TW202134051A - Electromagnetic wave shielding film - Google Patents
Electromagnetic wave shielding film Download PDFInfo
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- TW202134051A TW202134051A TW110100652A TW110100652A TW202134051A TW 202134051 A TW202134051 A TW 202134051A TW 110100652 A TW110100652 A TW 110100652A TW 110100652 A TW110100652 A TW 110100652A TW 202134051 A TW202134051 A TW 202134051A
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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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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B15/00—Layered products comprising a layer of metal
- B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
- B32B15/08—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
- B32B7/04—Interconnection of layers
- B32B7/12—Interconnection of layers using interposed adhesives or interposed materials with bonding properties
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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
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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
-
- 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
Abstract
Description
本發明係關於電磁波屏蔽膜。更詳細而言，本發明係關於用在印刷配線板之電磁波屏蔽膜。The present invention relates to electromagnetic wave shielding films. In more detail, the present invention relates to an electromagnetic wave shielding film used in a printed wiring board.
背景技術 印刷配線板在行動電話、照相機、筆記型電腦等電子設備中，廣泛被使用於在機構中組入電路。又，亦被利用於印表機打印頭這種可動部與控制部之連接上。於此等電子設備中需要電磁波屏蔽對策，即使對於使用在裝置內的印刷配線板，亦使用實施有電磁波屏蔽對策之屏蔽印刷配線板。Background technique Printed wiring boards are widely used in electronic devices such as mobile phones, cameras, and notebook computers to incorporate circuits in institutions. It is also used for the connection between the movable part and the control part of the printer head. Electromagnetic wave shielding measures are required in such electronic equipment, and even for printed wiring boards used in the device, shielded printed wiring boards with electromagnetic wave shielding measures are also used.
於屏蔽印刷配線板中，為了達成電磁波屏蔽對策，使用電磁波屏蔽膜(以下有時簡稱為「屏蔽膜」)。例如，接著於印刷配線板來使用的屏蔽膜具有金屬層等屏蔽層、及設置於該屏蔽層表面之導電性接著片。In shielded printed wiring boards, in order to achieve electromagnetic wave shielding countermeasures, electromagnetic wave shielding films (hereinafter sometimes referred to as "shielding films") are used. For example, a shielding film used next to a printed wiring board has a shielding layer such as a metal layer, and a conductive adhesive sheet provided on the surface of the shielding layer.
關於具有導電性接著片之屏蔽膜，例如已知有專利文獻1及2所揭示者。上述屏蔽膜係以導電性接著片露出之表面來與印刷配線板表面貼著之方式進行貼合而使用，具體而言，該屏蔽膜是以導電性接著片露出之表面來與設置於印刷配線板表面之覆蓋膜表面貼著之方式進行貼合而使用。該等導電性接著片通常於高溫/高壓條件下進行熱壓接，而接著及積層於印刷配線板。藉此，配置於印刷配線板上之屏蔽膜可發揮遮蔽來自印刷配線板外部的電磁波的性能(屏蔽性能)。
先行技術文獻
專利文獻Regarding a shielding film having a conductive adhesive sheet, for example, those disclosed in
[專利文獻1]日本特開2015-110769號公報 [專利文獻2]日本特開2012-28334號公報[Patent Document 1] Japanese Patent Application Publication No. 2015-110769 [Patent Document 2] JP 2012-28334 A
發明概要 發明欲解決之課題 近年來，對於屏蔽膜，有要求黏貼於印刷配線板時容易進行對位之性能的情形。因此，對於屏蔽膜有要求透明性之傾向。關於使透明性提高之方法，考慮使用例如層厚度較薄之透明導電層作為屏蔽膜之導電層。Summary of the invention The problem to be solved by the invention In recent years, there have been cases in which shielding films are required to be easily aligned when they are pasted on a printed wiring board. Therefore, there is a tendency to require transparency for shielding films. Regarding the method of improving the transparency, it is considered to use, for example, a transparent conductive layer with a thinner layer as the conductive layer of the shielding film.
然而，就以往的屏蔽膜而言，導電性接著劑層中之導電性粒子的調配量越增加，導電性會越提高，相對的，在已使用透明導電層之屏蔽膜中，若於導電性接著劑層中大量調配導電性粒子，則會有電性連接電阻值上升、導電性降低的問題。However, as for the conventional shielding film, the more the amount of conductive particles in the conductive adhesive layer is increased, the more the conductivity will be improved. In contrast, in the shielding film that has used a transparent conductive layer, the conductivity will increase. When a large amount of conductive particles are blended in the adhesive layer, the electrical connection resistance will increase and the conductivity will decrease.
本發明係鑑於上述而完成者，本發明之目的在於提供一種電磁波屏蔽膜，其即使於導電性接著劑層中大量調配導電性粒子的情況下，透明性仍優異且電性連接電阻值較低。 用以解決課題之手段The present invention was completed in view of the above. The object of the present invention is to provide an electromagnetic wave shielding film, which has excellent transparency and low electrical connection resistance even when a large amount of conductive particles are blended in a conductive adhesive layer . Means to solve the problem
本發明人等為達成上述目的反覆進行研究，結果發現：具有特定之層構造的電磁波屏蔽膜，即使於導電性接著劑層中大量調配導電性粒子的情況下，透明性仍優異且電性連接電阻值較低。本發明係基於上述見解而完成者。The inventors of the present invention have repeatedly studied to achieve the above-mentioned object, and found that an electromagnetic wave shielding film with a specific layer structure has excellent transparency and electrical connection even when a large number of conductive particles are blended in the conductive adhesive layer. The resistance value is low. The present invention was completed based on the above knowledge.
即，本發明提供一種電磁波屏蔽膜，依序積層有第1絕緣層、透明導電層、第2絕緣層及導電性接著劑層； 上述透明導電層係厚度為5~100nm的金屬層且由金、銀、銅、鈀、鎳、鋁或包含此等中之1種以上之金屬的合金構成； 上述第2絕緣層之厚度為50~1000nm； 上述導電性接著劑層包含黏結劑成分、及球狀或樹枝狀之導電性粒子； 上述導電性粒子之含有比率是相對於上述導電性接著劑層100質量%而為1~80質量%。That is, the present invention provides an electromagnetic wave shielding film in which a first insulating layer, a transparent conductive layer, a second insulating layer, and a conductive adhesive layer are sequentially laminated; The transparent conductive layer is a metal layer with a thickness of 5-100 nm and is made of gold, silver, copper, palladium, nickel, aluminum, or an alloy containing one or more of these metals; The thickness of the second insulating layer is 50~1000nm; The conductive adhesive layer includes a binder component and spherical or dendritic conductive particles; The content ratio of the conductive particles is 1 to 80% by mass with respect to 100% by mass of the conductive adhesive layer.
上述第2絕緣層與上述導電性接著劑層宜直接積層。Preferably, the second insulating layer and the conductive adhesive layer are directly laminated.
上述第2絕緣層宜分別於一面與上述導電性接著劑層直接積層、於另一面與上述透明導電層直接積層。Preferably, the second insulating layer is directly laminated with the conductive adhesive layer on one side and the transparent conductive layer on the other side.
上述導電性粒子之含有比率宜為相對於上述導電性接著劑層100質量%而為30~80質量%。The content ratio of the conductive particles is preferably 30 to 80% by mass relative to 100% by mass of the conductive adhesive layer.
上述電磁波屏蔽膜於依循JIS K 7361-1之測定方法下的總透光率宜為10%以上。The above-mentioned electromagnetic wave shielding film should preferably have a total light transmittance of 10% or more in accordance with the measurement method of JIS K 7361-1.
