JPWO2007013436A1 - Soft magnetic material - Google Patents
Soft magnetic material Download PDFInfo
- Publication number
- JPWO2007013436A1 JPWO2007013436A1 JP2007528470A JP2007528470A JPWO2007013436A1 JP WO2007013436 A1 JPWO2007013436 A1 JP WO2007013436A1 JP 2007528470 A JP2007528470 A JP 2007528470A JP 2007528470 A JP2007528470 A JP 2007528470A JP WO2007013436 A1 JPWO2007013436 A1 JP WO2007013436A1
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- Prior art keywords
- soft magnetic
- magnetic material
- temperature
- material according
- powder
- Prior art date
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Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01F—MAGNETS; INDUCTANCES; TRANSFORMERS; SELECTION OF MATERIALS FOR THEIR MAGNETIC PROPERTIES
- H01F1/00—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties
- H01F1/01—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials
- H01F1/03—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials characterised by their coercivity
- H01F1/12—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials characterised by their coercivity of soft-magnetic materials
- H01F1/14—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials characterised by their coercivity of soft-magnetic materials metals or alloys
- H01F1/20—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials characterised by their coercivity of soft-magnetic materials metals or alloys in the form of particles, e.g. powder
- H01F1/22—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials characterised by their coercivity of soft-magnetic materials metals or alloys in the form of particles, e.g. powder pressed, sintered, or bound together
- H01F1/24—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials characterised by their coercivity of soft-magnetic materials metals or alloys in the form of particles, e.g. powder pressed, sintered, or bound together the particles being insulated
- H01F1/26—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials characterised by their coercivity of soft-magnetic materials metals or alloys in the form of particles, e.g. powder pressed, sintered, or bound together the particles being insulated by macromolecular organic substances
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K9/00—Screening of apparatus or components against electric or magnetic fields
- H05K9/0073—Shielding materials
- H05K9/0081—Electromagnetic shielding materials, e.g. EMI, RFI shielding
- H05K9/0083—Electromagnetic shielding materials, e.g. EMI, RFI shielding comprising electro-conductive non-fibrous particles embedded in an electrically insulating supporting structure, e.g. powder, flakes, whiskers
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01F—MAGNETS; INDUCTANCES; TRANSFORMERS; SELECTION OF MATERIALS FOR THEIR MAGNETIC PROPERTIES
- H01F17/00—Fixed inductances of the signal type
- H01F17/04—Fixed inductances of the signal type with magnetic core
- H01F2017/048—Fixed inductances of the signal type with magnetic core with encapsulating core, e.g. made of resin and magnetic powder
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01F—MAGNETS; INDUCTANCES; TRANSFORMERS; SELECTION OF MATERIALS FOR THEIR MAGNETIC PROPERTIES
- H01F3/00—Cores, Yokes, or armatures
- H01F3/08—Cores, Yokes, or armatures made from powder
Abstract
バインダー樹脂中に軟磁性粉末を密に配向させた状態で架橋させて比重を大きくし、高温あるいは高温高湿環境下において寸法変化や磁気特性の変化が小さい軟磁性材料を提供する。軟磁性材料は、少なくとも扁平軟磁性粉末が架橋されたポリエステル系樹脂に分散してなるものであり、扁平軟磁性粉末を４５０〜５５０重量％、架橋されたポリエステル系樹脂を８０〜１２０重量％含有する。扁平軟磁性粉末は、ほぼ同一面内方向に配向している。Provided is a soft magnetic material in which soft magnetic powder is crosslinked in a densely oriented state in a binder resin to increase the specific gravity, and the dimensional change and magnetic property change are small in a high temperature or high temperature and high humidity environment. The soft magnetic material is formed by dispersing at least a flat soft magnetic powder in a crosslinked polyester resin, and contains 450 to 550% by weight of a flat soft magnetic powder and 80 to 120% by weight of a crosslinked polyester resin. To do. The flat soft magnetic powder is oriented in substantially the same in-plane direction.
Description
本発明は、いわゆるＲＦＩＤ（Ｒａｄｉｏ Ｆｒｅｑｕｅｎｃｙ Ｉｄｅｎｔｉｆｉｃａｔｉｏｎ）機能を有するモバイル端末での１３．５６ＭＨｚの周波数を用いる通信を改善するために、近傍金属の影響を減らす磁性材料に関し、比重が大きい軟磁性シートおよびその製造方法に関する。また、電子機器内の不要電磁波の干渉によって生じる電磁障害を抑制するための磁性材料に関する。 The present invention relates to a magnetic material that reduces the influence of nearby metals in order to improve communication using a 13.56 MHz frequency in a mobile terminal having a so-called RFID (Radio Frequency Identification) function. It relates to a manufacturing method. The present invention also relates to a magnetic material for suppressing electromagnetic interference caused by interference of unnecessary electromagnetic waves in electronic equipment.
近年、１３．５６ＭＨｚ帯で無線通信を行うＩＣタグ機能を有する携帯電話をはじめとするモバイル端未が実用化されている。この場合、小型、薄型の携帯電話の筐体内に送受信用のアンテナコイルを配置する用途があるが、電磁波シールド対策により金属筐体内もしくはメッキ等の導電化処理を施された筐体内面がこのアンテナコイルに近接して存在した場合、送受信時にアンテナコイルの周囲に発生する磁界の磁力線が金属表面に平行に走り、金属表面に渦電流を発生させるなど、通信に用いる磁界が大きく減衰し、通信距離が著しく短くなる現象が確認されている。この対策の一つの方法としては、アンテナコイルの平面と平行になるように磁性材料を配置し、アンテナコイルのインダクタンスを大きくし、通信距離を向上させることが提案されている（特許文献１）。 In recent years, mobile terminals such as mobile phones having an IC tag function for performing wireless communication in the 13.56 MHz band have been put into practical use. In this case, there is an application in which an antenna coil for transmission / reception is arranged in a casing of a small and thin mobile phone, but the inner surface of the casing that has been subjected to a conductive treatment such as plating or the like by electromagnetic wave shielding measures is used for this antenna. When it is in close proximity to the coil, the magnetic field lines generated around the antenna coil during transmission and reception run parallel to the metal surface, generating eddy currents on the metal surface, and so the magnetic field used for communication is greatly attenuated, resulting in a communication distance. Has been confirmed to be significantly shortened. As one of the countermeasures, it has been proposed to arrange a magnetic material so as to be parallel to the plane of the antenna coil, increase the inductance of the antenna coil, and improve the communication distance (Patent Document 1).
また、近年、テレビなどの家庭電気製品、パーソナルコンピューター、携帯電話などの移動体通信機器、医療機器などの電子機器が広く使われており、上記の電子機器から放出された不要電磁波が他の電子機器に誤作動を発生させるといった影響を及ぼす場合がある。そのため、このような電子機器において、不要電磁波を取り除くために電磁干渉抑制の目的で磁性材料が用いられている。 In recent years, electronic devices such as household electric appliances such as televisions, mobile communication devices such as personal computers and mobile phones, and medical devices have been widely used. It may affect the operation of the device. Therefore, in such an electronic device, a magnetic material is used for the purpose of suppressing electromagnetic interference in order to remove unnecessary electromagnetic waves.
ところで、携帯通信端末では、通信特性を向上させるために、アンテナコイルとシールド板との間に、磁性粉末を含有する軟磁性シートを配置したアンテナモジュールが用いられている。この場合、携帯通信端末等の小型化、薄型化に伴って、厚さが薄く透磁率が大きな軟磁性シートが要求されている。他方、通信移動端末等の電子機器に内蔵されるアンテナモジュールに対しては、モジュールの薄型化という要請と相反する要求、即ち、通信距離を更に向上させるということが要求されている。従って、通信携帯端末等には、それらの要求を同時に満たすことが求められている。 By the way, in a mobile communication terminal, an antenna module in which a soft magnetic sheet containing magnetic powder is disposed between an antenna coil and a shield plate is used to improve communication characteristics. In this case, with the miniaturization and thinning of portable communication terminals and the like, a soft magnetic sheet having a small thickness and a large magnetic permeability is required. On the other hand, for antenna modules built in electronic devices such as communication mobile terminals, there is a demand that contradicts the demand for thinning the module, that is, to further improve the communication distance. Accordingly, communication portable terminals and the like are required to satisfy these requirements simultaneously.
上述した要求に応えるべく、アンテナモジュールに使用する磁性シートを構成する磁性粉末のサイズの検討がなされている。例えば、アンテナモジュールに用いるべき磁性粉末の粒子サイズを大きくすることにより磁性シートの透磁率を高め、アンテナモジュールの通信距離を大きくすることができる。しかし、磁性粉末の粒子サイズを大きくすると、磁性シートの過電流損失に起因するパワーロスが顕著となり、ＩＣ読み出し電圧の低下及び通信距離が短くなるという問題が生ずる。 In order to meet the above-described requirements, the size of the magnetic powder constituting the magnetic sheet used in the antenna module has been studied. For example, by increasing the particle size of the magnetic powder to be used in the antenna module, the magnetic sheet can be increased in permeability and the communication distance of the antenna module can be increased. However, when the particle size of the magnetic powder is increased, the power loss due to the overcurrent loss of the magnetic sheet becomes remarkable, causing problems that the IC read voltage is lowered and the communication distance is shortened.
このため、前述の相反する要求に対しては、「磁性シートの透磁率を大きくすること」と「過電流損失を低滅すること」とのバランスをとるために、使用すべき磁性粉末のサイズの大型化に制限を加えると共に、磁性粉末の使用量（配合比）を少なくすることが試みられている。しかし、透磁率を大きくするためには磁性シートの比重を大きくする必要があるが、磁性粉末の使用量を少なくすると磁性シートの比重を大きくできないという欠点がある。よって、必要な磁気特性を確保するためには磁性シート厚を厚くしなければならず、アンテナモジュールの厚さを厚くせざるを得ない。 For this reason, in order to balance the above-mentioned conflicting demands, the size of the magnetic powder to be used should be balanced in order to balance “increasing the magnetic permeability of the magnetic sheet” and “decreasing the overcurrent loss”. Attempts have been made to limit the increase in size and reduce the amount of magnetic powder used (mixing ratio). However, in order to increase the magnetic permeability, it is necessary to increase the specific gravity of the magnetic sheet, but there is a drawback that the specific gravity of the magnetic sheet cannot be increased if the amount of magnetic powder used is reduced. Therefore, in order to ensure the required magnetic characteristics, the magnetic sheet thickness must be increased, and the antenna module must be increased in thickness.
そこで、以上のような問題の解決を意図した磁性シートとして、扁平な軟磁性粉末とバインダー樹脂として塩素化ポリエチレンと溶媒とを混合し、得られた軟磁性塗料を剥離基材上に塗布し、乾燥した後、剥離基材から剥離し、温度１８０℃、圧力３０ＭＰａで熱プレスすることにより、扁平な軟磁性粉末を面内方向に配向させた軟磁性シートが提案されている（特許文献２）。 Therefore, as a magnetic sheet intended to solve the above problems, flat soft magnetic powder and chlorinated polyethylene as a binder resin and a solvent are mixed, and the obtained soft magnetic paint is applied onto a release substrate, After drying, a soft magnetic sheet is proposed in which flat soft magnetic powder is oriented in the in-plane direction by peeling from a peeling substrate and hot pressing at a temperature of 180 ° C. and a pressure of 30 MPa (Patent Document 2). .
ところで、このような軟磁性シートにおいて、その透磁率を大きくしようとする場合、ガラス転移点Ｔｇが室温に比べて極端に低い樹脂を用いれば、軟磁性シート自体の軟化点が低くなるので、軟化点以上の熱を加えながらラミネーターや熱プレス装置で圧縮することによって軟磁性粉末を効率良く配向させることができ、比重を大きくすることができる。一方、このような軟磁性シートに対しては、更に、長期にわたって優れた寸法安定性や磁気特性安定性を示すことが要求される。これは、磁性シートの厚さが変化すると、これを用いたアンテナモジュールにおいて、アンテナコイルとシールド板の相対位置関係や、軟磁性シート自体の磁気特性が変化してしまい、通信特性が変化してしまうという問題が生ずるからである。このため、軟磁性シートを製造する際には、高分子結合剤を架橋させるために硬化剤を併用することが試みられている。
しかし、軟磁性塗料を剥離基材上に塗布した後に溶媒を乾燥させる際に、硬化剤とバインダー樹脂とが反応して硬化反応が開始し、更に熱を加えながらラミネータや熱プレス機を用いて圧縮すると硬化反応が更に進行し、ある程度まで圧縮した状態で巻き込んでいるエアーを含んだまま硬化してしまうため、その比重を意図した値まで大きくすることができない場合がある。また、バインダー樹脂のガラス転移点Ｔｇが低すぎると、軟磁性シートを高温あるいは高温高湿環境下に放置した際に、圧縮された軟磁性シートが緩み、厚さが戻ってしまうという問題がある。 However, when the solvent is dried after the soft magnetic paint is applied on the release substrate, the curing agent and the binder resin react with each other to start the curing reaction, and further using a laminator or a hot press machine while applying heat. When the compression is performed, the curing reaction further proceeds, and the resin is cured while containing air entrained in a compressed state to a certain extent, so that the specific gravity may not be increased to an intended value. Further, if the glass transition point Tg of the binder resin is too low, there is a problem that when the soft magnetic sheet is left in a high temperature or high temperature and high humidity environment, the compressed soft magnetic sheet is loosened and the thickness is returned. .
本発明は、前記問題点を解決するために提案されたものであり、バインダー樹脂中に軟磁性粉末を密に配向させた状態で架橋させて比重を大きくし、高温あるいは高温高湿環境下において寸法変化や磁気特性の変化が小さい軟磁性材料及びその製造方法、並びに本発明の磁性材料を利用する電子機器、例えばアンテナモジュールや携帯通信端末を提供することを目的とする。 The present invention has been proposed in order to solve the above-described problems, and the specific gravity is increased by cross-linking the soft magnetic powder in the binder resin in a densely oriented state under a high temperature or high temperature and high humidity environment. It is an object of the present invention to provide a soft magnetic material with a small dimensional change and magnetic property change, a manufacturing method thereof, and an electronic device using the magnetic material of the present invention, such as an antenna module or a portable communication terminal.
本発明者らは、軟磁性粉末として扁平な形状のものを使用し、バインダー樹脂としてポリエステル系樹脂を使用し、且つバインダー樹脂を架橋させることにより、上述の目的を達成できることを見出し、本発明を完成させるに至った。 The present inventors have found that the above-described object can be achieved by using a soft magnetic powder having a flat shape, using a polyester resin as a binder resin, and crosslinking the binder resin. It came to complete.
即ち、本発明は、少なくとも扁平軟磁性粉末が、架橋されたポリエステル系樹脂に分散してなる軟磁性材料を提供する。 That is, the present invention provides a soft magnetic material in which at least flat soft magnetic powder is dispersed in a crosslinked polyester resin.
また、本発明は、上述の軟磁性材料を備えた電子機器、例えば、軟磁性材料がアンテナコイルが形成された支持体に積層されていることを特徴とするアンテナモジュール、及びそのアンテナモジュールを備えた携帯通信端末を提供する。 The present invention also includes an electronic device including the above-described soft magnetic material, for example, an antenna module in which the soft magnetic material is laminated on a support body on which an antenna coil is formed, and the antenna module. A portable communication terminal is provided.
