TW200528490A - Aminate for wiring board - Google Patents

Abstract

A laminate for wiring board having a polyimide resin layer as insulating layer that has high thermal stability, low hygroscopicity and excellent dimensional stability, being capable of suppressing warp as a result of humidity accompanied by various problems attributed to adhesive layer, and that is slight in any difference of humidity expansion coefficient between TD direction and MD direction, being free of any in-plane anisotropy. This laminate for wiring board is one comprising at least one polyimide resin layer having its one or both major surfaces overlaid with a metal foil, wherein at least one of the polyimide resin layer comprises ≥ 10 mol% of polyimide structural units obtained from a 2,2'-dialkoxybenzidine or 2,2'-diphenoxybenzidine and a tetracarboxylic acid anhydride.

Description

200528490 (1) 九、發明說明 【發明所屬之技術領域】 本發明係有關用於可撓性印刷配線板、HDD懸浮體等 之配線基板用層合體者。 【先前技術】 近年來，電子機器之高性能化、高機能化及小型化急 φ 速進步，針對伴隨此電子機器所使用之電子部品、實裝此 等之基板亦被要求達更高密度、高性能者。針對可撓性印 刷配線板（以下，稱FPC )進行細線加工、多層形成等， 構成FPC材料亦被嚴格要求薄型化及尺寸安定性。 一般FPC之絕緣薄膜中，其具良好各特性之聚醯亞胺 樹脂所成之薄膜被廣泛利用之，絕緣薄膜與金屬間之絕緣 黏著層中其具良好低溫加工性之環氧樹脂、丙烯樹脂者被 使用之。惟，此等黏合層卻有造成耐熱性、熱性尺寸安定 φ 性下降之問題點存在。 爲解決此等問題’近年被採用來形成黏合層，直接塗 布聚醯亞胺樹脂層形成於金屬之方法者。如：特公平6 -93 5 3 7號公報中被揭示以不同熱膨脹係數之複數聚醯亞胺 使聚醯亞胺樹脂層進行多層化後，提供具良好黏合力及熱 性尺寸安定性之FPC方法。惟，此等聚醯亞胺其吸濕性大 ’因此’容易出現浸漬於焊料浴時之膨脹現象，細線加工 時吸濕後之尺寸變化產生接續不良等問題，又，一般導體 所使用之金屬其濕度膨脹係數爲〇或接近〇者，因此，吸 200528490 (2) 濕後之尺寸變化造成層合體之翹曲、卷曲、扭曲、 因素。 本發明相關之先行技術文獻如下所示之文獻者 〔專利文獻1〕特公平6 - 93 5 3 7號公報 〔專利文獻2〕特開平2 — 225 522號公報 〔專利文獻3〕特開200 1 — 1 1 1 77號公報 〔專利文獻4〕特開平5 - 27 1 4 1 0號公報 基於此背景，對於良好低吸濕性、吸濕後具尺 性之聚醯亞胺樹脂所成之FPC之要求提高，其所使 醯亞胺之改良被進行各種討論之。如：特開平2 -號公報及特開200 1 - 1 1 1 7 7號公報中被揭示有導入 脂後，提高疏水性，出現低吸濕性之聚醯亞胺者， 製造成本高、與金屬材料之黏合性不良之缺點存在 其他低吸濕化之組裝亦被揭示於特開平5 - 2 7 1 4 1 0 # 等’維持良好高耐熱性、低熱膨脹係數等之聚醯亞 、卻未能實現低吸濕性者。 另外’聚醯亞胺具有交互結合二羧酸成份與二 之構造，而，以二胺基聯苯基，此被甲氧基取代之 聯苯基類做爲二胺使用之聚醯亞胺被示例於特開 1 1 1 7 7號公報、特開平5 — 2 7 1 4 1 〇號公報中，惟， 示其具體例’未能預測此等是否具有任何特性者。 【發明內容】 等不良 寸安定 用之聚 225522 氟系樹 惟，其 。針對 號公報 胺特性 胺成份 二胺基 200 1 - 並未揭 -6- 200528490 (3) 本發明之目的係解決上記問題點，提供一種具有良好 耐熱性、熱性尺寸安定性、且，具有實現低吸濕性之聚醯 亞胺層的配線基板用層合體者。 本發明之特徵係於具有金屬箔於聚醯亞胺樹脂層單面 或雙面之層合體中，該聚醯亞胺樹脂層之至少1層含有10 莫耳％以上下記一般式（1 )所示構造單位之配線基板用層 合體者。200528490 (1) IX. Description of the invention [Technical field to which the invention belongs] The present invention relates to a laminate for a wiring board used for a flexible printed wiring board, an HDD suspension, and the like. [Previous technology] In recent years, the high-performance, high-performance, and miniaturization of electronic equipment has made rapid progress. For the electronic components used with this electronic equipment, the substrates mounted on them have also been required to achieve higher density, High performers. The flexible printed wiring board (hereinafter referred to as FPC) is subjected to thin wire processing, multilayer formation, and the like. The constituent FPC materials are also required to be thinner and more dimensionally stable. Among general FPC insulating films, films made of polyimide resins with good characteristics are widely used. In the insulating adhesive layer between the insulating film and the metal, the epoxy resin and acrylic resin have good low-temperature processability. Are used. However, these adhesive layers have a problem that the heat resistance and thermal dimensional stability are reduced. In order to solve these problems, a method of directly forming a polyimide resin layer on a metal has been used to form an adhesive layer. For example, it is disclosed in JP-A-6-93 5 3 7 that the polyimide resin layer is multilayered with a plurality of polyimide having different thermal expansion coefficients, and an FPC method with good adhesion and thermal dimensional stability is provided. . However, such polyimide has a large hygroscopicity, and therefore it is prone to the swelling phenomenon when immersed in a solder bath, and the dimensional change after moisture absorption during fine wire processing causes problems such as poor connection, and the metal used in general conductors The humidity expansion coefficient is 0 or close to 0. Therefore, the dimensional change after absorption 200528490 (2) causes the warpage, curl, distortion, and other factors of the laminate. The prior art documents related to the present invention are as follows [Patent Document 1] JP 6-93 5 3 7 [Patent Document 2] JP 2-225 522 [Patent Document 3] JP 200 1 — 1 1 1 77 [Patent Document 4] Japanese Patent Laid-Open No. 5-27 1 4 1 0 Based on this background, an FPC made of a polyimide resin with good low hygroscopicity and scale properties after moisture absorption The requirements are increasing, and the improvement of sulfonimine has been discussed in various ways. For example, Japanese Unexamined Patent Publication No. 2-and Japanese Unexamined Patent Publication No. 200 1-1 1 1 7 7 disclose that polyimide having improved hydrophobicity and low hygroscopicity after introduction of lipids has high manufacturing cost and The shortcomings of poor adhesion of metal materials are the existence of other low-hygroscopic assemblies, which are also disclosed in JP-A-Heisei 5-2 7 1 4 1 0 # etc., which maintain good high heat resistance, low thermal expansion coefficient, etc. Can achieve low hygroscopicity. In addition, the polyfluorene imine has a structure that combines a dicarboxylic acid component with two, and a diaminobiphenyl group, which is a methoxy-substituted biphenyl group, is used as a diamine. Examples are shown in JP-A No. 1 1 7 and JP-A No. 5-2 7 1 4 1 0. However, specific examples are shown in the following: 'It is impossible to predict whether these have any characteristics. [Summary of the Invention] Poly 225522 fluorine-based tree, etc., which is unsafe and stable. Aiming at the amine characteristic amine component diamine group 200 1-Undisclosed-6- 200528490 (3) The object of the present invention is to solve the problems mentioned above, and to provide a heat resistance, thermal dimensional stability, and low realization. A laminate for a wiring board of a hygroscopic polyimide layer. The present invention is characterized in that a laminated body having a metal foil on one side or both sides of a polyimide resin layer, and at least one layer of the polyimide resin layer contains 10 mol% or more of the general formula (1) below. Shows the laminated body for the wiring board of the structural unit.

