TW202035167A - 兩面覆金屬積層體及其製造方法、絕緣薄膜及電子電路基板 - Google Patents
兩面覆金屬積層體及其製造方法、絕緣薄膜及電子電路基板 Download PDFInfo
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- TW202035167A TW202035167A TW109102702A TW109102702A TW202035167A TW 202035167 A TW202035167 A TW 202035167A TW 109102702 A TW109102702 A TW 109102702A TW 109102702 A TW109102702 A TW 109102702A TW 202035167 A TW202035167 A TW 202035167A
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- metal
- insulating film
- clad laminate
- heating
- liquid crystal
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Abstract
本發明提供一種兩面覆金屬積層體之製造方法,其具有:在一對環狀帶(3)間連續供給絕緣薄膜與2片金屬箔之供給步驟、在環狀帶(3)間以金屬箔夾住絕緣薄膜的狀態下以特定的條件加熱加壓而作成積層體之加熱加壓步驟、及將積層體冷卻之冷卻步驟;其中絕緣薄膜之厚度為10~500 μm、面配向度為30%以上、MD方向的平均線膨脹係數為-40~0 ppm/K、TD方向的平均線膨脹係數為0~120 ppm/K。又,提供採用該製造方法而得之兩面覆金屬積層體、用於該製造方法的絕緣薄膜、使用該兩面覆金屬積層體的電子電路基板。
Description
本發明係關於一種兩面覆金屬積層體及其製造方法、一種該製造方法所使用的絕緣薄膜及一種使用兩面覆金屬積層體的電子電路基板。
熱塑性液晶聚合物(LCP)由於耐熱性、機械強度、電氣特性等優良,因此在電氣・電子領域及車用零件領域中被廣泛利用作為電子電路基板等的絕緣薄膜。
熱塑性液晶聚合物薄膜由於具有直鏈狀剛性分子鏈規則排列的結構,因此容易產生各向異性。於是,藉由T字模等將熱塑性液晶聚合物擠壓成形而得到的薄膜通常在平面內容易於擠出方向上產生高度的分子配向。其結果,於擠出方向及其垂直方向上,加熱時的線膨脹係數產生差異,而有外觀變形的可能性。
因此,使用熱塑性液晶聚合物薄膜作為絕緣薄膜來製造兩面覆金屬積層體時,採取以下方法:於進行降低熱塑性液晶聚合物薄膜具有的各向異性之處理後,與金屬箔積層而一體化。
關於使用熱塑性液晶聚合物薄膜來製造兩面覆金屬積層體的方法,已揭示多種製造技術。例如,專利文獻1已揭示一種製造撓性印刷電路板用積層板的方法,其係在一對環狀帶間連續供給由液晶聚合物構成的絕緣薄膜與金屬箔,並進行熱壓成形而製造撓性印刷電路板用積層板的方法。在此方法中,係規定金屬箔的表面粗糙度與熱壓成形時的加熱溫度。又,專利文獻2已揭示一種製造撓性積層板的方法,其係在一對環狀帶間連續供給由液晶聚合物構成的絕緣薄膜與金屬箔,並進行熱壓接合而製造撓性積層板的方法。在此方法中,係規定撓性積層板的最高溫度以及從環狀帶運出時的出口溫度。
[先前技術文獻]
[專利文獻]
[專利文獻1]日本特許第5411656號公報
[專利文獻2]日本特開2016-129949號公報
[發明欲解決之課題]
