JP6732065B2 - Flexible copper clad laminate and flexible circuit board - Google Patents
Flexible copper clad laminate and flexible circuit board Download PDFInfo
- Publication number
- JP6732065B2 JP6732065B2 JP2019027963A JP2019027963A JP6732065B2 JP 6732065 B2 JP6732065 B2 JP 6732065B2 JP 2019027963 A JP2019027963 A JP 2019027963A JP 2019027963 A JP2019027963 A JP 2019027963A JP 6732065 B2 JP6732065 B2 JP 6732065B2
- Authority
- JP
- Japan
- Prior art keywords
- copper foil
- layer
- polyimide layer
- copper
- clad laminate
- 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.)
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- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 title claims description 164
- 229910052802 copper Inorganic materials 0.000 title claims description 25
- 239000010949 copper Substances 0.000 title claims description 25
- 239000011889 copper foil Substances 0.000 claims description 130
- 229920001721 polyimide Polymers 0.000 claims description 84
- 239000004642 Polyimide Substances 0.000 claims description 65
- 229920006259 thermoplastic polyimide Polymers 0.000 claims description 41
- 230000009477 glass transition Effects 0.000 claims description 15
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- 238000002441 X-ray diffraction Methods 0.000 claims description 10
- 150000004985 diamines Chemical class 0.000 claims description 10
- 150000008065 acid anhydrides Chemical class 0.000 claims description 8
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 6
- 239000001294 propane Substances 0.000 claims description 6
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- 239000010410 layer Substances 0.000 description 94
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Landscapes
- Laminated Bodies (AREA)
Description
本発明は、携帯電話やスマートフォン、タブレットPC等の筐体の狭空間部分に収納させるために、ハゼ折り状に折り曲げたり、ハードディスクドライブのリードライトケーブルのような小さな曲率半径で連続的に繰り返し屈曲させる用途に適したフレキシブル回路基板（FPC）に用いられるフレキシブル銅張積層板に関するものである。なお、ハゼ折りとは、薄い筐体へ収納する為に折り目をつけて折り曲げるような態様をいい、以下、本明細書では、ＦＰＣの上面側が略１８０℃反転して下面側になるように折り曲げることを「ハゼ折り」と呼ぶことがある。 INDUSTRIAL APPLICABILITY The present invention folds into a goby shape or is continuously bent repeatedly with a small radius of curvature like a read/write cable of a hard disk drive in order to store it in a narrow space of a housing such as a mobile phone, a smart phone, or a tablet PC. The present invention relates to a flexible copper-clad laminate used for a flexible circuit board (FPC) suitable for the application. Note that the goby fold refers to a mode in which a fold is made to fold it in order to store it in a thin housing, and hereinafter, in the present specification, the FPC is bent so that the upper surface side is inverted by about 180° C. to be the lower surface side. This is sometimes called "goby folding".
近年、携帯電話、ノート型パソコン、デジタルカメラ、ゲーム機などに代表される電子機器は、小型化、薄型化、軽量化が急速に進み、これらに使用される材料に対して、小スペースにおいても部品を収納できる高密度で高性能な材料が望まれるようになっている。フレキシブル回路基板においても、スマートフォンやタブレットPC等の高性能小型電子機器の普及に伴い、部品収納の高密度化が進展したため、今まで以上に、より狭い筐体内にフレキシブル回路基板を収納する必要が出てきている。そのためフレキシブル回路基板の材料であるフレキシブル銅張積層板においても材料面からの耐ハゼ折性や耐屈曲特性の向上が求められてきている。 In recent years, electronic devices typified by mobile phones, laptop computers, digital cameras, game consoles, etc. have rapidly become smaller, thinner, and lighter, and the materials used for them can be used even in a small space. There is a growing demand for high density, high performance materials that can house components. With regard to flexible circuit boards as well, with the spread of high-performance small electronic devices such as smartphones and tablet PCs, the high density of parts storage has progressed.Therefore, it is necessary to house the flexible circuit board in a narrower housing than ever before. Is coming out. Therefore, even in the flexible copper-clad laminate, which is a material of the flexible circuit board, improvement of the goby bending resistance and the bending resistance from the material side has been demanded.
これらの課題に対して、フレキシブル銅張積層板に使用する銅箔においては微量の銀や錫等を添加することで加熱処理時に銅箔のアニールによる軟化が進むとともに、ある特定の方向（２００面）に結晶方位が揃った立方体集合組織の発達する特殊圧延銅箔が提案されている（特許文献１参照）。これにより銅箔に屈曲時のストレスが付加された場合、結晶内で発生する転移及びその移動が結晶粒界に蓄積することなく表面方向に移動することで結晶粒界でのクラック発生及び進展による破壊を抑制し優れた屈曲特性を発現する。 In order to solve these problems, in the copper foil used for the flexible copper-clad laminate, addition of a small amount of silver, tin, or the like causes the copper foil to be annealed and softened during the heat treatment, and a certain direction (200 ) Has proposed a special rolled copper foil in which a cubic texture with uniform crystallographic orientation develops (see Patent Document 1). When stress is applied to the copper foil at the time of bending by this, the dislocation and its movement occurring in the crystal move toward the surface direction without accumulating in the crystal grain boundary, which causes cracking and development at the crystal grain boundary. It suppresses breakage and exhibits excellent bending properties.
このような圧延銅箔については常温においては前述した特性を発現することが出来ず、このような立方体組織を発達させる為には、所定の熱処理によるアニールが必須である。このアニールに必要な熱量は、例えば、低温であれば１５０℃，６０分等の処理により、高温であれば３００℃以上で１分程度の時間で完結する。 Such rolled copper foil cannot exhibit the above-mentioned characteristics at room temperature, and annealing by a predetermined heat treatment is essential for developing such a cubic structure. The amount of heat required for this annealing is, for example, 150° C. for 60 minutes at a low temperature, and 300° C. or higher at a high temperature for about 1 minute.
一般的に、ポリイミドと銅箔から構成される銅張積層板を製造する方法として、銅箔上にポリイミド前駆体を塗布し乾燥、高温熱処理することで片面銅張積層板を得たのち、銅箔を熱ラミネート法にて圧着する工程により作製する方法や、予め熱可塑性ポリイミドを最外層に含むポリイミドフィルムを準備し、その両側に銅箔を熱ラミネート法により圧着する方式が知られている。この熱ラミネート方式は、一対の対向する熱圧着ロールを使用する簡易的方式で、その装置導入も比較的容易であるという利点を有している。しかしながら、この手法においては、熱ラミネート時の銅箔への入熱量が数秒程度の短時間であるため、圧延銅箔の立方体組織を発達させるほどの十分な熱量を与えることが出来ない。 Generally, as a method for producing a copper-clad laminate composed of polyimide and copper foil, a polyimide precursor is applied onto a copper foil, dried, and then heat-treated at high temperature to obtain a single-sided copper-clad laminate, and then copper. There are known a method of producing by a step of pressure-bonding a foil by a thermal laminating method, and a method of preparing a polyimide film containing thermoplastic polyimide as an outermost layer in advance and pressing a copper foil on both sides thereof by a thermal laminating method. This thermal laminating method is a simple method that uses a pair of opposing thermocompression-bonding rolls, and has the advantage of being relatively easy to introduce into the device. However, in this method, the amount of heat input to the copper foil at the time of thermal lamination is a short time of about several seconds, and therefore it is not possible to provide a sufficient amount of heat to develop the cubic structure of the rolled copper foil.
そこで、銅箔の柔軟性を向上させ、マイクロクラックやクラック等の欠陥不良を抑えるために、銅箔を熱ラミネート法により圧着した後に、アニール処理する手法が提案されている（特許文献２参照）。ところが、ここに示されたアニール処理の条件は、温度、時間とも広範囲な範囲しか示されておらず、具体的にどのようなアニール条件でその特性が向上するか明らかでなかった。また、特許文献２に示されたアニール処理の時間は２分以上とされているため、生産性が十分でない他、アニール処理による効果としては銅箔の弾性率に着目しているのみであり、（２００）面結晶配向等の立方体組織制御といった観点までは言及しておらず、より厳しい屈曲用途への展開に対し対応し得るとも言い難いものであった。 Therefore, in order to improve the flexibility of the copper foil and suppress defect defects such as microcracks and cracks, a method has been proposed in which the copper foil is pressure-bonded by a thermal lamination method and then annealed (see Patent Document 2). .. However, the annealing conditions shown here show only a wide range in terms of temperature and time, and it was not clear under what kind of annealing conditions the characteristics were improved. In addition, since the annealing time shown in Patent Document 2 is set to 2 minutes or more, the productivity is not sufficient, and the effect of the annealing treatment only focuses on the elastic modulus of the copper foil. It did not mention the point of view of controlling the cubic texture such as (200) plane crystal orientation, and it was hard to say that it could be applied to more severe bending applications.
一方、熱ロールによる熱ラミネート方式と異なるフレキシブル銅張積層板の製造方法として、複数のロールとスチールベルトを用いて熱ラミネートを実施する、いわゆるダブルベルト方式が提案されている（特許文献３参照）。この方式は、ロール本数等を増やすことにより、ラミネート時の十分な時間を確保することが出来るが、設備費用が膨大となることなどの問題がある。 On the other hand, as a method of manufacturing a flexible copper-clad laminate different from the heat laminating method using a heat roll, a so-called double belt method has been proposed in which heat lamination is performed using a plurality of rolls and a steel belt (see Patent Document 3). .. This method can secure a sufficient time at the time of lamination by increasing the number of rolls, but there is a problem that the equipment cost becomes huge.
本発明は、上記課題に鑑みてなされたものである。その目的は、耐熱性や寸法安定性に優れたポリイミドを絶縁層とするフレキシブル銅張積層板の製造において、一対の熱プレスロールによる簡易的な手法で、屈曲特性にも優れたフレキシブル銅張積層板を提供することにある。 The present invention has been made in view of the above problems. The purpose is to produce a flexible copper clad laminate that has excellent heat resistance and dimensional stability by using a pair of hot press rolls in a flexible copper clad laminate that uses a polyimide insulating layer as an insulating layer. To provide a plate.
上記課題を解決するため本発明者等が検討した結果、銅箔とポリイミドとを圧着する加熱圧着工程の温度Ｔ１と、後加熱を行う再加熱工程の温度Ｔ２について、銅箔と接する熱可塑性ポリイミド層のガラス転移温度（Tg）以上にＴ１を設定し、かつ、Ｔ１＜Ｔ２とすることで、再加熱工程（アニール処理）により銅箔の弾性率が低下するとともに、（２００）面の特定配向が進行し立方体組織を発達させることができ、配線基板に要求される高い耐折り曲げ性を発現するフレキシブル銅張積層板が得られることを見出し出し、本発明を完成した。 As a result of studies by the present inventors in order to solve the above problems, regarding the temperature T1 of the thermocompression bonding step of crimping the copper foil and the polyimide and the temperature T2 of the reheating step of performing the post-heating, the thermoplastic polyimide in contact with the copper foil By setting T1 above the glass transition temperature (Tg) of the layer and setting T1<T2, the elastic modulus of the copper foil decreases due to the reheating step (annealing treatment), and the specific orientation of the (200) plane It was found that a flexible copper clad laminate capable of developing a cubic structure and developing a high bending resistance required for a wiring board can be obtained, and completed the present invention.
