TWI734574B - Electromagnetic wave shielding sheet and electromagnetic wave shielding wiring circuit board - Google Patents
Electromagnetic wave shielding sheet and electromagnetic wave shielding wiring circuit board Download PDFInfo
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- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K1/00—Printed circuits
- H05K1/02—Details
- H05K1/0213—Electrical arrangements not otherwise provided for
- H05K1/0216—Reduction of cross-talk, noise or electromagnetic interference
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- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K9/00—Screening of apparatus or components against electric or magnetic fields
- H05K9/0073—Shielding materials
- H05K9/0081—Electromagnetic shielding materials, e.g. EMI, RFI shielding
- H05K9/0084—Electromagnetic shielding materials, e.g. EMI, RFI shielding comprising a single continuous metallic layer on an electrically insulating supporting structure, e.g. metal foil, film, plating coating, electro-deposition, vapour-deposition
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J7/00—Adhesives in the form of films or foils
- C09J7/20—Adhesives in the form of films or foils characterised by their carriers
- C09J7/29—Laminated material
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J9/00—Adhesives characterised by their physical nature or the effects produced, e.g. glue sticks
- C09J9/02—Electrically-conducting adhesives
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- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K1/00—Printed circuits
- H05K1/02—Details
- H05K1/0213—Electrical arrangements not otherwise provided for
- H05K1/0216—Reduction of cross-talk, noise or electromagnetic interference
- H05K1/0218—Reduction of cross-talk, noise or electromagnetic interference by printed shielding conductors, ground planes or power plane
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- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K2201/00—Indexing scheme relating to printed circuits covered by H05K1/00
- H05K2201/07—Electric details
- H05K2201/0707—Shielding
- H05K2201/0715—Shielding provided by an outer layer of PCB
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- Microelectronics & Electronic Packaging (AREA)
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- Shielding Devices Or Components To Electric Or Magnetic Fields (AREA)
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Abstract
本發明提供一種具有回流焊耐性及優良的冷熱循環可靠性且具有優異的高頻屏蔽性與良好的彎折耐性的電磁波屏蔽片、及使用了所述電磁波屏蔽片的配線電路基板。通過一種電磁波屏蔽片得到解決,所述電磁波屏蔽片的特徵在於,包括導電黏接劑層、金屬層與保護層,所述金屬層的與導電黏接劑層相接的所述金屬層的界面中,依據ISO 7668而求出的60°鏡面光澤度為10~800,且,所述金屬層具有多個開口部,且開口率為0.10%~20%。The present invention provides an electromagnetic wave shielding sheet having reflow resistance and excellent cold-heat cycle reliability, excellent high-frequency shielding properties and good bending resistance, and a wiring circuit board using the electromagnetic wave shielding sheet. It is solved by an electromagnetic wave shielding sheet, the electromagnetic wave shielding sheet is characterized in that it includes a conductive adhesive layer, a metal layer and a protective layer, and the interface of the metal layer and the conductive adhesive layer is connected to the metal layer Among them, the 60° specular gloss determined in accordance with ISO 7668 is 10 to 800, and the metal layer has a plurality of openings, and the opening ratio is 0.10% to 20%.
Description
本發明是有關於一種電磁波屏蔽片及電磁波屏蔽性配線電路基板,例如是有關於一種適合於與放出電磁波的零件的一部分接合來利用的電磁波屏蔽片(electromagnetic wave shielding sheet)以及使用了電磁波屏蔽片的電磁波屏蔽性配線電路基板。The present invention relates to an electromagnetic wave shielding sheet and an electromagnetic wave shielding wiring circuit board. For example, it relates to an electromagnetic wave shielding sheet suitable for use in joining with a part of a part that emits electromagnetic waves and uses an electromagnetic wave shielding sheet The electromagnetic wave shielding wiring circuit board.
以移動終端、個人電腦(personal computer,PC)、服務器(server)等為代表的各種電子設備中內置有印刷電路(printed wiring board)等配線電路基板。為了防止由來自外部的磁場或電波引起的誤動作,而且為了減少來自電氣信號的無用輻射,而在這些配線電路基板上設置有電磁波屏蔽結構。Various electronic devices represented by mobile terminals, personal computers (PC), servers, etc. have built-in wiring circuit boards such as printed wiring boards. In order to prevent malfunctions caused by external magnetic fields or electric waves, and to reduce unnecessary radiation from electrical signals, electromagnetic wave shielding structures are provided on these printed circuit boards.
隨著傳輸信號的高速傳輸化,也要求電磁波屏蔽片具有應對高頻雜訊的電磁波屏蔽性(以下,高頻屏蔽性)及減少高頻區域中的傳輸損耗(以下,有時稱為傳輸特性)。在專利文獻1中,公開了以層壓狀態具備厚度為0.5 μm~12 μm的金屬層、與各向異性導電黏接劑層的構成。並且記載了,根據此構成,會良好地遮蔽從電磁波屏蔽片的一面側向另一面側行進的電場波、磁場波及電磁波,並且減少傳輸損耗。
[現有技術文獻]With the high-speed transmission of transmission signals, electromagnetic wave shielding sheets are also required to have electromagnetic wave shielding properties against high-frequency noise (hereinafter, high-frequency shielding properties) and reduce transmission loss in the high-frequency region (hereinafter, sometimes referred to as transmission characteristics) ).
[專利文獻] [專利文獻1] 國際公開第2013/077108號 [專利文獻2] 日本專利特開2013-168643號公報[Patent Literature] [Patent Document 1] International Publication No. 2013/077108 [Patent Document 2] Japanese Patent Laid-Open No. 2013-168643
[發明所要解決的問題]
近年來,在以行動電話為代表的電子設備中,隨著傳輸信號的高速傳輸化,也要求這些中所內置的配線電路基板上的電磁波屏蔽片具有高頻屏蔽性及傳輸特性。因此,一直認為較佳的是在電磁波屏蔽片的導電層中像專利文獻1中所記載的那樣使用厚度為0.5 μm~12 μm的金屬層。
然而,將使用有金屬層的電磁波屏蔽片貼附於配線電路基板而成的電磁波屏蔽性配線電路基板存在如下的問題(以下,有時稱為回流焊耐性):在進行回流焊等加熱處理時,因從配線電路基板的內部產生的揮發成分而在層間發生浮起,並因發泡等而導致外觀不良及連接不良。針對此問題,例如在專利文獻2中是通過使用在金屬薄膜層具有多個針孔的金屬箔,使揮發成分從金屬薄膜層的針孔透過,而抑制了層間的浮起或發泡。
而且,電磁波屏蔽片的金屬層越厚越展現出更高的屏蔽性,另一方面斥力越高。藉此,將電磁波屏蔽片貼附於印刷電路而成的屏蔽印刷電路在組裝至框體中時,裂紋在彎折部分的產生、外觀不良、絕緣不良及雜訊洩漏的發生等成為問題。
另一方面,隨著近年來智慧型手機、平板終端等電子設備在世界範圍內的普及,而要求具有在廣泛的溫度條件下的可靠性。專利文獻1及專利文獻2的具備電磁波屏蔽片的配線電路基板在暴露於極端的溫度變化時,產生從配線電路基板剝離或中斷與接地電路的連接等問題(以下,冷熱循環可靠性)。[The problem to be solved by the invention]
In recent years, in electronic devices typified by mobile phones, with the increase in high-speed transmission of transmission signals, electromagnetic wave shielding sheets on the wiring circuit boards incorporated in these have also been required to have high-frequency shielding properties and transmission characteristics. Therefore, it has been considered that it is preferable to use a metal layer having a thickness of 0.5 μm to 12 μm as described in
本發明是鑒於所述背景而成,其目的在於提供一種具有回流焊耐性及優良的冷熱循環可靠性且具有優異的高頻屏蔽性與良好的彎折耐性的電磁波屏蔽片、及使用了所述電磁波屏蔽片的配線電路基板。 [解決問題的技術手段]The present invention is made in view of the background, and its object is to provide an electromagnetic wave shielding sheet having reflow resistance and excellent cold-heat cycle reliability, excellent high-frequency shielding properties and good bending resistance, and using the The wiring circuit board of the electromagnetic wave shielding sheet. [Technical means to solve the problem]
本發明者進行了積極研究,發現在以下的實施形態中可解決本發明的課題,從而完成了本發明。 即,本發明的電磁波屏蔽片的特徵在於,具有依次具備導電黏接劑層、金屬層、保護層的層壓體,與導電黏接劑層相接的所述金屬層的面中,依據國際標準化組織(International Organization for Standardization,ISO)7668而求出的60°鏡面光澤度為10~800,所述金屬層具有多個開口部,且開口率為0.10%~20%。 [發明的效果]The inventors conducted active studies and found that the problems of the present invention can be solved in the following embodiments, thereby completing the present invention. That is, the electromagnetic wave shielding sheet of the present invention is characterized in that it has a laminate having a conductive adhesive layer, a metal layer, and a protective layer in this order. The 60° specular gloss determined by the International Organization for Standardization (ISO) 7668 is 10 to 800, the metal layer has a plurality of openings, and the opening ratio is 0.10% to 20%. [Effects of the invention]
根據本發明,起到如下優異的效果,即:可提供一種回流焊耐性優異,即使在用於高頻傳輸電路的情況下也會呈現出優異的高頻屏蔽性,且具有良好的彎折耐性與冷熱循環暴露後仍高的連接可靠性的電磁波屏蔽片、及電磁波屏蔽性配線電路基板。According to the present invention, the following excellent effects are achieved, namely: it is possible to provide an excellent reflow resistance, excellent high-frequency shielding performance even when used in a high-frequency transmission circuit, and good bending resistance Electromagnetic wave shielding sheet and electromagnetic wave shielding wiring circuit board with high connection reliability even after exposure to cold and heat cycles.
以下,對應用本發明的實施方式的一例進行說明。另外,以下的圖中的各構件的尺寸(size)或比率是為了便於說明,並不限定於此。而且,在本說明書中,「任意的數A~任意的數B」的記載是指在所述範圍內包含數A作為下限值、包含數B作為上限值。而且,本說明書中的「片」不僅包含日本工業標準(Japanese Industrial Standards,JIS)中所定義的「片」,而且也包含「膜」。而且,本說明書中所指定的數值是利用實施方式或實施例中所揭示的方法而求出的值。Hereinafter, an example of an embodiment to which the present invention is applied will be described. In addition, the size or ratio of each member in the following figures is for convenience of description, and is not limited to this. In addition, in this specification, the description of "arbitrary number A to arbitrary number B" means that the number A is included as a lower limit and the number B is included as an upper limit in the above-mentioned range. Moreover, the "sheet" in this manual includes not only the "sheet" defined in the Japanese Industrial Standards (JIS), but also the "film". In addition, the numerical value specified in this specification is a value calculated|required by the method disclosed in an embodiment or an Example.
<電磁波屏蔽片>
本發明的電磁波屏蔽片具有至少依次具備導電黏接劑層、金屬層、保護層的層壓體。圖1是例示實施方式的電磁波屏蔽片10的剖面圖。如圖1中所示,電磁波屏蔽片10具有依次具備導電黏接劑層a1、金屬層a2及保護層a3的層壓體,金屬層a2配置在導電黏接劑層a1與保護層a3之間。
本發明的電磁波屏蔽片具備具有多個開口部a4,且開口率為0.10%~20%,進而與導電黏接劑層相接的所述金屬層的面中,依據ISO 7668而求出的60°鏡面光澤度為10~800的金屬層,因此特別是在傳輸高頻(例如從100 MHz到50 GHz)的信號的配線電路基板中,可展現出優異的傳輸特性等。
關於電磁波屏蔽片10,例如將作為被黏接體的配線電路基板與導電黏接劑層a1側的面貼合而形成電磁波屏蔽層,製作電磁波屏蔽性配線電路基板。即,金屬層a2的表面中,與配線電路基板中的信號配線相向的是與導電黏接劑層a1密接的表面。<Electromagnetic wave shielding sheet>
The electromagnetic wave shielding sheet of the present invention has a laminate having at least a conductive adhesive layer, a metal layer, and a protective layer in this order. FIG. 1 is a cross-sectional view illustrating an electromagnetic
[層壓硬化物的損耗正切] 而且,本發明的電磁波屏蔽片優選:將至少依次具備導電黏接劑層、金屬層、保護層的層壓體在170℃下熱壓30分鐘而成的層壓硬化物的125℃下的損耗正切為0.10以上。 藉此,可進一步提高冷熱循環可靠性。[Loss tangent of laminated hardened material] Furthermore, the electromagnetic wave shielding sheet of the present invention preferably: a laminate having at least an electrically conductive adhesive layer, a metal layer, and a protective layer in this order is heat-pressed at 170°C for 30 minutes. The loss at 125°C The tangent is 0.10 or more. In this way, the reliability of the cooling and heating cycle can be further improved.
