JP4549705B2 - Method for producing flexible laminate - Google Patents
Method for producing flexible laminate Download PDFInfo
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- JP4549705B2 JP4549705B2 JP2004077706A JP2004077706A JP4549705B2 JP 4549705 B2 JP4549705 B2 JP 4549705B2 JP 2004077706 A JP2004077706 A JP 2004077706A JP 2004077706 A JP2004077706 A JP 2004077706A JP 4549705 B2 JP4549705 B2 JP 4549705B2
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- laminated board
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- 238000004519 manufacturing process Methods 0.000 title claims description 23
- 229910052751 metal Inorganic materials 0.000 claims description 52
- 239000002184 metal Substances 0.000 claims description 52
- 239000011347 resin Substances 0.000 claims description 49
- 229920005989 resin Polymers 0.000 claims description 49
- 239000011888 foil Substances 0.000 claims description 46
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 35
- 238000000034 method Methods 0.000 claims description 31
- 239000011889 copper foil Substances 0.000 claims description 21
- 229920001721 polyimide Polymers 0.000 claims description 20
- 239000000243 solution Substances 0.000 claims description 20
- 230000008569 process Effects 0.000 claims description 18
- 239000009719 polyimide resin Substances 0.000 claims description 13
- 238000001035 drying Methods 0.000 claims description 7
- 238000002347 injection Methods 0.000 claims description 5
- 239000007924 injection Substances 0.000 claims description 5
- 239000002243 precursor Substances 0.000 claims description 4
- 238000010438 heat treatment Methods 0.000 claims description 3
- 239000010410 layer Substances 0.000 description 38
- 230000037303 wrinkles Effects 0.000 description 25
- 229910052802 copper Inorganic materials 0.000 description 14
- 239000010949 copper Substances 0.000 description 14
- 238000004804 winding Methods 0.000 description 10
- 239000004642 Polyimide Substances 0.000 description 7
- 239000007789 gas Substances 0.000 description 5
- 230000008859 change Effects 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- 239000010409 thin film Substances 0.000 description 4
- 229910045601 alloy Inorganic materials 0.000 description 3
- 239000000956 alloy Substances 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 239000000853 adhesive Substances 0.000 description 2
- 230000001070 adhesive effect Effects 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 230000001747 exhibiting effect Effects 0.000 description 2
- 230000009477 glass transition Effects 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 229920005575 poly(amic acid) Polymers 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 1
- 239000004962 Polyamide-imide Substances 0.000 description 1
- 239000004697 Polyetherimide Substances 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 1
- 229910052790 beryllium Inorganic materials 0.000 description 1
- ATBAMAFKBVZNFJ-UHFFFAOYSA-N beryllium atom Chemical compound [Be] ATBAMAFKBVZNFJ-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 239000007810 chemical reaction solvent Substances 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 239000011162 core material Substances 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000005489 elastic deformation Effects 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- 238000005187 foaming Methods 0.000 description 1
- 229920006015 heat resistant resin Polymers 0.000 description 1
- 239000011229 interlayer Substances 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 239000004973 liquid crystal related substance Substances 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 229920002312 polyamide-imide Polymers 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 229920001601 polyetherimide Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 238000007665 sagging Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 239000013585 weight reducing agent Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
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Description
本発明は、金属箔と樹脂層からなる長尺状のフレキシブル積層板の製造方法に関するものである。 The present invention relates to a method for producing a long flexible laminate comprising a metal foil and a resin layer.
フレキシブル積層板は、金属箔と樹脂層を積層したもので、可とう性を有することから、柔軟性や屈曲性が要求される部分に用いられ、電子機器の小型化、軽量化に貢献している。フレキシブル積層板の中でも、樹脂層にポリイミドを用いたものは、耐熱性や寸法安定性にも優れることから携帯電話や情報端末機に用いられる配線基板用途に広く用いられている。フレキシブル積層板を製造する方法としては、金属箔にフィルム状のポリイミドをエポキシ樹脂等の接着剤を用いて貼り合わせる方法や金属箔上にポリイミド樹脂溶液を直接塗工して製造する方法が挙げられるが、後者により得られるものは、接着剤による特性低下が少なくポリイミド樹脂の特性を生かしたフレキシブル銅張積層板を製造することができる。このようにしてフレキシブル積層板を製造する方法を示したものとして特許３０３４８３８号公報が参照される。 A flexible laminate is a laminate of metal foil and resin layer, and has flexibility, so it is used in areas where flexibility and flexibility are required, contributing to the downsizing and weight reduction of electronic devices. Yes. Among the flexible laminates, those using polyimide for the resin layer are widely used for wiring boards used in mobile phones and information terminals because they are excellent in heat resistance and dimensional stability. Examples of a method for producing a flexible laminate include a method in which a film-like polyimide is bonded to a metal foil using an adhesive such as an epoxy resin, and a method in which a polyimide resin solution is directly coated on a metal foil. However, what is obtained by the latter can produce a flexible copper-clad laminate that takes advantage of the properties of polyimide resin with little deterioration in properties due to the adhesive. Japanese Patent No. 3034838 is referred to as a method for producing a flexible laminate in this way.
