JP2020117651A - Millimeter wave module and its component part - Google Patents

Abstract

To provide a millimeter wave module that shows low attenuation property and has very low frequency dependency in a high frequency region over 30 GHz and its component part.SOLUTION: A millimeter wave module having a component obtained by molding a cyclic polyolefin, in which the cyclic polyolefin is made of a hydrogenated block copolymer that a hydrogenated body of a block copolymer containing at least one kind of an aromatic vinyl monomer unit and at least one kind of conjugated diene monomer, the hydrogenated block copolymer has a hydrogenated aromatic vinyl polymer block unit and a hydrogenated conjugated diene polymer block unit, the hydrogenated copolymer has at least two hydrogenated aromatic vinyl polymer block units, and has at least one hydrogenated conjugated diene polymer block unit.SELECTED DRAWING: None

Description

The present invention relates to a millimeter wave module including a circuit for high-speed and large-capacity communication using millimeter waves and peripheral components thereof, and a millimeter wave such as a transmitting/receiving antenna film, a millimeter wave radar cover, a connector, a housing, and a millimeter wave receiving/transmitting circuit board. Regarding module components.

Higher communication speeds and larger capacities have been advancing year by year. For example, current mobile phones using microwaves have reached the fourth generation (4G) of large capacity, high speed data communication. In the next-generation ultra-high-speed communication standard (fifth generation, 5G), radio communication with a frequency of more than 30 GHz is suitable for wide band, large capacity, and short-distance transmission, so higher frequency radio waves such as millimeter waves are used. ..
Further, millimeter waves, which are high-frequency radio waves, are suitable for rear-end collision prevention radars and the like because of their high straightness and are being adopted.

On the other hand, high frequency radio waves in the millimeter wave region are known to be reduced in the materials used for related parts such as circuits, antennas, sensors, covers, connectors, and casings due to the dielectric loss of those materials, which improves communication efficiency. Even if it is not lowered, the material used for the above-mentioned related parts is required to have a property of low dielectric constant, particularly low dielectric loss.
As an example of a millimeter wave module, particularly a millimeter wave communication module, a millimeter wave radar module includes a millimeter wave transmitting/receiving antenna, a radome, a housing, a connector, a radar board, a circuit board, a casing, and the like. In addition, the mobile phone includes an antenna, a receiver, a circuit board, and the like.

Resin molded parts and resin films are often used in these modules. Specifically, parts made of various kinds of resin such as antenna films, covers, connectors, casings, circuit boards, etc. Is used.
By the way, if the millimeter wave transmission of this resin component is insufficient or the millimeter wave is attenuated midway, noise may occur in the incoming and outgoing signal, the strength may decrease, and the receiving and sending accuracy may decrease. , It becomes impossible to obtain sufficient performance as a communication device or radar.
For this reason, there is a strong demand for a material having a small radio wave loss in the millimeter wave region of 30 GHz or higher.

Conventionally, ceramics have been widely used for such applications, but since ceramics are difficult to process and it is difficult to make them thin and lightweight, it is proposed to change the material to a polymer material that is inexpensive and easy to process. ing.
For example, Patent Document 1 discloses a method of manufacturing a dielectric waveguide line by using polytetrafluoroethylene having excellent dielectric properties and heating at high temperature.
Patent Document 2 discloses a method of manufacturing an inexpensive module by providing a circuit on a film-shaped polyimide resin.
Patent Document 3 uses a method of manufacturing a millimeter-wave antenna with a stable dielectric constant by using a specific thermoplastic liquid crystal polymer.
Patent Document 4 discloses a low dielectric resin film in which an intermediate layer of a multilayer film is a composite of a thermoplastic liquid crystal polymer and polyester.
Patent Document 5 discloses a low dielectric constant film in which fine pores are dispersedly formed in a polymer material.

Japanese Unexamined Patent Publication No. 2018-061249 JP 2002-151915 A Japanese Unexamined Patent Publication No. 2012-077117 JP, 2005-193657, A JP, 2018-021172, A

However, the method of Patent Document 1 requires a very complicated heating step, and it is difficult to reduce the wall thickness, and it is difficult to secure a low dielectric loss particularly in a high frequency region.
In the method of Patent Document 2, the high frequency characteristics are significantly inferior to those of polytetrafluoroethylene, and the hygroscopicity is large, so that the high frequency characteristics are extremely deteriorated by the moisture absorption.
The method of Patent Document 3 does not describe the dielectric characteristics in the ultrahigh frequency region, and the dielectric loss is not sufficiently low even within the scope of the invention.
Patent Document 4 does not describe the dielectric characteristics in the millimeter wave region.
Even with the method of Patent Document 5, the dielectric loss in the high frequency region is not sufficiently low.

