JP5807861B2 - Dielectric composition and method for producing the same - Google Patents

Dielectric composition and method for producing the same Download PDF

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JP5807861B2
JP5807861B2 JP2011137308A JP2011137308A JP5807861B2 JP 5807861 B2 JP5807861 B2 JP 5807861B2 JP 2011137308 A JP2011137308 A JP 2011137308A JP 2011137308 A JP2011137308 A JP 2011137308A JP 5807861 B2 JP5807861 B2 JP 5807861B2
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dielectric composition
composition
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JP2013001625A (en
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塩井　恒介
恒介 塩井
大橋　直樹
直樹 大橋
尚登 広崎
尚登 広崎
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Showa Denko KK
National Institute for Materials Science
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National Institute for Materials Science
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Description

本発明は、無機化合物を主体とする誘電体組成物とその製造方法に関する。さらに詳細には、高い比誘電率を有し、しかも従来よりも高い温度条件下でも使用可能な高温誘電体組成物とその製造方法に関する。   The present invention relates to a dielectric composition mainly composed of an inorganic compound and a method for producing the same. More specifically, the present invention relates to a high-temperature dielectric composition that has a high relative dielectric constant and can be used under higher temperature conditions than before, and a method for producing the same.

近年、地球温暖化問題に対して全世界的な注目が集まりつつあり、電気自動車やハイブリッドカー、次世代送電網等の普及によるＣＯ２排出量の削減或いはエネルギー効率の向上が強く求められている。これらには高い接合部温度を有するパワーモジュールが一般に用いられており、そのため、パワーモジュール周辺に配置される電子デバイスには、動作温度の高温化が要求されている。 In recent years, global attention has been gathered on the global warming problem, and there is a strong demand for reduction of CO 2 emissions or improvement of energy efficiency through the spread of electric vehicles, hybrid cars, next-generation power transmission networks, etc. . For these, a power module having a high junction temperature is generally used. Therefore, an electronic device disposed around the power module is required to have a high operating temperature.

誘電体はコンデンサー、サーミスター、フィルター、共振器、アンテナ、発信子などに広く用いられているが、代表的誘電体であるチタン酸バリウムは、キュリー点のために使用温度範囲の上限は１２５℃である。しかしながら、パワーモジュールの接合部温度は２００℃に達すると見込まれており、チタン酸バリウムにかわる高温度の条件下でも使用可能な誘電体組成物の開発が強く望まれている。
加えて、電気自動車、ハイブリッドカー等の車載用途を考えた場合、一般の車載部品と同様に電子デバイスにも小型軽量化が求められている。代表的誘電体であるチタン酸バリウムは１０００から２０００程度の高い比誘電率を有する誘電体であるが、現今の電子デバイスに対する小型軽量化の要請から、誘電体材料（誘電体組成物）には、一層の高誘電率化が強く求められている。 Dielectrics are widely used in capacitors, thermistors, filters, resonators, antennas, oscillators, etc., but barium titanate, a typical dielectric, has an upper temperature range of 125 ° C due to the Curie point. It is. However, the junction temperature of the power module is expected to reach 200 ° C., and development of a dielectric composition that can be used even under high temperature conditions replacing barium titanate is strongly desired.
In addition, when considering in-vehicle applications such as electric vehicles and hybrid cars, electronic devices are required to be smaller and lighter as well as general in-vehicle components. Barium titanate, which is a typical dielectric, is a dielectric having a high relative dielectric constant of about 1000 to 2000. However, due to the demand for reduction in size and weight of electronic devices at present, dielectric materials (dielectric compositions) There is a strong demand for higher dielectric constants.

チタン酸バリウムの使用温度範囲の上限を拡張する試みとして、Ｂａサイトの一部をＣａで置換し、さらにＤｙ２Ｏ３及びＭｇＯを添加する方法が検討されている（下記非特許文献１参照）。本方法によれば、キュリー点近傍における急激な比誘電率変化は抑制されるが、同時にキュリー点以下の使用可能温度域において比誘電率が低下するといった難点がある。 As an attempt to extend the upper limit of the operating temperature range of barium titanate, a method in which a part of the Ba site is replaced with Ca and Dy 2 O 3 and MgO are added has been studied (see Non-Patent Document 1 below). . According to this method, a rapid change in the relative dielectric constant in the vicinity of the Curie point is suppressed, but at the same time, there is a problem that the relative dielectric constant decreases in a usable temperature range below the Curie point.

窒化物、酸窒化物は、酸化物に比して共有結合性が高いことから、一般に酸化物よりも熱的相転移点が高い。チタン酸バリウムのキュリー点は相転移に起因するため、窒素を含有する誘電体材料は高いキュリー点を有するものと推察される。
チタン酸バリウムと同様の結晶構造であるペロブスカイト型構造をもつ窒化物、酸窒化物（窒化物、酸窒化物系ペロブスカイト型化合物）として、多種の化合物が知られている。特許文献１には、ペロブスカイト型構造を有する多種の窒化物、酸窒化物について、合成方法並びに誘電体特性について開示されており、加えて、９０から３７０Ｋ（−１８３から９７℃）の温度範囲で比誘電率に変化がないことが記載されている。しかしながら、誘電体特性に関する詳細は記載されて居らず、窒化物、酸窒化物系ペロブスカイト型化合物の誘電体的性質については明らかとなっていない。 Nitride and oxynitride generally have a higher thermal phase transition point than oxides because they have higher covalent bonding than oxides. Since the Curie point of barium titanate is caused by the phase transition, it is presumed that the dielectric material containing nitrogen has a high Curie point.
A wide variety of compounds are known as nitrides and oxynitrides (nitrides, oxynitride perovskite compounds) having a perovskite structure that is the same crystal structure as barium titanate. Patent Document 1 discloses a synthesis method and dielectric characteristics of various nitrides and oxynitrides having a perovskite structure, and in addition, in a temperature range of 90 to 370 K (−183 to 97 ° C.). It is described that there is no change in the dielectric constant. However, details regarding the dielectric properties are not described, and the dielectric properties of nitride and oxynitride perovskite compounds are not clear.

非特許文献２にはペロブスカイト型構造を有する多種の酸窒化物である、ＢａＴａＯ２Ｎ及びＳｒＴａＯ２Ｎが誘電体的性質を示し、その比誘電率はそれぞれ４９００、２９００程度であることが開示されている。しかしながら、現今の電子デバイスに対する小型軽量化の要請に答えるためには、非特許文献２に記載された比誘電率では十分とはいえない。 Non-Patent Document 2 discloses that various types of oxynitrides having a perovskite structure, BaTaO 2 N and SrTaO 2 N, exhibit dielectric properties and have a relative dielectric constant of about 4900 and 2900, respectively. ing. However, the relative permittivity described in Non-Patent Document 2 is not sufficient to meet the current demand for smaller and lighter electronic devices.

ＵＳ４７３４３９０号公報US Pat. No. 4,734,390

久保寺紀之 他 セラミックス ４５ （２０１０）４５３−４５７．Noriyuki Kubotera et al. Ceramics 45 (2010) 453-457. Ｙｏｕｎｇ−Ｉｌ Ｋｉｍ， ｅｔ． ａｌ．， Ｃｈｅｍ． Ｍａｔｅｒ．，１６ （２００４）１２６７−１２７６．Young-Il Kim, et. al. Chem. Mater. , 16 (2004) 1267-1276. Ｔｅｒｕｋｉ Ｍｏｔｏｈａｓｈｉ， ｅｔ． ａｌ．， Ｍａｔｅｒ． Ｒｅｓ． Ｂｕｌｌ．， ４４ （２００９）１８９９−１９０５．Teruki Motohashi, et. al. , Mater. Res. Bull. , 44 (2009) 1899-1905.

本発明は、上記のような問題を解決しようとするものであり、室温から２００℃の間にキュリー点を持たず、しかも従来知られている酸窒化物系ペロブスカイト型化合物よりも高い比誘電率を有する誘電体組成物及びその製造方法の提供を目的とする。   The present invention is intended to solve the above-mentioned problems, has no Curie point between room temperature and 200 ° C., and has a higher relative dielectric constant than the conventionally known oxynitride perovskite compounds. It is an object of the present invention to provide a dielectric composition having the above and a method for producing the same.

本発明者らは、上記課題を解決するために鋭意研究を重ねた結果、特定の化学組成を有する化合物が、室温から２００℃の間にキュリー点を持たず、しかも従来知られている酸窒化物系ペロブスカイト型化合物よりも高い比誘電率を有することを見いだし、以下に示す本発明を完成させるに至った。   As a result of intensive studies to solve the above problems, the present inventors have found that a compound having a specific chemical composition does not have a Curie point between room temperature and 200 ° C., and is a conventionally known oxynitriding process. It has been found that it has a relative dielectric constant higher than that of a physical perovskite type compound, and the present invention shown below has been completed.

[１]一般式：Ｍ（１）１−ｘＭ（２）ｘＭ（３）１−ｙＭ（４）ｙＯ２＋ｘ―ｙＮ１―ｘ＋ｙ
で示される組成であることを特徴とする誘電体組成物。
但し、Ｍ（１）元素はＹ，Ｌａ，Ｃｅ，Ｐｒ，Ｎｄ，Ｇｄから選ばれる1種以上の元素であり、Ｍ（２）元素はＭｇ，Ｃａ，Ｓｒ，Ｂａから選ばれる１種以上の元素であり、Ｍ（３）元素はＴｉ，Ｚｒから選ばれる１種以上の元素であり、Ｍ（４）元素はＶ，Ｎｂ，Ｔａから選ばれる１種以上の元素であり、Ｏ元素とＮ元素は酸素と窒素であり、０＜ｘ＜１かつ０≦ｙ≦１である。
[２]０＜ｘ≦０．９，０≦ｙ≦０．９であることを特徴とする上記[１]に記載の誘電体組成物。
[３]Ｍ（１）元素が、Ｌａ，Ｃｅ，Ｐｒ，Ｎｄから選ばれる一種以上であり、Ｍ（２）元素がＳｒ，Ｂａから選ばれる一種以上であることを特徴とする上記[２]に記載の誘電体組成物。
[４]Ｍ（１）元素がＬａ、Ｍ（２）元素がＢａ、Ｍ（３）元素がＴｉ、Ｍ（４）元素がＴａであることを特徴とする上記[３]に記載の誘電体組成物。 [1] General formula: M (1) 1-x M (2) x M (3) 1-y M (4) y O 2 + xy N 1-x + y
A dielectric composition characterized by having a composition represented by:
However, the M (1) element is one or more elements selected from Y, La, Ce, Pr, Nd, and Gd, and the M (2) element is one or more elements selected from Mg, Ca, Sr, and Ba. M (3) element is one or more elements selected from Ti and Zr, M (4) element is one or more elements selected from V, Nb, and Ta, and O element and N The elements are oxygen and nitrogen, and 0 <x <1 and 0 ≦ y ≦ 1.
[2] The dielectric composition as described in [1] above, wherein 0 <x ≦ 0.9 and 0 ≦ y ≦ 0.9.
[3] The above-mentioned [2], wherein the M (1) element is at least one selected from La, Ce, Pr, and Nd, and the M (2) element is at least one selected from Sr and Ba. The dielectric composition according to 1.
[4] The dielectric according to [3] above, wherein the M (1) element is La, the M (2) element is Ba, the M (3) element is Ti, and the M (4) element is Ta. Composition.

[５]以下の〔１〕〜〔３〕のいずれかの原料を加熱して、以下の〔４〕〜〔６〕のいずれかの中間化合物を生成する工程と、該中間化合物を還元性雰囲気中で加熱する工程とを含むことを特徴とする上記[１]〜[４]の何れか一項に記載の誘電体組成物の製造方法。
〔１〕Ｍ（１）元素、Ｍ（２）元素及びＭ（３）元素のうちの一又は二以上を含む化合物を一又は二以上含有してなる原料（但し、Ｍ（１）元素、Ｍ（２）元素及びＭ（３）元素は前記化合物の少なくともいずれか一つに含まれる）
〔２〕Ｍ（１）元素、Ｍ（２）元素及びＭ（４）元素のうちの一又は二以上を含む化合物を一又は二以上含有してなる原料（但し、Ｍ（１）元素、Ｍ（２）元素及びＭ（４）元素は前記化合物の少なくともいずれか一つに含まれる）
〔３〕Ｍ（１）元素、Ｍ（２）元素、Ｍ（３）元素及びＭ（４）元素のうちの一又は二以上を含む化合物を一又は二以上含有してなる原料（但し、Ｍ（１）元素、Ｍ（２）元素、Ｍ（３）元素及びＭ（４）元素は前記化合物の少なくともいずれか一つに含まれる）
〔４〕Ｍ（１）元素及び／又はＭ（２）元素と、Ｍ（３）元素とを含む化合物を一又は二以上含有してなる中間化合物（但し、Ｍ（１）元素、Ｍ（２）元素及びＭ（３）元素は前記化合物の少なくともいずれか一つに含まれる）
〔５〕Ｍ（１）元素及び／又はＭ（２）元素と、Ｍ（４）元素とを含む化合物を一又は二以上含有してなる中間化合物（但し、Ｍ（１）元素、Ｍ（２）元素及びＭ（４）元素は前記化合物の少なくともいずれか一つに含まれる）
〔６〕Ｍ（１）元素及び／又はＭ（２）元素と、Ｍ（３）元素及び／又はＭ（４）元素とを含む化合物を一又は二以上含有してなる中間化合物（但し、Ｍ（１）元素、Ｍ（２）元素、Ｍ（３）元素及びＭ（４）元素は前記化合物の少なくともいずれか一つに含まれる）
[６]前記化合物の少なくとも一つは酸化物であることを特徴とする上記[５]に記載の誘電体組成物の製造方法。
[７]以下の〔１〕〜〔３〕のいずれかの原料を加熱する工程を含むことを特徴とする上記[１]〜[４]の何れか一項に記載の誘電体組成物の製造方法。
〔１〕Ｍ（１）元素、Ｍ（２）元素及びＭ（３）元素のうちの一又は二以上を含む化合物を一又は二以上含有してなる原料（但し、Ｍ（１）元素、Ｍ（２）元素及びＭ（３）元素は前記化合物の少なくともいずれか一つに含まれる）
〔２〕Ｍ（１）元素、Ｍ（２）元素及びＭ（４）元素のうちの一又は二以上を含む化合物を一又は二以上含有してなる原料（但し、Ｍ（１）元素、Ｍ（２）元素及びＭ（４）元素は前記化合物の少なくともいずれか一つに含まれる）
〔３〕Ｍ（１）元素、Ｍ（２）元素、Ｍ（３）元素及びＭ（４）元素のうちの一又は二以上を含む化合物を一又は二以上含有してなる原料（但し、Ｍ（１）元素、Ｍ（２）元素、Ｍ（３）元素及びＭ（４）元素は前記化合物の少なくともいずれか一つに含まれる）。
[８]前記化合物の少なくとも一つは酸化物であることを特徴とする上記[７]に記載の誘電体組成物の製造方法。
[９]以下の〔１〕〜〔３〕のいずれかの原料を加熱する工程を含むことを特徴とする上記[１]〜[４]の何れか一項に記載の誘電体組成物の製造方法。
〔１〕Ｍ（１）元素及び／又はＭ（２）元素と、Ｍ（３）元素とを含む化合物を一又は二以上含有してなる原料（但し、Ｍ（１）元素、Ｍ（２）元素及びＭ（３）元素は前記化合物の少なくともいずれか一つに含まれる）
〔２〕Ｍ（１）元素及び／又はＭ（２）元素と、Ｍ（４）元素とを含む化合物を一又は二以上含有してなる原料（但し、Ｍ（１）元素、Ｍ（２）元素及びＭ（４）元素は前記化合物の少なくともいずれか一つに含まれる）
〔３〕Ｍ（１）元素及び／又はＭ（２）元素と、Ｍ（３）元素及び／又はＭ（４）元素とを含む化合物を一又は二以上含有してなる原料（但し、Ｍ（１）元素、Ｍ（２）元素、Ｍ（３）元素及びＭ（４）元素は前記化合物の少なくともいずれか一つに含まれる）。
[１０]前記化合物の少なくとも一つは酸化物であることを特徴とする上記[９]に記載の誘電体組成物の製造方法。 [5] A step of heating any of the following raw materials [1] to [3] to produce an intermediate compound of any of the following [4] to [6], and the intermediate compound in a reducing atmosphere The method for producing a dielectric composition as described in any one of [1] to [4] above, further comprising a step of heating in.
[1] A raw material containing one or more compounds containing one or more of M (1) element, M (2) element and M (3) element (provided that M (1) element, M (2) Element and M (3) element are included in at least one of the above compounds)
[2] A raw material containing one or more compounds containing one or more of M (1) element, M (2) element and M (4) element (provided that M (1) element, M (2) Element and M (4) element are included in at least one of the above compounds)
[3] A raw material containing one or more compounds containing one or more of M (1) element, M (2) element, M (3) element and M (4) element (provided that M (1) Element, M (2) element, M (3) element, and M (4) element are included in at least one of the above compounds)
[4] Intermediate compound containing one or more compounds containing M (1) element and / or M (2) element and M (3) element (provided that M (1) element, M (2 ) Element and M (3) element are included in at least one of the above compounds)
[5] Intermediate compound containing one or more compounds containing M (1) element and / or M (2) element and M (4) element (provided that M (1) element, M (2 ) Element and M (4) element are included in at least one of the above compounds)
[6] Intermediate compound comprising one or more compounds containing M (1) element and / or M (2) element and M (3) element and / or M (4) element (provided that M (1) Element, M (2) element, M (3) element, and M (4) element are included in at least one of the above compounds)
[6] The method for producing a dielectric composition as described in [5] above, wherein at least one of the compounds is an oxide.
[7] The production of the dielectric composition as described in any one of [1] to [4] above, which includes a step of heating any of the following raw materials [1] to [3] Method.
[1] A raw material containing one or more compounds containing one or more of M (1) element, M (2) element and M (3) element (provided that M (1) element, M (2) Element and M (3) element are included in at least one of the above compounds)
[2] A raw material containing one or more compounds containing one or more of M (1) element, M (2) element and M (4) element (provided that M (1) element, M (2) Element and M (4) element are included in at least one of the above compounds)
[3] A raw material containing one or more compounds containing one or more of M (1) element, M (2) element, M (3) element and M (4) element (provided that M (1) Element, M (2) element, M (3) element, and M (4) element are included in at least one of the compounds).
[8] The method for producing a dielectric composition as described in [7] above, wherein at least one of the compounds is an oxide.
[9] The production of the dielectric composition as described in any one of [1] to [4] above, which includes a step of heating any of the following raw materials [1] to [3] Method.
[1] A raw material containing one or more compounds containing M (1) element and / or M (2) element and M (3) element (however, M (1) element, M (2) Element and M (3) element are included in at least one of the above compounds)
[2] A raw material comprising one or more compounds containing M (1) element and / or M (2) element and M (4) element (however, M (1) element, M (2) Element and M (4) element are included in at least one of the above compounds)
[3] A raw material containing one or more compounds containing M (1) element and / or M (2) element and M (3) element and / or M (4) element (provided that M ( 1) Element, M (2) element, M (3) element and M (4) element are included in at least one of the above compounds).
[10] The method for producing a dielectric composition as described in [9] above, wherein at least one of the compounds is an oxide.

