JPH0257713B2 - - Google Patents
Info
- Publication number
- JPH0257713B2 JPH0257713B2 JP61106698A JP10669886A JPH0257713B2 JP H0257713 B2 JPH0257713 B2 JP H0257713B2 JP 61106698 A JP61106698 A JP 61106698A JP 10669886 A JP10669886 A JP 10669886A JP H0257713 B2 JPH0257713 B2 JP H0257713B2
- Authority
- JP
- Japan
- Prior art keywords
- heat
- printed wiring
- wiring board
- resistant
- weight
- 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.)
- Expired - Lifetime
Links
Landscapes
- Non-Metallic Protective Coatings For Printed Circuits (AREA)
Description
〔産業上の利用分野〕
本発明は耐熱性プリント配線板（特にフレキシ
ブルな耐熱性プリント配線板）及びその製造方法
に関する。更に詳しくは、極性有機溶媒可溶性芳
香族ポリアミドイミド樹脂又はその組成物をカバ
ーレイとすることを特徴とする耐熱性プリント配
線板（特に耐熱性フレキシブルプリント配線板）
とその製造方法に関するものである。
〔従来の技術〕
エレクトロニクス応用機器の小型化、軽量化、
高性能化が急速に進んでいる。この進歩を支えて
いるものの１つに周辺部品材料の著しい発展があ
る。とりわけ、プリント配線板の進歩は目ざまし
く、上記の小型軽量化及び高性能化に大きく寄与
してきた。最近は、その中でもフレキシブルプリ
ント配線板に注目が集まつてきており、これのよ
り一層の改良が望まれている。
即ち、プリント配線板には半田付等の工程に耐
えるだけの高い耐熱性が必要とされるが、この様
な耐熱性があつて、強度もあり、電気特性も優れ
て、しかも可撓性（フレキシビリテイがある）が
あるというような３拍子も４拍子も揃つた材料と
なると、いまだ実現していない。
今のところこれらの要請に最も近いものとして
は、ポリイミドフイルムに銅箔を接着したフレキ
シブル銅張板をパターニングしエツチングした
後、カバーレイフイルム（予め金型で穿孔した、
接着剤付きのポリイミドフイルム）を圧着被覆し
て製造したものがある（電子材料編集部編「プリ
ント配線技術」1983年６月10日、工業調査会発
行：参照）。
しかし、このものもカバーレイ被着において接
着剤を使用しているため、せつかくのポリイミド
の耐熱性が生かされず半田耐熱性に於いて不満足
のものとなつており、又ポリイミド樹脂の吸湿性
のため乾燥エージング工程に付さないと「ふく
れ」等の問題が起こるという問題点を有してい
た。
加えて、ポリイミドはもともと高価な樹脂であ
るところ、金型で型通り打ち抜く際に発生するロ
スが馬鹿にならず、多種多様のパターンに対応す
るための金型コスト及び手間の増加と相まつて高
価に過ぎるという欠点を有していた。
なお、工程が簡便で、コストも安い半田レジス
ト等のコーテイング剤によるオーバーコート方式
も開発されているが、耐熱性が著しく低いか、可
撓性が不足しているかのいずれかであり、安価で
あつても、性能的には前記のポリイミド系のプリ
ント配線板の域には達していない。
〔発明が解決しようとする問題点〕
この様な状況下にあつて、本発明者は高速化し
ている自動組み立てラインに対応しうる熱湿時の
寸法安定性、半田耐熱性を有し、可撓性も優れ、
且つ工程も簡単なカバーレイ（カバーコート）を
用いた耐熱プリント配線板、とくに耐熱フレキシ
ブルプリント配線板を提供すべく、鋭意検討を重
ねた結果、極性有機溶媒可溶性芳香族ポリアミド
イミド樹脂を用いることによつて、目的を達成で
きることを見出だし、本発明に到達した。
〔問題点を解決するための手段〕
即ち本発明は、
の繰返し単位からなり、還元粘度が0.5〜3.5であ
つて、且つ
Ｎ，Ｎ−ジメチルアセトアミド又はＮ−メチル
−２−ピロリドンに溶解するという特徴を持つ特
定の芳香族ポリアミドイミドを主成分とするカバ
ーレイを有する耐熱性フレキシブルプリント配線
板を提供するものである。
又、本発明は上記芳香族ポリアミドイミド樹脂
に高熱伝導性フイラーもしくは導電性金属微粉体
又は雲母を加えることにより一層その効果を向上
せしめた耐熱性フレキシブルプリント配線板も同
時に提供するものである。
以下本発明を詳しく説明する。
本発明に使用される芳香族ポリアミドイミド樹
脂は極性有機溶媒可溶性の芳香族ポリアミドイミ
ド樹脂であつて、一般式
（但し、ｎは２個以上の整数を表わす）の重合体
が用いられる。
本発明で用いる芳香族ポリアミドイミド樹脂の
還元粘度は0.5〜3.5である。還元粘度が低すぎる
と機械的強度及び可撓性が低下するし、還元粘度
が高すぎると極性有機溶媒に対する溶解度が低下
し実用的でなくなる。
これらの芳香族ポリアミドイミド樹脂は、公知
の方法、例えば
芳香族ジアミンと無水トリメツト酸クロライ
ドとを反応させるか或いは芳香族ジアソシアネ
ートとトリメツト酸無水物を反応させるかによつ
て製造することができる。
このうちの反応を代表例として以下に説明す
る。
[Industrial Application Field] The present invention relates to a heat-resistant printed wiring board (particularly a flexible heat-resistant printed wiring board) and a method for manufacturing the same. More specifically, a heat-resistant printed wiring board (especially a heat-resistant flexible printed wiring board) characterized by using a polar organic solvent-soluble aromatic polyamide-imide resin or a composition thereof as a coverlay.
