TWI382997B - Thermosetting resin composition containing modified polyimide resin - Google Patents

Description

包含改質聚醯亞胺樹脂之熱固性樹脂組成物Thermosetting resin composition containing modified polyimine resin

本發明係關於適用於可撓性電路板的熱固性樹脂組成物。本發明也關於可撓性電路板、膠黏劑膜、及用於使用該熱固性樹脂組成物製作的可撓性電路板之膜。本發明進一步係關於由使用熱固性樹脂組成物，膠黏劑膜或用於可撓性電路板的膜所製作的可撓性電路板及其類似者。The present invention relates to a thermosetting resin composition suitable for a flexible circuit board. The present invention also relates to a flexible circuit board, an adhesive film, and a film for a flexible circuit board produced using the thermosetting resin composition. The present invention is further directed to a flexible circuit board made of a thermosetting resin composition, an adhesive film or a film for a flexible circuit board, and the like.

近年來愈來愈需要較薄的輕量的，具有高填充密度的半導體零件。在滿足此需求的努力之中，已注意到使用可撓性電路板作為半導體零件的基材板。相較於剛硬電路板，可撓性電路板可具有較小的厚度及較輕重量，且因為其撓曲性及變形能力的特徵，其可撓曲且可填充。如此，可撓性電路板有利於高密度IC封裝及模組微型化，且已使用於TCP(捲帶式封裝(Tape Carrier Package))、COF(軟性膜上晶片(Chip On Flexible Film))及其類似者，而使其已實質上用於各種媒體裝置的微型化上。In recent years, there has been a growing need for thinner, lightweight semiconductor parts with high packing densities. In an effort to meet this demand, it has been noted that a flexible circuit board is used as a substrate board for semiconductor parts. A flexible circuit board can have a smaller thickness and a lighter weight than a rigid circuit board, and is flexible and can be filled because of its flexibility and deformability. In this way, the flexible circuit board is advantageous for high-density IC packaging and module miniaturization, and has been used in TCP (Tape Carrier Package), COF (Chip On Flexible Film), and It is similar, and it has been used substantially for the miniaturization of various media devices.

可撓性電路板一般係由形成三層膜而製作，其係由聚醯亞胺膜、銅箔、及膠黏劑組成，或由二層膜製作，其係由聚醯亞胺膜與導體層組成，隨後依據減去方法將導體層蝕刻以形成電路。雖然可使用相對低成本製作的三層膜已更通常使用作為膜，二層膜在用於具有高密度接線電路板得到普遍性，因為膠黏劑具有耐熱性及電氣絕緣的缺點。A flexible circuit board is generally made by forming a three-layer film composed of a polyimide film, a copper foil, and an adhesive, or a two-layer film made of a polyimide film and a conductor. The layer composition is then etched to form an electrical circuit in accordance with the subtractive method. Although a three-layer film which can be produced at a relatively low cost has been more commonly used as a film, a two-layer film is generally used for a circuit board having a high density because the adhesive has the disadvantages of heat resistance and electrical insulation.

二層膜分類為三種型態，即濺射型、澆鑄型、及層合型，依據製作方法而命名。澆鑄型膜的製作係將聚醯胺酸清漆塗覆在輾軋或電沈積的銅箔上且將其加熱亞胺酯化。層合型膜的製作係將銅箔與具有熱塑性聚醯亞胺的聚醯亞胺膜黏合(例如參見JP-A-4-33847及JP-A-4-33848)。濺射型膜的製作係將經由濺射而在聚醯亞胺膜上形成薄的導體層，隨後經由將濺射層作電鍍而增厚此導體層(例如參見JP-A-2-98994)。The two-layer film is classified into three types, namely, a sputtering type, a casting type, and a laminated type, and is named according to the production method. The cast film is produced by coating a polyamic acid varnish on a rolled or electrodeposited copper foil and heating it to imide esterification. The laminated film is produced by bonding a copper foil to a polyimide film having a thermoplastic polyimide. (For example, see JP-A-4-33847 and JP-A-4-33848). The sputtering type film is formed by forming a thin conductor layer on the polyimide film via sputtering, and then thickening the conductor layer by electroplating the sputtering layer (for example, see JP-A-2-98994) .

當使用銅箔形成導體層，一般經由減去方法進行電路形成。在此狀況下，重要者在降低導體層之厚度以形成細微傾斜接線。然而，困難者在於在製作步驟中使用超薄銅箔的操作，例如厚度少於12μm，在三層膜、澆鑄型二層膜、及使用銅箔的層合型二層膜的製作中。為了嘗試克服銅箔操作問題，已進行使用具有可剝離支撐膜超薄銅箔的方法，使用厚銅箔且隨後經由半蝕刻降低導體層厚度而製備三或二層膜方法，或其類似者。然而，此類方法需高成本且並非總是較佳。When a conductor layer is formed using a copper foil, circuit formation is generally performed via a subtractive method. Under this circumstance, it is important to reduce the thickness of the conductor layer to form a finely slanted wiring. However, it is difficult to use an ultra-thin copper foil in the production step, for example, a thickness of less than 12 μm, in the production of a three-layer film, a cast two-layer film, and a laminated two-layer film using copper foil. In an attempt to overcome the copper foil handling problem, a three- or two-layer film method, or the like, has been carried out using a method having a peelable supporting film ultra-thin copper foil using a thick copper foil and then reducing the thickness of the conductor layer by half etching. However, such methods require high cost and are not always preferred.

經由電鍍而製備濺射型二層膜適用於形成細微傾斜接線，因為可相對地容易地形成薄的導體層。然而，濺射方法須要昂貴及精密之真空裝置，且因此，此類膜不利於成本及產率。The preparation of a sputtering type two-layer film by electroplating is suitable for forming a finely inclined wiring because a thin conductor layer can be formed relatively easily. However, the sputtering method requires an expensive and sophisticated vacuum device, and therefore, such a film is disadvantageous in cost and productivity.

同時，絕緣層化學粗糙且經由無電電鍍及電鍍在其上形成導體層之方法已廣泛地使用於剛硬電路板的製作。此方法可達成高產率，且當此方法可用絕緣材料，如聚醯亞胺，使用於可撓性電路板，更可輕易地製作具有細微傾斜接線的可撓性電路板。At the same time, the method in which the insulating layer is chemically rough and the conductor layer is formed thereon by electroless plating and electroplating has been widely used in the fabrication of rigid boards. This method can achieve high yields, and when this method can be applied to a flexible circuit board using an insulating material such as polyimide, it is easier to fabricate a flexible circuit board having finely inclined wiring.

在製作雙面或多層化可撓性電路板中，形成導孔以達成介於各層之間的傳導。為達此目的，已廣泛地用雷射形成導孔。然而，當導體層引入銅箔，對應於部分為雷射加工的部份導體層必須預先經由蝕刻移除，從而需要複雜方法。當可經由無電電鍍及電鍍形成導體層，經由在雷射加工之後形成導體層可簡化製作步驟。In making a double-sided or multi-layered flexible circuit board, via holes are formed to achieve conduction between the layers. To this end, guide holes have been widely formed using lasers. However, when the conductor layer is introduced into the copper foil, a portion of the conductor layer corresponding to the partial laser processing must be removed by etching in advance, so that a complicated method is required. When the conductor layer can be formed by electroless plating and electroplating, the fabrication step can be simplified by forming a conductor layer after laser processing.

然而，依據慣常用於可撓性電路板的絕緣材料如聚醯亞胺，經由於化學粗糙之後在絕緣層電鍍會難以形成具有充分黏合強度的導體層，且也難於形成多層結構。因此，已有需要發展用於可撓性電路板之絕緣材料，於其上可輕易地執行經由電鍍形成具有卓越黏合強度的導體層。However, according to an insulating material conventionally used for a flexible circuit board such as polyimide, it is difficult to form a conductor layer having a sufficient adhesive strength by electroplating on the insulating layer after chemical roughening, and it is also difficult to form a multilayer structure. Therefore, there has been a need to develop an insulating material for a flexible circuit board on which a conductor layer having excellent adhesive strength can be easily formed by electroplating.

另一方面，具有彈性且可經由簡單方法鍍層的該材料，也可使用剛硬電路板而用於半導體零件。連接基材板與半導體可提供半導體零件。板與半導體具有大幅不同之熱膨脹係數，從而連接部分經常由加熱而受力，引起各種問題如不良的連接。如此，已有許多注意力在使用高可撓性的絕緣材料介於半導體與基材板之間而作為應力舒張材料。目前針對半導體零件使用的應力舒張材料包含矽橡膠為主的材料(參見JP－A－2000－336271)及多孔的氟樹脂為主的片材。然而，會難以在此類材料上經由於化學粗糙之後無電及電鍍形成具有充分的黏合強度導體層。On the other hand, the material which is elastic and can be plated by a simple method can also be used for a semiconductor component using a rigid circuit board. Connecting the substrate board to the semiconductor provides semiconductor components. The board and the semiconductor have greatly different coefficients of thermal expansion, so that the connecting portion is often stressed by heating, causing various problems such as poor connection. As such, much attention has been paid to the use of highly flexible insulating materials between the semiconductor and the substrate as a stress relaxation material. The stress relaxation materials currently used for semiconductor parts include ruthenium-based materials (see JP-A-2000-336271) and porous fluororesin-based sheets. However, it may be difficult to form a conductor layer having sufficient adhesion strength by electroless plating and electroplating on such materials.

JP－A－11－199669揭示一種具有聚丁二烯骨架的聚醯亞胺樹脂，且進一步揭示樹脂組成物之說明性實施例，其可經由結合具有聚丁二烯多元醇的聚醯亞胺樹脂與聚團聯異氰酸酯而製備，其可用作可撓性電路之外塗層材料。JP-A-11-199669 discloses a polyimide resin having a polybutadiene skeleton, and further discloses an illustrative embodiment of a resin composition which can be bonded via a polyimine having a polybutadiene polyol The resin is prepared by agglomerating the isocyanate, which can be used as a coating material other than a flexible circuit.

JP-A-11-246760揭示一種樹脂，可經由結合具有聚丁二烯骨架及聚矽氧烷骨架聚醯胺醯亞胺樹脂，與環氧樹脂而製備，且敘述該樹脂可適當地使用於電子零件之外塗層材料、液體密封膠、用於搪瓷電線的清漆、用於電氣絕緣的浸漬清漆、鑄造清漆、用於基質材料如雲母或玻璃布結合片的清漆、針對MCL層合板的清漆、用於摩擦材料的清漆、表面保護膜、抗焊層、膠黏劑層、在印刷板領域的層間絕緣膜、及其類似者、及電子零件如半導體元件。然而，可用作聚醯胺醯亞胺樹脂材料之聚矽氧烷樹脂一般含有具高揮發性的低分子矽氧烷成分。因此，該成分在乾燥及熱硬化之步驟中揮發，從而使印刷接線板及其類似者之表面呈髒的，經常造成各種缺陷如密封劑樹脂的膠黏失效，及其類似者。此外，因為將末端羧酸化的聚丁二烯化合物用作起始材料，需要在高溫下反應。如此，丁二烯骨架之氧化反應可能會引起分子內交聯，導致樹脂膠凝化之可能性。據此，需要更進一步控制反應。JP-A-11-246760 discloses a resin which can be prepared by combining a polybutadiene skeleton and a polyoxyalkylene skeleton polyamidoximine resin with an epoxy resin, and it is described that the resin can be suitably used. Coating materials other than electronic parts, liquid sealants, varnishes for enamel wires, impregnating varnishes for electrical insulation, casting varnishes, varnishes for matrix materials such as mica or glass cloth bonded sheets, varnishes for MCL laminates A varnish for a friction material, a surface protective film, a solder resist layer, an adhesive layer, an interlayer insulating film in the field of a printed board, and the like, and an electronic component such as a semiconductor element. However, the polyoxyalkylene resin which can be used as the material of the polyamidoximine resin generally contains a low molecular weight decane component having high volatility. Therefore, the component volatilizes in the drying and heat hardening steps, so that the surface of the printed wiring board and the like is dirty, often causing various defects such as adhesive failure of the sealant resin, and the like. Further, since a terminally carboxylated polybutadiene compound is used as a starting material, it is required to react at a high temperature. Thus, the oxidation reaction of the butadiene skeleton may cause intramolecular crosslinking, which may result in gelation of the resin. Accordingly, further control of the reaction is required.

JP-A-2003-292575揭示一種樹脂組成物，其製備可經由結合環氧樹脂與具有聚丁二烯骨架的聚醯亞胺樹脂，作為可用於提昇結構材料領域的熱固性樹脂組成物、印刷接線板之層間絕緣材料、耐熱性膠黏劑、半導體之絕緣材料、及其類似者。敘述於JP-A-2003-292575的聚醯亞胺樹脂在分子骨架中具有異氰尿酸酯環，從而提供一種分枝型結構。因此，具有許多交聯點的硬化材料會導致難以得到具有低彈性的硬化材料。此外，因為在聚醯亞胺中聚丁二烯結構之含量低，硬化材料的彈性模數傾向會高。如此，以撓曲性而言未令人滿意地。同時，如由實施例中可清楚看出，聚醯亞胺樹脂硬化材料的斷裂伸長量在15%或更低，從耐摺疊性而言也不充分。JP-A-2003-292575 discloses a resin composition which can be prepared by combining an epoxy resin and a polyimide resin having a polybutadiene skeleton as a thermosetting resin composition and a printed wiring which can be used in the field of structural materials for lifting. Interlayer insulating materials for boards, heat-resistant adhesives, insulating materials for semiconductors, and the like. The polyimine resin described in JP-A-2003-292575 has an isocyanurate ring in a molecular skeleton to provide a branched structure. Therefore, a hardened material having many crosslinking points may result in difficulty in obtaining a hardened material having low elasticity. Further, since the content of the polybutadiene structure in the polyimine is low, the elastic modulus of the hardened material tends to be high. As such, it is not satisfactory in terms of flexibility. Meanwhile, as is clear from the examples, the polyiminoimide resin hardening material has an elongation at break of 15% or less and is insufficient in terms of folding resistance.

如此，存在著不含上述缺點的適用於可撓性電路板熱固性樹脂組成物之需求。Thus, there is a need for a flexible circuit board thermosetting resin composition which does not have the above disadvantages.

據此，本發明之一項目的在提供新穎的熱固性樹脂組成物。Accordingly, one item of the present invention provides a novel thermosetting resin composition.

本發明另一項目的在提供新穎的熱固性樹脂組成物，其係用作絕緣材料而用於可撓性電路板及半導體裝置。Another object of the present invention is to provide a novel thermosetting resin composition for use as an insulating material for flexible circuit boards and semiconductor devices.

本發明另一項目的在提供新穎的熱固性樹脂組成物，其具有卓越的撓曲性及耐摺疊性。Another item of the present invention provides a novel thermosetting resin composition which has excellent flexibility and folding resistance.

本發明另一項目的在提供新穎的熱固性樹脂組成物，於其上可經由電鍍而容易地形成具有卓越的黏合強度的導體層。Another object of the present invention is to provide a novel thermosetting resin composition on which a conductor layer having excellent adhesive strength can be easily formed by electroplating.

於以下詳細的描述中將變得明顯的此類及其它目標，已由本案發明人達成，發現一種熱固性樹脂組成物，其中含有特別的改質線型聚醯亞胺樹脂，其係將末端二元羥化的聚丁二烯、二異氰酸酯化合物、及四酸二酐三種成分反應所得到，與一種特別的熱固性樹脂，具有卓越的撓曲性，機械強度及介電性質，且適用於形成可撓性電路板及其類似者的絕緣層。此外，本案發明人已發現此熱固性樹脂組成物可做熱硬化以形成硬化材料，於其上表面做電鍍可容易地形成具有卓越黏著性的導體層。Such and other objects which will become apparent in the following detailed description have been achieved by the inventors of the present invention, and have found a thermosetting resin composition containing a special modified linear polyimine resin which is end-to-end binary Hydroxylated polybutadiene, diisocyanate compound, and tetraacid dianhydride are obtained by reacting three components with a special thermosetting resin, which has excellent flexibility, mechanical strength and dielectric properties, and is suitable for forming flexible Insulation of a circuit board and the like. Further, the inventors of the present invention have found that the thermosetting resin composition can be thermally hardened to form a hardened material, and electroplating on the upper surface thereof can easily form a conductor layer having excellent adhesion.

據此，本發明提供以下各項：(1)一種熱固性樹脂組成物，其包含：(A)至少一種將末端二元羥化的聚丁二烯、二異氰酸酯化合物、及四酸酐反應所得到的改質線型聚醯亞胺樹脂；及(B)至少一種由下列各者所組成族群中選出的熱固性樹脂：環氧樹脂、雙順丁烯二醯亞胺樹脂、氰酸酯樹脂、雙烯丙基－奈二－醯亞胺(bis－allyl－nadi－imide)樹脂、乙烯基苄基醚樹脂、苯並噁嗪樹脂、雙順丁烯二醯亞胺與二胺之聚合物、及其混合物。Accordingly, the present invention provides the following: (1) A thermosetting resin composition comprising: (A) at least one of a polybutadiene, a diisocyanate compound, and a tetra-anhydride obtained by dihydroxylation of a terminal. a modified linear polyimine resin; and (B) at least one thermosetting resin selected from the group consisting of epoxy resin, bis-methyleneimine resin, cyanate resin, diallyl Bis-allyl-nadi-imide resin, vinyl benzyl ether resin, benzoxazine resin, polymer of bis-n-butylene diimide and diamine, and mixtures thereof .

(2)依據上述項目(1)的一種熱固性樹脂，其中改質線型聚醯亞胺樹脂(A)為一種改質線型聚醯亞胺樹脂，其係將末端二元羥化的聚丁二烯與二異氰酸酯化合物反應，其中所採用的相對量係使該二異氰酸酯化合物上異氰酸酯基團對該末端二元羥化的聚丁二烯上羥基基團的官能基團當量比例大於1，以製備聚丁二烯二異氰酸酯組成物，及經由將該聚丁二烯二異氰酸酯組成物與一種四酸二酐反應所得到。(2) A thermosetting resin according to the above item (1), wherein the modified linear polyimine resin (A) is a modified linear polyimine resin which is a terminally hydroxylated polybutadiene Reacting with a diisocyanate compound, wherein the relative amount is such that the isocyanate group on the diisocyanate compound has a functional group equivalent ratio of the hydroxyl group on the terminally hydroxylated polybutadiene to more than 1, to prepare a poly The butadiene diisocyanate composition is obtained by reacting the polybutadiene diisocyanate composition with a tetracarboxylic dianhydride.

(3)依據上述項目(1)的一種熱固性樹脂組成物，其中改質線型聚醯亞胺樹脂(A)為一種改質線型聚醯亞胺樹脂，其係將末端二元羥化的聚丁二烯與二異氰酸酯化合物反應，其中所採用的相對量係使該二異氰酸酯化合物上異氰酸酯基團對該末端二元羥化的聚丁二烯上羥基基團的的官能基團當量比例為1：1.5至1：2.5，以製備聚丁二烯二異氰酸酯組成物，及經由將該聚丁二烯二異氰酸酯組成物與一種四酸二酐反應所得到。(3) A thermosetting resin composition according to the above item (1), wherein the modified linear polyimine resin (A) is a modified linear polyimine resin which is a polybutylate which is terminally hydroxylated The diene is reacted with a diisocyanate compound in a relative amount such that the functional group equivalent ratio of the isocyanate group on the diisocyanate compound to the hydroxyl group on the polybutadiene which is hydroxylated to the terminal is 1: 1.5 to 1:2.5 to prepare a polybutadiene diisocyanate composition, and obtained by reacting the polybutadiene diisocyanate composition with a tetracarboxylic dianhydride.

(4)依據上述項目(1)的一種熱固性樹脂組成物，其中改質線型聚醯亞胺樹脂(A)為一種改質線型聚醯亞胺樹脂，其製作係將末端二元羥化的聚丁二烯與二異氰酸酯化合物反應，其中所採用的相對量係使該二異氰酸酯化合物上異氰酸酯基團對該末端二元羥化的聚丁二烯上羥基基團的的官能基團當量比例為1：1.5至1：2.5，以製備聚丁二烯二異氰酸酯組成物，及經由將該聚丁二烯二異氰酸酯組成物與一種四酸二酐反應反應，其中所採用的比例係允許起始材料二異氰酸酯化合物中異氰酸酯基團的官能基團當量X，起始材料末端二元羥化的聚丁二烯中羥基基團的官能基團當量W，及該四酸二酐中酸酐基團的官能基團當量Y，可滿足Y>X－W≧Y/5(W>0，X>0，Y>0)之關係。(4) A thermosetting resin composition according to the above item (1), wherein the modified linear polyimine resin (A) is a modified linear polyimine resin, which is produced by polymerizing a terminally hydroxylated polymer Butadiene is reacted with a diisocyanate compound in a relative amount such that the functional group equivalent ratio of the isocyanate group on the diisocyanate compound to the hydroxyl group on the terminally hydroxylated polybutadiene is 1 : 1.5 to 1:2.5 to prepare a polybutadiene diisocyanate composition, and reacting the polybutadiene diisocyanate composition with a tetraacid dianhydride, wherein the ratio used is a starting material The functional group equivalent X of the isocyanate group in the isocyanate compound, the functional group equivalent W of the hydroxyl group in the polybutadiene which is terminally hydroxylated at the end of the starting material, and the functional group of the anhydride group in the tetracarboxylic dianhydride The group equivalent Y can satisfy the relationship of Y>X-W≧Y/5 (W>0, X>0, Y>0).

