TWI392408B - Copper plate - Google Patents

Copper plate Download PDF

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Publication number
TWI392408B
TWI392408B TW095148761A TW95148761A TWI392408B TW I392408 B TWI392408 B TW I392408B TW 095148761 A TW095148761 A TW 095148761A TW 95148761 A TW95148761 A TW 95148761A TW I392408 B TWI392408 B TW I392408B
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Taiwan
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copper
adhesive
less
dianhydride
film
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TW095148761A
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Chinese (zh)
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TW200806104A (en
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Meguru Maeda
Koichi Sawasaki
Masahiro Oguni
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Du Pont Toray Co Ltd
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B15/00—Layered products comprising a layer of metal
    • B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B15/08—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B15/00—Layered products comprising a layer of metal
    • B32B15/20—Layered products comprising a layer of metal comprising aluminium or copper
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/28—Layered products comprising a layer of synthetic resin comprising synthetic resins not wholly covered by any one of the sub-groups B32B27/30 - B32B27/42
    • B32B27/281—Layered products comprising a layer of synthetic resin comprising synthetic resins not wholly covered by any one of the sub-groups B32B27/30 - B32B27/42 comprising polyimides
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
    • B32B7/04—Interconnection of layers
    • B32B7/12—Interconnection of layers using interposed adhesives or interposed materials with bonding properties
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J133/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J163/00—Adhesives based on epoxy resins; Adhesives based on derivatives of epoxy resins
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J179/00—Adhesives based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen, with or without oxygen, or carbon only, not provided for in groups C09J161/00 - C09J177/00
    • C09J179/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
    • C09J179/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Laminated Bodies (AREA)
  • Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)

Description

舖銅板Copper plate

本發明係有關於一種舖銅板，其適合使用於電氣電子機器領域之撓性印刷電路板、COF、TAB，更詳言之，係有關於一種蝕刻後之尺寸變化率小之舖銅板，該舖銅板係以聚醯亞胺薄膜作為基材，並於其單面或雙面具有銅。The present invention relates to a copper-clad laminate suitable for use in a flexible printed circuit board, COF, TAB in the field of electrical and electronic equipment, and more particularly to a copper-clad laminate having a small dimensional change rate after etching. The copper plate has a polyimide film as a substrate and has copper on one or both sides.

印刷電路基板被廣泛地使用於電子電機機器。其中，能夠折彎的撓性印刷電路板被廣泛地使用於個人電腦、行動電話等的折彎部分、硬碟等之必須折彎的部分。此等撓性印刷電路板的材料通常係使用舖銅板，該舖銅板係使用各種聚醯亞胺薄膜。Printed circuit boards are widely used in electronic machine machines. Among them, a flexible printed circuit board that can be bent is widely used in a bent portion of a personal computer, a mobile phone, or the like, and a portion that must be bent, such as a hard disk. The material of such flexible printed circuit boards is usually a copper-clad laminate using various polyimide films.

使用於舖銅板之聚醯亞胺薄膜的代表物，可舉出的有酸二酐成分使用焦蜜石酸二酐、二胺成分使用4,4’－二胺基二苯醚之聚醯亞胺薄膜。此種聚醯亞胺薄膜具有機械性、熱特性之平衡優良的結構，能廣泛地使用於工業上作為泛用製品。但是，雖然由焦蜜石酸二酐、及4,4’－二胺基二苯醚所構成的聚醯亞胺薄膜在具有容易彎曲之優點，相反面，因為太柔軟在裝載半導體時會有基材彎曲、接合不良的問題點。又，由焦蜜石酸二酐、及4,4’－二胺基二苯醚所構成的聚醯亞胺薄膜，因為熱膨脹係數(CTE)或吸濕膨脹係數(CHE)大、吸水率亦高，所以因熱或吸水所產生的尺寸變化大，會有在進行微細的配線形成時無法按照目標形成配線寬度或配線間隔之問題。Representative examples of the polyimide film used for the copper plate include an acid dianhydride component using pyromellitic dianhydride and a diamine component using 4,4'-diaminodiphenyl ether. Amine film. Such a polyimide film has a structure excellent in mechanical and thermal properties, and can be widely used industrially as a general-purpose product. However, although the polyimide film composed of pyromellitic dianhydride and 4,4'-diaminodiphenyl ether has an advantage of being easily bent, on the contrary, since it is too soft when loading a semiconductor The problem of bending and poor bonding of the substrate. Further, a polyimide film composed of pyromellitic dianhydride and 4,4'-diaminodiphenyl ether has a large coefficient of thermal expansion (CTE) or a coefficient of hygroscopic expansion (CHE) and a water absorption rate. When the size is high, the dimensional change due to heat or water absorption is large, and there is a problem that the wiring width or the wiring interval cannot be formed according to the target when fine wiring is formed.

為了解決如此的問題，有一種方法(例如，參照專利文獻1)，揭示使用聚醯亞胺薄膜以外之尺寸變化較小的基材例如液晶薄膜等，來形成撓性印刷電路板之方法，但是液晶薄膜之耐熱性比聚醯亞胺薄膜差，在進行焊料焊接時會有基材變形的問題。特別是近年來因為環境問題而擴大使用未使用鉛之無鉛焊料，幾乎所有的無鉛焊料的熔點比含鉛焊料高，使液晶薄膜之基材變形的問題變為更嚴重。In order to solve such a problem, there is a method (for example, refer to Patent Document 1), and a method of forming a flexible printed circuit board using a substrate having a small dimensional change other than a polyimide film, such as a liquid crystal film, is disclosed. The heat resistance of the liquid crystal film is inferior to that of the polyimide film, and there is a problem that the substrate is deformed during soldering. In particular, in recent years, lead-free solders using unused lead have been expanded due to environmental problems, and almost all lead-free solders have higher melting points than lead-containing solders, and the problem of deforming the substrate of the liquid crystal film becomes more serious.

專利文獻1：特開2005－297405號公報Patent Document 1: JP-A-2005-297405

因此，本發明之目的係提供一種撓性印刷電路板用之舖銅板，能夠解決如此之撓性印刷電路板的尺寸變化及耐熱性兩方的問題，能夠形成微細配線，且即便使用無鉛焊料亦不會變形。Accordingly, an object of the present invention is to provide a copper clad laminate for a flexible printed circuit board, which can solve the problems of dimensional change and heat resistance of such a flexible printed circuit board, can form fine wiring, and even use lead-free solder. Will not be deformed.

本發明為了達成上述目的，採用以下的構成。In order to achieve the above object, the present invention adopts the following constitution.

(1)一種舖銅板，係透過黏著劑，在使用以對苯二胺及4,4’－二胺基二苯醚作為二胺成分、以及以焦蜜石酸二酐及3,3’,4,4’－聯苯四羧酸二酐作為酸二酐成分所形成之聚醯亞胺薄膜之單面或雙面具有銅板。(1) A copper-clad laminate which is obtained by using an adhesive, p-phenylenediamine and 4,4'-diaminodiphenyl ether as a diamine component, and pyromellitic dianhydride and 3,3', The 4,4'-biphenyltetracarboxylic dianhydride has a copper plate on one side or both sides of the polyimide film formed of the acid dianhydride component.

(2)一種舖銅板，係不透過黏著劑，在使用以對苯二胺及4,4’－二胺基二苯醚作為二胺成分、以及以焦蜜石酸二酐及3,3’,4,4’－聯苯四羧酸二酐作為酸二酐成分所形成之聚醯亞胺薄膜之單面或雙面具有銅板。(2) A copper-clad laminate that is impermeable to adhesives, using p-phenylenediamine and 4,4'-diaminodiphenyl ether as the diamine component, and pyromellitic dianhydride and 3,3' The 4,4'-biphenyltetracarboxylic dianhydride has a copper plate on one side or both sides of the polyimide film formed by the acid dianhydride component.

(3)一種舖銅板，係透過黏著劑，在使用以對苯二胺及4,4’－二胺基二苯醚作為二胺成分、以及以焦蜜石酸二酐及3,3’,4,4’聯苯四羧酸二酐作為酸二酐成分所形成之聚醯亞胺薄膜之一面、另一面則未透過黏著劑而具有銅板。(3) A copper-clad laminate is obtained by using an adhesive, p-phenylenediamine and 4,4'-diaminodiphenyl ether as a diamine component, and pyromellitic dianhydride and 3,3', The 4,4' biphenyltetracarboxylic dianhydride has a copper plate as one side of the polyimide film formed by the acid dianhydride component and the other side does not pass through the adhesive.

(4)如(1)~(3)中任一項之舖銅板，其中聚醯亞胺薄膜的二胺成分係10~50莫耳%對苯二胺及50~90莫耳%4,4’－二胺基二苯醚，酸二酐成分係50~99莫耳%焦蜜石酸二酐及1~50莫耳%3,3’,4,4’聯苯四羧酸二酐。(4) The copper-clad laminate according to any one of (1) to (3), wherein the polyamine component of the polyimide film is 10 to 50 mol% of p-phenylenediamine and 50 to 90 mol% of 4,4 '-Diaminodiphenyl ether, acid dianhydride component is 50~99 mol% pyromic acid dianhydride and 1~50 mol% 3,3',4,4' biphenyltetracarboxylic dianhydride.

(5)如(1)~(4)中任一項之舖銅板，其中係使用彈性模數3~7GPa、在50~200℃之線膨脹係數為5~20ppm/℃、濕度膨脹係數為25ppm/%RH以下、吸水率為3%以下，在200℃ 1小時之加熱收縮率為0.10%以下之聚醯亞胺薄膜。(5) The copper-clad laminate according to any one of (1) to (4), wherein the elastic modulus is 3 to 7 GPa, the linear expansion coefficient is 5 to 20 ppm/° C. at 50 to 200 ° C, and the humidity expansion coefficient is 25 ppm. A polyimine film having a heat shrinkage ratio of 3% or less and a heat shrinkage rate of 0.10% or less at 200 ° C for 1 hour.

