TWI519412B - Flexible copper-clad lamination board - Google Patents
Flexible copper-clad lamination board Download PDFInfo
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- TWI519412B TWI519412B TW098108377A TW98108377A TWI519412B TW I519412 B TWI519412 B TW I519412B TW 098108377 A TW098108377 A TW 098108377A TW 98108377 A TW98108377 A TW 98108377A TW I519412 B TWI519412 B TW I519412B
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- clad laminate
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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
- B32B15/088—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin comprising polyamides
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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
- B32B15/20—Layered products comprising a layer of metal comprising aluminium or copper
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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
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/34—Layered products comprising a layer of synthetic resin comprising polyamides
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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
- B32B2307/00—Properties of the layers or laminate
- B32B2307/30—Properties of the layers or laminate having particular thermal properties
- B32B2307/306—Resistant to heat
- B32B2307/3065—Flame resistant or retardant, fire resistant or retardant
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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
- B32B2311/00—Metals, their alloys or their compounds
- B32B2311/12—Copper
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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
- B32B2311/00—Metals, their alloys or their compounds
- B32B2311/22—Nickel or cobalt
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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
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- Laminated Bodies (AREA)
- Parts Printed On Printed Circuit Boards (AREA)
Description
本發明係有關由聚醯亞胺樹脂組成之絕緣層與於其單面或雙面設置有銅箔之可撓性覆銅積層板。The present invention relates to an insulating layer composed of a polyimide resin and a flexible copper clad laminate provided with a copper foil on one or both sides thereof.
近年來，隨著行動電話或數位相機、數位攝影機、PDA、汽車導航器、硬碟等其他各種電子裝置之高機能化、小型化及輕量化，採用線路自由度高且薄型化容易的可撓性印刷基板，取代至今做為此等電子線路用基板材料使用之剛性基板之例子正在增加。而且，關於逐漸更高度化之此等裝置所使用之可撓性印刷基板，正增加更小型高密度化、多層化、細小化、高耐熱化等之需求。In recent years, with the high functionality, miniaturization, and weight reduction of various other electronic devices such as mobile phones, digital cameras, digital cameras, PDAs, car navigators, and hard disks, it is easy to use a line with high degree of freedom and thinness. The printed circuit board is increasing as an example of a rigid substrate used for the substrate material for electronic circuits. Further, there is a demand for a compact printed circuit board which is used for such a device which is gradually increased in size, such as a smaller size, a higher density, a higher thickness, a smaller size, and a higher heat resistance.
為了因應如此之要求，於專利文獻1等中，揭示一種於導體上直接塗佈形成聚醯亞胺樹脂層，且以熱膨脹係數不同之複數個聚醯亞胺樹脂層進行多層化而形成，藉此提供對於溫度變化之尺寸安定性、接著力，以及蝕刻後之平坦化等的信賴性優良之可撓性印刷基板。In order to cope with such a request, Patent Document 1 and the like disclose that a polyimine resin layer is directly coated on a conductor and formed by multilayering a plurality of polyimine resin layers having different thermal expansion coefficients. This provides a flexible printed circuit board having excellent dimensional stability, adhesion, and flatness after etching, and the like.
在如此之不具有可撓性印刷基板中所使用之接著劑層之覆銅積層板中，例如：如專利文獻2、專利文獻3、專利文獻4等，為了提高與樹脂層之接著力，而使用銅箔表面經粗糙化處理之銅箔。In the copper-clad laminate which does not have the adhesive layer used in the flexible printed circuit board, for example, as disclosed in Patent Document 2, Patent Document 3, and Patent Document 4, in order to improve the adhesion to the resin layer, A copper foil having a roughened copper surface is used.
然而，近年來，在進行電路的精細化之時，於電路加工後之電路端部和聚醯亞胺上易出現殘渣，而有必要去除殘渣。此外，在做為電路加工之電鍍步驟等中之銅箔表面之前處理步驟上須有電路表面的清洗。為了此目的，除了進行銅箔表面之酸清洗以外，也藉由以過氧化氫/硫酸等溶解銅之藥液做為主成分之化學研磨液進行研磨銅箔表面之步驟。然而，由於在使用上述之經粗糙化處理之銅箔所製成之覆銅積層板中，特別是在對此覆銅積層板進行電路加工後所得之可撓性印刷基板中，若實施此化學研磨，則化學研磨液會滲入電路之邊緣部分，而易造成電路之剝離強度降低，並且若進行電路線路之精細化，則會因電路剝離造成電路浮起並導致斷線，故必須改善。However, in recent years, at the time of refinement of the circuit, residues are liable to occur on the end portions of the circuit after the circuit processing and the polyimide, and it is necessary to remove the residue. In addition, the cleaning of the circuit surface is required in the processing steps before the surface of the copper foil in the electroplating step or the like of the circuit processing. For this purpose, in addition to the acid cleaning of the surface of the copper foil, the surface of the copper foil is polished by a chemical polishing liquid containing copper chemical solution such as hydrogen peroxide/sulfuric acid as a main component. However, in the copper clad laminate produced by using the above-mentioned roughened copper foil, particularly in the flexible printed circuit board obtained by performing circuit processing on the copper clad laminate, if the chemistry is carried out When the polishing is performed, the chemical polishing liquid penetrates into the edge portion of the circuit, and the peeling strength of the circuit is liable to be lowered, and if the circuit is refined, the circuit is lifted due to the peeling of the circuit and the wire is broken, so it is necessary to be improved.
