JP2007318177A - Double layer copper polyimide substrate - Google Patents
Double layer copper polyimide substrate Download PDFInfo
- Publication number
- JP2007318177A JP2007318177A JP2007210315A JP2007210315A JP2007318177A JP 2007318177 A JP2007318177 A JP 2007318177A JP 2007210315 A JP2007210315 A JP 2007210315A JP 2007210315 A JP2007210315 A JP 2007210315A JP 2007318177 A JP2007318177 A JP 2007318177A
- Authority
- JP
- Japan
- Prior art keywords
- layer
- polyimide
- copper
- thickness
- pct
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Withdrawn
Links
Abstract
Description
本発明は、プリント配線板、フレキシブルプリント配線板、ＴＡＢテープ、ＣＯＦテープ等の電子部品の素材となる金属被覆ポリイミド基板に関する。 The present invention relates to a metal-coated polyimide substrate used as a material for electronic components such as a printed wiring board, a flexible printed wiring board, a TAB tape, and a COF tape.
ポリイミドは、優れた耐熱性を有し、また機械的、電気的および化学的特性において他のプラスティック材料に比べ遜色のないことから、例えばプリント配線板（ＰＷＢ）、フレキシブルプリント配線板（ＦＰＣ）、テープ自動ボンディング用テープ（ＴＡＢ）、そしてチップオンフィルム（ＣＯＦ）等の電子部品用の絶縁基板材料として多用されている。この様なＰＷＢ，ＦＰＣ，またはＴＡＢ、ＣＯＦは、ポリイミドフィルムの少なくとも片面に金属導体層として主に銅を被覆した金属被膜ポリイミド基板を加工することによって得られている。 Polyimide has excellent heat resistance and is inferior to other plastic materials in mechanical, electrical and chemical properties. For example, printed wiring board (PWB), flexible printed wiring board (FPC), It is widely used as an insulating substrate material for electronic parts such as tape automatic bonding tape (TAB) and chip-on-film (COF). Such PWB, FPC, or TAB and COF are obtained by processing a metal-coated polyimide substrate in which at least one surface of a polyimide film is mainly coated with copper as a metal conductor layer.
金属被覆ポリイミド基板には、ポリイミドフィルムと金属箔とを接着剤を介して接合した３層銅ポリイミド基板と、ポリイミドフィルムに直接金属層を形成した２層銅ポリイミド基板がある。また２層銅ポリイミド基板には、市販の銅箔にポリイミドを成膜するキャスティング基板と、市販のポリイミドにスパッタおよび電気めっきまたは無電解めっき、もしくはその両方を併用し、直接金属を積層するめっき法により製造された２層銅ポリイミド基板（以下、２層めっき基板と略）がある。 Metal-coated polyimide substrates include a three-layer copper polyimide substrate obtained by bonding a polyimide film and a metal foil via an adhesive, and a two-layer copper polyimide substrate obtained by forming a metal layer directly on the polyimide film. In addition, for a two-layer copper polyimide substrate, a casting substrate that forms a polyimide film on a commercially available copper foil, and a plating method that directly laminates metal using sputtering and electroplating or electroless plating, or both, on a commercially available polyimide. There is a two-layer copper polyimide substrate (hereinafter abbreviated as a two-layer plating substrate) manufactured by
最近では特に携帯電子機器の小型、薄型化にともない、上記ＴＡＢ，ＣＯＦに対しても小型、薄型、すなわち高密度化が要求され、その配線ピッチ（配線幅／スペース幅）は益々狭くなっていることから、導体層（銅被膜）の厚みを薄く、自由にコントロールできる２層めっき基板が注目されている。 Recently, especially with the reduction in size and thickness of portable electronic devices, the above-mentioned TAB and COF are also required to be small and thin, that is, high density, and the wiring pitch (wiring width / space width) is becoming narrower. For this reason, a two-layer plated substrate that can be freely controlled by reducing the thickness of the conductor layer (copper coating) has attracted attention.
しかし、２層めっき基板は初期密着力こそ実用レベルにあるものの、耐熱環境における密着力や高温高湿環境における密着力など、信頼性に関わる密着力について従来の３層基板と比較して低く、不安が持たれている。したがって、市場からは３層基板と同等の密着力（４００Ｎ／ｍ程度）の確保が２層めっき基板には求められている。 However, although the two-layer plating substrate has an initial adhesion force at a practical level, the adhesion force related to reliability, such as the adhesion force in a heat-resistant environment and the adhesion force in a high-temperature and high-humidity environment, is lower than the conventional three-layer substrate, I have anxiety. Therefore, from the market, it is required for the two-layer plated substrate to ensure the same adhesion (about 400 N / m) as the three-layer substrate.
