TWI807242B - Electromagnetic wave shielding film and shielding printed wiring board - Google Patents
Electromagnetic wave shielding film and shielding printed wiring board Download PDFInfo
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- TWI807242B TWI807242B TW110100652A TW110100652A TWI807242B TW I807242 B TWI807242 B TW I807242B TW 110100652 A TW110100652 A TW 110100652A TW 110100652 A TW110100652 A TW 110100652A TW I807242 B TWI807242 B TW I807242B
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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
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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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- Microelectronics & Electronic Packaging (AREA)
- Physics & Mathematics (AREA)
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- Shielding Devices Or Components To Electric Or Magnetic Fields (AREA)
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- Electrochromic Elements, Electrophoresis, Or Variable Reflection Or Absorption Elements (AREA)
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Abstract
本發明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。 The present invention provides an electromagnetic wave shielding film, which has excellent transparency and low electrical connection resistance even when a large amount of conductive particles are prepared in a conductive adhesive layer.
本發明之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;前述透明導電層係厚度為5~100nm的金屬層且由金、銀、銅、鈀、鎳、鋁或此等之合金構成;前述第2絕緣層之厚度為50~1000nm;前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;前述導電性粒子之含有比率是相對於前述導電性接著劑層100質量%而為1~80質量%。 The electromagnetic shielding film of the present invention is laminated with a first insulating layer, a transparent conductive layer, a second insulating layer and a conductive adhesive layer in sequence; the aforementioned 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 thereof; the thickness of the aforementioned second insulating layer is 50-1000 nm; the aforementioned conductive adhesive layer includes a binder component and spherical or dendritic conductive particles; The adhesive agent layer is 100 mass % and 1-80 mass %.
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 an electromagnetic wave shielding film. More specifically, this invention relates to the electromagnetic wave shielding film used for a printed wiring board.
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。 Printed wiring boards are widely used in electronic devices such as mobile phones, cameras, and notebook computers to incorporate circuits in mechanisms. In addition, it is also used in the connection between the movable part and the control part of the print head of the printer. Electromagnetic wave shielding measures are required in such electronic equipment, and shielded printed wiring boards with electromagnetic wave shielding measures are also used for printed wiring boards used in devices.
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 shielding printed wiring boards, in order to achieve electromagnetic wave shielding measures, an electromagnetic wave shielding film (hereinafter sometimes simply referred to as "shielding film") is used. For example, a shielding film to be 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)。 Regarding shielding films having conductive adhesive sheets, for example, those disclosed in Patent Documents 1 and 2 are known. The above-mentioned shielding film is used by bonding the exposed surface of the conductive adhesive sheet to the surface of the printed wiring board. Specifically, the shielding film is used by bonding the exposed surface of the conductive adhesive sheet to the surface of the cover film provided on the surface of the printed wiring board. These conductive bonding sheets are usually thermocompressed under high temperature/high pressure conditions, and then bonded and laminated on the printed wiring board. Thereby, the shielding film arrange|positioned on a printed wiring board can exhibit the performance (shielding performance) of shielding the electromagnetic wave from the outside of a printed wiring board.
[專利文獻1]日本特開2015-110769號公報 [Patent Document 1] Japanese Patent Laid-Open No. 2015-110769
[專利文獻2]日本特開2012-28334號公報 [Patent Document 2] Japanese Unexamined Patent Publication No. 2012-28334
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。 In recent years, shielding films have sometimes been required to perform alignment easily when sticking to printed wiring boards. Therefore, transparency tends to be required for a barrier film. As a method of improving the transparency, for example, using a thin transparent conductive layer as the conductive layer of the shielding film is considered.
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, in conventional shielding films, the more the amount of conductive particles blended in the conductive adhesive layer increases, the higher the conductivity will be. On the contrary, in the shielding film that has used a transparent conductive layer, if a large amount of conductive particles are blended in the conductive adhesive layer, there will be a problem that the electrical connection resistance value 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。 The present invention was made in view of the above, and an object of the present invention is to provide an electromagnetic wave shielding film that has excellent transparency and low electrical connection resistance even when a large amount of conductive particles are blended in a conductive adhesive layer.