然而,專利文獻1所揭示的製造方法,其熱壓成形時的加熱溫度雖然在液晶聚合物的熔點以上,但是若使用各向異性強的熱塑性液晶聚合物薄膜,則有各向異性殘留的可能性。若各向異性殘留在薄膜上,則有積層板產生翹曲、變形,或是在鑽孔加工時產生毛邊、裂痕的可能性。又,專利文獻2所揭示的製造方法,由於熱壓接合時的加熱溫度小於液晶聚合物的熔點,因此與專利文獻1的方法一樣,若使用各向異性強的熱塑性液晶聚合物薄膜,則有各向異性殘留的可能性。
本發明係鑑於如以上的情況而完成者。亦即,本發明的課題為提供一種兩面覆金屬積層體及其製造方法,該兩面覆金屬積層體能夠使用由熱塑性液晶聚合物構成的各向異性強的絕緣薄膜,且兩面覆金屬積層體的熱塑性液晶聚合物層的面配向度小,加熱時的尺寸變化的各向異性亦小。又,提供一種適用於前述製造方法的絕緣薄膜及一種使用前述兩面覆金屬積層體的電子電路基板。
[用以解決課題之手段]
本發明人等發現藉由在一對環狀帶間以2片金屬箔夾住由熱塑性液晶聚合物構成的絕緣薄膜的狀態下,選擇特定的溫度、壓力及時間來進行加熱加壓,而令人驚訝地,絕緣薄膜的各向異性較為容易得到改善。又,發現即使不進行以往進行之預先用於減少熱塑性液晶聚合物薄膜具有的各向異性的處理,也能夠使用各向異性強的絕緣薄膜來得到各向異性減少的兩面覆金屬積層體。本發明係基於這樣的知識見解而能夠完成者。亦即,本發明具有如下述的構成。
(1)本發明之兩面覆金屬積層體之製造方法係一種具有將由熱塑性液晶聚合物構成的絕緣薄膜以2片金屬箔夾住之構成之兩面覆金屬積層體之製造方法,其特徵在於其具有:在一對環狀帶間連續供給前述絕緣薄膜與2片的前述金屬箔之供給步驟、在前述環狀帶間以2片的前述金屬箔夾住前述絕緣薄膜的狀態下進行加熱加壓而作成積層體之加熱加壓步驟、及將前述積層體冷卻之冷卻步驟;前述絕緣薄膜之厚度為10~500 μm、面配向度為30%以上、MD方向的平均線膨脹係數為-40~0 ppm/K、TD方向的平均線膨脹係數為0~120 ppm/K,將前述熱塑性液晶聚合物的熔點定為Tm(°C)時,前述加熱加壓步驟中的加熱溫度T(°C)滿足(Tm+20)<T≦(Tm+70),前述加熱加壓步驟中的壓力為0.5~10 MPa,前述加熱加壓步驟中的加熱加壓時間為30~360秒。
(2)本發明之兩面覆金屬積層體之製造方法能夠使所得到的兩面覆金屬積層體之去除金屬箔後的熱塑性液晶聚合物層,成為面配向度小於30%、MD方向的平均線膨脹係數為0~40 ppm/K、TD方向的平均線膨脹係數為0~40 ppm/K。
(3)本發明之兩面覆金屬積層體之製造方法較佳係前述金屬箔為銅箔。
(4)本發明之絕緣薄膜係一種用於兩面覆金屬積層體之製造方法的絕緣薄膜,該方法具有:在一對環狀帶間連續供給絕緣薄膜與2片金屬箔之供給步驟、在前述環狀帶間以2片的前述金屬箔夾住前述絕緣薄膜的狀態下進行加熱加壓而作成積層體之加熱加壓步驟、及將前述積層體冷卻之冷卻步驟;其特徵在於其係由熱塑性液晶聚合物構成,且厚度為10~500 μm、面配向度為30%以上、MD方向的平均線膨脹係數為-40~0 ppm/K、TD方向的平均線膨脹係數為0~120 ppm/K。
(5)本發明之兩面覆金屬積層體係一種兩面覆金屬積層體,其具有將由熱塑性液晶聚合物構成的絕緣薄膜以2片金屬箔夾住之構成,其特徵在於其係以前述(1)或前述(2)中記載之兩面覆金屬積層體之製造方法進行製造,且去除金屬箔後的熱塑性液晶聚合物層,係面配向度小於30%、MD方向的平均線膨脹係數為0~40 ppm/K、TD方向的平均線膨脹係數為0~40 ppm/K。
(6)本發明之兩面覆金屬積層體較佳係前述金屬箔為銅箔。
(7)本發明之電子電路基板係使用前述(5)或前述(6)記載之兩面覆金屬積層體。
