JPH03149227A - Resin composition - Google Patents
Resin compositionInfo
- Publication number
- JPH03149227A JPH03149227A JP28751489A JP28751489A JPH03149227A JP H03149227 A JPH03149227 A JP H03149227A JP 28751489 A JP28751489 A JP 28751489A JP 28751489 A JP28751489 A JP 28751489A JP H03149227 A JPH03149227 A JP H03149227A
- Authority
- JP
- Japan
- Prior art keywords
- diaminobenzanilide
- circuit board
- aromatic
- mol
- dianhydride
- 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
- 239000011342 resin composition Substances 0.000 title claims abstract description 7
- GTDPSWPPOUPBNX-UHFFFAOYSA-N ac1mqpva Chemical compound CC12C(=O)OC(=O)C1(C)C1(C)C2(C)C(=O)OC1=O GTDPSWPPOUPBNX-UHFFFAOYSA-N 0.000 claims abstract description 32
- 150000004984 aromatic diamines Chemical class 0.000 claims abstract description 15
- 229920001721 polyimide Polymers 0.000 claims abstract description 13
- 239000000203 mixture Substances 0.000 claims abstract description 12
- 239000004642 Polyimide Substances 0.000 claims abstract description 9
- 125000003118 aryl group Chemical group 0.000 claims abstract description 8
- 150000008065 acid anhydrides Chemical class 0.000 claims abstract description 4
- UDKYPBUWOIPGDY-UHFFFAOYSA-N 3-amino-n-(4-aminophenyl)benzamide Chemical compound C1=CC(N)=CC=C1NC(=O)C1=CC=CC(N)=C1 UDKYPBUWOIPGDY-UHFFFAOYSA-N 0.000 claims abstract 3
- XPAQFJJCWGSXGJ-UHFFFAOYSA-N 4-amino-n-(4-aminophenyl)benzamide Chemical compound C1=CC(N)=CC=C1NC(=O)C1=CC=C(N)C=C1 XPAQFJJCWGSXGJ-UHFFFAOYSA-N 0.000 claims abstract 3
- HLBLWEWZXPIGSM-UHFFFAOYSA-N 4-Aminophenyl ether Chemical compound C1=CC(N)=CC=C1OC1=CC=C(N)C=C1 HLBLWEWZXPIGSM-UHFFFAOYSA-N 0.000 claims abstract 2
- 125000006158 tetracarboxylic acid group Chemical group 0.000 claims description 8
- 150000004985 diamines Chemical class 0.000 claims description 4
- 238000006068 polycondensation reaction Methods 0.000 claims description 4
- 150000004982 aromatic amines Chemical class 0.000 claims description 2
- 239000011888 foil Substances 0.000 abstract description 11
- 229910052751 metal Inorganic materials 0.000 abstract description 8
- 239000002184 metal Substances 0.000 abstract description 8
- 150000000000 tetracarboxylic acids Chemical class 0.000 abstract 2
- VQVIHDPBMFABCQ-UHFFFAOYSA-N 5-(1,3-dioxo-2-benzofuran-5-carbonyl)-2-benzofuran-1,3-dione Chemical compound C1=C2C(=O)OC(=O)C2=CC(C(C=2C=C3C(=O)OC(=O)C3=CC=2)=O)=C1 VQVIHDPBMFABCQ-UHFFFAOYSA-N 0.000 abstract 1
- 229940051881 anilide analgesics and antipyretics Drugs 0.000 abstract 1
- 150000003931 anilides Chemical class 0.000 abstract 1
- 239000002253 acid Substances 0.000 description 20
- 150000001412 amines Chemical class 0.000 description 20
- 238000000034 method Methods 0.000 description 15
- 238000006243 chemical reaction Methods 0.000 description 14
- 239000002904 solvent Substances 0.000 description 7
- YDYSEBSNAKCEQU-UHFFFAOYSA-N 2,3-diamino-n-phenylbenzamide Chemical compound NC1=CC=CC(C(=O)NC=2C=CC=CC=2)=C1N YDYSEBSNAKCEQU-UHFFFAOYSA-N 0.000 description 6
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 6
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 5
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical group CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 5
- 239000000853 adhesive Substances 0.000 description 5
- 230000001070 adhesive effect Effects 0.000 description 5
- 239000011889 copper foil Substances 0.000 description 5
- 239000011248 coating agent Substances 0.000 description 4
- 238000000576 coating method Methods 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 238000005530 etching Methods 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 239000002798 polar solvent Substances 0.000 description 4
- 229920005575 poly(amic acid) Polymers 0.000 description 4
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 3
- GCAIEATUVJFSMC-UHFFFAOYSA-N benzene-1,2,3,4-tetracarboxylic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C(C(O)=O)=C1C(O)=O GCAIEATUVJFSMC-UHFFFAOYSA-N 0.000 description 3
- ZHDTXTDHBRADLM-UHFFFAOYSA-N hydron;2,3,4,5-tetrahydropyridin-6-amine;chloride Chemical compound Cl.NC1=NCCCC1 ZHDTXTDHBRADLM-UHFFFAOYSA-N 0.000 description 3
- 239000012046 mixed solvent Substances 0.000 description 3
- 239000012454 non-polar solvent Substances 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 239000008096 xylene Substances 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 2
- 150000007513 acids Chemical class 0.000 description 2
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 2
- 238000012661 block copolymerization Methods 0.000 description 2
- 238000005266 casting Methods 0.000 description 2
- 238000007334 copolymerization reaction Methods 0.000 description 2
- 229910001873 dinitrogen Inorganic materials 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 125000005462 imide group Chemical group 0.000 description 2
- 239000010410 layer Substances 0.000 description 2
- -1 nitoluene Chemical class 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000006798 ring closing metathesis reaction Methods 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- GQWNECFJGBQMBO-UHFFFAOYSA-N Molindone hydrochloride Chemical compound Cl.O=C1C=2C(CC)=C(C)NC=2CCC1CN1CCOCC1 GQWNECFJGBQMBO-UHFFFAOYSA-N 0.000 description 1
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 1
- 239000012790 adhesive layer Substances 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 150000008064 anhydrides Chemical class 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- SBZXBUIDTXKZTM-UHFFFAOYSA-N diglyme Chemical compound COCCOCCOC SBZXBUIDTXKZTM-UHFFFAOYSA-N 0.000 description 1
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 1
- 238000009499 grossing Methods 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 239000012212 insulator Substances 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 238000000059 patterning Methods 0.000 description 1
- 239000009719 polyimide resin Substances 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- CYIDZMCFTVVTJO-UHFFFAOYSA-N pyromellitic acid Chemical compound OC(=O)C1=CC(C(O)=O)=C(C(O)=O)C=C1C(O)=O CYIDZMCFTVVTJO-UHFFFAOYSA-N 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
- 230000037303 wrinkles Effects 0.000 description 1
Landscapes
- Paints Or Removers (AREA)
- Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
Abstract
Description
【発明の詳細な説明】
（産業上の利用分野）
耐熱性が優れ、寸法安定性に優れた高密度配線用のフレ
キシブルプリント回路基板用の樹脂組成物に関するもの
である。DETAILED DESCRIPTION OF THE INVENTION (Industrial Application Field) The present invention relates to a resin composition for a flexible printed circuit board for high-density wiring, which has excellent heat resistance and excellent dimensional stability.