[專利文獻1]日本特公平6-93537號公報[Patent Document 1] Japanese Patent Publication No. 6-93537
[專利文獻2]日本特開平2-292894號公報[Patent Document 2] Japanese Patent Laid-Open No. 2-292894
[專利文獻3]日本特開平6-169168號公報[Patent Document 3] Japanese Patent Laid-Open No. 6-169168
[專利文獻4]日本特開平8-335775號公報[Patent Document 4] Japanese Patent Laid-Open No. Hei 8-335775
本發明係提供一種耐熱性和尺寸安定性等優良、可對應於在電子機器類之領域中近年來急速進展之高積體化和高密度化之要求，且藉由提高銅箔與聚醯亞胺樹脂層間之接著可靠性而抑制化學研磨時之電路剝離之方法者。The present invention provides an excellent heat resistance, dimensional stability, and the like, and can meet the requirements of high integration and high density in recent years in the field of electronic equipment, and by improving copper foil and polyaluminum. A method of suppressing circuit peeling during chemical polishing by the subsequent reliability between the amine resin layers.
為了解決上述課題而致力研究後結果發現，將與聚醯亞胺樹脂層相接之銅箔之表面特性控制在特定範圍，即可提高銅箔與聚醯亞胺樹脂層間之接著可靠性，遂完成本發明。In order to solve the above problems, it has been found that the surface properties of the copper foil which is in contact with the polyimide layer are controlled to a specific range, and the subsequent reliability between the copper foil and the polyimide layer can be improved. The present invention has been completed.
換言之，本發明提供一種可撓性覆銅積層板，係於聚醯亞胺樹脂層之單面或雙面積層有銅箔之覆銅積層板，其中，前述銅箔之與聚醯亞胺樹脂層相接之銅箔表面係具有由包含矽烷耦合劑處理層之複數個處理層組成之表面處理層，此表面處理層係含有銅、鈷、鎳及鋅，鎳/(鎳+鈷+鋅)比為0.23以上(依ICP-AES(Inductively Coupled Plasma-Atomic Emission Spectroscopy，感應耦合電漿-原子發光光譜法)測定而得)，且鋅含量在0.2至0.6mg/dm2 之範圍，前述矽烷耦合劑處理層係由具有胺基之矽烷耦合劑所形成者。In other words, the present invention provides a flexible copper-clad laminate which is a copper-clad laminate having a single-sided or double-area layer of a polyimide foil, wherein the copper foil and the polyimide resin are The surface of the copper foil which is in contact with the layer has a surface treatment layer composed of a plurality of treatment layers comprising a layer treated with a decane coupling agent, the surface treatment layer containing copper, cobalt, nickel and zinc, nickel / (nickel + cobalt + zinc) The ratio is 0.23 or more (determined by ICP-AES (Inductively Coupled Plasma-Atomic Emission Spectroscopy), and the zinc content is in the range of 0.2 to 0.6 mg/dm 2 , the aforementioned decane coupling The agent treatment layer is formed of a decane coupling agent having an amine group.
以下表示本發明之可撓性覆銅積層板之較佳態樣。The preferred aspect of the flexible copper clad laminate of the present invention is shown below.
1)表面處理層中之矽烷耦合劑處理層係位於最外層者。1) The decane couplant treatment layer in the surface treatment layer is located at the outermost layer.
2)前述聚醯亞胺樹脂層係由複數層組成，與銅箔相接之聚醯亞胺樹脂層(A)係由熱塑性聚醯亞胺樹脂組成。2) The polyimine resin layer is composed of a plurality of layers, and the polyimide layer (A) which is in contact with the copper foil is composed of a thermoplastic polyimide resin.
3)銅箔係輥軋銅箔(亦稱壓延銅箔；rolled copper foil)，與聚醯亞胺樹脂層相接之經表面處理之銅箔表面之表面粗糙度(Rz)係在0.5至2μm之範圍。3) Copper foil rolled copper foil (also known as rolled copper foil), the surface roughness (Rz) of the surface treated copper foil which is in contact with the polyimide layer is 0.5 to 2 μm. The scope.
4)在聚醯亞胺樹脂層與銅箔之1mm寬度之初期接著力係0.6kN/m以上。4) The initial adhesion force of the polyimide film layer and the copper foil at a width of 1 mm is 0.6 kN/m or more.
本發明之覆銅積層板係樹脂層與銅箔之接著強度、耐熱性、阻燃性及尺寸安定性等優良，且精細電路加工性優良並且不會發生因化學研磨造成之剝離等不良情形。因此，作為可撓性印刷基板使用於電器、電子零件時，可適用於可靠性優良，特別是要求精細線路之用途。The copper clad laminate resin layer of the present invention and the copper foil are excellent in adhesion strength, heat resistance, flame retardancy, dimensional stability, and the like, and are excellent in fine circuit processability, and do not cause peeling due to chemical polishing. Therefore, when it is used for an electric or electronic component as a flexible printed circuit board, it is applicable to the reliability, and it is especially the use of a fine circuit.
以下，詳細說明本發明。Hereinafter, the present invention will be described in detail.
