JP2001176329A - Low dielectric material - Google Patents
Low dielectric materialInfo
- Publication number
- JP2001176329A JP2001176329A JP35451099A JP35451099A JP2001176329A JP 2001176329 A JP2001176329 A JP 2001176329A JP 35451099 A JP35451099 A JP 35451099A JP 35451099 A JP35451099 A JP 35451099A JP 2001176329 A JP2001176329 A JP 2001176329A
- Authority
- JP
- Japan
- Prior art keywords
- dielectric constant
- fluororesin
- low dielectric
- silica gel
- spherical silica
- 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.)
- Pending
Links
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、実質的に低誘電率
で、接着性、強度および粘性を改善した低誘電率材料に
関する。また、高速演算や高周波回路に最適なプリント
配線基板用材料、特にビルドアッププリント配線基板用
材料や、テープ巻きなどの電線被覆用材料として好適な
低誘電率材料に関する。The present invention relates to a low dielectric constant material having a substantially low dielectric constant and improved adhesion, strength and viscosity. Further, the present invention relates to a material for a printed wiring board which is most suitable for high-speed operation and a high-frequency circuit, in particular, a low dielectric constant material suitable as a material for a build-up printed wiring board and a material for covering an electric wire such as a tape.
【０００２】[0002]
【従来の技術】従来より、低誘電率多層プリント配線板
として、フッ素樹脂／ガラス繊維補強板がよく知られて
いるが、３５０℃以上の高温で接着させなければならな
い欠点があった。また、フッ素繊維織布や多孔質フッ素
樹脂シートを基材とする熱硬化性樹脂積層板や、ガラス
布を基材としフッ素樹脂粉末を混合した熱硬化性樹脂組
成物を用いる積層板等が知られているが、これらは高価
であるうえ、金属箔または金属メッキ層に対する接着性
に劣る等の欠点があった。2. Description of the Related Art Conventionally, a fluororesin / glass fiber reinforced board has been well known as a low dielectric constant multilayer printed wiring board, but has a disadvantage that it must be bonded at a high temperature of 350 ° C. or higher. Also known are thermosetting resin laminates based on fluorinated fiber fabrics and porous fluororesin sheets, and laminates using glass cloth as a base material and using a thermosetting resin composition mixed with a fluororesin powder. However, these are expensive and have disadvantages such as poor adhesion to a metal foil or a metal plating layer.
【０００３】さらに、特開昭６３−６９１０６号公報に
は、フッ素樹脂不織布を基材とする積層板が開示されて
いるが、フッ素樹脂の誘電率以下には誘電率が下がら
ず、またフッ素樹脂のみでは引張り強度が弱く、伸びが
大きく、さらに他の絶縁層に用いられる樹脂や、金属箔
または金属メッキ層との接着性に劣る問題があった。ま
た、特開平５−１８２５１８号公報には、最大粒径が２
μｍを超えない多孔性エーロゲルを用いた低誘電率材料
が開示されているが、粘性が高く、ハンドリングに問題
があった。Further, Japanese Patent Application Laid-Open No. 63-69106 discloses a laminate made of a fluororesin nonwoven fabric as a base material. However, the dielectric constant does not decrease below the dielectric constant of the fluororesin, Only with them, there is a problem that the tensile strength is low, the elongation is large, and the adhesiveness to a resin used for another insulating layer or a metal foil or a metal plating layer is poor. Japanese Patent Application Laid-Open No. 5-182518 discloses that the maximum particle size is 2
Although a low dielectric constant material using a porous airgel not exceeding μm is disclosed, there is a problem in handling due to high viscosity.
【０００４】低誘電率ビルドアッププリント配線基板用
材料についても同様の問題があり、特に金属との密着性
が悪い問題があった。また、低誘電率テープ巻きなどの
電線被覆用材料についても同様の問題があった。[0004] A similar problem also exists for a material for a low dielectric constant build-up printed wiring board, and in particular, a problem of poor adhesion to metal. In addition, there is a similar problem with electric wire coating materials such as low dielectric constant tape winding.
【０００５】すなわち、従来の電線被覆用材料はフッ素
樹脂の誘電率より下がらず、その解決方法として発泡に
よる低誘電率化が行われているが、気泡径のコントロー
ル、発泡倍率のコントロールが難しく、誘電率の値を調
節できない問題があった。また、テープ巻き用としては
未焼成フッ素樹脂を延伸し、ミクロポアをつくり、低誘
電率化を行っているが、径が小さいため誘電率の値をコ
ントロールできない問題もあった。[0005] That is, the conventional electric wire coating material does not fall below the dielectric constant of the fluororesin, and as a solution therefor, the dielectric constant is reduced by foaming. However, it is difficult to control the bubble diameter and the expansion ratio. There was a problem that the value of the dielectric constant could not be adjusted. For tape winding, unfired fluororesin is stretched to form micropores to reduce the dielectric constant. However, since the diameter is small, the value of the dielectric constant cannot be controlled.
【０００６】[0006]
【発明が解決しようとする課題】本発明は上記の問題を
解決し、実質的な誘電率を下げる方法と、接着性、強
度、粘性を改善する方法について鋭意検討した結果見い
だされたものである。SUMMARY OF THE INVENTION The present invention solves the above-mentioned problems, and has been found as a result of intensive studies on a method for lowering the substantial dielectric constant and a method for improving the adhesiveness, strength and viscosity. .
