JP2018061011A - Electromagnetic wave shielding sheet and printed wiring board - Google Patents
Electromagnetic wave shielding sheet and printed wiring board Download PDFInfo
- Publication number
- JP2018061011A JP2018061011A JP2017161889A JP2017161889A JP2018061011A JP 2018061011 A JP2018061011 A JP 2018061011A JP 2017161889 A JP2017161889 A JP 2017161889A JP 2017161889 A JP2017161889 A JP 2017161889A JP 2018061011 A JP2018061011 A JP 2018061011A
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- Prior art keywords
- layer
- electromagnetic wave
- wiring board
- wave shielding
- metal layer
- Prior art date
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Landscapes
- Laminated Bodies (AREA)
- Shielding Devices Or Components To Electric Or Magnetic Fields (AREA)
- Structure Of Printed Boards (AREA)
Abstract
Description
本発明は、電磁波を放出する部品の一部に接合して利用するのに好適な電磁波シールドシートおよびプリント配線板に関する。 The present invention relates to an electromagnetic wave shielding sheet and a printed wiring board that are suitable for use by joining to a part of a component that emits electromagnetic waves.
携帯端末、ＰＣ、サーバー等をはじめとする各種電子機器には、プリント配線板等の基板が内蔵されている。これらの基板には、外部からの磁場や電波による誤動作を防止するために、また、電気信号からの不要輻射を低減するために、電磁波シールド構造が設けられている。 Various electronic devices such as portable terminals, PCs, servers, and the like incorporate a substrate such as a printed wiring board. These substrates are provided with an electromagnetic wave shielding structure in order to prevent malfunction due to an external magnetic field or radio wave and to reduce unnecessary radiation from an electric signal.
特許文献１においては、シールドフィルムの一方面側から他方面側に進行する電界波、磁界波および電磁波を良好に遮蔽し、高周波信号系に適用しても良好な伝送特性を有するシールドフィルム、シールドプリント配線板およびシールドフィルムの製造方法を提供することを課題として、以下の構成が開示されている。即ち、層厚が０．５〜１２μｍの導電層と、異方導電層とを積層状態で備えたことを特徴とするシールドフィルムを開示する。そして、当該構成により、シールドフィルムの一方面側から他方面側に進行する電界波、磁界波、および電磁波を良好に遮蔽することができることが記載されている。 In Patent Document 1, a shield film and a shield that have good transmission characteristics even when applied to a high-frequency signal system, which shields well an electric field wave, a magnetic wave and an electromagnetic wave traveling from one side to the other side of the shield film. In order to provide a method for manufacturing a printed wiring board and a shield film, the following configurations are disclosed. That is, a shield film comprising a conductive layer having a layer thickness of 0.5 to 12 μm and an anisotropic conductive layer in a laminated state is disclosed. And it is described by the said structure that the electric field wave, magnetic field wave, and electromagnetic wave which advance from the one surface side of a shield film to the other surface side can be shielded favorably.
特許文献２においては、加熱プレスやハンダリフロー工程において発生する揮発成分によって、シールドプリント配線板の層間密着が破壊される問題を解決するために、電磁波シールドシートの金属薄膜層に径が０．１〜１０μｍ、穴数が１０〜１０００個／ｃｍ２であるピンホールを有する金属箔と導電性接着剤層からなるプリント配線板用シールドフィルムが記載されている。 In Patent Document 2, in order to solve the problem that the interlayer adhesion of the shield printed wiring board is broken by a volatile component generated in a heating press or a solder reflow process, the diameter of the metal thin film layer of the electromagnetic wave shield sheet is 0.1. There is described a shield film for a printed wiring board comprising a metal foil having a pinhole of 10 to 1000 μm and a number of holes of 10 to 1000 / cm 2 and a conductive adhesive layer.
伝送信号の高速伝送化に伴い、電磁波シールドシートも高周波用の高いシールド性及び高周波用の伝送特性が求められている。このため電磁波シールドシートの導電層には特許文献１で記載されるように金属層を用いるのが好適とされてきた。
しかし、金属層を用いた電磁波シールドシートをプリント配線板に張り付けたシールドプリント配線板はハンダリフローなどの加熱処理を行った際に、プリント配線板の内部から発生する揮発成分によって層間で浮きが発生し、発泡等により外観不良および接続不良となる問題があった（以下、ハンダリフロー耐性ということがある）。
この問題を解消するため、特許文献２では、ピンホールを有する金属層を電磁波シールドシートに適用することが提案されているが、上記ピンホールの径及び個数では、ハンダリフロー耐性は実用に耐えうる性能は発揮できていなかった。
一方で、シールドプリント配線板はメッキ液に浸漬する場合がある。これは露出している一部銅回路の表面をメッキするための工程であるが、通常メッキ液は酸性水溶液であるところ、メッキ液によって電磁波シールドシートの金属層が浸食され、金属層と導電性接着剤層が層間剥離する問題があった。（以下、メッキ液耐性ということがある）。また、金属層を有する電磁波シールドシートは反発力が高くハンドリング性が悪い問題があった。
With high-speed transmission of transmission signals, electromagnetic shielding sheets are also required to have high shielding properties for high frequencies and transmission characteristics for high frequencies. For this reason, it has been considered preferable to use a metal layer as described in Patent Document 1 for the conductive layer of the electromagnetic wave shielding sheet.
However, a shielded printed wiring board with an electromagnetic shielding sheet using a metal layer attached to the printed wiring board may float between the layers due to volatile components generated from the inside of the printed wiring board when heat treatment such as solder reflow is performed. However, there has been a problem of poor appearance and poor connection due to foaming or the like (hereinafter sometimes referred to as solder reflow resistance).
In order to solve this problem, Patent Document 2 proposes to apply a metal layer having pinholes to the electromagnetic wave shielding sheet. However, solder reflow resistance can withstand practical use with the diameter and number of pinholes. The performance was not able to be demonstrated.
On the other hand, the shield printed wiring board may be immersed in the plating solution. This is a process for plating the surface of some exposed copper circuits. Usually, the plating solution is an acidic aqueous solution, but the metal layer of the electromagnetic wave shielding sheet is eroded by the plating solution, and the metal layer is electrically conductive. There was a problem that the adhesive layer was delaminated. (Hereafter, it may be referred to as plating solution resistance.) Moreover, the electromagnetic wave shielding sheet having a metal layer has a problem of high repulsive force and poor handling properties.
本発明は、上記背景に鑑みて成されたものであり、その目的とするところは、メッキ液耐性、ハンダリフロー耐性および反発力が良好で、かつ折り曲げ後の接続信頼性が良好なだけでなく、高周波伝送回路に用いた場合においても高い電磁波シールド性を有する電磁波シールドシートを提供することである。 The present invention has been made in view of the above background, and the object thereof is not only good plating solution resistance, solder reflow resistance and repulsive force, but also good connection reliability after bending. Another object of the present invention is to provide an electromagnetic wave shielding sheet having high electromagnetic wave shielding properties even when used in a high frequency transmission circuit.
本発明者らが鋭意検討を重ねたところ、以下の態様において、本発明の課題を解決し得ることを見出し、本発明を完成するに至った。即ち、
本発明の電磁波シールドシートは、絶縁層と金属層と導電性接着剤層とから構成され、前記金属層は、面積０．７〜５０００μｍ２の開口部を１００〜２０００００個／ｃｍ２有し、かつ金属層の開口部において、数式（１）から求められるｗが０．８〜２．２であることを特徴とする。
そして、前記金属層の膜厚が、０．２〜５μｍであることを特徴とする。
また、前記金属層の開口部内部において、導電性接着剤層と絶縁層とが接着していることを特徴とする。
また、コプレーナ回路を有する配線板に電磁波シールドシートを張り合わせ、マイクロストリップ回路を有する配線板の信号配線と、電磁波シールドシートの絶縁層とを積層し、マイクロストリップ回路の信号配線に１０ＧＨｚのサイン波を流した際の、コプレーナ回路のクロストークが、−４５ｄＢ未満であることを特徴とする。
また、本発明は、前記電磁波シールドシート、カバーコート層、ならびに信号配線および絶縁性基材を有する配線板を備えることを特徴とするプリント配線板に関する。
As a result of extensive studies by the present inventors, it has been found that the problems of the present invention can be solved in the following modes, and the present invention has been completed. That is,
The electromagnetic wave shielding sheet of the present invention is composed of an insulating layer, a metal layer, and a conductive adhesive layer, and the metal layer has 100 to 200000 pieces / cm 2 of openings having an area of 0.7 to 5000 μm 2 . And in the opening part of a metal layer, w calculated | required from Numerical formula (1) is 0.8-2.2, It is characterized by the above-mentioned.
And the film thickness of the said metal layer is 0.2-5 micrometers, It is characterized by the above-mentioned.
Further, the conductive adhesive layer and the insulating layer are bonded inside the opening of the metal layer.
Also, an electromagnetic wave shielding sheet is attached to a wiring board having a coplanar circuit, a signal wiring of the wiring board having a microstrip circuit and an insulating layer of the electromagnetic wave shielding sheet are laminated, and a 10 GHz sine wave is applied to the signal wiring of the microstrip circuit. The crosstalk of the coplanar circuit when flowing is less than −45 dB.
The present invention also relates to a printed wiring board comprising the electromagnetic wave shielding sheet, a cover coat layer, a wiring board having a signal wiring and an insulating substrate.
本発明は、絶縁層と金属層と導電性接着剤層とから構成され、前記金属層が、面積０．７〜５０００μｍ２の開口部を、１００〜２０００００個／ｃｍ２有することにより、メッキ液耐性、ハンダリフロー耐性および反発力が良好で、かつ折り曲げ後の接続信頼性が良好なだけでなく、高周波伝送回路に用いた場合においても高い電磁波シールド性を有する電磁波シールドシートを提供することができる。
そして、金属層の膜厚が０．２〜５μｍの範囲にあることで、高い電磁波シールド性能とその他の物性とのバランスがより優れるものとなる。
また、本発明の電磁波シールドシートは１００ＭＨｚから５０ＧＨｚの周波数の信号を伝送する伝送回路に適用して、外部からの磁場や電波による誤動作を防止するとともに電気信号からの不要輻射を低減することができる効果がある。
The present invention comprises an insulating layer, a metal layer, and a conductive adhesive layer, and the metal layer has 100 to 200000 / cm 2 of openings having an area of 0.7 to 5000 μm 2 , thereby providing a plating solution. It is possible to provide an electromagnetic wave shielding sheet having not only good resistance, solder reflow resistance and repulsive force, but also good connection reliability after bending, and high electromagnetic shielding properties when used in a high frequency transmission circuit. .
And since the film thickness of a metal layer exists in the range of 0.2-5 micrometers, the balance of a high electromagnetic wave shielding performance and other physical properties will become more excellent.
In addition, the electromagnetic wave shielding sheet of the present invention can be applied to a transmission circuit that transmits a signal having a frequency of 100 MHz to 50 GHz to prevent malfunction caused by an external magnetic field or radio wave and reduce unnecessary radiation from an electric signal. effective.
以下、本発明を適用した実施形態の一例について説明する。尚、以降の図における各部材のサイズや比率は、説明の便宜上のものであり、これに限定されるものではない。また、本明細書において「任意の数Ａ〜任意の数Ｂ」なる記載は、当該範囲に数Ａが下限値として、数Ｂが上限値として含まれる。また、本明細書における「シート」とは、ＪＩＳにおいて定義される「シート」のみならず、「フィルム」も含むものとする。また、本明細書において特定する数値は、実施形態または実施例に開示した方法により求められる値である。 Hereinafter, an example of an embodiment to which the present invention is applied will be described. In addition, the size and ratio of each member in the following drawings are for convenience of explanation, and are not limited to this. In the present specification, the description “any number A to any number B” includes the number A as a lower limit and the number B as an upper limit in the range. The “sheet” in this specification includes not only “sheet” defined in JIS but also “film”. Moreover, the numerical value specified in this specification is a value calculated | required by the method disclosed by embodiment or an Example.
本発明に係る電磁波シールドシート１０は、導電性接着剤層１、金属層２、絶縁層３がこの順に積層された積層体からなる。電磁波シールドシート１０は、部品（不図示）上に導電性接着剤層１を配置し、接合処理により当該部品と接合することができる。接合処理は、接合できればよいが、熱処理または熱圧着処理が好適である。絶縁層３は、導電性接着剤層１、および金属層２を保護する役割を担い、金属層２より表層側に配置される。金属層２は、絶縁層３と導電性接着剤層１の間に挟持された層であり、主として電磁波をシールドする役割を担う。プリント配線板においては、部品内部の信号配線等から発生する電磁ノイズをシールドしたり、外部からの信号を遮蔽する役割を担う。
金属層２は、面積０．７〜５０００μｍ２の開口部４を１００〜２０００００個／ｃｍ２有し、かつ金属層の開口部において、数式（１）から求められるｗが０．８〜２．２である。
開口部４は、絶縁層３と導電性接着剤層１が接着している箇所でもあり、ハンダリフロー耐性およびメッキ液耐性を向上させる役割を担う。また、後述するように開口部４と非開口部の面積から計算される開口率を所定の範囲に設定することで、ハンダリフロー耐性及びメッキ液耐性と、高い電磁波シールド性とを両立することができる。
The electromagnetic wave shielding sheet 10 according to the present invention includes a laminate in which a conductive adhesive layer 1, a metal layer 2, and an insulating layer 3 are laminated in this order. The electromagnetic wave shielding sheet 10 can be joined to the component by disposing the conductive adhesive layer 1 on the component (not shown) and joining the component. The joining process is not limited as long as it can be joined, but heat treatment or thermocompression treatment is suitable. The insulating layer 3 plays a role of protecting the conductive adhesive layer 1 and the metal layer 2, and is disposed on the surface layer side from the metal layer 2. The metal layer 2 is a layer sandwiched between the insulating layer 3 and the conductive adhesive layer 1 and mainly plays a role of shielding electromagnetic waves. The printed wiring board plays a role of shielding electromagnetic noise generated from signal wiring or the like inside the component or shielding signals from the outside.
The metal layer 2 has 100 to 200000 openings / cm 2 having an area of 0.7 to 5000 μm 2 , and w obtained from the mathematical formula (1) is 0.8 to 2 in the opening of the metal layer. 2.
The opening 4 is also a portion where the insulating layer 3 and the conductive adhesive layer 1 are bonded, and plays a role of improving solder reflow resistance and plating solution resistance. In addition, as described later, by setting the aperture ratio calculated from the areas of the opening 4 and the non-opening to a predetermined range, it is possible to achieve both solder reflow resistance and plating solution resistance and high electromagnetic shielding properties. it can.
《金属層》
本発明の金属層は、電磁波および電界波を遮蔽する役割を担い、面積０．７〜５０００μｍ２の開口部を１００〜２０００００個／ｃｍ２有し、かつ金属層の開口部において、数式（１）から求められるｗが０．８〜２．２であることを特徴とする。このような特定の開口部を有することにより、高い電磁波シールド性と、ハンダリフロー耐性およびメッキ液耐性との両立が可能となる。同時に反発力を下げることができる。
《Metallic layer》
The metal layer of the present invention plays a role of shielding electromagnetic waves and electric field waves, and has 100 to 200000 openings / cm 2 with an area of 0.7 to 5000 μm 2. ) Obtained from (2) is 0.8 to 2.2. By having such a specific opening, it is possible to achieve both high electromagnetic shielding properties, solder reflow resistance, and plating solution resistance. At the same time, the repulsive force can be lowered.
＜開口部＞
本発明の金属層は全面に複数の開口部を有することを特徴とする。開口部はプリント配線板をハンダリフロー処理した際に、プリント配線板のポリイミドフィルムやカバーレイ接着剤に含まれる揮発成分を外部に逃がしカバーレイ接着剤および電磁波シールドシートの界面剥離による外観不良及び接続信頼性の低下を抑制する役割を担う。さらに図１の断面模式図に示すように、開口部内部で絶縁層と導電性接着剤層が接着することにより、絶縁層／金属層／導電性接着剤層同士の界面の接着力がより向上し、メッキ液耐性及び、ハンダリフロー耐性がさらに向上する。
<Opening>
The metal layer of the present invention is characterized by having a plurality of openings on the entire surface. When the printed wiring board is subjected to solder reflow processing, the openings let the volatile components contained in the polyimide film and coverlay adhesive of the printed wiring board escape to the outside, and poor appearance and connection due to interface peeling of the coverlay adhesive and electromagnetic shielding sheet It plays a role of suppressing the decline in reliability. Furthermore, as shown in the schematic cross-sectional view of FIG. 1, the adhesive force at the interface between the insulating layer / metal layer / conductive adhesive layer is further improved by bonding the insulating layer and the conductive adhesive layer inside the opening. In addition, plating solution resistance and solder reflow resistance are further improved.
開口部の一例を図２に示す。
開口部の形状は例えば、円、楕円、四角、多角形、星形、台形等、必要に応じて各形状を形成することができるが、製造コスト及び膜の強靭性の観点から、円および、楕円が好ましい。
An example of the opening is shown in FIG.
The shape of the opening can be formed as necessary, for example, a circle, an ellipse, a square, a polygon, a star, a trapezoid, etc., but from the viewpoint of manufacturing cost and film toughness, An ellipse is preferred.
開口部１個あたりの面積は０．７〜５０００μｍ２である。開口部の面積は１０〜４０００μｍ２が好ましく、２０〜２０００μｍ２がより好ましい。開口部面積を０．７μｍ２以上とすることで、絶縁層と導電性接着剤層が接着良好となり、ハンダリフロー耐性及びメッキ液耐性が優れたものとなる。開口部面積を５０００μｍ２以下とすることで、高い電磁波シールド性に優れたものとすることができる。 The area per opening is 0.7 to 5000 μm 2 . Area of the opening is preferably 10~4000μm 2, 20~2000μm 2 is more preferable. By setting the opening area to 0.7 μm 2 or more, the insulating layer and the conductive adhesive layer have good adhesion, and the solder reflow resistance and the plating solution resistance are excellent. By setting the opening area to 5000 μm 2 or less, it is possible to achieve high electromagnetic shielding properties.
開口部の個数は、１００〜２０００００個／ｃｍ２であり、１０００〜１５００００個／ｃｍ２がより好ましい。開口部の個数を１００個／ｃｍ２以上とすることで揮発成分を効率的に外部に出しやすくなるためハンダリフロー耐性を向上させることができる。加えて反発力を低下できる。開口部の数を２０００００個／ｃｍ２以下にすることで、高い電磁波シールド性を確保することができる。 The number of openings is 100 to 200000 pieces / cm 2 , and more preferably 1000 to 150,000 pieces / cm 2 . By setting the number of openings to 100 / cm 2 or more, the volatile component can be efficiently extracted to the outside, so that solder reflow resistance can be improved. In addition, the resilience can be reduced. By setting the number of openings to 200,000 pieces / cm 2 or less, high electromagnetic shielding properties can be secured.
