TWI344804B - Flexible laminate board and process - Google Patents
Flexible laminate board and process Download PDFInfo
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- TWI344804B TWI344804B TW094122032A TW94122032A TWI344804B TW I344804 B TWI344804 B TW I344804B TW 094122032 A TW094122032 A TW 094122032A TW 94122032 A TW94122032 A TW 94122032A TW I344804 B TWI344804 B TW I344804B
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- resin layer
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- polyimide
- metal
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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
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- 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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- 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
- B32B37/00—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding
- B32B37/14—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the properties of the layers
- B32B37/24—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the properties of the layers with at least one layer not being coherent before laminating, e.g. made up from granular material sprinkled onto a substrate
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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
- B32B37/00—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding
- B32B37/14—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the properties of the layers
- B32B37/24—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the properties of the layers with at least one layer not being coherent before laminating, e.g. made up from granular material sprinkled onto a substrate
- B32B2037/243—Coating
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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
- B32B2307/20—Properties of the layers or laminate having particular electrical or magnetic properties, e.g. piezoelectric
- B32B2307/206—Insulating
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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
- B32B2307/50—Properties of the layers or laminate having particular mechanical properties
- B32B2307/51—Elastic
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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
- B32B2307/50—Properties of the layers or laminate having particular mechanical properties
- B32B2307/538—Roughness
Landscapes
- Laminated Bodies (AREA)
Description
1344804 九、發明說明: 【發明所屬之技術領域】 <本發明係關於電子材料領域,特別為了形成電路而所 •採用之由金屬$與聚S!亞胺絕緣樹脂層所構成的可挽性積 .層板。 【先前技術】 聚醯亞胺4膜在熱特性、絕緣性、耐溶劑性等方面均 優越’已廣泛的使用為行動電話等電氣/電子機器零件的材 料。近年,隨行動電話等的薄型化、高功能化之演進,盆 機器零件材料所搭載的基板,已從剛性基板轉變為可挽性 印刷電路板。如此之可撓性印刷電路板乃廣泛的使用可許 性積層板,其中一部分的可撓性積層板在與此金屬结鄰^ 的絕緣樹脂層是使用環氧樹脂等點著性樹脂,而基底部的 絕緣樹脂層則使用聚醒亞胺樹脂。但是,因應近年的無錯 鲜錫,隨半導體元件安裝的時間縮短、高效率化,預測安 時的溫度、壓力將會上昇’此情況’於使用環氧樹脂的 可撓性積層板時,因為環氧樹脂的耐熱性等熱特性偏低, 因而有指出將產生較難因應高溫安裝的問題。 所以,已知如專利文獻丨便開發在與金屬箔鄰接的絕 4:树月日層’使用耐熱性較高之聚酿亞胺樹腊的可撓性積層 板,但是,即使此種由金屬箔與聚醯亞胺樹脂層所構成的 雙層可撓性積層板,因為载至目前為止仍需要在絕緣樹腊 層上疊層金屬落,因而金屬落所鄰接之聚醯亞胺樹脂層便 '曰'遍使用,熱可塑性聚酿亞胺樹月旨。但是,即使使用目前已 317J92 5 1344804 知的熱可塑性聚醯亞胺樹脂之可撓性積層板,實際上,並 無法承受因應高溫/高壓條件所施行半導體元件安裝的優 越熱特性,且未具備可撓性積層板的諸項特性。 [專利文獻1]WO〇2/〇85616號公報 [專利文獻2]曰本專利特開2〇〇3_338525號公報 [專利文獻3]曰本專利特開2〇〇3_264374號公報 另-方面,隨電子機器小型化的要求,便有開發在已 形成電路的配線基板上安裝半導體元件的技術。例如在專 利文獻2便揭示關於半導體裝置及其製造方法,在涵菩其 所記載技術在内之類似方法的技術中,當樹脂居於中^將 半導體7L件安裝於配線基板上時,為了使居中的樹脂成分 硬化或軟化,便將半導體元件與封裝夾具—起加敎至高 溫。關於此加熱溫度,在專利文獻2中記載加熱至28〇 : 3 0 (TC以上,但是此溫度將隨居 加熱至25(TC以上。此外,亦有樹脂未居中,而是使相鄰 丨金屬相互形成共晶的方法,此情況下,將加熱至更高溫戶。 如專利域2, +導體元件對基板的安裝,係在加執^,° 將半導體元件的凸塊朝配線基板的導體層加壓而安裝,此 情況下,積層板的導體電路所鄰接之半導體元件凸塊 突起部’因為在高溫狀態下被壓接於基板上並按壓接 因此若配線基板所鄰接樹脂層的耐熱性偏低、 材質的話,在銜接部分處將隨溫度而產生壓力集中現:人 配線基板之樹脂層上的電路、或部分半導體元件 ^ 於基板的絕緣樹脂層中,而產生無法執行穩定安裝的不^ 317J92 1344804 - 情況。 • 上述問題雖在配線基板中填充無機材料的話,便有可 能解決的情況,但是此情況下,將無法保持配線基板的彎 -曲性等,導致僅能使用在不同於工業上使用可撓性積層板 .之領域。有關著眼於耐熱性樹脂在高溫(3〇〇ΐ)下之彈性模 數的耐熱性樹脂組成物、及使用#之多㉟配線基板的技 術’ f專利文獻3中是有所記載。但是,專利文獻3所記 •載的樹脂組成物’可使用為半導體晶片的表面保護膜、半 導體封裝的層間絕緣膜、供半導體元件安裝用的基板層間 絕緣膜等方面,但是實際上針對在保持可撓性特性的狀態 下,適用於半導體安裝用途時的探討尚嫌不足,且與習知 可撓性積層板同樣’未考慮設計對安裝用途的適用。 f發明内容】 (發明所欲解決之課題) 提供-種不損及與金屬㈣之㈣性,且可 匕鄰接脂的玻璃轉移溫度㈣、虚 而溫區域(3贼)中的料彈性難,藉此可得到能承受^ 皿女裝條件㈣熱特性優越之可撓性積層板。 (供解決課題之手段) 為了解決上述課題經深人探料果,本發明人發現; 由將可撓性積層板的絕緣樹脂 ▲ ^ 可成為經提升_特性的可㈣騎定構造Μ 換句H &積層板’遂完成本發明. 換句本發明的可撓 的單面或雙面上,具有全屬〜… 知在絕_“ …有金屬泊的可撓性積層板 317192 1344804 i .緣樹脂層係由複數層聚醯亞胺樹脂所構成,且與金屬溪鄰 接至少1層的聚醯亞胺樹脂,在3 5〇。匸之儲存彈性模數為 ΙχΙΟ8至2M09Pa、破璃轉移溫度為3〇〇至4〇〇〇c的高彈性 .Μ知層所形成,而除高彈性樹脂層以外的樹脂層,至少具 、有1層線%脹係數為2〇χ 1 〇·6/Κ以下的低熱膨脹性樹脂 層,且絕緣樹脂層的高彈性樹脂層厚度比率在3至45%範 圍内。 其中,藉由滿足下述要件之任一者或以上,將可形成 更良好之可撓性積層板:〗)低熱膨脹性樹脂層之兩側為高 彈性樹脂層;2)構成與金屬箔鄰接之高彈性樹脂層的聚醯 亞胺樹脂係使用由均苯四曱酸二酐與二胺所製得者,二胺 ^使用含有5至80莫耳%之選自2,孓雙[4_(4_胺基苯氧基) j基]丙烷、1,4-雙(4-胺基苯氧基)苯、込弘雙^ —胺基苯氧基) 苯、4,4··雙(4-胺基笨氡基)聯苯中之至少】種二胺者‘,或 3)與聚醯亞胺樹脂層鄰接之金屬箔表面的表面粗糙度 •在0.6至範圍内。 再者,本發明的可撓性積層板之製造方法,係由至少 1層金屬箔與至少2層聚醯亞胺樹脂所構成;包含有下述 Y驟·】)在表面粗糙度(Rz)在0 6至】〇以m範圍内的金屬 焰表面上,塗佈著構成在3 5 〇°C之儲存彈性模數為1 X 1 2 ] 〇 Pa、玻璃轉移溫度為300至400。(:之高彈性樹脂 層,聚酿亞胺前驅物樹脂的步银;2)在±述聚酿亞胺前驅 物樹脂層上,塗佈著構成線膨脹係數在20X10.VK以下之 低熱膨脹性樹脂層的聚醯亞胺前驅物樹脂的步驟;以及3) 3)7)92 8 1344804 在金屬箔上設置複數層聚醯亞胺前驅物樹脂層的狀態下, 施行熱硬化處理的步驟。 以下,詳述有關本發明的可撓性積層板。 本發明的可挽性積層板係由絕緣樹脂層與金屬综所構 成,在絕緣樹脂層的單面或雙面上具有金屬箔。其中,絕 緣樹脂層係由複數層聚醯亞胺樹脂所構成’與金屬结鄰接 之至少1層聚醯亞胺樹脂層,係在35(rc儲存彈性模數為 JxlO8至2xl09Pa、玻璃轉移溫度在3〇〇至4〇〇。匸範圍内的 高彈性樹脂層所形成。此外,在絕緣樹脂層中,此高彈性 樹脂層的厚度比率必須在3至45%範圍内。另外,高彈性 樹脂層最好鄰接設置於低熱膨脹性樹脂層之二側。 本發明所使用的聚醯亞胺樹脂係適當選用周知的二胺 基化^物、與四羧酸或其去水物,組合該等,在有機溶劑 中進订反應,可得適合構成絕緣樹脂層各層特性者◎本發 明中,备稱「聚醯亞胺樹脂」時,係指以分子中具有醯亞 •胺鍵結的聚醯亞胺樹脂、或聚醯胺醯亞胺樹脂為主成分 者,未必一定要為單一聚醯亞胺樹脂,依情況亦可為與其 脂的混合物。當與其他樹脂成混合物之情況時,其他 樹脂係含有30%以下,最好在2〇%以下。此外,若較少量 的^,雖亦可調配入無機充填材,但是該等配方恐將損及 本發明可撓性積層板所具有的耐折性與電路加工性,因而 取好保留微量狀態。實質而言,絕緣樹脂層最好 胺樹脂層所構成。 & 本發明中,構成35(TC儲存彈性模數】x〗〇s至 317192 9 1344804 2Xl〇9]Pa、玻璃轉移溫度300至400°C範圍内之高彈性樹脂 層(以下簡稱「高彈性樹脂層j )的聚醯亞胺樹脂(以下簡稱 「南彈性聚酿亞胺樹脂」),在滿足其特性的前提下並無特 別限制’但是最好為具有下述一般式(I)所示結構單位的聚 醯亞胺樹脂。 