JP2005200581A - Low dielectric and heat-resistant styrene resin composition, resin molded article obtained by using the same, and molded part for electronic/communication instrument - Google Patents
Low dielectric and heat-resistant styrene resin composition, resin molded article obtained by using the same, and molded part for electronic/communication instrument Download PDFInfo
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本発明は、低誘電性で耐熱性を有するスチレン系樹脂組成物、またそれを用いた高周波帯域で使用可能な樹脂成形品並びに電子・通信機器用成形部品等に関するものである。 The present invention relates to a low-dielectric and heat-resistant styrene-based resin composition, a resin molded product that can be used in a high-frequency band, a molded part for electronic / communication equipment, and the like.
近年、情報通信機器類は情報処理速度等向上のため１ＧＨｚ以上の高周波領域で使用されてきており、そのため前記機器類に用いる部品等は高周波領域での伝送損失が小さいことが要求されている。例えばフレキシブルプリント配線基板ではポリイミドフィルムが多用されているが、ポリイミドフィルムの誘電率は３．５程度（＠２．４５ＧＨｚ）と大きいので、更なる低誘電率化が望まれている。例えば特許文献１に見られるように、電気絶縁性で低誘電率の材料として、各種ポリエチレン、エチレンプロピレン共重合体、ポリプロピレン、ポリブテン、ポリ４−メチルペンテン等の非極性α−オレフィンの単独ないし共重合体、ブタジエン、イソプレン、ペンタジエン、ヘキサジエン、オクタジエン、フェニルブタジエン、ジフェニルブタジエン等の共役ジエンの重合体や共重合体、スチレン、核置換スチレン、α−置換スチレン、ジビニルベンゼン、ビニルシクロヘキサン等の炭素環含有ビニルの単量体、共重合体等が記載されている。しかしながらオレフィン系の重合体や共重合体は、電気的特性には優れているが耐熱性が低い欠点がある。また前記スチレン系樹脂では、耐熱性の問題と共に、最近の鉛フリーの半田に対する半田耐熱性が問題となっている。 In recent years, information communication devices have been used in a high frequency region of 1 GHz or more in order to improve information processing speed and the like. Therefore, components used for the devices are required to have a small transmission loss in the high frequency region. For example, polyimide films are frequently used in flexible printed wiring boards, but since the dielectric constant of polyimide films is as large as about 3.5 (@ 2.45 GHz), further reduction in dielectric constant is desired. For example, as seen in Patent Document 1, as an electrically insulating and low dielectric constant material, various types of polyethylene, ethylene propylene copolymer, polypropylene, polybutene, poly-4-methylpentene, and other nonpolar α-olefins may be used alone or in combination. Polymers, copolymers and copolymers of conjugated dienes such as butadiene, isoprene, pentadiene, hexadiene, octadiene, phenylbutadiene, diphenylbutadiene, and carbocycles such as styrene, nucleus-substituted styrene, α-substituted styrene, divinylbenzene, vinylcyclohexane Contains vinyl monomers, copolymers, and the like. However, olefin-based polymers and copolymers have a drawback that they have excellent electrical characteristics but low heat resistance. In addition, the styrene resin has a problem of soldering heat resistance against recent lead-free solder as well as heat resistance.