＜開口率＞
本発明における金属層の開口率は、０．０５〜４０％であることが好ましい。開口率は開口部の面積と個数から調整できる。また、開口率は下記式１から求められる。
（式１）
開口率（％）＝単位面積あたりの開口部面積／（単位面積あたりの開口部面積＋単位面積あたりの非開口部面積）×１００
開口率の下限は、０．０５％が好ましく、１％がより好ましい。開口率の上限は、４０％が好ましく、３５％がより好ましい。
開口率を０．０５〜４０％の範囲にすることで、ハンダリフロー耐性及びメッキ液耐性と、高い電磁波シールド性能を保持し、反発力を低下することができる。
<Opening ratio>
The aperture ratio of the metal layer in the present invention is preferably 0.05 to 40%. The aperture ratio can be adjusted from the area and number of apertures. Further, the aperture ratio is obtained from the following formula 1.
(Formula 1)
Opening ratio (%) = opening area per unit area / (opening area per unit area + non-opening area per unit area) × 100
The lower limit of the aperture ratio is preferably 0.05%, more preferably 1%. The upper limit of the aperture ratio is preferably 40%, and more preferably 35%.
By setting the aperture ratio in the range of 0.05 to 40%, it is possible to maintain solder reflow resistance and plating solution resistance and high electromagnetic shielding performance, and to reduce the repulsive force.
開口率の測定は、例えば金属層を面方向から垂直にレーザー顕微鏡及び走査型電子顕微鏡（ＳＥＭ）で５００〜２０００倍に拡大した画像を用いて、開口部と非開口部を２値化し、単位面積当たりの２値化した色のピクセル数をそれぞれの面積とすることで求めることができる。 The aperture ratio is measured by binarizing the opening and non-opening using, for example, an image obtained by enlarging the metal layer by a laser microscope and a scanning electron microscope (SEM) 500 to 2000 times perpendicularly from the surface direction. It can be obtained by setting the number of binarized pixels per area as the respective areas.
＜開口部の分散性（ｗ）＞
本発明の金属層は全面に複数の開口部を有し、さらにこの開口部が下記数式（１）から求められるｗが０．８〜２．２である。より好ましくは１．０〜２．０であり、さらに好ましくは１．０〜１．８である。
Ｗは、平均最近隣距離、Ｅ［Ｗ］は、平均最近隣距離の期待値であり、下記数式（２）および数式（３）によって求めることができる値である。
ｄiは、開口部の中心点iから最近隣の開口部の中心点までの距離であり、ｎは、金属層の面積Ｓ中の開口部の個数である。
<Dispersibility of the opening (w)>
The metal layer of the present invention has a plurality of openings on the entire surface, and the opening w of the openings determined from the following formula (1) is 0.8 to 2.2. More preferably, it is 1.0-2.0, More preferably, it is 1.0-1.8.
W is the average nearest neighbor distance, and E [W] is an expected value of the average nearest neighbor distance, which is a value that can be obtained by the following formulas (2) and (3).
d i is the distance from the center point i of the opening to the center point of the nearest opening, and n is the number of openings in the area S of the metal layer.
数式（１）のｗは、開口部の配列の分散性を表す指標であり、ｗが１よりも低い値では、開口部はクラスター状でムラのある分布をとり、ｗが１に近い場合ランダム配列で分散し、ｗが１より高い値では規則的に配列した分散状態であることを示している。
ｗを０．８以上にすることで、開口部をムラなく全面に形成することができ、メッキ液耐性、反発力およびハンダリフロー耐性が向上する。ｗを２．２以下にすることで、特定周波数の共振を抑制できるため、クロストークの悪化を抑制し電磁波シールド性が向上する。なお、メッシュパターン等であって、開口部が最も等間隔で規則的に分散配列している状態の場合、ｗは２．４となる。このようなｗが２．４の場合も上述した通り、一部の周波数帯で共振を起こしやすく、電磁波シールド性が悪化する傾向がある。
W in Equation (1) is an index representing the dispersibility of the arrangement of the openings, and when w is lower than 1, the openings have a clustered and uneven distribution, and random when w is close to 1. When the values are distributed in an array and w is higher than 1, this indicates a regularly distributed state.
By setting w to 0.8 or more, the opening can be formed on the entire surface without unevenness, and the plating solution resistance, repulsive force and solder reflow resistance are improved. By setting w to 2.2 or less, resonance at a specific frequency can be suppressed, so that deterioration of crosstalk is suppressed and electromagnetic wave shielding properties are improved. In the case of a mesh pattern or the like in which the openings are regularly dispersed and arranged at equal intervals, w is 2.4. In the case where w is 2.4, as described above, resonance is likely to occur in some frequency bands, and the electromagnetic shielding properties tend to deteriorate.
数式（２）の平均最近隣距離および、数式（３）の平均最近隣距離の期待値の算出方法について説明する。まず、開口部を有する金属層の平面画像を取得する。倍率は開口部が５０から１００個が認識できる倍率であればよく、例えば、１０００〜５００００倍の倍率で開口部画像を取り込む。次いで、１００００μｍ２等の任意の面積Ｓを設定し、その面積内にある開口部の個数ｎをカウントすることで、数式（３）の平均最近隣距離の期待値を算出する。開口部の分散性（ｗ）を求めるための金属層の画像面積Ｓの設定は、開口部が少なくとも２０個程度入る領域とすることが好ましい。
カウントした開口部毎に隣り合う開口部の最も近い距離すなわち最近隣距離を測定することで数式（２）の平均最近隣距離を求める。開口部の個数及び開口部同士の距離を測定する際には、開口部の中心点を基準とする。開口部の中心点は開口部を、面積が最小となるよう長方形で囲み、この長方形の４隅から引いた直線の交点を中心点とする。上記の測定を異なる３箇所で行いその平均値を用いてｗを算出する。
A method for calculating the average nearest neighbor distance of Equation (2) and the expected value of the average nearest neighbor distance of Equation (3) will be described. First, a planar image of a metal layer having an opening is acquired. The magnification may be any magnification that can recognize 50 to 100 apertures. For example, an aperture image is captured at a magnification of 1000 to 50000 times. Next, an arbitrary area S such as 10000 μm 2 is set, and the expected value of the average nearest neighbor distance of Expression (3) is calculated by counting the number n of openings within the area. The setting of the image area S of the metal layer for obtaining the dispersibility (w) of the openings is preferably a region where at least about 20 openings are included.
The average nearest neighbor distance of Formula (2) is obtained by measuring the nearest distance between adjacent openings, that is, the nearest neighbor distance for each counted opening. When measuring the number of openings and the distance between the openings, the center point of the openings is used as a reference. The center point of the opening is defined by surrounding the opening with a rectangle so that the area is minimized, and the intersection of straight lines drawn from the four corners of the rectangle is the center point. The above measurement is performed at three different locations, and w is calculated using the average value.
金属層の厚みは０．２〜５μｍであることが好ましい。金属層の厚みは、０．５〜４．５μｍがより好ましく、１〜４μｍがさらに好ましい。金属層の厚みが１〜５μｍの範囲にあることで高い電磁波シールド性能と反発力とのバランスを取ることが可能となる。 The thickness of the metal layer is preferably 0.2 to 5 μm. As for the thickness of a metal layer, 0.5-4.5 micrometers is more preferable, and 1-4 micrometers is still more preferable. When the thickness of the metal layer is in the range of 1 to 5 μm, it is possible to balance high electromagnetic shielding performance and repulsive force.
金属層は、例えば金属箔、金属蒸着膜、金属メッキ膜を使用できる。
金属箔に使用する金属は、例えばアルミニウム、銅、銀、金等の導電性金属が好ましく、電磁波シールド性およびコストの面から銅、銀、アルミニウムがより好ましく、銅がさらに好ましい。銅は、例えば、圧延銅箔または電解銅箔を使用することが好ましく、電解銅箔がより好ましい。電解銅箔を使用すると金属層の厚みをより薄くできる。また、金属箔はメッキで形成してもよい。金属箔の厚みは１〜５μｍが好ましく、１．５〜４μｍがより好ましい。
As the metal layer, for example, a metal foil, a metal vapor deposition film, or a metal plating film can be used.
The metal used for the metal foil is preferably, for example, a conductive metal such as aluminum, copper, silver, or gold, more preferably copper, silver, or aluminum, and even more preferably copper from the viewpoint of electromagnetic shielding properties and cost. For example, rolled copper foil or electrolytic copper foil is preferably used as copper, and electrolytic copper foil is more preferable. When an electrolytic copper foil is used, the metal layer can be made thinner. The metal foil may be formed by plating. 1-5 micrometers is preferable and, as for the thickness of metal foil, 1.5-4 micrometers is more preferable.
金属蒸着膜及び金属メッキ膜に使用する金属は、例えばアルミニウム、銅、銀、金が好ましく、銅、銀がより好ましい。金属蒸着膜および金属メッキ膜の厚みは、０．２〜３μｍが好ましく、０．３〜２μｍがより好ましい。
金属層は薄膜化の点から蒸着膜が好ましい。電磁波シールド性の点からは金属箔が好ましい。
The metal used for a metal vapor deposition film and a metal plating film is preferably, for example, aluminum, copper, silver, or gold, and more preferably copper or silver. The thickness of the metal vapor deposition film and the metal plating film is preferably 0.2 to 3 μm, and more preferably 0.3 to 2 μm.
The metal layer is preferably a deposited film from the viewpoint of thinning. A metal foil is preferable from the viewpoint of electromagnetic shielding properties.
＜金属層の製造方法＞
開口部を有する金属層の製造方法は、例えば金属箔を機械的に打ち抜きをするパンチング方法、針状の突起を全面に突き刺し金属箔に開口部を形成する方法、金属箔上にパターンレジスト層を形成し金属箔をエッチングして開口部を形成する方法、スクリーン印刷によって所定のパターンに導電性ペーストを印刷する方法、所定のパターンでアンカー剤をスクリーン印刷しアンカー剤印刷面のみに金属メッキする方法、および特開２０１５‐６３７３０号公報に記載されている製造方法等が適用できる。すなわち、支持体に水溶性、又は溶剤可溶性インクをパターン印刷し、その表面に金属蒸着膜を形成しパターンを除去する。その表面に離形層を形成し電解メッキすることでキャリア付開口部を有する金属層を得ることができる。
<Production method of metal layer>
The method for producing a metal layer having openings includes, for example, a punching method in which a metal foil is mechanically punched, a method in which needle-like protrusions are pierced over the entire surface to form openings in the metal foil, and a pattern resist layer is formed on the metal foil. A method of forming and etching the metal foil to form openings, a method of printing a conductive paste in a predetermined pattern by screen printing, a method of screen printing an anchor agent in a predetermined pattern and metal plating only on the anchor agent printing surface And the manufacturing method described in JP-A-2015-63730 can be applied. That is, water-soluble or solvent-soluble ink is pattern-printed on the support, a metal vapor deposition film is formed on the surface, and the pattern is removed. A metal layer having an opening with a carrier can be obtained by forming a release layer on the surface and performing electrolytic plating.
《導電性接着剤層》
導電性接着剤層は、等方導電性接着剤層または異方導電性接着剤層から適宜選択できる。等方導電性接着剤層は、電磁波シールドシートを水平に置いた状態で、上下方向および水平方向に導電性を有する。また、異方導電性接着剤層は、電磁波シールドシートを水平に置いた状態で、上下方向のみに導電性を有する。
導電性接着剤層は、等方導電性あるいは異方導電性のいずれでもよく、異方導電性の場合、コストダウンが可能となるため好ましい。
導電性接着剤層は、導電性接着剤を使用して形成できる。導電性接着剤は、熱硬化性樹脂、硬化剤、および導電性微粒子を含む従来公知のものを任意に用いることが可能である。
<< Conductive adhesive layer >>
The conductive adhesive layer can be appropriately selected from an isotropic conductive adhesive layer or an anisotropic conductive adhesive layer. The isotropic conductive adhesive layer has conductivity in the vertical direction and the horizontal direction with the electromagnetic wave shielding sheet placed horizontally. The anisotropic conductive adhesive layer has conductivity only in the vertical direction with the electromagnetic wave shielding sheet placed horizontally.
The conductive adhesive layer may be either isotropic conductive or anisotropic conductive, and anisotropic conductive is preferable because cost can be reduced.
The conductive adhesive layer can be formed using a conductive adhesive. As the conductive adhesive, a conventionally known adhesive containing a thermosetting resin, a curing agent, and conductive fine particles can be arbitrarily used.
＜熱硬化性樹脂＞
熱硬化性樹脂は、硬化剤と反応可能な官能基を複数有する樹脂である。官能基は、例えば、水酸基、フェノール性水酸基、メトキシメチル基、カルボキシル基、アミノ基、エポキシ基、オキセタニル基、オキサゾリン基、オキサジン基、アジリジン基、チオール基、イソシアネート基、ブロック化イソシアネート基、ブロック化カルボキシル基、シラノール基等が挙げられる。熱硬化性樹脂は、例えば、アクリル樹脂、マレイン酸樹脂、ポリブタジエン系樹脂、ポリエステル樹脂、ポリウレタン樹脂、ポリウレタンウレア樹脂、エポキシ樹脂、オキセタン樹脂、フェノキシ樹脂、ポリイミド樹脂、ポリアミド樹脂、ポリアミドイミド樹脂、フェノール系樹脂、アルキド樹脂、アミノ樹脂、ポリ乳酸樹脂、オキサゾリン樹脂、ベンゾオキサジン樹脂、シリコーン樹脂、フッ素樹脂等の公知の樹脂が挙げられる。
熱硬化性樹脂は、単独または２種類以上併用できる。
<Thermosetting resin>
A thermosetting resin is a resin having a plurality of functional groups capable of reacting with a curing agent. Functional groups include, for example, hydroxyl group, phenolic hydroxyl group, methoxymethyl group, carboxyl group, amino group, epoxy group, oxetanyl group, oxazoline group, oxazine group, aziridine group, thiol group, isocyanate group, blocked isocyanate group, blocked A carboxyl group, a silanol group, etc. are mentioned. Thermosetting resins include, for example, acrylic resins, maleic resins, polybutadiene resins, polyester resins, polyurethane resins, polyurethane urea resins, epoxy resins, oxetane resins, phenoxy resins, polyimide resins, polyamide resins, polyamideimide resins, phenolic resins. Known resins such as resins, alkyd resins, amino resins, polylactic acid resins, oxazoline resins, benzoxazine resins, silicone resins, and fluorine resins can be used.
Thermosetting resins can be used alone or in combination of two or more.
これらの中でも屈曲性とハンダリフロー耐性の点から、ポリウレタン樹脂、ポリウレタンウレア樹脂、エポキシ樹脂、フェノキシ樹脂、ポリイミド樹脂、ポリアミド樹脂、ポリアミドイミド樹脂が好ましい。 Among these, polyurethane resin, polyurethane urea resin, epoxy resin, phenoxy resin, polyimide resin, polyamide resin, and polyamideimide resin are preferable from the viewpoint of flexibility and solder reflow resistance.
また、ポリアミド樹脂の中でも、窒素含有複素環およびアミド結合を有している樹脂であることが好ましい。ポリアミド樹脂が窒素含有複素環およびアミド結合を有することで、水素結合による金属表面への吸着力が向上するため、導電性微粒子の分散性向上、および金属層に対する接着力が向上する。そのため被着体との間で良好な接着界面が形成できるため電磁波シールドシートのハンダリフロー耐性及びメッキ液耐性が向上する。 Among polyamide resins, a resin having a nitrogen-containing heterocyclic ring and an amide bond is preferable. Since the polyamide resin has a nitrogen-containing heterocyclic ring and an amide bond, the adsorptive power to the metal surface by hydrogen bonding is improved, so that the dispersibility of the conductive fine particles is improved and the adhesion to the metal layer is improved. Therefore, since a favorable adhesive interface can be formed with the adherend, the solder reflow resistance and the plating solution resistance of the electromagnetic wave shielding sheet are improved.
ポリアミド樹脂が含む窒素含有複素環は、一つの環構造中に窒素原子を１〜３個含むことが好ましく、２個がより好ましい。また窒素含有複素環の構造は、５員環、および６員環が好ましい。
このような窒素含有複素環は、例えばイミダゾール、ピラゾール、オキサゾール、チアゾール、イミダゾリン、ピラジン、ピペリジン、ピペラジン、トリアゾール、トリアジン、メラミン、ベンゾイミダゾール、ベンゾトリアゾール、ベンゾチアゾール、プリン等が挙げられる。これらの中でもピペラジンが好ましい。本発明では、これらの窒素含有複素環を有するアミンをポリアミド樹脂の合成に使用することが好ましい。
The nitrogen-containing heterocycle contained in the polyamide resin preferably contains 1 to 3 nitrogen atoms, and more preferably 2 in one ring structure. The structure of the nitrogen-containing heterocyclic ring is preferably a 5-membered ring or a 6-membered ring.
Examples of such nitrogen-containing heterocycle include imidazole, pyrazole, oxazole, thiazole, imidazoline, pyrazine, piperidine, piperazine, triazole, triazine, melamine, benzimidazole, benzotriazole, benzothiazole, purine and the like. Among these, piperazine is preferable. In this invention, it is preferable to use the amine which has these nitrogen-containing heterocyclic rings for the synthesis | combination of a polyamide resin.
ポリアミド樹脂は、例えば、ジカルボン酸とジアミン等の脱水縮合反応よりアミド結合を形成する方法で合成するのが一般的であるところ、アミノカルボン酸の自己縮合反応させる方法、またはアミノカルボン酸の分子内環状化合物の開環重合させる方法、またはこれらの複合反応よりアミド結合を形成する方法等公知の方法でも合成できる。なお、合成時にジアミン以外のモノアミン、トリアミン等のアミン化合物を使用しても良い。 Polyamide resins are generally synthesized by a method of forming an amide bond by a dehydration condensation reaction of, for example, dicarboxylic acid and diamine. It can also be synthesized by a known method such as a method of ring-opening polymerization of a cyclic compound, or a method of forming an amide bond from these complex reactions. In addition, you may use amine compounds, such as monoamine other than diamine, a triamine, at the time of a synthesis | combination.
ポリアミド樹脂への窒素含有複素環の導入は、公知の合成方法が利用できるところ、窒素含有複素環を有するジアミン、窒素含有複素環を有するアミノカルボン酸、窒素含有複素環を有するモノアミンを使用して合成することが好ましい。ポリアミド樹脂を合成するために窒素含有複素環を有しないジアミンを使用することも好ましい。これによりアミド樹脂の性質（耐熱性や柔軟性）を向上できる。 The introduction of the nitrogen-containing heterocycle into the polyamide resin can be performed by using a known synthesis method, using a diamine having a nitrogen-containing heterocycle, an aminocarboxylic acid having a nitrogen-containing heterocycle, and a monoamine having a nitrogen-containing heterocycle. It is preferable to synthesize. It is also preferable to use a diamine that does not have a nitrogen-containing heterocycle in order to synthesize a polyamide resin. Thereby, the properties (heat resistance and flexibility) of the amide resin can be improved.