層壓硬化物可通過將電磁波屏蔽片在170℃下熱壓30分鐘進行硬化而形成。即,是指包括導電黏接劑層、金屬層、保護層及其他功能層,其中,具有硬化成分的層被進行了硬化的層壓體。The laminated hardened product can be formed by hardening the electromagnetic wave shielding sheet by hot pressing at 170°C for 30 minutes. That is, it refers to a laminate including a conductive adhesive layer, a metal layer, a protective layer, and other functional layers, in which the layer having a hardening component is hardened.
層壓硬化物是在熱壓前或者熱壓後從電磁波屏蔽片中除去剝離性片者,通過僅對一枚電磁波屏蔽片進行熱壓、或者利用層壓機等層壓多枚電磁波屏蔽片並進行熱壓中的任意一種方法均可獲得。 即,層壓硬化物是電磁波屏蔽片中與用於電磁波屏蔽性配線電路基板的電磁波屏蔽層相同的層壓構成部分。The laminated hardened product is the one in which the peelable sheet is removed from the electromagnetic wave shielding sheet before or after the heat pressing, and the electromagnetic wave shielding sheet is laminated by heat pressing only one electromagnetic wave shielding sheet, or by laminating multiple electromagnetic wave shielding sheets using a laminator, etc. Any method of hot pressing can be obtained. That is, the laminated cured product is the same laminated constituent part of the electromagnetic wave shielding sheet as the electromagnetic wave shielding layer used for the electromagnetic wave shielding printed circuit board.
具體而言,例如,準備兩枚電磁波屏蔽片,將各自的導電黏接劑層側的剝離性片剝離,並將露出的導電黏接劑層彼此貼合,在170℃30分鐘的條件下進行熱壓,將至少依次具備導電黏接劑層、金屬層、保護層的層壓體熱硬化而可製成層壓硬化物。Specifically, for example, two electromagnetic wave shielding sheets are prepared, the peelable sheets on the conductive adhesive layer side of each are peeled off, and the exposed conductive adhesive layers are bonded to each other, and the process is performed at 170°C for 30 minutes By hot pressing, a laminate having at least a conductive adhesive layer, a metal layer, and a protective layer is thermally cured to form a laminate cured product.
層壓硬化物的損耗正切是通過下述數式(3)而求出的數值,是使電磁波屏蔽片變形時產生的應力的緩和能力的指標。 數式(3) (層壓硬化物的損耗正切)= (層壓硬化物的損耗彈性係數E'')/(層壓硬化物的儲存彈性係數E') 作為一例,在圖5中示出層壓硬化物(實施例5)的動態黏彈性曲線。通過讀取某一溫度下的損耗彈性係數E''、儲存彈性係數E',並將這些數值應用於所述數式(3),可計算出對應的溫度下的損耗正切。就冷熱循環可靠性的觀點而言,層壓硬化物優選:在170℃下熱壓30分鐘後的125℃下的損耗正切為0.1以上。若層壓硬化物在170℃下熱壓30分鐘後的125℃下的損耗正切為0.1以上,則能夠充分地緩和因高溫暴露時的膨脹而產生的應力。層壓硬化物更優選:在170℃下熱壓30分鐘後的125℃下的損耗正切為0.13以上,進而優選為0.15以上。The loss tangent of the laminate cured product is a value obtained by the following formula (3), and is an index of the ability to relax the stress generated when the electromagnetic wave shielding sheet is deformed. Numerical formula (3) (Loss tangent of laminated hardened material)= (Loss elastic coefficient of laminated hardened material E'')/(Storage elastic coefficient of laminated hardened material E') As an example, the dynamic viscoelastic curve of the laminated hardened product (Example 5) is shown in FIG. 5. By reading the loss elastic coefficient E" and the storage elastic coefficient E'at a certain temperature, and applying these values to the equation (3), the loss tangent at the corresponding temperature can be calculated. From the viewpoint of the reliability of the cooling and heating cycle, the laminate cured product preferably has a loss tangent at 125°C of 0.1 or more after hot pressing at 170°C for 30 minutes. If the laminated hardened product has a loss tangent at 125°C of 0.1 or more after hot pressing at 170°C for 30 minutes, the stress due to expansion during high-temperature exposure can be sufficiently alleviated. It is more preferable that the laminate cured product has a loss tangent at 125°C of 0.13 or more after hot pressing at 170°C for 30 minutes, and more preferably 0.15 or more.
層壓硬化物的損耗正切可通過改變導電黏接劑層、金屬層、保護層、層壓硬化物中所具備的其他層中的任一者或者兩層以上的層的損耗彈性係數E''及儲存彈性係數E'來控制。這是因為通過改變層壓硬化物中所包括的一層或者兩層以上的層的損耗彈性係數E''及儲存彈性係數E',層壓硬化物的損耗彈性係數E''及儲存彈性係數E'會變化,從而使層壓硬化物的損耗正切變化。The loss tangent of the laminated hardened product can be determined by changing the loss elastic coefficient E of any one of the conductive adhesive layer, the metal layer, the protective layer, and the other layers included in the laminated hardened product, or the loss elasticity coefficient of two or more layers. And storage elasticity coefficient E'to control. This is because by changing the loss elastic coefficient E'' and storage elastic coefficient E'of one or two or more layers included in the laminated hardened product, the loss elastic coefficient E'' and storage elastic coefficient E of the laminated hardened product 'Will change, so that the loss tangent of the laminated hardened material changes.
作為改變層壓硬化物中所包括的一層或者兩層以上的層的損耗彈性係數E''及儲存彈性係數E'的方法的一例,可列舉保護層中的硬化劑量控制。即,通過增加或減少保護層中的硬化劑量,保護層的儲存彈性係數E'上升或下降。其結果,層壓硬化物的儲存彈性係數E'上升或下降,從而使層壓硬化物的損耗正切下降或上升。 作為控制層壓硬化物的損耗正切的方法,並無特別限定,可應用改變熱塑性樹脂或熱硬化性樹脂及硬化劑的種類或調配比、改變各層的厚度的比率、改變金屬層的種類等以往公知的方法。As an example of a method of changing the loss elastic coefficient E" and the storage elastic coefficient E'of one layer or two or more layers included in the laminated hardening substance, the hardening dose control in the protective layer can be cited. That is, by increasing or decreasing the hardening dose in the protective layer, the storage elastic coefficient E'of the protective layer increases or decreases. As a result, the storage elastic coefficient E'of the laminated hardened product increases or decreases, and the loss tangent of the laminated hardened product decreases or increases. The method for controlling the loss tangent of the laminated hardened product is not particularly limited. It can be used to change the type or blending ratio of thermoplastic resin or thermosetting resin and hardener, change the ratio of the thickness of each layer, change the type of metal layer, etc. Well-known method.
《金屬層》 本發明的金屬層具有對電磁波屏蔽片賦予高頻屏蔽性的功能。導電黏接劑層與金屬層的界面中的、金屬層與導電黏接劑層相接的一側的面中,依據ISO 7668而求出的60°鏡面光澤度為10~800。通過將60°鏡面光澤度控制為10~800的範圍,可兼顧彎折耐性與冷熱循環可靠性。關於60°鏡面光澤度的詳細情況、及通過控制60°鏡面光澤度而獲得的效果的詳細情況,將後述。 進而,本發明的金屬層具有多個開口部,且開口率為0.10%~20%。藉此,回流焊耐性提高,從而可抑制外觀不良的發生及連接可靠性的下降。"Metal Layer" The metal layer of the present invention has a function of imparting high-frequency shielding properties to the electromagnetic wave shielding sheet. In the interface between the conductive adhesive layer and the metal layer, on the side where the metal layer and the conductive adhesive layer are in contact, the 60° specular gloss calculated in accordance with ISO 7668 is 10 to 800. By controlling the 60° mirror gloss in the range of 10 to 800, it is possible to balance the bending resistance and the reliability of the cold and heat cycle. The details of the 60° specular glossiness and the details of the effects obtained by controlling the 60° specular glossiness will be described later. Furthermore, the metal layer of the present invention has a plurality of openings, and the opening ratio is 0.10% to 20%. Thereby, the reflow resistance is improved, and it is possible to suppress the occurrence of appearance defects and the decrease in connection reliability.
[60°鏡面光澤度] 60°鏡面光澤度是在ISO 7668中經標準化的參數,表示測定對象表面的光澤程度。鏡面光澤度可通過如下方式測定,即:以一定的入射角對測定對象表面照射光(入射光),利用檢測器檢測一定的角度的經反射的光(鏡面反射光),並將其數值化。 對測定對象表面照射的入射光在到達測定對象表面時,被反射或透過、吸收。而且,反射中有鏡面反射及漫反射,以與入射角相同的角度(反射角)反射的光是鏡面反射光,是在鏡面光澤度測定中被檢測的光。60°鏡面光澤度是入射角及反射角為60°時所測定的值。 在測定對象表面為金屬層的情況下,入射光的大部分會被反射。被反射的光以怎樣的比例成為鏡面反射與漫反射是由金屬層表面的粗糙程度決定的。圖2中示出粗糙程度不同的兩種測定對象表面的剖面圖。如圖2的(i)中所示,在粗糙程度小的測定對象表面,鏡面反射光的比例大,另一方面漫反射光變小,鏡面光澤度的值變大。另一方面,如圖2的(ii)中所示,在粗糙程度大的測定對象表面,鏡面反射光的比例小,另一方面漫反射光變大,鏡面光澤度的值變小。即,鏡面光澤度可作為預估測定對象表面的粗糙程度的指標來使用。[60°mirror gloss] The 60° specular gloss is a parameter standardized in ISO 7668, which represents the degree of gloss on the surface of the measured object. Specular gloss can be measured by irradiating light (incident light) on the surface of the object to be measured at a certain angle of incidence, using a detector to detect the reflected light (specular reflection light) at a certain angle, and digitizing it . The incident light irradiated to the surface of the object to be measured is reflected, transmitted, or absorbed when it reaches the surface of the object to be measured. In addition, there are specular reflection and diffuse reflection in reflection, and light reflected at the same angle (reflection angle) as the incident angle is specular reflection light, which is the light detected in the specular gloss measurement. The 60° specular gloss is the value measured when the incident angle and reflection angle are 60°. When the surface of the measurement object is a metal layer, most of the incident light will be reflected. The ratio of the reflected light to specular reflection and diffuse reflection is determined by the roughness of the surface of the metal layer. Fig. 2 shows cross-sectional views of two measurement object surfaces with different roughnesses. As shown in (i) of FIG. 2, on the surface of the measurement target with low roughness, the proportion of specular reflection light is large, while diffuse reflection light decreases, and the value of specular gloss increases. On the other hand, as shown in (ii) of FIG. 2, the ratio of specular reflection light is small on the surface of the measurement target with a large degree of roughness. On the other hand, the diffuse reflection light increases, and the value of the specular gloss decreases. That is, the mirror gloss can be used as an index for estimating the roughness of the surface of the measurement object.
另外,此金屬層的60°鏡面光澤度的值不會因加熱壓制等電磁波屏蔽層的形成步驟而變化。因此,電磁波屏蔽層中與導電黏接劑層相接的所述金屬層的面的60°鏡面光澤度也為10~800。In addition, the value of the 60° specular gloss of the metal layer does not change due to the steps of forming the electromagnetic wave shielding layer such as heating and pressing. Therefore, the 60° specular gloss of the surface of the metal layer in contact with the conductive adhesive layer in the electromagnetic wave shielding layer is also 10 to 800.
在彎折電磁波屏蔽片、及將其硬化而成的層壓硬化物或電磁波屏蔽性配線電路基板時,所包括的金屬層也一起被彎折。此時,在金屬層的表面的凹凸陡峭的情況下,有時會誘發金屬層的裂紋。即,在金屬層被彎折時,應力向凹凸的凹部集中,以凹部為起點在金屬層上產生裂紋。金屬層的裂紋會引發由金屬層的導電不良引起的屏蔽性的下降、或因裂紋端部刺破其他層而產生的外觀不良等問題。因此,就彎折耐性的觀點而言,金屬層的與導電黏接劑層相接的面的60°鏡面光澤度優選為10以上,更優選為20以上,進而優選為40以上。When the electromagnetic wave shielding sheet and the laminated hardened product or electromagnetic wave shielding wiring circuit board formed by curing the electromagnetic wave shielding sheet are bent, the metal layer included is also bent together. At this time, when the unevenness of the surface of the metal layer is steep, cracks in the metal layer may be induced. That is, when the metal layer is bent, stress is concentrated on the concave and convex portions, and cracks are generated in the metal layer from the concave portion as a starting point. Cracks in the metal layer cause problems such as a decrease in shielding properties due to poor conductivity of the metal layer, or poor appearance due to the end of the crack piercing other layers. Therefore, from the viewpoint of bending resistance, the 60° specular gloss of the surface of the metal layer in contact with the conductive adhesive layer is preferably 10 or more, more preferably 20 or more, and even more preferably 40 or more.
