TWI441569B - Method for preparing metal coated polyimide substrate - Google Patents
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Description
本發明係關於金屬被覆聚醯亞胺基板之製法，更具體地說，關於一種能夠降低加熱金屬被覆聚醯亞胺基板時尺寸變化的分散性、當作為COF使用時可進行穩固地接合、並且可以改善不良率的金屬被覆聚醯亞胺基板之製法。The present invention relates to a method for producing a metal-coated polyimide substrate, and more particularly to a dispersibility capable of reducing dimensional change when heating a metal-coated polyimide substrate, and capable of stably bonding when used as a COF, and A method for producing a metal-coated polyimide substrate having a defective rate can be improved.
近年來，作為封裝液晶螢幕顯示圖像用的驅動用半導體之半導體封裝用基板，金屬被覆聚醯亞胺基板已被廣泛使用。上述金屬被覆聚醯亞胺基板中所用的聚醯亞胺薄膜具有優良的耐熱性，並且在機械、電氣以及化學性能方面與其他塑膠材料相比也不遜色，因此，被作為例如印刷線路板(PWB)、撓性印刷線路板(FPC)、卷帶自動接合用帶(TAB)、覆晶薄膜(COF)等電子構件用的絕緣基板材料多方面使用。這種PWB、FPC、TAB和COF，可以使用在聚醯亞胺薄膜的至少一面上被覆金屬層的金屬被覆聚醯亞胺基板，對其進行加工而製得。In recent years, a metal-coated polyimide substrate has been widely used as a semiconductor package substrate for driving a semiconductor for driving a liquid crystal display image. The polyimide film used in the above-mentioned metal-coated polyimide substrate has excellent heat resistance and is inferior to other plastic materials in terms of mechanical, electrical and chemical properties, and is therefore used as, for example, a printed wiring board ( Insulating substrate materials for electronic components such as PWB), flexible printed wiring boards (FPC), tape automated bonding tape (TAB), and flip chip (COF) are used in many ways. Such PWB, FPC, TAB, and COF can be obtained by processing a metal-coated polyimide substrate coated with a metal layer on at least one side of a polyimide film.
其中，作為封裝液晶畫面顯示用驅動IC晶片的手段，COF特別引人注目。與以前的封裝手段TCP(Tape Carrier Package)相比，COF能夠進行細距(fine pitch)封裝，是能夠容易實現驅動IC小型化和降低成本的封裝手段。作為這種COF的製造方法，一般是使用使高耐熱性、高絕緣性樹脂聚醯亞胺薄膜與通常作為金屬導電體的良導體銅層黏合而得到的金屬被覆聚醯亞胺基板，使該銅層通過光刻蝕法形成精細圖案，並在所需要的地方鍍錫和被覆防焊膜而 製得的方法。Among them, COF is particularly attractive as a means of packaging a driver IC wafer for liquid crystal display. Compared with the conventional packaging method TCP (Tape Carrier Package), the COF can perform fine pitch packaging, and is a packaging means capable of easily achieving miniaturization of the driving IC and cost reduction. As a method for producing such a COF, a metal-coated polyimide substrate obtained by bonding a high heat resistance and high insulating resin polyimide film to a good conductor copper layer which is usually a metal conductor is used. The copper layer is formed into a fine pattern by photolithography, and is tinned and coated with a solder mask at a desired place. The method produced.
在製造上述金屬被覆聚醯亞胺基板時，作為在聚醯亞胺薄膜表面上形成金屬層的方法，例如可以首先通過濺射法形成包含鎳、鉻、鎳鉻合金等的金屬薄層，再在其上形成銅層以使其具有良好的導電性而製得。此外，為了使用於形成電路的導電層膜厚化，通常通過電鍍法，或者併用電鍍與無電鍍敷的方法形成銅等金屬導電體。When the metal-coated polyimide substrate is produced, as a method of forming a metal layer on the surface of the polyimide film, for example, a thin metal layer containing nickel, chromium, nickel-chromium alloy or the like may be first formed by a sputtering method, and then It is produced by forming a copper layer thereon to have good conductivity. Further, in order to increase the thickness of the conductive layer used for forming the circuit, a metal conductor such as copper is usually formed by a plating method or a combination of electroplating and electroless plating.
另外，上述由濺射法形成的金屬覆膜的厚度，通常為100~500nm。另外，金屬導電體的厚度，例如，當通過減成法形成電路時，通常為5~12μm。Further, the thickness of the metal film formed by the sputtering method is usually 100 to 500 nm. Further, the thickness of the metal conductor is, for example, 5 to 12 μm when the circuit is formed by a subtractive method.
這裏，當通過電鍍法形成金屬導電體時，可以使用例如連續電鍍裝置，該裝置具有至少兩個用於供給電鍍液的、槽內部與發揮陰極功能的電鍍面相對向地設置了陽極的電鍍槽，多個槽在薄膜輸送方向上並排設置；並具有向各電鍍槽供電的供電部和連續輸送薄膜狀基板用的機構。例如，已公開了一種連續電鍍的方法，該方法設置了多個具有陽極和電解液的電鍍槽，將具有厚度為3μm以下的金屬覆膜的絕緣體薄膜依次連續地供給到這些電鍍槽中，控制每個電鍍槽的通電量，使各電鍍槽中的通電量按照該薄膜的供給順序依次增加，可以連續地形成均勻良好的電鍍膜(例如參照專利文獻1)。Here, when a metal conductor is formed by an electroplating method, for example, a continuous plating apparatus having at least two electroplating baths for supplying a plating solution and having an anode disposed opposite to an electroplating surface functioning as a cathode function for supplying a plating solution may be used. A plurality of grooves are arranged side by side in the film transport direction; and a power supply portion for supplying power to each plating tank and a mechanism for continuously transporting the film-form substrate are provided. For example, a method of continuous plating has been disclosed which is provided with a plurality of plating baths having an anode and an electrolyte, and an insulator film having a metal film having a thickness of 3 μm or less is sequentially and continuously supplied to the plating tanks, and is controlled. The amount of energization per plating tank is increased in order of the amount of energization in each plating tank in the order of supply of the film, and a uniform and uniform plating film can be continuously formed (for example, see Patent Document 1).
通過如上所述的濺射法和電鍍法形成金屬層的金屬被覆聚醯亞胺基板，由於建立了容易實現金屬層的薄膜化，並且可以保持聚醯亞胺薄膜與金屬覆膜的平滑介面，同時獲得了充分的黏合強度的技術，因此用其製得的COF適合於 電路的細距化。因此，已經開始批量生產了內引線部具有25~30 μm節距的COF，並在繼續開發20 μm節距以下的細距COF。The metal-coated polyimide substrate having a metal layer formed by the sputtering method and the plating method as described above is easy to realize thinning of the metal layer, and can maintain a smooth interface between the polyimide film and the metal film. At the same time, a technique of obtaining sufficient adhesive strength is obtained, so that the COF obtained by the same is suitable for The fine pitch of the circuit. Therefore, COF having a pitch of 25 to 30 μm in the inner lead portion has been mass-produced, and fine-range COF below 20 μm pitch has been continuously developed.
可是，COF係通過內引線接合裝載半導體晶片，然後通過外引線封裝在液晶畫面上。通常，由於接合時供給的熱量會使COF的尺寸發生變化，因而要預先預測該變化量，並事先對COF上形成的電路，特別是內引線的節距和外引線的節距進行校正。特別是20 μm節距的COF，由於是狹窄節距，必需對引線的節距進行嚴格的校正。However, the COF is loaded with a semiconductor wafer by inner wire bonding and then encapsulated on a liquid crystal screen by an outer lead. Generally, since the amount of heat supplied by the bonding changes the size of the COF, the amount of change is predicted in advance, and the pitch formed on the COF, particularly the pitch of the inner leads and the pitch of the outer leads, are corrected in advance. Especially for COFs with a pitch of 20 μm, due to the narrow pitch, it is necessary to strictly correct the pitch of the leads.
但是，即使是在使用由上述濺射法和電鍍法形成金屬層的金屬被覆聚醯亞胺基板的情況下，對於20 μm節距的COF，接合時端部引線脫離所要接合的位置的比率也會增加，因而出現不良率提高的問題。加熱金屬被覆聚醯亞胺基板時尺寸變化的分散被認為是其主要原因。由於這種狀況，需要能夠進一步降低加熱時尺寸變化分散性的金屬被覆聚醯亞胺基板。However, even in the case of using a metal-coated polyimide substrate in which a metal layer is formed by the above-described sputtering method and plating method, the ratio of the position at which the end lead is disconnected at the time of joining is required for the COF of 20 μm pitch. It will increase, and thus the problem of an increase in the non-performing rate will arise. The dispersion of the dimensional change when heating the metal-coated polyimide substrate is considered to be the main reason. Due to such a situation, there is a need for a metal-coated polyimide substrate which can further reduce the dispersion of dimensional change upon heating.
【專利文獻1】特開平7一22473號公報(第1頁，第2頁)[Patent Document 1] Japanese Patent Publication No. 7-22473 (Page 1, page 2)
本發明的目的是鑒於上述以往技術的問題，提供能夠降低加熱金屬被覆聚醯亞胺基板時尺寸變化的分散性、當作為COF使用時可進行穩固地接合，並且可以改善不良率的金屬被覆聚醯亞胺基板之製法。In view of the problems of the prior art described above, it is an object of the present invention to provide a metal coating which can reduce the dimensional change of a heated metal-coated polyimide substrate, can be firmly bonded when used as a COF, and can improve a defect rate. The method for preparing a ruthenium imide substrate.