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 conducted repeated studies to achieve the above object, and found that an electromagnetic wave shielding film having a specific layer structure has excellent transparency and low electrical connection resistance even when a large amount of conductive particles is prepared in a conductive adhesive layer. This invention is completed based on the said 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, which is sequentially laminated with a first insulating layer, a transparent conductive layer, a second insulating layer and a conductive adhesive layer; the above-mentioned transparent conductive layer is a metal layer with a thickness of 5-100 nm and is composed of gold, silver, copper, palladium, nickel, aluminum or an alloy containing more than one of these metals; the thickness of the above-mentioned second insulating layer is 50-1000 nm; 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 relative 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。 The above-mentioned second insulating layer and the above-mentioned conductive adhesive layer are preferably 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。 The second insulating layer is preferably laminated directly on one side with the conductive adhesive layer and directly laminated with 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%。 It is preferable that the content ratio of the said electroconductive particle is 30-80 mass % with respect to 100 mass % of the said electroconductive adhesive agent layers.
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 total light transmittance of the above-mentioned electromagnetic wave shielding film in accordance with the measuring method of JIS K 7361-1 is preferably more than 10%.
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。 Moreover, this invention provides the shielded printed wiring board provided with the said electromagnetic wave shielding film.
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 shielding film of the present invention has excellent transparency and low electrical connection resistance regardless of whether a small amount of conductive particles or a large amount of conductive particles are blended in the conductive adhesive layer.
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
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.
[屏蔽膜] [shielding film]
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 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。 One embodiment of the shielding film of the present invention will be described below. FIG. 1 is a schematic cross-sectional view showing an embodiment of the shielding film of the present invention. The shielding film 1 of the present invention shown in Fig. 1 has sequentially The first insulating layer 11 , the transparent conductive layer 12 , the second insulating layer 13 and the conductive adhesive layer 14 .
(第1絕緣層) (1st insulating layer)
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。 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 a 1st insulating layer, a plastic base material (especially a plastic film), a glass plate, etc. are mentioned, for example. 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。 As for the resin constituting the above-mentioned plastic substrate, for example, polyolefin resins such as low-density polyethylene, linear low-density polyethylene, medium-density polyethylene, high-density polyethylene, ultra-low-density polyethylene, random copolymer polypropylene, block copolymer polypropylene, homopolypropylene, polybutene, polymethylpentene, ethylene-vinyl acetate copolymer (EVA), ionic polymer, ethylene-(meth)acrylic acid copolymer, ethylene-(meth)acrylate (random, alternating) copolymer, ethylene-butene copolymer, ethylene-hexene copolymer, etc.; Formic esters; polyesters such as polyethylene terephthalate (PET), polyethylene naphthalate, and polybutylene terephthalate (PBT); polycarbonate (PC); polyimide (PI); polyetheretherketone (PEEK); Acrylic resins such as polymethyl methacrylate (PMMA); acrylonitrile-butadiene-styrene copolymer (ABS); fluororesins; polyvinyl chloride; polyvinylidene chloride; cellulose resins such as cellulose triacetate (TAC); silicone resins, etc. The above-mentioned resins may be used alone or in combination of two or more. From the standpoint of more excellent transparency, among the above-mentioned resins, polyester and cellulose resins are preferable, and polyethylene terephthalate and cellulose triacetate are more preferable.
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 the adjacent layers such as the transparent conductive layer, the surface of the first insulating layer (especially the side surface of the transparent conductive layer) can also be subjected to physical treatments such as corona discharge treatment, plasma treatment, sandblasting treatment, ozone exposure treatment, flame exposure treatment, high voltage exposure treatment, and ionizing radiation treatment; chemical treatments such as chromic acid treatment; Surface treatment for improving adhesion is preferably 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 1-15 μm, preferably 3-10 μm. If the above-mentioned thickness is 1 μm or more, the shielding film and the protection of the transparent conductive layer can be more fully supported. When the said thickness is 15 micrometers or less, transparency and flexibility are excellent, and it is also economically advantageous. Furthermore, when the first insulating layer has a multi-layer structure, the thickness of the first insulating layer is the sum of the thicknesses of all the layers.