そこで耐熱性に優れた材料として、テトラフルオロエチレン樹脂（ＰＴＦＥ）のようにフッ素原子を分子鎖中に含有させたポリマー等が考えられているが、このような樹脂においても、前記の半田耐熱性の問題から用途が制限され広く使用されるには至っていない。そこで耐熱性を改良する目的で、ガラスファイバや無機化合物を多量に樹脂中に添加することも考えられているが、このような樹脂材料は誘電率が通常４以上となって、低誘電性の点から問題があった。さらにポリイミド樹脂等の多孔質化も検討されているが、吸水時の誘電特性の悪化や機械的特性の低下の問題があり、実用化には至っていないのが現状である。
よって本発明が解決しようとする課題は、１ＧＨｚ以上の高周波帯域で比誘電率が２．７０以下（＠２．４５ＧＨｚ）である低誘電性であると共に、少なくとも２６０℃で１２０秒の耐半田耐熱性を有する低誘電性、耐熱性スチレン系樹脂組成物を提供することにある。そしてこのスチレン系樹脂組成物を成形加工した樹脂成形品とすることによって、またこの樹脂成形品を用いた電子・通信機器用成形部品とすることによって、高周波帯域（１ＧＨｚ以上）において、比誘電率で２．７０以下（＠２．４５ＧＨｚ）の低誘電性で、かつ少なくとも２６０℃で１２０秒の半田耐熱性を有する電子・通信機器用の成形部品を提供することにある。 Therefore, the problem to be solved by the present invention is a low dielectric constant having a relative dielectric constant of 2.70 or less (@ 2.45 GHz) in a high frequency band of 1 GHz or higher and a solder heat resistance of at least 260 ° C. for 120 seconds. An object of the present invention is to provide a low-dielectric and heat-resistant styrene-based resin composition having a property. Then, by using a resin molded product obtained by molding this styrenic resin composition, or by forming a molded part for electronic / communication equipment using this resin molded product, the relative dielectric constant in a high frequency band (1 GHz or more). It is to provide a molded part for electronic / communication equipment having a low dielectric constant of 2.70 or less (@ 2.45 GHz) and a solder heat resistance of at least 260 ° C. for 120 seconds.
前記解決しようとする課題は、請求項１に記載されるように、シンジオタクチックポリスチレン１００重量部とＮ−フェニルマレイミド・スチレン共重合体１〜１０重量部および粘土鉱物１〜１０重量部からなる低誘電性、耐熱性スチレン系樹脂組成物とすることによって、解決される。 The problem to be solved is composed of 100 parts by weight of syndiotactic polystyrene, 1 to 10 parts by weight of an N-phenylmaleimide / styrene copolymer and 1 to 10 parts by weight of a clay mineral as described in claim 1. This can be solved by using a low dielectric and heat resistant styrene resin composition.
また請求項２に記載されるように、前記粘土鉱物が、サポナイト、ヘクトライト、モンモリロナイト、バイデライト、バーミキュライト、マイカから選ばれる一種である低誘電性、耐熱性スチレ系樹脂組成物とすることによって、解決される。 In addition, as described in claim 2, the clay mineral is a low dielectric, heat-resistant styrenic resin composition which is a kind selected from saponite, hectorite, montmorillonite, beidellite, vermiculite, mica, Solved.
そして請求項３に記載されるように、前記低誘電性、耐熱性スチレン系樹脂組成物を所定形状に成形加工した、１ＧＨｚ以上の高周波帯域で使用可能なスチレン系樹脂成形品とすることによって、また請求項４に記載されるように、前記スチレン系樹脂成形品を用いた、１ＧＨｚ以上の高周波帯域で使用可能な電子・通信機器用成形部品とすることによって、解決される。 And as described in claim 3, by making the low dielectric, heat-resistant styrene resin composition into a predetermined shape, a styrene resin molded product usable in a high frequency band of 1 GHz or more, Further, as described in claim 4, the problem is solved by using a molded part for electronic / communication equipment that can be used in a high frequency band of 1 GHz or more using the styrene resin molded product.
以上のような、シンジオタクチックポリスチレン１００重量部とＮ−フェニルマレイミド・スチレン共重合体１〜１０重量部および粘土鉱物１〜１０重量部からなるスチレン系樹脂組成物とすることによって、また前記粘土鉱物としてサポナイト、ヘクトライト、モンモリロナイト、バイデライト、バーミキュライト、マイカから選ばれる一種を選択することによって、１ＧＨｚ以上の高周波帯域で使用しても、比誘電率が２．７０以下（＠２．４５ＧＨｚ）の低誘電性であると共に、少なくとも２６０℃で１２０秒の半田耐熱性を有する優れたスチレン系樹脂組成物となる。 By making a styrenic resin composition comprising 100 parts by weight of syndiotactic polystyrene, 1 to 10 parts by weight of N-phenylmaleimide / styrene copolymer and 1 to 10 parts by weight of clay mineral as described above, the clay By selecting one kind of mineral selected from saponite, hectorite, montmorillonite, beidellite, vermiculite, mica, the relative dielectric constant is 2.70 or less (@ 2.45 GHz) even when used in a high frequency band of 1 GHz or more. An excellent styrene-based resin composition having a low dielectric property and a solder heat resistance of at least 260 ° C. for 120 seconds is obtained.