【０００７】[0007]
【課題を解決するための手段】すなわち、本発明は、フ
ッ素樹脂と、細孔容積が０．５〜３．５ｃｍ3／ｇで平
均粒径が２〜１００μｍである多孔質真球状シリカゲル
からなる、誘電率が１ＭＨｚにおいて３．０以下である
低誘電率材料を提供する。That is, the present invention comprises a fluororesin and a porous spherical silica gel having a pore volume of 0.5 to 3.5 cm 3 / g and an average particle size of 2 to 100 μm. , A low dielectric constant material having a dielectric constant of 3.0 or less at 1 MHz.
【０００８】[0008]
【発明の実施の形態】本発明において、フッ素樹脂とし
ては公知のものが使用できるが、テトラフルオロエチレ
ンの重合体またはテトラフルオロエチレンと他のモノマ
ーとの共重合体であることが好ましい。テトラフルオロ
エチレンの重合体またはテトラフルオロエチレンと他の
モノマーとの共重合体は、その他のフッ素樹脂より、電
気的特性の高周波における低誘電率、誘電正接および耐
熱性の向上などの点から有利である。DESCRIPTION OF THE PREFERRED EMBODIMENTS In the present invention, a known fluororesin can be used, but it is preferably a polymer of tetrafluoroethylene or a copolymer of tetrafluoroethylene and another monomer. A polymer of tetrafluoroethylene or a copolymer of tetrafluoroethylene and another monomer is more advantageous than other fluororesins in terms of low dielectric constant at high frequency of electric characteristics, dielectric loss tangent and improvement of heat resistance. is there.
【０００９】具体的には、ポリテトラフルオロエチレ
ン、テトラフルオロエチレン・パーフルオロ（アルコキ
シエチレン）共重合体、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体、テトラフルオロエチレ
ン・エチレン共重合体などが例示される。これらは、一
種単独で用いても二種以上を混合して用いてもよい。ま
た、フッ素樹脂の形状はパウダー状またはディスパージ
ョン状のものがよいが、他の樹脂と混合したエナメル状
のものでもよい。Specific examples include polytetrafluoroethylene, tetrafluoroethylene / perfluoro (alkoxyethylene) copolymer, tetrafluoroethylene / hexafluoropropylene copolymer, and tetrafluoroethylene / ethylene copolymer. You. These may be used alone or in combination of two or more. The shape of the fluororesin is preferably in the form of a powder or a dispersion, but may be in the form of an enamel mixed with another resin.
【００１０】本発明における多孔質真球状シリカゲルと
しては、細孔容積が０．５〜３．５ｃｍ3／ｇで、平均
粒径が２〜１００μｍのものが使用される。本発明にお
いて、真球状とは、シリカゲルの形状が長粒子径に対す
る短粒子径の比率が０．８〜１であるものをいい、特に
０．９５〜１であるものが望ましい。これは、特定の粒
径のものを使用することと合わせて、特にフッ素樹脂と
混合後の粘性から、中心粒径はあまり小さくない方が好
ましく、また後にフィルム状やシート状で用いられる際
の成形性等の観点から、中心粒径は大きすぎないことが
望ましいからである。The porous spherical silica gel used in the present invention has a pore volume of 0.5 to 3.5 cm 3 / g and an average particle size of 2 to 100 μm. In the present invention, the term "spherical" refers to a silica gel having a ratio of a short particle diameter to a long particle diameter of 0.8 to 1, particularly preferably 0.95 to 1. This is because it is preferable that the central particle size is not so small, especially from the viscosity after mixing with the fluororesin, in addition to using a specific particle size, and when the film or sheet is used later. This is because it is desirable that the center particle size is not too large from the viewpoint of moldability and the like.
【００１１】シリカゲルの細孔容積は、０．５ｃｍ3／
ｇ未満であると大量に配合しても低誘電率化効果が低
く、また、細孔容積が３．５ｃｍ3／ｇ以上のシリカゲ
ルは強度が弱く、各工程中で粒子の崩壊が起こり好まし
くない。特に望ましい細孔容積は、１〜３ｃｍ3／ｇで
ある。The pore volume of silica gel is 0.5 cm 3 /
If the amount is less than 0.1 g, the effect of lowering the dielectric constant is low even if it is blended in a large amount, and silica gel having a pore volume of 3.5 cm 3 / g or more has low strength, and particles are disintegrated in each step, which is not preferable. . Particularly preferred pore volume is 1 to 3 cm 3 / g.
【００１２】また、シリカゲルの平均粒径は、２〜１０
０μｍであるが、これは、上記したように、特にフッ素
樹脂と混合後の粘性から、中心粒径はあまり小さくない
方が好ましく、また後にフィルム状やシート状で用いら
れる等の観点から、中心粒径は大きすぎないことが望ま
しいからである。特に望ましいのは２．５〜３０μｍで
ある。これは、低誘電率化目的の際と同様に、平均粒径
が３０μｍより大きいと、多孔質真球状シリカゲルによ
って得られるアンカー密度が小さく不均一になりやす
い、または硬化物表面の凹凸が必要以上に激しくなっ
て、後に硬化物表面に施す導体の微細パターンが得難く
なるなどによる。平均粒径が２．５μｍより小さいと、
単純に樹脂に配合したことによって得られる凹凸が小さ
くなり、アンカー効果が得難くなることがある。このよ
うな観点から、シリカゲルの粒径として１μｍ以下のも
のおよび１５０μｍ以上のものは可及的に少量に制限す
ることが望ましい。The average particle size of silica gel is 2-10.
