JP2001181027A - Composite dielectric material - Google Patents
Composite dielectric materialInfo
- Publication number
- JP2001181027A JP2001181027A JP37380599A JP37380599A JP2001181027A JP 2001181027 A JP2001181027 A JP 2001181027A JP 37380599 A JP37380599 A JP 37380599A JP 37380599 A JP37380599 A JP 37380599A JP 2001181027 A JP2001181027 A JP 2001181027A
- Authority
- JP
- Japan
- Prior art keywords
- ceramics
- ether compound
- benzyl ether
- vol
- 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.)
- Pending
Links
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/13—Energy storage using capacitors
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明はコンデンサーを内蔵
した回路基板および複合部品やコンデンサーといった電
子部品に用いられる高い誘電率をもつ複合誘電体に関す
る。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a composite dielectric having a high dielectric constant used for a circuit board having a built-in capacitor, and an electronic component such as a composite component or a capacitor.
【０００２】[0002]
【従来の技術】近年、通信情報の急増に伴い、通信機の
小型化、軽量化、高速化が強く望まれており、これに対
応できる低誘電性電気絶縁材料が要求されている。特に
自動車電話、デジタル携帯電話等の携帯移動体通信、衛
星通信に使用される電波の周波数帯域はメガからギガＨ
ｚ帯の高周波帯域のものが使用されている。これらの通
信手段として、使用される通信機器の急速な発展の中
で、匡体および基板、電子素子の小型高密度実装化等が
図られている。2. Description of the Related Art In recent years, with the rapid increase of communication information, there has been a strong demand for miniaturization, weight reduction, and high speed of communication devices, and low dielectric insulating materials capable of coping with such demands have been demanded. In particular, the frequency band of radio waves used for portable mobile communications such as car phones and digital cellular phones, and satellite communications is from mega to giga-H.
A z-band high-frequency band is used. As these communication means, with the rapid development of communication equipment used, miniaturization and high-density mounting of housings, substrates, and electronic elements have been attempted.
【０００３】大容量のコンデンサーを得るには、一般的
に、対向電極の面積を広くすることや、層数を多くする
ことや、層間を薄くする必要があり、そのために基板や
部品サイズが大きくなったり、厚くなったりしてしま
う。In order to obtain a large-capacity capacitor, it is generally necessary to increase the area of the counter electrode, increase the number of layers, and reduce the thickness of the layers. It becomes thicker.
【０００４】そして、こうしたコンデンサーにおいて、
小型化を図るためには、誘電率の大きい材料を用いる必
要がある。[0004] In such a capacitor,
In order to reduce the size, it is necessary to use a material having a large dielectric constant.
【０００５】このような誘電体材料として、例えば、特
開平９−３１００６号公報には、特定構造のポリビニル
ベンジルエーテル化合物の硬化物を用いることが提案さ
れているが、高周波数帯域において高誘電率を達成する
には不十分であり、その要求特性を満たす材料の開発が
必要であった。As such a dielectric material, for example, Japanese Patent Application Laid-Open No. 9-31006 proposes to use a cured product of a polyvinyl benzyl ether compound having a specific structure, but has a high dielectric constant in a high frequency band. Therefore, it was not enough to achieve this, and it was necessary to develop a material that satisfied the required characteristics.
【０００６】[0006]
【発明が解決しようとする課題】本発明の目的は、大き
な比誘電率を得ることが可能であり、こうした大きな比
誘電率をようする用途、例えばコンデンサーを内蔵した
回路基板および複合部品やコンデンサー等といった電子
部品に用いられ、その要求特性に応じた対応が可能であ
る、緻密な複合誘電体を提供することである。SUMMARY OF THE INVENTION It is an object of the present invention to obtain a large relative permittivity, and to use such a large relative permittivity, such as a circuit board having a built-in capacitor, a composite component, a capacitor, and the like. An object of the present invention is to provide a dense composite dielectric which is used for such electronic components and can respond to the required characteristics.
【０００７】[0007]
【課題を解決するための手段】このような目的は、下記
の本発明によって達成される。 （１） 樹脂中にセラミクスが分散した複合誘電体にお
いて、前記樹脂がポリビニルベンジルエーテル化合物か
ら得られたものであり、前記セラミクスがＢａＴｉＯ3
系、（Ｂａ，Ｐｂ）ＴｉＯ3系、Ｂａ（Ｔｉ，Ｚｒ）Ｏ3
系、および（Ｂａ，Ｓｒ）ＴｉＯ3系から少なくとも選
ばれる組成を主成分とするセラミクスの１種以上であ
り、前記ポリビニルベンジルエーテル化合物と前記セラ
ミクスの粉末とが、その両者の合計量を１００vol%とし
たとき、前記セラミクスの粉末の含有量が３０vol%以上
７０vol%未満となる混合割合であり、１０MHz以上の高
周波数帯域での比誘電率が１０以上である複合誘電体。 （２） ポリビニルベンジルエーテル化合物とセラミク
スとの前記混合物を硬化して得られた上記（１）の複合
誘電体。 （３） ポリビニルベンジルエーテル化合物が下記式
（１）で表される上記（１）または（２）の複合誘電
体。This and other objects are achieved by the present invention described below. (1) In a composite dielectric in which ceramics are dispersed in a resin, the resin is obtained from a polyvinyl benzyl ether compound, and the ceramics is BaTiO 3.