また前記スチレン系樹脂組成物を用いた樹脂成形品とすることによって、１ＧＨｚ以上の高周波帯域で比誘電率が２．７０以下（＠２．４５ＧＨｚ）である低誘電性と、少なくとも２６０℃で１２０秒の半田耐熱性を有する電子・通信機器用部品の樹脂成形品として使用することができる。例えばフィルム状に成形した樹脂成形品は、銅箔と張り合わせることによって、プリント配線基板用の銅張積層板のような電子・通信機器用部品の樹脂成形品としての用途が考えられる。さらにそのような電子・通信機器用の部品は、１ＧＨｚ以上の高周波帯域で比誘電率が２．７０以下（＠２．４５ＧＨｚ）の低誘電性であると共に、少なくとも２６０℃で１２０秒の半田耐熱性を有する優れた電子・通信機器用部品とすることができる。例えばプリント配線基板用の銅張積層板や電子機器類のコネクタ等である。そしてこのような電子・通信機器用部品は、携帯電話、自動車用のナビゲーター、ＥＴＣ、アンテナ、ＰＣ等として、高周波帯域で使用可能な電子・通信機器として使用できる。 Further, by forming a resin molded article using the styrene-based resin composition, a low dielectric constant having a relative dielectric constant of 2.70 or less (@ 2.45 GHz) in a high frequency band of 1 GHz or more, and at least 120 ° C. at 260 ° C. It can be used as a resin molded product for electronic / communication equipment parts having a second solder heat resistance. For example, a resin molded product formed into a film shape can be used as a resin molded product for electronic / communication equipment parts such as a copper-clad laminate for printed wiring boards by bonding with a copper foil. Furthermore, such electronic / communication equipment components have a low dielectric constant with a relative dielectric constant of 2.70 or less (@ 2.45 GHz) in a high frequency band of 1 GHz or higher, and a solder heat resistance of at least 260 ° C. for 120 seconds. It can be set as an excellent component for electronic / communication equipment. For example, it is a copper-clad laminate for printed wiring boards, connectors for electronic devices, and the like. Such electronic / communication device parts can be used as electronic / communication devices that can be used in a high-frequency band, such as mobile phones, automobile navigators, ETCs, antennas, and PCs.
以下に本発明を詳細に説明する。請求項１に記載される発明は、シンジオタクチックポリスチレン１００重量部とＮ−フェニルマレイミド・スチレン共重合体１〜１０重量部および粘土鉱物１〜１０重量部からなる低誘電性、耐熱性スチレン系樹脂組成物であって、高周波帯域（１ＧＨｚ以上）において比誘電率が２．７０以下（＠２．４５ＧＨｚ）の低誘電性で、かつ半田耐熱性として少なくとも２６０℃、１２０秒に耐える耐熱性に優れたスチレン系樹脂組成物とすることができる。 The present invention is described in detail below. The invention described in claim 1 is a low-dielectric, heat-resistant styrene system comprising 100 parts by weight of syndiotactic polystyrene, 1 to 10 parts by weight of an N-phenylmaleimide / styrene copolymer and 1 to 10 parts by weight of a clay mineral. A resin composition having a low dielectric constant with a relative dielectric constant of 2.70 or less (@ 2.45 GHz) in a high frequency band (1 GHz or more) and a heat resistance that can withstand at least 260 ° C. for 120 seconds as a solder heat resistance. It can be set as the outstanding styrene-type resin composition.
