JP2008258559A - Laminated body for wiring board - Google Patents
Laminated body for wiring board Download PDFInfo
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- JP2008258559A JP2008258559A JP2007204106A JP2007204106A JP2008258559A JP 2008258559 A JP2008258559 A JP 2008258559A JP 2007204106 A JP2007204106 A JP 2007204106A JP 2007204106 A JP2007204106 A JP 2007204106A JP 2008258559 A JP2008258559 A JP 2008258559A
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- wiring board
- laminate
- polyimide resin
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- polyimide
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Abstract
Description
本発明は、金属層と絶縁層とからなり、ポリイミド樹脂を絶縁層とするフレキシブル配線基板やHDD(ハードディスクドライブ)サスペンションに使用される配線基板用積層体に関するものである。 The present invention relates to a laminate for a wiring board, which is composed of a metal layer and an insulating layer, and is used for a flexible wiring board or HDD (hard disk drive) suspension using a polyimide resin as an insulating layer.
一般的に電子機器に使用されるフレキシブル配線基板、これを形成するフレキシブル銅張積層板の絶縁層には、耐熱性、寸法安定性、電気特性等の諸特性に優れるポリイミド樹脂が広く用いられている。 In general, flexible resin boards that are used in electronic equipment and the insulating layer of the flexible copper clad laminate that forms them are made of polyimide resin that excels in heat resistance, dimensional stability, electrical characteristics, and other properties. Yes.
そして、これまでポリイミドを絶縁層とする様々なフレキシブル銅張積層板が検討されて来ている。例えば、特許文献1には、特定の樹脂構造を有するポリイミド樹脂からなるフレキシブル銅張積層板が開示されている。しかし、従来のポリイミド樹脂は、他の有機ポリマーに比べ耐熱性や電気絶縁性は優れているものの、吸湿率が大きいためにこれを加工して得られるフレキシブル配線基板を半田浴に浸漬した際に生じる膨れや、ポリイミド樹脂の吸湿後の寸法変化による電子機器の接続不良等の懸念があった。
And until now, various flexible copper clad laminates using polyimide as an insulating layer have been studied. For example,
そこで、ポリイミド樹脂の湿度環境変化による寸法安定性を改善するために、ポリイミド樹脂層を形成するポリイミド樹脂として、4,4’−ジアミノ−2,2’−ジメチルビフェニルを20モル%以上含有するジアミンを使用して得られたポリイミド樹脂の層を有する積層体が特許文献2に示されている。
Therefore, in order to improve the dimensional stability due to changes in the humidity environment of the polyimide resin, a diamine containing 20 mol% or more of 4,4′-diamino-2,2′-dimethylbiphenyl is used as the polyimide resin for forming the polyimide resin layer.
近年、電子機器の高性能化、高機能化が急速に進んでおり、これに伴い電子機器に用いられる電子部品やそれらを実装する基板に対しても、より高密度で高性能なものへと要求が高まっている。そして、電子機器は益々軽量化、小型化、薄型化の傾向にあり、電子部品を収容するスペースは狭まる一方である。これらの課題を解決する技術の1つに、フレキシブル配線基板上に半導体チップを実装する技術が注目されている。このいわゆるCOF(チップ・オン・フィルム)用途に使用されるフレキシブル配線基板は、製造工程の搬送のためにスプロケットホールを有しているが、その部分の破断と変形を生じやすいという問題から、これまでのフレキシブル配線基板の絶縁層は、その信頼性を維持するために40μm程度以上の一定の厚みを必要としていた。 In recent years, the performance and functionality of electronic devices have been rapidly increasing, and with this, electronic components used in electronic devices and the boards on which they are mounted have become higher density and higher performance. The demand is growing. Electronic devices are becoming increasingly lighter, smaller, and thinner, and the space for housing electronic components is becoming narrower. As one of the techniques for solving these problems, a technique for mounting a semiconductor chip on a flexible wiring board has attracted attention. The flexible wiring board used for this so-called COF (chip-on-film) application has sprocket holes for conveyance in the manufacturing process. In order to maintain the reliability, the insulating layer of the flexible wiring board up to the above requires a certain thickness of about 40 μm or more.
一方、折畳み型携帯電話や摺動型携帯電話等の可動部に用いられるフレキシブル配線基板においても同様に配線の高密度化が求められ、それに伴い高耐屈曲性も要求されるようになった。しかしながら、従来のフレキシブル配線基板は多層化や小屈曲半径化すると長期間の使用後に断線を発生するといった問題があり、折畳み型携帯電話や摺動型携帯電話の可動部に十分な耐屈曲性を有するものは必ずしも得られていなかった。そこで、寸法安定性、耐熱性、その他のポリイミド樹脂の優れた特性を生かしながら、耐屈曲性にも優れたフレキシブルブル配線基板を与える銅張積層板の開発が望まれていた。 On the other hand, a flexible wiring board used for a movable part such as a folding cellular phone or a sliding cellular phone is also required to have a high wiring density, and accordingly, a high bending resistance is also required. However, conventional flexible wiring boards have the problem of disconnection after a long period of use if they are multilayered or have a small bending radius, and sufficient bending resistance is provided for the movable parts of folding and sliding mobile phones. What it has was not necessarily obtained. Therefore, it has been desired to develop a copper-clad laminate that provides a flexible wiring board with excellent bending resistance while taking advantage of dimensional stability, heat resistance, and other excellent properties of polyimide resin.
また、HDDサスペンションの用途でも、絶縁層のポリイミド樹脂には、寸法安定性や吸湿率の低いものが好ましく使用されるが、これら特性の他にも、更に、強度に優れ、加工特性にも優れていることが好ましい。HDDサスペンション用途へ適用する場合の加工方法の1つとして、アルカリ水溶液によるエッチング液を用いたウエットエッチング法が知られており、加工部分のエッチング形状を良好なものにするにはエッチング速度が速いことが好ましい。以上のことから、エッチング特性に優れたHDDサスペンションに使用される積層体の開発も望まれていた。 Also for HDD suspension applications, the polyimide resin of the insulating layer is preferably one with low dimensional stability and low moisture absorption. In addition to these characteristics, it also has excellent strength and excellent processing characteristics. It is preferable. As one of processing methods when applied to HDD suspension applications, a wet etching method using an etching solution with an alkaline aqueous solution is known, and an etching rate is fast in order to improve the etching shape of the processed portion. Is preferred. From the above, it has been desired to develop a laminate used for an HDD suspension having excellent etching characteristics.
本発明は、熱膨張係数に代表される寸法安定性、COF実装時に要求される耐熱特性、その他のポリイミドの優れた特性を生かしながら、耐屈曲性にも優れたフレキシブル配線基板やエッチング特性に優れたHDDサスペンションに使用される配線基板用積層体を提供することを目的とする。 The present invention is excellent in flex wiring resistance and etching characteristics while taking advantage of dimensional stability typified by thermal expansion coefficient, heat resistance required for COF mounting, and other excellent characteristics of polyimide. Another object of the present invention is to provide a laminate for a wiring board used for an HDD suspension.
本発明者等は上記課題を解決するために検討を重ねた結果、絶縁層を構成するポリイミド樹脂に特定のポリイミド樹脂を採用することで上記課題を解決し得ることを見出し、本発明を完成した。 As a result of repeated studies to solve the above problems, the present inventors have found that the above problems can be solved by adopting a specific polyimide resin for the polyimide resin constituting the insulating layer, and the present invention has been completed. .
すなわち、本発明は、単層又は複数層からなるポリイミド樹脂層の少なくとも一方の面に金属層を有する配線基板用積層体において、重量平均分子量が150000〜800000の範囲にあるポリイミド前駆体樹脂をイミド化して得られるポリイミド樹脂層(A)を主たるポリイミド樹脂層とし、これを構成するポリイミド樹脂が下記一般式(1)、(2)及び(3)で表される構造単位からなることを特徴とする配線基板用積層体である。
上記ポリイミド樹脂層(A)は、厚さが5〜30μmで、引き裂き伝播抵抗が100〜400mNの範囲にあり、かつ、熱膨張係数が30×10-6/K以下であることがよい。また、上記ポリイミド樹脂層(A)は、ガラス転移温度が310℃以上で、かつ、400℃における弾性率が、0.1GPa以上であることがよい。そして、上記配線基板用積層体は、フレキシブル配線基板用積層体又はHDDサスペンション用積層体として適する。 The polyimide resin layer (A) preferably has a thickness of 5 to 30 μm, a tear propagation resistance in the range of 100 to 400 mN, and a thermal expansion coefficient of 30 × 10 −6 / K or less. The polyimide resin layer (A) preferably has a glass transition temperature of 310 ° C. or higher and an elastic modulus at 400 ° C. of 0.1 GPa or higher. The wiring board laminate is suitable as a flexible wiring board laminate or a HDD suspension laminate.
また、本発明は、上記フレキシブル配線基板用積層体を、配線加工して得られるフレキシブル配線基板の側部に所望形状のスプロケットホールを設けたことを特徴とするCOF用フレキシブル配線基板である。 The present invention also provides a flexible wiring board for COF, wherein a sprocket hole having a desired shape is provided in a side portion of a flexible wiring board obtained by wiring the laminate for a flexible wiring board.
以下、本発明を詳細に説明する。
本発明の配線基板用積層体は、ポリイミド樹脂層の少なくとも一方の面、すなわち、片側又は両側に金属層を有する。ポリイミド樹脂層と金属層を積層させる方法には、ポリイミド前駆体樹脂溶液(ポリアミド酸溶液ともいう。)を塗布した後、乾燥・硬化する所謂キャスト法、ポリイミドフィルムに熱可塑性のポリイミドを塗布した後に銅箔、ステンレスなどによる金属層を熱ラミネートする所謂ラミネート法、ポリイミドフィルムの表面にスパッタ処理により導通層を形成した後、電気めっきにより導体層を形成する所謂スパッタめっき法などがある。これらのいずれの方法を用いてもよいが、ポリイミド前駆体樹脂溶液を塗布した後、乾燥・硬化するキャスト法が最も適する。しかし、本発明はこれに限定されるものではない。
Hereinafter, the present invention will be described in detail.