System, (Ba, Pb) TiO 3 system, Ba (Ti, Zr) O 3
And at least one ceramic having a composition at least selected from the group consisting of (Ba, Sr) TiO 3 and the polyvinyl benzyl ether compound and the ceramics powder in a total amount of 100 vol%. The composite dielectric material has a mixing ratio in which the content of the ceramic powder is 30 vol% or more and less than 70 vol%, and has a relative dielectric constant of 10 or more in a high frequency band of 10 MHz or more. (2) The composite dielectric material according to (1), obtained by curing the mixture of a polyvinyl benzyl ether compound and ceramics. (3) The composite dielectric of the above (1) or (2), wherein the polyvinyl benzyl ether compound is represented by the following formula (1).
【０００８】[0008]
【化２】 Embedded image
【０００９】［式（１）中、Ｒ1はメチル基またはエチ
ル基を表し、Ｒ2は水素原子または炭素数１〜１０の炭
化水素基を表し、Ｒ3は水素原子またはビニルベンジル
基（ただし、水素原子とビニルベンジル基とのモル比は
６０：４０〜０：１００）を表し、ｎは２〜４の数であ
る。］ （４） 分散させるセラミクスの１００kHz〜１０MHzの
いずれかの周波数での比誘電率が９０〜１０００００で
ある上記（１）〜（３）のいずれかの複合誘電体。[In the formula (1), R 1 represents a methyl group or an ethyl group, R 2 represents a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms, and R 3 represents a hydrogen atom or a vinylbenzyl group (provided that , The molar ratio of the hydrogen atom to the vinylbenzyl group is 60:40 to 0: 100), and n is a number of 2 to 4. (4) The composite dielectric as described in any of (1) to (3) above, wherein the relative permittivity of the ceramic to be dispersed at any one of the frequencies of 100 kHz to 10 MHz is 90 to 100,000.
【００１０】なお、特開平９−３１００６号公報には、
ポリビニルベンジルエーテル化合物を、他の種々の充填
剤や強化繊維を配合し、成形材料や複合材料とすること
ができる旨の記載があり、充填剤としてチタン酸バリウ
ムウィスカーなども挙げられているが、その配合量につ
いては全く示されていない。[0010] Japanese Patent Application Laid-Open No. 9-31006 discloses that
There is a description that the polyvinyl benzyl ether compound can be used as a molding material or a composite material by blending other various fillers and reinforcing fibers, and barium titanate whiskers and the like are also mentioned as fillers. There is no indication of the compounding amount.
【００１１】[0011]
【発明の実施の形態】以下、本発明について詳細に説明
する。BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in detail.
【００１２】本発明の複合誘電体は、ポリビニルベンジ
ルエーテル化合物から得られた樹脂中にセラミクスを分
散させたものであり、１０MHz以上、好ましくは１００M
Hz〜１０GHzの高周波数帯域での比誘電率εが１０以
上、好ましくは１０〜５０である。The composite dielectric of the present invention is obtained by dispersing ceramics in a resin obtained from a polyvinyl benzyl ether compound, and is 10 MHz or more, preferably 100 MHz.
The relative dielectric constant ε in a high frequency band of Hz to 10 GHz is 10 or more, preferably 10 to 50.
【００１３】このように、高周波数帯域で、高いεを示
すため、こうした特性が要求される用途（例えばコンデ
ンサーを内蔵した回路基板および複合部品やコンデンサ
ー等といった電子部品）に適し、部品等の小型化が可能
になる。As described above, since it exhibits a high ε in a high frequency band, it is suitable for applications requiring such characteristics (for example, a circuit board having a built-in capacitor and an electronic component such as a composite component or a capacitor). Becomes possible.
【００１４】また、分散させるセラミクスの種類や量を
適宜変えることで、目的・用途に応じた特性をもつ複合
誘電体が得られる。By appropriately changing the type and amount of the ceramics to be dispersed, a composite dielectric having characteristics according to the purpose and application can be obtained.
【００１５】本発明に用いるポリビニルベンジルエーテ
ル化合物としては、式（１）で表されるものが好まし
い。The polyvinyl benzyl ether compound used in the present invention is preferably represented by the formula (1).
【００１６】[0016]
【化３】 Embedded image
【００１７】式（１）中、Ｒ1はメチル基またはエチル
基を表す。In the formula (1), R 1 represents a methyl group or an ethyl group.
【００１８】Ｒ2は水素原子または炭素数１〜１０の炭
化水素基を表す。Ｒ2で表される炭化水素基は、各々置
換基を有していてもよいアルキル基、アラルキル基、ア
リール基、等である。アルキル基としてはメチル基、エ
チル基、プロピル基、ブチル基等であり、アラルキル基
としてはベンジル基等であり、アリール基としてはフェ
ニル基等である。R 2 represents a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms. The hydrocarbon group represented by R 2 is an alkyl group, an aralkyl group, an aryl group, and the like, each of which may have a substituent. Examples of the alkyl group include a methyl group, an ethyl group, a propyl group and a butyl group, examples of the aralkyl group include a benzyl group, and examples of the aryl group include a phenyl group.