另一方面,就冷熱循環可靠性的觀點而言,積極研究的結果是發現如下結果,即:通過將金屬層的60°鏡面光澤度設為10~800的範圍,冷熱循環可靠性提高。認為這是因為即使在冷熱循環中,因導電黏接劑層的伸縮而發生了形狀變化的情況下,也通過使金屬層表面上所形成的凹凸適度粗糙,而維持了導電黏接劑層中的導電性填料與金屬層的接觸,從而抑制了連接電阻值的惡化。研究的結果是,更優選將金屬層的60°鏡面光澤度設為20~750的範圍,進而優選設為40~700的範圍。On the other hand, from the viewpoint of the reliability of the cooling and heating cycle, the result of active research is that by setting the 60° specular gloss of the metal layer in the range of 10 to 800, the reliability of the cooling and heating cycle is improved. It is believed that this is because even when the shape of the conductive adhesive layer changes due to the expansion and contraction of the conductive adhesive layer during the cooling and heating cycle, the unevenness formed on the surface of the metal layer is appropriately rough, and the conductive adhesive layer is maintained The conductive filler is in contact with the metal layer, thereby suppressing the deterioration of the connection resistance. As a result of the research, it is more preferable to set the 60° specular gloss of the metal layer to the range of 20 to 750, and still more preferably to the range of 40 to 700.
[60°鏡面光澤度的控制方法] 控制金屬層表面的60°鏡面光澤度的方法例如可列舉:在銅箔表面上附著粗化粒子,形成粗化處理面的方法、使用日本專利特開第2017-13473號公報中所記載的拋光器(buff)研磨金屬表面的方法、使用研磨布紙研磨金屬表面的方法、在具有所期望的凹凸的載體材上利用鍍敷等方法形成金屬層來轉印載體材的凹凸的方法、通過壓縮空氣將研磨材吹付至金屬表面的噴丸(shotblast)法。作為金屬層表面的60°鏡面光澤度的控制方法,並不限定於例示的方法,可應用以往公知的方法。[Method of controlling 60° mirror glossiness] The method of controlling the 60° specular gloss of the metal layer surface includes, for example, a method of attaching roughened particles to the surface of a copper foil to form a roughened surface, and polishing described in Japanese Patent Laid-Open No. 2017-13473 The method of buff polishing the metal surface, the method of polishing the metal surface using abrasive cloth, the method of forming a metal layer on the carrier with the desired unevenness by plating or other methods to transfer the unevenness of the carrier material, by compression The shotblast method in which air blows the abrasive onto the metal surface. The method of controlling the 60° specular gloss on the surface of the metal layer is not limited to the exemplified method, and a conventionally known method can be applied.
[金屬層的厚度] 金屬層的厚度優選為0.3 μm以上。通過將金屬層的厚度設為0.3 μm以上,可針對從配線電路基板產生的電磁波雜訊的波長,抑制透過,從而可展現出充分的高頻屏蔽性並且可抑制彎折時金屬層產生裂紋。金屬層的厚度更優選為0.5 μm以上。另一方面,金屬層的厚度優選為5.0 μm以下。通過將金屬層的厚度設為5.0 μm以下,可提高層壓硬化物的損耗正切,從而使冷熱循環可靠性提高。金屬層的厚度上限更優選為3.5 μm以下。[The thickness of the metal layer] The thickness of the metal layer is preferably 0.3 μm or more. By setting the thickness of the metal layer to 0.3 μm or more, it is possible to suppress transmission of the wavelength of electromagnetic noise generated from the printed circuit board, thereby exhibiting sufficient high-frequency shielding properties and suppressing cracks in the metal layer during bending. The thickness of the metal layer is more preferably 0.5 μm or more. On the other hand, the thickness of the metal layer is preferably 5.0 μm or less. By setting the thickness of the metal layer to 5.0 μm or less, the loss tangent of the laminated hardened product can be increased, and the reliability of the cooling and heating cycle can be improved. The upper limit of the thickness of the metal layer is more preferably 3.5 μm or less.
[金屬層的成分] 金屬層例如可使用金屬箔、金屬蒸鍍膜、金屬鍍敷膜。 金屬箔中使用的金屬例如優選為鋁、銅、銀、金等導電性金屬,使用一種金屬或者多種金屬的合金均可。就高頻屏蔽性及成本的方面而言,更優選為銅、銀、鋁,進而優選為銅。銅例如優選使用壓延銅箔或電解銅箔。 金屬蒸鍍膜及金屬鍍敷膜中使用的金屬例如優選使用鋁、銅、銀、金等導電性金屬的一種或多種金屬的合金,更優選為銅、銀。可將金屬箔、金屬蒸鍍膜、金屬鍍敷膜的其中一表面或者兩表面用金屬、或者防鏽劑等有機物予以包覆。[Composition of the metal layer] For the metal layer, for example, a metal foil, a metal vapor-deposited film, or a metal-plated film can be used. The metal used in the metal foil is preferably, for example, a conductive metal such as aluminum, copper, silver, gold, and the like, and one type of metal or an alloy of multiple types of metals may be used. In terms of high-frequency shielding properties and cost, copper, silver, and aluminum are more preferable, and copper is still more preferable. For copper, for example, rolled copper foil or electrolytic copper foil is preferably used. As the metal used in the metal vapor-deposition film and the metal-plated film, for example, an alloy of one or more metals of conductive metals such as aluminum, copper, silver, and gold is preferably used, and copper and silver are more preferable. One or both surfaces of metal foil, metal vapor-deposited film, and metal-plated film can be coated with metal or organic matter such as rust inhibitor.
[開口部] 金屬層具有多個開口部,其開口率為0.10%~20%。通過具有開口部,回流焊耐性提高。通過具有開口部,在對電磁波屏蔽性配線電路基板進行回流焊處理時,可使配線電路基板的聚醯亞胺膜或覆蓋層黏接劑中所含的揮發成分逃逸至外部,從而抑制由覆蓋層黏接劑及電磁波屏蔽片的界面剝離引起的外觀不良的發生。[Opening] The metal layer has a plurality of openings with an opening ratio of 0.10% to 20%. By having the opening, the reflow resistance is improved. By having an opening, when the electromagnetic wave shielding printed circuit board is reflowed, the volatile components contained in the polyimide film or cover layer adhesive of the printed circuit board can escape to the outside, thereby suppressing the cover The appearance of poor appearance caused by the peeling of the interface between the layer adhesive and the electromagnetic wave shielding sheet.
從金屬層表面觀察的開口部的形狀可視需要形成各形狀,例如正圓、橢圓、四邊形、多邊形、星形、梯形、枝狀等。從製造成本及金屬層的強韌性確保的觀點而言,開口部的形狀優選設為正圓及橢圓。The shape of the opening viewed from the surface of the metal layer can be formed into various shapes as necessary, such as a perfect circle, an ellipse, a quadrilateral, a polygon, a star, a trapezoid, a branch, and the like. From the viewpoint of manufacturing cost and ensuring the strength and toughness of the metal layer, the shape of the opening is preferably a perfect circle and an ellipse.
[金屬層的開口率] 金屬層的開口率為0.10%~20%的範圍,可利用下述數式(2)求出。 數式(2) (開口率[%])=(每單位面積中的開口部的面積)/(每單位面積中的開口部的面積+每單位面積中的非開口部的面積)×100[Aperture ratio of metal layer] The aperture ratio of the metal layer is in the range of 0.10% to 20%, which can be calculated by the following formula (2). Numerical formula (2) (Aperture ratio [%])=(Area of opening per unit area)/(Area of opening per unit area+Area of non-opening per unit area)×100
通過使開口率為0.10%以上,可使回流焊處理時的揮發成分充分逃逸,從而可抑制由覆蓋層黏接劑及電磁波屏蔽片的界面剝離引起的外觀不良的發生及連接可靠性的下降,因此優選。 另一方面,通過使開口率為20%以下,可減少通過開口部分的電磁波雜訊的量,從而提高屏蔽性,因此優選。以高的水準兼顧回流焊耐性與高頻屏蔽性的開口率的範圍更優選為0.30%~15%,進而優選為0.50%~6.5%。By setting the aperture ratio to 0.10% or more, the volatile components during the reflow process can be sufficiently escaped, and the occurrence of appearance defects and the decrease in connection reliability caused by the interface peeling of the cover layer adhesive and the electromagnetic wave shielding sheet can be suppressed. Therefore preferred. On the other hand, by setting the aperture ratio to 20% or less, the amount of electromagnetic wave noise passing through the aperture can be reduced and the shielding properties can be improved, which is preferable. The range of the aperture ratio that balances reflow resistance and high-frequency shielding properties at a high level is more preferably 0.30% to 15%, and still more preferably 0.50% to 6.5%.
特別是,在金屬層的60°鏡面光澤度在700以上的範圍內,且與導電黏接劑層的界面平滑的電磁波屏蔽片中,金屬層與導電黏接劑層的密接弱,存在在回流焊處理時,在金屬層與導電黏接劑層的界面處,揮發成分膨脹,而發生層間剝離或浮起等外觀不良的情況,但通過將開口率設為0.10%以上、優選為0.50%以上,可使揮發成分充分逃逸,從而可進一步抑制層間剝離或浮起的發生。In particular, in the electromagnetic wave shielding sheet where the 60° specular gloss of the metal layer is in the range of 700 or more and the interface with the conductive adhesive layer is smooth, the adhesion between the metal layer and the conductive adhesive layer is weak. During the soldering process, the volatile components swell at the interface between the metal layer and the conductive adhesive layer, resulting in poor appearance such as delamination or floating, but by setting the aperture ratio to 0.10% or more, preferably 0.50% or more , Can make the volatile components escape sufficiently, which can further suppress the occurrence of delamination or floating between layers.
開口率的測定例如可通過如下方式求出,即:使用利用雷射顯微鏡及掃描型電子顯微鏡(Scanning Electron Microscope,SEM)從金屬層的面方向垂直地放大500倍~2000倍而得的圖像,將開口部與非開口部二值化,將每單位面積中的二值化後的顏色的畫素數作為各自的面積。The aperture ratio can be measured, for example, by using a laser microscope and a scanning electron microscope (Scanning Electron Microscope, SEM) to vertically magnify an image obtained by 500 to 2000 times from the surface direction of the metal layer. , Binarize the opening and the non-opening, and use the number of pixels of the binarized color per unit area as the respective areas.
開口部平均一個的面積優選為0.7 μm2 ~5000 μm2 。更優選為10 μm2 ~4000 μm2 ,進而優選為20 μm2 ~2000 μm2 。通過將開口部面積設為0.7 μm2 以上,保護層與導電黏接劑層的黏接變得良好,回流焊耐性變得更優異。通過將開口部面積設為5000 μm2 以下,可使得在高的電磁波屏蔽性方面優異,因此優選。The average area of one opening is preferably 0.7 μm 2 to 5000 μm 2 . It is more preferably 10 μm 2 to 4000 μm 2 , and still more preferably 20 μm 2 to 2000 μm 2 . By setting the opening area to 0.7 μm 2 or more, the adhesion between the protective layer and the conductive adhesive layer becomes better, and the reflow resistance becomes more excellent. By setting the area of the opening to 5000 μm 2 or less, it is possible to make it excellent in high electromagnetic wave shielding properties, which is therefore preferable.
開口部的個數優選為100個/cm2 ~200000個/cm2 。更優選為1000個/cm2 ~150000個/cm2 ,進而優選為1000個/cm2 ~20000個/cm2 。通過將開口部的個數設為100個/cm2 以上,容易將揮發成分有效率地排出至外部,因此可進一步提高回流焊耐性。通過將開口部的數量設為200000個/cm2 以下,可確保高的電磁波屏蔽性,因此優選。The number of openings is preferably 100 openings/cm 2 to 200,000 openings/cm 2 . More preferably, it is 1,000 pieces/cm 2 to 150,000 pieces/cm 2 , and still more preferably 1,000 pieces/cm 2 to 20,000 pieces/cm 2 . By setting the number of openings to 100/cm 2 or more, it is easy to efficiently discharge volatile components to the outside, and therefore the reflow resistance can be further improved. By setting the number of openings to 200,000/cm 2 or less, high electromagnetic wave shielding properties can be ensured, which is preferable.
[具有開口部的金屬層的製造方法] 具有開口部的金屬層的製造方法可應用以往公知的方法,可應用在金屬箔上形成圖案抗蝕劑層並對金屬箔進行蝕刻而形成開口部的方法(i)、通過網版印刷以規定的圖案來印刷導電性糊的方法(ii)、以規定的圖案進行底塗劑(Anchor Agent)的網版印刷,並僅對底塗劑印刷面進行金屬鍍敷的方法(iii)、及日本專利特開2015-63730號公報中所記載的製造方法(iv)等。即,在支撐體上進行水溶性或溶劑可溶性的油墨的圖案印刷,在其表面形成金屬蒸鍍膜,並除去圖案。通過在其表面形成脫模層並進行電解鍍敷,可獲得帶載體材的具有開口部的金屬層。這些中,形成圖案抗蝕劑層並對金屬箔進行蝕刻的開口部形成方法(i)可精密地控制開口部的形狀,因此優選。但是,金屬層的製造方法並不限制於蝕刻方法(i),只要可控制開口部的形狀,也可以是其他方法。[Method for manufacturing metal layer with opening] The method for manufacturing the metal layer with openings can be a conventionally known method, and it can be applied to a method of forming a patterned resist layer on a metal foil and etching the metal foil to form an opening (i), using screen printing to define The method of printing the conductive paste with the pattern (ii), the screen printing of the primer (Anchor Agent) with a predetermined pattern, and the method of metal plating only on the printed surface of the primer (iii), and Japan The manufacturing method (iv) described in Japanese Patent Laid-Open No. 2015-63730, etc. That is, pattern printing of water-soluble or solvent-soluble ink is performed on the support, a metal vapor-deposited film is formed on the surface, and the pattern is removed. By forming a mold release layer on the surface and performing electrolytic plating, a metal layer with an opening with a carrier material can be obtained. Among these, the opening forming method (i) of forming a patterned resist layer and etching the metal foil can precisely control the shape of the opening, and therefore is preferable. However, the manufacturing method of the metal layer is not limited to the etching method (i), and other methods may be used as long as the shape of the opening can be controlled.