【化1】1344804 IX. Description of the Invention: [Technical Field to Which the Invention Is Applicable] The present invention relates to the susceptibility of a metal $ and a poly S! imine insulating resin layer in the field of electronic materials, particularly for forming a circuit. Product. Laminate. [Prior Art] Polyimine 4 film is superior in thermal properties, insulation properties, solvent resistance, etc. It has been widely used as a material for electrical/electronic machine parts such as mobile phones. In recent years, with the development of thinner and more functional mobile phones, the substrate on which the pot machine parts are mounted has been converted from a rigid substrate to a disposable printed circuit board. Such a flexible printed circuit board is widely used as a permittable laminate, and a part of the flexible laminate is in the insulating resin layer adjacent to the metal, using a resin such as epoxy resin, and the substrate The insulating resin layer of the part is made of a polyamidide resin. However, in response to the error-free fresh tin in recent years, as the time for mounting semiconductor components is shortened and the efficiency is increased, it is predicted that the temperature and pressure of the ampere will rise. This is the case when using a flexible laminate of epoxy resin because The heat resistance and the like of the epoxy resin are low, and it is pointed out that it is difficult to handle the high temperature. Therefore, it is known that, as in the patent document, it is known to use a flexible laminate of a heat-resistant high-density iodized tree wax adjacent to a metal foil adjacent to a metal foil, but even such a metal is used. A two-layer flexible laminate composed of a foil and a polyimide resin layer, since it is still required to laminate a metal drop on the insulating wax layer so that the metal polyimide adjacent to the polyimide layer '曰' is used all over, thermoplastic polystyrene tree. However, even if the flexible laminate of the thermoplastic polyimine resin known from 317J92 5 1344804 is used, it is practically incapable of withstanding the superior thermal characteristics of the semiconductor element mounting in response to high temperature/high pressure conditions, and is not provided. The characteristics of the flexible laminate. [Patent Document 1] WO 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 专利 另 另 另 另 另 另 另 另 另 另 另 另 另 另 另In order to miniaturize an electronic device, there has been developed a technique of mounting a semiconductor element on a wiring board on which a circuit has been formed. For example, Patent Document 2 discloses a semiconductor device and a method of manufacturing the same, and in a technique similar to the technique described in the Japanese Patent Application, in order to center the semiconductor when the resin is mounted on the wiring substrate, The resin component is hardened or softened, and the semiconductor component and the package jig are twisted to a high temperature. In this heating temperature, Patent Document 2 describes heating to 28 〇: 30 (TC or more, but this temperature will be heated to 25 (TC or more). In addition, the resin is not centered, but adjacent bismuth metal A method of forming a eutectic with each other, in which case it is heated to a higher temperature household. As in Patent Field 2, the mounting of the conductor element to the substrate is performed by applying a bump to the conductor layer of the wiring substrate. The semiconductor element bump projections adjacent to the conductor circuit of the laminated board are pressed against the substrate in a high temperature state and pressed, so that the heat resistance of the resin layer adjacent to the wiring substrate is biased. When the material is low, the pressure is concentrated with the temperature at the joint portion: the circuit on the resin layer of the human wiring substrate or a part of the semiconductor element is in the insulating resin layer of the substrate, and the stable mounting cannot be performed. 317J92 1344804 - Situation. • The above problem may be solved by filling the wiring board with inorganic materials. However, in this case, the wiring substrate cannot be bent. In the field of the use of a flexible laminate, which is different from the industrial use, a heat resistant resin composition focusing on the elastic modulus of the heat resistant resin at a high temperature (3 Å), and The technique of using the #35 wiring board is described in Patent Document 3. However, the resin composition described in Patent Document 3 can be used as a surface protective film for a semiconductor wafer or an interlayer insulating film for a semiconductor package. In the case of a substrate interlayer insulating film for mounting a semiconductor element, in actuality, it is not sufficient to be suitable for semiconductor mounting applications while maintaining flexibility characteristics, and is similar to a conventional flexible laminate. 'The design is not considered for the purpose of installation. f Inventive content】 (Problems to be solved by the invention) Provide a kind of glass transition temperature (four), virtual temperature region that does not damage the (four) nature of the metal (4) (3 thieves) The material elasticity is difficult, and it is possible to obtain a flexible laminate which can withstand the conditions of the women's clothing (4). (The means for solving the problem) The inventors discovered that the insulating resin ▲ ^ of the flexible laminated board can be upgraded and characterized by a (four) riding structure 换 a sentence H & laminated board '遂 to complete the present invention. The flexible single-sided or double-sided surface of the present invention has a full genus~... knowing that there is a flexible laminated board with metal mooring 317192 1344804 i. The edge resin layer is composed of a plurality of layers of polyimide resin. The polyimine resin which is composed of at least one layer adjacent to the metal stream has a storage elastic modulus of ΙχΙΟ8 to 2M09Pa and a glass transition temperature of 3〇〇 to 4〇〇〇c. The resin layer formed of the elastic layer is formed of at least one layer, and the resin layer other than the high elastic resin layer has at least one layer of a low thermal expansion resin layer having a coefficient of expansion of 2 〇χ 1 〇·6/Κ or less, and an insulating resin. The layer has a high elastic resin layer thickness ratio in the range of 3 to 45%. Among them, by satisfying any one or more of the following requirements, a more favorable flexible laminate can be formed: a) a low elastic expansion resin layer on both sides of the high elastic resin layer; 2) a structure adjacent to the metal foil The polyaniline resin of the high elastic resin layer is obtained by using pyromellitic dianhydride and a diamine, and the diamine is used in an amount of 5 to 80 mol% selected from 2, bismuth [4_( 4_Aminophenoxy)j-yl]propane, 1,4-bis(4-aminophenoxy)benzene, hydrazine bis-aminophenoxy) benzene, 4,4··bis (4 The surface roughness of the surface of the metal foil adjacent to the polyimine resin layer of the at least one of the biphenyl groups in the biphenyl group, or 3) is in the range of 0.6 to 10,000. Furthermore, the