U.S. patent application number 11/590611 was filed with the patent office on 2007-02-22 for etching solutions and processes for manufacturing flexible wiring boards.
This patent application is currently assigned to Sony Corporation. Invention is credited to Hiroshi Samukawa.
Application Number | 20070039921 11/590611 |
Document ID | / |
Family ID | 18707112 |
Filed Date | 2007-02-22 |
United States Patent
Application |
20070039921 |
Kind Code |
A1 |
Samukawa; Hiroshi |
February 22, 2007 |
Etching solutions and processes for manufacturing flexible wiring
boards
Abstract
An etching solution of the invention includes 3-65% by weight of
a diol containing 3 to 6 carbon atoms or a triol containing 4 to 6
carbon atoms, 10-55% by weight of an alkali compound, and water in
an amount of 0.75-3.0 times the amount of the alkali compound. Such
a solution may be used at 65.degree. C. or higher to rapidly etch a
polyimide resin layer having an imidation degree of 50-98% without
unfavorably affecting the working atmosphere.
Inventors: |
Samukawa; Hiroshi;
(Kanuma-shi, JP) |
Correspondence
Address: |
OSHA LIANG L.L.P.
1221 MCKINNEY STREET
SUITE 2800
HOUSTON
TX
77010
US
|
Assignee: |
Sony Corporation
Tokyo
JP
Sony Chemical & Information Device Corporation
Tokyo
JP
|
Family ID: |
18707112 |
Appl. No.: |
11/590611 |
Filed: |
October 30, 2006 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
|
|
09905052 |
Jul 12, 2001 |
7144817 |
|
|
11590611 |
Oct 30, 2006 |
|
|
|
Current U.S.
Class: |
216/13 ; 216/83;
252/79.1; 438/745 |
Current CPC
Class: |
G03F 7/40 20130101; G03F
7/405 20130101; C08J 2379/08 20130101; H05K 3/4614 20130101; C08J
7/12 20130101; H05K 2201/0166 20130101; H05K 3/28 20130101; H05K
2203/0783 20130101; H05K 2203/0793 20130101; H05K 2201/0154
20130101; H05K 3/002 20130101; H05K 2201/0195 20130101 |
Class at
Publication: |
216/013 ;
252/079.1; 216/083; 438/745 |
International
Class: |
H01B 13/00 20060101
H01B013/00; C09K 13/00 20060101 C09K013/00; B44C 1/22 20060101
B44C001/22; H01L 21/461 20060101 H01L021/461 |
Foreign Application Data
Date |
Code |
Application Number |
Jul 12, 2000 |
JP |
2000-210918 |
Claims
1. An etching solution suitable for etching a resin layer based on
a polyimide, the solution comprising an alcohol, water and an
alkali compound, wherein the alcohol is present in a range of from
3 to 65% by weight, the alkali compound is present in a range of
from 10 to 55% by weight and the water is present in a range of
from 0.75 to 3.0 times a weight of the alkali compound, and wherein
the alcohol is based on either one or both of a diol containing
from 3 to 6 carbon atoms and a triol containing from 4 to 6 carbon
atoms and the alkali compound is based on either one or both of an
alkali metal hydroxide and a quaternary ammonium hydroxide.
2. An etching solution suitable for etching a resin layer based on
a polyimide, the solution comprising an alcohol, water and an
alkali compound, wherein the alcohol is present in a range of from
3 to 65% by weight, the alkali compound is present in a range of
from 10 to 55% by weight and the water is present in a range of
from 0.85 to 2.5 times a weight of the alkali compound, and wherein
the alcohol is based on either one or both of a diol containing
from 3 to 6 carbon atoms and a triol containing from 4 to 6 carbon
atoms and the alkali compound is based on either one or both of an
alkali metal hydroxide and a quaternary ammonium hydroxide.
3. The etching solution of claim 1, wherein the alkali metal
hydroxide is based on at least one compound selected from a group
consisting of sodium hydroxide, potassium hydroxide and lithium
hydroxide.
4. The etching solution of claim 2, wherein the alkali metal
hydroxide is based on at least one compound selected from a group
consisting of sodium hydroxide, potassium hydroxide and lithium
hydroxide.
5. The etching solution of claim 1, wherein the quaternary ammonium
hydroxide is based on either one or both of tetramethylammonium
hydroxide and tetraethylammonium hydroxide.
6. The etching solution of claim 2, wherein the quaternary ammonium
hydroxide is based on either one or both of tetramethylammonium
hydroxide and tetraethylammonium hydroxide.
7. The etching solution of claim 1, wherein the diol is based on at
least one diol selected from a group consisting of 1,3-propanediol,
2,3-butanediol, 1,4-butanediol and 1,5-pentanediol.