(5)依據上述(1)至(4)項中任何一項的一種熱固性樹脂組成物，其中改質線型聚醯亞胺樹脂成分(A)為一種改質線型聚醯亞胺樹脂，其製作係進一步將額外的異氰酸酯化合物與依據上述(1)至(4)項中任何一項的改質線型聚醯亞胺樹脂反應，所採用的比例係允許起始材料二異氰酸酯化合物中異氰酸酯基團的官能基團當量X，起始材料末端二元羥化的聚丁二烯中羥基基團的官能基團當量W，四酸二酐中酸酐基團的官能基團當量Y，及新加入反應的異氰酸酯化合物中異氰酸酯基團的官能基團當量Z，滿足Y－(X－W)>Z≧0(W>0，X>0，Y>0，Z>0)之關係。(5) A thermosetting resin composition according to any one of the above items (1) to (4), wherein the modified linear polyimine resin component (A) is a modified linear polyimine resin, which is produced Further reacting the additional isocyanate compound with the modified linear polyimine resin according to any one of the above items (1) to (4) in a ratio allowing the isocyanate group in the starting material diisocyanate compound Functional group equivalent X, functional group equivalent W of the hydroxyl group in the polyhydroxylated polybutadiene at the end of the starting material, functional group equivalent Y of the anhydride group in the tetraacid dianhydride, and newly added reaction The functional group equivalent Z of the isocyanate group in the isocyanate compound satisfies the relationship of Y-(X-W)>Z≧0 (W>0, X>0, Y>0, Z>0).

(6)一種熱固性樹脂組成物，其包含：(A)一種改質線型聚醯亞胺樹脂，其分子中具有由下式(1－a)代表的聚丁二烯結構及由下式(1－b)代表的聚醯亞胺結構： (6) A thermosetting resin composition comprising: (A) a modified linear polyimine resin having a polybutadiene structure represented by the following formula (1-a) and having the following formula (1) -b) Represents the structure of polyimine:

其中R1代表經由從末端二元羥化的聚丁二烯上移除羥基基團所得到的殘基；R2代表經由從四酸二酐上移除酸酐基團所得到的殘基；及R3代表經由從二異氰酸酯化合物上移除異氰酸酯基團所得到的殘基，及(B)至少一種由下列各者所組成族群中選出的熱固性樹脂：環氧樹脂、雙順丁烯二醯亞胺樹脂、氰酸酯樹脂、雙烯丙基－奈二－醯亞胺樹脂、乙烯基苄基醚樹脂、苯並噁嗪樹脂、雙順丁烯二醯亞胺與二胺之聚合物、及其混合物。Wherein R1 represents a residue obtained by removing a hydroxyl group from a terminally hydroxylated polybutadiene; R2 represents a residue obtained by removing an acid anhydride group from a tetracarboxylic dianhydride; and R3 represents a residue obtained by removing an isocyanate group from a diisocyanate compound, and (B) at least one thermosetting resin selected from the group consisting of an epoxy resin, a bis-m-butylene iminoimide resin, A cyanate resin, a bisallyl-naphtho-imine resin, a vinyl benzyl ether resin, a benzoxazine resin, a polymer of a bis-sandimide and a diamine, and a mixture thereof.

(7)一種依據上述(1)至(6)中任何一項的熱固性樹脂組成物，其中在成分(A)中的改質線型聚醯亞胺樹脂中聚丁二烯結構的含量為45重量%或更多。(7) A thermosetting resin composition according to any one of (1) to (6) above, wherein the content of the polybutadiene structure in the modified linear polyimine resin in the component (A) is 45 by weight. %Or more.

(8)一種依據上述(1)至(6)中任何一項的熱固性樹脂組成物，其中在成分(A)中的改質線型聚醯亞胺樹脂中聚丁二烯結構的含量為60重量%或更多。(8) A thermosetting resin composition according to any one of (1) to (6) above, wherein the content of the polybutadiene structure in the modified linear polyimine resin in the component (A) is 60% by weight. %Or more.

(9)一種依據上述(1)至(8)中任何一項的熱固性樹脂組成物，其中R1代表從數目平均分子量在800至10000之末端二元羥化的聚丁二烯上移除羥基基團所得到的殘基。。(9) A thermosetting resin composition according to any one of (1) to (8) above, wherein R1 represents a hydroxyl group removed from a polybutadiene which is dihydroxylated at a terminal number average molecular weight of 800 to 10,000. The residue obtained by the group. .

(10)一種依據上述(1)至(9)中任何一項的熱固性樹脂組成物，其中熱固性樹脂組成物之硬化材料的彈性模數為100 MPa或更低，且斷裂伸長量為20%或更多。(10) The thermosetting resin composition according to any one of (1) to (9) above, wherein the hardening material of the thermosetting resin composition has a modulus of elasticity of 100 MPa or less and an elongation at break of 20% or More.

(11)一種依據上述(1)至(10)中任何一項的熱固性樹脂組成物，其中成分(A)與成分(B)的組成比例為100：1至1：1重量比，且在熱固性樹脂組成物中成分(A)與成分(B)的總含量為70重量%或更多。(11) A thermosetting resin composition according to any one of (1) to (10) above, wherein the composition ratio of the component (A) to the component (B) is from 100:1 to 1:1 by weight, and is thermosetting. The total content of the component (A) and the component (B) in the resin composition is 70% by weight or more.

(12)一種依據上述(1)至(11)中任何一項的熱固性樹脂組成物，其進一步包含填料。(12) A thermosetting resin composition according to any one of the above (1) to (11), further comprising a filler.

(13)一種依據上述(1)至(12)中任何一項的熱固性樹脂組成物，其中成分(B)的熱固性樹脂為環氧樹脂。(13) A thermosetting resin composition according to any one of (1) to (12) above, wherein the thermosetting resin of the component (B) is an epoxy resin.

(14)一種依據上述項目(13)的熱固性樹脂組成物，其進一步包含環氧硬化劑(14) A thermosetting resin composition according to the above item (13), which further comprises an epoxy hardener

(15)一種膠黏劑膜，其包含在支撐膜(B層)上形成內含依據上述(1)至(14)項中任何一項的熱固性樹脂組成物的熱固性樹脂組成物層(A層)。(15) An adhesive film comprising a thermosetting resin composition layer (layer A) containing a thermosetting resin composition according to any one of the above items (1) to (14) on a support film (layer B) ).

(16)一種膠黏劑膜，其中包含在作離型處理的支撐膜(B層)的離型處理表面上，形成內含依據上述(1)至(14)項中任何一項的熱固性樹脂組成物的熱固性樹脂組成物層(A層)。(16) An adhesive film comprising a thermosetting resin containing any one of the above items (1) to (14), which is contained on a release-treated surface of a release-treated support film (layer B) A thermosetting resin composition layer (layer A) of the composition.

(17)一種可撓性電路板，其包含在依據上述項(1)至(14)中任何一項的熱固性樹脂組成物之硬化材料上形成電路。(17) A flexible circuit board comprising the circuit formed on the hardening material of the thermosetting resin composition according to any one of the above items (1) to (14).

(18)一種多層可撓性電路板，其製作方法包含以下步驟(1)至(9)：(1)使用依據上述項目(15)或(16)中的膠黏劑膜層合可撓性電路板的一面或兩面；(2)去除或不去除B層；(3)熱硬化A層以形成絕緣層；(4)去除或不去除B層，當未在步驟(b)中移除B層；(5)在可撓性電路板中形成孔；(6)去除B層，當未在步驟(2)與(4)中移除B層；(7)將絕緣層作表面處理；(8)經由在絕緣層上電鍍而形成導體層；及(9)在絕緣層上將導體層形成電路。(18) A multilayer flexible circuit board comprising the following steps (1) to (9): (1) laminating flexibility using an adhesive film according to the above item (15) or (16) One or both sides of the board; (2) removing or removing the B layer; (3) thermally hardening the A layer to form the insulating layer; (4) removing or not removing the B layer, when the step B is not removed in step (b) a layer; (5) forming a hole in the flexible circuit board; (6) removing the B layer, when the layer B is not removed in steps (2) and (4); (7) treating the insulating layer as a surface; 8) forming a conductor layer by electroplating on the insulating layer; and (9) forming the conductor layer on the insulating layer to form an electric circuit.

(19)一種用於可撓性電路板之膜，其包含在耐熱性樹脂層(C層)上的依據上述(1)至(14)項中任何一項的熱固性樹脂組成物之硬化材料之絕緣層(A’層)。(19) A film for a flexible circuit board comprising a hardening material of a thermosetting resin composition according to any one of the above items (1) to (14) on a heat resistant resin layer (layer C) Insulation layer (A' layer).

(20)一種單面可撓性電路板，其製作係將依據上述項目(19)的用於可撓性電路板的膜之A’層作表面處理，經由在絕緣層上電鍍而形成導體層，且將導體層形成電路(21)一種用於可撓性電路板的膜，其包含依據上述(1)至(14)項中任何一項的熱固性樹脂組成物之硬化材料之絕緣層(A’層)，耐熱性樹脂層(C層)及銅箔(D層)，其中此膜具有如下順序的層化結構：A’層、C層、及D層。(20) A single-sided flexible circuit board produced by surface-treating a layer A' of a film for a flexible circuit board according to the above item (19), and forming a conductor layer by plating on the insulating layer And a conductor layer forming circuit (21), a film for a flexible circuit board, comprising the insulating layer of the hardening material of the thermosetting resin composition according to any one of the above items (1) to (14) (A) 'layer', a heat resistant resin layer (C layer) and a copper foil (D layer), wherein the film has a stratified structure in the following order: A' layer, C layer, and D layer.

(22)一種雙面可撓性電路板，其製作係在依據上述項目(21)之用於可撓性電路板的膜內孔形成，將作A'層作表面處理，經由在A’層之表面上電鍍而形成導體層，且將導體層與D層形成電路。(22) A double-sided flexible circuit board produced by forming a film inner hole for a flexible circuit board according to the above item (21), which is subjected to surface treatment of the A' layer via the A' layer The surface is plated to form a conductor layer, and the conductor layer and the D layer form an electrical circuit.

(23)一種用於可撓性電路板的膜，其包含依據上述(1)至(14)項中任何一項的熱固性樹脂組成物之硬化材料之絕緣層(A’層)與耐熱性樹脂層(C層)，其中此膜具有如下順序的層化結構：A’層、C層、及A’層。(23) A film for a flexible circuit board comprising the insulating layer (A' layer) of the hardening material of the thermosetting resin composition according to any one of the above items (1) to (14), and a heat resistant resin Layer (layer C), wherein the film has a stratified structure in the following order: A' layer, C layer, and A' layer.

(24)一種雙面可撓性電路板，其製作係在依據上述項目(23)之用於可撓性電路板的膜內形成孔，將作A'層作表面處理，經由在A’層之表面上電鍍而形成導體層，且將此導體層形成電路。(24) A double-sided flexible circuit board produced by forming a hole in a film for a flexible circuit board according to the above item (23), which is subjected to surface treatment by A' layer, via A' layer The surface is plated to form a conductor layer, and this conductor layer is formed into an electric circuit.

(25)一種內含半導體與基材板的半導體裝置，其係使用內含依據上述(1)至(14)項中任何一項的熱固性樹脂組成物之硬化材料黏合。(25) A semiconductor device comprising a semiconductor and a substrate, which is bonded using a hardening material containing the thermosetting resin composition according to any one of the above items (1) to (14).

本發明熱固性樹脂組成物之硬化材料具有卓越的撓曲性，機械強度及介電性質，且可容易地經由表面電鍍將在其上形成具有卓越黏著性的導體層。The hardening material of the thermosetting resin composition of the present invention has excellent flexibility, mechanical strength and dielectric properties, and can easily form a conductor layer having excellent adhesion thereon by surface plating.

較佳的具體實施例之詳細敘述DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENT

如下將詳細敘述本發明。The invention will be described in detail below.

本發明中，改質線型聚醯亞胺樹脂成分(A)為一種改質線型聚醯亞胺樹脂，其係將下列三種成分反應所得到：(a)末端二元羥化的聚丁二烯；(b)二異氰酸酯化合物；及(c)四酸二酐。In the present invention, the modified linear polyimine resin component (A) is a modified linear polyimine resin obtained by reacting the following three components: (a) terminally hydroxylated polybutadiene (b) a diisocyanate compound; and (c) a tetraacid dianhydride.

此改質線型聚醯亞胺樹脂可在分子中含有由下式(1－a)代表的聚丁二烯結構與由式(1－b)代表的聚醯亞胺結構兩者。在改質線型聚醯亞胺樹脂中聚丁二烯結構之含量宜在45重量%或更多，且更佳在60重量%或更多。當在改質線型聚醯亞胺樹脂中聚丁二烯結構之含量少於45重量%，本發明熱固性樹脂組成物之硬化材料傾向有不良的撓曲性。在改質線型聚醯亞胺樹脂中聚丁二烯結構部分之含量(重量%)可定義為末端二元羥化的聚丁二烯(a)對上述使用於反應中(a)至(c)三種成分之總重的重量比。This modified linear polyimine resin may contain both a polybutadiene structure represented by the following formula (1-a) and a polyamidene structure represented by the formula (1-b) in the molecule. The content of the polybutadiene structure in the modified linear polyimine resin is preferably 45% by weight or more, and more preferably 60% by weight or more. When the content of the polybutadiene structure in the modified linear polyimide resin is less than 45% by weight, the hardened material of the thermosetting resin composition of the present invention tends to have poor flexibility. The content (% by weight) of the polybutadiene moiety in the modified linear polyimide resin can be defined as terminally hydroxylated polybutadiene (a) for use in the above reactions (a) to (c) The weight ratio of the total weight of the three components.

在以上式中，R1代表經由從末端二元羥化的聚丁二烯上移除羥基基團所得到的殘基；R2代表經由從四酸二酐上移除酸酐基團所得到的殘基；及R3代表經由從二異氰酸酯化合物上移除異氰酸酯基團所得到的殘基。末端二元羥化的聚丁二烯之數目平均分子量宜在800至10000。在聚丁二烯之結構式(1－a)中，R1宜代表提供經由從數目平均分子量在800至10000的末端二元羥化的聚丁二烯中去除羥基基團所得到的殘基。當末端二元羥化的聚丁二烯之數目平均分子量為800或更低，改質聚醯亞胺樹脂傾向有不良的撓曲性。當數目平均分子量為10000或更多，改質聚醯亞胺樹脂傾向有不良的與熱固性樹脂之相容性且傾向有不良的耐熱性。在本發明中，數目平均分子量可經由凝膠滲透層析(GPC)方法測量，使用聚苯乙烯標準。在GPC方法中，尤其是，測量數目平均分子量係經由使用測量裝置LC－9A/RID－6A，由Shimadzu Corporation製作，管柱為Shodex K－800P/K－804L/K－804L，由Showa Denko K.K.製作，且動相為氯仿，管柱溫度40℃，且經使用聚苯乙烯標準的校正曲線而計算。In the above formula, R1 represents a residue obtained by removing a hydroxyl group from a terminally hydroxylated polybutadiene; R2 represents a residue obtained by removing an acid anhydride group from a tetracarboxylic dianhydride. And R3 represent a residue obtained by removing an isocyanate group from a diisocyanate compound. The number of terminally hydroxylated polybutadienes is preferably from 800 to 10,000. In the structural formula (1-a) of polybutadiene, R1 preferably represents a residue obtained by removing a hydroxyl group from a polybutadiene which is dihydroxylated at a terminal having a number average molecular weight of 800 to 10,000. When the number of terminally hydroxylated polybutadienes has an average molecular weight of 800 or less, the modified polyimine resin tends to have poor flexibility. When the number average molecular weight is 10,000 or more, the modified polyimine resin tends to have poor compatibility with a thermosetting resin and tends to have poor heat resistance. In the present invention, the number average molecular weight can be measured by a gel permeation chromatography (GPC) method using a polystyrene standard. In the GPC method, in particular, the measurement of the number average molecular weight is carried out by Shimadzu Corporation via the use of a measuring device LC-9A/RID-6A, the column is Shodex K-800P/K-804L/K-804L, by Showa Denko KK Manufactured, and the phase was chloroform, the column temperature was 40 ° C, and was calculated using a calibration curve using polystyrene standards.

在改質線型聚醯亞胺樹脂中，每一個分子中存在的聚丁二烯結構(1－a)之數目一般為1至10,000，且宜在1至100。每一個分子中存在的聚醯亞胺結構(1－b)之數目一般為1至100，且宜在1至10。In the modified linear polyimine resin, the number of polybutadiene structures (1-a) present in each molecule is generally from 1 to 10,000, and preferably from 1 to 100. The number of polyimine structures (1-b) present in each molecule is generally from 1 to 100, and preferably from 1 to 10.

改質線型聚醯亞胺樹脂之數目平均分子量未特別地限制，但一般可在5000至200000，且宜在10000至100000。The number average molecular weight of the modified linear polyimine resin is not particularly limited, but may generally be from 5,000 to 200,000, and preferably from 10,000 to 100,000.

改質線型聚醯亞胺樹脂之起始材料的成分(a)至(c)，可分別地由下式(a)至(c)代表。The components (a) to (c) of the starting material of the modified linear polyimine resin can be represented by the following formulas (a) to (c), respectively.

在式中的各個符號具有那些如上定義的相同意義。因改質線型聚醯亞胺樹脂單獨由上述二官能單體所合成，提供具有線型結構的改質聚醯亞胺樹脂。換言之，依據本發明的一項特徵，改質線型聚醯亞胺樹脂意指使用二官能單體作為起始材料的具有線型結構之改質聚醯亞胺樹脂。如此，在本發明中改質聚醯亞胺之線型結構可提供一種具有更卓越撓曲性熱的固性樹脂組成物。Each symbol in the formula has the same meaning as those defined above. Since the modified linear polyimine resin is synthesized from the above-mentioned difunctional monomer alone, a modified polyimine resin having a linear structure is provided. In other words, according to a feature of the present invention, the modified linear polyimine resin means a modified polyimine resin having a linear structure using a difunctional monomer as a starting material. Thus, the linear structure of the modified polyimine in the present invention can provide a curable resin composition having more excellent heat of flexibility.

宜用以下步驟以有效地得到在本發明中的改質線型聚醯亞胺樹脂首先，將聚丁二烯的成分(a)與二異氰酸酯化合物的成分(b)反應，使二異氰酸酯化合物中異氰酸酯基團對聚丁二烯中羥基基團的官能基團當量比例為大於1，以得到內含聚丁二烯二異氰酸酯的組成物。聚丁二烯二異氰酸酯可由下式(a－b)代表。The following procedure is preferably employed to effectively obtain the modified linear polyimine resin in the present invention. First, the component (a) of the polybutadiene is reacted with the component (b) of the diisocyanate compound to form an isocyanate in the diisocyanate compound. The functional group equivalent ratio of the group to the hydroxyl group in the polybutadiene is greater than 1, to obtain a composition containing the polybutadiene diisocyanate. The polybutadiene diisocyanate can be represented by the following formula (a-b).

在式(a－b)中，R1代表經由從末端二元羥化的聚丁二烯中去移除羥基基團所提供的殘基，R3代表經由從二異氰酸酯化合物中去移除異氰酸酯基團所提供的殘基，且n代表1至100之整數(1≦n≦100)。n宜代表1至10之整數(1≦n≦10)。在由式(a－b)代表的聚丁二烯異氰酸酯中，R1宜代表經由從數目平均分子量在800至10000之末端二元羥化的聚丁二烯中去移除羥基基團所提供的殘基。In the formula (a-b), R1 represents a residue provided by removing a hydroxyl group from a terminally hydroxylated polybutadiene, and R3 represents removal of an isocyanate group from a diisocyanate compound. The residue provided, and n represents an integer from 1 to 100 (1≦n≦100). n should preferably represent an integer from 1 to 10 (1≦n≦10). In the polybutadiene isocyanate represented by the formula (a-b), R1 is preferably represented by removal of a hydroxyl group from a polybutadiene which is dihydroxylated from a number average molecular weight of 800 to 10,000. Residues.

介於聚丁二烯與二異氰酸酯化合物之間的反應比例，宜使聚丁二烯中羥基基團對二異氰酸酯化合物中異氰酸酯基團的官能基團當量比例介於1：1.5至1：2.5之間。The ratio of the reaction between the polybutadiene and the diisocyanate compound is such that the ratio of the functional groups of the hydroxyl group in the polybutadiene to the isocyanate group in the diisocyanate compound is between 1:1.5 and 1:2.5. between.

然後，將聚丁二烯二異氰酸酯組成物與四酸二酐反應。四酸二酐的反應比例未特別地限制，但宜使在組成物中殘存的異氰酸酯基團降至最低。當X代表起始材料二異氰酸酯化合物中異氰酸酯基團的官能基團當量，W代表起始材料中末端二元羥化的聚丁二烯之羥基基團的官能基團當量，且Y代表四酸二酐中酸酐基團的官能基團當量，其較佳滿足Y>X－W≧Y/5(W>0，X>0，Y>0)之關係。The polybutadiene diisocyanate composition is then reacted with tetraacid dianhydride. The reaction ratio of the tetraacid dianhydride is not particularly limited, but it is preferred to minimize the isocyanate groups remaining in the composition. When X represents the equivalent of the functional group of the isocyanate group in the starting material diisocyanate compound, W represents the functional group equivalent of the hydroxyl group of the terminally hydroxylated polybutadiene in the starting material, and Y represents the tetraacid The functional group equivalent of the anhydride group in the dianhydride preferably satisfies the relationship of Y>X-W≧Y/5 (W>0, X>0, Y>0).

如此得到的改質線型聚醯亞胺樹脂在分子中含有由式(1－a)代表的聚丁二烯結構及由式(1－b)代表的醯亞胺結構兩者，如上述者。使用於本發明中的改質線型聚醯亞胺樹脂宜包含具有由下式(a－b－c)代表結構作為主成分的改質線型聚醯亞胺。The modified linear polyimine resin thus obtained contains both a polybutadiene structure represented by the formula (1-a) and a quinone imine structure represented by the formula (1-b) in the molecule, as described above. The modified linear polyimine resin used in the present invention preferably contains a modified linear polyimine having a structure represented by the following formula (a-b-c) as a main component.