method for producing a flexible laminate according to the present invention comprises at least one metal foil and at least two layers of a polyimide resin; and the following Y-steps are included in the surface roughness (Rz). On the surface of the metal flame in the range of 0 to 〇, the storage elastic modulus of the composition at 3 5 〇 ° C is 1 X 1 2 ] 〇Pa, and the glass transition temperature is 300 to 400. (: a high elastic resin layer, a step silver of a polyanilin precursor resin; 2) a low thermal expansion property of a linear expansion coefficient of 20×10. VK or less coated on the resin layer of the polyimide precursor precursor a step of a polyimine precursor resin of a resin layer; and 3) 3) 7) 92 8 1344804 A step of performing a heat hardening treatment in a state in which a plurality of layers of a polyimide intermediate resin layer are provided on a metal foil. Hereinafter, the flexible laminate of the present invention will be described in detail. The removable laminate of the present invention is composed of an insulating resin layer and a metal composite, and has a metal foil on one or both sides of the insulating resin layer. Wherein, the insulating resin layer is composed of a plurality of layers of polyimide resin, and at least one layer of the polyimide resin layer adjacent to the metal junction is at 35 (the storage elastic modulus of the rc is JxlO8 to 2xl09Pa, and the glass transition temperature is at 3〇〇 to 4〇〇. A highly elastic resin layer is formed in the range of 匸. Further, in the insulating resin layer, the thickness ratio of the high elastic resin layer must be in the range of 3 to 45%. In addition, the high elastic resin layer Preferably, it is disposed adjacent to both sides of the low heat-expandable resin layer. The polyimine resin used in the present invention is suitably selected from a known diamine compound, a tetracarboxylic acid or a dehydrated product thereof, and the like. When the reaction is carried out in an organic solvent, it is possible to obtain the characteristics of each layer of the insulating resin layer. In the present invention, when it is referred to as "polyimine resin", it means a polyazide having a quinone-amine bond in the molecule. The amine resin or the polyamidoximine resin as a main component may not necessarily be a single polyimine resin, and may be a mixture thereof with a fat. When it is mixed with other resins, the other resin is Contains less than 30%, the best 2% or less. In addition, if a small amount of ^ can be blended into the inorganic filler, these formulations may impair the folding resistance and circuit processability of the flexible laminate of the present invention. In essence, the insulating resin layer is preferably composed of an amine resin layer. & In the present invention, the composition 35 (TC storage elastic modulus) x 〇 s to 317192 9 1344804 2Xl 〇 9] Pa, A polyimide resin having a high elastic resin layer (hereinafter referred to as "high elastic resin layer j") having a glass transition temperature of 300 to 400 ° C (hereinafter referred to as "South Elastic Polyimide Resin") satisfies its characteristics. There is no particular limitation on the premise, but it is preferably a polyimine resin having the structural unit represented by the following general formula (I).
般式⑴中,Arl、A。係碳數12以上的2價芳香族殘 基;Ar2係碳數6以上的4 μ I t “ 上的Μ貝方香族殘基;k、】係指k+1==1〇 時的各構成單位莫耳比惠 关斗比羊’ k為20至95,丨為80至5 數值。 幻 其中 【化2】In the general formula (1), Arl, A. a divalent aromatic residue having 12 or more carbon atoms; 4 μl of the Ar 2 carbon number of 6 or more, and a kine group residue; k, ??? The constituent unit Moerby Hui is more than the sheep 'k is 20 to 95, and the 丨 is 80 to 5 numerical value.
Arl最好為如式(a)所示2價基。Arl is preferably a divalent group represented by the formula (a).
再者,Ar2最好為如式(b)所示 【化3】 4價基 〇Furthermore, Ar2 is preferably as shown in formula (b). [Chemical 3] 4-valent group 〇
以 (十_中之任〗:上為:: 317192 10 1344804 【化4] ω(10) in the ten: in the upper:: 317192 10 1344804 [chemical 4] ω
"'"OK0~|Qpa~OH' ω (ί) 高彈性聚醯亞胺樹脂在350°C之儲存彈性模數,必須 在lxlO8至2xl09Pa範圍内,尤以lxlO8至ixioka範圍為 佳。若此數值低於1 X 1 〇8pa,例如當高溫下安裝半導體元 件時,於此安裝溫度中,與金屬箔鄰接之絕緣樹脂層將呈 流動狀態,導致容易發生金屬配線沉陷情況。反之,高彈 性樹脂的儲存彈性模數超過2xl〇9pa,雖就從本發明目的 的高溫下熱特性觀點而言將屬較佳狀況,但是突顯可撓性 ,積層板彎曲特性的柔軟性恐將降低。此外,高彈性樹脂層 係玻璃轉移溫度(Tg)必須在3〇〇至4〇〇t範圍内,尤以 至380 C靶圍内更為有利。若玻璃轉移溫度低於的 名將如同上述,容易發生金屬配線沉陷的情況,而 撓性積層板㈣錫耐熱性亦將惡化。反之 度超過4〇(TC的爷,取搞Λ 石圾祸轉移微 好的㈣性。U W層與金屬㈣將無法獲得良 本發明可搢抖# a』 成,除上述# θ㈣絕緣樹脂層係由複數層所構 卜尚具有線膨腹係數 317)92"'"OK0~|Qpa~OH' ω (ί) The storage modulus of the highly elastic polyimide resin at 350 ° C must be in the range of lxlO8 to 2xl09Pa, especially in the range of lxlO8 to ixioka. If the value is lower than 1 X 1 〇 8 Pa, for example, when the semiconductor element is mounted at a high temperature, the insulating resin layer adjacent to the metal foil will flow in this mounting temperature, resulting in occurrence of metal wiring sinking. On the other hand, the high elastic resin has a storage elastic modulus of more than 2 x 1 〇 9 Pa, which is preferable from the viewpoint of the high-temperature heat characteristics of the object of the present invention, but the flexibility is exhibited, and the flexibility of the bending property of the laminated sheet is likely to be reduce. Further, the glass transition temperature (Tg) of the highly elastic resin layer must be in the range of 3 Torr to 4 Torr, particularly in the target range of 380 C. If the glass transition temperature is lower than the above, the metal wiring sinks easily, and the flexible laminate (4) tin heat resistance will also deteriorate. On the other hand, the degree exceeds 4 〇 (the TC's lord, take the Λ 圾 圾 圾 圾 圾 圾 圾 圾 圾 圾 圾 圾 圾 圾 圾 圾 圾 圾 圾 圾 圾 圾 圾 圾 圾 圾 圾 圾 圾 圾 圾 圾 圾 圾 圾 圾 圾 圾 圾 圾 圾 圾 圾 圾 圾 圾The structure of the complex layer has a line expansion coefficient of 317)92
(D 1344804 20χ】0·6/Κ·以下最好 取計〗X10 7/K至2〇x〗〇-6/k的低熱膨脹性樹 脂層。構成低熱膨勝性樹脂層的聚s!亞胺樹脂(以下亦稱 「低熱膨脹性聚醯亞脸與# 、—# ^ 亞胺树如」),在滿足其特性的前提下並 無特別限制,但是最接主g女丁、+ ^ 取好為具有下述一般式(Η)所示結構單位 的聚醯亞胺樹脂。 【化5】(D 1344804 20χ) 0·6/Κ· The following is the best calculation. X10 7/K to 2〇x〗 〇-6/k low thermal expansion resin layer. Poly s! Amine resin (hereinafter also referred to as "low thermal expansion poly yam face and #, -# ^ imine tree"), there is no special restriction on the premise of satisfying its characteristics, but the most important thing is the female g, D + It is preferably a polyimine resin having a structural unit represented by the following general formula (Η).