Among the 5G radio waves, WiGiG, which is a standard for short-distance communication, uses 60 GHz, and millimeter wave radar uses 77 GHz. Ultra high frequency radio waves are particularly used, and high millimeter wave transparency and low attenuation characteristics are required. However, in the conventional technology, the radio wave loss tends to increase with an increase in frequency, and components for millimeter wave communication and radar that meet such requirements have not yet been achieved.

The present invention has been made in view of the above problems, and an object of the present invention is to provide a millimeter wave module that exhibits low attenuation characteristics in a high frequency region of more than 30 GHz and has extremely low frequency dependence, and its components.

As a result of intensive studies, the present inventor has found that a module component formed by molding a hydrogenated block copolymer having a specific structure has excellent loss characteristics without frequency dependence in a region of 30 GHz or more, The present invention has been completed.
That is, the present invention has the following configurations.

[1] A millimeter-wave module having a component formed by molding and processing a cyclic polyolefin, wherein the cyclic polyolefin contains hydrogen of a block copolymer containing at least one aromatic vinyl monomer unit and at least one conjugated diene monomer unit. A hydrogenated block copolymer which is a hydrogenated block copolymer, which is a hydrogenated aromatic vinyl polymer block unit which is a hydrogenated polymer block comprising the aromatic vinyl monomer unit, and the conjugated diene monomer unit. A hydrogenated conjugated diene polymer block unit which is a hydrogenated product of the polymer block, wherein the hydrogenated block copolymer has at least two hydrogenated aromatic vinyl polymer block units, and the hydrogenated conjugated diene polymer block A millimeter wave module having at least one unit.

[2] The hydrogenated aromatic vinyl polymer block unit has a hydrogenation level of 90% or more, and the hydrogenated conjugated diene polymer block unit has a hydrogenation level of 95% or more. Millimeter wave module.
[3] The millimeter wave module according to [1] or [2], wherein the hydrogenated aromatic vinyl polymer block unit is made of hydrogenated polystyrene, and the content of the cyclic polyolefin in the cyclic polyolefin is 50 to 99 mol %.
[4] The millimeter wave module according to [1] or [2], wherein the hydrogenated conjugated diene polymer block unit is made of hydrogenated polybutadiene, and the content of the cyclic polyolefin in the cyclic polyolefin is 1 to 50 mol %.
[5] A transmitting/receiving antenna film, which is a component made of the cyclic polyolefin that constitutes the millimeter-wave module according to any one of [1] to [4].
[6] A component made of the cyclic polyolefin constituting the millimeter wave module according to any one of [1] to [4], and a millimeter wave module configuration selected from a millimeter wave radar cover, a connector, and a housing. parts.
[7] A circuit board for millimeter wave transmission/reception, which is a component made of the cyclic polyolefin that constitutes the millimeter wave module according to any one of [1] to [4].

Since the millimeter wave module according to the present invention uses a component made of a specific cyclic polyolefin, it exhibits a characteristic that the dielectric loss with respect to millimeter waves is low. Therefore, the film for the antenna of the radio wave transmission/reception system, the circuit board, the connector, the device cover, the sealing material, and the like, which are the components constituting the millimeter wave module, can be manufactured using the cyclic polyolefin. Therefore, the millimeter-wave module according to the present invention can be used as a module for a front or rear surveillance radar of an automobile, and also as a module in a short-distance communication system such as Wifi or a communication base station, which causes a communication error. This can contribute to reduction, improvement in communication speed, accuracy, and increase in capacity.

Embodiments of the present invention will be described in detail below. In addition, in the present specification, when the expression "to" is used, it is used as an expression including numerical values or physical properties before and after the expression.

