WO2023112921A1

WO2023112921A1 - Flexible waveguide

Info

Publication number: WO2023112921A1
Application number: PCT/JP2022/045885
Authority: WO
Inventors: 智章伊藤; 琢夫浅見; 和人杉山
Original assignee: 三井化学株式会社
Priority date: 2021-12-15
Filing date: 2022-12-13
Publication date: 2023-06-22

Abstract

Provided is a flexible waveguide comprising a rod-shaped dielectric and a conductor that covers the outer surface of the dielectric, wherein the dielectric satisfies the following (a) and (b). (a) The density of the dielectric is no more than １．５０ｇ／ｃｍ３. (b) The relative dielectric constant of the dielectric is no more than 2.3 as measured under the condition of a frequency of 10GHz, and the dielectric loss is no more than 0.0013 as measured under the condition of a frequency of 10GHz.

Description

flexible waveguide

The present invention relates to flexible waveguides.

Coaxial cables and metal rectangular waveguides are widely known as means for transmitting microwave and millimeter wave electrical signals.
In conventional coaxial cables, when used in an extremely high frequency band such as the millimeter wave band, the central conductor becomes extremely thin, so transmission loss does not decrease, and flexibility is required. .
As a means for solving these problems, Patent Document 1 describes a waveguide in which a thin conductor such as a metal is stuck on the surface of a flexible dielectric rod without gaps, and has a bent portion. It is described that it is possible to easily cope with the above-mentioned problems and reduce material costs and processing costs.

JP-A-8-195605

The present invention provides a flexible waveguide with improved flexibility while suppressing deterioration in the transmission efficiency of electrical signals in high frequency bands such as microwaves.

According to the present invention, the following flexible waveguide is provided.

[1]
A flexible waveguide comprising a rod-shaped dielectric and a conductor covering the outer surface of the dielectric,
A flexible waveguide wherein the dielectric satisfies (a) and (b) below.
(a) a density of 1.50 g/cm ³ or less (b) a dielectric constant of 2.3 or less measured at a frequency of 10 GHz and a dielectric loss of 0.0013 or less measured at a frequency of 10 GHz [2]
The flexible waveguide according to [1] above, wherein the content of fluorine atoms in the dielectric is 1% by mass or less when the entire dielectric is 100% by mass.
[3]
The flexible waveguide according to [1] or [2] above, wherein the dielectric contains 4-methyl-1-pentene (co)polymer.
[4]
The flexible waveguide according to [3] above, wherein the 4-methyl-1-pentene (co)polymer satisfies (i) and (ii) below.
(i) 15 to 100 mol% of the structural unit (P) derived from 4-methyl-1-pentene;
(ii) 0 to 85 mol % of structural units (Q) derived from at least one selected from α-olefins having 2 to 20 carbon atoms (excluding 4-methyl-1-pentene);
[5]
The flexible waveguide according to [3] or [4] above, wherein the 4-methyl-1-pentene (co)polymer satisfies (iii) to (v) below.
(iii) 60 to 100 mol% of the structural unit (P) derived from 4-methyl-1-pentene
(iv) 0 to 40 mol% of structural units (Q) derived from at least one selected from α-olefins having 2 to 20 carbon atoms (excluding 4-methyl-1-pentene) (v) DSC have a melting point (Tm) in the range of 200-250° C. [6]
The 4-methyl-1-pentene (co)polymer is a 4-methyl-1-pentene/α-olefin copolymer,
The flexible waveguide according to [3] or [4] above, wherein the 4-methyl-1-pentene/α-olefin copolymer satisfies (vi) to (viii) below.
(vi) 15 to 99 mol% of the structural unit (P) derived from 4-methyl-1-pentene
(vii) The structural unit (Q) derived from at least one selected from α-olefins having 2 to 20 carbon atoms (excluding 4-methyl-1-pentene) is 1 to 85 mol% (viii) DSC melting point (Tm) below 200 °C or no melting point observed [7]
the dielectric is
The above 4-methyl-1-pentene (co)polymer, and thermoplastic resin (excluding 4-methyl-1-pentene (co)polymer) or elastomer,
The content of the thermoplastic resin or elastomer in the dielectric is 1 part by mass or more and 50 parts by mass or less (however, the total amount of the 4-methyl-1-pentene (co)polymer and the thermoplastic resin or elastomer is 100 The flexible waveguide according to any one of [3] to [6] above, which is a mass part.
[8]
The flexible waveguide according to any one of [1] to [7] above, wherein the dielectric contains a cyclic olefin copolymer having a structure represented by the following general formula (2).

[In general formula (2), x and y represent copolymerization ratios and are real numbers satisfying 0/100≦y/x≦95/5. x, y are on a molar basis. n indicates the substitution number of the substituent Q and is a real number of 0≦n≦2. R ^a is a 2+n-valent group selected from the group consisting of hydrocarbon groups having 2 to 20 carbon atoms. R ^b is a hydrogen atom or a monovalent group selected from the group consisting of hydrocarbon groups having 1 to 10 carbon atoms. R ^c is a tetravalent group selected from the group consisting of hydrocarbon groups having 2 to 10 carbon atoms. Q is COOR ^d (R ^d is a hydrogen atom or a monovalent group selected from the group consisting of hydrocarbon groups having 1 to 10 carbon atoms). Each of R ^a , R ^b , R ^c and Q may be one kind, or may be two or more kinds in an arbitrary ratio. ]
[9]
the dielectric is
(A) one or more olefin-derived repeating units represented by the following general formula (I);
(B) a repeating unit derived from a cyclic non-conjugated diene represented by the following general formula (III);
(C) a repeating unit derived from one or more cyclic olefins represented by the following general formula (V);
A cyclic olefin copolymer having a crosslinkable group containing
In the cyclic olefin copolymer, the content of the repeating unit (B) derived from a cyclic non-conjugated diene is 5 mol% or more when the total number of moles of repeating units in the cyclic olefin copolymer is 100 mol%. The flexible waveguide according to any one of [1] to [8] above, which is 36 mol % or less.

[In general formula (I), R ³⁰⁰ represents a hydrogen atom or a linear or branched hydrocarbon group having 1 to 29 carbon atoms. ]

[In general formula (III), u is 0 or 1, v is 0 or 1, w is 0 or 1, and R ⁶¹ to R ⁷⁶ and R ^a1 and R ^b1 may be the same or different; A hydrogen atom, a halogen atom, an alkyl group having 1 to 20 carbon atoms, a halogenated alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 15 carbon atoms, or a cycloalkyl group having 6 to 20 carbon atoms. an aromatic hydrocarbon group, R ¹⁰⁴ is a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, t is a positive integer of 0 to 10, R ⁷⁵ and R ⁷⁶ are It may form a ring or polycycle. ]

[In general formula (V), u is 0 or 1, v is 0 or 1, w is 0 or 1, and R ⁶¹ to R ⁷⁸ and R ^a1 and R ^b1 may be the same or different. A hydrogen atom, a halogen atom, an alkyl group having 1 to 20 carbon atoms, a halogenated alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 15 carbon atoms, or a cycloalkyl group having 6 to 20 carbon atoms. It is an aromatic hydrocarbon group, and R ⁷⁵ to R ⁷⁸ may combine with each other to form a monocyclic or polycyclic ring. However, when u and v are both 0, at least one of R ⁶⁷ to R ⁷⁰ and R ⁷⁵ to R ⁷⁸ is a substituent other than a hydrogen atom. ]
[10]
The flexible waveguide according to any one of [1] to [9] above, wherein the dielectric is a foam.
[11]
The flexible waveguide according to any one of [1] to [10] above, wherein the conductor is any one selected from metal coating, tape, fabric and metal plating.

According to the present invention, it is possible to provide a flexible waveguide that suppresses a decrease in transmission efficiency of electrical signals in a high frequency band such as microwaves and has improved flexibility.

It is a figure showing typically an example of structure of a flexible waveguide of an embodiment concerning the present invention. It is a figure showing typically an example of structure of a flexible waveguide of an embodiment concerning the present invention.

Hereinafter, embodiments of the present invention will be described with reference to the drawings. In addition, in all the drawings, the same constituent elements are denoted by the same reference numerals, and the explanation thereof is omitted as appropriate. Also, the drawings are schematic diagrams and do not correspond to actual dimensional ratios. In addition, the numerical range "A to B" represents from A to B, unless otherwise specified. Moreover, in this embodiment, "(meth)acryl" means acryl, methacryl, or both acryl and methacryl. Furthermore, "cyclic olefin polymer" means a copolymer and/or a ring-opening polymer unless otherwise specified.

Since conventional waveguides are made of, for example, metal tubes, they do not have flexibility and may not be applicable to applications where bending is required.
The present inventors have made intensive studies to solve the above problems. As a result, by using a dielectric with highly controlled density, relative permittivity, and dielectric loss, it was possible to suppress the decline in the transmission efficiency of electrical signals even in high frequency bands such as microwaves, and to improve flexibility. The inventors have found that a flexible waveguide can be obtained, and completed the present invention.

That is, the flexible waveguide according to this embodiment is as follows.

A flexible waveguide comprising a rod-shaped dielectric and a conductor covering the outer surface of the dielectric,
A flexible waveguide wherein the dielectric satisfies (a) and (b) below.
(a) Density of 1.50 g/cm ³ or less (b) Relative permittivity of 2.3 or less measured at a frequency of 10 GHz and dielectric loss of 0.0013 or less measured at a frequency of 10 GHz

Further, in Patent Document 1, polyfluoroethylene-based fiber is exemplified as a flexible dielectric material.
According to the findings of the present inventors, polyfluoroethylene-based fibers, which have been exemplified as materials for conventional flexible dielectrics, have a high specific gravity as a polymer material, and moreover, they can be There was a problem that molding was difficult with the processing equipment applied to the material.
In the flexible waveguide according to the present embodiment, the dielectric can be easily manufactured using ordinary equipment such as an extruder, and a lightweight flexible waveguide can be obtained because of its low specific gravity. Also, when the conductor is formed by metal plating, the plating solution penetrates more easily than in the case where the polyethylene fluoride fiber is used as the dielectric, so a flexible waveguide that is easy to manufacture can be obtained.

Each configuration according to the present embodiment will be described in further detail below.

<Dielectric>
The shape of the dielectric used in the flexible waveguide according to this embodiment is rod-like. At this time, the rod shape includes those having an elongated shape regardless of length such as a rod shape, a stick shape, and a bar shape, and also includes those having a small cross-sectional area such as a line shape and a wire shape.
Furthermore, as the cross-sectional shape of the dielectric, various cross-sectional shapes such as circular, elliptical, rectangular, and irregular shapes can be applied.
The shape and cross-sectional shape of the dielectric used in the flexible waveguide according to this embodiment can be appropriately selected according to the application of the flexible waveguide according to this embodiment.

The density of the dielectric according to this embodiment is 1.50 g/cm ³ or less, preferably 1.30 g/cm ³ or less, more preferably 1.20 g/cm ³ or less, and even more preferably 1.10 g. /cm ³ or less, more preferably 1.00 g/cm ³ or less, more preferably 0.90 g/cm ³ or less, even more preferably 0.85 g/cm ³ or less, even more preferably 0.80 g/cm 3 or less, and even more preferably 0.80 g/cm ³ or less. It is preferably 0.70 g/cm ³ or less, more preferably 0.65 g/cm ³ or less. When the density of the dielectric is equal to or less than the above upper limit, the flexible waveguide becomes lightweight, and the handleability and workability of the flexible waveguide become better.
Also, the lower limit of the density of the dielectric according to this embodiment is not particularly limited, but is, for example, 0.01 g/cm ³ or more.