上記の構成によれば、室温から２００℃の間にキュリー点を持たず、しかも従来知られている酸窒化物系ペロブスカイト型化合物よりも高い比誘電率を有する誘電体組成物を提供することができる。つまり、高い比誘電率を有するとともに、従来よりも高い温度条件下でも誘電体として使用可能な誘電体組成物を提供することができる。   According to the above configuration, it is possible to provide a dielectric composition that does not have a Curie point between room temperature and 200 ° C. and has a higher relative dielectric constant than a conventionally known oxynitride perovskite compound. it can. That is, it is possible to provide a dielectric composition that has a high relative dielectric constant and can be used as a dielectric even under higher temperature conditions than before.

以下、本実施形態に係る誘電体組成物について詳細に説明する。
本実施形態の誘電体組成物は、
一般式：Ｍ（１）１−ｘＭ（２）ｘＭ（３）１−ｙＭ（４）ｙＯ２＋ｘ―ｙＮ１―ｘ＋ｙ
で示される組成からなることを特徴とする。
但し、Ｍ（１）元素はＹ，Ｌａ，Ｃｅ，Ｐｒ，Ｎｄ，Ｇｄから選ばれる1種以上の元素であり、Ｍ（２）元素はＭｇ，Ｃａ，Ｓｒ，Ｂａから選ばれる１種以上の元素であり、Ｍ（３）元素はＴｉ，Ｚｒから選ばれる１種以上の元素であり、Ｍ（４）元素はＶ，Ｎｂ，Ｔａから選ばれる１種以上の元素であり、Ｏ元素とＮ元素は酸素と窒素である。
なお、本発明の誘電体組成物には、本発明の効果を損なわない範囲内で他の元素を含有してもよい。また、製造工程で不可避的に導入される他の元素を含有してもよい。
なお、本実施形態において、上記ｘとｙの値は、０＜ｘ＜１，０≦ｙ≦１の範囲である。
以下、各元素及び上記ｘとｙの数値範囲の限定理由について詳細に説明する。 Hereinafter, the dielectric composition according to the present embodiment will be described in detail.
The dielectric composition of the present embodiment is
General formula: M (1) 1-x M (2) x M (3) 1-y M (4) y O 2 + xy N 1-x + y
It is characterized by comprising the composition shown by.
However, the M (1) element is one or more elements selected from Y, La, Ce, Pr, Nd, and Gd, and the M (2) element is one or more elements selected from Mg, Ca, Sr, and Ba. M (3) element is one or more elements selected from Ti and Zr, M (4) element is one or more elements selected from V, Nb, and Ta, and O element and N Elements are oxygen and nitrogen.
In addition, you may contain another element in the dielectric composition of this invention in the range which does not impair the effect of this invention. Moreover, you may contain the other element inevitably introduced in a manufacturing process.
In the present embodiment, the values of x and y are in the range of 0 <x <1, 0 ≦ y ≦ 1.
Hereinafter, the reasons for limiting each element and the numerical range of the above x and y will be described in detail.

Ｍ（１）元素について、好ましくは、Ｌａ，Ｃｅ，Ｐｒ，Ｎｄから選ばれる一種以上である。また、Ｍ（２）元素について、好ましくは、Ｓｒ，Ｂａから選ばれる一種以上である。
上記の一般式で表される組成の誘電体組成物において、Ｍ（１）及びＭ（２）元素のそれぞれが、Ｌａ，Ｃｅ，Ｐｒ，Ｎｄから選ばれる一種以上、及びＳｒ，Ｂａから選ばれる一種以上である場合に、室温から２００℃の間にキュリー点を持たず、しかも従来知られている酸窒化物系ペロブスカイト型化合物よりも高い比誘電率を有する誘電体組成物を得ることができる。
もっとも好ましいＭ（１），Ｍ（２），Ｍ（３）及びＭ（４）元素は、それぞれＬａ、Ｂａ、Ｔｉ、Ｔａである。Ｍ（１），Ｍ（２），Ｍ（３）及びＭ（４）元素を、それぞれＬａ、Ｂａ、Ｔｉ、Ｔａとした場合に、室温から２００℃の間にキュリー点を持たず、しかも従来知られている酸窒化物系ペロブスカイト型化合物よりも十分に高い比誘電率を有する誘電体組成物を得ることができる。 The M (1) element is preferably at least one selected from La, Ce, Pr, and Nd. The M (2) element is preferably at least one selected from Sr and Ba.
In the dielectric composition having the composition represented by the above general formula, each of the M (1) and M (2) elements is selected from one or more selected from La, Ce, Pr, and Nd, and Sr and Ba. When it is one or more, a dielectric composition having no Curie point between room temperature and 200 ° C. and having a higher relative dielectric constant than a conventionally known oxynitride perovskite compound can be obtained. .
The most preferred M (1), M (2), M (3) and M (4) elements are La, Ba, Ti and Ta, respectively. When the elements M (1), M (2), M (3), and M (4) are La, Ba, Ti, and Ta, respectively, they do not have a Curie point between room temperature and 200 ° C. A dielectric composition having a dielectric constant sufficiently higher than that of known oxynitride perovskite compounds can be obtained.

また、本実施形態において、上記ｘ及びｙの値は、０＜ｘ＜１，０≦ｙ≦１の範囲である。なお、０＜ｘ≦０．９，０≦ｙ≦０．９であることが好ましい。ｘ及びｙの値が０＜ｘ≦０．９，０≦ｙ≦０．９の範囲にある場合に、室温から２００℃の間にキュリー点を持たず、しかも従来知られている酸窒化物系ペロブスカイト型化合物よりも高い比誘電率を有する誘電体組成物を得ることができる。
より好ましいｘ及びｙの値は、０＜ｘ≦０．４，０≦ｙ≦０．５である。ｘ及びｙの値が０＜ｘ≦０．４，０≦ｙ≦０．５の範囲にある場合に、室温から２００℃の間にキュリー点を持たず、しかも従来知られている酸窒化物系ペロブスカイト型化合物よりも十分に高い比誘電率を有する誘電体組成物を得ることができる。
更に好ましいｘ及びｙの値は、０．０５＜ｘ≦０．２，０．０５≦ｙ≦０．１５である。ｘ及びｙの値が０．０５＜ｘ≦０．２，０．１５≦ｙ≦０．１５の範囲にある場合に、室温から２００℃の間にキュリー点を持たず、しかも従来知られている酸窒化物系ペロブスカイト型化合物よりも十分に高い比誘電率を有する誘電体組成物を得ることができる。
なお、誘電率の値がｘとｙの値によって変化する理由は定かではないが、イオン半径が異なる元素の固溶、或いは酸化数が異なる元素の固溶による窒素含有量の変化により結晶構造に適度な歪みが生じ、その結果誘電分極が生じやすくなる場合が考えられる。 In the present embodiment, the values of x and y are in the range of 0 <x <1, 0 ≦ y ≦ 1. It is preferable that 0 <x ≦ 0.9 and 0 ≦ y ≦ 0.9. A conventionally known oxynitride having no Curie point between room temperature and 200 ° C. when the values of x and y are in the range of 0 <x ≦ 0.9 and 0 ≦ y ≦ 0.9 A dielectric composition having a higher relative dielectric constant than the perovskite type compound can be obtained.
More preferable values of x and y are 0 <x ≦ 0.4 and 0 ≦ y ≦ 0.5. A conventionally known oxynitride having no Curie point between room temperature and 200 ° C. when the values of x and y are in the range of 0 <x ≦ 0.4 and 0 ≦ y ≦ 0.5 A dielectric composition having a dielectric constant sufficiently higher than that of the perovskite type compound can be obtained.
Further preferable values of x and y are 0.05 <x ≦ 0.2 and 0.05 ≦ y ≦ 0.15. When the values of x and y are in the range of 0.05 <x ≦ 0.2, 0.15 ≦ y ≦ 0.15, there is no Curie point between room temperature and 200 ° C., and it is conventionally known It is possible to obtain a dielectric composition having a dielectric constant sufficiently higher than that of the oxynitride-based perovskite compound.
The reason why the value of the dielectric constant changes depending on the values of x and y is not clear, but the crystal structure is changed by the change in nitrogen content due to the solid solution of elements having different ionic radii or the solution of elements having different oxidation numbers. It can be considered that moderate distortion is generated, and as a result, dielectric polarization is likely to occur.

次に、本実施形態に係る、誘電体組成物の製造方法について説明する。
本実施形態の誘電体組成物の製造方法は、上記した、
一般式：Ｍ（１）１−ｘＭ（２）ｘＭ（３）１−ｙＭ（４）ｙＯ２＋ｘ―ｙＮ１―ｘ＋ｙ
（但し、Ｍ（１）元素はＹ，Ｌａ，Ｃｅ，Ｐｒ，Ｎｄ，Ｇｄから選ばれる1種以上の元素であり、Ｍ（２）元素はＭｇ，Ｃａ，Ｓｒ，Ｂａから選ばれる１種以上の元素であり、Ｍ（３）元素はＴｉ，Ｚｒから選ばれる１種以上の元素であり、Ｍ（４）元素はＶ，Ｎｂ，Ｔａから選ばれる１種以上の元素であり、ＯとＮは酸素と窒素である。）で示される組成である誘電体組成物を得るために、以下の〔１〕〜〔３〕のいずれかの原料を加熱して、以下の〔４〕〜〔６〕のいずれかの中間化合物を生成する工程と、該中間化合物を還元性雰囲気中で加熱する工程とを含むことを特徴とする。
〔１〕Ｍ（１）元素、Ｍ（２）元素及びＭ（３）元素のうちの一又は二以上を含む化合物を一又は二以上含有してなる原料（但し、Ｍ（１）元素、Ｍ（２）元素及びＭ（３）元素は前記化合物の少なくともいずれか一つに含まれる）
〔２〕Ｍ（１）元素、Ｍ（２）元素及びＭ（４）元素のうちの一又は二以上を含む化合物を一又は二以上含有してなる原料（但し、Ｍ（１）元素、Ｍ（２）元素及びＭ（４）元素は前記化合物の少なくともいずれか一つに含まれる）
〔３〕Ｍ（１）元素、Ｍ（２）元素、Ｍ（３）元素及びＭ（４）元素のうちの一又は二以上を含む化合物を一又は二以上含有してなる原料（但し、Ｍ（１）元素、Ｍ（２）元素、Ｍ（３）元素及びＭ（４）元素は前記化合物の少なくともいずれか一つに含まれる）
〔４〕Ｍ（１）元素及び／又はＭ（２）元素と、Ｍ（３）元素とを含む化合物を一又は二以上含有してなる中間化合物（但し、Ｍ（１）元素、Ｍ（２）元素及びＭ（３）元素は前記化合物の少なくともいずれか一つに含まれる）
〔５〕Ｍ（１）元素及び／又はＭ（２）元素と、Ｍ（４）元素とを含む化合物を一又は二以上含有してなる中間化合物（但し、Ｍ（１）元素、Ｍ（２）元素及びＭ（４）元素は前記化合物の少なくともいずれか一つに含まれる）
〔６〕Ｍ（１）元素及び／又はＭ（２）元素と、Ｍ（３）元素及び／又はＭ（４）元素とを含む化合物を一又は二以上含有してなる中間化合物（但し、Ｍ（１）元素、Ｍ（２）元素、Ｍ（３）元素及びＭ（４）元素は前記化合物の少なくともいずれか一つに含まれる）
なお、中間化合物は、上記〔１〕〜〔３〕に示すような原料（合成用原料）を機械的に混合することにより得られた混合粉末、あるいは液相を介して混合する方法により得られた原料混合物を仮焼することにより得ることができる。 Next, a method for producing a dielectric composition according to this embodiment will be described.
The manufacturing method of the dielectric composition of the present embodiment is as described above.
General formula: M (1) 1-x M (2) x M (3) 1-y M (4) y O 2 + xy N 1-x + y
(However, the M (1) element is one or more elements selected from Y, La, Ce, Pr, Nd, and Gd, and the M (2) element is one or more elements selected from Mg, Ca, Sr, and Ba. M (3) element is one or more elements selected from Ti and Zr, M (4) element is one or more elements selected from V, Nb and Ta, and O and N Are oxygen and nitrogen.) In order to obtain a dielectric composition having the composition represented by (1) to [3], any one of the following [1] to [3] is heated, and the following [4] to [6] And a step of heating the intermediate compound in a reducing atmosphere.
[1] A raw material containing one or more compounds containing one or more of M (1) element, M (2) element and M (3) element (provided that M (1) element, M (2) Element and M (3) element are included in at least one of the above compounds)
[2] A raw material containing one or more compounds containing one or more of M (1) element, M (2) element and M (4) element (provided that M (1) element, M (2) Element and M (4) element are included in at least one of the above compounds)
[3] A raw material containing one or more compounds containing one or more of M (1) element, M (2) element, M (3) element and M (4) element (provided that M (1) Element, M (2) element, M (3) element, and M (4) element are included in at least one of the above compounds)
[4] Intermediate compound containing one or more compounds containing M (1) element and / or M (2) element and M (3) element (provided that M (1) element, M (2 ) Element and M (3) element are included in at least one of the above compounds)
[5] Intermediate compound containing one or more compounds containing M (1) element and / or M (2) element and M (4) element (provided that M (1) element, M (2 ) Element and M (4) element are included in at least one of the above compounds)
[6] Intermediate compound comprising one or more compounds containing M (1) element and / or M (2) element and M (3) element and / or M (4) element (provided that M (1) Element, M (2) element, M (3) element, and M (4) element are included in at least one of the above compounds)
The intermediate compound is obtained by a mixed powder obtained by mechanically mixing the raw materials (synthetic raw materials) as shown in the above [1] to [3], or by a method of mixing via a liquid phase. It can be obtained by calcining the raw material mixture.