q、d別係〇至4的數值。A Μ異的低級烧基; 以上的4價基。此外,在式(1)r;取好為下式(h)與⑴所示1 直接鍵結。 X係指S02、CO、〇或 【化6】q, d do not 〇 to the value of 4. A very different low-grade base; the above four-valent base. Further, in the formula (1)r; it is preferred that the following formula (h) is directly bonded to the one shown in (1). X means S02, CO, 〇 or [6]
(b) ω 上述一般式(II)所示單位妗m丄 結構單位。 ° ’最好為下式(III)所示 【化7】(b) ω The unit 妗m丄 structural unit shown in the above general formula (II). ° ' is preferably as shown in the following formula (III) [Chem. 7]
317192 12 1344804 一般式(Π)或(III)所示結構單位,可含有低熱膨脹性聚 ,醯亞胺樹脂之總聚醯亞胺結構單位的50莫耳%以上。 本%明所使用的金屬箔有銅箔、不銹鋼箔、合金箔等。 •其中’所謂「合金结」係指必須含有銅箱,且含有絡、錄、 .鋅、矽等元素中至少"重以上的金屬箱,銅含有率90%以 上的金屬箔。當使用金屬箔的情況,亦可利用鍍鋅、鍍鎳、 石夕烧偶合劑等施行表面處理。 隨著金屬配線的超細間距化,最好使用較薄的金屬 矚辖。就從此觀點而言,最好金屬结厚度為5至35ym,尤 以8至】8"m之範圍為佳。此外,所使用的金屬落最好在 與聚醯亞胺樹脂相鄰接面的表面粗度(Rz)為〇 6至】〇 #⑺ 把圍。當表面粗度(Rz)低於〇.6// m ,將無法維持金屬落 與聚醯亞胺樹脂層間的黏著性,反之,當以上的 情況,聚醯亞胺薄膜的透明性將降低,將妨礙半導體元件 ,裝。此外,藉由將金屬结的表面粗度(Rz)設定:上述 •範圍Θ ’將可降低電路加工時所發生的金屬成分殘留在聚 酿亞胺樹脂層的情況。如上述,表面粗度⑽在上述範圍々 内的金屬箔,將頗適於金屬配線的超細間距化。 本發明的可撓性積層板係由複數層聚醯亞胺樹脂形成 的絕緣樹脂層所構成的多層構造,且藉由將與金屬落曰鄰接 之至少1層聚酿亞胺樹脂層,設定為特定厚度範圍的上述 高彈性樹脂層’便可形成能承受高溫〆高塵安裝條件的可: 性積層板。其中,藉由將金屬结的厚度與表面粗度㈣气 定為上述範圍,則特別可適用於高密度安裝用途。 叹 3)7192 i3448°4 . 本發明的可撓性積層板係由複數層聚醯亞胺樹脂形成 * 的絕緣Μ脂層所構成的多層構造,最好的層構造可例示如 ' 下述1)至5)所示的層構造。其中,Μ係金屬箔,η係高彈 "性徽酿亞胺樹脂,L係低熱膨脹性聚酿亞胺樹脂,ρ係滿 足Η或L之儲存彈性模數或線膨脹係數以外的其他聚醒亞 胺樹脂。 1)M/H/L、2)M/H/L/H/M、3)M/H/L/H、4)M/H/L/P/M、 5)M/H/L/P、 # 而且,絕緣樹脂層中的H所佔厚度比率為3至45%, 最好在5至20%範圍内。其他的聚醯亞胺樹脂p,當為了 控制金屬箔蝕刻後的翹曲等情況而設置時,最好使用物理 特性近似Η的樹脂,特別以與H間的線膨脹係數差在 1 〇χ 10 /K以内者為佳。為了形成在絕緣樹脂層雙面上具有 金屬泊的可挽性積層板,在爾後對金屬箔施行加熱壓接的 方法將為較有利的做法,所以此情況下,與L相鄰接並積 _層的聚酿亞胺樹脂P’最好為線膨脹係數3〇χ1(Γ6/κ以上的 熱可塑性聚醯亞胺樹脂。 ^其次,雖說明本發明可撓性積層板之製造方法,但是 就已說明的可撓性積層板中相同内容加以整理簡單說明。 ^本發明的可换性積層板係在金屬辖上,塗佈聚酿亞胺 月J驅物Vi月曰’經乾燥後,施行熱破化處理,便可形成在金 | 屬箱單面上積層著聚酿亞胺樹脂層的積層板。在金屬结上( :塗佈的聚醯亞胺前驅物樹脂最好為溶液狀態,通常係& 解方'適田冷』中的狀態進行塗佈。聚酿亞胺前驅物樹脂 ; 14 317192 ⑧! 1344804 .^佈的金屬㉟面’表面粗糙度(RZ)最好在〇ι.6至】.〇_ •-摩巳®内。本發明可撓性積層板之製造方法中,在金肩溪上 直接塗佈的聚醯亞胺前驅物樹脂,係硬化後在35〇。€的儲 .存彈模數H08至2xl〇9Pa、玻璃轉移溫度為3〇〇至4〇〇 • 2的南彈性樹脂層。將構成此高彈性樹脂層的前驅物樹 脂三直接塗佈於金屬络上,便可獲得金屬·聚醯亞胺樹脂之 二、疋黏著強度。塗佈的手段並無特別的限制,可適當選擇 採用如:棒塗方式、凹版塗佈方式、輕式塗佈方式、模頭 •塗佈方式等周知方法。 主金屬箔所塗佈之聚醯亞胺前驅物樹脂層,當含有溶劑 的情況,便乾燥至適當範圍。此時的乾燥溫度,最好在聚 醯亞胺前驅物樹脂層未進行醯亞胺化反應的溫度下實施, 八肢而。最好在15〇c以下,尤以11〇至14〇。匸範圍為佳。 用此乾燥#驟’聚醯亞胺前驅物樹脂層中所含溶 切量最好以形成相當於聚醯亞胺前驅物樹脂丨〇〇重量份 φ的50重量份以下。 本發明的可撓性積層板,除上述高彈性樹脂層的㈣ 亞胺樹脂層之外,尚具有線膨脹係數2〇xHT6/K以下的低 …膨脹f生树脂層之聚酿亞胺樹脂I。低#膨服性樹脂層最 好如上述般在形成之構成高彈性樹脂層的聚醯亞胺前 物樹脂層上,以其前驅物狀態進行塗佈而形成。此低^ 脹性樹脂的前驅物樹脂,最好也是以溶液狀態進行塗佈, 當以含有溶劑之狀態進行塗佈的情況,最好如同上述 進行乾燥。 317192 15 1344804 在孟屬 >白上’逐次分別塗佈構成高彈性 膨脹性樹脂層的前驄私执日/、低热 Μ射,丨接心層’ '經乾燥後,為了能控制金 屬泊姓刻後的勉曲,丨杳:兄埜 紹…盆t 或好再設置1層聚酿亞胺前驅 物樹脂層。其中,张#应,,Ώ 積層的層最好是與上述高彈性樹脂層 么5 ” &理特性近似,特別以高彈性樹脂層與線膨脹 係數的差在I 〇 X 1 〇-6/κ LV免土 * 内者為侄。為了能形成在絕緣樹 脂層的雙面上具有金屬%沾技 、令兔屬沿的可撓性積層板,爾後藉由對金 屬搭施行加熱壓接的方法將為有利做法,所以此情況下: 低熱膨脹性樹脂層上所積層的㈣亞胺層,最好是線膨服 係數在3〇χ1()·6/Κ以上的熱可塑性㈣亞胺㈣。本發明 可撓性積層板中任意設置的聚醯亞胺樹脂層,亦如同上述 2個聚醯亞胺層的形成方法’經塗佈、乾燥便可形成。 如上述,若在金屬箔上對2或3以上的聚醯亞胺前驅 物樹脂層施行塗佈 '乾燥之後,再對金屬箔上的複數層聚 祕亞胺前驅物樹脂層施行加熱處理而熱硬化。加熱處理最 丨好通過多數硬化室來實施,此情況下,從〗5(rc附近起依 複數段、階段式昇温,最終加熱至2 5 〇以上,最好達3 〇〇 °C以上而醯亞胺化。若為了醯亞胺化而所施行加熱的最高 加熱/JDL度過兩的話’樹脂恐將分解,因而最好不要加熱至 比分解開始溫度低20°C的溫度以上。另外,此加熱處理亦 可接著上述乾燥步驟之後’繼續採用相同裝置實施。藉由 此步驟,聚醯亞胺前驅物樹脂便可實質的醯亞胺化。 在完成酿亞胺化的樹脂層上’配合必要再積層金屬 落。積層方法係將預定之金屬箔在沖壓或輥間加熱下,加 317192 1344804 歷而#施的方法較為簡便。其令,加熱溫度最好在與所積 .層金屬结相鄰接之聚酿亞胺樹脂層的玻璃轉移溫度以上。 又,在此所積層的金屬落可如同上述金屬落,當利用加熱 •:壓處理施行積層的情況,為了能保持與聚醯亞胺間的黏 著力,Rz以大於1 .〇 # m較為有利。 (發明之效果) 本發明的金屬層所鄰接之聚醯亞胺樹脂,因為具有截 至目前為止黏著性聚醯亞胺樹脂所不能達到的高Tg、在 • 350°C之高儲存彈性模數,因此將保持與金屬络間的高點著 性。所以,本發明的可撓性積層板因為絕緣樹脂層的耐熱 特性優越,因此頗適用為半導體元件之高溫安裝時,所採 用的COF(薄膜覆晶)(Chip 0n F彳化)用可撓性積層板。此 外’本發明的可撓性積層板係由複數層絕緣樹脂層所構 成’不僅其絕緣樹脂層的聚醯亞胺樹脂熱特性較高,且具 有行動電話等的彎曲部分所需要之高彎曲性,因此可使用 鲁於行動電話等小型電子機器方面,屬於具有工業價値的發 明。 【實施方式】 以下,針對本發明一實施例進行說明。另外,各薄膜 物性値係依下述方法進行測定。 1)玻璃轉移溫度(Tg)、高溫區域(350。〇的儲存彈性模 數’係將各合成例的聚醯亞胺前驅物樹脂所獲得聚醯亞胺 >專膜’利用Pheonietric Scientific公司製的動態黏彈性測定 裝置,測量依5。(: /mi進行昇溫時的動態黏彈性,求取Tg(tail 17 317192 ⑧ 占的極大値)及350T:之儲存彈性模數。 )熱知脹k數係知用精工工業公司製的TMA⑽型熱 機械分析裳置’依20ΐ /min昇溫速度' 51 /_降溫速度, -未取降溫時從100ΐ至24〇艺間的尺寸變化。 ‘ 3)與鋼结間的黏著力,係採用東洋精器製Suograph 在ΐ /皿下,依荷重元2kg、夾頭速度5〇mm/min,朝 ⑽度方向拉伸銅領,經測定而求得。評估基準係配合黏 著力’依下述進行評定。 〇:黏著力0.8kN/m以上 △.黏著力0‘5kN/m以上、低於〇 8kN/m X :黏著力低於0.5kN/m 4) 金屬鎢的表面粗縫度(rz)係根據JIS B 〇65 I,使用高 感度表面分布儀(KLA_Tencor公司製p_15),依測定速度 0.02mm/sec、曲率半徑2μηι的條件進行測定。 5) 可撓性積層板的銲錫财熱性係在所定溫度的銲錫槽 中浸潰10秒鐘,在不致發生金屬箱剝落、樹脂膨脹等現象 的溫度中,將最高溫度視為銲錫耐熱溫度。 實施例中的代號說明。 DMAc : Ν,:Ν’-二甲基乙醯胺 PMDA :均苯四曱酸二針 BPDA : 3,3’,4,4、聯苯四羧酸二酐 DSDA:二苯磺基-3,4,3·,4’-四幾酸二酐 BTDA :二苯曱酮-3,4,3,,4’·四羧酸二酐 ΒΑΡΡ : 2,2-雙[4-(4-胺基苯氧基)笨基]丙烷 3)7)92 1344804 BAPB : 4,4’_雙(4_胺基苯氧基)聯苯 丁PE-Q: 1,4-雙(4-胺基笨氧基)笨 TPE_H’· 1,3_雙(4·胺基苯氧基)笨 -m-TB:2,2'-二曱基-4,4’-二胺基聯苯 合成例〗至3 將BAPP與BAPB供應給DMAc中並溶解,接著再供 應PMDA,於室溫中㈣約3小時,便調製得在表^斤^ 組成成分所構成的聚醯亞胺前驅物樹脂溶液。 另外,在所有的合成例中,將四羧酸二酐成分與二胺 成分的比率設定為約100莫耳%化學計量。此外,表i中 的樹脂原料組成欄位的數値係指莫耳比率。 將所得的聚醯亞胺前驅物樹脂溶液塗佈於銅箔上,在 14 0 C以下的/jnL度中,將箾驅物樹脂層表面乾燥至不點手狀 怨,然後在]50至360°C溫度範圍中分開數階段的進行昇 •溫加熱,經醯亞胺化便形成厚度25#m的聚醯亞胺薄骐二 針對此聚醯亞胺薄膜,測定在35〇〇c之儲存彈性模數、破 璃轉移溫度(Tg)、及線膨脹係數。結果如表1所示。 合成例4、5 將BAPP與ΤΡΕ-Q供應給DMAc中並溶解,接著再 供應PMDA,於室溫中攪拌約3小時,便調製得在表】所 示組成成分所構成的聚醯亞胺前驅物樹脂溶液。此聚酿亞 胺前驅物樹脂溶液依合成例1相同的方法進行處理,而步 成聚酿亞胺薄膜’並評估其物性。結果如表〗所示。 317)92 19 1344804 合成例6、7 將BAPP與TPE-R供應給DMAc中並溶解,接著再供 應PMDA ’於室溫中攪拌約3小時,便調製得在夺】 組成成分所構成的聚醯亞胺前驅物樹脂溶液。此聚酿亞胺 前驅物樹脂溶液依合成例〗相同的方法進行處理,而,、 聚醯亞胺薄膜,並評估其物性。結果如表丨所示。