The dielectric constant of the dielectric according to the present embodiment measured at a frequency of 10 GHz is 2.3 or less, preferably 2.2 or less, more preferably 2.1 or less, and still more preferably 2.0 or less. It is more preferably 1.9 or less, more preferably 1.8 or less, still more preferably 1.7 or less. When the relative permittivity of the dielectric is equal to or less than the above upper limit, the transmission efficiency of electric signals is improved even in high frequency bands such as microwaves, millimeter waves, and terahertz waves.
Also, the lower limit of the dielectric constant of the dielectric according to this embodiment is not particularly limited, but is, for example, 0 or more.

The dielectric loss of the dielectric according to the present embodiment measured at a frequency of 10 GHz is 0.0013 or less, preferably 0.0012 or less, more preferably 0.0011 or less, still more preferably 0.0010 or less, and further preferably It is preferably 0.0009 or less, more preferably 0.0007 or less, still more preferably 0.0005 or less, still more preferably 0.0004 or less. When the dielectric loss of the dielectric is equal to or less than the above upper limit value, the transmission efficiency of electric signals is improved even in high frequency bands such as microwaves, millimeter waves, and terahertz waves.
Also, the lower limit of the dielectric loss of the dielectric according to this embodiment is not particularly limited, but is, for example, 0 or more.

In the dielectric according to the present embodiment, the content of fluorine atoms is preferably 1% by mass or less, more preferably 0.5% by mass or less when the entire dielectric is 100% by mass. 0.1% by mass or less is more preferable. When the content of fluorine atoms in the dielectric is equal to or less than the above upper limit, the density of the dielectric can be lowered, and a flexible waveguide with good handleability and workability can be obtained. The moldability of the dielectric is improved.
The lower limit of the content of fluorine atoms in the dielectric according to this embodiment is not particularly limited, but is, for example, 0% by mass or more. At this time, "0% by mass" includes values below the lower limit of detection.

Compounds used for such dielectrics include, for example, 4-methyl-1-pentene (co)polymers and cyclic olefin copolymers.
The compound used for the dielectric will be described in more detail below.

[4-methyl-1-pentene (co)polymer]
A preferred example of the compound used in the dielectric according to this embodiment is 4-methyl-1-pentene (co)polymer. The 4-methyl-1-pentene (co)polymer may be a 4-methyl-1-pentene polymer containing only the structural unit (P) derived from 4-methyl-1-pentene, or 4-methyl- A structural unit (P) derived from 1-pentene and a structural unit (Q) derived from an α-olefin having 2 to 20 carbon atoms other than 4-methyl-1-pentene, 4-methyl-1-pentene and the structural unit (Q) derived from an α-olefin having 2 to 20 carbon atoms other than 4-methyl-1-pentene is 100 mol% in total. -1-Pentene copolymer may be included.

Examples of α-olefins having 2 to 20 carbon atoms other than 4-methyl-1-pentene include ethylene, propylene, 1-butene, 1-hexene, 1-octene, 1-decene, 1-tetradecene, and 1-hexadecene. , 1-octadecene and the like. Preferred α-olefins are ethylene, propylene, 1-butene, 1-hexene, 1-octene, 1-decene, 1-hexadecene and 1-octadecene, more preferably ethylene, propylene, 1-butene and 1-octene. -decene, 1-hexadecene, 1-octadecene. The α-olefins may be used singly or in combination of two or more thereof.

The above 4-methyl-1-pentene (co)polymer preferably satisfies (i) and (ii) below.
(i) 15 to 100 mol% of the structural unit (P) derived from 4-methyl-1-pentene
(ii) Structural units (Q) derived from at least one selected from α-olefins having 2 to 20 carbon atoms (excluding 4-methyl-1-pentene) are 0 to 85 mol% of the above structural units When the amount is within the above range, the dielectric can be easily obtained by a normal molding method such as extrusion molding, and a flexible waveguide with low specific gravity, light weight and low cost can be obtained. In addition, when the conductor is formed by metal plating, the plating liquid easily permeates the conductor, so it is possible to provide an inexpensive flexible waveguide that is easy to manufacture.

A more preferable first form of the 4-methyl-1-pentene (co)polymer is a 4-methyl-1-pentene (co)polymer that satisfies (iii) to (v) below.
(iii) 60 to 100 mol% of the structural unit (P) derived from 4-methyl-1-pentene
(iv) 0 to 40 mol% of structural units (Q) derived from at least one selected from α-olefins having 2 to 20 carbon atoms (excluding 4-methyl-1-pentene) (v) DSC The melting point (Tm) measured at is in the range of 200 to 250 ° C.

In the first form of the 4-methyl-1-pentene (co)polymer, the structural unit (P) derived from 4-methyl-1-pentene is preferably 60 to 100 mol%, more preferably 70 to 99 mol %, more preferably 80 to 98 mol %, particularly preferably 90 to 95 mol %.
Further, in the first form of the 4-methyl-1-pentene (co)polymer, derived from at least one selected from α-olefins having 2 to 20 carbon atoms (excluding 4-methyl-1-pentene) The constituent unit (Q) used is preferably 0 to 40 mol%, more preferably 1 to 30 mol%, still more preferably 2 to 20 mol%, and particularly preferably 5 to 10 mol%.
Furthermore, in the first form of the 4-methyl-1-pentene (co)polymer, the melting point (Tm) measured by DSC is preferably 200 to 250°C, more preferably 205 to 245°C, and It is preferably 210 to 240°C, particularly preferably 220 to 235°C.
When the amount and melting point (Tm) of the above structural units are within the above ranges, the dielectric can be easily obtained by a normal molding method such as extrusion molding, and a flexible conductor with low specific gravity, light weight and low cost can be obtained. You can get a wave tube. In addition, when the conductor is formed by metal plating, the plating liquid easily permeates the conductor, so it is possible to provide an inexpensive flexible waveguide that is easy to manufacture.

In the first embodiment of the 4-methyl-1-pentene (co)polymer, the α-olefin having 2 to 20 carbon atoms other than 4-methyl-1-pentene is preferably ethylene, propylene, 1 -butene, 1-hexene, 1-octene, 1-decene, 1-tetradecene, 1-hexadecene, 1-octadecene, more preferably 1-hexene, 1-octene, 1-decene, 1-hexadecene, 1- Octadecene, particularly preferably 1-hexadecene and 1-octadecene. The α-olefins may be used singly or in combination of two or more thereof.
Such 4-methyl-1-pentene/α-olefin copolymers are available from Mitsui Chemicals, Inc., TPX (registered trademark) RT18, RT31, DX845, DX231, DX350, DX820, MX004, MX002, MX002O, DX310. etc.

As a second more preferable form of the 4-methyl-1-pentene (co)polymer, the 4-methyl-1-pentene (co)polymer is a 4-methyl-1-pentene/α-olefin copolymer. A 4-methyl-1-pentene/α-olefin copolymer (A), which is a coalescence (A) and satisfies (vi) to (viii) below, can be mentioned.
(vi) 15 to 99 mol% of the structural unit (P) derived from 4-methyl-1-pentene
(vii) The structural unit (Q) derived from at least one selected from α-olefins having 2 to 20 carbon atoms (excluding 4-methyl-1-pentene) is 1 to 85 mol% (viii) DSC Melting point (Tm) less than 200°C or no melting point observed

In the second form of the 4-methyl-1-pentene (co)polymer, the structural unit (P) derived from 4-methyl-1-pentene is preferably 15 to 99 mol%, more preferably 30 to 99 mol %, more preferably 50 to 98 mol %, particularly preferably 70 to 95 mol %.
Further, in the second form of the 4-methyl-1-pentene (co)polymer, derived from at least one selected from α-olefins having 2 to 20 carbon atoms (excluding 4-methyl-1-pentene) The constituent unit (Q) used is 1 to 85 mol%, preferably 1 to 70 mol%, still more preferably 2 to 50 mol%, and particularly preferably 5 to 30 mol%.
Further, in the second form of the 4-methyl-1-pentene (co)polymer, the melting point (Tm) measured by DSC is preferably less than 200°C or no melting point is observed, more preferably less than 150°C or No melting point is observed, more preferably below 135° C. or no melting point is observed, particularly preferably no melting point is observed.
When the amount and melting point (Tm) of the above structural units are within the above ranges, the dielectric can be easily obtained by a normal molding method such as extrusion molding, and a flexible conductor with low specific gravity, light weight and low cost can be obtained. You can get a wave tube. In addition, when the conductor is formed by metal plating, the plating liquid easily permeates the conductor, so it is possible to provide an inexpensive flexible waveguide that is easy to manufacture.

In the second embodiment of the 4-methyl-1-pentene (co)polymer, the α-olefin having 2 to 20 carbon atoms other than 4-methyl-1-pentene is preferably ethylene, propylene, 1 -butene, 1-hexene, 1-octene, 1-decene, 1-tetradecene, 1-hexadecene and 1-octadecene, more preferably ethylene, propylene, 1-butene, 1-hexene and 1-octene. , and particularly preferably ethylene and propylene. The α-olefins may be used singly or in combination of two or more thereof.

At this time, the first form and the second form may be used alone, may be used in combination with each other, or may be used in combination with other compounds.

As the dielectric according to the present embodiment, the above 4-methyl-1-pentene (co)polymer, thermoplastic resin (excluding 4-methyl-1-pentene (co)polymer) or elastomer. The content of the thermoplastic resin or elastomer in the dielectric is 1 part by mass or more and 50 parts by mass or less (however, the total amount of the 4-methyl-1-pentene (co)polymer and the thermoplastic resin or elastomer is 100 parts by mass.).

(4-methyl-1-pentene/α-olefin copolymer)
The 4-methyl-1-pentene/α-olefin copolymer in the present embodiment has 2 to 20 carbon atoms other than structural units (P) derived from 4-methyl-1-pentene and 4-methyl-1-pentene. Having a structural unit (Q) derived from the following α-olefin, a structural unit (P) derived from 4-methyl-1-pentene, and a carbon number of 2 to 20 other than the above 4-methyl-1-pentene is a 4-methyl-1-pentene copolymer containing 100 mol% in total of structural units (Q) derived from α-olefins.
The 4-methyl-1-pentene/α-olefin copolymer preferably contains 15 to 99 mol% of the structural unit (P) derived from 4-methyl-1-pentene and has 2 to 20 carbon atoms. The structural unit (Q) derived from at least one selected from α-olefins (excluding 4-methyl-1-pentene) is 1 to 85 mol %.

The proportion of the structural unit (P) derived from 4-methyl-1-pentene is preferably 15 to 99 mol%, more preferably 30 to 99 mol%, still more preferably 50 to 98 mol%, particularly preferably is 70 to 95 mol %.
Further, the ratio of the structural unit (Q) derived from the α-olefin is preferably 1 to 85 mol%, more preferably 1 to 70 mol%, still more preferably 2 to 50 mol%, particularly preferably 5 ~30 mol%.

When the ratio of the structural units (P) and (Q) is equal to or higher than the lower limit, the flexibility and lightness of the flexible waveguide using the dielectric are improved, and the structural unit ( When the proportions of P) and (Q) are equal to or less than the above upper limits, the flexibility and lightness of the flexible waveguide using the dielectric are further improved.
In other words, by highly controlling the ratio of the structural units (P) and (Q), the flexibility and lightness of the flexible waveguide according to the present invention can be well balanced. .