まずベースポリマーとなるシンジオタクチックポリスチレン（ＳＰＳ）について説明する。このＳＰＳは、メタロセン触媒を用いて製造することによって、結晶性で耐熱性に優れたポリスチレン系樹脂として得ることができる。その立体構造は、主鎖に対してベンゼン環が規則的に配列された構造で、非結晶のアタクチックポリスチレンやアイソタクチックポリスチレンとは異なる特性を有している。通常エンジニアリングプラスチックとして使用され、例えば出光石油化学社からザレックＳ−１０４として市販されている。本発明ではこのＳＰＳをベースポリマーとして使用することによって、低誘電性と半田耐熱性を備えたスチレン系樹脂組成物（ＳＰＳ組成物）を得ることができる。そしてＳＰＳ組成物は、ＳＰＳを１００重量部とし、これに他の添加剤を配合することによって得られる。 First, syndiotactic polystyrene (SPS) serving as a base polymer will be described. This SPS can be obtained as a polystyrene-based resin excellent in crystallinity and heat resistance by being produced using a metallocene catalyst. The three-dimensional structure is a structure in which benzene rings are regularly arranged with respect to the main chain, and has different characteristics from non-crystalline atactic polystyrene and isotactic polystyrene. It is usually used as an engineering plastic and is commercially available as, for example, Zalek S-104 from Idemitsu Petrochemical. In the present invention, by using this SPS as a base polymer, a styrene resin composition (SPS composition) having low dielectric properties and solder heat resistance can be obtained. The SPS composition is obtained by adding 100 parts by weight of SPS and adding other additives thereto.
前記添加剤としては、Ｎ−フェニルマレイミド・スチレン共重合体並びに粘土鉱物が、それぞれ１〜１０重量部の範囲で配合される。前記Ｎ−フェニルマレイミド・スチレン共重合体は、ＳＰＳ組成物を得る際の押出機等での混練時に、前記粘土鉱物の層間を広げるインターカレーション剤として作用する。このことによって広げられた粘土鉱物の層間にＳＰＳが入り込み、前記層間が剥離しＳＰＳ中に厚さが数ｎｍの粘土鉱物が分散されることになる。このことはまた、粘土鉱物の凝集を防止することにもなり好ましい。さらにＮ−フェニルマレイミド・スチレン共重合体は、単にＮ−フェニルマレイミドを添加する場合に比較して、ＳＰＳとの親和性が良いのでより均一なＳＰＳ組成物とすることができる。このようなＮ−フェニルマレイミド・スチレン共重合体は、例えば日本触媒社からポリイミレックスとして市販されている。 As the additive, N-phenylmaleimide / styrene copolymer and clay mineral are blended in the range of 1 to 10 parts by weight, respectively. The N-phenylmaleimide / styrene copolymer acts as an intercalation agent that expands the interlayer of the clay mineral during kneading in an extruder or the like when obtaining the SPS composition. As a result, SPS enters between the layers of the clay mineral spread, and the layers are separated to disperse the clay mineral having a thickness of several nm in the SPS. This is also preferable because it prevents aggregation of clay minerals. Furthermore, since the N-phenylmaleimide / styrene copolymer has a better affinity with SPS than when N-phenylmaleimide is simply added, a more uniform SPS composition can be obtained. Such an N-phenylmaleimide / styrene copolymer is commercially available, for example, as Polyimilex from Nippon Shokubai Co., Ltd.