すなわち、本発明は、ポリイミド層と、該ポリイミド層の一方の面に設けられた第１の銅箔層（Ａ１）と、該ポリイミド層のもう一方の面に設けられた第２の銅箔層（Ａ２）と、を備えたフレキシブル銅張積層板であって、以下のａ〜ｄの構成：
ａ）ポリイミド層は複数層からなり、前記銅箔層（Ａ１、Ａ２）との各積層面として第１の熱可塑性ポリイミド層（iiａ）と第２の熱可塑性ポリイミド層（iiｂ）とを備え、前記熱可塑性ポリイミド層（iiａ）及び前記熱可塑性ポリイミド層（iiｂ）のガラス転移温度がいずれも２６０℃以上であること；
ｂ）第１の銅箔層（Ａ１）は、厚さ（ｔ１）が９〜１８μｍの範囲内であり、Ｘ線回折によって求めた（２００）面の回折強度（Ｉ）と微粉末銅のＸ線回折によって求めた（２００）面の回折強度（Ｉ0）との関係がＩ／Ｉ0＞１００である銅箔からなること；
ｃ）第２の銅箔層（Ａ２）は、厚さ（ｔ２）が９〜１８μｍの範囲内であり、Ｘ線回折によって求めた（２００）面の回折強度（Ｉ）と微粉末銅のＸ線回折によって求めた（２００）面の回折強度（Ｉ0）との関係がＩ／Ｉ0＞１００であるラミネート面銅箔からなること；
ｄ）前記銅箔層（Ａ１）におけるＩ／Ｉ0の値（Ｉ1）と前記銅箔層（Ａ２）におけるＩ／Ｉ0の値（Ｉ2）の差が５〜１０の範囲内であること；
を具備するフレキシブル銅張積層板である。
That is, the present invention provides a polyimide layer, a first copper foil layer (A1) provided on one surface of the polyimide layer, and a second copper foil layer provided on the other surface of the polyimide layer. (A2) and a flexible copper clad laminate having the following configurations a to d:
a) The polyimide layer is composed of a plurality of layers, and includes a first thermoplastic polyimide layer (iia) and a second thermoplastic polyimide layer (iib) as respective laminated surfaces with the copper foil layers (A1, A2), The glass transition temperature of each of the thermoplastic polyimide layer (iia) and the thermoplastic polyimide layer (iib) is 260° C. or higher;
b) The first copper foil layer (A1) has a thickness (t1) in the range of 9 to 18 μm, the diffraction intensity (I) of the (200) plane determined by X-ray diffraction, and the X of fine copper powder. A copper foil having a relationship with the diffraction intensity (I 0 ) of the (200) plane obtained by line diffraction, which is I/I 0 >100;
c) The second copper foil layer (A2) has a thickness (t2) in the range of 9 to 18 μm, the diffraction intensity (I) of the (200) plane obtained by X-ray diffraction and the X of fine copper powder. A laminate-faced copper foil having a relationship with the diffraction intensity (I 0 ) of the (200) plane, which is determined by line diffraction, I/I 0 >100;
difference d) the copper foil layer (the value of I / I 0 in A1) (I 1) and the copper foil layer (A2) in the I / I 0 value (I 2) is within the range of 5 to 10 thing;
A flexible copper clad laminate having
本発明においては、前記熱可塑性ポリイミド層（iiａ）及び前記熱可塑性ポリイミド層（iiｂ）を構成する酸無水物成分が、ピロメリット酸二無水物、３,３’,４,４’−ビフェニルテトラカルボン酸二無水物、３,３’,４,４’−ベンゾフェノンテトラカルボン酸二無水物、及び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からなる群より選ばれる少なくとも１種であるのが好ましい。
また、前記熱可塑性ポリイミド層（iiａ）及び前記熱可塑性ポリイミド層（iiｂ）を構成するジアミン成分が、２,２’−ビス［４−（４−アミノフェノキシ）フェニル］プロパン、４,４’−ジアミノジフェニルエーテル、及び１,３−ビス（４−アミノフェノキシ）ベンゼンからなる群より選ばれる少なくとも１種であるのが好ましい。
ここで、前記熱可塑性ポリイミド層（iiａ）及び前記熱可塑性ポリイミド層（iiｂ）を構成する酸無水物成分の主成分がピロメリット酸二無水物であり、前記熱可塑性ポリイミド層（iiａ）及び前記熱可塑性ポリイミド層（iiｂ）を構成するジアミン成分の主成分が２,２’−ビス［４−（４−アミノフェノキシ）フェニル］プロパンであるのがより好ましい。
また、本発明は、これらのフレキシブル銅張積層板の前記銅箔層（Ａ１）及び前記銅箔層（Ａ２）を回路加工してなるフレキシブル回路基板である。
In the present invention, the acid anhydride component constituting the thermoplastic polyimide layer (iia) and the thermoplastic polyimide layer (iib) is pyromellitic dianhydride, 3,3′,4,4′-biphenyltetra. At least selected from the group consisting of carboxylic acid dianhydride, 3,3',4,4'-benzophenone tetracarboxylic acid dianhydride, and 3,3',4,4'-diphenylsulfone tetracarboxylic acid dianhydride It is preferably one type.
In addition, the diamine component forming the thermoplastic polyimide layer (iia) and the thermoplastic polyimide layer (iib) is 2,2′-bis[4-(4-aminophenoxy)phenyl]propane, 4,4′- It is preferably at least one selected from the group consisting of diaminodiphenyl ether and 1,3-bis(4-aminophenoxy)benzene.
Here, the main component of the acid anhydride component constituting the thermoplastic polyimide layer (iia) and the thermoplastic polyimide layer (iib) is pyromellitic dianhydride, and the thermoplastic polyimide layer (iia) and the More preferably, the main component of the diamine component constituting the thermoplastic polyimide layer (iib) is 2,2'-bis[4-(4-aminophenoxy)phenyl]propane.
Further, the present invention is a flexible circuit board obtained by circuit-processing the copper foil layer (A1) and the copper foil layer (A2) of these flexible copper clad laminates.
本発明のフレキシブル銅張積層板によれば、その製造の際の再加熱工程（アニール処理）により銅箔の弾性率が低下するとともに、（２００）面の特定配向が進行し立方体組織を発達させることができ、その結果、配線基板に要求される高い耐折り曲げ性を発現し得ることから、特に、スマートフォン等の小型液晶周りの折り曲げ部分等の耐折り曲げ性やハードディスクのリードライトケーブル等、連続屈曲が要求される電子部品に好適に用いることができる。 According to the flexible copper-clad laminate of the present invention, the elastic modulus of the copper foil is lowered by the reheating step (annealing treatment) in the production thereof, and the specific orientation of the (200) plane progresses to develop a cubic texture. As a result, the high bending resistance required for the wiring board can be exhibited, and in particular, the bending resistance of the bent portion around small liquid crystal such as smartphones and the continuous bending of hard disk read/write cables etc. It can be suitably used for electronic parts that require
以下、本発明に係るフレキシブル銅張積層板の製造方法について述べながら、ポリイミド層と、該ポリイミド層の両面に設けられた第１及び第２の銅箔層（Ａ１、Ａ２）とを備えたフレキシブル銅張積層板について説明する。
本発明のフレキシブル銅張積層板の製造方法では、銅箔（Ａ）と、該銅箔（Ａ）との積層面としての接着層を備えるポリイミドフィルム若しくは金属層付ポリイミド積層体（Ｂ）とを加熱圧着させるわけであるが、その加熱圧着には一対の熱プレスロールが用いられる。
Hereinafter, while describing a method for manufacturing a flexible copper-clad laminate according to the present invention, a flexible layer including a polyimide layer and first and second copper foil layers (A1, A2) provided on both surfaces of the polyimide layer. The copper clad laminate will be described.
In the method for manufacturing a flexible copper-clad laminate of the present invention, a copper foil (A) and a polyimide film or a polyimide laminate with a metal layer (B) having an adhesive layer as a laminated surface with the copper foil (A) are provided. Although it is heated and pressure-bonded, a pair of hot press rolls is used for the heat-pressure bonding.
熱プレスロールとしては、金属ロールやその表面を樹脂被覆した樹脂被覆金属ロール等が挙げられるが、銅箔（Ａ）とポリイミドフィルム若しくは金属層付ポリイミド積層体（Ｂ）との積層（ラミネート）は、比較的高温で行うことが好ましいことから、ロール表面に使用する材質の耐熱性やロール内部からの加熱を表面に伝熱する必要があり、そのような観点から金属ロールが好ましく、その表面の表面粗さ（Ｒａ）は０．０１〜５μｍ、特には０．１〜３μｍの粗面化状態とすることが好ましい。 Examples of the hot press roll include a metal roll and a resin-coated metal roll whose surface is coated with a resin. A laminate of a copper foil (A) and a polyimide film or a polyimide laminate with a metal layer (B) is used. Since it is preferable to carry out at a relatively high temperature, it is necessary to transfer the heat resistance of the material used for the roll surface and the heating from the inside of the roll to the surface. From such a viewpoint, a metal roll is preferable, The surface roughness (Ra) is preferably 0.01 to 5 μm, particularly preferably 0.1 to 3 μm.
本発明では、上記一対の熱プレスロール間に、銅箔（Ａ）とポリイミドフィルム若しくは金属層付ポリイミド積層体（Ｂ）とが導入され加熱圧着される。本明細書中では、この工程を加熱圧着工程というが、銅箔（Ａ）と加熱圧着される対象物は、ポリイミドフィルム若しくは金属層付ポリイミド積層体（Ｂ）であり、銅箔（Ａ）とポリイミドフィルムの接着層とが貼り合わされるか、又は、銅箔（Ａ）と金属層付ポリイミド積層体（Ｂ）における接着層とが貼り合わされる。 In the present invention, the copper foil (A) and the polyimide film or the polyimide laminate with a metal layer (B) are introduced between the pair of hot press rolls and thermocompression bonded. In this specification, this step is referred to as a thermocompression bonding step, but the object to be thermocompression bonded with the copper foil (A) is a polyimide film or a polyimide laminate with a metal layer (B), and the copper foil (A) The adhesive layer of the polyimide film is attached, or the copper foil (A) and the adhesive layer of the polyimide laminate with a metal layer (B) are attached.