上記問題を解決するため、本発明は、２層めっき基板において、初期密着力、および１５０℃大気中に１６８時間放置した後の耐熱密着力、さらに１２１℃、９５％、２気圧、１００時間のＰＣＴ試験（Pressure Cooker Test）後のＰＣＴ密着力が、すべて４００Ｎ／ｍ以上となる２層めっき基板の構造を提供することを目的とする。 In order to solve the above problems, the present invention provides an initial adhesion strength and heat-resistant adhesion strength after standing for 168 hours in the atmosphere at 150 ° C., and 121 ° C., 95%, 2 atmospheres, 100 hours. An object of the present invention is to provide a structure of a two-layer plated substrate in which the PCT adhesion after the PCT test (Pressure Cooker Test) is 400 N / m or more.
上記課題を解決するため、本発明に係る２層銅ポリイミド基板は、少なくともポリイミドフィルムと、該ポリイミドフィルム上に直接形成された金属シード層と、該金属シード層上に形成された銅層とからなり、前記金属シード層が接する側のポリイミドフィルム表面側には該フィルム表面側を改質して親水性官能基が導入されたポリイミド改質層を有し、その改質層厚みが硝酸銀染色法による評価で２００オングストローム以下となっている２層銅ポリイミド基板であって、前記基板の、初期密着力と、１５０℃大気中に１６８時間放置された後の耐熱密着力と、１２１℃、９５％、２気圧、１００時間のＰＣＴ試験後のＰＣＴ密着力とが、いずれも銅の導体層の厚み８μｍにおいて、４００Ｎ／ｍ以上であり、前記試験後の２層銅ポリイミド基板の、走査オージェ電子顕微鏡（ＳＡＭ）による深さ分析による、該ポリイミドフィルムと金属シード層との界面における、酸素相対濃度／Ｎｉ相対濃度が０．２６以下であることを特徴とするものである。
また、本発明における前記金属シード層を構成する金属は、少なくともニッケル、クロム、及びこれらの合金からなる群から選ばれたものであることが好ましい。
In order to solve the above problems, a two-layer copper polyimide substrate according to the present invention comprises at least a polyimide film, a metal seed layer directly formed on the polyimide film, and a copper layer formed on the metal seed layer. A polyimide modified layer in which a hydrophilic functional group is introduced by modifying the film surface side on the polyimide film surface side on which the metal seed layer is in contact, and the thickness of the modified layer is a silver nitrate dyeing method A two-layer copper polyimide substrate having a thickness of 200 angstroms or less as evaluated by the above, including an initial adhesion strength, a heat-resistant adhesion strength after being left in the atmosphere at 150 ° C. for 168 hours, and 121 ° C., 95%. The PCT adhesion strength after the PCT test at 2 atm and 100 hours is 400 N / m or more when the copper conductor layer has a thickness of 8 μm. The oxygen relative concentration / Ni relative concentration at the interface between the polyimide film and the metal seed layer, as determined by depth analysis using a scanning Auger electron microscope (SAM), is 0.26 or less. is there.
Moreover, it is preferable that the metal which comprises the said metal seed layer in this invention is chosen from the group which consists of nickel, chromium, and these alloys at least.
更に、本発明における前記ポリイミドフィルムは、主成分としてピロメリット酸二無水和物（ＰＭＤＡ）と４，４’−ジアミノジフェニルエーテル（ＯＤＡ）を含む、もしくは、主成分としてピロメリット酸二無水和物（ＰＭＤＡ）と４，４’−ジアミノジフェニルエーテル（ＯＤＡ）からなる成分とビフェニルテトラカルボン酸二無水和物（ＢＰＤＡ）と４，４’−ジアミノジフェニルエーテル（ＯＤＡ）からなる成分を含むものであることが好ましい。
また、本発明における前記改質層厚みは硝酸銀染色法による評価で５０オングストローム以上であることが好ましい。
更に、前記ポリイミドフィルム表面の改質は、プラズマ処理、コロナ放電または湿式処理により行われることが好ましい。
Furthermore, the polyimide film in the present invention contains pyromellitic dianhydride (PMDA) and 4,4′-diaminodiphenyl ether (ODA) as main components, or pyromellitic dianhydride (as main components) ( It is preferable that a component comprising PMDA) and 4,4′-diaminodiphenyl ether (ODA) and a component comprising biphenyltetracarboxylic dianhydride (BPDA) and 4,4′-diaminodiphenyl ether (ODA) are included.