（従来技術）
従来、フレキシブルプリント回路基板は、ポリイミドフ
ィルムと金属箔とを、接着剤で貼合わせて製造されてい
た。(Prior Art) Conventionally, flexible printed circuit boards have been manufactured by bonding a polyimide film and metal foil together with an adhesive.
ところが、接着剤はもともと耐熱性に劣るため、基板と
して耐熱性の良いポリイミドフィルム本来の耐熱性を発
揮させることが出来なかった。また、接着剤の高温時で
の寸法変化が大きいので、基板のカール、ネジレ、反り
などが発生し、その後のバターニング等の作業が困難で
あった。さらに、耐熱性が必要とされるフレキシブルプ
リント回路基板としては、金属箔上に直接ポリアミック
酸溶液を流延塗布し、加熱硬化させて接着剤層のないフ
レキシブルプリント回路基板を製造する方法が試みられ
ているが、これらはいずれも接着性の低いものしか得ら
れず、しかも寸法精度に優れ、良好な機械特性を満足す
るフレキシブルプリント回路基板は得られていないのが
現状である。However, since the adhesive originally has poor heat resistance, it has not been possible to utilize the inherent heat resistance of polyimide film, which has good heat resistance, as a substrate. Further, since the adhesive undergoes large dimensional changes at high temperatures, the substrate may curl, twist, warp, etc., making subsequent operations such as patterning difficult. Furthermore, for flexible printed circuit boards that require heat resistance, attempts have been made to manufacture flexible printed circuit boards without an adhesive layer by directly casting a polyamic acid solution onto metal foil and curing it with heat. However, with these methods, only products with low adhesiveness can be obtained, and at present, flexible printed circuit boards with excellent dimensional accuracy and satisfactory mechanical properties have not been obtained.
（発明が解決しようとする課ＩＩ）
本発明は、耐熱性が優れ、寸法安定性が優れしかも機械
特性の優れたフレキシブルプリント回路基板を工業的に
得ようとして、研究した結果得られたものである。(Problem II to be Solved by the Invention) The present invention was obtained as a result of research aimed at industrially obtaining a flexible printed circuit board with excellent heat resistance, excellent dimensional stability, and excellent mechanical properties. be.
すなわち芳香族ジアミン成分としである特定の剛直な成
分を使用することによって、ポリ−Ｎ、 Ｎ−ビスフエ
ノキシフェニルーピロメリットイミド構造を持ち耐熱性
や金属箔に対する優れた接着性を有し、しかも他の優れ
た特性を損なうことなく、熱安定性を有するフレキシブ
ルプリント回路基板ができることを見出し、本発明に到
達したものである。In other words, by using a specific rigid component as the aromatic diamine component, it has a poly-N, N-bisphenoxyphenylpyromellitimide structure and has excellent heat resistance and adhesion to metal foil. Furthermore, the present inventors have discovered that a flexible printed circuit board having thermal stability can be produced without impairing other excellent properties, and have thus arrived at the present invention.
（課題を解決するための手段）
３一
本発明は、芳香族テトラカルボン酸二無水物と芳香族ジ
アミンとの重縮合反応によって得られるポリイミドを基
材とするフレキシブル回路板において、絶縁体であるポ
リイミド層が、酸無水物として芳香族テトラカルボン酸
二無水物（Ａ）の中から選ばれた１種または２種類以上
の芳香族テトラカルボン酸二無水物と芳香族ジアミン（
Ｂ）として４．４１−ジアミノベンズアニリド（ＤＡＢ
ＡＮ）、および／または３．４１−ジアミノベンズアニ
リド（Ｄ Ａ Ｂ Ａ Ｎ）と４．４１−ジアミノジフ
ェニルエーテル（ＤＤＥ）の混合物からなり、かつ４．
４−ジアミノベンズアニリドおよび／または３，４１−
ジアミノベンズアニリドが、芳香族アミン成分の２０〜
８０モル％からなる芳香族ジアミンからなるポリイミド
樹脂組成物を用いることを特徴とするフレキシブルプリ
ント回路基板である。(Means for Solving the Problems) 31 The present invention provides a flexible circuit board based on polyimide obtained by a polycondensation reaction of an aromatic tetracarboxylic dianhydride and an aromatic diamine, which is an insulator. The polyimide layer contains one or more aromatic tetracarboxylic dianhydrides selected from aromatic tetracarboxylic dianhydrides (A) as acid anhydrides and aromatic diamine (
B) as 4,41-diaminobenzanilide (DAB
AN), and/or a mixture of 3,41-diaminobenzanilide (DABAN) and 4,41-diaminodiphenyl ether (DDE), and 4.
