TWI787249B - 覆金屬積層板、其製造方法、及電路基板 - Google Patents

覆金屬積層板、其製造方法、及電路基板 Download PDF

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TWI787249B
TWI787249B TW107111586A TW107111586A TWI787249B TW I787249 B TWI787249 B TW I787249B TW 107111586 A TW107111586 A TW 107111586A TW 107111586 A TW107111586 A TW 107111586A TW I787249 B TWI787249 B TW I787249B
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Taiwan
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metal
liquid crystal
crystal polymer
clad laminate
polymer film
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TW107111586A
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English (en)
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TW201841723A (zh
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中島崇裕
高橋健
新谷昌孝
小野寺稔
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日商可樂麗股份有限公司
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    • 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
    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • 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
    • B32B15/09—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 polyesters
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C65/00—Joining or sealing of preformed parts, e.g. welding of plastics materials; Apparatus therefor
    • B29C65/02—Joining or sealing of preformed parts, e.g. welding of plastics materials; Apparatus therefor by heating, with or without pressure
    • B29C65/18—Joining or sealing of preformed parts, e.g. welding of plastics materials; Apparatus therefor by heating, with or without pressure using heated tools
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
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    • B29C65/00—Joining or sealing of preformed parts, e.g. welding of plastics materials; Apparatus therefor
    • B29C65/02—Joining or sealing of preformed parts, e.g. welding of plastics materials; Apparatus therefor by heating, with or without pressure
    • B29C65/44—Joining a heated non plastics element to a plastics element
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    • B29C66/00—General aspects of processes or apparatus for joining preformed parts
    • B29C66/01—General aspects dealing with the joint area or with the area to be joined
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    • B29C66/10—Particular design of joint configurations particular design of the joint cross-sections
    • B29C66/11—Joint cross-sections comprising a single joint-segment, i.e. one of the parts to be joined comprising a single joint-segment in the joint cross-section
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    • B29C66/739—General aspects of processes or apparatus for joining preformed parts characterised by the composition, physical properties or the structure of the material of the parts to be joined; Joining with non-plastics material characterised by the intensive physical properties of the material of the parts to be joined, by the optical properties of the material of the parts to be joined, by the extensive physical properties of the parts to be joined, by the state of the material of the parts to be joined or by the material of the parts to be joined being a thermoplastic or a thermoset characterised by the material of the parts to be joined being a thermoplastic or a thermoset
