JPH07724B2 - Tetrafluoroethylene resin composition - Google Patents
Tetrafluoroethylene resin compositionInfo
- Publication number
- JPH07724B2 JPH07724B2 JP1103064A JP10306489A JPH07724B2 JP H07724 B2 JPH07724 B2 JP H07724B2 JP 1103064 A JP1103064 A JP 1103064A JP 10306489 A JP10306489 A JP 10306489A JP H07724 B2 JPH07724 B2 JP H07724B2
- Authority
- JP
- Japan
- Prior art keywords
- resin composition
- dielectric constant
- tetrafluoroethylene resin
- composition
- dielectric
- 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.)
- Expired - Fee Related
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
- H05K1/032—Organic insulating material consisting of one material
- H05K1/034—Organic insulating material consisting of one material containing halogen
-
- 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
Landscapes
- Compositions Of Macromolecular Compounds (AREA)
- Inorganic Insulating Materials (AREA)
Description
【発明の詳細な説明】 〔産業上の利用分野〕 この発明は、例えばマイクロ波用回路基板の誘電体材料
として好適な四フッ化エチレン樹脂組成物に関する。The present invention relates to a tetrafluoroethylene resin composition suitable as a dielectric material for a microwave circuit board, for example.
四フッ化エチレン樹脂（以下PTFEと称することがある）
は、その優れた電気的特性、耐熱性、耐薬品性等に基づ
き、種々の用途に使用されている。これを誘電体材料と
して用いる場合には、もちろんそのままでも用いられる
が、近年その電気的性質等を改質する目的で、各種の無
機充填材の添加による複合化が行なわれている。例えば
特開昭55−130008号では、マイクロ波用回路基板に使用
するための誘電率の高い誘電体材料として、PTFEに酸化
チタンとガラス繊維を混入してなる組成物が開示されて
いる。Tetrafluoroethylene resin (hereinafter sometimes referred to as PTFE)
Has been used in various applications based on its excellent electrical characteristics, heat resistance, chemical resistance, and the like. When it is used as a dielectric material, it can be used as it is, but in recent years, for the purpose of modifying its electrical properties and the like, compounding by adding various inorganic fillers has been performed. For example, JP-A-55-130008 discloses a composition in which titanium oxide and glass fiber are mixed in PTFE as a dielectric material having a high dielectric constant for use in a microwave circuit board.
ところで、酸化チタンは、チタン酸バリウムなどの他の
高誘電率充填材に比べて誘電損失が小さいことから、上
記誘電体材料での使用に好都合であるが、その半面誘電
率が他のものに比べると低いので、樹脂組成物の誘電率
を高めるには、PTFEに多量に混入する必要がある。とこ
ろが、酸化チタンは嵩密度が小さいために、多量に混入
した場合には、成形物に空隙が生じやすい。そして、こ
の空隙は、成形物の耐湿性を低下させ、電気的特性を不
安定にする原因となっている。また、空隙は酸化チタン
の配合量が高まるにつれて増加するから、配合量の高い
領域では、空隙の増加による誘電率の低下が無視できな
くなる。したがって、配合量を増やしても誘電率はそれ
ほど上がらない。さらに、空隙の増加は、成形物の機械
的強度の低下の原因になるなど、検討すべき幾つかの課
題が残されている。By the way, since titanium oxide has a smaller dielectric loss than other high-dielectric-constant fillers such as barium titanate, it is convenient for use in the above-mentioned dielectric material, but its half-face dielectric constant is different. Since it is lower than the comparison, it is necessary to mix a large amount with PTFE in order to increase the dielectric constant of the resin composition. However, since titanium oxide has a small bulk density, when mixed in a large amount, voids are likely to occur in the molded product. The voids reduce the moisture resistance of the molded product and make the electrical characteristics unstable. In addition, since the voids increase as the blending amount of titanium oxide increases, the decrease in the dielectric constant due to the increasing voids cannot be ignored in the region where the blending amount is high. Therefore, the dielectric constant does not increase so much even if the compounding amount is increased. Further, there are some problems left to be considered, such as an increase in voids causes a decrease in mechanical strength of the molded product.