このうち、ポリイミドフィルム（Ｂ）としては、前記銅箔（Ａ）との積層面に接着層を有していればよく、このようなものとしては、ガラス転移温度２６０℃以上である単層の熱可塑性ポリイミドフィルムのほか、非熱可塑性ポリイミド層の片面若しくは両面にガラス転移温度２６０℃以上の熱可塑性ポリイミド層を有する複数のポリイミド層から構成されるポリイミドフィルムが挙げられる。上記ポリイミドフィルム（Ｂ）は、公知の手法で製造準備することができる他、市販のポリイミドフィルムを使用することもできる。市販のポリイミドフィルムとしては、東レデュポン製のカプトンＥＮ等が挙げられる。また、市販の低熱膨張性ポリイミドフィルムに熱可塑性ポリイミド層（ii）を与えるポリイミド前駆体の樹脂溶液を塗布、硬化させてもよい。 Of these, the polyimide film (B) has only to have an adhesive layer on the surface laminated with the copper foil (A), and as such, a single layer having a glass transition temperature of 260° C. or higher can be used. In addition to the thermoplastic polyimide film, a polyimide film composed of a plurality of polyimide layers having a thermoplastic polyimide layer having a glass transition temperature of 260° C. or higher on one or both sides of a non-thermoplastic polyimide layer can be mentioned. The polyimide film (B) can be prepared by a known method, or a commercially available polyimide film can be used. Examples of commercially available polyimide films include Kapton EN manufactured by Toray DuPont. Further, a resin solution of a polyimide precursor that provides the thermoplastic polyimide layer (ii) may be applied and cured on a commercially available low thermal expansion polyimide film.
また、金属層付ポリイミド積層体（Ｂ）としては、銅箔等の金属箔上に単層若しくは複数層のポリイミド層を設けたものが挙げられる。ポリイミドが単層の場合、そのポリイミド層自体が接着層となるため、ポリイミドはガラス転移温度２６０℃以上の熱可塑性ポリイミド層（ii）からなる必要があるが、ポリイミドが複数層の場合には、少なくとも前記銅箔（Ａ）との積層される面が熱可塑性ポリイミド層（ii）であればよい。このような金属層付ポリイミド積層体（Ｂ）の構成としては、金属層／熱可塑性ポリイミド層（ii）／低熱膨張性ポリイミド層（ｉ）／熱可塑性ポリイミド層（ii）や、金属層／低熱膨張性ポリイミド層（ｉ）／熱可塑性ポリイミド層（ii）の構成が例示される。金属層付ポリイミド積層体（Ｂ）におけるポリイミドを複数層の構成とすることで、銅箔とポリイミドの接着強度や寸法安定性、半田耐熱性等のフレキシブル銅張積層板として要求される諸特性を満足することが出来る。なお、金属層を構成する金属箔としては、銅箔の他、アルミニウム箔、ステンレス箔が挙げられる。 Examples of the polyimide laminate with a metal layer (B) include those in which a single layer or a plurality of polyimide layers are provided on a metal foil such as a copper foil. When the polyimide is a single layer, since the polyimide layer itself becomes an adhesive layer, the polyimide needs to be composed of a thermoplastic polyimide layer (ii) having a glass transition temperature of 260° C. or higher, but when the polyimide has a plurality of layers, At least the surface on which the copper foil (A) is laminated should be the thermoplastic polyimide layer (ii). The composition of such a polyimide laminate with a metal layer (B) includes metal layer/thermoplastic polyimide layer (ii)/low thermal expansion polyimide layer (i)/thermoplastic polyimide layer (ii) and metal layer/low heat The constitution of the expandable polyimide layer (i)/thermoplastic polyimide layer (ii) is exemplified. By forming the polyimide in the metal layer-attached polyimide laminate (B) in a plurality of layers, various properties required for a flexible copper-clad laminate such as adhesive strength between copper foil and polyimide, dimensional stability, and solder heat resistance can be obtained. I can be satisfied. Examples of the metal foil forming the metal layer include copper foil, aluminum foil, and stainless steel foil.
上記金属層付ポリイミド積層体（Ｂ）は、より具体的には、片面フレキシブル銅張積層板として準備することができる。片面フレキシブル銅張積層板は、長尺状の銅箔上に前記低熱膨張性ポリイミド層（ｉ）や熱可塑性ポリイミド層（ii）を与えるポリイミド前駆体の樹脂溶液を逐次塗工乾燥し、硬化（イミド化）させることで得ることができる。本発明は、一対の熱プレスロールによる簡易的な手法でフレキシブル銅張積層板を連続的に効率よく製造することを１つの特徴としており、その観点から、金属層付ポリイミド積層体（Ｂ）を形成する銅箔は長尺状のものが用いられる。 More specifically, the metal layer-attached polyimide laminate (B) can be prepared as a single-sided flexible copper-clad laminate. The single-sided flexible copper-clad laminate is obtained by successively applying and drying a resin solution of a polyimide precursor which gives the low thermal expansion polyimide layer (i) or the thermoplastic polyimide layer (ii) on a long copper foil, and curing ( It can be obtained by imidization). One of the features of the present invention is to produce a flexible copper clad laminate continuously and efficiently by a simple method using a pair of hot press rolls. From that viewpoint, the polyimide laminate with a metal layer (B) is provided. The copper foil to be formed has a long shape.
このような形態の銅箔はロール状に巻き取ったものが銅箔メーカーから市販され、それを使用することができる。また、本発明によれば、製造されたフレキシブル銅張積層板の銅箔から回路加工され形成された回路が、銅箔の持つ屈曲性能を最大限発現可能なものとすることができ、その観点から、最初に片面フレキシブル銅張積層板とする際に用いる銅箔にも、後に一対の熱プレスロールで加熱圧着される銅箔（Ａ）と同じ圧延銅箔を使用することが好ましい。 The copper foil in such a form, which is wound into a roll, is commercially available from a copper foil maker and can be used. Further, according to the present invention, a circuit formed by processing a circuit from the copper foil of the manufactured flexible copper-clad laminate can be capable of maximally exhibiting the bending performance of the copper foil. Therefore, it is preferable to use the same rolled copper foil as the copper foil (A) to be heat-pressed by a pair of hot press rolls, also for the copper foil used when first forming the single-sided flexible copper-clad laminate.
ポリイミド層を構成する低熱膨張性ポリイミド層（ｉ）や熱可塑性ポリイミド層（ii）は、それらの特性を与えるその前駆体であるポリアミド酸をイミド化して得られるが、それらのポリアミド酸は、一般に公知のジアミンと酸二無水物とを求められるポリイミドの特性に合わせて適宜選択し、これらを有機溶媒中で合成することで得ることができる。重合される樹脂粘度は、例えば、５００ｃｐｓ以上３５，０００ｃｐｓ以下の範囲内とすることが好ましい。 The low thermal expansion polyimide layer (i) and the thermoplastic polyimide layer (ii) constituting the polyimide layer can be obtained by imidizing a polyamic acid that is a precursor thereof that gives these properties, and those polyamic acids are generally It can be obtained by appropriately selecting a known diamine and acid dianhydride according to the required properties of the polyimide and synthesizing these in an organic solvent. The resin viscosity to be polymerized is preferably in the range of 500 cps or more and 35,000 cps or less, for example.
ポリイミドの原料として用いられるジアミンとしては、例えば、4,6-ジメチル-ｍ-フェニレンジアミン、2,5-ジメチル-p-フェニレンジアミン、2,4-ジアミノメシチレン、4,4'-メチレンジ-o-トルイジン、4,4'-メチレンジ-2,6-キシリジン、4,4'-メチレン-2,6-ジエチルアニリン、2,4-トルエンジアミン、ｍ-フェニレンジアミン、p-フェニレンジアミン、4,4'-ジアミノジフェニルプロパン、3,3'-ジアミノジフェニルプロパン、4,4'-ジアミノジフェニルエタン、3,3'-ジアミノジフェニルエタン、4,4'-ジアミノジフェニルメタン、3,3'-ジアミノジフェニルメタン、2,2-ビス[4-(4-アミノフェノキシ)フェニル]プロパン、4,4'-ジアミノジフェニルスルフィド、3,3'-ジアミノジフェニルスルフィド、4,4'-ジアミノジフェニルスルホン、3,3'-ジアミノジフェニルスルホン、4,4'-ジアミノジフェニルエーテル、3,3-ジアミノジフェニルエーテル、1,3-ビス（3-アミノフェノキシ）ベンゼン、1,3-ビス（4-アミノフェノキシ）ベンゼン、1,4-ビス（4-アミノフェノキシ）ベンゼン、ベンジジン、3,3'-ジアミノビフェニル、3,3'-ジメチル-4,4'-ジアミノビフェニル、3,3'-ジメトキシベンジジン、4,4'-ジアミノ-p-テルフェニル、3,3'-ジアミノ-p-テルフェニル、ビス(p-アミノシクロヘキシル)メタン、ビス(p-β-アミノ-t-ブチルフェニル)エーテル、ビス(p-β-メチル-δ-アミノペンチル)ベンゼン、p-ビス(2-メチル-4-アミノペンチル)ベンゼン、p-ビス(1,1-ジメチル-5-アミノペンチル)ベンゼン、1,5-ジアミノナフタレン、2,6-ジアミノナフタレン、2,4-ビス(β-アミノ-t-ブチル)トルエン、2,4-ジアミノトルエン、ｍ-キシレン-2,5-ジアミン、p-キシレン-2,5-ジアミン、ｍ-キシリレンジアミン、p-キシリレンジアミン、2,6-ジアミノピリジン、2,5-ジアミノピリジン、2,5-ジアミノ-1,3,4-オキサジアゾール、ピペラジン、2,2'-ジメチル-4,4'-ジアミノビフェニル、3,7-ジアミノジベンゾフラン、1,5-ジアミノフルオレン、ジベンゾ-p-ジオキシン-2,7-ジアミン、4,4'-ジアミノベンジルなどが挙げられる。 Examples of the diamine used as a raw material of polyimide include, for example, 4,6-dimethyl-m-phenylenediamine, 2,5-dimethyl-p-phenylenediamine, 2,4-diaminomesitylene, 4,4′-methylenedi-o- Toluidine, 4,4'-methylenedi-2,6-xylidine, 4,4'-methylene-2,6-diethylaniline, 2,4-toluenediamine, m-phenylenediamine, p-phenylenediamine, 4,4' -Diaminodiphenylpropane, 3,3'-diaminodiphenylpropane, 4,4'-diaminodiphenylethane, 3,3'-diaminodiphenylethane, 4,4'-diaminodiphenylmethane, 3,3'-diaminodiphenylmethane, 2, 2-bis[4-(4-aminophenoxy)phenyl]propane, 4,4'-diaminodiphenyl sulfide, 3,3'-diaminodiphenyl sulfide, 4,4'-diaminodiphenyl sulfone, 3,3'-diaminodiphenyl Sulfone, 4,4'-diaminodiphenyl ether, 3,3-diaminodiphenyl ether, 1,3-bis(3-aminophenoxy)benzene, 1,3-bis(4-aminophenoxy)benzene, 1,4-bis(4 -Aminophenoxy)benzene, benzidine, 3,3'-diaminobiphenyl, 3,3'-dimethyl-4,4'-diaminobiphenyl, 3,3'-dimethoxybenzidine, 4,4'-diamino-p-terphenyl , 3,3'-diamino-p-terphenyl, bis(p-aminocyclohexyl)methane, bis(p-β-amino-t-butylphenyl) ether, bis(p-β-methyl-δ-aminopentyl) Benzene, p-bis(2-methyl-4-aminopentyl)benzene, p-bis(1,1-dimethyl-5-aminopentyl)benzene, 1,5-diaminonaphthalene, 2,6-diaminonaphthalene, 2, 4-bis(β-amino-t-butyl)toluene, 2,4-diaminotoluene, m-xylene-2,5-diamine, p-xylene-2,5-diamine, m-xylylenediamine, p-xylyl Diamine, 2,6-diaminopyridine, 2,5-diaminopyridine, 2,5-diamino-1,3,4-oxadiazole, piperazine, 2,2'-dimethyl-4,4'-diaminobiphenyl, 3,7-diaminodibenzofuran, 1,5-diaminofluorene, dibenzo-p-dioxin-2,7-diamine, 4,4'-diamino Benzyl etc. are mentioned.