又，本發明提供一種具備上述電磁波屏蔽膜的屏蔽印刷配線板。 發明效果Furthermore, the present invention provides a shielded printed wiring board provided with the electromagnetic wave shielding film. Invention effect
本發明之電磁波屏蔽膜，無論是於導電性接著劑層中少量調配導電性粒子的情況或大量調配導電性粒子的情況，透明性均優異，且電性連接電阻值較低。The electromagnetic wave shielding film of the present invention has excellent transparency and low electrical connection resistance regardless of the case where a small amount of conductive particles are mixed in the conductive adhesive layer or a case where a large amount of conductive particles are mixed.
用以實施發明之形態 [屏蔽膜] 本發明之屏蔽膜具有依序積層有第1絕緣層、透明導電層、第2絕緣層及導電性接著劑層的層構造。The form used to implement the invention [Shielding film] The shielding film of the present invention has a layer structure in which a first insulating layer, a transparent conductive layer, a second insulating layer, and a conductive adhesive layer are laminated in this order.
以下，就本發明之屏蔽膜之一實施形態進行說明。圖1係顯示本發明之屏蔽膜之一實施形態的剖面示意圖。圖1所示之本發明之屏蔽膜1，依序具有第1絕緣層11、透明導電層12、第2絕緣層13及導電性接著劑層14。Hereinafter, an embodiment of the shielding film of the present invention will be described. Fig. 1 is a schematic cross-sectional view showing an embodiment of the shielding film of the present invention. The
(第1絕緣層) 第1絕緣層係於本發明之屏蔽膜中保護透明導電層及作為透明導電層之支持體而起作用的透明基材。關於第1絕緣層，例如可列舉：塑膠基材(尤其是塑膠膜)、玻璃板等。第1絕緣層可為單層、亦可為相同種類或不同種類之積層體。(1st insulating layer) The first insulating layer is a transparent substrate that protects the transparent conductive layer and functions as a support for the transparent conductive layer in the shielding film of the present invention. As for the first insulating layer, for example, a plastic base material (especially a plastic film), a glass plate, etc. can be cited. The first insulating layer may be a single layer, or a laminate of the same type or different types.
關於構成上述塑膠基材之樹脂，例如可列舉：低密度聚乙烯、直鏈狀低密度聚乙烯、中密度聚乙烯、高密度聚乙烯、超低密度聚乙烯、無規共聚聚丙烯、嵌段共聚聚丙烯、均聚丙烯、聚丁烯、聚甲基戊烯、乙烯-乙酸乙烯酯共聚物(EVA)、離子聚合物、乙烯-(甲基)丙烯酸共聚物、乙烯-(甲基)丙烯酸酯(無規、交替)共聚物、乙烯-丁烯共聚物、乙烯-己烯共聚物等聚烯烴樹脂；聚胺基甲酸酯；聚對苯二甲酸乙二酯(PET)、聚萘二甲酸乙二酯、聚對苯二甲酸丁二酯(PBT)等聚酯；聚碳酸酯(PC)；聚醯亞胺(PI)；聚醚醚酮(PEEK)；聚醚醯亞胺；芳族聚醯胺、全芳香族聚醯胺等聚醯胺；聚苯硫醚；聚碸(PS)；聚醚碸(PES)；聚甲基丙烯酸甲酯(PMMA)等丙烯酸樹脂；丙烯腈-丁二烯-苯乙烯共聚物(ABS)；氟樹脂；聚氯乙烯；聚偏二氯乙烯；三醋酸纖維素(TAC)等纖維素樹脂；聚矽氧樹脂等。上述樹脂可僅使用一種、亦可使用二種以上。由透明性更加優異之觀點，以上述樹脂而言，其中較佳為聚酯、纖維素樹脂、更佳為聚對苯二甲酸乙二酯、三醋酸纖維素。Regarding the resin constituting the above-mentioned plastic substrate, for example, low-density polyethylene, linear low-density polyethylene, medium-density polyethylene, high-density polyethylene, ultra-low-density polyethylene, random copolymer polypropylene, block Copolypropylene, homopolypropylene, polybutene, polymethylpentene, ethylene-vinyl acetate copolymer (EVA), ionomer, ethylene-(meth)acrylic acid copolymer, ethylene-(meth)acrylic acid Polyolefin resins such as ester (random, alternating) copolymers, ethylene-butene copolymers, ethylene-hexene copolymers; polyurethane; polyethylene terephthalate (PET), polyethylene naphthalate Polyesters such as ethylene formate and polybutylene terephthalate (PBT); polycarbonate (PC); polyimide (PI); polyether ether ketone (PEEK); polyether imide; aromatic Polyamides, fully aromatic polyamides and other polyamides; polyphenylene sulfide; polysulfide (PS); polyether sulfide (PES); polymethylmethacrylate (PMMA) and other acrylic resins; acrylonitrile- Butadiene-styrene copolymer (ABS); fluororesin; polyvinyl chloride; polyvinylidene chloride; cellulosic resin such as cellulose triacetate (TAC); polysiloxane resin, etc. Only one kind of the above-mentioned resin may be used, or two or more kinds may be used. From the viewpoint of more excellent transparency, among the above resins, polyester and cellulose resin are preferred, and polyethylene terephthalate and cellulose triacetate are more preferred.
基於提高與透明導電層等鄰接層之密著性、保持性等之目的，第1絕緣層之表面(尤其是透明導電層側表面)亦可施以例如：電暈放電處理、電漿處理、噴砂加工處理、臭氧暴露處理、火焰暴露處理、高壓電撃暴露處理、離子化放射線處理等物理性處理；鉻酸處理等化學性處理；利用塗佈劑(底塗劑)之易接著處理等表面處理。用以提高密著性之表面處理宜對第1絕緣層中之透明導電層側之整個表面施行。For the purpose of improving the adhesion and retention of adjacent layers such as the transparent conductive layer, the surface of the first insulating layer (especially the surface on the side of the transparent conductive layer) can also be treated with corona discharge treatment, plasma treatment, etc. Sandblasting treatment, ozone exposure treatment, flame exposure treatment, high-voltage electric shock exposure treatment, ionizing radiation treatment and other physical treatments; chromic acid treatment and other chemical treatments; surface treatments such as easy bonding treatment using coating agent (primer) . The surface treatment for improving adhesion should be performed on the entire surface of the first insulating layer on the side of the transparent conductive layer.
第1絕緣層之厚度並無特別限定，但宜為1~15μm、較佳為3~10μm。若上述厚度為1μm以上，可更充分地支持屏蔽膜及保護透明導電層。若上述厚度為15μm以下，透明性及柔軟性優異，且在經濟上也是有利的。再者，第1絕緣層為複數層構造時，上述第1絕緣層之厚度為全部層厚度的合計。The thickness of the first insulating layer is not particularly limited, but is preferably 1 to 15 μm, preferably 3 to 10 μm. If the above thickness is 1 μm or more, the shielding film can be more fully supported and the transparent conductive layer can be protected. If the thickness is 15 μm or less, transparency and flexibility are excellent, and it is also economically advantageous. In addition, when the first insulating layer has a multiple-layer structure, the thickness of the first insulating layer is the total thickness of all layers.
(透明導電層) 上述透明導電層係於本發明之屏蔽膜中作為屏蔽層而起作用的要件。上述透明導電層可為單層、亦可為相同種類或不同種類之積層體。(Transparent conductive layer) The above-mentioned transparent conductive layer is a requirement for functioning as a shielding layer in the shielding film of the present invention. The above-mentioned transparent conductive layer may be a single layer, or may be a laminate of the same type or different types.
上述透明導電層係由金、銀、銅、鈀、鎳、鋁或包含此等中之1種以上之金屬的合金構成。如此之透明導電層具有屏蔽性能又不失透明性優異。The transparent conductive layer is made of gold, silver, copper, palladium, nickel, aluminum, or an alloy containing one or more of these metals. Such a transparent conductive layer has excellent shielding performance without losing transparency.