更に、本発明は、シート状の上述の軟磁性材料の製造方法であって、少なくとも扁平軟磁性粉末とポリエステル系樹脂と架橋剤と溶剤とを混合してなる軟磁性組成物を剥離基材上に塗布した後に、架橋反応が実質的に生じない温度で乾燥し、架橋反応が生ずる温度で圧縮する、軟磁性材料の製造方法を提供する。この場合、架橋反応が実質的に生じない温度で乾燥した後、架橋反応が生ずる温度で圧縮する前に、架橋反応が実質的に生じない温度で圧縮することが好ましい。 Furthermore, the present invention is a method for producing the above-mentioned soft magnetic material in sheet form, wherein a soft magnetic composition comprising at least a flat soft magnetic powder, a polyester resin, a crosslinking agent and a solvent is mixed on a release substrate. A method for producing a soft magnetic material is provided, which is dried at a temperature at which a cross-linking reaction does not substantially occur and then compressed at a temperature at which the cross-linking reaction occurs. In this case, after drying at a temperature at which the crosslinking reaction does not substantially occur, it is preferable to compress at a temperature at which the crosslinking reaction does not substantially occur before compression at a temperature at which the crosslinking reaction occurs.
また、本発明は、少なくとも扁平軟磁性粉末とポリエステル系樹脂と架橋剤と溶剤とを混合してなる軟磁性組成物を剥離基材上に塗布した後に、架橋反応が実質的に生じない温度で乾燥し、剥離基材を取り除くことを繰り返すことにより、少なくとも２枚の軟磁性組成物の乾燥シートを取得し、その少なくとも２枚の乾燥シートを積層し、架橋反応が生ずる温度で圧縮する、積層軟磁性シートの製造方法を提供する。この場合、少なくとも２枚の乾燥シートを積層した後、架橋反応が生ずる温度で圧縮する前に、架橋反応が実質的に生じない温度で圧縮することが好ましい。 The present invention also provides a temperature at which a crosslinking reaction does not substantially occur after a soft magnetic composition comprising at least a flat soft magnetic powder, a polyester resin, a crosslinking agent, and a solvent is applied onto a release substrate. By repeating the drying and removing the release substrate, at least two dry sheets of the soft magnetic composition are obtained, the at least two dry sheets are laminated, and compressed at a temperature at which a crosslinking reaction occurs. A method for producing a soft magnetic sheet is provided. In this case, after laminating at least two dry sheets, it is preferable to compress at a temperature at which crosslinking reaction does not substantially occur before compression at a temperature at which crosslinking reaction occurs.
本発明の軟磁性材料においては、バインダー樹脂であるポリエステル系樹脂に扁平な軟磁性粉末が密に配向しながら分散しており、その状態で当該ポリエステル系樹脂が架橋されているので、比重が大きく良好な磁気特性を示す。また、高温環境下、あるいは高温高湿環境下においても寸法変化が小さく、信頼性の高い軟磁性材料となる。また、ポリエステル系樹脂としてリン内添ポリエステル系樹脂を用いると、酸価を大きくすることができ、金属に対する優れた接着性を示すので、比重を大きくすることができる。従って、本発明の軟磁性材料は、環境試験後の寸法変化が小さく磁気特性の変化も小さいので、シート化し、これをアンテナモジュールに適用すれば、通信距離の向上を図ることが可能となる。しかもアンテナモジュールの薄型化及び軽量化も図ることができる。更に、このようなアンテナモジュールが金属筐体内に格納されたとしても、その通信性能の劣化が抑制され、初期の通信距離が維特される。よって、本発明の軟磁性材料は、ＲＦＩＤ用途や電波吸収体として有用であり、また、携帯用デジタルカメラ等の電子機器のノイズ電磁波吸収体として用いることができる。 In the soft magnetic material of the present invention, the flat soft magnetic powder is dispersed while being densely oriented in the polyester resin as the binder resin, and since the polyester resin is crosslinked in this state, the specific gravity is large. Good magnetic properties. Further, the dimensional change is small even in a high temperature environment or a high temperature and high humidity environment, and the soft magnetic material is highly reliable. Further, when a phosphorus-containing polyester-based resin is used as the polyester-based resin, the acid value can be increased and excellent adhesion to metal can be exhibited, so that the specific gravity can be increased. Therefore, the soft magnetic material of the present invention has a small dimensional change after an environmental test and a small change in magnetic characteristics. Therefore, if it is formed into a sheet and applied to an antenna module, the communication distance can be improved. In addition, the antenna module can be made thinner and lighter. Further, even if such an antenna module is stored in a metal casing, deterioration of the communication performance is suppressed, and the initial communication distance is maintained. Therefore, the soft magnetic material of the present invention is useful for RFID applications and radio wave absorbers, and can be used as a noise electromagnetic wave absorber for electronic devices such as portable digital cameras.
本発明の軟磁性材料は、少なくとも扁平軟磁性粉末が、架橋されたポリエステル系樹脂に分散してなるものであり、好ましくはシート形状の軟磁性材料である。 The soft magnetic material of the present invention is obtained by dispersing at least a flat soft magnetic powder in a crosslinked polyester resin, and is preferably a sheet-shaped soft magnetic material.
本発明の軟磁性材料においては、まず、軟磁性粉末として扁平軟磁性粉末を使用する。従って、扁平軟磁性材料を２次元の面内方向に配列させることにより、高い透磁率と大きな比重とを実現することができる。 In the soft magnetic material of the present invention, first, flat soft magnetic powder is used as soft magnetic powder. Therefore, high magnetic permeability and large specific gravity can be realized by arranging the flat soft magnetic materials in a two-dimensional in-plane direction.
扁平軟磁性粉末の原材料としては、任意の軟磁性合金を用いることができ、例えば、磁性ステンレス（Ｆｅ−Ｃｒ−Ａｌ−Ｓｉ合金）、センダスト（Ｆｅ−Ｓｉ−Ａ１合金）、パーマロイ（Ｆｅ−Ｎｉ合金）、ケイ素銅（Ｆｅ−Ｃｕ−Ｓｉ合金）、Ｆｅ−Ｓｉ合金、Ｆｅ−Ｓｉ―Ｂ（−Ｃｕ−Ｎｂ）合金、Ｆｅ−Ｎｉ−Ｃｒ−Ｓｉ合金、Ｆｅ−Ｓｉ−Ｃｒ合金、Ｆｅ−Ｓｉ−Ａｌ−Ｎｉ−Ｃｒ合金、フェライト等が挙げられる。これらの中でも、磁気特性の点からＦｅ−Ｓｉ−Ａｌ合金又はＦｅ−Ｓｉ−Ｃｒ−Ｎｉ合金を好ましく使用できる。 As a raw material of the flat soft magnetic powder, any soft magnetic alloy can be used, for example, magnetic stainless steel (Fe—Cr—Al—Si alloy), sendust (Fe—Si—A1 alloy), permalloy (Fe—Ni). Alloy), silicon copper (Fe—Cu—Si alloy), Fe—Si alloy, Fe—Si—B (—Cu—Nb) alloy, Fe—Ni—Cr—Si alloy, Fe—Si—Cr alloy, Fe— Si-Al-Ni-Cr alloy, ferrite, etc. are mentioned. Among these, Fe-Si-Al alloys or Fe-Si-Cr-Ni alloys can be preferably used from the viewpoint of magnetic properties.
これらの軟磁性合金に関し、複素比透磁率の実数部（透磁率）μ′の数値が比較的大きく（好ましくは３５以上）、複素比透磁率の虚数部（磁気損失）μ″の数値が比較的小さく（好ましくは１以下）、Ｑ値が比較的大きい（好ましくは２８以上）ものを使用することが好ましい。即ち、μ′の数値が大きいほど、ＲＦＩＤ通信アンテナコイル磁束が対応するアンテナコイルを通過しやすくなるのでアンテナの感度が向上し、虚数部μ″の数値が小さいほど、磁性材料渦電流損失に起因するパワーロスが小さくなり、ＩＣ呼び出し電圧が低下せず、通信距離を短くさせない。また、Ｑ値が大きくなればなるほど、共振周波数の選択性が高まり、感度が良くなる。なお、μ′やμ″の値は、磁性合金の組成や使用周波数によって変動するが、本発明の軟磁性材料では、透磁率μ′は３５以上であることが好ましい。透磁率μ′が３５以上であれば、携帯用モバイル電子機器に搭載した際の通信距離が１１０ｍｍ以上となり、利便性が向上する。また、軟磁性材料の比重は３．０以上であることが望ましい。より好ましくは３．２０以上である。軟磁性材料の比重を大きくすることによって、軟磁性材料の中に含まれる空気が少なくなり、難燃性を向上させることができる。 For these soft magnetic alloys, the value of the real part (permeability) μ ′ of the complex relative permeability is relatively large (preferably 35 or more), and the value of the imaginary part (magnetic loss) μ ″ of the complex relative permeability is compared. It is preferable to use an antenna coil with a small Q value (preferably 1 or less) and a relatively large Q value (preferably 28 or more), that is, the larger the value of μ ′, the corresponding antenna coil with the RFID communication antenna coil magnetic flux. The antenna sensitivity is improved because it easily passes, and the smaller the numerical value of the imaginary part μ ″, the smaller the power loss due to the magnetic material eddy current loss, the IC calling voltage does not decrease, and the communication distance does not shorten. Also, the higher the Q value, the higher the selectivity of the resonance frequency and the better the sensitivity. The values of μ ′ and μ ″ vary depending on the composition of the magnetic alloy and the operating frequency, but in the soft magnetic material of the present invention, the magnetic permeability μ ′ is preferably 35 or more. The magnetic permeability μ ′ is 35. In this way, the communication distance when mounted on a portable mobile electronic device is 110 mm or more, which improves convenience, and the specific gravity of the soft magnetic material is preferably 3.0 or more, more preferably 3. By increasing the specific gravity of the soft magnetic material, the air contained in the soft magnetic material is reduced, and the flame retardancy can be improved.
また、扁平軟磁性合金としては、渦電流損失の低減を目的にμ″の値を小さくするために、比較的抵抗が大きいものを使用することが好ましい。この場合、磁性合金の組成を変えることで抵抗を大きくすることができる。例えば、Ｆｅ−Ｓｉ−Ｃｒ合金の場合、Ｓｉの割合を９〜１５ｗｔ．％とすることが好ましい。 In addition, it is preferable to use a flat soft magnetic alloy having a relatively large resistance in order to reduce the value of μ ″ for the purpose of reducing eddy current loss. In this case, the composition of the magnetic alloy is changed. For example, in the case of an Fe—Si—Cr alloy, the Si ratio is preferably 9 to 15 wt.
本発明で使用する扁平軟磁性粉末としては、扁平な形状の軟磁性粉末を用いるが、好ましくは平均粒子径が３．５〜９０μｍ、平均厚さが０．３〜２．１μｍ、より好ましくは平均粒子径が１０〜５０μｍ、平均厚さが０.５〜１.５μｍである。従って、扁平率を好ましくは８〜２４、より好ましくは１５〜２２に設定する。なお、扁平軟磁性粉末の大きさを揃えるためには、必要に応じて、ふるい等を使用して分級すればよい。なお、軟磁性材料の透磁率を大きくするためには、扁平軟磁性粉末の粒子サイズを大きくして粒子同士の間隔を小さくし、且つ扁平な軟磁性粉末のアスペクト比を高めて軟磁性シートにおける反磁場の影響を小さくすることが有効である。 As the flat soft magnetic powder used in the present invention, a soft magnetic powder having a flat shape is used. Preferably, the average particle diameter is 3.5 to 90 μm, and the average thickness is 0.3 to 2.1 μm, more preferably. The average particle diameter is 10 to 50 μm, and the average thickness is 0.5 to 1.5 μm. Therefore, the flatness is preferably set to 8 to 24, more preferably 15 to 22. In addition, what is necessary is just to classify | classify using a sieve etc. as needed in order to arrange the magnitude | size of a flat soft magnetic powder. In order to increase the permeability of the soft magnetic material, the particle size of the flat soft magnetic powder is increased to reduce the interval between the particles, and the aspect ratio of the flat soft magnetic powder is increased to increase the aspect ratio of the soft magnetic material. It is effective to reduce the influence of the demagnetizing field.
本発明で使用する扁平軟磁性粉末のタップ密度（ＪＩＳ Ｋ ５１０１）と比表面積（ＢＥＴ法）とは互いに反比例する関係にあるが、非表面積が大きくなるとμ′の値だけでなく、大きくしたくないμ″の値も大きくなる傾向があるため、それらの数値範囲を好ましい範囲に設定する。具体的にはタップ密度を好ましくは０．５５〜１．４５ｇ／ｍｌ、より好ましくは０．６５〜１．０ｇ／ｍｌに設定し、一方、比表面積を好ましくは０．４０〜１．２０ｍ２／ｇ、より好ましくは０．６５〜１．００ｍ２／ｇに設定する。The tap density (JIS K 5101) and specific surface area (BET method) of the flat soft magnetic powder used in the present invention are inversely proportional to each other. However, when the non-surface area is increased, not only the value of μ ′ but also the value is increased. Therefore, the numerical value range is set to a preferable range. Specifically, the tap density is preferably 0.55 to 1.45 g / ml, more preferably 0.65. On the other hand, the specific surface area is preferably set to 0.40 to 1.20 m 2 / g, more preferably 0.65 to 1.00 m 2 / g.
また、扁平軟磁性粉末として、その表面を絶縁層で被覆したものを使用することができる。絶縁層で被覆した扁平軟磁性粉末を使用することにより、扁平軟磁性材料のμ′が低下し、Ｑが向上するので、ＲＦＩＤ（Ｒａｄｉｏ Ｆｒｅｑｕｅｎｃｙ Ｉｄｅｎｔｉｆｉｃａｔｉｏｎ）機能を有するモバイル端末の通信距離が向上する。絶縁層の形成方法としては、樹脂でコーティングする方法や加熱により酸化膜を形成する方法、さらには軟磁性粉末にスパッタ等の薄膜形成技術で酸化膜を形成する方法がある。酸化膜としてはＡｌ２Ｏ３、ＳｉＯ２等を用いることができる。コーティングする樹脂としては、アクリレート系、エステル系、ウレタン系、エポキシ系等の樹脂を用いることができる。Further, as the flat soft magnetic powder, a powder whose surface is covered with an insulating layer can be used. By using the flat soft magnetic powder coated with the insulating layer, μ ′ of the flat soft magnetic material is lowered and Q is improved, so that the communication distance of a mobile terminal having an RFID (Radio Frequency Identification) function is improved. As a method for forming the insulating layer, there are a method of coating with a resin, a method of forming an oxide film by heating, and a method of forming an oxide film on a soft magnetic powder by a thin film forming technique such as sputtering. As the oxide film, Al 2 O 3 , SiO 2 or the like can be used. As the resin to be coated, resins such as acrylate, ester, urethane, and epoxy can be used.
本発明で使用する扁平軟磁性材料は、絶縁層で被覆された扁平軟磁性粉末の使用が必須ではないが、使用する扁平軟磁性粉末の少なくとも５重量％程度を絶縁層被覆扁平軟磁性粉末を使用することが好ましい。 The flat soft magnetic material used in the present invention does not necessarily require the use of a flat soft magnetic powder coated with an insulating layer, but at least about 5% by weight of the flat soft magnetic powder used is made of an insulating layer coated flat soft magnetic powder. It is preferable to use it.