上記に例示した金属箔にポリイミド樹脂溶液を直接塗工してフレキシブル積層板を製造した場合の不良現象として、カール発生、波しわの発生、樹脂層の発泡、銅箔の酸化劣化等がある。これらの中で、フレキシブル積層板製造工程での波しわの発生は、製品の不良を招き歩留りを低下させることなどから、波しわのないフレキシブル積層板の製造方法の提供が求められていた。 Examples of defective phenomena when a flexible laminate is produced by directly applying a polyimide resin solution to the metal foil exemplified above include curling, wrinkling, resin layer foaming, and copper foil oxidation degradation. Among these, the occurrence of wrinkles in the manufacturing process of flexible laminates leads to product defects and decreases the yield, and therefore, it has been demanded to provide a method for producing flexible laminates without wrinkles.
不良現象の改良等を図る方法の１つに、特定のバーの曲面上に、金属箔を内側にして緊張状態で長手方向に滑らせる工程を含むフレキシブル金属箔積層板の金属箔と重合体薄膜層との層間の寸法差を補正する方法が特開昭６４−８０５３０号公報に開示されている。
特許文献２に示された方法によると、層間寸法差の補正によりカールが補正され後工程での取り扱いが容易になることが示されている。しかしながら、この特許文献に示された手段は、金属箔と重合体薄膜層との層間の寸法差を矯正することを目的とするもので、フレキシブル積層板製造時に発生する波しわを矯正することは事実上困難なものであった。
According to the method disclosed in
本発明の目的は、フレキシブル積層板製造工程に生じる波しわを矯正することのできるフレキシブル積層板の製造方法を提供することにある。 The objective of this invention is providing the manufacturing method of the flexible laminated board which can correct the wrinkle which arises in a flexible laminated board manufacturing process.
本発明者等は、上記課題を解決するためにその製造工程や方法を検討した結果、金属箔上に樹脂溶液からの樹脂層を形成した後、これを搬送する工程において、加熱雰囲気下でロールを用い、ロール面と前記金属箔と樹脂層とからなる積層板の金属箔面とを張力をかけた状態で密着させる工程を通過させることにより、波しわの矯正が可能なことを見出し本発明を完成するに至った。 As a result of studying the manufacturing process and method in order to solve the above problems, the present inventors have formed a resin layer from a resin solution on a metal foil, and then in a process of transporting the resin layer, the roll is heated in a heated atmosphere. The present invention finds that the wrinkle can be corrected by passing the step of bringing the roll surface and the metal foil surface of the laminate composed of the metal foil and the resin layer into close contact with each other in a tensioned state. It came to complete.
すなわち本発明は、金属箔とポリイミド樹脂層を有する長尺状のフレキシブル積層板の製造方法において、金属箔上に樹脂前駆体溶液を塗布し、加熱、乾燥、及び硬化してポリイミド樹脂層を形成した積層板とした後、150〜450℃の雰囲気下で、表面が金属製で半径100〜1500ｍｍの平坦化用ロールのロール面に金属箔面がロール円周長の2/5〜4/5の範囲で接するようにし、かつ積層板の流れ方向に張力をかけた状態で、ロール回転とともに積層板を1〜10ｍ/minの速度範囲で接触搬送する工程を経た後、長尺状のフレキシブル積層板を巻き取ることを連続的に行うことを特徴とするフレキシブル積層板の製造方法である。ここで、1)平坦化用ロールを2〜5個配置し、それぞれのロールにおいて上記条件で積層板を接触搬送すること、2)ロール面と金属箔面とを接触させる前又は後に圧縮ガス噴射装置を配置し、これから噴射される圧縮ガスによりたわみを除去する工程を設けること、3)積層板にかける張力が100〜300Ｎ/ｍの範囲であること、又は、4)金属箔が銅箔であることは本発明の好ましい態様である。 That is, the present invention relates to a method for producing a long flexible laminate having a metal foil and a polyimide resin layer, a resin precursor solution is applied on the metal foil , heated, dried and cured to form a polyimide resin layer. After forming the laminated plate, the metal foil surface is 2/5 to 4/5 of the roll circumferential length on the roll surface of a flattening roll having a radius of 100 to 1500 mm in an atmosphere of 150 to 450 ° C. After passing through the process of contacting and transporting the laminated plate at a speed range of 1 to 10 m / min with roll rotation in a state in which the contact is made in the range of and the tension is applied in the flow direction of the laminated plate, the long flexible laminate It is a manufacturing method of a flexible laminated board characterized by performing winding up a board continuously. Here, 1) Two to five flattening rolls are arranged, and the laminate is brought into contact with each roll under the above conditions. 2) Compressed gas injection before or after bringing the roll surface and the metal foil surface into contact with each other. Arrange the equipment and provide a process to remove the deflection by the compressed gas to be jetted from now on, 3) The tension applied to the laminate is in the range of 100-300 N / m, or 4) The metal foil is copper foil It is a preferred embodiment of the present invention.
以下、本発明について詳述する。
本発明はフレキシブル積層板の製造方法にかかるものであるが、ここで製造されるフレキシブル積層板は長尺状のものである。その単位としては、通常、巾200〜1500ｍｍのもので、50〜3000ｍのものとなる。フレキシブル積層板の製造工程の概略は、a)金属箔及び樹脂溶液を用意する工程、b)金属箔に樹脂溶液を塗布する工程、c)金属箔に塗布された樹脂溶液を乾燥又は硬化して積層体とする工程、d)積層体を巻き取ってロール状とする工程とがあるが、必要によりその他の工程が付加される。
Hereinafter, the present invention will be described in detail.