(6)如(1)或(3)~(5)中任一項之舖銅板，其中該黏著劑係選自環氧系黏著劑、丙烯酸系黏著劑、及聚醯亞胺系黏著劑中之至少1種所構成。(6) The copper plate of any one of (1) or (3) to (5), wherein the adhesive is selected from the group consisting of an epoxy adhesive, an acrylic adhesive, and a polyimide adhesive. It is composed of at least one of them.

(7)如(1)或(3)~(6)中任一項之舖銅板，其中該銅箔之黏著側的銅表面粗糙度(Rz)為0.1~10微米。(7) The copper-clad laminate according to any one of (1) or (3) to (6) wherein the copper surface of the copper foil has a surface roughness (Rz) of 0.1 to 10 μm.

(8)如(1)~(7)中任一項之舖銅板，其中全面蝕刻後的尺寸變化率係在－0.10%~0.10%的範圍。(8) The copper-clad laminate according to any one of (1) to (7), wherein the dimensional change rate after the total etching is in the range of -0.10% to 0.10%.

依照本發明，能夠提供一種舖銅板，其能夠形成微細的配線、且即便使用無鉛焊料亦不會變形，作為撓性印刷電路板的材料係有用的。According to the present invention, it is possible to provide a copper-clad laminate which can form fine wiring and which does not deform even when lead-free solder is used, and is useful as a material of a flexible printed circuit board.

本發明之舖銅板係使用聚醯亞胺薄膜作為基材，於該聚醯亞胺薄膜的單面或雙面具有銅板者。The copper-clad laminate of the present invention uses a polyimide film as a substrate, and has a copper plate on one or both sides of the polyimide film.

在此，作為基材之聚醯亞胺薄膜，係由以對苯二胺及4,4’－二胺基二苯醚作為二胺成分、以及以焦蜜石酸二酐及3,3’,4,4’－聯苯四羧酸二酐作為酸二酐成分所形成之聚醯亞胺薄膜。亦即，係以對苯二胺、4,4’－二胺基二苯醚、焦蜜石酸二酐、及3,3’,4,4’－聯苯四羧酸二酐作為必要成分，可以只有此種4種類，或是亦可以是除了此等4種類以外，亦添加少量其他成分所得到之聚醯亞胺薄膜。較佳是二胺成分使用10~50莫耳%對苯二胺、及50~90%4,4’－二胺基二苯醚，酸二酐成分使用50~99莫耳%焦蜜石酸二酐、及1~50莫耳%之3,3’,4,4’聯苯四羧酸二酐所構成之聚醯亞胺薄膜。更佳是彈性模數為3~7GPa，在50~200℃之線膨脹係數為5~20ppm/℃，濕度膨脹係數為25ppm/%RH以下，吸水率3%以下，在200℃ 1小時之加熱收縮率為0.10%以下之聚醯亞胺薄膜。因為對苯二胺太多時會變硬、太少時會變為太柔軟，以1~70莫耳%為佳，以5~60莫耳%為較佳，以10~50莫耳%為更佳。因為4,4’－二胺基二苯醚太多時會變為柔軟、太少時會變為硬，以20~99莫耳%為佳，以40~95莫耳%為較佳，以50~90莫耳%為更佳。因為焦蜜石酸二酐太多時會變硬、太少時會變為柔軟，以50~99莫耳%為佳，以60~90莫耳%為較佳，以65~85莫耳%為更佳。因為3,3’,4,4’－聯苯四羧酸二酐太多時會變為柔軟、太少時會變硬，以1~50莫耳%為佳，以10~40莫耳%為較佳，以15~35莫耳%為更佳。硬度指標之彈性模數以3~7GPa的範圍為佳，大於7GPa時太硬、小於3GPa時太柔軟。線膨脹係數以5~20ppm/℃為佳，大於20ppm/℃時熱所引起的尺寸變化太大，小於5ppm/℃時，因為與配線所使用的金屬之線膨脹係數的差異變大，容易產生翹曲。因為濕度膨脹係數大於25ppm/%RH時，因濕度所產生的尺寸變化太大，所以濕度膨脹係數以25ppm/%RH以下為佳。吸水率大於3%時，因為所吸入水的影響，薄膜的尺寸變化變大，以3%以下為佳。在200℃ 1小時的加熱收縮率大於0.10%時，因為熱所引起的尺寸變化變大，所以加熱收縮率以0.10%以下為佳。Here, the polyimide film as a substrate is composed of p-phenylenediamine and 4,4'-diaminodiphenyl ether as a diamine component, and pyromellitic dianhydride and 3,3'. , 4,4'-biphenyltetracarboxylic dianhydride as a polydiimine film formed by an acid dianhydride component. That is, p-phenylenediamine, 4,4'-diaminodiphenyl ether, pyromellitic dianhydride, and 3,3',4,4'-biphenyltetracarboxylic dianhydride are essential components. There may be only four such types, or a polyimine film obtained by adding a small amount of other components in addition to the above four types. Preferably, the diamine component uses 10 to 50 mol% of p-phenylenediamine, and 50 to 90% of 4,4'-diaminodiphenyl ether, and the acid dianhydride component uses 50 to 99 mol% of pyrogal acid. A polyanthracene film composed of dianhydride and 1 to 50 mol% of 3,3',4,4'biphenyltetracarboxylic dianhydride. More preferably, the modulus of elasticity is 3~7GPa, the coefficient of linear expansion at 50~200°C is 5~20ppm/°C, the coefficient of humidity expansion is below 25ppm/%RH, the water absorption rate is below 3%, and heating at 200°C for 1 hour. A polyimide film having a shrinkage ratio of 0.10% or less. Because it will become too hard when too much p-phenylenediamine is too little, it will become too soft when it is too little, preferably 1~70 mol%, preferably 5~60 mol%, and 10~50 mol%. Better. Because 4,4'-diaminodiphenyl ether will become soft when too much, too little will become hard, preferably 20~99 mol%, preferably 40~95 mol%, 50~90% of the mole is better. Because if the pyrogallate dianhydride is too hard, it will become soft, and when it is too little, it will become soft, preferably 50~99 mol%, preferably 60~90 mol%, 65~85 mol%. For better. Because 3,3',4,4'-biphenyltetracarboxylic dianhydride will become soft when too much, it will become hard when it is too little, preferably 1~50 mol%, 10~40 mol% Preferably, it is preferably 15 to 35 mol%. The modulus of elasticity of the hardness index is preferably in the range of 3 to 7 GPa, too hard when it is greater than 7 GPa, and too soft when it is less than 3 GPa. The linear expansion coefficient is preferably 5-20 ppm/°C, and the dimensional change caused by heat is too large when it is greater than 20 ppm/°C. When it is less than 5 ppm/°C, the difference in linear expansion coefficient of the metal used for wiring becomes large, which is easy to occur. Warping. Since the humidity expansion coefficient is larger than 25 ppm/% RH, the dimensional change due to humidity is too large, so the humidity expansion coefficient is preferably 25 ppm/% RH or less. When the water absorption rate is more than 3%, the dimensional change of the film becomes large due to the influence of the water to be inhaled, and it is preferably 3% or less. When the heat shrinkage rate at 200 ° C for 1 hour is more than 0.10%, the dimensional change due to heat is increased, so the heat shrinkage ratio is preferably 0.10% or less.

聚合方法能夠使用眾所周知的所有方法，例如：(1)預先將芳香族二胺溶解在有機極性溶劑中，隨後將芳香族四羧酸類成分以與芳香族二胺成分總量成為當量的方式加入來聚合之方法。As the polymerization method, all of the well-known methods can be used, for example, (1) the aromatic diamine is dissolved in an organic polar solvent in advance, and then the aromatic tetracarboxylic acid component is added in an equivalent amount to the total amount of the aromatic diamine component. The method of polymerization.

(2)預先將芳香族四羧酸類成分總量加入溶劑中，隨後將芳香族二胺成分以與芳香族四羧酸類成分總量成為等量的方式加入來聚合之方法。(2) A method in which a total amount of the aromatic tetracarboxylic acid component is added to a solvent in advance, and then the aromatic diamine component is added in an amount equivalent to the total amount of the aromatic tetracarboxylic acid component.

(3)將一方的芳香族二胺化合物加入溶劑中後，將相對於反應成分之芳香族四羧酸類化合物以成為95~105莫耳%比率的方式且按照反應所必要的時間混合後，添加另一方的芳香族二胺化合物，接著芳香族四羧酸類化合物以總芳香族二胺成分與總芳香族四羧酸類成分大致等量的方式添加，來進行聚合之方法。(3) After adding one aromatic diamine compound to a solvent, the aromatic tetracarboxylic acid compound of the reaction component is added in a ratio of 95 to 105 mol% and mixed for the time required for the reaction, and then added. The other aromatic diamine compound is added to the aromatic tetracarboxylic acid compound in such a manner that the total aromatic diamine component and the total aromatic tetracarboxylic acid component are substantially equalized to carry out polymerization.

(4)將芳香族四羧酸類化合物加入溶劑中後，將相對於反應成分之一方的芳香族二胺化合物以成為95~105莫耳%比率的方式且按照反應所必要的時間混合後，添加芳香族四羧酸類化合物，接著將另外一方的二胺化合物以總芳香族二胺成分與總芳香族四羧酸類成分大致等量的方式添加，來進行聚合之方法。(4) After the aromatic tetracarboxylic acid compound is added to the solvent, the aromatic diamine compound is added to the reaction component in a ratio of 95 to 105 mol% and mixed for the time required for the reaction, and then added. The aromatic tetracarboxylic acid compound is a method in which the other diamine compound is added in such a manner that the total aromatic diamine component and the total aromatic tetracarboxylic acid component are substantially equalized.