また、本発明においては、扁平軟磁性粉末として、例えばシランカップリング剤等のカップリング剤を用いてカップリング処理した軟磁性粉末を用いるようにしてもよい。カップリング処理した軟磁性粉末を用いることによって、扁平軟磁性粉末とバインダー樹脂であるポリエステル系樹脂との界面の補強効果を高め、比重や耐食性を向上させることができる。カップリング剤としては、例えば、γ−メタクリロキシプロピルトリメトキシシラン、γ−グリシドキシプロピルトリメトキシシラン、γ−グリシドキシプロピルメチルジエトキシシラン等を用いることができる。なお、前記カップリング処理は、予め軟磁性粉末に対して施しておいてもよいし、扁平軟磁性粉末とバインダー樹脂とを混合する際に同時に混合し、その結果前記カップリング処理が行われるようにしてもよい。 In the present invention, as the flat soft magnetic powder, for example, a soft magnetic powder subjected to a coupling treatment using a coupling agent such as a silane coupling agent may be used. By using the soft magnetic powder subjected to the coupling treatment, the reinforcing effect of the interface between the flat soft magnetic powder and the polyester resin as the binder resin can be enhanced, and the specific gravity and corrosion resistance can be improved. As the coupling agent, for example, γ-methacryloxypropyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropylmethyldiethoxysilane and the like can be used. The coupling treatment may be performed on the soft magnetic powder in advance, or when the flat soft magnetic powder and the binder resin are mixed at the same time, the coupling treatment is performed as a result. It may be.
本発明の軟磁性材料における扁平軟磁性粉末の使用量は、少なすぎると意図した磁気特性が得られず、多すぎると相対的にバインダー樹脂量が少なくなり、成形性が低下するので、好ましくは４００〜６００重量％、より好ましくは４５０〜５５０重量％である。 If the amount of the flat soft magnetic powder in the soft magnetic material of the present invention is too small, the intended magnetic properties cannot be obtained, and if it is too large, the amount of the binder resin is relatively small, and the moldability is reduced. It is 400 to 600% by weight, more preferably 450 to 550% by weight.
本発明においては、バインダー樹脂として、良好な加工性を有し、吸湿性が低く、シート化しても実用上の強度を保つことができ、扁平軟磁性粉末を多量に保持することが可能なポリエステル系樹脂を用いる。このようなポリエステル系樹脂の数平均分子量は、その数平均分子量が小さすぎると、得られるシート状の軟磁性材料の機械的強度が不充分となり、大きすぎると得られるシート状の軟磁性材料が固く脆くなるので、好ましくは３０００〜１０００００、より好ましくは８０００〜５００００、特に好ましくは１００００〜５００００である。 In the present invention, as a binder resin, a polyester that has good processability, low hygroscopicity, can maintain practical strength even when formed into a sheet, and can retain a large amount of flat soft magnetic powder. System resin is used. The number average molecular weight of such a polyester-based resin is such that if the number average molecular weight is too small, the mechanical strength of the resulting sheet-like soft magnetic material is insufficient, and if it is too large, the resulting sheet-like soft magnetic material is Since it becomes hard and brittle, Preferably it is 3000-100000, More preferably, it is 8000-50000, Most preferably, it is 10000-50000.
また、バインダー樹脂であるポリエステル系樹脂のガラス転位点は、低すぎると高温下での弾性率が低下して軟磁性粉末同士の接着力が不充分となり、高すぎると得られるシート状の軟磁性材料が固くなり、室温下での取り扱い性が低下し、また軟化点が高くなりすぎる傾向があり、軟磁性材料の圧縮や軟磁性粉末の配向が円滑に進まなくなるおそれがあるので、ガラス転移点は好ましくは−２０℃〜４０℃、より好ましくは−２０℃〜１０℃であり、軟化点が好ましくは１３０℃以下、より好ましくは１００℃以下である。 In addition, if the glass transition point of the polyester resin, which is a binder resin, is too low, the elastic modulus at high temperatures decreases and the adhesive strength between the soft magnetic powders becomes insufficient. The glass transition point because the material becomes hard, the handleability at room temperature decreases, the softening point tends to be too high, and the compression of the soft magnetic material and the orientation of the soft magnetic powder may not proceed smoothly. Is preferably −20 ° C. to 40 ° C., more preferably −20 ° C. to 10 ° C., and the softening point is preferably 130 ° C. or less, more preferably 100 ° C. or less.
バインダー樹脂であるポリエステル系樹脂の水酸基価（ＪＩＳ Ｋ １５５７）は、小さすぎると架橋が不十分となって機械的強度が不足し、軟磁性材料の厚み変化が大きくなるおそれがあり、大きすぎると吸湿性が高くなりすぎるおそれがあるので、好ましくは４．５ｍｇＫＯＨ／ｇ〜１５ｍｇＫＯＨ／ｇ、より好ましくは４.５ｍｇＫＯＨ／ｇ〜８ｍｇＫＯＨ／ｇである。 If the hydroxyl value (JIS K 1557) of the polyester resin that is the binder resin is too small, the crosslinking is insufficient and the mechanical strength is insufficient, and the thickness change of the soft magnetic material may be increased. Since there is a possibility that the hygroscopicity becomes too high, it is preferably 4.5 mgKOH / g to 15 mgKOH / g, more preferably 4.5 mgKOH / g to 8 mgKOH / g.
バインダー樹脂であるポリエステル系樹脂の酸価（滴定法）は、小さすぎると磁性粉末と樹脂との密着性が悪く、大きすぎると樹脂特性が低下するので、好ましくは２.０ｍｇＫＯＨ／ｇ〜４.０ｍｇＫＯＨ／ｇ、より好ましくは２ｍｇＫＯＨ／ｇ〜３ｍｇＫＯＨ／ｇ以下である。 If the acid value (titration method) of the polyester resin that is a binder resin is too small, the adhesion between the magnetic powder and the resin is poor, and if it is too large, the resin properties deteriorate, so that preferably 2.0 mg KOH / g to 4. It is 0 mgKOH / g, more preferably 2 mgKOH / g to 3 mgKOH / g or less.
本発明においては、軟磁性材料に難燃性を賦与する場合、難燃性を有するポリエステル系樹脂を用いることができ、そのような難燃性ポリエステル系樹脂としてリン内添ポリエステル系樹脂を用いることが好ましい。リン内添ポリエステル系樹脂は、分子中にリン酸残基を有するノンハロゲン系難燃剤であり、高い難燃性（ＵＬ９４ Ｖ−０）を示す。また、難燃化のために従来のように多量の難燃剤を添加する場合と異なり、環境試験後の透磁率の低下も小さい。 In the present invention, when imparting flame retardancy to the soft magnetic material, a flame-retardant polyester resin can be used, and a phosphorus-containing polyester resin is used as such a flame-retardant polyester resin. Is preferred. The phosphorus-added polyester resin is a non-halogen flame retardant having a phosphoric acid residue in the molecule, and exhibits high flame retardancy (UL94 V-0). Further, unlike the conventional case of adding a large amount of flame retardant for flame retardancy, the decrease in magnetic permeability after the environmental test is also small.
リン内添ポリエステル系樹脂としては、例えば、リン変性ポリエステル共重合体を挙げることができる。リン変性ポリエステル共重合体は、ポリエステル共重合体の主骨格にリン成分が導入されているものであり、ポリエステル成分とリン成分とを共重合させることにより得られる。ここでポリエステル成分としては、エチレングリコールと、テレフタル酸、ナフタレンカルボン酸、アジピン酸、セバシン酸又はイソフタル酸とから形成される高分子化合物や、１，４−ブタンジオールと、テレフタル酸、アジピン酸又はセバシン酸とから形成される高分子化合物や、１，６−ヘキサンジオールと、アジピン酸、セバシン酸又はイソフタル酸とから形成される高分子化合物等を使用することができる。またリン成分としては、ホスフォネート型ポリオール、ホスフェート型ポリオール、ビニルホスフォネート、アリルホスフォネート等を使用することができる。このように主骨格にリン成分を導入したポリエステル共重合体は、単にポリエステルにリン成分を混合分散させたものよりも高い難燃性を示す。 Examples of the phosphorus-added polyester resin include a phosphorus-modified polyester copolymer. The phosphorus-modified polyester copolymer has a phosphorus component introduced into the main skeleton of the polyester copolymer, and is obtained by copolymerizing a polyester component and a phosphorus component. Here, as the polyester component, a polymer compound formed from ethylene glycol and terephthalic acid, naphthalenecarboxylic acid, adipic acid, sebacic acid or isophthalic acid, 1,4-butanediol, terephthalic acid, adipic acid or A polymer compound formed from sebacic acid, a polymer compound formed from 1,6-hexanediol, and adipic acid, sebacic acid, or isophthalic acid can be used. As the phosphorus component, phosphonate type polyols, phosphate type polyols, vinyl phosphonates, allyl phosphonates and the like can be used. Thus, the polyester copolymer in which the phosphorus component is introduced into the main skeleton exhibits flame retardancy higher than that obtained by simply mixing and dispersing the phosphorus component in the polyester.
リン内添ポリエステル系樹脂のリン含有率は、ポリエステル系樹脂の主骨格の種類、リン成分（リン酸残基）の種類、軟磁性シートを構成するその他の成分の種類等に応じて、所定の難燃性を満足するように定めることができるが、少なすぎると十分な難燃性を実現できず、多すぎると樹脂物性が低下するので、好ましくは３．０〜１０重量％、より好ましくは３〜６重量％である。 The phosphorus content of the polyester resin with internal phosphorus is determined according to the type of the main skeleton of the polyester resin, the type of phosphorus component (phosphate residue), the type of other components constituting the soft magnetic sheet, and the like. Although it can be determined so as to satisfy the flame retardancy, if it is too small, sufficient flame retardancy cannot be realized, and if it is too much, the physical properties of the resin deteriorate, so preferably 3.0 to 10% by weight, more preferably 3 to 6% by weight.
本発明において、上述したようなポリエステル系樹脂と共に、本発明の効果を損なわない範囲で、エポキシ樹脂、ポリエステル系樹脂、アクリル系樹脂、脂肪族炭化水素樹脂、ロジン系樹脂、ナイロン樹脂、フェノール樹脂、ポリウレタン樹脂、メラミン樹脂、ポリアミン樹脂、尿素ホルムアルデヒド樹脂、ポリイソシアネートやエポキシ化合物とイソシアネート化合物やイミダゾール化合物との混合物等をバインダー樹脂として併用することができる。 In the present invention, together with the polyester resin as described above, an epoxy resin, a polyester resin, an acrylic resin, an aliphatic hydrocarbon resin, a rosin resin, a nylon resin, a phenol resin, within a range not impairing the effects of the present invention. A polyurethane resin, a melamine resin, a polyamine resin, a urea formaldehyde resin, a mixture of a polyisocyanate or an epoxy compound and an isocyanate compound or an imidazole compound can be used in combination as a binder resin.
本発明の軟磁性材料においては、前述したように、ポリエステル系樹脂が架橋されている。この架橋は、軟磁性粉末をポリエステル系樹脂に分散させる際に架橋剤を配合し、ポリエステル系樹脂と架橋剤との間で架橋反応させることにより達成される。このような架橋剤としては、ポリエステル系樹脂の架橋反応に従来より用いられている架橋剤を使用することができるが、特にブロックイソシアネートを架橋剤として使用することが好ましい。ここで、ブロックイソシアネートとは、イソシアネート化合物にブロック剤が付加し、イソシアネート基（−ＮＣＯ）が封鎖されたものであり、室温ではブロックイソシアネートが解離しないためポリエステル系樹脂が架橋されないが、ブロックイソシアネートの解離温度以上に加熱されるとブロック剤が解離し、活性化したイソシアネート化合物によってポリエステル系樹脂が架橋される。ブロック剤の解離温度は、８０℃〜１８０℃の範囲で選択できる。また、ブロックイソシアネートの具体例としては、コロネート２５０７（日本ポリウレタン社製）等を挙げることができる。 In the soft magnetic material of the present invention, as described above, the polyester resin is crosslinked. This crosslinking is achieved by blending a crosslinking agent when the soft magnetic powder is dispersed in the polyester resin and causing a crosslinking reaction between the polyester resin and the crosslinking agent. As such a crosslinking agent, the crosslinking agent conventionally used for the crosslinking reaction of a polyester-type resin can be used, However, It is preferable to use especially a block isocyanate as a crosslinking agent. Here, the blocked isocyanate is a compound in which a blocking agent is added to an isocyanate compound and an isocyanate group (-NCO) is blocked. Since the blocked isocyanate does not dissociate at room temperature, the polyester resin is not crosslinked. When heated above the dissociation temperature, the blocking agent dissociates, and the polyester resin is crosslinked by the activated isocyanate compound. The dissociation temperature of the blocking agent can be selected in the range of 80 ° C to 180 ° C. Specific examples of the blocked isocyanate include Coronate 2507 (manufactured by Nippon Polyurethane Co., Ltd.).
ここで、ブロックイソシアネートを使用する理由は、一般的な成膜技術である塗布方式によってシート状の軟磁性材料を製造する場合、架橋剤としてブロックされていないイソシアネートを用いると、溶剤の乾燥時にポリエステル系樹脂とイソシアネートが反応して硬化しまうのに対し、ブロックイソシアネートを用いるとブロックが脱離する温度以上に加熱されなければ反応が進行しないからである。また、溶剤の乾燥で軟磁性材料中にエアーを取り込んでしまうが、ポリエステル系樹脂とイソシアネートとの反応は、ブロック剤脱離温度以下では進行せずに、ブロック脱離後もゆっくり進むので、軟磁性材料を充分に圧縮してエアーを排除して軟磁性粉末を密に配向きせた状態で架橋反応を行うことができるからである。また、架橋によって軟磁性材料の機械的強度を大きくでき、更に、高温環境下や高温高湿環境下においても緩みの発生を抑制することがき、厚みの変化も抑制することができる。なお、架橋剤としてブロックイソシアネートを用いることによって、その解離温度以上にならなければ前記架橋反応が開始されないため、架橋反応が開始されない温度で十分に圧縮して軟磁性粉末を密に配向させた後に、解離温度以上でさらに圧縮して配向させることによって比重が大きなシート状の軟磁性材料得ることができる。 Here, the reason for using the blocked isocyanate is that when a sheet-like soft magnetic material is produced by a coating method, which is a general film forming technique, when an unblocked isocyanate is used as a crosslinking agent, the polyester is used when the solvent is dried. This is because when the block resin is used, the reaction does not proceed unless the resin is heated above the temperature at which the block is released. In addition, air is taken into the soft magnetic material due to drying of the solvent, but the reaction between the polyester resin and isocyanate does not proceed below the blocking agent desorption temperature and proceeds slowly after block desorption. This is because the cross-linking reaction can be performed in a state where the magnetic material is sufficiently compressed to exclude air and the soft magnetic powder is closely oriented. In addition, the mechanical strength of the soft magnetic material can be increased by crosslinking, and further, the occurrence of loosening can be suppressed even in a high temperature environment or a high temperature and high humidity environment, and a change in thickness can also be suppressed. By using blocked isocyanate as a cross-linking agent, the cross-linking reaction is not started unless the dissociation temperature is exceeded, so after sufficiently compressing the soft magnetic powder at a temperature at which the cross-linking reaction does not start and densely oriented By further compressing and orienting above the dissociation temperature, a sheet-like soft magnetic material having a large specific gravity can be obtained.