本發明者們為達到上述目的，對金屬被覆聚醯亞胺基板之製法反復專心研究，結果發現，在包括在聚醯亞胺薄膜表面上形成金屬覆膜的濺射步驟，以及在所得的聚醯亞胺薄膜的金屬覆膜上使用連續電鍍裝置形成金屬導電體的電鍍步驟的金屬被覆聚醯亞胺基板之製法中，在上述濺射步驟中，形成具有特定表面電阻的金屬覆膜，可以抑制濺射中受熱過程中的分散，而且可以降低後續電鍍時的陰極電流密度差，並且，在上述電鍍步驟中，控制特定的陰極電流密度，使電流密度分佈均勻化，同時調節特定的薄膜的輸送速度，可以抑制疊層結構的介面氧化，並且所得金屬被覆聚醯亞胺基板可以降低金屬層的殘留應力的分散程度，降低對其加熱時尺寸變化的分散程度，當作為COF使用時，可進行穩固地接合、並且可以改善不良率，從而完成了本發明。In order to achieve the above object, the present inventors have conducted intensive studies on the production method of a metal-coated polyimide substrate, and as a result, found that a sputtering step of forming a metal film on the surface of a polyimide film, and the obtained polymerization are obtained. In the method for producing a metal-coated polyimide substrate in which a metal conductor is formed by a continuous plating apparatus on a metal film of a quinone film, a metal film having a specific surface resistance is formed in the sputtering step, and The dispersion in the heating process during sputtering is suppressed, and the cathode current density difference at the subsequent plating can be reduced, and in the above plating step, the specific cathode current density is controlled to uniformize the current density distribution while adjusting the specific film. The conveying speed can suppress the interface oxidation of the laminated structure, and the obtained metal-coated polyimide substrate can reduce the dispersion degree of the residual stress of the metal layer and reduce the dispersion degree of the dimensional change when heating, and when used as a COF, The present invention has been completed by performing solid bonding and improving the defective ratio.
即，根據本發明的第1項發明，提供一種金屬被覆聚醯亞胺基板之製法，該方法包括在聚醯亞胺薄膜表面上形成金屬覆膜的濺射步驟、以及使用由輸送薄膜和向金屬覆膜供電的輥和具有與該金屬覆膜相對向的陽極的至少兩個槽的電鍍槽構成的連續電鍍裝置，在所得的聚醯亞胺薄膜的金屬覆膜上形成金屬導電體的電鍍步驟，其特徵在於滿足下述(1)和(2)的條件。That is, according to the first invention of the present invention, there is provided a method for producing a metal-coated polyimide substrate, which comprises a sputtering step of forming a metal film on the surface of the polyimide film, and a method of using the film and the film Electroplating of a metal conductor on a metal film of the obtained polyimide film by a continuous plating apparatus comprising a metal film-coated roller and a plating tank having at least two grooves of an anode opposed to the metal film The step is characterized in that the conditions of the following (1) and (2) are satisfied.
(1)在上述濺射步驟中，形成的金屬覆膜的表面電阻控制在0.1~1.0Ω/□。(1) In the above sputtering step, the surface resistance of the formed metal film is controlled to be 0.1 to 1.0 Ω/□.
(2)在上述電鍍步驟中，陰極電流密度係控制在：全部電鍍槽的平均陰極電流密度為1~3A/dm2 ，以及各電鍍槽 中陰極電流密度的最大值對最小值之比為1~5，同時將薄膜的輸送速度調節為80~300m/h。(2) In the above electroplating step, the cathode current density is controlled such that the average cathode current density of all the plating baths is 1 to 3 A/dm 2 , and the ratio of the maximum value to the minimum value of the cathode current densities in each plating bath is 1 ~5, at the same time adjust the film transport speed to 80 ~ 300m / h.
另外，根據本發明的第2項發明，提供一種金屬被覆聚醯亞胺基板之製法，其特徵在於在第1項發明中，上述陽極為不溶性陽極。Further, according to a second aspect of the invention, there is provided a method of producing a metal-coated polyimide substrate, characterized in that in the first invention, the anode is an insoluble anode.
另外，根據本發明的第3項發明，提供一種金屬被覆聚醯亞胺基板之製法，其特徵在於在第2項發明中，上述陰極電流密度係全部電鍍槽的平均陰極電流密度為1.5~3A/dm2 ，各電鍍槽中陰極電流密度的最大值對最小值之比為1~3，以及薄膜的輸送速度為100~300m/h。According to a third aspect of the invention, there is provided a method for producing a metal-coated polyimide substrate, characterized in that in the second invention, the cathode current density is an average cathode current density of 1.5 to 3 A in all plating tanks. /dm 2 , the ratio of the maximum value of the cathode current density to the minimum value in each plating bath is 1 to 3, and the conveying speed of the film is 100 to 300 m/h.
另外，根據本發明的第4項發明，提供一種金屬被覆聚醯亞胺基板之製法，其特徵在於在第1~3任一項發明中，上述金屬覆膜係由金屬種子層(seed layer)與其表面上形成的銅層所構成。According to a fourth aspect of the present invention, a metal coated polyimide substrate is provided, characterized in that in the invention according to any one of the first to third aspects, the metal coating is a metal seed layer. It consists of a copper layer formed on its surface.
另外，根據本發明的第5項發明，提供一種金屬被覆聚醯亞胺基板之製法，其特徵在於在第1~4任一項發明中，上述金屬導電體為銅。According to a fifth aspect of the invention, the metal coated polyimide substrate is produced according to any one of the first to fourth aspects of the invention, wherein the metal conductor is copper.
根據本發明的金屬被覆聚醯亞胺基板之製法，可以降低加熱所得的金屬被覆聚醯亞胺基板時尺寸變化的分散程度，當將其作為COF使用時，可進行穩固地接合，並且可以改善不良率。特別是當用於以開發中的20 μm節距為代表的細距COF時，由於接合時端部引線脫離所要接合的位置的比率下降，大幅改善了不良率，因此其工業價值非常大。According to the method for producing a metal-coated polyimide substrate of the present invention, the degree of dispersion of the dimensional change when the metal-coated polyimide substrate is heated can be reduced, and when it is used as a COF, it can be firmly bonded and can be improved. Bad rate. In particular, when used for a fine pitch COF represented by a 20 μm pitch in development, the ratio of the position at which the end lead is detached at the time of joining is lowered, and the defective ratio is greatly improved, so that the industrial value is very large.
具體實施方式detailed description
以下，對本發明的金屬被覆聚醯亞胺基板之製法進行具體說明。Hereinafter, the method for producing the metal-coated polyimide substrate of the present invention will be specifically described.
本發明的金屬被覆聚醯亞胺基板之製法是包括在聚醯亞胺薄膜表面上形成金屬覆膜的濺射步驟、以及使用由輸送薄膜和向金屬覆膜供電的輥和具有與該金屬覆膜相對向的陽極的至少兩個槽的電鍍槽構成的連續電鍍裝置，在所得的聚醯亞胺薄膜的金屬覆膜上形成金屬導電體的電鍍步驟的金屬被覆聚醯亞胺基板之製法，其特徵在於滿足下述(1)和(2)的條件。The metal-coated polyimide substrate of the present invention is prepared by a sputtering step comprising forming a metal film on a surface of a polyimide film, and using a roller for supplying a film and supplying a metal film, and having a metal coating a method for producing a metal-coated polyimide substrate having a plating step of forming a metal conductor on a metal film of a polyimide film obtained by a continuous plating device comprising at least two grooves of a film opposite to the anode of the film, It is characterized by satisfying the conditions of the following (1) and (2).
(1)在上述濺射步驟中，形成的金屬覆膜的表面電阻控制在0.1~1.0Ω/□。(1) In the above sputtering step, the surface resistance of the formed metal film is controlled to be 0.1 to 1.0 Ω/□.
(2)在上述電鍍步驟中，陰極電流密度係控制在：全部電鍍槽的平均陰極電流密度為1~3A/dm2 ，以及各電鍍槽中陰極電流密度的最大值對最小值之比為1~5，同時將薄膜的輸送速度調節為80~300m/h。(2) In the above electroplating step, the cathode current density is controlled such that the average cathode current density of all the plating baths is 1 to 3 A/dm 2 , and the ratio of the maximum value to the minimum value of the cathode current densities in each plating bath is 1 ~5, at the same time adjust the film transport speed to 80 ~ 300m / h.
在本發明的製造方法中，通過在滿足上述(1)和(2)的條件下進行濺射步驟和電鍍步驟，控制形成的金屬覆膜的表面電阻，同時使電鍍的平均陰極電流密度處於一定的範圍內，以減小疊層結構每層的電流密度差，降低所形成的金屬層的殘留應力的分散程度，並減少由供電導致的電鍍中斷時間，抑制疊層結構的介面氧化，是很重要的。這樣，可以降低加熱時尺寸變化的分散性，當作為COF使用時，可以製得能夠穩固地接合的金屬被覆聚醯亞胺基板。In the manufacturing method of the present invention, the surface resistance of the formed metal film is controlled by performing the sputtering step and the plating step under the conditions (1) and (2) above, while the average cathode current density of the plating is kept constant. In order to reduce the difference in current density of each layer of the laminated structure, reduce the dispersion degree of the residual stress of the formed metal layer, and reduce the plating interruption time caused by the power supply, and suppress the interface oxidation of the laminated structure, which is very important. Thus, the dispersibility of the dimensional change upon heating can be reduced, and when used as a COF, a metal-coated polyimide substrate which can be firmly joined can be obtained.
以下，對濺射步驟和電鍍步驟中形成的金屬層的殘留 應力的分散，就其在現有技術中的問題以及在本發明製造方法中的作用進行詳細的說明。Hereinafter, the residual of the metal layer formed in the sputtering step and the plating step The dispersion of stress is explained in detail in terms of problems in the prior art and in the manufacturing method of the present invention.
即，通常在使用金屬被覆聚醯亞胺基板形成COF的引線時，如上所述，在引線的形成時增加了受熱過程等，對光阻曝光用掩模上形成的圖案尺寸要進行一定的校正。這是為了事先預測直至與IC晶片接合時以及與液晶面板接合時由受熱過程等引起的引線節距變化的量，以防止脫離而進行的。That is, generally, when a metal-coated polyimide substrate is used to form a COF lead, as described above, a heating process or the like is added at the time of forming the lead, and a pattern size formed on the resist exposure mask is corrected. . This is to predict in advance the amount of change in the lead pitch caused by the heat receiving process or the like when joining the IC wafer and when bonding to the liquid crystal panel to prevent detachment.
另外，引線節距變化的主要原因，是由於聚醯亞胺薄膜、金屬層以及防焊膜等COF的構成構件的熱脹冷縮等導致的變形。這種由熱引起的變形是必然發生的現象，其變形量可以通過試驗預先掌握。然而，問題是，這種變形量並不一定，即是分散的，而且，這種變形量的分散性越大，且引線節距越細距化，則上述脫離的可能性就越大。作為這些COF構成構件發生分散的原因，就聚醯亞胺薄膜而言，成膜時的受熱過程、延伸的分散以及薄膜厚度的分散是主要原因，另外，就防焊膜而言，厚度的分散是主要原因。另一方面，就金屬層而言，雖然厚度的分散也是主要原因，但金屬層的殘留應力的分散也產生很大的影響。Further, the main cause of the change in the lead pitch is deformation due to thermal expansion and contraction of the constituent members of the COF such as a polyimide film, a metal layer, and a solder resist film. This heat-induced deformation is an inevitable phenomenon, and the amount of deformation can be grasped in advance by experiments. However, the problem is that the amount of deformation is not necessarily, that is, it is dispersed, and the greater the dispersion of the amount of deformation, and the finer the pitch of the lead, the greater the possibility of the above-described detachment. As a cause of dispersion of these COF constituent members, in the polyimide film, the heat transfer process, the dispersion of the stretching, and the dispersion of the film thickness at the time of film formation are the main reasons, and in the case of the solder resist film, the dispersion of the thickness Is the main reason. On the other hand, in the case of the metal layer, although the dispersion of the thickness is also the main cause, the dispersion of the residual stress of the metal layer also has a large influence.