また、ポリイミドの原料として用いられる酸無水物としては、例えば、ピロメリット酸二無水物、3,3',4,4'-ベンゾフェノンテトラカルボン酸二無水物、2,2',3,3'-ベンゾフェノンテトラカルボン酸二無水物、2,3,3',4'-ベンゾフェノンテトラカルボン酸二無水物、ナフタレン-1,2,5,6-テトラカルボン酸二無水物、ナフタレン-1,2,4,5-テトラカルボン酸二無水物、ナフタレン-1,4,5,8-テトラカルボン酸二無水物、ナフタレン-1,2,6,7-テトラカルボン酸二無水物、4,8-ジメチル-1,2,3,5,6,7-ヘキサヒドロナフタレン-1,2,5,6-テトラカルボン酸二無水物、4,8-ジメチル-1,2,3,5,6,7-ヘキサヒドロナフタレン-2,3,6,7-テトラカルボン酸二無水物、2,6-ジクロロナフタレン-1,4,5,8-テトラカルボン酸二無水物、2,7-ジクロロナフタレン-1,4,5,8-テトラカルボン酸二無水物、2,3,6,7-テトラクロロナフタレン-1,4,5,8-テトラカルボン酸二無水物、1,4,5,8-テトラクロロナフタレン-2,3,6,7-テトラカルボン酸二無水物、3,3',4,4'-ビフェニルテトラカルボン酸二無水物、2,2',3,3'-ビフェニルテトラカルボン酸二無水物、2,3,3',4'-ビフェニルテトラカルボン酸二無水物、3,3'',4,4''-p-テルフェニルテトラカルボン酸二無水物、2,2'',3,3''-p-テルフェニルテトラカルボン酸二無水物、2,3,3'',4''-p-テルフェニルテトラカルボン酸二無水物、2,2-ビス(2,3-ジカルボキシフェニル)-プロパン二無水物、2,2-ビス(3,4-ジカルボキシフェニル)-プロパン二無水物、ビス(2,3-ジカルボキシフェニル)エーテル二無水物、ビス(2,3-ジカルボキシフェニル)メタン二無水物、ビス(3.4-ジカルボキシフェニル)メタン二無水物、ビス(2,3-ジカルボキシフェニル)スルホン二無水物、ビス(3,4-ジカルボキシフェニル)スルホン二無水物、1,1-ビス(2,3-ジカルボキシフェニル)エタン二無水物、1,1-ビス(3,4-ジカルボキシフェニル)エタン二無水物、ペリレン-2,3,8,9-テトラカルボン酸二無水物、ペリレン-3,4,9,10-テトラカルボン酸二無水物、ペリレン-4,5,10,11-テトラカルボン酸二無水物、ペリレン-5,6,11,12-テトラカルボン酸二無水物、フェナンスレン-1,2,7,8-テトラカルボン酸二無水物、フェナンスレン-1,2,6,7-テトラカルボン酸二無水物、フェナンスレン-1,2,9,10-テトラカルボン酸二無水物、シクロペンタン-1,2,3,4-テトラカルボン酸二無水物、ピラジン-2,3,5,6-テトラカルボン酸二無水物、ピロリジン-2,3,4,5-テトラカルボン酸二無水物、チオフェン-,3,4,5-テトラカルボン酸二無水物、4,4'-オキシジフタル酸二無水物、2,3,6,7-ナフタレンテトラカルボン酸二無水物などが挙げられる。 Further, as the acid anhydride used as a raw material of the polyimide, for example, pyromellitic dianhydride, 3,3',4,4'-benzophenone tetracarboxylic dianhydride, 2,2',3,3' -Benzophenone tetracarboxylic dianhydride, 2,3,3',4'-benzophenone tetracarboxylic dianhydride, naphthalene-1,2,5,6-tetracarboxylic dianhydride, naphthalene-1,2, 4,5-Tetracarboxylic acid dianhydride, naphthalene-1,4,5,8-tetracarboxylic acid dianhydride, naphthalene-1,2,6,7-tetracarboxylic acid dianhydride, 4,8-dimethyl -1,2,3,5,6,7-hexahydronaphthalene-1,2,5,6-tetracarboxylic dianhydride, 4,8-dimethyl-1,2,3,5,6,7- Hexahydronaphthalene-2,3,6,7-tetracarboxylic dianhydride, 2,6-dichloronaphthalene-1,4,5,8-tetracarboxylic dianhydride, 2,7-dichloronaphthalene-1, 4,5,8-Tetracarboxylic acid dianhydride, 2,3,6,7-Tetrachloronaphthalene-1,4,5,8-tetracarboxylic acid dianhydride, 1,4,5,8-Tetrachloro Naphthalene-2,3,6,7-tetracarboxylic dianhydride, 3,3',4,4'-biphenyltetracarboxylic dianhydride, 2,2',3,3'-biphenyltetracarboxylic dianhydride Anhydride, 2,3,3',4'-biphenyltetracarboxylic dianhydride, 3,3'',4,4''-p-terphenyltetracarboxylic dianhydride, 2,2'', 3,3''-p-terphenyltetracarboxylic dianhydride, 2,3,3'',4''-p-terphenyltetracarboxylic dianhydride, 2,2-bis(2,3- Dicarboxyphenyl)-propane dianhydride, 2,2-bis(3,4-dicarboxyphenyl)-propane dianhydride, bis(2,3-dicarboxyphenyl)ether dianhydride, bis(2,3 -Dicarboxyphenyl)methane dianhydride, bis(3.4-dicarboxyphenyl)methane dianhydride, bis(2,3-dicarboxyphenyl)sulfone dianhydride, bis(3,4-dicarboxyphenyl)sulfone dianhydride Anhydride, 1,1-bis(2,3-dicarboxyphenyl)ethane dianhydride, 1,1-bis(3,4-dicarboxyphenyl)ethane dianhydride, perylene-2,3,8,9 -Tetracarboxylic acid dianhydride, perylene-3,4,9,10-tetracarboxylic acid dianhydride, perylene- 4,5,10,11-tetracarboxylic dianhydride, perylene-5,6,11,12-tetracarboxylic dianhydride, phenanthrene-1,2,7,8-tetracarboxylic dianhydride, phenanthrene -1,2,6,7-tetracarboxylic dianhydride, phenanthrene-1,2,9,10-tetracarboxylic dianhydride, cyclopentane-1,2,3,4-tetracarboxylic dianhydride , Pyrazine-2,3,5,6-tetracarboxylic dianhydride, pyrrolidine-2,3,4,5-tetracarboxylic dianhydride, thiophene-3,4,5-tetracarboxylic dianhydride , 4,4′-oxydiphthalic acid dianhydride, 2,3,6,7-naphthalenetetracarboxylic acid dianhydride and the like.
上記ジアミン及び酸無水物は、それぞれ１種のみを使用してもよく２種以上を併用することもできる。また、重合に使用される溶媒は、ジメチルアセトアミド、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種又は２種以上併用して使用することもできる。 The diamine and the acid anhydride may be used alone or in combination of two or more. Further, the solvent used for the polymerization includes dimethylacetamide, N-methylpyrrolidinone, 2-butanone, diglyme, xylene and the like, and one kind or a combination of two or more kinds can be used.
ポリイミド層を熱膨張係数１７×１０-6／Ｋ未満の低熱膨張性のポリイミド層（ｉ）とするには、原料の酸無水物成分としてピロメリット酸二無水物、3,3',4,4'-ビフェニルテトラカルボン酸二無水物を、ジアミン成分としては、2,2'-ジメチル-4,4'-ジアミノビフェニル、2-メトキシ-4，4’-ジアミノベンズアニリドを用いることがよく、特に好ましくは、ピロメリット酸二無水物及び2,2'-ジメチル-4,4'-ジアミノビフェニルを原料各成分の主成分とするものがよい。 To make the polyimide layer a low thermal expansion polyimide layer (i) having a thermal expansion coefficient of less than 17×10 −6 /K, pyromellitic dianhydride, 3,3′,4, and 4'-biphenyltetracarboxylic dianhydride, as the diamine component, 2,2'-dimethyl-4,4'-diaminobiphenyl, 2-methoxy-4,4'-diaminobenzanilide is often used, Particularly preferably, pyromellitic dianhydride and 2,2′-dimethyl-4,4′-diaminobiphenyl are the main components of the raw material components.
また、ポリイミド層をガラス転移温度が２６０℃以上の熱可塑性ポリイミド層（ii）とするには、原料の酸無水物成分としてピロメリット酸二無水物、3,3',4,4’-ビフェニルテトラカルボン酸二無水物、3,3',4,4’-ベンゾフェノンテトラカルボン酸二無水物、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を、ジアミン成分としては、2,2’-ビス[4-(4-アミノフェノキシ)フェニル]プロパン、4,4'-ジアミノジフェニルエーテル、1,3-ビス（4-アミノフェノキシ）ベンゼンを用いることがよく、特に好ましくはピロメリット酸二無水物及び2,2’-ビス[4-(4-アミノフェノキシ)フェニル]プロパンを原料各成分の主成分とするものがよい。 Further, in order to make the polyimide layer a thermoplastic polyimide layer (ii) having a glass transition temperature of 260° C. or higher, pyromellitic dianhydride, 3,3′,4,4′-biphenyl is used as a raw material acid anhydride component. Tetracarboxylic acid dianhydride, 3,3',4,4'-benzophenone tetracarboxylic acid dianhydride, 3,3',4,4'-diphenylsulfone tetracarboxylic acid dianhydride, as a diamine component, It is preferable to use 2,2'-bis[4-(4-aminophenoxy)phenyl]propane, 4,4'-diaminodiphenyl ether, 1,3-bis(4-aminophenoxy)benzene, particularly preferably pyromellitic It is preferable to use acid dianhydride and 2,2′-bis[4-(4-aminophenoxy)phenyl]propane as the main components of the raw material components.
本発明では、ポリイミドフィルムを使用する場合も、金属層付ポリイミド積層体を使用する場合のいずれの場合においても、銅箔（Ａ）との積層面は接着層とする必要がある。
接着層は、熱可塑性ポリイミド層（ii）から構成されるが、そのガラス転移温度は２６０℃以上であり、２８０℃〜３２０℃の範囲にあることが好ましい。熱可塑性ポリイミド層（ii）のガラス転移温度をこの範囲とすることで、フレキシブル銅張積層板をフレキシブル回路基板に加工にする際に求められる、銅箔とポリイミド面との間の接着強度や寸法安定性、部品実装時の半田接合に要求される半田耐熱性が優れたものとなる。
In the present invention, the laminated surface with the copper foil (A) needs to be an adhesive layer regardless of whether the polyimide film is used or the polyimide laminate with a metal layer is used.