Further, the modified layer thickness in the present invention is preferably 50 angstroms or more as evaluated by a silver nitrate staining method.
Furthermore, the modification of the polyimide film surface is preferably performed by plasma treatment, corona discharge or wet treatment.
本発明者らは、２層めっき基板の密着特性の変化を詳細に調査し、耐熱試験およびＰＣＴ試験後の密着力低下がポリイミドと金属界面のポリイミド改質状態に起因することを見出した。さらに、その厚さを定量的に規定することによって上記問題を解決することができることを見出し、本発明に至った。 The present inventors investigated in detail the change in adhesion characteristics of the two-layer plated substrate, and found that the decrease in adhesion strength after the heat resistance test and the PCT test was caused by the polyimide modification state at the polyimide / metal interface. Furthermore, the inventors have found that the above problem can be solved by defining the thickness quantitatively, and have reached the present invention.
ポリイミドフィルム表面にプラズマやコロナ放電、あるいは湿式の処理を行うと、表面にカルボキシル基や水酸基などの親水性官能基が導入され、金属との密着性を高くなることが知られている。しかし耐熱試験、あるいはＰＣＴ試験後密着力が低下した試料の試験片の剥離界面を詳細に分析した結果、これらの処理で生成した改質層によりシード層の酸化、あるいはポリイミド表面の脆弱化が生じ密着力低下の原因となっていることが明らかになった。 It is known that when plasma, corona discharge, or wet treatment is performed on the surface of the polyimide film, hydrophilic functional groups such as carboxyl groups and hydroxyl groups are introduced on the surface, thereby improving the adhesion to the metal. However, as a result of a detailed analysis of the peeling interface of the specimen of the specimen whose adhesion was reduced after the heat resistance test or PCT test, the seed layer was oxidized or the polyimide surface was weakened by the modified layer generated by these treatments. It became clear that it was the cause of the decrease in adhesion.
そこで、初期密着および耐熱密着、さらにはＰＣＴ密着を全てバランス良く確保するためには、ポリイミドと金属界面におけるポリイミド改質層の構造を制御する必要があることに着目して検討を重ねてきた。検討を進めるにあたり、改質層を定量的に評価する必要性を重要視し、本出願人が先に出願した特願２００２−１４３７２２号に記載された硝酸銀水溶液によって染色して透過電子顕微鏡（ＴＥＭ）で断面を観察する方法を確立した。 Therefore, in order to ensure all initial adhesion, heat-resistant adhesion, and PCT adhesion in a well-balanced manner, investigations have been made focusing on the need to control the structure of the polyimide-modified layer at the polyimide-metal interface. In proceeding with the study, importance was attached to the need to quantitatively evaluate the modified layer, and a transmission electron microscope (TEM) was stained with a silver nitrate aqueous solution described in Japanese Patent Application No. 2002-143722 previously filed by the present applicant. ) Established a method of observing the cross section.
この方法では、表面を改質処理したポリイミドにシード層を成膜後湿式エッチングにより除去し、該試料をミクロトームで断面切削する。そして、その切片を１０％〜２０％程度の濃度の硝酸銀水溶液に１時間以内の時間浸漬して改質層を染色した後、ＴＥＭで断面を観察する。改質層と結合したシード層成分に銀が置換析出することで、ＴＥＭにてはっきりとしたコントラストで観察でき、改質層厚さを定量的に評価できるものである。 In this method, a seed layer is formed on polyimide whose surface has been modified, and then removed by wet etching, and the sample is cut by a microtome. Then, the slice is immersed in an aqueous silver nitrate solution having a concentration of about 10% to 20% for a time within 1 hour to stain the modified layer, and then the cross section is observed with a TEM. When silver is substituted and deposited on the seed layer component bonded to the modified layer, it can be observed with a clear contrast by TEM, and the thickness of the modified layer can be quantitatively evaluated.