Although it is 0 μm, as described above, it is preferable that the center particle size is not so small, especially from the viscosity after mixing with the fluororesin, and from the viewpoint of being used later in the form of a film or sheet, This is because it is desirable that the particle size is not too large. Particularly desirable is 2.5 to 30 μm. This is because, when the average particle size is larger than 30 μm, the anchor density obtained by the porous spherical silica gel tends to be small and non-uniform as in the case of the purpose of lowering the dielectric constant. And it becomes difficult to obtain a fine pattern of a conductor to be subsequently applied to the surface of the cured product. When the average particle size is smaller than 2.5 μm,
Irregularities obtained by simply being blended with the resin are reduced, and it may be difficult to obtain an anchor effect. From such a viewpoint, it is desirable that the silica gel particles having a particle size of 1 μm or less and those having a particle size of 150 μm or more be limited to the smallest possible amount.
【００１３】本発明において、シリカゲルの細孔容積
は、気体吸着法（ＢＥＴ法）により、また平均粒径はコ
ールカウンター法（Ｅｌｅｃｔｒｏｎ Ｓｅｎｓｉｎｇ
Ｚｏｕｅ Ｍｅｔｈｏｄ法）により測定される。In the present invention, the pore volume of silica gel is determined by a gas adsorption method (BET method), and the average particle diameter is determined by a coal counter method (Electron Sensing).
It is measured by the Zoom Method method.
【００１４】本発明では、さらに、フッ素樹脂との混合
後の粘度を下げるために、またより最密充填とするため
に、異なる粒子径の２種類以上の多孔質真球状シリカゲ
ルを配合することも有効である。In the present invention, two or more kinds of porous spherical silica gels having different particle diameters may be blended in order to lower the viscosity after mixing with the fluororesin and to achieve the closest packing. It is valid.
【００１５】なお、このような本発明で使用される特定
のシリカゲルは、公知の方法、例えばシリカゾルスプレ
ードライ法、ケイ酸ソーダ乳化造粒反応法などにより容
易に得ることができる。The specific silica gel used in the present invention can be easily obtained by a known method, for example, a silica sol spray drying method, a sodium silicate emulsification granulation reaction method and the like.
【００１６】本発明はこのようなフッ素樹脂と多孔質真
球状シリカゲルとからなる。その混合比率は、目的、用
途に応じて幅広い比率、すなわち、質量で１：９９〜９
９：１から選ばれる比率での使用ができる。なかでも、
１０：９０〜９０：１０、特には、２５：７５〜７５：
２５での使用が一般的には望ましい。The present invention comprises such a fluororesin and a porous spherical silica gel. The mixing ratio may vary widely depending on the purpose and application, that is, 1:99 to 9 by mass.
It can be used at a ratio selected from 9: 1. Above all,
10: 90-90: 10, especially 25: 75-75:
Use at 25 is generally desirable.
【００１７】上記のフッ素樹脂と多孔質真球状シリカゲ
ルとの混合物には、これらの他に混合物の物性を改善す
る目的、例えば可とう性付与、接着性または親和性（特
に基材繊維との接着性や親和性）付与、耐燃焼性付与、
離型性付与、消泡性付与などの目的で、シリコーン系化
合物、フッ素系化合物、ノニオン系の耐熱性の界面活性
剤、シランカップリング剤、チタネートカップリング
材、ワックス類、ジエン系ゴム類、非晶性または低結晶
性の飽和ポリエステル樹脂、ウレタン樹脂、酢酸ビニル
樹脂、ポリエチレン樹脂などの化合物や樹脂類を、また
粘度調整剤としての反応型の低分子量化合物類（反応性
希釈剤）、例えばスチレンなどの芳香族ビニル化合物、
トリメチロールプロパントリ（メタ）アクリレートなど
のアクリレート類、モノグリシジルエーテルなどを、樹
脂成分の３０質量％未満の量で添加することもでき、特
にカップリング材類を他材料との接着性向上のために用
いることは望ましい。しかし、これらは全て誘電率を上
げる作用があるため、添加量はできるだけ少量にとどめ
ることが望ましい。The mixture of the above-mentioned fluororesin and the porous spherical silica gel may be used for the purpose of improving the physical properties of the mixture, for example, for imparting flexibility, adhesion or affinity (particularly adhesion to the base fiber). Properties and affinity), combustion resistance,
For the purpose of imparting release properties, imparting defoaming properties, silicone compounds, fluorine compounds, nonionic heat-resistant surfactants, silane coupling agents, titanate coupling materials, waxes, diene rubbers, Compounds or resins such as amorphous or low-crystalline saturated polyester resins, urethane resins, vinyl acetate resins, polyethylene resins, etc., and reactive low molecular weight compounds (reactive diluents) as viscosity modifiers, for example, Aromatic vinyl compounds such as styrene,
Acrylates such as trimethylolpropane tri (meth) acrylate, monoglycidyl ether, and the like can be added in an amount of less than 30% by mass of the resin component. Is desirable. However, since all of them have the effect of increasing the dielectric constant, it is desirable to keep the addition amount as small as possible.
【００１８】本発明では、フッ素樹脂と特定の多孔質真
球状シリカゲルを組み合わせることによるフィラー効果
で、フッ素樹脂層のみで使用しうる強度を発現できる。
また多孔質真球状シリカゲルの、表面にあるオープンポ
アによって生じるアンカー効果での強度発現もあり、多
孔度は高い方が望ましい。In the present invention, the strength which can be used only by the fluororesin layer can be exhibited by the filler effect by combining the fluororesin and the specific porous spherical silica gel.
In addition, since the porous spherical silica gel has strength due to an anchor effect generated by open pores on the surface, it is desirable that the porosity is high.
