trioxide, and nitrogen-containing heterocyclic compounds such as 4-(dimethylamino)pyridine and 1-methylimidazole; and preferred examples thereof include nitrogen-containing heterocyclic compounds. The melt polymerization may be further carried out by solid phase polymerization as necessary.

In addition, a weight-average molecular weight of the liquid crystal polymer is preferably 1,000,000 or less, more preferably 3,000 to 300,000, still more preferably 5,000 to 100,000, and particularly preferably 5,000 to 30,000. In a case where the weight-average molecular weight of the liquid crystal polymer is within the above-described range, the base material for a metamaterial is excellent in thermal conductivity, heat resistance, strength, and rigidity in the thickness direction.

Examples of the fluorine-based polymer include polytetrafluoroethylene, polychlorotrifluoroethylene, polyvinylidene fluoride, polyvinyl fluoride, a perfluoroalkoxy fluororesin, an ethylene tetrafluoride/propylene hexafluoride copolymer, an ethylene/ethylene tetrafluoride copolymer, and an ethylene/chlorotrifluoroethylene copolymer.

Among these, polytetrafluoroethylene is preferable.

In addition, examples of the fluorine-based polymer include a fluorinated α-olefin monomer, that is, an α-olefin monomer containing at least one fluorine atom; and a homopolymer and a copolymer optionally containing a constitutional unit derived from a non-fluorinated ethylenically unsaturated monomer reactive to the fluorinated α-olefin monomer.

Examples of the fluorinated α-olefin monomer include CF₂═CF₂, CHF═CF₂, CH₂—CF₂, CHCI═CHF, CClF═CF₂, CCl₂—CF₂, CClF═CClF, CHF═CCl₂, CH₂—CClF, CCl₂═CClF, CF₃CF—CF₂, CF₃CF═CHF, CF₃CH—CF₂, CF₃CH═CH₂, CHF₂CH═CHF, CF₃CF═CF₂, and perfluoro (alkyl having 2 to 8 carbon atoms) vinyl ether (for example, perfluoromethyl vinyl ether, perfluoropropyl vinyl ether, and perfluorooctyl vinyl ether). Among these, at least one monomer selected from the group consisting of tetrafluoroethylene (CF₂═CF₂), chlorotrifluoroethylene (CClF═CF₂), (perfluorobutyl)ethylene, vinylidene fluoride (CH₂—CF₂), and hexafluoropropylene (CF₂═CFCF₃) is preferable.

Examples of the non-fluorinated ethylenically unsaturated monomer include ethylene, propylene, butene, and an ethylenically unsaturated aromatic monomer (for example, styrene and α-methylstyrene).

The fluorinated α-olefin monomer may be used alone or in combination of two or more thereof.

In addition, the non-fluorinated ethylenically unsaturated monomer may be used alone or in combination of two or more thereof.

Examples of the fluorine-based polymer include poly(chlorotrifluoroethylene) (PCTFE), poly(chlorotrifluoroethylene-propylene), poly(ethylene-tetrafluoroethylene) (ETFE), poly(ethylene-chlorotrifluoroethylene) (ECTFE), poly(hexafluoropropylene), poly(tetrafluoroethylene) (PTFE), poly(tetrafluoroethylene-ethylene-propylene), poly(tetrafluoroethylene-hexafluoropropylene) (also referred to as a fluorinated ethylene-propylene copolymer (FEP)), poly(tetrafluoroethylene-propylene) (also referred to as a fluoroelastomer (FEPM)), poly(tetrafluoroethylene-perfluoropropylene vinyl ether), a copolymer having a tetrafluoroethylene main chain and a fully fluorinated alkoxy side chain (perfluoroalkoxy polymer; also referred to as a poly(tetrafluoroethylene-perfluoroalkyl vinyl ether) (PFA)) (for example, poly(tetrafluoroethylene-erfluoropropylene propyl vinyl ether)), polyvinyl fluoride (PVF), polyvinylidene fluoride (PVDF), poly(vinylidene fluoride-chlorotrifluoroethylene), perfluoropolyether, perfluorosulfonic acid, and perfluoropolyoxetane.

The fluorine-based polymer may be used alone or in combination of two or more thereof.

The fluorine-based polymer is preferably at least one of FEP, PFA, ETFE, or PTFE. These may have fibril-forming properties or non-fibril-forming properties. The FEP is available from Du Pont as the trade name of TEFLON (registered trademark) FEP or from DAIKIN INDUSTRIES, LTD. as the trade name of NEOFLON FEP; and the PFA is available from DAIKIN INDUSTRIES, LTD. as the trade name of NEOFLON PFA, from Du Pont as the trade name of TEFLON (registered trademark) PFA, or from Solvay Solexis as the trade name of HYFLON PFA.

The fluorine-based polymer preferably includes PTFE. The PTFE can be included as a PTFE homopolymer, a partially modified PTFE homopolymer, or a combination including one or both of these. The partially modified PTFE homopolymer preferably contains a constitutional unit derived from a comonomer other than tetrafluoroethylene in an amount of less than 1% by mass based on the total mass of the polymer.

The fluorine-based polymer may be a crosslinkable fluoropolymer having a crosslinkable group. The crosslinkable fluoropolymer can be crosslinked by a known crosslinking method in the related art. One of the representative crosslinkable fluoropolymers is a fluoropolymer having a (meth)acryloxy group. For example, the crosslinkable fluoropolymer can be represented by Formula:

H₂C═CR′COO—(CH₂)_n—R—(CH₂)_n—OOCR′═CH₂

in the formula, R is a fluorine-based oligomer chain having two or more constitutional units derived from the fluorinated α-olefin monomer or the non-fluorinated monoethylenically unsaturated monomer, R′ is H or —CH₃, and n is 1 to 4. R may be a fluorine-based oligomer chain having a constitutional unit derived from tetrafluoroethylene.

In order to initiate a radical crosslinking reaction through the (meth)acryloxy group in the fluorine-based polymer, by exposing the fluoropolymer having a (meth)acryloxy group to a free radical source, a crosslinked fluoropolymer network can be formed. The free radical source is not particularly limited, and suitable examples thereof include a photoradical polymerization initiator and an organic peroxide. Appropriate photoradical polymerization initiators and organic peroxides are well known in the art. The crosslinkable fluoropolymer is commercially available, and examples thereof include Viton B manufactured by Du Pont.

Examples of the polymerized substance of a compound which has a cyclic aliphatic hydrocarbon group and a group having an ethylenically unsaturated bond include thermoplastic resins having a constitutional unit formed from a monomer having a cyclic olefin such as norbornene and a polycyclic norbornene-based monomer, which is also referred to as a thermoplastic cyclic olefin-based resin.

The polymerized substance of a compound which has a cyclic aliphatic hydrocarbon group and a group having an ethylenically unsaturated bond may be a ring-opened polymer of the above-described cyclic olefin, a hydrogenated product of a ring-opened copolymer using two or more cyclic olefins, or an addition polymer of a cyclic olefin and a linear olefin or aromatic compound having an ethylenically unsaturated bond such as a vinyl group. In addition, a polar group may be introduced into the polymerized substance of a compound which has a cyclic aliphatic hydrocarbon group and a group having an ethylenically unsaturated bond.