[發明之效果]
本發明之兩面覆金屬積層體之製造方法能夠使用由熱塑性液晶聚合物構成的各向異性強的絕緣薄膜,而且能夠得到兩面覆金屬積層體的熱塑性液晶聚合物層的面配向度小且加熱時的尺寸變化的各向異性也小的兩面覆金屬積層體。
以下,詳細地說明本發明的實施形態。惟本發明的技術範圍並未受限於作為以下說明的具體例的實施形態。
(熱塑性液晶聚合物)
熱塑性液晶聚合物係指熔融時具有液晶狀態或者光學雙折射性質的熱塑性聚合物。作為熱塑性液晶聚合物,有在溶液狀態下展現液晶性的溶致性(lyotropic)液晶聚合物以及在熔融時展現液晶性的熱致性(thermotropic)液晶聚合物。熱塑性液晶聚合物依熱變形溫度而分類為I型、II型、III型,其可為任一型。
就熱塑性液晶聚合物而言,例如可列舉熱塑性芳香族液晶聚酯、或對其導入醯胺鍵的熱塑性芳香族液晶聚酯醯胺等。熱塑性液晶聚合物亦可為對芳香族聚酯或芳香族聚酯醯胺進一步導入醯亞胺鍵、碳酸酯鍵、碳二亞胺(carbodiimide)鍵或三聚異氰酸酯鍵等源自異氰酸酯的鍵結等之聚合物。
熱塑性液晶聚合物的熔點,以DSC法,較佳為220~400°C,更佳為260~380°C。熱塑性液晶聚合物的熔點若在前述範圍內,則能夠得到擠壓成形性優異且耐熱性優異的薄膜。
熱塑性液晶聚合物的分子具有剛性的棒狀結構,其係在分子與成形流動方向對齊的狀態下固化,因此其成形品的尺寸穩定性優異,但另一面則具有容易展現各向異性的特性。
(絕緣薄膜)
絕緣薄膜係將熱塑性液晶聚合物成形所製造的薄膜。從熱塑性液晶聚合物製造絕緣薄膜的成形方法並沒有特別的限定,可列舉充氣法或T字模法等擠壓成形法、鑄製法、壓延法等公知的成形方法。在此等之中,T字模法最為通用。然而,在以T字模法進行薄膜成形的情況下,通過T字模時於MD方向上施加剪力(shear),熱塑性液晶聚合物的分子進行配向而容易在MD方向上展現各向異性。此處,MD方向係指薄膜面內的成形流動方向(Machine Direction),TD方向係指與薄膜面內的MD方向垂直的方向。
絕緣薄膜的厚度為10~500 μm,較佳為15~400 μm。絕緣薄膜的厚度若在前述範圍內,則在環狀帶間以2片金屬箔夾住絕緣薄膜的狀態下進行加熱加壓時,能夠藉由聚合物分子的流動來減少各向異性。
如前所述,藉由T字模法從熱塑性液晶聚合物將薄膜成形時,在MD方向上施加剪力,薄膜進行配向而有在MD方向上展現各向異性的情形。以T字模法成形的薄膜大多係面配向度成為30%以上、MD方向的平均線膨脹係數成為-40~0 ppm/K、TD方向的平均線膨脹係數成為0~120 ppm/K。在本實施形態之兩面覆金屬積層體之製造方法中,如後所述,能夠使用面配向度為30%以上、MD方向的平均線膨脹係數為-40~0 ppm/K且TD方向的平均線膨脹係數為0~120 ppm/K之各向異性強的絕緣薄膜作為絕緣薄膜。
面配向度係以如下方的方式求得。首先,使用廣角X射線繞射裝置,從垂直於薄膜面的方向往薄膜面照射X射線,得到2維繞射影像。接著,藉由將所得到的2維繞射影像中的圓周方向的強度進行作圖,得到強度曲線。在所得到的強度曲線中,將測定強度的基底部分的積分值設為B、將從所測定的峰值部分減去基底部分之部分的積分值設為A時,以下式計算出面配向度。
面配向度(%)={A/(A+B)}×100
平均線膨脹係數係藉由依據JIS K7197的TMA法進行測定。
[兩面覆金屬積層體的製造裝置]
圖1為本實施形態之兩面覆金屬積層體的製造裝置20的示意截面圖。兩面覆金屬積層體的製造裝置20為液壓式雙帶加壓方式的製造裝置,其能夠在以2片金屬箔夾住絕緣薄膜的狀態下連續地加熱加壓而作成積層體,兩面覆金屬積層體的生產性優異。
