JP2008302696A - Method of manufacturing flexible metal foil laminated plate - Google Patents
Method of manufacturing flexible metal foil laminated plate Download PDFInfo
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- JP2008302696A JP2008302696A JP2008177294A JP2008177294A JP2008302696A JP 2008302696 A JP2008302696 A JP 2008302696A JP 2008177294 A JP2008177294 A JP 2008177294A JP 2008177294 A JP2008177294 A JP 2008177294A JP 2008302696 A JP2008302696 A JP 2008302696A
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C66/00—General aspects of processes or apparatus for joining preformed parts
- B29C66/70—General aspects of processes or apparatus for joining preformed parts characterised by the composition, physical properties or the structure of the material of the parts to be joined; Joining with non-plastics material
- B29C66/71—General aspects of processes or apparatus for joining preformed parts characterised by the composition, physical properties or the structure of the material of the parts to be joined; Joining with non-plastics material characterised by the composition of the plastics material of the parts to be joined
Abstract
Description
本発明は、電子工業分野において普及しつつある、フレキシブル金属箔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 flexible metal foil laminate, which is becoming widespread in the electronic industry field.
ポリイミド金属箔積層板は、主として可撓性を有するプリント配線板用の基材として使用され、その他に面状発熱体、電磁波シールド材料、フラットケーブル、包装材料等にも使用される。近年においては、プリント配線板を使用した電子機器が小型化、高密度化されるに伴い、部品・素子の高密度実装が可能な、ポリイミド金属箔積層板の利用が増大している。しかしながら、従来のフレキシブル金属箔積層板は、エポキシ樹脂等の接着剤を用いて、ポリイミドフィルムと金属箔とを貼り合わせることにより製造されているために、耐熱性・耐薬品性・電気特性等の特性は、使用される接着剤の特性に支配され、ポリイミドの優れた諸特性が十分に活かされず、特に耐熱性の点で十分なものではなかった。 The polyimide metal foil laminate is mainly used as a substrate for a flexible printed wiring board, and is also used for a planar heating element, an electromagnetic shielding material, a flat cable, a packaging material, and the like. In recent years, as electronic devices using printed wiring boards are miniaturized and densified, use of polyimide metal foil laminates capable of high-density mounting of components and elements is increasing. However, since conventional flexible metal foil laminates are manufactured by bonding polyimide film and metal foil using an adhesive such as epoxy resin, heat resistance, chemical resistance, electrical characteristics, etc. The characteristics were governed by the characteristics of the adhesive used, and the excellent characteristics of polyimide were not fully utilized, and the heat resistance was not particularly satisfactory.
この、接着剤を有する従来のフレキシブル金属箔積層板の欠点を克服するために、金属箔上にポリイミド溶液またはポリイミドの前駆体であるポリアミド酸溶液を直接流延塗布することにより、通常の接着剤層を有しない、絶縁層が全てポリイミドから成るフレキシブル金属箔積層板を得ようとする試みがなされている。また、ポリイミドフィルムの片面または両面に、接着性を有するポリイミドを積層し、このポリイミド積層体と金属箔とを重ね合わせ加熱圧着して、同様な絶縁層が全てポリイミドから成るフレキシブル金属箔積層板を得ようとする試みもなされている。 In order to overcome the disadvantages of the conventional flexible metal foil laminate having an adhesive, a normal adhesive is obtained by directly casting a polyimide solution or a polyamic acid solution which is a precursor of polyimide onto the metal foil. Attempts have been made to obtain a flexible metal foil laminate having no layers and the insulating layer being entirely made of polyimide. In addition, a polyimide film having adhesive properties is laminated on one or both sides of a polyimide film, and this polyimide laminate and a metal foil are superposed and heat-bonded to form a flexible metal foil laminate having a similar insulating layer made of polyimide. Attempts have also been made to gain.
しかし、これらの方法を用いて、例えば金属箔として銅箔を選択した場合、表面が平滑面である銅箔とポリイミドとの接着力は低く、満足なものは得られない。この欠点を克服するために、金属箔のポリイミドと接する面に対して、予めその表面に凹凸を付け、表面積を増すような各種の表面処理を施すことが行われている。 However, using these methods, for example, when a copper foil is selected as the metal foil, the adhesive strength between the copper foil having a smooth surface and the polyimide is low, and a satisfactory one cannot be obtained. In order to overcome this drawback, various surface treatments are performed on the surface of the metal foil that comes into contact with the polyimide in advance so that the surface is uneven and the surface area is increased.