The polymerized substance of a compound which has a cyclic aliphatic hydrocarbon group and a group having an ethylenically unsaturated bond may be used alone or in combination of two or more thereof.

A ring structure of the cyclic aliphatic hydrocarbon group may be a single ring, a fused ring in which two or more rings are fused, or a crosslinked ring.

Examples of the ring structure of the cyclic aliphatic hydrocarbon group include a cyclopentane ring, a cyclohexane ring, a cyclooctane ring, an isophorone ring, a norbornane ring, and a dicyclopentane ring.

The compound which has a cyclic aliphatic hydrocarbon group and a group having an ethylenically unsaturated bond may be a monofunctional ethylenically unsaturated compound or a polyfunctional ethylenically unsaturated compound.

The number of cyclic aliphatic hydrocarbon groups in the compound which has a cyclic aliphatic hydrocarbon group and a group having an ethylenically unsaturated bond may be 1 or more, and may be 2 or more.

It is sufficient that the polymerized substance of a compound which has a cyclic aliphatic hydrocarbon group and a group having an ethylenically unsaturated bond is a polymer obtained by polymerizing at least one compound which has a cyclic aliphatic hydrocarbon group and a group having an ethylenically unsaturated bond, and it may be a polymerized substance of two or more kinds of the compound which has a cyclic aliphatic hydrocarbon group and a group having an ethylenically unsaturated bond or a copolymer with other ethylenically unsaturated compounds having no cyclic aliphatic hydrocarbon group.

In addition, the polymerized substance of a compound which has a cyclic aliphatic hydrocarbon group and a group having an ethylenically unsaturated bond is preferably a cycloolefin polymer.

In the polyphenylene ether, from the viewpoint of dielectric loss tangent and heat resistance, the average number of molecular terminal phenolic hydroxyl groups per molecule (the number of terminal hydroxyl groups) is preferably 1 to 5 and more preferably 1.5 to 3.

The number of hydroxyl groups or the number of phenolic hydroxyl groups in the polyphenylene ether can be found, for example, from a standard value of a product of the polyphenylene ether. In addition, examples of the number of terminal hydroxyl groups or the number of terminal phenolic hydroxyl groups include a numerical value representing an average value of hydroxyl groups or phenolic hydroxyl groups per molecule of all polyphenylene ethers present in 1 mol of the polyphenylene ether.

The polyphenylene ether may be used alone or in combination of two or more thereof.

Examples of the polyphenylene ether include a polyphenylene ether including 2,6-dimethylphenol and at least one of bifunctional phenol or trifunctional phenol, and a compound mainly including the polyphenylene ether, such as poly(2,6-dimethyl-1,4-phenylene oxide). More specifically, for example, a compound having a structure represented by Formula (PPE) is preferable.

[Image Omitted]

In 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, and the sum of m and n represents an integer of 1 to 30.

Examples of the alkylene group in X described above include a dimethylmethylene group.

The aromatic polyether ketone is not particularly limited, and a known aromatic polyether ketone can be used.

The aromatic polyether ketone is preferably a polyether ether ketone.

The polyether ether ketone is one type of the aromatic polyether ketone, and is a polymer in which bonds are arranged in the order of an ether bond, an ether bond, and a carbonyl bond (ketone). It is preferable that the bonds are linked to each other by a divalent aromatic group.

The aromatic polyether ketone may be used alone or in combination of two or more thereof.

Examples of the aromatic polyether ketone include polyether ether ketone (PEEK) having a chemical structure represented by Formula (P1), polyether ketone (PEK) having a chemical structure represented by Formula (P2), polyether ketone ketone (PEKK) having a chemical structure represented by Formula (P3), polyether ether ketone ketone (PEEKK) having a chemical structure represented by Formula (P4), and polyether ketone ether ketone ketone (PEKEKK) having a chemical structure represented by Formula (P5).

[Image Omitted]

From the viewpoint of mechanical properties, each n of Formulae (P1) to (P5) is preferably 10 or more and more preferably 20 or more. On the other hand, from the viewpoint that the aromatic polyether ketone can be easily produced, n is preferably 5,000 or less and more preferably 1,000 or less. That is, n is preferably 10 to 5,000 and more preferably 20 to 1,000.

A content of the resin with respect to the total mass of the base material for a metamaterial is not particularly limited, but is preferably 50% by mass or more, more preferably 70% by mass or more, and still more preferably 90% by mass or more. The upper limit of the content of the resin is not particularly limited, and may be 100% by mass.

(Compound having functional group)

The base material for a metamaterial may contain a compound having a functional group.

From the viewpoint of crack suppressibility and adhesiveness with the pattern, the functional group is preferably at least one group selected from the group consisting of “covalent-bondable group with at least one of the conductive material or the material which transits from an insulator to a conductor, constituting the pattern”, “ion-bondable group with the conductive material or the like”, “hydrogen-bondable group with the conductive material or the like”, “dipole-interactable group with the conductive material or the like”, and “curing reactive group with the conductive material or the like”.

In a case where the base material for a metamaterial has a multilayer structure, the compound having a functional group is preferably contained in a layer in which the pattern is provided. For example, in a case where the base material for a metamaterial has a three-layer structure of a first layer, a second layer, and a third layer and the pattern is formed on the first layer, it is preferable that the first layer contains the compound having a functional group.

In addition, depending on the material constituting the base material, the compound having a functional group can also form the above-described bond or the like with the material constituting the base material.

The compound having a functional group may be a low-molecular-weight compound or a high-molecular-weight compound.

From the viewpoint of dielectric loss tangent of the base material for a metamaterial, the compound having a functional group is preferably a low-molecular-weight compound, and from the viewpoint of heat resistance and mechanical strength of the base material for a metamaterial, it is preferably a high-molecular-weight compound.

It is sufficient that the number of functional groups in the compound having a functional group is 1 or more, and it may be 2 or more. However, the number of functional groups in the compound having a functional group is preferably 2 or more, and from the viewpoint of reducing the dielectric loss tangent of the polymer film by setting the amount of functional groups to an appropriate amount, it is preferably 10 or less.

In addition, the compound having a functional group may have only one kind of functional group, or two or more kinds of functional groups.

From the viewpoint of adhesiveness with the pattern, 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 has a molecular weight of 100 or more and less than 1,000, and particularly preferably has a molecular weight of 200 or more and less than 1,000.

In a case where the compound having a functional group is a low-molecular-weight compound, the spread of the compound is narrow, and in order to increase the contact probability between the functional groups, a content of the compound having a functional group is preferably 10% by mass or more with respect to the total mass of the base material for a metamaterial.

In addition, from the viewpoint of adhesiveness with the pattern, the high-molecular-weight compound used as the compound having a functional group is preferably a polymer having a weight-average molecular weight of 1,000 or more, more preferably a polymer having a weight-average molecular weight of 2,000 or more, still more preferably a polymer having a weight-average molecular weight of 3,000 or more and 1,000,000 or less, and particularly preferably a polymer having a weight-average molecular weight of 5,000 or more and 200,000 or less.

Furthermore, from the viewpoint of dielectric loss tangent of the base material for a metamaterial and adhesiveness with the pattern, it is preferable that the resin and the compound having a functional group described above are compatible with each other. Here, the “compatible with each other” means that phase separation is not observed inside the base material for a metamaterial.

