JPH05214301A - Low thermally expansible adhesive film and wiring board using the same - Google Patents
Low thermally expansible adhesive film and wiring board using the sameInfo
- Publication number
- JPH05214301A JPH05214301A JP4020964A JP2096492A JPH05214301A JP H05214301 A JPH05214301 A JP H05214301A JP 4020964 A JP4020964 A JP 4020964A JP 2096492 A JP2096492 A JP 2096492A JP H05214301 A JPH05214301 A JP H05214301A
- Authority
- JP
- Japan
- Prior art keywords
- thermal expansion
- adhesive film
- wiring board
- polyimide
- low thermal
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Landscapes
- Production Of Multi-Layered Print Wiring Board (AREA)
- Manufacturing Of Printed Wiring (AREA)
- Laminated Bodies (AREA)
- Adhesive Tapes (AREA)
- Adhesives Or Adhesive Processes (AREA)
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は低熱膨張性接着フィルム
に係り、特にポリイミド多層配線基板の絶縁層および導
体金属層間の密着性の向上と基板内の熱応力の低減に有
用な低熱膨張性接着フィルムおよびそれを用いた配線基
板に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a low thermal expansion adhesive film, and particularly to a low thermal expansion adhesive useful for improving adhesion between insulating layers and conductive metal layers of a polyimide multilayer wiring board and reducing thermal stress in the board. The present invention relates to a film and a wiring board using the film.
【０００２】[0002]
【従来の技術】電子装置の配線基板においては、その多
層化並びに配線の微細化が進められているが、多層化に
は配線パターンが形成された複数のポリイミド基板を低
熱膨張性接着フィルムを介して熱圧着する方法が有用で
ある。その際、接着フィルムの熱膨張率が配線層や基板
の熱膨張率よりも大きいと熱応力によりクラックや反り
が生じ問題となる。これを抑制するためには配線層や基
板の材料とできるだけ近い熱膨張率を有する接着フィル
ムが望ましい。2. Description of the Related Art In wiring boards for electronic devices, multilayering and miniaturization of wiring are being promoted. For the multilayering, a plurality of polyimide substrates having wiring patterns are formed through a low thermal expansion adhesive film. A method of thermocompression bonding is useful. At that time, if the coefficient of thermal expansion of the adhesive film is larger than the coefficient of thermal expansion of the wiring layer or the substrate, thermal stress causes cracks or warpage, which becomes a problem. In order to suppress this, an adhesive film having a coefficient of thermal expansion as close as possible to the material of the wiring layer or the substrate is desirable.
【０００３】しかし、従来の低熱膨張性接着フィルム
（特開平２−２０４０２９号公報）は熱膨張率が大きく
問題である。一般にこうした樹脂の熱膨張率を下げるに
はシリカ等の熱膨張率の小さな無機粉末を加える方法が
知られている。しかし、電子装置等の微細配線基板の形
成に不可欠であるレーザーによる孔穿け加工の際、無機
物と有機物ではエッチングレートが異なるために、無機
粉末を充填したものでは正確な加工が困難である。However, the conventional low thermal expansion adhesive film (Japanese Patent Laid-Open No. 204029/1990) has a large coefficient of thermal expansion, which is a problem. Generally, a method of adding an inorganic powder having a small coefficient of thermal expansion such as silica is known to reduce the coefficient of thermal expansion of such a resin. However, when a hole is punched by a laser, which is indispensable for forming a fine wiring substrate of an electronic device or the like, an inorganic substance and an organic substance have different etching rates, and therefore, it is difficult to perform accurate machining with a substance filled with an inorganic powder.
【０００４】[0004]
【発明が解決しようとする課題】前記多層化に低熱膨張
率の接着フィルムを用いれば、配線材料や基板との熱応
力を抑えることができる。さらにレーザーによる微細配
線加工を可能とする充填剤としては有機物が有効であ
る。If an adhesive film having a low coefficient of thermal expansion is used for the above-mentioned multilayer structure, it is possible to suppress the thermal stress between the wiring material and the substrate. Furthermore, an organic material is effective as a filler that enables fine wiring processing with a laser.
【０００５】本発明の目的は、配線基板や配線材料との
熱応力が小さくレーザーによる微細加工が可能な低熱膨
張性接着フィルムを提供することにある。An object of the present invention is to provide a low thermal expansion adhesive film which has a small thermal stress with a wiring board or a wiring material and which can be finely processed by a laser.
【０００６】本発明の他の目的は、上記低熱膨張性接着
フィルムを用いた高密度多層配線基板を提供することに
ある。Another object of the present invention is to provide a high-density multilayer wiring board using the above low thermal expansion adhesive film.
【０００７】[0007]
【課題を解決するための手段】前記目的を達成する本発
明の要旨は次のとおりである。The gist of the present invention for achieving the above object is as follows.