しかしながら、金属箔に施された表面処理の粗さと、この面と接する接着剤層の厚みとの相関については、十分な議論がなされていなかった。すなわち、我々の検討によれば表面の凹凸に対して接着剤層の厚みが小さい場合には接着剤が凹凸に対して完全に埋め込まれることができず、接着不良の原因となることを見いだした。一方、接着剤層の厚みが表面の凹凸に対して非常に大きくした場合でも、接着力は一定の数値を越えることはなく、かつ接着剤層をあまり厚く構成することは接着剤の使用量の増加、塗布・乾燥工程の長時間化を招き、製造コストの増大に繋がるほか、絶縁層の厚みを必要以上に厚くしてしまうことを見いだした。 However, sufficient discussion has not been made about the correlation between the roughness of the surface treatment applied to the metal foil and the thickness of the adhesive layer in contact with this surface. That is, according to our study, when the thickness of the adhesive layer is small relative to the surface irregularities, it was found that the adhesive could not be completely embedded in the irregularities, resulting in poor adhesion. . On the other hand, even when the thickness of the adhesive layer is very large with respect to the unevenness of the surface, the adhesive strength does not exceed a certain value, and it is necessary to configure the adhesive layer too thick. In addition to increasing the time required for the coating and drying process, the manufacturing cost was increased, and the thickness of the insulating layer was increased more than necessary.
本発明は、優れた耐熱性・耐薬品性・電気特性等を有するポリイミドを絶縁体として用いたフレキシブル金属箔積層板において、金属箔とポリイミドとの間に十分な接着力を得ることができる、フレキシブル金属箔積層板の製造方法を提供するものである。 The present invention is a flexible metal foil laminate using a polyimide having excellent heat resistance, chemical resistance, electrical properties, etc. as an insulator, and can obtain a sufficient adhesive force between the metal foil and the polyimide. A method for producing a flexible metal foil laminate is provided.
本発明者らは鋭意検討した結果、フレキシブル金属箔積層板の金属／絶縁体界面での十分な接着力を得るために必要な接着剤層の厚みが、接着剤層と接する金属箔表面の凹凸の大きさと相関関係があることを見いだし、本発明を完成した。 As a result of intensive studies, the present inventors have found that the thickness of the adhesive layer necessary to obtain sufficient adhesive force at the metal / insulator interface of the flexible metal foil laminate is uneven on the surface of the metal foil in contact with the adhesive layer. As a result, the present invention has been completed.
すなわち、本発明は、
（１）二層の金属箔層の層間にポリイミド層を有するフレキシブル金属箔積層板の製造方法であって、該ポリイミド層が、該ポリイミドフィルムの両面に熱可塑性ポリイミドが形成された、三層構造のポリイミド積層体から成り、該ポリイミド積層体の両側に金属箔層を重ね合わせ、加熱圧着することによって製造されるフレキシブル金属箔積層板の製造方法であり、該熱可塑性ポリイミド層の厚みが、これと接する金属箔の表面の十点平均粗さの、100 ％以上であることを特徴とする、フレキシブル金属箔積層板の製造方法であり、また、
（２）二層の金属箔層の層間にポリイミド層を有するフレキシブル金属箔積層板の製造方法であって、一方の金属箔層上に、少なくとも該金属箔層に対して最も外側のポリイミド層が熱可塑性ポリイミドから成るポリイミド層が形成された、ポリイミド／金属箔積層体と、もう一方の金属箔層とを、該熱可塑性ポリイミド層と金属箔層とを重ね合わせ、加熱圧着することによって製造されるフレキシブル金属箔積層板の製造方法であり、該熱可塑性ポリイミド層の厚みが、これと接する金属箔の表面の十点平均粗さの、100 ％以上であることを特徴とする、フレキシブル金属箔積層板の製造方法であり、また、
（３）金属箔が、銅、鉄、ニッケル、クロム、モリブデン、アルミニウムおよびこれらを主体とする合金から成る金属箔から選択されるものであることを特徴とする、（１）または（２）記載のフレキシブル金属箔積層板の製造方法である。
以下、本発明を詳細に説明する。
That is, the present invention
(1) A method for producing a flexible metal foil laminate having a polyimide layer between two metal foil layers, wherein the polyimide layer is a three-layer structure in which a thermoplastic polyimide is formed on both sides of the polyimide film Is a method for producing a flexible metal foil laminate produced by laminating metal foil layers on both sides of the polyimide laminate and heat-pressing the polyimide laminate, and the thickness of the thermoplastic polyimide layer is A method for producing a flexible metal foil laminate, characterized in that it is 100% or more of the ten-point average roughness of the surface of the metal foil in contact with
(2) A method for producing a flexible metal foil laminate having a polyimide layer between two metal foil layers, wherein at least the outermost polyimide layer with respect to the metal foil layer is formed on one metal foil layer. A polyimide / metal foil laminate formed with a polyimide layer made of thermoplastic polyimide and the other metal foil layer are manufactured by overlaying the thermoplastic polyimide layer and the metal foil layer, and heat-pressing them. Flexible metal foil laminate, wherein the thickness of the thermoplastic polyimide layer is 100% or more of the ten-point average roughness of the surface of the metal foil in contact with the flexible metal foil, A method of manufacturing a laminate, and
(3) The metal foil is selected from metal foils made of copper, iron, nickel, chromium, molybdenum, aluminum, and alloys based on these, (1) or (2) This is a method for producing a flexible metal foil laminate.