4-diaminobenzanilide and/or 3,41-
Diaminobenzanilide is an aromatic amine component of 20~
This is a flexible printed circuit board characterized by using a polyimide resin composition comprising 80 mol% of aromatic diamine.
（作用）
本発明で使用する芳香族テトラカルボン酸二無水物は、
１．２．４．５−ベンゼンテトラカルボン酸二無水物、
３．３″、４．４−ビフェニルテトラカルボン酸二無水
物、３．３，４．４一ペンゾフェノンテトラヵルボン酸
二無水物、ジフェニルスルホン−３，３４，４−テトラ
カルボン酸二無水物および３．３″、４．４−ジフエニ
ルエーテルテトラカルポン酸二無水物などであり、これ
らのＩ種または２種類以上の混合物を用いることができ
る。中でも１．２．４．５−ベンゼンテトラカルボン酸
二無水物は、剛直な成分として作用し、３．３．４．４
−ビフェニルテトラカルボン酸二無水物と３．３″、４
．４〜ジフェニルエーテルテトラカルポン酸二無水物は
屈曲性に富む成分として作用する。本発明の口的におい
ては、３．３°、４．４°ーベンゾフェノンテトラカル
ポン酸二無水物か、あるいは１．２．４．５−ベンゼン
テトラカルボン酸二無水物と３．３．４．４−ビフェニ
ルテトラカルボン酸二無水物の２種類の酸無水物を併用
して使用することが好ましい。本発明で芳香族ジアミン
成分として使用するジアミンは、分子内に屈曲性に富む
エーテル結合を持つ４．４１−ジアミノジフェニルエー
テルと剛直な結合を有するジアミノベンズアニリドの２
または３種類のジアミンの混合物である。(Action) The aromatic tetracarboxylic dianhydride used in the present invention is
1.2.4.5-benzenetetracarboxylic dianhydride,
3.3″, 4.4-biphenyltetracarboxylic dianhydride, 3.3,4.4-penzophenonetetracarboxylic dianhydride, diphenylsulfone-3,34,4-tetracarboxylic dianhydride and 3.3'', 4,4-diphenyl ether tetracarboxylic dianhydride, and these I types or a mixture of two or more types can be used. Among them, 1.2.4.5-benzenetetracarboxylic dianhydride acts as a rigid component, and 3.3.4.4
- biphenyltetracarboxylic dianhydride and 3.3″, 4
．． 4-Diphenyl ether tetracarboxylic dianhydride acts as a component with high flexibility. In the present invention, 3.3°, 4.4°-benzophenonetetracarboxylic dianhydride or 1.2.4.5-benzenetetracarboxylic dianhydride and 3.3.4 It is preferable to use two types of acid anhydrides, 4-biphenyltetracarboxylic dianhydride, in combination. The diamines used as the aromatic diamine component in the present invention are 4,41-diaminodiphenyl ether, which has a highly flexible ether bond in the molecule, and diaminobenzanilide, which has a rigid bond.
Or a mixture of three types of diamines.
ジアミン成分の構成比は、ジアミノベンズアニリドが芳
香族ジアミンの２０〜８０モル％の範囲が好ましい。The composition ratio of the diamine component is preferably in the range of 20 to 80 mol% of diaminobenzanilide based on the aromatic diamine.
ジアミノベンズアニリドが、２０モル％以下では、剛直
な分子構造を導入する効果が発現しないため寸法安定性
が悪くなる。If the amount of diaminobenzanilide is less than 20 mol %, the effect of introducing a rigid molecular structure will not be exhibited, resulting in poor dimensional stability.
また、ジアミノベンズアニリドの添加量の上限はジアミ
ノベンズアニリドが１００モル％では剛直すぎて密着が
悪くなり、実用的に好ましくなくジアミノベンズアニリ
ドの添加量は、８０モル％以下が好ましい。Further, the upper limit of the amount of diaminobenzanilide added is 100 mol%, which is too rigid and poor adhesion, which is not practical, and the amount of diaminobenzanilide added is preferably 80 mol% or less.
芳香族テトラカルボン酸二無水物（Ａ）と芳香族ジアミ
ンＣＢ）との反応は、非プロトン性極性溶媒中で行われ
る。The reaction between the aromatic tetracarboxylic dianhydride (A) and the aromatic diamine CB) is carried out in an aprotic polar solvent.
非プロトン性極性溶媒は、叱ドジメチルホルムアミド（
ＤＭＦ）、Ｎ、Ｎ−ジメチルアセトアミド（ＤＭＡｃ）
、Ｎ−メチル−２−ピロリドン（ＮＭＰ）、テト
ラヒド口フラン（ＩＨＦ）、ジグライムなどである。The aprotic polar solvent is dimethylformamide (
DMF), N,N-dimethylacetamide (DMAc)
, N-methyl-2-pyrrolidone (NMP), Tet
These include rahidofuran (IHF) and diglyme.
非プロトン性極性溶媒は、１種類のみ用いてもよいし、
２種類以上を混合して用いてもよい。Only one type of aprotic polar solvent may be used,
A mixture of two or more types may be used.
