JPH0768728A - Manufacture of flexible metal polyimide laminated plate - Google Patents
Manufacture of flexible metal polyimide laminated plateInfo
- Publication number
- JPH0768728A JPH0768728A JP5218260A JP21826093A JPH0768728A JP H0768728 A JPH0768728 A JP H0768728A JP 5218260 A JP5218260 A JP 5218260A JP 21826093 A JP21826093 A JP 21826093A JP H0768728 A JPH0768728 A JP H0768728A
- Authority
- JP
- Japan
- Prior art keywords
- polyamic acid
- boiling point
- solvent
- flexible metal
- drying
- 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
Classifications
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K1/00—Printed circuits
- H05K1/02—Details
- H05K1/03—Use of materials for the substrate
- H05K1/0313—Organic insulating material
- H05K1/032—Organic insulating material consisting of one material
- H05K1/0346—Organic insulating material consisting of one material containing N
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K1/00—Printed circuits
- H05K1/02—Details
- H05K1/03—Use of materials for the substrate
- H05K1/0393—Flexible materials
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K3/00—Apparatus or processes for manufacturing printed circuits
- H05K3/02—Apparatus or processes for manufacturing printed circuits in which the conductive material is applied to the surface of the insulating support and is thereafter removed from such areas of the surface which are not intended for current conducting or shielding
- H05K3/022—Processes for manufacturing precursors of printed circuits, i.e. copper-clad substrates
Landscapes
- Laminated Bodies (AREA)
- Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明はフレキシブル金属ポリイ
ミド積層板の製造方法に関する。フレキシブル金属ポリ
イミド積層板はプリント基板、その他の用途に供され
る。FIELD OF THE INVENTION The present invention relates to a method for producing a flexible metal-polyimide laminate. The flexible metal-polyimide laminate is used for printed circuit boards and other applications.
【０００２】[0002]
【従来の技術】フレキシブル金属ポリイミド積層板（Ｆ
ＭＣＬ＝Flexible Metal Clad Laminate）は可とう性を
有するプリント回路基盤等を製造するための素材であっ
て、プリント回路収容の容器等が小型化されることなど
より、その利用度が増大している。また、近年、耐熱性
が良い、薄型化が簡単であるなどの理由から、接着剤層
を介さない、ポリイミドと金属箔の二層からなるフレキ
シブル金属ポリイミド積層板に対する要求が増えてい
る。2. Description of the Related Art Flexible metal-polyimide laminate (F
MCL = Flexible Metal Clad Laminate) is a material for manufacturing flexible printed circuit boards and the like, and its utilization is increasing due to the miniaturization of containers for containing printed circuits. . Further, in recent years, there has been an increasing demand for a flexible metal-polyimide laminate having two layers of polyimide and a metal foil without an adhesive layer for reasons such as good heat resistance and easy thinning.
【０００３】接着剤層を介さずにポリイミドを金属箔に
貼付ける方法として、有機溶剤で希釈したポリアミド酸
を金属箔に塗工し、乾燥後、イミド化するといった方法
がある。しかして、この方法を用いる場合、ポリアミド
酸を塗工した金属箔がカールし、塗工端部が折れ曲がる
為に、ＦＭＣＬの収率が落ちるという問題点があった。As a method for pasting polyimide on a metal foil without an adhesive layer, there is a method in which a polyamic acid diluted with an organic solvent is applied to the metal foil, dried and then imidized. However, when this method is used, the metal foil coated with polyamic acid is curled, and the coated end portion is bent, so that the yield of FMCL is lowered.
【０００４】[0004]
【発明が解決しようとする課題】以上の点に鑑み、本発
明は、カールしないフレキシブル金属ポリイミド積層板
の製造方法を供することを目的とする。In view of the above points, the present invention aims to provide a method for producing a curled flexible metal-polyimide laminate.
