JPH093208A - Composite dielectric, printed wiring board and production of composite dielectric - Google Patents
Composite dielectric, printed wiring board and production of composite dielectricInfo
- Publication number
- JPH093208A JPH093208A JP7176724A JP17672495A JPH093208A JP H093208 A JPH093208 A JP H093208A JP 7176724 A JP7176724 A JP 7176724A JP 17672495 A JP17672495 A JP 17672495A JP H093208 A JPH093208 A JP H093208A
- Authority
- JP
- Japan
- Prior art keywords
- fluororesin
- composite dielectric
- dielectric
- polyphenylene sulfide
- resin
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Classifications
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K1/00—Printed circuits
- H05K1/02—Details
- H05K1/03—Use of materials for the substrate
- H05K1/0313—Organic insulating material
- H05K1/0353—Organic insulating material consisting of two or more materials, e.g. two or more polymers, polymer + filler, + reinforcement
- H05K1/0373—Organic insulating material consisting of two or more materials, e.g. two or more polymers, polymer + filler, + reinforcement containing additives, e.g. fillers
Abstract
Description
【０００１】[0001]
【産業上の利用分野】この発明は、例えば低誘電特性を
有して高周波用の誘電体基板として用いられるような複
合誘電体、プリント配線基板および複合誘電体の製造方
法に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a composite dielectric having a low dielectric property and used as a dielectric substrate for high frequencies, a printed wiring board and a method for producing the composite dielectric.
【０００２】[0002]
【従来の技術】従来、低誘電特性を有するプリント配線
基板およびその製造方法としては、例えば次のような構
成がある。すなわち、ガラスクロス（長いガラスファイ
バを布状と成したもの）を基材として用いて、この基材
に四フッ化エチレン樹脂を含浸および焼成処理を数回繰
返したシートを重ね、基材とシートとの間にパーフロオ
ロアルコキシ樹脂層（ＰＦＡ樹脂層）もしくはパーフル
オロエチレンプロピル樹脂層を形成し、さらに最外層に
配置される金属箔との間にも上述の樹脂層をフィルム状
に成して或はコーティング法により形成し、積重ねられ
たシート、金属箔を一体的に加熱圧着して一体化形成す
るものである。2. Description of the Related Art Conventionally, a printed wiring board having a low dielectric property and a method for manufacturing the same have the following structures, for example. That is, using glass cloth (fabric made of long glass fiber as a base material) as a base material, a sheet obtained by repeating impregnation with a tetrafluoroethylene resin and firing treatment several times is laminated on the base material, and the base material and the sheet are stacked. To form a perfluoroalkoxy resin layer (PFA resin layer) or a perfluoroethylenepropyl resin layer, and further form the above-mentioned resin layer in a film form between the outermost metal foil and the metal foil. Alternatively, the sheet and the metal foil, which are formed by a coating method and stacked, are integrally heat-pressed to be integrally formed.
【０００３】一方、低誘電特性を有する熱硬化性樹脂層
板としては、例えば特開昭６３−１５４７４８号公報に
記載の構成がある。すなわち、熱硬化性樹脂１００重量
部に対してフッ素樹脂粉末を５〜２５０重量部添加し、
ガラス織布もしくはガラス不織布に含浸乾燥して得たプ
リプレグを単独で、または低い誘電率を必要とする層と
して挿入し、積層形成するものである。On the other hand, as a thermosetting resin layer plate having a low dielectric property, there is a structure described in, for example, JP-A-63-154748. That is, 5 to 250 parts by weight of fluororesin powder is added to 100 parts by weight of the thermosetting resin,
A prepreg obtained by impregnating and drying a glass woven fabric or a glass nonwoven fabric is inserted alone or as a layer requiring a low dielectric constant to form a laminate.
【０００４】このように、高周波用のプリント配線基板
等において比誘電率εｒ、誘電正接ｔａｎδの小さいも
のが要求される場合には、フッ素樹脂をベースとし、こ
のフッ素樹脂に対してガラスクロス等の充填材を組合わ
せて、比誘電率εｒが３以下、誘電正接ｔａｎδが０．
００１０程度のものが構成される。As described above, when a high-frequency printed wiring board or the like is required to have a small relative permittivity εr and a small dielectric loss tangent tan δ, a fluororesin is used as a base, and a glass cloth or the like is used for the fluororesin. When the fillers are combined, the relative dielectric constant εr is 3 or less and the dielectric loss tangent tan δ is 0.
About 0010 is configured.
【０００５】しかしフッ素樹脂は一般に四フッ化エチレ
ン樹脂ディスパージョンを用いるので高価となるうえ、
ガラスクロスに対して四フッ化エチレン樹脂ディスパー
ジョンを含浸し、含浸後において乾燥および焼成する処
理を数回繰返す工程が必要であって、さらに形成すべき
基板の厚さに応じて樹脂含浸シートを所定枚数重ねて積
層板を得るので、製造工程が複雑化するのみならず、製
造コストが高くなる問題点があった。However, the fluororesin is generally expensive because it uses a tetrafluoroethylene resin dispersion.
It is necessary to repeat the process of impregnating the glass cloth with the tetrafluoroethylene resin dispersion, drying and firing after impregnation several times, and further to prepare the resin-impregnated sheet according to the thickness of the substrate to be formed. Since a predetermined number of sheets are stacked to obtain a laminated plate, there is a problem that the manufacturing process is complicated and the manufacturing cost is increased.
【０００６】また従来の積層板はその熱膨張係数が積層
板に平行な方向では１５〜２０×１０-6／℃であり、積
層板の厚さ方向では１５０〜２００×１０-6／℃であっ
て、平行方向と厚み方向との熱膨張係数に大差が存在す
るため、温度変化による積層板の寸法変化が大で温度変
化に起因して、そり、ねじれが発生し、プリント配線基
板のスルーホールなどの電気導通不良の発生原因となる
問題点があった。Further, the conventional laminate has a coefficient of thermal expansion of 15 to 20 × 10 −6 / ° C. in the direction parallel to the laminate and 150 to 200 × 10 −6 / ° C. in the thickness direction of the laminate. However, since there is a large difference in the coefficient of thermal expansion between the parallel direction and the thickness direction, the dimensional changes of the laminated plate due to temperature changes are large, and warpage and twisting occur due to temperature changes, causing the printed wiring board to pass through. There is a problem that causes defective electrical continuity such as holes.