Hereinafter, the present invention will be described in detail.
以上説明したように、本発明によれば、金属箔と絶縁層との界面での必要十分な接着力を有する、耐熱性・耐薬品性・電気特性等に優れたフレキシブル金属箔積層板を製造することができる。このことにより、接着剤層である熱可塑性ポリイミド層の厚みを必要最小限度とし、製造コストを削減することができる。さらに、絶縁層の厚みをできるだけ薄くしたフレキシブル金属箔積層板を製造することができる。 As described above, according to the present invention, a flexible metal foil laminate having excellent and sufficient heat resistance, chemical resistance, electrical properties, etc., having necessary and sufficient adhesion at the interface between the metal foil and the insulating layer is manufactured. can do. As a result, the thickness of the thermoplastic polyimide layer, which is the adhesive layer, can be made the minimum necessary, and the manufacturing cost can be reduced. Furthermore, the flexible metal foil laminated board which made the thickness of the insulating layer as thin as possible can be manufactured.
本発明に用いられる金属箔の種類には特に制限はなく、銅および銅合金、鉄、ニッケル、クロム、モリブデン、アルミニウム、ステンレス鋼、ベリリウム銅合金などが使用できる。
本発明に用いられる金属箔の厚みは特に制限はないが、通常5 〜175 μｍの範囲内であり、好ましくは9 〜105 μｍの範囲内のものが一般に用いられる。
There is no restriction | limiting in particular in the kind of metal foil used for this invention, Copper and copper alloy, iron, nickel, chromium, molybdenum, aluminum, stainless steel, beryllium copper alloy, etc. can be used.
The thickness of the metal foil used in the present invention is not particularly limited, but is usually in the range of 5 to 175 μm, and preferably in the range of 9 to 105 μm.
本発明に用いられる金属箔上に、金属単体やその酸化物などの無機物、あるいはアミノシラン、エポキシシラン、メルカプトシラン等のカップリング剤を形成したり、金属箔表面にサンドブラスト処理、ホーニング処理、コロナ処理、プラズマ処理、エッチング処理等の処理を併用することも可能である。 On the metal foil used in the present invention, an inorganic substance such as a single metal or its oxide, or a coupling agent such as aminosilane, epoxysilane, mercaptosilane, or the like, sandblasting, honing, corona treatment on the surface of the metal foil It is also possible to use treatments such as plasma treatment and etching treatment in combination.
本発明の絶縁層としてのポリイミド層は、ポリイミドフィルムの両面に、熱可塑性ポリイミドを積層することによって形成される三層構造のポリイミド積層体である。ここで用いられるポリイミドフィルムは、市販されているポリイミドフィルムを使用しても、流延法、射出法、延伸法等で形成したものを使用してもよい。 The polyimide layer as an insulating layer of the present invention is a three-layered polyimide laminate formed by laminating thermoplastic polyimide on both sides of a polyimide film. The polyimide film used here may be a commercially available polyimide film or a film formed by a casting method, an injection method, a stretching method, or the like.
