TWI784065B - Polyimide membrane - Google Patents
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- TWI784065B TWI784065B TW107135205A TW107135205A TWI784065B TW I784065 B TWI784065 B TW I784065B TW 107135205 A TW107135205 A TW 107135205A TW 107135205 A TW107135205 A TW 107135205A TW I784065 B TWI784065 B TW I784065B
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- C08J5/18—Manufacture of films or sheets
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B15/00—Layered products comprising a layer of metal
- B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
- B32B15/08—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/28—Layered products comprising a layer of synthetic resin comprising synthetic resins not wholly covered by any one of the sub-groups B32B27/30 - B32B27/42
- B32B27/281—Layered products comprising a layer of synthetic resin comprising synthetic resins not wholly covered by any one of the sub-groups B32B27/30 - B32B27/42 comprising polyimides
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- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
- C08G73/1067—Wholly aromatic polyimides, i.e. having both tetracarboxylic and diamino moieties aromatically bound
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- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
- C08G73/1075—Partially aromatic polyimides
- C08G73/1078—Partially aromatic polyimides wholly aromatic in the diamino moiety
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- C08K3/013—Fillers, pigments or reinforcing additives
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- C08L79/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen or carbon only, not provided for in groups C08L61/00 - C08L77/00
- C08L79/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
- C08L79/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
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- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K1/00—Printed circuits
- H05K1/02—Details
- H05K1/03—Use of materials for the substrate
- H05K1/0313—Organic insulating material
- H05K1/032—Organic insulating material consisting of one material
- H05K1/0346—Organic insulating material consisting of one material containing N
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- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K1/00—Printed circuits
- H05K1/02—Details
- H05K1/03—Use of materials for the substrate
- H05K1/0313—Organic insulating material
- H05K1/0353—Organic insulating material consisting of two or more materials, e.g. two or more polymers, polymer + filler, + reinforcement
- H05K1/0373—Organic insulating material consisting of two or more materials, e.g. two or more polymers, polymer + filler, + reinforcement containing additives, e.g. fillers
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- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K3/00—Apparatus or processes for manufacturing printed circuits
- H05K3/46—Manufacturing multilayer circuits
- H05K3/4644—Manufacturing multilayer circuits by building the multilayer layer by layer, i.e. build-up multilayer circuits
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2307/00—Properties of the layers or laminate
- B32B2307/70—Other properties
- B32B2307/732—Dimensional properties
- B32B2307/734—Dimensional stability
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2457/00—Electrical equipment
- B32B2457/08—PCBs, i.e. printed circuit boards
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- C08J2379/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen, or carbon only, not provided for in groups C08J2361/00 - C08J2377/00
- C08J2379/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
- C08J2379/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
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- C—CHEMISTRY; METALLURGY
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Abstract
本發明提供一種能夠良好地用於沿不同方向形成有配線之金屬配線基板或多層構造之基板等的新穎聚醯亞胺膜。 於第1態樣中,於聚醯亞胺膜中,將MD方向之熱膨脹係數(αTMD )、TD方向之熱膨脹係數(αTTD )均設為2~7 ppm/℃,將|αTMD -αTTD |設為2 ppm/℃以下,將MD方向之濕度膨脹係數(αHMD )、TD方向之濕度膨脹係數(αHTD )均設為3~16 ppm/%RH,且將|αHMD -αHTD |設為5 ppm/%RH以下。 於第2態樣中,於聚醯亞胺膜中,將MD方向之拉伸彈性模數(EMD )、TD方向之拉伸彈性模數(ETD )均設為5~9 GPa,將|EMD -ETD |設為2 GPa以下,將面內各向異性指數(MT比)設為13以下,且將靜摩擦係數與動摩擦係數兩者均設為0.8以下。The present invention provides a novel polyimide film that can be favorably used for metal wiring boards, multilayer substrates, and the like on which wirings are formed in different directions. In the first aspect, in the polyimide film, the coefficient of thermal expansion in the MD direction (αT MD ) and the thermal expansion coefficient in the TD direction (αT TD ) are set to 2 to 7 ppm/°C, and |αT MD - αT TD | is set below 2 ppm/°C, the humidity expansion coefficient in the MD direction (αH MD ) and the humidity expansion coefficient in the TD direction (αH TD ) are both set to 3-16 ppm/%RH, and |αH MD - αH TD | is set to 5 ppm/%RH or less. In the second aspect, in the polyimide film, both the tensile modulus of elasticity in the MD direction (E MD ) and the tensile modulus of elasticity in the TD direction (E TD ) are set to 5 to 9 GPa, and the |E MD −E TD | is 2 GPa or less, the in-plane anisotropy index (MT ratio) is 13 or less, and both the static friction coefficient and the dynamic friction coefficient are 0.8 or less.
Description
本發明係關於一種聚醯亞胺膜等。The present invention relates to a polyimide film and the like.
隨著電子製品之輕量化、小型化、高密度化,對可撓性印刷配線板(FPC)之需求擴大。FPC具有於絕緣性膜上形成有包含金屬箔之電路之構造,就耐熱性、尺寸穩定性而言,絕緣性膜一直以來偏好使用聚醯亞胺膜。With the light weight, miniaturization and high density of electronic products, the demand for flexible printed wiring board (FPC) is expanding. FPC has a structure in which a circuit including metal foil is formed on an insulating film. In terms of heat resistance and dimensional stability, a polyimide film has been favored for the insulating film.
隨著行動電話等之高功能化及小型化,對於FPC要求較高之撓曲性及尺寸穩定性,為了解決該等問題,業界進行有各種嘗試,作為其一,已知使用彈性模數未達4 GPa之聚醯亞胺膜作為基礎膜及覆蓋膜之可撓性印刷配線板(參照專利文獻1)。該技術藉由調整聚醯亞胺膜之彈性模數而控制附覆蓋層之可撓性印刷配線板之剛度值,可實現良好之撓曲性與尺寸穩定性。 然而,隨著近年來行動裝置之發展,對FPC要求之尺寸穩定性之要求日益嚴格,先前技術已逐漸無法應對。With the increase in functionality and miniaturization of mobile phones, etc., high flexibility and dimensional stability are required for FPC. In order to solve these problems, various attempts have been made in the industry. As one of them, it is known that using elastic modulus is not A polyimide film up to 4 GPa is used as a base film and a cover film for a flexible printed wiring board (refer to Patent Document 1). This technology controls the rigidity value of the flexible printed wiring board with a cover layer by adjusting the elastic modulus of the polyimide film, so as to achieve good flexibility and dimensional stability. However, with the development of mobile devices in recent years, the requirements for the dimensional stability of FPC have become increasingly stringent, and the previous technologies have gradually been unable to cope.
又,隨著電子零件安裝件數之增加,為了於印刷配線板之有限空間內安裝多個電子零件,亦需將軟硬結合板(rigid-flex)之類之適於三維安裝之基板或可撓性印刷配線板進行3層板、4層板等多層化。 作為對多層可撓性印刷配線板要求之特性,可列舉較薄而能夠自由彎折、回彈性(spring back)較小,業界曾製作使用聚醯亞胺膜作為芯基板並藉由接著劑層進行增層之多層可撓性印刷配線板,但由於電路加工後之尺寸穩定性較低,故於安裝電子零件時之位置精度、或層間之尺寸精度上存在課題。Also, with the increase in the number of electronic parts installed, in order to install multiple electronic parts in the limited space of the printed wiring board, it is also necessary to use rigid-flex boards (rigid-flex) and other substrates suitable for three-dimensional installation Flexible printed wiring boards are multi-layered such as 3-layer boards and 4-layer boards. As the characteristics required for multi-layer flexible printed wiring boards, it can be thin and can be bent freely, and the spring back is small. The industry has made polyimide film as the core substrate and through the adhesive layer. Multi-layer flexible printed wiring boards with build-up, but due to the low dimensional stability after circuit processing, there are problems in the positional accuracy when mounting electronic components or the dimensional accuracy between layers.
另一方面,於電子零件之安裝中,由於液晶電視或筆記型電腦、智慧型手機等電子機器之薄型化、高功能化、高精細化,於對顯示器進行驅動之IC(Integrated Circuit,積體電路)之安裝時,要求特別微細且高密度之配線,為了應對於此,開發出在可撓性配線板上直接安裝IC之COF(Chip On Film,薄膜覆晶)方式,並已實用化。On the other hand, in the installation of electronic parts, due to the thinning, high-functioning, and high-definition of electronic equipment such as LCD TVs, notebook computers, and smart phones, ICs (Integrated Circuit, integrated circuits) that drive displays Circuits) requires extremely fine and high-density wiring. In order to cope with this, the COF (Chip On Film) method of directly mounting ICs on flexible wiring boards has been developed and put into practical use.
COF與FPC相比要求更高之尺寸精度,因此,用於COF之覆銅積層板係採用能夠應對配線之微細化、不使用接著劑而直接於聚醯亞胺膜上形成銅層之雙層型。對此有於膜上藉由濺鍍/鍍覆法形成銅層之方法、於銅箔上流延聚醯胺酸後使之醯亞胺化之方法,主流為藉由易實現銅層之薄膜化而有利於微細配線之濺鍍/鍍覆法所形成之雙層覆銅積層板。Compared with FPC, COF requires higher dimensional accuracy. Therefore, the copper-clad laminate used for COF adopts a double layer that can cope with the miniaturization of wiring and directly forms a copper layer on the polyimide film without using an adhesive. type. In this regard, there is a method of forming a copper layer on the film by sputtering/plating, and a method of imidizing it after casting polyamide on the copper foil. The mainstream is to easily realize the thinning of the copper layer. And it is beneficial to the double-layer copper-clad laminate formed by the sputtering/plating method of fine wiring.
然而,先前之聚醯亞胺膜無法用於需安裝複數個電子零件、且需要尺寸精度之方向不固定之設計複雜之可撓性印刷基板。However, the previous polyimide films cannot be used for complex-designed flexible printed substrates that need to mount a plurality of electronic components and require dimensional accuracy in an unstable direction.
如此則例如需要將可撓性印刷基板分成安裝對顯示器進行驅動之IC之部分、及搭載複數個電子機器而需進行複雜電路設計之部分進行設計,從而較大地制約了電子機器之設計。 先前技術文獻 專利文獻In this way, for example, it is necessary to divide the design of the flexible printed circuit board into a part where an IC for driving a display is installed, and a part where complex circuit design is required for mounting a plurality of electronic devices, thereby greatly restricting the design of electronic devices. Prior Art Documents Patent Documents
[專利文獻1]日本專利特開2007-208087號公報[Patent Document 1] Japanese Patent Laid-Open No. 2007-208087
[發明所欲解決之問題][Problem to be solved by the invention]
本發明之目的在於提供一種新穎之聚醯亞胺膜。 [解決問題之技術手段]The object of the present invention is to provide a novel polyimide film. [Technical means to solve the problem]
本發明者等人為了解決上述可撓性印刷基板等中之各種課題,反覆進行聚醯亞胺膜之特性改良,結果發現,特定物性會影響膜之尺寸穩定性,並且藉由將該物性設為特定值,即便用於形成有不同方向之配線、或安裝有複數個零件、或採用多層構造等不限於特定方向之複雜設計之基板,亦可實現優異之尺寸穩定性等,從而完成本發明。The inventors of the present invention have repeatedly improved the properties of the polyimide film in order to solve various problems in the above-mentioned flexible printed circuit board, and found that specific physical properties affect the dimensional stability of the film, and by setting the physical properties is a specific value, even if it is used for a substrate with wiring in different directions, or a substrate with a plurality of parts mounted, or a multilayer structure that is not limited to a specific direction, it can achieve excellent dimensional stability, etc., thereby completing the present invention. .