【００１９】また、本発明では、多孔質真球状シリカゲ
ルを組み合わせることによって接着性も改善しうるが、
これは硬化物表面に自然にできる凹凸や、または硬化物
表面を化学処理や研磨等物理的な処理を施すことによっ
て露出した多孔質真球状シリカゲルの多孔による凹凸
や、さらには同様に硬化物表面に露出した多孔質真球状
シリカゲルを、化学処理によって溶かしだして凹凸を形
成しこれによるアンカー効果を向上させることもでき
る。In the present invention, the adhesion can be improved by combining porous spherical silica gel.
This is due to the unevenness that can be naturally formed on the surface of the cured product, or the unevenness due to the porosity of porous spherical silica gel exposed by subjecting the surface of the cured product to physical treatment such as chemical treatment or polishing. The porous spherical silica gel exposed to the surface can be melted out by a chemical treatment to form irregularities, thereby improving the anchor effect.
【００２０】多孔質真球状シリカゲルは接着性の改善に
おいて凹凸を導入するためにも効果的に用いられてお
り、表面に露出させ、さらに溶かし出す等の操作を行う
場合には、やはりより空隙率の高いシリカゲルの使用が
望ましい。[0020] Porous spherical silica gel is also effectively used to introduce irregularities in the improvement of adhesiveness. When an operation such as exposing to the surface and further dissolving is performed, the porosity is also increased. It is desirable to use silica gel having a high molecular weight.
【００２１】多孔質真球状シリカゲルを硬化物表面に露
出させるために用いられる処理としては化学処理や研磨
等物理的な処理があげられる。具体的には化学処理とし
てはソフトエッジなどの酸化処理、研磨等物理的な処理
としてはｎ軸オシレーション研磨機（ｎ＝２〜８）、ス
クラブ研磨機等による処理があげられるが、これに限定
されない。The treatment used to expose the porous spherical silica gel to the surface of the cured product includes physical treatment such as chemical treatment and polishing. Specifically, the chemical treatment includes oxidation using a soft edge or the like, and the physical treatment such as polishing includes treatment using an n-axis oscillation polisher (n = 2 to 8), a scrub polisher, or the like. Not limited.
【００２２】酸化処理に用いられる酸化剤としては硝
酸、硫酸、クロム酸、クロム酸塩、過マンガン酸塩、オ
ゾンなどが用いられる。また、多孔質真球状シリカゲル
を溶かし出す化学処理に用いられる薬剤としては、フッ
化水素酸、水酸化ナトリウム溶液などがあげられるが、
これに限定されない。As the oxidizing agent used for the oxidation treatment, nitric acid, sulfuric acid, chromic acid, chromate, permanganate, ozone and the like are used. Examples of the chemicals used in the chemical treatment for dissolving the porous spherical silica gel include hydrofluoric acid and sodium hydroxide solution.
It is not limited to this.
【００２３】多孔質真球状シリカゲルはそのままでも使
用できるが、フッ素樹脂との密着性を改良する目的で表
面処理したものを使用することも好適であり、この方法
としては、シランカップリング剤やチタネートカップリ
ング剤などのカップリング材処理、フッ素系界面活性剤
などのノニオン系の耐熱性界面活性剤処理などが例示さ
れ、適宜組み合わせて使用できる。Although the porous spherical silica gel can be used as it is, it is also preferable to use a surface-treated silica gel for the purpose of improving the adhesion to the fluororesin. This method includes a silane coupling agent and a titanate. Examples include treatment with a coupling agent such as a coupling agent, treatment with a nonionic heat-resistant surfactant such as a fluorine-based surfactant, and the like, which can be used in appropriate combination.
【００２４】フッ素樹脂と多孔質真球状シリカゲルから
なる材料のシート状やフィルム状への成形方法としては
公知の種々の方法が採用できる。例えば、プリント配線
材などのシートとして成形する方法としては、大別して
フッ素樹脂ディスパージョンを用いる方法と、フッ素樹
脂粉体を用いる方法の二つがあげられるが、これに限定
されない。Various known methods can be used for forming a material comprising a fluororesin and a porous spherical silica gel into a sheet or film. For example, as a method of forming a sheet of a printed wiring material or the like, there are roughly two methods, a method using a fluororesin dispersion and a method using a fluororesin powder, but are not limited thereto.
【００２５】フッ素樹脂ディスパージョンを用いる場
合、あらかじめフッ素樹脂ディスパージョンを多孔質真
球状シリカゲルと適当な混合機で混合しておき、そこへ
適当な基材を含浸させたのち３００〜３９０℃の温度条
件下で５〜３０ｍｉｎ焼成し、成形シートを得ることが
できる。水性フッ素樹脂ディスパージョンとしてはアフ
ロンＰＴＦＥ／ＡＤ−１（商品名旭硝子社製）、アフロ
ンＰＴＦＥ／ＡＤ−６３９（商品名旭硝子社製）などが
例示できる。When a fluororesin dispersion is used, the fluororesin dispersion is mixed in advance with a porous spherical silica gel with a suitable mixer, and a suitable base material is impregnated therein. The molded sheet can be obtained by firing for 5 to 30 minutes under the conditions. Examples of the aqueous fluororesin dispersion include Aflon PTFE / AD-1 (trade name, manufactured by Asahi Glass Co., Ltd.) and Aflon PTFE / AD-639 (trade name, manufactured by Asahi Glass Co., Ltd.).