The present invention relates to a method for producing a flexible laminate, and the flexible laminate produced here is a long one. The unit is usually one having a width of 200 to 1500 mm and 50 to 3000 m. The outline of the manufacturing process of the flexible laminate is as follows: a) preparing a metal foil and a resin solution, b) applying a resin solution to the metal foil, c) drying or curing the resin solution applied to the metal foil. There are a step of forming a laminate, and d) a step of winding the laminate into a roll shape, but other steps are added if necessary.
本発明で用いる金属箔は、特にその種類について制限されるものではないが、好ましくは、銅箔又はステンレス箔から選択される。本発明で銅箔という場合には、銅箔合金を含むものとして定義される。銅箔合金とは、銅を必須として含有し、クロム、ジルコニウム、ニッケル、シリコン、亜鉛、ベリリウム等の銅以外の少なくとも１種以上の異種の元素を含有する合金箔を指し、銅含有率90重量％以上のものを言う。金属箔の厚みは、5〜100μｍの範囲が好ましく、特には12〜50μｍの範囲が好ましい。この厚みが5μｍに満たないと製造工程において積層板にカールが生じ搬送が困難となり、また、100μｍを超えると積層板とした際に十分な屈曲性が得られないため好ましくない。 The metal foil used in the present invention is not particularly limited with respect to the type, but is preferably selected from copper foil or stainless steel foil. In the present invention, the term “copper foil” is defined as including a copper foil alloy. A copper foil alloy refers to an alloy foil containing copper as an essential component and containing at least one kind of different elements other than copper, such as chromium, zirconium, nickel, silicon, zinc, and beryllium, and a copper content of 90 wt. Say something more than%. The thickness of the metal foil is preferably in the range of 5 to 100 μm, particularly preferably in the range of 12 to 50 μm. If this thickness is less than 5 μm, curling occurs in the laminate in the manufacturing process, making it difficult to convey, and if it exceeds 100 μm, sufficient flexibility cannot be obtained when the laminate is used, which is not preferable.
樹脂としては、耐熱性樹脂であることが好ましく、具体的には、ポリイミド樹脂、液晶樹脂等が例示される。ポリイミド樹脂としては、ポリイミド、ポリアミドイミド、ポリエーテルイミド等その構造中にイミド結合を有するものであればよい。この樹脂は均一厚みに塗布するために、樹脂溶液の形で使用される。ここで、樹脂溶液という場合、その前駆体樹脂溶液の状態をも含む。樹脂溶液とするために使用される溶剤としては、樹脂を溶解し、沸点が低いものが好ましいが、樹脂合成の際に使用される反応溶剤を除去することなくそのまま使用することもできる。 The resin is preferably a heat resistant resin, and specific examples include polyimide resins and liquid crystal resins. Any polyimide resin may be used as long as it has an imide bond in its structure, such as polyimide, polyamideimide, or polyetherimide. This resin is used in the form of a resin solution in order to apply to a uniform thickness. Here, the term “resin solution” includes the state of the precursor resin solution. The solvent used for forming the resin solution is preferably a solvent that dissolves the resin and has a low boiling point. However, the solvent can be used as it is without removing the reaction solvent used in the resin synthesis.
金属箔上に樹脂溶液を塗工する方法としては、公知の手段を用いることができる。具体的には、ブレードコータ方式、ナイフコータ方式、リバースコータ方式等が挙げられる。 As a method of applying the resin solution on the metal foil, a known means can be used. Specific examples include a blade coater method, a knife coater method, and a reverse coater method.
上記塗工工程で、金属箔上に樹脂溶液が塗工された後、通常は樹脂溶液中の溶媒を除去するため、又は重合反応を促進させるため、乾燥や加熱を行い金属箔上に樹脂層が形成された積層板とされる。樹脂前駆体溶液を塗布した場合は、ここで硬化される。乾燥後の樹脂層の好ましい厚み範囲は、6〜80μｍの範囲であり、特に好ましくは、12〜50μｍの範囲である。樹脂層の厚みが6μｍに満たないと、積層板として実際に使用するには強度が不十分であり、一方、80μｍを超えると柔軟性及び屈曲性が不十分となる。 After the resin solution is coated on the metal foil in the coating process, the resin layer is usually dried or heated to remove the solvent in the resin solution or to accelerate the polymerization reaction. The laminate is formed. When the resin precursor solution is applied, it is cured here. The preferable thickness range of the resin layer after drying is in the range of 6 to 80 μm, and particularly preferably in the range of 12 to 50 μm. If the thickness of the resin layer is less than 6 μm, the strength is insufficient for practical use as a laminate, while if it exceeds 80 μm, the flexibility and the flexibility are insufficient.
