TW202106519A - Production method of metal-clad laminate - Google Patents

Production method of metal-clad laminate Download PDF

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TW202106519A
TW202106519A TW109120156A TW109120156A TW202106519A TW 202106519 A TW202106519 A TW 202106519A TW 109120156 A TW109120156 A TW 109120156A TW 109120156 A TW109120156 A TW 109120156A TW 202106519 A TW202106519 A TW 202106519A
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Taiwan
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metal
clad laminate
manufacturing
liquid crystal
sided
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TW109120156A
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Chinese (zh)
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高橋健
中島崇裕
佐佐木翔真
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日商可樂麗股份有限公司
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    • 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
    • B29C63/00—Lining or sheathing, i.e. applying preformed layers or sheathings of plastics; Apparatus therefor
    • B29C63/02—Lining or sheathing, i.e. applying preformed layers or sheathings of plastics; Apparatus therefor using sheet or web-like material
    • 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
    • B29C43/00—Compression moulding, i.e. applying external pressure to flow the moulding material; Apparatus therefor
    • B29C43/22—Compression moulding, i.e. applying external pressure to flow the moulding material; Apparatus therefor of articles of indefinite length
    • B29C43/24—Calendering
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B21—MECHANICAL METAL-WORKING WITHOUT ESSENTIALLY REMOVING MATERIAL; PUNCHING METAL
    • B21D—WORKING OR PROCESSING OF SHEET METAL OR METAL TUBES, RODS OR PROFILES WITHOUT ESSENTIALLY REMOVING MATERIAL; PUNCHING METAL
    • B21D17/00—Forming single grooves in sheet metal or tubular or hollow articles
    • B21D17/04—Forming single grooves in sheet metal or tubular or hollow articles by rolling
    • 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
    • B29C43/00—Compression moulding, i.e. applying external pressure to flow the moulding material; Apparatus therefor
    • B29C43/003—Compression moulding, i.e. applying external pressure to flow the moulding material; Apparatus therefor characterised by the choice of material
    • 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
    • B29C43/00—Compression moulding, i.e. applying external pressure to flow the moulding material; Apparatus therefor
    • B29C43/32—Component parts, details or accessories; Auxiliary operations
    • 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
    • B29C43/00—Compression moulding, i.e. applying external pressure to flow the moulding material; Apparatus therefor
    • B29C43/32—Component parts, details or accessories; Auxiliary operations
    • B29C43/52—Heating or cooling
    • 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
    • B29C59/00—Surface shaping of articles, e.g. embossing; Apparatus therefor
    • B29C59/02—Surface shaping of articles, e.g. embossing; Apparatus therefor by mechanical means, e.g. pressing
    • B29C59/04—Surface shaping of articles, e.g. embossing; Apparatus therefor by mechanical means, e.g. pressing using rollers or endless belts
    • 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
    • B29C63/00—Lining or sheathing, i.e. applying preformed layers or sheathings of plastics; Apparatus therefor
    • B29C63/0004—Component parts, details or accessories; Auxiliary operations
    • 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
    • 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
    • B29C66/40—General aspects of joining substantially flat articles, e.g. plates, sheets or web-like materials; Making flat seams in tubular or hollow articles; Joining single elements to substantially flat surfaces
    • B29C66/41—Joining substantially flat articles ; Making flat seams in tubular or hollow articles
    • 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
    • B29C66/70—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
    • B29C66/74—Joining plastics material to non-plastics material
    • B29C66/742—Joining plastics material to non-plastics material to metals or their alloys
    • 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
    • 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
    • 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
    • B32B38/00—Ancillary operations in connection with laminating processes
    • 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
    • B32B43/00—Operations specially adapted for layered products and not otherwise provided for, e.g. repairing; Apparatus therefor
    • B32B43/006—Delaminating
    • 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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29L—INDEXING SCHEME ASSOCIATED WITH SUBCLASS B29C, RELATING TO PARTICULAR ARTICLES
    • B29L2009/00—Layered products
    • B29L2009/003—Layered products comprising a metal layer

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  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Manufacturing & Machinery (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Laminated Bodies (AREA)

Abstract

Provided is a method of efficiently producing a metal-clad laminate subjected to a shaping treatment. In the production method, a long single-sided metal-clad laminate (A) in which a metal layer is bonded to one side of a thermoplastic liquid crystal polymer film, and a long metal shaping sheet (B) in which at least one surface is a shaping surface are prepared. Then the long single-sided metal-clad laminate (A) and the long metal shaping sheet (B) are introduced into a pair of pressure rollers (r1 , r2 ) for thermo-compression bonding in which a surface of the thermoplastic liquid crystal polymer film in the single-sided metal-clad laminate (A) is in contact with the shaping surface of the metal shaping sheet (B) to produce a metal-clad laminate.

Description

覆金屬之積層體的製造方法Method for manufacturing metal-clad laminate

本發明係關於一種覆金屬之積層體(或剝離了另一面的金屬賦形薄片的覆金屬之積層體)的製造方法，該覆金屬之積層體係在包含可形成光學上異向性的熔融相的熱塑性聚合物(以下，有將其稱為熱塑性液晶聚合物的情形)的薄膜(以下，有將其稱為熱塑性液晶聚合物薄膜的情形)的一面積層金屬層，在另一面，積層前述熱塑性液晶聚合物薄膜側的表面為賦形面的金屬賦形薄片。The present invention relates to a method for manufacturing a metal-clad laminate (or a metal-clad laminate from which the metal-shaped sheet on the other side is peeled off). The metal-clad laminate system includes a molten phase that can form an optically anisotropic Thermoplastic polymer (hereinafter, sometimes referred to as thermoplastic liquid crystal polymer) film (hereinafter, sometimes referred to as thermoplastic liquid crystal polymer film) has a metal layer on one area, and on the other side, the aforementioned thermoplastic The surface on the side of the liquid crystal polymer film is a metal shaped sheet with a shaped surface.

熱塑性液晶聚合物薄膜，係作為高耐熱性、低吸濕性、高頻特性等優異的材料而為人所知，近年來作為高速傳輸用電子電路材料而受到矚目。在用於電子電路基板用途的情況下，使用熱塑性液晶聚合物薄膜和金屬箔的覆金屬之積層體，但在電路加工步驟中的貼合加工中，有覆金屬之積層體所具備的熱塑性液晶聚合物薄膜和接合薄片(bonding sheet)的層間接著性並不充分的情況。以往，為了提高與接合薄片的層間接著性，而在熱塑性液晶聚合物薄膜的一面具備金屬層的單面覆金屬之積層體中，對另一面的熱塑性液晶聚合物薄膜的表面進行賦予凹凸形狀的賦形處理。The thermoplastic liquid crystal polymer film is known as an excellent material with high heat resistance, low moisture absorption, and high frequency characteristics, and in recent years has attracted attention as an electronic circuit material for high-speed transmission. In the case of electronic circuit board applications, a metal-clad laminate of a thermoplastic liquid crystal polymer film and metal foil is used, but in the bonding process in the circuit processing step, there is a thermoplastic liquid crystal that the metal-clad laminate has When the interlayer adhesion between the polymer film and the bonding sheet is insufficient. In the past, in order to improve the interlayer adhesion with the bonding sheet, in a single-sided metal-clad laminate having a metal layer on one side of the thermoplastic liquid crystal polymer film, the surface of the thermoplastic liquid crystal polymer film on the other side was provided with irregularities. Shaping treatment.

專利文獻1(日本特開2016-10967號公報)中揭示了如下的附有金屬箔的液晶聚合物薄膜的製造方法：具有依序重疊第1金屬箔、液晶聚合物薄膜、和第2金屬箔並進行加熱加壓的步驟，前述第2金屬箔的重疊於前述液晶聚合物薄膜的面為消光面，對前述消光面施加脫模處理。Patent Document 1 (Japanese Patent Application Laid-Open No. 2016-10967) discloses a method of manufacturing a liquid crystal polymer film with metal foil as follows: a first metal foil, a liquid crystal polymer film, and a second metal foil are sequentially stacked The step of heating and pressing is performed, the surface of the second metal foil overlapping the liquid crystal polymer film is a matte surface, and the matte surface is subjected to a mold release treatment.

又，專利文獻2(日本特開2006-179609號公報)中揭示了一種積層配線基板的製造法，並揭示了熱塑性樹脂為液晶聚合物，該積層配線基板的製造法的特徵為：以鹼混合溶液為藥液，對各個熱塑性樹脂層中的至少一面施加藥液粗化處理，將經施加前述處理的面重疊於其他單位基板的面而形成具有2個以上的層的積層板，將前述積層板進行加熱、加壓處理。 [先前技術文獻] [專利文獻]In addition, Patent Document 2 (Japanese Patent Laid-Open No. 2006-179609) discloses a method for manufacturing a multilayer wiring board, and discloses that the thermoplastic resin is a liquid crystal polymer, and the characteristic of the method for manufacturing the multilayer wiring board is that it is mixed with alkali The solution is a chemical solution, and at least one surface of each thermoplastic resin layer is subjected to a chemical solution roughening treatment, and the surface subjected to the aforementioned treatment is superimposed on the surface of the other unit substrate to form a laminated board having two or more layers. The board is heated and pressurized. [Prior Technical Literature] [Patent Literature]

專利文獻1：日本特開2016-10967號公報 專利文獻2：日本特開2006-179609號公報Patent Document 1: Japanese Patent Application Publication No. 2016-10967 Patent Document 2: Japanese Patent Application Publication No. 2006-179609

[發明欲解決之課題][The problem to be solved by the invention]

又，在將覆金屬之積層體用於高速傳輸用電子電路的情況下，由於在成為傳輸線路的金屬層中產生表皮效應(skin effect)，因此金屬層的高頻特性，即傳輸損失係依存於其表面粗糙度。因此，使用表面粗糙度小的低粗糙度的金屬層者，係傳輸損失變小，即高頻特性變佳，因此是較理想的。In addition, when a metal-clad laminate is used in an electronic circuit for high-speed transmission, a skin effect is generated in the metal layer that becomes the transmission line, so the high-frequency characteristics of the metal layer, that is, the transmission loss is dependent on Because of its surface roughness. Therefore, it is preferable to use a metal layer with a low surface roughness and a low roughness because the transmission loss is reduced, that is, the high-frequency characteristics are improved.

然而，在如專利文獻1所示，藉由將第1金屬箔、液晶聚合物薄膜、和為了賦形處理而之後加以剝離的第2金屬箔重疊並進行加熱加壓，來一次性地使其積層一體化的情況下，若第1金屬箔使用低粗糙度者，則為了提高第1金屬箔和液晶聚合物薄膜的層間接著性而需要加熱至液晶聚合物薄膜的熔點附近(或熔點以上)。在該情況下，高溫的熱也籠罩在之後剝離的第2金屬箔和液晶聚合物薄膜的界面，即使欲對第2金屬箔施加脫模處理，也因由表面的凹凸所產生的錨定效果而層間接著性變高，因此變得很難剝離第2金屬箔。However, as shown in Patent Document 1, the first metal foil, the liquid crystal polymer film, and the second metal foil that is peeled off for the shaping treatment are superimposed and heated and pressurized to make them all at once. In the case of laminated integration, if a low roughness is used for the first metal foil, it is necessary to heat to near the melting point of the liquid crystal polymer film (or above the melting point) in order to improve the interlayer adhesion between the first metal foil and the liquid crystal polymer film. . In this case, the high-temperature heat also covers the interface between the second metal foil and the liquid crystal polymer film that will be peeled off later. Even if the second metal foil is to be released from the mold, the anchoring effect due to the unevenness on the surface is also affected. Since the layer adhesion becomes higher, it becomes difficult to peel the second metal foil.

再者，熱塑性液晶聚合物薄膜，係液晶聚合物分子因加熱加壓而容易進行配向，因此若在如上述的高溫下進行加熱加壓，則配向會大幅變化，所得到的覆金屬之積層體的翹曲變大，而且尺寸變化變大，從而形成電路基板變得困難。Furthermore, the thermoplastic liquid crystal polymer film is a liquid crystal polymer molecule that is easy to align by heating and pressing. Therefore, if heating and pressing at a high temperature as described above, the alignment will change significantly, and the resulting metal-clad laminate The warpage becomes larger, and the size change becomes larger, so that it becomes difficult to form a circuit board.

又，在如專利文獻2施加藥液粗化處理的情況下，雖然能夠對熱塑性樹脂層的表面賦予微細的凹凸，但為了施加藥液處理而處理步驟變多，生產效率降低。再者，由於將附著於經施加藥液處理的表面的藥劑完全去除是困難的，因此有在所得到的電路基板中，因雜質的存在而發生不良狀況的情況。In addition, when the chemical solution roughening treatment is applied as in Patent Document 2, although fine irregularities can be provided to the surface of the thermoplastic resin layer, the processing steps for applying the chemical solution treatment increase, and the production efficiency is reduced. Furthermore, since it is difficult to completely remove the drug adhering to the surface treated with the chemical solution, the resulting circuit board may be defective due to the presence of impurities.

由此，本發明的目的在於提供一種尺寸變化小且效率佳地製造經賦形處理的覆金屬之積層體的方法。 [用以解決課題之手段]Therefore, the object of the present invention is to provide a method for efficiently manufacturing a shaped metal-clad laminate with small dimensional changes. [Means to solve the problem]

本發明的發明人等，為了達成上述目的而銳意檢討，結果發現：藉由各自獨立地進行單面覆金屬之積層體的製造和單面覆金屬之積層體的賦形處理，能夠在賦形處理之際避免高溫下的加熱加壓，因此能夠抑制覆金屬之積層體的尺寸變化。然後，發現準備在熱塑性液晶聚合物薄膜的一面接著金屬層的單面覆金屬之積層體，將單面覆金屬之積層體和金屬賦形薄片連續地進行熱壓接，從而能夠效率佳地進行賦形處理，進而完成本發明。The inventors of the present invention have intensively studied in order to achieve the above-mentioned object. As a result, they have found that by independently performing the production of a single-sided metal-clad laminate and the forming process of the single-sided metal-clad laminate, it is possible to form During the treatment, heating and pressing at high temperatures is avoided, so that the dimensional change of the metal-clad laminate can be suppressed. Then, it was discovered that a single-sided metal-clad laminate with a metal layer attached to one side of the thermoplastic liquid crystal polymer film was prepared, and the single-sided metal-clad laminate and the metal shaped sheet were continuously thermocompression bonded, so that it could be carried out efficiently. The shaping process has completed the present invention.

