JP2011249836A - Coil-type electronic component and manufacturing method thereof - Google Patents
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- 229910052742 iron Inorganic materials 0.000 claims abstract description 94
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- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 29
- 238000000034 method Methods 0.000 claims description 29
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- 238000002149 energy-dispersive X-ray emission spectroscopy Methods 0.000 claims description 20
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- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 15
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- UCNNJGDEJXIUCC-UHFFFAOYSA-L hydroxy(oxo)iron;iron Chemical compound [Fe].O[Fe]=O.O[Fe]=O UCNNJGDEJXIUCC-UHFFFAOYSA-L 0.000 claims 1
- 230000004907 flux Effects 0.000 abstract description 30
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- 229910018125 Al-Si Inorganic materials 0.000 description 3
- 229910018520 Al—Si Inorganic materials 0.000 description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 3
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- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 2
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- 229910002796 Si–Al Inorganic materials 0.000 description 1
- JQEFXLZKSTUUEC-UHFFFAOYSA-N [Si].[Fe].[Fe] Chemical compound [Si].[Fe].[Fe] JQEFXLZKSTUUEC-UHFFFAOYSA-N 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
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Abstract
Description
本発明は、コイル型電子部品およびその製造方法に関し、特に、回路基板上への面実装が可能な小型化されたコイル型電子部品に適した軟磁性合金を用いたコイル型電子部品、およびその製造方法に関する。 The present invention relates to a coil-type electronic component and a method for manufacturing the same, and more particularly to a coil-type electronic component using a soft magnetic alloy suitable for a miniaturized coil-type electronic component that can be surface-mounted on a circuit board, and the same It relates to a manufacturing method.
従来、高周波で用いられるチョークコイルの磁性コアとして、フェライトコアや金属薄板のカットコアや、圧粉磁芯が使用されている。
フェライトに比較して、金属磁性体を用いると、高い飽和磁束密度を得られる利点がある。一方、金属磁性体そのものは、絶縁性が低いので、絶縁処理を施す必要がある。
特許文献１には、表面酸化被膜を有するＦｅ−Ａｌ−Ｓｉ粉末と結着剤からなる混合物を圧縮成形後、酸化性雰囲気中で熱処理することが提案されている。該特許文献によれば、酸化性雰囲気中で熱処理することで、圧縮成形時に合金粉末表面の絶縁層が破れたところに酸化層（アルミナ）を形成して、低いコア損失で良好な直流重畳特性を持つ複合磁性材料が得られるとしている。
特許文献２には、金属磁性体粒子を主成分とし、ガラスを含有する金属磁性体ペーストを用いて形成される金属磁性体層と、銀等の金属を含有する導体ペーストを用いて形成される導体パターンを積層して、積層体内にコイルパターンが形成された積層型電子部品、そして、この積層型電子部品は窒素雰囲気中において４００℃以上の温度で焼成されていることが記載されている。
Conventionally, as a magnetic core of a choke coil used at a high frequency, a ferrite core, a cut core of a thin metal plate, or a dust core has been used.
Compared to ferrite, the use of a metal magnetic material has an advantage of obtaining a high saturation magnetic flux density. On the other hand, since the metal magnetic body itself has low insulation, it is necessary to perform insulation treatment.
Patent Document 1 proposes that a mixture of Fe-Al-Si powder having a surface oxide film and a binder is subjected to heat treatment in an oxidizing atmosphere after compression molding. According to the patent document, by performing heat treatment in an oxidizing atmosphere, an oxide layer (alumina) is formed where the insulating layer on the surface of the alloy powder is broken during compression molding, and good DC superposition characteristics with low core loss. It is said that a composite magnetic material having
Patent Document 2 is formed using a metal magnetic material layer formed using a metal magnetic material paste containing metal magnetic particles as a main component and glass, and a conductor paste containing a metal such as silver. It is described that a laminated electronic component in which a conductor pattern is laminated and a coil pattern is formed in the laminated body, and that this laminated electronic component is fired at a temperature of 400 ° C. or higher in a nitrogen atmosphere.
特許文献１の複合磁性材料では、あらかじめ表面に酸化被膜を形成したＦｅ−Ａｌ−Ｓｉ粉末を使用して成形を行うので、圧縮成形時には大きな圧力が必要であった。
また、パワーインダクタのような、より大きな電流を流す必要がある電子部品に適用する場合においては、さらなる小型化に十分応えられるものではない、という課題があった。
また、特許文献２の積層型電子部品では、金属磁性体粒子を均一にガラス被覆する制御が必要であり、窒素雰囲気を利用しなければならず、生産コストが上がる課題があった。
In the composite magnetic material of Patent Document 1, since molding is performed using Fe—Al—Si powder having an oxide film formed on the surface in advance, a large pressure is required at the time of compression molding.
In addition, when applied to an electronic component such as a power inductor that needs to pass a larger current, there is a problem that it cannot sufficiently meet further downsizing.
Moreover, in the multilayer electronic component of Patent Document 2, it is necessary to control the metal magnetic particles to be uniformly coated with glass, and a nitrogen atmosphere must be used, which increases the production cost.
本発明は、上記の事情に鑑みてなされたものであって、低コストにて生産することができ、かつ、高い透磁率と高い飽和磁束密度の両方の特性を兼ね備えた磁性体を備えたコイル型電子部品及びその製造方法を提供するものである。 The present invention has been made in view of the above circumstances, and can be produced at low cost, and a coil including a magnetic body having both characteristics of high magnetic permeability and high saturation magnetic flux density A mold electronic component and a manufacturing method thereof are provided.
本発明者らは、上記目的を達成すべく鋭意研究を重ねた結果、鉄、ケイ素および鉄より酸化しやすい元素を含有する軟磁性合金の粒子と結合材とを混合して成形し、その成形体を酸素雰囲気で熱処理して結合材を分解させ、軟磁性合金の粒子の表面を酸化させ酸化層を形成させると、熱処理前の透磁率よりも熱処理後の透磁率が高くなるという現象を見出した。そして、その熱処理した成形体は酸化層を介して軟磁性合金の粒子同士が結合されていることが見出された。 As a result of intensive studies to achieve the above object, the inventors of the present invention mixed and molded soft magnetic alloy particles containing iron, silicon, and an element that is easier to oxidize than iron and a binder. When the body is heat-treated in an oxygen atmosphere to decompose the binder, and the surface of the soft magnetic alloy particles is oxidized to form an oxide layer, the magnetic permeability after heat treatment becomes higher than the magnetic permeability before heat treatment. It was. Then, it was found that the heat-treated molded body had soft magnetic alloy particles bonded together through an oxide layer.
本発明は、これらの知見に基づいて完成に至ったものであり、以下のとおりのものである。
（１）素体の内部あるいは表面にコイルを有するコイル型電子部品であって、
素体は、鉄、ケイ素および鉄より酸化しやすい元素を含有する軟磁性合金の粒子（「合金粒子」、「軟磁性体粒子」ともいう）群から構成され、各軟磁性合金粒子の表面には当該粒子を酸化して形成した酸化層が生成され、当該酸化層は当該合金粒子に比較して鉄より酸化しやすい元素を多く含み、粒子同士は当該酸化層を介して結合されており、かつ前記粒子同士を結合している前記酸化層は同一の相であることを特徴とするコイル型電子部品。
（２）軟磁性体粒子同士を結合する部分の酸化層の厚みは、結合に関与しない軟磁性体粒子表面の酸化層よりも厚いことを特徴とする（１）に記載のコイル型電子部品。
（３）軟磁性体粒子同士を結合する部分の酸化層の厚みは、結合に関与しない軟磁性体粒子表面の酸化層よりも薄いことを特徴とする（１）に記載のコイル型電子部品。
（４）軟磁性体粒子のうち少なくとも一部は５０ｎｍ以上の厚さをもつ酸化層を有する粒子であることを特徴とする（１）または（２）に記載のコイル型電子部品。
（５）前記鉄より酸化しやすい元素は、クロムであることを特徴とする（１）から（４）のいずれか１つに記載のコイル型電子部品。
（６）前記軟磁性合金は、クロム２〜８ｗｔ％、ケイ素１．５〜７ｗｔ％、鉄８８〜９６．５ｗｔ％の組成であることを特徴とする（５）に記載のコイル型電子部品。
（７）前記鉄より酸化しやすい元素は、アルミニウムであることを特徴とする（１）から（４）のいずれか１つに記載のコイル型電子部品。
（８）前記軟磁性合金は、アルミニウム２〜８ｗｔ％、ケイ素１．５〜１２ｗｔ％、鉄８０〜９６．５ｗｔ％の組成であることを特徴とする（７）に記載のコイル型電子部品。
（９）軟磁性体粒子の算術平均粒径は、３０μｍ以下であることを特徴とする（１）から（８）のいずれか１つに記載のコイル型電子部品。
（１０）前記酸化層は、前記軟磁性体粒子側から見て外側に向かって、
前記鉄成分の含有量が低下し、且、前記酸化しやすい元素の含有量が増加する第一の酸化層と、
前記鉄成分の含有量が増加し、且、前記酸化しやすい元素の含有量が低下する第二の酸化層と、
をこの順番でこの順番で含むことを特徴とする（１）から（９）のいずれか１つに記載のコイル型電子部品。
（１１）前記軟磁性体粒子側から見て外側に向かって、
前記第一の酸化層にて、前記ケイ素の含有量について変曲点を有することを特徴とする（１０）に記載のコイル型電子部品。
（１２）走査型電子顕微鏡を用いたエネルギー分散型Ｘ線分析によるＺＡＦ法で算出した鉄に対する酸化しやすい元素のピーク強度比が前記粒子における鉄に対する酸化しやすい元素のピーク強度比よりも大きい酸化層であることを特徴とする（１）から（１１）のいずれか１つに記載のコイル型電子部品。
（１３）前記コイルは、その端部が前記素体の表面に形成された導体膜と電気的に接続されていることを特徴とする（１）から（１２）のいずれか１つに記載のコイル型電子部品。
（１４）前記コイルが、素体の内部に形成されたコイル導体であることを特徴とする（１）から（１３）のいずれか１つのコイル型電子部品。
（１５）コイル導体は、導体パターンであり、素体と同時に焼成された導体であることを特徴とする（１４）記載のコイル型電子部品。
（１６）当該酸化層における鉄に比較して酸化しやすい金属は、クロムであることを特徴とする（１４）または（１５）のコイル型電子部品。
（１７）当該酸化層における鉄に比較して酸化しやすい金属は、アルミニウムであることを特徴とする（１４）または（１５）のコイル型電子部品。
（１８）素体にコイルが設けられたコイル型電子部品の製造方法において、
バインダーと、鉄、ケイ素および鉄より酸化しやすい元素を含有する軟磁性合金粒子との混合物をプレスして成形体を得る工程と、
前記成形体を酸素を含む雰囲気で熱処理して、前記軟磁性合金粒子の表面に酸化層を形成し前記軟磁性合金粒子同士を酸化層を介して結合させて素体を得る工程と、
前記素体にコイルおよび外部取り出し用の電極を設ける工程と、
を含むコイル型電子部品の製造方法。
（１９）素体にコイルが設けられたコイル型電子部品の製造方法において、
バインダーと、鉄、ケイ素および鉄より酸化しやすい元素を含有する軟磁性合金粒子との混合物をシート状に加工し、
当該シートにコイル用導電パターンを形成して積層し成形体を得る工程と、
前記成形体を酸素を含む雰囲気で熱処理して、前記軟磁性合金粒子の表面に酸化層を形成し、前記軟磁性合金粒子同士を酸化層を介して結合させて内部にコイルを有する素体を得る工程と、
前記素体に外部取り出し用の電極を設ける工程と、
を含むコイル型電子部品の製造方法。
（２０）前記酸素雰囲気が大気雰囲気であることを特徴とする（１８）または（１９）に記載のコイル型電子部品の製造方法。
The present invention has been completed based on these findings, and is as follows.
(1) A coil-type electronic component having a coil inside or on the surface of an element body,
The element body is composed of a group of soft magnetic alloy particles (also referred to as “alloy particles” or “soft magnetic particles”) containing elements that are more easily oxidized than iron, silicon, and iron, and is formed on the surface of each soft magnetic alloy particle. Produces an oxide layer formed by oxidizing the particles, the oxide layer contains more elements that are easier to oxidize than iron compared to the alloy particles, and the particles are bonded via the oxide layer, And the said oxide layer which has couple | bonded the said particle | grains is the same phase, The coil type electronic component characterized by the above-mentioned.
(2) The coil-type electronic component according to (1), wherein the thickness of the oxide layer at the portion where the soft magnetic particles are bonded to each other is thicker than the oxide layer on the surface of the soft magnetic particles not related to bonding.
(3) The coil-type electronic component according to (1), wherein the thickness of the oxide layer at the portion where soft magnetic particles are bonded to each other is thinner than the oxide layer on the surface of the soft magnetic particles not related to bonding.
(4) The coil-type electronic component according to (1) or (2), wherein at least a part of the soft magnetic particles is a particle having an oxide layer having a thickness of 50 nm or more.
(5) The coil-type electronic component according to any one of (1) to (4), wherein the element that is more easily oxidized than iron is chromium.
(6) The coil-type electronic component according to (5), wherein the soft magnetic alloy has a composition of 2-8 wt% chromium, 1.5-7 wt% silicon, and 88-96.5 wt% iron.
(7) The coil-type electronic component according to any one of (1) to (4), wherein the element that is more easily oxidized than iron is aluminum.
(8) The coil-type electronic component according to (7), wherein the soft magnetic alloy has a composition of aluminum 2 to 8 wt%, silicon 1.5 to 12 wt%, and iron 80 to 96.5 wt%.
(9) The arithmetic average particle diameter of the soft magnetic particles is 30 μm or less. The coil-type electronic component according to any one of (1) to (8),
(10) The oxide layer is outward as seen from the soft magnetic particle side.
A first oxide layer in which the content of the iron component decreases and the content of the easily oxidizable element increases;
A second oxide layer in which the content of the iron component is increased and the content of the easily oxidizable element is decreased;
Are included in this order in this order. The coil-type electronic component according to any one of (1) to (9).
(11) Toward the outside as viewed from the soft magnetic particle side,
The coil-type electronic component according to (10), wherein the first oxide layer has an inflection point with respect to the silicon content.
(12) An oxidation in which the peak intensity ratio of the easily oxidizable element to iron calculated by the ZAF method by energy dispersive X-ray analysis using a scanning electron microscope is larger than the peak intensity ratio of the easily oxidizable element to iron in the particles The coil-type electronic component according to any one of (1) to (11), wherein the coil-type electronic component is a layer.
(13) The coil according to any one of (1) to (12), wherein an end portion of the coil is electrically connected to a conductor film formed on a surface of the element body. Coil type electronic components.
(14) The coil-type electronic component according to any one of (1) to (13), wherein the coil is a coil conductor formed inside the element body.
(15) The coil-type electronic component according to (14), wherein the coil conductor is a conductor pattern and is a conductor fired simultaneously with the element body.
(16) The coil-type electronic component according to (14) or (15), wherein the metal that is more easily oxidized than iron in the oxide layer is chromium.
(17) The coil-type electronic component according to (14) or (15), wherein the metal that is more easily oxidized than iron in the oxide layer is aluminum.