The adhesive layer is composed of the thermoplastic polyimide layer (ii), and its glass transition temperature is 260° C. or higher, preferably in the range of 280° C. to 320° C. By setting the glass transition temperature of the thermoplastic polyimide layer (ii) within this range, the adhesive strength and dimensions between the copper foil and the polyimide surface, which are required when processing a flexible copper-clad laminate into a flexible circuit board. The stability and the soldering heat resistance required for soldering when mounting components are excellent.
一方、低熱膨張性ポリイミド層（ｉ）は、ポリイミド層全体の熱膨張係数が銅箔（Ａ）の熱膨張係数に近い１２〜２３ｐｐｍ／Ｋとなるように、１７ｐｐｍ／Ｋ未満の熱膨張係数であることが好ましく、より好ましくは５〜１０ｐｐｍ／Ｋの範囲である。これにより、ポリイミド層全体の熱膨張係数を銅箔（Ａ）の熱膨張係数とあわせることが可能となり、フレキシブル銅張積層体の反りや、エッチング後、加熱後の寸法変化率を抑制することが容易となる。 On the other hand, the low thermal expansion polyimide layer (i) has a thermal expansion coefficient of less than 17 ppm/K so that the thermal expansion coefficient of the entire polyimide layer is 12 to 23 ppm/K, which is close to the thermal expansion coefficient of the copper foil (A). It is preferably in the range of 5 to 10 ppm/K. This makes it possible to match the coefficient of thermal expansion of the entire polyimide layer with the coefficient of thermal expansion of the copper foil (A), and suppress the warpage of the flexible copper-clad laminate and the dimensional change rate after etching and after heating. It will be easy.
本発明のフレキシブル銅張積層板の製造に用いられる銅箔（Ａ）は、圧延銅箔を使用することが好ましい。圧延銅箔としては、熱圧着及び後工程のアニール時に（２００）面の結晶配向が進行するように添加元素としてＡｇやＳｎを添加した銅合金箔が挙げられる。公知のものとしてＪＸ日鉱金属製のＨＡ銅箔や日立電線製のＨＰＦ箔が挙げられる。銅箔（Ａ）の厚さは特に限定されないが、一般的には、５〜１００μｍの範囲が有利であり、７〜５０μｍの範囲が好ましく、屈曲時の銅箔に付加される応力緩和の観点からは９〜１８μｍの範囲がより好ましい。 A rolled copper foil is preferably used as the copper foil (A) used for producing the flexible copper-clad laminate of the present invention. Examples of the rolled copper foil include a copper alloy foil to which Ag or Sn is added as an additive element so that the crystal orientation of the (200) plane progresses during thermocompression bonding and annealing in the subsequent process. Known examples include HA copper foil made by JX Nippon Mining Metals and HPF foil made by Hitachi Cable. The thickness of the copper foil (A) is not particularly limited, but in general, a range of 5 to 100 μm is advantageous, a range of 7 to 50 μm is preferable, and a viewpoint of stress relaxation added to the copper foil during bending. Is more preferably in the range of 9 to 18 μm.
次に、本発明における銅箔（Ａ）とポリイミドフィルム若しくは金属層付ポリイミド積層体（Ｂ）との加熱圧着条件について説明する。ラミネート温度Ｔ１、すなわち加熱圧着工程における熱プレスロールの温度としては、銅箔（Ａ）と接着層のポリイミドとの接着性の観点から、熱可塑性ポリイミド層（ii）のポリイミドのガラス転移温度以上とする必要があり、好ましくは３００〜４００℃であるのがよい。また、加熱ロール間の線圧を５０〜５００Ｋｇ／ｃｍ、ロール通過時間を２〜５秒間の条件下で加熱圧着することが望ましい。ラミネートの雰囲気としては大気雰囲気、イナート雰囲気が挙げられるが銅箔酸化変色防止の観点からイナート雰囲気であることが望ましい。ここでイナート雰囲気とは、不活性雰囲気と同義であり、窒素やアルゴン等の不活性ガスで置換され実質的に酸素を含まない状態をいう。 Next, the thermocompression bonding conditions of the copper foil (A) and the polyimide film or the polyimide laminate with a metal layer (B) in the present invention will be described. The lamination temperature T1, that is, the temperature of the hot press roll in the thermocompression bonding step, is from the viewpoint of the adhesiveness between the copper foil (A) and the polyimide of the adhesive layer, to the glass transition temperature of the polyimide of the thermoplastic polyimide layer (ii) or higher. Temperature is preferably 300 to 400° C. Further, it is desirable to perform thermocompression bonding under the conditions that the linear pressure between the heating rolls is 50 to 500 Kg/cm and the roll passage time is 2 to 5 seconds. Examples of the atmosphere for lamination include an air atmosphere and an inert atmosphere, but an inert atmosphere is preferable from the viewpoint of preventing oxidation and discoloration of copper foil. Here, the inert atmosphere has the same meaning as an inert atmosphere, and is a state in which the atmosphere is replaced with an inert gas such as nitrogen or argon and does not substantially contain oxygen.
ここで銅箔（Ａ）の熱処理による（２００）面結晶配向について詳細に説明する。一般的に前述した銅箔は熱処理により軟化が進み弾性率が低下し柔らかくなるとともに、（２００）面の優先配向が進行し立方体組織が発達する。（２００）面の結晶配向については半軟化温度以上の温度にて所定の時間処理することにより進行するが、少なくとも３００℃以上の温度で１０秒〜６０秒が必要である。本発明のように一対の熱プレスロールにより加熱圧着する方法においては、その生産性を確保する観点からロールによる圧着が１０秒以内の瞬時に実施されるため、加熱圧着工程の後に再加熱工程のアニール工程を組み合わせることが必要となる。 Here, the (200) plane crystal orientation of the copper foil (A) by heat treatment will be described in detail. Generally, the above-mentioned copper foil is softened by heat treatment to lower its elastic modulus and become soft, and the preferential orientation of the (200) plane progresses to develop a cubic structure. Regarding the crystal orientation of the (200) plane, it progresses by treating it at a temperature of a semi-softening temperature or higher for a predetermined time, but at least a temperature of 300° C. or higher for 10 to 60 seconds is required. In the method of thermocompression bonding with a pair of hot press rolls as in the present invention, since crimping with a roll is instantaneously performed within 10 seconds from the viewpoint of securing the productivity, the reheating step after the thermocompression bonding step is performed. It is necessary to combine annealing steps.
ここで再加熱工程（アニール処理）は、ラミネート温度Ｔ１以上の温度で熱処理することが必要である。ラミネート温度Ｔ１以下の温度であると、一度、加熱圧着工程において部分的に再結晶化した銅箔の結晶組織を再度結晶成長させることが出来ず、（２００）面結晶配向による立方体組織が十分進行することが出来ない。つまり、加熱圧着工程のラミネートで進んだ部分的再結晶を更に進行させるには再加熱工程の熱処理温度Ｔ２をラミネート温度Ｔ１以上に設定することが重要となる。この場合、後工程の再加熱工程の温度は３００℃以上の場合１０秒〜６０秒程度の処理時間で十分である。一方で４００℃を超えて設定した場合はポリイミドの耐熱劣化や加熱による反り等の問題が生じてくるため、４００℃以下に設定することが好ましい。 Here, in the reheating step (annealing treatment), it is necessary to perform heat treatment at a temperature equal to or higher than the laminating temperature T1. If the temperature is lower than the laminating temperature T1, the crystal structure of the partially recrystallized copper foil cannot be re-grown once in the thermocompression bonding process, and the cubic structure due to the (200) plane crystal orientation is sufficiently advanced. I can't do it. That is, it is important to set the heat treatment temperature T2 in the reheating step to the laminating temperature T1 or higher in order to further promote the partial recrystallization that has progressed in the laminating in the thermocompression bonding step. In this case, when the temperature of the reheating step of the subsequent step is 300° C. or higher, a treatment time of about 10 seconds to 60 seconds is sufficient. On the other hand, if the temperature is set to be higher than 400°C, problems such as heat resistance deterioration of the polyimide and warpage due to heating will occur.
このような再加熱工程を経ることで、前記加熱圧着工程後の銅箔（Ａ）の厚み方向でのＸ線回折によって求めた（２００）面の回折強度（I）と微粉末銅のX線回折によって求めた（２００）面回折強度（Io）との関係をI／Io＞１００となるようにすることが可能となる。ここで、I値およびIo値はＸ線回折法によって測定することができ、銅箔の厚み方向のＸ線回折とは、銅箔の表面（圧延銅箔の場合は圧延面）における配向性を確認するものであり、（２００）面の強度（Ｉ）はＸ線回折で求めた（２００）面の強度積分値を示す。また、強度（Io）は、微粉末銅（関東化学社製銅粉末試薬Ｉ級、３２５メッシュ、純度９９．９９％以上）の（２００）面の強度積分値を示す。 Through such a reheating step, the diffraction intensity (I) of the (200) plane obtained by X-ray diffraction in the thickness direction of the copper foil (A) after the thermocompression bonding step and the X-ray of fine copper powder It is possible to set the relationship with the (200) plane diffraction intensity (Io) obtained by diffraction so that I/Io>100. Here, the I value and the Io value can be measured by an X-ray diffraction method, and the X-ray diffraction in the thickness direction of the copper foil means the orientation on the surface of the copper foil (rolled surface in the case of rolled copper foil). This is to be confirmed, and the intensity (I) of the (200) plane indicates the integrated value of the intensity of the (200) plane obtained by X-ray diffraction. In addition, the strength (Io) indicates the integrated value of the strength of the (200) plane of fine powder copper (Kanto Chemical Co., Ltd. copper powder reagent grade I, 325 mesh, purity 99.99% or more).
再加熱工程のアニールの手段は制限されないが、連続して搬送されるポリイミドフィルム又は金属層付ポリイミド積層体（Ｂ）や銅箔（Ａ）を均一な温度環境下に置くことを考慮すると、工程の一区画を炉型ブースとし、熱風で加熱することが好ましい。また、熱風には、銅箔表面の変質等の影響を防止するために加熱窒素とすることが好ましい。この窒素による加熱は温度条件をより高くするには限界があることから、その他の加熱手段を付加することができる。好ましい加熱手段は搬送路の近傍に加熱ヒーターを設けることが挙げられる。なお、加熱ヒーターは複数個設置することも可能で、その種類は同じであっても異なるものであってもよい。 Means for annealing in the reheating step is not limited, but considering that the polyimide film or the polyimide laminate with metal layer (B) and the copper foil (A) that are continuously conveyed are placed in a uniform temperature environment, It is preferable to use one section as a furnace booth and heat with hot air. Further, the hot air is preferably heated nitrogen in order to prevent the influence of alteration or the like on the surface of the copper foil. Since the heating with nitrogen has a limit in increasing the temperature condition, other heating means can be added. A preferable heating means is to provide a heater in the vicinity of the conveyance path. It should be noted that a plurality of heating heaters can be installed, and the types thereof may be the same or different.