本發明之可撓性覆銅積層板係由做為絕緣層之聚醯亞胺樹脂層(也稱為絕緣層)與銅箔組成。銅箔可使用例如依輥軋銅箔、電解銅箔等習知之製造方法所得者。銅箔較佳的厚度範圍為6至35μm，且以9至18μm之範圍更佳。若銅箔之厚度未達6μm，則在如大量生產覆銅積層板時之生產線之製造步驟中，惟恐有難以調整張力等之情形，反之，如超過35μm，則覆銅積層板之彎曲性變差。The flexible copper clad laminate of the present invention is composed of a polyimide film (also referred to as an insulating layer) as an insulating layer and a copper foil. As the copper foil, for example, a conventional production method such as a rolled copper foil or an electrolytic copper foil can be used. The copper foil preferably has a thickness in the range of 6 to 35 μm and more preferably in the range of 9 to 18 μm. If the thickness of the copper foil is less than 6 μm, it is difficult to adjust the tension or the like in the manufacturing steps of the production line such as mass production of the copper clad laminate. On the contrary, if it exceeds 35 μm, the bendability of the copper clad laminate becomes difference.
為了提高與做為絕緣層之聚醯亞胺樹脂層間之密著力，所使用之銅箔係具有由包含矽烷耦合劑處理層之複數個處理層組成之表面處理層。除了矽烷耦合劑處理層以外，處理層以包含糙化處理層為佳。In order to increase the adhesion to the polyimide layer of the insulating layer, the copper foil used has a surface treatment layer composed of a plurality of processing layers including a decane coupling agent treatment layer. In addition to the decane couplant treatment layer, the treatment layer preferably comprises a roughened layer.
用以形成粗糙化處理層之粗糙化處理之程度以表面粗糙度(Rz)在0.5至2μm之範圍為佳、以0.5至1μm之範圍更佳。再此，所謂表面粗糙度(Rz)，係指由JIS B0601(1994)所定義之10點平均粗糙度。此粗糙化處理係使金屬粒子(粗糙化粒子)附著於銅箔表面等而提高表面粗糙度。藉此，在絕緣層與銅箔間可產生定錨效應(anchor effect)而提高密著力。若上述表面粗糙度(Rz)未達0.5μm，則無法期待對絕緣層之定錨效應，而密著力低落。此外，若表面粗糙度(Rz)超過2μm，則粗糙化粒子在電路加工中之蝕刻時未去除，而惟恐有做為蝕刻殘留物而存在於電路端部或絕緣層上之情形。而且，此蝕刻殘留物在精細加工時有導致電路間之所謂短路或遷移(migration)之銅洗提等不良情形之可能性。The degree of roughening treatment for forming the roughened layer is preferably in the range of 0.5 to 2 μm in the surface roughness (Rz) and more preferably in the range of 0.5 to 1 μm. Here, the surface roughness (Rz) means a 10-point average roughness defined by JIS B0601 (1994). This roughening treatment causes the metal particles (roughened particles) to adhere to the surface of the copper foil or the like to improve the surface roughness. Thereby, an anchor effect can be generated between the insulating layer and the copper foil to improve the adhesion. If the surface roughness (Rz) is less than 0.5 μm, the anchoring effect on the insulating layer cannot be expected, and the adhesion is low. Further, if the surface roughness (Rz) exceeds 2 μm, the roughened particles are not removed during the etching in the circuit processing, and there is a fear that they are present on the circuit end or the insulating layer as an etching residue. Moreover, this etching residue has a possibility of causing a problem such as so-called short circuit or migration of copper between circuits during fine processing.
在此粗糙化處理中所使用之粗糙化粒子可單獨使用銅、或使用銅+鎳或銅+鈷+鎳等合金。此外，使粗糙化粒子附著後也可進一步藉由銅、鎳或鎳+鈷進行處理。惟，由於電路加工性優良，不會因化學研磨而發生剝離，此粗糙化處理層整個必須為銅、鎳、鈷。當在粗糙化處理中僅使用銅時，則易氧化且易造成變色等。此外，若使用銅及鎳或僅使用鎳，則雖對於化學研磨之耐性增強，但不易溶於電路加工時所使用之銅電鍍液，而惟恐有易產生蝕刻殘留物之情形。若使用銅及鈷或僅使用鈷，則耐酸性惡化，而在化學研磨時有易發生電路剝離之可能性。The roughened particles used in the roughening treatment may be copper alone or an alloy such as copper + nickel or copper + cobalt + nickel. Further, after the roughened particles are attached, they may be further treated with copper, nickel or nickel + cobalt. However, since the circuit processability is excellent, peeling does not occur due to chemical polishing, and the roughened layer must be entirely made of copper, nickel, or cobalt. When only copper is used in the roughening treatment, it is easily oxidized and easily causes discoloration or the like. Further, when copper or nickel or nickel alone is used, the chemical polishing resistance is enhanced, but it is not easily dissolved in the copper plating solution used in the circuit processing, and there is a fear that etching residues are likely to occur. When copper or cobalt is used or only cobalt is used, acid resistance is deteriorated, and there is a possibility that circuit peeling is likely to occur during chemical polishing.