この時、上記非プロトン性極性溶媒と相溶性がある非極
性溶媒を混合して使用してもよい。At this time, a non-polar solvent that is compatible with the aprotic polar solvent may be used in combination.
特ニトルエン、キシレン、ソルベントナフサなどの芳香
族炭化水素は、塗膜表面を平滑に仕上げる目的で良く使
用される。In particular, aromatic hydrocarbons such as nitoluene, xylene, and solvent naphtha are often used for the purpose of smoothing the surface of the coating film.
混合溶媒における非極性溶媒の割合は、３０重量％以下
であることが好ましい。これは非極性溶媒が３０重量％
以上では溶媒の溶解力が低下しポリアミック酸が析出す
るためである。The proportion of the nonpolar solvent in the mixed solvent is preferably 30% by weight or less. This is 30% by weight of non-polar solvent.
This is because the solvent's dissolving power decreases and polyamic acid precipitates.
本発明においてもっとも好ましい溶媒は、ＮＭＰと比較
的沸点の高い芳香族炭化水素との組み合わせである。The most preferred solvent in the present invention is a combination of NMP and an aromatic hydrocarbon having a relatively high boiling point.
ポリイミドの重縮合反応は、一般に良く乾燥した芳香族
ジアミン成分（Ｂ）を脱水精製した溶媒に溶解し、これ
に閉環率９８％、より好ましくは９９％以上の良く乾燥
した芳香族テトラカルボン酸二無水物（Ａ）を添加して
反応を進める。２種類以上のアミンや酸を反応させると
き、その添加の順や量比が問題になる。The polycondensation reaction of polyimide is generally carried out by dissolving a well-dried aromatic diamine component (B) in a dehydrated and purified solvent, and adding a well-dried aromatic tetracarboxylic acid diamine with a ring closure rate of 98%, more preferably 99% or more. The anhydride (A) is added to advance the reaction. When two or more types of amines or acids are reacted, the order of addition and quantitative ratio become issues.
ポリイミドの重縮合反応は（イ）全アミン成分フー
を先に溶媒に溶解し、その後酸成分を添加し反応させる
ランダム共重合的な方法と、（ロ）特定の一種類のアミ
ンと酸をまず反応させてアミン末端または酸末端のポリ
マとし、しかる後にこの末端を成長させ、残りのアミン
成分と酸成分を添加して重合を完結させるブロック共重
合的な方法がある。The polycondensation reaction of polyimide involves two methods: (a) a random copolymerization method in which all the amine components are first dissolved in a solvent, and then an acid component is added and reacted; and (b) a method in which one specific type of amine and an acid are first dissolved. There is a block copolymerization method in which the polymer is reacted to form an amine-terminated or acid-terminated polymer, and then this terminus is grown, and the remaining amine component and acid component are added to complete the polymerization.
本発明においては、ランダム共重合的な方法、あるいは
ブロック共重合的な方法のどちらでも充分目的に叶う特
性の優れたフレキシブル回路用組成物を得ることができ
る。したがって本発明では、（イ）、（ロ）のどちらの
重合方法も採用することができる。ただし、２種類以上
の酸、アミンをそれぞれ別に反応させて得られたポリア
ミック酸を化学反応を伴わずに単純な混合だけでしよう
することは、樹脂組成物の線膨張係数のばらつきが出や
すくなり好ましくない。本発明で使用される金属箔は、
一般に銅箔が用いられるが、アルミ箔、ニッケル箔、ス
テンレス箔、タングステン箔なども用いることができる
。In the present invention, a composition for flexible circuits having excellent properties that satisfies the purpose can be obtained by either a random copolymerization method or a block copolymerization method. Therefore, in the present invention, either of the polymerization methods (a) and (b) can be employed. However, if polyamic acids obtained by reacting two or more types of acids and amines are simply mixed together without any chemical reaction, the linear expansion coefficient of the resin composition will likely vary. Undesirable. The metal foil used in the present invention is
Copper foil is generally used, but aluminum foil, nickel foil, stainless steel foil, tungsten foil, etc. can also be used.
金属箔は３〜２００μの厚さのものが使用され、表面は
粗面化悠理を施されているものが好ましい。The metal foil used has a thickness of 3 to 200 microns, and preferably has a roughened surface.
ポリイミドの溶液を金属箔に塗布する方法は、ロータリ
ーコーター、ナイフコーター、ドクターブレード、フロ
ーコーター等の公知の塗布手段で３０〜１０００ｐの均
一な厚さに流延塗布する方法がとられる。The polyimide solution is applied to the metal foil by casting to a uniform thickness of 30 to 1000 p using a known coating means such as a rotary coater, knife coater, doctor blade, or flow coater.
次いで加熱によりポリアミック酸溶液の溶媒を除去し、
かつイミド環の形成を行うが、１００℃から３５０℃ま
で０．５時間未満だと膜厚にもよるが、脱溶媒が不十分
であったり、イミドの閉環が不十分で特性が十分に発揮
されないことがある。また例えば、■００℃で３０分、
ついで１５０℃で３０分、２００℃で３０分、２５０℃
で３０分、３００℃で３０分、３５０℃で２０分という
具合に段階的に昇温してもよい。加熱雰囲気も空気中で
さしつかえない場合もあるが減圧下ないしは不活性ガス
を流しながら非酸化性状態下に行う方が好ましい。この
様にして形成されたポリイミド皮膜層は一般的に５〜２
００μである。Next, the solvent of the polyamic acid solution is removed by heating,
In addition, an imide ring is formed, but if the temperature is raised from 100°C to 350°C for less than 0.5 hours, depending on the film thickness, solvent removal may be insufficient or imide ring closure may be insufficient, resulting in insufficient performance. It may not be done. For example, ■ 30 minutes at 00℃,
Then 30 minutes at 150℃, 30 minutes at 200℃, 250℃
The temperature may be increased stepwise such as 30 minutes at 300°C, 30 minutes at 350°C, and so on. Although the heating atmosphere may be in air in some cases, it is preferable to conduct the heating under reduced pressure or under non-oxidizing conditions while flowing an inert gas. The polyimide film layer formed in this way generally has 5 to 2
It is 00μ.