and its manufacturing method. [Conventional technology] Making electronics application equipment smaller and lighter;
High performance is progressing rapidly. One of the things supporting this progress is the remarkable development of peripheral component materials. In particular, the progress of printed wiring boards has been remarkable and has greatly contributed to the above-mentioned reduction in size and weight and improvement in performance. Recently, attention has been focused on flexible printed wiring boards, and further improvements in these boards are desired. In other words, printed wiring boards must have high heat resistance to withstand processes such as soldering. When it comes to materials that have both triple and quadruple time signatures (with flexibility), this has not yet been achieved. At present, the closest thing to these requirements is to pattern and etch a flexible copper-clad board made by bonding copper foil to a polyimide film, and then create a coverlay film (previously perforated with a mold).
Some are manufactured by pressure-coating a polyimide film with adhesive (see "Printed Wiring Technology," edited by the Electronic Materials Editorial Department, June 10, 1983, published by Kogyo Kenkyukai). However, since adhesive is used to attach the coverlay, the heat resistance of polyimide is not fully utilized, resulting in unsatisfactory soldering heat resistance, and the moisture absorption of polyimide resin Therefore, if it is not subjected to a dry aging process, problems such as "blistering" occur. In addition, since polyimide is originally an expensive resin, the loss that occurs when punching it out with a mold is significant, and the cost and labor required to accommodate a wide variety of patterns increases, making it expensive. It had the disadvantage of being too large. In addition, overcoating methods using coating agents such as solder resists have been developed, which have a simple process and are inexpensive, but they either have extremely low heat resistance or lack flexibility, and are inexpensive. Even if there is, the performance does not reach the level of the polyimide-based printed wiring board mentioned above. [Problems to be Solved by the Invention] Under these circumstances, the present inventor has developed a material that has dimensional stability in hot and humid conditions, soldering heat resistance, and is compatible with the increasingly high-speed automatic assembly lines. Excellent flexibility,