【０００５】[0005]
【課題を解決するための手段】本発明者らは、上記目的
を達成する為に、鋭意検討した結果、有機溶剤に溶解し
たポリアミド酸を、金属箔上に塗工、乾燥する際、有機
溶剤の沸点よりも低い温度で乾燥すると、カールを防げ
ることを見出した。しかして、該方法では乾燥速度が遅
く、生産性が非常に悪い。そこで、さらに鋭意検討した
結果、有機溶剤として沸点が異なる２種以上の混合溶剤
を用い、かつ、乾燥工程において、ポリアミド酸塗工金
属箔を、低沸点溶剤の沸点より高く、高沸点溶剤の沸点
より低い温度で乾燥させると、有機溶剤に溶解したポリ
アミド酸の厚さ方向の濃度勾配が小さくなり、表面と内
部の乾燥速度の違いによる収縮率の差を低減でき、カー
ルを防げ、かつ、乾燥速度も速く、生産性が向上するこ
とを見出し、本発明を完成した。[Means for Solving the Problems] The inventors of the present invention have conducted extensive studies in order to achieve the above object. As a result, when a polyamic acid dissolved in an organic solvent is applied onto a metal foil and dried, an organic solvent is used. It was found that curling can be prevented by drying at a temperature lower than the boiling point of. However, in this method, the drying speed is slow and the productivity is very poor. Therefore, as a result of further diligent studies, a mixed solvent of two or more kinds having different boiling points was used as the organic solvent, and in the drying step, the polyamic acid-coated metal foil was higher than the boiling point of the low boiling point solvent and the boiling point of the high boiling point solvent. When dried at a lower temperature, the concentration gradient of the polyamic acid dissolved in the organic solvent in the thickness direction becomes smaller, the difference in shrinkage ratio due to the difference in the drying speed between the surface and the inside can be reduced, curling can be prevented, and drying is possible. The present invention has been completed by finding that the speed is high and the productivity is improved.
【０００６】即ち、本発明は、沸点が異なる２種以上の
有機溶剤に溶解したポリアミド酸を、金属箔上に塗工、
乾燥した後、ポリアミド酸をイミド化させてフレキシブ
ル金属ポリイミド積層板を製造する方法において、ポリ
アミド酸塗工金属箔を、低沸点溶剤の沸点より高く、高
沸点溶剤の沸点より低い温度で乾燥させた後、ポリアミ
ド酸をイミド化させることを特徴とするフレキシブル金
属ポリイミド積層板の製造方法である。That is, according to the present invention, a polyamic acid dissolved in two or more kinds of organic solvents having different boiling points is coated on a metal foil,
After drying, in the method for producing a flexible metal-polyimide laminate by imidizing polyamic acid, the polyamic acid-coated metal foil was dried at a temperature higher than the boiling point of the low boiling point solvent and lower than the boiling point of the high boiling point solvent. After that, the method for producing a flexible metal-polyimide laminate is characterized by imidizing polyamic acid.
【０００７】本発明に用いる有機溶剤は、２種以上の溶
剤からなる混合溶剤であり、少なくとも１種類はＮ，Ｎ
−ジメチルホルムアミド、Ｎ，Ｎ−ジメチルアセトアミ
ド、Ｎ−メチルピロリドン等のポリアミド酸を溶解する
高沸点溶剤である。混合する有機溶剤としては、Ｎ，Ｎ
−ジメチルホルムアミド、Ｎ，Ｎ−ジメチルアセトアミ
ド、トルエン、キシレン、酢酸エチル、酢酸メチル、ア
セトン、メタノール、エタノール、プロパノール等の低
沸点溶剤が挙げられるが、ポリアミド酸を溶解する溶剤
と相溶性の良い溶剤であれば、ポリアミド酸を溶解する
溶剤でも、ポリアミド酸を溶解しない溶剤でも適宜使用
することが出来る。これらの中から沸点の異なるものを
１種以上ずつ、合計で２種以上用いれば良い。ここで、
低沸点溶剤とは混合溶剤のなかで相対的に沸点の低いも
のをいい、高沸点溶剤とは相対的に沸点の高いものをい
う。The organic solvent used in the present invention is a mixed solvent composed of two or more kinds of solvents, at least one kind of which is N, N.
It is a high boiling solvent that dissolves polyamic acid such as dimethylformamide, N, N-dimethylacetamide, and N-methylpyrrolidone. As the organic solvent to be mixed, N, N
-Low boiling point solvents such as dimethylformamide, N, N-dimethylacetamide, toluene, xylene, ethyl acetate, methyl acetate, acetone, methanol, ethanol, propanol, etc., but a solvent that is compatible with a solvent that dissolves polyamic acid. If so, a solvent that dissolves a polyamic acid or a solvent that does not dissolve a polyamic acid can be used as appropriate. Among these, one or more kinds having different boiling points may be used, and two or more kinds in total may be used. here,
The low boiling point solvent means a solvent having a relatively low boiling point among mixed solvents, and the high boiling point solvent means a solvent having a relatively high boiling point.
