JPH02198837A - Preparation of circuit base board - Google Patents
Preparation of circuit base boardInfo
- Publication number
- JPH02198837A JPH02198837A JP1623589A JP1623589A JPH02198837A JP H02198837 A JPH02198837 A JP H02198837A JP 1623589 A JP1623589 A JP 1623589A JP 1623589 A JP1623589 A JP 1623589A JP H02198837 A JPH02198837 A JP H02198837A
- Authority
- JP
- Japan
- Prior art keywords
- polyimide resin
- diamine
- film
- circuit base
- arom
- 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.)
- Granted
Links
- 229920001721 polyimide Polymers 0.000 claims abstract description 42
- 239000009719 polyimide resin Substances 0.000 claims abstract description 30
- 229910052751 metal Inorganic materials 0.000 claims abstract description 26
- 239000002184 metal Substances 0.000 claims abstract description 26
- 150000004985 diamines Chemical class 0.000 claims abstract description 9
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 claims abstract description 5
- 150000008064 anhydrides Chemical class 0.000 claims abstract description 4
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims abstract description 4
- 238000004519 manufacturing process Methods 0.000 claims description 9
- -1 aromatic tetracarboxylic acid Chemical class 0.000 claims description 8
- 238000000034 method Methods 0.000 claims description 6
- 150000004984 aromatic diamines Chemical class 0.000 claims description 4
- 125000005907 alkyl ester group Chemical group 0.000 claims description 3
- 239000000126 substance Substances 0.000 claims 2
- 239000011888 foil Substances 0.000 abstract description 13
- 230000001070 adhesive effect Effects 0.000 abstract description 12
- 125000003277 amino group Chemical group 0.000 abstract description 4
- UITKHKNFVCYWNG-UHFFFAOYSA-N 4-(3,4-dicarboxybenzoyl)phthalic acid Chemical compound C1=C(C(O)=O)C(C(=O)O)=CC=C1C(=O)C1=CC=C(C(O)=O)C(C(O)=O)=C1 UITKHKNFVCYWNG-UHFFFAOYSA-N 0.000 abstract description 3
- IPZJQDSFZGZEOY-UHFFFAOYSA-N dimethylmethylene Chemical compound C[C]C IPZJQDSFZGZEOY-UHFFFAOYSA-N 0.000 abstract description 2
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 abstract description 2
- 150000000000 tetracarboxylic acids Chemical class 0.000 abstract 2
- 229920006122 polyamide resin Polymers 0.000 abstract 1
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 description 18
- 238000006243 chemical reaction Methods 0.000 description 18
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 14
- 239000000243 solution Substances 0.000 description 13
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 12
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 12
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 9
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 9
- 239000000853 adhesive Substances 0.000 description 9
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical group [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 7
- 239000011889 copper foil Substances 0.000 description 7
- 239000000843 powder Substances 0.000 description 7
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 6
- 229910052757 nitrogen Inorganic materials 0.000 description 6
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 6
- 238000003756 stirring Methods 0.000 description 6
- 239000004642 Polyimide Substances 0.000 description 5
- 238000010438 heat treatment Methods 0.000 description 5
- 238000000576 coating method Methods 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 239000011248 coating agent Substances 0.000 description 3
- 238000004821 distillation Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000005457 ice water Substances 0.000 description 3
- 239000010410 layer Substances 0.000 description 3
- 239000011259 mixed solution Substances 0.000 description 3
- 239000002244 precipitate Substances 0.000 description 3
- 238000010926 purge Methods 0.000 description 3
- 238000007363 ring formation reaction Methods 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- YBRVSVVVWCFQMG-UHFFFAOYSA-N 4,4'-diaminodiphenylmethane Chemical compound C1=CC(N)=CC=C1CC1=CC=C(N)C=C1 YBRVSVVVWCFQMG-UHFFFAOYSA-N 0.000 description 2
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 2
- 239000004593 Epoxy Substances 0.000 description 2
- 238000005266 casting Methods 0.000 description 2
- 239000011247 coating layer Substances 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 239000003822 epoxy resin Substances 0.000 description 2
- 239000004744 fabric Substances 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 229920000647 polyepoxide Polymers 0.000 description 2
- XBTHNZXADRSYPR-UHFFFAOYSA-N 3-(1,1,1,3,3,3-hexafluoro-2-phenylpropan-2-yl)benzene-1,2-diamine Chemical compound NC1=CC=CC(C(C=2C=CC=CC=2)(C(F)(F)F)C(F)(F)F)=C1N XBTHNZXADRSYPR-UHFFFAOYSA-N 0.000 description 1
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 1
- SUAKHGWARZSWIH-UHFFFAOYSA-N N,N‐diethylformamide Chemical compound CCN(CC)C=O SUAKHGWARZSWIH-UHFFFAOYSA-N 0.000 description 1
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 1
- 230000005856 abnormality Effects 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 229920000800 acrylic rubber Polymers 0.000 description 1
- 238000012644 addition polymerization Methods 0.000 description 1
- 238000007259 addition reaction Methods 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical group [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000006210 cyclodehydration reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000012024 dehydrating agents Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- AJFDBNQQDYLMJN-UHFFFAOYSA-N n,n-diethylacetamide Chemical compound CCN(CC)C(C)=O AJFDBNQQDYLMJN-UHFFFAOYSA-N 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229920005575 poly(amic acid) Polymers 0.000 description 1
- 229920000058 polyacrylate Polymers 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 230000007261 regionalization Effects 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
Landscapes
- Laminated Bodies (AREA)
- Polymers With Sulfur, Phosphorus Or Metals In The Main Chain (AREA)
- Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
Abstract
Description
【発明の詳細な説明】
［発明の目的］
〈産業上の利用分野）
本発明は、金属板や金属箔にポリイミド樹脂フィルムを
直接接着した、耐熱性、接着性に優れた回路基板の製造
方法に関する。[Detailed Description of the Invention] [Object of the Invention] (Field of Industrial Application) The present invention provides a method for manufacturing a circuit board with excellent heat resistance and adhesive properties, in which a polyimide resin film is directly adhered to a metal plate or metal foil. Regarding.
