JP6420138B2 - Millimeter-wave-permeable resin parts and millimeter-wave radome and millimeter-wave radar having the same - Google Patents

Description

  The present invention relates to a resin component having a low dielectric constant and a low dielectric loss tangent and having millimeter-wave transparency and excellent impact resistance, shape stability, and the like, and includes this, and transmits or receives millimeter waves The present invention relates to a millimeter wave radome (antenna cover) for storing or protecting an antenna module, and a millimeter wave radar including the radome.

2. Description of the Related Art Conventionally, wireless communication including a millimeter wave radar that transmits and receives millimeter waves that are radio waves of 30 GHz to 300 GHz, sensors, and the like have been actively developed, and application examples thereof have been widely proposed. Some of them have already been put into practical use, such as a sensor for instantaneously detecting the position and speed of a moving person or object, an imaging apparatus for security check, and the like.
The millimeter wave radar usually includes an antenna module that transmits or receives millimeter waves and a radome that stores or protects the antenna module. Of these, the radome is usually a resin molded body and has various shapes depending on the application, but the entire radome is formed of a material that easily transmits radio waves, or only a specific portion corresponding to a radio wave path. Some of them are made of a material that easily transmits radio waves.

  The molding material for the radome constituting the millimeter wave radar is disclosed in the following Patent Documents 1 to 3, and the like.

  Patent Document 1 discloses a millimeter wave radar including an antenna base having a transmission / reception antenna (antenna module), a housing for fixing the antenna base, and at least one of a radome or a radar cover that covers the antenna base. As the radar cover, a millimeter wave radar is disclosed in which the relative dielectric constant of the portion in the side surface direction of the transmission / reception antenna is larger than that of the front portion of the transmission / reception antenna. Further, there is a description that the radome or radar cover in the front portion of the transmission / reception antenna mainly contains polycarbonate, syndiotactic polystyrene, polypropylene, or a hybrid material with ABS resin mainly composed of these resins.

  In Patent Document 2, in a molded article that has a decorative layer between a base material layer and a transparent resin layer and is disposed in the beam path of a radio wave radar device, the dielectric loss tangent at the beam frequency is 0.0005 or less. A resin molded article formed from a thermoplastic resin having a relative dielectric constant of 3 or less is disclosed. And as this thermoplastic resin, it has been conventionally described that cyclopolyolefin is preferable to a known polypropylene resin.

  Patent Document 3 discloses a resin composition comprising a polybutylene terephthalate resin suitable as a material for parts such as circuit substrates and radomes that require a low dielectric constant, and a cyclic olefin resin having a glass transition temperature of 100 ° C. or higher. Things are disclosed.

JP 2004-31696 A JP 2007-13722 A JP 2013-43942 A

  As described above, as a millimeter wave radar, only a specific portion corresponding to a radio wave path is provided with a radome formed of a material that easily transmits radio waves, or the entire part is formed of a material that easily transmits radio waves. Some have a radome. In any case, the portion corresponding to the path of the radio wave needs to have at least excellent dielectric properties, mechanical properties, and shape stability.

  An object of the present invention is to provide a resin component excellent in millimeter wave permeability, impact resistance, shape stability, and the like, and a millimeter wave radome and a millimeter wave radar including the resin component.

The present invention is a millimeter-wave radar and a resin part (hereinafter, also referred to as “millimeter-wave transmitting resin part”) suitable as a radome that is a member constituting the millimeter-wave radar and a constituent member of the radome, and is described below.
1. [A] A resin component that transmits millimeter waves, comprising a thermoplastic resin composition containing a rubbery polymer reinforced resin and [B] a polyolefin resin.
2. The rubbery polymer reinforced resin [A] consists of (A1) a rubbery polymer reinforced vinyl resin and (A2) (co) polymeric resin, and the rubbery polymer reinforced vinyl resin (A1) is: A polymer part derived from at least one rubber polymer selected from diene rubber, acrylic rubber, ethylene / α-olefin rubber, hydrogenated diene rubber and silicone rubber, and a vinyl resin part The (co) polymer resin (A2) is at least one selected from a structural unit derived from an aromatic vinyl compound, a structural unit derived from a vinyl cyanide compound, and a structural unit derived from a (meth) acrylic acid alkyl ester compound. 3. The resin part as described in 1 or 2 above.
3. The content ratio of the rubbery polymer reinforced resin [A] and the polyolefin resin [B] is 30 to 95% by mass and 5 to 70% by mass, respectively, when the total of both is 100% by mass. The resin component according to 1 or 2.
4). 4. The resin part as described in 2 or 3 above, wherein the ethylene / α-olefin rubber is an ethylene / α-olefin copolymer.
5. A millimeter wave radome comprising the resin component according to any one of 1 to 4 above.
6). A millimeter wave radar comprising the millimeter wave radome described in 5 above.
In this specification, “transmitting millimeter waves” means that the relative dielectric constant at a frequency of about 77 GHz, measured based on JIS R1660-1, is less than 2.8, and the dielectric loss tangent (tan δ) is 9. It means having a performance of less than 0 × 10 ⁻³ . Further, “excellent in shape stability” has the performance that the molding shrinkage in the MD direction and the TD direction of the test piece, both measured in accordance with JIS K7152-4, is less than 1.1%. Means that.

Since the millimeter wave transmitting resin component of the present invention is made of a resin material having a low relative dielectric constant and a low dielectric loss tangent (tan δ), the millimeter wave can be transmitted without being reflected or absorbed. Since it is excellent in stability and the like, it is suitable as a component of a millimeter wave radome or millimeter wave radar.
The radome for millimeter waves of the present invention is suitable for storing or protecting an antenna module that transmits or receives millimeter waves. The millimeter-wave radome of the present invention can be entirely made of the millimeter-wave transparent resin component of the present invention, and in particular, only the portion corresponding to the path related to millimeter wave transmission or reception is It can be made to consist of the millimeter-wave transparent resin part of invention.
The millimeter wave radar of the present invention is suitable as a device for transmitting or receiving millimeter waves.

It is a schematic sectional drawing which shows an example of the millimeter wave transparent resin component of this invention, the radome for millimeter waves provided with this, and a millimeter wave radar. It is a schematic sectional drawing which shows the other example of the millimeter wave radome and millimeter wave radar provided with the millimeter wave transparent resin component of this invention. It is a schematic sectional drawing which shows the other example of the millimeter wave radome and millimeter wave radar provided with the millimeter wave transparent resin component of this invention. It is a schematic sectional drawing which shows the other example of the millimeter wave radome and millimeter wave radar provided with the millimeter wave transparent resin component of this invention. It is a schematic sectional drawing which shows the other example of the millimeter wave transparent resin component of this invention, and the radome for millimeter waves. It is a schematic sectional drawing which shows the other example of the millimeter wave radar of this invention provided with the millimeter wave transparent resin component of FIG. 5, and the radome for millimeter waves. It is a schematic sectional drawing which shows the other example of the millimeter wave radar of this invention.

The present invention contains a rubbery polymer reinforced resin [A] (hereinafter also referred to as “component [A]”) and a polyolefin resin [B] (hereinafter also referred to as “component [B]”). A millimeter-wave transmitting resin component made of a specific thermoplastic resin composition, a millimeter-wave radome (hereinafter also referred to as “radome”) including the resin component, and a millimeter-wave including the radome and an antenna module. The radar is illustrated in FIGS.
1 to 7, the millimeter wave transmitting resin component of the present invention is a resin component denoted by reference numeral 60. Further, the radome of the present invention is a component that stores or protects an antenna module that transmits or receives millimeter waves, which is indicated by reference numeral 70, and includes only a millimeter wave transmissive resin component 60, as shown in FIGS. The article may be an article, or as shown in FIG. 3, it may be a composite article comprising a millimeter wave transmissive resin part 60 and another part 62. The millimeter wave radar of the present invention suitable for wireless communication, sensors, and the like can be configured by the millimeter wave transmitting resin component and radome of the present invention.