【０００８】本発明に用いるポリアミド酸としては、ポ
リイミドフィルムにした際、耐屈曲性が２５０００回以
上（ＪＩＳ Ｐ−８１１５、張力１ｋｇ、曲率半径０．
３８ｍｍ）、引張弾性率４００ｋｇ／ｍｍ2 以下、金属
箔との９０゜ピール強度が０．４ｋｇ／ｃｍ以上であ
る、 対称型芳香族メタ置換第１級ジアミンと対称型芳香
族パラ置換第１級ジアミンとを当量比で１０〜６０：９
０〜４０で混合した後、芳香族テトラカルボン酸無水物
と反応させて生成したポリアミド酸、 対称型芳香族メタ置換第１級ジアミンと芳香族テト
ラカルボン酸無水物と反応させて生成したポリアミド酸
（ａ）と、対称型芳香族パラ置換第１級ジアミンと芳香
族テトラカルボン酸無水物と反応させて生成したポリア
ミド酸（ｂ）とを当量比で１０〜６０：９０〜４０で混
合したポリアミド酸、 が好ましく、特に好ましくは、、において、対称型
芳香族メタ置換第１級ジアミンが次式（１） （但し、上記の式でＸはＯ、ＳＯ2 、ＣＯ、ＣＨ2 、Ｃ
（ＣＨ3 ）2 、Ｃ（ＣＦ3 ）2 あるいは直結を表す）で
あるポリアミド酸であるが、特に限定されるものではな
く、必要に応じ、公知のものを適宜選択出来る。The polyamic acid used in the present invention has a flex resistance of 25,000 times or more when formed into a polyimide film (JIS P-8115, tension 1 kg, curvature radius 0.
38 mm), tensile modulus of 400 kg / mm 2 or less, 90 ° peel strength with metal foil of 0.4 kg / cm or more, symmetric aromatic meta-substituted primary diamine and symmetric aromatic para-substituted primary diamine Equivalent ratio of diamine and 10-60: 9
Polyamic acid produced by mixing with 0 to 40 and then reacting with aromatic tetracarboxylic acid anhydride, polyamic acid produced by reacting with symmetrical aromatic meta-substituted primary diamine and aromatic tetracarboxylic acid anhydride Polyamide obtained by mixing (a) with a polyamic acid (b) produced by reacting a symmetric aromatic para-substituted primary diamine and an aromatic tetracarboxylic acid anhydride in an equivalent ratio of 10 to 60:90 to 40. The acid is particularly preferable, and the symmetric aromatic meta-substituted primary diamine is represented by the following formula (1): (However, in the above formula, X is O, SO 2 , CO, CH 2 , C
The polyamic acid which is (CH 3 ) 2 , C (CF 3 ) 2 or represents a direct bond) is not particularly limited, and known ones can be appropriately selected as necessary.
【０００９】本発明に用いる金属箔としては、銅、軟質
アルミニウム、ニッケル、金、銀およびこれらを含有す
る合金等が挙げられるが、好ましくは、引張弾性率が４
５００ｋｇ／ｍｍ2 以下（変形量が１％以下におい
て）、対折れ強さが２０回以上（ＭＩＴ試験機、張力５
００ｇ、曲率半径０．３８ｍｍ）のものであり、その中
でも電導性・エッチング性より銅が最も好ましい。Examples of the metal foil used in the present invention include copper, soft aluminum, nickel, gold, silver and alloys containing these, and preferably the tensile elastic modulus is 4 or less.
500 kg / mm 2 or less (deformation amount is 1% or less), anti-bending strength is 20 times or more (MIT tester, tension 5
00g, radius of curvature 0.38 mm), and of these, copper is the most preferable in terms of electrical conductivity and etching property.
【００１０】ポリアミド酸を塗工する金属箔面は、接着
力を向上させるために、塗工表面積を増やすために、銅
箔の表面処理等で良く行われる電解メッキにより粒子を
付着させたり、交流エッチング等を行い、塗工表面積を
増やすことが好ましく、また、ポリアミド酸に適したシ
ランカップリング処理、チタネートカップリング処理等
を行い接着力を向上させても良い。On the metal foil surface coated with polyamic acid, in order to improve the adhesive strength and to increase the coating surface area, particles are attached by electrolytic plating which is often carried out in the surface treatment of copper foil and the like. It is preferable to increase the coating surface area by performing etching or the like, and the adhesive force may be improved by performing silane coupling treatment, titanate coupling treatment or the like suitable for polyamic acid.