(式中，ΑΓι爲具有1個以上芳香環之4價有機基者 ’R爲碳數1〜6之烴基者。） 本發明配線基板用層合體係於單層或多層聚醯亞胺樹 脂層單面或雙面中具有層合金屬箔構造者。聚醯亞胺樹脂 層之至少一層含有10莫耳％以上之該一般式（1 )所示構 _ 造單位者。 一般式（1 )所示構造單位中，式中之 Ar!爲具有1 個以上芳香環之4價有機基者，由芳香族四羧酸或其酸二 酐等所產生之芳香族四羧酸殘基者。因此，ΑΓ]可藉由所 使用之芳香族四羧酸之說明而明朗。一般，合成具該構造 單位之聚醯亞胺時，多半使用芳香族四羧酸二酐者，因此 ’利用芳香族四羧酸二酐進行理想Ar!之以下說明之。 做爲該芳香族四羧酸二酐者，並未特別限定，可使用 公知者。具體例如：均苯四酸二酐、3，3,，4，4, 一二苯 甲酮四羧酸二酐、2，2 ’，3，3，一二苯甲酮四羧酸二酐、2 200528490 (4)(In the formula, AΓι is a tetravalent organic group having one or more aromatic rings, and 'R is a hydrocarbon group having 1 to 6 carbon atoms.) The laminated system for a wiring substrate of the present invention is a single-layer or multi-layer polyimide resin layer. Laminated metal foil structure on one or both sides. At least one layer of the polyimide resin layer contains 10 mol% or more of the structural unit represented by the general formula (1). In the structural unit represented by the general formula (1), Ar! In the formula is a tetravalent organic group having one or more aromatic rings, and an aromatic tetracarboxylic acid generated from an aromatic tetracarboxylic acid or an acid dianhydride thereof. Residues. Therefore, ΑΓ] can be made clear by the description of the aromatic tetracarboxylic acid used. In general, when synthesizing a polyfluorene imide having this structural unit, an aromatic tetracarboxylic dianhydride is mostly used, so 'the ideal Ar! Using an aromatic tetracarboxylic dianhydride is explained below. The aromatic tetracarboxylic dianhydride is not particularly limited, and a known one can be used. Specific examples: pyromellitic dianhydride, 3,3,, 4,4, monobenzophenone tetracarboxylic dianhydride, 2,2 ', 3,3, monobenzophenone tetracarboxylic dianhydride, 2 200528490 (4)

，3，3，，4’一二苯甲酮四羧酸二酐、萘一2，3，6，7-四 羧酸二酐、萘一 1，2，5，6 —四羧酸二酐、萘—1，2，4 ，5 —四羧酸二酐、萘—1，4，5，8—四羧酸二酐、萘一 1 ，2，6，7 —四羧酸二酐、4，8 —二甲基一1，2，3，5，6 ，7 —六氫萘一1，2，5，6—四羧酸二酐、4，8—二甲基 —1，2，3，5，6，7 —六氫萘—1，2，5，6 —四羧酸二酐 、4，8 -二甲基一1，2，3，5，6，7 -六氫萘—2，3，6 ，7 —四羧酸二酐、2，6 —二氯萘一1，4，5，8_四羧酸 二酐、2，7 —二氯萘—1，4，5，8_ 四羧酸二酐、2，3， 6，7 —四氯萘一1，4，5，8 —四羧酸二酐、1，4，5，8 — 四氯萘一2，3，6，7 —四羧酸二酐、3，3’，4，4’一聯苯 四羧酸二酐、2，2 ’，3，3 ’ —聯苯四羧酸二酐、2，3，3 ’ ，4 ’ —聯苯四羧酸二酐、3，3 ”，4，4 ” 一 p —三聯苯四羧酸 二酐、2，2 ’’，3，3 ’’ 一 p —三聯苯四羧酸二酐、2，3，3 ’’ ，4”一 p —三聯苯四羧酸二酐、2，2 —雙（2，3 —二羧基 苯基）一丙烷二酐、2，2-雙（3，4 一二羧基苯基）一丙 烷二酐、雙（2，3 -二羧基苯基）醚二酐、雙（2，3 —二 羧基苯基）甲烷二酐、雙（3，4 一二羧基苯基）甲烷二酐 、雙（2，3 —二羧基苯基）磺二酐、雙（3，4 一二羧基苯 基）磺二酐、1，1—雙（2，3 -二羧基苯基）乙烷二酐、 1，1—雙（3，4 一二羧基苯基）乙烷二酐、茈—2，3，8 ，9 一四羧酸二酐、茈一3，4，9，1 0 -四羧酸二酐、茈一 4，5，1 0，1 1 -四羧酸二酐、託一5，6，1 1，1 2 —四羧酸 二酐、菲—1，2，7，8 —四羧酸二酐、菲—1，2，6，7 — 200528490 (5) 四羧酸二酐、菲—1，2，9，10 —四羧酸二酐、環戊烷一：[ ，2，3，4 —四羧酸二酐、吼嗪一2，3，5’ 6—四羧酸二 酐、吡咯烷—2，3 ’ 4，5 —四羧酸二酐、噻吩一 2，3，4 ，5 —四羧酸二酐、4，4’一羥基二酞酸二酐等例。又，此 等可單獨使用，亦可含倂2種以上使用之。 其中又以選自均苯四酸二酐（PMDA)、萘—2，3，6 ，7 —四羧酸二酐（NTCDA)及 3，3’，4，4· 一聯苯四羧 φ 酸二酐（BPDA)者爲較佳。特別使用PMDA或NTCDA者 爲實現低熱膨脹係數最爲理想者。使用混合適於此量之 BPDA後，可調整與金屬箔相同程度之熱膨脹係數，亦可 調整實用上所要求之2 0Ppm/°C以下之値。藉由此可抑制 層合體之翹曲、卷曲等之產生。此等芳香族四殘酸二野亦 可倂用其他芳香族四羧酸二酐，而以整體之5 0莫耳％以上 者宜’更佳者爲70莫耳％以上使用之。亦即，四羧酸二酐 之選定時’具體而言’於聚合加熱後取得聚醯亞胺之熱膨 φ 脹係數與熱分解溫度、玻璃轉移溫度等使用目的下，選擇 適於出現必要特性者宜。 M S € $用於本發明聚醯亞胺樹脂時之必須成份所使 用之二胺爲下記一般式（2 )所示之 芳香族二胺者。, 3,3,4'-benzophenonetetracarboxylic dianhydride, naphthalene-1,2,3,6,7-tetracarboxylic dianhydride, naphthalene-1,2,5,6-tetracarboxylic dianhydride Naphthalene-1,2,4,5-tetracarboxylic dianhydride, naphthalene-1,4,5,8-tetracarboxylic dianhydride, naphthalene-1,2,6,7-tetracarboxylic dianhydride, 4 , 8-dimethyl-1,2,3,5,6,7-hexahydronaphthalene-1,2,5,6-tetracarboxylic dianhydride, 4,8-dimethyl-1,2,3 , 5,6,7-hexahydronaphthalene-1,2,5,6-tetracarboxylic dianhydride, 4,8-dimethyl-1,2,3,5,6,7-hexahydronaphthalene-2 , 3,6,7-tetracarboxylic dianhydride, 2,6-dichloronaphthalene-1,4,5,8_tetracarboxylic dianhydride, 2,7-dichloronaphthalene-1,4,5,8_ Tetracarboxylic dianhydride, 2,3,6,7-tetrachloronaphthalene-1,4,5,8-tetracarboxylic dianhydride, 1,4,5,8-tetrachloronaphthalene-1,2,3,6, 7-tetracarboxylic dianhydride, 3,3 ', 4,4'-biphenyltetracarboxylic dianhydride, 2,2', 3,3'-biphenyltetracarboxylic dianhydride, 2,3,3 ' , 4'-biphenyltetracarboxylic dianhydride, 3,3 ", 4,4" -p-terphenyltetracarboxylic dianhydride, 2,2 ", 3,3 '' P-terphenyltetracarboxylic dianhydride, 2,3,3 '', 4 ''-p-terphenyltetracarboxylic dianhydride, 2,2-bis (2,3-dicarboxyphenyl) -propane Dianhydride, 2,2-bis (3,4-dicarboxyphenyl) monopropane dianhydride, bis (2,3-dicarboxyphenyl) ether dianhydride, bis (2,3-dicarboxyphenyl) methane Dianhydride, bis (3,4-dicarboxyphenyl) methane dianhydride, bis (2,3-dicarboxyphenyl) sulfonic dianhydride, bis (3,4-dicarboxyphenyl) sulfonic dianhydride, 1, 1-bis (2,3-dicarboxyphenyl) ethane dianhydride, 1,1-bis (3,4-dicarboxyphenyl) ethane dianhydride, fluorene-2,3,8,9-tetracarboxylic Acid dianhydride, hydrazone 3,4,9,1 0 -tetracarboxylic dianhydride, hydrazone 4,5,1,0,1 1 -tetracarboxylic dianhydride, Troine 5,6,1 1,1 2 —Tetracarboxylic dianhydride, phenanthrene 1,2,7,8 —tetracarboxylic dianhydride, phenanthrene 1,2,6,7 — 200528490 (5) tetracarboxylic dianhydride, phenanthrene 1,2,9 , 10-tetracarboxylic dianhydride, cyclopentane-1: [， 2,3,4-tetracarboxylic dianhydride, oxazine-2,3,5 '6-tetracarboxylic dianhydride, pyrrolidine-2, 3 '4, 5 Examples of tetracarboxylic dianhydride, thiophene-2,3,4,5-tetracarboxylic dianhydride, 4,4'-hydroxydiphthalic dianhydride, etc. These can be used alone or can contain two kinds of fluorene Used above. Among them, selected from pyromellitic dianhydride (PMDA), naphthalene-2,3,6,7-tetracarboxylic dianhydride (NTCDA) and 3,3 ', 4,4 · biphenyl Tetracarboxylic φ acid dianhydride (BPDA) is preferred. Especially those who use PMDA or NTCDA are ideal for achieving low thermal expansion coefficient. After using a BPDA that is suitable for this amount, the thermal expansion coefficient can be adjusted to the same degree as the metal foil, and it can also be adjusted to less than 20Ppm / ° C, which is practically required. This can suppress the occurrence of warpage and curl of the laminate. These aromatic tetra-residual acid di-fields may also be used with other aromatic tetracarboxylic dianhydrides, and it is preferable to use 50 mol% or more as a whole ', and more preferably 70 mol% or more. That is, when the tetracarboxylic dianhydride is selected, 'specifically', the thermal expansion φ expansion coefficient, thermal decomposition temperature, and glass transition temperature of the polyimide obtained after the polymerization heating are selected to suit the necessary characteristics. Anyone should. M S € $ The diamine used as an essential component in the polyfluorene imine resin of the present invention is an aromatic diamine represented by the following general formula (2).