本発明の誘電体組成物の合成用原料として用いられる、上記〔１〕〜〔３〕に記載の化合物の少なくとも一つは酸化物であることが好ましい。なお、酸化物のほかに、加熱により酸化物を形成する化合物、あるいは上記元素を含有する複化合物を用いてもよい。   It is preferable that at least one of the compounds described in the above [1] to [3] used as a raw material for synthesis of the dielectric composition of the present invention is an oxide. In addition to oxides, compounds that form oxides by heating, or complex compounds containing the above elements may be used.

また、上記合成用原料の混合方法は、粉末状の合成用原料（原料粉末）を機械的に混合する方法と、液相を介して混合する方法が挙げられる。
機械的に混合する場合は、溶媒を用いない乾式ミルによっても混合可能だが、一般には湿式ミルにより溶媒とともに混合し混合スラリーとするほうが好ましい。溶媒を用いた湿式ミル方を用いたほうが、この混合スラリーを蒸発乾固することにより、短時間で微視的に均一な混合粉末を得ることができる。
なお、ミルの種類としては、ボールミル、振動ミル、アトリッションミル等を用いることができるが、設備費用の観点からはボールミルが適している。また、湿式ミルで混合する際に用いる溶媒は、エタノール、メタノール、イソプロパノール、ヘキサン、アセトン、水等を挙げることができるが、安全性等及び原料粉末の酸化防止を勘案すると、エタノール、ヘキサンの何れかが好ましい。 Examples of the method for mixing the raw materials for synthesis include a method of mechanically mixing powdery raw materials for synthesis (raw material powder) and a method of mixing via a liquid phase.
When mixing mechanically, it can be mixed by a dry mill that does not use a solvent, but it is generally preferable to mix with a solvent by a wet mill to form a mixed slurry. When the wet mill method using a solvent is used, this mixed slurry is evaporated to dryness, whereby a microscopically uniform mixed powder can be obtained in a short time.
In addition, as a kind of mill, a ball mill, a vibration mill, an attrition mill or the like can be used, but a ball mill is suitable from the viewpoint of equipment cost. In addition, examples of the solvent used for mixing in the wet mill include ethanol, methanol, isopropanol, hexane, acetone, water, and the like. Is preferred.

また、原料粉末と溶媒の比率は、得られる混合スラリーの粘度によって決定される。好ましい混合スラリーの粘度は、５０から５００ｃｐｓである。混合スラリーの粘度が５０ｃｐｓより小さいと、混合スラリーの乾燥に要するエネルギー量が増大するため好ましくない。一方、混合スラリーの粘度が５００ｃｐｓを越えると、均一な混合粉末を得るのに長時間を要するため好ましくない。
得られた混合スラリーは、乾燥機等に静置して溶媒を蒸発させてもよいが、スプレードライヤーを用いると、原料粉末の再分離を心配することなく、さらに短時間で、溶媒を除去した混合粉末を得ることができる。また、スプレードライヤーを用いて得られた混合粉末は、数十から数百μｍの顆粒状を呈しているため、流動性に優れ、取り扱いが容易となる。 Moreover, the ratio of the raw material powder and the solvent is determined by the viscosity of the obtained mixed slurry. A preferred mixed slurry has a viscosity of 50 to 500 cps. If the viscosity of the mixed slurry is less than 50 cps, the amount of energy required for drying the mixed slurry increases, which is not preferable. On the other hand, when the viscosity of the mixed slurry exceeds 500 cps, it takes a long time to obtain a uniform mixed powder, which is not preferable.
The obtained mixed slurry may be left in a dryer or the like to evaporate the solvent. However, using a spray dryer, the solvent was removed in a shorter time without worrying about re-separation of the raw material powder. A mixed powder can be obtained. Moreover, since the mixed powder obtained using the spray dryer has a granular form of several tens to several hundreds of μm, it is excellent in fluidity and easy to handle.

また、液相を介して原料粉末を混合して原料混合物とする場合について説明する。
本発明の誘電体組成物の合成に用いられる原料混合物は、共沈法、金属アルコキシド法、ゲル化法（非特許文献３参照）等の液相を介する方法によっても得ることができる。誘電体組成物の合成に液相を介する方法により得られた原料混合物を用いた場合は、原料粉末を機械的に混合した場合よりも短時間での焼成により所望の誘電体組成物を得ることができる。 Moreover, the case where a raw material powder is mixed through a liquid phase to make a raw material mixture will be described.
The raw material mixture used for the synthesis of the dielectric composition of the present invention can also be obtained by a method via a liquid phase, such as a coprecipitation method, a metal alkoxide method, a gelation method (see Non-Patent Document 3). When a raw material mixture obtained by a liquid phase method is used for synthesis of a dielectric composition, a desired dielectric composition is obtained by firing in a shorter time than when raw material powders are mechanically mixed. Can do.

本発明の誘電体組成物の合成には、上述したような、原料粉末の機械的混合により得られた混合粉末、あるいは液相を介した方法により得られた原料混合物を仮焼することにより得られる中間化合物のほかに、中間化合物同士の混合物、或いは中間化合物と原料粉末との混合物等を用いることができる。この場合の混合方法は、上記した原料粉末の混合方法と同様の方法を用いることができる。   The dielectric composition of the present invention is synthesized by calcining a mixed powder obtained by mechanical mixing of raw material powders as described above, or a raw material mixture obtained by a method via a liquid phase. In addition to the intermediate compound, a mixture of intermediate compounds or a mixture of intermediate compound and raw material powder can be used. As the mixing method in this case, the same method as the above-described raw material powder mixing method can be used.

また、中間化合物を構成する上記〔４〕〜〔６〕に記載の化合物の少なくとも一つは酸化物であることが好ましい。なお、Ｍ（１），Ｍ（２），Ｍ（３）及びＭ（４）元素を、それぞれＬａ、Ｂａ、Ｔｉ、Ｔａとした場合については、中間化合物として、
Ｌａ２Ｔｉ２Ｏ７，ＬａＴｉＯ３，Ｌａ２ＴｉＯ５，Ｌａ４Ｔｉ３Ｏ１２，Ｌａ１．３３Ｔｉ８Ｏ１６，Ｌａ５Ｔｉ４Ｏ１５,Ｌａ９Ｔｉ７Ｏ２７，Ｌａ４Ｔｉ９Ｏ２４，Ｌａ５Ｔｉ５Ｏ１７，Ｌａ２Ｔｉ３Ｏ９，Ｂａ２Ｔｉ６Ｏ１３，ＢａＴｉ２Ｏ５，Ｂａ２ＴｉＯ４，ＢａＴｉ６Ｏ１３，ＢａＴｉＯ３，Ｂａ２Ｔｉ５．５Ｏ１３，ＢａＴｉ８Ｏ１６，Ｂａ６Ｔｉ１７Ｏ４０,ＢａＴｉ５Ｏ１１，ＢａＴｉ４Ｏ９，Ｂａ２Ｔｉ９Ｏ２０，Ｂａ２Ｔｉ１３Ｏ２２，Ｂａ４Ｔｉ１２Ｏ２７，Ｂａ４Ｔｉ１３Ｏ３０
ＢａＬａ４Ｔｉ４Ｏ１５，ＢａＬａ２Ｔｉ３Ｏ１０，Ｂａ２Ｌａ４Ｔｉ５Ｏ１８,Ｂａ３．９９Ｌａ８．９４Ｔｉ１８Ｏ５４，Ｂａ０．９９８Ｌａ２．２３５Ｔｉ４．５Ｏ１３．５
ＬａＴａＯ４，Ｌａ３ＴａＯ７，ＬａＴａ７Ｏ１９，ＬａＴａ３Ｏ９，Ｂａ５Ｔａ４Ｏ１５，ＢａＴａ２Ｏ６,Ｂａ２Ｔａ１５Ｏ３２，Ｂａ３Ｔａ５Ｏ１５，Ｂａ４Ｔａ２Ｏ９
Ｌａ３Ｔｉ１．９２Ｔａ１．０８Ｏ１１，Ｌａ６Ｔｉ３．８４Ｔａ２．１６Ｏ２２
などが例示できる。 Moreover, it is preferable that at least one of the compounds described in [4] to [6] constituting the intermediate compound is an oxide. In the case where the elements M (1), M (2), M (3) and M (4) are La, Ba, Ti and Ta, respectively,
La 2 Ti 2 O 7 , LaTiO 3 , La 2 TiO 5 , La 4 Ti 3 O 12 , La 1.33 Ti 8 O 16 , La 5 Ti 4 O 15 , La 9 Ti 7 O 27 , La 4 Ti 9 O 24 , La 5 Ti 5 O 17 , La 2 Ti 3 O 9 , Ba 2 Ti 6 O 13 , BaTi 2 O 5 , Ba 2 TiO 4 , BaTi 6 O 13 , BaTiO 3 , Ba 2 Ti 5.5 O 13 , BaTi 8 O 16 , Ba 6 Ti 17 O 40 , BaTi 5 O 11 , BaTi 4 O 9 , Ba 2 Ti 9 O 20 , Ba 2 Ti 13 O 22 , Ba 4 Ti 12 O 27 , Ba 4 Ti 13 O 30
BaLa 4 Ti 4 O 15 , BaLa 2 Ti 3 O 10 , Ba 2 La 4 Ti 5 O 18 , Ba 3.99 La 8.94 Ti 18 O 54 , Ba 0.998 La 2.235 Ti 4.5 O 13 .5
LaTaO 4 , La 3 TaO 7 , LaTa 7 O 19 , LaTa 3 O 9 , Ba 5 Ta 4 O 15 , BaTa 2 O 6 , Ba 2 Ta 15 O 32 , Ba 3 Ta 5 O 15 , Ba 4 Ta 2 O 9
La 3 Ti 1.92 Ta 1.08 O 11 , La 6 Ti 3.84 Ta 2.16 O 22
Etc. can be exemplified.

上記した中間化合物は、酸化物若しくは加熱により酸化物を形成する化合物である混合粉末または原料混合物を空気中で加熱（仮焼）することにより得られる。なお、後述する窒化処理工程の反応性を勘案し、加熱温度（仮焼成温度）は１４００℃以下であることが好ましい。仮焼成温度が１４００℃を超えると、生成した中間化合物の粒径が大きくなるため、窒化処理工程での反応性が低下し好ましくない。   The above-mentioned intermediate compound can be obtained by heating (calcining) a mixed powder or a raw material mixture, which is an oxide or a compound that forms an oxide by heating, in air. In consideration of the reactivity of the nitriding process described later, the heating temperature (temporary firing temperature) is preferably 1400 ° C. or lower. When the pre-baking temperature exceeds 1400 ° C., the particle size of the generated intermediate compound becomes large, which is not preferable because the reactivity in the nitriding treatment process is lowered.

尚、上記した酸化物群は、あくまでも中間化合物例を示したものであり、上記した酸化物群を構成するＬａ、Ｂａ、Ｔｉ及びＴａのそれぞれを、Ｍ（１），Ｍ（２），Ｍ（３）及びＭ（４）元素（Ｍ（１）元素はＹ，Ｌａ，Ｃｅ，Ｐｒ，Ｎｄ，Ｇｄから選ばれる1種以上の元素であり、Ｍ（２）元素はＭｇ，Ｃａ，Ｓｒ，Ｂａから選ばれる１種以上の元素であり、Ｍ（３）元素はＴｉ，Ｚｒから選ばれる１種以上の元素であり、Ｍ（４）元素はＶ，Ｎｂ，Ｔａから選ばれる１種以上の元素）とした場合においても、同様の効果が得られる。また、上記した酸化物とＭ（１）元素の酸化物、Ｍ（２）元素の酸化物からなる複酸化物を用いても同様の効果が得られる。   The above-described oxide group is merely an example of an intermediate compound, and La, Ba, Ti, and Ta constituting the above-described oxide group are represented by M (1), M (2), M (3) and M (4) element (M (1) element is one or more elements selected from Y, La, Ce, Pr, Nd, Gd, and M (2) element is Mg, Ca, Sr, One or more elements selected from Ba, M (3) element is one or more elements selected from Ti, Zr, and M (4) element is one or more elements selected from V, Nb, Ta In the case of (element), the same effect can be obtained. The same effect can be obtained by using a double oxide composed of the above-described oxide, M (1) element oxide, and M (2) element oxide.

また、本実施形態に係る誘電体組成物は、上述したような原料（合成用原料）を還元性雰囲気で加熱（焼成）することにより製造することも可能である。
つまり、本実施形態に係る誘電体組成物の製造方法は、以下の〔７〕〜〔９〕のいずれかの原料を還元性雰囲気中で加熱する工程を含んでもよい。
〔７〕Ｍ（１）元素、Ｍ（２）元素及びＭ（３）元素のうちの一又は二以上を含む化合物を一又は二以上含有してなる原料（但し、Ｍ（１）元素、Ｍ（２）元素及びＭ（３）元素は前記化合物の少なくともいずれか一つに含まれる）
〔８〕Ｍ（１）元素、Ｍ（２）元素及びＭ（４）元素のうちの一又は二以上を含む化合物を一又は二以上含有してなる原料（但し、Ｍ（１）元素、Ｍ（２）元素及びＭ（４）元素は前記化合物の少なくともいずれか一つに含まれる）
〔９〕Ｍ（１）元素、Ｍ（２）元素、Ｍ（３）元素及びＭ（４）元素のうちの一又は二以上を含む化合物を一又は二以上含有してなる原料（但し、Ｍ（１）元素、Ｍ（２）元素、Ｍ（３）元素及びＭ（４）元素は前記化合物の少なくともいずれか一つに含まれる）
このように、本実施形態に係る誘電体組成物は、上述したような中間化合物を生成せず、原料を直接還元窒化する方法でも製造することができる。 In addition, the dielectric composition according to the present embodiment can also be manufactured by heating (baking) the above-described raw material (synthetic raw material) in a reducing atmosphere.
That is, the method for manufacturing a dielectric composition according to this embodiment may include a step of heating any of the following raw materials [7] to [9] in a reducing atmosphere.
[7] A raw material containing one or more compounds containing one or more of M (1) element, M (2) element and M (3) element (provided that M (1) element, M (2) Element and M (3) element are included in at least one of the above compounds)
[8] A raw material containing one or more compounds containing one or more of M (1) element, M (2) element, and M (4) element (provided that M (1) element, M (2) Element and M (4) element are included in at least one of the above compounds)
[9] A raw material containing one or more compounds containing one or more of M (1) element, M (2) element, M (3) element and M (4) element (provided that M (1) Element, M (2) element, M (3) element, and M (4) element are included in at least one of the above compounds)
As described above, the dielectric composition according to this embodiment can be manufactured by a method in which the raw material is directly reduced and nitrided without generating the intermediate compound as described above.

また、本実施形態に係る誘電体組成物は、上述したような中間化合物を出発原料として、この出発原料を還元性雰囲気で加熱（焼成）することにより製造することも可能である。
つまり、本実施形態に係る誘電体組成物の製造方法は、以下の〔１０〕〜〔１２〕のいずれかの原料（中間化合物）を還元性雰囲気中で加熱する工程を含んでもよい。
〔１０〕Ｍ（１）元素及び／又はＭ（２）元素と、Ｍ（３）元素とを含む化合物を一又は二以上含有してなる原料（但し、Ｍ（１）元素、Ｍ（２）元素及びＭ（３）元素は前記化合物の少なくともいずれか一つに含まれる）
〔１１〕Ｍ（１）元素及び／又はＭ（２）元素と、Ｍ（４）元素とを含む化合物を一又は二以上含有してなる原料（但し、Ｍ（１）元素、Ｍ（２）元素及びＭ（４）元素は前記化合物の少なくともいずれか一つに含まれる）
〔１２〕Ｍ（１）元素及び／又はＭ（２）元素と、Ｍ（３）元素及び／又はＭ（４）元素とを含む化合物を一又は二以上含有してなる原料（但し、Ｍ（１）元素、Ｍ（２）元素、Ｍ（３）元素及びＭ（４）元素は前記化合物の少なくともいずれか一つに含まれる） In addition, the dielectric composition according to the present embodiment can be produced by using the above-described intermediate compound as a starting material and heating (baking) the starting material in a reducing atmosphere.
That is, the method for manufacturing a dielectric composition according to this embodiment may include a step of heating any of the following raw materials (intermediate compounds) [10] to [12] in a reducing atmosphere.
[10] A raw material containing one or more compounds containing M (1) element and / or M (2) element and M (3) element (however, M (1) element, M (2) Element and M (3) element are included in at least one of the above compounds)
[11] A raw material containing one or more compounds containing M (1) element and / or M (2) element and M (4) element (however, M (1) element, M (2) Element and M (4) element are included in at least one of the above compounds)
[12] A raw material containing one or more compounds containing M (1) element and / or M (2) element and M (3) element and / or M (4) element (provided that M ( 1) Element, M (2) element, M (3) element, and M (4) element are included in at least one of the above compounds)

上記の原料混合物、混合粉末、中間化合物あるいは中間化合物を含む混合物を還元性雰囲気中で焼成（窒化処理工程）する際は、嵩密度４０％以下の充填率に保持した状態で焼成するとよい。嵩密度とは粉末の体積充填率であり、一定容器に充填したときの質量と体積の比を化合物の理論密度で割った値である。嵩密度を４０％以下の状態に保持したまま焼成するのは、原料混合物、混合粉末、中間化合物あるいは中間化合物を含む混合物の周りに自由な空間がある状態で焼成することにより、原料混合物、混合粉末、中間化合物あるいは中間化合物を含む混合物と雰囲気ガスとの反応性が向上するためである。   When the above raw material mixture, mixed powder, intermediate compound or mixture containing the intermediate compound is fired in a reducing atmosphere (nitriding treatment step), it is preferably fired in a state where the bulk density is maintained at 40% or less. The bulk density is the volume filling rate of the powder, and is a value obtained by dividing the ratio of mass to volume when filling a certain container by the theoretical density of the compound. Firing while maintaining the bulk density at 40% or less is achieved by firing the raw material mixture, mixed powder, intermediate compound or mixture containing the intermediate compound with a free space around the raw material mixture, mixing This is because the reactivity of the powder, the intermediate compound or the mixture containing the intermediate compound and the atmospheric gas is improved.