即，本發明可用以下的態樣構成。 [態樣1] 一種覆金屬之積層體的製造方法，其至少具備： 準備在熱塑性液晶聚合物薄膜的一面接著金屬層的長條狀的單面覆金屬之積層體(A)、及至少一表面為賦形面的長條狀的金屬賦形薄片(B)的步驟；和 以前述單面覆金屬之積層體(A)的熱塑性液晶聚合物薄膜面和前述金屬賦形薄片(B)的賦形面接觸的方式配置，朝向一對加壓輥(r1 , r2 )導入的熱壓接步驟。 [態樣2] 如態樣1記載的覆金屬之積層體的製造方法，其進一步具備： 在熱壓接步驟後，從前述單面覆金屬之積層體(A)的熱塑性液晶聚合物薄膜面剝離前述金屬賦形薄片(B)的剝離步驟。 [態樣3] 如態樣1或2記載的覆金屬之積層體的製造方法，其中在以前述熱塑性液晶聚合物薄膜的熔點(Tm)而言的情況下，熱壓接溫度為(Tm-150)℃以上且小於(Tm)℃(較佳為(Tm-130)℃以上(Tm-5)℃以下，更佳為(Tm-110)℃以上(Tm-10)℃以下)。 [態樣4] 如態樣1至3中任一態樣記載的覆金屬之積層體的製造方法，其中前述單面覆金屬之積層體(A)和前述金屬賦形薄片(B)的剝離強度為0.5N/mm以下(較佳為0.2N/mm以下，更佳為0.1N/mm以下)。 [態樣5] 如態樣1至4中任一態樣記載的覆金屬之積層體的製造方法，其中前述金屬賦形薄片(B)的賦形面的表面粗糙度(Rz)為1.0～7.0μm(較佳為1.5～5.5μm，更佳為2.0～4.5μm)。 [態樣6] 如態樣1至5中任一態樣記載的覆金屬之積層體的製造方法，其中， 在準備步驟中，進一步準備長條狀的脫模緩衝材(C)， 在熱壓接步驟中，在前述單面覆金屬之積層體(A)及前述金屬賦形薄片(B)的未接觸側中的至少一側配置前述脫模緩衝材(C)，朝向一對加壓輥(r1 , r2 )導入。 [態樣7] 如態樣6記載的覆金屬之積層體的製造方法，其中前述脫模緩衝材(C)和前述單面覆金屬之積層體(A)或前述金屬賦形薄片(B)的剝離強度為0.1N/mm以下(較佳為0.05N/mm以下，更佳為0.03N/mm以下)。 [態樣8] 如態樣6或7記載的覆金屬之積層體的製造方法，其中前述脫模緩衝材(C)係從包含耐熱性樹脂薄膜、耐熱性複合薄膜、耐熱性不織布、及至少一面具備脫模層的金屬箔的群組選出。 [態樣9] 如態樣6至8中任一態樣記載的覆金屬之積層體的製造方法，其中前述脫模緩衝材(C)的至少一面的表面粗糙度(Rz)為2.0μm以下(較佳為1.8μm以下，更佳為1.5μm以下)。 [態樣10] 如態樣6至9中任一態樣記載的覆金屬之積層體的製造方法，其中在前述熱壓接步驟中，以成為(r1 )/(C)/(A)/(B)/(r2 )的順序的方式，將單面覆金屬之積層體(A)、金屬賦形薄片(B)及脫模緩衝材(C)重疊而導入於一對加壓輥(r1 , r2 )之間。 [態樣11] 如態樣10記載的覆金屬之積層體的製造方法，其中在前述熱壓接步驟中，加壓輥(r2 )係加熱溫度比加壓輥(r1 )高。 [態樣12] 如態樣1至11中任一態樣記載的覆金屬之積層體的製造方法，其中分別準備複數個長條狀的單面覆金屬之積層體(A)及長條狀的金屬賦形薄片(B)，製造複數個覆金屬之積層體。 [態樣13] 如依附於態樣6至9中任一態樣的情況下的態樣11記載的覆金屬之積層體的製造方法，其中在前述熱壓接步驟中，將脫模緩衝材(C)重疊而導入於複數組的包含單面覆金屬之積層體(A)及金屬賦形薄片(B)的積層體之間。 [態樣14] 如態樣13記載的覆金屬之積層體的製造方法，其中在前述熱壓接步驟中，以成為(r1 )/(B)/(A)/(C)/(A)/(B)/(r2 )的順序的方式，將單面覆金屬之積層體(A)、金屬賦形薄片(B)及脫模緩衝材(C)重疊而導入於一對加壓輥(r1 , r2 )之間。 [態樣15] 如依附於態樣6至9中任一態樣的情況下的態樣11或態樣12記載的覆金屬之積層體的製造方法，其中在前述熱壓接步驟中，以與一對加壓輥(r1 , r2 )中的至少一個加壓輥相接的方式，將脫模緩衝材(C)重疊而導入。 [態樣16] 如態樣15記載的覆金屬之積層體的製造方法，其中在前述熱壓接步驟中，以成為(r1 )/(C)/(B)/(A)/(A)/(B)/(C)/(r2 )、或者是(r1 )/(C)/(A)/(B)/(B)/(A)/(C)/(r2 )的順序的方式，將單面覆金屬之積層體(A)、金屬賦形薄片(B)及脫模緩衝材(C)重疊而導入於一對加壓輥(r1 , r2 )之間。That is, the present invention can be configured in the following aspects. [Aspect 1] A method for manufacturing a metal-clad laminate, comprising at least: preparing a long strip of one-sided metal-clad laminate (A) with a metal layer attached to one side of a thermoplastic liquid crystal polymer film, and at least one The step of forming an elongated metal-shaped flake (B) with a shaped surface on the surface; and using the thermoplastic liquid crystal polymer film surface of the aforementioned single-sided metal-clad laminate (A) and the aforementioned metal-shaped flake (B) It is arranged in such a way that the shaped surface is in contact, and is directed toward the thermocompression bonding step of a pair of pressure rollers (r 1 , r 2 ). [Aspect 2] The method for manufacturing a metal-clad laminate as described in Aspect 1, further comprising: after the thermocompression bonding step, from the surface of the thermoplastic liquid crystal polymer film of the single-sided metal-clad laminate (A) The peeling step of peeling the aforementioned metal-shaped sheet (B). [Aspect 3] The method for manufacturing a metal-clad laminate as described in aspect 1 or 2, wherein in terms of the melting point (Tm) of the aforementioned thermoplastic liquid crystal polymer film, the thermocompression bonding temperature is (Tm- 150)°C or higher and less than (Tm)°C (preferably (Tm-130)°C or higher (Tm-5)°C or lower, more preferably (Tm-110)°C or higher (Tm-10)°C or lower). [Aspect 4] The method for producing a metal-clad laminate as described in any one of the aspects 1 to 3, wherein the single-sided metal-clad laminate (A) and the metal-shaped sheet (B) are peeled off The strength is 0.5 N/mm or less (preferably 0.2 N/mm or less, more preferably 0.1 N/mm or less). [Aspect 5] The method for manufacturing a metal-clad laminate as described in any one of aspects 1 to 4, wherein the surface roughness (Rz) of the shaped surface of the aforementioned metal shaped sheet (B) is 1.0 to 7.0 μm (preferably 1.5 to 5.5 μm, more preferably 2.0 to 4.5 μm). [Aspect 6] The method for manufacturing a metal-clad laminate as described in any one of aspects 1 to 5, wherein, in the preparation step, a strip-shaped release buffer material (C) is further prepared, and the In the crimping step, the release buffer material (C) is placed on at least one of the non-contact sides of the single-sided metal-clad laminate (A) and the metal shaped sheet (B), and the release buffer material (C) is placed toward a pair of press Roll (r 1 , r 2 ) is introduced. [Aspect 7] The method for manufacturing a metal-clad laminate according to aspect 6, wherein the release buffer material (C) and the single-sided metal-clad laminate (A) or the metal-shaped sheet (B) The peel strength is 0.1 N/mm or less (preferably 0.05 N/mm or less, more preferably 0.03 N/mm or less). [Aspect 8] The method for producing a metal-clad laminate as described in aspect 6 or 7, wherein the release buffer material (C) is selected from a heat-resistant resin film, a heat-resistant composite film, a heat-resistant nonwoven fabric, and at least A group of metal foils with a release layer on one side is selected. [Aspect 9] The method for manufacturing a metal-clad laminate as described in any one of aspects 6 to 8, wherein the surface roughness (Rz) of at least one side of the release buffer material (C) is 2.0 μm or less (Preferably 1.8 μm or less, more preferably 1.5 μm or less). [Aspect 10] The method for manufacturing a metal-clad laminate as described in any one of the aspects 6 to 9, wherein in the thermal compression bonding step, (r 1 )/(C)/(A) /(B)/(r 2 ) in order to superimpose the single-sided metal-clad laminate (A), the metal shaped sheet (B) and the release buffer material (C) and introduce them to a pair of pressure rollers (r 1 , r 2 ). [Aspect 11] The method for manufacturing a metal-clad laminate as described in aspect 10, wherein in the thermal compression bonding step, the pressure roller (r 2 ) is heated at a higher temperature than the pressure roller (r 1 ). [Aspect 12] The method for manufacturing a metal-clad laminate as described in any one of the aspects 1 to 11, wherein a plurality of elongated single-sided metal-clad laminates (A) and elongated shapes are respectively prepared The metal-shaped flakes (B) of, make a plurality of metal-clad laminates. [Aspect 13] The method for manufacturing a metal-clad laminate described in Aspect 11 in the case of being attached to any of Aspects 6 to 9, wherein in the aforementioned thermocompression bonding step, the release buffer material (C) It is superposed and introduced between a plurality of laminates including a single-sided metal-clad laminate (A) and a metal-shaped sheet (B). [Aspect 14] The method for manufacturing a metal-clad laminate as described in aspect 13, wherein in the aforementioned thermocompression bonding step, (r 1 )/(B)/(A)/(C)/(A) )/(B)/(r 2 ) in order to superimpose the single-sided metal-clad laminate (A), metal shaped sheet (B) and release buffer material (C) into a pair of press Between the rollers (r 1 , r 2 ). [Aspect 15] The method for manufacturing a metal-clad laminate described in Aspect 11 or Aspect 12 in the case of being attached to any of Aspects 6 to 9, wherein in the aforementioned thermocompression bonding step, In the form of contact with at least one of the pair of pressure rollers (r 1 , r 2 ), the release buffer material (C) is overlapped and introduced. [Aspect 16] The method for manufacturing a metal-clad laminate as described in Aspect 15, wherein in the aforementioned thermocompression bonding step, the value becomes (r 1 )/(C)/(B)/(A)/(A) )/(B)/(C)/(r 2 ), or (r 1 )/(C)/(A)/(B)/(B)/(A)/(C)/(r 2 ) In the order of the method, the single-sided metal-clad laminate (A), the metal shaped sheet (B) and the release buffer material (C) are overlapped and introduced between a pair of pressure rollers (r 1 , r 2 ) .

此外，申請專利範圍及/或說明書及/或圖式中所揭示的至少兩個構成要素的任何組合也包含在本發明內。特別是，申請專利範圍中所記載的請求項的兩個以上的任何組合也包含在本發明內。 [發明之效果]In addition, any combination of at least two constituent elements disclosed in the scope of the patent application and/or the specification and/or the drawings is also included in the present invention. In particular, any combination of two or more of the claims described in the scope of the patent application is also included in the present invention. [Effects of Invention]

若根據本發明的話，則能夠藉由準備單面覆金屬之積層體及金屬賦形薄片，在以單面覆金屬之積層體的熱塑性液晶聚合物薄膜面和金屬賦形薄片的賦形面接觸的方式配置的狀態下，朝向一對加壓輥導入以進行熱壓接，來連續地進行賦形處理，因此能夠效率佳地製造尺寸變化受到抑制的覆金屬之積層體。According to the present invention, by preparing a single-sided metal-clad laminate and a metal shaped sheet, the thermoplastic liquid crystal polymer film surface of the single-sided metal-clad laminate can be brought into contact with the shaped surface of the metal shaped sheet In the state of being arranged in a manner, it is introduced toward a pair of pressure rollers for thermocompression bonding to continuously perform the shaping process, and therefore, it is possible to efficiently manufacture a metal-clad laminate with suppressed dimensional changes.

[用以實施發明的形態][Form to implement the invention]

本發明的覆金屬之積層體的製造方法，能夠連續地製造使金屬賦形薄片積層在單面覆金屬之積層體的熱塑性液晶聚合物薄膜面的覆金屬之積層體、或經賦形處理的覆金屬之積層體。 此外，在本發明中，所謂的覆金屬之積層體，若為在熱塑性液晶聚合物薄膜的一面具備金屬層，且在另一面具備金屬賦形薄片的覆金屬之積層體、或在熱塑性液晶聚合物薄膜的一面具備金屬層，且另一面被賦形處理的覆金屬之積層體的話即可，也可以適宜具備其他附帶物(例如，脫模緩衝材)。The method for producing a metal-clad laminate of the present invention can continuously produce a metal-clad laminate in which a metal shaped sheet is laminated on the surface of a thermoplastic liquid crystal polymer film of a metal-clad laminate on one side, or a shaped-processed metal-clad laminate Metal-clad laminates. In addition, in the present invention, the so-called metal-clad laminate is a metal-clad laminate having a metal layer on one side of a thermoplastic liquid crystal polymer film and a metal-shaped flake on the other side, or a thermoplastic liquid crystal polymer film. The metal-clad laminate may be provided with a metal layer on one side of the material film, and a metal-clad laminate whose other side has been subjected to a shaping treatment, and other incidental materials (for example, a release buffer material) may be provided as appropriate.

(熱塑性液晶聚合物薄膜) 本發明的製造方法所使用的熱塑性液晶聚合物薄膜係由能夠熔融成形的液晶性聚合物形成。此熱塑性液晶聚合物，係可形成光學上異向性的熔融相的聚合物，若為能夠熔融成形的液晶性聚合物的話，則對於其化學構成沒有特別的限定，但例如，能舉出：熱塑性液晶聚酯、或在其中導入醯胺鍵的熱塑性液晶聚酯醯胺等。(Thermoplastic liquid crystal polymer film) The thermoplastic liquid crystal polymer film used in the production method of the present invention is formed of a liquid crystal polymer that can be melt-molded. This thermoplastic liquid crystal polymer is a polymer that can form an optically anisotropic melt phase. If it is a liquid crystal polymer that can be melt-formed, there is no particular limitation on its chemical composition, but for example: Thermoplastic liquid crystal polyester, or thermoplastic liquid crystal polyester amide with amide bond introduced therein, etc.

又，熱塑性液晶聚合物可以是在芳香族聚酯或芳香族聚酯醯胺中進一步導入醯亞胺鍵、碳酸酯鍵、碳二亞胺鍵、或三聚異氰酸酯鍵等的源自異氰酸酯的鍵等的聚合物。In addition, the thermoplastic liquid crystal polymer may be an isocyanate-derived bond further introduced into an aromatic polyester or aromatic polyester amide, such as an imine bond, a carbonate bond, a carbodiimide bond, or a trimeric isocyanate bond. And other polymers.

作為本發明中所使用的熱塑性液晶聚合物的具體例，能舉出由分類成以下例示的(1)至(4)的化合物及其衍生物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有適當的範圍是不言而喻的。As specific examples of the thermoplastic liquid crystal polymer used in the present invention, known thermoplastic liquid crystal polyesters and thermoplastic liquid crystal polyesters derived from the compounds classified into (1) to (4) and their derivatives exemplified below can be cited Amide. However, in order to form a polymer that can form an optically anisotropic melt phase, it is self-evident that the combination of various raw material compounds has an appropriate range.

(1)芳香族或脂肪族二醇(代表例參照表1) [表1]

Figure 02_image001
(1) Aromatic or aliphatic diols (refer to Table 1 for representative examples) [Table 1]
Figure 02_image001

(2)芳香族或脂肪族二羧酸(代表例參照表2) [表2]

Figure 02_image003
(2) Aromatic or aliphatic dicarboxylic acid (refer to Table 2 for representative examples) [Table 2]
Figure 02_image003

芳香族羥基羧酸(代表例參照表3) [表3]

Figure 02_image005
Aromatic hydroxycarboxylic acid (refer to Table 3 for representative examples) [Table 3]
Figure 02_image005

(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) [表4]

Figure 02_image007
(4) Aromatic diamine, aromatic hydroxylamine or aromatic amino carboxylic acid (refer to Table 4 for representative examples) [Table 4]
Figure 02_image007

作為由這些原料化合物所得到的熱塑性液晶聚合物的代表例，能舉出具有表5及6所示的構造單元的共聚物。As representative examples of thermoplastic liquid crystal polymers obtained from these raw material compounds, copolymers having structural units shown in Tables 5 and 6 can be cited.

[表5]

Figure 02_image009
[表6]
Figure 02_image011
[table 5]
Figure 02_image009
[Table 6]
Figure 02_image011

這些共聚物之中，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，特別是，較佳為(i)包含對羥基苯甲酸和6-羥基-2-萘甲酸的重複單元的共聚物、或(ii)包含從包含對羥基苯甲酸及6-羥基-2-萘甲酸的群組所選出的至少一種芳香族羥基羧酸、至少一種芳香族二醇、和至少一種芳香族二羧酸的重複單元的共聚物。Among these copolymers, a polymer containing at least p-hydroxybenzoic acid and/or 6-hydroxy-2-naphthoic acid as a repeating unit is preferred. In particular, it is preferred that (i) contains p-hydroxybenzoic acid and 6-hydroxybenzoic acid. A copolymer of repeating units of hydroxy-2-naphthoic acid, or (ii) containing at least one aromatic hydroxycarboxylic acid selected from the group consisting of p-hydroxybenzoic acid and 6-hydroxy-2-naphthoic acid, at least one aromatic A copolymer of a diol and at least one repeating unit of an aromatic dicarboxylic acid.

例如，在(i)的共聚物方面，在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下，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)，在熱塑性液晶聚合物中理想的是(A)/(B)=10/90～90/10左右，更佳可為(A)/(B)=15/85～85/15左右，再更佳可為(A)/(B)=20/80～80/20左右。For example, in the copolymer of (i), when the thermoplastic liquid crystal polymer contains at least repeating units of p-hydroxybenzoic acid and 6-hydroxy-2-naphthoic acid, the repeating unit (A) of p-hydroxybenzoic acid and repeating The molar ratio (A)/(B) of 6-hydroxy-2-naphthoic acid of unit (B) is ideally (A)/(B)=10/90～90/10 in the thermoplastic liquid crystal polymer , More preferably (A)/(B)=15/85～85/15 or so, and still more preferably (A)/(B)=20/80～80/20 or so.

又，在(ii)的共聚物的情況下，從包含對羥基苯甲酸及6-羥基-2-萘甲酸的群組所選出的至少一種芳香族羥基羧酸(C)、從包含4,4’-二羥基聯苯、氫醌、苯基氫醌、及4,4’-二羥基二苯基醚的群組所選出的至少一種芳香族二醇(D)、和從包含對苯二甲酸、間苯二甲酸及2,6-萘二甲酸的群組所選出的至少一種芳香族二羧酸(E)的熱塑性液晶聚合物中的各重複單元的莫耳比，可以是芳香族羥基羧酸(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，更佳可為(C)：(D)：(E)=(35～75)：(32.5～12.5)：(32.5～12.5)左右，再更佳可為(C)：(D)：(E)=(40～70)：(30～15)：(30～15)左右。In the case of the copolymer of (ii), at least one aromatic hydroxycarboxylic acid (C) selected from the group consisting of p-hydroxybenzoic acid and 6-hydroxy-2-naphthoic acid is selected from the group consisting of 4,4 At least one aromatic diol (D) selected from the group of'-dihydroxybiphenyl, hydroquinone, phenylhydroquinone, and 4,4'-dihydroxydiphenyl ether, and from containing terephthalic acid The molar ratio of each repeating unit in the thermoplastic liquid crystal polymer of at least one aromatic dicarboxylic acid (E) selected from the group of isophthalic acid and 2,6-naphthalenedicarboxylic acid may be an aromatic hydroxycarboxylic acid Acid (C): the aforementioned aromatic diol (D): the aforementioned aromatic dicarboxylic acid (E)=(30～80): (35～10): about (35～10), more preferably (C) ：(D):(E)=(35～75):(32.5～12.5):(32.5～12.5) or so, even more preferably (C):(D):(E)=(40～70) : (30-15): (30-15) or so.