關於上述合金，例如可列舉：銀/銅合金、銀/鋅合金、銀/錫合金、銀/鈀合金、銀/鎳合金、銀/鋁合金、銀/鉍合金、銀/鍺合金、銀/釔合金、銀/釹合金、銀/鈧合金、銀/銦合金、銀/銻合金、銀/鎵合金等。以上述金屬而言，其中，由使電磁波屏蔽性能更優異之觀點，較佳為銅、銀，由於焊料回焊時或高溫高溼環境下使用屏蔽膜時，可抑制銀被硫成分硫化或被汗等中所含之氯腐蝕之觀點，較佳為銀/銅合金。Regarding the above alloys, for example, silver/copper alloys, silver/zinc alloys, silver/tin alloys, silver/palladium alloys, silver/nickel alloys, silver/aluminum alloys, silver/bismuth alloys, silver/germanium alloys, silver/ Yttrium alloy, silver/neodymium alloy, silver/scandium alloy, silver/indium alloy, silver/antimony alloy, silver/gallium alloy, etc. Among the above metals, copper and silver are preferred from the standpoint of improving electromagnetic wave shielding performance. Since the shielding film is used during solder reflow or in a high-temperature and high-humidity environment, silver can be prevented from being sulfided by sulfur components or being vulcanized. From the viewpoint of corrosion of chlorine contained in sweat, etc., a silver/copper alloy is preferable.
上述透明導電層之厚度宜為5~100nm、較佳為10~50nm。藉由上述厚度為5nm以上，可維持屏蔽性能。藉由上述厚度為100nm以下，屏蔽膜之透明性優異。再者，透明導電層為複數層構造時，上述透明導電層之厚度為全部層厚度的合計。又，透明導電層之厚度可利用穿透式電子顯微鏡(TEM)測定透明導電層之剖面而算出。The thickness of the transparent conductive layer is preferably 5-100 nm, preferably 10-50 nm. With the above thickness of 5nm or more, the shielding performance can be maintained. Since the above thickness is 100 nm or less, the transparency of the shielding film is excellent. In addition, when the transparent conductive layer has a multiple-layer structure, the thickness of the transparent conductive layer is the total thickness of all layers. In addition, the thickness of the transparent conductive layer can be calculated by measuring the cross section of the transparent conductive layer with a transmission electron microscope (TEM).
上述透明導電層之形成方法並無特別限定，例如可列舉：電解、蒸鍍(例如真空蒸鍍)、濺鍍、CVD法、金屬有機(MO)、鍍敷、壓延加工等。其中，由製造容易性之觀點，較佳為利用蒸鍍或濺鍍所形成之透明導電層。The method of forming the transparent conductive layer is not particularly limited, and examples include electrolysis, vapor deposition (for example, vacuum vapor deposition), sputtering, CVD, metal organic (MO), plating, and rolling. Among them, from the viewpoint of ease of manufacture, a transparent conductive layer formed by vapor deposition or sputtering is preferred.
(第2絕緣層) 第2絕緣層為用以保護透明導電層的透明層。藉由第2絕緣層介存於透明導電層與導電性接著劑層之間，可抑制透明性及連接穩定性之降低。上述透明性及連接穩定性之降低推測其原因為：透明導電層因為與導電性接著劑層中之導電性粒子摩擦而損傷之故。第2絕緣層可為單層或複數層。(Second insulating layer) The second insulating layer is a transparent layer for protecting the transparent conductive layer. Since the second insulating layer is interposed between the transparent conductive layer and the conductive adhesive layer, the decrease in transparency and connection stability can be suppressed. The reason for the above-mentioned decrease in transparency and connection stability is presumed to be that the transparent conductive layer is damaged by friction with the conductive particles in the conductive adhesive layer. The second insulating layer may be a single layer or multiple layers.
第2絕緣層宜包含黏結劑成分。關於上述黏結劑成分，可列舉：熱塑性樹脂、熱硬化性樹脂、活性能量線硬化性化合物等。關於上述熱塑性樹脂、熱硬化型樹脂及活性能量線硬化型化合物，分別可列舉：作為後述的導電性接著劑層能夠包含之黏結劑成分所例示者。上述黏結劑成分可僅使用一種、亦可使用二種以上。The second insulating layer preferably contains a binder component. As for the above-mentioned binder component, a thermoplastic resin, a thermosetting resin, an active energy ray curable compound, etc. can be mentioned. Regarding the above-mentioned thermoplastic resin, thermosetting resin, and active energy ray-curing compound, respectively, those exemplified as binder components that can be contained in the conductive adhesive layer described below are exemplified. Only one kind of the above-mentioned binder component may be used, or two or more kinds may be used.
第2絕緣層中之上述黏結劑成分之含量並無特別限定，但宜為相對於第2絕緣層100質量%而為70質量%以上、較佳為80質量%以上、更佳為90質量%以上。若上述含量為70質量%以上，柔軟性會更加優異，朝小直徑孔穴的填埋性優異，連接穩定性更加優異。The content of the binder component in the second insulating layer is not particularly limited, but it is preferably 70% by mass or more, preferably 80% by mass or more, and more preferably 90% by mass relative to 100% by mass of the second insulating layer. above. If the above content is 70% by mass or more, flexibility will be more excellent, filling of small diameter holes will be excellent, and connection stability will be more excellent.
於無損本發明效果之範圍內，第2絕緣層亦可含有上述黏結劑成分以外的其他成分。關於上述其他成分，例如可列舉：硬化劑、硬化促進劑、塑化劑、阻燃劑、消泡劑、黏度調整劑、抗氧化劑、稀釋劑、防沉劑、填充劑、調平劑、偶合劑、紫外線吸收劑、黏著賦予樹脂、抗結塊劑等。上述其他成分可僅使用一種、亦可使用二種以上。As long as the effect of the present invention is not impaired, the second insulating layer may contain components other than the above-mentioned binder components. Regarding the above-mentioned other components, for example, hardeners, hardening accelerators, plasticizers, flame retardants, defoamers, viscosity modifiers, antioxidants, diluents, anti-settling agents, fillers, leveling agents, and even Mixtures, UV absorbers, adhesion-imparting resins, anti-caking agents, etc. Only one kind of the above-mentioned other components may be used, or two or more kinds may be used.
第2絕緣層之厚度為50~1000nm、較佳為100~300nm。藉由上述厚度為50nm以上，屏蔽性能及連接穩定性優異。藉由上述厚度為1000nm以下，透明性及連接穩定性優異。再者，第2絕緣層為複數層構造時，上述第2絕緣層之厚度為全部層厚度的合計。The thickness of the second insulating layer is 50 to 1000 nm, preferably 100 to 300 nm. With the above thickness of 50 nm or more, the shielding performance and connection stability are excellent. Since the above thickness is 1000 nm or less, transparency and connection stability are excellent. In addition, when the second insulating layer has a multiple-layer structure, the thickness of the second insulating layer is the total thickness of all layers.
由保護上述透明導電層之觀點，第2絕緣層宜與上述導電性接著劑層直接積層，尤佳為分別於一面與上述導電性接著劑層直接積層、於另一面與上述透明導電層直接積層。From the viewpoint of protecting the transparent conductive layer, the second insulating layer is preferably laminated directly with the conductive adhesive layer, and it is particularly preferable to laminate directly with the conductive adhesive layer on one side and the transparent conductive layer on the other side. .