【０００８】（１）ビスマレイミドおよびポリイミド粉
末を含むポリアミック酸組成物からなり、加熱硬化後の
熱膨張係数が（５〜３０）×１０~6である低熱膨張性接
着フィルム。(1) A low thermal expansion adhesive film comprising a polyamic acid composition containing bismaleimide and polyimide powder and having a thermal expansion coefficient of (5 to 30) × 10 to 6 after heat curing.
【０００９】（２）表面に金属配線を設けた有機絶縁層
が接着フィルムを介して複数積層されてなる多層配線基
板において、前記接着フィルムがビスマレイミドおよび
ポリイミド粉末を含むポリアミック酸組成物からなり、
加熱硬化後の熱膨張係数が（５〜３０）×１０~6である
低熱膨張性接着フィルムである多層配線基板。(2) In a multilayer wiring board in which a plurality of organic insulating layers each having a metal wiring on the surface thereof are laminated with an adhesive film interposed therebetween, the adhesive film comprises a polyamic acid composition containing bismaleimide and polyimide powder,
A multilayer wiring board which is a low thermal expansion adhesive film having a thermal expansion coefficient of (5 to 30) × 10 to 6 after heat curing.
【００１０】前記ポリイミド粉末の熱膨張係数は２０×
１０~6以下であり、前記組成物中の含有量が３０〜７０
重量％配合する。このようなポリイミド粉末としては、The coefficient of thermal expansion of the polyimide powder is 20 ×
10 to 6 or less, and the content in the composition is 30 to 70
Blend by weight percent. As such a polyimide powder,
【００１１】[0011]
【化１】 [Chemical 1]
【００１２】式〔１〕および／または式〔２〕とWith the formula [1] and / or the formula [2]
【００１３】[0013]
【化２】 [Chemical 2]
【００１４】式〔３〕 （ただし、Ｒはアルキル基、フッ素化アルキル基、アル
コキシル基、フッ素化アルコキシル基、アシル基、ハロ
ゲンから選ばれ、ｐは０〜４の整数、ｍは０〜２の整
数、ｎは０〜３の整数である。）から構成されるポリイ
ミドからなる。Formula [3] (wherein R is selected from an alkyl group, a fluorinated alkyl group, an alkoxyl group, a fluorinated alkoxyl group, an acyl group, and halogen, p is an integer of 0 to 4, and m is 0 to 2). An integer, n is an integer of 0 to 3).
【００１５】前記分子の構成単位は次の各式から選ばれ
る。The constitutional unit of the molecule is selected from the following formulas.
【００１６】[0016]
【化３】 [Chemical 3]
【００１７】[0017]
【化４】 [Chemical 4]
【００１８】（ただし、Ｒはアルキル基、フッ素化アル
キル基、アルコキシル基、フッ素化アルコキシル基、ア
シル基、ハロゲンから選ばれ、ｋは０〜３の整数、ｐは
０〜４の整数、ｍは０〜２の整数、ｎは０〜３の整数で
ある。） 前記ポリイミド粉末はイミド化率が２０〜９５％のポリ
イミドが望ましい。(Wherein R is selected from an alkyl group, a fluorinated alkyl group, an alkoxyl group, a fluorinated alkoxyl group, an acyl group, and halogen, k is an integer of 0 to 3, p is an integer of 0 to 4, and m is An integer of 0 to 2 and n is an integer of 0 to 3.) The polyimide powder is preferably a polyimide having an imidization ratio of 20 to 95%.
【００１９】前記式〔４〕〜〔１２〕で示される骨格を
有するポリイミドは、芳香族アミノジカルボン酸誘導体
の単独重合、または芳香族ジアミンもしくは芳香族ジイ
ソシアネートと芳香族テトラカルボン酸誘導体との反応
によって得ることができる。テトラカルボン酸誘導体
は、エステル、酸無水物、酸塩化物がある。The polyimide having a skeleton represented by the above formulas [4] to [12] can be obtained by homopolymerization of an aromatic aminodicarboxylic acid derivative or a reaction between an aromatic diamine or aromatic diisocyanate and an aromatic tetracarboxylic acid derivative. Obtainable. The tetracarboxylic acid derivative includes an ester, an acid anhydride and an acid chloride.
【００２０】ジアミノカルボン酸誘導体は、４−アミノ
フタル酸、４−アミノ−５−メチルフタル酸、４−（ｐ
−アニリノ）−フタル酸、４−（３，５−ジメチル−４
−アニリノ）フタル酸あるいはこれらのエステル、酸無
水物、酸塩化物等が挙げられる。The diaminocarboxylic acid derivative includes 4-aminophthalic acid, 4-amino-5-methylphthalic acid and 4- (p
-Anilino) -phthalic acid, 4- (3,5-dimethyl-4)
-Anilino) phthalic acid or esters thereof, acid anhydrides, acid chlorides and the like.