即,本發明係關於以下之發明等。 [1] 一種聚醯亞胺膜,其MD方向之熱膨脹係數(αTMD )、TD方向之熱膨脹係數(αTTD )均為2~7 ppm/℃,|αTMD -αTTD |為2 ppm/℃以下,MD方向之濕度膨脹係數(αHMD )、TD方向之濕度膨脹係數(αHTD )均為3~16 ppm/%RH,且|αHMD -αHTD |為5 ppm/%RH以下。 [2] 一種聚醯亞胺膜,其MD方向之拉伸彈性模數(EMD )、TD方向之拉伸彈性模數(ETD )均為5~9 GPa,|EMD -ETD |為2 GPa以下,面內各向異性指數(MT比)為13以下,且靜摩擦係數與動摩擦係數兩者均為0.8以下。 [3] 如[1]或[2]記載之聚醯亞胺膜,其係選自(於複數個部位)形成有不同方向之配線之基板、安裝有複數個電子零件之基板、及具有多層構造之基板中之至少1種基板用之聚醯亞胺膜。 [4] 如[1]至[3]中任一項記載之聚醯亞胺膜,其滿足環剛度75 mN/cm以下。 [5] 如[1]至[4]中任一項記載之聚醯亞胺膜,其包含如下聚醯亞胺,上述聚醯亞胺以包含對苯二胺之芳香族二胺成分、及選自由均苯四甲酸二酐與3,3'-4,4'-聯苯四羧酸二酐所組成之群中之1種以上之酸酐成分作為聚合成分。 [6] 如[1]至[5]中任一項記載之聚醯亞胺膜,其含有無機粒子。 [7] 如[1]至[6]中任一項記載之聚醯亞胺膜,其包含如下聚醯亞胺,且含有0.05質量%以上之平均粒徑0.03~1 μm之無機粒子,上述聚醯亞胺以包含35莫耳%以上之對苯二胺之芳香族二胺成分、及選自由均苯四甲酸二酐與3,3'-4,4'-聯苯四羧酸二酐所組成之群中之1種以上之酸酐成分作為聚合成分。 [8] 一種基板,其具備如[1]至[7]中任一項記載之聚醯亞胺膜與金屬層。 [9] 一種基板(配線板),其具備如[1]至[7]中任一項記載之聚醯亞胺膜與形成於該膜上之配線(金屬配線)。 [10] 如[9]記載之基板,其(於複數個部位)形成有不同方向之配線(金屬配線)。 [11] 如[10]記載之基板,其至少於沿聚醯亞胺膜之MD方向及TD方向之兩個方向上形成有配線。 [12] 如[9]至[11]中任一項記載之基板,其配線橫斷方向之熱膨脹係數處於2~8 ppm/℃之範圍。 [13] 一種覆蓋膜,其包含如[1]至[7]中任一項記載之聚醯亞胺膜。 [14] 如[13]記載之覆蓋膜,其中聚醯亞胺膜之厚度為5~25 μm。 [15] 如[13]或[14]記載之覆蓋膜,其係選自(於複數個部位)形成有不同方向之配線之基板、安裝有複數個電子零件之基板、及具有多層構造之基板中之至少1種基板用之覆蓋膜。 [16] 一種電子零件安裝基板,其具備如[8]至[15]中任一項記載之基板及/或覆蓋膜。 [17] 如[16]記載之基板,其安裝有複數個電子零件。 [18] 如[17]記載之基板,其具備至少於沿聚醯亞胺膜之MD方向及TD方向之兩個方向上形成有配線之基板,於該配線上分別安裝有電子零件。 [19] 一種基板,其具有具備如[8]至[18]中任一項記載之基板及/或覆蓋膜之多層構造。 [發明之效果]That is, the present invention relates to the following inventions and the like. [1] A polyimide film, the coefficient of thermal expansion in the MD direction (αT MD ) and the thermal expansion coefficient in the TD direction (αT TD ) are both 2-7 ppm/°C, and |αT MD - αT TD | is 2 ppm/°C Below ℃, the humidity expansion coefficient in MD direction (αH MD ) and the humidity expansion coefficient in TD direction (αH TD ) are both 3-16 ppm/%RH, and |αH MD -αH TD | is below 5 ppm/%RH. [2] A polyimide film, the tensile modulus of elasticity in the MD direction (E MD ) and the tensile modulus of elasticity in the TD direction (E TD ) are both 5 to 9 GPa, | E MD - E TD | 2 GPa or less, the in-plane anisotropy index (MT ratio) is 13 or less, and both the static friction coefficient and the dynamic friction coefficient are 0.8 or less. [3] The polyimide film as described in [1] or [2], which is selected from substrates on which wiring in different directions is formed (at multiple locations), substrates on which multiple electronic components are mounted, and multilayered substrates. A polyimide film for at least one of the substrates of the structure. [4] The polyimide film according to any one of [1] to [3], which satisfies a ring stiffness of 75 mN/cm or less. [5] The polyimide film according to any one of [1] to [4], comprising a polyimide having an aromatic diamine component including p-phenylenediamine, and One or more acid anhydride components selected from the group consisting of pyromellitic dianhydride and 3,3'-4,4'-biphenyltetracarboxylic dianhydride are used as polymerization components. [6] The polyimide film according to any one of [1] to [5], which contains inorganic particles. [7] The polyimide film according to any one of [1] to [6], which contains the following polyimide, and contains 0.05% by mass or more of inorganic particles with an average particle diameter of 0.03 to 1 μm, the above-mentioned Polyimide is an aromatic diamine component containing more than 35 mol% p-phenylenediamine, and is selected from pyromellitic dianhydride and 3,3'-4,4'-biphenyltetracarboxylic dianhydride One or more acid anhydride components in the formed group are used as polymerization components. [8] A substrate comprising the polyimide film and the metal layer according to any one of [1] to [7]. [9] A substrate (wiring board) comprising the polyimide film according to any one of [1] to [7] and wiring (metal wiring) formed on the film. [10] The substrate according to [9], in which wiring (metal wiring) in different directions is formed (at a plurality of locations). [11] The substrate according to [10], wherein wiring is formed in at least two directions along the MD direction and the TD direction of the polyimide film. [12] The substrate according to any one of [9] to [11], wherein the thermal expansion coefficient in the transverse direction of the wiring is in the range of 2 to 8 ppm/°C. [13] A cover film comprising the polyimide film according to any one of [1] to [7]. [14] The cover film according to [13], wherein the polyimide film has a thickness of 5 to 25 μm. [15] The cover film as described in [13] or [14], which is selected from substrates on which wirings in different directions are formed (in a plurality of locations), substrates on which a plurality of electronic components are mounted, and substrates having a multilayer structure A cover film for at least one of the substrates. [16] A substrate for mounting electronic components, comprising the substrate and/or cover film according to any one of [8] to [15]. [17] The substrate as described in [16], on which a plurality of electronic components are mounted. [18] The substrate according to [17], which includes a substrate having wiring formed in at least two directions along the MD direction and the TD direction of the polyimide film, and electronic components are respectively mounted on the wiring. [19] A substrate having a multilayer structure including the substrate and/or cover film according to any one of [8] to [18]. [Effect of Invention]
於本發明中,可獲得一種新穎之聚醯亞胺膜。於本發明中,尤其可提供一種不限於一個方向而於不同方向(MD方向及TD方向等)乃至所有方向上尺寸穩定性均優異之膜。 又,於本發明中,可提供一種表面平滑性優異之聚醯亞胺膜。此種膜於操作性方面優異,可效率良好地抑制於捲取時等產生皺褶、應用於基板時發生搬送不良、於膜表面產生損傷等。 進而,於本發明中,亦可提供一種不僅具備上述特性、並且兼備彎折特性等物性之聚醯亞胺膜。In the present invention, a novel polyimide film can be obtained. In the present invention, it is possible to provide a film excellent in dimensional stability not only in one direction but in different directions (MD direction, TD direction, etc.) or all directions. Also, in the present invention, a polyimide film excellent in surface smoothness can be provided. Such a film is excellent in handleability, and can efficiently suppress the occurrence of wrinkles during winding, etc., the occurrence of poor transport when applied to a substrate, and the occurrence of scratches on the film surface. Furthermore, in the present invention, it is also possible to provide a polyimide film having not only the above-mentioned characteristics but also physical properties such as bending characteristics.
此種本發明之聚醯亞胺膜尤其由於具備如上所述良好之尺寸穩定性(進而,良好之尺寸穩定性與優異之表面平滑性或優異之物性相輔相成),故而能夠良好地用於形成不同方向(例如膜之寬度方向及長度方向)之配線(特別是窄間距之配線)、或安裝複數個電子零件、或形成多層構造之基板等。This kind of polyimide film of the present invention especially because possesses above-mentioned good dimensional stability (and then, good dimensional stability and excellent surface smoothness or excellent physical properties complement each other), so can be well used for forming different Direction (such as the width direction and length direction of the film) wiring (especially narrow-pitch wiring), or mounting multiple electronic components, or forming a substrate with a multilayer structure, etc.
[聚醯亞胺膜] 本發明之聚醯亞胺膜於熱膨脹性係數、濕度膨脹係數、摩擦係數、拉伸彈性模數、面內各向異性指數等物性方面滿足特定範圍(值)。再者,本發明之聚醯亞胺膜只要滿足此種特定範圍之物性中之至少任一者即可,亦可將該等加以組合而滿足。於較佳態樣中,將該等加以組合而滿足。[Polyimide Film] The polyimide film of the present invention satisfies specific ranges (values) in physical properties such as thermal expansion coefficient, humidity expansion coefficient, friction coefficient, tensile elastic modulus, and in-plane anisotropy index. In addition, the polyimide film of this invention should just satisfy at least any one of the physical properties of the said specific range, and these may be combined and satisfied. In a preferable aspect, these are combined and are satisfied.
又,聚醯亞胺膜只要至少於膜之一面(單面)滿足此種物性值即可,亦可於兩面(一面及另一面)均具有此種物性值。In addition, the polyimide film only needs to satisfy such physical property values on at least one side (single side) of the film, and may have such physical property values on both sides (one side and the other side).
關於聚醯亞胺膜之熱膨脹係數,MD方向(機械搬送方向、長邊方向、縱向、長度方向、行進方向)之熱膨脹係數(αTMD )及/或TD方向(寬度方向、橫向、與MD方向垂直之方向)之熱膨脹係數(αTTD )(尤其是αTMD 及αTTD 兩者)例如可為12 ppm/℃以下(例如10 ppm/℃以下),較佳為8 ppm/℃以下(例如2~7 ppm/℃),更佳為7 ppm/℃以下(例如2.5~6.5 ppm/℃),若為6 ppm℃以下(例如3~6 ppm/℃)則進而更佳。Regarding the thermal expansion coefficient of the polyimide film, the thermal expansion coefficient (αT MD ) in the MD direction (machine conveying direction, longitudinal direction, longitudinal direction, longitudinal direction, and traveling direction) and/or the TD direction (width direction, transverse direction, and MD direction) Vertical direction) thermal expansion coefficient (αT TD ) (especially both αT MD and αT TD ) can be, for example, 12 ppm/°C or less (eg, 10 ppm/°C or less), preferably 8 ppm/°C or less (eg, 2 ~7 ppm/°C), more preferably 7 ppm/°C or less (for example, 2.5 to 6.5 ppm/°C), and even more preferably 6 ppm or less (for example, 3 to 6 ppm/°C).
又,於聚醯亞胺膜中,|αTMD -αTTD |例如可為6 ppm/℃以下(例如5 ppm/℃以下),較佳為4 ppm/℃以下(例如3.5 ppm/℃以下),進而較佳為3 ppm/℃以下(例如2.5 ppm/℃以下),尤其可為2 ppm/℃以下,若為1.5 ppm/℃以下則進而更佳。Also, in the polyimide film, |αT MD -αT TD | can be, for example, 6 ppm/°C or less (eg, 5 ppm/°C or less), preferably 4 ppm/°C or less (eg, 3.5 ppm/°C or less) , and more preferably 3 ppm/°C or less (for example, 2.5 ppm/°C or less), especially 2 ppm/°C or less, and even more preferably 1.5 ppm/°C or less.
藉由減小熱膨脹係數,容易抑制因熱引起之尺寸變化(膨脹)。因此,例如能夠抑制安裝電子零件時之加工溫度下之基板之膨脹,降低安裝不良之發生風險。 又,藉由減小|αTMD -αTTD |,可於多方向上均衡地抑制此種尺寸變化或膨脹。因此,例如不會將電子零件之安裝方向限定於一個方向上,電路設計之自由度飛躍性提高。By reducing the coefficient of thermal expansion, it is easy to suppress dimensional change (expansion) due to heat. Therefore, for example, the expansion of the substrate at the processing temperature when mounting electronic components can be suppressed, and the risk of occurrence of mounting failure can be reduced. Furthermore, by reducing |αT MD −αT TD |, such dimensional change or expansion can be suppressed in a balanced manner in multiple directions. Therefore, for example, the mounting direction of electronic components is not limited to one direction, and the degree of freedom of circuit design is greatly improved.
再者,熱膨脹係數之測定方法並無特別限定,例如可於溫度範圍50~200℃、升溫速度10℃/min之條件下測定。Furthermore, the method for measuring the coefficient of thermal expansion is not particularly limited, for example, it can be measured under the conditions of a temperature range of 50°C to 200°C and a heating rate of 10°C/min.
關於聚醯亞胺膜之濕度膨脹係數,MD方向之濕度膨脹係數(αHMD )及/或TD方向之濕度膨脹係數(αHTD )(尤其是αHMD 及αHTD 兩者)例如為20 ppm/%RH以下(例如18 ppm/%RH以下),較佳為16 ppm/%RH以下(例如3~16 ppm/%RH),更佳為15 ppm/%RH以下(例如4~15 ppm/%RH),若為14 ppm/%RH以下(例如5~14 ppm/℃)則進而更佳。Regarding the humidity expansion coefficient of the polyimide film, the humidity expansion coefficient in the MD direction (αH MD ) and/or the humidity expansion coefficient in the TD direction (αH TD ) (in particular, both αH MD and αH TD ) is, for example, 20 ppm/ Below %RH (such as below 18 ppm/%RH), preferably below 16 ppm/%RH (such as 3-16 ppm/%RH), more preferably below 15 ppm/%RH (such as 4-15 ppm/% RH), it is more preferable if it is 14 ppm/%RH or less (for example, 5-14 ppm/°C).
又,於聚醯亞胺膜中,|αHMD -αHTD |例如為6 ppm/%RH以下,較佳為5 ppm/%RH以下,更佳為4 ppm/%RH以下,若為3 ppm/%RH以下(例如2.5 ppm/%RH以下、2 ppm/%RH以下)則進而更佳。Also, in the polyimide film, |αH MD -αH TD | is, for example, 6 ppm/%RH or less, preferably 5 ppm/%RH or less, more preferably 4 ppm/%RH or less, and if it is 3 ppm /%RH or less (for example, 2.5 ppm/%RH or less, 2 ppm/%RH or less) is still more preferable.
藉由減小濕度膨脹係數,容易抑制因濕度引起之尺寸變化。因此,例如能夠減輕因安裝電子零件之步驟之濕度所引起之基板之尺寸變化,降低安裝不良之發生風險。 又,藉由減小|αHMD -αHTD |,可於多方向上均衡地抑制此種尺寸變化。因此,例如不會將電子零件之安裝方向限定於一個方向上,電路設計之自由度飛躍性提高。By reducing the coefficient of humidity expansion, it is easy to suppress dimensional changes caused by humidity. Therefore, for example, the dimensional change of the substrate due to the humidity in the step of mounting electronic components can be reduced, and the risk of occurrence of mounting failure can be reduced. Also, by reducing |αH MD −αH TD |, such dimensional changes can be suppressed in a balanced manner in multiple directions. Therefore, for example, the mounting direction of electronic components is not limited to one direction, and the degree of freedom of circuit design is greatly improved.
再者,濕度膨脹係數之測定方法並無特別限定,例如可於溫度範圍25℃、濕度範圍25~70 ppm/%RH之條件下測定。Furthermore, the method for measuring the humidity expansion coefficient is not particularly limited, for example, it can be measured under the conditions of a temperature range of 25° C. and a humidity range of 25-70 ppm/%RH.
聚醯亞胺膜之MD方向之拉伸彈性模數(EMD )及/或TD方向之拉伸彈性模數(ETD )(尤其是EMD 及ETD 兩者)可為12 GPa以下(例如10 GPa以下),較佳為9 GPa以下(例如5~9 GPa),進而較佳為8.5 GPa以下(例如5.5~8.5 GPa),尤其可為8 GPa以下(例如6~8 GPa)。又,EMD 及/或ETD 之下限值並無特別限定,就搬送性等觀點而言,可設為3 GPa、4 GPa、5 GPa等。 滿足此種EMD 及/或ETD 之膜可減小回彈性、尤其是配線基板之回彈性,容易減輕將電子零件組入至電子機器中時對連接部位之應力(stress)。The tensile modulus of elasticity in the MD direction (E MD ) and/or the tensile modulus of elasticity in the TD direction (E TD ) of the polyimide film (especially both E MD and E TD ) may be 12 GPa or less ( For example, 10 GPa or less), preferably 9 GPa or less (for example, 5-9 GPa), more preferably 8.5 GPa or less (for example, 5.5-8.5 GPa), especially 8 GPa or less (for example, 6-8 GPa). Also, the lower limit of E MD and/or E TD is not particularly limited, and may be 3 GPa, 4 GPa, 5 GPa, etc. from the viewpoint of transportability or the like. A film that satisfies such EMD and/or ETD can reduce resilience, especially the resilience of a wiring substrate, and easily relieve the stress on the connection part when electronic components are assembled into electronic equipment.