^ 合成例8317192 12 1344804 The structural unit represented by the general formula (Π) or (III) may contain 50 mol% or more of the total polyamidene structural unit of the low thermal expansion polyimide resin. The metal foil used in the present invention includes copper foil, stainless steel foil, alloy foil, and the like. • The term “alloy alloy” refers to a metal foil that contains a copper box and contains at least a metal box of at least the weight of the elements such as lanthanum, lanthanum, lanthanum, and the like, and has a copper content of 90% or more. When a metal foil is used, surface treatment may be performed by galvanizing, nickel plating, orthopedic coupling agent or the like. As the metal wiring is ultra-fine pitched, it is preferable to use a thinner metal. From this point of view, it is preferable that the metal junction has a thickness of 5 to 35 μm, particularly preferably 8 to 8 "m. Further, it is preferable that the metal falling layer used has a surface roughness (Rz) of 〇 6 to 〇 ( #(7) in the adjoining surface with the polyimide resin. When the surface roughness (Rz) is lower than 〇.6//m, the adhesion between the metal falling layer and the polyimide layer of the polyimide resin layer cannot be maintained, and conversely, when the above case, the transparency of the polyimide film is lowered. It will hinder the semiconductor component and mount it. Further, by setting the surface roughness (Rz) of the metal junction: the above range Θ ', the metal component which occurs during the circuit processing can be reduced in the case of the polyimine resin layer. As described above, the metal foil having the surface roughness (10) in the above range 颇 is quite suitable for the ultrafine pitch of the metal wiring. The flexible laminate of the present invention is a multilayer structure composed of an insulating resin layer formed of a plurality of layers of polyimide resin, and is set to at least one layer of the polyimide resin layer adjacent to the metal drop. The above-mentioned high elastic resin layer of a specific thickness range can form a laminate which can withstand high temperature and high dust installation conditions. Among them, by setting the thickness of the metal junction and the surface roughness (4) to the above range, it is particularly suitable for high-density mounting applications. Sigh 3) 7192 i3448°4. The flexible laminated board of the present invention is a multilayer structure composed of an insulating resin layer formed of a plurality of layers of polyimide resin, and the best layer structure can be exemplified as follows. ) to the layer structure shown in 5). Among them, lanthanide metal foil, η-based high-elastic "genic yoke imine resin, L-based low thermal expansion poly aniline resin, ρ system meets the storage elastic modulus or linear expansion coefficient of Η or L Wake up the imine resin. 1) M/H/L, 2) M/H/L/H/M, 3) M/H/L/H, 4) M/H/L/P/M, 5) M/H/L/ P, # Moreover, the ratio of the thickness of H in the insulating resin layer is from 3 to 45%, preferably from 5 to 20%. When the other polyimide resin p is provided for controlling warpage after etching of the metal foil, it is preferable to use a resin having a physical property similar to that of yttrium, in particular, a difference in linear expansion coefficient with H is 1 〇χ 10 Those who are within /K are better. In order to form a removable laminate having metal mooring on both sides of the insulating resin layer, it is advantageous to apply a method of heating and crimping the metal foil, so in this case, adjacent to L and concatenated _ The layer of the polyimide resin P' is preferably a thermoplastic resin having a linear expansion coefficient of 3〇χ1 (Γ6/κ or more. ^ Next, although the method for producing the flexible laminate of the present invention is described, The same contents in the flexible laminated board have been described and succinctly explained. ^ The replaceable laminated board of the present invention is applied on a metal jurisdiction, and the coated polyimide II squirrel Vi 曰 经The thermal cracking treatment can form a laminate in which a layer of a polyimide resin layer is laminated on a gold plate. On the metal junction (the coated polyimide precursor resin is preferably in a solution state, It is usually coated in the state of 'Solution' in the 'Apparel Cold'. The polyurethane-precursor resin; 14 317192 8! 1344804 . The metal surface of the cloth is 'surface roughness (RZ) is best in 〇ι .6 to 】. 〇 _ _ _ 巳 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 Polyurethane precursor resin coated directly on the shoulder sill, after hardening at 35 〇. The storage and storage modulus is H08 to 2xl〇9Pa, and the glass transition temperature is 3〇〇 to 4〇〇• 2 The south elastic resin layer is obtained by directly coating the precursor resin 3 constituting the high elastic resin layer on the metal mesh to obtain the adhesive strength of the metal/polyimine resin. The coating method is not particularly limited. As a limitation, a well-known method such as a bar coating method, a gravure coating method, a light coating method, a die coating method, etc. may be appropriately selected. The polyimine precursor resin layer coated by the main metal foil is When the solvent is contained, it is dried to an appropriate range. The drying temperature at this time is preferably carried out at a temperature at which the polyimide phase of the polyimide precursor resin layer is not subjected to the hydrazine imidization reaction, preferably at 15 〇c. In the following, especially from 11 〇 to 14 〇. The range of 匸 is preferred. The amount of cleavage in the resin layer of the dried yttrium imide precursor is preferably used to form a resin corresponding to the polyimide precursor. 