WO2023112921A1 - 可撓性導波管 - Google Patents

可撓性導波管 Download PDF

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Publication number
WO2023112921A1
WO2023112921A1 PCT/JP2022/045885 JP2022045885W WO2023112921A1 WO 2023112921 A1 WO2023112921 A1 WO 2023112921A1 JP 2022045885 W JP2022045885 W JP 2022045885W WO 2023112921 A1 WO2023112921 A1 WO 2023112921A1
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Prior art keywords
methyl
pentene
dielectric
carbon atoms
group
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English (en)
French (fr)
Japanese (ja)
Inventor
智章 伊藤
琢夫 浅見
和人 杉山
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Mitsui Chemicals Inc
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Mitsui Chemicals Inc
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01P—WAVEGUIDES; RESONATORS, LINES, OR OTHER DEVICES OF THE WAVEGUIDE TYPE
    • H01P3/00—Waveguides; Transmission lines of the waveguide type
    • H01P3/12—Hollow waveguides
    • H01P3/127—Hollow waveguides with a circular, elliptic, or parabolic cross-section
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01P—WAVEGUIDES; RESONATORS, LINES, OR OTHER DEVICES OF THE WAVEGUIDE TYPE
    • H01P3/00—Waveguides; Transmission lines of the waveguide type
    • H01P3/12—Hollow waveguides
    • H01P3/14—Hollow waveguides flexible