又,於聚醯亞胺膜中,|EMD -ETD |之值例如可為3 GPa以下(例如2.5 GPa以下),較佳為2 GPa以下(例如1.8 GPa以下),進而較佳為1.5 GPa以下(例如1.2 GPa以下),尤其可為1 GPa以下(例如0.8 GPa以下、0.7 GPa以下、0.6 GPa以下、0.5 GPa以下)。 此種EMD 與ETD 之差較小之膜不論彎折方向均可獲得良好之撓曲性,因此能夠縮小配線基板等之空間,亦能夠應對電子機器之小型化。In addition, in the polyimide film, the value of |E MD - E TD | can be, for example, 3 GPa or less (for example, 2.5 GPa or less), preferably 2 GPa or less (for example, 1.8 GPa or less), and more preferably 1.5 GPa or less. GPa or less (eg, 1.2 GPa or less), especially 1 GPa or less (eg, 0.8 GPa or less, 0.7 GPa or less, 0.6 GPa or less, 0.5 GPa or less). Such a film with a small difference between EMD and ETD can obtain good flexibility regardless of the bending direction, so it can reduce the space of a wiring board and the like, and can also cope with the miniaturization of electronic equipment.
再者,拉伸彈性模數之測定方法並無特別限定,例如可於拉伸速度100 mm/min之條件下測定。Furthermore, the method for measuring the tensile elastic modulus is not particularly limited, for example, it can be measured under the condition of a tensile speed of 100 mm/min.
聚醯亞胺膜之面內各向異性指數(MT比)例如為20以下(例如18以下),較佳為15以下(例如14以下),更佳為13以下,進而較佳為12以下,若為10以下(例如9以下)則進而更佳。 具有此種面內各向異性指數之膜容易減輕翹曲、尤其是金屬積層基板等之翹曲。因此,容易以良好之產率製作配線基板。The in-plane anisotropy index (MT ratio) of the polyimide film is, for example, 20 or less (eg, 18 or less), preferably 15 or less (eg, 14 or less), more preferably 13 or less, and more preferably 12 or less, It is still more preferable if it is 10 or less (for example, 9 or less). A film having such an in-plane anisotropy index tends to reduce warpage, especially warpage of metal laminated substrates and the like. Therefore, it is easy to produce a wiring board with good yield.
再者,面內各向異性指數之測定方法並無特別限定,例如可藉由下文記述之方法測定。In addition, the measuring method of an in-plane anisotropy index is not specifically limited, For example, it can measure by the method described below.
關於聚醯亞胺膜之摩擦係數,靜摩擦係數及/或動摩擦係數(尤其是靜摩擦係數及動摩擦係數兩者)可為1.2以下(例如1以下),較佳為0.8以下(例如0.1~0.75),進而較佳為0.7以下(例如0.15~0.65),亦可為0.6以下(例如0.2~0.6)。Regarding the coefficient of friction of the polyimide film, the coefficient of static friction and/or the coefficient of dynamic friction (especially both the coefficient of static friction and the coefficient of dynamic friction) may be 1.2 or less (for example, 1 or less), preferably 0.8 or less (for example, 0.1 to 0.75), Furthermore, it is preferably 0.7 or less (for example, 0.15 to 0.65), and may be 0.6 or less (for example, 0.2 to 0.6).
滿足此種摩擦係數之膜於操作性方面優異,可效率良好地抑制於捲取成捲筒狀等時產生皺褶、形成金屬層時發生搬送不良、產生損傷等情況。A film that satisfies such a coefficient of friction is excellent in handleability, and can efficiently suppress occurrence of wrinkles when winding up into a roll, etc., and occurrence of poor transport or damage when forming a metal layer.
再者,摩擦係數之測定方法並無特別限定,例如可於荷重200 g及測定速度120 mm/min之條件下測定。Furthermore, the method for measuring the coefficient of friction is not particularly limited, for example, it can be measured under the conditions of a load of 200 g and a measurement speed of 120 mm/min.
聚醯亞胺膜之環剛度例如為150 mN/cm以下(例如100 mN/cm以下),較佳為75 mN/cm以下,更佳為60 mN/cm以下,若為50 mN/cm以下則進而更佳。The ring stiffness of the polyimide film is, for example, 150 mN/cm or less (for example, 100 mN/cm or less), preferably 75 mN/cm or less, more preferably 60 mN/cm or less, and if it is 50 mN/cm or less then And then even better.
具有此種環剛度之聚醯亞胺膜可減小回彈性、尤其是配線基板等之回彈性,容易減輕將電子零件組入至電子機器中時對連接部位之應力。The polyimide film with such ring rigidity can reduce the resilience, especially the resilience of the wiring board, etc., and it is easy to reduce the stress on the connection part when the electronic parts are assembled into the electronic machine.
再者,環剛度之測定方法並無特別限定,例如可藉由下文記述之方法測定。In addition, the measuring method of ring stiffness is not specifically limited, For example, it can measure by the method described below.
聚醯亞胺膜可包含無機粒子(或填料)。作為無機粒子,並無特別限定,例如可列舉:氧化物(例如氧化鈦、二氧化矽等)、無機酸鹽[例如碳酸鹽(例如碳酸鈣)、磷酸鹽(例如磷酸鈣、磷酸氫鈣)等]。The polyimide film may contain inorganic particles (or fillers). The inorganic particles are not particularly limited, and examples include: oxides (such as titanium oxide, silicon dioxide, etc.), inorganic acid salts [such as carbonates (such as calcium carbonate), phosphates (such as calcium phosphate, calcium hydrogen phosphate) Wait].
無機粒子之平均粒徑例如可為0.01~5 μm,較佳為0.02~2 μm(例如0.03~1 μm),進而較佳為0.05~0.5 μm左右。 再者,無機粒子之平均粒徑例如係在分散於DMAc(N,N-二甲基乙醯胺)中之漿料狀態下,於利用堀場製作所製造之雷射繞射/散射式粒徑分佈測定裝置LA-920測得之粒度分佈中,將中值粒徑定義為平均粒徑。The average particle diameter of the inorganic particles may be, for example, 0.01-5 μm, preferably 0.02-2 μm (for example, 0.03-1 μm), and more preferably about 0.05-0.5 μm. In addition, the average particle diameter of the inorganic particles is, for example, in the state of a slurry dispersed in DMAc (N,N-dimethylacetamide), using a laser diffraction/scattering particle size distribution method manufactured by Horiba Seisakusho. In the particle size distribution measured by measuring device LA-920, the median particle size is defined as the average particle size.
無機粒子之含量只要無損本發明之效果則並無特別限定,例如相對於聚醯亞胺膜,可為0.05質量%以上,較佳為0.1~1.5質量%,進而較佳為0.2~1.0質量%。The content of the inorganic particles is not particularly limited as long as the effects of the present invention are not impaired. For example, it may be 0.05% by mass or more, preferably 0.1 to 1.5% by mass, and more preferably 0.2 to 1.0% by mass relative to the polyimide film. .
聚醯亞胺膜之厚度並無特別限定,可根據用途等適當選擇。聚醯亞胺膜之厚度例如可為1~200 μm(例如2~150 μm),較佳為3~100 μm(例如4~90 μm),進而較佳為5~80 μm(例如6~60 μm),亦可為7~50 μm、10~40 μm等。The thickness of the polyimide film is not particularly limited, and can be appropriately selected according to applications and the like. The thickness of the polyimide film can be, for example, 1-200 μm (such as 2-150 μm), preferably 3-100 μm (such as 4-90 μm), and more preferably 5-80 μm (such as 6-60 μm). μm), or 7-50 μm, 10-40 μm, etc.
聚醯亞胺膜(或構成聚醯亞胺膜之聚醯亞胺)之玻璃轉移溫度並無特別限定,例如可為200℃以上(例如250~450℃),較佳為250℃以上(例如280~400℃),進而較佳為300℃以上(例如330~400℃)。The glass transition temperature of the polyimide film (or the polyimide constituting the polyimide film) is not particularly limited, for example, it may be above 200°C (for example, 250 to 450°C), preferably above 250°C (for example, 280 to 400°C), more preferably 300°C or higher (for example, 330 to 400°C).
聚醯亞胺膜可具有相對較大之尺寸。此種聚醯亞胺膜之長度可為1 m以上(例如5 m以上)、10 m以上(例如20 m以上),較佳為30 m以上(例如40 m以上),進而較佳為50 m以上(例如100 m以上),亦可為200 m以上、300 m以上、500 m以上、1000 m以上、2000 m以上、3000 m以上、5000 m以上等。Polyimide films can have relatively large dimensions. The length of this polyimide film can be more than 1 m (for example, more than 5 m), more than 10 m (for example, more than 20 m), preferably more than 30 m (for example, more than 40 m), and more preferably 50 m More than (for example, 100 m or more), 200 m or more, 300 m or more, 500 m or more, 1000 m or more, 2000 m or more, 3000 m or more, 5000 m or more, etc.
再者,聚醯亞胺膜之長度之上限值並無特別限定,例如可為30000 m、20000 m、10000 m等。Furthermore, the upper limit of the length of the polyimide film is not particularly limited, for example, it may be 30000 m, 20000 m, 10000 m or the like.
聚醯亞胺膜之寬度並無特別限定,例如可為30 mm以上(例如45 mm以上),較佳為150 mm以上(例如155 mm以上),進而較佳為200 mm以上(例如250 mm以上),亦可為500 mm以上、1000 mm以上、1500 mm以上等。The width of the polyimide film is not particularly limited. For example, it can be more than 30 mm (for example, more than 45 mm), preferably more than 150 mm (for example, more than 155 mm), and more preferably more than 200 mm (for example, more than 250 mm). ), it can also be more than 500 mm, more than 1000 mm, more than 1500 mm, etc.
再者,聚醯亞胺膜之寬度之上限值並無特別限定,例如可為10000 mm、8000 mm、5000 mm、4000 mm、3000 mm、2000 mm、1500 mm等。Furthermore, the upper limit of the width of the polyimide film is not particularly limited, for example, it may be 10000 mm, 8000 mm, 5000 mm, 4000 mm, 3000 mm, 2000 mm, 1500 mm and the like.
聚醯亞胺膜可為經捲取之狀態,即捲筒狀(捲筒)。The polyimide film may be rolled up, that is, in the form of a roll (roll).
(聚醯亞胺及聚醯亞胺膜之製造方法) 聚醯亞胺膜(或構成聚醯亞胺膜之聚醯亞胺、或聚醯胺酸)通常係以芳香族二胺成分與酸酐成分(四羧酸成分)作為聚合成分。再者,聚合成分只要以芳香族二胺成分與酸酐成分作為主成分,則亦可包含其他聚合成分。 製造聚醯亞胺膜時並無特別限定,首先,藉由使芳香族二胺成分與酸酐成分於有機溶劑中進行聚合而獲得聚醯胺酸(polyamic acid)溶液。(Manufacturing method of polyimide and polyimide film) Polyimide film (or polyimide or polyamic acid constituting polyimide film) is usually made of aromatic diamine component and acid anhydride Component (tetracarboxylic acid component) as a polymerization component. In addition, as long as the polymerization component has an aromatic diamine component and an acid anhydride component as a main component, it may contain other polymerization components. There are no particular limitations on the production of the polyimide film. First, a polyamic acid solution is obtained by polymerizing the aromatic diamine component and the acid anhydride component in an organic solvent.
本發明之聚醯亞胺膜尤佳為可包含對苯二胺作為芳香族二胺成分。藉由如此使用包含對苯二胺之芳香族二胺成分,容易效率良好地獲得具有如上特性、物性之聚醯亞胺膜。 芳香族二胺成分亦可包含對苯二胺以外者。作為此種對苯二胺以外之上述芳香族二胺成分之具體例,可列舉:間苯二胺、聯苯胺、對苯二胺、4,4'-二胺基二苯醚、3,4'-二胺基二苯醚、4,4'-二胺基二苯甲烷、4,4'-二胺基二苯碸、3,3'-二甲基-4,4'-二胺基二苯甲烷、1,5-二胺基萘、3,3'-二甲氧基聯苯胺、1,4-雙(3-甲基-5-胺基苯基)苯及該等之醯胺形成性衍生物。該等可單獨使用1種,亦可將2種以上混合使用。 作為芳香族二胺成分,較佳為對苯二胺與4,4'-二胺基二苯醚及/或3,4'-二胺基二苯醚之組合。其中,調整具有提高膜之拉伸彈性模數之效果的對苯二胺、3,4'-二胺基二苯醚之二胺成分之量,而調整所獲得之聚醯亞胺膜之拉伸彈性模數之下限值(例如設為5 GPa以上)會使搬送性亦變得良好,因此較佳。Particularly preferably, the polyimide film of the present invention may contain p-phenylenediamine as an aromatic diamine component. By using the aromatic diamine component containing p-phenylenediamine in this way, it becomes easy and efficient to obtain the polyimide film which has the above-mentioned characteristics and physical properties. The aromatic diamine component may also contain things other than p-phenylenediamine. Specific examples of the aforementioned aromatic diamine components other than p-phenylenediamine include m-phenylenediamine, benzidine, p-phenylenediamine, 4,4'-diaminodiphenyl ether, 3,4 '-Diaminodiphenyl ether, 4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylene, 3,3'-dimethyl-4,4'-diamino Diphenylmethane, 1,5-diaminonaphthalene, 3,3'-dimethoxybenzidine, 1,4-bis(3-methyl-5-aminophenyl)benzene and their amides Formative derivatives. These may be used individually by 1 type, and may mix and
作為上述酸酐成分之具體例,可列舉:均苯四甲酸、3,3',4,4'-聯苯四羧酸、2,3',3,4'-聯苯四羧酸、3,3',4,4'-二苯甲酮四羧酸、2,3,6,7-萘四羧酸、2,2-雙(3,4-二羧基苯基)醚、吡啶-2,3,5,6-四羧酸及該等之醯胺形成性衍生物等芳香族四羧酸酐成分,較佳為均苯四甲酸二酐、3,3',4,4'-聯苯四羧酸二酐。該等可單獨使用1種,亦可將2種以上混合使用。Specific examples of the above-mentioned acid anhydride components include pyromellitic acid, 3,3',4,4'-biphenyltetracarboxylic acid, 2,3',3,4'-biphenyltetracarboxylic acid, 3, 3',4,4'-benzophenone tetracarboxylic acid, 2,3,6,7-naphthalene tetracarboxylic acid, 2,2-bis(3,4-dicarboxyphenyl)ether, pyridine-2, Aromatic tetracarboxylic anhydride components such as 3,5,6-tetracarboxylic acid and their amide-forming derivatives, preferably pyromellitic dianhydride, 3,3',4,4'-biphenyltetra Carboxylic dianhydride. These may be used individually by 1 type, and may mix and
其中,作為芳香族二胺成分及酸酐成分之尤佳組合,可列舉選自由對苯二胺、4,4'-二胺基二苯醚及3,4'-二胺基二苯醚所組成之群中之1種以上之芳香族二胺成分與選自由均苯四甲酸二酐及3,3',4,4'-聯苯四羧酸二酐所組成之群中之1種以上之酸酐成分的組合。Among them, as a particularly preferable combination of the aromatic diamine component and the acid anhydride component, there are selected from the group consisting of p-phenylenediamine, 4,4'-diaminodiphenyl ether and 3,4'-diaminodiphenyl ether. One or more aromatic diamine components in the group and one or more kinds selected from the group consisting of pyromellitic dianhydride and 3,3',4,4'-biphenyltetracarboxylic dianhydride A combination of anhydride components.