本発明における接着剤としての熱可塑性ポリイミドとは、主鎖にイミド構造を有するポリマーであって、ガラス転移温度が、好ましくは150 〜350 ℃の範囲内にあり、このガラス転移温度以上の温度領域では、弾性率が急激に低下するものを言う。 The thermoplastic polyimide as an adhesive in the present invention is a polymer having an imide structure in the main chain, and its glass transition temperature is preferably in the range of 150 to 350 ° C., and a temperature range equal to or higher than this glass transition temperature. Then, it means that the elastic modulus decreases rapidly.
また、本発明のポリイミド層は、金属箔にポリイミドおよび／または熱可塑性ポリイミドを積層し、これにもう一方の金属箔を重ね合わせ加熱圧着する場合の該ポリイミドおよび／または熱可塑性ポリイミドでもある。該ポリイミド層は、金属箔層との接着に関わる最も表側の層が熱可塑性ポリイミドであればよく、単一の層でも、異なる多層のポリイミド層から成ってもよい。該表側の層のポリイミド以外は、必ずしも熱可塑性ポリイミドである必要はない。また、該表側の層さえ熱可塑性ポリイミドであるならば、複数のポリイミド成分から成る傾斜材料でもよい。 The polyimide layer of the present invention is also a polyimide and / or thermoplastic polyimide when polyimide and / or thermoplastic polyimide are laminated on a metal foil, and another metal foil is laminated and heat-pressed on the metal foil. In the polyimide layer, the outermost layer involved in adhesion to the metal foil layer may be a thermoplastic polyimide, and may be composed of a single layer or different multilayer polyimide layers. Other than the polyimide of the front side layer, it is not always necessary to be a thermoplastic polyimide. Further, a gradient material composed of a plurality of polyimide components may be used as long as the front layer is a thermoplastic polyimide.
本発明における、絶縁層であるポリイミド層の厚みは特に制限はないが、通常5 〜150 μｍの範囲内であり、好ましくは8 〜50μｍの範囲内のものが一般に用いられる。 In the present invention, the thickness of the polyimide layer, which is an insulating layer, is not particularly limited, but is usually in the range of 5 to 150 μm, and preferably in the range of 8 to 50 μm.
本発明のポリイミド層またはポリイミドフィルムの表面に、サンドブラスト処理、ホーニング処理、コロナ処理、プラズマ処理、エッチング処理等の処理を施してもよい。 You may perform processes, such as a sandblasting process, a honing process, a corona process, a plasma process, an etching process, on the surface of the polyimide layer or polyimide film of this invention.
本発明では、ポリイミド層を形成するために、ポリイミドフィルムに熱可塑性ポリイミドを積層するか、あるいは金属箔にポリイミドおよび／または熱可塑性ポリイミドを積層するが、このポリイミドおよび／または熱可塑性ポリイミドは、該ポリイミド、または該ポリイミドの前駆体が溶媒に溶解した状態でポリイミドフィルム上あるいは金属箔上に塗布し、これをタックフリーの状態まで加熱することが好ましい。塗布する方法には特に限定はなく、コンマコーター、ナイフコーター、ロールコーター、リバースコーター、ダイコーター、グラビアコーター、ワイヤーバー等公知の塗布装置を使用することができる。また、加熱方法には熱風、熱窒素、遠赤外線、高周波等公知の方法を使用することができる。 In the present invention, in order to form a polyimide layer, thermoplastic polyimide is laminated on a polyimide film, or polyimide and / or thermoplastic polyimide is laminated on a metal foil. This polyimide and / or thermoplastic polyimide is It is preferable that polyimide or a precursor of the polyimide is applied on a polyimide film or a metal foil in a state dissolved in a solvent and heated to a tack-free state. The coating method is not particularly limited, and a known coating device such as a comma coater, a knife coater, a roll coater, a reverse coater, a die coater, a gravure coater, or a wire bar can be used. Moreover, well-known methods, such as a hot air, a hot nitrogen, a far infrared ray, and a high frequency, can be used for a heating method.