そこで、この発明は、上記従来技術にみられる課題を解
決し、耐湿性および機械的強度に優れ、高誘電率で誘電
損失の小さい四フッ化エチレン樹脂組成物の提供をその
目的とする。Therefore, an object of the present invention is to provide a tetrafluoroethylene resin composition that solves the problems found in the above-mentioned prior art, is excellent in moisture resistance and mechanical strength, and has a high dielectric constant and a small dielectric loss.
上記目的を達成するために、この発明では、四フッ化エ
チレン樹脂、酸化チタン、チタン酸カルシウムおよび導
電性炭素物質を含有してなる四フッ化エチレン樹脂組成
物を構成する。In order to achieve the above object, the present invention provides a tetrafluoroethylene resin composition containing a tetrafluoroethylene resin, titanium oxide, calcium titanate and a conductive carbon substance.
本発明では、高誘電率充填材として酸化チタンとチタン
酸カルシウムが併用され、これらは目的とする組成物の
電気的特性に応じ、組成物中に両者を合わせて40〜80重
量％の範囲で使用されるが、誘電率、耐湿性等の点から
好ましい配合量は、50〜70重量％である。さらに、酸化
チタンとチタン酸カルシウムの比率は、組成物の誘電率
と誘電損失の兼合いにより選定される。In the present invention, titanium oxide and calcium titanate are used in combination as a high dielectric constant filler, and these are in the range of 40 to 80% by weight in the composition, depending on the electrical characteristics of the composition. Although used, the preferable blending amount is 50 to 70% by weight from the viewpoint of dielectric constant, moisture resistance and the like. Furthermore, the ratio of titanium oxide to calcium titanate is selected in consideration of the balance between the dielectric constant and the dielectric loss of the composition.
また、本発明において、誘電性炭素物質としては、その
材質は特に限定されることはなく、例えばファーネスブ
ラック、アセチレンブラック、チャンネルブラックなど
のカーボンブラック、あるいはグラファイト、炭素繊維
等の種々の材質のものの使用が可能であり、さらに形状
についても、粉末状、粒子状、繊維状、繊維粉末状な
ど、各種形状のものが採用される。そして、これら導電
性炭素物質の配合量は、組成物の絶縁抵抗をあまり低下
させない程度に選択されるが、好ましくは組成物中に0.
005〜0.1重量％の範囲で使用される。さらに、導電性炭
素物質は一種に限らず、必要に応じ二種以上組み合わせ
て使用してもよい。In the present invention, the material of the dielectric carbon material is not particularly limited, and for example, carbon black such as furnace black, acetylene black, and channel black, or various materials such as graphite and carbon fiber can be used. It can be used, and as for the shape, various shapes such as powder, particle, fiber, and fiber powder are adopted. Then, the blending amount of these conductive carbon substances is selected to such an extent that the insulation resistance of the composition is not significantly lowered, but preferably 0 in the composition.
Used in the range of 005 to 0.1% by weight. Further, the conductive carbon material is not limited to one kind, and may be used in combination of two or more kinds as necessary.
なお、PTFEに配合するこれらの充填材は、あらかじめカ
ップリング剤等の表面処理剤を用いて処理すると、母材
であるPTFEに対する親和性が増すので、樹脂組成物を成
形したときの耐湿性や機械的強度がさらに向上し好都合
である。また、本発明では、その目的および効果を損な
わない程度に他の充填材、顔料などを添加することは何
ら差し支えない。Incidentally, these fillers to be mixed with PTFE, if previously treated with a surface treatment agent such as a coupling agent, the affinity for the base material PTFE increases, so that the moisture resistance and the moisture resistance at the time of molding the resin composition It is advantageous because the mechanical strength is further improved. Further, in the present invention, other fillers, pigments and the like may be added to the extent that the objects and effects thereof are not impaired.