【００１９】Ｒ3は水素原子またはビニルベンジル基を
表し、水素原子は式（１）の化合物を合成する場合の出
発化合物に由来するものであり、水素原子とビニルベン
ジル基とのモル比は６０：４０〜０：１００が好まし
く、より好ましくは４０：６０〜０：１００である。R 3 represents a hydrogen atom or a vinylbenzyl group, and the hydrogen atom is derived from the starting compound when synthesizing the compound of the formula (1), and the molar ratio of the hydrogen atom to the vinylbenzyl group is 60. : 40 to 0: 100 is preferable, and more preferably 40:60 to 0: 100.
【００２０】ｎは２〜４の数である。N is a number from 2 to 4.
【００２１】なお、Ｒ3の水素原子とビニルベンジル基
とのモル比を上記範囲とすることにより、誘電体を得る
際の硬化反応を十分に進行させることができ、また十分
な誘電特性を得ることができる。これに対し、Ｒ3が水
素原子である未反応物が多くなると硬化反応が十分に進
行しなくなり、十分な誘電特性が得られなくなる。By setting the molar ratio of the hydrogen atom of R 3 to the vinylbenzyl group within the above range, the curing reaction for obtaining the dielectric can be sufficiently advanced, and sufficient dielectric properties can be obtained. be able to. On the other hand, when the number of unreacted substances in which R 3 is a hydrogen atom increases, the curing reaction does not proceed sufficiently and sufficient dielectric properties cannot be obtained.
【００２２】式（１）で表される化合物の具体例をＲ1
等の組合せで以下に示すが、これらに限定されるもので
はない。A specific example of the compound represented by the formula (1) is R 1
Are shown below, but are not limited thereto.
【００２３】[0023]
【化４】 Embedded image
【００２４】式（１）で表される化合物は、式（１）に
おいてＲ3＝Ｈであるポリフェノールと、ビニルベンジ
ルハライドとを反応させることにより得られる。この詳
細については、特開平９−３１００６号公報の記載を参
照することができる。The compound represented by the formula (1) is obtained by reacting a polyphenol in which R 3 = H in the formula (1) with vinylbenzyl halide. For the details, reference can be made to the description in JP-A-9-31006.
【００２５】本発明のポリビニルベンジルエーテル化合
物は単独で使用しても２種類以上を併用してもよい。The polyvinyl benzyl ether compounds of the present invention may be used alone or in combination of two or more.
【００２６】本発明のポリビニルベンジルエーテル化合
物は、それのみを樹脂材料として重合して用いてもよ
く、他のモノマーと共重合させて用いてもよく、さらに
は、他の樹脂と組み合わせて使用することができる。The polyvinyl benzyl ether compound of the present invention may be used by polymerizing it alone as a resin material, or may be used by copolymerizing with other monomers, and further used in combination with another resin. be able to.
【００２７】共重合可能なモノマーとしては、例えばス
チレン、ビニルトルエン、ジビニルベンゼン、ジビニル
ベンジルエーテル、アリルフェノール、アリルオキシベ
ンゼン、ジアリルフタレート、アクリル酸エステル、メ
タクリル酸エステル、ビニルピロリドン等が挙げられ
る。これらのモノマーの配合割合は、ポリビニルベンジ
ルエーテル化合物に対して、２〜５０質量％程度であ
る。Examples of the copolymerizable monomer include styrene, vinyl toluene, divinyl benzene, divinyl benzyl ether, allyl phenol, allyl oxybenzene, diallyl phthalate, acrylate, methacrylate, and vinylpyrrolidone. The mixing ratio of these monomers is about 2 to 50% by mass based on the polyvinyl benzyl ether compound.
【００２８】また、組み合わせて使用することが可能な
樹脂としては、例えばビニルエステル樹脂、不飽和ポリ
エステル樹脂、マレイミド樹脂、ポリフェノールのポリ
シアナート樹脂、エポキシ樹脂、フェノール樹脂、ビニ
ルベンジル化合物等の熱硬化性樹脂や、例えばポリエー
テルイミド、ポリエーテルスルホン、ポリアセタール、
ジシクロペンタジエン系樹脂等の熱可塑性樹脂がある。
その配合割合は、本発明のポリビニルベンジルエーテル
化合物に対して５〜９０質量％程度である。中でも好ま
しくは、ビニルエステル樹脂、不飽和ポリエステル樹
脂、マレイミド樹脂、ポリフェノールのポリシアナート
樹脂、エポキシ樹脂およびこれらの混合物からなる群か
ら選ばれる少なくとも１種である。Examples of the resin which can be used in combination include thermosetting resins such as vinyl ester resin, unsaturated polyester resin, maleimide resin, polycyanate resin of polyphenol, epoxy resin, phenol resin and vinyl benzyl compound. And, for example, polyetherimide, polyether sulfone, polyacetal,
There is a thermoplastic resin such as a dicyclopentadiene resin.
The compounding ratio is about 5 to 90% by mass based on the polyvinyl benzyl ether compound of the present invention. Among them, preferred is at least one selected from the group consisting of vinyl ester resins, unsaturated polyester resins, maleimide resins, polyphenol polycyanate resins, epoxy resins and mixtures thereof.