ポリイミドフィルムまたは金属箔上に、所望のポリイミド層が形成された後、層中の揮発成分を十分除去し、またポリイミドの前駆体を塗布した場合には縮合反応を完了せしめるため、十分に加熱することが必要である。この場合の加熱方法も、上記に準じた各種の公知の方法を使用することができる。加熱温度は、積層されるポリイミドのガラス転移温度より以上の温度が好ましい。ポリイミドフィルムの両面にポリイミド層が形成されている場合には、加熱途中での他の物体との接触を避けるため、エアフロート方式を用いることは特に有用である。また、金属箔層上に形成した場合には、金属箔の酸化劣化を避けるため、不活性ガス中で加熱することも有用である。 After the desired polyimide layer is formed on the polyimide film or metal foil, the volatile components in the layer are sufficiently removed, and when a polyimide precursor is applied, heat is sufficiently applied to complete the condensation reaction. It is necessary. As the heating method in this case, various known methods according to the above can be used. The heating temperature is preferably higher than the glass transition temperature of the laminated polyimide. When a polyimide layer is formed on both sides of the polyimide film, it is particularly useful to use an air float method in order to avoid contact with other objects during heating. Moreover, when formed on a metal foil layer, in order to avoid the oxidative deterioration of metal foil, it is also useful to heat in an inert gas.
本発明において非常に重要なことは、接着剤層である熱可塑性ポリイミド層の厚みを、これと接する金属箔の表面の十点平均粗さ（以下、Rzと表記する）の、100 ％以上とすることである。表面粗さの数値は、JIS B 0601（表面粗さの定義と表示）における、Rzを用いる。 What is very important in the present invention is that the thickness of the thermoplastic polyimide layer as the adhesive layer is 100% or more of the ten-point average roughness (hereinafter referred to as Rz) of the surface of the metal foil in contact therewith. It is to be. For the numerical value of the surface roughness, Rz in JIS B 0601 (Definition and display of surface roughness) is used.
本発明にあるようなフレキシブル金属箔積層板の、金属／絶縁層界面の接着力において、接着剤層の厚みが、これと接する金属箔の表面のRzの100 ％未満である場合には、接着剤が金属箔の表面の凹凸を完全に埋め込むことができず、金属箔と接着剤層との間に微小な空隙を生ずるおそれがある。この空隙の存在はフレキシブル金属箔積層板の金属／絶縁層界面の接着力を低下させるのみならず、半田処理など高温加工工程での膨れ・剥離の原因ともなる。 When the thickness of the adhesive layer is less than 100% of Rz on the surface of the metal foil in contact with the metal / insulating layer interface of the flexible metal foil laminate as in the present invention, The agent cannot completely fill the unevenness of the surface of the metal foil, and there is a possibility that a minute gap is generated between the metal foil and the adhesive layer. The presence of this void not only lowers the adhesive force at the metal / insulating layer interface of the flexible metal foil laminate, but also causes swelling and peeling in high-temperature processing steps such as soldering.
一方、接着剤層の厚みが、これと接する金属箔の表面のRzの100 ％以上である場合には、このような問題は生じない。しかしながら、接着剤層の厚みを増していった場合には接着力も増加してゆくが、その厚みが120 ％を越えた場合には接着力の値はほぼ平衡に達し、さらに150 ％を越えても、120 ％の時の数値を越えることはないことを見いだした。なお、接着剤層の厚みをこの数値を超えていたずらに増すことは、ポリイミドフィルムあるいは金属箔に接着剤を塗布・乾燥する工程において、乾燥の長時間化や塗面の均一性の保持の困難さなど、技術的あるいは経済的な問題を引き起こす。このことから、接着剤層の厚みの上限は、これと接する金属表面のRzの300 ％未満、好ましくは200 ％未満、さらに好ましくは150 ％未満、さらにより好ましくは120 ％未満である。絶縁層がより薄いことが要求される積層板に対して、絶縁層の一部をなす接着剤層の厚みが、物性を損なわない範囲、すなわち上記した範囲でできる限り薄くあるべきなのは自明である。 On the other hand, when the thickness of the adhesive layer is 100% or more of Rz on the surface of the metal foil in contact with the adhesive layer, such a problem does not occur. However, as the thickness of the adhesive layer increases, the adhesive strength also increases. However, when the thickness exceeds 120%, the value of the adhesive strength almost reaches equilibrium, and further exceeds 150%. However, we found that the figure at 120% would never be exceeded. Increasing the thickness of the adhesive layer beyond this value is difficult to maintain the uniformity of the coating surface for a long time in the process of applying and drying the adhesive on the polyimide film or metal foil. Cause technical or economic problems. From this, the upper limit of the thickness of the adhesive layer is less than 300%, preferably less than 200%, more preferably less than 150%, and even more preferably less than 120% of Rz of the metal surface in contact therewith. It is obvious that the thickness of the adhesive layer that forms a part of the insulating layer should be as thin as possible within the range that does not impair the physical properties, that is, the above-described range, for the laminated board that requires a thinner insulating layer. .
