CN1255087A - 用于印刷电路板的超薄导电层 - Google Patents
用于印刷电路板的超薄导电层 Download PDFInfo
- Publication number
- CN1255087A CN1255087A CN98804932A CN98804932A CN1255087A CN 1255087 A CN1255087 A CN 1255087A CN 98804932 A CN98804932 A CN 98804932A CN 98804932 A CN98804932 A CN 98804932A CN 1255087 A CN1255087 A CN 1255087A
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- Prior art keywords
- layer
- releasing agent
- agent layer
- metal
- carrier film
- Prior art date
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- Granted
Links
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Images
Classifications
-
- 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
- B32B3/00—Layered products comprising a layer with external or internal discontinuities or unevennesses, or a layer of non-planar shape; Layered products comprising a layer having particular features of form
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B15/00—Layered products comprising a layer of metal
- B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
- B32B15/08—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
-
- 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
- B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
- B32B7/04—Interconnection of layers
- B32B7/06—Interconnection of layers permitting easy separation
-
- 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
- B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
- B32B7/04—Interconnection of layers
- B32B7/12—Interconnection of layers using interposed adhesives or interposed materials with bonding properties
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- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K3/00—Apparatus or processes for manufacturing printed circuits
- H05K3/02—Apparatus or processes for manufacturing printed circuits in which the conductive material is applied to the surface of the insulating support and is thereafter removed from such areas of the surface which are not intended for current conducting or shielding
- H05K3/022—Processes for manufacturing precursors of printed circuits, i.e. copper-clad substrates
- H05K3/025—Processes for manufacturing precursors of printed circuits, i.e. copper-clad substrates by transfer of thin metal foil formed on a temporary carrier, e.g. peel-apart copper