（従来の技術）
従来使用されている回路基板は、（１）金属箔または金
属板上に接着剤を介して基材を接着したもの、（２）金
属箔または金属板をエポキシ樹脂系接着剤或いはエポキ
シ樹脂含浸ガラスクロスで１５０℃以上の高温で加熱加
圧一体化したもの、（３）金属箔または金属板上にポリ
アミド酸樹脂溶液を直接塗布し、少なくとも３００℃以
上の高温でイミド化させたものである。(Prior Art) Conventionally used circuit boards are (1) metal foil or metal plate with a base material bonded via adhesive, and (2) metal foil or metal plate bonded with epoxy resin adhesive. Alternatively, epoxy resin-impregnated glass cloth is integrated by heating and pressing at a high temperature of 150°C or higher; (3) A polyamic acid resin solution is directly applied onto metal foil or a metal plate and imidized at a high temperature of at least 300°C or higher. It is something that
しかし、（１）の回路基板は接着剤の耐熱性が低く回路
基板として不適当である。 （２）の回路基板は、使
用するエポキシ樹脂系接着剤またはエポキシ樹脂含浸ガ
ラスクロスが可撓性、低誘電特性に劣る欠点がある。
また（３）ではポリイミド前駆体の組成によって生成ポ
リイミド膜と金属箔または金属板との接着力が不十分と
なり、回路パターン形成時に剥離現象を生じ不良の原因
どなる欠点がある。However, in the circuit board (1), the adhesive has low heat resistance and is unsuitable as a circuit board. The circuit board (2) has the disadvantage that the epoxy resin adhesive or epoxy resin-impregnated glass cloth used is poor in flexibility and low dielectric properties.
In addition, (3) has the disadvantage that the adhesion between the produced polyimide film and the metal foil or metal plate is insufficient due to the composition of the polyimide precursor, resulting in a peeling phenomenon during circuit pattern formation, which can lead to defects.
（発明が解決しようとする課題）
本発明は、上記の欠点を解消するためになされたもので
、接着剤層の介在がなく、耐熱性、接着性、可撓性に優
れたもので回路パターン形成時に剥離現象を生じない回
路基板の製造方法を提供しようとするものである。(Problems to be Solved by the Invention) The present invention has been made in order to eliminate the above-mentioned drawbacks. It is an object of the present invention to provide a method for manufacturing a circuit board that does not cause a peeling phenomenon during formation.
［発明の構成］
（課題を解決するための手段）
本発明者は、上記の目的を達成しようと鋭意研究を重ね
た結果、接着剤を介在させることなく、特定のポリイミ
ド樹脂フィルムを直接に金属箔や金属板に接着すれば上
記目的が達成されることを見いだし、本発明を完成した
ものである。[Structure of the Invention] (Means for Solving the Problems) As a result of extensive research to achieve the above object, the present inventor has discovered that a specific polyimide resin film can be directly bonded to a metal without intervening an adhesive. The inventors have discovered that the above object can be achieved by adhering to foil or metal plates, and have completed the present invention.