(2) 其中’ R爲具有與一般式（1) R相同意義者，碳數 1〜6之烴基者，惟，較佳者爲i〜4之烷基或6之芳基者。 更理想者爲乙基及η -丙基或苯基。 -9- 200528490 (6) 本發明所使用之聚醯亞胺樹脂較理想者係使芳香"族四 羧酸二酐與含10莫耳％以上該一般式（2 )所示芳香族二 胺之二胺進行反應後可取得之。 本發明中與該一般式（2)所示之芳香族二胺之同時 可使用90莫耳％以下比例之其他二胺者，藉由此，可做爲 共聚型之聚醯亞胺者。 一般式（η所示之構造單位係於至少丨層聚醯亞胺 樹脂層中含有10〜100莫耳％，較佳者爲π〜1〇〇莫耳％ , 更佳者爲70Μ00莫耳％，最佳者爲90〜1〇〇吴耳％。 ° m — 苯二胺 2’5_二甲基-p—苯二胺、2’4—二胺基均三甲苯、4 4，一亞甲基二—甲苯胺、4,4,_亞甲基二— 甲苯胺、4，4’一亞甲甚 Ί 7_ 妃干棊〜2, 6一 一乙基苯胺、2, 4一甲 做爲一般式（2 )所示之芳香族二胺以外之其他二胺 例者並未特別限定，一般如，4，6 一二田甚 一二胺基二苯基 ，一二胺基二苯基 苯基乙院、4 ’ 4,一二胺基二苯基 苯基甲烷、2, 2—雙〔4(4〜胺基 4，4’一二胺基二苯基硫醚、3，3, 4，4’ —二胺基二苯基硕、3，3，一 苯二胺、m —苯二胺、ρ〜苯二胺、4,4 丙烷、3，3’ —二胺基二苯基丙烷、4 , 4 乙烷、3，3 ’ —二胺基 甲烷、3，3 ’ 一二胺基 苯氧基）苯基〕丙烷 一二胺基二苯基硫醚 二胺基二苯硕、4, 4,一二胺基二苯醚、3, 3〜二胺基一苯 醚、1，3 -雙（3〜胺基苯氧基）苯、丨，3^_雙（“胺= 本氧基）本、1’ 4 —雙（4 —日右其茶结甘、-η· ^ 4妝基本氧基）苯、聯苯胺、3 ，3 ’ —二胺基聯苯基、3，3，一二甲基— 4 一 ~胺基聯 -10 200528490 \—/ 基、 苯苯 胺 苯 聯 基 氧 I 甲基 二胺,一 一一 3 一(2) where 'R is a hydrocarbon group having the same meaning as that of the general formula (1) R and having a carbon number of 1 to 6, but more preferably an alkyl group of i to 4 or an aryl group of 6. More preferred are ethyl and n-propyl or phenyl. -9- 200528490 (6) The polyfluorene imide resin used in the present invention is preferably an aromatic "group tetracarboxylic dianhydride and an aromatic diamine represented by the general formula (2) above 10 mol%. Diamine can be obtained after the reaction. In the present invention, the aromatic diamine represented by the general formula (2) can be used in combination with other diamines at a ratio of 90 mol% or less, and can be used as a copolymerized polyimide. The structural unit represented by general formula (η) is that at least one polyimide resin layer contains 10 to 100 mole%, preferably π to 100 mole%, and more preferably 70M00 mole%. The best is 90% to 100% of the ear. ° m — phenylenediamine 2'5_dimethyl-p-phenylenediamine, 2'4-diamine mesitylene, 4 4, 1 Methyl di-toluidine, 4,4, _methylene di-toluidine, 4,4'-methylene hydrazone, 7_ congener dry condensate ~ 2,6-monoethylaniline, 2,4-monomethyl as Examples of diamines other than the aromatic diamines represented by the general formula (2) are not particularly limited, and generally, for example, 4,6 di-field di-diamino diphenyl, mono-diamino diphenyl benzene Glycogen, 4 '4, monodiaminodiphenylphenylmethane, 2, 2-bis [4 (4 ~ amino4,4'-diaminodiphenylsulfide, 3, 3, 4 , 4'-diaminodiphenylsulfone, 3,3, monophenyldiamine, m-phenylenediamine, ρ ~ phenylenediamine, 4,4 propane, 3,3'-diaminodiphenylpropane , 4, 4 ethane, 3,3'-diaminomethane, 3,3'-diaminophenoxy) phenyl] propane-diaminodiphenyl Sulfide diamino diphenyl ether, 4, 4, monodiamino diphenyl ether, 3, 3 ~ diamino monophenyl ether, 1, 3-bis (3 ~ aminophenoxy) benzene, 丨, 3 ^ _bis ("amine = benzyloxy) benzyl, 1 '4 -bis (4-days right tea tea sweet, -η · ^ 4 makeup basic oxygen) benzene, benzidine, 3,3'- Diamino biphenyl, 3,3, monodimethyl-4 4-amino group-10 200528490 \ /, phenylaniline phenylbenzyloxy I methyldiamine, one one one three one