關於上述芳香族二胺成分中之對苯二胺之調配比率,就獲得上述範圍之熱膨脹係數、並對膜賦予適當強度、防止移行性不良等方面而言,相對於芳香族二胺成分總量,可於15莫耳%以上(例如18莫耳%以上)之範圍內選擇,通常為20莫耳%以上(例如25莫耳%以上),較佳為30莫耳%以上(例如31莫耳%以上),較佳為33莫耳%以上,更佳為35莫耳%以上。 作為上述酸酐成分中之調配比率(莫耳比),只要無損本發明之效果則並無特別限定,例如於包含3,3',4,4'-聯苯四羧酸二酐之情形時,相對於酸酐成分總量,3,3',4,4'-聯苯四羧酸二酐之含量較佳為15莫耳%以上,更佳為20莫耳%以上,進而較佳為25莫耳%以上(例如超過25莫耳%、26莫耳%以上、27莫耳%以上等)。 藉由以此種包含芳香族二胺成分與酸酐成分之聚醯胺酸作為聚醯亞胺膜之原料(前驅物),容易將聚醯亞胺膜之熱膨脹係數等於膜之MD方向、TD方向上均調整至上述範圍,因此較佳。Regarding the blending ratio of p-phenylenediamine in the above-mentioned aromatic diamine component, in terms of obtaining the thermal expansion coefficient in the above-mentioned range, imparting appropriate strength to the film, and preventing poor migration, etc. , can be selected in the range of more than 15 mol% (for example, more than 18 mol%), usually more than 20 mol% (for example, more than 25 mol%), preferably more than 30 mol% (for example, 31 mol%) % or more), preferably more than 33 mol%, more preferably more than 35 mol%. The compounding ratio (molar ratio) of the above-mentioned acid anhydride components is not particularly limited as long as the effect of the present invention is not impaired. For example, when 3,3',4,4'-biphenyltetracarboxylic dianhydride is included, Relative to the total amount of anhydride components, the content of 3,3',4,4'-biphenyltetracarboxylic dianhydride is preferably at least 15 mol%, more preferably at least 20 mol%, even more preferably 25 mol% More than mol% (for example, more than 25 mol%, more than 26 mol%, more than 27 mol%, etc.). By using such polyamic acid containing aromatic diamine components and acid anhydride components as the raw material (precursor) of the polyimide film, it is easy to make the thermal expansion coefficient of the polyimide film equal to the MD direction and TD direction of the film Both are adjusted to the above-mentioned range, so it is preferable.
又,於本發明中,作為用於形成聚醯胺酸溶液之有機溶劑之具體例,例如可列舉:二甲基亞碸、二乙基亞碸等亞碸系溶劑,N,N-二甲基甲醯胺、N,N-二乙基甲醯胺等甲醯胺系溶劑,N,N-二甲基乙醯胺、N,N-二乙基乙醯胺等乙醯胺系溶劑,N-甲基-2-吡咯啶酮、N-乙烯基-2-吡咯啶酮等吡咯啶酮系溶劑,苯酚、鄰/間/對甲酚、二甲苯酚、鹵化苯酚、鄰苯二酚等酚系溶劑,或六甲基磷醯胺、γ-丁內酯等非質子性極性溶劑,該等較理想為單獨使用或作為使用2種以上之混合物使用,進而亦可使用二甲苯、甲苯等芳香族烴。In addition, in the present invention, specific examples of the organic solvent used to form the polyamic acid solution include, for example, dimethyl sulfide, diethyl sulfide, and other sulfide-based solvents, N,N-dimethyl N, N-dimethylacetamide, N, N-diethylacetamide and other formamide solvents, Pyrrolidone-based solvents such as N-methyl-2-pyrrolidone and N-vinyl-2-pyrrolidone, phenol, o/m/p-cresol, xylenol, halogenated phenol, catechol, etc. Phenolic solvents, or aprotic polar solvents such as hexamethylphosphamide and γ-butyrolactone, which are preferably used alone or as a mixture of two or more, and xylene, toluene, etc. can also be used Aromatic hydrocarbons.
聚合方法可藉由公知之任意方法進行,例如以下之方法: (1)先於溶劑中添加全部量之芳香族二胺成分,其後,以與全部量之芳香族二胺成分成為當量(等莫耳)之方式添加酸酐成分,進行聚合。 (2)先於溶劑中添加全部量之酸酐成分,其後,以與酸酐成分成為當量之方式添加芳香族二胺成分,進行聚合。 (3)於溶劑中添加一芳香族二胺成分(a1)後,以相對於反應成分成為95~105莫耳%之比率將一酸酐成分(b1)混合反應所需時間後,添加另一芳香族二胺成分(a2),繼而,以全部之芳香族二胺成分與全部之酸酐成分成為大致當量之方式添加另一酸酐成分(b2),進行聚合。 (4)於溶劑中添加一酸酐成分(b1)後,以相對於反應成分成為95~105莫耳%之比率將一芳香族二胺成分(a1)混合反應所需時間後,添加另一酸酐成分(b2),繼而,以全部之芳香族二胺成分與全部之酸酐成分成為大致當量之方式添加另一芳香族二胺成分(a2),進行聚合。 (5)使一芳香族二胺成分與酸酐成分以某一者過量之方式於溶劑中反應,製備聚醯胺酸溶液(A),使另一芳香族二胺成分與酸酐成分以某一者過量之方式於另一溶劑中反應,製備聚醯胺酸溶液(B)。將如此獲得之各聚醯胺酸溶液(A)與(B)進行混合,完成聚合。此時,於製備聚醯胺酸溶液(A)時芳香族二胺成分過量之情形時,於聚醯胺酸溶液(B)中將酸酐成分設為過量,又,於聚醯胺酸溶液(A)中酸酐成分過量之情形時,於聚醯胺酸溶液(B)中將芳香族二胺成分設為過量,將聚醯胺酸溶液(A)與(B)進行混合,以該等反應所使用之全部之芳香族二胺成分與全部之酸酐成分成為大致當量之方式進行調整。再者,聚合方法並不限定於該等,亦可採用其他公知方法。The polymerization method can be carried out by any known method, such as the following method: (1) Add the entire amount of aromatic diamine components to the solvent first, and then add the aromatic diamine components in an equivalent amount to the total amount of the aromatic diamine components (e.g. Mole) way to add acid anhydride components, polymerization. (2) The entire amount of the acid anhydride component is added to the solvent, and then the aromatic diamine component is added so as to be equivalent to the acid anhydride component, and polymerized. (3) After adding an aromatic diamine component (a1) to the solvent, mix and react an acid anhydride component (b1) at a ratio of 95 to 105 mol% relative to the reaction component for the required time, then add another aromatic diamine component (a1) The aromatic diamine component (a2), and then another acid anhydride component (b2) is added so that the whole aromatic diamine component and the whole acid anhydride component become substantially equivalent, and it superposes|polymerizes. (4) After adding one acid anhydride component (b1) to the solvent, mix one aromatic diamine component (a1) at a ratio of 95 to 105 mol% relative to the reaction components and react for the required time, then add another acid anhydride Component (b2) and another aromatic diamine component (a2) are added so that all the aromatic diamine components and all the acid anhydride components may become substantially equivalent, and it superposes|polymerizes. (5) Make an aromatic diamine component and an acid anhydride component react in a solvent in an excess of one of them to prepare a polyamic acid solution (A), and make another aromatic diamine component and an acid anhydride component use a certain one The excess is reacted in another solvent to prepare polyamic acid solution (B). The respective polyamic acid solutions (A) and (B) thus obtained are mixed to complete the polymerization. At this time, when the aromatic diamine component is excessive when preparing the polyamic acid solution (A), the acid anhydride component is set to be excessive in the polyamic acid solution (B), and the polyamic acid solution ( When the acid anhydride component in A) is excessive, make the aromatic diamine component excessive in the polyamic acid solution (B), mix the polyamic acid solution (A) and (B), and react All the aromatic diamine components and all the acid anhydride components used were adjusted so that it might become substantially equivalent. In addition, the polymerization method is not limited to these, and other well-known methods can also be used.
如此獲得之聚醯胺酸溶液通常含有5~40重量%之固形物成分,較佳為含有10~30重量%之固形物成分。又,其黏度利用布氏(Brookfield)黏度計所測得之測定值通常為10~2000 Pa・s,為了確保穩定之送液,較佳為100~1000 Pa・s。又,有機溶劑溶液中之聚醯胺酸可部分地醯亞胺化。The polyamic acid solution thus obtained generally contains 5 to 40% by weight of solid content, preferably 10 to 30% by weight of solid content. In addition, the viscosity measured by a Brookfield viscometer is usually 10 to 2000 Pa·s, preferably 100 to 1000 Pa·s in order to ensure stable liquid delivery. Also, polyamic acid in an organic solvent solution can be partially imidized.
其次,說明聚醯亞胺膜之製造方法。作為製造聚醯亞胺膜之方法,可列舉如下方法:將聚醯胺酸(polyamic acid)溶液流延成膜狀,利用熱脫環化脫溶劑而獲得聚醯亞胺膜;及於聚醯胺酸溶液中混合環化觸媒及脫水劑,化學地脫環化而製作凝膠膜,對其進行加熱脫溶劑,藉此獲得聚醯亞胺膜。後者所獲得之聚醯亞胺膜之熱膨脹係數或濕度膨脹係數可被抑制得較低,因此較佳。Next, a method for producing the polyimide film will be described. As a method for manufacturing a polyimide film, the following methods can be enumerated: polyamic acid (polyamic acid) solution is cast into a film shape, and a polyimide film is obtained by thermal decyclization and desolventization; A cyclization catalyst and a dehydrating agent are mixed in an amine acid solution, and chemically decyclized to form a gel film, which is heated to remove the solvent, thereby obtaining a polyimide film. The latter is preferable since the thermal expansion coefficient or the humidity expansion coefficient of the obtained polyimide film can be suppressed low.
於化學地脫環化之方法中,首先製備上述聚醯胺酸溶液。再者,於本發明中,該聚醯胺酸溶液中通常可含有如上所述之無機粒子。In the method of chemical decyclization, the above-mentioned polyamic acid solution is first prepared. Furthermore, in the present invention, the polyamic acid solution may generally contain the above-mentioned inorganic particles.
此處使用之聚醯胺酸溶液可為已預先進行聚合之聚醯胺酸溶,又,可為使之含有無機粒子時依序進行聚合者。The polyamic acid solution used here may be a polyamic acid solution that has been polymerized in advance, or may be polymerized sequentially when it contains inorganic particles.
上述聚醯胺酸溶液可含有環化觸媒(醯亞胺化觸媒)、脫水劑、凝膠化延遲劑等。The polyamic acid solution may contain a cyclization catalyst (imidization catalyst), a dehydrating agent, a gelling retarder, and the like.
作為環化觸媒,可列舉胺類,例如脂肪族三級胺(三甲胺、三伸乙基二胺等)、芳香族三級胺(二甲基苯胺等)、雜環三級胺(例如異喹啉、吡啶、β-甲基吡啶等)等。該等可單獨使用1種,亦可將2種以上混合使用。As the cyclization catalyst, amines such as aliphatic tertiary amines (trimethylamine, triethylenediamine, etc.), aromatic tertiary amines (dimethylaniline, etc.), heterocyclic tertiary amines (such as isoquinoline, pyridine, β-picoline, etc.), etc. These may be used individually by 1 type, and may mix and
作為脫水劑,可列舉酸酐,例如脂肪族羧酸酐(例如乙酸酐、丙酸酐、丁酸酐等)、芳香族羧酸酐(例如苯甲酸酐等)等。該等可單獨使用1種,亦可將2種以上混合使用。 作為凝膠化延遲劑,並無特別限定,可使用乙醯丙酮等。Examples of the dehydrating agent include acid anhydrides such as aliphatic carboxylic anhydrides (eg, acetic anhydride, propionic anhydride, butyric anhydride, etc.), aromatic carboxylic anhydrides (eg, benzoic anhydride, etc.), and the like. These may be used individually by 1 type, and may mix and
作為由聚醯胺酸溶液製造聚醯亞胺膜之方法,可列舉如下方法:使聚醯胺酸溶液(尤其是含有環化觸媒及脫水劑之聚醯胺酸溶液)於支持體上流延而成型為膜狀,於支持體上進行一部分之醯亞胺化而形成具有自我支持性之凝膠膜後,自支持體剝離,進行加熱乾燥/醯亞胺化,進行熱處理。As a method for producing a polyimide film from a polyamic acid solution, the following method can be cited: casting a polyamic acid solution (especially a polyamic acid solution containing a cyclization catalyst and a dehydrating agent) on a support It is formed into a film, and a part of the imidization is carried out on the support to form a self-supporting gel film, which is peeled off from the support, heat-dried/imidized, and then heat-treated.