其中，在形成構成金屬層的金屬導電體的電鍍過程中，作為電鍍膜中殘留的應力分散的主要原因，聚醯亞胺薄膜上形成的陰極的電流密度(以下稱為陰極電流密度)的變化量具有最大的影響。也就是說，當通過電鍍法，在聚醯亞胺薄膜表面上的由濺射形成的金屬覆膜上形成金屬導電體時，通常，在電鍍的初期階段，由於該金屬覆膜與其上形 成的電鍍膜很薄而電阻很大，因而不得不使電鍍槽的電流密度極大地降低。之後，在達到一定電鍍厚度的成長階段，因注重生產性和經濟性而採取使電鍍槽的電流密度急劇增大的方法。例如，在以前的方法中，經電鍍槽形成的疊層結構的電鍍膜，在由濺射形成的金屬覆膜的緊鄰上層，以0.001~0.01A/dm2 的電流密度形成，而在最表層，以0.5~1.0A/dm2 的電流密度形成。此時全部電鍍槽的平均電流密度為0.3~0.7A/dm2 。通常，電鍍膜的殘留應力與陰極電流密度成正比，具有若電流密度高則應力也增大的傾向。因此，在以前的方法中，通過如上所述寬範圍的電流密度在疊層結構上形成電鍍膜的每層的殘留應力差係明顯地非常大，這是尺寸變化分散的主要原因。Among them, in the electroplating process of forming the metal conductor constituting the metal layer, the current density (hereinafter referred to as cathode current density) of the cathode formed on the polyimide film is changed as a main cause of stress dispersion remaining in the plating film. The amount has the greatest impact. That is, when a metal conductor is formed on a metal film formed by sputtering on the surface of a polyimide film by electroplating, usually, in the initial stage of electroplating, due to the metal film formed thereon The plating film is very thin and has a large electrical resistance, so that the current density of the plating bath has to be greatly reduced. Thereafter, in the growth stage in which a certain plating thickness is reached, a method of sharply increasing the current density of the plating tank is taken in consideration of productivity and economy. For example, in the prior method, the plating film of the laminated structure formed by the plating tank is formed at a current density of 0.001 to 0.01 A/dm 2 in the immediately adjacent upper layer of the metal film formed by sputtering, and is at the outermost layer. It is formed at a current density of 0.5 to 1.0 A/dm 2 . At this time, the average current density of all the plating tanks is 0.3 to 0.7 A/dm 2 . Generally, the residual stress of the plating film is proportional to the cathode current density, and the stress tends to increase if the current density is high. Therefore, in the prior method, the residual stress difference of each layer in which the plating film is formed on the laminated structure by the wide range of current densities as described above is remarkably very large, which is the main cause of dimensional dispersion dispersion.
作為抑制這種電鍍膜每層的殘留應力差的手段，可以考慮保持電鍍初期階段的極低電流密度不變，繼續進行電鍍，但是這樣給生產力帶來極大的障礙，必需建立極長的生產線，因而不現實。例如，當以平均電流密度0.1A/dm2 電鍍至厚度為8 μm時，電鍍時間必需達到5小時。另外，在極低電流密度下的電鍍雖然對降低殘留應力很有效，但是由於對伸長率、抗拉強度、耐折曲性等其他重要的電鍍膜的物性產生影響，因而認為在現行的使用COF的組裝步驟中，引起接合以外的麻煩的可能性很高。另外，在低電流密度下製得的電鍍膜由於耐折曲性變差，因而在COF的接合時斷路等的可能性增大。並且，在經濟性方面，平均電流密度也需要確保在一定的值以上。As means for suppressing the residual stress difference of each layer of the plating film, it is possible to continue the electroplating by keeping the extremely low current density in the initial stage of electroplating constant, but this poses a great obstacle to productivity, and it is necessary to establish an extremely long production line. It is therefore unrealistic. For example, when plating at an average current density of 0.1 A/dm 2 to a thickness of 8 μm, the plating time must be 5 hours. In addition, electroplating at extremely low current densities is effective for reducing residual stress, but it is considered to be in the current use of COF due to influence on physical properties of other important plating films such as elongation, tensile strength, and flex resistance. In the assembly step, there is a high possibility of causing troubles other than bonding. Further, since the plating film produced at a low current density is deteriorated in the bending resistance, there is a possibility that the plating of the COF is broken or the like during the joining. Moreover, in terms of economy, the average current density also needs to be secured above a certain value.
相比之下，在本發明的金屬被覆聚醯亞胺基板之製法 中，如上所述，通過在滿足上述(1)和(2)的條件下進行濺射步驟和電鍍步驟，控制形成的金屬覆膜的表面電阻，同時使電鍍的平均陰極電流密度處於一定的範圍內，以減小疊層結構每層的電流密度差，降低所形成的金屬層的殘留應力的分散程度，並減少由供電導致的電鍍中斷時間，抑制疊層結構的介面氧化。由此，提高了生產力。In contrast, the method for preparing a metal-coated polyimide substrate of the present invention In the above, as described above, the surface resistance of the formed metal film is controlled by performing the sputtering step and the plating step under the conditions (1) and (2) above, while the average cathode current density of the plating is in a certain range. In order to reduce the difference in current density of each layer of the laminated structure, the degree of dispersion of the residual stress of the formed metal layer is reduced, and the plating interruption time caused by the power supply is reduced, and the interface oxidation of the laminated structure is suppressed. As a result, productivity is increased.
作為本發明的金屬被覆聚醯亞胺基板之製法，包括在聚醯亞胺薄膜表面上形成金屬覆膜的濺射步驟和在所得聚醯亞胺薄膜的金屬覆膜上形成金屬導電體的電鍍步驟。即，在聚醯亞胺薄膜表面上形成極薄的金屬覆膜，再通過電鍍法增厚到所需的厚度。The method for producing a metal-coated polyimide substrate of the present invention comprises a sputtering step of forming a metal film on the surface of the polyimide film and plating for forming a metal conductor on the metal film of the obtained polyimide film. step. That is, an extremely thin metal film is formed on the surface of the polyimide film, and then thickened to a desired thickness by electroplating.
1. 濺射步驟Sputtering step
作為上述濺射步驟，除上述(1)的條件以外，對其沒有特別的限制，可以在聚醯亞胺薄膜表面上，在形成所需厚度金屬覆膜的，通常金屬被覆聚醯亞胺基板之製法中所使用的條件下進行。這裏，作為上述濺射中所用的裝置，對其沒有特別的限制，可以使用具有由含有構成金屬覆膜的元素的規定組成構成的靶的磁控管濺射裝置等。As the sputtering step, in addition to the conditions of the above (1), it is not particularly limited, and a metal-coated polyimide substrate may be formed on the surface of the polyimide film in a metal film of a desired thickness. It is carried out under the conditions used in the preparation method. Here, the apparatus used for the sputtering is not particularly limited, and a magnetron sputtering apparatus or the like having a target having a predetermined composition of an element constituting the metal coating can be used.
作為上述製造方法中使用的聚醯亞胺薄膜，對其沒有特別的限制，可以使用Kapton EN(東麗．杜邦製造)、Upilex S(宇部興產製造)、Apical(卡卡製造)等市售的聚醯亞胺薄膜。另外，作為聚醯亞胺薄膜的厚度，對其沒有特別的限制，若考慮確保其彎曲性，較佳為25~50μm。The polyimine film used in the above production method is not particularly limited, and Kapton EN (manufactured by Toray DuPont), Upilex S (manufactured by Ube Industries), and Apical (card) can be used. Commercially available polyimide film, such as card manufacturing. Further, the thickness of the polyimide film is not particularly limited, and it is preferably 25 to 50 μm in consideration of ensuring the flexibility.
作為上述濺射過程中形成的金屬覆膜，對其沒有特別的限制，為了確保其與聚醯亞胺的黏合力以及其耐熱性等 的可靠性，作為金屬種子層，可以從鎳、鉻、鉬等金屬或者鎳鉻合金等它們的合金中選擇，但較佳係相對於總量含5~30質量%鉻的鎳鉻合金。另外，其厚度較佳為5~50nm。換句話說，因為當用於COF等並將金屬層通過蝕刻形成電子電路時，與作為良導體的銅的蝕刻性有很大差別的合金組成和厚度都是不合適的。The metal film formed in the above sputtering process is not particularly limited, and the adhesion to the polyimide and the heat resistance thereof are ensured. The reliability of the metal seed layer may be selected from metals such as nickel, chromium, molybdenum or the like, or alloys such as nickel-chromium alloy, but is preferably a nickel-chromium alloy containing 5 to 30% by mass of chromium based on the total amount. Further, the thickness thereof is preferably 5 to 50 nm. In other words, since when used for COF or the like and the metal layer is formed by etching to form an electronic circuit, the alloy composition and thickness which are greatly different from the etching property of copper as a good conductor are not suitable.
另外，為了降低表面電阻以確保進行電鍍前的導電性，較佳係繼續通過濺射在上述金屬覆膜表面上形成銅層。作為此時的銅層，要控制表面電阻為滿足(1)的條件的規定值。換句話說，當厚度低於50nm時，則不能獲得足夠的導電性，將對之後電鍍的銅析出的均勻性產生不良影響。另一方面，若厚度超過500nm，雖然在產生導電性方面較好，但由於濺射對聚醯亞胺薄膜的熱過程提高而對基板的尺寸變化、變形等產生影響，恐怕對COF等製得的產品會產生不良影響。Further, in order to lower the surface resistance to ensure conductivity before plating, it is preferred to continue to form a copper layer on the surface of the above metal film by sputtering. As the copper layer at this time, the surface resistance is controlled to a predetermined value satisfying the condition of (1). In other words, when the thickness is less than 50 nm, sufficient conductivity cannot be obtained, which adversely affects the uniformity of precipitation of copper which is subsequently plated. On the other hand, when the thickness exceeds 500 nm, it is preferable in terms of electrical conductivity. However, since the thermal process of the polyimide film is increased by sputtering, the size change and deformation of the substrate are affected, and it is likely to be produced for COF or the like. The product will have an adverse effect.