(5)在溶劑中，使一方的芳香族二胺成分及芳香族四羧酸類中任一者過剩的方式來進行反應而調製聚醯胺酸溶液(A)，在另外溶劑中，使另外一方的芳香族二胺成分及芳香族四羧酸類中任一者過剩的方式來進行反應而調製聚醯胺酸溶液(B)。混合如此所得到的各聚醯胺酸溶液(A)及(B)，使其完成聚合之方法。此時，在調製聚醯胺酸溶液(A)時使芳香族二胺成分過剩時，在調製聚醯胺酸溶液(B)時使芳香族四羧酸成分過剩，又，在調製聚醯胺酸溶液(A)時使芳香族四羧酸成分過剩時，在調製聚醯胺酸溶液(B)時使芳香族二胺成分過剩，將聚醯胺酸溶液(A)及(B)以此等反應所使用的總芳香族二胺成分與總芳香族四羧酸類成分為大致等量的方式進行調製。(5) The polyamine acid solution (A) is prepared by reacting one of the aromatic diamine component and the aromatic tetracarboxylic acid in excess in the solvent, and the other solvent is added to the other solvent. The polyaminic acid solution (B) is prepared by reacting one of the aromatic diamine component and the aromatic tetracarboxylic acid in excess. Each of the polyamic acid solutions (A) and (B) thus obtained is mixed to complete the polymerization. In this case, when the polydiamine acid solution (A) is prepared, when the aromatic diamine component is excessive, the aromatic tetracarboxylic acid component is excessively prepared when the polyaminic acid solution (B) is prepared, and the polyamine is further prepared. When the aromatic tetracarboxylic acid component is excessive in the acid solution (A), when the polyamic acid solution (B) is prepared, the aromatic diamine component is excessive, and the polyaminic acid solutions (A) and (B) are used. The total aromatic diamine component used in the reaction is prepared in such a manner that the total aromatic tetracarboxylic acid component is substantially equal.

而且，聚合方式未限定於此等，亦可使用其他眾所周知的方法。Further, the polymerization method is not limited to this, and other well-known methods may be used.

又，在本發明，形成聚醯胺酸溶液所使用的有機溶劑之具體例可舉出的有例如二甲基亞碸、二乙基亞碸等亞碸系溶劑、N,N－二甲基甲醯胺、N,N－二乙基甲醯胺等甲醯胺系溶劑、N,N－二甲基乙醯胺、N,N－二乙基乙醯胺等乙醯胺系溶劑、N－甲基－2－吡咯啶酮、N－乙烯基－2－吡咯啶酮等吡咯啶酮系溶劑、苯酚、鄰、間、或對甲酚、二甲苯酚、鹵化苯酚、兒茶酚等苯酚系溶劑、或是六甲基磷醯胺、γ－丁內酯等非質子性極性溶劑，以單獨或以混合物的方式使用此等為佳，而且亦可使用如二甲苯、甲苯之芳香族烴。Further, in the present invention, specific examples of the organic solvent used for forming the polyaminic acid solution include, for example, an hydrazine solvent such as dimethyl hydrazine or diethyl hydrazine, and N,N-dimethyl group. A methacrylate solvent such as formamide or N,N-diethylformamide, an acetamide solvent such as N,N-dimethylacetamide or N,N-diethylacetamide, or N - Pyrrolidone-based solvents such as methyl-2-pyrrolidone and N-vinyl-2-pyrrolidone, phenol, o-, m-, or p-cresol, xylenol, halogenated phenol, catechol, etc. a solvent or an aprotic polar solvent such as hexamethylphosphonium or γ-butyrolactone, preferably used singly or as a mixture, and an aromatic hydrocarbon such as xylene or toluene may also be used. .

如此進行所得到的聚醯胺酸溶液含有固體成分5~40重量%，以10~30重量%為佳。又，其黏度依照布魯克菲爾德黏度計(Brookfield viscosity meter)之測定值為10~2000Pa．s，以100~1000Pa．s之物為佳，適合用以穩定地輸送液體。又，亦可以將有機溶劑溶液中的聚醯胺酸加以醯亞胺化。The polyamic acid solution thus obtained contains a solid content of 5 to 40% by weight, preferably 10 to 30% by weight. Moreover, the viscosity is 10 to 2000 Pa according to the Brookfield viscosity meter. s, with 100~1000Pa. s is preferred for stable delivery of liquids. Further, the polylysine in the organic solvent solution may be imidized by hydrazine.

接著，說明本發明之聚醯亞胺薄膜的製法。Next, a process for producing the polyimide film of the present invention will be described.

製造聚醯亞胺薄膜之方法可舉出的有將聚醯胺酸溶液流延成薄膜狀，並使其熱脫環化脫溶劑，而得聚醯亞胺薄膜之方法；及在聚醯胺酸溶液混合環化觸媒及脫水劑，來使其化學脫環化而製成凝膠薄膜，再藉由將其加熱脫溶劑而得到聚醯亞胺薄膜之方法，因為後者之方法所得到的聚醯亞胺薄膜能夠將熱膨脹係數抑制得較低，乃是較佳。The method for producing a polyimide film is a method in which a polyaminic acid solution is cast into a film and thermally de-cyclized to obtain a polyimine film; and a polyamine A method of mixing a cyclized catalyst and a dehydrating agent to form a gel film by chemical deaeration, and then desolvating the solution to obtain a polyimine film by a method of the latter It is preferred that the polyimide film can suppress the coefficient of thermal expansion to a low level.

而且，為了提高薄膜的滑性之目的，亦可添加二氧化矽或氧化鋁等各種填料。所使用之此等填料的粒徑以使用平均粒徑為0.1~1微米之物為佳。平均粒徑小於0.1微米時，薄膜的滑性變差，又，平均粒徑大於1微米時製造薄膜時凝聚體的存在增加，乃是不佳。而且，使用平均粒徑大於1微米之填料時，在薄膜表上之大小為20微米以上的突起變為多於10個/5公分×5公分，又，高度為2微米以上的突起變為多於3個/5公分×5公分。由於該尺寸之突起的存在量會造成導電不通，又，因為容易造成戳破光阻膜厚度之不良，乃是不佳。Further, various fillers such as cerium oxide or aluminum oxide may be added for the purpose of improving the smoothness of the film. The particle size of the fillers used is preferably from 0.1 to 1 μm. When the average particle diameter is less than 0.1 μm, the slipperiness of the film is deteriorated, and when the average particle diameter is more than 1 μm, the presence of aggregates at the time of film formation is increased, which is not preferable. Further, when a filler having an average particle diameter of more than 1 μm is used, the protrusion having a size of 20 μm or more on the film surface becomes more than 10/5 cm × 5 cm, and the protrusion having a height of 2 μm or more becomes more At 3/5 cm x 5 cm. Since the amount of protrusions of this size may cause conduction failure, it is not preferable because the thickness of the photoresist film is easily broken.

做為在舖銅板上所具有之隔著黏著劑的銅板所使用之銅箔，其黏著側的銅表面粗糙度(Rz)以0.1~10微米為佳。表面粗糙度比此更粗時，做為撓性印刷電路板在高頻信號區域使用時，表皮效果引起電流流動變為困難，而難以使用在高頻信號區域。在此所稱表面粗糙度(Rz)係指依據JISB 0601－1994「表面粗糙度的定義及表示」之5.1「十點平均粗糙度的定義」所規定之Rz。As the copper foil used for the copper plate with the adhesive interposed on the copper plate, the copper surface roughness (Rz) on the adhesive side is preferably 0.1 to 10 μm. When the surface roughness is thicker than this, when the flexible printed circuit board is used in a high-frequency signal region, the skin effect becomes difficult to cause current flow, and it is difficult to use it in the high-frequency signal region. The surface roughness (Rz) referred to herein means Rz defined in 5.1 "Definition of Ten Point Average Roughness" in accordance with JIS B 0601-1994 "Definition and Expression of Surface Roughness".

聚醯亞胺薄膜之厚度沒有特別限定，以5~125微米為佳，以9~75微米為較佳，以11~55微米為更佳。厚度太厚時作為捲筒狀時會有容易捲取不齊，太薄時會有容易產生皺紋的問題。The thickness of the polyimide film is not particularly limited, and is preferably 5 to 125 μm, preferably 9 to 75 μm, and more preferably 11 to 55 μm. When the thickness is too thick, it may be easily wound up when it is in the form of a roll, and when it is too thin, there is a problem that wrinkles are likely to occur.

在上述的聚醯亞胺薄膜之單面或雙面，隔著黏著劑或是以無黏著劑的方式來形成銅板。使用黏著劑時黏著劑以選自環氧系黏著劑、丙烯酸系黏著劑、及聚醯亞胺系黏著劑中之至少1種為佳。亦能夠在此等黏著劑中，添加使其具有柔軟性的目的之各種橡膠、可塑劑、硬化劑、磷系等的難燃劑、及其他各種添加劑。又，聚醯亞胺系黏著劑的樹脂成分多半是使用以聚醯亞胺系黏著劑為主之熱塑性聚醯亞胺，但是亦可使用熱固性聚醯亞胺。又，聚醯亞胺系黏著劑亦可使用熱塑性聚醯亞胺薄膜作為黏著劑。On one or both sides of the above-mentioned polyimide film, a copper plate is formed by an adhesive or a non-adhesive agent. When the adhesive is used, at least one selected from the group consisting of an epoxy adhesive, an acrylic adhesive, and a polyimide adhesive is preferred. It is also possible to add various rubbers, plasticizers, hardeners, phosphorus-based flame retardants, and the like, which are useful for the purpose of imparting flexibility to these adhesives, and various other additives. Further, most of the resin component of the polyimine-based adhesive is a thermoplastic polyimide which is mainly composed of a polyimide-based adhesive, but a thermosetting polyimide may also be used. Further, as the polyimide-based adhesive, a thermoplastic polyimide film can also be used as the adhesive.