酸化チタンは、チタン酸カルシウムに比べると誘電率は
低いが、誘電損失が小さいという特性があり、一方、チ
タン酸カルシウムは、誘電損失が大きいものの誘電率は
高いという特性がある。そこで、本発明による樹脂組成
物では、高誘電率で且つ誘電損失の小さいものを得るた
めに、両者を併用し、さらに小量の導電性炭化物質を加
えている。この場合、酸化チタンとチタン酸カルシウム
の併用により互いの利点が生かされることとなり、この
ためそれぞれ単独で配合するときに比べると、誘電率と
誘電損失のバランスの調整が容易になると共に、少ない
配合量で同等の効果が得られる。しかも、これに少量の
導電性炭化物質を添加することにより、それら高誘電率
充填材の配合量をさらに減らすことができる。その結
果、この樹脂組成物は、シート状などに成形したとき
に、空隙の発生が大幅に減少し、耐湿性ならびに機械的
強度の良好なものとなる。Titanium oxide has a characteristic that the dielectric constant is lower than that of calcium titanate, but the dielectric loss is small, while calcium titanate has a characteristic that the dielectric constant is high although the dielectric loss is large. Therefore, in the resin composition according to the present invention, in order to obtain a resin composition having a high dielectric constant and a small dielectric loss, both of them are used together and a small amount of a conductive carbide substance is added. In this case, the combined use of titanium oxide and calcium titanate will bring out the advantages of each other, and as a result, it will be easier to adjust the balance between the dielectric constant and the dielectric loss, and a smaller amount will be used, as compared with the case where they are mixed alone. The same effect can be obtained by the amount. Moreover, by adding a small amount of conductive carbide to this, the amount of the high dielectric constant filler compounded can be further reduced. As a result, when this resin composition is molded into a sheet or the like, the generation of voids is significantly reduced, and the moisture resistance and mechanical strength are improved.
なお、本発明による樹脂組成物においては、粒径の小さ
い酸化チタンの粒子が、比較的大きな粒径のチタン酸カ
ルシウム粒子を取り囲んで大きな粒子となり、そしてカ
ーボンブラックなどの導電性炭素物質は、それら集合粒
子間の隙間に入り込むことにより、組成物の誘電損失を
増加させることなく、その誘電率を高めているものと推
察される。In the resin composition according to the present invention, particles of titanium oxide having a small particle size are large particles surrounding calcium titanate particles having a relatively large particle size, and conductive carbon substances such as carbon black are It is presumed that the dielectric constant of the composition is increased without increasing the dielectric loss of the composition by entering the gaps between the aggregated particles.
以下、本発明を実施例をもって具体的に説明するが、本
発明は何らこれらの実施例に限定されるものではない。Hereinafter, the present invention will be specifically described with reference to examples, but the present invention is not limited to these examples.
実施例１ 60重量部のチタン酸カルシウム（富士チタン工業社製C
T）と20重量部の酸化チタン（チタン工業社製KV−300
0）と0.01重量部のカーボンブラック（デグサ社製XE2）
をそれぞれシラン系カップリング剤を用いて表面処理し
た後、これらを40重量部のイソプロピルアルコールと40
重量部のメタノールからなる混合液に分散させ、そして
この分散液に20重量部の四フッ化エチレン樹脂固形分を
含む水性分散液（三井デュポンフロロケミカル社製テフ
ロン41J）を加えて撹拌し、共凝析させた。この共凝析
物を乾燥させ、本発明による樹脂組成物を得た。Example 1 60 parts by weight of calcium titanate (C by Fuji Titanium Industry Co., Ltd.
T) and 20 parts by weight of titanium oxide (KV-300 manufactured by Titanium Industry Co., Ltd.
0) and 0.01 parts by weight of carbon black (Degussa XE 2 )
After surface-treating each of them with a silane coupling agent, 40 parts by weight of isopropyl alcohol and 40
Dispersed in a mixed solution consisting of parts by weight of methanol, and added to this dispersion an aqueous dispersion containing 20 parts by weight of tetrafluoroethylene resin solids (Teflon 41J manufactured by Mitsui DuPont Fluorochemicals Co., Ltd.), stirred and mixed. Coagulated. This co-coagulated product was dried to obtain a resin composition according to the present invention.
次に、この組成物に液体潤滑剤としてソルベントナフサ
（出光石油化学社製IP−1620）を加え、室温下に12時間
放置した後、ロールで圧延して厚さ0.61mmのシート状に
成形し、さらにこのシートを370℃で５分間の焼成を行
ない、シート状の誘電体材料を得た。第１表に組成物の
割合を示した。Next, solvent naphtha (IP-1620 manufactured by Idemitsu Petrochemical Co., Ltd.) was added to this composition as a liquid lubricant, and the mixture was allowed to stand at room temperature for 12 hours and then rolled with a roll to form a sheet having a thickness of 0.61 mm. Further, this sheet was fired at 370 ° C. for 5 minutes to obtain a sheet-shaped dielectric material. Table 1 shows the composition ratios.