(18) In a method for manufacturing a coil-type electronic component in which a coil is provided on an element body,
A step of pressing a mixture of a binder and soft magnetic alloy particles containing iron, silicon, and an element more easily oxidized than iron to obtain a molded body,
Heat treating the compact in an atmosphere containing oxygen, forming an oxide layer on the surface of the soft magnetic alloy particles, and bonding the soft magnetic alloy particles to each other through the oxide layer to obtain an element body;
Providing the element with a coil and an electrode for external extraction;
A method of manufacturing a coil-type electronic component including:
(19) In a method for manufacturing a coil-type electronic component in which a coil is provided on an element body,
Processing a mixture of a binder and soft magnetic alloy particles containing iron, silicon, and an element that is easier to oxidize than iron into a sheet,
Forming a conductive pattern for a coil on the sheet and laminating it to obtain a molded body; and
The molded body is heat-treated in an atmosphere containing oxygen to form an oxide layer on the surface of the soft magnetic alloy particles, and the soft magnetic alloy particles are bonded to each other through the oxide layer to form an element body having a coil inside. Obtaining a step;
Providing an electrode for external extraction on the element;
A method of manufacturing a coil-type electronic component including:
(20) The method for manufacturing a coil-type electronic component according to (18) or (19), wherein the oxygen atmosphere is an air atmosphere.
本発明によれば、各軟磁性体粒子の絶縁層として、当該粒子を酸化して形成した酸化層を用いているので、絶縁のために、樹脂、ガラスを軟磁性体粒子に混合する必要がない。また、あらかじめ表面に酸化処理したＦｅ−Ａｌ−Ｓｉ粉末と比較して、成形時に大きな圧力をかける必要がない。そのため、低コストにて生産することができ、かつ、高い透磁率と高い飽和磁束密度の両方の特性を兼ね備えた磁性体を得ることができる。 According to the present invention, since an oxide layer formed by oxidizing the particles is used as the insulating layer of each soft magnetic particle, it is necessary to mix resin and glass with the soft magnetic particles for insulation. Absent. Moreover, it is not necessary to apply a large pressure at the time of molding as compared with Fe-Al-Si powder whose surface is previously oxidized. Therefore, it is possible to obtain a magnetic body that can be produced at low cost and has both high magnetic permeability and high saturation magnetic flux density.
本明細書において「粒子を酸化して形成した酸化層」は粒子の自然酸化以上の酸化反応により形成された酸化層であり、粒子による成形体を酸化性雰囲気で熱処理することにより粒子の表面と酸素とを反応させ成長させた酸化層をいう。なお、「層」は組成上、構造上、物性上、外観上、及び／又は製造工程上等によりほかと識別できる層であり、その境界は明確であるもの、明確でないものを含み、また、粒子上で連続膜であるもの、一部に非連続部分を有するものを含むものである。ある態様では、「酸化層」は粒子全体を被覆する連続酸化膜である。また、このような酸化層は本明細書で特定されるいずれかの特徴を有するものであり、粒子の表面の酸化反応により成長した酸化層は、別の方法により被覆された酸化膜層と識別され得るものである。また、本明細書において「より多い」、「よりし易い」等比較を表す表現は実質的な差異を意味し、機能、構造、作用効果において有意な差異を奏する程度の差異を意味する。
以下、本発明の電子部品用軟磁性合金を用いた素体の第１の実施形態について、図１および図２を参照して説明する。
In the present specification, an “oxidized layer formed by oxidizing particles” is an oxidized layer formed by an oxidation reaction that is greater than the natural oxidation of the particles. An oxide layer grown by reacting with oxygen. In addition, “layer” is a layer that can be distinguished from others by composition, structure, physical properties, appearance, and / or manufacturing process, etc., and includes boundaries that are clear and unclear, Including those that are continuous films on the particles and those that have discontinuous portions in part. In some embodiments, the “oxide layer” is a continuous oxide film that covers the entire particle. In addition, such an oxide layer has any of the characteristics specified in this specification, and an oxide layer grown by an oxidation reaction on the surface of the particle is distinguished from an oxide film layer coated by another method. It can be done. In the present specification, expressions representing comparisons such as “more” and “easy to do” mean substantial differences, and mean differences that exhibit significant differences in function, structure, and effect.
Hereinafter, a first embodiment of an element body using the soft magnetic alloy for electronic parts of the present invention will be described with reference to FIGS. 1 and 2.
図１は、本実施形態の電子部品用軟磁性合金を用いた素体１０の外観を示す側面図である。
本実施形態の電子部品用軟磁性合金を用いた素体１０は、巻線型チップインダクタのコイルを巻回するためのコアとして用いられるものである。ドラム型のコア１１は、回路基板等の実装面に並行に配設されコイルを巻回するための板状の巻芯部１１ａと、巻芯部１１ａの互いに対向する端部にそれぞれ配設された一対の鍔部１１ｂ、１１ｂを備え、外観はドラム型を呈する。コイルの端部は、鍔部１１ｂ、１１ｂの表面に形成された外部導体膜１４に電気的に接続されている。
本実施形態の電子部品用軟磁性合金を用いた素体１０は、鉄（Ｆｅ）、ケイ素（Ｓｉ）および鉄より酸化しやすい元素を含有する軟磁性合金の粒子群から構成され、各軟磁性体粒子の表面は当該粒子が酸化した酸化層が形成され、当該酸化層は当該合金粒子に比較してクロムを多く含み、粒子同士は、当該酸化層を介して結合されていること特徴とする。
以下の記載は、元素名または、元素記号にて記す。
FIG. 1 is a side view showing an external appearance of an element body 10 using a soft magnetic alloy for electronic parts according to the present embodiment.
The element body 10 using the soft magnetic alloy for electronic parts of the present embodiment is used as a core for winding a coil of a wire-wound chip inductor. The drum-shaped core 11 is disposed in parallel with a mounting surface of a circuit board or the like, and is disposed at a plate-shaped core portion 11a for winding a coil, and opposite ends of the core portion 11a. A pair of flanges 11b and 11b are provided, and the appearance is drum-shaped. The end of the coil is electrically connected to the outer conductor film 14 formed on the surface of the flanges 11b and 11b.
The element body 10 using the soft magnetic alloy for electronic parts of the present embodiment is composed of particles of soft magnetic alloy containing iron (Fe), silicon (Si), and an element that is easier to oxidize than iron, and each soft magnetism. The surface of the body particles is formed with an oxide layer formed by oxidation of the particles, the oxide layer contains more chromium than the alloy particles, and the particles are bonded via the oxide layer. .
The following description is indicated by element names or element symbols.
図２は、本実施形態の電子部品用軟磁性合金を用いた素体１０の断面の拡大模式図であり、素体の厚さ方向の断面をＳＥＭ（走査型電子顕微鏡）を用いて３０００倍で撮影して得られた組成像に基づいて作成したものである。
上記の模式図における複数の粒子、および酸化層の識別は、以下のようにして行うことができる。まず、素体の中心を通る厚さ方向の断面が露出するように研磨し、得られた断面について、走査型電子顕微鏡（ＳＥＭ）を用いて３０００倍で撮影して組成像を得る。
走査型電子顕微鏡（ＳＥＭ）では、構成元素の違いにより、組成像にコントラスト（明度）の違いとして表れる。
次に、上記で得られた組成像について、各画素を３段階の明度ランクに分類する。明度ランクは、上記組成像中で粒子の断面の輪郭がすべて確認できる粒子のうち、各粒子の断面の長軸寸法ｄ１と短軸寸法ｄ２の単純平均Ｄ＝（ｄ１＋ｄ２）／２が原料粒子（酸化層が形成されていない原料としての合金粒子）の平均粒径（ｄ５０％）より大きい粒子の組成コントラストを中心明度ランクとし、上記組成像中でこの明度ランクに該当する部分は粒子１と判断することができる。また、組成コントラストが上記中心明度ランクより暗い明度ランクの部分は酸化層２と判断することができる。なお、望ましくは、複数測定する。
また、上記中心明度ランクより明るい明度ランクの部分は空孔３と判断することができる。
酸化層２の厚みの測定は、粒子と酸化層２の境界面から、酸化層２と空孔３との境界面までの最短距離を酸化層２の厚みとすることにて、求めることができる。
FIG. 2 is an enlarged schematic view of a cross section of the element body 10 using the soft magnetic alloy for electronic parts of the present embodiment. A cross section in the thickness direction of the element body is 3000 times using a SEM (scanning electron microscope). It was created based on the composition image obtained by photographing at 1.
The plurality of particles and the oxide layer in the above schematic diagram can be identified as follows. First, it polishes so that the cross section of the thickness direction which passes the center of an element | base_body may be exposed, and it image | photographs 3000 times using a scanning electron microscope (SEM) about the obtained cross section, and obtains a composition image.
In a scanning electron microscope (SEM), the composition image shows a difference in contrast (brightness) due to a difference in constituent elements.
Next, for the composition image obtained above, each pixel is classified into three levels of brightness ranks. In the lightness rank, among the particles in which the outline of the cross section of each particle can be confirmed in the composition image, the simple average D = (d1 + d2) / 2 of the major axis dimension d1 and minor axis dimension d2 of each particle cross section is the raw material particle ( The composition contrast of the particles larger than the average particle diameter (d50%) of the alloy particles as the raw material on which the oxide layer is not formed) is set as the central brightness rank, and the portion corresponding to this brightness rank in the composition image is determined as the particle 1 can do. Further, the portion of the lightness rank where the composition contrast is darker than the central lightness rank can be determined as the oxide layer 2. Preferably, a plurality of measurements are performed.
Further, the portion of the lightness rank brighter than the central lightness rank can be determined as the hole 3.
The thickness of the oxide layer 2 can be measured by setting the shortest distance from the boundary surface between the particle and the oxide layer 2 to the boundary surface between the oxide layer 2 and the void 3 as the thickness of the oxide layer 2. .
酸化層２の厚みは、具体的には以下のように求めることができる。素体１０の厚さ方向の断面をＳＥＭ（走査型電子顕微鏡）を用いて１０００倍ないし３０００倍で撮影し、得られた組成像の１粒子について画像処理ソフトウェアを用いて重心を求め、その重心点から半径方向にＥＤＳ（エネルギー分散型X線分析装置）で線分析を行う。酸素濃度が重心点での酸素濃度の３倍以上の領域を酸化物と判定し（即ち、測定のブレを考慮し３倍を閾値としそれ未満は非酸化層と判定するということであり、実際の酸化層の酸素濃度は１００倍以上にもなり得る）、粒子外周部までを酸化層２の厚みとして測長する。ある態様においては、酸化層の領域は本明細書で記載するいずれかの方法（明度ランクによる識別法、酸素濃度による識別法、後述する組成比による識別法、ピーク強度比による識別法等）、あるいはその他酸素元素の存在（濃度）と関連付けられる公知のいずれかの方法から、適宜、評価方法を選択して画定することができる。
なお、ある態様では、酸化層を有する軟磁性体粒子の平均粒径は、原料粒子（成形、熱処理前の粒子）の平均粒径と実質的にあるいはほぼ同じである。
Specifically, the thickness of the oxide layer 2 can be obtained as follows. A cross section in the thickness direction of the element body 10 was photographed at 1000 to 3000 times using an SEM (scanning electron microscope), and the center of gravity of one particle of the obtained composition image was obtained using image processing software. A line analysis is performed in the radial direction from the point using an EDS (energy dispersive X-ray analyzer). A region where the oxygen concentration is at least three times the oxygen concentration at the center of gravity is determined as an oxide (that is, considering a measurement blur and a threshold value of three times is determined as a non-oxidized layer). The oxygen concentration of the oxide layer can be 100 times or more), and the length up to the outer periphery of the particle is measured as the thickness of the oxide layer 2. In some embodiments, the region of the oxide layer may be any of the methods described herein (identification method by lightness rank, identification method by oxygen concentration, identification method by composition ratio described later, identification method by peak intensity ratio, etc.), Alternatively, an evaluation method can be appropriately selected and defined from any known method associated with the presence (concentration) of other oxygen elements.
In some embodiments, the average particle diameter of the soft magnetic particles having an oxide layer is substantially or substantially the same as the average particle diameter of the raw material particles (particles before forming and heat treatment).
合金粒子の表面に形成された酸化層２の厚みは、１つの合金粒子においても、部分により異なる厚みとすることができる。
態様として、全体として、合金粒子表面の酸化層（空孔３に隣接する酸化層）よりも厚い酸化層で結合されている合金粒子同士とすることで、高強度の効果を得られる。
また別の態様として、全体として、合金粒子表面の酸化層（空孔３に隣接する酸化層）よりも薄い酸化層で結合されている合金粒子同士とすることで、高透磁率の効果を得られる。
さらに別の態様として少なくとも軟磁性体粒子群の一部は、５０ｎｍ以上の厚さをもつ酸化層（表面酸化層として）を部分的に有する粒子である。
本発明において、前記粒子同士を結合している前記酸化層は、同一の相である。同一の相とは、粒子間の酸化層中に空隙が実質的に無く（酸化層が隣接する空孔以外には）同一の結晶より構成され連続的に結合していることであり、透過型電子顕微鏡（ＴＥＭ）により確認することができる。また、結晶の構造は、図４に示すようにＸ線回折分析装置により確認することができる。
酸化層の構造、組成、厚み等は、後述するように、原料粒子の組成、粒子間の距離（充填率）、熱処理温度、熱処理時間、熱処理雰囲気中の酸素量等により制御することができる。酸化層の厚みは、粒子間でもばらつくが、ある態様では、実質的に全ての或いはほとんどの酸化層は１０〜２００ｎｍの範囲で厚みを有する。
別の態様として、前記酸化層は、前記合金粒子側から見て、前記鉄成分の含有量が低下し、且、前記酸化しやすい元素の含有量が増加する第一の酸化層と、前記鉄成分の含有量が低下し、且、前記酸化しやすい元素の含有量が低下する第二の酸化層と、を含むことが好ましい。
さらに、前記合金粒子側から見て、前記第一の酸化層にて、前記クロム（Ｃｒ）の含有量について変曲点（すなわち、含有量の変化を示す線の傾きがゼロの点）を有することがより好ましい。なお、第一の酸化層と第二の酸化層との境界は明瞭でもよいし、曖昧でもよい。
この構造は、図５に示すようにＥＤＳ（エネルギー分散型X線分析装置）にて確認でき、飽和磁束密度の低下を抑制する効果が得られる。
The thickness of the oxide layer 2 formed on the surface of the alloy particles can be different depending on the part even in one alloy particle.
As an aspect, a high-strength effect can be obtained by making the alloy particles bonded together by an oxide layer thicker than the oxide layer on the surface of the alloy particles (the oxide layer adjacent to the holes 3).
Moreover, as another aspect, the effect of high magnetic permeability is obtained by making the alloy particles bonded together by an oxide layer thinner than the oxide layer on the surface of the alloy particles (the oxide layer adjacent to the holes 3) as a whole. It is done.
In still another embodiment, at least a part of the soft magnetic particle group is a particle partially having an oxide layer (as a surface oxide layer) having a thickness of 50 nm or more.
In the present invention, the oxide layers bonding the particles are in the same phase. The same phase means that the oxide layer between particles is substantially free of voids (other than the adjacent voids of the oxide layer) and is composed of the same crystal and is continuously bonded. This can be confirmed with an electron microscope (TEM). The crystal structure can be confirmed by an X-ray diffraction analyzer as shown in FIG.
As will be described later, the structure, composition, thickness, and the like of the oxide layer can be controlled by the composition of the raw material particles, the distance between the particles (filling rate), the heat treatment temperature, the heat treatment time, the amount of oxygen in the heat treatment atmosphere, and the like. The thickness of the oxide layer varies between particles, but in some embodiments, substantially all or most of the oxide layer has a thickness in the range of 10-200 nm.