在式(a－b－c)中，R1代表經由從末端二元羥化的聚丁二烯中去移除羥基基團所提供的殘基，R2代表經由從四酸二酐中去除酸酐基團所提供的殘基，R3代表經由從二異氰酸酯化合物中去移除異氰酸酯基團所提供的殘基，且n與m各自代表1至100之整數(1≦n≦100)。各個n與m宜代表1至10之整數(1≦n≦10)。在由式(a－b－c)代表的聚丁二烯異氰酸酯中，R1宜代表經由從數目平均分子量在800至10000之末端二元羥化的聚丁二烯中去移除羥基基團所提供的殘基。In the formula (a-b-c), R1 represents a residue provided by removing a hydroxyl group from a terminally hydroxylated polybutadiene, and R2 represents removal of an acid anhydride group from a tetraacid dianhydride. The residue provided by the group, R3 represents a residue provided by removing the isocyanate group from the diisocyanate compound, and n and m each represent an integer of 1 to 100 (1≦n≦100). Each of n and m preferably represents an integer of 1 to 10 (1≦n≦10). In the polybutadiene isocyanate represented by the formula (a-b-c), R1 preferably represents removal of a hydroxyl group via polybutadiene which is dihydroxylated from a number average molecular weight of 800 to 10,000. The residue provided.

為了將在組成物中殘存的異氰酸酯基團降至最低，在反應中宜使異氰酸酯基團消失，經由FT－ER或其類似者而確定。如此得到改質聚醯亞胺樹脂之末端基團可由下式(1－c)或下式(1－d)代表。In order to minimize the isocyanate groups remaining in the composition, it is preferred to eliminate the isocyanate groups in the reaction, which is determined by FT-ER or the like. The terminal group of the thus obtained modified polyimine resin can be represented by the following formula (1-c) or the following formula (1-d).

在式(1－c)與(1－d)中的符號具有那些如上定義的相同意義。The symbols in the formulae (1-c) and (1-d) have the same meanings as defined above.

在改質線型聚醯亞胺樹脂組成物的製作中，內含改質線型聚醯亞胺樹脂的具有較高分子量的組成物，可將所得到的聚丁二烯二異氰酸酯組成物與四酸二酐反應，隨後進一步與額外的二異氰酸酯化合物反應。在此案例中，異氰酸酯化合物的反應比例未特別地限制。當X代表起始材料二異氰酸酯化合物中異氰酸酯基團的官能基團當量，W代表起始材料中末端二元羥化的聚丁二烯之羥基基團的官能基團當量，Y代表四酸二酐中酸酐基團的官能基團當量，且Z代表額外的異氰酸酯化合物中異氰酸酯基團的官能基團當量，其較佳滿足Y－(X－W)>Z≧0(W>0，X>0，Y>0，Z>0)之關係。In the preparation of the modified linear polyimine resin composition, a composition having a higher molecular weight containing a modified linear polyimine resin, and the obtained polybutadiene diisocyanate composition and tetraacid The dianhydride is reacted and subsequently further reacted with an additional diisocyanate compound. In this case, the reaction ratio of the isocyanate compound is not particularly limited. When X represents the equivalent of the functional group of the isocyanate group in the starting material diisocyanate compound, W represents the functional group equivalent of the hydroxyl group of the terminally hydroxylated polybutadiene in the starting material, and Y represents the tetraacid The functional group equivalent of the anhydride group in the anhydride, and Z represents the functional group equivalent of the isocyanate group in the additional isocyanate compound, which preferably satisfies Y-(X-W)>Z≧0 (W>0, X> 0, Y>0, Z>0) relationship.

使用於本發明中的改質聚醯亞胺樹脂包含二種化學結構單元：由上述式(1－a)代表的聚丁二烯結構與由上述式(1－b)代表的聚醯亞胺結構。為使樹脂組成物具有彈性，一般而言，將橡膠樹脂如聚丁二烯樹脂直接與樹脂組成物混合。然而，非極性橡膠樹脂在高度極性熱固性樹脂組成物中易引起相分離。特別地，當橡膠樹脂之含量高，會難以得到穩定的組成物。此外，許多內含橡膠樹脂的樹脂組成物顯示不充分的耐熱性。相反地，聚醯亞胺樹脂具有耐熱性與高極性，與熱固性樹脂組成物有相對卓越的相容性。因使用於本發明中的改質線型聚醯亞胺樹脂在分子中具有此聚醯亞胺結構及可提供撓曲性的聚丁二烯結構兩者，可提供具有卓越的撓曲性及耐熱性兩者特性之材料。此外，適合的與熱固性樹脂之相容性也可提供一種適用於形成穩定的熱固性樹脂組成物的材料。The modified polyimine resin used in the present invention contains two chemical structural units: a polybutadiene structure represented by the above formula (1-a) and a polyimide represented by the above formula (1-b) structure. In order to impart elasticity to the resin composition, in general, a rubber resin such as a polybutadiene resin is directly mixed with the resin composition. However, non-polar rubber resins are liable to cause phase separation in highly polar thermosetting resin compositions. In particular, when the content of the rubber resin is high, it is difficult to obtain a stable composition. Further, many resin compositions containing a rubber resin exhibit insufficient heat resistance. On the contrary, the polyimide resin has heat resistance and high polarity, and has relatively excellent compatibility with the thermosetting resin composition. Since the modified linear polyimine resin used in the present invention has both the polyimide structure and the polybutadiene structure which provides flexibility in the molecule, it can provide excellent flexibility and heat resistance. Material of both characteristics. In addition, suitable compatibility with the thermosetting resin can also provide a material suitable for forming a stable thermosetting resin composition.

在使用於本發明中的改質聚醯亞胺樹脂中，可能經由控制起始材料的反應比例而改變聚丁二烯結構與聚醯亞胺結構的組成物比例。高比例的聚丁二烯結構會使本發明熱固性樹脂組成物成為具有更卓越撓曲性的材料，而高比例的聚醯亞胺結構會造成具有更卓越耐熱性的材料。如上所述，當在改質線型聚醯亞胺樹脂中聚丁二烯結構之含量少於45重量%，改質線型聚醯亞胺樹脂傾向有不良的的撓曲性。因此，在須要撓曲性的用途中如可撓性電路板及其類似者，聚丁二烯結構之含量宜在45重量%或更多。同時，目前已知具有聚丁二烯結構或聚醯亞胺結構的化合物傾向於具有低介電常數及低介電損失正切。使用於本發明中的改質線型聚醯亞胺樹脂具有兩者結構，從而使本發明熱固性樹脂組成物為絕緣材料，也有卓越的介電性質，尤其是，當改質線型聚醯亞胺樹脂中具有較高的聚丁二烯結構含量，將比熱固性樹脂組成物具有更加改進的介電性質。In the modified polyimine resin used in the present invention, it is possible to change the composition ratio of the polybutadiene structure to the polyimine structure by controlling the reaction ratio of the starting material. A high proportion of the polybutadiene structure makes the thermosetting resin composition of the present invention a material having superior flexibility, and a high proportion of the polyimide structure results in a material having superior heat resistance. As described above, when the content of the polybutadiene structure in the modified linear polyimide resin is less than 45% by weight, the modified linear polyimide resin tends to have poor flexibility. Therefore, in applications requiring flexibility, such as a flexible circuit board and the like, the polybutadiene structure is preferably contained in an amount of 45% by weight or more. Meanwhile, compounds having a polybutadiene structure or a polyamidene structure are currently known to have a low dielectric constant and a low dielectric loss tangent. The modified linear polyimine resin used in the present invention has both structures, so that the thermosetting resin composition of the present invention is an insulating material, and also has excellent dielectric properties, especially when the modified linear polyimide resin is used. It has a higher polybutadiene structure content and will have more improved dielectric properties than the thermosetting resin composition.

在末端二元羥化的聚丁二烯之中的成分(a)，其係用作在本發明中改質聚醯亞胺樹脂之起始材料，術語“末端二元羥化的”意指在兩端具有羥基基團的聚丁二烯。在聚丁二烯分子之中的不飽和鍵結可能氫化。末端二元羥化的聚丁二烯的特定實施例包括例如可購自Nippon Soda公司的G－1000、G－3000、GI－1000、及GI－3000，及可購自Idemitsu Petrochemical公司的R－45EPI，及其類似者。Component (a) among the terminally hydroxylated polybutadienes, which is used as a starting material for the modified polyimine resin in the present invention, the term "terminally hydroxylated" means Polybutadiene having a hydroxyl group at both ends. The unsaturated bond in the polybutadiene molecule may be hydrogenated. Specific examples of terminally dihydroxylated polybutadiene include, for example, G-1000, G-3000, GI-1000, and GI-3000, available from Nippon Soda Corporation, and R-, available from Idemitsu Petrochemical Corporation. 45EPI, and the like.

用作為在本發明中改質聚醯亞胺樹脂之起始材料的二異氰酸酯化合物的成分(b)之實施例包括二異氰酸酯如甲苯－2,4－二異氰酸酯、甲苯－2,6－二異氰酸酯、六伸甲基二異氰酸酯、二伸甲苯二異氰酸酯、二苯基甲烷二異氰酸酯、及異佛爾酮二異氰酸酯。Examples of the component (b) of the diisocyanate compound used as a starting material for modifying the polyimine resin in the present invention include diisocyanates such as toluene-2,4-diisocyanate and toluene-2,6-diisocyanate. , Hexamethylene diisocyanate, di-toluene diisocyanate, diphenylmethane diisocyanate, and isophorone diisocyanate.

用作為在本發明中改質聚醯亞胺樹脂之起始材料的四酸二酐之成分(c)的特定實施例包括焦蜜石二酸酐、苯甲酮四羧基二酐，聯苯四羧基二酐、萘四羧基二酐、5－(2,5－二酮基四氫呋喃基)－3－甲基－環己烯－1,2－二酸酐、3,3',4,4'－二苯基碸四羧基二酐、1,3,3a,4,5,9b－六氫－5－(四氫－2,5－二酮基－3－呋喃甲醯基)－萘並[1,2－C]呋喃－1,3－二酮、及其類似者。Specific examples of the component (c) used as the starting material of the modified polyimine resin in the present invention include pyromellitic dianhydride, benzophenone tetracarboxy dianhydride, and biphenyl tetracarboxyl group. Dihydride, naphthalene tetracarboxy dianhydride, 5-(2,5-dionetetrahydrofuryl)-3-methyl-cyclohexene-1,2-dianhydride, 3,3',4,4'-di Phenylhydrazine tetracarboxy dianhydride, 1,3,3a,4,5,9b-hexahydro-5-(tetrahydro-2,5-diketo-3-mercaptomethyl)-naphtho[1, 2-C]furan-1,3-dione, and the like.

在製作依據本發明的改質聚醯亞胺樹脂之中，介於末端二元羥化的聚丁二烯與二異氰酸酯化合物之間的反應，可在有機溶劑之中於80℃或更低的反應溫度條件之下進行，且反應時間一般為1至8小時。若須要，可在觸媒之存在下進行反應。可進行介於聚丁二烯二異氰酸酯組成物與四酸二酐之間的反應，使在如上反應得到的內含聚丁二烯二異氰酸酯組成物溶液冷卻至室溫，將四酸二酐加入溶液中，且在120至180℃之反應溫度條件下將其反應，且反應時間為2至24小時。一般在觸媒之存在下進行反應。此外，可將有機溶劑加入反應系統中。若須要，可將如此得到反應溶液過濾以去除不溶的物質。在此方法中，改質線型聚醯亞胺樹脂組成物可呈清漆而得到。可經由在反應中控制溶劑量或經由於反應之後加入溶劑而適當地調整清漆中的溶劑含量。此外，於介於聚丁二烯二異氰酸酯組成物與四酸二酐之間的反應之後，可反應額外的二異氰酸酯，以得到較高分子量的改質線型聚醯亞胺樹脂。在此案例中，額外的二異氰酸酯化合物可逐滴加入聚丁二烯二異氰酸酯組成物與四酸二酐之反應混合物中，且在120至180℃的反應溫度條件下反應，且反應時間為2至24小時。In the preparation of the modified polyimine resin according to the present invention, the reaction between the terminally hydroxylated polybutadiene and the diisocyanate compound may be at 80 ° C or lower in an organic solvent. The reaction is carried out under the reaction temperature conditions, and the reaction time is usually from 1 to 8 hours. If necessary, the reaction can be carried out in the presence of a catalyst. The reaction between the polybutadiene diisocyanate composition and the tetraacid dianhydride can be carried out, and the solution containing the polybutadiene diisocyanate contained in the above reaction is cooled to room temperature, and tetracarboxylic dianhydride is added. The solution is reacted at a reaction temperature of 120 to 180 ° C for a reaction time of 2 to 24 hours. The reaction is generally carried out in the presence of a catalyst. Further, an organic solvent may be added to the reaction system. If necessary, the reaction solution thus obtained can be filtered to remove insoluble matter. In this method, the modified linear polyimine resin composition can be obtained as a varnish. The solvent content in the varnish can be appropriately adjusted by controlling the amount of the solvent in the reaction or by adding a solvent after the reaction. Further, after the reaction between the polybutadiene diisocyanate composition and the tetraacid dianhydride, an additional diisocyanate may be reacted to obtain a higher molecular weight modified linear polyimine resin. In this case, an additional diisocyanate compound may be added dropwise to the reaction mixture of the polybutadiene diisocyanate composition and the tetraacid dianhydride, and reacted at a reaction temperature of 120 to 180 ° C, and the reaction time is 2 Up to 24 hours.

可使用於上述各反應中的有機溶劑之實施例包括例如極性溶劑如N,N'－二甲基甲醯胺、N,N'－二乙基甲醯胺、N,N'－二甲基乙醯胺、N,N'－二乙基乙醯胺、二甲基亞碸、二乙基亞碸、N－甲基－2－吡咯烷酮、四甲基尿素、γ－丁內酯、環己酮、二甘醇二甲醚、三甘醇二甲醚、二甘醇一***乙酸酯、丙二醇單甲基醚乙酸酯、及丙二醇單***乙酸酯。此類溶劑，可合併二或更多者而使用。此外，若須要，可選擇性地合併使用非極性溶劑如芳族烴。Examples of the organic solvent which can be used in each of the above reactions include, for example, a polar solvent such as N,N'-dimethylformamide, N,N'-diethylformamide, N,N'-dimethyl Acetamine, N,N'-diethylacetamidine, dimethyl hydrazine, diethyl hydrazine, N-methyl-2-pyrrolidone, tetramethyl urea, γ-butyrolactone, cyclohexyl Ketone, diglyme, triethylene glycol dimethyl ether, diethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate, and propylene glycol monoethyl ether acetate. Such a solvent may be used in combination of two or more. Further, if necessary, a nonpolar solvent such as an aromatic hydrocarbon may be selectively used in combination.

可使用於上述各反應的觸媒之實施例包括例如第三胺類如四甲基丁烷二胺、苄二甲胺、三乙醇胺、三乙胺、N,N'－二甲基六氫吡啶、α－甲苄二甲胺、N－甲基嗎福啉及三乙二胺；及有機金屬觸媒如月桂酸二丁基錫、二甲基錫二氯化物、環酸鈷、及環酸鋅；及其類似者。此類觸媒可合併二或更多者而使用。特別地，最佳觸媒為三乙二胺。Examples of the catalyst which can be used in each of the above reactions include, for example, a third amine such as tetramethylbutanediamine, benzdimethylamine, triethanolamine, triethylamine, N,N'-dimethylhexahydropyridine , α-methylbenzyl dimethylamine, N-methylmorpholine and triethylenediamine; and organometallic catalysts such as dibutyltin laurate, dimethyltin dichloride, cobalt cyclamate, and zinc cyclamate; And similar. Such catalysts can be used in combination with two or more. In particular, the most preferred catalyst is triethylenediamine.

本發明熱固性樹脂組成物的主要成分包含上述改質聚醯亞胺樹脂的成分(A)與至少在一種選自下列各項的熱固性樹脂之成分(B)：環氧樹脂、雙順丁烯二醯亞胺樹脂、氰酸酯樹脂、雙烯丙基－奈二－醯亞胺樹脂、乙烯基苄基醚樹脂、苯並噁嗪樹脂、及雙順丁烯二醯亞胺與二胺之聚合物。特別較佳的熱固性樹脂為環氧樹脂，其可在最低的溫度硬化。可混合且使用二或更多類型的熱固性樹脂。The main component of the thermosetting resin composition of the present invention comprises the component (A) of the above modified polyimine resin and the component (B) of at least one thermosetting resin selected from the group consisting of epoxy resin and bis-butene. Polymerization of quinone imine resin, cyanate resin, bisallyl-naphthyl-imine resin, vinyl benzyl ether resin, benzoxazine resin, and bis-xetylene diimine and diamine Things. A particularly preferred thermosetting resin is an epoxy resin which hardens at the lowest temperature. Two or more types of thermosetting resins can be mixed and used.

環氧樹脂之實施例包括那些在分子中具有二或更多官能基團者，例如雙酚A型環氧樹脂、雙酚F型環氧樹脂、酚酚醛清漆型環氧樹脂、雙酚S型環氧樹脂、烷基酚酚醛清漆型環氧樹脂、雙酚型環氧樹脂、萘型環氧樹脂、二環戊二烯型環氧樹脂、源自酚與具有酚系羥基基團的芳族醛之縮合產物的環氧化反應產物、三甘油基異氰尿酸酯、及脂環族環氧樹脂。此類環氧樹脂可合併二或更多者而使用。Examples of the epoxy resin include those having two or more functional groups in the molecule, such as bisphenol A type epoxy resin, bisphenol F type epoxy resin, phenol novolak type epoxy resin, bisphenol S type Epoxy resin, alkylphenol novolak type epoxy resin, bisphenol type epoxy resin, naphthalene type epoxy resin, dicyclopentadiene type epoxy resin, aromatic derived from phenol and phenolic hydroxyl group An epoxidation reaction product of a condensation product of an aldehyde, triglyceryl isocyanurate, and an alicyclic epoxy resin. Such epoxy resins can be used in combination of two or more.

當使用環氧樹脂，一般需要使用環氧硬化劑。環氧硬化劑之實施例包括例如胺為主的硬化劑、胍為主的硬化劑、咪唑為主的硬化劑、酚為主的硬化劑、酸酐為主的硬化劑、環氧基加合物、及其微封裝產物、及其類似者。特別地，以胺為主的硬化劑及咪唑為主的硬化劑為較佳，此係基於樹脂組成物的清漆之黏度穩定性的觀點。環氧硬化劑可合併二或更多者而使用。此外，硬化促進劑如苯基膦、硼酸鏻、3－(3,4－二氯苯基)－1,1－二甲基尿素或其類似者也可合併使用。When an epoxy resin is used, an epoxy hardener is generally required. Examples of the epoxy hardener include, for example, an amine-based hardener, a bismuth-based hardener, an imidazole-based hardener, a phenol-based hardener, an acid anhydride-based hardener, and an epoxy-based adduct. , and its microencapsulated products, and the like. In particular, an amine-based hardener and an imidazole-based hardener are preferred, and this is based on the viewpoint of the viscosity stability of the varnish of the resin composition. The epoxy hardener can be used in combination of two or more. Further, a hardening accelerator such as phenylphosphine, strontium borate, 3-(3,4-dichlorophenyl)-1,1-dimethylurea or the like may also be used in combination.

環氧硬化劑的特定實施例包括例如胺為主的硬化劑如二聚胺基氰；咪唑為主的硬化劑如2－苯基－4－甲基－5－羥甲基咪唑及2,4－二胺基－6－[2'－甲基咪唑基－(1')]－乙基－s－三嗪異氰尿酸加合物；酚為主的硬化劑如內含三嗪－結構的酚酚醛清漆樹脂(例如PHENOLITE 7050系列，可購自Dainippon Ink and Chemicals公司)；及其類似者。Specific examples of epoxy hardeners include, for example, amine-based hardeners such as dimeric amine cyanide; imidazole-based hardeners such as 2-phenyl-4-methyl-5-hydroxymethylimidazole and 2,4 -diamino-6-[2'-methylimidazolyl-(1')]-ethyl-s-triazine isocyanuric acid adduct; phenol-based hardener such as triazine-structured Phenolic novolac resins (e.g., PHENOLITE 7050 series, available from Dainippon Ink and Chemicals); and the like.

雙順丁烯二醯亞胺樹脂之實施例包括4,4'－苯基甲烷雙順丁烯二醯亞胺“BMI－S”，可購自Mitsui Chemicals公司，聚苯基甲烷順丁烯二醯亞胺“BMI－M－20”，可購自Mitsui Chemicals公司，及其類似者。Examples of the bis-m-butylene iminoimide resin include 4,4'-phenylmethanebis-sandimimide "BMI-S" available from Mitsui Chemicals, Inc., polyphenylmethane butene The quinone imine "BMI-M-20" is commercially available from Mitsui Chemicals, Inc. and the like.

氰酸酯樹脂之實施例包括雙酚型氰酸酯類如“Primaset BA200”，可購自Lonza公司，及“Primaset BA230S”，可購自Lonza公司；雙酚H型氰酸酯類如“Prunaset LECY”，可購自Lonna；公司，及“Arocy L10”，可購自Vantico Inc.；酚醛清漆型氰酸酯類如“Primaset PT30”，可購自Lonza公司，及“Arocy XU371”，可購自Vantico Inc.；二環戊二烯型氰酸酯類如“Arocy XP71787 02L”，可購自Vantico Inc.；及其類似者。Examples of cyanate resins include bisphenol type cyanates such as "Primaset BA200" available from Lonza Corporation, and "Primaset BA230S" available from Lonza Corporation; bisphenol H type cyanates such as "Prunaset" LECY", available from Lonna; the company, and "Arocy L10", available from Vantico Inc.; novolak-type cyanate esters such as "Primaset PT30", available from Lonza, and "Arocy XU371", available From Vantico Inc.; dicyclopentadiene type cyanate such as "Arocy XP71787 02L", available from Vantico Inc.; and the like.