還元性雰囲気中で焼成する際の焼成温度は、８００から１５００℃の温度範囲とする。これにより所望の誘電体組成物が得られるが、好ましい温度範囲は８００〜１２００℃である。焼成温度が８００℃よりも低いと所望の誘電体組成物を得るのに長時間を要し、１５００℃よりも高いと誘電体組成物の表面において熱分解が始まるため、何れも好ましくない。
また、焼成時間は１時間から２０時間程度であるが、より均一な誘電体組成物とするために、繰り返し焼成を行っても差し支えない。繰り返し焼成を行う場合は、２回目以降の焼成前に一回目の焼成物を解砕混合して均一性を高めるとよい。
焼成雰囲気は、還元性雰囲気とする。なお、窒素、アンモニアから選ばれる一種以上と、必要に応じて水素を加えた雰囲気中が好ましい。もっとも好ましいのはアンモニア雰囲気中である。雰囲気ガスは、焼成炉中に充填された状態でも差し支えないが、雰囲気ガスの気流中で焼成する方が望ましい。ガス流量は、通常１０ｍｌ／分以上である。 The firing temperature when firing in a reducing atmosphere is in the temperature range of 800 to 1500 ° C. Although a desired dielectric composition is obtained by this, a preferable temperature range is 800-1200 degreeC. If the firing temperature is lower than 800 ° C., it takes a long time to obtain a desired dielectric composition, and if it is higher than 1500 ° C., thermal decomposition starts on the surface of the dielectric composition, which is not preferable.
The firing time is about 1 to 20 hours, but repeated firing may be performed to obtain a more uniform dielectric composition. In the case of repeatedly firing, it is preferable to improve uniformity by crushing and mixing the first fired product before the second and subsequent firings.
The firing atmosphere is a reducing atmosphere. In addition, the atmosphere in which at least one selected from nitrogen and ammonia and hydrogen as necessary is added is preferable. Most preferred is in an ammonia atmosphere. The atmosphere gas may be in a state where it is filled in a firing furnace, but it is preferable to perform the firing in an atmosphere gas flow. The gas flow rate is usually 10 ml / min or more.

また、中間化合物あるいは中間化合物を含む混合物を充填する容器の材質としては、アルミナ、カルシア、マグネシア、黒鉛或いは窒化硼素を使用することが出来る。
焼成開始時は、一旦減圧もしくは真空状態として、炉内の残留空気を炉外に排気するか、若しくは、使用する雰囲気ガスを用いて炉内に残留している空気をパージする必要があるが、後者の場合、残留空気の除去には長時間を要するため、減圧もしくは真空状態とする方が好ましい。 Further, alumina, calcia, magnesia, graphite or boron nitride can be used as the material for the container filled with the intermediate compound or the mixture containing the intermediate compound.
At the start of firing, it is necessary to temporarily reduce the pressure in a reduced pressure or vacuum state and exhaust the residual air in the furnace to the outside of the furnace, or purge the residual air in the furnace using the atmospheric gas to be used. In the latter case, since it takes a long time to remove residual air, it is preferable to use a reduced pressure or vacuum state.

本発明の誘電体組成物の焼結体を作製する場合には、少量の焼結助剤を用いることができる。焼結助剤としては、アルカリ金属、アルカリ土類金属、珪素、ビスマス、硼素の酸化物、フッ化物などが挙げられる。一般に焼結助剤の添加量は、０．１から１０重量％程度である。   When producing a sintered body of the dielectric composition of the present invention, a small amount of sintering aid can be used. Examples of the sintering aid include alkali metals, alkaline earth metals, silicon, bismuth, boron oxides, fluorides, and the like. Generally, the addition amount of the sintering aid is about 0.1 to 10% by weight.

また、本発明に係る誘電体組成物を用いて、積層焼結体を作製することも可能である。
この積層焼結体を作製する場合は、本発明の誘電体組成物粉末に、焼結助剤、バインダー、溶媒、その他添加剤を加えて、混練して、セラミック・スラリーを形成する。バインダーとしては、ポリビニルブチラール樹脂やポリビニルアルコール、アクリル酸ポリマー等を使用することができる。溶媒としては、エタノールやイソプロピルアルコール、水等を使用することができる。
得られたセラミック・スラリーを、ＰＥＴフィルムなどの長尺のベース・フィルムに、ドクターブレード、ロールコータなどの塗布機を用いてシート状に塗布し、セラミック・グリーンシートとする。 Moreover, it is also possible to produce a laminated sintered body by using the dielectric composition according to the present invention.
When producing this laminated sintered body, a sintering aid, a binder, a solvent and other additives are added to the dielectric composition powder of the present invention and kneaded to form a ceramic slurry. As the binder, polyvinyl butyral resin, polyvinyl alcohol, acrylic acid polymer, or the like can be used. As the solvent, ethanol, isopropyl alcohol, water, or the like can be used.
The obtained ceramic slurry is applied to a long base film such as a PET film in the form of a sheet using an application machine such as a doctor blade or a roll coater to obtain a ceramic green sheet.

また、積層セラミックコンデンサーを作製する場合は、このセラミック・グリーンシートに、スクリーン印刷等によって導電ペーストを塗布し、内部電極金属層を形成する。この内部電極金属層の形成に用いる導電ペーストには、Ｐｔ，Ｐｄ，Ａｇ，Ｃｕ，Ｎｉ等の金属粉末をバインダーに分散したものを用いる。
内部電極金属層が形成されたセラミック・グリーンシートを、所定形状に打ち抜いて、これらを積み重ね、圧着してセラミック積層体を得る。この積層体を切断分割して、積層体チップとする。この積層体チップを加熱し、脱バインダーした後、焼成する。
焼成後の積層体チップに導電ペーストを焼き付けることにより外部電極を形成して、積層セラミックコンデンサーを得る。また、未焼成の積層体チップに導電ペーストを塗布してセラミック誘電体層の焼成と同時に焼き付けるようにしてもよい。 When a multilayer ceramic capacitor is manufactured, a conductive paste is applied to the ceramic green sheet by screen printing or the like to form an internal electrode metal layer. As the conductive paste used for forming the internal electrode metal layer, a metal powder such as Pt, Pd, Ag, Cu, or Ni dispersed in a binder is used.
The ceramic green sheets on which the internal electrode metal layer is formed are punched into a predetermined shape, and these are stacked and pressure-bonded to obtain a ceramic laminate. This laminate is cut and divided to obtain laminate chips. The laminate chip is heated, debindered, and then fired.
An external electrode is formed by baking a conductive paste on the fired multilayer chip to obtain a multilayer ceramic capacitor. Alternatively, a conductive paste may be applied to an unsintered multilayer chip and baked simultaneously with the firing of the ceramic dielectric layer.

本発明の誘電体組成物は、誘電体組成物粉末と樹脂とを混合した複合体を作製することにより、コンデンサーとしての機能を有する回路基板材料とすることもできる。
この場合の樹脂は、熱可塑性、熱硬化性樹脂のいずれでも良いが、はんだ耐熱性などの点から、好ましくは熱硬化性樹脂を用いる。熱可塑性樹脂では、ポリフェニレンエーテル樹脂、ポリフェニレンスルフィド樹脂、ポリエーテルサルフォン樹脂、ポリエーテルイミド樹脂、液晶ポリマー樹脂、ポリスチレン樹脂、ポリエチレン樹脂、フッ素樹脂などを用いることができる。また、熱硬化性樹脂では、エポキシ樹脂、フェノール樹脂、ポリイミド樹脂、アクリル樹脂、シアネート樹脂、ベンゾシクロブテン樹脂など一般的にプリント配線板の絶縁層に使用される樹脂を用いることができる。特に、熱硬化収縮性、粘性などの点からエポキシ樹脂が好ましい。エポキシ樹脂とは分子構造中にエポキシ基（オキシラン環）を２個以上含むプレポリマーおよび、それと硬化剤とを組合せた樹脂である。また、この硬化剤には、フェノールノボラック樹脂、ビスフェノールＡ型ノボラック樹脂、アミノトリアジン化合物、ナフトール化合物など、従来から用いられている硬化剤を用いることができる。 The dielectric composition of the present invention can be used as a circuit board material having a function as a capacitor by producing a composite in which a dielectric composition powder and a resin are mixed.
The resin in this case may be either thermoplastic or thermosetting resin, but is preferably a thermosetting resin from the viewpoint of solder heat resistance. As the thermoplastic resin, polyphenylene ether resin, polyphenylene sulfide resin, polyether sulfone resin, polyetherimide resin, liquid crystal polymer resin, polystyrene resin, polyethylene resin, fluorine resin, or the like can be used. Moreover, in thermosetting resin, resin generally used for the insulating layer of a printed wiring board, such as an epoxy resin, a phenol resin, a polyimide resin, an acrylic resin, a cyanate resin, a benzocyclobutene resin, can be used. In particular, an epoxy resin is preferable from the viewpoint of thermosetting shrinkage and viscosity. The epoxy resin is a resin obtained by combining a prepolymer containing two or more epoxy groups (oxirane rings) in a molecular structure and a curing agent. Moreover, conventionally used curing agents such as a phenol novolak resin, a bisphenol A type novolak resin, an aminotriazine compound, and a naphthol compound can be used as the curing agent.

複合体を作製する際の誘電体組成物粉末の樹脂への分散方法は、超音波分散、３本ロール、クレアミックス、ホモジナイザー、メディア分散機、自転・公転ミキサーなど、従来の方法を用いることができるが、分散状態の制御の点で３本ロール、メディア分散機、自転・公転ミキサーから選ばれる一種を用いるのが好ましい。
尚、誘電体組成物粉末を樹脂中に均一に分散させるための方法として、誘電体組成物粉末表面の修飾、分散剤の添加、溶剤の添加などが行われる。誘電体組成物粉末の表面の修飾としてはロジン処理、酸性処理、塩基性処理など、また、分散剤としてはノニオン性、カチオン性、アニオン性の界面活性剤、多価カルボン酸などの湿潤剤、両親和性物質、高立体障害の置換基を有する樹脂などが挙げられる。 As a method for dispersing the dielectric composition powder in the resin when producing the composite, conventional methods such as ultrasonic dispersion, three rolls, CLEARMIX, homogenizer, media disperser, and rotation / revolution mixer may be used. However, from the viewpoint of controlling the dispersion state, it is preferable to use one selected from three rolls, a media disperser, and a rotation / revolution mixer.
As a method for uniformly dispersing the dielectric composition powder in the resin, modification of the surface of the dielectric composition powder, addition of a dispersant, addition of a solvent, and the like are performed. As a modification of the surface of the dielectric composition powder, rosin treatment, acid treatment, basic treatment, etc., as a dispersant, nonionic, cationic, anionic surfactant, wetting agent such as polyvalent carboxylic acid, Examples thereof include amphoteric substances and resins having highly sterically hindered substituents.

以上のようにして、誘電体組成物粉末と樹脂、さらに適宜、溶剤、分散剤などからなるペースト溶液を、スピンナー、スクリーン印刷、ブレードコーター、ダイコーターなどを用いて基板上に塗布し、製膜した後、ホットプレート、オーブンなどの加熱装置を用いて、溶剤の除去や熱硬化を行うことによって回路基板材料を得ることができる。
基板は有機系基板、無機系基板、およびこれらの基板に回路の構成材料が配置されたものから選択できる。
上記の複合体は、プリント配線基板の内蔵キャパシタ作製に用いられる他、多層基板の層間絶縁膜、周波数フィルター、無線用アンテナ、電磁シールドなど、多くの電子部品、装置への適用が可能である。 As described above, a dielectric composition powder and a resin, and a paste solution composed of a solvent, a dispersant, etc., as appropriate, are applied onto a substrate using a spinner, screen printing, blade coater, die coater, etc. After that, the circuit board material can be obtained by removing the solvent or thermosetting using a heating device such as a hot plate or an oven.
The substrate can be selected from an organic substrate, an inorganic substrate, and a substrate in which circuit constituent materials are arranged.
In addition to being used for the production of a built-in capacitor on a printed wiring board, the above composite can be applied to many electronic components and devices such as an interlayer insulating film, a frequency filter, a radio antenna, and an electromagnetic shield of a multilayer board.

以下、本発明を実施例に基づいて具体的に説明するが、本発明はこれらの実施例にのみ限定されるものではない。   EXAMPLES Hereinafter, although this invention is demonstrated concretely based on an Example, this invention is not limited only to these Examples.