Definitions

  • 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.
  • 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.
  • 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.
  • 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.
  • the following flexible waveguide is provided.
  • 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.
  • the 4-methyl-1-pentene (co)polymer is a 4-methyl-1-pentene/ ⁇ -olefin copolymer
  • 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.
  • 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).
  • 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 repeating units in the cyclic olefin copolymer is 100 mol%.
  • R 300 represents a hydrogen atom or a linear or branched hydrocarbon group having 1 to 29 carbon atoms.
  • 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;
  • 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.
  • 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.
  • the conductor is any one selected from metal coating, tape, fabric and metal plating.
  • 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.
  • 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.
  • polyfluoroethylene-based fiber is exemplified as a flexible dielectric material.
  • 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.
  • 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.
  • 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.
  • the shape of the dielectric used in the flexible waveguide according to this embodiment is rod-like.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • dielectrics 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.
  • 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 ⁇ -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 ⁇ -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 ⁇ -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 ⁇ -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.
  • the ⁇ -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.
  • Structural units (Q) derived from at least one selected from ⁇ -olefins having 2 to 20 carbon atoms (excluding 4-methyl-1-pentene) are 0 to 85 mol% of the above structural units
  • 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.
  • 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.
  • the melting point (Tm) measured at is in the range of 200 to 250 ° C.
  • 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 %.
  • 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 %.
  • 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%.
  • 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.
  • 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.
  • 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.
  • the ⁇ -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 ⁇ -olefins may be used singly or in combination of two or more thereof.
  • Such 4-methyl-1-pentene/ ⁇ -olefin copolymers are available from Mitsui Chemicals, Inc., TPX (registered trademark) RT18, RT31, DX845, DX231, DX350, DX820, MX004, MX002, MX002O, DX310. etc.
  • the 4-methyl-1-pentene (co)polymer is a 4-methyl-1-pentene/ ⁇ -olefin copolymer.
  • a 4-methyl-1-pentene/ ⁇ -olefin copolymer (A), which is a coalescence (A) and satisfies (vi) to (viii) below, can be mentioned.
  • the structural unit (Q) derived from at least one selected from ⁇ -olefins having 2 to 20 carbon atoms (excluding 4-methyl-1-pentene) is 1 to 85 mol%
  • 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 %.
  • 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 %.
  • the structural unit (Q) 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 %.
  • 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%.
  • 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.
  • 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.
  • 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.
  • the ⁇ -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 ⁇ -olefins may be used singly or in combination of two or more thereof.
  • 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.
  • the above 4-methyl-1-pentene (co)polymer, thermoplastic resin (excluding 4-methyl-1-pentene (co)polymer) or elastomer 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.).
  • the 4-methyl-1-pentene/ ⁇ -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 ⁇ -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 ⁇ -olefins.
  • the 4-methyl-1-pentene/ ⁇ -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 ⁇ -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 %.
  • the ratio of the structural unit (Q) derived from the ⁇ -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%.
  • 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.
  • the flexibility and lightness of the flexible waveguide according to the present invention can be well balanced. .
  • Examples of ⁇ -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 ⁇ -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 ⁇ -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 thermoplastic resin or elastomer
  • resin or elastomer thermoplastic resin or elastomer
  • 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, styren
  • thermoplastic resins and elastomers may be used singly or in combination of two or more.
  • -1-pentene ethylene/ ⁇ -olefin copolymer, propylene/ ⁇ -olefin copolymer, 1-butene/ ⁇ -olefin copolymer, ethylene/vinyl acetate copolymer, styrene elastomer, rosin resin, Terpene resin, petroleum resin, ethylene/ ⁇ -olefin/diene copolymer, propylene/ ⁇ -olefin/diene copolymer, 1-butene/ ⁇ -olefin/diene copolymer, polybutadiene rubber, polyisoprene rubber, neoprene rubber, nitrile rubber, butyl rubber, polyisobutylene rubber, and silicone rubber.
  • rosin-based resin examples include natural rosin, polymerized rosin, modified rosin modified with maleic acid, fumaric acid, (meth)acrylic acid, and rosin derivatives.
  • rosin derivatives examples 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.
  • terpene-based resin examples include resins composed of ⁇ -pinene, ⁇ -pinene, limonene, dipentene, terpenephenol, terpene alcohol, terpene aldehyde, etc. ⁇ -pinene, ⁇ -pinene, limonene, dipentene, etc. , ⁇ -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/ ⁇ -methylstyrene copolymer petroleum resin, ⁇ -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
  • 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.
  • rosin-based resins 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.
  • 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
  • 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).
  • 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.
  • Rd is a hydrogen atom or a monovalent group selected from the group consisting of hydrocarbon groups having 1 to 10 carbon atoms.
  • R a , R b , R c and Q may be one kind, or may be two or more kinds in an arbitrary ratio.
  • the structure of R a may be used alone or in combination of two or more.
  • R b examples 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.
  • R a is as defined above.
  • 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.
  • 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.
  • 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 ⁇ -olefins and cyclic olefins
  • X Ring-opening polymers or hydrogenated products thereof
  • Y Vinyl alicyclic hydrocarbon polymers
  • Z Other polymers explain.
  • W A copolymer of ethylene or an ⁇ -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 ⁇ -olefin having 3 to 30 carbon atoms and structural units derived from a cyclic olefin.
  • 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.
  • 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 ⁇ -olefin are structural units derived from ethylene or linear or branched ⁇ -olefins having 3 to 30 carbon atoms as described below.
  • 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.
  • ethylene is preferred.
  • Two or more of these structural units derived from ethylene or ⁇ -olefin may be contained within a range that does not impair the effects of the present invention.
  • 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.
  • u is 0 or 1
  • v is 0 or a positive integer
  • w is 0 or 1.
  • the ring represented by w is a 6-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. .
  • alkyl groups include methyl, ethyl, propyl, isopropyl, amyl, hexyl, octyl, decyl, dodecyl, and octadecyl.
  • 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.
  • 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.
  • 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.
  • x and d are 0 or 1 or more positive integers, and y and z are 0, 1 or 2.
  • 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.
  • R95 and R92 or R95 and R99 may be bonded to each other to form a monocyclic or polycyclic aromatic ring.
  • 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.
  • 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 -).
  • R95 and R92 or R95 and R99 may combine with each other to form a monocyclic or polycyclic aromatic ring.
  • R 95 and R 92 may combine with each other to form a monocyclic or polycyclic aromatic ring.
  • cyclic olefin represented by general formula (10) has the following structure.
  • 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-docosen
  • 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.
  • 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.
  • the "(W) copolymer of ethylene or ⁇ -olefin and cyclic olefin” includes ethylene and tetracyclo[4.4.0.1 2,5 . 1 7,10 ]-3-dodecene is preferred.
  • 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.
  • 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. .
  • 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.
  • 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 ⁇ -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 dimethyl
  • 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.
  • 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.
  • vinyl compounds include vinyl aromatic compounds and vinyl alicyclic hydrocarbon compounds.
  • vinyl aromatic compounds include styrene, ⁇ -methylstyrene, ⁇ -ethylstyrene, ⁇ -propylstyrene, ⁇ -isopropylstyrene, ⁇ -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.
  • vinylcyclohexanes such as vinylcyclohexane and 3-methylisopropenylcyclohexane
  • Copolymerizable monomers include ⁇ -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, me
  • 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.
  • 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.
  • 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.
  • (W) a copolymer of ethylene or an ⁇ -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.
  • dielectric 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.
  • R 300 represents a hydrogen atom or a linear or branched hydrocarbon group having 1 to 29 carbon atoms.
  • 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;
  • 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.
  • 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.
  • R 67 to R 70 and R 75 to R 78 is a substituent other than a hydrogen atom.
  • 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.
  • 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 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.
  • 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. .
  • 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%.
  • 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.
  • 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.
  • R 300 represents a hydrogen atom or a linear or branched hydrocarbon group having 1 to 29 carbon atoms.
  • 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.
  • 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).
  • a cyclic non-conjugated diene represented by the following general formula (IIIa) corresponding to the above general formula (III) is used.
  • 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.
  • 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
  • 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).
  • a cyclic olefin monomer represented by the following general formula (Va) corresponding to the above general formula (V) is used.
  • 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; .
  • 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.
  • 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 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.
  • 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.
  • 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
  • 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.
  • 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.
  • 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).
  • a structural unit derived from a cyclic olefin other than the cyclic olefin e.g., general formula (VIa), general formula (VIIa)]
  • the content of the structural unit is 1 represented by the general formula (I).
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • the chemical blowing agent is blended with the composition and mixed homogeneously before charging into the extruder.
  • 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.
  • the material of the conductor is not particularly limited, but examples thereof include conductors such as metals and compositions containing conductors.
  • 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.
  • FIG. 1 shows an example of the structure of a flexible waveguide 100 according to this embodiment.
  • 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. .
  • Dielectric compound 1 4-methyl-1-pentene/ ⁇ -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 ⁇ -olefin: 6 mol%), melting point 228°C, fluorine atom content: 0% by mass
  • Dielectric compound 2 4-methyl-1-pentene/ ⁇ -olefin copolymer (content of structural unit (P) derived from 4-methyl-1-pentene: 72.5 mol%, from ⁇ -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.
  • TIBAL triisobutylaluminum
  • 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 .
  • 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.
  • 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
  • Tm Melting point
  • 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.
  • 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 ⁇ m.
  • 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.
  • 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.
  • chemical blowing agent Hydrocerol trademark
  • Clariant trademark of Clariant
  • 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.
  • Hydrocerol trademark
  • Example 7 A flexible waveguide was produced in the same manner as in Example 6, except that dielectric compound 2 was used.
  • 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.
  • Measurement method A detailed description will be given of a method of measuring the flexible waveguides of the fabricated examples and comparative examples.
  • 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.
  • 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.
  • 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.

