TW202234982A - Electromagnetic wave shield film - Google Patents
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- TW202234982A TW202234982A TW110142284A TW110142284A TW202234982A TW 202234982 A TW202234982 A TW 202234982A TW 110142284 A TW110142284 A TW 110142284A TW 110142284 A TW110142284 A TW 110142284A TW 202234982 A TW202234982 A TW 202234982A
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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
- B32B15/095—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 comprising polyurethanes
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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
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/40—Layered products comprising a layer of synthetic resin comprising polyurethanes
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- C09J9/00—Adhesives characterised by their physical nature or the effects produced, e.g. glue sticks
- C09J9/02—Electrically-conducting adhesives
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- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K9/00—Screening of apparatus or components against electric or magnetic fields
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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- Y02A30/00—Adapting or protecting infrastructure or their operation
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- Chemical & Material Sciences (AREA)
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Abstract
Description
本發明係關於電磁波屏蔽膜。The present invention relates to an electromagnetic wave shielding film.
背景技術 於作為行動裝置之智慧型手機、平板電腦等中,為了遮蔽從內部產生的電磁波或從外部入侵的電磁波,使用貼附有電磁波屏蔽膜的附屏蔽的撓性印刷配線板(以下亦記載為「屏蔽印刷配線板」)。電磁波屏蔽膜所使用的屏蔽層係藉由利用蒸鍍、濺鍍、鍍覆等形成的薄膜金屬層、或高度填充摻合有導電性填料的導電性膏等而形成。如果未來5G等真的普及,為了進行大容量資料的通信,要發展高頻、高速傳輸,更加需要電子設備的雜訊對策。 Background technique In smartphones, tablet computers, etc., which are mobile devices, in order to shield electromagnetic waves generated from the inside or electromagnetic waves intruded from the outside, a shielded flexible printed wiring board with an electromagnetic wave shielding film attached (hereinafter also referred to as "" Shielded Printed Wiring Board”). The shielding layer used for the electromagnetic wave shielding film is formed by a thin-film metal layer formed by vapor deposition, sputtering, plating, or the like, or a conductive paste highly filled with a conductive filler, or the like. If 5G and the like are really popularized in the future, in order to communicate large-capacity data, to develop high-frequency and high-speed transmission, noise countermeasures for electronic equipment will be more necessary.
一般而言,電磁波屏蔽膜係由屏蔽層及保護層(絕緣層)構成,該屏蔽層係成為遮蔽電磁波的本體,該保護層(絕緣層)係用以保護該屏蔽層免受來自外部的衝撃或化學品、溶劑、水等的影響。Generally speaking, an electromagnetic wave shielding film is composed of a shielding layer and a protective layer (insulating layer), the shielding layer is the body that shields electromagnetic waves, and the protective layer (insulating layer) is used to protect the shielding layer from external shocks or the effects of chemicals, solvents, water, etc.
對於配置於撓性印刷配線板的電磁波屏蔽膜要求柔軟性,對於其構成要件的保護層亦要求柔軟性。Flexibility is required for an electromagnetic wave shielding film arranged on a flexible printed wiring board, and flexibility is also required for a protective layer constituting the element.
關於這種配置於撓性印刷配線板的電磁波屏蔽膜,於專利文獻1中揭示有一種電磁波屏蔽膜,其具備:具有凹凸的導電性屏蔽層、及被覆前述凹凸的接著劑層;且前述凹凸之最大山部高度的值比前述接著劑層的厚度大。Regarding the electromagnetic wave shielding film arranged on such a flexible printed wiring board, Patent Document 1 discloses an electromagnetic wave shielding film including a conductive shielding layer having irregularities, an adhesive layer covering the irregularities, and the irregularities The value of the maximum peak height is larger than the thickness of the aforementioned adhesive layer.
又,於專利文獻2中揭示一種電磁波屏蔽膜,其特徵在於:具備屏蔽層、及積層於上述屏蔽層的絕緣層,且上述絕緣層包含氧化矽微粒子,上述絕緣層中之前述氧化矽微粒子的含量為10~50wt%。Further, Patent Document 2 discloses an electromagnetic wave shielding film comprising a shielding layer and an insulating layer laminated on the shielding layer, wherein the insulating layer contains silicon oxide fine particles, and the silicon oxide fine particles in the insulating layer are The content is 10~50wt%.
又,於專利文獻3中揭示一種樹脂組成物,特徵在於:其係作為保護層用的樹脂組成物,該保護層用於上述電磁波屏蔽膜,該樹脂組成物包含非晶性聚酯樹脂、硬化劑及白色顏料;上述非晶性聚酯樹脂之數量平均分子量Mn小於20,000,玻璃轉移點Tg為40℃以上,上述硬化劑係選自於由封端異氰酸酯、己烷二異氰酸酯之三羥甲基丙烷加成物及環己烷二異氰酸酯之三聚異氰酸酯加成物所構成群組中之至少1種。 先行技術文獻 專利文獻 In addition, Patent Document 3 discloses a resin composition which is a resin composition for a protective layer used in the above-mentioned electromagnetic wave shielding film, the resin composition comprising an amorphous polyester resin, a cured agent and white pigment; the number-average molecular weight Mn of the above-mentioned amorphous polyester resin is less than 20,000, the glass transition point Tg is above 40°C, and the above-mentioned hardener is selected from the group consisting of blocked isocyanate, hexane diisocyanate, trimethylol At least one of the group consisting of a propane adduct and a trimer isocyanate adduct of cyclohexane diisocyanate. prior art literature Patent Literature
[專利文獻1]國際公開第2016/088381號 [專利文獻2]日本特開2019-046871號公報 [專利文獻3]國際公開第2019/188983號 [Patent Document 1] International Publication No. 2016/088381 [Patent Document 2] Japanese Patent Laid-Open No. 2019-046871 [Patent Document 3] International Publication No. 2019/188983
發明概要 發明欲解決之課題 一般而言,柔軟性較高的保護層,其玻璃轉移點與交聯密度較低。若保護層之玻璃轉移點較低,會有以捲材狀保管電磁波屏蔽膜時容易發生黏著的問題。又,若構成保護層的樹脂的交聯密度較低,在藉由熱壓將電磁波屏蔽膜配置在為使印刷配線板中之接地電路露出而設置的開口部等之高低差位置(以下亦簡單記載為「印刷配線板之高低差位置」)時,保護層容易產生局部較薄的部位,從而保護層之物理性強度會降低或溼氣容易穿透保護層。其結果,有電磁波屏蔽膜之耐熱性、耐溼性容易降低的問題。 Summary of Invention The problem to be solved by the invention Generally speaking, the protective layer with higher flexibility has lower glass transition point and lower crosslink density. If the glass transition point of the protective layer is low, there is a problem that sticking is likely to occur when the electromagnetic wave shielding film is stored in the form of a roll. In addition, if the crosslinking density of the resin constituting the protective layer is low, the electromagnetic wave shielding film is placed at the height difference position such as the opening provided for exposing the ground circuit in the printed wiring board by hot pressing (hereinafter also simplified). When it is described as "the height difference position of the printed wiring board"), the protective layer is likely to be locally thin, so that the physical strength of the protective layer will be reduced or the moisture will easily penetrate the protective layer. As a result, there is a problem that the heat resistance and moisture resistance of the electromagnetic wave shielding film tend to be lowered.