The laminate for a wiring board of the present invention has a metal layer on at least one surface of the polyimide resin layer, that is, on one side or both sides. For the method of laminating the polyimide resin layer and the metal layer, a polyimide precursor resin solution (also referred to as a polyamic acid solution) is applied, followed by drying and curing, a so-called casting method, after applying a polyimide polyimide to a polyimide film. There is a so-called laminating method in which a metal layer made of copper foil, stainless steel or the like is thermally laminated, a so-called sputter plating method in which a conductive layer is formed on the surface of a polyimide film by sputtering and then a conductor layer is formed by electroplating. Any of these methods may be used, but the casting method in which the polyimide precursor resin solution is applied and then dried and cured is most suitable. However, the present invention is not limited to this.
ポリイミド樹脂層は、単層であっても、また複数層であってもよい。但し、接着層としてエポキシ樹脂層などポリイミド以外の樹脂層を設けると耐熱性の低下を招くことから、実質的にはポリイミド以外の樹脂層を有しないことが必要である。また、ポリイミド樹脂層は、主たる層として、ポリイミド樹脂層(A)を有する。本発明で、主たる層とは、ポリイミド樹脂層の全厚みの60%以上、好ましくは70%以上の厚みを有する層をいう。 The polyimide resin layer may be a single layer or a plurality of layers. However, if a resin layer other than polyimide, such as an epoxy resin layer, is provided as an adhesive layer, the heat resistance is lowered, and therefore it is necessary that the resin layer substantially not include polyimide. Moreover, the polyimide resin layer has a polyimide resin layer (A) as a main layer. In the present invention, the main layer refers to a layer having a thickness of 60% or more, preferably 70% or more of the total thickness of the polyimide resin layer.
ポリイミド樹脂層(A)は、上記一般式(1)、(2)及び(3)で表される構造単位から構成されている。また、l、m、nは各構造単位の存在モル比(全構造単位の合計を1としたとき)を示し、lは0.6〜0.9、好ましくは0.6〜0.89、mは0.1〜0.3、nは0.01〜0.2の範囲の数である。より好ましくは、lは0.7〜0.80、mは0.15〜0.25、nは0.05〜0.15の範囲であることがよい。 The polyimide resin layer (A) is composed of structural units represented by the above general formulas (1), (2) and (3). L, m, and n represent the molar ratio of each structural unit (when the total of all structural units is 1), l is 0.6 to 0.9, preferably 0.6 to 0.89, m is a number in the range of 0.1 to 0.3 and n is in the range of 0.01 to 0.2. More preferably, l is 0.7 to 0.80, m is 0.15 to 0.25, and n is 0.05 to 0.15.
一般式(1)の構造単位は主に低熱膨張性と高耐熱性等の性質を向上させ、一般式(2)の構造単位は主に強靭性や接着性等の性質を向上させると考えられるが、相乗効果や分子量の影響があるため厳密ではない。しかし、強靭性等を増加させるためには、一般式(2)の構造単位を増やすことが有効である。一般式(3)の構造単位は低熱膨張性と強靭性のバランスを良好に調整すると考えられる。 The structural unit of the general formula (1) mainly improves properties such as low thermal expansion and high heat resistance, and the structural unit of the general formula (2) mainly improves properties such as toughness and adhesiveness. However, it is not exact because of synergistic effects and molecular weight effects. However, in order to increase toughness and the like, it is effective to increase the structural unit of the general formula (2). The structural unit of the general formula (3) is considered to favorably adjust the balance between low thermal expansion and toughness.
一般式(1)において、Rは炭素数1〜6の低級アルキル基、フェニル基又はハロゲンを示す。本発明における一般式(1)で表される構造単位の好ましい例としては、下記式(4)で表される構造単位が例示される。
一般式(2)において、Ar1は上記式(a)及び(b)から選択される2価の芳香族基のいずれかを示す。式(a)及び(b)において、Ar3は上記式(c)又は(d)から選択される2価の芳香族基のいずれかを示す。Ar1の好ましい例としては、下記式(e)、(f)及び(g)で表される2価の芳香族基が例示される。 In the general formula (2), Ar 1 represents any of divalent aromatic groups selected from the above formulas (a) and (b). In the formulas (a) and (b), Ar 3 represents either a divalent aromatic group selected from the above formulas (c) or (d). Preferable examples of Ar 1 include divalent aromatic groups represented by the following formulas (e), (f) and (g).
また、一般式(3)において、Ar2は、3,4’−ジアミノジフェニルエーテル又は4,4’−ジアミノジフェニルエーテルのいずれかの残基(アミノ基をとって残る基)を示す。 In the general formula (3), Ar 2 represents any residue of 3,4'-diaminodiphenyl ether or 4,4'-diaminodiphenyl ether (a group remaining after taking an amino group).
ポリイミド樹脂層(A)を構成するポリイミド樹脂は、重量平均分子量が150000〜800000、好ましくは200000〜800000の範囲にあるポリイミド前駆体樹脂をイミド化して得られる。重量平均分子量の値が150000に満たないと、フィルムの引裂き伝播抵抗が弱くなり、800000を超えると均一なフィルムの作製が困難となる。重量平均分子量はGPC法によってポリスチレン換算の値を求めることができる。なお、ポリイミド前駆体樹脂をイミド化して得られるポリイミド樹脂の重量平均分子量も、ポリイミド前駆体樹脂状態で測定されるものと略等しいため、ポリイミド前駆体樹脂の重量平均分子量をもってポリイミド樹脂の重量平均分子量と見做すことができる。 The polyimide resin constituting the polyimide resin layer (A) is obtained by imidizing a polyimide precursor resin having a weight average molecular weight in the range of 150,000 to 800,000, preferably 200000 to 800,000. When the value of the weight average molecular weight is less than 150,000, the tear propagation resistance of the film becomes weak, and when it exceeds 800,000, it becomes difficult to produce a uniform film. The weight average molecular weight can be determined in terms of polystyrene by the GPC method. In addition, since the weight average molecular weight of the polyimide resin obtained by imidizing the polyimide precursor resin is substantially equal to that measured in the polyimide precursor resin state, the weight average molecular weight of the polyimide resin is equal to the weight average molecular weight of the polyimide precursor resin. Can be considered.
ポリイミド樹脂層の合計の厚さは、好ましくは10〜40μm、より好ましくは15〜30μmの範囲にあることがよい。また、ポリイミド樹脂層(A)の厚さは5〜35μm、好ましくは5〜30μm、より好ましくは10〜30μmの範囲とすることがよい。ポリイミド樹脂層(A)の厚みをこの範囲にすることで、屈曲性に優れたフレキシブル配線用基板とすることができる。 The total thickness of the polyimide resin layer is preferably in the range of 10 to 40 μm, more preferably 15 to 30 μm. The thickness of the polyimide resin layer (A) is 5 to 35 μm, preferably 5 to 30 μm, more preferably 10 to 30 μm. By setting the thickness of the polyimide resin layer (A) within this range, a flexible wiring substrate having excellent flexibility can be obtained.
また、ポリイミド樹脂層(A)の引裂き伝播抵抗を100〜400mN、有利には130〜350mNとすることで、ポリイミド樹脂層の厚みを薄くしても、破断や変形しにくく、屈曲性にも優れたフレキシブル配線基板用積層体とすることができる。また、熱膨張係数を30×10-6/K以下、有利には25×10-6/K以下とすることで、カール等の変形を制御することができる。更に、ポリイミド樹脂層(A)のガラス転移温度を310℃以上、有利には310〜500℃とし、400℃における弾性率を0.1GPa以上、有利には0.15〜5GPaの範囲とすることで、高温実装が可能となり、COF用途に特に適したフレキシブル配線基板用積層体とすることができる。このような特性のポリイミド樹脂層(A)とするには、ポリイミド樹脂層(A)を構成する構造単位や分子量を最適範囲とすることによって得ることができる。 In addition, by setting the tear propagation resistance of the polyimide resin layer (A) to 100 to 400 mN, preferably 130 to 350 mN, even if the polyimide resin layer is thin, it is difficult to break or deform and has excellent flexibility. It can be set as the laminated body for flexible wiring boards. Further, by setting the thermal expansion coefficient to 30 × 10 −6 / K or less, preferably 25 × 10 −6 / K or less, deformation such as curling can be controlled. Furthermore, the glass transition temperature of the polyimide resin layer (A) is 310 ° C. or higher, preferably 310 to 500 ° C., and the elastic modulus at 400 ° C. is 0.1 GPa or higher, preferably 0.15 to 5 GPa. Thus, high-temperature mounting is possible, and a flexible printed circuit board laminate particularly suitable for COF applications can be obtained. The polyimide resin layer (A) having such characteristics can be obtained by setting the structural unit and molecular weight constituting the polyimide resin layer (A) within the optimum range.
本発明のポリイミド樹脂は、上述したように複数層によって形成することもできる。ポリイミド樹脂層(A)及びポリイミド樹脂層(A)以外の他のポリイミド樹脂層を構成するポリイミド樹脂は、原料のジアミンと酸無水物とを溶媒の存在下で重合し、ポリイミド前駆体樹脂とした後、熱処理によりイミド化することによって製造することができる。溶媒は、ジメチルアセトアミド、ジメチルホルムアミド、N-メチルピロリジノン、2-ブタノン、ジグライム、キシレン等が挙げられ、1種若しくは2種以上併用して使用することもできる。 The polyimide resin of the present invention can be formed of a plurality of layers as described above. Polyimide resin constituting the polyimide resin layer (A) and other polyimide resin layers other than the polyimide resin layer (A) is a polyimide precursor resin obtained by polymerizing raw material diamine and acid anhydride in the presence of a solvent. Thereafter, it can be produced by imidization by heat treatment. Examples of the solvent include dimethylacetamide, dimethylformamide, N-methylpyrrolidinone, 2-butanone, diglyme, xylene and the like, and they can be used alone or in combination of two or more.