As another aspect, the oxide layer includes a first oxide layer in which the content of the iron component is reduced and the content of the easily oxidizable element is increased as viewed from the alloy particle side, and the iron It is preferable to include a second oxide layer in which the content of the component is reduced and the content of the easily oxidizable element is reduced.
Furthermore, when viewed from the alloy particle side, the first oxide layer has an inflection point (that is, a point where the slope of the line indicating the change in content is zero) with respect to the chromium (Cr) content. It is more preferable. The boundary between the first oxide layer and the second oxide layer may be clear or ambiguous.
This structure can be confirmed with an EDS (energy dispersive X-ray analyzer) as shown in FIG. 5, and an effect of suppressing a decrease in saturation magnetic flux density is obtained.
上記電子部品用軟磁性合金を用いた素体における粒子の組成比は次のようにして確認することができる。まず、原料粒子を粒子の中心を通る断面が露出するように研磨し、得られた断面を走査型電子顕微鏡（ＳＥＭ）を用いて３０００倍で撮影した組成像について、粒子の中心付近の１μｍ□の組成をエネルギー分散型Ｘ線分析（ＥＤＳ）によりＺＡＦ法で算出する。次に、上記電子部品用軟磁性合金素体のほぼ中心を通る厚さ方向の断面が露出するように研磨し、得られた断面を走査型電子顕微鏡（ＳＥＭ）を用いて３０００倍で撮影した組成像中から、粒子の断面の輪郭がすべて確認できる粒子のうち各粒子の断面の長軸寸法ｄ１と短軸寸法ｄ２の単純平均Ｄ＝（ｄ１＋ｄ２）／２が原料粒子の平均粒径（ｄ５０％）より大きい粒子を抽出し、その長軸と短軸の交点付近の１μｍ□の組成をエネルギー分散型Ｘ線分析（ＥＤＳ）によりＺＡＦ法で算出し、これを上記原料粒子における組成比と対比することで上記電子部品用軟磁性合金を用いた素体中の合金粒子の組成比を知ることができる（原料粒子の組成は公知であるためZAF法で算出された組成同士を比較することで素体中の合金粒子の組成を求めることができる）。
上記電子部品用軟磁性合金を用いた素体における酸化層の厚さは、上記方法で同定した粒子１，１の表面に存在する酸化層の粒子１の表面からの厚さの最厚部の厚さｔ１と最薄部の厚さｔ２の単純平均から求めた平均厚さＴ＝（ｔ１＋ｔ２）／２とした。
The composition ratio of the particles in the element body using the soft magnetic alloy for electronic parts can be confirmed as follows. First, a raw material particle is polished so that a cross section passing through the center of the particle is exposed, and a composition image obtained by photographing the obtained cross section at 3000 times using a scanning electron microscope (SEM) is 1 μm □ near the center of the particle. Is calculated by the ZAF method by energy dispersive X-ray analysis (EDS). Next, polishing was performed so that a cross section in the thickness direction passing through substantially the center of the soft magnetic alloy body for electronic parts was exposed, and the obtained cross section was photographed at 3000 times using a scanning electron microscope (SEM). Of the particles in which the outline of the cross section of each particle can be confirmed from the composition image, the simple average D = (d1 + d2) / 2 of the long axis dimension d1 and the short axis dimension d2 of each particle cross section is the average particle diameter (d50 %) Is extracted, and the composition of 1 μm □ near the intersection of the major axis and minor axis is calculated by energy dispersive X-ray analysis (EDS) by the ZAF method, and this is compared with the composition ratio in the raw material particles. By doing so, the composition ratio of the alloy particles in the element body using the above-mentioned soft magnetic alloy for electronic parts can be known (the composition of the raw material particles is known, so by comparing the compositions calculated by the ZAF method) Determine the composition of alloy particles in the element body You bet it is).
The thickness of the oxide layer in the element body using the soft magnetic alloy for electronic parts is the thickest part of the thickness of the oxide layer existing on the surface of the particles 1 and 1 identified by the above method from the surface of the particle 1. The average thickness T = (t1 + t2) / 2 obtained from a simple average of the thickness t1 and the thickness t2 of the thinnest part was used.
本発明の一つの態様として、酸化しやすい元素の例として、クロムの態様をあげる。
本実施形態の電子部品用軟磁性合金を用いた素体１０は、クロム２〜８ｗｔ％、ケイ素１．５〜７ｗｔ％、鉄８８〜９６．５ｗｔ％を含有する複数の粒子１，１と、粒子１の表面に生成された酸化層２を備える。酸化層２は、少なくとも鉄及びクロムを含み、透過型電子顕微鏡を用いたエネルギー分散型Ｘ線分析による鉄に対するクロムのピーク強度比Ｒ２が粒子における鉄に対するクロムのピーク強度比Ｒ１よりも実質的に大きい（例えばＲ２はＲ１の数倍以上、数十倍以上）。また、複数の粒子間には、空孔３が存在する箇所もある。
上記電子部品用軟磁性合金素体について、前記酸化層２における鉄に対するクロムのピーク強度比Ｒ２と、前記粒子１における鉄に対するクロムの強度比Ｒ１は、それぞれ次のようにして求めることができる。まず、上記組成像における粒子１の内部の長軸ｄ１と短軸ｄ２とが交わる点を中心とした１μｍ□の組成をＳＥＭ−ＥＤＳで求める。次に、上記組成像における粒子１の表面の酸化層２の最厚部の厚さｔ１と最薄部の厚さｔ２から平均厚さＴ＝（ｔ１＋ｔ２）／２に相当する酸化層厚さの部位における酸化層の厚さの中心点を中心とした１μｍ□の組成についてＳＥＭ−ＥＤＳで求める。そして、粒子１の内部における鉄の強度Ｃ１ＦｅＫａ、クロムの強度Ｃ１ＣｒＫａより、鉄に対するクロムのピーク強度比Ｒ１＝Ｃ１ＣｒＫａ／Ｃ１ＦｅＫａを求めることができる。また、酸化層２の厚さの中心点における鉄の強度Ｃ２ＦｅＫａ、クロムの強度Ｃ２ＣｒＫａより、鉄に対するクロムのピーク強度比Ｒ２＝Ｃ２ＣｒＫａ／Ｃ２ＦｅＫａを求めることができる。
One embodiment of the present invention is a chromium embodiment as an example of an easily oxidizable element.
The element body 10 using the soft magnetic alloy for electronic parts of the present embodiment includes a plurality of particles 1 and 1 containing 2 to 8 wt% chromium, 1.5 to 7 wt% silicon, and 88 to 96.5 wt% iron, An oxide layer 2 generated on the surface of the particle 1 is provided. The oxide layer 2 contains at least iron and chromium, and the peak intensity ratio R2 of chromium to iron by energy dispersive X-ray analysis using a transmission electron microscope is substantially larger than the peak intensity ratio R1 of chromium to iron in the particles. Large (for example, R2 is several times or more, several tens of times or more of R1). In addition, there are places where the pores 3 exist between the plurality of particles.
For the soft magnetic alloy body for electronic parts, the peak intensity ratio R2 of chromium to iron in the oxide layer 2 and the intensity ratio R1 of chromium to iron in the particles 1 can be determined as follows. First, a 1 μm square composition centering on the point where the major axis d1 and the minor axis d2 inside the particle 1 in the composition image intersect is obtained by SEM-EDS. Next, the oxide layer thickness corresponding to the average thickness T = (t1 + t2) / 2 from the thickness t1 and the thickness t2 of the thinnest portion of the oxide layer 2 on the surface of the particle 1 in the above composition image. The composition of 1 μm square centered on the center point of the thickness of the oxide layer at the site is determined by SEM-EDS. Then, it is possible to obtain strength C1 FeKa of iron in the interior of the particle 1, than the intensity C1 CrKa chromium, the peak intensity of the chromium to iron ratio R1 = C1 CrKa / C1 FeKa. Further , the chromium peak intensity ratio R2 = C2CrKa / C2FeKa can be obtained from the iron strength C2FeKa and the chromium strength C2CrKa at the center point of the thickness of the oxide layer 2.
また、本発明の電子部品用軟磁性合金を用いた素体において、隣接する粒子１，１の表面に生成された酸化層を介して結合されていることは、上記組成像に基づいて作成される図２に示されるような模式図より確認することができる。また、隣接する粒子１，１の表面に生成された酸化層を介して結合されていることは、電子部品用軟磁性合金を用いた素体の磁気特性、強度の向上として現れる。 In addition, in the element body using the soft magnetic alloy for electronic parts of the present invention, it is created based on the composition image that it is bonded to the surface of the adjacent particles 1 and 1 through the oxidized layer. It can be confirmed from the schematic diagram as shown in FIG. Further, the fact that they are bonded to the surfaces of adjacent particles 1 and 1 through an oxide layer appears as an improvement in the magnetic properties and strength of the element body using the soft magnetic alloy for electronic parts.
本発明の電子部品用軟磁性合金を用いた素体を製造するには、態様の一つとして、最初に、クロム、ケイ素、鉄含有する原料粒子に例えば熱可塑性樹脂などの結合剤を添加し、攪拌混合させて造粒物を得る。次に、この造粒物を圧縮成形して成形体を形成し、得られた成形体を大気中で４００〜９００℃で熱処理する。この大気中で熱処理を行うことで、混合した熱可塑性樹脂を脱脂するとともに、もともと粒子中に存在し熱処理により表面に移動してきたクロムと、粒子の主成分である鉄を酸素と結合させながら、金属酸化物からなる酸化層を粒子表面に生成させ、かつ隣接する粒子の表面の酸化層同士を結合させる。生成された酸化層（金属酸化物層）は、主にＦｅとクロムからなる酸化物であり、粒子間の絶縁を確保し電子部品用軟磁性合金を用いた素体を提供することができる。
原料粒子の例としては、水アトマイズ法で製造した粒子、原料粒子の形状の例として、球状、扁平状があげられる。
In order to produce an element body using the soft magnetic alloy for electronic parts of the present invention, as one embodiment, first, a binder such as a thermoplastic resin is added to raw material particles containing chromium, silicon, and iron. The mixture is stirred and mixed to obtain a granulated product. Next, this granulated product is compression molded to form a molded body, and the obtained molded body is heat-treated at 400 to 900 ° C. in the atmosphere. By performing heat treatment in the atmosphere, the mixed thermoplastic resin is degreased, while chromium that originally existed in the particles and moved to the surface by the heat treatment, and iron, which is the main component of the particles, are combined with oxygen, An oxide layer made of a metal oxide is formed on the particle surface, and the oxide layers on the surfaces of adjacent particles are bonded to each other. The generated oxide layer (metal oxide layer) is an oxide mainly composed of Fe and chromium, and can provide an element body using a soft magnetic alloy for electronic parts while ensuring insulation between particles.
Examples of the raw material particles include particles produced by the water atomization method, and examples of the shape of the raw material particles include a spherical shape and a flat shape.
本発明において、酸素雰囲気下にて熱処理温度をあげると結合剤は分解し、軟磁性合金体は酸化される。このため、成形体の熱処理条件として、大気中、４００〜９００℃で、１分以上保持することが好ましい。この温度範囲内で熱処理を行うことで、優れた酸化層を形成することができる。より好ましくは、６００〜８００℃である。大気中以外の条件、例えば、酸素分圧が大気と同程度の雰囲気中で熱処理してもよい。還元雰囲気又は非酸化雰囲気では、熱処理により金属酸化物からなる酸化層の生成が行われないため、粒子同士が燒結し体積抵抗率は著しく低下する。
雰囲気中の酸素濃度、水蒸気量については特に限定されないが、生産面から考慮すると、大気あるいは乾燥空気であることが望ましい。
熱処理温度が４００℃を越えると優れた強度と優れた体積抵抗率を得ることができる。
一方、熱処理温度が、９００℃を超えると、強度は増加するものの、体積抵抗率の低下が発生する。
上記熱処理温度中の保持時間は、１分以上とすることによりＦｅとクロムを含む金属酸化物からなる酸化層が生成されやすい。酸化層厚は一定値で飽和するため保持時間の上限はあえて設定しないが、生産性を考慮し２時間以下とすることが妥当である。
以上のとおり、熱処理条件を、上記範囲とすることで優れた強度と優れた体積抵抗率を同時に満たし、酸化層を有する軟磁性合金を用いた素体とすることができる。
つまり、熱処理温度、熱処理時間、熱処理雰囲気中の酸素量等により、酸化層の形成を制御している。
In the present invention, when the heat treatment temperature is raised in an oxygen atmosphere, the binder is decomposed and the soft magnetic alloy body is oxidized. For this reason, it is preferable to hold | maintain for 1 minute or more at 400-900 degreeC in air | atmosphere as the heat processing conditions of a molded object. By performing heat treatment within this temperature range, an excellent oxide layer can be formed. More preferably, it is 600-800 degreeC. You may heat-process in conditions other than air | atmosphere, for example, the atmosphere whose oxygen partial pressure is comparable as air | atmosphere. In a reducing atmosphere or a non-oxidizing atmosphere, an oxide layer made of a metal oxide is not generated by heat treatment, so that the particles are sintered together and the volume resistivity is remarkably lowered.
The oxygen concentration and the amount of water vapor in the atmosphere are not particularly limited, but in consideration of production, air or dry air is desirable.
When the heat treatment temperature exceeds 400 ° C., excellent strength and excellent volume resistivity can be obtained.
On the other hand, when the heat treatment temperature exceeds 900 ° C., the strength increases but the volume resistivity decreases.
When the holding time during the heat treatment temperature is 1 minute or longer, an oxide layer made of a metal oxide containing Fe and chromium is likely to be generated. Since the oxide layer thickness saturates at a constant value, the upper limit of the holding time is not set, but considering the productivity, it is appropriate to set it to 2 hours or less.
As described above, by setting the heat treatment condition within the above range, it is possible to obtain an element body using a soft magnetic alloy having both an excellent strength and an excellent volume resistivity and having an oxide layer.
That is, the formation of the oxide layer is controlled by the heat treatment temperature, the heat treatment time, the amount of oxygen in the heat treatment atmosphere, and the like.
本発明の電子部品用軟磁性合金素体においては、上記の処理を鉄−ケイ素−鉄よりも酸化しやすい元素の合金粉に適用することで、高い透磁率と高い飽和磁束密度とを得ることができる。そして、この高い透磁率により、従来に比べてより小型の軟磁性合金素体でより大きい電流を流すことが可能な電子部品を得ることができる。
そして、軟磁性合金の粒子を樹脂またはガラスで結合させたコイル部品と異なり、樹脂もガラスも使わず、大きな圧力をかけて成形することもないので低コストにて生産することができる。
また、本実施形態の電子部品用軟磁性合金素体においては、高い飽和磁束密度を維持しつつ、大気中の熱処理後においても、素体表面へのガラス成分等の浮き出しが防止され、高い寸法安定性を有する小型のチップ状電子部品を提供することができる。
In the soft magnetic alloy body for electronic parts of the present invention, high magnetic permeability and high saturation magnetic flux density are obtained by applying the above treatment to an alloy powder of an element that is more easily oxidized than iron-silicon-iron. Can do. And by this high magnetic permeability, it is possible to obtain an electronic component that allows a larger current to flow with a smaller soft magnetic alloy body than in the prior art.
Unlike a coil component in which soft magnetic alloy particles are bonded with resin or glass, neither resin nor glass is used, and molding is not performed with a large pressure, so that it can be produced at low cost.