上述所謂支持體可列舉金屬製轉筒或環帶作為一例,只要材質均勻則並無特別限定。Examples of the above-mentioned so-called support include a metal drum or an endless belt, and there are no particular limitations as long as the material is uniform.
上述凝膠膜藉由自支持體之受熱及/或自熱風或電加熱器等熱源之受熱而通常被加熱至20~200℃、較佳為40~150℃進行閉環反應,使游離之有機溶劑等揮發成分乾燥,藉此變得具有自我支持性而自支持體剝離。The above-mentioned gel film is usually heated to 20-200°C, preferably 40-150°C by heating from the support and/or heat from a heat source such as a hot air or an electric heater, so that the free organic solvent Wait for the volatile components to dry, thereby becoming self-supporting and peeling off from the support.
上述自支持體剝離之凝膠膜可進行延伸處理。作為延伸處理,只要能夠以特定倍率組合向搬送方向(MD)之延伸與向寬度方向(TD)之延伸等,則其裝置、方法並無限定。關於用以製成具有本發明之效果之膜之延伸倍率,通常於200℃以上之溫度下,例如MD方向之延伸倍率(MDX)通常為1.05~1.9倍,較佳為1.1~1.6倍,進而較佳為1.1~1.3倍。TD之延伸倍率(TDX)通常為MD之延伸倍率(MDX)之1.05~1.3倍,較佳為1.1~1.25倍,進而較佳為1.1~1.2倍。The above-mentioned gel film peeled off from the support can be stretched. As the stretching process, the apparatus and method are not limited as long as stretching in the conveyance direction (MD) and stretching in the width direction (TD) can be combined at a specific magnification. Regarding the stretching ratio used to make the film having the effect of the present invention, usually at a temperature above 200° C., for example, the stretching ratio (MDX) in the MD direction is usually 1.05 to 1.9 times, preferably 1.1 to 1.6 times, and then Preferably it is 1.1 to 1.3 times. The elongation ratio (TDX) of TD is usually 1.05 to 1.3 times the elongation ratio (MDX) of MD, preferably 1.1 to 1.25 times, and more preferably 1.1 to 1.2 times.
可藉由熱風及/或電加熱器等對上述膜於250~500℃之溫度下進行15秒~30分鐘之熱處理。The film may be heat-treated at a temperature of 250-500° C. for 15 seconds to 30 minutes by hot air and/or an electric heater.
關於膜之厚度,較佳為以成為特定厚度(例如7~75 μm,較佳為10~50 μm,進而較佳為10~40 μm)之方式調整固形物成分濃度、黏度、於支持體上流延之聚合物量。Regarding the thickness of the film, it is preferable to adjust the solid content concentration, viscosity, and flow on the support so that it becomes a specific thickness (for example, 7 to 75 μm, preferably 10 to 50 μm, and more preferably 10 to 40 μm). Extend the amount of polymer.
較佳為進一步對如此獲得之聚醯亞胺膜進行退火處理。藉此可引起膜之熱鬆弛而將加熱收縮率抑制得較小。作為退火處理之溫度,並無特別限定,較佳為200℃以上且500℃以下,更佳為200℃以上且370℃以下,尤佳為210℃以上且350℃以下。藉由退火處理所引起之熱鬆弛,可將200℃下之加熱收縮率抑制為上述範圍內,因此尺寸精度變得更高,從而較佳。It is preferable to further anneal the polyimide film thus obtained. Thereby, thermal relaxation of the film can be induced and the heat shrinkage rate can be suppressed to be small. The temperature of the annealing treatment is not particularly limited, but is preferably 200°C to 500°C, more preferably 200°C to 370°C, and particularly preferably 210°C to 350°C. The heat shrinkage rate at 200° C. can be suppressed within the above-mentioned range by the thermal relaxation caused by the annealing treatment, so that the dimensional accuracy becomes higher, which is preferable.
又,為了使所獲得之聚醯亞胺膜具有接著性,可對膜表面進行電暈處理或電漿處理之類之電性處理、或者噴砂處理之類之物理處理,該等物理處理可依據常規方法進行。進行電漿處理之情形時之氣氛之壓力並無特別限定,通常為13.3~1330 kPa之範圍,較佳為13.3~133 kPa(100~1000 Torr)之範圍,更佳為80.0~120 kPa(600~900 Torr)之範圍。Also, in order to make the obtained polyimide film have adhesiveness, electrical treatment such as corona treatment or plasma treatment, or physical treatment such as sandblasting can be carried out on the surface of the film. Such physical treatment can be based on conventional method. The pressure of the atmosphere in the case of plasma treatment is not particularly limited, usually in the range of 13.3 to 1330 kPa, preferably in the range of 13.3 to 133 kPa (100 to 1000 Torr), more preferably in the range of 80.0 to 120 kPa (600 Torr) ~900 Torr).
進行電漿處理之氣氛含有至少20莫耳%之惰性氣體,較佳為含有50莫耳%以上之惰性氣體,更佳為含有80莫耳%以上,最佳為含有90莫耳%以上。上述惰性氣體包括He、Ar、Kr、Xe、Ne、Rn、N2 及該等之2種以上之混合物。尤佳之惰性氣體為Ar。進而,亦可對上述惰性氣體混合氧氣、空氣、一氧化碳、二氧化碳、四氯化碳、氯仿、氫氣、氨氣、四氟甲烷(四氟化碳)、三氯氟乙烷、三氟甲烷等。作為可用作本發明之電漿處理之氣氛之較佳混合氣體之組合,可列舉:氬氣/氧氣、氬氣/氨氣、氬氣/氦氣/氧氣、氬氣/二氧化碳、氬氣/氮氣/二氧化碳、氬氣/氦氣/氮氣、氬氣/氦氣/氮氣/二氧化碳、氬氣/氦氣、氦氣/空氣、氬氣/氦氣/甲矽烷、氬氣/氦氣/乙矽烷等。The atmosphere for plasma treatment contains at least 20 mole % of inert gas, preferably more than 50 mole % of inert gas, more preferably more than 80 mole %, most preferably more than 90 mole %. The above-mentioned inert gases include He, Ar, Kr, Xe, Ne, Rn, N 2 and mixtures of two or more of these. A particularly preferred inert gas is Ar. Furthermore, oxygen, air, carbon monoxide, carbon dioxide, carbon tetrachloride, chloroform, hydrogen, ammonia, tetrafluoromethane (tetrafluoromethane), trichlorofluoroethane, trifluoromethane, etc. may be mixed with the inert gas. As the combination of the preferred mixed gas that can be used as the atmosphere of plasma treatment of the present invention, can enumerate: argon/oxygen, argon/ammonia, argon/helium/oxygen, argon/carbon dioxide, argon/ Nitrogen/Carbon Dioxide, Argon/Helium/Nitrogen, Argon/Helium/Nitrogen/Carbon Dioxide, Argon/Helium, Helium/Air, Argon/Helium/Monosilane, Argon/Helium/Disilane Wait.
實施電漿處理時之處理電力密度並無特別限定,較佳為200 W・min/m2 以上,更佳為500 W・min/m2 以上,最佳為1000 W・min/m2 以上。進行電漿處理之電漿照射時間較佳為1秒~10分鐘。藉由將電漿照射時間設定為該範圍內,可充分發揮電漿處理之效果而不會伴隨膜之劣化。電漿處理之氣體種類、氣體壓力、處理密度並不限定於上述條件,亦有於大氣中進行之情況。There is no particular limitation on the treatment power density when performing plasma treatment, but it is preferably at least 200 W·min/m 2 , more preferably at least 500 W·min/m 2 , most preferably at least 1000 W·min/m 2 . The plasma irradiation time for plasma treatment is preferably 1 second to 10 minutes. By setting the plasma irradiation time within this range, the effect of the plasma treatment can be fully exerted without accompanying deterioration of the film. The gas type, gas pressure, and processing density of plasma treatment are not limited to the above conditions, and may be performed in the atmosphere.
再者,本發明之聚醯亞胺膜如上所述具備特定之特性、物性,此種態樣可藉由適當選擇上述條件等而調整。Furthermore, the polyimide film of the present invention has specific characteristics and physical properties as described above, and such aspects can be adjusted by appropriately selecting the above-mentioned conditions and the like.
例如,摩擦係數可藉由調整無機粒子(或填料)之含量,改變聚醯亞胺膜之表面粗糙度,從而最佳化至特定範圍。例如藉由採用對聚醯亞胺膜添加0.3~1.0質量%之平均粒徑0.05~0.5 μm之無機粒子之方法,容易效率良好地達成。For example, the coefficient of friction can be optimized to a specific range by adjusting the content of inorganic particles (or fillers) and changing the surface roughness of the polyimide film. For example, it can be achieved easily and efficiently by employing a method of adding 0.3 to 1.0% by mass of inorganic particles having an average particle diameter of 0.05 to 0.5 μm to a polyimide film.
關於拉伸彈性模數、熱膨脹係數、濕度膨脹係數、各向異性指數,例如,藉由於聚醯胺酸之聚合步驟中,將對苯二胺及3,3',4,4'-聯苯四羧酸二酐之含量調整至特定範圍,進而,於製膜步驟中,將MD及TD之延伸倍率調整至特定範圍,從而可設為本發明之範圍。 例如,芳香族二胺成分中之對苯二胺之調配比率相對於芳香族二胺成分總量為30莫耳%以上,3,3',4,4'-聯苯四羧酸二酐之含量相對於酸酐成分總量為20莫耳%以上,於200℃以上之溫度下MD方向之延伸倍率為1.05~1.9倍,TD方向之延伸倍率為MD之倍率之1.10~1.20倍。Regarding tensile elastic modulus, coefficient of thermal expansion, coefficient of humidity expansion, and anisotropy index, for example, in the polymerization step of polyamic acid, p-phenylenediamine and 3,3',4,4'-biphenyl The content of the tetracarboxylic dianhydride is adjusted to a specific range, and further, in the film forming step, the stretch ratios of MD and TD are adjusted to a specific range, and can be set as the range of the present invention. For example, the blending ratio of p-phenylenediamine in the aromatic diamine component is 30 mol% or more relative to the total amount of the aromatic diamine component, and the ratio of 3,3',4,4'-biphenyltetracarboxylic dianhydride The content is more than 20 mol% relative to the total amount of anhydride components, and the elongation ratio in the MD direction is 1.05 to 1.9 times at a temperature above 200°C, and the elongation ratio in the TD direction is 1.10 to 1.20 times the MD ratio.
關於環剛度,例如於將聚醯胺酸之聚合步驟中之對苯二胺及3,3',4,4'-聯苯四羧酸二酐之含量、以及製膜步驟中之MD及TD之延伸倍率設為上述範圍之情形時,藉由將聚醯亞胺膜設為特定厚度(例如60 μm以下),可調整至特定範圍。Regarding ring stiffness, for example, the content of p-phenylenediamine and 3,3',4,4'-biphenyltetracarboxylic dianhydride in the polyamic acid polymerization step, and MD and TD in the film forming step When the elongation ratio is in the above range, it can be adjusted to a specific range by making the polyimide film a specific thickness (for example, 60 μm or less).
如此獲得之聚醯亞胺膜具有如上所述之特性。因此,具備優異之尺寸穩定性、表面平滑性、彎折特性等,如下所述適用於各種用途,尤其適於形成:形成有不同方向之配線(圖案)之基板、安裝有複數個電子零件之基板、具有多層構造之基板等。The polyimide film thus obtained has the properties described above. Therefore, it has excellent dimensional stability, surface smoothness, bending characteristics, etc., and is suitable for various purposes as follows, especially suitable for forming: substrates with wiring (patterns) in different directions, substrates with multiple electronic components mounted Substrates, substrates with multilayer structures, etc.
[金屬積層體、金屬配線板] 本發明之聚醯亞胺膜可良好地用於與金屬層(金屬箔)積層而形成基板[金屬積層體(金屬積層板、金屬積層基板)]。本發明之聚醯亞胺膜尤其適合用作電路基板用、特別是可撓性印刷基板(FPC)用之膜等。[Metal Laminate, Metal Wiring Board] The polyimide film of the present invention can be favorably used for laminating with a metal layer (metal foil) to form a substrate [metal laminate (metal laminate, metal laminate substrate)]. The polyimide film of the present invention is particularly suitable as a film for circuit boards, especially for flexible printed circuit boards (FPC), and the like.
因此,本發明包含具備(使用)上述聚醯亞胺膜之基板。即,此種基板(金屬積層體)具備上述聚醯亞胺膜與金屬層。Therefore, the present invention includes a substrate provided with (using) the above polyimide film. That is, such a substrate (metal laminate) includes the aforementioned polyimide film and metal layer.
構成金屬層(金屬箔)之金屬之種類並無特別限定,例如可列舉:銅(銅單質、銅合金等)、不鏽鋼及其合金、鎳(鎳單質、鎳合金等)、鋁(鋁單質、鋁合金等)等。The type of metal constituting the metal layer (metal foil) is not particularly limited, for example, copper (copper element, copper alloy, etc.), stainless steel and its alloys, nickel (nickel element, nickel alloy, etc.), aluminum (aluminum element, Aluminum alloy, etc.) etc.
金屬較佳為銅。藉由將此種金屬層與聚醯亞胺膜進行積層而獲得金屬積層基板。又,亦可利用於該等金屬表面形成有防銹層或耐熱層(例如鍍鉻、鍍鋅等鍍覆處理)、矽烷偶合劑等者。較佳為銅及/或包含鎳、鋅、鐵、鉻、鈷、鉬、鎢、釩、鈹、鈦、錫、錳、鋁、磷、矽等中之至少1種以上之成分與銅之銅合金,該等良好地用於電路加工方面。作為尤其理想之金屬層,可列舉藉由壓延或電解鍍覆所形成之銅等。The metal is preferably copper. A metal laminated substrate is obtained by laminating such a metal layer and a polyimide film. In addition, it can also be used for the metal surface formed with a rust-proof layer or a heat-resistant layer (such as chrome plating, zinc plating, etc.), silane coupling agent, and the like. Preferably copper and/or copper containing at least one of nickel, zinc, iron, chromium, cobalt, molybdenum, tungsten, vanadium, beryllium, titanium, tin, manganese, aluminum, phosphorus, silicon, etc. and copper Alloys, which are well used in circuit processing. Copper formed by rolling or electrolytic plating is mentioned as a particularly preferable metal layer.