-
- 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
- B32B2307/00—Properties of the layers or laminate
- B32B2307/20—Properties of the layers or laminate having particular electrical or magnetic properties, e.g. piezoelectric
- B32B2307/202—Conductive
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2457/00—Electrical equipment
- B32B2457/08—PCBs, i.e. printed circuit boards
-
- 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
- H05K2201/00—Indexing scheme relating to printed circuits covered by H05K1/00
- H05K2201/03—Conductive materials
- H05K2201/0302—Properties and characteristics in general
- H05K2201/0317—Thin film conductor layer; Thin film passive component
-
- 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
- H05K2201/00—Indexing scheme relating to printed circuits covered by H05K1/00
- H05K2201/03—Conductive materials
- H05K2201/0332—Structure of the conductor
- H05K2201/0335—Layered conductors or foils
- H05K2201/0355—Metal foils
-
- 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
- H05K2201/00—Indexing scheme relating to printed circuits covered by H05K1/00
- H05K2201/03—Conductive materials
- H05K2201/0332—Structure of the conductor
- H05K2201/0335—Layered conductors or foils
- H05K2201/0358—Resin coated copper [RCC]
-
- 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
- H05K2203/00—Indexing scheme relating to apparatus or processes for manufacturing printed circuits covered by H05K3/00
- H05K2203/07—Treatments involving liquids, e.g. plating, rinsing
- H05K2203/0756—Uses of liquids, e.g. rinsing, coating, dissolving
- H05K2203/0769—Dissolving insulating materials, e.g. coatings, not used for developing resist after exposure
-
- H—ELECTRICITY
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Abstract
本发明公开一种包金属的叠层的产品(10),其包含:载体膜(11)、水溶性的脱模剂层或分离层(12),其沉积在载体膜(11)上并可以机械方式由载体膜(11)剥离、以及沉积在分离层(12)上的超薄金属层(13)。还公开了用于制造该包金属叠层(10)的方法。
Description
相关申请的交叉参数
本申请的优先权源于1979年3月13日申请的申请号为60/047019的临时申请。
发明背景
电子技术界一直持续致力于寻求增强例如为集成电路使用的印刷电路板之类的产品的性能,以便满足用户对于更高性能更低成本的计算机和电子设备需求。在电子技术界内的努力要解决的问题包含希望增加速度和功能且要求降低元件和相互连接部分的尺寸。其中可供降低互连电路尺寸的方法包含电路板的设计要使该电路板具有较小较细的线条和间隙,以便增加板上的线路的密度。增加线路密度导致形成较少的电路层数和较小的较轻的电子器件。
印刷电路板电路可以应用刚性的玻璃纤维增强塑料或者柔性薄膜上,其上粘附用于形成导电线路连接的金属箔。电路板可以包含按一层、两层或多层的互连电路。具有三或更多层的电路板可以利用多个层叠在一起的二层板形成一多层结构,或者可以通过顺序地添加绝缘层和电路(层)由二层板构成。