The present invention relates to a millimeter wave module having a component obtained by molding and processing a cyclic polyolefin, wherein the cyclic polyolefin comprises a block copolymer containing at least one aromatic vinyl monomer unit and at least one conjugated diene monomer unit. A hydrogenated product (hereinafter referred to as “hydrogenated block copolymer”), which is a hydrogenated product of a polymer block (hereinafter referred to as “hydrogenated aromatic vinyl polymer”) including the aromatic vinyl monomer unit. Block unit”) and a hydrogenated polymer block consisting of the conjugated diene monomer unit (hereinafter, referred to as “hydrogenated conjugated diene polymer block unit”). A millimeter wave module having at least two hydrogenated aromatic vinyl polymer block units and at least one hydrogenated conjugated diene polymer block unit.

<Cyclic polyolefin>
As mentioned above, the cyclic polyolefin of the present invention is a resin comprising the hydrogenated block copolymer.
The hydrogenated block copolymer has the hydrogenated aromatic vinyl polymer block unit and the hydrogenated conjugated diene polymer block unit.
The hydrogenated block copolymer has at least two hydrogenated aromatic vinyl polymer block units and at least one hydrogenated conjugated diene polymer block unit.
As will be described later, the term “block” refers to a polymerized segment of a copolymer, which represents microlayer separation from a polymerized segment that is structurally or compositionally different in the copolymer, as described later. Thus, for example, "having at least two block units" means having at least two polymerized segments of the copolymer that represent microlayer separation from polymerized segments that are structurally or compositionally different within the hydrogenated block copolymer. Say that.

The aromatic vinyl monomer that is a raw material of the aromatic vinyl monomer unit is a monomer represented by the general formula (1).

ここでＲは水素又はアルキル基、Ａｒはフェニル基、ハロフェニル基、アルキルフェニル基、アルキルハロフェニル基、ナフチル基、ピリジニル基、またはアントラセニル基である。

Here, R is hydrogen or an alkyl group, Ar is a phenyl group, a halophenyl group, an alkylphenyl group, an alkylhalophenyl group, a naphthyl group, a pyridinyl group, or an anthracenyl group.

The alkyl group has 1 to 6 carbon atoms which may be mono- or multi-substituted with a functional group such as a halo group, a nitro group, an amino group, a hydroxy group, a cyano group, a carbonyl group, and a carboxyl group. Including.
Ar is preferably a phenyl group or an alkylphenyl group, more preferably a phenyl group.
Examples of the aromatic vinyl monomer include styrene, α-methylstyrene, vinyltoluene (including all isomers, especially p-vinyltoluene), ethylstyrene, propylstyrene, butylstyrene, vinylbiphenyl, vinylnaphthalene, vinylanthracene. (All isomers), and mixtures thereof.

The conjugated diene monomer is not particularly limited as long as it is a monomer having two conjugated double bonds.
Examples of the conjugated diene monomer include 1,3-butadiene, 2-methyl-1,3-butadiene, 2-methyl-1,3 pentadiene, isoprene and its similar compounds, and a mixture thereof.

The polybutadiene, which is a polymer of 1,3-butadiene, has either a 1,2-configuration which gives an equivalent of 1-butene repeating units upon hydrogenation or a 1,4-configuration which gives an equivalent of ethylene repeating units upon hydrogenation. Can be included.

The hydrogenated product of the polymerizable block composed of the aromatic vinyl monomer and the conjugated diene monomer containing 1,3-butadiene is included in the hydrogenated block copolymer used in the present invention. Preferably, the hydrogenated block copolymer is a block copolymer without functional groups.
In addition, "having no functional group" means that there is no functional group in the block copolymer, that is, a group containing an element other than carbon and hydrogen.

A preferred example of the hydrogenated aromatic vinyl polymer block unit is hydrogenated polystyrene, and a preferred example of the hydrogenated conjugated diene polymer block unit is hydrogenated polybutadiene.
And, as a preferable embodiment of the hydrogenated block copolymer, a hydrogenated triblock or pentablock copolymer of styrene and butadiene can be mentioned, and it is preferable that it does not contain any other functional group or structural modifier.
A "block" is defined as a polymerized segment of a copolymer that represents a microlayer separation from a structurally or compositionally different polymerized segment of the copolymer. Microlayer separation occurs because the polymerized segments are immiscible in the block copolymer.
Micro-layer separation and block copolymers have been extensively discussed in "Block Polymers-Designer Soft Materials", PHYSICS TODAY, February 1999, pp. 32-38.