また前記粘土鉱物は、サポナイト、ヘクトライト、モンモリロナイト、バイデライト、バーミキュライト、マイカから選ばれる一種が使用可能である。このような粘土鉱物は、Ｎ−フェニルマレイミド・スチレン共重合体によって広げられ、剥離した層間にＳＰＳが入り込み易く、またＳＰＳ中に厚さが数ｎｍの粘土鉱物がナノオーダーで分散されるようにするためである。このことにより少量の粘土鉱物の添加でも、ＳＰＳやＮ−フェニルマレイミド・スチレン共重合体との接触面積を大きくでき、高温時の変形（流動）を抑えることになり、少なくとも２６０℃で１２０秒に耐える半田耐熱性が得られることになる。このように微細な粘土鉱物を使用することによって、凝集が起こり難くかつ均一にＳＰＳ組成物中に分散され、また少量の添加量で効果が得られるため、比誘電率（εｒ）を増加させることなく半田耐熱性が得られることになる。 As the clay mineral, one kind selected from saponite, hectorite, montmorillonite, beidellite, vermiculite and mica can be used. Such a clay mineral is spread by an N-phenylmaleimide / styrene copolymer so that SPS can easily enter between the peeled layers, and a clay mineral having a thickness of several nanometers is dispersed in the nanometer order in the SPS. It is to do. This makes it possible to increase the contact area with SPS and N-phenylmaleimide / styrene copolymer even when a small amount of clay mineral is added, and to suppress deformation (flow) at high temperature, at least at 260 ° C. for 120 seconds. Withstands solder heat resistance. By using such fine clay minerals, aggregation hardly occurs and is uniformly dispersed in the SPS composition, and an effect can be obtained with a small amount of addition, so that the relative dielectric constant (ε r ) is increased. Thus, solder heat resistance can be obtained.
そして前記各添加剤の配合量は、Ｎ−フェニルマレイミド・スチレン共重合体が１重量部未満であると、粘土鉱物に対するインターカレーション効果が十分に発揮されず、また１０重量部を超えて配合すると、特に比誘電率（εｒ）が大きくなり１ＧＨｚ以上のような高周波帯域での使用に問題を生じるので好ましくない。また粘土鉱物の配合量が１重量部未満であると、少なくとも２６０℃で１２０秒に耐える半田耐熱性が得られず、また１０重量部を超えて配合すると比誘電率（εｒ）が２．７０（＠２．４５ＧＨ）以上となり、高周波帯域での使用ができずまた機械的特性も低下するので好ましくない。 When the amount of each additive is less than 1 part by weight of the N-phenylmaleimide / styrene copolymer, the intercalation effect on the clay mineral is not sufficiently exhibited, and more than 10 parts by weight is blended. In this case, the relative permittivity (ε r ) is particularly large, which causes a problem in use in a high frequency band such as 1 GHz or more, which is not preferable. If the blending amount of the clay mineral is less than 1 part by weight, solder heat resistance that can withstand at least 260 ° C. for 120 seconds cannot be obtained, and if it exceeds 10 parts by weight, the relative dielectric constant (ε r ) is 2. 70 (@ 2.45 GH) or more, which is not preferable because it cannot be used in a high frequency band and the mechanical characteristics are also deteriorated.
そしてより好ましくは、請求項２に記載されるようにサポナイト、ヘクトライト、モンモリロナイト、バイデライト、バーミキュライト、マイカから選ばれる粘土鉱物を用いる。特にそのサイズが、短径１０ｎｍ以下で、アスペクト比が１０以上のものがよい。このような粘土鉱物を用いることにより、Ｎ−フェニルマレイミド・スチレン共重合体によって層間が広げられまた剥離し易くすることができる。さらにＳＰＳ中に厚さが数ｎｍの粘土鉱物が、ナノオーダーで分散され易くなる。このことはより少量の粘土鉱物の添加によって、ＳＰＳやＮ−フェニルマレイミド・スチレン共重合体との接触面積をより大きくすることになり、また高温時の変形（流動）を抑えることにもなる。そして少なくとも２６０℃で１２０秒に耐える半田耐熱性が得られ易くなる。さらに凝集も起こり難くかつ均一にＳＰＳ組成物中に分散され、添加量も少量で効果があるため比誘電率（εｒ）を増加させることなく、半田耐熱性が得られることになる。なお、本発明で好ましい粘土鉱物は、ヘクトライト、モンモリロナイトである。 More preferably, as described in claim 2, a clay mineral selected from saponite, hectorite, montmorillonite, beidellite, vermiculite and mica is used. In particular, the size is preferably a minor axis of 10 nm or less and an aspect ratio of 10 or more. By using such a clay mineral, the interlayer can be expanded and peeled easily by the N-phenylmaleimide / styrene copolymer. Furthermore, clay minerals having a thickness of several nm are easily dispersed in the nanometer order in the SPS. This means that the addition of a smaller amount of clay mineral increases the contact area with SPS and N-phenylmaleimide / styrene copolymer, and also suppresses deformation (flow) at high temperatures. And it becomes easy to obtain solder heat resistance which can endure 120 seconds at 260 ° C. Further, aggregation hardly occurs and is uniformly dispersed in the SPS composition. Since the effect is small, the solder heat resistance can be obtained without increasing the relative dielectric constant (ε r ). Preferred clay minerals in the present invention are hectorite and montmorillonite.