《導電黏接劑層》 導電黏接劑層可使用導電性樹脂組成物來形成。導電性樹脂組成物包含黏合劑樹脂及導電性填料。黏合劑樹脂可使用熱塑性樹脂、或者熱硬化性樹脂及硬化劑、中的任一者。導電黏接劑層可使用各向同性導電黏接劑層或各向異性導電黏接劑層中的任一者。各向同性導電黏接劑層在將電磁波屏蔽片水平放置的狀態下,在上下方向及水平方向上具有導電性。而且,各向異性導電黏接劑層在將電磁波屏蔽片水平放置的狀態下,僅在上下方向上具有導電性。導電黏接劑層可為各向同性導電性或各向異性導電性中的任一者,在為各向異性導電性的情況下,成本降低成為可能,因此優選。"Conductive Adhesive Layer" The conductive adhesive layer can be formed using a conductive resin composition. The conductive resin composition includes a binder resin and a conductive filler. As the binder resin, any one of a thermoplastic resin, a thermosetting resin, and a curing agent can be used. The conductive adhesive layer may use either an isotropic conductive adhesive layer or an anisotropic conductive adhesive layer. The isotropic conductive adhesive layer has conductivity in the vertical and horizontal directions when the electromagnetic wave shielding sheet is placed horizontally. In addition, the anisotropic conductive adhesive layer has conductivity only in the vertical direction when the electromagnetic wave shielding sheet is placed horizontally. The conductive adhesive layer may be either isotropic conductivity or anisotropic conductivity. In the case of anisotropic conductivity, cost reduction is possible, which is preferable.
[熱塑性樹脂] 作為熱塑性樹脂,可列舉:聚烯烴系樹脂、乙烯基系樹脂、苯乙烯-丙烯酸系樹脂、二烯系樹脂、萜烯樹脂、石油樹脂、纖維素系樹脂、聚醯胺樹脂、聚氨基甲酸酯樹脂、聚酯樹脂、聚碳酸酯樹脂、聚醯亞胺樹脂、液晶聚合物、氟樹脂等。雖無特別限定,但就傳輸損耗的觀點而言,優選為低介電常數、低介電損耗正切的材料,就特性阻抗的觀點而言,優選為低介電常數的材料,可列舉液晶聚合物或氟系樹脂等。熱塑性樹脂可單獨使用或併用兩種以上。[Thermoplastic resin] Examples of thermoplastic resins include polyolefin resins, vinyl resins, styrene-acrylic resins, diene resins, terpene resins, petroleum resins, cellulose resins, polyamide resins, and polyurethanes. Ester resin, polyester resin, polycarbonate resin, polyimide resin, liquid crystal polymer, fluororesin, etc. Although not particularly limited, from the viewpoint of transmission loss, materials with low dielectric constant and low dielectric loss tangent are preferable, and from the viewpoint of characteristic impedance, materials with low dielectric constant are preferable, such as liquid crystal polymerization. Materials or fluorine-based resins, etc. The thermoplastic resin can be used alone or in combination of two or more kinds.
[熱硬化性樹脂] 熱硬化性樹脂是具有多個能夠與硬化劑反應的官能基的樹脂。官能基例如可列舉:羥基、酚性羥基、甲氧基甲基、羧基、氨基、環氧基、氧雜環丁基、惡唑啉基、惡嗪基、氮丙啶基、硫醇基、異氰酸酯基、嵌段型異氰酸酯基、嵌段型羧基、矽醇基等。熱硬化性樹脂例如可列舉:丙烯酸樹脂、馬來酸樹脂、聚丁二烯系樹脂、聚酯樹脂、聚氨基甲酸酯樹脂、聚氨基甲酸酯脲樹脂、環氧樹脂、氧雜環丁烷樹脂、苯氧基樹脂、聚醯亞胺樹脂、聚醯胺樹脂、聚醯胺醯亞胺樹脂、酚系樹脂、醇酸樹脂、氨基樹脂、聚乳酸樹脂、惡唑啉樹脂、苯並惡嗪樹脂、矽酮樹脂、氟樹脂等公知的樹脂。熱硬化性樹脂可單獨使用或併用兩種以上。[Thermosetting resin] The thermosetting resin is a resin having a plurality of functional groups capable of reacting with a curing agent. Examples of functional groups include hydroxyl groups, phenolic hydroxyl groups, methoxymethyl groups, carboxyl groups, amino groups, epoxy groups, oxetanyl groups, oxazoline groups, oxazinyl groups, aziridinyl groups, thiol groups, Isocyanate group, blocked isocyanate group, blocked carboxyl group, silanol group, etc. Examples of thermosetting resins include acrylic resins, maleic acid resins, polybutadiene resins, polyester resins, polyurethane resins, polyurethane urea resins, epoxy resins, and oxetane resins. Alkyl resin, phenoxy resin, polyimide resin, polyimide resin, polyimide resin, phenolic resin, alkyd resin, amino resin, polylactic acid resin, oxazoline resin, benzoxan Known resins such as oxazine resin, silicone resin, and fluororesin. The thermosetting resin can be used singly or in combination of two or more kinds.
這些中,就回流焊耐性的方面而言,優選為聚氨基甲酸酯樹脂、聚氨基甲酸酯脲樹脂、聚酯樹脂、環氧樹脂、苯氧基樹脂、聚醯亞胺樹脂、聚醯胺樹脂、聚醯胺醯亞胺樹脂。Among these, in terms of reflow resistance, polyurethane resins, polyurethane urea resins, polyester resins, epoxy resins, phenoxy resins, polyimide resins, and polyamide resins are preferred. Amine resin, polyamide imide resin.
[硬化劑] 硬化劑具有多個能夠與熱硬化性樹脂的官能基反應的官能基。硬化劑例如可列舉:環氧化合物、含有酸酐基的化合物、異氰酸酯化合物、氮丙啶化合物、胺化合物、酚化合物、有機金屬化合物等公知的化合物。硬化劑可單獨使用或併用兩種以上。[hardener] 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 epoxy compounds, acid anhydride group-containing compounds, isocyanate compounds, aziridine compounds, amine compounds, phenol compounds, and organometallic compounds. The hardener can be used alone or in combination of two or more kinds.
關於硬化劑,優選相對於熱硬化性樹脂100質量份而包含各種硬化劑1質量份~50質量份,更優選為3質量份~40質量份,進而優選為3質量份~30質量份。Regarding the curing agent, it is preferable to include 1 to 50 parts by mass of various curing agents with respect to 100 parts by mass of the thermosetting resin, more preferably 3 to 40 parts by mass, and still more preferably 3 to 30 parts by mass.
熱塑性樹脂及熱硬化性樹脂可單獨使用任一者或者將兩者混合來併用。The thermoplastic resin and the thermosetting resin can be used alone or in a mixture of both.
[導電性填料] 導電性填料具有對導電黏接劑層賦予導電性的功能。導電性填料中,作為原材料,例如優選為金、鉑、銀、銅及鎳等導電性金屬及其合金、以及導電性聚合物的微粒子,就價格與導電性的方面而言,更優選為銀。而且,就降低成本的觀點而言,也優選非單一原材料的微粒子而是將金屬或樹脂作為核體,並具有對核體的表面進行包覆的包覆層的複合微粒子。此處,核體優選從價格低廉的鎳、二氧化矽、銅及其合金、以及樹脂中適當選擇。包覆層優選為導電性金屬或導電性聚合物。導電性金屬例如可列舉:金、鉑、銀、鎳、錳、及銦等、以及其合金。而且,導電性聚合物可列舉聚苯胺、聚乙炔等。這些之中,就價格與導電性的方面而言,優選為銀。[Conductive filler] The conductive filler has a function of imparting conductivity to the conductive adhesive layer. Among the conductive fillers, as the raw material, for example, conductive metals such as gold, platinum, silver, copper, and nickel, and their alloys, and conductive polymer particles are preferred. In terms of price and conductivity, silver is more preferred. . Furthermore, from the viewpoint of cost reduction, it is also preferable to use metal or resin as a core body instead of fine particles of a single raw material and have a coating layer covering the surface of the core body. Here, the core body is preferably appropriately selected from inexpensive nickel, silicon dioxide, copper and alloys thereof, and resins. The coating layer is preferably a conductive metal or a conductive polymer. Examples of conductive metals include gold, platinum, silver, nickel, manganese, and indium, and alloys thereof. Furthermore, the conductive polymer includes polyaniline, polyacetylene, and the like. Among these, in terms of price and conductivity, silver is preferred.
關於導電性填料的形狀,只要可獲得所期望的導電性即可,形狀並無限定。具體而言,例如優選為球狀、薄片狀、葉狀、樹枝狀、板狀、針狀、棒狀、葡萄狀。而且,也可將這些不同形狀的導電性填料混合兩種。導電性填料可單獨使用或併用兩種以上。Regarding the shape of the conductive filler, as long as the desired conductivity can be obtained, the shape is not limited. 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. Furthermore, these conductive fillers of different shapes may be mixed two kinds. The conductive filler can be used alone or in combination of two or more kinds.
導電性填料的平均粒徑為D50 平均粒徑,就充分地確保導電性的觀點而言,優選為2 μm以上,更優選為5 μm以上,進而優選為設為7 μm以上。通過使導電性填料的D50 平均粒徑為2 μm以上,即使對於冷熱循環試驗時的導電黏接劑層的膨脹,導電性填料彼此也會充分接觸,從而可確保導通路徑。另一方面,就兼顧導電黏接劑層的薄度的觀點而言,優選為30 μm以下,更優選為20 μm以下,進而優選設為15 μm以下。通過將D50 平均粒徑設為30 μm以下,可抑制彎折時導電性填料刺破保護層的現象。D50 平均粒徑可利用雷射繞射/散射法粒度分佈測定裝置等而求出。The average particle diameter of the conductive filler is the D 50 average particle diameter, and from the viewpoint of sufficiently ensuring conductivity, it is preferably 2 μm or more, more preferably 5 μm or more, and even more preferably 7 μm or more. By setting the D 50 average particle size of the conductive filler to be 2 μm or more, even in the case of expansion of the conductive adhesive layer during the thermal cycle test, the conductive fillers are sufficiently in contact with each other, and the conduction path can be ensured. On the other hand, from the viewpoint of achieving both the thickness of the conductive adhesive layer, the thickness is preferably 30 μm or less, more preferably 20 μm or less, and still more preferably 15 μm or less. By setting the average particle size of D 50 to 30 μm or less, it is possible to suppress the phenomenon that the conductive filler pierces the protective layer during bending. The average particle diameter of D 50 can be determined by a laser diffraction/scattering particle size distribution measuring device or the like.
導電性填料在導電黏接劑層中的含有率優選為35質量%~90質量%,更優選為39質量%~70質量%,進而優選為40質量%~65質量%。通過設為35質量%以上,導電黏接劑層與接地配線的連接變得良好,因此高頻屏蔽性、冷熱循環可靠性提高。另一方面,通過設為90質量%以下,回流焊耐性、彎折耐性提高。The content of the conductive filler in the conductive adhesive layer is preferably 35% by mass to 90% by mass, more preferably 39% by mass to 70% by mass, and still more preferably 40% by mass to 65% by mass. By setting it as 35% by mass or more, the connection between the conductive adhesive layer and the ground wiring becomes good, and therefore the high-frequency shielding properties and the reliability of the cooling and heating cycle are improved. On the other hand, by setting it as 90% by mass or less, reflow resistance and bending resistance are improved.
出於提高所期望的物性或賦予功能的目的,導電性樹脂組成物另外可調配矽烷偶聯劑、防鏽劑、還原劑、抗氧化劑、顏料、染料、黏著賦予樹脂、塑化劑、紫外線吸收劑、消泡劑、流平調整劑、填充劑、阻燃劑等作為任意成分。例如,可出於調整導電黏接劑層的黏彈性的目的來添加碳粒子。碳粒子可列舉碳黑、科琴黑、乙炔黑、碳奈米管、石墨烯等。For the purpose of improving the desired physical properties or imparting functions, the conductive resin composition can be additionally formulated with silane coupling agents, rust inhibitors, reducing agents, antioxidants, pigments, dyes, adhesive imparting resins, plasticizers, and ultraviolet absorbers. As optional ingredients, such as antifoaming agents, leveling regulators, fillers, flame retardants, etc. For example, carbon particles may be added for the purpose of adjusting the viscoelasticity of the conductive adhesive layer. Examples of carbon particles include carbon black, Ketjen black, acetylene black, carbon nanotubes, and graphene.