In this specification, “(meth) acryl” means acryl and methacryl, “(meth) acrylate” means acrylate and methacrylate, “(meth) acryloyl group” means acryloyl group and methacryloyl group, “Polymer” means homopolymers and copolymers.
The melting point of the thermoplastic resin according to JIS K 7121 (hereinafter referred to as “Tm”) was measured by measuring the endothermic change at a constant heating rate of 20 ° C. per minute using a differential scanning calorimeter (DSC). This is a value obtained by reading the peak temperature of the obtained endothermic pattern.

  Hereinafter, the thermoplastic resin composition constituting the millimeter wave transmitting resin component of the present invention will be described. This thermoplastic resin composition essentially comprises components [A] and [B], but may further contain other thermoplastic resins and additives (both described later).

  The component [A] is a component containing a rubbery polymer reinforced vinyl resin in which the rubbery polymer part and the vinyl resin part are chemically bonded, and preferably the component [A] It is a resin component containing 25 mass% or more (100 mass% may be sufficient) with respect to the whole. In the present invention, the component [A] includes a rubber-based polymer-reinforced vinyl resin and a vinyl-based resin that does not include a rubber-like polymer part and includes one or more structural units derived from a vinyl-based monomer. A combination with a resin may also be used.

  The rubber polymer reinforced vinyl resin preferably has a rubber polymer part obtained by polymerizing a vinyl monomer in the presence of the rubber polymer and a vinyl resin part chemically. Bonded graft resin, particularly preferably derived from at least one rubber polymer selected from diene rubber, acrylic rubber, ethylene / α-olefin rubber, hydrogenated diene rubber and silicone rubber The rubber polymer reinforced vinyl resin (A1) in which the polymer part (hereinafter also referred to as “rubber polymer part”) and the vinyl resin part are chemically bonded.

  The rubbery polymer constituting the rubbery polymer part may be a homopolymer or a copolymer as long as it is rubbery at 25 ° C. The rubbery polymer may be a crosslinked polymer or a non-crosslinked polymer.

  Examples of the diene rubber include homopolymers such as polybutadiene, polyisoprene, and polychloroprene; styrene / butadiene copolymers, styrene / butadiene / styrene copolymers, acrylonitrile / butadiene copolymers, and acrylonitrile / styrene / butadiene copolymers. Styrene / butadiene copolymer rubbers such as styrene / isoprene copolymers, styrene / isoprene copolymers, styrene / isoprene / styrene copolymers, styrene / isoprene copolymer rubbers such as acrylonitrile / styrene / isoprene copolymers, etc. . These copolymers may be block copolymers or random copolymers.

The acrylic rubber is preferably methyl acrylate, ethyl acrylate, n-propyl acrylate, n-butyl acrylate, 2-ethylhexyl acrylate, ethoxyethoxyethyl acrylate, methoxytripropylene glycol acrylate, 4-hydroxybutyl acrylate, lauryl methacrylate. A rubber obtained by (co) polymerizing a monomer containing a (meth) acrylic acid alkyl ester compound such as stearyl methacrylate. These (meth) acrylic acid alkyl ester compounds can be used alone or in combination of two or more.
In addition to the (meth) acrylic acid alkyl ester compounds, the monomers include aromatic vinyl compounds such as styrene, α-methylstyrene, and vinyl toluene; vinyl cyanide compounds such as acrylonitrile and methacrylonitrile; methacrylic acid Various vinyl monomers such as modified silicone and fluorine-containing vinyl compound may be contained in the range of 30% by mass or less.

  The ethylene / α-olefin rubber is a copolymer rubber comprising a structural unit derived from ethylene and a structural unit derived from α-olefin, or, in addition to these structural units, further derived from a non-conjugated diene. It is a copolymer rubber containing a structural unit. When the component [A] includes a rubbery polymer part derived from ethylene / α-olefin rubber, the ethylene unit amount constituting the ethylene / α-olefin rubber is the millimeter-wave transmission according to the present invention. From the viewpoint of mechanical properties and molded appearance in the resin part, it is preferably 30 to 85% by mass, more preferably 40 to 80% by mass, and still more preferably 45 to 75% by mass.

  Examples of the α-olefin include propylene, 1-butene, 1-pentene, 1-hexene, 4-methyl-1-pentene, 1-heptene, 1-octene, 1-decene, 1-dodecene, 1-hexadecene, -Eicosen and the like. These α-olefins can be used alone or in combination of two or more. The number of carbon atoms of the α-olefin is preferably from 3 to 20, more preferably from 3 to 12, and even more preferably from 3 to 8, from the viewpoints of mechanical properties and molded appearance in the millimeter wave transmitting resin component of the present invention.

Examples of the nonconjugated dienes include alkenyl norbornene, cyclic dienes, and aliphatic dienes. These non-conjugated dienes can be used alone or in combination of two or more.
When the ethylene / α-olefin-based rubber is an ethylene / α-olefin / non-conjugated diene copolymer rubber, the upper limit of the content ratio of the structural unit derived from the non-conjugated diene is the ethylene / α-olefin-based rubber. When the total amount of the structural units to constitute is 100% by mass, it is preferably 15% by mass, more preferably 10% by mass, and still more preferably 5% by mass.

  The ethylene / α-olefin rubber is an ethylene having a Tm of preferably 0 ° C. to 120 ° C., more preferably 10 ° C. to 100 ° C., and even more preferably 30 ° C. to 80 ° C., from the viewpoint of millimeter wave permeability. -It is an alpha-olefin copolymer. Such an ethylene / α-olefin-based rubber is more preferably a copolymer comprising a structural unit derived from ethylene and a structural unit derived from an α-olefin having 3 to 8 carbon atoms, Preferred are ethylene / propylene copolymers, ethylene / 1-butene copolymers, and ethylene / 1-octene copolymers, and particularly preferred are ethylene / propylene copolymers.

The hydrogenated diene rubber is 1,3-butadiene, isoprene, piperylene, 1,3-pentadiene, methylpentadiene, phenylbutadiene, 3,4-dimethyl-1,3-hexadiene, 4,5-diethyl-1, A hydrogenated homopolymer or copolymer having a structural unit derived from a conjugated diene compound such as 3-octadiene or chloroprene (hereinafter referred to as “hydrogenated diene (co) polymer rubber”). It is.
Examples of the hydrogenated diene-based (co) polymer rubber include a hydrogenated product of a block copolymer having the following structure. That is, a polymer block P composed of a structural unit derived from an aromatic vinyl compound; a double bond portion of a polymer composed of a structural unit derived from a conjugated diene compound having a 1,2-vinyl bond content exceeding 25 mol%. Polymer block Q obtained by hydrogenation of 95 mol% or more; 95 mol% or more of a double bond portion of a polymer comprising a structural unit derived from a conjugated diene compound having a 1,2-vinyl bond content of 25 mol% or less Hydrogenated polymer block R formed by hydrogenation; and 95 mol% or more of a double bond portion of a copolymer composed of a structural unit derived from an aromatic vinyl compound and a structural unit derived from a conjugated diene compound. Is a block copolymer composed of a combination of two or more of the polymer blocks S.

The molecular structure of the block copolymer may be branched, radial, or a combination thereof. The block structure may be a diblock, triblock, multiblock, or a combination thereof.
As the structure of the block copolymer, P- (QP) n, (PQ) n, P- (QR) n, R- (QR) n, (QR) n , P- (SP) n, (PS) n, P- (SR) n, R- (SR) n, (S-R) n, P- (QRS) ) N, (PQR-S) n [n is an integer of 1 or more. PQQ, PQPQ, PQR, PSR, and RQR are preferable.

Examples of the aromatic vinyl compound used for forming the polymer blocks P and S constituting the block copolymer include styrene, α-methylstyrene, methylstyrene, vinylxylene, monochlorostyrene, dichlorostyrene, monobromostyrene, dibromo. Examples thereof include styrene, fluorostyrene, p-tert-butylstyrene, ethylstyrene, vinylnaphthalene and the like. These compounds can be used alone or in combination of two or more. Of these, styrene is preferred.
The content ratio of the polymer block P constituting the block copolymer is preferably 0 to 65% by mass, more preferably 10 to 40% by mass with respect to the whole polymer.