他のポリイミド樹脂層を構成するポリイミド樹脂原料となるジアミンとしては、H2N−Ar4−NH2によって表される化合物が挙げられ、Ar4としては下記によって表わされる芳香族ジアミン残基が例示される。 Examples of the diamine which is a polyimide resin raw material constituting another polyimide resin layer include compounds represented by H 2 N—Ar 4 —NH 2 , and examples of Ar 4 include aromatic diamine residues represented by the following: Is done.
これらの中でも、4,4’−ジアミノジフェニルエーテル(4,4’−DAPE)、1,3−ビス(4−アミノフェノキシ)ベンゼン(TPE−R)、1,3−ビス(3−アミノフェノキシ)ベンゼン(APB)、2,2−ビス(4−アミノフェノキシフェニル)プロパン(BAPP)が好適なものとして例示される。 Among these, 4,4′-diaminodiphenyl ether (4,4′-DAPE), 1,3-bis (4-aminophenoxy) benzene (TPE-R), 1,3-bis (3-aminophenoxy) benzene (APB), 2,2-bis (4-aminophenoxyphenyl) propane (BAPP) is exemplified as a preferable example.
また、酸無水物としては、O(OC)2Ar5(CO)2Oによって表される化合物が挙げられ、Ar5としては、下記式で表わされる芳香族酸二無水物残基が例示される。 Examples of the acid anhydride include a compound represented by O (OC) 2 Ar 5 (CO) 2 O, and examples of Ar 5 include an aromatic acid dianhydride residue represented by the following formula. The
これらの中でも、ピロメリット酸二無水物(PMDA)、3,3’,4,4’−ビフェニルテトラカルボン酸二無水物(BPDA)、3,3’,4,4’−ベンゾフェノンテトラカルボン酸二無水物(BTDA)、3,3’,4,4’−ジフェニルスルホンテトラカルボン酸二無水物(DSDA)が好適なものとして例示される。 Among these, pyromellitic dianhydride (PMDA), 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride (BPDA), 3,3 ′, 4,4′-benzophenone tetracarboxylic acid Anhydride (BTDA), 3,3 ′, 4,4′-diphenylsulfone tetracarboxylic dianhydride (DSDA) is exemplified as a preferable one.
ポリイミド樹脂層(A)を構成するポリイミド樹脂原料となるジアミン及び酸無水物としては、上記一般式(1)、(2)及び(3)の説明から理解されるが、ジアミンとしてはTPE−R、APB、4,4’−DAPE等があり、酸無水物としてはPMDAがある。そして、ポリイミド樹脂層(A)を構成するポリイミド樹脂原料となるジアミン及び酸無水物は、上記式及びモル比を満足する限り、2又は4以上のジアミン及び酸無水物を使用してもよく、他のジアミン及び酸無水物を使用してもよい。 As a diamine and an acid anhydride as a polyimide resin raw material constituting the polyimide resin layer (A), it can be understood from the explanation of the above general formulas (1), (2) and (3). , APB, 4,4′-DAPE, etc., and PMDA is an acid anhydride. And, the diamine and acid anhydride as the polyimide resin raw material constituting the polyimide resin layer (A) may use two or more diamines and acid anhydrides as long as the above formula and molar ratio are satisfied, Other diamines and acid anhydrides may be used.
ポリイミド樹脂の分子量は、原料のジアミンと酸無水物のモル比で主に制御可能である。ポリイミド樹脂層(A)を構成するポリイミド樹脂は、その前駆体(溶液)を、イミド化することにより得られる。そして、他のポリイミド樹脂層として良接着性のポリイミド樹脂層を使用する場合は、この他のポリイミド樹脂層は有利には、金属層と接するように設け、ポリイミド樹脂層(A)は他のポリイミド樹脂層と接するように設けることがよい。ポリイミド樹脂層(A)を2種以上使用する場合も、相対的に良接着性のポリイミド樹脂層(A)を金属層と接するように設けることがよい。 The molecular weight of the polyimide resin can be mainly controlled by the molar ratio of the raw material diamine and acid anhydride. The polyimide resin constituting the polyimide resin layer (A) can be obtained by imidizing the precursor (solution). And when using a polyimide resin layer with good adhesion as the other polyimide resin layer, this other polyimide resin layer is advantageously provided in contact with the metal layer, and the polyimide resin layer (A) is another polyimide resin layer. It is preferable to be provided so as to be in contact with the resin layer. Even when two or more types of polyimide resin layers (A) are used, it is preferable to provide a relatively good adhesive polyimide resin layer (A) in contact with the metal layer.
金属層は、銅、アルミニウム、鉄、銀、パラジウム、ニッケル、クロム、モリブデン、タングステン、亜鉛及びそれらの合金等の導電性金属を挙げることができ、これらの中でもステンレス、銅箔又は銅を90%以上含む合金銅箔が好ましい。金属層のポリイミド樹脂と接している面の表面粗さ(Rz)は、3.5μm以下であることが好ましく、1.5μm以下の電解銅箔がより好ましい。フレキシブル配線基板用積層体用の金属層としては、銅箔又は銅を90%以上含む合金銅箔が好ましく、HDDサスペンション用積層体の金属層としては、一方の面がステンレス箔で、他方の面が銅箔又は銅を90%以上含む合金銅箔であることが好ましい。 Examples of the metal layer include conductive metals such as copper, aluminum, iron, silver, palladium, nickel, chromium, molybdenum, tungsten, zinc, and alloys thereof. Among these, 90% of stainless steel, copper foil, or copper is used. The alloy copper foil containing above is preferable. The surface roughness (Rz) of the surface in contact with the polyimide resin of the metal layer is preferably 3.5 μm or less, and more preferably an electrolytic copper foil of 1.5 μm or less. The metal layer for the flexible printed circuit board laminate is preferably a copper foil or an alloy copper foil containing 90% or more of copper. The metal layer of the HDD suspension laminate is a stainless steel foil on the other side. Is preferably a copper foil or an alloy copper foil containing 90% or more of copper.
ポリイミド樹脂層を複数層とする場合、ポリイミド樹脂層(A)以外の樹脂層は、ポリイミド樹脂層(A)の少なくとも一方の面に隣接して設けることが好ましい。ポリイミド樹脂層(A)を(A)層、ポリイミド樹脂層(A)以外の他のポリイミド樹脂層を(II)層、金属層をM層と表した場合、本発明の好ましいフレキシブル配線基板用積層体の好ましい積層順としては、次のような構造が例示される。 When a plurality of polyimide resin layers are used, the resin layers other than the polyimide resin layer (A) are preferably provided adjacent to at least one surface of the polyimide resin layer (A). When the polyimide resin layer (A) is represented as (A) layer, the polyimide resin layer other than the polyimide resin layer (A) is represented as (II) layer, and the metal layer is represented as M layer, the preferred laminate for flexible wiring board of the present invention Examples of preferable stacking order of the body include the following structures.
M層/(A)層
M層/(A)層/(II)層
M層/(II)層/(A)層
M層/(II)層/(A)層/(II)層
M層/(A)層/(A)層/(A)層
M層/(A)層/(II)層/(A)層
M層/(A)層/(II)層/M層
M層/(II)層/(A)層/(II)層/M層
M layer / (A) layer
M layer / (A) layer / (II) layer
M layer / (II) layer / (A) layer
M layer / (II) layer / (A) layer / (II) layer
M layer / (A) layer / (A) layer / (A) layer
M layer / (A) layer / (II) layer / (A) layer
M layer / (A) layer / (II) layer / M layer
M layer / (II) layer / (A) layer / (II) layer / M layer
本発明では、上記M層/(A)層/(A)層/(A)層の様に、一般式(1)、(2)及び(3)の範囲で構造単位の種類又はモル比等を変えた複数種のポリイミド樹脂層(A)を複数層設けたものであってもよい。このように積層構成を工夫することで、実装時に要求される耐熱性とスプロケットホールの破断などのしにくい、COF用途により適した積層体とすることができる。なお、HDDサスペンション用積層体である場合は、好ましくは両面がM層となる。 In the present invention, as in the case of the above-mentioned M layer / (A) layer / (A) layer / (A) layer, the type or molar ratio of the structural unit, etc. within the range of the general formulas (1), (2) and (3) A plurality of different types of polyimide resin layers (A) may be provided. Thus, by devising the laminated structure, it is possible to obtain a laminated body that is more suitable for COF applications, which is resistant to heat resistance and sprocket hole breakage required during mounting. In the case of the HDD suspension laminate, preferably both sides are M layers.
金属層上へのポリイミド樹脂の形成は、ポリイミド前駆体状態で金属箔上に直接塗布して形成することが好ましく、この際、重合された樹脂粘度を500〜70000cpsの範囲とすることが好ましい。ポリイミド絶縁層を複数層とする場合、異なる構成成分からなるポリイミド前駆体樹脂の上に他のポリイミド前駆体樹脂を順次塗布して形成することができる。ポリイミド絶縁層が3層以上からなる場合、同一の構成のポリイミド前駆体樹脂を2回以上使用してもよい。なお、樹脂溶液の塗布面となる金属層表面に対して適宜表面処理した後に塗布を行ってもよい。 Formation of the polyimide resin on the metal layer is preferably performed by directly applying the polyimide resin on the metal foil in a polyimide precursor state, and in this case, the polymerized resin viscosity is preferably in the range of 500 to 70000 cps. When making a polyimide insulating layer into multiple layers, it can form by apply | coating another polyimide precursor resin sequentially on the polyimide precursor resin which consists of a different structural component. When the polyimide insulating layer is composed of three or more layers, the polyimide precursor resin having the same configuration may be used twice or more. In addition, you may apply | coat, after surface-treating suitably with respect to the metal layer surface used as the application surface of a resin solution.