在本發明中所使用之銅箔係在表面處理層中(較佳為在上述粗糙化處理層中或在粗糙化處理層上)含有鋅0.2至0.6mg/dm2 。當將含有鋅之層設置於粗糙化處理層上時，可藉由析出處理而形成層。在本發明中，可一面藉由此鋅處理抑制銅氧化，一面抑制因化學研磨造成之電路剝離。若鋅之含量未達0.2mg/dm2 ，則因氧化造成之電路變色或氧化而造成銅箔脆化，而易導致電路斷線。此外，由於若鋅之含量超過0.6mg/dm2 ，則鋅本身不耐酸，而易發生因化學研磨造成之電路剝離，並且易發生斷線。同時，關於上述析出處理，只要為電解電鍍等可在銅箔之表面使上述之金屬以預定量析出之手段，則無特別限制。The copper foil used in the present invention contains 0.2 to 0.6 mg/dm 2 of zinc in the surface treatment layer (preferably in the above roughening treatment layer or on the roughened layer). When the layer containing zinc is provided on the roughened layer, the layer can be formed by a precipitation treatment. In the present invention, it is possible to suppress the peeling of the circuit by chemical polishing while suppressing the oxidation of copper by the zinc treatment. If the content of zinc is less than 0.2 mg/dm 2 , the copper foil is embrittled due to discoloration or oxidation of the circuit caused by oxidation, which may easily cause the circuit to be broken. Further, if the content of zinc exceeds 0.6 mg/dm 2 , the zinc itself is not resistant to acid, and the peeling of the circuit due to chemical polishing is liable to occur, and disconnection is liable to occur. Meanwhile, the precipitation treatment is not particularly limited as long as it is a means for depositing the above-described metal in a predetermined amount on the surface of the copper foil by electrolytic plating or the like.
為了更提高與絕緣層之密著力，在本發明中所使用之銅箔係具有由具有胺基之矽烷耦合劑所形成之矽烷耦合劑處理層。此矽烷耦合劑處理層以存在於表面處理層之最外層為佳。具有胺基之矽烷耦合劑可舉例如：N-2-(胺基乙基)γ-胺基丙基三甲氧基矽烷、N-3-(4-(3-胺基丙氧基)丁氧基)丙基-3-胺基丙基三甲氧基矽烷、N-苯基-3-胺丙基三甲氧基矽烷等。此等矽烷耦合劑可單獨使用、或組合2種以上使用，當使用複數種時，只要含有1種以上具有胺基之矽烷耦合劑即可。此外，在進行矽烷耦合劑處理前，為了更顯露與絕緣層間之密著力之目的，也可進行鉻酸鹽處理。In order to further improve the adhesion to the insulating layer, the copper foil used in the present invention has a decane coupling agent treatment layer formed of a decane coupling agent having an amine group. This decane couplant treatment layer is preferably present at the outermost layer of the surface treatment layer. The decane coupling agent having an amine group may, for example, be N-2-(aminoethyl)γ-aminopropyltrimethoxydecane or N-3-(4-(3-aminopropoxy)butoxy Phenyl-3-aminopropyltrimethoxydecane, N-phenyl-3-aminopropyltrimethoxydecane, and the like. These decane coupling agents may be used singly or in combination of two or more. When a plurality of kinds are used, one or more decane coupling agents having an amine group may be contained. Further, chromate treatment may be performed for the purpose of further revealing the adhesion to the insulating layer before the decane coupling agent treatment.
矽烷耦合劑處理方法可例示如：當使用上述耦合劑時，首先，於做為溶劑之水中使預定量之耦合劑溶解後，塗佈於上述之金屬析出處理後之銅箔表面上並使其乾燥之方法。此時，依需要，也可進行加熱處理。此外，對於銅箔表面塗佈溶於水中之耦合劑之方法，可使用例如：浸漬法、噴淋法、噴霧法等習知方法。The decane coupling agent treatment method is exemplified by, for example, when the above-mentioned coupling agent is used, first, a predetermined amount of the coupling agent is dissolved in water as a solvent, and then applied to the surface of the copper foil after the metal precipitation treatment described above, and The method of drying. At this time, heat treatment may be performed as needed. Further, as a method of applying a coupling agent dissolved in water to the surface of the copper foil, a conventional method such as a dipping method, a shower method, or a spray method can be used.
經由上述處理，整個銅箔之表面處理層係含有銅、鈷、鎳及鋅。而且，必須令鎳/(鎳+鈷+鋅)比為0.23以上，且以在0.24至0.3之範圍為佳。若鎳/(鎳+鈷+鋅)比未達0.23，則在化學研磨時在電路端部容易發生電路剝離。在此，銅、鈷、鎳及鋅之測定係依ICP-AES測定而得者，並以記載於實施例之條件進行測定。Through the above treatment, the surface treatment layer of the entire copper foil contains copper, cobalt, nickel, and zinc. Further, the ratio of nickel/(nickel + cobalt + zinc) must be 0.23 or more, and preferably in the range of 0.24 to 0.3. If the ratio of nickel/(nickel+cobalt+zinc) is less than 0.23, circuit peeling tends to occur at the end of the circuit during chemical polishing. Here, the measurement of copper, cobalt, nickel, and zinc is carried out by ICP-AES measurement, and the measurement is carried out under the conditions described in the examples.