上述製造方法中有關的(1)的條件在上述濺射步驟中，控制所形成的金屬覆膜的表面電阻為0.1~1.0Ω/□。也就是說，通過降低濺射中形成的金屬覆膜的表面電阻，可以提高自電鍍初期階段的電流密度，因此可以提高平均陰極電流密度。然而，使上述金屬覆膜表面電阻的降低，即是使上述金屬覆膜厚度的增加，這時，濺射使聚醯亞胺薄膜受到的熱量增加，必然分散程度也增大。結果，COF的接合時引線位置偏離的危險性增加。因此，在本發明製造方法中，上述金屬覆膜的表面電阻要在由濺射產生熱量的增加導致的分散程度不至於很大的範圍內選擇。The condition (1) in the above production method controls the surface resistance of the formed metal film to be 0.1 to 1.0 Ω/□ in the sputtering step. That is, by lowering the surface resistance of the metal film formed during sputtering, the current density in the initial stage of electroplating can be increased, so that the average cathode current density can be increased. However, the reduction in the surface resistance of the above metal film is such that the thickness of the metal film is increased. In this case, the heat absorbed by the polyimide film is increased by sputtering, and the degree of dispersion is inevitably increased. As a result, the risk of deviation of the lead position when the COF is joined increases. Therefore, in the production method of the present invention, the surface resistance of the above metal film is selected within a range in which the degree of dispersion due to an increase in heat generated by sputtering is not so large.
換句話說，當金屬覆膜的表面電阻低於0.1Ω/□時，濺射熱過程的分散程度增大，接合時位置的偏離增加。另一方面，若金屬覆膜的表面電阻超過1.0Ω/□，則電鍍初期階段陰極電流密度必需控製得極低，從而增大了電鍍的疊層結構的每層陰極電流密度差。或者，若以超過1.0Ω/□的狀態強制增大陰極電流密度，則會增大鍍膜的殘留應力。另外，為了減小濺射的熱過程的分散程度，並且減小陰極電流密度差，金屬覆膜的表面電阻較佳係控制在0.2~0.8Ω/□。In other words, when the surface resistance of the metal film is less than 0.1 Ω/□, the degree of dispersion of the sputtering heat process increases, and the deviation of the position at the time of bonding increases. On the other hand, if the surface resistance of the metal coating exceeds 1.0 Ω/□, the cathode current density in the initial stage of electroplating must be controlled to be extremely low, thereby increasing the difference in cathode current density per layer of the laminated structure of the plating. Alternatively, if the cathode current density is forcibly increased in a state exceeding 1.0 Ω/□, the residual stress of the plating film is increased. Further, in order to reduce the degree of dispersion of the thermal process of sputtering and to reduce the difference in cathode current density, the surface resistance of the metal film is preferably controlled to 0.2 to 0.8 Ω/□.
作為上述金屬覆膜的表面電阻的控制方法，由於其表面電阻受濺射中形成的金屬覆膜的厚度、純度、結晶粒徑等的影響，因而要獲得所需的表面電阻，可以通過選擇濺射條件而進行。例如，在真空下進行的磁控管濺射中，在由濺射形成銅層的場合，通過使銅層的厚度為300~10nm，可以使金屬覆膜的表面電阻為0.1~1.0Ω/□。As a method of controlling the surface resistance of the above metal film, since the surface resistance is affected by the thickness, purity, crystal grain size, and the like of the metal film formed during sputtering, it is possible to obtain a desired surface resistance by selecting a sputtering. The shooting conditions are carried out. For example, in magnetron sputtering performed under vacuum, when a copper layer is formed by sputtering, the surface resistance of the metal film can be 0.1 to 1.0 Ω/□ by making the thickness of the copper layer 300 to 10 nm. .
2. 電鍍步驟2. Plating step
作為上述電鍍步驟，除了上述(2)的條件以外，對其沒有特別的限制，可以在聚醯亞胺薄膜上形成的滿足(1)條件的金屬覆膜上，使用連續電鍍裝置，在形成金屬導電體，通常金屬被覆聚醯亞胺基板之製法中所使用的條件下進行。The plating step is not particularly limited, except for the conditions of the above (2), and a metal plating film which satisfies the condition (1) formed on the polyimide film can be formed by using a continuous plating apparatus. The conductor is usually carried out under the conditions used in the production method of the metal-coated polyimide substrate.
另外，上述連續電鍍裝置是由輸送薄膜和向金屬覆膜供電的輥和具有與該金屬覆膜相對向的陽極的至少兩個槽的電鍍槽構成的裝置，例如，由於可以大幅節約設置空間，使用在輸送線方向上並排設置了根據電鍍厚度等而定的必 要數目的豎型電鍍槽的裝置。這裏，將具有金屬覆膜的一定寬度的聚醯亞胺薄膜以一定的速度依次連續地供給到電鍍槽中，在金屬覆膜上連續地形成電鍍層。即，可以使用通常金屬被覆聚醯亞胺基板之製法中所用的連續電鍍裝置，該裝置具有與金屬覆膜接觸的可以供電的具有導電性的輥、在該金屬覆膜相對向的位置設置了陽極的電鍍槽、向該槽內供給薄膜的與電鍍液接觸並輸送的薄膜輸送機構。Further, the above continuous plating apparatus is constituted by a transporting film and a plating tank for supplying power to the metal coating and a plating tank having at least two grooves of the anode opposed to the metal coating, for example, since the installation space can be greatly saved, Use in the direction of the conveying line side by side according to the plating thickness, etc. The number of vertical plating bath devices. Here, a polyimide film having a certain width of a metal film is sequentially supplied to the plating tank at a constant speed, and a plating layer is continuously formed on the metal film. That is, a continuous plating apparatus used in a method of generally coating a metal-coated polyimide substrate having a conductive roller which is in contact with a metal film and capable of supplying electricity, and a position where the metal film is opposed to each other may be used. A plating tank for the anode, a film transport mechanism that supplies a film to the tank and is in contact with and transported by the plating solution.
作為上述金屬導電體，對其沒有特別的限制，在COF等中較佳係做為電路材料，並且可以使用電鍍被覆的導電性優良的金屬或合金，較佳為銅。此時作為所用的電鍍液，可以使用通常銅電鍍中所用的市售的硫酸銅電鍍液。The metal conductor is not particularly limited, and is preferably used as a circuit material in COF or the like, and a metal or an alloy having excellent conductivity, which is preferably plated, can be used. At this time, as the plating solution to be used, a commercially available copper sulfate plating solution which is usually used in copper plating can be used.
上述製造方法中有關的(2)條件，在上述電鍍步驟中是陰極電流密度係控制在全部電鍍槽的平均陰極電流密度為1~3A/dm2 ，以及各電鍍槽中陰極電流密度的最大值對最小值之比為1~5，同時將薄膜的輸送速度調節為80~300m/h。換句話說，是為了降低滿足(1)條件的金屬覆膜上形成的金屬層的殘留應力的分散程度，抑制接合時的位置偏離，而使電鍍的各層的平均陰極電流密度處於一定的範圍內，以減小疊層結構每層的電流密度差。不過，作為電鍍的平均陰極電流密度，就抑制接合時的位置偏離而言，減小疊層結構每層的陰極電流密度差即可，但是，考慮到要確保耐折曲性以及生產性、經濟性方面，本發明製造方法的電鍍步驟中，使用上述(2)的條件。The condition (2) in the above manufacturing method is that the cathode current density is controlled in the plating step to control the average cathode current density of all the plating tanks to be 1 to 3 A/dm 2 , and the maximum value of the cathode current density in each plating bath. The ratio of the minimum value is 1 to 5, and the conveying speed of the film is adjusted to 80 to 300 m/h. In other words, in order to reduce the degree of dispersion of the residual stress of the metal layer formed on the metal film satisfying the condition (1), the positional deviation at the time of bonding is suppressed, and the average cathode current density of each layer of the plating is within a certain range. To reduce the current density difference of each layer of the laminated structure. However, as the average cathode current density of plating, the difference in cathode current density per layer of the laminated structure can be reduced in terms of suppressing the positional deviation at the time of bonding, but it is considered to ensure the flexibility and productivity and economy. In terms of the electroplating step of the production method of the present invention, the conditions of the above (2) are used.
換句話說，作為陰極電流密度，當全部電鍍槽的平均陰極電流密度低於1A/dm2 時，則難以確保其耐折曲性。 另一方面，若平均陰極電流密度超過3A/dm2 ，則難以抑制殘留應力的分散。另外，在確保可靠性和經濟性方面，全部電鍍槽的平均陰極電流密度較佳為1.5~3A/dm2 。In other words, as the cathode current density, when the average cathode current density of all the plating tanks is less than 1 A/dm 2 , it is difficult to ensure the bending resistance. On the other hand, when the average cathode current density exceeds 3 A/dm 2 , it is difficult to suppress dispersion of residual stress. Further, in terms of ensuring reliability and economy, the average cathode current density of all the plating tanks is preferably 1.5 to 3 A/dm 2 .
並且，通過控制各電鍍槽中陰極電流密度的最大值對最小值之比為1~5，使疊層結構各層內電流密度分佈均一化，可以實現構成金屬層的金屬導電體的殘留應力進一步均一化。這樣，可以使疊層結構整體的殘留應力均一化，從而抑制分散。換句話說，若上述陰極電流密度的最大值對最小值之比超過5，則由電流密度差導致的殘留應力差增大，從而增大了分散性。另外，為了使殘留應力均一化，陰極電流密度較佳使陰極電流密度最大值對最小值之比為1~3。Further, by controlling the ratio of the maximum value to the minimum value of the cathode current density in each plating bath to be 1 to 5, the current density distribution in each layer of the laminated structure is uniformized, and the residual stress of the metal conductor constituting the metal layer can be further uniformed. Chemical. Thus, the residual stress of the entire laminated structure can be made uniform, thereby suppressing dispersion. In other words, if the ratio of the maximum value to the minimum value of the cathode current density exceeds 5, the residual stress difference caused by the difference in current density increases, thereby increasing the dispersibility. Further, in order to uniformize the residual stress, the cathode current density is preferably such that the ratio of the maximum value of the cathode current density to the minimum value is 1 to 3.