Further, in the soft magnetic alloy element body for electronic parts of the present embodiment, the glass component and the like are prevented from being raised on the surface of the element body even after heat treatment in the atmosphere while maintaining a high saturation magnetic flux density. A small chip-like electronic component having stability can be provided.
次に、本発明の電子部品の第１の実施形態について、図１、図２、図６および図７を参照して説明する。図１および図２は先の電子部品用軟磁性合金素体の実施形態と重複するので説明を省略する。図６は、本実施形態の電子部品を示す一部を透視した側面図である。また、図７は、本実施形態の電子部品の内部構造を示す縦断面図である。本実施形態の電子部品２０は、コイル型電子部品として巻線型チップインダクタである。上述した電子部品用軟磁性合金を用いた素体１０であるドラム型のコア１１と、前記素体１０からなり、ドラム型のコア１１の両鍔部１１ｂ、１１ｂ間をそれぞれ連結する図示省略した一対の板状コア１２，１２を有する。コア１１の鍔部１１ｂ、１１ｂの実装面には一対の外部導体膜１４，１４がそれぞれ形成されている。また、コア１１の巻芯部１１ａには絶縁被覆導線からなるコイル１５が巻回されて巻回部１５ａが形成されるとともに、両端部１５ｂ、１５ｂが鍔部１１ｂ、１１ｂの実装面の外部導体膜１４，１４にそれぞれ熱圧着接合されている。外部導体膜１４，１４は、素体１０の表面に形成された焼付導体層１４ａと、この焼付導体層１４ａ上に積層形成されたＮｉメッキ層１４ｂ、およびＳｎメッキ層１４ｃを備える。上述した板状コア１２，１２は、樹脂系接着剤によりドラム型のコア１１の鍔部１１ｂ、１１ｂに接着されている。 Next, a first embodiment of the electronic component of the present invention will be described with reference to FIGS. 1, 2, 6 and 7. Since FIG. 1 and FIG. 2 overlap with the previous embodiment of the soft magnetic alloy body for electronic parts, description thereof will be omitted. FIG. 6 is a side view illustrating a part of the electronic component of the present embodiment. FIG. 7 is a longitudinal sectional view showing the internal structure of the electronic component of the present embodiment. The electronic component 20 of this embodiment is a wire-wound chip inductor as a coil-type electronic component. A drum-type core 11 that is an element body 10 using the above-described soft magnetic alloy for electronic parts, and the both ends 11b and 11b of the drum-type core 11 are connected to each other and are not shown. It has a pair of plate-like cores 12 and 12. A pair of outer conductor films 14 and 14 are formed on the mounting surfaces of the flange portions 11b and 11b of the core 11, respectively. In addition, a coil 15 made of an insulating coated conductor is wound around the core portion 11a of the core 11 to form a winding portion 15a, and both end portions 15b and 15b are external conductors on the mounting surface of the flange portions 11b and 11b. The membranes 14 and 14 are thermocompression bonded respectively. The external conductor films 14 and 14 include a baked conductor layer 14 a formed on the surface of the element body 10, a Ni plated layer 14 b and a Sn plated layer 14 c stacked on the baked conductor layer 14 a. The plate-like cores 12 and 12 described above are bonded to the flanges 11b and 11b of the drum-type core 11 with a resin adhesive.
本実施形態の電子部品２０は、クロム、ケイ素、鉄を含有する複数の粒子と、該粒子の表面に生成され、少なくとも鉄及びクロムを含み、走査型電子顕微鏡を用いたエネルギー分散型Ｘ線分析によりＺＡＦ法で算出した鉄に対するクロムのピーク強度比が前記粒子における鉄に対するクロムのピーク強度比よりも大きい酸化層と、を備え、隣接する前記粒子の表面に生成された酸化層同士が結合されている上述した電子部品用軟磁性合金を用いた素体１０をコア１１として備える。また、素体１０の表面には、少なくとも一対の外部導体膜１４，１４が形成されている。本実施形態の電子部品２０における電子部品用軟磁性合金を用いた素体１０については上述と重複するので説明を省略する。 The electronic component 20 of the present embodiment includes a plurality of particles containing chromium, silicon, and iron, and is generated on the surface of the particles and includes at least iron and chromium, and energy dispersive X-ray analysis using a scanning electron microscope And an oxide layer in which the peak intensity ratio of chromium to iron calculated by the ZAF method is larger than the peak intensity ratio of chromium to iron in the particles, and the oxide layers generated on the surfaces of the adjacent particles are bonded to each other. An element body 10 using the above-described soft magnetic alloy for electronic parts is provided as a core 11. Further, at least a pair of external conductor films 14 and 14 are formed on the surface of the element body 10. Since the element body 10 using the soft magnetic alloy for electronic components in the electronic component 20 of the present embodiment overlaps with the above description, the description thereof is omitted.
コア１１は、少なくとも巻芯部１１ａを有し、巻芯部１１ａの断面の形状は、板状（長方形）、円形、楕円をとることができる。
さらに、前記巻芯部１１ａの端部に少なくとも鍔部１１を有することが好ましい。
鍔部１１があると、巻芯部１１ａに対するコイルの位置を鍔部１１で制御しやすくなり、インダクタンスなどの特性が安定する。
コア１１の態様は、一つの鍔を有する態様、二つ鍔を有する態様（ドラムコア）、巻芯部１１ａの軸長方向を実装面に対して垂直に配置する態様、水平に配置する態様がある。
特に、巻芯部１１ａの軸の一方のみに鍔を有し、巻芯部１１ａの軸長方向を実装面に対して垂直に配置した態様は、低背化をするのに好ましい。
The core 11 has at least a core part 11a, and the cross-sectional shape of the core part 11a can be plate-shaped (rectangular), circular, or oval.
Furthermore, it is preferable to have at least the flange part 11 at the end of the winding core part 11a.
When the flange portion 11 is provided, the position of the coil with respect to the core portion 11a can be easily controlled by the flange portion 11, and characteristics such as inductance are stabilized.
The core 11 includes an aspect having one ridge, an aspect having two ridges (drum core), an aspect in which the axial length direction of the winding core portion 11a is disposed perpendicular to the mounting surface, and an aspect in which the core 11 is disposed horizontally. .
In particular, an aspect in which only one of the shafts of the core part 11a has a flange and the axial length direction of the core part 11a is arranged perpendicular to the mounting surface is preferable for reducing the height.
外部導体膜１４は、電子部品用軟磁性合金を用いた素体１０の表面に形成されており、前記外部導体膜１４に前記コイルの端部が接続されている。
外部導体膜１４は、焼き付け導体膜、樹脂導体膜がある。電子部品用軟磁性合金素体１０への焼き付け導体膜の形成例としては、銀にガラスを添加したペーストを、所定の温度で焼き付ける方法がある。電子部品用軟磁性合金を用いた素体１０への樹脂導体膜の形成例としては、銀とエポキシ樹脂とを含有するペーストを塗布し、所定の温度処理する方法がある。焼き付け導体膜の場合、導体膜形成後、熱処理できる。
The outer conductor film 14 is formed on the surface of the element body 10 using a soft magnetic alloy for electronic parts, and the end of the coil is connected to the outer conductor film 14.
The external conductor film 14 includes a baked conductor film and a resin conductor film. As an example of forming a baked conductor film on the soft magnetic alloy body 10 for electronic parts, there is a method of baking a paste obtained by adding glass to silver at a predetermined temperature. As an example of forming the resin conductor film on the element body 10 using the soft magnetic alloy for electronic parts, there is a method of applying a paste containing silver and an epoxy resin and performing a predetermined temperature treatment. In the case of a baked conductor film, heat treatment can be performed after the conductor film is formed.
コイルの材質としては、銅、銀がある。コイルに絶縁被膜を施すことが好ましい。
コイルの形状としては、平角線、角線、丸線がある。平角線、角線の場合、巻き線間の隙間を小さくできるため、電子部品の小型化をするのに好ましい。
The coil material includes copper and silver. It is preferable to apply an insulating coating to the coil.
The coil shape includes a flat wire, a square wire, and a round wire. In the case of a rectangular wire or a square wire, the gap between the windings can be reduced, which is preferable for reducing the size of the electronic component.
本実施形態の電子部品２０における電子部品用軟磁性合金を用いた素体１０の表面の外部導体膜１４，１４の焼付導体膜層１４ａは、具体的な例としては、以下のようにして形成することができる。
上述した素体１０であるコア１１の鍔部１１ｂ、１１ｂの実装面に、金属粒子とガラスフリットとを含む焼付型の電極材料ペースト（本実施例では焼付型Ａｇペースト）を塗布し、大気中で熱処理を行うことで、素体１０の表面に直接電極材を焼結固着させる。またさらに、形成された焼付導体膜層１４ａの表面に電解メッキでＮｉ，Ｓｎの金属メッキ層を形成してもよい。
As a specific example, the baked conductor film layer 14a of the outer conductor films 14 and 14 on the surface of the element body 10 using the soft magnetic alloy for electronic components in the electronic component 20 of the present embodiment is formed as follows. can do.
A baking-type electrode material paste containing metal particles and glass frit (a baking-type Ag paste in this embodiment) is applied to the mounting surfaces of the flanges 11b and 11b of the core 11 that is the element body 10 described above. The electrode material is directly sintered and fixed to the surface of the element body 10 by performing a heat treatment. Furthermore, a metal plating layer of Ni or Sn may be formed on the surface of the formed baked conductor film layer 14a by electrolytic plating.
また、本実施形態の電子部品２０は、態様の一つとして以下の製造方法によっても得ることができる。
具体的な組成の例として、クロム２〜８ｗｔ％、ケイ素１．５〜７ｗｔ％、鉄８８〜９６．５ｗｔ％を含有する原料粒子と結合剤とを含む材料を成形し、得られた成形体の少なくても実装面となる表面に金属粉末とガラスフリットを含む焼付型の電極材料ペーストを塗布した後、得られた成形体を大気中４００〜９００℃で熱処理する。またさらに、形成された焼付導体層上に金属メッキ層を形成してもよい。この方法によれば、粒子の表面に酸化層が生成されるとともに隣接する粒子の表面の酸化層同士が結合された電子部品用軟磁性合金素体とこの素体の表面の導体膜の焼付導体層とを同時に形成することができ、製造プロセスを簡略化することができる。
鉄よりもクロムの方が酸化しやすいので、純鉄に比較して、酸化雰囲気で熱を加えたときに、鉄の酸化が進みすぎることを抑制できる。クロム以外としてアルミニウムをあげることができる。
Moreover, the electronic component 20 of this embodiment can be obtained also with the following manufacturing methods as one of the aspects.
As an example of a specific composition, a molded body obtained by molding a material containing raw material particles containing 2 to 8 wt% chromium, 1.5 to 7 wt% silicon, and 88 to 96.5 wt% iron and a binder is obtained. At least, a baking type electrode material paste containing metal powder and glass frit is applied to the surface to be the mounting surface, and the obtained molded body is heat-treated at 400 to 900 ° C. in the atmosphere. Furthermore, a metal plating layer may be formed on the formed baked conductor layer. According to this method, an oxide layer is formed on the surface of the particles and the oxide layers on the surfaces of the adjacent particles are bonded to each other, and the baked conductor of the conductor film on the surface of the element body The layers can be formed at the same time, and the manufacturing process can be simplified.
Since chromium is easier to oxidize than iron, it is possible to prevent iron from being excessively oxidized when heat is applied in an oxidizing atmosphere as compared to pure iron. Aluminum can be cited as other than chromium.
次に、本発明の電子部品用軟磁性合金素体の実施形態の変形例について、図８を参照して説明する。図８は、変形例の一例の電子部品用軟磁性合金を用いた素体１０’を示す内部構造の透視図である。本変形例の素体１０’は、外観が直方体状を呈し、内部には蔓巻螺旋状に巻回された内部コイル３５が埋設されており、内部コイル３５の両端部の引出部がそれぞれ素体１０’の互いに対向する一対の端面に露出されている。素体１０’は、内部に埋設された内部コイル３５とともに積層体チップ３１を構成する。本変形例の電子部品用軟磁性合金素体１０’は、先の第１の実施形態の電子部品用軟磁性合金素体１０と同様に、クロム、ケイ素、鉄を含有する複数の粒子と、粒子の表面に生成され、少なくとも鉄及びクロムを含み、走査型電子顕微鏡を用いたエネルギー分散型Ｘ線分析による鉄に対するクロムのピーク強度比が粒子における鉄に対するクロムのピーク強度比よりも大きい酸化層と、を備え、隣接する粒子の表面に生成された酸化層同士が結合されていることを特徴とする。
本変形例の電子部品用軟磁性合金素体１０’においても、先の第１の実施形態の電子部
品用軟磁性合金素体１０と同様の作用・効果を有する。
Next, a modification of the embodiment of the soft magnetic alloy body for electronic parts of the present invention will be described with reference to FIG. FIG. 8 is a perspective view of an internal structure showing an element body 10 ′ using a soft magnetic alloy for electronic parts as an example of a modification. The element body 10 ′ of the present modification has a rectangular parallelepiped appearance, and an internal coil 35 wound in a spiral shape is embedded in the element body 10 ′. The body 10 'is exposed at a pair of end faces facing each other. The element body 10 ′ constitutes the multilayer chip 31 together with the internal coil 35 embedded therein. Similar to the soft magnetic alloy body 10 for electronic parts of the first embodiment, the soft magnetic alloy body 10 ′ for electronic parts of the present modification includes a plurality of particles containing chromium, silicon, and iron, An oxide layer formed on the surface of the particle, containing at least iron and chromium, and having a peak intensity ratio of chromium to iron by energy dispersive X-ray analysis using a scanning electron microscope larger than the peak intensity ratio of chromium to iron in the particle The oxide layers generated on the surfaces of adjacent particles are bonded to each other.
The electronic component soft magnetic alloy body 10 ′ of the present modification also has the same operations and effects as the electronic component soft magnetic alloy body 10 of the first embodiment.
次に、本発明の電子部品の実施形態の変形例について、図９を参照して説明する。図９は、変形例の一例の電子部品４０を示す内部構造の透視図である。本変形例の電子部品４０は、上述した変形例の電子部品用軟磁性合金を用いた素体１０’の互いに対向する一対の端面およびその近傍に、内部コイル３５の露出された引出部と接続するように形成された一対の外部導体膜３４、３４を備える。外部導体膜３４，３４は、図示省略するが、先の第１の実施形態の電子部品２０の外部導体膜１４，１４と同様に、焼付導体層と、この焼付導体層上に積層形成されたＮｉメッキ層、Ｓｎメッキ層を備える。本変形例の電子部品４０においても、先の第１の実施形態の電子部品２０と同様の作用・効果を有する。 Next, a modification of the embodiment of the electronic component of the present invention will be described with reference to FIG. FIG. 9 is a perspective view of an internal structure showing an electronic component 40 as an example of a modification. The electronic component 40 of the present modified example is connected to the exposed drawing portion of the internal coil 35 on the pair of opposed end surfaces of the element body 10 ′ using the soft magnetic alloy for electronic components of the modified example described above and in the vicinity thereof. A pair of outer conductor films 34, 34 are formed. Although not shown in the drawings, the outer conductor films 34 and 34 are formed on the baked conductor layer and the baked conductor layer in the same manner as the outer conductor films 14 and 14 of the electronic component 20 of the first embodiment. Ni plating layer and Sn plating layer are provided. The electronic component 40 of the present modification also has the same operations and effects as the electronic component 20 of the first embodiment.