すなわち、本発明は、
＜Ａ＞ ３．３′，４， ４．４’−ベンゾフェノン
テトラカルボン酸（その無水物及び低級アルキルエステ
ルを含む）を９５モル％以上の主成分として含む芳香族
テトラカルボン酸と、
（Ｂ）−数式（Ｉ）又は（ｎ）
（但し、式中Ｘは、ＣＨ，、Ｏ，ＳＯ２゜Ｃ，（ＣＨ３
） ２ 、 Ｃ（ＣＦ３ ） ２又はＳを、Ｒ１Ｒ２は
ＣＨ，、Ｃ２Ｈ，、ＯＣＨ３又はＱＣ２Ｈ５を、Ｒ３、
Ｒ４はＣ２Ｈ１１を、Ｒ５はフェニル基又はシクロヘキ
サン基を表し、Ｒ１−Ｒ４はいずれもＲ５に関しアミノ
基のオルソ位に置換されている）で示される芳香族ジア
ミンを９０モル％以上の主成分として含むジアミンとを
反応させてなるポリイミド樹脂フィルムを、金属箔又は
金属板に対して直接に接着することを特徴とする回路基
板の製造方法である。That is, the present invention provides <A> an aromatic tetracarboxylic acid containing 95 mol% or more of 3.3',4,4.4'-benzophenone tetracarboxylic acid (including its anhydride and lower alkyl ester) as a main component; acid, (B) - formula (I) or (n) (wherein X is CH,, O, SO2°C, (CH3
)2, C(CF3)2 or S, R1R2 is CH,, C2H,, OCH3 or QC2H5, R3,
R4 represents C2H11, R5 represents a phenyl group or a cyclohexane group, and R1-R4 are all substituted at the ortho position of the amino group with respect to R5) Contains 90 mol% or more of an aromatic diamine as a main component This method of manufacturing a circuit board is characterized in that a polyimide resin film formed by reacting with a diamine is directly adhered to a metal foil or a metal plate.
本発明に用いる（Ａ）芳香族テトラカルボン酸に含まれ
る３、３′、 ４．４’−ベンゾフェノンテトラカルボ
ン酸は、３．３”、 ４．４’−ベンゾフェノンテトラ
カルボン酸並びにその無水物及び低級アルキルエステル
を意味する。 （Ａ）芳香族テトラカルボン酸は３．
３′、 ４．４’−ベンゾフェノンテトラカルボン酸が
全量であることが望ましいが、それ以外の芳香族テトラ
カルボン酸を５モル％未満含んでもよい。The 3,3', 4,4'-benzophenone tetracarboxylic acid contained in the aromatic tetracarboxylic acid (A) used in the present invention includes 3.3", 4,4'-benzophenone tetracarboxylic acid and its anhydride and It means lower alkyl ester. (A) Aromatic tetracarboxylic acid is 3.
Although it is desirable that the total amount is 3', 4,4'-benzophenonetetracarboxylic acid, it may contain less than 5 mol% of other aromatic tetracarboxylic acids.
本発明に用いる（Ｂ）ジアミンは、次の一蝦式％式％（
）
（但し、式中Ｘは、ＣＨ２，Ｏ，ＳＯ２゜Ｃ（ＣＨ３）
２ 、 Ｃ（ＣＦ３ ） ２又はＳを、Ｒ′Ｒ２はＣ
Ｈ，、Ｃ２Ｈ，、ＯＣＨ，又はＱＣ２Ｈ５を、Ｒ３，Ｒ
’はＣ２Ｈｓを、Ｒ６はフェニル基又はシクロヘキサン
基を表し′、そしてＲ１−Ｒ４はいずれもＲｓに関しア
ミノ基のオルソ位に置換されている）で示される芳香族
ジアミンを含んでいる。 この構造式（Ｉ）又は（ＩＩ
）の芳香族ジアミンとしては、３．３′−ジメチル−５
□５′−ジエチル−４，４′−ジアミノジフェニルメタ
ン、３．３ ′，４， ５．５’−テトラエチル−４，
４′−ジアミノジフェニルメタン、３．３′−ジメチル
−４，４′−ジアミノジシクロヘキシルメタン、３，３
′−ジメトキシ−４，４′−ジアミノジフェニルメタン
、３．３′−ジェトキシ−４゜４′−ジアミノジフェニ
ルメタン、３．３′−ジエチル−４，４’−ジアミノジ
フェニルエーテル、３．３′−ジメトキシ−４，４′−
ジアミノジフェニルエーテル、３゜３′−メチル−４，
４′−ジアミノジフェニルスルホン、３．３′−ジエチ
ル−４，４′−ジアミノジフェニルスルホン、３．３′
−ジメトキシ−４，４′−ジアミノジフェニルスルホン
、３．３−ジェトキシ−４，４′−ジアミノジフェニル
スルホン、３，３′−ジメチル−４，４′−ジアミノジ
フェニルプロパン、３．３′−ジエチル−４，４′−ジ
アミノジフェニルプロパン、３，３′−ジメトキシ−４
４′〜ジアミノジフエニルプロパン、３．３′−ジェト
キシ−４，４′−ジアミノジフェニルプロパン、３．３
’−ジメチル−４，４′−ジアミノジフェニルスルファ
イド、３．３′−ジエチル−４，４′−ジアミノジフェ
ニルスルファイド、３，３′−ジメトキシ−４，４′−
ジアミノジフェニルスルファイド、３．３′−ジェトキ
シ−４，４′−ジアミノジフェニルスルファイド、４．
４′−ジメチル−５，５′〜ジアミノジフエニルへキサ
フルオロプロパン等が挙げられ、これらは単独又は２種
以上混合して用いることができる。The diamine (B) used in the present invention has the following formula:
) (However, in the formula, X is CH2, O, SO2゜C(CH3)
2, C(CF3) 2 or S, R'R2 is C