    • B29C66/7392—General aspects of processes or apparatus for joining preformed parts characterised by the composition, physical properties or the structure of the material of the parts to be joined; Joining with non-plastics material characterised by the intensive physical properties of the material of the parts to be joined, by the optical properties of the material of the parts to be joined, by the extensive physical properties of the parts to be joined, by the state of the material of the parts to be joined or by the material of the parts to be joined being a thermoplastic or a thermoset characterised by the material of the parts to be joined being a thermoplastic or a thermoset characterised by the material of at least one of the parts being a thermoplastic
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    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
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    • B29C66/8126—General aspects of the pressing elements, i.e. the elements applying pressure on the parts to be joined in the area to be joined, e.g. the welding jaws or clamps characterised by the composition, by the structure, by the intensive physical properties or by the optical properties of the material constituting the pressing elements, e.g. constituting the welding jaws or clamps characterised by the intensive physical properties or by the optical properties of the material constituting the pressing elements, e.g. constituting the welding jaws or clamps
    • B29C66/81265—Surface properties, e.g. surface roughness or rugosity
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
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    • B29C66/80—General aspects of machine operations or constructions and parts thereof
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    • B29C66/814—General aspects of the pressing elements, i.e. the elements applying pressure on the parts to be joined in the area to be joined, e.g. the welding jaws or clamps characterised by the design of the pressing elements, e.g. of the welding jaws or clamps
    • B29C66/8145—General aspects of the pressing elements, i.e. the elements applying pressure on the parts to be joined in the area to be joined, e.g. the welding jaws or clamps characterised by the design of the pressing elements, e.g. of the welding jaws or clamps characterised by the constructional aspects of the pressing elements, e.g. of the welding jaws or clamps
    • B29C66/81457—General aspects of the pressing elements, i.e. the elements applying pressure on the parts to be joined in the area to be joined, e.g. the welding jaws or clamps characterised by the design of the pressing elements, e.g. of the welding jaws or clamps characterised by the constructional aspects of the pressing elements, e.g. of the welding jaws or clamps comprising a block or layer of deformable material, e.g. sponge, foam, rubber