雙烯丙基－奈二－醯亞胺樹脂之實施例包括二苯基甲烷－4,4'－雙(烯丙基奈二)醯亞胺“BANI－M”，可購自Maruzen Petrochemical公司，及其類似者。Examples of bisallyl-naphtho-imine resin include diphenylmethane-4,4'-bis(allylnaphthalene)imide "BANI-M" available from Maruzen Petrochemical. And similar.

乙烯基苄基醚樹脂之實施例包括V－1000X，可購自Showa Highpolymer公司，那些敘述於美國專利4116936、美國專利4170711、美國專利4278708、JP－A－9－31006、JP－A－2001－181383、JP－A－2001－253992、JP－A－2003－277440、JP－A－2003－283076、WO 02/083610；及其類似者。Examples of vinyl benzyl ether resins include V-1000X, available from Showa Highpolymer, which are described in U.S. Patent 4,116,936, U.S. Patent 4,170,071, U.S. Patent 4,278,708, JP-A-9-31,006, JP-A-2001- 181383, JP-A-2001-253992, JP-A-2003-277440, JP-A-2003-283076, WO 02/083610, and the like.

苯並噁嗪樹脂之實施例包括“B－a型苯並噁嗪”及“B－m型苯並噁嗪”，可購自Shikoku Corporation，及其類似者。Examples of the benzoxazine resin include "B-a type benzoxazine" and "B-m type benzoxazine", which are commercially available from Shikoku Corporation, and the like.

雙順丁烯二醯亞胺化合物與二胺化合物之聚合物的熱固性樹脂之實施例包括可購自Printec公司的“TECHMIGHT E2020”，及其類似者。Examples of thermosetting resins of polymers of bis-methyleneimine compound and diamine compound include "TECHMIGHT E2020" available from Printec Corporation, and the like.

在本發明熱固性樹脂組成物之中，介於成分(A)與成分(b)之間的重量比(A)：(B)較佳範圍在100：1至1；1。在全部樹脂中，熱固性樹脂組成物中成分(A)與成分(B)的總含量宜在70重量%或更多。當其不在此範圍之中，在一些案例中可能無法充分地得到本發明的有利效應。In the thermosetting resin composition of the present invention, the weight ratio (A) between the component (A) and the component (b): (B) is preferably in the range of 100:1 to 1; In all the resins, the total content of the component (A) and the component (B) in the thermosetting resin composition is preferably 70% by weight or more. When it is not within this range, the advantageous effects of the present invention may not be sufficiently obtained in some cases.

若須要，本發明熱固性樹脂組成物可進一步的包含填料。填料可能為有機填料或無機填料。可合併且使用二或更多填料。無機填料含量未特別地限制，但在熱固性樹脂組成物中宜加入的範圍在50重量%或更低。當含量高於50重量%，熱固性樹脂組成物會有不良的雷射加工性質，且其硬化材料會變得有高的彈性模數，剛硬且脆。據此，該材料不是較佳的，且從而不適合用於可撓性電路板。The thermosetting resin composition of the present invention may further comprise a filler if necessary. The filler may be an organic filler or an inorganic filler. Two or more fillers can be combined and used. The content of the inorganic filler is not particularly limited, but it is preferably included in the thermosetting resin composition in the range of 50% by weight or less. When the content is more than 50% by weight, the thermosetting resin composition may have poor laser processing properties, and the hardened material may have a high modulus of elasticity, which is hard and brittle. Accordingly, the material is not preferred and thus is not suitable for use in a flexible circuit board.

無機填料之實施例包括二氧化矽、氧化鋁、硫酸鋇、滑石粉、黏土、雲母粉末、氫氧化鋁、氫氧化鎂、碳酸鈣、碳酸鎂、氧化鎂、氮化硼、硼酸鋁、鈦酸鋇、鈦酸鍶、鈦酸鈣、鈦酸鎂、鈦酸鉍、氧化鈦、鋯酸鋇、鋯酸鈣、及其類似者。特別較佳為二氧化矽。無機填料之平均粒徑宜在5μm或更低。有機填料之實施例包括丙烯酸橡膠微粒、矽微粒及其類似者。有機填料之平均粒徑也宜在5μm或更低。測量平均粒徑其可採用雷射繞射/散射類型粒徑分佈測量裝置LA－500，由Horiba公司製作本發明熱固性樹脂組成物中可加入各種樹脂添加劑，除了成分(A)與(B)之外的樹脂成分，及其類似者，而未偏離可達成本發明之效應的範圍。樹脂添加劑之實施例包括黏稠劑如歐本(orben)及班登(bendone)；矽氧烷為主的、氟為主的、或丙烯酸系為主的消泡劑；平坦劑；提供黏合劑如咪唑為主的、噻唑為主的、或***為主的試藥；表面處理劑如矽烷耦合劑；著色劑如鄰苯二甲醯青藍藍色、鄰苯二甲醯青藍綠色、碘綠色、雙偶氮基黃色、及碳黑；阻焰劑如內含磷的化合物、內含溴的化合物、氫氧化鋁、及氫氧化鎂；及氧化反應抑制劑如磷為主的氧化反應抑制劑及酚為主的氧化反應抑制劑。Examples of the inorganic filler include cerium oxide, aluminum oxide, barium sulfate, talc, clay, mica powder, aluminum hydroxide, magnesium hydroxide, calcium carbonate, magnesium carbonate, magnesium oxide, boron nitride, aluminum borate, and titanic acid. Barium, barium titanate, calcium titanate, magnesium titanate, barium titanate, titanium oxide, barium zirconate, calcium zirconate, and the like. Particularly preferred is cerium oxide. The average particle diameter of the inorganic filler is preferably 5 μm or less. Examples of the organic filler include acrylic rubber particles, ruthenium particles, and the like. The average particle diameter of the organic filler is also preferably 5 μm or less. The average particle diameter can be measured by using a laser diffraction/scattering type particle size distribution measuring device LA-500, and various thermosetting resin compositions of the present invention can be added to the composition of the thermosetting resin of the present invention, except for the components (A) and (B). The outer resin component, and the like, without departing from the scope of the effect of the invention. Examples of the resin additive include a thickener such as orben and bendone; a siloxane-based, fluorine-based or acrylic-based defoaming agent; a flattening agent; and a binder such as Imidazole-based, thiazole-based, or triazole-based reagents; surface treatment agents such as decane coupling agents; colorants such as phthalic acid blue blue, phthalic acid blue green, iodine Green, bisazo yellow, and carbon black; flame retardant such as phosphorus-containing compound, bromine-containing compound, aluminum hydroxide, and magnesium hydroxide; and oxidation reaction inhibitor such as phosphorus-based oxidation inhibition Agent and phenol-based oxidation reaction inhibitor.

本發明熱固性樹脂組成物可用呈一種膠黏劑膜的形式，其包含熱固性樹脂組成物層(A層)及支撐膜(B層)，其為用於製作可撓性電路板的適合形式。The thermosetting resin composition of the present invention may be in the form of an adhesive film comprising a thermosetting resin composition layer (layer A) and a support film (layer B), which is a suitable form for producing a flexible circuit board.

膠黏劑膜可依據一項已知於熟悉此技藝之人士的方法製作，例如經由將本發明熱固性樹脂組成物溶解在有機溶劑之中以製備樹脂清漆，將此樹脂清漆施用在支撐膜上，且經由加熱或熱空氣吹風乾燥有機溶劑以形成熱固性樹脂組成物層。The adhesive film can be produced according to a method known to those skilled in the art, for example, by dissolving the thermosetting resin composition of the present invention in an organic solvent to prepare a resin varnish, and applying the resin varnish to the support film, And drying the organic solvent by heating or hot air blowing to form a thermosetting resin composition layer.

在製作膠黏劑膜中將支撐膜(B層)作為支撐，且在製作可撓性電路板中最後剝離或移除。支撐膜之實施例包括例如聚烯烴類如聚乙烯及聚氯乙烯的膜；聚酯如聚對酞酸乙二醇酯(以下可稱為"PET")與聚萘酸乙二醇酯的膜；聚碳酸酯、與離型紙、金屬箔如銅箔，及其類似者。同時，耐熱性樹脂如聚醯亞胺、聚醯胺、聚醯胺醯亞胺及液晶聚合物可用於支撐膜。當以銅箔用作為支撐膜，可經由採用氯化鐵(II)，氯化銅(II)或其類似者的蝕刻液體作蝕刻而移除銅箔。此支撐膜可作表面粗糙處理、電暈處理、或離型處理。更佳為作離型處理，基於可剝離性質，雖然未特別地限制支撐膜之厚度，一般在10至150μm，且較佳範圍在25至50μm。The support film (layer B) is supported as a support in the production of the adhesive film, and finally peeled off or removed in the fabrication of the flexible circuit board. Examples of the support film include films such as polyolefins such as polyethylene and polyvinyl chloride; polyesters such as polyethylene terephthalate (hereinafter may be referred to as "PET") and polyethylene naphthalate film. Polycarbonate, release paper, metal foil such as copper foil, and the like. Meanwhile, heat resistant resins such as polyimide, polyamine, polyamidimide, and liquid crystal polymer can be used for the support film. When a copper foil is used as the support film, the copper foil can be removed by etching using an etching liquid of iron (II) chloride, copper (II) chloride or the like. The support film can be subjected to surface roughening treatment, corona treatment, or release treatment. More preferably, it is a release treatment, and based on the peelable property, although the thickness of the support film is not particularly limited, it is generally from 10 to 150 μm, and preferably from 25 to 50 μm.

用於製備清漆的有機溶劑之實施例包括例如酮如丙酮、甲基乙基酮、及環己酮；乙酸酯類如乙酸乙酯、乙酸丁酯、2－乙氧基乙醇(賽璐蘇)乙酸酯、丙二醇單甲基醚乙酸酯、及二甘醇一***乙酸酯；2－乙氧基乙醇(賽璐蘇)；二甘醇一***類如丁基二甘醇一***；芳族烴類如甲苯及二甲苯；二甲基甲醯胺；二甲基乙醯胺；N－甲基吡咯烷酮；及其類似者。各有機溶劑可合併二或更多者而使用。Examples of the organic solvent used for the preparation of the varnish include, for example, ketones such as acetone, methyl ethyl ketone, and cyclohexanone; acetates such as ethyl acetate, butyl acetate, 2-ethoxyethanol (Cesare) Acetate, propylene glycol monomethyl ether acetate, and diethylene glycol monoethyl ether acetate; 2-ethoxyethanol (Cesare); diethylene glycol monoethyl ether such as butyl diglycol monoethyl ether; Aromatic hydrocarbons such as toluene and xylene; dimethylformamide; dimethylacetamide; N-methylpyrrolidone; and the like. Each organic solvent may be used in combination of two or more.

雖然乾燥條件未特別地限制，重要者在於在乾燥步驟期間儘可能將硬化熱固性樹脂組成物的程序降至最低，以維持膠黏劑膜之膠黏能力。當有大量的有機溶劑保持在膠黏劑膜中，有機溶劑可能會引起於硬化之後的膜起水泡。如此，一般進行乾燥步驟使在熱固性樹脂組成物中的有機溶劑含量變得5重量%或更低，且宜在3重量%或更低，此係基於熱固性樹脂組成物之總重。雖然可變化特定的乾燥條件，取決於熱固性樹脂組成物之硬化性質及在清漆中有機溶劑的用量，例如內含30至60重量%有機溶劑的清漆可在80至120℃乾燥3至13分鐘。熟悉此技藝的專業人士可經由隨意的簡單實驗而決定較佳的乾燥條件。Although the drying conditions are not particularly limited, it is important to minimize the procedure for hardening the thermosetting resin composition during the drying step to maintain the adhesive ability of the adhesive film. When a large amount of organic solvent is held in the adhesive film, the organic solvent may cause blisters in the film after hardening. Thus, the drying step is generally carried out so that the content of the organic solvent in the thermosetting resin composition becomes 5% by weight or less, and preferably 3% by weight or less, based on the total weight of the thermosetting resin composition. Although the specific drying conditions can be varied, depending on the hardening property of the thermosetting resin composition and the amount of the organic solvent in the varnish, for example, the varnish containing 30 to 60% by weight of the organic solvent can be dried at 80 to 120 ° C for 3 to 13 minutes. Professionals familiar with this art can determine preferred drying conditions through random and simple experiments.

可使用於熱固性樹脂組成物層(A層)的熱固性樹脂組成物為如上述者。熱固性樹脂組成物層(A層)之厚度一般範圍可在5至500μm。取決於膠黏劑膜的用途，可變化A層厚度較佳的範圍。在一項案例中，膠黏劑膜經由堆積方法用於生產多層可撓性電路板，用以形成電路的導體層一般厚度在5至70μm，從而使對應於層間絕緣層的A層的厚度範圍宜在10至100μm。The thermosetting resin composition which can be used for the thermosetting resin composition layer (layer A) is as described above. The thickness of the thermosetting resin composition layer (layer A) may generally range from 5 to 500 μm. Depending on the use of the adhesive film, a preferred range of thickness of layer A can be varied. In one case, the adhesive film is used to produce a multilayer flexible circuit board by a stacking method, and the conductor layer for forming the circuit is generally 5 to 70 μm thick so that the thickness of the layer A corresponding to the interlayer insulating layer is made. It should be between 10 and 100 μm.

A層可經由保護膜所保護。經由保護膜的保護可預防塵黏合及樹脂組成物層的表面刮傷。於疊層製程期間將保護膜剝離。作為支撐膜的相同材料可用於保護膜。保護膜之厚度未特別地限制，但較佳的範圍在1至40μm。The A layer can be protected by a protective film. The surface of the resin composition layer can be prevented from being scratched by the protection of the protective film. The protective film is peeled off during the lamination process. The same material as the support film can be used for the protective film. The thickness of the protective film is not particularly limited, but a preferred range is from 1 to 40 μm.

本發明的膠黏劑膜可特別適宜用於多層可撓性電路板的製作。如下記述多層可撓性電路板的生產方法。本發明的膠黏劑膜可適合經由真空層合器而層合為可撓性電路板。在此使用的可撓性電路板主要可包含基材如聚酯基材、聚醯亞胺基材、聚醯胺醯亞胺基材、或液晶聚合物基材，及形成在基材一面或兩面上的圖案化導體層(電路)。此外，此可撓性電路板可為多層可撓性電路板，其中包含供選擇形成的積體電路與絕緣層且在一面或兩面上具有積體電路，且可用膠黏劑膜進一步增加層數。基於將絕緣層黏合至電路板之觀點，宜使積體電路的表面係預先經由表面處理劑如過氧化氫/硫酸及可購自MEC Co,Ltd的MECetchBOND而作粗糙化。The adhesive film of the present invention is particularly suitable for use in the fabrication of multilayer flexible circuit boards. The production method of the multilayer flexible circuit board is described below. The adhesive film of the present invention can be suitably laminated to a flexible circuit board via a vacuum laminate. The flexible circuit board used herein may mainly comprise a substrate such as a polyester substrate, a polyimide substrate, a polyimide substrate, or a liquid crystal polymer substrate, and is formed on one side of the substrate or Patterned conductor layers (circuits) on both sides. In addition, the flexible circuit board can be a multi-layer flexible circuit board, which comprises an optional integrated circuit and an insulating layer, and has an integrated circuit on one or both sides, and can further increase the number of layers by using an adhesive film. . From the viewpoint of bonding the insulating layer to the circuit board, it is preferable to roughen the surface of the integrated circuit in advance via a surface treating agent such as hydrogen peroxide/sulfuric acid and MECetchBOND available from MEC Co., Ltd.

商購的真空層合器之實施例包括例如由Nichigo-Morton公司製作的真空塗抹器，由Meiki公司製作的真空與壓力層合器，由Hitachi工業公司製作的滾動型乾燥塗覆器，由Hitachi AIC公司製作的真空層合器，及其類似者。Examples of commercially available vacuum laminators include, for example, a vacuum applicator manufactured by Nichigo-Morton Co., a vacuum and pressure laminator manufactured by Meiki, a rolling type dry applicator manufactured by Hitachi Industries, Inc., by Hitachi A vacuum laminate made by AIC, and the like.

在疊層方法之中當膠黏劑膜具有保護膜，經由於去除保護膜之後對膠黏劑膜施加壓力且加熱，將膠黏劑膜黏合至電路板。在疊層條件之中，若須要，可將膠黏劑膜及電路板預熱，且黏合溫度宜在70至140℃而黏合壓力宜在1至11 kgf/cm² ，且疊層宜於空氣減壓下20mmHg或更低之下進行。疊層可經由批式方法或連續滾動方法達成。In the lamination method, when the adhesive film has a protective film, the adhesive film is adhered to the circuit board by applying pressure and heating to the adhesive film after removing the protective film. In the lamination condition, if necessary, the adhesive film and the circuit board may be preheated, and the bonding temperature is preferably 70 to 140 ° C and the bonding pressure is preferably 1 to 11 kgf / cm ² , and the laminate is suitable for air. It is carried out under reduced pressure of 20 mmHg or less. The laminate can be achieved via a batch method or a continuous rolling method.

於將膠黏劑膜層合至電路板之後，將膠黏劑膜冷卻至的周圍室溫且將支撐膜剝離。然後，將壓至電路板上的熱固性樹脂組成物層作熱硬化。一般而言，選擇的熱硬化條件範圍在150至220℃之溫度，時間為20至180分鐘，且更佳的範圍在溫度160至200℃，時間為30至120分鐘。當其中支撐膜有作離型處理或具有可剝離層如矽或其類似者，可於熱固性樹脂組成物的熱硬化之後，或於熱硬化及孔形成之後剝離支撐膜。After laminating the adhesive film to the circuit board, the adhesive film is cooled to ambient room temperature and the support film is peeled off. Then, the thermosetting resin composition layer pressed onto the circuit board is thermally hardened. In general, the selected thermosetting conditions range from 150 to 220 ° C for a period of from 20 to 180 minutes, and more preferably from 160 to 200 ° C for a period of from 30 to 120 minutes. When the support film is subjected to release treatment or has a peelable layer such as ruthenium or the like, the support film may be peeled off after thermal hardening of the thermosetting resin composition, or after heat hardening and pore formation.

於形成內含熱固性樹脂組成物之硬化材料的絕緣層之後，如須要，可經由鑽機、雷射，電漿，或其組合，在電路板中形成各種孔如導孔(via hole)及導孔(through hole)。特別地，一般可用雷射如二氧化碳氣體雷射及YAG雷射以形成孔。After forming the insulating layer of the hardening material containing the thermosetting resin composition, if necessary, various holes such as via holes and via holes may be formed in the circuit board via a drill, a laser, a plasma, or a combination thereof. (through hole). In particular, lasers such as carbon dioxide gas lasers and YAG lasers are generally available to form holes.

然後，將絕緣層(熱固性樹脂組成物之硬化材料)作表面處理。針對表面處理，可使用除污(desmearing)製程之方法，其可與除污同時進行。一般將氧化劑用作為除污製程的試藥。氧化劑之實施例包括例如高錳酸鹽類如高錳酸鉀及高錳酸鈉、重鉻酸鹽類、臭氧、過氧化氫/硫酸、硝酸、及其類似者。較佳者，進行此處理可使用鹼性的高錳酸鹽溶液例如高錳酸鉀或高錳酸鈉的水性氫氧化鈉溶液，其在經由堆積方法製作多層印刷電路板中廣泛地用作為針對粗糙絕緣層的氧化劑。在使用氧化劑作處理之前，可以膨潤劑處理絕緣層。於使用氧化劑處理之後，一般使用還原劑將絕緣層作中和處理。Then, the insulating layer (hardened material of the thermosetting resin composition) is subjected to surface treatment. For surface treatment, a desmearing process can be used, which can be carried out simultaneously with decontamination. The oxidizing agent is generally used as a reagent for the decontamination process. Examples of the oxidizing agent include, for example, permanganates such as potassium permanganate and sodium permanganate, dichromate, ozone, hydrogen peroxide/sulfuric acid, nitric acid, and the like. Preferably, this treatment can be carried out using an alkaline permanganate solution such as potassium permanganate or sodium permanganate in an aqueous sodium hydroxide solution, which is widely used in the production of multilayer printed circuit boards by a deposition method. An oxidizing agent for a rough insulating layer. The insulating layer may be treated with a swelling agent prior to treatment with an oxidizing agent. After treatment with an oxidizing agent, the insulating layer is typically neutralized using a reducing agent.

如情況許可，如上述之除污製程可增加經由電鍍而形成的導體層之剝離強度，且如此也可使絕緣層粗糙，從而使此層不均勻。一般而言，需要形成不均勻的表面，以在經由電鍍的絕緣層上形成具有高剝離強度的導體層。然而，不均勻的表面將影響導體圖案化成為電路的準確度，且不利者將難於為了增加剝離強度採用增強不均勻性而形成細微圖案。當本發明熱固性樹脂組成物實質上不含填料，甚至雖然使用上述氧化劑作表面處理，硬化材料表面未製作成不均勻的。然而，依據本發明熱固性樹脂組成物，甚至當其中導體層形成在該平坦的經由電鍍的硬化材料表面上，導體層具有高剝離強度，且可形成具有卓越黏合的細微圖案化的電路。當本發明熱固性樹脂組成物實質上不含填料，絕緣層的表面粗糙(Ra值)可為500 nm或更低，再更佳為400 nm或更低，且再更佳為300 nm或更低。Ra值為在全部測量區域的平均高度值。特別地，Ra值為在測量區域由平均線表面上測量的算術平均絕對高度值，且可由以下公式(1)代表。在式中，M及N代表在各排列方向上的許多數據。As the case may be, the decontamination process as described above may increase the peel strength of the conductor layer formed by electroplating, and thus the insulating layer may be roughened to make the layer uneven. In general, it is necessary to form a non-uniform surface to form a conductor layer having high peel strength on an insulating layer via electroplating. However, a non-uniform surface will affect the accuracy of patterning the conductor into a circuit, and it will be disadvantageous that it will be difficult to form a fine pattern by increasing the unevenness in order to increase the peel strength. When the thermosetting resin composition of the present invention contains substantially no filler, even if the above oxidizing agent is used as the surface treatment, the surface of the hardened material is not made uneven. However, according to the thermosetting resin composition of the present invention, even when a conductor layer is formed on the flat surface of the hardened material via electroplating, the conductor layer has high peel strength, and a fine patterning circuit having excellent adhesion can be formed. When the thermosetting resin composition of the present invention contains substantially no filler, the surface roughness (Ra value) of the insulating layer may be 500 nm or less, more preferably 400 nm or less, and still more preferably 300 nm or less. . The Ra value is the average height value in all measurement areas. Specifically, the Ra value is an arithmetic mean absolute height value measured on the average line surface in the measurement area, and can be represented by the following formula (1). In the formula, M and N represent a lot of data in each arrangement direction.