H,, C2H,, OCH, or QC2H5, R3, R
' represents C2Hs, R6 represents a phenyl group or a cyclohexane group,' and R1 to R4 are all substituted at the ortho position of the amino group with respect to Rs. This structural formula (I) or (II
), the aromatic diamine is 3,3'-dimethyl-5
□5'-diethyl-4,4'-diaminodiphenylmethane, 3.3',4, 5.5'-tetraethyl-4,
4'-diaminodiphenylmethane, 3.3'-dimethyl-4,4'-diaminodicyclohexylmethane, 3,3
'-Dimethoxy-4,4'-diaminodiphenylmethane, 3.3'-jethoxy-4゜4'-diaminodiphenylmethane, 3.3'-diethyl-4,4'-diaminodiphenyl ether, 3.3'-dimethoxy-4 ,4'-
Diaminodiphenyl ether, 3°3'-methyl-4,
4'-diaminodiphenylsulfone, 3.3'-diethyl-4,4'-diaminodiphenylsulfone, 3.3'
-dimethoxy-4,4'-diaminodiphenylsulfone, 3,3-jethoxy-4,4'-diaminodiphenylsulfone, 3,3'-dimethyl-4,4'-diaminodiphenylpropane, 3,3'-diethyl- 4,4'-diaminodiphenylpropane, 3,3'-dimethoxy-4
4'-diaminodiphenylpropane, 3.3'-jethoxy-4,4'-diaminodiphenylpropane, 3.3
'-Dimethyl-4,4'-diaminodiphenylsulfide, 3,3'-diethyl-4,4'-diaminodiphenylsulfide, 3,3'-dimethoxy-4,4'-
Diaminodiphenylsulfide, 3.3'-jethoxy-4,4'-diaminodiphenylsulfide, 4.
Examples include 4'-dimethyl-5,5' to diaminodiphenylhexafluoropropane, and these can be used alone or in combination of two or more.
また、この芳香族ジアミンの他に１０モル％未満の他の
ジアミンを配合することもできる。In addition to this aromatic diamine, less than 10 mol % of other diamines can also be blended.
（Ａ＞の芳香族テトラカルボン酸と（Ｂ）ジアミンの反
応は、はぼ等モルを有機溶媒中で３０℃以下、好ましく
は０℃以下の反応温度下に３〜１２時間付加反応させた
後、脱水剤を加えて１００℃で脱水環化して次の構造式
（ＩＩＩ）あるいは（ＩＶ）のポリイミド樹脂が得られ
る。The reaction between the aromatic tetracarboxylic acid (A) and the diamine (B) is carried out after an addition reaction of approximately equimolar amounts in an organic solvent at a reaction temperature of 30°C or lower, preferably 0°C or lower for 3 to 12 hours. , a dehydrating agent is added and cyclodehydration is carried out at 100° C. to obtain a polyimide resin of the following structural formula (III) or (IV).
・・・・・・＜Ｉ［） ・・・・・・（ＩＶ） （但し、式中Ｘは、ＣＨ２，Ｏ，Ｓｏ、。・・・・・・＜I[) ・・・・・・(IV) (However, in the formula, X is CH2, O, So.
Ｃ（ＣＨ３）２．Ｃ（ＣＦ□）２又はＳを、Ｒ′Ｒ２は
、ＣＨ，、Ｃ，Ｈ，、ＯＣＨ，又はＱＣ，Ｈ，を、Ｒ３
，Ｒ’はＣｚ Ｈｓを、ａｌｌは、Ｃ６Ｈ，又はシクロ
ヘキサン基を、ｎは整数をそれぞれ表し、そしてＲ１−
Ｒ４はいずれもＲ５に関しアミノ基のオルソ位に置換さ
れている）この付加重合反応において用いる有機溶媒と
しては、例えばジメチルスルホオキシド、Ｎ、Ｎ−ジメ
チルボルムアミド、Ｎ、Ｎ−ジエチルホルムアミド、Ｎ
、Ｎ−ジメチルアセトアミド、Ｎ、Ｎ−ジエチルアセト
アミド、Ｎ−メチル−２−ピロリドン、ヘキサメチレン
ホスホアミド等が用いられる。C(CH3)2. C(CF□)2 or S, R'R2 is CH,, C, H,, OCH, or QC, H, R3
, R' represents Cz Hs, all represents C6H or a cyclohexane group, n represents an integer, and R1-
R4 is substituted at the ortho position of the amino group with respect to R5) Examples of the organic solvent used in this addition polymerization reaction include dimethyl sulfoxide, N,N-dimethylformamide, N,N-diethylformamide, N
, N-dimethylacetamide, N,N-diethylacetamide, N-methyl-2-pyrrolidone, hexamethylenephosphoamide, etc. are used.