＜実施例１＞
まず、誘電体組成物の合成用原料として炭酸バリウム粉末、酸化ランタン粉末及び酸化チタン粉末を用いて、中間化合物を合成した。
具体的には、本発明における一般式において、ｘを表１に示す値、またｙ＝０とした組成の誘電体組成物となるよう、炭酸バリウム粉末、酸化ランタン粉末及び酸化チタン粉末を、表１に示す割合で秤取し、溶媒としてエタノールを用いた湿式ボールミルにより均一に混合し混合スラリーとした。次に、得られたスラリーを蒸発乾固して混合粉末とした後、この混合粉末を解砕した粉末をアルミナ製容器に配置し、空気中、１１００℃で２時間焼成し、中間化合物を合成した。なお、得られた中間化合物をメノー乳鉢で解砕し、粉末Ｘ線回折装置により生成相を同定したところ、Ｌａ２Ｔｉ２Ｏ７，ＢａＴｉＯ３および少量のＬａ２Ｏ３からなることがわかった。
次に、得られた中間化合物をアルミナ製ボートに配置し、アンモニア気流中１１００℃で６時間焼成し、誘電体組成物を生成した。得られた誘電体組成物は濃赤色から赤褐色を呈していた。また、得られた誘電体組成物の結晶構造は、粉末Ｘ線回折法により窒素を含有するペロブスカイト相であることが確認された。また、その組成は、Ｌａ０．９Ｂａ０．１ＴｉＯ２Ｎ０．９であった。
また、誘電率の測定には、得られた誘電体組成物の粉末を１０ＭＰａの圧力で直径１０ｍｍ、厚さ１ｍｍ程度の円板状に成形し、更に、２００ＭＰａの圧力でＣＩＰ成形した試料を用いた。試料の成形体密度を測定した後、導電性ペーストを塗布し、真空中、３００Ｋ、１００ｋＨｚで静電容量を測定した。比誘電率は、得られた静電容量の値から、特許第３２４６００１号公報に記載された方法に準拠して、リヒトネッカーの対数混合則を用いて補正を行った。なお、実施例１の場合の比誘電率は、１１０００であった。なお、実施例２〜１１の比誘電率は、実施例１の比誘電率を１００とした場合の相対値として表１に示す。
次に、得られた誘電体組成物の試料を冷却・加熱装置に装填し、真空中、−１３０℃から８００℃までの温度範囲で比誘電率の変化を調べた。比誘電率には、チタン酸バリウムのキュリー・ワイス効果に相当する顕著な変化、すなわち、強誘電体から常誘電体への相転移を示す変化は認められず、本発明の誘電体組成物は広範な温度範囲で使用可能であることがわかった。 <Example 1>
First, an intermediate compound was synthesized using barium carbonate powder, lanthanum oxide powder and titanium oxide powder as raw materials for synthesis of the dielectric composition.
Specifically, in the general formula in the present invention, barium carbonate powder, lanthanum oxide powder, and titanium oxide powder are expressed in the form of a dielectric composition having a composition in which x is a value shown in Table 1 and y = 0. The mixture was weighed at a ratio shown in 1 and uniformly mixed by a wet ball mill using ethanol as a solvent to obtain a mixed slurry. Next, the obtained slurry is evaporated to dryness to obtain a mixed powder, and then the powder obtained by pulverizing the mixed powder is placed in an alumina container and baked in air at 1100 ° C. for 2 hours to synthesize an intermediate compound. did. The obtained intermediate compound was crushed in a menor mortar and the product phase was identified by a powder X-ray diffractometer. As a result, it was found that the intermediate compound was composed of La 2 Ti 2 O 7 , BaTiO 3 and a small amount of La 2 O 3 . .
Next, the obtained intermediate compound was placed in an alumina boat and baked at 1100 ° C. for 6 hours in an ammonia stream to produce a dielectric composition. The obtained dielectric composition was dark red to reddish brown. The crystal structure of the obtained dielectric composition was confirmed to be a perovskite phase containing nitrogen by powder X-ray diffraction. Further, the composition was La 0.9 Ba 0.1 TiO 2 N 0.9 .
The dielectric constant was measured by using a sample obtained by molding the obtained dielectric composition powder into a disk shape having a diameter of about 10 mm and a thickness of about 1 mm at a pressure of 10 MPa, and further performing CIP molding at a pressure of 200 MPa. It was. After measuring the density of the molded body of the sample, a conductive paste was applied, and the capacitance was measured at 300 K and 100 kHz in a vacuum. The specific permittivity was corrected from the obtained capacitance value using the Lichtnecker logarithmic mixing rule in accordance with the method described in Japanese Patent No. 3246001. The relative dielectric constant in the case of Example 1 was 11000. The relative dielectric constants of Examples 2 to 11 are shown in Table 1 as relative values when the relative dielectric constant of Example 1 is 100.
Next, a sample of the obtained dielectric composition was loaded into a cooling / heating device, and the change in relative dielectric constant was examined in a temperature range from −130 ° C. to 800 ° C. in a vacuum. In the relative dielectric constant, no significant change corresponding to the Curie-Weiss effect of barium titanate, that is, a change indicating a phase transition from a ferroelectric to a paraelectric, is not observed. It was found that it can be used in a wide temperature range.

＜実施例２＞
実施例２は、炭酸バリウム粉末、酸化ランタン粉末及び酸化チタン粉末を表１に示す割合を用いた以外は、実施例１と同様の方法で誘電体組成物を生成した。なお、得られた中間化合物の生成相を同定したところ、実施例１と同様に、Ｌａ２Ｔｉ２Ｏ７，ＢａＴｉＯ３および少量のＬａ２Ｏ３からなることがわかった。
得られた誘電体組成物の結晶構造は粉末Ｘ線回折法により窒素を含有するペロブスカイト相であることが確認された。また、その組成はＬａ０．９５Ｂａ０．０５ＴｉＯ２．０５Ｎ０．９５であった。また、その比誘電率は実施例１の比誘電率を１００とすると、８５．２であった。
実施例２の誘電体組成物は実施例１の誘電体組成物と同じ結晶構造を有し、かつ、実施例１の誘電体組成物と組成の成分は同じであるから、実施例１の誘電体組成物と同様に、広範な温度範囲で強誘電体として使用可能であると考えられる。 <Example 2>
In Example 2, a dielectric composition was produced in the same manner as in Example 1 except that barium carbonate powder, lanthanum oxide powder and titanium oxide powder were used in the proportions shown in Table 1. Incidentally, was identified product phase of the resulting intermediate compound was synthesized in analogy to Example 1, it was found to consist of La 2 Ti 2 O 7, BaTiO 3 and a small amount of La 2 O 3.
The crystal structure of the obtained dielectric composition was confirmed to be a perovskite phase containing nitrogen by powder X-ray diffraction. The composition was La 0.95 Ba 0.05 TiO 2.05 N 0.95 . The relative dielectric constant was 85.2, where the relative dielectric constant of Example 1 was 100.
Since the dielectric composition of Example 2 has the same crystal structure as the dielectric composition of Example 1, and the components of the composition are the same as those of Example 1, the dielectric composition of Example 1 Like body compositions, it is believed that they can be used as ferroelectrics over a wide temperature range.

＜実施例３＞
実施例３は、炭酸バリウム粉末、酸化ランタン粉末及び酸化チタン粉末を表１に示す割合を用いた以外は、実施例１と同様の方法で誘電体組成物を生成した。なお、得られた中間化合物の生成相を同定したところ、実施例１と同様に、Ｌａ２Ｔｉ２Ｏ７，ＢａＴｉＯ３および少量のＬａ２Ｏ３からなることがわかった。
得られた誘電体組成物の結晶構造は粉末Ｘ線回折法により窒素を含有するペロブスカイト相であることが確認された。また、その組成はＬａ０．９２５Ｂａ０．０７５ＴｉＯ２．０７５Ｎ０．９２５であった。また、その比誘電率は実施例１の比誘電率を１００とすると、９３．３であった。
実施例３の誘電体組成物は実施例１の誘電体組成物と同じ結晶構造を有し、かつ、実施例１の誘電体組成物と組成の成分は同じであるから、実施例１の誘電体組成物と同様に、広範な温度範囲で強誘電体として使用可能であると考えられる。 <Example 3>
In Example 3, a dielectric composition was produced in the same manner as in Example 1 except that barium carbonate powder, lanthanum oxide powder and titanium oxide powder were used in the proportions shown in Table 1. Incidentally, was identified product phase of the resulting intermediate compound was synthesized in analogy to Example 1, it was found to consist of La 2 Ti 2 O 7, BaTiO 3 and a small amount of La 2 O 3.
The crystal structure of the obtained dielectric composition was confirmed to be a perovskite phase containing nitrogen by powder X-ray diffraction. Further, the composition was La 0.925 Ba 0.075 TiO 2.075 N 0.925 . The relative dielectric constant was 93.3, where the relative dielectric constant of Example 1 was 100.
Since the dielectric composition of Example 3 has the same crystal structure as the dielectric composition of Example 1, and the components of the composition are the same as those of Example 1, the dielectric composition of Example 1 Like body compositions, it is believed that they can be used as ferroelectrics over a wide temperature range.

＜実施例４＞
実施例４は、炭酸バリウム粉末、酸化ランタン粉末及び酸化チタン粉末を表１に示す割合を用いた以外は、実施例１と同様の方法で誘電体組成物を生成した。なお、得られた中間化合物の生成相を同定したところ、実施例１と同様に、Ｌａ２Ｔｉ２Ｏ７，ＢａＴｉＯ３および少量のＬａ２Ｏ３からなることがわかった。
得られた誘電体組成物の結晶構造は粉末Ｘ線回折法により窒素を含有するペロブスカイト相であることが確認された。また、その組成はＬａ０．９１Ｂａ０．０９ＴｉＯ２．０９Ｎ０．９１であった。また、その比誘電率は実施例１の比誘電率を１００とすると、９８．０であった。
実施例４の誘電体組成物は実施例１の誘電体組成物と同じ結晶構造を有し、かつ、実施例１の誘電体組成物と組成の成分は同じであるから、実施例１の誘電体組成物と同様に、広範な温度範囲で強誘電体として使用可能であると考えられる。 <Example 4>
In Example 4, a dielectric composition was produced in the same manner as in Example 1 except that the barium carbonate powder, lanthanum oxide powder, and titanium oxide powder were used in the proportions shown in Table 1. Incidentally, was identified product phase of the resulting intermediate compound was synthesized in analogy to Example 1, it was found to consist of La 2 Ti 2 O 7, BaTiO 3 and a small amount of La 2 O 3.
The crystal structure of the obtained dielectric composition was confirmed to be a perovskite phase containing nitrogen by powder X-ray diffraction. The composition was La 0.91 Ba 0.09 TiO 2.09 N 0.91 . The relative dielectric constant was 98.0, where the relative dielectric constant of Example 1 was 100.
Since the dielectric composition of Example 4 has the same crystal structure as the dielectric composition of Example 1 and the components of the composition are the same as those of Example 1, the dielectric composition of Example 1 Like body compositions, it is believed that they can be used as ferroelectrics over a wide temperature range.

＜実施例５＞
実施例５は、炭酸バリウム粉末、酸化ランタン粉末及び酸化チタン粉末を表１に示す割合を用いた以外は、実施例１と同様の方法で誘電体組成物を生成した。なお、得られた中間化合物の生成相を同定したところ、実施例１と同様に、Ｌａ２Ｔｉ２Ｏ７，ＢａＴｉＯ３および少量のＬａ２Ｏ３からなることがわかった。
得られた誘電体組成物の結晶構造は粉末Ｘ線回折法により窒素を含有するペロブスカイト相であることが確認された。また、その組成はＬａ０．８９Ｂａ０．１１ＴｉＯ２．１１Ｎ０．８９であった。また、その比誘電率は実施例１の比誘電率を１００とすると、９８．１であった。
実施例５の誘電体組成物は実施例１の誘電体組成物と同じ結晶構造を有し、かつ、実施例１の誘電体組成物と組成の成分は同じであるから、実施例１の誘電体組成物と同様に、広範な温度範囲で強誘電体として使用可能であると考えられる。 <Example 5>
In Example 5, a dielectric composition was produced in the same manner as in Example 1 except that the barium carbonate powder, lanthanum oxide powder and titanium oxide powder were used in the proportions shown in Table 1. Incidentally, was identified product phase of the resulting intermediate compound was synthesized in analogy to Example 1, it was found to consist of La 2 Ti 2 O 7, BaTiO 3 and a small amount of La 2 O 3.
The crystal structure of the obtained dielectric composition was confirmed to be a perovskite phase containing nitrogen by powder X-ray diffraction. Further, the composition was La 0.89 Ba 0.11 TiO 2.11 N 0.89 . The relative dielectric constant was 98.1, where the relative dielectric constant of Example 1 was 100.
Since the dielectric composition of Example 5 has the same crystal structure as the dielectric composition of Example 1, and the components of the composition are the same as those of Example 1, the dielectric composition of Example 1 Like body compositions, it is believed that they can be used as ferroelectrics over a wide temperature range.

＜実施例６＞
実施例６は、炭酸バリウム粉末、酸化ランタン粉末及び酸化チタン粉末を表１に示す割合を用いた以外は、実施例１と同様の方法で誘電体組成物を生成した。なお、得られた中間化合物の生成相を同定したところ、実施例１と同様に、Ｌａ２Ｔｉ２Ｏ７，ＢａＴｉＯ３および少量のＬａ２Ｏ３からなることがわかった。
得られた誘電体組成物の結晶構造は粉末Ｘ線回折法により窒素を含有するペロブスカイト相であることが確認された。また、その組成はＬａ０．８７５Ｂａ０．１２５ＴｉＯ２．１２５Ｎ０．８７５であった。また、その比誘電率は実施例１の比誘電率を１００とすると、９４．２であった。
実施例６の誘電体組成物は実施例１の誘電体組成物と同じ結晶構造を有し、かつ、実施例１の誘電体組成物と組成の成分は同じであるから、実施例１の誘電体組成物と同様に、広範な温度範囲で強誘電体として使用可能であると考えられる。 <Example 6>
In Example 6, a dielectric composition was produced in the same manner as in Example 1 except that barium carbonate powder, lanthanum oxide powder and titanium oxide powder were used in the proportions shown in Table 1. Incidentally, was identified product phase of the resulting intermediate compound was synthesized in analogy to Example 1, it was found to consist of La 2 Ti 2 O 7, BaTiO 3 and a small amount of La 2 O 3.
The crystal structure of the obtained dielectric composition was confirmed to be a perovskite phase containing nitrogen by powder X-ray diffraction. Further, the composition was La 0.875 Ba 0.125 TiO 2.125 N 0.875 . The relative dielectric constant was 94.2, assuming that the relative dielectric constant of Example 1 was 100.
Since the dielectric composition of Example 6 has the same crystal structure as the dielectric composition of Example 1, and the components of the composition are the same as those of Example 1, the dielectric composition of Example 1 Like body compositions, it is believed that they can be used as ferroelectrics over a wide temperature range.

＜実施例７＞
実施例７は、炭酸バリウム粉末、酸化ランタン粉末及び酸化チタン粉末を表１に示す割合を用いた以外は、実施例１と同様の方法で誘電体組成物を生成した。なお、得られた中間化合物の生成相を同定したところ、実施例１と同様に、Ｌａ２Ｔｉ２Ｏ７，ＢａＴｉＯ３および少量のＬａ２Ｏ３からなることがわかった。
得られた誘電体組成物の結晶構造は粉末Ｘ線回折法により窒素を含有するペロブスカイト相であることが確認された。また、その組成はＬａ０．８５Ｂａ０．１５ＴｉＯ２．１５Ｎ０．８５であった。また、その比誘電率は実施例１の比誘電率を１００とすると、８８．８であった。
実施例７の誘電体組成物は実施例１の誘電体組成物と同じ結晶構造を有し、かつ、実施例１の誘電体組成物と組成の成分は同じであるから、実施例１の誘電体組成物と同様に、広範な温度範囲で強誘電体として使用可能であると考えられる。 <Example 7>
In Example 7, a dielectric composition was produced in the same manner as in Example 1 except that the barium carbonate powder, lanthanum oxide powder and titanium oxide powder were used in the proportions shown in Table 1. Incidentally, was identified product phase of the resulting intermediate compound was synthesized in analogy to Example 1, it was found to consist of La 2 Ti 2 O 7, BaTiO 3 and a small amount of La 2 O 3.
The crystal structure of the obtained dielectric composition was confirmed to be a perovskite phase containing nitrogen by powder X-ray diffraction. Further, the composition was La 0.85 Ba 0.15 TiO 2.15 N 0.85 . The relative dielectric constant was 88.8, where the relative dielectric constant of Example 1 was 100.
Since the dielectric composition of Example 7 has the same crystal structure as the dielectric composition of Example 1, and the components of the composition are the same as those of Example 1, the dielectric composition of Example 1 Like body compositions, it is believed that they can be used as ferroelectrics over a wide temperature range.

＜実施例８＞
実施例８は、炭酸バリウム粉末、酸化ランタン粉末及び酸化チタン粉末を表１に示す割合を用いた以外は、実施例１と同様の方法で誘電体組成物を生成した。なお、得られた中間化合物の生成相を同定したところ、実施例１と同様に、Ｌａ２Ｔｉ２Ｏ７，ＢａＴｉＯ３および少量のＬａ２Ｏ３からなることがわかった。
得られた誘電体組成物の結晶構造は粉末Ｘ線回折法により窒素を含有するペロブスカイト相であることが確認された。また、その組成はＬａ０．８Ｂａ０．２ＴｉＯ２．２Ｎ０．８であった。また、その比誘電率は実施例１の比誘電率を１００とすると、８３．９であった。
実施例８の誘電体組成物は実施例１の誘電体組成物と同じ結晶構造を有し、かつ、実施例１の誘電体組成物と組成の成分は同じであるから、実施例１の誘電体組成物と同様に、広範な温度範囲で強誘電体として使用可能であると考えられる。 <Example 8>
In Example 8, a dielectric composition was produced in the same manner as in Example 1 except that the barium carbonate powder, lanthanum oxide powder and titanium oxide powder were used in the proportions shown in Table 1. Incidentally, was identified product phase of the resulting intermediate compound was synthesized in analogy to Example 1, it was found to consist of La 2 Ti 2 O 7, BaTiO 3 and a small amount of La 2 O 3.
The crystal structure of the obtained dielectric composition was confirmed to be a perovskite phase containing nitrogen by powder X-ray diffraction. Further, the composition was La 0.8 Ba 0.2 TiO 2.2 N 0.8 . The relative dielectric constant was 83.9, assuming that the relative dielectric constant of Example 1 was 100.
Since the dielectric composition of Example 8 has the same crystal structure as the dielectric composition of Example 1, and the components of the composition are the same as those of Example 1, the dielectric composition of Example 1 Like body compositions, it is believed that they can be used as ferroelectrics over a wide temperature range.