Examples of α-olefins leading to the structural unit (Q) include ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 1-octene, 1-decene, 1-undecene, 1-dodecene and 1-tetradecene. , 1-hexadecene, 1-octadecene, 1-eicosene, etc. Linear α-olefins having 2 to 20 carbon atoms, preferably 2 to 15 carbon atoms, more preferably 2 to 10 carbon atoms, 3- methyl-1-butene, 3-methyl-1-pentene, 3-ethyl-1-pentene, 4,4-dimethyl-1-pentene, 4-methyl-1-hexene, 4,4-dimethyl-1-hexene, Examples include branched α-olefins having 5 to 20 carbon atoms, preferably 5 to 15 carbon atoms such as 4-ethyl-1-hexene and 3-ethyl-1-hexene. Among these, ethylene, propylene, 1-butene, 1-pentene, 1-hexene and 1-octene are preferred, and propylene is particularly preferred.

(thermoplastic resin or elastomer)
The thermoplastic resin or elastomer (hereinafter also referred to as "resin or elastomer") is not particularly limited, and examples thereof include the following resins and rubbers.

Thermoplastic polyolefin resins (excluding the above 4-methyl-1-pentene (co)polymers), specifically low density, medium density, high density polyethylene, high pressure low density polyethylene, isotactic polypropylene, syndiotactic polypropylene, poly 1-butene, poly 4-methyl-1-pentene, poly 3-methyl-1-butene;
Thermoplastic polyamide resins, specifically aliphatic polyamides (nylon 6, nylon 11, nylon 12, nylon 66, nylon 610, nylon 612);
Thermoplastic polyester resins, specifically polyethylene terephthalate, polybutylene terephthalate, polyester elastomer;
Thermoplastic vinyl aromatic resins, specifically polystyrene, ABS resin, AS resin, styrene elastomer (styrene-butadiene-styrene block polymer, styrene-isoprene-styrene block polymer, styrene-isobutylene-styrene block polymer, and the aforementioned hydrogenated products);
Thermoplastic polyurethane; vinyl chloride resin; vinylidene chloride resin; acrylic resin; ethylene-vinyl acetate copolymer; ethylene-methacrylic acid acrylate copolymer; ionomer; ethylene-vinyl alcohol copolymer; polyacetal; polyphenylene oxide; polyphenylene sulfide polyimide; polyarylate; polysulfone; polyether sulfone; rosin resin; terpene resin;
Olefin-based thermoplastic elastomers, specifically, ethylene/α-olefin copolymers, propylene/α-olefin copolymers, 1-butene/α-olefin copolymers, cyclic olefin copolymers, chlorinated polyolefins;
Copolymer elastomers, specifically ethylene/α-olefin/diene copolymer, propylene/α-olefin/diene copolymer, 1-butene/α-olefin/diene copolymer, polybutadiene rubber, polyisoprene Examples include rubber, neoprene rubber, nitrile rubber, butyl rubber, halogenated butyl rubber, polyisobutylene rubber, natural rubber, and silicone rubber.

These thermoplastic resins and elastomers may be used singly or in combination of two or more.

Among these, low density, medium density, high density polyethylene, high pressure low density polyethylene, isotactic polypropylene, syndiotactic polypropylene, poly 1-butene, poly 4-methyl-1-pentene, poly 3-methyl-1 -butene, ethylene/α-olefin copolymer, propylene/α-olefin copolymer, 1-butene/α-olefin copolymer, polystyrene, styrene elastomer, ethylene/vinyl acetate copolymer, ethylene/methacrylic acid Acrylate copolymers, ionomers, fluorine resins, rosin resins, terpene resins and petroleum resins, ethylene/α-olefin/diene copolymers, propylene/α-olefin/diene copolymers, 1-butene/α- Olefin-diene copolymer, polybutadiene rubber, polyisoprene rubber, neoprene rubber, nitrile rubber, butyl rubber, polyisobutylene rubber, and silicone rubber are preferred, and more preferred forms are isotactic polypropylene, poly-1-butene, and poly-4-methyl. -1-pentene, ethylene/α-olefin copolymer, propylene/α-olefin copolymer, 1-butene/α-olefin copolymer, ethylene/vinyl acetate copolymer, styrene elastomer, rosin resin, Terpene resin, petroleum resin, ethylene/α-olefin/diene copolymer, propylene/α-olefin/diene copolymer, 1-butene/α-olefin/diene copolymer, polybutadiene rubber, polyisoprene rubber, neoprene rubber, nitrile rubber, butyl rubber, polyisobutylene rubber, and silicone rubber.

Examples of the rosin-based resin include natural rosin, polymerized rosin, modified rosin modified with maleic acid, fumaric acid, (meth)acrylic acid, and rosin derivatives. Examples of the rosin derivative include esterified products of the natural rosin, polymerized rosin or modified rosin, phenol-modified products and esterified products thereof. Further, hydrogenated products thereof can also be mentioned.

Examples of the terpene-based resin include resins composed of α-pinene, β-pinene, limonene, dipentene, terpenephenol, terpene alcohol, terpene aldehyde, etc. α-pinene, β-pinene, limonene, dipentene, etc. , α-methylstyrene, isopropenyltoluene, and other aromatic-modified terpene-based resins obtained by polymerizing aromatic monomers. Hydrogenated products thereof can also be mentioned.

Examples of the petroleum resins include aliphatic petroleum resins whose main raw material is C5 fraction of tar naphtha, aromatic petroleum resins whose main raw material is C9 fraction, and copolymerized petroleum resins thereof. That is, C5 petroleum resin (resin obtained by polymerizing C5 fraction of naphtha cracked oil), C9 petroleum resin (resin obtained by polymerizing C9 fraction of naphtha cracked oil), C5C9 copolymer petroleum resin (resin obtained by polymerizing C5 fraction of naphtha cracked oil), and C9 fraction), styrene/α-methylstyrene copolymer petroleum resin, α-methylstyrene polymer petroleum resin, isopropenyltoluene polymer petroleum resin, etc., and tar naphtha fraction Styrenes, indenes, coumarone, other coumarone-indene resins containing dicyclopentadiene, etc., alkylphenol resins represented by condensation products of p-tert-butylphenol and acetylene, o-xylene, p-xylene or Xylene-based resins obtained by reacting m-xylene with formalin are also included.

Also, one or more resins selected from the group consisting of rosin-based resins, terpene-based resins and petroleum resins are preferably hydrogenated derivatives because of their excellent weather resistance and discoloration resistance. The ring and ball softening point of the resin is preferably in the range of 40 to 180°C. The number average molecular weight (Mn) molecular weight of the resin measured by GPC is preferably in the range of about 100 to 10,000.

Commercially available products may be used as one or more resins selected from the group consisting of rosin-based resins, terpene-based resins and petroleum resins.

Assuming that the total amount of the 4-methyl-1-pentene (co)polymer and the resin or elastomer is 100 parts by mass, the lower limit of the 4-methyl-1-pentene (co)polymer content in the composition is preferably 50 parts by mass, more preferably 55 parts by mass, particularly preferably 60 parts by mass, and the upper limit of the 4-methyl-1-pentene (co)polymer content is preferably 99 parts by mass, more preferably is 95 parts by weight, particularly preferably 90 parts by weight.

[Cyclic olefin copolymer]
A preferred example of the compound used for the dielectric according to this embodiment is a cyclic olefin copolymer containing a structure represented by the following general formula (2).

In general formula (2), x and y represent copolymerization ratios and are real numbers satisfying 0/100≤y/x≤95/5. x, y are on a molar basis. n indicates the substitution number of the substituent Q and is a real number of 0≦n≦2. R ^a is a 2+n-valent group selected from the group consisting of hydrocarbon groups having 2 to 20 carbon atoms. R ^b is a hydrogen atom or a monovalent group selected from the group consisting of hydrocarbon groups having 1 to 10 carbon atoms. R ^c is a tetravalent group selected from the group consisting of hydrocarbon groups having 2 to 10 carbon atoms. Q is COOR ^d (Rd is a hydrogen atom or a monovalent group selected from the group consisting of hydrocarbon groups having 1 to 10 carbon atoms). Each of R ^a , R ^b , R ^c and Q may be one kind, or may be two or more kinds in an arbitrary ratio.

In general formula (2) above, R ^a is preferably one or more divalent groups selected from hydrocarbon groups having 2 to 12 carbon atoms, more preferably n=0. is a divalent group represented by general formula (3), most preferably a divalent group in which p is 0 or 1 in general formula (3) below. The structure of R ^a may be used alone or in combination of two or more.

Here, in general formula (3), p is an integer of 0-2.
In the above general formula (2), examples of R ^b include a hydrogen atom, methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, 2-methylpropyl group and the like. , preferably a hydrogen atom and/or a methyl group, most preferably a hydrogen atom.

Further, in the above general formula (2), the divalent group represented by the following general formula (A) when n = 0 is represented by the following general formulas (4) to (6), etc. groups.

In general formulas (4) to (6), R ^a is as defined above.
Moreover, the type of polymerization is not at all limited in this embodiment, and various known polymerization types such as addition polymerization and ring-opening polymerization can be applied. Examples of addition polymerization include random copolymers, block copolymers, alternating copolymers, and the like. In this embodiment, it is preferable to use a random copolymer from the viewpoint of improving the flexibility and lightness of the flexible waveguide using the dielectric.
When the structure of the resin used as the main component is as described above, the flexibility and lightness of the flexible waveguide using the dielectric material are improved, and the flexibility has good handling and workability. A waveguide can be obtained.

(Example of polymer containing alicyclic structure in at least part of repeating structural unit)
The polymers represented by the general formula (2) are broadly classified into the following four types of polymers (W) to (Z).
(W) Copolymers of ethylene or α-olefins and cyclic olefins (X) Ring-opening polymers or hydrogenated products thereof (Y) Vinyl alicyclic hydrocarbon polymers (Z) Other polymers explain.

((W) copolymer of ethylene or α-olefin and cyclic olefin)
(W) A copolymer of ethylene or an α-olefin and a cyclic olefin is a cyclic olefin copolymer represented by general formula (7). For example, it consists of structural units derived from ethylene or a linear or branched α-olefin having 3 to 30 carbon atoms and structural units derived from a cyclic olefin.

In general formula (7), R ^a is a divalent group selected from the group consisting of hydrocarbon groups having 2 to 20 carbon atoms, preferably 2 to 12 carbon atoms.
R ^b is a hydrogen atom or a monovalent group selected from the group consisting of hydrocarbon groups having 1 to 28 carbon atoms, preferably 1 to 10 carbon atoms, more preferably 1 to 5 carbon atoms.
Incidentally, each of Ra ^and ^Rb may be one kind, or two or more kinds thereof may be contained in an arbitrary ratio.

x and y indicate the copolymerization ratio and are real numbers satisfying 5/95≤y/x≤95/5. Preferably 50/50≤y/x≤95/5, more preferably 55/45≤y/x≤80/20. x, y are on a molar basis.

(Structural unit derived from ethylene or α-olefin)
Structural units derived from ethylene or α-olefins are structural units derived from ethylene or linear or branched α-olefins having 3 to 30 carbon atoms as described below.

Specifically, ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 3-methyl-1-butene, 3-methyl-1-pentene, 3-ethyl-1-pentene, 4-methyl-1 -pentene, 4-methyl-1-hexene, 4,4-dimethyl-1-hexene, 4,4-dimethyl-1-pentene, 4-ethyl-1-hexene, 3-ethyl-1-hexene, 1-octene , 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, 1-eicosene and the like. Among these, ethylene is preferred. Two or more of these structural units derived from ethylene or α-olefin may be contained within a range that does not impair the effects of the present invention.

(Structural Unit Derived from Cyclic Olefin)
The cyclic olefin-derived structural unit is at least one selected from the group consisting of cyclic olefin-derived structural units represented by the following general formula (8), general formula (9) and general formula (10).
The cyclic olefin represented by general formula (8) has the following structure.