【００２６】フッ素樹脂粉体を用いる場合、あらかじめ
フッ素樹脂粉体を多孔質真球状シリカゲルと適当な混合
機で混合しておく。これを３００〜３９０℃の温度条件
下で５〜３０ｍｉｎ、厚さ０．０５〜５ｍｍにプレスす
ることによって、成形シートを得ることができる。また
は混合物をビレットに成形して厚さ０．０５〜５ｍｍに
スカイブすることにより、成形フィルムを得ることがで
きる。フッ素樹脂粉体としてはモールディングパウダー
アフロンＰＴＦＥ Ｇ１６３（商品名旭硝子社製）、フ
ァインパウダーアフロンＰＴＦＥ ＣＤ−１（商品名旭
硝子社製）、アフロンＰＴＦＥ Ｌ−１６９Ｊ（商品名
旭硝子社製）等が例示できる。When a fluororesin powder is used, the fluororesin powder is previously mixed with a porous spherical silica gel by a suitable mixer. By pressing this under a temperature condition of 300 to 390 ° C. for 5 to 30 min and a thickness of 0.05 to 5 mm, a molded sheet can be obtained. Alternatively, a molded film can be obtained by molding the mixture into a billet and skiving to a thickness of 0.05 to 5 mm. Examples of the fluororesin powder include molding powder Aflon PTFE G163 (trade name, manufactured by Asahi Glass Co., Ltd.), fine powder Aflon PTFE CD-1 (trade name, manufactured by Asahi Glass Co., Ltd.), and Aflon PTFE L-169J (trade name, manufactured by Asahi Glass Co., Ltd.). .
【００２７】本発明によって得られるフッ素樹脂と特定
のシリカゲルからなる低誘電率材料の誘電率は、１ＭＨ
ｚにおいて３．０以下であり、特に２．０以下であるも
のを容易に得ることができる。このような本発明低誘電
率材料の好ましい用途としては、低誘電率プリント配線
基板用材料であり、低誘電率電線被覆用材料である。The dielectric constant of the low dielectric constant material comprising the fluororesin and the specific silica gel obtained by the present invention is 1 MH
Those having z of 3.0 or less, particularly 2.0 or less, can be easily obtained. Preferred applications of the low dielectric constant material of the present invention are low dielectric constant printed wiring board materials and low dielectric constant electric wire coating materials.
【００２８】本発明材料を、フッ素樹脂成形シート、フ
ッ素樹脂フィルムとしてプリント配線用材料に用いる場
合、そのまま用いてもよいし、基材と組み合わせて用い
てもよい。この基材としては、ガラス布、フッ素繊維、
フッ素樹脂繊維、耐熱性エンジニアリングプラスチック
繊維、低誘電率熱可塑性樹脂繊維、低誘電率熱硬化性樹
脂繊維等の例示しうる繊維の中の一種または二種以上か
らなる混抄不織布など、公知の物を使用できる。When the material of the present invention is used for a printed wiring material as a fluororesin molded sheet or fluororesin film, it may be used as it is or in combination with a base material. As this substrate, glass cloth, fluorine fiber,
Known materials, such as fluororesin fibers, heat-resistant engineering plastic fibers, low dielectric constant thermoplastic resin fibers, and mixed nonwoven fabrics composed of one or more types of fibers such as low-dielectric constant thermosetting resin fibers. Can be used.
【００２９】この基材はそのままでも使用できるが、フ
ッ素樹脂との密着性を改良する目的で表面処理したもの
を使用することが好適であり、この方法としては、シラ
ンカップリング材やチタネートカップリング剤などのカ
ップリング剤処理、フッ素系界面活性剤などのノニオン
系の耐熱性界面活性剤処理などが例示され、適宜組み合
わせて使用できる。This substrate can be used as it is, but it is preferable to use a surface-treated one for the purpose of improving the adhesion to the fluororesin. Examples thereof include a treatment with a coupling agent such as an agent, and a treatment with a nonionic heat-resistant surfactant such as a fluorine-based surfactant, which can be used in an appropriate combination.
【００３０】また前述のビレットをスカイブすることに
よって得られた成形フィルムは本発明の低誘電率テープ
巻きなどの電線被覆用材料として好適に使用できる。こ
の場合、成形フィルムはそのまま用いてもよいし、熱可
塑性樹脂およびフィルム等と積層して用いてもよい。The molded film obtained by skiving the above-mentioned billet can be suitably used as a material for covering an electric wire such as a low dielectric constant tape wound according to the present invention. In this case, the molded film may be used as it is, or may be used by being laminated with a thermoplastic resin, a film, or the like.
【００３１】さらに、本発明のフッ素樹脂と多孔質真球
状シリカゲルを混合したものは、シート状またはフィル
ム状にしてこれらの用途に用いるほかに、そのままビル
ドアッププリント配線基板の絶縁層用ワニス、またはレ
ジストインキの材料としても使用できる。なお、その場
合は、上記プリント基板として用いられるときよりさら
に、粘性が低くかつチキソ性を持つこと等が要求され
る。Further, the mixture of the fluororesin of the present invention and porous spherical silica gel may be used in these applications in the form of a sheet or film, or may be used as it is as a varnish for an insulating layer of a build-up printed circuit board, or It can also be used as a material for resist ink. In this case, it is required to have a lower viscosity and a thixotropic property than when used as the printed circuit board.
【００３２】[0032]
【実施例】（誘電率低減効果）誘電率測定のためのテス
トピースサイズは、２００ｍｍ×１２０ｍｍ×３ｍｍ
（厚さ）で、この両面に導電ペーストを塗って配線し、
１ＭＨｚにおいて誘電率を測定した。Example (Effect of reducing dielectric constant) The test piece size for dielectric constant measurement was 200 mm x 120 mm x 3 mm
(Thickness), apply conductive paste on both sides and wire,
The dielectric constant was measured at 1 MHz.