本発明において、ブロックイソシアネートとして、その解離温度が低すぎると、後述する軟磁性材料の製造時の軟磁性塗料の圧縮が十分に進まないうちに架橋が始まって比重や透磁率を十分に確保し難くなり、更に、軟磁性塗料に用いた後述する溶剤の乾燥除去に支障が生ずるおそれがあり、解離温度が高すぎると、後述する軟磁性材料の製造時に用いる剥離基材に熱による損傷を与えるおそれがあるので、好ましくは１００℃〜１８０℃、より好ましくは１２０℃〜１６０℃である。なお、ポリエステル系樹脂を架橋する反応は、室温でも非常にゆっくりと進行するので、解離温度に加熱した後、室温で長時間放置すれば、ポリエステル系樹脂は完全に架橋し硬化する。 In the present invention, if the dissociation temperature is too low as the blocked isocyanate, crosslinking starts before the soft magnetic coating material is sufficiently compressed during the production of the soft magnetic material described later, and sufficient specific gravity and magnetic permeability are secured. In addition, there is a risk that it will hinder the dry removal of the solvent used in the soft magnetic paint, which will be described later. If the dissociation temperature is too high, the release substrate used in the production of the soft magnetic material described later will be damaged by heat. Since there exists a possibility, Preferably it is 100 to 180 degreeC, More preferably, it is 120 to 160 degreeC. Since the reaction for crosslinking the polyester resin proceeds very slowly even at room temperature, the polyester resin is completely crosslinked and cured if it is left at room temperature for a long time after heating to the dissociation temperature.
ブロックイソシアネートの使用割合は、少なすぎるとポリエステル系樹脂の架橋が不十分となり、厚み変化が大きくなりすぎるおそれがあり、多すぎるとシート比重が高くならないので、ポリエステル系樹脂の好ましくは０．５質量％〜１０質量％、より好ましくは１質量％〜８質量％である。 If the amount of the blocked isocyanate is too small, the polyester resin may not be sufficiently crosslinked, and the thickness change may be too large. If the amount is too large, the specific gravity of the sheet does not increase. % To 10% by mass, more preferably 1% to 8% by mass.
本発明の軟磁性材料を構成する架橋されたポリエステル系樹脂は、以上説明したポリエステル系樹脂が架橋剤で架橋されているものであり、その軟磁性材料中における含有量は、少なすぎるとシート比重が高くならなくなり、多すぎるとμ′が高くならないので、好ましくは６０〜１５０重量％、より好ましくは８０〜１２０重量％である。 The cross-linked polyester resin constituting the soft magnetic material of the present invention is the above-described polyester resin cross-linked with a cross-linking agent. If the content in the soft magnetic material is too small, the specific gravity of the sheet is low. However, if it is too large, μ ′ does not increase, so it is preferably 60 to 150% by weight, more preferably 80 to 120% by weight.
本発明の軟磁性材料において、例えばＵＬ９４のＶ−１というような充分な難燃性を確保するためには、耐熱性、物性の低下、高温条件下、加水分解性、表面性等に影響を与えない程度に他の難燃剤を添加することもできる。 In the soft magnetic material of the present invention, in order to ensure sufficient flame retardancy such as UL94 V-1, for example, the heat resistance, physical property degradation, high temperature conditions, hydrolyzability, surface properties, etc. are affected. Other flame retardants can be added to such an extent that they are not given.
なお、以上説明した本発明の軟磁性材料は、バインダー樹脂としてガラス転移点Ｔｇが比較的低いポリエステル系樹脂を使用し、またそのガラス転移点よりも高い解離温度を示すブロックイソシアネートを架橋剤として用いているので、軟磁性材料の製造時に、扁平軟磁性粉末が同一面内に配向するように、ブロックイソシアネートの解離温度を超えないように加熱すると収縮し、比重と透磁率とが大きくなる。また、ブロックイソシアネートの解離温度以上に加熱するとポリエステル系樹脂が架橋するので、ポリエステル系樹脂を架橋させていない従来の磁性シートに比べて、高温、あるいは高温高湿環境下において緩みがなく、厚さなどの寸法変化が小さい。具体的には、本発明の軟磁性材料は、６０℃〜９５℃の高温環境下に放置した後の寸法変化が３％以下とすることができる。更に、温度４０℃〜９０℃、相対湿度６０〜９５％の高温高湿下に放置した後の寸法変化が３％以下とすることができる。従って、携帯電話やデジタルカメラ等の電子機器に使用される磁性シートの一般的な使用温度範囲は−２５℃〜８５℃であり、高温高湿条件は６０℃、９５Ｒｈ％であるところ、これらの評価に対して高温側で問題となる寸法変化を少なくすることに対して本発明の軟磁性材料は有用である。更に、本発明の軟磁性材料は、ポリエステル系樹脂が架橋しているので、材料自体の機械的強度が高くなっているため、熱変化等の物理的衝撃が加えられたり、所望の形状に型抜き等をしても、軟磁性材料端面からの粉落ち等がないという長所も有する。 The soft magnetic material of the present invention described above uses a polyester resin having a relatively low glass transition point Tg as a binder resin, and uses a blocked isocyanate having a dissociation temperature higher than the glass transition point as a crosslinking agent. Therefore, when the soft magnetic material is manufactured, the flat soft magnetic powder is contracted by heating so as not to exceed the dissociation temperature of the blocked isocyanate so that the flat soft magnetic powder is aligned in the same plane, and the specific gravity and the magnetic permeability are increased. In addition, when heated above the dissociation temperature of the blocked isocyanate, the polyester resin crosslinks. Therefore, compared with conventional magnetic sheets that do not crosslink the polyester resin, there is no loosening in high temperature or high temperature and high humidity environments. The dimensional change such as is small. Specifically, the soft magnetic material of the present invention can have a dimensional change of 3% or less after being left in a high temperature environment of 60 ° C. to 95 ° C. Furthermore, the dimensional change after being left under high temperature and high humidity at a temperature of 40 ° C. to 90 ° C. and a relative humidity of 60 to 95% can be 3% or less. Therefore, the general operating temperature range of magnetic sheets used in electronic devices such as mobile phones and digital cameras is -25 ° C to 85 ° C, and high temperature and high humidity conditions are 60 ° C and 95Rh%. The soft magnetic material of the present invention is useful for reducing the dimensional change which becomes a problem on the high temperature side for evaluation. Further, since the soft magnetic material of the present invention has a polyester resin cross-linked, the mechanical strength of the material itself is high, so that a physical impact such as a heat change is applied or a desired shape is molded. Even if it is removed, there is an advantage that there is no powder falling off the end face of the soft magnetic material.
本発明の軟磁性材料は、少なくとも扁平軟磁性粉末とポリエステル系樹脂と架橋剤とを、常法に従って混合して得た軟磁性組成物を、架橋反応が生ずる温度で圧縮することにより製造することができる。ここで、架橋反応が生ずる温度で圧縮すると、架橋反応が開始し始めると同時に、架橋反応が充分に進行していない間は、組成物が収縮しつつ且つ扁平軟磁性粉末が圧縮方向に対して垂直な面の面内方向に配向するので、比重が増大し且つ磁気特性が良好となる。更に、架橋反応が進行すると、ポリエステル系樹脂全体が架橋して収縮が抑制され、寸法安定性が向上する。 The soft magnetic material of the present invention is manufactured by compressing a soft magnetic composition obtained by mixing at least a flat soft magnetic powder, a polyester resin, and a crosslinking agent according to a conventional method at a temperature at which a crosslinking reaction occurs. Can do. Here, when compression is performed at a temperature at which the crosslinking reaction occurs, the crosslinking reaction starts to start, and at the same time, while the crosslinking reaction is not sufficiently advanced, the composition is contracting and the flat soft magnetic powder is in the compression direction. Since it is oriented in the in-plane direction of the vertical surface, the specific gravity increases and the magnetic properties are improved. Furthermore, when the cross-linking reaction proceeds, the entire polyester resin is cross-linked, shrinkage is suppressed, and dimensional stability is improved.
ところで、軟磁性組成物を調製する際、組成物に過度に強い剪断力を加えると扁平軟磁性粉末の形状が維持し難くなり、しかも扁平軟磁性粉末を一定の面内方向へ配向させなければならないから、軟磁性組成物の流動性を高め、比較的低い粘度に設定することが好ましい。また、軟磁性材料をシート化することが求められている。その場合、シート形成のために塗布法を利用することを念頭に置くと、軟磁性組成物の粘度を下げることが必要となるから、軟磁性組成物には、バインダー樹脂としてのポリエステル系樹脂を溶解する溶剤を併用することが好ましい。そのような溶剤としては、例えば、メチルエチルケトン、ベンゼン、トルエン、キシレン等の芳香族炭化水素化合物、シクロヘキサノン、メチルイソブチルケトン等のケトン化合物を用いることができる。但し、軟磁性組成物の粘度が小さすぎるとシート状の軟磁性材料の比重が小さくなりすぎる傾向があり、大きすぎると塗布が困難となったり、塗布筋ができてしまったりという問題がある。そこで、溶剤の使用量は、軟磁性組成物中の固形分が好ましくは５０〜７０重量％となるようにする。 By the way, when preparing a soft magnetic composition, if an excessively strong shear force is applied to the composition, it becomes difficult to maintain the shape of the flat soft magnetic powder, and the flat soft magnetic powder must be oriented in a certain in-plane direction. Therefore, it is preferable to increase the fluidity of the soft magnetic composition and set it to a relatively low viscosity. Moreover, it is required to form a soft magnetic material into a sheet. In that case, since it is necessary to lower the viscosity of the soft magnetic composition in consideration of using a coating method for forming a sheet, the soft magnetic composition may include a polyester resin as a binder resin. It is preferable to use a solvent that dissolves in combination. As such a solvent, for example, aromatic hydrocarbon compounds such as methyl ethyl ketone, benzene, toluene and xylene, and ketone compounds such as cyclohexanone and methyl isobutyl ketone can be used. However, if the viscosity of the soft magnetic composition is too small, the specific gravity of the sheet-like soft magnetic material tends to be too small, and if it is too large, there is a problem that coating becomes difficult or coating stripes are formed. Therefore, the amount of the solvent used is preferably such that the solid content in the soft magnetic composition is 50 to 70% by weight.
シート状の軟磁性材料は、少なくとも扁平軟磁性粉末とポリエステル系樹脂と架橋剤と溶剤とを混合してなる軟磁性組成物を剥離基材上に塗布した後に、架橋反応が実質的に生じない温度で乾燥し、架橋反応が生ずる温度で圧縮することにより製造できる。 The sheet-like soft magnetic material has substantially no cross-linking reaction after a soft magnetic composition comprising at least a flat soft magnetic powder, a polyester-based resin, a cross-linking agent, and a solvent is applied onto a release substrate. It can be produced by drying at a temperature and pressing at a temperature at which a crosslinking reaction occurs.
まず、少なくとも扁平軟磁性粉末とポリエステル系樹脂と架橋剤と溶剤とを混合して軟磁性組成物を調製する。具体的には、ポリエステル系樹脂を溶剤に溶解し、その溶液に軟磁性粉末と架橋剤とを添加混合すればよい。 First, a soft magnetic composition is prepared by mixing at least a flat soft magnetic powder, a polyester-based resin, a crosslinking agent, and a solvent. Specifically, a polyester resin is dissolved in a solvent, and soft magnetic powder and a crosslinking agent are added and mixed in the solution.
次に、軟磁性組成物を剥離基材上に塗布する。塗布する方法としては、コーター、ドクターブレード法等の一般的な塗布方法を採用することができる。このとき、形成される軟磁性組成物の塗布厚は、前記塗布方式で所望の厚さに調節することができる。また、この塗布の際、塗布された軟磁性組成物に磁場を加えることによって、扁平軟磁性粉末を塗布面内方向に配向させ、軟磁性粉末を高密度に充填することが可能となる。また、比重を向上させるためにプレス操作を行ってもよい。 Next, the soft magnetic composition is applied onto the release substrate. As a coating method, a general coating method such as a coater or a doctor blade method can be employed. At this time, the coating thickness of the formed soft magnetic composition can be adjusted to a desired thickness by the coating method. In addition, by applying a magnetic field to the applied soft magnetic composition at the time of application, it becomes possible to orient the flat soft magnetic powder in the in-plane direction of the application and to fill the soft magnetic powder with high density. Moreover, you may perform press operation in order to improve specific gravity.
ここで、剥離基材としては、ポリエチレンテレフタレート、ポリエチレンナフタレートポリイミド、ポリフェニレンスルフィド、ポリプロピレンオキサイド、ポリエチレン、ポリプロピレン、ポリアミド等を挙げることができる。これら基材の厚みは通常数μｍ〜数百μｍとすることができる。また、剥離基材の軟磁性組成物の塗布面には公知の離型剤を塗布しておいてもよい。 Here, examples of the release substrate include polyethylene terephthalate, polyethylene naphthalate polyimide, polyphenylene sulfide, polypropylene oxide, polyethylene, polypropylene, and polyamide. The thickness of these base materials can usually be several μm to several hundred μm. Moreover, you may apply | coat a well-known mold release agent to the application surface of the soft magnetic composition of a peeling base material.
次に、剥離基材に塗布した軟磁性組成物を、架橋反応が実質的に生じない温度で乾燥する。架橋反応が生じてしまう温度で乾燥すると、扁平軟磁性粉末を同一面内方向に配向させることができず、磁性特性が不充分となるからである。ここで、架橋反応が実質的に生じない温度における「実質的に生じない」とは、ラミネータや熱プレスにより扁平軟磁性粉末を同一面内方向に配向させることが可能な範囲での架橋反応については許容する意味である。具体的には、架橋剤としてブロックイソシアネートを使用した場合、“架橋反応が実質的に生じない温度”とは、そのブロックイソシアネートの解離温度未満の温度のことである。一方、“架橋反応が生じる温度”とは、そのブロックイソシアネートの解離温度以上の温度のことである。 Next, the soft magnetic composition applied to the release substrate is dried at a temperature at which a crosslinking reaction does not substantially occur. This is because, when dried at a temperature at which a crosslinking reaction occurs, the flat soft magnetic powder cannot be oriented in the same in-plane direction, and the magnetic properties become insufficient. Here, “substantially does not occur” at a temperature at which crosslinking reaction does not substantially occur means that the crosslinking soft reaction powder can be oriented in the same in-plane direction by a laminator or a hot press. Is an acceptable meaning. Specifically, when a blocked isocyanate is used as a crosslinking agent, the “temperature at which a crosslinking reaction does not substantially occur” refers to a temperature lower than the dissociation temperature of the blocked isocyanate. On the other hand, the “temperature at which a crosslinking reaction occurs” is a temperature equal to or higher than the dissociation temperature of the blocked isocyanate.