再者,金屬層只要形成於聚醯亞胺膜之至少一面即可,亦可形成於聚醯亞胺膜之兩面。In addition, the metal layer only needs to be formed on at least one side of the polyimide film, and may be formed on both sides of the polyimide film.
金屬積層基板中,金屬層之厚度並無特別限定,例如可為1~150 μm(例如1.5~100 μm、2~80 μm、3~50 μm等)左右,亦可為2~12 μm左右。In metal laminate substrates, the thickness of the metal layer is not particularly limited, and may be, for example, about 1 to 150 μm (for example, 1.5 to 100 μm, 2 to 80 μm, 3 to 50 μm, etc.), or about 2 to 12 μm.
金屬積層基板只要具備聚醯亞胺膜及金屬層,則其積層形態並無特別限定,根據聚醯亞胺膜之使用目的等,例如可直接積層聚醯亞胺膜與金屬層,亦可經由接著層(接著劑層)而積層(貼合)聚醯亞胺膜與金屬箔。As long as the metal-laminated substrate has a polyimide film and a metal layer, the lamination form is not particularly limited. According to the purpose of the polyimide film, for example, the polyimide film and the metal layer can be directly laminated, or through The polyimide film and the metal foil are laminated (laminated) next to the layer (adhesive layer).
構成接著層之接著成分並無特別限定,例如可為熱硬化性樹脂、熱塑性樹脂之任意者。The adhesive component constituting the adhesive layer is not particularly limited, and may be any of thermosetting resin and thermoplastic resin, for example.
此種金屬積層基板之製造方法並無特別限定,可根據金屬積層基板之形態等而依據先前公知之製造方法製造。一般為如下方法:例如於聚醯亞胺膜之一面或兩面藉由濺鍍法形成以鎳鉻為主成分之金屬層,於該金屬層上藉由電解鍍覆積層以銅為主成分之層。代表性之本發明之金屬積層基板(覆銅積層體、覆銅積層板)例如係藉由於聚醯亞胺膜之兩面設置鎳鉻合金層,於其上利用電解鍍覆形成特定厚度(例如厚度2~12 μm)之銅而獲得。The manufacturing method of such a metal laminated board is not specifically limited, According to the form etc. of a metal laminated board, it can manufacture according to the conventionally well-known manufacturing method. Generally, the method is as follows: For example, a metal layer mainly composed of nickel and chromium is formed on one or both sides of the polyimide film by sputtering, and a layer mainly composed of copper is deposited on the metal layer by electrolytic plating. . A representative metal laminate substrate (copper-clad laminate, copper-clad laminate) of the present invention is, for example, provided with a nickel-chromium alloy layer on both sides of a polyimide film, on which a specific thickness (such as a
於金屬積層基板中,藉由對金屬層進行蝕刻,可形成所需配線(金屬配線、配線圖案)。In the metal build-up substrate, desired wiring (metal wiring, wiring pattern) can be formed by etching the metal layer.
因此,本發明亦包含具備上述聚醯亞胺膜與形成於該膜上之配線(金屬配線)之基板(金屬配線板、金屬配線基板)。此種金屬配線基板通常可為可撓性印刷基板。Therefore, the present invention also includes a substrate (metal wiring board, metal wiring board) including the above-mentioned polyimide film and wiring (metal wiring) formed on the film. Such metal wiring substrates are generally flexible printed substrates.
再者,配線(配線電路、金屬配線)只要形成於聚醯亞胺膜之至少一面即可,亦可形成於聚醯亞胺膜之兩面。Furthermore, wiring (wiring circuit, metal wiring) may be formed on at least one side of the polyimide film, and may be formed on both sides of the polyimide film.
於此種金屬配線基板中,配線(例如同一膜面上之配線)可形成於一個部位或複數個部位,於形成於複數個部位之情形時,可沿同一個方向或不同方向形成配線。In such a metal wiring board, wiring (for example, wiring on the same film surface) can be formed in one location or in multiple locations, and when formed in a plurality of locations, wiring can be formed in the same direction or in different directions.
於本發明中,尤其可沿不同方向(複數個部位之不同方向)形成配線。作為沿不同方向形成之態樣,並無特別限定,例如可至少於沿聚醯亞胺膜之MD方向及TD方向之兩個方向上形成配線。 即,可於聚醯亞胺膜至少形成沿聚醯亞胺膜之MD方向之配線(以配線橫斷方向作為TD方向之配線)及沿聚醯亞胺膜之TD方向之配線(以配線橫斷方向作為MD方向之配線)。In the present invention, in particular, wiring can be formed in different directions (different directions at a plurality of locations). The mode of forming in different directions is not particularly limited. For example, wiring may be formed in at least two directions along the MD direction and the TD direction of the polyimide film. That is, wiring along the MD direction of the polyimide film can be formed at least on the polyimide film (taking the wiring transverse direction as the wiring in the TD direction) and wiring along the TD direction of the polyimide film (taking the wiring transverse direction as the wiring in the TD direction) The disconnecting direction is regarded as the wiring in the MD direction).
再者,配線之尺寸(間距)並無特別限定,即便為窄間距,亦可效率良好地形成。關於此種配線之尺寸,例如線寬可為30 μm以下(例如20 μm以下、15 μm以下、10 μm以下)左右,線間(線間隔)可為40 μm以下(例如20 μm以下、15 μm以下、10 μm以下)左右。In addition, the size (pitch) of wiring is not specifically limited, Even if it is a narrow pitch, it can form efficiently. Regarding the size of such wiring, for example, the line width can be about 30 μm or less (for example, 20 μm or less, 15 μm or less, 10 μm or less), and the line (line spacing) can be 40 μm or less (for example, 20 μm or less, 15 μm less than 10 μm) or so.
於金屬配線基板(構成金屬配線基板之聚醯亞胺膜)中,配線橫斷方向之熱膨脹係數大多會反映聚醯亞胺膜之熱膨脹係數而較小,例如可為12 ppm/℃以下(例如10 ppm/℃以下),較佳為8 ppm/℃以下(例如2~8 ppm/℃),更佳為7 ppm/℃以下(例如3~7 ppm/℃),若為6 ppm℃以下(例如3~6 ppm/℃)則進而更佳。In metal wiring boards (polyimide films that make up metal wiring boards), the thermal expansion coefficient in the cross-sectional direction of the wiring mostly reflects the thermal expansion coefficient of the polyimide film and is relatively small, for example, it can be below 12 ppm/°C (for example 10 ppm/°C or less), preferably 8 ppm/°C or less (for example, 2-8 ppm/°C), more preferably 7 ppm/°C or less (for example, 3-7 ppm/°C), if it is 6 ppm or less ( For example, 3 to 6 ppm/°C) is even more preferable.
再者,於複數個部位或不同方向上形成配線之情形時,較佳為均滿足上述熱膨脹係數。例如於沿MD方向及TD方向形成配線之情形時,較佳為該等之配線橫斷方向(即TD方向及MD方向)之熱膨脹係數均滿足上述熱膨脹係數。Furthermore, when wiring is formed in a plurality of places or in different directions, it is preferable that all of them satisfy the above-mentioned coefficient of thermal expansion. For example, when the wiring is formed along the MD direction and the TD direction, it is preferable that the thermal expansion coefficients of the wiring transverse directions (that is, the TD direction and the MD direction) all satisfy the above-mentioned thermal expansion coefficients.
又,於複數個部位或不同方向上形成配線之情形時,較佳為於所有部位或配線橫斷方向上,熱膨脹係數較小,進而該等之差異較小。 例如於沿MD方向及TD方向形成配線之情形(即,將配線橫斷方向設為TD方向及MD方向之情形)時,金屬配線基板(構成金屬配線基板之聚醯亞胺膜)中之|αTMD -αTTD |大多會反映上述聚醯亞胺膜中之值而較小,例如為7 ppm/℃以下(例如6 ppm/℃以下),較佳為5 ppm/℃以下(例如4.5 ppm/℃以下),進而較佳為4 ppm/℃以下(例如3.5 ppm/℃以下),尤其可為3 ppm/℃以下,若為2.5 ppm/℃以下、2 ppm/℃以下、1.5 ppm/℃以下等則進而更佳。 再者,|αTMD -αTTD |之值可為各配線中之值(或其平均值),亦可使用不同配線中之αTMD 及αTTD 而算出。 例如於形成以MD方向作為配線橫斷方向之配線A、以TD方向作為配線橫斷方向之配線B之情形時,可將配線A中之|αTMD -αTTD |或配線B中之|αTMD -αTTD |(或該等之平均值)作為上述值,亦可由配線A(之橫斷方向)中之αTMD 及配線B(之橫斷方向)中之αTTD 之值求出|αTMD -αTTD |。Also, when wiring is formed in a plurality of locations or in different directions, it is preferable that the coefficient of thermal expansion is small in all the locations or in the transverse direction of the wiring, so that the difference is small. For example, when the wiring is formed along the MD direction and the TD direction (that is, when the wiring transverse direction is set to the TD direction and the MD direction), the metal wiring board (polyimide film constituting the metal wiring board) | αT MD -αT TD |Most will reflect the above-mentioned value in the polyimide film and be smaller, such as 7 ppm/°C or less (eg, 6 ppm/°C or less), preferably 5 ppm/°C or less (eg, 4.5 ppm /°C or less), more preferably 4 ppm/°C or less (for example, 3.5 ppm/°C or less), especially 3 ppm/°C or less, if it is 2.5 ppm/°C or less, 2 ppm/°C or less, 1.5 ppm/°C or less The following are even better. In addition, the value of |αT MD - αT TD | may be a value (or an average value thereof) in each wiring, and may be calculated using αT MD and αT TD in different wirings. For example, when forming the wiring A with the MD direction as the wiring transverse direction and the wiring B with the TD direction as the wiring transverse direction, you can use |αT MD - αT TD | in the wiring A or |αT in the wiring B MD - αT TD | (or their average value) can also be obtained from the values of αT MD in wiring A (in the transverse direction) and αT TD in wiring B (in the transverse direction) as the above value | αT MD - αT TD |.
藉由減小熱膨脹係數,容易抑制因熱引起之尺寸變化(膨脹)。因此,能夠抑制例如安裝電子零件時之加工溫度下之基板之膨脹,降低安裝不良之發生風險。 又,藉由減小|αTMD -αTTD |,能夠於多方向上抑制此種尺寸變化或膨脹。因此,例如不會將電子零件之安裝方向限定於一個方向上,電路設計之自由度飛躍性提高。By reducing the coefficient of thermal expansion, it is easy to suppress dimensional change (expansion) due to heat. Therefore, it is possible to suppress the expansion of the substrate at the processing temperature when mounting electronic components, for example, and reduce the risk of defective mounting. Furthermore, by reducing |αT MD −αT TD |, it is possible to suppress such a dimensional change or expansion in multiple directions. Therefore, for example, the mounting direction of electronic components is not limited to one direction, and the degree of freedom of circuit design is greatly improved.
金屬配線基板(可撓性印刷基板)之製造方法並無特別限定,可採用公知方法,尤其可藉由半加成法或減成法製造。The method of manufacturing the metal wiring board (flexible printed circuit board) is not particularly limited, and known methods can be used, especially semi-additive or subtractive methods.
於更具體之態樣中,可藉由如下方法(半加成法)製造:採用光微影法於覆銅積層體(例如銅厚度1~3 μm左右之覆銅積層板)上圖案化出配線(配線電路),將欲形成配線之部位之抗蝕劑層剝離後,於露出之薄銅層上藉由電解鍍銅而形成配線(例如銅厚度7~10 μm之配線),其後去除抗蝕劑層、薄銅層、基底金屬層;或可藉由如下方法(減成法)製造:採用光微影法於覆銅積層體(例如銅厚度7~10 μm之覆銅積層板)上圖案化出配線電路,藉由蝕刻去除不形成配線之部位之銅層、基底金屬層後,剝離抗蝕劑層。In a more specific aspect, it can be manufactured by the following method (semi-additive method): use photolithography to pattern a copper-clad laminate (such as a copper-clad laminate with a copper thickness of about 1-3 μm) Wiring (wiring circuit), after peeling off the resist layer of the part where the wiring is to be formed, the wiring is formed on the exposed thin copper layer by electrolytic copper plating (such as wiring with a copper thickness of 7-10 μm), and then removed Resist layer, thin copper layer, base metal layer; or can be manufactured by the following method (subtractive method): using photolithography on copper-clad laminates (such as copper-clad laminates with a copper thickness of 7-10 μm) The wiring circuit is patterned on the top, and the copper layer and the base metal layer in the parts where no wiring is formed are removed by etching, and the resist layer is peeled off.
視需要亦可於配線(銅配線等)上藉由無電電鍍法形成0.1~0.5 μm之錫或金。If necessary, 0.1 to 0.5 μm of tin or gold can be formed on wiring (copper wiring, etc.) by electroless plating.
又,為了保護電路,可於必要部分積層阻焊劑,亦可積層以覆蓋膜。或可將阻焊劑與覆蓋膜加以組合以分別保護必要部位。Moreover, in order to protect a circuit, a solder resist may be laminated|stacked on the necessary part, and a cover film may be laminated|stacked. Alternatively, a solder resist and a cover film can be combined to separately protect necessary parts.
[覆蓋膜] 本發明之聚醯亞胺膜亦可構成覆蓋膜。因此,本發明亦包含包括上述聚醯亞胺膜之覆蓋膜。[Cover Film] The polyimide film of the present invention can also constitute a cover film. Therefore, the present invention also includes a cover film comprising the above-mentioned polyimide film.
此種覆蓋膜尤其可為選自形成有不同方向之配線之基板(上述金屬配線基板、上述金屬配線基板中聚醯亞胺膜不為上述聚醯亞胺膜之金屬配線基板等)、安裝有複數個零件之基板(下文記述之安裝基板等)、及具有多層構造之基板(下文記述之基板等)中之至少1種基板用之覆蓋膜。In particular, such a cover film can be selected from substrates on which wirings in different directions are formed (the above-mentioned metal wiring substrates, metal wiring substrates in which the polyimide film in the above-mentioned metal wiring substrates is not the above-mentioned polyimide film, etc.), A cover film for at least one of substrates with multiple parts (mounting substrates described below, etc.) and substrates with a multilayer structure (substrates described below, etc.).