導電性樹脂組成物可將至此為止說明的材料混合並加以攪拌而獲得。攪拌例如可使用分散機(dispermat)、均質機等公知的攪拌裝置。The conductive resin composition can be obtained by mixing and stirring the materials described so far. For stirring, for example, a known stirring device such as a dispermat and a homogenizer can be used.
導電黏接劑層的製作可使用公知的方法。例如,通過將導電性樹脂組成物塗敷於剝離性片上並進行乾燥而形成導電黏接劑層的方法、或者也可通過使用T字模那樣的擠出成形機將導電性樹脂組成物擠出為片狀來形成。A known method can be used for the preparation of the conductive adhesive layer. For example, a method of forming a conductive adhesive layer by coating a conductive resin composition on a peelable sheet and drying it, or extruding the conductive resin composition into an extruder using an extruder such as a T-die Flake to form.
塗敷方法例如可使用凹版塗布方式、吻合式塗布方式、模塗方式、唇塗方式、缺角輪塗布方式、刮刀方式、輥塗方式、刀式塗布方式、噴霧塗布方式、棒塗方式、旋塗方式、浸漬塗布方式等公知的塗敷方法。在塗敷時,優選進行乾燥步驟。乾燥步驟例如可使用熱風乾燥機、紅外線加熱器等公知的乾燥裝置。For the coating method, for example, gravure coating method, kiss coating method, die coating method, lip coating method, chipped wheel coating method, doctor blade method, roll coating method, knife coating method, spray coating method, bar coating method, spin coating method, etc. can be used. Well-known coating methods such as coating method and dip coating method. At the time of coating, it is preferable to perform a drying step. For the drying step, for example, a known drying device such as a hot air dryer and an infrared heater can be used.
導電黏接劑層的厚度優選為2 μm~30 μm,更優選為3 μm~15 μm,進而優選為4 μm~9 μm。通過使厚度處於2 μm~30 μm的範圍,可提高冷熱循環可靠性與回流焊耐性。The thickness of the conductive adhesive layer is preferably 2 μm to 30 μm, more preferably 3 μm to 15 μm, and still more preferably 4 μm to 9 μm. By setting the thickness in the range of 2 μm to 30 μm, the reliability of the cooling and heating cycle and the resistance to reflow soldering can be improved.
《保護層》 保護層可使用以往公知的樹脂組成物來形成。 樹脂組成物可包含導電性樹脂組成物中所說明的熱塑性樹脂或熱硬化性樹脂及硬化劑以及視需要的所述任意成分。另外,保護層及導電黏接劑層中使用的熱硬化性樹脂、硬化劑可相同或不同。"The protective layer" The protective layer can be formed using a conventionally known resin composition. The resin composition may contain the thermoplastic resin or the thermosetting resin and the curing agent described in the conductive resin composition, and the optional components as required. In addition, the thermosetting resin and curing agent used in the protective layer and the conductive adhesive layer may be the same or different.
樹脂組成物可利用與導電性樹脂組成物同樣的方法來獲得。The resin composition can be obtained by the same method as the conductive resin composition.
而且,保護層也可使用將聚酯、聚碳酸酯、聚醯亞胺、聚醯胺醯亞胺、聚醯胺、聚苯硫醚、聚醚醚酮等絕緣性樹脂成形而成的膜。In addition, the protective layer can also use a film formed by molding insulating resins such as polyester, polycarbonate, polyimide, polyimide, polyamide, polyphenylene sulfide, and polyether ether ketone.
保護層的厚度通常為2 μm~10 μm左右。The thickness of the protective layer is usually about 2 μm to 10 μm.
《電磁波屏蔽片的製造方法》 電磁波屏蔽片的製作方法可使用公知的方法。 例如,可列舉:方法(i)在剝離性片上形成導電黏接劑層,將導電黏接劑層重疊於帶載體材的具有開口部的電解銅箔(也稱為帶載體材的銅箔)的電解銅箔面側並進行層壓後,將載體材剝離。然後,將剝離了載體材的面與另行形成於剝離性片上的保護層重疊並進行層壓;方法(ii)在剝離性片上形成保護層,將保護層重疊於帶載體材的具有開口部的電解銅箔的電解銅箔面側並進行層壓後,將載體材剝離。然後,將剝離了載體材的面與另行形成於剝離性片上的導電黏接劑層重疊並進行層壓;方法(iii)在帶載體材的具有開口部的電解銅箔的電解銅箔面側塗敷樹脂組成物來形成保護層,並貼合剝離性片。之後,將載體材剝離,重疊另行形成於剝離性片上的導電黏接劑層並進行層壓;方法(iv)在剝離性片上形成導電黏接劑層,將導電黏接劑層重疊於帶載體材的銅箔的電解銅箔面側並進行層壓後,將載體材剝離。然後,將剝離了載體材的面與另行形成於剝離性片上的保護層重疊並進行層壓,之後利用針狀的治具對電磁波屏蔽片形成開口部;方法(v)將形成於剝離性片上的保護層重疊於帶載體材的具有開口部的電解銅箔的電解銅箔面側並進行層壓後,將載體材剝離。然後,在剝離了載體材的面上形成導電黏接劑層;方法(vi)在剝離性片上形成導電黏接劑層,將具有開口部的壓延銅箔的表面中,60°鏡面光澤度為10~800的面與導電黏接劑層重疊並進行層壓後,將與導電黏接劑層層壓的另一個面與另行形成於剝離性片上的保護層重疊並進行層壓;方法(vii)在剝離性片上形成保護層,將具有開口部的壓延銅箔的表面中,60°鏡面光澤度為10~800的面的另一個面與導電黏接劑層重疊並進行層壓後,將與保護層層壓的另一個面與另行形成於剝離性片上的導電黏接劑層重疊並進行層壓;方法(viii)在具有開口部的壓延銅箔的表面中,60°鏡面光澤度為10~800的面的另一個面上塗敷樹脂組成物而形成保護層,並貼合剝離性片。之後,將另一個面與另行形成於剝離性片上的導電黏接劑層重疊並進行層壓;方法(ix)在具有開口部的壓延銅箔的表面中,60°鏡面光澤度為10~800的面上塗敷導電性樹脂組成物而形成導電黏接劑層,並貼合剝離性片。之後,將另一個面與另行形成於剝離性片上的保護層重疊並進行層壓;等。"Manufacturing Method of Electromagnetic Wave Shielding Sheet" A known method can be used for the manufacturing method of the electromagnetic wave shielding sheet. For example, the method (i) forming a conductive adhesive layer on a peelable sheet, and superimposing the conductive adhesive layer on an electrolytic copper foil with an opening with a carrier material (also referred to as a copper foil with a carrier material) After laminating the surface side of the electrolytic copper foil, the carrier material is peeled off. Then, the surface from which the carrier material is peeled and the protective layer separately formed on the peelable sheet are superimposed and laminated; method (ii) forming a protective layer on the peelable sheet, and superimposing the protective layer on the opening of the carrier material After the electrolytic copper foil is laminated on the electrolytic copper foil surface side, the carrier material is peeled off. Then, the surface from which the carrier material is peeled and the conductive adhesive layer separately formed on the peelable sheet are superimposed and laminated; method (iii) on the side of the electrolytic copper foil surface of the electrolytic copper foil with openings of the carrier material The resin composition is applied to form a protective layer, and the releasable sheet is bonded. After that, the carrier material is peeled off, and the conductive adhesive layer separately formed on the peelable sheet is superimposed and laminated; method (iv) forming a conductive adhesive layer on the peelable sheet, and overlaying the conductive adhesive layer on the tape carrier After laminating the electrolytic copper foil surface side of the copper foil of the material, the carrier material is peeled off. Then, the surface from which the carrier material is peeled and the protective layer separately formed on the peelable sheet are superimposed and laminated, and then an opening is formed on the electromagnetic wave shielding sheet with a needle-shaped jig; method (v) is formed on the peelable sheet The protective layer of is overlapped on the electrolytic copper foil surface side of the electrolytic copper foil with openings of the carrier material and laminated, and then the carrier material is peeled off. Then, a conductive adhesive layer is formed on the surface from which the carrier material is peeled; the method (vi) is to form a conductive adhesive layer on the peelable sheet, and the surface of the rolled copper foil with openings has a 60° mirror gloss After the surface of 10 to 800 is overlapped with the conductive adhesive layer and laminated, the other surface laminated with the conductive adhesive layer is overlapped with the protective layer separately formed on the peelable sheet and laminated; method (vii ) A protective layer is formed on the peelable sheet, and the other surface of the rolled copper foil with openings that has a 60° mirror gloss of 10 to 800 is overlapped with the conductive adhesive layer and laminated, and then the The other side laminated with the protective layer overlaps and laminates the conductive adhesive layer separately formed on the peelable sheet; method (viii) on the surface of the rolled copper foil with openings, 60° specular gloss is The other surface of the 10-800 surface is coated with a resin composition to form a protective layer, and a peelable sheet is bonded. After that, the other side is overlapped with the conductive adhesive layer separately formed on the peelable sheet and laminated; method (ix) on the surface of the rolled copper foil with openings, the 60° specular gloss is 10 to 800 The conductive resin composition is coated on the surface of the slab to form a conductive adhesive layer, and the peelable sheet is attached. After that, the other surface is overlapped with a protective layer separately formed on the peelable sheet and laminated; etc.
電磁波屏蔽片除了導電黏接劑層、金屬層及保護層以外,也可包括其他功能層。其他功能層是具有硬塗性、水蒸氣阻擋性、氧氣阻擋性、導熱性、低介電常數性、高介電常數性、或耐熱性等功能的層。In addition to the conductive adhesive layer, the metal layer and the protective layer, the electromagnetic wave shielding sheet may also include other functional layers. The other functional layer is a layer having functions such as hard coat properties, water vapor barrier properties, oxygen barrier properties, thermal conductivity, low dielectric constant, high dielectric constant, or heat resistance.
本發明的電磁波屏蔽片可用於需要屏蔽電磁波的各種用途。例如,柔性印刷電路自不待言,也可用於剛性印刷電路、覆晶薄膜(Chip On Film,COF)、卷帶自動結合(Tape Automated Bonding,TAB)、柔性連接器、液晶顯示器、觸控螢幕等。而且,也可用作個人電腦的殼體、建材的壁及窗玻璃等建材、阻斷車輛、船舶、飛機等的電磁波的構件。The electromagnetic wave shielding sheet of the present invention can be used for various applications that need to shield electromagnetic waves. For example, it goes without saying that flexible printed circuits can also be used for rigid printed circuits, Chip On Film (COF), Tape Automated Bonding (TAB), flexible connectors, liquid crystal displays, touch screens, etc. . In addition, it can also be used as a component for building materials such as the housing of a personal computer, the wall of building materials and window glass, and a member that blocks electromagnetic waves in vehicles, ships, and airplanes.
本發明的電磁波屏蔽片當在導電黏接劑層中的黏合劑樹脂中使用熱塑性樹脂時,通過使所含的熱塑性樹脂以固體狀態存在,並利用與配線電路基板的熱壓,使熱塑性樹脂熔融並在冷卻後再次固體化,而可獲得所期望的黏接強度。In the electromagnetic wave shielding sheet of the present invention, when a thermoplastic resin is used for the adhesive resin in the conductive adhesive layer, the thermoplastic resin contained is present in a solid state, and the thermoplastic resin is melted by hot pressing with the wiring circuit board And solidified again after cooling, and the desired bonding strength can be obtained.
本發明的電磁波屏蔽片當在導電黏接劑層中的黏合劑樹脂中使用熱硬化性樹脂時,通過使所含的熱硬化性樹脂與硬化劑以未硬化狀態存在(B階段),並利用與配線電路基板的熱壓進行硬化(C階段),而可獲得所期望的黏接強度。另外,所述未硬化狀態包含硬化劑的一部分進行了硬化的半硬化狀態。In the electromagnetic wave shielding sheet of the present invention, when a thermosetting resin is used for the binder resin in the conductive adhesive layer, the thermosetting resin and curing agent contained in the sheet are present in an uncured state (stage B), and use It is hardened by hot pressing with the printed circuit board (C stage), and the desired bonding strength can be obtained. In addition, the uncured state includes a semi-cured state in which a part of the hardener is hardened.
另外,為了防止異物的附著,通常以將剝離性片貼附於導電黏接劑層及保護層的狀態來保存電磁波屏蔽片。In addition, in order to prevent the adhesion of foreign matter, the electromagnetic wave shielding sheet is usually stored in a state where the peelable sheet is attached to the conductive adhesive layer and the protective layer.
剝離性片為對紙或塑膠等基材進行了公知的剝離處理的片。The peelable sheet is a sheet obtained by subjecting a base material such as paper or plastic to a known peeling treatment.