窒素含有複素環は、アミン化合物の合計１００モル％中に２０〜１００モル％使用することが好ましく、４０〜１００モル％がより好ましい。窒素含有複素環を２０〜１００モル％使用することでハンダリフロー耐性を向上させることができる。 The nitrogen-containing heterocyclic ring is preferably used in an amount of 20 to 100 mol%, more preferably 40 to 100 mol%, in a total of 100 mol% of the amine compound. Solder reflow resistance can be improved by using 20-100 mol% of nitrogen-containing heterocycles.
窒素複素環を有するアミン化合物は、窒素複素環の水中における酸解離定数（ｐＫａ）が３〜１１であることが好ましい。ｐＫａが３〜１１であることでカルボン酸との反応速度が向上しアミド樹脂の収率が向上する。 The amine compound having a nitrogen heterocycle preferably has an acid dissociation constant (pKa) in water of the nitrogen heterocycle of 3 to 11. When pKa is 3 to 11, the reaction rate with the carboxylic acid is improved, and the yield of the amide resin is improved.
窒素含有複素環を有しないアミン化合物は、例えばエチレンジアミン、テトラメチレンジアミン、ブタンジアミン、ヘキサメチレンジアミン、ヘプタメチレンジアミン、ｐ−ジアミノメチルシクロヘキサン、ビス（ｐ−アミノシクロヘキシル）メタン、ｍ−キシレンジアミン、イソホロンジアミン、ダイマージアミン等の公知の化合物が挙げられる。 Examples of the amine compound having no nitrogen-containing heterocycle include ethylenediamine, tetramethylenediamine, butanediamine, hexamethylenediamine, heptamethylenediamine, p-diaminomethylcyclohexane, bis (p-aminocyclohexyl) methane, m-xylenediamine, and isophorone. Well-known compounds, such as diamine and dimer diamine, are mentioned.
ジカルボン酸は、例えばアジピン酸、アゼライン酸、セバチン酸、ウンデカン二酸、ドデカン二酸、ダイマー酸、イソフタル酸、テレフタル酸、１、４−シクロヘキサンジカルボン酸、５−ヒドロキシイソフタル酸、５−スルホイソフタル酸ナトリウム等が挙げられる。これらの中でも１、４−シクロヘキサンジカルボン酸、ダイマー酸は、アミド樹脂の溶剤に対する溶解性が向上するため好ましい。 Examples of dicarboxylic acids include adipic acid, azelaic acid, sebacic acid, undecanedioic acid, dodecanedioic acid, dimer acid, isophthalic acid, terephthalic acid, 1,4-cyclohexanedicarboxylic acid, 5-hydroxyisophthalic acid, and 5-sulfoisophthalic acid. Sodium etc. are mentioned. Among these, 1,4-cyclohexanedicarboxylic acid and dimer acid are preferable because the solubility of the amide resin in the solvent is improved.
アミノカルボン酸は、例えば１１−アミノウンデカン酸、１２−アミノドデカン酸、４−アミノメチル安息香酸、４−アミノメチルシクロヘキサンカルボン酸等が挙げられる。また、アミノカルボン酸の分子内環状化合物として、例えばβ−ラクタム、ε−カプロラクタム、ラウリンラクタム、α−ピロリドン、α−ピペリドン等が挙げられる。 Examples of the aminocarboxylic acid include 11-aminoundecanoic acid, 12-aminododecanoic acid, 4-aminomethylbenzoic acid, 4-aminomethylcyclohexanecarboxylic acid, and the like. Examples of the intramolecular cyclic compound of aminocarboxylic acid include β-lactam, ε-caprolactam, laurin lactam, α-pyrrolidone, α-piperidone and the like.
また、ポリアミド樹脂は、アミド結合にホルマリンとアルコールとを付加させたＮ−アルコキシメチル基を形成することでアルコール可溶性が得られる。Ｎ−アルコキシメチル基を有することでポリアミド樹脂は、融点が低下し、可とう性が向上し、溶解性もより向上する。 In addition, the polyamide resin is soluble in alcohol by forming an N-alkoxymethyl group in which formalin and alcohol are added to an amide bond. By having an N-alkoxymethyl group, the polyamide resin has a lower melting point, improved flexibility, and improved solubility.
ポリアミド樹脂は、無溶剤下での一括仕込みで脱水縮合反応、脱アルコール反応、開環重合反応等により合成することができる。その際には、原料と一緒に予め水を仕込んでおき、この水を留去しながら脱水反応を行うこともできる。この反応は常圧下、減圧下のいずれで行ってもよい。ポリアミド樹脂の分子量及びアミン価は、ポリアミド樹脂を合成する際のジアミンとジカルボン酸との仕込み比率や反応時間及び減圧度を変更することで調整できる。 The polyamide resin can be synthesized by dehydration condensation reaction, dealcoholization reaction, ring-opening polymerization reaction or the like by batch preparation in the absence of a solvent. In that case, water can be charged together with the raw material, and the dehydration reaction can be carried out while distilling off the water. This reaction may be carried out under normal pressure or reduced pressure. The molecular weight and amine value of the polyamide resin can be adjusted by changing the charging ratio of diamine and dicarboxylic acid when synthesizing the polyamide resin, the reaction time, and the degree of vacuum.
熱硬化性樹脂の酸価は、１〜５０ｍｇＫＯＨ／ｇが好ましく、３〜３０ｍｇＫＯＨ／ｇがより好ましい。酸価を１〜５０ｍｇＫＯＨ／ｇとすることでハンダリフロー耐性がより向上する。 1-50 mgKOH / g is preferable and, as for the acid value of a thermosetting resin, 3-30 mgKOH / g is more preferable. By setting the acid value to 1 to 50 mgKOH / g, the solder reflow resistance is further improved.
熱硬化性樹脂の重量平均分子量は、２００００〜１０００００が好ましい。重量平均分子量は、２００００〜１０００００とすることでメッキ液耐性を向上させることができる。 The weight average molecular weight of the thermosetting resin is preferably 20,000 to 100,000. By setting the weight average molecular weight to 20,000 to 100,000, the plating solution resistance can be improved.
熱硬化性樹脂は、導電性接着剤層の固形分中の含有量が、１０〜８０重量％配合することが好ましく、１５〜８０重量％がより好ましい。上記配合の範囲にすることで、ハンダリフロー耐性とメッキ液耐性を向上させることができる。 The content of the thermosetting resin in the solid content of the conductive adhesive layer is preferably 10 to 80% by weight, and more preferably 15 to 80% by weight. By making it the range of the said mixing | blending, solder reflow tolerance and plating solution tolerance can be improved.
＜硬化剤＞
硬化剤は、熱硬化性樹脂の官能基と反応可能な官能基を複数有している。硬化剤は、例えばエポキシ化合物、酸無水物基含有化合物、イソシアネート化合物、アジリジン化合物、アミン化合物、フェノール化合物、有機金属化合物等の公知の化合物が挙げられる。
硬化剤は、単独または２種類以上併用できる。
<Curing agent>
The curing agent has a plurality of functional groups that can react with the functional groups of the thermosetting resin. Examples of the curing agent include known compounds such as an epoxy compound, an acid anhydride group-containing compound, an isocyanate compound, an aziridine compound, an amine compound, a phenol compound, and an organometallic compound.
A hardening | curing agent can be used individually or in combination with 2 or more types.
硬化剤は、熱硬化性樹脂１００重量部に対して各種１〜５０重量部含むことが好ましく、３〜３０重量部がより好ましく、３〜２０重量部がさらに好ましい。 It is preferable that 1-50 weight part of various hardening | curing agents are included with respect to 100 weight part of thermosetting resins, 3-30 weight part is more preferable, and 3-20 weight part is further more preferable.
＜導電性微粒子＞
導電性微粒子は、導電性接着剤層に導電性を付与する機能を有する。導電性微粒子は、素材としては、例えば金、白金、銀、銅およびニッケル等の導電性金属およびその合金、ならびに導電性ポリマーの微粒子が好ましく、価格と導電性の面から銀がより好ましい。
また単一素材の微粒子ではなく金属や樹脂を核体とし、核体の表面を被覆した被覆層を有する複合微粒子もコストダウンの観点から好ましい。ここで核体は、価格が安いニッケル、シリカ、銅およびその合金、ならびに樹脂から適宜選択することが好ましい。被覆層は、導電性金属または導電性ポリマーが好ましい。導電性金属は、例えば、金、白金、銀、ニッケル、マンガン、およびインジウム等、ならびにその合金が挙げられる。また導電性ポリマーは、ポリアニリン、ポリアセチレン等が挙げられる。これらの中でも価格と導電性の面から銀が好ましい。
<Conductive fine particles>
The conductive fine particles have a function of imparting conductivity to the conductive adhesive layer. The conductive fine particles are preferably, for example, conductive metals such as gold, platinum, silver, copper and nickel, and alloys thereof, and conductive polymer fine particles, and silver is more preferable from the viewpoint of cost and conductivity.
In addition, composite fine particles having a coating layer in which a metal or a resin is used as a core and the surface of the core is covered, are preferable from the viewpoint of cost reduction. Here, the core is preferably selected appropriately from inexpensive nickel, silica, copper and alloys thereof, and resins. The coating layer is preferably a conductive metal or a conductive polymer. Examples of the conductive metal include gold, platinum, silver, nickel, manganese, indium, and alloys thereof. Examples of the conductive polymer include polyaniline and polyacetylene. Among these, silver is preferable from the viewpoints of price and conductivity.
導電性微粒子の形状は、所望の導電性が得られればよく形状は限定されない。具体的には、例えば、球状、フレーク状、葉状、樹枝状、プレート状、針状、棒状、ブドウ状が好ましい。また、これらの異なる形状の導電性微粒子を２種類混合しても良い。
導電性微粒子は、単独または２種類以上併用できる。
The shape of the conductive fine particles is not limited as long as desired conductivity is obtained. Specifically, for example, a spherical shape, a flake shape, a leaf shape, a dendritic shape, a plate shape, a needle shape, a rod shape, and a grape shape are preferable. Moreover, you may mix two types of electroconductive fine particles of these different shapes.
The conductive fine particles can be used alone or in combination of two or more.
導電性微粒子の平均粒子径は、Ｄ５０平均粒子径であり、異方性を充分に確保する観点から、２μｍ以上が好ましく、５μｍ以上がより好ましく、７μｍ以上とすることが更に好ましい。一方、導電性接着剤層の薄さと両立させる観点からは、３０μｍ以下が好ましく、２０μｍ以下がより好ましく、１５μｍ以下とすることが更に好ましい。Ｄ５０平均粒子径は、レーザー回折・散乱法粒度分布測定装置等により求めることができる。 The average particle diameter of the conductive fine particles is a D50 average particle diameter, and is preferably 2 μm or more, more preferably 5 μm or more, and further preferably 7 μm or more from the viewpoint of sufficiently ensuring anisotropy. On the other hand, from the viewpoint of making the conductive adhesive layer thin, 30 μm or less is preferable, 20 μm or less is more preferable, and 15 μm or less is even more preferable. The D50 average particle diameter can be determined by a laser diffraction / scattering particle size distribution measuring apparatus or the like.
導電性微粒子は、熱硬化性樹脂の固形分１００重量部に対して、１０〜７００重量部を配合することが好ましく、２０〜５００重量部がより好ましい。
含有量が２０〜５００重量部であることにより、ハンダリフロー耐性がより良好な電磁波シールドシートとすることができる。
The conductive fine particles are preferably blended in an amount of 10 to 700 parts by weight and more preferably 20 to 500 parts by weight with respect to 100 parts by weight of the solid content of the thermosetting resin.
When the content is 20 to 500 parts by weight, an electromagnetic wave shielding sheet with better solder reflow resistance can be obtained.
導電性接着剤は、他に任意成分としてシランカップリング剤、防錆剤、還元剤、酸化防止剤、顔料、染料、粘着付与樹脂、可塑剤、紫外線吸収剤、消泡剤、レベリング調整剤、充填剤、難燃剤などを配合できる。 Conductive adhesives include silane coupling agents, rust inhibitors, reducing agents, antioxidants, pigments, dyes, tackifying resins, plasticizers, UV absorbers, antifoaming agents, leveling regulators as optional components. Fillers and flame retardants can be blended.
導電性接着剤は、これまで説明した材料を混合し攪拌して得ることができる。攪拌は、例えばディスパーマット、ホモジナイザー等に公知の攪拌装置を使用できる。 The conductive adhesive can be obtained by mixing and stirring the materials described so far. For the stirring, for example, a known stirring device can be used for a disperse mat, a homogenizer or the like.
導電性接着剤層の作製は、公知の方法を使用できる。例えば、導電性接着剤を剥離性シート上に塗工して乾燥することで導電層を形成する方法、または、Ｔダイのような押出成形機を使用して導電性接着剤をシート状に押し出すことで形成することもできる。 A known method can be used for producing the conductive adhesive layer. For example, a method of forming a conductive layer by applying a conductive adhesive on a peelable sheet and drying, or extruding the conductive adhesive into a sheet using an extruder such as a T-die It can also be formed.
塗工方法は、例えば、グラビアコート方式、キスコート方式、ダイコート方式、リップコート方式、コンマコート方式、ブレード方式、ロールコート方式、ナイフコート方式、スプレーコート方式、バーコート方式、スピンコート方式、ディップコート方式等の公知の塗工方法を使用できる。塗工に際して、乾燥工程を行うことが好ましい。乾燥工程は、例えば、熱風乾燥機、赤外線ヒーター等の公知の乾燥装置を使用できる。 Coating methods include, for example, gravure coating method, kiss coating method, die coating method, lip coating method, comma coating method, blade method, roll coating method, knife coating method, spray coating method, bar coating method, spin coating method, dip coating. A known coating method such as a method can be used. In coating, it is preferable to perform a drying step. In the drying step, for example, a known drying device such as a hot air dryer or an infrared heater can be used.
導電性接着剤層の厚みは、２〜１００μｍが好ましく、４〜５０μｍがより好ましく、６〜１５μｍがさらに好ましい。厚みが２〜１００μｍの範囲にあることでハンダリフロー耐性と、その他の物性とのバランスを取り易くなる。 2-100 micrometers is preferable, as for the thickness of a conductive adhesive layer, 4-50 micrometers is more preferable, and 6-15 micrometers is further more preferable. When the thickness is in the range of 2 to 100 μm, it becomes easy to balance the solder reflow resistance and other physical properties.
《絶縁層》
絶縁層は、従来公知の絶縁性樹脂組成物を使用して形成できる。
絶縁性樹脂組成物は、導電性接着剤で説明した熱硬化性樹脂および硬化剤を必要に応じて上記任意成分を含むことができる。なお、絶縁層および導電性接着剤層に使用する熱硬化性樹脂、硬化剤は、同一、または異なっていてもよい。
《Insulating layer》
The insulating layer can be formed using a conventionally known insulating resin composition.
The insulating resin composition can contain the said arbitrary component as needed for the thermosetting resin demonstrated with the conductive adhesive, and the hardening | curing agent. The thermosetting resin and the curing agent used for the insulating layer and the conductive adhesive layer may be the same or different.
絶縁性樹脂組成物は、導電性接着剤と同様の方法で得ることが出来る。 The insulating resin composition can be obtained by the same method as that for the conductive adhesive.
また、絶縁層は、ポリエステル、ポリカーボネート、ポリイミド、ポリフェニレンサルファイド等の絶縁性樹脂を成形したフィルムを使用することもできる。 The insulating layer may be a film formed of an insulating resin such as polyester, polycarbonate, polyimide, polyphenylene sulfide or the like.
絶縁層の厚みは、通常２〜１０μｍ程度である。 The thickness of the insulating layer is usually about 2 to 10 μm.
導電接着剤層および絶縁層の未硬化時のガラス転移温度（Ｔｇ）は、それぞれ独立に、−１０〜８０℃が好ましく、−５〜７０℃がより好ましい。また、導電接着剤層と絶縁層のガラス転移温度（Ｔｇ）の温度の差分は４０℃以下が好ましく、３０℃以下がより好ましく、２０℃以下がさらに好ましい。ガラス転移温度（Ｔｇ）の差分が４０℃以下であることで、後述する熱圧着時に金属層の開口部に導電接着剤層と絶縁層とが流入しやすくなりメッキ液耐性が向上する。また折り曲げ後の接続抵抗値の上昇が抑制される。 The glass transition temperature (Tg) when the conductive adhesive layer and the insulating layer are uncured is preferably independently −10 to 80 ° C., more preferably −5 to 70 ° C. Moreover, the difference in temperature between the glass transition temperature (Tg) of the conductive adhesive layer and the insulating layer is preferably 40 ° C. or less, more preferably 30 ° C. or less, and further preferably 20 ° C. or less. When the difference in glass transition temperature (Tg) is 40 ° C. or less, the conductive adhesive layer and the insulating layer easily flow into the opening of the metal layer at the time of thermocompression bonding described later, and the plating solution resistance is improved. Further, an increase in connection resistance value after bending is suppressed.
《電磁波シールドシート》
本発明の電磁波シールドシートは、少なくとも絶縁層、開口部を有する金属層、および導電性接着剤層を備える。
本発明の電磁波シールドシートは、面積０．７〜５０００μｍ２の開口部を、１００〜２０００００個／ｃｍ２有する金属層を備えているため、特に高周波（例えば、１００ＭＨｚから５０ＧＨｚ）の信号を伝送する配線板でクロストーク等をより抑制することができる。
<Electromagnetic wave shield sheet>
The electromagnetic wave shielding sheet of the present invention includes at least an insulating layer, a metal layer having an opening, and a conductive adhesive layer.
Electromagnetic shield sheet of the present invention, the opening area 0.7～5000Myuemu 2, due to the provision of a metal layer having 100-200000 cells / cm 2, in particular transmission of signals of a high frequency (e.g., 50 GHz from 100 MHz) Crosstalk and the like can be further suppressed by the wiring board.
また、本発明の電磁波シールドシートは、コプレーナ回路を有する配線板に張り合わせ、マイクロストリップライン回路を有する配線板の信号配線と、電磁波シールドシートの絶縁層とを積層し、マイクロストリップライン回路の信号配線に１０ＧＨｚのサイン波を流した際の、コプレーナ回路のクロストークが、−４５ｄＢ未満である、という優れた電磁波シールド性を有することができる。 The electromagnetic wave shielding sheet of the present invention is laminated on a wiring board having a coplanar circuit, and a signal wiring of the wiring board having a microstrip line circuit and an insulating layer of the electromagnetic wave shielding sheet are laminated to form a signal wiring of the microstrip line circuit. The coplanar circuit has an excellent electromagnetic wave shielding property that the crosstalk of the coplanar circuit is less than −45 dB when a sine wave of 10 GHz is applied.