From the viewpoint of compatibility, dielectric loss tangent of the base material for a metamaterial, and adhesiveness with the pattern, a difference between the SP value of the resin, which is determined by Hoy method, and the SP value of the compound having a functional group, which is determined by Hoy method, is preferably 5 MPa^0.5or less. The lower limit value thereof is 0 MPa^0.5.

The solubility parameter value (SP value) determined by Hoy method is calculated from the molecular structure of the resin by the method described in Polymer Handbook fourth edition. In addition, in a case where the resin is a mixture of a plurality of types of resins, the SP value is obtained by calculating an SP value of each constitutional unit.

The covalent-bondable group is not particularly limited as long as the group is capable of forming a covalent bond with the conductive material or the like, and examples thereof include an epoxy group, an oxetanyl group, an isocyanate group, an acid anhydride group, a carbodiimide group, a N-hydroxy ester group, a glyoxal group, an imidoester group, a halogenated alkyl group, a thiol group, a hydroxy group, a carboxy group, an amino group, an amide group, an isocyanate group, an aldehyde group, and a sulfonic acid group. Among these, from the viewpoint of adhesiveness with the pattern, the covalent-bondable group is preferably at least one functional group selected from the group consisting of an epoxy group, an oxetanyl group, an N-hydroxy ester group, an isocyanate group, an imide ester group, a halogenated alkyl group, and a thiol group, and particularly preferably an epoxy group.

Examples of the ion-bondable group with the conductive material or the like include a cationic group and an anionic group.

The above-described cationic group is preferably an onium group. Examples of the onium group include an ammonium group, a pyridinium group, a phosphonium group, an oxonium group, a sulfonium group, a selenonium group, and an iodonium group. Among these, from the viewpoint of adhesiveness with the pattern, an ammonium group, a pyridinium group, a phosphonium group, or a sulfonium group is preferable, an ammonium group or a phosphonium group is more preferable, and an ammonium group is particularly preferable.

The anionic group is not particularly limited, and examples thereof include a phenolic hydroxyl group, a carboxy group, —SO₃H, —OSO₃H, —PO₃H, —OPO₃H₂, —CONHSO₂—, and —SO₂NHSO₂—. Among these, 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 preferable, a phosphoric acid group or a carboxy group is more preferable, and a carboxy group is still more preferable.

Examples of the hydrogen-bondable group with the conductive material or the like include a group having a hydrogen-bond-donating moiety and a group having a hydrogen-bond-accepting moiety.

It is sufficient that the hydrogen-bond-donating moiety has a structure having an active hydrogen atom capable of hydrogen bonding, and a structure represented by X—H is preferable.

X represents a heteroatom, and is preferably a nitrogen atom or an oxygen atom.

From the viewpoint of adhesiveness with the pattern, as the above-described hydrogen-bond-donating moiety, at least one structure selected from the group consisting of a hydroxy group, a carboxy group, a primary amide group, a secondary amide group, a primary amino group, a secondary amino group, a primary sulfonamide group, a secondary sulfonamide group, an imide group, a urea bond, and a urethane bond is preferable; at least one structure selected from the group consisting of a hydroxy group, a carboxy group, a primary amide group, a secondary amide group, a primary sulfonamide group, a secondary sulfonamide group, a maleimide group, a urea bond, and a urethane bond is more preferable; at least one structure selected from the group consisting of a hydroxy group, a carboxy group, a primary amide group, a secondary amide group, a primary sulfonamide group, a secondary sulfonamide group, and a maleimide group is still more preferable; and at least one structure selected from the group consisting of a hydroxy group and a secondary amide group is particularly preferable.

The above-described hydrogen-bond-accepting moiety may be a structure containing an atom with an unshared electron pair, and a structure containing an oxygen atom with an unshared electron pair is preferable; at least one structure selected from the group consisting of a carbonyl group (including a carbonyl structure such as a carboxy group, an amide group, an imide group, a urea bond, and a urethane bond) and a sulfonyl group (including a sulfonyl structure such as a sulfonamide group) is more preferable; and a carbonyl group (including a carbonyl structure such as a carboxy group, an amide group, an imide group, a urea bond, and a urethane bond) is particularly preferable.

As the hydrogen-bondable group, a group having both the hydrogen-bond-donating moiety and the hydrogen-bond-accepting moiety described above is preferable; it is preferable to have a carboxy group, an amide group, an imide group, a urea bond, a urethane bond, or a sulfonamide group; and it is more preferable to have a carboxy group, an amide group, an imide group, or a sulfonamide group.

It is sufficient that the dipole-interactable group with the conductive material or the like is a group having a polarized structure other than the above-described structure represented by X—H (X represents a heteroatom, for example, a nitrogen atom or an oxygen atom) in the hydrogen-bondable group, and suitable examples thereof include a group in which atoms with different electronegativities are bonded to each other.

As a combination of the atoms with different electronegativities, 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 is preferable; and a combination of at least one atom selected from the group consisting of an oxygen atom, a nitrogen atom, and a sulfur atom, and a carbon atom is more preferable.

Among these, from the viewpoint of adhesiveness with the pattern, a combination of a nitrogen atom and a carbon atom or a combination of a carbon atom, a nitrogen atom, an oxygen atom, and a sulfur atom is preferable, and specifically, a cyano group, a cyanuric group, or a sulfonic acid amide group is more preferable.

Preferred examples of the compound having a curing reactive group with the conductive material or the like include the following curable compound.

The curable compound is a compound which is cured by irradiation with heat or light (for example, visible light, ultraviolet rays, near-infrared rays, far-infrared rays, electron beam, or the like). Examples of such a curable compound include an epoxy compound, a cyanate ester compound, a vinyl compound, a silicone compound, an oxazine compound, a maleimide compound, an allyl compound, an acrylic compound, a methacrylic compound, and a urethane compound. These may be used alone or in combination of two or more thereof. Among these, from the viewpoint of characteristics such as compatibility with the resin and heat resistance, at least one selected from the group consisting of an epoxy compound, a cyanate ester compound, a vinyl compound, a silicone compound, an oxazine compound, a maleimide compound, and an allyl compound is preferable; and at least one selected from the group consisting of an epoxy compound, a cyanate ester compound, a vinyl compound, an allyl compound, and a silicone compound is more preferable.

From the viewpoint of crack suppressibility and adhesiveness with the pattern, a content of the compound having a functional group with respect to the total mass of the base material for a metamaterial is preferably 0.01% by mass to 10% by mass, more preferably 0.03% by mass to 5% by mass, and still more preferably 0.05% by mass to 3% by mass.

In a case where the base material for a metamaterial has a multilayer structure, from the viewpoint of crack suppressibility and adhesiveness with the pattern, the content of the compound having a functional group with respect to the total mass of the layer containing the compound having a functional group is preferably 0.5% by mass to 15% by mass, more preferably 0.7% by mass to 10% by mass, and still more preferably 1% by mass to 5% by mass.

(Filler)

The base material for a metamaterial may contain at least one filler. The filler may be an organic filler or an inorganic filler.

Examples of the organic filler include particles of a liquid crystal polymer, polyolefin, a fluorine-based polymer, and the like.