本発明の配線基板用積層体は、上記したように金属箔上にポリイミド前駆体樹脂を塗布することにより製造することができるが、1層以上のポリイミドフィルムを銅箔にラミネートして製造することもできる。このように製造された配線基板用積層体は金属箔を片面のみに有する片面配線基板用積層体としてもよく、また、金属箔を両面に有する両面配線基板用積層体とすることもできる。これら配線基板用積層体において、金属箔に銅箔を使用したものは、それぞれ片面銅張積層板、両面銅張積層板と呼ばれている。両面配線基板用積層体は、片面配線基板用積層体を形成後、金属箔を熱プレスにより圧着する方法、2枚の金属箔層間にポリイミドフィルムを挟み熱プレスにより圧着する方法等によって得ることができる。本発明の配線基板用積層体がフレキシブル配線基板用積層体である場合は、片面銅張積層板、両面銅張積層板等が適する。HDDサスペンション用積層体である場合は、片面を銅箔等の導体層とし、他の面をステンレス箔等の弾性体金属層とした両面配線基板用積層体が適する。なお、配線基板用積層体からフレキシブル配線基板又はHDDサスペンションを製造する方法は公知である。例えば、金属箔層をエッチングして所定の回路を形成する方法がある。 The laminate for a wiring board of the present invention can be produced by applying a polyimide precursor resin on a metal foil as described above, but it is produced by laminating one or more layers of polyimide film on a copper foil. You can also. The laminated body for a wiring board thus manufactured may be a laminated body for a single-sided wiring board having a metal foil only on one side, or may be a laminated body for a double-sided wiring board having a metal foil on both sides. Of these laminates for wiring boards, those using copper foil as the metal foil are called a single-sided copper-clad laminate and a double-sided copper-clad laminate, respectively. The double-sided wiring board laminate can be obtained by forming a single-sided wiring board laminate and then crimping the metal foil by hot pressing, sandwiching a polyimide film between two metal foil layers, and crimping by hot pressing. it can. When the laminate for a wiring board of the present invention is a laminate for a flexible wiring board, a single-sided copper-clad laminate, a double-sided copper-clad laminate, etc. are suitable. In the case of a laminate for HDD suspension, a laminate for a double-sided wiring board in which one side is a conductor layer such as copper foil and the other side is an elastic metal layer such as stainless steel foil is suitable. A method for manufacturing a flexible wiring board or an HDD suspension from a wiring board laminate is known. For example, there is a method of forming a predetermined circuit by etching a metal foil layer.
ポリイミド樹脂層には、本発明の目的を損なわない範囲で各種充填剤や添加剤を含有させてもよい。 The polyimide resin layer may contain various fillers and additives as long as the object of the present invention is not impaired.
本発明のフレキシブル配線基板用積層体は、COF用途に適している。本発明のCOF用フレキシブル配線基板は、上記フレキシブル配線基板用積層体を、配線加工して得られるフレキシブル配線基板の端部に所望形状のスプロケットホールを設けてなる。 The laminate for a flexible wiring board of the present invention is suitable for COF applications. The flexible wiring board for COF of the present invention is provided with a sprocket hole having a desired shape at the end of a flexible wiring board obtained by wiring the above-mentioned laminate for flexible wiring board.
COF用フレキシブル配線基板の一例をその平面図を示す図1により説明する。COF用フレキシブル配線基板1とする手段は特に限定されるものではないが、ポリイミド樹脂層と金属箔からなる積層体の両側端に一定間隔でスプロケットホール2を形成し、任意の配線回路を形成し、ソルダーレジスト層を形成する方法が一般的である。
An example of the flexible wiring board for COF will be described with reference to FIG. The means for making the
具体的には、まず、フレキシブル配線基板用積層体を所定幅(例えば、35mm)にスリットしテープ状にし、幅方向に対してその両側端部にスプロケットホール2を開孔する。開孔は、通常金型により所望の形状に空けられる。その一例としては、一辺が1.98mmの正方形の孔を4.75mm間隔に空けたものが挙げられる。次に、感光性樹脂の塗布、写真法による感光性樹脂層のパターニング、酸による導体層のエッチング、感光性樹脂層の剥離により導体のパターニングを行い、パターニングされた導体上に、更に無電解すずめっき、無電解ニッケル−金めっき、無電解ニッケル−金めっきなどのめっき処理を行い、永久レジストにより導体層のカバーを施すことでCOF用フレキシブル配線基板を得ることができる。
Specifically, first, the laminate for a flexible wiring board is slit to a predetermined width (for example, 35 mm) to form a tape, and
このようにして得られたフレキシブル配線基板はポリイミド基材の上に所定の配線回路パターンを有し、銅箔の表面はめっきにより覆われ、更にコネクションに必要な部分以外の導体は絶縁体で保護されている。また、COF用のフレキシブル配線基板はテープ状の形態を示し、その両側端部には搬送用のスプロケットホールを有する。このCOF用のフレキシブル配線基板には、液晶駆動用のIC等の半導体が実装され、絶縁性の樹脂で封止され、半導体毎の個片に分割され、液晶パネルなどに接続される。これらの工程において、スプロケットホールに鎖歯車、いわゆるスプロケットを組み合わせてテープ搬送を行なう。この際に、スプロケット部分の強度が不足すると、スプロケットホールからテープの切断が発生する問題が生じる。 The flexible wiring board thus obtained has a predetermined wiring circuit pattern on the polyimide substrate, the surface of the copper foil is covered with plating, and conductors other than those necessary for connection are protected with an insulator. Has been. Further, the flexible wiring board for COF has a tape-like form, and has sprocket holes for conveyance at both ends. A semiconductor such as an IC for driving liquid crystal is mounted on the flexible wiring board for COF, sealed with an insulating resin, divided into individual pieces for each semiconductor, and connected to a liquid crystal panel or the like. In these processes, tape transport is performed by combining a sprocket hole with a chain gear, so-called sprocket. At this time, if the strength of the sprocket portion is insufficient, there arises a problem that the tape is cut from the sprocket hole.
本発明によれば、配線基板用積層体を構成する絶縁層のポリイミド樹脂の耐熱性が高く、寸法安定性に優れたものであるばかりでなく、強靭でもあることから、ポリイミド樹脂層の厚みを薄くすることができ、耐屈曲性の優れたフレキシブル配線基板用積層体とすることができる。したがって、特にスプロケットホールなどの破断、変形が問題とされやすいCOF用途に適して用いることができる。また、本発明の配線基板用積層体に用いられるポリイミド樹脂層はエッチング特性も良好であることから、HDDサスペンション用積層体としても好適に使用される。 According to the present invention, since the polyimide resin of the insulating layer constituting the laminate for a wiring board is not only high in heat resistance and excellent in dimensional stability but also tough, the thickness of the polyimide resin layer is reduced. It can be made thin and it can be set as the laminated body for flexible wiring boards excellent in bending resistance. Therefore, it can be used particularly suitable for COF applications where breakage and deformation of sprocket holes and the like are likely to be problematic. Further, since the polyimide resin layer used in the laminate for a wiring board of the present invention has good etching characteristics, it is also suitably used as a laminate for an HDD suspension.
以下、実施例に基づいて、本発明の内容を具体的に説明するが、本発明はこれらの実施
例の範囲に限定されるものではない。
Hereinafter, the content of the present invention will be specifically described based on examples, but the present invention is not limited to the scope of these examples.
実施例等に用いた略号を下記に示す。
・PMDA :ピロメリット酸二無水物
・BPDA :3,3',4,4'-ビフェニルテトラカルボン酸二無水物
・BTDA :3,3',4,4'-ベンゾフェノンテトラカルボン酸二無水物
・TPE-R :1,3-ビス(4-アミノフェノキシ)ベンゼン
・APB :1,3-ビス(3-アミノフェノキシ)ベンゼン
・m-TB :2,2'-ジメチルベンジジン
・PDA :1,4-ジアミノベンゼン
・BAPP :2,2-ビス(4-アミノフェノキシフェニル)プロパン
・NBOA :2,7-ビス(4-アミノフェノキシ)ナフタレン
・3,4'-DAPE:3,4'-ジアミノジフェニルエーテル
・4,4'-DAPE:4,4'-ジアミノジフェニルエーテル
・DANPG:1,3-ビス(4-アミノフェノキシ)-2,2-ジメチルプロパン
・DMAc :N,N-ジメチルアセトアミド
Abbreviations used in Examples and the like are shown below.
-PMDA: pyromellitic dianhydride-BPDA: 3,3 ', 4,4'-biphenyltetracarboxylic dianhydride-BTDA: 3,3', 4,4'-benzophenone tetracarboxylic dianhydride TPE-R: 1,3-bis (4-aminophenoxy) benzene, APB: 1,3-bis (3-aminophenoxy) benzene, m-TB: 2,2'-dimethylbenzidine, PDA: 1,4- Diaminobenzene, BAPP: 2,2-bis (4-aminophenoxyphenyl) propane, NBOA: 2,7-bis (4-aminophenoxy) naphthalene, 3,4'-DAPE: 3,4'-diaminodiphenyl ether, 4 , 4'-DAPE: 4,4'-diaminodiphenyl ether, DANPG: 1,3-bis (4-aminophenoxy) -2,2-dimethylpropane, DMAc: N, N-dimethylacetamide
また、実施例中の各種物性の測定方法と条件を以下に示す。なお、以下ポリイミドフィルムと表現したものは、配線基板用積層体(以下、CCLともいう)の銅箔をエッチング除去して得られたポリイミドフィルムを指す。 In addition, measurement methods and conditions for various physical properties in the examples are shown below. In addition, what was expressed as a polyimide film below refers to the polyimide film obtained by etching away the copper foil of the laminated body for wiring boards (henceforth CCL).
[引き裂き伝播抵抗の測定]
63.5mm×50mmの試験片を準備し、試験片に長さ12.7mmの切り込みを入れ、東洋精機社製の軽荷重引き裂き試験機を用い測定した。なお、CCL引き裂き伝播抵抗とは金属層とポリイミド樹脂層とからなるCCLについて測定したものを指し、PI引き裂き伝播抵抗とはCCLの銅箔をエッチング除去して得られたポリイミドフィルムについて測定したものを指す。また、ポリイミドフィルムは、CCLの銅箔をエッチング除去して得られたポリイミドフィルムを指す。
[Measurement of tear propagation resistance]
A test piece of 63.5 mm × 50 mm was prepared, a cut of 12.7 mm in length was put into the test piece, and measurement was performed using a light load tear tester manufactured by Toyo Seiki Co., Ltd. In addition, CCL tear propagation resistance refers to that measured for CCL consisting of a metal layer and a polyimide resin layer, and PI tear propagation resistance refers to that measured for a polyimide film obtained by etching away the CCL copper foil. Point to. Moreover, a polyimide film points out the polyimide film obtained by etching away the copper foil of CCL.