ポリイミドフィルムを真空中で乾燥後、プラズマやコロナ放電等で処理し、シード層をスパッタリングにより成膜した試料を種々の条件で作製し、前述の硝酸銀染色法で評価した改質層厚みと初期密着力、耐熱密着力、そしてＰＣＴ密着力との関係を調査した。 After the polyimide film is dried in vacuum, it is treated with plasma, corona discharge, etc., and the seed layer is formed by sputtering under various conditions. The modified layer thickness and initial adhesion evaluated by the silver nitrate staining method described above are used. The relationship between strength, heat-resistant adhesion, and PCT adhesion was investigated.
その結果、ポリイミド表面の改質層厚さを２００オングストローム以下とし、その上にニッケル、クロム、またはこれらの合金からなるシード層を形成した後、電気銅めっきもしくは無電解銅めっき、また両者を併用して銅層を形成した構造にすれば、初期密着力、耐熱密着力およびＰＣＴ密着力のすべてが、８μｍの銅厚において４００Ｎ／ｍ以上である２層めっき基板が得られることを見出した。逆に、ポリイミド染色層の厚みが２００オングストローム以上の場合、初期密着力は高い値が得られるもの、耐熱密着力およびＰＣＴ密着力の低下が顕著であった。 As a result, the modified layer thickness on the polyimide surface was set to 200 angstroms or less, and after forming a seed layer made of nickel, chromium, or an alloy thereof, electrolytic copper plating or electroless copper plating, or a combination of both Thus, it was found that if a structure having a copper layer is formed, a two-layer plated substrate having an initial adhesion strength, heat-resistant adhesion strength and PCT adhesion strength of 400 N / m or more at a copper thickness of 8 μm can be obtained. On the other hand, when the thickness of the polyimide dyed layer was 200 angstroms or more, a high initial adhesion strength was obtained, and the heat adhesion strength and PCT adhesion strength were significantly reduced.
なお、前記各密着力は、銅厚が厚くなるほど高い値を示す傾向にあるが、本発明での密着力の測定は、現在汎用されている銅厚８μｍでの測定を基準として実施した。 In addition, although each said adhesive force exists in the tendency which shows a high value, so that copper thickness becomes thick, the measurement of the adhesive force in this invention was implemented on the basis of the measurement by the copper thickness of 8 micrometers currently used widely.
また、前記本発明を実現するには、使用するポリイミドは、ピロメリット酸二無水和物（ＰＭＤＡ）と４，４‘−ジアミノジフェニルエーテル（ＯＤＡ）を主成分とするもの、もしくはピロメリット酸二無水和物（ＰＭＤＡ）と４，４‘−ジアミノジフェニルエーテル（ＯＤＡ）からなる成分とビフェニルテトラカルボン酸二無水和物（ＢＰＤＡ）と４，４’−ジアミノジフェニルエーテル（ＯＤＡ）からなる成分を主成分とするものであることが好ましい。 In order to realize the present invention, the polyimide used is composed of pyromellitic dianhydride (PMDA) and 4,4′-diaminodiphenyl ether (ODA) as main components, or pyromellitic dianhydride. The main component is a component composed of a Japanese product (PMDA) and 4,4′-diaminodiphenyl ether (ODA), and a component composed of biphenyltetracarboxylic dianhydride (BPDA) and 4,4′-diaminodiphenyl ether (ODA). It is preferable.
次に実施例によって本発明を更に詳細に説明する。 Next, the present invention will be described in more detail by way of examples.
（ＰＭＤＡ＋ＯＤＡ）と（ＢＰＤＡ＋ＯＤＡ）を主成分とするポリイミドフィルム（カプトン１５０ＥＮ：東レデュポン社製）の表面をプラズマ処理により改質し、ニッケル・クロム合金のシード層を形成後、８μｍの銅層を形成させた試料を作成した。この改質層厚さが３００オングストロームの試料を、１５０℃大気中に１６８時間の条件で耐熱試験したところ、密着力が５００Ｎ／ｍから１８０Ｎ／mに低下した。耐熱試験前後の試験片の剥離個所を走査オージェ電子顕微鏡(SAM)で深さ方向分析した結果を耐熱試験前を図１、耐熱試験後を図２に示す。図中の縦方向の実線は、ポリイミドとシード層の界面を示す。なお、密着力の測定は、いずれも、ＪＰＣＡ ＢＭ０１−１１．５．３に準じて実施した。 The surface of a polyimide film (Kapton 150EN: manufactured by Toray DuPont) containing (PMDA + ODA) and (BPDA + ODA) as main components is modified by plasma treatment to form a nickel / chromium alloy seed layer, and then an 8 μm copper layer is formed. A prepared sample was prepared. When a heat resistance test was performed on a sample having a modified layer thickness of 300 angstroms in the atmosphere at 150 ° C. for 168 hours, the adhesion decreased from 500 N / m to 180 N / m. The results of depth direction analysis of the peeled portions of the test piece before and after the heat test with a scanning Auger electron microscope (SAM) are shown in FIG. 1 before the heat test and in FIG. 2 after the heat test. The solid line in the vertical direction in the figure indicates the interface between the polyimide and the seed layer. In addition, all measurement of the adhesive force was implemented according to JPCA BM01-11.5.3.