大多数多层电路板通常是通过利用在玻璃纤维中浸渍热固性聚合物(称为“预浸处理”)层将带电路的双面板层叠成一叠层来制造的。通常通过利用预浸处理层和一层金属箔添加在最外带线路的层。在双面芯层电路上的线路连接通常通过利用衬底技术制造的,而外金属导电层是按半添加(semi-additive)法成形的。利用贯穿板的机械钻孔和镀覆导电金属将多个电路层电连接。
通过将涂有热固性树脂的箔层叠到带有电路的双面板上制造顺序组装的板。所涂的树脂层用作可控的隔离层,将组装的电路层与双面电路板分开。在各电路层之间的电连接是通过等离子或激光钻孔接着镀覆形成的连接孔形成的。利用半添加法使组装的电路完成电路化。各组装的层可以层叠形成多层电路。
电路板设计者需要衬底材料,在其上可按高精确度形成极细的线条和间隙。薄金属箔通常是一种优选的衬底,用于在电路板上形成的电路线路。使用较厚的箔会导致浪费更多的金属,和降低可达到的线路密度。金属膜最一般的方式是通过电沉积形成的。电沉积形成的金属膜通常必须限定其最小厚度,即大于1微米,以避免出现孔洞和间断点。
目前在工业中使用的金属膜通常最小厚度为5微米。在印刷电路板中使用更薄的金属膜将使得能够形成密度更密集的线路和降低产品成本。开发得到更薄的铜膜的制造方法是很有意义的。用于得到很薄的金属膜和将其置于叠层上的已有方法是受限的。
4357395号美国专利公开了一种包铜的叠层,其是通过首先在铝载体上形成二氧化硅层,然后在该二氧化硅层上溅射铜膜。然后将该铜层层叠到一衬底上,再将该衬底和二氧化硅层以机械方式剥离,使留下的铜层露出。实例表明按照这种方法得到厚度为5-10微米的铜膜。
在4357395号美国专利中公开的方法不适合于制造具有超薄(0.1-0.3微米)的铜箔的包铜叠层,这是因为当将载体和二氧化硅层以机械方式分开时,超薄铜箔易于撕坏。
4431710号美国专利公开了带有铜箔的铝箔,其中在100℃-250℃的温度下利用气相沉积将铜沉积在铝箔上。实验证明铜箔的厚度为5微米。在层叠到衬底上之后,利用0.5-2.0磅/英寸的剥离作用力取下铝载体。该公开文献讨论了利用这种方法在剥离强度实验中的变异性。高剥离强度和变异性对于厚度小于1微米的超薄的箔是有害的。此外,作为示范的箔根据污染的情况对剥离强度有明显的影响。
5262247号美国专利介绍了一种由铜载体层、铬酸盐分离层、铜镍合金层以及最终的铜箔层组成的箔。在进行层叠时,去掉铜载体层和铬酸盐层。形成的金属化的衬底需要对铜镍合金层进行蚀刻以便露出铜层。应当强调指出,该薄铜箔层厚度必须为1-10微米。铜箔层厚度低于1微米是不能用的,因为为去掉铜镍合金层所需的蚀刻步骤。蚀刻铜镍层也蚀刻了底铜层。
在本技术领域为了制造印刷电路板需要一种得到超薄金属箔叠层的方法。
发明概述
本发明的目的是提供一种在制造印刷电路板时使用的包金属的叠层,该叠层具有超薄的金属箔,该金属箔有助于在其上形成非常细的线条和间隙。
本发明的另一个目的是提供一种大规模生产用于制造印刷电路板时使用的包金属的叠层的方法,该叠层具有超薄的金属箔,该金属箔有助于在其上形成非常细的线条和间隙。
本发明的再一个目的是提供一种用于多层中的金属箔并形成电路板,该金属箔是超薄的从而能够在其上形成非常细的线条。
本发明提供一种用于制造印刷电路板的包金属的叠层,该叠层具有超薄的金属箔,该金属箔最大厚度约为1微米。
本发明还提供一种用于制造印刷电路板的包金属的叠层的方法,该叠层具有超薄的金属箔,该金属箔最大厚度约为1微米。
附图简述
图1是表示根据本发明构成的包金属的叠层的中间产品的断面图。
图2是表示根据本发明构成的另一种包金属的叠层的断面图。
图3-6是表示根据本发明的另外一些实施例的断面图。
发明详述
本发明涉及超薄金属导电层,是通过在已经涂布有一种有机脱模剂的聚合物或金属载体膜上以气相沉积或导电金属溅射形成的。然后可以将金属导电层粘合到印刷电路板衬底(例如以环氧树脂为基础的叠层)上。此后,可以将载体膜由聚合物脱模剂上分离,留下粘结到衬底上的金属导电层。利用这种方案,形成实用的厚度范围处在0.005-1.0微米(50-10000埃)的金属导电层。
根据本发明,可以制造的在制造印刷电路板时使用的包金属的叠层产品,包含聚合物或金属箔载体层、形成在载体层上形成的聚合物分离层、形成在脱模剂层上形成的超薄金属层。在图1中表示的是根据本发明制造的包金属的中间产品10。该中间产品10由载体膜11构成,其涂有聚合物脱模剂层12,在该层12上再施加有超薄金属导电层13。
在图2中表示的是这里标注为20的包金属叠层产品的另一实施例。在图2中表示的实施例中,载体膜21涂有聚合物脱模剂层或分离层22。主超薄金属导电层23沉积在脱模剂层22上。在主超薄金属导电层23的顶面上是辅助金属层24,最好也是通过溅射或者气相沉积形成的。
如在图3中所示,该包金属的中间产品30的另一实施例包含:载体膜31、脱模剂层或分离层32以及主超薄金属导电层33。在金属导电层23上沉积粘附层35。
如在图4中所示,该包金属的中间产品40的另一实施例包含:载体膜41、脱模剂层42、主超薄金属导电层43、辅助金属层44以及粘附层45。
如在图5中所示,该包金属的中间产品50的另一实施例包含:载体膜51、脱模剂层52、主超薄金属导电层52以及粘附层54。这一实施例还包含两层电路板用树脂叠层材料,或者预浸处理的材料,分别标注为56和57。