次に、軟磁性組成物の乾燥シートを、架橋反応が生ずる温度で圧縮する。この場合、扁平軟磁性粉末を同一面内方向に配向させ、最終的に架橋反応を完結させる。これは、架橋反応が生ずる温度で加熱しても、架橋反応が一瞬のうちに完結するのではなく、架橋反応が完結するまでには相応の時間が必要だからである。 Next, the dry sheet of the soft magnetic composition is compressed at a temperature at which a crosslinking reaction occurs. In this case, the flat soft magnetic powder is oriented in the same in-plane direction, and finally the crosslinking reaction is completed. This is because even if heating is performed at a temperature at which the cross-linking reaction occurs, the cross-linking reaction is not completed in an instant, and a corresponding time is required until the cross-linking reaction is completed.
なお、架橋反応が実質的に生じない温度で乾燥した後、架橋反応が生ずる温度で圧縮する前に、架橋反応が実質的に生じない温度で圧縮してもよい。この場合、架橋反応が生ずる温度で圧縮する際、既に扁平軟磁性粉末を同一面内方向に配向させているので、主として架橋反応だけが生ずる。 In addition, after drying at a temperature at which the cross-linking reaction does not substantially occur, the film may be compressed at a temperature at which the cross-linking reaction does not substantially occur before being compressed at a temperature at which the cross-linking reaction occurs. In this case, when compressing at a temperature at which a crosslinking reaction occurs, the flat soft magnetic powder has already been oriented in the same in-plane direction, so that only the crosslinking reaction mainly occurs.
次に、シート状の軟磁性材料を積層して製造する方法の概略を説明する。 Next, an outline of a method for stacking and manufacturing sheet-like soft magnetic materials will be described.
まず、少なくとも扁平軟磁性粉末とポリエステル系樹脂と架橋剤とを混合してなる軟磁性組成物を剥離基材上に塗布した後に、架橋反応が実質的に生じない温度で乾燥し、剥離基材を取り除くことを繰り返すことにより、少なくとも２枚の軟磁性組成物の乾燥シートを取得する。 First, a soft magnetic composition formed by mixing at least a flat soft magnetic powder, a polyester-based resin, and a crosslinking agent is applied onto a release substrate, and then dried at a temperature at which a crosslinking reaction does not substantially occur. By repeating the removal, at least two dry sheets of the soft magnetic composition are obtained.
次に、その少なくとも２枚の乾燥シートを積層し、架橋反応が生ずる温度で圧縮する。この場合、扁平軟磁性粉末を同一面内方向に配向させ、最終的に架橋反応を完結させる。また、少なくとも２枚の乾燥シートを積層した後、架橋反応が生ずる温度で圧縮する前に、架橋反応が実質的に生じない温度で圧縮した場合、架橋反応が生ずる温度で圧縮する際、既に扁平軟磁性粉末を同一面内方向に配向させているので、主として架橋反応だけが生ずる。 Next, the at least two dry sheets are laminated and compressed at a temperature at which a crosslinking reaction occurs. In this case, the flat soft magnetic powder is oriented in the same in-plane direction, and finally the crosslinking reaction is completed. In addition, when at least two dry sheets are laminated and then compressed at a temperature at which the crosslinking reaction does not substantially occur before being compressed at a temperature at which the crosslinking reaction occurs, when the compression is performed at a temperature at which the crosslinking reaction occurs, Since the soft magnetic powder is oriented in the same in-plane direction, only the crosslinking reaction mainly occurs.
本発明の軟磁性材料は、非接触式ＩＣカードやＩＣタグなどのＲＦＩＤシステム等における磁束収束体として、あるいは一般の電波吸収体として有用である。即ち、ＲＦＩＤ用フレキシブルシールド材、携帯用デジタルカメラ等の電子機器のノイズ電磁波吸収体として有用である。よって、本発明の軟磁性材料を備えた映像機器などの各種電子機器も本発明の一部である。 The soft magnetic material of the present invention is useful as a magnetic flux converging body in an RFID system such as a non-contact type IC card or IC tag, or as a general electromagnetic wave absorber. That is, it is useful as a noise electromagnetic wave absorber for electronic devices such as RFID flexible shield materials and portable digital cameras. Therefore, various electronic devices such as video equipment provided with the soft magnetic material of the present invention are also part of the present invention.
具体的には、本発明の軟磁性材料は、非接触データ通信用のアンテナモジュールに好ましく適用できる。このようなアンテナモジュールは、支持体としてのベース基板の一面にシート状の軟磁性材料と、他面に金属シールド板とをそれぞれ両面テープで積層し、更に軟磁性材料上に銅やアルミニウムなどの金属パターンからなるアンテナコイルが形成された構造を有する。アンテナコイルは、非接触ＩＣタグ機能のためのものであって、外部のリーダライタのアンテナ部と誘導結合により通信を行うためのものである。また、アンテナコイルは、信号処理回路部と接続されている。このような信号処理回路部は、非接触データ通信に必要な信号処理回路及び情報を格納したＩＣチップや同調用コンデンサなどの電子部品で構成されており、アンテナコイルの内部に配置されていてもよく、外部に配置されていてもよい。また、ベース基板に取り付けられる外部接続部を介して、携帯通信端末のプリント基板に接続されている。ここで、ベース基板としては、ポリイミド、ポリエチレンテレフタレート、ポリエチレンテレナフタレートなどのプラスチックフィルムを主体とする絶縁性フレキシブル基板でもよく、ガラスエポキシ基板などのリジッド基板でもよい。また、金属シールド板は、アンテナモジュールの共振周波数の粗調用に用いられており、携帯通信端末に組み込んだ状態でアンテナモジュールの共振周波数に大きな変化を生じさせないように設けられている。そのような金属シールド板としては、ステンレス板、銅板、アルミニウム板等が挙げられる。 Specifically, the soft magnetic material of the present invention can be preferably applied to an antenna module for non-contact data communication. In such an antenna module, a sheet-like soft magnetic material is laminated on one surface of a base substrate as a support and a metal shield plate is laminated on the other surface with double-sided tape, and copper, aluminum, or the like is further laminated on the soft magnetic material. It has a structure in which an antenna coil made of a metal pattern is formed. The antenna coil is for a non-contact IC tag function, and communicates with the antenna unit of an external reader / writer by inductive coupling. The antenna coil is connected to the signal processing circuit unit. Such a signal processing circuit unit is composed of a signal processing circuit necessary for non-contact data communication and an electronic component such as an IC chip storing information and a tuning capacitor, and may be disposed inside the antenna coil. It may be arranged outside. Moreover, it is connected to the printed circuit board of the mobile communication terminal via an external connection part attached to the base substrate. Here, the base substrate may be an insulating flexible substrate mainly composed of a plastic film such as polyimide, polyethylene terephthalate, or polyethylene terephthalate, or may be a rigid substrate such as a glass epoxy substrate. Further, the metal shield plate is used for coarse adjustment of the resonance frequency of the antenna module, and is provided so as not to cause a large change in the resonance frequency of the antenna module when incorporated in the mobile communication terminal. Examples of such metal shield plates include stainless steel plates, copper plates, aluminum plates, and the like.
このようなアンテナモジュールを備えた携帯電話等の携帯通信端末でリーダライタとデータ通信を行う場合、アンテンモジュールをリーダライタのアンテナ部に近接させる。すると、リーダライタのアンテナ部から発信された電磁波あるいは高周波磁界が、アンテナモジュールのアンテナコイル内を通過することでアンテナコイルに電磁波あるいは高周波磁界の強さに応じた誘導電流が発生する。この誘導電流は信号処理回路部において整流され、ＩＣチップに記録された情報の読み出し電圧に変換される。読み出された情報は信号処理回路部において変調され、アンテナコイルを介してリーダライタのアンテナ部へ送信される。 When data communication is performed with a reader / writer using a mobile communication terminal such as a mobile phone provided with such an antenna module, the anten module is brought close to the antenna unit of the reader / writer. Then, an electromagnetic wave or a high frequency magnetic field transmitted from the antenna unit of the reader / writer passes through the antenna coil of the antenna module, so that an induced current corresponding to the strength of the electromagnetic wave or the high frequency magnetic field is generated in the antenna coil. This induced current is rectified in the signal processing circuit unit and converted into a read voltage for information recorded in the IC chip. The read information is modulated in the signal processing circuit unit and transmitted to the antenna unit of the reader / writer via the antenna coil.
次に、本発明を適用した軟磁性シートの具体的な実施について、実験結果を基に説明する。 Next, specific implementation of the soft magnetic sheet to which the present invention is applied will be described based on experimental results.
実施例１Ａ〜４Ａ
表１に示した配合成分をプラネタリーミキサー又はディゾルバーにより均一に混合することにより軟磁性塗料を調製した。これらの塗料においては、バインダーとして、水酸基価が６．０ＫＯＨｍｇ／ｇ、数平均分子量は２４０００、ガラス転移点４℃、リン含有率３．９重量％のリン内添ポリエステル樹脂（バイロン５３７，東洋紡績社製）を用いた。また、架橋剤として、ブロックイソシアネート（日本ポリウレタン社製、商品名コロネート２５０７）を用いた。また、軟磁性粉末としては、Ｆｅ−Ｓｉ−Ｃｒ−Ｎｉ粉末（ＪＥＭＣＯ社）、Ｆｅ−Ｓｉ−Ａｌ粉末（株式会社メイト）、ＳｉＯ２被覆Ｆｅ−Ｓｉ−Ｃｒ−Ｎｉ粉末（ＪＥＭＣＯ社製粉末に対し、振動スパッタ装置を用いて５〜１０ｎｍ厚のＳｉＯ２被膜を形成した粉末）又はアクリル樹脂被覆Ｆｅ−Ｓｉ−Ｃｒ−Ｎｉ粉末（ＪＥＭＣＯ社製粉末の表面をシランカップリング剤で処理した後、０.０１μｍ〜０.１μｍ厚のアクリル系樹脂コートした粉末）を用いた。Examples 1A-4A
A soft magnetic paint was prepared by uniformly mixing the ingredients shown in Table 1 with a planetary mixer or dissolver. In these coating materials, a phosphorus-added polyester resin (Byron 537, Toyobo Co., Ltd.) having a hydroxyl value of 6.0 KOHmg / g, a number average molecular weight of 24,000, a glass transition point of 4 ° C., and a phosphorus content of 3.9% by weight as a binder. Used). In addition, blocked isocyanate (manufactured by Nippon Polyurethane Co., Ltd., trade name Coronate 2507) was used as a crosslinking agent. As the soft magnetic powder, Fe-Si-Cr-Ni powder (JEMCO Inc.), Fe-Si-Al powder (manufactured Mate), SiO 2 coated Fe-Si-Cr-Ni powder (the JEMCO Co. powder On the other hand, after treating the surface of the powder made of SiO 2 coating having a thickness of 5 to 10 nm using a vibration sputtering apparatus or acrylic resin-coated Fe-Si-Cr-Ni powder (JEMCO company powder with a silane coupling agent, 0.01 μm to 0.1 μm thick acrylic resin-coated powder) was used.
得られた軟磁性塗料を、片面に剥離処理が施された剥離ポリエステルテレフタレートフィルム（剥離ＰＥＴフィルム）（帝人社）に、塗料固形分が１８０ｇ／ｍ２となるようにロールコーターで塗布し、１１５℃で乾燥し、剥離ＰＥＴフィルムに支持された未硬化軟磁性シートを得た。The obtained soft magnetic coating material was applied to a release polyester terephthalate film (exfoliated PET film) (Teijin Ltd.) having a release treatment on one side with a roll coater so that the solid content of the paint was 180 g / m 2. It dried at 0 degreeC and the uncured soft magnetic sheet supported by the peeling PET film was obtained.
次に、剥離ＰＥＴフィルムを取り除いた未硬化軟磁性シートを５枚積層し、ラミネータのロールとロールの間（上下のロールの温度を１５０℃、線圧を１３．４ｋｇｆ／ｃｍ、ラインスピードを０．５ｍ／分に設定した。）を２０回通して圧縮によって配向させながら架橋硬化させ、軟磁性シートを得た。 Next, five uncured soft magnetic sheets from which the peeled PET film was removed were laminated, and between the laminator rolls (the temperature of the upper and lower rolls was 150 ° C., the linear pressure was 13.4 kgf / cm, and the line speed was 0. Was set to 5 m / min.) And passed through 20 times to be crosslinked and cured while being oriented by compression to obtain a soft magnetic sheet.
比較例１Ａ
バインダーとしてガラス転移点Ｔｇが室温以上（３５℃）で水酸基価の低いポリエステル樹脂（ユニチカ社製、商品名ＵＥ３５００、水酸基価＝４）を用いる以外、実施例１Ａと同様の操作により、架橋硬化した軟磁性シートを得た。Comparative Example 1A
It was crosslinked and cured in the same manner as in Example 1A, except that a polyester resin having a glass transition point Tg of room temperature or higher (35 ° C.) and a low hydroxyl value (trade name UE3500, trade name: UE3500, hydroxyl value = 4) was used as the binder. A soft magnetic sheet was obtained.
比較例２Ａ
架橋剤であるブロックイソシアネートを添加せず、他は実施例１Ａと同様の操作により、架橋硬化した磁性シートを作製した。Comparative Example 2A
A cross-linked and hardened magnetic sheet was prepared in the same manner as in Example 1A, except that the blocked isocyanate as a cross-linking agent was not added.
得られた架橋硬化した軟磁性シート（実施例１Ａ〜４Ａ及び比較例１Ａ〜２Ａ）について、シートの厚さ、磁気特性（透磁率μ′、磁気損失μ"、性能係数Ｑ）、比重、及び通信距離を測定した。また、８５℃、８５％Ｒｈの高温高湿環境下に９６時間保持した後の軟磁性シートの厚さ、及び磁気特性（μ′、μ"、Ｑ）を測定し、さらに前記環境試験前後における軟磁性シートの厚み変化率、比重変化率及びμ′変化率を算出した。なお、通信距離は、作製した軟磁性シートをアンテナ装置とシールド板の間に配置して携帯電話に搭載し、その時の通信距離を測定した。実効透磁率μ′は、直径７ｍｍのリング状のサンプルを作製し、これに導線コイルを５ターン巻いてインピーダンスアナライザーを用いてキャリア周波数（１３．５６ＭＨｚ）における交流透磁率を測定し、定量化することにより得た。結果を表２に示す。 For the obtained cross-linked and hardened soft magnetic sheets (Examples 1A to 4A and Comparative Examples 1A to 2A), the thickness of the sheet, magnetic properties (permeability μ ′, magnetic loss μ ″, performance coefficient Q), specific gravity, and The communication distance was measured, and the thickness and magnetic properties (μ ′, μ ″, Q) of the soft magnetic sheet after being kept in a high temperature and high humidity environment of 85 ° C. and 85% Rh for 96 hours were measured, Furthermore, the thickness change rate, specific gravity change rate, and μ ′ change rate of the soft magnetic sheet before and after the environmental test were calculated. Note that the communication distance was measured by placing the produced soft magnetic sheet between the antenna device and the shield plate and mounting it on a cellular phone. The effective magnetic permeability μ ′ is quantified by preparing a ring-like sample having a diameter of 7 mm, winding a conductive wire coil on this sample for 5 turns, and measuring the AC magnetic permeability at a carrier frequency (13.56 MHz) using an impedance analyzer. Was obtained. The results are shown in Table 2.
なお、磁気特性の判定は、透磁率μ′を指標として以下の基準で行った。 The magnetic characteristics were determined based on the following criteria using the permeability μ ′ as an index.
