200914537 九、發明說明 【發明所屬之技術領域】 本發明係關於作爲多層印刷配線板之層間絕緣用，優 尤其是可撓多層印刷配線板之層間絕緣用，之較佳的樹脂 組成物。又，本發明亦關於由該樹脂組成物調製之用以形 成多層印刷配線板之層間絕緣層的接著膜、由該樹脂組成 物形成層間絕緣層之多層印刷配線板。 【先前技術】 可撓多層印刷配線板由於即使對於狹窄的空間亦可折 曲組裝，故於朝向小型化、薄型化進展之媒體器材等爲不 可或缺者。作爲可撓多層印刷配線板之層間絕緣所用的材 料，例如，於專利文獻1中曾揭示具有聚丁二烯構造之聚 醯亞胺與環氧樹脂等所構成之樹脂組成物，並揭示出由該 樹脂組成物所得到之層間絕緣層有優異的柔軟性、機械強 度、介電特性等。 〔專利文獻1〕日本專利特開2006-03 70 83號公報 【發明內容】 (發明所欲解決之問題） 本發明之目的在於提供適於可撓多層印刷配線板之層 間絕緣用之樹脂組成物。 (用以解決課題之手段） -5- 200914537 專利文獻1中之樹脂組成物中所含有的聚醯亞胺，其 末端爲酸酐基或羧基等，由於此等基容易與環氧基反應水 解而生成酯鍵’故若考慮使用於精密電子零件時，就絕緣 可靠性等之考量，須減低甚至排除樹脂組成物中之此等基 的存在。鑑於此點，本發明者等爲於具有聚丁二烯構造的 聚醯亞胺中，使羧基降低甚至排除之目的，乃使用在末端 導入苯酚構造的聚醯亞胺樹脂，並對樹脂組成物進行評估 ，其結果，發現可得到同樣的柔軟性、機械強度、介電特 性等皆優異的層間絕緣層。另一方面，於以樹脂組成物作 爲層間絕緣層使用之外，爲了在熱膨脹率及黏著性（tack )之抑制等之目的，含入以氧化矽爲代表之無機塡充材的 方法乃周知者，而於含有該苯酚末端聚醯亞胺與環氧樹脂 的組成物中，無機塡充材容易沈降，欲得到均一的樹脂組 成物有困難，是其問題。本發明者等經刻意硏究之下，發 現藉由使用較通常所使用之無機塡充材之比表面積遠較小 的範圍者，無機塡充材可容易地分散而可得到均一的樹脂 組成物。 本發明者等基於上述發現而完成了本發明。亦即，本 發明包含下述內容： 〔1〕含有下述成分（A) 、 （B)及（C)之多層印 刷配線板之層間絕緣用樹脂組成物： (A)於分子內具有聚丁二烯構造、胺基甲酸酯構造 、醯亞胺構造，且於分子末端具有苯酚構造之聚醯亞胺樹 脂， -6- 200914537 (B )環氧樹脂， (C )比表面積爲18~50m2/g之無機塡充材。 〔2〕含有下述成分（A) 、 （B)及（C)之多層印 刷配線板之層間絕緣用樹脂組成物： (A )經由〔a〕使1分子中具有2個以上的醇性羥基 之聚丁二烯多元醇化合物、及〔b〕二異氰酸酯化合物進 行反應，作成二異氰酸酯預聚物，再使〔c〕四元酸二酐 、及〔d〕1分子中具有2個以上的苯酚性羥基之多官能苯 酚化合物進行反應所製得之於分子末端具有苯酚構造之聚 醯亞胺樹脂； (B )環氧樹脂； (C)比表面積爲18〜50m2/g之無機塡充材。 〔3〕如上述〔1〕或〔2〕之樹脂組成物，其中’成 分（C)之無機塡充材之比表面積爲18〜40m2/g。 〔4〕如上述〔1〕或〔2〕之樹脂組成物，其中’成 分（C)之無機塡充材之比表面積爲18〜35m2/g。 〔5〕如上述〔1〕或〔2〕之樹脂組成物，其中，成 分（C)之無機塡充材之比表面積爲20〜30m2/g。 〔6〕如上述〔1〕或〔2〕之樹脂組成物，其中，無 機塡充材爲二氧化矽。 〔7〕如上述〔1〕或〔2〕之樹脂組成物，其中，苯 酚系化合物爲酚醛清漆樹脂。 〔8〕如上述〔1〕或〔2〕之樹脂組成物，其中，聚 丁二烯多元醇化合物爲氫化聚丁二烯多元醇化合物。 -7- 200914537 〔9〕如上述〔2〕之樹脂組成物，其係於成分（A ) 之聚醯亞胺樹脂中，相對於反應成分〔a〕1分子中具有2 個以上的醇性羥基之聚丁二烯多元醇的羥基，反應成分〔 b〕二異氰酸酯化合物的異氰酸酯基之官能基當量比爲1: 1.5~1 : 2.5的比例下進行反應。 〔1 〇〕如上述〔1〕或〔2〕之樹脂組成物，其進而含 有成分〔D〕在1分子中具有2個以上的苯酚性羥基之多 官能苯酚化合物。 〔1 1〕如上述〔1 0〕之樹脂組成物，其相對於成分（ A)之聚醯亞胺樹脂、成分（B)之環氧樹脂及成分（D) 之多官能苯酚化合物的合計1 〇 〇重量％，含有成分（A ) 40〜85重量％，成分（B) 15〜40重量％，成分（D) 0~20 重量％。 〔1 2〕一種多層印刷配線板之層間絕緣層形成用接著 膜’其特徵爲，係由上述〔1〕或〔2〕項之樹脂組成物於 支持體上形成層者。 〔1 3〕一種多層印刷配線板，其係藉由上述〔1〕或 〔2〕項之樹脂組成物形成層間絕緣層者。 (發明之效果） 依據本發明，可提供柔軟性、機械強度、介電特性等 皆優異之適用於可撓多層印刷配線板之層間絕緣用樹脂組 成物。 -8 - 200914537 【實施方式】 (用以實施發明之最佳形態） 本發明中之成分（A)之聚醯亞胺樹脂，於分子內具 有聚丁二烯構造、胺基甲酸酯構造、醯亞胺構造，且於分 子末端具有苯酚構造。於該於分子末端具有苯酚構造之聚 醯亞胺樹脂可使用反應成分〔a〕〜〔d〕以下述方法製得 。亦即， 使〔a〕1分子中具有2個以上的醇性羥基之聚丁二烯 多元醇化合物、及〔b〕二異氰酸酯化合物進行反應，作 成二異氰酸酯預聚物，然後，使〔c〕四元酸二酐、及〔d 〕1分子中具有2個以上的苯酚性羥基之多官能苯酚化合 物進行反應。 作爲〔a〕1分子中具有2個以上的醇性羥基之聚丁二 烯多元醇化合物，以數平均分子量爲300〜5,000者爲佳。 於數平均分子量爲3 00以下之情況，改質聚醯亞胺樹脂會 有柔軟性欠佳之傾向。於5,000以上之情況，改質聚醯亞 胺樹脂之與熱硬化性樹脂之相溶性會有欠佳之傾向，且耐 熱性、耐藥品性亦會有欠佳之傾向。 又，本發明中，數平均分子量係以凝膠滲透層析（ GPC )法（聚苯乙烯換算）測定之値。依據GPC法之數平 均分子量，具體而言，作爲測定裝置係用昭和電工（股） 製Shodex GPC System 21，作爲管柱係用昭和電工（股） 製 Shodex LF-804/KF-803/KF-804，移動相係用 NMP，於 管柱溫度40°C測定，用標準聚苯乙烯之檢量線可求出。作 200914537 爲該聚丁二烯多元醇，可單獨使用亦可混合使用分子內的 不飽和鍵經氫化之氫化聚丁二烯多元醇。又，作爲該聚丁 二烯多元醇以於分子末端具有羥基之聚丁二烯多元醇爲佳 。又，所謂醇性羥基，係指脂肪族烴構造之氫原子以羥基 (hydroxyl )取代的形態存在之氫氧基。作爲該聚丁二烯 多元醇之具體例，可舉出例如：G- 1 000、G-2000、G-3 000 、GI- 1 000、GI-2000 (以上爲日本曹達（股）製），11-4 5 EPI (出光石油化學（股）公司製）等。 〔b〕二異氰酸酯化合物爲分子內有2個異氰酸酯基 之化合物，可舉出例如：甲苯-2,4-二異氰酸酯、甲苯-2,6-二異氰酸酯、六亞甲基二異氰酸酯、二甲苯二異氰酸酯、 二苯基甲烷二異氰酸酯、異佛酮二異氰酸酯等。 〔c〕四元酸二酐爲分子內有2個酸酐基之化合物， 可舉出：均苯四甲酸二酐、二苯甲酮四羧酸二酐、聯苯四 羧酸二酐、萘四羧酸二酐、5- (2,5 -二氧四氫呋喃）-3 -甲 基環己烯-1,2 -二羧酸酐、3,3’-4,4’ -二苯颯四羧酸二酐、 1，3,3&，4,5,91?-六氫-5(四氫-2,5-二氧-3-呋喃）萘并〔1，2-C〕呋喃-1,3-二酮等。 〔d〕作爲1分子中有2個以上之苯酚性羥基之多官 能苯酚化合物’可舉出例如：雙酚A、雙酚F、雙酚S、 二苯酚、酚醛清漆樹脂、烷基酚醛清漆樹脂、雙酚A型清 漆樹脂、含有二環戊二烯構造之酚醛清漆樹脂、含有三哄 構造之酚醛清漆樹脂、含有聯苯骨架之酚醛清漆樹脂、含 有苯基之酚醛清漆樹脂、萜烯改質酚醛樹脂、聚乙烯酚類 -10- 200914537 等。尤以烷基酚醛清漆樹脂爲佳。又，所謂苯酚性羥基係 指芳香環構造之氫原子以羥基取代之形態而存在的羥基。 爲有效率地得到本發明中之聚醯亞胺樹脂，以依照下 述順序爲佳。首先使反應成分〔a〕之聚丁二烯多元醇與 反應成分〔b〕之二異氰酸酯化合物，以相對於該聚丁二 烯多元醇之羥基的二異氰酸酯化合物之異氰酸酯基之官能 基當量爲超過1的比例進行反應。聚丁二烯多元醇與二異 氰酸酯化合物之反應比例，以相對於該聚丁二烯之羥基的 二異氰酸酯之異氰酸酯基之官能基當量爲1:1.5~1:2·5 的比例爲佳。 於反應成分〔a〕爲在分子末端有羥基之聚丁二烯多 元醇之情況，該聚丁二烯多元醇可以下式（a’）表示。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a preferred resin composition for interlayer insulation of a multilayer printed wiring board, particularly for interlayer insulation of a flexible multilayer printed wiring board. Further, the present invention relates to a film for forming an interlayer insulating layer of a multilayer printed wiring board prepared by the resin composition, and a multilayer printed wiring board in which an interlayer insulating layer is formed of the resin composition. [Prior Art] Since the flexible multilayer printed wiring board can be flexibly assembled even in a narrow space, it is indispensable for media equipment that is becoming smaller and thinner. As a material for interlayer insulation of a flexible multilayer printed wiring board, for example, Patent Document 1 discloses a resin composition composed of a polybutadiene structure having a polybutadiene structure and an epoxy resin, and discloses that The interlayer insulating layer obtained by the resin composition has excellent flexibility, mechanical strength, dielectric properties, and the like. [Problem to be Solved by the Invention] It is an object of the present invention to provide a resin composition suitable for interlayer insulation of a flexible multilayer printed wiring board. . (Means for Solving the Problem) -5-200914537 The polyimine contained in the resin composition of Patent Document 1 has an acid anhydride group or a carboxyl group at the terminal, and is easily hydrolyzed by reaction with an epoxy group. When an ester bond is formed, it is necessary to reduce or even exclude the presence of such a group in the resin composition in consideration of insulation reliability and the like in consideration of use in precision electronic parts. In view of the above, the inventors of the present invention have used a polyimine resin having a phenol structure at the terminal end and a resin composition for the purpose of reducing or even eliminating a carboxyl group in a polyimide having a polybutadiene structure. As a result of the evaluation, it was found that an interlayer insulating layer excellent in flexibility, mechanical strength, dielectric properties, and the like was obtained. On the other hand, in order to use a resin composition as an interlayer insulating layer, a method of incorporating an inorganic ruthenium material represented by ruthenium oxide is known for the purpose of suppressing thermal expansion coefficient and adhesion (tack). On the other hand, in the composition containing the phenolic terminal polyimine and the epoxy resin, the inorganic cerium filler is likely to settle, and it is difficult to obtain a uniform resin composition, which is a problem. The inventors of the present invention have found that the inorganic ceramium can be easily dispersed to obtain a uniform resin composition by using a range in which the specific surface area of the inorganic cerium filler which is generally used is much smaller. . The present inventors completed the present invention based on the above findings. In other words, the present invention includes the following: [1] A resin composition for interlayer insulation of a multilayer printed wiring board comprising the following components (A), (B) and (C): (A) having a polybutene in a molecule a diene structure, a urethane structure, a quinone imine structure, and a phenolic structure of a polyimine resin at the molecular end, -6-200914537 (B) epoxy resin, (C) specific surface area of 18 to 50 m2 /g of inorganic enamel filling. [2] A resin composition for interlayer insulation of a multilayer printed wiring board comprising the following components (A), (B) and (C): (A) having two or more alcoholic hydroxyl groups in one molecule via [a] The polybutadiene polyol compound and the [b] diisocyanate compound are reacted to form a diisocyanate prepolymer, and [c] tetrabasic dianhydride and [d] 1 molecule have two or more phenols. A polyhydroxyimine resin having a phenol structure at a molecular terminal obtained by reacting a polyfunctional phenol compound of a hydroxyl group; (B) an epoxy resin; (C) an inorganic cerium filler having a specific surface area of 18 to 50 m 2 /g. [3] The resin composition according to the above [1] or [2], wherein the inorganic ceramium filler of the component (C) has a specific surface area of 18 to 40 m 2 /g. [4] The resin composition according to the above [1] or [2], wherein the inorganic ceramium filler of the component (C) has a specific surface area of 18 to 35 m 2 /g. [5] The resin composition according to the above [1] or [2], wherein the inorganic ceramate of the component (C) has a specific surface area of 20 to 30 m 2 /g. [6] The resin composition according to the above [1] or [2] wherein the inorganic ruthenium filler is ruthenium dioxide. [7] The resin composition according to the above [1] or [2] wherein the phenol-based compound is a novolac resin. [8] The resin composition according to the above [1] or [2] wherein the polybutadiene polyol compound is a hydrogenated polybutadiene polyol compound. [9] The resin composition of the above [2], which is contained in the polyimine resin of the component (A), and has two or more alcoholic hydroxyl groups in the molecule of the reaction component [a]. The hydroxyl group of the polybutadiene polyol is reacted with a functional group equivalent ratio of the isocyanate group of the reaction component [b] diisocyanate compound of 1:1.5 to 1:2.5. [1] The resin composition of the above [1] or [2], which further contains a polyfunctional phenol compound having a component [D] having two or more phenolic hydroxyl groups in one molecule. [1 1] The total composition of the resin composition of the above [10] with respect to the polyamidene resin of the component (A), the epoxy resin of the component (B), and the polyfunctional