このように、接着剤層の厚みを、これと接する金属表面のRzの、100 ％以上とすることによって、金属箔と絶縁層との界面での必要十分な接着力を有し、かつ製造コストに優れ、絶縁層の薄いフレキシブル金属箔積層板を製造することができることを見いだした。 Thus, by setting the thickness of the adhesive layer to 100% or more of the Rz of the metal surface in contact with the adhesive layer, it has a necessary and sufficient adhesive force at the interface between the metal foil and the insulating layer, and the manufacturing cost. It has been found that a flexible metal foil laminate having an excellent insulating property and a thin insulating layer can be produced.
上記のごとくして得られたポリイミド積層体あるいはポリイミド／金属箔積層体と金属箔とを重ね合わせ、加熱圧着することによりフレキシブル金属箔積層板が完成する。この加熱圧着する方法は、熱ロールを用いて熱ラミネートする方法やホットプレス等公知の方法を適宜使用することができる。加熱条件は、用いられる熱可塑性ポリイミドのガラス転移温度に依存するが、好ましくはガラス転移温度以上、より好ましくはこの点より20℃以上あればよい。加圧条件は、一般に20〜150kg/cm2 の範囲が用いられる。 The polyimide laminate or polyimide / metal foil laminate obtained as described above and the metal foil are superposed and heat-pressed to complete a flexible metal foil laminate. As a method for heat-pressing, a known method such as hot laminating using a hot roll or hot pressing can be appropriately used. The heating conditions depend on the glass transition temperature of the thermoplastic polyimide used, but are preferably at least the glass transition temperature, more preferably at least 20 ° C. from this point. As the pressurizing condition, a range of 20 to 150 kg / cm 2 is generally used.
以下の実施例によって、本発明を更に詳細に説明する。
［実施例１〜２、比較例１〜２］
市販のポリイミドフィルム（鐘淵化学工業製, アピカルAH, 厚み;25 μｍ）に、熱可塑性ポリイミドの前駆体であるポリアミド酸溶液（三井東圧化学製, PI-A）を、塗工機によってポリイミドフィルムの両面に塗布・乾燥してポリイミド積層体を得た。この時、各面のポリアミド酸溶液の塗工厚みを、乾燥後の厚みとして、比較例１は0.3 μｍ、比較例２は1.0 μｍ、実施例１は2.0 μｍ、実施例２は3.0 μｍとなるようにした。
The following examples illustrate the invention in more detail.
[Examples 1-2, Comparative Examples 1-2]
Polyamide acid solution (manufactured by Mitsui Toatsu Chemicals, PI-A), which is a precursor of thermoplastic polyimide, is applied to a commercially available polyimide film (Kanebuchi Chemical Industry, Apical AH, thickness: 25 μm) with a coating machine. The polyimide laminate was obtained by coating and drying on both sides of the film. At this time, the coating thickness of the polyamic acid solution on each surface is 0.3 μm in Comparative Example 1, 1.0 μm in Comparative Example 2, 2.0 μm in Example 1, and 3.0 μm in Example 2 as the thickness after drying. I did it.
このポリイミド積層体に対し、圧延銅箔（ジャパンエナジー製, BHY-02B-T,厚み;18 μｍ, Rz;1.85 μｍ）を、ポリイミド積層体の各々の面に重ね合わせ、ホットプレスを用いて加熱圧着した。なお銅箔の表面粗さは、表面粗さ計（小坂研究所製, サーフコーダーSE-30D）で測定したRzの値である。 Rolled copper foil (manufactured by Japan Energy, BHY-02B-T, thickness; 18 μm, Rz; 1.85 μm) is superimposed on each surface of the polyimide laminate, and heated using a hot press. Crimped. The surface roughness of the copper foil is a value of Rz measured with a surface roughness meter (manufactured by Kosaka Laboratory, Surfcoder SE-30D).
得られたフレキシブル金属箔積層板について、各金属箔／ポリイミド界面のピール強度を測定した。以上、実施例１、２、比較例１、２の結果を〔表１〕に示す。 About the obtained flexible metal foil laminated sheet, the peel strength of each metal foil / polyimide interface was measured. The results of Examples 1 and 2 and Comparative Examples 1 and 2 are shown in [Table 1].