如在图6中所示,该包金属的中间产品60的另一实施例包含:载体膜61、脱模剂层62、主要超薄金属导电层63、辅助金属层64以及粘附层65,此外还包含两层树脂叠层材料66和67。
表示和讨论这些不同的实施例是为示范性地说明可有广泛的各种各样的选择层数以组成这些中间产品。
最好,载体膜包含一种柔性的尺寸稳定的材料,其具有良好的抗撕和抗化学腐蚀的性能。该载体膜应当能够承受高于环境温度。最好,载体膜由具有低吸湿性和低残留溶剂的材料构成,因为,水分和溶剂能干扰金属化步骤。适合的材料包含聚合物膜或金属箔。金属箔是优选的,因为金属箔往往在高的温度下具有高的抗拉强度,低吸湿性以及低残留溶剂。
在下面的实例中采用的载体膜是电镀的铜箔或聚合物膜。能够形成适宜的载体膜的其它金属箔包含轧制的或电沉积的金属和金属合金,包括钢、铝(Alcoa,AllFoils)以及铜(Gould Inc.,Oak Mitsui Inc.)。预计某些聚合物膜也会适合于实施本发明。适合的聚合物膜的实例包含聚酯例如聚对苯二甲酸乙二酯、聚对苯二甲酸丁二酯和萘二甲酸乙二酯(Kaladex,ICIAmerica)、聚丙烯、聚氟乙烯(Tedlar,DuPont)、聚酰亚胺(Kapton,DuPont;Upilex,UBE Industries)以及尼龙(Capran,AlliedSignal)。
脱模剂层(在图1中的11、在图2中的21、在图3中的31)的使用为便利于载体膜和超薄金属层的分离。为了避免撕裂问题(导致不能实现将超薄金属层转移到在叠层下的衬底上),设计有脱模剂层以便在分离层和载体膜之间的界面处剥离。其后利用等离子体、氧化环境、强光或适当的溶剂除去分离层。通过用溶剂冲洗除去该层较好,用水溶液更好。在无脱模剂层的方法中以及在采用脱模剂层的方法(其中在分离层和超薄金属层之间的界面处剥离)中,通常都不能完全将超薄金属层转移到衬底上。
分离层(在图1中的12、在图2中的22等)是由聚合材料构成的。最好,分离层是一种可溶于水的材料,以便于由超薄金属层除去。由于光刻胶在碱性溶液环境中显影,使用一种可溶于碱性溶液的分离层是最为优选的。使用的聚合物是一种能良好形成膜的材料。借助于一种挥发性基料例如氢氧化铵(有助于提高溶解性)用水涂覆该聚合物。分离层还可包含水溶性的表面活性剂,以便改进溶液浸润性并控制干化缺陷。
正如在下面例子详细介绍的,涂覆一种常用的脱模剂层或分离层,其成分包含聚乙烯吡咯烷酮(PVP)聚合物、表面活性剂和水。在该实例中介绍的分离层配方的湿重组分为10%PVP和0.5%表面活性剂。预计下列配方也是适合于实施本发明的,即,其中包含的PVP的范围为1%-50%,表面活性剂的范围为0%-5%。在本发明中优选使用的PVP的分子量范围约在10000-5000000。预计这样一种脱模剂层是可成功用于实施本发明的,即包含一种聚合物例如为改变酸性的丙烯酸聚合物、丙烯酸共聚物、氨基甲酸乙酯和聚酯,羧酸官能的苯乙烯丙烯酸树脂(S.C.Johnson Wax,Joncryl)、聚乙烯醇(Air Products & Chemicals,Airvol)以及纤维素基聚合物。其它可以用在本发明的分离层的适宜的水溶性的表面活性剂包含:烷芳醚醇(Rohm & Haas,TritonX100)、丙三醇、乙氧基化蓖麻油(CasChem Inc.,Surfactol 365),以及氟代脂肪的聚酯(3M Corporation,Fluorad430)。施加的脱模剂层配方的量应足以达到干重量约为10-1000毫克/平方英寸,厚度约为0.1-10微米。最好,施加的脱模剂层配方的量应足以达到干重量约为100-400毫克/平方英寸,厚度约为1-4微米。
正如在下面实例中介绍的,利用一种Desk III溅射装置通过溅射可以在分离层上沉积薄的主导电金属层(在图1中的13,在图2中的23等)。预计在本技术领域中公知的溅射或气相沉积方法都可成功地应用在本发明中。主金属层用作作为后来的电路部分的电镀种层。在如下的实例中,该金属层是由金、铬或铜构成的。其它适宜的金属包含但不局限于锡、镍、铝、钛、锌、铬锌合金、黄铜、青铜以及它们的合金。该金属层可以由适宜金属的混合物构成。主金属层的厚度约为0.005-1.0微米(50-10000埃)。特别优选的主金属层的厚度约为0.1-0.3微米(1000-3000埃)。
还可使用辅助金属层(例如在2图中的24、在图4中的44、在图6中的64),用于保护主金属层不受氧化、在叠层的过程中增加粘接力、或用作防止金属迁移的阻挡层。辅助金属层的厚度约为0.001-0.1微米(10-1000埃)。特别优选的辅助金属层的厚度约为0.01-0.03微米(100-300埃)。为了形成该辅助金属层,在第一金属层上沉积一层锌、铟、锡、钴、铝、铬、镍、镍铬合金、黄铜或青铜。其它适合的金属包含镁、钛、锰、铋、钼、银、金、钨、锆、锑和铬锌合金。辅助金属层防止由金属化室取出之后在第一金属层中的金属氧化,并增加对热固性树脂类的粘接力。
还可以将粘接剂层涂覆在该金属层上(例如在图3中的35、在图4中的45等)。使用粘接剂层是为了增加金属层和接着层叠的衬底层之间的粘结。该粘接剂层可以是有机化合物、有机金属化合物或无机化合物,涂覆厚度约为0.0005-10微米(5-100000埃)。可以采用多层结构例如有机金属化合物层接着是有机化合物层。当使用有机金属化合物层时,例如硅烷,其涂层厚度为0.0005-0.005微米(5-500埃)。当使用有机化合物粘接剂层时,例如为热塑性、热固性聚合物或者它们的混合物,其涂层厚度为0.1-10微米(1000-100000埃)。