(透明導電層) (transparent conductive layer)
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。 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 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 above-mentioned transparent conductive layer is composed of gold, silver, copper, palladium, nickel, aluminum or an alloy containing one or more of these metals. Such a transparent conductive layer has shielding performance without losing excellent 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。 Examples of the above alloys include 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 alloys, silver/neodymium alloys, silver/scandium alloys, silver/indium alloys, silver/antimony alloys, and silver/gallium alloys. Among the above metals, copper and silver are preferable from the standpoint of better electromagnetic wave shielding performance, and silver/copper alloys are preferable from the standpoint of preventing silver from being vulcanized by sulfur components or corroded by chlorine contained in sweat, etc. during solder reflow or when using a shielding film in a high-temperature and high-humidity environment.
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 above-mentioned transparent conductive layer is preferably 5-100 nm, preferably 10-50 nm. When the above-mentioned thickness is 5 nm or more, shielding performance can be maintained. When the said thickness is 100 nm or less, the transparency of a shielding film is excellent. Furthermore, when the transparent conductive layer has a multi-layer structure, the thickness of the transparent conductive layer is the sum of the thicknesses of all the 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 for forming the above-mentioned transparent conductive layer is not particularly limited, for example, electrolysis, evaporation (such as vacuum evaporation), sputtering, CVD, metal-organic (MO), plating, calendering, etc. can be mentioned. Among them, from the viewpoint of ease of manufacture, a transparent conductive layer formed by vapor deposition or sputtering is preferable.
(第2絕緣層) (2nd insulating layer)
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。 The second insulating layer is a transparent layer for protecting the transparent conductive layer. By interposing the second insulating layer between the transparent conductive layer and the conductive adhesive layer, it is possible to suppress a decrease in transparency and connection stability. The decrease in the above-mentioned transparency and connection stability is presumed to be because 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 a plurality of 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. Examples of the binder component include thermoplastic resins, thermosetting resins, active energy ray-curable compounds, and the like. Regarding the above-mentioned thermoplastic resin, thermosetting resin, and active energy ray-curable compound, respectively, those exemplified as adhesive components that can be contained in the conductive adhesive layer described later are mentioned. The said binder component may use only 1 type, and may use 2 or more types.
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 is preferably at least 70% by mass, preferably at least 80% by mass, more preferably at least 90% by mass, relative to 100% by mass of the second insulating layer. When the above-mentioned content is 70% by mass or more, the flexibility will be more excellent, the filling property into small-diameter holes will be better, and the 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。 The second insulating layer may contain components other than the above-mentioned binder components within the range that does not impair the effects of the present invention. Regarding the above-mentioned other components, for example, hardeners, hardening accelerators, plasticizers, flame retardants, defoamers, viscosity modifiers, antioxidants, thinners, anti-settling agents, fillers, leveling agents, coupling agents, ultraviolet absorbers, tackifying resins, anti-blocking agents, etc. can be mentioned. The above-mentioned other components may be used alone or in combination of two or more.
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 50-1000 nm, preferably 100-300 nm. When the above-mentioned thickness is 50 nm or more, shielding performance and connection stability are excellent. When the said thickness is 1000 nm or less, transparency and connection stability are excellent. Furthermore, when the second insulating layer has a multi-layer structure, the thickness of the second insulating layer is the sum of the thicknesses of all the 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 above-mentioned transparent conductive layer, the second insulating layer is preferably directly laminated with the above-mentioned conductive adhesive layer, and it is especially preferable to directly laminate with the above-mentioned conductive adhesive layer on one side, and on the other side and the upper layer. The above-mentioned transparent conductive layer is directly laminated.
(導電性接著劑層) (conductive adhesive layer)
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。 The conductive adhesive layer has, for example, adhesiveness for bonding the shielding film of the present invention to a printed wiring board, and conductivity for electrically connecting to the transparent conductive layer. Moreover, it can also function as a shielding layer exhibiting shielding performance together with the above-mentioned transparent conductive layer. The above-mentioned conductive adhesive layer may be any of 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 above-mentioned conductive adhesive layer contains a binder component and spherical or dendritic (dendrite) 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。 Examples of the binder component include thermoplastic resins, thermosetting resins, active energy ray-curable compounds, and the like. The said binder component may use only 1 type, and may use 2 or more types.
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 aforementioned thermoplastic resins, for example, polystyrene resins, vinyl acetate resins, polyester resins, polyolefin resins (such as polyethylene resins, polypropylene resin compositions, etc.), polyimide resins, acrylic resins, etc. can be cited. The above-mentioned thermoplastic resins may be used alone or in combination of two or more.