ポリイミド樹脂からフィルムを製造する場合は、ポリイ
ミド溶液を離型紙またはフィルムにコーティングしてつ
くる。 この場合、ポリイミド溶液はポリイミド樹脂５
〜４０重量％、好ましくは１０〜３０重量％溶液とし、
かつ固有粘度が０．５〜６旧／Ｑ、特に０．１〜４ ｔ
ｉ＋／ｇである溶液を用いることがポリイミドの物性及
び塗布・乾燥工程での経済性から好ましい、 ポリイミ
ド樹脂溶液を離型紙またはフィルムにコーティングする
操作は流延塗布して行われるが、具体的には次のような
方法で行われる。 離型紙又はフィルムにポリイミド樹
脂溶液を製膜用スリットから吐出させて均一な厚さ（−
数的には１０〜３００μｌとなるように調節される）の
塗膜層が形成される。 他のコーティング手段としては
、ロールコータ−、ナイフコーター、コンマコーター
ドクターブレード、フローコーターなどの他の公知の手
段を利用することも可能である。When manufacturing a film from polyimide resin, it is made by coating release paper or film with a polyimide solution. In this case, the polyimide solution is polyimide resin 5
~40% by weight, preferably 10-30% by weight solution;
and has an intrinsic viscosity of 0.5 to 6 old/Q, especially 0.1 to 4 t
It is preferable to use a solution with i+/g from the viewpoint of the physical properties of polyimide and the economic efficiency of the coating and drying process.The operation of coating a release paper or film with a polyimide resin solution is carried out by casting, but specifically is done in the following way. A polyimide resin solution is discharged onto a release paper or film through a film forming slit to form a uniform thickness (-
A coating layer (numerically adjusted to 10 to 300 μl) is formed. Other coating methods include roll coater, knife coater, and comma coater.
It is also possible to utilize other known means such as a doctor blade, flow coater, etc.
このようにして調製されたポリイミド塗布層を加熱して
脱溶媒を行う、 加熱温度は一般的には１００〜２００
℃で、好ましくは１００〜１８０℃である。The polyimide coating layer prepared in this way is heated to remove the solvent, and the heating temperature is generally 100-200℃.
℃, preferably 100 to 180℃.
こうして離型紙又はフィルム上にポリイミド樹脂フィル
ムを形成し、その後、離型紙やフィルムを剥がしてポリ
イミド樹脂フィルムを得る。A polyimide resin film is thus formed on the release paper or film, and then the release paper or film is peeled off to obtain a polyimide resin film.
このポリイミド樹脂のフィルムは、銅箔、アルミニウム
箔、ニッケル箔、その他金属板等に加熱加圧接着する。This polyimide resin film is bonded to copper foil, aluminum foil, nickel foil, other metal plates, etc. under heat and pressure.
加熱加圧接着する方法は、金属箔や金属板上にフィル
ムを直接重ねた後、加熱加圧してポリイミドフィルムを
融着させる。 この時の温度は２００〜３００℃、好ま
しくは１５０〜２９０℃の範囲である。 金属箔や金属
板はポリイミドフィルムを間に介して多層化することも
できる。The heating and pressure bonding method involves directly stacking a film on metal foil or a metal plate, and then applying heat and pressure to fuse the polyimide film. The temperature at this time is in the range of 200 to 300°C, preferably 150 to 290°C. The metal foil or metal plate can also be multilayered with a polyimide film interposed therebetween.
（作用）
本発明の回路基板の製造方法は、新規なポリイミド樹脂
フィルムを直接に銅箔などと接着させることによって、
その効果を奏するものである。(Function) The method for manufacturing a circuit board of the present invention involves directly adhering a novel polyimide resin film to a copper foil or the like.
This will produce that effect.
この新規なポリイミド樹脂はフィルム形成能力に優れて
おり、このフィルムを接着剤の介在なしで金属板や金属
箔に融着させることができる。 かかる製造方法によっ
てポリイミド樹脂本来の耐熱性は保持される。This new polyimide resin has excellent film-forming ability, and the film can be fused to a metal plate or metal foil without the intervention of an adhesive. This manufacturing method maintains the inherent heat resistance of the polyimide resin.
（実施例） 次に本発明を実施例によって説明する。(Example) Next, the present invention will be explained by examples.
