201202022 六、發明說明： 【發明所屬之技術領域】 本發明係關於一種單面覆金屬積層體的製造方法，係 製造在具有由熱塑性樹脂所構成之接著面之絕緣性薄膜上 接著金屬箔而成之單面覆金屬積層體的方法。 【先前技術】 近年來由於電氣機器之小型化.輕量化.高機能化之發 展’使軟性電路基板（flexible circuit board)之使用隨之 增加，例如在其表面具有熱塑性之聚醯亞胺薄膜及液晶聚 合物薄膜等絕緣薄膜上熱壓合（thermocompression)金屬 而成之覆金屬積層體，即為適於使用之例。具有此種構造 之積層體，其製造法一般係採用將絕緣薄膜與金屬箔以滾 輪對滾輪（rol卜to-roll)之方式輸送，一邊加熱一邊使其 通過一對之加壓滾輪之間而連續地進行熱壓合的方法。 例如在專利文獻1中所揭示之提案，係在对熱性薄膜 之兩面具有熱塑性樹脂層之接著片之單面上熱壓合金屬羯 時’藉由在熱壓合裝置之加壓面與接著片之間配置保護材 料，而防止未積層金屬箔之側之熱塑性樹脂層熔接於金屬 滾輪及保護薄膜之方法。然而，在該方法中，因缺少用以 進行均勻加壓之壓力緩衝效果，特別在使用薄之接著片及 薄之金屬箔時，由於加壓不均，而有產生未接著之部份及 接著強度弱之部份之虞’並且亦可能在接著片與金屬羯之 層間形成空隙，而有發生皺紋等外觀不良之缺陷。 另外’在專利文獻2中所揭示之提案，係在將液晶聚 322680 4 201202022 , 合物薄膜與金屬箔重疊並以金屬加壓滚輪進行熱壓合時， 在與金屬加壓滾輪接觸之面上再重疊耐熱性樹脂薄膜而製 造積層體之方法。以該方法，在製造目的之積層體與滾輪 之間係介置有耐熱性樹脂薄膜，因此可期待產生一定之緩 衝效果，但相反地，其加壓滾輪之熱傳導至被積層體之傳 熱效果卻會受阻’因此使金屬箔與液晶聚合物薄膜之接著 力降低，而可能發生接著力不均之情形。 另外，在專利文獻3中所揭示之提案，係將熱塑性聚 合物薄膜與被接著體於滾輪間進行熱處理且同時使其壓合 之積層體之製造方法，其中，將熱塑性聚合物薄膜與被接 著體重疊，在從其兩側以被覆材包夾之狀態下進行壓合， 藉此而使薄膜與被接著體在短時間中強穩地壓合。惟該方 法中’會有因為保護材料與加熱加壓面直接接觸而使保護 讨科易於劣化，因此減少保護材料之再利用次數 ，而增加 製造成本等之缺點。同時，其亦有與專利文獻1同樣之情 衫’在使用薄之熱塑性聚合物薄膜及薄之被接著體時，會 有易於形成未接著部份及弱接著部份之虞慮，此外亦可能 發生層間空隙及皺紋等。 [先前技術文獻] [聲利文獻] [專利文獻1]日本特開2008-272958號公報 [專利文獻2] W02004/108397號公報 [專利文獻3]日本特開2001-88219號公報 【發明内容】 5 322680 201202022 (發明欲解決之課題） 因此’本發明之目的係提供一種使絕緣性薄膜與金屬 箱之層間密接性佳，接著強度不會不均，抑制皺紋等外觀 不良之發生，且可工業生產性佳地製造單面覆金屬積層體 的方法。 a (解決課題之手段） 本發明人等為解決上述先前技術之問題而精心研究之 結果，發現將絕緣性薄膜與金屬箔之組合以間隔薄膜為中心 而形成上下對稱之2組並予以重疊，經加壓滾輪進行熱壓人 後’不會有薄膜熔接至加壓滾輪上之虞，並且由於使加壓穿 輪間之壓力更均勻地傳導，因此可防止接著強度不均、及皺 紋之發生等，而且若從間隔薄膜剝離，即可一次獲得2組此 種品質安定之單面覆金屬積層體，而完成本發明。 亦即，本發明之單面覆金屬積層體的製造方法，係製 造在具有由熱塑性樹脂所構成之接著面之絕緣性薄膜（八） 上接著有金屬箔（B)之單面覆金屬積層體的方法，其特徵係 使用表面及内面皆為表面粗度（RZ)2· 〇#in以下之間隔薄 膜（C)，並在一對之加壓滾輪（rl、r2)之間以 (rl)/(B)/(A)/(C)/(A)/(B)/(r2)之順序，將絕緣性薄膜 (A)、金屬箔（B)、及間隔薄膜（C)重疊並熱壓合，從間隔薄 膜（C)剝離而獲得2個單面覆金屬積層體。 (發明之效果） 依據本發明，可以優良之工業生產性製造不產生敵紋 及接著強度不均’且絕緣性薄膜與金屬箔之層間密接性佳 322680 6 201202022 之尚品質之單面覆金屬積層體。亦即，相鼓於、 本發明之製造方法玎大幅提高工業生產欵率；u往之方法， 低之成本製成高品質之單面覆金屬積層體。，因此可以更 所獲得之單面覆金屬積層體，具有高品 此外’本發明 貝可' n (reliability)優良’故可適合使用於作為例养性 案（fine pattern)時所需之電路基板、及夕如形成精細圖 之基板材料。 >層電路基板用 【實施方式】 以下詳細說明本發明。 單面覆金屬積層體 本發明中，係在一對之加壓滾輪（rl、r2)之門、 屬箱（B)/絕緣性薄膜（A)/間隔薄膜（c)/絕緣性薄膜M金 屬副之順序重疊並熱壓合，之後從間隔薄膜(c;二/金 而同時製造2個在絕緣性薄骐（A)上接著金屬f§(B)而=， 、，巴琢性溥膜（A)，只要是 由熱塑性樹脂所構紅接著W可經由熱壓合 _有 上貼合金屬細者即可，並無特別之限定，_可= 如：i)由熱塑性樹脂薄臈所構成者；以及其他例如⑴在 耐熱性樹料敎單面上設置熱塑性樹脂層㈣成接著面 者；iii)在耐熱性樹脂薄膜之兩面上設置熱塑性樹脂層， 並以其中任-者作為與金心之接著面者^此外，亦可 使用將其中之1種或2種以上重疊而製成複數層者。 其中，D由熱塑性樹月旨薄膜所構成之 之例，可列舉如聚對笨二甲酸乙二_脂、 322680 7 201202022 二酯樹脂、聚碳酸酯樹脂、丙烯腈/苯乙烯共聚樹脂、熱塑 性聚醯亞胺樹脂、液晶聚合物等，其中在加工性、電氣特 性、耐熱性等觀點上，以液晶聚合物或熱塑性聚醯亞胺樹 脂較佳。 液晶聚合物之例，可列舉如由如下之（1)至（4)分類之 化合物及其衍生物所導出之周知之熱向型液晶 (thermotropic liquidcrystal)聚酯、熱向型液晶聚酯醯 胺等。 (0芳族或脂族二羥基化合物 (2) 芳族或脂族二羧酸 (3) 芳族經基叛酸 (4) 芳族二胺、芳族經基胺或芳族胺基叛酸 由此等原料化合物所獲得之液晶聚合物中，又以分子 中不含脂族鏈之芳族液晶聚合物較佳。此類液晶聚合物之代 表例，可列舉如以6-羥基_2一萘曱酸及對羥基苯甲酸為原料 所製成且含有下述式所示構成單位之共聚物 。其中，下述式 中之m2及m為顯示各構成單位之存在莫耳數比的正數。201202022 SUMMARY OF THE INVENTION Technical Field The present invention relates to a method for producing a single-sided metal-clad laminate, which is produced by laminating an insulating film having an adhesive surface made of a thermoplastic resin. A method of coating a metal layer on one side. [Prior Art] In recent years, due to the miniaturization of electric machines, the development of lightweight and high-performance, the use of flexible circuit boards has increased, for example, thermoplastic polyimide films on their surfaces and A metal-clad laminate obtained by thermocompressing a metal on an insulating film such as a liquid crystal polymer film is an example suitable for use. The laminated body having such a structure is generally produced by transporting an insulating film and a metal foil by a roller-to-roll, and heating it while passing between a pair of pressing rollers. A method of performing thermal compression bonding continuously. For example, in the proposal disclosed in Patent Document 1, when the metal crucible is thermocompression-bonded on one surface of the succeeding sheet having the thermoplastic resin layer on both sides of the thermal film, 'by the pressurizing surface and the adhesive sheet of the thermocompression bonding apparatus A method of preventing the thermoplastic resin layer on the side of the unlaminated metal foil from being welded to the metal roller and the protective film by disposing a protective material therebetween. However, in this method, due to the lack of a pressure buffering effect for uniform pressurization, particularly when a thin back sheet and a thin metal foil are used, due to uneven pressure, there is a non-adult part and then It is also possible to form a gap between the underlying sheet and the layer of the metal crucible, and there is a defect that the appearance is poor such as wrinkles. Further, the proposal disclosed in Patent Document 2 is a method in which a liquid crystal poly 322680 4 201202022 film is laminated on a metal foil and is thermally pressed by a metal pressure roller, on the surface in contact with the metal pressure roller. A method of producing a laminate by superposing a heat resistant resin film. According to this method, a heat-resistant resin film is interposed between the laminate and the roller for the purpose of production, so that a certain cushioning effect can be expected, but conversely, the heat transfer of the pressure roller to the heat transfer effect of the laminated body However, it will be hindered, so that the adhesion between the metal foil and the liquid crystal polymer film is lowered, and uneven adhesion may occur. Further, the proposal disclosed in Patent Document 3 is a method for producing a laminate in which a thermoplastic polymer film and a substrate are heat-treated between rolls, and simultaneously pressed, wherein a thermoplastic polymer film is followed. The body is superposed and pressed together in a state of being sandwiched by the covering material on both sides, whereby the film and the adherend are strongly pressed in a short time. However, in this method, since the protective material is in direct contact with the heated and pressed surface, the protection is easily deteriorated, so that the number of reuse of the protective material is reduced, and the manufacturing cost is increased. At the same time, it also has the same feelings as in Patent Document 1 'When a thin thermoplastic polymer film and a thin adherend are used, there is a concern that it is easy to form a