作為上述陰極電流密度的控制方法，通常，在電鍍初期階段，即金屬覆膜的表面電阻高的區域，上述連續電鍍裝置的各電鍍槽內，電流密度極易集中在與供電輥接近的電鍍液入口介面處，相反電鍍槽底部電流密度大幅降低，因此，為了抑制電鍍槽入口處電流密度的集中，需要在聚醯亞胺薄膜上的金屬覆膜與陽極之間設置適當的電流遮罩板的方法等，而對其手段沒有特別的限制。例如，作為電流遮罩板，可以採取在絕緣板上設置開口部，調節其開口面積的方法，通常使其在電流密度集中的電鍍液介面附近較小，相反使電流密度小的電鍍槽底部較大。As a method of controlling the cathode current density, generally, in an initial stage of electroplating, that is, a region where the surface resistance of the metal film is high, in each plating tank of the continuous plating apparatus, the current density is easily concentrated in the plating solution close to the power supply roller. At the inlet interface, the current density at the bottom of the plating bath is greatly reduced. Therefore, in order to suppress the concentration of current density at the entrance of the plating bath, it is necessary to provide a suitable current mask between the metal coating on the polyimide film and the anode. The method and the like, and there is no particular limitation on the means thereof. For example, as a current mask, a method of providing an opening on an insulating plate and adjusting an opening area thereof may be generally performed in a vicinity of a plating liquid interface in which current density is concentrated, and a bottom of the plating tank having a smaller current density. Big.
另外，通過將薄膜的輸送速度調節為80~300m/h，在將半導體晶片通過接合封裝在COF上並將半導體晶片用樹脂密封時，可以避免引線表面鍍錫保護膜脫落的問 題。也就是說，由於上述連續電鍍裝置由多個電鍍槽和供電部以及輸送機構構成，當使用該裝置將金屬導電體形成疊層結構時，由於要向金屬覆膜及其上形成的電鍍膜供電，因而會出現聚醯亞胺基板處於電鍍液外的時間，即疊層結構的各層之間電鍍的中斷時間。若該電鍍中斷時間較長，則在將所得基板通過刻蝕形成引線，並在其表面上通過無電鍍敷形成鍍錫膜後，在將半導體晶片通過接合封裝在COF上並將半導體晶片用樹脂密封時，會出現引線表面的鍍錫保護膜發生脫落的危險性問題。Further, by adjusting the transport speed of the film to 80 to 300 m/h, when the semiconductor wafer is packaged on the COF by bonding and the semiconductor wafer is sealed with a resin, the peeling of the tin plating protective film on the lead surface can be avoided. question. That is, since the above continuous plating apparatus is composed of a plurality of plating tanks, a power supply portion, and a conveying mechanism, when the metal conductor is formed into a laminated structure using the apparatus, the metal film and the plating film formed thereon are supplied with power. Thus, there is a time when the polyimide substrate is outside the plating solution, that is, the interruption time of plating between the layers of the laminated structure. If the plating interruption time is long, the obtained substrate is formed by etching to form a lead, and a tin-plated film is formed by electroless plating on the surface thereof, and then the semiconductor wafer is packaged on the COF by bonding and the semiconductor wafer is resin-coated. When sealing, there is a risk that the tin-plated protective film on the surface of the lead will fall off.
更具體地說，已知當將半導體晶片進行樹脂密封時，當經受3小時150℃的熱負荷時，在引線表層部位錫與銅發生合金化時會產生由於擴散速度差而產生的空隙，即所謂的柯肯達爾(Kirkendall)空隙。在由上述連續電鍍裝置製得鍍銅膜的疊層結構中，由下層對合金化所需銅離子的供給，由於疊層結構介面狀態而發生延遲。在銅離子供給處於延遲的狀態下，引線表層部位在沒有下層供給銅離子的狀態下，存在銅向錫一側擴散而使空隙急劇增加、擴大的危險。而疊層結構介面越是氧化，即在電鍍液外的電鍍中斷時間越長，則其危險性越大。因此，通過使薄膜的輸送速度達到一定速度以上，使電鍍的中斷時間處於一定時間以內，可以抑制疊層結構介面的氧化，從而抑制引線表面鍍錫保護膜的脫落。More specifically, it is known that when a semiconductor wafer is subjected to resin sealing, when subjected to a heat load of 150 ° C for 3 hours, a void due to a difference in diffusion speed occurs when alloying tin with copper at the surface portion of the lead, that is, The so-called Kirkendall gap. In the laminated structure in which the copper plating film is produced by the above continuous plating apparatus, the supply of copper ions required for alloying by the lower layer is delayed due to the interface state of the laminated structure. When the supply of copper ions is delayed, in the state in which the copper layer ions are not supplied to the surface layer portion of the lead, there is a possibility that copper diffuses toward the tin side and the voids sharply increase and expand. The more oxidized the interface of the laminated structure, that is, the longer the plating interruption time outside the plating solution, the greater the risk. Therefore, by setting the transport speed of the film to a certain speed or higher and the interruption time of the plating to be within a certain period of time, the oxidation of the laminated structure interface can be suppressed, and the fall of the tin plating protective film on the lead surface can be suppressed.
換句話說，當薄膜的輸送速度低於80m/h時，即使使供電部小型化，電鍍中斷時間也會達到約30秒以上，上述脫落的危險性增大。另一方面，若薄膜的輸送速度超過 300m/h，則會發生基板上產生缺陷等的危險。另外，為了使引線表面的鍍錫保護膜不發生脫落，較佳薄膜的輸送速度達到100m/h以上。In other words, when the transport speed of the film is less than 80 m/h, even if the power supply portion is downsized, the plating interruption time becomes about 30 seconds or more, and the risk of the above-described dropping is increased. On the other hand, if the film transport speed exceeds At 300 m/h, there is a risk of defects or the like on the substrate. Further, in order to prevent the tin-plated protective film on the surface of the lead from falling off, the transport speed of the film is preferably 100 m/h or more.
作為上述連續電鍍裝置中使用的陽極，對其沒有特別的限制，可以使用可溶性或不溶性陽極，然而，其中，通過使用不溶性陽極，可以在顯示更好效果的電鍍條件下進行。這時，較佳全部電鍍槽的平均陰極電流密度控制在1.5~3.0A/dm2 ，各電鍍槽中陰極電流密度的最大值對最小值之比控制在1~3，同時將薄膜的輸送速度調節為100~300m/h。另外，通常，在鍍銅中，可溶性陽極成問題的是含磷的銅球表面上產生的碎屑等混入電鍍液中，出現使電鍍外觀品質下降的問題，為防止該問題，可以使用不溶性陽極，而在金屬被覆聚醯亞胺基板之製法中，從抑制殘留應力的分散、電鍍膜耐折曲性等角度出發，使用不溶性陽極可以使電鍍電流密度條件、基板輸送速度最佳化。這是因為，不溶性陽極所具有的表面電位的均一性、電極間距離的均一性發揮作用，與可溶性陽極相比更容易實現電流密度的均一化。The anode used in the above continuous plating apparatus is not particularly limited, and a soluble or insoluble anode can be used, however, by using an insoluble anode, it can be carried out under plating conditions showing a better effect. At this time, it is preferable that the average cathode current density of all the plating tanks is controlled to be 1.5 to 3.0 A/dm 2 , and the ratio of the maximum value of the cathode current density to the minimum value in each plating tank is controlled to 1 to 3, and the conveying speed of the film is adjusted. It is 100~300m/h. In addition, in copper plating, in general, the problem of the soluble anode is that the debris generated on the surface of the phosphorus-containing copper ball is mixed into the plating solution, and there is a problem that the appearance quality of the plating is lowered. To prevent this problem, an insoluble anode can be used. In the method for producing a metal-coated polyimide substrate, the plating current density condition and the substrate transport speed can be optimized by using an insoluble anode from the viewpoint of suppressing dispersion of residual stress and bending resistance of the plating film. This is because the uniformity of the surface potential and the uniformity of the distance between the electrodes of the insoluble anode function, and it is easier to achieve uniformization of the current density than the soluble anode.
作為上述可溶性陽極，對其沒有特別的限制，可以使用含有構成所形成的金屬導電體的元素的市售陽極，對於獲得銅導體的情況，可以使用在鈦盒中填充含磷銅球的陽極。The soluble anode is not particularly limited, and a commercially available anode containing an element constituting the formed metal conductor can be used. For the case of obtaining a copper conductor, an anode in which a phosphorus-containing copper ball is filled in a titanium case can be used.
作為不溶性陽極，對其沒有特別的限制，可以使用以鈦為基體，表面上形成鉑或其氧化物薄膜的陽極等，較佳例如具有在鈦網表面塗敷氧化銥結構的陽極。The insoluble anode is not particularly limited, and an anode having a film of platinum or an oxide film formed thereon on the surface of titanium may be used. For example, an anode having a ruthenium oxide structure coated on the surface of the titanium mesh is preferably used.
以下，藉由本發明的實施例和比較例對本發明進行更具體的說明，但是本發明並不受此等實施例之任何限定。另外，在實施例和比較例中使用的金屬覆膜的表面電阻和金屬被覆聚醯亞胺基板作為COF使用時的評價方法如下。Hereinafter, the present invention will be more specifically described by the examples and comparative examples of the present invention, but the present invention is not limited to these examples. In addition, the surface resistance of the metal film used in the examples and the comparative examples and the evaluation method of the metal-coated polyimide substrate as COF were as follows.
(1)金屬覆膜表面電阻的測定：按照JIS K 7194使用四探針法進行。(1) Measurement of surface resistance of metal film: It was carried out in accordance with JIS K 7194 using a four-probe method.