＜実施例９＞
実施例９は、炭酸バリウム粉末、酸化ランタン粉末及び酸化チタン粉末を表１に示す割合を用いた以外は、実施例１と同様の方法で誘電体組成物を生成した。なお、得られた中間化合物の生成相を同定したところ、実施例１と同様に、Ｌａ２Ｔｉ２Ｏ７，ＢａＴｉＯ３および少量のＬａ２Ｏ３からなることがわかった。
得られた誘電体組成物の結晶構造は粉末Ｘ線回折法により窒素を含有するペロブスカイト相であることが確認された。また、その組成はＬａ０．７Ｂａ０．３ＴｉＯ２．３Ｎ０．７であった。また、その比誘電率は実施例１の比誘電率を１００とすると、８２．４であった。
実施例９の誘電体組成物は実施例１の誘電体組成物と同じ結晶構造を有し、かつ、実施例１の誘電体組成物と組成の成分は同じであるから、実施例１の誘電体組成物と同様に、広範な温度範囲で強誘電体として使用可能であると考えられる。 <Example 9>
In Example 9, a dielectric composition was produced in the same manner as in Example 1 except that barium carbonate powder, lanthanum oxide powder and titanium oxide powder were used in the proportions shown in Table 1. Incidentally, was identified product phase of the resulting intermediate compound was synthesized in analogy to Example 1, it was found to consist of La 2 Ti 2 O 7, BaTiO 3 and a small amount of La 2 O 3.
The crystal structure of the obtained dielectric composition was confirmed to be a perovskite phase containing nitrogen by powder X-ray diffraction. Further, the composition was La 0.7 Ba 0.3 TiO 2.3 N 0.7 . The relative dielectric constant was 82.4, where the relative dielectric constant of Example 1 was 100.
Since the dielectric composition of Example 9 has the same crystal structure as the dielectric composition of Example 1, and the components of the composition are the same as those of Example 1, the dielectric composition of Example 1 Like body compositions, it is believed that they can be used as ferroelectrics over a wide temperature range.

＜実施例１０＞
実施例１０は、炭酸バリウム粉末、酸化ランタン粉末及び酸化チタン粉末を表１に示す割合を用いた以外は、実施例１と同様の方法で誘電体組成物を生成した。なお、得られた中間化合物の生成相を同定したところ、実施例１と同様に、Ｌａ２Ｔｉ２Ｏ７，ＢａＴｉＯ３および少量のＬａ２Ｏ３からなることがわかった。
得られた誘電体組成物の結晶構造は粉末Ｘ線回折法により窒素を含有するペロブスカイト相であることが確認された。また、その組成はＬａ０．６Ｂａ０．４ＴｉＯ２．４Ｎ０．６であった。また、その比誘電率は実施例１の比誘電率を１００とすると、７９．９であった。
実施例１０の誘電体組成物は実施例１の誘電体組成物と同じ結晶構造を有し、かつ、実施例１の誘電体組成物と組成の成分は同じであるから、実施例１の誘電体組成物と同様に、広範な温度範囲で強誘電体として使用可能であると考えられる。 <Example 10>
In Example 10, a dielectric composition was produced in the same manner as in Example 1 except that barium carbonate powder, lanthanum oxide powder and titanium oxide powder were used in the proportions shown in Table 1. Incidentally, was identified product phase of the resulting intermediate compound was synthesized in analogy to Example 1, it was found to consist of La 2 Ti 2 O 7, BaTiO 3 and a small amount of La 2 O 3.
The crystal structure of the obtained dielectric composition was confirmed to be a perovskite phase containing nitrogen by powder X-ray diffraction. Further, the composition was La 0.6 Ba 0.4 TiO 2.4 N 0.6 . The relative dielectric constant was 79.9, where the relative dielectric constant of Example 1 was 100.
Since the dielectric composition of Example 10 has the same crystal structure as the dielectric composition of Example 1, and the components of the composition are the same as those of Example 1, the dielectric composition of Example 1 Like body compositions, it is believed that they can be used as ferroelectrics over a wide temperature range.

＜実施例１１＞
実施例１１は、炭酸バリウム粉末、酸化ランタン粉末及び酸化チタン粉末を表１に示す割合を用いた以外は、実施例１と同様の方法で誘電体組成物を生成した。なお、得られた中間化合物の生成相を同定したところ、実施例１と同様に、Ｌａ２Ｔｉ２Ｏ７，ＢａＴｉＯ３および少量のＬａ２Ｏ３からなることがわかった。
得られた誘電体組成物の結晶構造は粉末Ｘ線回折法により窒素を含有するペロブスカイト相であることが確認された。また、その組成はＬａ０．５Ｂａ０．５ＴｉＯ２．５Ｎ０．５であった。また、その比誘電率は実施例１の比誘電率を１００とすると、７１．１であった。
実施例１１の誘電体組成物は実施例１の誘電体組成物と同じ結晶構造を有し、かつ、実施例１の誘電体組成物と組成の成分は同じであるから、実施例１の誘電体組成物と同様に、広範な温度範囲で強誘電体として使用可能であると考えられる。 <Example 11>
In Example 11, a dielectric composition was produced in the same manner as in Example 1 except that barium carbonate powder, lanthanum oxide powder and titanium oxide powder were used in the proportions shown in Table 1. Incidentally, was identified product phase of the resulting intermediate compound was synthesized in analogy to Example 1, it was found to consist of La 2 Ti 2 O 7, BaTiO 3 and a small amount of La 2 O 3.
The crystal structure of the obtained dielectric composition was confirmed to be a perovskite phase containing nitrogen by powder X-ray diffraction. Further, the composition was La 0.5 Ba 0.5 TiO 2.5 N 0.5 . The relative dielectric constant was 71.1, where the relative dielectric constant of Example 1 was 100.
Since the dielectric composition of Example 11 has the same crystal structure as the dielectric composition of Example 1, and the components of the composition are the same as those of Example 1, the dielectric composition of Example 1 Like body compositions, it is believed that they can be used as ferroelectrics over a wide temperature range.

Figure 0005807861
Figure 0005807861

＜実施例１２＞
誘電体組成物の合成用原料として炭酸バリウム粉末、酸化ランタン粉末、酸化チタン粉末及び酸化タンタル粉末を用いて、中間化合物を合成した。
具体的には、本発明における一般式において、ｘ＝０．１、またｙを表２に示す値とした組成の誘電体組成物となるよう、炭酸バリウム粉末、酸化ランタン粉末及び酸化チタン粉末を、表２に示す割合で秤取し、溶媒としてエタノールを用いた湿式ボールミルにより均一に混合し混合スラリーとした。次に、得られたスラリーを蒸発乾固して混合粉末とした後、この混合粉末を解砕した粉末をアルミナ製容器に配置し、空気中、１３００℃で２時間焼成し、中間化合物を合成した。なお、得られた中間化合物をメノー乳鉢で解砕し、粉末Ｘ線回折装置により生成相を同定したところ、Ｌａ２Ｔｉ２Ｏ７，ＬａＴａＯ４，ＢａＴｉＯ３および少量のＬａ２Ｏ３からなることがわかった。
次に、得られた中間化合物をアルミナ製ボートに配置し、アンモニア気流中１２００℃で６時間焼成し、誘電体組成物を生成した。得られた誘電体組成物は濃赤色から赤褐色を呈していた。また、得られた誘電体組成物の結晶構造は、粉末Ｘ線回折法により窒素を含有するペロブスカイト相であることが確認された。また、その組成は、Ｌａ０．９Ｂａ０．１Ｔｉ０．９５Ｔａ０．０５Ｏ２。０５Ｎ０．９５であった。
続いて、実施例１〜１１と同様にして比誘電率の測定を行った。なお、実施例１２〜２２の比誘電率は、実施例１の比誘電率を１００とした場合の相対値として表２に示す。
次に、得られた誘電体組成物の試料を冷却・加熱装置に装填し、真空中、−１３０℃から８００℃までの温度範囲で比誘電率の変化を調べた。実施例１と同様に、比誘電率には、チタン酸バリウムのキュリー・ワイス効果に相当する顕著な変化は認められず、本発明の誘電体組成物は広範な温度範囲で使用可能であることがわかった。 <Example 12>
Intermediate compounds were synthesized using barium carbonate powder, lanthanum oxide powder, titanium oxide powder and tantalum oxide powder as raw materials for synthesis of the dielectric composition.
Specifically, in the general formula in the present invention, barium carbonate powder, lanthanum oxide powder, and titanium oxide powder are used so that the dielectric composition has a composition in which x = 0.1 and y is a value shown in Table 2. The mixture was weighed at the ratio shown in Table 2 and uniformly mixed with a wet ball mill using ethanol as a solvent to obtain a mixed slurry. Next, the obtained slurry is evaporated to dryness to obtain a mixed powder, and then the powder obtained by pulverizing the mixed powder is placed in an alumina container and baked in air at 1300 ° C. for 2 hours to synthesize an intermediate compound. did. In addition, when the obtained intermediate compound was crushed with a menor mortar and the generated phase was identified by a powder X-ray diffractometer, it was composed of La 2 Ti 2 O 7 , LaTaO 4 , BaTiO 3 and a small amount of La 2 O 3. I understood.
Next, the obtained intermediate compound was placed in an alumina boat and baked at 1200 ° C. for 6 hours in an ammonia stream to produce a dielectric composition. The obtained dielectric composition was dark red to reddish brown. The crystal structure of the obtained dielectric composition was confirmed to be a perovskite phase containing nitrogen by powder X-ray diffraction. Further, the composition was La 0.9 Ba 0.1 Ti 0.95 Ta 0.05 O 2.05 N 0.95.
Subsequently, the relative dielectric constant was measured in the same manner as in Examples 1-11. The relative dielectric constants of Examples 12 to 22 are shown in Table 2 as relative values when the relative dielectric constant of Example 1 is 100.
Next, a sample of the obtained dielectric composition was loaded into a cooling / heating device, and the change in relative dielectric constant was examined in a temperature range from −130 ° C. to 800 ° C. in a vacuum. As in Example 1, there was no significant change in the dielectric constant corresponding to the Curie-Weiss effect of barium titanate, and the dielectric composition of the present invention can be used in a wide temperature range. I understood.

＜実施例１３＞
実施例１３は、炭酸バリウム粉末、酸化ランタン粉末、酸化チタン粉末及び酸化タンタル粉末を表２に示す割合を用いた以外は、実施例１２と同様の方法で誘電体組成物を生成した。なお、得られた中間化合物の生成相を同定したところ、実施例１２と同様に、Ｌａ２Ｔｉ２Ｏ７，ＬａＴａＯ４，ＢａＴｉＯ３および少量のＬａ２Ｏ３からなることがわかった。
得られた誘電体組成物の結晶構造は粉末Ｘ線回折法により窒素を含有するペロブスカイト相であることが確認された。また、その組成はＬａ０．９Ｂａ０．１Ｔｉ０．９２５Ｔａ０．０７５Ｏ２。０２５Ｎ０．９７５であった。また、その比誘電率は実施例１の比誘電率を１００とすると、１３０．０であった。
実施例１３の誘電体組成物は実施例１２の誘電体組成物と同じ結晶構造を有し、かつ、実施例１２の誘電体組成物と組成の成分は同じであるから、実施例１２の誘電体組成物と同様に、広範な温度範囲で強誘電体として使用可能であると考えられる。 <Example 13>
In Example 13, a dielectric composition was produced in the same manner as in Example 12 except that barium carbonate powder, lanthanum oxide powder, titanium oxide powder and tantalum oxide powder were used in the proportions shown in Table 2. Incidentally, was identified product phase of the resulting intermediate compound was synthesized in analogy to Example 12, it was found to consist of La 2 Ti 2 O 7, LaTaO 4, BaTiO 3 and a small amount of La 2 O 3.
The crystal structure of the obtained dielectric composition was confirmed to be a perovskite phase containing nitrogen by powder X-ray diffraction. Further, the composition was La 0.9 Ba 0.1 Ti 0.925 Ta 0.075 O 2.025 N 0.975. The relative dielectric constant was 130.0, where the relative dielectric constant of Example 1 was 100.
Since the dielectric composition of Example 13 has the same crystal structure as that of Example 12, and the components of the composition are the same as those of Example 12, the dielectric composition of Example 12 is the same. Like body compositions, it is believed that they can be used as ferroelectrics over a wide temperature range.

＜実施例１４＞
実施例１４は、炭酸バリウム粉末、酸化ランタン粉末、酸化チタン粉末及び酸化タンタル粉末を表２に示す割合を用いた以外は、実施例１２と同様の方法で誘電体組成物を生成した。なお、得られた中間化合物の生成相を同定したところ、実施例１２と同様に、Ｌａ２Ｔｉ２Ｏ７，ＬａＴａＯ４，ＢａＴｉＯ３および少量のＬａ２Ｏ３からなることがわかった。
得られた誘電体組成物の結晶構造は粉末Ｘ線回折法により窒素を含有するペロブスカイト相であることが確認された。また、その組成はＬａ０．９Ｂａ０．１Ｔｉ０．９１Ｔａ０．０９Ｏ２。０１Ｎ０．９９であった。また、その比誘電率は実施例１の比誘電率を１００とすると、１２９．４であった。
実施例１４の誘電体組成物は実施例１２の誘電体組成物と同じ結晶構造を有し、かつ、実施例１２の誘電体組成物と組成の成分は同じであるから、実施例１２の誘電体組成物と同様に、広範な温度範囲で強誘電体として使用可能であると考えられる。 <Example 14>
In Example 14, a dielectric composition was produced in the same manner as in Example 12, except that barium carbonate powder, lanthanum oxide powder, titanium oxide powder and tantalum oxide powder were used in the proportions shown in Table 2. Incidentally, was identified product phase of the resulting intermediate compound was synthesized in analogy to Example 12, it was found to consist of La 2 Ti 2 O 7, LaTaO 4, BaTiO 3 and a small amount of La 2 O 3.
The crystal structure of the obtained dielectric composition was confirmed to be a perovskite phase containing nitrogen by powder X-ray diffraction. Further, the composition was La 0.9 Ba 0.1 Ti 0.91 Ta 0.09 O 2.01 N 0.99. The relative dielectric constant was 129.4, where the relative dielectric constant of Example 1 was 100.
Since the dielectric composition of Example 14 has the same crystal structure as that of Example 12, and the components of the composition are the same as those of Example 12, the dielectric composition of Example 12 is the same. Like body compositions, it is believed that they can be used as ferroelectrics over a wide temperature range.

＜実施例１５＞
実施例１５は、炭酸バリウム粉末、酸化ランタン粉末、酸化チタン粉末及び酸化タンタル粉末を表２に示す割合を用いた以外は、実施例１２と同様の方法で誘電体組成物を生成した。なお、得られた中間化合物の生成相を同定したところ、実施例１２と同様に、Ｌａ２Ｔｉ２Ｏ７，ＬａＴａＯ４，ＢａＴｉＯ３および少量のＬａ２Ｏ３からなることがわかった。
得られた誘電体組成物の結晶構造は粉末Ｘ線回折法により窒素を含有するペロブスカイト相であることが確認された。また、その組成はＬａ０．９Ｂａ０．１Ｔｉ０．９Ｔａ０．１Ｏ２Ｎであった。また、その比誘電率は実施例１の比誘電率を１００とすると、１２７．４であった。
実施例１５の誘電体組成物は実施例１２の誘電体組成物と同じ結晶構造を有し、かつ、実施例１２の誘電体組成物と組成の成分は同じであるから、実施例１２の誘電体組成物と同様に、広範な温度範囲で強誘電体として使用可能であると考えられる。 <Example 15>
In Example 15, a dielectric composition was produced in the same manner as in Example 12 except that barium carbonate powder, lanthanum oxide powder, titanium oxide powder, and tantalum oxide powder were used in the proportions shown in Table 2. Incidentally, was identified product phase of the resulting intermediate compound was synthesized in analogy to Example 12, it was found to consist of La 2 Ti 2 O 7, LaTaO 4, BaTiO 3 and a small amount of La 2 O 3.
The crystal structure of the obtained dielectric composition was confirmed to be a perovskite phase containing nitrogen by powder X-ray diffraction. Further, the composition was La 0.9 Ba 0.1 Ti 0.9 Ta 0.1 O 2 N. The relative dielectric constant was 127.4, where the relative dielectric constant of Example 1 was 100.
Since the dielectric composition of Example 15 has the same crystal structure as that of Example 12, and the components of the composition are the same as those of Example 12, the dielectric composition of Example 12 is the same. Like body compositions, it is believed that they can be used as ferroelectrics over a wide temperature range.

