Polyimide substrate and method of manufacturing a printed wiring board using the substrate

Disclosed is a method of preparing a copper-polyimide substrate comprising applying an electroless copper plating to the surface of a polyimide resin, wherein the surface of a polyimide resin is first etched so as to form a hydrophilic denatured layer on the surface of the said polyimide resin and, after a catalyst is imparted to the substrate, the substrate is copper-plated and thereafter heat-treated at a temperature of 120.degree. C. or higher thereby to modify the hydrophilic denatured layer to a heat-resistant copper-diffusion preventing layer. Also disclosed is a method of preparing a printed wiring board having the copper-polyimide substrate, comprising a first step of etching the surface of a polyimide resin substrate, a second step of applying a catalyst to the substrate followed by electroless plating thereof to give a copper-polyimide substrate, and a third step of forming a circuit on the thus prepared copper-polyimide substrate; which is characterized in that a hydrophilic denatured layer is formed on the surface of the polyimide resin by the etching of the first-step treatment, and the substrate is heat-treated at a temperature of 120.degree. C. or higher after the copper-plating treatment of the second step or before the circuit-forming treatment of the third step to be effected by plating a conductive metal on the surface of the substrate by the use of a free cyan or cyan compound, whereby the hydrophilic denatured layer is modified into a heat-resistant copper-diffusion preventing layer. The metal plating layer has an excellent adhesion strength capable of withstanding thermal shocks. The substrate can be used for producing electronic parts having high reliability with stable operationability.

FIELD OF THE INVENTION 
The present invention concerns a copper-polyimide substrate, in which a 
copper plating layer capable of withstanding long-time high-temperature 
treatment at 150.degree. C. or higher and sufficiently resistant to 
thermal shocks caused by soldering, etc., is formed partially or entirely 
on the surface of a polyimide resin, as well as a method of manufacturing 
a printed wiring board using the substrate. 
BACKGROUND OF THE INVENTION 
Since polyimide resins have excellent heat resistance and are comparable to 
other plastic materials in view of mechanical, electrical and chemical 
properties, they are often used as insulating materials such as electric 
appliances. Printed wiring boards (PWB), flexible printed circuits (FPC), 
tape automated bonding (TAB), etc. are manufactured by applying 
photoetching to a copper layer formed on the polyimide resin. 
Copper-polyimide substrates as the material used for such PWB, FPC and TAB 
have generally been prepared by a lamination method of appending a 
polyimide resin and a copper foil by means of adhesives . However, in a 
substrate prepared by the lamination method, impurities such as chloride 
ions or sulfate ions are adsorbed to an adhesive layer present at the 
boundary between the copper layer and the polyimide resin of the substrate 
upon etching treatment for the copper layer or peeling treatment for the 
photoresist, which may lead to a trouble such as insulation failure in a 
case where distance between circuits formed on the substrate is 
particularly narrow. In order to overcome such a drawback, there has been 
studied a method of forming a metal layer directly to the surface of the 
polyimide resin not by way of the adhesive, etc. 
As the method described above there has been known a method of depositing a 
metal layer directly to the surface of the polyimide resin by means of 
sputtering, ion plating, vapour deposition, etc., a method of coating a 
solution of a polyamic acid as a precursor for a polyimide on the metal 
layer and, thereafter imidizing the polyamide to obtain a substrate or a 
method of forming a metal plating layer on the surface of a polyimide 
resin by means of electroless , plating. 
Among the methods described above, in the method of depositing the metal 
layer directly to the surface of the polyimide resin, for example, by 
means of sputtering, ion plating and vapour deposition, since residual 
stresses are formed in the copper layer deposited on the surface of the 
polyimide resin, stresses are concentrated to the boundary between the 
polyimide resin and the copper film layer when a heat treatment is further 
applied to the substrate to remarkably reduce the adhesion of the copper 
film, which may be some time lead to the peeling of the film. 
Further, a polyimide resin deposited with a copper film by means of 
sputtering, ion plating or vapour deposition has often been heated for 
improving the adhesion of the metal film layer, but a problem is also 
brought about that copper diffuses into the polyimide resin and deposited 
as copper oxide particles, thereby remarkably deteriorating the electric 
property and mechanical property of the substrate. 
In order to overcome these problems, it has also been proposed a method of 
forming an intermediate chromium or nickel layer between a polyimide resin 
and a copper film to obtain a three-layered structure, applying heat 
treatment to the stricture, thereby absorbing the stresses concentrated to 
the boundary in this intermediate layer to prevent reduction of adhesion 
and peeling of the copper film, as well as to prevent the deposition of 
copper oxide caused by the diffusion of copper in the polyimide resin. 
However, in a case of forming circuits by using the substrate obtained by 
the method and applying patterning, for example, by means of subtracting 
method, since the metal layer formed on the polyimide resin contains 
metals such as chromium or nickel in addition to copper, other metals such 
as chromium or nickel cannot be removed completely but remain as they are 
when treated with a standard etching solution prepared for the removal of 
copper, failing to obtain satisfactory circuit formation. 
In addition, if chromium or nickel is contained in the metal layer, 
electrical conductivity is poor as compared with the case that the layer 
is formed out of pure copper and, if such a substrate is used as 
electronic material part, reliability is remarkably reduced. Further, even 
with such a method, when TAB is manufactured based on the resultant 
substrate, the adhesion strength of the metal layer is utmost 4 lb/in, 
which is less than 6 lb/in required so far for TAB or printed wiring 
board. 
Further, among the substrate forming methods described above, a method of 
coating a polyamic acid solution as a precursor of the polyimide on a 
metal film, and then polyidizing imidizing the same thereby obtaining a 
copper-polyimide substrate without using the intermediate adhesive layer 
has been disclosed in U.S. Pat. Nos. 3682960, 4148969 and 4496794, etc. 
However, in the copper-polyimide substrate obtained by the method, the 
resin portion of the substrate shrinks remarkably since dehydrating 
condensation also occurs upon polyimidization of the polyamic acid, which 
makes it extremely difficult to provide smoothness for the substrate and 
the substrate lacks in dimensional stability. 
Furthermore, the polyimide resin portion in the substrate obtained by the 
method is remarkably lower in the mechanical strength as compared with the 
polyimide resin usually supplied in a film-like shape. The reason is 
because the chemical structure of the polyimide resin obtained by the 
above-mentioned method is different from that of the polyimide resin 
supplied in the film-like shape and, although the bondability with the 
metal layer can be improved, mechanical property such as elongation is 
poor. Furthermore, in a case where the polyamide acid is coated on the 
copper film, since a copper portion reacts with amide groups and diffuses 
into the resin portion, electric property of the substrate is deteriorated 
and reliability as electronic material is neither sufficient. 
Further, the third method for obtaining the copper-polyimide substrate is a 
method of applying metal coating to the surface of the polyimide resin by 
means of electroless plating. In this method, etching treatment is usually 
applied to the surface of the polyimide resin, thereby providing 
hydrophilic property, adsorbing thereon palladium, etc. as a catalyst and 
then applying electroless plating. 
U.S. Pat. No. 3767538 describes a method of producing a substrate applied 
with a metal coating by means of electroless plating. The feature of the 
process resides in applying etching to the surface of the polyimide resin 
using a solution of sulfuric acid and hydrochloric acid, or mechanically 
impinging fine particles such as sands to the surface, further, applying 
etching if required by means of sodium hydroxide, heating the surface to 
remove water content, and then immersing it into a colloidal palladium 
bath, thereby effecting a catalyst activation treatment. Subsequently, a 
silver plating layer having steam permeability is continuously formed on 
the surface of the polyimide resin by means of electroless plating, 
heating the substrate to 150.degree. C. for removing water content and, 
thereafter, applying electrolytic copper plating to the silver film 
thereby obtaining a copper-polyimide substrate. 
However, nothing is reported for the value of the adhesion of the metal 
layer to the substrate manufactured by the method and, further, since the 
silver film is directly formed on the surface of the polyimide resin in 
this method, there is a possibility that insulation failure may be caused 
between circuits due to silver migration under a high temperature and a 
high humidity, thus defectively lacking in the reliability in a case of 
using the TAB tape, etc., manufactured by using the resultant substrate as 
electronic parts. 
U.S. Pat. No. 3573937 suggests another method of forming a metal layer by 
applying electroless plating to the surface of a polyimide resin. The 
method resides in applying a catalyst to the surface of a polyimide resin, 
then forming a plated resist layer, applying nickel-phosphor alloy 
electroless plating, heating the substrate at a temperature of 190.degree. 
C. for strengthening the bonding between the plated layer and the 
polyimide resin and, subsequently, electrolytically plating copper or 
applying or soldering copper thereon, to obtain a substrate. However, the 
maximum adhesion of the metal layer is reported to be 5.0 lb/in according 
to the non-standard test. While the literature suggests nothing about the 
stability of the adhesion against thermal shocks such as soldering, there 
is a possibility of causing problems regarding this. 
Japanese Patent Laid-Open Sho 63-259083 discloses a method of applying 
electroless nickel or cobalt plating partially or entirely to the surface 
of a polyimide resin and applying electrolytic copper plating thereon, 
thus forming a metal film having a great bondability capable of 
withstanding thermal shocks such as soldering on a polyimide resin. 
The feature of the methods resides in applying etching to the surface of 
the polyimide resin with an aqueous solution containing an amine of 
H.sub.2 N(CH.sub.2).sub.n NH.sub.2 (n represents an integer between 2 and 
6), an alkali metal hydroxide and an alcohol of a structure soluble in 
water, providing a catalyst, applying electroless nickel and cobalt 
plating and, finally, applying electrolytic copper plating. 
The adhesion of the metal layer in the disclosed example of the substrate 
obtained by the method is 10.0 lb/in according to IPC-TM-650 Method 2.4.9. 
As Received Method A and 5.0 lb/in according to IPC-TM-650 Method 2.4.9. 
After Solder Float Method C, by which the adhesion satisfactory to some 
extent can be nickel and cobalt in the substrate obtained by the 
above-mentioned method could be removed finally by means of an iron 
chloride etching solution, if the substrate is utilized for a TAB tape, 
with narrow width and interval of lead, the copper lead cannot maintain 
the shape till the complete removal of the nickel and cobalt layer due to 
the difference of the solubility of nickel and cobalt relative to iron 
chloride and, accordingly, reliability is poor when the TAB tape is 
assembled as an electronic part. Further, in a case of forming a copper 
layer by electroless copper plating directly to the surface of the 
polyimide resin by the above-mentioned method, it has been shown that the 
copper layer is peeled off in IPC-TM-650 Method 2.4.9. After Solder Float 
Method C. Thus, at present, it has not yet been actually established a 
technique capable of directly forming a copper layer having adhesion 
capable of withstanding thermal shock such as soldering partially or 
entirely on the surface of the polyimide resin substrate. 
Further, in a case of using a substrate obtained by applying an electroless 
plating to the polyimide resin as described above, applying patterning to 
form a copper layer of a desired width and then applying plating to the 
copper layer by using a solution containing a free cyan or cyan compound 
thereby preparing a wiring board, there has also been found a problem that 
the copper layer is peeled off from the surface of the polyimide resin. 