製造裝置20設置有絕緣薄膜的捲11、以及積層於絕緣薄膜的兩面的2片金屬箔的捲12。從捲11拉出的絕緣薄膜係以夾在從捲12拉出的2片金屬箔中的狀態下供給至2台輸送裝置14之間。
製造裝置20於上方及下方具有2台輸送裝置14。輸送裝置14係藉由2個環狀帶輥1、2驅動環狀帶3。輸送裝置14在其內部具有內藏有加熱器塊5及冷卻塊6的加壓塊4。2台輸送裝置14可將被投入至其之間的絕緣薄膜及金屬箔以指定的壓力連續地加壓並加熱,之後進行冷卻。環狀帶3的材質並沒有特別的限定,能夠使用金屬、樹脂、橡膠等,但從耐熱性、及熱膨脹少之點來看,以金屬為佳。
加壓塊4具有能夠將絕緣薄膜及金屬箔以指定的壓力加壓的能力。加壓塊4的內部填充有油。加壓塊4內的油能夠進行加壓。若以油壓進行加壓,則能夠對薄膜面內均一地施加壓力,因此不易引起外觀不良。加熱器塊5具有將絕緣薄膜及金屬箔加熱至熱塑性液晶聚合物的熔點以上的指定溫度的功能。冷卻塊6具有以指定的冷卻速度將絕緣薄膜及金屬箔冷卻至熱塑性液晶聚合物的固化溫度以下的溫度的功能。
製造裝置20具備用於輸送絕緣薄膜及金屬箔的多個導輥7。又,製造裝置20能夠將藉由2台輸送裝置14所一體化之包含絕緣薄膜與金屬箔的積層體作為捲13而捲取。
作為金屬箔,能夠使用銅、銅合金、鋁、鋁合金、鐵、鐵合金等金屬箔。用於電子電路基板等的用途時,係以銅箔為佳。
金屬箔的厚度較佳為5~100 μm,更佳為7~50 μm。金屬箔的厚度若超過100 μm,則因熱傳導的關係,而有製造裝置20中的熱塑性液晶聚合物的加熱熔融不充分的可能性。又,為了提升與絕緣薄膜的密著性,金屬箔係以施加表面處理為佳。就表面處理方法而言,有粗化處理、偶合劑等的塗布、酸・鹼處理、氧化處理等方法。這些表面處理方法可適當地使用公知的方法。
[兩面覆金屬積層體之製造方法]
本實施形態之兩面覆金屬積層體之製造方法具有:(1)在一對環狀帶間連續供給絕緣薄膜與2片金屬箔之供給步驟、(2)在環狀帶間以2片金屬箔夾住絕緣薄膜的狀態下進行加熱加壓而作成積層體之加熱加壓步驟、(3)將積層體冷卻之冷卻步驟、以及(4)捲取積層體之捲取步驟。圖1中顯示此等的4個步驟。兩面覆金屬積層體之製造方法的各步驟能夠以分批方式實施,但從生產性之點來看,較佳為以連續方式實施者。以下針對各步驟進行説明。
(供給步驟)
供給步驟係在製造裝置20的2台輸送裝置14所具有的一對環狀帶3間連續供給絕緣薄膜與2片金屬箔之步驟。絕緣薄膜係從捲11供給,積層於絕緣薄膜的兩面的2片金屬箔係從捲12供給。
(加熱加壓步驟)
加熱加壓步驟係在環狀帶3間以2片金屬箔夾住絕緣薄膜的狀態下進行加熱加壓而作成積層體之步驟。
本發明人等使用具有強的各向異性的絕緣薄膜,針對其各向異性的減少方法進行探討。使用製造裝置20,對在環狀帶3間將2片金屬箔與絕緣薄膜加熱加壓時的溫度、壓力及時間進行各種探討。其結果闡明:(1)若加熱至熱塑性液晶聚合物的熔點以上的特定溫度,則熱塑性液晶聚合物熔融,在熔融狀態下聚合物分子間的纏結係解開而熔融黏度急遽下降,熔融聚合物的流動性大幅增加;(2)藉由在特定壓力下於特定時間維持高流動狀態,而成形時形成的聚合物分子的配向被破壞,各向異性大幅減少;(3)進行冷卻而將絕緣薄膜的聚合物分子的配向被破壞的狀態固定化,藉此而金屬箔所夾住的熱塑性液晶聚合物層的面配向度變小,加熱時的尺寸變化的各向異性也變小。