さらに、本発明における電子部品用軟磁性合金素体を構成する複数の粒子の組成は、２≦クロム≦８ｗｔ％で、かつ、１．５≦ケイ素≦７ｗｔ％、８８≦鉄≦９６．５％を含有とすることが好ましい。この範囲のとき、本発明の電子部品用軟磁性合金素体は、さらに、高い強度と高い体積抵抗率を示す。
一般的に、軟磁性合金はＦｅ量が多いほど高飽和磁束密度のため直流重畳特性に有利であるものの、高温多湿時に錆が発生やその錆の脱落等が磁性素子としての使用時に問題となっている。
また、磁性合金へのクロム添加が耐食性に効果があることはステンレス鋼に代表されるようによく知られている。しかしながら、クロムを含有する上記合金粉末を用いて非酸化性雰囲気中で熱処理を行った圧粉磁心では、絶縁抵抗計で測定した比抵抗が１０−１Ωcmと粒子間での渦電流損失が発生しない程度の値は有しているものの、外部導体膜を形成するには１０５Ωcm以上の比抵抗が必要であり、外部導体膜の焼付導体層上への金属メッキ層を形成することができなかった。
Furthermore, the composition of the plurality of particles constituting the soft magnetic alloy body for electronic parts in the present invention is 2 ≦ chrome ≦ 8 wt%, 1.5 ≦ silicon ≦ 7 wt%, and 88 ≦ iron ≦ 96.5%. It is preferable to contain. In this range, the soft magnetic alloy body for electronic parts of the present invention further exhibits high strength and high volume resistivity.
Generally, a soft magnetic alloy has a higher saturation magnetic flux density and is more advantageous for direct current superposition characteristics as the amount of Fe increases. However, rust is generated at high temperature and high humidity, and the rust falls off when used as a magnetic element. ing.
It is well known that the addition of chromium to a magnetic alloy has an effect on corrosion resistance, as represented by stainless steel. However, in a powder magnetic core that is heat-treated in a non-oxidizing atmosphere using the above alloy powder containing chromium, the specific resistance measured by an insulation resistance meter is 10 −1 Ωcm, and eddy current loss occurs between particles. However, the specific resistance of 10 5 Ωcm or more is necessary to form the outer conductor film, and a metal plating layer can be formed on the baked conductor layer of the outer conductor film. There wasn't.
そこで、本発明では、上記組成を有する原料粒子と結合剤とを含む成形体を、酸化雰囲気中で熱処理することで粒子の表面に金属酸化物層からなる酸化層を生成させ、かつ隣接する粒子の表面の酸化層同士を結合させことで、高い強度を得るものである。得られた電子部品用軟磁性合金素体の体積抵抗率ρＶは、１０５Ωｃｍ以上と大幅に向上し、素体の表面に形成された外部導体膜の焼付導体層上へのＮｉ、Ｓｎ等の金属メッキ層をメッキ延びを生じさせることなく形成することが可能となった。 Therefore, in the present invention, a molded body containing the raw material particles having the above composition and a binder is heat-treated in an oxidizing atmosphere to generate an oxide layer composed of a metal oxide layer on the surface of the particles, and adjacent particles. High strength can be obtained by bonding the oxide layers on the surface of each other. The volume resistivity ρV of the obtained soft magnetic alloy body for electronic parts is greatly improved to 10 5 Ωcm or more, and Ni, Sn, etc. on the baked conductor layer of the outer conductor film formed on the surface of the body It is possible to form the metal plating layer without causing plating elongation.
さらに好ましい形態の本発明の電子部品用軟磁性合金素体において、組成を限定する理由を説明する。
複数の粒子の組成中のクロムの含有量が、２ｗｔ％未満では、体積抵抗率は低く、外部導体膜の焼付導体層上への金属メッキ層をメッキ延びを生じさせることなく形成することができない。
The reason why the composition of the soft magnetic alloy body for electronic parts according to the present invention is further limited will be described.
When the chromium content in the composition of the plurality of particles is less than 2 wt%, the volume resistivity is low, and the metal plating layer on the baked conductor layer of the outer conductor film cannot be formed without causing plating elongation. .
また、クロムが８ｗｔ％より多い場合にも、体積抵抗率は低く、外部導体膜の焼付導体層上への金属メッキ層をメッキ延びを生じさせることなく形成することができない。
また、上記特許文献１に記載されたようにＦｅ−Ｓｉ−Ａｌ粉末を用い大気中熱処理により酸化物の被覆を形成したものは、被覆がクロムを含まない酸化物である。このため、その体積抵抗率は１０５Ωcmに比べて低く、外部導体膜の焼付導体層上への金属メッキ層をメッキ延びを生じさせることなく形成することができない。
Further, even when the amount of chromium is more than 8 wt%, the volume resistivity is low, and a metal plating layer on the baked conductor layer of the outer conductor film cannot be formed without causing plating extension.
In addition, as described in Patent Document 1 described above, when an oxide coating is formed by heat treatment in the atmosphere using Fe—Si—Al powder, the coating does not contain chromium. For this reason, the volume resistivity is lower than 10 5 Ωcm, and a metal plating layer on the baked conductor layer of the outer conductor film cannot be formed without causing plating extension.
上記電子部品用軟磁性合金素体において、複数の粒子の組成中のＳｉは体積抵抗率の改善の作用を有するが、１．５ｗｔ％未満ではその効果は得られず、一方、７ｗｔ％より大きい場合にも、その効果は十分でなく、その体積抵抗率は１０５Ωcmに満たないため、外部導体膜の焼付導体層上への金属メッキ層をメッキ延びを生じさせることなく形成することができない。また、Ｓｉは透磁率の改善の作用も有するが、７ｗｔ％より大きい場合には、Ｆｅ含有量の相対的低下による飽和磁束密度の低下と成形性の悪化に伴う透磁率および飽和磁束密度の低下が生じる。 In the above-described soft magnetic alloy body for electronic parts, Si in the composition of a plurality of particles has an effect of improving volume resistivity, but the effect is not obtained when it is less than 1.5 wt%, while it is larger than 7 wt%. Even in this case, the effect is not sufficient, and the volume resistivity is less than 10 5 Ωcm, so that the metal plating layer on the baked conductor layer of the outer conductor film cannot be formed without causing plating extension. . Si also has the effect of improving the magnetic permeability. However, when it is larger than 7 wt%, the saturation magnetic flux density is decreased due to the relative decrease in the Fe content and the magnetic permeability and the saturation magnetic flux density are decreased due to the deterioration of the formability. Occurs.
クロム以外の酸化されやすい元素としてアルミニウムを用いた場合は、アルミニウム２〜８ｗｔ％、ケイ素１．５〜１２ｗｔ％、鉄８０〜９６．５ｗｔ％が好ましい。
複数の粒子の組成中のアルミニウムの含有量が、２ｗｔ％未満では、体積抵抗率は低く、外部導体膜の焼付導体層上への金属メッキ層をメッキ延びを生じさせることなく形成することができない。また、アルミニウムの含有量が、８ｗｔ％より大きい場合には、Ｆｅ含有量の相対的低下による飽和磁束密度の低下が生じる。
防錆の観点から、クロム２〜８ｗｔ％、ケイ素１．５〜７ｗｔ％、鉄８８〜９６．５ｗｔ％の組成であることが好ましい。
なお、鉄、クロム、ケイ素の合金粒子に、鉄、アルミニウム、ケイ素の合金粒子を混合（例えば合金粒子合計の５０ｗｔ％未満）したものでも適用可能である。
When aluminum is used as an easily oxidizable element other than chromium, aluminum is preferably 2 to 8 wt%, silicon is 1.5 to 12 wt%, and iron is 80 to 96.5 wt%.
When the content of aluminum in the composition of the plurality of particles is less than 2 wt%, the volume resistivity is low, and the metal plating layer on the baked conductor layer of the outer conductor film cannot be formed without causing plating elongation. . Further, when the aluminum content is larger than 8 wt%, the saturation magnetic flux density is reduced due to the relative reduction of the Fe content.
From the viewpoint of rust prevention, the composition is preferably 2-8 wt% chromium, 1.5-7 wt% silicon, and 88-96.5 wt% iron.
In addition, iron, chromium, and silicon alloy particles mixed with iron, aluminum, and silicon alloy particles (for example, less than 50 wt% of the total alloy particles) are also applicable.
上記電子部品用軟磁性合金素体において、複数の粒子の組成中の鉄の含有量が８８ｗｔ％未満では飽和磁束密度の低下と成形性の悪化に伴う透磁率および飽和磁束密度の低下が生じる。また、鉄の含有量が９６．５ｗｔ％より大きい場合には、クロム含有量、ケイ素含有量の相対的低下により体積抵抗率が低下する。 In the soft magnetic alloy body for electronic parts described above, when the iron content in the composition of the plurality of particles is less than 88 wt%, the saturation magnetic flux density and the permeability and the saturation magnetic flux density are reduced due to the deterioration of the formability. Further, when the iron content is larger than 96.5 wt%, the volume resistivity decreases due to a relative decrease in the chromium content and the silicon content.
本発明において、さらに、複数の粒子の平均粒径は原料粒子の平均粒子径ｄ５０％（算術平均）に換算したときに５〜３０μｍであることがより望ましい。また、上記複数の粒子の平均粒径は、素体の断面を、走査型電子顕微鏡（ＳＥＭ）を用いて３０００倍で撮影した組成像中から、粒子の断面の輪郭がすべて確認できる粒子について、各粒子の断面の長軸寸法ｄ１と短軸寸法ｄ２の単純平均Ｄ＝（ｄ１＋ｄ２）／２の総和を上記粒子の個数で割った値で近似することもできる。 In the present invention, the average particle size of the plurality of particles is more preferably 5 to 30 μm when converted to the average particle size d50% (arithmetic average) of the raw material particles. In addition, the average particle diameter of the plurality of particles is a particle whose cross section of the particle can be confirmed from the composition image obtained by photographing the cross section of the element body at 3000 times using a scanning electron microscope (SEM). It can also be approximated by a value obtained by dividing the sum of the simple average D = (d1 + d2) / 2 of the major axis dimension d1 and minor axis dimension d2 of each particle by the number of the particles.
合金金属粒子群は、粒度分布を持ち、必ずしも真球でなくいびつな形状をとなっている。
また、立体である合金金属粒子を２次元（平面）でみるとき、どこの断面で観察するかで見かけ大きさが異なる。
このため、本発明の平均粒径では、測定する粒子数を多くすることで、粒子径を評価する。
このため、少なくても下記条件にて該当する粒子数を少なくとも１００以上測定することが望ましい。
具体的方法は、粒子断面にて最大となる径を長軸とし、長軸の長さを２等分した点を求める。
その点が含まれ粒子断面にて最小となる径を短軸とする。これを長軸寸法、短軸寸法と定義する。
測定する粒子は、粒子断面にて最大となる径が大きい粒子を大きい順に順番に並べ、粒子断面の累計比率が、走査型電子顕微鏡（ＳＥＭ）の画像から、粒子の断面の輪郭がすべて確認できない粒子と、空孔と、酸化層を除いた面積の９５％になる大きさのものを測定する。
上記平均粒径がこの範囲内にあると、高い飽和磁束密度（１．４Ｔ以上）と高い透磁率（２７以上）を得られるともに、１００ｋＨｚ以上の周波数においても、粒子内で渦電流損失が生じるのが抑制される。
なお、本明細書において、開示する具体的数値は、ある態様では約そのような数値であること意味し、また、範囲の記載において上限および・または下限の数値はある態様では範囲に含まれており、ある態様では含まれていない。また、ある態様では数値は平均値、典型値、中央値等を意味する。
The alloy metal particle group has a particle size distribution and is not necessarily a perfect sphere but an irregular shape.
Further, when the three-dimensional alloy metal particles are viewed two-dimensionally (planar), the apparent size differs depending on which cross-section is observed.
For this reason, in the average particle diameter of the present invention, the particle diameter is evaluated by increasing the number of particles to be measured.
For this reason, it is desirable to measure at least 100 or more corresponding particles under the following conditions.
A specific method is to obtain a point obtained by taking the maximum diameter in the particle cross section as a major axis and dividing the length of the major axis into two equal parts.
The shortest axis is the diameter that includes that point and is the smallest in the particle cross section. This is defined as the major axis dimension and the minor axis dimension.
The particles to be measured are arranged in order from the largest particle having the largest diameter in the particle cross section, and the total cross-sectional ratio of the particle cross section cannot be confirmed from the image of the scanning electron microscope (SEM). Particles, vacancies, and particles that are 95% of the area excluding the oxide layer are measured.
When the average particle size is within this range, a high saturation magnetic flux density (1.4 T or more) and a high magnetic permeability (27 or more) can be obtained, and eddy current loss occurs in the particles even at a frequency of 100 kHz or more. Is suppressed.
Note that in this specification, specific numerical values disclosed herein mean that the numerical values are approximately such in certain embodiments, and upper and / or lower numerical values in the description of ranges are included in the ranges in certain embodiments. And not included in some embodiments. In some embodiments, the numerical value means an average value, a typical value, a median value, or the like.
以下、本発明を実施例及び比較例によってさらに具体的に説明するが、本発明はこれらにより何ら限定されるものではない。 EXAMPLES Hereinafter, although an Example and a comparative example demonstrate this invention further more concretely, this invention is not limited at all by these.
電子部品用軟磁性合金を用いた素体の磁気特性の良し悪しを判断するのに、原料粒子の充填率が８０体積％となるように成形圧力を６〜１２ｔｏｎ／ｃｍ２の間で調整して外径１４ｍｍ、内径８ｍｍ、厚さ３ｍｍのトロイダル状に成形し、大気中で熱処理を施したのち、得られた素体に直径０．３ｍｍのウレタン被覆銅線からなるコイルを２０ターン巻回して試験試料とした。飽和磁束密度Ｂｓの測定は、振動試料型磁力計（東英工業社製：ＶＳＭ）を用いて行い、透磁率μの測定は、Ｌクロムメーター（アジレントテクノロジー社製：４２８５Ａ）を用いて測定周波数１００ｋＨｚで測定した。飽和磁束密度Ｂｓが、０．７Ｔ以上を良と判定した。透磁率μが２０以上のものを良と判定した。 In order to judge whether the magnetic properties of the element body using the soft magnetic alloy for electronic parts are good or bad, the molding pressure is adjusted between 6 and 12 ton / cm 2 so that the filling rate of the raw material particles becomes 80% by volume. After forming into a toroidal shape with an outer diameter of 14 mm, an inner diameter of 8 mm, and a thickness of 3 mm, and heat-treating in the atmosphere, a coil made of urethane-coated copper wire with a diameter of 0.3 mm is wound around the obtained element body for 20 turns. This was used as a test sample. The saturation magnetic flux density Bs is measured using a vibrating sample magnetometer (manufactured by Toei Kogyo Co., Ltd .: VSM), and the permeability μ is measured using an L chrome meter (manufactured by Agilent Technologies: 4285A). Measurement was performed at 100 kHz. The saturation magnetic flux density Bs was determined to be 0.7T or higher. A material having a permeability μ of 20 or more was determined to be good.