上記樹脂層は、単層のみからなるものでもよいが、好ましくは複数層からなるものがよい。樹脂層を複数層のポリイミド樹脂層とする場合、金属箔と接する樹脂層に良好な接着性を示すものを使用することが好ましい。良接着性を示すポリイミド樹脂としては、そのガラス転移温度が350℃以下のものが挙げられる。また、金属箔と接しない中間層には、寸法安定性の点から温度変化に対する寸法変化率、すなわち線膨張係数が30×10-6/℃以下、特には20×10-6/℃以下の低熱膨張性樹脂を使用することが好ましい。ポリイミド樹脂層を2層以上の複数層で形成する場合、低熱膨張性樹脂層の厚み（L）とそれより線膨張係数が高い高熱膨張性樹脂層の厚み（H）比は、H/L＝0.1〜0.5の範囲とすることが有利である。ここで、厚みLとHは各樹脂層が複数の樹脂層からなる場合はその合計厚みをいう。また、ポリイミド層が多層である場合にも、全ポリイミド層としての線膨張係数は、30×10-6/℃以下とすることが好ましい。 The resin layer may be composed of only a single layer, but is preferably composed of a plurality of layers. When the resin layer is a plurality of polyimide resin layers, it is preferable to use a resin layer exhibiting good adhesiveness in contact with the metal foil. Examples of the polyimide resin exhibiting good adhesiveness include those having a glass transition temperature of 350 ° C. or lower. In addition, the intermediate layer not in contact with the metal foil has a dimensional change rate with respect to a temperature change in terms of dimensional stability, that is, a linear expansion coefficient of 30 × 10 −6 / ° C. or less, particularly 20 × 10 −6 / ° C. or less. It is preferable to use a low thermal expansion resin. When the polyimide resin layer is formed of two or more layers, the ratio of the low thermal expansion resin layer thickness (L) to the high thermal expansion resin layer having a higher linear expansion coefficient (H) is H / L = The range of 0.1 to 0.5 is advantageous. Here, the thicknesses L and H refer to the total thickness when each resin layer is composed of a plurality of resin layers. Even when the polyimide layer is a multilayer, the linear expansion coefficient as the total polyimide layer is preferably 30 × 10 −6 / ° C. or less.
乾燥又は硬化して積層体とする工程が終了後、積層体を巻き取ってロール状とする工程を行う。本発明では、このロール状とする工程中に平坦化工程を設けてもよく、一旦積層体をロール状に巻き取り（仮巻き取りという）したのち、再度これを巻き出して平坦化工程に送り、そこで平坦化したのち積層体を巻き取ってロール状としてもよい。後者の方法は設備が小型化できるという利点があるが、前者の方法は連続的に生産できるため生産性が優れるという利点があるので、前者の方法が有利である。なお、平坦化工程を有しない巻き取りは公知の方法が採用できるが、積層体に波しわが生じやすく、不良品率が高くなる。したがって、本発明では積層体を巻き取ってロール状とする工程又は仮巻取り後にロール状とする工程のいずれかに平坦化工程を設ける。 After the step of drying or curing to form a laminate, the step of winding the laminate to form a roll is performed. In the present invention, a flattening step may be provided in the roll forming step. After the laminate is wound up into a roll shape (referred to as temporary winding), it is unwound again and sent to the flattening step. Then, after flattening there, the laminate may be wound to form a roll. The latter method has the advantage that the equipment can be miniaturized, but the former method is advantageous because the former method has the advantage of being excellent in productivity because it can be produced continuously. In addition, although a well-known method can be employ | adopted for the winding which does not have a planarization process, a wrinkle tends to arise in a laminated body and the defect-goods rate becomes high. Therefore, in the present invention, a planarization step is provided in either the step of winding the laminate to form a roll or the step of forming a roll after provisional winding.
加熱又は乾燥して得られた積層体を平坦化する工程は、積層体を巻き取りロールに搬送するライン内に設けられる。以下、これを図面により説明する。図１はこの平坦化工程を説明するための説明図であり、積層体１はガイドロール4を経由して平坦化用ロール2及び3の金属表面と接触して、平坦化処理されてガイドロール5を経由して図示されない巻取りロールに送られてロール状に巻取られる。この平坦化用ロールは、図面では2個の例を示しているが、少なくとも１個以上であればよく、好ましくは複数個を用いることがよく、2〜5個が適している。1個の平坦化用ロールでもしわを矯正することは可能であるが、複数個を用いると、積層板と平坦化用ロールの接着する時間を長くすることができるため、しわの矯正がより容易となる。 The step of flattening the laminate obtained by heating or drying is provided in a line that conveys the laminate to a take-up roll. This will be described below with reference to the drawings. FIG. 1 is an explanatory diagram for explaining the flattening process. The laminate 1 is brought into contact with the metal surfaces of the flattening rolls 2 and 3 via the guide roll 4 and is flattened to be a guide roll. It is sent to a take-up roll (not shown) via 5 and taken up in a roll shape. Although two examples of the flattening roll are shown in the drawing, at least one flattening roll may be used, and a plurality of flattening rolls are preferably used, and 2 to 5 are suitable. Although it is possible to correct wrinkles with a single flattening roll, it is easier to correct wrinkles by using a plurality of flattening rolls because the time taken to bond the laminate and the flattening roll can be increased. It becomes.