將熱塑性液晶聚合物的熔點定為Tm(°C)時,加熱加壓步驟中的加熱溫度T(°C)必須滿足(Tm+20)<T≦(Tm+70)。加熱加壓步驟中的加熱溫度T(°C)更佳為(Tm+20)<T≦(Tm+60)。加熱加壓步驟中的加熱溫度若在前述式的範圍內,則能夠大幅降低熱塑性液晶聚合物的熔融黏度,使聚合物分子流動,解開分子間的纏結,能夠大幅減少各向異性。加熱溫度T(°C)若超過(Tm+70),則有會使熱塑性液晶聚合物劣化、或是熔融聚合物流動並從金屬箔突出而汙染裝置的疑慮。
加熱加壓步驟中的壓力為0.5~10 MPa,較佳為0.8~8 MPa。加熱加壓步驟中的壓力若在0.5 MPa以上,則絕緣薄膜與金屬箔充分地密著,因此能夠輕易地將熱傳導到絕緣薄膜上。又,加熱加壓步驟中的壓力若在10 MPa以下,則絕緣薄膜的厚度不會大幅減少,因此熔融聚合物流動而趨向各向異性的可能性低。
加熱加壓步驟中的加熱加壓時間為30~360秒,較佳為60~300秒。加熱加壓時間若在前述範圍內,則能夠確保將熱塑性液晶聚合物熔融而減少各向異性的時間。
在具有上述加熱加壓步驟的本實施形態之製造方法中,即使使用面配向度為30%以上、MD方向的平均線膨脹係數為-40~0 ppm/K、TD方向的平均線膨脹係數為0~120 ppm/K之各向異性強的絕緣薄膜,也能夠將兩面覆金屬積層體的熱塑性液晶聚合物層作成各向異性少的層。各向異性少的熱塑性液晶聚合物層係面配向度小於30%、MD方向的平均線膨脹係數為0~40 ppm/K、TD方向的平均線膨脹係數為0~40 ppm/K的聚合物層。
還有,只要為面配向度、MD方向的平均線膨脹係數及TD方向的平均線膨脹係數中任一項數值比前述各向異性強的絕緣薄膜更小的絕緣薄膜,則能夠用作本實施形態之兩面覆金屬積層體之製造方法的絕緣薄膜。又,絕緣薄膜的面配向度較佳為80%以下。
在本實施形態之製造方法中,如上所述,就大幅改善熱塑性液晶聚合物層的各向異性的理由而言,可認為如下。由於絕緣薄膜被夾在2片金屬箔中而在被拘束的狀態下進行加熱,因此即便熔融聚合物的熔融黏度大幅下降,熔融聚合物流動,其形態也不會大幅崩塌。於是推測這是因為在該狀態下,藉由薄膜內部的聚合物分子的微自由運動,而聚合物分子的配向變得隨機。
(冷卻步驟)
冷卻步驟係將加熱加壓步驟中得到的積層體冷卻至熱塑性液晶聚合物的固化溫度以下的溫度之步驟。將加熱加壓步驟中進行加熱加壓而減少各向異性的絕緣薄膜予以冷卻固化,而作成各向異性被緩和減少的熱塑性液晶聚合物層。在冷卻步驟中,較佳為以不使成形應變殘留的方式均等地冷卻。
(捲取步驟)
在製造裝置20中經過加熱加壓步驟及冷卻步驟所一體化的積層體,係作為兩面覆金屬積層體而被捲取成捲取捲13。又,亦可不進行捲取步驟,而切取作為指定長度的長方形的兩面覆金屬積層體來推疊。製造裝置20的線速度係調整成能夠確保30~360秒作為加熱加壓步驟中的加熱加壓時間的速度。
(兩面覆金屬積層體)
本實施形態之兩面覆金屬積層體係使用前述的兩面覆金屬積層體的製造裝置20並依據兩面覆金屬積層體之製造方法來製造。若根據本實施形態之兩面覆金屬積層體之製造方法,由於使用的絕緣薄膜的各向異性大幅改善,因此兩面覆金屬積層體的熱塑性液晶聚合物層的面配向度小,且其加熱時的尺寸變化的各向異性也小。亦即,所得到的兩面覆金屬積層體之去除金屬箔後的熱塑性液晶聚合物層,係面配向度小於30%、MD方向的平均線膨脹係數為0~40 ppm/K、TD方向的平均線膨脹係數為0~40 ppm/K。還有,熱塑性液晶聚合物層的面配向度較佳為20%以下。
兩面覆金屬積層體由於其熱塑性液晶聚合物層的各向異性減少,因此不易產生翹曲或變形,並且在鑽孔加工時不易產生毛邊或裂痕。