為了不使作為撓性印刷電路板在封裝時產生不良，舖銅板的整面在蝕刻後尺寸變化率以－0.10%~0.10%的範圍內為佳，以－0.05%~0.05%的範圍內為較佳，以－0.03%~0.03%的範圍內為更佳。In order not to cause defects in the package as a flexible printed circuit board, the dimensional change rate of the entire surface of the copper clad plate after etching is preferably in the range of -0.10% to 0.10%, and in the range of -0.05% to 0.05%. Preferably, it is more preferably in the range of -0.03% to 0.03%.

實施例Example

以下藉由實施例來具體地說明。又，實施例所使用之聚醯亞胺薄膜係使用依照合成例1~6的方法製膜所得到之物，但是未限定於此等。又，比較例1~2所使用之聚醯亞胺薄膜係使用依照合成例7~8的方法製膜所得到之物，而且，實施例所使用的黏著劑係使用合成例9~10的方法所調製得到之物，但是未限定於此等。The following is specifically explained by way of examples. Further, the polyimide film used in the examples was obtained by forming a film according to the methods of Synthesis Examples 1 to 6, but it is not limited thereto. Further, the polyimide films used in Comparative Examples 1 and 2 were obtained by film formation according to the methods of Synthesis Examples 7 to 8, and the adhesives used in the examples were the methods of Synthesis Examples 9 to 10. The prepared matter is not limited to this.

又，在合成例所得到的聚醯亞胺薄膜及實施例所得到的舖銅板之各種特性係使用以下方法評價。Further, various properties of the polyimide film obtained in the synthesis example and the copper plate obtained in the examples were evaluated by the following methods.

(1)薄膜厚度使用Mitutoyo製LIGHTMATIC(系列318)厚度計，依照以下進行測定。亦即，從整面任意選擇15處，測定該15處的厚度，算出其平均作為厚度。(1) Film thickness The thickness was measured using the LIGHTMATIC (series 318) thickness meter manufactured by Mitutoyo according to the following. That is, 15 places were arbitrarily selected from the entire surface, and the thickness of the 15 places was measured, and the average was calculated as the thickness.

(2)線膨脹係數使用島津製作所製之TMA－50熱機械分析裝置，以測定溫度範圍：50~200℃、升溫速度：10℃/分鐘的條件測定。使負荷為0.25N，首先從35℃以10℃/分鐘升溫，將溫度上升至300℃。在300℃保持5分鐘，隨後以10℃/分鐘降溫，將溫度下降至35℃，在35℃保持30分鐘，而且，隨後以10℃/分鐘升溫，將溫度上升至300℃。讀取第2次從35℃升溫至300℃時之數據，從50~200℃的部分之平均算出線膨脹係數。(2) The coefficient of linear expansion was measured using a TMA-50 thermomechanical analyzer manufactured by Shimadzu Corporation at a temperature range of 50 to 200 ° C and a temperature increase rate of 10 ° C / minute. The load was set to 0.25 N, and the temperature was first raised from 35 ° C at 10 ° C / min, and the temperature was raised to 300 ° C. The temperature was maintained at 300 ° C for 5 minutes, then lowered at 10 ° C / minute, the temperature was lowered to 35 ° C, held at 35 ° C for 30 minutes, and then the temperature was raised at 10 ° C / minute, and the temperature was raised to 300 ° C. The data obtained when the temperature was raised from 35 ° C to 300 ° C in the second time was read, and the linear expansion coefficient was calculated from the average of the portions of 50 to 200 ° C.

(3)彈性模數使用A&D製RTM－250 TENSIRON萬能試驗機，以拉伸速度：100毫米/分鐘的條件測定。測力傳感器為10Kgf，測定精確度為±0.5%原物尺寸，測定應力－變形曲線，從應力－變形曲線的開始上升部分的直線傾斜(依照2N至15N之2點間的最小平方法算出)、初期試料長度、試料寬度、試料厚度如以下算出。(3) The modulus of elasticity was measured using a RTM-250 TENSIRON universal testing machine manufactured by A&D at a tensile speed of 100 mm/min. The load cell is 10Kgf, the measurement accuracy is ±0.5% of the original size, the stress-strain curve is measured, and the straight line is inclined from the beginning of the stress-deformation curve (calculated according to the least square method between 2N and 15N) The initial sample length, sample width, and sample thickness were calculated as follows.

彈性模數＝(直線部分的傾斜×初期試料長度)/(試料寬度×試料厚度)Modulus of elasticity = (inclination of straight line × initial sample length) / (sample width × sample thickness)

(4)濕度膨脹係數在25℃將薄膜安裝於ULVAC製TM7000爐內，將乾燥空氣送入爐內，乾燥2小時後，從HC－1型水蒸氣產生裝置供氣，將TM7000爐內增濕至90%RH，從此期間之尺寸變化求得濕度膨脹係數。加濕時間為7小時。讀取從3RH%至90RH%之數據，從3~90 RH%的部分之平均算出濕度膨脹係數。(4) Humidity expansion coefficient The film was installed in a ULVAC TM7000 furnace at 25 ° C, and the dry air was sent to the furnace. After drying for 2 hours, the gas was supplied from the HC-1 type steam generating device to humidify the TM7000 furnace. From 90% RH, the coefficient of humidity expansion is obtained from the dimensional change during this period. The humidification time is 7 hours. The data from 3RH% to 90RH% is read, and the humidity expansion coefficient is calculated from the average of the parts from 3 to 90 RH%.

(5)吸水率在98%RH的環境下之乾燥器內靜置2天，評價相對於乾燥時重量之增加重量。(5) The water absorption rate was allowed to stand in a desiccator in an environment of 98% RH for 2 days, and the weight was increased with respect to the weight at the time of drying.

(6)加熱收縮率準備20公分×20公分的薄膜，測定放置在已調整為25℃、60%RH之房間內2天後之薄膜尺寸(L1)，接著在200℃加溫60分鐘後，測定再次放置在已調整為25℃、60%RH之房間內2天後之薄膜尺寸(L2)，依照下述式計算來評價。(6) Heat shrinkage ratio A film of 20 cm × 20 cm was prepared, and the film size (L1) placed in a room adjusted to 25 ° C and 60% RH for 2 days was measured, followed by heating at 200 ° C for 60 minutes. The film size (L2) which was placed again in the room adjusted to 25 ° C and 60% RH for 2 days was measured and evaluated according to the following formula.

加熱收縮率＝－[(L2－L1)/L1]×100Heating shrinkage rate = -[(L2-L1)/L1]×100

(7)尺寸變化率測定舖銅板蝕刻前後之尺寸變化率之進行，係藉由在溫度25℃、濕度60%的條件下，使用CNC畫像處理測定系統(Nikon(股)製、NEXIV VMR－3020)，於舖銅板蝕刻前後，測定在視野：1.165毫米×0.875毫米(4倍)於舖銅板表面的MD方向以210毫米間隔貼上之2片6毫米圖形護帶的圓中心距離來算出。蝕刻前的距離為L3，蝕刻後的距離為L4，銅蝕刻前後都是在測定前將試樣放在溫度25℃、濕度60%的條件下一晚，來排除因聚醯亞胺吸水的影響。尺寸變化率係使用測定2點間距離5次之值的平均值，依照下述式計算得到。(7) Dimensional change rate measurement The dimensional change rate before and after the copper plating was etched was performed by using a CNC image processing system (Nikon, NEXIV VMR-3020) at a temperature of 25 ° C and a humidity of 60%. ), before and after the copper plating, the measurement of the field of view: 1.165 mm × 0.875 mm (4 times) on the surface of the copper plate in the MD direction at 210 mm intervals of 2 pieces of 6 mm The circle center distance of the graphic band is calculated. The distance before etching is L3, and the distance after etching is L4. Before and after copper etching, the sample is placed at a temperature of 25 ° C and a humidity of 60% for the next night to eliminate the influence of water absorption by polyimide. . The dimensional change rate was calculated using the average value of the value of the distance between two points of five points, and was calculated according to the following formula.

尺寸變化率(%)＝[(L3－L4)/(L3)]×100Dimensional change rate (%) = [(L3-L4) / (L3)] × 100

(合成例1)(Synthesis Example 1)

以莫耳比65/35/80/20的比例準備焦蜜石酸二酐(分子量218.12)/3,3’,4,4’－聯苯四羧酸二酐(分子量294.22)/4,4’－二胺基二苯醚(分子量200.24)/對苯二胺(分子量108.14)，以製成為DMAc(N,N－二甲基乙醯胺)中之18.5重量%溶液進行聚合，得到聚醯胺酸。將由乙酸酐(分子量102.09)及異喹啉所構成的轉化劑，以相對於聚醯胺酸溶液為50重量%的比例混合、攪拌。此時，調製成相對於聚醯胺酸之醯胺酸基，乙酸酐及異喹啉各自為2.0及0.4莫耳當量。將所得到的混合物，藉由T型狹縫型模頭流延於旋轉中之100℃的不鏽鋼製滾筒上，得到殘揮發成分為55重量%、厚度約0.20毫米之具有自撐性的凝膠薄膜。將該凝膠薄膜從滾筒剝下，把持其兩端，在加熱爐進行200℃×30秒、350℃×30秒、550℃×30秒處理，得到厚度25微米之聚醯亞胺薄膜。物性如表1所示。Preparation of pyromellitic dianhydride (molecular weight 218.12) / 3,3',4,4'-biphenyltetracarboxylic dianhydride (molecular weight 294.22) / 4,4 in a molar ratio of 65/35/80/20 '-Diaminodiphenyl ether (molecular weight: 200.24) / p-phenylenediamine (molecular weight: 108.14), which was polymerized as a 18.5% by weight solution in DMAc (N,N-dimethylacetamide) to obtain polyfluorene. Amino acid. A conversion agent composed of acetic anhydride (molecular weight: 102.09) and isoquinoline was mixed and stirred at a ratio of 50% by weight based on the polyamic acid solution. At this time, it was prepared to be 2.0 and 0.4 mol equivalent per acetic acid group and polyquinoline relative to the proline group of polylysine. The obtained mixture was cast on a rotating stainless steel drum at 100 ° C by a T-slit die to obtain a self-supporting gel having a residual content of 55 wt% and a thickness of about 0.20 mm. film. The gel film was peeled off from the roll, and both ends were held, and treated in a heating furnace at 200 ° C × 30 seconds, 350 ° C × 30 seconds, and 550 ° C × 30 seconds to obtain a polyimide film having a thickness of 25 μm. The physical properties are shown in Table 1.