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。 Examples of the above-mentioned thermosetting resin include both resins having thermosetting properties (thermosetting resins) and resins obtained by curing the above-mentioned thermosetting resins. As for the said thermosetting resin, a phenol resin, an epoxy resin, a urethane resin, a urethane urea resin, a melamine resin, an alkyd resin, etc. are mentioned, for example. The above-mentioned thermosetting resins may be used alone or in combination of two or more.
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。 Examples of the epoxy resins include bisphenol epoxy resins, spiro epoxy resins, naphthalene epoxy resins, biphenyl epoxy resins, terpene epoxy resins, glycidyl ether epoxy resins, glycidylamine epoxy resins, and novolac epoxy resins.
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。 Examples of the bisphenol epoxy resin include bisphenol A epoxy resin, bisphenol F epoxy resin, bisphenol S epoxy resin, and tetrabromobisphenol A epoxy resin. about As said glycidyl ether type epoxy-type resin, ginseng (glycidoxy phenyl) methane, tetrakis (glycidoxy phenyl) ethane, etc. are mentioned, for example. Tetraglycidyldiaminodiphenylmethane etc. are mentioned about the said glycidylamine type epoxy resin. Examples of the novolac epoxy resin include cresol novolak epoxy resins, phenol novolac epoxy resins, α-naphthol novolac epoxy resins, and brominated phenol novolak epoxy resins.
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。 Examples of the active energy ray-curable compound include both compounds curable by irradiation with active energy rays (active energy ray-curable compounds) and compounds obtained by curing the above-mentioned active energy ray-curable compounds. The active energy ray-curing compound is not particularly limited, but examples thereof include polymerizable compounds having at least two radical reactive groups (for example, (meth)acryl groups) in the molecule. The above-mentioned active energy ray-curing 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。 Among the above-mentioned binder components, 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 placed on the printed wiring board, and then the adhesive component is hardened by pressing and heating, so that 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, the monomer component of a thermoplastic resin may also be contained about the component which comprises the said binder component. When the adhesive component contains a monomer component, temporary adhesiveness, reworkability, and adhesion after heat and pressure are applied to 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 above-mentioned binder component contains a thermosetting resin, a curing agent for promoting a thermosetting reaction may be included with respect to the components constituting the above-mentioned binder component. The said hardening|curing agent can be selected suitably according to the kind of the said thermosetting resin. The above curing agents may be used alone or in combination of two or more.
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 ratio of the adhesive component in the conductive adhesive layer is not particularly limited, but is preferably 20 to 99% by mass, preferably 30 to 80% by mass, more preferably 40 to 70% by mass, based on 100% by mass of the total amount of the conductive adhesive layer. When the said content rate is 20 mass % or more, the adhesiveness with respect to a printed wiring board will become more excellent. Electroconductive particle can be fully contained as the said content rate is 99 mass % or less.
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。 Spherical electroconductive particle and/or dendritic electroconductive particle are used for the said electroconductive particle. By using the said spherical or dendritic electroconductive particle, even when it mix|blends a large amount, it is excellent in transparency, and it is excellent in connection stability. When spherical electroconductive particle is 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。 As said electroconductive particle, a metal particle, a metal-coated resin particle, a carbon filler, etc. are mentioned, for example. The said electroconductive particle may use only 1 type, and may use 2 or more types.
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 metal constituting the coating portion of the metal particles and the metal-coated resin particles include gold, silver, copper, nickel, and zinc. The above-mentioned metals may be used alone or in combination of two or more.
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 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 silver-coated alloy particles include silver-coated copper alloy particles in which alloy particles containing copper (for example, copper alloy particles made of an alloy of copper, nickel, and zinc) are coated with silver. The above-mentioned metal particles can be produced by electrolysis, atomization, reduction 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, silver particles, silver-coated copper particles, and silver-coated copper alloy particles are preferable as the above-mentioned metal particles. Silver-coated copper particles and silver-coated copper alloy particles are preferable from the viewpoint of excellent electrical conductivity, suppression of oxidation and aggregation of metal particles, and cost reduction of metal particles.