phenol compound of the component (D) 〇〇% by weight, containing component (A) 40 to 85% by weight, component (B) 15 to 40% by weight, and component (D) 0 to 20% by weight. [2] A film for forming an interlayer insulating layer of a multilayer printed wiring board, wherein the resin composition of the above [1] or [2] is formed on a support. [13] A multilayer printed wiring board which is formed by forming the interlayer insulating layer from the resin composition of the above [1] or [2]. (Effect of the Invention) According to the present invention, it is possible to provide a resin composition for interlayer insulation which is excellent in flexibility, mechanical strength, dielectric properties and the like, which is suitable for a flexible multilayer printed wiring board. -8 - 200914537 (Embodiment) The polyimine resin of the component (A) in the present invention has a polybutadiene structure and a urethane structure in a molecule. The quinone imine structure has a phenol structure at the molecular end. The polyimine resin having a phenol structure at the molecular end can be obtained by the following methods using the reaction components [a] to [d]. In other words, the polybutadiene polyol compound having two or more alcoholic hydroxyl groups in [a] molecule and the [b] diisocyanate compound are reacted to form a diisocyanate prepolymer, and then [c] A tetrabasic acid dianhydride and a polyfunctional phenol compound having two or more phenolic hydroxyl groups in one molecule of [d] are reacted. The polybutadiene polyol compound having two or more alcoholic hydroxyl groups in one molecule of [a] is preferably a number average molecular weight of from 300 to 5,000. In the case where the number average molecular weight is 300 or less, the modified polyimine resin tends to have poor flexibility. In the case of 5,000 or more, the compatibility of the modified polyimine resin with the thermosetting resin tends to be inferior, and the heat resistance and chemical resistance tend to be poor. Further, in the present invention, the number average molecular weight is measured by a gel permeation chromatography (GPC) method (in terms of polystyrene). According to the number average molecular weight of the GPC method, Shodex GPC System 21 manufactured by Showa Denko Co., Ltd. is used as a measuring device, and Shodex LF-804/KF-803/KF- is used as a column system. 804, the mobile phase is measured by NMP at a column temperature of 40 ° C, and can be obtained by using a standard polystyrene calibration line. 200914537 is a polybutadiene polyol which may be used alone or in combination with a hydrogenated polybutadiene polyol which is hydrogenated in an intramolecular unsaturated bond. Further, as the polybutadiene polyol, a polybutadiene polyol having a hydroxyl group at a molecular terminal is preferred. Further, the alcoholic hydroxyl group means a hydroxyl group in which a hydrogen atom of an aliphatic hydrocarbon structure is substituted with a hydroxyl group. Specific examples of the polybutadiene polyol include, for example, G-1 000, G-2000, G-3 000, GI-1 000, and GI-2000 (the above are manufactured by Japan Soda Co., Ltd.). 11-4 5 EPI (produced by Idemitsu Petrochemical Co., Ltd.). [b] The diisocyanate compound is a compound having two isocyanate groups in the molecule, and examples thereof include toluene-2,4-diisocyanate, toluene-2,6-diisocyanate, hexamethylene diisocyanate, and xylene. Isocyanate, diphenylmethane diisocyanate, isophorone diisocyanate, and the like. [c] The tetrabasic acid dianhydride is a compound having two acid anhydride groups in the molecule, and examples thereof include pyromellitic dianhydride, benzophenone tetracarboxylic dianhydride, biphenyltetracarboxylic dianhydride, and naphthalene tetra Carboxylic dianhydride, 5-(2,5-dioxotetrahydrofuran)-3-methylcyclohexene-1,2-dicarboxylic anhydride, 3,3'-4,4'-diphenyltetracarboxylic acid Anhydride, 1,3,3&,4,5,91?-hexahydro-5(tetrahydro-2,5-dioxo-3-furan)naphtho[1,2-c]furan-1,3- Diketone and the like. [d] The polyfunctional phenol compound which has two or more phenolic hydroxyl groups in one molecule is exemplified by bisphenol A, bisphenol F, bisphenol S, diphenol, novolak resin, and alkyl novolac resin. , bisphenol A type varnish resin, novolac resin containing dicyclopentadiene structure, novolak resin containing triterpene structure, novolak resin containing biphenyl skeleton, novolac resin containing phenyl group, terpene modification Phenolic resin, polyvinyl phenols-10-200914537, etc. In particular, an alkyl novolac resin is preferred. Further, the phenolic hydroxyl group means a hydroxyl group in which a hydrogen atom of an aromatic ring structure is substituted with a hydroxyl group. In order to obtain the polyimine resin of the present invention efficiently, it is preferred to follow the order described below. First, the polybutadiene polyol of the reaction component [a] and the diisocyanate compound of the reaction component [b] are substituted with the functional group equivalent of the isocyanate group of the diisocyanate compound of the hydroxyl group of the polybutadiene polyol. The ratio of 1 is reacted. The reaction ratio of the polybutadiene polyol to the diisocyanate compound is preferably from 1:1.5 to 1:2.5, based on the functional group equivalent of the isocyanate group of the diisocyanate of the hydroxyl group of the polybutadiene. In the case where the reaction component [a] is a polybutadiene polyol having a hydroxyl group at the molecular terminal, the polybutadiene polyol can be represented by the following formula (a').
HO、/OHHO, /OH
Rl (a ) (R1表示具有聚丁二烯構造之2價有機基） 反應成分〔b〕之二異氰酸酯化合物可用下式（b)表 示。 OCN—R2—NCO (b) (R2表示2價之有機基） 反應成分〔c〕之四元酸二酐可用下式（c)表示。 -11 - 200914537Rl (a ) (R1 represents a divalent organic group having a polybutadiene structure) The diisocyanate compound of the reaction component [b] can be represented by the following formula (b). OCN—R 2 —NCO (b) (R 2 represents a divalent organic group) The tetrabasic acid dianhydride of the reaction component [c] can be represented by the following formula (c). -11 - 200914537
(c) (R3表示4價之有機基） 使上述於分子末端有羥基之聚丁二烯多 酸酯化合物反應得到之二異氰酸酯預聚物可 )表不。 Η Η OCN+J丫丫1^I·(“) 0 0 (R1及R2係與上述同義，η表示1以上 SnSlOO)之整數。較佳者爲η表示1以上1 10 )之整數） 接著，使上述反應中得到之二異氰酸酯S 成分〔c〕之四元酸二酐及反應成分〔d〕之多 合物反應。反應比例並無特別限定，以儘量使 殘留異氰酸酯基爲佳。爲儘量使組成物中不殘 基，以於反應中用FT-IR確認異氰酸酯基之# 反應順序，可舉出：首先使四元酸二酐反應孩 能苯酚化合物反應的方法；與同時添加四元酸 能苯酚化合物使其反應的方法。於同時添加之 認爲酸酐基會優先與異氰酸酯基反應而形成聚 後，殘留之異氰酸酯基會與多官能苯酚化合物 醇與二異氰 T 式（a，-b 1〇〇以下（！ 〇以下（i $ 聚物與反應 官能苯酚化 組成物中不 留異氰酸酯 失爲佳。依 ，再使多官 二酐及多官 情況，吾人 醯亞胺。然 反應，可於 -12- 200914537 末端導入苯酚構造。 以反應成分〔a〕之聚丁二烯多元醇之羥基的官能基 當量爲W，以反應成分〔b〕之二異氰酸酯化合物之異氰 酸酯基的官能基當量爲X，以反應成分〔〇〕之四元酸二 酐的官能基當量爲 Y，以反應成分〔d〕之多官能苯酚化 合物的官能基當量爲Z之情況，反應成分〔c〕及〔d〕以 使用滿足Y<X-W<Y + Z的關係之比例爲佳。 於作爲反應成分〔a〕係使用於分子末端有羥基之聚 丁二烯多元醇之情況，本發明中之成分（A)之聚醯亞胺 具有下式Ο-a)及（Ι-b)之構造。 --R2(c) (R3 represents a tetravalent organic group) The diisocyanate prepolymer obtained by reacting the above polybutadiene polyester compound having a hydroxyl group at the terminal of the molecule can be represented. Η Η OCN+J丫丫1^I·(") 0 0 (R1 and R2 are synonymous with the above, η represents an integer of 1 or more SnS100). Preferably, η represents an integer of 1 or more and 10)) Next, The tetrabasic acid dianhydride of the diisocyanate S component [c] obtained in the above reaction and the complex of the reaction component [d] are reacted. The reaction ratio is not particularly limited, and the residual isocyanate group is preferably as much as possible. There is no residue in the composition, and the reaction sequence of the isocyanate group is confirmed by FT-IR in the reaction, and a method of first reacting a tetrabasic acid dianhydride with a phenol compound can be mentioned; A method in which a phenol compound is allowed to react. It is considered that an acid anhydride group preferentially reacts with an isocyanate group to form a poly group, and the residual isocyanate group is combined with a polyfunctional phenol compound alcohol and a diisocyanate formula (a, -b 1 ). 〇〇 ( ! ! ! ! ! ! ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( -12- 200914537 Terminal introduction of phenol The functional group equivalent of the hydroxyl group of the polybutadiene polyol of the reaction component [a] is W, and the functional group equivalent of the isocyanate group of the diisocyanate compound of the reaction component [b] is X, and the reaction component [〇] The functional group equivalent of the tetrabasic acid dianhydride is Y, and the functional group equivalent of the polyfunctional phenol compound of the reaction component [d] is Z, and the reaction components [c] and [d] are used to satisfy Y<X-W<lt; The ratio of the relationship of Y + Z is preferably. When the reaction component [a] is used in the case of a polybutadiene polyol having a hydroxyl group at the terminal of the molecule, the polyimine of the component (A) of the present invention has Structure of Ο-a) and (Ι-b). --R2
(1-a) 0 0(1-a) 0 0