試験前は高い密着力が得られており、図１に示すように、剥離個所はポリイミド内部であるのに対し、試験後はシード層が酸化しポリイミドとシード層の界面で剥離していた。これはポリイミドの改質層に含まれる酸素によりシード層が酸化されて、ポリイミドとの化学的な結合力がなくなり密着力が低下したものと理解できる。 Prior to the test, high adhesion was obtained. As shown in FIG. 1, the peeled portion was inside the polyimide, whereas after the test, the seed layer was oxidized and peeled off at the interface between the polyimide and the seed layer. It can be understood that this is because the seed layer is oxidized by oxygen contained in the modified layer of polyimide, the chemical bonding force with polyimide is lost, and the adhesion is reduced.
一方、改質層厚さが５０オングストロームの試料では、耐熱試験後も４５０Ｎ／ｍと高い密着力が得られた。この試験片の剥離個所をＳＡＭで深さ方向分析した結果を耐熱試験前を図３、耐熱試験後を図４に示す。図３、４に示すように、耐熱試験前後共、剥離個所は、ポリイミド内部であり、改質層が薄いとシード層の酸化は認められず、高い密着力が維持できていることがわかる。 On the other hand, in the sample having a modified layer thickness of 50 Å, a high adhesion strength of 450 N / m was obtained even after the heat resistance test. The result of depth direction analysis of the peeled portion of this test piece by SAM is shown in FIG. 3 before the heat test and in FIG. 4 after the heat test. As shown in FIGS. 3 and 4, it can be seen that the peeled portion is inside the polyimide both before and after the heat resistance test, and when the modified layer is thin, oxidation of the seed layer is not recognized and high adhesion can be maintained.
実施例１と同様の試料を作成し、改質層厚さが３００オングストロームの試料を、１２１℃、９５％、２気圧、１００時間の条件でＰＣＴ試験したところ、密着力が５００Ｎ／ｍから２０Ｎ／ｍに大きく低下した。ＰＣＴ試験前後の試験片の剥離個所・シード層側を走査オージェ電子顕微鏡(ＳＡＭ)で深さ方向分析した結果をＰＣＴ試験前を図５、試験後を図６に示す。 A sample similar to that in Example 1 was prepared, and a sample having a modified layer thickness of 300 Å was subjected to a PCT test under the conditions of 121 ° C., 95%, 2 atm, and 100 hours. The adhesion strength was 500 N / m to 20 N. / M greatly decreased. FIG. 5 shows the result of depth direction analysis of the peeled portion / seed layer side of the test piece before and after the PCT test using a scanning Auger electron microscope (SAM), and FIG. 6 shows the result after the test.
試験前後共にポリイミドがシード層の上に密着しており、剥離個所はポリイミド
内部であることがわかる。ＰＣＴ試験での密着力の低下はポリイミド自身の脆弱化によるものと理解できる。
It can be seen that the polyimide is in close contact with the seed layer both before and after the test, and the peeled portion is inside the polyimide. It can be understood that the decrease in adhesion in the PCT test is due to weakening of the polyimide itself.
一方、改質層厚さが５０オングストロームの試料では、ＰＣＴ試験後も５１０Ｎ／ｍと高い密着力が得られた。この試験片の剥離個所を同じくＳＡＭで観察した結果を試験前を図７、試験後を図８に示す。この場合も剥離個所はポリイミド内部であるが、改質層が薄いとポリイミドの脆弱化が起こらず、高い密着力が維持できていた。 On the other hand, in the sample having a modified layer thickness of 50 Å, a high adhesion strength of 510 N / m was obtained even after the PCT test. The result of observing the peeled portion of the test piece with SAM is shown in FIG. 7 before the test and in FIG. 8 after the test. In this case as well, the peeled portion was inside the polyimide. However, if the modified layer was thin, the polyimide was not weakened and high adhesion could be maintained.