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 5-15 μm, more preferably 5-10 μm. The above-mentioned median particle size is the median particle size of all the spherical conductive particles and/or dendritic conductive particles in the above-mentioned conductive adhesive layer, and refers to the particle size of 50% of the cumulative value in the particle size distribution obtained by the laser diffraction/scattering method. When the said median diameter exists in the said range, in this invention which uses electroconductive particle, connection stability becomes more excellent. The above-mentioned median diameter can be measured by, for example, a laser diffraction particle size distribution analyzer (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 rate of the said electroconductive particle in the said electroconductive adhesive layer is preferably 1-80 mass % with respect to 100 mass % of electroconductive adhesive layer, Preferably it is 20-70 mass %, More preferably, it is 30-60 mass %. In the shielding film of the present invention, whether the conductive adhesive layer contains a small amount of about 1% by mass In the case of the above-mentioned electroconductive particles, even in the case of including as much as 80% by mass of the above-mentioned electroconductive particles, the connection resistance value is low and the connection stability is also excellent.
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。 In the range which does not impair the effect of this invention, the said electroconductive adhesive agent layer may contain other components other than the said each component. About the said other component, the component contained in the well-known or usual adhesive agent layer can be mentioned. Examples of the above-mentioned other components include hardening accelerators, plasticizers, flame retardants, defoamers, viscosity modifiers, antioxidants, thinners, anti-settling agents, fillers, leveling agents, coupling agents, ultraviolet absorbers, colorants, anti-blocking agents, and the like. The above-mentioned other components may be used alone or in combination of two or more. Furthermore, the content of conductive particles other than spherical conductive particles and dendritic conductive particles is, for example, less than 10 parts by mass, preferably less than 5 parts by mass, more preferably less than 1 part by mass relative to 100 parts by mass of spherical conductive particles and/or dendritic conductive particles.
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 3-20 μm, preferably 5-15 μm. When the said thickness is 3 micrometers or more, shielding performance will be more excellent. When the said thickness is 20 micrometers or less, the surface of electroconductive particle exists in the tendency for the surface of a layer to come closer or to be exposed from the surface, and connection stability will become 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 [adhesive layer thickness/D50] of the conductive adhesive layer thickness to D50 of the conductive particles is not particularly limited, but is preferably 0.2-1.5, preferably 0.5-1.0. When the said ratio is 0.2 or more, the adhesiveness with respect to to-be-adhered bodies, such as a printed wiring board, becomes more favorable. If the said ratio is 1.5 or less, the quantity of the electroconductive particle exposed from the surface of an electroconductive adhesive layer will increase, and connection stability will become 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 (peeling film) on the conductive adhesive layer side. The separator is laminated so as to be peelable from the masking film of the present invention. The separator is a requirement 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。 Examples of the separator include: polyethylene terephthalate (PET) film, polyethylene film, polypropylene film, fluorine-based release agent, or plastic film or paper coated with a release agent such as a long-chain alkyl acrylate release agent.
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 separator is preferably 10-200 μm, preferably 15-150 μm. When the said thickness is 10 micrometers or more, protection performance is more excellent. When the said thickness is 200 micrometers or less, it becomes easy to peel off a separator at the time of 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. Examples of the above-mentioned other layers include other insulating layers, antireflection layers, antiglare layers, antifouling layers, hard coat layers, ultraviolet absorbing layers, and anti-Newton ring layers.
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 masking film of the present invention is excellent in transparency. The total light transmittance of the shielding film of the present invention is preferably at least 10%, preferably at least 20%, more preferably at least 50%, and most preferably at least 65% under the measurement method of JIS K 7361-1. The above-mentioned total light transmittance can be measured using a known spectrometer. In addition, the said total light transmittance was measured about 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 is preferably 95% or less, preferably 92% or less, more preferably 90% or less in accordance with the measurement method of JIS K 7361-1. The said haze value can be measured using a well-known spectrometer. In addition, the said haze value was measured about the laminated body which used the 1st insulating layer and the said electroconductive 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 suitable for use in printed wiring boards or wireless power transmission systems, especially for flexible printed wiring boards (FPC) or electromagnetic induction wireless power transmission systems. The shielding film of the present invention has low electrical connection resistance regardless of whether a small amount of conductive particles or a large amount of conductive particles are mixed in the conductive adhesive layer. In addition, it is excellent in transparency, and it is easy to align on a printed wiring board or an adherend such as a coil for power supply or power transmission in a wireless power transmission system. Therefore, the shielding film of this invention can be used suitably as the electromagnetic wave shielding film for flexible printed wiring boards.