【０００７】さらにフッ素樹脂以外の他の樹脂にフッ素
系材料を混用して、誘電特性を改良して、誘電損失の低
い基板を得ようとする場合、フッ素樹脂層は他の材料に
対して親和性が悪い（すなわちフッ素樹脂は表面エネル
ギが小さいので、他の樹脂とブレンドしてもアンカ効果
で接合しているのみで、他の材料に対しても界面がフッ
素樹脂と化学結合をすることがなく、接着が極めて困難
である状態のこと）ので、フッ素系樹脂と他の材料との
界面で剥離が生じたり、混合樹脂が溶解分離したスキン
層が形成され実用的基板にならない問題点があった。Further, when a fluorine-based material is mixed with a resin other than the fluororesin to improve the dielectric properties and obtain a substrate with low dielectric loss, the fluororesin layer has an affinity for other materials. Poor performance (that is, fluororesin has a small surface energy, so even if it is blended with other resins, it is only joined by the anchor effect, and the interface with other materials may chemically bond with the fluororesin. However, there is a problem that peeling may occur at the interface between the fluororesin and other materials, or a skin layer in which the mixed resin is melted and separated is formed, making it a practical substrate. It was
【０００８】要するに、従来構成にあっては、フッ素系
樹脂をベースとして充填材やフッ素樹脂以外の他の樹脂
材料を混合して誘電体が形成されるので、このフッ素樹
脂は他の材料との親和性が悪く、充填材料に対する接着
性が悪化し、またフッ素樹脂以外の他の樹脂材との混合
においては、相溶は不可能であって、フッ素樹脂以外の
他の樹脂材料中にフッ素樹脂が島状に点在する現象が生
じる。加えて、形成された板の反りや歪みが生じ、また
上述のようなスキン層が形成された場合には、このスキ
ン層は熱的な作用により剥がれやすくなり、このスキン
層が容易に剥がれるという問題点は銅張積層板とした時
に致命的欠陥となる。In short, in the conventional structure, since the dielectric material is formed by mixing the filler and the resin material other than the fluororesin with the fluororesin as the base, the fluororesin is not mixed with other materials. The affinity is poor, the adhesiveness to the filling material deteriorates, and when mixed with other resin materials other than fluororesin, compatibility is impossible, and fluororesin is contained in resin materials other than fluororesin. The phenomenon that the islands are scattered in an island shape occurs. In addition, warpage or distortion of the formed plate occurs, and when the skin layer as described above is formed, the skin layer is easily peeled off by a thermal action, and the skin layer is easily peeled off. The problem is a fatal defect when using a copper clad laminate.
【０００９】[0009]
【発明が解決しようとする課題】この発明の請求項１記
載の発明は、充填材との親和性に優れるポリフェニレン
・サルファイド樹脂（ＰＰＳ）をベースとし、このＰＰ
Ｓに充填材およびフッ素樹脂（低分子量ポリテトラフル
オロエチレン）を配合することにより、誘電率および誘
電正接などの電気特性を改善することができると共に、
充填材としてガラス短繊維（ガラスファイバ）を添加す
ることで、曲げ強度および曲げ弾性などの機械的強度の
向上を図ることができるうえ、上記３者の配合量を調整
することで、比誘電率、誘電正接の調整が容易で、かつ
低誘電特性をもった複合誘電体の提供を目的とする。The invention according to claim 1 of the present invention is based on a polyphenylene sulfide resin (PPS) excellent in affinity with a filler,
By blending S with a filler and a fluororesin (low molecular weight polytetrafluoroethylene), electrical characteristics such as dielectric constant and dielectric loss tangent can be improved, and
By adding short glass fibers (glass fibers) as a filler, the mechanical strength such as bending strength and bending elasticity can be improved, and the relative permittivity can be adjusted by adjusting the compounding amount of the above three members. It is an object of the present invention to provide a composite dielectric having a low dielectric property, whose dielectric loss tangent can be easily adjusted.
【００１０】この発明の請求項２記載の発明は、上記請
求項１記載の発明の目的と併せて、上述のポリフェニレ
ン・サルファイド樹脂、フッ素樹脂、ガラス短繊維の配
合比率を特定割合に設定することで、高周波用として要
請される低い比誘電率を確保しつつ、機械的強度をさら
に向上させることができる複合誘電体の提供を目的とす
る。According to a second aspect of the present invention, in addition to the object of the first aspect of the present invention, the compounding ratio of the above polyphenylene sulfide resin, fluororesin, and glass short fiber is set to a specific ratio. Then, an object of the present invention is to provide a composite dielectric body capable of further improving mechanical strength while ensuring a low relative permittivity required for high frequencies.
【００１１】この発明の請求項３記載の発明は、上記請
求項１もしくは２記載の発明の目的と併せて、上述のポ
リフェニレン・サルファイド樹脂、フッ素樹脂、ガラス
短繊維の組成物の射出後、加熱圧縮成形することで、ガ
ラス短繊維の配向性をなくして、縦方向、横方向の向き
の相違にかかわらず一様な電気特性、機械特性を得るこ
とができ、また板の反りや歪みおよびスキン層の発生を
解消することができ、寸法変化が小さく、アニソトロピ
ー率および寸法安定性に優れた複合誘電体の提供を目的
とする。According to the invention of claim 3 of the present invention, in addition to the object of the invention of claim 1 or 2, heating is carried out after injection of the composition of polyphenylene sulfide resin, fluororesin and short glass fiber. By compression molding, the orientation of short glass fibers can be eliminated and uniform electrical and mechanical properties can be obtained regardless of the orientation in the longitudinal and transverse directions. It is an object of the present invention to provide a composite dielectric which can eliminate the generation of layers, has a small dimensional change, and has an excellent anisotropy rate and dimensional stability.