P 苯 聯 三 雙 基 胺P phenyleneditribis amine

P 基 己 環 基 胺 雙 f 烷 三 第 I 基 胺 1 雙 、 醚 \)/ 基 苯 基P-based hexyl amine bis f alkane tri-I amine 1 bis, ether \) / ylphenyl

聯甲 石 三 I 雙 I P 苯 \)y 基 戊 基 胺 1 5 I 基 甲 基 胺 I 4 I 基 甲 苯 Nly 基 戊 雙 苯 \ί/ 基 戊 基 胺 I 5 1 基 甲 萘 胺二 萘 胺二 I 6 /|\ 雙 - 4 基 第Dimethytrin I double IP benzene \) y-pentylamine 1 5 I-methylmethylamine I 4 I-methyltoluene Nly-pentylbiphenyl \ ί / pentylamine I 5 1-methylnaphthylamine dinaphthylamine I 6 / | \ double-4 base

2苯2 ^ ^ ^ 甲一二 } P 基 基、甲 丁 胺二 I 二苯 三 I I 4 6 m 、 苯 甲 基 胺 苯 甲 胺 m 苯 甲 胺二 5 Ρ 啶 rx 基 胺 5 啶 批 基 5 三 基 一 醚4 基苯{ 胺基雙 二胺一 F卜 9 4 1 噁 4 甲 } 二基 1 氧 2f苯 ， 基 2 胺 ， 苯 3 聯 、 基 嗪胺 吡二 〇 化，一例 氫4等 六b基 Λ>一苯 ¾基聯 此等中又以4，4’一二胺基二苯醚（DAPE) 、1，3 一 雙（4 一胺基苯氧基）苯（TPE - R)、卩一苯二胺（戶一 PDA) 、2，2,一二甲基一 4，4’一二胺基聯苯（m—TB)等 φ 爲較佳使用者。又，使用此等二胺時，該理想之使用比例 爲總二胺之〇〜50莫耳％，更佳者爲〇〜30莫耳％。 做成聚醯亞胺樹脂層前驅物之聚醯胺酸係使上記所示 芳香族二胺成份與芳香族四羧酸二酐成份以0.9〜1.1莫耳 比使用之，於有機極性溶媒中可藉由聚合之公知方法製造 之。亦即，使芳香族二胺溶解於氮氣流下，N，N -二甲 基乙酿胺、N —甲基一 2 -吡咯烷酮等有機溶媒後，加入芳 香族四羧酸二酐後，室溫下反應3〜4小時後取得。此時， 分子末端亦可以芳香族單胺基或二竣酸酐進行密封之。 -11 - 200528490 (8) 使用含有萘骨架之芳香族四羧酸二酐成份時，如：將 芳香族二胺成份溶於氮氣流下m -甲酚後，加入觸媒與芳 基族四羧酸二酐成份後，於約1 90 °C下加熱1 0小時，之後 ，恢復至室內後，更反應8小時後取得。 將該反應取得之聚醯胺酸溶液於載體之金屬箔上或金 屬箔上所形成黏合層上利用塗佈機進行塗佈後，藉由熱醯 亞胺化法或化學醯亞胺化法進行醯亞胺化後，取得本發明 φ 之配線基板用層合體。熱醯亞胺化係於1 5 (TC以下之溫度 下進行2〜60分鐘之預備乾燥，一般於130〜3 60 °C溫度下 2〜3 0分鐘熱處理後進行之。化學醯亞胺化係藉由加入脫水 劑與觸媒於聚醯胺酸後進行之。做爲所使用之金屬箔者以 銅箔或SUS箔者宜，該理想厚度之範圍亦爲50// m以下 ，較理想者爲5〜4 0 // m。銅箔厚度其較薄者適於精細圖案 之形成，由其觀點視之以8〜1 5 // m之範圍者爲宜。 聚醯亞胺樹脂層可爲單層，亦可爲多層者。多層之聚 φ 醯亞胺樹脂層時，塗佈聚醯胺酸溶液後，重覆進行乾燥操 作之後，進行熱處理後去除溶劑，此更於高溫下進行熱處 理後藉由醯亞胺化後，可形成多層構造之聚醯亞胺系樹脂 層。此時，所形成聚醯亞胺樹脂層總厚度以3〜7 5 // m者宜 。多層時，其至少一層務必含有1 0莫耳％以上之一般式（ 1 )所示構造單位之聚醯亞胺樹脂層（以下，亦稱本聚酿 亞胺樹脂層）者，該厚度爲聚醯亞胺樹脂層整體之30 %以 上者宜，50 %以上者爲更佳者。 又，於雙面製造具有金屬箔之配線基板用層合體時， -12- 2005284902 Benzene 2 ^ ^ ^ Methyl 1,2} P group, Methylamine II I Diphenyltriene II 4 6 m, benzylamine benzylamine m benzylamine 5 P pyridine rx base amine 5 pyridine group 5 Triyl monoether 4 base benzene {amine bis diamine-F 9 4 1 ox 4 methyl} diyl 1 ox 2f benzene, radical 2 amine, benzene 3 diphenyl, hydrazine pyrimide dioxin, an example of hydrogen 4 etc. Hexa-byl Λ > monophenyl ¾yl, and 4,4'-diaminodiphenyl ether (DAPE), 1,3 bis (4-aminophenoxy) benzene (TPE-R) , 卩 -phenylenediamine (household PDA), 2,2, -dimethyl-4,4'-diaminobiphenyl (m-TB), etc. φ are preferred users. When these diamines are used, the ideal use ratio is 0 to 50 mole% of the total diamine, and more preferably 0 to 30 mole%. The polyamidic acid used as the precursor of the polyimide resin layer is made by using the aromatic diamine component and the aromatic tetracarboxylic dianhydride component shown in the above description at a molar ratio of 0.9 to 1.1. It can be used in organic polar solvents. It is manufactured by a known method of polymerization. That is, the aromatic diamine is dissolved in a nitrogen stream, and organic solvents such as N, N-dimethylethylamine and N-methyl-2-pyrrolidone are added, and then aromatic tetracarboxylic dianhydride is added. Obtained after 3 to 4 hours of reaction. At this time, the molecular terminal may be sealed with an aromatic monoamine group or a dibasic acid anhydride. -11-200528490 (8) When using an aromatic tetracarboxylic dianhydride component containing a naphthalene skeleton, such as: dissolving the aromatic diamine component in m-cresol under a nitrogen stream, add a catalyst and an aromatic tetracarboxylic acid After the dianhydride component, it was heated at about 1 90 ° C for 10 hours, and after recovering to the room, it was obtained after 8 hours of reaction. The polyamic acid solution obtained by the reaction is coated on a carrier metal foil or an adhesive layer formed on the metal foil by a coater, and then is subjected to a thermal fluorination method or a chemical fluorination method. After the imidization, a laminate for a wiring substrate of φ of the present invention was obtained. Hot ammonium imidization is preliminarily dried at a temperature below 15 ° C for 2 to 60 minutes. Generally, it is heat-treated at a temperature of 130 to 3 60 ° C for 2 to 30 minutes. Chemical ammonium imidization It is carried out after adding dehydrating agent and catalyst to polyamic acid. As the metal foil to be used, copper foil or SUS foil is preferred. The ideal thickness range is also 50 // m or less, which is more ideal. It is 5 ~ 4 0 // m. The thinner copper foil is suitable for the formation of fine patterns. From its point of view, it is appropriate to range from 8 to 1 5 // m. The polyimide resin layer may be A single layer may also be a multi-layer. For a multi-layer poly (φ) imide resin layer, after applying a polyamic acid solution, repeating a drying operation, and then performing a heat treatment to remove the solvent, and then performing a heat treatment at a high temperature The polyimide resin layer having a multilayer structure can be formed by fluorene imidization. At this time, the total thickness of the fluorene resin layer to be formed is preferably 3 to 7 5 // m. In the case of multiple layers, at least One layer must contain a polyimide resin layer of the structural unit represented by the general formula (1) above 10 mol% (hereinafter, also referred to as this For imine resin layer), the thickness is preferably 30% or more of the entire polyimide resin layer, and 50% or more is more preferable. In addition, when a laminate for a wiring substrate having a metal foil is manufactured on both sides, , -12- 200528490