特別地，由Veeco Instruments公司製作的非接觸表面粗糙計WYKO NT3300可用以測量表面粗糙度。In particular, a non-contact surface roughness meter WYKO NT3300 manufactured by Veeco Instruments can be used to measure surface roughness.

於表面處理之後，在絕緣層之表面上電鍍而形成導體層。形成導體層可經由合併無電電鍍及電鍍之方法。此外，也可形成使用導體層作鍍層的電阻相反圖案化，從而使導體層可僅經由無電電鍍而形成。於形成導體層之後，經由將此層於150至200℃之溫度退火20至90分鐘，可進一步的改善且穩定化導體層之剝離強度。After the surface treatment, a conductor layer is formed by electroplating on the surface of the insulating layer. Forming the conductor layer can be accomplished by a combination of electroless plating and electroplating. Further, it is also possible to form a reverse resistance patterning using a conductor layer as a plating layer, so that the conductor layer can be formed only by electroless plating. After the conductor layer is formed, the peel strength of the conductor layer can be further improved and stabilized by annealing the layer at a temperature of 150 to 200 ° C for 20 to 90 minutes.

可經由一些方法將導體層作圖案化加工以形成電路，例如減去方法，半添加方法，或已知於一位熟悉此技藝的專業人士的其類似者。在減去方法之中，無電鍍層的銅層之厚度為0.1至3μm，且宜在0.3至2μm。電路板的製作可經由電鍍層而在銅層上形成(板鍍層的層)，其厚度在3至35μm，較佳為厚度在5至20μm，隨後使用氯化鐵(II)、氯化銅(II)或其類似者的蝕刻液體形成抗蝕阻劑(etching resist)，且然後形成導體圖案且剝離此抗蝕刻層。另一方面，在半添加方法中，電路板的製作可經由無電鍍層的銅層形成，其厚度在0.1至3μm，且宜在0.3至2μm，隨後形成圖案化抵抗層(patterned resist)、電鍍銅，且剝離此抵抗。The conductor layer can be patterned by some method to form an electrical circuit, such as a subtractive method, a semi-additive method, or a similarity known to a person skilled in the art. Among the subtractive methods, the copper layer of the electroless plating layer has a thickness of 0.1 to 3 μm, and preferably 0.3 to 2 μm. The circuit board can be formed on the copper layer via a plating layer (layer of the plate plating) having a thickness of 3 to 35 μm, preferably 5 to 20 μm, followed by iron (II) chloride and copper chloride ( The etching liquid of II) or the like forms an etching resist, and then forms a conductor pattern and peels off the etching resistant layer. On the other hand, in the semi-additive method, the fabrication of the circuit board can be formed via a copper layer of an electroless plating layer having a thickness of 0.1 to 3 μm, and preferably 0.3 to 2 μm, followed by formation of a patterned resist, plating Copper, and peel off this resistance.

在支撐膜上具有耐熱性樹脂層(耐熱性樹脂膜)的膜，即內含熱固性樹脂組成物層(A層)與耐熱性樹脂層(C層)的膜，可用作可撓性電路板的基膜。同時，內含熱固性樹脂組成物層(A層)、耐熱性樹脂層(C層)、及銅箔(D層)的膜，可同樣地用作用於可撓性電路板的基膜。在此案例中，此基膜具有內含A層、C層、及D層順序的層化結構。在此之類基膜中，此類基膜的耐熱性樹脂層不會剝離且形成可撓性電路板的一部份。A film having a heat resistant resin layer (heat resistant resin film) on a support film, that is, a film containing a thermosetting resin composition layer (layer A) and a heat resistant resin layer (layer C), which can be used as a flexible circuit board Base film. At the same time, a film containing a thermosetting resin composition layer (A layer), a heat resistant resin layer (C layer), and a copper foil (D layer) can be similarly used as a base film for a flexible circuit board. In this case, the base film has a layered structure containing the order of the A layer, the C layer, and the D layer. In the base film such as this, the heat resistant resin layer of such a base film is not peeled off and forms a part of the flexible circuit board.

內含耐熱性樹脂層(C層)及絕緣層(A’層)，在其上形成包含本發明熱固性樹脂組成物之硬化材料的膜，可用作單面可撓性電路板的基膜。此外，在類似的方法之中，內含A’層、C層、及A’層順序的層化結構之膜，及具有內含A’層，C層及銅箔(D層)順序的層化結構之膜也可用作雙面可撓性電路板基膜。A heat-resistant resin layer (C layer) and an insulating layer (A' layer) are contained therein, and a film containing a hardening material of the thermosetting resin composition of the present invention is formed thereon, and can be used as a base film of a single-sided flexible circuit board. Further, among similar methods, a film containing a layered structure of the A' layer, the C layer, and the A' layer, and a layer having an A' layer, a C layer, and a copper foil (D layer) order The film of the structure can also be used as a base film for a double-sided flexible circuit board.

可使用於耐熱性樹脂層的耐熱性樹脂之實施例包括聚醯亞胺樹脂、芳族聚醯胺(aramid)樹脂、聚醯胺醯亞胺樹脂、液晶聚合物、及其類似者。特別較佳為聚醯亞胺樹脂及聚醯胺醯亞胺樹脂。基於使用於可撓性電路板中行為，宜使耐熱性樹脂的斷裂強度在100 MPa或更高，斷裂伸長量在5%或更多，在20至150℃的熱膨脹係數為40 ppm或更低，且玻璃態轉化溫度為200℃或更較高，或降解溫度在300℃或更高。Examples of the heat resistant resin which can be used for the heat resistant resin layer include a polyimide resin, an aromatic aramid resin, a polyamide amine imide resin, a liquid crystal polymer, and the like. Particularly preferred are polyimine resin and polyamidoximine resin. Based on the behavior used in the flexible circuit board, it is preferred that the heat-resistant resin has a breaking strength of 100 MPa or more, an elongation at break of 5% or more, and a thermal expansion coefficient of 40 ppm or less at 20 to 150 °C. And the glass transition temperature is 200 ° C or higher, or the degradation temperature is 300 ° C or higher.

具有該性質的宜使用的耐熱性樹脂可為商購可獲得的膜狀的，與一些耐熱性樹脂，且其已知的實施例包括例如可購自Ube Industries公司的聚醯亞胺膜“UPILEX－S”，可購自Du Pont－Toray Co.,Ltd的聚醯亞胺膜“KAPTON”，可購自Kaneka Corporation的聚醯亞胺膜“APICAL”，可購自Teijin Advanced Films公司的“ARAMICA”，可購自Kuraray公司的液晶聚合物膜“VECSTAR”，可購自Sumitomo Bakelite公司的聚醚醚酮膜“SUMILITE FS－1100C”，及其類似者。A heat resistant resin which is preferably used in this property may be commercially available in the form of a film, and some heat resistant resins, and known examples thereof include, for example, a polyimide film "UPILEX" available from Ube Industries, Inc. -S", a polyimine film "KAPTON" available from Du Pont-Toray Co., Ltd., a polyimide film available from Kaneka Corporation "APICAL", available from Teijin Advanced Films, Inc. "ARAMICA" A liquid crystal polymer film "VECSTAR" available from Kuraray Co., Ltd., available from Sumitomo Bakelite, a polyetheretherketone film "SUMILITE FS-1100C", and the like.

抗張斷裂強度、斷裂伸長量、及彈性模數的測定係依據一項敘述於JIS(日本工業標準)K 7127的方法。熱膨脹係數與玻璃轉移溫度的測定係依據一項敘述於XIS K 7197的方法。同時，在一項案例中，其中玻璃態轉化溫度高於降解溫度且實質上未觀察到玻璃態轉化溫度，適用“玻璃態轉化溫度在200℃或更較高”之定義。降解溫度定義為係依據一項敘述於JIS K7120方法所測量的質量降低比例為5%的溫度。The tensile strength at break, the elongation at break, and the modulus of elasticity are determined in accordance with a method described in JIS (Japanese Industrial Standard) K 7127. The coefficient of thermal expansion and the measurement of the glass transition temperature are based on a method described in XIS K 7197. Meanwhile, in one case, in which the glass transition temperature is higher than the degradation temperature and substantially no glass transition temperature is observed, the definition of "glass transition temperature at 200 ° C or higher" is applied. The degradation temperature is defined as the temperature at which the mass reduction ratio measured by the JIS K7120 method is 5%.

耐熱性樹脂層之厚度一般可在2至150μm，且較佳範圍在10至50μm。此耐熱性樹脂層(C層)可為表面處理層。表面處理之實施例包括乾燥處理如表面粗糙處理、電暈放電處理、及電漿處理；化學處理如溶劑處理、酸處理、及鹼處理；噴沙處理；機械磨光處理；及其類似者。基於黏合至A層之觀點，特別較佳者使耐熱性樹脂層作電漿處理。The thickness of the heat resistant resin layer may generally be from 2 to 150 μm, and preferably from 10 to 50 μm. This heat resistant resin layer (layer C) may be a surface treated layer. Examples of the surface treatment include drying treatment such as surface roughening treatment, corona discharge treatment, and plasma treatment; chemical treatment such as solvent treatment, acid treatment, and alkali treatment; sandblasting treatment; mechanical polishing treatment; and the like. From the viewpoint of bonding to the A layer, it is particularly preferable to subject the heat resistant resin layer to a plasma treatment.

針對單面可撓性電路板的基膜，其中包含絕緣層(A')及耐熱性樹脂層(C)，可依如下方法製作。首先，採用如製作上述膠黏劑膜的相同方法，將本發明熱固性樹脂組成物溶在有機溶劑之中以製備樹脂清漆，將此樹脂清漆施用於耐熱性樹脂膜上，且經由加熱或熱空氣吹風將有機溶劑乾燥，以形成熱固性樹脂組成物層。有機溶劑乾燥條件及其類似者相似於那些上述膠黏劑膜的製作。熱固性樹脂組成物層之厚度較佳的範圍在5至15μm。The base film of the single-sided flexible circuit board including the insulating layer (A') and the heat-resistant resin layer (C) can be produced as follows. First, the thermosetting resin composition of the present invention is dissolved in an organic solvent in the same manner as in the production of the above-mentioned adhesive film to prepare a resin varnish, which is applied to a heat resistant resin film, and heated or heated air. The organic solvent is dried by blowing to form a thermosetting resin composition layer. The organic solvent drying conditions and the like are similar to those of the above adhesive film. The thickness of the thermosetting resin composition layer is preferably in the range of 5 to 15 μm.

然後，將此熱固性樹脂組成物層熱硬化，以形成內含熱固性樹脂組成物之硬化材料的絕緣層其。一般而言，熱硬化條件的選擇範圍在150至220℃之溫度，時間為20至180分鐘，且更佳範圍在160至200℃之溫度，時間為30至120分鐘。Then, the thermosetting resin composition layer is thermally hardened to form an insulating layer containing a hardening material of the thermosetting resin composition. In general, the thermosetting conditions are selected from a temperature of from 150 to 220 ° C for a period of from 20 to 180 minutes, and more preferably from 160 to 200 ° C for a period of from 30 to 120 minutes.

針對雙面可撓性電路板的基膜，其中包含三層的絕緣層(A’層)、耐熱性樹脂層(C層)、及銅箔(D層)，其可且經由上述步驟製作，經由將熱固性樹脂組成物形成入銅覆蓋疊層膜上之一層中，此銅覆蓋疊層膜包含耐熱性樹脂層(C層)及銅箔(D層)。此銅覆蓋疊層膜可為澆鑄型二層CCL(鍍銅層合物)、濺射型二層CCL、層合型二層CCL、三層CCL、或其類似者。銅箔厚度宜在12μm或18μm。The base film for the double-sided flexible circuit board includes three layers of an insulating layer (A' layer), a heat resistant resin layer (C layer), and a copper foil (D layer), which can be produced through the above steps. The copper-clad laminate film includes a heat-resistant resin layer (C layer) and a copper foil (D layer) by forming a thermosetting resin composition into one layer on the copper-clad laminate film. The copper-clad laminate film may be a cast type two-layer CCL (copper-plated laminate), a sputtering type two-layer CCL, a laminated type two-layer CCL, a three-layer CCL, or the like. The thickness of the copper foil is preferably 12 μm or 18 μm.

商購二層CCL之實施例包括ESPANEX SC(可購自Nippon Steel Chemical公司)，NEOFLEX I<CM>及NEOFLEX I<LM>(可購自Mitsui Chemicals公司)，S'PERFLEX(可購自Sumitomo Metal Mining Co.,Ltd)及其類似者，且商購三層CCL之實施例包括NIKAFLEX F-50VC1(可購自Nikkan Industries公司)及其類似者。Examples of commercially available two-layer CCL include ESPANEX SC (available from Nippon Steel Chemical), NEOFLEX I <CM> and NEOFLEX I <LM> (available from Mitsui Chemicals), S'PERFLEX (available from Sumitomo Metal) Mining Co., Ltd. and the like, and examples of commercially available three-layer CCLs include NIKAFLEX F-50VC1 (available from Nikkan Industries, Inc.) and the like.

針對雙面可撓性電路板之膜的基膜，其中包含絕緣層(A’層)的三層、耐熱性樹脂層(C層)、及絕緣層(A’ 層)，可由如下方式製作。首先，在一製作上述膠黏劑膜的類似方法之中，將本發明熱固性樹脂組成物溶在有機溶劑之中以製備樹脂清漆。將樹脂清漆施用於支撐膜，且經由加熱或熱空氣吹風將有機溶劑乾燥以形成熱固性樹脂組成物層。有機溶劑、乾燥條件及其類似者相似於那些製作上述膠黏劑膜者。熱固性樹脂組成物層厚度的較佳範圍在5至15μm。A base film for a film of a double-sided flexible circuit board, comprising three layers of an insulating layer (A' layer), a heat resistant resin layer (C layer), and an insulating layer (A' Layer) can be made as follows. First, among the similar methods of producing the above adhesive film, the thermosetting resin composition of the present invention is dissolved in an organic solvent to prepare a resin varnish. The resin varnish is applied to the support film, and the organic solvent is dried via heating or hot air blowing to form a thermosetting resin composition layer. Organic solvents, drying conditions and the like are similar to those used to make the above adhesive films. The thickness of the thermosetting resin composition layer is preferably in the range of 5 to 15 μm.

然後，將所得到的膠黏劑膜分別地層合在耐熱性樹脂膜的兩面。層合條件相似於那些上述者。當熱固性樹脂組成物層預先形成在之上耐熱性膜的一面上，膠黏劑膜可以僅層合至另一表面。隨後，將各熱固性樹脂組成物層熱硬化以形成的絕緣層熱固性樹脂組成物之硬化材料。一般而言，熱硬化條件係選在150至220℃之溫度範圍，時間為20至180分鐘，且更佳係選在160至200℃之溫度範圍，時間為30至120分鐘。Then, the obtained adhesive films were separately laminated on both surfaces of the heat resistant resin film. The lamination conditions are similar to those described above. When the thermosetting resin composition layer is previously formed on one side of the upper heat resistant film, the adhesive film may be laminated only to the other surface. Subsequently, each thermosetting resin composition layer is thermally hardened to form a hardened material of the insulating layer thermosetting resin composition. In general, the thermosetting conditions are selected from a temperature range of from 150 to 220 ° C for a period of from 20 to 180 minutes, and more preferably from 160 to 200 ° C for a period of from 30 to 120 minutes.

如下將記述由用於可撓性電路板的基膜生產可撓性電路板的方法。針對內含A’層、C層、及A’層的基膜，於熱硬化之後，首先，經由鑽機、雷射、電漿或其類似者在電路板之中形成導孔，以達成介於兩面之間的傳導。針對內含A’層、C層、及D層的基膜，經由相似的方法在電路板中形成導孔。特別地，一般可用雷射如二氧化碳氣體雷射或YAG雷射，以形成孔。A method of producing a flexible circuit board from a base film for a flexible circuit board will be described as follows. For the base film containing the A' layer, the C layer, and the A' layer, after the heat hardening, first, a via hole is formed in the circuit board through a drill, a laser, a plasma, or the like to achieve Conduction between the two sides. A via hole is formed in the circuit board by a similar method for the base film containing the A' layer, the C layer, and the D layer. In particular, a laser such as a carbon dioxide gas laser or a YAG laser can be generally used to form a hole.

然後，將絕緣層，即熱固性樹脂組成物之硬化材料作表面處理。絕緣層的表面處理可相似於那些針對如上述膠黏劑膜所用者。於進行表面處理之後，在絕緣層之表面上電鍍以形成導體層。經由電鍍之方法形成導體可在類似於膠黏劑膜的方法之中進行。於形成導體層之後，可經由將此層於150至200℃之溫度退火20至90分鐘而進一步改良且穩定導體層之剝離強度。Then, the insulating layer, that is, the hardening material of the thermosetting resin composition is surface-treated. The surface treatment of the insulating layer can be similar to those used for the adhesive film as described above. After the surface treatment, electroplating is performed on the surface of the insulating layer to form a conductor layer. Forming the conductor by electroplating can be carried out in a method similar to an adhesive film. After the formation of the conductor layer, the peel strength of the conductor layer can be further improved and stabilized by annealing the layer at a temperature of 150 to 200 ° C for 20 to 90 minutes.

隨後，將導體層作圖案化加工以形成電路，從而得到可撓性電路板。當使用內含A層、C層、及D層的基膜，也將銅箔的D層形成電路。可用例如減去方法，半添加方法或已知於一位熟悉此技藝的專業人士的類似方法，以達成形成各電路。其細節相同於那些針對上述膠黏劑膜者。Subsequently, the conductor layer is patterned to form an electric circuit, thereby obtaining a flexible circuit board. When the base film containing the A layer, the C layer, and the D layer is used, the D layer of the copper foil is also formed into a circuit. A circuit, for example, a subtractive method, a semi-additive method, or a similar method known to a person skilled in the art can be used to achieve the formation of the circuits. The details are the same as those for the above adhesive film.

使用如上本發明的述膠黏劑膜，例如經由與如此得到單或雙面可撓性電路板形成多層，可製作多層可撓性電路板。The multilayer flexible circuit board can be produced by using the above-described adhesive film of the present invention, for example, by forming a single layer or a double-sided flexible circuit board in this manner.

本發明熱固性樹脂組成物也可用作形成介於半導體與基材板之間應力舒張層之材料(參見JP－A－2000336271)。例如，可經由使用本發明的膠黏劑膜，採用上述方法的類似方法，形成所有或部分的在基材板最上方絕緣層，且可將半導體連接於其中，而製作內含半導體與(和熱固性樹脂組成物之硬化材料黏合的)基材板的半導體裝置。在此案例中，膠黏劑膜的熱固性樹脂組成物層的厚度範圍可在10至1000μm，隨意選擇的。在本發明熱固性樹脂組成物上電鍍可形成導體層。如此，可容易地經由也在基材板上提供應力舒張的絕緣層上作電鍍及圖案化的電路而形成導體層。The thermosetting resin composition of the present invention can also be used as a material for forming a stress relaxation layer between a semiconductor and a substrate sheet (see JP-A-2000336271). For example, by using the adhesive film of the present invention, all or part of the insulating layer at the top of the substrate sheet can be formed by a similar method as described above, and a semiconductor can be bonded thereto to fabricate an inclusive semiconductor and (and A semiconductor device of a substrate sheet to which a hardening material of a thermosetting resin composition is bonded. In this case, the thickness of the thermosetting resin composition layer of the adhesive film may be in the range of 10 to 1000 μm, which is arbitrarily selected. Electroplating on the thermosetting resin composition of the present invention can form a conductor layer. Thus, the conductor layer can be easily formed by a circuit that is plated and patterned on the insulating layer that also provides stress relaxation on the substrate board.

於以下舉例的具體其實施例之敘述中，本發明的其它特徵將變得明顯的，在此係本發明的說明且不應作為其限制。Other features of the invention will be apparent from the following description of the preferred embodiments of the invention.

實施例Example

在以下實施例中，術語“份”意指重量份。In the following examples, the term "parts" means parts by weight.

製備實施例1. 生產改質線型聚醯亞胺樹脂(改質線型聚醯亞胺樹脂清漆A)。Preparation Example 1. Production of a modified linear polyimine resin (modified linear polyimine resin varnish A).