（実施例１）
温度計、撹拌装置、環流コンデンサーおよび乾燥窒素ガ
ス吹き込み口を備えた４つロセパラブルフラスコに精製
した無水の４．４″−ジアミノベンズアニリド１２５．
０ｇ （アミン成分の５５モル％）をとり、これに無水
のトメチルー２−ピロリドン８０重量％とキシレン２０
重量％の混合溶剤を、全仕込み原料中の固形分割合が１
５重量％になるだけの量を加え、窒素ガスを流しながら
溶解した。(Example 1) Purified anhydrous 4.4"-diaminobenzanilide 125.
Take 0g (55 mol% of the amine component) and add 80% by weight of anhydrous tomethyl-2-pyrrolidone and 20% xylene.
% by weight of the mixed solvent, the solid content of the total raw materials is 1.
An amount of 5% by weight was added and dissolved while nitrogen gas was flowing.
次いで精製した１、２，４．５−ベンゼンテトラカルボ
ン酸二無水物１１８Ｊｇ （酸成分の５５モル％）を撹
拌しながら少量ずつ添加するが発熱反応であるため、外
部水槽に約１５℃の冷水を循環させてこれを冷却した。Next, 118 Jg of purified 1,2,4.5-benzenetetracarboxylic dianhydride (55 mol% of the acid component) is added little by little while stirring, but since it is an exothermic reaction, cold water at about 15°C is placed in an external water tank. was cooled by circulation.
− 添加後、内部温度を２０℃に設定し、５時間反応した。− After the addition, the internal temperature was set at 20°C and the reaction was carried out for 5 hours.
次に精製した無水の４．４１−ジアミノジフエニルエー
テル９Ｌ１ｇ（アミン成分の４５モル％）を撹拌しなが
ら少量ずつ添加し、更に統いて、精製した１、２．４．
５−ベンゼンテトラカルボン酸二無水物９７．１ｇ（酸
成分の４５モル％）を撹拌しながら少量ずつ添加した。Next, 1 g of purified anhydrous 4.41-diaminodiphenyl ether (9L 1 g (45 mol% of the amine component)) was added little by little with stirring, and the mixture was further mixed.
97.1 g (45 mol % of the acid component) of 5-benzenetetracarboxylic dianhydride was added little by little with stirring.
添加後、内部温度を２０℃に設定し、５時間撹拌し、反
応を終了した。After the addition, the internal temperature was set at 20° C. and stirred for 5 hours to complete the reaction.
反応における酸／アミン（モル比）は１．０１であり、
トメチルー２−ピロリドン中０．５重量％溶液の固有粘
度は（ＬＨｌ（ａｔ ３０℃）であった。The acid/amine (molar ratio) in the reaction is 1.01,
The intrinsic viscosity of a 0.5% by weight solution in tomethyl-2-pyrrolidone was (LHl at 30°C).
このポリイミド溶液を銅箔上に流延塗布した後乾燥器に
入れ１００℃から３５０℃まで連続的に２時間かけて昇
温した。This polyimide solution was cast onto a copper foil, then placed in a dryer and heated continuously from 100°C to 350°C over 2 hours.
この様にして製造されたフレキシブルプリント回路用基
板は、寸法変化率が０．１３％で、エッチング後のフィ
ルムの引っ張り強度は２５Ｋｇ／■−と優れたフレキシ
ブル回路板であった。The flexible printed circuit board manufactured in this manner had a dimensional change rate of 0.13% and a tensile strength of the film after etching of 25 kg/■-, which was an excellent flexible circuit board.
（実施例２）
実施例１と同様な装置および方法で、３．４２−ジアミ
ノベンズアニリド１７（Ｌ４ｇ （アミン成分の７５モ
ル％）と１．２．４．５−ベンゼンテトラカルボン酸二
無水物１５２４ｇ （酸成分の７５モル％）を２０℃で
５時間反応させた。(Example 2) Using the same apparatus and method as in Example 1, 3.42-diaminobenzanilide 17 (L4 g (75 mol% of the amine component)) and 1.2.4.5-benzenetetracarboxylic dianhydride were prepared. 1524 g (75 mol % of the acid component) was reacted at 20° C. for 5 hours.
次いで、４．４−ジアミノジフェニルエーテル５０．１
ｇ（アミン成分の２５モル％）と１．２．４．５−ベン
ゼンテトラカルボン酸二無水物５（Ｌ７ｇ （酸成分の
２５モル％）を添加し２０℃で５時間反応させた。反応
における酸／アミン（モル比）は０．９３である。また
生成物の固有粘度は０．９０であった。Then 4,4-diaminodiphenyl ether 50.1
g (25 mol% of the amine component) and 1.2.4.5-benzenetetracarboxylic dianhydride 5 (L7g (25 mol% of the acid component) were added and reacted at 20°C for 5 hours. The acid/amine (molar ratio) was 0.93.The intrinsic viscosity of the product was 0.90.
このポリアミフク酸溶液を銅箔上に流延塗布した後乾燥
器に入れ、１００℃で３０分間、１５０℃で３０分間、
２００℃で３０分間、２５０℃で２０分間、３００℃で
ｌＯ分間それぞれ加熱した後、９０メの円筒に巻き付け
、３００℃から３５０℃まで連続的ｌこ１時間かけてＪ
ｌ温し、アニールした。This polyamifucic acid solution was cast onto copper foil, placed in a dryer, heated to 100°C for 30 minutes, and heated to 150°C for 30 minutes.