(導電性接著劑層) 上述導電性接著劑層具有用以將例如本發明之屏蔽膜接著於印刷配線板之接著性、及用以與上述透明導電層電性連接之導電性。又，亦可與上述透明導電層一同作為發揮屏蔽性能之屏蔽層而起作用。上述導電性接著劑層可為單層或複數層任一者。(Conductive adhesive layer) The conductive adhesive layer has adhesiveness for adhering, for example, the shielding film of the present invention to a printed wiring board, and conductivity for electrically connecting with the transparent conductive layer. Moreover, it can also function as a shielding layer which exhibits shielding performance together with the said transparent conductive layer. The above-mentioned conductive adhesive layer may be a single layer or a plurality of layers.
上述導電性接著劑層含有黏結劑成分及球狀或樹枝狀(dendrite狀)之導電性粒子。The conductive adhesive layer contains a binder component and spherical or dendritic conductive particles.
關於上述黏結劑成分，可列舉：熱塑性樹脂、熱硬化性樹脂、活性能量線硬化性化合物等。上述黏結劑成分可僅使用一種、亦可使用二種以上。As for the above-mentioned binder component, a thermoplastic resin, a thermosetting resin, an active energy ray curable compound, etc. can be mentioned. Only one kind of the above-mentioned binder component may be used, or two or more kinds may be used.
關於上述熱塑性樹脂，例如可列舉：聚苯乙烯系樹脂、乙酸乙烯酯系樹脂、聚酯系樹脂、聚烯烴系樹脂(例如聚乙烯系樹脂、聚丙烯系樹脂組成物等)、聚醯亞胺系樹脂、丙烯酸系樹脂等。上述熱塑性樹脂可僅使用一種、亦可使用二種以上。Regarding the above-mentioned thermoplastic resins, for example, polystyrene resins, vinyl acetate resins, polyester resins, polyolefin resins (for example, polyethylene resins, polypropylene resin compositions, etc.), polyimides are mentioned. Series resins, acrylic resins, etc. Only one type of the above-mentioned thermoplastic resin may be used, or two or more types may be used.
關於上述熱硬化型樹脂，可列舉具有熱硬化性之樹脂(熱硬化性樹脂)及使上述熱硬化性樹脂硬化而獲得之樹脂兩者。關於上述熱硬化性樹脂，例如可列舉：酚系樹脂、環氧系樹脂、胺基甲酸酯系樹脂、胺基甲酸酯脲系樹脂、三聚氰胺系樹脂、醇酸系樹脂等。上述熱硬化型樹脂可僅使用一種、亦可使用二種以上。Regarding the above-mentioned thermosetting resin, both a resin having thermosetting properties (thermosetting resin) and a resin obtained by curing the above-mentioned thermosetting resin can be cited. Regarding the above-mentioned thermosetting resins, for example, phenol resins, epoxy resins, urethane resins, urethane urea resins, melamine resins, alkyd resins, and the like can be cited. Only one type of the above-mentioned thermosetting resin may be used, or two or more types may be used.
關於上述環氧系樹脂，例如可列舉：雙酚型環氧系樹脂、螺環型環氧系樹脂、萘型環氧系樹脂、聯苯型環氧系樹脂、萜烯型環氧系樹脂、環氧丙基醚型環氧系樹脂、環氧丙基胺型環氧系樹脂、酚醛型環氧系樹脂等。Regarding the above epoxy resins, for example, bisphenol epoxy resins, spiro epoxy resins, naphthalene epoxy resins, biphenyl epoxy resins, terpene epoxy resins, Glycidyl ether type epoxy resins, glycidyl amine type epoxy resins, novolac type epoxy resins, etc.
關於上述雙酚型環氧系樹脂，例如可列舉：雙酚A型環氧系樹脂、雙酚F型環氧系樹脂、雙酚S型環氧系樹脂、四溴雙酚A型環氧系樹脂等。關於上述環氧丙基醚型環氧系樹脂，例如可列舉：參(環氧丙氧基苯基)甲烷、肆(環氧丙氧基苯基)乙烷等。關於上述環氧丙基胺型環氧系樹脂，可舉例：四環氧丙基二胺基二苯基甲烷等。關於上述酚醛型環氧系樹脂，例如可列舉：甲酚酚醛型環氧系樹脂、苯酚酚醛型環氧系樹脂、α-萘酚酚醛型環氧系樹脂、溴化苯酚酚醛型環氧系樹脂等。Regarding the above-mentioned bisphenol type epoxy resins, for example, bisphenol A type epoxy resins, bisphenol F type epoxy resins, bisphenol S type epoxy resins, and tetrabromobisphenol A type epoxy resins can be cited. Resin etc. Regarding the glycidyl ether type epoxy resin, for example, ginseng (glycidoxy phenyl) methane, tetra (glycidoxy phenyl) ethane, and the like can be mentioned. Regarding the above-mentioned glycidylamine type epoxy resin, tetraglycidyldiaminodiphenylmethane and the like can be exemplified. Regarding the above-mentioned novolac epoxy resins, for example, cresol novolac epoxy resins, phenol novolac epoxy resins, α-naphthol novolac epoxy resins, and brominated phenol novolac epoxy resins can be cited. Wait.
上述活性能量線硬化型化合物，可列舉可藉由活性能量線照射而硬化之化合物(活性能量線硬化性化合物)及使上述活性能量線硬化性化合物硬化而獲得之化合物兩者。關於活性能量線硬化性化合物，並無特別限定，但可舉例：於分子中具有至少2個自由基反應性基(例如(甲基)丙烯醯基)之聚合性化合物等。上述活性能量線硬化型化合物可僅使用一種、亦可使用二種以上。The active energy ray-curable compound includes both a compound that can be cured by active energy ray irradiation (active energy ray-curable compound) and a compound obtained by curing the active energy ray-curable compound. The active energy ray-curable compound is not particularly limited, but examples thereof include polymerizable compounds having at least two radical reactive groups (for example, (meth)acryloyl groups) in the molecule. The active energy ray-curable compound may be used alone, or two or more kinds may be used.
關於上述黏結劑成分，其中較佳為熱硬化型樹脂。此時，為了接著於印刷配線板，可將本發明之屏蔽膜配置於印刷配線板上，其後，利用加壓及加熱而使黏結劑成分硬化，與印刷配線板之接著性變為良好。Regarding the above-mentioned binder component, among them, a thermosetting resin is preferable. At this time, in order to adhere to the printed wiring board, the shielding film of the present invention can be arranged on the printed wiring board, and then the adhesive component is cured by pressing and heating, and the adhesiveness with the printed wiring board becomes good.
上述黏結劑成分包含熱塑性樹脂時，關於構成上述黏結劑成分之成分亦可包含熱塑性樹脂之單體成分。藉由黏結劑成分包含單體成分，暫時黏貼性或重工性、對被接著體施予加熱加壓後之密著性變為良好。When the said binder component contains a thermoplastic resin, about the component which comprises the said binder component, you may contain the monomer component of a thermoplastic resin. Since the binder component contains a monomer component, the temporary adhesiveness, reworkability, and adhesion after heating and pressing the adherend become good.
上述黏結劑成分包含熱硬化型樹脂時，關於構成上述黏結劑成分之成分，亦可包含用以促進熱硬化反應的硬化劑。上述硬化劑可根據上述熱硬化性樹脂之種類而適當選擇。上述硬化劑可僅使用一種、亦可使用二種以上。When the binder component includes a thermosetting resin, the components constituting the binder component may also include a curing agent for accelerating the thermosetting reaction. The curing agent can be appropriately selected according to the type of the thermosetting resin. Only one type of the above-mentioned curing agent may be used, or two or more types may be used.