【００１２】この発明の請求項４記載の発明は、上記請
求項１，２もしくは３記載の複合誘電体の少なくとも片
面に金属箔（銅箔、アルミ箔など）を配置して、再加熱
加圧して一体形成されたプリント配線基板と成すこと
で、上記請求項１，２もしくは３記載の発明の目的と併
せて、再加熱加圧時にＰＰＳ、フッ素樹脂、ガラス短繊
維からなる成形物の少なくとも片面に金属箔を同時に接
着することでができ、ＰＰＳの接着性により金属箔を成
形物に対して強固に接着することができると共に、一様
な電気特性、機械特性を有し、かつ低誘電特性をもった
プリント配線基板の提供を目的とする。According to a fourth aspect of the present invention, a metal foil (copper foil, aluminum foil, etc.) is arranged on at least one surface of the composite dielectric according to the first, second or third aspect, and reheated and pressed. In addition to the object of the invention according to claim 1, 2 or 3, at least one surface of a molded article made of PPS, fluororesin, and glass short fiber is formed at the time of reheating and pressurizing. The metal foil can be adhered to the molded product at the same time by the adhesion of PPS, and the metal foil can be firmly adhered to the molded product due to the adhesive property of PPS, and also has a low dielectric property. It is intended to provide a printed wiring board having the above.
【００１３】この発明の請求項５記載の発明は、ポリフ
ェニレン・サルファイド樹脂、フッ素樹脂、ガラス短繊
維を特定配合比率にて均一に分散混合した組成物を射出
した後に、加熱圧縮成形して複合誘電体を製造すること
で、低コストおよび高生産性を確保しつつ、板の反りや
歪み、スキン層の発生がなく一様で均一な電気特性、機
械特性をもった低誘電特性複合誘電体を製造することが
できる複合誘電体の製造方法の提供を目的とする。According to a fifth aspect of the present invention, a composite dielectric is prepared by injecting a composition in which polyphenylene sulfide resin, fluororesin and short glass fiber are uniformly dispersed and mixed at a specific mixing ratio, and then heat compression molding is performed. By manufacturing the body, while maintaining low cost and high productivity, a low dielectric property composite dielectric with uniform and uniform electrical and mechanical properties without warpage or distortion of the plate or skin layer is obtained. An object of the present invention is to provide a method for manufacturing a composite dielectric that can be manufactured.
【００１４】[0014]
【課題を解決するための手段】この発明の請求項１記載
の発明は、樹脂をガラス短繊維で補強した複合誘電体で
あって、上記樹脂はポリフェニレン・サルファイド樹脂
とフッ素樹脂との複合体に設定された複合誘電体である
ことを特徴とする。The invention according to claim 1 of the present invention is a composite dielectric in which a resin is reinforced by glass short fibers, wherein the resin is a composite of polyphenylene sulfide resin and fluororesin. It is characterized by being a set composite dielectric.
【００１５】この発明の請求項２記載の発明は、上記請
求項１記載の発明の構成と併せて、上記ポリフェニレン
・サルファイド樹脂と上記フッ素樹脂と上記ガラス短繊
維との配合比を、ポリフェニレン・サルファイド樹脂が
３０〜６０wt％、フッ素樹脂が１５〜５５wt％、ガラス
短繊維が１０〜４０wt％の割合に設定された複合誘電体
であることを特徴とする。According to a second aspect of the present invention, in addition to the constitution of the first aspect of the invention, the compounding ratio of the polyphenylene sulfide resin, the fluororesin and the glass short fiber is set to polyphenylene sulfide. The composite dielectric is characterized in that the resin content is 30 to 60 wt%, the fluororesin content is 15 to 55 wt%, and the short glass fiber content is 10 to 40 wt%.
【００１６】この発明の請求項３記載の発明は、上記請
求項１もしくは２記載の発明の構成と併せて、上記ポリ
フェニレン・サルファイド樹脂、フッ素樹脂およびガラ
ス短繊維の組成物の射出後、加熱圧縮成形された複合誘
電体であることを特徴とする。According to a third aspect of the present invention, in addition to the structure of the first or second aspect of the invention, the composition of the polyphenylene sulfide resin, the fluororesin and the glass short fiber is injected and then heat-pressed. It is characterized in that it is a molded composite dielectric.
【００１７】この発明の請求項４記載の発明は、上記請
求項１，２もしくは３記載の複合誘電体の少なくとも片
面に金属箔を配置して、再加熱加圧して一体化成形され
たプリント配線基板であることを特徴とする。The invention according to claim 4 of the present invention is a printed wiring integrally formed by arranging a metal foil on at least one surface of the composite dielectric according to claim 1, 2 or 3 and reheating and pressing. It is a substrate.
【００１８】この発明の請求項５記載の発明は、ポリフ
ェニレン・サルファイド樹脂３０〜６０wt％と、フッ素
樹脂１５〜５５wt％と、充填材としてのガラス短繊維１
０〜４０wt％とを均一に分散混合した組成物が射出され
た後に、加熱圧縮成形して製造される複合誘電体の製造
方法であることを特徴とする。According to a fifth aspect of the present invention, the polyphenylene sulfide resin is 30 to 60 wt%, the fluororesin is 15 to 55 wt%, and the glass short fiber 1 as a filler is used.
It is characterized in that it is a method for producing a composite dielectric, which is produced by injecting a composition in which 0 to 40 wt% is uniformly dispersed and mixed, and then heat compression molding.
【００１９】[0019]
【発明の作用及び効果】この発明の請求項１記載の発明
によれば、充填材との親和性に優れるポリフェニレン・
サルファイド樹脂（ＰＰＳ）をベースとし、このＰＰＳ
に充填材およびフッ素樹脂を配合したので、比誘電率ε
ｒおよび誘電正接ｔａｎδなどの電気特性を改善するこ
とができると共に、充填材としてガラス短繊維（ガラス
ファイバ）を添加したので、曲げ強度および曲げ弾性な
どの機械的強度の向上を図ることができるうえ、上述の
３者（すなわちＰＰＳ、フッ素樹脂、ガラス短繊維）の
配合量を調整することで、比誘電率εｒ、誘電正接ｔａ
ｎδの調整が容易となる効果がある。また高周波用とし
て要求される低誘電特性を備えることができる効果があ
る。According to the invention described in claim 1 of the present invention, polyphenylene, which has an excellent affinity with the filler,
This PPS is based on sulfide resin (PPS)
Since the filler and fluororesin were mixed in, the relative permittivity ε
In addition to improving electrical properties such as r and dielectric loss tangent tan δ, glass short fibers (glass fibers) are added as a filler, so that mechanical strength such as bending strength and bending elasticity can be improved. , The relative dielectric constant εr and the dielectric loss tangent ta can be adjusted by adjusting the compounding amounts of the above three members (that is, PPS, fluororesin, and glass short fiber).