The content of the hydrogenated aromatic vinyl polymer block unit is preferably 50 to 99 mol%, more preferably 60 to 90 mol% with respect to the cyclic polyolefin.
If the ratio of the hydrogenated aromatic vinyl polymer block units is at least the above lower limit, the rigidity will not be reduced, and if it is at most the above upper limit, the brittleness will not be deteriorated.

Further, the content of the hydrogenated conjugated diene polymer block unit is preferably 1 to 50 mol%, more preferably 10 to 40 mol% with respect to the cyclic polyolefin.
When the ratio of the hydrogenated conjugated diene polymer block unit is at least the above lower limit, brittleness does not deteriorate, and when it is at most the above upper limit, rigidity does not decrease.

As described above, the polyolefin according to the present invention is a “cyclic polyolefin”, and the “cyclic” means that the hydrogenated aromatic vinyl polymer block unit has an alicyclic ring produced by hydrogenation of an aromatic ring. Refers to the formula structure.

The hydrogenated block copolymers of the present invention are triblock, multiblock, tapered blocks such as SBS, SBSBS, SIS, SISIS, and SISBS (where S is polystyrene, B is polybutadiene and I is polyisoprene). , And block copolymers, including star block copolymers.

The hydrogenated block copolymers of the present invention include a segment of aromatic vinyl polymer at each end. Therefore, the hydrogenated block copolymer of the present invention has at least two hydrogenated aromatic vinyl polymer block units. Then, at least one hydrogenated conjugated diene polymer block unit is provided between the two hydrogenated aromatic vinyl polymer block units.

The pre-hydrogenated block copolymer comprising the hydrogenated blocks may contain some additional blocks, which may be attached at any position of the triblock polymer backbone. Thus, the linear blocks include, for example, SBS, SBSB, SBSBS, and SBSBSB. The copolymer may be branched and the polymerized chains may be attached at any position along the backbone of the copolymer.

The lower limit of the weight average molecular weight (Mw) of the hydrogenated block copolymer is preferably 30,000 or more, more preferably 40,000 or more, still more preferably 45,000 or more, and particularly preferably 50,000 or more. The upper limit of Mw is preferably 120,000 or less, more preferably 100,000 or less, further preferably 95,000 or less, particularly preferably 90,000 or less, most preferably 85,000 or less, and very preferably 80. It is less than 1,000.
When Mw is at least the above lower limit, mechanical strength does not decrease, and when it is at most the above upper limit, moldability does not deteriorate.
Mw herein is determined using gel permeation chromatography (GPC).

The hydrogenation level of the block copolymer is preferably 90% or more hydrogenated aromatic vinyl polymer block units, 95% or more hydrogenated conjugated diene polymer block units, more preferably 95% hydrogenated aromatic vinyl polymer block units. %, the hydrogenated conjugated diene polymer block unit is 99% or more, more preferably the hydrogenated aromatic vinyl polymer block unit is 98% or more, the hydrogenated conjugated diene polymer block unit is 99.5% or more, particularly The hydrogenation is preferably 99.5% or more in the hydrogenated aromatic vinyl polymer block unit and 99.5% or more in the hydrogenated conjugated diene polymer block unit.
Such high levels of hydrogenation are preferred to reduce the dielectric loss of millimeter wave modules.
The hydrogenation level of the hydrogenated aromatic vinyl polymer block unit indicates the proportion of the aromatic vinyl polymer block unit saturated by hydrogenation, and the hydrogenation level of the hydrogenated conjugated diene polymer block unit is the conjugated diene The percentage of polymer block units saturated by hydrogenation is shown.

Hydrogenation levels of hydrogenated aromatic vinyl polymer block units and hydrogenated conjugated diene polymer block units are determined using proton NMR.

The melt flow rate (MFR) of the cyclic polyolefin of the present invention is not particularly limited, but is usually 0.1 g/10 min or more, preferably 0.5 g/10 min or more from the viewpoint of the molding method and the appearance of the molded product. is there. It is usually 200 g/10 minutes or less, preferably 100 g/10 minutes or less, and more preferably 50 g/10 minutes or less from the viewpoint of material strength.
MFR was measured according to JIS K7210 (1999) under the conditions of a measurement temperature of 230° C. and a measurement load of 21.18N.