Examples of the inorganic filler 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 thermal expansion coefficient, it is preferable that the base material for a metamaterial contains silica particles.

In a case where the base material for a metamaterial has a multilayer structure, from the viewpoint of improving smoothness of the pattern formed on the surface of the base material for a metamaterial, it is preferable that the filler is contained in a layer other than the layer having the surface on which the pattern is formed. For example, in a case where the base material for a metamaterial has a three-layer structure of a first layer, a second layer, and a third layer and the pattern is formed on the first layer, it is preferable that the second layer or the third layer contains the filler.

From the viewpoint of thermal expansion coefficient and adhesiveness with the pattern, an average particle diameter of the filler is preferably 5 nm to 20 μm, more preferably 10 nm to 10 μm, still more preferably 20 nm to 1 μm, and particularly preferably 25 nm to 500 nm.

In the present disclosure, the average particle diameter of the filler is obtained by arithmetically averaging particle diameters of 50 particles randomly selected from an image of a scanning electron microscope (SEM).

From the viewpoint of thermal expansion coefficient of the base material for a metamaterial and adhesiveness with the pattern, a content of the filler with respect to the total mass of the base material for a metamaterial is preferably 10% by mass to 40% by mass, more preferably 15% by mass to 35% by mass, and still more preferably 20% by mass to 30% by mass.

In a case where the base material for a metamaterial has a multilayer structure, from the viewpoint of reducing the thermal expansion coefficient, the content of the filler with respect to the total mass of the layer containing the filler is preferably 20% by mass to 70% by mass, more preferably 30% by mass to 65% by mass, and still more preferably 40% by mass to 60% by mass.

(Additive)

The base material for a metamaterial may contain various additives, and examples thereof include a polymerization initiator, a dispersant, a surfactant, a crosslinking agent, and an antioxidant.

In addition, as the base material for a metamaterial, a woven fabric such as a glass cloth, a nonwoven fabric, or the like may be used by being impregnated with the above-described resin. Furthermore, a layer may be formed on at least one surface of the glass cloth or the like, impregnated with the above-described resin, using the above-described material such as the resin to be a base material for a metamaterial, having a multilayer structure.

A thickness of the base material for a metamaterial is not particularly limited, and from the viewpoint of handleability, it is preferably 5 μm to 200 μm, more preferably 10 μm to 180 μm, and still more preferably 15 μm to 150 μm.

[Metamaterial]

The metamaterial according to the present disclosure includes a base material for a metamaterial and a pattern provided on a surface of the base material for a metamaterial, in which the pattern is composed of at least one of a conductive material or a material which transits from an insulator to a conductor. The base material for a metamaterial is described above, and thus the description thereof will be omitted here.

From the viewpoint of cost reduction, in the metamaterial according to the present disclosure, a ratio of a product of a thickness of the pattern and a storage elastic modulus of the pattern at 25° C. to a product of a thickness of the base material for a metamaterial and a storage elastic modulus of the base material for a metamaterial at 25° C. (Product of thickness of pattern and storage elastic modulus of pattern at 25° C./Product of thickness of base material for metamaterial and storage elastic modulus of base material for metamaterial at 25° C.) is preferably less than 10, more preferably 0.01 to 1.0, and still more preferably 0.03 to 0.5.

(Pattern)

The pattern is composed of at least one of a conductive material or a material which transits from an insulator to a conductor.

The conductive material preferably contains a metal, and more preferably is one or more selected from the group consisting of gold, silver, platinum, copper, and aluminum. Among these, from the viewpoint of smoothness of the pattern, crack suppressibility, and the like, at least one of gold or copper is particularly preferable.

A 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.

As the material which transits from an insulator to a conductor, a material which transits from an insulator to a conductor by heating, light irradiation, or applying a voltage can be used.

The material which transits from an insulator to a conductor is preferably one or more selected from the group consisting of a phase change material, a semiconductor, a conductive oxide, and a carbon material.

In the present disclosure, the phase change material means a material which causes a phase change between an amorphous phase and a crystalline phase by Joule heat due to an electric pulse.

Examples of the phase change material include vanadium oxide, an antimony tellurium (SbTe) alloy, a germanium tellurium (GeTe) alloy, a germanium antimony tellurium (GeSbTe) alloy, an indium antimony tellurium (InSbTe) alloy, and a silver indium antimony tellurium (AgInSbTe) alloy. Among these, from the viewpoint of easily controlling a temperature and a voltage at which the insulator is transited to the conductor, smoothness of the pattern, crack suppressibility, and the like, vanadium oxide or a GeSbTe alloy is preferable.

Examples of the semiconductor include a p-type x-conjugated polymer, a condensed polycyclic compound, a triarylamine compound, a hetero 5-membered ring compound, a phthalocyanine compound, and a porphyrin compound.

Examples of the conductive oxide include indium tin oxide (ITO), indium zinc oxide (IZO), zinc oxide (ZnO), and indium gallium zinc oxide (IGZO).

Examples of the carbon material include carbon nanotube and graphene.

The pattern may include a plurality of structural bodies. The pattern may include two or more structural bodies having different shapes, sizes, and the like.

A shape of the structural body is not particularly limited, but is preferably a shape capable of inducing a dielectric or magnetic response change by generating a charge bias, a current, or the like in the structural body or between adjacent structural bodies due to an interaction between the electric field, the magnetic field, or the like of an electromagnetic wave in a terahertz band, which is incident on the metamaterial.

The shape of the structural body is not particularly limited, and examples thereof include a C-shape, a U-shape, a double ring shape, a V-shape, an L-shape, a lattice shape, a spiral shape, a square shape, a circular shape, and a cross shape in an in-plane direction of the base material for a metamaterial. The structural body is composed of the conductive material or the material which transits from an insulator to a conductor.

The structural body is preferably a split-ring resonator. The split-ring resonator means a structural body having a C-shape or a U-shape, and has a gap indicated by a reference numeral G in FIG. 1.

A size of the structural body is not particularly limited, but is preferably equal to or less than a wavelength size of the incident electromagnetic wave in the terahertz band.

In the present disclosure, the maximum length of the structural body means a length which is longest in a case where a straight line is drawn from one end to the other end of the structural body in the in-plane direction of the base material for a metamaterial.

From the viewpoint of smoothness of the pattern, a width of the structural body is preferably 3 μm to 25 μm.

In addition, in a case where the structural body is a split-ring resonator, from the viewpoint of smoothness of the pattern, the gap is preferably 1 μm to 15 μm.

A distance between the structural bodies is preferably appropriately changed according to the shape, size, and the like of the structural body, and for example, it can be set to 30 μm to 400 μm.

A disposition position of the structural body on the surface of the base material for a metamaterial is not particularly limited, and is preferably a disposition in which the structural body resonates with the electromagnetic wave in the terahertz band.

In addition, the structural body may be disposed on the surface of the base material for a metamaterial, in which a periodic structure is formed such that the amount of phase shift of the electromagnetic wave in the terahertz band is continuously increased or decreased as the region goes from the center of the surface of the base material for a metamaterial to the outer side. Examples of the above-described periodic structure include a structure in which structural bodies having different diameters are arranged in a concentric circle. A change width of the diameter of the structural bodies arranged in a concentric circle can be set to 10 μm to 200 μm.