(1-b) 具體之反應條件’例如，反應成分〔a〕之聚丁二烯 多元醇與反應成分〔b〕之二異氰酸酯化合物之反應，可 於有機溶劑中，反應溫度8 0 °C以下，反應時間通常爲2〜8 小時之條件下進行。又，必要時亦可在觸媒存在下進行。 接著，在該反應溶液中添加四元酸二酐及多官能苯酚化合 物，於反應溫度120〜160°C，反應時間5~24小時之條件 下進行。反應通常係於觸媒存在下進行。又，亦可再添加 -13- 200914537 有機溶劑而進行。 於此反應中，由於異氰酸酯基與酸酐基之反應而形成 醯亞胺鍵之同時亦會產生二氧化碳，故藉由測定反應前後 之重量減少，求出二氧化碳之莫耳數，可計算形成之醯亞 胺基之莫耳數。 反應完成後，視需要亦可將反應溶液過濾以除去不溶 物。如此，可得到清漆（varnish )狀態之聚醯亞胺樹脂。 清漆中之溶劑量可藉由調整反應時之溶劑量或於反應後添 加溶劑等而適當地調整。本發明中之聚醯亞胺樹脂，通常 可於上述清漆狀態下用來調製組成物。於單離的情況，例 如，藉由在不良溶劑之甲醇中逐次添加得到之清漆，使聚 醯亞胺沈澱可得到固體。 作爲上述各反應中所使用之溶劑，可舉出例如： N，N’-二甲基甲醯胺' Ν,Ν’-二乙基甲醯胺、Ν,Ν’-二甲基乙 醯胺、Ν，Ν’-二乙基乙醯胺、二甲亞硼、二乙亞颯、Ν-甲 基-2-吡咯烷酮、四甲脲、r-丁內酯、環己酮、二甘醇二 甲醚、三甘醇二甲醚、乙酸卡必醇酯、丙二醇單甲醚乙酸 酯、丙二醇單乙醚乙酸酯等之極性溶劑。此等溶劑亦可2 種以上混合使用。又，視需要亦可適當地混合使用芳香族 烴等之非極性溶劑。 作爲上述各反應中所使用之觸媒，可舉出例如：四甲 基丁烷二胺、苄基二甲胺、三乙醇胺、三乙胺、Ν, N，-二 甲基哌Π定（piperidine) 、α-甲基辛基二甲胺、N_乙基嗎 林、三乙二胺等之三級胺、或二丁基錫月桂酸酯' 二甲基 -14- 200914537 錫二氯、萘酸鈷、萘酸鋅等之有機金屬觸媒等。此等觸媒 亦可2種以上混合使用。作爲觸媒，尤以使用三乙二胺爲 最佳。 作爲本發明中之環氧樹脂，可舉出例如：雙酚A型環 氧樹脂、雙酚F型環氧樹脂' 酚醛清漆樹脂、雙酚S型環 氧樹脂、烷基酚醛清漆樹脂、聯苯酚型環氧樹脂、萘型環 氧樹脂、二環戊二烯型環氧樹脂、與具有苯酚與苯酚性羥 基之芳香族醛的縮合物之環氧化物、縮水甘油基異三聚氰 酸酯、脂環型環氧樹脂等之於1分子中有2個以上的官能 基之環氧樹脂。此等環氧樹脂亦可2種以上混合使用。再 者，以使用雙酚A型環氧樹脂爲佳。 本發明之組成物中，視需要亦可調配環氧樹脂硬化劑 。作爲環氧樹脂硬化劑，可舉出例如：胺系硬化劑、脈（ g u a n i d i n e )系硬化劑、咪唑系硬化劑、苯酚系硬化劑、酸 酐系硬化劑、或此等之環氧加成物與微膠囊化者等。尤其 就樹脂組成物作成爲清漆時之黏度安定性等之考量以苯酚 系硬化劑爲佳。環氧樹脂硬化劑亦可2種以上混合使用。 作爲環氧樹脂硬化劑之具體例，可舉出例如：作爲胺 系硬化劑之雙氰胺、作爲咪唑系硬化劑之咪唑矽烷、2-苯 基-4 -甲基-5-羥甲基咪唑、2,4-二胺基-6-〔 2’ -甲基咪唑-( 1’）〕-乙基-S-三哄異三聚氰酸加成物、作爲苯酚系硬化 劑之含有三哄構造之酚醛清漆樹脂（例如，Phen〇lite705 0 系列：大日本油墨化學（股）公司製）等。 作爲本發明之聚醯亞胺樹脂組成物，爲了成分（A ) -15- 200914537 之聚醯亞胺樹脂與成分（B )之環氧樹脂的硬化時之交聯 密度等之控制，以倂用成分（D ) 1分子中有2個以上之 苯酚性羥基之多官能苯酚化合物爲佳。藉由倂用成分（D )可提高成分（A )與成分（B )之交聯密度，藉此可降低 於玻璃轉化溫度以上的溫度中之熱膨脹等。爲提高前述交 聯密度、降低熱膨脹，樹脂組成物中之成分（A )與成分 (B)與成分（D )之調配比例，較佳者爲，相對於此等之 合計100重量％， （ A )爲 40〜85重量％，成分（B )爲 15~40重量％，成分（D)爲0~20重量％。成分（A)中的 苯酚性羥基（X )與成分（D )中之苯酚性羥基（Z )之合 計，與成分（B )中之環氧基（y )之莫耳比，以（x + z ) / (y)爲0.7〜1.3爲佳。 作爲成分（D )之1分子中有2個以上之苯酚性羥基 之多官能苯酚化合物之例，可舉出與上述反應成分〔d] 相同者。 本發明之熱硬化性聚醯亞胺樹脂組成物，視需要亦可 倂用硬化促進劑。可舉出例如：三聚氰胺、雙氰胺、鳥糞 胺及其衍生物、胺類、有1個羥基之苯酚類、有機膦類、 鱗鹽類、4級銨鹽類、多鹽基酸酐、光陽離子觸媒、氰酸 酯化合物、異氰酸酯化合物、嵌段異氰酸酯化合物等。 本發明之樹脂組成物中可含有比表面積爲18〜5 〇m2/g 之無機塡充材。作爲無機塡充材之例，可舉出：二氧化石夕 、氧化鋁等。尤以二氧化矽爲佳。無機塡充材亦可2種以 上混合使用。無機塡充材之調配量並無特別限定，較佳者 -16- 200914537 爲，可於樹脂組成物中添加10〜50質量％之範圍內。若未 滿1 0質量％，會有難以得到熱膨脹率及黏著（tack )改善 等效果之傾向。若超過5 〇質量％，不僅雷射加工性變差’ 且硬化物之彈性係數亦變高，有成爲硬脆的材料之傾向。 又，無機塡充材之比表面積可於18〜50m2/g之範圍內 使用。若在此範圍外，塡料會有沈降之傾向，致清漆難以 維持長時間之安定。比表面積的範圍之下限以20m2/g以 上爲更佳。比表面積的範圍之上限以 40m2/g爲佳，以 35m2/g爲更佳，以30m2/g以下爲特佳。例如，比表面積 之範圍以18〜40m2/g爲佳，以18〜35m2/g之範圍爲更佳， 以20〜30m2/g之範圍爲特佳。 比表面積之分析，可藉由在粉體粒子表面之佔有面積 爲已知的分子，使其於液態氮的溫度下吸附，由其量來求 出試料之比表面積之所謂的「BET法」求出。最常被使用 者爲藉由惰性氣體之低溫低濕物理吸附之BET法。 本發明之樹脂組成物中，亦可於可發揮本發明之效果 的範圍內調配各種樹脂添加劑與成分（A )及（B )以外之 樹脂成分等。作爲樹脂添加劑之例，可舉出：歐魯便、膨 潤土等之增黏劑、矽氧烷（silicone )系、氟系或鹼系之 消泡劑、平滑劑、咪唑系、噻唑系、三唑系等之密著賦予 劑、矽烷耦合劑等之表面處理劑、酞菁藍、酞菁綠、碘綠 、二重氮黃、碳黑等之著色劑、含磷化合物、含溴化合物 、氫氧化鋁、氫氧化鎂等難燃劑、磷酸系氧化防止劑、苯 酚系氧化防止劑等之氧化防止劑。 -17- 200914537 本發明之樹脂組成物，尤其適合使用作爲多層印刷配 線板之層間絕緣用。尤其較佳之可使用的形態爲由樹脂組 成物層（A層）及支持體膜（B層）所構成之接著膜及樹 脂組成物層（A層）形成於銅箔上之RCC型之接著膜之形 態。 接著膜可依照同業業者之公知方法製造，例如，使本 發明之熱硬化性樹脂組成物溶解於有機溶劑中調製成清漆 ，將此清漆塗佈於支持體膜及銅箔上，藉由加熱或吹熱風 等使有機溶劑乾燥以形成熱硬化性樹脂組成物層。 支持體膜（B層）爲製造接著膜時之作爲支持體者， 於多層印刷配線板之製造中，於最後須將其剝離或除去者 。作爲支持體膜，可舉出例如：聚乙烯、聚氯乙烯等之聚 烯烴、聚對苯二甲酸乙二酯（以下亦簡稱爲「PET」）、 聚萘酸乙二酯等之聚酯、聚碳酸酯、以及脫模紙或銅箔等 之金屬箔等。亦可使用聚醯亞胺、聚醯胺、聚醯胺醯亞胺 、液晶聚合物等之耐熱性樹脂。又，於以銅箔作爲支持體 膜使用之情況，可用氯化鐵、氯化銅等之蝕刻液藉由蝕刻 而去除。支持體膜亦可施行霧面（mat)處理、電暈處理 之外，於考量剝離性時，以施行脫模處理爲更佳。支持體 膜之厚度並無特別限定，通常可用10〜150 μπι，以25~50 μηι的範圍爲佳。 於RCC型之情況，銅箔係作爲多層印刷配線板的導 體層之一部份使用。通常可舉出電解銅箔、軋製銅箔，亦 可用極薄銅箔。極薄銅箔亦可附帶有載體銅箔。銅箔之厚 -18- 200914537 度並無特別限定，欲形成微細間距的配線’以用極薄銅箔 爲佳。 作爲用以調製清漆之有機溶劑，可舉出例如：丙酮、 甲乙酮、環己酮等之酮類、乙酸乙酯、乙酸丁酯、溶纖素 乙酸酯、丙二醇單甲醚乙酸酯、卡必醇乙酸酯等之乙酸酯 類、溶纖素、丁基卡必醇等之卡必醇類、甲苯、二甲苯等 之芳香族烴類、二甲基甲醯胺、二甲基乙醯胺、N-甲基吡 咯烷酮等。有機溶劑亦可組合2種以上使用。 乾燥條件並無特別限定，爲保持接著力，於乾燥時須 儘可能不進行熱硬化性樹脂組成物之硬化是重要的。又， 若於接著膜中有多量有機溶劑殘留，會成爲硬化後發生鼓 起的原因，故熱硬化性樹脂組成物中之有機溶劑之含有比 例通常宜乾燥至5質量％以下，以3質量％以下爲佳。具 體的乾燥條件係依熱硬化性樹脂組成物與清漆中之有機溶 劑量而異，例如，於含有3 0〜60質量％之有機溶劑之清漆 ，通常可於8 0〜120 °C下乾燥3〜13分鐘左右。同業業者可 藉由簡單的實驗而設定適當之較佳的乾燥條件。 樹脂組成物層（A層）之厚度通常可定爲5~5 00 μπι 之範圍。Α層之厚度的較佳範圍依接著膜之用途而異，於 用於藉由層疊（build-up )工法製造多層印刷配線板之情 況，形成線路之導體層之厚度通常爲5~7 0 μπι，故相當於 層間絕緣層之Α層之厚度以10〜100 μιη之範圍爲佳。 Α層亦可用保護膜保護。藉由用保護膜保護，可防止 樹脂組成物層表面之塵埃等至附著與發生刮痕。保護膜可 200914537 於層合（laminate )時剝離。作爲保護膜可用與支持膜同 樣的材料。保護膜之厚度並無特別限定，以1〜40 μιη的範 圍爲佳。 本發明之接著膜可藉由真空層合機而較佳地層合於線 路基板上。此處所使用之內層線路基板，主要可舉出：聚 酯基板、聚醯亞胺基板、聚醯胺醯亞胺基板、液晶聚合物 基板等之內層線路基板。又，本發明之接著膜亦可使用於 使多層印刷配線板更進一步多層化之目的。又，線路表面 藉由過氧化氫/硫酸、默克艾奇邦得（MEC Etch Bond )( MEC (股）公司製）等之表面處理劑預先進行粗化處理， 就絕緣層與線路基板之密著性之考量爲較佳者。 作爲市售之真空層合機，可舉出例如：Nichig0_ Morton Co _ Ltd.製之 Vacuum Applicator、名機製作所（股 )製之真空加壓式層合機、日立Techno Engineering (股 )製之輥式Dry Coater、日立AIC Inc·製之真空層合機等 〇 於層合之中，於接著膜有保護膜之情況，於除去該保 護膜後’將接著膜一邊加壓及加熱之下壓合於線路基板上 。層合之條件係對接著膜及線路基板視需要施以預熱，壓 合溫度以70〜140°C爲佳，壓合壓力以定爲l~llkgf /cm2 爲佳，以在空氣壓20mmHg以下之減壓下進行層合爲佳。 又，層合之方法可爲批次式，亦可爲用輥之連續式。 於由樹脂組成物層（A層）及支持體膜（B層）所構 成的接著膜之情況，係採行下述般之步驟。將接著膜層合 -20- 200914537 於基板後，冷卻至室溫附近，將支持體膜剝離。然後，對 層合於線路基板之熱硬化性樹脂組成物進行加熱硬化。加 熱硬化之條件通常可選擇在150~220°C、20分鐘〜180分 鐘之範圍，更佳者可選擇在 160〜200 °C、30分鐘〜120分 鐘之範圍。又，於支持體膜有脫模處理或矽氧烷（ silicone )等之剝離層之情況，可於熱硬化性樹脂組成物 之加熱硬化後或加熱硬化及開孔後將支持體膜剝離。 於形成樹脂組成物之硬化物所成之絕緣層後，視需要 亦可對線路基板進行鑽孔、雷射、電漿、或此等之組合等 方法進行開孔以形成通孔（via hole )或穿孔（through hole )。尤以藉由二氧化碳雷射或YAG雷射等之雷射進行 開孔常被採用。 接著，進行絕緣層之表面處理。表面處理可採用去污 步驟（desumia process)中所用之方法，亦可用兼備去污 步驟之形態進行。作爲去污步驟中所用之藥品，通常爲氧 化劑。作爲氧化劑，可舉出例如：過錳酸鹽（過錳酸鉀、 過錳酸鈉等）、重鉻酸鹽、臭氧、過氧化氫/硫酸、硝酸 等。以於藉由層疊（b u i 1 d - u p )工法製造多層印刷配線板 中之絕緣層的粗化所廣爲使用之氧化劑爲佳。以用鹼性過 錳酸溶液（例如過錳酸鉀、過錳酸鈉之氫氧化鈉水溶液） 進行處理爲佳。於以氧化劑處理之前亦可進行藉由膨潤劑 之處理。又，於藉由氧化劑之處理後通常係進行藉由還原 劑之中和處理。 上述般的去污步驟亦兼具有用以提高藉由鍍敷形成之 -21 - 200914537 導體層的剝離強度而使絕緣體層表面粗化以設置凹凸之目 的。 於進行表面處理後，於絕緣體層表面藉由鍍敷形成導 體層。導體層形成可藉由組合非電鍍敷與電鍍的方法施行 。又，亦可形成與導體層相反的圖案之鍍敷光阻層，僅藉 由非電鍍敷形成導體層。導體層形成後，可藉由在 150~200 °C下進行 20〜90分鐘之退火（anneal)處理，使 導體層之剝離強度更進一步提高並安定化。 作爲導體層之線路加工以形成線路的方法，可用同業 業者所公知的減去法、半加成法等。於減去法之情況，非 電銅鍍敷層之厚度爲0.1〜3 μιη，以0_3〜2 μιη爲佳。在其 上形成電鍍層（面板（panel)鍍敷層）3~35 μηι (以5〜20 μπι之厚度爲佳）之後，形成蝕刻光阻層，藉由以氯化鐵 、氯化銅等之蝕刻液進行蝕刻而形成導體圖案後，將蝕刻 光阻層剝離，藉此可得到線路基板。又，於半加成法之情 況，係於形成非電銅鍍敷層之厚度〇.1~3 μιη (以0.3〜2 μιη爲佳）之非電銅鍍敷層後，形成圖案光阻層，然後於 銅電鍍後將其剝離，藉此可得到線路基板。 於在銅箔上形成樹脂組成物層（Α層）之RC C型的接 著膜之情況，係採行下述般的步驟。將接著膜層合於線路 基板上，如上述般使熱硬化性樹脂組成物加熱硬化。然後 ，如上述般進行開孔，藉由軟蝕刻進行通孔之表面處理。 然後，進行非電鍍敷，如上述般用減去法等，可得到線路 基板。作爲所使用之銅箔，通常係使用1 2或1 8 μηι品之 -22- 200914537 電解銅箔，可舉出例如：三井金屬礦業（股）製「DFF」 、「NS-VLP」、日礦金屬（股）製「JTC」等。又，亦可 因應細線條（fine line )之要求而使用極薄之銅箔，可舉 出例如：三井金屬礦業（股）製「Micro Thin Ex」、曰本 電解（股）製「YSMAP」等。 以下，就本發明之內容藉由實施例具體地做說明，惟 本實施例並非用以對本發明做任何限制者。 〔製造例1〕 <聚醯亞胺樹脂之製造（聚醯亞胺樹脂清漆A) > 於附有攪拌裝置、溫度計及冷凝器之燒杯中，加入作 爲溶劑之 r -丁內酯 203.07g、304.60g 之 Solveso 150，再 加入異佛酮二異氰酸酯88.8g(0.4莫耳）與氫化聚丁二烯 二醇（羥基値 48_5KOH-mg/g，分子量 2 3 1 3 ) 23 1.3 g ( 0.1 莫耳）、與聚丁二烯二醇（羥基値52.6KOH-mg/g，分子 量2133) 213_3g(0.1莫耳），於70°C下反應4小時。然 後，加入壬基酚醛清漆樹脂（羥基當量229.4g/eq，平均 4.27官能基，平均計算分子量979.5g/莫耳）195.9g(0.2 莫耳）與乙二醇雙三苯六甲酸酐41.0g(0.1莫耳），以2 小時之時間昇溫至1 5 0 °C，使其反應1 2小時。 反應後成爲透明之褐色液體，得到不揮發份爲6 0 %， 黏度爲1 5Pa · s ( 25 °C )之聚醯亞胺樹脂溶液。將得到之 聚醯亞胺樹脂之溶液塗佈於KB r板上，對使溶劑揮發所得 之試樣測定紅外線吸收光譜之結果，異氰酸酯基之特性吸 -23- 200914537 收之2270cm·1完全消失，確認出在725 CHT1與178()01^1 與1720CHT1之醯亞胺環之吸收。又於154(^1^1處確認出 胺基甲酸酯鍵之吸收。又，隨著醯亞胺化之進行所產生之 二氧化碳之發生量，藉由燒杯中加入之重量變化的追蹤得 知爲8.8g(0.2莫耳）。乙二醇雙三苯六甲酸酐之酸酐的 官能基當量爲0.2莫耳，二氧化碳之產生量亦爲0.2莫耳 ，得到之結論爲酸酐全部用於醯亞胺之形成，並無羧酸酐 存在。 藉此可做如下之結論：異氰酸酯基內有0.2莫耳係轉 變成醯亞胺鍵，其餘的異氰酸酯基則與氫化聚丁二烯二醇 與聚丁二烯二醇之羥基及壬基酚醛清漆樹脂中的苯酚性羥 基一起形成胺基甲酸酯鍵，而於樹脂中賦予壬基酚醛清漆 樹脂之苯酚性羥基，而可得到部分的苯酚性羥基經改質成 爲胺基甲酸酯之改質的聚胺基甲酸酯醯亞胺樹脂。 〔製造例2〕 <聚醯亞胺樹脂之製造（聚醯亞胺樹脂清漆B) > 於附有攪拌裝置、溫度計及冷凝器之燒杯中，加入作 爲溶劑之乙酸乙二醇酯292.09g、292.09g之Solveso 150 ，再加入異佛酮二異氰酸酯88.8g (0.4莫耳）與聚丁二烯 二醇（羥基値 52_6KOH-mg/g，分子量 2 1 3 3 ) 426.6g ( 0.2 莫耳），於70°C下反應4小時。然後，加入壬基酚醛清漆 樹脂（羥基當量229.4 g/eq，平均4.27官能基，平均計算 分子量979.5g/莫耳）195.9g(0.2莫耳）與乙二醇雙三苯 -24- 200914537 六甲酸酐41.0g ( 0.1莫耳），以2小時之時間昇 °C，使其反應1 2小時。 反應後成爲透明之褐色液體，得到不揮發份 黏度爲12Pa · s ( 25 t )之聚醯亞胺樹脂溶液。 聚醯亞胺樹脂之溶液塗佈於KBr板上，對使溶劑 之試樣測定紅外線吸收光譜之結果，異氰酸酯基 收之2270CHT1完全消失，確認出在725 CHT1與 與1 720(:1^1之醯亞胺環之吸收。又於1 540CHT1 胺基甲酸酯鍵之吸收。又，隨著醯亞胺化之進行 二氧化碳之發生量，藉由燒杯中加入之重量變化 知爲8.8g(0.2莫耳）。乙二醇雙三苯六甲酸酐 官能基當量爲0.2莫耳，二氧化碳之產生量亦爲 ，得到之結論爲酸酐全部用於醯亞胺之形成，並 存在。藉此可做如下之結論：異氰酸酯基內有〇. 轉變成醯亞胺鍵，其餘的異氰酸酯基則與氫化聚 醇與聚丁二烯二醇之羥基及壬基酚醛清漆樹脂中 羥基一起形成胺基甲酸酯鍵，而於樹脂中賦予壬 漆樹脂之苯酚性羥基，而可得到部分的苯酚性羥 成爲胺基甲酸酯之改質的聚胺基甲酸酯醯亞胺樹, <參考例1> 添加作爲成分（A )之製造例1所得之聚醯 組成物清漆A 40份、作爲成分（B)之雙酚A清 樹脂之乙二醇單乙醚乙酸酯（以下記爲EDGAc ) -溫至1 50 爲 5 6%， 將得到之 揮發所得 之特性吸 1 780cm·1 處確認出 所產生之 的追蹤得 之酸酐的 0.2莫耳 無羧酸酐 .2莫耳係 丁二烯二 的苯酚性 基酚醛清 基經改質 亞胺樹脂 漆型環氧 及 Ipuzol -25- 200914537 15 0 (芳香族烴系混合溶劑：出光石油化學（股）製）混 合清漆（固形份5 0 %，環氧當量21 0，日本環氧樹脂（股 )製「157S70」）10.9份、咪唑衍生物（日本環氧樹脂（ 股）製「P200H50」）0·5份、球形二氧化矽（比表面積 8 0m2/g ) 6份、以及甲苯1〇份、7 丁內酯5.5份，調製成 清漆狀之樹脂組成物。 <參考例2 > 添加作爲成分（A )之製造例1所得之聚醯亞胺樹脂 組成物清漆A 40份、作爲成分（B)之雙酚A清漆型環氧 樹脂之E D G A c及I p u ζ ο 1 1 5 0混合清漆（固形份5 0 %，環 氧當量210’曰本環氧樹脂（股）製「157S70」）1〇_9份 、咪唑衍生物（日本環氧樹脂（股）製「P200H50」）0.5 份、球形二氧化矽（比表面積6.2m2/g) 6份、以及甲苯 1 〇份，調製成清漆狀之樹脂組成物。 <參考例3> 添加作爲成分（A )之製造例2所得之聚醯亞胺樹脂 組成物清漆B 4〇份、作爲成分（B)之雙酚A清漆型環氧 樹脂之EDGAc及Ipuzol 150混合清漆（固形份50%，環 氧當量210，日本環氧樹脂（股）製r 157S70」）ι〇·9份 、咪唑衍生物（日本環氧樹脂（股）製「P200H50」）0.5 份、球形二氧化矽（比表面積8 0 m2 / g ) 6份、以及甲苯1 〇 份、r 丁內酯5.5份，調製成清漆狀之樹脂組成物。 -26- 200914537 <參考例4> 添加作爲成分（A )之製造例2所得之聚醯亞胺樹脂 組成物清漆B 40份、作爲成分（B)之雙酚A清漆型環氧 樹脂之EDGAc及Ipuzol 150混合清漆（固形份50°/。，環 氧當量210，日本環氧樹脂（股）製「157S70」）10.9份 、咪唑衍生物（曰本環氧樹脂（股）製「P200H50」）0.5 份、球形二氧化矽（比表面積6.2m2/g) 6份、以及甲苯 1 〇份’調製成清漆狀之樹脂組成物。 〔實施例1〕 添加作爲成分（A )之製造例1所得之聚醯亞胺樹脂 組成物清漆A 40份、作爲成分（B)之雙酚A清漆型環氧 樹脂之EDGAc及Ipuz〇l 150混合清漆（固形份50%，環 氧當量210，日本環氧樹脂（股）製「157S7〇」）ι〇·9份 、咪嗖衍生物（日本環氧樹脂（股）製「ρ2〇〇Η5〇」）ο」 份' 球形二氧化矽（比表面積30m2/g ) 6份、以及甲苯1〇 份、r 丁內酯2份，調製成清漆狀之樹脂組成物。 〔實施例2〕 添加作爲成分（A )之製造例2所得之聚醯亞胺樹脂 組成物清漆B 40份、作爲成分（B)之雙酚A清漆型環氧 樹脂之EDGAc及Ipuzol 150混合清漆（固形份50%，環 氧當量210，曰本環氧樹脂（股）製「157S7〇」）ι〇·9份 -27- 200914537 、咪唑衍生物（日本環氧樹脂（股）製「P200H50」）0.5 份、球形二氧化矽（比表面積30m2/g ) 6份、以及甲苯1〇 份、r 丁內酯2份，調製成清漆狀之樹脂組成物。 〔實施例3〕 添加作爲成分（A )之製造例1所得之聚醯亞胺樹脂 組成物清漆A 40份、作爲成分（B)之雙酚A清漆型環氧 樹脂之EDGAc及Ipuzol 1 50混合清漆（固形份50%，環 氧當量210，日本環氧樹脂（股）製「157S70」）10.9份 、咪唑衍生物（日本環氧樹脂（股）製「P200H50」）0.5 份、球形二氧化矽（比表面積20m2/g) 6份、以及甲苯10 份、r 丁內酯4份，調製成清漆狀之樹脂組成物。 〔實施例4〕 添加作爲成分（A )之製造例2所得之聚醯亞胺樹脂 組成物清漆B 40份、作爲成分（B)之雙酚A清漆型環氧 樹脂之EDGAc及Ipuzol 150混合清漆（固形份50%，環 氧當量210，曰本環氧樹脂（股）製r157S7〇」）1〇9份 、咪哩衍生物（曰本環氧樹脂（股）製「P2〇〇H50」）0.5 份、球形—氧化砂（比表面積20m2/g) 6份、以及甲苯10 份、r 丁內酯4份’調製成清漆狀之樹脂組成物。 〔實施例5〕 添加作爲成分（A )之製造例1所得之聚醯亞胺樹脂 -28- 200914537 組成物清漆A40份、作爲成分（B)之雙酚A清漆型環氧 樹脂之EDGAc及Ipuzol 1 50混合清漆（固形份50% ,環 氧當量210，曰本環氧樹脂（股）製「157S70」）10.9份 、咪唑衍生物（日本環氧樹脂（股）製「P2 00H50」）0.5 份、球形氧化鋁（比表面積22m2/g ) 6份、以及甲苯1〇 份，調製成清漆狀之樹脂組成物。 〔實施例6〕 添加作爲成分（A )之製造例2所得之聚醯亞胺樹脂 組成物清漆B 40份、作爲成分（B)之雙酚A清漆型環氧 樹脂之EDGAc及Ipuzol 150混合清漆（固形份50%，環 氧當量210，日本環氧樹脂（股）製「157S70」）10.9份 、咪唑衍生物（日本環氧樹脂（股）製「P200H50」）0.5 份、球形氧化鋁（比表面積22m2/g ) 6份、以及甲苯10 份，調製成清漆狀之樹脂組成物。 <分散性> 於參考例1〜4中，使清漆於室溫下靜置約1 2小時， 則塡料沈降，清漆發生分離，而實施例1〜6中，塡料則維 持著均一分散之狀態。 〔實施例7〕 就實施例1中得到之清漆，在脫模處理聚對苯二甲酸 乙二酯（厚3 8 μπι ’以下簡稱爲PET )上，將其樹脂組成 -29- 200914537 物用塗佈機以使乾燥後之樹脂厚度成爲60 Pm的方式進行 塗佈，於80〜120°C (平均l〇〇°C )下乾燥12分鐘，形成 樹脂組成物層，得到接著膜。 〔實施例8〕 就實施例2中得到之清漆： '以與實施例7同樣的做法 ，在PET上形成樹脂組成物層 ，得到接著膜。 〔實施例9〕 就實施例3中得到之清漆’ 以與實施例7同樣的做法 ，在PET上形成樹脂組成物層 ，得到接著膜。 〔實施例1 0〕 就實施例4中得到之清漆， 以與實施例7同樣的做法 ，在PET上形成樹脂組成物層， ，得到接著膜。 〔實施例11〕 就實施例5中得到之清漆’ 以與實施例7同樣的做法 ，在PET上形成樹脂組成物層： 1得到接著膜。 〔實施例1 2〕 就實施例6中得到之清漆’ 以與實施例7同樣的做法 ，在PET上形成樹脂組成物層^ ’得到接著膜。 將實施例7-12中所得到之接著膜，於180。(：下加熱硬 -30- 200914537 化9 0分鐘。各樹脂組成物之硬化物特性示於表1。又，拉 伸斷裂強度測定係依據日本工業規格（JI s ) κ 7 1 2 7進行。 又’介電特性係用空洞共振攝動法（阿吉連特技術（股） 公司製Ε8362Β)進行評估。特性値示於表1。 <比較例1 > 作爲比較例1係使環氧樹脂製之層間絕緣材料（味之 素精密技術（股）公司製ABF-GXcodel3)於18〇。(：下進 行加熱硬化9 0分鐘得到硬化物。與上述同樣地，硬化物 之特性値示於表1。 〔表1〕 實施例 7 實施例 8 實施例 9 實施例 10 實施例 11 實施例 12 比較例 1 彈性係數(MPa) 57 131 88 151 66 141 4000 拉伸強度(MPa) 13 13 15 20 16 16 93 斷裂伸長度(％) 105 65 73 53 76 45 5 介電係數(1 GHz) 2.42 2.48 2.54 2.75 2.83 2.84 3.35 介電正切(1 GHz) 0.008 0.007 0.006 0.007 0.008 0.006 0.012 〔實施例1 3〕 與銅箔之密著力（其1 ) 將實施例7中得到之接著膜，分別在銅箔（日礦金屬 (股）製，JTC箔）之S面及Μ面，藉由名機製作所（股 )製真空層合機（丨aminator )，於溫度 1〇〇 t 、壓力 7kgf/cm2、氣壓5mmHg以下之條件進行單面層合，分別 -31 - 200914537 準備銅箔/接著膜/PET之三層品。然後，將脫模處理PET 剝離’同樣地層合至經默克艾奇邦得（Μ E C E t c h Β ο n d ) CZ8100處理之覆銅積層板上。然後，於120°c進行3〇分 鐘’再於1 80°C進行90分鐘之加熱硬化。用得到之基板測 定樹脂/銅箔的界面之剝離強度，得S面之剝離強度爲 (K66kgf/Cm，Μ面之剝離強度爲1.22kgf/cm。又，剝離強 度測定係依據JIS C648 1進行評估，銅箔厚度定爲18 μηι 〔實施例1 4〕 與銅箔之密著力（其2) 用實施例8得到之接著膜，以與實施例1 3同樣的做 法測定樹脂/銅箔的界面之剝離強度，得S面之剝離強度 爲〇_73kgf/cm，Μ面之剝離強度爲1.05kgf/cm。 〔實施例1 5〕 與銅箔之密著力（其3) 用實施例9得到之接著膜，以與實施例1 3同樣的做 法測定樹脂/銅箔的界面之剝離強度，得S面之剝離強度 爲〇.50kgf/cm，Μ面之剝離強度爲l.〇4kgf/cm。 〔實施例1 6〕 與銅箔之密著力（其4) 用實施例1 0得到之接著膜，以與實施例1 3同樣的做 -32- 200914537 法測定樹脂/銅箔的界面之剝離強度，得s面之剝離強度 爲〇.67kgf/cm，Μ面之剝離強度爲0.94kgf/cm。 〔實施例1 7〕 與銅箔之密著力（其5) 用實施例1 1得到之接著膜，以與實施例1 3同樣的做 法測定樹脂/銅箔的界面之剝離強度，得S面之剝離強度 爲〇.46kgf/cm，Μ面之剝離強度爲1.13kgf/cm。 〔實施例1 8〕 與銅箔之密著力（其6) 用實施例1 2得到之接著膜，以與實施例1 3同樣的做 法測定樹脂/銅箔的界面之剝離強度，得S面之剝離強度 爲0.44kgf/cm，Μ面之剝離強度爲l.〇6kgf/cm。 <比較例2 > 用環氧樹脂製之層間絕緣材料（味之素精密技術（股 )製ABF-GXc〇del3 )，以與實施例13同樣的做法測定樹 脂/銅箔的界面之剝離強度，得 S面之剝離強度爲 〇.29kgf/cm，Μ面之剝離強度爲LOkgf/cm。 實施例1 3 -1 8、比較例2之結果彙整於表2。可知： 實施例者，即使對於銅箔之S面般的平滑之表面亦顯示良 好的密著性。 -33- 200914537 〔表2〕 實施例 實施例 實施例 實施例 實施例 實施例 比較例 13 14 15 16 17 18 2 S 面(kgf/cm) 0.66 0.73 0.50 0.67 0.46 0.44 0.29 Μ 面(kgf/cm) 1.22 1.05 1.04 0.94 1.13 1.06 1.44 〔實施例1 9〕 有關鍍敷層剝離（其1 ) 將實施例8中得到之接著膜，在經默克艾奇邦得（ MEC Etch Bond) CZ8100處理之覆銅積層板上，藉由名機 製作所（股）製真空層合機（laminator )，於溫度100°C 、壓力7kgf/cm2、氣壓5mmHg以下之條件於兩面進行層 合。然後，將脫模處理PET剝離，於18(TC進行30分鐘 之加熱硬化形成絕緣層。兼備去污步驟之絕緣層之表面處 理製程，係使用阿托特克（日本）公司製之下述藥液： 膨潤劑「Swelling Dip Securiganth」、 氧化劑「Concentrate Compact CP」（過锰酸驗溶液 )> 還原劑「Reduction solution Securiganth P-500」。 於溫度8 0 °C以膨潤劑溶液進行表面處理5分鐘，然後 於溫度80°C以氧化劑進行表面處理5分鐘，最後於40°C 下以還原劑溶液進行中和處理5分鐘。然後對絕緣層表面 賦予非電銅鍍敷之觸媒後，於非電銅鍍敷液中於3 2 °C浸漬 分鐘，形成1.5 μπι之非電銅鍍敷皮膜。將此以150°C 進行3 0分鐘乾燥後，進行酸洗淨，以含磷銅板作爲陽極 -34- 200914537 ，以陰極電流密度2.0 A/dm2進行12分鐘銅電鍍，形成銅 電鍍皮膜。然後，再於1 80 °C進行30分鐘退火處理。得到 之導體層之剝離強度爲0.71 kgf/cm。又，剝離強度測定係 依據JIS C6481進行評估，導體鍍層厚度定爲約25 μιη。 (比較例3 ) 用環氧樹脂製之層間絕緣材料（味之素精密技術（月$ )公司製ABF-GXcodel3 )，以與實施例19同樣的做法形 成絕緣層。用阿托特克（日本）公司製之藥液同樣地進行 表面處理。 於溫度60°C藉由膨潤劑溶液進行5分鐘表面處理，然 後，於溫度8 0 °C藉由氧化劑進行1 5分鐘表面處理，最後 ，於4〇°C藉由還原劑溶液進行5分鐘中和處理。又，得到 之導體層之剝離強度爲〇.6kgf/cm。 〔製造例3〕 <線狀改質聚醯亞胺樹脂之製造（線狀改質聚醯亞胺 樹脂清漆C ) > 於反應器中，將50g之G-3 000 ( 2官能性羥基末端 聚丁二烯，數平均分子量=5 047 ( GPC法），羥基當量 = 1798g/eq.，固形份100重量％，日本曹達（股）製）、 23.5g之Ipuzol 150、二丁基錫月桂酸酯0.0 05 g混合，使 其均一地溶解。於達到均一時昇溫至5〇°c，再邊攪拌邊添 加甲苯-2,4-二異氰酸酯（異氰酸酯基當量=8 7.08 g/eq.) -35- 200914537 4.8g，使其反應約3小時。然後’將Iti ，再對其添加二苯甲酮四羧酸二酐（酵 )8.96g、三乙二胺〇.〇7g、乙酸乙二醇 業（股）公司製）40.4g’邊攪拌下昇潘 應約4小時。對藉由FT-IR之2250cm 失得到確認。以NC Ο波峰之消失之確 ，使反應物降溫至室溫後以100網目之 狀改質聚醯亞胺樹脂（線狀改質聚醯亞 線狀改質聚醯亞胺樹脂清漆A之β s ( 2 5 °c，Ε型黏度計） 酸値= l6_9mgKOH/g 固形份=5 0重量％ <參考例5 > 添加35份之作爲成分（A)之於製 亞胺樹脂清漆C、1 0 · 9份之作爲成分（ 型環氧樹脂之EDGAc及buz。1 150 5 0%，環氧當量’日本環氧樹脂（ ) '酚醛清漆（大日本油墨化學（股： 」）4.5份、球形二氧化砂（比表面積 及甲苯10份、T 丁內酯2份，調製成 物。 分散性 :反應物冷卻至室溫 :酐當量=161.ig/eq 酯（Diacel化學工 l至1 3 0 °C，進行反 1的NCO波峰之消 認視爲反應的終點 濾布過濾，得到線 胺樹脂清漆C )。 i狀·黏度=7.5 P a . 造例3得到之聚醯 B )之雙酚A清漆 混合清漆（固形份 股）製「1 5 7 S 7 0」 )製「TD2090-60M 4.1m2/g) 6 份、以 清漆狀之樹脂組成 -36- 200914537 於比較例4中，即令使清漆於室溫下靜置約1 2小時 調料亦可維持著均一分散之狀態。 <物性値> 對比較例4中得到之清漆，以與實施例7同樣的做法 在PET上形成樹脂組成物層，得到接著膜’於1 8 0 °C進行 加熱硬化90分鐘。硬化物之特性値示於表3。又，用比較 例4所得之接著膜，以與實施例1 3同樣的做法測定樹脂/ 靖箔的界面之剝離強度，得S面之剝離強度爲〇.55kgf/Cm ’ Μ面之剝離強度爲〇.67kgf/cm。 〔表3〕 參考例5 彈性係數（MPa) 33 拉伸強度（MPa) 12 斷裂伸長度（％ ) 67 介電係數（1GHz ) 2.64 介電正切（1GHz ) 0.013 -37-(1-b) Specific reaction conditions 'For example, the reaction of the polybutadiene polyol of the reaction component [a] with the diisocyanate compound of the reaction component [b] can be carried out in an organic solvent at a reaction temperature of 80 ° C or less. The reaction time is usually carried out under the conditions of 2 to 8 hours. Moreover, it may be carried out in the presence of a catalyst if necessary. Next, a tetrabasic acid dianhydride and a polyfunctional phenol compound are added to the reaction solution, and the reaction is carried out at a reaction temperature of 120 to 160 ° C for a reaction time of 5 to 24 hours. The reaction is usually carried out in the presence of a catalyst. Further, it can be carried out by adding -13- 200914537 organic solvent. In this reaction, carbon dioxide is generated by the reaction of an isocyanate group with an acid anhydride group to form a quinone bond, so that the weight of the carbon dioxide can be determined by measuring the weight loss before and after the reaction, and the formation of the carbon dioxide can be calculated. The number of moles of the amine group. After the reaction is completed, the reaction solution may be filtered as needed to remove insoluble matter. Thus, a varnished polyimide resin can be obtained. The amount of the solvent in the varnish can be appropriately adjusted by adjusting the amount of the solvent at the time of the reaction or adding a solvent or the like after the reaction. The polyimine resin of the present invention can be usually used to prepare a composition in the above varnish state. In the case of isolation, for example, the obtained varnish is successively added in methanol of a poor solvent to precipitate a polyimine to obtain a solid. Examples of the solvent used in each of the above reactions include N,N'-dimethylformamide' Ν, Ν'-diethylformamide, hydrazine, Ν'-dimethylacetamide. , Ν, Ν'-diethylacetamide, dimethyl boron, diethyl hydrazine, hydrazine-methyl-2-pyrrolidone, tetramethyl urea, r-butyrolactone, cyclohexanone, diethylene glycol A polar solvent such as methyl ether, triethylene glycol dimethyl ether, carbitol acetate, propylene glycol monomethyl ether acetate, or propylene glycol monoethyl ether acetate. These solvents may also be used in combination of two or more kinds. Further, a nonpolar solvent such as an aromatic hydrocarbon may be appropriately mixed as needed. Examples of the catalyst used in each of the above reactions include tetramethylbutanediamine, benzyldimethylamine, triethanolamine, triethylamine, hydrazine, and N-dimethylpiperidine (piperidine). a tertiary amine such as α-methyloctyldimethylamine, N-ethylmorphine or triethylenediamine, or dibutyltin laurate 'dimethyl-14- 200914537 tin dichloride, cobalt naphthalate An organic metal catalyst such as zinc naphthalate or the like. These catalysts may also be used in combination of two or more kinds. As the catalyst, triethylenediamine is particularly preferred. Examples of the epoxy resin in the present invention include bisphenol A type epoxy resin, bisphenol F type epoxy resin 'novolak resin, bisphenol S type epoxy resin, alkyl novolac resin, and biphenol. Type epoxy resin, naphthalene type epoxy resin, dicyclopentadiene type epoxy resin, epoxide with condensate of phenol and phenolic hydroxyl group aromatic aldehyde, glycidyl isocyanurate, An epoxy resin having two or more functional groups in one molecule, such as an alicyclic epoxy resin. These epoxy resins may be used in combination of two or more kinds. Further, it is preferred to use a bisphenol A type epoxy resin. In the composition of the present invention, an epoxy resin hardener may be formulated as needed. Examples of the epoxy resin curing agent include an amine curing agent, a guanidine curing agent, an imidazole curing agent, a phenol curing agent, an acid anhydride curing agent, or the like, and an epoxy adduct thereof. Microencapsulators, etc. In particular, a phenol-based curing agent is preferred in consideration of viscosity stability when the resin composition is used as a varnish. The epoxy resin hardener may be used in combination of two or more kinds. Specific examples of the epoxy resin curing agent include dicyandiamide as an amine curing agent, imidazolium as an imidazole curing agent, and 2-phenyl-4-methyl-5-hydroxymethylimidazole. And 2,4-diamino-6-[ 2'-methylimidazolium-( 1 ')]-ethyl-S-trimisomeric cyanuric acid adduct, as a phenolic curing agent A novolak resin (for example, Phen〇lite 705 0 series: manufactured by Dainippon Ink Chemical Co., Ltd.). The polyimine resin composition of the present invention is used for the control of the crosslinking density of the epoxy resin of the component (A) -15-200914537 and the epoxy resin of the component (B). Component (D) A polyfunctional phenol compound having two or more phenolic hydroxyl groups in one molecule is preferred. By using the component (D), the crosslinking density of the component (A) and the component (B) can be increased, whereby thermal expansion or the like at a temperature higher than the glass transition temperature can be lowered. In order to increase the crosslinking density and lower the thermal expansion, the ratio of