電子部品用軟磁性合金を用いた素体の強度の良し悪しを判断するのに、図１０に示す測定方法を用いて以下の通り、３点曲げ破断応力を測定した。３点曲げ破断応力を測定するための試験片は、原料粒子の充填率が８０体積％となるように成形圧力を６〜１２ｔｏｎ／ｃｍ２の間で調整して長さ５０ｍｍ、幅１０ｍｍ、厚さ４ｍｍの板状の成形体に成形したのち、大気中で熱処理を施したものである。
３点曲げ破断応力が１．０ｋｇｆ／ｍｍ２以上を良とした。
飽和磁束密度Ｂｓ、透磁率μ、３点曲げ破断応力とも良のものを、合格とした。
In order to judge whether the strength of the element body using the soft magnetic alloy for electronic parts was good or bad, the measurement method shown in FIG. The test piece for measuring the three-point bending rupture stress has a length of 50 mm, a width of 10 mm, and a thickness by adjusting the molding pressure between 6 and 12 ton / cm 2 so that the filling rate of the raw material particles is 80% by volume. After forming into a 4 mm plate-shaped molded body, heat treatment was performed in the air.
A three-point bending rupture stress of 1.0 kgf / mm 2 or more was considered good.
A material having good saturation magnetic flux density Bs, magnetic permeability μ, and 3-point bending rupture stress was regarded as acceptable.
さらに、電子部品用軟磁性合金を用いた素体の体積抵抗率の良し悪しを判断するのに、図１１に示すように、ＪＩＳ−Ｋ６９１１に準じて測定を行った。体積抵抗率を測定するための試験片は、原料粒子の充填率が８０体積％となるように成形圧力を６〜１２ｔｏｎ／ｃｍ２の間で調整して直径１００ｍｍ、厚さ２ｍｍの円板状に成形したのち、大気中で熱処理を施したものである。
体積抵抗率が、１×１０−３Ωｃｍ以上を可、１×１０−１Ωｃｍ以上を良、１×１０５Ωｃｍ以上を優と判断した。１×１０−１Ωｃｍ以上であれば、高周波で使用したときに、渦電流による損失を小さくできる。さらに、１×１０５Ωｃｍ以上であれば、湿式メッキによる導体層上への金属メッキ層を形成できる。
Furthermore, in order to judge whether the volume resistivity of the element body using the soft magnetic alloy for electronic parts is good or bad, as shown in FIG. 11, measurement was performed according to JIS-K6911. The test piece for measuring the volume resistivity is a disc having a diameter of 100 mm and a thickness of 2 mm by adjusting the molding pressure between 6 and 12 ton / cm 2 so that the filling rate of the raw material particles becomes 80% by volume. And then heat treated in the air.
The volume resistivity was determined to be 1 × 10 −3 Ωcm or higher, 1 × 10 −1 Ωcm or higher was judged to be good, and 1 × 10 5 Ωcm or higher was judged to be excellent. If it is 1 × 10 −1 Ωcm or more, loss due to eddy current can be reduced when used at a high frequency. Furthermore, if it is 1 × 10 5 Ωcm or more, a metal plating layer can be formed on the conductor layer by wet plating.
また、電子部品用軟磁性合金素体の表面の外部導体膜の焼付導体層上への金属メッキ層の形成の良し悪しを判断するのに、以下に述べる実施例では、電子部品用軟磁性合金素体の形状をドラム型とした。
得られた電子部品試料の外部導体膜上への金属メッキ層の形成の良し悪しの判断は、拡大鏡を用いた目視外観判断により、Ｎｉ、Ｓｎメッキが焼付導体層上に連続的に形成され、かつ焼付導体層からその周囲へのメッキ延びの発生がないものを○とし、その他を×とした。
In addition, in order to judge whether or not the metal plating layer is formed on the baked conductor layer of the outer conductor film on the surface of the soft magnetic alloy body for electronic parts, in the embodiment described below, the soft magnetic alloy for electronic parts is used. The shape of the element body was a drum shape.
Whether or not the metal plating layer is formed on the outer conductor film of the obtained electronic component sample is judged by visual appearance judgment using a magnifying glass, Ni and Sn plating are continuously formed on the baked conductor layer. In addition, the case where there was no occurrence of the plating extending from the baked conductor layer to the periphery thereof was rated as ◯, and the others as x.
（実施例１）
電子部品用軟磁性合金素体を得るための原料粒子として、平均粒子径（ｄ５０％）が１０μｍの水アトマイズ粉で、組成比がクロム：５ｗｔ％、ケイ素：３ｗｔ％、鉄：９２ｗｔ％の合金粉（エプソンアトミックス（株）社製 PF-20F）を用いた。上記原料粒子の平均粒子径ｄ５０％は、粒度分析計(日機装社製：９３２０ＨＲＡ）を用いて測定した。また、上記粒子を粒子の中心を通る断面が露出するまで研磨し、得られた断面を走査型電子顕微鏡（ＳＥＭ：日立ハイテクノロジー社製Ｓ−４３００ＳＥ／Ｎ）を用いて３０００倍で撮影した組成像について、粒子の中心付近と表面近傍それぞれの１μｍ□の組成をエネルギー分散型Ｘ線分析（ＥＤＳ）によりＺＡＦ法で算出し、粒子の中心付近における上記の組成比と粒子の表面近傍における上記の組成比とがほぼ等しいことを確認した。
次に、上記粒子とポリビニルブチラール（積水化学社製：エスレックBL：固形分３０ｗｔ％濃度溶液）を湿式転動攪拌装置にて混合し造粒物を得た。
得られた造粒粉を、複数の粒子の充填率が８０体積％となるように、成形圧力を６〜１２ｔｏｎ／ｃｍ２の間で調整して、長さ５０ｍｍ、幅１０ｍｍ、厚さ４ｍｍの角板状の成形体と、直径１００ｍｍ、厚さ２ｍｍの円板状の成形体と、外径１４ｍｍ、内径８ｍｍ、厚さ３ｍｍのトロイダル状の成形体、および巻芯部（幅１．０ｍｍ×高さ０．３６ｍｍ×長さ１．４ｍｍ）の両端に角鍔（幅１．６ｍｍ×高さ０．６ｍｍ×厚さ０．３ｍｍ）を有するドラム型のコア成形体と、一対の板状コア成形体（長さ２．０ｍｍ×幅０．５ｍｍ×厚さ０．２ｍｍ）を得た。
上記で得られた円板状の成形体、トロイダル状の成形体、ドラム型の成形体、一対の板状成形体について、大気中、７００℃で６０分の熱処理を行った。
Example 1
As raw material particles for obtaining a soft magnetic alloy body for electronic parts, an aqueous atomized powder having an average particle size (d50%) of 10 μm, and a composition ratio of chromium: 5 wt%, silicon: 3 wt%, iron: 92 wt% Powder (PF-20F manufactured by Epson Atmix Co., Ltd.) was used. The average particle diameter d50% of the raw material particles was measured using a particle size analyzer (manufactured by Nikkiso Co., Ltd .: 9320HRA). Moreover, the composition was obtained by polishing the particles until a cross section passing through the center of the particles was exposed, and photographing the obtained cross section at 3000 times using a scanning electron microscope (SEM: S-4300SE / N manufactured by Hitachi High-Technology Corporation). For the image, the composition of 1 μm square near the center of the particle and near the surface is calculated by the ZAF method by energy dispersive X-ray analysis (EDS), and the above composition ratio near the particle center and the above surface near the particle surface. It was confirmed that the composition ratio was almost equal.
Next, the above particles and polyvinyl butyral (manufactured by Sekisui Chemical Co., Ltd .: ESREC BL: solid content 30 wt% concentration solution) were mixed with a wet rolling stirrer to obtain a granulated product.
The obtained granulated powder is adjusted to a molding pressure of 6 to 12 ton / cm 2 so that the filling rate of a plurality of particles is 80% by volume, and has a length of 50 mm, a width of 10 mm, and a thickness of 4 mm. A square plate-shaped molded body, a disk-shaped molded body having a diameter of 100 mm and a thickness of 2 mm, a toroidal molded body having an outer diameter of 14 mm, an inner diameter of 8 mm, and a thickness of 3 mm, and a core portion (width 1.0 mm × A drum-shaped core molded body having square ridges (width 1.6 mm × height 0.6 mm × thickness 0.3 mm) at both ends of a height of 0.36 mm × length of 1.4 mm, and a pair of plate-like cores A molded body (length 2.0 mm × width 0.5 mm × thickness 0.2 mm) was obtained.
The disk-shaped molded body, the toroidal molded body, the drum-shaped molded body, and the pair of plate-shaped molded bodies obtained above were subjected to heat treatment at 700 ° C. for 60 minutes in the atmosphere.
上記円板状の成形体の熱処理により得られた円板状の素体について、ＪＩＳ−Ｋ６９１１に準じて体積抵抗率の測定を行い、結果を表１に示した。
また上記ドラム型の成形体の熱処理で得られたドラム型の素体について、巻芯部のほぼ中心を通る厚さ方向の断面が露出するように研磨し、その断面を、走査型電子顕微鏡（ＳＥＭ）を用いて３０００倍で撮影し組成像を得た。次に、上記で得られた組成像について、各画素を３段階の明度ランクに分類し、上記組成像中で粒子の断面の輪郭がすべて確認できる粒子のうち、各粒子の断面の長軸寸法ｄ１と短軸寸法ｄ２の単純平均Ｄ＝（ｄ１＋ｄ２）／２が原料粒子の平均粒径（ｄ５０％）より大きい粒子の組成コントラストを中心明度ランクとし、上記組成像中でこの明度ランクに該当する部分を粒子１と判断した。また、組成コントラストが上記中心明度ランクより暗い明度ランクの部分を酸化層２と判断した。また、上記中心明度ランクより明るい明度ランクの部分を空孔３と判断し、得られた結果を模式図として図２に示した。
The disk-shaped body obtained by heat treatment of the disk-shaped molded body was measured for volume resistivity according to JIS-K6911. The results are shown in Table 1.
Further, the drum-shaped element obtained by the heat treatment of the drum-shaped molded body is polished so that a cross section in the thickness direction passing through almost the center of the core portion is exposed, and the cross section is scanned with a scanning electron microscope ( SEM) was used to obtain a composition image. Next, with respect to the composition image obtained above, each pixel is classified into three levels of brightness ranks, and among the particles that can confirm all the cross-sectional contours of the particles in the composition image, the major axis dimension of each particle cross-section The compositional contrast of particles whose simple average D = (d1 + d2) / 2 of d1 and minor axis dimension d2 is larger than the average particle diameter (d50%) of the raw material particles is set as the central lightness rank, and this lightness rank corresponds to this lightness rank in the composition image. The part was judged as particle 1. The portion of the lightness rank where the composition contrast is darker than the central lightness rank was determined as the oxide layer 2. Further, the lightness rank portion brighter than the central lightness rank is determined as the hole 3, and the obtained result is shown in FIG. 2 as a schematic diagram.
次に、上記組成像中から、粒子の断面の輪郭がすべて確認できる粒子のうち各粒子の断面の長軸寸法ｄ１と短軸寸法ｄ２の単純平均Ｄ＝（ｄ１＋ｄ２）／２が原料粒子の平均粒径（ｄ５０％）より大きい粒子を抽出し、その長軸と短軸の交点付近の１μｍ□の組成をエネルギー分散型Ｘ線分析（ＥＤＳ）によりＺＡＦ法で算出し、これを上記原料粒子における組成比と対比して、上記素体における複数の粒子の組成比が原料粒子の組成比とほぼあるいは実質的に等しいことを確認した。 Next, out of the above composition images, among the particles in which all the cross-sectional contours of the particles can be confirmed, the simple average D = (d1 + d2) / 2 of the major axis dimension d1 and minor axis dimension d2 of each particle cross section is the average of the raw material particles Particles larger than the particle size (d50%) are extracted, and the composition of 1 μm □ near the intersection of the major and minor axes is calculated by the energy dispersive X-ray analysis (EDS) by the ZAF method, In contrast to the composition ratio, it was confirmed that the composition ratio of the plurality of particles in the element body was almost or substantially equal to the composition ratio of the raw material particles.
次に、上記組成像における粒子１の内部の長軸ｄ１と短軸ｄ２とが交わる点を中心とした１μｍ□の組成をＳＥＭ−ＥＤＳで求め、その結果を図３（Ａ）に示した。次に、上記組成像における粒子１の表面の酸化層２の最厚部の厚さｔ１と最薄部の厚さｔ２から平均厚さＴ＝（ｔ１＋ｔ２）／２に相当する酸化層厚さの部位における酸化層の厚さの中心点を中心とした１μｍ□の組成についてＳＥＭ−ＥＤＳで求め、図３（Ｂ）に示した。図３（Ａ）より、粒子１の内部における鉄の強度Ｃ１ＦｅＫａが４２００ｃｏｕｎｔ、クロムの強度Ｃ１ＣｒＫａが１００ｃｏｕｎｔ、鉄に対するクロムのピーク強度比Ｒ１＝Ｃ１ＣｒＫａ／Ｃ１ＦｅＫａが０．０２４である。図３（Ｂ）より、酸化層２の厚さの中心点における鉄の強度Ｃ２ＦｅＫａが３０００ｃｏｕｎｔ、クロムの強度Ｃ２ＣｒＫａが１８００ｃｏｕｎｔ、鉄に対するクロムのピーク強度比Ｒ２＝Ｃ２ＣｒＫａ／Ｃ２ＦｅＫａが０．６０であり、前記粒子の内部における鉄に対するクロムのピーク強度比Ｒ１よりも大きいことがわかる。
また、本発明の電子部品用軟磁性合金素体において、隣接する粒子１，１の表面に生成された酸化層２，２同士が結合されていることは、上記組成像に基づいて作成された図２に示す模式図より確認することができた。
Next, the composition of 1 μm □ centered on the point where the major axis d1 and the minor axis d2 inside the particle 1 in the composition image intersect was obtained by SEM-EDS, and the result is shown in FIG. Next, the oxide layer thickness corresponding to the average thickness T = (t1 + t2) / 2 from the thickness t1 and the thickness t2 of the thinnest portion of the oxide layer 2 on the surface of the particle 1 in the above composition image. The composition of 1 μm square centered on the central point of the thickness of the oxide layer at the site was determined by SEM-EDS and shown in FIG. From FIG. 3 (A), the iron strength C1 FeKa inside the particle 1 is 4200 counts, the chromium strength C1 CrKa is 100 counts, and the peak intensity ratio of chromium to iron R1 = C1 CrKa / C1 FeKa is 0.024. FIG. 3B shows that the iron strength C2 FeKa at the central point of the thickness of the oxide layer 2 is 3000 counts, the chromium strength C2 CrKa is 1800 counts, and the peak strength ratio of chromium to iron R2 = C2 CrKa / C2 FeKa is 0. 60, which is greater than the peak intensity ratio R1 of chromium to iron inside the particles.
Moreover, in the soft magnetic alloy body for electronic parts of this invention, it was created based on the said composition image that the oxide layers 2 and 2 produced | generated on the surface of the adjacent particle | grains 1 and 1 were couple | bonded. It could be confirmed from the schematic diagram shown in FIG.
以上の結果より、本実施例１の電子部品用軟磁性合金素体は、クロム２〜８ｗｔ％、ケイ素１．５〜７ｗｔ％、鉄８８〜９６．５ｗｔ％を含有する複数の粒子１，１と、粒子１の表面に生成された酸化層を備え、酸化層は、少なくとも鉄及びクロムを含み、透過型電子顕微鏡を用いたエネルギー分散型Ｘ線分析による鉄に対するクロムのピーク強度比が粒子における鉄に対するクロムのピーク強度比よりも大きいものであることを確認した。
また、上記トロイダル状の成形体の熱処理により得られたトロイダル状の素体について、直径０．３ｍｍのウレタン被覆銅線からなるコイルを２０ターン巻回して試験試料とした。飽和磁束密度Ｂｓの測定は、振動試料型磁力計（東英工業社製：ＶＳＭ）を用いて行い、透磁率μの測定は、ＬＣＲメーター（アジレントテクノロジー社製：４２８５Ａ）を用いて測定周波数１００ｋＨｚで測定した。得られた結果を表１に示した。
From the above results, the soft magnetic alloy body for an electronic component of Example 1 has a plurality of particles 1, 1 containing 2-8 wt% chromium, 1.5-7 wt% silicon, and 88-96.5 wt% iron. And an oxide layer generated on the surface of the particle 1, the oxide layer containing at least iron and chromium, and the peak intensity ratio of chromium to iron by energy dispersive X-ray analysis using a transmission electron microscope is in the particle It was confirmed that it was larger than the peak intensity ratio of chromium to iron.