  The polymer blocks Q, R and S are formed by hydrogenating a pre-hydrogenation block copolymer obtained using a conjugated diene compound and an aromatic vinyl compound. Examples of the conjugated diene compound used for forming the polymer blocks Q, R and S include 1,3-butadiene, isoprene, 1,3-pentadiene, chloroprene and the like. These compounds can be used alone or in combination of two or more. Of these, 1,3-butadiene and isoprene are preferred because they can be utilized industrially and have excellent physical properties.

The hydrogenation rates of the polymer blocks Q, R and S are all 95 mol% or more, preferably 96 mol% or more.
The 1,2-vinyl bond content in the polymer block Q is preferably more than 25 mol% and 90 mol% or less, more preferably 30 to 80 mol%.
The 1,2-vinyl bond content in the polymer block R is preferably 25% mol or less, more preferably 20 mol% or less.

The 1,2-vinyl bond content in the polymer block S is preferably 25 to 90 mol%, more preferably 30 to 80 mol%.
Further, the content ratio of the structural unit derived from the aromatic vinyl compound in the polymer block S is preferably 25% by mass or less, more preferably 20% by mass or less.

Examples of the hydrogenated diene (co) polymer rubber include hydrogenated polybutadiene, hydrogenated styrene / butadiene rubber, styrene / ethylene butylene / olefin crystal block polymer, olefin crystal / ethylene butylene / olefin crystal block polymer, styrene / ethylene butylene / Examples thereof include styrene block polymers, hydrogenated products of butadiene / acrylonitrile copolymers, and the like.
In the hydrogenated diene (co) polymer rubber, the hydrogenation ratio with respect to the diene (co) polymer before hydrogenation is preferably 10 to 95%, more preferably 20 to 70%, still more preferably 30. ~ 65%.

  The hydrogenated diene (co) polymer rubber has a weight average molecular weight (Mw) of preferably 10,000 to 1,000,000, more preferably 30,000 to 800,000, and even more preferably 50,000 to 500,000.

The silicone rubber is preferably a polyorganosiloxane polymer having a polymerizable unsaturated bond (carbon-carbon double bond), and particularly preferably has a structural unit represented by the following general formula (1). A modified polyorganosiloxane rubber obtained by cocondensation of one or more types of organosiloxane (i) and a graft crossing agent (ii).
[R ¹ _n SiO] _{(4-n) / 2} (1)
(In the formula, R ¹ represents a substituted or unsubstituted monovalent hydrocarbon group, and n represents an integer of 0 to 3. When there are a plurality of R ^{1 s} , they may be the same as or different from each other.)

R ¹ in the general formula (1), that is, the monovalent hydrocarbon group includes an alkyl group such as a methyl group, an ethyl group, a propyl group, and a butyl group; an aryl group such as a phenyl group and a tolyl group; a vinyl group; An alkenyl group such as an allyl group; and a group in which some of the hydrogen atoms bonded to carbon atoms in these hydrocarbon groups are substituted with a halogen atom, a cyano group, or the like; and at least one of the alkyl group hydrogen atoms is a mercapto group Examples include substituted groups.

The organosiloxane (i) is linear, branched or cyclic and preferably has a cyclic structure. Specifically, hexamethylcyclotrisiloxane, octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, dodecamethylcyclohexasiloxane, trimethyltriphenylcyclotrisiloxane, tetramethyltetraphenylcyclotetrasiloxane, octaphenylcyclotetrasiloxane, etc. Is mentioned. These can be used alone or in combination of two or more.
The organosiloxane (i) is a polycondensate that has been condensed in advance using one or more of the compounds represented by the general formula (1), for example, having a weight average molecular weight (Mw) of about 500 to 10,000. It may be an organosiloxane. The polyorganosiloxane may be a polyorganosiloxane whose molecular chain end is sealed with a functional group such as a hydroxyl group, an alkoxy group, a trimethylsilyl group, or a methyldiphenylsilyl group.

Examples of the graft crossing agent (ii) include vinylmethyldimethoxysilane, p-vinylphenylmethyldimethoxysilane, 1- (p-vinylphenyl) methyldimethylisopropoxysilane, 2- (p-vinylphenyl) ethylenemethyldimethoxysilane, 3- (p-vinylphenoxy) propylmethyldiethoxysilane, 1- (o-vinylphenyl) -1,1,2-trimethyl-2,2-dimethoxydisilane, allylmethyldimethoxysilane, γ-methacryloxypropylmethyldimethoxy A compound having a carbon-carbon unsaturated bond and an alkoxysilyl group, such as silane; a silane compound having a mercapto group (thiol group), such as γ-mercaptopropylmethylmethyldimethoxysilane; a silane compound having an amino group; tetravinyl Tetramethyl And cyclosiloxane.
When the organosiloxane (i) contains a polymerizable unsaturated bond, the graft crossing agent (ii) to be used may or may not have a polymerizable unsaturated bond.

In the case of producing the modified polyorganosiloxane rubber, the organosiloxane (i) and the graft crossing agent (ii) are subjected to shear mixing in the presence of an emulsifier such as alkylbenzene sulfonic acid using a homomixer or the like to condense. It can be a method or the like. The upper limit of the amount of the graft crossing agent (ii) used is preferably 50% by mass, more preferably 10% by mass, and still more preferably 5% when the total amount with the organosiloxane (i) is 100% by mass. % By mass.
In the production of the modified polyorganosiloxane rubber, a crosslinking agent may be added in order to improve impact resistance. Examples of the crosslinking agent include trifunctional crosslinking agents such as methyltrimethoxysilane, phenyltrimethoxysilane, and ethyltriethoxysilane, and tetrafunctional crosslinking agents such as tetraethoxysilane. When a crosslinking agent is used, the upper limit of the amount used is usually 10 parts by mass, preferably 5 parts by mass when the total amount of the organosiloxane (i) and the graft crossing agent (ii) is 100 parts by mass. .
The weight average molecular weight (Mw) of the modified polyorganosiloxane rubber is preferably 30,000 to 1,000,000.

  On the other hand, the vinyl resin part constituting the rubber polymer reinforced vinyl resin (A1) is a part derived from a vinyl resin containing a structural unit derived from a vinyl monomer. This vinyl resin part may contain only one type of structural unit derived from a vinyl monomer, or may contain two or more types of structural units derived from a vinyl monomer. Good.

Examples of the vinyl monomers include aromatic vinyl compounds, vinyl cyanide compounds, (meth) acrylic acid ester compounds, maleimide compounds, unsaturated acid anhydrides, carboxyl group-containing unsaturated compounds, amino group-containing unsaturated compounds. Amide group-containing unsaturated compounds, hydroxyl group-containing unsaturated compounds, oxazoline group-containing unsaturated compounds, and the like. These compounds may be used alone or in combination of two or more.
In the present invention, the vinyl resin part preferably includes a structural unit derived from an aromatic vinyl compound from the viewpoints of molding appearance and shape stability in the millimeter wave transmitting resin component of the present invention. From the above viewpoint, the lower limit of the content of the structural unit derived from the aromatic vinyl compound contained in the vinyl resin part is preferably 50% by mass, more preferably 60% by mass, and even more preferably 70% by mass. .

  The aromatic vinyl compound is not particularly limited as long as it is a compound having at least one vinyl bond and at least one aromatic ring. However, it shall not have a substituent such as a functional group. Examples thereof include styrene, α-methylstyrene, o-methylstyrene, p-methylstyrene, β-methylstyrene, ethylstyrene, p-tert-butylstyrene, vinyltoluene, vinylxylene, vinylnaphthalene and the like. These compounds can be used alone or in combination of two or more. Of these, styrene and α-methylstyrene are preferable, and styrene is particularly preferable.

  Examples of the vinyl cyanide compound include acrylonitrile, methacrylonitrile, ethacrylonitrile, α-ethylacrylonitrile, α-isopropylacrylonitrile and the like. These compounds can be used alone or in combination of two or more. Of these, acrylonitrile is preferred.

  Examples of the (meth) acrylate compound include methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, Isobutyl (meth) acrylate, sec-butyl (meth) acrylate, tert-butyl (meth) acrylate, hexyl (meth) acrylate, n-octyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, Examples include cyclohexyl (meth) acrylate, phenyl (meth) acrylate, benzyl (meth) acrylate, and the like. These compounds can be used alone or in combination of two or more.