【００２１】芳香族ジアミンとしては、ｐ−フェニレン
ジアミン、２，５−ジアミノトルエン、２，５−ジアミ
ノキシレン、ジアミノジュレン（２，３，５，６−テト
ラメチル−ｐ−フェニレンジアミン）、２，５−ジアミ
ノベンゾトリフルオライド、２，５−ジアミノアニソー
ル、２，５−ジアミノアセトフェノン、２，５−ジアミ
ノベンゾフェノン、２，５−ジアミノジフェニル、２，
５−ジアミノフルオロベンゼン、ベンジジン、ｏ−トリ
ジン、ｍ−トリジン、３，３’−ジメトキシベンジジ
ン、３，３’，５，５’−テトラメチルベンジジン、
３，３’−ジ（トリフルオロメチル）ベンジジン、３，
３’−ジアセチルベンジジン、３，３’−ジフルオロベ
ンジジン、オクタフルオロベンジジン、４，４’−ジア
ミノターフェニル等がある。また、これらのジイソシア
ネート化合物も同様に用いられる。As the aromatic diamine, p-phenylenediamine, 2,5-diaminotoluene, 2,5-diaminoxylene, diaminodurene (2,3,5,6-tetramethyl-p-phenylenediamine), 2 , 5-diaminobenzotrifluoride, 2,5-diaminoanisole, 2,5-diaminoacetophenone, 2,5-diaminobenzophenone, 2,5-diaminodiphenyl, 2,
5-diaminofluorobenzene, benzidine, o-tolidine, m-tolidine, 3,3'-dimethoxybenzidine, 3,3 ', 5,5'-tetramethylbenzidine,
3,3′-di (trifluoromethyl) benzidine, 3,
There are 3'-diacetylbenzidine, 3,3'-difluorobenzidine, octafluorobenzidine, 4,4'-diaminoterphenyl and the like. Further, these diisocyanate compounds are also used.
【００２２】テトラカルボン酸誘導体としてはピロメリ
ット酸、メチルピロメリット酸、ジメチルピロメリット
酸、ジ（トリフルオロメチル）ピロメリット酸、３，
３’，４，４’−ビフェニルテトラカルボン酸、ｐ−
（３，４−ジカルボキシフェニル）ベンゼン等がある。
またこれらの酸無水物、酸塩化物、エステルなどが挙げ
られる。As the tetracarboxylic acid derivative, pyromellitic acid, methylpyromellitic acid, dimethylpyromellitic acid, di (trifluoromethyl) pyromellitic acid, 3,
3 ', 4,4'-biphenyltetracarboxylic acid, p-
(3,4-dicarboxyphenyl) benzene and the like.
Moreover, these acid anhydrides, acid chlorides, esters, etc. are mentioned.
【００２３】前記により得られたポリイミド前駆体の溶
媒を完全に取り除いた後粉砕し、平均粒径１μｍ以下の
ポリアミック酸粉末を得る。次に該ポリアミック酸粉末
を加熱してイミド化しポリイミド粉末とする。その際、
加熱温度を制御することによりイミド化率を２０〜９５
％とすることでポリマ分子の一部にアミド結合を残した
ポリイミド粉末を得ることができる。この場合、ポリア
ミック酸のイミド化率が９５％を超えると、ポリイミド
粉末とベース樹脂との密着性に問題が生じ易い。The solvent of the polyimide precursor obtained above is completely removed and then pulverized to obtain a polyamic acid powder having an average particle size of 1 μm or less. Next, the polyamic acid powder is heated to be imidized to obtain a polyimide powder. that time,
By controlling the heating temperature, the imidization ratio can be adjusted to 20 to 95.
By setting the ratio to%, a polyimide powder in which an amide bond is left in a part of the polymer molecule can be obtained. In this case, if the imidization ratio of the polyamic acid exceeds 95%, a problem tends to occur in the adhesion between the polyimide powder and the base resin.
【００２４】また、ポリアミック酸を加熱硬化して得た
ポリイミドを粒径１μｍ以下に粉砕した後、２０％ＫＯ
Ｈ溶液中で十分攪拌し、イミド結合を一部アミド結合に
変化する。ろ別した該粉末を十分に水洗乾燥すればイミ
ド化率が２０〜９５％の低熱膨張性ポリイミド粉末を得
ることができる。その際、ポリアミック酸のイミド化率
が９５％を超えると該粉末とベース樹脂との間の密着性
に問題が生じ易い。Also, polyimide obtained by heating and curing polyamic acid was crushed to a particle size of 1 μm or less, and then 20% KO.
After sufficiently stirring in the H solution, the imide bond is partially converted into an amide bond. If the powder separated by filtration is sufficiently washed with water and dried, a low thermal expansion polyimide powder having an imidization ratio of 20 to 95% can be obtained. At that time, if the imidization ratio of the polyamic acid exceeds 95%, a problem tends to occur in the adhesion between the powder and the base resin.