As the cyclic polyolefin of the present invention, a commercially available product can be used, and specific examples thereof include Zelas (registered trademark) manufactured by Mitsubishi Chemical Corporation.

<Other ingredients>
The cyclic polyolefin of the present invention may contain, as other components, a compounding agent that is commonly used in resin compositions, within a range that does not impair the effects of the present invention.
Examples of such compounding agents include heat stabilizers, ultraviolet absorbers, light stabilizers, antioxidants, antistatic agents, crystal nucleating agents, rust preventives, inorganic fillers, glass fibers, foaming agents, and pigments. Are listed. Among these, the antioxidant preferably contains a phenol-based, sulfur-based, or phosphorus-based antioxidant, and the antioxidant is 0.1 to 2 parts by mass with respect to 100 parts by mass of the cyclic polyolefin. It is preferably contained.

Further, a resin component or an elastomer component other than the cyclic polyolefin may be contained within a range not impairing the effects of the present invention.
Examples of such resin components include polyethylene resin, polypropylene resin, ethylene-α-olefin copolymer resin, propylene-α-olefin copolymer resin, ethylene-vinyl acetate copolymer resin, ethylene-acrylic ester copolymer resin. , Ethylene-(meth)acrylic acid copolymer resin, polystyrene resin, polyvinyl chloride resin, polyester resin, polyamide resin, ethylene-vinyl alcohol copolymer, acrylic resin, and petroleum resin styrene-conjugated diene block Examples thereof include copolymer resins.

The blending of these other components may be added by kneading into the cyclic polyolefin by a kneading method that is commonly used for melt-kneading a thermoplastic resin, or by dissolving it in an organic solvent together with the cyclic polyolefin. It doesn't matter.

<Method for forming cyclic polyolefin>
The cyclic polyolefin of the present invention can be obtained as a molded product by a molding method which is commonly used for melt molding of thermoplastic resins.
As a molding processing method, injection molding, extrusion molding, rotational molding, hot press molding, and 3D printing molding method can be applied.

As the injection molding, in addition to ordinary injection molding, co-injection molding, insert injection molding, direct long fiber kneading injection molding, and the like can be applied.
As the extrusion molding, T-die film molding, sheet molding, air-cooled inflation film molding, water-cooled inflation film molding, pipe molding, profile extrusion molding, extrusion lamination molding and the like can be applied. For example, injection molding can be preferably used for manufacturing a millimeter-wave radar casing or cover, T-die film molding can be preferably used for antenna film manufacturing, and sheet molding or heat press molding can be preferably used for circuit boards. ..
In such extrusion molding, a laminated molded article can be obtained by coextruding another resin together with the cyclic polyolefin resin of the present invention within a range that does not impair the effects of the present invention.

Further, it is also preferable that the cyclic polyolefin of the present invention is dissolved in an organic solvent and then applied on another molded article, a film, a sheet or the like as a base material and dried to be used as a coating film.
The organic solvent used for coating is not particularly limited as long as it can dissolve the cyclic polyolefin of the present invention. Examples of compounds that are industrially easily available and easily removed by drying include aromatic organic solvents such as benzene, toluene and xylene; aliphatic organic solvents such as hexane and heptane; fats such as furan, cyclohexane and cycloheptane. Cyclic organic solvents; polar organic solvents such as dimethylformamide, dimethylsulfoxide and the like can be mentioned.
Of these, cyclohexane is preferable from the viewpoint of solubility.

The thickness of the molded product using the cyclic polyolefin of the present invention should be finely determined depending on the purpose and application, but it is 1 to 5 mm when manufactured by injection molding, 30 μm to 5 mm when manufactured by film molding, When manufactured by solution coating, 1 to 10 μm is generally suitably used.

The molded product obtained from the cyclic polyolefin of the present invention can be subjected to various processes as the next step.
For the film or sheet, for example, any of uniaxial, biaxial, and oblique stretching processes may be adopted, but biaxial stretching in which the degree of molecular orientation is easier to control is preferable. For stretching, a known uniaxial stretching machine, simultaneous biaxial stretching machine, sequential biaxial stretching machine or the like can be used.