具体的には、例えば以下のようにして、電磁波シールド性を評価することができる。
まず、コプレーナ回路を用意する。
コプレーナ回路とはポリイミドフィルム等の絶縁性基材の片面側に信号配線がプリントされた平面伝送回路の一つであり、本発明においてコプレーナ回路はポリイミドフィルム上に２本の信号配線を挟む形でグランド配線が平行に形成された回路を用いる。尚、前述したコプレーナ回路は、対向する面にグランド設置用のグランドパターンが、スルーホールを介して設置されている。
コプレーナ回路の信号配線と反対側の絶縁性基材面に電磁波シールドシートの導電接着剤層面を張り合わせ、熱圧着によって電磁波シールド層を形成する。
Specifically, for example, the electromagnetic wave shielding property can be evaluated as follows.
First, a coplanar circuit is prepared.
The coplanar circuit is one of planar transmission circuits in which signal wiring is printed on one side of an insulating base material such as polyimide film. In the present invention, the coplanar circuit is formed by sandwiching two signal wirings on a polyimide film. A circuit in which ground wirings are formed in parallel is used. In the above-described coplanar circuit, a ground pattern for grounding is installed on the opposite surface through a through hole.
The conductive adhesive layer surface of the electromagnetic wave shielding sheet is bonded to the insulating base material surface opposite to the signal wiring of the coplanar circuit, and the electromagnetic wave shielding layer is formed by thermocompression bonding.
次に、別途用意したマイクロストリップライン回路を有するプリント配線基板の信号配線をコプレーナ回路に形成した電磁波シールド層の絶縁層面に積層する。この時、信号配線が電磁波シールド層側になるよう積層し、測定用のテストピースが得られる。このテストピースのコプレーナ回路およびマイクロストリップライン回路に、ネットワークアナライザを接続し、マイクロストリップライン回路の信号配線に１０ＭＨｚから２０ＧＨｚのサイン波を流した際の、コプレーナ回路におけるクロストークを測定し、電磁波シールド性を評価することができる。
尚、上述のコプレーナ回路およびマイクロストリップライン回路上には、接着剤付きポリイミドカバーレイフィルムを貼りつけるが、ネットワークアナライザのプローブを接続するため回路の一部を露出させている。
Next, signal wiring of a printed wiring board having a separately prepared microstrip line circuit is laminated on the insulating layer surface of the electromagnetic wave shielding layer formed in the coplanar circuit. At this time, the signal wiring is laminated so as to be on the electromagnetic wave shielding layer side, and a test piece for measurement is obtained. Connect a network analyzer to the coplanar circuit and microstrip line circuit of this test piece, measure crosstalk in the coplanar circuit when a sine wave of 10 MHz to 20 GHz is passed through the signal wiring of the microstrip line circuit, and shield the electromagnetic wave Sex can be evaluated.
A polyimide coverlay film with an adhesive is attached on the above-described coplanar circuit and microstrip line circuit, but a part of the circuit is exposed to connect the probe of the network analyzer.
本発明において、マイクロストリップライン回路の信号配線に１０ＧＨｚのサイン波を流した際の、コプレーナ回路のクロストークは、−４５ｄＢ未満が好ましく、−５０ｄＢ未満がより好ましく、−５５ｄＢ未満がさらに好ましい。クロストークが−４５ｄＢ未満になることで、高い電磁波シールド性を得ることができる。 In the present invention, the crosstalk of the coplanar circuit when a sine wave of 10 GHz is passed through the signal wiring of the microstrip line circuit is preferably less than −45 dB, more preferably less than −50 dB, and even more preferably less than −55 dB. When the crosstalk is less than −45 dB, high electromagnetic shielding properties can be obtained.
本発明の電磁波シールドシートは、反発力が３０ｍＮ/ｍｍ 以下であることが好ましい。面積０．７〜５０００μｍ２の開口部を１００〜２０００００個／ｃｍ２有し、かつ金属層の開口部において、数式（１）から求められるｗが０．８〜２．２である金属層を備えているため、金属層が有する反発力を低減し電磁波シールドシートとしての反発力を３０ｍＮ/ｍｍ 以下にすることができる。上記の反発力とすることで、後述するプリント配線板のハンドリング性が向上し、狭い筐体内に実装した際に電子部品の不具合を低減する。 The electromagnetic wave shielding sheet of the present invention preferably has a repulsive force of 30 mN / mm or less. A metal layer having 100 to 200,000 openings / cm 2 having an area of 0.7 to 5000 μm 2 and having w of 0.8 to 2.2 obtained from the formula (1) in the opening of the metal layer. Since it has, the repulsive force which a metal layer has can be reduced and the repulsive force as an electromagnetic wave shield sheet can be 30 mN / mm or less. By using the above repulsive force, the handling property of a printed wiring board, which will be described later, is improved, and defects of electronic components are reduced when mounted in a narrow casing.
電磁波シールドシートは、導電性接着剤層に含まれる熱硬化性樹脂と硬化剤が未硬化状態で存在し（Ｂステージ）、配線板と加熱圧着により硬化することで（Ｃステージ）、所望の接着強度を得ることが出来る。なお、前記未硬化状態は、硬化剤の一部が硬化した半硬化状態を含む。 The electromagnetic wave shielding sheet has a thermosetting resin and a curing agent contained in the conductive adhesive layer in an uncured state (B stage), and is cured by thermocompression bonding with the wiring board (C stage) to achieve desired adhesion. Strength can be obtained. The uncured state includes a semi-cured state in which a part of the curing agent is cured.
剥離性シートは、紙やプラスチック等の基材に公知の剥離処理を行ったシートである。 The peelable sheet is a sheet obtained by performing a known peeling treatment on a substrate such as paper or plastic.
なお電磁波シールドシートは、異物の付着を防止するため、導電性接着剤層および絶縁層に剥離性シートを貼り付けた状態で保存することが一般的である。 Note that the electromagnetic wave shielding sheet is generally stored in a state where a peelable sheet is attached to the conductive adhesive layer and the insulating layer in order to prevent adhesion of foreign matters.
電磁波シールドシートは、絶縁層、金属層、および導電性接着剤層のほかに、他の機能層を備えることができる。他の機能層とは、ハードコート性、水蒸気バリア性、酸素バリア性、熱伝導性、低誘電率、高誘電率性または耐熱性等の機能を有する層である。 The electromagnetic wave shielding sheet can include other functional layers in addition to the insulating layer, the metal layer, and the conductive adhesive layer. The other functional layer is a layer having functions such as hard coat property, water vapor barrier property, oxygen barrier property, thermal conductivity, low dielectric constant, high dielectric constant or heat resistance.
本発明の電磁波シールドシートは、電磁波をシールドする必要がある様々な用途に使用できる。例えば、フレキシブルプリント配線板は元より、リジッドプリント配線板、ＣＯＦ、ＴＡＢ、フレキシブルコネクタ、液晶ディスプレイ、タッチパネル等に使用できる。また、パソコンのケース、建材の壁および窓ガラス等の建材、車両、船舶、航空機等の電磁波を遮蔽する部材としても使用できる。 The electromagnetic wave shielding sheet of the present invention can be used for various applications where electromagnetic waves need to be shielded. For example, flexible printed wiring boards can be used for rigid printed wiring boards, COFs, TABs, flexible connectors, liquid crystal displays, touch panels, and the like. Moreover, it can also be used as a member for shielding electromagnetic waves from a case of a personal computer, a building material such as a wall of a building material and a window glass, a vehicle, a ship, and an aircraft.
＜電磁波シールドシートの作製方法＞
電磁波シールドシートの作製において、導電性接着剤層と金属層とを積層する方法は、公知の方法を使用できる。
例えば、（ｉ）剥離性シート上に導電性接着剤層を形成し、銅キャリア付開口部を有する電解銅箔の電解銅箔面側に導電性接着剤層を重ねてラミネートした後に、銅キャリアを剥がす。そして、銅キャリアを剥がした面と、別途剥離性シート上に形成した絶縁層とを重ねてラミネートする方法、（ii）剥離性シート上に絶縁層を形成し、銅キャリア付開口部を有する電解銅箔の電解銅箔面側に絶縁層を重ねてラミネートした後に、銅キャリアを剥がす。そして、銅キャリアを剥がした面と、別途剥離性シート上に形成した導電性接着剤層とを重ねてラミネートする方法、（iii）銅キャリア付開口部を有する電解銅箔の電
解銅箔面側に絶縁性樹脂組成物を塗工して絶縁層を形成し剥離性シートを張り合わせる。その後銅キャリアを剥がし、別途剥離性シート上に形成した導電性接着剤層とを重ねてラミネートする方法、（iv）剥離性シート上に導電性接着剤層を形成し、銅キャリア付電解銅箔の電解銅箔面側に導電性接着剤層を重ねてラミネートした後に、銅キャリアを剥がす。そして、銅キャリアを剥がした面と、別途剥離性シート上に形成した絶縁層とを重ねてラミネートした後、針状の治具で電磁波シールドシートに開口部を形成する方法等が挙げられる。
<Method for producing electromagnetic wave shielding sheet>
In the production of the electromagnetic wave shielding sheet, a known method can be used for laminating the conductive adhesive layer and the metal layer.
For example, (i) after forming a conductive adhesive layer on a peelable sheet and laminating the conductive adhesive layer on the electrolytic copper foil surface side of an electrolytic copper foil having an opening with a copper carrier, Remove. And a method of laminating and laminating the surface from which the copper carrier is peeled off and an insulating layer separately formed on the peelable sheet, and (ii) electrolysis having an insulating layer formed on the peelable sheet and having an opening with a copper carrier. After laminating the insulating layer on the electrolytic copper foil surface side of the copper foil, the copper carrier is peeled off. And the method of laminating | stacking the surface which peeled the copper carrier, and the electroconductive adhesive layer separately formed on the peelable sheet, (iii) The electrolytic copper foil surface side of the electrolytic copper foil which has an opening part with a copper carrier An insulating resin composition is applied to the substrate to form an insulating layer, and a peelable sheet is laminated. Thereafter, the copper carrier is peeled off and laminated with a conductive adhesive layer separately formed on a peelable sheet, and (iv) a conductive adhesive layer is formed on the peelable sheet, and an electrolytic copper foil with a copper carrier. After laminating and laminating a conductive adhesive layer on the electrolytic copper foil surface side, the copper carrier is peeled off. And after laminating | stacking by laminating | stacking and laminating | stacking the surface which peeled the copper carrier, and the insulating layer separately formed on the peelable sheet, the method etc. which form an opening part in an electromagnetic wave shield sheet with a needle-shaped jig | tool are mentioned.
《プリント配線板》
本発明のプリント配線板は、電磁波シールドシート、カバーコート層、ならびに信号配線とグランド配線とを有する回路パターンおよび絶縁性基材を有する配線板を備えており、電磁波シールドシートが、絶縁層と金属層と導電性接着剤層とから構成され、前記金属層は、面積０．７〜５０００μｍ２の開口部を１００〜２０００００個／ｃｍ２有し、かつ金属層の開口部において、数式（１）から求められるｗが０．８〜２．２である。
<Printed wiring board>
The printed wiring board of the present invention includes an electromagnetic wave shielding sheet, a cover coat layer, a circuit pattern having a signal wiring and a ground wiring, and a wiring board having an insulating substrate. The electromagnetic wave shielding sheet includes an insulating layer and a metal. The metal layer has 100 to 200000 openings / cm 2 with an area of 0.7 to 5000 μm 2 , and in the opening of the metal layer, the formula (1) W calculated from is 0.8 to 2.2.
本発明のプリント配線板において、電磁波シールド層は、絶縁層と金属層と導電性接着剤層とから構成される電磁波シールドシートを熱圧着してなり、
金属層は、面積０．７〜５０００μｍ２の開口部を、１００〜２０００００個／ｃｍ２有しており、かつ金属層の開口部において、数式（１）から求められるｗが０．８〜２．２である。
配線板は、絶縁性基材の表面に信号配線とグランド配線とを有する回路パターンを有し、
前記配線板上に、信号配線とグランド配線とを絶縁保護し、グランド配線上の少なくとも一部に開口部を有するカバーコート層を形成し、
前記電磁波シールドシートの導電性接着剤層面を、前記カバーコート層上に配置した後、前記電磁波シールドシートを熱圧着し、金属層の開口部内部において、導電性接着剤層と絶縁層とを互いに流入させ開口部の内部で接着させることにより、製造することができる。
In the printed wiring board of the present invention, the electromagnetic shielding layer is formed by thermocompression bonding of an electromagnetic shielding sheet composed of an insulating layer, a metal layer, and a conductive adhesive layer,
The metal layer has 100 to 200,000 openings / cm 2 with an area of 0.7 to 5000 μm 2 , and w calculated from Equation (1) is 0.8 to 2 in the opening of the metal layer. .2.
The wiring board has a circuit pattern having signal wiring and ground wiring on the surface of the insulating substrate,
On the wiring board, the signal wiring and the ground wiring are insulated and protected, and a cover coat layer having an opening in at least a part of the ground wiring is formed,
After the conductive adhesive layer surface of the electromagnetic wave shielding sheet is disposed on the cover coat layer, the electromagnetic wave shielding sheet is thermocompression bonded, and the conductive adhesive layer and the insulating layer are mutually bonded inside the opening of the metal layer. It can be manufactured by allowing it to flow in and bonding inside the opening.
また、例えば、電磁波シールド層は、絶縁層と金属層と導電性接着剤層とから構成される電磁波シールドシートを熱圧着してなり、
金属層は、面積０．７〜５０００μｍ２の開口部を１００〜２０００００個／ｃｍ２有しており、かつ金属層の開口部において、数式（１）から求められるｗが０．８〜２．２である。
配線板は、絶縁性基材の表面に信号配線とグランド配線とを有する回路パターンを有し、裏面にグランドパターンを有し、スルーホールを介してグランド配線とグランドパターンが導通しており、
前記配線板の絶縁性基材表面上に、前記回路パターンを絶縁保護するカバーコート層を形成し、
前記電磁波シールドシートの導電性接着剤層面を、絶縁性基材裏面のグランドパターンを含む裏面全面に配置した後、前記電磁波シールドシートを熱圧着し、金属層の開口部内部において、導電性接着剤層と絶縁層とを互いに流入させ開口部の内部で接着させることにより、製造することができる。
Further, for example, the electromagnetic wave shielding layer is formed by thermocompression bonding of an electromagnetic wave shielding sheet composed of an insulating layer, a metal layer, and a conductive adhesive layer.
The metal layer has 100 to 200000 openings / cm 2 having an area of 0.7 to 5000 μm 2 , and w obtained from the mathematical formula (1) is 0.8 to 2 in the opening of the metal layer. 2.
The wiring board has a circuit pattern having a signal wiring and a ground wiring on the surface of the insulating substrate, has a ground pattern on the back surface, and the ground wiring and the ground pattern are conducted through a through hole,
On the insulating substrate surface of the wiring board, a cover coat layer for insulating and protecting the circuit pattern is formed,
After the conductive adhesive layer surface of the electromagnetic wave shielding sheet is disposed on the entire back surface including the ground pattern on the back surface of the insulating base material, the electromagnetic wave shielding sheet is thermocompression-bonded, and the conductive adhesive is formed inside the opening of the metal layer. A layer and an insulating layer can be made to flow into each other and bonded inside the opening.
なお、スルーホールは、メッキ処理されていることが好ましい。
また、スルーホールの位置は、任意の場所に、任意の個数設けることができる。
Note that the through hole is preferably plated.
In addition, any number of through holes can be provided at any location.
カバーコート層は、配線板の信号配線を覆い、外部環境から保護する絶縁材料である。カバーコート層は、熱硬化性接着剤付きポリイミドフィルム、熱硬化型もしくは紫外線硬化型のソルダーレジスト、または感光性カバーレイフィルムが好ましく、微細加工をするためには感光性カバーレイフィルムがより好ましい。またカバーコート層は、ポリイミド等の耐熱性と柔軟性を備えた公知の樹脂を使用するのが一般的である。カバーコート層の厚みは、通常１０〜１００μｍ程度である。 The cover coat layer is an insulating material that covers the signal wiring of the wiring board and protects it from the external environment. The cover coat layer is preferably a polyimide film with a thermosetting adhesive, a thermosetting or ultraviolet curable solder resist, or a photosensitive coverlay film, and more preferably a photosensitive coverlay film for fine processing. The cover coat layer generally uses a known resin having heat resistance and flexibility such as polyimide. The thickness of the cover coat layer is usually about 10 to 100 μm.
回路パターンは、アースを取るグランド配線、電子部品に電気信号を送る信号配線を含み、両者は銅箔をエッチング処理することで形成することが一般的である。回路パターンの厚みは、通常１〜５０μｍ程度である。 The circuit pattern includes a ground wiring for grounding and a signal wiring for sending an electrical signal to an electronic component, and both are generally formed by etching a copper foil. The thickness of the circuit pattern is usually about 1 to 50 μm.
絶縁性基材は、ポリエステル、ポリカーボネート、ポリイミド、ポリフェニレンサルファイド、液晶ポリマー等の屈曲可能なプラスチックが好ましく、液晶ポリマーおよびポリイミドがより好ましい。これらの中でも高周波の信号を伝送するプリント配線板の用途を考慮すると比誘電率および誘電正接が低い液晶ポリマーがさらに好ましい。
配線板がリジッド配線板の場合、絶縁性基材の構成材料は、ガラスエポキシが好ましい。これらのような絶縁性基材を備えることで配線板は高い耐熱性が得られる。
The insulating base material is preferably a bendable plastic such as polyester, polycarbonate, polyimide, polyphenylene sulfide, or liquid crystal polymer, and more preferably a liquid crystal polymer or polyimide. Among these, a liquid crystal polymer having a low relative dielectric constant and dielectric loss tangent is more preferable in consideration of the use of a printed wiring board that transmits a high-frequency signal.
When the wiring board is a rigid wiring board, the constituent material of the insulating substrate is preferably glass epoxy. By providing such an insulating substrate, the wiring board can have high heat resistance.
本発明のプリント配線板の一例について、図１を参照して説明する。
電磁波シールドシート１０は、絶縁層３、開口部を有する金属層２、導電性接着剤層１を含む構成である。
An example of the printed wiring board of the present invention will be described with reference to FIG.
The electromagnetic wave shielding sheet 10 includes an insulating layer 3, a metal layer 2 having an opening, and a conductive adhesive layer 1.
カバーコート層８は、配線板の信号配線を覆い外部環境から保護する絶縁材料である。 The cover coat layer 8 is an insulating material that covers the signal wiring of the wiring board and protects it from the external environment.
回路パターンは、アースを取るグランド配線５、電子部品に電気信号を送る信号配線６を含む。両者は銅箔をエッチング処理することで形成することが一般的である。 The circuit pattern includes a ground wiring 5 for grounding and a signal wiring 6 for sending an electric signal to an electronic component. Both are generally formed by etching a copper foil.