使用的有机金属化合物包含基于锆、钛和硅的材料。可广泛使用基于硅的有机金属化合物(通称为硅烷或耦合剂)。可以涂覆单纯的耦合剂或者在其溶解在适当的溶剂中之后涂覆。适当的耦合剂通常具有硅烷-可水解的端基,其端基为烷氧基、酸基,或胺官能团,以及端有机官能端基。可水解的端基与金属表面反应,而有机官能团结合到层叠有金属的衬底层上。在涂覆之前,如果溶解在酸性介质中,可以先使耦合剂进行水解反应。所用的包含一些化合物例如N-(2-氨乙基)-3-氨丙基三甲氧基硅烷(Dow Corning,Huls America Inc.)和3-环氧丙基丙氧基三甲氧基硅烷(Dow Corning,Huls America Inc.)。由热塑性、热固性聚合物或者它们的混合物组成的有机粘接剂层是适宜的粘接剂层。这些粘接剂可基于聚酰亚胺树脂、环氧树脂、聚酯树脂、丙烯酸树脂、丁二烯橡胶等。可得到一种有用的粘接剂是聚酯-环氧树脂物系(Cortaulds,Z-FlexTM)。
在使用中可以将树脂层涂覆到金属层或粘接剂层(如果有)上,其中需要控制绝缘层厚度。这种使用包括组装技术。通常树脂是利用适当溶剂涂覆的热固性物系。如果需要在层叠到电路板上之前另外固化,则在干燥之后,树脂可固化到半固化的状态。可以利用单一半固化的树脂层。最好使用两树脂层,其中下面的第一树脂层(主树脂层)固化的程度大于第二树脂层。第一树脂层用作可控的绝缘间隙层,厚度约为5-500微米,最好为20-50微米。适当的树脂物系包含(但不局限于):环氧树脂以酚坚膜剂或双氰胺坚膜剂固化的、氰酸盐酯类、双马来酰亚胺和聚酰亚胺物系。第二树脂层可以具有与第一树脂层不同的成分,然而为了达到良好的层间粘接,最好第二树脂层的成分与第一树脂层的成分相类似。第二树脂层用作粘接层以及在层叠的过程中用作为空隙填充层,厚度约为5-500微米,最好为20-50微米。
“在适当的层叠条件下层叠”是指在制造电路板叠层时实际采用的适当的温度和压力条件下层叠,持续适当的时间段,以便将各层粘接在一起。
如下的非限定性实例完全意在说明。
实例1
由Ube Industries得到Upilex50微米的聚酰亚胺薄膜。溅射0.15微米(1500埃)的铜,接着是0.01微米(100埃)的镍铬合金。对试样加压以便形成电路板用叠层。将四层称为FR406(AlliedSignal)的预浸处理层FR-4置于在玻璃纤维增强的Teflon片上。一不锈钢压板在该片之下。将上述结构金属面向下置于在预浸处理层FR-406上。将第二层玻璃纤维增强的Teflon片置于顶面上,并覆盖上第二不锈钢压板。将该层叠物置于在预热在350(°F)下的压力机中,在50磅/英寸2下持续1.2小时。试图剥离该膜,但是困难的。按180°的角度测量剥离强度,发现其变化范围为1-5磅/英寸。金属覆盖层尺寸为100微米的切片部分并没有转移而是留在该膜上。金属覆盖层“被撕裂”。试图二次进行上述实验,发现金属覆盖层未由载体膜上剥离。金属足够强地粘接到该载体膜,使得在试图剥离的过程中膜被撕裂。
实例2
由Gould Inc.得到1盎司电镀铜箔的试样,作为载体膜。通过利用18号绕线杆在铜载体层上涂覆分离层配方P1(表1)以形成脱模剂层。接着涂覆到载体膜上,在160℃下将脱模剂层干燥约2分钟。该涂层是透明的。利用DeskIII溅射装置且利用空气作为工艺气体在透明的分离层上溅射金导电层。金沉积3分钟。利用显微镜检验金涂层的边缘,发现沉积约为0.3微米(3000埃)厚的金层。
对试样加压以形成电路板用叠层。将四层称为FR406(AlliedSignal)的预浸处理环氧树脂层FR-4置于在玻璃纤维增强的Teflon片上。一不锈钢压板在该片之下。将上述结构金属面向下置于在预浸处理层FR-406上。将第二层玻璃纤维增强的Teflon片置于顶面上,并覆盖上第二不锈钢压板。将该层叠物置于在预热在350°F下的压力机中,在50磅/英寸2下持续1.2小时。在冷却到室温之后,易于剥离铜载体膜,表明分离完全随金属覆盖层转移,通过用温水冲洗该表面除去脱模剂,露出明亮的金属表面。
表1、分离层配方P1的组成
成分 | 来源 | 数量 | |
聚乙烯吡咯烷酮 | IPC | Technologies | 5.00克 |
Surfactol | 365 | CasChem | 0.025克 |
水 | 44.975克 |
实例3
由Gould Inc.得到1盎司电镀铜箔的试样,作为载体膜。通过利用18号绕线杆在铜载体层上涂覆配方P1(表1)形成脱模剂层。接着涂覆到载体膜上,在160℃下将分离层干燥约2分钟。该涂层是透明的。利用DeskIII溅射装置且利用空气作为工艺气体在透明的分离层上溅射金导电层。沉积金持续3分钟。利用可视显微镜检验金涂层的边缘,发现沉积约0.3微米(3000埃)厚的金层。利用18号绕线杆在金层上涂覆配方R2(表2)形成第一树脂层。在约50℃下干燥约1小时,然后在约65℃下保持约1小时,最后在170℃下约固化6分钟。利用18号绕线条在第一层上涂覆配方R1形成第二树脂层。按照与在第一树脂层相同的条件干燥第二树脂层。