【００３３】［例１（実施例）］ポリテトラフルオロエ
チレン樹脂粉体１００質量部に対してフルオロシランカ
ップリング剤処理を施した多孔質真球状シリカゲル（商
品名旭硝子社製サンスフェアＨ−３３、細孔容積２．０
ｃｍ3／ｇ、平均粒子径３μｍ、長径に対する短径の比
率０．９５〜１）１００質量部を混合し、混合物（Ｐ
１）を得た。この混合物（Ｐ１）を３９０℃で１５ｍｉ
ｎプレス成形して、フッ素樹脂量５０％のシート状硬化
物（Ｑ１）を得た。この硬化物（Ｑ１）の誘電率は１．
４５であった。Example 1 (Example) Porous spherical silica gel (Sunsphere H-33 manufactured by Asahi Glass Co., Ltd., obtained by treating 100 parts by mass of a polytetrafluoroethylene resin powder with a fluorosilane coupling agent) Pore volume 2.0
cm 3 / g, an average particle diameter of 3 μm, and a ratio of the minor axis to the major axis of 0.95 to 1) 100 parts by mass were mixed, and the mixture (P
1) was obtained. This mixture (P1) was added at 390 ° C. for 15 mi.
By n-press molding, a sheet-shaped cured product (Q1) having a fluororesin content of 50% was obtained. The dielectric constant of this cured product (Q1) is 1.
45.
【００３４】［例２（実施例）］ポリテトラフルオロエ
チレン樹脂粉体１００質量部に対して多孔質真球状シリ
カゲル（例１と同じ商品名旭硝子社製サンスフェアＨ−
３３）を１００質量部混合し、混合物（Ｐ２）を得た。
この混合物（Ｐ２）を３９０℃で１５ｍｉｎプレス成形
して、フッ素樹脂量５０％のシート状硬化物（Ｑ２）を
得た。この硬化物（Ｑ２）の誘電率は１．２３であっ
た。Example 2 (Example) Porous spherical silica gel (Sunsphere H-manufactured by Asahi Glass Co., Ltd. under the same trade name as in Example 1) was added to 100 parts by mass of polytetrafluoroethylene resin powder.
33) was mixed with 100 parts by mass to obtain a mixture (P2).
This mixture (P2) was press-molded at 390 ° C. for 15 minutes to obtain a sheet-like cured product (Q2) having a fluororesin content of 50%. The dielectric constant of this cured product (Q2) was 1.23.
【００３５】［例３（実施例）］混合物（Ｐ１）を金型
に充填し３９０℃で３０ｍｉｎ圧縮成形して、フッ素樹
脂量５０％のビレットを得、これをスカイブしてシート
状硬化物（Ｑ３）を得た。この硬化物（Ｑ３）で電線を
被覆し誘電率を測定したところ１．４８であった。同じ
く硬化物（Ｑ３）を電線に巻き付けて誘電率を測定した
ところ１．４６であった。Example 3 (Example) The mixture (P1) was filled in a mold and compression-molded at 390 ° C. for 30 minutes to obtain a billet having a fluororesin content of 50%, which was skived and cured into a sheet-like cured product ( Q3) was obtained. An electric wire was covered with this cured product (Q3), and the dielectric constant was measured to be 1.48. Similarly, when the cured product (Q3) was wound around an electric wire and the dielectric constant was measured, it was 1.46.
【００３６】［例４（比較例）］ポリテトラフルオロエ
チレン樹脂粉体をそのまま３９０℃で１５ｍｉｎプレス
成形して、樹脂量１００％のシート状硬化物（Ｒ１）を
得た。この硬化物（Ｒ１）の誘電率は例１に比べ高い
１．９５であった。Example 4 (Comparative Example) A polytetrafluoroethylene resin powder was directly press-molded at 390 ° C. for 15 minutes to obtain a sheet-shaped cured product (R1) having a resin amount of 100%. The dielectric constant of this cured product (R1) was 1.95, which was higher than that of Example 1.
【００３７】［例５（比較例）］ポリテトラフルオロエ
チレン樹脂粉体をそのまま３９０℃で３０ｍｉｎ圧縮成
形して、フッ素樹脂量５０％のビレットを得、これをス
カイブしてシート状硬化物（Ｒ２）を得た。この硬化物
（Ｒ２）で例３と同様に電線を被覆し誘電率を測定した
ところ例３より高い２．１であった。同じく硬化物（Ｒ
２）を例３と同様に電線に巻き付けて誘電率を測定した
ところ例３より高い１．９７であった。Example 5 (Comparative Example) A polytetrafluoroethylene resin powder was directly compression-molded at 390 ° C. for 30 minutes to obtain a billet having a fluorine resin content of 50%, which was skived and cured into a sheet-like cured product (R2 ) Got. An electric wire was coated with the cured product (R2) in the same manner as in Example 3, and the dielectric constant was measured. Similarly cured product (R
2) was wound around an electric wire in the same manner as in Example 3, and the dielectric constant was measured.
【００３８】（接着性付与効果）接着力測定は碁盤目試
験によって行った。(Adhesiveness-providing effect) The adhesive strength was measured by a grid test.
【００３９】［例６（実施例）］硬化物（Ｑ１）の片面
に、厚さ１８μｍの銅箔を重ね、１８０℃、２時間、２
ＭＰａで成形し、厚さ０．５ｍｍの銅張り積層板（Ｓ
１）を得た。Example 6 (Example) A copper foil having a thickness of 18 μm was placed on one side of the cured product (Q1),
0.5mm thick copper-clad laminate (S
1) was obtained.