【００２９】本発明のポリビニルベンジルエーテル化合
物自体、あるいはこの化合物と他のモノマーまたは熱硬
化性樹脂とを含有してなる硬化性樹脂組成物の重合およ
び硬化は、公知の方法で行うことができる。硬化は、硬
化剤の存在下または不存在下のいずれでも可能である。
硬化剤としては、例えば過酸化ベンゾイル、メチルエチ
ルケトンパーオキシド、ジクミルパーオキシド、ｔ−ブ
チルパーベンゾエート等の公知のラジカル重合開始剤を
使用することができる。使用量は、ポリビニルベンジル
エーテル化合物１００質量部に対して０〜１０質量部で
ある。Polymerization and curing of the polyvinyl benzyl ether compound of the present invention itself or a curable resin composition containing this compound and another monomer or a thermosetting resin can be carried out by a known method. Curing is possible either in the presence or absence of a curing agent.
As the curing agent, a known radical polymerization initiator such as benzoyl peroxide, methyl ethyl ketone peroxide, dicumyl peroxide, and t-butyl perbenzoate can be used. The amount used is 0 to 10 parts by mass based on 100 parts by mass of the polyvinyl benzyl ether compound.
【００３０】硬化温度は、硬化剤の使用の有無および硬
化剤の種類によっても異なるが、十分に硬化させるため
には、２０〜２５０℃、好ましくは５０〜２５０℃であ
る。The curing temperature varies depending on whether or not a curing agent is used and the type of the curing agent, but is in the range of 20 to 250 ° C., preferably 50 to 250 ° C. for sufficient curing.
【００３１】また、硬化の調整のために、ハイドロキノ
ン、ベンゾキノン、銅塩等を配合してもよい。In addition, hydroquinone, benzoquinone, copper salt and the like may be blended for adjusting the curing.
【００３２】本発明に用いるセラミクス粉末は高い比誘
電率を持つことを必要とする。The ceramic powder used in the present invention needs to have a high relative dielectric constant.
【００３３】比誘電率が、１００kHz以上のいずれかの
周波数で、好ましくはおよそ９０以上のセラミクス粉末
をポリビニルベンジルエーテル化合物から得られる樹脂
中に分散させることで、より高い比誘電率の複合誘電体
を得ることが可能である。By dispersing a ceramic powder having a relative dielectric constant of any frequency of 100 kHz or higher, preferably about 90 or higher, in a resin obtained from a polyvinyl benzyl ether compound, a composite dielectric having a higher relative dielectric constant can be obtained. It is possible to obtain
【００３４】本発明に用いるセラミクス粉末は、上述の
ように、高い比誘電率を持つ粉末であればよく、２種類
以上用いてもよいが、以下の組成を主成分とする誘電体
の粉末から選択される。併せて１００kHz〜１０MHzのい
ずれかの周波数における比誘電率εを示す。As described above, the ceramic powder used in the present invention may be a powder having a high relative dielectric constant, and two or more kinds may be used. Selected. In addition, the relative dielectric constant ε at any frequency from 100 kHz to 10 MHz is shown.
【００３５】BaTiO3系[ε=1500]、(Ba,Pb)TiO3系[ε=60
00]、Ba(Ti,Zr)O3系[ε=9000]、(Ba,Sr)TiO3系[ε=700
0]。BaTiO 3 [ε = 1500], (Ba, Pb) TiO 3 [ε = 60
00], Ba (Ti, Zr) O 3 system [ε = 9000], (Ba, Sr) TiO 3 system [ε = 700
0].
【００３６】好ましくは、以下の組成を主成分とする誘
電体の粉末から選択される。Preferably, it is selected from dielectric powders having the following compositions as main components.
【００３７】BaTiO3系、Ba(Ti,Zr)O3系。BaTiO 3 system, Ba (Ti, Zr) O 3 system.
【００３８】セラミクス粉末は単結晶や多結晶の粉末で
もよい。The ceramic powder may be a single crystal or polycrystal powder.
【００３９】また、副成分としてMn酸化物、Nb2O5、V2O
5、SiO2、B2O3、ガラス等を含有してもよい。さらに、
セラミクス粉末は、入手しやすい既存の誘電体材料を用
いてもよい。例えば、廃棄セラミクスや、セラミクッス
コンデンサー用の焼結前の粉末などである。これらには
Ｑや、焼結性向上、温特改善などといった目的で副成分
としてMg、Ca、Sr、Ba等のアルカリ土類金属の酸化物や
Mn、Co、Ni等の遷移金属の酸化物や、Nb、V、Mo、W等の
酸化物のドナーやY、Sc、La等の希土類元素の酸化物
や、SiO2、B2O3、ガラスなどが含まれている場合があ
る。Mn oxide, Nb 2 O 5 , V 2 O
5 , SiO 2 , B 2 O 3 , glass and the like may be contained. further,
The ceramic powder may use an easily available existing dielectric material. For example, it is a waste ceramic or a powder before sintering for a ceramics condenser. These include oxides of alkaline earth metals such as Mg, Ca, Sr, and Ba as subcomponents for the purpose of improving Q, sinterability, temperature characteristics, and the like.
Oxides of transition metals such as Mn, Co, and Ni, donors of oxides such as Nb, V, Mo, and W, oxides of rare earth elements such as Y, Sc, and La, and SiO 2 , B 2 O 3 , Glass and the like may be included.
【００４０】また、本発明に用いるセラミクス粉末は、
１００kHz以上、好ましくは１００kHz〜１０MHzのいず
れかの周波数で比誘電率が９０以上であることが好まし
く、より好ましくは９０〜１０００００である。The ceramic powder used in the present invention is as follows:
The dielectric constant is preferably 90 or more, more preferably 90 to 100,000 at a frequency of 100 kHz or more, preferably 100 kHz to 10 MHz.