上述導電性接著劑層中之黏結劑成分之含有比率並無特別限定，但宜為相對於導電性接著劑層之總量100質量%而為20~99質量%、較佳為30~80質量%、更佳為40~70質量%。若上述含有比率為20質量%以上，對於印刷配線板之密著性會更加優異。若上述含有比率為99質量%以下，可充分地含有導電性粒子。The content of the binder component in the conductive adhesive layer is not particularly limited, but it is preferably 20 to 99% by mass, preferably 30 to 80% by mass relative to 100% by mass of the total amount of the conductive adhesive layer %, more preferably 40 to 70% by mass. If the above content ratio is 20% by mass or more, the adhesion to the printed wiring board will be more excellent. If the said content ratio is 99 mass% or less, electroconductive particle can fully be contained.
就上述導電性粒子而言，使用球狀導電性粒子及/或樹枝狀導電性粒子。藉由使用上述球狀或樹枝狀導電性粒子，即使是大量調配的情況下，透明性仍優異且連接穩定性優異。使用球狀導電性粒子時，透明性更加優異。For the above-mentioned conductive particles, spherical conductive particles and/or dendritic conductive particles are used. By using the spherical or dendritic conductive particles described above, even in the case of a large amount of compounding, the transparency is excellent and the connection stability is excellent. When spherical conductive particles are used, transparency is more excellent.
就上述導電性粒子而言，例如可列舉：金屬粒子、金屬被覆樹脂粒子、碳填料等。上述導電性粒子可僅使用一種、亦可使用二種以上。Examples of the aforementioned conductive particles include metal particles, metal-coated resin particles, and carbon fillers. As for the said electroconductive particle, only 1 type may be used, and 2 or more types may be used.
構成上述金屬粒子及上述金屬被覆樹脂粒子之被覆部的金屬，例如可列舉：金、銀、銅、鎳、鋅等。上述金屬可僅使用一種、亦可使用二種以上。Examples of the metals constituting the metal particles and the coated portions of the metal-coated resin particles include gold, silver, copper, nickel, and zinc. Only one kind of the above-mentioned metals may be used, or two or more kinds may be used.
就上述金屬粒子而言，具體例如可列舉：銅粒子、銀粒子、鎳粒子、銀被覆銅粒子、金被覆銅粒子、銀被覆鎳粒子、金被覆鎳粒子、銀被覆合金粒子等。上述銀被覆合金粒子例如可列舉：利用銀被覆包含銅之合金粒子(例如由銅、鎳及鋅之合金構成之銅合金粒子)的銀被覆銅合金粒子等。上述金屬粒子可藉由電解法、霧化法或還原法等來製作。Specific examples of the aforementioned metal particles include copper particles, silver particles, nickel particles, silver-coated copper particles, gold-coated copper particles, silver-coated nickel particles, gold-coated nickel particles, and silver-coated alloy particles. Examples of the above-mentioned silver-coated alloy particles include silver-coated copper alloy particles in which alloy particles containing copper (for example, copper alloy particles composed of an alloy of copper, nickel, and zinc) are coated with silver. The above-mentioned metal particles can be produced by an electrolysis method, an atomization method, a reduction method, or the like.
其中，以上述金屬粒子而言，較佳為銀粒子、銀被覆銅粒子、銀被覆銅合金粒子。由導電性優異、可抑制金屬粒子之氧化及凝集、且可降低金屬粒子成本之觀點，宜為銀被覆銅粒子、銀被覆銅合金粒子。Among them, the above-mentioned metal particles are preferably silver particles, silver-coated copper particles, and silver-coated copper alloy particles. From the viewpoint of excellent electrical conductivity, suppression of oxidation and aggregation of metal particles, and reduction of the cost of metal particles, silver-coated copper particles and silver-coated copper alloy particles are preferable.
上述導電性粒子之中值粒徑(D50)並無特別限定，但宜為5~15μm、較佳為5~10μm。上述中值粒徑為上述導電性接著劑層中之所有球狀導電性粒子及/或樹枝狀導電性粒子之中值粒徑，指利用雷射繞射/散射法求得的粒度分布中累計值50%的粒徑。藉由上述中值粒徑為上述範圍內，於使用導電性粒子之本發明中，連接穩定性更加優異。上述中值粒徑可藉由例如雷射繞射式粒徑分布測定裝置(商品名「SALD-2200」、島津製作所股份有限公司製)測定。The median diameter (D50) of the conductive particles is not particularly limited, but is preferably 5 to 15 μm, more preferably 5 to 10 μm. The above median particle size is the median particle size of all spherical conductive particles and/or dendritic conductive particles in the conductive adhesive layer, and refers to the cumulative particle size distribution obtained by the laser diffraction/scattering method Value 50% of the particle size. Since the above-mentioned median diameter is within the above-mentioned range, in the present invention using conductive particles, the connection stability is more excellent. The aforementioned median particle size can be measured by, for example, a laser diffraction particle size distribution measuring device (trade name "SALD-2200", manufactured by Shimadzu Corporation).
上述導電性接著劑層中之上述導電性粒子之含有比率宜為相對於導電性接著劑層100質量%而為1~80質量%、較佳為20~70質量%、更佳為30~60質量%。於本發明之屏蔽膜中，導電性接著劑層無論是包含1質量%左右之少量的上述導電性粒子的情形，乃至包含多達80質量%之上述導電性粒子的情形，連接電阻值皆較低、連接穩定性亦優異。The content of the conductive particles in the conductive adhesive layer is preferably 1 to 80% by mass relative to 100% by mass of the conductive adhesive layer, preferably 20 to 70% by mass, more preferably 30 to 60 quality%. In the shielding film of the present invention, whether the conductive adhesive layer contains a small amount of the above-mentioned conductive particles of about 1% by mass, or even a case where it contains up to 80% by mass of the above-mentioned conductive particles, the connection resistance value is relatively high. Low and excellent connection stability.
於無損本發明效果之範圍內，上述導電性接著劑層亦可含有上述各成分以外的其他成分。關於上述其他成分，可舉例公知乃至慣用的接著劑層中所含的成分。以上述其他成分而言，例如可列舉：硬化促進劑、塑化劑、阻燃劑、消泡劑、黏度調整劑、抗氧化劑、稀釋劑、防沉劑、填充劑、調平劑、偶合劑、紫外線吸收劑、著色劑、抗結塊劑等。上述其他成分可僅使用一種、亦可使用二種以上。再者，球狀導電性粒子及樹枝狀導電性粒子以外的導電性粒子的含量係相對於球狀導電性粒子及/或樹枝狀導電性粒子100質量份為例如小於10質量份、較佳為小於5質量份、更佳為小於1質量份。Within a range that does not impair the effects of the present invention, the above-mentioned conductive adhesive layer may contain other components other than the above-mentioned components. Regarding the above-mentioned other components, components contained in a known or commonly used adhesive layer can be exemplified. The above-mentioned other components include, for example, hardening accelerators, plasticizers, flame retardants, defoamers, viscosity modifiers, antioxidants, diluents, anti-settling agents, fillers, leveling agents, and coupling agents , UV absorbers, colorants, anti-caking agents, etc. Only one kind of the above-mentioned other components may be used, or two or more kinds may be used. In addition, the content of conductive particles other than spherical conductive particles and dendritic conductive particles is, for example, less than 10 parts by mass relative to 100 parts by mass of spherical conductive particles and/or dendritic conductive particles, and is preferably It is less than 5 parts by mass, more preferably less than 1 part by mass.
上述導電性接著劑層之厚度並無特別限定，但宜為3~20μm、較佳為5~15μm。若上述厚度為3μm以上，屏蔽性能更加優異。若上述厚度為20μm以下，則會有導電性粒子的表面更靠近層表面或從表面露出之傾向，連接穩定性會更加優異。The thickness of the conductive adhesive layer is not particularly limited, but is preferably 3 to 20 μm, preferably 5 to 15 μm. If the above-mentioned thickness is 3 μm or more, the shielding performance is more excellent. If the thickness is 20 μm or less, the surface of the conductive particles tends to be closer to the surface of the layer or exposed from the surface, and the connection stability will be more excellent.