non-subsequent portion and a weakly subsequent portion, and it is also possible Interlayer voids, wrinkles, etc. occur. [PRIOR ART DOCUMENT] [Patent Document 1] Japanese Laid-Open Patent Publication No. 2008-27219 (Patent Document 3) Japanese Laid-Open Patent Publication No. 2001-88219 5 322 680 201202022 (Problems to be Solved by the Invention) Therefore, the object of the present invention is to provide an excellent adhesion between the insulating film and the metal case, and the strength is not uneven, and the occurrence of appearance defects such as wrinkles is suppressed. A method of producing a single-sided metal-clad laminate in a productive manner. (Means for Solving the Problem) As a result of intensive studies to solve the problems of the prior art described above, the present inventors have found that the combination of the insulating film and the metal foil forms two groups of upper and lower symmetry centering on the spacer film and superimposes them. After the hot pressing of the pressure roller, there is no flaw in the film welding to the pressure roller, and since the pressure between the pressure rollers is more uniformly transmitted, uneven strength and wrinkles can be prevented. And, if it is peeled off from the spacer film, two sets of such a single-sided metal-clad laminate having such a stable quality can be obtained at one time, and the present invention has been completed. That is, the method for producing the single-sided metal-clad laminate according to the present invention is a one-side metal-clad laminate in which an insulating film (8) having a bonding surface made of a thermoplastic resin is followed by a metal foil (B). The method is characterized in that the surface and the inner surface are both a film (C) having a surface roughness (RZ) 2 · 〇 #in or less, and (rl) between a pair of pressure rollers (rl, r2) In the order of /(B)/(A)/(C)/(A)/(B)/(r2), the insulating film (A), the metal foil (B), and the spacer film (C) are superposed and heated. The film was peeled and peeled off from the spacer film (C) to obtain two single-sided metal-clad laminates. (Effects of the Invention) According to the present invention, it is possible to produce a single-sided metal-clad layer which is excellent in industrial productivity and which does not cause enemies and subsequent unevenness in strength and which has good adhesion between the insulating film and the metal foil. 322680 6 201202022 body. That is to say, the manufacturing method of the present invention greatly increases the industrial production rate; and the method of the invention is to produce a high-quality single-sided metal-clad laminate at a low cost. Therefore, the single-sided metal-clad laminate which can be obtained more preferably has a high quality and is excellent in the reliability of the present invention, so that it can be suitably used for a circuit substrate which is required as a fine pattern. And the formation of a fine-grained substrate material. > Layer circuit substrate [Embodiment] Hereinafter, the present invention will be described in detail. Single-sided metal-clad laminate In the present invention, it is a pair of pressing rollers (rl, r2), a box (B) / an insulating film (A) / a spacer film (c) / an insulating film M metal The sub-orders are overlapped and thermocompressiond, and then from the spacer film (c; two / gold while two are fabricated on the insulating thin crucible (A) followed by the metal f § (B) =, ,, 琢 琢 溥 film (A) is not particularly limited as long as it is made of a thermoplastic resin and then W can be bonded to the metal by thermal compression. _ can be = i) composed of a thin resin of thermoplastic resin And other, for example, (1) providing a thermoplastic resin layer on one surface of the heat-resistant tree material (4) as a back surface; iii) providing a thermoplastic resin layer on both sides of the heat-resistant resin film, and using any of them as the gold core In addition, one or two or more of them may be used to form a plurality of layers. Wherein, D is an example of a thermoplastic resin film, and examples thereof include poly(p-phenylene terephthalate), 322680 7 201202022 diester resin, polycarbonate resin, acrylonitrile/styrene copolymer resin, and thermoplastic poly A quinone imine resin, a liquid crystal polymer, etc., and a liquid crystal polymer or a thermoplastic polyimide resin is preferable in terms of workability, electrical characteristics, heat resistance, and the like. Examples of the liquid crystal polymer include well-known thermotropic liquid crystal polyesters derived from the compounds classified by the following (1) to (4) and derivatives thereof, and thermal-oriented liquid crystal polyester decylamine. Wait. (0 aromatic or aliphatic dihydroxy compound (2) aromatic or aliphatic dicarboxylic acid (3) aromatic transbasic acid (4) aromatic diamine, aromatic transamine or aromatic amine traconic acid The liquid crystal polymer obtained by the raw material compound is preferably an aromatic liquid crystal polymer containing no aliphatic chain in the molecule. Representative examples of such a liquid crystal polymer include, for example, 6-hydroxy-2. A naphthoic acid and a p-hydroxybenzoic acid are used as a raw material and contain a copolymer of the following formula: m2 and m in the following formula are positive numbers showing the molar ratio of each constituent unit.