又，芳香族羥基羧酸(C)之中源自6-羥基-2-萘甲酸的重複單元的莫耳比率，例如，可以是85莫耳%以上，較佳可為90莫耳%以上，更佳可為95莫耳%以上。芳香族二羧酸(E)之中源自2,6-萘二甲酸的重複單元的莫耳比率，例如，可以是85莫耳%以上，較佳可為90莫耳%以上，更佳可為95莫耳%以上。In addition, the molar ratio of the repeating unit derived from 6-hydroxy-2-naphthoic acid in the aromatic hydroxycarboxylic acid (C) may be, for example, 85 mol% or more, and preferably 90 mol% or more. More preferably, it may be 95 mol% or more. The molar ratio of the repeating unit derived from 2,6-naphthalenedicarboxylic acid in the aromatic dicarboxylic acid (E), for example, may be 85 mol% or more, preferably 90 mol% or more, more preferably It is more than 95 mol%.

又，芳香族二醇(D)可以是源自從包含氫醌、4,4’-二羥基聯苯、苯基氫醌、及4,4’-二羥基二苯基醚的群組所選出的彼此不同的二種芳香族二醇的重複單元(D1)和(D2)，在此情況下，二種芳香族二醇的莫耳比可以是(D1)/(D2)=23/77～77/23，更佳可為25/75～75/25，再更佳可為30/70～70/30。In addition, the aromatic diol (D) may be derived from a group selected from the group consisting of hydroquinone, 4,4'-dihydroxybiphenyl, phenylhydroquinone, and 4,4'-dihydroxydiphenyl ether The repeating units (D1) and (D2) of two different aromatic diols, in this case, the molar ratio of the two aromatic diols can be (D1)/(D2)=23/77～ 77/23, more preferably 25/75 to 75/25, still more preferably 30/70 to 70/30.

又，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較佳為(D)/(E)=95/100～100/95。若偏離此範圍的話，則有聚合度不會提高而機械強度降低的傾向。In addition, the molar ratio of the repeating structural unit derived from the aromatic diol and the repeating structural unit derived from the aromatic dicarboxylic acid is preferably (D)/(E)=95/100 to 100/95. If it deviates from this range, the degree of polymerization does not increase and the mechanical strength tends to decrease.

此外，本發明中所謂的可形成光學上異向性的熔融相，係能夠藉由例如將試料擺在高溫載台，在氮氣環境下升溫加熱，觀察試料的透射光來認定。In addition, the so-called optically anisotropic molten phase in the present invention can be confirmed by, for example, placing a sample on a high-temperature stage, heating it in a nitrogen atmosphere, and observing the transmitted light of the sample.

作為熱塑性液晶聚合物，較佳者為熔點(以下稱為Tm0 )例如在200～360℃的範圍內者，較佳為在240～350℃的範圍內者，再更佳為Tm0 為260～330℃者。此外，熔點能夠使用微差掃描熱卡計觀察熱塑性液晶聚合物樣品的熱行為來得到。即，將熱塑性液晶聚合物樣品以10℃/min的速度升溫而使其完全熔融後，將熔融物以10℃/min的速度冷卻至50℃，求出在再次以10℃/min的速度升溫後所出現的吸熱峰的位置，作為熱塑性液晶聚合物樣品的熔點。The thermoplastic liquid crystal polymer preferably has a melting point (hereinafter referred to as Tm 0 ), for example, a temperature in the range of 200 to 360°C, preferably a temperature in the range of 240 to 350°C, and more preferably a Tm 0 of 260 ~330℃. In addition, the melting point can be obtained by observing the thermal behavior of the thermoplastic liquid crystal polymer sample using a differential scanning calorimeter. That is, after the thermoplastic liquid crystal polymer sample is heated at a rate of 10°C/min to completely melt, the melt is cooled to 50°C at a rate of 10°C/min, and the temperature is increased again at a rate of 10°C/min. The position of the endothermic peak that appeared later was taken as the melting point of the thermoplastic liquid crystal polymer sample.

又，熱塑性液晶聚合物，從熔融成形性的觀點來看，例如，可以具有在(Tm0 +20)℃的剪斷速度1000/s的熔融黏度30～120Pa．s，較佳為可具有熔融黏度50～100Pa．s。In addition, the thermoplastic liquid crystal polymer, from the viewpoint of melt moldability, for example, may have a melt viscosity of 30 to 120 Pa at a shear rate of 1000/s at (Tm 0 +20)°C. s, preferably may have a melt viscosity of 50-100Pa. s.

在無損本發明的效果的範圍內，前述熱塑性液晶聚合物中可以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(polyphenylene sulfide)、聚醚醚酮、氟樹脂等熱塑性聚合物、各種添加劑、填充劑等。To the extent that the effect of the present invention is not impaired, polyethylene terephthalate, modified polyethylene terephthalate, polyolefin, polycarbonate, polyaromatic ester, and poly(ethylene terephthalate) may be added to the aforementioned thermoplastic liquid crystal polymer. Thermoplastic polymers such as amide, polyphenylene sulfide, polyether ether ketone, fluororesin, various additives, fillers, etc.

本發明的製造方法所使用的熱塑性液晶聚合物薄膜，係例如，將前述熱塑性液晶聚合物的熔融混練物進行擠出成形而得到。作為擠出成形法，可使用任意的方法，但公知的T模法、吹脹(inflation)法等在工業上是有利的。特別是在吹脹法方面，不僅對熱塑性液晶聚合物薄膜的機械軸方向(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，由於能夠在MD方向、TD方向上均勻地延伸，因此可得到控制了MD方向和TD方向上的分子配向性、介電特性等的熱塑性液晶聚合物薄膜。The thermoplastic liquid crystal polymer film used in the production method of the present invention is obtained, for example, by extrusion molding the molten kneaded product of the thermoplastic liquid crystal polymer. As the extrusion molding method, any method can be used, but the well-known T-die method, inflation method, etc. are industrially advantageous. Especially in the inflation method, stress is not only applied to the mechanical axis direction of the thermoplastic liquid crystal polymer film (hereinafter referred to as the MD direction), but also in the direction orthogonal to it (hereinafter referred to as the TD direction). It stretches uniformly in the MD and TD directions, so that a thermoplastic liquid crystal polymer film with controlled molecular orientation and dielectric properties in the MD and TD directions can be obtained.

例如，在利用T模法的擠出成形方面，可以將從T模擠出的熔融體薄片，並非僅對熱塑性液晶聚合物薄膜的MD方向而是對其和TD方向雙方同時延伸來製膜，或者可以將從T模擠出的熔融體薄片暫時在MD方向上延伸，接著在TD方向上延伸來製膜。For example, in terms of extrusion molding using the T-die method, the melt sheet extruded from the T-die can be stretched not only in the MD direction of the thermoplastic liquid crystal polymer film but in both the TD direction at the same time to form a film. Alternatively, the melt sheet extruded from the T die may be temporarily stretched in the MD direction and then stretched in the TD direction to form a film.

又，在利用吹脹法的擠出成形方面，可以對從環形模所熔融擠出的圓筒狀薄片以既定的拉延比(draw ratio)(相當於MD方向的延伸倍率)及吹脹比(blow ratio)(相當於TD方向的延伸倍率)進行延伸來製膜。In addition, in the extrusion molding by the inflation method, the cylindrical sheet melted and extruded from the ring die can be given a predetermined draw ratio (corresponding to the stretching ratio in the MD direction) and inflation ratio. (Blow ratio) (corresponding to the stretching magnification in the TD direction) is stretched to form a film.

這樣的擠出成形的延伸倍率，作為MD方向的延伸倍率(或拉延比)，例如，可以是1.0～10左右，較佳可為1.2～7左右，再更佳可為1.3～7左右。又，作為TD方向的延伸倍率(或吹脹比)，例如，可以是1.5～20左右，較佳可為2～15左右，再更佳可為2.5～14左右。The stretching ratio of such extrusion molding, as the stretching ratio (or drawing ratio) in the MD direction, may be, for example, about 1.0-10, preferably about 1.2-7, and more preferably about 1.3-7. In addition, the stretch magnification (or inflation ratio) in the TD direction may be, for example, about 1.5-20, preferably about 2-15, and more preferably about 2.5-14.

又，可以根據需要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。熱處理條件能夠根據目的適宜設定，例如，可以藉由在相對於熱塑性液晶聚合物的熔點(Tm0 )，為(Tm0 -10)℃以上(例如，(Tm0 -10)～(Tm0 +30)℃左右，較佳為(Tm0 )～(Tm0 +20)℃左右)下加熱數小時，來使熱塑性液晶聚合物薄膜的熔點(Tm)上升。此外，熱塑性液晶聚合物薄膜的熔點(Tm)能夠使用微差掃描熱卡計觀察熱塑性液晶聚合物薄膜樣品的熱行為來得到。即，求出在將熱塑性液晶聚合物薄膜樣品以10℃/min的速度升溫之際所出現的吸熱峰的位置，作為熱塑性液晶聚合物薄膜的熔點(Tm)。In addition, a known or commonly used heat treatment can be performed as needed to adjust the melting point and/or thermal expansion coefficient of the thermoplastic liquid crystal polymer film. The heat treatment conditions can be appropriately set according to the purpose. For example, it can be determined by setting the melting point (Tm 0 ) of the thermoplastic liquid crystal polymer to (Tm 0 -10)°C or higher (for example, (Tm 0 -10) to (Tm 0 + It is heated at about 30)°C, preferably (Tm 0 ) to (Tm 0 +20)°C) for several hours to increase the melting point (Tm) of the thermoplastic liquid crystal polymer film. In addition, the melting point (Tm) of the thermoplastic liquid crystal polymer film can be obtained by observing the thermal behavior of the thermoplastic liquid crystal polymer film sample using a differential scanning calorimeter. That is, the position of the endothermic peak that appears when the sample of the thermoplastic liquid crystal polymer film is heated at a rate of 10° C./min is determined as the melting point (Tm) of the thermoplastic liquid crystal polymer film.

(單面覆金屬之積層體) 本發明的製造方法所使用的單面覆金屬之積層體，係在前述熱塑性液晶聚合物薄膜的一面配設金屬層者。此外，單面覆金屬之積層體可以使用市售品，但例如，單面覆金屬之積層體的製造方法，對於熱塑性液晶聚合物薄膜，可以藉由熱壓接來使金屬箔接著作為金屬層，也可以藉由濺鍍、蒸鍍、無電解鍍敷等來使金屬層形成。從生產效率及簡便性的觀點來看，較佳為對於熱塑性液晶聚合物薄膜，藉由熱壓接來使金屬箔接著的方法。(Laminated body with single-sided metal clad) The single-sided metal-clad laminate used in the production method of the present invention has a metal layer on one side of the aforementioned thermoplastic liquid crystal polymer film. In addition, commercially available products can be used for single-sided metal-clad laminates. For example, in the production method of single-sided metal-clad laminates, for thermoplastic liquid crystal polymer films, the metal foil can be joined as a metal layer by thermocompression bonding. It is also possible to form the metal layer by sputtering, vapor deposition, electroless plating, or the like. From the viewpoint of production efficiency and simplicity, a method of bonding a metal foil by thermocompression bonding to a thermoplastic liquid crystal polymer film is preferable.

單面覆金屬之積層體可使用長條狀物。在此情況下，長條狀物可以是捲取於輥上的輥形狀，也可以是並非捲取於輥上的非輥形狀。長條狀物的長度只要能夠連續地搬送則沒有特別的限定，可以是100m以上(例如100～500m)。作為使金屬箔接著於熱塑性液晶聚合物薄膜的方法，較佳為藉由基於卷對卷方式的輥加壓或雙皮帶加壓(double belt press)，來使熱塑性液晶聚合物薄膜和金屬箔重疊並連續地進行熱壓接的方法。Long strips can be used for single-sided metal-clad laminates. In this case, the elongated object may have a roll shape wound on a roll, or a non-roll shape that is not wound on a roll. The length of the elongated article is not particularly limited as long as it can be continuously conveyed, and it may be 100 m or more (for example, 100 to 500 m). As a method for adhering the metal foil to the thermoplastic liquid crystal polymer film, it is preferable to overlap the thermoplastic liquid crystal polymer film and the metal foil by roll pressing or double belt press based on a roll-to-roll method. And continuous thermal compression bonding method.

單面覆金屬之積層體的熱塑性液晶聚合物薄膜和金屬層的剝離強度，可以是0.6N/mm以上，較佳可為0.8N/mm以上，更佳可為1.0N/mm以上。又，單面覆金屬之積層體的熱塑性液晶聚合物薄膜和金屬層的剝離強度的上限沒有特別的限制，但例如，可以是2.0N/mm以下。此處，剝離強度係參考JIS C 5016-1994(90°方向撕下)所測定的剝離強度(撕下強度)。The peel strength of the thermoplastic liquid crystal polymer film and the metal layer of the single-sided metal-clad laminate may be 0.6 N/mm or more, preferably 0.8 N/mm or more, and more preferably 1.0 N/mm or more. In addition, the upper limit of the peel strength of the thermoplastic liquid crystal polymer film and the metal layer of the single-sided metal-clad laminate is not particularly limited, but it may be 2.0 N/mm or less, for example. Here, the peel strength refers to the peel strength (tear strength) measured with reference to JIS C 5016-1994 (90° direction tearing).

本發明的製造方法，係獨立地進行單面覆金屬之積層體的準備(例如，利用熱塑性液晶聚合物薄膜及金屬箔的熱壓接之單面覆金屬之積層體的製造)和單面覆金屬之積層體的賦形處理(即，與金屬賦形薄片的熱壓接)。因此，能夠在賦形處理之際避免高溫下的加熱加壓，其結果，能夠抑制覆金屬之積層體的尺寸變化，同時能夠抑制因各材料的熱膨脹的差異所造成的皺摺的產生。The manufacturing method of the present invention is to independently prepare a single-sided metal-clad laminate (for example, the production of a single-sided metal-clad laminate by thermocompression bonding of a thermoplastic liquid crystal polymer film and a metal foil) and a single-sided laminate The forming process of the metal laminate (ie, the thermal compression bonding with the metal forming sheet). Therefore, heating and pressing at high temperatures can be avoided during the shaping process. As a result, the dimensional change of the metal-clad laminate can be suppressed, and the generation of wrinkles due to the difference in thermal expansion of each material can be suppressed.

作為形成金屬層的金屬，沒有特別的限制，例如，可以是金、銀、銅、鐵、錫、鎳、鋁、鉻或它們的合金金屬等。在使金屬箔接著作為金屬層的情況下，例如，可以是以前述金屬所形成的金屬箔，從導電性、操作性、及成本等的觀點來看，較佳為銅箔、不銹鋼箔。作為銅箔，能夠使用藉由壓延法、電解法所製造者。又，對於金屬箔，可以在無損本發明的覆金屬之積層體的高頻特性的範圍內，進行通常所施加的粗化處理等的表面處理。The metal forming the metal layer is not particularly limited. For example, it may be gold, silver, copper, iron, tin, nickel, aluminum, chromium, or their alloy metals. When the metal foil is connected as a metal layer, for example, it may be a metal foil formed of the aforementioned metal. From the viewpoints of conductivity, handleability, and cost, copper foil and stainless steel foil are preferred. As the copper foil, those manufactured by a rolling method or an electrolytic method can be used. In addition, the metal foil can be subjected to surface treatment such as roughening treatment that is usually applied within a range that does not impair the high-frequency characteristics of the metal-clad laminate of the present invention.

金屬層的厚度，能夠根據需要適宜設定，例如，可以是1～50μm左右，更佳可為9～35μm的範圍內。The thickness of the metal layer can be appropriately set according to needs, and for example, it may be about 1-50 μm, and more preferably may be in the range of 9-35 μm.

(金屬賦形薄片) 本發明的製造方法所使用的金屬賦形薄片係以金屬所形成的薄片，至少一表面為賦形面。金屬賦形薄片可使用長條狀物。長條狀物可以是捲取於輥上的輥形狀，也可以是並非捲取於輥上的非輥形狀。長條狀物的長度只要能夠連續地搬送則沒有特別的限定，可以是100m以上(例如100～500m)。(Metal shaped flakes) The metal shaped flake used in the manufacturing method of the present invention is a flake formed of metal, and at least one surface is a shaped surface. Long strips can be used for metal-shaped flakes. The elongated object may have a roll shape wound on a roll, or a non-roll shape that is not wound on a roll. The length of the elongated article is not particularly limited as long as it can be continuously conveyed, and it may be 100 m or more (for example, 100 to 500 m).

金屬賦形薄片較佳為至少一表面具有賦形面的金屬箔。作為形成金屬賦形薄片的金屬，沒有特別的限制，例如，可以是金、銀、銅、鐵、錫、鎳、鋁、鉻或它們的合金金屬等。在使用金屬箔的情況下，例如，可以是以前述金屬所形成的金屬箔，從操作性、及成本等的觀點來看，較佳為銅箔、不銹鋼箔。作為這些金屬箔，能夠使用藉由壓延法、電解法所製造者，為了得到所要的賦形面可以進行粗化處理等的表面處理。The metal shaped flake is preferably a metal foil with a shaped surface on at least one surface. There is no particular limitation on the metal forming the metal-shaped flakes. For example, it may be gold, silver, copper, iron, tin, nickel, aluminum, chromium, or their alloy metals. When a metal foil is used, for example, it may be a metal foil formed of the aforementioned metal, and from the viewpoints of handleability, cost, etc., copper foil and stainless steel foil are preferred. As these metal foils, those manufactured by a rolling method or an electrolytic method can be used, and surface treatments such as roughening treatment can be performed in order to obtain a desired shaped surface.

又，從抑制因在熱壓接時的熱膨脹所造成的翹曲的觀點來看，形成金屬賦形薄片的金屬較佳為具有與形成單面覆金屬之積層體的金屬層的金屬相同程度的熱膨脹係數的材質(例如，相同種類的金屬)。特別是，較佳為金屬層及金屬賦形薄片皆為銅箔。In addition, from the viewpoint of suppressing warpage due to thermal expansion during thermocompression bonding, the metal forming the metal-shaped flakes preferably has the same level as the metal forming the metal layer of the single-sided metal-clad laminate The material with the coefficient of thermal expansion (for example, the same type of metal). In particular, it is preferable that both the metal layer and the metal shaped sheet are copper foil.