On the other hand, recently with elevation of the integration degree of IC, 
LSI and the like electronic devices, it has become expected that a high 
heat energy is to be irradiated from IC, LSI or the like device to a 
substrate for a long period of time when such a device is fitted to the 
substrate. Under the situation, the substrate is required to have a 
heat-stability stability as its characteristic when a high heat is 
imparted to the substrate for a long period of time. 
The reliability of a substrate with respect to the high-temperature 
resistance characteristic thereof under the condition of a high 
temperature ambient for a long period of time may often be determined by 
examining the change, if any, of the characteristic values of the 
substrate, after the substrate to be examined has been stored in an 
atmosphere of 150.degree. C. for a period of 1000 hours. 
Regarding the adhesion strength of the metal layer after the 
above-mentioned heat-resistance test, for example, in the case of TAB, a 
critical value of 1.0 lb/in or more is required. However, it has been 
found that the adhesion strength of the conventional substrate is lowered 
to 0.5 lb/in after the heat-resistance resistance test, which means that 
not only the substrate could not satisfy the above-mentioned indispensable 
value when it has been exposed to a high temperature ambient for a long 
period of time but also the metal layer would be peeled off from the 
substrate because of the lowering of the adhesion strength of the layer to 
the substrate when IC, LSI or the like device is fitted to the substrate 
and a high heat energy to be irradiated from such device is imparted to 
the substrate for a long period of time. 
SUMMARY OF THE INVENTION 
It is, accordingly, an object of the present invention to provide a method 
of manufacturing a copper-polyimide substrate prepared by forming 
partially or entirely on the surface of a resin a copper film having such 
a high adhesion as sufficiently withstanding thermal shocks such as caused 
by soldering by means of electroless plating, having sufficient 
electrical, mechanical and thermal reliability when used in electronic 
parts such as TAB and being free from extreme lowering of the adhesion 
strength of the metal layer when exposed to a high heat ambient for a long 
period of time, as well as a method of manufacturing a printed wiring 
board using such a substrate. 
The present inventors have made various studies for the reason why it is 
impossible to obtain a copper film having such a high adhesion as capable 
of withstanding thermal shocks such as caused by soldering in the 
copper-polyimide substrate obtained by the electroless plating method and, 
as a result, have found that a denatured layer of poor heat resistance is 
often formed on the surface of a polyimide resin by applying pre-treatment 
of electroless plating in the method conducted so far and, upon applying 
electroless plating and applying thermal shocks such as by soldering to 
the substrate in this state, the plating layer tends to easily peel off 
from the interface between the denatured layer portion or the polyimide 
resin and the denatured layer, further, that since the denatured layer is 
dissolved by a free cyan or cyan compound used in the case of 
manufacturing a printed wiring board, etc. by using the substrate, peeling 
of the metal layerfrom the surface of the substrate is also promoted 
therewith, as well as that the denatured layer can be converted into 
thermally resistant structure by applying heat treatment within an 
appropriate temperature range to the substrate containing the denatured 
layer. 
The present inventors have further found that the substrate thus prepared 
may sufficiently be used in small-capacity electronic parts as it is, but 
when it is used in a large-capacity electronic part and is receives a 
high-temperature heat irradiation for a long period of time, copper would 
diffuse into the inside of the polyimide resin from the plated interface 
to often cause peeling from the inside of the resin into which copper has 
diffused or from the interface between the diffused copper and the resin; 
that diffusion of copper into the resin is extremely promoted when the 
substrate is exposed to a high temperature in an oxidizing atmosphere, for 
example, when it is stored in a high-temperature air for a long period of 
time; and that diffusion of copper into the inside of a polyimide resin 
under such a high-temperature oxidizing atmosphere may remarkably be 
lowered by forming a particular hydrophilic denatured layer on the surface 
of the polyimide resin by etching-treatment with a particular chemical 
such as sulfuric acid or the like in the pre-etching followed by 
conducting heat-treatment of the substrate after electroless plating 
thereof to thereby modify the structure of the said hydrophilic denatured 
layer into one which is heat-resistant and which may prevent diffusion of 
copper into a polyimide resin, and accordingly even though the thus 
modified substrate is exposed to an oxidizing atmosphere such as air at a 
high temperature for a long period of time, lowering of the adhesion 
strength of the metal layer may noticeably be prevented. On the basis of 
such findings, the present inventors have accomplished the present 
invention. 
Specifically, in order to overcome the foregoing problems, the present 
invention provides a method of manufacturing a copper-polyimide substrate 
by applying electroless copper plating to the surface of a polyimide resin 
optionally followed by applying electrolytic copper-plating thereto, 
wherein the surface of a polyimide resin is first etched to form a 
hydrophilic denatured layer thereon, and after a catalyst is imparted 
thereto, the surface of the substrate is subjected to electroless 
copper-plating and then optionally to electrolytic copper- lating, and 
thereafter the substrate is heat-treated at a temperature of 120.degree. 
C. or higher so as to midify the previously formed hydrophilic denaturated 
layer to further a heat-resistant copper diffusion-preventing layer; and 
also provides a method of manufacturing a printed wiring board using such 
a substrate. As one preferred embodiment, sulfuric acid is used in the 
etching step. As another preferred embodiment, the etching step is 
effected by two-stage procedure where a diamine is used in the first stage 
etching and a quaternary ammonium hydroxide is used in the second stage 
etching. Accordingly, the hydrophilic denatured layer to be formed on the 
surface of a polyimide resin by the etching treatment is modified into a 
layer having an excellent heat-resistance and an excellent copper 
diffusion-preventing property by the heat-treatment to be effected after 
the electroless copper-plating, whereby the quality of the 
copper-polyimide substrate or the printed wiring board having the 
substrate, when used in a large-capacity electronic part, can remarkably 
be improved by the present invention. 
DETAILED DESCRIPTION OF THE INVENTION 
Generally, upon manufacturing a copper-polyimide substrate by electroless 
plating, it is necessary to render the surface of the resin hydrophilic by 
applying an etching treatment to the surface of the polyimide resin for 
providing a catalyst in order to promote the plating prior to applying the 
plating treatment. An etching solution generally used for providing the 
hydrophilic property to the polyimide resin, there can be mentioned an 
alkaline solution such as an aqueous solution of an amine compound, e.g., 
hydrazine or ethylene diamine, or an aqueous solution of an alkali metal 
hydroxide, which may contain alcohols such as ethanol . 
This is because, although a polyimide is chemically stable, the imide 
groups of constituting a polyimide can be reduced and cleaved by a strong 
reducing agent such as hydrazine or the like and the carbonyl groups can 
be hydrolyzed with an alkali, whereby the thus treated part of the 
polyimide is decomposed to a polyamic acid containing hydrophilic carboxyl 
groups and accordingly the surface of the thus treated polyimide may be 
relatively easily hydrophilicated. 
The thus formed hydrophilic denatured layer has a fairly poor 
heat-resistance as compared with the original polyimide of itself. 
However, by the studies of the present inventors, it has been found that 
the denatured layer may be restored again to have a thermally stable 
structure by heat-treatment of the substrate, after plated, at a 
temperature ranging from 120.degree. to 420.degree. C. so as to dehydrate 
and condensate the said denatured layer to again polyimidize the layer. 
However, even in the case of the substrate as heat-treated after plated by 
electroless plating, lowering of the adhesion strength of the metal layer 
to the substrate has been found inevitable when the substrate has been 
kept in a high-temperature air atmosphere for a long period of time. 
By the present inventors observation, it is noted that the above-mentioned 
problems occur only in the case when a metal layer is formed on a part or 
all of one surface of a polyimide resin but they do not in the case when a 
metal layer is entirely formed on all the surfaces of a polyimide resin. 
Additionally, even when a metal layer is formed only on a part or all of 
one surface of a polyimide resin, lowering of the adhesion strength of the 
metal layer to the substrate does not occur only if the substrate is 
heated in an oxygen-free atmosphere, for example at a high temperature of 
150.degree. C., for a long period of time. 
In order to overcome the problems, the present inventors have observed the 
distribution of elements in the plated interface of a substrate, which has 
been kept in an air at 150.degree. C. for 1000 hours, by means of AES, 
they have admitted that copper and oxygen have diffused into the inside of 
the resin in the depth of several hundreds .ANG. from the plated 
interface. After successive peeling test of peeling the metal layer from 
the substrate, it has also been found that peeling occurs from the inside 
of the copper-diffused resin or from the interface between the 
copper-diffused part and the non-diffused part. 
From the above-mentioned facts, it may be considered that when a polyimide 
resin substrate as plated by electroless plating and thereafter 
heat-treated is kpet in a high-temperature air atmophsere for a long 
period of time without forming metal layers entirely over the all surfaces 
of the polyimide resin, oxygen would penetrate into the inside of the 
substrate resin from the part thereof which has not been coated with a 
metal layer to reach the plated interface to cause reaction of copper and 
the polyimide or diffusion of copper into the polyimide, since the 
polyimide has an easily oxygen-permeable structure, and, as a result, the 
adhesion strength of the metal layer to the substrate would thereby be 
lowered. 
Under the situation, the present invention has been accomplished on the 
basis of the finding that the hydrophilic denatured layer as formed by 
hydrophilicating the surface of a polyimide resin by etching with an 
etching agent of a certain kind can be modified to have a thermally stable 
structure by heat-treatment of the denatured layer after electroless 
plating thereof while the thus modified structure may have a property of 
hardly causing diffusion of copper into the inside of the polyimide resin 
even after the substrate is kept in a high-temperature air atmosphere for 
a long period of time. 
In accordance with the method of the present invention, one preferred 
embodiment of the etching agent to be used for imparting hydrophilicity to 
the polyimide resin substrate is sulfuric acid. 
The present inventors have studied and have found that the denatured layer 
to be formed by etching of a polyimide reisn with sulfuric acid is 
naturally different from the denatured layer to be formed by reduction of 
a hydrazine monohydrate which is generally used in the hydrophilicating 
treatment of the kind or from the denatured layer to be formed by 
hydrolysis with an alkali; and that when the substrate having such a 
denatured layer as formed by etching treatment with sulfuric acid is 
heat-treated at a temperature of 120.degree. C. or higher, the resulting 
substrate may have an excellent thermal stability and may also be modified 
into one having a structure where copper could hardly diffuse into the 
inside of the polyimide resin even though the substrate is kept in a 
high-temperature air atmosphere for a long period of time. 
Accordingly, the substrate thus hydrophilicated by etching with sulfuric 
acid and thereafter subjected to electroless plating followed by 
heat-treatment at a determined temperature is free from peeling of the 
metal layer even when a thermal shock, for example, by soldering is 
imparted thereto Regarding the adhesion strength of the metal layer to the 
substrate, the mean value is 9.5 lb./in. according to IPC-TM-650 Method 
2.4.9. As Received Method A; while it is 8.4 lb./in. according to 
IPC-TM-650 Method 2.4.9. After Solder Float Method C. That is, the 
adhesion strength is extremely high. After the substrate has been kept in 
an air of 150.degree. C. for 1000 hours, the adehsion strength of the 
metal layer still is high to be 3.0 lb./in. or more. Therefore, electronic 
parts such as TAB as manufactured by using the substrate may sufficiently 
satisfy the necessary values. 