This has the effect of facilitating the adjustment of nδ. Further, there is an effect that the low dielectric property required for high frequencies can be provided.
【００２０】この発明の請求項２記載の発明によれば、
上記請求項１記載の発明の効果と併せて、上記３者の配
合比をポリフェニレン・サルファイド樹脂３０〜６０wt
％、フッ素樹脂１５〜５５wt％、ガラス短繊維１０〜４
０wt％に設定したので、高周波用として要請される低い
比誘電率を確保しつつ、機械的強度をさらに向上させる
ことができる効果がある。According to the second aspect of the present invention,
In addition to the effect of the invention according to claim 1, the compounding ratio of the above three is 30 to 60 wt% of polyphenylene sulfide resin.
%, Fluororesin 15-55 wt%, glass short fiber 10-4
Since it is set to 0 wt%, there is an effect that the mechanical strength can be further improved while ensuring the low relative permittivity required for high frequencies.
【００２１】因に、ポリフェニレン・サルファイド樹脂
が６０wt％を超過すると、比誘電率εｒが高くなり、逆
に３０wt％未満の場合には、機械的強度が低下し、フッ
素樹脂が５５wt％を超過すると、このフッ素樹脂からガ
スが発生し、ボイドの増加により基板の機械的強度が低
下し、逆に１５wt％未満の場合には低い比誘電率εｒを
得ることが困難となり、ガラス短繊維が４０wt％を超過
すると、比誘電率εｒが高くなり、逆に１０wt％未満の
場合には曲げ強度、曲げ弾性の機械的強度が低下する
が、この発明では上記３者の配合比を上述の如く設定す
ることにより、低い比誘電率の確保と、機械的強度の向
上との両立を図ることができる効果がある。Incidentally, when the polyphenylene sulfide resin exceeds 60 wt%, the relative dielectric constant εr increases, and when it is less than 30 wt%, the mechanical strength decreases and when the fluororesin exceeds 55 wt%. However, gas is generated from this fluororesin, the mechanical strength of the substrate decreases due to the increase of voids, and conversely, when it is less than 15 wt%, it becomes difficult to obtain a low relative permittivity εr, and the glass short fiber is 40 wt%. If it exceeds, the relative permittivity εr increases, and conversely, if it is less than 10 wt%, the bending strength and the mechanical strength of bending elasticity decrease. However, in the present invention, the mixing ratio of the above three is set as described above. As a result, there is an effect that both a low relative permittivity and an improvement in mechanical strength can be achieved.
【００２２】この発明の請求項３記載の発明によれば、
上記請求項１もしくは２記載の発明の効果と併せて、上
述のポリフェニレン・サルファイド樹脂、フッ素樹脂、
ガラス短繊維の組成物の射出後、加熱圧縮成形すること
で複合誘電体を構成したので、ガラス短繊維（ガラスフ
ァイバ）が射出成形時において樹脂の流れた方向に沿っ
てその長さ方向がそろいやすい点を、射出後において加
熱圧縮成形することで、ガラス短繊維の配向性をなくし
て、縦方向、横方向の向きの相違にかかわらず、一様な
電気特性、機械特性を得ることができ、また板の反りや
歪み及びスキン層の発生を解消することができ、アニソ
トロピー率（断面が層状になっているものにおける、層
の形成具合を示す指標で、アニソトロピー率の高いもの
程、はっきりとした層状を呈するので、このアニソトロ
ピー率は小さい方が望ましい）および寸法変化が小さ
く、寸法安定性に優れる効果がある。According to the third aspect of the present invention,
In addition to the effect of the invention according to claim 1 or 2, the above polyphenylene sulfide resin, fluororesin,
Since the composite dielectric was constructed by heat compression molding after injection of the glass short fiber composition, the glass short fibers (glass fibers) have the same length direction along the resin flow direction during injection molding. The easy point is that by performing heat compression molding after injection, the orientation of short glass fibers can be eliminated and uniform electrical and mechanical properties can be obtained regardless of the difference in the orientation in the longitudinal and transverse directions. Moreover, it is possible to eliminate warpage and distortion of the plate and the occurrence of a skin layer, and an anisotropy rate (an index showing the degree of layer formation in a layered cross section, the higher the anisotropy rate, the more clearly Since it has a layered structure, it is desirable that the anisotropy rate is small) and the dimensional change is small, and the dimensional stability is excellent.
【００２３】この発明の請求項４記載の発明によれば、
上記請求項１，２もしくは３記載の複合誘電体の少なく
とも片面に金属箔を配置して、再加熱加圧して一体形成
されることでプリント配線基板を構成したので、上記請
求項１，２もしくは３記載の破滅位の効果と併せて、再
加熱加圧時に、ポリフェニレン・サルファイド樹脂ＰＰ
Ｓ、フッ素樹脂、ガラス短繊維からなる成形物の少なく
とも片面に金属箔を同時に接着することができ、ＰＰＳ
の接着性により金属箔を成形物に対して強固に接着する
ことができると共に、一様な電気特性、機械特性を有
し、かつ低誘電特性をもったプリント配線基板を得るこ
とができる効果がある。According to the invention described in claim 4 of the present invention,
The printed wiring board is configured by arranging a metal foil on at least one surface of the composite dielectric according to claim 1, 2 or 3 and reheating and pressing to integrally form the printed wiring board. In addition to the effect of the catastrophic effect described in 3, the polyphenylene sulfide resin PP is used when reheating and pressurizing.
A metal foil can be simultaneously adhered to at least one surface of a molded article made of S, fluororesin, and glass short fiber.
The effect of being able to firmly adhere the metal foil to the molded product by the adhesive property of, and to obtain a printed wiring board having uniform electric properties and mechanical properties and having low dielectric properties. is there.
【００２４】この発明の請求項５記載の発明によれば、
ポリフェニレン・サルファイド樹脂３０〜６０wt％と、
フッ素樹脂１５〜５５wt％と、充填材としてのガラス短
繊維１０〜４０wt％とが均一に分散混合された組成物は
射出成形され、しかる後に加熱圧縮成形して複合誘電体
が製造される。According to the invention described in claim 5 of the present invention,
Polyphenylene sulfide resin 30 to 60 wt%,
A composition in which 15 to 55 wt% of a fluororesin and 10 to 40 wt% of glass short fibers as a filler are uniformly dispersed and mixed is injection molded, and then heat compression molded to produce a composite dielectric.