【００４１】なお、誘電率が高く誘電損失の大きなセラ
ミクスの比誘電率を高周波で測定するのは非常に難しい
ため、コンデンサーで測定する従来の周波数での値を用
いている。Since it is very difficult to measure the relative dielectric constant of ceramics having a high dielectric constant and a large dielectric loss at a high frequency, a value at a conventional frequency measured by a capacitor is used.
【００４２】セラミクス粉末の粒径は、樹脂との混練性
等を考えると、平均粒径０．２〜１００μm 程度が好ま
しい。粒径が小さくなると、樹脂との混練がしにくくな
る。また、粒径が大きくなると、不均一となり、均一な
分散を行うことができず、粉末の含有量が多い組成の成
形の際に、緻密な成形体が得られない。The average particle size of the ceramic powder is preferably about 0.2 to 100 μm in consideration of the kneadability with the resin. If the particle size is small, kneading with the resin becomes difficult. On the other hand, when the particle diameter is large, the particles become non-uniform, and uniform dispersion cannot be performed, and a dense molded body cannot be obtained when molding a composition having a large powder content.
【００４３】本発明の複合誘電体は、ポリビニルベンジ
ルエーテル化合物から得られる樹脂とセラミクスとを主
成分とするものであるが、ポリビニルベンジルエーテル
化合物とセラミクス粉末との合計量を１００vol%とした
とき、セラミクス粉末の含有量は３０vol%以上７０vol%
未満であり、好ましくは４０vol%以上６０vol%以下の範
囲である。The composite dielectric of the present invention contains a resin obtained from a polyvinyl benzyl ether compound and ceramics as main components. When the total amount of the polyvinyl benzyl ether compound and the ceramics powder is 100 vol%, The content of ceramic powder is more than 30vol% and 70vol%
And preferably in the range of 40 vol% or more and 60 vol% or less.
【００４４】セラミクス粉末が７０vol%以上であると、
プレス成形の際、流動性が非常に悪くなり、緻密な成形
物が得られなくなる。その結果、水等の侵入が容易にな
り電気特性の劣化につながる。また、比誘電率の低下が
みられる。一方、セラミクス粉末の量が３０vol%未満で
あると、誘電率の高いセラミクス粉末を含有する効果が
あまりみられない。When the content of the ceramic powder is 70 vol% or more,
During press molding, the fluidity becomes very poor, and a dense molded product cannot be obtained. As a result, intrusion of water or the like becomes easy, which leads to deterioration of electric characteristics. In addition, a decrease in the relative dielectric constant is observed. On the other hand, when the amount of the ceramic powder is less than 30 vol%, the effect of containing the ceramic powder having a high dielectric constant is not so much seen.
【００４５】本発明の複合誘電体は各成分を上記の範囲
内で適宜設定することにより、大きな比誘電率を得るこ
とが可能となる。The composite dielectric of the present invention can obtain a large relative dielectric constant by appropriately setting each component within the above range.
【００４６】本発明の複合誘電体は以下のような製造方
法に従うことが好ましい。The composite dielectric of the present invention preferably follows the manufacturing method as described below.
【００４７】まず、セラミクス粉末とポリビニルベンジ
ルエーテル化合物を所定量ずつ調合して混合する。な
お、混合は、例えば、乾式混合によっても行えるが、ボ
ールミル、攪拌機等でトルエン、キシレン等の有機溶剤
中で十分に混合でするのが望ましい。First, a predetermined amount of the ceramic powder and the polyvinyl benzyl ether compound are prepared and mixed. The mixing can be performed by, for example, dry mixing, but it is preferable that the mixing is sufficiently performed in an organic solvent such as toluene or xylene using a ball mill, a stirrer, or the like.
【００４８】このスラリーを９０〜１２０℃で乾燥し、
ポリビニルベンジルエーテル化合物とセラミクス粉末の
固まりを得る。この固まりを粉砕してポリビニルベンジ
ルエーテル化合物とセラミクスの混合粉末を得る。スラ
リーから混合粉末にする方法は、スプレードライヤー等
の顆粒製造装置を用いてもよい。The slurry is dried at 90 to 120 ° C.
A mass of the polyvinyl benzyl ether compound and the ceramic powder is obtained. This mass is pulverized to obtain a mixed powder of a polyvinyl benzyl ether compound and ceramics. As a method of converting the slurry into a mixed powder, a granule producing apparatus such as a spray dryer may be used.
【００４９】混合粉末の平均粒径は５０〜１０００μm
程度とすればよい。The average particle size of the mixed powder is 50 to 1000 μm
It should be about the degree.
【００５０】次に、この混合粉末を１００〜１５０℃で
所望の形状にプレス成形し、この成形物を１００〜２０
０℃、３０〜１８０分硬化させる。また必要に応じてス
テップキュアしてもよい。この硬化に際しては、前述の
硬化剤等の添加剤を存在させてもよい。Next, the mixed powder is press-molded into a desired shape at 100 to 150 ° C.
Cure at 0 ° C. for 30-180 minutes. Step curing may be performed as necessary. At the time of this curing, an additive such as the above-mentioned curing agent may be present.