［実施例３〜５、比較例３］
市販のポリイミドフィルム（鐘淵化学工業製, アピカルAH, 厚み;25 μｍ）に、熱可塑性ポリイミドの前駆体であるポリアミド酸溶液（三井東圧化学製, PI-A）を、塗工機によってポリイミドフィルムの両面に塗布・乾燥してポリイミド積層体を得た。この時、各面のポリアミド酸溶液の塗工厚みを、乾燥後の厚みとして、比較例３は0.3 μｍ、実施例３は0.5 μｍ、実施例４は1.0 μｍ、実施例５は2.0 μｍとなるようにした。
[Examples 3 to 5, Comparative Example 3]
Polyamide acid solution (manufactured by Mitsui Toatsu Chemicals, PI-A), which is a precursor of thermoplastic polyimide, is applied to a commercially available polyimide film (Kanebuchi Chemical Industry, Apical AH, thickness: 25 μm) with a coating machine. The polyimide laminate was obtained by coating and drying on both sides of the film. At this time, the coating thickness of the polyamic acid solution on each surface is 0.3 μm in Comparative Example 3, 0.5 μm in Example 3, 1.0 μm in Example 4, and 2.0 μm in Example 5 as the thickness after drying. I did it.
このポリイミド積層体に対し、ステンレス箔（日新製鋼製, SUS304H-TA, 厚み;50 μｍ, Rz;0.47 μｍ）を、ポリイミド積層体の各々の面に重ね合わせ、ホットプレスを用いて加熱圧着した。なおステンレス箔の表面粗さは、表面粗さ計（小坂研究所製, サーフコーダーSE-30D）で測定したRzの値である。
得られたフレキシブル金属箔積層板について、各ステンレス箔／ポリイミド界面のピール強度を測定した。以上、実施例３〜５、比較例３の結果を〔表２〕に示す。
Stainless steel foil (manufactured by Nisshin Steel, SUS304H-TA, thickness: 50 μm, Rz; 0.47 μm) was superimposed on each surface of the polyimide laminate and heat-pressed using a hot press. . The surface roughness of the stainless steel foil is a value of Rz measured with a surface roughness meter (manufactured by Kosaka Laboratory, Surfcoder SE-30D).
About the obtained flexible metal foil laminated sheet, the peel strength of each stainless steel foil / polyimide interface was measured. The results of Examples 3 to 5 and Comparative Example 3 are shown in [Table 2].
［実施例６〜７、比較例４〜５］
上記圧延銅箔に、ポリアミド酸溶液（三井東圧化学製, PI-KBP2 ）を、塗工機によって塗布・乾燥し、更にその上に熱可塑性ポリイミドの前駆体であるポリアミド酸溶液（三井東圧化学製, PI-A）を塗布・乾燥してポリイミド／金属箔積層体を得た。この時、ポリアミド酸溶液の塗工厚みを、PI-KBP2 については全ての実施例において乾燥後の厚みとして、13μｍとなるように、PI-Aについては乾燥後の厚みとして、比較例４は0.3 μｍ、比較例５は1.0 μｍ、実施例６は2.0 μｍ、実施例７は3.0 μｍとなるようにした。
[Examples 6-7, Comparative Examples 4-5]
A polyamic acid solution (Mitsui Toatsu Chemical Co., Ltd., PI-KBP2) is applied and dried on the rolled copper foil by a coating machine, and then a polyamic acid solution (Mitsui Toatsu), which is a precursor of thermoplastic polyimide, is further applied thereto. Chemical-made PI-A) was applied and dried to obtain a polyimide / metal foil laminate. At this time, the coating thickness of the polyamic acid solution was set to 13 μm as the thickness after drying in all Examples for PI-KBP2, and as the thickness after drying for PI-A, and 0.3 for Comparative Example 4 μm, Comparative Example 5 was 1.0 μm, Example 6 was 2.0 μm, and Example 7 was 3.0 μm.
このポリイミド／金属箔積層体のポリイミド側に、上記圧延銅箔を重ね合わせ、ホットプレスを用いて加熱圧着した。
得られたフレキシブル金属箔積層板について、圧延銅箔／ポリイミド界面のピール強度を測定した。以上、実施例６〜７、比較例４〜５の結果を〔表３〕に示す。
The rolled copper foil was superposed on the polyimide side of this polyimide / metal foil laminate, and hot-pressed using a hot press.
About the obtained flexible metal foil laminated sheet, the peel strength of the rolled copper foil / polyimide interface was measured. The results of Examples 6 to 7 and Comparative Examples 4 to 5 are shown in [Table 3].