(2)金屬被覆聚醯亞胺基板作為COF使用時的評價：使用所得金屬被覆聚醯亞胺基板，通過減成法，形成內引線部為20 μm節距、外引線部為35 μm節距的引線圖案，在引線表面通過無電鍍敷法形成厚度為0.6 μm的覆錫膜。然後，為了抑制鍍錫膜中產生晶鬚的目的，在120℃下進行60分鐘熱處理，再在所需部位形成厚度為10 μm的防焊膜層，為了使其熱硬化的目的，在120℃下進行2小時熱處理。熱處理後，為了使內引線部與IC晶片的基座部接合，將接合部在420℃下熱壓合1秒鐘，然後在IC晶片及其周圍部位塗敷熱固化性樹脂，在150℃下進行3小時熱處理，將IC晶片用樹脂封閉。然後，為了將外引線部位與液晶面板ITO電極進行ACF接合，將接合部位在200℃下熱壓合5秒鐘。(2) Evaluation of the metal-coated polyimide substrate as COF: The obtained metal-coated polyimide substrate was subjected to a subtractive method to form a pitch of 20 μm for the inner lead portion and a pitch of 35 μm for the outer lead portion. The lead pattern was formed on the surface of the lead by a non-electroplating method to form a tin-coated film having a thickness of 0.6 μm. Then, in order to suppress the generation of whiskers in the tin plating film, heat treatment was performed at 120 ° C for 60 minutes, and a solder resist layer having a thickness of 10 μm was formed at a desired portion. For the purpose of heat curing, at 120 ° C The heat treatment was carried out for 2 hours. After the heat treatment, in order to bond the inner lead portion to the base portion of the IC wafer, the joint portion was thermocompression-bonded at 420 ° C for 1 second, and then a thermosetting resin was applied to the IC wafer and its surrounding portion at 150 ° C. The heat treatment was performed for 3 hours, and the IC wafer was sealed with a resin. Then, in order to perform ACF bonding of the outer lead portion and the liquid crystal panel ITO electrode, the joint portion was thermocompression-bonded at 200 ° C for 5 seconds.
進行以上處理之後，觀察內引線部和外引線部的接合部，求出由位置偏離導致的脫落等不良的發生率。After the above processing, the joint portion between the inner lead portion and the outer lead portion was observed, and the incidence of defects such as detachment due to the positional deviation was obtained.
另外，顯示鍍錫的脫落性的指標，使用進行加速實驗的評價結果。即，使用Roam & Hass公司製造的無電鍍敷液Tinposit LT－34，在引線表面上形成厚度為0.6 μm 的鍍錫膜後，在160℃下處理24小時，在該引線部位表面上貼上透明帶，充分黏合後，剝離透明帶，在200倍的金屬顯微鏡下確認有無錫鍍膜的脫落。In addition, an index indicating the peeling property of tin plating was used, and the evaluation result of the accelerated experiment was used. That is, a thickness of 0.6 μm was formed on the surface of the lead using the electroless plating solution Tinposit LT-34 manufactured by Roam & Hass. After the tin plating film was treated at 160 ° C for 24 hours, a transparent tape was attached to the surface of the lead portion, and after sufficiently bonding, the transparent tape was peeled off, and it was confirmed that the tin-free plating film was peeled off under a metal microscope of 200 times.
另外，實施例和比較例中使用的連續電鍍裝置如下。Further, the continuous plating apparatuses used in the examples and comparative examples are as follows.
第1圖表示了上述連續電鍍裝置的簡略結構的一個實例。在第1圖中，連續電鍍裝置是具有用於輸送薄膜2和向金屬覆膜及電鍍膜供電的不銹鋼製的供電輥3、以及在電鍍槽1內使薄膜2反轉的反轉輥4、17個裝有陽極5的電鍍槽1在輸送方向上並排設置的裝置的一個實例。Fig. 1 shows an example of a schematic structure of the above continuous plating apparatus. In the first embodiment, the continuous plating apparatus is provided with a stainless steel power supply roller 3 for transporting the film 2 and supplying power to the metal film and the plating film, and a reverse roller 4 for reversing the film 2 in the plating tank 1. An example of a device in which 17 electroplating tanks 1 equipped with an anode 5 are arranged side by side in the conveying direction.
另外，在實施例和比較例中，各電鍍槽的槽內電鍍長度，即浸漬於電鍍液的距離為3000mm，各電鍍槽間用於向電鍍面供電而在電鍍液外輸送基板的距離為700mm。另外，使用的電鍍槽數目，是基於各條件合理需要的槽數。另外，陽極與金屬覆膜和電鍍膜之間設置了具有各種形狀的電流遮罩板。此外，鍍銅液使用含硫酸180g/L、硫酸銅80g/L、氯離子50mg/L、以及為確保鍍銅膜平滑性等目的而添加的規定量的有機添加劑的鍍銅液。Further, in the examples and the comparative examples, the plating length of each plating tank, that is, the distance immersed in the plating solution was 3000 mm, and the distance between each plating tank for supplying power to the plating surface and the substrate outside the plating liquid was 700 mm. . In addition, the number of plating tanks used is based on the number of tanks reasonably required for each condition. In addition, a current mask having various shapes is disposed between the anode and the metal film and the plating film. Further, as the copper plating solution, a copper plating solution containing a predetermined amount of an organic additive added for the purpose of ensuring 180 g/L of sulfuric acid, 80 g/L of copper sulfate, 50 mg/L of chloride ion, and the like for ensuring smoothness of a copper plating film is used.
(實施例1)(Example 1)
首先，通過在真空環境中運行的磁控管濺射裝置，聚醯亞胺薄膜使用Kapton 150 EN(東麗．杜邦製造)，在真空度保持為0.01~0.1Pa的腔內，於150℃下進行1分鐘的加熱處理。接著，使用相對於總量含20質量%鉻的鎳鉻合金靶和銅靶，在聚醯亞胺薄膜表面上形成厚度為20nm的鎳鉻合金層和厚度為300nm的銅層。所得金屬覆膜的表面電阻為0.1Ω/□。First, the polyimide film was sprayed in a vacuum environment using a Kapton 150 EN (manufactured by Toray DuPont) in a cavity maintained at a vacuum of 0.01 to 0.1 Pa at 150 ° C. Heat treatment was performed for 1 minute. Next, a nickel-chromium alloy layer having a thickness of 20 nm and a copper layer having a thickness of 300 nm were formed on the surface of the polyimide film using a nickel-chromium alloy target and a copper target containing 20% by mass of chromium based on the total amount. The surface resistance of the obtained metal film was 0.1 Ω/□.
然後，使用所得的濺射後的聚醯亞胺薄膜，使用上述連續電鍍裝置(電鍍槽數：17槽)，在銅覆膜上層疊鍍銅層，製得形成了銅導體的金屬被覆聚醯亞胺基板。這裡，作為上述連續電鍍裝置的陽極，使用鈦盒中填充含磷的銅球、盒周圍用聚丙烯製得的基質(基底)覆蓋的可溶性陽極。另外，全部電鍍槽的平均電流密度(以下，也稱為總平均電流密度)控制在1.0A/dm2 ，以及各電鍍槽內陰極電流密度的最大值對最小值之比控制在5，同時薄膜的輸送速度調節為80m/h，直至厚度達到8μm，形成由電鍍膜構成的銅導體。Then, using the obtained sputtered polyimide film, a copper plating layer was laminated on the copper film by using the above-described continuous plating apparatus (the number of plating tanks: 17 grooves) to obtain a metal-coated polyimide having a copper conductor. Imine substrate. Here, as the anode of the above continuous plating apparatus, a soluble anode filled with a phosphorus-containing copper ball in a titanium case and a substrate (base) made of polypropylene around the case is used. In addition, the average current density (hereinafter, also referred to as total average current density) of all the plating tanks is controlled at 1.0 A/dm 2 , and the ratio of the maximum value to the minimum value of the cathode current density in each plating bath is controlled at 5 while the film The conveying speed was adjusted to 80 m/h until the thickness reached 8 μm, and a copper conductor composed of a plating film was formed.
然後，使用所得的金屬被覆聚醯亞胺基板，按照上述“金屬被覆聚醯亞胺基板作為COF使用時的評價方法”，求出COF接合部的位置偏離的不良發生率、引線斷路發生率以及鍍錫膜脫落發生率。結果列於表1。Then, using the obtained metal-coated polyimide substrate, the occurrence rate of the positional deviation of the COF joint portion, the occurrence rate of the lead disconnection, and the rate of occurrence of the lead disconnection of the COF joint portion and the "method of evaluation when the metal-coated polyimide substrate is used as COF" The incidence of tin plating film shedding. The results are shown in Table 1.
(實施例2)(Example 2)
除了各電鍍槽內陰極電流密度的最大值對最小值之比控制在3以外，與實施例1同樣地操作，使用所得的金屬被覆聚醯亞胺基板，按照上述“金屬被覆聚醯亞胺基板作為COF使用時的評價方法”，求出COF接合部的位置偏離的不良發生率、引線斷路發生率以及鍍錫膜脫落發生率。結果列於表1。The obtained metal-coated polyimide substrate was used in the same manner as in Example 1 except that the ratio of the maximum value to the minimum value of the cathode current density in each plating bath was controlled to 3, in accordance with the above-mentioned "metal-coated polyimide substrate". As an evaluation method at the time of use of COF, the occurrence rate of the positional deviation of the COF joint portion, the occurrence rate of the lead wire breakage, and the incidence rate of the tin plating film were determined. The results are shown in Table 1.
(實施例3)(Example 3)
上述連續電鍍裝置的電鍍槽數為12槽，總平均電流密度控制在1.5A/dm2 ，以及各電鍍槽內陰極電流密度的最大值對最小值之比控制在3，除此以外，與實施例1同樣 地操作，使用所得的金屬被覆聚醯亞胺基板，按照上述“金屬被覆聚醯亞胺基板作為COF使用時的評價方法”，求出COF接合部的位置偏離的不良發生率、引線斷路發生率以及鍍錫膜脫落發生率。結果列於表1。The number of plating tanks of the continuous plating apparatus is 12 grooves, the total average current density is controlled at 1.5 A/dm 2 , and the ratio of the maximum value to the minimum value of the cathode current density in each plating tank is controlled to 3, and In the same manner as in Example 1, the obtained metal-coated polyimide substrate was used, and the "metal-coated polyimide substrate was used as a method for evaluating COF use", and the defect occurrence rate and lead of the COF joint portion were determined. The incidence of disconnection and the incidence of tin plating film shedding. The results are shown in Table 1.
上述連續電鍍裝置的電鍍槽數為6槽，總平均電流密度控制在3.0A/dm2 ，除此以外，與實施例1同樣地操作，使用所得的金屬被覆聚醯亞胺基板，按照上述“金屬被覆聚醯亞胺基板作為COF使用時的評價方法”，求出COF接合部的位置偏離的不良發生率、引線斷路發生率以及鍍錫膜脫落發生率。結果列於表1。The obtained metal-coated polyimide substrate was used in the same manner as in Example 1 except that the number of plating tanks in the continuous plating apparatus was 6 slots and the total average current density was controlled to 3.0 A/dm 2 . The metal-coated polyimide substrate was used as an evaluation method for COF use, and the occurrence rate of the COF junction portion, the occurrence rate of the lead disconnection, and the incidence rate of the tin-plated film were determined. The results are shown in Table 1.