（軟磁性粉末としてFe-Si-Crを使用した場合）
◎：４２≦μ′
○：３８≦μ′＜４２
△：３４≦μ′＜３８
×： μ′＜３４ (When Fe-Si-Cr is used as soft magnetic powder)
A: 42 ≦ μ ′
○: 38 ≦ μ ′ <42
Δ: 34 ≦ μ ′ <38
×: μ ′ <34
（軟磁性粉末としてFe-Si-Alを使用した場合）
◎：６５≦μ′
○：６０≦μ′＜６５
△：５５≦μ′＜６０
×： μ′＜５５ (When using Fe-Si-Al as soft magnetic powder)
A: 65 ≦ μ ′
○: 60 ≦ μ ′ <65
Δ: 55 ≦ μ ′ <60
×: μ ′ <55
（軟磁性粉末としてSiO2被覆Fe-Si-Crを使用した場合）
◎：４２≦μ′
○：３８≦μ′＜４２
△：３４≦μ′＜３８
×： μ′＜３４ (When using SiO 2 coated Fe-Si-Cr as soft magnetic powder)
A: 42 ≦ μ ′
○: 38 ≦ μ ′ <42
Δ: 34 ≦ μ ′ <38
×: μ ′ <34
（軟磁性粉末としてアクリル樹脂被覆Fe-Si-Crを使用した場合）
◎：４２≦μ′
○：３８≦μ′＜４２
△：３４≦μ′＜３８
×： μ′＜３４ (When using acrylic resin-coated Fe-Si-Cr as soft magnetic powder)
A: 42 ≦ μ ′
○: 38 ≦ μ ′ <42
Δ: 34 ≦ μ ′ <38
×: μ ′ <34
また、比重変化率、μ′変化率及びシート厚の変化率の評価は、以下の基準で行った。 The specific gravity change rate, μ ′ change rate, and sheet thickness change rate were evaluated according to the following criteria.
（比重変化率）
◎： １％未満
○： １以上３％未満
△： ３％以上５％未満
×： ５％以上(Specific gravity change rate)
◎: Less than 1% ○: 1 or more and less than 3% △: 3% or more and less than 5% ×: 5% or more
（μ′変化率）
◎： １％未満
○： １以上３％未満
△： ３％以上５％未満
×： ５％以上(Μ ′ change rate)
◎: Less than 1% ○: 1 or more and less than 3% △: 3% or more and less than 5% ×: 5% or more
（シート厚の変化率）
◎：１％未満
○：１％以上３％未満
△：３％以上５％未満
×：５％以上(Change rate of sheet thickness)
◎: Less than 1% ○: 1% or more and less than 3% △: 3% or more and less than 5% ×: 5% or more
この表２から、実施例１Ａ〜４Ａでは、高温高湿環境下においても寸法変化や磁気特性の変化が小さい軟磁性シートが得られたことが解る。例えば、比較例２Ａと各実施例とを比べた場合、実施例においては軟磁性シートの厚み変化率が小さく、また、比較例1と比べた場合、各実施例の軟磁性シートは、環境試験後の磁気特性の低下も少ないことが解る。 From Table 2, it can be seen that in Examples 1A to 4A, soft magnetic sheets with small dimensional changes and magnetic property changes were obtained even in a high temperature and high humidity environment. For example, when the comparative example 2A is compared with each example, the thickness change rate of the soft magnetic sheet is small in the example, and when compared with the comparative example 1, the soft magnetic sheet of each example is an environmental test. It can be seen that there is little decrease in the magnetic properties later.
実施例１Ｂ
表３に示した配合（重量部）に従って、リン内添ポリエステル樹脂（バイロン５３７、東洋紡績社製）と、扁平な軟磁性粉末（Ｆｅ−Ｓｉ−Ｃｒ−Ｎｉ、ＪＥＭＣＯ社製）と、シランカップリング剤（ＳＨ６０４０、東レダウコーニング）と、イソプロピルアルコール（ＩＰＡ）と、ブロックイソシアネート（コロネート２５０７、日本ポリウレタン社）とを混合して軟磁性塗料を調製し、その軟磁性塗料を、剥離ＰＥＴフィルム（帝人社）に、塗料固形分が１８０ｇ／ｍ２となるようにロールコーターで塗布し、１１５℃で１０分間乾燥し、剥離ＰＥＴフィルムに支持された未硬化の軟磁性シートを得た。Example 1B
According to the formulation (parts by weight) shown in Table 3, phosphorus-added polyester resin (Byron 537, manufactured by Toyobo Co., Ltd.), flat soft magnetic powder (Fe-Si-Cr-Ni, manufactured by JEMCO), and silane cup A ring agent (SH 6040, Toray Dow Corning), isopropyl alcohol (IPA), and blocked isocyanate (Coronate 2507, Nippon Polyurethane Co., Ltd.) are mixed to prepare a soft magnetic paint. Teijin Ltd.) was applied with a roll coater so that the solid content of the paint would be 180 g / m 2 and dried at 115 ° C. for 10 minutes to obtain an uncured soft magnetic sheet supported by a peeled PET film.
次に、剥離ＰＥＴフィルムを取り除いた未硬化軟磁性シートを５枚積層し、ラミネータのロールとロールの間（上下のロールの温度を１１０℃、線圧を３．３ｋｇｆ／ｃｍ、ラインスピードを０．５ｍ／分に設定した。）を１０回通して圧縮して未硬化の軟磁性シート中の軟磁性粉末を配向させ、更に、１５０℃で５Ｋｇ／ｃｍ２の圧力で１０分間圧縮することによって架橋硬化させ、軟磁性シートを得た。得られた軟磁性シートは、比重が大きく、高温、高温高湿環境下に放置しても磁気特性の低下が小さかった。Next, five uncured soft magnetic sheets from which the peeled PET film was removed were laminated, and between the laminator rolls (the temperature of the upper and lower rolls was 110 ° C., the linear pressure was 3.3 kgf / cm, and the line speed was 0. By pressing 10 times to orient the soft magnetic powder in the uncured soft magnetic sheet and further compressing at 150 ° C. with a pressure of 5 kg / cm 2 for 10 minutes. Crosslinking and curing was performed to obtain a soft magnetic sheet. The obtained soft magnetic sheet had a large specific gravity, and even when it was left in a high temperature, high temperature and high humidity environment, the magnetic properties were hardly deteriorated.
実施例２Ｂ
ラミネータを用いた圧縮を行わない以外は、実施例１Ｂの操作を繰り返すことにより、架橋硬化した軟磁性シートを得た。得られた軟磁性シートは、比重が大きく、高温、高温高湿環境下に放置しても磁気特性の低下が小さかった。Example 2B
A soft magnetic sheet that was crosslinked and cured was obtained by repeating the operation of Example 1B, except that compression using a laminator was not performed. The obtained soft magnetic sheet had a large specific gravity, and even when it was left in a high temperature, high temperature and high humidity environment, the magnetic properties were hardly deteriorated.
実施例３Ｂ
剥離ＰＥＴフィルムに塗布された軟磁性塗料の乾燥温度を１２５℃とする以外は、実施例１Ｂと同様の操作を繰り返すことにより、架橋硬化した軟磁性シートを得た。得られた軟磁性シートは、軟磁性塗料の１２５℃での乾燥時にブロックイソシアネートのブロックが解離して一部架橋が進行しているため、μ′と比重の数値が実施例１Ｂの場合よりも若干小さかったが、実用上問題のない数値であった。Example 3B
A cross-linked and hardened soft magnetic sheet was obtained by repeating the same operation as in Example 1B, except that the drying temperature of the soft magnetic paint applied to the peeled PET film was 125 ° C. In the obtained soft magnetic sheet, when the soft magnetic coating material was dried at 125 ° C., the block of the blocked isocyanate was dissociated and partially cross-linked, so the values of μ ′ and specific gravity were higher than those in Example 1B. Although it was slightly small, it was a numerical value that had no practical problem.
比較例１Ｂ
ブロックイソシアネートに代えて、イソシアネート（コロネートＨＬ、日本ポリウレタン社製）を使用する以外は、実施例１Ｂと同様の操作を繰り返すことにより、架橋硬化した軟磁性シートを得た。得られた軟磁性シートは、ブロックされていないイソシアネートを用いたので乾燥させる工程でイソシアネートとリン内添ポリエステル系樹脂が架橋しており、比重を大きくすることができなかった。Comparative Example 1B
A crosslinked and hardened soft magnetic sheet was obtained by repeating the same operation as in Example 1B except that isocyanate (Coronate HL, manufactured by Nippon Polyurethane Co., Ltd.) was used in place of the blocked isocyanate. Since the obtained soft magnetic sheet used unblocked isocyanate, the isocyanate and the phosphorus-containing polyester resin were cross-linked in the drying step, and the specific gravity could not be increased.
比較例２Ｂ
ブロックイソシアネートを使用せず且つ軟磁性塗料の乾燥温度を１２０℃とする以外は、実施例１Ｂの操作を繰り返すことにより、未硬化の軟磁性シートを得た。次に、剥離ＰＥＴフィルムを取り除いた未硬化軟磁性シートを５枚積層し、ラミネータによる圧縮を行わずに、１５０℃で５Ｋｇ／ｃｍ２の圧力で１０分間圧縮することによって架橋硬化させ、軟磁性シートを得た。得られた軟磁性シートは、架橋されていないので、環境試験後の比重と磁気特性とが低下した。Comparative Example 2B
An uncured soft magnetic sheet was obtained by repeating the operation of Example 1B, except that no blocked isocyanate was used and the drying temperature of the soft magnetic paint was set to 120 ° C. Next, five uncured soft magnetic sheets from which the peeled PET film was removed were stacked and crosslinked and cured by compression at 150 ° C. and a pressure of 5 kg / cm 2 for 10 minutes without performing compression with a laminator, and soft magnetic A sheet was obtained. Since the obtained soft magnetic sheet was not crosslinked, the specific gravity and magnetic properties after the environmental test were lowered.
得られた架橋硬化した軟磁性シート（実施例１Ｂ〜３Ｂ及び比較例１Ｂ〜２Ｂ）について、磁気特性（透磁率μ′、磁気損失μ"、性能係数Ｑ）及び比重を測定した。また、６０℃、９５％Ｒｈの高温高湿環境下に１９２時間保持した後の軟磁性シートの磁気特性（μ′、μ"、Ｑ）を測定し、さらに前記環境試験前後における軟磁性シートの比重変化率及びμ′変化率を算出し、実施例１Ａの場合と同様に評価した。結果を表３に示す。 With respect to the obtained crosslinked and hardened soft magnetic sheets (Examples 1B to 3B and Comparative Examples 1B to 2B), the magnetic characteristics (permeability μ ′, magnetic loss μ ″, performance coefficient Q) and specific gravity were measured. The magnetic properties (μ ′, μ ″, Q) of the soft magnetic sheet after being held for 192 hours in a high-temperature and high-humidity environment at 95 ° C. and 95% Rh were measured, and the specific gravity change rate of the soft magnetic sheet before and after the environmental test And the change rate of μ ′ were calculated and evaluated in the same manner as in Example 1A. The results are shown in Table 3.
なお、磁気特性の判定は、透磁率μ′を指標として以下の基準で行った。 The magnetic characteristics were determined based on the following criteria using the permeability μ ′ as an index.
（軟磁性粉末としてFe-Si-Cr-Niを使用）
◎：４２≦μ′
○：３８≦μ′＜４２
△：３４≦μ′＜３８
×： μ′＜３４
(Fe-Si-Cr-Ni is used as soft magnetic powder)
A: 42 ≦ μ ′
○: 38 ≦ μ ′ <42
Δ: 34 ≦ μ ′ <38
×: μ ′ <34
実施例４Ｂ
表４に示した配合（重量部）に従って、リン内添ポリエステル樹脂（バイロン５３７、東洋紡績社製）と、扁平な軟磁性粉末（Ｆｅ−Ｓｉ−Ａｌ、株式会社メイト製）と、シランカップリング剤（ＳＨ６０４０、東レダウコーニング）と、イソプロピルアルコール（ＩＰＡ）と、ブロックイソシアネート（コロネート２５０７、日本ポリウレタン社）と混合して軟磁性塗料を調製し、その軟磁性塗料を、剥離ＰＥＴフィルム（帝人社）に、塗料固形分が１８０ｇ／ｍ２となるようにロールコーターで塗布し、１１５℃で１０分間乾燥し、剥離ＰＥＴフィルムに支持された未硬化軟磁性シートを得た。Example 4B
According to the formulation (parts by weight) shown in Table 4, phosphorus-added polyester resin (Byron 537, manufactured by Toyobo Co., Ltd.), flat soft magnetic powder (Fe-Si-Al, manufactured by Mate Co., Ltd.), and silane coupling Agent (SH6040, Toray Dow Corning), isopropyl alcohol (IPA), and blocked isocyanate (Coronate 2507, Nippon Polyurethane Co., Ltd.) were mixed to prepare a soft magnetic coating material. ) Was applied with a roll coater so that the solid content of the coating was 180 g / m 2 and dried at 115 ° C. for 10 minutes to obtain an uncured soft magnetic sheet supported by a peeled PET film.
次に、剥離ＰＥＴフィルムを取り除いた未硬化軟磁性シートを５枚積層し、ラミネータのロールとロールの間（上下のロールの温度を１１０℃、線圧を３．３ｋｇｆ／ｃｍ、ラインスピードを０．５ｍ／分に設定した。）を１０回通して圧縮によって配向させ、更に、１５０℃で６Ｋｇ／ｃｍ２の圧力で１０分間圧縮することによって架橋硬化させ、軟磁性シートを得た。得られた軟磁性シートは、比重が大きく、高温、高温高湿環境下に放置しても磁気特性の低下が小さかった。Next, five uncured soft magnetic sheets from which the peeled PET film was removed were laminated, and between the laminator rolls (the temperature of the upper and lower rolls was 110 ° C., the linear pressure was 3.3 kgf / cm, and the line speed was 0. Is set to 5 m / min.) By passing 10 times through compression, and further crosslinked and cured by compression at 150 ° C. under a pressure of 6 kg / cm 2 for 10 minutes to obtain a soft magnetic sheet. The obtained soft magnetic sheet had a large specific gravity, and even when it was left in a high temperature, high temperature and high humidity environment, the magnetic properties were hardly deteriorated.
実施例５Ｂ
ラミネータを用いた圧縮を行わない以外は、実施例４Ｂの操作を繰り返すことにより、架橋硬化した軟磁性シートを得た。得られた軟磁性シートは、比重が大きく、高温、高温高湿環境下に放置しても磁気特性の低下が小さかった。Example 5B
Except for not performing compression using a laminator, the procedure of Example 4B was repeated to obtain a crosslinked and hardened soft magnetic sheet. The obtained soft magnetic sheet had a large specific gravity, and even when it was left in a high temperature, high temperature and high humidity environment, the magnetic properties were hardly deteriorated.
実施例６Ｂ
剥離ＰＥＴフィルムに塗布された軟磁性塗料の乾燥温度を１２５℃とする以外は、実施例４Ｂと同様の操作を繰り返すことにより、架橋硬化した軟磁性シートを得た。得られた軟磁性シートは、軟磁性塗料の１２５℃での乾燥時にブロックイソシアネートのブロックが解離して一部架橋が進行しているため、μ′と比重の数値が実施例４Ｂの場合よりも若干小さかったが、実用上問題のない数値であった。Example 6B
A crosslink-cured soft magnetic sheet was obtained by repeating the same operation as in Example 4B, except that the drying temperature of the soft magnetic coating applied to the release PET film was 125 ° C. In the obtained soft magnetic sheet, when the soft magnetic coating material was dried at 125 ° C., the block of the blocked isocyanate was dissociated and partially cross-linked, so the values of μ ′ and specific gravity were higher than those in Example 4B. Although it was slightly small, it was a numerical value that had no practical problem.