the component (A) to the component (B) to the component (D) in the resin composition is preferably 100% by weight based on the total amount (A) It is 40 to 85% by weight, the component (B) is 15 to 40% by weight, and the component (D) is 0 to 20% by weight. The total of the phenolic hydroxyl group (X) in the component (A) and the phenolic hydroxyl group (Z) in the component (D), and the molar ratio of the epoxy group (y) in the component (B) to (x + z ) / (y) is preferably 0.7 to 1.3. An example of the polyfunctional phenol compound having two or more phenolic hydroxyl groups in one molecule of the component (D) is the same as the above-mentioned reaction component [d]. The thermosetting polyimine resin composition of the present invention may be a hardening accelerator if necessary. Examples thereof include melamine, dicyandiamide, andguanine and derivatives thereof, amines, phenols having one hydroxyl group, organic phosphines, scaly salts, tetrabasic ammonium salts, polybasic acid anhydrides, and light. A cationic catalyst, a cyanate compound, an isocyanate compound, a blocked isocyanate compound, or the like. The resin composition of the present invention may contain an inorganic cerium filler having a specific surface area of 18 to 5 〇m 2 /g. Examples of the inorganic cerium filler include: cerium oxide, alumina, and the like. Especially cerium oxide is preferred. The inorganic enamel filler can also be used in combination of two or more types. The blending amount of the inorganic ceramium filler is not particularly limited, and it is preferably -16-200914537, which can be added in the range of 10 to 50% by mass in the resin composition. If it is less than 10% by mass, it tends to be difficult to obtain effects such as a coefficient of thermal expansion and an improvement in tack. When it exceeds 5 〇 mass%, not only the laser workability is deteriorated, but also the elastic modulus of the cured product is also high, and there is a tendency to become a hard and brittle material. Further, the specific surface area of the inorganic cerium filler can be used in the range of 18 to 50 m2/g. If it is outside this range, the mash will have a tendency to settle, making it difficult to maintain the varnish for a long period of time. The lower limit of the range of the specific surface area is more preferably 20 m 2 /g or more. The upper limit of the range of the specific surface area is preferably 40 m 2 /g, more preferably 35 m 2 /g, and particularly preferably 30 m 2 /g or less. For example, the specific surface area is preferably in the range of 18 to 40 m 2 /g, more preferably in the range of 18 to 35 m 2 /g, and particularly preferably in the range of 20 to 30 m 2 /g. The analysis of the specific surface area can be carried out by the so-called "BET method" in which the specific surface area of the sample is adsorbed at a temperature of liquid nitrogen by a known molecule on the surface of the powder particle. Out. The most frequently used is the BET method of low temperature and low humidity physical adsorption by an inert gas. In the resin composition of the present invention, various resin additives and resin components other than the components (A) and (B) may be blended in a range in which the effects of the present invention are exerted. Examples of the resin additive include a tackifier such as urethane or bentonite, a silicone system, a fluorine-based or alkali-based antifoaming agent, a smoothing agent, an imidazole-based compound, a thiazole system, and a triazole. a surface treatment agent such as a adhesion imparting agent or a decane coupling agent, a coloring agent such as phthalocyanine blue, phthalocyanine green, iodine green, disazo yellow, carbon black, a phosphorus-containing compound, a bromine-containing compound, or a hydroxide An oxidation inhibitor such as a flame retardant such as aluminum or magnesium hydroxide, a phosphate oxidation inhibitor, or a phenol oxidation inhibitor. -17- 200914537 The resin composition of the present invention is particularly suitably used for interlayer insulation as a multilayer printed wiring board. Particularly preferred form that can be used is an RCC-type adhesive film in which an adhesive film composed of a resin composition layer (A layer) and a support film (B layer) and a resin composition layer (A layer) are formed on a copper foil. The form. Then, the film can be produced by a method known to a person skilled in the art. For example, the thermosetting resin composition of the present invention is dissolved in an organic solvent to prepare a varnish, and the varnish is applied onto a support film and a copper foil by heating or The organic solvent is dried by blowing hot air or the like to form a thermosetting resin composition layer. The support film (layer B) is a support for the production of the adhesive film, and it must be peeled off or removed at the end of the manufacture of the multilayer printed wiring board. Examples of the support film include polyolefins such as polyethylene and polyvinyl chloride, polyesters such as polyethylene terephthalate (hereinafter also referred to as "PET"), and polyethylene naphthalate. Polycarbonate, metal foil such as release paper or copper foil, and the like. A heat resistant resin such as polyimine, polyamine, polyamidimide or a liquid crystal polymer can also be used. Further, in the case where the copper foil is used as the support film, it can be removed by etching using an etching solution such as ferric chloride or copper chloride. The support film may also be subjected to a mat treatment or a corona treatment, and when the peelability is considered, it is more preferable to perform a mold release treatment. The thickness of the support film is not particularly limited, and it is usually 10 to 150 μm, preferably 25 to 50 μm. In the case of the RCC type, the copper foil is used as a part of the conductor layer of the multilayer printed wiring board. Usually, an electrolytic copper foil or a rolled copper foil is used, and an extremely thin copper foil can also be used. The ultra-thin copper foil may also be accompanied by a carrier copper foil. The thickness of the copper foil -18-200914537 is not particularly limited, and it is preferable to use a very thin copper foil to form a fine pitch wiring. Examples of the organic solvent used to prepare the varnish include ketones such as acetone, methyl ethyl ketone, and cyclohexanone, ethyl acetate, butyl acetate, fibrin acetate, propylene glycol monomethyl ether acetate, and card. Acetate such as alcoholic acid acetate, cellulase, carbitol, etc., aromatic hydrocarbons such as toluene and xylene, dimethylformamide, dimethylacetamidine Amine, N-methylpyrrolidone, and the like. The organic solvent may be used in combination of two or more kinds. The drying conditions are not particularly limited, and it is important to keep the bonding force, and it is important to harden the thermosetting resin composition as much as possible during drying. In addition, when a large amount of the organic solvent remains in the adhesive film, the bulging occurs after the curing. Therefore, the content of the organic solvent in the thermosetting resin composition is usually desirably dried to 5% by mass or less, and 3% by mass. The following is better. The specific drying conditions vary depending on the amount of the organic solvent in the thermosetting resin composition and the varnish. For example, the varnish containing 30 to 60% by mass of an organic solvent can be usually dried at 80 to 120 ° C. ~13 minutes or so. The industry can set appropriate and optimal drying conditions by simple experimentation. The thickness of the resin composition layer (layer A) can be usually set in the range of 5 to 500 μπι. The preferred range of the thickness of the ruthenium layer varies depending on the use of the film. For the case of manufacturing a multilayer printed wiring board by a build-up process, the thickness of the conductor layer forming the line is usually 5 to 70 μm. Therefore, the thickness of the tantalum layer corresponding to the interlayer insulating layer is preferably in the range of 10 to 100 μm. The enamel layer can also be protected with a protective film. By protecting with a protective film, it is possible to prevent dust and the like on the surface of the resin composition layer from adhering and scratching. The protective film can be peeled off at 200914537 when laminated. As the protective film, the same material as the support film can be used. The thickness of the protective film is not particularly limited, and is preferably in the range of 1 to 40 μm. The adhesive film of the present invention can be preferably laminated to a wiring substrate by a vacuum laminator. The inner layer wiring substrate used herein mainly includes an inner layer wiring substrate such as a polyester substrate, a polyimide substrate, a polyimide film, or a liquid crystal polymer substrate. Further, the adhesive film of the present invention can also be used for the purpose of further multilayering the multilayer printed wiring board. Further, the surface of the wiring is preliminarily roughened by a surface treatment agent such as hydrogen peroxide/sulfuric acid or MEC Etch Bond (manufactured by MEC Co., Ltd.), and the insulating layer is densely bonded to the wiring substrate. The consideration of sex is better. As a commercially available vacuum laminator, for example, a