50 parts by weight or less of the weight part φ. The flexible laminate of the present invention In addition to the (IV) imide resin layer of the above-mentioned highly elastic resin layer, it has a low expansion coefficient of 2〇xHT6/K or less...the expanded i-resin layer of the expanded resin layer I. The low #expandable resin layer is the most The polyimine precursor resin layer constituting the highly elastic resin layer formed as described above is formed by coating in a precursor state. The precursor resin of the low-expansion resin is preferably also a solution. In the case of coating in a state where it is applied in a state containing a solvent, it is preferable to carry out drying as described above. 317192 15 1344804 Applying a layer of a highly elastically expandable resin layer successively to each other in the genus > Carrying the day /, low heat shot, 丨 心 ' ' ' After drying, in order to control the distortion of the metal poetry after the engraving, 丨杳: Xiong Ye Shao... pot t or better set up a layer of polyimine precursor Resin layer. Wherein, the layer of the ##,, Ώ layer is preferably similar to the above-mentioned high elastic resin layer, in particular, the difference between the high elastic resin layer and the linear expansion coefficient is I 〇 X 1 〇 -6 / κ LV is free of soil * The inside is made of yt. In order to form a flexible laminate which has a metal-based technique on both sides of the insulating resin layer and a rabbit edge, the method of heating and crimping the metal is performed. It will be advantageous, so in this case: The (iv) imine layer laminated on the low heat-expandable resin layer is preferably a thermoplastic (tetra) imine (4) having a linear expansion coefficient of 3 〇χ 1 ()·6/Κ or more. The polyimine resin layer arbitrarily provided in the flexible laminate of the present invention can also be formed by coating and drying the same as the method for forming the two polyimide layers. As described above, if it is on a metal foil 2 or more of the polyimine precursor resin layer is subjected to coating 'drying, and then the plurality of layers of the polyimine precursor resin layer on the metal foil are heat-treated and heat-hardened. Hardened room to implement, in this case, from 〖5 (near rc) The stage temperature rises, and finally heats up to 25 〇 or more, preferably up to 3 〇〇 ° C and yttrium. If the maximum heating / JDL of the heat applied for hydrazine imidization exceeds two, 'resin fear It will decompose, so it is best not to heat it to a temperature 20 ° C lower than the decomposition start temperature. In addition, this heat treatment may be followed by the same apparatus after the above drying step. By this step, the polyimine precursor The resin can be substantially imidized. On the finished imidized resin layer, 'the necessary metal layer is laminated. The layering method is to heat the predetermined metal foil under stamping or roller, and add 317192 1344804. The method of applying is relatively simple, and the heating temperature is preferably above the glass transition temperature of the polyamidide resin layer adjacent to the accumulated metal layer. Further, the metal layer deposited here may be as described above. In the case where the metal layer is deposited by heating or pressure treatment, in order to maintain the adhesion with the polyimide, it is advantageous that Rz is greater than 1. 〇 # m. (Effect of the invention) The metal layer of the present invention adjacent Polyimine resin, because of the high Tg that can not be achieved by the adhesive polyimide resin up to now, and the high storage elastic modulus at 350 ° C, will maintain high dot-to-metal Therefore, since the flexible laminated board of the present invention is excellent in heat resistance characteristics of the insulating resin layer, it is suitable for use in high-temperature mounting of semiconductor elements, and COF (film over-filming) (Chip 0n F )) used is flexible. Further, the flexible laminate sheet of the present invention is composed of a plurality of layers of an insulating resin layer. Not only the polyimide resin of the insulating resin layer has high thermal characteristics, but also has a curved portion of a mobile phone or the like. Because of its high flexibility, it can be used in small electronic devices such as mobile phones, and it is an invention with industrial price. [Embodiment] Hereinafter, an embodiment of the present invention will be described. Further, each of the film properties was measured by the following method. 1) Glass transition temperature (Tg), high temperature region (350. Storage elastic modulus of ') is obtained by using polypyridinium precursor resin of each synthesis example> Polycrystalline film made by Pheonietric Scientific Co., Ltd. The dynamic viscoelasticity measuring device measures the dynamic viscoelasticity at a temperature rise of 5 (: /mi, and obtains the Tg (maximum tail of tail 17 317192 8) and the storage elastic modulus of 350T:) The number system knows that the TMA (10) type thermomechanical analysis made by Seiko Industrial Co., Ltd. 