【００２５】このように材料を全て混合して射出成形す
るので、特性の均一化を図ることができ、かつ射出成形
により低コスト化および高い生産性を確保することがで
きる。しかも、射出成形後に加熱圧縮成形を施すので、
板の反りや歪み、スキン層の発生がなく一様な電気特
性、機械特性をもった低誘電特性複合誘電体を製造する
ことができる効果がある。Since all the materials are mixed and injection-molded as described above, the characteristics can be made uniform, and the injection molding can ensure low cost and high productivity. Moreover, since heat compression molding is performed after injection molding,
There is an effect that it is possible to manufacture a low dielectric constant composite dielectric having uniform electrical properties and mechanical properties without warping or distortion of a plate or generation of a skin layer.
【００２６】また上述のポリフェニレン・サルファイド
樹脂、フッ素樹脂、ガラス短繊維は何れも耐熱性、難燃
性、耐薬品性に優れたコンポジット（composite)である
ため、その組成物は従来のガラスクロス、樹脂含浸シー
トの積層板と比較して、内部まで均一でアニソトロピー
率が小さいという特徴を有すると共に、寸法安定性、吸
水率が小さく、高温、高湿、高周波条件下においても優
れた電気特性を示すので、信頼性の高い高周波用の複合
誘電体となる効果がある。Since the above-mentioned polyphenylene sulfide resin, fluororesin, and glass short fiber are all composites having excellent heat resistance, flame retardancy, and chemical resistance, the composition thereof is a conventional glass cloth, Compared with the laminated sheet of resin-impregnated sheet, it has the characteristics that it is uniform to the inside and has a small anisotropy rate, and also has small dimensional stability and water absorption rate, and shows excellent electrical characteristics even under high temperature, high humidity, and high frequency conditions. Therefore, there is an effect that it becomes a highly reliable composite dielectric for high frequencies.
【００２７】[0027]
【実施例】この発明の一実施例を以下図面に基づいて詳
述する。 （実施例１）ポリフェニレン・サルファイド樹脂（以下
単にＰＰＳと略記する）をベースとし、このＰＰＳを５
５wt％、フッ素樹脂（低分子量ポリテトラフルオロエチ
レン）を１５wt％、充填材として用いるガラス短繊維と
してのＥガラスファイバを３０wt％の割合で均一に分散
混合した組成物を形成し、この組成物で射出成形に適し
たペレットを形成する。DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS One embodiment of the present invention will be described below in detail with reference to the drawings. (Example 1) Based on polyphenylene sulfide resin (hereinafter abbreviated as PPS), this PPS was mixed with 5
5% by weight, 15% by weight of fluororesin (low molecular weight polytetrafluoroethylene), and 30% by weight of E glass fiber as a short glass fiber used as a filler were uniformly dispersed and mixed to form a composition. Form pellets suitable for injection molding.
【００２８】次に、上述のペレットを温度１４０℃で約
４時間乾燥処理した後に、射出成形機を用いて次の条件
下にて射出成形して厚さ２．４mmの板（複合誘電体）を
形成する。Next, the above pellets were dried at a temperature of 140 ° C. for about 4 hours, and then injection-molded using an injection molding machine under the following conditions to obtain a 2.4 mm-thick plate (composite dielectric). To form.
【００２９】射出成形時の条件 シリンダ温度……３４０℃ 金 型 温度……１４０℃ 次に上述の板の両面に厚さ３５μｍの電解銅箔を配置し
て、複合樹脂の溶解温度（ＰＴＦＥの融点３２７℃、Ｐ
ＰＳの融点２９０℃）以上の温度、例えば３４０℃で、
かつ圧力１ＭＰａの条件下にて約２０分間再加熱圧縮し
て一体成形された基板（プリント配線基板）を製造し
た。 Conditions for injection molding Cylinder temperature: 340 ° C. Mold temperature: 140 ° C. Next, electrolytic copper foil with a thickness of 35 μm is arranged on both sides of the above plate, and the melting temperature of the composite resin (melting point of PTFE) 327 ° C, P
At a temperature above the melting point of PS (290 ° C), for example 340 ° C,
Moreover, the substrate (printed wiring board) integrally molded was manufactured by reheating and compressing for about 20 minutes under a pressure of 1 MPa.
【００３０】このようにして製造されたプリント配線基
板の諸特性すなわち比誘電率εｒ、誘電正接ｔａｎδ、
銅箔引きはがし強さ、ドリル摩耗、スルーホールめっき
強さ、吸水率、熱膨張係数を評価するために各種の測定
を実行し、その実測値を次の［表１］に示す。Various characteristics of the thus-produced printed wiring board, that is, the relative permittivity εr, the dielectric loss tangent tan δ,
Various measurements were carried out in order to evaluate the peeling strength of copper foil, drill wear, through-hole plating strength, water absorption, and coefficient of thermal expansion, and the measured values are shown in the following [Table 1].
【００３１】（実施例２）ＰＰＳをベースとし、このＰ
ＰＳを３６wt％、フッ素樹脂（低分子量ポリテトラフル
オロエチレン）を５４wt％、充填材として用いるガラス
短繊維としてのＥガラスファイバを１０wt％の割合で均
一に分散混合した組成物を形成し、この組成物で射出成
形に適したペレットを形成する。Example 2 Based on PPS, this P
A composition was prepared by uniformly dispersing and mixing PS in an amount of 36 wt%, fluororesin (low molecular weight polytetrafluoroethylene) in an amount of 54 wt%, and E glass fiber as a short glass fiber used as a filler in an amount of 10 wt%. To form pellets suitable for injection molding.
【００３２】次に、上述のペレットを温度１４０℃で約
４時間乾燥処理した後に、射出成形機を用い次の条件下
にて射出成形して厚さ２．４mmの板（複合誘電体）を形
成する。Next, the above pellets were dried at a temperature of 140 ° C. for about 4 hours, and then injection-molded under the following conditions using an injection molding machine to form a plate (composite dielectric) having a thickness of 2.4 mm. Form.