  Examples of the maleimide compound include maleimide, N-methylmaleimide, N-isopropylmaleimide, N-butylmaleimide, N-dodecylmaleimide, N-phenylmaleimide, N- (2-methylphenyl) maleimide, N- (4-methyl). Phenyl) maleimide, N- (2,6-dimethylphenyl) maleimide, N- (2,6-diethylphenyl) maleimide, N- (2-methoxyphenyl) maleimide, N-benzylmaleimide, N- (4-hydroxyphenyl) ) Maleimide, N-naphthylmaleimide, N-cyclohexylmaleimide and the like. Of these, N-phenylmaleimide is preferred. These compounds can be used alone or in combination of two or more. In the case where a structural unit derived from a maleimide compound is introduced into the polymer chain, for example, a method in which maleic anhydride is copolymerized and then imidized can be applied.

Examples of the unsaturated acid anhydride include maleic anhydride, itaconic anhydride, citraconic anhydride, and 2,3-dimethylmaleic anhydride. These compounds can be used alone or in combination of two or more.
Examples of the carboxyl group-containing unsaturated compound include (meth) acrylic acid, ethacrylic acid, maleic acid, fumaric acid, itaconic acid, crotonic acid, cinnamic acid and the like. These compounds can be used alone or in combination of two or more.

Examples of the amino group-containing unsaturated compound include aminoethyl acrylate, propylaminoethyl acrylate, dimethylaminomethyl acrylate, diethylaminomethyl acrylate, 2-dimethylaminoethyl acrylate, aminoethyl methacrylate, and propylaminoethyl methacrylate. , Dimethylaminomethyl methacrylate, diethylaminomethyl methacrylate, 2-dimethylaminoethyl methacrylate, phenylaminoethyl methacrylate, p-aminostyrene, N-vinyldiethylamine, N-acetylvinylamine, acrylicamine, methacrylamine, N- Examples include methylacrylamine. These compounds can be used alone or in combination of two or more.
Examples of the amide group-containing unsaturated compound include acrylamide, N-methylacrylamide, methacrylamide, N-methylmethacrylamide and the like. These compounds can be used alone or in combination of two or more.

  Examples of the hydroxyl group-containing unsaturated compound include hydroxymethyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, (meth ) Having hydroxyl groups such as 2-hydroxybutyl acrylate, 3-hydroxybutyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate ( (Meth) acrylic acid ester; o-hydroxystyrene, m-hydroxystyrene, p-hydroxystyrene, o-hydroxy-α-methylstyrene, m-hydroxy-α-methylstyrene, p-hydroxy-α-methylstyrene, 2- Hydroxy Cyl-α-methylstyrene, 3-hydroxymethyl-α-methylstyrene, 4-hydroxymethyl-α-methylstyrene, 4-hydroxymethyl-1-vinylnaphthalene, 7-hydroxymethyl-1-vinylnaphthalene, 8-hydroxy Methyl-1-vinylnaphthalene, 4-hydroxymethyl-1-isopropenylnaphthalene, 7-hydroxymethyl-1-isopropenylnaphthalene, 8-hydroxymethyl-1-isopropenylnaphthalene, p-vinylbenzyl alcohol, 3-hydroxy- Examples include 1-propene, 4-hydroxy-1-butene, cis-4-hydroxy-2-butene, trans-4-hydroxy-2-butene, and 3-hydroxy-2-methyl-1-propene. These compounds can be used alone or in combination of two or more.

  Examples of the epoxy group-containing unsaturated compound include glycidyl (meth) acrylate, 3,4-oxycyclohexyl (meth) acrylate, vinyl glycidyl ether, allyl glycidyl ether, methallyl glycidyl ether, monoglycidyl maleate, diglycidyl maleate Monoglycidyl itaconate, diglycidyl itaconate, monoglycidyl allyl succinate, diglycidyl allyl succinate, glycidyl p-styrenecarboxylate, 2-methylpropenyl glycidyl ether, styrene-p-glycidyl ether, and the like. These compounds can be used alone or in combination of two or more.

  Examples of the unsaturated compound containing an oxazoline group include vinyl oxazoline, 4-methyl-2-vinyl-2-oxazoline, 5-methyl-2-vinyl-2-oxazoline, 2-vinyl-4,4-dimethyl-2-oxazoline. 2-isopropenyl-2-oxazoline, 4-methyl-2-isopropenyl-2-oxazoline, 5-methyl-2-isopropenyl-2-oxazoline, 2-isopropenyl-4,4-dimethyl-2-oxazoline Etc.

When the vinyl resin part includes a structural unit derived from an aromatic vinyl compound, it may be a vinyl resin part composed of one or more structural units derived from an aromatic vinyl compound, or an aromatic vinyl. It may be a vinyl copolymer part composed of a structural unit derived from a compound and a structural unit derived from another vinyl monomer. In the latter case, as the other vinyl monomer, a vinyl cyanide compound or a (meth) acrylic acid ester compound is preferable from the viewpoint of molding appearance and the like in the millimeter wave transmitting resin component of the present invention.
In the present invention, when the vinyl-based resin part includes a structural unit derived from an aromatic vinyl compound and a structural unit derived from a vinyl cyanide compound, the total amount of these structural units is the millimeter wave of the present invention. From the viewpoints of molding appearance, shape stability, chemical resistance and the like in the permeable resin part, the amount is preferably 70 to 100% by mass, more preferably 80 to 100% by mass, and more preferably 80% to 100% by mass, further. Preferably it is 85-100 mass%. In addition, the content ratio of the structural unit derived from the aromatic vinyl compound and the structural unit derived from the vinyl cyanide compound is preferably 55 to 95 masses when the total of these is 100 mass% from the above viewpoint. % And 5-45 mass%, More preferably, it is 60-90 mass% and 10-40 mass%, More preferably, it is 65-80 mass% and 20-35 mass%.

  The content ratio of the rubber polymer part and the vinyl resin part constituting the rubber polymer reinforced vinyl resin (A1) is from the viewpoint of mechanical properties and molded appearance in the millimeter wave transmitting resin part of the present invention. When the total of these is 100% by mass, preferably 40 to 85% by mass and 15 to 60% by mass, more preferably 50 to 80% by mass and 20 to 50% by mass, and still more preferably 55 to 75% by mass. And 25 to 45% by mass.

The graft ratio of the rubbery polymer reinforced vinyl resin (A1), which is a graft resin, is preferably 20% or more, more preferably 30% or more, and still more preferably 35, from the viewpoints of mechanical properties and molding appearance. ~ 65%.
The graft ratio can be determined by the following formula.
Graft rate (%) = {(S−T) / T} × 100
In the above formula, S represents 1 g of rubbery polymer reinforced vinyl resin (A1) in 20 ml of acetone, shaken with a shaker for 2 hours under a temperature condition of 25 ° C., and then a temperature condition of 5 ° C. Below, it is the mass (g) of the insoluble part obtained by centrifuging for 60 minutes with a centrifuge (rotation speed: 23,000 rpm), and separating an insoluble part and a soluble part, and T is a rubbery polymer. It is the mass (g) of the rubber-like polymer contained in 1 gram of the reinforced vinyl resin (A1). The mass of the rubbery polymer can be obtained by a method of calculating from a polymerization prescription and a polymerization conversion rate, a method of obtaining from an infrared absorption spectrum (IR), and the like.

  The rubbery polymer reinforced vinyl resin (A1) includes a rubbery polymer reinforced vinyl resin (diene rubbery polymer reinforced vinyl) having a polymer part derived from a diene rubber and a vinyl resin part. Resin), a polymer part derived from an acrylic rubber, and a rubbery polymer reinforced vinyl resin (acrylic rubbery polymer reinforced vinyl resin) having a vinyl resin part, an ethylene / α-olefin rubber Polymer part derived from rubber and polymer derived from hydrogenated diene rubber, rubber polymer reinforced vinyl resin (ethylene / α-olefin rubber polymer reinforced vinyl resin) having vinyl resin part A rubbery polymer reinforced vinyl resin (hydrogenated diene rubbery polymer reinforced vinyl resin), a polymer part derived from silicone rubber, and a vinyl resin part. And a rubbery polymer reinforced vinyl resin (silicone rubbery polymer reinforced vinyl resin). These may be used alone or in combination of two or more. That is, the thermoplastic resin composition may contain only one kind of rubber polymer reinforced vinyl resin (A1), or may contain two or more kinds in combination.