The concentration of sulfuric acid to be used in the above-mentioned 
sulfuric acid-etching treatment is desirably 30% by weight or more, more 
preferably 80% by weight or more. If the sulfuric acid concentration is 
less than 30% by weight, it is difficult to hydrophilicate a polyimide 
resin even though the resin is heated during the treatment. Where the 
sulfuric acid concentration is to fall within the range offrom 30 to 80% 
by weight, hydrophilication of a polyimide resin may well be effected 
under the condition of an elevated temperature of 50.degree. C. or higher 
or at room temperature. In the latter case, the treatment is effected for 
a long period of time. If the sulfuric acid concentration is more than 80% 
by weight, hydrophilication of the surface of a polyimide resin may well 
be effected even at room temperature for a short period of time. 
In accordance with another preferred embodiment of the method of the 
present invention of hydrophilicating the polyimide resin substrate, the 
etching treatment is effected by a two-stage procedure in which etching of 
the first stage is effected by the use of a diamine of a general formula 
H.sub.2 N(CH.sub.2).sub.n NH.sub.2 (where n represents an integer of from 
2 to 6) or a hydrate thereof and etching of the second stage is effected 
by the use of a solution containing a quaternay ammonium hydroxide of a 
general formula: 
##STR1## 
where R.sup.1 and R.sup.2 independently represent an alkyl group having 
from 1 to 4 carbon atoms; R.sup.3 represents an alkyl group having from 1 
to 18 carbon atoms or an alkenyl group having from 1 selected from the 
group consisting of to 18 carbon atoms; R.sup.4 is selected from the group 
consisting of an alkyl group having from 1 to 18 carbon atoms, an alkenyl 
group having from 1 to 18 carbon atoms, a benzyl group, and an alkylbenzyl 
group in which the alkyl moiety has from 1 to 18 carbon atoms. 
Needless to say, it is a matter of course that the same excellent 
heat-resistance and copper diffusion preventing effect can be attained 
also in the case as that attained in the above-mentioned case where the 
hydrophilication treatment is effected by the use of sulfuric acid, after 
electroless plating of the resulting substrate followed by heat-treatment 
thereof. 
The reason why the etching treatment is effected by the above-mentioned 
two-stage procedure is because the low molecular diamine which has a high 
chemical affinity to the polyimide resin may penetrate into the inside of 
the polyimide resin to thereby make the chemical bond of the polyimide as 
a polymer unstable by the first stage etching treatment and additionally, 
the thus chemically unstabilized portions of the polymer are hydrolyzed 
with a weak alkali such as the above-mentioned quaternay ammonium 
hydroxide by the second stage etching treatment whereby the surface of the 
polyimide resin may finally be hydrophilicated to be finely rough with 
ease. 
However, if the etching solution to be used in the first stage etching 
treatment and the etching solution to be used in the second stage etching 
treatment are blended and the polyimide resin is etched with the resulting 
blend etching solution, the effect of the present invention cannot be 
attained since the effects of the both solutions are counter-balanced with 
each other. 
On the other hand, if the etching treatment is effected in the presence of 
a strong reducing agent such as hydrazine, the adhesion strength of the 
metal layer to the substrate would extremely lower when the substrate is 
exposed to a high-temperature oxidizing atmosphere as mentioned above. 
The substrate as obtained by plating the substrate as etched by the said 
two-stage etching treatment by electroless plating followed by 
heat-treatment of the resulting substrate at a determined temperature in 
accordance with the method of the present invention does not cause peeling 
of the metal layer from the substrate even though a thermal shock, for 
exmaple, by soldering is imparted thereto, like the substrate as etched 
with sulfuric acid. 
Regarding the adhesion strength of the metal layer to the substrate after 
heat-treatment, the mean value is 8.0 lb/in. according to IPC-TM-650 
Method 2.4.9. As Received Method A; while it is 7.4 lb.in. according to 
IPC-TM-650 Method 2.4.9. After Solder Float Method C. That is, the 
adhesion strength is extremely high. After the substrate has been kept in 
an air of 150.degree. C. for 1000 hours, the adhesion strength of the 
metal layer still is high to be 4.0 lb.in or more. Therefore, electronic 
parts such as TAB as manufactured by using the substrate may sufficiently 
satisfy the necessary values, and additionally, the reliability of the 
substrate in the parts is fully high. 
In the diamine of a general formula H.sub.2 N(CH.sub.2).sub.n NH.sub.2 to 
be used in the first stage of the said two-stage etching treatment, the 
value n represents an integer of from 2 to 6. This is because the diamine 
having a lower molecular weight is to have a higher affinity to polyimides 
and therefore etching of polyimides with the diamine having a lower 
molecular weight is easier. Where n is 7 or more, the diamines would have 
a poor affinity to polyimides and therefore could not display a sufficient 
etching effect. 
As typical examples of the quaternary ammonium hydroxide of the 
above-mentioned general formula, which are preferably employed in the 
second stage etching treatment of the present invention, there are 
mentioned tetramethylammonium hydroxide, tetraethylammonium hydroxide, 
tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, 
benzyltrimethylammonium hydroxide, phenyltrimethylammonium hydroxide, 
dodecyltrimethylammonium hydroxide, octadecyltrimathylammonium hydroxide, 
dodecyltriethylammonium hydroxide, octadecyltriethylammonium hydroxide, 
dodecyltripropylammonium hydroxide, benzyldimethyloctadecylammonium 
hydroxide, and p-dodecylbenzyltrimethylammonium hydroxide. The etching 
solution to be employed in the second etching step is preferably in the 
form of an aqueous solution or alcoholic solution containing the 
hydroxide. 
A catalyst is imparted to the surface of the thus etched polyimide resin 
for the purpose of promoting the successive plating, and the resin is 
plated by electroless plating and thereafter heat-treated. The last 
heat-treatment is effected for the purpose of re-modifying the chemical 
structure of the hydrophilic denatured layer formed by the previous 
etching treatment, and it is naturally different from an ordinary 
heat-treatment which is generally effected in an ordinary electroless 
plating at a temperature of 70.degree. to 150.degree. C. for the purpose 
of removal of water. 
Specifically, the heat-treatment of the present invention is effected for 
the purpose of modifying the chemical structure of the hydrophilic 
denatured layer as formed on the resin substrate to one which is thermal 
stable and in which copper hardly diffuses even when the substrate is kept 
in a high-temperature oxidizing atmosphere for a long period of time. 
Therefore, the proper temperature necessary for the heat-treatment varies 
in accordance with the means to be employed for effecting the 
heat-treatment. For instance, where the heat-treatment is effected by the 
use of a vacuum heating furnace, the temperature is necessarily 
120.degree. C. or higher, preferably 150.degree. C. or higher. Where the 
heat-treatment is effected by the use of an ordinary heating furnace in an 
inert gas atmosphere in air, the temperature is necessarily 250.degree. C. 
or higher. 
If the temperature for the heat-treatment is lower than the said range, 
modification of the hydrophilic denatured layer would hardly occur. 
However, where the heat-treatment is effected at a too high temperature 
for a too long period of time, the chemical structure of the polyimide 
resin itself would be decomposed to deteriorate the excellent intrinsic 
characteristics of the polyimide resin of itself. For instance, where the 
substrate is heat-treated in a heating furnace having a nitrogen 
atmosphere kept at 460.degree. C., no chemical change of the polyimide 
resin occurs within a heat-treatment time of 15 minutes with no change of 
the characteristics of the resin. However, if the heat-treatment is 
effected for a period of 15 minutes or more under the same condition, the 
chemical structure of the polyimide resin would begin to decompose whereby 
the mechanical and electrical characteristics of the substrate would be 
deteriorated. If such a deteriorated substrate is used in forming 
electronic parts, the reliability of the parts would lower. 
As mentioned above, the conditions of the heat-treatment in the method of 
the present invention are in close contact with the kind of the 
heat-treatment means, the heating temperature and the heating time and 
therefore could not be defined indiscriminately. Accordingly, it is 
desired that the conditions of the heat treatment are previously 
determined on the basis of preliminary experiments or the like, in 
practically and actually carrying out the method of the present invention. 
The polyimide resin to be used in the present invention may be anyone 
obtainable by imidizing a polyamic acid by thermal or chemical 
dehydro-condensation of the amide groups and the carboxyl groups of the 
acid, which includes, for example, Kapton (trade name of product 
manufactured by Dupont-Toray Co.,Ltd.) having the folloiwng chemical 
formula: 
##STR2## 
as well as Upilex (trade name of product manufactured by Ube Industries, 
Ltd.) having the following chemical formula: 
##STR3## 
The step of applying the heat-treatment in the present invention is 
different depending upon the desired plating positions to the polyimide 
resin. That is, in a case of applying plating partially to the surface of 
the polyimide resin, the heat-treatment in accordance with the present 
invention may be applied either after electroless plating or after the 
electrolytic plating applied subsequently. Since steams generated upon 
heat-treatment permeate to escape from the surface of the polyimide resin, 
neither the swelling at the plating interface nor the peeling of the 
plating layer occurs. 
In a case of applying plating to the entire surface of the polyimide resin, 
it is necessary to apply the heat treatment after the electroless plating 
or at a stage when an electrolytically plated thin layer of less than 5 
microns has been formed. If heat-treatment is applied after the copper 
plating layer has been formed on the entire surface of the polyimide resin 
in a thickness of more than 5 microns, since steams evolved upon 
heat-treatment cannot completely permeate through the copper films, it may 
cause a worry that swelling may occur along the interface of the plating 
layer or the plating layer may be peeled off. 
Further, the heat-treatment conducted in the present invention can be 
applied, not in the production step of the electroless-plated substrate, 
but in the production step for various printed wiring boards, manufactured 
by utilizing the resulting substrate. That is, such as printed wiring 
board is usually obtained by patterning a copper-polyimide substrate 
prepared by electroless plating such that a metal layer of a desired width 
is formed by the patterning treatment and then applying plating treatment 
to the metal layer by using a solution containing a free cyan or cyan 
compound. However, in the thus obtained wiring board, the metal layer 
often peels off from the surface of the substrate to deteriorate the 
reliability of the products. The present inventors have studied on this 
phenomenon and, as a result, confirmed thit is caused by the reason that 
the denatured layer of the polyimide resin formed by the electroless 
plating pre-treatment is exposed to the surface of the substrate by the 
patterning treatment and dissolved by a solution containing a free cyan or 
cyan compound, which makes the deposition of the metal layer unstable on 
the surface of the substrate to cause peeling. 
Accordingly, when applying a heat-treatment within a temperature range from 
120.degree. to 420.degree. C. to a substrate before applying the plating 
treatment to the substrate by using the cyan solution, thereby imidizing 
the denatured layer so as to be less soluble to the solution containing 
the free cyan or cyan compound, it is possible to prevent the peeling of 
the metal layer of the substrate. 
Further, in the present invention, there is no particular restriciton on 
the atmosphere of the heat-treatment. That is, any of aerial, inert gas or 
vacuum atmosphere can be employed for the heat-treatment to obtain the 
same result. However, a long-time heat-treatment in an aerial atmosphere 
would cause gradual proceeding of diffusion of the copper into the 
polyimide resin substrate and, as a result, the adhesion the copper layer 
would become easily oxidized. Because of the reasons, it is most 
recommended that the heat-treatment in the method of the present invention 
is effected in an oxygen-free atmosphere. 