性上，以較好為在2〇〇至4〇(Tc之範圍，更好為在250至 350 C之範圍内具有往光學異向性（〇pticai ly anis〇tr〇py) 8 322680 201202022 之熔融相的轉移溫度者較佳。又，液晶聚合物中在不減損其 特性之範圍内，亦可調配例潤滑劑、抗氧化劑、填充劑等。 將液晶聚合物予以薄膜化之方法，可例舉如τ模且法（τ die method)、層合體延伸法、充氣法（inflati〇n meth〇d) 等。其中，若使用充氣法及層合體延伸法，則不只會在薄膜 之機械抽方向（MD方向）施加應力，亦會在與其垂直之方向 (TD方向）施加應力，因此，可製成其MD方向與TD方向之 機械性質達成平衡之薄膜。液晶聚合物薄膜亦可使用市售商 品，例如KURARAY公司製造之Vecstar(註冊商標）、及日本 G0RE-TEX公司製造之BIAC、STABIAX(均為註冊商標）等。 此外，熱塑性聚醯亞胺樹脂係可藉由將其前驅物之聚 醯胺酸進行酿亞胺化（硬化）而形成，其中之聚醯胺酸可藉由 將一般已知之二胺與酸酐在溶劑存在下進行反應而製成。 熱塑性聚酿亞胺樹脂中所使用之前驅物，係以具有下 述通式（1)所示之構造單位之前驅物較佳。通式（1)中，ΑΓ3 表示式（2)、式（3)或式（4)所示之2價芳基；An表示式（5) 或式（6)所示之4價芳基；r2係獨立地表示碳原子數1至6 之1價烴基或烷氧基；V及W獨立地表示單鍵或選自由碳 原子數1至15之2價烴基、〇、s、CO、S〇2、或C0NH中之 2價基；mi獨立地表示0至4之整數；P表示構成單位之存 在莫耳比’為0.1至1.0之值。Sexually, preferably in the range of 2〇〇 to 4〇 (Tc, more preferably in the range of 250 to 350 C) to optical anisotropy (〇pticai ly anis〇tr〇py) 8 322680 201202022 The transfer temperature of the molten phase is preferably one. Further, the liquid crystal polymer may be formulated with a lubricant, an antioxidant, a filler, etc. within a range that does not detract from the characteristics. The method of thinning the liquid crystal polymer may be exemplified. For example, the τ die method, the laminate extension method, the inflating method (inflati〇n meth〇d), etc., if the inflation method and the laminate extension method are used, not only in the mechanical drawing direction of the film When the stress is applied in the (MD direction), stress is applied in the direction perpendicular thereto (TD direction), so that a film in which the mechanical properties of the MD direction and the TD direction are balanced can be obtained. The liquid crystal polymer film can also be used as a commercial product. For example, Vecstar (registered trademark) manufactured by KURARAY Co., Ltd., and BIAC, STABIAX (both registered trademarks) manufactured by G0RE-TEX Corporation of Japan, etc. In addition, thermoplastic polyimide resin can be obtained by agglomerating its precursors. Amino acid Formed by hardening, wherein the polyamine can be prepared by reacting a generally known diamine with an acid anhydride in the presence of a solvent. The precursor used in the thermoplastic polyimide resin has The structural unit precursor represented by the following formula (1) is preferred. In the formula (1), ΑΓ3 represents a divalent aryl group represented by the formula (2), the formula (3) or the formula (4); a tetravalent aryl group represented by the formula (5) or the formula (6); r2 each independently represents a monovalent hydrocarbon group or alkoxy group having 1 to 6 carbon atoms; and V and W independently represent a single bond or are selected from carbon a divalent hydrocarbon group having 1 to 15 atomic number, hydrazine, s, CO, S 〇 2, or a valent group in C0NH; mi independently represents an integer of 0 to 4; and P represents a molar unit of a constituent unit of 0.1. To a value of 1.0.
9 322680 3 2012020229 322680 3 201202022
(R2)BM /R2)mi (R2)mi (R2)i"i -(2) (R2)mi (R2)mi (R2)mi (R2)[ni 4 ) …(5) …⑷ 其中使用之二胺，可例舉如4, 4’ -二胺基二苯基醚、2’ -曱氧基-4, 4’-二胺基苯甲酼苯胺、1，4-雙（4-胺基笨氧基） 笨、1，3-雙（4-胺基苯氧基）笨、2, 2,-雙[4-(4-胺基笨氧基） 笨]丙烷、2, 2，-二曱基-4, 4，-二胺基聯苯、3, 3，-二羥基 -4, 4’ -二胺基聯苯、4, 4,-二胺基苯曱醯苯胺等。酸酐之例， 可列舉如均苯四曱酸二酐（pyromel 1 itic dianhydride)、 3, 3，4, 4’ -聯苯四羧酸二酐、3, 3’，4, 4’ -二苯基砜四羧酸 二野、4, 4’ -氧雙鄰苯二曱酸酐（4, 4, -oxydiphthal ic anhydride)等》二胺及酸酐可分別只使用其1種，亦可併 用2種以上。聚醯亞胺樹脂並不限定為由如上述之二胺與 酸酐所製成者。 絕緣性薄臈（A)在使用熱塑性聚醯亞胺樹脂薄膜時，該 薄膜可由聚醯亞胺樹脂前驅物之聚酿胺酸經由拉幅法 (tentering)及鑄製法（cast method)等一般已知之方法使 其薄膜化。其代表方法之一之拉幅法，為將聚醯胺酸溶液 流延至旋轉之滾輪，以聚醯胺酸之膠體薄膜之狀態自旋轉 322680 10 201202022 / 之滾輪上剝離，之後再經拉幅爐（tentei* 〇ven)進行加熱/ - 硬化（醯亞胺化）而製成聚醯亞胺薄膜之方法。鑄製法為在 任意之支持基材上將聚酿胺酸溶液塗佈、乾燥後，經熱處 理而硬化（醯亞胺化）以製成聚醯亞胺薄膜之方法。醯亞胺 化可藉由例如在80至400°C之溫度條件下於1至60分鐘之 時間範圍内加熱而進行。又，聚醯亞胺樹脂在不減損其特性 之範圍内，亦可調配例如潤滑劑、抗氧化劑、填充劑等。 絕緣性薄膜（A)，在使用ii)在耐熱性樹脂薄膜之單面 上設置熱塑性樹脂層者、或iii)在耐熱性樹脂薄膜之兩面 上設置熱塑性樹脂層者時，該耐熱性樹脂薄膜只要是其熱 變形溫度係比熱塑性樹脂層高者即可，並無特別之限定， 其中以非熱塑性之聚醯亞胺樹脂薄膜較佳。非熱塑性聚醯 亞胺樹脂係與熱塑性聚醯亞胺相同，可藉由將一般已知之 二胺與酸酐在溶劑存在下反應而製成，其中可藉由改變其 所使用之原料組合而製成耐熱性之聚醯亞胺樹脂。該非熱 塑性聚醯亞胺樹脂薄膜有市售商品，可列舉如Du Pont-Toray 股份公司製造之 Kapton ΕΝ、Kapton Η、Kapton V(均 為商品名）；鐘淵化學股份公司製造之APICAL NPI(商品 名）；宇部興產股份公司製造之UPILEX-S(商品名）等。非 熱塑性聚醯亞胺樹脂薄膜，以玻璃轉移溫度在300°C以上 者為佳，並且以在由滾輪所致之熱壓合之溫度下亦不變形 者更佳。 此外，在耐熱性樹脂薄膜之單面或兩面所設置之熱塑 性樹脂層，只要是由至少在熱壓合之加熱溫度以下具有玻 322680 201202022 璃轉變溫度之樹脂所形成者即可，且樹脂之種類並無特別 之限定，其例可列舉如熱塑性聚醯亞胺樹脂、熱塑性液晶 聚合物、聚醚醚酮、聚萘二曱酸乙二酯等。又，該熱塑性 樹脂層，可藉由在财熱性樹脂薄膜上接合熱塑性樹脂薄膜 而形成，亦可藉由將其前驅物以鑄製法等塗佈而形成。 絕緣性薄膜（A)之厚度，以5至200 ym為佳，10至 100/zm更佳。絕緣性薄膜（A)過薄時會減低其剛性，在覆 金屬積層體之製造步驟中及在使用所得之積層體之配線基 板之加工步驟中，有產生皺紋及破裂等缺陷之虞。另一方 面，在其過厚時，會使其絕緣性薄膜缺乏柔軟性，在覆金 屬積層體之製造步驟中會使滚輪對滚輪（roll-to-roll)之 輸送產生困難，此外，會發生經電路加工之配線基板不易 裝入狹小框體中等之缺陷。 本發明中使用之金屬箔（B)之材質並無特別之限定， 可例舉如金、銀、銅、不銹鋼、鎳、鋁等。其中，在導電 性、操作容易性、價格等之觀點上，以銅箔及不銹鋼箔較 佳。其中之銅箔，可使用以任意之壓延法（rol 1 ing process) 及電解法所製成者。此外，對於金屬箔，在提高其與絕緣 薄膜之接著力之目的下，亦可預先進行粗化處理等物理性 表面處理，以及酸洗淨、UV處理、電漿處理等化學性表面 處理。 金屬箔（B)之厚度，以1至100/zm為佳，5至7〇em 更佳，8至20/zm之範圍又更佳。若使金屬箔之厚度減低， 則在電路加工中易於形成精細圖案之觀點上為較佳，惟過 12 322680 201202022 薄時’不只在覆金屬積層體的製造步驟中容易於金屬箔產 生皺紋，且在經電路加工之配線基板中亦容易發生配線斷 裂，而有使作為配線基板之可靠性減損之虞慮。相反地在 在其過厚時，在金屬箔經蝕刻加工而形成電路時，在電路 侧面上容易發生漸縮（taper)之情形，對精細圖案之形成為 不利。 本發明中所使用之間隔薄膜（c)，除了須有耐熱壓合 溫度之耐熱性之外，亦必須在熱壓合後可容易地與絕緣性 薄膜（A)剝離。在後者之觀點上，以使用間隔薄膜（c)之表 面及内面均為表面粗度（RZ)2. 〇以m以下者為佳，以〇· 5至 1.5/zm者更佳。在易於同時確保耐熱性與表面平滑性方 面’間隔薄膜（C)係以使用非熱塑性之聚醢亞胺薄膜及聚醯 胺薄膜等财熱性樹脂薄膜、或紹箔及不錢鋼箔等金屬箔較 佳。此外，亦可使用樹脂薄膜之表面及内面具有金屬箔之 複合薄膜。間隔薄膜（C)在表面及内面之表面粗度（Rz)超過 2.0从m時’由於錨定作用（anchoring effect)會使絕緣性 薄膜（A)與間隔薄膜（C)之層間密接力提高，使由絕緣性薄 膜（A)及金屬镇（B)所製成之單面覆金屬積層體在從間隔薄 膜（C)剝離時之剝離阻力增加，因此而有使單面覆 體產生斷裂及皺紋等外觀上缺陷之虞慮。 θ 對於間隔薄膜（C)，在增加其熱壓合後與絕緣性薄臈 (Α)之剝離性之目的上，以將間隖薄膜（〇之單面或雙面進 行離型處理為佳。離型處理之具體方法，可列舉如在門s 薄膜（C)上設置聚矽氧（silicone)樹脂、氟系樹脂等耐 322680 13 201202022 型樹脂皮膜之方法等。 間隔薄膜（C)之厚度，較好在10至300 //m，更好在 20至150/zm，又更好在30至100/zm之範圍。間隔薄膜（C) 過薄時，使熱壓合時之壓力均勻分散之壓力缓衝效果會降 低，而使製成之覆金屬積層體之絕緣性薄膜（A)與金屬箔（B) 之層間密接性會有不均之虞慮。另一方面，在其過厚時， 可能會阻礙滾輪對滚輪之方式之輸送，或是在熱壓合後從 覆金屬積層體剝離時有使作業性變差之虞慮。 就絕緣性薄膜（A)、金屬箔（B)、及間隔薄膜（C)之組 合而言，在熱壓合步驟中之操作容易性及經濟性（材料成 本、間隔薄膜之再利用性等）、及製成之單面覆金屬積層體 的特性（機械特性、電氣特性、熱特性、加工性等）之觀點 上，較佳為：其絕緣性薄膜（A)係使用厚度10至100 之液晶聚合物薄膜、或在至少一方之表面上具有熱塑性樹 脂層之聚醯亞胺薄膜；其金屬箔（B)係使用厚度5至70/zm 之銅箔；其間隔薄膜（C)係使用表面及内面皆為表面粗度 (Rz)2. 0//m以下，且厚度為5至70/zm之鋁箔。 在一對之加壓滚輪（rl、r2)之間，將以 (rl)/(B)/(A)/(C)/(A)/(B)/(r2)之順序重疊之絕緣性薄 膜（A)、金屬箔（B)、及間隔薄膜（C)進行熱壓合時，可使用 具備具有加熱裝置之一對之加壓滾輪的一般已知之加熱加 壓裝置。此時，對於絕緣性薄膜（A)、金屬箔（B)、及間隔 薄膜（C)，若各自將捲成滚輪狀之長形材料與加熱加壓裝置 組合使用，即可連續製造單面覆金屬積層體。此外，加壓 14 322680 201202022 滾輪之溫度及加壓滾輪之壓力 於絕緣性賴⑴讀錄定，惟由 fl⑻良好地接著’因此，以比熱塑性樹 而與金屬 低m操作為佳。例如在絕緣 θ 點稍 物薄膜時，以比其溶點低5至丨G『c之溫_用液晶聚合 比其熔點低20至8〇。(：之溫度範圍 胍^ 7奴佳，以 -,ΛΛ 啤災隹。此外，丨”好 壓力在20至200kN/m之範圍時又為更佳 “加壓 本發明中，隔著間隔薄膜（ 緣性薄膜U)及金屬_由於係形成以間隔二 心而？立於對稱位置之關係，故其一對之力•衰輪)為中 r2)可β又為相同之溫度而進行熱壓合， r 必要之熱損失。此外’由於加壓滚輪均與金屬f =不 因此，加壓滾輪上之熱傳導不易受阻。又，在經熱二， 如下述實施例中之說明，其絕緣性薄膜(A)與間隔薄： 之層間剝離強度為G.1’以下而極易於剝離，可防止盆 接著強度不均、鈹紋之發生’因此，可生產性良好地獲得 高品質之單面覆金屬積層體。再者，雖然本發明係藉:介 置間隔4膜（C)而從2組之絕緣性薄膜（A)及金屬箱⑻獲 得單面覆金屬積層體’但亦可另檢討藉由介置間隔薄獏 並使用2組之（B)/(A)/(B)組合，而一次製成2個在兩面具 有金屬箔之雙面覆金屬積層體的變化例。 ' 實施例 以下，以實施例具體說明本發明，惟本發明並不限定 於以下之内容。此外，在後述之本發明實施例中，除非特 322680 15 201202022 別限定，其加工條件、測定（評估）之條件係如下述中所述。 [表面粗度之測定] 依照JIS B 0601，使用觸針式表面粗度測定器（TENC〇R 公司製造’TENCORP-10)’以負载l〇0/zN、掃描速度2〇"m/ 秒鐘、測定距離800 //m之條件測定rz(十點平均粗度）。 [間隔薄膜（C)之剝離性之評估] 將經熱壓合後而含有間隔薄膜（C)之積層物 (B/A/C/A/B) ’以對其加廢滾輪之長方向切割成寬度1〇丽、 對其層合進行方向（MD方向）切割成長度15〇mm而製備成板 條狀剝離性試驗片’並將其絕緣性薄膜（A)與間隔薄膜（c) 之層間剝離性依照J IS K 6854-3(T型剝離）測定。其中之 剝離速度定為100mm/分鐘。 [覆金屬積層體之密接性之評估] 將所付之早面覆金屬積層體對其層合進行方向（MD方 向）切割成長度150mm，使用市售之蝕刻液（ADEKACHELUMICA FE-210 ’ ADEKA股份公司製造）以減色法（subtractive method)蝕刻鋼箔，並沿著其層合進行方向而形成寬度imin、 長度100mm之直線導體圖案7(參考第3圖）。其中，直線 導體圖案7’係在單面覆金屬積層體之寬方向（加壓滾輪之 長方向）之中央位置、由中央往寬方向在左右各間隔30mm 之位置上形成3處圖案，而作為密接性試驗片。對該密接 性試驗片之3條直線導體圖案，依照JISC 6471 8. 1之方 法B(往180°方向之拉離）測定其從絕緣性薄膜（A)剝離之 強度。之後，3條之剝離強度之平均值係以1. OkN/m以上 16 322680 201202022 '時為良好，0.5kN/m以上且未達^⑽^時為尚可，未達 -〇.5kN/m時為不良之3等級評估其「密接性」.此外，3條 之剝離強度中之最大值與最小值之差係評估為「密接性之 不均程度」。 (實施例1) 準備將厚度為50ym、寬度為7〇mm之液晶聚合物薄臈 1(熔點320。〇捲成滾輪狀之長形薄獏以作為絕緣性薄膜 (A)，另準備將厚度為12ym、寬度為7〇咖之市售之電解 銅羯2(表面粗度Rz:絕緣性薄膜積層面16ym、露出面 1.4 vm)捲成滾輪狀之長形銅箔以作為金屬箔（B)，再準備 將厚度為50/zm、寬度為70mm之鋁箔3(表面及内面均為表 面粗度Rz : 1.2/zm)捲成滚輪狀之長形鋁箔以作為間隔薄 膜（C)。如第1圖所不，將此等分別裝設至絕緣性薄膜饋出 滾輪A、金屬箔饋出滾輪8、間隔薄臈饋出滚輪c，再在— 對之加壓錄4(小1*2)之_"铸_而晶聚合物薄 膜1/㈣3/液晶聚合物薄膜"電解銅2”之順序重疊並 供給（如第2圖），其經熱壓後使其自然冷卻，並使用剝離 滾輪6而將㈣3與液晶聚合物薄膜i層間剝離，_ 3 則由間隔薄膜捲取滾輪C，回收，貼合有液晶聚合物薄膜丄 及電_2之單面覆鋼積層體5則各由設置在2處之製 品捲取滾輪X所回收。 之後，再使電解2、液晶聚合物薄膜！、及 均以0.7m/分鐘之速度移動，並在2個均為表 之加壓滾輪4之間，以其浪輪間壓力撕q^壓合， 322680 17 201202022 熱壓合後再經自然冷卻使該積層物冷卻，並由間隔薄膜捲 取滚輪C’回收铭箔3，且由設置在2處之製品捲取滾輪X 各回收實施例1中之單面覆銅積層體5。其中，實施例1 所使用之裝置之加壓滾輪4均為由長度130mm、滾輪直徑 150mm之碳鋼製金屬滾輪所構成。 在上述實施例1中，熱壓合後之液晶聚合物薄膜i與 鋁箔3之層間剝離係無缺陷而極順利地進行，且分別以目 視觀察回收之早面覆銅積層體5之液晶聚合物薄膜面及電 解銅箔面時，完全未確認到發生破裂及皺紋、表面粗彳造之 情形。實施例1之單面覆銅積層體5在製造過程中，在經 加壓滾輪4熱壓合後到送入剝離滾輪6之前，切割前述剝 離試驗片’對其測定液晶聚合物薄膜1與鋁羯3之層間剝 離性之結果，確認其界面剝離之數值為無法測得之程度， 可極良好地剝離。此外’從由2處回收之單面覆銅積：體 5中之一方，如上述般操作而製成密接性試驗片後，評估 其液晶聚合物薄膜1與電解銅箔2之密接性之結果，依3 條之直線導體圖案所得之剝離強度之平均值而評估之「密 接性」為良好。此外，由該3條之剝離強度中之最大值與 最小值之差所求k「密接性之不輕度」為QQ3kN/m、， 而確認液晶聚合物薄臈丨與電解銅箔2係在面内均勻地 著。其結果如表1所示。 ""^ (實施例2) 除了間隔薄膜（C)係使用厚度5〇_之非熱塑性《市 售之财熱性聚醯亞胺薄膜3(Tg: 34(rc，表面及内面均為 322680 18 201202022 粗度Rz : 〇 9 a m)以 巧彳^ 卜’其餘與實施例1同樣地操作而獲 传貫施=之單面覆金屬積層體。 實％例2中’在熱壓合後之液晶聚合物薄膜1與财熱 曰:細^胺薄膜3之層間剝離係無缺陷而極順利地進行，以 土：▲、回收之單面覆銅積層體5之表面及内面時，完全 Ί破裂及κ、表面粗糖之情形。另外，在使用剝 離試驗片之測定中，i上 碟5忍其界面剝離為0. 07kN/m。此外， =密接性試驗片而進行之評估中其「密接性」良好，「密 不句程度」為〇. 〇2kN/m，而確認到液晶聚合物薄膜 =電解鋼落2係在面内均勻地接著。其結果如表1所示。 (實施例3) 間隔薄膜（〇係使用雙面覆銅積層體（新曰鐵化學 a司’ ESPANEX μ系列產品⑽12_25_12CEG))以外， 其餘與實〜例1進行同樣操作而獲得實_ 3之單面覆銅 積層體。該雙面覆鋼積層體中，其中心具有厚度加^ \=樹脂作為絕緣層’且在其兩面分別設置厚度12_ 之、=确㈣之露出面之表面粗度⑽)均為U，。 在實施例3之塑；生 表化·中，在熱壓合後之液晶聚合物薄膜 1 ’」、、、性聚酿亞胺薄膜3之層間剝離係無缺陷而極順利 地^丁」以目視觀察回枚之單面覆銅積層體5之表面及内 面時，元全未確認到破裂及敵紋、表面 粗糙之情形。此外， 在使^離氧驗片之測定中，確認其界面剝離為G·幢N/m; ^依據密接性試驗片而進行之評估中，其「賴性」良好， 密接佳之不均程度」為〇.03kN/m，而確認到單面覆銅積 19 322680 201202022 層體5係在面内均勻地接著。其結果如表1所示。 (比較例1) 除了間隔薄膜（C)係使用厚度為25//m且表面及内面 具有熱塑性聚醯亞胺之複合聚醯亞胺薄膜以外，其餘與實 施例1同樣地操作而獲得比較例1之單面覆銅積層體。該 複合聚醯亞胺薄膜，係在約21//m之非熱塑性聚醯亞胺之 兩側設置約2 // m之熱塑性聚醯亞胺而成者，由熱塑性聚醯 亞胺所構成之表面及内面之表面粗度（Rz)為2. 3以111。 該比較例1中，作為間隔薄膜而使用之複合聚醯亞胺 薄膜並無法順利地從熱壓後之液晶聚合物薄膜1剝離，在 使用剝離試驗片之測定中為0.50kN/m，確認到凝聚破壞 (cohesive fai lure)。此外，以目視觀察回收之單面覆銅 積層體5之表面及内面時，在液晶聚合物薄膜表面之整面 確認到因凝聚破壞而造成之粗糙情形。另一方面，在依密 接性試驗片而進行之評估中，其「密接性」雖為尚可，但 「密接性之不均程度」為0. 15kN/m，與實施例之結果比 較，可知其單面覆銅積層體5之面内之接著性不均勻。其 結果如表1所示。 (比較例2) 除了不使用間隔薄膜（C)以外，其餘與實施例1同樣 地操作而製成比較例2之單面覆銅積層體，其中在經熱壓 合並冷卻後，雖欲使單面覆銅積層體分離，但其作為絕緣 性薄膜（A)而使用之液晶聚合物薄膜1彼此之間發生熱熔 接，在採取剝離試驗片之測定中為0. 70kN/m，確認到凝聚 20 322680 201202022 . 破壞。並且，該所得之單面覆銅積層體在以目視觀察後， ^ 在液晶聚合物薄膜之表面整面確認到因凝聚破壞而造成之 粗糙情形，無法製成外觀良好之單面覆銅積層體。 (比較例3) 除了在一對之加壓滾輪4之間以"電解銅箔2/液晶聚 合物薄膜1/鋁箔3"之順序重疊以外，其餘與實施例1同樣 地操作而製成比較例3之單面覆銅積層體。 該比較例3中，雖只可獲得1個單面覆銅積層體，但 熱壓合後之液晶聚合物薄膜1與鋁箔3之層間剝離係順利 地進行，且在回收之單面覆銅積層體5之表面及内面完全 未確認到破裂及皺紋、表面粗糙之情形。此外，在依據剝 離試驗片而進行之測定中，確認界面剝離為0.01kN/m，在 依據密接性試驗片而進行之評估中，「密接性」為尚可。但 其「密接性之不均程度」為0. 17kN/m，與實施例之結果比 較，可知其面内之接著均勻性不佳。 (比較例4) 除了在一對之加壓滾輪4之間以’’鋁箔3/電解銅箔2/ 液晶聚合物薄膜1/鋁箔3’ ’之順序重疊以外，其餘與實施 例1同樣地操作而製成比較例4之單面覆銅積層體。 該比較例4中，與比較例3同樣地只可製成1個單面 覆銅積層體，但熱壓合後之液晶聚合物薄膜1與鋁箱3之 層間剝離係順利地進行，且在回收之單面覆銅積層體5之 表面及内面完全未確認到破裂及皺紋、表面粗糙之情形。 此外，在依據剝離試驗片而進行之測定中，確認界面剝離 21 322680 201202022 為0.01kN/m，在依據密接性試驗片而進行之評估中，「密 接性」良好。但其「密接性之不均情形」為〇.〇7kN/m，與 實施例之結果比較’可知其面内接著之均勻性不佳。 【表1】 間隔薄膜(C) 加壓滾輪間之 材料構成 (A)-(C)剝 離性 (A)-(B) 密接性 UHB)密接性 之不於格私 復銅積層 實施例1 銘箔（厚度50/^m，Rzl. 2 urn) B/A/C/A/B 無法測定 良好 〇.03kN/m 瓶i外觀 良好 實施例2 實施例3 耐熱性聚姐亞胺薄膜(厚 度 50#m，Rz〇. 9/zin) 雙面復銅積層體(厚度 B/A/C/A/B 0.07kN/m 良好 〇.02kN/m 良好 μη, Rzl.0//m) B/A/C/A/B 0.04kN/m 良好 〇. 03kN/m 良好 比較例1 比較例2 複合聚醯亞胺薄膜(厚度 25/zin, Rz2. 3^m) 無 B/A/C/A/B B/A/A/B 0.50kN/m 尚可 0.15kN/m 不良 比較例3 B箔（厚度 5〇；wm, Rzl.-f β!〇) B/A/C u. (UKiN/m 0.01kN/m 尚可 〇.17kN/m 不良 良好 比較例4 銘箔C厚度50/zm, Rzl.2 _β^)___ C/B/A/C 0.01kN/m 良好 0.07kN/m 良好 由以上之結果可知，若依據本發明之製造方法，即可 以良好之X#生紐製造*會發生皺紋及接著強度不均， 且絕緣性賴與金射I之層間密接性優良之高品質之單面 覆金屬積層體。此外，本發料受上述實卿態之限定， 可作各種之變化。 【圖式簡單說明】 第1圖係說明本發明之實施形態之單面覆金屬積層體 之製造裝置之側面示意圖。 第2圖係將加壓滾輪附近放大之示意圖。 第3圖係說明在評估絕緣性薄膜與金屬ϋ之密接性時 所使用之試驗片之平面示意圖。 【主要元件符號說明】 322680 22 201202022 液晶.聚合物薄膜（絕緣性薄膜（A )) 電解銅箔（金屬箔（B)) 3 鋁箔（間隔薄膜（C)) 4 加壓滾輪 5 單面覆銅積層體 6 剝離滚輪 7 直線導體圖案 A 絕緣性薄膜饋出滾輪 B 金屬箔饋出滾輪 C 間隔薄膜饋出滾輪 C， 間隔薄膜捲取滾輪 MD 層合進行方向 rl 、r 2 —對之加壓滚輪 X 製品捲取滚輪 23 322680(R2)BM /R2)mi (R2)mi (R2)i"i -(2) (R2)mi (R2)mi (R2)mi (R2)[ni 4 ) (5) (4) where The diamine may, for example, be 4,4'-diaminodiphenyl ether, 2'-decyloxy-4,4'-diaminobenzimidamide, 1,4-bis(4-amino group) Stupid oxy) stupid, 1,3-bis(4-aminophenoxy) stupid, 2, 2,-bis[4-(4-aminophenyloxy) stupid] propane, 2, 2,-di Mercapto-4,4,-diaminobiphenyl, 3,3,-dihydroxy-4,4'-diaminobiphenyl, 4,4,-diaminobenzoquinone, and the like. Examples of the acid anhydride include pyromel 1 itic dianhydride, 3, 3, 4, 4'-biphenyltetracarboxylic dianhydride, and 3,3',4,4'-diphenyl. The diamine and the acid anhydride may be used alone or in combination of two or more kinds of diamines and acid anhydrides. . The polyimine resin is not limited to those made of the above-mentioned diamine and acid anhydride. Insulating thin crucible (A) When a thermoplastic polyimide film is used, the film may be obtained from a tentering and casting method of a polyacrylamide resin precursor polylactoic acid. The method is known to make it thin. One of the representative methods of the tenter method is to cast a polyaminic acid solution to a rotating roller, and peel it off from a rotating 322680 10 201202022 / roller in the state of a colloidal acid colloidal film, and then pass through a tenter furnace. (tentei* 〇ven) A method of forming a polyimide film by heating/hardening (醯imination). The casting method is a method in which a polyacrylic acid solution is coated and dried on an arbitrary supporting substrate, and then subjected to heat treatment to be hardened (imidized) to form a polyimide film. The ruthenium imidization can be carried out, for example, by heating at a temperature of from 80 to 400 ° C for a period of from 1 to 60 minutes. Further, the polyimine resin may be blended with, for example, a lubricant, an