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Publication number Priority date Publication date Assignee Title
JP2015185858A (ja) * 2014-03-20 2015-10-22 福井県 可撓性導波管
WO2017033668A1 (ja) * 2015-08-26 2017-03-02 ソニーセミコンダクタソリューションズ株式会社 コネクタ装置及び通信装置
CN207743385U (zh) * 2017-04-28 2018-08-17 广州司南天线设计研究所有限公司 空间立体移相器
JP2020010234A (ja) * 2018-07-10 2020-01-16 オリンパス株式会社 可撓性導波管、可撓性導波管の製造方法および可撓性導波管を用いる映像伝送装置

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JPS5399954A (en) * 1977-02-14 1978-08-31 Junkosha Co Ltd Conductor line
JPS5875301A (ja) * 1982-07-09 1983-05-07 Junkosha Co Ltd 伝送線路
JP2020117651A (ja) * 2019-01-28 2020-08-06 Ｍｃｐｐイノベーション合同会社 ミリ波モジュール及びその構成部品

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2015185858A (ja) * 2014-03-20 2015-10-22 福井県 可撓性導波管
WO2017033668A1 (ja) * 2015-08-26 2017-03-02 ソニーセミコンダクタソリューションズ株式会社 コネクタ装置及び通信装置
CN207743385U (zh) * 2017-04-28 2018-08-17 广州司南天线设计研究所有限公司 空间立体移相器
JP2020010234A (ja) * 2018-07-10 2020-01-16 オリンパス株式会社 可撓性導波管、可撓性導波管の製造方法および可撓性導波管を用いる映像伝送装置

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