Vacuum Applicator manufactured by Nichig 0_Morton Co. Ltd., a vacuum press laminator manufactured by a machine manufacturer, and a roller manufactured by Hitachi Techno Engineering Co., Ltd. A vacuum laminator made by Dry Coater or Hitachi AIC Inc. is laminated, and when the film is provided with a protective film, after the protective film is removed, the film is pressed under pressure and heated. On the circuit substrate. The lamination condition is to preheat the adhesive film and the circuit substrate as needed, and the pressing temperature is preferably 70 to 140 ° C, and the pressing pressure is preferably 1 to llkgf /cm 2 , and the air pressure is 20 mmHg or less. It is preferred to carry out lamination under reduced pressure. Further, the laminating method may be a batch type or a continuous type using a roll. In the case of the adhesive film composed of the resin composition layer (layer A) and the support film (layer B), the following procedure is employed. After the film was laminated to -20-200914537 on the substrate, it was cooled to near room temperature, and the support film was peeled off. Then, the thermosetting resin composition laminated on the wiring substrate is heat-hardened. The conditions for the heat hardening are usually selected from the range of 150 to 220 ° C for 20 minutes to 180 minutes, and more preferably for the range of 160 to 200 ° C for 30 minutes to 120 minutes. Further, in the case where the support film is subjected to release treatment or a release layer such as silicone, the support film can be peeled off after heat curing of the thermosetting resin composition, or after heat curing and opening. After forming the insulating layer formed by the cured product of the resin composition, the circuit substrate may be drilled, laser, plasma, or a combination thereof to form a via hole as needed. Or through hole. In particular, opening by means of a laser such as a carbon dioxide laser or a YAG laser is often employed. Next, the surface treatment of the insulating layer is performed. The surface treatment may be carried out by a method used in a desumia process or in the form of a decontamination step. As the drug used in the decontamination step, it is usually an oxidizing agent. Examples of the oxidizing agent include permanganate (potassium permanganate, sodium permanganate, etc.), dichromate, ozone, hydrogen peroxide/sulfuric acid, nitric acid, and the like. It is preferable that the oxidizing agent widely used for the roughening of the insulating layer in the multilayer printed wiring board by the lamination (b u i 1 d - u p ) method. It is preferred to carry out the treatment with an alkaline permanganic acid solution (e.g., potassium permanganate or sodium permanganate in an aqueous solution of sodium hydroxide). Treatment with a swelling agent can also be carried out prior to treatment with an oxidizing agent. Further, after the treatment with an oxidizing agent, the neutralization treatment by a reducing agent is usually carried out. The above-described decontamination step also has the purpose of increasing the peeling strength of the conductor layer formed by plating and roughening the surface of the insulator layer to provide irregularities. After the surface treatment, a conductor layer is formed on the surface of the insulator layer by plating. The formation of the conductor layer can be carried out by a combination of electroless plating and electroplating. Further, a plating resist layer having a pattern opposite to the conductor layer may be formed, and the conductor layer may be formed only by electroless plating. After the formation of the conductor layer, the peeling strength of the conductor layer can be further improved and stabilized by annealing at 150 to 200 ° C for 20 to 90 minutes. As a method of forming a line of a conductor layer to form a line, a subtractive method, a semi-additive method, or the like which is well known to those skilled in the art can be used. In the case of subtraction, the thickness of the electroless copper plating layer is 0.1 to 3 μm, preferably 0 to 3 to 2 μηη. After forming a plating layer (panel plating layer) of 3 to 35 μm (preferably a thickness of 5 to 20 μm), an etching photoresist layer is formed by using iron chloride, copper chloride or the like. After the etching solution is etched to form a conductor pattern, the etching photoresist layer is peeled off, whereby a wiring substrate can be obtained. Further, in the case of the semi-additive method, a non-electric copper plating layer having a thickness of 非.1 to 3 μm (preferably 0.3 to 2 μmη) is formed to form a patterned photoresist layer. Then, after copper plating, it is peeled off, whereby a wiring substrate can be obtained. In the case of forming an RC C type bonded film of a resin composition layer (tantalum layer) on a copper foil, the following procedure is employed. The adhesive film was laminated on the wiring substrate, and the thermosetting resin composition was heat-hardened as described above. Then, opening was performed as described above, and the surface treatment of the via holes was performed by soft etching. Then, electroless plating is performed, and the wiring substrate can be obtained by subtraction or the like as described above. As the copper foil to be used, a -22-200914537 electrolytic copper foil of 12 or 18 μm is usually used, and for example, "DFF", "NS-VLP", and Nippon Mining, manufactured by Mitsui Mining & Mining Co., Ltd. Metal (stock) system "JTC" and so on. In addition, it is possible to use a very thin copper foil in accordance with the requirements of a fine line, and examples thereof include "Micro Thin Ex" manufactured by Mitsui Mining & Mining Co., Ltd., and "YSMAP" manufactured by Sakamoto Electrolysis Co., Ltd. . In the following, the present invention is specifically described by way of examples, but the present embodiment is not intended to limit the invention. [Manufacturing Example 1] <Production of Polyimine Resin Resin (Polyimide Resin Varnish A) > In a beaker equipped with a stirring device, a thermometer, and a condenser, 203.07 g of r-butyrolactone as a solvent and 304.60 g of Solveso were added as a solvent. 150, further added isophorone diisocyanate 88.8g (0.4 moles) and hydrogenated polybutadiene diol (hydroxy 値 48_5KOH-mg / g, molecular weight 2 3 1 3 ) 23 1.3 g (0.1 mole), and poly Butadiene diol (hydroxy hydrazine 52.6 KOH-mg/g, molecular weight 2133) 213_3 g (0.1 mol) was reacted at 70 ° C for 4 hours. Then, a nonyl novolac resin (hydroxyl equivalent of 229.4 g/eq, an average of 4.27 functional groups, an average molecular weight of 979.5 g/mole) of 195.9 g (0.2 mol) and ethylene glycol bistriphenylhexahydride 41.0 g (0.1) was added. Mohr), heated to 150 °C in 2 hours, and allowed to react for 12 hours. After the reaction, it became a transparent brown liquid, and a polyiminoimine resin solution having a nonvolatile content of 60% and a viscosity of 15 Pa·s (25 ° C) was obtained. The obtained solution of the polyimide resin was applied to a KBr plate, and the infrared absorption spectrum of the sample obtained by volatilizing the solvent was measured. The characteristic of the isocyanate group was completely disappeared by 2270 cm·1. The absorption of the imine ring at 725 CHT1 and 178() 01^1 and 1720CHT1 was confirmed. Further, the absorption of the urethane bond was confirmed at 154 (^1^1). Further, as the amount of carbon dioxide generated by the imidization of the oxime was observed by the change in the weight change added to the beaker It is 8.8 g (0.2 mol). The anhydride of ethylene glycol bistriphenyl hexacarboxylic anhydride has a functional group equivalent of 0.2 mol, and the amount of carbon dioxide produced is also 0.2 mol. It is concluded that the acid anhydride is all used for quinone imine. Formed, no carboxylic anhydride is present. From this, the following conclusion can be made: 0.2 moles in the isocyanate group is converted into a quinone bond, and the remaining isocyanate groups are combined with hydrogenated polybutadiene diol and polybutadiene. The hydroxy group of the alcohol and the phenolic hydroxyl group in the nonyl novolac resin form a urethane bond, and the phenolic hydroxyl group of the nonyl novolak resin is imparted to the resin, and a part of the phenolic hydroxyl group is modified to become Modified urethane phthalimide resin of urethane. [Production Example 2] <Production of Polyimine Resin Resin (Polyimide Resin Varnish B) > In a beaker equipped with a stirring device, a thermometer, and a condenser, 292.09 g of ethylene glycol ester as a solvent and 292.09 g of Solveso were added as a solvent. 150, then add isopropanone diisocyanate 88.8g (0.4 mol) and polybutadiene diol (hydroxy oxime 52_6KOH-mg / g, molecular weight 2 1 3 3) 426.6g (0.2 m), at 70 ° C The reaction was carried out for 4 hours. Then, a nonyl novolac resin (hydroxyl equivalent 229.4 g/eq, an average of 4.27 functional groups, an average molecular weight of 979.5 g/mole), 195.9 g (0.2 mol) and ethylene glycol bistriphenyl-24-200914537 hexacarboxylic anhydride were added. 