【００４０】［例７（実施例）］硬化物（Ｑ１）の片面
をスクラブ研磨機で処理した後、処理面に、厚さ１８μ
ｍの銅箔を重ね、１８０℃、２時間、２ＭＰａで成形
し、厚さ０．４ｍｍの銅張り積層板（Ｓ２）を得た。Example 7 (Example) After one surface of the cured product (Q1) was treated with a scrub polisher, the treated surface was coated with a 18 μm thick film.
m of copper foil was stacked at 180 ° C. for 2 hours at 2 MPa to obtain a copper-clad laminate (S2) having a thickness of 0.4 mm.
【００４１】［例８（実施例）］硬化物（Ｑ１）の片面
をスクラブ研磨機で処理した後、０．４ｍｏｌ／Ｌの水
酸化ナトリウム溶液（２５℃）に１時間浸漬した。取り
出した後、よく水洗、乾燥させた。処理面に、厚さ１８
μｍの銅箔を重ね、１８０℃、２時間、２ＭＰａで成形
し、厚さ０．４ｍｍの銅張り積層板（Ｓ３）を得た。Example 8 (Example) One surface of the cured product (Q1) was treated with a scrub polisher and then immersed in a 0.4 mol / L sodium hydroxide solution (25 ° C.) for 1 hour. After being taken out, it was thoroughly washed with water and dried. Thickness 18 on the treated surface
A copper foil of μm was overlaid and formed at 180 ° C. for 2 hours at 2 MPa to obtain a copper-clad laminate (S3) having a thickness of 0.4 mm.
【００４２】［例９（比較例）］硬化物（Ｒ１）の片面
に、厚さ１８μｍの銅箔を重ね、１８０℃、２時間、２
ＭＰａで成形し、厚さ０．１ｍｍの銅張り積層板（Ｔ
１）を得た。Example 9 (Comparative Example) A copper foil having a thickness of 18 μm was placed on one surface of the cured product (R1) at 180 ° C. for 2 hours.
A copper-clad laminate (T
1) was obtained.
【００４３】Ｓ１〜Ｓ３、Ｔ１の銅張り積層板の銅箔接
着性評価結果を表１に示す。接着力の評価基準はつぎの
とおりである。 ◎：０．１ＭＰａ以上、 ○：０．０１ＭＰａ以上、かつ０．１ＭＰａ未満、 ×：０．０１ＭＰａ未満。Table 1 shows the results of evaluating the copper foil adhesion of the copper-clad laminates of S1 to S3 and T1. The evaluation criteria for the adhesive strength are as follows. ◎: 0.1 MPa or more, ：: 0.01 MPa or more and less than 0.1 MPa, ×: less than 0.01 MPa.
【００４４】[0044]
【表１】 [Table 1]
【００４５】（粘性に及ぼす効果）粘性をＢ型粘度計２
号ローターを使用し、２３℃にて回転数６ｒｐｍ、６０
ｒｐｍについて、それぞれ測定を行った。(Effect on Viscosity) The viscosity was measured using a B-type viscometer 2
No. 6 rotor at 23 ° C., 60
The measurement was performed for each rpm.
【００４６】［例１０（実施例）］水分散型ポリテトラ
フルオロエチレン樹脂（固形分量１００質量部）に対し
てフルオロシランカップリング剤処理を施した多孔質真
球状シリカゲル（例１と同じ商品名旭硝子社製サンスフ
ェアＨ−３３）１００質量部を混合し、混合物（Ｐ３）
を得た。混合物（Ｐ３）の粘度は、回転数６ｒｐｍのと
きは１７０ｃＰ、回転数６０ｒｐｍのときは１３０ｃＰ
であった。Example 10 (Example) A porous spherical silica gel obtained by treating a water-dispersed polytetrafluoroethylene resin (solid content: 100 parts by mass) with a fluorosilane coupling agent (the same trade name as in Example 1) 100 parts by mass of Sunsphere H-33 manufactured by Asahi Glass Co., Ltd. were mixed, and the mixture (P3) was mixed.
I got The viscosity of the mixture (P3) is 170 cP at a rotation speed of 6 rpm and 130 cP at a rotation speed of 60 rpm.
Met.
【００４７】［例１１（実施例）］水分散型ポリテトラ
フルオロエチレン樹脂（固形分量１００質量部）に対し
てフルオロシランカップリング剤処理を施した多孔質真
球状シリカゲル（商品名旭硝子社製サンスフェアＨ−１
２２、細孔容積１．７ｃｍ3／ｇ、平均粒子径１２μ
ｍ、長径に対する短径の比率０．９５〜１）１００質量
部を混合し、混合物（Ｐ４）を得た。混合物（Ｐ４）の
粘度は、回転数６ｒｐｍのときは１５０ｃＰ、回転数６
０ｒｐｍのときは１２０ｃＰであった。Example 11 (Example) A porous spherical silica gel obtained by subjecting a water-dispersed polytetrafluoroethylene resin (solid content: 100 parts by mass) to a fluorosilane coupling agent treatment (trade name: Suns manufactured by Asahi Glass Co., Ltd.) Fair H-1
22, pore volume 1.7 cm 3 / g, average particle diameter 12μ
m, a ratio of the minor axis to the major axis of 0.95 to 1) and 100 parts by mass were mixed to obtain a mixture (P4). The viscosity of the mixture (P4) is 150 cP at a rotation speed of 6 rpm, and 6
At 0 rpm, it was 120 cP.