金屬賦形薄片的賦形面，從使電路加工中的與接合薄片的層間接著性提高的觀點來看，例如，表面粗糙度(Rz)可以是1.0～7.0μm。本發明的製造方法，可以轉印金屬賦形薄片的賦形面的表面粗糙度(Rz)，在熱塑性液晶聚合物薄膜的表面形成與金屬賦形薄片相同的表面粗糙度(Rz)的凹凸。又，金屬賦形薄片的賦形面的表面粗糙度(Rz)較佳可為1.5～5.5μm，更佳可為2.0～4.5μm。此處，在本發明中，所謂的表面粗糙度(Rz)，係使用接觸式表面粗糙度計，顯示參考JIS B 0601-1994測定的十點平均粗糙度，在基準長度的粗糙度曲線中，表示從最高的山頂起依序到第5高為止的山高的平均、和從最深的谷底起依序到第5深為止的谷深的平均的和。The shaped surface of the metal shaped sheet may have a surface roughness (Rz) of 1.0 to 7.0 μm from the viewpoint of improving the adhesion to the layer of the bonding sheet during circuit processing. The production method of the present invention can transfer the surface roughness (Rz) of the shaped surface of the metal shaped flake to form irregularities with the same surface roughness (Rz) as the metal shaped flake on the surface of the thermoplastic liquid crystal polymer film. In addition, the surface roughness (Rz) of the shaped surface of the metal shaped flake is preferably 1.5 to 5.5 μm, more preferably 2.0 to 4.5 μm. Here, in the present invention, the so-called surface roughness (Rz) is a contact-type surface roughness meter that shows the ten-point average roughness measured with reference to JIS B 0601-1994. In the roughness curve of the reference length, It represents the sum of the average of the mountain heights from the highest mountain top to the fifth highest, and the average of the valley depths from the deepest valley bottom to the fifth deepest.

從在熱壓接後使金屬賦形薄片的剝離變得容易的觀點來看，可以對金屬賦形薄片的賦形面施加脫模處理。作為脫模處理的方法，例如，可以是在金屬賦形薄片的賦形面塗布脫模劑以設置脫模層的方法。作為脫模劑，例如，可舉出：矽氧系樹脂、氟系樹脂等。From the viewpoint of facilitating the peeling of the metal shaped sheet after thermocompression bonding, a mold release treatment may be applied to the shaped surface of the metal shaped sheet. As a method of the mold release treatment, for example, a method of applying a mold release agent to the shaped surface of a metal shaped sheet to provide a mold release layer. As a mold release agent, a silicone resin, a fluorine resin, etc. are mentioned, for example.

金屬賦形薄片的厚度能夠根據需要適宜設定，例如，可以是5～50μm左右，更佳可為9～35μm的範圍內。The thickness of the metal-shaped flakes can be appropriately set as required, and for example, it may be about 5-50 μm, and more preferably may be in the range of 9-35 μm.

(脫模緩衝材) 就本發明的製造方法而言，可以根據需要而使用脫模緩衝材。脫模緩衝材可以使用長條狀物。長條狀物可以是捲取於輥上的輥形狀，也可以是並非捲取於輥上的非輥形狀。長條狀物的長度只要能夠連續地搬送則沒有特別的限定，可以是100m以上(例如100～500m)。(Release buffer material) In the production method of the present invention, a release buffer material can be used as needed. Long strips can be used as the release buffer material. The elongated object may have a roll shape wound on a roll, or a non-roll shape that is not wound on a roll. The length of the elongated article is not particularly limited as long as it can be continuously conveyed, and it may be 100 m or more (for example, 100 to 500 m).

作為脫模緩衝材，只要能夠在熱壓接後從鄰接的被接著體剝離，具有耐熱性，具有緩衝性則沒有特別的限定，可舉出：非熱塑性的聚醯亞胺薄膜、聚芳醯胺薄膜、Teflon(註冊商標)薄膜等的耐熱性樹脂薄膜；耐熱性複合薄膜(例如，包含複數個耐熱性樹脂薄膜的複合薄膜、包含金屬箔和耐熱性樹脂薄膜的複合薄膜)；以耐熱性纖維(例如，耐熱性樹脂纖維、金屬纖維)所構成的耐熱性不織布；及在至少一面具備脫模層(例如，矽氧系樹脂、氟系樹脂等的脫模劑的塗布層)的金屬箔(例如，鋁箔、不銹鋼箔等)等。這些脫模緩衝材可以單獨使用或組合二種以上使用。此外，從使熱壓接後的與被接著體的剝離變得容易的觀點來看，可以對脫模緩衝材(例如，耐熱性樹脂薄膜、耐熱性複合薄膜、或耐熱性不織布)施加脫模處理。作為脫模處理的方法，可舉出上述的方法。 這些脫模緩衝材之中，從耐熱性及緩衝性(彈回彈性)優異的觀點來看，較佳為耐熱性樹脂薄膜、耐熱性複合薄膜、及耐熱性不織布。The release buffer material is not particularly limited as long as it can be peeled from the adjacent adherend after thermocompression bonding, has heat resistance, and has cushioning properties. Examples include non-thermoplastic polyimide films and polyarylenes. Heat-resistant resin films such as amine films, Teflon (registered trademark) films, etc.; heat-resistant composite films (for example, composite films containing a plurality of heat-resistant resin films, composite films containing metal foil and heat-resistant resin films); Heat-resistant non-woven fabric composed of fibers (for example, heat-resistant resin fibers, metal fibers); and metal foil provided with a release layer (for example, a coating layer of a release agent such as silicone resin, fluorine resin, etc.) on at least one side (For example, aluminum foil, stainless steel foil, etc.) and so on. These release buffer materials can be used alone or in combination of two or more kinds. In addition, from the viewpoint of facilitating the peeling from the adherend after thermocompression bonding, the release buffer material (for example, a heat-resistant resin film, a heat-resistant composite film, or a heat-resistant non-woven fabric) can be released. deal with. As a method of mold release treatment, the above-mentioned method can be mentioned. Among these release cushioning materials, from the viewpoint of excellent heat resistance and cushioning properties (resilient resilience), heat-resistant resin films, heat-resistant composite films, and heat-resistant non-woven fabrics are preferred.

脫模緩衝材的厚度能夠根據需要適宜設定，例如，可以是5～300μm左右，較佳可為10～150μm，更佳可為25～75μm的範圍內。The thickness of the release buffer material can be appropriately set according to needs, for example, it may be about 5 to 300 μm, preferably 10 to 150 μm, and more preferably 25 to 75 μm.

脫模緩衝材的至少一面的表面粗糙度(Rz)，從使熱壓接後的與被接著體(單面覆金屬之積層體或金屬賦形薄片)的剝離變得容易的觀點來看，可以是2.0μm以下，較佳可為1.8μm以下，更佳可為1.5μm以下。又，脫模緩衝材的至少一面的表面粗糙度(Rz)的下限沒有特別的限定，例如，可以是0.05μm以上，較佳可為0.10μm以上，更佳可為0.15μm以上。The surface roughness (Rz) of at least one side of the release buffer material, from the viewpoint of facilitating the peeling from the adherend (single-side metal-clad laminate or metal-shaped sheet) after thermocompression bonding, It may be 2.0 μm or less, preferably 1.8 μm or less, and more preferably 1.5 μm or less. In addition, the lower limit of the surface roughness (Rz) of at least one surface of the release buffer material is not particularly limited. For example, it may be 0.05 μm or more, preferably 0.10 μm or more, and more preferably 0.15 μm or more.

(覆金屬之積層體的製造方法) 本發明的覆金屬之積層體的製造方法，至少具備： 準備在熱塑性液晶聚合物薄膜的一面接著金屬層的長條狀的單面覆金屬之積層體(A)、及至少一表面為賦形面的長條狀的金屬賦形薄片(B)的步驟；和 以前述單面覆金屬之積層體(A)的熱塑性液晶聚合物薄膜面和前述金屬賦形薄片(B)的賦形面接觸的方式配置，朝向一對加壓輥(r1 , r2 )導入的熱壓接步驟。(Method for manufacturing metal-clad laminate) The method for manufacturing a metal-clad laminate of the present invention at least includes: preparing a long strip-shaped, single-sided, metal-clad laminate with a metal layer attached to one side of a thermoplastic liquid crystal polymer film ( A), and a step of forming a long metal shaped sheet (B) with at least one surface as a shaped surface; and using the thermoplastic liquid crystal polymer film surface of the aforementioned single-sided metal-clad laminate (A) and the aforementioned metal The shaped sheet (B) is arranged in such a way that the shaping surface is in contact, and is directed toward the thermocompression bonding step of a pair of pressure rollers (r 1 , r 2 ).

單面覆金屬之積層體(A)及金屬賦形薄片(B)，只要能夠以長條狀物的形式導入至加壓輥則沒有特別的限定，例如，可以直接搬送在熱壓接步驟的上游製造的長條狀物來使用，也可以準備捲出輥。 在直接使用在上游製造的長條狀物的情況下，例如，可以將熱塑性液晶聚合物薄膜和金屬箔重疊並連續地進行熱壓接來製造單面覆金屬之積層體(A)，不進行捲取地，直接在搬送方向的下游，與另外準備的金屬賦形薄片(B)重疊。在此情況下，以單面覆金屬之積層體(A)的熱塑性液晶聚合物薄膜面和金屬賦形薄片(B)的賦形面接觸的方式進行配置來重疊。 在準備捲出輥的情況下，各捲出輥，係以如下的方向配置：單面覆金屬之積層體(A)和金屬賦形薄片(B)鄰接，且單面覆金屬之積層體(A)的熱塑性液晶聚合物薄膜面和金屬賦形薄片(B)的賦形面接觸。The single-sided metal-clad laminate (A) and the metal shaped sheet (B) are not particularly limited as long as they can be introduced to the pressure roller in the form of a strip. For example, they can be directly transported in the thermocompression bonding step. It can be used as a long strip manufactured upstream, and a roll-out roll can also be prepared. In the case of directly using the elongated article manufactured upstream, for example, the thermoplastic liquid crystal polymer film and the metal foil can be overlapped and continuously thermocompression bonded to produce a single-sided metal-clad laminate (A). The winding place is directly downstream in the conveying direction and overlaps with the separately prepared metal shaped sheet (B). In this case, the surface of the thermoplastic liquid crystal polymer film of the single-sided metal-clad laminate (A) and the shaped surface of the metal shaped sheet (B) are arranged and overlapped. In the case of preparing the unwinding roll, each unwinding roll is arranged in the following direction: the single-sided metal-clad laminate (A) and the metal shaped sheet (B) are adjacent to each other, and the single-sided metal-clad laminate ( The thermoplastic liquid crystal polymer film surface of A) is in contact with the shaped surface of the metal shaped sheet (B).

本發明的覆金屬之積層體的製造方法， 可以在準備步驟中，進一步準備長條狀的脫模緩衝材(C)， 在熱壓接步驟中，在前述單面覆金屬之積層體(A)及前述金屬賦形薄片(B)的未接觸側中的至少一側配置前述脫模緩衝材(C)，朝向一對加壓輥(r1 , r2 )導入。In the method of manufacturing a metal-clad laminate of the present invention, in the preparation step, a strip-shaped release buffer material (C) may be further prepared. In the thermocompression bonding step, the single-sided metal-clad laminate (A ) And at least one side of the non-contact side of the metal shaped sheet (B), the release buffer material (C) is arranged, and the release buffer material (C) is introduced toward a pair of pressure rollers (r 1 , r 2 ).

藉由使用脫模緩衝材(C)，由於脫模緩衝材(C)發揮緩衝的作用，因此能夠在單面覆金屬之積層體(A)和金屬賦形薄片(B)的熱壓接中分散來自加壓輥的壓力，能夠提高金屬賦形薄片(B)的賦形面對熱塑性液晶聚合物薄膜的表面的轉印性。例如，在加壓輥(r1 , r2 )的加熱溫度高的情況、或加壓壓力低的情況、加壓時間短的情況下，藉由脫模緩衝材(C)的存在，使壓力的均勻性提高的效果高。By using the release buffer material (C), since the release buffer material (C) plays a buffering role, it can be used in the thermal compression bonding of the single-sided metal-clad laminate (A) and the metal shaped sheet (B) Dispersing the pressure from the pressure roller can improve the transferability of the shaped surface of the metal shaped sheet (B) to the surface of the thermoplastic liquid crystal polymer film. For example, when the heating temperature of the pressure rollers (r 1 , r 2 ) is high, or the pressure is low, or the pressure time is short, the presence of the release buffer material (C) makes the pressure The uniformity improvement effect is high.

在使用脫模緩衝材(C)的情況下，在單面覆金屬之積層體(A)及金屬賦形薄片(B)的未接觸的面中，脫模緩衝材(C)可以以與單面覆金屬之積層體(A)及/或金屬賦形薄片(B)鄰接的方式配置。In the case of using the release buffer material (C), in the non-contact surface of the single-sided metal-clad laminate (A) and the metal shaped sheet (B), the release buffer material (C) can be combined with the single The metal-clad laminate (A) and/or the metal shaped sheet (B) are arranged in a manner adjacent to each other.

例如，可以將脫模緩衝材(C)以與單面覆金屬之積層體(A)的金屬層鄰接的方式配置，覆金屬之積層體係以至少(C)/(A)/(B)的順序形成的方式進行熱壓接。藉由使脫模緩衝材(C)與單面覆金屬之積層體(A)的金屬層側鄰接，脫模緩衝材(C)發揮抑制熱從單面覆金屬之積層體(A)側傳來的隔熱材的作用，因此能夠防止熱塑性液晶聚合物薄膜被從金屬層側無謂地加熱，抑制液晶聚合物分子會容易進行配向的情形。For example, the release buffer material (C) can be arranged adjacent to the metal layer of the single-sided metal-clad laminate (A), and the metal-clad laminate system has at least (C)/(A)/(B) Thermal compression bonding is performed in sequential formation. By making the release buffer material (C) adjacent to the metal layer side of the single-sided metal-clad laminate (A), the release buffer material (C) suppresses heat transfer from the single-sided metal-clad laminate (A) side The function of the coming heat insulating material can therefore prevent the thermoplastic liquid crystal polymer film from being unnecessarily heated from the metal layer side, and suppress the situation in which the liquid crystal polymer molecules are easily aligned.

又，在熱壓接步驟中，加壓輥(r1 , r2 )中的至少一者係經加熱的加壓輥(hr)，可以以成為從該經加熱的加壓輥(hr)起(hr)/(B)/(A)的順序，或者是，在使用脫模緩衝材(C)的情況下，(hr)/(B)/(A)/(C)或者(hr)/(C)/(B)/(A)的順序的方式予以導入。藉由從金屬賦形薄片(B)側加熱單面覆金屬之積層體(A)，能夠效率佳地將熱傳遞至單面覆金屬之積層體(A)的施加賦形處理的熱塑性液晶聚合物薄膜面，因此能夠調整成防止熱塑性液晶聚合物薄膜被無謂地加熱的加熱加壓條件，能夠有效率地進行賦形處理。Furthermore, in the thermocompression bonding step, at least one of the pressure rollers (r 1 , r 2 ) is a heated pressure roller (hr), and it can be set from the heated pressure roller (hr) (hr)/(B)/(A), or, in the case of using release buffer material (C), (hr)/(B)/(A)/(C) or (hr)/ (C)/(B)/(A) order to be introduced. By heating the single-sided metal-clad laminate (A) from the metal-shaped sheet (B) side, the heat can be efficiently transferred to the single-sided metal-clad laminate (A) by applying shaping treatment to thermoplastic liquid crystal polymerization Therefore, it is possible to adjust the heating and pressing conditions to prevent the thermoplastic liquid crystal polymer film from being unnecessarily heated, so that the shaping treatment can be efficiently performed.

本發明的覆金屬之積層體的製造方法，可以分別準備複數個長條狀的單面覆金屬之積層體(A)及長條狀的金屬賦形薄片(B)，製造複數個覆金屬之積層體。The method of manufacturing a metal-clad laminate of the present invention can prepare a plurality of long single-sided metal-clad laminates (A) and long metal-shaped flakes (B) to produce a plurality of metal-clad laminates. Layered body.

在製造複數個覆金屬之積層體的情況下，可以在熱壓接步驟中，將脫模緩衝材(C)重疊而導入於複數組的包含單面覆金屬之積層體(A)及金屬賦形薄片(B)的積層體之間。In the case of manufacturing a plurality of metal-clad laminates, in the thermocompression bonding step, the release buffer material (C) can be superimposed and introduced into the plurality of single-sided metal-clad laminates (A) and metal forming Between the laminates of the shaped flakes (B).

又，在製造複數個覆金屬之積層體的情況下，可以在熱壓接步驟中，以與一對加壓輥(r1 , r2 )中的至少一個加壓輥相接的方式，將脫模緩衝材(C)重疊而導入。In addition, in the case of manufacturing a plurality of metal-clad laminates, in the thermocompression bonding step, at least one of the pair of pressure rollers (r 1 , r 2 ) may be in contact with The release buffer material (C) is superimposed and introduced.

此處，複數個單面覆金屬之積層體(A)可以相同也可以不同。又，複數個金屬賦形薄片(B)可以相同也可以不同。Here, a plurality of single-sided metal-clad laminates (A) may be the same or different. In addition, a plurality of metal-shaped flakes (B) may be the same or different.

又，進一步地，所得到的複數個覆金屬之積層體可以相同也可以不同。Furthermore, the obtained plurality of metal-clad laminates may be the same or different.