還有,當關注於去除金屬箔後的熱塑性液晶聚合物層的規定時,本實施形態之兩面覆金屬積層體亦能夠使用與本實施形態之兩面覆金屬積層體之製造方法不同的製造方法來製造。亦即亦能夠在進行以往之預先用於減少絕緣薄膜具有的各向異性的處理後,藉由在以2片金屬箔夾住該絕緣薄膜的狀態下進行加熱加壓而作成積層體之方法來製造。然而,本實施形態之兩面覆金屬積層體與前述利用以往的方法所製造的兩面覆金屬積層體之差異,目前難以藉由其結構或特性來直接特定。因此,為了表明本實施形態之兩面覆金屬積層體係與利用其他製造方法而得到的兩面覆金屬積層體不同,而將本實施形態之兩面覆金屬積層體以其製造方法來規定。
以往係預先進行用於減少熱塑性液晶聚合物薄膜具有的各向異性的處理,然而本實施形態之兩面覆金屬積層體之製造方法能夠省略這樣的步驟。亦即,本實施形態之兩面覆金屬積層體之製造方法為一種製造步驟較以往更簡略化且生產性更優異的製造方法。
作為兩面覆金屬積層體的用途,有電氣・電子領域或車用零件領域中的印刷電路板或模組基板等電子電路基板。又,作為其他的用途,有高耐熱性的撓性印刷基板、太陽能板基板、高頻用配線基板等。特別是具有對於將絕緣薄膜作為基板使用之撓性覆銅積層板的適合性。
[實施例]
以下使用實施例與比較例,進一步具體地說明本發明的實施形態,但本發明並不受限於此等例子。
實施例及比較例中使用的材料係如下所述。
(1)絕緣薄膜
絕緣薄膜1:將上野製藥公司製LCP樹脂(產品編號A-5000、熔點280°C、結晶溫度230°C)以單軸擠壓機與T字模進行製膜而得之厚度12 μm、100 μm、480 μm及600 μm的薄膜
絕緣薄膜2:將Polyplastics公司製LCP樹脂(產品編號C950RX、熔點320°C、結晶溫度275°C)以單軸擠壓機與T字模進行製膜而得之厚度100 μm的薄膜
絕緣薄膜3:將上野製藥公司製LCP樹脂(產品編號P-9000、熔點340°C、結晶溫度305°C)以單軸擠壓機與T字模進行製膜而得之厚度100 μm的薄膜
(2)金屬箔
銅箔:三井金屬礦業公司製、產品編號TQ-M7-VSP、厚度12 μm
(實施例1~8、比較例1~5)
使用圖1所示的製造裝置20,在使表1中記載的各種市售絕緣薄膜的兩面與2片金屬箔接觸的狀態下,以表1中記載的各種條件進行加熱加壓步驟而作成積層體,之後進行冷卻,製作兩面覆金屬積層體。
針對所得到的各兩面覆金屬積層體,將其浸於以三氯化鐵為主成分之基板製作用蝕刻液(Sunhayato公司製、蝕刻液 H-20L),溶解去除銅箔後,取出各熱塑性液晶聚合物層。所得到的熱塑性液晶聚合物層係在水洗後自然乾燥。
針對各熱塑性液晶聚合物層,依據下方記載的方法,評價面配向度、平均線膨脹係數。又,針對各兩面覆金屬積層體,評價銅箔剝離強度。將評價結果示於表1。
(面配向度)
使用全自動多目的X射線繞射裝置(Rigaku股份有限公司製、SmartLab(3kW)、2D-WAXS構成),進行X射線繞射,將測定條件示於下方。
X射線源:Cu密封管
施加電壓:40kV
電流:40mA
X射線輸出:1.6kW
偵檢器:多維像素偵檢器 HyPix-3000
X射線照射方向:垂直於薄膜面
累計時間:10分鐘
解析2θ角度範圍:10°~30°
2維繞射影像的圓周方向上將強度進行作圖時的取樣寬度:5°
從測定熱塑性液晶聚合物層時的強度減去作為對照之在未將同一層設置於裝置而測定時的強度,當作熱塑性液晶聚合物層的強度。
在所得到的2維繞射影像(圖2(a))中,藉由將強度對圓周方向的旋轉角度β進行作圖,得到圖2(b)的強度曲線。在圖2(b)中,將圓周360°分的測定強度的基底部分的積分值(基底面積)設為B、將從所測定的峰值部分減去基底部分之部分的積分值(峰值面積)設為A。此時,以下式計算出面配向度。
面配向度(%)={A/(A+B)}×100
面配向度小於30%時,判定為合格。