以下、実施例に基づき本発明をより詳細に説明する。なお、下記の実施例における各特性評価は、以下の方法により行った。 Hereinafter, the present invention will be described in more detail based on examples. In addition, each characteristic evaluation in the following examples was performed by the following methods.
［ＸＲＤによる結晶方位I/Ioの測定］
銅箔の（２００）面結晶方位についてはＭｏ対陰極を用いたＸＲＤ法により微粉末銅のＸ線回折によって求めた（２００）面回折強度（Io）に対して試料の（２００）面回折強度（I）を算出しI/Io値として定義した。
[Measurement of crystal orientation I/Io by XRD]
Regarding the (200) plane crystallographic orientation of the copper foil, the (200) plane diffraction intensity (Io) of the sample was compared with the (200) plane diffraction intensity of the fine copper powder obtained by XRD method using Mo anticathode. (I) was calculated and defined as I/Io value.
［屈曲特性の測定］
銅箔／ポリイミド／銅箔で構成された両面フレキシブル銅張積層板に対して市販のフォトレジストフィルムを貼り合せて、所定のパターン形成用マスクで露光した後、フォトレジストフィルムを貼り合せた側の銅箔が残るように反対面の銅箔を全面エッチオフしたのち、残った銅箔にＬ／Ｓ＝１００μｍ／１００μｍのパターンが形成されるようにレジスト層を硬化形成した（L：回路線幅、S：回路線間スペース幅）。次に、硬化レジスト箇所を現像して所定のパターン形成に不要な銅箔をエッチング除去し、更に硬化レジスト層をアルカリ液にて剥離除去することで試験サンプルを作製した。試験パターンにカバーレイを張り付けた後にＩＰＣ試験装置を用いて、屈曲半径ｒ＝１．５ｍｍ、ストローク２５ｍｍ、摺動速度を１５００ｃｐｍとした。屈曲寿命の判定としてはサンプルに所定の電圧を印可しながら屈曲試験を実施し、電気抵抗値が１０％上昇したサンプルを配線断線とみなし屈曲回数とした。下記実施例及び比較例では、キャスト面銅箔に所定のパターンを形成した場合（ラミネート面銅箔（基材２）は除去）の屈曲特性と、ラミネート面銅箔（基材２）に所定のパターンを形成した場合の屈曲特性（キャスト面銅箔は除去）とを、それぞれ評価した。
[Measurement of bending characteristics]
A commercially available photoresist film is attached to a double-sided flexible copper clad laminate composed of copper foil/polyimide/copper foil, exposed with a mask for pattern formation, and then the photoresist film is attached to the side. After completely etching off the copper foil on the opposite side so that the copper foil remains, a resist layer is formed by curing so that a pattern of L/S=100 μm/100 μm is formed on the remaining copper foil (L: circuit line width , S: space width between circuit lines). Next, a cured resist portion was developed to remove an unnecessary copper foil for forming a predetermined pattern by etching, and the cured resist layer was peeled off with an alkaline solution to prepare a test sample. After applying the coverlay to the test pattern, the bending radius r was 1.5 mm, the stroke was 25 mm, and the sliding speed was 1500 cpm using an IPC tester. As a judgment of the bending life, a bending test was carried out while applying a predetermined voltage to the sample, and the sample in which the electric resistance value increased by 10% was regarded as a wiring disconnection, and the bending frequency was set. In the following Examples and Comparative Examples, the bending characteristics when a predetermined pattern is formed on the cast surface copper foil (the laminate surface copper foil (base material 2) is removed) and the predetermined characteristics for the laminate surface copper foil (base material 2) The bending characteristics when the pattern was formed (the copper foil on the cast surface was removed) were evaluated.
［半田耐熱性試験の測定］
市販のフォトレジストフィルムを銅箔／ポリイミド／銅箔で構成された両面フレキシブル銅張積層板に貼り合せて、所定のパターン形成用マスクで露光した後、銅箔表裏面それぞれの同位置に１ｍｍの円形パターンのレジスト層を硬化形成する。次に、硬化レジスト箇所を現像して所定のパターン形成に不要な銅箔層をエッチング除去し、更に硬化レジスト層をアルカリ液にて剥離除去することで試験サンプルを作製した。サンプルを乾燥させた後に、温度の異なる半田浴槽に１０秒浸漬し銅箔の膨れ、剥がれの現象が発生しない温度を測定しこの温度を半田耐熱温度とした。
[Measurement of solder heat resistance test]
A commercially available photoresist film was attached to a double-sided flexible copper-clad laminate composed of copper foil/polyimide/copper foil, exposed with a mask for forming a predetermined pattern, and then 1 mm at the same position on each of the front and back surfaces of the copper foil. A circular resist layer is cured and formed. Next, a cured resist portion was developed to remove a copper foil layer unnecessary for forming a predetermined pattern by etching, and the cured resist layer was peeled and removed with an alkaline solution to prepare a test sample. After the sample was dried, it was immersed in a solder bath at different temperatures for 10 seconds, and the temperature at which the phenomenon of swelling and peeling of the copper foil did not occur was measured and this temperature was taken as the solder heat resistance temperature.
［ピール強度の測定］
市販のフォトレジストフィルムを銅箔／ポリイミド／銅箔で構成された積層体にラミネートし所定のパターン形成用マスクで露光した後、銅配線幅が１ｍｍのパターンになるようにレジスト層を硬化形成する。次に、硬化レジスト箇所を現像して所定のパターン形成に不要な銅箔層をエッチング除去し、更に硬化レジスト層をアルカリ液にて剥離除去することで試験サンプルを作製した。サンプルを乾燥させた後に、東洋精機株式会社製引っ張り試験器（ストログラフ M-1）にて１８０°引き剥がし法によりピール強度を測定した。
[Measurement of peel strength]
A commercially available photoresist film is laminated on a laminate composed of copper foil/polyimide/copper foil, exposed by a predetermined pattern forming mask, and then a resist layer is formed by curing so that a copper wiring width becomes a pattern of 1 mm. .. Next, a cured resist portion was developed to remove a copper foil layer unnecessary for forming a predetermined pattern by etching, and the cured resist layer was peeled and removed with an alkaline solution to prepare a test sample. After the sample was dried, the peel strength was measured by a 180° peeling method using a tensile tester (Strograph M-1) manufactured by Toyo Seiki Co., Ltd.
［寸法変化率の測定］
寸法変化率の測定は、以下の手順で行った。
まず、３００ｍｍ角の試料（フレキシブル銅張積層板）を用い、２００ｍｍ間隔にてドライフィルムレジストを露光、現像することによって、位置測定用ターゲットを形成した。更に温度２３±２℃、相対湿度５０±５％の雰囲気中にてエッチング前(常態)の寸法を測定した後に、試験片のターゲット以外の銅をエッチング(液温４０℃以下、時間１０分以内)により除去した。温度２３±２℃、相対湿度５０±５％の雰囲気中に２４±４時間静置後、位置ターゲット間の距離を測定した。縦方向及び横方向の各３箇所の常態に対する寸法変化率を算出し、各々の平均値をもってエッチング後の寸法を測定した。次に、本試験片を２５０℃のオーブンで１時間加熱処理し、その後の位置ターゲット間の距離を測定する。縦方向及び横方向の各３箇所の常態に対する寸法変化率を算出し、各々の平均値をもって加熱処理後の寸法変化率とする。加熱寸法変化率は下記数式により出した。
エッチング後寸法変化率（％）＝(Ｂ−Ａ)／Ａ × １００
Ａ ； レジスト現像後のターゲット間距離
Ｂ ； 配線形成後のターゲット間距離
加熱寸法変化率（％）＝(Ｄ−Ｃ)／Ｃ × １００
Ｃ ； 配線形成後のターゲット間距離
Ｄ ； 加熱後のターゲット間距離
[Measurement of dimensional change rate]
The dimensional change rate was measured by the following procedure.
First, a 300 mm square sample (flexible copper clad laminate) was used to expose and develop a dry film resist at 200 mm intervals to form a position measurement target. Furthermore, after measuring the dimensions before etching (normal state) in an atmosphere of a temperature of 23±2°C and a relative humidity of 50±5%, copper other than the target of the test piece is etched (liquid temperature 40°C or less, time within 10 minutes). ). After standing still in an atmosphere having a temperature of 23±2° C. and a relative humidity of 50±5% for 24±4 hours, the distance between the position targets was measured. The rate of dimensional change in the normal state at each of three locations in the vertical direction and the horizontal direction was calculated, and the dimension after etching was measured with the average value of each. Next, this test piece is heat-treated in an oven at 250° C. for 1 hour, and then the distance between the position targets is measured. The dimensional change rate for the normal state at each of three locations in the vertical direction and the horizontal direction is calculated, and the average value of each is used as the dimensional change rate after the heat treatment. The heating dimensional change rate was calculated by the following mathematical formula.
Dimensional change rate after etching (%)=(B−A)/A×100
A: Target distance after resist development B: Target distance after wiring formation Heating dimensional change rate (%)=(D−C)/C×100
C: Target distance after wiring formation D: Target distance after heating
［反りの測定］
フレキシブル銅張積層板から１０ｃｍ×１０ｃｍサイズのシートを作成し、このシートを机上に載置したときに最も机の面から浮き上がった部分の机の面からの高さを、ノギスを用いて測定した。その高さを反り量とし、反り量が２ｍｍ未満の場合「反りがない」と評価した。
[Measurement of warpage]
A sheet with a size of 10 cm×10 cm was prepared from the flexible copper-clad laminate, and the height of the part most lifted from the desk surface when the sheet was placed on the desk was measured using a caliper. .. The height was taken as the amount of warp, and when the amount of warp was less than 2 mm, it was evaluated as “no warp”.
［ガラス転移温度の測定］
銅箔上にポリアミド酸の樹脂溶液を塗布、熱処理し積層体とした。この積層体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（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）を求めた。
[Measurement of glass transition temperature]
A resin solution of polyamic acid was applied onto copper foil and heat-treated to obtain a laminate. The polyimide film (10 mm×22.6 mm) obtained by etching away the copper foil of this laminate was subjected to DMA to increase the dynamic viscoelasticity when the temperature was raised from 20° C. to 500° C. at 5° C./min. The measurement was performed to determine the glass transition temperature Tg (tanδ maximum value).
［熱膨張係数の測定］
銅箔をエッチングして得られたポリイミドフィルムを、セイコーインスツルメンツ製のサーモメカニカルアナライザーを使用し、２５０℃まで昇温し、更にその温度で１０分保持した後、５℃/分の速度で冷却し、２４０℃から１００℃までの平均熱膨張係数(線熱膨張係数)を求めた。
[Measurement of coefficient of thermal expansion]
The polyimide film obtained by etching the copper foil was heated up to 250°C using a thermomechanical analyzer manufactured by Seiko Instruments, held at that temperature for 10 minutes, and then cooled at a rate of 5°C/minute. The average thermal expansion coefficient (linear thermal expansion coefficient) from 240° C. to 100° C. was determined.