比較例３Ｂ
ブロックイソシアネートに代えて、イソシアネート（コロネートＨＬ、日本ポリウレタン社製）を使用する以外は、実施例４Ｂと同様の操作を繰り返すことにより、架橋硬化した軟磁性シートを得た。得られた軟磁性シートは、ブロックされていないイソシアネートを用いたので乾燥させる工程でイソシアネートとリン内添ポリエステル系樹脂が架橋しており、比重を大きくすることができなかった。Comparative Example 3B
A crosslinked and hardened soft magnetic sheet was obtained by repeating the same operation as in Example 4B except that isocyanate (Coronate HL, manufactured by Nippon Polyurethane Co., Ltd.) was used in place of the blocked isocyanate. Since the obtained soft magnetic sheet used unblocked isocyanate, the isocyanate and the phosphorus-containing polyester resin were cross-linked in the drying step, and the specific gravity could not be increased.
比較例４Ｂ
ブロックイソシアネートを使用せず且つ軟磁性塗料の乾燥温度を１２０℃とする以外は、実施例４Ｂの操作を繰り返すことにより、未硬化の軟磁性シートを得た。次に、剥離ＰＥＴフィルムを取り除いた未硬化軟磁性シートを５枚積層し、ラミネータによる圧縮を行わずに、１５０℃で６Ｋｇ／ｃｍ２の圧力で１０分間圧縮することによって架橋硬化させ、軟磁性シートを得た。得られた軟磁性シートは、架橋されていないので、環境試験後の比重と磁気特性とが低下した。Comparative Example 4B
An uncured soft magnetic sheet was obtained by repeating the operation of Example 4B, except that no blocked isocyanate was used and the drying temperature of the soft magnetic paint was set to 120 ° C. Next, five uncured soft magnetic sheets from which the peeled PET film was removed were stacked and crosslinked and cured by compression at 150 ° C. and a pressure of 6 kg / cm 2 for 10 minutes without being compressed by a laminator. A sheet was obtained. Since the obtained soft magnetic sheet was not crosslinked, the specific gravity and magnetic properties after the environmental test were lowered.
得られた架橋硬化した軟磁性シート（実施例４Ｂ〜６Ｂ及び比較例３Ｂ〜４Ｂ）について、磁気特性（透磁率μ′、磁気損失μ"、性能係数Ｑ）及び比重を測定した。また、６０℃、９５％Ｒｈの高温高湿環境下に１９２時間保持した後の軟磁性シートの磁気特性（μ′、μ"、Ｑ）を測定し、さらに前記環境試験前後における軟磁性シートの比重変化率及びμ′変化率を算出し、実施例１Ａの場合と同様に評価した。結果を表４に示す。 The obtained cross-linked and hardened soft magnetic sheets (Examples 4B to 6B and Comparative Examples 3B to 4B) were measured for magnetic properties (permeability μ ′, magnetic loss μ ″, performance coefficient Q) and specific gravity. The magnetic properties (μ ′, μ ″, Q) of the soft magnetic sheet after being held for 192 hours in a high-temperature and high-humidity environment at 95 ° C. and 95% Rh were measured, and the specific gravity change rate of the soft magnetic sheet before and after the environmental test And the change rate of μ ′ were calculated and evaluated in the same manner as in Example 1A. The results are shown in Table 4.
なお、磁気特性の判定は、透磁率μ′を指標として以下の基準で行った。 The magnetic characteristics were determined based on the following criteria using the permeability μ ′ as an index.
（軟磁性粉末としてFe-Si-Alを使用）
◎：６５≦μ′
○：６０≦μ′＜６５
△：５５≦μ′＜６０
×： μ′＜５５
(Fe-Si-Al is used as soft magnetic powder)
A: 65 ≦ μ ′
○: 60 ≦ μ ′ <65
Δ: 55 ≦ μ ′ <60
×: μ ′ <55
実施例７Ｂ
表５に示したように、リン内添ポリエステル樹脂に代えて、水酸基価が５．０ＫＯＨｍｇ／ｇのポリエステル樹脂（バイロン５００、東洋紡績社製）を使用する以外は、実施例１Ｂの操作を繰り返すことにより、架橋硬化した軟磁性シートを得た。得られた軟磁性シートは、比重が大きく、高温、高温高湿環境下に放置しても磁気特性の低下が小さかった。Example 7B
As shown in Table 5, the operation of Example 1B was repeated except that a polyester resin having a hydroxyl value of 5.0 KOHmg / g (Byron 500, manufactured by Toyobo Co., Ltd.) was used instead of the phosphorus-added polyester resin. As a result, a crosslinked and hardened soft magnetic sheet was obtained. The obtained soft magnetic sheet had a large specific gravity, and even when it was left in a high temperature, high temperature and high humidity environment, the magnetic properties were hardly deteriorated.
実施例８Ｂ
実施例１Ｂの操作を繰り返したところ、得られた軟磁性シートは、比重が大きく、高温乾燥環境下、高温高湿環境下に放置しても磁気特性の低下が小さく、再現性ある実施例であった。Example 8B
When the operation of Example 1B was repeated, the obtained soft magnetic sheet had a large specific gravity, and even when left in a high-temperature dry environment or a high-temperature and high-humidity environment, the magnetic properties were not significantly reduced, and in a reproducible example. there were.
実施例９Ｂ
リン内添ポリエステル樹脂の配合量を１００重量部から７５重量部とし、新たにメラミンシアヌレート（ＭＣ６１０、日産化学工業社製）２５重量部を配合すること以外は、実施例１Ｂの操作を繰り返すことにより、架橋硬化した軟磁性シートを得た。得られた軟磁性シートは、比重が大きく、高温、高温高湿環境下に放置しても磁気特性の低下が小さかった。また、燃焼試験を行ったところ、ＵＬ９４ Ｖ−０の基準を満たしていた。Example 9B
The procedure of Example 1B is repeated except that the amount of the polyester resin added with phosphorus is 100 to 75 parts by weight and 25 parts by weight of melamine cyanurate (MC610, manufactured by Nissan Chemical Industries, Ltd.) is newly added. Thus, a cross-linked and hardened soft magnetic sheet was obtained. The obtained soft magnetic sheet had a large specific gravity, and even when it was left in a high temperature, high temperature and high humidity environment, the magnetic properties were hardly deteriorated. Further, when a combustion test was performed, the UL94 V-0 standard was satisfied.
比較例５Ｂ
ブロックイソシアネートを使用しない以外は、実施例７Ｂの操作を繰り返すことにより、架橋硬化した軟磁性シートを得た。得られた軟磁性シートは、架橋されていないので、環境試験後の比重と磁気特性とが低下した。Comparative Example 5B
Except not using block isocyanate, the operation of Example 7B was repeated to obtain a crosslinked and hardened soft magnetic sheet. Since the obtained soft magnetic sheet was not crosslinked, the specific gravity and magnetic properties after the environmental test were lowered.
比較例６Ｂ
リン内添ポリエステル樹脂に代えて、リン外添ポリエステル樹脂（ポリエステル（バイロン５００、東洋紡績社）：リン酸エステル（ＣＲ７４１、大八化学社）＝１００：３）を使用すること以外は、実施例８Ｂと同様の操作を繰り返すことにより、架橋硬化した軟磁性シートを得た。得られた積層軟磁性シートは、積層面で剥離が見られ、環境試験後には積層軟磁性シートが個々の軟磁性シートに剥離分離した。Comparative Example 6B
Except for using a phosphorus externally added polyester resin (polyester (Byron 500, Toyobo Co., Ltd.): phosphoric ester (CR741, Daihachi Chemical Co., Ltd.) = 100: 3) instead of the phosphorus internally added polyester resin. By repeating the same operation as in 8B, a crosslinked and hardened soft magnetic sheet was obtained. The obtained laminated soft magnetic sheet was peeled on the laminated surface, and after the environmental test, the laminated soft magnetic sheet was separated into individual soft magnetic sheets.
比較例７Ｂ
表５に示した配合（重量部）に従って、リン内添ポリエステル樹脂（バイロン５３７、東洋紡績社製）と、扁平な軟磁性粉末（Ｆｅ−Ｓｉ−Ｃｒ−Ｎｉ、ＪＥＭＣＯ社製）と、ブロックイソシアネート（コロネート２５０７、日本ポリウレタン社）と混合して軟磁性塗料を調製し、その軟磁性塗料を、剥離ＰＥＴフィルム（帝人社）に、塗料固形分が１８０ｇ／ｍ２となるようにロールコーターで塗布し、１１５℃で１０分間乾燥し、剥離ＰＥＴフィルムに支持された未硬化軟磁性シートを得た。Comparative Example 7B
In accordance with the formulation (parts by weight) shown in Table 5, phosphorus-added polyester resin (Byron 537, manufactured by Toyobo Co., Ltd.), flat soft magnetic powder (Fe-Si-Cr-Ni, manufactured by JEMCO), and blocked isocyanate (Coronate 2507, Nippon Polyurethane Co., Ltd.) to prepare a soft magnetic paint, and apply the soft magnetic paint to a peeled PET film (Teijin) with a roll coater so that the solid content of the paint is 180 g / m 2. And dried at 115 ° C. for 10 minutes to obtain an uncured soft magnetic sheet supported by a peeled PET film.
次に、剥離ＰＥＴフィルムを取り除いた未硬化軟磁性シートを５枚積層し、ラミネータのロールとロールの間（上下のロールの温度を１１０℃、線圧を３．３ｋｇｆ／ｃｍ、ラインスピードを０．５ｍ／分に設定した。）を１０回通して圧縮によって配向させ、更に、１５０℃で６Ｋｇ／ｃｍ２の圧力で１０分間圧縮することによって架橋硬化させ、軟磁性シートを得た。得られた軟磁性シートは、シランカップリング剤を使用していないので、圧縮しても比重が増大しなかった。Next, five uncured soft magnetic sheets from which the peeled PET film was removed were laminated, and between the laminator rolls (the temperature of the upper and lower rolls was 110 ° C., the linear pressure was 3.3 kgf / cm, and the line speed was 0. Is set to 5 m / min.) By passing 10 times through compression, and further crosslinked and cured by compression at 150 ° C. under a pressure of 6 kg / cm 2 for 10 minutes to obtain a soft magnetic sheet. Since the obtained soft magnetic sheet did not use a silane coupling agent, the specific gravity did not increase even when compressed.
得られた架橋硬化した軟磁性シート（実施例７Ｂ〜９Ｂ及び比較例５Ｂ〜７Ｂ）について、磁気特性（透磁率μ′、磁気損失μ"、性能係数Ｑ）及び比重を測定した。また、高温乾燥環境下又は高温高湿環境下（高温乾燥条件 ８５℃、１０％Ｒｈ以下；高温高湿条件 ６０℃、９５％Ｒｈ）に１９２時間保持した後の軟磁性シートの磁気特性（μ′、μ"、Ｑ）を測定し、さらに前記環境試験前後における軟磁性シートの比重変化率及びμ′変化率を算出し、実施例１Ａの場合と同様に評価した。結果を表５に示す。 With respect to the obtained cross-linked and hardened soft magnetic sheets (Examples 7B to 9B and Comparative Examples 5B to 7B), magnetic characteristics (permeability μ ′, magnetic loss μ ″, performance coefficient Q) and specific gravity were measured. Magnetic properties (μ ′, μ) of the soft magnetic sheet after being held in a dry environment or a high temperature and high humidity environment (high temperature drying conditions 85 ° C., 10% Rh or less; high temperature high humidity conditions 60 ° C., 95% Rh) for 192 hours “, Q) was measured, and the specific gravity change rate and μ ′ change rate of the soft magnetic sheet before and after the environmental test were calculated and evaluated in the same manner as in Example 1A. The results are shown in Table 5.
なお、磁気特性の判定は、透磁率μ′を指標として以下の基準で行った。 The magnetic characteristics were determined based on the following criteria using the permeability μ ′ as an index.
（軟磁性粉末としてFe-Si-Cr-Niを使用）
◎：４２≦μ′
○：３８≦μ′＜４２
△：３４≦μ′＜３８
×： μ′＜３４
(Fe-Si-Cr-Ni is used as soft magnetic powder)
A: 42 ≦ μ ′
○: 38 ≦ μ ′ <42
Δ: 34 ≦ μ ′ <38
×: μ ′ <34
実施例１０Ｂ
表６に示したように、リン内添ポリエステル樹脂に代えて、水酸基価５．０ＫＯＨｍｇ／ｇのポリエステル樹脂（バイロン５００、東洋紡績社製）を使用する以外は、実施例４Ｂの操作を繰り返すことにより、架橋硬化した軟磁性シートを得た。得られた軟磁性シートは、比重が大きく、高温、高温高湿環境下に放置しても磁気特性の低下が小さかった。Example 10B
As shown in Table 6, the operation of Example 4B is repeated except that a polyester resin having a hydroxyl value of 5.0 KOHmg / g (Byron 500, manufactured by Toyobo Co., Ltd.) is used instead of the phosphorus-added polyester resin. Thus, a cross-linked and hardened soft magnetic sheet was obtained. The obtained soft magnetic sheet had a large specific gravity, and even when it was left in a high temperature, high temperature and high humidity environment, the magnetic properties were hardly deteriorated.
実施例１１Ｂ
実施例４Ｂの操作を繰り返したところ、得られた軟磁性シートは、比重が大きく、高温、高温高湿環境下に放置しても磁気特性の低下が小さく、再現性ある実施例であった。Example 11B
When the operation of Example 4B was repeated, the obtained soft magnetic sheet had a large specific gravity and had a low reproducibility even when left in a high temperature, high temperature, high humidity environment, and was a reproducible example.
実施例１２Ｂ
更に、メラミンシアヌレート（ＭＣ６１０、日産化学工業株式会社製）３５重量部を配合すること以外は、実施例４Ｂの操作を繰り返すことにより、架橋硬化した軟磁性シートを得た。得られた軟磁性シートは、比重が大きく、高温、高温高湿環境下に放置しても磁気特性の低下が小さかった。また、燃焼試験を行ったところ、ＵＬ９４ Ｖ−０の基準を満たしていた。Example 12B
Furthermore, a crosslink-cured soft magnetic sheet was obtained by repeating the operation of Example 4B except that 35 parts by weight of melamine cyanurate (MC610, manufactured by Nissan Chemical Industries, Ltd.) was blended. The obtained soft magnetic sheet had a large specific gravity, and even when it was left in a high temperature, high temperature and high humidity environment, the magnetic properties were hardly deteriorated. Further, when a combustion test was performed, the UL94 V-0 standard was satisfied.
比較例８Ｂ
ブロックイソシアネートを使用しない以外は、実施例１０Ｂの操作を繰り返すことにより、架橋硬化した軟磁性シートを得た。得られた軟磁性シートは、架橋されていないので、環境試験後の比重と磁気特性とが低下した。Comparative Example 8B
Except not using block isocyanate, the operation of Example 10B was repeated to obtain a crosslinked and hardened soft magnetic sheet. Since the obtained soft magnetic sheet was not crosslinked, the specific gravity and magnetic properties after the environmental test were lowered.