於該方法取得之單面配線基板用層合體之聚醯亞跑 上直接或形成黏合層後，使金屬箔藉由加熱壓延卷 針對此加熱壓延時之熱加壓溫度並未特別限定，-使用聚醯亞胺樹脂之玻璃轉移溫度以上者宜。又， 加壓壓力亦依其所使用加壓機器種類而定，一般焉 k g / c m 2者宜。此時所使用之理想金屬箔更可使用拆 述之金屬箔者，理想之厚度亦爲 50//m以下，更 5 〜4 0 // m。 構成本發明配線基板用層合體之聚醯亞胺樹脂 性可藉由一般式（2 )所示之芳香族二胺與此倂用 他芳香族二胺以及芳香族四羧酸或其酸二酐相互名 後抑制之。理想之聚醯亞胺樹脂層其膨脹係數爲 °C以下，23°C中貯存彈性率爲6GPa以下，且，吸 0.8 wt %以下者，而，由耐熱性觀點視之，其玻璃轉 以 3 5 0 °C以上，且，熱重量分析中5 %重量減少 φ 以5%)爲5 00〜60CTC者宜，其溫度膨脹係數於TD 向均爲l〇ppm/%RH者爲更佳者。另外，5%重量減 亦稱熱分解溫度。 【實施方式】 〔發明實施之最佳形態〕 以下，以實施例爲基準，進行本發明內容之具 ’惟，本發明未受限於此等實施例者。 下記代表實施例等所使用之略稱。 g樹脂層 t取得。 -般爲所 有關熱 "〜500 目同於上 :佳者爲 ί層之特 後之其 •種組合 3 0 p p m / :濕率爲 ί移溫度 溫度（ 、MD方 丨少溫度 體說明 -13- 200528490 (10) • PMDA:均苯四甲酸二酐 • BPDA: 3，3’，4，4’ —聯苯四竣酸二酐 • m — MOB : 2，2’一二甲氧基聯苯胺 • m—EOB: 2，2’ —二乙氧基聯苯胺 • m — P0B : 2，2’一二—η —丙基烴基聯苯胺 • m — ΡHOB : 2 ’ 2’一二-苯基羥基聯苯胺 • DAPE: 4，4’一 二胺基二苯醚 • m— TB: 2，2’一二甲基聯苯胺 • TPE— R: 1，3-雙（4 一胺基苯氧基）苯 • BAPP : 2，2-雙（4 一胺基苯氧基苯基）丙 • DMAc: N，N—二甲基乙醯胺 又，以下代表賓施例中之各種物性測定方法與 〔玻璃轉移溫度（Tg )、貯存彈性率（E')〕 以動態熱機械分析（DMA )裝置進行測定各養 取得聚醯亞胺薄膜（l〇mm x22.6mm )以 5°C /分鐘 昇溫至5 0 0 °C時之動態黏彈性，求取玻璃轉移溫度 極大値）及23°C、1 00°C之貯存彈性率（Hi及E、 〔線膨脹係數（CTE )之測定〕 以熱機械分析（TMA )裝置使3mm X 1 5mm尸 醯亞胺薄膜加入5 · 0g荷重之同時以一定昇溫速度 〜2 6 0。(：之溫度範圍下進行張力試驗。針對溫度由葬 薄膜之延伸量求出線膨脹係數。 烷 條件。 f施例所 由 2 0°C (tan δ οο ) 0 [寸之聚 由 3 0°C $醯亞胺 -14- 200528490 (11) 〔熱分解溫度（Td5% )之測定〕 以熱重量分析（TG)裝置使10〜20mg之聚醯亞胺薄 膜以一定速度測定30°C舁溫至5 5 0 °C時之重量變化，求出 5%重量減少溫度（Td5% )。 〔吸濕率（RMA)之測定〕 將4cmx20cm之聚醯亞胺薄膜（各3片）於120°C下 進行乾燥2小時後，於23 t /50%RH之恆溫恆濕室中靜置 24小時以上，藉由下式求出其前後之重量變化。 RMA ( % )=〔（吸濕後重量一乾燥後重量）/乾燥後 重量〕xl00 〔濕度膨脹係數（CHE )之測定〕 設置鈾刻光阻層於35cmx35cm之聚醯亞胺/銅箔層合 體之銅箔上，將此於一邊爲30cm正方形之四邊上形成以 間隔1 0 cm直徑1 cm之點配置1 2處之圖案。使蝕刻光阻 開孔部露出銅箔部份進行蝕刻後，取得具有殘存1 2處銅 箔點之CHE測定用聚醯亞胺薄膜。該薄膜於12〇1：下進行 乾燥2小時後，於23t/50%RH之恆溫恆濕機中靜置24 小時，藉由二維測長機進行測定銅箔點間之尺寸變化（ 0〜50%RH)，求出濕度膨脹係數。 〔實施例〕 - 15- 200528490 (12) 〔合成例1〜1 8〕 合成實施例1〜2 1及比較例1所使用之聚醯胺酸。 於氮氣流下，將表1所示之二胺於1 0 0 可分離燒瓶 中進行攪拌，同時溶於43g之溶劑DMAc。再加入表！所The temperature and temperature of the metal foil by heating and rolling to delay the heating and pressing time after the adhesive layer is directly or directly formed on the polyurethane of the laminate for the single-sided wiring substrate obtained by this method is not particularly limited. Polyimide resins are preferred above the glass transition temperature. In addition, the pressurizing pressure also depends on the type of pressurizing machine used, and generally 焉 k g / cm 2 is appropriate. For the ideal metal foil used at this time, the metal foil can be used, and the ideal thickness is also 50 // m or less, more 5 to 4 0 // m. The polyimide resin constituting the laminate for a wiring substrate of the present invention can be made of an aromatic diamine represented by the general formula (2) and other aromatic diamines and aromatic tetracarboxylic acids or acid dianhydrides thereof. Mutual names suppress them. An ideal polyimide resin layer has a coefficient of expansion of ° C or lower, a storage elasticity of 6 GPa or lower at 23 ° C, and a weight of 0.8 wt% or less. From the viewpoint of heat resistance, the glass is converted to 3 Above 50 ° C, and 5% weight reduction (5% by weight) in thermogravimetric analysis is preferably from 500 to 60CTC, and the temperature expansion coefficient in the TD direction is 10 ppm /% RH is more preferred. In addition, 5% weight loss is also called thermal decomposition temperature. [Embodiment] [Best Mode for Implementing Invention] Hereinafter, the content of the present invention will be described with reference to the examples. However, the present invention is not limited to those examples. The following represents abbreviations used in Examples and the like. g resin layer t is obtained. -Generally all related heat " ~ 500 The same as above: Jiazhe is a special feature of the tier layer 30 ppm /: Moisture rate is shift temperature temperature (, MD side 丨 less temperature body description- 13- 200528490 (10) • PMDA: pyromellitic dianhydride • BPDA: 3,3 ', 4,4' —biphenyltetracarboxylic dianhydride • m — MOB: 2,2'-dimethoxyl Aniline • m—EOB: 2,2 ′ —diethoxybenzidine • m — P0B: 2,2′—1,2—n —propylhydrocarbyl benzidine • m — PBHOB: 2 '2'-diphenyl Hydroxybenzidine • DAPE: 4,4'-diamine diphenyl ether • m— TB: 2,2'-dimethylbenzidine • TPE— R: 1,3-bis (4 monoaminophenoxy ) Benzene • BAPP: 2,2-bis (4-aminoaminophenoxyphenyl) propane • DMAc: N, N-dimethylacetamidamine. Glass transition temperature (Tg), storage elasticity (E ')] were measured with a dynamic thermomechanical analysis (DMA) device to obtain a polyimide film (10 mm x 22.6 mm), and the temperature was raised to 5 ° C / min. Dynamic viscoelasticity at 5 0 0 ° C Glass transition temperature is extremely high) and 23 ° C, 100 ° C storage elasticity (Hi and E, [Measurement of Linear Expansion Coefficient (CTE)]] 3mm X 1 5mm cadaver with thermomechanical analysis (TMA) device The amine film is loaded with a load of 5.0 g while performing a tension test at a temperature rising rate of ~ 2 0. (: temperature range. The coefficient of linear expansion is obtained from the elongation of the film for the temperature. Alkane conditions. FExample by 2 0 ° C (tan δ οο) 0 [Inch of poly by 30 ° C $ 醯 imine-14- 200528490 (11) [Measurement of thermal decomposition temperature (Td5%)] Using a thermogravimetric analysis (TG) device 10 ～ 20mg of polyimide film is measured at a certain speed to measure the weight change from 30 ° C to 55 ° C, and the 5% weight reduction temperature (Td5%) is determined. [Measurement of moisture absorption rate (RMA) ] After drying a 4cmx20cm polyimide film (3 pieces each) at 120 ° C for 2 hours, let it stand in a constant temperature and humidity room at 23 t / 50% RH for more than 24 hours. Weight change before and after. RMA (%) = [(Weight after moisture absorption—Weight after drying) / Weight after drying] × l00 [Measurement of Humidity Expansion Coefficient (CHE) 〕 Set a uranium engraved photoresist layer on a copper foil of 35cmx35cm polyimide / copper foil laminate, and place this on the four sides of a 30cm square with a distance of 10 cm and a diameter of 1 cm. pattern. After the copper foil portion of the etching resist opening portion was exposed and etched, a polyimide film for CHE measurement having 12 copper foil points remaining was obtained. The film was dried for 2 hours at 1201: and then left to stand in a constant temperature and humidity machine at 23t / 50% RH for 24 hours. The size change between copper foil points was measured by a two-dimensional length measuring machine (0 ~ 50% RH) to determine the humidity expansion coefficient. [Example]-15- 200528490 (12) [Synthesis Examples 1 to 1 8] Polyamic acids used in Synthesis Examples 1 to 21 and Comparative Example 1. Under a nitrogen stream, the diamine shown in Table 1 was stirred in a 100 separable flask while being dissolved in 43 g of the solvent DMAc. Join the table again! All