次に、実施例、比較例に用いたポリアミド酸の合成例を示す。
（合成例１）
熱電対及び攪拌機を備えるとともに窒素導入が可能な反応容器に、N,N−ジメチルアセトアミドを入れ、この反応容器に2,2-ビス[4-(4-アミノフェノキシ)フェニル]プロパン(BAPP)を投入して容器中で撹拌しながら溶解させた。次に、ピロメリット酸二無水物（PMDA）をモノマーの投入総量が１２wt％となるように投入した。その後、３時間撹拌を続けて重合反応を行い、ポリアミド酸aの樹脂溶液を得た。このポリアミド酸ａから得られたポリイミドのガラス転移点温度は３１０℃で、線熱膨張係数は４５ｐｐｍ／Ｋであった。
Next, a synthesis example of the polyamic acid used in Examples and Comparative Examples will be shown.
(Synthesis example 1)
A reaction vessel equipped with a thermocouple and a stirrer and capable of introducing nitrogen was charged with N,N-dimethylacetamide, and 2,2-bis[4-(4-aminophenoxy)phenyl]propane (BAPP) was placed in this reaction vessel. It was charged and dissolved while stirring in a container. Next, pyromellitic dianhydride (PMDA) was added so that the total amount of the monomers added was 12 wt %. Then, stirring was continued for 3 hours to carry out a polymerization reaction to obtain a resin solution of polyamic acid a. The glass transition temperature of the polyimide obtained from this polyamic acid a was 310° C., and the linear thermal expansion coefficient was 45 ppm/K.
（合成例２）
熱電対及び攪拌機を備えると共に窒素導入が可能な反応容器に、N,N−ジメチルアセトアミドを入れ、この反応容器に2,2'−ジメチル−4,4'−ジアミノビフェニル（ｍ-TB）を投入して容器中で攪拌しながら溶解させた。次に、3,3',4,4'−ビフェニルテトラカルボン酸二無水物（BPDA）およびピロメリット酸二無水物（PMDA）をモノマーの投入総量が１５wt％、各酸無水物のモル比率（BPDA：PMDA）が２０：８０となるように投入した。その後、３時間撹拌を続けて重合反応を行い、ポリアミド酸ｂの樹脂溶液を得た。このポリアミド酸ｂから得られたポリイミドのガラス転移点温度は３８０℃で、線熱膨張係数は８ｐｐｍ／Ｋであった。
(Synthesis example 2)
N,N-Dimethylacetamide was placed in a reaction vessel equipped with a thermocouple and a stirrer and capable of introducing nitrogen, and 2,2'-dimethyl-4,4'-diaminobiphenyl (m-TB) was placed in this reaction vessel. It was then dissolved in the container with stirring. Next, 3,3',4,4'-biphenyltetracarboxylic dianhydride (BPDA) and pyromellitic dianhydride (PMDA) were added at a total monomer loading of 15 wt% and the molar ratio of each acid anhydride ( BPDA:PMDA) was added at 20:80. Then, stirring was continued for 3 hours to carry out a polymerization reaction to obtain a resin solution of polyamic acid b. The glass transition temperature of the polyimide obtained from this polyamic acid b was 380° C., and the linear thermal expansion coefficient was 8 ppm/K.
（合成例３）
熱電対及び攪拌機を備えるとともに窒素導入が可能な反応容器に、N,N−ジメチルアセトアミドを入れ、この反応容器に2,2-ビス[4-(4-アミノフェノキシ)フェニル]プロパン(BAPP)を投入して容器中で撹拌しながら溶解させた。次に、3,3',4,4'−ベンゾフェノンテトラカルボン酸二無水物（BTDA）をモノマーの投入総量が１２wt％となるように投入した。その後、３時間撹拌を続けて重合反応を行い、ポリアミド酸ｃの樹脂溶液を得た。このポリアミド酸ｃから得られたポリイミドのガラス転移点温度は２４０℃で、線熱膨張係数は４２ｐｐｍ／Ｋであった。
(Synthesis example 3)
A reaction vessel equipped with a thermocouple and a stirrer and capable of introducing nitrogen was charged with N,N-dimethylacetamide, and 2,2-bis[4-(4-aminophenoxy)phenyl]propane (BAPP) was placed in this reaction vessel. It was charged and dissolved while stirring in a container. Next, 3,3′,4,4′-benzophenone tetracarboxylic acid dianhydride (BTDA) was added so that the total amount of the monomers added was 12 wt %. Then, stirring was continued for 3 hours to carry out a polymerization reaction to obtain a resin solution of polyamic acid c. The glass transition temperature of the polyimide obtained from this polyamic acid c was 240° C., and the linear thermal expansion coefficient was 42 ppm/K.
（実施例１）
厚さ１２μｍで長尺状の圧延銅箔（JX日鉱日石金属製HA箔；I/Io=7）の片面に合成例１で調製したポリアミド酸ａの樹脂溶液を硬化後の厚みが２．２μｍとなるように均一に塗布した後（第一層目）、１３０℃で加熱乾燥し溶媒を除去した。次に、この塗布面側に合成例２で調製したポリアミド酸ｂの樹脂溶液を硬化後の厚みが７．６μｍとなるように均一に塗布し（第二層目）、１３５℃で加熱乾燥し溶媒を除去した。更に、この塗布面側に第一層目で塗布したものと同じポリアミド酸ａの樹脂溶液を硬化後の厚みが２．２μｍとなるように均一に塗布し（第三層目）、１３０℃で加熱乾燥し溶媒を除去した。この長尺状の積層体を１３０℃から開始して３００℃まで段階的に温度が上がるように設定した連続硬化炉にて、合計６分程度の時間をかけて熱処理し、ポリイミド層の厚みが１２μｍの片面フレキシブル銅張積層板を得た（基材１）。
(Example 1)
1. A 12 μm thick long rolled copper foil (JX Nippon Mining & Metals HA foil; I/Io=7) was coated on one side with the resin solution of the polyamic acid a prepared in Synthesis Example 1 to give a thickness of 2. After being uniformly applied so as to have a thickness of 2 μm (first layer), it was heated and dried at 130° C. to remove the solvent. Next, the resin solution of the polyamic acid b prepared in Synthesis Example 2 was uniformly applied on the coated surface side so that the thickness after curing was 7.6 μm (second layer), and dried by heating at 135° C. The solvent was removed. Further, the same resin solution of polyamic acid a as that applied in the first layer was applied evenly to the application surface side so that the thickness after curing would be 2.2 μm (third layer), and at 130° C. It was dried by heating and the solvent was removed. This continuous laminate was heat-treated in a continuous curing furnace set to start at 130° C. and gradually increase to 300° C. over a total time of about 6 minutes to obtain a polyimide layer having a thickness of A 12 μm single-sided flexible copper-clad laminate was obtained (base material 1).
次に、この片面フレキシブル銅張積層板（基材１）のポリイミド層の表面に対して、基材２として長尺状の圧延銅箔（JX日鉱日石金属製HA箔；I/Io=7）を加熱圧着した。ラミネート装置としては、ラミネートする長尺状の基材を巻出し軸からガイドロールを経由して搬送し、イナート雰囲気下の炉内において一対の対向する金属ロール（表面粗さRa=０．１５μm）により加熱圧着させる方式を適用した。熱圧着条件は、温度３６０℃、圧力１３０Ｋｇ／ｃｍ、通過時間；２〜５秒とした（ラミネート：加熱圧着工程）。その後、380℃の加熱熱風炉にて６０秒加熱処理を行って（再加熱工程）、両面フレキシブル銅張積層板を得た。表１には各実施例に用いた基材、熱ラミネート温度とアニール条件を示す。 Next, with respect to the surface of the polyimide layer of this single-sided flexible copper clad laminate (base material 1), a long rolled copper foil (JX Nippon Mining & Metals HA foil; I/Io=7) was used as the base material 2. ) Was thermocompression bonded. As a laminating device, a long base material to be laminated is conveyed from the unwinding shaft via a guide roll, and a pair of opposing metal rolls (surface roughness Ra=0.15 μm) in a furnace under an inert atmosphere. The method of applying heat and pressure is applied. The thermocompression bonding conditions were a temperature of 360° C., a pressure of 130 Kg/cm, and a passage time of 2 to 5 seconds (laminating: thermocompression bonding process). After that, heat treatment was performed for 60 seconds in a hot air oven at 380° C. (reheating step) to obtain a double-sided flexible copper clad laminate. Table 1 shows the base material used in each example, the thermal laminating temperature and the annealing conditions.
上記で得られた両面フレキシブル銅張積層板における、ポリアミド酸の樹脂溶液を塗布した銅箔（「キャスト面銅箔」という）と、加熱圧着工程でラミネートした銅箔（基材２：「ラミネート面銅箔」という）とについて、それぞれ厚み方向でのＸ線回折によって求めた（２００）面の回折強度（I）と微粉末銅のＸ線回折によって求めた（２００）面回折強度（Io）との比Ｉ／Ｉｏ値を表２に示す。また、屈曲特性、及び半田耐熱性を表２に示す。キャスト面銅箔では、（２００面）Ｉ／Ｉｏが１９５であり、ＩＰＣ試験による屈曲回数は１７００万回であった。一方のラミネート面銅箔では、（２００面）Ｉ／Ｉｏが１８５、ＩＰＣ試験による屈曲回数は１６００万回でありキャスト面銅箔と同等の屈曲特性を有していた。また、半田耐熱温度は３５０℃であり実用上十分なレベルであった。 In the double-sided flexible copper-clad laminate obtained above, a copper foil coated with a resin solution of polyamic acid (referred to as “cast surface copper foil”) and a copper foil laminated in a thermocompression bonding process (base material 2: “laminated surface”). Copper foil"), and the diffraction intensity (I) of the (200) plane obtained by X-ray diffraction in the thickness direction and the (200) plane diffraction intensity (Io) obtained by X-ray diffraction of fine copper powder. Table 2 shows the ratio I/Io value of. Table 2 shows bending characteristics and solder heat resistance. The cast face copper foil had a (200 face) I/Io of 195, and the number of times of bending by the IPC test was 17 million times. On the other hand, the laminate-faced copper foil had an I/Io of (200) of 185, and the number of bends by the IPC test was 16 million times, which was equivalent to that of the cast-faced copper foil. The solder heat resistance temperature was 350° C., which was a practically sufficient level.
（実施例２）
基材１に用いる銅箔と、基材２の銅箔として、それぞれ長尺状の厚さ１２μｍの圧延銅箔（日立金属製HPF-ST-X）を用いた以外は実施例１と同様にして、両面フレキシブル銅張積層板を得た。得られた両面フレキシブル銅張積層板についての評価結果を表２に示す。キャスト面銅箔では、（２００面）Ｉ／Ｉｏが２０５であり、ＩＰＣ試験による屈曲回数は１６００万回であった。一方のラミネート面銅箔の（２００面）Ｉ／Ｉｏは２００であり、ＩＰＣ試験による屈曲回数は１７００万回でありキャスト面同等の屈曲特性を有していた。また、半田耐熱温度は３５０℃であった。
(Example 2)
As the copper foil used for the base material 1 and the copper foil of the base material 2, a long rolled copper foil having a thickness of 12 μm (HPF-ST-X manufactured by Hitachi Metals) was used, respectively, in the same manner as in Example 1. Thus, a double-sided flexible copper clad laminate was obtained. Table 2 shows the evaluation results of the obtained double-sided flexible copper-clad laminate. The cast face copper foil had an (200 face) I/Io of 205, and the number of bendings by the IPC test was 16 million times. One (200) I/Io of the copper foil on the laminated surface was 200, and the number of times of bending by the IPC test was 17 million times, which had bending characteristics equivalent to those of the cast surface. The solder heat resistance temperature was 350°C.