【００５１】なお、電極の形成は、Ｃｕ等の金属箔で粉
末を挟んでプレスしながら硬化させて行うことや、完全
硬化する前の段階で片面もしくは両面にＣｕ箔等の金属
箔を張り付け、プレスしながら硬化させて行うことや、
プレスで金属箔をつけて仮硬化させた後、別に熱処理に
よって硬化を進めて行うことや、成形物を硬化させた
後、金属の蒸着やスパッタ、無電解めっきや（樹脂）電
極等の塗布により行うことができる。The electrode may be formed by pressing the powder with a metal foil of Cu or the like while pressing and curing, or by attaching a metal foil such as a Cu foil on one or both surfaces before the complete curing. Hardening while pressing,
After pre-curing by applying a metal foil with a press and then proceeding with curing by a separate heat treatment, or after curing the molded product, metal vapor deposition or sputtering, electroless plating or (resin) electrode coating etc. It can be carried out.
【００５２】本発明の複合誘電体は、上述のように、セ
ラミクス粉末を、ポリビニルベンジルエーテル化合物の
重合ないし硬化前に混合することが好ましいが、場合に
よっては、重合ないし硬化後に混合してもよい。ただ
し、完全に硬化した後におけるセラミクス粉末の混合は
望ましくない。As described above, in the composite dielectric of the present invention, it is preferable that the ceramics powder is mixed before the polymerization or curing of the polyvinyl benzyl ether compound, but in some cases, it may be mixed after the polymerization or curing. . However, mixing of the ceramics powder after it is completely cured is not desirable.
【００５３】[0053]
【実施例】以下、本発明を実施例によって具体的に説明
する。 実施例１ まず、セラミクス粉末とポリビニルベンジルエーテル化
合物を表１に示す組成になるように調合してトルエン中
で十分に混合し、これを９０〜１２０℃で約２ｈ乾燥さ
せた。次に、これを粉砕して、セラミクスとポリビニル
ベンジルエーテル化合物の混合粉末を得た。この混合粉
末の平均粒径は５０〜１０００μm であった。この粉末
を６．５cm×５cmの金型に入れて、１２０〜２００℃で
２ｈ硬化させて、目的の組成物を得た。The present invention will be specifically described below with reference to examples. Example 1 First, a ceramics powder and a polyvinyl benzyl ether compound were prepared so as to have the composition shown in Table 1, mixed well in toluene, and dried at 90 to 120 ° C. for about 2 hours. Next, this was pulverized to obtain a mixed powder of ceramics and a polyvinyl benzyl ether compound. The average particle size of the mixed powder was 50 to 1000 μm. This powder was placed in a 6.5 cm × 5 cm mold and cured at 120 to 200 ° C. for 2 hours to obtain a target composition.
【００５４】なお、セラミクス粉末は、ＢａＴｉＯ
3（平均粒径０．５μm ）、Ｂａ（Ｔｉ，Ｚｒ）Ｏ3系
（平均粒径５μm ）を用いた。The ceramic powder was BaTiO.
3 (average particle size 0.5 μm) and Ba (Ti, Zr) O 3 (average particle size 5 μm) were used.
【００５５】ポリビニルベンジルエーテル化合物は、式
（１）において、Ｒ1がメチル基、Ｒ2がベンジル基、Ｒ
3の水素原子とビニルベンジル基とのモル比が、水素原
子：ビニルベンジル基＝０：１００、ｎ＝３のものであ
る。In the polyvinyl benzyl ether compound, R 1 is a methyl group, R 2 is a benzyl group, R
Molar ratio of hydrogen atoms and the vinylbenzyl group of 3 is a hydrogen atom: vinyl benzyl group = 0: is of 100, n = 3.
【００５６】次に、上記の各組成物について、約１．０
mm角の棒状試料（約６．５mm長さ）を作製し、比誘電率
（２GHz）を空洞共振器摂動法により測定（ヒューレッ
トパカード（株）製 83620A、8757Cを使用）した。Next, for each of the above compositions, about 1.0
A rod-shaped sample (approximately 6.5 mm in length) having a square mm was prepared, and the relative dielectric constant (2 GHz) was measured by a cavity resonator perturbation method (using 83620A and 8757C manufactured by Hewlett-Packard Co., Ltd.).
【００５７】また、緻密さは成形物の表面に水を数滴落
として約１分で内部に浸透するかどうかにより評価し、
浸透しにくいものをより緻密であると評価した。The compactness is evaluated by dropping a few drops of water on the surface of the molded product and seeing whether it penetrates the interior in about 1 minute.
Those that hardly penetrated were evaluated as more dense.
【００５８】結果を表１に示す。Table 1 shows the results.
【００５９】[0059]
【表１】 [Table 1]
【００６０】実施例２ 実施例１と同じポリビニルベンジルエーテル化合物と実
施例１と同じセラミクス粉末を以下のように組み合わせ
て、実施例１と同様にして組成物を得た。Example 2 A composition was obtained in the same manner as in Example 1 by combining the same polyvinyl benzyl ether compound as in Example 1 and the same ceramic powder as in Example 1 as follows.