(電磁波屏蔽膜之製造方法) (Manufacturing method of electromagnetic wave shielding film)
就本發明之屏蔽膜之製造方法進行說明。 The manufacturing method of the masking film of this invention is demonstrated.
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 manufacture of the shielding film 1 of the present invention shown in FIG. 1, at first the first insulating layer 11 is formed into a transparent conductive layer 12. The formation of the transparent conductive layer 12 is preferably performed by evaporation or sputtering. The above-mentioned vapor deposition method and sputtering method can employ known or commonly used methods. Thus, by forming a transparent conductive layer by vapor deposition method or sputtering method, the conductive layer which has moderate thickness and transparency can be manufactured easily.
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, for example, a resin composition for forming the second insulating layer 13 may be coated (coated) on the surface of the formed transparent conductive layer 12, and the solvent may be removed and/or a part thereof may be cured as necessary.
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 (vehicle) in addition to the components contained in the second insulating layer. As a solvent, for example, toluene, acetone, methyl ethyl ketone, methanol, ethanol, propanol, ethyl acetate, propyl acetate, butyl acetate, dimethylformamide, etc. are 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 known coating method can also be used. For example, coating machines such as a gravure roll coater, reverse roll coater, touch roll coater, die coater, dip roll coater, bar coater, knife coater, spray coater, chip coater, direct coater, slot die coater, etc. can be used.
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 adhesive layer 14 can be coated (coated) on the surface of the formed second insulating layer, and the solvent can be removed and/or a part of it can be cured as necessary.
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 above-mentioned adhesive composition contains, for example, a solvent (vehicle) in addition to each component contained in the above-mentioned conductive adhesive layer. As for the solvent, those exemplified as solvents that can be contained in the above-mentioned resin composition can be mentioned. The solid content concentration of the said adhesive composition can be set suitably according to the thickness etc. of the electroconductive adhesive layer to be formed.
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。 A well-known coating method can also be used when coating the said adhesive composition. For example, the coater used for coating of the said resin composition mentioned above is mentioned as an example.
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 production method, the method of sequentially forming each layer (direct coating method) was described, but it is not limited to this method. For example, it can also be produced by laminating and sequentially laminating each layer formed on a temporary base material such as a separation membrane or a base material (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。 A printed wiring board can be produced using the shielding film of the present invention. For example, by bonding the conductive adhesive layer of the shielding film of the present invention to a printed wiring board (for example, a cover film), a shielded printed wiring board having the shielding film of the present invention bonded to the printed wiring board can be obtained. In the said shielded printed wiring board, the said electroconductive adhesive layer can also be heat-cured.
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 the electroconductive particle in a table shows the ratio in a conductive adhesive agent layer.
比較例1 Comparative example 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。 A silver/copper alloy layer (thickness 10 nm) was formed on the surface of the PET film (thickness 6 μm) by sputtering. Then, use a wire bar to coat the adhesive composition obtained by mixing epoxy resin solution and conductive particles A (silver-coated copper powder, spherical shape, median diameter 5 μm) on the surface of the alloy layer, and heat at 120° C. for 1 minute to form a conductive adhesive layer (thickness 5 μm). As mentioned above, the masking film of the comparative example 1 was produced. Moreover, the compounding quantity of the epoxy resin solution and electroconductive particle A was set to the quantity which made the ratio of the epoxy resin in the electroconductive adhesive layer 70 mass %, and the ratio of electroconductive particle A was 30 mass %.
比較例2~4 Comparative example 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)。 Except having changed the kind and content ratio of electroconductive particle as shown in Table 1, it carried out similarly to the comparative example 1, and produced each masking film. Moreover, electroconductive particle B is a silver-coated copper powder (dendritic shape, median diameter 5 micrometers).
實施例1 Example 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。 A silver/copper alloy layer (thickness 10 nm) was formed on the surface of the PET film (thickness 6 μm) by sputtering. Next, a polyester resin composition was coated on the surface of the alloy layer using a wire bar, 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 conductive particles A was coated on the surface of the resin layer using a wire bar, and heated at 120° C. for 1 minute to form a conductive adhesive layer (thickness 5 μm). As described above, the masking film of Example 1 was produced. Also, epoxy resin The compounding quantity of liquid and electroconductive particle A was set so that the ratio of the epoxy resin in the electroconductive adhesive layer may be 70 mass %, and the ratio of electroconductive particle A shall be 30 mass %.