antioxidant, a filler, or the like, within a range not detracting from its characteristics. In the insulating film (A), when ii) a thermoplastic resin layer is provided on one surface of the heat-resistant resin film, or iii) a thermoplastic resin layer is provided on both surfaces of the heat-resistant resin film, the heat-resistant resin film is only required The heat distortion temperature is preferably higher than that of the thermoplastic resin layer, and is not particularly limited, and a non-thermoplastic polyimide film is preferred. The non-thermoplastic polyimine resin is the same as the thermoplastic polyimine, and can be produced by reacting a generally known diamine with an acid anhydride in the presence of a solvent, which can be produced by changing the combination of raw materials used therein. Heat resistant polyimide resin. The non-thermoplastic polyimide film is commercially available, and examples thereof include Kapton®, Kapton®, and Kapton V (all trade names) manufactured by Du Pont-Toray Co., Ltd.; and APICAL NPI manufactured by Zhongyuan Chemical Co., Ltd. Name); UPILEX-S (trade name) manufactured by Ube Industries Co., Ltd., etc. The non-thermoplastic polyimide film has a glass transition temperature of 300 ° C or higher, and is preferably not deformed at the temperature of the heat compression by the roller. In addition, the thermoplastic resin layer provided on one side or both sides of the heat-resistant resin film may be formed of a resin having a glass transition temperature of at least 322680 201202022 at least below the heating temperature of the thermocompression bonding, and the kind of the resin. There is no particular limitation, and examples thereof include a thermoplastic polyimide resin, a thermoplastic liquid crystal polymer, polyether ether ketone, and polyethylene naphthalate. Further, the thermoplastic resin layer can be formed by bonding a thermoplastic resin film to a heat-sensitive resin film, or can be formed by coating a precursor thereof by a casting method or the like. The thickness of the insulating film (A) is preferably 5 to 200 μm, more preferably 10 to 100/zm. When the insulating film (A) is too thin, the rigidity thereof is reduced, and defects such as wrinkles and cracks are generated in the manufacturing step of the metal-clad laminate and in the processing step of using the wiring board of the obtained laminate. On the other hand, when it is too thick, the insulating film lacks flexibility, and in the manufacturing step of the metal-clad laminate, the roller-to-roll conveyance is difficult, and in addition, it may occur. The wiring board processed by the circuit is not easily loaded into a narrow frame or the like. The material of the metal foil (B) used in the present invention is not particularly limited, and examples thereof include gold, silver, copper, stainless steel, nickel, aluminum, and the like. Among them, copper foil and stainless steel foil are preferable from the viewpoints of conductivity, ease of handling, and price. Among them, the copper foil can be produced by any of the rol 1 ing process and the electrolysis method. Further, for the purpose of improving the adhesion of the metal foil to the insulating film, physical surface treatment such as roughening treatment, and chemical surface treatment such as pickling, UV treatment, and plasma treatment may be performed in advance. The thickness of the metal foil (B) is preferably from 1 to 100/zm, more preferably from 5 to 7 〇em, and even more preferably from 8 to 20/zm. If the thickness of the metal foil is reduced, it is preferable from the viewpoint of easily forming a fine pattern in circuit processing, but when 12 322680 201202022 is thin, it is easy to cause wrinkles in the metal foil not only in the manufacturing step of the metal-clad laminate, but also In the wiring board processed by the circuit, the wiring is likely to be broken, which may detract from the reliability of the wiring board. Conversely, when the metal foil is etched to form a circuit when it is too thick, a taper tends to occur on the side of the circuit, which is disadvantageous for the formation of a fine pattern. The spacer film (c) used in the present invention must be easily peeled off from the insulating film (A) after thermocompression bonding in addition to heat resistance at a heat-resistant press-bonding temperature. From the viewpoint of the latter, the surface and the inner surface of the spacer film (c) are both surface roughness (RZ) 2. 〇 is preferably m or less, and more preferably 〇 5 to 1.5/zm. In terms of ease of ensuring heat resistance and surface smoothness, the spacer film (C) is made of a non-thermoplastic polyimide film or a polyimide film, or a metal foil such as a foil or a steel foil. Preferably. Further, a composite film having a metal foil on the surface of the resin film and the inner surface thereof may be used. When the surface roughness and the surface roughness (Rz) of the spacer film (C) exceeds 2.0 from m, the interlayer adhesion between the insulating film (A) and the spacer film (C) is improved by the anchoring effect. When the single-sided metal-clad laminate made of the insulating film (A) and the metal town (B) is peeled off when peeled off from the spacer film (C), the single-sided cover is broken and wrinkled. Such as the appearance of defects. θ For the spacer film (C), it is preferable to carry out the release treatment of the thin film (single side or both sides of the crucible) for the purpose of increasing the peeling property after the thermocompression bonding and the insulating thin film (Α). The specific method of the release treatment is, for example, a method of providing a resin film of 322680 13 201202022 type such as a silicone resin or a fluorine resin on the film (C) of the door s. The thickness of the spacer film (C), It is preferably in the range of 10 to 300 // m, more preferably 20 to 150/zm, and still more preferably in the range of 30 to 100/zm. When the spacer film (C) is too thin, the pressure during thermocompression is uniformly dispersed. The pressure buffering effect is lowered, and the interlayer adhesion between the insulating film (A) and the metal foil (B) of the metal-clad