【００２５】前記低熱膨張性ポリイミド粉末の配合割合
は、樹脂分総量の３０〜７０重量％が望ましい。３０重
量％未満では十分な低熱膨張率化が達成できず、７０重
量％を超えるとフィルムの接着性が低下する。The mixing ratio of the low thermal expansion polyimide powder is preferably 30 to 70% by weight based on the total amount of the resin content. If it is less than 30% by weight, a sufficiently low coefficient of thermal expansion cannot be achieved, and if it exceeds 70% by weight, the adhesiveness of the film is deteriorated.
【００２６】本発明の低熱膨張性接着フィルムは、ポリ
イミド前駆体であるポリアミック酸溶液にビスマレイミ
ドを１０〜７０重量％含む組成物に、低熱膨張性ポリイ
ミド粉末を加え十分混練し、流延塗布することにより成
膜する。The low thermal expansion adhesive film of the present invention is obtained by adding a low thermal expansion polyimide powder to a composition containing bismaleimide in an amount of 10 to 70% by weight of a polyamic acid solution which is a polyimide precursor, sufficiently kneading, and cast-casting. To form a film.
【００２７】前記ポリアミック酸は、Ｎ−メチルピロリ
ドン、ジメチルアセトアミド、ジメチルホルムアミド、
クレゾール、フェノール等の非プロトン性極性溶媒中で
芳香族ジアミンおよびテトラカルボン酸二無水物を反応
させて得る。The polyamic acid may be N-methylpyrrolidone, dimethylacetamide, dimethylformamide,
Obtained by reacting an aromatic diamine and a tetracarboxylic dianhydride in an aprotic polar solvent such as cresol or phenol.
【００２８】前記芳香族ジアミンとしては、ビス〔４−
（３−アミノフェノキシ）フェニル〕スルホン、２，
２’−ビス〔４−８−パラアミノフェノキシ）フェニ
ル〕プロパン、３，３’−ジメチル−４，４’−ジアミ
ノジフェニルメタン、２，２−ビス〔４−（パラアミノ
フェニキシ）フェニル〕ヘキサフルオロプロパン等が望
ましく、またこれらの混合物を用いてもよい。As the aromatic diamine, bis [4-
(3-aminophenoxy) phenyl] sulfone, 2,
2'-bis [4-8-paraaminophenoxy) phenyl] propane, 3,3'-dimethyl-4,4'-diaminodiphenylmethane, 2,2-bis [4- (paraaminophenoxy) phenyl] hexafluoropropane, etc. Are desirable, and mixtures of these may be used.
【００２９】前記テトラカルボン酸二無水物としては、
３，３’，４，４’−ベンゾフェノンテトラカルボン酸
二無水物、２，２−ビス〔４−（３，４−ジカルボキシ
フェノキシ）フェニル〕プロパン酸二無水物、２，２−
ビス〔４−（３，４−ジカルボキシフェノキシ）フェニ
ル〕ヘキサフルオロプロパン酸二無水物、３，３’，
４，４’−ジフェニルエーテルテトラカルボン酸二無水
物、３，３’，４，４’−ジフェニルスルフォンテトラ
カルボン酸二無水物、２，２−ビス（３，４−ジカルボ
キシフェニル）プロパン酸二無水物、２，２−ビス
（３，４−ジカルボキシフェニル）ヘキサフルオロプロ
パン酸二無水物等が望ましく、またこれらの混合物を用
いてもよい。As the tetracarboxylic dianhydride,
3,3 ′, 4,4′-benzophenone tetracarboxylic acid dianhydride, 2,2-bis [4- (3,4-dicarboxyphenoxy) phenyl] propanoic acid dianhydride, 2,2-
Bis [4- (3,4-dicarboxyphenoxy) phenyl] hexafluoropropanoic acid dianhydride, 3,3 ′,
4,4'-diphenyl ether tetracarboxylic acid dianhydride, 3,3 ', 4,4'-diphenyl sulfone tetracarboxylic acid dianhydride, 2,2-bis (3,4-dicarboxyphenyl) propanoic acid dianhydride , 2,2-bis (3,4-dicarboxyphenyl) hexafluoropropanoic acid dianhydride and the like, and a mixture thereof may be used.
【００３０】また、組成物に配合するビスマレイミドの
具体例としては、ビス（４−マレイミドフェニル）メタ
ン、ビス（４−マレイミドフェニル）エーテル、２，２
−ビス〔４−（４−マレイミドフェノキシ）フェニル〕
プロパン、２，２−ビス〔４−（４−マレイミドフェノ
キシ）フェニル〕ヘキサフルオロプロパン等がありこれ
らを単独あるいは混合して用いてもよい。これらのビス
マレイミドの配合割合は、樹脂分総量の１０〜７０重量
％が望ましく、特に２０〜５０重量％が好ましい。ビス
マレイミドを１０重量％以上混合することで三次元網目
構造が形成され、加熱圧着の繰り返しに対する接着物の
耐層間剥離の信頼性が保持できる。なお、ビスマレイミ
ドが７０重量％を超えると接着フィルムの靱性が低下す
る。Specific examples of the bismaleimide compounded in the composition include bis (4-maleimidophenyl) methane, bis (4-maleimidophenyl) ether, and 2,2.