Further, the film or sheet made of the cyclic polyolefin of the present invention may be laminated with another film or sheet to form a composite laminate. Examples of the film to be laminated include, for example, paper, aluminum foil, cellophane, woven cloth, non-woven cloth, and polymer film (for example, high density polyethylene, medium density polyethylene, low density polyethylene, ethylene/vinyl acetate copolymer, ethylene). -Olefin polymers such as acrylic acid ester copolymer, ionomer, polypropylene, poly-1-butene, poly-4-methylpentene-1; vinyl such as polyvinyl chloride, polyvinylidene chloride, polystyrene, polyacrylate, polyacrylonitrile, etc. Copolymer: Polyamide such as Nylon 6, Nylon 66, Nylon 7, Nylon 10, Nylon 11, Nylon 12, Nylon 610, Polymeta-xylylene adipamide; Polyester such as polyethylene terephthalate, polyethylene terephthalate/isophthalate, polybutylene terephthalate A film of polyvinyl alcohol, ethylene/vinyl alcohol copolymer, polycarbonate or the like).

Furthermore, one type of the above-mentioned film may be used alone, or two or more types may be used in combination, and depending on the type of the substrate, it may be stretched.
In particular, uniaxially or biaxially oriented polypropylene film, oriented nylon film, oriented polyethylene terephthalate film, oriented polystyrene film are used. Further, a substrate obtained by coating the above substrate with polyvinylidene chloride, polyvinyl alcohol, or the like, or a substrate obtained by vapor deposition of aluminum, alumina, silica, or a mixture of alumina and silica may be used.
As a method for laminating, known dry lamination, heat lamination, wet lamination, sandwich lamination, or the like can be used.

After the molded processed product is obtained from the cyclic polyolefin of the present invention, the surface thereof can be treated as necessary.
As the treatment method used, corona treatment, flame treatment, plasma treatment, metal vapor deposition processing, silica vapor deposition processing, alumina vapor deposition processing, uneven embossing processing, needle punching processing, plating processing and the like can be used.
For example, it is particularly preferable to use corona treatment to impart hydrophilicity, paintability, and adhesiveness to the surface.

<Method for manufacturing millimeter-wave module and its components>
The millimeter wave module of the present invention is manufactured by assembling each module component including a component obtained by molding and processing the cyclic polyolefin of the present invention (hereinafter, simply referred to as "resin molded component"). Examples of this module component include a millimeter wave transmitting/receiving antenna, radome, housing, connector, radar board, circuit board, casing, receiver, and the like. Examples of the resin molded component forming the millimeter wave module include a millimeter wave transmitting/receiving antenna film, a millimeter wave transmitting/receiving circuit board, a housing, a connector, and a millimeter wave radar cover.

The method for producing a resin molded component constituting the millimeter wave module of the present invention is not particularly limited, for example, when producing a millimeter wave transmitting and receiving antenna film, various transmission lines on the molded film made of the cyclic polyolefin of the present invention, For example, a known or common transmission line such as a coaxial line, a strip line, a microstrip line, a coplanar line, or a parallel line is formed.
Further, in the case of manufacturing a millimeter-wave transmitting and receiving circuit board, for example, a thin film of silicon dioxide is laminated on the molded product made of the cyclic polyolefin of the present invention, metal wiring is further formed on the thin film, and etching is required. It can be obtained by forming a simple circuit.
In addition, the housing, the connector, and the like can be obtained by embedding related parts and terminals by a known method or by fitting them with other parts.

Hereinafter, the present invention will be described in more detail with reference to examples, but the present invention is not limited to the examples. In the following examples and comparative examples, various physical properties were measured by the following methods.

<Melt flow rate (MFR)>
・Equipment...Made by Toyo Seiki Seisakusho: Melt Indexer・Temperature...230℃
・Orifice hole diameter: 2 mm
・Load... 21.18N

<Molecular weight>
・Device: Tosoh Corporation: GPC HLC-832GPC/HT
・Detector: MIRAN: 1A infrared spectrophotometer (measurement wavelength: 3.42 μm)
・Column: Showa Denko KK: AD806M/S 3 pcs (column calibration: Toso monodisperse polystyrene (A500, A2500, F1, F2, F4, F10, F20, F40, F288 0.5 mg/ml each) Solution) was measured, and the logarithmic value of the elution volume and the molecular weight were approximated by a cubic formula.
・Measurement temperature…135℃
・Concentration...20mg/10mL
・Injection volume: 0.2 ml
・Solvent...Orthodichlorobenzene・Flow rate...1.0 ml/min