於設置有如上述之表面處理層之銅箔之表面處理層之面上積層做為絕緣層之聚醯亞胺樹脂層。構成此聚醯亞胺樹脂層之聚醯亞胺樹脂一般係下述式(1)所示，可使用實質上等莫耳之二胺成分與酸二酐成分，並依在有機極性溶劑中進行聚合之習知方法製造。A polyimide layer of a polyimide resin layer as an insulating layer is laminated on the surface of the surface treatment layer provided with the copper foil of the surface treatment layer as described above. The polyimine resin constituting the polyimide resin layer is generally represented by the following formula (1), and substantially a molar component such as a diamine component and an acid dianhydride component can be used, and the organic polar solvent can be used. Manufacturing by conventional methods of polymerization.
在通式(1)中，Ar1 係具有1個以上芳香族環之4價有機基，Ar2 係具有1個以上芳香族環之2價有機基。而且，Ar1 係酸二酐之殘基，Ar2 係二胺之殘基。In the general formula (1), Ar 1 has a tetravalent organic group having one or more aromatic rings, and Ar 2 has a divalent organic group having one or more aromatic rings. Further, the residue of Ar 1 is an acid dianhydride and the residue of an Ar 2 -based diamine.
酸二酐可舉例如：由O(CO)2 -Ar1 -(CO)2 O所表示之芳香族酸二酐。較佳的Ar1 可例示如：下述所示之4價有機基。The acid dianhydride may, for example, be an aromatic acid dianhydride represented by O(CO) 2 -Ar 1 -(CO) 2 O. Desirable Ar 1 is exemplified by a tetravalent organic group shown below.
酸二酐可單獨或混合2種以上使用。此等之中尤以使用從均苯四甲酸二酐(PMDA)、3,3’,4,4’-聯苯四甲酸二酐(BPDA)、3,3’,4,4’-二苯甲酮四甲酸二酐(BTDA)、3,3’,4,4’-二苯基碸四甲酸二酐(DSDA)、4,4’-氧二酞酸二酐(ODPA)之中選出者為佳。The acid dianhydride may be used alone or in combination of two or more. Among them, pyromellitic dianhydride (PMDA), 3,3',4,4'-biphenyltetracarboxylic dianhydride (BPDA), 3,3',4,4'-diphenyl are especially used. Among the ketone tetracarboxylic dianhydride (BTDA), 3,3',4,4'-diphenylphosphonium tetracarboxylic dianhydride (DSDA), 4,4'-oxydiphthalic acid dianhydride (ODPA) It is better.
二胺可舉例如：由H2 N-Ar2 -NH2 所表示之芳香族二胺。較佳的Ar2 可例示如：下述所示之2價有機基。The diamine may, for example, be an aromatic diamine represented by H 2 N-Ar 2 —NH 2 . Desirable Ar 2 is exemplified by a divalent organic group shown below.
此等二胺中，較佳者可例示如：二胺基二苯基醚(DAPE)、2,2’-二甲基-4,4’-二胺基聯苯(以下稱為m-TB)、對苯二胺(p-PDA)、1,3-雙(4-胺基苯氧基)苯(TPE-R)、1,3-雙(3-胺基苯氧基)苯(APB)、1,4-雙(4-胺基苯氧基)苯(TPE-Q)、2,2-雙(4-(4-胺基苯氧基)苯基]丙烷(BAPP)。Among these diamines, preferred are, for example, diaminodiphenyl ether (DAPE) and 2,2'-dimethyl-4,4'-diaminobiphenyl (hereinafter referred to as m-TB). ), p-phenylenediamine (p-PDA), 1,3-bis(4-aminophenoxy)benzene (TPE-R), 1,3-bis(3-aminophenoxy)benzene (APB) ), 1,4-bis(4-aminophenoxy)benzene (TPE-Q), 2,2-bis(4-(4-aminophenoxy)phenyl]propane (BAPP).
關於使用於聚合之溶劑，可舉例如：二甲基乙醯胺、N-甲基吡咯啶酮、2-丁酮、二乙二醇二甲醚、二甲苯等，關於此等，可使用1種或併用2種以上。此外，關於聚合所得之聚醯胺酸(聚醯亞胺前驅物)之樹脂黏度，以500cps至35000cps之範圍為佳。Examples of the solvent used for the polymerization include dimethylacetamide, N-methylpyrrolidone, 2-butanone, diethylene glycol dimethyl ether, and xylene. For these, 1 can be used. Two or more kinds are used in combination or in combination. Further, the resin viscosity of the polylysine (polyimine precursor) obtained by the polymerization is preferably in the range of 500 cps to 35,000 cps.
本發明之可撓性覆銅積層板之聚醯亞胺樹脂層可為由單層組成者或由複數層組成者，為了使可撓性覆銅積層板之尺寸安定性、以及與銅箔之接著強度成為優良者，以作成複數層為佳。當令聚醯亞胺樹脂層為複數層時，以線膨脹係數(CTE)為30×10-6 (1/K)以下(較佳為1至30×10-6 (1/K)之範圍)之低線膨脹係數之樹脂層做為主要之聚醯亞胺樹脂層(B)，於其單面或雙面上設置熱塑性聚醯亞胺樹脂層為佳。以與銅箔相接之側之聚醯亞胺樹脂層(A)做為熱塑性聚醯亞胺樹脂層為佳。The polyimine resin layer of the flexible copper-clad laminate of the present invention may be composed of a single layer or a plurality of layers, in order to make the dimensional stability of the flexible copper-clad laminate, and copper foil Then, the strength is excellent, and it is preferable to form a plurality of layers. When the polyimine resin layer is a plurality of layers, the coefficient of linear expansion (CTE) is 30 × 10 -6 (1/K) or less (preferably in the range of 1 to 30 × 10 -6 (1/K)) The resin layer having a low coefficient of linear expansion is preferably used as the main polyimide resin layer (B), and a thermoplastic polyimide film layer is preferably provided on one or both sides thereof. The polyimide layer (A) on the side in contact with the copper foil is preferably a thermoplastic polyimide film layer.