<電磁波屏蔽性配線電路基板> 電磁波屏蔽性配線電路基板包括由本發明的電磁波屏蔽片形成的電磁波屏蔽層、面塗層、以及包括具有信號配線與接地配線的電路圖案及絕緣性基材的配線電路基板。 配線電路基板在絕緣性基材的表面包括具有信號配線及接地配線的電路圖案,通過在所述配線電路基板上形成對信號配線及接地配線進行絕緣保護,在接地配線上的至少一部分具有通路的面塗層,並將電磁波屏蔽片的導電黏接劑層面配置在所述面塗層上,之後,對所述電磁波屏蔽片進行熱壓,使導電黏接劑層流入至通路內部與接地配線黏接,藉此可製造電磁波屏蔽性配線電路基板。<Electromagnetic wave shielding wiring circuit board> The electromagnetic wave shielding wiring circuit board includes an electromagnetic wave shielding layer formed of the electromagnetic wave shielding sheet of the present invention, a top coat, and a wiring circuit board including a circuit pattern having signal wiring and ground wiring, and an insulating base material. The wiring circuit board includes a circuit pattern having signal wiring and ground wiring on the surface of the insulating base material, and the signal wiring and the ground wiring are insulated and protected by forming on the wiring circuit board, so that at least a part of the ground wiring has a path The conductive adhesive layer of the electromagnetic wave shielding sheet is arranged on the surface coating, and then the electromagnetic wave shielding sheet is thermally pressed to make the conductive adhesive layer flow into the via and adhere to the ground wiring Then, an electromagnetic wave shielding wiring circuit board can be manufactured by this.
針對本發明的電磁波屏蔽性配線電路基板的一例,參照圖3進行說明。電磁波屏蔽層12為包括導電黏接劑層a1、金屬層a2、保護層a3的構成。An example of the electromagnetic wave shielding printed circuit board of the present invention will be described with reference to FIG. 3. The electromagnetic
面塗層8為對配線電路基板的信號配線進行覆蓋並保護其免受外部環境的破壞的絕緣材料。面塗層優選為帶熱硬化性黏接劑的聚醯亞胺膜、熱硬化型或紫外線硬化型的阻焊劑、或者感光性覆蓋膜,為了進行微細加工,更優選為感光性覆蓋膜。而且,面塗層通常是使用聚醯亞胺等具有耐熱性與柔軟性的公知的樹脂。面塗層的厚度通常為10 μm~100 μm左右。The
電路圖案包括接地的接地配線5、將電性信號發送至電子零件的信號配線6。兩者通常是通過對銅箔進行蝕刻處理而形成。電路圖案的厚度通常為1 μm~50 μm左右。The circuit pattern includes a
絕緣性基材9是電路圖案的支撐體,優選為聚酯、聚碳酸酯、聚醯亞胺、聚苯硫醚、液晶聚合物等能夠彎曲的塑膠,更優選為液晶聚合物及聚醯亞胺。這些中,若考慮傳輸高頻的信號的配線電路基板的用途,則進而優選為相對介電常數及介電損耗正切低的液晶聚合物。 在配線電路基板為剛性電路的情況下,絕緣性基材的構成材料優選為玻璃環氧。通過包括像這些這樣的絕緣性基材,配線電路基板獲得高的耐熱性。The insulating substrate 9 is a support for the circuit pattern, and is preferably a bendable plastic such as polyester, polycarbonate, polyimide, polyphenylene sulfide, liquid crystal polymer, and more preferably liquid crystal polymer and polyamide. amine. Among these, considering the use of a wiring circuit board for transmitting high-frequency signals, it is more preferable to use a liquid crystal polymer having a low relative permittivity and a low dielectric loss tangent. When the printed circuit board is a rigid circuit, the constituent material of the insulating base material is preferably glass epoxy. By including insulating base materials such as these, the printed circuit board obtains high heat resistance.
電磁波屏蔽片10與配線電路基板的熱壓通常在溫度150℃~190℃左右、壓力1 MPa~3 MPa左右、時間1分鐘~60分鐘左右的條件下進行。通過熱壓,導電黏接劑層1與面塗層8密接,並且導電黏接劑層1發生流動而填埋形成於面塗層8的通路11,藉此在與接地配線5之間實現導通。通過熱壓,熱硬化性樹脂進行反應而硬化,成為電磁波屏蔽層12。另外,也有時為了促進硬化,而在熱壓後以150℃~190℃進行30分鐘~90分鐘的後固化。The hot pressing of the electromagnetic
所述通路11的開口面積優選為0.8 mm2
以下,並且優選為0.008 mm2
以上。通過設為所述範圍,可縮窄接地配線的區域,從而可實現印刷電路的小型化。通路的形狀並無特別限定,可根據用途使用圓、正方形、長方形、三角形及不定形等中的任一種。經過這些步驟,獲得電磁波屏蔽性配線電路基板7。The opening area of the
就可更有效果地抑制電磁波的洩漏的方面而言,優選將電磁波屏蔽層層壓於配線電路基板的兩面。此外,本發明的電磁波屏蔽性配線電路基板中的電磁波屏蔽層除了對電磁波進行遮蔽以外,還可用作接地電路,藉此,通過省略接地電路的一部分,縮小配線電路基板的面積,成本降低成為可能,並且可組裝至框體內的狹小區域。In terms of suppressing the leakage of electromagnetic waves more effectively, it is preferable to laminate electromagnetic wave shielding layers on both sides of the printed circuit board. In addition, the electromagnetic wave shielding layer in the electromagnetic wave shielding printed circuit board of the present invention can be used as a grounding circuit in addition to shielding electromagnetic waves. By this, by omitting a part of the grounding circuit, the area of the printed circuit board is reduced and the cost is reduced. It is possible and can be assembled into a small area inside the frame.
而且,關於信號配線,並無特別限定,可在包括一根信號配線的單端(single ended)、包括兩根信號配線的差動電路的任一電路中使用,但優選為差動電路。另一方面,當在配線電路基板的電路圖案面積中存在制約,難以並聯形成接地電路時,也可不在信號電路的橫向設置接地電路,而將電磁波屏蔽層用作接地電路,製成在厚度方向上具有接地的印刷電路結構。Furthermore, the signal wiring is not particularly limited, and it can be used in either a single ended (single ended) circuit including one signal wiring or a differential circuit including two signal wirings, but a differential circuit is preferable. On the other hand, when there are restrictions on the circuit pattern area of the printed circuit board and it is difficult to form a ground circuit in parallel, the ground circuit may not be provided in the lateral direction of the signal circuit, and the electromagnetic wave shielding layer may be used as the ground circuit to be formed in the thickness direction. It has a grounded printed circuit structure.
本發明的電磁波屏蔽性配線電路基板優選除了搭載於液晶顯示器、觸控螢幕等以外,還搭載於筆記本式PC、行動電話、智慧型手機、平板終端等電子設備。 [實施例]The electromagnetic wave shielding printed circuit board of the present invention is preferably mounted on electronic devices such as notebook PCs, mobile phones, smart phones, and tablet terminals in addition to liquid crystal displays, touch screens, and the like. [Example]
以下,通過實施例對本發明進行更詳細的說明,但本發明並不限定於以下的實施例。而且,實施例中的「份」表示「質量份」,「%」表示「質量%」。Hereinafter, the present invention will be explained in more detail through examples, but the present invention is not limited to the following examples. In addition, "parts" in the examples means "parts by mass", and "%" means "% by mass".
另外,樹脂的酸值、重量平均分子量(Mw)、玻璃化轉變溫度(Tg)、及導電性填料的平均粒徑的測定是利用以下的方法來進行。In addition, the acid value of the resin, the weight average molecular weight (Mw), the glass transition temperature (Tg), and the average particle diameter of the conductive filler are measured by the following methods.
《黏合劑樹脂的酸值的測定》 酸值是依據JIS K0070進行測定。在帶塞錐形瓶中精密地量取約1 g的試樣,加入四氫呋喃/乙醇(容量比:四氫呋喃/乙醇=2/1)混合液100 mL進行溶解。向其中加入酚酞試液作為指示劑,以0.1 N醇性氫氧化鉀溶液進行滴定,將指示劑保持淡紅色30秒鐘的時刻設為終點。根據下式求出酸值(單位:mgKOH/g)。 酸值(mgKOH/g)=(5.611×a×F)/S 其中, S:試樣的採取量(g) a:0.1N醇性氫氧化鉀溶液的消耗量(mL) F:0.1N醇性氫氧化鉀溶液的滴定度"Determination of acid value of binder resin" The acid value is measured in accordance with JIS K0070. Accurately measure about 1 g of the sample in a stoppered Erlenmeyer flask, add 100 mL of tetrahydrofuran/ethanol (volume ratio: tetrahydrofuran/ethanol=2/1) mixture to dissolve. A phenolphthalein test solution was added as an indicator, and titration was performed with a 0.1 N alcoholic potassium hydroxide solution, and the time when the indicator remained light red for 30 seconds was set as the end point. Calculate the acid value (unit: mgKOH/g) according to the following formula. Acid value (mgKOH/g)=(5.611×a×F)/S in, S: The amount of sample taken (g) a: Consumption of 0.1N alcoholic potassium hydroxide solution (mL) F: The titer of 0.1N alcoholic potassium hydroxide solution
《黏合劑樹脂的重量平均分子量(Mw)的測定》 重量平均分子量(Mw)的測定是使用東曹(Tosoh)股份有限公司製造的膠體滲透層析儀(Gel Permeation Chromatograph,GPC)「HPC-8020」。GPC是根據溶解於溶媒(THF;四氫呋喃(tetrahydrofuran))中的物質的分子大小的差異而對其進行分離定量的液相色譜儀。本發明中的測定是串聯地連接兩根「LF-604」(昭和電工股份有限公司製造:迅速分析用GPC管柱:6 mmID×150 mm大小)而用作管柱,並以流量0.6 mL/min、管柱溫度40℃的條件來進行,重量平均分子量(Mw)的確定是通過聚苯乙烯換算來進行。"Determination of the weight average molecular weight (Mw) of the binder resin" The weight average molecular weight (Mw) was measured using a gel permeation chromatography (Gel Permeation Chromatograph, GPC) "HPC-8020" manufactured by Tosoh Co., Ltd. GPC is a liquid chromatograph that separates and quantifies substances dissolved in a solvent (THF; tetrahydrofuran) based on their molecular size differences. In the measurement of the present invention, two "LF-604" (manufactured by Showa Denko Co., Ltd.: GPC column for rapid analysis: 6 mmID×150 mm size) are connected in series and used as a column, and the flow rate is 0.6 mL/ Min, the column temperature is 40°C, and the weight average molecular weight (Mw) is determined by polystyrene conversion.
《黏合劑樹脂的玻璃化轉變溫度(Tg)》 Tg的測定是通過差示掃描量熱測定(梅特勒-托利多(Mettler Toledo)公司製造的「DSC-1」)來測定。"Glass Transition Temperature (Tg) of Adhesive Resin" The Tg is measured by differential scanning calorimetry ("DSC-1" manufactured by Mettler Toledo).
《導電性填料的平均粒徑測定》 D50 平均粒徑是使用雷射繞射·散射法粒度分佈測定裝置LS13320(貝克曼庫爾特(Beckman Coulter)公司製造),並通過旋風乾燥粉體樣品模塊(tornado dry powder sample module)測定導電性填料而獲得的數值,且為粒徑累積分佈中的累積值為50%的粒徑。另外,將折射率的設定設為1.6。"Measurement of the average particle size of conductive filler" The average particle size of D 50 is measured by using a laser diffraction and scattering method particle size distribution analyzer LS13320 (manufactured by Beckman Coulter), and the powder sample is dried by a cyclone Module (tornado dry powder sample module) is the value obtained by measuring the conductive filler, and it is the particle size whose cumulative value in the cumulative particle size distribution is 50%. In addition, the refractive index is set to 1.6.