Next, the present invention will be explained in more , detail by way of 
the following examples, which, however, are not intended to restrict the 
scope of the present invention. 
Briefly, in Examples 1 to 19, sulfuric acid was used in etching the 
polyimide resin. Characteristics of the substrates prepared are shown 
therein. Additionally, using the substrates prepared, TAB tapes were 
prepared, characteristics of which are also shown therein. Comparative 
Examples 1 to 4 gave comparative samples, which were compared with the 
samples prepared in Examples 1 to 19. 
In Examples 20 to 40, etching of the polyimide resin was effected by 
two-stage procedure, where the first step etching was effected with a 
diamine and the second step etching with a quaternary ammonium hydroxide. 
Characteristics of the substrates prepared are shown therein. 
Additionally, using the substrates prepared, TAB tapes were prepared, 
characteristics of which are also shown therein. Comparative Examples 5 to 
9 gave comparative samples, which were compared with the sampels prepared 
in Examples 20 to 40.

A. EXAMPLES AND COMATIVE EXAMPLES WHERE ETCHING OF POLYIMIDE RESIN IS 
EFFECTED WITH SULFURIC ACID 
EXAMPLE 1 
A polyimide resin film sample (Kapton 200H, manufactured by Dupont-Toray 
Co.,Ltd.) having a size of 30 cm.times.30 cm was etched by dipping it in 
an aqueous solution containing 90% by weight of sulfuric acid and having a 
temperature of 25.degree. C. for one minute with one surface thereof being 
shielded. After washed with water, OPC-80 Catalyst M (manufactured by 
Okuno Chemical Industries, Co., Ltd.) was applied to the sample and 
treated therewith for 5 minutes at 25.degree. C. Then the sample was again 
fully washed with water, and OPC-555 Accelerator (manufactured by Okuno 
Chemical Industries, Co., Ltd.) was applied thereto to effect acceleration 
treatment of the sample at 25.degree. C. for 7 minutes. After washed with 
water, the surface of film sample was dried at 20.degree. C. for 2 
minutes. After the pre-treatment, the sample was then copper-plated by 
electroless plating under the conditions mentioned below. 
______________________________________ 
Bath Compositon 
CuSO.sub.4.5H.sub.2 O 
10 g/liter 
EDTA.2Na 30 g/liter 
37% HCHO 5 ml/liter 
2,2'-Bipyridyl 10 mg/liter 
PEG #1000 0.5 g/liter 
Plating Condition 
Temperature 65.degree. C. 
Stirring Air 
Time 5 minutes 
______________________________________ 
The thickness of the resulting electroless plated copper was 0.2 micron. 
Then, the substrate was stood still in a vacuum heating furnace in which 
the temperature was elevated at a rate of 10.degree. C./min.under degree 
of 10.sup.-4 Torr, whereupon the substrate was heat-treated therein at 
400.degree. C. for one hour and then cooled to room temperature. 
Further, the substrate was electrolytically copper-plated under the 
conditions mentioned below. 
______________________________________ 
Bath Composition 
CuSO.sub.4.5H.sub.2 O 
80 g/liter 
H.sub.2 SO.sub.4 150 g/liter 
Electrolysis Condition 
Temperature 25.degree. C. 
Cathode Current Density 
3 A/dm.sup.2 
Stirring Air and Cathode Locker 
Time one hour 
______________________________________ 
The thickness of the thus formed copper film on the substrate was 35 
microns. The adhesion strength of the film was 9.8 lb/in as a mean value 
according to IPC-TM-650 Method 2.4.9. As Received Method A and was 8.2 
lb/in as a mean value according to IPC-TM-650 Method 2.4.9. After Solder 
Float Method C. 
Next, the substrate was put in air at 150.degree. C. for 1000 hours and the 
adhesion strength of the copper film was measured to be 3.5 lb/in. 
Additionally, it was confirmed that the difference in the adhesion strength 
depending on different portions of the substrate was slight and therefore 
a substantially uniform plated film was formed on the substrate. 
These facts demonstrate that the substrate formed has a sufficient 
reliability in a case of using it in electronic parts such as TAB. 
EXAMPLE 2 
A copper-polyimide substrate was prepared in the same manner as in Example 
1 except that a polyimide reisn film of Kapton 100H (manufactured by 
Dupont-Toray Co., Ltd.) was used. 
The adhesion strength of the copper film to the substrate was 9.0 lb./in. 
as a mean value according to IPC-TM-650 Method 2.4.9. As Received Method A 
and was 7.5 lb./in. as a mean value according to IPC-TM-650 Method 2.4.9. 
After Solder Float Method C. 
Next, the substrate was kept in air at 150.degree. C. for 1000 hours and 
the adhesion strength of the copper film was measured to be 3.2 lb/in. 
Additionally, it was confirmed that the difference in the adhesion strength 
depending on different portions of the substrate was slight and therefore 
a substantially uniform plated film was formed on the substrate. 
These facts demonstrate that the substrate formed has a sufficient 
reliability in a case of using it in electronic parts such as TAB. 
EXAMPLE 3 
A copper-polyimide substrate was prepared in the same manner as in Example 
1 except that a polyimide resin film of Kapton 500H (manufactured by 
Dupont-Toray Co., Ltd.) was used. 
The adhesion strength of the copper film to the substrate was 9.9 lb./in. 
as a mean value according to IPC-TM-650 Method 2.4.9. As Received Method A 
and was 8.5 lb./in. as a mean value according to IPC-TM-650 Method 2.4.9. 
After Solder Float Method C. 
Next, the substrate was kept in air at 150.degree. C. for 1000 hours and 
the adhesion strength of the copper film was measured to be 3.6 lb./in. 
Additionally, it was confirmed that the difference in the adhesion strength 
depending on different portions of the substrate was slight and therefore 
a substantially uniform plated film was formed on the substrate. 
These facts demonstrate that the substrate formed has a sufficient 
reliability in a case of using it in electronic parts such as TAB. 
EXAMPLE 4 
A copper-polyimide substrate was prepared in the same manner as in Example 
1 except that a polyimide resin film of Kapton 200 V (manufactured by 
Dupont-Toray Co., Ltd.) was used. 
The adhesion strength of the copper film to the substrate was 9.8 lb./in. 
as a mean value according to IPC-TM-650 Method 2.4.9. As Received Method A 
and was 8.2 lb./in. as a mean value according to IPC-TM-650 Method 2.4.9. 
After Solder Float Method C. 
Next, the substrate was kept in air at 150.degree. C. for 1000 hours and 
the adhesion strength of the copper film was measured to be 3.4 lb./in. 
Additionally, it was confirmed that the difference in the adhesion strength 
depending on different portions of the substrate was slight and therefore 
a substantially uniform plated film was formed on the substrate. 
These facts demonstrate that the substrate formed has a sufficient 
reliability in a case of using it in electronic parts such as TAB. 
EXAMPLE 5 
A copper-polyimide substrate was prepared in the same manner as in Example 
1 except that a polyimide resin film of Upilex 50ss (manufactured by Ube 
Industries, Ltd.) was used. 
The adhesion strength of the copper film to the substrate was 10.2 lb/in as 
a mean value according to IPC-TM-650 Method 2.4.9. As Received Method A 
and was 8.6 lb/in.as a mean value according to IPC-TM-650 Mehtod 2.4.9. 
After Solder Float Method C. 
Next, the substrate was kept in air at 150.degree. C. for 1000 hours and 
the adhesion strength of the copper film was measured to be 5.6 lb./in.. 
Additionally, it was confirmed that the difference in the adhesion strength 
depending on different portions of the substrate was slight and therefore 
a substantially uniform plated film was formed on the substrate. 
These facts demonstrate that the substrate fromed has a sufficient 
reliability in a case of using it in electronic parts such as TAB. 
EXAMPLE 6 
A copper-polyimide substrate was prepared in the same manner as in Example 
1 except that a polyimide resin film of NPI 50 (manufactured by 
Kanegafuchi Chemical Industry Co., Ltd.) was used. 
The adhesion strength of the copper film to the substrate was 9.8 lb./in. 
as a mean value according to IPC-TM-650 Method 2.4.9. As Received Method A 
and was 7.9 lb./in. as a mean value according to IPC-TM-650 Method 2.4.9. 
After Solder Float Method C. 
Next, the substrate was kept in air at 150.degree. C. for 1000 hours and 
the adhesion strength of the copper film was measured to be 3.6 lb./in.. 
Additionally, it was confirmed that the difference in the adhesion strength 
depending on different portions of the substrate was slight and therefore 
a substantially uniform plated film was formed on the substrate. 
These facts demonstrate that the substrate formed has a sufficient 
reliability in a case of using it in electronic parts such as TAB. 
EXAMPLE 7 
A copper-polyimide substrate was prepared in the same manner as in Example 
1, except that the both surfaces of the polyimide resin film were entirely 
copper-plated without shielding one surface thereof and thereafter 
heat-treated in the same manner. 
The adhesion strength of the copper film to the substrate was 7.8 lb/in.as 
a mean value according to IPC-TM-650 Method 2.4.9. As Received Method A 
and was 6.7 lb./in. as a mean value according to IPC-TM-650 Method 2.4.9. 
After Solder Float Method C. 
Next, the substrate was kept in air at 150.degree. C. for 1000 hours and 
the adhesion strength of the copper film was measured to be 5.9 lb./in.. 
Additionally, it was confirmed that the difference in the adhesion strength 
depending on different portions of the substrate was slight and therefore 
a substantially uniform plated film was formed on the substrate. 
These facts demonstrate that the substrate formed has a sufficient 
reliability in a case of using it in electronic parts such as TAB. 
EXAMPLE 8 
A copper polyimide substrate was prepared in the same manner as in Example 
1, except that etching of the surface of the polyimide resin film was 
effected with an aqueous solution containing 30% by weight of sulfuric 
acid at 50.degree. C. for 5 minutes. 
The adhesion strength of the copper film to the substrate was 8.6 lb./in. 
as a mean value according to IPC-TM-650 Method 2.4.9. As Received Method A 
and was 6.8 lb./in. as a mean value according to IPC-TM-650 Method 2.4.9. 
After Solder Float Method C. 
Next, the substrate was kept in air at 150.degree. C. for 1000 hours and 
the adhesion strength of the copper film was measured to be 3.0 lb/in. 
Additionally, it was confirmed that the difference in the adhesion strength 
depending on different portions of the substrate was slight and therefore 
a substantially uniform plated film was formed on the substrate. 
These facts demonstrate that the substrate formed has a sufficient 
reliability in a case of using it in electronic parts such as TAB. 
EXAMPLE 9 
A copper-polyimide substrate was prepared in the same manner as in Example 
1, except that etching of the surface of the polyimide resin film was 
effected with an aqueous solution containing 98% by weight of sulfuric 
acid (concentrated sulfuric acid solution) at room temperature for 10 
seconds. 
The adhesion strength of the copper film to the substrate was 11.2 lb./in. 
as a mean value according to IPC-TM-650 Method 2.4.9. As Received Method A 
and was 9.7 lb./in. as a mean value according to IPC-TM-650 Method 2.4.9. 
After Solder Flaot Method C. 
Next, the substrate was kept in air at 150.degree. C. for 1000 hours and 
the adhesion strength of the copper film was measured to be 4.0 lb./in.. 