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C66/00—General aspects of processes or apparatus for joining preformed parts
    • B29C66/80—General aspects of machine operations or constructions and parts thereof
    • B29C66/83—General aspects of machine operations or constructions and parts thereof characterised by the movement of the joining or pressing tools
    • B29C66/834—General aspects of machine operations or constructions and parts thereof characterised by the movement of the joining or pressing tools moving with the parts to be joined
    • B29C66/8341—Roller, cylinder or drum types; Band or belt types; Ball types
    • B29C66/83411—Roller, cylinder or drum types
    • B29C66/83413—Roller, cylinder or drum types cooperating rollers, cylinders or drums
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C66/00—General aspects of processes or apparatus for joining preformed parts
    • B29C66/80—General aspects of machine operations or constructions and parts thereof
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    • B29C66/834—General aspects of machine operations or constructions and parts thereof characterised by the movement of the joining or pressing tools moving with the parts to be joined
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    • B29C66/83411—Roller, cylinder or drum types
    • B29C66/83415—Roller, cylinder or drum types the contact angle between said rollers, cylinders or drums and said parts to be joined being a non-zero angle
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    • B32B37/0046—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by constructional aspects of the apparatus
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    • B32B37/06—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the heating method
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    • B32B37/14—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the properties of the layers
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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
    • H05K1/03—Use of materials for the substrate
    • 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
    • H05K3/00—Apparatus or processes for manufacturing printed circuits
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    • C—CHEMISTRY; METALLURGY
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    • C08G63/065—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from hydroxycarboxylic acids the hydroxy and carboxylic ester groups being bound to aromatic rings
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Abstract

提供一種覆金屬積層板及其製造方法。前述覆金屬積層板係至少積層了熱塑性液晶聚合物薄膜和金屬薄片的覆金屬積層板，在基於JIS Z 8741的光澤度(20°)方面，與和金屬薄片的接合面為相反側的熱塑性液晶聚合物薄膜側的表面為55以上。覆金屬積層板的製造方法至少具備：準備熱塑性液晶聚合物薄膜2和金屬薄片6的步驟；和將前述熱塑性液晶聚合物薄膜2和前述金屬薄片6導入一對加熱輥間，使它們壓接的步驟，且前述一對加熱輥係在與前述熱塑性液晶聚合物薄膜相接的側至少具備金屬彈性輥，前述金屬彈性輥係表面的十點平均粗糙度Rz為0.2以下。

Description

覆金屬積層板、其製造方法、及電路基板 [關聯申請案]
本案主張2017年4月7日於日本申請的日本特願2017-076564的優先權，藉由參照而引用其整體作為構成本申請案的一部分。
本發明係關於具備熱塑性液晶聚合物薄膜和金屬層的覆金屬積層板、及其製造方法。
以往，具備了熱塑性液晶聚合物薄膜的覆金屬積層板，由於在具有源自熱塑性液晶聚合物薄膜的優異的低吸濕性、耐熱性、耐藥品性及電氣性質的同時，也具有優異的尺寸穩定性，因此被使用作為柔性配線板或半導體安裝用的電路基板等的電路基板的材料。
特別是，在熱塑性液晶聚合物薄膜的單面積層了金屬薄片的單面覆金屬積層板，係以在未積層金屬薄片之側的薄膜面施加有電路形成加工的微帶電路等的形態被使用的需求升高。