所得到的覆金屬之積層體(在熱塑性液晶聚合物薄膜的一面積層金屬層，在另一面具備金屬賦形薄片的覆金屬之積層體)，係熱塑性液晶聚合物薄膜和金屬賦形薄片之間的剝離強度(P1)可以是0.5N/mm以下，較佳可為0.2N/mm以下，更佳可為0.1N/mm以下。 又，所得到的覆金屬之積層體，係熱塑性液晶聚合物薄膜和金屬層之間的剝離強度(P2)，例如，可以是0.6N/mm以上，較佳可為0.8N/mm以上，更佳可為1.0N/mm以上。又，熱塑性液晶聚合物薄膜和金屬層的剝離強度的上限沒有特別的限制，可以是2.0N/mm以下。 又，所得到的覆金屬之積層體，係將熱塑性液晶聚合物薄膜和金屬賦形薄片之間的剝離強度(P1)除以熱塑性液晶聚合物薄膜和金屬層之間的剝離強度(P2)的值(P1/P2)可以是0.6以下，較佳可為0.4以下，更佳可為0.2以下。The obtained metal-clad laminate (a metal-clad laminate with a metal layer on one area of the thermoplastic liquid crystal polymer film and a metal-shaped sheet on the other side) is between the thermoplastic liquid crystal polymer film and the metal-shaped sheet The peel strength (P1) can be 0.5 N/mm or less, preferably 0.2 N/mm or less, and more preferably 0.1 N/mm or less. In addition, the obtained metal-clad laminate is the peel strength (P2) between the thermoplastic liquid crystal polymer film and the metal layer. For example, it may be 0.6 N/mm or more, preferably 0.8 N/mm or more, and more Preferably, it is 1.0 N/mm or more. In addition, the upper limit of the peel strength between the thermoplastic liquid crystal polymer film and the metal layer is not particularly limited, and it may be 2.0 N/mm or less. In addition, the obtained metal-clad laminate is obtained by dividing the peel strength (P1) between the thermoplastic liquid crystal polymer film and the metal shaped sheet by the peel strength (P2) between the thermoplastic liquid crystal polymer film and the metal layer The value (P1/P2) may be 0.6 or less, preferably 0.4 or less, and more preferably 0.2 or less.

又，所得到的覆金屬之積層體，係將熱塑性液晶聚合物薄膜的厚度方向之中金屬層側的配向度f(f1)除以金屬賦形薄片側(或賦形處理面側)的配向度f(f2)的值(f1/f2)可以是1.05～1.40，較佳可為1.10～1.35，更佳可為1.15～1.30。在本發明中，在單面覆金屬之積層體(A)和金屬賦形薄片(B)的熱壓接步驟中，也許由於能夠避免在無謂的高溫(例如，熱塑性液晶聚合物薄膜的熔點以上)下進行加熱加壓，從而能夠抑制金屬賦形薄片側的分子配向變化，因此能夠將熱塑性液晶聚合物薄膜的厚度方向的配向度設為特定的關係。此處，熱塑性液晶聚合物薄膜的厚度方向之中所謂的金屬層側的配向度，係指在將熱塑性液晶聚合物薄膜在厚度方向上分成兩等分的情況下的與金屬層相接的側的部分的配向度，熱塑性液晶聚合物薄膜的厚度方向之中所謂的金屬賦形薄片側(賦形處理面側)的配向度，係指在將熱塑性液晶聚合物薄膜在厚度方向上分成兩等分的情況下的與金屬賦形薄片相接的側(經賦形處理的面側)的部分的配向度。In addition, the obtained metal-clad laminate is obtained by dividing the degree of alignment f(f1) on the metal layer side in the thickness direction of the thermoplastic liquid crystal polymer film by the alignment on the metal shaped sheet side (or the shaped surface side) The value (f1/f2) of the degree f(f2) may be 1.05 to 1.40, preferably 1.10 to 1.35, and more preferably 1.15 to 1.30. In the present invention, in the thermocompression bonding step of the single-sided metal-clad laminate (A) and the metal shaped sheet (B), it may be possible to avoid unnecessary high temperatures (for example, the melting point of the thermoplastic liquid crystal polymer film). Heating and pressing under) can suppress the change in molecular alignment on the metal-shaped sheet side, and therefore the degree of alignment in the thickness direction of the thermoplastic liquid crystal polymer film can be set in a specific relationship. Here, the degree of alignment of the metal layer side in the thickness direction of the thermoplastic liquid crystal polymer film refers to the side contacting the metal layer when the thermoplastic liquid crystal polymer film is divided into two equal parts in the thickness direction. The degree of alignment of the portion of the thermoplastic liquid crystal polymer film in the thickness direction of the so-called metal-shaped sheet side (shaping treatment surface side) refers to the degree of division of the thermoplastic liquid crystal polymer film into two in the thickness direction The degree of alignment of the part on the side (surface side subjected to the shaping treatment) that is in contact with the metal shaped sheet in the case of dividing.

此處，所謂的配向度f，係指提供高分子的結晶區域的配向程度的指標，依以下的方式算出。配向度f，能夠使用理學電機製旋轉對陰極X線繞射裝置Ru-200，X線輸出使用電壓40kV、電流100mA、靶材CuKα(λ=1.5405A)並依以下的方式進行測定。結晶配向的變化能夠藉由廣角X線照片來求出。首先，在MD方向上切出將覆金屬之積層體的金屬賦形薄片剝離，將金屬層進行蝕刻處理以去除所得到的薄膜，安裝於樣品支架，使X線從Edge方向入射，將繞射圖像曝光於成像板。然後，能夠將所得到的繞射圖像轉換為配向分布曲線，從繞射強度對圓周方向β角的曲線的波峰的半高寬H，由以下的公式(1)算出簡便的配向度f。 f=(180-H)/180   (1) 式中，H為半高寬。 在熱塑性液晶聚合物薄膜中的金屬層側和金屬賦形薄片側(賦形處理面側)兩處，進行配向度f的測定。 又，半高寬H，可以是將基於廣角X線繞射測定的繞射角2θ=15°～30°(例如，約20°附近((110)面))進行圓環積分所得到的強度分布的波峰的半高寬。Here, the degree of alignment f refers to an index that provides the degree of alignment of the crystal regions of the polymer, and is calculated in the following manner. The degree of orientation f can be measured by using the Rigaku Electric mechanism to rotate the cathode X-ray diffraction device Ru-200. The X-ray output uses a voltage of 40kV, a current of 100mA, and a target material of CuKα (λ=1.5405A), and can be measured in the following way. The change in crystal orientation can be determined from a wide-angle radiograph. First, cut out in the MD direction and peel off the metal shaped sheet of the metal-clad laminate. The metal layer is etched to remove the resulting thin film, and it is mounted on the sample holder. X-rays are incident from the Edge direction and diffracted. The image is exposed to the imaging plate. Then, the obtained diffraction image can be converted into an alignment distribution curve, and a simple alignment degree f can be calculated from the following formula (1) from the half-height width H of the peak of the curve of the diffraction intensity versus the β angle in the circumferential direction. f=(180-H)/180 (1) In the formula, H is the half-height width. The measurement of the degree of alignment f was performed at two places on the metal layer side and the metal shaped sheet side (shaping treatment surface side) in the thermoplastic liquid crystal polymer film. In addition, the half-height width H may be the intensity obtained by performing ring integration of the diffraction angle 2θ=15°-30° (for example, around 20° ((110) plane)) based on the wide-angle X-ray diffraction measurement The half-height width of the peak of the distribution.

以下，一邊參照圖式一邊說明具體的實施形態。圖1係供說明基於第1實施形態的覆金屬之積層體的製造方法用的側面示意圖。 如圖1所示，第1實施形態中，係在一對加壓輥(r1 , r2 )的上游側，準備：將單面覆金屬之積層體(A)捲出的單面覆金屬之積層體捲出輥11、及將金屬賦形薄片(B)捲出的金屬賦形薄片捲出輥12。Hereinafter, specific embodiments will be described with reference to the drawings. Fig. 1 is a schematic side view for explaining a method of manufacturing a metal-clad laminate according to the first embodiment. As shown in Figure 1, in the first embodiment, on the upstream side of a pair of pressure rollers (r 1 , r 2 ), prepare: a single-sided metal-clad laminate (A) rolled out The laminated body roll-out roll 11 and the metal-shaped sheet roll-out roll 12 that rolls out the metal-shaped sheet (B).

此處，第1實施形態中，係以單面覆金屬之積層體(A)及金屬賦形薄片(B)在一對加壓輥(r1 , r2 )間成為(r1 )/(A)/(B)/(r2 )的順序的方式，配置各捲出輥。Here, in the first embodiment, the single-sided metal-clad laminate (A) and the metal shaped sheet (B) are formed between a pair of pressure rollers (r 1 , r 2 ) as (r 1 )/( A)/(B)/(r 2 ) is arranged in the order of each unwinding roller.

具體而言，在一對加壓輥(r1 , r2 )的上游側，以單面覆金屬之積層體(A)的熱塑性液晶聚合物薄膜面和金屬賦形薄片(B)的賦形面接觸的方式，配置單面覆金屬之積層體捲出輥11及金屬賦形薄片捲出輥12。Specifically, on the upstream side of a pair of pressure rollers (r 1 , r 2 ), the thermoplastic liquid crystal polymer film surface of the single-sided metal-clad laminate (A) and the metal shaped sheet (B) are shaped In the surface contact method, a single-sided metal-clad laminate unwinding roll 11 and a metal shaped sheet unwinding roll 12 are arranged.

如圖1所示，相對於一對加壓輥(r1 , r2 )，配置各捲出輥後，如箭頭方向所示，從各捲出輥捲出單面覆金屬之積層體(A)、及金屬賦形薄片(B)，相對於一對加壓輥(r1 , r2 )，導入於由箭頭所示的MD方向(或層疊方向)上，在一對加壓輥(r1 , r2 )中予以熱壓接，形成覆金屬之積層體(D)((A)/(B))。 As shown in Fig. 1 , after disposing each unwinding roller with respect to a pair of pressure rollers (r 1, r 2 ), as shown in the arrow direction, a single-sided metal-clad laminate (A ), and the metal shaped sheet (B), with respect to a pair of pressure rollers (r 1 , r 2 ), introduced in the MD direction (or lamination direction) indicated by the arrow, on the pair of pressure rollers (r 1 , r 2 ) are thermally compressed to form a metal-clad laminate (D)((A)/(B)).

在一對加壓輥(r1 , r2 )中，將單面覆金屬之積層體(A)、及金屬賦形薄片(B)依此順序重疊而導入，在既定的加熱溫度下，施加壓力。本發明的製造方法中，係直接使用所準備的單面覆金屬之積層體(A)來製造，因此能夠在與金屬賦形薄片(B)的熱壓接步驟中，避免在無謂的高溫(例如，熱塑性液晶聚合物薄膜的熔點以上)下進行加熱加壓。其結果，能夠抑制覆金屬之積層體的尺寸變化，同時能夠抑制因各材料的熱膨脹的差異所造成的皺摺的產生，進一步地，能夠使單面覆金屬之積層體(A)的熱塑性液晶聚合物薄膜面和金屬賦形薄片(B)的賦形面的剝離性提高。In a pair of pressure rollers (r 1 , r 2 ), the single-sided metal-clad laminate (A) and the metal shaped sheet (B) are superimposed and introduced in this order, and applied at a predetermined heating temperature pressure. In the manufacturing method of the present invention, the prepared single-sided metal-clad laminate (A) is used as it is to manufacture. Therefore, it is possible to avoid unnecessary high temperatures during the thermocompression bonding step with the metal shaped sheet (B). For example, heating and pressing are performed at the melting point of the thermoplastic liquid crystal polymer film or higher). As a result, the dimensional change of the metal-clad laminate can be suppressed, and the generation of wrinkles caused by the difference in thermal expansion of each material can be suppressed. Furthermore, the thermoplastic liquid crystal of the single-sided metal-clad laminate (A) can be made The releasability of the polymer film surface and the shaped surface of the metal shaped sheet (B) is improved.

作為加壓輥，能夠使用公知的加熱加壓裝置，例如，可舉出：金屬輥、橡膠輥、樹脂被覆金屬輥等。一對加壓輥(r1 , r2 )係彼此可以使用相同者，也可以使用不同者。例如，從提高加熱的效率的觀點來看，加壓輥(r1 )可以是金屬輥，又，加壓輥(r2 )可以與加壓輥(r1 )一樣而為金屬輥，也可以是橡膠輥或樹脂被覆金屬輥。As the pressure roller, a known heating and pressing device can be used, and examples thereof include metal rollers, rubber rollers, and resin-coated metal rollers. The pair of pressure rollers (r 1 , r 2 ) may be the same or different. For example, from the viewpoint of improving heating efficiency, the pressure roller (r 1 ) may be a metal roller, and the pressure roller (r 2 ) may be a metal roller like the pressure roller (r 1 ), or It is a rubber roller or a resin-coated metal roller.

又，一對加壓輥(r1 , r2 )可以僅加熱其中一個，也可以雙方都加熱。在雙方都加熱的情況下，加壓輥(r1 , r2 )的各加熱溫度彼此可以相同也可以不同。例如，較佳為配設在金屬賦形薄片(B)側的加壓輥係溫度高者，在如圖1所示的第1實施形態的情況下，配設在金屬賦形薄片(B)側的加壓輥(r2 )係加熱溫度可以比加壓輥(r1 )高。在該情況下，例如，藉由金屬賦形薄片(B)所相接的加壓輥(r2 )的加熱溫度較高，能夠將熱從金屬賦形薄片(B)朝向單面覆金屬之積層體(A)的熱塑性液晶聚合物薄膜面(施加賦形處理的面)側傳遞，因此可以實現有效率地施加賦形處理，同時能夠抑制覆金屬之積層體的尺寸變化。在加壓輥(r2 )係加熱溫度比加壓輥(r1 )高的情況下，例如，加壓輥(r2 )的加熱溫度和加壓輥(r1 )的加熱溫度的溫度差可以是20～200℃，較佳可為25～150℃，更佳可為30～100℃。In addition, the pair of pressure rollers (r 1 , r 2 ) may heat only one of them, or both of them may be heated. When both of them are heated, the heating temperatures of the pressure rollers (r 1 , r 2 ) may be the same or different from each other. For example, it is preferable to arrange the pressure roller system on the side of the metal shaped sheet (B) with a higher temperature. In the case of the first embodiment as shown in FIG. 1, it is arranged on the metal shaped sheet (B). The heating temperature of the pressure roller (r 2 ) on the side may be higher than that of the pressure roller (r 1 ). In this case, for example, the heating temperature of the pressure roller (r 2 ) in contact with the metal-shaped sheet (B) is relatively high, so that the heat can be transferred from the metal-shaped sheet (B) to the one-sided metal-clad The layered body (A) is transferred from the side of the thermoplastic liquid crystal polymer film surface (the surface to which the shaping treatment is applied), so that the shaping treatment can be efficiently applied, and at the same time, the dimensional change of the metal-clad layered body can be suppressed. When the heating temperature of the pressure roller (r 2 ) is higher than that of the pressure roller (r 1 ), for example, the temperature difference between the heating temperature of the pressure roller (r 2 ) and the heating temperature of the pressure roller (r 1) It may be 20 to 200°C, preferably 25 to 150°C, and more preferably 30 to 100°C.

又，關於熱壓接溫度、加壓輥的壓力條件，沒有特別的限制，但從使金屬賦形薄片(B)的賦形面的凹凸的轉印性提高的觀點來看，例如，相對於熱塑性液晶聚合物薄膜的熔點(Tm)，熱壓接溫度，例如，可以是(Tm-150)℃以上，較佳可為(Tm-130)℃以上(例如，(Tm-100)℃以上)，更佳可為(Tm-110)℃以上(例如，(Tm-90)℃以上)。又，從金屬賦形薄片(B)的剝離性的提高、及抑制尺寸變化及皺摺的產生的觀點來看，可以小於(Tm)℃，較佳可為(Tm-5)℃以下，更佳可為(Tm-10)℃以下。此外，熱壓接溫度，可以是加壓輥(r1 , r2 )的加熱溫度，在一對加壓輥(r1 , r2 )的加熱溫度係彼此不同的情況下，加壓輥(r1 , r2 )的加熱溫度之中任一較高的加熱溫度可以是熱壓接溫度。 又，加壓壓力可以是16.0t/m(156.8kN/m)以下，較佳可為8.0t/m(78.4kN/m)以下的範圍內。加壓壓力的下限沒有特別的限制，可以是0.5t/m(4.9kN/m)以上。此外，加壓壓力係將賦予加壓輥的力(壓接荷重)除以通過加壓輥間的材料之中的最大寬度的值。In addition, there are no particular restrictions on the thermocompression bonding temperature and the pressure conditions of the pressure roller, but from the viewpoint of improving the transferability of the unevenness of the shaped surface of the metal shaped sheet (B), for example, relative to The melting point (Tm) and thermocompression bonding temperature of the thermoplastic liquid crystal polymer film, for example, may be (Tm-150)°C or higher, preferably (Tm-130)°C or higher (for example, (Tm-100)°C or higher) , More preferably (Tm-110)°C or higher (for example, (Tm-90)°C or higher). In addition, from the viewpoints of improving the releasability of the metal-shaped sheet (B) and suppressing the generation of dimensional changes and wrinkles, it may be less than (Tm)°C, preferably (Tm-5)°C or less, and more Preferably, the temperature is below (Tm-10)°C. In addition, the thermocompression bonding temperature may be the heating temperature of the pressure rollers (r 1 , r 2 ). When the heating temperature of the pair of pressure rollers (r 1 , r 2 ) is different from each other, the pressure roller ( Any higher heating temperature among the heating temperatures of r 1 , r 2) may be the thermocompression bonding temperature. In addition, the pressurizing pressure may be 16.0 t/m (156.8 kN/m) or less, preferably 8.0 t/m (78.4 kN/m) or less. The lower limit of the pressurizing pressure is not particularly limited, and may be 0.5 t/m (4.9 kN/m) or more. In addition, the pressing pressure is a value obtained by dividing the force applied to the pressing roller (pressure contact load) by the maximum width among the materials passing between the pressing rollers.