電磁波シールドシート１０と、配線板との加熱圧着は、温度１５０〜１９０℃程度、圧力１〜３ＭＰａ程度、時間１〜６０分程度の条件で行うことが一般的である。加熱圧着により導電性接着剤層１とカバーコート層８が密着するとともに、導電性接着剤層１が流動して穴１１を埋めることでグランド配線５との間で導通が取れる。さらに熱硬化性樹脂を使用した場合、加熱圧着により熱硬化性樹脂と硬化剤が反応する。
同時に金属層２の開口部４内部に導電接着剤層１と絶縁層３が流入し開口部４内部で接着し硬化する。開口部内部で接着し硬化することで、導電接着剤層１、金属層２、絶縁層３の接着強度が増強されメッキ液耐性が大幅に向上する。
なお、硬化を促進させるため、加熱圧着後に１５０〜１９０℃で３０〜９０分間ポストキュアを行う場合もある。なお、電磁波シールドシートは、加熱圧着後に電磁波シールド層ということがある。
Generally, the thermocompression bonding between the electromagnetic wave shielding sheet 10 and the wiring board is performed under conditions of a temperature of about 150 to 190 ° C., a pressure of about 1 to 3 MPa, and a time of about 1 to 60 minutes. The conductive adhesive layer 1 and the cover coat layer 8 are brought into close contact with each other by thermocompression bonding, and the conductive adhesive layer 1 flows and fills the hole 11 so that conduction with the ground wiring 5 can be obtained. Further, when a thermosetting resin is used, the thermosetting resin and the curing agent react by thermocompression bonding.
At the same time, the conductive adhesive layer 1 and the insulating layer 3 flow into the opening 4 of the metal layer 2 and are bonded and cured inside the opening 4. By bonding and curing inside the opening, the adhesive strength of the conductive adhesive layer 1, the metal layer 2, and the insulating layer 3 is enhanced, and the plating solution resistance is greatly improved.
In order to accelerate curing, post-curing may be performed at 150 to 190 ° C. for 30 to 90 minutes after thermocompression bonding. In addition, an electromagnetic wave shield sheet may be called an electromagnetic wave shield layer after thermocompression bonding.
前記電磁波シールド層は配線基板の両面に形成することが、電磁波の漏れをより効果的に抑制できる点から好ましい。本発明の電磁波シールドシートは、絶縁層と金属層と導電性接着剤層とから構成され、前記金属層は、面積０．７〜５０００μｍ２の開口部を１００〜２０００００個／ｃｍ２有し、かつ金属層の開口部において、数式（１）から求められるｗが０．８〜２．２であるため、両面に張り付けられ電磁波シールド層を形成した後、リフロー処理した場合においても、内部残留ガスを外部に排出するため発泡が生じない。加えて、本発明のプリント配線板における電磁波シールドシート１０は電磁波を遮蔽する他に、グランド回路として利用でき、それにより、グランド回路の一部を省略し、プリント配線板の面積を縮小することでコストダウンが可能となり筐体内の狭い領域に組み込むことができる。 The electromagnetic wave shielding layer is preferably formed on both surfaces of the wiring board from the viewpoint that electromagnetic wave leakage can be more effectively suppressed. The electromagnetic wave shielding sheet of the present invention is composed of an insulating layer, a metal layer, and a conductive adhesive layer, and the metal layer has 100 to 200000 pieces / cm 2 of openings having an area of 0.7 to 5000 μm 2 . And in the opening part of a metal layer, since w calculated | required from Formula (1) is 0.8-2.2, even when it reflow-processes after sticking on both surfaces and forming an electromagnetic wave shield layer, internal residual gas Foaming does not occur because it is discharged to the outside. In addition, the electromagnetic shielding sheet 10 in the printed wiring board of the present invention can be used as a ground circuit in addition to shielding electromagnetic waves, thereby omitting a part of the ground circuit and reducing the area of the printed wiring board. The cost can be reduced, and it can be incorporated in a narrow area in the housing.
また、信号配線に関して、特に限定するものではなく、一本の信号配線からなるシングルエンド、２本の信号配線からなる差動回路のどちらの回路にも使用可能であるが、差動回路がより好ましい。一方、プリント配線板の回路パターン面積に制約があり、グランド回路を並列に形成することが難しい場合においては、信号回路の横にはグランド回路を設けず、シールドシートをグランド回路として用いて、厚み方向にグランドを有するプリント配線板構造にすることもできる。 In addition, the signal wiring is not particularly limited, and can be used for either a single-ended circuit composed of one signal wiring or a differential circuit composed of two signal wirings. preferable. On the other hand, if the circuit pattern area of the printed wiring board is limited and it is difficult to form the ground circuit in parallel, the ground circuit is not provided beside the signal circuit, and the shield sheet is used as the ground circuit. A printed wiring board structure having a ground in the direction can also be used.
本発明のプリント配線板は、液晶ディスプレイ、タッチパネル等のほか、ノートＰＣ、携帯電話、スマートフォン、タブレット端末等の電子機器に備える（搭載する）ことが好ましい。 The printed wiring board of the present invention is preferably provided (installed) in an electronic device such as a notebook PC, a mobile phone, a smartphone, or a tablet terminal in addition to a liquid crystal display, a touch panel, or the like.
以下、本発明を実施例により更に詳細に説明するが、本発明は以下の実施例に限定されるものではない。また、実施例中の「部」とあるのは「重量部」を、「％」とあるのは「重量％」を其々表すものとする。 EXAMPLES Hereinafter, although an Example demonstrates this invention still in detail, this invention is not limited to a following example. In the examples, “part” means “part by weight”, and “%” means “% by weight”.
なお、樹脂の酸価と重量平均分子量（Ｍｗ）とガラス転移温度（Ｔｇ）、導電性微粒子の平均粒子径、および金属層の開口部の分散性（ｗ）の測定は次の方法で行なった。 The acid value, weight average molecular weight (Mw) and glass transition temperature (Tg) of the resin, the average particle diameter of the conductive fine particles, and the dispersibility (w) of the opening of the metal layer were measured by the following methods. .
＜樹脂の酸価の測定＞
酸価はＪＩＳ Ｋ００７０に準じて測定した。共栓三角フラスコ中に試料約１ｇを精密
に量り採り、テトラヒドロフラン／エタノール（容量比：テトラヒドロフラン／エタノール＝２／１）混合液１００ｍｌを加えて溶解する。これに、フェノールフタレイン試液を指示薬として加え、０．１Ｎアルコール性水酸化カリウム溶液で滴定し、指示薬が淡紅色を３０秒間保持した時を終点とした。酸価は次式により求めた（単位：ｍｇＫＯＨ／ｇ）。
酸価（ｍｇＫＯＨ／ｇ）＝（５．６１１×ａ×Ｆ）／Ｓ
ただし、
Ｓ：試料の採取量（ｇ）
ａ：０．１Ｎアルコール性水酸化カリウム溶液の消費量（ｍｌ）
Ｆ：０．１Ｎアルコール性水酸化カリウム溶液の力価
<Measurement of acid value of resin>
The acid value was measured according to JIS K0070. About 1 g of a sample is accurately weighed in a stoppered Erlenmeyer flask, and 100 ml of a tetrahydrofuran / ethanol (volume ratio: tetrahydrofuran / ethanol = 2/1) mixed solution is added and dissolved. To this was added a phenolphthalein test solution as an indicator and titrated with a 0.1N alcoholic potassium hydroxide solution. The end point was when the indicator retained a light red color for 30 seconds. The acid value was determined by the following formula (unit: mgKOH / g).
Acid value (mgKOH / g) = (5.611 × a × F) / S
However,
S: Sample collection amount (g)
a: Consumption of 0.1N alcoholic potassium hydroxide solution (ml)
F: Potency of 0.1N alcoholic potassium hydroxide solution
＜樹脂の重量平均分子量（Ｍｗ）の測定＞
重量平均分子量（Ｍｗ）の測定は東ソー株式会社製ＧＰＣ（ゲルパーミエーションクロマトグラフィー）「ＨＰＣ−８０２０」を用いた。ＧＰＣは溶媒（ＴＨＦ；テトラヒドロフラン）に溶解した物質をその分子サイズの差によって分離定量する液体クロマトグラフィーである。本発明における測定は、カラムに「ＬＦ−６０４」（昭和電工株式会社製：迅速分析用ＧＰＣカラム：６ｍｍＩＤ×１５０ｍｍサイズ）を直列に２本接続して用い、流量０．６ｍｌ／ｍｉｎ、カラム温度４０℃の条件で行い、重量平均分子量（Ｍｗ）の決定はポリスチレン換算で行った。
<Measurement of weight average molecular weight (Mw) of resin>
The weight average molecular weight (Mw) was measured by using GPC (gel permeation chromatography) “HPC-8020” manufactured by Tosoh Corporation. GPC is liquid chromatography that separates and quantifies substances dissolved in a solvent (THF; tetrahydrofuran) based on the difference in molecular size. For the measurement in the present invention, “LF-604” (manufactured by Showa Denko KK: GPC column for rapid analysis: 6 mm ID × 150 mm size) is connected in series to the column, the flow rate is 0.6 ml / min, the column temperature. It carried out on the conditions of 40 degreeC, and the determination of the weight average molecular weight (Mw) was performed in polystyrene conversion.
＜樹脂のガラス転移温度（Ｔｇ）＞
Ｔｇの測定は、示差走査熱量測定（メトラー・トレド社製「ＤＳＣ−１」）によって測定した。
<Glass transition temperature (Tg) of resin>
Tg was measured by differential scanning calorimetry (“DSC-1” manufactured by METTLER TOLEDO).
＜導電性微粒子の平均粒子径測定＞
Ｄ５０平均粒子径は、レーザー回折・散乱法粒度分布測定装置ＬＳ１３３２０（ベックマン・コールター社製）を使用し、トルネードドライパウダーサンプルモジュールにて、導電性微粒子を測定して得た数値であり、粒子径累積分布における累積値が５０％の粒子径である。なお、屈折率の設定は１．６とした。
<Measurement of average particle size of conductive fine particles>
The D50 average particle size is a numerical value obtained by measuring conductive fine particles with a tornado dry powder sample module using a laser diffraction / scattering particle size distribution analyzer LS13320 (manufactured by Beckman Coulter, Inc.). The cumulative value in the cumulative distribution is the particle diameter of 50%. The refractive index was set to 1.6.
＜開口部の分散性（ｗ）の測定＞
金属層の開口部が２０個程度入るように、レーザー顕微鏡ＶＫ-Ｘ１００（キーエンス
社製）を用いて２０００倍の倍率で金属層の平面画像を取得した。
一例を挙げると、図２は後述する銅箔１５の開口部取得画像である。取得した画像から、画像内の金属層の面積Ｓ、開口部の個数ｎおよび開口部毎の最近隣距離を測定し、数式（２）数式（３）から、平均最近隣距離の期待値と平均最近隣距離を算出し、数式（１）によってｗを求めた。
<Measurement of dispersibility (w) of opening>
A planar image of the metal layer was obtained at a magnification of 2000 times using a laser microscope VK-X100 (manufactured by Keyence Corporation) so that about 20 openings of the metal layer could enter.
As an example, FIG. 2 is an opening acquisition image of a copper foil 15 to be described later. From the acquired image, the area S of the metal layer in the image, the number n of the openings, and the nearest neighbor distance for each opening are measured, and the expected value and the average of the nearest neighbor distance are calculated from Equation (2) and Equation (3). The nearest neighbor distance was calculated, and w was obtained from Equation (1).
続いて、実施例で使用した原料を以下に示す。
＜原料＞
導電性微粒子１：複合微粒子（核体の銅１００重量部に対して銀が１０重量部被覆されたデンドライト状の微粒子）平均粒径Ｄ５０：１１．０μｍ 福田金属箔粉工業社製
電解銅箔：「ＭＴ１８ＳＤ−Ｈ（１８μｍの銅キャリアに３μｍの電解銅箔）」（三井金属社製）
エポキシ化合物：「ＪＥＲ８２８」（ビスフェノールＡ型エポキシ樹脂 エポキシ当量＝１８９ｇ／ｅｑ）三菱化学社製
アジリジン化合物：「ケミタイトＰＺ−３３」日本触媒社製
Then, the raw material used in the Example is shown below.
<Raw material>
Conductive fine particles 1: Composite fine particles (dendritic fine particles in which 10 parts by weight of silver is coated on 100 parts by weight of core copper) Average particle diameter D50: 11.0 μm Electrolytic copper foil manufactured by Fukuda Metal Foil Powder Industry Co., Ltd .: “MT18SD-H (18 μm copper carrier with 3 μm electrolytic copper foil)” (Mitsui Metals)
Epoxy compound: “JER828” (bisphenol A type epoxy resin, epoxy equivalent = 189 g / eq) Aziridine compound: “Chemite PZ-33” manufactured by Nippon Shokubai Co., Ltd.
＜金属層＞
表１に記載する銅キャリア付き銅箔１〜１７を使用した。
The copper foils 1-17 with a copper carrier described in Table 1 were used.
＜バインダー樹脂＞
［合成例１］
攪拌機、温度計、還流冷却器、滴下装置、窒素導入管を備えた反応容器に、アジピン酸とテレフタル酸及び３−メチル−１，５−ペンタンジオールから得られる数平均分子量（以下、「Ｍｎ」という）＝１００６であるジオール４１４部、ジメチロールブタン酸８部、イソホロンジイソシアネート１４５部、及びトルエン４０部を仕込み、窒素雰囲気下９０℃で３時間反応させた。これに、トルエン３００部を加えて、末端にイソシアネート基を有するウレタンプレポリマーの溶液を得た。次に、イソホロンジアミン２７部、ジ−ｎ−ブチルアミン３部、２−プロパノール３４２部、及びトルエン５７６部を混合したものに、得られたウレタンプレポリマーの溶液８１６部を添加し、７０℃で３時間反応させ、ポリウレタン樹脂の溶液を得た。これに、トルエン１４４部、２−プロパノール７２部を加えて、固形分３０％であるポリウレタン樹脂（熱硬化性樹脂１）溶液を得た。重量平均分子量は５４，０００、Ｔｇは−７℃、酸価は５ｍｇＫＯＨ／ｇであった。
<Binder resin>
[Synthesis Example 1]
A number average molecular weight (hereinafter referred to as “Mn”) obtained from adipic acid, terephthalic acid and 3-methyl-1,5-pentanediol in a reaction vessel equipped with a stirrer, a thermometer, a reflux condenser, a dropping device, and a nitrogen introduction tube. Diol = 414, dimethylol butanoic acid 8 parts, isophorone diisocyanate 145 parts and toluene 40 parts were charged and reacted at 90 ° C. for 3 hours in a nitrogen atmosphere. To this, 300 parts of toluene was added to obtain a urethane prepolymer solution having an isocyanate group at the terminal. Next, 816 parts of the obtained urethane prepolymer solution was added to a mixture of 27 parts of isophoronediamine, 3 parts of di-n-butylamine, 342 parts of 2-propanol, and 576 parts of toluene. It was made to react for a time and the solution of the polyurethane resin was obtained. To this, 144 parts of toluene and 72 parts of 2-propanol were added to obtain a polyurethane resin (thermosetting resin 1) solution having a solid content of 30%. The weight average molecular weight was 54,000, Tg was −7 ° C., and the acid value was 5 mgKOH / g.
［合成例２］
攪拌機、温度計、還流冷却器、滴下装置、窒素導入管を備えた反応容器に、アジピン酸と３−メチル−１，５−ペンタンジオール及び１，６−ヘキサンカーボネートジオールとから得られるＭｎ＝９８１であるジオール３９０部、ジメチロールブタン酸１６部、イソホロンジイソシアネート１５８部、及びトルエン４０部を仕込み、窒素雰囲気下９０℃で３時間反応させた。これに、トルエン３００部を加えて、末端にイソシアネート基を有するウレタンプレポリマーの溶液を得た。次に、イソホロンジアミン２９部、ジ−ｎ−ブチルアミン３部、２−プロノール３４２部、及びトルエン５７６部を混合したものに、得られたウレタンプレポリマーの溶液８１４部を添加し、７０℃で３時間反応させ、ポリウレタン樹脂の溶液を得た。これに、トルエン１４４部、２−プロパノール７２部を加えて、固形分３０％であるポリウレタン樹脂（熱硬化性樹脂２）溶液を得た。重量平均分子量は４３，０００、Ｔｇは−５℃、酸価は１０ｍｇＫＯＨ／ｇであった。
[Synthesis Example 2]
Mn = 981 obtained from adipic acid, 3-methyl-1,5-pentanediol and 1,6-hexane carbonate diol in a reaction vessel equipped with a stirrer, thermometer, reflux condenser, dropping device, and nitrogen introduction tube Diol 390, dimethylolbutanoic acid 16 parts, isophorone diisocyanate 158 parts, and toluene 40 parts were charged and reacted at 90 ° C. for 3 hours in a nitrogen atmosphere. To this, 300 parts of toluene was added to obtain a urethane prepolymer solution having an isocyanate group at the terminal. Next, 814 parts of the resulting urethane prepolymer solution was added to a mixture of 29 parts of isophorone diamine, 3 parts of di-n-butylamine, 342 parts of 2-pronol, and 576 parts of toluene. It was made to react for a time and the solution of the polyurethane resin was obtained. To this, 144 parts of toluene and 72 parts of 2-propanol were added to obtain a polyurethane resin (thermosetting resin 2) solution having a solid content of 30%. The weight average molecular weight was 43,000, Tg was −5 ° C., and the acid value was 10 mgKOH / g.
［合成例３］
攪拌機、温度計、還流冷却器、滴下装置、窒素導入管を備えた反応容器に、アジピン酸と３−メチル−１，５−ペンタンジオールとから得られるＭｎ＝１００２であるジオール３５２部、ジメチロールブタン酸３２部、イソホロンジイソシアネート１７６部、及びトルエン４０部を仕込み、窒素雰囲気下９０℃で３時間反応させた。これに、トルエン３００部を加えて、末端にイソシアネート基を有するウレタンプレポリマーの溶液を得た。次に、イソホロンジアミン３２部、ジ−ｎ−ブチルアミン４部、２−プロパノール３４２部、及びトルエン５７６部を混合したものに、得られたウレタンプレポリマーの溶液８１０部を添加し、７０℃で３時間反応させ、ポリウレタンポリウレア樹脂の溶液を得た。これに、トルエン１４４部、２−プロパノール７２部を加えて、固形分３０％であるポリウレタン樹脂（熱硬化性樹脂３）溶液を得た。重量平均分子量は３５，０００、Ｔｇは−１℃、酸価は２１ｍｇＫＯＨ／ｇであった。
[Synthesis Example 3]
A reaction vessel equipped with a stirrer, a thermometer, a reflux condenser, a dropping device, and a nitrogen introduction tube, 352 parts of diol having Mn = 1002 obtained from adipic acid and 3-methyl-1,5-pentanediol, dimethylol 32 parts of butanoic acid, 176 parts of isophorone diisocyanate and 40 parts of toluene were charged and reacted at 90 ° C. for 3 hours in a nitrogen atmosphere. To this, 300 parts of toluene was added to obtain a urethane prepolymer solution having an isocyanate group at the terminal. Next, 810 parts of the obtained urethane prepolymer solution was added to a mixture of 32 parts of isophoronediamine, 4 parts of di-n-butylamine, 342 parts of 2-propanol, and 576 parts of toluene, It was made to react for a time and the solution of the polyurethane polyurea resin was obtained. To this, 144 parts of toluene and 72 parts of 2-propanol were added to obtain a polyurethane resin (thermosetting resin 3) solution having a solid content of 30%. The weight average molecular weight was 35,000, Tg was -1 ° C, and the acid value was 21 mgKOH / g.