In a case where the base material for a metamaterial contains the compound having a functional group, the pattern preferably has a functional group such as an amino group and a hydroxy group.

In a case where the compound having a functional group has a covalent-bondable group, the pattern preferably has a functional group such as an amino group, a hydroxy group, an epoxy group, an oxetanyl group, an N-hydroxy ester group, and an imide ester group.

In a case where the compound having a functional group has an ion-bondable group, 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, and a piperidyl group.

In a case where the compound having a functional group has a hydrogen-bondable group, the pattern preferably has a group having a hydrogen-bond-donating moiety or a group having a hydrogen-bond-accepting moiety.

In a case where the compound having a functional group has a dipole-interactable group, the pattern preferably has a dipole-interactable group.

The above-described functional group may be introduced into the surface of the base material for a metamaterial on the side in contact with the base material for a metamaterial, by performing a chemical treatment or the like.

From the viewpoint of cost reduction, a thickness of the pattern is preferably less than 5 μm, more preferably 0.05 μm to 4 μm, still more preferably 0.1 μm to 3 μm, and particularly preferably 0.3 μm to 1 μm.

An embodiment of the metamaterial will be described with reference to FIG. 1. However, the metamaterial is not limited thereto.

As shown in FIG. 1, a metamaterial 10 includes a base material 11 for a metamaterial, and a pattern 12 provided on a surface of the base material 11 for a metamaterial.

In FIG. 1, the pattern 12 includes a plurality of structural bodies 12a. In FIG. 1, the maximum length of the structural body 12a is indicated by a reference numeral L, the width of the structural body 12a is indicated by a reference numeral W, the gap of the structural body 12a is indicated by a reference numeral G, and the distance between the structural bodies is indicated by a reference numeral X.

The applications of the metamaterial according to the present disclosure are not particularly limited, and examples thereof include a flat lens, a diffraction grating, a wavelength filter, a polarizer, a sensor, a reflector, and a flat prism.

In addition, the use environment thereof is not particularly limited, and the metamaterial may be mounted on an electronic apparatus or the like or may be installed outdoors as a wavelength filter.

[Laminate]

The laminate according to the present disclosure includes the above-described metamaterial and an organic film provided on a surface of the metamaterial on the pattern side. The organic film may have a monolayer structure or a multilayer structure.

From the viewpoint of suppressing occurrence of corrosion in the pattern, a moisture permeability of the organic film in an environment of a temperature of 40° C. and a relative humidity of 90% is preferably 3,000 g/(m²·24 hours) or less, more preferably 2,000 g/(m²·24 hours) or less, still more preferably 1,500 g/(m²·24 hours) or less, and particularly preferably 1,000 g/(m²·24 hours) or less.

The organic film can contain a resin. The resin is as described above, and the description thereof will be omitted here.

A content of the resin with respect 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 still more preferably 30% by mass to 70% by mass.

The organic film may contain an ultraviolet absorber. As a result, it is possible to improve weather fastness of the laminate and to improve suitability of the laminate for applications of being installed outdoors.

Examples of the ultraviolet absorber include a conjugated diene compound, an aminodiene compound, a salicylate compound, a benzophenone compound, a benzotriazole compound, an acrylonitrile compound, a hydroxyphenyltriazine compound, an indole compound, and a triazine compound.

In addition, in a case where the organic film has a multilayer structure, the organic film preferably includes a layer containing the ultraviolet absorber.

From the viewpoint of weather fastness and prevention of bleed out, a content of the ultraviolet absorber with respect to the total mass of the organic film is preferably 0.01% by mass to 30% by mass, more preferably 0.1% by mass to 10% by mass, and still more preferably 0.5% by mass to 5% by mass.

The organic film may contain the above-described additives.

A thickness of the organic film is not particularly limited, but from the viewpoint that transmission characteristics of the electromagnetic wave are not impaired, it is preferably 20 μm or less, more preferably 10 μm or less, and still more preferably 5 μm or less. The lower limit thereof is not particularly limited, but is 0.5 μm or more in many cases.

A method for manufacturing the laminate is not particularly limited, and the laminate may be formed by adding the above-described resin and the like to a solvent as necessary to form a composition, and applying the composition onto the surface of the metamaterial and drying the composition. In addition, the laminate may be manufactured by applying the composition onto a temporary support and drying the composition to form an organic film, producing a transfer sheet, and transferring the organic film from the transfer sheet to a surface of the metamaterial.

[Manufacturing Method of Metamaterial]

The manufacturing method of a metamaterial according to the present disclosure includes a step of disposing at least one of a conductive material or a material which transits from an insulator to a conductor on a surface of the above-described base material for a metamaterial; and a step of patterning the conductive material or the material which transits from an insulator to a conductor, which is disposed on the surface of the base material for a metamaterial, to form a pattern.

The disposition of at least one of the conductive material or the material which transits from an insulator to a conductor on the surface of the base material for a metamaterial can be carried out by a method such as a sputtering method and a vapor deposition method.

The method of patterning the conductive material or the material which transits from an insulator to a conductor is not particularly limited, and examples thereof include a method of forming a resist pattern on a surface of a sputtered film or a deposited film, etching and removing the sputtered film not covered with the resist pattern, and then removing the resist pattern.

The base material for a metamaterial used in the manufacturing method of a metamaterial according to the present disclosure is not particularly limited as long as it satisfies the above-described condition of the thermal dimensional change rate, and a commercially available base material may be used or a base material manufactured by a known method in the related art may be used.

In a case of manufacturing the base material for a metamaterial, it is preferable that a manufacturing method thereof includes a step of subjecting a base material to a stretching treatment, and as a result, a thermal dimensional change rate of the base material for a metamaterial can be controlled. The commercially available film may be subjected to a stretching treatment and used as the base material for a metamaterial. An example of the manufacturing method of the base material for a metamaterial is shown in Examples.

The stretching treatment is preferably performed in a temperature environment equal to or lower than a glass transition temperature of the base material; more preferably performed in a temperature environment lower than the glass transition temperature of the base material by 5° C. or higher; and still more preferably performed in a temperature environment lower than the glass transition temperature of the base material by 10° C. or higher.

In the present disclosure, the glass transition temperature of the base material before the stretching treatment is measured by the following method.

The base material piece is enclosed in a measuring pan, and using a differential scanning calorimeter, the glass transition temperature is obtained from a thermogram obtained by raising the temperature at a rate of 20° C./min, in which the baseline and the intersection temperature of the tangent line at the inflection point are obtained.

As the differential scanning calorimeter, DSC6200 manufactured by Seiko Instruments Inc. or similar apparatus can be used.

EXAMPLES

Hereinafter, the above-described embodiment will be specifically described with reference to Examples, but the above-described embodiment is not limited to Examples. Unless otherwise specified, the unit of numerical values in Table 1 is part by mass. In addition, the content in Table 1 indicates a content as the solid content.

Synthesis Example 1: Synthesis of Liquid Crystal Polyester LC-A

A reactor including a stirrer, a torque meter, a nitrogen gas introduction pipe, a thermometer, and a reflux condenser was prepared.