'slows the temperature at 20 ΐ /min' 51 / _ cooling rate, - the dimensional change from 100 ΐ to 24 未 when no cooling is taken. ' 3) The adhesion between the steel knots was determined by using a Toograph made by Toyo Seiki under the ΐ / dish, with a weight of 2 kg and a chuck speed of 5 〇 mm/min, and stretching the copper collar in the direction of (10) degrees. The evaluation criteria are based on adhesions as assessed below. 〇: adhesion force 0.8kN/m or more △. adhesion force 0'5kN/m or more, lower than 〇8kN/m X: adhesion less than 0.5kN/m 4) surface roughness (rz) of metal tungsten is based on JIS B 〇 65 I was measured using a high-sensitivity surface spreader (p_15, manufactured by KLA_Tencor Co., Ltd.) under the conditions of a measurement speed of 0.02 mm/sec and a radius of curvature of 2 μm. 5) The soldering heat of the flexible laminate is immersed in a solder bath of a predetermined temperature for 10 seconds, and the highest temperature is regarded as the solder heat-resistant temperature at a temperature at which metal box peeling or resin expansion does not occur. Description of the code in the embodiment. DMAc : Ν,:Ν'-dimethylacetamide PMDA: pyromellitic acid two-needle BPDA: 3,3',4,4,biphenyltetracarboxylic dianhydride DSDA: diphenylsulfonyl-3, 4,3·,4'-tetracarboxylic acid dianhydride BTDA: benzophenone-3,4,3,,4'·tetracarboxylic dianhydride ΒΑΡΡ : 2,2-bis[4-(4-amino group Phenoxy)phenyl]propane 3)7)92 1344804 BAPB: 4,4'-bis(4-aminophenoxy)biphenylbutene PE-Q: 1,4-bis(4-amino phenyl) Base) stupid TPE_H'· 1,3_bis(4.aminophenoxy) stupid-m-TB: 2,2'-dimercapto-4,4'-diaminobiphenyl synthesis example to 3 BAPP and BAPB were supplied to DMAc and dissolved, and then PMDA was supplied, and at room temperature (d) for about 3 hours, a polyimine precursor resin solution composed of the components of the composition was prepared. Further, in all the synthesis examples, the ratio of the tetracarboxylic dianhydride component to the diamine component was set to be about 100 mol% stoichiometric. Further, the number of columns of the resin raw material composition in Table i means the molar ratio. The obtained polyimine precursor resin solution is coated on a copper foil, and the surface of the ruthenium resin layer is dried to a point of no suffocation at /jnL of 14 0 C or less, and then at 50 to 360 In the temperature range of °C, the temperature is heated in several stages, and the polyimide is imidized to form a polytheneimine film of thickness 25#m. The film is deposited at 35〇〇c. Elastic modulus, glass transition temperature (Tg), and coefficient of linear expansion. The results are shown in Table 1. Synthesis Examples 4 and 5 BAPP and ΤΡΕ-Q were supplied to DMAc and dissolved, and then PMDA was supplied, and stirred at room temperature for about 3 hours to prepare a polyimine precursor composed of the components shown in the table. Resin solution. This polyimide precursor resin solution was treated in the same manner as in Synthesis Example 1 to form a polyimide film, and its physical properties were evaluated. The results are shown in the table. 317) 92 19 1344804 Synthesis Example 6, 7 BAPP and TPE-R were supplied to DMAc and dissolved, and then PMDA was stirred for about 3 hours at room temperature to prepare a composition of the composition. Imine precursor resin solution. This polyamidene precursor resin solution was treated in the same manner as in the synthesis example, and a polyimide film was evaluated and its physical properties were evaluated. The results are shown in the table. ^ Synthesis Example 8
將BAPP供I給DMAc巾並溶解,接著再依序供應 PMDA、DSDA,於室溫中攪拌約3小時,便調製得在表】 所示組成成分所構成的聚醯亞胺前驅物樹脂溶液。τ此聚醯 亞胺前驅物樹脂溶液依合成例丨相同的方法進行严理 形成聚酿亞胺4膜,並評估其物性。結果如表1所示 合成例9 '、 將BAPF供應給DMAc中並溶解,接著再依序供應 PMDA、BTDA,於室溫中擾拌約3小時,便調製得在们 #所示組成成分所構成的聚醯亞胺前驅物樹脂溶液。此聚醯 亞胺前驅物樹脂溶液依合成例]相同的方法進行處理,而 形成聚醯亞胺薄膜,並評估其物性。結果如表1所示。 合成例10 ''BAPP was supplied to the DMAc towel and dissolved, and then PMDA and DSDA were sequentially supplied, and stirred at room temperature for about 3 hours to prepare a polyimine precursor resin solution composed of the components shown in the table. The rhodium imine precursor resin solution was subjected to the same method as in the synthesis example to form a polyimide II film, and its physical properties were evaluated. The results are shown in Synthesis Example 9' shown in Table 1, BAPF was supplied to DMAc and dissolved, and then PMDA and BTDA were sequentially supplied, and the mixture was stirred at room temperature for about 3 hours to prepare the composition shown in ##. A polyimine precursor resin solution is formed. This polyimine precursor resin solution was treated in the same manner as in the synthesis example to form a polyimide film, and its physical properties were evaluated. The results are shown in Table 1. Synthesis Example 10 ''