After heating at 200°C for 30 minutes, 250°C for 20 minutes, and 300°C for 10 minutes, it was wrapped around a 90mm cylinder and heated continuously from 300°C to 350°C for 1 hour.
The sample was heated to 100 mL and annealed.
この様にして製造されたフレキシブルプリント回路用基
板は、寸法変化率が０．０９％で、エッチング後のフィ
ルムの引っ張り強度は３２Ｋｇ／ａｍ”と優れた回路板
であった。The flexible printed circuit board manufactured in this way had a dimensional change rate of 0.09%, and the tensile strength of the film after etching was 32 Kg/am'', making it an excellent circuit board.
（実施例３）
実施例１と同様な装置で、４．４°−ジアミノベンズア
ニリド９０４ｇ （アミン成分の４０モル％）と３．４
′−ジアミノベンズアニリド７９−５ｇ （アミン成分
の３５モル％）と４．４１−ジアミノジフエニルニーテ
ル５Ｌ１ｇ （アミン虞分の２５モル％）をとり、これ
に無水のＮ−メチル−２−ピσリドン８０重量％とキシ
レン２０重量％の混合溶剤を、全仕込み原料中の固形分
割合が１５重量％になるだけの量を加え、窒素ガスを流
しながら溶解した。次いで、精製した１、２．４．５−
ベンゼンテトラカルボン酸二無水物１７１．８ｇ （酸
成分の７５モル％）と３．３．４．４″−ビフェニルテ
トラカルボン酸二無水物７フー２ｇ （酸成分の２５モ
ル％）を添加し、２０℃で５時間反応させた。(Example 3) In the same apparatus as in Example 1, 904 g of 4.4°-diaminobenzanilide (40 mol% of the amine component) and 3.4°
79-5 g of '-diaminobenzanilide (35 mol % of the amine component) and 1 g of 4.41-diaminodiphenylniter (25 mol % of the amine component) are added to A mixed solvent of 80% by weight of σ lidone and 20% by weight of xylene was added in an amount sufficient to make the solid content ratio in the total raw materials 15% by weight, and dissolved while flowing nitrogen gas. Then purified 1,2.4.5-
171.8 g of benzenetetracarboxylic dianhydride (75 mol % of the acid component) and 2 g of 3.3.4.4''-biphenyltetracarboxylic dianhydride (25 mol % of the acid component) were added, The reaction was carried out at 20°C for 5 hours.
反応における酸／アミン（モル比）は１．０５である。The acid/amine (molar ratio) in the reaction is 1.05.
生成物の固有粘度は０．８５であった。The product had an intrinsic viscosity of 0.85.
実施例１と同様な方法でフレキシブル回路用基板を作成
したが、寸法変化率が０．１７％であり、エッチング後
のフィルムの引張り強度は２７ｋｇ／ｗ″と優れた回路
板であった。A flexible circuit board was produced in the same manner as in Example 1, and the dimensional change rate was 0.17%, and the tensile strength of the film after etching was 27 kg/w'', making it an excellent circuit board.
（実施例４）
実施例１と同様な装置および方法て、１．２．４．５−
ベンゼンテトラカルボン酸二無水物にかえてジフェニル
ホン−３，３″４．４′−テトラカルボン酸二無水物を
用いて検討した。反応後、実施例１と同様な方１３一
法でフレキシブル回路用基板を作成したところ、寸法変
化率が０．１５％であり、エッチング後のフィルムの引
張り強度は３０ｋｇ／■■８と優れた回路板であった。(Example 4) Using the same apparatus and method as in Example 1, 1.2.4.5-
An investigation was conducted using diphenylphone-3,3''4,4'-tetracarboxylic dianhydride instead of benzenetetracarboxylic dianhydride. After the reaction, a flexible circuit was prepared using the same method as in Example 1. When a circuit board was prepared, the dimensional change rate was 0.15%, and the tensile strength of the film after etching was 30 kg/■■8, making it an excellent circuit board.
（比較例１）
実施例１と同様な装置および方法で、４．４”−ジアミ
ノベンズアニリド２２．７ｇ （アミン成分のｌＯモル
％）と１．２．４．５−ベンゼンテトラカルボン酸二無
水物２０４ｇ （酸成分のｌＯモル％）を２０℃で５時
間反応させた。(Comparative Example 1) Using the same apparatus and method as in Example 1, 22.7 g of 4.4"-diaminobenzanilide (lO mol% of the amine component) and 1.2.4.5-benzenetetracarboxylic dianhydride were prepared. 204 g (lO mol% of acid component) were reacted at 20° C. for 5 hours.
次いで、４．４−ジアミノジフェニルエーテル１８０゜
２ｇ （アミン成分の９０モル％）と１．２．４．５−
ベンゼンテトラカルボン酸二無水物１８２．６ｇ （酸
成分の９０モル％）を添加し２０℃で５時間反応させた
。反応における酸／アミン（モル比）は０．９３である
。Next, 180°2 g of 4.4-diaminodiphenyl ether (90 mol% of the amine component) and 1.2.4.5-
182.6 g of benzenetetracarboxylic dianhydride (90 mol % of the acid component) was added and reacted at 20° C. for 5 hours. The acid/amine (molar ratio) in the reaction is 0.93.
実施例１と同様な方法でフレキシブル回路用基板を作成
したが、寸法変化率が−４，６％でありカールが激しく
回路用基板としては不適当であった。A flexible circuit board was prepared in the same manner as in Example 1, but the dimensional change rate was -4.6% and curling was severe, making it unsuitable as a circuit board.