比較例９Ｂ
リン内添ポリエステル樹脂に代えて、リン外添ポリエステル樹脂（ポリエステル（バイロン５００、東洋紡績社）：リン酸エステル（ＣＲ７４１、大八化学社）＝１００：３）を使用すること以外は、実施例１１Ｂと同様の操作を繰り返すことにより、架橋硬化した軟磁性シートを得た。得られた積層軟磁性シートは、積層面で剥離が見られ、環境試験後には積層軟磁性シートが個々の軟磁性シートに剥離分離した。Comparative Example 9B
Except for using a phosphorus externally added polyester resin (polyester (Byron 500, Toyobo Co., Ltd.): phosphoric ester (CR741, Daihachi Chemical Co., Ltd.) = 100: 3) instead of the phosphorus internally added polyester resin. By repeating the same operation as 11B, a cross-linked and hardened soft magnetic sheet was obtained. The obtained laminated soft magnetic sheet was peeled on the laminated surface, and after the environmental test, the laminated soft magnetic sheet was separated into individual soft magnetic sheets.
比較例１０Ｂ
表６に示した配合（重量部）に従って、リン内添ポリエステル樹脂（バイロン５３７、東洋紡績社製）と、扁平な軟磁性粉末（Ｆｅ−Ｓｉ−Ａｌ、株式会社メイト製）と、ブロックイソシアネート（コロネート２５０７、日本ポリウレタン社）と混合して軟磁性塗料を調製し、その軟磁性塗料を、剥離ＰＥＴフィルム（帝人社）に、塗料固形分が１８０ｇ／ｍ２となるようにロールコーターで塗布し、１１５℃で１０分間乾燥し、剥離ＰＥＴフィルムに支持された未硬化軟磁性シートを得た。Comparative Example 10B
According to the formulation (parts by weight) shown in Table 6, phosphorus-added polyester resin (Byron 537, manufactured by Toyobo Co., Ltd.), flat soft magnetic powder (Fe-Si-Al, manufactured by Mate Corporation), and blocked isocyanate ( (Coronate 2507, Nippon Polyurethane Co., Ltd.) to prepare a soft magnetic paint, and the soft magnetic paint is applied to a release PET film (Teijin) with a roll coater so that the solid content of the paint is 180 g / m 2. And dried at 115 ° C. for 10 minutes to obtain an uncured soft magnetic sheet supported by a peeled PET film.
次に、剥離ＰＥＴフィルムを取り除いた未硬化軟磁性シートを５枚積層し、ラミネータのロールとロールの間（上下のロールの温度を１１０℃、線圧を３．３ｋｇｆ／ｃｍ、ラインスピードを０．５ｍ／分に設定した。）を１０回通して圧縮によって配向させ、更に、１５０℃で６Ｋｇ／ｃｍ２の圧力で１０分間圧縮することによって架橋硬化させ、軟磁性シートを得た。得られた軟磁性シートは、シランカップリング剤を使用していないので、圧縮しても比重が増大しなかった。Next, five uncured soft magnetic sheets from which the peeled PET film was removed were laminated, and between the laminator rolls (the temperature of the upper and lower rolls was 110 ° C., the linear pressure was 3.3 kgf / cm, and the line speed was 0. Is set to 5 m / min.) By passing 10 times through compression, and further crosslinked and cured by compression at 150 ° C. under a pressure of 6 kg / cm 2 for 10 minutes to obtain a soft magnetic sheet. Since the obtained soft magnetic sheet did not use a silane coupling agent, the specific gravity did not increase even when compressed.
得られた架橋硬化した軟磁性シート（実施例１０Ｂ〜１２Ｂ及び比較例８Ｂ〜１０Ｂ）について、磁気特性（透磁率μ′、磁気損失μ"、性能係数Ｑ）及び比重を測定した。また、高温乾燥環境下又は高温高湿環境下（高温条件 ８５℃、１０％Ｒｈ以下；高温高湿条件 ６０℃、９５％Ｒｈ）に１９２時間保持した後の軟磁性シートの磁気特性（μ′、μ"、Ｑ）を測定し、さらに前記環境試験前後における軟磁性シートの比重変化率及びμ′変化率を算出し、実施例１Ａの場合と同様に評価した。結果を表６に示す。 The obtained cross-linked and hardened soft magnetic sheets (Examples 10B to 12B and Comparative Examples 8B to 10B) were measured for magnetic properties (permeability μ ′, magnetic loss μ ″, performance coefficient Q) and specific gravity. Magnetic properties (μ ′, μ ″) of soft magnetic sheet after being held for 192 hours in a dry environment or in a high temperature and high humidity environment (high temperature condition 85 ° C., 10% Rh or less; high temperature high humidity condition 60 ° C., 95% Rh) Q) was measured, and the specific gravity change rate and μ ′ change rate of the soft magnetic sheet before and after the environmental test were calculated and evaluated in the same manner as in Example 1A. The results are shown in Table 6.
なお、磁気特性の判定は、透磁率μ′を指標として以下の基準で行った。 The magnetic characteristics were determined based on the following criteria using the permeability μ ′ as an index.
（軟磁性粉末としてFe-Si-Alを使用）
◎：６５≦μ′
○：６０≦μ′＜６５
△：５５≦μ′＜６０
×： μ′＜５５
(Fe-Si-Al is used as soft magnetic powder)
A: 65 ≦ μ ′
○: 60 ≦ μ ′ <65
Δ: 55 ≦ μ ′ <60
×: μ ′ <55
実施例１３Ｂ〜実施例１７Ｂ、比較例１１Ｂ〜１２Ｂ
表７に示した配合（重量部）に従って、リン内添ポリエステル樹脂（バイロン５３７、東洋紡績社製）と、扁平な軟磁性粉末（Ｆｅ−Ｓｉ−Ｃｒ−Ｎｉ、ＪＥＭＣＯ社製）と、シランカップリング剤と、ＩＰＡと、ブロックイソシアネート（コロネート２５０７、日本ポリウレタン社）とを混合して軟磁性塗料を調製し、その軟磁性塗料を、剥離ＰＥＴフィルム（帝人社）に、塗料固形分が１８０ｇ／ｍ２となるようにロールコーターで塗布し、１１５℃で１０分間乾燥し、剥離ＰＥＴフィルムに支持された未硬化軟磁性シートを得た。Example 13B to Example 17B, Comparative Examples 11B to 12B
According to the formulation (parts by weight) shown in Table 7, phosphorus-added polyester resin (Byron 537, manufactured by Toyobo Co., Ltd.), flat soft magnetic powder (Fe-Si-Cr-Ni, manufactured by JEMCO), and silane cup A ring agent, IPA, and blocked isocyanate (Coronate 2507, Nippon Polyurethane Co., Ltd.) are mixed to prepare a soft magnetic coating, and the soft magnetic coating is applied to a release PET film (Teijin) with a solid content of 180 g / It was coated by a roll coater so that m 2, dried for 10 minutes at 115 ° C., to obtain an uncured soft magnetic sheet supported on release PET film.
なお、使用した軟磁性粉末のパーセント粒径、比表面積、飽和磁化、保持力、タップ密度、扁平度を表７に示す。 Table 7 shows the percent particle diameter, specific surface area, saturation magnetization, coercive force, tap density, and flatness of the soft magnetic powder used.
得られた架橋硬化した軟磁性シート（実施例１３Ｂ〜１７Ｂ及び比較例１１Ｂ〜１２Ｂ）について、磁気特性（透磁率μ′、磁気損失μ"、性能係数Ｑ）及び比重を測定した。また、高温乾燥環境下又は高温高湿環境下（高温乾燥条件 ８５℃、１０％Ｒｈ以下；高温高湿条件 ６０℃、９５％Ｒｈ）に１９２時間保持した後の軟磁性シートの磁気特性（μ′、μ"、Ｑ）を測定し、さらに前記環境試験前後における軟磁性シートの比重変化率及び透磁率変化率を算出し、実施例１Ａの場合と同様に評価した。結果を表７に示す。 The obtained cross-linked and hardened soft magnetic sheets (Examples 13B to 17B and Comparative Examples 11B to 12B) were measured for magnetic properties (permeability μ ′, magnetic loss μ ″, performance coefficient Q) and specific gravity. Magnetic properties (μ ′, μ) of the soft magnetic sheet after being held in a dry environment or a high temperature and high humidity environment (high temperature drying conditions 85 ° C., 10% Rh or less; high temperature high humidity conditions 60 ° C., 95% Rh) for 192 hours “, Q) was measured, and the specific gravity change rate and permeability change rate of the soft magnetic sheet before and after the environmental test were calculated and evaluated in the same manner as in Example 1A. The results are shown in Table 7.
なお、磁気特性の判定は、透磁率μ′を指標として以下の基準で行った。 The magnetic characteristics were determined based on the following criteria using the permeability μ ′ as an index.
（軟磁性粉末としてFe-Si-Cr-Niを使用）
◎：４２≦μ′
○：３８≦μ′＜４２
△：３４≦μ′＜３８
×： μ′＜３４
(Fe-Si-Cr-Ni is used as soft magnetic powder)
A: 42 ≦ μ ′
○: 38 ≦ μ ′ <42
Δ: 34 ≦ μ ′ <38
×: μ ′ <34
表７から解るように、実施例１３Ｂ〜１７Ｂの軟磁性シートは、タップ密度が０．５５〜１．４５ｇ／ｍｌの範囲内にあり、しかも比表面積が０．４〜１．２０ｍ２／ｇの範囲内にあるので、透磁率μ′とＱとが大きな値を示した。As can be seen from Table 7, the soft magnetic sheets of Examples 13B to 17B have a tap density in the range of 0.55 to 1.45 g / ml and a specific surface area of 0.4 to 1.20 m 2 / g. Therefore, the magnetic permeability μ ′ and Q showed large values.
一方、比較例１１Ｂの軟磁性シートは、タップ密度が１．４５ｇ／ｍｌを超え、比表面積が０．４ｍ２／ｇを下回っているので、Ｑの値は大きいものの、透磁率μ′の値が小さかった。比較例１２Ｂの軟磁性シートは、タップ密度が０．５５ｇ／ｍｌを下回り、比表面積が１．２０ｍ２／ｇを超えているので、透磁率μ′の値は大きいものの、Ｑの値が小さかった。On the other hand, the soft magnetic sheet of Comparative Example 11B has a tap density of more than 1.45 g / ml and a specific surface area of less than 0.4 m 2 / g. Was small. The soft magnetic sheet of Comparative Example 12B has a tap density of less than 0.55 g / ml and a specific surface area of more than 1.20 m 2 / g. Therefore, although the value of permeability μ ′ is large, the value of Q is small. It was.
実施例１８Ｂ、比較例１３Ｂ
実施例１５Ｂ（架橋あり）と比較例２Ｂ（架橋なし）の軟磁性シートをアンテナ装置とシールド板の間に配置して携帯電話に搭載し、環境試験前後（６０℃、９５％Ｒｈ、１９２ｈｒ）前後の通信距離を測定した。得られた結果を表８に示す。Example 18B, Comparative Example 13B
The soft magnetic sheets of Example 15B (with crosslinking) and Comparative Example 2B (without crosslinking) were placed between the antenna device and the shield plate and mounted on the mobile phone, before and after the environmental test (60 ° C., 95% Rh, 192 hr). The communication distance was measured. Table 8 shows the obtained results.
表８から解るように、バインダー樹脂を架橋させた実施例１８Ｂの軟磁性シートの通信距離は、環境試験前後で実質的な変化が認められないが、バインダー樹脂を架橋させていない比較例１３Ｂの軟磁性シートの通信距離は、環境試験前後で大きく変動した。 As can be seen from Table 8, the communication distance of the soft magnetic sheet of Example 18B in which the binder resin was crosslinked was not substantially changed before and after the environmental test, but in Comparative Example 13B in which the binder resin was not crosslinked. The communication distance of the soft magnetic sheet greatly fluctuated before and after the environmental test.
本発明の軟磁性材料は、バインダー樹脂中に軟磁性粉末を密に配向させた状態で架橋させて比重を大きくしたものであるので、高温あるいは高温高湿環境下において寸法変化や磁気特性の変化が小さい電子機器、例えばアンテナモジュールや携帯通信端末に有用である。
The soft magnetic material of the present invention is a material in which soft magnetic powder is cross-linked in a densely oriented state in the binder resin to increase the specific gravity. Therefore, the dimensional change and magnetic property change under high temperature or high temperature and high humidity environment. This is useful for electronic devices having a small size, such as antenna modules and portable communication terminals.
Claims (27)
27. The production method according to claim 26, wherein after the lamination of at least two dry sheets, the compression is carried out at a temperature at which the crosslinking reaction does not substantially occur before being compressed at the temperature at which the crosslinking reaction occurs.
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| JP4849047B2 (en) * | 2007-09-28 | 2011-12-28 | ソニー株式会社 | Portable electronic devices |
| JP4818339B2 (en) | 2007-10-29 | 2011-11-16 | ソニーケミカル＆インフォメーションデバイス株式会社 | Magnetic sheet |
| JP5574395B2 (en) * | 2008-04-04 | 2014-08-20 | 国立大学法人東北大学 | Composite material and manufacturing method thereof |
| JP4636113B2 (en) * | 2008-04-23 | 2011-02-23 | Ｔｄｋ株式会社 | Flat soft magnetic material and method for producing the same |
| KR101413210B1 (en) * | 2012-05-14 | 2014-07-01 | 주식회사 엠피코 | Composite for shielding electromagnetic interference, manufacturing method of the same, and sheet comprising with the same |
| EP2963658A4 (en) * | 2013-02-26 | 2016-11-09 | Nitto Denko Corp | Soft magnetic thermosetting film and soft magnetic film |
| JP5822146B2 (en) | 2013-03-29 | 2015-11-24 | パウダーテック株式会社 | Composite magnetic powder for noise suppression |
| JP6256361B2 (en) * | 2015-01-27 | 2018-01-10 | 東洋インキＳｃホールディングス株式会社 | Magnetic sheet for non-contact power transmission |
| JP6409943B2 (en) * | 2017-11-17 | 2018-10-24 | 東洋インキＳｃホールディングス株式会社 | Magnetic sheet for non-contact power transmission |
| JP6719607B2 (en) | 2018-02-20 | 2020-07-08 | Ｄｏｗａエレクトロニクス株式会社 | Silicon oxide coated soft magnetic powder and method for producing the same |
| US11749441B2 (en) * | 2019-01-11 | 2023-09-05 | Kyocera Corporation | Core component, method of manufacturing same, and inductor |
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| JP2005162803A (en) * | 2003-12-01 | 2005-06-23 | Nof Corp | Flame-retardant electromagnetic wave-shielding material |
Also Published As
| Publication number | Publication date |
|---|---|
| TWI484508B (en) | 2015-05-11 |
| TW201434058A (en) | 2014-09-01 |
| WO2007013436A1 (en) | 2007-02-01 |
| TWI512768B (en) | 2015-12-11 |
| TWI482181B (en) | 2015-04-21 |
| JP4811607B2 (en) | 2011-11-09 |
| TW200731299A (en) | 2007-08-16 |
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