-Bis [4- (4-maleimidophenoxy) phenyl]
There are propane, 2,2-bis [4- (4-maleimidophenoxy) phenyl] hexafluoropropane and the like, and these may be used alone or in combination. The mixing ratio of these bismaleimides is preferably 10 to 70% by weight, and particularly preferably 20 to 50% by weight, based on the total amount of the resin. By mixing bismaleimide in an amount of 10% by weight or more, a three-dimensional network structure is formed, and the reliability of delamination resistance of the adhesive material against repeated thermocompression bonding can be maintained. If the amount of bismaleimide exceeds 70% by weight, the toughness of the adhesive film will decrease.
【００３１】前記低熱膨張性接着フィルムのＧＰＣ法に
よる平均分子量は１００００〜５０００００であること
が望ましい。５０００００を超えるとポリアミック酸と
しての粘度が高くなりフィルムの形成が困難となり、１
００００未満では脆くなる。The average molecular weight of the low thermal expansion adhesive film by the GPC method is preferably 10,000 to 500,000. If it exceeds 500000, the viscosity as a polyamic acid becomes high, making it difficult to form a film.
If it is less than 0000, it becomes brittle.
【００３２】接着フィルムの成形は、前記低熱膨張性ポ
リイミド粉末を配合した組成物をガラス板、ステンレス
板などに流延塗布し、乾燥することによって形成するこ
とができる。この場合の乾燥温度、乾燥時間は用いた組
成物モノマおよび溶剤によって異なるが、ポリイミド，
ビスマレイミドの重合温度よりも低いことが必要であ
る。The adhesive film can be formed by casting the composition containing the low thermal expansion polyimide powder on a glass plate, a stainless steel plate or the like and drying it. The drying temperature and drying time in this case depend on the composition monomer and solvent used, but the polyimide,
It must be lower than the polymerization temperature of bismaleimide.
【００３３】前記の接着フィルムを銅箔、ポリイミドフ
ィルム等の基材の間に挾んで加熱圧着し、多層配線板を
得る。この際の加熱温度としては、接着フィルムの軟化
点以上の温度が好ましい。The above-mentioned adhesive film is sandwiched between base materials such as copper foil and polyimide film and heat-pressed to obtain a multilayer wiring board. The heating temperature at this time is preferably a temperature above the softening point of the adhesive film.
【００３４】なお、加熱圧着後の銅箔に対する引き剥が
し強度は７００ｇｆ／ｃｍ以上であることが好ましい。The peel strength of the copper foil after the thermocompression bonding is preferably 700 gf / cm or more.
【００３５】[0035]
【作用】密着性、流動性を向上させるためにフレキシブ
ル骨格を有するポリイミドに熱膨張率の小さなポリイミ
ド粉末を充填したことにより、フィルム全体としての熱
膨張率を小さくすることができる。By filling the polyimide having a flexible skeleton with polyimide powder having a small coefficient of thermal expansion in order to improve the adhesiveness and fluidity, the coefficient of thermal expansion of the entire film can be reduced.
【００３６】また、ポリイミドの一部にアミド結合を残
したことで、ベース樹脂との密着性がよくなり均一な組
成物が得られる。更にまた、ポリイミド粉末とベース樹
脂のアブレーションに必要なエネルギー密度は、共に１
Ｊ／ｃｍ2前後であるためにエキシマレーザー加工も問
題なく微細孔を正確に形成することができる。By leaving an amide bond in a part of the polyimide, the adhesion with the base resin is improved and a uniform composition can be obtained. Furthermore, the energy density required for ablation of the polyimide powder and the base resin is 1
Since it is around J / cm 2, it is possible to form fine holes accurately without any problem in excimer laser processing.
【００３７】[0037]
〔実施例１〜３および比較例１〜３〕３,３',４,４'−
ベンゾフェノンテトラカルボン酸二無水物３２２ｇと、
２,２'−ビス〔４−（パラアミノフェノキシ）フェニ
ル〕プロパン４１０ｇとをジメチルアセトアミド中で反
応させてポリアミック酸ワニスを得た。このワニスにビ
ス（４−マレイミド）メタン２９０ｇを溶解し、樹脂分
濃度２０％、粘度５０ポイズの樹脂組成物（１）を得
た。[Examples 1 to 3 and Comparative Examples 1 to 3] 3,3 ', 4,4'-
322 g of benzophenone tetracarboxylic dianhydride,
2,2′-bis [4- (paraaminophenoxy) phenyl] propane (410 g) was reacted in dimethylacetamide to obtain a polyamic acid varnish. 290 g of bis (4-maleimido) methane was dissolved in this varnish to obtain a resin composition (1) having a resin content concentration of 20% and a viscosity of 50 poise.