（比較例２）
実施例１と同様な装置および方法で、４．４−ジアミノ
ベンズアニリド２０４．５ｇ （アミン成分の９０モル
％）と３．３．４．４−ビフェニルテトラカルポン酸二
無水物２４６．３ｇ （酸虞分の９０モル％）を２０℃
で５時間反応させた。(Comparative Example 2) Using the same apparatus and method as in Example 1, 204.5 g of 4.4-diaminobenzanilide (90 mol% of the amine component) and 3.3.4.4-biphenyltetracarboxylic dianhydride were added. 246.3g (90 mol% of acid content) at 20℃
The reaction was carried out for 5 hours.
次いで、４．４−ジアミノジフェニルエーテル２０．０
ｇ（アミン成分の１０モル％）と１．２．４．５−ベン
ゼンテトラカルボン酸二無水物２０−３ｇ （酸成分の
ｌθモル％）は０−９３である。Then 4,4-diaminodiphenyl ether 20.0
g (10 mol % of the amine component) and 20-3 g of 1.2.4.5-benzenetetracarboxylic dianhydride (lθ mol % of the acid component) are 0-93.
実施例１と同様な方法でフレキシブル回路用基板を作成
したが、塗膜がもろく、また柔軟性に乏しいため銅箔と
の密着性が悪く接着強度が０．３５１［ｇ／＋＋ｎ”
しかなく、回路用基板としては不適当であった。A flexible circuit board was prepared in the same manner as in Example 1, but the coating film was brittle and had poor flexibility, resulting in poor adhesion to the copper foil and an adhesive strength of 0.351 [g/++n''.
Therefore, it was unsuitable for use as a circuit board.
（比較例３）
実施例１と同様な装置および方法で、４．４１−ジアミ
ノベンズアニリド２２７．３ｇと３．３．４．４”−ビ
フェニルテトラカルボン酸二無水物２９Ｌ３ｇを２０℃
で５時間反応させた。(Comparative Example 3) Using the same apparatus and method as in Example 1, 227.3 g of 4.41-diaminobenzanilide and 29 L3 g of 3.3.4.4''-biphenyltetracarboxylic dianhydride were heated at 20°C.
The reaction was carried out for 5 hours.
実施例１と同様な方法でフレキシブル回路用基板を作成
したが、塗膜がかたく柔軟性に乏しいため銅箔との密着
性が悪く接着強度が０．２８Ｋｇ／龍：しがなく、回路
用基板としては不適当であった。A flexible circuit board was made in the same manner as in Example 1, but the coating was hard and inflexible, resulting in poor adhesion to the copper foil and adhesive strength of 0.28 kg/Ryu: Shigainaru, circuit board. It was inappropriate as such.
（比較例４）
実施例１と同様な装置および方法で、４，４−ジアミノ
ジフェニルエーテル５０４ｇと１．２．４．５−ベンゼ
ンテトラカルボン酸二無水物５４−Ｏｇを添加し２０℃
で５時間反応させた。実施例１と同様な方法でフレキシ
ブル回路用基板を作成したが、寸法変化率が高く、カー
ルやシワが激しく、回路用基板としては不適当であった
。(Comparative Example 4) Using the same apparatus and method as in Example 1, 504 g of 4,4-diaminodiphenyl ether and 54-Og of 1.2.4.5-benzenetetracarboxylic dianhydride were added and heated at 20°C.
The reaction was carried out for 5 hours. Although a flexible circuit board was produced in the same manner as in Example 1, the dimensional change rate was high and curls and wrinkles were severe, making it unsuitable as a circuit board.
（発明の効果）
本発明によれば、優れた耐熱性と金属箔と樹脂との密着
性の良いフレキシブル回路基板用組成物を得ることがで
きる。すなわち、ポリ−Ｎ％Ｎ′−ビスフェノキシフェ
ニル−ビロメリットイミドに剛直な芳香族ジアミンとし
てジアミノベンズアニリドを配することにより、耐熱性
を始めとする優れた性質と、高密着とを両立させること
ができる。(Effects of the Invention) According to the present invention, it is possible to obtain a composition for a flexible circuit board that has excellent heat resistance and good adhesion between metal foil and resin. That is, by disposing diaminobenzanilide as a rigid aromatic diamine in poly-N%N'-bisphenoxyphenyl-biromellitimide, it is possible to achieve both excellent properties such as heat resistance and high adhesion. Can be done.