実施例 １
三ロフラスコに乾燥窒素を通じてフラスコ内を窒素で置
換した後、３．３′，４， ５．５’−テトラエチル−
４，４′−ジアミノジフェニルメタン３１０ｇを入れ、
これにＮ−メチル−２−ピロリドン（Ｎ Ｍ Ｐ ）
２５３０１を加え溶解した。 溶解後、０°Ｃに冷却し
て撹拌しながら３．３′，４， ４．４’−ベンゾフェ
ノンテトラカルボン酸無水物３２２ｇを加えた。 反応
熱を氷水中で抑えながら６時間攪拌を続けて反応させた
。Example 1 After purging the inside of the flask with nitrogen by passing dry nitrogen into a three-ring flask, 3.3',4,5.5'-tetraethyl-
Add 310 g of 4,4'-diaminodiphenylmethane,
To this, N-methyl-2-pyrrolidone (NMP)
25301 was added and dissolved. After dissolving, the mixture was cooled to 0°C and 322 g of 3.3',4,4.4'-benzophenonetetracarboxylic acid anhydride was added while stirring. The reaction was continued with stirring for 6 hours while suppressing the reaction heat in ice water.
次いで反応溶液に脱水剤である無水酢酸４０８１、およ
びピリジン４０１１を加え、１００℃で酢酸を留出させ
ながら３時間の閉環反応を行った。 その後、無水酢酸
／ピリジンを減圧下で留出除去させてイミド化を完結さ
せた。 イミド化反応後、反応溶液をメタノールと水の
混合溶液に投入してポリイミド樹脂を析出させ、析出物
を乾燥して黄色のポリイミド樹脂粉末（固有粘度２．５
６１／ｇ）５９０９を得た。 得られたポリイミド樹脂
粉末１５０ｇをシクロヘキサノン８５０１に溶解して、
離型フィルム上に流延塗布によって厚さ３５μｍに均一
にコーティングし、１５０℃で加熱乾燥してポリイミド
フィルムを得た。 このフィルムを厚さ３５μｌの銅箔
に重ね、２９０℃で１０分間加圧してポリイミド樹脂フ
ィルムを絶縁層とする回路基板を製造した。Next, dehydrating agents acetic anhydride 4081 and pyridine 4011 were added to the reaction solution, and a ring-closing reaction was carried out for 3 hours while distilling acetic acid out at 100°C. Thereafter, acetic anhydride/pyridine was removed by distillation under reduced pressure to complete imidization. After the imidization reaction, the reaction solution is poured into a mixed solution of methanol and water to precipitate polyimide resin, and the precipitate is dried to produce yellow polyimide resin powder (intrinsic viscosity 2.5
61/g) 5909 was obtained. 150 g of the obtained polyimide resin powder was dissolved in cyclohexanone 8501,
A release film was coated uniformly to a thickness of 35 μm by casting and dried by heating at 150° C. to obtain a polyimide film. This film was stacked on a copper foil having a thickness of 35 μl and pressed at 290° C. for 10 minutes to produce a circuit board having the polyimide resin film as an insulating layer.
実施例 ２
三ロフラスコに乾燥窒素を通じてフラスコ内を窒素で置
換した後、４，４′−ジメチル−５，５′−ジアミノジ
フェニルへキサフルオロプロパン３６２ｇを入れ、これ
にＮ−メチル−２−ピロリドン（ＮＭＰ）３４２０１を
加えて溶解した。 溶解後０℃に冷却して攪拌しながら
３．３′，４， ４．４’−ベンゾフェノンテトラカル
ボン酸無水物３２２ｇを加えた。 反応熱を氷水中で抑
えながら６時間攪拌を続は反応させた。Example 2 After purging the inside of the flask with nitrogen by passing dry nitrogen into a three-ring flask, 362 g of 4,4'-dimethyl-5,5'-diaminodiphenylhexafluoropropane was added, and N-methyl-2-pyrrolidone ( NMP) 34201 was added and dissolved. After dissolving, the mixture was cooled to 0° C. and 322 g of 3.3',4,4.4'-benzophenone tetracarboxylic anhydride was added while stirring. The reaction was continued with stirring for 6 hours while suppressing the reaction heat in ice water.
次いで反応溶液に脱水剤である無水酢酸４０８１、およ
びピリジン４０１加え、１００℃で酢酸を留出させなが
ら３時間の閉環反応を行った。 その後無水酢酸／ピリ
ジンを減圧下で留出除去させてイミド化を完結させた。Next, acetic anhydride 4081 and pyridine 401 as dehydrating agents were added to the reaction solution, and a ring-closing reaction was carried out at 100° C. for 3 hours while distilling acetic acid. Thereafter, acetic anhydride/pyridine was removed by distillation under reduced pressure to complete imidization.
イミド化反応後、反応溶液をメタノールと水の混合溶
液に投入してポリイミド樹脂を析出させ、析出物を乾燥
して黄色のポリイミド樹脂粉末（固有粘度３．４４ ｃ
＋＋／ｇ ） ６４０ｇを得な、 得られたポリイミ
ド樹脂粉末１５０ｇをシクロヘキサノン８５０１に溶解
し、離型フィルム上に流延塗布して厚さ３５μｌに均一
にコーティングし、１５０℃で加熱乾燥してポリイミド
フィルムを得た。 このフィルムを厚さ３５μ椙の銅箔
に重ね、２９０℃で１０分間加圧してポリイミド樹脂を
絶縁層とする回路基板を製造した。After the imidization reaction, the reaction solution was poured into a mixed solution of methanol and water to precipitate the polyimide resin, and the precipitate was dried to form a yellow polyimide resin powder (intrinsic viscosity: 3.44 c).