本發明係為了解決上述問題而完成的發明,本發明之目的係提供一種在以捲材狀保管時不易發生黏著、且耐溼性及耐撓曲性優異的電磁波屏蔽膜。 用以解決課題之手段 The present invention was made in order to solve the above-mentioned problems, and an object of the present invention is to provide an electromagnetic wave shielding film which does not easily cause sticking when stored in a roll form, and which is excellent in moisture resistance and deflection resistance. means of solving problems
本發明之電磁波屏蔽膜,特徵在於:其係積層有保護層及屏蔽層者,上述保護層包含胺基甲酸酯系樹脂及平均粒徑為10μm以下之非導電性填料,該胺基甲酸酯系樹脂之酸值為2000~4000g/eq、且Tg為0℃以上;相對於上述保護層之全體重量,上述非導電性填料之重量比率為10~40重量%。The electromagnetic wave shielding film of the present invention is characterized in that a protective layer and a shielding layer are laminated, wherein the protective layer contains a urethane resin and a non-conductive filler having an average particle size of 10 μm or less, the urethane The acid value of the ester-based resin is 2000-4000 g/eq, and the Tg is 0°C or higher; the weight ratio of the non-conductive filler is 10-40 wt % relative to the entire weight of the protective layer.
於本發明之電磁波屏蔽膜中,保護層所含之胺基甲酸酯系樹脂之酸值為2000~4000g/eq。 若酸值在上述範圍,交聯密度就成為適度範圍,故在藉由熱壓將電磁波屏蔽膜配置於印刷配線板之高低差位置時,保護層不易產生局部較薄的部位。因此,保護層之物理性強度不易降低或溼氣不易穿透保護層。其結果,電磁波屏蔽膜之耐撓曲性及耐溼性變得良好。 若酸值小於2000g/eq,則交聯密度會變高、保護層會變硬。其結果,保護層之韌性容易降低、耐撓曲性亦容易降低。 若酸值大於4000g/eq,則交聯密度會變低,在藉由熱壓將電磁波屏蔽膜配置於印刷配線板之高低差位置時,保護層容易產生局部較薄的部位。其結果,耐溼性容易極度降低。 In the electromagnetic wave shielding film of the present invention, the acid value of the urethane resin contained in the protective layer is 2000-4000 g/eq. When the acid value is in the above range, the crosslinking density is in an appropriate range, so that when the electromagnetic wave shielding film is arranged at the height difference position of the printed wiring board by hot pressing, the protective layer is less likely to be locally thin. Therefore, the physical strength of the protective layer is not easily reduced or moisture is not easily penetrated through the protective layer. As a result, the deflection resistance and moisture resistance of the electromagnetic wave shielding film become favorable. When the acid value is less than 2000 g/eq, the crosslinking density becomes high and the protective layer becomes hard. As a result, the toughness of the protective layer tends to decrease, and the deflection resistance also tends to decrease. If the acid value is more than 4000 g/eq, the crosslinking density will be low, and when the electromagnetic wave shielding film is arranged at the height difference position of the printed wiring board by hot pressing, the protective layer is likely to be locally thin. As a result, the moisture resistance tends to be extremely reduced.
於本發明之電磁波屏蔽膜中,保護層所含之胺基甲酸酯系樹脂之Tg為0℃以上。 因此,以捲材狀保管本發明之電磁波屏蔽膜時,不易發生黏著。 In the electromagnetic wave shielding film of this invention, Tg of the urethane resin contained in a protective layer is 0 degreeC or more. Therefore, when the electromagnetic wave shielding film of the present invention is stored in the form of a roll, sticking is less likely to occur.
於本發明之電磁波屏蔽膜中,保護層包含平均粒徑為10μm以下之非導電性填料,且相對於保護層之全體重量,非導電性填料之重量比率為10~40重量%。 若保護層包含上述重量比率的平均粒徑為10μm以下之非導電性填料,在藉由熱壓將電磁波屏蔽膜配置於印刷配線板之高低差位置時,可防止保護層所含之胺基甲酸酯系樹脂流動而使保護層之一部分變薄。其結果,電磁波屏蔽膜之耐溼性及耐撓曲性變得良好。 若非導電性填料之重量比率小於10重量%,不易獲得包含非導電性填料時的效果,耐溼性容易降低。 若非導電性填料之重量比率大於40重量%,則保護層會變硬、柔軟性容易降低。其結果,耐撓曲性容易變低。 In the electromagnetic wave shielding film of the present invention, the protective layer includes a non-conductive filler with an average particle diameter of 10 μm or less, and the weight ratio of the non-conductive filler is 10 to 40 wt % relative to the entire weight of the protective layer. If the protective layer contains a non-conductive filler with an average particle diameter of 10 μm or less in the above weight ratio, when the electromagnetic wave shielding film is placed at the height difference position of the printed wiring board by hot pressing, the aminomethyl group contained in the protective layer can be prevented. The ester-based resin flows to thin a part of the protective layer. As a result, the moisture resistance and deflection resistance of the electromagnetic wave shielding film become favorable. If the weight ratio of the non-conductive filler is less than 10% by weight, the effect when the non-conductive filler is included is difficult to obtain, and the moisture resistance tends to decrease. If the weight ratio of the non-conductive filler exceeds 40% by weight, the protective layer becomes hard and the flexibility tends to decrease. As a result, the deflection resistance tends to decrease.
於本發明之電磁波屏蔽膜中,上述保護層宜更包含環氧系樹脂。 若保護層包含環氧系樹脂,在藉由熱壓將電磁波屏蔽膜配置於印刷配線板時,可抑制保護層所含之胺基甲酸酯系樹脂流動。 In the electromagnetic wave shielding film of the present invention, the protective layer preferably further contains an epoxy resin. When the protective layer contains an epoxy resin, the flow of the urethane resin contained in the protective layer can be suppressed when the electromagnetic wave shielding film is arranged on a printed wiring board by hot pressing.
於本發明之電磁波屏蔽膜中,上述胺基甲酸酯系樹脂與上述環氧系樹脂之重量比宜為胺基甲酸酯系樹脂/環氧系樹脂=4~49。 若上述重量比小於4,則環氧系樹脂會變過多、保護層容易變硬。其結果,保護層之柔軟性降低、耐撓曲性降低。 若上述重量比大於49,則環氧系樹脂變少、保護層變柔軟,不易獲得包含環氧系樹脂的效果。 In the electromagnetic wave shielding film of the present invention, the weight ratio of the urethane-based resin to the epoxy-based resin is preferably urethane-based resin/epoxy-based resin=4-49. When the said weight ratio is less than 4, an epoxy resin will become too much, and a protective layer will become hard easily. As a result, the flexibility of the protective layer is lowered, and the deflection resistance is lowered. When the said weight ratio exceeds 49, the epoxy resin becomes small and a protective layer becomes soft, and it becomes difficult to acquire the effect containing an epoxy resin.
於本發明之電磁波屏蔽膜中,上述胺基甲酸酯系樹脂之Tg宜為0~60℃。 若胺基甲酸酯系樹脂之Tg為0~60℃,在將本發明之電磁波屏蔽膜熱壓於印刷配線板時,由於保護層具有適度的流動性,故可防止保護層之一部分變薄、從而使電磁波屏蔽膜之耐溼性及耐撓曲性降低。 In the electromagnetic wave shielding film of the present invention, the Tg of the urethane resin is preferably 0 to 60°C. If the Tg of the urethane-based resin is 0 to 60° C., when the electromagnetic wave shielding film of the present invention is hot-pressed on a printed wiring board, the protective layer has moderate fluidity, so that part of the protective layer can be prevented from becoming thin. , thereby reducing the moisture resistance and flex resistance of the electromagnetic wave shielding film.