示之四羧酸二酐。隨後，將溶液於室溫下持續攪拌3〜4個 小時進行聚合反應後，取得做爲聚醯亞胺前驅物之18種 聚醯胺酸之黃〜茶褐色黏稱溶液。分別之聚醜 胺酸溶液之；®原黏度〔D sp/C )爲之範圍內者。另外 ，重量平均分子量Mw示於袠j。Shown as a tetracarboxylic dianhydride. Subsequently, the solution was continuously stirred at room temperature for 3 to 4 hours to carry out the polymerization reaction, and then 18 kinds of polyamic acid yellow to tea brown viscous solutions were obtained as precursors of polyimide. Polyurethane solution, respectively; the original viscosity [D sp / C] is within the range. The weight average molecular weight Mw is shown in 袠 j.

- 16- 200528490 (13)-16- 200528490 (13)

〔表1〕 合成例 二胺 (g) PMDA (g) BPDA (g) PA V sp/C (dl/g) Mw xlO3 1 m-MOB 3.45 3.08 A 5.7 263 2 m-MOB3.88 2.73 0.92 B 5.3 259 3 m-MOB 3.07 3.45 C 4.9 225 4 m-EOB 3.62 2.90 D 4.5 150 5 m-EOB 3.54 2.27 0.71 E 4.1 474 6 m-EOB 3.25 3.27 F 3.4 58 7 m-POB 3.78 2.74 G 5.8 112 8 m-POB 3.70 2.15 0.68 H 5.2 58 9 m-POB 3.41 3.11 I 4.6 160 10 DAPE 2.39 2.61 J 150 11 m-PHOB 4.10 2.43 K 218 12 m-PHOB 3.99 1.89 0.64 L 208 13 m-EOB 1.96 DAPE 1.45 3.11 M 120 14 m-POB 2.67 TPE-R1.12 2.74 N 188 15 m-MOB 3.44 TPE-R 0.46 2.69 0.91 0 220 16 m-PHOB 2.17 m-TB 0.43 TRE-R 0.60 4.38 P 215 17 m-POB 2.36 m-TB 1.36 2.80 Q 229 18 BAPP 5.00 2.50 0.18 R 325 -17- 200528490 (14) 〔實施例1〕 使合成例1〜18取得之聚醯胺酸（Pa) A〜R洛 工之前進行添加DMAC調整黏度爲約25〇p〇is者c 佈機於分別3 5 # Π1厚度之銅箔上塗佈Μ乾纟喿彳麦辟 1 5 // m後，於5 0〜1 3 0 °C下進行乾燥2〜6 〇分鐘後， 於 130°C、160。。、200。。、2 3 0。。、2 8 〇。〇、3 2 〇 〇〇 下各進行2〜3 0分鐘階段性熱處理後，形成担 φ 銅箔上，取得1 8種層合體。將合成例丨取得之黃 A溶液取得之層合體做爲層合體A，以τ胃彳目胃^ 使用合成例1 〇取得之聚醯胺酸J溶液取得之層合 成比較例。另外’使用合成例1 8取得之聚醯胺酸 所取得之層合體R係爲評定後記實施例層合體Μ] 聚醯亞胺層之單層特性者。 針對實施例1之層合體Α〜R，使用氯化鐵溶液 銅箔進行鈾刻去除後，作成1 8種聚醯亞胺薄膜， φ 定玻璃轉移溫度（Tg )、貯存彈性率（E’）、熱膨 (CTE ) 、5%重量減少溫度（Td5% )、吸濕率（ 及濕度膨脹係數（CHE)。 各測定結果示於表2。 〖液於塗 利用塗 厚約爲 更分別 、3 60 〇C 胺層於 醯胺酸 〇又， 體J做 R溶液 〜M3之 後，使 進行測 脹係數 RMA ) -18- 200528490 (15) 〔表2〕[Table 1] Synthesis Example Diamine (g) PMDA (g) BPDA (g) PA V sp / C (dl / g) Mw xlO3 1 m-MOB 3.45 3.08 A 5.7 263 2 m-MOB3.88 2.73 0.92 B 5.3 259 3 m-MOB 3.07 3.45 C 4.9 225 4 m-EOB 3.62 2.90 D 4.5 150 5 m-EOB 3.54 2.27 0.71 E 4.1 474 6 m-EOB 3.25 3.27 F 3.4 58 7 m-POB 3.78 2.74 G 5.8 112 8 m- POB 3.70 2.15 0.68 H 5.2 58 9 m-POB 3.41 3.11 I 4.6 160 10 DAPE 2.39 2.61 J 150 11 m-PHOB 4.10 2.43 K 218 12 m-PHOB 3.99 1.89 0.64 L 208 13 m-EOB 1.96 DAPE 1.45 3.11 M 120 14 m-POB 2.67 TPE-R1.12 2.74 N 188 15 m-MOB 3.44 TPE-R 0.46 2.69 0.91 0 220 16 m-PHOB 2.17 m-TB 0.43 TRE-R 0.60 4.38 P 215 17 m-POB 2.36 m-TB 1.36 2.80 Q 229 18 BAPP 5.00 2.50 0.18 R 325 -17- 200528490 (14) [Example 1] Polyamic acid (Pa) A ~ R obtained in Synthesis Examples 1 ~ 18 was added before adding DMAC to adjust the viscosity to approximately 25〇〇〇〇c c cloth machine 3 5 # Π1 thickness of copper foil coated with M dry wheat Maipi 1 5 // m, then dried at 50 ~ 130 ° C 2 ~ After 60 minutes, at 130 ° C, 16 0. . , 200. . , 2 3 0. . , 2 8 〇. After performing stepwise heat treatment for 2 to 30 minutes each at 〇, 3 2 〇 00, a copper foil with a diameter of φ was formed, and 18 kinds of laminates were obtained. The laminated body obtained from the yellow A solution obtained in Synthesis Example 丨 was referred to as the laminated body A, and the stomach was treated with τ stomach and stomach stomach. ^ A comparative example of the layer obtained by using the polyamic acid J solution obtained in Synthesis Example 10. In addition, the layered product R obtained using the polyamic acid obtained in Synthesis Example 18 is the one in which the monolayer characteristics of the polyimide layer of the post-exemplary layered product M] are evaluated. Regarding the laminates A to R of Example 1, after removing uranium by using copper foil of ferric chloride solution, 18 kinds of polyimide films were prepared, and the glass transition temperature (Tg) and storage elastic modulus (E ') were determined. , Thermal expansion (CTE), 5% weight reduction temperature (Td5%), moisture absorption (and humidity expansion coefficient (CHE)). The results of each measurement are shown in Table 2. [Liquid-on-coating uses coating thicknesses of about 3, 3, and 3]. 60 ℃ amine layer on glutamic acid, and the body J is made R solution ~ M3, so that the expansion coefficient RMA is measured) -18- 200528490 (15) [Table 2]