【００３８】次に、ジメチルアセトアミド中でｐ−フェ
ニレンジアミンと３,３',４,４'−ビフェニルテトラカ
ルボン酸二無水物を反応させて得たポリアミック酸ワニ
スを水中に再沈し、溶媒を完全に取り除いた後粉砕、乾
燥してポリアミック酸粉末を得た。このポリアミック酸
粉末を窒素雰囲気中、１５０℃で３０分加熱しイミド化
率３０％のポリイミド粉末とし、前記樹脂組成物（１）
に加え十分混練、均一に分散させ樹脂組成物（２）を得
た。この樹脂組成物（２）をガラス板に流延、１００℃
で１時間乾燥後ガラス板より剥離させたフィルムを鉄枠
に固定、さらに２００℃３０分加熱して、膜厚２５μｍ
の本発明の接着フィルムを得た。Next, the polyamic acid varnish obtained by reacting p-phenylenediamine and 3,3 ', 4,4'-biphenyltetracarboxylic dianhydride in dimethylacetamide was reprecipitated in water to remove the solvent. After being completely removed, it was ground and dried to obtain a polyamic acid powder. The polyamic acid powder is heated in a nitrogen atmosphere at 150 ° C. for 30 minutes to obtain a polyimide powder having an imidization ratio of 30%, and the resin composition (1) is used.
Was sufficiently kneaded and uniformly dispersed to obtain a resin composition (2). This resin composition (2) was cast on a glass plate at 100 ° C.
The film peeled off from the glass plate after being dried for 1 hour was fixed on an iron frame and further heated at 200 ° C for 30 minutes to give a film thickness of 25 µm.
The adhesive film of the present invention was obtained.
【００３９】この接着フィルムを厚さ２０μｍの銅箔と
ポリイミドフィルム（デュポン社製カプトンフィルム：
芳香族ポリイミドフィルム）の間に挾み、４０ｋｇｆ／
ｃｍ2、２５０℃で加熱，圧着した。A 20 μm thick copper foil and a polyimide film (Kapton film manufactured by DuPont:
Between the aromatic polyimide film), 40kgf /
It was heated at 250 ° C. in cm 2 and pressure-bonded.
【００４０】低熱膨張性ポリイミド粉末の配合量を変え
た接着フィルムの諸特性を表１に示す。熱膨張係数は昇
温速度５℃／分で測定し、５０〜２００℃の平均値を示
した。引剥し強さは９０°ピール法により引張速度０．
５ｍｍ／分で測定した。Table 1 shows various properties of the adhesive film in which the compounding amount of the low thermal expansion polyimide powder is changed. The thermal expansion coefficient was measured at a temperature rising rate of 5 ° C / min, and an average value of 50 to 200 ° C was shown. Peel strength was measured by the 90 ° peel method at a pulling speed of 0.
It was measured at 5 mm / min.
【００４１】[0041]
【表１】 [Table 1]
【００４２】〔実施例４〕３,３',４,４'−ベンゾフェ
ノンテトラカルボン酸二無水物、２,２'−ビス〔４−
（パラアミノフェノキシ）フェニル〕プロパン、ビス
（４−マレイミド）メタンの３：３：４の割合で配合し
た組成物に、低熱膨張率のポリイミド粉末を配合し、実
施例１と同様にして接着フィルムを作成した。なお、上
記ポリイミド粉末はｐ−フェニレンジアミン：３,３',
４,４'−ビフェニルテトラカルボン酸二無水物が１：１
で合成したものである。Example 4 3,3 ′, 4,4′-benzophenone tetracarboxylic dianhydride, 2,2′-bis [4-
(Para-aminophenoxy) phenyl] propane and bis (4-maleimido) methane were mixed at a ratio of 3: 3: 4 with a polyimide powder having a low coefficient of thermal expansion, and an adhesive film was prepared in the same manner as in Example 1. Created. The polyimide powder is p-phenylenediamine: 3,3 ′,
4,4'-biphenyltetracarboxylic dianhydride is 1: 1
It was synthesized in.
【００４３】本実施例により接着フィルムの熱膨張係数
は１８ｐｐｍ／℃，銅箔引剥し強さは１３００ｇｆ／ｃ
ｍであった。According to this example, the thermal expansion coefficient of the adhesive film was 18 ppm / ° C., and the copper foil peeling strength was 1300 gf / c.
It was m.
【００４４】〔実施例５〕実施例３および実施例４によ
り得た膜厚２０μｍの接着フィルムを厚さ２５μｍのカ
プトンフィルム２枚に挾み、加熱，圧着して得たシート
をＫｒＦレーザ（エネルギー密度１．５Ｊ／ｃｍ2）を
用いて加工し、ＳＥＭにより観察したところ内径５０μ
ｍの均一な孔を形成することができた。Example 5 The sheet obtained by sandwiching the adhesive film having a film thickness of 20 μm obtained in Example 3 and Example 4 on two Kapton films having a thickness of 25 μm and heating and pressing the resulting film was subjected to KrF laser (energy). It was processed using a density of 1.5 J / cm 2 ) and observed by SEM.
m uniform holes could be formed.