於本發明之電磁波屏蔽膜中,上述胺基甲酸酯系樹脂之重量平均分子量宜為100,000~2,000,000、較佳為170,000~500,000。 若胺基甲酸酯系樹脂之重量平均分子量在上述範圍,因為胺基甲酸酯系樹脂成為適度的硬度及流動性,故可使電磁波屏蔽膜之耐熱性、耐溼性及耐撓曲性提高。 In the electromagnetic wave shielding film of the present invention, the weight average molecular weight of the urethane resin is preferably 100,000-2,000,000, preferably 170,000-500,000. If the weight-average molecular weight of the urethane resin is in the above range, the urethane resin has moderate hardness and fluidity, so that the heat resistance, moisture resistance, and deflection resistance of the electromagnetic wave shielding film can be improved. improve.
於本發明之電磁波屏蔽膜中,上述非導電性填料宜為選自於由氧化矽及有機磷酸鹽所構成群組中之至少1種。 由該等材料構成之非導電性填料可使電磁波屏蔽膜之耐溼性及耐撓曲性適當地提高。 In the electromagnetic wave shielding film of the present invention, the non-conductive filler is preferably at least one selected from the group consisting of silicon oxide and organic phosphate. The non-conductive filler composed of these materials can appropriately improve the moisture resistance and deflection resistance of the electromagnetic wave shielding film.
於本發明之電磁波屏蔽膜中,上述屏蔽層亦可為導電性接著劑層。 又,於本發明之電磁波屏蔽膜中,上述屏蔽層可為金屬層,且在上述屏蔽層其未積層有上述保護層之側之面亦可進一步積層有接著劑層。 本發明之電磁波屏蔽膜無論哪個態樣皆可適當地遮蔽電磁波。又,在電磁波屏蔽膜以捲材狀保管時不易發生黏著,電磁波屏蔽膜之耐熱性、耐溼性及耐撓曲性充分地變高。 發明效果 In the electromagnetic wave shielding film of the present invention, the shielding layer may be a conductive adhesive layer. Furthermore, in the electromagnetic wave shielding film of the present invention, the shielding layer may be a metal layer, and an adhesive layer may be further laminated on the side of the shielding layer on which the protective layer is not laminated. The electromagnetic wave shielding film of the present invention can appropriately shield electromagnetic waves in any form. In addition, when the electromagnetic wave shielding film is stored in the form of a roll, sticking is unlikely to occur, and the heat resistance, moisture resistance, and deflection resistance of the electromagnetic wave shielding film are sufficiently high. Invention effect
於本發明之電磁波屏蔽膜中,保護層包含胺基甲酸酯系樹脂及平均粒徑為10μm以下之非導電性填料,該胺基甲酸酯系樹脂之酸值為2000~4000g/eq、且Tg為0℃以上;相對於保護層之全體重量,非導電性填料之重量比率為10~40重量%。 因此,胺基甲酸酯系樹脂之交聯密度會成為適度範圍,電磁波屏蔽膜之耐撓曲性及耐溼性會變得良好。又,因為胺基甲酸酯系樹脂之Tg為0℃以上,故在以捲材狀保管電磁波屏蔽膜時,不易發生黏著。又,藉由保護層中包含預定的非導電性填料,在藉由熱壓將電磁波屏蔽膜配置於印刷配線板時,可防止保護層所含之胺基甲酸酯系樹脂流動而使保護層之一部分變薄。因此,保護層不易產生局部較薄的部位。其結果,電磁波屏蔽膜之耐溼性及耐撓曲性變得良好。 In the electromagnetic wave shielding film of the present invention, the protective layer comprises a urethane resin and a non-conductive filler with an average particle diameter of 10 μm or less, and the acid value of the urethane resin is 2000-4000 g/eq, and Tg is 0°C or higher; the weight ratio of the non-conductive filler is 10 to 40 wt % relative to the entire weight of the protective layer. Therefore, the crosslinking density of the urethane-based resin will be in an appropriate range, and the deflection resistance and moisture resistance of the electromagnetic wave shielding film will be favorable. In addition, since the Tg of the urethane resin is 0° C. or higher, when the electromagnetic wave shielding film is stored in the form of a roll, sticking is unlikely to occur. In addition, by including a predetermined non-conductive filler in the protective layer, when the electromagnetic wave shielding film is placed on a printed wiring board by hot pressing, the urethane-based resin contained in the protective layer can be prevented from flowing and the protective layer can be A part is thinned. Therefore, the protective layer is less likely to be locally thin. As a result, the moisture resistance and deflection resistance of the electromagnetic wave shielding film become favorable.
用以實施發明之形態 以下,具體地說明本發明之電磁波屏蔽膜。然而,本發明並不限定於以下實施形態,可於不變更本發明主旨之範圍內進行適當變更後應用。 Form for carrying out the invention Hereinafter, the electromagnetic wave shielding film of this invention is demonstrated concretely. However, the present invention is not limited to the following embodiments, and can be appropriately changed and applied within the scope of not changing the gist of the present invention.
圖1係示意性顯示本發明之電磁波屏蔽膜之一例的剖面圖。
圖1所示之電磁波屏蔽膜10為依序積層有保護層20、金屬層30及導電性接著劑層40的電磁波屏蔽膜。
於電磁波屏蔽膜10中,金屬層30係作為遮蔽電磁波的屏蔽層而起作用。
以下說明各構成。
FIG. 1 is a cross-sectional view schematically showing an example of the electromagnetic wave shielding film of the present invention.
The electromagnetic
(保護層)
於電磁波屏蔽膜10中,保護層20包含胺基甲酸酯系樹脂及非導電性填料。
(The protective layer)
In the electromagnetic
保護層20所含之胺基甲酸酯系樹脂之酸值為2000~4000g/eq。酸值宜為2100~3900g/eq、較佳為2500~3500g/eq。
若酸值在上述範圍,交聯密度就成為適度範圍,故在藉由熱壓將電磁波屏蔽膜配置於印刷配線板之高低差位置時,保護層不易產生局部較薄的部位。因此,保護層之物理性強度不易降低或溼氣不易穿透保護層。其結果,電磁波屏蔽膜之耐撓曲性及耐溼性變得良好。
若酸值小於2000g/eq,則交聯密度會變高、保護層會變硬。其結果,保護層之韌性降低、耐撓曲性容易降低。
若酸值大於4000g/eq,則交聯密度會變低,在藉由熱壓將電磁波屏蔽膜配置於印刷配線板之高低差位置時,保護層容易產生局部較薄的部位。其結果,耐溼性容易極度降低。
The acid value of the urethane resin contained in the
保護層20所含之胺基甲酸酯系樹脂之Tg為0℃以上。Tg宜為0~60℃、較佳為30~60℃。
若胺基甲酸酯系樹脂之Tg為0℃以上,在以捲材狀保管電磁波屏蔽膜10時,不易發生黏著。
又,若胺基甲酸酯系樹脂之Tg為0~60℃,在將本發明之電磁波屏蔽膜熱壓於印刷配線板時,保護層會形成適度的流動性。
又,製作本發明之電磁波屏蔽膜時,有時於轉印膜形成保護層。此時,保護層與轉印膜之密著性提高。
再者,胺基甲酸酯系樹脂之Tg係指根據JIS K7121之示差掃描熱量測定(DSC)所測得的值。
The Tg of the urethane resin contained in the