laminate produced may be uneven. On the other hand, when it is too thick , may hinder the conveyance of the roller to the roller, or may cause deterioration of workability when peeling off from the metal-clad laminate after thermocompression bonding. Insulating film (A), metal foil (B), And the combination of the spacer film (C), ease of operation and economy in the thermal compression step (material cost, interval) From the viewpoint of the recyclability of the film, etc., and the properties (mechanical properties, electrical properties, thermal properties, processability, etc.) of the produced single-sided metal-clad laminate, it is preferred that the insulating film (A) is A liquid crystal polymer film having a thickness of 10 to 100 or a polyimide film having a thermoplastic resin layer on at least one of the surfaces; a metal foil (B) using a copper foil having a thickness of 5 to 70/zm; and a spacer film (C) is an aluminum foil whose surface and inner surface are both surface roughness (Rz) 2.0 or less and has a thickness of 5 to 70/zm. Between a pair of pressure rollers (rl, r2), Insulating film (A), metal foil (B), and spacer film which are superposed in the order of (rl) / (B) / (A) / (C) / (A) / (B) / (r2) C) When performing thermocompression bonding, a generally known heating and pressurizing device having a pressure roller having a pair of heating means can be used. At this time, the insulating film (A), the metal foil (B), and the spacer film are used. (C), if each of the elongated materials rolled into a roll shape is used in combination with a heating and pressurizing device, the single-sided metal-clad laminate can be continuously produced. Further, the pressure is 14 322680 20120. 2022 The temperature of the roller and the pressure of the pressure roller are determined by the insulation (1), but f(8) is well followed. Therefore, it is better to operate at a lower m than the thermoplastic tree. For example, when insulating the θ point film , with a temperature lower than the melting point of 5 to 丨G 『C _ liquid crystal polymerization is 20 to 8 低 lower than its melting point. (: The temperature range 胍 ^ 7 slave Jia, to -, 啤 beer disaster. In addition, 丨"Good pressure is better in the range of 20 to 200 kN/m." Pressurization In the present invention, the spacer film (edge film U) and the metal layer are formed by the interval centering. Standing in a symmetrical position, the pair of forces and the decaying wheel are in the middle r2) and β can be thermocompression at the same temperature, r necessary heat loss. In addition, since the pressure roller and the metal f = no, the heat conduction on the pressure roller is not easily hindered. Further, in the case of the heat treatment, as described in the following examples, the insulating film (A) and the space between the layers are: the peeling strength between the layers is G.1' or less, and the peeling strength is extremely easy to be peeled off, and the uneven strength of the pot can be prevented. The occurrence of crepe patterns', therefore, a high-quality single-sided metal-clad laminate can be obtained with good productivity. Furthermore, although the present invention is to obtain a single-sided metal-clad laminate from two sets of insulating films (A) and metal boxes (8) by interposing the film 4 (C), it is also possible to review the thinning interval by intervening. Further, two sets of (B)/(A)/(B) combinations were used, and two variants of the double-sided metal-clad laminate having metal foil on both sides were produced at one time. EXAMPLES Hereinafter, the present invention will be specifically described by way of Examples, but the present invention is not limited to the following. Further, in the embodiment of the invention to be described later, the conditions of the processing conditions and the measurement (evaluation) are as described below unless otherwise specified in 322680 15 201202022. [Measurement of surface roughness] According to JIS B 0601, a stylus type surface roughness measuring instrument ("TENCORP-10 manufactured by TENC〇R") was used to load l〇0/zN, scanning speed 2〇"m/sec The clock and the measurement distance of 800 //m were used to determine rz (ten-point average roughness). [Evaluation of the peeling property of the spacer film (C)] The laminate (B/A/C/A/B) containing the spacer film (C) after thermocompression bonding is cut in the long direction of the scrap roller The width is 1 、, and the lamination direction (MD direction) is cut into a length of 15 〇 mm to prepare a strip-like peeling test piece 'and the interlayer of the insulating film (A) and the spacer film (c) The peelability was measured in accordance with J IS K 6854-3 (T-type peeling). The peeling speed was set at 100 mm/min. [Evaluation of the adhesion of the metal-clad laminate] The early-surface metal-clad laminate was cut into a length of 150 mm in the direction of lamination (using the commercially available etching solution (ADEKACHELUMICA FE-210 'ADEKA shares) The company manufactures a steel foil by a subtractive method and forms a linear conductor pattern 7 of a width imin and a length of 100 mm along the direction of lamination (refer to Fig. 3). The linear conductor pattern 7' is formed at three positions in the width direction of the single-sided metal-clad laminate (longitudinal direction of the pressure roller), and three patterns are formed at positions spaced apart from each other by 30 mm from the center to the width direction. Adhesion test piece. The three linear conductor patterns of the adhesion test piece were measured for the strength of peeling from the insulating film (A) in accordance with the method B (pulling in the 180° direction) of JIS C 6471. After that, the average of the peel strengths of the three strips is 1. OkN/m or more and 16 322680 201202022 'when it is good, 0.5kN/m or more and less than ^(10)^ is acceptable, not up to -5. 