【００３３】射出成形時の条件 シリンダ温度……３４０℃ 金 型 温度……１４０℃ 次に上述の板の両面に厚さ３５μｍの電解銅箔を配置し
て、複合樹脂の溶融温度（ＰＴＦＥの融点３２７℃、Ｐ
ＰＳの融点２９０℃）以上の温度、例えば３４０℃で、
かつ圧力１ＭＰａの条件下にて約２０分間再加熱圧縮し
て一体形成された基板（プリント配線基板）を製造し
た。 Conditions for injection molding Cylinder temperature: 340 ° C. Mold temperature: 140 ° C. Next, electrolytic copper foil with a thickness of 35 μm is arranged on both sides of the above plate, and the melting temperature of the composite resin (melting point of PTFE) 327 ° C, P
At a temperature above the melting point of PS (290 ° C), for example 340 ° C,
Further, the substrate (printed wiring board) integrally formed was manufactured by reheating and compressing for about 20 minutes under a pressure of 1 MPa.
【００３４】このようにして製造されたプリント配線基
板の諸特性すなわち比誘電率εｒ、誘電正接ｔａｎδ、
銅箔引きはがし強さ、ドリル摩耗、スルーホールめっき
強さ、吸水率、熱膨脹係数を評価するために各種の測定
を実行し、その実測値を次の［表１］に示す。Various characteristics of the thus-produced printed wiring board, that is, the relative permittivity εr, the dielectric loss tangent tan δ,
Various measurements were performed in order to evaluate the peeling strength of copper foil, drill wear, through-hole plating strength, water absorption, and coefficient of thermal expansion, and the measured values are shown in [Table 1] below.
【００３５】（比較例１）上述の実施例１、実施例２の
複合誘電体ないしプリント配線基板に対して諸特性を比
較するために次の条件下にて比較品を製造した。すなわ
ちＰＰＳを６０wt％、充填材としてのＥガラスファイバ
を４０wt％の割合で均一に分散混合した組成物を形成
し、この組成物で射出成形に適したペレットを形成す
る。Comparative Example 1 A comparative product was manufactured under the following conditions in order to compare various characteristics with the composite dielectrics or printed wiring boards of Examples 1 and 2 described above. That is, a composition in which PPS is 60 wt% and E glass fiber as a filler is uniformly dispersed and mixed in a proportion of 40 wt% is formed, and the composition is used to form pellets suitable for injection molding.
【００３６】次に、上述のペレットを温度１４０℃で約
４時間乾燥処理した後に、射出成形機を用いて、シリン
ダ温度３４０℃、金型温度１４０℃の上述と同一の条件
下にて射出成形して厚さ２．４mmの板（複合誘電体）を
形成する。次に上述の板の両面に厚さ３５μｍの電解銅
箔を配置して、使用樹脂の溶融温度（ＰＰＳの融点２９
０℃）以上の温度、例えば３４０℃で、かつ圧力１ＭＰ
ａの条件下にて約２０分間再加熱圧縮して一体成形され
た比較品としての基板（プリント配線基板）を製造し
た。Next, after drying the above pellets at a temperature of 140 ° C. for about 4 hours, injection molding was performed using an injection molding machine under the same conditions as described above at a cylinder temperature of 340 ° C. and a mold temperature of 140 ° C. Then, a plate (composite dielectric) having a thickness of 2.4 mm is formed. Next, electrolytic copper foil having a thickness of 35 μm is arranged on both sides of the above-mentioned plate, and the melting temperature of the resin used (melting point of PPS 29
0 ° C) or higher temperature, eg 340 ° C, and pressure 1MP
A board (printed wiring board) as a comparative product integrally manufactured by reheating and compressing under the condition of a for about 20 minutes was manufactured.
【００３７】このようにして製造された比較品のプリン
ト基板の諸特性すなわち比誘電率εｒ、誘電正接ｔａｎ
δ、銅箔引きはがし強さ、ドリル摩耗、スルーホールめ
っき強さ、吸水率、熱膨脹係数を評価するために各種の
測定を実行し、その測定値を次の［表１］に示す。Various characteristics of the comparative printed circuit board manufactured in this manner, that is, the relative permittivity εr and the dielectric loss tangent tan.
[delta], copper foil peeling strength, drill wear, through-hole plating strength, water absorption, and coefficient of thermal expansion were subjected to various measurements, and the measured values are shown in [Table 1] below.
【００３８】[0038]
【表１】 [Table 1]
【００３９】上述の［表１］における実施例１、実施例
２と比較例１との対比により明らかなように、本実施例
の複合誘電体ないしプリント配線基板は高周波用として
要求されるに充分な低誘電特性（比誘電率および誘電正
接の項参照）を有していることがわかる。As is clear from the comparison of Examples 1 and 2 and Comparative Example 1 in the above [Table 1], the composite dielectric or printed wiring board of this Example is sufficient for high frequency use. It can be seen that it has excellent low dielectric properties (see the terms of relative permittivity and dielectric loss tangent).
【００４０】以上要するに本実施例の複合誘電体は、充
填材との親和性に優れるＰＰＳをベースとし、このＰＰ
Ｓに充填材およびフッ素樹脂を配合したので、比誘電率
εｒおよび誘電正接ｔａｎδなどの電気特性を改善する
ことができると共に、充填材としてガラス短繊維（ガラ
スファイバ）を添加したので、曲げ強度および曲げ弾性
などの機械的強度の向上を図ることができるうえ、上述
の３者（すなわちＰＰＳ、フッ素樹脂、ガラス短繊維）
の配合量を調整することで、比誘電率εｒ、誘電正接ｔ
ａｎδの調整が容易となる効果がある。また高周波用と
して要求される低誘電特性を備えることができる効果が
ある。In summary, the composite dielectric of this embodiment is based on PPS, which has excellent affinity with the filler, and
Since S is mixed with a filler and a fluororesin, electrical characteristics such as relative permittivity εr and dielectric loss tangent tanδ can be improved, and since short glass fiber (glass fiber) is added as a filler, bending strength and In addition to being able to improve mechanical strength such as flexural elasticity, the above three factors (ie PPS, fluororesin, short glass fiber)
The relative permittivity εr and the dielectric loss tangent t can be adjusted by adjusting the compounding amount of
This has the effect of facilitating the adjustment of an δ. Further, there is an effect that the low dielectric property required for high frequencies can be provided.