【００４５】〔実施例６〕実施例２において、ポリイミ
ド粉末のイミド化率を５０％として同様に接着フィルム
作製した。その結果、熱膨張係数１８ｐｐｍ、銅箔引き
剥がし強さ１２００ｇ／ｃｍであった。Example 6 An adhesive film was produced in the same manner as in Example 2, except that the imidization ratio of the polyimide powder was 50%. As a result, the thermal expansion coefficient was 18 ppm, and the copper foil peeling strength was 1200 g / cm.
【００４６】〔比較例４〕前記低熱膨張性ポリイミド粉
末の代わりにシリカ粉（平均粒径１μｍ）を用いた以外
は実施例４と同様にしてシートを作製し、同様の条件で
ＫｒＦレーザ加工したところ、接着フィルム層中のシリ
カ粒子が除去されず均一な孔を形成することができなか
った。Comparative Example 4 A sheet was prepared in the same manner as in Example 4 except that silica powder (average particle size 1 μm) was used in place of the low thermal expansion polyimide powder, and KrF laser processing was performed under the same conditions. However, the silica particles in the adhesive film layer were not removed and uniform pores could not be formed.
【００４７】[0047]
【発明の効果】本発明の低熱膨張性接着フィルムを用い
ることにより、低熱膨張性で、かつ、レーザー加工性に
優れた配線基板を提供することができる。また、該配線
基板は熱応力による反りやクラックの発生が少なく、高
信頼性の多層配線基板を提供することができる。By using the low thermal expansion adhesive film of the present invention, a wiring board having low thermal expansion and excellent laser processability can be provided. Further, the wiring board is less likely to be warped or cracked due to thermal stress, and a highly reliable multilayer wiring board can be provided.
───────────────────────────────────────────────────── フロントページの続き (51)Int.Cl.5 識別記号 庁内整理番号 ＦＩ 技術表示箇所 Ｈ０５Ｋ 3/38 Ｅ 7011−4Ｅ 3/46 Ｔ 6921−4Ｅ (72)発明者 片桐 純一 茨城県日立市久慈町4026番地 株式会社日 立製作所日立研究所内 (72)発明者 岡部 義昭 茨城県日立市久慈町4026番地 株式会社日 立製作所日立研究所内 (72)発明者 池田 孝栄 茨城県日立市久慈町4026番地 株式会社日 立製作所日立研究所内 (72)発明者 高橋 昭雄 茨城県日立市久慈町4026番地 株式会社日 立製作所日立研究所内─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. 5 Identification code Internal reference number FI Technical indication location H05K 3/38 E 7011-4E 3/46 T 6921-4E (72) Inventor Junichi Katagiri Hitachi Ibaraki Prefecture 4026 Kuji Town, Kuji Town, Hitachi Research Laboratory, Hitachi Ltd. (72) Inventor Yoshiaki Okabe, Kuji Town, Hitachi City, Hitachi City, Ibaraki Prefecture 4026, Hitachi Research Laboratory, Hitachi, Ltd. (72) Inventor Akio Takahashi 4026, Kuji Town, Hitachi City, Ibaraki Prefecture Hitachi Research Laboratory, Hitachi, Ltd.
Claims (9)
むポリアミック酸組成物からなり、加熱硬化後の熱膨張
係数が（５〜３０）×１０~6／℃であることを特徴とす
る低熱膨張性接着フィルム。1. A low thermal expansion adhesive film comprising a polyamic acid composition containing bismaleimide and polyimide powder and having a thermal expansion coefficient of (5 to 30) × 10 to 6 / ° C. after heat curing. ..
重量％であることを特徴とする請求項１記載の低熱膨張
性接着フィルム。2. The amount of the bismaleimide compounded is 10 to 70.
The low thermal expansion adhesive film according to claim 1, wherein the low thermal expansion adhesive film is in weight%.
１０~6／℃以下で、前記組成物中の含有量が３０〜７０
重量％であることを特徴とする請求項１または２に記載
の低熱膨張性接着フィルム。3. The coefficient of thermal expansion of the polyimide powder is 20 ×
In 10 ~ 6 / ° C. or less, the content in the composition is 30 to 70
The low thermal expansion adhesive film according to claim 1 or 2, wherein the low thermal expansion adhesive film is in a weight percentage.
９５％のポリイミドからなることを特徴とする請求項
１，２または３に記載の低熱膨張性接着フィルム。4. The imidization ratio of the polyimide powder is 20 to.
The low thermal expansion adhesive film according to claim 1, wherein the adhesive film is made of 95% polyimide.