【００６１】Ba(TiZr)O3系のセラミクス粉末(60vol%)-
ポリビニルベンジルエーテル化合物(40vol%)［実施例１
の試料No.13の組成と同じ］ BaTiO3のセラミクス粉末(60vol%)-ポリビニルベンジル
エーテル化合物(40vol%)［実施例１の試料No.６の組成
と同じ］Ba (TiZr) O 3 ceramic powder (60 vol%)
Polyvinyl benzyl ether compound (40 vol%) [Example 1
The same as the composition of sample No. 13 of BaTiO 3 ] Ceramic powder of BaTiO 3 (60 vol%)-polyvinyl benzyl ether compound (40 vol%) [same as the composition of sample No. 6 of Example 1]
【００６２】これらの試料について、０．０１〜１０GH
zの周波数で測定した比誘電率を図１に示す。なお、測
定は実施例１と同様としたが、１００MHz（0.1GHz）以
下の周波数での測定はインピーダンスアナライザ（ヒュ
ーレットパカード（株）製4291A）を用いて行った。こ
の１００MHz以下の周波数での測定用試料は、上記組成
の混合粉末を１００〜１５０℃で板状にプレス成形し、
これにＣｕ箔（１８μm 厚）を両面につけて１００〜２
００℃でプレスしながら硬化させ、これを５mm角に切断
したものである。For these samples, 0.01 to 10 GH
FIG. 1 shows the relative dielectric constant measured at the frequency z. The measurement was performed in the same manner as in Example 1, but the measurement at a frequency of 100 MHz (0.1 GHz) or less was performed using an impedance analyzer (4291A manufactured by Hewlett-Packard Co., Ltd.). The sample for measurement at a frequency of 100 MHz or less is formed by pressing the mixed powder having the above composition into a plate at 100 to 150 ° C.
A Cu foil (18 μm thick) is applied to both sides, and 100 to 2
It is cured while being pressed at 00 ° C., and cut into 5 mm square.
【００６３】図１より、１GHz以上の高周波数帯域にお
いても、高い比誘電率を示すことがわかる。また、特性
に応じ、組成を選択することができることもわかる。FIG. 1 shows that a high dielectric constant is exhibited even in a high frequency band of 1 GHz or more. Also, it can be seen that the composition can be selected according to the characteristics.
【００６４】[0064]
【発明の効果】本発明によれば、高い比誘電率をもち、
緻密な複合誘電体が得られる。また、要求される用途に
応じた特性を得ることも可能である。According to the present invention, it has a high relative dielectric constant,
A dense composite dielectric is obtained. It is also possible to obtain characteristics according to the required use.
【図１】本発明の複合誘電体の比誘電率の周波数特性を
示すグラフである。FIG. 1 is a graph showing a frequency characteristic of a relative dielectric constant of a composite dielectric of the present invention.
───────────────────────────────────────────────────── フロントページの続き (51)Int.Cl.7 識別記号 ＦＩ テーマコート゛(参考） // Ｃ０７Ｃ 41/16 Ｃ０７Ｃ 41/16 43/215 43/215 Ｆターム(参考） 4G031 AA05 AA06 AA11 AA12 AA32 BA09 4H006 AA03 AB91 GP03 5E001 AB01 AC09 AE00 AE02 AE03 AH00 AH01 AH03 AH05 AH07 AH08 AJ01 AJ02 5G303 AA01 AA05 AA10 AB06 BA12 CA01 CA09 CB03 CB25 CB32 CB35 CB39 5G305 AA06 AA14 AB09 BA15 BA24 BA26 CA13 CC02 CD01 ──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. 7 Identification symbol FI Theme coat ゛ (Reference) // C07C 41/16 C07C 41/16 43/215 43/215 F-term (Reference) 4G031 AA05 AA06 AA11 AA12 AA32 BA09 4H006 AA03 AB91 GP03 5E001 AB01 AC09 AE00 AE02 AE03 AH00 AH01 AH03 AH05 AH07 AH08 AJ01 AJ02 5G303 AA01 AA05 AA10 AB06 BA12 CA01 CA09 CB03 CB25 CB32 CB35 CB39 5G305 AA06 AA13 AB
Claims (4)
体において、 前記樹脂がポリビニルベンジルエーテル化合物から得ら
れたものであり、 前記セラミクスがＢａＴｉＯ3系、（Ｂａ，Ｐｂ）Ｔｉ
Ｏ3系、Ｂａ（Ｔｉ，Ｚｒ）Ｏ3系、および（Ｂａ，Ｓ
ｒ）ＴｉＯ3系から少なくとも選ばれる組成を主成分と
するセラミクスの１種以上であり、 前記ポリビニルベンジルエーテル化合物と前記セラミク
スの粉末とが、その両者の合計量を１００vol%としたと
き、前記セラミクスの粉末の含有量が３０vol%以上７０
vol%未満となる混合割合であり、 １０MHz以上の高周波数帯域での比誘電率が１０以上で
ある複合誘電体。1. A composite dielectric in which ceramics are dispersed in a resin, wherein the resin is obtained from a polyvinyl benzyl ether compound, wherein the ceramics is a BaTiO 3 -based, (Ba, Pb) Ti
O 3 system, Ba (Ti, Zr) O 3 system, and (Ba, S
r) at least one kind of ceramics whose main component is at least a composition selected from TiO 3 -based materials, wherein the polyvinyl benzyl ether compound and the ceramics powder have a total volume of both of which is 100 vol%. Powder content of 30 vol% or more 70
A composite dielectric material having a mixing ratio of less than vol% and a relative dielectric constant of 10 or more in a high frequency band of 10 MHz or more.
ラミクスとの前記混合物を硬化して得られた請求項１の
複合誘電体。2. The composite dielectric according to claim 1, obtained by curing said mixture of a polyvinyl benzyl ether compound and ceramics.