例如，專利文獻1(日本特開2000-343610號公報)中記載了：將熱塑性液晶聚合物薄膜和金屬薄片進行輥壓接而成的單面覆金屬積層板。在此文獻中記載了：在將熱塑性液晶聚合物薄膜和金屬薄片積層而作成單面覆金屬積層板之際，使用一對耐熱橡膠輥和加熱金屬輥。
[先前技術文獻] [專利文獻]
專利文獻1：日本特開2000-343610號公報
專利文獻1中所得到的單面覆金屬積層板，係藉由使用耐熱橡膠輥作為加熱輥，而耐熱橡膠輥會追隨薄膜的凹凸，能夠實現熱塑性液晶聚合物薄膜和金屬薄片的均勻積層，其結果，能夠使熱塑性液晶聚合物薄膜和金屬薄片的接著強度或尺寸穩定性提升。
另一方面，如熱塑性液晶聚合物薄膜的高耐熱性薄膜的積層，在積層溫度達到260℃以上且使用橡膠輥的情況，會因長時間的積層而超過橡膠輥的耐熱性而過熱。若使用過熱的橡膠輥，則橡膠表面和薄膜的剝離性會降低，因此會使薄膜表面產生剝離傷。
另外，專利文獻1中所得到的單面覆金屬積層板，對於近年來需求升高的微帶電路等的緻密的電路圖案所被要求的傳輸特性，未必能夠充分應對。
本發明的目的，係在於提供熱塑性液晶聚合物薄膜表面的表面平滑性獲得改善的覆金屬積層板。
本發明的另外的目的，係在於提供能夠達成良好的傳輸特性的覆金屬積層板。
本發明的再另外的目的，係在於提供一種製造方法，其即使是在以卷對卷方式來連續地長時間製造的情況，也效率佳地製造熱塑性液晶聚合物薄膜表面的表面平滑性優異的覆金屬積層板。
本發明人等，為了達成上述目的而銳意檢討的結果，首先發現了：(1)在形成微帶或帶線路等的電路圖案之際，雖在單面覆金屬積層板的未積層金屬薄片的側的薄膜面形成有由蒸鍍或導電性糊等所產生的傳輸線路是有效的，但就謀求傳輸特性的進一步提升而言，單面覆金屬積層板的薄膜面的表面狀態會對傳輸特性等的電路特性產生重大影響。掌握了：(2)另一方面，在具有非金屬光澤的熱塑性液晶聚合物薄膜，若使用光澤度作為指標，便能夠準確地評價會對傳輸特性造成影響之薄膜整體的表面狀態，而這是以往藉由表面粗糙度的評價所難以實現的。而進一步銳意檢討的結果，發現：(3)在使用具有表面追隨性並且具有特定的表面粗糙度的金屬彈性輥(具有金屬表面的彈性輥)來取代熱塑性液晶聚合物薄膜會接觸的橡膠輥的情況，可將金屬彈性輥的平滑性轉印於熱塑性液晶聚合物薄膜表面，因此而可對液晶聚合物薄膜表面賦予特定的光澤度，及(4)在液晶聚合物薄膜表面具有這樣的光澤度的覆金屬積層板上，能夠形 成傳輸特性優異的電路圖案，進一步還發現：(5)在使用了這樣的金屬彈性輥的情況，即使是以卷對卷方式來連續地長時間製造，也藉由金屬彈性輥所帶來的表面耐久性、與薄膜的剝離性，而可有效地防止熱塑性液晶聚合物薄膜表面受到剝離傷，完成了本發明。
即，本發明係可以以下的態樣構成。
[態樣1]
一種覆金屬積層板，係至少積層了熱塑性液晶聚合物薄膜和金屬薄片的覆金屬積層板，在基於JIS Z 8741的光澤度(20°)方面，與和金屬薄片的接合面為相反側的熱塑性液晶聚合物薄膜表面為55以上(較佳為60以上，更佳為65以上)。
[態樣2]
態樣1所記載的覆金屬積層板，係熱塑性液晶聚合物薄膜的熔點為290℃以上(較佳為300℃~400℃，更佳為315℃~380℃)之覆金屬積層板。
[態樣3]
態樣1或2所記載的覆金屬積層板，係進一步具備形成在前述熱塑性液晶聚合物表面的金屬蒸鍍層之覆金屬積層板。
[態樣4]
態樣1至3中任一態樣所記載的覆金屬積層板，係在長邊方向上具有100m以上的長度之覆金屬積層板。
[態樣5]
一種覆金屬積層板的製造方法，係藉由卷對卷方式而在熱塑性液晶聚合物薄膜的表面接合了金屬薄片之覆金屬積層板的製造方法，其至少具備：準備熱塑性液晶聚合物薄膜和金屬薄片的步驟；和將前述熱塑性液晶聚合物薄膜和前述金屬薄片導入一對加熱輥間，使前述熱塑性液晶聚合物薄膜和前述金屬薄片在前述一對加熱輥間壓接的步驟，且前述一對加熱輥係在與前述熱塑性液晶聚合物薄膜相接的側至少具備金屬彈性輥，前述金屬彈性輥係表面的十點平均粗糙度Rz為0.2μm以下(例如，0.01~0.2μm)。
[態樣6]
於態樣5所記載的覆金屬積層板的製造方法中，前述一對加熱輥係以金屬輥和金屬彈性輥所構成之覆金屬積層板的製造方法。
[態樣7]
於態樣6所記載的覆金屬積層板的製造方法中，前述金屬輥係內部加熱式的金屬輥之覆金屬積層板的製造方法。
[態樣8]
於態樣5至7中任一態樣所記載的覆金屬積層板的製造方法中，前述金屬彈性輥係以輥狀的耐熱性橡膠、和形成在其周圍的金屬表面層所構成之覆金屬積層板的製造方法。
[態樣9]
於態樣8所記載的覆金屬積層板的製造方法中，前述耐熱性橡膠的硬度為70~100，且金屬表面層的厚度為100~1000μm之覆金屬積層板的製造方法。
[態樣10]
一種電路基板，係在如態樣1至4中任一態樣所記載的覆金屬積層板上形成有電路面。
[態樣11]
態樣10所記載的電路基板，其中前述電路圖案係形成在熱塑性液晶聚合物薄膜表面或金屬蒸鍍層表面上。
又，申請專利範圍及/或說明書及/或圖式中所公開的至少2個構成要素的任何組合也包含在本發明中。特別是申請專利範圍中所記載的2個以上請求項的任何組合也包含在本發明中。
本發明的覆金屬積層板由於熱塑性液晶聚合物薄膜表面極平滑，且具有特定的光澤度，因此能夠利用平滑的熱塑性液晶聚合物薄膜表面，而形成應對電路圖案的微間距化的緻密的電路圖案。而由這樣的覆金屬積層板，能夠製造顯示優異的傳輸特性的電路基板。
此外，本發明中，由於使用特定的金屬彈性輥，因此能夠以卷對卷方式來效率佳地製造前述覆金屬積層板。特別是，即使是進行長時間運轉的情況，也不僅能夠抑制熱塑性液晶聚合物薄膜的剝離傷的產生，而能夠在熱塑性液晶聚合物薄膜表面上維持特定的光澤度。
2:熱塑性液晶聚合物薄膜
6:金屬薄片
7:一對加熱輥
8:金屬彈性輥
9:加熱金屬輥
10:連續熱壓裝置
13:蒸鍍用加熱輥
19:單面覆金屬積層板
21、22:捲出輥
23:雙面覆金屬積層板
應可由參考了添附之圖式的以下的合適實施形態的說明而更清楚地理解本發明。然而，實施形態及圖式係僅用於圖示及說明者，不該被用於限定本發明的範圍。本發明的範圍係藉由添附的請求項而限定。在添附圖式中，複數個圖式中的同一元件符號係表示同一部分。
圖1係用以說明本發明的一實施形態的覆金屬積層板的製造步驟中所使用的連續熱壓裝置的概略圖。
圖2係用以說明本發明的一實施形態的覆金屬積層板的製造步驟中所使用的蒸鍍裝置的概略圖。
[實施發明之形態] [覆金屬積層板的製造方法]
本發明的一實施形態，係藉由卷對卷方式而在熱塑性液晶聚合物薄膜的表面接合了金屬薄片之覆金屬積層板的製造方法。前述製造方法至少包含：準備熱塑性液晶聚合物薄膜和金屬薄片的步驟；和將前述熱塑性液晶聚合物薄膜及前述金屬薄片導入一對加熱輥間，使前述熱塑性液晶聚合物薄膜及前述金屬薄片在加熱輥間壓接的步驟。
例如，於圖1顯示本發明的一實施形態的覆金屬積層板的製造步驟中所使用的連續熱壓裝置10。連續熱壓裝置10具有至少具備金屬彈性輥8的一對加熱輥 7。圖1中，一對加熱輥7係以金屬彈性輥8和加熱金屬輥9所構成，分別地，熱塑性液晶聚合物薄膜2從捲出輥22，而金屬薄片6從捲出輥21被捲出，被導入往一對加熱輥7。
在加熱輥7，係以在熱塑性液晶聚合物薄膜2接觸著金屬彈性輥8側，且金屬薄片6接觸著加熱金屬輥9側的狀態，熱塑性液晶聚合物薄膜2及金屬薄片6在既定的溫度及壓力下，按照既定的積層速度被熱壓接，而製作出單面覆金屬積層板19。所得到的單面覆金屬積層板具有以金屬薄片層、熱塑性液晶聚合物薄膜層的順序進行了積層的積層構造。