41.0 g (0.1 mol), and allowed to react for 2 hours in 2 hours. After the reaction, it became a transparent brown liquid, and a polyiminoimine resin solution having a nonvolatile content of 12 Pa·s (25 t) was obtained. The solution of the polyimide resin was applied to a KBr plate, and the infrared absorption spectrum of the sample of the solvent was measured. The isocyanate group 2270CHT1 completely disappeared, and it was confirmed that it was 725 CHT1 and 1 720 (:1^1). Absorption of the quinone ring, and absorption of the urethane bond at 1 540 CHT1. Further, with the amount of carbon dioxide generated by the imidization, the weight change by adding the beaker is 8.8 g (0.2 mo The ethylene glycol bistriphenyl hexahydride anhydride functional group equivalent is 0.2 mol, and the carbon dioxide is also produced. It is concluded that the acid anhydride is all used for the formation of quinone imine, and the following conclusion can be made. The isocyanate group has a ruthenium group. The other isocyanate group forms a urethane bond with the hydroxyl group of the hydrogenated polyalcohol and the polybutadiene diol and the hydroxyl group of the nonyl phenol novolak resin. The phenolic hydroxyl group of the enamel resin is imparted to the resin, and a partially phenolic hydroxyl group is obtained, which is a modified urethane amide of the urethane. <Reference Example 1> 40 parts of the polyfluorene composition varnish A obtained as the component (A), and ethylene glycol monoethyl ether acetate of the bisphenol A clear resin as the component (B) (hereinafter referred to as the following) It is EDGAc) - the temperature is up to 1 50 is 5 6%, and the characteristics obtained by volatilization are absorbed at 1 780 cm·1 to confirm the resulting trace amount of the anhydride of 0.2 mol of the non-carboxylic anhydride. 2 molybdenic butadiene A phenolic phenolic novolac based modified imine resin lacquer epoxy and Ipuzol -25- 200914537 15 0 (aromatic hydrocarbon mixed solvent: manufactured by Idemitsu Petrochemical Co., Ltd.) mixed varnish (solid content 50%) , epoxy equivalent of 21 0, "157S70" manufactured by Nippon Epoxy Co., Ltd.) 10.9 parts, imidazole derivative ("P200H50" manufactured by Nippon Epoxy Co., Ltd.) 0.5 parts, spherical cerium oxide (specific surface area) 8 0 m 2 /g ) 6 parts, and 1 part of toluene and 5.5 parts of 7 butyrolactone were prepared into a varnish-like resin composition. <Reference Example 2 > 40 parts of the polyamidene resin composition varnish A obtained in Production Example 1 as the component (A), EDGA c and I of the bisphenol A varnish type epoxy resin as the component (B) Pu ζ ο 1 1 5 0 mixed varnish (solid content 50%, epoxy equivalent 210' 「 环氧树脂 epoxy resin (shares) made "157S70") 1 〇 _9 parts, imidazole derivatives (Japanese epoxy resin ) "P200H50") 0.5 parts, spherical cerium oxide (specific surface area 6.2 m2 / g) 6 parts, and toluene 1 part, to prepare a varnish-like resin composition. <Reference Example 3> The polyacrylamide resin composition varnish B obtained as the component (A) was added with 4 parts of varnish, and the bisphenol A varnish type epoxy resin as the component (B) was EDGAc and Ipuzol 150. Mixed varnish (solid content: 50%, epoxy equivalent 210, r 157S70, manufactured by Nippon Epoxy Co., Ltd.)) 〇 9 parts, imidazole derivative ("P200H50" manufactured by Nippon Epoxy Co., Ltd.), 0.5 parts, 6 parts of spherical ceria (specific surface area 80 m 2 / g), and 1 part of toluene and 5.5 parts of r-butyrolactone were prepared into a varnish-like resin composition. -26- 200914537 <Reference Example 4> 40 parts of the polyimine resin composition varnish B obtained in Production Example 2 of the component (A), and EDGAc and Ipuzol 150 of the bisphenol A varnish type epoxy resin as the component (B) were added. 10.9 parts of varnish (solid content: 50°/., epoxy equivalent 210, “157S70” manufactured by Nippon Epoxy Co., Ltd.), and 0.5 parts of imidazole derivative (“P200H50” manufactured by Epoxy Epoxy Co., Ltd.), spherical Cerium dioxide (specific surface area: 6.2 m 2 /g) 6 parts, and toluene 1 〇 part' was prepared into a varnish-like resin composition. [Example 1] 40 parts of the polyamidene resin composition varnish A obtained in Production Example 1 as the component (A), EDGAc and Ipuz〇l 150 of the bisphenol A varnish type epoxy resin as the component (B) were added. Mixed varnish (50% solid content, epoxy equivalent 210, "157S7〇" made by Nippon Epoxy Resin Co., Ltd.) 〇 〇 9 parts, imirene derivative (Japanese epoxy resin) 〇") "Parts" spherical cerium oxide (specific surface area: 30 m2 / g) 6 parts, and 1 part of toluene and 2 parts of r-butyrolactone to prepare a varnish-like resin composition. [Example 2] 40 parts of the polyamidene resin composition varnish B obtained in Production Example 2 of the component (A), EDGAc and Ipuzol 150 mixed varnish of the bisphenol A varnish type epoxy resin as the component (B) were added. (solid content: 50%, epoxy equivalent 210, "157S7〇" manufactured by Epoxy Epoxy Resin Co., Ltd.) 〇 〇 9 parts -27- 200914537, imidazole derivative ("P200H50" made by Japan Epoxy Resin Co., Ltd." 0.5 parts of spherical cerium oxide (specific surface area: 30 m 2 /g) 6 parts, and 1 part of toluene and 2 parts of r-butyrolactone were prepared into a varnish-like resin composition. [Example 3] 40 parts of the polyamidene resin composition varnish A obtained as the component (A), and EDGAc and Ipuzol 1 50 of the bisphenol A varnish type epoxy resin as the component (B) were added. 10.9 parts of varnish (50% solid content, epoxy equivalent 210, "157S70" made by Nippon Epoxy Co., Ltd.), 0.5 part of imidazole derivative ("P200H50" made by Nippon Epoxy Co., Ltd.), spherical cerium oxide (Specific surface area: 20 m 2 /g) 6 parts, and 10 parts of toluene and 4 parts of r-butyrolactone were prepared into a resin composition in the form of a varnish. [Example 4] 40 parts of the polyimine resin composition varnish B obtained in Production Example 2 of the component (A), EDGAc and Ipuzol 150 mixed varnish of the bisphenol A varnish type epoxy resin as the component (B) were added. (50% solid content, epoxy equivalent 210, r157S7〇 manufactured by Epoxy Epoxy Resin Co., Ltd.) 1〇9 parts, imirene derivative ("P2〇〇H50" manufactured by Epoxy Epoxy Co., Ltd.) 0.5 parts, spherical-oxidized sand (specific surface area 20 m2/g) 6 parts, and 10 parts of toluene and 4 parts of r-butyrolactone were prepared into a varnish-like resin composition. [Example 5] The polyimine resin -28-200914537 obtained as the component (A) was added as a component (A). A 40 parts of the composition varnish A, and the EDGAc and Ipuzol of the bisphenol A varnish type epoxy resin as the component (B). 1 50 mixed varnish (50% solid content, epoxy equivalent 210, "157S70" manufactured by Epoxy Epoxy Co., Ltd.) 10.9 parts, and an imidazole derivative ("P2 00H50" manufactured by Nippon Epoxy Co., Ltd.) 0.5 parts A spherical alumina (specific surface area: 22 m 2 /g) of 6 parts and 1 part of toluene were prepared into a varnish-like resin composition. [Example 6] 40 parts of the polyimine resin composition varnish B obtained in Production Example 2 of the component (A), EDGAc and Ipuzol 150 mixed varnish of the bisphenol A varnish type epoxy resin as the component (B) were added. (solid content: 50%, epoxy equivalent 210, "157S70" manufactured by Nippon Epoxy Co., Ltd.) 10.9 parts, imidazole derivative ("P200H50" manufactured by Nippon Epoxy Co., Ltd.) 0.5 parts, spherical alumina (ratio A surface area of 22 m 2 /g of 6 parts and 10 parts of toluene were prepared into a resin composition in the form of a varnish. <Dispersibility> In Reference Examples 1 to 4, when the varnish was allowed to stand at room temperature for about 12 hours, the mash was sedimented and the varnish was separated, and in Examples 1 to 6, the mash was maintained uniform. Dispersed state. [Example 7] The varnish obtained in Example 1 was coated with polyethylene terephthalate (thickness 3 8 μπι 'hereinafter referred to as PET) and its resin composition was coated with -29-200914537. The cloth machine was applied so as to have a resin thickness after drying of 60 Pm, and dried at 80 to 120 ° C (average 10 ° C) for 12 minutes to form a resin composition layer, thereby obtaining a film. [Example 8] The varnish obtained in Example 2: 'A resin composition layer was formed on PET in the same manner as in Example 7 to obtain a film. [Example 9] The varnish obtained in Example 3 was formed into a resin composition layer on PET in the same manner as in Example 7 to obtain a film. [Example 10] With respect to the varnish obtained in Example 4, a resin composition layer was formed on PET in the same manner as in Example 7 to obtain a film. [Example 11] The varnish obtained in Example 5 was formed into a resin composition layer on PET in the same manner as in Example 7: 1. A film was obtained. [Example 1 2] The varnish obtained in Example 6 was formed into a resin composition layer on PET in the same manner as in Example 7 to obtain a film. The film obtained in Examples 7-12 was used at 180. (The lower heat-hardening -30-200914537 was 90 minutes. The cured property of each resin composition is shown in Table 1. Moreover, the tensile breaking strength was measured according to Japanese Industrial Standards (JI s) κ 7 1 2 7 . Further, the dielectric properties were evaluated by a cavity resonance perturbation method (Ε8362Β manufactured by Agilent Technologies Co., Ltd.). The characteristics are shown in Table 1. <Comparative Example 1 > As Comparative Example 1, an interlayer insulating material made of an epoxy resin (ABF-GXcodel3 manufactured by Ajinomoto Seiki Co., Ltd.) was placed at 18 Torr. (: The cured product was heat-cured for 90 minutes to obtain a cured