8. The etching solution of claim 2, wherein the diol is based on at
least one diol selected from a group consisting of 1,3-propanediol,
2,3-butanediol, 1,4-butanediol and 1,5-pentanediol.
9.-18. (canceled)
Description
FIELD OF THE INVENTION
[0001] The present invention relates to the technique for wiring
boards, particularly to the technique for forming an opening in a
resin layer on the surface of a metal wiring of a flexible wiring
board.
PRIOR ART
[0002] Wiring boards having a metal wiring and a resin layer such
as flexible wiring boards have been widely used in the field of
electronic apparatus.
[0003] A process for manufacturing such a flexible wiring board is
explained with reference to FIG. 8(a)-(e).
[0004] Reference numeral 115 in FIG. 8(a) represents a metal
wiring, and a base film 111 is applied on the surface of this metal
wiring 115.
[0005] Opposite to the side of this metal wiring 115 on which base
film 111 is applied, a coating solution containing a polyimide
precursor polyamic acid is applied and dried to form a precursor
layer 122 based on the polyamic acid (FIG. 8(b)).
[0006] Then, the assembly is heated to imidate the polyamic acid
contained in precursor layer 122.
[0007] Reference numeral 123 in FIG. 8(c) represents a resin layer
consisting of the polyimide formed by imidating precursor layer
122.
[0008] Then, a resist coating solution is applied on the surface of
resin layer 123 in this state, and exposed and developed to form an
alkali-resistant resist layer patterned in a predetermined
shape.
[0009] Reference numeral 125 in FIG. 8(d) represents a resist layer
patterned during the process above. This resist layer 125 has an
opening 130 formed by patterning, and resin layer 123 is exposed at
the bottom of this opening 130.
[0010] Then, the assembly is immersed into an etching solution to
remove resin layer 123 exposed at the bottom of opening 130
(etching) When resin layer 123 is removed and metal wiring 115 is
exposed at the bottom of opening 130, the assembly is removed from
the etching solution and the etching solution is washed off the
assembly with warmed water and then resist layer 125 is separated
to give a flexible wiring board shown by reference numeral 110 in
FIG. 8(e).
[0011] Resin layer 123 formed on the surface of this flexible
wiring board 110 has openings 130 at the bottom of which is exposed
metal wiring 115.
[0012] When bumps of another flexible wiring board are brought into
contact with metal wiring 115 via such openings 130, both flexible
wiring boards are electrically connected into a flexible wiring
board of multilayer structure.
[0013] Known etching solutions used for the process of etching
resin layer 123 include those containing an alkali metal, a
hydrazine alkali metal, ethanolamine and water as disclosed in JPA
97081/1998 and those containing an alkali metal, an alcohol, an
amine and water as disclosed in JPA 195214/1998.
[0014] These etching solutions have strong power to dissolve
polyimides, but when such etching solutions are heated to increase
etching speed, highly toxic organic solvents such as hydrazine or
amines evaporate to unfavorably affect the working atmosphere.
[0015] Amine-free solutions consisting of an alkali compound such
as tetramethylammonium hydroxide dissolved in a lower alcohol such
as ethanol, n-propanol or isopropanol have been proposed (JPA
103531/1983).
[0016] However, these lower alcohols have high volatility and
flammability so that they also unfavorably affect the working
atmosphere in the same manner as amines.
[0017] Aqueous tetramethylammonium hydroxide solutions are known as
low-toxicity etching solutions, but cannot serve to etch cured
polyimide resin layers because of the limited power to dissolve
polyimides.
[0018] Such low-dissolving etching solutions are used by applying
and drying a raw resin solution based on a polyamic acid to form a
polyimide precursor layer having an imidation degree of 8-15% and
then etching said polyimide precursor layer.
[0019] In this case, however, the polyimide precursor layer is
patterned by etching and then imidated by heat treatment with the
result that the patterned polyimide precursor layer is contracted
during the heat treatment to lower the precision of the
pattern.
[0020] An amine is sometimes added to such low-dissolving etching
solutions to shorten the time for etching the polyimide precursor
layer, but the amine coordinates with the polar group of the
polyamic acid in the polyimide precursor layer and remains in the
polyimide precursor layer even after the post-etching washing
process.
[0021] If the polyimide precursor layer is calcined in this state,
a highly toxic gas such as amine gas or amine decomposition product
gas is generated to unfavorably affect the working atmosphere.
Moreover, ion contamination of the final flexible wiring board is
aggravated by the ammonium ion probably derived from an amine
decomposition product and remaining in the polyimide resin layer
formed by imidation.