在一反應容器之中，將50 g的G－3000(一種末端二元羥化的聚丁二烯，數目平均分子量＝5047(GPC方法)，羥基當量＝1798 g/eq.，固含量＝100重量%，可購自Nippon Soda公司)；23.5 g的IPUSOL 150(芳族烴為主的混合溶劑，可購自Idemitsu Petrochemical公司)；及0.005 g的二丁基錫月桂酸鹽均勻地混合且溶解。將此均勻混合物加熱至50℃，且將4.8 g的甲苯－2,4－二異氰酸酯(異氰酸酯當量＝87.08 g/eq.)加入其中，且於攪拌下將生成的混合物反應大約3小時。隨後將反應混合物冷卻至室溫，於其中加入8.96 g的苯甲酮四羧基二酐(酸酐當量＝161.1 g/eq.)、0.07g的三乙二胺、及40.4 g的乙基二甘醇乙酸酯(可購自Daicel Chemical Industries公司)。將於攪拌中將所生成的混合物加熱至130℃且反應大約4小時。經由FT－IR觀察到在2250 cm^{－ 1} 的NCO吸收峰消失。滿確定NCO吸收峰消失且如此考量反應完成，將反應混合物冷卻至室溫且使用100篩孔的濾膜布過濾以得到改質線型聚醯亞胺樹脂(改質線型聚醯亞胺樹脂清漆A)。In a reaction vessel, 50 g of G-3000 (a terminally hydroxylated polybutadiene, number average molecular weight = 5047 (GPC method), hydroxyl equivalent = 1798 g / eq., solid content = 100 % by weight, available from Nippon Soda Corporation; 23.5 g of IPUSOL 150 (aromatic hydrocarbon-based mixed solvent available from Idemitsu Petrochemical); and 0.005 g of dibutyltin laurate are uniformly mixed and dissolved. This homogeneous mixture was heated to 50 ° C, and 4.8 g of toluene-2,4-diisocyanate (isocyanate equivalent = 87.08 g/eq.) was added thereto, and the resulting mixture was reacted under stirring for about 3 hours. The reaction mixture was then cooled to room temperature, to which 8.96 g of benzophenone tetracarboxy dianhydride (anhydride equivalent = 161.1 g/eq.), 0.07 g of triethylenediamine, and 40.4 g of ethyl diglycol were added. Acetate (available from Daicel Chemical Industries, Inc.). The resulting mixture was heated to 130 ° C with stirring and reacted for about 4 hours. By FT-IR was observed in the 2250 cm ^- NCO ¹ absorption peak disappeared. After confirming that the NCO absorption peak disappeared and the reaction was completed as described above, the reaction mixture was cooled to room temperature and filtered using a 100-mesh filter cloth to obtain a modified linear polyimine resin (modified linear polyimine resin varnish A) ).

改質線型聚醯亞胺樹脂清漆之性質A：黏度＝7.5 Pa．s(25℃，E型黏度計)酸數目＝16.9 mgKOH/g固含量＝50重量%數目平均分子量＝13723聚丁二烯結構部分的含量＝50 * 100/(50＋4.8＋8.96)＝78.4重量%Properties of modified linear polyimine resin varnish A: viscosity = 7.5 Pa. s (25 ° C, E-type viscometer) number of acids = 16.9 mg KOH / g solid content = 50% by weight number average molecular weight = 13723 polybutadiene structural part content = 50 * 100 / (50 + 4.8 + 8.96) = 78.4 weight%

製備實施例2. 生產改質線型聚醯亞胺樹脂(改質線型聚醯亞胺樹脂清漆B)。Preparation Example 2. Production of a modified linear polyimine resin (modified linear polyimine resin varnish B).

在一反應容器之中，將50 g的G－3000(一種末端二元羥化的聚丁二烯，數目平均分子量＝5047(GPC方法)，羥基當量＝1798 g/eq.，固含量＝100重量%，可購自Nippon Soda公司)；23.5 g的IPUSOL 150(芳族烴為主的混合溶劑，可購自Idemitsu Petrochemical公司)；及0.007 g的月桂酸二丁基錫均勻地混合且溶解。將此均勻混合物加熱至50℃，且將4.8 g的甲苯－2,4－二異氰酸酯(異氰酸酯當量＝87.08 g/eq.)加入其中，且於攪拌下將生成的混合物反應大約3小時。隨後將反應混合物冷卻至室溫，於其中加入8.83 g的苯甲酮四羧基二酐(酸酐當量＝161.1 g/eq.)、0.07 g的三乙二胺、及74.09 g的乙基二甘醇乙酸酯(可購自Daicel Chemical Industries公司)。於攪拌中將所生成的混合物加熱至130℃且反應大約4小時。當經由FT－TR確定在2250 cm^{－ 1} 的NCO吸收峰消失，可進一步將1.43 g的甲苯－2,4－二異氰酸酯(異氰酸酯當量＝87.08 g/eq.)加入混合物中，且將混合物攪拌而允許再一次於130℃反應2至6小時，經由FT－IR觀察NCO吸收峰的消失。當確定NCO吸收峰消失，考量反應完成，且將反應混合物冷卻至室溫且使用100篩孔的濾膜布過濾以得到改質聚醯亞胺樹脂(改質線型聚醯亞胺樹脂清漆B)。In a reaction vessel, 50 g of G-3000 (a terminally hydroxylated polybutadiene, number average molecular weight = 5047 (GPC method), hydroxyl equivalent = 1798 g / eq., solid content = 100 % by weight, available from Nippon Soda Corporation; 23.5 g of IPUSOL 150 (aromatic hydrocarbon-based mixed solvent available from Idemitsu Petrochemical); and 0.007 g of dibutyltin laurate uniformly mixed and dissolved. This homogeneous mixture was heated to 50 ° C, and 4.8 g of toluene-2,4-diisocyanate (isocyanate equivalent = 87.08 g/eq.) was added thereto, and the resulting mixture was reacted under stirring for about 3 hours. The reaction mixture was then cooled to room temperature, to which 8.83 g of benzophenone tetracarboxy dianhydride (anhydride equivalent = 161.1 g/eq.), 0.07 g of triethylenediamine, and 74.09 g of ethyl diglycol were added. Acetate (available from Daicel Chemical Industries, Inc.). The resulting mixture was heated to 130 ° C with stirring and reacted for about 4 hours. When it is determined by FT-TR at 2250 cm ^- NCO ¹ absorption peak disappeared, may further 1.43 g of toluene-2,4-diisocyanate (isocyanate equivalent weight = 87.08 g / eq) added to the mixture, and the mixture was stirred and It was allowed to react again at 130 ° C for 2 to 6 hours, and the disappearance of the NCO absorption peak was observed by FT-IR. When it was confirmed that the NCO absorption peak disappeared, the reaction was completed, and the reaction mixture was cooled to room temperature and filtered using a 100-mesh filter cloth to obtain a modified polyimine resin (modified linear polyimide resin varnish B). .

改質線型聚醯亞胺樹脂清漆B之性質：黏度＝7.0 Pa．s(25℃，E型黏度計)酸數目＝6.9 mgKOH/g固含量＝40重量%數目平均分子量＝19890聚丁二烯結構部分的含量＝50 * 100/(50＋4.8＋8.83＋1.43)＝76.9重量%The properties of the modified linear polyimine resin varnish B: viscosity = 7.0 Pa. s (25 ° C, E-type viscometer) acid number = 6.9 mg KOH / g solid content = 40% by weight number average molecular weight = 19,908 polybutadiene structural portion content = 50 * 100 / (50 + 4.8 + 8.83 + 1.43) =76.9 wt%

實施例1.Example 1.

將40份的得自製備實施例1的改質線型聚醯亞胺樹脂清漆A之成分(A)、8份的雙酚A型環氧樹脂的成分(B)(環氧當量：185，“EPTKOTE 828”可購自Japan poxy Resins公司)、及6.5份的內含三嗪結構的酚酚醛清漆樹脂(“PHENOLITE LA－7054”可購自Dainippon Ink and Chemicals公司)之甲基乙基酮(以下稱為MEK)清漆相混合，以製備熱固性樹脂組成物的清漆。隨後經由壓模塗覆器將熱固性樹脂組成物施用到經離型處理的聚對酞酸乙二醇酯(以下稱為PET)(膜厚38μm)上使組成物於乾燥之後的樹脂厚度為70μpm。於80至120℃(平均100℃)將此施用的組成物乾燥6分鐘以形成熱固性樹脂組成物層，其中殘存的溶劑含量在大約1重量%，從而得到一種膠黏劑膜。然後將此膠黏劑膜纏繞成捲狀並在熱固性樹脂組成物層之表面黏合厚15μm的聚丙烯膜。將此捲膠黏劑膜切成507 mm之寬度，以得到薄片狀的膠黏劑膜，其尺寸為507 x 336 mm。40 parts of the component (A) of the modified linear polyimine resin varnish A obtained in Preparation Example 1, and the component (B) of 8 parts of the bisphenol A type epoxy resin (epoxy equivalent: 185, " EPTKOTE 828" is available from Japan poxy Resins Co., Ltd., and 6.5 parts of methyl ethyl ketone ("PHENOLITE LA-7054" commercially available from Dainippon Ink and Chemicals) containing a triazine structure. A varnish called MEK) is mixed to prepare a varnish of the thermosetting resin composition. Subsequently, the thermosetting resin composition was applied to a release-treated polyethylene terephthalate (hereinafter referred to as PET) (film thickness: 38 μm) via a die coater so that the thickness of the resin after drying of the composition was 70 μm. . This applied composition was dried at 80 to 120 ° C (average 100 ° C) for 6 minutes to form a thermosetting resin composition layer in which the residual solvent content was about 1% by weight, thereby obtaining an adhesive film. Then, the adhesive film was wound into a roll and a polypropylene film having a thickness of 15 μm was adhered to the surface of the thermosetting resin composition layer. The roll of the adhesive film was cut to a width of 507 mm to obtain a sheet-like adhesive film having a size of 507 x 336 mm.

實施例2.Example 2.

將40份的得自製備實施例1的改質線型聚醯亞胺樹脂清漆A之成分(A)、3份的雙酚A型環氧基松香之成分(B)(環氧當量：185，“EPIKOTE 828”可購自Japan poxy Resins公司)、9.1份的聯苯型環氧樹脂(環氧當量：290，“NC－3000－H”可購自Nippon Kayaku公司)、6.5份的內含三嗪結構的酚酚醛清漆樹脂(“PHENOLITE LA－7054”可購自Dainippon Ink and Chemicals公司)之MEK清漆、及3.9份的MEK相混合，以製備熱固性樹脂組成物的清漆。然後，採用如實施例1相同方法，經由壓模塗覆器將熱固性樹脂組成物施用於經離型處理處PET膜上，使組成物於乾燥之後的樹脂厚度為70μm。於80至120℃(平均100℃)將此施用的組成物乾燥6分鐘以形成熱固性樹脂組成物層，其中殘存的溶劑含量在大約1重量%，從而得到一種膠黏劑膜。然後將此膠黏劑膜纏繞成捲狀並在熱固性樹脂組成物層之表面黏合厚15μm的聚丙烯膜。將此捲膠黏劑膜切成507 mm之寬度，以得到薄片狀的膠黏劑膜，其尺寸為507 x 336 mm。40 parts of the component (A) of the modified linear polyimine resin varnish A obtained in Preparation Example 1, and 3 parts of the component (B) of bisphenol A type epoxy rosin (epoxy equivalent: 185, "EPIKOTE 828" available from Japan poxy Resins), 9.1 parts of biphenyl type epoxy resin (epoxy equivalent: 290, "NC-3000-H" available from Nippon Kayaku), 6.5 parts containing three A phenol novolac resin ("PHENOLITE LA-7054" available from Dainippon Ink and Chemicals) of MEX varnish and 3.9 parts of MEK were mixed to prepare a varnish of the thermosetting resin composition. Then, the thermosetting resin composition was applied to the PET film at the release treatment by a die coater in the same manner as in Example 1, and the thickness of the resin after drying of the composition was 70 μm. This applied composition was dried at 80 to 120 ° C (average 100 ° C) for 6 minutes to form a thermosetting resin composition layer in which the residual solvent content was about 1% by weight, thereby obtaining an adhesive film. Then, the adhesive film was wound into a roll and a polypropylene film having a thickness of 15 μm was adhered to the surface of the thermosetting resin composition layer. The roll of the adhesive film was cut to a width of 507 mm to obtain a sheet-like adhesive film having a size of 507 x 336 mm.

實施例3.Example 3.

將40份的得自製備實施例1的改質線型聚醯亞胺樹脂清漆A之成分(A)、4份的雙酚A型環氧樹脂的成分(B)(環氧當量：185，“EPIKOTB 828”可購自Japan poxy Resins公司)、4.5份的四甲基型，雙酚型環氧樹脂(環氧當量：190，“YX－4000”可購自Japan poxy Resins公司)、及6.5份的內含三嗪結構的酚酚醛清漆樹脂(“PHENOLITE LA－7054”可購自Dainippon Ink and Chemicals公司)之MBK清漆相混合，以製備熱固性樹脂組成物的清漆。然後，採用如實施例1相同方法，經由壓模塗覆器將熱固性樹脂組成物施用於經離型處理處PET膜上，使組成物於乾燥之後的樹脂厚度為70μm。於80至120℃(平均100℃)將此施用的組成物乾燥6分鐘以形成熱固性樹脂組成物層，其中殘存的溶劑含量在大約1重量%，從而得到一種膠黏劑膜。然後將此膠黏劑膜纏繞成捲狀並在熱固性樹脂組成物層之表面黏合厚15μm的聚丙烯膜。將此捲膠黏劑膜切成507 mm之寬度，以得到薄片狀的膠黏劑膜，其尺寸為507 x 336 mm。40 parts of the component (A) of the modified linear polyimine resin varnish A obtained in Preparation Example 1, and the component (B) of 4 parts of the bisphenol A type epoxy resin (epoxy equivalent: 185, " EPIKOTB 828" is available from Japan poxy Resins), 4.5 parts of tetramethyl type, bisphenol type epoxy resin (epoxy equivalent: 190, "YX-4000" available from Japan poxy Resins), and 6.5 parts The MBK varnish containing a triazine structure-containing phenol novolac resin ("PHENOLITE LA-7054" available from Dainippon Ink and Chemicals Co., Ltd.) was mixed to prepare a varnish of the thermosetting resin composition. Then, the thermosetting resin composition was applied to the PET film at the release treatment by a die coater in the same manner as in Example 1, and the thickness of the resin after drying of the composition was 70 μm. This applied composition was dried at 80 to 120 ° C (average 100 ° C) for 6 minutes to form a thermosetting resin composition layer in which the residual solvent content was about 1% by weight, thereby obtaining an adhesive film. Then, the adhesive film was wound into a roll and a polypropylene film having a thickness of 15 μm was adhered to the surface of the thermosetting resin composition layer. The roll of the adhesive film was cut to a width of 507 mm to obtain a sheet-like adhesive film having a size of 507 x 336 mm.

實施例4.Example 4.

將40份的得自製備實施例1的改質線型聚醯亞胺樹脂清漆A之成分(A)、4份的雙酚A型環氧樹脂的成分(B)(環氧當量185，“EPIKOTE 828”，可購自Japan poxy Resins公司)、4份的苯基甲烷類型多官能基環氧樹脂(環氧當量：170，“EPPN－502H”，可購自Nippon Kayaku公司)、6.5份的內含三嗪結構的酚酚醛清漆樹脂(“PHENOLITE LA－7054”，可購自Dainippon Ink and Chemicals公司)之MEK清漆、及1份的MEK相混合，以製備熱固性樹脂組成物。然後，採用如實施例1相同方法，經由壓模塗覆器將熱固性樹脂組成物施用於經離型處理處PET膜上，使組成物於乾燥之後的樹脂厚度為70μm。於80至120℃(平均100℃)將此施用的組成物乾燥6分鐘以形成熱固性樹脂組成物層，其中殘存的溶劑含量在大約1重量%，從而得到一種膠黏劑膜。然後將此膠黏劑膜纏繞成捲狀並在熱固性樹脂組成物層之表面黏合厚15μm的聚丙烯膜。將此捲膠黏劑膜切成507 mm之寬度，以得到薄片狀的膠黏劑膜，其尺寸為507 x 336 mm。40 parts of the component (A) of the modified linear polyimine resin varnish A obtained in Preparation Example 1, and the component (B) of 4 parts of the bisphenol A type epoxy resin (epoxy equivalent 185, "EPIKOTE 828", available from Japan poxy Resins), 4 parts of phenylmethane type polyfunctional epoxy resin (epoxy equivalent: 170, "EPPN-502H", available from Nippon Kayaku), 6.5 parts A MEK varnish containing a triazine structure-containing phenol novolak resin ("PHENOLITE LA-7054", available from Dainippon Ink and Chemicals), and 1 part of MEK were mixed to prepare a thermosetting resin composition. Then, the thermosetting resin composition was applied to the PET film at the release treatment by a die coater in the same manner as in Example 1, and the thickness of the resin after drying of the composition was 70 μm. This applied composition was dried at 80 to 120 ° C (average 100 ° C) for 6 minutes to form a thermosetting resin composition layer in which the residual solvent content was about 1% by weight, thereby obtaining an adhesive film. Then, the adhesive film was wound into a roll and a polypropylene film having a thickness of 15 μm was adhered to the surface of the thermosetting resin composition layer. The roll of the adhesive film was cut to a width of 507 mm to obtain a sheet-like adhesive film having a size of 507 x 336 mm.

實施例5.Example 5.

將40份的得自製備實施例1的改質線型聚醯亞胺樹脂清漆A之成分(A)、8份的雙酚A型環氧樹脂的成分(B)(環氧當量185，“EPIKOTE 828”可購自Japan poxy Resins公司)、6.5份的內含三嗪結構的酚酚醛清漆樹脂(“PHENOLITE LA－7054”可購自Dainippon Ink and Chemicals公司)之MEK清漆、8份的球形二氧化矽(平均粒徑：1.1 pm)、及4份的IPUSOL 150(芳族烴為主的混合溶劑，可購自Idemitsu Petrochemical公司)相混合，以製備熱固性樹脂組成物。然後，採用如實施例1相同方法，經由壓模塗覆器將熱固性樹脂組成物施用於經離型處理處PET膜上，使組成物於乾燥之後的樹脂厚度為70μm。於80至120℃(平均100℃)將此施用的組成物乾燥6分鐘以形成熱固性樹脂組成物層，其中殘存的溶劑含量在大約1重量%，從而得到一種膠黏劑膜。然後將此膠黏劑膜纏繞成捲狀並在熱固性樹脂組成物層之表面黏合厚15μm的聚丙烯膜。將此捲膠黏劑膜切成507 mm之寬度，以得到薄片狀的膠黏劑膜，其尺寸為507 x 336 mm。40 parts of the component (A) of the modified linear polyimine resin varnish A obtained in Preparation Example 1, and 8 parts of the bisphenol A type epoxy resin (B) (epoxy equivalent 185, "EPIKOTE 828" available from Japan poxy Resins Co., Ltd., 6.5 parts of phenol novolac resin containing "triazine structure" ("PHENOLITE LA-7054" available from Dainippon Ink and Chemicals), 8 parts of spherical dioxide矽 (average particle diameter: 1.1 pm), and 4 parts of IPUSOL 150 (aromatic hydrocarbon-based mixed solvent, available from Idemitsu Petrochemical Co., Ltd.) were mixed to prepare a thermosetting resin composition. Then, the thermosetting resin composition was applied to the PET film at the release treatment by a die coater in the same manner as in Example 1, and the thickness of the resin after drying of the composition was 70 μm. This applied composition was dried at 80 to 120 ° C (average 100 ° C) for 6 minutes to form a thermosetting resin composition layer in which the residual solvent content was about 1% by weight, thereby obtaining an adhesive film. Then, the adhesive film was wound into a roll and a polypropylene film having a thickness of 15 μm was adhered to the surface of the thermosetting resin composition layer. The roll of the adhesive film was cut to a width of 507 mm to obtain a sheet-like adhesive film having a size of 507 x 336 mm.

實施例6.Example 6.

將40份的得自製備實施例1的改質線型聚醯亞胺樹脂清漆A之成分(A)、8份的雙酚A型環氧樹脂的成分(B)(環氧當量：185，“EPIKOTE 828”可購自Japan poxy Resins公司)；0.5份的咪唑為主的硬化劑(2,4－二胺基－6－[2'－甲基咪唑基－(1')]－乙基－s－三嗪異氰尿酸加合物“CUREZOL 2MA－OK”可購自Shikoku Corporation)、10份的球形二氧化矽(平均粒徑：1.1μm)、及4份的“1PUSOL 150”(芳族烴為主的混合溶劑，可購自Idemitsu Petrochemical公司)相混合，以製備熱固性樹脂組成物。然後，採用如實施例1相同方法，經由壓模塗覆器將熱固性樹脂組成物施用於經離型處理處PET膜上，使組成物於乾燥之後的樹脂厚度為70μm。於80至120℃(平均100℃)將此施用的組成物乾燥6分鐘以形成熱固性樹脂組成物層，其中殘存的溶劑含量在大約1重量%，從而得到一種膠黏劑膜。然後將此膠黏劑膜纏繞成捲狀並在熱固性樹脂組成物層之表面黏合厚15μm的聚丙烯膜。將此捲膠黏劑膜切成507 mm之寬度，以得到薄片狀的膠黏劑膜，其尺寸為507 x 336 mm。40 parts of the component (A) of the modified linear polyimine resin varnish A obtained in Preparation Example 1, and the component (B) of 8 parts of the bisphenol A type epoxy resin (epoxy equivalent: 185, " EPIKOTE 828" is available from Japan poxy Resins); 0.5 part of an imidazole-based hardener (2,4-diamino-6-[2'-methylimidazolyl-(1')]-ethyl- S-triazine isocyanuric acid adduct "CUREZOL 2MA-OK" available from Shikoku Corporation), 10 parts of spherical ceria (average particle size: 1.1 μm), and 4 parts of "1PUSOL 150" (aromatic A hydrocarbon-based mixed solvent, available from Idemitsu Petrochemical Co., Ltd., was mixed to prepare a thermosetting resin composition. Then, the thermosetting resin composition was applied to the PET film at the release treatment by a die coater in the same manner as in Example 1, and the thickness of the resin after drying of the composition was 70 μm. This applied composition was dried at 80 to 120 ° C (average 100 ° C) for 6 minutes to form a thermosetting resin composition layer in which the residual solvent content was about 1% by weight, thereby obtaining an adhesive film. Then, the adhesive film was wound into a roll and a polypropylene film having a thickness of 15 μm was adhered to the surface of the thermosetting resin composition layer. The roll of the adhesive film was cut to a width of 507 mm to obtain a sheet-like adhesive film having a size of 507 x 336 mm.

實施例7.Example 7.