In general formula (8), u is 0 or 1, v is 0 or a positive integer, and w is 0 or 1. When w is 1, the ring represented by w is a 6-membered ring, and when w is 0, the ring is a 5-membered ring. R ⁶¹ to R ⁷⁸ as well as R ^a1 and R ^b1 may be the same or different and each is a hydrogen atom, a halogen atom or a hydrocarbon group.

The halogen atom is a fluorine atom, chlorine atom, bromine atom or iodine atom. The hydrocarbon group usually includes an alkyl group having 1 to 20 carbon atoms, a halogenated alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 15 carbon atoms and an aromatic hydrocarbon group. .

More specifically, alkyl groups include methyl, ethyl, propyl, isopropyl, amyl, hexyl, octyl, decyl, dodecyl, and octadecyl. Examples of halogenated alkyl groups include groups in which the above alkyl groups having 1 to 20 carbon atoms are substituted with one or more halogen atoms. The cycloalkyl group includes cyclohexyl and the like, and the aromatic hydrocarbon group includes phenyl, naphthyl and the like.

Furthermore, in the above general formula (8), R ⁷⁵ and R ⁷⁶ , R ⁷⁷ and R ⁷⁸ , R ⁷⁵ and R ⁷⁷ , R ⁷⁶ and R ⁷⁸ , R ⁷⁵ and R ⁷⁸ , or Each of R ⁷⁶ and R ⁷⁷ may be combined, ie together, to form a monocyclic or polycyclic group. Furthermore, the monocyclic or polycyclic rings thus formed may have double bonds. Specific examples of monocyclic or polycyclic groups formed here include the following.

In the above examples, the carbon atom numbered 1 or 2 represents the carbon atom to which R ⁷⁵ (R ⁷⁶ ) or R ⁷⁷ (R ⁷⁸ ) is bonded in the general formula (8).

R ⁷⁵ and R ⁷⁶ or R ⁷⁷ and R ⁷⁸ may form an alkylidene group. The alkylidene group usually has 2 to 20 carbon atoms. Specific examples of alkylidene groups include ethylidene, propylidene, isopropylidene, and the like.

The cyclic olefin represented by general formula (9) has the following structure.

In general formula (9), x and d are 0 or 1 or more positive integers, and y and z are 0, 1 or 2. In addition, R ⁸¹ to R ⁹⁹ may be the same or different and each is a hydrogen atom, a halogen atom, an aliphatic hydrocarbon group, an aromatic hydrocarbon group or an alkoxy group, and R ⁸⁹ and R ⁹⁰ are bonded and the carbon atom to which R ⁹³ is bonded or the carbon atom to which R ⁹¹ is bonded may be bonded directly or via an alkylene group having 1 to 3 carbon atoms. When y=z=0, ^R95 and ^R92 or ^R95 and ^R99 may be bonded to each other to form a monocyclic or polycyclic aromatic ring.
As the halogen atom, the same halogen atom as in the above formula (8) can be exemplified.

The aliphatic hydrocarbon group includes an alkyl group having 1 to 20 carbon atoms or a cycloalkyl group having 3 to 15 carbon atoms. More specifically, alkyl groups include methyl, ethyl, propyl, isopropyl, amyl, hexyl, octyl, decyl, dodecyl, octadecyl, and the like. Cycloalkyl groups include cyclohexyl and the like.

Aromatic hydrocarbon groups include aryl groups and aralkyl groups, and specific examples include phenyl, tolyl, naphthyl, benzyl, and phenylethyl.

Alkoxy groups include methoxy, ethoxy, propoxy, and the like. Here, the carbon atom to which R ⁸⁹ and R ⁹⁰ are bonded and the carbon atom to which R ⁹³ is bonded or the carbon atom to which R ⁹¹ is bonded are directly or an alkylene group having 1 to 3 carbon atoms may be connected via That is, when the above two carbon atoms are bonded via an alkylene group, R ⁸⁹ and R ⁹³ , or R ⁹⁰ and R ⁹¹ jointly form a methylene group (--CH ₂ -), an ethylene group (-CH ₂ CH ₂ -) or a propylene group (-CH ₂ CH ₂ CH ₂ -).

Furthermore, when y=z=0, ^R95 and ^R92 or ^R95 and ^R99 may combine with each other to form a monocyclic or polycyclic aromatic ring. Specifically, when y=z=0, the following aromatic rings formed by R ⁹⁵ and R ⁹² are exemplified.

l is the same as d in the general formula (9).
The cyclic olefin represented by general formula (10) has the following structure.

In general formula (10), R ¹⁰⁰ and R ¹⁰¹ may be the same or different and each represents a hydrogen atom or a hydrocarbon group having 1 to 5 carbon atoms, and f satisfies 1≦f≦18. The hydrocarbon group having 1 to 5 carbon atoms is preferably an alkyl group, a halogenated alkyl group or a cycloalkyl group. Specific examples of these are clear from the specific examples of R ⁶¹ to R ⁷⁸ in formula (8) above.

Specific examples of the structural unit (B) derived from the cyclic olefin represented by the above general formula (8), (9) or (10) include bicyclo-2-heptene derivatives (bicyclohept-2-ene derivatives ), tricyclo-3-decene derivative, tricyclo-3-undecene derivative, tetracyclo-3-dodecene derivative, pentacyclo-4-pentadecene derivative, pentacyclopentadecadiene derivative, pentacyclo-3-pentadecene derivative, pentacyclo-4-hexadecene derivative , pentacyclo-3-hexadecene derivative, hexacyclo-4-heptadecene derivative, heptacyclo-5-eicosene derivative, heptacyclo-4-eicosene derivative, heptacyclo-5-heneicosene derivative, octacyclo-5-docosene derivative, nonacyclo-5-pentacosene derivative, nonacyclo-6-hexacosene derivatives, cyclopentadiene-acenaphthylene adduct derivatives, 1,4-methano-1,4,4a,9a-tetrahydrofluorene derivatives, 1,4-methano-1,4,4a,5,10, 10a-hexahydroanthracene derivatives, cycloalkylene derivatives having 3 to 20 carbon atoms, and the like.

Among the structural units (B) derived from cyclic olefins represented by the above general formulas (8), (9) and (10), tetracyclo[4.4.0.1 ^2,5 . 1 ^7,10 ]-3-dodecene derivative, hexacyclo[6.6.1.1 ^3,6 . 1 ^{10, 13} . 0 ^{2, 7} . 0 ^9,14 ]-4-heptadecene derivatives and derivatives of compounds represented by the following structures are exemplified as preferred embodiments.

5-phenyl-bicyclo[2.2.1]hept-2-ene

5-methyl-5-phenyl-bicyclo[2.2.1]hept-2-ene

5-tolyl-bicyclo[2.2.1]hept-2-ene

5-(ethylphenyl)-bicyclo[2.2.1]hept-2-ene

5-(isopropylphenyl)-bicyclo[2.2.1]hept-2-ene

5-(α-naphthyl)-bicyclo[2.2.1]hept-2-ene

5-(biphenyl)-bicyclo[2.2.1]hept-2-ene

5,6-(diphenyl)-bicyclo[2.2.1]hept-2-ene

1,4-methano-1,4,4a,9a-tetrahydrofluorene

1,4-methano-1,4,4a,5,10,10a-hexahydroanthracene

　Cyclopentadiene-acenaphthylene adduct

　Cyclopentadiene-benzyne adduct

benzonorbornadiene derivative

Also, particularly preferably, the cyclic olefin is tetracyclo[4.4.0.1 ^2,5 . 1 ^7,10 ]-3-dodecene, 1,4-methano-1,4,4a,9a-tetrahydrofluorene, cyclopentadiene-benzine adducts and cyclopentadiene-acenaphthylene adducts, Most preferably, tetracyclo[4.4.0.1 ^2,5 . 1 ^7,10 ]-3-dodecene.

The cyclic olefin represented by the general formula (8) or (9) as described above can be produced by subjecting cyclopentadiene and olefins having the corresponding structure to Diels-Alder reaction. Two or more kinds of structural units derived from cyclic olefins represented by these general formulas (8), (9) or (10) may be contained. In addition, those polymerized using the above monomers can be modified as necessary, in which case the structure of the structural units derived from the monomers can be changed. For example, depending on conditions, a benzene ring or the like in a monomer-derived structural unit can be converted to a cyclohexyl ring by hydrogenation treatment.

In the present embodiment, the "(W) copolymer of ethylene or α-olefin and cyclic olefin" includes ethylene and tetracyclo[4.4.0.1 ^2,5 . 1 ^7,10 ]-3-dodecene is preferred.

In addition, the type of copolymerization is not limited at all in the present embodiment, and various known copolymerization types such as random copolymers, block copolymers, and alternating copolymers can be applied, but random copolymers are preferable. be.

((X) ring-opening polymer or hydrogenated product thereof)
(X) The ring-opening polymer or its hydrogenated product is a cyclic olefin polymer containing a structural unit represented by general formula (5) among the structures listed as preferred examples in general formula (2) above. .

Also, the cyclic olefin polymer may have a polar group. Polar groups include hydroxyl, carboxyl, alkoxy, epoxy, glycidyl, oxycarbonyl, carbonyl, amino and ester groups.

A cyclic olefin polymer is usually obtained by polymerizing a cyclic olefin, specifically by ring-opening polymerization of an alicyclic olefin. A cyclic olefin polymer having a polar group can be obtained, for example, by introducing a compound having a polar group into the cyclic olefin polymer through a modification reaction, or by using a monomer containing a polar group as a copolymerization component. Obtained by copolymerization.