胺基甲酸酯系樹脂之重量平均分子量宜為100,000~2,000,000、較佳為170,000~500,000。 若胺基甲酸酯系樹脂之重量平均分子量在上述範圍,胺基甲酸酯系樹脂就會形成適度的硬度及流動性,故可使保護層之耐熱性、耐溼性及耐撓曲性提高。 再者,胺基甲酸酯系樹脂的重量平均分子量可使用以下條件的凝膠滲透層析法(GPC)測定。 測定器:ALLiance GPC System(Waters製) 管柱:Shodex GPC KF-806L(昭和電工) 管柱溫度:40℃ 試料濃度:0.05wt%/THF 注入量:10μL 標準試料:東曹:標準PS 500、Shodex標準PS SM-105(套組) The weight average molecular weight of the urethane resin is preferably 100,000 to 2,000,000, preferably 170,000 to 500,000. If the weight-average molecular weight of the urethane resin is within the above range, the urethane resin will have appropriate hardness and fluidity, so that the heat resistance, moisture resistance, and flex resistance of the protective layer can be improved. improve. In addition, the weight average molecular weight of a urethane resin can be measured using the gel permeation chromatography (GPC) of the following conditions. Measuring device: ALLiance GPC System (manufactured by Waters) Column: Shodex GPC KF-806L (Showa Denko) Column temperature: 40℃ Sample concentration: 0.05wt%/THF Injection volume: 10 μL Standard sample: Tosoh: Standard PS 500, Shodex Standard PS SM-105 (set)
保護層20所含之非導電性填料之平均粒徑為10μm以下,且相對於保護層20之全體重量,非導電性填料之重量比率為10~40重量%。又,非導電性填料之重量比率宜為10~35重量%、較佳為10~25質量%。
若保護層20包含上述重量比率的非導電性填料,在藉由熱壓將電磁波屏蔽膜配置於印刷配線板時,可防止保護層所含之胺基甲酸酯系樹脂流動而使保護層之一部分變薄。因此,保護層不易產生局部較薄的部位。其結果,電磁波屏蔽膜之耐溼性及耐撓曲性變得良好。尤其是若非導電性填料之重量比率為10~25質量%,電磁波屏蔽膜之耐撓曲性更加良好。
若非導電性填料之重量比率小於10重量%,不易獲得包含非導電性填料時的效果,耐溼性容易降低。
若非導電性填料之重量比率大於40重量%,則保護層變硬、柔軟性容易降低。其結果,耐撓曲性容易變低。
The average particle size of the non-conductive filler contained in the
又,非導電性填料之平均粒徑宜為100nm~10μm。 若非導電性填料之平均粒徑為100nm以上,可適當地防止保護層所含之胺基甲酸酯系樹脂流動而使保護層之一部分變薄。 若非導電性填料之平均粒徑為10μm以下,可薄化保護層全體之厚度。 In addition, the average particle diameter of the non-conductive filler is preferably 100 nm to 10 μm. If the average particle diameter of the non-conductive filler is 100 nm or more, the urethane resin contained in the protective layer can be appropriately prevented from flowing, and a part of the protective layer can be thinned. If the average particle size of the non-conductive filler is 10 μm or less, the thickness of the entire protective layer can be reduced.
非導電性填料宜為選自於由氧化矽及有機磷酸鹽所構成群組中之至少1種。其等之中,以氧化矽為佳。 由該等材料構成之非導電性填料可使電磁波屏蔽膜之耐溼性及耐撓曲性適當地提高。 The non-conductive filler is preferably at least one selected from the group consisting of silicon oxide and organic phosphate. Among them, silicon oxide is preferred. The non-conductive filler composed of these materials can appropriately improve the moisture resistance and deflection resistance of the electromagnetic wave shielding film.
非導電性填料為氧化矽時,可為膠質氧化矽、氣相式氧化矽、藉由溼式法合成的溼式氧化矽、藉由乾式法合成的乾式氧化矽、多孔性氧化矽、無孔性氧化矽、疏水性氧化矽、實施過各種表面處理的親水性氧化矽。When the non-conductive filler is silicon oxide, it can be colloidal silicon oxide, fumed silicon oxide, wet silicon oxide synthesized by wet method, dry silicon oxide synthesized by dry method, porous silicon oxide, non-porous silicon oxide Hydrophobic silicon oxide, hydrophobic silicon oxide, and hydrophilic silicon oxide with various surface treatments.
疏水性氧化矽例如可藉由將以乾式法合成的非晶質氧化矽或以溼式法合成的非晶質氧化矽,對存在於該等非晶質氧化矽表面之矽烷醇基實施用以賦予疏水性的表面處理來製造。 關於所述表面處理,例如可舉下述處理:以石蠟、棕櫚蠟、醯胺蠟、聚乙烯蠟等蠟類被覆非晶質氧化矽表面的處理。獲得的疏水性氧化矽由於非晶質氧化矽表面之矽烷醇基業經蠟層被覆,故顯示疏水性。又,亦可舉下述處理:對非晶質氧化矽添加四甲基矽烷、乙烯基三氯矽烷、乙烯基三甲氧基矽烷、含環氧基矽烷、二甲基二氯矽烷等有機矽化合物或含胺基的有機化合物等,並利用水解等進行改質的處理。藉此獲得的疏水性氧化矽係非晶質氧化矽表面之矽烷醇基已與有機矽化合物等進行化學反應者,於其表面具有烷基等疏水性基。 Hydrophobic silicon oxide can be used, for example, by applying dry-synthesized amorphous silicon oxide or wet-synthesized amorphous silicon oxide to the silanol groups present on the surface of the amorphous silicon oxide. Manufactured with hydrophobic surface treatment. The surface treatment includes, for example, a treatment in which the surface of amorphous silicon oxide is coated with waxes such as paraffin wax, carnauba wax, amide wax, and polyethylene wax. The obtained hydrophobic silicon oxide exhibits hydrophobicity because the silanol base on the surface of the amorphous silicon oxide is covered with a wax layer. Moreover, the following treatment can also be mentioned: adding an organosilicon compound such as tetramethylsilane, vinyltrichlorosilane, vinyltrimethoxysilane, epoxy-containing silane, and dimethyldichlorosilane to amorphous silicon oxide Or amine group-containing organic compounds, etc., and are modified by hydrolysis or the like. The obtained hydrophobic silicon oxide-based amorphous silicon oxide surface has a hydrophobic group such as an alkyl group on the surface of the silanol group that has been chemically reacted with an organosilicon compound or the like.
關於所述疏水性氧化矽,可列舉:AEROSIL R972、AEROSIL R974、AEROSIL R976、AEROSIL R104、AEROSIL R106、AEROSIL R202、AEROSIL R805、AEROSIL R812、AEROSIL R812S、AEROSIL R816、AEROSIL R7200、AEROSIL R8200、AEROSIL R9200(以上為日本AEROSIL(股)製)、SYLOPHOBIC 200、SYLOPHOBIC 704、SYLOPHOBIC 505、SYLOPHOBIC 603(以上為富士SILYSIA化學股份有限公司製)等。As the hydrophobic silica, AEROSIL R972, AEROSIL R974, AEROSIL R976, AEROSIL R104, AEROSIL R106, AEROSIL R202, AEROSIL R805, AEROSIL R812, AEROSIL R812S, AEROSIL R816, AEROSIL R7200, AEROSIL R8200, AEROSIL R9200 ( The above are Japan AEROSIL (stock), SYLOPHOBIC 200, SYLOPHOBIC 704, SYLOPHOBIC 505, SYLOPHOBIC 603 (the above are made by Fuji Silysia Chemical Co., Ltd.), etc.