使用するポリイミドフィルムとして、カプトン１００Ｖ（東レデュポン社製：ＰＭＤＡ＋ＯＤＡを主成分とする）と、前記カプトン１５０ＥＮを真空中で乾燥後、プラズマやコロナ放電等で処理し、シード層をスパッタリングにより成膜した試料を種々の条件で作製し、硝酸銀水溶液によって染色して透過電子顕微鏡（ＴＥＭ）で断面を観察する方法で改質層厚みを評価した。 As a polyimide film to be used, Kapton 100V (manufactured by Toray DuPont: PMDA + ODA as a main component) and Kapton 150EN were dried in a vacuum and then treated with plasma or corona discharge, and a seed layer was formed by sputtering. Samples were prepared under various conditions, and the thickness of the modified layer was evaluated by a method of observing a cross section with a transmission electron microscope (TEM) after staining with an aqueous silver nitrate solution.
改質層厚みと初期密着力、耐熱密着力、そしてＰＣＴ密着力との関係を調査した結果を図９〜１１に示す。図中の破線は、それぞれの密着力の最大値の傾向を示すものであり、初期密着力と耐熱密着力とＰＣＴ密着力が、同時に４００Ｎ／ｍ以上であるためには、少なくとも改質層厚さが２００オングストローム以下であることが必要であることがわかる。 The results of investigating the relationship between the modified layer thickness and the initial adhesion, heat-resistant adhesion, and PCT adhesion are shown in FIGS. The broken line in the figure shows the tendency of the maximum value of each adhesion force, and in order for the initial adhesion force, the heat-resistant adhesion force and the PCT adhesion force to be 400 N / m or more at the same time, at least the modified layer thickness It can be seen that the length needs to be 200 angstroms or less.
初期密着力については、調査したすべての試料で４００Ｎ／ｍ以上の値が得られたが、耐熱密着力およびＰＣＴ密着力については、改質層厚さが２００オングストローム以上になると４００Ｎ／ｍ以上の値を満足する条件はなかった。 Regarding the initial adhesion, a value of 400 N / m or more was obtained for all the investigated samples. However, the heat-resistant adhesion and the PCT adhesion were 400 N / m or more when the modified layer thickness was 200 angstroms or more. There was no condition to satisfy the value.
しかし、２００オングストローム以下では初期密着力が高くなる条件を選べば、初期密着力、耐熱密着力、そしてＰＣＴ密着力のすべてが４００Ｎ／ｍを満足する基板が製造できることがわかった。たとえば、図９〜１１に示すように、改質層厚さ１８０オングストロームで、初期密着力７６０Ｎ／ｍ、耐熱密着力４４０Ｎ／ｍ、ＰＣＴ密着力４２０Ｎ／ｍ、改質層厚さ７０オングストロームで、初期密着力８２０Ｎ／ｍ、耐熱密着力４２０Ｎ／ｍ、ＰＣＴ密着力６００Ｎ／ｍ、改質層厚さ５０オングストロームで、初期密着力７２０Ｎ／ｍ、耐熱密着力４５０Ｎ／ｍ、ＰＣＴ密着力５１０Ｎ／ｍ、の各密着力を有する２層銅ポリイミド基板が得られた。 However, it has been found that if conditions under which the initial adhesion strength is increased below 200 angstroms are selected, a substrate that satisfies all of the initial adhesion strength, heat-resistant adhesion strength, and PCT adhesion strength of 400 N / m can be produced. For example, as shown in FIGS. 9 to 11, with a modified layer thickness of 180 angstroms, an initial adhesion strength of 760 N / m, a heat resistant adhesion strength of 440 N / m, a PCT adhesion strength of 420 N / m, and a modified layer thickness of 70 angstroms, Initial adhesion 820 N / m, heat adhesion 420 N / m, PCT adhesion 600 N / m, modified layer thickness 50 angstrom, initial adhesion 720 N / m, heat adhesion 450 N / m, PCT adhesion 510 N / m Thus, a two-layer copper polyimide substrate having each of the following adhesive strengths was obtained.