[熱膨張係数(CTE)の測定]
ポリイミドフィルム(3mm×15mm)を、熱機械分析(TMA)装置にて5.0gの荷重を加えながら20℃/minの昇温速度で30℃から260℃の温度範囲で引張り試験を行った。温度に対するポリイミドフィルムの伸び量から熱膨張係数を測定した。
[Measurement of coefficient of thermal expansion (CTE)]
The polyimide film (3 mm × 15 mm) was subjected to a tensile test in a temperature range of 30 ° C. to 260 ° C. at a temperature increase rate of 20 ° C./min while applying a 5.0 g load with a thermomechanical analysis (TMA) apparatus. The thermal expansion coefficient was measured from the amount of elongation of the polyimide film with respect to temperature.
[ガラス転移温度(Tg)、貯蔵弾性率(E')]
ポリイミドフィルム(10mm×22.6 mm)をDMAにて20℃から500℃まで5℃/分で昇温させたときの動的粘弾性を測定し、ガラス転移温度Tg(tanδ極大値)及び400℃の貯蔵弾性率(E')を求めた。
[Glass transition temperature (Tg), storage elastic modulus (E ′)]
The dynamic viscoelasticity when a polyimide film (10 mm × 22.6 mm) was heated from 20 ° C. to 500 ° C. at 5 ° C./min was measured by DMA, and the glass transition temperature Tg (tan δ maximum value) and 400 were measured. The storage elastic modulus (E ′) at 0 ° C. was determined.
[接着強度の測定]
接着力は、テンションテスターを用い、幅1mmのCCLの樹脂側を両面テープによりアルミ板に固定し、銅を180°方向に50mm/minの速度で剥離してピール強度を求めた。
[Measurement of adhesive strength]
The adhesive strength was determined by using a tension tester, fixing the resin side of a CCL having a width of 1 mm to an aluminum plate with a double-sided tape, and peeling the copper in a 180 ° direction at a speed of 50 mm / min to obtain the peel strength.
[接着強度の測定(ステンレス箔)]
接着力は、テンションテスターを用い、幅1mmの積層体の樹脂側を両面テープによりアルミ板に固定し、ステンレス箔を90°方向に50mm/minの速度で剥離してピール強度を求めた。
[Measurement of adhesive strength (stainless steel foil)]
The adhesion strength was determined by using a tension tester to fix the resin side of the 1 mm wide laminate to the aluminum plate with double-sided tape, and peeling the stainless steel foil in the 90 ° direction at a speed of 50 mm / min to obtain the peel strength.
[PIエッチング速度]
エッチング速度は金属箔上にポリイミド層を形成した積層体を用い、基準エッチング液(エチレンジアミン11.0wt%、エチレングリコール22.0wt%、水酸化カリウム33.5wt%の水溶液)を用いて測定する。測定は、まず、金属箔上にポリイミド層を形成した積層体全体の厚みを測定し、次いで金属箔を残したままの状態で、80℃の上記基準エッチング液に浸漬してポリイミド樹脂が全てなくなる時間を測定し、初期の厚みをエッチングに要した時間で割った値をエッチング速度とした。
[PI etching rate]
The etching rate is measured using a laminate in which a polyimide layer is formed on a metal foil and using a reference etching solution (aqueous solution of 11.0 wt% ethylenediamine, 22.0 wt% ethylene glycol, 33.5 wt% potassium hydroxide). In the measurement, first, the thickness of the entire laminate in which the polyimide layer is formed on the metal foil is measured, and then the polyimide resin is completely removed by immersing in the reference etching solution at 80 ° C. while leaving the metal foil. The time was measured, and the value obtained by dividing the initial thickness by the time required for etching was defined as the etching rate.
[吸湿率の測定]
ポリイミドフィルム(4cm×20cm)を、120℃で2時間乾燥した後、23℃/50%RHの恒温恒湿機で24時間静置し、その前後の重量変化から次式により求めた。
吸湿率(%)=[(吸湿後重量−乾燥後重量)/乾燥後重量]×100
[Measurement of moisture absorption rate]
A polyimide film (4 cm × 20 cm) was dried at 120 ° C. for 2 hours, and then allowed to stand for 24 hours in a constant temperature and humidity chamber of 23 ° C./50% RH.
Moisture absorption rate (%) = [(weight after moisture absorption−weight after drying) / weight after drying] × 100
[湿度膨張係数(CHE)の測定]
35cm×35cmのポリイミド/銅箔積層体の銅箔上に、エッチングレジスト層を設け、これを一辺が30cmの正方形の四辺に10cm間隔で直径1mmの点が16箇所配置するパターンに形成した。エッチングレジスト開孔部の銅箔露出部分をエッチングし、16箇所の銅箔残存点を有するCHE測定用ポリイミドフィルムを得た。このフィルムを120℃で2時間乾燥した後、23℃/30%RH・50%RH・70%RHの恒温恒湿機で各湿度において24時間静置し、二次元測長機により測定した各湿度での銅箔点間の寸法変化から湿度膨張係数(ppm/%RH)を求めた。
[Measurement of humidity expansion coefficient (CHE)]
An etching resist layer was provided on a copper foil of a polyimide / copper foil laminate of 35 cm × 35 cm, and this was formed into a pattern in which 16 points with a diameter of 1 mm were arranged at intervals of 10 cm on four sides of a square with a side of 30 cm. The exposed portion of the copper foil in the opening portion of the etching resist was etched to obtain a CHE measurement polyimide film having 16 copper foil remaining points. After drying this film at 120 ° C. for 2 hours, each film was allowed to stand for 24 hours at 23 ° C./30% RH / 50% RH / 70% RH constant temperature and humidity at 24 ° C. and measured with a two-dimensional measuring machine. The humidity expansion coefficient (ppm /% RH) was determined from the dimensional change between the copper foil points at humidity.
[MIT耐折性の評価]
東洋精機製作所社製のMIT耐揉疲労試験機DA型を用い、試験を行った。CCLを幅15mm、長さ130mm以上の短冊状サイズにカットし、L/S=150/200μmのパターンに回路加工し、屈曲回数を測定した。なお、測定条件は荷重500g、屈曲角度270℃、屈曲速度175rpm、屈曲半径R=0.8mmとした。
[Evaluation of MIT folding resistance]
The test was conducted using an MIT fatigue resistance tester DA type manufactured by Toyo Seiki Seisakusho. The CCL was cut into a strip size having a width of 15 mm and a length of 130 mm or more, processed into a pattern of L / S = 150/200 μm, and the number of bendings was measured. The measurement conditions were a load of 500 g, a bending angle of 270 ° C., a bending speed of 175 rpm, and a bending radius R = 0.8 mm.
[搬送性評価]
スプロケットホールの変形による搬送性評価は、CCLを35mm幅にスリットしテープ状にし、両側端部にTABテープ用スプライサーを用いて35super規格のスプロケットホールを形成して行った。ここで、スプロケットホールのホールピッチは4.75mm、ホール形状は一辺が1.42mmの正方形、テープエッジからホール中心線までの距離は0.6mmとした。そして、このスプロケットホール付きテープの銅箔部を塩化第二鉄溶液で除去し、スプロケットホール付きポリイミドフィルムテープを得、OLBボンダーにてロール・トゥ・ロールでの搬送試験を行った。○は良好、×は不良を示す。
[Transportability evaluation]
The evaluation of the transportability by deformation of the sprocket hole was performed by slitting the CCL to a width of 35 mm to form a tape, and forming a 35super standard sprocket hole using a TAB tape splicer at both ends. Here, the hole pitch of the sprocket holes was 4.75 mm, the hole shape was a square with a side of 1.42 mm, and the distance from the tape edge to the hole center line was 0.6 mm. And the copper foil part of this tape with a sprocket hole was removed with the ferric chloride solution, the polyimide film tape with a sprocket hole was obtained, and the conveyance test by the roll to roll was done with the OLB bonder. ○ indicates good and × indicates poor.
[PIエッチング形状]
ステンレス箔上に絶縁層を有する積層体に電解銅箔(厚み12μm、表面粗さRz0.7)を絶縁層の上に重ね合わせ、真空プレス機を用いて、面圧15Mpa、温度320℃、プレス時間20分の条件で加熱圧着した。次に、この積層体の銅箔面にエッチングレジスト層を公知の方法にて形成せしめた後、塩化第二鉄水溶液に38℃で20秒間浸漬して銅箔を選択的に除去した後、この銅箔をエッチングマスクとして露出したポリイミド樹脂層をエチレンジアミン11.0wt%、エチレングリコール22.0wt%及び水酸化カリウム33.5wt%を含有するエッチング水溶液に浸漬して所定のパターンとなるようにエッチングを行い、顕微鏡でエッチング後の形状を観察した。
[PI etching shape]
An electrolytic copper foil (thickness 12 μm, surface roughness Rz0.7) is superimposed on the insulating layer on the laminate having the insulating layer on the stainless steel foil, and the surface pressure is 15 Mpa, the temperature is 320 ° C., using a vacuum press. Thermocompression bonding was performed for 20 minutes. Next, after an etching resist layer was formed on the copper foil surface of the laminate by a known method, the copper foil was selectively removed by immersing in an aqueous ferric chloride solution at 38 ° C. for 20 seconds. The exposed polyimide resin layer with the copper foil as an etching mask is immersed in an etching aqueous solution containing 11.0 wt% ethylenediamine, 22.0 wt% ethylene glycol, and 33.5 wt% potassium hydroxide so as to form a predetermined pattern. The shape after etching was observed with a microscope.