(合成例2)(Synthesis Example 2)

以莫耳比65/35/80/20的比例準備焦蜜石酸二酐(分子量218.12)/3,3’,4,4’－聯苯四羧酸二酐(分子量294.22)/4,4’－二胺基二苯醚(分子量200.24)/對苯二胺(分子量108.14)，以製成為DMAc(N,N－二甲基乙醯胺)中之18.5重量%溶液進行聚合，得到聚醯胺酸。將由乙酸酐(分子量102.09)及異喹啉所構成的轉化劑，以相對於聚醯胺酸溶液為50重量%的比例混合、攪拌。此時，調製成相對於聚醯胺酸之醯胺酸基，乙酸酐及異喹啉各自為2.0及0.4莫耳當量。將所得到的混合物，藉由T型狹縫型模頭流延於旋轉中之100℃的不鏽鋼製滾筒上，得到殘揮發成分為55重量%、厚度約0.30毫米之具有自撐性的凝膠薄膜。將該凝膠薄膜從滾筒剝下，把持其兩端，在加熱爐進行200℃×30秒、350℃×30秒、550℃×30秒處理，得到厚度38微米之聚醯亞胺薄膜。物性如表1所示。Preparation of pyromellitic dianhydride (molecular weight 218.12) / 3,3',4,4'-biphenyltetracarboxylic dianhydride (molecular weight 294.22) / 4,4 in a molar ratio of 65/35/80/20 '-Diaminodiphenyl ether (molecular weight: 200.24) / p-phenylenediamine (molecular weight: 108.14), which was polymerized as a 18.5% by weight solution in DMAc (N,N-dimethylacetamide) to obtain polyfluorene. Amino acid. A conversion agent composed of acetic anhydride (molecular weight: 102.09) and isoquinoline was mixed and stirred at a ratio of 50% by weight based on the polyamic acid solution. At this time, it was prepared to be 2.0 and 0.4 mol equivalent per acetic acid group and polyquinoline relative to the proline group of polylysine. The obtained mixture was cast on a rotating stainless steel drum of 100 ° C by a T-slit die to obtain a self-supporting gel having a residual content of 55 wt% and a thickness of about 0.30 mm. film. The gel film was peeled off from the roll, and both ends were held, and subjected to treatment at 200 ° C × 30 seconds, 350 ° C × 30 seconds, and 550 ° C × 30 seconds in a heating furnace to obtain a polyimide film having a thickness of 38 μm. The physical properties are shown in Table 1.

(合成例3)(Synthesis Example 3)

以莫耳比3/1/3/1的比例準備焦蜜石酸二酐(分子量218.12)/3,3’,4,4’－聯苯四羧酸二酐(分子量294.22)/4,4’－二胺基二苯醚(分子量200.24)/對苯二胺(分子量108.14)，以製成為DMAc(N,N－二甲基乙醯胺)中之18.5重量%溶液進行聚合，得到聚醯胺酸。將由乙酸酐(分子量102.09)及異喹啉所構成的轉化劑，以相對於聚醯胺酸溶液為50重量%的比例混合、攪拌。此時，調製成相對於聚醯胺酸之醯胺酸基，乙酸酐及異喹啉各自為2.0及0.4莫耳當量。將所得到的混合物，藉由T型狹縫型模頭流延於旋轉中之100℃的不鏽鋼製滾筒上，得到殘揮發成分為55重量%、厚度約0.20毫米之具有自撐性的凝膠薄膜。將該凝膠薄膜從滾筒剝下，把持其兩端，在加熱爐進行200℃×30秒、350℃×30秒、550℃×30秒處理，得到厚度25微米之聚醯亞胺薄膜。物性如表1所示。Preparation of pyromellitic dianhydride (molecular weight 218.12) / 3,3',4,4'-biphenyltetracarboxylic dianhydride (molecular weight 294.22) / 4,4 in a molar ratio of 3/1/3/1 '-Diaminodiphenyl ether (molecular weight: 200.24) / p-phenylenediamine (molecular weight: 108.14), which was polymerized as a 18.5% by weight solution in DMAc (N,N-dimethylacetamide) to obtain polyfluorene. Amino acid. A conversion agent composed of acetic anhydride (molecular weight: 102.09) and isoquinoline was mixed and stirred at a ratio of 50% by weight based on the polyamic acid solution. At this time, it was prepared to be 2.0 and 0.4 mol equivalent per acetic acid group and polyquinoline relative to the proline group of polylysine. The obtained mixture was cast on a rotating stainless steel drum at 100 ° C by a T-slit die to obtain a self-supporting gel having a residual content of 55 wt% and a thickness of about 0.20 mm. film. The gel film was peeled off from the roll, and both ends were held, and treated in a heating furnace at 200 ° C × 30 seconds, 350 ° C × 30 seconds, and 550 ° C × 30 seconds to obtain a polyimide film having a thickness of 25 μm. The physical properties are shown in Table 1.

(合成例4)(Synthesis Example 4)

以莫耳比4/1/4/1的比例準備焦蜜石酸二酐(分子量218.12)/3,3’,4,4’－聯苯四羧酸二酐(分子量294.22)/4,4’－二胺基二苯醚(分子量200.24)/對苯二胺(分子量108.14)，以製成為DMAc(N,N－二甲基乙醯胺)中之18.5重量%溶液進行聚合，得到聚醯胺酸。將由乙酸酐(分子量102.09)及異喹啉所構成的轉化劑，以相對於聚醯胺酸溶液為50重量%的比例混合、攪拌。此時，調製成相對於聚醯胺酸之醯胺酸基，乙酸酐及異喹啉各自為2.0及0.4莫耳當量。將所得到的混合物，藉由T型狹縫型模頭流延於旋轉中之100℃的不鏽鋼製滾筒上，得到殘揮發成分為55重量%、厚度約0.10毫米之具有自撐性的凝膠薄膜。將該凝膠薄膜從滾筒剝下，把持其兩端，在加熱爐進行200℃×30秒、350℃×30秒、550℃×30秒處理，得到厚度12.5微米之聚醯亞胺薄膜。物性如表1所示。Preparation of pyromellitic dianhydride (molecular weight 218.12) / 3,3',4,4'-biphenyltetracarboxylic dianhydride (molecular weight 294.22) / 4,4 in a molar ratio of 4/1/4/1 '-Diaminodiphenyl ether (molecular weight: 200.24) / p-phenylenediamine (molecular weight: 108.14), which was polymerized as a 18.5% by weight solution in DMAc (N,N-dimethylacetamide) to obtain polyfluorene. Amino acid. A conversion agent composed of acetic anhydride (molecular weight: 102.09) and isoquinoline was mixed and stirred at a ratio of 50% by weight based on the polyamic acid solution. At this time, it was prepared to be 2.0 and 0.4 mol equivalent per acetic acid group and polyquinoline relative to the proline group of polylysine. The obtained mixture was cast on a rotating stainless steel drum at 100 ° C by a T-slit die to obtain a self-supporting gel having a residual content of 55 wt% and a thickness of about 0.10 mm. film. The gel film was peeled off from the roll, and both ends were held, and subjected to treatment at 200 ° C × 30 seconds, 350 ° C × 30 seconds, and 550 ° C × 30 seconds in a heating furnace to obtain a polyimide film having a thickness of 12.5 μm. The physical properties are shown in Table 1.

(合成例5)(Synthesis Example 5)

以莫耳比9/1/8/2的比例準備焦蜜石酸二酐(分子量218.12)/3,3’,4,4’－聯苯四羧酸二酐(分子量294.22)/4,4’－二胺基二苯醚(分子量200.24)/對苯二胺(分子量108.14)，以製成為DMAc(N,N－二甲基乙醯胺)中之18.5重量%溶液進行聚合，得到聚醯胺酸。將由乙酸酐(分子量102.09)及異喹啉所構成的轉化劑，以相對於聚醯胺酸溶液為50重量%的比例混合、攪拌。此時，調製成相對於聚醯胺酸之醯胺酸基，乙酸酐及異喹啉各自為2.0及0.4莫耳當量。將所得到的混合物，藉由T型狹縫型模頭流延於旋轉中之100℃的不鏽鋼製滾筒上，得到殘揮發成分為55重量%、厚度約0.07毫米之具有自撐性的凝膠薄膜。將該凝膠薄膜從滾筒剝下，把持其兩端，在加熱爐進行200℃×30秒、350℃×30秒、550℃×30秒處理，得到厚度9微米之聚醯亞胺薄膜。物性如表1所示。Preparation of pyromellitic dianhydride (molecular weight 218.12) / 3,3',4,4'-biphenyltetracarboxylic dianhydride (molecular weight 294.22) / 4,4 in a molar ratio of 9/1/8/2 '-Diaminodiphenyl ether (molecular weight: 200.24) / p-phenylenediamine (molecular weight: 108.14), which was polymerized as a 18.5% by weight solution in DMAc (N,N-dimethylacetamide) to obtain polyfluorene. Amino acid. A conversion agent composed of acetic anhydride (molecular weight: 102.09) and isoquinoline was mixed and stirred at a ratio of 50% by weight based on the polyamic acid solution. At this time, it was prepared to be 2.0 and 0.4 mol equivalent per acetic acid group and polyquinoline relative to the proline group of polylysine. The obtained mixture was cast on a rotating stainless steel drum of 100 ° C by a T-slit die to obtain a self-supporting gel having a residual content of 55 wt% and a thickness of about 0.07 mm. film. The gel film was peeled off from the roll, and both ends were held, and treated in a heating furnace at 200 ° C × 30 seconds, 350 ° C × 30 seconds, and 550 ° C × 30 seconds to obtain a polyimide film having a thickness of 9 μm. The physical properties are shown in Table 1.