940.9 g (5.0 mol) of 6-hydroxy-2-naphthoic acid, 377.9 g (2.5 mol) of 4-hydroxyacetaminophen, 415.3 g (2.5 mol) of isophthalic acid, and 867.8 g (8.4 mol) of acetic acid anhydride were charged into the above-described reactor, the gas in the reactor was replaced with nitrogen gas, and the mixture was heated from room temperature (23° C.) to 143° C. over 60 minutes while being stirred under a nitrogen gas stream and was refluxed at 143° C. for 1 hour.

Thereafter, the mixture was heated from 150° C. to 300° C. over 5 hours while distilling off by-product acetic acid and unreacted acetic acid anhydride and maintained at 300° C. for 30 minutes, and the resultant was taken out from the reactor and cooled to room temperature. The obtained solid matter was crushed with a crusher, thereby obtaining powdery liquid crystal polyester A1.

The liquid crystal polyester A1 obtained above was heated from room temperature to 160° C. over 2 hours and 20 minutes in a nitrogen atmosphere, further heated from 160° C. to 180° C. over 3 hours and 20 minutes, maintained at 180° C. for 5 hours to carry out solid phase polymerization, cooled, and crushed with a crusher, thereby obtaining powdery liquid crystal polyester A2.

The liquid crystal polyester A2 was heated from room temperature (23° C.) to 180° C. over 1 hour and 20 minutes in a nitrogen atmosphere, further heated from 180° C. to 240° C. over 5 hours, maintained at 240° C. for 5 hours to carry out solid phase polymerization, and cooled, thereby obtaining powdery liquid crystal polyester LC-A.

Preparation Example 1: Preparation of Filler F-1

1034.99 g (5.5 mol) of 2-hydroxy-6-naphthoic acid, 378.33 g (1.75 mol) of 2,6-naphthalenedicarboxylic acid, 83.07 g (0.5 mol) of terephthalic acid, 272.52 g (2.475 mol) of hydroquinone (0.225 mol excess with respect to the total molar amount of the 2,6-naphthalenedicarboxylic acid and the terephthalic acid), 1226.87 g (12 mol) of acetic acid anhydride, and 0.17 g of 1-methylimidazole as a catalyst were charged into the above-described reactor. After the gas in the reactor was replaced with nitrogen gas, the mixture was heated from room temperature to 145° C. over 15 minutes while being stirred in a nitrogen gas stream and was refluxed at 145° C. for 1 hour.

Next, the mixture was heated from 145° C. to 310° C. over 3 hours 30 minutes while distilling off by-product acetic acid and unreacted acetic acid anhydride and maintained at 310° C. for 3 hours, and solid liquid crystal polyester LC-B was taken out and cooled to room temperature. The flow start temperature of the liquid crystal polyester LC-B was 265° C.

Using a jet mill (manufactured by KURIMOTO Ltd., KJ-200), the liquid crystal polyester LC-B was crushed to obtain a filler F-1. An average particle diameter of the filler F-1 was 9 μm.

Example 1

The liquid crystal polyester shown in Table 1 was added to N-methylpyrrolidone, and the mixture was stirred at 140° C. for 4 hours in a nitrogen atmosphere to form a solution, and allowed to pass through a sintered fiber metal filter having a nominal pore diameter of 10 μm and then allowed to pass through a sintered fiber metal filter having the same nominal pore diameter of 10 μm to obtain a composition A.

A filler shown in Table 1 was added to the composition A, and the mixture was stirred at 25° C. for 30 minutes to obtain a composition B.

The contents of the liquid crystal polyester and the filler in the composition A and the composition B are shown in Table 1. The concentration of solid contents of the liquid crystal polyester in the composition A and the composition B was set to 10% by mass.

Next, the composition A and the composition B were allowed to pass through a sintered fiber metal filter having a nominal pore diameter of 10 μm and then allowed to pass through a sintered fiber metal filter having the same nominal pore diameter of 10 μm.

The composition A and the composition B were fed to a casting die equipped with a multi-manifold for co-casting, and cast on an aluminum foil having a thickness of 50 μm as a support to produce an original film for stretching, having a three-layer structure of a layer formed of the composition B (referred to as a first layer in Table 1), a layer formed the composition A (referred to as a second layer in Table 1), and a layer formed of the composition B (referred to as a third layer in Table 1). The aluminum foil was in contact with the third layer.

The above-described base material was dried at 40° C. for 4 hours to remove the solvent from the base material, and the base material was further heated from room temperature (25° C.) to 290° C. at 1° C./min under a nitrogen atmosphere to perform a heat treatment of maintaining the temperature for 2 hours, and the base material was cooled to room temperature, and then the aluminum foil was peeled off and further heated at 200° C. for 1 minute.

In a case where the original film piece was enclosed in a measuring pan, and using a differential scanning calorimeter (DSC6200) manufactured by Seiko Instruments Inc., a glass transition temperature was obtained from a thermogram obtained by raising the temperature at a rate of 20° C./min, in which the baseline and the intersection temperature of the tangent line at the inflection point were obtained, it was 184° C.

The above-described original film was stretched in a temperature environment lower than the glass transition temperature by 10° C. to obtain a base material for a metamaterial. With regard to a thermal dimension change rate of the base material, it was adjusted at a stretching ratio using a calibration curve between the stretching ratio and the thermal dimensional change rate, which had been created in adjusted, and in a case where the film thickness changed by 1% or more due to the stretching, the thickness of the original film was adjusted and corrected.

In the base material for a metamaterial, the thickness of the first layer after the stretching was 15 μm, the thickness of the second layer after the stretching was 35 μm, and the thickness of the third layer after the stretching was 10 μm.

In a case where a thermal dimensional change rate of the base material for a metamaterial produced as described above was measured by the following method, it was-0.1% (contraction).

The base material for a metamaterial was cut into a size of 30 mm×120 mm to produce a test piece.

Markings were put on the test piece at intervals of 10 cm, and the test piece was allowed to stand in an environment of 25° C. and a relative humidity of 60% for 24 hours to be humidity-adjusted, and then the intervals of the markings were measured (the measured value is denoted as L0).

Next, the test piece was allowed to stand in a hot air dryer at 90° C. for 24 hours, and then allowed to stand in an environment of 25° C. and a relative humidity of 60% for 24 hours to be humidity-adjusted, and the intervals of the markings were measured (the measured value is denoted as L1).

L0 and L1 were substituted into the following expression to calculate the thermal dimensional change rate.

Thermal dimensional change rate [%]=((L1-L0)/L0)×100 In a case where a dielectric loss tangent of the base material for a metamaterial produced as described above was measured by the following terahertz time-domain spectroscopy (THz-TDS), it was 0.003.

First, the base material for a metamaterial was cut into a test piece having a size of 100 mm×100 mm.

Next, an optical system for transmission-type terahertz spectroscopy was produced, and a dielectric loss tangent of the test piece was measured from a change in time waveform of the electric field (frequency: 1 THz) before and after insertion of the test piece in an environment of a temperature of 25° C. and a humidity of 10% RH.

In a case where a thermal expansion coefficient of the base material for a metamaterial produced as described above was measured by the following method, it was 42 ppm/K.

First, the base material for a metamaterial was cut into a test piece having a size of 5 mm×20 mm.