＜実施例１６＞
実施例１６は、炭酸バリウム粉末、酸化ランタン粉末、酸化チタン粉末及び酸化タンタル粉末を表２に示す割合を用いた以外は、実施例１２と同様の方法で誘電体組成物を生成した。なお、得られた中間化合物の生成相を同定したところ、実施例１２と同様に、Ｌａ２Ｔｉ２Ｏ７，ＬａＴａＯ４，ＢａＴｉＯ３および少量のＬａ２Ｏ３からなることがわかった。
得られた誘電体組成物の結晶構造は粉末Ｘ線回折法により窒素を含有するペロブスカイト相であることが確認された。また、その組成はＬａ０．９Ｂａ０．１Ｔｉ０．８９Ｔａ０．１１Ｏ１．９９Ｎ１．０１であった。また、その比誘電率は実施例１の比誘電率を１００とすると、１２５．１であった。
実施例１６の誘電体組成物は実施例１２の誘電体組成物と同じ結晶構造を有し、かつ、実施例１２の誘電体組成物と組成の成分は同じであるから、実施例１２の誘電体組成物と同様に、広範な温度範囲で強誘電体として使用可能であると考えられる。 <Example 16>
In Example 16, a dielectric composition was produced in the same manner as in Example 12, except that barium carbonate powder, lanthanum oxide powder, titanium oxide powder and tantalum oxide powder were used in the proportions shown in Table 2. Incidentally, was identified product phase of the resulting intermediate compound was synthesized in analogy to Example 12, it was found to consist of La 2 Ti 2 O 7, LaTaO 4, BaTiO 3 and a small amount of La 2 O 3.
The crystal structure of the obtained dielectric composition was confirmed to be a perovskite phase containing nitrogen by powder X-ray diffraction. Further, the composition was La 0.9 Ba 0.1 Ti 0.89 Ta 0.11 O 1.99 N 1.01. The relative dielectric constant was 125.1, where the relative dielectric constant of Example 1 was 100.
Since the dielectric composition of Example 16 has the same crystal structure as the dielectric composition of Example 12, and the components of the composition are the same as those of Example 12, the dielectric composition of Example 12 Like body compositions, it is believed that they can be used as ferroelectrics over a wide temperature range.

＜実施例１７＞
実施例１７は、炭酸バリウム粉末、酸化ランタン粉末、酸化チタン粉末及び酸化タンタル粉末を表２に示す割合を用いた以外は、実施例１２と同様の方法で誘電体組成物を生成した。なお、得られた中間化合物の生成相を同定したところ、実施例１２と同様に、Ｌａ２Ｔｉ２Ｏ７，ＬａＴａＯ４，ＢａＴｉＯ３および少量のＬａ２Ｏ３からなることがわかった。
得られた誘電体組成物の結晶構造は粉末Ｘ線回折法により窒素を含有するペロブスカイト相であることが確認された。また、その組成はＬａ０．９Ｂａ０．１Ｔｉ０．８７５Ｔａ０．１２５Ｏ１．９７５Ｎ１．０２５であった。また、その比誘電率は実施例１の比誘電率を１００とすると、１２２．６であった。
実施例１７の誘電体組成物は実施例１２の誘電体組成物と同じ結晶構造を有し、かつ、実施例１２の誘電体組成物と組成の成分は同じであるから、実施例１２の誘電体組成物と同様に、広範な温度範囲で強誘電体として使用可能であると考えられる。 <Example 17>
In Example 17, a dielectric composition was produced in the same manner as in Example 12 except that barium carbonate powder, lanthanum oxide powder, titanium oxide powder and tantalum oxide powder were used in the proportions shown in Table 2. Incidentally, was identified product phase of the resulting intermediate compound was synthesized in analogy to Example 12, it was found to consist of La 2 Ti 2 O 7, LaTaO 4, BaTiO 3 and a small amount of La 2 O 3.
The crystal structure of the obtained dielectric composition was confirmed to be a perovskite phase containing nitrogen by powder X-ray diffraction. Further, the composition was La 0.9 Ba 0.1 Ti 0.875 Ta 0.125 O 1.975 N 1.025. The relative dielectric constant was 122.6, assuming that the relative dielectric constant of Example 1 was 100.
Since the dielectric composition of Example 17 has the same crystal structure as that of Example 12, and the components of the composition are the same as those of Example 12, the dielectric composition of Example 12 is the same. Like body compositions, it is believed that they can be used as ferroelectrics over a wide temperature range.

＜実施例１８＞
実施例１８は、炭酸バリウム粉末、酸化ランタン粉末、酸化チタン粉末及び酸化タンタル粉末を表２に示す割合を用いた以外は、実施例１２と同様の方法で誘電体組成物を生成した。なお、得られた中間化合物の生成相を同定したところ、実施例１２と同様に、Ｌａ２Ｔｉ２Ｏ７，ＬａＴａＯ４，ＢａＴｉＯ３および少量のＬａ２Ｏ３からなることがわかった。
得られた誘電体組成物の結晶構造は粉末Ｘ線回折法により窒素を含有するペロブスカイト相であることが確認された。また、その組成はＬａ０．９Ｂａ０．１Ｔｉ０．８５Ｔａ０．１５Ｏ１．９５Ｎ１．０５であった。また、その比誘電率は実施例１の比誘電率を１００とすると、１２１．３であった。
実施例１８の誘電体組成物は実施例１２の誘電体組成物と同じ結晶構造を有し、かつ、実施例１２の誘電体組成物と組成の成分は同じであるから、実施例１２の誘電体組成物と同様に、広範な温度範囲で強誘電体として使用可能であると考えられる。 <Example 18>
In Example 18, a dielectric composition was produced in the same manner as in Example 12, except that barium carbonate powder, lanthanum oxide powder, titanium oxide powder and tantalum oxide powder were used in the proportions shown in Table 2. Incidentally, was identified product phase of the resulting intermediate compound was synthesized in analogy to Example 12, it was found to consist of La 2 Ti 2 O 7, LaTaO 4, BaTiO 3 and a small amount of La 2 O 3.
The crystal structure of the obtained dielectric composition was confirmed to be a perovskite phase containing nitrogen by powder X-ray diffraction. Further, the composition was La 0.9 Ba 0.1 Ti 0.85 Ta 0.15 O 1.95 N 1.05. The relative dielectric constant was 121.3, where the relative dielectric constant of Example 1 was 100.
Since the dielectric composition of Example 18 has the same crystal structure as that of Example 12, and the components of the composition are the same as those of Example 12, the dielectric composition of Example 12 is the same. Like body compositions, it is believed that they can be used as ferroelectrics over a wide temperature range.

＜実施例１９＞
実施例１９は、炭酸バリウム粉末、酸化ランタン粉末、酸化チタン粉末及び酸化タンタル粉末を表２に示す割合を用いた以外は、実施例１２と同様の方法で誘電体組成物を生成した。なお、得られた中間化合物の生成相を同定したところ、実施例１２と同様に、Ｌａ２Ｔｉ２Ｏ７，ＬａＴａＯ４，ＢａＴｉＯ３および少量のＬａ２Ｏ３からなることがわかった。
得られた誘電体組成物の結晶構造は粉末Ｘ線回折法により窒素を含有するペロブスカイト相であることが確認された。また、その組成はＬａ０．９Ｂａ０．１Ｔｉ０．８Ｔａ０．２Ｏ１．９Ｎ１．１であった。また、その比誘電率は実施例１の比誘電率を１００とすると、１１７．４であった。
実施例１９の誘電体組成物は実施例１２の誘電体組成物と同じ結晶構造を有し、かつ、実施例１２の誘電体組成物と組成の成分は同じであるから、実施例１２の誘電体組成物と同様に、広範な温度範囲で強誘電体として使用可能であると考えられる。 <Example 19>
In Example 19, a dielectric composition was produced in the same manner as in Example 12, except that barium carbonate powder, lanthanum oxide powder, titanium oxide powder and tantalum oxide powder were used in the proportions shown in Table 2. Incidentally, was identified product phase of the resulting intermediate compound was synthesized in analogy to Example 12, it was found to consist of La 2 Ti 2 O 7, LaTaO 4, BaTiO 3 and a small amount of La 2 O 3.
The crystal structure of the obtained dielectric composition was confirmed to be a perovskite phase containing nitrogen by powder X-ray diffraction. Further, the composition was La 0.9 Ba 0.1 Ti 0.8 Ta 0.2 O 1.9 N 1.1. The relative dielectric constant was 117.4, where the relative dielectric constant of Example 1 was 100.
Since the dielectric composition of Example 19 has the same crystal structure as that of Example 12, and the components of the composition are the same as those of Example 12, the dielectric composition of Example 12 is the same. Like body compositions, it is believed that they can be used as ferroelectrics over a wide temperature range.

＜実施例２０＞
実施例２０は、炭酸バリウム粉末、酸化ランタン粉末、酸化チタン粉末及び酸化タンタル粉末を表２に示す割合を用いた以外は、実施例１２と同様の方法で誘電体組成物を生成した。なお、得られた中間化合物の生成相を同定したところ、実施例１２と同様に、Ｌａ２Ｔｉ２Ｏ７，ＬａＴａＯ４，ＢａＴｉＯ３および少量のＬａ２Ｏ３からなることがわかった。
得られた誘電体組成物の結晶構造は粉末Ｘ線回折法により窒素を含有するペロブスカイト相であることが確認された。また、その組成はＬａ０．９Ｂａ０．１Ｔｉ０．７Ｔａ０．３Ｏ１．８Ｎ１．２であった。また、その比誘電率は実施例１の比誘電率を１００とすると、１０９．５であった。
実施例２０の誘電体組成物は実施例１２の誘電体組成物と同じ結晶構造を有し、かつ、実施例１２の誘電体組成物と組成の成分は同じであるから、実施例１２の誘電体組成物と同様に、広範な温度範囲で強誘電体として使用可能であると考えられる。 <Example 20>
In Example 20, a dielectric composition was produced in the same manner as in Example 12 except that the barium carbonate powder, lanthanum oxide powder, titanium oxide powder and tantalum oxide powder were used in the proportions shown in Table 2. Incidentally, was identified product phase of the resulting intermediate compound was synthesized in analogy to Example 12, it was found to consist of La 2 Ti 2 O 7, LaTaO 4, BaTiO 3 and a small amount of La 2 O 3.
The crystal structure of the obtained dielectric composition was confirmed to be a perovskite phase containing nitrogen by powder X-ray diffraction. Further, the composition was La 0.9 Ba 0.1 Ti 0.7 Ta 0.3 O 1.8 N 1.2. The relative dielectric constant was 109.5, where the relative dielectric constant of Example 1 was 100.
Since the dielectric composition of Example 20 has the same crystal structure as the dielectric composition of Example 12, and the components of the composition are the same as those of Example 12, the dielectric composition of Example 12 is the same. Like body compositions, it is believed that they can be used as ferroelectrics over a wide temperature range.

＜実施例２１＞
実施例２１は、炭酸バリウム粉末、酸化ランタン粉末、酸化チタン粉末及び酸化タンタル粉末を表２に示す割合を用いた以外は、実施例１２と同様の方法で誘電体組成物を生成した。なお、得られた中間化合物の生成相を同定したところ、実施例１２と同様に、Ｌａ２Ｔｉ２Ｏ７，ＬａＴａＯ４，ＢａＴｉＯ３および少量のＬａ２Ｏ３からなることがわかった。
得られた誘電体組成物の結晶構造は粉末Ｘ線回折法により窒素を含有するペロブスカイト相であることが確認された。また、その組成はＬａ０．９Ｂａ０．１Ｔｉ０．６Ｔａ０．４Ｏ１．７Ｎ１．３であった。また、その比誘電率は実施例１の比誘電率を１００とすると、１０３．４であった。
実施例２１の誘電体組成物は実施例１２の誘電体組成物と同じ結晶構造を有し、かつ、実施例１２の誘電体組成物と組成の成分は同じであるから、実施例１２の誘電体組成物と同様に、広範な温度範囲で強誘電体として使用可能であると考えられる。 <Example 21>
In Example 21, a dielectric composition was produced in the same manner as in Example 12 except that barium carbonate powder, lanthanum oxide powder, titanium oxide powder and tantalum oxide powder were used in the proportions shown in Table 2. Incidentally, was identified product phase of the resulting intermediate compound was synthesized in analogy to Example 12, it was found to consist of La 2 Ti 2 O 7, LaTaO 4, BaTiO 3 and a small amount of La 2 O 3.
The crystal structure of the obtained dielectric composition was confirmed to be a perovskite phase containing nitrogen by powder X-ray diffraction. Further, the composition was La 0.9 Ba 0.1 Ti 0.6 Ta 0.4 O 1.7 N 1.3. The relative dielectric constant was 103.4, where the relative dielectric constant of Example 1 was 100.
Since the dielectric composition of Example 21 has the same crystal structure as that of Example 12, and the components of the composition are the same as those of Example 12, the dielectric composition of Example 12 is the same. Like body compositions, it is believed that they can be used as ferroelectrics over a wide temperature range.

＜実施例２２＞
実施例２２は、炭酸バリウム粉末、酸化ランタン粉末、酸化チタン粉末及び酸化タンタル粉末を表２に示す割合を用いた以外は、実施例１２と同様の方法で誘電体組成物を生成した。なお、得られた中間化合物の生成相を同定したところ、実施例１２と同様に、Ｌａ２Ｔｉ２Ｏ７，ＬａＴａＯ４，ＢａＴｉＯ３および少量のＬａ２Ｏ３からなることがわかった。
得られた誘電体組成物の結晶構造は粉末Ｘ線回折法により窒素を含有するペロブスカイト相であることが確認された。また、その組成はＬａ０．９Ｂａ０．１Ｔｉ０．５Ｔａ０．５Ｏ１．６Ｎ１．４であった。また、その比誘電率は実施例１の比誘電率を１００とすると、１０１．０であった。
実施例２２の誘電体組成物は実施例１２の誘電体組成物と同じ結晶構造を有し、かつ、実施例１２の誘電体組成物と組成の成分は同じであるから、実施例１２の誘電体組成物と同様に、広範な温度範囲で強誘電体として使用可能であると考えられる。 <Example 22>
In Example 22, a dielectric composition was produced in the same manner as in Example 12 except that barium carbonate powder, lanthanum oxide powder, titanium oxide powder and tantalum oxide powder were used in the proportions shown in Table 2. Incidentally, was identified product phase of the resulting intermediate compound was synthesized in analogy to Example 12, it was found to consist of La 2 Ti 2 O 7, LaTaO 4, BaTiO 3 and a small amount of La 2 O 3.
The crystal structure of the obtained dielectric composition was confirmed to be a perovskite phase containing nitrogen by powder X-ray diffraction. Further, the composition was La 0.9 Ba 0.1 Ti 0.5 Ta 0.5 O 1.6 N 1.4. The relative dielectric constant was 101.0, where the relative dielectric constant of Example 1 was 100.
Since the dielectric composition of Example 22 has the same crystal structure as the dielectric composition of Example 12, and the components of the composition are the same as those of Example 12, the dielectric composition of Example 12 is the same. Like body compositions, it is believed that they can be used as ferroelectrics over a wide temperature range.