As described above, the component [A] according to the present invention may be composed of a rubber polymer reinforced vinyl resin and a vinyl resin not including the rubber polymer portion. In this case, the content ratio of both is set so that the content ratio of the rubber polymer part constituting the rubber polymer reinforced vinyl resin is 15 to 65% by mass with respect to the whole component [A]. Is done.
In the case of the above embodiment, the rubbery polymer reinforced vinyl resin is preferably the rubbery polymer reinforced vinyl resin (A1). On the other hand, the vinyl resin is preferably an aromatic vinyl compound, a vinyl cyanide compound, a (meth) acrylic ester compound, a maleimide compound, an unsaturated acid anhydride, a carboxyl group-containing unsaturated compound, or an amino group-containing unsaturated compound. It is a (co) polymer resin obtained by using at least one selected from a compound, an amide group-containing unsaturated compound, a hydroxyl group-containing unsaturated compound, and an oxazoline group-containing unsaturated compound. Among them, a (co) polymer resin (A2) comprising at least one selected from a structural unit derived from an aromatic vinyl compound, a structural unit derived from a vinyl cyanide compound, and a structural unit derived from a (meth) acrylic acid alkyl ester compound. Is particularly preferred.

  Examples of the (co) polymer resin (A2) include polystyrene, acrylonitrile / styrene copolymer, acrylonitrile / α-methylstyrene copolymer, acrylonitrile / styrene / methyl methacrylate copolymer, acrylonitrile / α-methylstyrene / methacrylic. Examples include acid methyl copolymer and polymethyl methacrylate. These may be used alone or in combination of two or more.

  Next, the component [B] is preferably a non-modified (co) polymer composed of at least one structural unit derived from an α-olefin having 2 or more carbon atoms. In the present invention, a particularly preferred component [B] is a polyolefin resin comprising at least one structural unit derived from an α-olefin having 2 to 10 carbon atoms.

  Examples of the α-olefin include ethylene, propylene, butene-1, pentene-1, hexene-1, 3-methylbutene-1, 4-methylpentene-1, 3-methylhexene-1, and the like. These can be used alone or in combination of two or more. Of these, ethylene, propylene, butene-1, 3-methylbutene-1 and 4-methylpentene-1 are preferable, and propylene is particularly preferable.

  Examples of the polyolefin resin consisting only of structural units derived from α-olefin include polyethylene, polypropylene, ethylene / propylene copolymer, polybutene-1, and ethylene / butene-1 copolymer. Of these, polyethylene, polypropylene, and propylene / ethylene copolymers are preferred, and polypropylene resins containing 85% by mass or more of propylene units based on all structural units from the viewpoint of mechanical properties, molding appearance, and millimeter wave permeability. That is, polypropylene and ethylene / propylene copolymer are more preferable. Examples of the ethylene / propylene copolymer include a random copolymer and a block copolymer, and a random copolymer is particularly preferable.

The component [B] may be crystalline or amorphous. Preferably, it has a crystallinity of 20% or more by X-ray diffraction at room temperature.
Tm of the said component [B] becomes like this. Preferably it is 40 degreeC or more.
The molecular weight of the component [B] is not particularly limited, but the melt mass flow rate (hereinafter also referred to as “MFR”) according to JIS K7210 is preferably 0.01 from the viewpoint of mechanical properties and molding appearance. It is -500g / 10min, More preferably, it is 0.05-100g / 10min, and what has the molecular weight corresponded to each value is preferable.

  The said thermoplastic resin composition may contain only 1 type of component [B], and may contain it in combination of 2 or more types.

  The content ratios of the components [A] and [B] contained in the thermoplastic resin composition are as follows. From the viewpoint of millimeter wave permeability, shape stability, and mechanical properties, when the total of both is 100% by mass, And preferably 35 to 95% by mass and 5 to 65% by mass, more preferably 50 to 90% by mass and 10 to 50% by mass, still more preferably 65 to 85% by mass and 15 to 35% by mass.

As described above, the thermoplastic resin composition according to the present invention may contain other thermoplastic resins in addition to the components [A] and [B]. When the other thermoplastic resin is contained, the upper limit of the content is preferably 30 parts by mass, more preferably 20 parts by mass with respect to 100 parts by mass in total of the components [A] and [B].
As another thermoplastic resin, a resin obtained by hydrogenating a copolymer containing a modified polyolefin resin, a structural unit derived from an aromatic vinyl compound, and a structural unit derived from a conjugated diene compound (hereinafter, “ Hydrogenated styrene / diene resin ”, styrene / diene resin, polycarbonate resin, polyamide resin, polyester resin, polyvinyl chloride resin, polyvinylidene chloride resin, fluorine resin, and the like. Some modified polyolefin resins and hydrogenated styrene / diene resins improve the compatibility of components [A] and [B] depending on the type of component [A].

  Examples of the modified polyolefin resin include a resin having a functional group such as a carboxylic acid group, an acid anhydride group, an epoxy group, a hydroxyl group, an amino group, and a silane group; an aromatic vinyl compound in the presence of an unmodified polyolefin resin; A graft copolymer resin obtained by polymerizing a vinyl monomer containing a vinyl cyanide compound can be used. As the (non-modified) polyolefin-based resin before modification, a random unit composed of a structural unit derived from polyethylene, polypropylene, poly-1-butene, polyisobutylene, and propylene and a structural unit derived from ethylene and / or 1-butene. Copolymer or block copolymer, ethylene / propylene / nonconjugated diene copolymer comprising a structural unit derived from ethylene, a structural unit derived from propylene, and a structural unit derived from nonconjugated diene (50% by mass or less) A copolymer comprising a structural unit derived from a polymer, polymethylpentene or cyclopentadiene and a structural unit derived from ethylene and / or propylene, a structural unit derived from ethylene or propylene, and another vinyl monomer; A random copolymer comprising structural units derived from (50% by mass or less) or Lock copolymers.

  Among the modified polyolefin resins, resins having a carboxylic acid group or an acid anhydride group are used as compatibilizers, in particular, the component [A] is a diene rubbery polymer reinforced vinyl resin or ethylene / α-olefin resin. It is suitable when a rubbery polymer reinforced vinyl resin is included.

  The graft copolymer resin that can be used as the modified polyolefin resin is preferably a graft copolymer obtained by polymerizing a vinyl monomer containing an aromatic vinyl compound and a vinyl cyanide compound in the presence of a propylene resin. It is a copolymer resin. This vinyl monomer may include other monomers copolymerizable with an aromatic vinyl compound or a vinyl cyanide compound. The graft ratio in the graft copolymer resin is preferably 20 to 200%, more preferably 30 to 150%, and still more preferably 40 to 120%.

  The properties of the propylene-based resin are not particularly limited, but the melt mass flow rate (MFR) measured under conditions of a temperature of 230 ° C. and a load of 2.16 kg is preferably 1 to 100 g / 10 minutes, more preferably 5 to 5 minutes. 50 g / 10 min, more preferably 5-30 g / 10 min. Further, the molecular weight distribution (Mw / Mn) measured by GPC is preferably 1.2 to 10, more preferably 1.5 to 8, still more preferably 2 to 6, and Tm is preferably 150 ° C. to 170. ° C, more preferably 155 ° C to 167 ° C. The propylene resin is preferably a propylene homopolymer.

  The vinyl monomers used for forming the graft copolymer resin are exemplified as vinyl monomers used for forming the vinyl resin portion in the rubbery polymer reinforced vinyl resin (A1). The monomer description applies.

  The content ratio of the propylene-based resin in the graft copolymer resin is preferably 5 to 70% by mass, more preferably 10 to 60% by mass, and still more preferably 20 to 50% when the graft copolymer resin is 100% by mass. % By mass.