上述導電性接著劑層厚度與導電性粒子之D50之比[接著劑層厚度/D50]並無特別限定，但宜為0.2~1.5、較佳為0.5~1.0。若上述比為0.2以上，對印刷配線板等被接著體之接著性變得更良好。若上述比為1.5以下，從導電性接著劑層表面露出之導電性粒子之量會變多，連接穩定性會更加優異。The ratio of the thickness of the conductive adhesive layer to the D50 of the conductive particles [adhesive layer thickness/D50] is not particularly limited, but is preferably 0.2 to 1.5, preferably 0.5 to 1.0. If the above-mentioned ratio is 0.2 or more, the adhesiveness to an adherend such as a printed wiring board becomes better. If the above ratio is 1.5 or less, the amount of conductive particles exposed from the surface of the conductive adhesive layer will increase, and the connection stability will be more excellent.
本發明之屏蔽膜亦可於導電性接著劑層側具有分隔件(剝離膜)。分隔件係以可從本發明之屏蔽膜剝離的方式積層。分隔件為用以被覆導電性接著劑層予以保護之要件，於使用本發明的屏蔽膜時被剝離。The shielding film of the present invention may have a separator (release film) on the side of the conductive adhesive layer. The separator is laminated so as to be peelable from the shielding film of the present invention. The separator is an essential element for covering and protecting the conductive adhesive layer, and is peeled off when the shielding film of the present invention is used.
以上述分隔件而言，例如可列舉：聚對苯二甲酸乙二酯(PET)膜、聚乙烯膜、聚丙烯膜、氟系剝離劑或利用丙烯酸長鏈烷基酯系剝離劑等剝離劑進行表面塗覆之塑膠膜或紙類等。For the above-mentioned separator, for example, a polyethylene terephthalate (PET) film, a polyethylene film, a polypropylene film, a fluorine-based release agent, or a release agent such as a long-chain alkyl acrylate-based release agent can be used. Plastic film or paper for surface coating.
上述分隔件之厚度宜為10~200μm、較佳為15~150μm。若上述厚度為10μm以上，保護性能更加優異。若上述厚度為200μm以下，於使用時容易剝離分隔件。The thickness of the above-mentioned separator is preferably 10 to 200 μm, preferably 15 to 150 μm. If the above thickness is 10 μm or more, the protection performance is more excellent. If the above-mentioned thickness is 200 μm or less, it is easy to peel off the separator during use.
本發明之屏蔽膜亦可具有第1絕緣層、透明導電層、第2絕緣層及導電性接著劑層以外的其他層。關於上述其他層，例如可列舉：其他絕緣層、抗反射層、防眩層、防污層、硬塗層、紫外線吸收層、防牛頓環層等。The shielding film of the present invention may have layers other than the first insulating layer, the transparent conductive layer, the second insulating layer, and the conductive adhesive layer. The above-mentioned other layers include, for example, other insulating layers, anti-reflection layers, anti-glare layers, anti-fouling layers, hard coat layers, ultraviolet absorbing layers, anti-Newton ring layers, and the like.
本發明之屏蔽膜之透明性優異。本發明之屏蔽膜於依循JIS K 7361-1之測定方法下的總透光率宜為10%以上、較佳為20%以上、更佳為50%以上、尤佳為65%以上。上述總透光率可使用公知之分光光譜儀進行測定。再者，上述總透光率係就以第1絕緣層與上述導電性接著劑層作為兩端層之積層體進行測定。The shielding film of the present invention is excellent in transparency. The total light transmittance of the shielding film of the present invention according to the measurement method of JIS K 7361-1 is preferably 10% or more, preferably 20% or more, more preferably 50% or more, and particularly preferably 65% or more. The above-mentioned total light transmittance can be measured using a known spectrophotometer. In addition, the said total light transmittance was measured with the laminated body which used the 1st insulating layer and the said conductive adhesive layer as both end layers.
本發明之屏蔽膜於依循JIS K 7361-1之測定方法下的霧度值宜為95%以下、較佳為92%以下、更佳為90%以下。上述霧度值可使用公知之分光光譜儀進行測定。再者，上述霧度值係就以第1絕緣層與上述導電性接著劑層作為兩端層之積層體進行測定。The haze value of the shielding film of the present invention in accordance with the measurement method of JIS K 7361-1 is preferably 95% or less, preferably 92% or less, and more preferably 90% or less. The above-mentioned haze value can be measured using a known spectrophotometer. In addition, the said haze value was measured with the laminated body which used the 1st insulating layer and the said conductive adhesive layer as both end layers.
本發明之屏蔽膜宜用於印刷配線板用途或無線電力傳輸系統用途，尤佳為用於可撓性印刷配線板(FPC)用途或電磁感應式無線電力傳輸系統用途。本發明之屏蔽膜，無論是在導電性接著劑層中少量調配導電性粒子的情況或大量調配導電性粒子的情況，電性連接電阻值均較低。又，透明性優異、容易於印刷配線板或無線電力送電系統中之供電或送電的線圈等被接著體上進行對位。因此，本發明之屏蔽膜可適合用作可撓性印刷配線板用的電磁波屏蔽膜。The shielding film of the present invention is preferably used for printed wiring board applications or wireless power transmission system applications, and is particularly preferably used for flexible printed wiring board (FPC) applications or electromagnetic induction wireless power transmission system applications. The shielding film of the present invention has a low electrical connection resistance value regardless of the case where a small amount of conductive particles are blended in the conductive adhesive layer or a case where a large amount of conductive particles are blended. In addition, it has excellent transparency and is easy to align on the bonded body such as a printed wiring board or a coil for power supply or power transmission in a wireless power transmission system. Therefore, the shielding film of the present invention can be suitably used as an electromagnetic wave shielding film for flexible printed wiring boards.
(電磁波屏蔽膜之製造方法) 就本發明之屏蔽膜之製造方法進行說明。(Manufacturing method of electromagnetic wave shielding film) The manufacturing method of the shielding film of the present invention will be described.
於圖1所示之本發明之屏蔽膜1之製作上，首先於第1絕緣層11上形成透明導電層12。透明導電層12之形成宜藉由蒸鍍法或濺鍍法進行。上述蒸鍍法及濺鍍法可採用公知乃至慣用的方法。如此，藉由利用蒸鍍法或濺鍍法形成透明導電層，可容易製造具有適度的厚度及透明性之導電層。In the production of the
接著，可於已形成之透明導電層12表面例如塗佈(塗敷)第2絕緣層13形成用樹脂組成物，並視需要而去除溶媒及/或使其一部分硬化而形成。Next, the resin composition for forming the second insulating
上述樹脂組成物例如除了上述第2絕緣層所含之各成分外，還包含溶劑(溶媒)。溶劑方面，例如可列舉：甲苯、丙酮、甲乙酮、甲醇、乙醇、丙醇、乙酸乙酯、乙酸丙酯、乙酸丁酯、二甲基甲醯胺等。上述樹脂組成物之固體成分濃度係根據欲形成之第2絕緣層之厚度等而適當設定。The resin composition includes, for example, a solvent (solvent) in addition to the components contained in the second insulating layer. As for the solvent, for example, toluene, acetone, methyl ethyl ketone, methanol, ethanol, propanol, ethyl acetate, propyl acetate, butyl acetate, dimethylformamide, etc. may be mentioned. The solid content concentration of the above-mentioned resin composition is appropriately set according to the thickness of the second insulating layer to be formed, and the like.