(合成例6)(Synthesis Example 6)

以莫耳比3/2/3/2的比例準備焦蜜石酸二酐(分子量218.12)/3,3’,4,4’－聯苯四羧酸二酐(分子量294.22)/4,4’－二胺基二苯醚(分子量200.24)/對苯二胺(分子量108.14)，以製成為DMAc(N,N－二甲基乙醯胺)中之18.5重量%溶液進行聚合，得到聚醯胺酸。將由乙酸酐(分子量102.09)及異喹啉所構成的轉化劑，以相對於聚醯胺酸溶液為50重量%的比例混合、攪拌。此時，調製成相對於聚醯胺酸之醯胺酸基，乙酸酐及異喹啉各自為2.0及0.4莫耳當量。將所得到的混合物，藉由T型狹縫型模頭流延於旋轉中之100℃的不鏽鋼製滾筒上，得到殘揮發成分為55重量%、厚度約0.05毫米之具有自撐性的凝膠薄膜。將該凝膠薄膜從滾筒剝下，把持其兩端，在加熱爐進行200℃×30秒、350℃×30秒、550℃×30秒處理，得到厚度6微米之聚醯亞胺薄膜。物性如表1所示。Preparation of pyromellitic dianhydride (molecular weight 218.12) / 3,3',4,4'-biphenyltetracarboxylic dianhydride (molecular weight 294.22) / 4,4 in a molar ratio of 3/2/3/2 '-Diaminodiphenyl ether (molecular weight: 200.24) / p-phenylenediamine (molecular weight: 108.14), which was polymerized as a 18.5% by weight solution in DMAc (N,N-dimethylacetamide) to obtain polyfluorene. Amino acid. A conversion agent composed of acetic anhydride (molecular weight: 102.09) and isoquinoline was mixed and stirred at a ratio of 50% by weight based on the polyamic acid solution. At this time, it was prepared to be 2.0 and 0.4 mol equivalent per acetic acid group and polyquinoline relative to the proline group of polylysine. The obtained mixture was cast on a rotating stainless steel drum at 100 ° C by a T-slit die to obtain a self-supporting gel having a residual content of 55 wt% and a thickness of about 0.05 mm. film. The gel film was peeled off from the roll, and both ends were held, and treated in a heating furnace at 200 ° C × 30 seconds, 350 ° C × 30 seconds, and 550 ° C × 30 seconds to obtain a polyimide film having a thickness of 6 μm. The physical properties are shown in Table 1.

(合成例7)(Synthesis Example 7)

以莫耳比50/50的比例準備焦蜜石酸二酐(分子量218.12)/4,4’－二胺基二苯醚(分子量200.24)，以製成為DMF(N,N－二甲基甲醯胺)中之18.5重量%溶液進行聚合，得到聚醯胺酸。將由乙酸酐(分子量102.09)及異喹啉所構成的轉化劑，以相對於聚醯胺酸溶液為50重量%的比例混合、攪拌。此時，調製成相對於聚醯胺酸之醯胺酸基，乙酸酐及異喹啉各自為2.0及0.4莫耳當量。將所得到的混合物，藉由T型狹縫型模頭流延於旋轉中之100℃的不鏽鋼製滾筒上，得到殘揮發成分為55重量%、厚度約0.20毫米之具有自撐性的凝膠薄膜。將該凝膠薄膜從滾筒剝下，把持其兩端，在加熱爐進行200℃×30秒、350℃×30秒、550℃×30秒處理，得到厚度25微米之聚醯亞胺薄膜。物性如表1所示。Prepare pyromic acid dianhydride (molecular weight 218.12) / 4,4'-diaminodiphenyl ether (molecular weight 200.24) in a molar ratio of 50/50 to prepare DMF (N, N-dimethyl A) The 18.5 wt% solution in the decylamine was polymerized to give polylysine. A conversion agent composed of acetic anhydride (molecular weight: 102.09) and isoquinoline was mixed and stirred at a ratio of 50% by weight based on the polyamic acid solution. At this time, it was prepared to be 2.0 and 0.4 mol equivalent per acetic acid group and polyquinoline relative to the proline group of polylysine. The obtained mixture was cast on a rotating stainless steel drum at 100 ° C by a T-slit die to obtain a self-supporting gel having a residual content of 55 wt% and a thickness of about 0.20 mm. film. The gel film was peeled off from the roll, and both ends were held, and treated in a heating furnace at 200 ° C × 30 seconds, 350 ° C × 30 seconds, and 550 ° C × 30 seconds to obtain a polyimide film having a thickness of 25 μm. The physical properties are shown in Table 1.

(合成例8)(Synthesis Example 8)

以莫耳比50/50的比例準備焦蜜石酸二酐(分子量218.12)/C(分子量200.20)，以製成為DMF(N,N－二甲基甲醯胺)中之18.5重量%溶液進行聚合，得到聚醯胺酸。將由乙酸酐(分子量102.09)及異喹啉所構成的轉化劑，以相對於聚醯胺酸溶液為50重量%的比例混合、攪拌。此時，調製成相對於聚醯胺酸之醯胺酸基，乙酸酐及異喹啉各自為2.0及0.4莫耳當量。將所得到的混合物，藉由T型狹縫型模頭流延於旋轉中之100℃的不鏽鋼製滾筒上，得到殘揮發成分為55重量%、厚度約0.10毫米之具有自撐性的凝膠薄膜。將該凝膠薄膜從滾筒剝下，把持其兩端，在加熱爐進行200℃×30秒、350℃×30秒、550℃×30秒處理，得到厚度12.5微米之聚醯亞胺薄膜。物性如表1所示。Pyruvate dianhydride (molecular weight 218.12) / C (molecular weight 200.20) was prepared at a molar ratio of 50/50 to prepare a 18.5% by weight solution in DMF (N,N-dimethylformamide). Polymerization gives polyamic acid. A conversion agent composed of acetic anhydride (molecular weight: 102.09) and isoquinoline was mixed and stirred at a ratio of 50% by weight based on the polyamic acid solution. At this time, it was prepared to be 2.0 and 0.4 mol equivalent per acetic acid group and polyquinoline relative to the proline group of polylysine. The obtained mixture was cast on a rotating stainless steel drum at 100 ° C by a T-slit die to obtain a self-supporting gel having a residual content of 55 wt% and a thickness of about 0.10 mm. film. The gel film was peeled off from the roll, and both ends were held, and subjected to treatment at 200 ° C × 30 seconds, 350 ° C × 30 seconds, and 550 ° C × 30 seconds in a heating furnace to obtain a polyimide film having a thickness of 12.5 μm. The physical properties are shown in Table 1.

(合成例9)(Synthesis Example 9)

在600重量份甲基異丁基酮中，於30℃混合攪拌50重量份油化Shell(股)製環氧樹脂「EPICOAT」834、100重量份東都化成(股)含磷環氧樹脂FX279BEK75、6重量份住友化學(股)製硬化劑4,4’－DDS、100重量份JSR(股)NBR(PNR－1H)、30重量份昭和電工(股)製氫氧化鋁，得到黏著劑溶液。50 parts by weight of an epoxy resin "EPICOAT" 834, 100 parts by weight of Dongdu Chemicals Co., Ltd. phosphorus-containing epoxy resin FX279BEK75, mixed with 30 parts by weight of methyl isobutyl ketone at 30 ° C, 6 parts by weight of a hardener 4,4'-DDS made by Sumitomo Chemical Co., Ltd., 100 parts by weight of JSR (shared) NBR (PNR-1H), and 30 parts by weight of aluminum hydroxide produced by Showa Denko Co., Ltd., to obtain an adhesive solution.

(合成例10)(Synthesis Example 10)

在600重量份甲基異丁基酮中，於30℃混合攪拌50重量份油化Shell(股)製環氧樹脂「EPICOAT」828、80重量份東都化成(股)含磷環氧樹脂FX279BEK75、6重量份住友化學(股)製硬化劑4,4’－DDS、100重量份JSR(股)NBR(PNR－1H)、10重量份昭和電工(股)製氫氧化鋁，得到黏著劑溶液。50 parts by weight of an epoxy resin "EPICOAT" 828, 80 parts by weight of Dongdu Chemicals Co., Ltd. phosphorus-containing epoxy resin FX279BEK75, mixed with 30 parts by weight of methyl isobutyl ketone at 30 ° C, 6 parts by weight of a hardener 4,4'-DDS made by Sumitomo Chemical Co., Ltd., 100 parts by weight of JSR (shared) NBR (PNR-1H), and 10 parts by weight of aluminum hydroxide produced by Showa Denko Co., Ltd., to obtain an adhesive solution.