Claims (1)
ミンとの重縮合反応によって得られるフレキシブルプリ
ント回路基板用の樹脂組成物において、 （Ａ） 酸無水物として芳香族テトラカルボン酸二無水
物の中から選ばれた１種または２種以上の混合物から成
る芳香族テトラカルボン酸二無水物と、 （Ｂ） ジアミンとして４，４’−ジアミノベンズアニ
リドおよび／または３，４’−ジアミノベンズアニリド
と４，４’−ジアミノジフェニルエーテルの混合物から
なる芳香族ジアミンであり、かつ４，４’−ジアミノベ
ンズアニリドおよび／または３，４’−ジアミノベンズ
アニリドが、芳香族アミン成分の２０〜８０モル％から
なる芳香族ジアミンとを反応させてなるポリイミドであ
ることを特徴とするフレキシブルプリント回路基板用の
樹脂組成物。(1) In a resin composition for a flexible printed circuit board obtained by a polycondensation reaction of an aromatic tetracarboxylic dianhydride and an aromatic diamine, (A) an aromatic tetracarboxylic dianhydride as the acid anhydride; An aromatic tetracarboxylic dianhydride consisting of one type or a mixture of two or more selected from the above, and (B) 4,4'-diaminobenzanilide and/or 3,4'-diaminobenzanilide as a diamine. An aromatic diamine consisting of a mixture of 4,4'-diaminodiphenyl ether, and 4,4'-diaminobenzanilide and/or 3,4'-diaminobenzanilide constitutes 20 to 80 mol% of the aromatic amine component. A resin composition for a flexible printed circuit board, characterized in that it is a polyimide obtained by reacting with an aromatic diamine.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP28751489A JPH03149227A (en) | 1989-11-06 | 1989-11-06 | Resin composition |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP28751489A JPH03149227A (en) | 1989-11-06 | 1989-11-06 | Resin composition |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH03149227A true JPH03149227A (en) | 1991-06-25 |
Family
ID=17718327
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP28751489A Pending JPH03149227A (en) | 1989-11-06 | 1989-11-06 | Resin composition |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH03149227A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2012043186A1 (en) * | 2010-09-28 | 2012-04-05 | 東レ株式会社 | Resin composition and manufacturing process therefor |
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|---|---|---|---|---|
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| GB1391502A (en) * | 1971-06-30 | 1975-04-23 | Westinghouse Electric Corp | Heavy gauge resinous films |
| JPS6119634A (en) * | 1984-07-06 | 1986-01-28 | Japan Synthetic Rubber Co Ltd | Production of organic solvent-soluble polyimide compound |
| JPS6128526A (en) * | 1984-07-20 | 1986-02-08 | Japan Synthetic Rubber Co Ltd | Production of organic solvent-soluble polyimide compound |
| JPS6151033A (en) * | 1984-08-18 | 1986-03-13 | Japan Synthetic Rubber Co Ltd | Production of organic solvent-soluble polyimide compound |
| JPS61162526A (en) * | 1985-01-11 | 1986-07-23 | Idemitsu Kosan Co Ltd | Novel polyamide-imide resin and production thereof |
| JPS6281421A (en) * | 1985-10-07 | 1987-04-14 | Idemitsu Kosan Co Ltd | Novel block copolymer and its production |
| JPS6296561A (en) * | 1985-10-24 | 1987-05-06 | Idemitsu Kosan Co Ltd | Resin composition and production thereof |
| JPS62280224A (en) * | 1986-05-28 | 1987-12-05 | Toray Ind Inc | Polyamide-imide film |
| JPS6384188A (en) * | 1986-09-29 | 1988-04-14 | 新日鐵化学株式会社 | Manufacture of flexible printed circuit substrate |
| JPS63239998A (en) * | 1987-03-27 | 1988-10-05 | 新日鐵化学株式会社 | Manufacture of wiring material |
| JPS63245988A (en) * | 1986-11-20 | 1988-10-13 | 新日鐵化学株式会社 | Flexible printed circuit and manufacture of the same |
| JPH0280241A (en) * | 1988-09-16 | 1990-03-20 | Sumitomo Electric Ind Ltd | Flexible wiring base |
| JPH02219641A (en) * | 1989-02-20 | 1990-09-03 | Sumitomo Electric Ind Ltd | Flexible wiring board |
-
1989
- 1989-11-06 JP JP28751489A patent/JPH03149227A/en active Pending
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| US3580737A (en) * | 1968-01-18 | 1971-05-25 | Westinghouse Electric Corp | Chemical radiusing conductor edges of flat cable |
| GB1391502A (en) * | 1971-06-30 | 1975-04-23 | Westinghouse Electric Corp | Heavy gauge resinous films |
| JPS6119634A (en) * | 1984-07-06 | 1986-01-28 | Japan Synthetic Rubber Co Ltd | Production of organic solvent-soluble polyimide compound |
| JPS6128526A (en) * | 1984-07-20 | 1986-02-08 | Japan Synthetic Rubber Co Ltd | Production of organic solvent-soluble polyimide compound |
| JPS6151033A (en) * | 1984-08-18 | 1986-03-13 | Japan Synthetic Rubber Co Ltd | Production of organic solvent-soluble polyimide compound |
| JPS61162526A (en) * | 1985-01-11 | 1986-07-23 | Idemitsu Kosan Co Ltd | Novel polyamide-imide resin and production thereof |
| JPS6281421A (en) * | 1985-10-07 | 1987-04-14 | Idemitsu Kosan Co Ltd | Novel block copolymer and its production |
| JPS6296561A (en) * | 1985-10-24 | 1987-05-06 | Idemitsu Kosan Co Ltd | Resin composition and production thereof |
| JPS62280224A (en) * | 1986-05-28 | 1987-12-05 | Toray Ind Inc | Polyamide-imide film |
| JPS6384188A (en) * | 1986-09-29 | 1988-04-14 | 新日鐵化学株式会社 | Manufacture of flexible printed circuit substrate |
| JPS63245988A (en) * | 1986-11-20 | 1988-10-13 | 新日鐵化学株式会社 | Flexible printed circuit and manufacture of the same |
| JPS63239998A (en) * | 1987-03-27 | 1988-10-05 | 新日鐵化学株式会社 | Manufacture of wiring material |
| JPH0280241A (en) * | 1988-09-16 | 1990-03-20 | Sumitomo Electric Ind Ltd | Flexible wiring base |
| JPH02219641A (en) * | 1989-02-20 | 1990-09-03 | Sumitomo Electric Ind Ltd | Flexible wiring board |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2012043186A1 (en) * | 2010-09-28 | 2012-04-05 | 東レ株式会社 | Resin composition and manufacturing process therefor |
| CN103119085A (en) * | 2010-09-28 | 2013-05-22 | 东丽株式会社 | Resin composition and manufacturing process therefor |
| JP5747822B2 (en) * | 2010-09-28 | 2015-07-15 | 東レ株式会社 | Resin composition and method for producing the same |
| CN103119085B (en) * | 2010-09-28 | 2015-08-26 | 东丽株式会社 | Resin combination and manufacture method thereof |
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