（実施例３）
市販のポリイミドフィルム（カプトンEN）の両面に合成例１にて合成したポリアミド酸ａの樹脂溶液を塗布乾燥した後、大気雰囲気にて硬化を行い、熱・BR>ツ塑性ポリイミドを含むポリイミドイミドフィルムを得た（基材１）。このポリイミドフィルムの両側に実施例１で示した銅箔（基材２）を実施例１と同様にして３６０℃の温度で熱ラミネートし、その後、熱風加熱炉にて３８０℃１分間の加熱処理を行い、両面フレキシブル銅張積層体を得た。得られた両面フレキシブル銅張積層板についての評価結果を表２に示す。ラミネート面側の銅箔の（２００面）Ｉ／Ｉｏは１９８であり、ＩＰＣ試験による屈曲回数は１３００万回であった。半田耐熱温度は３２０℃であった。
(Example 3)
Polyimide imide film containing heat/BR> plastic plastic polyimide after coating and drying resin solution of polyamic acid a synthesized in Synthesis Example 1 on both sides of commercially available polyimide film (Kapton EN) Was obtained (base material 1). The copper foil (base material 2) shown in Example 1 was heat laminated on both sides of this polyimide film at a temperature of 360° C. in the same manner as in Example 1 and then heat-treated in a hot air heating furnace at 380° C. for 1 minute. Then, a double-sided flexible copper-clad laminate was obtained. Table 2 shows the evaluation results of the obtained double-sided flexible copper-clad laminate. The (200 side) I/Io of the copper foil on the laminating surface side was 198, and the number of bendings by the IPC test was 13 million times. The solder heat resistance temperature was 320°C.
（比較例１）
実施例１と同様にして片面銅張積層板（基材１）を作製した後、実施例１で示した銅箔（基材２）を用いて、ラミネート条件を表１の条件にて実施した。そして、再加熱工程の熱処理を行わずに、比較例１に係る両面フレキシブル銅張積層板を得た。得られた両面フレキシブル銅張積層板についての評価結果を表２に示す。キャスト面銅箔では、（２００面）Ｉ／Ｉｏが１９５であり、ＩＰＣ試験による屈曲回数は１７００万回であった。一方のラミネート面銅箔の（２００面）Ｉ／Ｉｏは８７とキャスト面銅箔や実施例におけるラミネート面銅箔の約半分に満たず、ＩＰＣ試験による屈曲回数は７００万回と実施例の５０％以下であった。
(Comparative Example 1)
After producing a single-sided copper-clad laminate (base material 1) in the same manner as in Example 1, the copper foil (base material 2) shown in Example 1 was used and laminating was performed under the conditions shown in Table 1. .. Then, the double-sided flexible copper clad laminate according to Comparative Example 1 was obtained without performing the heat treatment in the reheating step. Table 2 shows the evaluation results of the obtained double-sided flexible copper-clad laminate. The cast face copper foil had a (200 face) I/Io of 195, and the number of times of bending by the IPC test was 17 million times. The (200 face) I/Io of one of the laminated surface copper foils was 87, which was less than about half of the cast surface copper foil and the laminated surface copper foil in the examples, and the number of bending times by the IPC test was 7 million times and 50 of the examples. % Or less.
（比較例２）
加熱圧着工程におけるラミネート温度Ｔ１を３８０℃にし、また、再加熱工程を３５０℃６０秒で行った以外は実施例１と同様にして、比較例２に係る両面フレキシブル銅張積層板を得た。得られた両面フレキシブル銅張積層板についての評価結果を表２に示す。キャスト面銅箔では、（２００面）Ｉ／Ｉｏが１９５であり、ＩＰＣ試験による屈曲回数は１７００万回であった。一方のラミネート面銅箔の（２００面）Ｉ／Ｉｏはラミネート後から向上せず９０であり、ＩＰＣ試験による屈曲回数は７６０万回であった。
(Comparative example 2)
A double-sided flexible copper clad laminate according to Comparative Example 2 was obtained in the same manner as in Example 1 except that the laminating temperature T1 in the thermocompression bonding step was 380° C. and the reheating step was performed at 350° C. for 60 seconds. Table 2 shows the evaluation results of the obtained double-sided flexible copper-clad laminate. The cast face copper foil had a (200 face) I/Io of 195, and the number of times of bending by the IPC test was 17 million times. The (200 face) I/Io of one of the laminated copper foils was not improved after the lamination and was 90, and the number of bendings by the IPC test was 7.6 million.
（比較例３）
加熱圧着工程におけるラミネート温度Ｔ１を３８０℃にし、また、再加熱工程を３５０℃６００秒で行った以外は実施例１と同様にして、比較例３に係る両面フレキシブル銅張積層板を得た。得られた両面フレキシブル銅張積層板についての評価結果を表２に示す。再加熱工程の時間を延長させてもラミネート面銅箔の（２００面）Ｉ／Ｉｏは８９であり、ＩＰＣ試験による屈曲回数は７２０万回であった。
(Comparative example 3)
A double-sided flexible copper clad laminate according to Comparative Example 3 was obtained in the same manner as in Example 1 except that the laminating temperature T1 in the thermocompression bonding step was set to 380° C. and the reheating step was performed at 350° C. for 600 seconds. Table 2 shows the evaluation results of the obtained double-sided flexible copper-clad laminate. Even when the time of the reheating step was extended, the (200 side) I/Io of the copper foil on the laminated surface was 89, and the number of times of bending by the IPC test was 7.2 million times.
（比較例４）
基材１の片面フレキシブル銅張積層板を得るにあたり、実施例１において第一層目と第三層目で使用したポリアミド酸のかわりに、それぞれ合成例３で示したポリアミド酸ｃを用いた以外は実施例１と同様にして、比較例４に係る両面フレキシブル銅張積層板を得た。得られた両面フレキシブル銅張積層板についての評価結果を表２に示す。ラミネート面銅箔（２００面）Ｉ／Ｉｏは１８９と向上しＩＰＣ試験による屈曲回数は１５５０万回とキャスト面銅箔と同等まで発現したが、半田耐熱性が２５０℃であり部品実装時の半田リフロー等に耐えられないレベルであった。
(Comparative Example 4)
In obtaining the single-sided flexible copper-clad laminate of the substrate 1, except that the polyamic acid c shown in Synthesis Example 3 was used instead of the polyamic acid used in the first layer and the third layer in Example 1, respectively. In the same manner as in Example 1, a double-sided flexible copper-clad laminate according to Comparative Example 4 was obtained. Table 2 shows the evaluation results of the obtained double-sided flexible copper-clad laminate. Laminated surface copper foil (200 surfaces) I/Io was improved to 189, and the number of bends by the IPC test was 15.5 million times, which was equivalent to that of cast surface copper foil, but the solder heat resistance was 250°C and the solder when mounting components It was a level that could not withstand reflow.
尚、本実施例後のフレキシブル銅張積層板のピール強度、寸法変化率、反りについて評価したが何れの実施例もピール強度は０．８ｋＮ／ｍであった。エッチング後の寸法変化率、加熱寸法変化率何れも０．１％以内であり、反りも２ｍｍ以下であった。つまり、フレキシブル銅張積層板に要求される特性は保持しており実用上の問題もないことを確認した。 The peel strength, the dimensional change rate, and the warp of the flexible copper-clad laminates after this Example were evaluated, and the peel strength was 0.8 kN/m in all Examples. Both the dimensional change rate after etching and the dimensional change rate upon heating were within 0.1%, and the warpage was 2 mm or less. That is, it was confirmed that the characteristics required for the flexible copper-clad laminate were retained and that there was no problem in practical use.
Claims (5)
ａ）ポリイミド層は複数層からなり、前記銅箔層（Ａ１、Ａ２）との各積層面として第１の熱可塑性ポリイミド層（iiａ）と第２の熱可塑性ポリイミド層（iiｂ）とを備え、前記熱可塑性ポリイミド層（iiａ）及び前記熱可塑性ポリイミド層（iiｂ）のガラス転移温度がいずれも２６０℃以上であること；
ｂ）第１の銅箔層（Ａ１）は、厚さ（ｔ１）が９〜１８μｍの範囲内であり、Ｘ線回折によって求めた（２００）面の回折強度（Ｉ）と微粉末銅のＸ線回折によって求めた（２００）面の回折強度（Ｉ0）との関係がＩ／Ｉ0＞１００である銅箔からなること；
ｃ）第２の銅箔層（Ａ２）は、厚さ（ｔ２）が９〜１８μｍの範囲内であり、Ｘ線回折によって求めた（２００）面の回折強度（Ｉ）と微粉末銅のＸ線回折によって求めた（２００）面の回折強度（Ｉ0）との関係がＩ／Ｉ0＞１００であるラミネート面銅箔からなること；
ｄ）前記銅箔層（Ａ１）におけるＩ／Ｉ0の値（Ｉ1）と前記銅箔層（Ａ２）におけるＩ／Ｉ0の値（Ｉ2）の差が５〜１０の範囲内であること；
を具備するフレキシブル銅張積層板。 A polyimide layer, a first copper foil layer (A1) provided on one surface of the polyimide layer, and a second copper foil layer (A2) provided on the other surface of the polyimide layer, A flexible copper clad laminate having the following configurations a to d:
a) The polyimide layer is composed of a plurality of layers, and includes a first thermoplastic polyimide layer (iia) and a second thermoplastic polyimide layer (iib) as respective laminated surfaces with the copper foil layers (A1, A2), The glass transition temperature of each of the thermoplastic polyimide layer (iia) and the thermoplastic polyimide layer (iib) is 260° C. or higher;
b) The first copper foil layer (A1) has a thickness (t1) in the range of 9 to 18 μm, and the diffraction intensity (I) of the (200) plane obtained by X-ray diffraction and the X of fine copper powder. A copper foil having a relationship with the diffraction intensity (I 0 ) of the (200) plane obtained by line diffraction, which is I/I 0 >100;
c) The second copper foil layer (A2) has a thickness (t2) in the range of 9 to 18 μm, the diffraction intensity (I) of the (200) plane obtained by X-ray diffraction and the X of fine copper powder. A laminate-faced copper foil having a relationship with the diffraction intensity (I 0 ) of the (200) plane, which is determined by line diffraction, I/I 0 >100;
difference d) the copper foil layer (the value of I / I 0 in A1) (I 1) and the copper foil layer (A2) in the I / I 0 value (I 2) is within the range of 5 to 10 thing;
A flexible copper clad laminate having
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