在此，所謂熱塑性聚醯亞胺樹脂層，係指線膨脹係數(CTE)超過30×10-6 (1/K)，且玻璃轉移溫度為330℃以下者。較佳的熱塑性聚醯亞胺樹脂層係線膨脹係數在30×10-6 至60×10-6 (1/K)，且玻璃轉移溫度在200至330℃之範圍者。若主要的聚醯亞胺樹脂層(B)之CTE大於30×10-6 /℃，則形成覆銅積層板時惟恐有翹曲加劇之情形，此外，由於尺寸安定性降低，故不適做為製品。主要的聚醯亞胺樹脂層(B)之厚度宜為全聚醯亞胺樹脂層之厚度之50%以上，以70至95%為佳。Here, the thermoplastic polyimide resin layer means a coefficient of linear expansion (CTE) of more than 30 × 10 -6 (1/K) and a glass transition temperature of 330 ° C or lower. The preferred thermoplastic polyimide film has a coefficient of linear expansion of from 30 × 10 -6 to 60 × 10 -6 (1/K) and a glass transition temperature of from 200 to 330 °C. If the CTE of the main polyimine resin layer (B) is more than 30 × 10 -6 / ° C, there is a fear that warpage is intensified when a copper clad laminate is formed, and since dimensional stability is lowered, it is not suitable as product. The thickness of the main polyimide resin layer (B) is preferably 50% or more of the thickness of the wholly polyimine resin layer, preferably 70 to 95%.
關於形成聚醯亞胺樹脂層之方法並無特別限定，宜為例如：將做為聚醯亞胺樹脂之前驅物之聚醯胺酸之樹脂溶液直接塗佈於經表面處理之銅箔表面，並在150℃以下之溫度將樹脂溶液中所含之溶劑去除某種程度後，再在100至450(較佳為250至450℃)之溫度範圍進行5至40分鐘左右之熱處理，而進行溶劑之乾燥及醯亞胺化。當將聚醯亞胺樹脂層設置成2層以上時，宜在將第一聚醯胺酸之樹脂溶液塗佈、乾燥後，將第二聚醯胺酸之樹脂溶液塗佈、乾燥，以下同樣進行，依序將第三以後之聚醯胺酸之樹脂溶液塗佈、乾燥後，一起在250至450℃之溫度範圍進行5至40分鐘左右之熱處理，而進行醯亞胺化。若熱處理之溫度低於100℃，則聚醯亞胺之脫水閉環反應無法充分進行，相反地若超過450℃，則惟恐聚醯亞胺樹脂層及銅箔會因氧化等而劣化之情形。The method for forming the polyimide layer of the polyimide resin is not particularly limited, and it is preferably, for example, that the resin solution of poly-proline which is a precursor of the polyimide resin is directly coated on the surface of the surface-treated copper foil. And removing the solvent contained in the resin solution to a certain extent at a temperature of 150 ° C or lower, and then performing heat treatment for about 5 to 40 minutes at a temperature range of 100 to 450 (preferably 250 to 450 ° C) to carry out a solvent. Drying and hydrazine imidization. When the polyimine resin layer is provided in two or more layers, it is preferred to apply and dry the second polyaminic acid resin solution after applying and drying the first polyaminic acid resin solution. After the coating, the third and later polyphosphonic acid resin solution is applied and dried, and then heat-treated at a temperature ranging from 250 to 450 ° C for about 5 to 40 minutes to carry out hydrazine imidization. When the temperature of the heat treatment is less than 100 ° C, the dehydration ring-closure reaction of the polyimine is not sufficiently performed. On the other hand, if it exceeds 450 ° C, the polyimide film and the copper foil may be deteriorated by oxidation or the like.
聚醯亞胺樹脂層之厚度宜在6至45μm之範圍，以在9至40μm之範圍為佳。若絕緣層之厚度未達6μm，則在製造覆銅積層板等時於搬運中惟恐出現皺摺產生等之不良情形，反之，若超過45μm，則在製造覆銅積層板時惟恐在尺寸安定性或彎曲性等方面會發生問題。The thickness of the polyimide layer of the polyimide resin is preferably in the range of 6 to 45 μm, preferably in the range of 9 to 40 μm. When the thickness of the insulating layer is less than 6 μm, there is a fear that wrinkles may occur during transportation during the production of a copper clad laminate or the like. On the other hand, if it exceeds 45 μm, dimensional stability may be unpredictable when manufacturing a copper clad laminate. Or problems such as bending.