(平均線膨脹係數)
依據JIS K 7197,藉由TMA法,求出MD方向、TD方向在23~200°C的溫度範圍下的平均線膨脹係數(ppm/K)。膨脹時為+(正)的數值,收縮時為-(負)的數值。
(銅箔剝離強度)
依據JIS C 6481,測定將兩面覆金屬積層體的銅箔以寬度10mm、速度50mm/分鐘進行180°剝離時的剝離力(N/mm)。
銅箔剝離強度為0.5N/mm以上時,判定為良好。
[表1]
實施例1 | 實施例2 | 實施例3 | 實施例4 | 實施例5 | 實施例6 | 實施例7 | 實施例8 | 比較例1 | 比較例2 | 比較例3 | 比較例4 | 比較例5 | |||
絕緣薄膜 | 厚度 | µm | 12 | 100 | 100 | 100 | 100 | 480 | 100 | 100 | 100 | 100 | 100 | 600 | 100 |
面配向度 | % | 63.5 | 56.8 | 56.8 | 56.8 | 56.8 | 48.9 | 36.2 | 67.8 | 56.8 | 56.8 | 56.8 | 56.2 | 56.8 | |
平均 線膨脹係數 | MD | ppm/K | -20.8 | -19.1 | -19.1 | -19.1 | -19.1 | -15.6 | -17.8 | -19.8 | -19.1 | -19.1 | -19.1 | -5.6 | -19.1 |
TD | ppm/K | 90.7 | 81.5 | 81.5 | 81.5 | 81.5 | 75.4 | 80.7 | 86.5 | 81.5 | 81.5 | 81.5 | 76.4 | 81.5 | |
熔點 | °C | 280 | 280 | 280 | 280 | 280 | 280 | 320 | 340 | 280 | 280 | 280 | 280 | 280 | |
加熱加壓 條件 | 加熱溫度 | °C | 320 | 320 | 320 | 305 | 350 | 320 | 355 | 370 | 280 | 360 | 320 | 320 | 320 |
壓力 | MPa | 2 | 0.5 | 2 | 10 | 2 | 2 | 2 | 2 | 2 | 2 | 2 | 2 | 0.1 | |
加熱加壓時間 | 秒 | 30 | 180 | 180 | 360 | 180 | 360 | 180 | 180 | 180 | 30 | 15 | 360 | 180 | |
銅箔積層體的 熱塑性液晶 聚合物層 的特性 | 厚度 | µm | 11 | 100 | 100 | 100 | 98 | 475 | 100 | 100 | 100 | 74 | 100 | 500 | 100 |
面配向度 | % | 4.2 | 12.5 | 5.1 | 3.2 | 3.9 | 4.8 | 7.8 | 13.4 | 50.8 | 6.2 | 17.8 | 23.8 | 23.3 | |
平均 線膨脹係數 | MD | ppm/K | 6.7 | 28.9 | 17.8 | 19.8 | 17.6 | 24.3 | 21.8 | 23.7 | -4.5 | -0.9 | -3.8 | 1.2 | 38.5 |
TD | ppm/K | 32.1 | 30.7 | 22.1 | 21.6 | 23.5 | 29.8 | 26.3 | 22.9 | 67.3 | 37.8 | 57.9 | 45.7 | 44.1 | |