以上のようなＳＰＳ組成物は、請求項３に記載されるように、通常の押出し成形、Ｔダイ、インフレーション成形やプレス成形によって、所望のスチレン系樹脂成形品とすることができる。例えばフィルム状の樹脂成形品としたものは、銅箔と貼り合わせることによってプリント配線基板用の銅張積層板として使用できる。さらには、電子機器類のコネクタ等が考えられる。そしてこのようして得られた樹脂成形品は、その特性が１ＧＨｚ以上の高周波帯域で比誘電率が２．７０以下（＠２．４５ＧＨｚ）の低誘電性であると共に、少なくとも２６０℃で１２０秒の半田耐熱性を有するので、電子・通信機器用部品の樹脂成形品として用いることができる。 As described in claim 3, the SPS composition as described above can be made into a desired styrenic resin molded article by ordinary extrusion molding, T-die, inflation molding or press molding. For example, a film-like resin molded product can be used as a copper-clad laminate for a printed wiring board by bonding to a copper foil. Furthermore, a connector of an electronic device can be considered. The resin molded product thus obtained has a low dielectric constant with a specific dielectric constant of 2.70 or less (@ 2.45 GHz) in a high frequency band of 1 GHz or higher, and at least 260 ° C. for 120 seconds. Therefore, it can be used as a resin molded product for electronic / communication equipment parts.
すなわち請求項４に記載されるように、１ＧＨｚ以上の高周波帯域で使用でき、比誘電率が２．７０以下（＠２．４５ＧＨｚ）の低誘電性で、半田耐熱性に優れた電子・通信機器用部品とすることができる。例えばプリント配線基板に使用できる銅張積層板であり、同軸ケーブルのコネクタ等である。そしてこのような部品は、携帯電話、自動車のナビゲータ、ＥＴＣ、アンテナやＰＣ等の部品として有用なものとなる。 That is, as described in claim 4, an electronic / communication device that can be used in a high frequency band of 1 GHz or more, has a low dielectric constant of 2.70 or less (@ 2.45 GHz), and has excellent solder heat resistance. Parts. For example, it is a copper-clad laminate that can be used for a printed wiring board, such as a connector for a coaxial cable. Such parts are useful as parts for mobile phones, automobile navigators, ETC, antennas, PCs, and the like.
表１に記載する実施例並びに比較例によって、本発明の効果を確認した。すなわち、５０ｍｍΦの同方向２軸押出機中でＳＰＳ（出光石油化学社のザレックＳ−１０４、密度１．０１ｇ／ｃｍ３）を混練溶融し、これに前記押出機のサイドフィード押出機からＮ−フェニルマレイミド・スチレン共重合体としてのポリイミレックス（日本触媒社製）と、アスペクト比が１００および５００の粘土鉱物として、ルーセンタイトＳＷＮ（コープケミカル社製）を所定量添加し混練・分散させた。ついで吐出したＳＰＳ組成物を冷却した後、ペレタイズした。 The effects of the present invention were confirmed by the examples and comparative examples described in Table 1. That is, SPS (Zarek S-104, Idemitsu Petrochemical Co., Ltd., density 1.01 g / cm 3 ) was kneaded and melted in a 50 mmφ co-directional twin-screw extruder, and N- Polyimilex (manufactured by Nippon Shokubai Co., Ltd.) as a phenylmaleimide / styrene copolymer and a predetermined amount of Lucentite SWN (manufactured by Co-op Chemical) as a clay mineral having an aspect ratio of 100 and 500 were added and kneaded and dispersed. Next, the discharged SPS composition was cooled and then pelletized.