Next, using a thermomechanical analyzer (TMA), a tensile load of 1 g was applied to both ends of the test piece, the temperature was raised from 25° C. to 150° C. at a rate of 5° C./min, and the thermal expansion coefficient was calculated from a slope of a TMA curve between 125° C. and 50° C. in a case where the temperature was lowered to 25° C.

The base material for a metamaterial was cut into a test piece having a size of 10 mm×150 mm.

In a case where a storage elastic modulus of the above-described test piece was measured under conditions of a distance between chucks of 100 mm, a temperature of 25° C., and a relative humidity of 50%, in conformity with the method described in JIS K 7127 (1999), it was 4.0 GPa.

A sputtered copper film having a thickness of 0.5 μm was formed on the surface of the first layer of the above-described base material for a metamaterial.

A resist pattern was formed on the surface of the sputtered film, the sputtered film not covered with the resist pattern was etched and removed, and then the resist pattern was removed to form a pattern including a plurality of C-shaped split-ring resonators, thereby obtaining a metamaterial.

The split-ring resonator had a width of 15 μm, a maximum length of 92 μm, a C-shape in a shape viewed from a normal direction of the base material, a gap of 10 μm, and a distance between the split-ring resonators of 200 μm.

The above-described pattern was cut out into a size of 5 mm×5 mm to produce a test piece.

In a case where a storage elastic modulus of the above-described test piece was measured using a scanning probe microscope (SPA400, manufactured by SII NanoTechnology Inc.) in a VE-AFM mode under conditions of a temperature of 25° C. and a relative humidity of 50%, it was 30 GPa.

A composition containing 98.0 parts by mass of a cycloolefin polymer P-1 (manufactured by JSR Corporation, ARTON (registered trademark) F3500), 2 parts by mass of an ultraviolet absorber having the following structure, and 400 parts by mass of dichloromethane was applied onto the surface of the metamaterial produced as described above on the pattern side, dried, and formed into an organic film having a thickness of 10 μm, thereby obtaining a laminate.

In a case where a moisture permeability was measured under conditions of a temperature of 40° C., a relative humidity of 90%, and 24 hours of standing, in conformity with the method of JIS Z 0208 (1976), it was 360 g/(m². 24 hours).

[Image Omitted]

Example 2

The liquid crystal polyester shown in Table 1 was added to N-methylpyrrolidone, and the mixture was stirred at 140° C. for 4 hours in a nitrogen atmosphere to form a solution, and allowed to pass through a sintered fiber metal filter having a nominal pore diameter of 10 μm and allowed to pass through a sintered fiber metal filter having the same nominal pore diameter of 10 μm.

A compound M-1 having a functional group (aminophenol-type epoxy resin, jER630LSD, manufactured by Mitsubishi Chemical Corporation, having an epoxy group which was a hydrogen-bondable group with the conductive material (copper) constituting the pattern) was added to the liquid crystal polyester after passing through the filter, and the mixture was stirred at 25° C. for 30 minutes to obtain a composition C.

The contents of the liquid crystal polyester and the compound M-1 having a functional group in the composition C are shown in Table 1. The concentration of solid contents of the liquid crystal polyester in the composition C was set to 10% by mass.

The composition A, composition B, and composition C prepared in Example 1 were fed to a casting die equipped with a multi-manifold for co-casting, and cast on an aluminum foil having a thickness of 50 μm as a support to produce a base material having a three-layer structure of a layer formed of the composition C and having a thickness of 15 μm (referred to as a first layer in Table 1), a layer formed the composition A and having a thickness of 35 μm (referred to as a second layer in Table 1), and a layer formed of the composition B and having a thickness of 10 μm (referred to as a third layer in Table 1). The aluminum foil was in contact with the third layer.

A glass transition temperature of the base material was measured by the same method as in Example 1, and the base material was stretched in a temperature environment lower than the glass transition temperature by 10° C. to obtain a base material for a metamaterial.

In the base material for a metamaterial, the thickness of the first layer was 15 μm, the thickness of the second layer was 35 μm, and the thickness of the third layer was 10 μm.

A metamaterial and a laminate were produced in the same manner as in Example 1, except that the base material for a metamaterial was changed to the above-described base material for a metamaterial.

In a case where a thermal dimensional change rate of the base material was measured by the same method as in Example 1, it was-0.1% (contraction).

In a case where a dielectric loss tangent of the base materials was measured by the same method as in Example 1, it was 0.003.

In a case where a thermal expansion coefficient of the base material was measured by the same method as in Example 1, it was 42 ppm/K.

Example 3

A base material for a metamaterial, a metamaterial, and a laminate were produced in the same manner as in Example 1, except that the stretching conditions of the base material were changed such that the thermal dimensional change rate of the base material was-0.3%.

In the base material for a metamaterial, the thickness of the first layer was 15 μm, the thickness of the second layer was 35 μm, and the thickness of the third layer was 10 μm.

In a case where a thermal dimensional change rate of the base material was measured by the same method as in Example 1, it was-0.3% (contraction).

In a case where a dielectric loss tangent of the base materials was measured by the same method as in Example 1, it was 0.003.

In a case where a thermal expansion coefficient of the base material was measured by the same method as in Example 1, it was 42 ppm/K.

Example 4

In the base material for a metamaterial, the thickness of the first layer was 15 μm, the thickness of the second layer was 35 μm, and the thickness of the third layer was 10 μm.

In a case where a thermal dimensional change rate of the base material was measured by the same method as in Example 1, it was-0.5% (contraction).

In a case where a dielectric loss tangent of the base materials was measured by the same method as in Example 1, it was 0.003.

In a case where a thermal expansion coefficient of the base material was measured by the same method as in Example 1, it was 42 ppm/K.

Example 5

A metamaterial and a laminate were produced in the same manner as in Example 1, except that the filler F-1 was changed to a filler F-2. The details of the filler F-2 are as follows.

In a case where a thermal dimensional change rate of the base material was measured by the same method as in Example 1, it was-0.3% (contraction).

In a case where a dielectric loss tangent of the base materials was measured by the same method as in Example 1, it was 0.002.

In a case where a thermal expansion coefficient of the base material was measured by the same method as in Example 1, it was 42 ppm/K.

Filler F-2: copolymer particles of ethylene tetrafluoride and perfluoroalkoxy ethylene (PFA) (melting point: 280° C., average particle diameter: 0.2 μm to 0.5 μm, dielectric loss tangent: 0.001)

Example 6

As a base material, a cycloolefin polymer film having a thickness of 100 μm (manufactured by ZEON CORPORATION, ZEONOR (registered trademark) ZF-14; glass transition temperature: 136° C., elastic modulus: 2.1 GPa; described as PF-1 in Table 1) was prepared.

The base material was stretched in a temperature environment lower than the glass transition temperature by 10° C. to obtain a base material for a metamaterial, having a thickness of 100 μm.

A metamaterial and a laminate were produced in the same manner as in Example 1, except that the base material for a metamaterial was changed to the above-described base material for a metamaterial.

In a case where a thermal dimensional change rate of the base material was measured by the same method as in Example 1, it was-0.8% (contraction).

In a case where a dielectric loss tangent of the base materials was measured by the same method as in Example 1, it was less than 0.001.