平坦化用ロールの大きさは、その半径が100〜1500ｍｍの範囲にあることが必要であるが、好ましくは150〜1000ｍｍの範囲である。半径が100ｍｍ未満では、ロールの曲率が大きいために、樹脂層と金属箔が塑性変形を起こし積層板にカールが生じ易い。また、半径1500ｍｍを超えると積層板をロールに密着させ、しわを矯正するために必要な張力をかけることが困難となる。ロールの材質は、金属、セラミックス等の剛性及び耐熱性の高い材料が好ましいが、積層板表面の金属箔の品質保持のためには、そのロール表面は金属製であることが必要となる。その場合、表面に防錆処理を施すことが好ましい。 The size of the flattening roll needs to have a radius in the range of 100 to 1500 mm, but is preferably in the range of 150 to 1000 mm. When the radius is less than 100 mm, the curvature of the roll is large, so that the resin layer and the metal foil are plastically deformed and the laminate is likely to be curled. On the other hand, when the radius exceeds 1500 mm, it becomes difficult to apply the tension necessary to make the laminated sheet adhere to the roll and correct wrinkles. The material of the roll is preferably a material having high rigidity and heat resistance, such as metal or ceramics, but the roll surface needs to be made of metal in order to maintain the quality of the metal foil on the surface of the laminate. In that case, it is preferable to subject the surface to rust prevention treatment.
この平坦化工程は、加熱雰囲気下で行われる。一般に、フレキシブル積層板の樹脂層に使用される樹脂のガラス転移温度や熱変形温度は150℃以上であるため、それ以下の温度域では弾性変形のみを起こすので樹脂層のしわを矯正することは困難である。また、450℃を超える温度では、樹脂層の化学構造自体が変化してしまうため好ましくない。したがって、搬送工程における雰囲気温度は150〜450℃の範囲であることが必要であり、好ましくは200〜450℃の範囲である。特に、樹脂層をポリイミド樹脂とする場合、上記の理由から300〜400℃雰囲気下で接触させ搬送することが好ましい。 This planarization step is performed in a heated atmosphere. Generally, since the glass transition temperature and heat distortion temperature of the resin used for the resin layer of the flexible laminate are 150 ° C or higher, only elastic deformation occurs in the temperature range below that, so it is not possible to correct the wrinkles of the resin layer. Have difficulty. Further, a temperature exceeding 450 ° C. is not preferable because the chemical structure itself of the resin layer changes. Therefore, the atmospheric temperature in the conveyance process needs to be in the range of 150 to 450 ° C, and preferably in the range of 200 to 450 ° C. In particular, when the resin layer is a polyimide resin, it is preferable that the resin layer is brought into contact and transported in an atmosphere of 300 to 400 ° C. for the above reason.
搬送工程においては、平坦化用ロールの曲面上に積層体の金属箔面を内側にして密着させるが、この際には、積層板には、積層板流れ方向に張力をかけた状態で行われる。積層板にかける張力は、平坦化用ロールの前後に必要に応じて配置される圧縮ガス噴射装置、例えばエアターン6及び7から噴出する空気の圧力、ロールの回転速度、積層板の搬送速度等で制御することができる。積層板にかかる張力の範囲は100〜300Ｎ/ｍの範囲にあることが好ましい。この範囲が、100Ｎ/ｍ未満では、積層板の金属箔面をロール上に平坦に密着させることが困難である場合があり、また、300Ｎ/ｍを超える圧力では、搬送工程中に積層板が流れ方向に引き伸ばされ、寸法変化率に異方性が生じる恐れがある。 In the conveying process, the metal foil surface of the laminate is brought into close contact with the curved surface of the flattening roll, and in this case, the laminate is performed in a state where tension is applied to the laminate flow direction. . The tension applied to the laminated plate is determined by the pressure of the compressed gas injection device arranged as necessary before and after the flattening roll, for example, the pressure of air ejected from the air turns 6 and 7, the rotational speed of the roll, the conveying speed of the laminated plate, etc. Can be controlled. The range of tension applied to the laminate is preferably in the range of 100 to 300 N / m. If this range is less than 100 N / m, it may be difficult to make the metal foil surface of the laminated plate flatly adhere to the roll, and if the pressure exceeds 300 N / m, the laminated plate may not be It is stretched in the flow direction, and anisotropy may occur in the dimensional change rate.
この圧縮ガス噴射装置、具体的にはエアターンは、図面では平坦化用ロール2の前及び3の後にそれぞれ配置した例を示しているが、平坦化用ロールやガイドロールの配置位置等を調整することにより、0であってもよい。但し、平坦化用ロールを2個以上使用する場合には、少なくとも平坦化用ロール1個あたり1個のエアターンを設けることが好ましい。特に、平坦化用ロールを2個以上使用する場合には、各ロール間にエアターンを配置することが好ましい。このエアターンは張力を調整するだけでなく、たわみを除去し、平坦化を確実にさせる。
したがって、積層板の金属箔面とロール面とを密着させる前又は後で、圧縮ガス噴射装置で空気又は窒素等を噴射してたわみ除去を行うことが好ましい。このたわみ除去工程を設けることで、金属箔面とロール面が全ての部分において均一に密着し易くなり、更に、積層板がロールから離れた後のしわの再発を防止することができる。
This compressed gas injection device, specifically, the air turn is shown in the drawing as an example where it is arranged before and after the flattening
Therefore, it is preferable to perform deflection removal by injecting air or nitrogen with a compressed gas injection device before or after the metal foil surface and roll surface of the laminate are brought into close contact with each other. By providing this deflection removing step, the metal foil surface and the roll surface can be easily and uniformly adhered to each other, and further, the recurrence of wrinkles after the laminate is separated from the roll can be prevented.