フィルムを介して複数積層されてなる多層配線基板にお
いて、前記接着フィルムがビスマレイミドおよびポリイ
ミド粉末を含むポリアミック酸組成物からなり、加熱硬
化後の熱膨張係数が（５〜３０）×１０~6／℃である低
熱膨張性接着フィルムであることを特徴とする多層配線
基板。5. A multilayer wiring board comprising a plurality of organic insulating layers each having a metal wiring on the surface thereof, which are laminated via an adhesive film, wherein the adhesive film is made of a polyamic acid composition containing bismaleimide and polyimide powder. A multilayer wiring board, which is a low thermal expansion adhesive film having a coefficient of thermal expansion after curing of (5 to 30) × 10 to 6 / ° C.
重量％であることを特徴とする請求項５記載の多層配線
基板。6. The amount of the bismaleimide compounded is 10 to 70.
The multilayer wiring board according to claim 5, wherein the multilayer wiring board has a weight percentage.
１０~6／℃以下であり、前記組成物中の含有量が３０〜
７０重量％であることを特徴とする請求項５または６に
記載の多層配線基板。7. The coefficient of thermal expansion of the polyimide powder is 20 ×
And at 10 ~ 6 / ° C. or less, the content in the composition is 30 to
70% by weight, The multilayer wiring board according to claim 5 or 6, wherein
しイミド化率で２０〜９５％のポリイミドからなること
を特徴とする請求項５，６または７に記載の多層配線基
板。8. The multilayer wiring board according to claim 5, 6 or 7, wherein said polyimide powder is made of polyimide having a partial amide bond and having an imidization ratio of 20 to 95%.
ミドであることを特徴とする請求項５〜８のいずれかに
記載の多層配線基板。9. The multilayer wiring board according to claim 5, wherein the organic insulating layer provided with the metal wiring is polyimide.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP4020964A JPH05214301A (en) | 1992-02-06 | 1992-02-06 | Low thermally expansible adhesive film and wiring board using the same |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP4020964A JPH05214301A (en) | 1992-02-06 | 1992-02-06 | Low thermally expansible adhesive film and wiring board using the same |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH05214301A true JPH05214301A (en) | 1993-08-24 |
Family
ID=12041862
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP4020964A Pending JPH05214301A (en) | 1992-02-06 | 1992-02-06 | Low thermally expansible adhesive film and wiring board using the same |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH05214301A (en) |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6399891B1 (en) | 1999-06-29 | 2002-06-04 | Sony Chemicals Corporation | Multilayer boards |
| WO2005084948A1 (en) * | 2004-03-04 | 2005-09-15 | Toray Industries, Inc. | Heat-resistant resin laminated film, multilayer film with metal layer including same, and semiconductor device |
| WO2007013758A1 (en) * | 2005-07-27 | 2007-02-01 | Lg Chem. Ltd. | Metallic laminate and method of manufacturing the same |
| WO2009084533A1 (en) * | 2007-12-28 | 2009-07-09 | Mitsui Mining & Smelting Co., Ltd. | Copper foil with resin and process for producing copper foil with resin |
| JP2009173017A (en) * | 2007-12-28 | 2009-08-06 | Mitsui Mining & Smelting Co Ltd | Resin-coated copper foil and process for producing resin-coated copper foil |
| JP2019123864A (en) * | 2018-01-17 | 2019-07-25 | 東レ株式会社 | Resin composition, cured film, method for producing relief pattern of cured film, electronic component, semiconductor device, method for producing electronic component, and method for producing semiconductor device |
-
1992
- 1992-02-06 JP JP4020964A patent/JPH05214301A/en active Pending
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6399891B1 (en) | 1999-06-29 | 2002-06-04 | Sony Chemicals Corporation | Multilayer boards |
| CN100464973C (en) * | 1999-06-29 | 2009-03-04 | 索尼化学株式会社 | Multi-layer substrates |
| WO2005084948A1 (en) * | 2004-03-04 | 2005-09-15 | Toray Industries, Inc. | Heat-resistant resin laminated film, multilayer film with metal layer including same, and semiconductor device |
| WO2007013758A1 (en) * | 2005-07-27 | 2007-02-01 | Lg Chem. Ltd. | Metallic laminate and method of manufacturing the same |
| US8034460B2 (en) | 2005-07-27 | 2011-10-11 | Lg Chem, Ltd. | Metallic laminate and method of manufacturing the same |
| WO2009084533A1 (en) * | 2007-12-28 | 2009-07-09 | Mitsui Mining & Smelting Co., Ltd. | Copper foil with resin and process for producing copper foil with resin |
| JP2009173017A (en) * | 2007-12-28 | 2009-08-06 | Mitsui Mining & Smelting Co Ltd | Resin-coated copper foil and process for producing resin-coated copper foil |
| JP2019123864A (en) * | 2018-01-17 | 2019-07-25 | 東レ株式会社 | Resin composition, cured film, method for producing relief pattern of cured film, electronic component, semiconductor device, method for producing electronic component, and method for producing semiconductor device |
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