将四层称为FR406(AlliedSignal)的预浸处理层FR-4置于在玻璃纤维增强的Teflon片上。一不锈钢压板在该片之下。将上述结构金属面向下置于在预浸处理层FR-406上。将第二层玻璃纤维增强的Teflon片置于顶面上,并覆盖上第二不锈钢压板。将该层叠物置于在预热在350°F下的压力机中,在50磅/英寸2下持续1.2小时。在冷却到室温之后,断裂该层叠物并除去玻璃纤维增强的Teflon片显示出未包覆的叠层。将上述结构置于在未包覆的叠层顶面上,使树脂面接触该叠层。接着利用不锈钢压力板将玻璃纤维增强的Teflon片覆盖该结构。将第二不锈钢压力板置于在该叠层之下。将该层叠物置于在预热在350°F下的压力机中,在50磅/英寸2下持续1.2小时。在冷却到室温之后,易于剥离铜载体膜,表明分离层完全随金属覆盖层转移,通过用温水冲洗该表面除去脱模剂,露出明亮的金属表面。
表2 树脂配方R1的组成
成分 | 来源 | 数量 | ||
Epon | 1031A70 | Shell | Chemical | 1.98克 |
DER732 | Dow | Chemical | 5.67克 | |
PKHS-40 | Phenoxy | 18.16克 | ||
Associates | ||||
Ciba | 1138A85 | Ciba | Geigy | 15.91克 |
Quatrex | 640 | Dow | Chemical | 22.69克 |
BT2110 | Mitsbishi | Gas | 34.97克 | |
Chemical | ||||
DMF | 7.37克 | |||
Methyl Ethyl Ketone | 46.13克 |
表3 分离层配方P2的组成
成分 | 来源 | 数量 |
聚乙烯吡咯烷酮,PVP-K120 | ISP Technologies | 5.00克 |
Surfactol 365 | CasChem | 0.025克 |
水 | 44.975 |
这种配方P2不同于P1处在于选择PVP-K120,其平均分子量为2900000。在配方P1中使用的PVP是PVP-90,其平均分子量为1270000。对于涂层和膜配方希望较高的分子量,而为了增加层的溶解性希望较低的分子量。
实例4-7
由Gould Inc得到1/2盎司电镀的高温拉伸铜箔的试样,作为载体膜。通过利用18号绕线杆在载体膜上涂覆脱模剂配方P2,并在160℃下干燥约2分钟。该涂层是透明的,并测量值为250毫克/平方英尺。利用氩作为工艺气体在P2涂层上溅射不同的金属组合物:
金属层 | 说明 | |
实例4 | 金,3000埃 | |
实例5 | 铬,100-200埃 | |
实例6 | 铜,300埃接着铬,100埃 | 薄铬层用作铜和该叠层之间的钝化层 |
实例7 | 铜,1500埃接着锌,50-100埃 | 薄锌层用作铜和该叠层之间的钝化层。当将该结构在压力机中加热时,锌与薄铜层形成合金黄铜 |
该结构是属于图1中所示的形式。
在实例6和实例7中,将由硅烷构成的粘接剂层涂覆到金属层上。将γ-环氧丙基丙氧基三甲氧基硅烷按0.5%加入到甲醇和水的混合物(其中甲醇占90%和水占10%)中,形成一种的溶液。将该溶液涂覆在金属表面上并在90℃下干燥1分钟。
对试样加压以形成电路板用叠层。将四层称为FR406(AlliedSignal)的预浸处理环氧树脂层FR-4置于在玻璃纤维增强的Teflon片上。一不锈钢压板在该片之下。将上述结构金属面向下置于在预浸处理层FR-406上。将第二层玻璃纤维增强的Teflon片置于顶面上,并覆盖上第二不锈钢压板。将该层叠物置于在预热在350(°F)下的压力机中,在50磅/英寸2下持续1.2小时。在冷却到室温之后,易于剥离该铜载体膜,表明分离层完全随金属覆盖层转移。通过用温水冲洗该表面除去脱模剂,露出明亮的金属表面。
在实例6和7中,按180°的角度测量取下载体层所需的剥离力。测定的该剥离力是十分低的,并且是高度重现的。在实例6中测量为0.025磅/英寸,而在实例6中测量为0.015磅/英寸。
实例8
由Ube Industries得到Upilex50微米的聚酰亚胺薄膜。利用18号绕线杆将配方P2涂覆在载体膜上,并在160℃下干燥2分钟。该涂层是透明的,测量值为250毫克/平方英尺。利用DeskIII溅射装置且利用空气作为工艺气体在透明的的分离层上溅射金导电层。沉积金持续3分钟。利用显微镜检验金涂层的边缘,发现沉积约0.3微米(3000埃)厚的金层。
对试样加压以便形成电路板用叠层。将四层称为FR406(AlliedSignal)的预浸处理层FR-4置于在玻璃纤维增强的Teflon片上。一不锈钢压板在该片之下。将上述结构金属面向下置于在预浸处理层FR-406上。将第二层玻璃纤维增强的Teflon片置于顶面上,并覆盖上第二不锈钢压板。将该层叠物置于在预热在350(°F)下的压力机中,在50磅/英寸2下持续1.2小时。在冷却到室温之后,易于剥离该铜载体膜,表明分离层完全随金属覆盖层转移。通过用温水冲洗该表面除去脱模剂,露出明亮的金属表面。
实移9
由Ube Industries得到Upilex50微米的聚酰亚胺薄膜。利用18号绕线杆将脱模剂配方P2涂覆在载体膜上,并在160℃下干燥2分钟。该涂层是透明的,测量值为250毫克/平方英尺。利用由CVC Products,Inc制造的CVE真空室在透明的涂层上气相沉积铜层。沉积金持续约4分钟。
将由硅烷构成的粘接剂层涂覆到金属层上。将γ-环氧丙基丙氧基三甲基硅烷按0.5%加入到甲醇和水的混合物(其中甲醇占90%和水占10%)中,形成一种的溶液。将该溶液涂覆在金属表面上并在90℃下干燥1分钟。