積層板の金属箔面とロール面を密着させる範囲は、ロールの円周長の2/5〜4/5とすることが必要である。すなわち、この平坦化用ロールが半径rの円柱状とすれば、この円周は２πｒとなるので、4/5πｒ〜8/5πｒの範囲で接触させる。この密着範囲が、ロール円周長の2/5に満たないと、十分にしわを抑制することができない。また、密着範囲が、ロール円周長の4/5を超えると、積層板の金属箔面とロール面との接触面を全ての範囲で均一に密着させることが困難となり、その結果、本発明の効果が有効に発現できなくなる。 The range in which the metal foil surface of the laminate and the roll surface are in close contact with each other needs to be 2/5 to 4/5 of the circumferential length of the roll. That is, if the flattening roll has a cylindrical shape with a radius r, the circumference is 2πr, and the contact is made in the range of 4 / 5πr to 8 / 5πr. If this adhesion range is less than 2/5 of the circumferential length of the roll, wrinkles cannot be sufficiently suppressed. Further, if the adhesion range exceeds 4/5 of the roll circumferential length, it becomes difficult to uniformly adhere the contact surface between the metal foil surface of the laminate and the roll surface over the entire range, and as a result, the present invention The effect of can not be expressed effectively.
搬送工程における、搬送速度は1〜10ｍ/minとする。1ｍ/minに満たない速度では、積層板が加熱雰囲気下におかれる時間が長くなり、積層板にカールが生じ易くなり、10ｍ/minを超える速度では、金属箔とロールの密着する時間が短くなり、十分にしわを矯正することが困難となる。 The conveyance speed in the conveyance process is 1 to 10 m / min. When the speed is less than 1 m / min, the time for which the laminated plate is placed in a heated atmosphere becomes longer, and the laminated plate is likely to curl. It becomes difficult to correct wrinkles sufficiently.
金属箔及びフレキシブル積層板は、上記の塗工工程、乾燥工程、平坦化工程を含む巻取り工程を連続的に搬送され、巻きずれ、しわ、たるみ等が生じないように、引き続き張力をかけながら、プラスチックあるいは紙製のコア材に巻き取られる。このように全工程を連続的に行うことにより、フレキシブル積層板を生産性よく製造することができる。しかしながら、乾燥工程を経た積層板を仮巻き取りしたのち、あらためて平坦化工程を含む巻取り工程に付すこともできる。 The metal foil and the flexible laminate are continuously conveyed through the winding process including the coating process, the drying process, and the flattening process, and continuously applying tension so that winding deviation, wrinkles, sagging, etc. do not occur. It is wound around a core material made of plastic or paper. Thus, a flexible laminated board can be manufactured with high productivity by performing all the processes continuously. However, after the laminated board which passed through the drying process is temporarily wound, it can be subjected to a winding process including a flattening process.
本発明のフレキシブル積層板の製造方法によれば、積層板の金属箔面の凹凸やしわを矯正することが可能である。その結果、平滑な積層板が得られ、後工程での取り扱いを容易にすることができ、また、積層板の金属箔をエッチング加工した時に発生する樹脂層の寸法変化のばらつきを最小限に減少することができ、産業上の利用価値が高い。 According to the method for producing a flexible laminate of the present invention, it is possible to correct irregularities and wrinkles on the metal foil surface of the laminate. As a result, a smooth laminate can be obtained, which can be handled easily in the subsequent process, and the variation in the dimensional change of the resin layer that occurs when the metal foil of the laminate is etched is minimized. Can be industrially useful.
以下に本発明の実施例を示し、本発明を更に詳しく説明するが、本発明はこれに限定されるものではない。 Examples of the present invention will be described below to explain the present invention in more detail. However, the present invention is not limited thereto.
実施例１
樹脂溶液として、N,N-ジメチルアセトアミドに溶解したポリアミック酸樹脂溶液A（2500 cp/24℃）とポリアミック酸樹脂溶液B（28000 cp/24℃）を用意した。金属箔として幅540ｍｍ、長さ540ｍ、厚さ12μmの長尺状の電解銅箔を用意した。この銅箔を連続的に搬送しながら銅箔上に樹脂溶液をA、B、Aの順になるように3層状に均一に塗布した。この塗布済みの銅箔を、フローティング方式の加熱炉にて90〜130℃で6分間乾燥した後、130〜360℃で20分間加熱硬化して、銅箔上にポリイミド薄膜層を有する銅張積層板を得た。ここでポリイミド薄膜層の厚みを測定したところ、40μｍであった。
Example 1
As resin solutions, polyamic acid resin solution A (2500 cp / 24 ° C.) and polyamic acid resin solution B (28000 cp / 24 ° C.) dissolved in N, N-dimethylacetamide were prepared. A long electrolytic copper foil having a width of 540 mm, a length of 540 m, and a thickness of 12 μm was prepared as a metal foil. While continuously transporting this copper foil, the resin solution was uniformly applied on the copper foil in three layers so as to be in the order of A, B, and A. This coated copper foil is dried at 90-130 ° C for 6 minutes in a floating heating furnace, then heat-cured at 130-360 ° C for 20 minutes, and a copper-clad laminate having a polyimide thin film layer on the copper foil I got a plate. Here, when the thickness of the polyimide thin film layer was measured, it was 40 μm.