【００１１】この金属箔の厚さは好ましくは５〜１００
μｍ程度である。The thickness of this metal foil is preferably 5-100.
It is about μm.
【００１２】金属箔がエッチング加工等によりパターン
化される場合は、ＦＭＣＬの寸法を金属箔の寸法とみな
し、次に、ＦＭＣＬから金属箔を化学的に全面エッチン
グしてポリイミドフィルムだけにした時の寸法をポリイ
ミドフィルムの寸法とみなした場合、その寸法差がパタ
ーンの平滑性に影響するため、±０．３％以内であるこ
とが好ましい。特に好ましくはその寸法差は±０．１％
以内である。When the metal foil is patterned by etching or the like, the size of the FMCL is regarded as the size of the metal foil, and then the entire metal foil is chemically etched from the FMCL to form only the polyimide film. When the dimension is regarded as the dimension of the polyimide film, the dimension difference affects the smoothness of the pattern, so that it is preferably within ± 0.3%. Particularly preferably, the dimensional difference is ± 0.1%
Within.
【００１３】また、このＦＭＣＬが１５０℃以上の高温
で使用されたり、ＦＭＣＬの一部が電子回路にパターン
化され、その回路とＩＣのベアーチップとが金のワイヤ
ーボンドで結ばれる場合には、２００℃以上の雰囲気温
度で、金属箔とポリイミドとのピール強度が０．５ｋｇ
／ｃｍ以上であることが好ましい。When the FMCL is used at a high temperature of 150 ° C. or higher, or when a part of the FMCL is patterned into an electronic circuit and the circuit and the bare chip of the IC are connected by a gold wire bond, Peel strength between metal foil and polyimide is 0.5kg at ambient temperature of 200 ℃ or more.
/ Cm or more is preferable.
【００１４】塗工方法としては、ダイコーター、コンマ
コーター、ロールコーター、バーコーター等、従来公知
の方法が採用できる。好ましくは、ダイコーター、コン
マコーターである。ポリアミド酸の塗工厚さは、イミド
化後のフィルムとして５〜１００μｍ程度になる厚さが
好ましい。As a coating method, conventionally known methods such as a die coater, a comma coater, a roll coater and a bar coater can be adopted. A die coater and a comma coater are preferable. The coating thickness of the polyamic acid is preferably about 5 to 100 μm as a film after imidization.
【００１５】乾燥方法としては、低沸点溶剤の沸点より
高く、高沸点溶剤より低い温度で乾燥させる。As a drying method, drying is performed at a temperature higher than the boiling point of the low boiling point solvent and lower than that of the high boiling point solvent.
【００１６】乾燥後のイミド化方法は、イナートオーブ
ンによるバッチ法でも、イミド化炉による連続式でも、
公知の方法が用いられ、特にその方法、条件に限定はな
い。イミド化は通常２００〜４５０℃で行なわれる。The imidization method after drying may be a batch method using an inert oven or a continuous method using an imidizing furnace.
A known method is used, and the method and conditions are not particularly limited. The imidization is usually performed at 200 to 450 ° C.