Further, a test sample was prepared by winding 20 turns of a coil made of urethane-coated copper wire having a diameter of 0.3 mm with respect to the toroidal element obtained by heat treatment of the toroidal molded body. The saturation magnetic flux density Bs is measured using a vibrating sample magnetometer (manufactured by Toei Kogyo Co., Ltd .: VSM), and the permeability μ is measured using an LCR meter (manufactured by Agilent Technologies: 4285A) at a measurement frequency of 100 kHz. Measured with The obtained results are shown in Table 1.
また、上記で得られた角板状の成形体について、大気中において、熱処理温度１５０℃、２００℃、３００℃、５００℃、６００℃、７００℃、８００℃、１０００℃でそれぞれ６０分間熱処理して得られた角板状の素体および室温にて放置した角板状の成形体について、３点曲げ破断応力を測定した結果を表１及び表２に示した。
また、上記ドラム型の素体の両鍔部の実装面に、焼付型のＡｇ導体膜ペーストを塗布し、大気中、約３０分かけて７００℃まで昇温し、７００℃で１０分保持し、その後約３０分かけて降温することにより、導体膜材料の焼付処理を行い、外部導体膜の焼付導体層を形成した。さらに、該導体膜表面上に、電解メッキ法にて、Ｎｉ（厚さ２μm）、Ｓｎ（厚さ７μm）を形成した。
In addition, the square plate-like molded body obtained above was heat-treated in air for 60 minutes at 150 ° C., 200 ° C., 300 ° C., 500 ° C., 600 ° C., 700 ° C., 800 ° C., and 1000 ° C., respectively. Tables 1 and 2 show the results of measuring the three-point bending rupture stress of the obtained square plate-like body and the square plate-like molded body left at room temperature.
Also, a baking-type Ag conductor film paste is applied to the mounting surfaces of both flange portions of the drum-type element body, and the temperature is raised to 700 ° C. in the atmosphere over about 30 minutes and held at 700 ° C. for 10 minutes. Thereafter, the conductor film material was baked by lowering the temperature over about 30 minutes to form a baked conductor layer of the outer conductor film. Furthermore, Ni (thickness 2 μm) and Sn (thickness 7 μm) were formed on the surface of the conductor film by electrolytic plating.
得られた結果を表１に示した。
この結果、素体の強度が７．４ｋｇｆ／ｍｍ２、磁気特性としての飽和磁束密度Ｂｓが１．５１Ｔ、透磁率μが４５で体積抵抗率が４．２×１０５Ωｃｍ、金属めっき層の形成性が○、および、それぞれ良好な測定結果及び判断結果が得られた。なお、透磁率μについては、熱処理前にも測定を行った。その結果を表３に示した。
次に、上記ドラム型素体の巻芯部に絶縁被覆導線からなるコイルを巻回するとともに両端部をそれぞれ前記外部導体膜に熱圧着接合し、さらに、上記板状成形体の熱処理で得られた板状の素体を前記ドラム型の素体の鍔部の両側にそれぞれ樹脂系接着剤で接着して巻線型チップインダクタを得た。
The obtained results are shown in Table 1.
As a result, the strength of the element body was 7.4 kgf / mm 2 , the saturation magnetic flux density Bs as magnetic characteristics was 1.51 T, the magnetic permeability μ was 45, the volume resistivity was 4.2 × 10 5 Ωcm, and the metal plating layer Formability was good, and good measurement results and judgment results were obtained. Note that the permeability μ was also measured before the heat treatment. The results are shown in Table 3.
Next, a coil made of an insulating coated conductor is wound around the core portion of the drum-type element body, and both end portions are thermocompression-bonded to the external conductor film, respectively, and further obtained by heat treatment of the plate-shaped molded body. The plate-shaped element body was bonded to both sides of the flange portion of the drum-shaped element body with a resin adhesive to obtain a wire-wound chip inductor.
（実施例２）
原料粒子の組成比を、クロム：３ｗｔ％、ケイ素：５ｗｔ％、鉄：９２ｗｔ％とした以外は、実施例１と同様にして、評価試料を作成し、得られた結果を表１及び表２に示した。
表１および表２に示すとおり、磁気特性としての飽和磁束密度Ｂｓが１．４６Ｔ、透磁率μが４３で、素体の強度が２．８ｋｇｆ／ｍｍ２、体積抵抗率が２．０×１０５Ωｃｍ、金属めっき層の形成性が○で、実施例１と同様、良好な測定結果及び判断結果が得られた。また、ＳＥＭ−ＥＤＳによる分析の結果、熱処理により粒子表面に形成された金属酸化物（酸化層）により粒子同士が結合され、該酸化層は合金粒子に比較して鉄よりも酸化しやすい元素（ここではクロム）が多く含む酸化物であることが確認できた。
(Example 2)
An evaluation sample was prepared in the same manner as in Example 1 except that the composition ratio of the raw material particles was changed to chromium: 3 wt%, silicon: 5 wt%, and iron: 92 wt%. Tables 1 and 2 show the obtained results. It was shown to.
As shown in Tables 1 and 2, the saturation magnetic flux density Bs as magnetic characteristics is 1.46 T, the permeability μ is 43, the strength of the element body is 2.8 kgf / mm 2 , and the volume resistivity is 2.0 × 10. As with Example 1, good measurement results and judgment results were obtained. Moreover, as a result of analysis by SEM-EDS, particles are bonded to each other by a metal oxide (oxide layer) formed on the particle surface by heat treatment, and the oxide layer is more easily oxidized than iron as compared with alloy particles ( Here, it was confirmed that the oxide was rich in chromium.
（実施例３）
原料粒子の平均粒子径（ｄ５０％）を６μｍにした以外は、実施例１と同様にして、評価試料を作成し、得られた結果を表１及び表２に示した。
表１および表２に示すとおり、磁気特性としての飽和磁束密度Ｂｓが１．４５Ｔ、透磁率μが２７で、素体の強度が６．６ｋｇｆ／ｍｍ２、体積抵抗率が３．０×１０５Ωｃｍ、金属めっき層の形成性が○、実施例１と同様、良好な測定結果及び判断結果が得られた。また、ＳＥＭ−ＥＤＳによる分析の結果、熱処理により粒子表面に形成された金属酸化物（酸化層）により粒子同士が結合され、該酸化層は合金粒子に比較して鉄よりも酸化しやすい元素（ここではクロム）が多く含む酸化物であることが確認できた。
(Example 3)
An evaluation sample was prepared in the same manner as in Example 1 except that the average particle diameter (d50%) of the raw material particles was changed to 6 μm, and the obtained results are shown in Tables 1 and 2.
As shown in Tables 1 and 2, the saturation magnetic flux density Bs as magnetic characteristics is 1.45 T, the permeability μ is 27, the strength of the element body is 6.6 kgf / mm 2 , and the volume resistivity is 3.0 × 10. As in Example 1, good measurement results and judgment results were obtained. Moreover, as a result of analysis by SEM-EDS, particles are bonded to each other by a metal oxide (oxide layer) formed on the particle surface by heat treatment, and the oxide layer is more easily oxidized than iron as compared with alloy particles ( Here, it was confirmed that the oxide was rich in chromium.
（実施例４）
原料粒子の平均粒子径（ｄ５０％）を３μｍにした以外は、実施例１と同様にして、評価試料を作成し、得られた結果を表１及び表２に示した。
表１および表２に示すとおり、磁気特性としての飽和磁束密度Ｂｓが１．３８Ｔ、透磁率μが２０で、素体の強度が７．６ｋｇｆ／ｍｍ２、体積抵抗率が７．０×１０５Ωｃｍ、金属メッキ層の形成性が○で、実施例１と同様、良好な測定結果及び判断結果が得られた。また、ＳＥＭ−ＥＤＳによる分析の結果、熱処理により粒子表面に形成された金属酸化物（酸化層）により粒子同士が結合され、該酸化層は合金粒子に比較して鉄よりも酸化しやすい元素（ここではクロム）が多く含む酸化物であることが確認できた。
Example 4
An evaluation sample was prepared in the same manner as in Example 1 except that the average particle diameter (d50%) of the raw material particles was changed to 3 μm, and the obtained results are shown in Tables 1 and 2.
As shown in Tables 1 and 2, the saturation magnetic flux density Bs as magnetic characteristics is 1.38 T, the permeability μ is 20, the strength of the element body is 7.6 kgf / mm 2 , and the volume resistivity is 7.0 × 10. As with Example 1, good measurement results and judgment results were obtained. Moreover, as a result of analysis by SEM-EDS, particles are bonded to each other by a metal oxide (oxide layer) formed on the particle surface by heat treatment, and the oxide layer is more easily oxidized than iron as compared with alloy particles ( Here, it was confirmed that the oxide was rich in chromium.
（実施例５）
原料粒子の組成比をクロム：９．５ｗｔ％、ケイ素：３ｗｔ％、鉄：８７．５ｗｔ％とした以外は、実施例１と同様にして、評価試料を作成し、得られた測定結果及び判断結果を表１および表２に示した。
表１および表２に示すとおり、磁気特性としての飽和磁束密度Ｂｓが１．３６Ｔ、透磁率μが３３で素体の強度が７．４ｋｇｆ／ｍｍ２、体積抵抗率が４．７×１０−３Ωｃｍ、金属めっきの形成性が×、あった。クロムが８ｗｔ％を超えると本実施例では、体積抵抗率が低下することがわかった。また、ＳＥＭ−ＥＤＳによる分析の結果、熱処理により粒子表面に形成された金属酸化物（酸化層）により粒子同士が結合され、該酸化層は合金粒子に比較して鉄よりも酸化しやすい元素（ここではクロム）が多く含む酸化物であることが確認できた。
(Example 5)
An evaluation sample was prepared in the same manner as in Example 1 except that the composition ratio of the raw material particles was chromium: 9.5 wt%, silicon: 3 wt%, and iron: 87.5 wt%. The results are shown in Tables 1 and 2.
As shown in Tables 1 and 2, the saturation magnetic flux density Bs as magnetic characteristics is 1.36 T, the magnetic permeability μ is 33, the strength of the element body is 7.4 kgf / mm 2 , and the volume resistivity is 4.7 × 10 − There was 3 Ωcm, and the formability of metal plating was x. It was found that when the chromium content exceeds 8 wt%, the volume resistivity decreases in this example. Moreover, as a result of analysis by SEM-EDS, particles are bonded to each other by a metal oxide (oxide layer) formed on the particle surface by heat treatment, and the oxide layer is more easily oxidized than iron as compared with alloy particles ( Here, it was confirmed that the oxide was rich in chromium.
（実施例６）
原料粒子の組成比をクロム：５ｗｔ％、ケイ素：１ｗｔ％、鉄：９４ｗｔ％とした以外は、実施例１と同様にして、評価試料を作成し、得られた測定結果及び判断結果を表１および表２に示した。
表１および表２に示すとおり、磁気特性としての飽和磁束密度Ｂｓが１．５８Ｔ、透磁率μが２６で、素体の強度が１８ｋｇｆ／ｍｍ２、体積抵抗率が８．３×１０−３Ωｃｍ、金属めっきの形成性が×であることがわかった。また、ＳＥＭ−ＥＤＳによる分析の結果、熱処理により粒子表面に形成された金属酸化物（酸化層）により粒子同士が結合され、該酸化層は合金粒子に比較して鉄よりも酸化しやすい元素（ここではクロム）が多く含む酸化物であることが確認できた。
(Example 6)
An evaluation sample was prepared in the same manner as in Example 1 except that the composition ratio of the raw material particles was changed to chromium: 5 wt%, silicon: 1 wt%, and iron: 94 wt%. The obtained measurement results and judgment results are shown in Table 1. And in Table 2.
As shown in Tables 1 and 2, the saturation magnetic flux density Bs as magnetic characteristics is 1.58 T, the magnetic permeability μ is 26, the strength of the element body is 18 kgf / mm 2 , and the volume resistivity is 8.3 × 10 −3. It was found that Ωcm and metal plating formability were x. Moreover, as a result of analysis by SEM-EDS, particles are bonded to each other by a metal oxide (oxide layer) formed on the particle surface by heat treatment, and the oxide layer is more easily oxidized than iron as compared with alloy particles ( Here, it was confirmed that the oxide was rich in chromium.
（実施例７）
大気中での処理温度を、１０００℃とした以外は、実施例１と同様にして、インダクタ部品を得た。測定及び判断結果を表１に示す。
表１および表２に示すとおり、磁気特性としての飽和磁束密度Ｂｓが１．５０Ｔ、透磁率μが５０で素体の強度が２０ｋｇｆ／ｍｍ２、体積抵抗率が２．０×１０２Ωｃｍ、金属めっきの形成性が×であった。熱処理温度を高くした本参考例では、３点曲げ破断応力が増加したが、体積抵抗率が実施例１に比較して低下した。また、ＳＥＭ−ＥＤＳによる分析の結果、熱処理により粒子表面に形成された金属酸化物（酸化層）により粒子同士が結合され、該酸化層は合金粒子に比較して鉄よりも酸化しやすい元素（ここではクロム）が多く含む酸化物であることが確認できた。
(Example 7)
An inductor component was obtained in the same manner as in Example 1 except that the treatment temperature in the atmosphere was 1000 ° C. Table 1 shows the measurement and judgment results.
As shown in Table 1 and Table 2, the saturation magnetic flux density Bs as magnetic characteristics is 1.50 T, the magnetic permeability μ is 50, the strength of the element body is 20 kgf / mm 2 , the volume resistivity is 2.0 × 10 2 Ωcm, The formability of metal plating was x. In this reference example in which the heat treatment temperature was increased, the three-point bending rupture stress was increased, but the volume resistivity was lower than that in Example 1. Moreover, as a result of analysis by SEM-EDS, particles are bonded to each other by a metal oxide (oxide layer) formed on the particle surface by heat treatment, and the oxide layer is more easily oxidized than iron as compared with alloy particles ( Here, it was confirmed that the oxide was rich in chromium.
（実施例８）
原料粒子の組成比をケイ素：９．５ｗｔ％、アルミニウム：５．５ｗｔ％、鉄：８５ｗｔ％とした以外は、実施例１と同様にして、評価試料を作成し、得られた測定結果及び判断結果を表１および表２に示した。
表１および表２に示すとおり、磁気特性としての飽和磁束密度Ｂｓが０．７７Ｔ、透磁率μが３２で素体の強度が１．４ｋｇｆ／ｍｍ２、体積抵抗率が８．０×１０３Ωｃｍ、金属めっきの形成性が×、であった。体積抵抗率が低く、外部導体膜の焼付導体層上への金属メッキ層の形成を行なうことができないことがわかった。また、ＳＥＭ−ＥＤＳによる分析の結果、熱処理により粒子表面に形成された金属酸化物（酸化層）により粒子同士が結合され、該酸化層は合金粒子に比較して鉄よりも酸化しやすい元素（ここではアルミニウム）が多く含む酸化物であることが確認できた。
(Example 8)
An evaluation sample was prepared in the same manner as in Example 1 except that the composition ratio of the raw material particles was silicon: 9.5 wt%, aluminum: 5.5 wt%, and iron: 85 wt%. The results are shown in Tables 1 and 2.