こうして得られた積層板には、流れ方向に10〜20ｍｍピッチで高さ1〜2ｍｍ程度の波状の凹凸（波しわ）が生じていた。引き続き、この積層板を270℃雰囲気下で、半径300ｍｍの1個の金属製平坦化用ロール曲面上に銅箔面を内側にし、且つ積層板の流れ方向に200Ｎ/ｍの張力をかけた状態で前記ロール面と銅箔面とをロールの円周長の7/10の範囲で密着させ、平坦化用ロールの回転と共に積層板を5m/minの速度で搬送したところ、しわが矯正され外観上平坦なフレキシブル銅張積層板が得られた。その後、フレキシブル銅張積層板は搬送だけのために用いられるロール上を通過させ巻き取られた。得られたフレキシブル銅張積層板は波しわがない良外観のものであった。 The laminated plate thus obtained had wavy irregularities (wave wrinkles) having a pitch of 10 to 20 mm and a height of 1 to 2 mm in the flow direction. Subsequently, the laminate was placed on a single metal flattening roll curved surface with a radius of 300 mm with a copper foil surface inside and a tension of 200 N / m applied in the flow direction of the laminate in a 270 ° C. atmosphere. When the roll surface and the copper foil surface are brought into close contact within a range of 7/10 of the circumferential length of the roll, and the laminate is conveyed at a speed of 5 m / min along with the rotation of the flattening roll, the wrinkles are corrected and the appearance is improved. An upper flat flexible copper clad laminate was obtained. Thereafter, the flexible copper clad laminate was passed over a roll used only for conveyance and wound up. The obtained flexible copper clad laminate had a good appearance with no wrinkles.
実施例２
実施例1と同様にして作成した積層板を、220℃雰囲気下で、半径300ｍｍの1個の平坦化用金属製ロール曲面上に銅箔面を内側にし、且つ積層板の流れ方向に220Ｎ/ｍの張力をかけた状態で前記ロール面と銅箔面とをロールの円周長の1/2の範囲で密着させ、ロールの回転と共に積層板を5ｍ/minの速度で搬送したところ、しわが矯正され外観上平坦なフレキシブル銅張積層板が得られた。その後、フレキシブル銅張積層板は搬送だけのために用いられるロール上を通過させ巻き取られた。得られたフレキシブル銅張積層板は波しわがない良外観のものであった。
Example 2
A laminated board prepared in the same manner as in Example 1 was placed at a temperature of 220 ° C. in a flow direction of the laminated board with a copper foil surface on one flat metal roll curved surface having a radius of 300 mm in an atmosphere of 220 ° C. When the roll surface and the copper foil surface are brought into close contact with each other in the range of 1/2 of the circumferential length of the roll with the tension of m applied, the laminate is conveyed at a speed of 5 m / min as the roll rotates. A flexible copper clad laminate that was straightened and smooth in appearance was obtained. Thereafter, the flexible copper clad laminate was passed over a roll used only for conveyance and wound up. The obtained flexible copper clad laminate had a good appearance with no wrinkles.
実施例３
実施例1と同様にして作成した積層板を、200℃雰囲気下で、半径200ｍｍの1個の平坦化用金属製ロール曲面上に銅箔面を内側にし、且つ積層板の流れ方向に100Ｎ/ｍの張力をかけた状態で前記ロール面と銅箔面とをロールの円周長の1/2の範囲で密着させ、ロールの回転と共に積層板を5ｍ/minの速度で搬送したところ、しわが矯正され外観上平坦なフレキシブル銅張積層板が得られた。その後、フレキシブル銅張積層板は搬送だけのために用いられるロール上を通過させ巻き取られた。得られたフレキシブル銅張積層板は波しわがない良外観のものであった。
Example 3
A laminated board prepared in the same manner as in Example 1 was placed at a temperature of 200 ° C. on a flattened metal roll curved surface having a radius of 200 mm with a copper foil surface inside, and 100 N / in the flow direction of the laminated board. When the roll surface and the copper foil surface are brought into close contact with each other in the range of 1/2 of the circumferential length of the roll with the tension of m applied, the laminate is conveyed at a speed of 5 m / min as the roll rotates. A flexible copper clad laminate that was straightened and smooth in appearance was obtained. Thereafter, the flexible copper clad laminate was passed over a roll used only for conveyance and wound up. The obtained flexible copper clad laminate had a good appearance with no wrinkles.
実施例4
実施例1と同様にして作成した積層板を、360℃雰囲気下で、半径300ｍｍの3個の連続した平坦化用の金属製ロール曲面上に銅箔面を内側にし、且つ積層板の流れ方向に130Ｎ/ｍの張力をかけた状態で前記ロール面と銅箔面とをロールの円周長の1/2の範囲で密着させ、ロールの回転と共に積層板を1m/minの速度で搬送したところ、しわが矯正され外観上平坦なフレキシブル銅張積層板が得られた。その後、フレキシブル銅張積層板は搬送だけのために用いられるロール上を通過させ巻き取られた。得られたフレキシブル銅張積層板は波しわがない良外観のものであった。
Example 4
Laminate produced in the same manner as in Example 1, in a 360 ° C. atmosphere, with a copper foil surface on the inside of three continuous metal roll curved surfaces with a radius of 300 mm, and the flow direction of the laminate With the tension of 130 N / m applied to the roll surface, the roll surface and the copper foil surface were brought into close contact with each other in the range of 1/2 of the circumferential length of the roll, and the laminate was conveyed at a speed of 1 m / min with the rotation of the roll. A wrinkle-corrected flexible copper-clad laminate was obtained. Thereafter, the flexible copper clad laminate was passed over a roll used only for conveyance and wound up. The obtained flexible copper clad laminate had a good appearance with no wrinkles.