++/g) 640 g of polyimide resin powder was obtained. 150 g of the obtained polyimide resin powder was dissolved in cyclohexanone 8501, cast onto a release film to uniformly coat it to a thickness of 35 μl, and heated and dried at 150° C. to form a polyimide resin powder. Got the film. This film was layered on a 35 μm thick copper foil and pressed at 290° C. for 10 minutes to produce a circuit board with polyimide resin as an insulating layer.
実施例 ３
三ロフラスコに乾燥窒素を通じてフラスコ内を窒素で置
換した後、３．３′−ジメチル−５，５′−ジエチル−
４，４′−ジアミノジフェニルメタン２８２ｇを入れ、
これにＮ−メチル−２−ピロリドン（ＮＭＰ）２４２０
１を加え溶解した。 溶解後、０℃に冷却し撹拌しなが
ら３．３′，４， ４．４’−ベンゾフェノンテトラカ
ルボン酸無水物３２２ｇを加えた。 反応熱を氷水中で
抑えながら６時間撹拌を続けて反応させた。Example 3 After purging the inside of the flask with nitrogen by passing dry nitrogen into a three-loaf flask, 3,3'-dimethyl-5,5'-diethyl-
Add 282 g of 4,4'-diaminodiphenylmethane,
To this, N-methyl-2-pyrrolidone (NMP) 2420
1 was added and dissolved. After dissolving, the mixture was cooled to 0° C. and 322 g of 3.3',4,4.4'-benzophenonetetracarboxylic anhydride was added while stirring. The reaction was continued with stirring for 6 hours while suppressing the reaction heat in ice water.
次いで、反応溶液に脱水剤である無水酢酸４０８１、お
よびピリジン４０１１＋を加え、１００℃で酢酸を留出
させながら３時間の閉環反応を行った。 その後無水酢
酸／ピリジンを減圧下で留出除去させてイミド化を完結
させた。 イミド化反応後、反応溶液をメタノールと水
の混合溶液に投入してポリイミド樹脂を析出させ、析出
物を乾燥して黄色のポリイミド樹脂粉末（固有粘度２．
３３ ｄｌ／Ｑ ”）５６４ｇを得た。 得られたポリ
イミド樹脂１５０ｇをシクロヘキサノン８５０１に溶解
して、離型フィルム上に流延塗布し厚さ３５μ僅に均一
にコーティングし、１５０℃で加熱乾燥してポリイミド
フィルムを得た。 このフィルムを厚さ３５μｍの銅箔
に重ね、２９０℃で１０分間加圧してポリイミド樹脂を
絶縁層とする回路基板を製造した。Next, acetic anhydride 4081 and pyridine 4011+, which are dehydrating agents, were added to the reaction solution, and a ring-closing reaction was carried out for 3 hours while distilling acetic acid out at 100°C. Thereafter, acetic anhydride/pyridine was removed by distillation under reduced pressure to complete imidization. After the imidization reaction, the reaction solution is poured into a mixed solution of methanol and water to precipitate the polyimide resin, and the precipitate is dried to produce a yellow polyimide resin powder (intrinsic viscosity 2.
33 dl/Q'') 564 g of the obtained polyimide resin was dissolved in cyclohexanone 8501, cast and coated on a release film to a thickness of 35 μm, and dried by heating at 150°C. A polyimide film was obtained. This film was stacked on a 35 μm thick copper foil and pressed at 290° C. for 10 minutes to produce a circuit board having the polyimide resin as an insulating layer.
比較例
市販の厚さ２５μｌのポリイミドフィルムと実施例で用
いた銅箔とをアクリルゴム系接着剤を用いて室温で０．
７ｋｇ／ ｃｎ’の条件で加圧して回路基板を製造しな
。Comparative Example A commercially available polyimide film with a thickness of 25 μl and the copper foil used in the example were bonded together using an acrylic rubber adhesive at room temperature.
Manufacture circuit boards under pressure of 7 kg/cn'.
実施例１〜３及び比較例で得られた回路基板のポリイミ
ドフィルムと銅箔との接着力（ＡＳＴＭ−Ｄ−１８７５
に準じて測定）、耐はんだ性〈ＪＩｓ−Ｃ−６４８１に
準じて測定）を試験しなので、その結果を第１表に示し
た。 本発明の回路基板は外観の異常がなく、接着力も
優れており、本発明の効果が認められた。Adhesion strength between the polyimide film and copper foil of the circuit board obtained in Examples 1 to 3 and Comparative Example (ASTM-D-1875
The results are shown in Table 1. The results are shown in Table 1. The circuit board of the present invention had no abnormality in appearance and had excellent adhesive strength, and the effects of the present invention were recognized.