Figure 0005807861
Figure 0005807861

＜比較例１＞
本発明における一般式のｘとｙを、ｘ＝０，ｙ＝０とした組成の酸窒化物を合成した。
まず、酸化ランタン粉末及び酸化チタン粉末を用いて、中間化合物の合成を行った。具体的には、酸化ランタン粉末及び酸化チタン粉末を、表３に示す割合で秤取し、溶媒としてエタノールを用いた湿式ボールミルにより均一に混合し混合スラリーとした。次に、得られたスラリーを蒸発乾固して混合粉末とした後、この混合粉末を解砕した粉末をアルミナ製容器に配置し、空気中、１１００℃で２時間焼成し、中間化合物を合成した。なお、得られた中間化合物をメノー乳鉢で解砕し、粉末Ｘ線回折装置により生成相を同定したところ、Ｌａ２Ｔｉ２Ｏ７および少量のＬａ２Ｏ３からなることがわかった。
次に、得られた中間化合物をアルミナ製ボートに配置し、アンモニア気流中１１００℃で６時間焼成し、誘電体組成物を生成した。得られた誘電体組成物は濃赤色から赤褐色を呈していた。また、得られた誘電体組成物の結晶構造は、粉末Ｘ線回折法により窒素を含有するペロブスカイト相であることが確認された。また、その組成は、ＬａＴｉＯ２Ｎであった。
続いて、実施例１〜１１と同様にして比誘電率の測定を行った。なお、比較例１の比誘電率は、実施例１の比誘電率を１００とした場合の相対値として表３に示す。 <Comparative Example 1>
An oxynitride having a composition in which x and y in the general formula in the present invention were set to x = 0 and y = 0 was synthesized.
First, an intermediate compound was synthesized using lanthanum oxide powder and titanium oxide powder. Specifically, lanthanum oxide powder and titanium oxide powder were weighed in the proportions shown in Table 3, and uniformly mixed by a wet ball mill using ethanol as a solvent to obtain a mixed slurry. Next, the obtained slurry is evaporated to dryness to obtain a mixed powder, and then the powder obtained by pulverizing the mixed powder is placed in an alumina container and baked in air at 1100 ° C. for 2 hours to synthesize an intermediate compound. did. In addition, when the obtained intermediate compound was crushed with a menor mortar and the generated phase was identified by a powder X-ray diffractometer, it was found to be composed of La 2 Ti 2 O 7 and a small amount of La 2 O 3 .
Next, the obtained intermediate compound was placed in an alumina boat and baked at 1100 ° C. for 6 hours in an ammonia stream to produce a dielectric composition. The obtained dielectric composition was dark red to reddish brown. The crystal structure of the obtained dielectric composition was confirmed to be a perovskite phase containing nitrogen by powder X-ray diffraction. The composition was LaTiO 2 N.
Subsequently, the relative dielectric constant was measured in the same manner as in Examples 1-11. The relative dielectric constant of Comparative Example 1 is shown in Table 3 as relative values when the relative dielectric constant of Example 1 is 100.

＜比較例２＞
本発明における一般式のｘとｙを、ｘ＝１，ｙ＝０とした組成の酸化物を合成した。
酸化バリウム粉末及び酸化チタン粉末を用いて、チタン酸バリウムを合成した。具体的には、酸化バリウム粉末及び酸化チタン粉末を、表３に示す割合で秤取し、溶媒としてエタノールを用いた湿式ボールミルにより均一に混合し混合スラリーとした。次に、得られたスラリーを蒸発乾固して混合粉末とした後、アルミナ製容器に配置し、空気中、１１００℃で２時間焼成した。得られた生成物をメノー乳鉢で解砕し、粉末Ｘ線回折装置により生成相を同定したところ、ＢａＴｉＯ３からなることがわかった。
続いて、実施例１〜１１と同様にして比誘電率の測定を行った。なお、比較例２の比誘電率は、実施例１の比誘電率を１００とした場合の相対値として表３に示す。 <Comparative Example 2>
An oxide having a composition in which x and y in the general formula in the present invention are x = 1 and y = 0 was synthesized.
Barium titanate was synthesized using barium oxide powder and titanium oxide powder. Specifically, barium oxide powder and titanium oxide powder were weighed in the proportions shown in Table 3, and uniformly mixed by a wet ball mill using ethanol as a solvent to obtain a mixed slurry. Next, the obtained slurry was evaporated to dryness to obtain a mixed powder, which was then placed in an alumina container and baked in air at 1100 ° C. for 2 hours. The obtained product was crushed with a menor mortar, and the product phase was identified by a powder X-ray diffractometer. As a result, it was found to be composed of BaTiO 3 .
Subsequently, the relative dielectric constant was measured in the same manner as in Examples 1-11. The relative dielectric constant of Comparative Example 2 is shown in Table 3 as relative values when the relative dielectric constant of Example 1 is 100.

Figure 0005807861
Figure 0005807861

＜実施例２３＞
実施例１で用いた誘電体組成物の粉末に、Ｂ２Ｏ３；６３ｍｏｌ％、ＳｉＯ２；３ｍｏｌ％、Ｌｉ２Ｏ；３４ｍｏｌ％の組成を有する焼結助剤を５ｍｏｌ％添加し、成形助剤（バインダー）として少量のポリビニルアルコールを用いて成形し、４００℃で脱バインダーを行った。その後に窒素雰囲気中、１０００℃で焼結した。得られた焼結体は気孔率が０．１％以下であった。 <Example 23>
A sintering aid having a composition of B 2 O 3 ; 63 mol%, SiO 2 ; 3 mol%, Li 2 O; 34 mol% was added to the dielectric composition powder used in Example 1 in an amount of 5 mol%. Molding was performed using a small amount of polyvinyl alcohol as an agent (binder), and the binder was removed at 400 ° C. Thereafter, sintering was performed at 1000 ° C. in a nitrogen atmosphere. The obtained sintered body had a porosity of 0.1% or less.

＜実施例２４＞
エポキシ樹脂の主剤としてジシクロペンタジエン系のＨＰ７２００（大日本インキ工業（株）製）；２０重量部、硬化剤としてフェノールノボラック系のＴＤ−２１３１（大日本インキ工業（株）製）；８重量部、硬化促進剤としてトリフェニルホスフィン（北興化学（株）製）；０．２８重量部、溶剤γ−ブチロラクトン；３０．５重量部を混合し、エポキシ樹脂溶液を作製した。この樹脂溶液に、無機フィラーとして、実施例１で用いた誘電体組成物粉末；２１５重量部を混合して、複合体（樹脂組成物）を調整した。このとき、無機フィラーと樹脂の合計量を１００体積％としたとき、無機フィラーの含有量は６５体積％であった。
次に、３本ロールを用いてこの樹脂組成物を混練したのち、厚さ３００μｍのアルミ基板上にダイコーターを用いて塗布し、オーブンを用いて、８０℃×２０分間で乾燥させ溶剤を除去した後、１７０℃×１時間で樹脂を硬化させ、膜厚１０μｍの回路基板材料としての誘電体組成物を得た。
次に、この誘電体組成物にアルミ電極を蒸着法により形成し、ＪＩＳ Ｋ６９１１に準拠して比誘電率を測定した結果、比誘電率は６５０であった。 <Example 24>
Dicyclopentadiene-based HP7200 (manufactured by Dainippon Ink Industries, Ltd.) as the main component of the epoxy resin; 20 parts by weight; phenol novolac TD-2131 (manufactured by Dainippon Ink Industries, Ltd.) as the curing agent; 8 parts by weight Then, 0.28 parts by weight of triphenylphosphine (made by Hokuko Chemical Co., Ltd.) as a curing accelerator; 30.5 parts by weight of solvent γ-butyrolactone; 30.5 parts by weight were mixed to prepare an epoxy resin solution. To this resin solution, 215 parts by weight of the dielectric composition powder used in Example 1 was mixed as an inorganic filler to prepare a composite (resin composition). At this time, when the total amount of the inorganic filler and the resin was 100% by volume, the content of the inorganic filler was 65% by volume.
Next, after kneading this resin composition using three rolls, it was applied to a 300 μm thick aluminum substrate using a die coater and dried in an oven at 80 ° C. for 20 minutes to remove the solvent. Then, the resin was cured at 170 ° C. for 1 hour to obtain a dielectric composition as a circuit board material having a thickness of 10 μm.
Next, an aluminum electrode was formed on this dielectric composition by vapor deposition, and the relative dielectric constant was measured in accordance with JIS K6911. As a result, the relative dielectric constant was 650.

本発明の誘電体組成物は、室温から２００℃の間にキュリー点を持たず、しかも従来知られている酸窒化物系ペロブスカイト型化合物よりも高い比誘電率を有することから、パワーモジュール周辺に配置される電子デバイスに好適である。今後、本発明が、大いに活用され、産業の発展に大きく寄与することが期待できる。   Since the dielectric composition of the present invention does not have a Curie point between room temperature and 200 ° C., and has a higher relative dielectric constant than a conventionally known oxynitride perovskite compound, Suitable for the electronic device to be arranged. In the future, it can be expected that the present invention will be greatly utilized and greatly contribute to industrial development.

Claims (7)

一般式：Ｍ（１）１−ｘＭ（２）ｘＭ（３）１−ｙＭ（４）ｙＯ２＋ｘ―ｙＮ１―ｘ＋ｙ
で示される組成からなることを特徴とする誘電体組成物。
但し、Ｍ（１）元素はＬａであり、Ｍ（２）元素はＢａであり、Ｍ（３）元素はＴｉであり、Ｍ（４）元素はＴａであり、ＯとＮは酸素と窒素であり、０＜ｘ≦０．５かつ０．０５≦ｙ≦０．５である。 General formula: M (1) 1-x M (2) x M (3) 1-y M (4) y O 2 + xy N 1-x + y
A dielectric composition comprising:
However, the M (1) element is La, the M (2) element is Ba, the M (3) element is Ti, the M (4) element is Ta, and O and N are oxygen and nitrogen. Yes, 0 <x ≦ 0.5 and 0.05 ≦ y ≦ 0.5. 以下の〔１〕〜〔３〕のいずれかの原料を加熱して、以下の〔４〕〜〔６〕のいずれかの中間化合物を生成する工程と、該中間化合物を還元性雰囲気中で加熱する工程とを含むことを特徴とする請求項１に記載の誘電体組成物の製造方法。
〔１〕Ｍ（１）元素、Ｍ（２）元素及びＭ（３）元素のうちの一又は二以上を含む化合物を一又は二以上含有してなる原料（但し、Ｍ（１）元素、Ｍ（２）元素及びＭ（３）元素は前記化合物の少なくともいずれか一つに含まれる）、
〔２〕Ｍ（１）元素、Ｍ（２）元素及びＭ（４）元素のうちの一又は二以上を含む化合物を一又は二以上含有してなる原料（但し、Ｍ（１）元素、Ｍ（２）元素及びＭ（４）元素は前記化合物の少なくともいずれか一つに含まれる）、
〔３〕Ｍ（１）元素、Ｍ（２）元素、Ｍ（３）元素及びＭ（４）元素のうちの一又は二以上を含む化合物を一又は二以上含有してなる原料（但し、Ｍ（１）元素、Ｍ（２）元素、Ｍ（３）元素及びＭ（４）元素は前記化合物の少なくともいずれか一つに含まれる）
〔４〕Ｍ（１）元素及び／又はＭ（２）元素と、Ｍ（３）元素とを含む化合物を一又は二以上含有してなる中間化合物（但し、Ｍ（１）元素、Ｍ（２）元素及びＭ（３）元素は前記化合物の少なくともいずれか一つに含まれる）
〔５〕Ｍ（１）元素及び／又はＭ（２）元素と、Ｍ（４）元素とを含む化合物を一又は二以上含有してなる中間化合物（但し、Ｍ（１）元素、Ｍ（２）元素及びＭ（４）元素は前記化合物の少なくともいずれか一つに含まれる）
〔６〕Ｍ（１）元素及び／又はＭ（２）元素と、Ｍ（３）元素及び／又はＭ（４）元素とを含む化合物を一又は二以上含有してなる中間化合物（但し、Ｍ（１）元素、Ｍ（２）元素、Ｍ（３）元素及びＭ（４）元素は前記化合物の少なくともいずれか一つに含まれる） Heating the raw material of any of the following [1] to [3] to produce an intermediate compound of any of the following [4] to [6], and heating the intermediate compound in a reducing atmosphere The method for producing a dielectric composition according to claim 1, further comprising:
[1] A raw material containing one or more compounds containing one or more of M (1) element, M (2) element and M (3) element (provided that M (1) element, M (2) Element and M (3) element are included in at least one of the above compounds),
[2] A raw material containing one or more compounds containing one or more of M (1) element, M (2) element and M (4) element (provided that M (1) element, M (2) Element and M (4) element are included in at least one of the above compounds),
[3] A raw material containing one or more compounds containing one or more of M (1) element, M (2) element, M (3) element and M (4) element (provided that M (1) Element, M (2) element, M (3) element, and M (4) element are included in at least one of the above compounds)
[4] Intermediate compound containing one or more compounds containing M (1) element and / or M (2) element and M (3) element (provided that M (1) element, M (2 ) Element and M (3) element are included in at least one of the above compounds)
[5] Intermediate compound containing one or more compounds containing M (1) element and / or M (2) element and M (4) element (provided that M (1) element, M (2 ) Element and M (4) element are included in at least one of the above compounds)
[6] Intermediate compound comprising one or more compounds containing M (1) element and / or M (2) element and M (3) element and / or M (4) element (provided that M (1) Element, M (2) element, M (3) element, and M (4) element are included in at least one of the above compounds) 前記化合物の少なくとも一つは酸化物であることを特徴とする請求項２に記載の誘電体組成物の製造方法。   The method for producing a dielectric composition according to claim 2, wherein at least one of the compounds is an oxide. 以下の〔１〕〜〔３〕のいずれかの原料を還元性雰囲気中で加熱する工程を含むことを特徴とする請求項１に記載の誘電体組成物の製造方法。
〔１〕Ｍ（１）元素、Ｍ（２）元素及びＭ（３）元素のうちの一又は二以上を含む化合物を一又は二以上含有してなる原料（但し、Ｍ（１）元素、Ｍ（２）元素及びＭ（３）元素は前記化合物の少なくともいずれか一つに含まれる）、
〔２〕Ｍ（１）元素、Ｍ（２）元素及びＭ（４）元素のうちの一又は二以上を含む化合物を一又は二以上含有してなる原料（但し、Ｍ（１）元素、Ｍ（２）元素及びＭ（４）元素は前記化合物の少なくともいずれか一つに含まれる）、
〔３〕Ｍ（１）元素、Ｍ（２）元素、Ｍ（３）元素及びＭ（４）元素のうちの一又は二以上を含む化合物を一又は二以上含有してなる原料（但し、Ｍ（１）元素、Ｍ（２）元素、Ｍ（３）元素及びＭ（４）元素は前記化合物の少なくともいずれか一つに含まれる） The method for producing a dielectric composition according to claim 1, further comprising a step of heating any of the following raw materials [1] to [3] in a reducing atmosphere.
[1] A raw material containing one or more compounds containing one or more of M (1) element, M (2) element and M (3) element (provided that M (1) element, M (2) Element and M (3) element are included in at least one of the above compounds),
[2] A raw material containing one or more compounds containing one or more of M (1) element, M (2) element and M (4) element (provided that M (1) element, M (2) Element and M (4) element are included in at least one of the above compounds),
[3] A raw material containing one or more compounds containing one or more of M (1) element, M (2) element, M (3) element and M (4) element (provided that M (1) Element, M (2) element, M (3) element, and M (4) element are included in at least one of the above compounds) 前記化合物の少なくとも一つは酸化物であることを特徴とする請求項４に記載の誘電体組成物の製造方法。   The method for producing a dielectric composition according to claim 4, wherein at least one of the compounds is an oxide. 以下の〔１〕〜〔３〕のいずれかの原料を還元性雰囲気中で加熱する工程を含むことを特徴とする請求項１に記載の誘電体組成物の製造方法。
〔１〕Ｍ（１）元素及び／又はＭ（２）元素と、Ｍ（３）元素とを含む化合物を一又は二以上含有してなる原料（但し、Ｍ（１）元素、Ｍ（２）元素及びＭ（３）元素は前記化合物の少なくともいずれか一つに含まれる）
〔２〕Ｍ（１）元素及び／又はＭ（２）元素と、Ｍ（４）元素とを含む化合物を一又は二以上含有してなる原料（但し、Ｍ（１）元素、Ｍ（２）元素及びＭ（４）元素は前記化合物の少なくともいずれか一つに含まれる）
〔３〕Ｍ（１）元素及び／又はＭ（２）元素と、Ｍ（３）元素及び／又はＭ（４）元素とを含む化合物を一又は二以上含有してなる原料（但し、Ｍ（１）元素、Ｍ（２）元素、Ｍ（３）元素及びＭ（４）元素は前記化合物の少なくともいずれか一つに含まれる） The method for producing a dielectric composition according to claim 1, further comprising a step of heating any of the following raw materials [1] to [3] in a reducing atmosphere.
[1] A raw material containing one or more compounds containing M (1) element and / or M (2) element and M (3) element (however, M (1) element, M (2) Element and M (3) element are included in at least one of the above compounds)
[2] A raw material comprising one or more compounds containing M (1) element and / or M (2) element and M (4) element (however, M (1) element, M (2) Element and M (4) element are included in at least one of the above compounds)
[3] A raw material containing one or more compounds containing M (1) element and / or M (2) element and M (3) element and / or M (4) element (provided that M ( 1) Element, M (2) element, M (3) element, and M (4) element are included in at least one of the above compounds) 前記化合物の少なくとも一つは酸化物であることを特徴とする請求項６に記載の誘電体
組成物の製造方法。 The method for producing a dielectric composition according to claim 6, wherein at least one of the compounds is an oxide.
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