［合成例４］
攪拌機、温度計、滴下装置、還流冷却器、ガス導入管を備えた反応容器に、水酸基価１１０ｍｇＫＯＨ／ｇのポリテトラメチレングリコール１０１．１部、ジメチロールブタン酸２１．９部、溶剤としてメチルエチルケトン６０部を仕込み、窒素気流下、攪拌しながら６０℃まで加熱し、均一になるまで溶解した。続いてこの反応容器に、イソホロンジイソシアネート５２．１部を投入し、８０℃で８時間反応を行った。室温に冷却後、メチルエチルケトンで希釈することで固形分５０％のカルボキシル基を含有するポリウレタン樹脂（熱硬化性樹脂４）溶液を得た。重量平均分子量は２８,０００、Ｔｇは−１０℃、酸
価は４７ｍｇＫＯＨ／ｇであった。
[Synthesis Example 4]
In a reaction vessel equipped with a stirrer, a thermometer, a dropping device, a reflux condenser, and a gas introduction tube, 101.1 parts of polytetramethylene glycol having a hydroxyl value of 110 mgKOH / g, 21.9 parts of dimethylolbutanoic acid, and methyl ethyl ketone 60 as a solvent The portion was charged, heated to 60 ° C. with stirring under a nitrogen stream, and dissolved until uniform. Subsequently, 52.1 parts of isophorone diisocyanate was added to the reaction vessel, and the reaction was performed at 80 ° C. for 8 hours. After cooling to room temperature, a polyurethane resin (thermosetting resin 4) solution containing a carboxyl group with a solid content of 50% was obtained by diluting with methyl ethyl ketone. The weight average molecular weight was 28,000, Tg was −10 ° C., and the acid value was 47 mgKOH / g.
［合成例５］
攪拌機、温度計、滴下装置、還流冷却器、ガス導入管を備えた反応容器にメチルエチルケトン５０部を入れ、容器に窒素ガスを注入しながら８０℃に加熱して、同温度でメタクリル酸３部、ｎーブチルメタクリレート３２部、ラウリルメタクリレート６５部、２，２’−アゾビスイソブチロニトリル４部の混合物を１時間かけて滴下して重合反応を行った。滴下終了後、さらに８０℃で３時間反応させた後、アゾビスイソブチロニトリル１部をメチルエチルケトン５０部に溶解させたものを添加し、さらに８０℃で１時間反応を継続した後、室温まで冷却した。次いでメチルエチルケトンで希釈することで固形分３０％のカルボキシル基を含有するアクリル樹脂（熱硬化性樹脂５）溶液を得た。重量平均分子量は２７，０００、Ｔｇは−１１℃、酸価は２０ｍｇＫＯＨ／ｇであった。
[Synthesis Example 5]
Into a reaction vessel equipped with a stirrer, thermometer, dripping device, reflux condenser, and gas introduction tube, 50 parts of methyl ethyl ketone was added, heated to 80 ° C. while injecting nitrogen gas into the vessel, and 3 parts of methacrylic acid at the same temperature, A mixture of 32 parts of n-butyl methacrylate, 65 parts of lauryl methacrylate and 4 parts of 2,2′-azobisisobutyronitrile was added dropwise over 1 hour to carry out a polymerization reaction. After completion of the dropwise addition, the mixture was further reacted at 80 ° C. for 3 hours, then 1 part of azobisisobutyronitrile dissolved in 50 parts of methyl ethyl ketone was added, and the reaction was further continued at 80 ° C. for 1 hour. Cooled down. Next, an acrylic resin (thermosetting resin 5) solution containing a carboxyl group having a solid content of 30% was obtained by dilution with methyl ethyl ketone. The weight average molecular weight was 27,000, Tg was −11 ° C., and the acid value was 20 mgKOH / g.
［合成例６］
攪拌機、温度計、滴下装置、還流冷却器、ガス導入管を備えた反応容器にメチルエチルケトン５０部を入れ、容器に窒素ガスを注入しながら８０℃に加熱して、同温度でメタクリル酸３部、ｎーブチルメタクリレート７２部、ラウリルメタクリレート２５部、２，２’−アゾビスイソブチロニトリル４部の混合物を１時間かけて滴下して重合反応を行った。滴下終了後、さらに８０℃で３時間反応させた後、アゾビスイソブチロニトリル１部をメチルエチルケトン５０部に溶解させたものを添加し、さらに８０℃で１時間反応を継続した後、室温まで冷却した。次いでメチルエチルケトンで希釈することで固形分３０％のカルボキシル基を含有するアクリル樹脂（熱硬化性樹脂６）を得た。重量平均分子量は２４,０００、Ｔｇは−４０℃、酸価は２０ｍｇＫＯＨ／ｇであった。
[Synthesis Example 6]
Into a reaction vessel equipped with a stirrer, thermometer, dripping device, reflux condenser, and gas introduction tube, 50 parts of methyl ethyl ketone was added, heated to 80 ° C. while injecting nitrogen gas into the vessel, and 3 parts of methacrylic acid at the same temperature, A mixture of 72 parts of n-butyl methacrylate, 25 parts of lauryl methacrylate and 4 parts of 2,2′-azobisisobutyronitrile was added dropwise over 1 hour to carry out a polymerization reaction. After completion of the dropwise addition, the mixture was further reacted at 80 ° C. for 3 hours, then 1 part of azobisisobutyronitrile dissolved in 50 parts of methyl ethyl ketone was added, and the reaction was further continued at 80 ° C. for 1 hour. Cooled down. Next, an acrylic resin (thermosetting resin 6) containing a carboxyl group having a solid content of 30% was obtained by dilution with methyl ethyl ketone. The weight average molecular weight was 24,000, Tg was −40 ° C., and the acid value was 20 mgKOH / g.
［合成例７］
撹拌機、還流冷却管、窒素導入管、導入管、温度計を備えた４口フラスコに、ポリカーボネートジオ−ル（クラレポリオールＣ−２０２０）１９３．８部、主鎖用の酸無水物基含有化合物としてテトラヒドロ無水フタル酸（リカシッドＴＨ：新日本理化株式会社製）２９．２部、溶剤としてトルエン３５０部を仕込み、窒素気流下、攪拌しながら６０℃ まで昇温し、均一に溶解させた。続いてこのフラスコを１１０℃に昇温し、３時間反応させた。その後、４０℃に冷却後、ビスフェノールＡ型エポキシ化合物（ＹＤ−８１２５：新日鐵化学株式会社製：エポキシ当量＝１７５ｇ／ｅｑ）３４．２部、触媒としてトリフェニルホスフィン４部を添加して１１０℃に昇温し、８時間反応させた。室温まで冷却後、側鎖用の酸無水物基含有化合物としてテトラヒドロ無水フタル酸１５．２１部を添加し、１１０℃で３時間反応させた。室温まで冷却後、トルエンで固形分３０％になるよう調整し、付加型ポリエステル樹脂溶液（熱硬化性樹脂７）を得た。重量平均分子量は５０,
０００、Ｔｇは２０℃、酸価は１９ｍｇＫＯＨ／ｇであった。
[Synthesis Example 7]
In a 4-neck flask equipped with a stirrer, reflux condenser, nitrogen inlet pipe, inlet pipe, thermometer, 193.8 parts of polycarbonate diol (Kuraray polyol C-2020), acid anhydride group-containing compound for main chain As a solvent, 29.2 parts of tetrahydrophthalic anhydride (Licacid TH: manufactured by Shin Nippon Rika Co., Ltd.) and 350 parts of toluene as a solvent were added, and the mixture was heated to 60 ° C. with stirring in a nitrogen stream and dissolved uniformly. Subsequently, the flask was heated to 110 ° C. and reacted for 3 hours. Then, after cooling to 40 ° C., 34.2 parts of a bisphenol A type epoxy compound (YD-8125: manufactured by Nippon Steel Chemical Co., Ltd .: epoxy equivalent = 175 g / eq) and 4 parts of triphenylphosphine as a catalyst were added to form 110 parts. The temperature was raised to 0 ° C. and reacted for 8 hours. After cooling to room temperature, 15.21 parts of tetrahydrophthalic anhydride was added as an acid anhydride group-containing compound for the side chain and reacted at 110 ° C. for 3 hours. After cooling to room temperature, the mixture was adjusted with toluene to a solid content of 30% to obtain an addition-type polyester resin solution (thermosetting resin 7). The weight average molecular weight is 50,
000, Tg was 20 ° C., and the acid value was 19 mgKOH / g.
［合成例８］
撹拌機、還流冷却管、窒素導入管、導入管、温度計を備えた４口フラスコに、ポリカーボネートジオ−ル（クラレポリオールＣ−２０４１）１９１．３部、主鎖用の酸無水物基含有化合物としてテトラヒドロ無水フタル酸（リカシッドＨＮＡ−１００：新日本理化株式会社製）３４．６部、溶剤としてトルエン３５０部を仕込み、窒素気流下、攪拌しながら６０℃まで昇温し、均一に溶解させた。続いてこのフラスコを１１０℃に昇温し、３時間反応させた。その後、４０℃に冷却後、ビスフェノールＡ型エポキシ化合物（ＹＤ−８１２５：新日鐵化学株式会社製：エポキシ当量＝１７５ｇ／ｅｑ）３１．９部、触媒としてトリフェニルホスフィン４部を添加して１１０℃に昇温し、８時間反応させた。室温まで冷却後、側鎖用の酸無水物基含有化合物としてテトラヒドロ無水フタル酸１６．７８部を添加し、１１０℃で３時間反応させた。室温まで冷却後、トルエンで固形分３０％になるよう調整し、付加型ポリエステル樹脂（熱硬化性樹脂８）溶液を得た。重量平均分子量は１３２,０００、Ｔｇは−１５℃、酸価は２０ｍｇＫＯＨ／ｇであった。
[Synthesis Example 8]
In a four-necked flask equipped with a stirrer, reflux condenser, nitrogen inlet tube, inlet tube, thermometer, 191.3 parts of polycarbonate diol (Kuraray polyol C-2041), acid anhydride group-containing compound for the main chain 34.6 parts of tetrahydrophthalic anhydride (Licacid HNA-100: manufactured by Shin Nippon Rika Co., Ltd.) and 350 parts of toluene as a solvent were heated to 60 ° C. with stirring in a nitrogen stream and dissolved uniformly. . Subsequently, the flask was heated to 110 ° C. and reacted for 3 hours. Then, after cooling to 40 ° C., 31.9 parts of a bisphenol A type epoxy compound (YD-8125: manufactured by Nippon Steel Chemical Co., Ltd .: epoxy equivalent = 175 g / eq) and 4 parts of triphenylphosphine as a catalyst were added to form 110 parts. The temperature was raised to 0 ° C. and reacted for 8 hours. After cooling to room temperature, 16.78 parts of tetrahydrophthalic anhydride was added as an acid anhydride group-containing compound for the side chain and reacted at 110 ° C. for 3 hours. After cooling to room temperature, the mixture was adjusted to 30% solid content with toluene to obtain an addition-type polyester resin (thermosetting resin 8) solution. The weight average molecular weight was 132,000, Tg was −15 ° C., and the acid value was 20 mgKOH / g.
［合成例９］
撹拌機、還流冷却管、窒素導入管、導入管、温度計を備えた４口フラスコに、ポリカーボネートジオ−ル（クラレポリオールＣ−２０９０）１９５．１部、主鎖用の酸無水物基含有化合物としてテトラヒドロ無水フタル酸（リカシッドＴＨ：新日本理化株式会社製）２９．２部、溶剤としてトルエン３５０部を仕込み、窒素気流下、攪拌しながら６０℃ まで昇温し、均一に溶解させた。続いてこのフラスコを１１０℃に昇温し、３時間反応させた。その後、４０℃に冷却後、ビスフェノールＡ型エポキシ化合物（ＹＤ−８１２５：新日鐵化学株式会社製：エポキシ当量＝１７５ｇ／ｅｑ）２６部、触媒としてトリフェニルホスフィン４部を添加して１１０℃に昇温し、８時間反応させた。室温まで冷却後、側鎖用の酸無水物基含有化合物としてテトラヒドロ無水フタル酸１１．５６部を添加し、１１０℃で３時間反応させた。室温まで冷却後、トルエンで固形分３０％になるよう調整し、付加型ポリエステル樹脂溶液（熱硬化性樹脂９）を得た。重量平均分子量は１５,００
０、Ｔｇは−２５℃、酸価は２５ｍｇＫＯＨ／ｇであった。
[Synthesis Example 9]
In a four-necked flask equipped with a stirrer, reflux condenser, nitrogen inlet tube, inlet tube, thermometer, 195.1 parts of polycarbonate diol (Kuraray polyol C-2090), acid anhydride group-containing compound for main chain As a solvent, 29.2 parts of tetrahydrophthalic anhydride (Licacid TH: manufactured by Shin Nippon Rika Co., Ltd.) and 350 parts of toluene as a solvent were added, and the mixture was heated to 60 ° C. with stirring in a nitrogen stream and dissolved uniformly. Subsequently, the flask was heated to 110 ° C. and reacted for 3 hours. Then, after cooling to 40 ° C., 26 parts of a bisphenol A type epoxy compound (YD-8125: manufactured by Nippon Steel Chemical Co., Ltd .: epoxy equivalent = 175 g / eq) and 4 parts of triphenylphosphine as a catalyst were added to 110 ° C. The temperature was raised and reacted for 8 hours. After cooling to room temperature, 11.56 parts of tetrahydrophthalic anhydride was added as an acid anhydride group-containing compound for the side chain and reacted at 110 ° C. for 3 hours. After cooling to room temperature, the mixture was adjusted to 30% solid content with toluene to obtain an addition-type polyester resin solution (thermosetting resin 9). Weight average molecular weight is 15,000
0, Tg was −25 ° C., and the acid value was 25 mgKOH / g.
［合成例１０］
撹拌機、還流冷却管、窒素導入管、導入管、温度計を備えた４口フラスコに、セバシン酸５４．５部、５−ヒドロキシイソフタル酸５．５部、ダイマージアミン「プリアミン１０７４」（クローダジャパン株式会社製、アミン価２１０．０ｍｇＫＯＨ／ｇ）１４８．４部、イオン交換水を１００部仕込み、発熱の温度が一定になるまで撹拌した。温度が安定したら１１０℃まで昇温し、水の流出を確認してから、３０分後に温度を１２０℃に昇温し、その後、３０分ごとに１０℃ずつ昇温しながら脱水反応を続けた。温度が２３０℃になったら、そのままの温度で３時間反応を続け、約２ＫＰａの真空下で、１時間保持した。その後、温度を低下し、トルエン１４６部、２−プロパノール１４６部で希釈して、ポリアミド樹脂（熱硬化性樹脂１１）溶液を得た。重量平均分子量は３６,０００、Ｔｇは５℃、酸価は１２ｍｇＫＯＨ／ｇであった。
[Synthesis Example 10]
In a four-necked flask equipped with a stirrer, reflux condenser, nitrogen inlet tube, inlet tube, and thermometer, 54.5 parts of sebacic acid, 5.5 parts of 5-hydroxyisophthalic acid, dimeramine “PRIAMINE 1074” (Cloda Japan) 148.4 parts of amine value 210.0 mg KOH / g) and 100 parts of ion-exchanged water were added, and the mixture was stirred until the temperature of heat generation became constant. When the temperature was stabilized, the temperature was raised to 110 ° C., and after confirming the outflow of water, the temperature was raised to 120 ° C. after 30 minutes, and then the dehydration reaction was continued while raising the temperature by 10 ° C. every 30 minutes. . When the temperature reached 230 ° C., the reaction was continued for 3 hours at the same temperature, and held for 1 hour under a vacuum of about 2 KPa. Thereafter, the temperature was lowered and diluted with 146 parts of toluene and 146 parts of 2-propanol to obtain a polyamide resin (thermosetting resin 11) solution. The weight average molecular weight was 36,000, Tg was 5 ° C., and the acid value was 12 mgKOH / g.
［合成例１１］
攪拌機及び還流脱水装置を備えたフラスコに、ジカルボン酸成分としてダイマー酸（クローダージャパン社製、Ｐｒｉｐｏｌ１００９）１００重量部、及びジアミン成分としてピペラジン１４．８９重量部を仕込んだ。１１５℃／時間の割合で２３０℃にまで昇温し、６時間反応を継続してポリアミド樹脂（熱硬化性樹脂１２）を得た。重量平均分子量は２９,０００、Ｔｇは１５℃、酸価は７ｍｇＫＯＨ／ｇであった。
[Synthesis Example 11]
A flask equipped with a stirrer and a reflux dehydrator was charged with 100 parts by weight of dimer acid (Pripol 1009, manufactured by Croder Japan) as a dicarboxylic acid component, and 14.89 parts by weight of piperazine as a diamine component. The temperature was raised to 230 ° C. at a rate of 115 ° C./hour, and the reaction was continued for 6 hours to obtain a polyamide resin (thermosetting resin 12). The weight average molecular weight was 29,000, Tg was 15 ° C., and the acid value was 7 mgKOH / g.
合成例１〜１１で得られたバインダー樹脂を表２に示す。
＜導電性接着剤＞
［導電性接着剤１］
固形分換算で熱硬化性樹脂２を１００部、導電性微粒子１を６０部、エポキシ化合物を１０部、アジリジン化合物を０．５部容器に仕込み、不揮発分濃度が４０％になるように混合溶剤（トルエン：イソプロピルアルコール＝２：１（重量比））を加えディスパーで１０分攪拌して導電性接着剤１を得た。
<Conductive adhesive>
[Conductive adhesive 1]
100 parts of thermosetting resin 2 in terms of solid content, 60 parts of conductive fine particles 1, 10 parts of epoxy compound, 0.5 part of aziridine compound are mixed in a mixed solvent so that the nonvolatile content concentration is 40%. (Toluene: isopropyl alcohol = 2: 1 (weight ratio)) was added and stirred with a disper for 10 minutes to obtain a conductive adhesive 1.
［導電性接着剤２〜１５］
表３および４に記載した樹脂、導電性微粒子、および硬化剤の種類、および配合量に変更した以外は、実施例１の導電性接着剤１と同様にして、導電性接着剤２〜１５を得た。
[Conductive adhesive 2-15]
Except having changed into the kind of resin, electroconductive fine particle, and hardening | curing agent which were described in Table 3 and 4, and the compounding quantity, it carried out similarly to the electroconductive adhesive 1 of Example 1, and set the electroconductive adhesives 2-15. Obtained.