［実施例８〜１０、比較例６］
上記圧延銅箔に、ポリアミド酸溶液（三井東圧化学製, PI-KBP2 ）を、塗工機によって塗布・乾燥し、更にその上に熱可塑性ポリイミドの前駆体であるポリアミド酸溶液（三井東圧化学製, PI-A）を塗布・乾燥してポリイミド／金属箔積層体を得た。この時、ポリアミド酸溶液の塗工厚みを、PI-KBP2 については全ての実施例において乾燥後の厚みとして、13μｍとなるように、PI-Aについては乾燥後の厚みとして、比較例６は0.3 μｍ、実施例８は1.0 μｍ、実施例９は2.0 μｍ、実施例１０は3.0 μｍとなるようにした。
[Examples 8 to 10, Comparative Example 6]
A polyamic acid solution (Mitsui Toatsu Chemical Co., Ltd., PI-KBP2) is applied and dried on the rolled copper foil by a coating machine, and then a polyamic acid solution (Mitsui Toatsu), which is a precursor of thermoplastic polyimide, is further applied thereto. Chemical-made PI-A) was applied and dried to obtain a polyimide / metal foil laminate. At this time, the coating thickness of the polyamic acid solution was set to 13 μm as the thickness after drying in all Examples for PI-KBP2, and as the thickness after drying for PI-A, and 0.3 for Comparative Example 6 μm, Example 8 was 1.0 μm, Example 9 was 2.0 μm, and Example 10 was 3.0 μm.
このポリイミド／金属箔積層体のポリイミド側に、上記ステンレス箔を重ね合わせ、ホットプレスを用いて加熱圧着した。
得られたフレキシブル金属箔積層板について、ステンレス箔／ポリイミド界面のピール強度を測定した。以上、実施例８〜１０、比較例６の結果を〔表４〕に示す。
The above stainless steel foil was superposed on the polyimide side of this polyimide / metal foil laminate, and thermocompression bonded using a hot press.
About the obtained flexible metal foil laminated sheet, the peel strength of the stainless steel foil / polyimide interface was measured. The results of Examples 8 to 10 and Comparative Example 6 are shown in [Table 4].
Claims (3)
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2015081345A (en) * | 2013-10-22 | 2015-04-27 | 達邁科技股▲分▼有限公司 | Polyimide film incorporating polyimide powder matting agent and manufacturing method thereof |
| US9267057B2 (en) | 2011-12-16 | 2016-02-23 | Taimide Technology Incorporated | Polyimide film incorporating polyimide powder delustrant, and manufacture thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH06314877A (en) * | 1993-04-30 | 1994-11-08 | Mitsui Toatsu Chem Inc | Manufacture of long-sized double-faced flexible metal laminated board |
| JPH07193349A (en) * | 1993-12-27 | 1995-07-28 | Mitsui Toatsu Chem Inc | Manufacture of polyimide metal foil laminated board |
| JPH07202417A (en) * | 1993-12-28 | 1995-08-04 | Shin Etsu Chem Co Ltd | Flexible printed wiring board |
-
2008
- 2008-07-07 JP JP2008177294A patent/JP2008302696A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH06314877A (en) * | 1993-04-30 | 1994-11-08 | Mitsui Toatsu Chem Inc | Manufacture of long-sized double-faced flexible metal laminated board |
| JPH07193349A (en) * | 1993-12-27 | 1995-07-28 | Mitsui Toatsu Chem Inc | Manufacture of polyimide metal foil laminated board |
| JPH07202417A (en) * | 1993-12-28 | 1995-08-04 | Shin Etsu Chem Co Ltd | Flexible printed wiring board |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US9267057B2 (en) | 2011-12-16 | 2016-02-23 | Taimide Technology Incorporated | Polyimide film incorporating polyimide powder delustrant, and manufacture thereof |
| JP2015081345A (en) * | 2013-10-22 | 2015-04-27 | 達邁科技股▲分▼有限公司 | Polyimide film incorporating polyimide powder matting agent and manufacturing method thereof |
| CN104553183A (en) * | 2013-10-22 | 2015-04-29 | 达迈科技股份有限公司 | Multilayer polyimide film containing polyimide powder matting agent and method for producing same |
| CN104553183B (en) * | 2013-10-22 | 2017-02-15 | 达迈科技股份有限公司 | Multilayer polyimide film containing polyimide powder matting agent and method for producing same |
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