このペレタイズされたコンパウンドを用い、射出成形機で１．５ｍｍΦ×１００ｍｍの試料を作製し、空洞共振摂動法によって２．４５ＧＨｚにおける誘電特性（比誘電率εｒ）を測定した。比誘電率εｒが２．７０以下のものが好ましいものとした。また射出成形機で、３５ｍｍ(長さ)×５ｍｍ（幅）×０．５ｍｍ（厚さ）の試料を作製し、２６０℃の鉛フリー半田浴中に１２０秒間浸漬した場合の変形の度合いを観察して、半田耐熱性とした。全く変形のないものを合格として○印で、一部分でも変形が見られたものは不合格として×印で示した。結果を表１に記載した。 Using this pelletized compound, a sample of 1.5 mmΦ × 100 mm was prepared with an injection molding machine, and dielectric properties (relative permittivity ε r ) at 2.45 GHz were measured by a cavity resonance perturbation method. It is preferable that the relative dielectric constant ε r is 2.70 or less. In addition, a 35 mm (length) x 5 mm (width) x 0.5 mm (thickness) sample was prepared with an injection molding machine, and the degree of deformation was observed when immersed in a lead-free solder bath at 260 ° C for 120 seconds. Thus, it was made solder heat resistant. Those that were not deformed at all were marked as ◯, and those that were partially deformed were marked as unacceptable as x. The results are shown in Table 1.
表１から明らかなとおり、実施例１〜１２に記載される本発明のＳＰＳ組成物は、いずれも比誘電率（εｒ）が２．７０以下の低誘電性であり、半田耐熱性も十分に実用的なものであることが判る。詳細に説明すると、ＳＰＳ１００重量部にＮ−フェニルマレイミド・スチレン共重合体を１〜１０重量部並びに粘土鉱物１〜１０重量部を添加したＳＰＳ組成物は、比誘電率が２．７０以下（＠２．４５ＧＨｚ）で、２６０℃、１２０秒の半田耐熱性を有し、高周波領域（１ＧＨｚ以上）で十分使用可能な優れた低誘電性・耐熱性のＳＰＳ組成物であることが判る。 As is clear from Table 1, all of the SPS compositions of the present invention described in Examples 1 to 12 have a low dielectric constant with a relative dielectric constant (ε r ) of 2.70 or less, and have sufficient solder heat resistance. It turns out to be practical. More specifically, an SPS composition in which 1 to 10 parts by weight of N-phenylmaleimide / styrene copolymer and 1 to 10 parts by weight of clay mineral are added to 100 parts by weight of SPS has a relative dielectric constant of 2.70 or less (@ It can be seen that this is an excellent low dielectric and heat resistant SPS composition that has a solder heat resistance of 260 ° C. and 120 seconds at 2.45 GHz and can be sufficiently used in a high frequency region (1 GHz or more).