此外，本發明的製造方法可以根據需要而在加壓輥的下游側設置冷卻輥。冷卻輥較佳為設置在加壓輥與第1剝離輥之間。冷卻輥可以以一對輥構成，也可以以一個單獨輥構成。In addition, in the manufacturing method of the present invention, a cooling roll may be provided on the downstream side of the pressure roll as needed. The cooling roll is preferably provided between the pressure roll and the first peeling roll. The cooling roll may be composed of a pair of rolls, or may be composed of a single roll.

本發明的製造方法中，可以進一步具備：在熱壓接步驟後，從單面覆金屬之積層體(A)的熱塑性液晶聚合物薄膜面剝離金屬賦形薄片(B)的剝離步驟。剝離步驟中，例如，可以在通過一對加壓輥(r1 , r2 )後，使用該一對加壓輥(r1 , r2 )作為剝離輥，立刻從單面覆金屬之積層體(A)剝離金屬賦形薄片(B)，也可以使用與加壓輥分開配設的至少一個剝離輥，從單面覆金屬之積層體(A)剝離金屬賦形薄片(B)。The manufacturing method of the present invention may further include a peeling step of peeling the metal-shaped sheet (B) from the thermoplastic liquid crystal polymer film surface of the metal-clad laminate (A) after the thermocompression bonding step. In the peeling step, for example, after passing through a pair of pressure rollers (r 1 , r 2 ), the pair of pressure rollers (r 1 , r 2 ) can be used as peeling rollers to immediately remove the metal-clad laminate from one side (A) To peel the metal shaped sheet (B), at least one peeling roller provided separately from the pressure roller may be used to peel the metal shaped sheet (B) from the single-sided metal-clad laminate (A).

例如，在圖1所示的第1實施形態中，藉由上述熱壓接步驟所得到的覆金屬之積層體(D)((A)/(B))，係藉由通過剝離輥21、21，而在(A)/(B)間剝離，製造覆金屬之積層體(E)，捲取於覆金屬之積層體捲取輥31。藉由金屬賦形薄片(B)的剝離所得到的覆金屬之積層體(E)，係以金屬層/熱塑性液晶聚合物薄膜的順序積層，金屬賦形薄片(B)的賦形面的凹凸被轉印於熱塑性液晶聚合物薄膜的未接著金屬層的側的表面。即，覆金屬之積層體(E)的熱塑性液晶聚合物薄膜的未接著金屬層的側的表面粗糙度(Rz)可以是1.0～7.0μm，較佳可為1.5～5.5μm，更佳可為2.0～4.5μm。For example, in the first embodiment shown in FIG. 1, the metal-clad laminate (D) ((A)/(B)) obtained by the above-mentioned thermocompression bonding step is passed through the peeling roller 21, 21. It is peeled between (A)/(B) to produce a metal-clad laminate (E), which is wound on a metal-clad laminate winding roller 31. The metal-clad laminate (E) obtained by peeling the metal-shaped sheet (B) is laminated in the order of metal layer/thermoplastic liquid crystal polymer film, and the unevenness of the shaped surface of the metal-shaped sheet (B) It is transferred to the surface of the thermoplastic liquid crystal polymer film on the side where the metal layer is not adhered. That is, the surface roughness (Rz) of the thermoplastic liquid crystal polymer film of the metal-clad laminate (E) on the side where the metal layer is not adhered may be 1.0 to 7.0 μm, preferably 1.5 to 5.5 μm, and more preferably 2.0～4.5μm.

本發明的製造方法中，只要能夠進行剝離步驟，則單面覆金屬之積層體(A)和金屬賦形薄片(B)之間的剝離強度可以適宜設定。例如，單面覆金屬之積層體(A)和金屬賦形薄片(B)之間的剝離強度較佳為0.5N/mm以下，更佳為0.2N/mm以下，再更佳為0.1N/mm以下。下限沒有特別的限制，可以是0N/mm。本發明的製造方法，在熱壓接步驟中，藉由較低溫下的加熱加壓，能夠直接在單面覆金屬之積層體(A)和金屬賦形薄片(B)的層間接著性低的狀態下施加賦形處理。In the production method of the present invention, as long as the peeling step can be performed, the peeling strength between the single-sided metal-clad laminate (A) and the metal-shaped sheet (B) can be appropriately set. For example, the peel strength between the single-sided metal-clad laminate (A) and the metal shaped sheet (B) is preferably 0.5 N/mm or less, more preferably 0.2 N/mm or less, and even more preferably 0.1 N/mm. mm or less. The lower limit is not particularly limited, and may be 0 N/mm. In the production method of the present invention, in the thermocompression bonding step, heat and pressure at a lower temperature can be directly applied to the layer of the single-sided metal-clad laminate (A) and the metal-shaped sheet (B) with low adhesion In the state, the shaping process is applied.

被剝離的金屬賦形薄片(B)係由金屬賦形薄片捲取輥32捲取。本發明的製造方法中，被剝離的金屬賦形薄片(B)可以根據需要而再利用。The peeled metal shaped sheet (B) is taken up by the metal shaped sheet winding roller 32. In the production method of the present invention, the peeled metal shaped sheet (B) can be reused as needed.

又，圖2係供說明基於第2實施形態的覆金屬之積層體的製造方法用的側面示意圖。對於具有與圖1相同的作用的構件，給予相同的符號，省略說明。如圖2所示，第2實施形態中，係在一對加壓輥(r1 , r2 )的上游側，準備：將單面覆金屬之積層體(A)捲出的單面覆金屬之積層體捲出輥11、將金屬賦形薄片(B)捲出的金屬賦形薄片捲出輥12、及將脫模緩衝材(C)捲出的脫模緩衝材捲出輥13。In addition, FIG. 2 is a schematic side view for explaining the manufacturing method of the metal-clad laminate based on the second embodiment. The members having the same functions as those in FIG. 1 are given the same symbols, and descriptions are omitted. As shown in Figure 2, in the second embodiment, on the upstream side of a pair of pressure rollers (r 1 , r 2 ), prepare: a single-sided metal-clad laminate (A) rolled out of a single-sided metal-clad laminate The laminated body unwinding roller 11, the metal shaped sheet unwinding roller 12 that unwinds the metal shaped sheet (B), and the release buffer material unwinding roll 13 that unwinds the release buffer material (C).

此處，第2實施形態中，係以單面覆金屬之積層體(A)、金屬賦形薄片(B)及脫模緩衝材(C)在一對加壓輥(r1 , r2 )間成為(r1 )/(C)/(A)/(B)/(r2 )的順序的方式，配置各捲出輥。Here, in the second embodiment, a single-sided metal-clad laminate (A), a metal shaped sheet (B), and a release buffer material (C) are placed on a pair of pressure rollers (r 1 , r 2 ) The winding-up rollers are arranged in the order of (r 1 )/(C)/(A)/(B)/(r 2 ).

具體而言，在一對加壓輥(r1 , r2 )的上游側，以單面覆金屬之積層體(A)的熱塑性液晶聚合物薄膜面和金屬賦形薄片(B)的賦形面接觸的方式，配置單面覆金屬之積層體捲出輥11及金屬賦形薄片捲出輥12，進一步地，以單面覆金屬之積層體(A)的金屬層面和脫模緩衝材(C)接觸的方式，配置脫模緩衝材捲出輥13。Specifically, on the upstream side of a pair of pressure rollers (r 1 , r 2 ), the thermoplastic liquid crystal polymer film surface of the single-sided metal-clad laminate (A) and the metal shaped sheet (B) are shaped In the surface contact method, a single-sided metal-clad laminate roll-out roll 11 and a metal shaped sheet roll-out roll 12 are arranged, and further, the metal layer of the single-sided metal-clad laminate (A) and the release buffer material ( C) For the contact method, the release buffer material roll-out roller 13 is arranged.

如圖2所示，相對於一對加壓輥(r1 , r2 )，配置各捲出輥後，如箭頭方向所示，從各捲出輥捲出單面覆金屬之積層體(A)、金屬賦形薄片(B)、及脫模緩衝材(C)，相對於一對加壓輥(r1 , r2 )，導入於由箭頭所示的MD方向(或層疊方向)上，在一對加壓輥(r1 , r2 )中予以熱壓接，形成覆金屬之積層體(F)((C)/(A)/(B))。 As shown in Fig. 2 , after disposing each unwinding roller with respect to a pair of pressure rollers (r 1 , r 2 ), as shown in the arrow direction, a single-sided metal-clad laminate (A ), the metal shaped sheet (B), and the release buffer material (C) are introduced in the MD direction (or lamination direction) indicated by the arrow with respect to a pair of pressure rollers (r 1 , r 2 ), A pair of pressure rollers (r 1 , r 2 ) are thermally compressed to form a metal-clad laminate (F) ((C)/(A)/(B)).

如圖2所示，在第2實施形態中，由於使用脫模緩衝材(C)，因此能夠藉由其緩衝性使來自一對加壓輥(r1 , r2 )的壓力分散，能夠使金屬賦形薄片(B)的賦形面的凹凸形狀對熱塑性液晶聚合物薄膜的轉印性提高。再者，由於將脫模緩衝材(C)重疊在單面覆金屬之積層體(A)的金屬層側，因此脫模緩衝材(C)也發揮將來自加壓輥(r1 )的熱加以隔熱的作用，能夠抑制熱無謂地傳遞至熱塑性液晶聚合物薄膜的金屬層側的表面，能夠抑制尺寸變化。特別是，在加壓輥(r1 , r2 )的加熱溫度高的情況、或加壓壓力低的情況、加壓時間短的情況下，施加的壓力容易發生不均，因此藉由使用脫模緩衝材(C)來使壓力的均勻性提高的效果高。As shown in FIG. 2, in the second embodiment, since the release cushion material (C) is used, the pressure from the pair of pressure rollers (r 1 , r 2 ) can be dispersed due to its cushioning properties, and the pressure from the pair of pressure rollers (r 1, r 2) can be dispersed. The uneven shape of the shaped surface of the metal shaped sheet (B) improves the transferability of the thermoplastic liquid crystal polymer film. Furthermore, since the release buffer material (C) is superimposed on the metal layer side of the single-sided metal-clad laminate (A), the release buffer material (C) also exerts heat from the pressure roller (r 1) The effect of heat insulation can suppress unnecessary heat transfer to the surface of the thermoplastic liquid crystal polymer film on the metal layer side, and can suppress dimensional changes. In particular, when the heating temperature of the pressure rollers (r 1 , r 2 ) is high, or when the pressure is low, or when the pressure time is short, unevenness of the applied pressure is likely to occur. Therefore, the use of The mold cushioning material (C) has a high effect of improving the uniformity of pressure.

本發明的製造方法中，可以藉由至少一個剝離輥，從由熱壓接步驟所得到的覆金屬之積層體(具備單面覆金屬之積層體(A)和金屬賦形薄片(B)的覆金屬之積層體、或單面覆金屬之積層體(A)的熱塑性液晶聚合物薄膜面被賦形處理的覆金屬之積層體的具備脫模緩衝材(C)的覆金屬之積層體)剝離脫模緩衝材(C)。例如，可以在通過一對加壓輥(r1 , r2 )後，使用該一對加壓輥(r1 , r2 )作為剝離輥，立刻從覆金屬之積層體剝離脫模緩衝材(C)，也可以使用與加壓輥分開配設的至少一個剝離輥，從覆金屬之積層體剝離脫模緩衝材(C)。In the manufacturing method of the present invention, at least one peeling roll can be used to obtain a metal-clad laminate (a one-sided metal-clad laminate (A) and a metal-shaped sheet (B) obtained by the thermocompression bonding step). A metal-clad laminate or a metal-clad laminate with a single-sided metal-clad laminate (A) whose thermoplastic liquid crystal polymer film surface is shaped and a metal-clad laminate with a release buffer material (C)) Peel the release buffer material (C). For example, after passing through a pair of pressure rollers (r 1 , r 2 ), the pair of pressure rollers (r 1 , r 2 ) can be used as peeling rollers to immediately peel off the release buffer material ( C) It is also possible to use at least one peeling roller provided separately from the pressure roller to peel the release buffer material (C) from the metal-clad laminate.

在本發明的製造方法中，金屬賦形薄片(B)的剝離、及脫模緩衝材(C)的剝離順序能夠根據覆金屬之積層體的態樣適宜設定。In the manufacturing method of the present invention, the peeling order of the metal shaped sheet (B) and the peeling buffer material (C) can be appropriately set according to the state of the metal-clad laminate.

例如，在圖2所示的第2實施形態中，由上述熱壓接步驟所得到的覆金屬之積層體(F)((C)/(A)/(B))，係藉由通過第1剝離輥21、21來在(C)/(A)間剝離，而製造覆金屬之積層體(D)。藉由脫模緩衝材(C)的剝離所得到的覆金屬之積層體(D)，係以單面覆金屬之積層體(A)的金屬層/單面覆金屬之積層體(A)的熱塑性液晶聚合物薄膜/金屬賦形薄片(B)的順序積層。For example, in the second embodiment shown in FIG. 2, the metal-clad laminate (F)((C)/(A)/(B)) obtained by the above-mentioned thermocompression bonding step is obtained by passing through the first 1 The peeling rollers 21 and 21 peel between (C)/(A) to produce a metal-clad laminate (D). The metal-clad laminate (D) obtained by peeling off the release buffer material (C) is the metal layer of the single-sided metal-clad laminate (A) / the single-sided metal-clad laminate (A) The thermoplastic liquid crystal polymer film/metal shaped sheet (B) is laminated in the order.

本發明的製造方法中，只要能夠進行剝離步驟，則脫模緩衝材(C)和單面覆金屬之積層體(A)或金屬賦形薄片(B)之間的剝離強度可以適宜設定。In the production method of the present invention, as long as the peeling step can be performed, the peeling strength between the release buffer material (C) and the single-sided metal-clad laminate (A) or the metal shaped sheet (B) can be appropriately set.

例如，脫模緩衝材(C)和單面覆金屬之積層體(A)或金屬賦形薄片(B)之間的剝離強度較佳為0.1N/mm以下，更佳為0.05N/mm以下，再更佳為0.03N/mm以下。下限沒有特別的限制，可以是0N/mm。For example, the peel strength between the release buffer material (C) and the single-sided metal-clad laminate (A) or the metal shaped sheet (B) is preferably 0.1 N/mm or less, more preferably 0.05 N/mm or less , And more preferably 0.03N/mm or less. The lower limit is not particularly limited, and may be 0 N/mm.

被剝離的脫模緩衝材(C)係由脫模緩衝材捲取輥33捲取。本發明的製造方法中，被剝離的脫模緩衝材(C)能夠根據需要而再利用。The peeled release buffer material (C) is taken up by the release buffer material take-up roller 33. In the manufacturing method of this invention, the release cushion material (C) peeled can be reused as needed.

剝離了脫模緩衝材(C)的覆金屬之積層體(D)，係藉由通過第2剝離輥22、22來在(A)/(B)間剝離，而製造覆金屬之積層體(E)，捲取於覆金屬之積層體捲取輥31。The metal-clad laminate (D) from which the release buffer material (C) is peeled off is peeled between (A)/(B) by the second peeling rollers 22, 22 to produce the metal-clad laminate ( E), it is wound on the metal-clad laminate winding roller 31.

又，圖3係供說明基於第3實施形態的覆金屬之積層體的製造方法用的側面示意圖。如圖3所示，第3實施形態中，係以單面覆金屬之積層體(A)、金屬賦形薄片(B)及脫模緩衝材(C)在一對加壓輥(r1 , r2 )間成為(r1 )/(C)/(A)/(B)/(C)/(r2 )的順序的方式，配置各捲出輥。此處，對於具有與圖2相同的作用的構件，給予相同的符號，省略說明。Moreover, FIG. 3 is a schematic side view for explaining the manufacturing method of the metal-clad laminated body based on 3rd Embodiment. As shown in Figure 3, in the third embodiment, a single-sided metal-clad laminate (A), a metal shaped sheet (B) and a release buffer material (C) are placed on a pair of pressure rollers (r 1 , The interval between r 2 ) is (r 1 )/(C)/(A)/(B)/(C)/(r 2 ), and each unwinding roller is arranged. Here, members having the same functions as those in FIG. 2 are given the same reference numerals, and the description is omitted.

在圖3所示的第3實施形態中，以在一對加壓輥(r1 , r2 )間成為(C)/(A)/(B)/(C)的方式所重疊的覆金屬之積層體(F)，係在(C)/(A)間及(B)/(C)間剝離脫模緩衝材(C)，而製造覆金屬之積層體(D)，之後，從覆金屬之積層體(D)剝離金屬賦形薄片(B)，而製造覆金屬之積層體(E)。In the third embodiment shown in FIG. 3, the metal clad overlapped so as to become (C)/(A)/(B)/(C) between a pair of pressure rollers (r 1 , r 2) The laminate (F) is to peel off the release buffer material (C) between (C)/(A) and between (B)/(C) to produce a metal-clad laminate (D). The metal laminate (D) peels off the metal shaped sheet (B) to produce a metal-clad laminate (E).