<Polymer block ratio>
[Measurement by carbon NMR]
・Apparatus: Bruker Co.: AVANCE400 spectrometer ・Solvent: Orthodichlorobenzene-h4/paradichlorobenzene-d4 mixed solvent ・Concentration: 0.3 g/2.5 mL
・Measurement... ¹³ C-NMR
・Resonance frequency: 400 MHz
・Total number of times…1536
・Flip angle: 45° ・Data acquisition time: 1.5 seconds ・Pulse repetition time: 15 seconds ・Measured temperature: 100°C
・¹ H irradiation... Complete decoupling

<Hydrogenation rate of hydrogenated aromatic vinyl polymer block unit, hydrogenated conjugated diene polymer block unit>
[Measurement by proton NMR]
・Apparatus: JASCO 400YH spectrometer ・Solvent: Deuterated chloroform ・Concentration: 0.045g/1.0mL
・Measurement... ¹ H-NMR
・Resonance frequency: 400 MHz
・Total number of times: 8
・Measurement temperature…18.5℃
-Hydrogenated aromatic vinyl polymer block unit hydrogenation rate: 6.8 to 7.5 ppm integrated value reduction rate-Hydrogenated conjugated diene polymer block unit hydrogenation rate: 5.7 to 6.4 ppm integrated value reduction rate

<Molding>
With an in-line screw type injection molding machine (IS130 manufactured by Toshiba Machine Co., Ltd.), a molding temperature of 250° C., a mold temperature of 80° C., a molding speed of 200 mm/sec, an injection time of 25 seconds, a cooling time of 30 seconds, 2 mm×10 cm. A flat plate of 10 cm was prepared. However, regarding the material of the comparative example, the mold temperature was set to 40° C. according to the solidification behavior of the material.

<Measurement of dielectric constant and dielectric loss>
The measurement was performed using a transmission attenuation measuring jig with a dielectric lens.
-Apparatus: manufactured by KEYSIGHT: Vector network analyzer N5227A,
VIRGINIA DIODES: Millimeter wave module WR10-VNAX,
KEYSIGHT: Network Analyzer E8361A.
・Measurement environment: 26°C, humidity 40%
・Measurement frequency: 10 GHz, 50 GHz, 77 GHz

(Example 1)
As a cyclic polyolefin, Mitsubishi Chemical's Zelas (registered trademark) MC930 was used to prepare a flat plate by injection molding, which was used as a millimeter wave module.
The dielectric constant and the dielectric loss of the obtained millimeter wave module were measured. The results are shown in Table 1.

[Zelas MC930]
Density (ASTM D792): 0.94g / cm 3
-MFR (230°C, 21.16N): 2g/10 minutes-Mw: 75,600
Hydrogenated aromatic vinyl polymer block unit: hydrogenated polystyrene having a polymer block ratio of 68 mol% and a hydrogenation rate of 99.5% or more. Hydrogenated conjugated diene polymer block unit: polymer block ratio of 32 mol% and a hydrogenation rate of 99. 5% or more hydrogenated polybutadiene/pentablock structure, total hydrogenation rate: 99.5% or more

(Example 2)
Zelas (registered trademark) MC931 manufactured by Mitsubishi Chemical Co., Ltd. was used as the cyclic polyolefin, and other evaluations were performed in the same manner as in Example 1. The results are shown in Table 1.

[Zelas MC931]
Density (ASTM D792): 0.94g / cm 3
-MFR (230°C, 21.16N): 35g/10 minutes-Mw: 54,200
Hydrogenated aromatic vinyl polymer block unit: Polymer block ratio 66 mol%, hydrogenated polystyrene having a hydrogenation rate of 99.5% or more Hydrogenated conjugated diene polymer block unit: Polymer block ratio 34 mol%, hydrogenation rate 99. 5% or more hydrogenated polybutadiene/pentablock structure, total hydrogenation rate: 99.5% or more

(Comparative Example 1)
The styrene-butadiene copolymer resin KRATON (registered trademark) D1155J manufactured by KRATON was used in place of the cyclic polyolefin, and the other evaluations were performed in the same manner as in Example 1. The results are shown in Table 1.