將40份的得自製備實施例1的改質線型聚醯亞胺樹脂清漆A之成分(A)、8份的雙酚A型環氧樹脂的成分(B)(環氧當量：185，“EPIKOTE 828”可購自Japan poxy Resins公司)、0.5份的二聚胺基氰(“EPLKURE DICY7”可購自Japan poxy Resins公司)、10份的球形二氧化矽(平均粒徑：1.1μm)、及4份的IPUSOL 150(芳族烴為主的混合溶劑，可購自Idemitsu Petrochemical公司)相混合，以製備熱固性樹脂組成物。然後，採用如實施例1相同方法，經由壓模塗覆器將熱固性樹脂組成物施用於經離型處理處PET膜上，使組成物於乾燥之後的樹脂厚度為70μm。於80至120℃(平均100℃)將此施用的組成物乾燥6分鐘以形成熟固性樹脂組成物層，其中殘存的溶劑含量在大約1重量%，從而得到一種膠黏劑膜。然後將此膠黏劑膜纏繞成捲狀並在熱固性樹脂組成物層之表面黏合厚15μm的聚丙烯膜。將此捲膠黏劑膜切成507 mm之寬度，以得到薄片狀的膠黏劑膜，其尺寸為507 x 336 mm。40 parts of the component (A) of the modified linear polyimine resin varnish A obtained in Preparation Example 1, and the component (B) of 8 parts of the bisphenol A type epoxy resin (epoxy equivalent: 185, " EPIKOTE 828" is available from Japan poxy Resins, 0.5 parts of dimeric amino cyanide ("EPLKURE DICY7" is available from Japan poxy Resins), 10 parts of spherical ceria (average particle size: 1.1 μm), And 4 parts of IPUSOL 150 (aromatic hydrocarbon-based mixed solvent available from Idemitsu Petrochemical Co., Ltd.) were mixed to prepare a thermosetting resin composition. Then, the thermosetting resin composition was applied to the PET film at the release treatment by a die coater in the same manner as in Example 1, and the thickness of the resin after drying of the composition was 70 μm. This applied composition was dried at 80 to 120 ° C (average 100 ° C) for 6 minutes to form a mature solid resin composition layer in which the residual solvent content was about 1% by weight, thereby obtaining an adhesive film. Then, the adhesive film was wound into a roll and a polypropylene film having a thickness of 15 μm was adhered to the surface of the thermosetting resin composition layer. The roll of the adhesive film was cut to a width of 507 mm to obtain a sheet-like adhesive film having a size of 507 x 336 mm.

於180℃分別將得自實施例1至7的膠黏劑膜作熱硬化90分鐘。各熱固性樹脂組成物之硬化材料之性質展示於表1。抗張斷裂強度測量係依據日本工業標準(JIS)K7127。使用可購自Agilent Technologies公司的E8362B，經由腔穴共振擾動方法評估介電性質。The adhesive films obtained in Examples 1 to 7 were each thermally hardened at 180 ° C for 90 minutes. The properties of the hardened material of each thermosetting resin composition are shown in Table 1. The tensile strength measurement is based on Japanese Industrial Standard (JIS) K7127. Dielectric properties were evaluated via cavity resonance perturbation methods using E8362B, available from Agilent Technologies.

比較例1.Comparative Example 1.

此外，於170℃將環氧樹脂之層間絕緣材料(ABF－SHcode9K可購自Ajinomoto Fine－Techno公司)熱硬化90分鐘，製作比較例1之硬化材料，且此硬化材料之性質也展示於表1。Further, an epoxy interlayer insulating material (ABF-SHcode9K available from Ajinomoto Fine-Techno Co., Ltd.) was thermally cured at 170 ° C for 90 minutes to prepare a hardened material of Comparative Example 1, and the properties of the hardened material are also shown in Table 1. .

實施例8.Example 8.

生產多層可撓性電路板(No.1)Production of multilayer flexible circuit boards (No.1)

將一種內含厚12μm的銅箔與厚25μm的聚醯亞胺膜之雙面二層CCL形成電路，以製備具有直徑0.2mm的導孔之電路板。於從各膠黏劑膜上剝離聚丙烯膜之後，將得自實施例1的膠黏劑膜層合在電路板兩面，使各自熱固性樹脂組成物層覆蓋電路。於以下條件之下使用由Meiki Co.,Ltd製作的真空層合器進行層合：130℃之溫度，壓力為7 kgf/cm² ，且在5mmHg或更低的氣壓下。然後，將經離型處理的PET膜剝離，於180℃將各熱固性樹脂組成物層熱硬化30分鐘以形成絕緣層，且經由雷射而形成導孔。絕緣層的表面處理方法伴隨著使用可購自Atotech Japan的以下試藥進行除污程序：氧化劑"Concentrate Compact CP"(一種鹼性的高錳酸鹽溶液)；及還原劑"Reduction Solution Securiganth P－500"。A double-sided two-layer CCL containing a copper foil having a thickness of 12 μm and a polyimide film having a thickness of 25 μm was formed into a circuit to prepare a circuit board having a via hole having a diameter of 0.2 mm. After the polypropylene film was peeled off from each of the adhesive films, the adhesive film obtained in Example 1 was laminated on both sides of the circuit board so that the respective thermosetting resin composition layers covered the circuit. Lamination was carried out using a vacuum laminate manufactured by Meiki Co., Ltd. under the following conditions: a temperature of 130 ° C, a pressure of 7 kgf / cm ² , and a pressure of 5 mmHg or less. Then, the release-treated PET film was peeled off, and each thermosetting resin composition layer was thermally cured at 180 ° C for 30 minutes to form an insulating layer, and via holes were formed via laser. The surface treatment method of the insulating layer is accompanied by the following decontamination procedure using the following reagents available from Atotech Japan: oxidant "Concentrate Compact CP" (an alkaline permanganate solution); and reducing agent "Reduction Solution Securiganth P- 500".

使用氧化劑溶液於80℃將此絕緣層作表面作處理10分鐘，且然後使用此還原劑溶液於40℃作中和處理5分鐘。然後，將無電銅電鍍觸媒加入絕緣層之表面，且於32℃將生成的產物浸泡在無電銅電鍍液體之中30分鐘，以形成厚1.5μm的無電銅膜。於150℃將此乾燥30分鐘，做酸洗，且使用磷化銅板陽極做電鍍銅，採用陰極電流密度2.0 A/dm² ，電鍍12分鐘，以形成銅電鍍膜。之後，於180℃可進一步將其退火30分鐘。如此得到的導體層之剝離強度為1.2 kgf/cm，其測量係依據JIS C6481，且導體電鍍的厚度在約30μm。This insulating layer was treated with an oxidizing agent solution at 80 ° C for 10 minutes, and then neutralized using this reducing agent solution at 40 ° C for 5 minutes. Then, an electroless copper plating catalyst was added to the surface of the insulating layer, and the resulting product was immersed in an electroless copper plating liquid at 32 ° C for 30 minutes to form an electroless copper film having a thickness of 1.5 μm. This was dried at 150 ° C for 30 minutes, acid-washed, and electroplated copper was used using a copper phosphide plate anode, and a cathode current density of 2.0 A/dm ^{2 was applied} for 12 minutes to form a copper plating film. Thereafter, it was further annealed at 180 ° C for 30 minutes. The conductor layer thus obtained had a peel strength of 1.2 kgf/cm, which was measured in accordance with JIS C6481, and the thickness of the conductor plating was about 30 μm.

實施例9.Example 9.

生產多層可撓性電路板(No.2)採用如實施例8相同方法，使用得自實施例5的膠黏劑膜，製作四層印刷電路板。如此得到導體層之剝離強度為0.8 kgf/cm。Production of Multilayer Flexible Circuit Board (No. 2) A four-layer printed circuit board was produced by the same method as in Example 8 using the adhesive film obtained in Example 5. The peel strength of the conductor layer thus obtained was 0.8 kgf/cm.

實施例10.Example 10.

生產多層可撓性電路板(No.3)採用如實施例8相同方法，使用得自實施例6的膠黏劑膜，製作四層印刷電路板。如此得到導體層之剝離強度為1.0 kgf/cm。Production of Multilayer Flexible Circuit Board (No. 3) A four-layer printed circuit board was produced by the same method as in Example 8 using the adhesive film obtained in Example 6. The peel strength of the conductor layer thus obtained was 1.0 kgf/cm.

實施例11.Example 11.

生產多層可撓性電路板(No.4)採用如實施例8相同方法，使用得自實施例7的膠黏劑膜，製作四層印刷電路板。如此得到導體層之剝離強度為0.9 kgf/cm。Production of Multilayer Flexible Circuit Board (No. 4) A four-layer printed circuit board was produced by the same method as in Example 8 using the adhesive film obtained in Example 7. The peel strength of the conductor layer thus obtained was 0.9 kgf/cm.

實施例12.Example 12.

生產單面可撓性電路板經由壓模塗覆器，將實施例5中敘述的熱固性樹脂組成物清漆施用於聚醯亞胺膜(25μm)上，使乾燥之後的樹脂厚度為10μm，且在80至120℃(平均100℃)乾燥6分鐘以形成熟固性樹脂組成物層，其中殘存的溶劑含量在大約1重量%，從而製備基膜。然後將基膜纏繞成捲狀並在熱固性樹脂組成物層之表面黏合厚15μm的聚丙烯膜。將此捲基膜切成507 mm之寬度，以得到薄片狀的膠黏劑膜，其尺寸為507 x 336 mm。其後，從基膜上剝離聚丙烯膜，且於180℃將基膜熱硬化30分鐘以得到用於可撓性電路板的薄膜。然後，於如同實施例8相同條件之下將樹脂層作表面處理，作無電鍍層，且作電鍍層，以得到單面可撓性電路板。之後，此可進一步於180℃退火30分鐘。如此得到導體層之剝離強度為0.8 kgf/cm，其測量係依據JIS C6481，且導體電鍍的厚度在約30μm。The single-sided flexible circuit board was produced by applying the thermosetting resin composition varnish described in Example 5 to a polyimide film (25 μm) via a die coater so that the thickness of the resin after drying was 10 μm, and The film was dried at 80 to 120 ° C (average 100 ° C) for 6 minutes to form a mature solid resin composition layer in which the residual solvent content was about 1% by weight to prepare a base film. Then, the base film was wound into a roll and a polypropylene film having a thickness of 15 μm was adhered to the surface of the thermosetting resin composition layer. The base film of this roll was cut to a width of 507 mm to obtain a sheet-like adhesive film having a size of 507 x 336 mm. Thereafter, the polypropylene film was peeled off from the base film, and the base film was thermally hardened at 180 ° C for 30 minutes to obtain a film for a flexible circuit board. Then, the resin layer was subjected to surface treatment under the same conditions as in Example 8 to obtain an electroless plating layer and as a plating layer to obtain a one-sided flexible circuit board. This can then be further annealed at 180 ° C for 30 minutes. The peel strength of the conductor layer thus obtained was 0.8 kgf/cm, the measurement was in accordance with JIS C6481, and the thickness of the conductor plating was about 30 μm.

實施例13.Example 13.

生產雙面可撓性電路板(No.1)經由壓模塗覆器，將實施例5中敘述的熱固性樹脂組成物清漆，施用於內含厚12μm銅箔與厚25μm聚醯亞胺膜的二層CCL聚醯亞胺的表面單面，使乾燥之後的樹脂厚度為10μm，且於80至120℃(平均100℃)乾燥6分鐘以形成熟固性樹脂組成物層，其中殘存的溶劑含量在大約1重量%。然後將生成的膜纏繞成捲狀並在熱固性樹脂組成物之表面黏合厚15μm的聚丙烯膜。將此捲基膜切成507 mm之寬度，以得到薄片狀的膠黏劑膜，其尺寸為507 x 336 mm。其後，從此薄片狀的膜上剝離聚丙烯膜，且於180℃將此膜熱硬化30分鐘以得到用於可撓性電路板的薄膜。然後，於如同實施例8相同條件之下將樹脂層作表面處理，作無電鍍層，且作電鍍層，以得到雙面可撓性電路板。之後，此可進一步於180℃退火30分鐘。如此得到導體層之剝離強度為0.8 kgf/cm，其測量係依據JIS C6481，且導體電鍍的厚度在約30μm。Production of a double-sided flexible circuit board (No. 1) The varnish of the thermosetting resin composition described in Example 5 was applied via a die coater to a copper foil having a thickness of 12 μm and a polyimide film having a thickness of 25 μm. The surface of the two-layer CCL polyimide is single-sided, the thickness of the resin after drying is 10 μm, and dried at 80 to 120 ° C (average 100 ° C) for 6 minutes to form a mature solid resin composition layer, wherein the residual solvent content At about 1% by weight. The resulting film was then wound into a roll and a polypropylene film having a thickness of 15 μm was adhered to the surface of the thermosetting resin composition. The base film of this roll was cut to a width of 507 mm to obtain a sheet-like adhesive film having a size of 507 x 336 mm. Thereafter, the polypropylene film was peeled off from the sheet-like film, and the film was thermally cured at 180 ° C for 30 minutes to obtain a film for a flexible wiring board. Then, the resin layer was subjected to surface treatment under the same conditions as in Example 8 to obtain an electroless plating layer and as a plating layer to obtain a double-sided flexible circuit board. This can then be further annealed at 180 ° C for 30 minutes. The peel strength of the conductor layer thus obtained was 0.8 kgf/cm, the measurement was in accordance with JIS C6481, and the thickness of the conductor plating was about 30 μm.

實施例14.Example 14.

生產雙面可撓性電路板(No.2)經由壓模塗覆器，將實施例5中敘述的熱固性樹脂組成物清漆施用在離型處理PET膜上，使乾燥之後的樹脂厚度為10μm，且於80至120℃(平均100℃)乾燥6分鐘以形成熱固性樹脂組成物層，其中殘存的溶劑含量在大約1%之重量，從而得到一種膠黏劑膜。然後將生成的膜纏繞成捲狀並在熱固性樹脂組成物之表面黏合厚15μm的聚丙烯膜。將此捲膠黏劑膜切成507 mm之寬度，以得到薄片狀的膠黏劑膜，其尺寸為507 x 336 mm。其後，於從各膠黏劑膜上剝離聚丙烯膜之後，將膠黏劑膜層合在厚25μm的聚醯亞胺膜之兩面。以下條件之下採用Meiki Co.,Ltd製作的真空層合器於進行層合：130℃之溫度，壓力在7 kgf/cm² ；且氣壓為5mmHg或更低。然後，將經離型處理PET膜剝離；且於180℃將熱固性樹脂組成物熱硬化30分鐘以得到用於可撓性電路板的薄膜。之後，經由以高錳酸鹽的鹼性氧化劑處理將硬化樹脂層的表面粗糙化，且作無電鍍層及電鍍層，以形成雙面可撓性電路板。之後，再於180℃退火30分鐘。如此得到導體層之剝離強度為0.8 kgf/cm，其測量係依據JIS C6481，且導體電鍍的厚度約30μm。The double-sided flexible circuit board (No. 2) was produced, and the thermosetting resin composition varnish described in Example 5 was applied onto the release-treated PET film via a die coater so that the thickness of the resin after drying was 10 μm. And drying at 80 to 120 ° C (average 100 ° C) for 6 minutes to form a thermosetting resin composition layer in which the residual solvent content is about 1% by weight, thereby obtaining an adhesive film. The resulting film was then wound into a roll and a polypropylene film having a thickness of 15 μm was adhered to the surface of the thermosetting resin composition. The roll of the adhesive film was cut to a width of 507 mm to obtain a sheet-like adhesive film having a size of 507 x 336 mm. Thereafter, after the polypropylene film was peeled off from each of the adhesive films, the adhesive film was laminated on both sides of a polyimide film having a thickness of 25 μm. A vacuum laminate manufactured by Meiki Co., Ltd. was used under the following conditions for lamination: a temperature of 130 ° C, a pressure of 7 kgf / cm ² ; and a gas pressure of 5 mmHg or less. Then, the release-treated PET film was peeled off; and the thermosetting resin composition was thermally hardened at 180 ° C for 30 minutes to obtain a film for a flexible circuit board. Thereafter, the surface of the hardened resin layer is roughened by treatment with an alkaline oxidizing agent of permanganate, and an electroless plating layer and a plating layer are formed to form a double-sided flexible circuit board. Thereafter, it was annealed at 180 ° C for 30 minutes. The peel strength of the conductor layer thus obtained was 0.8 kgf/cm, which was measured in accordance with JIS C6481, and the thickness of the conductor plating was about 30 μm.

比較例2.Comparative Example 2.

採用如實施例8相同方法，使用環氧樹脂(ABF-SHcode9K可購自Ajinomoto Fine-Techno公司)之層間絕緣材料，製作四層印刷電路板。絕緣層的表面處理方法伴隨著使用可購自Atotech Japan的以下試藥進行除污程序：膨潤劑"Swelling Dip Securiganth P"、氧化劑"Concentrate Compact CP"(鹼性的高錳酸鹽溶液)、及還原劑"Reduction Solution Securiganth P-500"。A four-layer printed circuit board was produced in the same manner as in Example 8 using an interlayer insulating material of an epoxy resin (ABF-SHcode 9K available from Ajinomoto Fine-Techno Co., Ltd.). The surface treatment method of the insulating layer is accompanied by a decontamination procedure using the following reagents available from Atotech Japan: a swelling agent "Swelling Dip Securiganth P", an oxidizing agent "Concentrate Compact CP" (alkaline permanganate solution), and Reducing agent "Reduction Solution Securiganth P-500".

於80℃使用膨潤劑溶液將絕緣層作表面處理5分鐘，然後使用氧化劑於80℃將此表面作處理10分鐘，且最後使用還原劑溶液於40℃作中和作處理5分鐘。如此得到導體層之剝離強度為1.0 kgf/cm。The insulating layer was surface treated with a swelling agent solution at 80 ° C for 5 minutes, and then the surface was treated with an oxidizing agent at 80 ° C for 10 minutes, and finally treated with a reducing agent solution at 40 ° C for 5 minutes. The peel strength of the conductor layer thus obtained was 1.0 kgf/cm.

絕緣層表面之評估。Evaluation of the surface of the insulation.

於使用氧化劑作表面處理之後，經由SEM觀察實施例8、9、10、及11、及比較例2的絕緣層表面。由SEM顯微觀察結果闡明，經由電鍍，在實施例8中導體層形成在平坦表面上，且在實施例9、10、及11、及比較例2中，導體層形成在粗糙化表面上。表2顯示經由非接觸表面粗糙計(WYKO NT3300，由Veeco Instruments公司製作)測量，使用氧化劑作表面處理之後的各絕緣層之表面粗糙度(Ra值)結果。After the surface treatment with an oxidizing agent, the surfaces of the insulating layers of Examples 8, 9, 10, and 11, and Comparative Example 2 were observed by SEM. The results of SEM microscopic observation revealed that the conductor layer was formed on the flat surface in Example 8 by electroplating, and in Examples 9, 10, and 11, and Comparative Example 2, the conductor layer was formed on the roughened surface. Table 2 shows the results of surface roughness (Ra value) of each insulating layer after surface treatment using an oxidizing agent as measured by a non-contact surface roughness meter (WYKO NT3300, manufactured by Veeco Instruments Co., Ltd.).

工業可應用性。Industrial applicability.

本發明熱固性樹脂組成物之硬化材料具有卓越的撓曲性、機械強度、及介電性質。此外，具有卓越黏著性的導體層可經由電鍍而輕易地形成在硬化材料表面上，從而使此硬化材料可適宜用作為用於可撓性電路板之絕緣材料，尤其是一種多層可撓性電路板。此外，甚至當其中硬化材料不具有不均勻的表面，可在其上形成具有高剝離強度的導體層。如此，本發明熱固性樹脂組成物可以適宜用於須要形成細微圖案電路的可撓性電路板。The hardening material of the thermosetting resin composition of the present invention has excellent flexibility, mechanical strength, and dielectric properties. In addition, the conductor layer having excellent adhesion can be easily formed on the surface of the hardened material by electroplating, so that the hardened material can be suitably used as an insulating material for a flexible circuit board, especially a multilayer flexible circuit. board. Further, even when the hardened material does not have a non-uniform surface, a conductor layer having high peel strength can be formed thereon. Thus, the thermosetting resin composition of the present invention can be suitably used for a flexible circuit board which requires formation of a fine pattern circuit.

明顯地，從上述教示可能有許多本發明的改良及變化。因此可瞭解，在附加的申請專利範圍之中，相較於如尤其在此記述者之外，可另外本發明實施。Obviously, many modifications and variations of the present invention are possible in light of the above teachings. It is therefore to be understood that within the scope of the appended claims, the invention may be practiced otherwise than as specifically described herein.

上述所有專利及其它參考文獻之全文在此併入本文為參考文獻，如同在其原文所述般。All of the above-identified patents and other references are hereby incorporated by reference herein in its entirety in its entirety in its entirety.

當考量配合伴隨的圖式，經由參考以下詳細的描述，將可以輕易地更完全瞭解本發明且變得更瞭解許多伴隨的優點，其中：圖1為實施例8經表面處理的絕緣層表面的SEM顯微照片(放大1,000倍)；圖2為實施例9經表面處理的絕緣層表面的SEM顯微照片(放大1,000倍)；圖3為實施例10經表面處理的絕緣層表面的SEM顯微照片(放大1,000倍)；圖4為實施例11經表面處理的絕緣層表面的SEM顯微照片(放大1,000倍)；及圖5為比較例2經表面處理的絕緣層表面的SEM顯微照片(放大1,000倍)。The present invention will be readily more fully understood and will become more fully understood by reference to the accompanying drawings in the <RTIgt; SEM micrograph (magnification 1,000 times); FIG. 2 is an SEM micrograph (1000 magnifications) of the surface of the surface treated insulating layer of Example 9; FIG. 3 is an SEM display of the surface of the surface treated insulating layer of Example 10. Micrograph (1,000 magnifications); FIG. 4 is an SEM micrograph (1000 magnifications) of the surface of the surface treated insulating layer of Example 11; and FIG. 5 is an SEM micrograph of the surface of the surface treated insulating layer of Comparative Example 2. Photo (magnification 1,000 times).