【００４１】さらに、上記３者の配合比をＰＰＳ３０〜
６０wt％、フッ素樹脂１５〜５５wt％、ガラス短繊維１
０〜４０wt％に設定したので、高周波用として要請され
る低い比誘電率を確保しつつ、機械的強度をさらに向上
させることができる効果がある。Further, the mixing ratio of the above three is PPS30-.
60 wt%, fluororesin 15-55 wt%, glass short fiber 1
Since it is set to 0 to 40 wt%, there is an effect that the mechanical strength can be further improved while ensuring the low relative permittivity required for high frequencies.
【００４２】因に、ＰＰＳが６０wt％を超過すると、比
誘電率εｒが高くなり、逆に３０wt％未満の場合には機
械的強度が低下し、フッ素樹脂が５５wt％を超過する
と、このフッ素樹脂からガスが発生し、ボイドの増加に
より基板の機械的強度が低下し、逆に１５wt％未満の場
合には低い比誘電率εｒを得ることが困難となり、ガラ
ス短繊維が４０wt％を超過すると、比誘電率εｒ高くな
り、逆に１０wt％未満の場合には曲げ強度、曲げ弾性の
機械的強度が低下するが、この発明では上記３者の配合
比を上述の如く設定することにより、低い比誘電率の確
保と、機械的強度の向上との両立を図ることができる効
果がある。Incidentally, when PPS exceeds 60 wt%, the relative dielectric constant εr increases, and when it is less than 30 wt%, the mechanical strength decreases, and when the fluororesin exceeds 55 wt%, this fluororesin Gas is generated, the mechanical strength of the substrate decreases due to the increase of voids, and conversely, when it is less than 15 wt%, it becomes difficult to obtain a low relative permittivity εr, and when the glass short fiber exceeds 40 wt%, When the relative permittivity εr becomes high, and conversely, when it is less than 10 wt%, the bending strength and the mechanical strength of bending elasticity decrease, but in the present invention, by setting the compounding ratio of the above three as described above, a low ratio can be obtained. There is an effect that both the securing of the dielectric constant and the improvement of the mechanical strength can be achieved.
【００４３】しかも、上述のＰＰＳ、フッ素樹脂、ガラ
ス短繊維の組成物の射出後、加熱圧縮成形することで複
合誘電体を構成したので、ガラス短繊維（ガラスファイ
バ）が射出成形時において樹脂の流れた方向に沿ってそ
の長さ方向がそろいやすい点を、射出後において加熱圧
縮成形することで、ガラス短繊維の配向性をなくして、
縦方向、横方向の向きの相違にかかわらず、一様な電気
特性、機械特性を得ることができ、また板の反りや歪み
及びスキン層の発生を解消することができ、アニソトロ
ピー率断面が層状になっているものにおける、層の形式
具合を示す指標で、アニソトロピー率の高いもの程、は
っきりとした層状を呈するので、このアニソトロピー率
は小さい方が望ましい）および寸法変化が小さく、寸法
安定性に優れる効果がある。Moreover, since the composite dielectric is constructed by heat compression molding after injecting the composition of PPS, fluororesin, and glass short fiber described above, the glass short fiber (glass fiber) is made of resin during injection molding. The point that the length direction is easily aligned along the flowing direction, by heat compression molding after injection, eliminate the orientation of short glass fibers,
Uniform electrical and mechanical properties can be obtained regardless of the orientation in the vertical and horizontal directions, warpage and distortion of the plate and the occurrence of skin layers can be eliminated, and the anisotropy rate cross section is layered. It is an index showing the type of layer in the layer, and the higher the anisotropy rate is, the more clearly the layered state is exhibited. Therefore, the smaller the anisotropy rate is, the smaller the dimensional change and the dimensional stability. It has an excellent effect.
【００４４】また本実施例のプリント配線基板は、上述
の複合誘電体の両面に金属箔を配置して、再加熱加圧し
て一体形成されるので、再加熱加圧時に、ＰＰＳ、フッ
素樹脂、ガラス短繊維からなる成形物の両面に金属箔を
同時に接着することができ、ＰＰＳの接着性により金属
箔を成形物に対して強固に接着することができると共
に、一様な電気特性、機械特性を有し、かつ低誘電特性
をもったプリント配線基板を得ることができる効果があ
る。Further, since the printed wiring board of the present embodiment is integrally formed by disposing metal foils on both sides of the above-mentioned composite dielectric and reheating and pressing, PPS, fluororesin, A metal foil can be simultaneously adhered to both sides of a molded article made of short glass fibers, and the metal foil can be firmly adhered to the molded article due to the adhesiveness of PPS, and uniform electrical and mechanical properties can be obtained. There is an effect that it is possible to obtain a printed wiring board having a low dielectric property.
【００４５】さらに、本実施例の製造方法によれば、Ｐ
ＰＳ３０〜６０wt％と、フッ素樹脂１５〜５５wt％と、
充填材としてのガラス短繊維１０〜４０wt％とが均一に
分散混合された組成物が射出成形された後に、加熱圧縮
成形して複合誘電体が製造される。Further, according to the manufacturing method of this embodiment, P
PS 30-60 wt%, fluororesin 15-55 wt%,
A composite in which 10-40 wt% of glass short fibers as a filler is uniformly dispersed and mixed is injection-molded and then heat-compression-molded to produce a composite dielectric.
【００４６】このように材料を全て混合して射出成形す
るので、特性の均一化を図ることができ、かつ射出成形
により低コスト化および高い生産性を確保することがで
きる。しかも、射出成形後に加熱圧縮成形を施すので、
板の反りや歪み、スキン層の発生がなく一様な電気特
性、機械特性をもった低誘電特性複合誘電体を製造する
ことができる効果がある。Since all the materials are mixed and injection-molded in this way, the characteristics can be made uniform, and the injection molding can ensure low cost and high productivity. Moreover, since heat compression molding is performed after injection molding,
There is an effect that it is possible to manufacture a low dielectric constant composite dielectric having uniform electrical properties and mechanical properties without warping or distortion of a plate or generation of a skin layer.