上述連續電鍍裝置的電鍍槽數為15槽，使用不溶性陽極，總平均電流密度控制在1.5A/dm2 ，各電鍍槽內陰極電流密度的最大值對最小值之比控制在3，以及薄膜的輸送速度調節為100m/h，除此以外，與實施例1同樣地操作，使用所得的金屬被覆聚醯亞胺基板，按照上述“金屬被覆聚醯亞胺基板作為COF使用時的評價方法”，求出COF接合部的位置偏離的不良發生率、引線斷路發生率以及鍍錫膜脫落發生率。結果列於表1。另外，作為不溶性陽極，是在鈦網表面上塗敷氧化銥的陽極，在電鍍槽內與金屬覆膜和電鍍膜相對向地設置。The number of plating tanks of the above continuous plating apparatus is 15 slots, the insoluble anode is used, the total average current density is controlled at 1.5 A/dm 2 , and the ratio of the maximum value of the cathode current density to the minimum value in each plating bath is controlled at 3, and the film is In the same manner as in Example 1, except that the transport speed was adjusted to 100 m/h, the obtained metal-coated polyimide substrate was used, and the above-mentioned "metal-coated polyimide substrate was used as a method for evaluating COF use". The occurrence rate of the positional deviation of the COF joint portion, the occurrence rate of the lead wire breakage, and the incidence rate of the tin plating film fall were determined. The results are shown in Table 1. Further, as the insoluble anode, an anode coated with ruthenium oxide on the surface of the titanium mesh is provided in the plating tank so as to face the metal film and the plating film.
上述連續電鍍裝置的電鍍槽數為23槽，使用不溶性陽極，總平均電流密度控制在1.5A/dm2 ，各電鍍槽內陰極 電流密度的最大值對最小值之比控制在2，以及薄膜的輸送速度調節為150m/h，除此以外，與實施例1同樣地操作，使用所得的金屬被覆聚醯亞胺基板，按照上述“金屬被覆聚醯亞胺基板作為COF使用時的評價方法”，求出COF接合部的位置偏離的不良發生率、引線斷路發生率以及鍍錫膜脫落發生率。結果列於表1。另外，作為不溶性陽極，將在鈦網表面上塗敷氧化銥的陽極，在電鍍槽內與金屬覆膜和電鍍膜相對向地設置。The number of plating tanks of the above continuous plating apparatus is 23 slots, the insoluble anode is used, and the total average current density is controlled at 1.5 A/dm 2 , and the ratio of the maximum value of the cathode current density to the minimum value in each plating bath is controlled at 2, and the film is In the same manner as in Example 1, except that the transport speed was adjusted to 150 m/h, the obtained metal-coated polyimide substrate was used, and the above-mentioned "metal coated polyimide substrate was used as a method for evaluating COF use". The occurrence rate of the positional deviation of the COF joint portion, the occurrence rate of the lead wire breakage, and the incidence rate of the tin plating film fall were determined. The results are shown in Table 1. Further, as the insoluble anode, an anode of ruthenium oxide is coated on the surface of the titanium mesh, and is provided in the plating tank so as to face the metal film and the plating film.
上述連續電鍍裝置的電鍍槽數為8槽，使用不溶性陽極，總平均電流密度控制在3.0A/dm2 ，各電鍍槽內陰極電流密度的最大值對最小值之比控制在3，以及薄膜的輸送速度調節為100m/h，除此以外，與實施例1同樣地操作，使用所得的金屬被覆聚醯亞胺基板，按照上述“金屬被覆聚醯亞胺基板作為COF使用時的評價方法”，求出COF接合部的位置偏離的不良發生率、引線斷路發生率以及鍍錫膜脫落發生率。結果列於表1。另外，作為不溶性陽極，將在鈦網表面上塗敷氧化銥的陽極，在電鍍槽內與金屬覆膜和電鍍膜相對向地設置。The number of plating tanks of the above continuous plating apparatus is 8 tanks, the insoluble anode is used, the total average current density is controlled at 3.0 A/dm 2 , and the ratio of the maximum value of the cathode current density to the minimum value in each plating tank is controlled at 3, and the film is In the same manner as in Example 1, except that the transport speed was adjusted to 100 m/h, the obtained metal-coated polyimide substrate was used, and the above-mentioned "metal-coated polyimide substrate was used as a method for evaluating COF use". The occurrence rate of the positional deviation of the COF joint portion, the occurrence rate of the lead wire breakage, and the incidence rate of the tin plating film fall were determined. The results are shown in Table 1. Further, as the insoluble anode, an anode of ruthenium oxide is coated on the surface of the titanium mesh, and is provided in the plating tank so as to face the metal film and the plating film.
除了通過濺射形成厚度為10nm的銅層，金屬覆膜的表面電阻為1.0 Ω/□以外，與實施例1同樣地操作，使用所得的金屬被覆聚醯亞胺基板，按照上述“金屬被覆聚醯亞胺基板作為COF使用時的評價方法”，求出COF接合部的位置偏離的不良發生率、引線斷路發生率以及鍍錫膜 脫落發生率。結果列於表1。In the same manner as in Example 1, except that a copper layer having a thickness of 10 nm was formed by sputtering and the surface resistance of the metal film was 1.0 Ω/□, the obtained metal-coated polyimide substrate was used, and the above-mentioned "metal coating was carried out. The yttrium imide substrate is used as an evaluation method when COF is used, and the defect occurrence rate of the COF junction portion, the lead disconnection occurrence rate, and the tin plating film are obtained. The incidence of shedding. The results are shown in Table 1.
通過濺射形成厚度為10nm的銅層，金屬覆膜的表面電阻為1.0 Ω/□，以及上述連續電鍍裝置的電鍍槽數為6槽，總平均電流密度控制在3.0A/dm2 ，除此以外，與實施例1同樣地操作，使用所得的金屬被覆聚醯亞胺基板，按照上述“金屬被覆聚醯亞胺基板作為COF使用時的評價方法”，求出COF接合部的位置偏離的不良發生率、引線斷路發生率以及鍍錫膜脫落發生率。結果列於表1。A copper layer having a thickness of 10 nm is formed by sputtering, the surface resistance of the metal film is 1.0 Ω/□, and the number of plating tanks of the above continuous plating apparatus is 6 grooves, and the total average current density is controlled at 3.0 A/dm 2 , In the same manner as in the first embodiment, the obtained metal-coated polyimide substrate was used, and the positional deviation of the COF joint portion was determined according to the "method of evaluating the use of the metal-coated polyimide substrate as COF". Incidence, incidence of lead disconnection, and incidence of tin plating loss. The results are shown in Table 1.
通過濺射形成厚度為10nm的銅層，金屬覆膜的表面電阻為1.0 Ω/口，上述連續電鍍裝置的電鍍槽數為15槽，使用不溶性陽極，總平均電流密度控制在1.5A/dm2 ，各電鍍槽內陰極電流密度的最大值對最小值之比控制在3，以及薄膜的輸送速度調節為100m/h，除此以外，與實施例1同樣地操作，使用所得的金屬被覆聚醯亞胺基板，按照上述“金屬被覆聚醯亞胺基板作為COF使用時的評價方法”，求出COF接合部的位置偏離的不良發生率、引線斷路發生率以及鍍錫膜脫落發生率。結果列於表1。另外，作為不溶性陽極，將在鈦網表面上塗敷氧化銥的陽極，在電鍍槽內與金屬覆膜和電鍍膜相對向地設置。A copper layer having a thickness of 10 nm was formed by sputtering, the surface resistance of the metal film was 1.0 Ω/□, the number of plating tanks of the above continuous plating apparatus was 15 grooves, and the total average current density was controlled at 1.5 A/dm 2 using an insoluble anode. The obtained metal coated polyfluorene was used in the same manner as in Example 1 except that the ratio of the maximum value to the minimum value of the cathode current density in each plating bath was controlled to 3, and the transport speed of the film was adjusted to 100 m/h. The imine substrate was subjected to the above-described "method for evaluating the use of a metal-coated polyimide substrate as a COF" to determine a defect occurrence rate of a positional deviation of a COF joint portion, a lead wire breakage rate, and a tin plating film peeling occurrence rate. The results are shown in Table 1. Further, as the insoluble anode, an anode of ruthenium oxide is coated on the surface of the titanium mesh, and is provided in the plating tank so as to face the metal film and the plating film.
通過濺射形成厚度為10nm的銅層，金屬覆膜的表面電阻為1.0 Ω/□，上述連續電鍍裝置的電鍍槽數為8槽，使用不溶性陽極，總平均電流密度控制在3.0A/dm2 ，各 電鍍槽內陰極電流密度的最大值對最小值之比控制在3，以及薄膜的輸送速度調節為100m/h，除此以外，與實施例1同樣地操作，使用所得的金屬被覆聚醯亞胺基板，按照上述“金屬被覆聚醯亞胺基板作為COF使用時的評價方法”，求出COF接合部的位置偏離的不良發生率、引線斷路發生率以及鍍錫膜脫落發生率。結果列於表1。另外，作為不溶性陽極，將在鈦網表面上塗敷氧化銥的陽極，在電鍍槽內與金屬覆膜和電鍍膜相對向地設置。A copper layer having a thickness of 10 nm was formed by sputtering, the surface resistance of the metal film was 1.0 Ω/□, the number of plating tanks of the above continuous plating apparatus was 8 grooves, and the total average current density was controlled at 3.0 A/dm 2 using an insoluble anode. The obtained metal coated polyfluorene was used in the same manner as in Example 1 except that the ratio of the maximum value to the minimum value of the cathode current density in each plating bath was controlled to 3, and the transport speed of the film was adjusted to 100 m/h. The imine substrate was subjected to the above-described "method for evaluating the use of a metal-coated polyimide substrate as a COF" to determine a defect occurrence rate of a positional deviation of a COF joint portion, a lead wire breakage rate, and a tin plating film peeling occurrence rate. The results are shown in Table 1. Further, as the insoluble anode, an anode of ruthenium oxide is coated on the surface of the titanium mesh, and is provided in the plating tank so as to face the metal film and the plating film.
除了通過濺射形成厚度為1000nm的銅層，金屬覆膜的表面電阻為0.09 Ω/□以外，與實施例1同樣地操作，使用所得的金屬被覆聚醯亞胺基板，按照上述“金屬被覆聚醯亞胺基板作為COF使用時的評價方法”，求出COF接合部的位置偏離的不良發生率、引線斷路發生率以及鍍錫膜脫落發生率。結果列於表1。In the same manner as in Example 1, except that a copper layer having a thickness of 1000 nm was formed by sputtering and the surface resistance of the metal film was 0.09 Ω/□, the obtained metal-coated polyimide substrate was used, and the above-mentioned "metal coating was carried out. The yttrium imide substrate was used as an evaluation method in the case of using COF, and the occurrence rate of the positional deviation of the COF joint portion, the occurrence rate of the lead wire breakage, and the incidence rate of the tin plating film were determined. The results are shown in Table 1.