覆蓋膜係覆蓋配線或零件(電子零件)者,因此,覆蓋膜之尺寸穩定性等亦會對形成之配線或安裝之零件產生影響。因此,使覆蓋膜亦發揮優異之尺寸穩定性等變得重要。The cover film covers wiring or parts (electronic parts), therefore, the dimensional stability of the cover film also affects the formed wiring or mounted parts. Therefore, it is important to make the cover film exhibit excellent dimensional stability and the like.
覆蓋膜可僅由聚醯亞胺膜構成,亦可由聚醯亞胺膜與接著層(接著劑層)構成。The cover film may be composed of only a polyimide film, or may be composed of a polyimide film and an adhesive layer (adhesive layer).
覆蓋膜(或構成覆蓋膜之聚醯亞胺膜)之厚度並無特別限定,例如可為1~100 μm,較佳為3~50 μm,進而較佳為5~25 μm左右。 又,覆蓋膜中,接著層之厚度並無特別限定,例如可為1~300 μm(例如2~200 μm),較佳為3~150 μm(例如5~100 μm),亦可為1~80 μm(例如3~60 μm,較佳為5~50 μm,進而較佳為10~30 μm)。The thickness of the cover film (or the polyimide film constituting the cover film) is not particularly limited, and may be, for example, 1-100 μm, preferably 3-50 μm, and more preferably about 5-25 μm. In addition, in the cover film, the thickness of the adhesive layer is not particularly limited, for example, it can be 1-300 μm (for example, 2-200 μm), preferably 3-150 μm (for example, 5-100 μm), and it can also be 1-300 μm. 80 μm (for example, 3-60 μm, preferably 5-50 μm, more preferably 10-30 μm).
再者,覆蓋膜例如用於覆蓋金屬配線基板之金屬層(金屬配線板之配線)。此種金屬配線基板(金屬配線板)包含基礎膜(基材膜)與金屬層(配線)。基礎膜可為上述聚醯亞胺膜,亦可為不為上述聚醯亞胺膜之聚醯亞胺膜,尤其可將覆蓋膜及基礎膜兩者均設為上述聚醯亞胺膜。 藉由如此於覆蓋膜與金屬配線基板之基礎膜兩者組合上述聚醯亞胺膜,能夠效率良好地發揮優異之尺寸穩定性等。In addition, a cover film is used for covering the metal layer (wiring of a metal wiring board) of a metal wiring board, for example. Such a metal wiring board (metal wiring board) includes a base film (base film) and a metal layer (wiring). The base film may be the above-mentioned polyimide film or a polyimide film other than the above-mentioned polyimide film. In particular, both the cover film and the base film may be the above-mentioned polyimide film. By combining the above-mentioned polyimide film on both the cover film and the base film of the metal wiring board in this way, excellent dimensional stability and the like can be efficiently exhibited.
[安裝基板] 本發明亦包含具備上述金屬配線基板(金屬配線板)及/或上述覆蓋膜之安裝基板(電子零件安裝基板)。此種安裝基板例如可為薄膜覆晶膜(COF)基板。[Mounting board] The present invention also includes a mounting board (electronic component mounting board) including the above-mentioned metal wiring board (metal wiring board) and/or the above-mentioned cover film. Such a mounting substrate may be, for example, a chip-on-film (COF) substrate.
於此種安裝基板中,安裝零件(電子零件)可為1個,亦可為複數個,尤其可為複數個。於本發明中,即便於安裝複數個零件之情形時,亦能夠效率良好地發揮優異之尺寸穩定性等。因此,即便為複數個零件,亦能夠實現高精度之安裝。In such a mounting substrate, the mounting component (electronic component) may be one, or plural, especially plural. In the present invention, even when a plurality of components are mounted, excellent dimensional stability and the like can be efficiently exhibited. Therefore, high-precision mounting can be realized even with a plurality of parts.
於代表性態樣中,可於沿不同方向形成有配線之基板之配線上安裝零件。於更具體之安裝基板中,具備至少於沿聚醯亞胺膜之MD方向及TD方向之兩個方向上形成有配線(金屬配線)之基板(金屬配線基板),可於該配線上分別安裝電子零件。In a representative aspect, components can be mounted on wiring of a substrate on which wiring is formed in different directions. In a more specific mounting substrate, there is provided a substrate (metal wiring substrate) on which wiring (metal wiring) is formed in at least two directions along the MD direction and the TD direction of the polyimide film, and can be separately mounted on the wiring. electronic parts.
再者,作為零件(電子零件),可根據用途選擇,並無特別限定,例如可列舉:IC晶片、電容器、電晶體、記憶體、電感器等。該等零件可單獨使用或將2種以上組合使用。In addition, as a component (electronic component), it can be selected according to a use, and it is not specifically limited, For example, an IC chip, a capacitor, a transistor, a memory, an inductor, etc. are mentioned. These components may be used alone or in combination of two or more.
[具有多層構造之基板] 本發明之聚醯亞胺膜亦適合用作構成具有多層構造之基板之膜。[Substrate having a multilayer structure] The polyimide film of the present invention is also suitably used as a film constituting a substrate having a multilayer structure.
此種具有多層構造之基板代表性而言可為具有至少具備上述金屬配線基板及/或上述覆蓋膜之多層構造之基板。根據此種具有多層構造之基板,儘管為多層構造,但亦可發揮優異之尺寸穩定性等,能夠形成高精度之多層構造基板。尤其於多層構造基板中,必須進行層間連接,根據本發明之聚醯亞胺膜,能夠以較高之位置精度利用導孔實現層間連接。Typically, such a substrate having a multilayer structure may be a substrate having a multilayer structure including at least the above-mentioned metal wiring board and/or the above-mentioned cover film. According to such a substrate having a multilayer structure, excellent dimensional stability and the like can be exhibited despite having a multilayer structure, and a high-precision multilayer structure substrate can be formed. Especially in multi-layer structure substrates, interlayer connections must be made. According to the polyimide film of the present invention, interlayer connections can be realized by using guide holes with high positional accuracy.
例如具有多層構造之基板(例如多層可撓性印刷基板)通常包含積層之複數層金屬配線基板、及覆蓋其最外層之金屬配線基板(或金屬配線基板之配線)之覆蓋膜,該複數層金屬配線基板(基礎膜)及/或覆蓋膜之至少一者可為上述聚醯亞胺膜。For example, a substrate with a multilayer structure (such as a multilayer flexible printed circuit board) usually includes a multi-layer metal wiring substrate laminated and a cover film covering the outermost metal wiring substrate (or wiring of the metal wiring substrate). At least one of the wiring board (base film) and/or the cover film may be the aforementioned polyimide film.
具有多層構造之基板尤佳為構成金屬配線基板之基礎膜及構成覆蓋膜之膜全部(或構成具有多層構造之基板之全部之聚醯亞胺膜)為上述聚醯亞胺膜。In the substrate having a multilayer structure, it is preferable that all of the base film and cover film constituting the metal wiring substrate (or the polyimide film constituting the entirety of the substrate having a multilayer structure) be the polyimide film described above.
只要發揮本發明之效果,則本發明包含在本發明之技術範圍內將上述構成進行各種組合之態樣。 [實施例]As long as the effects of the present invention are exhibited, the present invention includes various combinations of the above-mentioned constitutions within the technical scope of the present invention. [Example]
其次,列舉實施例進而具體地說明本發明,但本發明並不受該等實施例之任何限定。Next, the present invention will be described concretely by giving examples, but the present invention is not limited by these examples.
再者,於實施例中,PPD表示對苯二胺,4,4'-ODA表示4,4'-二胺基二苯醚,PMDA表示均苯四甲酸二酐,BPDA表示3,3',4,4'-聯苯四羧酸二酐,DMAc表示N,N-二甲基乙醯胺。Furthermore, in the examples, PPD represents p-phenylenediamine, 4,4'-ODA represents 4,4'-diaminodiphenyl ether, PMDA represents pyromellitic dianhydride, BPDA represents 3,3', 4,4'-biphenyltetracarboxylic dianhydride, DMAc means N,N-dimethylacetamide.
[實施例1~3] (聚醯亞胺膜之製作) 以莫耳比40/60/30/70之比率準備PPD(分子量108.14)、4,4'-ODA(分子量200.24)、BPDA(分子量294.22)、PMDA(分子量218.12),製成DMAc中20重量%溶液,進行聚合,而獲得3500 poise之聚醯胺酸溶液。於其中添加相對於樹脂重量為0.3重量%之平均粒徑0.3 μm之二氧化矽之DMAc漿料,充分攪拌使之分散。 於該溶液中分別以17重量%之比率混合乙酸酐(分子量102.09)與β-甲基吡啶,進行攪拌。使所獲得之混合物自T型狹縫口模流延至旋轉之75℃之不鏽鋼製轉筒上,進行剝離,而獲得殘留揮發成分為55重量%、厚度約為0.05 mm之具有自我支持性之凝膠膜。 將該凝膠膜於65℃下沿搬送方向延伸1.25倍後,於加熱爐內,一面沿與搬送方向垂直之方向延伸1.45倍,一面連續進行250℃下50秒、400℃下75秒之熱處理。藉由調整搬送速度,而獲得厚度13 μm、25 μm、35 μm之聚醯亞胺膜。[Examples 1-3] (Preparation of polyimide film) PPD (molecular weight 108.14), 4,4'-ODA (molecular weight 200.24), BPDA (molecular weight 294.22), PMDA (molecular weight 218.12), made into a 20% by weight solution in DMAc, and polymerized to obtain a polyamic acid solution of 3500 poise. A DMAc slurry of silicon dioxide with an average particle diameter of 0.3 μm was added thereto at 0.3% by weight relative to the weight of the resin, and stirred sufficiently to disperse it. In this solution, acetic anhydride (molecular weight: 102.09) and (beta)-picoline were mixed and stirred at the ratio of 17 weight%. The obtained mixture was flow-cast from a T-shaped slit die to a rotating stainless steel drum at 75°C, and peeled off to obtain a self-supporting gel with a residual volatile content of 55% by weight and a thickness of about 0.05 mm. film. After stretching the gel film 1.25 times in the direction of conveyance at 65°C, heat treatment at 250°C for 50 seconds and 400°C for 75 seconds in a heating furnace while stretching 1.45 times in a direction perpendicular to the direction of conveyance . By adjusting the transport speed, polyimide films with a thickness of 13 μm, 25 μm, and 35 μm were obtained.
[實施例4] 使用平均粒徑0.1 μm之二氧化矽之DMAc漿料,除此以外,藉由與實施例1~3相同之程序獲得厚度50 μm之聚醯亞胺膜。[Example 4] A polyimide film having a thickness of 50 μm was obtained by the same procedure as in Examples 1 to 3 except that a DMAc slurry of silica having an average particle diameter of 0.1 μm was used.
[實施例5、6] 將PPD、4,4'-ODA、BPDA、PMDA設為莫耳比20/80/35/65之比率,使用平均粒徑0.1 μm之二氧化矽,除此以外,藉由與實施例1~3相同之程序獲得厚度13 μm、25 μm之聚醯亞胺膜。[Examples 5 and 6] PPD, 4,4'-ODA, BPDA, and PMDA were set to a molar ratio of 20/80/35/65, and silica with an average particle size of 0.1 μm was used. In addition, Polyimide films with a thickness of 13 μm and 25 μm were obtained by the same procedure as in Examples 1-3.
[比較例1] 將PPD、4,4'-ODA、BPDA、PMDA設為莫耳比35/65/30/70之比率,不添加粒子,沿搬送方向延伸1.20倍,沿與搬送方向垂直之方向延伸1.45倍,除此以外,藉由與實施例1~3相同之程序獲得厚度25 μm之聚醯亞胺膜。[Comparative Example 1] Set PPD, 4,4'-ODA, BPDA, and PMDA to a molar ratio of 35/65/30/70, without adding particles, extend 1.20 times along the conveying direction, and extend along the direction perpendicular to the conveying direction Except that the direction was stretched 1.45 times, a polyimide film having a thickness of 25 μm was obtained by the same procedure as in Examples 1 to 3.
[比較例2] 將PPD、4,4'-ODA、BPDA、PMDA設為莫耳比30/70/25/75之比率,沿搬送方向延伸1.15倍,沿與搬送方向垂直之方向延伸1.40倍,除此以外,藉由與實施例1~3相同之程序獲得厚度38 μm之聚醯亞胺膜。[Comparative Example 2] Set PPD, 4,4'-ODA, BPDA, and PMDA to a molar ratio of 30/70/25/75, extend 1.15 times along the conveying direction, and extend 1.40 times along the direction perpendicular to the conveying direction , except that, a polyimide film having a thickness of 38 μm was obtained by the same procedure as in Examples 1 to 3.
對該等膜進行以下之各特性之評價,將其結果示於表1。只要無特別說明,則各評價係於25℃、60%RH之環境中實施。These films were evaluated for the following characteristics, and the results are shown in Table 1. Unless otherwise specified, each evaluation was carried out in an environment of 25° C. and 60% RH.
(1)拉伸彈性模數 使用RTM-250(A & D製造),於拉伸速度:100 mm/min之條件下測定。(1) Tensile modulus of elasticity was measured using RTM-250 (manufactured by A & D) under the condition of tensile speed: 100 mm/min.
(2)熱膨脹係數(CTE) 使用TMA-60(島津製作所製造),於測定溫度範圍:50~200℃、升溫速度:10℃/min之條件下測定。(2) Coefficient of thermal expansion (CTE) Using TMA-60 (manufactured by Shimadzu Corporation), it was measured under the conditions of a measurement temperature range: 50°C to 200°C, and a temperature increase rate: 10°C/min.
(3)濕度膨脹係數(CHE) 使用TM-9400(ULVAC理工製造),於溫度25℃、測定濕度範圍:25~70%RH之條件下測定。(3) Humidity expansion coefficient (CHE) Using TM-9400 (manufactured by ULVAC Riko), it was measured at a temperature of 25° C. and a measurement humidity range of 25 to 70% RH.
(4)摩擦係數 將樣品之支持體面與非支持體面重疊並固定於滑動測試儀(Techno Needs公司製造),於荷重200 g下以測定速度120 mm/min之速度測定靜摩擦係數與動摩擦係數。(4) Coefficient of friction Overlap the support surface and the non-support surface of the sample and fix them on a sliding tester (manufactured by Techno Needs Co., Ltd.), and measure the coefficient of static friction and coefficient of dynamic friction at a speed of 120 mm/min under a load of 200 g.