於塗佈上述樹脂組成物時，亦可使用公知之塗佈法。例如可使用：凹版輥塗佈機、逆輥塗佈機、接觸輥塗佈機、模嘴塗佈機、浸漬輥塗佈機、棒塗佈機、刮刀(Knife)塗佈機、噴塗佈機、缺角輪塗佈機、直接塗佈機、槽模塗佈機等塗佈機。When coating the above-mentioned resin composition, a well-known coating method can also be used. For example, it can be used: gravure roll coater, reverse roll coater, contact roll coater, die nozzle coater, dip roll coater, bar coater, knife coater, spray cloth Coating machines such as machine, chipped wheel coater, direct coater, slot die coater, etc.
接著，可於已形成之第2絕緣層表面塗佈(塗敷)導電性接著劑層14形成用之接著劑組成物，並視需要而去除溶媒及/或使其一部分硬化而形成。Next, the adhesive composition for forming the conductive
上述接著劑組成物例如除了上述導電性接著劑層所含之各成分外，還包含溶劑(溶媒)。溶劑方面，可舉例作為上述樹脂組成物能包含之溶劑所例示者。上述接著劑組成物之固體成分濃度可根據欲形成之導電性接著劑層之厚度等而適當設定。The adhesive composition includes, for example, a solvent (solvent) in addition to the components contained in the conductive adhesive layer. The solvent can be exemplified as the solvent contained in the above-mentioned resin composition. The solid content concentration of the above-mentioned adhesive composition can be appropriately set according to the thickness of the conductive adhesive layer to be formed, and the like.
於塗佈上述接著劑組成物時，亦可使用公知之塗佈法。例如可舉已例示作為用於上述樹脂組成物之塗佈之塗佈機。When applying the above-mentioned adhesive composition, a well-known coating method can also be used. For example, a coater that has been exemplified as the coating machine used for the coating of the above-mentioned resin composition can be cited.
再者，於上述製造方法中係就依序形成各層而製作之方法(直接塗佈法)進行說明，但並不限定於此方法，例如亦可藉由將個別地形成於分離膜等暫時基材或基材上之各層予以層壓而依序貼合之方法(層壓法)來製作。In addition, in the above-mentioned manufacturing method, a method (direct coating method) of sequentially forming each layer is described, but it is not limited to this method. For example, it may be formed by separately forming a temporary substrate such as a separation membrane The material or the layers on the substrate are laminated and laminated in order (lamination method).
可使用本發明之屏蔽膜來製作印刷配線板。例如，藉由將本發明之屏蔽膜之導電性接著劑層貼合於印刷配線板(例如覆蓋膜)，可獲得於印刷配線板貼合有本發明屏蔽膜之屏蔽印刷配線板。於上述屏蔽印刷配線板中，上述導電性接著劑層亦可進行熱硬化。 [實施例]The shielding film of the present invention can be used to make a printed wiring board. For example, by attaching the conductive adhesive layer of the shielding film of the present invention to a printed wiring board (for example, a cover film), a shielding printed wiring board having the shielding film of the present invention attached to the printed wiring board can be obtained. In the shield printed wiring board, the conductive adhesive layer may be thermally cured. [Example]
以下，基於實施例更詳細地說明本發明，但本發明並不僅限定於此等實施例。再者，表中之導電性粒子之含有比率表示導電性接著劑層中之比率。Hereinafter, the present invention will be described in more detail based on examples, but the present invention is not limited to these examples. In addition, the content ratio of conductive particles in the table indicates the ratio in the conductive adhesive layer.
比較例1 利用濺鍍法於PET膜(厚度6μm)之表面形成銀/銅合金層(厚度10nm)。然後，使用線棒於上述合金層表面塗佈已將環氧樹脂溶液及導電性粒子A(銀包銅粉、球狀、中值粒徑5μm)調配混合而獲得之接著劑組成物，於120℃下加熱1分鐘，藉此形成導電性接著劑層(厚度5μm)。如上所述，製作比較例1之屏蔽膜。又，環氧樹脂溶液及導電性粒子A之調配量設定為導電性接著劑層中之環氧樹脂之比率為70質量%、導電性粒子A之比率為30質量%的量。Comparative example 1 Sputtering was used to form a silver/copper alloy layer (thickness 10nm) on the surface of the PET film (thickness 6μm). Then, use a wire rod to coat the surface of the alloy layer with an epoxy resin solution and conductive particles A (silver-coated copper powder, spherical shape, median diameter of 5μm), and the adhesive composition obtained by blending and mixing, at 120 By heating for 1 minute at °C, a conductive adhesive layer (thickness 5 μm) was formed. As described above, the shielding film of Comparative Example 1 was produced. In addition, the blending amount of the epoxy resin solution and the conductive particles A was set such that the ratio of the epoxy resin in the conductive adhesive layer was 70% by mass and the ratio of the conductive particles A was 30% by mass.
比較例2~4 除了如表1所示地變更導電性粒子之種類及含有比率外，與比較例1同樣進行製作各屏蔽膜。又，導電性粒子B為銀包銅粉(樹枝狀、中值粒徑5μm)。Comparative example 2~4 Except that the type and content ratio of conductive particles were changed as shown in Table 1, each shielding film was produced in the same manner as in Comparative Example 1. In addition, the conductive particles B are silver-coated copper powder (dendritic shape, median diameter of 5 μm).
實施例1 利用濺鍍法於PET膜(厚度6μm)之表面形成銀/銅合金層(厚度10nm)。接著，使用線棒於合金層表面塗佈聚酯系樹脂組成物，於100℃下加熱1分鐘，藉此形成樹脂層(厚度50nm)。然後，使用線棒於上述樹脂層表面塗佈已將環氧樹脂溶液及導電性粒子A調配混合而獲得之接著劑組成物，於120℃下加熱1分鐘，藉此形成導電性接著劑層(厚度5μm)。如上所述，製作實施例1之屏蔽膜。又，環氧樹脂溶液及導電性粒子A之調配量設定為導電性接著劑層中之環氧樹脂之比率為70質量%、導電性粒子A之比率為30質量%的量。Example 1 Sputtering was used to form a silver/copper alloy layer (thickness 10nm) on the surface of the PET film (thickness 6μm). Next, the polyester resin composition was coated on the surface of the alloy layer using a wire rod, and heated at 100°C for 1 minute to form a resin layer (thickness: 50 nm). Then, the adhesive composition obtained by mixing the epoxy resin solution and the conductive particles A was applied on the surface of the resin layer using a wire rod, and heated at 120°C for 1 minute to form the conductive adhesive layer ( Thickness 5μm). As described above, the shielding film of Example 1 was produced. In addition, the blending amount of the epoxy resin solution and the conductive particles A was set such that the ratio of the epoxy resin in the conductive adhesive layer was 70% by mass and the ratio of the conductive particles A was 30% by mass.
實施例2~4及比較例5、6 除了如表1所示地變更樹脂層之厚度外，與實施例1同樣進行，製作各屏蔽膜。Examples 2 to 4 and Comparative Examples 5 and 6 Except having changed the thickness of the resin layer as shown in Table 1, it carried out similarly to Example 1, and produced each shielding film.
實施例5 除了如表1所示地變更導電性粒子之含有比率外，與實施例1同樣進行，製作屏蔽膜。Example 5 Except having changed the content ratio of conductive particles as shown in Table 1, it carried out similarly to Example 1, and produced the shielding film.
實施例6~8及比較例7、8 除了如表1所示地變更樹脂層之厚度外，與實施例5同樣進行，製作各屏蔽膜。Examples 6 to 8 and Comparative Examples 7 and 8 Except having changed the thickness of the resin layer as shown in Table 1, it carried out similarly to Example 5, and produced each shielding film.
實施例9 除了如表1所示地變更導電性粒子之種類外，與實施例1同樣進行，製作屏蔽膜。Example 9 Except having changed the kind of electroconductive particle as shown in Table 1, it carried out similarly to Example 1, and produced the shielding film.