【００４８】［例１２（比較例）］テトラエトキシシラ
ンのエタノール溶液をアンモニア水により加水分解し
た。エタノール中の分散粒子の形成後、重合工程の間に
生じた空隙が維持され、超高多孔性微粒子が生成される
ように、超臨界乾燥／抽出により溶媒エタノールを除去
した。これらの操作によって得られた、約８０％の多孔
度および約１０ｎｍの細孔直径を有するシリカエーロゲ
ル粒子を、６００℃で２時間熱処理し、さらにフルオロ
シラン処理した。得られた粉体１００質量部を、水分散
型ポリテトラフルオロエチレン樹脂（固形分量１００質
量部）と混合し、混合物（Ｕ１）を得た。混合物（Ｕ
１）の粘度は、回転数６ｒｐｍのときは４８０ｃＰ、回
転数６０ｒｐｍのときは２９０ｃＰであった。また、上
記操作により得られた熱処理後の粉体中心粒径は０．３
μｍであった。Example 12 (Comparative Example) A solution of tetraethoxysilane in ethanol was hydrolyzed with aqueous ammonia. After the formation of the dispersed particles in ethanol, the solvent ethanol was removed by supercritical drying / extraction so that the voids created during the polymerization step were maintained and ultra-high porosity fine particles were produced. The silica airgel particles having a porosity of about 80% and a pore diameter of about 10 nm obtained by these operations were heat-treated at 600 ° C. for 2 hours, and further treated with fluorosilane. 100 parts by mass of the obtained powder was mixed with a water-dispersed polytetrafluoroethylene resin (solid content: 100 parts by mass) to obtain a mixture (U1). Mixture (U
The viscosity of 1) was 480 cP at a rotation speed of 6 rpm and 290 cP at a rotation speed of 60 rpm. Further, the powder center particle diameter after heat treatment obtained by the above operation is 0.3
μm.
【００４９】[0049]
【発明の効果】本発明は、実質的に低誘電率で、基材に
対しての接着性がよく強度も十分である。また、シート
状やフィルム状に成形するに際して粘性を適度に調整で
きるので操作が容易である。したがって、低誘電率の高
速演算や高周波回路に最適なプリント配線基板特にビル
ドアッププリント配線基板用材料や低誘電率のテープ巻
きなどの電線被覆用材料として好適であるなど広い用途
に適用できる。The present invention has a substantially low dielectric constant, good adhesion to a substrate, and sufficient strength. In addition, since the viscosity can be appropriately adjusted when forming into a sheet or a film, the operation is easy. Therefore, the present invention can be applied to a wide range of applications, such as being suitable as a material for a printed wiring board, particularly a build-up printed wiring board, and a material for covering an electric wire such as a tape wound with a low dielectric constant, which is optimal for high-speed arithmetic operation and high-frequency circuits with a low dielectric constant.
───────────────────────────────────────────────────── フロントページの続き Ｆターム(参考） 4J002 BD121 BD151 DJ016 FA096 FD016 GQ00 GQ01 5G303 AA05 AB06 AB12 BA12 CA01 CA09 CB30 5G305 AA06 AA14 AB10 AB15 AB34 BA15 BA24 BA26 CA38 CA51 CC02 CD01 ──────────────────────────────────────────────────続 き Continued on the front page F term (reference) 4J002 BD121 BD151 DJ016 FA096 FD016 GQ00 GQ01 5G303 AA05 AB06 AB12 BA12 CA01 CA09 CB30 5G305 AA06 AA14 AB10 AB15 AB34 BA15 BA24 BA26 CA38 CA51 CC02 CD01
Claims (4)
ｃｍ3／ｇで平均粒径が２〜１００μｍである多孔質真
球状シリカゲルからなる、誘電率が１ＭＨｚにおいて
３．０以下である低誘電率材料。1. A fluororesin having a pore volume of 0.5 to 3.5.
A low-permittivity material having a dielectric constant of 3.0 or less at 1 MHz, comprising a porous spherical silica gel having an average particle size of 2 to 100 μm in cm 3 / g.
重合体またはテトラフルオロエチレンと他のモノマーと
の共重合体である請求項１記載の低誘電率材料。2. The low dielectric constant material according to claim 1, wherein the fluororesin is a polymer of tetrafluoroethylene or a copolymer of tetrafluoroethylene and another monomer.
項１または２記載の低誘電率材料。3. The low dielectric constant material according to claim 1, which is used as a material for printed circuit boards.
または２記載の低誘電率材料。4. The method according to claim 1, which is used as a material for covering electric wires.
Or the low dielectric constant material according to 2.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP35451099A JP2001176329A (en) | 1999-12-14 | 1999-12-14 | Low dielectric material |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP35451099A JP2001176329A (en) | 1999-12-14 | 1999-12-14 | Low dielectric material |
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| JP2001176329A true JP2001176329A (en) | 2001-06-29 |
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| JP35451099A Pending JP2001176329A (en) | 1999-12-14 | 1999-12-14 | Low dielectric material |
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| JP2006286352A (en) * | 2005-03-31 | 2006-10-19 | Sumitomo Bakelite Co Ltd | Resin composition, layered product, wiring board and its manufacturing method |
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| US7586047B2 (en) | 2004-01-14 | 2009-09-08 | Sumitomo Electric Industries, Ltd. | Method for manufacturing patterned porous molded product or nonwoven fabric, and electric circuit component |
| JP2010502772A (en) * | 2006-09-04 | 2010-01-28 | ライプニッツ−インスティトゥート フィア ノイエ マテリアーリエン ゲマインニュッツィヒ ゲゼルシャフト ミット ベシュレンクタ ハフトゥング | Composition for coating electrical conductors and method for preparing such a composition |
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