(5)各向異性指數(MT比) 使用SST-2500(野村商事製造之Sonic Sheet Tester),測定MD方向及TD方向之超音波脈衝傳播速度VMD
、VTD
,算出由下式1所定義之各向異性指數(MT比)。 (式1):MT比=|(VMD 2
-VTD 2
)/((VMD 2
+VTD 2
)/2)×100|(5) Anisotropy index (MT ratio) Using SST-2500 (Sonic Sheet Tester manufactured by Nomura Corporation), measure the ultrasonic pulse propagation speed V MD and V TD in the MD direction and TD direction, and calculate the value defined by the following
(6)環剛度 使用環剛度測試機DA(東洋精機製作所製造),於樣品寬度20 mm、環長50 mm、壓縮距離20 mm之條件下測定。(6) Ring stiffness Using a ring stiffness tester DA (manufactured by Toyo Seiki Seisakusho), it was measured under the conditions of a sample width of 20 mm, a ring length of 50 mm, and a compression distance of 20 mm.
[表1]
根據上表之結果,可知實施例之聚醯亞胺膜於特定物性方面處於特定範圍。因此,可確認為表面平滑性(進而操作性)優異、MD方向與TD方向上之尺寸穩定性均優異之(進而無論於膜之哪一方向上,尺寸穩定性均優異之)聚醯亞胺膜。According to the results in the above table, it can be seen that the polyimide film of the embodiment is in a specific range in terms of specific physical properties. Therefore, it can be confirmed that the polyimide film is excellent in surface smoothness (and thus handleability), and excellent in dimensional stability in both MD and TD directions (and also excellent in dimensional stability regardless of the direction of the film). .
(覆銅積層板之製作) 於表2所示之聚醯亞胺膜之支持體面藉由濺鍍法形成鎳鉻層(Ni:Cr=80:20,厚度25 nm)及銅層(厚度100 nm)後,藉由使用硫酸銅鍍液之電解鍍覆而形成厚度8 μm之銅層。(Manufacturing of copper-clad laminates) A nickel-chromium layer (Ni:Cr=80:20, thickness 25 nm) and a copper layer (thickness 100 nm) were formed on the support surface of the polyimide film shown in Table 2 by sputtering. nm), a copper layer with a thickness of 8 μm was formed by electrolytic plating using a copper sulfate plating solution.
對所獲得之覆銅積層板進行以下之項目評價。將結果示於表2。再者,於表2中,「聚醯亞胺膜」一項之「實施例1」意指「於實施例1中所獲得之聚醯亞胺膜」(其他亦相同)。The following items were evaluated for the obtained copper-clad laminates. The results are shown in Table 2. Furthermore, in Table 2, "Example 1" in the item "polyimide film" means "the polyimide film obtained in Example 1" (others are also the same).
(7)翹曲 將覆銅積層板裁切成70 mm×70 mm之大小,固定端部5 mm,利用JIS1級曲尺測定下垂量。(7) Warpage Cut the copper-clad laminate into a size of 70 mm x 70 mm, fix the end 5 mm, and measure the sag with a
[表2]
根據上述表2之結果,可知藉由實施例中所獲得之膜,可將覆銅積層體之翹曲抑制得相對較小。From the results in Table 2 above, it can be seen that the warpage of the copper-clad laminate can be suppressed relatively small by the films obtained in Examples.
(評價用可撓性印刷基板之製作) 依據常規方法,使用液狀抗蝕劑於上述獲得之覆銅積層板之銅層上製作膜厚5 μm之負型抗蝕劑,藉由蝕刻去除銅層及鎳鉻層後,剝離抗蝕劑。 繼而,於無電鍍錫液(Shipley Far East製造之鍍錫液TINPOSIT LT-34)中於70℃下浸漬5分鐘,而形成厚度0.5 μm之鍍膜,製作如圖1所示於基板(聚醯亞胺膜)1上具有兩處以MD方向及TD方向作為配線橫斷方向且30 μm間距(線寬15 μm、線間15 μm)之電子零件連接部分(配線)2的評價用可撓性印刷基板。 對所獲得之可撓性印刷基板進行以下之項目評價,將結果示於表3。(Fabrication of flexible printed circuit boards for evaluation) According to the conventional method, a negative resist with a film thickness of 5 μm was prepared on the copper layer of the copper-clad laminate obtained above using a liquid resist, and the copper was removed by etching layer and NiCr layer, the resist is stripped. Then, immerse in an electroless tin plating solution (TINPOSIT LT-34 manufactured by Shipley Far East) at 70°C for 5 minutes to form a coating film with a thickness of 0.5 μm, as shown in Figure 1. A flexible printed circuit board for evaluation with two electronic component connection parts (wiring) 2 on the amine film) 1 with the MD direction and the TD direction as the wiring transverse direction and a pitch of 30 μm (15 μm in line width and 15 μm in between lines) . The following items were evaluated about the obtained flexible printed circuit board, and the result is shown in Table 3.
(8)熱膨脹係數(CTE) 使用TMA-60(島津製作所製造),於測定溫度範圍:50~200℃、升溫速度:10℃/min之條件下測定。再者,關於熱膨脹係數,針對以MD方向作為配線橫斷方向之間距,測定MD方向之熱膨脹係數(αTMD ),針對以TD方向作為配線橫斷方向之間距,測定TD方向之熱膨脹係數(αTTD ),使用該等熱膨脹係數算出熱膨脹係數之差之絕對值(|αTMD -αTTD |,於表中為|MD-TD|)。(8) Coefficient of thermal expansion (CTE) Using TMA-60 (manufactured by Shimadzu Corporation), it was measured under the conditions of a measurement temperature range: 50° C. to 200° C., and a temperature increase rate: 10° C./min. Furthermore, regarding the thermal expansion coefficient, the thermal expansion coefficient in the MD direction (αT MD ) was measured for the MD direction as the distance between the wiring transverse directions, and the thermal expansion coefficient in the TD direction (αT MD ) was measured for the TD direction as the distance in the wiring transverse direction. TD ), using these coefficients of thermal expansion to calculate the absolute value of the difference in coefficient of thermal expansion (|αT MD −αT TD |, in the table, |MD−TD|).
(9)尺寸穩定性 於上述獲得之評價用可撓性印刷基板之兩處電子零件連接部分上分別配置評價用半導體晶片(IC),使用覆晶接合機,於載台溫度150℃、工具溫度360℃下壓接1秒,獲得如圖2所示安裝有半導體晶片3之基板。其後,測定安裝部位之配線部之外形尺寸(L4),並根據壓接前之測定值(L3),基於下式算出伸長率,求出30個樣品之標準偏差而評價尺寸穩定性。 伸長率(%)={(L4-L3)/L3}×100(9) Dimensional stability Place semiconductor chips (ICs) for evaluation on the two electronic component connection parts of the flexible printed circuit board for evaluation obtained above, and use a flip-chip bonding machine at a stage temperature of 150°C and a tool temperature Press bonding at 360° C. for 1 second to obtain a substrate mounted with a
[表3]
根據上述表3之結果,可知於實施例中,可效率良好地反映實施例1~4中所獲得之聚醯亞胺膜之CTE值,可實現較高之尺寸穩定性,可減小尺寸穩定性之差異。According to the results in Table 3 above, it can be seen that in the examples, the CTE values of the polyimide films obtained in Examples 1 to 4 can be efficiently reflected, higher dimensional stability can be achieved, and dimensional stability can be reduced. gender differences.
(評價用覆蓋膜之製作) 製備包含聚醯胺醯亞胺樹脂(東洋紡製造,VYLOMAX HR16-NN)70重量份、液狀環氧樹脂(Mitsubishi Chemical製造,jER828,環氧當量190)50重量份、固態環氧樹脂(Mitsubishi Chemical製造,jER1001,環氧當量480)50重量份、氧化鋁(住友化學製造,AA04,平均粒徑0.4 μm)60重量份、硬化劑(4,4'-二胺基二苯碸)8重量份,並以N-甲基-2-吡咯啶酮作為溶劑之固形物成分40質量%之樹脂組合物A。 利用棒式塗佈機於表4所示之聚醯亞胺膜1上塗佈該樹脂組合物,於150℃下乾燥30分鐘,製作附有乾燥後之厚度為15 μm之B階段接著劑4的聚醯亞胺膜,作為覆蓋膜(圖3)。(Preparation of cover film for evaluation) A preparation containing 70 parts by weight of polyamide imide resin (manufactured by Toyobo, VYLOMAX HR16-NN) and 50 parts by weight of liquid epoxy resin (manufactured by Mitsubishi Chemical, jER828, epoxy equivalent 190) , Solid epoxy resin (manufactured by Mitsubishi Chemical, jER1001, epoxy equivalent 480) 50 parts by weight, alumina (manufactured by Sumitomo Chemical, AA04, average particle diameter 0.4 μm) 60 parts by weight, hardener (4,4'-diamine 8 parts by weight of base diphenyl (diphenylsulfone), and use N-methyl-2-pyrrolidone as the resin composition A of 40% by mass of the solid content of the solvent. Use a bar coater to coat the resin composition on the
(評價用多層可撓性印刷基板之製作) 於表4所示之聚醯亞胺膜1之支持體面藉由濺鍍法形成鎳鉻層(Ni:Cr=95:5,厚度10 nm)及銅層(厚度100 nm)後,以相同方式於非支持體面亦形成鎳鉻層、銅層2'。繼而,藉由使用硫酸銅鍍液之電解鍍覆於兩面形成厚度8 μm之銅層2',而製作雙面覆銅積層板(圖4)。進而,依據常規方法,使用液狀抗蝕劑製作膜厚5 μm之負型抗蝕劑,藉由蝕刻去除銅層及鎳鉻層後,剝離抗蝕劑,而製作圖5所示之於兩面具有銅配線2之雙面可撓性印刷基板,將其作為內層基板。 繼而,使用表4所示之聚醯亞胺膜1,僅於單面形成銅配線2,除此以外,以與雙面可撓性印刷基板相同之方式製作單面可撓性印刷基板。 進而,製備包含丙烯腈-丁二烯橡膠(日本瑞翁製造,Nipol 1043,腈含量29%)70重量份、液狀環氧樹脂(Mitsubishi Chemical製造,jER828,環氧當量190)50重量份、固態環氧樹脂(Mitsubishi Chemical製造,jER1001,環氧當量480)50重量份、氧化鋁(住友化學製造,AA04,平均粒徑0.4 μm)60重量份、硬化劑(4,4'-二胺基二苯碸)8重量份,且以甲基異丁基酮作為溶劑之固形物成分40質量%之樹脂組合物B。 利用棒式塗佈機於上述獲得之單面可撓性印刷基板之膜面塗佈該樹脂組合物,於150℃下乾燥10分鐘,而製作附有乾燥後之厚度為15 μm之接著劑的單面可撓性印刷基板(圖6),作為外層基板。 繼而,於上述獲得之內層基板之兩面使MD及TD方向一致地依序重疊外層基板、覆蓋膜,於150℃、3 MPa之條件下進行30分鐘之熱壓接,而製作圖7所示之評價用多層可撓性印刷基板。 對所獲得之多層可撓性印刷基板評價以下之項目。將結果示於表4。 (10)翹曲(B法) 將多層可撓性印刷基板裁切成70 mm×70 mm之大小,靜置於平板上,利用JIS1級曲尺測定4點距離平板上之高度,採用最大值。(Fabrication of Multilayer Flexible Printed Boards for Evaluation) On the support surface of the
[表4]
根據上述表4之結果,可知藉由使用實施例中所獲得之聚醯亞胺膜,即便為多層構造基板,亦可將翹曲抑制得較小。 [產業上之可利用性]From the results in Table 4 above, it can be seen that warpage can be suppressed to be small even if it is a multilayer substrate by using the polyimide film obtained in the examples. [Industrial availability]
本發明之聚醯亞胺膜於尺寸穩定性或操作性方面優異。又,本發明之聚醯亞胺膜亦能夠賦予彎折特性等。 本發明之聚醯亞胺膜尤其不僅於一個方向上尺寸穩定性均優異,且於不同方向上,進而無論於哪一方向上,尺寸穩定性均優異,因此,可良好地用作用於以窄間距設置不同方向(例如MD方向及TD方向)之配線、或安裝複數個電子零件、或設為多層構造等之聚醯亞胺膜。The polyimide film of the present invention is excellent in dimensional stability and handleability. In addition, the polyimide film of the present invention can also impart bending properties and the like. In particular, the polyimide film of the present invention is excellent in dimensional stability not only in one direction, but also in different directions, and no matter in which direction, it is excellent in dimensional stability. Polyimide film for wiring in different directions (such as MD direction and TD direction), or for mounting multiple electronic components, or for multi-layer structure.
1‧‧‧聚醯亞胺膜2‧‧‧配線(圖案)2'‧‧‧金屬層(銅層)3‧‧‧電子零件(半導體晶片等)4‧‧‧接著層(接著劑)1‧‧‧polyimide
圖1係於聚醯亞胺膜上形成有不同方向之配線電路圖案之基板之俯視圖。 圖2係於圖1之基板之配線電路圖案上安裝有電子零件之基板之俯視圖。 圖3係覆蓋膜之剖視圖。 圖4係於兩面設置有金屬層之聚醯亞胺膜(雙面覆銅積層板)之剖視圖。 圖5係於兩面設置有配線之聚醯亞胺膜(雙面可撓性印刷基板)之剖視圖。 圖6係於一面設置配線且於另一面設置接著劑層之聚醯亞胺膜(設置有接著劑層之可撓性印刷基板)之剖視圖。 圖7係多層可撓性印刷基板之剖視圖。FIG. 1 is a top view of a substrate with wiring circuit patterns in different directions formed on a polyimide film. FIG. 2 is a plan view of a substrate on which electronic components are mounted on the wiring circuit pattern of the substrate in FIG. 1 . Fig. 3 is a cross-sectional view of the cover film. Fig. 4 is a cross-sectional view of a polyimide film (double-sided copper-clad laminate) provided with metal layers on both sides. Fig. 5 is a cross-sectional view of a polyimide film (double-sided flexible printed substrate) provided with wiring on both sides. 6 is a cross-sectional view of a polyimide film (flexible printed substrate provided with an adhesive layer) with wiring on one side and an adhesive layer on the other side. Fig. 7 is a cross-sectional view of a multi-layer flexible printed substrate.
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