繼而,以下示出實施例中所使用的原料。 《原料》 導電性填料1:複合微粒子(相對於作為核體的銅100質量份而包覆有10質量份的銀的樹突狀的微粒子)平均粒徑D50 :12.0 μm 福田金屬箔粉工業公司製造 導電性填料2:複合微粒子(相對於作為核體的銅100質量份而包覆有10質量份的銀的樹突狀的微粒子)平均粒徑D50 :1.0 μm 福田金屬箔粉工業公司製造 導電性填料3:複合微粒子(相對於作為核體的銅100質量份而包覆有10質量份的銀的樹突狀的微粒子)平均粒徑D50 :6.0 μm 福田金屬箔粉工業公司製造 導電性填料4:複合微粒子(相對於作為核體的銅100質量份而包覆有10質量份的銀的樹突狀的微粒子)平均粒徑D50 :17.0 μm 福田金屬箔粉工業公司製造 導電性填料5:複合微粒子(相對於作為核體的銅100質量份而包覆有10質量份的銀的樹突狀的微粒子)平均粒徑D50 :32.0 μm 福田金屬箔粉工業公司製造 黏合劑樹脂:酸值5 mgKOH/g、Mw為54,000、Tg為-7℃的聚氨基甲酸酯脲樹脂(東洋化工(TOYO CHEM)公司製造) 環氧化合物:「JER828」(雙酚A型環氧樹脂 環氧當量=189 g/eq)三菱化學公司製造 氮丙啶化合物:「凱米泰特(Chemitite)PZ-33」日本催化劑公司製造 顏料:碳黑「MA100」三菱化學公司製造 載體材:「恩布萊特(emblet)S25」尤尼吉可(UNITIKA)公司製造Next, the raw materials used in the examples are shown below. "Raw material" Conductive filler 1: Composite fine particles (dendritic fine particles coated with 10 parts by mass of silver relative to 100 parts by mass of copper as a core) Average particle size D 50 : 12.0 μm Fukuda Metal Foil Powder Industry Company-manufactured conductive filler 2: Composite fine particles (dendritic fine particles coated with 10 parts by mass of silver relative to 100 parts by mass of copper as a core) Average particle size D 50 : 1.0 μm Fukuda Metal Foil & Powder Industry Co., Ltd. Manufacture of conductive filler 3: Composite fine particles (dendritic fine particles coated with 10 parts by mass of silver relative to 100 parts by mass of copper as a core) Average particle size D 50 : 6.0 μm manufactured by Fukuda Metal Foil & Powder Industry Co., Ltd. Conductive filler 4: Composite fine particles (dendritic fine particles coated with 10 parts by mass of silver relative to 100 parts by mass of copper as a core) Average particle size D 50 : 17.0 μm, manufactured by Fukuda Metal Foil & Powder Co., Ltd. Conductive Filler 5: Composite fine particles (dendritic fine particles coated with 10 parts by mass of silver relative to 100 parts by mass of copper as the core) Average particle size D 50 : 32.0 μm Adhesive manufactured by Fukuda Metal Foil Industry Co., Ltd. Resin: Polyurethane urea resin with acid value of 5 mgKOH/g, Mw of 54,000 and Tg of -7°C (manufactured by TOYO CHEM) Epoxy compound: "JER828" (bisphenol A epoxy Resin epoxy equivalent = 189 g/eq) Aziridine compound manufactured by Mitsubishi Chemical Corporation: "Chemitite PZ-33" manufactured by Japan Catalyst Co., Ltd. Pigment: carbon black "MA100" Carrier material manufactured by Mitsubishi Chemical Corporation: ""EmbletS25" manufactured by UNITIKA
將所使用的帶載體材的銅箔示於表1。 這些帶載體材的銅箔是通過在載體材上所形成的銅箔上形成圖案抗蝕劑層,並對銅箔進行蝕刻來形成開口部的方法,而形成的具有表1中所示的厚度及開口率等的銅箔。Table 1 shows the copper foil with carrier material used. These copper foils with a carrier material are formed by forming a patterned resist layer on the copper foil formed on the carrier material, and etching the copper foil to form openings, and have the thickness shown in Table 1. And copper foil such as aperture ratio.
[表1]
<導電黏接劑層1的製造>
以固形成分換算,將黏合劑樹脂100份、導電性填料1 47份、環氧化合物10份及氮丙啶化合物0.5份裝入至容器中,以不揮發成分濃度成為40%的方式添加混合溶劑(甲苯:異丙醇=2:1(質量比)),並利用分散機攪拌10分鐘,獲得導電性樹脂組成物。<Production of conductive
利用棒塗機,以乾燥厚度成為10 μm的方式將導電性樹脂組成物塗敷於剝離性片上,利用100℃的電烘箱進行2分鐘乾燥,藉此獲得導電黏接劑層1。Using a bar coater, the conductive resin composition was coated on the peelable sheet so that the dry thickness became 10 μm, and dried in an electric oven at 100° C. for 2 minutes, thereby obtaining a conductive
<導電黏接劑層2~導電黏接劑層12的製造>
除了改變導電性填料的種類及添加量以外,以與導電黏接劑層1同樣的方法製作表2~表5中所示的導電黏接劑層2~導電黏接劑層12。<Manufacturing of Conductive Adhesive Layer 2-
[實施例1]
以固形成分換算,加入黏合劑樹脂100份、環氧化合物30份以及氮丙啶化合物7.5份,利用分散機攪拌10分鐘,藉此獲得樹脂組成物。使用棒塗機,將所獲得的樹脂組成物以乾燥厚度成為5 μm的方式塗敷於帶載體材的銅箔A1,利用100℃的電烘箱進行2分鐘乾燥,形成保護層1,將微黏著剝離性片貼合於保護層1。[Example 1]
In terms of solid content, 100 parts of the binder resin, 30 parts of the epoxy compound, and 7.5 parts of the aziridine compound were added, and stirred with a disperser for 10 minutes to obtain a resin composition. Using a bar coater, the obtained resin composition was applied to a copper foil A1 with a carrier material so that the dry thickness became 5 μm, and dried in an electric oven at 100°C for 2 minutes to form a
繼而,剝離帶載體材的銅箔A1的載體材,對銅箔面進行拋光研磨,將銅箔面的60°鏡面光澤度調整為表2所示的值,製成銅箔2。在研磨後的銅箔面上貼合導電黏接劑層4,藉此獲得包括「剝離性片/保護層1/銅箔2/導電黏接劑層4/剝離性片」的電磁波屏蔽片。銅箔2與導電黏接劑層4的貼合是在溫度90℃、壓力3 kgf/cm2
下,通過熱層壓機來貼合。Then, the carrier material of the copper foil A1 with the carrier material was peeled, the copper foil surface was polished, and the 60° mirror gloss of the copper foil surface was adjusted to the value shown in Table 2, and the
[實施例2~實施例33、比較例1~比較例4] 除了像表1~表5所示的那樣變更導電黏接劑層、保護層及銅箔的種類以外,與實施例1同樣地進行,藉此分別獲得實施例2~實施例33、比較例1~比較例4的電磁波屏蔽片。在銅箔表面的60°鏡面光澤度的目標值與載體材的值不同的情況下,通過適當利用拋光研磨來研磨表面或者將表面粗糙化等,來調整60°鏡面光澤度。[Example 2 to Example 33, Comparative Example 1 to Comparative Example 4] Except that the types of conductive adhesive layer, protective layer, and copper foil were changed as shown in Tables 1 to 5, the same procedure as in Example 1 was carried out to obtain Examples 2 to 33 and Comparative Example 1, respectively. ~ The electromagnetic wave shielding sheet of Comparative Example 4. When the target value of the 60° mirror gloss on the copper foil surface is different from the value of the carrier material, the 60° mirror gloss is adjusted by appropriately polishing the surface or roughening the surface.
針對所獲得的電磁波屏蔽片,利用如下方法進行各層的厚度、金屬層的60°鏡面光澤度、及電磁波屏蔽片的損耗正切的測定。With respect to the obtained electromagnetic wave shielding sheet, the thickness of each layer, the 60° specular gloss of the metal layer, and the loss tangent of the electromagnetic wave shielding sheet were measured by the following methods.
《各層厚度的測定》 電磁波屏蔽片的熱壓後的導電黏接劑層、金屬層及保護層的厚度是通過以下的方法測定。 將電磁波屏蔽片的導電黏接劑層側的剝離性片剝離,將露出的導電黏接劑層與聚醯亞胺膜(東麗杜邦(Toray-Dupont)公司製造的「卡普頓(Kapton)200EN」)貼合,在2 MPa、170℃的條件下熱壓30分鐘。將其切斷為寬度5 mm、長度5 mm左右的大小後,將環氧樹脂(派特牢包克斯(Petropoxy)154,丸東(maruto)公司製造)0.05 g滴加至載玻片上,並黏接電磁波屏蔽片,獲得載玻片/電磁波屏蔽片/聚醯亞胺膜的構成的層壓體。針對所獲得的層壓體,使用剖面拋光機(Cross section polisher)(日本電子公司製造,SM-09010)從聚醯亞胺膜側通過離子束照射進行切斷加工,獲得電磁波屏蔽片的熱壓後的測定試樣。"Measurement of the thickness of each layer" The thickness of the conductive adhesive layer, the metal layer, and the protective layer after hot pressing of the electromagnetic wave shielding sheet is measured by the following method. The peelable sheet on the conductive adhesive layer side of the electromagnetic wave shielding sheet is peeled off, and the exposed conductive adhesive layer and the polyimide film ("Kapton" manufactured by Toray-Dupont Co., Ltd.) are peeled off. 200EN”) bonding and hot pressing at 2 MPa and 170°C for 30 minutes. After cutting it into a size of 5 mm in width and 5 mm in length, 0.05 g of epoxy resin (Petropoxy 154, manufactured by Maruto Co., Ltd.) was dropped onto the glass slide. Then, the electromagnetic wave shielding sheet is bonded to obtain a laminate of glass slide/electromagnetic wave shielding sheet/polyimide film. For the obtained laminate, a cross section polisher (manufactured by JEOL Co., Ltd., SM-09010) was cut from the polyimide film side by ion beam irradiation to obtain a hot press of the electromagnetic wave shielding sheet. After the measurement sample.
使用雷射顯微鏡(基恩士(KEYENCE)公司製造,VK-X100)觀察所獲得的測定試樣的剖面,根據觀察所得的放大圖像來測定各層的厚度。倍率設為500倍~2000倍。The cross section of the obtained measurement sample was observed using a laser microscope (manufactured by KEYENCE, VK-X100), and the thickness of each layer was measured based on the enlarged image obtained by the observation. The magnification is set from 500 times to 2000 times.
《60°鏡面光澤度的測定》 電磁波屏蔽片的金屬層的60°鏡面光澤度是通過以下的方法測定。 將電磁波屏蔽片的導電黏接劑層側的剝離性片剝離,在露出的導電黏接劑層上以殘留黏著帶(米其邦(Nichiban)公司製造的「CT1835」)的端部的方式貼合黏著帶,從黏著帶的端部進行剝離,剝離導電黏接劑層/黏著帶。除去導電黏接劑層,針對露出的金屬層的表面,使用光澤儀(glossmeter)(畢克(BYK)公司製造,微三角度光澤儀(Micro-Tri-Gloss))測定鏡面光澤度,將測定角度60°的測定值作為60°鏡面光澤度。"Measurement of 60° Mirror Gloss" The 60° specular gloss of the metal layer of the electromagnetic wave shielding sheet was measured by the following method. The peelable sheet on the conductive adhesive layer side of the electromagnetic wave shielding sheet is peeled off, and the end of the adhesive tape ("CT1835" manufactured by Nichiban) is pasted on the exposed conductive adhesive layer. Join the adhesive tape, peel off from the end of the adhesive tape, and peel off the conductive adhesive layer/adhesive tape. The conductive adhesive layer is removed, and the surface of the exposed metal layer is measured using a glossmeter (manufactured by BYK, Micro-Tri-Gloss) and measuring the gloss of the mirror surface. The measured value at an angle of 60° is regarded as 60° specular gloss.
《層壓硬化物的損耗正切的測定》 層壓硬化物的損耗正切是通過以下的方法測定。 首先,準備兩枚寬度50 mm、長度50 mm的電磁波屏蔽片,將各自的導電黏接劑層側的剝離性片剝離,將露出的導電黏接劑層彼此貼合,在170℃、2.0 MPa、30分鐘的條件下壓接,使其熱硬化,獲得層壓硬化物。之後,將層壓硬化物的中心部分裁剪成寬度5 mm、長度30 mm,作為試樣。將此試樣設置在動態黏彈性測定裝置(動態黏彈性測定裝置DVA-200,IT測量控制公司製造)中,在升溫速度:10℃/分鐘、測定頻率:1 Hz、應變:0.08%的條件下進行動態黏彈性測定,根據所獲得的動態黏彈性曲線讀取125℃下的損耗彈性係數E''、儲存彈性係數E',計算出層壓硬化物的損耗正切。"Determination of Loss Tangent of Laminated Hardened Material" The loss tangent of the laminate cured product is measured by the following method. First, prepare two electromagnetic wave shielding sheets with a width of 50 mm and a length of 50 mm. The peelable sheets on the conductive adhesive layer side are peeled off, and the exposed conductive adhesive layers are bonded to each other at 170°C, 2.0 MPa , Crimping under the condition of 30 minutes to make it heat-cured to obtain a laminated hardened product. After that, the central part of the laminated hardened product was cut to a width of 5 mm and a length of 30 mm, as a sample. Set this sample in a dynamic viscoelasticity measuring device (DVA-200, a dynamic viscoelasticity measuring device, manufactured by IT Measurement and Control Co., Ltd.) under the conditions of heating rate: 10°C/min, measuring frequency: 1 Hz, and strain: 0.08% The dynamic viscoelasticity measurement is carried out under the following conditions, and the loss elastic coefficient E" and storage elastic coefficient E'at 125°C are read according to the obtained dynamic viscoelastic curve, and the loss tangent of the laminated hardened product is calculated.
使用所獲得的電磁波屏蔽片進行下述評價。將結果示於表2~表5。The following evaluation was performed using the obtained electromagnetic wave shielding sheet. The results are shown in Table 2 to Table 5.