比較例1〜２
実施例1において、ロール面と銅箔面との密着範囲を、ロール円周長の1/5の範囲とした以外は同様の操作を行った。この場合、搬送工程にて積層板とロールは均一に密着せず、ロール上を搬送し終わった後にも積層板にはしわが残った状態のままであった。
また、実施例1において、常温雰囲気下で、その他は同様の条件で操作を行った。この場合、搬送工程において積層板とロールは均一に密着したが、ロール上を搬送した後にしわが再生した。搬送後のしわの状態は、搬送前とほとんど変わらなかった。
Comparative Examples 1-2
In Example 1, the same operation was performed except that the adhesion range between the roll surface and the copper foil surface was set to a range of 1/5 of the roll circumferential length. In this case, the laminated plate and the roll were not in close contact with each other in the conveyance step, and wrinkles remained on the laminated plate even after conveyance on the roll was completed.
Further, in Example 1, the operation was performed under the same conditions under the normal temperature atmosphere. In this case, the laminate and the roll were in close contact with each other in the transporting process, but wrinkles were regenerated after transporting on the roll. The state of wrinkles after transport was almost the same as before transport.
比較例３〜４
実施例２及び実施例4において、常温雰囲気下で行った以外は同様の操作を行った。この場合、搬送工程において積層板とロールは均一に密着しなかった。また、ロール上を搬送し終わった後のしわの状態は、搬送前とほとんど同じであった。
Comparative Examples 3-4
In Example 2 and Example 4, the same operation was performed except that it was performed in a room temperature atmosphere. In this case, the laminate and the roll were not uniformly adhered in the conveying step. Moreover, the state of the wrinkle after the conveyance on the roll was almost the same as that before the conveyance.
１：積層板
２、３：平坦化用ロール
４、５：ガイドロール
６、７：エアターン
1: Laminated
Claims (5)
In the manufacturing method of the elongate flexible laminated board which has metal foil and a polyimide resin layer, it applied to the resin precursor solution on metal foil , and it was set as the laminated board which formed the polyimide resin layer by heating, drying, and hardening . After that, in an atmosphere of 150 to 450 ° C., the metal foil surface is in contact with the roll surface of the flattening roll having a radius of 100 to 1500 mm in a range of 2/5 to 4/5 of the roll circumferential length in a metal atmosphere. In a state where tension is applied in the flow direction of the laminate, and after passing through the step of contacting and transporting the laminate at a speed range of 1 to 10 m / min with roll rotation, the long flexible laminate is taken up. The manufacturing method of the flexible laminated board characterized by performing continuously.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR100864160B1 (en) * | 2006-04-11 | 2008-10-16 | 주식회사 엘지화학 | Method for preparing copper-clad-laminate and apparatus for preparing the same |
| JP4872596B2 (en) * | 2006-10-26 | 2012-02-08 | パナソニック電工株式会社 | Wrinkle removal device for combination material |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS54111673A (en) * | 1978-02-21 | 1979-09-01 | Kanegafuchi Chemical Ind | Flexible printed circuit board |
| JPS5574838A (en) * | 1978-11-30 | 1980-06-05 | Kanegafuchi Chem Ind Co Ltd | Manufacturing of composite sheet |
| JPS6374635A (en) * | 1986-09-18 | 1988-04-05 | 日立化成工業株式会社 | Manufacture of flexible printed substrate |
| JPH0332832A (en) * | 1989-06-30 | 1991-02-13 | Mitsui Toatsu Chem Inc | Preparation of flexible metal foil laminated sheet |
| JPH05177804A (en) * | 1991-12-27 | 1993-07-20 | Mitsui Toatsu Chem Inc | Manufacturing device of flexible metallic foil laminated sheet |
-
2004
- 2004-03-18 JP JP2004077706A patent/JP4549705B2/en not_active Expired - Lifetime
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS54111673A (en) * | 1978-02-21 | 1979-09-01 | Kanegafuchi Chemical Ind | Flexible printed circuit board |
| JPS5574838A (en) * | 1978-11-30 | 1980-06-05 | Kanegafuchi Chem Ind Co Ltd | Manufacturing of composite sheet |
| JPS6374635A (en) * | 1986-09-18 | 1988-04-05 | 日立化成工業株式会社 | Manufacture of flexible printed substrate |
| JPH0332832A (en) * | 1989-06-30 | 1991-02-13 | Mitsui Toatsu Chem Inc | Preparation of flexible metal foil laminated sheet |
| JPH05177804A (en) * | 1991-12-27 | 1993-07-20 | Mitsui Toatsu Chem Inc | Manufacturing device of flexible metallic foil laminated sheet |
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