In order to provide a heat-resistant printed wiring board, especially a heat-resistant flexible printed wiring board, using a coverlay (cover coat) that is easy to process, we have conducted extensive research and have decided to use aromatic polyamide-imide resin soluble in polar organic solvents. Therefore, the inventors have discovered that the object can be achieved, and have arrived at the present invention. [Means for solving the problems] That is, the present invention has the following features: A cover whose main component is a specific aromatic polyamideimide, which consists of repeating units of The present invention provides a heat-resistant flexible printed wiring board having a wire. The present invention also provides a heat-resistant flexible printed wiring board whose effects are further improved by adding a highly thermally conductive filler, conductive metal fine powder, or mica to the aromatic polyamide-imide resin. The present invention will be explained in detail below. The aromatic polyamide-imide resin used in the present invention is an aromatic polyamide-imide resin soluble in a polar organic solvent, and has the general formula (However, n represents an integer of 2 or more) is used. The aromatic polyamideimide resin used in the present invention has a reduced viscosity of 0.5 to 3.5. If the reduced viscosity is too low, the mechanical strength and flexibility will decrease, and if the reduced viscosity is too high, the solubility in polar organic solvents will decrease, making it impractical. These aromatic polyamide-imide resins can be produced by a known method, for example, by reacting an aromatic diamine with trimethic anhydride chloride or reacting an aromatic diasocyanate with trimethic anhydride. . One of these reactions will be described below as a representative example.
次に参考例、実施例及び比較例をあげて本発明
を説明する。
参考例１：耐熱性絶縁インクＡの製造例
４，4′−ジアミノジフエニルエーテル
（DADPE）無水トリメリツト酸クロライド
（TMAC）から合成した極性有機溶媒可溶性の芳
香族ポリアミドイミド（PAI：還元粘度1.3）100
重量部にＮ−メチル−２ピロリドン（NMP）
400重量部を加え、該PAIをNMP中に溶解させて
耐熱性絶縁インクＡを得た。
参考例：２耐熱性絶縁インクＢの製造例
実施例１と同様にDADPEとTMACから合成
した極性有機溶媒可溶性の芳香族ポリアミドイミ
ド（PAI：還元粘度1.4）100重量部にNMP470重
量部を加え、該PAIをNMP中に溶解する。
次いで、窒化ホウ酸（昭和電工社製、粒径1.7μ
ｍ）17重量部を上記PAI樹脂溶液と混合し、万能
混練機で均一に分散させ耐熱性絶縁インクＢを得
た。
参考例３：耐熱性絶縁インクＣの製造例
DADPEとTMACから合成した極性有機溶媒
可溶性の芳香族ポリアミドイミド（PAI：還元粘
度1.4）100重量部にNMP490重量部を加え、該
PAIを溶解する。
次いで雲母（マイカ）（玉木マイカ社製、粒径
46μｍ）48重量部をNMP90重量部に分散させた
溶液と上記PAI樹脂溶液とを混合し、ニーダーで
マイカを均一分散させ耐熱性絶縁インクＣを得
た。
参考例４：耐熱性絶縁インクＤの製造例
DADPEとTMACから合成した極性有機溶媒
可溶性の芳香族ポリアミドイミド（PAI：還元粘
度1.5）120重量部にNMP480重量部を加え、該
PAIをNMP中に溶解する。次いでアルミニウム
粉末（平均粒径15μｍ福田金属箔粉工業製ALC用
フアイン）54重量部をNMP108重量部に分散さ
せた溶液と上記PAI樹脂溶液とを混合し、ニーダ
ーでアルミニウム粉末を均一分散させ耐熱性絶縁
インクＤを得た。
実施例
通常のフレキシブルプリント基板用片面胴張り
板（銅箔厚35μｍ、カプトン厚25μｍ、接着剤厚
25μｍ）を用いフオトレジスト法よりエツチング
パターンを形成し、次いで塩化第二鉄液でエツチ
ングし、さらにエツチングレジストを除去して、