表中的略號：PMDA(焦蜜石酸二酐)BPDA(3,3’,4,4’－聯苯四羧酸二酐)4,4’－ODA(4,4’－二胺基二苯醚)PPD(對苯二胺) Abbreviation in the table: PMDA (pyristate dianhydride) BPDA (3,3',4,4'-biphenyltetracarboxylic dianhydride) 4,4'-ODA (4,4'-diamino group Diphenyl ether) PPD (p-phenylenediamine)

(實施例1)(Example 1)

使用在合成例1製膜所得到的聚醯亞胺薄膜，在其一面塗布合成例9的黏著劑，並於150℃×5分鐘加熱乾燥，來形成乾燥膜厚度10微米的黏著劑層。將該一面具有黏著劑之聚醯亞胺薄膜、與表面粗糙度(Rz)為1.5微米之1/2英兩銅箔(古河CIRCUIT FOIL(股)製、FO－WS18)，使用熱輥層壓機，以層壓溫度160℃、層壓壓力196N/cm(20kgf/cm)、層壓速度1.5公尺/分鐘的條件進行熱層壓，來製造單面撓性舖銅板。使用所得到的舖銅板，測定銅全面蝕刻前後之尺寸變化率時，尺寸變化率為0.010%。Using the polyimide film obtained by the film formation of Synthesis Example 1, the adhesive of Synthesis Example 9 was applied on one surface, and dried by heating at 150 ° C for 5 minutes to form an adhesive layer having a dry film thickness of 10 μm. A polyimide film having an adhesive on one side and a 1/2 inch copper foil having a surface roughness (Rz) of 1.5 μm (Furukawa CIRCUIT FOIL Co., FO-WS18), using a hot roll laminator A single-sided flexible copper clad laminate was produced by heat lamination at a lamination temperature of 160 ° C, a lamination pressure of 196 N/cm (20 kgf/cm), and a lamination speed of 1.5 m/min. Using the obtained copper plate, the dimensional change rate of the copper before and after the overall etching was measured, and the dimensional change rate was 0.010%.

(實施例2)(Example 2)

除了使用在合成例5製膜所得到的聚醯亞胺薄膜以外，完全與實施例1同樣地進行，來製造單面舖銅板。測定銅全面蝕刻前後之尺寸變化率時，尺寸變化率為0.015%。A single-sided copper clad laminate was produced in the same manner as in Example 1 except that the polyimide film obtained by the film formation in Synthesis Example 5 was used. When the dimensional change rate of copper before and after full etching was measured, the dimensional change rate was 0.015%.

(實施例3)(Example 3)

除了使用在合成例4製膜所得到的聚醯亞胺薄膜以外，完全與實施例1同樣地進行，來製造單面舖銅板。測定銅全面蝕刻前後之尺寸變化率時，尺寸變化率為0.002%。A single-sided copper clad laminate was produced in the same manner as in Example 1 except that the polyimide film obtained by the film formation of Synthesis Example 4 was used. When the dimensional change rate of the copper before and after the overall etching was measured, the dimensional change rate was 0.002%.

(實施例4)(Example 4)

除了使用在合成例6製膜所得到的聚醯亞胺薄膜以外，完全與實施例1同樣地進行，來製造單面舖銅板。測定銅全面蝕刻前後之尺寸變化率時，尺寸變化率為0.048%。A single-sided copper clad laminate was produced in the same manner as in Example 1 except that the polyimide film obtained by the film formation of Synthesis Example 6 was used. When the dimensional change rate of copper before and after full etching was measured, the dimensional change rate was 0.048%.

(實施例5)(Example 5)

使用在合成例2製膜所得到的聚醯亞胺薄膜，在真空槽到達壓力1×10－3Pa後，在氬氣壓力1×10－1Pa，藉由DC磁控管濺鍍機將鎳/鉻＝95/5(重量比)的鎳鉻合金以厚度5奈米的方式濺鍍於一面，進而以厚度50奈米的方式濺鍍銅。接著，藉由使用硫酸銅浴之電解鍍金以2A/dm2的電流密度條件層積6微米厚度的銅層，來製造單面舖銅板。又，硫酸銅浴的組成係使用在80克/升五水合硫酸銅、200克/升硫酸、50毫克/升鹽酸中添加適量的添加劑而成之溶液。使用所得到的舖銅板，測定銅全面蝕刻前後之尺寸變化率時，尺寸變化率為0.008%。Using the polyimide film obtained by the film formation in Synthesis Example 2, after the vacuum tank reached a pressure of 1 × 10 -3 Pa, the pressure was 1 × 10 -1 Pa at an argon pressure, and the nickel was controlled by a DC magnetron sputtering machine. A chromium-95/5 (by weight) nickel-chromium alloy was sputtered on one side with a thickness of 5 nm, and copper was sputter-coated at a thickness of 50 nm. Next, a single-sided copper clad laminate was produced by laminating a copper layer having a thickness of 6 μm at a current density of 2 A/dm 2 by electrolytic gold plating using a copper sulfate bath. Further, the composition of the copper sulfate bath was a solution obtained by adding an appropriate amount of an additive to 80 g/liter of copper sulfate pentahydrate, 200 g/liter of sulfuric acid, and 50 mg/liter of hydrochloric acid. Using the obtained copper plate, the dimensional change rate of the copper before and after the overall etching was measured, and the dimensional change rate was 0.008%.

(實施例6)(Example 6)

使用在合成例3製膜所得到的聚醯亞胺薄膜，在其兩面塗布合成例10的黏著劑，並於150℃×5分鐘加熱乾燥，來形成乾燥膜厚度10微米的黏著劑層。將該兩面具有黏著劑之聚醯亞胺薄膜、與表面粗糙度(Rz)為1.5微米之1/2英兩銅箔(古河CIRCUIT FOIL(股)製、FO－WS18)，使用熱輥層壓機，以層壓溫度160℃、層壓壓力196N/cm(20kgf/cm)、層壓速度1.5公尺/分鐘的條件進行熱層壓，來製造兩面舖銅板。使用所得到的兩面舖銅板，測定銅全面蝕刻前後之尺寸變化率時，尺寸變化率為－0.008%。Using the polyimide film obtained by the film formation of Synthesis Example 3, the adhesive of Synthesis Example 10 was applied to both surfaces thereof, and dried by heating at 150 ° C for 5 minutes to form an adhesive layer having a dry film thickness of 10 μm. A polyimide film having an adhesive on both sides and a 1/2 inch copper foil having a surface roughness (Rz) of 1.5 μm (Furukawa CIRCUIT FOIL Co., FO-WS18) was used, and a hot roll laminator was used. A double-sided copper clad laminate was produced by heat lamination at a lamination temperature of 160 ° C, a lamination pressure of 196 N/cm (20 kgf/cm), and a lamination speed of 1.5 m/min. Using the obtained two-sided copper plate, the dimensional change rate was -0.008% when the dimensional change rate of the copper before and after the overall etching was measured.

(實施例7)(Example 7)

使用在合成例2製膜所得到的聚醯亞胺薄膜，在真空槽到達壓力1×10－3Pa後，在氬氣壓力1×10－1Pa，藉由DC磁控管濺鍍機將鎳/鉻＝90/10(重量比)的鎳鉻合金以厚度3奈米的方式濺鍍於兩面，進而以厚度10奈米的方式濺鍍銅。接著，藉由使用硫酸銅浴之電解鍍金以2A/dm2的電流密度條件層積5微米厚度的銅層，來製造雙面舖銅板。又，硫酸銅浴的組成係使用在80克/升五水合硫酸銅、200克/升硫酸、50毫克/升鹽酸中添加適量的添加劑而成之溶液。使用所得到的雙面舖銅板，測定銅全面蝕刻前後之尺寸變化率時，尺寸變化率為0.005%。Using the polyimide film obtained by the film formation in Synthesis Example 2, after the vacuum tank reached a pressure of 1 × 10 -3 Pa, the pressure was 1 × 10 -1 Pa at an argon pressure, and the nickel was controlled by a DC magnetron sputtering machine. A nickel-chromium alloy having a chromium content of 90/10 (weight ratio) was sputtered on both sides in a thickness of 3 nm, and copper was sputtered in a thickness of 10 nm. Next, a double-layer copper clad laminate was produced by laminating a copper layer having a thickness of 5 μm at a current density of 2 A/dm 2 by electrolytic gold plating using a copper sulfate bath. Further, the composition of the copper sulfate bath was a solution obtained by adding an appropriate amount of an additive to 80 g/liter of copper sulfate pentahydrate, 200 g/liter of sulfuric acid, and 50 mg/liter of hydrochloric acid. Using the obtained double-sided copper plate, the dimensional change rate was 0.005% when the dimensional change rate of the copper before and after the overall etching was measured.

(實施例8)(Example 8)