親水性氧化矽例如可藉由將以乾式法合成的非晶質氧化矽或以溼式法合成的非晶質氧化矽,不對存在於該等非晶質氧化矽表面之矽烷醇基進行化學改質來製造。 關於所述親水性氧化矽,可列舉:AEROSIL 90、AEROSIL 130、AEROSIL 150、AEROSIL 200、AEROSIL 300、AEROSIL 380、AEROSIL OX50、AEROSIL EG50、AEROSIL TT600(以上為日本AEROSIL(股)製)、SYLYSIA 250、SYLYSIA 350、SYLYSIA 450、SYLYSIA 550、SYLYSIA 740(以上為富士SILYSIA化學股份有限公司製)等。 Hydrophilic silicon oxide can be used, for example, by combining dry-synthesized amorphous silicon oxide or wet-synthesized amorphous silicon oxide without chemically modifying the silanol groups present on the surface of the amorphous silicon oxide. quality to manufacture. The hydrophilic silicon oxides include: AEROSIL 90, AEROSIL 130, AEROSIL 150, AEROSIL 200, AEROSIL 300, AEROSIL 380, AEROSIL OX50, AEROSIL EG50, AEROSIL TT600 (the above are manufactured by Japan AEROSIL Co., Ltd.), SYLYSIA 250 , SYLYSIA 350, SYLYSIA 450, SYLYSIA 550, SYLYSIA 740 (the above are manufactured by Fuji Silysia Chemical Co., Ltd.), etc.
非導電性填料為有機磷酸鹽時,可列舉多磷酸鹽及次磷酸金屬鹽(phosphinic acid metal salt)等。關於次磷酸金屬鹽,可使用鋁鹽、鈉鹽、鉀鹽、鎂鹽及鈣鹽等,其中又以鋁鹽為佳。關於多磷酸鹽,可使用三聚氰胺鹽、甲胺鹽、乙胺鹽、二乙胺鹽、三乙胺鹽、乙二胺鹽、哌𠯤鹽、吡啶鹽、三𠯤鹽及銨鹽等,其中又以三聚氰胺鹽為佳。When the non-conductive filler is an organic phosphate, a polyphosphate, a phosphinic acid metal salt, or the like can be mentioned. As metal hypophosphite salts, aluminum salts, sodium salts, potassium salts, magnesium salts, calcium salts, etc. can be used, and among them, aluminum salts are preferred. As for polyphosphates, melamine salts, methylamine salts, ethylamine salts, diethylamine salts, triethylamine salts, ethylenediamine salts, piperine salts, pyridinium salts, trisamine salts, ammonium salts, etc. can be used, among which Preferably, melamine salts are used.
保護層20之厚度並無特別限定,但宜為1~100μm、較佳為2~50μm。
若保護層之厚度小於1μm,因為保護層過薄,故容易破損。
若保護層之厚度大於100μm,則電磁波屏蔽膜整體會變厚、變得不易處理。又,保護層之柔軟性降低。
The thickness of the
保護層20宜進而具有環氧系樹脂。
若保護層20包含環氧系樹脂,在藉由熱壓將電磁波屏蔽膜10配置於印刷配線板時,可抑制保護層所含之胺基甲酸酯系樹脂流動。
The
環氧系樹脂之酸值宜為100~500g/eq、較佳為150~450g/eq。The acid value of the epoxy resin is preferably 100 to 500 g/eq, preferably 150 to 450 g/eq.
於電磁波屏蔽膜10中,保護層20中之胺基甲酸酯系樹脂與環氧系樹脂之重量比宜為胺基甲酸酯系樹脂/環氧系樹脂=4~49、較佳為10~40。
若上述重量比小於4,則環氧系樹脂變過多、保護層容易變硬。其結果,保護層之柔軟性會降低、耐撓曲性會降低。
若上述重量比大於49,則環氧系樹脂會變少、保護層會變得柔軟,不易獲得包含環氧系樹脂的效果。
In the electromagnetic
於保護層20中視需要亦可包含硬化促進劑、賦黏劑、抗氧化劑、顏料、染料、塑化劑、紫外線吸收劑、消泡劑、調平劑、填充材、阻燃劑、黏度調節劑、抗結塊劑等。The
(金屬層)
電磁波屏蔽膜10之金屬層30只要可屏蔽電磁波即可,並無特別限定,宜由選自於由銅層、銀層及鋁層所構成群組中之至少1種構成。
此等金屬層之導電性高,可適當屏蔽電磁波。
(metal layer)
The
金屬層30之厚度並無特別限定,但宜為0.01~10μm。
金屬層之厚度小於0.01μm時,難以獲得充分的屏蔽效果。
若金屬層之厚度大於10μm,則電磁波屏蔽膜變得難以撓曲。
The thickness of the
於電磁波屏蔽膜10中,金屬層30亦可具有貫通孔。
電磁波屏蔽膜10將被熱壓於印刷配線板。此時,在導電性接著劑層40與金屬層30之間可能會產生揮發成分。
在金屬層30未形成有貫通孔時,會有該揮發成分因熱而膨脹、致使金屬層30與導電性接著劑層40剝離之情形。然而,若於金屬層30形成有貫通孔,因為揮發成分可通過貫通孔,故可防止金屬層30與導電性接著劑層40剝離。
In the electromagnetic
(導電性接著劑層)
導電性接著劑層40包含接著性樹脂組成物與金屬粒子。
又,導電性接著劑層40亦可進一步包含阻燃劑、阻燃助劑、硬化促進劑、賦黏劑、抗氧化劑、顏料、染料、塑化劑、紫外線吸收劑、消泡劑、調平劑、填充材、黏度調節劑等。
(Conductive Adhesive Layer)
The conductive
關於導電性接著劑層40所含之接著性樹脂組成物之材料並無特別限定,可使用:苯乙烯系樹脂組成物、乙酸乙烯酯系樹脂組成物、聚酯系樹脂組成物、聚乙烯系樹脂組成物、聚丙烯系樹脂組成物、醯亞胺系樹脂組成物、醯胺系樹脂組成物、丙烯酸系樹脂組成物等熱塑性樹脂組成物;或酚系樹脂組成物、環氧系樹脂組成物、胺基甲酸酯系樹脂組成物、三聚氰胺系樹脂組成物、醇酸系樹脂組成物等熱硬化性樹脂組成物等。
其等之中,以聚酯系樹脂組成物為佳。
接著性樹脂組成物之材料可為其等中之單獨一種,亦可為二種以上之組合。
The material of the adhesive resin composition contained in the conductive
關於導電性接著劑層40所含之金屬粒子可列舉:銀、銅、鎳、鋁、於銅實施鍍銀之銀包銅等。
此等金屬粒子因為導電性優異,故可對導電性接著劑層40適當地賦予導電性。
此等金屬粒子可單獨一種包含於導電性接著劑層40中,亦可複數種包含於導電性接著劑層40中。
The metal particles contained in the conductive
金屬粒子之尺寸並無特別限定,但平均粒徑宜為0.5~20μm。The size of the metal particles is not particularly limited, but the average particle size is preferably 0.5 to 20 μm.