實施例10~12及比較例9、10 除了如表1所示地變更樹脂層之厚度外，與實施例9同樣進行，製作各屏蔽膜。Examples 10-12 and Comparative Examples 9, 10 Except having changed the thickness of the resin layer as shown in Table 1, it carried out similarly to Example 9, and produced each shielding film.
(評價) 針對於實施例及比較例獲得之各屏蔽膜如下所述進行評價。評價結果記載於表中。再者，僅使用PET膜(厚度6μm)作為參考例1之評價對象。又，表中之「OL」表示因為超載而超過作為測定極限之100Ω的值。(Evaluation) The shielding films obtained in Examples and Comparative Examples were evaluated as follows. The evaluation results are described in the table. In addition, only PET film (thickness 6 μm) was used as the evaluation target of Reference Example 1. In addition, "OL" in the table indicates a value that exceeds 100Ω, which is the measurement limit, due to overload.
(1)連接電阻值 準備如下印刷配線基板：於由聚醯亞胺膜構成之基底構件上形成模擬接地圖案之2條銅箔圖案(4mm寬、1mm間距)，於其上形成有由絕緣性接著劑層及聚醯亞胺膜構成之覆蓋膜(絕緣膜)。於銅箔圖案之表面設有鍍金層作為表面層。再者，於覆蓋膜形成有直徑0.8mm之模擬接地連接部的圓形開口部。使用加壓機將已於各實施例及比較例中製成之屏蔽膜與印刷配線基板於溫度170℃、時間30分鐘、壓力：2~3MPa的條件下進行接著。接著屏蔽膜後，以電阻計測定2條銅箔圖案間之電阻值，評價銅箔圖案與導電性接著片之連接性，作為連接電阻值。(1) Connection resistance value Prepare the following printed wiring board: form two copper foil patterns (4mm width, 1mm pitch) that simulate ground patterns on a base member made of polyimide film, and an insulating adhesive layer and polyamide are formed thereon. Covering film (insulating film) composed of imine film. A gold-plated layer is provided on the surface of the copper foil pattern as a surface layer. In addition, a circular opening that simulates a ground connection portion with a diameter of 0.8 mm is formed in the cover film. The shielding film and the printed wiring board prepared in each of the Examples and Comparative Examples were bonded using a pressing machine under the conditions of a temperature of 170° C., a time of 30 minutes, and a pressure of 2 to 3 MPa. After the shielding film was followed, the resistance value between the two copper foil patterns was measured with a resistance meter, and the connectivity between the copper foil pattern and the conductive adhesive sheet was evaluated as the connection resistance value.
(2)總透光率 針對於實施例及比較例獲得之屏蔽膜，依循JIS K7361-1使用霧度儀裝置(商品名「NDH4000」、日本電色工業股份有限公司製)，以PET膜面成為積分球側之方式照射測定光進行測定。(2) Total light transmittance Regarding the shielding films obtained in the Examples and Comparative Examples, a haze meter device (trade name "NDH4000", manufactured by Nippon Denshoku Industries Co., Ltd.) was used in accordance with JIS K7361-1, and the PET film surface was irradiated with the integrating sphere side. Measure light for measurement.
◎[表1]
(表1)
於使用厚度10nm之銀/銅合金層作為透明導電層時，即使大量調配30~50質量%的導電性粒子的情況下，本發明之屏蔽膜之總透光率仍較高、透明性優異、連接電阻值較低、連接穩定性優異(實施例1~12)。又，使用球狀導電性粒子之情形(實施例1~4)，相對於使用樹枝狀導電性粒子之情形(實施例9~12)，有總透光率較高、透明性優異之傾向。另一方面，於銀/銅合金層與導電性接著劑層之間不具有樹脂層之情形(比較例1~4)，且於30質量%以上之大量調配條件下，結果為連接電阻值較高。又，樹脂層之厚度為2000nm以上之情形亦相同，結果為連接電阻值較高(比較例5~10)。When a silver/copper alloy layer with a thickness of 10nm is used as a transparent conductive layer, even when a large amount of 30-50% by mass of conductive particles is used, the shielding film of the present invention still has a high total light transmittance, excellent transparency, The connection resistance value is low, and the connection stability is excellent (Examples 1 to 12). In addition, in the case of using spherical conductive particles (Examples 1 to 4), compared to the case of using dendritic conductive particles (Examples 9 to 12), the total light transmittance tends to be higher and the transparency is excellent. On the other hand, when there is no resin layer between the silver/copper alloy layer and the conductive adhesive layer (Comparative Examples 1 to 4), and under the condition of a large amount of 30% by mass or more, the result is that the connection resistance value is relatively high. high. In addition, the same was true when the thickness of the resin layer was 2000 nm or more. As a result, the connection resistance value was high (Comparative Examples 5 to 10).
1:屏蔽膜 11:第1絕緣層 12:透明導電層 13:第2絕緣層 14:導電性接著劑層1: shielding film 11: The first insulating layer 12: Transparent conductive layer 13: The second insulating layer 14: Conductive adhesive layer
圖1係顯示本發明之電磁波屏蔽膜之一實施形態的剖面示意圖。Fig. 1 is a schematic cross-sectional view showing an embodiment of the electromagnetic wave shielding film of the present invention.
1:屏蔽膜 1: shielding film
11:第1絕緣層 11: The first insulating layer
12:透明導電層 12: Transparent conductive layer
13:第2絕緣層 13: The second insulating layer
14:導電性接著劑層 14: Conductive adhesive layer
Claims (6)
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| JP (1) | JP6956926B1 (en) |
| KR (1) | KR20220124684A (en) |
| CN (1) | CN114762470A (en) |
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| KR102594352B1 (en) * | 2022-10-13 | 2023-10-26 | 주식회사 유라 | High-speed communication cable for autovehicles with improved electromagnetic wave shielding performance and manufacturing method thereof |
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| JPH02271697A (en) * | 1989-04-13 | 1990-11-06 | Nitto Denko Corp | Electrostatic and electromagnetic wave shielding material |
| JP2001185894A (en) * | 1999-10-12 | 2001-07-06 | Bridgestone Corp | Electromagnetic wave-shield glass |
| JP4491929B2 (en) * | 2000-07-27 | 2010-06-30 | 株式会社ブリヂストン | Electromagnetic wave shielding light transmissive laminate, method for producing the same, and method for mounting the same |
| JP2002246788A (en) * | 2000-12-12 | 2002-08-30 | Nisshinbo Ind Inc | Transparent electromagnetic radiation shielding material |
| JP2005183652A (en) * | 2003-12-19 | 2005-07-07 | Fuji Photo Film Co Ltd | Electromagnetic wave shielding material and its manufacturing method, and display |
| JP5672201B2 (en) | 2011-09-07 | 2015-02-18 | デクセリアルズ株式会社 | Anisotropic conductive film and method for manufacturing connection structure |
| WO2015068611A1 (en) | 2013-11-07 | 2015-05-14 | 東洋インキＳｃホールディングス株式会社 | Electroconductive adhesive, electroconductive adhesive sheet, wiring device, and method for manufacturing wiring device |
| JP6512804B2 (en) * | 2014-12-05 | 2019-05-15 | 日東電工株式会社 | Transparent conductive film laminate and use thereof |
| JP6516108B2 (en) * | 2017-08-10 | 2019-05-22 | 東洋インキＳｃホールディングス株式会社 | Electromagnetic wave shield laminate for vacuum forming, and electromagnetic wave shield molded body using the same |
| JP6863908B2 (en) * | 2018-01-12 | 2021-04-21 | タツタ電線株式会社 | Electromagnetic wave shield film |
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