これは、改質層の厚さを薄く制御することで、界面でのシード層の酸化やポリイミドの脆弱化を抑制できたためである。 This is because by controlling the thickness of the modified layer to be thin, the oxidation of the seed layer and the weakening of the polyimide at the interface can be suppressed.
Claims (5)
前記金属シード層が接する側のポリイミドフィルム表面側には該フィルム表面側を改質して親水性官能基が導入されたポリイミド改質層を有し、その改質層厚みが硝酸銀染色法による評価で２００オングストローム以下となっている２層銅ポリイミド基板であって、
前記基板の、初期密着力と、１５０℃大気中に１６８時間放置された後の耐熱密着力と、１２１℃、９５％、２気圧、１００時間のＰＣＴ試験後のＰＣＴ密着力とが、いずれも銅の導体層の厚み８μｍにおいて、４００Ｎ／ｍ以上であり、
前記試験後の２層銅ポリイミド基板の、走査オージェ電子顕微鏡（ＳＡＭ）による深さ分析による、該ポリイミドフィルムと金属シード層との界面における、酸素相対濃度／Ｎｉ相対濃度が０．２６以下であることを特徴とする２層銅ポリイミド基板。 At least a polyimide film, a metal seed layer directly formed on the polyimide film, and a copper layer formed on the metal seed layer,
The polyimide film surface on the side in contact with the metal seed layer has a polyimide modified layer in which a hydrophilic functional group is introduced by modifying the film surface, and the thickness of the modified layer is evaluated by a silver nitrate staining method. A two-layer copper polyimide substrate having a thickness of 200 angstroms or less,
The initial adhesion strength of the substrate, the heat-resistant adhesion strength after being left in the atmosphere at 150 ° C. for 168 hours, and the PCT adhesion strength after the PCT test at 121 ° C., 95%, 2 atm, 100 hours are all. When the thickness of the copper conductor layer is 8 μm, it is 400 N / m or more,
The oxygen relative concentration / Ni relative concentration at the interface between the polyimide film and the metal seed layer is 0.26 or less by the depth analysis of the two-layer copper polyimide substrate after the test by a scanning Auger electron microscope (SAM). A two-layer copper polyimide substrate characterized by the above.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2007210315A JP2007318177A (en) | 2007-08-10 | 2007-08-10 | Double layer copper polyimide substrate |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2007210315A JP2007318177A (en) | 2007-08-10 | 2007-08-10 | Double layer copper polyimide substrate |
Related Parent Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2002149595A Division JP4517564B2 (en) | 2002-05-23 | 2002-05-23 | 2-layer copper polyimide substrate |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JP2007318177A true JP2007318177A (en) | 2007-12-06 |
Family
ID=38851690
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2007210315A Withdrawn JP2007318177A (en) | 2007-08-10 | 2007-08-10 | Double layer copper polyimide substrate |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2007318177A (en) |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2009154521A (en) * | 2007-12-27 | 2009-07-16 | Lg Electronics Inc | Flexible film and display having the same |
| JP2010005800A (en) * | 2008-06-24 | 2010-01-14 | Sumitomo Metal Mining Co Ltd | Two-layered flexible substrate, its method of manufacturing, printed-wiring board using the two-layered flexible substrate, and its method of manufacturing |
| WO2010098235A1 (en) | 2009-02-25 | 2010-09-02 | 日鉱金属株式会社 | Metal-coated polyimide resin substrate with excellent thermal aging resistance properties |
| WO2010098236A1 (en) | 2009-02-25 | 2010-09-02 | 日鉱金属株式会社 | Metal-clad polyimide resin substrate with excellent thermal aging resistance characteristics |
| JP2010260328A (en) * | 2009-04-10 | 2010-11-18 | Jx Nippon Mining & Metals Corp | Method of manufacturing two-layer copper clad laminated sheet, and two-layer copper clad laminated sheet |
| JP2010278222A (en) * | 2009-05-28 | 2010-12-09 | Nitto Denko Corp | Both-surface wiring circuit board and method of manufacturing the same |
| JP2012194014A (en) * | 2011-03-16 | 2012-10-11 | Sumitomo Metal Mining Co Ltd | Adhesion evaluation method of bilayer plating substrate |
| KR20200060228A (en) | 2018-11-22 | 2020-05-29 | 스미토모 긴조쿠 고잔 가부시키가이샤 | Flexible substrate |
-
2007
- 2007-08-10 JP JP2007210315A patent/JP2007318177A/en not_active Withdrawn