圖2中，顯示本發明的一實施形態的覆金屬積層板的製造步驟中所使用的蒸鍍裝置。如圖2所示，所得到的單面覆金屬積層板19係從捲出輥12，以金屬薄片6面接觸蒸鍍用加熱輥13的方式，藉由導引輥15被導入。換言之，液晶聚合物薄膜2係不接觸蒸鍍用加熱輥13，而以朝向蒸鍍用加熱輥13的外側的狀態被導入。接著，在被導入蒸鍍用加熱輥13的單面覆金屬積層板19，係對存在於蒸鍍用加熱輥13的外側的液晶聚合物薄膜2，形成金屬蒸鍍層(銅蒸鍍層)。金屬蒸鍍層，係藉由對配置在蒸鍍用加熱輥13的下方之具有蒸鍍源的坩堝17，照射來自電子槍18的電子束以加熱蒸鍍源來進行。形成有金屬蒸鍍層的雙面覆金屬積層板23，係藉由導引輥16來引導，而藉由捲取輥14來捲取。所得到的雙面覆金屬積層板，係具有以金屬薄片層、熱塑性液晶聚合物薄膜層、金屬蒸鍍層的順序進行了積層的積層構造。
(熱塑性液晶聚合物薄膜)
熱塑性液晶聚合物薄膜，係由能夠熔融成形的液晶聚合物所形成。此熱塑性液晶聚合物(有簡稱為液晶聚合物的情況)，若為能夠熔融成形的液晶聚合物的話，則對於其化學性構成並沒有特別的限定，但能舉出例如：熱塑性液晶聚酯、或在其中導入有醯胺鍵的熱塑性液晶聚酯醯胺等。
此外，熱塑性液晶聚合物可以是進一步在芳香族聚酯或芳香族聚酯醯胺中導入有醯亞胺鍵、碳酸酯鍵、碳二亞胺鍵或異三聚氰酸酯鍵等的源自異氰酸酯的鍵等的聚合物。
就本發明中所使用的熱塑性液晶聚合物的具體例而言，係能舉出由被分類成以下例示的(1)至(4)的化合物及其衍生物所導出的公知的熱塑性液晶聚酯及熱塑性液晶聚酯醯胺。但是，為了形成可形成光學上異向性的熔融相的聚合物，各種原料化合物的組合係有適當的範圍，這是當然的。
(1)芳香族或脂肪族二醇(代表例參照表1)
Figure 107111586-A0202-12-0010-1
(2)芳香族或脂肪族二羧酸(代表例參照表2)
Figure 107111586-A0202-12-0011-2
芳香族羥基羧酸(代表例參照表3)
Figure 107111586-A0202-12-0012-11
(4)芳香族二胺、芳香族羥基胺或芳香族胺基羧酸(代表例參照表4)
Figure 107111586-A0202-12-0012-4
作為可由這些原料化合物所得到的液晶聚合物的代表例，而能舉出具有表5及6中所示的構造單元的共聚物。
Figure 107111586-A0202-12-0013-5
Figure 107111586-A0202-12-0014-6
這些共聚物當中，較佳為至少包含對羥基苯甲酸及/或6-羥基-2-萘甲酸作為重複單元的聚合物，特 佳為(i)包含對羥基苯甲酸和6-羥基-2-萘甲酸的重複單元的聚合物、(ii)包含選自包含對羥基苯甲酸及6-羥基-2-萘甲酸的群組的至少一種芳香族羥基羧酸、和選自包含4,4’-二羥基聯苯及氫醌的群組的至少一種芳香族二醇、和選自包含對苯二甲酸、間苯二甲酸及2,6-萘二甲酸的群組的至少一種芳香族二羧酸之重複單元的聚合物。
例如，(i)的聚合物中，熱塑性液晶聚合物至少包含對羥基苯甲酸和6-羥基-2-萘甲酸的重複單元的情況，重複單元(A)的對羥基苯甲酸和重複單元(B)的6-羥基-2-萘甲酸的莫耳比(A)/(B)，係在液晶聚合物中理想為(A)/(B)=10/90~90/10左右，更佳為(A)/(B)=15/85~85/15左右(例如50/50~85/15)，進一步較佳為(A)/(B)=20/80~80/20(例如60/40~80/20)左右。
此外，(ii)的聚合物的情況，選自包含對羥基苯甲酸及6-羥基-2-萘甲酸的群組的至少一種芳香族羥基羧酸(C)、選自包含4,4’-二羥基聯苯及氫醌的群組的至少一種芳香族二醇(D)、和選自包含對苯二甲酸、間苯二甲酸及2,6-萘二甲酸的群組的至少一種芳香族二羧酸(E)之液晶聚合物中的各重複單元的莫耳比，係可為芳香族羥基羧酸(C)：前述芳香族二醇(D)：前述芳香族二羧酸(E)=(30~80)：(35~10)：(35~10)左右，更佳係可為(C)：(D)：(E)=(35~75)：(32.5~12.5)：(32.5~12.5)左右，進一步較佳係可為(C)：(D)：(E)=(40~70)：(30~15)：(30~15)左右。
此外，源自芳香族二醇的重複構造單元和源自芳香族二羧酸的重複構造單元的莫耳比，係較佳為(D)/(E)=95/100~100/95。若偏離此範圍的話，則會有聚合度不提高而機械強度降低的傾向。
又，本發明中所謂的熔融時的光學異向性，係指例如藉由將試料擺在加熱台，在氮氣環境下升溫加熱，並觀察試料的透射光而能夠認定。
作為熱塑性液晶聚合物之較佳者，為熔點(以下稱為M0p)為260~360℃的範圍者，進一步較佳為M0p為270~350℃者。又，M0p係藉由利用微差掃描熱卡計(島津製作所(股)的DSC)來測定出現主吸熱峰的溫度而求出。
對於前述熱塑性液晶聚合物，也可以在無損本發明的效果的範圍內添加聚對苯二甲酸乙二酯、改性聚對苯二甲酸乙二酯、聚烯烴、聚碳酸酯、聚芳香酯、聚醯胺、聚苯硫醚、聚醚醚酮、氟樹脂等熱塑性聚合物、各種添加劑，也可以因應需要而添加填充劑。
本發明中所使用的熱塑性液晶聚合物薄膜，係將熱塑性液晶聚合物進行擠出成形而可得到。只要能夠控制熱塑性液晶聚合物的堅硬的棒狀分子的方向，便能夠應用任意的擠出成形法，公知的T模法、層疊體拉伸法、吹脹法等在工業上是有利的。特別是在吹脹法或層疊體拉伸法，係不僅對薄膜的機械加工方向(以下，簡稱為MD方向)施加應力，還對與其正交的方向(以下，簡稱為TD方向)施加應力，可得到控制了MD方向和TD 方向上的介電特性的薄膜。
此外，也可以因應需要而進行公知或慣用的熱處理，調整熱塑性液晶聚合物薄膜的熔點及/或熱膨脹係數。熱處理條件係能夠因應目的而適宜設定，例如，也可以藉由在熱塑性液晶聚合物的熔點(M0p)-10℃以上(例如，M0p-10~M0p+30℃左右，較佳為M0p~M0p+20℃左右)加熱數小時，而使熱塑性液晶聚合物薄膜的熔點(Tm)上升。
熱塑性液晶聚合物薄膜的熔點(Tm)，係可於得到薄膜的期望的耐熱性及加工性的目的上，在200~400℃左右的範圍內選擇，較佳為250~360℃左右，更佳為260~340℃左右。
熱塑性液晶聚合物薄膜係較佳為等向性越高，等向性的指標的分子配向度SOR為0.8~1.4，較佳為0.9~1.3，更佳為1.0~1.2，特佳為1.0~1.1。
此處，分子配向度SOR(Segment Orientation Ratio)，係指給與關於構成分子之嵌段的分子配向的程度之指標，與以往的MOR(Molecular Orientation Ratio)不同，是考慮了物體的厚度的值。
在本發明中所使用的熱塑性液晶聚合物薄膜，從用於覆金屬積層板的觀點，其薄膜的膜厚較佳為在10~200μm的範圍內，更佳為15~150μm的範圍內。
(金屬薄片)
金屬薄片(以下，也有稱為金屬箔的情況)，係於覆 金屬積層板，被積層在熱塑性液晶聚合物薄膜的單面上。就本發明的金屬箔的材料而言，並沒有特別的限制，能舉出例如：銅、金、銀、鎳、鋁、及不銹鋼等，從導電性、處理性、及成本等觀點，較佳為使用銅箔或不銹鋼箔，特佳為使用銅箔。銅箔，若為可在電路基板中使用的銅箔的話，便沒有特別的限定，可以是壓延銅箔、電解銅箔中任一者。
此外，對於金屬箔，通常也可以施加對銅箔所施加的酸清洗等的化學性處理。此外，較佳為6~200μm的範圍內，更佳為9~40μm的範圍內，進一步較佳為10~20μm的範圍內。這是因為厚度過薄的情況，會有在覆金屬積層板的製造步驟中，於金屬箔產生皺摺等的變形之虞，而厚度過厚的情況，例如，在作為柔性配線板使用的情況，會有彎折性能降低的情況。