合成例1〜13
ポリイミド前駆体樹脂A2〜M2を合成するため、窒素気流下で、表1に示したジアミンを500mlのセパラブルフラスコの中で攪拌しながら溶剤DMAc約200〜300gに溶解させた。次いで、表1に示したテトラカルボン酸二無水物を加えた。その後、溶液を室温で4時間攪拌を続けて重合反応を行い、ポリイミド前駆体樹脂(ポリアミック酸)A2〜M2の黄〜茶褐色の粘稠な溶液を得た。それぞれのポリイミド前駆体樹脂溶液の25℃での粘度を測定し、表1にまとめた。なお、粘度は、恒温水槽付のコーンプレート式粘度計(トキメック社製)にて、25℃で測定した。また、GPCによる測定した重量平均分子量(Mw)を表8に示した。表1中、ジアミン及びテトラカルボン酸二無水物の使用量の単位はgである。
Synthesis Examples 1-13
In order to synthesize the polyimide precursor resins A 2 to M 2 , the diamines shown in Table 1 were dissolved in about 200 to 300 g of the solvent DMAc while stirring in a 500 ml separable flask under a nitrogen stream. Subsequently, the tetracarboxylic dianhydride shown in Table 1 was added. Thereafter, the solution was stirred at room temperature for 4 hours to carry out a polymerization reaction to obtain a yellow-brown viscous solution of polyimide precursor resin (polyamic acid) A 2 to M 2 . The viscosity at 25 ° C. of each polyimide precursor resin solution was measured and summarized in Table 1. The viscosity was measured at 25 ° C. with a cone plate viscometer (manufactured by Tokimec Co., Ltd.) equipped with a constant temperature water bath. Table 8 shows the weight average molecular weight (Mw) measured by GPC. In Table 1, the unit of the amount of diamine and tetracarboxylic dianhydride used is g.
実施例1〜6
A2〜F2のポリイミド前駆体樹脂の溶液を、それぞれ銅箔A(厚さ12μmの電解銅箔、表面粗さRz:0.7μm)上にアプリケータを用いて塗布し、50〜130℃で2〜60分間乾燥した後、更に130℃、160℃、200℃、230℃、280℃、320℃、360℃で各2〜30分段階的な熱処理を行い、銅箔上にポリイミド層を形成して、CCLを得た。
Examples 1-6
A polyimide precursor resin solution of A 2 to F 2 was applied on copper foil A (12 μm thick electrolytic copper foil, surface roughness Rz: 0.7 μm) using an applicator, and 50 to 130 ° C. Then, heat treatment is performed at 130 ° C., 160 ° C., 200 ° C., 230 ° C., 280 ° C., 320 ° C., and 360 ° C. for 2 to 30 minutes each to form a polyimide layer on the copper foil. To obtain CCL.
塩化第二鉄水溶液を用いて銅箔をエッチング除去してポリイミドフィルムA2〜F2を作成し、引裂き伝播抵抗、熱膨張係数(CTE)、ガラス転移温度(Tg)、400℃での貯蔵弾性率(E’)、180度ピール強度、PIエッチング速度、吸湿率を求めた。
なお、ポリイミドフィルムA2〜F2のポリイミドは、対応するポリイミド前駆体A2〜F2から得られたことを意味する。
Copper foil is removed by etching using ferric chloride aqueous solution to prepare polyimide films A 2 to F 2 , tear propagation resistance, coefficient of thermal expansion (CTE), glass transition temperature (Tg), storage elasticity at 400 ° C. The rate (E ′), 180 degree peel strength, PI etching rate, and moisture absorption were determined.
Incidentally, the polyimide of the polyimide film A 2 to F 2 means that obtained from the corresponding polyimide precursor A 2 to F 2.
比較例1〜4
ポリイミド前駆体樹脂としてG2〜I2及びM2を使用した以外は、実施例1と同様にして、ポリイミドフィルムG2〜I2及びM2を作成し、物性を測定した。ポリイミドフィルムA2〜I2及びM2の特性を表2に示す。
Comparative Examples 1-4
Except that G 2 to I 2 and M 2 were used as the polyimide precursor resin, polyimide films G 2 to I 2 and M 2 were prepared and measured for physical properties in the same manner as in Example 1. Table 2 shows the characteristics of the polyimide films A 2 to I 2 and M 2 .
実施例7
銅箔Aを使用し、この銅箔上に合成例10で調製したポリイミド前駆体樹脂J2の溶液を硬化後の厚みが1.9μmの厚みになるように均一に塗布し、130℃で加熱乾燥し溶剤を除去した。次に、その上に合成例1で調製したポリイミド前駆体樹脂A2の溶液を硬化後の厚みが21μmの厚みになるように均一に塗布し、70〜130℃で加熱乾燥し溶剤を除去した。更に、その上にポリイミド前駆体樹脂J2の溶液を硬化後の厚みが2.1μmの厚みになるように均一に塗布し、140℃で加熱乾燥し溶剤を除去した。この後、130℃、160℃、200℃、230℃、280℃、320℃、360℃で各2〜30分段階的な熱処理によりイミド化を行い、3層のポリイミド樹脂層からなる合計厚み25μmの絶縁樹脂層が銅箔上に形成された積層体を得た。銅箔上の各ポリイミド樹脂層の厚みは、J2/A2/J2の順に、1.9μm/21μm/2.1μmである。その後、過酸化水素/硫酸系のエッチング液を用いて銅箔を8μmの厚さになるまでエッチングし、CCLとしての積層体(M8)を得た。
Example 7
Using the copper foil A, a solution of the polyimide precursor resin J 2 prepared in Synthesis Example 10 thickness after curing is uniformly coated to a thickness of 1.9μm on the copper foil, heating at 130 ° C. Dry and remove the solvent. Next, the solution of the polyimide precursor resin A 2 prepared in Synthesis Example 1 was uniformly applied thereon so that the thickness after curing was 21 μm, and the solvent was removed by heating at 70 to 130 ° C. . Further, a solution of the polyimide precursor resin J 2 was uniformly applied thereon so that the thickness after curing was 2.1 μm, and dried by heating at 140 ° C. to remove the solvent. Thereafter, imidization is performed by stepwise heat treatment at 130 ° C., 160 ° C., 200 ° C., 230 ° C., 280 ° C., 320 ° C., and 360 ° C. for 2 to 30 minutes each, and the total thickness of three polyimide resin layers is 25 μm. The laminated body in which the insulating resin layer was formed on the copper foil was obtained. The thickness of each polyimide resin layer on the copper foil is 1.9 μm / 21 μm / 2.1 μm in the order of J 2 / A 2 / J 2 . Thereafter, the copper foil was etched to a thickness of 8 μm using a hydrogen peroxide / sulfuric acid based etchant to obtain a laminate (M8) as CCL.
実施例8
合成例10で調製したポリイミド前駆体樹脂J2に代えて、合成例12で調製したポリイミド前駆体樹脂L2を使用した以外は、実施例7と同様に行い、3層のポリイミド樹脂層からなる合計厚み25μmの絶縁樹脂層が銅箔上に形成された積層体を得た。銅箔上の各ポリイミド樹脂層の厚みは、L2/A2/L2の順に、1.9μm/21μm/2.1μmである。その後、過酸化水素/硫酸系のエッチング液を用いて銅箔を8μmの厚さになるまでエッチングし、積層体(M9)を得た。
Example 8
Instead of the polyimide precursor resin J 2 prepared in Synthesis Example 10, except for using a polyimide precursor resin L 2 prepared in Synthesis Example 12 were performed in the same manner as in Example 7, made of a polyimide resin layer of 3-layer A laminated body in which an insulating resin layer having a total thickness of 25 μm was formed on a copper foil was obtained. The thickness of each polyimide resin layer on the copper foil is 1.9 μm / 21 μm / 2.1 μm in the order of L 2 / A 2 / L 2 . Thereafter, the copper foil was etched to a thickness of 8 μm using a hydrogen peroxide / sulfuric acid based etching solution to obtain a laminate (M9).
実施例9
銅箔Aを使用し、この銅箔上に合成例1で調製したポリイミド前駆体樹脂A2の溶液を硬化後の厚みが23μmの厚みになるように均一に塗布し、70〜130℃で加熱乾燥し溶剤を除去した。次に、その上に合成例11で調製したポリイミド前駆体樹脂K2の溶液を硬化後の厚みが2μmの厚みになるように均一に塗布し、140℃で加熱乾燥し溶剤を除去した。この後、室温から360℃まで約5hrかけて熱処理しイミド化させ、2層のポリイミド樹脂層からなる合計厚み25μmの絶縁樹脂層が銅箔上に形成された積層体を得た。銅箔上の各ポリイミド樹脂層の厚みは、A2/K2の順に、23μm/2μmである。その後、過酸化水素/硫酸系のエッチング液を用いて銅箔を8μmの厚さになるまでエッチングし、積層体(M10)を得た。
Example 9
Using copper foil A, uniformly apply the solution of polyimide precursor resin A 2 prepared in Synthesis Example 1 on this copper foil so that the thickness after curing is 23 μm, and heat at 70 to 130 ° C. Dry and remove the solvent. Next, a solution of the polyimide precursor resin K 2 prepared in Synthesis Example 11 was uniformly applied thereon so that the thickness after curing was 2 μm, and the solvent was removed by heating and drying at 140 ° C. Then, it heat-processed over about 5 hours from room temperature to 360 degreeC, and it imidated, and obtained the laminated body in which the insulating resin layer of the total thickness of 25 micrometers which consists of two polyimide resin layers was formed on copper foil. The thickness of each polyimide resin layer on the copper foil is 23 μm / 2 μm in the order of A 2 / K 2 . Thereafter, the copper foil was etched to a thickness of 8 μm using a hydrogen peroxide / sulfuric acid based etching solution to obtain a laminate (M10).
比較例5
銅箔Aを使用し、この銅箔上に合成例13で調製したポリイミド前駆体樹脂M2の溶液を均一に塗布し、この後、130℃、160℃、200℃、230℃、280℃、320℃、360℃で各2〜30分段階的な熱処理によりイミド化を行い、厚み38μmの絶縁樹脂層が銅箔上に形成された積層体を得た。その後、その後、過酸化水素/硫酸系のエッチング液を用いて銅箔を8μmの厚さになるまでエッチングし、積層体(M11)を得た。特性評価結果を表3に示す。
Comparative Example 5
Using the copper foil A, a solution of the polyimide precursor resin M 2 prepared in Synthesis Example 13 was uniformly coated on the copper foil, thereafter, 130 ℃, 160 ℃, 200 ℃, 230 ℃, 280 ℃, Imidization was performed by stepwise heat treatment at 320 ° C. and 360 ° C. for 2 to 30 minutes to obtain a laminate in which an insulating resin layer having a thickness of 38 μm was formed on the copper foil. Thereafter, the copper foil was etched to a thickness of 8 μm using a hydrogen peroxide / sulfuric acid based etching solution to obtain a laminate (M11). The characteristic evaluation results are shown in Table 3.