配線回路パターンを得た。
次に参考例１〜４に記載した極性有機溶媒可溶
性ポリアミドイミド（ソクシール（登録商標）ニ
ツポン高度紙工業社製）を主成分とする各種の樹
脂組成物からなる耐熱性絶縁インクＡ，Ｂ，Ｃ，
Ｄをラインケメタルスクリーン（165メツシユ、
乳剤厚10μｍ）を用いスクリーン印刷法で上記配
線回路パターン上に所定パターンの膜厚を約10μ
ｍになるように印刷した。続いて、この配線回路
パターンを80℃のホツトプレート上で10分予備乾
燥後、アルミニウム製の当て板に、印刷面が表面
になるように固定して250℃で10分熱処理し、溶
媒を除去してフレキシブル配線回路板を得た。
上記の方法で得たフレキシブル配線回路板を用
い、ハンダ耐熱性、耐折性、密着性、耐電圧につ
いて恒温恒湿下（40℃，90％RH）及び冷熱衝撃
下（−55℃30分〜125℃30分）での特性評価を行
つた。この等の結果を表−１に示すが、優れたフ
レキシブルプリント配線回路板であることがわか
る。
なお、ハンダ耐熱性の試験を300℃，20秒とい
う、より厳しい条件で行つた場合、フイラーの入
つていない耐熱性絶縁インクＡでは、カール（そ
り）が発生した。又、フイラー入りの耐熱性絶縁
インク（例えばＣ）において耐折性が若干低目に
出ているが、実用上全く問題がない耐折性である
ことを付言しておく。
特性評価の各測定は次に示す通り行つた。
ハンダ耐熱性：試験片を260℃のハンダ浴に
10秒間浸漬し、ふくれ、はがれの発生状態を観
察。
耐折れ性：JIS P8115に準じ、MIT型試験器
でＲ＝0.38、荷重500ｇで測定。
クロスカツトテープ法、即ち塗膜をつくり
JIS K5400基盤目試験に準じてクロスカツト
し、PETテープを付着、次いで引き剥がして
１〜100個の中の残存升目を数える。
耐電圧：試験片にAC500Vの電圧を１分間印
加し、異常の有無を観察。
Next, the present invention will be explained with reference to Reference Examples, Examples, and Comparative Examples. Reference Example 1: Production example of heat-resistant insulating ink A Polar organic solvent soluble aromatic polyamideimide (PAI: reduced viscosity 1.3) synthesized from 4,4'-diaminodiphenyl ether (DADPE) and trimellitic anhydride (TMAC) 100
N-methyl-2-pyrrolidone (NMP) in weight part
400 parts by weight was added and the PAI was dissolved in NMP to obtain heat-resistant insulating ink A. Reference Example: 2 Production Example of Heat-resistant Insulating Ink B 470 parts by weight of NMP was added to 100 parts by weight of polar organic solvent-soluble aromatic polyamideimide (PAI: reduced viscosity 1.4) synthesized from DADPE and TMAC in the same manner as in Example 1. The PAI is dissolved in NMP. Next, boric acid nitride (manufactured by Showa Denko, particle size 1.7μ
m) 17 parts by weight were mixed with the above PAI resin solution and uniformly dispersed using a universal kneader to obtain heat-resistant insulating ink B. Reference Example 3: Production example of heat-resistant insulating ink C 490 parts by weight of NMP was added to 100 parts by weight of polar organic solvent-soluble aromatic polyamideimide (PAI: reduced viscosity 1.4) synthesized from DADPE and TMAC.
Dissolve PAI. Next, mica (manufactured by Tamaki Mica Co., Ltd., particle size
A solution prepared by dispersing 48 parts by weight of NMP in 90 parts by weight of NMP was mixed with the above PAI resin solution, and the mica was uniformly dispersed using a kneader to obtain heat-resistant insulating ink C. Reference Example 4: Production example of heat-resistant insulating ink D Add 480 parts by weight of NMP to 120 parts by weight of polar organic solvent-soluble aromatic polyamideimide (PAI: reduced viscosity 1.5) synthesized from DADPE and TMAC.