導電性接著劑層40所含之金屬粒子之重量比率宜為2~60wt%、較佳為10~40wt%。
若金屬粒子之重量比率小於2wt%,電磁波屏蔽膜之屏蔽性容易降低。
若金屬粒子之重量比率大於60wt%,則導電性接著劑層會變脆,電磁波屏蔽膜變得容易破損。
又,若金屬粒子之重量比率為40wt%以下,導電性接著劑層可獲得各向異性導電性。
The weight ratio of the metal particles contained in the conductive
電磁波屏蔽膜10中,導電性接著劑層40可具有各向同性導電性,亦可具有各向異性導電性。
若導電性接著劑層40具有各向異性導電性,於配置有電磁波屏蔽膜10之印刷配線板中,高頻信號之輸電特性變得良好。
In the electromagnetic
導電性接著劑層40之厚度並無特別限定,可視需要適當設定,但宜為0.5~30.0μm。
若導電性接著劑層之厚度小於0.5μm,不易獲得良好的導電性。
若導電性接著劑層之厚度大於30.0μm,則電磁波屏蔽膜整體之厚度變厚、變得不易處理。
The thickness of the conductive
於電磁波屏蔽膜10中,亦可於保護層20與金屬層30之間形成有錨固塗佈層。
關於錨固塗佈層之材料,可列舉:胺基甲酸酯樹脂、丙烯酸樹脂、以胺基甲酸酯樹脂為外殼且以丙烯酸樹脂為核心之核殼型複合樹脂、環氧樹脂、醯亞胺樹脂、醯胺樹脂、三聚氰胺樹脂、酚樹脂、脲甲醛樹脂、使聚異氰酸酯與苯酚等封端劑反應而獲得之封端異氰酸酯、聚乙烯醇、聚乙烯吡咯啶酮等。
In the electromagnetic
雖然上述電磁波屏蔽膜10具備導電性接著劑層40,但本發明之電磁波屏蔽膜亦可將導電性接著劑層改為具備非導電性之接著劑層。Although the electromagnetic
接著,針對將電磁波屏蔽膜10配置於印刷配線板的屏蔽印刷配線板之製造方法進行說明。Next, the manufacturing method of the shielding printed wiring board which arrange|positions the electromagnetic
(印刷配線板準備步驟)
圖2A為剖面圖,其係示意性顯示使用本發明之電磁波屏蔽膜的屏蔽印刷配線板之製造方法中之印刷配線板準備步驟。
於本步驟中,準備印刷配線板50,其係由基材膜51、配置於基材膜51上且包含接地電路52a之印刷電路52、及覆蓋印刷電路52之覆蓋膜53構成。再者,於保護膜53形成有使接地電路52a露出之開口部53a。
(Printed wiring board preparation steps)
2A is a cross-sectional view schematically showing a printed wiring board preparation step in a method of manufacturing a shielded printed wiring board using the electromagnetic wave shielding film of the present invention.
In this step, the printed
(電磁波屏蔽膜配置步驟)
圖2B為剖面圖,其係示意性顯示使用本發明之電磁波屏蔽膜的屏蔽印刷配線板之製造方法中之電磁波屏蔽膜配置步驟。
於本步驟中,係以使電磁波屏蔽膜10之導電性接著劑層40與印刷配線板50之覆蓋膜53接觸之方式,將電磁波屏蔽膜10配置於印刷配線板50。
(Electromagnetic wave shielding film arrangement steps)
2B is a cross-sectional view schematically showing a step of disposing the electromagnetic wave shielding film in the manufacturing method of the shielded printed wiring board using the electromagnetic wave shielding film of the present invention.
In this step, the electromagnetic
(熱壓步驟)
圖2C為剖面圖,其係示意性顯示使用本發明之電磁波屏蔽膜的屏蔽印刷配線板之製造方法中之熱壓步驟。
接著,朝箭頭方向對配置有電磁波屏蔽膜10之印刷配線板50進行熱壓,藉此將電磁波屏蔽膜10熱壓於印刷配線板50。
(Heat pressing step)
2C is a cross-sectional view schematically showing a heat pressing step in a method of manufacturing a shielded printed wiring board using the electromagnetic wave shielding film of the present invention.
Next, the printed
由於保護層20包含平均粒徑為10μm以下之非導電性填料,且相對於保護層20之全體重量,非導電性填料之重量比率為10~40重量%,故進行熱壓時可防止保護層20所含之胺基甲酸酯系樹脂流動而使保護層之一部分變薄。因此,保護層20不易產生局部較薄的部位。其結果,電磁波屏蔽膜之耐溼性及耐撓曲性變得良好。Since the
又,藉由熱壓,導電性接著劑層40會填埋開口部53a,使導電性接著劑層40與接地電路52a接觸。
因此,金屬層30與接地電路52a電性連接,電磁波屏蔽性提高。
In addition, by hot pressing, the conductive
關於熱壓之條件並無特別限定,可舉例如150~200℃、2~5MPa、1~60min之條件。The conditions of the hot pressing are not particularly limited, and examples thereof include conditions of 150 to 200° C., 2 to 5 MPa, and 1 to 60 minutes.
圖2D為剖面圖,其係示意性顯示使用本發明之電磁波屏蔽膜所製造的屏蔽印刷配線板之一例。
經過以上步驟,如圖2D所示,可製造使用電磁波屏蔽膜10之屏蔽印刷配線板1。
2D is a cross-sectional view schematically showing an example of a shielded printed wiring board manufactured using the electromagnetic wave shielding film of the present invention.
After the above steps, as shown in FIG. 2D, the shielded printed wiring board 1 using the electromagnetic
接著,說明本發明之電磁波屏蔽膜之另一態樣。
圖3係示意性顯示本發明之電磁波屏蔽膜之另一例的剖面圖。
圖3所示之電磁波屏蔽膜110係依序積層有保護層120與導電性接著劑層140之電磁波屏蔽膜。
於電磁波屏蔽膜110中,導電性接著劑層140具有各向同性導電性,並作為遮蔽電磁波之屏蔽層而起作用。
Next, another aspect of the electromagnetic wave shielding film of the present invention will be described.
FIG. 3 is a cross-sectional view schematically showing another example of the electromagnetic wave shielding film of the present invention.
The electromagnetic
於電磁波屏蔽膜110中,保護層120之較佳態樣與上述電磁波屏蔽膜10之保護層120相同。In the electromagnetic
以下,就電磁波屏蔽膜110中之導電性接著劑層140之較佳態樣進行說明。Hereinafter, a preferred aspect of the conductive
導電性接著劑層140包含接著性樹脂組成物與金屬粒子。
又,導電性接著劑層140亦可進一步包含阻燃劑、阻燃助劑、硬化促進劑、賦黏劑、抗氧化劑、顏料、染料、塑化劑、紫外線吸收劑、消泡劑、調平劑、填充材、黏度調節劑等。
The conductive
關於導電性接著劑層140所含之接著性樹脂組成物之材料並無特別限定,可使用:苯乙烯系樹脂組成物、乙酸乙烯酯系樹脂組成物、聚酯系樹脂組成物、聚乙烯系樹脂組成物、聚丙烯系樹脂組成物、醯亞胺系樹脂組成物、醯胺系樹脂組成物、丙烯酸系樹脂組成物等熱塑性樹脂組成物;或酚系樹脂組成物、環氧系樹脂組成物、胺基甲酸酯系樹脂組成物、三聚氰胺系樹脂組成物、醇酸系樹脂組成物等熱硬化性樹脂組成物等。
其等之中,以聚酯系樹脂組成物為佳。
接著性樹脂組成物之材料可為其等中之單獨一種,亦可為二種以上之組合。
The material of the adhesive resin composition contained in the conductive
關於導電性接著劑層140所含之金屬粒子可列舉:銀、銅、鎳、鋁、於銅實施鍍銀之銀包銅等。
此等金屬粒子因為導電性優異,故可對導電性接著劑層140適當地賦予導電性。
此等金屬粒子可單獨一種包含於導電性接著劑層140中,亦可複數種包含於導電性接著劑層140中。
The metal particles contained in the conductive
金屬粒子之尺寸並無特別限定,但平均粒徑宜為0.5~20μm。The size of the metal particles is not particularly limited, but the average particle size is preferably 0.5 to 20 μm.
導電性接著劑層140所含之金屬粒子之重量比率宜為40重量%以上、較佳為40~60重量%。
若金屬粒子之重量比率為40重量%以上,導電性接著劑層140可獲得各向同性導電性。
The weight ratio of the metal particles contained in the conductive
[實施例] 以下,顯示更具體地說明本發明之實施例,但本發明並不限定於此等實施例。 [Example] Hereinafter, although the Example which demonstrates this invention more concretely is shown, this invention is not limited to these Examples.