Additionally, it was confirmed that the difference in the adhesion strength 
depending on different portions of the substrate was slight and therefore 
a substantially uniform plated film was formed on the substrate. 
These facts demonstrate that the substrate formed has a sufficient 
reliability in a case of using it in electronic parts such as TAB. 
EXAMPLE 10 
A copper-polyimide substrate was prepared in the same manner as in Example 
7, except that the entire surface of the polyimide resin film was plated 
by electroless plating and then electrolytically copper-plated over the 
surface thereof in a thickness of 5 microns and the resulting substrate 
film was then heat-treated in the same manner. 
The adhesion strength of the copper film to the substrate was 6.9 lb./in. 
as a mean value according to IPC-TM-650 Method 2.4.9. As Received Method A 
and was 6.4 lb./in. as a mean value according to IPC-TM-650 Method 2.4.9. 
After Solder Float Method C. 
Next, the substrate was kept in air at 150.degree. C. for 1000 hours and 
the adhesion strength of the copper film was measured to be 5.0 lb./in.. 
Additionally, it was confirmed that the difference in the adhesion strength 
depending on different portions of the substrate was slight and therefore 
a substantially uniform plated film was formed on the substrate. 
These facts demonstrate that the substrate formed has a sufficient 
reliability in a case of using it in electronic parts such as TAB. 
EXAMPLE 11 
A copper-polyimide substrate was prepared in the same manner as in Example 
1, except that an electrolytic copper-plated film having a thickness of 35 
microns was formed directly after the electroless plating without 
heat-treatment of the electrolessplated film and thereafter the thus 
plated substrate was heat-treated in the same manner. 
The adhesion strength of the copper film to the substrate : was 9.5 lb./in. 
as a mean value according to IPC-TM-650 Method 2.4.9. As Received Method A 
and was 7.8 lb./in. as a mean value according to IPC-TM-650 Method 2.4.9. 
After Solder Float Method C. 
Next, the substrate was kept in air at 150.degree. C. for 1000 hours and 
the adhesion strength of the copper film was measured to be 3.0 lb./in.. 
Additionally, it was confirmed that the difference in the adhesion strength 
depending on different portions of the substrate was slight and therefore 
a substantially uniform plated film was formed on the substrate. 
These facts demonstrate that the substrate formed has a sufficient 
reliability in a case of using it in electronic parts such as TAB. 
EXAMPLE 12 
A copper-polyimide substrate was formed in the same manner as in Exmaple 1, 
except that the temperature-elevating speed in the heat-treatment in the 
vacuum heating furnace was 30.degree. C./min. and the heat-treatment was 
effected at 420.degree. C. for one hour. 
The adhesion strength of the copper film to the substrate was 10.4 lb./in. 
as a mean value in accordance with IPC-TM-650 Method 2.4.9. As Received 
Method A and was 8.2 lb./in as a mean value according to IPC-TM-650 Method 
2.4.9. After Solder Float Method C. 
Next, the substrate was kept in air at 150.degree. C. for 1000 hours and 
the adhesion strength of the copper film was measured to be 3.9 lb./in.. 
Additionally, it was confirmed that the difference in the adhesion strength 
depending on different portions of the substrate was slight and therefore 
a substantially uniform plated film was formed on the substrate. 
These facts demonstrate that the substrate formed has a sufficient 
reliability in a case of using it in electronic parts such as TAB. 
EXAMPLE 13 
A copper-polyimide substrate was prepared in the same manner as in Example 
1, except that the temperature-elevating speed in the heat treatment in 
the vacuum heating furnace was 20.degree. C./min and the heat-treatment 
was effected at 150.degree. C. for 24 hours. 
The adhesion strength of the copper film to the substrate was 8.4 lb./in. 
as a mean value according to IPC-TM-650 Method 2.4.9. As Received Method A 
and was 7.4 lb./in. as a mean value according to IPC-TM-650 Method 2.4.9. 
After Solder Float Method C. 
Next, the substrate was kept in air at 150.degree. C. for 1000 hours and 
the adhesion strength of the copper film was measured to be 3.0 lb./in.. 
Additionally, it was confirmed that the difference in the adhesion strength 
depending on different portions of the subsrtate was slight and therefore 
a substantially uniform plated film was formed on the substrate. 
These facts demonstrate that the substrate formed has a sufficient 
reliability in a case of using it in electronic parts such as TAB. 
EXAMPLE 14 
A copper-polyimide substrate was formed in the same manner as in Example 1, 
except that the heat-treatment was effected at 250.degree. C. for 12 
hours. 
The adhesion strength of the copper film to the substrate was 8.5 lb./in. 
as a mean value according to IPC-TM-650 Method 2.4.9. As Received Method A 
and was 7.2 lb./in. as a mean value according to IPC-TM-650 Method 2.4.9. 
After Solder Float Method C. 
Next, the substrate was kept in air at 150.degree. C. for 1000 hours and 
the adhesion strength of the copper film was measured to be 3.2 lb./in.. 
Additionally, it was confirmed that the difference in the adhesion strength 
depending on different portions of the substrate was slight and therefore 
a substantially uniform plated film was formed on the substrate. 
These facts demonstrate that the substrate formed has a sufficient 
reliability in a case of using it in electronic parts such as TAB. 
EXAMPLE 15 
A copper-polyimide substrate was formed in the same manner as in Example 1, 
except that the heat-treatment was effected in a heating furnace having a 
nitrogen atmosphere of 400.degree. C. 
The adhesion strength of the copper film to the substrate was 10.6 lb./in. 
as a mean value according to IPC-TM-650 Method 2.4.9. As Received Method A 
and was 7.4 lb./in. as a mean value according to IPC-TM-650 Method 2.4.9. 
After Solder Float Method C. 
Next, the substrate was kept in air at 150.degree. C for 1000 hours and the 
adhesion strength of the copper film was measured to be 3.5 lb./in.. 
Additionally, it was confirmed that the difference in the adhesion strength 
depending on different portions of the substrate was slight and therefore 
a substantially uniform plated film was formed on the substrate. 
These facts demonstrate that the substrate formed has a sufficient 
reliability in a case of using it in electronic parts such as TAB. 
EXAMPLE 16 
A copper-polyimide substrate having a copper film on one surface thereof 
was formed in the same manner as in Example 6, except that the 
heat-treatment was effected in an ordinary heating furnace having an 
aerial atmosphere of 400.degree. C. 
The adhesion strength of the copper film to the substrate was 8.7 lb./in. 
as a mean value according to IPC-TM-650 Method 2.4.9. As Received Method A 
and was 7.2 lb./in. as a mean value according to IPC-TM-650 Method 2.4.9. 
After Solder Float Method C. 
Next, the substrate was kept in air at 150.degree. C for 1000 hours and the 
adhesion strength of the copper film was measured to be 3.1 lb./in.. 
Additionally, it was confirmed that the difference in the adhesion strength 
depending on different portions of the substrate was slight and therefore 
a substantially uniform plated film was formed on the substrate. 
These facts demonstrate that the substrate formed has a sufficient 
reliability in a case of using it in electronic parts such as TAB. 
EXAMPLE 17 
A copper-polyimide substrate was formed in the same manner as in Example 1, 
except that the heat-treatment was effected in a heating furnace having a 
nitrogen atmosphere of 480.degree. C. 
The adhesion strength of the copper film to the substrate was 10.1 lb./in. 
as a mean value according to IPC-TM-650 Method 2.4.9. As Received Method A 
and was 7.6 lb./in. as a mean value according to IPC-TM-650 Method 2.4.9. 
After Solder Float Method C. 
Next, the substrate was kept in air at 150.degree. C. for 1000 hours and 
the adhesion strength of the copper film was measured to be 3.9 lb./in.. 
Additionally, it was confirmed that the difference in the adhesion strength 
depending on different portions of the substrate was slight and therefore 
a substantially uniform plated film was formed on the substrate. 
These facts demonstrate that the substrate formed has a sufficient 
reliability in a case of using it in electronic parts such as TAB. 
EXAMPLE 18 
Using a copper-polyimide substrate as formed in the same manner as in 
Example 1, a TAB tape was manufactured in accordance with the process 
mentioned below. 
Precisely, a negative photo-resist was first coated over the copper film of 
the substrate uniformly in a thickness of 40 microns and dried at 
70.degree. C. for 20 minutes. Afterwards, the substrate was masked with a 
mask in such a way that leads having a lead width of 70 microns and a lead 
distance of 60 microns in the inner lead parts could be formed on the 
substrate, and the photo-resist layer was then irradiated with ultraviolet 
rays of 1000 mJ/cm.sup.2 through the mask and thereafter developed. 
Next, electrolytic copper-plating was applied to the electroless 
copper-plated film as exposed by the previous development, under the 
conditions mentioned below. 
______________________________________ 
Bath Composition 
CuSO.sub.4.5H.sub.2 O 
80 g/liter 
H.sub.2 SO.sub.4 180 g/liter 
Electrolysis Condition 
Temperature 25.degree. C. 
Cathode Current Density 
3 A/dm.sup.2 
Stirring Air and Cathode Locker 
Time one hour 
______________________________________ 
Next, the resist layer was removed, and the electroless copper-plated film 
thus exposed was removed by treatment with an aqueous solution of 20% by 
weight of cupric chloride at 25.degree. C. for one minute whereupon the 
electrolytic copper-plated film acted as a mask. 
Afterwards, a rubber photo-resist was uniformly coated on the entire 
surface of the substrate in a thickness of 5 microns, and a device 
hole-forming mask was applied to the surface composed of the polyimide 
resin and the rubber photo-resist in such a way that the copper leads 
could be positioned in the device hole to be formed. Under the condition, 
the photo-resist layer was exposed and developed, and thereafter the 
substrate was dipped in a hydrazine monohydrate solution at 40.degree. C. 
for 15 minutes so as to dissolve the polyimide resin. Then, the rubber 
photo-resist was removed. 
After the above-mentioned procedure, a TAB tape with copper leads having a 
lead thickness of 35 microns, a lead width of 70 microns and a lead 
distance of 70 microns was obtained 
Where the TAB tape was used as an electronic part, not only the electric 
and mechanical properties as well as heat-resistance were good but also 
the long-time thermal stability was sufficiently reliable. Additionally, 
in preparing the TAB tape, there was no problem on the peeling of the 
copper layer and the TAB tape was manufactured stably. 
EXAMPLE 19 
In Example 18, the heat-treatment was not applied to the step of 
manufacturing the copper-polyimide substrate but applied to the substrate 
formed with a circuit for the copper-lead portion in the next step by 
heating the substrate for one hour in a heating furnace of a nitrogen gas 
atmosphere maintained at 400.degree. C., and then gold plating was applied 
to the copper layer of the substrate by using a gold plating solution N-44 
containing gold potassium cyanide with a concentration of 17 g/liter 
(manufactured by N.E. Chemcat Co., Ltd.), under the following conditions. 
______________________________________ 
Plating Condition 
______________________________________ 
Temperature 70.degree. C. 
Cathode Current Density 
1 A/dm.sup.2 
Stirring Cathode Locker 
Time 9 minutes 
______________________________________ 
Peeling of the plated layer on the substrate of the obtained TAB tape did 
not occur. Since the TAB tape is excellent in electrical and mechanical 
properties, as well as in thermal properties, it has sufficient 
reliability as an electronic material. 