除了通過濺射形成厚度為5nm的銅層，金屬覆膜的表面電阻為1.1 Ω/□以外，與實施例1同樣地操作，使用所得的金屬被覆聚醯亞胺基板，按照上述“金屬被覆聚醯亞胺基板作為COF使用時的評價方法”，求出COF接合部的位置偏離的不良發生率、引線斷路發生率以及鍍錫膜脫落發生率。結果列於表1。In the same manner as in Example 1, except that a copper layer having a thickness of 5 nm was formed by sputtering and the surface resistance of the metal film was 1.1 Ω/□, the obtained metal-coated polyimide substrate was used, and the above-mentioned "metal coating was carried out. The yttrium imide substrate was used as an evaluation method in the case of using COF, and the occurrence rate of the positional deviation of the COF joint portion, the occurrence rate of the lead wire breakage, and the incidence rate of the tin plating film were determined. The results are shown in Table 1.
上述連續電鍍裝置的電鍍槽數為20槽，總平均電流密度控制在0.9A/dm2 ，除此以外，與實施例1同樣地操作， 使用所得的金屬被覆聚醯亞胺基板，按照上述“金屬被覆聚醯亞胺基板作為COF使用時的評價方法”，求出COF接合部的位置偏離的不良發生率、引線斷路發生率以及鍍錫膜脫落發生率。結果列於表1。The obtained metal-coated polyimide substrate was used in the same manner as in Example 1 except that the number of plating tanks in the continuous plating apparatus was 20 grooves and the total average current density was controlled to 0.9 A/dm 2 . The metal-coated polyimide substrate was used as an evaluation method for COF use, and the occurrence rate of the COF junction portion, the occurrence rate of the lead disconnection, and the incidence rate of the tin-plated film were determined. The results are shown in Table 1.
上述連續電鍍裝置的電鍍槽數為5槽，總平均電流密度控制在3.5A/dm2 ，除此以外，與實施例1同樣地操作，使用所得的金屬被覆聚醯亞胺基板，按照上述“金屬被覆聚醯亞胺基板作為COF使用時的評價方法”，求出COF接合部的位置偏離的不良發生率、引線斷路發生率以及鍍錫膜脫落發生率。結果列於表1。The obtained metal-coated polyimide substrate was used in the same manner as in Example 1 except that the number of plating tanks in the continuous plating apparatus was 5 slots and the total average current density was controlled to 3.5 A/dm 2 . The metal-coated polyimide substrate was used as an evaluation method for COF use, and the occurrence rate of the COF junction portion, the occurrence rate of the lead disconnection, and the incidence rate of the tin-plated film were determined. The results are shown in Table 1.
除了各電鍍槽內陰極電流密度的最大值對最小值之比控制在6以外，與實施例1同樣地操作，使用所得的金屬被覆聚醯亞胺基板，按照上述“金屬被覆聚醯亞胺基板作為COF使用時的評價方法”，求出COF接合部的位置偏離的不良發生率、引線斷路發生率以及鍍錫膜脫落發生率。結果列於表1。The obtained metal-coated polyimide substrate was used in the same manner as in Example 1 except that the ratio of the maximum value to the minimum value of the cathode current density in each plating bath was controlled to be 6, in accordance with the above-mentioned "metal-coated polyimide substrate". As an evaluation method at the time of use of COF, the occurrence rate of the positional deviation of the COF joint portion, the occurrence rate of the lead wire breakage, and the incidence rate of the tin plating film were determined. The results are shown in Table 1.
除了上述連續電鍍裝置的電鍍槽數為16槽，薄膜的輸送速度調節為70m/h以外，與實施例1同樣地操作，使用所得的金屬被覆聚醯亞胺基板，按照上述“金屬被覆聚醯亞胺基板作為COF使用時的評價方法”，求出COF接合部的位置偏離的不良發生率、引線斷路發生率以及鍍錫膜脫落發生率。結果列於表1。The obtained metal-coated polyimide substrate was used in the same manner as in Example 1 except that the number of plating tanks of the continuous plating apparatus was 16 grooves and the conveying speed of the film was adjusted to 70 m/h, and the above-mentioned "metal-coated polyimide" was used. The imide substrate was used as an evaluation method in the case of using COF, and the occurrence rate of the positional deviation of the COF joint portion, the occurrence rate of the lead wire breakage, and the incidence rate of the tin plating film were determined. The results are shown in Table 1.
由表1可知，在實施例1~11中，在濺射步驟中，形成的金屬覆膜的表面電阻被控制在0.1~1.0 Ω/□，在電鍍步驟中，對於陰極電流密度，全部電鍍槽的平均陰極電流密度被控制在1~3A/dm2 ，以及各電鍍槽內陰極電流密度的最大值對最小值之比被控制在1~5，同時薄膜的輸送速度被調節為80~300m/h，由於照本發明的製造方法製造金屬被覆聚醯亞胺基板，COF接合部位置偏離的不良發生率、引線斷路發生率以及鍍錫膜脫落發生率均低於0.01%，可判斷為良好。As can be seen from Table 1, in Examples 1 to 11, in the sputtering step, the surface resistance of the formed metal film was controlled to be 0.1 to 1.0 Ω/□, and in the plating step, all the plating tanks were used for the cathode current density. The average cathode current density is controlled at 1~3A/dm 2 , and the ratio of the maximum value to the minimum value of the cathode current density in each plating bath is controlled to 1~5, and the conveying speed of the film is adjusted to 80~300m/ h, the metal-coated polyimide substrate was produced by the production method of the present invention, and the occurrence rate of the COF joint portion deviation, the occurrence rate of the lead wire breakage, and the occurrence rate of the tin-plated film peeling were all less than 0.01%, and it was judged to be good.
相比之下，在比較例1~6中，由於金屬覆膜的表面電阻、全部電鍍槽的平均陰極電流密度、各電鍍槽內陰極電流密度的最大值對最小值之比或者薄膜的輸送速度總有一項不滿足這些條件，因此COF接合部位置偏離的不良發生率、引線斷路發生率或者鍍錫膜脫落發生率總有一項為0.01%以上，在這些條件下得到的金屬被覆聚醯亞胺基板在生產性、產率和可靠性方面還不能說足夠好。In contrast, in Comparative Examples 1 to 6, the surface resistance of the metal film, the average cathode current density of all the plating baths, the ratio of the maximum value to the minimum value of the cathode current density in each plating bath, or the transport speed of the film. There is always one that does not satisfy these conditions. Therefore, there is always a defect rate of occurrence of the positional deviation of the COF joint portion, the incidence of lead disconnection, or the incidence of tin plating film shedding is 0.01% or more. Under these conditions, the metal is coated with polyimide. The substrate cannot be said to be sufficiently good in terms of productivity, productivity and reliability.
由以上內容可知，由本發明製造方法製得的金屬被覆聚醯亞胺基板適合用於以內引線為20 μm節距、外引線為35 μm節距為代表的細距COF。這樣，在IC與液晶面板的組裝步驟中內引線部與IC晶片、以及外引線部與液晶面板的接合時的脫落等問題、引線斷路等問題、以及鍍錫膜脫落等發生的可能性可以得到充分的抑制。並且，本發明的製造方法，由於還可以預期電鍍生產性的提高，因此在生產性和經濟性方面也是有效的。根據本發明製得的金屬 被覆聚醯亞胺基板，除了COF以外，還可以適用於PWB、FPC、TAB等撓性線路板中。From the above, it is understood that the metal-coated polyimide substrate obtained by the production method of the present invention is suitably used for a fine pitch COF represented by a pitch of 20 μm for inner leads and a pitch of 35 μm for outer leads. As described above, in the assembly process of the IC and the liquid crystal panel, problems such as dropping of the inner lead portion and the IC chip, and bonding of the outer lead portion and the liquid crystal panel, problems such as disconnection of the lead, and occurrence of dropping of the tin plating film can be obtained. Full inhibition. Further, the production method of the present invention is also effective in terms of productivity and economy since it is also expected to improve the productivity of electroplating. Metal made according to the invention The coated polyimide substrate can be applied to flexible wiring boards such as PWB, FPC, and TAB in addition to COF.
1‧‧‧電鍍槽1‧‧‧ plating bath
2‧‧‧薄膜2‧‧‧film
3‧‧‧供電輥3‧‧‧Power supply roller
4‧‧‧反轉輥4‧‧‧Reverse roll
5‧‧‧陽極5‧‧‧Anode
第1圖表示本發明金屬被覆聚醯亞胺基板之製法中所用的連續電鍍裝置簡略結構的一個實例的圖，Fig. 1 is a view showing an example of a schematic configuration of a continuous plating apparatus used in the method for producing a metal-coated polyimide substrate of the present invention.
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| CN102021576B (en) | 2010-09-30 | 2012-06-27 | 深圳市信诺泰创业投资企业(普通合伙) | Method for continuously producing flexible copper clad laminates |
| CN102477549B (en) * | 2010-11-25 | 2014-04-16 | 中国电子科技集团公司第十八研究所 | Method for depositing semiconductor film on flexible substrate |
| CN102477550B (en) * | 2010-11-25 | 2014-04-16 | 中国电子科技集团公司第十八研究所 | Device for depositing semiconductor film on flexible substrate |
| JP5858286B2 (en) * | 2012-01-11 | 2016-02-10 | 住友金属鉱山株式会社 | Method for electrolytic plating long conductive substrate and method for producing copper clad laminate |
| CN104247576B (en) * | 2012-04-24 | 2017-05-31 | 住友金属矿山株式会社 | 2 layers of flexible wiring substrate and flexible wiring and its manufacture method |
| CN104216149B (en) * | 2014-09-30 | 2017-03-22 | 南京中电熊猫液晶显示科技有限公司 | Liquid crystal display panel with repair wire structure |
| WO2016208609A1 (en) * | 2015-06-26 | 2016-12-29 | 住友金属鉱山株式会社 | Conductive substrate |
| JP6880723B2 (en) | 2016-12-27 | 2021-06-02 | 住友金属鉱山株式会社 | Double-sided metal laminate, double-sided metal laminate manufacturing method, and pattern image transfer method |
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