(實施例1) 將酸值為3300g/eq、Tg為40℃的胺基甲酸酯樹脂A(製造商:東洋紡公司製、重量平均分子量:200,000)、環氧樹脂(酸值:170g/eq)、及作為非導電性填料之氧化矽粒子(平均粒徑:2μm)按表1所示之比率進行混練,製成保護層用組成物。 再者,表1中之組成之數值表示重量%。 (Example 1) Urethane resin A (manufacturer: Toyobo Co., Ltd., weight average molecular weight: 200,000), epoxy resin (acid value: 170 g/eq), and non- The silicon oxide particles (average particle diameter: 2 μm) of the conductive filler were kneaded at the ratio shown in Table 1 to prepare a composition for a protective layer. In addition, the numerical value of the composition in Table 1 represents weight %.
接著,準備於單面實施過剝離處理之聚對苯二甲酸乙二酯膜作為轉印膜。 然後,於轉印膜之剝離處理面塗佈保護層用組成物,使用電烤箱於100℃下加熱2分鐘,製成厚度5μm的保護層。 之後,藉由無電鍍覆於保護層上形成2μm銅層。該銅層成為屏蔽層。 Next, as a transfer film, a polyethylene terephthalate film having been subjected to peeling treatment on one side was prepared. Then, the composition for protective layers was coated on the peeling treatment surface of the transfer film, and heated at 100° C. for 2 minutes using an electric oven to prepare a protective layer with a thickness of 5 μm. After that, a 2 μm copper layer was formed on the protective layer by electroless plating. This copper layer becomes the shielding layer.
接著,將作為接著性樹脂組成物之熱塑性聚酯樹脂40重量份、作為導電性填料之銀包銅粉(平均粒徑:12μm)60重量份進行混練,製成導電性接著劑。 然後,於銅層上塗佈製成的導電性接著劑,使用電烤箱於100℃下加熱2分鐘,製成厚度20μm之導電性接著劑層。 經過上述步驟,製作實施例1之電磁波屏蔽膜。 Next, 40 parts by weight of thermoplastic polyester resin as an adhesive resin composition and 60 parts by weight of silver-coated copper powder (average particle size: 12 μm) as a conductive filler were kneaded to prepare a conductive adhesive. Then, the prepared conductive adhesive was coated on the copper layer, and heated at 100° C. for 2 minutes using an electric oven to prepare a conductive adhesive layer with a thickness of 20 μm. After the above steps, the electromagnetic wave shielding film of Example 1 was fabricated.
(實施例2~3)及(比較例1~8) 除了使用表1所示種類之胺基甲酸酯樹脂作為用於保護層之胺基甲酸酯系樹脂,並如表1所示改變保護層之組成外,以與實施例1相同方式製作出實施例2~3及比較例1~8之電磁波屏蔽膜。 (Examples 2 to 3) and (Comparative Examples 1 to 8) Produced in the same manner as in Example 1 except that the urethane resin of the type shown in Table 1 was used as the urethane resin for the protective layer, and the composition of the protective layer was changed as shown in Table 1. The electromagnetic wave shielding films of Examples 2 to 3 and Comparative Examples 1 to 8.
再者,實施例及比較例中之胺基甲酸酯樹脂B~E之酸值、重量平均分子量、Tg如表1所示。In addition, the acid value, weight average molecular weight, and Tg of the urethane resins B to E in Examples and Comparative Examples are shown in Table 1.
[表1] [Table 1]
(電阻值試驗)
圖4A及圖4B係顯示電阻值試驗之方法的示意圖。
首先,如圖4A所示,準備試驗基板55,該試驗基板55係於基材膜51形成金屬墊52b且配置有覆蓋膜53者,該覆蓋膜53具有使金屬墊52b露出的2個開口部53a。又,開口部53a之直徑設為1mm。
接著,將各實施例及各比較例之電磁波屏蔽膜10以使導電性接著劑層40與覆蓋膜53接觸之方式配置於試驗基板55。
然後,使用加壓機於170℃、3MPa、30min之條件下進行熱壓,藉此製成圖4B所示之試驗用屏蔽基板2。
接著,如圖4B所示,將電阻測定器R連接於2個金屬墊52b,測定剛製造後的試驗用屏蔽基板2之導電性接著劑層40之電阻值(厚度方向的電阻值),將測定結果顯示於表1。
又,對試驗用屏蔽基板2於260℃、1min之條件下施加5次熱衝撃後,以相同方法測定試驗用屏蔽基板2之導電性接著劑層40之電阻值(厚度方向的電阻值),將測定結果顯示於表1。
又,將試驗用屏蔽基板2於85℃、85%RH之高溫高溼環境下放置500hr後,以相同方法測定試驗用屏蔽基板2之導電性接著劑層40之電阻值(厚度方向的電阻值),將測定結果顯示於表1。
(resistance value test)
4A and 4B are schematic diagrams showing the method of resistance value testing.
First, as shown in FIG. 4A , a
(耐撓曲性試驗) 圖5係示意性顯示耐撓曲性試驗的圖。 利用以下方法評價電磁波屏蔽膜之耐撓曲性。 (flexural resistance test) FIG. 5 is a diagram schematically showing a flexural resistance test. The deflection resistance of the electromagnetic wave shielding film was evaluated by the following method.
<操作(i)>
首先,準備試驗用印刷配線基板60,其係於由25μm聚醯亞胺膜構成之基材構件上形成3條銅箔圖案(銅箔厚度12μm、線寬8mm)、再於該等銅箔圖案上積層有由絕緣性接著劑層及聚醯亞胺膜構成之覆蓋膜(絕緣膜厚度37.5μm)者,前述3條銅箔圖案係形成了模擬配線基板之電路。
<Operation (i)>
First, a printed
<操作(ii)>
接著,將各實施例及各比較例之電磁波屏蔽膜10與試驗用印刷配線基板60,以電磁波屏蔽膜10之接著劑層與印刷配線基板60之覆蓋膜相接之方式,使用加壓機以溫度:170℃、時間:30分鐘、壓力:2~3MPa之條件進行接著,製成積層體61。
<Operation (ii)>
Next, the electromagnetic
<操作(iii)>
接著,製作治具,其係於厚度2mm之烤板71上以平行之方式固定有2片厚度0.4mm之矩形玻璃環氧樹脂板72者。然後,將積層體61以使電磁波屏蔽膜10在外側之方式進行彎折,並以此狀態保持於治具中的2片玻璃環氧樹脂板72之間。
<Operation (iii)>
Next, a jig is produced, which is fixed on a
<操作(iv)>
然後,於以彎折狀態保持之積層體61上載置厚度2mm之烤板73及1kg之標準砝碼74,保持10秒。
<Operation (iv)>
Then, the
<操作(v)>
保持10秒後,去除烤板73及標準砝碼74,將積層體61放置1分鐘。
<Operation (v)>
After holding for 10 seconds, the
反覆10次上述操作(iv)~(v)之動作,以目視觀察各實施例及各比較例之電磁波屏蔽膜之保護層,評價耐撓曲性。 評價基準如下。將結果顯示於表1。 ◎:未觀察到裂紋 ○:觀察到裂紋,但保護層下之層(銅層)未從裂紋部位露出 ╳:觀察到裂紋,且保護層下之層(銅層)從裂紋部位露出 The operations of the above-mentioned operations (iv) to (v) were repeated 10 times, and the protective layers of the electromagnetic wave shielding films of the respective Examples and Comparative Examples were visually observed to evaluate the deflection resistance. The evaluation criteria are as follows. The results are shown in Table 1. ⊚: No crack was observed ○: Cracks are observed, but the layer (copper layer) under the protective layer is not exposed from the cracked portion ╳: Cracks are observed, and the layer (copper layer) under the protective layer is exposed from the cracked portion
(黏著試驗) 圖6係示意性顯示黏著試驗的圖。 利用以下方法評價保護層之耐黏著性。 (adhesion test) Figure 6 is a diagram schematically showing the adhesion test. The blocking resistance of the protective layer was evaluated by the following method.