Although the explanation has been made for the production method of TAB 
tapes in Examples 18 and 19, it has been confirmed that similar excellent 
effect can be obtained also for the application to the manufacture of 
various other electronic parts such as circuit wiring boards, for example, 
printed wiring boards, flexible printed circuits, etc. 
COMATIVE EXAMPLE 1 
A copper-polyimide substrate was prepared in the same manner as in Example 
1, except that etching of the surface of the polyimide resin was effected 
by the use of an aqueous solution of 50% by weight of hydrazine 
monohydrate at room temperature for 2 minutes. 
The adhesion strength of the copper film to the substrate was 9.2 lb./in. 
as a mean value according to IPC-TM-650 Method 2.4.9. As Received Method A 
and was 7.6 lb./in. as a mean value according to IPC-TM-650 Method 2.4.9. 
After Solder Float Method C. 
However, after the substrate was kept in air at 150.degree. C. for 1000 
hours, the adhesion strength of the copper film lowered to 0.8 lb./in.. 
Accordingly, it is noted that where the substrate is formed into an 
electronic part such as TAB, the part is to have a problem of lacking in 
the reliability to the long-time heat history. 
COMATIVE EXAMPLE 2 
A copper-polyimide substrate was prepared in the same manner as in Example 
1, except that the heat-treatment after the electroless plating was not 
carried out. 
The adhesion strength of the copper film to the substrate was 5.8 lb./in. 
as a mean value according to IPC-TM-650 Method 2.4.9. As Received Method A 
and was 0.9 lb./in as a mean value according to IPC-TM-650 Method 2.4.9. 
After Solder Float Method C. 
Accordingly, it is noted that where the substrate is formed into an 
electronic part such as TAB, there would be a possibility of peeling of 
leads from the substrate in bonding of leads and IC chips and the part is 
lacking in the reliability in the actual use thereof. 
COMATIVE EXAMPLE 3 
A copper-polyimide substrate was prepared in the same manner as in Example 
1, except that the heat-treatment after the electroless planting was 
effected in air at 20.degree. C. for 24 hours. 
The adhesion strength of the copper film to the substrate was 5.8 lb./in as 
a mean value according to IPC-TM-650 Method 2.4.9. As Received Method A, 
whilst the copper film peeled off from the substrate in the test according 
to IPC-TM-650 Method 2.4.9. After Solder Float Method C. 
Accordingly, it is noted that the substrate could not be used as an 
electronic part such as TAB. 
COMATIVE EXAMPLE 4 
A copper-polyimide substrate was prepared in the same manner as in Example 
1, except that the heat-treatment after the electroless plating was 
effected in air at 430.degree. C. for 30 minutes. 
In the obtained substrate, a part of the polyimide resin carbonized. 
Accordingly, it is understood that the substrate thus heat-treated at such 
a high temperature could not be used as an electronic part such as TAB. 
B. EXAMPLES AND COMATIVE EXAMPLES WHERE ETCHING OF POLYIMIDE RESIN IS 
EFFECTIED BY TWO-STAGE PROCEDURE COMPRISING FIRST-STEP ETCHING WITH 
DIAMINE AND SECOND-STEP ETCHING WITH QUATERNARY AMMONIUM HYDROXIDE 
EXAMPLE 20 
A polyimide resin film sample (Kapton 200H, manufactured by Dupont-Toray 
Co., Ltd.) having a size of 30 cm.times.30 cm was etched by dipping it in 
ethylenediamine at 25.degree. C. for 5 minutes (first-step etching), then 
washed with water and then again etched by dipping it in an aqueous 
solution of 20% by weight of tetraethylammonium hydroxide for 5 minutes 
(second-step etching), whereupon one surface of the sample was shielded. 
Then, the substrate sample was washed with water and OPC-80 Catalyst M 
(manufactured by Okuno Chemical Industries, Co., Ltd.) was applied to the 
sample and treated therewith for 5 minutes at 25.degree. C. The sample was 
again fully washed with water, and OPC-555 Accelerator (manufactured by 
Okuno Chemical Industries, Co., Ltd.) was applied thereto to effect 
acceleration treatment of the sample at 25.degree. C. for 7 minutes. The 
sample was then fully washed with water. After the pre-treatment, the 
shiled as applied to one surface of the sample was removed, and the sample 
was subjected to electroless copper-plating under the conditions mentioned 
below. 
______________________________________ 
Bath Composition 
CuSO.sub.4.5H.sub.2 O 
10 g/liter 
EDTA.2Na 30 g/liter 
37% HCHO 5 ml/liter 
2,2'-Bipyridyl 10 mg/liter 
PEG #1000 0.5 g/liter 
Plating Condition 
Temperature 65.degree. C. 
Stirring Air 
Time 5 minutes 
______________________________________ 
The thickness of the resulting electroless plated copper film was 0.2 
micron. 
Then, the substrate was stood still in a vacuum heating furnace in which 
the temperature was elevated at a rate of 10.degree. C./min. under a 
vacuum degree of 10.sup.-4 Torr, whereupon the substrate was heat-treated 
therein at 400.degree. C. for one hour and then cooled to room 
temperature. 
Further, the substrate was elecrolytically copper-plated under the 
conditions mentioned below. 
______________________________________ 
Bath Composition 
CuSO.sub.4.5H.sub.2 O 
80 g/liter 
H.sub.2 SO.sub.4 150 g/liter 
Electrolysis Condition 
Temperature 25.degree. C. 
Cathode Current Density 
3 A/dm.sup.2 
Stirring Air and Cathode Locker 
Time one hour 
______________________________________ 
The thickness of the formed copper film on the substrate was 35 microns. 
The adhesion of the film was 8.0 lb/in as a mean value according to 
IPC-TM-650 Method 2.4.9. As Received Method A and was 7.4 lb./in. as a 
mean value according to IPC-TM-650 Method 2.4.9. After Solder Float Method 
C. 
Next, the substrate was kept in air at 150.degree. C. for 1000 hours and 
the adhesion strength of the copper film was measured to be 4.3 lb./in.. 
Additionally, it was confirmed that the difference in the adhesion strength 
depending on different portions of the substrate was slight and therefore 
a substantially uniform plated film was formed on the substrate. 
These facts demonstrate that the substrate formed has a sufficient 
reliability in a case of using it in electronic parts such as TAB. 
EXAMPLE 21 
A copper-polyimide substrate was prepared in the same manner as in Example 
20, except that a polyimide resin film of Kapton 100H (manufactured by 
Dupont-Toray Co., Ltd.) was used. 
The adhesion strength of the copper film to the substrate was 7.8 lb./in. 
as a mean value according to IPC-TM-650 Method 2.4.9. As Received Method A 
and was 7.1 lb./in. as a mean value according to IPC-TM-650 Method 2.4.9. 
After Solder Float Method C. 
Next, the substrate was kept in air at 150.degree. C. for 1000 hours, and 
the adhesion strength of the copper film was measured to be 4.0 lb./in.. 
Additionally, it was confirmed that the difference in the adhesion strength 
depending on different portions of the substrate was slight and therefore 
a substantially uniform plated film was formed on the substrate. 
These facts demonstrate that the substrate formed has a sufficient 
reliability in a case of using it in electronic parts such as TAB. 
EXAMPLE 22 
A copper-polyimide substrate was prepared in the same manner as in Example 
20, except that a polyimide resin film of Kapton 500H (manufactured by 
Dupont-Toray Co., Ltd.) was used. 
The adhesion strength of the copper film to the substrate was 8.4 lb./in. 
as a mean value according to IPC-TM-650 Method 2.4.9. As Received Method A 
and was 7.6 lb./in. as a mean value according to IPC-TM-650 Method 2.4.9. 
After Solder Float Method C. 
Next, the substrate was kept in air at 150.degree. C. for 1000 hours, and 
the adhesion strength of the copper film was measured to be 4.5 lb./in.. 
Additionally, it was confirmed that the difference in the adhesion strength 
depending on different portions of the substrate was slight and therefore 
a substantially uniform plated film was formed on the substrate. 
These facts demonstrate that the substrate formed has a sufficient 
reliability in a case of using it in electronic parts such as TAB. 
EXAMPLE 23 
A copper-polyimide substrate was prepared in the same manner as in Example 
20, except that a polyimide resin film of Kapton 200 V (manufactured by 
Dupont-Toray Co., Ltd.) was used. 
The adhesion strength of the copper film to the substrate was 8.2 lb./in. 
as a mean value according to IPC-TM-650 Method 2.4.9. As Received Method A 
and was 7.5 lb./in. as a mean value according to IPC-TM-650 Method 2.4.9. 
After Solder Float Method C. 
Next, the substrate was kept in air at 150.degree. C. for 1000 hours and 
the adhesion strength of the copper film was measured to be 4.4 lb./in.. 
Additionally, it was confirmed that the difference in the adhesion strength 
depending on different portions of the substrate was slight and therefore 
a substantially uniform plated film was formed on the substrate. 
These facts demonstrate that the substrate formed has a sufficient 
reliability in a case of using it in electronic parts such as TAB. 
EXAMPLE 24 
A copper-polyimide substrate was prepared in the same manner as in Example 
20, except that a polyimide resin film of Upilex 50ss (manufactured by Ube 
Industries, Ltd.) was used. 
The adhesion strength of the copper film to the substrate was 8.6 lb./in. 
as a mean value according to IPC-TM-650 Method 2.4.9. As Received Method A 
and was 7.7 lb./in. as a mean value according to IPC-TM-650 Method 2.4.9. 
After Solder Float Method C. 
Next, the substrate was kept in air at 150.degree. C. for 1000 hours and 
the adhesion strength of the copper film was measured to be 5.8 lb./in.. 
Additionally, it was confirmed that the difference in the adhesion strength 
depending on different portions of the substrate was slight and therefore 
a substantially uniform plated film was formed on the substrate. 
These facts demonstrate that the substrate formed has a sufficient 
reliability in a case of using it in electronic part such as TAB. 
EXAMPLE 25 
A copper-polyimide substrate was prepared in the same manner as in Example 
20, except that a polyimide resin film of NPI 50 (manufactured by 
Kanegafuchi Chemical Industry Co., Ltd.) was used. 
The adhesion strength of the copper film to the substrate was 8.3 lb./in. 
as a mean value according to IPC-TM-650 Method 2.4.9. As Received Method A 
and was 7.6 lb./in. as a mean value according to IPC-TM-650 Method 2.4.9. 
After Solder Float Method C. 
Next, the substrate was kept in air at 150.degree. C. for 1000 hours and 
the adhesion strength of the copper film was measured to be 4.4 lb./in.. 
Additionally, it was confirmed that the difference in the adhesion strength 
depending on different portions of the substrate was slight and therefore 
a substantially uniform plated film was formed on the substrate. 
These facts demonstrate that the substrate formed has a sufficient 
reliability in a case of using it in electronic parts such as TAB. 
EXAMPLE 26 
A copper-polyimide substrate was prepared in the same manner as in Example 
20, except that the both surfaces of the polyimide resin film were 
entirely copper-plated without shielding one surface thereof and 
thereafter heat-treated in the same manner. 