［実施例１］
導電性接着剤１をバーコーターで乾燥厚みが１０μｍになるように剥離性シート上に塗工し、１００℃の電気オーブンで２分間乾燥することで導電性接着剤層を得た。
尚、導電性接着剤層のガラス転移温度Ｔｇは−３℃であった。
[Example 1]
The conductive adhesive 1 was coated on the peelable sheet with a bar coater so as to have a dry thickness of 10 μm, and dried in an electric oven at 100 ° C. for 2 minutes to obtain a conductive adhesive layer.
The glass transition temperature Tg of the conductive adhesive layer was −3 ° C.
別途、固形分換算で熱硬化性樹脂２を１００部、エポキシ化合物１０部およびアジリジン硬化剤１部を加えディスパーで１０分攪拌することで絶縁性樹脂組成物１を得た。次いで得られた絶縁性樹脂組成物をバーコーターを使用して乾燥厚みが５μｍになるように、銅箔１に塗工し、１００℃の電気オーブンで２分間乾燥した後、絶縁層に微粘着剥離性シートを張り合わせた。
尚、この絶縁層のガラス転移温度Ｔｇは−５℃であった。
Separately, 100 parts of thermosetting resin 2 in terms of solid content, 10 parts of epoxy compound and 1 part of aziridine curing agent were added and stirred for 10 minutes with a disper to obtain insulating resin composition 1. Next, the obtained insulating resin composition was applied to copper foil 1 using a bar coater so that the dry thickness was 5 μm, dried in an electric oven at 100 ° C. for 2 minutes, and then slightly adhered to the insulating layer. A peelable sheet was laminated.
The insulating layer had a glass transition temperature Tg of −5 ° C.
次いで、銅箔１の銅キャリアを剥がし、銅箔面に導電性接着剤層を張り合わせることで、「剥離性シート／絶縁層／銅箔１／導電性接着剤層／剥離性シート」からなる電磁波シールドシートを得た。銅箔１と導電性接着剤層の貼り合せは、温度は９０℃、圧力は３ｋｇｆ／ｃｍ２で、熱ラミネーターにより貼り合わせた。 Next, the copper carrier of the copper foil 1 is peeled off, and a conductive adhesive layer is bonded to the copper foil surface, thereby comprising “peelable sheet / insulating layer / copper foil 1 / conductive adhesive layer / peelable sheet”. An electromagnetic wave shielding sheet was obtained. The copper foil 1 and the conductive adhesive layer were bonded at a temperature of 90 ° C. and a pressure of 3 kgf / cm 2 with a thermal laminator.
［実施例２〜１５、比較例１〜３］
実施例１の銅箔１を表１に記載した銅箔２〜銅箔１７または電解銅箔に変更した以外は、実施例１と同様に行うことで実施例２〜１５、比較例１〜３の電磁波シールドシートをそれぞれ得た。
[Examples 2-15, Comparative Examples 1-3]
Examples 2 to 15 and Comparative Examples 1 to 3 are carried out in the same manner as Example 1 except that the copper foil 1 of Example 1 is changed to the copper foil 2 to copper foil 17 or the electrolytic copper foil described in Table 1. Each electromagnetic shielding sheet was obtained.
［実施例１６］
導電性接着剤２をバーコーターで乾燥厚みが１０μｍになるように剥離性シート上に塗工し、１００℃の電気オーブンで２分間乾燥することで導電性接着剤層を得た。
[Example 16]
The conductive adhesive 2 was coated on the peelable sheet with a bar coater so as to have a dry thickness of 10 μm, and dried in an electric oven at 100 ° C. for 2 minutes to obtain a conductive adhesive layer.
別途、固形分換算で熱硬化性樹脂２を１００部、エポキシ化合物１０部およびアジリジン硬化剤１部を加えディスパーで１０分攪拌することで絶縁性樹脂組成物１を得た。次いで得られた絶縁性樹脂組成物１をバーコーターを使用して乾燥厚みが５μｍになるように、銅箔４に塗工し、１００℃の電気オーブンで２分間乾燥した後、絶縁層に微粘着剥離性シートを張り合わせた。
尚、この絶縁層のガラス転移温度は−５℃であった。
Separately, 100 parts of thermosetting resin 2 in terms of solid content, 10 parts of epoxy compound and 1 part of aziridine curing agent were added and stirred for 10 minutes with a disper to obtain insulating resin composition 1. Next, the obtained insulating resin composition 1 was coated on copper foil 4 using a bar coater so that the dry thickness was 5 μm, dried in an electric oven at 100 ° C. for 2 minutes, and then finely coated on the insulating layer. An adhesive peelable sheet was laminated.
The insulating layer had a glass transition temperature of −5 ° C.
次いで、銅箔４の銅キャリアを剥がし、銅箔面に導電性接着剤層を張り合わせることで、「剥離性シート／絶縁層／銅箔１／導電性接着剤層／剥離性シート」からなる電磁波シールドシートを得た。銅箔４と導電性接着剤層の貼り合せは、温度は９０℃、圧力は３ｋｇｆ／ｃｍ２で、熱ラミネーターにより貼り合わせた。 Next, the copper carrier of the copper foil 4 is peeled off, and a conductive adhesive layer is bonded to the copper foil surface, thereby comprising “peelable sheet / insulating layer / copper foil 1 / conductive adhesive layer / peelable sheet”. An electromagnetic wave shielding sheet was obtained. The copper foil 4 and the conductive adhesive layer were bonded at a temperature of 90 ° C. and a pressure of 3 kgf / cm 2 with a thermal laminator.
［実施例１７〜２９］
実施例１６のバインダー樹脂および導電性微粒子の量を表５〜８に記載した通りに変更した以外は、実施例１２と同様に行うことで実施例１７〜２９の電磁波シールドシートをそれぞれ得た。
[Examples 17 to 29]
The electromagnetic wave shielding sheets of Examples 17 to 29 were obtained in the same manner as in Example 12 except that the amounts of the binder resin and conductive fine particles in Example 16 were changed as described in Tables 5 to 8.
得られた電磁波シールドシートを用いて、下記評価を行った。結果を表５〜８に示す。
なお、表７および８中の「＊ガラス転移温度（Ｔｇ）差」とは、導電接着剤層と絶縁層のガラス転移温度（Ｔｇ）の温度の差分（℃）である。
＊ガラス転移温度（Ｔｇ）差＝｜導電接着剤層のＴｇ−絶縁層のＴｇ｜
The following evaluation was performed using the obtained electromagnetic wave shielding sheet. The results are shown in Tables 5-8.
“* Glass transition temperature (Tg) difference” in Tables 7 and 8 is the difference (° C.) between the glass transition temperature (Tg) of the conductive adhesive layer and the insulating layer.
* Glass transition temperature (Tg) difference = | Tg of conductive adhesive layer−Tg of insulating layer |
＜ハンダリフロー耐性＞
ハンダリフロー耐性は、電磁波シールドシートと溶融半田とを接触させた後の、外観変化の有無により評価した。ハンダリフロー耐性が高い電磁波シールドシートは、外観が変化しないが、ハンダリフロー耐性が低い電磁波シールドシートは、発泡や剥がれが発生する。
まず、幅２５ｍｍ・長さ７０ｍｍの電磁波シールドシートの導電性接着剤層の剥離性シートを剥がし、露出した導電性接着剤層と、総厚６４μｍの金メッキ処理された銅張積層板（金メッキ０．３μｍ／ニッケルメッキ１μｍ／銅箔１８μｍ／接着剤２０μｍ／ポリイミドフィルム２５μｍ）の金メッキ面を１５０℃、２．０ＭＰａ、３０分の条件で圧着し、熱硬化させて積層体を得た。得られた積層体を幅１０ｍｍ・縦６５ｍｍの大きさに切り取り試料を作製した。得られた試料を４０℃、９０％ＲＨの雰囲気下で７２時間放置した。その後、試料のポリイミドフィルム面を下にして２５０℃の溶融半田上に１分間浮かべ、次いで試料を取り出し、その外観を目視で観察し、発泡、浮き、剥がれ等の異常の有無を次の基準で評価した。
◎：外観変化全く無し。
〇：小さな発泡がわずかに観察される。
△：小さな発泡が多数観察される。
×：激しい発泡や剥がれが観察される。
<Solder reflow resistance>
Solder reflow resistance was evaluated by the presence or absence of changes in appearance after contacting the electromagnetic wave shielding sheet and the molten solder. The appearance of the electromagnetic wave shielding sheet having high solder reflow resistance does not change, but the electromagnetic wave shielding sheet having low solder reflow resistance causes foaming or peeling.
First, the peelable sheet of the conductive adhesive layer of the electromagnetic shield sheet having a width of 25 mm and a length of 70 mm was peeled off, and the exposed conductive adhesive layer and a copper-clad laminate (gold plated 0. A gold-plated surface of 3 μm / nickel plating 1 μm / copper foil 18 μm / adhesive 20 μm / polyimide film 25 μm) was pressure-bonded under the conditions of 150 ° C., 2.0 MPa, 30 minutes, and thermally cured to obtain a laminate. The obtained laminate was cut into a size of 10 mm width and 65 mm length to prepare a sample. The obtained sample was left for 72 hours in an atmosphere of 40 ° C. and 90% RH. Then, float on the molten solder at 250 ° C. for 1 minute with the polyimide film surface of the sample facing down, then take out the sample, visually observe its appearance, and check for the presence or absence of abnormalities such as foaming, floating, and peeling according to the following criteria. evaluated.
A: No change in appearance.
A: Small foaming is slightly observed.
Δ: Many small bubbles are observed.
X: Vigorous foaming and peeling are observed.
＜電磁波シールド性＞
電磁波シールド性は、クロストークを測定して評価した。クロストークは以下の測定用試料を用いて評価した。
（コプレーナ回路を有する配線板の製造）
図３に、測定に用いたコプレーナ回路を有するフレキシブルプリント配線板（以下、コプレーナ回路を有する配線板ともいう）２０の主面側の模式的平面図を、図４に、裏面側の模式的平面図を示す。まず、厚さ５０μｍのポリイミドフィルム５０の両面に、厚さ１２μｍの圧延銅箔を積層した両面ＣＣＬ「Ｒ−Ｆ７７５」（パナソニック社製）を用意した。そして、矩形状の４つのコーナー部近傍に、其々６か所のスルーホール５１（直径０．１ｍｍ）を設けた。尚、図中においては、図示の便宜上、各コーナー部にスルーホール５１を２つのみ示している。次いで、無電解メッキ処理を行った後に、電解メッキ処理を行って１０μｍの銅メッキ膜５２を形成し、スルーホール５１を介して両主面間の導通を確保した。その後、図３に示すように、ポリイミドフィルム５０の主面に長さが１０ｃｍの２本の信号配線５３、およびその外側に信号配線５３と並行なグランド配線５４、およびグランド配線５４から延在され、ポリイミドフィルム５０短手方向のスルーホール５１を含む領域にグランドパターン（ｉ）５５を形成した。
<Electromagnetic wave shielding>
The electromagnetic wave shielding property was evaluated by measuring crosstalk. Crosstalk was evaluated using the following measurement samples.
(Manufacture of wiring boards with coplanar circuits)
FIG. 3 is a schematic plan view of a main surface side of a flexible printed wiring board (hereinafter, also referred to as a wiring board having a coplanar circuit) 20 having a coplanar circuit used for measurement, and FIG. 4 is a schematic plan view of a back surface side. The figure is shown. First, double-sided CCL “R-F775” (manufactured by Panasonic Corporation) in which a rolled copper foil having a thickness of 12 μm was laminated on both sides of a polyimide film 50 having a thickness of 50 μm was prepared. And six through holes 51 (diameter 0.1 mm) were provided in the vicinity of the four rectangular corner portions. In the drawing, for convenience of illustration, only two through holes 51 are shown at each corner. Next, after performing an electroless plating process, an electroplating process was performed to form a 10 μm copper plating film 52, and conduction between both main surfaces was ensured through the through holes 51. Thereafter, as shown in FIG. 3, two signal wirings 53 having a length of 10 cm are formed on the main surface of the polyimide film 50, and a ground wiring 54 parallel to the signal wiring 53 and the ground wiring 54 are extended outside thereof. The ground pattern (i) 55 was formed in a region including the through-hole 51 in the short direction of the polyimide film 50.
その後、ポリイミドフィルム５０の裏面に形成された銅箔をエッチングして、グランドパターン（ｉ）５５に対応する位置に、図４に示すような裏面側グランドパターン（ｉｉ）５６を得た。回路の外観、公差の検査仕様はＪＰＣＡ規格（ＪＰＣＡ−ＤＧ０２）とした。次に、ポリイミドフィルム５０の主面側に、ポリイミドフィルム８ａ（厚さ１２．５μｍ）と絶縁性接着剤層８ｂ（厚さ１５μｍ）とで構成されるカバーコート層８「ＣＩＳＶ１２１５（ニッカン工業社製）」を貼り付けた（図３参照）。尚、図３においては、信号配線５３等の構造がわかるように、カバーコート層８を透視図で示した。その後、カバーコート層８から露出した銅箔パターンにニッケルメッキ（不図示）を行い、次いで金メッキ（不図示）処理を行った。 Thereafter, the copper foil formed on the back surface of the polyimide film 50 was etched to obtain a back surface side ground pattern (ii) 56 as shown in FIG. 4 at a position corresponding to the ground pattern (i) 55. The inspection specification of the appearance and tolerance of the circuit was the JPCA standard (JPCA-DG02). Next, on the main surface side of the polyimide film 50, a cover coat layer 8 “CISV1215 (manufactured by Nikkan Kogyo Co., Ltd.) composed of a polyimide film 8a (thickness 12.5 μm) and an insulating adhesive layer 8b (thickness 15 μm). ) ”Was pasted (see FIG. 3). In FIG. 3, the cover coat layer 8 is shown in a perspective view so that the structure of the signal wiring 53 and the like can be understood. Thereafter, the copper foil pattern exposed from the cover coat layer 8 was subjected to nickel plating (not shown), and then gold plating (not shown).
次に図５に示すように、導電性接着剤層１、金属層２、絶縁層３の積層体からなる電磁波シールドシート１０を用意し、電磁波シールドシート１０の導電性接着剤層１上に設けられた剥離処理シート（不図示）を剥がした。そして、電磁波シールドシート１０の導電性接着剤層１を内側としてコプレーナ回路を有する配線板２０の裏全面側に、１５０℃、２．０ＭＰａ、３０分の条件で圧着することにより電磁波シールドシート付きコプレーナ回路を有する配線板２０を得た。図５においては、裏面側グランドパターン（ｉｉ）５６を透視図で示した。 Next, as shown in FIG. 5, an electromagnetic wave shielding sheet 10 composed of a laminate of the conductive adhesive layer 1, the metal layer 2, and the insulating layer 3 is prepared and provided on the conductive adhesive layer 1 of the electromagnetic wave shielding sheet 10. The obtained release treatment sheet (not shown) was peeled off. Then, the coplanar with an electromagnetic wave shielding sheet is bonded to the entire back surface side of the wiring board 20 having a coplanar circuit with the conductive adhesive layer 1 of the electromagnetic wave shielding sheet 10 as an inner side at 150 ° C., 2.0 MPa, for 30 minutes. A wiring board 20 having a circuit was obtained. In FIG. 5, the back surface side ground pattern (ii) 56 is shown in a perspective view.
（マイクロストリップライン回路を有する配線板の製造）
別途、図６及び図７に示すようにマイクロストリップライン回路を有する配線板３０を作製した。まず、厚さ１２μｍの圧延銅箔を積層した両面ＣＣＬ「Ｒ−Ｆ７７５」（パナソニック社製）を用意した。そして、一方の面に長さが１０ｃｍの２本の信号配線３５をエッチングによって形成した。回路の外観、公差の検査仕様はＪＰＣＡ規格（ＪＰＣＡ−ＤＧ０２）とした。次に、信号配線３５側に、ポリイミドフィルム３１ａ（厚さ１２．５μｍ）と絶縁性接着剤層３１ｂ（厚さ１５μｍ）とで構成されるカバーレイ３１「ＣＩＳＶ１２１５（ニッカン工業社製）」を貼り付けた（図６参照）。尚、図６においては、信号配線３５等の構造がわかるように、カバーレイ３１を透視図で示した。その後、カバーレイ３１から露出した信号配線３５にニッケルメッキ（不図示）を行い、次いで金メッキ（不図示）処理を行った。また、ポリイミドフィルム３３の裏面側にはグランド層３４が設けられている。
(Manufacture of wiring boards having microstrip line circuits)
Separately, a wiring board 30 having a microstrip line circuit was produced as shown in FIGS. First, double-sided CCL “R-F775” (manufactured by Panasonic Corporation) in which rolled copper foil having a thickness of 12 μm was laminated was prepared. Then, two signal wirings 35 having a length of 10 cm were formed on one surface by etching. The inspection specification of the appearance and tolerance of the circuit was the JPCA standard (JPCA-DG02). Next, a coverlay 31 “CISV1215 (manufactured by Nikkan Kogyo)” composed of a polyimide film 31a (thickness 12.5 μm) and an insulating adhesive layer 31b (thickness 15 μm) is attached to the signal wiring 35 side. (See FIG. 6). In FIG. 6, the coverlay 31 is shown in a perspective view so that the structure of the signal wiring 35 and the like can be understood. Thereafter, the signal wiring 35 exposed from the coverlay 31 was subjected to nickel plating (not shown) and then gold plating (not shown). A ground layer 34 is provided on the back side of the polyimide film 33.
（テストピースの作製）
次いで、マイクロストリップライン回路を有する配線板３０の信号配線３５側とコプレーナ回路を有する配線板２０の電磁波シールドシート１０側とが接触するように積層させ治具で固定した。積層体の模式的平面図を図８及び図９に示す。図８は図３のＸＩ−ＸＩ切断部断面図に相当し、図９は図３のＸＩＩ−ＸＩＩ切断部断面図に相当する。
マイクロストリップライン回路を有する配線板３０の露出した信号配線３５と、コプレーナ回路を有する配線板２０の露出した信号配線５３にネットワークアナライザＥ５０７１Ｃ（アジレント・ジャパン社製）を接続し、マイクロストリップライン回路を有する配線板３０の信号配線３５には１０ＭＨｚ〜２０ＧＨｚのサイン波を入力し、その時のコプレーナ回路を有する配線板２０におけるクロストークを測定し、この値によって電磁波シールド性の影響を確認した。
尚、信号配線３５のＬ／Ｓ（ライン／スペース）は特性インピーダンスが±５Ωに入るよう適宜調整した。グランド配線５４の幅は１００μｍ、グランド配線５４と信号配線５３の間の距離は１ｍｍとした。
実施例９、１１及び、比較例２の測定データを図１１に示す。
測定したクロストークを下記の基準で評価した。
◎：１０ＧＨｚにおけるクロストークが−５５ｄＢ未満
〇：１０ＧＨｚにおけるクロストークが−５５ｄＢ以上、−４５ｄＢ未満
×：１０ＧＨｚにおけるクロストークが−４５ｄＢ以上
(Production of test piece)
Next, the wiring board 30 having the microstrip line circuit was laminated so that the signal wiring 35 side of the wiring board 30 and the electromagnetic wave shielding sheet 10 side of the wiring board 20 having the coplanar circuit were in contact with each other, and fixed with a jig. A schematic plan view of the laminate is shown in FIGS. 8 corresponds to a cross-sectional view taken along line XI-XI in FIG. 3, and FIG. 9 corresponds to a cross-sectional view taken along line XII-XII in FIG.