Specific examples of alicyclic olefins used to obtain cyclic olefin polymers include bicyclo[2.2.1]-hept-2-ene (common name: norbornene), 5-methyl-bicyclo[2 .2.1]-hept-2-ene, 5,5-dimethyl-bicyclo[2.2.1]-hept-2-ene, 5-ethyl-bicyclo[2.2.1]-hept-2- ene, 5-butyl-bicyclo[2.2.1]-hept-2-ene, 5-hexyl-bicyclo[2.2.1]-hept-2-ene, 5-octyl-bicyclo[2.2. 1]-hept-2-ene, 5-octadecyl-bicyclo[2.2.1]-hept-2-ene, 5-ethylidene-bicyclo[2.2.1]-hept-2-ene, 5-methylidene -bicyclo[2.2.1]-hept-2-ene, 5-vinyl-bicyclo[2.2.1]-hept-2-ene, 5-propenyl-bicyclo[2.2.1]-hept- 2-ene, 5-methoxy-carbinyl-bicyclo[2.2.1]-hept-2-ene, 5-cyano-bicyclo[2.2.1]-hept-2-ene, 5-methyl-5- Methoxycarbonyl-bicyclo[2.2.1]-hept-2-ene, 5-ethoxycarbonyl-bicyclo[2.2.1]-hept-2-ene, bicyclo[2.2.1]-hept-5 -enyl-2-methylpropionate, bicyclo[2.2.1]-hept-5-enyl-2-methyloctanate, bicyclo[2.2.1]-hept-2-ene-5,6- Dicarboxylic anhydride, 5-hydroxymethylbicyclo[2.2.1]-hept-2-ene, 5,6-di(hydroxymethyl)-bicyclo[2.2.1]-hept-2-ene, 5 -hydroxy-i-propylbicyclo[2.2.1]-hept-2-ene, 5,6-dicarboxy-bicyclo[2.2.1]-hept-2-ene, bicyclo[2.2.1 ]-hept-2-ene-5,6-dicarboxylic imide, 5-cyclopentyl-bicyclo[2.2.1]-hept-2-ene, 5-cyclohexyl-bicyclo[2.2.1]-hept- 2-ene, 5-cyclohexenyl-bicyclo[2.2.1]-hept-2-ene, 5-phenyl-bicyclo[2.2.1]-hept-2-ene, tricyclo[4.3.0 .1 ^2,5 ]deca-3,7-diene (common name: dicyclopentadiene), tricyclo[4.3.0.1 ^2,5 ]dec-3-ene, tricyclo[4.4.0.1 ^2,5 ]undeca-3,7-diene, tricyclo[4.4.0.1 ^2,5 ]undeca-3,8-diene, tricyclo[4.4.0.1 ^2,5 ]undeca-3- ene, tetracyclo[7.4.0.1 ^10,13 . 0 ^2,7 ]-trideca-2,4,6-11-tetraene (alias: 1,4-methano-1,4,4a,9a-tetrahydrofluorene), tetracyclo[8.4.0.1 ^11,14 . 0 ^3,8 ]-tetradeca-3,5,7,12-11-tetraene (alias: 1,4-methano-1,4,4a,5,10,10a-hexahydroanthracene), tetracyclo[4.4 .0.1 ^2,5 . 1 ^7,10 ]-dodeca-3-ene (common name: tetracyclododecene), 8-methyl-tetracyclo[4.4.0.1 ^2,5 . 1 ^7,10 ]-dodeca-3-ene, 8-ethyl-tetracyclo[4.4.0.1 ^2,5 . 1 ^7,10 ]-dodeca-3-ene, 8-methylidene-tetracyclo[4.4.0.1 ^2,5 . 1 ^7,10 ]-dodeca-3-ene, 8-ethylidene-tetracyclo[4.4.0.1 ^2,5 . 1 ^7,10 ]-dodeca-3-ene, 8-vinyl-tetracyclo[4.4.0.1 ^2,5 . 1 ^7,10 ]-dodeca-3-ene, 8-propenyl-tetracyclo[4.4.0.1 ^2,5 . 1 ^7,10 ]-dodeca-3-ene, 8-methoxycarbonyl-tetracyclo[4.4.0.1 ^2,5 . 1 ^7,10 ]-dodeca-3-ene, 8-methyl-8-methoxycarbonyl-tetracyclo[4.4.0.1 ^2,5 . 1 ^7,10 ]-dodeca-3-ene, 8-hydroxymethyl-tetracyclo[4.4.0.1 ^2,5 . 1 ^7,10 ]-dodeca-3-ene, 8-carboxy-tetracyclo[4.4.0.1 ^2,5 . 1 ^7,10 ]-dodeca-3-ene, 8-cyclopentyl-tetracyclo[4.4.0.1 ^2,5 . 1 ^7,10 ]-dodeca-3-ene, 8-cyclohexyl-tetracyclo[4.4.0.1 ^2,5 . 1 ^7,10 ]-dodeca-3-ene, 8-cyclohexenyl-tetracyclo[4.4.0.1 ^2,5 . 1 ^7,10 ]-dodeca-3-ene, 8-phenyl-tetracyclo[4.4.0.1 ^2,5 . 1 ^7,10 ]-dodeca-3-ene, pentacyclo[6.5.1.1 ^3,6 . 0 ^{2, 7} . 0 ^9,13 ]-pentadeca-3,10-diene, pentacyclo[7.4.0.1 ^3,6 . 1 ^{10, 13} . 0 ^2,7 ]-pentadeca-4,11-diene norbornene-based monomers; cyclobutene, cyclopentene, cyclohexene, 3,4-dimethylcyclopentene, 3-methylcyclohexene, 2-(2-methylbutyl)-1-cyclohexene , cyclooctene, 3a,5,6,7a-tetrahydro-4,7-methano-1H-indene, monocyclic cycloalkenes such as cycloheptene; vinyl alicyclic hydrocarbon monomers such as vinylcyclohexene and vinylcyclohexane ; alicyclic conjugated diene-based monomers such as cyclopentadiene and cyclohexadiene; Alicyclic olefins can be used either alone or in combination of two or more.

A copolymerizable monomer can be copolymerized as necessary. Specific examples thereof include ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 3-methyl-1-butene, 3-methyl-1-pentene, 3-ethyl-1-pentene, 4-methyl- 1-pentene, 4-methyl-1-hexene, 4,4-dimethyl-1-hexene, 4,4-dimethyl-1-pentene, 4-ethyl-1-hexene, 3-ethyl-1-hexene, 1- Ethylene or α-olefins having 2 to 20 carbon atoms such as octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, 1-eicosene; cyclobutene, cyclopentene, cyclohexene, 3,4- Cycloolefins such as dimethylcyclopentene, 3-methylcyclohexene, 2-(2-methylbutyl)-1-cyclohexene, cyclooctene, 3a,5,6,7a-tetrahydro-4,7-methano-1H-indene; 1,4 - non-conjugated dienes such as hexadiene, 4-methyl-1,4-hexadiene, 5-methyl-1,4-hexadiene, and 1,7-octadiene; These monomers can be used either alone or in combination of two or more.

The method for polymerizing the alicyclic olefin is not particularly limited, and can be carried out according to known methods. These ring-opening polymers are preferably used after being hydrogenated in terms of stability, flexibility and light weight. A known method can be used for the hydrogenation method.

((Y) vinyl alicyclic hydrocarbon polymer)
(Y) The vinyl alicyclic hydrocarbon polymer is a hydrogenated product of a (co)polymer obtained by using a vinyl aromatic hydrocarbon compound as a monomer or obtained by using a vinyl alicyclic hydrocarbon compound as a monomer. It is a (co)polymer that is obtained. Examples of vinyl compounds include vinyl aromatic compounds and vinyl alicyclic hydrocarbon compounds.

Examples of vinyl aromatic compounds include styrene, α-methylstyrene, α-ethylstyrene, α-propylstyrene, α-isopropylstyrene, α-t-butylstyrene, 2-methylstyrene, 3-methylstyrene, 4-methylstyrene. , 2,4-diisopropylstyrene, 2,4-dimethylstyrene, 4-t-butylstyrene, 5-t-butyl-2-methylstyrene, monochlorostyrene, dichlorostyrene, monofluorostyrene, 4-phenylstyrene, etc. etc. can be mentioned.

Vinyl alicyclic hydrocarbon compounds include vinylcyclohexanes such as vinylcyclohexane and 3-methylisopropenylcyclohexane; 4-vinylcyclohexene, 4-isopropenylcyclohexene, 1-methyl-4-vinylcyclohexene, 1-methyl-4 -isopropenylcyclohexene, 2-methyl-4-vinylcyclohexene, 2-methyl-4-isopropenylcyclohexene, and other vinylcyclohexenes.

In the present embodiment, other monomers copolymerizable with the aforementioned monomers may be copolymerized. Copolymerizable monomers include α-olefin monomers such as ethylene, propylene, isobutene, 2-methyl-1-butene, 2-methyl-1-pentene, 4-methyl-1-pentene; Cyclopentadiene-based monomers such as pentadiene, 1-methylcyclopentadiene, 2-methylcyclopentadiene, 2-ethylcyclopentadiene, 5-methylcyclopentadiene, 5,5-dimethylcyclopentadiene and dicyclopentadiene; cyclobutene, cyclopentene, monocyclic olefin monomers such as cyclohexene; conjugated diene monomers such as butadiene, isoprene, 1,3-pentadiene, furan, thiophene, and 1,3-cyclohexadiene; acrylonitrile, methacrylonitrile, α-chloroacrylonitrile Nitrile-based monomers such as; methyl methacrylate, ethyl methacrylate, propyl methacrylate, butyl methacrylate, methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, etc. monomers; unsaturated fatty acid-based monomers such as acrylic acid, methacrylic acid and maleic anhydride; phenylmaleimide; methyl vinyl ether; heterocyclic ring-containing vinyl compound-based monomers such as N-vinylcarbazole and N-vinyl-2-pyrrolidone A body etc. are mentioned.

From the viewpoint of the flexibility, lightness, mechanical strength, etc. of the flexible waveguide using the dielectric, the mixture of the above monomers used for polymerization is a vinyl aromatic hydrocarbon compound and/or a vinyl alicyclic compound. It preferably contains 50% by mass or more, preferably 70 to 100% by mass, more preferably 80 to 100% by mass, of the hydrocarbon compound of the formula. The monomer mixture may contain both the vinyl aromatic hydrocarbon compound and the vinyl alicyclic hydrocarbon compound.

The method for polymerizing the vinyl aromatic hydrocarbon compound or the vinyl alicyclic hydrocarbon compound is not particularly limited, and can be carried out according to known methods. A (co)polymer obtained from a vinyl aromatic hydrocarbon compound is preferably used as a hydrogenated product from the viewpoint of stability, flexibility and light weight. A known method can be used for the hydrogenation method.

The hydrogenated product of the (co)polymer obtained from the vinyl aromatic hydrocarbon compound preferably has a hydrogenation rate of phenyl groups of 95% or more, more preferably 99% or more. The hydrogenation treatment hydrogenates the phenyl groups in the resin structure to form cyclohexyl groups.

((Z) other polymers)
(Z) Other polymers include, for example, monocyclic cycloalkene polymers, alicyclic conjugated diene-based monomer polymers, and aromatic olefin polymers. Even structures not included in Y) can be arbitrarily selected within the scope of general formula (2). For example, those obtained by copolymerizing the above (W) to (Y) with each other or known copolymerizable monomers can be mentioned.

Among the four types of polymers roughly classified by (W) to (Z) above, preferred in terms of optical properties is (W) a copolymer of ethylene or an α-olefin and a cycloolefin, and among these, the most preferred. is ethylene tetracyclo[4.4.0.1 ^2,5 . 1 ^7,10 ]-3-dodecene copolymer.

Another form of the dielectric that satisfies the above requirements is the dielectric:
(A) one or more olefin-derived repeating units represented by the following general formula (I);
(B) a repeating unit derived from a cyclic non-conjugated diene represented by the following general formula (III);
(C) a repeating unit derived from one or more cyclic olefins represented by the following general formula (V);
A cyclic olefin copolymer having a crosslinkable group containing
In the cyclic olefin copolymer, the content of the repeating unit (B) derived from a cyclic non-conjugated diene is 5 mol% or more when the total number of moles of repeating units in the cyclic olefin copolymer is 100 mol%. It is preferably 36 mol % or less.

In general formula (I), R ³⁰⁰ represents a hydrogen atom or a linear or branched hydrocarbon group having 1 to 29 carbon atoms.

In general formula (III), u is 0 or 1, v is 0 or 1, w is 0 or 1, R ⁶¹ to R ⁷⁶ and R ^a1 and R ^b1 may be the same or different; A hydrogen atom, a halogen atom, an alkyl group having 1 to 20 carbon atoms, a halogenated alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 15 carbon atoms, or an aromatic group having 6 to 20 carbon atoms. R ¹⁰⁴ is a hydrogen atom or an alkyl group having 1 to 10 carbon atoms; t is a positive integer ^of 0 to ¹⁰ ; Alternatively, it may form a polycyclic ring.

In general formula (V), u is 0 or 1, v is 0 or 1, w is 0 or 1, R ⁶¹ to R ⁷⁸ and R ^a1 and R ^b1 may be the same or different; A hydrogen atom, a halogen atom, an alkyl group having 1 to 20 carbon atoms, a halogenated alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 15 carbon atoms, or an aromatic group having 6 to 20 carbon atoms. is a group hydrocarbon group, and R ⁷⁵ to R ⁷⁸ may combine with each other to form a monocyclic or polycyclic ring. However, when u and v are both 0, at least one of R ⁶⁷ to R ⁷⁰ and R ⁷⁵ to R ⁷⁸ is a substituent other than a hydrogen atom.