【００４７】また上述のＰＰＳ、フッ素樹脂、ガラス短
繊維は何れも耐熱性、難燃性、耐薬品性に優れたコンポ
ジット（composite ）であるため、その組成物は従来の
ガラスクロス、樹脂含浸シートの積層板と比較して、内
部まで均一でアニソトロピー率が小さいという特徴を有
すると共に、寸法安定性、吸水率が小さく、高温、高
湿、高周波条件下においても優れた電気特性を示すの
で、信頼性が高い高周波用の複合誘電体となる効果があ
る。Since the above-mentioned PPS, fluororesin and short glass fiber are all composites having excellent heat resistance, flame retardancy and chemical resistance, the composition thereof is a conventional glass cloth or resin impregnated sheet. Compared with the laminated plate of No. 1, it has the characteristics of being uniform to the inside and having a small anisotropy rate, and also has small dimensional stability and water absorption, and exhibits excellent electrical characteristics even under high temperature, high humidity, and high frequency conditions. There is an effect that it becomes a high frequency composite dielectric.
【００４８】なお、上述の充填材に対してＡｌ2 Ｏ
3 （アルミナ）、ＴｉＯ2 （酸化チタン）、ＢａＴｉＯ
3 （チタン酸バリウム）などを併用してもよい。Al 2 O was added to the above-mentioned filler.
3 (alumina), TiO 2 (titanium oxide), BaTiO 3
You may use together 3 (barium titanate).
───────────────────────────────────────────────────── フロントページの続き (51)Int.Cl.6 識別記号 庁内整理番号 ＦＩ 技術表示箇所 Ｃ０８Ｌ 81/02 ＬＲＧ Ｃ０８Ｌ 81/02 ＬＲＧ // Ｂ２９Ｋ 81:00 Ｃ０８Ｋ 7:14 ─────────────────────────────────────────────────── ─── Continuation of front page (51) Int.Cl. 6 Identification code Internal reference number FI Technical display location C08L 81/02 LRG C08L 81/02 LRG // B29K 81:00 C08K 7:14
Claims (5)
であって、上記樹脂はポリフェニレン・サルファイド樹
脂とフッ素樹脂との複合体に設定された、複合誘電体。1. A composite dielectric in which a resin is reinforced with short glass fibers, wherein the resin is a composite of polyphenylene sulfide resin and fluororesin.
上記フッ素樹脂と上記ガラス短繊維との配合比を、ポリ
フェニレン・サルファイド樹脂が３０〜６０wt％、フッ
素樹脂が１５〜５５wt％、ガラス短繊維が１０〜４０wt
％の割合に設定された請求項１記載の複合誘電体。2. The compounding ratio of the polyphenylene sulfide resin, the fluororesin, and the glass short fiber is 30 to 60 wt% for the polyphenylene sulfide resin, 15 to 55 wt% for the fluororesin, and 10 to 40 wt for the glass short fiber.
The composite dielectric according to claim 1, which is set to a ratio of%.
フッ素樹脂およびガラス短繊維の組成物の射出後、加熱
圧縮成形された請求項１もしくは２記載の複合誘電体。3. The polyphenylene sulfide resin,
The composite dielectric according to claim 1 or 2, which is heat-compression-molded after injection of the composition of fluororesin and short glass fiber.
電体の少なくとも片面に金属箔を配置して、再加熱加圧
して一体化成形されたプリント配線基板。4. A printed wiring board integrally formed by arranging a metal foil on at least one surface of the composite dielectric according to claim 1, 2 or 3 and reheating and pressing.
６０wt％と、フッ素樹脂１５〜５５wt％と、充填材とし
てのガラス短繊維１０〜４０wt％とを均一に分散混合し
た組成物が射出された後に、加熱圧縮成形して製造され
る複合誘電体の製造方法。5. A polyphenylene sulfide resin 30 to
A composite dielectric produced by heat compression molding after injecting a composition in which 60 wt%, 15 to 55 wt% of a fluororesin, and 10 to 40 wt% of glass short fibers as a filler are uniformly dispersed and mixed. Production method.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP7176724A JP3001400B2 (en) | 1995-06-19 | 1995-06-19 | High frequency printed wiring board and method of manufacturing the same |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP7176724A JP3001400B2 (en) | 1995-06-19 | 1995-06-19 | High frequency printed wiring board and method of manufacturing the same |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH093208A true JPH093208A (en) | 1997-01-07 |
| JP3001400B2 JP3001400B2 (en) | 2000-01-24 |
Family
ID=16018678
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP7176724A Expired - Fee Related JP3001400B2 (en) | 1995-06-19 | 1995-06-19 | High frequency printed wiring board and method of manufacturing the same |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3001400B2 (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20040051749A (en) * | 2002-12-11 | 2004-06-19 | 아텍엔지니어링 주식회사 | Manufacturing method of PTFE composite board |
| CN113423775A (en) * | 2019-02-27 | 2021-09-21 | 索尔维特殊聚合物美国有限责任公司 | Poly (arylene sulfide) compositions having high dielectric properties |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH059299A (en) * | 1991-07-04 | 1993-01-19 | Dainippon Ink & Chem Inc | Slurry composition |
| JPH0539370A (en) * | 1991-05-29 | 1993-02-19 | Dainippon Ink & Chem Inc | Polyarylene sulfide resin prepreg and its molded article |
-
1995
- 1995-06-19 JP JP7176724A patent/JP3001400B2/en not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0539370A (en) * | 1991-05-29 | 1993-02-19 | Dainippon Ink & Chem Inc | Polyarylene sulfide resin prepreg and its molded article |
| JPH059299A (en) * | 1991-07-04 | 1993-01-19 | Dainippon Ink & Chem Inc | Slurry composition |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20040051749A (en) * | 2002-12-11 | 2004-06-19 | 아텍엔지니어링 주식회사 | Manufacturing method of PTFE composite board |
| CN113423775A (en) * | 2019-02-27 | 2021-09-21 | 索尔维特殊聚合物美国有限责任公司 | Poly (arylene sulfide) compositions having high dielectric properties |
| US20220106457A1 (en) * | 2019-02-27 | 2022-04-07 | Solvay Specialty Polymers Usa, Llc | Poly(arylene sulphide) composition having high dielectric performance |
Also Published As
| Publication number | Publication date |
|---|---|
| JP3001400B2 (en) | 2000-01-24 |
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