In a case where a thermal expansion coefficient of the base material was measured by the same method as in Example 1, it was 82 ppm/K.

Example 7

As a base material, a liquid crystal polymer film having a thickness of 50 μm (manufactured by Kuraray Co., Ltd., VECTRA (registered trademark) CTQ; glass transition temperature: 214° C., elastic modulus: 3.6 GPa; referred to as PF-2 in Table 1) was prepared.

The base material was stretched in a temperature environment lower than the glass transition temperature by 10° C. to obtain a base material for a metamaterial, having a thickness of 50 μm.

A metamaterial and a laminate were produced in the same manner as in Example 1, except that the base material for a metamaterial was changed to the above-described base material for a metamaterial.

In a case where a thermal dimensional change rate of the base material was measured by the same method as in Example 1, it was-0.3% (contraction).

In a case where a dielectric loss tangent of the base materials was measured by the same method as in Example 1, it was 0.002.

In a case where a thermal expansion coefficient of the base material was measured by the same method as in Example 1, it was 19 ppm/K.

Example 8

A base material for a metamaterial having a thickness of 90 μm, a metamaterial, and a laminate were produced in the same manner as in Example 6, except that the stretching conditions of the base material were changed such that the thermal dimensional change rate of the base material was-10%.

In a case where a thermal dimensional change rate of the base material was measured by the same method as in Example 1, it was-10% (contraction).

In a case where a dielectric loss tangent of the base materials was measured by the same method as in Example 1, it was less than 0.001.

In a case where a thermal expansion coefficient of the base material was measured by the same method as in Example 1, it was 82 ppm/K.

Comparative Example 1

A base material for a metamaterial, a metamaterial, and a laminate were produced in the same manner as in Example 6, except that the stretching treatment was not performed on the base material.

In a case where a thermal dimensional change rate of the base material was measured by the same method as in Example 1, it was 0%.

In a case where a dielectric loss tangent of the base materials was measured by the same method as in Example 1, it was less than 0.001.

In a case where a thermal expansion coefficient of the base material was measured by the same method as in Example 1, it was 82 ppm/K.

<<Evaluation of Crack Suppressibility>>

The metamaterial before being formed into a laminate with the organic film, which was produced in Examples and Comparative Examples, was cut out into a size including 100 split-ring resonators and used as a test piece.

The test piece was put into a heat shock tester (manufactured by ESPEC Corp., thermal shock tester TSA series).

The test piece was allowed to stand at −65° C. for 30 minutes, allowed to stand at 125° C. for 30 minutes, and then allowed to stand until the temperature was changed to −65° C. This procedure was considered as one cycle and was repeated for 150 cycles, and then the environment was returned to a temperature of 25° C. and a relative humidity of 55%.

The test piece was observed with an optical microscope and evaluated based on the following evaluation standard. The results are shown in Table 2.

(Evaluation Standard)

A: in the split-ring resonators, the occurrence of cracks was not observed.

B: in 1 or more and 5 or less of the split-ring resonators, the occurrence of cracks was observed, but there was no problem in practical use.

C: occurrence of cracks was observed in 6 or more of the split-ring resonators.

<<Evaluation of Wrinkle Suppressibility>>

The test piece was put into a heat shock tester (manufactured by ESPEC Corp., thermal shock tester TSA series).

The test piece was observed with an optical microscope and evaluated based on the following evaluation standard. The results are shown in Table 2.

(Evaluation Standard)

A: in the split-ring resonators, the occurrence of wrinkles was not observed.

B: in 1 or more and 5 or less of the split-ring resonators, the occurrence of wrinkles was observed, but there was no problem in practical use.

C: occurrence of wrinkles was observed in 6 or more of the split-ring resonators.

TABLE 1

Thermal

First layer

dimen-

Compound

Second layer
Third layer

sional

Liquid

having

Liquid

Liquid

change

crystal
Cycloolefin
functional

crystal

crystal

rate

polyester
polymer
group

polyester
Filler

polyester

Presence
of base

Con-

Con-

Con-

Con-

Con-

Con-

or
material

tent

tent

tent

tent

tent

tent

absence
for

(part

(part

(part
Thick-

(part

(part
Thick-

(part
Thick-
of
meta-

by

by

by
ness

by

by
ness

by
ness
stretching
material

Type
mass)
Type
mass )
Type
mass)
(μm)
Type
mass)
Type
mass)
(μm)
Type
mass)
(μm)
treatment
(%)

Exam-
LC-A
100
—
—
—
—
15
LC-A
50
F-1
50
35
LC-A
100
10
Presence
−0.1

ple 1

Exam-
LC-A
99
—
—
M-1
1
15
LC-A
50
F-1
50
35
LC-A
100
10
Presence
−0.1

ple 2

Exam-
LC-A
100
—
—
—
—
15
LC-A
50
F-1
50
35
LC-A
100
10
Presence
−0.3

ple 3

Exam-
LC-A
100
—
—
—
—
15
LC-A
50
F-1
50
35
LC-A
100
10
Presence
−0.5

ple 4

Exam-
LC-A
100
—
—
—
—
15
LC-A
50
F-2
50
35
LC-A
100
10
Presence
−0.3

ple 5

Exam-
—
—
PF-1
100
—
—
100
—
—
—
—
—
—
—
—
Presence
−0.8

ple 6

Exam-
—
—
PF-2
100
—
—
50
—
—
—
—
—
—
—
—
Presence
−0.3

ple 7

Exam-
—
—
PF-1
100
—
—
90
—
—
—
—
—
—
—
—
Presence
−10

ple 8

Com-
—
—
PF-1
100
—
—
100
—
—
—
—
—
—
—
—
Absence
0

parative

Exam-

ple 1

TABLE 2

Ratio of product of thickness of

pattern and storage elastic

Base material for metamaterial
modulus of pattern to product of

Thermal

Thermal
thickness of base material for

dimensional
Dielectric
expansion
metamaterial and storage elastic
Evaluation of
Evaluation of

change rate
loss
coefficient
modulus of base material for
crack
wrinkle

(%)
tangent
(ppm/K)
metamaterial
suppressibility
suppressibility

Example 1
−0.1
0.003
42
0.06
B
A

Example 2
−0.1
0.003
42
0.06
A
A

Example 3
−0.3
0.003
42
0.06
A
A

Example 4
−0.5
0.003
42
0.06
A
A

Example 5
−0.3
0.002
42
0.06
A
A

Example 6
−0.8
<0.001
82
0.07
A
A

Example 7
−0.3
0.002
19
0.08
A
A

Example 8
−10
<0.001
82
0.08
A
C

Comparative
0
<0.001
82
0.07
C
A

Example 1

From Table 2, it was found that the crack suppressibility and the wrinkle suppressibility in the base material for a metamaterial, the metamaterial, and the laminate obtained in Examples were excellent as compared with the base material for a metamaterial, the metamaterial, and the laminate obtained in Comparative Examples.

The disclosure of JP2022-030214 filed on Feb. 28, 2022 is incorporated in the present specification by reference. All documents, patent applications, and technical standards described in the present specification are incorporated herein by reference to the same extent as in a case of being specifically and individually noted that individual documents, patent applications, and technical standards are incorporated herein by reference.