十點平均粗糙度Rz，也可以為例如0.1μm以上。特別是，若為2.0μm以下，則可以得到具有良好的高頻特性且緊貼強度優異的覆金屬積層板1。特別是從高頻特性和緊貼強度的均衡來看，更佳為0.1~1.5μm的範圍內，更佳為在0.3~1.1μm的範圍內。又，十點平均粗糙度Rz，係表示藉由後述實施例中所記載的方法所測定的值。
(熱塑性液晶聚合物薄膜及金屬薄片的熱壓接步驟)
本發明的製造方法具備熱塑性液晶聚合物薄膜及金屬薄片的熱壓接步驟，前述熱壓接步驟具備將熱塑性液 晶聚合物薄膜及金屬薄片導入一對加熱輥間，使兩者壓接的步驟。
一對加熱輥係至少在與熱塑性液晶聚合物薄膜相接的側具備金屬彈性輥。前述金屬彈性輥係具有金屬表面的彈性輥，前述金屬表面具有十點平均粗糙度Rz為0.2μm以下的極平滑表面。十點平均粗糙度Rz的下限值並沒有特別的限制，但例如，可以是0.01μm以上。
藉由使具有這樣的平滑性極高的表面的金屬彈性輥一邊與熱塑性液晶聚合物薄膜接觸，且一邊在一對加熱輥間使其壓接，而可以利用金屬彈性輥帶來的表面追隨性來抑制壓接不均，並同時使金屬表面所形成的特定的表面粗糙度的形狀反映至熱塑性液晶聚合物薄膜。其結果，可以對覆金屬積層板的熱塑性液晶聚合物薄膜表面賦予特定的光澤度。
特別是，在金屬彈性輥，肇因於金屬表面，而能夠提高輥表面溫度的散熱性，因此即使是持續長時間高溫的壓接的情況，也能夠抑制與熱塑性液晶聚合物薄膜的剝離性的惡化，因此能夠抑制在熱塑性液晶聚合物薄膜產生剝離皺摺等的剝離傷。
金屬彈性輥，若為表面具有特定的平滑金屬面的彈性輥的話，便沒有特別的限定，但從改良轉印性的觀點，較佳係也可為以輥狀的耐熱性橡膠、和形成在其周圍的金屬表面層所構成的金屬彈性輥(以下，稱為金屬橡膠輥)。
在金屬橡膠輥，從提高熱壓接時的壓接性的 觀點，橡膠輥部分可以是橡膠硬度70~100左右，較佳為橡膠硬度75~90左右。此處，橡膠硬度係由利用基於JIS K 6301的A型的彈簧式硬度試驗機的試驗所得到的值。硬度70以上的橡膠可藉由在矽酮系橡膠、氟系橡膠等的合成橡膠或天然橡膠中，添加硫化劑、鹼性物質等的硫化促進劑而得到。
金屬橡膠輥的金屬表面層的厚度，例如可以是100~1000μm，較佳為150~800μm，更佳為200~500μm。金屬表面層係由耐熱性及剛性優異的金屬(例如，鎳、不銹鋼等)所形成，且根據厚度或材質，而可以是圓筒狀的鍍覆層，也可以是將金屬板加工而作成圓筒狀者。
在一對加熱輥中，就與金屬薄片接觸的側的輥而言，係能夠根據加熱手段適宜選擇。就加熱處理手段而言，係能夠使用例如，熱風式的加熱處理爐、熱風循環乾燥機、熱輥、陶瓷加熱器、利用IR(遠紅外線)的熱處理裝置或併用此等的方法。
例如，加熱手段為來自外部的加熱手段的情況，可舉出：金屬輥、金屬彈性輥、耐熱性橡膠輥等。此外，加熱手段為內部加熱的情況，係較佳使用內部加熱式的金屬輥(加熱金屬輥)。
利用一對加熱輥的積層時，積層溫度能夠因應熱塑性液晶聚合物薄膜的熔點(Tm)來適宜設定，例如，可以是比熔點(Tm)低40℃的溫度至比熔點低5℃的溫度，即Tm-40℃~Tm-5℃的範圍內，亦可較佳為Tm-35℃~Tm-7℃的範圍內，更佳為Tm-30℃~Tm-10℃的範圍內。
利用一對加熱輥的積層時的壓力，從對熱塑性液晶聚合物薄膜賦予良好的光澤的觀點，作為面壓而可以例如為15~70kg/cm2左右，較佳為20~60kg/cm2左右，較佳為25~55kg/cm2左右。
此外，也可以因應需要，而對於藉由加熱輥所接合的熱塑性液晶聚合物薄膜及金屬薄片的單面覆金屬積層板，為了使兩者的層間接著性提高，而進一步進行熱處理。
就加熱處理手段而言，例如，能夠使用熱風式的加熱處理爐、熱風循環乾燥機、熱輥、陶瓷加熱器、利用IR(遠紅外線)的熱處理裝置或併用此等的方法。此外，從防止金屬薄片表面氧化的觀點，較佳為在使用經加熱的氮氣，在氧濃度為0.1%以下的惰性氣體環境下進行加熱處理。此外，熱處理可以在拉緊下或未拉緊下進行，較佳為在未拉緊下進行。
使熱處理溫度為Ta(℃)的情況，例如，熱處理溫度Ta(℃)可以是比熱塑性液晶聚合物薄膜的熔點Tm(℃)高的溫度(Tm<Ta)，較佳為相對於Tm(℃)而高1℃以上小於50℃的溫度(Tm+1≦Ta<Tm+50)，更佳為高1℃以上30℃以下的溫度(Tm+1≦Ta≦Tm+30)，進一步較佳為高2℃以上20℃以下的溫度(Tm+2≦Ta≦Tm+20)。
此外，在既定熱處理溫度Ta的熱處理時間(卷對卷 方式的情況，係任意一點通過熱處理溫度Ta的時間)較佳為1秒鐘~10分鐘，更佳為5秒鐘~8分鐘，進一步較佳為8秒鐘~5分鐘，特佳為8秒鐘~3分鐘。
(金屬蒸鍍步驟)
本發明的製造方法可以進一步具備：對單面覆金屬積層板的熱塑性液晶聚合物薄膜表面蒸鍍金屬的金屬蒸鍍步驟。從提高生產效率的觀點，關於金屬蒸鍍步驟，亦較佳為以卷對卷方式來進行。該情況，在蒸鍍用腔室內，以單面覆金屬積層板的金屬薄片面會接觸蒸鍍用加熱輥的方式，將單面覆金屬積層板導入蒸鍍用加熱輥，以蒸鍍用加熱輥狀，對熱塑性液晶聚合物薄膜面形成金屬蒸鍍層。
金屬蒸鍍，係藉由例如真空蒸鍍來進行，其加熱樣式，可舉出例如：電阻加熱、電子束加熱、高頻加熱等。例如，利用電阻加熱的情況，在真空蒸鍍裝置中的蒸鍍用腔室內，載置放入了蒸鍍源(例如，銅、金、銀、鎳、鋁、及不銹鋼等的金屬，較佳為銅，特佳為純度為99%以上的銅)的蒸鍍舟(藉由電阻體的鎢或鉬所形成者)。接著，將電流流入此蒸鍍用舟而進行加熱，能夠藉此而將金屬蒸鍍在熱塑性液晶聚合物薄膜的表面上，在單面覆金屬積層板中的熱塑性液晶聚合物薄膜的表面形成金屬蒸鍍層。
此外，利用電子束加熱的情況，在真空氣體環境中，將蒸鍍源放入坩堝，將電子束照射在坩堝以加 熱蒸鍍源，能夠藉此而將金屬蒸鍍在熱塑性液晶聚合物薄膜的表面上，在單面覆金屬積層板中的熱塑性液晶聚合物薄膜的表面形成金屬蒸鍍層，得到雙面覆金屬積層板。
此外，在金屬蒸鍍層的形成，從使熱塑性液晶聚合物薄膜和金屬蒸鍍層的緊貼力提升的觀點，蒸鍍用加熱輥的表面溫度係熱塑性液晶聚合物薄膜的熱變形溫度(Tdef)以上，較佳為熱塑性液晶聚合物薄膜的熔點(Tm)以下。例如，相對於熱塑性液晶聚合物薄膜的熔點(Tm)，而蒸鍍用加熱輥的表面溫度可以設為Tm-65℃~Tm-0.5℃，也可以較佳為Tm-55℃~Tm-1℃，更佳為Tm-45℃~Tm-1.5℃。若在熱塑性液晶聚合物薄膜的熱變形溫度以上進行蒸鍍，則蒸鍍粒子(在蒸鍍時飛散的粒子)會潛入到加熱而變軟的薄膜之中，因此也能對具有極平滑的表面的熱塑性液晶聚合物薄膜，形成具有良好的緊貼性的金屬蒸鍍層。
此外，在本實施形態中，從使卷對卷方式的生產性提高的觀點，較佳為將蒸鍍速度設定為1nm/s以上5nm/s以下。
此外，在本實施形態中，較佳為將卷對卷方式的熱塑性液晶聚合物薄膜2的移動速度設定為0.1m/分鐘~5m/分鐘。
[覆金屬積層板]
本發明的一態樣的覆金屬積層板，係至少積層了熱塑性液晶聚合物薄膜和金屬薄片的覆金屬積層板，在基於JIS Z 8741的光澤度(20°)方面，與和金屬薄片的接合面為相反側的熱塑性液晶聚合物薄膜表面為55以上的覆金屬積層板。此處，覆金屬積層板於具有前述光澤度的熱塑性液晶聚合物薄膜表面上具備金屬蒸鍍層的情況，可以藉由將金屬蒸鍍層進行蝕刻除去，來確認熱塑性液晶聚合物薄膜表面的光澤度。