A network analyzer E5071C (manufactured by Agilent Japan) is connected to the exposed signal wiring 35 of the wiring board 30 having the microstripline circuit and the exposed signal wiring 53 of the wiring board 20 having the coplanar circuit, and the microstripline circuit is connected. A sine wave of 10 MHz to 20 GHz was input to the signal wiring 35 of the wiring board 30 having the crosstalk in the wiring board 20 having the coplanar circuit at that time, and the influence of the electromagnetic wave shielding property was confirmed by this value.
The L / S (line / space) of the signal wiring 35 was adjusted as appropriate so that the characteristic impedance was within ± 5Ω. The width of the ground wiring 54 was 100 μm, and the distance between the ground wiring 54 and the signal wiring 53 was 1 mm.
The measurement data of Examples 9 and 11 and Comparative Example 2 are shown in FIG.
The measured crosstalk was evaluated according to the following criteria.
A: Crosstalk at 10 GHz is less than -55 dB O: Crosstalk at 10 GHz is -55 dB or more, less than -45 dB X: Crosstalk at 10 GHz is -45 dB or more
＜メッキ液耐性＞
幅４０ｍｍ・長さ４０ｍｍの電磁波シールドシートの導電性接着剤層の剥離性シートを剥がし、露出した導電性接着剤層と、幅５０ｍｍ・長さ５０ｍｍカプトン５００Ｈを１５０℃、２．０ＭＰａ、３０分の条件で圧着し、熱硬化させて積層体を得た。得られた積層体の電磁波シールドシートの絶縁層側に、ＪＩＳＫ５４００に準じてクロスカットガイドを使用し、間隔が１ｍｍの碁盤目を１００個作成した。その後、１０％塩酸水溶液に２０分浸漬させ、水洗いを行った後乾燥させた。碁盤目部に粘着テープを強く圧着させ、テープの端を４５°の角度で一気に引き剥がし、碁盤目の状態を下記の基準で判断した。
◎：どの格子の目も剥がれない。
〇：カットの交差点における塗膜の小さな剥がれ。明確に５％を上回らない。
△：塗膜がカットの線に沿って部分的、全面的に剥がれている。１５％以上３５％未満。×：塗膜がカットの線に沿って部分的、全面的に剥がれている。３５％以上。
<Plating solution resistance>
Peel off the peelable sheet of the conductive adhesive layer of the 40 mm wide and 40 mm long electromagnetic shield sheet, and expose the exposed conductive adhesive layer and the 50 mm wide and 50 mm long Kapton 500H at 150 ° C., 2.0 MPa, 30 minutes. The laminate was obtained by pressure bonding under the above conditions and thermosetting. On the insulating layer side of the electromagnetic wave shielding sheet of the obtained laminate, a cross cut guide was used according to JISK5400, and 100 grids with an interval of 1 mm were created. Then, it was immersed in a 10% hydrochloric acid aqueous solution for 20 minutes, washed with water and then dried. The adhesive tape was strongly pressed against the grid area, the ends of the tape were peeled off at a 45 ° angle, and the grid pattern was judged according to the following criteria.
A: The eyes of any lattice are not peeled off.
○: Small peeling of the coating film at the intersection of cuts. Clearly not exceed 5%.
(Triangle | delta): The coating film has peeled off partially and entirely along the line of cut. 15% or more and less than 35%. X: The coating film is peeled off partially or entirely along the cut line. 35% or more.
＜反発力＞
反発力はＪＰＣＡ−ＴＭ００２ ８．４．２に記載の試験条件に準じてスティフネス（ｓｔｉｆｆｎｅｓｓ）値を測定して評価した。ＪＰＣＡ−ＴＭ００２ ８．４．２に記載のパターンＡ（Ｌ／Ｓ：１．０／１．０ｍｍ、ライン数：３往復（六本））の片面ＣＣＬを用意した。次いで、電磁波シールドシートを幅２ｃｍ・長さ６ｃｍの大きさに準備し試料とした。導電性接着剤層側の剥離性シートを剥がし、前述の片面ＣＣＬと１５０℃、２ＭＰａ、３０ｍｉｎの条件で圧着させた後、幅１．５ｃｍ、長さ３ｃｍにカットして絶縁層側の剥離性シートを剥がし、ＪＰＣＡ−ＴＭ００２ ８．４．２に記載の試験条件にてスティフネス（ｓｔｉｆｆｎｅｓｓ）値を測定した。なお結果は以下の判定基準に従い評価した。なお、反発力が高すぎると、例えばＦＰＣを折り曲げて電子機器の内部に収納する場合、ＦＰＣの信号配線に負担が掛かり、断線する恐れがあるなどのデメリットがある。
◎ ： 反発力が５０ｍＮ／ｍｍ未満。非常に良好な結果である。
○ ： 反発力が５０ｍＮ／ｍｍ以上、１００ｍＮ／ｍｍ未満。良好な結果である。
△ ： 反発力が１００ｍＮ／ｍｍ以上、１５０ｍＮ／ｍｍ未満。実用上問題ない。
× ： 反発力が１５０ｍＮ／ｍｍ以上。実用不可。
<Repulsive force>
The repulsive force was evaluated by measuring the stiffness value according to the test conditions described in JPCA-TM002 8.4.2. A single-sided CCL of pattern A (L / S: 1.0 / 1.0 mm, number of lines: 3 reciprocations (six)) described in JPCA-TM002 8.4.2 was prepared. Next, an electromagnetic wave shielding sheet was prepared in a size of 2 cm wide and 6 cm long to prepare a sample. The peelable sheet on the side of the conductive adhesive layer is peeled off and bonded to the above-mentioned single-sided CCL under the conditions of 150 ° C., 2 MPa, 30 min, then cut to a width of 1.5 cm and a length of 3 cm to peel off the insulating layer side. The sheet was peeled off, and the stiffness value was measured under the test conditions described in JPCA-TM002 8.4.2. The results were evaluated according to the following criteria. If the repulsive force is too high, for example, when the FPC is bent and stored inside the electronic device, there is a demerit that the signal wiring of the FPC is burdened and may be disconnected.
A: Repulsive force is less than 50 mN / mm. Very good result.
○: Repulsive force is 50 mN / mm or more and less than 100 mN / mm. It is a good result.
(Triangle | delta): Repulsive force is 100 mN / mm or more and less than 150 mN / mm. There is no problem in practical use.
X: Repulsive force is 150 mN / mm or more. Not practical.
＜折り曲げ後の接続信頼性＞
電磁波シールドシートを幅２０ｍｍ、長さ５０ｍｍの大きさに準備し試料２５とした。図１０（１）の平面図を示して説明すると電磁波シールドシート２５から剥離性シートを剥がし、露出した導電性接着剤層２５ｂを、別に作製したフレキシブルプリント配線板（厚み２５μｍのポリイミドフィルム２１上に、互いに電気的に接続されていない厚み１８μｍの銅箔回路２２Ａ、および銅箔回路２２Ｂが形成されており、銅箔回路２２Ａ上に、厚み３７．５μｍの、直径１．６ｍｍのスルーホール２４を有する接着剤付きポリイミドカバーレイ２３が積層された配線板）に１５０℃、２ＭＰａ、３０分の条件で圧着し、電磁波シールドシートの導電性接着剤層２５ｂおよび絶縁層２５ａを硬化させることで試料を得た。次いで、試料の絶縁層２５ａ側の剥離性シートを除去し、図１０（４）の平面図に示す２２Ａ−２２Ｂ間の初期接続抵抗値を、三菱化学製「ロレスターＧＰ」のＢＳＰプローブを用いて測定した。その後、図１０（４）の平面図に示すＥ−Ｅ’に沿って山折りを１０回繰り返した後、２２Ａ−２２Ｂ間の折り曲げ後の接続抵抗値を測定した。下記式で算出した値を折り曲げ後の接続信頼性として評価した。なお、図１０（２）は、図１０（１）のＤ−Ｄ’断面図、図１０（３）は図１０（１）のＣ−Ｃ’断面図である。同様に図１０（５）は、図１０（４）のＤ−Ｄ’断面図、図１０（６）は図１０（４）のＣ−Ｃ’断面図である。折り曲げ後の接続信頼性の評価基準は以下の通りである。
折り曲げ後の接続信頼性（％）＝折り曲げ後の接続抵抗値／初期接続抵抗値×１００
◎：２００％未満 非常に良好な結果である。
○：２００％以上４００％未満 良好な結果である。
△：４００％以上６００％未満 実用上問題ない。
×：６００％以上 実用不可
<Connection reliability after bending>
An electromagnetic wave shielding sheet having a width of 20 mm and a length of 50 mm was prepared as Sample 25. The plan view of FIG. 10A will be described. The peelable sheet is peeled off from the electromagnetic shielding sheet 25, and the exposed conductive adhesive layer 25b is formed on a separately prepared flexible printed wiring board (polyimide film 21 having a thickness of 25 μm). A copper foil circuit 22A and a copper foil circuit 22B having a thickness of 18 μm that are not electrically connected to each other are formed, and a through hole 24 having a diameter of 1.6 mm and a thickness of 37.5 μm is formed on the copper foil circuit 22A. The polyimide cover lay 23 with adhesive having a laminated structure is pressure-bonded at 150 ° C. and 2 MPa for 30 minutes to cure the conductive adhesive layer 25b and the insulating layer 25a of the electromagnetic wave shielding sheet. Obtained. Next, the peelable sheet on the insulating layer 25a side of the sample was removed, and the initial connection resistance value between 22A and 22B shown in the plan view of FIG. 10 (4) was measured using a BSP probe of “Lorester GP” manufactured by Mitsubishi Chemical. It was measured. Then, after repeating mountain folding 10 times along EE ′ shown in the plan view of FIG. 10 (4), the connection resistance value after bending between 22A and 22B was measured. The value calculated by the following formula was evaluated as the connection reliability after bending. 10 (2) is a sectional view taken along the line DD ′ of FIG. 10 (1), and FIG. 10 (3) is a sectional view taken along the line CC ′ of FIG. 10 (1). Similarly, FIG. 10 (5) is a DD ′ sectional view of FIG. 10 (4), and FIG. 10 (6) is a CC ′ sectional view of FIG. 10 (4). The evaluation criteria for the connection reliability after bending are as follows.
Connection reliability after bending (%) = connection resistance value after bending / initial connection resistance value × 100
A: Less than 200% Very good result.
○: 200% or more and less than 400% Good results.
Δ: 400% or more and less than 600% No problem in practical use.
X: 600% or more
１ 導電性接着剤層
２ 金属層
３ 絶縁層
４ 開口部
５ グランド配線
６ 信号配線
７ プリント配線板
８ カバーコート層
９ 絶縁性基材
１０ 電磁波シールドシート
１１ 穴
２０ コプレーナ回路を有する配線板
３０ マイクロストリップライン回路を有する配線板
３１ カバーレイ
３４ グランド層
３５ 信号配線
３３、５０ ポリイミドフィルム
５１ スルーホール
５２ 銅メッキ膜
５３ 信号配線
５４ グランド配線
５５ グランドパターン（ｉ）
５６ 裏面側グランドパターン（ｉｉ）
DESCRIPTION OF SYMBOLS 1 Conductive adhesive layer 2 Metal layer 3 Insulating layer 4 Opening part 5 Ground wiring 6 Signal wiring 7 Printed wiring board 8 Cover coat layer 9 Insulating base material 10 Electromagnetic wave shielding sheet 11 Hole 20 Wiring board 30 with a coplanar circuit Microstrip Wiring board 31 having line circuit Coverlay
34 Ground layer 35 Signal wiring 33, 50 Polyimide film 51 Through hole 52 Copper plating film 53 Signal wiring 54 Ground wiring 55 Ground pattern (i)
56 Back side ground pattern (ii)
Claims (10)
前記金属層は、面積０．７〜５０００μｍ２の開口部を１００〜２０００００個／ｃｍ２有し、かつ金属層の開口部において、下記数式（１）から求められるｗが０．８〜２．２であることを特徴とする電磁波シールドシート。
Ｗは、平均最近隣距離、Ｅ［Ｗ］は、平均最近隣距離の期待値であり、下記数式（２）および数式（３）によって求めることができる値である。
ｄiは、開口部の中心点iから最近隣の開口部の中心点までの距離であり、ｎは、金属層の面積Ｓ中の開口部の個数である。 It is composed of an insulating layer, a metal layer, and a conductive adhesive layer,
The metal layer has 100 to 200000 openings / cm 2 having an area of 0.7 to 5000 μm 2 , and w obtained from the following formula (1) is 0.8 to 2 in the opening of the metal layer. 2. An electromagnetic wave shielding sheet, wherein
W is the average nearest neighbor distance, and E [W] is an expected value of the average nearest neighbor distance, which is a value that can be obtained by the following formulas (2) and (3).
di is the distance from the center point i of the opening to the center point of the nearest opening, and n is the number of openings in the area S of the metal layer.
電磁波シールドシート。 The electromagnetic wave shielding sheet according to any one of claims 1 to 4, wherein the repulsive force is 30 mN / mm or less.
電磁波シールド層は、絶縁層と金属層と導電性接着剤層とから構成される電磁波シールドシートを熱圧着してなり、
金属層は、面積０．７〜５０００μｍ２の開口部を１００〜２０００００個／ｃｍ２有し、かつ金属層の開口部において、下記数式（１）から求められるｗが０．８〜２．２であって、
配線板は、絶縁性基材の表面に信号配線とグランド配線とを有する回路パターンを有し、
前記配線板上に、信号配線とグランド配線とを絶縁保護し、グランド配線上の少なくとも一部に開口部を有するカバーコート層を形成し、
前記電磁波シールドシートの導電性接着剤層面を、前記カバーコート層上に配置した後、前記電磁波シールドシートを熱圧着し、金属層の開口部内部において、導電性接着剤層と絶縁層とを互いに流入させ開口部の内部で接着させる、プリント配線板の製造方法。
Ｗは、平均最近隣距離、Ｅ［Ｗ］は、平均最近隣距離の期待値であり、下記数式（２）および数式（３）によって求めることができる値である。
ｄiは、開口部の中心点iから最近隣の開口部の中心点までの距離であり、ｎは、金属層の面積Ｓ中の開口部の個数である。 A method for producing a printed wiring board comprising an electromagnetic wave shielding layer, a cover coat layer, and a wiring board,
The electromagnetic shielding layer is formed by thermocompression bonding of an electromagnetic shielding sheet composed of an insulating layer, a metal layer, and a conductive adhesive layer.
The metal layer has 100 to 200000 openings / cm 2 having an area of 0.7 to 5000 μm 2 , and w obtained from the following formula (1) is 0.8 to 2.2 in the opening of the metal layer. Because
The wiring board has a circuit pattern having signal wiring and ground wiring on the surface of the insulating substrate,
On the wiring board, the signal wiring and the ground wiring are insulated and protected, and a cover coat layer having an opening in at least a part of the ground wiring is formed,
After the conductive adhesive layer surface of the electromagnetic wave shielding sheet is disposed on the cover coat layer, the electromagnetic wave shielding sheet is thermocompression bonded, and the conductive adhesive layer and the insulating layer are mutually bonded inside the opening of the metal layer. A method for producing a printed wiring board, wherein the printed wiring board is allowed to flow and adhere inside the opening.
W is the average nearest neighbor distance, and E [W] is an expected value of the average nearest neighbor distance, which is a value that can be obtained by the following formulas (2) and (3).
di is the distance from the center point i of the opening to the center point of the nearest opening, and n is the number of openings in the area S of the metal layer.
電磁波シールド層は、絶縁層と金属層と導電性接着剤層とから構成される電磁波シールドシートを熱圧着してなり、
金属層は、面積０．７〜５０００μｍ２の開口部を、１００〜２０００００個／ｃｍ２有し、かつ金属層の開口部において、下記数式（１）から求められるｗが０．８〜２．２であって、
配線板は、絶縁性基材の表面に信号配線とグランド配線とを有する回路パターンを有し、裏面にグランドパターンを有し、スルーホールを介してグランド配線とグランドパターンが導通しており、
前記配線板の絶縁性基材表面上に、前記回路パターンを絶縁保護するカバーコート層を形成し、
前記電磁波シールドシートの導電性接着剤層面を、絶縁性基材裏面のグランドパターンを含む裏面全面に配置した後、前記電磁波シールドシートを熱圧着し、金属層の開口部内部において、導電性接着剤層と絶縁層とを互いに流入させ開口部の内部で接着させる、プリント配線板の製造方法。
Ｗは、平均最近隣距離、Ｅ［Ｗ］は、平均最近隣距離の期待値であり、下記数式（２）および数式（３）によって求めることができる値である。
ｄiは、開口部の中心点iから最近隣の開口部の中心点までの距離であり、ｎは、金属層の面積Ｓ中の開口部の個数である。 A method for producing a printed wiring board comprising an electromagnetic wave shielding layer, a cover coat layer, and a wiring board,
The electromagnetic shielding layer is formed by thermocompression bonding of an electromagnetic shielding sheet composed of an insulating layer, a metal layer, and a conductive adhesive layer.
The metal layer has 100 to 200000 / cm 2 openings with an area of 0.7 to 5000 μm 2 , and w obtained from the following mathematical formula (1) is 0.8 to 2 in the openings of the metal layer. 2
The wiring board has a circuit pattern having a signal wiring and a ground wiring on the surface of the insulating substrate, has a ground pattern on the back surface, and the ground wiring and the ground pattern are conducted through a through hole,
On the insulating substrate surface of the wiring board, a cover coat layer for insulating and protecting the circuit pattern is formed,
After the conductive adhesive layer surface of the electromagnetic wave shielding sheet is disposed on the entire back surface including the ground pattern on the back surface of the insulating base material, the electromagnetic wave shielding sheet is thermocompression-bonded, and the conductive adhesive is formed inside the opening of the metal layer. A method of manufacturing a printed wiring board, wherein a layer and an insulating layer are caused to flow into each other and adhered inside the opening.
W is the average nearest neighbor distance, and E [W] is an expected value of the average nearest neighbor distance, which is a value that can be obtained by the following formulas (2) and (3).
di is the distance from the center point i of the opening to the center point of the nearest opening, and n is the number of openings in the area S of the metal layer.
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| JP6202177B1 (en) | 2017-09-27 |
| JP2018060987A (en) | 2018-04-12 |
| JP6645484B2 (en) | 2020-02-14 |
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