In the cyclic olefin copolymer, the content of the repeating unit (B) derived from the cyclic non-conjugated diene is preferably 5 mol% when the total number of moles of the repeating units in the cyclic olefin copolymer is 100 mol%. 36 mol % or more, more preferably 10 mol % or more and 33 mol % or less, still more preferably 20 mol % or more and 30 mol % or less.
When the content of the repeating unit (B) derived from the cyclic non-conjugated diene is within the above range, the dielectric material obtained from the cyclic olefin-based copolymer is an electric conductor in a high frequency band such as microwaves, millimeter waves, or terahertz waves. Excellent signal transmission efficiency. Furthermore, the flexibility, lightness, and mechanical properties of the flexible waveguide using the dielectric are improved.
Further, when the content of the repeating unit (B) derived from the cyclic non-conjugated diene is equal to or less than the above upper limit, the moldability and solubility of the cyclic olefin copolymer are improved, and the microwave, millimeter wave, or The transmission efficiency of electrical signals in high frequency bands such as terahertz waves is improved. When the content of the repeating unit (B) derived from the cyclic non-conjugated diene is at least the above lower limit, the flexibility, lightness, and mechanical properties of the flexible waveguide using the dielectric material become better. .

In the cyclic olefin-based copolymer, the content of the olefin-derived repeating unit (A) is preferably 20 mol% or more and 80 mol% when the total number of moles of the repeating units in the cyclic olefin-based copolymer is 100 mol%. mol% or less, more preferably 30 mol% or more and 75 mol% or less, more preferably 40 mol% or more and 70 mol% or less, particularly preferably 50 mol% or more and 70 mol% or less, a repeating unit derived from a cyclic non-conjugated diene The content of (B) is 5 mol% or more and 36 mol% or less, preferably 10 mol% or more and 33 mol% or less, more preferably 20 mol% or more and 30 mol% or less, and the cyclic olefin-derived repeating unit (C) is preferably 1 mol % or more and 30 mol % or less, more preferably 5 mol % or more and 25 mol % or less, and still more preferably 7 mol % or more and 20 mol % or less.
When the content of the repeating unit (B) derived from the cyclic non-conjugated diene is within the above range, the dielectric material obtained from the cyclic olefin-based copolymer is an electric conductor in a high frequency band such as microwaves, millimeter waves, or terahertz waves. Excellent signal transmission efficiency. Furthermore, the flexibility, lightness, and mechanical properties of the flexible waveguide using the dielectric are improved.

The olefin monomer, which is one of the raw materials for copolymerization of the cyclic olefin copolymer, is a monomer that gives the skeleton represented by the above formula (I) by addition copolymerization, and is represented by the following general formula (Ia). is an olefin.

In general formula (Ia) above, R ³⁰⁰ represents a hydrogen atom or a linear or branched hydrocarbon group having 1 to 29 carbon atoms. Examples of olefins represented by formula (Ia) include ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 3-methyl-1-butene, 3-methyl-1-pentene, 3-ethyl -1-pentene, 4-methyl-1-pentene, 4-methyl-1-hexene, 4,4-dimethyl-1-hexene, 4,4-dimethyl-1-pentene, 4-ethyl-1-hexene, 3 -ethyl-1-hexene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, 1-eicosene and the like. Among these, ethylene and propylene are preferred, and ethylene is particularly preferred, from the viewpoint of obtaining a crosslinked product (Q) having superior heat resistance, mechanical properties, dielectric properties, transparency and gas barrier properties. Two or more kinds of olefin monomers represented by the general formula (Ia) may be used.

The cyclic non-conjugated diene monomer, which is one of the raw materials for copolymerization of the cyclic olefin copolymer, undergoes addition copolymerization to form the structural unit represented by the above formula (III). Specifically, a cyclic non-conjugated diene represented by the following general formula (IIIa) corresponding to the above general formula (III) is used.

In general formula (IIIa) above, u is 0 or 1, v is 0 or a positive integer, preferably an integer of 0 or more and 2 or less, more preferably 0 or 1, w is 0 or 1, R ⁶¹ to R ⁷⁶ , R ^a1 and R ^b1 may be the same or different, and may be a hydrogen atom, a halogen atom, an alkyl group having 1 to 20 carbon atoms, a halogenated alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 15 carbon atoms or an aromatic hydrocarbon group having 6 to 20 carbon atoms; R ¹⁰⁴ is a hydrogen atom or an alkyl group having 1 to 10 carbon atoms; It is a positive integer, and R ⁷⁵ and R ⁷⁶ may combine with each other to form a monocyclic or polycyclic ring.

The cyclic non-conjugated diene represented by the general formula (IIIa) is not particularly limited, but includes, for example, a cyclic non-conjugated diene represented by the following chemical formula. Of these, 5-vinyl-2-norbornene, 8-vinyl-9-methyltetracyclo[4.4.0.1 ^2,5 . 1 ^7,10 ]-3-dodecene is preferred, and 5-vinyl-2-norbornene is particularly preferred.

The cyclic non-conjugated diene represented by the above general formula (IIIa) can also be specifically represented by the following general formula (IIIb).

n in general formula (IIIb) is an integer of 0 to 10, R ¹ is a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, and R ² is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms is.

The cyclic olefin-based copolymer of the present embodiment contains structural units derived from the cyclic non-conjugated diene represented by the general formula (III), so that the side chain portion, that is, the portion other than the main chain of the copolymerization It is characterized by having a double bond.

The cyclic olefin monomer, which is one of the raw materials for copolymerization of the cyclic olefin copolymer, undergoes addition copolymerization to form the structural unit represented by the above general formula (V). Specifically, a cyclic olefin monomer represented by the following general formula (Va) corresponding to the above general formula (V) is used.

In the above general formula (Va), u is 0 or 1, v is 0 or a positive integer, preferably an integer of 0 or more and 2 or less, more preferably 0 or 1, w is 0 or 1, R ⁶¹ to R ⁷⁸ , R ^a1 and R ^b1 may be the same or different, and may be a hydrogen atom, a halogen atom, an alkyl group having 1 to 20 carbon atoms, a halogenated alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 15 carbon atoms or an aromatic hydrocarbon group having 6 to 20 carbon atoms, and R ⁷⁵ to R ⁷⁸ may be bonded together to form a monocyclic or polycyclic ring; .

As specific examples of the cyclic olefin represented by the general formula (Va), compounds described in International Publication No. 2006/118261 can be used.
Cyclic olefins represented by the general formula (Va) include bicyclo[2.2.1]-2-heptene (also referred to as norbornene), tetracyclo[4.4.0.1 ^2,5 . 1 ^7,10 ]-3-dodecene (also called tetracyclododecene) is preferred, and tetracyclo[4.4.0.1 ^2,5 . 1 ^7,10 ]-3-dodecene is more preferred. Since these cyclic olefins have a rigid ring structure, the elastic modulus of the copolymer and the crosslinked product can be easily maintained, and since they do not contain heterogeneous double bond structures, there is an advantage that the crosslinking can be easily controlled.

By using the olefin monomer represented by the general formula (Ia) and the cyclic olefin represented by the general formula (Va) as copolymerization components, the solubility of the cyclic olefin copolymer in solvents is further improved. Therefore, moldability is improved.

The cyclic olefin-based copolymer includes (A) repeating units derived from one or more olefins represented by general formula (I), and (B) repeating units derived from a cyclic non-conjugated diene represented by general formula (III). and (C) in addition to repeating units derived from one or more cyclic olefins represented by general formula (V), a cyclic non-conjugated diene represented by general formula (III) and represented by general formula (V) It may be composed of repeating units derived from cyclic olefins other than cyclic olefins and/or chain polyenes.
In this case, as raw materials for copolymerization of the cyclic olefin-based copolymer, the olefin monomer represented by the general formula (Ia), the cyclic non-conjugated diene monomer represented by the general formula (IIIa), and the general formula (Va) In addition to the cyclic olefin monomer, a cyclic olefin monomer other than the cyclic non-conjugated diene monomer represented by the general formula (IIIa) and the cyclic olefin monomer represented by the general formula (Va), and / or a chain polyene monomer is used. be able to.
Such cyclic olefin monomers and linear polyene monomers include cyclic olefins represented by the following general formula (VIa) or (VIIa), or linear polyenes represented by the following general formula (VIIIa). Two or more different types of these cyclic olefins and linear polyenes may be used.

In general formula (VIa), x and d are 0 or an integer of 1 or more, preferably an integer of 0 or more and 2 or less, more preferably 0 or 1, y and z are 0, 1 or 2, and R ⁸¹ to R ⁹⁹ may be the same or different, and are a hydrogen atom, a halogen atom, an aliphatic hydrocarbon group which is an alkyl group having 1 to 20 carbon atoms or a cycloalkyl group having 3 to 15 carbon atoms, and the number of carbon atoms 6 to 20 aromatic hydrocarbon groups or alkoxy groups, the carbon atom to which R ⁸⁹ and R ⁹⁰ are bonded and the carbon atom to which R ⁹³ is bonded or the carbon atom to which R ⁹¹ is bonded , may be bonded directly or via an alkylene group having 1 to 3 carbon atoms, and when y=z=0, R ⁹⁵ and R ⁹² or R ⁹⁵ and R ⁹⁹ are bonded to each other to form a monocyclic Alternatively, it may form a polycyclic aromatic ring.

In general formula (VIIa), R ¹⁰⁰ and R ¹⁰¹ may be the same or different and represent a hydrogen atom or a hydrocarbon group having 1 to 5 carbon atoms, and f is 1≦f≦18.

In general formula (VIIIa), R ²⁰¹ to R ²⁰⁶ may be the same or different and are a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, and P is a linear chain having 1 to 20 carbon atoms. or branched hydrocarbon groups, which may contain double and/or triple bonds.

As specific examples of the cyclic olefins represented by general formulas (VIa) and (VIIa), compounds described in paragraphs 0037 to 0063 of International Publication No. 2006/118261 can be used.

Specific examples of linear polyenes represented by the general formula (VIIIa) include 1,4-hexadiene, 3-methyl-1,4-hexadiene, 4-methyl-1,4-hexadiene, 5-methyl-1 ,4-hexadiene, 4,5-dimethyl-1,4-hexadiene, 7-methyl-1,6-octadiene, DMDT, 1,3-butadiene, 1,5-hexadiene and the like. Cyclizing polyenes obtained by cyclizing polyenes such as 1,3-butadiene and 1,5-hexadiene may also be used.

A cyclic olefin-based copolymer is represented by a structural unit derived from a linear polyene represented by the general formula (VIIIa), or a cyclic non-conjugated diene represented by the general formula (III) and a general formula (V). When a structural unit derived from a cyclic olefin other than the cyclic olefin [e.g., general formula (VIa), general formula (VIIa)] is included, the content of the structural unit is 1 represented by the general formula (I). Repeating units derived from at least one olefin, repeating units derived from at least one cyclic non-conjugated diene represented by the general formula (III), and repeating units derived from at least one cyclic olefin represented by the general formula (V) It is generally 0.1 to 100 mol %, preferably 0.1 to 50 mol %, relative to the total number of moles of repeating units.

Using the olefin monomer represented by the general formula (I), the cyclic olefin represented by the general formula (VIa) or (VIIa), and the linear polyene represented by the general formula (VIIIa) as copolymerization components As a result, the effects of the present embodiment are obtained, and the solubility of the cyclic olefin copolymer in the solvent is further improved, resulting in good moldability. Among these, cyclic olefins represented by general formula (VIa) or (VIIa) are preferred. Since these cyclic olefins have a rigid ring structure, the elastic modulus of the copolymer and the crosslinked product can be easily maintained, and since they do not contain heterogeneous double bond structures, there is an advantage that the crosslinking can be easily controlled.