<回流焊耐性> 回流焊耐性是進行以下的試驗並通過外觀變化的有無來評價。回流焊耐性高的電磁波屏蔽片的外觀不變化,但回流焊耐性低的電磁波屏蔽片發生發泡或剝離。 首先,將寬度25 mm、長度70 mm的電磁波屏蔽片的導電黏接劑層的剝離性片剝離,將露出的導電黏接劑層與總厚64 μm的經鍍金處理的覆銅層壓板(鍍金0.3 μm/鍍鎳1 μm/銅箔18 μm/黏接劑20 μm/聚醯亞胺膜25 μm)的鍍金面在170℃、2.0 MPa、30分鐘的條件下進行壓接,使其熱硬化而獲得層壓體。將所獲得的層壓體切割成寬度10 mm、長度65 mm的大小而製作試樣。將所獲得的試樣在40℃、90%RH的氣體環境下放置72小時。之後,使試樣的聚醯亞胺膜面朝下在250℃的熔融焊料上漂浮1分鐘,繼而取出試樣,以目視觀察其外觀,按照以下基準評價有無發泡、浮起、剝離等異常。 ◎:外觀完全無變化。 極其良好。 〇:觀察到少量小的發泡。 良好。 Δ:觀察到大量小的發泡。 可實用。 ×:觀察到嚴重的發泡或剝離。 不可實用。<Reflow resistance> The resistance to reflow soldering was evaluated by the following tests and the presence or absence of changes in appearance. The appearance of the electromagnetic wave shielding sheet with high reflow resistance does not change, but the electromagnetic wave shielding sheet with low reflow resistance undergoes foaming or peeling. First, the peelable sheet of the conductive adhesive layer of the electromagnetic wave shielding sheet with a width of 25 mm and a length of 70 mm is peeled off, and the exposed conductive adhesive layer is separated from the gold-plated copper-clad laminate (gold-plated 0.3 μm/nickel-plated 1 μm/copper foil 18 μm/adhesive 20 μm/polyimide film 25 μm) The gold-plated surface is crimped at 170°C, 2.0 MPa, and 30 minutes to make it thermally hardened And a laminate is obtained. The obtained laminate was cut into a size of 10 mm in width and 65 mm in length to prepare samples. The obtained sample was placed in a gas environment of 40° C. and 90% RH for 72 hours. After that, the polyimide film of the sample was floated on the molten solder at 250°C for 1 minute, and then the sample was taken out to visually observe its appearance, and evaluate whether there are abnormalities such as foaming, floating, peeling, etc. according to the following criteria . ◎: There is no change in appearance at all. Very good. ○: A small amount of small foaming is observed. Good. Δ: A large amount of small foaming is observed. Can be practical. ×: Severe foaming or peeling is observed. Not practical.
<彎折耐性> 將寬度20 mm、長度100 mm的電磁波屏蔽片的導電黏接劑層的剝離性片剝離,將露出的導電黏接劑層與寬度20 mm、長度100 mm的卡普頓(Kapton)500H在150℃、2.0 MPa、30分鐘的條件下壓接,使其熱硬化,獲得試樣。以使所獲得的試樣的電磁波屏蔽層成為外側的方式彎折180度,在彎折部位載置1000 g的砝碼10秒鐘,之後,將彎折的部位恢復至原本的平面狀態,再次載置1000 g的砝碼10秒鐘,將這設為彎折次數1次。利用基恩士(KEYENCE)(股)製造的顯微鏡「VHX-900」觀察電磁波屏蔽片中是否產生了裂紋,評價未發生裂紋的情況下可彎折的次數。 計數在施加1000 g負荷的彎折部中產生裂紋之前的彎折次數。評價基準如下。 ◎:10次以上。 極其良好。 〇:7次以上且不足10次。 良好。 Δ:2次以上且不足7次。 可實用。 ×:不足2次。 不可實用。<Bending resistance> Peel off the conductive adhesive layer of the electromagnetic wave shielding sheet with a width of 20 mm and a length of 100 mm, and separate the exposed conductive adhesive layer from the Kapton 500H with a width of 20 mm and a length of 100 mm. Crimping was performed under the conditions of ℃, 2.0 MPa, and 30 minutes to heat-harden to obtain a sample. The obtained sample was bent 180 degrees so that the electromagnetic wave shielding layer of the sample was outside, and a 1000 g weight was placed on the bent portion for 10 seconds. After that, the bent portion was restored to its original flat state. Place a weight of 1000 g for 10 seconds and set this as the number of bends once. Use the microscope "VHX-900" manufactured by KEYENCE (stock) to observe whether there are cracks in the electromagnetic wave shielding sheet, and evaluate the number of times that it can be bent without cracks. Count the number of flexures before cracks occur in the flexure where a 1000 g load is applied. The evaluation criteria are as follows. ◎: 10 times or more. Very good. ○: 7 times or more and less than 10 times. Good. Δ: 2 times or more and less than 7 times. Can be practical. ×: Less than 2 times. Not practical.
<高頻屏蔽性> 關於高頻屏蔽性,依據美國材料與試驗協會(American Society for Testing and Materials,ASTM)D4935,使用肯考姆(keycom)公司製造的同軸管型的屏蔽效果測定系統,獲得不進行對被黏接體的熱壓接而對電磁波屏蔽片進行硬化而成的試樣。然後,針對所述試樣,在100 MHz~15 GHz條件下進行電磁波的照射,測定電磁波衰減的衰減量,並依照以下的基準進行標記。對電磁波屏蔽片進行硬化而成的試樣是通過在150℃、2.0 MPa、30分鐘的條件下對附著有剝離性片的電磁波屏蔽片進行熱壓,並將剝離性片剝離而獲得。另外,衰減量的測定值為分貝(單位;dB)。 ◎:照射15 GHz的電磁波時的衰減量不足-55 dB。極其良好。 〇:照射15 GHz的電磁波時的衰減量為-55 dB以上且不足-50 dB。良好。 Δ:照射15 GHz的電磁波時的衰減量為-50 dB以上且不足-45 dB。可實用。 ×:照射15 GHz的電磁波時的衰減量為-45 dB以上。不可實用。<High frequency shielding ability> Regarding high-frequency shielding performance, according to American Society for Testing and Materials (ASTM) D4935, a coaxial tube-type shielding effect measurement system manufactured by Keycom is used to obtain a non-bonding effect. A sample obtained by curing the electromagnetic wave shielding sheet by thermocompression bonding of the body. Then, the sample was irradiated with electromagnetic waves under the conditions of 100 MHz to 15 GHz, and the amount of attenuation of the electromagnetic wave attenuation was measured, and marking was performed in accordance with the following standards. The sample obtained by curing the electromagnetic wave shielding sheet was obtained by hot pressing the electromagnetic wave shielding sheet to which the peelable sheet was attached under the conditions of 150° C., 2.0 MPa, and 30 minutes, and peeling the peelable sheet. In addition, the measured value of the attenuation is decibels (unit; dB). ◎: The attenuation when irradiating 15 GHz electromagnetic waves is less than -55 dB. Extremely good. ○: The amount of attenuation when irradiating 15 GHz electromagnetic waves is -55 dB or more and less than -50 dB. good. Δ: The amount of attenuation when irradiating electromagnetic waves of 15 GHz is more than -50 dB and less than -45 dB. Can be practical. ×: The amount of attenuation when irradiating 15 GHz electromagnetic waves is -45 dB or more. Not practical.
<冷熱循環可靠性>
冷熱循環可靠性是通過測定冷熱循環前後經由小開口通路的連接電阻值來評價。以下示出評價的具體方法。
將電磁波屏蔽片準備成寬度20 mm、長度50 mm的大小。將各實施例及比較例的電磁波屏蔽片的剝離性片剝離,將露出的導電黏接劑層在170℃、2 MPa、30分鐘的條件下壓接於另行製作的柔性印刷電路。具體而言,如圖4中所示,作為印刷電路,使用在厚度25 μm的聚醯亞胺膜21上形成有彼此未電性連接的厚度18 μm的銅箔電路22A及銅箔電路22B,並在銅箔電路22A上層壓有厚度37.5 μm、具有直徑1.1 mm(通路面積為1.0 mm2
)的圓形通路24的帶黏接劑的聚醯亞胺覆蓋層23的電路。然後,在170℃、2 MPa、30分鐘的條件下進行壓接後,使電磁波屏蔽片的導電黏接劑層25b及保護層25a硬化,藉此獲得試樣。繼而,除去試樣的保護層25a側的剝離性片,使用三菱化學分析技術(MitsubishiChemical Analytech)製造的「勞萊斯塔(Loresta)GP」BSP探針來測定圖4的(4)的平面圖中所示的22A-22B間的初期連接電阻值。另外,圖4的(2)為圖4的(1)的D-D'剖面圖,圖4的(3)為圖4的(1)的C-C'剖面圖。同樣地,圖4的(5)為圖4的(4)的D-D'剖面圖,圖4的(6)為圖4的(4)的C-C'剖面圖。將試樣投入至冷熱衝擊裝置(「TSE-11-A」,愛斯佩克(Espec)公司製造),在高溫暴露:125℃、15分鐘、低溫暴露:-50℃、15分鐘的暴露條件下實施200次交替暴露。之後,與初期同樣地測定試樣的連接電阻值。冷熱循環可靠性的評價基準如下。
◎:(交替暴露後的連接電阻值)/(初期連接電阻值)不足1.5。極其良好。
○:(交替暴露後的連接電阻值)/(初期連接電阻值)為1.5以上且不足3.0。良好。
Δ:(交替暴露後的連接電阻值)/(初期連接電阻值)為3.0以上且不足5.0。可實用。
×:(交替暴露後的連接電阻值)/(初期連接電阻值)為5.0以上。不可實用。<Reliability of Cooling and Heating Cycles> The reliability of cooling and heating cycles is evaluated by measuring the connection resistance value through the small opening passage before and after the cooling and heating cycle. The specific method of evaluation is shown below. Prepare the electromagnetic wave shielding sheet with a width of 20 mm and a length of 50 mm. The peelable sheet of the electromagnetic wave shielding sheet of each Example and Comparative Example was peeled off, and the exposed conductive adhesive layer was crimped to a separately produced flexible printed circuit under the conditions of 170° C., 2 MPa, and 30 minutes. Specifically, as shown in FIG. 4, as a printed circuit, a
[表2]
[表3]
[表4]
[表5]
a1:導電黏接劑層
a2:金屬層
a3:保護層
a4:開口部
5:接地配線
6:信號配線
7:電磁波屏蔽性配線電路基板
8:面塗層
9:絕緣性基材
10:電磁波屏蔽片
11:通路
12:電磁波屏蔽層
21:聚醯亞胺膜
22A、22B:銅箔電路
23:帶黏接劑的聚醯亞胺覆蓋層
24:圓形通路
25a:保護層
25b:導電黏接劑層a1: Conductive adhesive layer
a2: metal layer
a3: protective layer
a4: opening
5: Ground wiring
6: Signal wiring
7: Electromagnetic wave shielding wiring circuit board
8: Top coat
9: Insulating base material
10: Electromagnetic wave shielding sheet
11: Access
12: Electromagnetic wave shielding layer
21:
圖1是例示本實施方式的電磁波屏蔽片的剖面圖。 圖2是例示粗糙程度不同的表面的鏡面反射光/漫反射光的比例比較的圖。 圖3是表示本實施方式的電磁波屏蔽性配線電路基板的一例的示意性切斷部剖面圖。 圖4是冷熱循環可靠性評價的示意性平面圖及切斷部剖面圖。 圖5是層壓硬化物(實施例5)的動態黏彈性曲線。FIG. 1 is a cross-sectional view illustrating the electromagnetic wave shielding sheet of this embodiment. FIG. 2 is a diagram illustrating a comparison of the ratio of specular reflection light/diffuse reflection light on surfaces with different roughnesses. 3 is a schematic cross-sectional view of a cut portion showing an example of the electromagnetic wave shielding printed circuit board of the present embodiment. Fig. 4 is a schematic plan view and a cross-sectional view of a cut portion of the reliability evaluation of the cooling and heating cycle. Figure 5 is a dynamic viscoelastic curve of a laminated hardened product (Example 5).
a1:導電黏接劑層 a1: Conductive adhesive layer
a2:金屬層 a2: metal layer
a3:保護層 a3: protective layer
a4:開口部 a4: opening
10:電磁波屏蔽片 10: Electromagnetic wave shielding sheet
Claims (6)
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JP2017147276A (en) * | 2016-02-15 | 2017-08-24 | 東洋インキScホールディングス株式会社 | Electromagnetic wave shield sheet, electromagnetic wave shield wiring circuit board and electronic apparatus |
CN107409483A (en) * | 2015-02-25 | 2017-11-28 | 东洋油墨Sc控股株式会社 | Electromagnetic shielding piece, electromagnetic shielding wired circuit board and e-machine |
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JP2013168643A (en) | 2012-01-17 | 2013-08-29 | Toyo Ink Sc Holdings Co Ltd | Electromagnetic wave shield sheet and manufacturing method of wiring board with electromagnetic wave shield layer |
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