銅箔積層體 的特性 | 銅箔剝離強度 | N/mm | 0.7 | 0.7 | 0.8 | 0.8 | 0.7 | 0.8 | 0.7 | 0.8 | 0.5 | 0.8 | 0.7 | 0.8 | 0.6 |
從表1的評價結果來看,實施例1~8皆係面配向度小於30%、MD方向及TD方向的平均線膨脹係數為0~40 ppm/K,並且在銅箔剝離強度上亦具有良好的性能。另一方面,比較例1的加熱加壓步驟中的加熱溫度低,因此面配向度與平均線膨脹係數並不佳。比較例2的加熱加壓步驟中的加熱溫度過高,因此MD方向的平均線膨脹係數不佳。比較例3的加熱加壓步驟中的加熱加壓時間短,因此平均線膨脹係數不佳。比較例4的絕緣薄膜厚度過大,TD方向的平均線膨脹係數不佳。比較例5的加熱加壓步驟中的壓力小,因此TD方向的平均線膨脹係數不佳。
1,2:環狀帶輥
3:環狀帶
4:加壓塊
5:加熱器塊
6:冷卻塊
7:導輥
11,12,13:捲
14:輸送裝置
20:製造裝置
[圖1]為本實施形態之兩面覆金屬積層體的製造裝置的示意截面圖。
[圖2]圖2(a)為X射線繞射的2維繞射影像,圖2(b)為強度曲線。
1,2:環狀帶輥
3:環狀帶
4:加壓塊
5:加熱器塊
6:冷卻塊
7:導輥
11,12,13:捲
14:輸送裝置
20:製造裝置
Claims (7)
- 一種兩面覆金屬積層體之製造方法,其係具有將由熱塑性液晶聚合物構成的絕緣薄膜以2片金屬箔夾住之構成的兩面覆金屬積層體之製造方法,其特徵在於具有: 在一對環狀帶間連續供給該絕緣薄膜與2片的該金屬箔之供給步驟、 在該環狀帶間以2片的該金屬箔夾住該絕緣薄膜的狀態下進行加熱加壓而作成積層體之加熱加壓步驟、及 將該積層體冷卻之冷卻步驟;其中 該絕緣薄膜之厚度為10~500 μm、面配向度為30%以上、MD方向的平均線膨脹係數為-40~0 ppm/K、TD方向的平均線膨脹係數為0~120 ppm/K, 將該熱塑性液晶聚合物的熔點定為Tm(°C)時,該加熱加壓步驟中的加熱溫度T(°C)滿足(Tm+20)<T≦(Tm+70), 該加熱加壓步驟中的壓力為0.5~10 MPa, 該加熱加壓步驟中的加熱加壓時間為30~360秒。
- 如請求項1之兩面覆金屬積層體之製造方法,其中所得到的兩面覆金屬積層體之去除該金屬箔後的熱塑性液晶聚合物層,係面配向度小於30%、MD方向的平均線膨脹係數為0~40 ppm/K、TD方向的平均線膨脹係數為0~40 ppm/K。
- 如請求項1或2之兩面覆金屬積層體之製造方法,其中該金屬箔為銅箔。
- 一種絕緣薄膜,其係用於兩面覆金屬積層體之製造方法的絕緣薄膜,該方法具有:在一對環狀帶間連續供給絕緣薄膜與2片金屬箔之供給步驟、在該環狀帶間以2片的該金屬箔夾住該絕緣薄膜的狀態下進行加熱加壓而作成積層體之加熱加壓步驟、及將該積層體冷卻之冷卻步驟;其特徵在於 其係由熱塑性液晶聚合物構成,且 厚度為10~500 μm、面配向度為30%以上、MD方向的平均線膨脹係數為-40~0 ppm/K、TD方向的平均線膨脹係數為0~120 ppm/K。
- 一種兩面覆金屬積層體,其係具有將由熱塑性液晶聚合物構成的絕緣薄膜以2片金屬箔夾住之構成的兩面覆金屬積層體,其特徵在於 其係以如請求項1之兩面覆金屬積層體之製造方法進行製造,且 去除該金屬箔後的熱塑性液晶聚合物層,係面配向度小於30%、MD方向的平均線膨脹係數為0~40 ppm/K、TD方向的平均線膨脹係數為0~40 ppm/K。
- 如請求項5之兩面覆金屬積層體,其中該金屬箔為銅箔。
- 一種電子電路基板,其使用如請求項5或6之兩面覆金屬積層體。
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