上記したシート状誘電体材料の特性を調べるため、その
両面に厚さ12μｍのテトラフルオロエチレン−ヘキサフ
ルオロプロピレン共重合樹脂を介してそれぞれ厚さ35μ
ｍの銅箔を重ね、加熱プレスで加圧成形して銅張積層板
を得た。そして、この積層板について、常態および吸水
処理後における誘電率、誘電正接、絶縁抵抗および吸水
率を測定し、その試験結果を第２表に示した。In order to investigate the characteristics of the above-mentioned sheet-shaped dielectric material, a thickness of 35 μm was applied to each side of the 12 μm-thick tetrafluoroethylene-hexafluoropropylene copolymer resin.
m copper foils were overlaid and pressure-molded by a hot press to obtain a copper-clad laminate. Then, the dielectric constant, the dielectric loss tangent, the insulation resistance and the water absorption of the laminated plate were measured in the normal state and after the water absorption treatment, and the test results are shown in Table 2.
なお、これらの試験は、JIS規格C6481−1976「印刷回路
用銅張積層板試験方法」により行なった。These tests were performed according to JIS standard C6481-1976 "Test method for copper clad laminate for printed circuit".
実施例２〜４、比較例１〜３ 第１表に示した配合割合（重量比）により、実施例１と
同様にして銅張積層板を作製し、実施例１と同様な試験
を行なった。その結果を第２表に示した。Examples 2 to 4 and Comparative Examples 1 to 3 A copper clad laminate was prepared in the same manner as in Example 1 with the compounding ratios (weight ratios) shown in Table 1, and the same tests as in Example 1 were performed. . The results are shown in Table 2.
〔発明の効果〕 本発明の組成物は、高誘電率でありながら誘電損失が小
さく、しかも耐湿性に優れるという顕著な効果を有する
ものである。そして、この組成物は、例えばマイクロ波
用回路基板の誘電体材料として用いると好都合であり、
また、かかる用途に限らず他の広範囲の用途にも有用で
ある。 [Effect of the Invention] The composition of the present invention has a remarkable effect that it has a high dielectric constant, a small dielectric loss, and excellent moisture resistance. And, this composition is conveniently used as a dielectric material of a circuit board for microwaves,
Moreover, it is useful not only for such applications but also for a wide range of other applications.
なお、実施例として示さないが、カーボンブラックに代
えて、例えばグラファイト等の他の導電性炭素物質を配
合した場合にも、同様な傾向が見られた。Although not shown as an example, a similar tendency was observed when other conductive carbon substances such as graphite were blended in place of carbon black.
Claims (1)
ン酸カルシウムおよび導電性炭素物質を含有してなる四
フッ化エチレン樹脂組成物。1. A tetrafluoroethylene resin composition comprising a tetrafluoroethylene resin, titanium oxide, calcium titanate and a conductive carbon substance.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1103064A JPH07724B2 (en) | 1989-04-21 | 1989-04-21 | Tetrafluoroethylene resin composition |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1103064A JPH07724B2 (en) | 1989-04-21 | 1989-04-21 | Tetrafluoroethylene resin composition |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH02281064A JPH02281064A (en) | 1990-11-16 |
| JPH07724B2 true JPH07724B2 (en) | 1995-01-11 |
Family
ID=14344241
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP1103064A Expired - Fee Related JPH07724B2 (en) | 1989-04-21 | 1989-04-21 | Tetrafluoroethylene resin composition |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH07724B2 (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP5349067B2 (en) * | 2009-02-03 | 2013-11-20 | 日東電工株式会社 | High dielectric constant insulating sheet and manufacturing method thereof |
| US10256009B2 (en) | 2014-06-19 | 2019-04-09 | Saint-Gobain Performance Plastics Corporation | Laser-markable insulation material for wire or cable assemblies |
| US9881714B2 (en) | 2014-06-19 | 2018-01-30 | Saint-Gobain Performance Plastics Corporation | Laser-markable insulation material for wire or cable assemblies |
-
1989
- 1989-04-21 JP JP1103064A patent/JPH07724B2/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| JPH02281064A (en) | 1990-11-16 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| LAPS | Cancellation because of no payment of annual fees |