實施例2~4及比較例5、6 Embodiment 2~4 and comparative example 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。 Except having changed the thickness of the resin layer as shown in Table 1, it carried out similarly to Example 1, and each masking film was produced.
實施例5 Example 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。 Except having changed the content ratio of electroconductive particle as shown in Table 1, it carried out similarly to Example 1, and produced the masking film.
實施例6~8及比較例7、8 Embodiment 6~8 and comparative example 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。 Except having changed the thickness of the resin layer as shown in Table 1, it carried out similarly to Example 5, and each masking film was produced.
實施例9 Example 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。 Except having changed the kind of electroconductive particle as shown in Table 1, it carried out similarly to Example 1, and produced the masking film.
實施例10~12及比較例9、10 Embodiment 10~12 and comparative example 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。 Except having changed the thickness of the resin layer as shown in Table 1, it carried out similarly to Example 9, and each masking film was produced.
(評價) (evaluate)
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。 Each masking film obtained by the Example and the comparative example was evaluated as follows. The evaluation results are shown in the table. In addition, only the PET film (thickness 6 micrometers) was used as the evaluation object of the reference example 1. In addition, "OL" in the table represents the value exceeding 100Ω which is the measurement limit due to overload.
(1)連接電阻值 (1) Connection resistance value
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。 Prepare the printed wiring board as follows: 2 copper foil patterns (4 mm wide, 1 mm pitch) for simulating grounding patterns are formed on the base member made of polyimide film, and an insulating adhesive layer and poly Covering film (insulating film) made of imide film. A gold-plated layer is provided on the surface of the copper foil pattern as a surface layer. Furthermore, a circular opening simulating a ground connection portion with a diameter of 0.8 mm was formed in the cover film. The masking film and the printed wiring board prepared in each example and comparative example were bonded under the conditions of temperature 170° C., time 30 minutes, and pressure: 2 to 3 MPa using a press machine. After the shielding film is applied, the resistance value between the two copper foil patterns is measured with a resistance meter, and the connection between the copper foil pattern and the conductive adhesive sheet is evaluated as the connection resistance value.
(2)總透光率 (2) Total light transmittance
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。 The masking films obtained in Examples and Comparative Examples were measured by irradiating measurement light with the PET film surface facing the integrating sphere side using a haze meter (trade name "NDH4000", manufactured by Nippon Denshoku Industries Co., Ltd.) in accordance with JIS K7361-1.
◎[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 the transparent conductive layer, the shielding film of the present invention still has high total light transmittance, excellent transparency, low connection resistance, and excellent connection stability even when a large amount of conductive particles is prepared in an amount of 30-50% by mass (Examples 1-12). Moreover, the case of using spherical electroconductive particle (Examples 1-4) tended to have a high total light transmittance and excellent transparency compared with the case of using dendritic electroconductive particle (Example 9-12). On the other hand, in the case where there is no resin layer between the silver/copper alloy layer and the conductive adhesive layer (Comparative Examples 1-4), and under the conditions of a large amount of 30% by mass or more, The result is a higher connection resistance value. In addition, the case where the thickness of the resin layer was 2000 nm or more was the same, and as a result, the connection resistance value was high (comparative examples 5 to 10).
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
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JP2001185894A (en) * | 1999-10-12 | 2001-07-06 | Bridgestone Corp | Electromagnetic wave-shield glass |
JP2002246788A (en) * | 2000-12-12 | 2002-08-30 | Nisshinbo Ind Inc | Transparent electromagnetic radiation shielding material |
TW201636217A (en) * | 2014-12-05 | 2016-10-16 | Nitto Denko Corp | Transparent conductive film laminate and use therefor |
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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 |
JP2002246788A (en) * | 2000-12-12 | 2002-08-30 | Nisshinbo Ind Inc | Transparent electromagnetic radiation shielding material |
TW201636217A (en) * | 2014-12-05 | 2016-10-16 | Nitto Denko Corp | Transparent conductive film laminate and use therefor |
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