使用在合成例6製膜所得到的聚醯亞胺薄膜，在真空槽到達壓力1×10－3Pa後，在氬氣壓力1×10－1Pa，藉由DC磁控管濺鍍機將鎳/鉻＝90/10(重量比)的鎳鉻合金以厚度3奈米的方式濺鍍於一面，進而以厚度10奈米的方式濺鍍銅。接著，藉由使用硫酸銅浴之電解鍍金以2A/dm2的電流密度條件層積12微米厚度的銅層，來製造單面舖銅板。又，硫酸銅浴的組成係使用在80克/升五水合硫酸銅、200克/升硫酸、50毫克/升鹽酸中添加適量的添加劑而成之溶液。使用所得到的單面舖銅板，在形成有銅層的面之相反面塗布合成例8的黏著劑，並於150℃×5分鐘加熱乾燥，來形成乾燥膜厚度10微米的黏著劑層。將該一面具有黏著劑之聚醯亞胺薄膜、與表面粗糙度(Rz)為1.5微米之1/3英兩銅箔(古河CIRCUIT FOTL(股)製、FO－WS12)，使用熱輥層壓機，以層壓溫度160℃、層壓壓力196N/cm(20kgf/cm)、層壓速度1.5公尺/分鐘的條件進行熱層壓，來製造單面隔著黏結劑、另一面無黏結劑的雙面撓性舖銅板。使用所得到的雙面舖銅板，測定銅全面蝕刻前後之尺寸變化率時，尺寸變化率為－0.052%。Using the polyimide film obtained by the film formation in Synthesis Example 6, after the vacuum tank reached a pressure of 1 × 10 -3 Pa, the pressure was 1 × 10 -1 Pa at an argon pressure, and the nickel was controlled by a DC magnetron sputtering machine. A nickel-chromium alloy having a chromium content of 90/10 (weight ratio) was sputter-plated to one side in a thickness of 3 nm, and copper was sputter-coated at a thickness of 10 nm. Next, a single-sided copper clad laminate was produced by laminating a copper layer having a thickness of 12 μm at a current density of 2 A/dm 2 by electrolytic gold plating using a copper sulfate bath. Further, the composition of the copper sulfate bath was a solution obtained by adding an appropriate amount of an additive to 80 g/liter of copper sulfate pentahydrate, 200 g/liter of sulfuric acid, and 50 mg/liter of hydrochloric acid. Using the obtained single-sided copper plate, the adhesive of Synthesis Example 8 was applied to the surface opposite to the surface on which the copper layer was formed, and dried by heating at 150 ° C for 5 minutes to form an adhesive layer having a dry film thickness of 10 μm. A polyimide film having an adhesive on one side and a 1/3 inch copper foil having a surface roughness (Rz) of 1.5 μm (Furukawa CIRCUIT FOTL (share), FO-WS12), using a hot roll laminator Hot lamination at a lamination temperature of 160 ° C, a lamination pressure of 196 N/cm (20 kgf/cm), and a lamination speed of 1.5 m/min to produce a single-sided adhesive without a binder and a non-adhesive agent on the other side. Double-sided flexible copper clad laminate. The dimensional change rate was -0.052% when the dimensional change rate of the copper before and after the overall etching was measured using the obtained double-layer copper plate.

(比較例1)(Comparative Example 1)

除了使用在合成例7製膜所得到的聚醯亞胺薄膜以外，完全與實施例1同樣地進行，來製造單面舖銅板。測定銅全面蝕刻前後之尺寸變化率時，尺寸變化率為－0.122%。A single-sided copper clad laminate was produced in the same manner as in Example 1 except that the polyimide film obtained by the film formation in Synthesis Example 7 was used. When the dimensional change rate of copper before and after full etching was measured, the dimensional change rate was -0.122%.

(比較例2)(Comparative Example 2)

除了使用在合成例8製膜所得到的聚醯亞胺薄膜以外，完全與實施例1同樣地進行，來製造單面舖銅板。測定銅全面蝕刻前後之尺寸變化率時，尺寸變化率為－0.132%。A single-sided copper clad laminate was produced in the same manner as in Example 1 except that the polyimide film obtained by the film formation of Synthesis Example 8 was used. When the dimensional change rate of copper before and after full etching was measured, the dimensional change rate was -0.132%.

(比較例3)(Comparative Example 3)

除了使用在合成例7製膜所得到的聚醯亞胺薄膜以外，完全與實施例8同樣地進行，來製造雙面舖銅板。測定銅全面蝕刻前後之尺寸變化率時，尺寸變化率為－0.105%。A double-sided copper clad laminate was produced in the same manner as in Example 8 except that the polyimide film obtained by the film formation in Synthesis Example 7 was used. When the dimensional change rate of copper before and after full etching was measured, the dimensional change rate was -0.15%.

整理實施例1~8及比較例1~3的尺寸變化率，如表2所示。The dimensional change ratios of Examples 1 to 8 and Comparative Examples 1 to 3 were as shown in Table 2.

產業上之利用可能性Industrial use possibility

依照本發明，能夠提供一種舖銅板，適合作為尺寸安定性或耐熱性優良的撓性印刷電路板用。According to the present invention, it is possible to provide a copper clad laminate which is suitable for use as a flexible printed circuit board excellent in dimensional stability or heat resistance.

Claims (6)

一種舖銅板，係透過黏著劑，在以對苯二胺及4,4’-二胺基二苯醚作為二胺成分、以及以焦蜜石酸二酐及3,3’,4,4’-聯苯四羧酸二酐作為酸二酐成分所形成之彈性模數為3~7GPa、在50~200℃之線膨脹係數為5~20ppm/℃、濕度膨脹係數為25ppm/%RH以下、吸水率為3%以下，在200℃ 1小時之加熱收縮率為0.10%以下之聚醯亞胺薄膜之單面或雙面具有銅板，全面蝕刻後的尺寸變化率係在-0.10%~0.10%的範圍。 A copper-plated board which is made of an adhesive, using p-phenylenediamine and 4,4'-diaminodiphenyl ether as a diamine component, and pyromellitic dianhydride and 3,3', 4, 4' - biphenyltetracarboxylic dianhydride has an elastic modulus of 3 to 7 GPa as an acid dianhydride component, a linear expansion coefficient of 5 to 20 ppm/° C. at 50 to 200 ° C, and a humidity expansion coefficient of 25 ppm/% RH or less. The water absorption rate is 3% or less, and the polyimide film having a heat shrinkage ratio of 0.10% or less at 200 ° C for 1 hour has a copper plate on one side or both sides, and the dimensional change rate after the overall etching is -0.10% to 0.10%. The scope. 一種舖銅板，係不透過黏著劑在以對苯二胺及4,4’-二胺基二苯醚作為二胺成分、以及以焦蜜石酸二酐及3,3’,4,4’-聯苯四羧酸二酐作為酸二酐成分所形成之彈性模數為3~7GPa、在50~200℃之線膨脹係數為5~20ppm/℃、濕度膨脹係數為25ppm/%RH以下、吸水率為3%以下，在200℃ 1小時之加熱收縮率為0.10%以下之聚醯亞胺薄膜之單面或雙面具有銅板，全面蝕刻後的尺寸變化率係在-0.10%~0.10%的範圍。 A copper-clad laminate which is impervious to adhesives in the presence of p-phenylenediamine and 4,4'-diaminodiphenyl ether as a diamine component, and with pyromellitic dianhydride and 3,3',4,4' - biphenyltetracarboxylic dianhydride has an elastic modulus of 3 to 7 GPa as an acid dianhydride component, a linear expansion coefficient of 5 to 20 ppm/° C. at 50 to 200 ° C, and a humidity expansion coefficient of 25 ppm/% RH or less. The water absorption rate is 3% or less, and the polyimide film having a heat shrinkage ratio of 0.10% or less at 200 ° C for 1 hour has a copper plate on one side or both sides, and the dimensional change rate after the overall etching is -0.10% to 0.10%. The scope. 一種舖銅板，係透過黏著劑，在以對苯二胺及4,4’-二胺基二苯醚作為二胺成分、以及以焦蜜石酸二酐及3,3’,4,4’-聯苯四羧酸二酐作為酸二酐成分所形成之彈性模數為3~7GPa、在50~200℃之線膨脹係數為5~20ppm/℃、濕度膨脹係數為25ppm/%RH以下、吸水率為3%以下，在200℃ 1小時之加熱收縮率為0.10%以下之聚 醯亞胺薄膜之一面具有銅板、另一面則未透過黏著劑而具有銅板，全面蝕刻後的尺寸變化率係在-0.10%~0.10%的範圍。 A copper-plated board which is made of an adhesive, using p-phenylenediamine and 4,4'-diaminodiphenyl ether as a diamine component, and pyromellitic dianhydride and 3,3', 4, 4' - biphenyltetracarboxylic dianhydride has an elastic modulus of 3 to 7 GPa as an acid dianhydride component, a linear expansion coefficient of 5 to 20 ppm/° C. at 50 to 200 ° C, and a humidity expansion coefficient of 25 ppm/% RH or less. The water absorption rate is 3% or less, and the heat shrinkage rate at 200 ° C for 1 hour is 0.10% or less. The bismuth imide film has a copper plate on one side and a copper plate on the other side without an adhesive, and the dimensional change rate after the overall etching is in the range of -0.10% to 0.10%. 如申請專利範圍第1至3項中任一項之舖銅板，其中聚醯亞胺薄膜的二胺成分係10~50莫耳%之對苯二胺及50~90莫耳%之4,4’-二胺基二苯醚，酸二酐成分係50~99莫耳%之焦蜜石酸二酐及1~50莫耳%之3,3’,4,4’-聯苯四羧酸二酐。 The copper-clad laminate according to any one of claims 1 to 3, wherein the polyamine component has a diamine component of 10 to 50 mol% of p-phenylenediamine and 50 to 90 mol% of 4,4 '-Diaminodiphenyl ether, acid dianhydride component 50~99 mol% of pyrethic acid dianhydride and 1~50 mol% of 3,3',4,4'-biphenyltetracarboxylic acid Diacid anhydride. 如申請專利範圍第1或3項之舖銅板，其中黏著劑係選自環氧系黏著劑、丙烯酸系黏著劑、及聚醯亞胺系黏著劑中之至少1種所構成。 A copper clad plate according to claim 1 or 3, wherein the adhesive is selected from at least one of an epoxy adhesive, an acrylic adhesive, and a polyimide adhesive. 如申請專利範圍第1或3項之舖銅板，其中該銅箔之黏著側的銅表面粗糙度(Rz)為0.1~10微米。 For example, in the copper plate of the first or third aspect of the patent application, the copper surface roughness (Rz) of the adhesive side of the copper foil is 0.1 to 10 μm.
TW095148761A 2005-12-26 2006-12-25 Copper plate TWI392408B (en)

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Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH05271438A (en) * 1992-07-21 1993-10-19 Ube Ind Ltd Composite polyimide sheet
JPH1077353A (en) * 1995-10-03 1998-03-24 Ube Ind Ltd Aromatic polyimide film and copper foil-laminated film

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH05271438A (en) * 1992-07-21 1993-10-19 Ube Ind Ltd Composite polyimide sheet
JPH1077353A (en) * 1995-10-03 1998-03-24 Ube Ind Ltd Aromatic polyimide film and copper foil-laminated film

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