実施例7〜9で得られた積層体(M8)〜(M10)は、ポリイミド樹脂層が多層で構成されており、本発明の大きな特徴であるポリイミド樹脂層の引裂き強さと他の諸特性のバランスをポリイミド樹脂層(A)で担保しながら、他の層でカール制御、金属箔との接着性などポリイミド層が単層では制御困難な制御を行っており、特に、約400℃の高温で行われる半導体素子実装時における配線の沈み込みのない、変形もないCOF用フレキシブル配線基板としたものである。表3からも分かるように、積層体(M8)〜(M10)は、高接着強度、高耐熱性、高引裂き伝播抵抗、低吸湿の積層体で、かつ、MIT耐折性も300回以上と高屈曲特性にも優れている。また、スプロケットホールの変形による搬送性評価を行った結果、実施例7〜9は良好な搬送性を示した。比較例5はテープの破断が発生した。 In the laminates (M8) to (M10) obtained in Examples 7 to 9, the polyimide resin layer is composed of multiple layers, and the tear strength of the polyimide resin layer, which is a major feature of the present invention, and other characteristics. While the balance is secured by the polyimide resin layer (A), curling is controlled by other layers, and the polyimide layer is difficult to control such as adhesion to the metal foil, especially at a high temperature of about 400 ° C. This is a flexible wiring board for COF which does not sink and does not deform when the semiconductor element is mounted. As can be seen from Table 3, the laminates (M8) to (M10) are laminates having high adhesive strength, high heat resistance, high tear propagation resistance, low moisture absorption, and MIT folding resistance of 300 times or more. Excellent in high bending properties. Moreover, as a result of carrying out evaluation by the deformation | transformation of a sprocket hole, Examples 7-9 showed favorable conveyance. In Comparative Example 5, the tape was broken.
実施例10〜15
ポリイミド前駆体樹脂A2の溶液を、銅箔A上にアプリケータを用いて各実施例で厚みを変化させて塗布し、50〜130℃で2〜60分間乾燥した後、更に130℃、160℃、200℃、230℃、280℃、320℃、360℃で各2〜30分段階的な熱処理を行い、銅箔上に表4に記載した厚みのポリイミド樹脂層を形成したCCLを得た。
塩化第二鉄水溶液を用いて銅箔をエッチング除去してポリイミドフィルムO〜Tを作成し、引裂き伝播抵抗、熱膨張係数(CTE)、PIエッチング速度、吸湿率を求めた。結果を表4に示す。
Examples 10-15
The polyimide precursor resin A 2 solution was applied onto the copper foil A using an applicator while changing the thickness in each example, dried at 50 to 130 ° C. for 2 to 60 minutes, and then further 130 ° C. and 160 ° C. CCL with a polyimide resin layer having a thickness described in Table 4 formed on a copper foil was obtained by performing stepwise heat treatment at 2 ° C. for 2 to 30 minutes at 200 ° C., 230 ° C., 280 ° C., 320 ° C. and 360 ° C. .
The polyimide foils OT were prepared by etching away the copper foil using a ferric chloride aqueous solution, and the tear propagation resistance, the coefficient of thermal expansion (CTE), the PI etching rate, and the moisture absorption rate were determined. The results are shown in Table 4.
実施例16〜17
ジアミンに対するテトラカルボン酸二無水物のモル比(酸二無水物/ジアミン)を0.990又は0.996とした以外は合成例1と同様にして重量平均分子量(Mw)が異なるポリイミド前駆体樹脂を合成した。これらのポリイミド前駆体樹脂溶液を銅箔A上にアプリケータを用いて塗布し、50〜130℃で2〜60分間乾燥した後、更に130℃、160℃、200℃、230℃、280℃、320℃、360℃で各2〜30分段階的な熱処理を行い、銅箔上にポリイミド層を形成してCCLを得た。
塩化第二鉄水溶液を用いて銅箔をエッチング除去してポリイミドフィルムX、Yを作成し、引裂き伝播抵抗、熱膨張係数(CTE)を求めた。
Examples 16-17
A polyimide precursor resin having a different weight average molecular weight (Mw) as in Synthesis Example 1 except that the molar ratio of tetracarboxylic dianhydride to diamine (acid dianhydride / diamine) was 0.990 or 0.996. Was synthesized. After applying these polyimide precursor resin solutions on copper foil A using an applicator and drying at 50 to 130 ° C. for 2 to 60 minutes, 130 ° C., 160 ° C., 200 ° C., 230 ° C., 280 ° C., Stepwise heat treatment was performed at 320 ° C. and 360 ° C. for 2 to 30 minutes, and a polyimide layer was formed on the copper foil to obtain CCL.
The copper foil was etched away using a ferric chloride aqueous solution to prepare polyimide films X and Y, and the tear propagation resistance and the coefficient of thermal expansion (CTE) were determined.
比較例6
ジアミンに対するテトラカルボン酸二無水物のモル比(酸二無水物/ジアミン)を0.988とした以外は合成例1と同様にしてポリイミド前駆体樹脂を合成した。このポリイミド前駆体樹脂溶液を銅箔A上にアプリケータを用いて塗布し、50〜130℃で2〜60分間乾燥した後、更に130℃、160℃、200℃、230℃、280℃、320℃、360℃で各2〜30分段階的な熱処理を行い、銅箔上にポリイミド層を形成してCCLを得た。
塩化第二鉄水溶液を用いて銅箔をエッチング除去してポリイミドフィルムZを作成し、引裂き伝播抵抗、熱膨張係数(CTE)を求めた。結果を表5に示す。
Comparative Example 6
A polyimide precursor resin was synthesized in the same manner as in Synthesis Example 1 except that the molar ratio of tetracarboxylic dianhydride to diamine (acid dianhydride / diamine) was 0.988. This polyimide precursor resin solution was applied onto copper foil A using an applicator, dried at 50 to 130 ° C. for 2 to 60 minutes, and then further 130 ° C., 160 ° C., 200 ° C., 230 ° C., 280 ° C., 320 CCL was obtained by performing stepwise heat treatment at 360 ° C. for 2 to 30 minutes to form a polyimide layer on the copper foil.
A polyimide film Z was prepared by etching away the copper foil using an aqueous ferric chloride solution, and the tear propagation resistance and the coefficient of thermal expansion (CTE) were determined. The results are shown in Table 5.
実施例18
銅箔B(12μm厚みの圧延銅箔、表面粗さRz:1.0μm)を使用し、この銅箔上に合成例11で調製したポリイミド前駆体樹脂K2の溶液を硬化後の厚みが1.6μmの厚みになるように均一に塗布し、130℃で加熱乾燥し溶剤を除去した。次に、その上に合成例1で調製したポリイミド前駆体樹脂A2の溶液を硬化後の厚みが8.7μmの厚みになるように均一に塗布し、70〜130℃で加熱乾燥し溶剤を除去した。更に、その上にポリイミド前駆体樹脂K2の溶液を硬化後の厚みが1.7μmの厚みになるように均一に塗布し、140℃で加熱乾燥し溶剤を除去した。この後、130℃、160℃、200℃、230℃、280℃、320℃、360℃で各2〜30分段階的な熱処理によりイミド化を行い、3層のポリイミド樹脂層からなる合計厚み12μmの絶縁樹脂層が銅箔上に形成されたCCL(M18)を得た。銅箔上の各ポリイミド樹脂層の厚みは、K2/A2/K2の順に、1.6μm/8.7μm/1.7μmである。
Example 18
Copper foil B (rolled copper foil having a thickness of 12 μm, surface roughness Rz: 1.0 μm) was used, and the thickness of the polyimide precursor resin K 2 prepared in Synthesis Example 11 on this copper foil was 1 after curing. The film was uniformly applied to a thickness of 6 μm and dried by heating at 130 ° C. to remove the solvent. Next, the solution of the polyimide precursor resin A 2 prepared in Synthesis Example 1 on the thickness after curing was uniformly applied so as to have a thickness of 8.7 .mu.m, the solvent was dried by heating at 70 to 130 ° C. Removed. Further, a solution of the polyimide precursor resin K 2 was uniformly applied thereon so that the thickness after curing was 1.7 μm, and the solvent was removed by heating and drying at 140 ° C. Thereafter, imidization is performed by stepwise heat treatment at 130 ° C., 160 ° C., 200 ° C., 230 ° C., 280 ° C., 320 ° C. and 360 ° C. for 2 to 30 minutes each, and the total thickness of three polyimide resin layers is 12 μm. CCL (M18) having an insulating resin layer formed on a copper foil was obtained. The thickness of each polyimide resin layer on the copper foil is 1.6 μm / 8.7 μm / 1.7 μm in the order of K 2 / A 2 / K 2 .
実施例19
ポリイミド前駆体樹脂A2の硬化後厚みが10.2μmである以外は、実施例18と同様に行い、3層のポリイミド樹脂層からなる合計厚み13.5μmの絶縁樹脂層が銅箔上に形成されたCCL(M19)を得た。銅箔上の各ポリイミド樹脂層の厚みは、K2/A2/K2の順に、1.6μm/10.2μm/1.7μmである。
Example 19
An insulating resin layer having a total thickness of 13.5 μm consisting of three polyimide resin layers is formed on the copper foil, except that the thickness after curing of the polyimide precursor resin A 2 is 10.2 μm. CCL (M19) was obtained. The thickness of each polyimide resin layer on the copper foil is 1.6 μm / 10.2 μm / 1.7 μm in the order of K 2 / A 2 / K 2 .