これに対して、比較例１〜１１に見られる本発明範囲を外れるＳＰＳ組成物は、比誘電率または半田耐熱性のいずれかが満足しない結果となっている。すなわち、Ｎ−フェニルマレイミド・スチレン共重合体の添加量が本発明の下限値未満のものは、比較例２、４、５および８に見られるように、粘土鉱物の添加量に関係なく半田耐熱性に問題があることがわかる。また逆にその添加量が本発明の上限値を超える場合は、比較例３および７に見られるように粘土鉱物の添加量が多くなると、比誘電率が２．７１以上となり好ましくない。さらに比較例６および９に見られるように粘土鉱物の添加量が少なくなると、半田耐熱性が満足しなくなる。また比較例１０、１１に見られるように、Ｎ−フェニルマレイミド・スチレン共重合体量が本発明の範囲内であっても、粘土鉱物の添加量が本発明の下限値未満であると半田耐熱性が満足されず、粘土鉱物の添加量が本発明の上限値を超えると、比誘電率が２．７１となって好ましくないことがわかる。なお比較例１に示すように、Ｎ−フェニルマレイミド・スチレン共重合体並びに粘土鉱物を添加しないものは、半田耐熱性が全く得られないものであった。 On the other hand, the SPS composition outside the scope of the present invention seen in Comparative Examples 1 to 11 has a result that either the dielectric constant or the solder heat resistance is not satisfied. That is, when the addition amount of the N-phenylmaleimide / styrene copolymer is less than the lower limit of the present invention, as seen in Comparative Examples 2, 4, 5 and 8, the solder heat resistance is independent of the addition amount of the clay mineral. It turns out that there is a problem with sex. On the other hand, when the addition amount exceeds the upper limit of the present invention, as seen in Comparative Examples 3 and 7, when the addition amount of the clay mineral is increased, the relative dielectric constant is not less than 2.71. Further, as seen in Comparative Examples 6 and 9, when the amount of clay mineral added is reduced, the solder heat resistance is not satisfied. Further, as seen in Comparative Examples 10 and 11, even when the amount of N-phenylmaleimide / styrene copolymer is within the range of the present invention, the amount of the clay mineral added is less than the lower limit value of the present invention. When the added amount of clay mineral exceeds the upper limit of the present invention, the relative dielectric constant becomes 2.71, which is not preferable. As shown in Comparative Example 1, when N-phenylmaleimide / styrene copolymer and clay mineral were not added, solder heat resistance was not obtained at all.
以上のような本発明の電子・通信機器用成形部品は、比誘電率が２．７０以下の低誘電率で半田耐熱性に優れたＳＰＳ組成物によって製造されているので、１ＧＨｚ以上の高周波帯域で使用する種々の電子・通信機器の成形部品として、有用なものである。 The molded part for electronic / communication equipment according to the present invention as described above is manufactured by an SPS composition having a low dielectric constant of 2.70 or less and excellent heat resistance of solder, and therefore, a high frequency band of 1 GHz or more. It is useful as a molded part of various electronic / communication equipment used in
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH03124750A (en) * | 1989-10-09 | 1991-05-28 | Idemitsu Kosan Co Ltd | Electrical insulating film and capacitor |
| JPH07331003A (en) * | 1994-06-09 | 1995-12-19 | Otsuka Chem Co Ltd | Low dielectric resin composition |
| JP2000040421A (en) * | 1998-07-24 | 2000-02-08 | Idemitsu Petrochem Co Ltd | Electric part |
| JP2000216511A (en) * | 1999-01-22 | 2000-08-04 | Idemitsu Petrochem Co Ltd | Multilayer printed wiring board |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH03124750A (en) * | 1989-10-09 | 1991-05-28 | Idemitsu Kosan Co Ltd | Electrical insulating film and capacitor |
| JPH07331003A (en) * | 1994-06-09 | 1995-12-19 | Otsuka Chem Co Ltd | Low dielectric resin composition |
| JP2000040421A (en) * | 1998-07-24 | 2000-02-08 | Idemitsu Petrochem Co Ltd | Electric part |
| JP2000216511A (en) * | 1999-01-22 | 2000-08-04 | Idemitsu Petrochem Co Ltd | Multilayer printed wiring board |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| EP2991111A1 (en) * | 2013-04-26 | 2016-03-02 | Olympus Corporation | Image pickup apparatus |
| EP2991111A4 (en) * | 2013-04-26 | 2017-04-05 | Olympus Corporation | Image pickup apparatus |
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