又，在圖3所示的第3實施形態中，一對加壓輥(r1 , r2 )的各加熱溫度彼此可以相同也可以不同，例如，與第1實施形態同樣地，金屬賦形薄片(B)側的加壓輥(r2 )係加熱溫度可以比加壓輥(r1 )高。藉由與和金屬賦形薄片(B)鄰接的脫模緩衝材(C)相接的加壓輥(r2 )的加熱溫度較高，能夠有效率地將熱從金屬賦形薄片(B)朝向單面覆金屬之積層體(A)的熱塑性液晶聚合物薄膜面(施加賦形處理的面)側傳遞。In addition, in the third embodiment shown in FIG. 3 , the heating temperatures of the pair of pressure rollers (r 1 , r 2 ) may be the same or different from each other. For example, as in the first embodiment, the metal is shaped The heating temperature of the pressure roller (r 2 ) on the side of the sheet (B) may be higher than that of the pressure roller (r 1 ). The heating temperature of the pressure roller (r 2 ) in contact with the release buffer material (C) adjacent to the metal shaped sheet (B) is high, so that the heat can be efficiently removed from the metal shaped sheet (B) Transfer to the side of the thermoplastic liquid crystal polymer film surface (the surface to which the shaping treatment is applied) of the single-sided metal-clad laminate (A).

又，圖4係供說明基於第4實施形態的覆金屬之積層體的製造方法用的側面示意圖。如圖4所示，第4實施形態中，係以單面覆金屬之積層體(A)、金屬賦形薄片(B)及脫模緩衝材(C)在一對加壓輥(r1 , r2 )間成為(r1 )/(B)/(A)/(C)/(A)/ (B)/(r2 )的順序的方式，配置各捲出輥。此處，對於具有與圖2相同的作用的構件，給予相同的符號，省略說明。In addition, FIG. 4 is a schematic side view for explaining the manufacturing method of the metal-clad laminate based on the fourth embodiment. As shown in Figure 4, in the fourth embodiment, a single-sided metal-clad laminate (A), a metal shaped sheet (B) and a release buffer material (C) are placed on a pair of pressure rollers (r 1 , Between r 2 ) becomes the order of (r 1 )/(B)/(A)/(C)/(A)/(B)/(r 2 ), and each unwinding roller is arranged. Here, members having the same functions as those in FIG. 2 are given the same reference numerals, and the description is omitted.

在圖4所示的第4實施形態中，以在一對加壓輥(r1 , r2 )間成為(B)/(A)/(C)/(A)/(B)的方式所重疊的覆金屬之積層體(F)，係剝離脫模緩衝材(C)，而製造2個覆金屬之積層體(D)，之後，從覆金屬之積層體(D)剝離金屬賦形薄片(B)，而製造2個覆金屬之積層體(E)。In the fourth embodiment shown in FIG. 4, it becomes (B)/(A)/(C)/(A)/(B) between a pair of pressure rollers (r 1 , r 2 ). The overlapped metal-clad laminate (F) is peeled off the release buffer material (C) to produce two metal-clad laminates (D), and then the metal shaped sheet is peeled from the metal-clad laminate (D) (B), and manufacture 2 metal-clad laminates (E).

在圖4所示的第4實施形態中，能夠製造複數個覆金屬之積層體，生產效率佳。2個覆金屬之積層體(D)彼此可以相同也可以不同。同樣地，2個覆金屬之積層體(E)亦彼此可以相同也可以不同。In the fourth embodiment shown in FIG. 4, a plurality of metal-clad laminates can be manufactured, and the production efficiency is good. The two metal-clad laminates (D) may be the same or different from each other. Similarly, the two metal-clad laminates (E) may be the same or different from each other.

在圖4所示的第4實施形態中，脫模緩衝材(C)係在兩面上，與單面覆金屬之積層體(A)重疊，因此較佳為在兩面配設脫模層。In the fourth embodiment shown in FIG. 4, the release buffer material (C) is on both sides and overlaps the single-sided metal-clad laminate (A), so it is preferable to provide a release layer on both sides.

又，在圖4所示的第4實施形態中，在得到相同的覆金屬之積層體的情況下，從在熱壓接步驟抑制因熱膨脹的差異所造成的皺摺的產生的觀點來看，一對加壓輥(r1 , r2 )可以相同，加熱溫度可以相同。In the fourth embodiment shown in FIG. 4, in the case of obtaining the same metal-clad laminate, from the viewpoint of suppressing the generation of wrinkles due to differences in thermal expansion in the thermocompression bonding step, A pair of pressure rollers (r 1 , r 2 ) may be the same, and the heating temperature may be the same.

再者，圖5係供說明基於第5實施形態的覆金屬之積層體的製造方法用的側面示意圖。如圖5所示，第5實施形態中，係以單面覆金屬之積層體(A)、金屬賦形薄片(B)及脫模緩衝材(C)在一對加壓輥(r1 , r2 )間成為(r1 )/(C)/(B)/(A)/(A)/(B) /(C)/(r2 )的順序的方式，配置各捲出輥。此處，對於具有與圖2相同的作用的構件，給予相同的符號，省略說明。Furthermore, FIG. 5 is a schematic side view for explaining the manufacturing method of the metal-clad laminate based on the fifth embodiment. As shown in Figure 5, in the fifth embodiment, a single-sided metal-clad laminate (A), a metal shaped sheet (B), and a release buffer material (C) are placed on a pair of pressure rollers (r 1 , Between r 2 ) becomes the order of (r 1 )/(C)/(B)/(A)/(A)/(B)/(C)/(r 2 ), and each unwinding roller is arranged. Here, members having the same functions as those in FIG. 2 are given the same reference numerals, and the description is omitted.

在圖5所示的第5實施形態中，以在一對加壓輥(r1 , r2 )間成為(C)/(B)/(A)/(A)/(B)/(C)的方式所重疊的覆金屬之積層體(F)，係剝離脫模緩衝材(C)，而製造2個覆金屬之積層體(D)，之後，從覆金屬之積層體(D)剝離金屬賦形薄片(B)，而製造2個覆金屬之積層體(E)。In the fifth embodiment shown in FIG. 5, it becomes (C)/(B)/(A)/(A)/(B)/(C) between a pair of pressure rollers (r 1 , r 2) The metal-clad laminate (F) overlapped by the method of) is peeled off the release buffer material (C) to produce two metal-clad laminates (D), and then peeled from the metal-clad laminate (D) The metal is shaped into a flake (B), and two metal-clad laminates (E) are produced.

在圖5所示的第5實施形態中，能夠製造複數個覆金屬之積層體，生產效率佳。2個覆金屬之積層體(D)彼此可以相同也可以不同。同樣地，2個覆金屬之積層體(E)亦彼此可以相同也可以不同。In the fifth embodiment shown in FIG. 5, a plurality of metal-clad laminates can be manufactured, and the production efficiency is good. The two metal-clad laminates (D) may be the same or different from each other. Similarly, the two metal-clad laminates (E) may be the same or different from each other.

再者，圖6係供說明基於第6實施形態的覆金屬之積層體的製造方法用的側面示意圖。如圖6所示，第6實施形態中，係以單面覆金屬之積層體(A)、金屬賦形薄片(B)及脫模緩衝材(C)在一對加壓輥(r1 , r2 )間成為(r1 )/(C)/(A)/(B)/(B)/ (A)/(C)/(r2 )的順序的方式，配置各捲出輥。此處，對於具有與圖2相同的作用的構件，給予相同的符號，省略說明。In addition, FIG. 6 is a schematic side view for explaining the manufacturing method of the metal-clad laminate based on the sixth embodiment. As shown in Figure 6, in the sixth embodiment, a single-sided metal-clad laminate (A), a metal shaped sheet (B), and a release buffer material (C) are placed on a pair of pressure rollers (r 1 , Between r 2 ) becomes the order of (r 1 )/(C)/(A)/(B)/(B)/(A)/(C)/(r 2 ), and each unwinding roller is arranged. Here, members having the same functions as those in FIG. 2 are given the same reference numerals, and the description is omitted.

在圖6所示的第6實施形態中，以在一對加壓輥(r1 , r2 )間成為(C)/(A)/(B)/(B)/(A)/(C)的方式所重疊的覆金屬之積層體(F)，係剝離脫模緩衝材(C)，而製造2個覆金屬之積層體(D)，之後，從覆金屬之積層體(D)剝離金屬賦形薄片(B)，而製造2個覆金屬之積層體(E)。In the sixth embodiment shown in FIG. 6, it is assumed that between a pair of pressure rollers (r 1 , r 2 ) becomes (C)/(A)/(B)/(B)/(A)/(C) The metal-clad laminate (F) overlapped by the method of) is peeled off the release buffer material (C) to produce two metal-clad laminates (D), and then peeled from the metal-clad laminate (D) The metal is shaped into a flake (B), and two metal-clad laminates (E) are produced.

在圖6所示的第6實施形態中，能夠製造複數個覆金屬之積層體，生產效率佳。2個覆金屬之積層體(D)彼此可以相同也可以不同。同樣地，2個覆金屬之積層體(E)亦彼此可以相同也可以不同。 [實施例]In the sixth embodiment shown in FIG. 6, a plurality of metal-clad laminates can be manufactured, and the production efficiency is good. The two metal-clad laminates (D) may be the same or different from each other. Similarly, the two metal-clad laminates (E) may be the same or different from each other. [Example]

以下，藉由實施例更詳細地說明本發明，但本實施例對本發明不構成任何限定。此外，在以下的實施例及比較例中，藉由下述的方法評價剝離性、及翹曲。Hereinafter, the present invention will be explained in more detail with examples, but the present examples do not constitute any limitation to the present invention. In addition, in the following Examples and Comparative Examples, peelability and warpage were evaluated by the following methods.

[剝離強度] 在實施例1及2中，分別得到在熱壓接後、剝離聚醯亞胺薄膜(C)及金屬賦形薄片(B)前的覆金屬之積層體，從該覆金屬之積層體製作3mm寬的剝離試驗片，根據JIS C 6471，藉由90°法，以50mm/min的速度，測定分別在單面覆金屬之積層體(E)與金屬賦形薄片(B)的界面、及單面覆金屬之積層體(E)與聚醯亞胺薄膜(C)的界面進行剝離時的強度(N/mm)。[Peel strength] In Examples 1 and 2, a metal-clad laminate was obtained after thermocompression bonding and before peeling off the polyimide film (C) and the metal-shaped sheet (B), and 3 mm was produced from the metal-clad laminate. The wide peel test piece is measured by the 90° method in accordance with JIS C 6471 at a speed of 50 mm/min on one side of the metal-clad laminate (E) and the metal shaped sheet (B). The strength (N/mm) when peeling off the interface between the metal-coated laminate (E) and the polyimide film (C).

[剝離性評價] 連續地將單面覆金屬之積層體與金屬賦形薄片間進行剝離，將在長度20m以上中，觀察不到皺摺、變形、剝離不良、材料破壞者評價為A，將觀察到者評價為B。[Evaluation of Peelability] The single-sided metal-clad laminate and the metal shaped sheet were continuously peeled off. In the length of 20m or more, no wrinkles, deformation, peeling failure, or material damage were observed as A, and the observer was evaluated as B.

[翹曲測定] 由單面覆金屬之積層體採取寬度250mm、長度250mm的樣品，將樣品置於水平的桌台上，以刻度尺測定樣品的4個角落之中自桌台浮得最高的部分的高度，將其作為翹曲。將翹曲小於5mm者評價為A，將確認有5mm以上的翹曲者評價為B。[Warpage measurement] Take a sample with a width of 250 mm and a length of 250 mm from a single-sided metal-clad laminate, place the sample on a horizontal table, and measure the height of the highest part of the sample from the table among the four corners of the sample with a scale. It acts as warpage. A person with a warpage of less than 5 mm was evaluated as A, and a person with a warpage of 5 mm or more was evaluated as B.

(製造例1) 在熱塑性液晶聚合物薄膜(Kuraray股份有限公司製「Bextor」(註冊商標)，熔點310℃，厚度50μm)的單面，重疊銅箔(福田金屬箔粉工業股份有限公司製，「CF-H9A-DS-HD2」，厚度12μm)，使用直徑為300mm的金屬輥，將金屬輥的表面溫度設定為260℃，將加壓壓力設定為8t/m，以速度3.0m/min使其通過而進行熱壓接，製作熱塑性液晶聚合物薄膜/銅箔的構成的單面覆金屬之積層體(A)。(Manufacturing example 1) On one side of a thermoplastic liquid crystal polymer film ("Bextor" (registered trademark) manufactured by Kuraray Co., Ltd., melting point 310°C, thickness 50μm), a copper foil (manufactured by Futian Metal Foil Industrial Co., Ltd., "CF-H9A- DS-HD2", thickness 12μm), using a metal roll with a diameter of 300mm, the surface temperature of the metal roll is set to 260°C, the pressure is set to 8t/m, and the heat is passed through at a speed of 3.0m/min. Press bonding to produce a single-sided metal-clad laminate (A) composed of a thermoplastic liquid crystal polymer film/copper foil.

(實施例1) 以捲出輥的形式，分別準備：在製造例1所得到的單面覆金屬之積層體(A)、作為金屬賦形薄片(B)的電解銅箔(JX金屬股份有限公司製「JX-EFL-V2」，厚度12μm，賦形面的表面粗糙度(Rz)2.0μm)、及作為保護材(C)的聚醯亞胺薄膜(Kaneka股份有限公司製「Apical NPI」，厚度75μm)，以在一對加壓輥(r1 , r2 )間成為r1 /C/A/B/r2 的順序的方式導入。分別使用直徑為300mm的金屬輥作為一對加壓輥(r1 , r2 )，將金屬輥的表面溫度設定為200℃，將加壓壓力設定為8t/m，以速度3.0m/min使其通過一對加壓輥(r1 , r2 )而進行熱壓接。(Example 1) In the form of unwinding rolls, prepared separately: the single-sided metal-clad laminate (A) obtained in Manufacturing Example 1 and the electrolytic copper foil (JX Metal Co., Ltd.) as the metal shaped sheet (B) "JX-EFL-V2" manufactured by the company, thickness 12μm, surface roughness (Rz) 2.0μm of the shaped surface, and polyimide film as a protective material (C) ("Apical NPI" manufactured by Kaneka Co., Ltd.) , A thickness of 75 μm), which is introduced in the order of r 1 /C/A/B/r 2 between a pair of pressure rollers (r 1 , r 2 ). Use metal rollers with a diameter of 300mm as a pair of pressure rollers (r 1 , r 2 ), set the surface temperature of the metal rollers to 200°C, set the pressure to 8t/m, and set the speed at 3.0m/min. This is thermocompression-bonded by a pair of pressure rollers (r 1 , r 2 ).

熱壓接後，如圖2所示，通過一對加壓輥(r1 , r2 )後，使用一對剝離輥(21)來將聚醯亞胺薄膜(C)分離，然後藉由一對剝離輥(22)來將單面覆金屬之積層體(E)和金屬賦形薄片(B)分離，得到金屬賦形薄片(B)的表面形狀被轉印於熱塑性液晶聚合物薄膜面的單面覆金屬之積層體(E)。將金屬賦形薄片(B)的剝離性、及所得到的單面覆金屬之積層體(E)的翹曲測定結果顯示於表7。單面覆金屬之積層體(E)和金屬賦形薄片(B)之間的剝離強度為0.05N/mm以下。又，單面覆金屬之積層體(E)和聚醯亞胺薄膜(C)之間的剝離強度，係完全沒有接著而無法測定。After thermocompression bonding, as shown in Figure 2, after passing through a pair of pressure rollers (r 1 , r 2 ), a pair of peeling rollers (21) are used to separate the polyimide film (C), and then a pair of pressure rollers (r 1, r 2) are used to separate the polyimide film (C). Separate the single-sided metal-clad laminate (E) and the metal-shaped sheet (B) on the peeling roller (22) to obtain the surface shape of the metal-shaped sheet (B) transferred to the surface of the thermoplastic liquid crystal polymer film Single-sided metal-clad laminate (E). Table 7 shows the releasability of the metal-shaped sheet (B) and the warpage measurement results of the obtained one-sided metal-clad laminate (E). The peel strength between the single-sided metal-clad laminate (E) and the metal shaped sheet (B) is 0.05 N/mm or less. In addition, the peel strength between the single-sided metal-clad laminate (E) and the polyimide film (C) was not adhered at all and could not be measured.

(實施例2) 除了將金屬輥的表面溫度設定為240℃外，與實施例1同樣地製作單面覆金屬之積層體(E)。將金屬賦形薄片(B)的剝離性、及所得到的單面覆金屬之積層體(E)的翹曲測定結果顯示於表7。單面覆金屬之積層體(E)和金屬賦形薄片(B)之間的剝離強度為0.08N/mm以下。又，單面覆金屬之積層體(E)和聚醯亞胺薄膜(C)之間的剝離強度，係完全沒有接著而無法測定。(Example 2) Except that the surface temperature of the metal roll was set to 240°C, a single-sided metal-clad laminate (E) was produced in the same manner as in Example 1. Table 7 shows the releasability of the metal-shaped sheet (B) and the warpage measurement results of the obtained one-sided metal-clad laminate (E). The peel strength between the single-sided metal-clad laminate (E) and the metal shaped sheet (B) is 0.08 N/mm or less. In addition, the peel strength between the single-sided metal-clad laminate (E) and the polyimide film (C) was not adhered at all and could not be measured.