The adhesion strength of the copper film to the substrate was 7.5 lb./in. 
as a mean value according to IPC-TM-650 Method 2.4.9. As Received Method A 
and was 6.5 lb./in as a mean value according to IPC-TM-650 Method 2.4.9. 
After Solder Float Method C. 
Next, the substrate was kept in air at 150.degree. C. for 1000 hours and 
the adhesion strength of the copper film was measured to be 5.9 lb./in.. 
Additionally, it was confirmed that the difference in the adhesion strength 
depending on different portions of the substrate was slight and therefore 
a substantially uniform plated film was formed on the substrate. 
These facts demonstrate that the substrate formed has a sufficient 
reliability in a case of using it in electronic parts such as TAB. 
EXAMPLE 27 
A copper-polyimide substrate was prepared in the same manner as in Example 
20, except that the surface of the polyimide resin film was first dipped 
in ethylenediamine monohydrate at 25.degree. C. for 10 minutes (first-step 
etching), then washed with water, and then dipped in an aqueous solution 
of 20% by weight of tetramethylammonium hydroxide at 25.degree. C. for 5 
minutes (second-step etching). 
The adhesion strength of the copper film to the substrate was 7.9 lb./in. 
as a mean value according to IPC-TM-650 Method 2.4.9. As Received Method A 
and was 7.0 lb./in. as a mean value according to IPC-TM-650 Method 2.4.9. 
After Solder Float Method C. 
Next, the substrate was kept in air at 150.degree. C. for 1000 hours and 
the adhesion strength of the copper film was measured to be 4.0 lb./in.. 
Additionally, it was confirmed that the difference in the adhesion strength 
depending on different portions of the substrate was slight and therefore 
a substantially uniform plated film was formed on the substrate. 
These facts demonstrate that the substrate formed has a sufficient 
reliability in a case of using it in electronic parts such as TAB. 
EXAMPLE 28 
A copper-polyimide substrate was prepared in the same manner as in Example 
20, except that the surface of the polyimide resin film was first dipped 
in ethylenediamine at 25.degree. C. for 5 minutes (first-step etching), 
then washed with water and then dipped in an aqueous solution of 10% by 
weight of tetrabutylammonium hydroxide at 50.degree. C. for 5 minutes 
(secondstep etching). 
The adhesion strength of the copper film to the substrate was 7.2 lb./in. 
as a mean value according to IPC-TM-650 Method 2.4.9. As Received Method A 
and was 7.2 lb./in. as a mean value according to IPC-TM-650 Method 2.4.9. 
After Solder Float Method C. 
Next, the substrate was kept in air at 150.degree. C. for 1000 hours and 
the adhesion strength of the copper film was measured to be 4.0 lb./in.. 
Additionally, it was confirmed that the difference in the adhesion strength 
depending on different portions of the substrate was slight and therefore 
a substantially uniform plated film was formed on the substrate. 
These facts demonstrate that the substrate formed has a sufficient 
reliability in a case of using it in electronic parts such as TAB. 
EXAMPLE 29 
A copper-polyimide substrate was prepared in the same manner as in Example 
20, except that the surface of the polyimide resin film was dipped in 
ethylenediamine monohydrate at 25.degree. C. for 10 minutes (first-step 
etching), then washed with water and then dipped in an aqueous solution of 
40% by weight of benzyltrimethylammonium hydroxide at 50.degree. C. for 10 
minutes (secondstep etching). 
The adhesion strength of the copper film to the substrate was 7.6 lb./in. 
as a mean value according to IPC-TM-650 Method 2.4.9. As Received Method A 
and was 7.0 lb./in. as a mean value according to IPC-TM-650 Method 2.4.9. 
After Solder Float Method C. 
Next, the substrate was kept in air at 150.degree. C. for 1000 hours and 
the adhesion strength of the copper film was measured to be 4.1 lb./in.. 
Additionally, it was conformed that the difference in the adhesion strength 
depending on different portions of the substrate was slight and therefore 
a substantially uniform plated film was formed on the substrate. 
These facts demonstrate that the substrate formed has a sufficient 
reliability in a case of using it in electronic parts such as TAB. 
EXAMPLE 30 
A copper-polyimide substrate was prepared in the same manner as in Example 
20, except that the surface of the polyimide resin film was dipped in 
ethylenediamine at 25.degree. C. for 5 minutes (first-step etching), then 
washed with water, and then dipped in a methanol solution of 10% by weight 
of octadecyltrimethylammonium hydroxide at 40.degree. C. for 10 minutes 
(second-step etching). 
The adhesion strength of the copper film to the substrate was 7.0 lb./in. 
as a mean value according to IPC-TM-650 Method 2.4.9. As Received Method A 
and was 6.8 lb./in. as a mean value according to IPC-TM-650 Method 2.4.9. 
After Solder Float Method C. 
Next, the substrate was kept in air at 150.degree. C. for 1000 hours and 
the adhesion strength of the copper film was measured to be 3.8 lb./in.. 
Additionally, it was confirmed that the difference in the adhesion strength 
depending on different portions of the substrate was slight and therefore 
a substantially uniform plated film was formed on the substrate. 
These facts demonstrate that the substrate formed has a sufficient 
reliability in a case of using it in electronic parts such as TAB. 
EXAMPLE 31 
A copper-polyimide substrate was prepared in the same manner as in Example 
20, except that the surface of the polyimide resin film was dipped in 
1,6-diaminohexane at 50.degree. C. for 10 minutes (first-step etching), 
then washed with water, and then dipped in an aqueous solution of 20% by 
weight of tetraethylmmonium ammonium hydroxide at 25.degree. C. for 5 
minutes (second-step etching). 
The adhesion strength of the copper film to the substrate was 7.5 lb./in. 
as a mean value according to IPC-TM-650 Method 2.4.9. As Received Method A 
and was 7.0 lb./in. as a mean value according to IPC-TM-650-Method 2.4.9 
After Solder Float Method C. 
Next, the substrate was kept i air at 150.degree. C. for 1000 hours and the 
adhesion strength of the copper film was measured to be 4.0 lb./in.. 
Additionally, it was confirmed that the difference in the adhesion strength 
depending on different portions of the substrate was slight and therefore 
a substantially uniform plated film was formed on the substrate. 
These facts demonstrate that the substrate formed has a sufficient 
reliability in a case of using it in electronic parts such as TAB. 
EXAMPLE 32 
A copper-polyimide substrate was prepared in the same manner as in Example 
26, except that the both surfaces of the polyimide resin film were 
copper-plated by electroless plating, then electrolytically copper-plated 
to form a copper-plated film having a thickness of 5 microns on each 
surface, and then heat-treated in the same manner. 
The adhesion strength of the copper film to the substrate was 6.7 lb./in. 
as a mean value according to IPC-TM-650 Method 2.4.9. As Received Method A 
and was 6.3 lb./in. as a mean value according to IPC-TM-650 Method 2.4.9. 
After Solder Float Method C. 
Next, the substrate was kept in air at 150.degree. C. for 1000 hours and 
the adhesion strength of the copper film was measured to be 5.5 lb./in.. 
Additionally, it was confirmed that the difference in the adhesion strength 
depending on different portions of the substrate was slight and therefore 
a substantially uniform plated film was formed on the substrate. 
These facts demonstrate that the substrate formed has a sufficient 
reliability in a case of using it in electronic parts such as TAB. 
EXAMPLE 33 
A copper-polyimide substrate was prepared in the same manner as in Example 
20, except that an electrolytic copper-plated film having a thickness of 
35 microns was formed directly after the electroless plating without 
heat-treatment of the electroless-plated film and thereafter the thus 
plated substrate was heat-treated in the same manner. 
The adhesion strength of the copper film to the substrate was 7.7 lb./in. 
as a mean value according to IPC-TM-650 Method 2.4.9. As Received Method A 
and was 7.1 lb./in. as a mean value according to IPC-TM-650 Method 2.4.9. 
After Solder Float Method C. 
Next, the substrate was kept in air at 150.degree. C. for 1000 hours and 
the adhesion strength of the copper film was measured to be 4.1 lb./in.. 
Additionally, it was confirmed that the difference in the adhesion strength 
depending on different portions of the substrate was slight and therefore 
a substantially uniform plated film was formed on the substrate. 
These facts demonstrate that the substrate formed has a sufficient 
reliability in a case of using it in electronic parts such as TAB. 
EXAMPLE 34 
A copper-polyimide substrate was prepared in the same manner as in Example 
20, except that the temperature-elevating speed in the heat-treatment in 
the vacuum heating furnace was 30.degree. C./min. and the heat-treatment 
was effected at 420.degree. C. for one hour. 
The adhesion strength of the copper film to the substrate was 8.8 lb./in. 
as a mean value according to IPC-TM-650 Method 2.4.9. As Received Method A 
and was 8.0 lb./in. as a mean value according to IPC-TM-650 Method 2.4.9. 
After Solder Float Method C. 
Next, the substrate was kept in air at 150.degree. C. for 1000 hours and 
the adhesion strength of the copper film was measured to be 4.7 lb./in.. 
Additionally, it was confirmed that the difference in the adhesion strength 
depending on different portions of the substrate was slight and therefore 
a substantially uniform plated film was formed on the substrate. 
These facts demonstrate that the substrate formed has a sufficient 
reliability in a case of using it in electronic parts such as TAB. 
EXAMPLE 35 
A copper-polyimide substrate was prepared in the same manner as in Example 
20, except that the temperature-elevating speed in the heat-treatment in 
the vacuum heating furnace was 20 .degree. C./min. and the heat-treatment 
was effected at 150.degree. C. for 24 hours. 
The adhesion strength of the copper film to the substrate 7.5 lb./in. as a 
mean value according to IPC-TM-650 Method 2.4.9. As Received Method A and 
was 7.0 lb./in. as a mean value according to IPC-TM-650Method 2.4.9. After 
Solder Float Method C. 
Next, the substrate was kept in air at 150.degree. C. for 1000 hours and 
the adhesion strength of the copper film was measured to be 3.9 lb./in.. 
Additionally, it was confirmed that the difference in the adhesion strength 
depending on different portions of the substrate was slight and therefore 
a substantially uniform plated film was formed on the substrate. 
These facts demonstrate that the substrate formed has a sufficient 
reliability in a case of using it in electronic parts such as TAB. 
EXAMPLE 36 
A copper-polyimide substrate was prepared in the same manner as in Example 
20, except that the heat-treatment was effected at 250.degree. C. for 12 
hours. 
The adhesion strength of the copper film to the substrate was 7.4 lb./in. 
as a mean value according to IPC-TM-650 Method 2.4.9. As Received Method A 
and was 6.8 lb./in. as a mean value according to IPC-TM-650 Method 2.4.9. 
After Solder Float Method C. 
Next, the substrate was kept in air at 150.degree. C. for 1000 hours and 
the adhesion strength of the copper film was measured to be 3.8 lb./in. . 
Additionally, it was confirmed that the difference in the adhesion strength 
depending on different portions of the substrate was slight and therefore 
a substantially uniform plated film was formed on the substrate. 
These facts demonstrate that the substrate formed has a sufficient 
reliability in a case of using it in electronic parts such as TAB. 
EXAMPLE 37 
A copper-polyimide substrate was prepared in the same manner as in Example 
20, except that the heat-treatment was effected in a heating furnace 
having a nitrogen atmosphere of 400.degree. C. 