前述覆金屬積層板，係源自特定的製造方法，而熱塑性液晶聚合物薄膜表面極平滑，因此其表面的基於JIS Z 8741-1997的光澤度(20°)成為55以上。熱塑性液晶聚合物薄膜表面的光澤度(20°)的上限沒有特別的限定，但通常亦可以是200以下。
本發明人等判明了：在具有非金屬光澤的熱塑性液晶聚合物薄膜，形成微間距等的緻密的電路圖案的情況，能夠藉由光澤度來準確地評價對傳輸特性造成影響的薄膜的表面狀態。即，推量如下：在熱塑性液晶聚合物薄膜，以在微細的範圍所測定的表面粗糙度並不能準確地評價薄膜表面的整體的平滑性，而另一方面，在巨觀的範圍所測定的光澤度則可以評價薄膜表面的整體的平滑性，因此能夠利用光澤度作為傳輸特性的評價基準。
熱塑性液晶聚合物薄膜表面的光澤度(20°)，較佳為60以上(例如，60~120)，更佳為65以上(例如，65~100)。光澤度(20°)表示藉由後述實施例中所記載的方法所測定的值。
此外，熱塑性液晶聚合物薄膜表面的光澤度(20°)，即使是進行以卷對卷方式的連續運轉的情況也很難降低，因此例如，以卷對卷方式來連續運轉了60分鐘的情況的熱塑性液晶聚合物薄膜表面的光澤度保持率，可以是95%以上(例如，95~105%)，較佳為97%以上(例如，97~103%)。又，連續運轉了60分鐘的情況的光澤度保持率，能夠藉由以下的公式來算出。
光澤度保持率=(連續運轉60分鐘後的光澤度/剛運轉後的光澤度)×100
此處，「剛運轉後的光澤度」係指在剛開始了藉由卷對卷方式之運轉後所得到的積層體樣品的熱塑性液晶聚合物薄膜表面的光澤度，「連續運轉60分鐘後的光澤度」係在連續運轉60分鐘後所得到的積層體樣品的熱塑性液晶聚合物薄膜表面的光澤度。
特別是，在本發明的較佳態樣，即使是以往以卷對卷方式的製造有困難的高熔點的熱塑性液晶聚合物薄膜，也可以不形成剝離傷地製成單面覆金屬積層板。這樣的高熔點薄膜的熔點，係可以為例如290℃以上(例如300℃~400℃)，亦可以較佳為315℃~380℃。
源自這樣的熱塑性液晶聚合物薄膜表面的平滑性，而具備在熱塑性液晶聚合物表面所形成的金屬蒸鍍層的雙面覆金屬積層板，可以顯示優異的傳輸特性。金屬蒸鍍層的厚度，可以為例如0.05μm~1.0μm，更佳為0.1μm~0.8μm。
本發明的覆金屬積層板係由於以卷對卷方式所形成，因此與用批量壓製方式所形成的覆金屬積層板不同，能夠效率佳地製造大尺寸的覆金屬積層板。例如，覆金屬積層板可以在長邊方向上具有100m以上的長度。
[電路基板]
本發明的一態樣的電路基板，係在前述覆金屬積層板上形成有電路面的電路基板。電路面能夠藉由公知的扣除法、加成法、半加成法等來形成。電路(金屬層)的厚度，可以為例如10~14μm，較佳為11~13μm。
電路面較佳為可以被形成在熱塑性液晶聚合物薄膜面或金屬蒸鍍層面。此外，可以對金屬蒸鍍層，進一步形成金屬鍍覆層，在前述金屬鍍覆面上形成電路面。
又，電路基板可以因應需要，藉由公知或慣用地進行的各種製造方法來形成貫穿孔等。該情況，電路基板中，可以形成有貫穿孔鍍覆層，形成有貫穿孔鍍覆層的狀態的電路(金屬層)的厚度，可以為例如20~40μm，較佳為25~35μm。
本發明的電路基板因傳輸特性特優，而能夠特別適合使用來作為高頻電路基板。高頻電路，不僅是包含僅傳輸高頻訊號的電路者，也包含在同一平面上併設將高頻訊號轉換為低頻訊號，將所生成的低頻訊號輸出至外部的傳輸路徑、或供給為了驅動應對高頻的零件所供給的電源用的傳輸路徑等傳輸並非高頻訊號的訊號的傳輸路徑的電路。
[實施例]
以下，藉由實施例更詳細地說明本發明，但本發明不受本實施例的任何限定。又，在以下的實施例及比較例中，藉由下述的方法而測定了各種物性。
[光澤度]
按照JIS Z 8741，將樣品放置在平坦的桌上，用光澤度計(Suga機械股份有限公司製的「GC-1」)測定了入射角20°的樣品光澤度(gloss度)。又，光澤度計的校正係使用附屬的校正板進行。
[傳輸特性]
介電率測定係在頻率10GHz藉由共振擾動法來實施。將應對40~67GHz的探針連接至微波Network Analyzer(Agilent公司製)，在40GHz及60GHz測定了傳輸損失。
[表面粗糙度]
表面粗糙度係按照JIS B0601：1994，使用接觸式表面粗糙度計(Mitutoyo(股)製，型式：SJ-201)而測定了十點平均粗糙度(Rz)。更詳細而言，十點平均粗糙度(Rz)係從粗糙度曲線，在其平均線的方向上抽樣基準長度，以μm表示了從最高到第5高的山頂(凸的頂點)的標高的平均值、和從最深到第5深的谷底(凹的底點)的標高的平均值的和。
[熔點]
熔點係使用微差掃描熱卡計，而觀察薄膜的熱行為來得到。即，將製作的薄膜以20℃/分鐘的速度升溫，而使其完全熔融後，將熔融物以50℃/分鐘的速度驟冷至50℃，將在再次以20℃/分鐘的速度升溫時出現的吸熱峰的位置當成是熱塑性液晶聚合物薄膜的熔點。
[熱變形溫度]
熱變形溫度係使用熱機械分析裝置，而觀察薄膜的熱行為來得到。即，將所製作的薄膜製成寬度5mm長度20mm的試驗片，以夾頭間距離15mm，以拉伸荷重0.01N、升溫速度10℃/分鐘的條件測定試驗片的長度方向的熱膨脹量，並將其反曲點當成是熱塑性液晶聚合物薄膜的熱變形溫度。
[實施例1] (1)熱塑性液晶聚合物薄膜的製作
使用單軸擠出機，在280~300℃下將包含6-羥基-2-萘甲酸單元(27莫耳%)、對羥基苯甲酸單元(73莫耳%)的熱致液晶聚酯進行加熱混練後，由直徑40mm、狹縫間隔0.6mm的吹脹模擠出，得到了厚度50μm的熱塑性液晶聚合物薄膜。此熱塑性液晶聚合物薄膜的熔點Tm為282℃，熱變形溫度Tdef為230℃。
(2)單面覆金屬積層板的製作
一邊參照圖1，一邊說明單面覆金屬積層板的製作。準備在前述(1)製作的熱塑性液晶聚合物薄膜、和厚度12μm的壓延銅箔(JX日鑛日石金屬(股)製，商品名：BHYX-HA-V2，Rz：0.9μm)分別作為熱塑性液晶聚合物薄膜2及金屬薄片6。另一方面，在連續熱輥壓裝置10分別安裝金屬彈性輥8、和加熱金屬輥9作為積層用加熱輥7，以熱塑性液晶聚合物薄膜2接觸金屬彈性輥8側，金屬薄片6接觸加熱金屬輥9側的方式導入，將熱塑性液晶聚合物薄膜2及金屬薄片6進行熱壓接，製作了單面覆金屬積層板19。
此處，金屬彈性輥8係在硬度90度的耐熱性橡膠輥的外周安裝厚度380μm的金屬帶，金屬彈性輥的金屬表面具有十點表面粗糙度Rz：0.2μm以下。此外，加熱金屬輥9的表面溫度係270℃，在耐熱橡膠輥與加熱金屬輥之間施加在熱塑性液晶聚合物薄膜及銅箔的壓力，以面壓換算為40kg/cm2。此外，積層速度為3m/分鐘。在此條件下，使熱塑性液晶聚合物薄膜沿著耐熱橡膠輥移動後，使銅箔與熱塑性液晶聚合物薄膜接合在一起，得到了積層板。
另外，在此積層板中，為了提高熱塑性液晶聚合物薄膜及金屬薄片的層間接著性，然後，藉由夾持輥，在線上解除捲取張力，將製作的積層板進行了利用IR的加熱處理。
又，在熱處理爐內從150℃起慢慢地升溫，熱處理裝置的熱處理時間(即，積層板的任一點通過既定的熱處理溫度的時間)，係以任一點花10秒鐘通過Tm+5℃(Tm：薄膜熔點)的方式設定，進行了熱處理。
對在開始運轉60分鐘後所製造的單面覆金屬積層板，用目視觀察熱塑性液晶聚合物薄膜面的表面狀態，同時測定了熱塑性液晶聚合物薄膜面的光澤度。將結果顯示於表7。
(3)銅蒸鍍層的形成
一邊參照圖2，一邊說明銅蒸鍍層的形成。採用使用了真空蒸鍍裝置(Rock技研工業(股)製，商品名：RVC-W-300)的卷對卷方式，在上述單面覆金屬積層板19的液晶聚合物薄膜2面形成了銅蒸鍍層(厚度：0.3μm)。