Dissolve PAI in NMP. Next, a solution in which 54 parts by weight of aluminum powder (ALC fine manufactured by Fukuda Metal Foil and Powder Industries, Ltd., with an average particle size of 15 μm) is dispersed in 108 parts by weight of NMP is mixed with the above PAI resin solution, and the aluminum powder is uniformly dispersed with a kneader to achieve heat resistance. Insulating ink D was obtained. Example Single-sided body panel for ordinary flexible printed circuit board (copper foil thickness 35μm, Kapton thickness 25μm, adhesive thickness
An etching pattern was formed using a photoresist method (25 μm), then etched with a ferric chloride solution, and the etching resist was removed.
A wiring circuit pattern was obtained. Next, heat-resistant insulating inks A, B, and C are made of various resin compositions whose main component is polar organic solvent-soluble polyamideimide (Socsil (registered trademark) manufactured by Nippon Kokoshi Kogyo Co., Ltd.) described in Reference Examples 1 to 4. ，
D for Reinke metal screen (165 meters,
A film thickness of approximately 10 μm is applied to the above wiring circuit pattern using a screen printing method using emulsion (emulsion thickness: 10 μm).
It was printed to be m. Next, this wiring circuit pattern was pre-dried for 10 minutes on a hot plate at 80℃, then fixed on an aluminum backing plate with the printed side facing up and heat treated at 250℃ for 10 minutes to remove the solvent. A flexible wiring circuit board was obtained. Using the flexible wiring circuit board obtained by the above method, the solder heat resistance, folding durability, adhesion, and voltage resistance were tested under constant temperature and humidity (40℃, 90%RH) and thermal shock (-55℃ 30 minutes ~ Characteristics were evaluated at 125°C for 30 minutes). The results are shown in Table 1, and it can be seen that the flexible printed circuit board was excellent. Note that when the solder heat resistance test was conducted under more severe conditions of 300° C. for 20 seconds, curling occurred in heat-resistant insulating ink A that did not contain filler. Also, it should be noted that although the folding durability of the heat-resistant insulating ink containing filler (for example, C) is slightly low, it is a folding durability that does not pose any practical problems. Each measurement for characteristic evaluation was performed as shown below. Solder heat resistance: test piece in a 260℃ solder bath
Dip for 10 seconds and observe whether it bulges or peels. Bending resistance: Measured according to JIS P8115 using an MIT tester at R = 0.38 and a load of 500g. Cross-cut tape method, that is, creating a coating film
Cross-cut according to the JIS K5400 board test, attach PET tape, then peel it off and count the remaining squares from 1 to 100. Withstand voltage: Apply a voltage of AC500V to the test piece for 1 minute and observe whether there is any abnormality.
以上のように、本発明の耐熱性プリント配線板
は、このところ、重要視されているハンダ耐熱性
の点で優れた性能を有し、その他の物性、例えば
耐折れ性、密着性、耐電圧性においても優れてい
る上、長期使用に対する信頼性も極めて高いとい
う卓越した効果を有するものである。
加えて、本発明の耐熱性プリント配線板は、煩
雑でコストアツプにつながる後処理工程（エージ
ング）を必要とせず、特別な金型も要しない、材
料ロスの無い極めて経済的且つ簡便な製造方法を
採ることができるという優れた効果も合わせ有す
るものである。
As described above, the heat-resistant printed wiring board of the present invention has excellent performance in terms of solder heat resistance, which has been emphasized recently, and has other physical properties such as bending resistance, adhesion, and voltage resistance. In addition to being excellent in terms of performance, it also has the outstanding effect of being extremely reliable for long-term use. In addition, the heat-resistant printed wiring board of the present invention does not require a complicated and cost-increasing post-processing process (aging), does not require a special mold, and has an extremely economical and simple manufacturing method that eliminates material loss. It also has the excellent effect of being able to be used.