对试样加压以形成电路板用叠层。将六层称为FR408(AlliedSignal)的预浸处理环氧树脂层FR-4置于在玻璃纤维增强的Teflon片上。一不锈钢压板在该片之下。将上述结构金属面向下置于在预浸处理层FR-408上。将第二层玻璃纤维增强的Teflon片置于顶面上,并覆盖上第二不锈钢压板。将该层叠物置于在预热在350(°F)下的压力机中,在50磅/英寸2下持续1.2小时。在冷却到室温之后,易于剥离该聚酰亚胺膜,表明夹层完全随金属覆盖层转移。通过用温水冲洗该表面除去脱模剂,露出明亮的金属表面。
按180°的角度测量取下载体层所需的剥离力,并发现测定的该剥离力是十分低的,为0.010磅/英寸,并且是高度重现的。
实例10
由Oak-Mitsui得到1/2盎司电镀高温拉伸铜箔的试样,作为载体膜。通过利用18号绕线杆在载体膜上涂覆脱模剂配方P2,并在160℃下干燥约2分钟。该涂层是透明的,并测量值为250毫克/平方英尺。利用由CVC Products,Inc制造的CVE真空室在透明的的涂层上气相沉积铜层。沉积金持续约4分钟。
对试样加压以形成电路板用叠层。将四层称为FR406(AlliedSignal)的预浸处理环氧树脂层FR-4置于在玻璃纤维增强的Teflon片上。一不锈钢压板在该片之下。将上述结构金属面向下置于在预浸处理层FR-406上。将第二层玻璃纤维增强的Teflon片置于顶面上,并覆盖上第二不锈钢压板。将该层叠物置于在预热在350(°F)下的压力机中,在50磅/英寸2下持续1.2小时。在冷却到室温之后,易于剥离该铜载体膜,表明夹层完全随金属覆盖层转移。通过用温水冲洗该表面除去脱模剂,露出明亮的金属表面。
Claims (18)
1 一种用于制造印刷电路板的包金属的叠层产品,该产品包含:
(a)载体膜;
(b)覆盖该载体膜的脱模剂层,该脱模剂层包含一种水溶性的聚合物,该脱模剂层能够以机械方式由该载体膜剥离;以及
(c)沉积在该脱模剂层上的导电金属层,该导电金属层最大厚度为10000埃。
2 根据权利要求1所述的叠层产品,其中的脱模剂层包含聚乙烯吡咯烷酮。
3 根据权利要求2所述的叠层产品,其中在脱模剂层中的聚乙烯吡咯烷酮的分子量在10000-5000000之间。
4 根据权利要求1所述的叠层产品,其中的载体层是聚合物膜。
5 根据权利要求1所述的叠层产品,其中的载体层是金属箔。
6 根据权利要求1所述的叠层产品,其中还包含在金属层上的粘接剂层,该粘接剂层在与脱模剂层相反的一面上。
7 根据权利要求1所述的叠层产品,其中还包含粘接在导电金属层上的至少一层半固化树脂叠层。
8 一种用于制造印刷电路板的包金属的叠层的中间产品,该产品包含:
(a)载体膜;
(b)覆盖该载体膜的脱模剂层,该脱模剂层包含一种有机聚合物,便利于该脱模剂层能够以机械方式由该载体膜剥离;
(c)沉积在该脱模剂层上的主导电金属层,该导电金属层最大厚度为10000埃;以及
(d)沉积在主金属层上的辅助金属层,该金属层的最大厚度为300埃。
9 根据权利要求8所述的叠层产品,其中的脱模剂层包含聚乙烯吡咯烷酮。
10 根据权利要求9所述的叠层产品,其中在脱模剂层中的聚乙烯吡咯烷酮的分子量在10000-5000000之间。
11 根据权利要求8所述的叠层产品,其中的载体层是聚合物膜。
12 根据权利要求8所述的叠层产品,其中的载体层是金属箔。
13 根据权利要求8所述的叠层产品,其中还包含在金属层上的粘接剂层,该粘接剂层在与脱模剂层相反的一面上。
14 根据权利要求8所述的叠层产品,其中还包含粘接在导电金属层上的至少一层半固化树脂叠层。
15 一种用于制造包金属的叠层产品的方法,该方法包含的步骤有:
(a)提供尺寸稳定材料的载体膜;
(b)将脱模剂层沉积在该载体膜上,该脱模剂层包含一种水溶性的聚合物,该脱模剂层能够以机械方式由该载体膜剥离;
(c)在该脱模剂层上形成一导电金属层,该金属层包含的金属选自铜、金、铬、锡、镍、铝、钛、锌及其混合物,该金属层的最大厚度为10000埃;
(d)将该金属层粘结到树脂电路板叠层上;以及
(e)由该金属层剥离该载体膜,而不损伤附着到电路板叠层上的金属层。
16 根据权利要求15所述的方法,其中的脱模剂层由聚乙烯吡咯烷酮形成。
17 一种用于制造包金属的叠层中间产品的方法,该方法包含的步骤有:
(a)提供尺寸稳定材料的载体膜;
(b)将一脱模剂层沉积在该载体膜上,该脱模剂层包含一种水溶性的聚合物,该脱模剂层能够以机械方式由该载体膜剥离;
(c)在该脱模剂层上形成一导电金属层,该金属层的金属选自铜、金、铬、锡、镍、铝、钛、锌及其混合物,该金属层的最大厚度为1微米;
(d)将第一树脂电路板叠层施加到该金属层上并半固化该树脂;
(e)将第二树脂电路板叠层施加到第一树脂电路板叠层上并半固化该第二层,同时固化该第一层;以及
(f)剥离该载体膜,而不损伤导电金属层。
18 根据权利要求17所述的方法,其中的脱模剂层是聚乙烯吡咯烷酮。
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US4701997P | 1997-05-14 | 1997-05-14 | |
US60/047,019 | 1997-05-14 |
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CN1255087A true CN1255087A (zh) | 2000-05-31 |
CN1110408C CN1110408C (zh) | 2003-06-04 |