比較例7
銅箔Aを使用し、この銅箔上に合成例13で調製したポリイミド前駆体樹脂M2の溶液を硬化後の厚みが9.0μmの厚みになるように均一に塗布し、70〜130℃で加熱乾燥し溶剤を除去した。次に、その上に合成例11で調製したポリイミド前駆体樹脂K2の溶液を硬化後の厚みが2.0μmの厚みになるように均一に塗布し、130℃で加熱乾燥し溶剤を除去した。この後、130℃、160℃、200℃、230℃、280℃、320℃、360℃で各2〜30分段階的な熱処理によりイミド化を行い、2層のポリイミド樹脂層からなる合計厚み11μmの絶縁樹脂層が銅箔上に形成されたCCL(M20)を得た。銅箔上の各ポリイミド樹脂層の厚みは、M2/K2の順に、9.0μm/2.0μmである。特性評価結果を表6に示す。
Comparative Example 7
Using the copper foil A, a solution of the polyimide precursor resin M 2 prepared in Synthesis Example 13 was uniformly applied onto the copper foil so that the thickness after curing was 9.0 μm, and the temperature was 70 to 130 ° C. And dried by heating to remove the solvent. Next, the solution of the polyimide precursor resin K 2 prepared in Synthesis Example 11 was uniformly applied thereon so that the thickness after curing was 2.0 μm, and the solvent was removed by heating at 130 ° C. . Thereafter, imidization is performed by stepwise heat treatment at 130 ° C., 160 ° C., 200 ° C., 230 ° C., 280 ° C., 320 ° C., and 360 ° C. for 2 to 30 minutes each, and the total thickness of the two polyimide resin layers is 11 μm. A CCL (M20) having an insulating resin layer formed on a copper foil was obtained. The thickness of each polyimide resin layer on the copper foil is 9.0 μm / 2.0 μm in the order of M 2 / K 2 . The characteristic evaluation results are shown in Table 6.
実施例20
ステンレス箔A(20μm厚みのステンレス箔、新日本製鐵株式会社製、SUS304)を使用し、このステンレス箔上に合成例1で調製したポリイミド前駆体樹脂A2の溶液を硬化後の厚みが10μmの厚みになるように均一に塗布し、110℃で加熱乾燥し溶剤を除去した。この後、130℃〜360℃で各2〜30分段階的な熱処理によりイミド化を行い、厚み10μmのポリイミド樹脂の絶縁樹脂層がステンレス箔上に形成された積層体を得た。この積層体について表7に示す物性を測定した。
Example 20
Using stainless steel foil A (20 μm thick stainless steel foil, SUS304, manufactured by Nippon Steel Corp., SUS304), the thickness of the polyimide precursor resin A 2 prepared in Synthesis Example 1 on this stainless steel foil is 10 μm after curing. The film was uniformly coated so as to have a thickness of 1, and heated and dried at 110 ° C. to remove the solvent. Thereafter, imidization was performed by stepwise heat treatment at 130 ° C. to 360 ° C. for 2 to 30 minutes to obtain a laminate in which an insulating resin layer of polyimide resin having a thickness of 10 μm was formed on the stainless steel foil. The physical properties shown in Table 7 were measured for this laminate.
実施例21
ステンレス箔A上に、合成例1で調製したポリイミド前駆体樹脂A2の溶液を硬化後の厚みが8.5μmの厚みになるように均一に塗布し、110℃で加熱乾燥し溶剤を除去した。更に、その上に合成例14で調製したポリイミド前駆体樹脂Vの溶液を硬化後の厚みが1.5μmの厚みになるように均一に塗布し、110℃で加熱乾燥し溶剤を除去した。この後、130℃〜360℃で各2〜30分段階的な熱処理によりイミド化を行い、2層のポリイミド樹脂層からなる合計厚み10μmの絶縁樹脂層がステンレス箔上に形成された積層体を得た。この積層体について表7に示す物性を測定した。
Example 21
On the stainless steel foil A, the solution of the polyimide precursor resin A 2 prepared in Synthesis Example 1 was uniformly applied so that the thickness after curing was 8.5 μm, and the solvent was removed by heating at 110 ° C. . Further, the polyimide precursor resin V solution prepared in Synthesis Example 14 was uniformly applied thereon so that the thickness after curing was 1.5 μm, and the solvent was removed by heating at 110 ° C. Thereafter, imidization is performed by stepwise heat treatment at 130 ° C. to 360 ° C. for 2 to 30 minutes, and a laminate in which an insulating resin layer having a total thickness of 10 μm formed of two polyimide resin layers is formed on a stainless steel foil is obtained. Obtained. The physical properties shown in Table 7 were measured for this laminate.
実施例22
ステンレス箔A上に、合成例15で調製したポリイミド前駆体樹脂Uの溶液を硬化後の厚みが1.0μmの厚みになるように均一に塗布し、110℃で加熱乾燥し溶剤を除去した。次に、その上に合成例1で調製したポリイミド前駆体樹脂A2の溶液を硬化後の厚みが7.5μmの厚みになるように均一に塗布し、110℃で加熱乾燥し溶剤を除去した。更に、その上に合成例14で調製したポリイミド前駆体樹脂Vの溶液を硬化後の厚みが1.5μmの厚みになるように均一に塗布し、110℃で加熱乾燥し溶剤を除去した。この後、130℃〜360℃で各2〜30分段階的な熱処理によりイミド化を行い、3層のポリイミド樹脂層からなる合計厚み10μmの絶縁樹脂層がステンレス箔上に形成された積層体を得た。この積層体について表7に示す物性を測定した。
Example 22
On the stainless steel foil A, the solution of the polyimide precursor resin U prepared in Synthesis Example 15 was uniformly applied so that the thickness after curing was 1.0 μm, and the solvent was removed by heating and drying at 110 ° C. Next, a solution of the polyimide precursor resin A 2 prepared in Synthesis Example 1 was uniformly applied thereon so that the thickness after curing was 7.5 μm, and the solvent was removed by heating at 110 ° C. . Further, the polyimide precursor resin V solution prepared in Synthesis Example 14 was uniformly applied thereon so that the thickness after curing was 1.5 μm, and the solvent was removed by heating at 110 ° C. Thereafter, imidization is performed by stepwise heat treatment at 130 ° C. to 360 ° C. for 2 to 30 minutes, and a laminated body in which an insulating resin layer having a total thickness of 10 μm formed of three polyimide resin layers is formed on a stainless steel foil. Obtained. The physical properties shown in Table 7 were measured for this laminate.
なお、合成例14(ポリイミド前駆体樹脂Vの合成)は、PMDA14.37 g、BTDA5.31 g、APB23.83 g、DMAc257 gを使用し、合成例1〜13と同様にして重合反応を行った。合成例15(ポリイミド前駆体樹脂Uの合成)は、PMDA6.03 g、BTDA13.37 g、DANPG19.6 g、DMAc261 gを使用し、合成例1〜13と同様にして重合反応を行った In Synthesis Example 14 (Synthesis of Polyimide Precursor Resin V), PMDA 14.37 g, BTDA 5.31 g, APB 23.83 g, and DMAc 257 g were used, and a polymerization reaction was performed in the same manner as Synthesis Examples 1-13. It was. In Synthesis Example 15 (synthesis of polyimide precursor resin U), PMDA 6.03 g, BTDA 13.37 g, DANPG 19.6 g, and DMAc 261 g were used, and a polymerization reaction was performed in the same manner as in Synthesis Examples 1 to 13.
1 COF用フレキシブル配線基板
2 スプロケットホール
1 Flexible wiring board for
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Cited By (5)
Publication number | Priority date | Publication date | Assignee | Title |
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JP2010157571A (en) * | 2008-12-26 | 2010-07-15 | Nippon Steel Chem Co Ltd | Laminated body for flexible wiring board |
JP2010202681A (en) * | 2009-02-27 | 2010-09-16 | Nippon Steel Chem Co Ltd | Polyimide film |
JP2014167132A (en) * | 2014-06-19 | 2014-09-11 | Nippon Steel & Sumikin Chemical Co Ltd | Polyimide film |
KR20170122196A (en) * | 2015-02-26 | 2017-11-03 | 우베 고산 가부시키가이샤 | Manufacturing method of copper clad laminate |
JP2019130876A (en) * | 2018-02-03 | 2019-08-08 | 日鉄ケミカル&マテリアル株式会社 | Metal clad laminate sheet and method for producing the same |
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JPH08134212A (en) * | 1994-11-14 | 1996-05-28 | Hitachi Ltd | Wiring structure and production thereof |
JPH09174756A (en) * | 1995-12-26 | 1997-07-08 | Nitto Denko Corp | Polyimide-metal foil composite film |
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Cited By (10)
Publication number | Priority date | Publication date | Assignee | Title |
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JP2010157571A (en) * | 2008-12-26 | 2010-07-15 | Nippon Steel Chem Co Ltd | Laminated body for flexible wiring board |
JP2010202681A (en) * | 2009-02-27 | 2010-09-16 | Nippon Steel Chem Co Ltd | Polyimide film |
JP2014167132A (en) * | 2014-06-19 | 2014-09-11 | Nippon Steel & Sumikin Chemical Co Ltd | Polyimide film |
KR20170122196A (en) * | 2015-02-26 | 2017-11-03 | 우베 고산 가부시키가이샤 | Manufacturing method of copper clad laminate |
KR102039341B1 (en) | 2015-02-26 | 2019-11-01 | 우베 고산 가부시키가이샤 | Manufacturing method of copper clad laminate |
JP2019130876A (en) * | 2018-02-03 | 2019-08-08 | 日鉄ケミカル&マテリアル株式会社 | Metal clad laminate sheet and method for producing the same |
KR20190094291A (en) * | 2018-02-03 | 2019-08-13 | 닛테츠 케미컬 앤드 머티리얼 가부시키가이샤 | Metal-clad laminate and method for producing same |
CN110116527A (en) * | 2018-02-03 | 2019-08-13 | 日铁化学材料株式会社 | Metal-clad and its manufacturing method |
JP6996997B2 (en) | 2018-02-03 | 2022-01-17 | 日鉄ケミカル&マテリアル株式会社 | Metal-clad laminate and its manufacturing method |
KR102619451B1 (en) * | 2018-02-03 | 2024-01-02 | 닛테츠 케미컬 앤드 머티리얼 가부시키가이샤 | Metal-clad laminate and method for producing same |
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