product. The characteristics of the cured product are shown in Table 1 in the same manner as above. [Table 1] Example 7 Example 8 Example 9 Example 10 Example 11 Example 12 Comparative Example 1 Elastic coefficient (MPa) 57 131 88 151 66 141 4000 Tensile strength (MPa) 13 13 15 20 16 16 93 Elongation at break (%) 105 65 73 53 76 45 5 Dielectric coefficient (1 GHz) 2.42 2.48 2.54 2.75 2.83 2.84 3.35 Dielectric tangent (1 GHz) 0.008 0.007 0.006 0.007 0.008 0.006 0.012 [Example 1 3] Adhesion to copper foil (1) The adhesive film obtained in Example 7 was respectively used in copper foil ( S-surface and kneading surface of JT foil, JTC foil, by vacuum laminator (丨aminator) manufactured by Nihon Seiki Co., Ltd., at a temperature of 1〇〇t, a pressure of 7kgf/cm2, and a pressure of 5mmHg. The following conditions were single-sided lamination, respectively -31 - 200914537 Preparation of copper foil / adhesive film / PET three-layer product. Then, stripping PET stripping 'samely laminated to Merck Aiqibang (Μ ECE Tch Β ο nd ) CZ8100 treated copper clad laminate. Then, at 120 °c 3 The minutes were further heat-hardened at 180 ° C for 90 minutes. The peel strength of the interface of the resin/copper foil was measured using the obtained substrate, and the peel strength of the S surface was (K66 kgf/cm, and the peel strength of the dough was 1.22 kgf). Further, the peel strength was evaluated in accordance with JIS C648 1 and the thickness of the copper foil was set to 18 μηι [Example 14] adhesion to copper foil (2). The film obtained in Example 8 was used to Example 1 3 The peel strength of the interface of the resin/copper foil was measured in the same manner, and the peel strength of the S surface was 〇73 kgf/cm, and the peel strength of the knead surface was 1.05 kgf/cm. [Example 1 5] With copper The adhesion strength of the foil (3) The peeling strength of the interface of the resin/copper foil was measured by the same procedure as in Example 13 using the film obtained in Example 9, and the peel strength of the S surface was 〇50 kgf/cm. The peeling strength of the kneading surface was 1. 4 kgf/cm. [Example 1 6] Adhesion to copper foil (4) The film obtained in Example 10 was used in the same manner as in Example 13 -32 - 200914537 The peel strength of the interface of the resin/copper foil was measured by the method, and the peel strength of the s surface was 〇.67 kgf/cm. Strength of 0.94kgf / cm. [Example 1 7] Adhesion to copper foil (5) Using the film obtained in Example 1 1 , the peel strength at the interface of the resin/copper foil was measured in the same manner as in Example 13 to obtain the S surface. The peel strength was 〇46 kgf/cm, and the peel strength of the dough was 1.13 kgf/cm. [Example 1 8] Adhesion to copper foil (6) Using the film obtained in Example 12, the peel strength at the interface of the resin/copper foil was measured in the same manner as in Example 13 to obtain the S surface. The peel strength was 0.44 kgf/cm, and the peel strength of the dough was 1. 6 kgf/cm. <Comparative Example 2> The peeling of the interface of the resin/copper foil was measured in the same manner as in Example 13 using an interlayer insulating material made of an epoxy resin (ABF-GXc〇del3 manufactured by Ajinomoto Precision Technology Co., Ltd.). The strength, the peel strength of the S surface was 〇.29 kgf/cm, and the peel strength of the kneading surface was LOkgf/cm. Example 1 3 - 18. The results of Comparative Example 2 are summarized in Table 2. It is understood that the examples show good adhesion even to the smooth surface of the S-face of the copper foil. -33- 200914537 [Table 2] EXAMPLES EXAMPLES EXAMPLES EXAMPLES EXAMPLES Comparative Example 13 14 15 16 17 18 2 S Surface (kgf/cm) 0.66 0.73 0.50 0.67 0.46 0.44 0.29 Μ Surface (kgf/cm) 1.22 1.05 1.04 0.94 1.13 1.06 1.44 [Example 1 9] Regarding the peeling of the plating layer (1) The film obtained in Example 8 was coated with copper by Merck Etch Bond CZ8100. The laminator was laminated on both sides by a vacuum laminator manufactured by a famous machine manufacturer at a temperature of 100 ° C, a pressure of 7 kgf / cm 2 , and a pressure of 5 mmHg or less. Then, the release-treated PET was peeled off, and 18 (TC was heat-hardened for 30 minutes to form an insulating layer. The surface treatment process of the insulating layer having the decontamination step was performed using the following drug manufactured by Attotec (Japan) Co., Ltd. Liquid: Swelling agent "Swelling Dip Securiganth", oxidant "Concentrate Compact CP" (permanganic acid test solution) > Reducing agent "Reduction solution Securiganth P-500". Surface treatment with a swelling solution at a temperature of 80 °C 5 After a minute, the surface treatment was carried out with an oxidizing agent at a temperature of 80 ° C for 5 minutes, and finally neutralized with a reducing agent solution at 40 ° C for 5 minutes. Then, after the non-electric copper plating catalyst was applied to the surface of the insulating layer, The non-electrolytic copper plating solution was immersed at 32 ° C for a minute to form a non-electric copper plating film of 1.5 μm. This was dried at 150 ° C for 30 minutes, and then acid-washed to use a phosphorus-containing copper plate as an anode. -34- 200914537, copper plating was carried out for 12 minutes at a cathode current density of 2.0 A/dm2 to form a copper plating film, and then annealed at 180 ° C for 30 minutes. The peel strength of the obtained conductor layer was 0.71 kgf/cm. Further, the peel strength measurement was evaluated in accordance with JIS C6481, and the thickness of the conductor plating layer was set to be about 25 μm. (Comparative Example 3) Interlayer insulating material made of epoxy resin (Ajinomoto Precision Technology (Monthly)) ABF- GXcodel3), an insulating layer was formed in the same manner as in Example 19. The surface treatment was carried out in the same manner as the chemical solution prepared by Attotec (Japan) Co., Ltd., and the surface treatment was carried out by a swelling solution at a temperature of 60 ° C for 5 minutes. Then, the surface treatment was carried out by an oxidizing agent at a temperature of 80 ° C for 15 minutes, and finally, the neutralization treatment was carried out by a reducing agent solution at 4 ° C for 5 minutes. Further, the peeling strength of the obtained conductor layer was 〇.6 kgf. /cm. [Manufacturing Example 3] <Production of Linear Modified Polyimine Resin (Linear Modified Polyimine Resin Varnish C) > In the reactor, 50 g of G-3 000 (2-functional hydroxyl-terminated polybutadiene) , number average molecular weight = 5 047 (GPC method), hydroxyl equivalent = 1798 g / eq., solid content 100% by weight, manufactured by Japan Soda Co., 23.5 g of Ipuzol 150, dibutyl tin laurate 0.0 05 g, It is uniformly dissolved. When the temperature was reached, the temperature was raised to 5 ° C, and then toluene-2,4-diisocyanate (isocyanate group equivalent = 8 7.08 g / eq.) -35 - 200914537 4.8 g was added while stirring, and the reaction was allowed to proceed for about 3 hours. Then, 'Iti, then add benzophenone tetracarboxylic dianhydride (fermented) 8.96g, triethylenediamine 〇.〇7g, acetic acid glycol (stock) company) 40.4g' while stirring Sheng Pan should be about 4 hours. It was confirmed by the loss of 2250 cm by FT-IR. In the disappearance of the NC Ο wave peak, the reactant was cooled to room temperature and then modified into a polymethylene imine resin in the form of 100 mesh (linear modified polyfluorene-like modified polyimine resin varnish A β s ( 2 5 °c, Ε-type viscometer) 値 = l6_9mgKOH / g solids = 50% by weight <Reference Example 5 > 35 parts of the component (A) to the imine resin varnish C and 10.0 parts were added as components (EDGAc and buz of the epoxy resin type: 1 150 5 0%, ring) Oxygen equivalent 'Japanese epoxy resin ( ) 'Vinyl varnish (Japan Pharmaceutical Co., Ltd.) 4.5 parts, spherical silica sand (specific surface area, 10 parts of toluene, 2 parts of T-butyrolactone, prepared into a product. Dispersibility : The reactants were cooled to room temperature: anhydride equivalent = 161.ig / eq ester (Diacel Chemicals l to 130 ° C, the elimination of the NCO peak of the reverse 1 is regarded as the end of the reaction filter cloth to obtain the linear amine Resin varnish C). I-form, viscosity = 7.5 P a . 醯 90 得到 得到 得到 TD TD TD TD TD TD TD TD TD TD TD TD TD TD TD TD TD TD TD TD TD TD TD TD TD TD TD TD TD TD TD TD TD TD TD TD TD TD TD TD TD TD TD TD TD 4.1 m 2 /g) 6 parts, varnish-like resin composition -36- 200914537 In Comparative Example 4, the varnish was allowed to stand at room temperature for about 12 hours, and the seasoning was maintained in a state of uniform dispersion. <Physical properties> With respect to the varnish obtained in Comparative Example 4, a resin composition layer was formed on PET in the same manner as in Example 7 to obtain a film of the following, which was heat-cured at 180 ° C for 90 minutes. The properties of the cured product are shown in Table 3. Further, the peeling strength at the interface of the resin/jing foil was measured in the same manner as in Example 13 using the film obtained in Comparative Example 4, and the peel strength of the S surface was 〇.55 kgf/cm. 67.67kgf/cm. [Table 3] Reference Example 5 Elasticity coefficient (MPa) 33 Tensile strength (MPa) 12 Elongation at break (%) 67 Dielectric coefficient (1 GHz) 2.64 Dielectric tangent (1 GHz) 0.013 -37-