The form of the dielectric used in the flexible waveguide according to this embodiment is preferably foam. By using foam as the dielectric, it is possible to reduce the weight of the flexible waveguide while maintaining the transmission efficiency of electric signals even in high frequency bands such as microwaves, millimeter waves, and terahertz waves.

<Dielectric manufacturing method>
The dielectric according to this embodiment can be obtained, for example, by molding a (co)polymer composition into a specific shape. The (co)polymer composition includes, for example, a composition containing 4-methyl-1-pentene (co)polymer and the like, and also includes a composition having only one kind of resin as a constituent material.
The molding apparatus and molding conditions are not particularly limited, and conventionally known molding apparatuses and molding conditions can be employed, but it is preferable to use an extrusion molding apparatus.
Examples of the dielectric molding method according to the present embodiment include injection molding, extrusion molding (film/sheet extrusion, profile extrusion, fiber extrusion, strand extrusion, net extrusion, etc.), vacuum molding, blow molding, press molding, and air pressure. Known thermoforming methods such as molding, calendar molding, bead molding, batch foaming, injection foaming, extrusion foaming, press foaming and foam blow molding can be used. That is, the dielectric according to the present embodiment includes, for example, an injection-molded article, an extrusion-molded article, a vacuum-molded article, a blow-molded article, a press-molded article, a pressure-molded article, a calendar-molded article, a bead-molded article, an injection foamed article, an extruded article, and a Examples include foams, press foams, foam blow moldings, batch foams, and the like.
The dielectric according to this embodiment is preferably an extrusion molded article or an injection molded article.

(Method for preparing (co)polymer composition)
The composition according to the present embodiment is prepared by mixing or melting and kneading each component with a dry blend, a tumbler mixer, a Banbury mixer, a single screw extruder, a twin screw extruder, a high speed twin screw extruder, a hot roll, etc. can do.

(Dielectric molding method)
The dielectric according to this embodiment can be obtained, for example, by molding the composition into a specific shape using a molding device.
A foaming agent may be used when molding the dielectric according to the present embodiment, and examples of the foaming agent include chemical foaming agents and physical foaming agents.
Chemical foaming agents include sodium bicarbonate, ammonium bicarbonate, various carboxylates, sodium borohydride, azodicarbamide, N,N-dinitrosopentamethylenetetramine, P,P-oxybis(benzenesulfonylhydrazide). , azobisisobutyronitrile, p-toluenesulfonyl hydrazide, sodium bicarbonate sodium citrate, and the like.
Physical blowing agents include carbon dioxide, nitrogen, a mixture of carbon dioxide and nitrogen, and the like, all of which can be supplied in a gaseous, liquid, or supercritical state.

It is preferred that the chemical blowing agent is blended with the composition and mixed homogeneously before charging into the extruder.
When carbon dioxide is used as the physical blowing agent, it is preferred that the composition is kneaded and plasticized in the extruder and then injected directly into the extruder.

The expansion ratio of the composition is not particularly limited, and can be determined as appropriate in consideration of various physical properties of the obtained dielectric.

<Conductor>
The material of the conductor is not particularly limited, but examples thereof include conductors such as metals and compositions containing conductors.
Metals used for conductors include, but are not limited to, metals such as copper, silver, gold, alloys, carbon, and the like.

The conductor is preferably one selected from metal coating, tape, fabric and metal plating, but is not limited to these.
The shape of the metal used for the conductor is not particularly limited, but may be pin-like, linear, layered, particulate, scale-like, fibrous, nanotube, or the like.
The conductor includes a metal layer portion arranged so as to cover the outer peripheral portion of the internal dielectric, and it is preferable to use a metal layer with good conductivity.
A tape may be used as the conductor, and among them, a metal tape having a metal layer and a conductive adhesive layer is preferably used. By using the metal tape, it is possible to cope with bending without greatly changing the cross-sectional shape, suppress a decrease in the transmission efficiency of electrical signals, and improve adhesion. . Furthermore, high-precision metal processing is no longer required, and can be supplied at a low manufacturing cost.

<Flexible waveguide 100>
Here, the flexible waveguide 100 according to this embodiment will be described with reference to the drawings.

FIG. 1 shows an example of the structure of a flexible waveguide 100 according to this embodiment. Regarding the rod-shaped dielectric 110, a plurality of conductive linear flat foil yarns as conductors 120 are braided around the rod-shaped dielectric 110 in the longitudinal direction (braided cord). structure). The conductor of this structure is formed, for example, by bundling a plurality of fine metal wires having a circular cross section into a single strand of fine metal wires, and then finishing a braided structure using a required number of strands. By doing so, it is possible to cope with bending without greatly changing the cross-sectional shape, and it is possible to suppress a decrease in the transmission efficiency of electric signals. Furthermore, high-precision metal processing is no longer required, and can be supplied at a low manufacturing cost.

FIG. 2 shows an example of the structure of the flexible waveguide 100 according to this embodiment. Rod-shaped dielectric 110 is configured such that metal plating layer 130 is formed as conductor 120 (plating structure). The plating structure has the same effect as the braided structure, but the electroplating process can be used to finish the fine metal wire strands into a braided structure, which has the advantage of further reducing the number of manufacturing steps. .

Although the embodiments of the present invention have been described above, these are examples of the present invention, and various configurations other than those described above can also be adopted.

It should be noted that the present invention is not limited to the above-described embodiments, and includes modifications, improvements, etc. within the scope of achieving the object of the present invention.

EXAMPLES Next, the present invention will be specifically described with reference to Examples, but the present invention is not limited to these.

(material)
Details of the materials used to fabricate the flexible waveguide are as follows.

Dielectric compound 1: 4-methyl-1-pentene/α-olefin copolymer (manufactured by Mitsui Chemicals, Inc., product name: MX004, content of structural unit (P) derived from 4-methyl-1-pentene : 94 mol%, content of structural unit (Q) derived from α-olefin: 6 mol%), melting point 228°C, fluorine atom content: 0% by mass

Dielectric compound 2: 4-methyl-1-pentene/α-olefin copolymer (content of structural unit (P) derived from 4-methyl-1-pentene: 72.5 mol%, from α-olefin Content of derived structural unit (Q): 27.5 mol%), melting point: none (not observed), fluorine atom content: 0% by mass
300 ml of n-hexane (dried over activated alumina under a dry nitrogen atmosphere) and 450 ml of 4-methyl-1-pentene were placed in a fully nitrogen-substituted 1.5 L SUS autoclave equipped with a stirring blade. Charged at 23°C. The autoclave was charged with 0.75 ml of a 1.0 mmol/ml toluene solution of triisobutylaluminum (TIBAL), and a stirrer was turned.
Next, the autoclave was heated to an internal temperature of 60° C., and pressurized with propylene to a total pressure (gauge pressure) of 0.40 MPa.

Subsequently, 1 mmol of methylaluminoxane and 0.01 mmol of diphenylmethylene (1-ethyl-3-t-butyl-cyclopentadienyl) (2,7-di-t- 0.34 ml of a toluene solution containing butyl-fluorenyl)zirconium dichloride was injected into the autoclave with nitrogen to initiate the polymerization reaction. During the polymerization reaction, the internal temperature of the autoclave was adjusted to 60°C.

60 minutes after the start of polymerization, 5 ml of methanol was injected into the autoclave with nitrogen to stop the polymerization reaction, and then the pressure inside the autoclave was released to atmospheric pressure. After depressurization, acetone was added to the reaction solution while stirring the reaction solution to obtain a polymerization reaction product containing a solvent.

Next, the resulting polymerization reaction product containing the solvent was dried at 100° C. for 12 hours under reduced pressure to obtain 36.9 g of powdery 4-methyl-1-pentene/α-olefin copolymer (for dielectric Compound 2) was obtained.

Dielectric compound 3: copolymer of ethylene and cyclic olefin (tetracyclo[4.4.0.1 ^2,5 .1 ^7,10 ]-3-dodecene) (manufactured by Mitsui Chemicals, general formula (2) Compound represented by, y/x = 65/35), fluorine atom content: 0 mass%

Dielectric compound 4: Cyclic olefin copolymer having a crosslinkable group (content of repeating units (A) derived from one or more olefins represented by general formula (I): 55.7 mol%, general formula Content of repeating unit (B) derived from cyclic non-conjugated diene represented by (III): 8.6 mol%, repeating unit (C) derived from one or more cyclic olefins represented by general formula (V) content: 35.7 mol%), fluorine atom content: 0 mass%
Ethylene and tetracyclo[4.4.0.1 ^2,5 . 1 ^7,10 ]-3-dodecene and 5-vinyl-2-norbornene were terpolymerized. An ethylene/hydrogen mixed gas was blown into the liquid phase from the side of the polymerization vessel, and 0.032 mmol Ti/h of a toluene solution of the transition metal compound (1) synthesized by the method described later and represented by the chemical formula below was added, and methylaluminoxane was added. A toluene solution of 20 mmol·Al/h and tetracyclo[4.4.0.1 ^2,5 . 1 ^7,10 ]-3-dodecene was fed continuously at a rate of 139 mL/h, and a cyclohexane solution of 5-vinyl-2-norbornene and cyclohexane were each fed at a rate of 1 L/h (average residence time: 30 minutes). After 2 hours from the start of raw material feeding, sampling was performed for a specified time, and the resulting polymerization solution was suspended in 1 L of water containing 20 ml of concentrated hydrochloric acid and stirred at 400 rpm for 30 minutes. The aqueous layer was removed, and after distilling off the solvent, the residue was dried under reduced pressure at 130° C. for 10 hours to obtain a cyclic olefin copolymer having a crosslinkable group (dielectric compound 4).

The transition metal compound (1) represented by the above chemical formula was synthesized by the following method.
30 ml of toluene, 1.98 g (10.0 mmol) of 4-t-butylaniline, 1.64 g (11.0 mmol) of 3-phenylsalicylaldehyde and a small amount of p-toluenesulfone as a catalyst were placed in a 100 ml reactor which was sufficiently purged with nitrogen. Acid was added and stirred at reflux for 12 hours. After allowing to cool to room temperature, the catalyst was removed by filtration and the mixture was concentrated under reduced pressure. The residue was purified by recrystallization using methanol to obtain a recrystallized product.
1.65 g (5.00 mmol) of the above recrystallized product and 40 ml of anhydrous diethyl ether were charged into a 100 ml reactor fully purged with nitrogen, and cooled to -78°C. 3.14 ml of n-butyllithium (n-hexane solution, 1.59 M, 5.00 mmol) was added dropwise thereto over 5 minutes, and then the temperature was slowly raised to room temperature. After stirring at room temperature for 2.5 hours, it was gradually added to a slurry of 2.50 ml (1.00 M, 2.50 mmol) of titanium tetrachloride toluene solution cooled to -78°C in anhydrous diethyl ether. After the addition, the mixture was stirred for 17 hours while the temperature was slowly raised to room temperature. The slurry was concentrated under reduced pressure, 25 ml of methylene chloride was added, the slurry was filtered, and the filtrate was concentrated. After the residue was dissolved in 15 ml of ether, the precipitated solid was collected and washed with 15 ml of n-hexane. By drying the obtained solid under reduced pressure, 0.540 g (yield 28%) of transition metal compound (1) was obtained.

Dielectric compound 5: Tetrafluoroethylene polymer (manufactured by Mitsui Chemours Fluoro Products Co., Ltd., product name: Teflon (registered trademark) PTFE), fluorine atom content: 76% by mass

Elastomer: Olefin-based thermoplastic elastomer (manufactured by Mitsui Chemicals, Inc., trade name Milastomer (registered trademark) 5030NS), fluorine atom content: 0% by mass

(Method for measuring physical properties of materials)
Physical properties of each material were measured by the following methods.