Claims (1)
つて、且つ、 Ｎ，Ｎ−ジメチルアセトアミド又はＮ−メチル
−２−ピロリドンに溶解するという特徴を持つ特
定の芳香族ポリアミドイミドを主成分とするカバ
ーレイを有する耐熱性フレキシブルプリント配線
板。 ２ の繰返し単位からなり、還元粘度が0.5〜3.5であ
つて、且つ、 Ｎ，Ｎ−ジメチルアセトアミド又はＮ−メチル−
２−ピロリドンに溶解するという特徴を持つ特定
の芳香族ポリアミドイミドと高熱伝導性フイラー
もしくは導電性金属微粉体又は雲母を主成分とす
るカバーレイを有する耐熱性フレキシブルプリン
ト配線板。[Claims] 1 The main component is a specific aromatic polyamideimide, which consists of repeating units of Heat-resistant flexible printed wiring board with coverlay. 2 N,N-dimethylacetamide or N-methyl-
A heat-resistant flexible printed wiring board having a coverlay mainly composed of a specific aromatic polyamide-imide that is soluble in 2-pyrrolidone and a highly thermally conductive filler, conductive metal fine powder, or mica.
Priority Applications (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP10669886A JPS62263692A (en) | 1986-05-12 | 1986-05-12 | Heat-resistant printed wiring board and manufacture of the same |
| JP2837390A JPH0767007B2 (en) | 1986-05-12 | 1990-02-09 | Method for manufacturing heat resistant printed wiring board |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP10669886A JPS62263692A (en) | 1986-05-12 | 1986-05-12 | Heat-resistant printed wiring board and manufacture of the same |
Related Child Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2837390A Division JPH0767007B2 (en) | 1986-05-12 | 1990-02-09 | Method for manufacturing heat resistant printed wiring board |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS62263692A JPS62263692A (en) | 1987-11-16 |
| JPH0257713B2 true JPH0257713B2 (en) | 1990-12-05 |
Family
ID=14440235
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP10669886A Granted JPS62263692A (en) | 1986-05-12 | 1986-05-12 | Heat-resistant printed wiring board and manufacture of the same |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS62263692A (en) |
Families Citing this family (18)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB2265021B (en) * | 1992-03-10 | 1996-02-14 | Nippon Steel Chemical Co | Photosensitive materials and their use in forming protective layers for printed circuit and process for preparation of printed circuit |
| EP2408836B1 (en) * | 2009-03-16 | 2014-12-10 | Sun Chemical B.V. | Liquid coverlays for flexible printed circuit boards |
| US9668360B2 (en) | 2009-10-29 | 2017-05-30 | Sun Chemical Corporation | Polyamideimide adhesives for printed circuit boards |
| CN105164585B (en) | 2013-04-18 | 2020-02-21 | 太阳油墨制造株式会社 | Laminated structure, flexible printed circuit board, and manufacturing method thereof |
| JP6306296B2 (en) | 2013-07-09 | 2018-04-04 | 太陽インキ製造株式会社 | Photosensitive thermosetting resin composition and flexible printed wiring board |
| JP6372988B2 (en) | 2013-10-09 | 2018-08-15 | 太陽インキ製造株式会社 | Photosensitive thermosetting resin composition and flexible printed wiring board |
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| JP7300619B2 (en) | 2019-01-11 | 2023-06-30 | 太陽ホールディングス株式会社 | Laminated structures, dry films, cured products thereof, and electronic components |
| JP2020167352A (en) | 2019-03-29 | 2020-10-08 | 太陽インキ製造株式会社 | Dry film and printed wiring board |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS55143056A (en) * | 1979-04-26 | 1980-11-08 | Sumitomo Bakelite Co Ltd | Manufacture of wiring structure for electronic circuit |
-
1986
- 1986-05-12 JP JP10669886A patent/JPS62263692A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPS62263692A (en) | 1987-11-16 |
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