第
表
（単位）
［発明の効果〕
以上の説明および第１表から明らかなように、本発明の
回路基板の製造方法によれば、耐熱性、接着力、可視性
に優れており、接着剤の介在がなくても剥離現象を生じ
ない回路基板を得ることができる。Table (Units) [Effects of the Invention] As is clear from the above explanation and Table 1, the method for manufacturing a circuit board of the present invention has excellent heat resistance, adhesive strength, and visibility, and It is possible to obtain a circuit board that does not cause peeling even without the intervention of.
Claims (1)
ルボン酸（その無水物及び低級アルキルエステルを含む
）を９５モル％以上の主成分として含む芳香族テトラカ
ルボン酸と、 （Ｂ）一般式（ I ）又は（II） ▲数式、化学式、表等があります▼ ・・・・・・（
I ） ▲数式、化学式、表等があります▼ ・・・・・・（I
I） （但し、式中Ｘは、ＣＨ＿２，Ｏ，ＳＯ＿２，Ｃ（ＣＨ
＿３）＿２，Ｃ（ＣＦ＿３）＿２又はＳを、Ｒ＾１，Ｒ
＾２はＣＨ＿３，Ｃ＿２Ｈ＿５，ＯＣＨ＿３又はＯＣ＿
２Ｈ＿５を、Ｒ＾３，Ｒ＾４はＣ＾２Ｈ＾５を、Ｒ＾５
はフェニル基又はシクロヘキサン基を表し、Ｒ＾１〜Ｒ
＾４はいずれもＲ＾５に関しアミノ基のオルソ位に置換
されている）で示される芳香族ジアミンを９０モル％以
上の主成分として含むジアミンとを反応させてなるポリ
イミド樹脂フィルムを、金属箔又は金属板に対して直接
に接着することを特徴とする回路基板の製造方法。[Scope of Claims] 1 (A) An aromatic tetracarboxylic acid containing 95 mol% or more of 3,3',4,4-benzophenone tetracarboxylic acid (including its anhydride and lower alkyl ester) as a main component; , (B) General formula (I) or (II) ▲There are mathematical formulas, chemical formulas, tables, etc.▼ ・・・・・・(
I) ▲There are mathematical formulas, chemical formulas, tables, etc.▼ ・・・・・・(I
I) (However, in the formula, X is CH_2, O, SO_2, C(CH
_3)_2,C(CF_3)_2 or S, R^1,R
^2 is CH_3, C_2H_5, OCH_3 or OC_
2H_5, R^3, R^4 is C^2H^5, R^5
represents a phenyl group or a cyclohexane group, R^1~R
A polyimide resin film obtained by reacting a diamine containing as a main component 90 mol% or more of an aromatic diamine represented by Or a method for manufacturing a circuit board, characterized by directly bonding it to a metal plate.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1016235A JP2712082B2 (en) | 1989-01-27 | 1989-01-27 | Circuit board manufacturing method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1016235A JP2712082B2 (en) | 1989-01-27 | 1989-01-27 | Circuit board manufacturing method |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH02198837A true JPH02198837A (en) | 1990-08-07 |
| JP2712082B2 JP2712082B2 (en) | 1998-02-10 |
Family
ID=11910893
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP1016235A Expired - Lifetime JP2712082B2 (en) | 1989-01-27 | 1989-01-27 | Circuit board manufacturing method |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2712082B2 (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH04299885A (en) * | 1990-12-17 | 1992-10-23 | E I Du Pont De Nemours & Co | Tetrapolyimide film that incorporates benzophenone tetracarboxylic acid two anhydride |
| JP2002368393A (en) * | 2001-06-05 | 2002-12-20 | Toray Eng Co Ltd | Method for manufacturing metal wiring circuit board |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6115825A (en) * | 1984-06-29 | 1986-01-23 | Lion Corp | Toothpaste composition |
| JPS62208690A (en) * | 1985-10-31 | 1987-09-12 | 三井東圧化学株式会社 | Flexible printed circuit and manufacture of the same |
-
1989
- 1989-01-27 JP JP1016235A patent/JP2712082B2/en not_active Expired - Lifetime
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6115825A (en) * | 1984-06-29 | 1986-01-23 | Lion Corp | Toothpaste composition |
| JPS62208690A (en) * | 1985-10-31 | 1987-09-12 | 三井東圧化学株式会社 | Flexible printed circuit and manufacture of the same |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH04299885A (en) * | 1990-12-17 | 1992-10-23 | E I Du Pont De Nemours & Co | Tetrapolyimide film that incorporates benzophenone tetracarboxylic acid two anhydride |
| JP2002368393A (en) * | 2001-06-05 | 2002-12-20 | Toray Eng Co Ltd | Method for manufacturing metal wiring circuit board |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2712082B2 (en) | 1998-02-10 |
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