[Melting point (Tm)]
The melting point of each material was measured by the following method.
Using a DSC measuring device (DSC220C) manufactured by Seiko Instruments Inc., about 5 mg of a measurement sample is packed in an aluminum pan for measurement, heated to 290 ° C. at 100 ° C./min, held at 290 ° C. for 5 minutes, and then heated for 10 minutes. The melting point (Tm) was calculated from the apex of the crystalline melting peak when the temperature was lowered to -100°C at a rate of °C/min.

[Fluorine Atom Content, Presence or Absence of Fluorine]
The fluorine atom content in each material was measured by the following method.
Each material was weighed and combusted in the combustion tube of the analyzer. The gas generated by combustion was absorbed by the solution to obtain an absorption liquid. A portion of the absorption liquid was then analyzed by ion chromatography to determine the proportion of fluorine atoms in the dielectric. At this time, when the ratio of fluorine atoms in the detected molecule is 1% by mass or less when the entire dielectric is 100% by mass, the "presence or absence of fluorine: no" : Yes. Conditions in each step are as follows.

(Combustion/absorption conditions)
System: AQF-2100, GA-210 (manufactured by Mitsubishi Chemical)
Electric furnace temperature: Inlet 900°C, Outlet 1000°C
Gas: Ar/ _O2 200 mL/min
_O2 400 mL/min
Absorption liquid: solvent H ₂ O ₂ 90 μg/mL,
Internal standard P 4 μg/mL or Br 8 μg/mL
Absorbing liquid volume: 20 mL

(Ion chromatography analysis conditions)
System: ICS1600 (manufactured by DIONEX)
_Mobile phase: 2.7 mmol/L _Na2CO3 /0.3 mmol/L _NaHCO3
Flow rate: 1.50 mL/min
Detector: Electrical conductivity detector Injection volume: 20 μL

(Manufacturing method)
The method of manufacturing the flexible waveguides of each example and comparative example will be described in detail.

[Example 1]
Dielectric compound 1 was extruded with a 45 mm extruder (set temperature: 280° C.) through an elliptical die with a long diameter of 24 mm and a short diameter of 15 mm in cross section to produce a dielectric.
A flexible waveguide was fabricated by electroplating the surface of this dielectric and depositing copper as a conductor so that the thickness of the plated layer was 200 μm.

[Example 2] to [Example 4]
In Example 2, the same method as in Example 1 was used, except that instead of the dielectric compound 1 in Example 1, a mixture of dielectric compound 2 and elastomer in the blending amounts shown in Table 1 was used. made flexible waveguides respectively.
In Examples 3 and 4, flexible conductors were fabricated in the same manner as in Example 1, except that dielectric compound 3 or dielectric compound 4 was used in place of dielectric compound 1 in Example 1. I made each wave tube.

[Example 5]
4-methyl-1-pentene-based polymer MX004 (manufactured by Mitsui Chemicals, Inc., MFR: 23, dielectric compound 1) per 100 parts by mass, chemical blowing agent Hydrocerol (trademark) CF (manufactured by Clariant) as a blowing agent 2 parts by mass was added, a dielectric was produced in the same manner as in Example 1, and the surface of this dielectric was electroplated to produce a flexible waveguide.

[Example 6]
A flexible waveguide was produced in the same manner as in Example 1, except that dielectric compound 1 was injection molded under the following conditions to produce a dielectric.
(Injection molding conditions)
2 parts by mass of a chemical foaming agent Hydrocerol (trademark) CF (manufactured by Clariant) was added as a foaming agent to 100 parts by mass of dielectric compound 1, and the cylinder temperature of the injection molding machine was set to 280°C and the mold temperature was set to 280°C. was set to 60° C., injection molding was carried out using an elliptical mold having a major diameter of 25 mm and a minor diameter of 15 mm to produce a dielectric.

[Example 7]
A flexible waveguide was produced in the same manner as in Example 6, except that dielectric compound 2 was used.

[Comparative Example 1]
An elliptical dielectric with a major diameter of 24 mm and a minor diameter of 15 mm was produced from a round bar of the dielectric compound 5 by a cutting method, and the surface of this dielectric was electroplated in the same manner as in Example 1, A flexible waveguide was fabricated by depositing a metal plating of copper as a conductor.
At this time, the flexible waveguide was not sufficiently plated to the dielectric.

(Measuring method)
A detailed description will be given of a method of measuring the flexible waveguides of the fabricated examples and comparative examples.

[Relative permittivity, dielectric loss]
The relative permittivity and dielectric loss of each dielectric were measured for the flexible waveguides obtained in each example and comparative example.
The flexible waveguide obtained in each example and comparative example was attached to a cylindrical cavity resonator, and measured by a cylindrical cavity resonator method (TM010 method) according to JIS C2565-1992 at a temperature of 23°C and a measurement frequency of 10 GHz. The dielectric constant and dielectric loss were measured under the conditions of Table 1 shows the results.

[density]
The density of each dielectric obtained in each example and comparative example was measured according to ASTM D1505.

The dielectric constants and dielectric losses of the flexible waveguides of Examples 1 to 7 are as shown in Table 1, and even in high frequency bands such as microwaves, the decrease in the transmission efficiency of electrical signals is suppressed, and the It has been found that one has been obtained which functions satisfactorily as a flexible waveguide.
On the other hand, in the flexible waveguide of Comparative Example 1, the plating was not sufficiently adhered to the dielectric, and the flexible waveguide could not function satisfactorily. Also, the flexible waveguide of Comparative Example 1 was not sufficiently flexible as compared with the flexible waveguides of Examples.

As described above, according to the present invention, it is possible to obtain a flexible waveguide that suppresses a decrease in transmission efficiency of electric signals in a high frequency band such as microwaves and that has improved flexibility.
Furthermore, even if the waveguide has a bent portion, it can be easily accommodated, and the material cost, processing cost, weight, and process load can be reduced.

This application claims priority based on Japanese Patent Application No. 2021-203092 filed on December 15, 2021, and the entire disclosure thereof is incorporated herein.

100 flexible waveguide 110 dielectric 120 gas outlet 130 metal plating

Claims

A flexible waveguide comprising a rod-shaped dielectric and a conductor covering the outer surface of the dielectric,
A flexible waveguide, wherein the dielectric satisfies (a) and (b) below.
(a) Density of 1.50 g/cm 3 or less (b) Relative permittivity of 2.3 or less measured at a frequency of 10 GHz and dielectric loss of 0.0013 or less measured at a frequency of 10 GHz
The flexible waveguide according to claim 1, wherein the content of fluorine atoms in the dielectric is 1% by mass or less when the entire dielectric is 100% by mass.
The flexible waveguide according to claim 1 or 2, wherein said dielectric comprises 4-methyl-1-pentene (co)polymer.
4. The flexible waveguide according to claim 3, wherein said 4-methyl-1-pentene (co)polymer satisfies (i) and (ii) below.
(i) 15 to 100 mol% of the structural unit (P) derived from 4-methyl-1-pentene
(ii) 0 to 85 mol% of structural units (Q) derived from at least one selected from α-olefins having 2 to 20 carbon atoms (excluding 4-methyl-1-pentene);
5. The flexible waveguide according to claim 3, wherein the 4-methyl-1-pentene (co)polymer satisfies (iii) to (v) below.
(iii) 60 to 100 mol% of the structural unit (P) derived from 4-methyl-1-pentene
(iv) 0 to 40 mol% of structural units (Q) derived from at least one selected from α-olefins having 2 to 20 carbon atoms (excluding 4-methyl-1-pentene) (v) DSC The melting point (Tm) measured at is in the range of 200 to 250 ° C.
The 4-methyl-1-pentene (co)polymer is a 4-methyl-1-pentene/α-olefin copolymer,
5. The flexible waveguide according to claim 3, wherein the 4-methyl-1-pentene/α-olefin copolymer satisfies (vi) to (viii) below.
(vi) 15 to 99 mol% of the structural unit (P) derived from 4-methyl-1-pentene
(vii) The structural unit (Q) derived from at least one selected from α-olefins having 2 to 20 carbon atoms (excluding 4-methyl-1-pentene) is 1 to 85 mol% (viii) DSC Melting point (Tm) less than 200°C or no melting point observed
the dielectric is
The 4-methyl-1-pentene (co)polymer, and thermoplastic resin (excluding 4-methyl-1-pentene (co)polymer) or elastomer,
The content of the thermoplastic resin or elastomer in the dielectric is 1 part by mass or more and 50 parts by mass or less (however, the total amount of the 4-methyl-1-pentene (co)polymer and the thermoplastic resin or elastomer is 100 parts by mass. The flexible waveguide according to any one of claims 3 to 6, which is a mass part.
The flexible waveguide according to any one of claims 1 to 7, wherein the dielectric contains a cyclic olefin copolymer having a structure represented by the following general formula (2).

[In general formula (2), x and y represent copolymerization ratios and are real numbers satisfying 0/100≦y/x≦95/5. x, y are on a molar basis. n indicates the substitution number of the substituent Q and is a real number of 0≦n≦2. R a is a 2+n-valent group selected from the group consisting of hydrocarbon groups having 2 to 20 carbon atoms. R b is a hydrogen atom or a monovalent group selected from the group consisting of hydrocarbon groups having 1 to 10 carbon atoms. R c is a tetravalent group selected from the group consisting of hydrocarbon groups having 2 to 10 carbon atoms. Q is COOR d (R d is a hydrogen atom or a monovalent group selected from the group consisting of hydrocarbon groups having 1 to 10 carbon atoms). Each of R a , R b , R c and Q may be one kind, or may be two or more kinds in an arbitrary ratio. ]
the dielectric is
(A) one or more olefin-derived repeating units represented by the following general formula (I);
(B) a repeating unit derived from a cyclic non-conjugated diene represented by the following general formula (III);
(C) a repeating unit derived from one or more cyclic olefins represented by the following general formula (V);
A cyclic olefin copolymer having a crosslinkable group containing
In the cyclic olefin copolymer, the content of the repeating unit (B) derived from a cyclic non-conjugated diene is 5 mol% or more when the total number of moles of the repeating units in the cyclic olefin copolymer is 100 mol%. The flexible waveguide according to any one of claims 1 to 8, which is 36 mol% or less.

[In general formula (I), R 300 represents a hydrogen atom or a linear or branched hydrocarbon group having 1 to 29 carbon atoms. ]

[In general formula (III), u is 0 or 1, v is 0 or 1, w is 0 or 1, and R 61 to R 76 and R a1 and R b1 may be the same or different; A hydrogen atom, a halogen atom, an alkyl group having 1 to 20 carbon atoms, a halogenated alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 15 carbon atoms, or a cycloalkyl group having 6 to 20 carbon atoms. an aromatic hydrocarbon group, R 104 is a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, t is a positive integer of 0 to 10, R 75 and R 76 are It may form a ring or polycycle. ]

[In general formula (V), u is 0 or 1, v is 0 or 1, w is 0 or 1, and R 61 to R 78 and R a1 and R b1 may be the same or different. A hydrogen atom, a halogen atom, an alkyl group having 1 to 20 carbon atoms, a halogenated alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 15 carbon atoms, or a cycloalkyl group having 6 to 20 carbon atoms. It is an aromatic hydrocarbon group, and R 75 to R 78 may combine with each other to form a monocyclic or polycyclic ring. However, when u and v are both 0, at least one of R 67 to R 70 and R 75 to R 78 is a substituent other than a hydrogen atom. ]
The flexible waveguide according to any one of claims 1 to 9, wherein said dielectric is foam.
The flexible waveguide according to any one of claims 1 to 10, wherein the conductor is any one selected from metal coating, tape, fabric and metal plating.