【００１７】[0017]
【実施例】以下、実施例により本発明をさらに具体的に
説明する。 実施例１ 攪拌機、還流冷却器及び窒素導入管を備えた容器で、
１，３−ビス（３−アミノフェノキシ）ベンゼン２９４
ｇ（０．８０モル）及び４，４’−ジアミノジフェニル
エーテル２４０ｇ（１．２０モル）をＮ，Ｎ−ジメチル
アセトアミド（以下ＤＭＡｃと略す）４５００ｍｌに溶
解した。この溶液に窒素雰囲気下において３，３’，
４，４’−ベンゾフェノンテトラカルボン酸二無水物６
４４ｇ（２．０モル）を添加し、１０℃で２４時間攪拌
してポリアミド酸溶液を得た。このポリアミド酸溶液を
ＤＭＡｃとＮ−メチルピロリドン（以下ＮＭＰと略す）
の１対１（重量比）の混合溶媒で１２．５％（樹脂固形
分１００重量部に対して溶剤含有量７００重量部）まで
希釈し、粘度を２２０００ｃｐｓに調節し、ダイコータ
ーを用いて圧延銅箔（厚さ３５μｍ、幅４５ｃｍ）に塗
工幅４０ｃｍ、塗工厚さ１２０μｍでコーティングし
た。このポリアミド酸塗工銅箔を、炉長６ｍの熱風乾燥
機にて、乾燥温度１８０℃、ライン速度４ｍ／ｍｉｎで
乾燥させた。ポリアミド酸がべたつく（タックする）こ
となく、巻き取ることが出来た。カール性の評価は、こ
のポリアミド酸塗工銅箔を縦横１００ｍｍの正方形に切
り取り、平らなガラス板の上に置き、銅箔の四隅の反り
返り高さ（以下耳立ち高さと言う）を測定した。結果を
表１に示す。EXAMPLES The present invention will be described in more detail below with reference to examples. Example 1 A container equipped with a stirrer, a reflux condenser and a nitrogen inlet tube,
1,3-bis (3-aminophenoxy) benzene 294
g (0.80 mol) and 240 g (1.20 mol) of 4,4′-diaminodiphenyl ether were dissolved in 4500 ml of N, N-dimethylacetamide (hereinafter abbreviated as DMAc). In this solution under nitrogen atmosphere 3,3 ',
4,4'-benzophenone tetracarboxylic acid dianhydride 6
44 g (2.0 mol) was added and stirred at 10 ° C. for 24 hours to obtain a polyamic acid solution. This polyamic acid solution is treated with DMAc and N-methylpyrrolidone (hereinafter abbreviated as NMP).
1: 1 (weight ratio) mixed solvent to 12.5% (solvent content 700 parts by weight relative to resin solids 100 parts by weight), adjust the viscosity to 22000 cps, and roll using a die coater A copper foil (thickness 35 μm, width 45 cm) was coated with a coating width of 40 cm and a coating thickness of 120 μm. This polyamic acid-coated copper foil was dried with a hot air dryer having a furnace length of 6 m at a drying temperature of 180 ° C. and a line speed of 4 m / min. The polyamic acid could be wound up without sticking. To evaluate the curling property, this polyamic acid-coated copper foil was cut into squares of 100 mm in length and width, placed on a flat glass plate, and the warp heights of the four corners of the copper foil (hereinafter referred to as ear heights) were measured. The results are shown in Table 1.
【００１８】実施例２ 攪拌機、還流冷却器及び窒素導入管を備えた容器で、
４，４’−ビス（３−アミノフェノキシ）ビフェニル２
２１ｇ（０．６０モル）及び４，４’−ジアミノジフェ
ニルエーテル２８０ｇ（１．４０モル）をＮＭＰ３００
０ｍｌに溶解し、０℃付近まで冷却し、窒素雰囲気下に
於いてピロメリット酸二無水物４３６ｇ（２．０モル）
を加え、０℃付近で２時間攪拌した。次に上記溶液を室
温に戻し、窒素雰囲気下で約２０時間攪拌を行った。こ
うして得られたポリアミド酸溶液をＮ，Ｎ−ジメチルホ
ルムアミド（以下ＤＭＦと略す）で２０．０％（樹脂固
形分１００重量部に対して溶剤含有量４００重量部）ま
で希釈し、粘度を１２００００ｃｐｓに調節し、実施例
１と同様のコーターを用いて圧延銅箔（厚さ３５μｍ、
幅４５ｃｍ）に塗工幅４０ｃｍ、塗工厚さ１２０μｍで
コーティングした。このポリアミド酸塗工銅箔を、炉長
６ｍの熱風乾燥機にて、乾燥温度１８０℃、ライン速度
４ｍ／ｍｉｎで乾燥させた。ポリアミド酸がべたつく
（タックする）ことなく、巻き取ることが出来た。この
ポリアミド酸塗工銅箔を、実施例１と同様の方法で評価
した。結果を表１に示す。Example 2 A container equipped with a stirrer, a reflux condenser and a nitrogen inlet tube,
4,4'-bis (3-aminophenoxy) biphenyl 2
21 g (0.60 mol) and 4,4'-diaminodiphenyl ether (280 g, 1.40 mol) were added to NMP300.
Dissolve in 0 ml, cool to around 0 ° C., and under a nitrogen atmosphere, 436 g (2.0 mol) of pyromellitic dianhydride.