Run 層合體 Tg e，23 E ’ 1 0 0 GTE T d 5 % RMA CHE No. (°C ) (GPa) (GPa) (PPm/ (°C ) (wt°/〇) (ppm/%RH) °C ) TD MD 1 A 403 10.79 10.47 -3.6 457 2 B 365 10.30 9.26 -0.9 48 1 1.69 9.8 9.7 3 C 430 10.20 9.12 8.7 477 1.3 5 9.7 7.6 4 D 3 78 9.5 1 8.08 -7.7 43 1 1.3 1 0.3 0.3 5 E 3 78 6.80 5.36 14 434 1.27 5.4 5.5 6 F 270 5.40 4.48 58 443 0.88 9.4 8.8 7 G 3 78 4.90 3.91 -1 1 426 0.64 -2.2 -0.5 8 H 365 4.49 3.95 24 439 0.83 -1.0 0 9 I 276 3.80 2.82 66 42 1 0.76 -7.9 -7.2 10 J 3 87 2.48 2.22 41 >505 1.70 34 36 11 K 3 94 5.17 4.50 17 539 0.55 -2.1 -1.6 12 L 3 9 1 4.95 4.35 5 1 543 0.68 -4.1 -4.2 13 M 376 4.6 3.66 2 1 465 1.37 9.7 9.9 14 N 3 7 1 5.6 17 437 0.55 -1.2 -1.8 15 0 360 9.1 7.1 482 1.43 6.9 7.5 16 P 370 4.5 15.1 528 0.69 氺 * 17 Q 3 74 8.7 12.0 490 1.03 3. 1 2.7 1 8 R 3 11 3. 1 一· 56.1 490 0.64 -19- 200528490 (16) 〔實施例2〕 以2 5 // m之厚度均勻塗佈合成例1 8所調製之聚醯胺 酸R溶液於1 8 // m厚之銅箔後，於1 3 〇 °C下加熱乾燥後去 除溶劑。接著’以1 9 5 // m之厚度均勻塗佈合成例5所調 製之聚醯胺酸E溶液使層合於其上，於7 0 °C〜1 3 0 °C下進 行加熱乾燥後，去除溶劑。更於聚醯胺酸E層上以3 7 // m 之厚度均勻塗佈合成例1 8所調製之聚醯胺酸R溶液後， φ 於1 3 5 °C下進行加熱乾燥後去除溶劑。之後，由室溫至 3 60 °C進行5小時之熱處理，醯亞胺化後，取得銅箔上形 成3層聚醯亞胺系樹脂層所成總厚度約爲25 # m之絕緣樹 脂層之層合體Μ 1。銅箔上所塗佈聚醯胺酸樹脂層乾燥後 之厚度依R/E/R之順序約爲2.5# 111/19“ m/3.5// m者。 〔實施例3〜4〕 與實施例2同法取得銅箔上形成3層聚醯亞胺系樹脂 φ 層所成總厚度約爲25 // m絕緣樹脂層之層合體M2及M3 。銅箔上所塗佈聚醯胺酸溶液種類與乾燥後之厚度依序爲 M2 爲 R 約 2.5/ζιπ/Ο 約 19//m/R 約 3.5//m 者，M3 爲 R 約 2.5 # m/Q 約 19 μ m/R 約 3.5 // m 者。 針對實施例2〜4所取得之層合體Ml〜M3進行測定黏 合性強度。又，使用氯化鐵水溶液使銅箔進行蝕刻去除後 ’作成聚醯亞胺薄膜後，測定3層聚醯亞胺層之熱膨脹係 數（CTE)。 各測定結果如表3所示。 -20- 200528490 (17) 〔表3〕 實施例 層合體 層構造 黏接性 CTE (kN/m) (ppm/°C ) 2 Ml R/E/R 1.4 17 3 M2 R/0/R 1 .5 16 4 M3 R/Q/R 1 .4 20 〔產業上可利用性〕 本發明配線基板用層合體其做成絕緣層之聚醯亞胺樹 脂層具有良好耐熱性，同時亦具良好低吸濕、及尺寸安定 性者，不會伴隨源於黏合層各種問題，可有效抑制藉由濕 度之翹曲。又，絕緣層之聚醯樹脂層於TD方向與MD方 向之濕度膨脹係數差極小，因此其特徵係於內面未具異構 性者，可廣泛適用於電子材料領域之部品者。特別是適用 # 於FPC、HDD懸浮用基板等者。 -21 -Run Laminate Tg e, 23 E '1 0 0 GTE T d 5% RMA CHE No. (° C) (GPa) (GPa) (PPm / (° C) (wt ° / 〇) (ppm /% RH) ° C) TD MD 1 A 403 10.79 10.47 -3.6 457 2 B 365 10.30 9.26 -0.9 48 1 1.69 9.8 9.7 3 C 430 10.20 9.12 8.7 477 1.3 5 9.7 7.6 4 D 3 78 9.5 1 8.08 -7.7 43 1 1.3 1 0.3 0.3 5 E 3 78 6.80 5.36 14 434 1.27 5.4 5.5 6 F 270 5.40 4.48 58 443 0.88 9.4 8.8 7 G 3 78 4.90 3.91 -1 1 426 0.64 -2.2 -0.5 8 H 365 4.49 3.95 24 439 0.83 -1.0 0 9 I 276 3.80 2.82 66 42 1 0.76 -7.9 -7.2 10 J 3 87 2.48 2.22 41 > 505 1.70 34 36 11 K 3 94 5.17 4.50 17 539 0.55 -2.1 -1.6 12 L 3 9 1 4.95 4.35 5 1 543 0.68 -4.1 -4.2 13 M 376 4.6 3.66 2 1 465 1.37 9.7 9.9 14 N 3 7 1 5.6 17 437 0.55 -1.2 -1.8 15 0 360 9.1 7.1 482 1.43 6.9 7.5 16 P 370 4.5 15.1 528 0.69 氺 * 17 Q 3 74 8.7 12.0 490 1.03 3. 1 2.7 1 8 R 3 11 3. 1 1 · 56.1 490 0.64 -19- 200528490 (16) [Example 2] Uniformly coated the polymer prepared in Synthesis Example 1 with a thickness of 2 5 // m After the sulfamic acid R solution is in a 1 8 // m thick copper foil, After drying at 130 ° C, the solvent was removed. Next, the polyamic acid E solution prepared in Synthesis Example 5 was uniformly coated with a thickness of 1 9 5 // m to laminate the polyimide E solution thereon, followed by heating and drying at 70 ° C to 130 ° C. Remove the solvent. Furthermore, the polyamino acid R solution prepared in Synthesis Example 18 was uniformly coated on the polyamino acid E layer at a thickness of 3 7 // m, and then the solvent was removed by heating and drying at φ 1 35 ° C. After that, heat treatment was performed at room temperature to 3 60 ° C for 5 hours. After the imidization, the insulating resin layer having a total thickness of about 25 # m formed by forming three polyimide resin layers on the copper foil was obtained. Laminate M1. The thickness of the polyamine resin layer applied on the copper foil after drying