  Among the modified polyolefin resins, the graft copolymer resin is suitable as a compatibilizing agent, particularly when the component [A] contains an ethylene / α-olefin rubbery polymer reinforced vinyl resin.

  Next, in the hydrogenated styrene / diene resin, the content ratio of the structural unit derived from the aromatic vinyl compound and the structural unit derived from the conjugated diene compound is preferably 10 to 90% by mass and 10%, respectively. -90% by mass, more preferably 30-90% by mass and 10-70% by mass, and even more preferably 50-80% by mass and 20-50% by mass of a copolymer (hereinafter referred to as “precursor”) as hydrogen. It is a resin obtained by addition.

The precursor is a block copolymer in which the content of 1,2- and 3,4-vinyl bonds, which are the microstructure of the diene portion, is 10 to 80% when the total amount of vinyl bonds is 100%. X is a polymer block composed of a structural unit derived from an aromatic vinyl compound, Y is a polymer block composed of a structural unit derived from a conjugated diene compound, and X / Y is an aromatic vinyl compound and a conjugate. Random copolymer block consisting of structural units derived from both diene compounds, Z is a polymer block consisting of structural units derived from both aromatic vinyl compounds and conjugated diene compounds, and aromatic vinyl compounds When it is set as the taper block from which the derived structural unit increases gradually, it is illustrated by following (1)-(10).
(1) XY
(2) XYX
(3) XYZ
(4) X-Y1-Y2 (Y1 vinyl bond is preferably 20% or more, Y2 vinyl bond is preferably less than 20%)
(5) X / Y
(6) XX / Y
(7) XX / YZ
(8) XX / YX
(9) ZX / YZ
(10) ZXY

As the aromatic vinyl compound, the description of the compound exemplified as the aromatic vinyl compound used for forming the vinyl resin portion is applied, and styrene is preferable.
The conjugated diene compound is a case where the rubbery polymer portion in the rubbery polymer reinforced vinyl resin (A1) is derived from a hydrogenated diene rubber, which is used to form the hydrogenated diene rubber. The description of the compound exemplified as the conjugated diene compound used is applied, and 1,3-butadiene is preferable.

  The hydrogenated styrene-diene resin is a resin in which 10 to 95%, more preferably 20 to 70%, more preferably 30 to 65% of the double bond portion contained in the precursor is hydrogenated. It is preferable that

  The hydrogenated styrene / diene resin is used as a compatibilizing agent, in particular, the component [A] is an ethylene / α-olefin rubber polymer reinforced vinyl resin, acrylic rubber polymer reinforced vinyl resin or silicone rubber. It is suitable when a high polymer reinforced vinyl resin is included.

  The thermoplastic resin composition according to the present invention may contain an additive as described above. These additives include fillers that improve the mechanical properties of resin parts, plasticizers, antioxidants, UV absorbers, anti-aging agents, flame retardants, stabilizers, weathering agents, light stabilizers, heat stabilizers, electrification Examples thereof include an inhibitor, a water repellent, an oil repellent, an antifoaming agent, an antibacterial agent, an antiseptic, and a colorant (pigment, dye, etc.).

According to the thermoplastic resin composition, the dielectric loss tangent at a frequency of 77 GHz is preferably 3.0 × 10 ^{−3 to} 10.0 × 10 ⁻³ , more preferably 3.3 × 10 ^{−3 to} 8.0 ×. 10 ⁻³ , more preferably 3.5 × 10 ^{−3 to} 7.0 × 10 ⁻³ . The relative dielectric constant can be preferably 2.4 to 2.8, more preferably 2.5 to 2.7, and still more preferably 2.5 to 2.6.

The millimeter wave transmitting resin component or the millimeter wave radome of the present invention was obtained by melting the thermoplastic resin composition or a mixture of raw material components thereof and then subjecting it to a conventionally known molding method such as injection molding. Can be.
The millimeter wave transmitting resin component 60 of the present invention can be used alone as the millimeter wave radome 70 depending on its shape (see FIGS. 1, 2, 5, and 6). Further, the millimeter wave transmitting resin part 60 of the present invention can be combined with other resin parts 62, 66, etc. to form a millimeter wave radome 70 (see FIGS. 3, 4 and 7).

  The shapes of the millimeter-wave transmitting resin component and the millimeter-wave radome of the present invention are not particularly limited, and can have curved surface portions, corner portions, etc. as shown in FIGS. It can be according to the shape such as.

  1, 2, 3, 4, and 7 show a millimeter wave radar in which an antenna module 12 that can transmit and receive as a single body is stored or protected by a millimeter wave radome 70. Two antennas, for example, a transmitting antenna module 12A and a receiving antenna module 12B, are stored or protected by a millimeter wave radome 70 (FIG. 5) having a partition 64 that absorbs or reflects millimeter waves. Show. The antenna modules 12, 12 </ b> A, 12 </ b> B may be disposed on the antenna base 14 made of, for example, a resin or an inorganic material (metal, ceramics, etc.). The millimeter wave radome 70 may be disposed on the antenna base 14 directly or via another member. In FIGS. 1, 2, 3, 4, 6, and 7, the antenna base 14 is a flat plate. However, the antenna base 14 is not limited to this, and has a curved plate, a concavo-convex cross section, or a zigzag cross section. There may be.

  The millimeter wave radar 10 of FIG. 1 and FIG. 2 is an aspect including a millimeter wave radome 70 made of a hemispherical millimeter wave transmitting resin component 60 having the same thickness throughout. Millimeter waves can be transmitted and received throughout the right side of the drawing. In order to enable transmission / reception of millimeter waves only in a specific direction from the antenna module 12, a part having a thick part that is too thick or too thin than the preferred length despite being made of the same thermoplastic resin composition. Thus, it is possible to adopt an aspect including the millimeter wave transmissive resin component 60 in which the transmittance of the millimeter wave having a specific wavelength is made different.

The millimeter wave radar 20 of FIG. 3 is a mode in which a millimeter wave radome 70 is formed by combining a millimeter wave transmitting resin part 60 and another resin part 62 that absorbs or reflects millimeter waves, and an antenna module. 12 can transmit and receive millimeter waves only in a specific direction.
The millimeter wave radar 30 of FIG. 4 is an aspect including a millimeter wave radome 70 including a millimeter wave transmissive resin component 60 and another millimeter wave transmissive resin component 66, and the antenna base 14 in the entire right side of the drawing. Millimeter wave transmission and reception are possible. The other millimeter wave transmitting resin component 66 may be made of the thermoplastic resin composition according to the present invention, or may be made of a conventionally known resin composition.

  FIG. 5 shows a rectangular parallelepiped millimeter wave transmission made of the thermoplastic resin composition according to the present invention, except that the partition 64 is made thicker and the millimeter wave permeability with other parts is different. 6 shows a resin component 60 or a millimeter wave radome 70. The millimeter wave radar 40 of FIG. 6 including the resin component 60 is configured to store the transmitting antenna module 12A and the receiving antenna module 12B separately by the partitioning portion 64. In the case of the millimeter wave radar 40 having such a configuration, the wraparound of the millimeter wave from the transmission antenna unit to the reception antenna unit is suppressed by the partition unit 64. 5 shows the integrated millimeter-wave transmitting resin component 60 or the millimeter-wave radome 70 provided with the partition portion 64. However, as another embodiment, the partition portion 64 is made of a material that absorbs or reflects millimeter waves. A millimeter-wave radar including a millimeter-wave radome 70 formed of a member made of

Fig. 7 shows the focus of attention on the core technology of the Intelligent Transport System (ITS) aimed at reducing vehicle congestion and reducing accidents. C. C. It is the schematic of the millimeter wave radar 50 as components, such as a sensor suitable for (adaptive cruise control).
The basic structure of FIG. 7 is a combination of FIG. 3 and FIG. 4, and the antenna module 12 disposed on the antenna base 14 is replaced by a millimeter wave transmissive resin component 60, another millimeter wave transmissive resin component 66, and It is stored by a millimeter wave radome composed of another resin component 62 that absorbs or reflects millimeter waves. And between the millimeter wave transparent resin part 60 and the other millimeter wave transparent resin part 66, it is a layer which does not ask | require millimeter wave permeability, Comprising: The decoration layer 68 which forms the design in the front surface of a vehicle is provided. The design drawn by the decorative layer 68 can be recognized from the other millimeter wave transmitting resin component 66 side. The decorative layer 68 can be formed by printing, painting, vapor deposition, or the like.
Although not shown in the figure, a millimeter wave radar in which the other millimeter wave transmitting resin parts 66 in FIG.