Was added, and the mixture was stirred at about 0 ° C. for 2 hours. Next, the solution was returned to room temperature and stirred under a nitrogen atmosphere for about 20 hours. The polyamic acid solution thus obtained was diluted with N, N-dimethylformamide (hereinafter abbreviated as DMF) to 20.0% (solvent content: 400 parts by weight based on 100 parts by weight of resin solid content) to obtain a viscosity of 120,000 cps. Adjustment, using the same coater as in Example 1, rolled copper foil (thickness 35 μm,
The coating width was 45 cm and the coating width was 40 cm and the coating thickness was 120 μm. This polyamic acid-coated copper foil was dried with a hot air dryer having a furnace length of 6 m at a drying temperature of 180 ° C. and a line speed of 4 m / min. The polyamic acid could be wound up without sticking. This polyamic acid-coated copper foil was evaluated in the same manner as in Example 1. The results are shown in Table 1.
【００１９】比較例１ 実施例１と同様にして得られたポリアミド酸の希釈溶液
を、実施例１と同一のコーターを用いて圧延銅箔（厚さ
３５μｍ、幅４５ｃｍ）に塗工幅４０ｃｍ、塗工厚さ１
２０μｍでコーティングした。このポリアミド酸塗工銅
箔を、炉長６ｍの熱風乾燥機にて、乾燥温度１２０℃、
ライン速度４ｍ／ｍｉｎで乾燥させた。ポリアミド酸の
べたつきが見られた。このポリアミド酸塗工銅箔を、実
施例１と同様の方法で評価した。結果を表１に示す。Comparative Example 1 A dilute solution of polyamic acid obtained in the same manner as in Example 1 was applied to a rolled copper foil (thickness: 35 μm, width: 45 cm) with a coating width of 40 cm, using the same coater as in Example 1. Coating thickness 1
It was coated with 20 μm. This polyamic acid-coated copper foil was dried with a hot air dryer having a furnace length of 6 m at a drying temperature of 120 ° C.
It was dried at a line speed of 4 m / min. Stickiness of polyamic acid was observed. This polyamic acid-coated copper foil was evaluated in the same manner as in Example 1. The results are shown in Table 1.
【００２０】比較例２ 実施例１と同様にして得られたポリアミド酸の希釈溶液
を、実施例１と同一のコーターを用いて圧延銅箔（厚さ
３５μｍ、幅４５ｃｍ）に塗工幅４０ｃｍ、塗工厚さ１
２０μｍでコーティングした。このポリアミド酸塗工銅
箔を、炉長６ｍの熱風乾燥機にて、乾燥温度２２０℃、
ライン速度４ｍ／ｍｉｎで乾燥させた。ポリアミド酸が
べたつく（タックする）ことなく、巻き取ることが出来
た。このポリアミド酸塗工銅箔を、実施例１と同様の方
法で評価した。結果を表１に示す。Comparative Example 2 A dilute solution of a polyamic acid obtained in the same manner as in Example 1 was applied to a rolled copper foil (thickness: 35 μm, width: 45 cm) with a coating width of 40 cm, using the same coater as in Example 1. Coating thickness 1
It was coated with 20 μm. This polyamic acid-coated copper foil was dried with a hot air dryer having a furnace length of 6 m at a drying temperature of 220 ° C.
It was dried at a line speed of 4 m / min. The polyamic acid could be wound up without sticking. This polyamic acid-coated copper foil was evaluated in the same manner as in Example 1. The results are shown in Table 1.
【００２１】比較例３ 実施例１と同様にして得られたポリアミド酸溶液をＮ，
Ｎ−ジメチルアセトアミド（以下ＤＭＡｃと略す）で１
２．５％（樹脂固形分１００重量部に対して溶剤含有量
７００重量部）まで希釈し、粘度を２１０００ｃｐｓに
調節し、実施例１と同一のコーターを用いて圧延銅箔
（厚さ３５μｍ、幅４５ｃｍ）に塗工幅４０ｃｍ、塗工
厚さ１２０μｍでコーティングした。このポリアミド酸
塗工銅箔を、炉長６ｍの熱風乾燥機にて、乾燥温度１２
０℃、ライン速度４ｍ／ｍｉｎで乾燥させた。ポリアミ
ド酸のべたつきが見られた。このポリアミド酸塗工銅箔
を、実施例１と同様の方法で評価した。結果を表１に示
す。Comparative Example 3 A polyamic acid solution obtained in the same manner as in Example 1 was treated with N,
1 with N-dimethylacetamide (hereinafter abbreviated as DMAc)
Diluted to 2.5% (solvent content 700 parts by weight with respect to 100 parts by weight of resin solids), adjusting the viscosity to 21000 cps, and using the same coater as in Example 1, rolled copper foil (thickness 35 μm, The coating width was 45 cm and the coating width was 40 cm and the coating thickness was 120 μm. This polyamic acid-coated copper foil was dried at a drying temperature of 12 with a hot air dryer having a furnace length of 6 m.