首先,於厚度50μm、縱向尺寸40mm、橫向尺寸40mm之聚對苯二甲酸乙二酯膜80之上表面,塗佈各實施例及各比較例之保護層用組成物,使用電烤箱於100℃下加熱2分鐘,製作厚度5μm的保護層,藉此製成黏著試驗用試驗體81。First, on the upper surface of the
接著,如圖6所示,將二片黏著試驗用試驗體81以保護層20位於下方、聚對苯二甲酸乙二酯膜80位於上方之方式重疊於鋁板91上,再於黏著試驗用試驗體81上配置鋁板92。
然後,從鋁板91及鋁板92之上下施加2kg壓力,於常溫下維持此狀態3日。
之後,取出黏著試驗用試驗體81,觀察是否發生黏著,評價耐黏著性。
評價基準如下。將結果顯示於表1。
○:黏著試驗用試驗體81容易剝離,未發生黏著。
╳:一個黏著試驗用試驗體81之保護層20與另一個黏著試驗用試驗體81之聚對苯二甲酸乙二酯膜80黏住,各黏著試驗用試驗體81不易剝離,發生黏著。
Next, as shown in FIG. 6 , the two
如表1所示,發現若保護層所含之胺基甲酸酯樹脂之酸值為2000~4000g/eq,則耐撓曲性為良好。 又,發現若保護層所含之胺基甲酸酯樹脂之Tg為0℃以上,不易發生黏著。 又,發現若於保護層中包含平均粒徑為10μm以下之非導電性填料,且所含非導電性填料相對於保護層之全體重量為10~40重量%,則耐溼性及耐撓曲性提高。 As shown in Table 1, it was found that when the acid value of the urethane resin contained in the protective layer was 2000 to 4000 g/eq, the deflection resistance was favorable. In addition, it was found that when the Tg of the urethane resin contained in the protective layer is 0°C or higher, it is difficult to cause sticking. In addition, it was found that when the protective layer contains a non-conductive filler with an average particle diameter of 10 μm or less, and the non-conductive filler is contained in an amount of 10 to 40% by weight with respect to the total weight of the protective layer, moisture resistance and deflection resistance are improved. Sexual improvement.
1:屏蔽印刷配線板
2:試驗用屏蔽基板
10,110:電磁波屏蔽膜
20,120:保護層
30:金屬層
40,140:導電性接著劑層
50:印刷配線板
51:基材膜
52:印刷電路
52a:接地電路
52b:金屬墊
53:覆蓋膜
53a:開口部
55:試驗基板
60:試驗用印刷配線基板
61:積層體
71,73:烤板
72:玻璃環氧樹脂板
74:標準砝碼
80:聚對苯二甲酸乙二酯膜
81:黏著試驗用試驗體
91,92:鋁板
R:電阻測定器
1: Shielded printed wiring board
2: Shielding substrate for test
10,110: Electromagnetic wave shielding film
20,120: Protective layer
30: Metal layer
40,140: Conductive Adhesive Layer
50: Printed wiring board
51: substrate film
52: Printed
圖1係示意性顯示本發明之電磁波屏蔽膜之一例的剖面圖。 圖2A為剖面圖,其係示意性顯示使用本發明之電磁波屏蔽膜的屏蔽印刷配線板之製造方法中之印刷配線板準備步驟。 圖2B為剖面圖,其係示意性顯示使用本發明之電磁波屏蔽膜的屏蔽印刷配線板之製造方法中之電磁波屏蔽膜配置步驟。 圖2C為剖面圖,其係示意性顯示使用本發明之電磁波屏蔽膜的屏蔽印刷配線板之製造方法中之熱壓步驟。 圖2D為剖面圖,其係示意性顯示使用本發明之電磁波屏蔽膜所製造的屏蔽印刷配線板之一例。 圖3係示意性顯示本發明之電磁波屏蔽膜之另一例的剖面圖。 圖4A係顯示電阻值試驗之方法的示意圖。 圖4B係顯示電阻值試驗之方法的示意圖。 圖5係示意性顯示耐撓曲性試驗的圖。 圖6係示意性顯示黏著試驗的圖。 FIG. 1 is a cross-sectional view schematically showing an example of the electromagnetic wave shielding film of the present invention. 2A is a cross-sectional view schematically showing a printed wiring board preparation step in a method of manufacturing a shielded printed wiring board using the electromagnetic wave shielding film of the present invention. 2B is a cross-sectional view schematically showing a step of disposing the electromagnetic wave shielding film in the manufacturing method of the shielded printed wiring board using the electromagnetic wave shielding film of the present invention. 2C is a cross-sectional view schematically showing a heat pressing step in a method of manufacturing a shielded printed wiring board using the electromagnetic wave shielding film of the present invention. 2D is a cross-sectional view schematically showing an example of a shielded printed wiring board manufactured using the electromagnetic wave shielding film of the present invention. FIG. 3 is a cross-sectional view schematically showing another example of the electromagnetic wave shielding film of the present invention. FIG. 4A is a schematic diagram showing the method of the resistance value test. FIG. 4B is a schematic diagram showing the method of the resistance value test. FIG. 5 is a diagram schematically showing a flexural resistance test. Figure 6 is a diagram schematically showing the adhesion test.
10:電磁波屏蔽膜 10: Electromagnetic wave shielding film
20:保護層 20: Protective layer
30:金屬層 30: Metal layer
40:導電性接著劑層 40: Conductive adhesive layer
Claims (8)
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KR (1) | KR102558231B1 (en) |
CN (1) | CN115486215B (en) |
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CN101683022B (en) * | 2007-05-09 | 2012-07-04 | 东丽株式会社 | Conductive board, electromagnetic shielding board for plasma display and method for manufacturing conductive board |
JP2015129226A (en) * | 2014-01-08 | 2015-07-16 | 日東電工株式会社 | Film type adhesive, dicing tape with film type adhesive, method for manufacturing semiconductor device, and semiconductor device |
CN107079611A (en) * | 2014-12-05 | 2017-08-18 | 拓自达电线株式会社 | Electromagnetic shielding film |
JP2018039959A (en) * | 2016-09-09 | 2018-03-15 | タツタ電線株式会社 | Conductive adhesive composition |
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WO2019012590A1 (en) * | 2017-07-10 | 2019-01-17 | タツタ電線株式会社 | Electromagnetic wave shield film, and shielded printed wiring board equipped with same |
JP2019046871A (en) | 2017-08-30 | 2019-03-22 | タツタ電線株式会社 | Electromagnetic wave shield film, shield printed wiring board, and method for manufacturing shield printed wiring board |
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TW201943330A (en) | 2018-03-29 | 2019-11-01 | 日商拓自達電線股份有限公司 | Resin composition for protective layer of electromagnetic wave-shielding film, electromagnetic wave-shielding film, and method for producing electromagnetic wave-shielding film |
JP7070061B2 (en) * | 2018-05-11 | 2022-05-18 | Dic株式会社 | Conductive adhesive composition |
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