Claims (28)

一種熱固性樹脂組成物，其包含：(A)至少一種將末端二元羥化的聚丁二烯、二異氰酸酯化合物、及四酸酐反應所得到的改質線型聚醯亞胺樹脂；與(B)至少一種由下列各者所組成族群中選出的熱固性樹脂：環氧樹脂、雙順丁烯二醯亞胺樹脂、氰酸酯樹脂、雙烯丙基-奈二-醯亞胺(bis-allyl-nadi-imide)樹脂、乙烯基苄基醚樹脂、苯並噁嗪樹脂、雙順丁烯二醯亞胺與二胺之聚合物、及其混合物。 A thermosetting resin composition comprising: (A) at least one modified linear polyimine resin obtained by reacting a terminally hydroxylated polybutadiene, a diisocyanate compound, and a tetraanhydride; and (B) At least one thermosetting resin selected from the group consisting of epoxy resin, bis-maleimide resin, cyanate resin, bis-allyl-imine (bis-allyl- Nadi-imide) a resin, a vinyl benzyl ether resin, a benzoxazine resin, a polymer of bis-synylene diimide and a diamine, and mixtures thereof. 如申請專利範圍第1項之熱固性樹脂組成物，其中該改質線型聚醯亞胺樹脂(A)為一種改質線型聚醯亞胺樹脂，其經由如下方式製得：將末端二元羥化的聚丁二烯與二異氰酸酯化合物反應，其中所採用的相對量係使該二異氰酸酯化合物上異氰酸酯基團對該末端二元羥化的聚丁二烯上羥基基團的官能基團當量比例大於1，以得到聚丁二烯二異氰酸酯組成物，及將該聚丁二烯二異氰酸酯組成物與一種四酸二酐反應。 The thermosetting resin composition of claim 1, wherein the modified linear polyimine resin (A) is a modified linear polyimine resin which is obtained by dihydroxylation of a terminal The polybutadiene is reacted with a diisocyanate compound in a relative amount such that the isocyanate group on the diisocyanate compound has a functional group equivalent ratio of the hydroxyl group on the terminally hydroxylated polybutadiene to be greater than 1, to obtain a polybutadiene diisocyanate composition, and to react the polybutadiene diisocyanate composition with a tetracarboxylic dianhydride. 如申請專利範圍第1項之熱固性樹脂組成物，其中該改質線型聚醯亞胺樹脂(A)為一種改質線型聚醯亞胺 樹脂，其經由如下方式製得：將末端二元羥化的聚丁二烯與二異氰酸酯化合物反應，其中所採用的相對量係使該二異氰酸酯化合物上異氰酸酯基團對該末端二元羥化的聚丁二烯上羥基基團的的官能基團當量比例為1：1.5至1：2.5，以得到聚丁二烯二異氰酸酯組成物，及將該聚丁二烯二異氰酸酯組成物與一種四酸二酐反應所得到。 The thermosetting resin composition of claim 1, wherein the modified linear polyimine resin (A) is a modified linear polyimine a resin obtained by reacting a terminally hydroxylated polybutadiene with a diisocyanate compound in a relative amount such that the isocyanate group on the diisocyanate compound is dihydroxylated to the terminal The functional group equivalent ratio of the hydroxyl group on the polybutadiene is 1:1.5 to 1:2.5 to obtain a polybutadiene diisocyanate composition, and the polybutadiene diisocyanate composition and a tetraacid The dianhydride reaction is obtained. 如申請專利範圍第1項之熱固性樹脂組成物，其中該改質線型聚醯亞胺樹脂(A)為一種改質線型聚醯亞胺樹脂，其經由如下方式製得：將末端二元羥化的聚丁二烯與二異氰酸酯化合物反應，其中所採用的相對量係使該二異氰酸酯化合物上異氰酸酯基團對該末端二元羥化的聚丁二烯上羥基基團的的官能基團當量比例為1：1.5至1：2.5，以得到聚丁二烯二異氰酸酯組成物，及將該聚丁二烯二異氰酸酯組成物與一種四酸二酐反應反應，其中所採用的比例係使起始材料二異氰酸酯化合物中異氰酸酯基團的官能基團當量X，起始材料末端二元羥化的聚丁二烯中羥基基團的官能基團當量W，及該四酸二酐中酸酐基團的官能基團當量Y，可滿足Y>X-W≧Y/5(W>0，X>0，Y>0)之關係。 The thermosetting resin composition of claim 1, wherein the modified linear polyimine resin (A) is a modified linear polyimine resin which is obtained by dihydroxylation of a terminal The polybutadiene is reacted with a diisocyanate compound, wherein the relative amount employed is the ratio of the functional group equivalent of the isocyanate group on the diisocyanate compound to the hydroxyl group on the terminally hydroxylated polybutadiene. a ratio of 1:1.5 to 1:2.5 to obtain a polybutadiene diisocyanate composition, and reacting the polybutadiene diisocyanate composition with a tetraacid dianhydride, wherein the ratio used is a starting material The functional group equivalent X of the isocyanate group in the diisocyanate compound, the functional group equivalent W of the hydroxyl group in the dihydroxylated polybutadiene at the terminal of the starting material, and the functionality of the anhydride group in the tetracarboxylic dianhydride The group equivalent Y can satisfy the relationship of Y>XW≧Y/5 (W>0, X>0, Y>0). 如申請專利範圍第1項之熱固性樹脂組成物，其中該改質線型聚醯亞胺樹脂(A)為進一步改質的線型聚醯亞胺樹脂，其經由如下方式製得：將末端二元羥化的聚丁二烯、第一種二異氰酸酯化合物、及四酸酐反應以得到改質線型聚醯亞胺樹脂，然後將該改質線型聚醯亞胺樹脂與 額外的異氰酸酯化合物反應，其中所採用的比例係使該第一種二異氰酸酯化合物中異氰酸酯基團的官能基團當量X，該末端二元羥化的聚丁二烯中羥基基團的官能基團當量W，該四酸二酐中酸酐基團的官能基團當量Y，及該額外的異氰酸酯化合物中異氰酸酯基團的官能基團當量Z，滿足Y-(X-W)>Z≧0(W>0，X>0，Y>0，Z>0)之關係。 The thermosetting resin composition of claim 1, wherein the modified linear polyimine resin (A) is a further modified linear polyimine resin, which is obtained by: terminal dihydroxyl The polybutadiene, the first diisocyanate compound, and the tetra-anhydride are reacted to obtain a modified linear polyimine resin, and then the modified linear polyimide resin is The additional isocyanate compound is reacted in a ratio such that the functional group equivalent of the isocyanate group in the first diisocyanate compound is X, and the functional group of the hydroxyl group in the terminally hydroxylated polybutadiene The equivalent weight W, the functional group equivalent Y of the acid anhydride group in the tetracarboxylic dianhydride, and the functional group equivalent Z of the isocyanate group in the additional isocyanate compound satisfy Y-(XW)>Z≧0 (W>0 , X>0, Y>0, Z>0) relationship. 一種熱固性樹脂組成物，其包含：(A)至少一種改質線型聚醯亞胺樹脂，其分子中具有由下式(1-a)代表的聚丁二烯結構及由下式(1-b)代表的聚醯亞胺結構： 其中R1代表經由從末端二元羥化的聚丁二烯上移除羥基基團所得到的殘基；R2代表經由從四酸二酐上移除酸酐基團所得到的殘基；及R3代表經由從二異氰酸酯化合物上移除異氰酸酯基團所得到的殘基，及(B)至少一種由下列各者所組成族群中選出的熱固性樹脂：環氧樹脂、雙順丁烯二醯亞胺樹脂、氰酸酯樹脂 、雙烯丙基-奈二-醯亞胺(bis-allyl-nadi-imide)樹脂、乙烯基苄基醚樹脂、苯並噁嗪樹脂、雙順丁烯二醯亞胺與二胺之聚合物、及其混合物。A thermosetting resin composition comprising: (A) at least one modified linear polyimine resin having a polybutadiene structure represented by the following formula (1-a) and having the following formula (1-b) ) represents the structure of polyimine: Wherein R1 represents a residue obtained by removing a hydroxyl group from a terminally hydroxylated polybutadiene; R2 represents a residue obtained by removing an acid anhydride group from a tetracarboxylic dianhydride; and R3 represents a residue obtained by removing an isocyanate group from a diisocyanate compound, and (B) at least one thermosetting resin selected from the group consisting of an epoxy resin, a bis-m-butylene iminoimide resin, Cyanate resin, bis-allyl-nadi-imide resin, vinyl benzyl ether resin, benzoxazine resin, bis-xetylene diimide and two Amine polymers, and mixtures thereof. 如申請專利範圍第1項之熱固性樹脂組成物，其中在改質線型聚醯亞胺樹脂(A)中聚丁二烯結構的含量為45重量%或更多。 The thermosetting resin composition of claim 1, wherein the content of the polybutadiene structure in the modified linear polyimine resin (A) is 45% by weight or more. 如申請專利範圍第1項之熱固性樹脂組成物，其中在改質線型聚醯亞胺樹脂(A)中聚丁二烯結構的含量為60重量%或更多。 The thermosetting resin composition of claim 1, wherein the content of the polybutadiene structure in the modified linear polyimine resin (A) is 60% by weight or more. 如申請專利範圍第1項之熱固性樹脂組成物，其中R1代表從數目平均分子量在800至10000之末端二元羥化的聚丁二烯上移除羥基基團所得到的殘基。 The thermosetting resin composition of claim 1, wherein R1 represents a residue obtained by removing a hydroxyl group from a polybutadiene which is dihydroxylated at a terminal number average molecular weight of 800 to 10,000. 如申請專利範圍第1項之熱固性樹脂組成物，其中該熱固性樹脂組成物之硬化材料的彈性模數為100 MPa或更低，且斷裂伸長量為20%或更多。 The thermosetting resin composition of claim 1, wherein the hardening material of the thermosetting resin composition has a modulus of elasticity of 100 MPa or less and an elongation at break of 20% or more. 如申請專利範圍第1項之熱固性樹脂組成物，其中成分(A)與成分(B)的組成比例為100：1至1：1重量比，且在熱固性樹脂組成物中成分(A)與成分(B)的總含量為70重量%或更多。 The thermosetting resin composition of claim 1, wherein the composition ratio of the component (A) to the component (B) is from 100:1 to 1:1 by weight, and the component (A) and the component in the thermosetting resin composition The total content of (B) is 70% by weight or more. 如申請專利範圍第1項之熱固性樹脂組成物，其另外包含填料。 The thermosetting resin composition of claim 1, which additionally comprises a filler. 如申請專利範圍第1項之熱固性樹脂組成物，其中該熱固性樹脂(B)包含環氧樹脂。 The thermosetting resin composition of claim 1, wherein the thermosetting resin (B) comprises an epoxy resin. 如申請專利範圍第13項之熱固性樹脂組成物，其 另外包含環氧硬化劑。 A thermosetting resin composition as claimed in claim 13 Also contains an epoxy hardener. 一種膠黏劑膜，其包含：(A)一種熱固性樹脂組成物層，其包含如申請專利範圍第1項之熱固性樹脂組成物；及(B)一種支撐膜，其中該熱固性樹脂組成物層(A)形成在該支撐膜(B)之上。 An adhesive film comprising: (A) a thermosetting resin composition layer comprising the thermosetting resin composition as claimed in claim 1; and (B) a support film, wherein the thermosetting resin composition layer ( A) is formed on the support film (B). 一種膠黏劑膜，其包含；(A)一種熱固性樹脂組成物層，其包含如申請專利範圍第1項之熱固性樹脂組成物；及(B)一種做過離型處理且具有離型處理表面的支撐膜，其中該熱固性樹脂組成物層(A)形成在該支撐膜(B)的離型處理表面之上。 An adhesive film comprising: (A) a thermosetting resin composition layer comprising the thermosetting resin composition as claimed in claim 1; and (B) a release treatment having a release treated surface The support film in which the thermosetting resin composition layer (A) is formed on the release treatment surface of the support film (B). 一種可撓性電路板，其包含形成在如申請專利範圍第1項之熱固性樹脂組成物的硬化材料上之電路。 A flexible circuit board comprising a circuit formed on a hardened material of a thermosetting resin composition as in the first aspect of the patent application. 一種多層可撓性電路板，其製造方法包含：(1)使用如申請專利範圍第15項之膠黏劑膜而層合可撓性電路板的一面或兩面；(2)熱硬化該熱固性樹脂組成物層(A)以形成絕緣層；(3)在該可撓性電路板中形成孔；(4)將該絕緣層作表面處理，以得到經表面處理的絕緣層； (5)經由電鍍在該經表面處理的絕緣層上形成導體層；及(6)在該經表面處理的絕緣層上將該導體層形成電路，其間選擇下列時機之一移除該支撐膜(B)：(1)介於該層合與該熱硬化之間；(ii)介於該熱硬化與該形成孔之間；或(iii)介於該形成孔與將該絕緣層作表面處理之間。 A multilayer flexible circuit board comprising: (1) laminating one or both sides of a flexible circuit board using an adhesive film as claimed in claim 15; (2) thermally hardening the thermosetting resin Forming the layer (A) to form an insulating layer; (3) forming a hole in the flexible circuit board; (4) surface-treating the insulating layer to obtain a surface-treated insulating layer; (5) forming a conductor layer on the surface-treated insulating layer by electroplating; and (6) forming the conductor layer on the surface-treated insulating layer to form a circuit, and removing the supporting film by selecting one of the following timings ( B): (1) between the lamination and the thermal hardening; (ii) between the thermal hardening and the forming of the hole; or (iii) interposed between the forming hole and the surface of the insulating layer between. 一種多層可撓性電路板，其製造方法包含：(1)使用如申請專利範圍第16項之膠黏劑膜而層合可撓性電路板的一面或兩面；(2)熱硬化該熱固性樹脂組成物層(A)以形成絕緣層；(3)在該可撓性電路板中形成孔；(4)將該絕緣層作表面處理，以得到經表面處理的絕緣層；(5)經由電鍍在該經表面處理的絕緣層上形成導體層；及(6)在該經表面處理的絕緣層上將該導體層形成電路，其間選擇下列時機之一移除該支撐膜(B)：(1)介於該層合與該熱硬化之間；(ii)介於該熱硬化與該形成孔之間；或(iii)介於該形成孔與將該絕緣層作表面處理之間。 A multilayer flexible circuit board comprising: (1) laminating one or both sides of a flexible circuit board using an adhesive film as claimed in claim 16; (2) thermally hardening the thermosetting resin Forming the layer (A) to form an insulating layer; (3) forming a hole in the flexible circuit board; (4) surface-treating the insulating layer to obtain a surface-treated insulating layer; (5) via electroplating Forming a conductor layer on the surface-treated insulating layer; and (6) forming the conductor layer on the surface-treated insulating layer, and removing the supporting film (B) by selecting one of the following timings: (1) Between the lamination and the thermal hardening; (ii) between the thermal hardening and the forming of the hole; or (iii) between the forming the hole and the surface treatment of the insulating layer. 一種用於可撓性電路板的膜，其包含：(A')一種絕緣層，其包含如申請專利範圍第1項之熱固性樹脂組成物的硬化材料；及(C)一種耐熱性樹脂層，其中該絕緣層(A)形成在該耐熱性樹脂層(C)之上。 A film for a flexible circuit board comprising: (A') an insulating layer comprising a hardening material of a thermosetting resin composition as claimed in claim 1; and (C) a heat resistant resin layer, The insulating layer (A) is formed on the heat resistant resin layer (C). 一種單面可撓性電路板，其經由如下方式製得：將如申請專利範圍第20項之可撓性電路板的膜上絕緣層(A')作表面處理，以得到經表面處理的絕緣層，經由電鍍在該經表面處理的絕緣層上形成導體層，及將該導體層形成電路。 A single-sided flexible circuit board obtained by surface-treating an insulating layer (A') of a flexible circuit board as claimed in claim 20 to obtain surface-treated insulation A layer is formed on the surface-treated insulating layer by electroplating, and the conductor layer is formed into an electrical circuit. 一種用於可撓性電路板的膜，其包含：(A')一種絕緣層，其包含如申請專利範圍第1項之熱固性樹脂組成物的硬化材料；(C)一種耐熱性樹脂層；及(D)一種銅箔，其中該膜具有順序為絕緣層(A')，耐熱性樹脂層(C)、及銅箔(D)的層化結構。 A film for a flexible circuit board comprising: (A') an insulating layer comprising a hardening material of a thermosetting resin composition as claimed in claim 1; (C) a heat resistant resin layer; (D) A copper foil in which the film has a layered structure of an insulating layer (A'), a heat resistant resin layer (C), and a copper foil (D). 一種雙面的可撓性電路板，其經由如下方式製得：在如申請專利範圍第22項之用於可撓性電路板的膜中形成孔，將該絕緣層(A')作表面處理，以得到經表面處理的絕緣層，經由電鍍在該經表面處理的絕緣層之表面而形成導體層，及將該導體層與該銅箔(D)形成電路。 A double-sided flexible circuit board produced by forming a hole in a film for a flexible circuit board as in claim 22 of the patent application, and surface-treating the insulating layer (A') To obtain a surface-treated insulating layer, a conductor layer is formed on the surface of the surface-treated insulating layer by electroplating, and the conductor layer and the copper foil (D) are formed into an electric circuit. 一種用於可撓性電路板的膜，其包含：： (A')第一絕緣層，其包含如申請專利範圍第1項之熱固性樹脂組成物的硬化材料；(C)耐熱性樹脂層；及(A")第二絕緣層，其包含如申請專利範圍第1項之熱固性樹脂組成物的硬化材料，其中該膜具有順序為第一絕緣層(A')，耐熱性樹脂層(C)，及第二絕緣層(A")的層化結構。 A film for a flexible circuit board comprising: (A') a first insulating layer comprising a hardening material of a thermosetting resin composition as claimed in claim 1; (C) a heat resistant resin layer; and (A") a second insulating layer comprising a patent application The hardening material of the thermosetting resin composition of the first aspect, wherein the film has a layered structure in which the order is the first insulating layer (A'), the heat resistant resin layer (C), and the second insulating layer (A"). 一種雙面的可撓性電路板，其經由如下方式製得：在如申請專利範圍第24項之用於可撓性電路板的膜中形成孔，將該第一絕緣層(A')與該第二絕緣層(A")作表面處理，以得到第一與第二經表面處理的絕緣層，經由電鍍在該第一與第二經表面處理的絕緣層上形成第一與第二導體層，及將該第一與第二導體層形成電路。 A double-sided flexible circuit board obtained by forming a hole in a film for a flexible circuit board according to claim 24 of the patent application, the first insulating layer (A') and The second insulating layer (A" is surface-treated to obtain first and second surface-treated insulating layers, and first and second conductors are formed on the first and second surface-treated insulating layers via electroplating a layer, and forming the first and second conductor layers into a circuit. 一種半導體裝置，其包含半導體與基材板，其係使用內含如申請專利範圍第1項之熱固性樹脂組成物的硬化材料所黏合。 A semiconductor device comprising a semiconductor and a substrate sheet bonded using a hardening material containing a thermosetting resin composition as in the first aspect of the patent application. 一種製造多層可撓性電路板之方法，其包含：(1)使用如申請專利範圍第15項之膠黏劑膜層合可撓性電路板的一面或兩面；(2)熱硬化該熱固性樹脂組成物層(A)以形成絕緣層；(3)在該可撓性電路板中形成孔；(4)將該絕緣層作表面處理，以得到經表面處理的絕緣層； (5)經由電鍍在該經表面處理的絕緣層上形成導體層；及(6)在該經表面處理的絕緣層上將該導體層形成電路，其間選擇下列時機之一移除該支撐膜(B)：(1)介於該層合與該熱硬化之間；(ii)介於該熱硬化與該形成孔之間；或(iii)介於該形成孔與將該絕緣層作表面處理之間。 A method of manufacturing a multilayer flexible circuit board comprising: (1) laminating one or both sides of a flexible circuit board using an adhesive film as set forth in claim 15; (2) thermally hardening the thermosetting resin Forming the layer (A) to form an insulating layer; (3) forming a hole in the flexible circuit board; (4) surface-treating the insulating layer to obtain a surface-treated insulating layer; (5) forming a conductor layer on the surface-treated insulating layer by electroplating; and (6) forming the conductor layer on the surface-treated insulating layer to form a circuit, and removing the supporting film by selecting one of the following timings ( B): (1) between the lamination and the thermal hardening; (ii) between the thermal hardening and the forming of the hole; or (iii) interposed between the forming hole and the surface of the insulating layer between. 一種製造多層可撓性電路板之方法，其包含：(1)使用如申請專利範圍第16項之膠黏劑膜層合可撓性電路板的一面或兩面；(2)熱硬化該熱固性樹脂組成物層(A)以形成絕緣層；(3)在該可撓性電路板中形成孔；(4)將該絕緣層作表面處理，以得到經表面處理的絕緣層；(5)經由電鍍在該經表面處理的絕緣層上形成導體層；及(6)在該經表面處理的絕緣層上將該導體層形成電路，其間選擇下列時機之一移除該支撐膜(B)：(1)介於該層合與該熱硬化之間；(ii)介於該熱硬化與該形成孔之間；或(iii)介於該形成孔與將該絕緣層作表面處理之間。A method of manufacturing a multilayer flexible circuit board comprising: (1) laminating one or both sides of a flexible circuit board using an adhesive film as claimed in claim 16; (2) thermally hardening the thermosetting resin Forming the layer (A) to form an insulating layer; (3) forming a hole in the flexible circuit board; (4) surface-treating the insulating layer to obtain a surface-treated insulating layer; (5) via electroplating Forming a conductor layer on the surface-treated insulating layer; and (6) forming the conductor layer on the surface-treated insulating layer, and removing the supporting film (B) by selecting one of the following timings: (1) Between the lamination and the thermal hardening; (ii) between the thermal hardening and the forming of the hole; or (iii) between the forming the hole and the surface treatment of the insulating layer.