The adhesion strength of the copper film to the substrate was 8.0 lb./in. 
as a mean value according to IPC-TM-650 Method 2.4.9. As Received Method A 
and was 7.5 lb./in. as a mean value according to IPC-TM-650 Method 2.4.9. 
After Solder Float Method C. 
Next, the substrate was kept in air at 150.degree. C. for 1000 hours and 
the adhesion strength of the copper film was measured to be 4.4 lb./in.. 
Additionally, it was confirmed that the difference in the adhesion strength 
depending on different portions of the substrate was slight and therefore 
a substantially uniform plated film was formed on the substrate. 
These facts demonstrate that the substrate formed has a sufficient 
reliability in a case of using it in electronic parts such as TAB. 
EXAMPLE 38 
A copper-polyimide substrate having a copper film on one surface thereof 
was prepared in the same manner as in Example 20, except that the 
heat-treatment was effected in an ordinary heating furnace having an 
aerial atmosphere of 400.degree. C. 
The adhesion strength of the copper film to the substrate was 7.4 lb./in. 
as a mean value according to IPC-TM-650 Method 2.4.9. As Received Method A 
and was 6.7 lb./in. as a mean value according to IPC-TM-650 Method 2.4.9. 
After Solder Float Method C. 
Next, the substrate was kept in air at 150.degree. C. for 1000 hours and 
the adhesion strength of the copper film was measured to be 4.2 lb./in. . 
Additionally, it was confirmed that the difference in the adhesion strength 
depending on different portions of the substrate was slight and therefore 
a substantially uniform plated film was formed on the substrate. 
These facts demonstrate that the substrate formed has a sufficient 
reliability in a case of using it in electronic parts such as TAB. 
EXAMPLE 39 
A copper-polyimide substrate was prepared in the same manner as in Example 
20, except that the heat-treatment was effected in a heating furnace 
having a nitrogen atmosphere of 480.degree. C. for 5 minutes. 
The adhesion strength of the copper film to the substrate was 8.4 lb./in. 
as a mean value according to IPC-TM-650 Method 2.4.9. As Received Method A 
and was 7.8 lb./in. as a mean value according to IPC-TM-650 Method 2.4.9. 
After Solder Float Method C. 
Next, the substrate was kept in air at 150.degree. C. for 1000 hours and 
the adhesion strength of the copper film was measured to be 4.7 lb./in. . 
Additionally, it was confirmed that the difference in the adhesion strength 
depending on different portions of the substrate was slight and therefore 
a substantially uniform plated film was formed on the substrate. 
EXAMPLE 40 
Using a copper-polyimide substrate as prepared in the same manner as in 
Example 20, a TAB tape was manufactured in accordance with the process 
mentioned below. 
Precisely, a negative photo-resist was first coated over the copper film of 
the substrate uniformly in a thickness of 40 microns and dried at 
70.degree. C. for 20 minutes. Afterwards, the substrate was masked with a 
mask in such a way that leads having a lead width of 70 microns and a lead 
distance of 60 microns in the inner lead parts could be formed on the 
substrate, and the photo-resist layer was then irradiated with ultraviolet 
rays of 1000 mJ/cm.sup.2 through the mask and thereafter developed. Next, 
electrolytic copper-plating was applied to the electroless copper-plated 
film as exposed by the previous development, under the conditions 
mentioned below. 
______________________________________ 
Bath Composition 
CuSO.sub.4.5H.sub.2 O 
80 g/liter 
H.sub.2 SO.sub.4 180 g/liter 
Electrolysis Condition 
Temperature 25.degree. C. 
Cathode Current Density 
3 A/cm.sup.2 
Stirring Air and Cathode Locker 
Time one hour 
______________________________________ 
Next, the resist layer was removed, and the electroless copper-plated film 
thus exposed was removed by treatment with an aqueous solution of 20% by 
weight of cupric chloride at 25.degree. C. for one minute whereupon the 
electrolytic copper-plated film acted as a mask. 
Afterwards, a rubber photo-resist was uniformly coated on the entire 
surface of the substrate in a thickness of 5 microns, and a device 
hole-forming mask was applied to the surface composed of the polyimide 
resin and the rubber photo-resist in such a way that the copper leads 
could be positioned in the device hole to be formed. Under the condition, 
the photo-resist layer was exposed and developed, and thereafter the 
substrate was dipped in a hydrazine monohydrate solution at 40.degree. C. 
for 15 minutes so as to dissolve the polyimide resin. Then, the rubber 
photo-resist was removed. 
After the above-mentioned procedure, a TAB tape with copper leads having a 
lead thickness of 35 microns, a lead width of 70 microns and a lead 
distance of 60 microns was obtained. 
Where the TAB tape was used as an electronic part, not only the electric 
and mechanical properties as well as heat-resistance were good but also 
the long-time thermal stability was sufficiently reliable. Additionally, 
in preparing the TAB tape, there was no problem on the peeling of the 
copper layer and the TAB tape was manufactured stably. 
EXAMPLE 41 
In Example 40, the heat-treatment was not applied to the step of 
manufacturing the copper-polyimide substrate but applied to the substrate 
formed with a circuit for the copper-lead portion in the next step by 
heating the substrate for one hours in a heating furnace of a nitrogen gas 
atmosphere maintained at 400.degree. C., and then gold plating was applied 
to the copper layer of the substrate by using a gold plating solution N-44 
containing gold potassium cyanide with a concentration of 17 g/liter 
(manufactured by N.E. Chemcat Co., Ltd.), under the following conditions. 
______________________________________ 
Plating Condition 
______________________________________ 
Temperature 70.degree. C. 
Cathode Current Density 
1 A/dm.sup.2 
Stirring Cathode Locker 
Time 9 minutes 
______________________________________ 
Peeling of the plated layer on the substrate of the obtained TAB tape did 
not occur. Since the TAB tape is excellent in electrical and mechanical 
properties, as well as in thermal properties, it has sufficient 
reliability as an electronic material. 
Although the explanation has been made for the production method of TAB 
tapes in Examples 40 and 41, it has been confirmed that similar excellent 
effect can be obtained also for the application to the manufacture of 
various other electronic parts such as circuit wiring boards, for example, 
printed wiring boards, flexible printed circuits, etc. 
COMATIVE EXAMPLE 6 
A copper-polyimide substrate was prepared in the same manner as in Example 
20, except that etching of the surface of the polyimide resin was effected 
by the use of an aqueous solution of 50% by weight of hydrazine 
monohydrate at room temperature for 2 minutes. 
The adhesion strength of the copper film to the substrate was 9.2 lb./in. 
as a mean value according to IPC-TM-650 Method 2.4.9. As Received Method A 
and was 7.6 lb./in. as a mean value according to IPC-TM-650 Method 2.4.9. 
After Solder Float Method C. 
However, after the substrate was kept in air at 150.degree. C. for 1000 
hours, the adhesion strength of the copper film was only 0.5 lb./in.. 
Accordingly, it is noted that where the substrates is formed into an 
electronic part such as TAB, the part is to have a problem of lacking in 
the reliability to the long-time heat history. 
COMATIVE EXAMPLE 7 
A copper-polyimide substrate was prepared in the same manner as in Example 
20, except that the etching of the surface of the polyimide resin was 
effected by the use of an aqueous solution containing 20% by weight, to 
the total weight, of ethylene diamine and 16% by weight, to the total 
weight, of tetraethylammonium hydroxide. 
The adhesion strength of the copper film to the substrate was 4.8 lb./in. 
as a mean value according to IPC-TM-650 Method 2.4.9. As Received Method A 
and was 2.0 lb./in. as a mean value according to IPC-TM-650 Method 2.4.9. 
After Solder Float Method C. 
Next, the substrate was kept in air at 150.degree. C. for 1000 hours and 
the adhesion strength of the copper film was measured to be only 0.5 
lb./in.. 
Accordingly, it is noted that where the substrate is formed into an 
electronic part such as TAB, the part is to have a problem of lacking in 
the reliability to the long-time heat history. 
COMATIVE EXAMPLE 8 
A copper-polyimide substrate was prepared in the same manner as in Example 
20, except that the heat-treatment after the electroless plating was not 
carried out. 
The adhesion strength of the copper film to the substrate was 5.5 lb./in. 
as a mean value according to IPC-TM-650 Method 2.4.9. As Received Method 
A; whilst the metal layer peeled off from the surface of the substrate in 
the test according to IPC-TM-650 Method 2.4.9. After Solder Float Method 
C. 
Accordingly, it is noted that the substrate could not be used as an 
electronic part such as TAB. 
COMATIVE EXAMPLE 9 
A copper-polyimide substrate was prepared in the same manner as in Example 
20, except that the heat-treatment after the electroless plating was 
effected in air at 200.degree. C. for 24 hours. 
The adhesion strength of the copper film to the substrate was 5.8 lb./in. 
as a mean value according to IPC-TM-650 Method 2.4.9. As Received Method 
A; whilst the copper film peeled off from the surface of the substrate in 
the test according to to IPC-TM-650 Method 2.4.9. After Solder Float 
Method C. 
Accordingly, it is noted that the substrate could not be used as an 
electronic part such as TAB. 
COMATIVE EXAMPLE 10 
A copper-polyimide substrate was prepared in the same manner as in Example 
20, except that the heat-treatment after the electroless plating was 
effected in air at 430.degree. C. for 30 minutes. 
In the obtained substrate, a part of the polyimide resin , carbonized. 
Accordingly, it is understood that the substrate thus heat-treated at such 
a high temperature could not be used as an electronic part such as TAB. 
As mentioned above, in accordance with the method of the present invention 
where a part or all of the surfaces of a polyimide resin substrate are 
plated by electroless plating followed by electrolytically plating to give 
an adhesive-free copper-polyimide substrate, etching is effected as a 
pretreatment prior to the electroless plating, by the use of sulfuric acid 
or by means of a two-stage procedure where the first-step etching is 
effected with a diamine and the second-step etching is with aquaternary 
ammonium hydroxide, then a catalyst is applied to the thus etched 
substrate, and then the substrate is heat-treated at a particularly 
defined temperature, whereby the thermally unstable denatured layer as 
formed on the surface of the polyimide resin by the said etching treatment 
can be modified to a thermally stable structure in which copper hardly 
diffuses into the inside of the polyimide resin even after the substrate 
has been exposed in a high-temperature oxidizing atmosphere for a long 
period of time. Accordingly, not only the plated metal layer as formed on 
the substrate may have a high adhesion strength sufficiently withstanding 
thermal shocks such as soldering or the like but also extreme lowering of 
the adhesion strength of the metal layer to the substrate may be prevented 
even when the substrate is kept in a high-temperature oxidizing atmosphere 
for a long period of time. 
Further, in the case of manufacturing an electronic part such as a TAB tape 
by using the substrate, since products having sufficiently high 
reliability in electrical, mechanical and thermal points of view can be 
obtained and since peeling of metal layer does not upon production, the 
present invention can provide an excellent effect of improving the 
performance of products and capable of attaining stable operation. 
While the invention has been described in detail and with reference to 
specific embodiments thereof, it will be apparent to one skilled in the 
art that various changes and modifications can be made therein without 
departing from the spirit and scope thereof.