更具體而言，將單面覆金屬積層板19放置在裝載機側，將開放窗完全封閉後，進行抽真空，與此同時地將蒸鍍用加熱輥13的溫度設為100℃。
接著，取出銅錠，以銅的總重量成為450g的方式加入銅粒料。又，使用對銅粒料進行作為前處理的利用過硫酸鈉水的清洗，之後，用蒸餾水清洗者。
接著，確認蒸鍍用腔室內的真空度成為7×10-3Pa後，將蒸鍍用加熱輥13的設定溫度設為(Tm-15)℃(Tm：薄膜熔點)。之後，使電子槍18的EMI(放射電流值)的輸出提高，使坩堝17中的銅熔融。又，此時，以蒸鍍速度成為2.7nm/s的方式調整了EMI輸出值。
接著，確認蒸鍍用加熱輥13的溫度到達前述設定溫度(Tm-15)℃，蒸鍍用腔室內的真密度成為 5×10-3Pa以下後，在將單面覆金屬積層板19的搬送速度設定為0.5m/分鐘的狀態下，進行銅的蒸鍍處理，形成具有0.3μm的厚度的銅蒸鍍層，得到了雙面覆金屬積層板23。
(4)微帶電路的形成
使用製作的雙面覆金屬積層板23，具有在在背面形成了導體箔的板狀介電體基板的表面形成了線狀的導體箔的構造，製作了傳達電磁波的50Ω的傳輸路徑(微帶線)。
具體而言，將雙面覆金屬積層板23的金屬蒸鍍面作為種晶層，在其上形成阻劑的圖案後，進行電解鍍銅而使電路成長。之後，除去阻劑，蝕刻電路間的種晶層，從而形成厚度12μm的電路圖案。另外，進行貫穿孔鍍覆，從而製作電路的厚度為30μm的微帶電路基板，測定了其傳輸特性。將所得到的結果顯示在表7。
[實施例2] (1)熱塑性液晶聚合物薄膜的製作
使用單軸擠出機，在350℃下將包含6-羥基-2-萘甲酸單元(20莫耳%)、對羥基苯甲酸單元(80莫耳%)的熱致液晶聚酯進行加熱混練後，由直徑40mm、狹縫間隔0.6mm的吹脹模擠出，得到了厚度50μm的熱塑性液晶聚合物薄膜。此熱塑性液晶聚合物薄膜的熔點Tm為325℃，熱變形溫度Tdef為310℃。 (2)除了使用在前述(1)所得到的熱塑性液晶聚合物薄膜作為熱塑性液晶聚合物薄膜，將加熱金屬輥5的表面溫度設為300℃外，與實施例1同樣地操作而製作了單面覆金屬積層板。之後，除了將蒸鍍用加熱輥13的設定溫度設為(Tm-15)℃(Tm：薄膜熔點)外，與實施例1同樣地操作而製作了雙面覆金屬積層板、微帶電路基板。將各種物性顯示在表7。
[實施例3及4]
除了針對實施例1及2的單面覆金屬積層板，分別使用剛開始運轉後所製造的單面覆金屬積層板，取代在開始運轉60分鐘後所得到的單面覆金屬積層板外，分別與實施例1及2同樣地操作，得到了雙面覆金屬積層板、微帶電路基板。將各種物性顯示在表7。
[比較例1]
除了使用耐熱性橡膠輥[樹脂被覆金屬輥(由利Roll機械(股)製，商品名：Super-Tempex，樹脂厚度：1.7cm)，直徑：40cm]，取代金屬彈性輥外，與實施例1同樣地操作而製作了單面覆金屬積層板。之後，與實施例1同樣地操作而得到了雙面覆金屬積層板、微帶電路基板。將各種物性顯示在表7。
[比較例2]
除了使用耐熱性橡膠輥[樹脂被覆金屬輥(由利Roll 機械(股)製，商品名：Super-Tempex，樹脂厚度：1.7cm)，直徑：40cm]，取代金屬彈性輥外，與實施例2同樣地操作而製作了單面覆金屬積層板。之後，與實施例2同樣地操作而得到了雙面覆金屬積層板、微帶電路基板。將各種物性顯示在表7。
[比較例3及4]
除了針對比較例1及2的單面覆金屬積層板，分別使用剛開始運轉後所製造的單面覆金屬積層板，取代在開始運轉60分鐘後所得到的單面覆金屬積層板外，分別與比較例1及2同樣地操作，得到了雙面覆金屬積層板、微帶電路基板。將各種物性顯示在表7。
Figure 107111586-A0202-12-0034-7
如表7所示，實施例1及2，即使是連續運轉60分鐘的情況，液晶聚合物薄膜表面也都沒有皺摺產生，都保持良好的表面狀態。另外，即使與顯示剛運轉後的覆金屬積層板的實施例3及4比較，實施例1及2的光澤度也不遜色，即使是進行長時間的連續運轉後，液晶聚合物薄膜表面係光澤度高的水準。連續運轉60分鐘後的光澤度保持率，在實施例1及2中為98.5%及101%。
另外，反映這樣的高光澤度，在實施例1~4所得到的微帶電路基板的傳輸損失，在40GHz及60GHz雙方下，顯示比比較例小的值。
另一方面，比較例1及2，隨著連續運轉，而液晶聚合物薄膜對耐熱橡膠輥的附著變得強勁，確認了在60分鐘後在液晶聚合物薄膜面產生明顯的剝離皺摺。此外，針對沒有皺摺產生的部分，光澤度低，表面的光澤感比實施例1及2差。
此外，由比較例3及4可知，使用耐熱橡膠輥的情況，橡膠輥表面所形成的微細的條紋被轉印，因此即使是剛開始運轉後，液晶聚合物薄膜面的光澤度也比實施例1及2差。而比較例3及4，相較於實施例，傳輸損失皆較差。此外，連續運轉60分鐘後的光澤度保持率，在比較例1及2中為77%及92%，若與實施例1及2相比，則光澤度明顯降低。
[產業上之可利用性]
如根據本發明，則能夠得到液晶聚合物薄膜表面具有以往未曾有的光澤面的覆金屬積層板。而能夠由這樣的覆金屬積層板提供具有優異的傳輸特性的電路基板。
如上所述，一邊參照圖式，一邊說明了本發明的合適的實施例，但若為同業，則應可看本案說明書而在顯而易見的範圍內輕易推測出各種變更及修正。因此，該種的變更及修正會解釋為由申請專利範圍所限定的發明範圍內者。
2:熱塑性液晶聚合物薄膜
6:金屬薄片
7:一對加熱輥
8:金屬彈性輥
9:加熱金屬輥
10:連續熱壓裝置
19:單面覆金屬積層板
21:捲出輥
22:捲出輥

Claims (11)

  1. 一種覆金屬積層板，係至少積層了熱塑性液晶聚合物薄膜和金屬薄片的覆金屬積層板，在基於JIS Z 8741的光澤度(20°)方面，與和金屬薄片的接合面為相反側的熱塑性液晶聚合物薄膜表面為55以上。
  2. 如請求項1的覆金屬積層板，其中熱塑性液晶聚合物薄膜的熔點為290℃以上。
  3. 如請求項1或2的覆金屬積層板，其進一步具備形成在該熱塑性液晶聚合物表面的金屬蒸鍍層。
  4. 如請求項1或2的覆金屬積層板，其在長邊方向上具有100m以上的長度。
  5. 一種覆金屬積層板的製造方法，係藉由卷對卷方式，在熱塑性液晶聚合物薄膜的表面接合了金屬薄片之覆金屬積層板的製造方法，至少具備：準備熱塑性液晶聚合物薄膜和金屬薄片的步驟；和將該熱塑性液晶聚合物薄膜和該金屬薄片導入一對加熱輥間，使該熱塑性液晶聚合物薄膜和該金屬薄片在該一對加熱輥間壓接的步驟，且該一對加熱輥，係在與該熱塑性液晶聚合物薄膜相接的側至少具備金屬彈性輥，該金屬彈性輥係表面的十點平均粗糙度Rz為0.2μm以下。
  6. 如請求項5的覆金屬積層板的製造方法，其中該一對加熱輥係以金屬輥和金屬彈性輥所構成。
  7. 如請求項6的覆金屬積層板的製造方法，其中該金屬輥係內部加熱式的金屬輥。
  8. 如請求項5至7中任一項的覆金屬積層板的製造方法，其中該金屬彈性輥係以輥狀的耐熱性橡膠、和形成在其周圍的金屬表面層所構成。
  9. 如請求項8的覆金屬積層板的製造方法，其中該耐熱性橡膠的硬度為70~100，金屬表面層的厚度為100μm~1000μm。
  10. 一種電路基板，係在如請求項1至4中任一項的覆金屬積層板上形成有電路圖案。
  11. 如請求項10的電路基板，其中該電路圖案係形成在熱塑性液晶聚合物薄膜表面或金屬蒸鍍層表面。
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