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2009154521A (en) * | 2007-12-27 | 2009-07-16 | Lg Electronics Inc | Flexible film and display having the same |
| JP2010005800A (en) * | 2008-06-24 | 2010-01-14 | Sumitomo Metal Mining Co Ltd | Two-layered flexible substrate, its method of manufacturing, printed-wiring board using the two-layered flexible substrate, and its method of manufacturing |
| WO2010098235A1 (en) | 2009-02-25 | 2010-09-02 | 日鉱金属株式会社 | Metal-coated polyimide resin substrate with excellent thermal aging resistance properties |
| WO2010098236A1 (en) | 2009-02-25 | 2010-09-02 | 日鉱金属株式会社 | Metal-clad polyimide resin substrate with excellent thermal aging resistance characteristics |
| JP2010260328A (en) * | 2009-04-10 | 2010-11-18 | Jx Nippon Mining & Metals Corp | Method of manufacturing two-layer copper clad laminated sheet, and two-layer copper clad laminated sheet |
| JP2010278222A (en) * | 2009-05-28 | 2010-12-09 | Nitto Denko Corp | Both-surface wiring circuit board and method of manufacturing the same |
| JP2012194014A (en) * | 2011-03-16 | 2012-10-11 | Sumitomo Metal Mining Co Ltd | Adhesion evaluation method of bilayer plating substrate |
| KR20200060228A (en) | 2018-11-22 | 2020-05-29 | 스미토모 긴조쿠 고잔 가부시키가이샤 | Flexible substrate |
| KR20240023561A (en) | 2018-11-22 | 2024-02-22 | 스미토모 긴조쿠 고잔 가부시키가이샤 | Flexible substrate |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP5178064B2 (en) | Metal layer laminate having metal surface roughened layer and method for producing the same | |
| JP2007318177A (en) | Double layer copper polyimide substrate | |
| JP4517564B2 (en) | 2-layer copper polyimide substrate | |
| KR100859614B1 (en) | Composite copper foil and method for production thereof | |
| KR101133488B1 (en) | Non-adhesive-type flexible laminate and method for production thereof | |
| JP4923903B2 (en) | Copper-coated polyimide substrate with high heat-resistant adhesion | |
| JPWO2008152974A1 (en) | Method for producing metal-coated polyimide resin substrate with excellent heat aging characteristics | |
| JP3888587B2 (en) | Etching method of flexible substrate | |
| JP2008307737A (en) | Laminate, wiring board and its manufacturing method | |
| WO2010098235A1 (en) | Metal-coated polyimide resin substrate with excellent thermal aging resistance properties | |
| TW200934657A (en) | Adhesive-free flexible laminate | |
| JP4683646B2 (en) | Copper or copper alloy foil for printed circuit boards | |
| JP2007069561A (en) | Two-layered flexible substrate and manufacturing method therefor | |
| JP2007208251A (en) | Substrate for flexible board, flexible board using it, and manufacturing method thereof | |
| JP2003011273A (en) | Metallized polyimide film | |
| WO2010098236A1 (en) | Metal-clad polyimide resin substrate with excellent thermal aging resistance characteristics | |
| JP4385297B2 (en) | Two-layer flexible substrate and manufacturing method thereof | |
| JP4385298B2 (en) | Two-layer flexible substrate and manufacturing method thereof | |
| JP2006175634A (en) | Metal-polyimide substrate | |
| JP2006013152A (en) | Two-layer flexible board and manufacturing method thereof | |
| JP2009004588A (en) | Copper clad polyimide substrate | |
| JP2003011272A (en) | Metallized polyimide film | |
| JP2003318532A (en) | Flexible printed wiring board | |
| JP2004075913A (en) | Metal-clad polyimide substrate | |
| JP2021172006A (en) | Copper-clad laminate, and method for manufacturing copper-clad laminate |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| A621 | Written request for application examination |
Free format text: JAPANESE INTERMEDIATE CODE: A621 Effective date: 20070829 |
|
| A521 | Written amendment |
Effective date: 20090826 Free format text: JAPANESE INTERMEDIATE CODE: A523 |
|
| A761 | Written withdrawal of application |
Free format text: JAPANESE INTERMEDIATE CODE: A761 Effective date: 20100416 |