將BAPF供應給DMAc中並溶解,接著再供應歷A 於室溫中攪拌約3小時,便調製得在表】所示組成成分所 構成的聚❹胺前‘_難毅。此㈣亞胺前驅物樹脂 溶液依合成例!相同的方法進行處理,而形成聚醒亞胺薄 膜’並評估其物性。結果如表】所示。 317192 20 1344804 液。此聚醯亞胺前驅物樹脂溶液依合成例1相同的方法進 行處理’而形成聚醯亞胺薄膜,經測定線膨脹係數,結果 為 2.5ppm。 (實施例1) 在厚度12" m、表面粗糙度RZ為0.7# m的銅结上, 將合成例1所調製得聚醯亞胺前驅物樹脂溶液,依硬化後 的厚度為6从m之方式進行塗佈,並在低於j 4〇。匸的溫度中 進行5分鐘乾燥。於此上面,將合成例12所調製之聚=亞 胺前驅物樹脂溶液,依硬化後的厚度為29以m之方式進行 ^佈,並於低於nor的溫度中進行15分鐘乾燥。更於= 等2層的聚醯亞胺前驅物樹脂層上,將合成例1所調整的 小亞私·如驅物樹脂溶液,依硬化後的厚度為6 #⑴之 式進行塗佈,並於低於14〇t:的溫度中進行5分鐘乾燥方 在150至36(rc的溫度範圍中分開數階段,階段性的昇溫 加熱15分鐘,可製得在絕緣樹脂層單面上具有鋼强;= >性積層板。 ^ 對所獲得可撓性積層板的銅箔利用蝕刻處理,加工 所定電路。針對此可撓性積層板,評估與銅㈣的黏著性.、、 且評估銲錫耐熱性,結果顯示出與銅搭間的黏著性 〇.8kN/m以上,銲錫耐熱溫度達4〇〇ΐ以上的 評估結果如表2所示。 果。 實施例2至7 在實施例I中,將形成第】層及第3層之高彈性樹月匕 層的聚醯亞胺前驅物樹脂層種類,改變為合成例2至7中曰 317192 22 1344804 。針對此可撓性積 箔間的黏著性、銲The BAPF is supplied to the DMAc and dissolved, and then the supply of the A is stirred at room temperature for about 3 hours to prepare the polyamine which is composed of the components shown in the table. This (iv) imine precursor resin solution is based on synthesis! The same method was carried out to form a polyimide film, and the physical properties were evaluated. The results are shown in the table. 317192 20 1344804 Liquid. This polyimine precursor resin solution was treated in the same manner as in Synthesis Example 1 to form a polyimide film having a linear expansion coefficient of 2.5 ppm. (Example 1) On a copper junction having a thickness of 12 " m and a surface roughness RZ of 0.7 #m, the polyimine precursor resin solution prepared in Synthesis Example 1 was cured to a thickness of 6 m from m. The method is applied and is below 4 〇. Dry at 5 minutes in the temperature of the crucible. Herein, the poly-imine precursor resin solution prepared in Synthesis Example 12 was subjected to a thickness of 29 m after hardening, and dried at a temperature lower than norne for 15 minutes. Further, the small sub-private/resin resin solution adjusted in Synthesis Example 1 was coated on the polyimine precursor resin layer of the second layer, and the thickness after hardening was 6 #(1), and Drying at a temperature lower than 14 〇t: for 5 minutes, in a temperature range of 150 to 36 (the temperature range of rc is separated, and the temperature is heated for 15 minutes in a stepwise manner to obtain a steel strength on one side of the insulating resin layer. ;= > Slabs. ^ The copper foil of the obtained flexible laminate is etched to process the specified circuit. For this flexible laminate, the adhesion to copper (4) is evaluated, and the solder heat resistance is evaluated. The results show that the adhesion between the copper and the copper is 8 kN/m or more, and the evaluation results of the solder heat resistance temperature of 4 〇〇ΐ or more are shown in Table 2. In the example I, The type of the polyimine precursor resin layer forming the high elastic tree layer of the first layer and the third layer was changed to 曰317192 22 1344804 in Synthesis Examples 2 to 7. For the adhesion between the flexible foils Sex, welding
所製得的樹脂層’並製作可挽性積層板 層板的高彈性樹脂層面,進行評估與鋼 錫耐熱性。評估結果如表2所示。 比較例1至4 在實施例1中,將形成第1層及 層的聚醯亞胺前驅物樹脂層義,改變為::?早性钿脂 中所製得的樹脂層,並製作可撓性至:1 積層板將第】層樹脂當作評估面,進行^對此7撓佳 著性、銲錫耐熱性。評估結果如表2^間的點 (表 2) τ 第1層及第3層的聚醯亞胺 前驅物樹脂層種類 ^------ 與銅箔間的黏著性 鲜錫对熱溫度 (0〇 實施例I 合成例I '--- 〇 $400 實施例2 合成例2 ^—____ 〇 $400 實施例3 合成例3 —--- 〇 ^400 實施例4 合成例4 ~__ 〇 $400 實施例5 合成例5 -~~~~-_ 〇 2400 貫施例6 合成例6 ---_ 〇 ^400 實施例7 合成例7 --—~~~— 〇 ^400 比較例1 合成例8 ' —______ 〇 370 比較例2 合成例9 --H △ 360 比較例3 合成例】0 〜〜~~ 〇 390 比較例<4 合成例Π ^400 317192 23The obtained resin layer' was made into a highly elastic resin layer of a pliable laminated ply, and evaluated for heat resistance to steel tin. The evaluation results are shown in Table 2. Comparative Examples 1 to 4 In Example 1, the polyimine precursor resin forming the first layer and the layer was layered and changed to: ? The resin layer obtained in the early blush was made flexible to: 1 The laminated layer was used as the evaluation surface of the resin, and the soldering heat resistance was improved. The evaluation results are as shown in Table 2 (Table 2) τ The first and third layers of polyimine precursor resin layer type ^------ Adhesive bright tin between copper foil and hot temperature (0) Example I Synthesis Example I '---〇$400 Example 2 Synthesis Example 2^-____ 〇$400 Example 3 Synthesis Example 3 —--- 〇^400 Example 4 Synthesis Example 4 ~__ 〇$400 Implementation Example 5 Synthesis Example 5 -~~~~-_ 〇2400 Example 6 Synthesis Example 6 --- 〇 ^ 400 Example 7 Synthesis Example 7 ---~~~- 〇^400 Comparative Example 1 Synthesis Example 8 '-______ 〇 370 Comparative Example 2 Synthesis Example 9 - H △ 360 Comparative Example 3 Synthesis Example 0 to ~~~ 〇390 Comparative Example <4 Synthesis Example Π ^400 317192 23
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KR100926884B1 (en) * | 2006-04-27 | 2009-11-16 | 에스케이에너지 주식회사 | Flexible Metal Foil Laminate |
JP4777206B2 (en) * | 2006-09-29 | 2011-09-21 | 新日鐵化学株式会社 | Method for producing flexible copper-clad laminate |
JP4823953B2 (en) * | 2007-03-27 | 2011-11-24 | 新日鐵化学株式会社 | Method for producing flexible laminate |
CN101754856A (en) * | 2007-08-03 | 2010-06-23 | Kaneka株式会社 | Multilayer polyimide film, laminate and metal-clad laminate |
CN101724266B (en) * | 2008-10-20 | 2012-07-04 | 比亚迪股份有限公司 | Polyimide material, preparation method thereof, metal laminated plate containing same and preparation method thereof |
KR20100048474A (en) * | 2008-10-31 | 2010-05-11 | 에스케이에너지 주식회사 | Flexible metal-clad laminate and a method of manufacturing the same |
JP5615253B2 (en) | 2010-12-20 | 2014-10-29 | エスケー イノベーション シーオー., エルティーディー. | Method for producing thick film polyimide flexible metal laminate |
KR101514221B1 (en) * | 2011-12-07 | 2015-04-23 | 에스케이이노베이션 주식회사 | manufacturing method of multi layer polyimide flexible metal-clad laminate |
JP2013131423A (en) * | 2011-12-22 | 2013-07-04 | Hitachi Cable Ltd | Electrically insulated electric wire and coil |
KR101416782B1 (en) * | 2012-04-24 | 2014-07-08 | 에스케이이노베이션 주식회사 | Flexilbe Metal Clad Laminate |
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