It was dried at 0 ° C. and a line speed of 4 m / min. Stickiness of polyamic acid was observed. This polyamic acid-coated copper foil was evaluated in the same manner as in Example 1. The results are shown in Table 1.
【００２２】比較例４ 比較例３と同様にして得られたポリアミド酸の希釈溶液
を、実施例１と同一のコーターを用いて圧延銅箔（厚さ
３５μｍ、幅４５ｃｍ）に塗工幅４０ｃｍ、塗工厚さ１
２０μｍでコーティングした。このポリアミド酸塗工銅
箔を、炉長６ｍの熱風乾燥機にて、乾燥温度１８０℃、
ライン速度４ｍ／ｍｉｎで乾燥させた。ポリアミド酸が
べたつく（タックする）ことなく、巻き取ることが出来
た。このポリアミド酸塗工銅箔を、実施例１と同様の方
法で評価した。結果を表１に示す。Comparative Example 4 A dilute solution of polyamic acid obtained in the same manner as in Comparative Example 3 was applied to a rolled copper foil (thickness: 35 μm, width: 45 cm) with a coating width of 40 cm, using the same coater as in Example 1. Coating thickness 1
It was coated with 20 μm. This polyamic acid-coated copper foil was dried with a hot air dryer having a furnace length of 6 m at a drying temperature of 180 ° C.
It was dried at a line speed of 4 m / min. The polyamic acid could be wound up without sticking. This polyamic acid-coated copper foil was evaluated in the same manner as in Example 1. The results are shown in Table 1.
【００２３】[0023]
【表１】 注 沸点 ＤＭＡｃ １６６．１℃ ＮＭＰ ２０２ ℃ ＤＭＦ １５３．０℃ タック性なし：べたつくこともなく、巻き取ることがで
きた。 タック性あり：べたついて巻き取ることができなかっ
た。 耳立ち高さ： ポリアミド酸塗工銅箔を縦横１００ｍｍ
の正方形に切り取り、平らなガラス板の上に置いた時
の、銅箔の四隅の反り返り高さをいう。[Table 1] Note Boiling point DMAc 166.1 ° C. NMP 202 ° C. DMF 153.0 ° C. No tackiness: It was possible to wind without stickiness. Tackiness: Sticky and could not be wound up. Ear height: Polyamide acid coated copper foil 100 mm in length and width
The height of the copper foil's four corners when it is cut out into squares and placed on a flat glass plate.
【００２４】[0024]
【発明の効果】本発明によれば、乾燥工程において、沸
点が異なる２種以上の有機溶剤に溶解したポリアミド酸
を塗工した金属箔を低沸点溶剤の沸点より高く、高沸点
溶剤の沸点より低い温度で乾燥させることにより、ポリ
アミド酸塗工金属箔のカールを防ぎ、フレキシブル金属
ポリイミド積層板の収率を向上させることができる。According to the present invention, in the drying step, the metal foil coated with polyamic acid dissolved in two or more organic solvents having different boiling points is higher than the low boiling point solvent and higher than the high boiling point solvent. By drying at a low temperature, the curling of the polyamic acid-coated metal foil can be prevented, and the yield of the flexible metal-polyimide laminate can be improved.
フロントページの続き (72)発明者 竹村 康男 愛知県名古屋市南区丹後通２丁目１番地 三井東圧化学株式会社内 (72)発明者 山村 武 愛知県名古屋市南区丹後通２丁目１番地 三井東圧化学株式会社内 (72)発明者 大坪 英二 愛知県名古屋市南区丹後通２丁目１番地 三井東圧化学株式会社内Front page continued (72) Inventor Yasuo Takemura 2-1, Tangodori, Minami-ku, Aichi Prefecture Mitsui Toatsu Chemical Co., Ltd. (72) Inventor Takeshi Yamamura 2-1-1, Tangodori, Minami-ku, Aichi Prefecture Mitsui Toatsu Chemical Co., Ltd. (72) Inventor Eiji Otsubo 2-chome, Tango-dori, Minami-ku, Nagoya, Aichi Prefecture Mitsui Toatsu Chemical Co., Ltd.