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CN98804932A Expired - Fee Related CN1110408C (zh) | 1997-05-14 | 1998-05-13 | 制造印刷电路板的包金属叠层产品及该产品的制法 |
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US (2) | US6596391B2 (zh) |
EP (1) | EP0996534A1 (zh) |
JP (1) | JP2001525127A (zh) |
KR (1) | KR20010012203A (zh) |
CN (1) | CN1110408C (zh) |
AU (1) | AU7569598A (zh) |
CA (1) | CA2289628A1 (zh) |
WO (1) | WO1998051485A1 (zh) |
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- 1998-05-11 US US09/075,732 patent/US6596391B2/en not_active Expired - Fee Related
- 1998-05-13 JP JP54940598A patent/JP2001525127A/ja active Pending
- 1998-05-13 WO PCT/US1998/009615 patent/WO1998051485A1/en not_active Application Discontinuation
- 1998-05-13 KR KR19997010152A patent/KR20010012203A/ko not_active Application Discontinuation
- 1998-05-13 CN CN98804932A patent/CN1110408C/zh not_active Expired - Fee Related
- 1998-05-13 AU AU75695/98A patent/AU7569598A/en not_active Abandoned
- 1998-05-13 CA CA002289628A patent/CA2289628A1/en not_active Abandoned
- 1998-05-13 EP EP98923389A patent/EP0996534A1/en not_active Withdrawn
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2000
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Cited By (5)
Publication number | Priority date | Publication date | Assignee | Title |
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CN105208771A (zh) * | 2008-12-24 | 2015-12-30 | 吉坤日矿日石金属株式会社 | 带载体的金属箔 |
CN101841979A (zh) * | 2009-03-13 | 2010-09-22 | 味之素株式会社 | 包覆有金属的叠层板 |
TWI576034B (zh) * | 2012-10-04 | 2017-03-21 | Jx Nippon Mining & Metals Corp | Method for manufacturing multilayer printed wiring board and base substrate |
CN109154068A (zh) * | 2017-04-28 | 2019-01-04 | (株)进永R&S | 金层压铜膜及其制造方法 |
CN114274546A (zh) * | 2021-12-06 | 2022-04-05 | 中国电子科技集团公司第三十九研究所 | 一种层合结构复合材料制件表面金属化方法 |
Also Published As
Publication number | Publication date |
---|---|
WO1998051485A1 (en) | 1998-11-19 |
AU7569598A (en) | 1998-12-08 |
JP2001525127A (ja) | 2001-12-04 |
KR20010012203A (ko) | 2001-02-15 |
US6596391B2 (en) | 2003-07-22 |
EP0996534A1 (en) | 2000-05-03 |
CN1110408C (zh) | 2003-06-04 |
CA2289628A1 (en) | 1998-11-19 |
US6500566B1 (en) | 2002-12-31 |
US20010055676A1 (en) | 2001-12-27 |
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