  Hereinafter, the present invention will be described in more detail with reference to an example in which a hemispherical resin molded product (60, 70) shown in FIG. 1 is manufactured using a thermoplastic resin composition made of the raw materials shown in Tables 1 to 3. However, as long as the gist of the present invention is not exceeded, the present invention is not limited to such examples. In the following, “part” and “%” are based on mass unless otherwise specified.

1. Production raw materials for resin molded products The raw materials used in Examples 1 to 19 and Comparative Examples 1 to 4 are as follows. The measurement of the graft rate was performed according to the method described above.

1-1. Raw material (A)
A rubbery polymer reinforced resin in which various rubbery polymer reinforced vinyl resins and acrylonitrile / styrene copolymer resin were combined was used.

1-1-1. ABS
A diene rubbery polymer reinforced vinyl resin having a graft ratio of 55% obtained by emulsion polymerization of styrene and acrylonitrile in the presence of polybutadiene rubber having a gel fraction of 86% and an average particle size of 290 nm; It is a rubbery polymer reinforced resin made of acrylonitrile / styrene copolymer resin. The graft ratio in the diene rubber polymer reinforced vinyl resin is 55%, the polybutadiene rubber content in the rubber polymer reinforced resin is 40.5%, the acrylonitrile unit amount is 17.0%, and the styrene unit amount. Was 42.5%. The intrinsic viscosity [η] (measured in methyl ethyl ketone at 30 ° C.) of the ungrafted acrylonitrile / styrene copolymer resin (acetone soluble component) was 0.45 dl / g.

1-1-2. AES (EPR)
In a toluene solvent, obtained by solution polymerization of styrene and acrylonitrile in the presence of an ethylene / propylene copolymer rubber having an ethylene unit amount of 78%, a propylene unit amount of 22%, and a Tm of 40 ° C., It is a rubbery polymer reinforced resin comprising an ethylene / α-olefin rubbery polymer reinforced vinyl resin and an ungrafted acrylonitrile / styrene copolymer resin. The graft ratio of the ethylene / α-olefin rubbery polymer reinforced vinyl resin is 55%, the content of ethylene / propylene copolymer rubber contained in the rubbery polymer reinforced resin is 30%, and the acrylonitrile unit amount is 24%. The styrene unit amount was 46%. The intrinsic viscosity [η] (measured in methyl ethyl ketone at 30 ° C.) of the ungrafted acrylonitrile / styrene copolymer resin (acetone soluble component) was 0.5 dl / g.

1-1-3. AES (EPDM)
Ethylene / propylene / ethylene propylene unit having an ethylene unit amount of 63%, a propylene unit amount of 32%, a dicyclopentadiene unit amount of 5% and a Mooney viscosity (ML _{1 + 4} , 100 ° C.) of 33 in a toluene solvent. A rubber comprising an ethylene / α-olefin rubber polymer-reinforced vinyl resin obtained by polymerizing styrene and acrylonitrile in the presence of a dicyclopentadiene copolymer rubber and an ungrafted acrylonitrile / styrene copolymer resin. Polymer-reinforced resin. The graft ratio of the ethylene / α-olefin rubbery polymer reinforced vinyl resin is 60%, the content of the ethylene / propylene / dicyclopentadiene copolymer rubber contained in the rubbery polymer reinforced resin is 30%, and an acrylonitrile unit. The amount was 23%, and the styrene unit amount was 47%. The intrinsic viscosity [η] (measured in methyl ethyl ketone at 30 ° C.) of the ungrafted acrylonitrile / styrene copolymer resin (acetone soluble component) was 0.45 dl / g.

1-1-4. PX (DR)
Hydrogenated diene obtained by polymerizing methyl methacrylate, styrene and acrylonitrile in toluene solvent in the presence of hydrogenated styrene-ethylene-butylene-ethylene block copolymer “Dynalon 4600P” (trade name) manufactured by JSR It is a rubber polymer reinforced resin comprising a vinyl rubber polymer reinforced vinyl resin and an ungrafted methyl methacrylate / acrylonitrile / styrene copolymer resin. The graft ratio in the hydrogenated diene rubber polymer reinforced vinyl resin is 45%, the hydrogenated diene rubber content in the rubber polymer reinforced resin is 30%, the methyl methacrylate unit amount is 50%, The acrylonitrile unit amount was 10%, and the styrene unit amount was 10%. The intrinsic viscosity [η] (measured in methyl ethyl ketone at 30 ° C.) of the ungrafted methyl methacrylate / acrylonitrile / styrene copolymer resin (acetone soluble component) was 0.48 dl / g.

1-1-5. ASA
In a glass flask equipped with a stirrer, 85 parts of ion-exchanged water, 0.7 parts of potassium rosinate, 0.45 parts of sodium bicarbonate, 0.15 parts of sodium carbonate, sodium naphthalenesulfonate formalin condensation in a nitrogen stream 0.5 part salt and 0.03 part sodium dithionite were added. As a monomer, 5 parts of n-butyl acrylate was added, and the temperature was increased while stirring. When the internal temperature reached 75 ° C., 0.12 part of potassium persulfate was added to initiate polymerization. After polymerization for 1 hour, 0.06 part of potassium persulfate, 44.5 parts of n-butyl acrylate and 0.5 part of allyl methacrylate were continuously added over 3 hours, and the polymerization was further continued for 1 hour. Thereafter, it is cooled to 65 ° C., 33 parts of ion-exchanged water, 0.8 part of potassium rosinate and 0.07 part of tert-butyl hydroperoxide are added, 0.4 parts of sodium pyrophosphate, and 7 water of ferrous sulfate. A solution obtained by dissolving 0.01 part of Japanese product and 0.3 part of glucose in 15 parts of ion-exchanged water, 10.95 parts of styrene, and 4.05 parts of acrylonitrile were added, and the temperature was raised to 75 ° C. After polymerization for 1 hour, 25.55 parts of styrene, 9.45 parts of acrylonitrile, 0.1 part of tert-dodecyl mercaptan and 0.2 part of tert-butyl hydroperoxide were continuously added over 4 hours. The polymerization was continued for 1 hour. After coagulation with a magnesium sulfate solution, washing with water and drying, a rubbery polymer reinforced resin was obtained. The graft ratio of acrylic rubber polymer reinforced vinyl resin contained in this rubber polymer reinforced resin is 40%, and the content of ungrafted acrylonitrile / styrene copolymer resin (acetone soluble component) is 30%. The intrinsic viscosity [η] of this acetone-soluble component (in methyl ethyl ketone, 30 ° C.) was 0.43 dl / g.