本發明之可撓性覆銅積層板當然可為僅於聚醯亞胺樹脂層之單面側具備有銅箔之單面覆銅積層板，也可為於聚醯亞胺樹脂層之雙面具備有銅箔之雙面覆銅積層板。再者，為了得到雙面覆銅積層板，可在形成單面覆銅積層板後，經由使聚醯亞胺樹脂層面對面並藉由熱壓予以壓合而形成、或將銅箔壓合於單面覆銅積層板之聚醯亞胺樹脂層上而形成等而得到。The flexible copper-clad laminate of the present invention may of course be a single-sided copper-clad laminate provided with a copper foil on only one side of the polyimide layer, or may be a double-sided layer of the polyimide layer. It has a double-sided copper-clad laminate with copper foil. Furthermore, in order to obtain a double-sided copper-clad laminate, after forming a single-sided copper-clad laminate, it may be formed by pressing the polyimide layer with a face-to-face and press-bonding by hot pressing, or pressing the copper foil to the copper foil. It is obtained by forming a polyimine resin layer on a single-sided copper-clad laminate.
本發明之可撓性覆銅積層板，在聚醯亞胺樹脂層與銅箔之1mm寬度之初期接著力以0.6kN/m以上為佳、以0.8至2.0kN/m更佳。此初期接著力係以記載於實施例之條件測定而得之值。為了得到此初期接著力，除了以與銅箔相接之聚醯亞胺樹脂層做為熱塑性聚醯亞胺樹脂層以外，可經由令銅箔之表面處理層中之特定金屬之量在上述範圍而達成。In the flexible copper-clad laminate of the present invention, the initial adhesion force of the polyimide film layer and the copper foil at a first width of 1 mm is preferably 0.6 kN/m or more, more preferably 0.8 to 2.0 kN/m. The initial adhesion force is a value measured by the conditions described in the examples. In order to obtain this initial adhesion, the amount of the specific metal in the surface treatment layer of the copper foil may be in the above range, except that the polyimide layer which is in contact with the copper foil is used as the thermoplastic polyimide resin layer. And reached.
以下，依據實施例更詳細說明本發明。再者，在以下之實施例中，只要未特別說明，各種評估即為依下述而得者。Hereinafter, the present invention will be described in more detail based on examples. Further, in the following examples, various evaluations are obtained as follows unless otherwise specified.
銅箔與聚醯亞胺樹脂層之間之接著力，係對於於銅箔上形成由聚醯亞胺樹脂組成之絕緣層而得之可撓性覆銅積層板，進行電路加工成線寬1mm，使用東洋精機股份有限公司製拉伸測試機(Strograph M1)，將銅箔朝180℃方向剝下而測得。The adhesive force between the copper foil and the polyimide layer is a flexible copper-clad laminate obtained by forming an insulating layer composed of a polyimide resin on a copper foil, and is processed into a line width of 1 mm. The tensile tester (Strograph M1) manufactured by Toyo Seiki Co., Ltd. was used, and the copper foil was peeled off at 180 ° C to measure.
銅箔之表面金屬層之金屬量之測定係藉由ICP-AES(Perkin Elmer公司製Optima 4300DV)實施。測定係以具有表面處理層之銅箔做為樣品，在將樣品2g以硝酸及鹽酸進行分解處理後，將容量固定於100mL，稀釋10倍後實施。The measurement of the amount of metal of the surface metal layer of the copper foil was carried out by ICP-AES (Optima 4300DV, manufactured by Perkin Elmer Co., Ltd.). In the measurement, a copper foil having a surface-treated layer was used as a sample, and after dissolving 2 g of the sample with nitric acid and hydrochloric acid, the capacity was fixed at 100 mL and diluted 10 times.
化學研磨耐性之測定，係對於可撓性覆銅積層板，進行電路加工成線寬1mm，並在40℃浸漬於過氧化氫2.5wt%/硫酸10wt%之化學研磨液中2分鐘後，使用200倍之光學顯微鏡從絕緣層側確認電路端部有無變色。The chemical polishing resistance was measured by linearly processing a flexible copper-clad laminate into a line width of 1 mm and immersing it in a chemical polishing solution of hydrogen peroxide (2.5 wt% / sulfuric acid 10 wt%) at 40 ° C for 2 minutes. A 200-fold optical microscope confirms the presence or absence of discoloration at the end of the circuit from the side of the insulating layer.
在具備熱電偶及攪拌機並且可導入氮氣之反應容器中裝入N,N-二甲基乙醯胺。在此反應容器中一面攪拌一面使2,2’-二甲基-4,4’-二胺基聯苯(m-TB)在容器中溶解。接著，加入3,3’,4,4’-聯苯四甲酸二酐及均苯四甲酸二酐(PMDA)。以使單體之投入總量成為15wt%，且各酸酐之莫耳比例(BPDA：PMDA)成為20：80之方式投入。之後，持續攪拌3小時，而得到聚醯胺酸之樹脂溶液a。聚醯胺酸之樹脂溶液a之溶液黏度為20000cps。由此聚醯胺酸所得之聚醯亞胺顯示25×10-6 (1/K)以下之低線膨脹係數，而具有非熱塑性之性質。N,N-dimethylacetamide was placed in a reaction vessel equipped with a thermocouple and a stirrer and capable of introducing nitrogen. 2,2'-Dimethyl-4,4'-diaminobiphenyl (m-TB) was dissolved in the vessel while stirring in the reaction vessel. Next, 3,3',4,4'-biphenyltetracarboxylic dianhydride and pyromellitic dianhydride (PMDA) were added. The total amount of the monomers to be charged was 15% by weight, and the molar ratio of each of the acid anhydrides (BPDA: PMDA) was 20:80. Thereafter, stirring was continued for 3 hours to obtain a resin solution a of poly-proline. The solution viscosity of the polyaminic acid resin solution a was 20000 cps. The polyimine obtained from the polyamic acid thus exhibits a low coefficient of linear expansion of 25 × 10 -6 (1/K) or less, and has a non-thermoplastic property.