[KRATON D1155J]
Density (ASTM D792): 0.95g / cm 3
・MFR (230°C, 21.16N): 5g/10 minutes ・Mw: 99,500
-Aromatic vinyl polymer block unit: polystyrene with a polymer block ratio of 40 mol% and a hydrogenation rate of 0%-conjugated diene polymer block unit: polymer block ratio: 60 mol%, polybutadiene with a hydrogenation ratio of 0%, triblock structure, total Hydrogenation rate: 0%

(Comparative example 2)
The hydrogenated styrene-butadiene copolymer resin KRATON (registered trademark) G1652M manufactured by KRATON was used in place of the cyclic polyolefin, and the same evaluation as in Example 1 was carried out except for the above. The results are shown in Table 1.

[KRATON G1652M]
Density (ASTM D792): 0.91g / cm 3
・MFR (230°C, 21.16N): 6g/10 minutes ・Mw: 68,500
-Aromatic vinyl polymer block unit: polystyrene having a polymer block ratio of 29 mol% and hydrogenation rate of 0%-hydrogenated conjugated diene polymer block unit: 71 mol% of polymer block ratio and hydrogenated polybutadiene-triblock having a hydrogenation ratio of 99% Structure, total hydrogenation rate: 45 mol%

<Comparative example 3>
The hydrogenated styrene-butadiene copolymer resin KRATON (registered trademark) A1535HU manufactured by KRATON was used in place of the cyclic polyolefin, and the other evaluations were performed in the same manner as in Example 1. The results are shown in Table 1.

[KRATON A1535HU]
Density (ASTM D792): 0.96g / cm 3
-MFR (230°C, 21.16N): <1g/10 minutes-Mw: 234,000
-Aromatic vinyl polymer block unit: polystyrene with a polymer block ratio of 58 mol% and hydrogenation rate of 0%-hydrogenated conjugated diene polymer block unit: polymer block ratio: 42 mol%, hydrogenated polybutadiene with a hydrogenation ratio of 99%-tri Block structure, total hydrogenation rate: 19 mol%

<Evaluation result>
As shown in Table 1, in Examples 1 and 2 using the cyclic polyolefin of the present invention, it was found that the low dielectric constant and the low dielectric loss were stable from the low frequency region to the high frequency region.
On the other hand, in Comparative Example 1 using the unhydrogenated copolymer resin and Comparative Examples 2 and 3 in which the aromatic vinyl polymer block unit was not hydrogenated, the dielectric loss was particularly high at each frequency, and the high frequency region was high. It was found that high-performance millimeter-wave devices cannot be manufactured because the dielectric loss rises sharply.

Claims (7)

A millimeter-wave module having a part formed by molding a cyclic polyolefin,
The cyclic polyolefin comprises a hydrogenated block copolymer that is a hydrogenated block copolymer containing at least one aromatic vinyl monomer unit and at least one conjugated diene monomer unit,
The hydrogenated block copolymer is a hydrogenated product of a polymer block composed of the aromatic vinyl monomer unit, a hydrogenated aromatic vinyl polymer block unit, and a hydrogenated product of a polymer block composed of the conjugated diene monomer unit. Having a conjugated diene polymer block unit,
The millimeter-wave module, wherein the hydrogenated block copolymer has at least two hydrogenated aromatic vinyl polymer block units and at least one hydrogenated conjugated diene polymer block unit. The millimeter wave module according to claim 1, wherein the hydrogenated aromatic vinyl polymer block unit has a hydrogenation level of 90% or more, and the hydrogenated conjugated diene polymer block unit has a hydrogenation level of 95% or more. .. The millimeter wave module according to claim 1 or 2, wherein the hydrogenated aromatic vinyl polymer block unit is made of hydrogenated polystyrene, and the content rate in the cyclic polyolefin is 50 to 99 mol%. The millimeter wave module according to claim 1 or 2, wherein the hydrogenated conjugated diene polymer block unit is made of hydrogenated polybutadiene, and the content of the cyclic polyolefin is 1 to 50 mol%. A transmission/reception antenna film, which is a component made of the cyclic polyolefin constituting the millimeter wave module according to any one of claims 1 to 4. A millimeter wave module component that is a component made of the cyclic polyolefin that constitutes the millimeter wave module according to any one of claims 1 to 4, and is selected from a millimeter wave radar cover, a connector, and a housing. A millimeter wave receiving/transmitting circuit board which is a component made of the cyclic polyolefin constituting the millimeter wave module according to any one of claims 1 to 4.