As shown in Tables 1 and 2, the saturation magnetic flux density Bs as magnetic characteristics is 0.77 T, the permeability μ is 32, the strength of the element body is 1.4 kgf / mm 2 , and the volume resistivity is 8.0 × 10 3. The formation was Ωcm and the metal plating was x. It has been found that the volume resistivity is low and the metal plating layer cannot be formed on the baked conductor layer of the outer conductor film. Moreover, as a result of analysis by SEM-EDS, particles are bonded to each other by a metal oxide (oxide layer) formed on the particle surface by heat treatment, and the oxide layer is more easily oxidized than iron as compared with alloy particles ( Here, it was confirmed that the oxide contained a large amount of aluminum.
（比較例１）
原料粒子の組成比を、クロム：１ｗｔ％、ケイ素：６．５ｗｔ％、鉄：９２．５ｗｔ％とした以外は、実施例１と同様にして、評価試料を作成し、得られた測定結果及び判断結果を表１および表２に示した。
表１および表２に示すとおり、磁気特性としての飽和磁束密度Ｂｓが１．３６Ｔ、透磁率μが１７で、素体の強度が４．２ｋｇｆ／ｍｍ２、体積抵抗率が４．９×１０Ωｃｍ、金属めっき層の形成性が×、であった。また、ＳＥＭ−ＥＤＳによる分析の結果、Ｃｒが２ｗｔ％未満の本比較例では、熱処理により粒子表面に形成された金属酸化物（酸化層）は、合金粒子に比較して鉄よりも酸化しやすい元素（ここではクロム）を多く含む酸化物ではなく、そのため体積抵抗率が低いことがわかった。
(Comparative Example 1)
An evaluation sample was prepared in the same manner as in Example 1 except that the composition ratio of the raw material particles was changed to chromium: 1 wt%, silicon: 6.5 wt%, and iron: 92.5 wt%. The judgment results are shown in Tables 1 and 2.
As shown in Tables 1 and 2, the saturation magnetic flux density Bs as magnetic characteristics is 1.36 T, the permeability μ is 17, the strength of the element body is 4.2 kgf / mm 2 , and the volume resistivity is 4.9 × 10 Ωcm. The formability of the metal plating layer was x. Further, as a result of analysis by SEM-EDS, in this comparative example in which Cr is less than 2 wt%, the metal oxide (oxide layer) formed on the particle surface by heat treatment is more easily oxidized than iron as compared with alloy particles. It was found that the volume resistivity was low because it was not an oxide rich in elements (here chromium).
（参考例１）
熱処理を行わなかったこと以外は、実施例１と同様にして、評価試料を作成し、得られた測定結果及び判断結果を表１および表２に示した。
表１および表２に示すとおり、磁気特性としての飽和磁束密度Ｂｓが１．５０Ｔ、透磁率μが３５素体の強度が０．５４ｋｇｆ／ｍｍ２、体積抵抗率が１．４×１０５Ωｃｍ、であった。尚、本参考例においては、金属メッキ層の形成性について、試料の作成および評価を省略した。ＳＥＭ−ＥＤＳ分析の結果、本参考例では、粒子の表面には金属酸化物からなる酸化層の生成が行われなかった。このため、体積抵抗率が実施例に比較してやや低下した。
(Reference Example 1)
An evaluation sample was prepared in the same manner as in Example 1 except that the heat treatment was not performed, and the obtained measurement results and judgment results are shown in Tables 1 and 2.
As shown in Tables 1 and 2, the saturation magnetic flux density Bs as magnetic properties is 1.50 T, the permeability μ is 35 element body strength is 0.54 kgf / mm 2 , and the volume resistivity is 1.4 × 10 5 Ωcm. ,Met. In this reference example, the preparation and evaluation of the sample were omitted for the formability of the metal plating layer. As a result of SEM-EDS analysis, in this reference example, an oxide layer made of a metal oxide was not generated on the surface of the particles. For this reason, the volume resistivity slightly decreased as compared with the Examples.
（参考例２）
大気中での処理温度を、３００℃とした以外は、実施例１と同様にして、評価試料を作成し、得られた測定結果及び判断結果を表１および表２に示した。
表１および表２に示すとおり、磁気特性としての飽和磁束密度Ｂｓが１．５０Ｔ、透磁率μが３５で、素体の強度が０．８３ｋｇｆ／ｍｍ２、体積抵抗率が１．４×１０５Ωｃｍであった。尚、本参考例においては、金属メッキ層の形成性について、試料の作成および評価を省略した。ＳＥＭ−ＥＤＳ分析の結果、本参考例では熱処理温度が４００℃より低いために、粒子の表面には金属酸化物からなる酸化層の生成が十分に行われていないことがわかった。このため、体積抵抗率が実施例に比較してやや低下した。
(Reference Example 2)
An evaluation sample was prepared in the same manner as in Example 1 except that the treatment temperature in the atmosphere was 300 ° C. Tables 1 and 2 show the measurement results and determination results obtained.
As shown in Tables 1 and 2, the saturation magnetic flux density Bs as magnetic characteristics is 1.50 T, the magnetic permeability μ is 35, the strength of the element body is 0.83 kgf / mm 2 , and the volume resistivity is 1.4 × 10. It was 5 Ωcm. In this reference example, the preparation and evaluation of the sample were omitted for the formability of the metal plating layer. As a result of SEM-EDS analysis, it was found that an oxide layer made of a metal oxide was not sufficiently formed on the surface of the particles because the heat treatment temperature was lower than 400 ° C. in this reference example. For this reason, the volume resistivity slightly decreased as compared with the Examples.
（実施例９）
次に、積層タイプの実施例を示す。
実施例１と同じ合金粒子を用い、積層数が２０層で、形状が３．２ｍｍ×１．６ｍｍ×０．８ｍｍとなる、素体内部にコイルを有するコイル型電子部品を作成した。
まず、合金金属粒子８５ｗｔ％、ブチルカルビトール（溶剤）１３ｗｔ％で、ポリビニルブチラール（バインダ）２ｗｔ％の混合物をダイコータの塗工機にて、厚み４０μｍのシート状に加工し、次にＡｇ粒子８５ｗｔ％、ブチルカルビトール（溶剤）１３ｗｔ％で、ポリビニルブチラール（バインダ）２ｗｔ％の導体ペーストをシートに塗布し、導電パターンを形成した。
次に導電パターンを形成したシートを積層しプレス圧 ２ｔｏｎ／ｃｍ２にて積層体を得た。
この積層体を、大気下で８００℃、２ｈｒの条件で熱処理し素体を得た。
この内部にコイルが形成された素体のコイルの引き出し部が露出している面および実装面に、Ａｇを含むペーストを塗布し、７００℃、１０ｍｉｎ熱処理をして、金属メッキ層を形成したコイル型電子部品を得た。磁気特性としての飽和磁束密度Ｂｓは１．４１Ｔ、透磁率μは１５であった。なお、熱処理前の透磁率μは１３であった。金属のメッキ層の形成はＮｉであった。また、ＳＥＭ−ＥＤＳによる分析の結果、熱処理により粒子表面に形成された金属酸化物（酸化層）により粒子同士が結合され、該酸化層は合金粒子に比較して鉄よりも酸化しやすい元素（ここではクロム）が多く含む酸化物であることが確認できた。
なお、実施例１から４での粒子は結合部分の厚みが合金粒子表面の酸化層よりも厚かったものが確認された。実施例５、６での粒子は結合部分の厚みが合金粒子表面の酸化層よりも薄かったものが確認された。実施例１から８の粒子の酸化層の厚みが５０ｎｍ以上であったものが確認された。
Example 9
Next, a laminated type embodiment will be shown.
Using the same alloy particles as in Example 1, a coil-type electronic component having 20 layers and a shape of 3.2 mm × 1.6 mm × 0.8 mm and having a coil inside the element body was produced.
First, a mixture of 85 wt% of alloy metal particles, 13 wt% of butyl carbitol (solvent) and 2 wt% of polyvinyl butyral (binder) is processed into a sheet having a thickness of 40 μm using a die coater coating machine, and then 85 wt% of Ag particles. %, Butyl carbitol (solvent) 13 wt%, polyvinyl butyral (binder) 2 wt% conductor paste was applied to the sheet to form a conductive pattern.
Next, the sheet | seat in which the conductive pattern was formed was laminated | stacked, and the laminated body was obtained with the press pressure of 2 ton / cm < 2 >.
This laminated body was heat-treated under conditions of 800 ° C. and 2 hours in the atmosphere to obtain an element body.
A coil in which a metal plating layer is formed by applying a paste containing Ag to the exposed surface and mounting surface of the coil body in which the coil is formed and heat-treating at 700 ° C. for 10 minutes. A mold electronic component was obtained. The saturation magnetic flux density Bs as magnetic characteristics was 1.41 T, and the magnetic permeability μ was 15. The magnetic permeability μ before the heat treatment was 13. The formation of the metal plating layer was Ni. Moreover, as a result of analysis by SEM-EDS, particles are bonded to each other by a metal oxide (oxide layer) formed on the particle surface by heat treatment, and the oxide layer is more easily oxidized than iron as compared with alloy particles ( Here, it was confirmed that the oxide was rich in chromium.
In addition, it was confirmed that the particles in Examples 1 to 4 had a bond portion thicker than the oxide layer on the surface of the alloy particles. In the particles of Examples 5 and 6, it was confirmed that the thickness of the bonded portion was thinner than the oxide layer on the surface of the alloy particles. It was confirmed that the thickness of the oxide layer of the particles of Examples 1 to 8 was 50 nm or more.
本発明の電子部品用軟磁性合金素体および該素体を用いた電子部品は、回路基板上への
面実装が可能な小型化された電子部品に好適である。特に、大電流を流すパワーインダクタに用いた場合、部品の小型化に好適である。
The soft magnetic alloy element body for electronic parts of the present invention and the electronic part using the element body are suitable for miniaturized electronic parts that can be surface-mounted on a circuit board. In particular, when it is used for a power inductor through which a large current flows, it is suitable for miniaturization of parts.
１：粒子
２：酸化層
３：空孔
１０，１０’：電子部品用軟磁性合金を用いた素体
１１：ドラム型のコア
１１ａ：巻芯部
１１ｂ：鍔部
１２：板状コア
１４：外部導体膜
１４ａ：焼付導体膜層
１４ｂ：Ｎｉメッキ層
１４ｃ：Ｓｎメッキ層
１５：コイル
１５ａ：巻回部
１５ｂ：端部（接合部）
２０：電子部品（巻線型チップインダクタ）
３１：積層体チップ
３４：外部導体膜
３５：内部コイル
４０：電子部品（積層型チップインダクタ）
ｄ１：長軸寸法
ｄ２：短軸寸法
1: Particle 2: Oxidation layer 3: Hole 10, 10 ': Element body using soft magnetic alloy for electronic parts 11: Drum-shaped core 11a: Winding core part 11b: Eaves part 12: Plate core 14: External Conductor film 14a: Baking conductor film layer 14b: Ni plating layer 14c: Sn plating layer 15: Coil 15a: Winding part 15b: End part (joining part)
20: Electronic component (wire-wound chip inductor)
31: Multilayer chip 34: External conductor film 35: Internal coil 40: Electronic component (multilayer chip inductor)
d1: Long axis dimension d2: Short axis dimension
Claims (20)
素体は、鉄、ケイ素および鉄より酸化しやすい元素を含有する軟磁性合金の粒子群から構成され、各軟磁性合金粒子の表面には当該粒子を酸化して形成した酸化層が生成され、当該酸化層は当該合金粒子に比較して鉄より酸化しやすい元素を多く含み、粒子同士は当該酸化層を介して結合されており、かつ、前記粒子同士を結合している前記酸化層は同一の相であることを特徴とするコイル型電子部品。 A coil-type electronic component having a coil inside or on the surface of an element body,
The element body is composed of a group of soft magnetic alloy particles containing elements that are more easily oxidized than iron, silicon, and iron, and an oxide layer formed by oxidizing the particles is generated on the surface of each soft magnetic alloy particle. The oxide layer contains more elements that are easier to oxidize than iron compared to the alloy particles, the particles are bonded through the oxide layer, and the oxide layers that bond the particles are the same. A coil-type electronic component characterized by being in a phase.
前記鉄成分の含有量が低下し、且、前記酸化しやすい元素の含有量が増加する第一の酸化層と、
前記鉄成分の含有量が増加し、且、前記酸化しやすい元素の含有量が低下する第二の酸化層と、
をこの順番で含むことを特徴とする請求項１から９のいずれか１項に記載のコイル型電子部品。 The oxide layer is directed outward from the soft magnetic particle side,
A first oxide layer in which the content of the iron component decreases and the content of the easily oxidizable element increases;
A second oxide layer in which the content of the iron component is increased and the content of the easily oxidizable element is decreased;
The coil-type electronic component according to claim 1, comprising:
前記第一の酸化層にて、前記クロムの含有量について変曲点を有することを特徴とする請求項１０に記載のコイル型電子部品。 Looking outward from the soft magnetic particle side,
The coil-type electronic component according to claim 10, wherein the first oxide layer has an inflection point with respect to the chromium content.
バインダーと、鉄、ケイ素および鉄より酸化しやすい元素を含有する軟磁性合金粒子との混合物をプレスして成形体を得る工程と、
前記成形体を酸素を含む雰囲気で熱処理して、前記軟磁性合金粒子の表面に酸化層を形成し前記軟磁性合金粒子同士を酸化層を介して結合させて素体を得る工程と、
前記素体にコイルおよび外部取り出し用の電極を設ける工程と、
を含むコイル型電子部品の製造方法。 In a manufacturing method of a coil-type electronic component in which a coil is provided in an element body,
A step of pressing a mixture of a binder and soft magnetic alloy particles containing iron, silicon, and an element more easily oxidized than iron to obtain a molded body,
By heat-treating the formed shaped body in an atmosphere containing oxygen, obtaining a body of the soft magnetic alloy grains to form an oxide layer on the surface of the soft magnetic alloy particles are bonded through the oxide layer,
Providing the element with a coil and an electrode for external extraction;
A method of manufacturing a coil-type electronic component including:
バインダーと、鉄、ケイ素および鉄より酸化しやすい元素を含有する磁性合金粒子との混合物をシート状に加工し、
当該シートにコイル用導電パターンを形成して積層し成形体を得る工程と、
前記成形体を酸素を含む雰囲気で熱処理して、前記軟磁性合金粒子の表面に酸化層を形成し、前記軟磁性合金粒子同士を酸化層を介して結合させて内部にコイルを有する素体を得る工程と、
前記素体に外部取り出し用の電極を設ける工程と、
を含むコイル型電子部品の製造方法。 In a manufacturing method of a coil-type electronic component in which a coil is provided in an element body,
Processing a mixture of a binder and magnetic alloy particles containing iron, silicon, and an element more easily oxidized than iron into a sheet,
Forming a conductive pattern for a coil on the sheet and laminating it to obtain a molded body; and
By heat-treating the formed shaped body in an atmosphere containing oxygen, body having a soft magnetic oxide layer is formed on the surface of the alloy particles, the coils inside the soft magnetic alloy grains by bonding via the oxide layer And obtaining
Providing an electrode for external extraction on the element;
A method of manufacturing a coil-type electronic component including:
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