記式（１）で表される請求項１または２の複合誘電体。 【化１】 ［式（１）中、Ｒ1はメチル基またはエチル基を表し、
Ｒ2は水素原子または炭素数１〜１０の炭化水素基を表
し、Ｒ3は水素原子またはビニルベンジル基（ただし、
水素原子とビニルベンジル基とのモル比は６０：４０〜
０：１００）を表し、ｎは２〜４の数である。］3. The composite dielectric according to claim 1, wherein the polyvinyl benzyl ether compound is represented by the following formula (1). Embedded image [In the formula (1), R 1 represents a methyl group or an ethyl group;
R 2 represents a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms, and R 3 represents a hydrogen atom or a vinylbenzyl group (provided that
The molar ratio between the hydrogen atom and the vinylbenzyl group is 60: 40-
0: 100), and n is a number of 2 to 4. ]
０MHzのいずれかの周波数での比誘電率が９０〜１００
０００である請求項１〜３のいずれかの複合誘電体。4. The dispersion of ceramics from 100 kHz to 1
The relative dielectric constant at any frequency of 0 MHz is 90-100
The composite dielectric material according to any one of claims 1 to 3, wherein
Priority Applications (8)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP37380599A JP2001181027A (en) | 1999-12-28 | 1999-12-28 | Composite dielectric material |
| US09/748,261 US6908960B2 (en) | 1999-12-28 | 2000-12-27 | Composite dielectric material, composite dielectric substrate, prepreg, coated metal foil, molded sheet, composite magnetic substrate, substrate, double side metal foil-clad substrate, flame retardant substrate, polyvinylbenzyl ether resin composition, thermosettin |
| KR10-2000-0087640A KR100459501B1 (en) | 1999-12-28 | 2000-12-28 | Composite Dielectric Material, Composite Dielectric Substrate, Prepreg, Coted Metal Foil, and Molded Sheet |
| EP20000311721 EP1113459A3 (en) | 1999-12-28 | 2000-12-28 | Composite dielectric material containing ceramic powders and substrate coated with this material |
| KR1020030033706A KR100606355B1 (en) | 1999-12-28 | 2003-05-27 | Prepreg, Composite Magnetic Substrate, Substrate, Double Side Metal Foil-Clad Substrate, Flame Retardant Substrate, Polyvinylbenzyl Ether Resin Composition, Thermosetting Polyvinylbenzyl Ether Resin Composition, and Method for Preparing Thermosetting Polyvinylbenzyl Ether Resin Composition |
| US11/045,159 US20050130446A1 (en) | 1999-12-28 | 2005-01-31 | Composite dielectric material, composite dielectric substrate, prepreg, coated metal foil, molded sheet, composite magnetic substrate, substrate, double side metal foil-clad substrate, flame retardant substrate, polyvinylbenzyl ether resin composition, thermosetting polyvinylbenzyl ether resin composition, and method for preparing thermosetting polyvinylbenzyl ether resin composition |
| US11/045,286 US20050130447A1 (en) | 1999-12-28 | 2005-01-31 | Composite dielectric material, composite dielectric substrate, prepreg, coated metal foil, molded sheet, composite magnetic substrate, substrate, double side metal foil-clad substrate, flame retardant substrate, polyvinylbenzyl ether resin composition, and method for preparing thermosetting polyvinylbenzyl ether resin composition |
| US11/045,160 US20050154110A1 (en) | 1999-12-28 | 2005-01-31 | Composite dielectric material, composite dielectric substrate, prepreg, coated metal foil, molded sheet, composite magnetic substrate, substrate, double side metal foil-clad substrate, flame retardant substrate, polyvinylbenzyl ether resin composition, thermosetting polyvinylbenzyl ether resin composition, and method for preparing thermosetting polyvinylbenzyl ether resin composition |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP37380599A JP2001181027A (en) | 1999-12-28 | 1999-12-28 | Composite dielectric material |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JP2001181027A true JP2001181027A (en) | 2001-07-03 |
Family
ID=18502792
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP37380599A Pending JP2001181027A (en) | 1999-12-28 | 1999-12-28 | Composite dielectric material |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2001181027A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2005174711A (en) * | 2003-12-10 | 2005-06-30 | Tdk Corp | Dielectric ceramic powder, manufacturing method of dielectric ceramic powder, and compound dielectric material |
| CN100359612C (en) * | 2004-09-03 | 2008-01-02 | 江苏大学 | Medium low temperature sintered high voltage ceramic capacitor medium |
| KR101452077B1 (en) * | 2012-12-28 | 2014-10-16 | 삼성전기주식회사 | Dielectric composition and multi-layered ceramic capacitor |
-
1999
- 1999-12-28 JP JP37380599A patent/JP2001181027A/en active Pending
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2005174711A (en) * | 2003-12-10 | 2005-06-30 | Tdk Corp | Dielectric ceramic powder, manufacturing method of dielectric ceramic powder, and compound dielectric material |
| CN100359612C (en) * | 2004-09-03 | 2008-01-02 | 江苏大学 | Medium low temperature sintered high voltage ceramic capacitor medium |
| KR101452077B1 (en) * | 2012-12-28 | 2014-10-16 | 삼성전기주식회사 | Dielectric composition and multi-layered ceramic capacitor |
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