在具備熱電偶及攪拌機並且可導入氮氣之反應容器中裝入N,N-二甲基乙醯胺。在此反應容器中一面攪拌一面使2,2-雙[4-(4-胺基苯氧基)苯基]丙烷在容器中溶解。接著，加入均苯四甲酸二酐，使單體之投入總量成為12wt%。之後，持續攪拌3小時，而得到聚醯胺酸之樹脂溶液b。聚醯胺酸之樹脂溶液b之溶液黏度為3000cps。由此聚醯胺酸所得之聚醯亞胺顯示超過30×10-6 (1/K)之線膨脹係數，而具有熱塑性之性質。N,N-dimethylacetamide was placed in a reaction vessel equipped with a thermocouple and a stirrer and capable of introducing nitrogen. 2,2-bis[4-(4-aminophenoxy)phenyl]propane was dissolved in the vessel while stirring in the reaction vessel. Next, pyromellitic dianhydride was added so that the total amount of the monomer was 12 wt%. Thereafter, stirring was continued for 3 hours to obtain a resin solution b of poly-proline. The solution viscosity of the polyaminic acid resin solution b was 3000 cps. The polyimine obtained from the polyamic acid thus exhibits a coefficient of linear expansion exceeding 30 × 10 -6 (1/K) and has thermoplastic properties.
準備做為表面處理層之經具有胺基之矽烷耦合劑矽烷耦合劑處理且含有表1所示之金屬元素之輥軋銅箔做為銅箔。此銅箔之厚度為18μm，表面粗糙度(Rz)為0.8μm。於此銅箔上，依序塗佈合成例2中所調製出之聚醯胺酸之樹脂溶液b與合成例1中所調製出之聚醯胺酸之樹脂溶液a並乾燥後，最後在300℃以上進行熱處理約10分鐘，而得到聚醯亞胺樹脂層之厚度為25μm之可撓性單面覆銅積層板。同時，在聚醯亞胺樹脂層中，由聚醯胺酸之樹脂溶液a所得之層為23μm、由聚醯胺酸之樹脂溶液b所得之層為2μm。此覆銅積層板之1mm剝離之初期接著力為1.0kN/m。此外，在將此樣品進行化學研磨後，在電路端部無法確認有變色。結果如表2所示。A rolled copper foil which was treated as a surface treatment layer and which was treated with an amine group-containing decane coupling agent decane coupling agent and which contained the metal element shown in Table 1 was prepared as a copper foil. This copper foil had a thickness of 18 μm and a surface roughness (Rz) of 0.8 μm. On the copper foil, the resin solution b of the polyamic acid prepared in Synthesis Example 2 and the resin solution a of the polyamic acid prepared in Synthesis Example 1 were sequentially coated and dried, and finally at 300. The heat treatment was carried out at a temperature of ° C or higher for about 10 minutes to obtain a flexible single-sided copper-clad laminate having a thickness of 25 μm of the polyimide layer. Meanwhile, in the polyimide layer, the layer obtained from the resin solution a of the poly-proline was 23 μm, and the layer obtained from the resin solution b of the poly-proline was 2 μm. The initial adhesion force of the 1 mm peeling of the copper clad laminate was 1.0 kN/m. Further, after the sample was chemically polished, discoloration could not be confirmed at the end of the circuit. The results are shown in Table 2.
除了使用表面金屬量不同之表1所示之輥軋銅箔以外，其餘與實施例1同樣進行，而評估剝離強度、化學研磨耐性。結果如表2所示。The peeling strength and the chemical polishing resistance were evaluated in the same manner as in Example 1 except that the rolled copper foil shown in Table 1 having a different surface metal amount was used. The results are shown in Table 2.
在表1中，Ni比係鎳量/(鎳量+鈷量+鋅量)。In Table 1, Ni is the amount of nickel / (the amount of nickel + the amount of cobalt + the amount of zinc).
實施例1、2中所得之覆銅積層板係在化學研磨處理後在電路端部未觀察到有變色，而確認未發生電路剝離。另一方面，比較例1、2則確認在整個電路端部皆有因電路剝離造成之變色。In the copper clad laminate obtained in Examples 1 and 2, no discoloration was observed at the end of the circuit after the chemical polishing treatment, and it was confirmed that no circuit peeling occurred. On the other hand, in Comparative Examples 1 and 2, it was confirmed that the entire circuit end had discoloration due to circuit peeling.
如此，本發明中所得之可撓性覆銅積層板，因在化學研磨後不會產生電路剝離，所以可靠性高，並且確認為適於精細加工用途之材料。As described above, the flexible copper-clad laminate obtained in the present invention has high reliability because it does not cause circuit peeling after chemical polishing, and is confirmed to be a material suitable for fine processing.
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