1-1-6. SX
A mixture of 1.5 parts of p-vinylphenylmethyldimethoxysilane and 98.5 parts of octamethylcyclotetrasiloxane was added to 300 parts of an aqueous solution in which 2.0 parts of dodecylbenzenesulfonic acid was dissolved in distilled water. The mixture was stirred and emulsified for 3 minutes. The emulsified dispersion is transferred to a separable flask equipped with a condenser, a nitrogen gas inlet, and a stirrer. Under stirring, the emulsion is heated at 90 ° C. for 6 hours to undergo a condensation reaction, and cooled at 5 ° C. for 24 hours to complete the reaction. It was. As a result, a latex containing a modified polyorganosiloxane rubber with a condensation rate of 92.8% was obtained. Thereafter, the latex was neutralized to pH 7 by adding an aqueous sodium carbonate solution. The volume average particle diameter of the modified polyorganosiloxane rubber was 280 nm.
Next, in a glass flask equipped with a stirrer, 40 parts of the modified polyorganosiloxane rubber, 100 parts of ion exchange water, 1.5 parts of sodium dodecylbenzenesulfonate, 0.1 part of tert-dodecyl mercaptan, 15 parts of styrene and Acrylonitrile (5 parts) was accommodated and heated to 45 ° C. with stirring. Thereafter, an activator aqueous solution comprising 0.1 part of ethylenediaminetetraacetic acid sodium salt, 0.003 part of ferrous sulfate, 0.2 part of sodium formaldehyde sulfoxylate dihydrate and 15 parts of ion-exchanged water, and diisopropylbenzene 0.1 part of hydroperoxide was added to initiate polymerization. And after 1 hour, incremental polymerization consisting of 50 parts of ion-exchanged water, 1 part of sodium dodecylbenzenesulfonate, 0.1 part of tert-dodecyl mercaptan, 0.2 part of diisopropyl hydroperoxide, 30 parts of styrene and 10 parts of acrylonitrile. The ingredients were added continuously over 3 hours and polymerization was continued. After the addition was complete, stirring was continued for 1 hour.
Thereafter, 0.2 part of 2,2-methylene-bis (4-ethylene-6-tert-butylphenol) was added to terminate the polymerization, and a latex containing a rubbery polymer reinforced resin was obtained. Next, 2 parts of calcium chloride was added to the latex to coagulate the resin component, washed with water and dried (75 ° C., 24 hours) to recover a white powder (rubber polymer reinforced resin). The polymerization conversion rate is 97.2%, the graft ratio of the silicone rubber polymer reinforced vinyl resin contained in this rubber polymer reinforced resin is 90%, and the limit of acetone soluble content (acrylonitrile / styrene copolymer resin) The viscosity [η] (in methyl ethyl ketone, 30 ° C.) was 0.47 dl / g.

1-1-7. AS (acrylonitrile / styrene copolymer resin)
An acrylonitrile / styrene copolymer resin having a styrene unit amount of 70% and an acrylonitrile unit amount of 30% was used. The intrinsic viscosity [η] (measured in methyl ethyl ketone at 30 ° C.) was 0.40 dl / g.

1-2. Raw material (B)
A block type polypropylene “Novatec BC6C” (trade name) manufactured by Nippon Polypro Co., Ltd. was used.

1-3. Raw material (C)
The following SBC, PP-g-AS and mPO were used as compatibilizers.

1-3-1. SBC
A hydrogenated styrene / butadiene / butylene / styrene block copolymer “Tuftec P2000” (trade name) manufactured by Asahi Kasei Chemicals Corporation was used. MFR (temperature 190 ° C., load 2.16 kg) is 3 g / 10 min.

1-3-2. PP-g-AS
A graft resin mixture obtained by polymerizing styrene and acrylonitrile in the presence of polypropylene having an MFR (temperature: 230 ° C., load: 2.16 kg) in a toluene solvent in the presence of 10 g / 10 min. The graft ratio in the graft resin contained in the graft resin composition was 43.3%, the content of polypropylene contained in the graft resin composition was 41%, the acrylonitrile unit amount was 17%, and the styrene unit amount was 42%. .

1-3-3. mPO
An acid-modified low molecular weight polypropylene resin “Yumex 1001” (trade name) manufactured by Sanyo Chemical Industries, Ltd. was used. The acid value is 26.

2. Production and physical property evaluation of resin parts for radome Examples 1 to 20 and Comparative Examples 1 to 4
After the raw materials (A), (B) and (C) were mixed at a ratio shown in Tables 1 to 3 by a Henschel mixer, this mixture was mixed with a twin-screw extruder “TEX44αII” (model) manufactured by Nippon Steel Corporation. Name) and melt-kneaded (cylinder setting temperature: 180 ° C. to 220 ° C.) to obtain pellets made of the thermoplastic resin composition. This pellet was subjected to injection molding to obtain a hemispherical molded product (reference numerals 60 and 70 in FIG. 1) having an outer diameter of 50 mm and a wall thickness of 2 mm. Among these, about Example 3, 6, 12, 15, 16 and 20, the surface was visually observed for the presence or absence of black or silver, and the molded appearance was evaluated. Moreover, the test piece of the predetermined shape was produced from the pellet, and it used for the following evaluation. The results are shown in Tables 1 to 3.

2-1. Dielectric constant and dielectric loss tangent (tan δ)
Using a device manufactured by Agilent Technologies, the relative dielectric constant and dielectric loss tangent at a frequency of about 77 GHz were measured by the cut-off cylindrical waveguide method (JIS R1660-1).

2-2. Impact Resistance Charpy impact strength was measured at a temperature of 23 ° C. according to ISO 179. The unit is “kJ / m ² ”.
2-3. Mold Shrinkage According to JIS K7152-4, the mold shrinkage rate of the test piece was measured at a temperature of 23 ° C. in the MD direction and the TD direction, respectively.
○: Less than 0.8% △: 0.8% to 1.2%
X: 1.2% excess 2-4. Flowability In accordance with ISO 1133, the melt mass flow rate was measured under the conditions of a temperature of 220 ° C. and a load of 98N. The unit is “g / 10 minutes”.

From Tables 1 to 3, the following can be understood.
The comparative example 1 is an example using the thermoplastic resin composition which consists only of a raw material (A), and is inferior to impact resistance and shape stability. Comparative Examples 2 to 4 are examples using a thermoplastic resin composition consisting only of the raw material (B), and although impact resistance was obtained, millimeter wave permeability was not sufficient.
On the other hand, according to Examples 1-20, it is excellent in all of millimeter wave permeability, impact resistance, and shape stability. In particular, according to Examples 11 to 20 using the thermoplastic resin composition further containing the raw material (C), it can be seen that the low dielectric loss tangent is further reduced and the millimeter wave permeability is more excellent. In Examples 3, 6, 12, 15, 16, and 20, no solids or silver was observed on the surface of the hemispherical molded product.

  The millimeter-wave transparent resin component, millimeter-wave radome, and millimeter-wave radar of the present invention are attracting attention as the core technology of an intelligent road traffic system (ITS) that aims to reduce vehicle congestion and reduce accidents. C. C. It can be used as a component such as a sensor suitable for (adaptive cruise control).

10, 20, 30, 40, 50: Millimeter wave radar 12, 12A, 12B: Antenna module 14: Antenna base 60: Millimeter wave transmitting resin component 62: Resin component for absorbing or reflecting millimeter wave 64: Partition 66: Other millimeter wave transparent resin parts 68: Decorative layer 70: Millimeter wave radome

Claims (6)

[A] a rubber polymer reinforced resin, and [B] a thermoplastic resin composition containing a polyolefin resin, which is a resin component that transmits millimeter waves,
The rubbery polymer reinforced resin [A] comprises (A1) a rubbery polymer reinforced vinyl resin and (A2) a (co) polymer resin,
The rubber polymer reinforced vinyl-based resin (A1) is a polymer unit derived from ethylene · alpha-olefin rubber, at least one rubbery polymer selected from hydrogenated diene rubber and silicone rubber, vinyl It is a graft resin that is chemically bonded to the system resin part,
The (co) polymer resin (A2) is at least one selected from a structural unit derived from an aromatic vinyl compound, a structural unit derived from a vinyl cyanide compound, and a structural unit derived from a (meth) acrylic acid alkyl ester compound. Resin parts characterized by comprising The vinyl resin portion in the rubbery polymer reinforced vinyl resin (A1) includes a structural unit derived from an aromatic vinyl compound and a structural unit derived from a vinyl cyanide compound,
The total amount of the structural unit derived from the aromatic vinyl compound and the structural unit derived from the vinyl cyanide compound is 70 to 100% by mass with respect to the total amount of the vinyl resin part. Resin parts.   The content ratios of the rubbery polymer reinforced resin [A] and the polyolefin resin [B] are 30 to 95% by mass and 5 to 70% by mass, respectively, when the total of both is 100% by mass. Item 3. The resin part according to Item 1 or 2. The resin part according to any one of claims 1 to 3 , wherein the ethylene / α-olefin rubber is an ethylene / α-olefin copolymer.   A radome for millimeter waves comprising the resin component according to any one of claims 1 to 4. A millimeter wave radar comprising the millimeter wave radome according to claim 5.

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