5kN/m In the case of the poor grade 3, the "adhesiveness" was evaluated. In addition, the difference between the maximum value and the minimum value of the three peel strengths was evaluated as "the degree of unevenness of the adhesion". (Example 1) A liquid crystal polymer crucible 1 having a thickness of 50 μm and a width of 7 mm was prepared (melting point 320. An elongated thin crucible rolled into a roll shape was used as an insulating film (A), and thickness was additionally prepared. An elongated copper foil rolled into a roll shape as a metal foil (B) of a commercially available electrolytic copper crucible 2 (surface roughness Rz: insulating thin film layer 16 μm, exposed surface 1.4 vm) of a width of 7 y. Further, an aluminum foil 3 having a thickness of 50/zm and a width of 70 mm (the surface and the inner surface are both surface roughness Rz: 1.2/zm) are rolled into a roll-shaped elongated aluminum foil as a spacer film (C). 1 is not shown, these are respectively installed to the insulating film feeding roller A, the metal foil feeding roller 8, the spacer thin-twist feeding roller c, and then pressurizing the recording 4 (small 1*2) The _"cast _ crystal polymer film 1 / (4) 3 / liquid crystal polymer film " electrolytic copper 2" in the order of overlapping and supply (as shown in Figure 2), it is naturally cooled after hot pressing, and using stripping The roller 6 peels off the (4) 3 and the liquid crystal polymer film i layer, and the _ 3 rolls up the roller C from the spacer film, and recovers the liquid crystal polymer film 丄 and the electricity _2 The steel-clad laminates 5 are each collected by the product take-up rolls X provided at two places. Thereafter, the electrolysis 2, the liquid crystal polymer film, and both are moved at a speed of 0.7 m/min, and both are Between the pressure roller 4 of the watch, the pressure between the waves is torn together, 322680 17 201202022 After hot pressing, the laminate is cooled by natural cooling, and the roller is retracted by the spacer film winding roller C'. The foil 3 and the single-sided copper-clad laminate 5 of the first embodiment are collected from the product winding roller X disposed at two places. The pressure roller 4 of the apparatus used in the embodiment 1 is each 130 mm in length. In the first embodiment, the interlayer peeling of the liquid crystal polymer film i and the aluminum foil 3 after the thermocompression bonding is performed without any defects, and is smoothly performed, and is visually observed and recovered. In the case of the liquid crystal polymer film surface and the electrolytic copper foil surface of the copper-clad laminate 5, no cracking, wrinkles, or rough surface formation was observed at all. The single-sided copper-clad laminate 5 of Example 1 was in the manufacturing process. Medium, after being pressed by the pressure roller 4, to the peeling Before the roller 6, the peeling test piece was cut, and the peeling property between the liquid crystal polymer film 1 and the aluminum crucible 3 was measured, and it was confirmed that the value of the interface peeling was unmeasurable, and it was excellently peeled off. From the one side of the single-sided copper-clad product: one of the bodies 5, the adhesion test piece was processed as described above, and the adhesion between the liquid crystal polymer film 1 and the electrolytic copper foil 2 was evaluated. The "adhesiveness" evaluated by the average of the peel strengths of the three linear conductor patterns is good. Further, the difference between the maximum and minimum values of the three peel strengths is not as good as the "adhesiveness". The degree is "QQ3kN/m", and it is confirmed that the liquid crystal polymer thin layer and the electrolytic copper foil 2 are uniformly formed in the plane. The results are shown in Table 1. ""^ (Example 2) In addition to the spacer film (C), a non-thermoplastic "commercially available thermal polyimine film 3 (Tg: 34 (rc, both surface and inner surface) of 322680 is used. 18 201202022 Roughness Rz : 〇9 am) The same operation as in Example 1 was carried out to obtain a single-sided metal-clad laminate in the same manner as in Example 1. In Example 2, 'after hot pressing The liquid crystal polymer film 1 and the enthalpy of the heat enthalpy film 3 are smoothly formed without defects, and the soil is completely ruptured when the surface and the inner surface of the single-sided copper-clad laminate 5 are recovered. And the case of κ, surface rough sugar. In addition, in the measurement using the peeling test piece, the i-disc 5 endures the interface peeling to 0.07 kN/m. In addition, the evaluation of the adhesion test piece is "adhesive" It is good that the degree of "tightness" is k2kN/m, and it is confirmed that the liquid crystal polymer film = electrolytic steel falling 2 is uniformly followed in the plane. The results are shown in Table 1. (Example 3) Spacer film (other than double-sided copper-clad laminate (new 曰铁化学a division ESPANEX μ series product (10) 12_25_12CEG)) The rest of the same operation as in Example 1 is carried out to obtain a single-sided copper-clad laminate having a solid thickness of 3. In the double-sided steel-clad laminate, the center has a thickness plus a resin as an insulating layer and is respectively disposed on both sides thereof. The surface roughness (10) of the exposed surface of the thickness 12_ and = (4) is U. In the plasticization of the third embodiment, in the biofilming, the liquid crystal polymer film 1'" after the thermocompression bonding, and the interlaminar stripping layer of the polyacrylimide film 3 are flawless and extremely smooth. When the surface and the inner surface of the single-sided copper-clad laminate 5 were visually observed, the cracks, the enemies, and the rough surface were not confirmed. In addition, in the measurement of the oxygen-removing test piece, it was confirmed that the interface peeling was G· Building N/m; ^ In the evaluation based on the adhesion test piece, the "reliability" was good, and the adhesion was excellent. It is 03.03kN/m, and it is confirmed that the single-sided copper-clad product 19 322680 201202022 The layer 5 body is uniformly followed in the plane. The results are shown in Table 1. (Comparative Example 1) A comparative example was obtained in the same manner as in Example 1 except that the spacer film (C) was a composite polyimide film having a thickness of 25 / / m and a thermoplastic polyimide on the surface and the inner surface. 