is about 2.5 # 111/19 "m / 3.5 // m in the order of R / E / R. [Examples 3 to 4] and Examples 2 Obtain the laminates M2 and M3 with a total thickness of about 25 // m insulating resin layer formed by forming 3 layers of polyfluorene-based resin φ layer on copper foil in the same way. Type of polyamic acid solution applied on copper foil And the thickness after drying is in order: M2 is R about 2.5 / ζιπ / Ο about 19 // m / R about 3.5 // m, and M3 is R about 2.5 # m / Q about 19 μm / R about 3.5 // m. The adhesive strength was measured for the laminates M1 to M3 obtained in Examples 2 to 4. In addition, after the copper foil was etched and removed using an aqueous solution of ferric chloride, a polyimide film was formed, and then the three-layer polymerization was measured. Coefficient of thermal expansion (CTE) of the sulfonium imine layer. The results of each measurement are shown in Table 3. -20- 200528490 (17) [Table 3] Example CTE (kN / m) (ppm / °) C) 2 Ml R / E / R 1.4 17 3 M2 R / 0 / R 1 .5 16 4 M3 R / Q / R 1. 4 20 [Industrial Applicability] The laminated body for a wiring substrate of the present invention is made of Polyimide resin layer of insulation layer has good heat resistance At the same time, those with good low moisture absorption and dimensional stability will not be accompanied by various problems caused by the adhesive layer, which can effectively suppress the warpage due to humidity. In addition, the polymer resin layer of the insulating layer is in the TD direction and the MD direction. The difference in humidity expansion coefficient is extremely small, so its characteristics are for those who are not heterogeneous on the inside, which can be widely used in parts in the field of electronic materials. Especially suitable # for FPC, HDD suspension substrates, etc. -21-

Claims (1)

200528490 (1) 十、申請專利範圍 1 · 一種配線基板用層合體，其特徵係於聚醯亞胺樹 脂層單面或雙面上具有金屬箔之層合體中， 、 土 ^ 1層該聚 醯亞胺樹脂層爲含有1 〇莫耳％以上之下記一般式（1 )戶 示構造單位者，200528490 (1) X. Patent application scope 1 · A laminate for a wiring board, which is characterized in that a polyimide resin layer has a metal foil on one or both sides of the laminate, and ^ 1 layer of the polymer The imine resin layer is a unit containing a structural unit of general formula (1) below 10 mol%, 式中，Ar!爲具有〗個以上芳香環之4價有機基者，R 爲碳數1〜6之烴基者。 2 ·如申請專利範圍第1項之配線基板用層合體，其 中該聚醯亞胺樹脂層之線膨脹係數爲3 0 p p m / °C以下，2 3 °C之貯存彈性率爲6 G P a以下，且，吸濕率爲〇 · 8 wt %以下 者。 3 ·如申請專利範圍第1項之配線基板用層合體，其 中該聚醯亞胺樹脂層位於熱重量分析中5 %重量減少溫度 (T d 5 % )爲5 0 0〜6 0 0 °C的範圍。 -22- 200528490 七、指定代表圖： (一） 、本案指定代表圖為：無 (二） 、本代表圖之元件代表符號簡單說明：無In the formula, Ar! Is a tetravalent organic group having at least one aromatic ring, and R is a hydrocarbon group having 1 to 6 carbon atoms. 2 · The laminated body for wiring substrates according to item 1 of the scope of patent application, wherein the linear expansion coefficient of the polyimide resin layer is 30 ppm / ° C or less, and the storage elastic modulus at 2 3 ° C is 6 GP a or less And, the moisture absorption is 0.8 wt% or less. 3. The laminated body for wiring substrates according to item 1 of the scope of patent application, wherein the polyimide resin layer is located in a 5% weight reduction temperature (T d 5%) in thermal weight analysis of 50 0 to 6 0 ° C Range. -22- 200528490 7. Designated Representative Map: (1) The designated representative map in this case is: None (II) The component representative symbols of the representative map are simply explained: None 八、本案若有化學式時，請揭示最能顯示發明特徵的化學 式：8. If there is a chemical formula in this case, please disclose the chemical formula that best shows the characteristics of the invention: -4--4-