(比較例1) 若除了使用熱塑性液晶聚合物薄膜(L)(Kuraray股份有限公司製「Bextor」(註冊商標)，熔點310℃，厚度50μm)和銅箔(M)(福田金屬箔粉工業股份有限公司製「CF-H9A-DS-HD2」，厚度12μm)，來取代單面覆金屬之積層體(A)外，與實施例1同樣地，和金屬賦形薄片(B)及保護材(C)一起，以在一對加壓輥(r1 , r2 )間成為r1 /C/M/L/B/r2 的順序的方式導入，製作單面覆金屬之積層體(E)，則認為熱塑性液晶聚合物薄膜(L)和銅箔(M)間的剝離強度低，在剝離金屬賦形薄片(B)之際，連在熱塑性液晶聚合物薄膜(L)和銅箔(M)間也會局部地發生剝離。(Comparative Example 1) In addition to using thermoplastic liquid crystal polymer film (L) ("Bextor" (registered trademark) manufactured by Kuraray Co., Ltd., melting point 310°C, thickness 50μm) and copper foil (M) (Fukuda Metal Foil Industrial Co., Ltd.) "CF-H9A-DS-HD2" manufactured by the company, thickness 12μm), instead of single-sided metal-clad laminate (A), similar to Example 1, and metal-shaped sheet (B) and protective material (C) ) Is introduced in the order of r 1 /C/M/L/B/r 2 between a pair of pressure rollers (r 1 , r 2 ) to produce a single-sided metal-clad laminate (E), It is considered that the peeling strength between the thermoplastic liquid crystal polymer film (L) and the copper foil (M) is low. When the metal shaped sheet (B) is peeled off, it is also connected between the thermoplastic liquid crystal polymer film (L) and the copper foil (M). Peeling will occur locally.

(比較例2) 若除了將金屬輥的表面溫度設定為320℃外，與比較例1同樣地製作單面覆金屬之積層體(E)，則認為雖然熱塑性液晶聚合物薄膜(L)和銅箔(M)間的剝離強度充分變高，但熱塑性液晶聚合物薄膜(L)和金屬賦形薄片(B)之間的剝離強度也變高，因此在剝離熱塑性液晶聚合物薄膜(L)和金屬賦形薄片(B)之際，連續地發生皺摺、變形、剝離不良、及薄膜的材料破壞中的任一者，又，認為有翹曲也變大的傾向。(Comparative example 2) If a single-sided metal-clad laminate (E) is produced in the same manner as in Comparative Example 1, except that the surface temperature of the metal roll is set to 320°C, it is considered that the gap between the thermoplastic liquid crystal polymer film (L) and the copper foil (M) is The peeling strength is sufficiently high, but the peeling strength between the thermoplastic liquid crystal polymer film (L) and the metal-shaped sheet (B) is also high, so the peeling of the thermoplastic liquid crystal polymer film (L) and the metal-shaped sheet (B) In the case of ), any one of wrinkles, deformation, peeling failure, and material destruction of the film occurs continuously, and it is considered that the warpage also tends to increase.

[表7] 　 輥表面溫度[℃] 剝離性 翹曲[mm] 實施例1 200 A A(0) 實施例2 240 A A(1.5) [Table 7] Roll surface temperature [℃] Peelability Warpage [mm] Example 1 200 A A(0) Example 2 240 A A(1.5)

如表7所示，在實施例1及2方面，由於預先製造單面覆金屬之積層體(A)，因此能夠將金屬輥表面溫度設定為較低的溫度，藉此，單面覆金屬之積層體與金屬賦形薄片間不會牢固地緊貼著，又，熱塑性液晶聚合物薄膜的分子配向也不會變化，剝離性、翹曲皆為良好的結果。 [產業上利用之可能性]As shown in Table 7, in the aspects of Examples 1 and 2, since the single-sided metal-clad laminate (A) was manufactured in advance, the surface temperature of the metal roll can be set to a lower temperature, whereby the single-sided metal-clad The laminate and the metal-shaped sheet do not adhere firmly, and the molecular orientation of the thermoplastic liquid crystal polymer film does not change, and the peelability and warpage are good results. [Possibility of Industrial Utilization]

若根據本發明的製造方法的話，則能夠效率佳地製造經賦形處理的覆金屬之積層體，所得到的覆金屬之積層體，由於轉印有凹凸，因此與接合薄片的層間接著性優異，電路加工性良好。因此，所得到的覆金屬之積層體能夠有效地用作在電氣．電子領域、或事務機器．精密機器領域、功率半導體領域等中所使用的零件，例如，電路基板(特別是毫米波雷達用基板)。According to the manufacturing method of the present invention, it is possible to efficiently manufacture a shaped metal-clad laminate, and the resulting metal-clad laminate has excellent adhesion to the layer of the bonding sheet due to the transfer of unevenness. , The circuit processability is good. Therefore, the resulting metal-clad laminate can be effectively used in electrical applications. Electronic field, or business machine. Parts used in the field of precision equipment, power semiconductors, etc., for example, circuit boards (especially boards for millimeter wave radar).

如上所述，一邊參照圖式，一邊說明了本發明的合適的實施形態，但若為該業者的話，則看了本件說明書，便可以在顯而易見的範圍內輕易推測出各種變更及修正。由此，這樣的變更及修正係解釋為由申請專利範圍所決定的發明的範圍內者。As described above, the suitable embodiments of the present invention have been described with reference to the drawings. However, if you are a professional, you can easily guess various changes and corrections within an obvious range after reading this manual. Therefore, such changes and amendments are interpreted as being within the scope of the invention determined by the scope of the patent application.

11:單面覆金屬之積層體捲出輥 12:金屬賦形薄片捲出輥 13:脫模緩衝材捲出輥 21,22:剝離輥 31:覆金屬之積層體捲取輥 32:金屬賦形薄片捲取輥 33:脫模緩衝材捲取輥 r1 ,r2 :加壓輥 A:單面覆金屬之積層體 B:金屬賦形薄片 C:脫模緩衝材 D,E,F:覆金屬之積層體11: Single-sided metal-clad laminate roll-out roll 12: Metal-shaped sheet roll-out roll 13: Release buffer material roll-out roll 21, 22: Peeling roll 31: Metal-clad laminate roll-up 32: Metallic Shaped sheet take-up roller 33: Release buffer material take-up roller r 1 , r 2 : Pressure roller A: Single-sided metal-clad laminate B: Metal shaped sheet C: Release buffer material D, E, F: Metal-clad laminate

此發明可以由參考添附圖式的以下的合適實施形態的說明而更加清楚地理解。然而，實施形態及圖式係僅僅用於圖示及說明者，不該被用來決定此發明的範圍。此發明的範圍係由添附的申請專利範圍決定。圖式未必是以一定的比例尺表示，在表現出本發明的原理上進行了誇大。 圖1係供說明基於本發明的第1實施形態的覆金屬之積層體的製造方法用的側面示意圖。 圖2係供說明基於本發明的第2實施形態的覆金屬之積層體的製造方法用的側面示意圖。 圖3係供說明基於本發明的第3實施形態的覆金屬之積層體的製造方法用的側面示意圖。 圖4係供說明基於本發明的第4實施形態的覆金屬之積層體的製造方法用的側面示意圖。 圖5係供說明基於本發明的第5實施形態的覆金屬之積層體的製造方法用的側面示意圖。 圖6係供說明基於本發明的第6實施形態的覆金屬之積層體的製造方法用的側面示意圖。This invention can be understood more clearly by referring to the description of the following suitable embodiments with reference to the attached drawings. However, the embodiments and drawings are only for illustration and description, and should not be used to determine the scope of the invention. The scope of this invention is determined by the scope of the attached patent application. The drawings are not necessarily represented on a certain scale, and are exaggerated in order to show the principle of the present invention. Fig. 1 is a schematic side view for explaining a method of manufacturing a metal-clad laminate based on the first embodiment of the present invention. Fig. 2 is a schematic side view for explaining a method of manufacturing a metal-clad laminate based on a second embodiment of the present invention. Fig. 3 is a schematic side view for explaining a method of manufacturing a metal-clad laminate based on a third embodiment of the present invention. Fig. 4 is a schematic side view for explaining a method of manufacturing a metal-clad laminate according to a fourth embodiment of the present invention. Fig. 5 is a schematic side view for explaining a method of manufacturing a metal-clad laminate according to a fifth embodiment of the present invention. Fig. 6 is a schematic side view for explaining a method of manufacturing a metal-clad laminate according to a sixth embodiment of the present invention.

11:單面覆金屬之積層體捲出輥 11: Single-sided metal-clad laminate roll-out roll

12:金屬賦形薄片捲出輥 12: Metal shaped sheet roll-out roll

21:剝離輥 21: Peeling roller

31:覆金屬之積層體捲取輥 31: Metal-clad laminate winding roll

32:金屬賦形薄片捲取輥 32: Metal shaped sheet take-up roll

r1,r2:加壓輥 r 1 , r 2 : pressure roller

A:單面覆金屬之積層體 A: Single-sided metal-clad laminate

B:金屬賦形薄片 B: Metal shaped flakes

D,E:覆金屬之積層體 D, E: Metal-clad laminate

Claims (16)

一種覆金屬之積層體的製造方法，其至少具備： 準備在熱塑性液晶聚合物薄膜的一面接著金屬層的長條狀的單面覆金屬之積層體(A)、及至少一表面為賦形面的長條狀的金屬賦形薄片(B)的步驟；和 以該單面覆金屬之積層體(A)的熱塑性液晶聚合物薄膜面和該金屬賦形薄片(B)的賦形面接觸的方式配置，朝向一對加壓輥(r1 , r2 )導入的熱壓接步驟。A method for manufacturing a metal-clad laminate, comprising at least: a long strip of metal-clad laminate (A) with a metal layer attached to one side of a thermoplastic liquid crystal polymer film, and at least one surface as a shaped surface The step of forming a long strip of metal-shaped flake (B); and contacting the surface of the thermoplastic liquid crystal polymer film of the single-sided metal-clad laminate (A) with the shaped surface of the metal-shaped flake (B) It is arranged in a way, and a thermocompression bonding step introduced toward a pair of pressure rollers (r 1 , r 2 ). 如請求項1的覆金屬之積層體的製造方法，其進一步具備： 在熱壓接步驟後，從該單面覆金屬之積層體(A)的熱塑性液晶聚合物薄膜面剝離該金屬賦形薄片(B)的剝離步驟。For example, the method for manufacturing a metal-clad laminate of claim 1, which further includes: After the thermocompression bonding step, a peeling step of peeling the metal-shaped sheet (B) from the thermoplastic liquid crystal polymer film surface of the single-sided metal-clad laminate (A). 如請求項1或2的覆金屬之積層體的製造方法，其中在以該熱塑性液晶聚合物薄膜的熔點(Tm)而言的情況下，熱壓接溫度為(Tm-150)℃以上且小於(Tm)℃。The method for manufacturing a metal-clad laminate according to claim 1 or 2, wherein in terms of the melting point (Tm) of the thermoplastic liquid crystal polymer film, the thermocompression bonding temperature is (Tm-150)°C or more and less than (Tm)°C. 如請求項1至3中任一項的覆金屬之積層體的製造方法，其中該單面覆金屬之積層體(A)和該金屬賦形薄片(B)的剝離強度為0.5N/mm以下。The method for manufacturing a metal-clad laminate according to any one of claims 1 to 3, wherein the peel strength of the single-sided metal-clad laminate (A) and the metal shaped sheet (B) is 0.5 N/mm or less . 如請求項1至4中任一項的覆金屬之積層體的製造方法，其中該金屬賦形薄片(B)的賦形面的表面粗糙度(Rz)為1.0～7.0μm。The method for manufacturing a metal-clad laminate according to any one of claims 1 to 4, wherein the surface roughness (Rz) of the shaped surface of the metal shaped sheet (B) is 1.0 to 7.0 μm. 如請求項1至5中任一項的覆金屬之積層體的製造方法，其中， 在準備步驟中，進一步準備長條狀的脫模緩衝材(C)， 在熱壓接步驟中，在該單面覆金屬之積層體(A)及該金屬賦形薄片(B)的未接觸側中的至少一側配置該脫模緩衝材(C)，朝向一對加壓輥(r1 , r2 )導入。The method of manufacturing a metal-clad laminate according to any one of claims 1 to 5, wherein, in the preparation step, a strip-shaped release buffer material (C) is further prepared, and in the thermal compression bonding step, the The release buffer material (C) is arranged on at least one of the non-contact side of the single-sided metal-clad laminate (A) and the metal shaped sheet (B), facing a pair of pressure rollers (r 1 , r 2 ) Import. 如請求項6的覆金屬之積層體的製造方法，其中該脫模緩衝材(C)和該單面覆金屬之積層體(A)或該金屬賦形薄片(B)的剝離強度為0.1N/mm以下。The method for manufacturing a metal-clad laminate according to claim 6, wherein the peeling strength of the release buffer material (C) and the single-sided metal-clad laminate (A) or the metal shaped sheet (B) is 0.1N /mm or less. 如請求項6或7的覆金屬之積層體的製造方法，其中該脫模緩衝材(C)係從包含耐熱性樹脂薄膜、耐熱性複合薄膜、耐熱性不織布、及至少一面具備脫模層的金屬箔的群組選出。The method for manufacturing a metal-clad laminate according to claim 6 or 7, wherein the release buffer material (C) is made from a heat-resistant resin film, a heat-resistant composite film, a heat-resistant non-woven fabric, and at least one side with a release layer The group of metal foil is selected. 如請求項6至8中任一項的覆金屬之積層體的製造方法，其中該脫模緩衝材(C)的至少一面的表面粗糙度(Rz)為2.0μm以下。The method for manufacturing a metal-clad laminate according to any one of claims 6 to 8, wherein the surface roughness (Rz) of at least one side of the release buffer material (C) is 2.0 μm or less. 如請求項6至9中任一項的覆金屬之積層體的製造方法，其中在該熱壓接步驟中，以成為(r1 )/(C)/(A)/(B)/(r2 )的順序的方式，將單面覆金屬之積層體(A)、金屬賦形薄片(B)及脫模緩衝材(C)重疊而導入於一對加壓輥(r1 , r2 )之間。The method for manufacturing a metal-clad laminate according to any one of claims 6 to 9, wherein in the thermal compression bonding step, (r 1 )/(C)/(A)/(B)/(r 2 ) In a sequential method, the single-sided metal-clad laminate (A), the metal shaped sheet (B) and the release buffer material (C) are superimposed and introduced into a pair of pressure rollers (r 1 , r 2 ) between. 如請求項10的覆金屬之積層體的製造方法，其中在該熱壓接步驟中，加壓輥(r2 )係加熱溫度比加壓輥(r1 )高。The method for manufacturing a metal-clad laminate according to claim 10, wherein in the thermal compression bonding step, the pressure roller (r 2 ) is heated at a higher temperature than the pressure roller (r 1 ). 如請求項1至11中任一項的覆金屬之積層體的製造方法，其中分別準備複數個長條狀的單面覆金屬之積層體(A)及長條狀的金屬賦形薄片(B)，製造複數個覆金屬之積層體。The method for manufacturing a metal-clad laminate according to any one of claims 1 to 11, wherein a plurality of elongated single-sided metal-clad laminates (A) and elongated metal shaped sheets (B ), to manufacture a plurality of metal-clad laminates. 如依附於請求項6至9中任一項的情況下的請求項11的覆金屬之積層體的製造方法，其中在該熱壓接步驟中，將脫模緩衝材(C)重疊而導入於複數組的包含單面覆金屬之積層體(A)及金屬賦形薄片(B)的積層體之間。For example, the method for manufacturing the metal-clad laminate of claim 11 in the case of being attached to any one of claims 6 to 9, wherein in the thermal compression bonding step, the release buffer material (C) is overlapped and introduced into Between the multiple arrays of laminates including single-sided metal-clad laminates (A) and metal-shaped flakes (B). 如請求項13的覆金屬之積層體的製造方法，其中在該熱壓接步驟中，以成為(r1 )/(B)/(A)/(C)/(A)/(B)/(r2 )的順序的方式，將單面覆金屬之積層體(A)、金屬賦形薄片(B)及脫模緩衝材(C)重疊而導入於一對加壓輥(r1 , r2 )之間。The method for manufacturing a metal-clad laminate according to claim 13, wherein in the thermocompression bonding step, (r 1 )/(B)/(A)/(C)/(A)/(B)/ (r 2 ) The single-sided metal-clad laminate (A), the metal shaped sheet (B), and the release buffer material (C) are superimposed and introduced into a pair of pressure rollers (r 1 , r) in the order of (r 2) 2 ) Between. 如依附於請求項6至9中任一項的情況下的請求項11或請求項12的覆金屬之積層體的製造方法，其中在該熱壓接步驟中，以與一對加壓輥(r1 , r2 )中的至少一個加壓輥相接的方式，將脫模緩衝材(C)重疊而導入。If attached to any one of claims 6 to 9, the method for manufacturing a metal-clad laminate of claim 11 or claim 12, wherein in the thermal compression bonding step, a pair of pressure rollers ( In the mode that at least one pressure roller in r 1 , r 2 ) is in contact with each other, the release buffer material (C) is overlapped and introduced. 如請求項15的覆金屬之積層體的製造方法，其中在該熱壓接步驟中，以成為(r1 )/(C)/(B)/(A)/(A)/(B)/ (C)/(r2 )、或者是(r1 )/(C)/(A)/(B)/(B)/(A)/(C)/(r2 )的順序的方式，將單面覆金屬之積層體(A)、金屬賦形薄片(B)及脫模緩衝材(C)重疊而導入於一對加壓輥(r1 , r2 )之間。The method for manufacturing a metal-clad laminate according to claim 15, wherein in the thermocompression bonding step, (r 1 )/(C)/(B)/(A)/(A)/(B)/ (C)/(r 2 ) or (r 1 )/(C)/(A)/(B)/(B)/(A)/(C)/(r 2 ) The single-sided metal-clad laminate (A), the metal shaped sheet (B), and the release buffer material (C) are overlapped and introduced between a pair of pressure rollers (r 1 , r 2 ).
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