1 single-sided copper-clad laminate. The composite polyimine film is composed of a thermoplastic polyimide obtained by setting a thermoplastic polyimide of about 2 // m on both sides of a non-thermoplastic polyimide of about 21/m. The surface roughness of the surface and the inner surface (Rz) is 2.3 to 111. In the comparative example 1, the composite polyimide film used as the spacer film was not peeled off smoothly from the liquid crystal polymer film 1 after the hot pressing, and it was confirmed to be 0.50 kN/m in the measurement using the peeling test piece. Cohesive fai lure. Further, when the surface and the inner surface of the recovered single-sided copper clad laminate 5 were visually observed, the roughness of the surface of the liquid crystal polymer film was confirmed to be rough due to aggregation failure. On the other hand, in the evaluation based on the adhesion test piece, although the "adhesiveness" is acceptable, the "degree of unevenness of the adhesion" is 0.15 kN/m, which is compared with the results of the examples. The adhesion in the plane of the one-sided copper clad laminate 5 is uneven. The results are shown in Table 1. (Comparative Example 2) A single-sided copper-clad laminate of Comparative Example 2 was produced in the same manner as in Example 1 except that the spacer film (C) was not used, and after cooling and hot-pressing, The surface of the liquid crystal polymer film 1 used as the insulating film (A) was thermally fused to each other, and was measured to be 0. 70 kN/m in the measurement of the peeling test piece. 322680 201202022 . Destruction. Further, after the obtained single-sided copper-clad laminate was visually observed, it was confirmed that the surface of the liquid crystal polymer film was rough due to aggregation failure, and it was impossible to produce a single-sided copper-clad laminate having a good appearance. . (Comparative Example 3) The same procedure as in Example 1 was carried out except that the pair of pressure rollers 4 were overlapped in the order of "electrolytic copper foil 2/liquid crystal polymer film 1/aluminum foil 3" The single-sided copper-clad laminate of Example 3. In the comparative example 3, only one single-sided copper-clad laminate was obtained, but the interlayer peeling of the liquid-polymer polymer film 1 and the aluminum foil 3 after the thermocompression bonding was smoothly performed, and the single-sided copper-clad laminate was recovered. The surface and the inner surface of the body 5 were not confirmed to have cracks, wrinkles, or rough surfaces. Further, in the measurement by the peeling test piece, it was confirmed that the interface peeling was 0.01 kN/m, and in the evaluation based on the adhesion test piece, "adhesiveness" was acceptable. However, the degree of "unevenness of adhesion" was 0.17 kN/m, which was inferior to the results of the examples, and it was found that the in-plane uniformity was not good. (Comparative Example 4) Operations were carried out in the same manner as in Example 1 except that the pair of press rolls 4 were overlapped in the order of ''aluminum foil 3/electrolytic copper foil 2/liquid crystal polymer film 1/aluminum foil 3''. The single-sided copper-clad laminate of Comparative Example 4 was produced. In Comparative Example 4, only one single-sided copper-clad laminate was produced in the same manner as in Comparative Example 3, but the interlayer peeling of the liquid crystal polymer film 1 and the aluminum box 3 after the thermocompression bonding was smoothly performed, and The surface and the inner surface of the single-sided copper-clad laminate 5 which was recovered were not confirmed to have cracks, wrinkles, or rough surfaces. Further, in the measurement by the peeling test piece, it was confirmed that the interface peeling 21 322680 201202022 was 0.01 kN/m, and the "adhesiveness" was good in the evaluation based on the adhesion test piece. However, the "unevenness of adhesion" is 〇.〇7kN/m, and compared with the results of the examples, it is understood that the uniformity in the plane is not good. [Table 1] Spacer film (C) Material composition between pressure roller (A)-(C) Peelability (A)-(B) Adhesion UHB) Adhesion is not in the form of a copper composite layer Example 1 Foil (thickness 50/^m, Rzl. 2 urn) B/A/C/A/B could not be measured well 〇.03kN/m bottle i good appearance Example 2 Example 3 heat-resistant polysodiumimine film (thickness 50 #m,Rz〇. 9/zin) Double-sided copper-clad laminate (thickness B/A/C/A/B 0.07kN/m good 〇.02kN/m good μη, Rzl.0//m) B/A /C/A/B 0.04kN/m Good 〇. 03kN/m Good Comparative Example 1 Comparative Example 2 Composite polyimide film (thickness 25/zin, Rz2. 3^m) No B/A/C/A/ BB/A/A/B 0.50kN/m is still 0.15kN/m. Poor Comparative Example 3 B foil (thickness 5〇; wm, Rzl.-f β!〇) B/A/C u. (UKiN/m 0.01 kN/m 尚可〇.17kN/m Poor good comparison example 4 Ming foil C thickness 50/zm, Rzl.2 _β^)___ C/B/A/C 0.01kN/m Good 0.07kN/m Good by the above As a result, according to the production method of the present invention, it is possible to produce a high-quality single-sided metal covering which is excellent in wrinkles and subsequent strength unevenness, and which is excellent in adhesion between layers of insulation and gold I. Laminated body. In addition, the present invention is subject to the above-described real state, and various changes can be made. BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is a side view showing a manufacturing apparatus of a single-sided metal-clad laminate according to an embodiment of the present invention. Fig. 2 is a schematic view showing the vicinity of the pressure roller. Fig. 3 is a plan view showing the test piece used in the evaluation of the adhesion between the insulating film and the metal crucible. [Main component symbol description] 322680 22 201202022 Liquid crystal. Polymer film (insulating film (A)) Electrolytic copper foil (metal foil (B)) 3 Aluminum foil (spacer film (C)) 4 Pressure roller 5 Single-sided copper Laminated body 6 Peeling roller 7 Straight conductor pattern A Insulating film feeding roller B Metal foil feeding roller C Spacer film feeding roller C, spacer film winding roller MD Lamination direction rl, r 2 - Pressure roller X product winding roller 23 322680