Claims (2)
したポリアミド酸を、金属箔上に塗工、乾燥した後、ポ
リアミド酸をイミド化させてフレキシブル金属ポリイミ
ド積層板を製造する方法において、ポリアミド酸塗工金
属箔を、低沸点溶剤の沸点より高く、高沸点溶剤の沸点
より低い温度で乾燥させることを特徴とするフレキシブ
ル金属ポリイミド積層板の製造方法。1. A method for producing a flexible metal-polyimide laminate by applying polyamic acid dissolved in two or more kinds of organic solvents having different boiling points onto a metal foil, drying the polyamic acid, and imidizing the polyamic acid. A method for producing a flexible metal-polyimide laminate, comprising drying a polyamic acid-coated metal foil at a temperature higher than the boiling point of a low boiling point solvent and lower than the boiling point of a high boiling point solvent.
ミド、Ｎ，Ｎ−ジメチルアセトアミドおよびＮ−メチル
ピロリドンからなる群から選ばれた少なくとも１種であ
り、低沸点溶剤がＮ，Ｎ−ジメチルホルムアミド、Ｎ，
Ｎ−ジメチルアセトアミド、トルエン、キシレン、酢酸
エチル、酢酸メチル、アセトン、メタノール、エタノー
ルおよびプロパノールからなる群から選ばれた少なくと
も１種であることを特徴とする請求項１に記載のフレキ
シブル金属ポリイミド積層板の製造方法。2. The high-boiling solvent is at least one selected from the group consisting of N, N-dimethylformamide, N, N-dimethylacetamide and N-methylpyrrolidone, and the low-boiling solvent is N, N-dimethylformamide. , N,
The flexible metal polyimide laminate according to claim 1, which is at least one selected from the group consisting of N-dimethylacetamide, toluene, xylene, ethyl acetate, methyl acetate, acetone, methanol, ethanol and propanol. Manufacturing method.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP5218260A JPH0768728A (en) | 1993-09-02 | 1993-09-02 | Manufacture of flexible metal polyimide laminated plate |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP5218260A JPH0768728A (en) | 1993-09-02 | 1993-09-02 | Manufacture of flexible metal polyimide laminated plate |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH0768728A true JPH0768728A (en) | 1995-03-14 |
Family
ID=16717092
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP5218260A Pending JPH0768728A (en) | 1993-09-02 | 1993-09-02 | Manufacture of flexible metal polyimide laminated plate |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0768728A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2007281361A (en) * | 2006-04-11 | 2007-10-25 | Asahi Kasei Corp | Polyimide printed circuit board and polyimide printed wiring board |
| WO2019163860A1 (en) * | 2018-02-23 | 2019-08-29 | 富士フイルム株式会社 | Film production method, laminate production method, semiconductor device production method, and film formation composition |
| KR20220068600A (en) * | 2020-11-19 | 2022-05-26 | 피아이첨단소재 주식회사 | Polyamic acid composition and polyimide comprising the same |
-
1993
- 1993-09-02 JP JP5218260A patent/JPH0768728A/en active Pending
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2007281361A (en) * | 2006-04-11 | 2007-10-25 | Asahi Kasei Corp | Polyimide printed circuit board and polyimide printed wiring board |
| WO2019163860A1 (en) * | 2018-02-23 | 2019-08-29 | 富士フイルム株式会社 | Film production method, laminate production method, semiconductor device production method, and film formation composition |
| KR20200110402A (en) * | 2018-02-23 | 2020-09-23 | 후지필름 가부시키가이샤 | Film production method, laminate production method, semiconductor device production method, and film-forming composition |
| CN111819306A (en) * | 2018-02-23 | 2020-10-23 | 富士胶片株式会社 | Method for producing film, method for producing laminate, method for producing semiconductor device, and composition for film formation |
| JPWO2019163860A1 (en) * | 2018-02-23 | 2021-02-12 | 富士フイルム株式会社 | A film manufacturing method, a laminate manufacturing method, a semiconductor device manufacturing method, and a film forming composition. |
| KR20220068600A (en) * | 2020-11-19 | 2022-05-26 | 피아이첨단소재 주식회사 | Polyamic acid composition and polyimide comprising the same |
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