[0022] In any way, rapid and precise etching was difficult without
unfavorably affecting the working atmosphere.
[0023] An object of the present invention is to rapidly and
precisely etch resin layers without using a highly toxic solvent in
order to overcome the disadvantages of the prior art as described
above.
DISCLOSURE OF THE INVENTION
[0024] First, the imidation degree of polyimide used as an
essential factor of the present invention is explained.
[0025] Reference numeral 50 in FIG. 3(a) represents a polyimide
precursor polyamic acid, and said polyamic acid 50 is dehydrated to
ring closure by heating or other means (imidation) into a
polyimide.
[0026] Reference numeral 55 in FIG. 3(b) represents the polyimide
formed by imidating the polyamic acid, and said polyimide 55 has
benzene rings 51 and cyclic imides 53. On the contrary, polyamic
acid 50 has benzene rings 51 without cyclic imides as shown in FIG.
3(a).
[0027] We were interested in the difference in structure between
these polyamic acid 50 and polyimide 55 and defined the extent of
imidation (imidation degree) of polyimide in the present invention
by equation (1) below. Imidation degree
(%)=(PS.sub.1770/PS.sub.1500)(PI.sub.1770/PI.sub.1500).times.100
(1) where PI.sub.1770, PS.sub.1770, PI.sub.1500 and PS.sub.1500
represent absorption intensities measured by a Fourier transform
infrared spectrophotometer at wavelengths of 1770 cm.sup.-1 and
1500 cm.sup.-1, and specifically PS.sub.1770 and PS.sub.1500
represent the absorption intensities of a polyimide sample under
test at wavelengths of 1770 cm.sup.-1 and 1500 cm.sup.-1 while
PI.sub.1770 and PI.sub.1500 represent the absorption intensities of
said polyimide sample completely imidated (imidation degree 100%)
at wavelengths of 1770 cm.sup.-1 and 1500 cm.sup.-1.
[0028] In the present invention, polyimide samples calcined at
350.degree. C. for 15 minutes are supposed to have an imidation
degree of 100%.
[0029] As the infrared absorption at these wavelengths 1770
cm.sup.-1 and 1500 cm.sup.-1 results from the skeletal vibration of
cyclic imide and benzene ring, the content of cyclic imide or the
extent of imidation of polyimide in a polyimide sample can be
numerically expressed by substituting the ratio of absorption
intensities at these wavelengths in the polyimide sample
(PS.sub.1770/PS.sub.1500) and the ratio of absorption intensities
at these wavelengths in the polyimide sample completely imidated
(PI.sub.1770/PI.sub.1500) into equation (1) above.
[0030] As used herein, the term polyimide implies not only
completely imidated polyimides but also those containing a
polyimide precursor represented by a polyamic acid.
[0031] The present invention is defined by the imidation degree (%)
as described above.
[0032] The present invention provides an etching solution suitable
for etching a resin layer based on a polyimide, the solution
comprising an alcohol, water and an alkali compound, wherein the
alcohol is present in a range of from 3 to 65% by weight, the
alkali compound is present in a range of from 10 to 55% by weight
and the water is present in a range of from 0.75 to 3.0 times a
weight of the alkali compound, and wherein the alcohol is based on
either one or both of a diol containing from 3 to 6 carbon atoms
and a triol containing from 4 to 6 carbon atoms and the alkali
compound is based on either one or both of an alkali metal
hydroxide and a quaternary ammonium hydroxide.
[0033] The present invention provides an etching solution suitable
for etching a resin layer based on a polyimide, the solution
comprising an alcohol, water and an alkali compound, wherein the
alcohol is present in a range of from 3 to 65% by weight, the
alkali compound is present in a range of from 10 to 55% by weight
and the water is present in a range of from 0.85 to 2.5 times the
weight of the alkali compound, and wherein the alcohol is based on
either one or both of a diol containing from 3 to 6 carbon atoms
and a triol containing from 4 to 6 carbon atoms and the alkali
compound is based on either one or both of an alkali metal
hydroxide and a quaternary ammonium hydroxide.
[0034] The present invention provides the etching solution, wherein
the alkali metal hydroxide is based on at least one compound
selected from a group consisting of sodium hydroxide, potassium
hydroxide and lithium hydroxide.
[0035] The present invention provides the etching solution, wherein
the quaternary ammonium hydroxide is based on either one or both of
tetramethylammonium hydroxide and tetraethylammonium hydroxide.
[0036] The present invention provides the etching solution, wherein
the diol is based on at least one diol selected from a group
consisting of 1,3-propanediol, 2,3-butanediol, 1,4-butanediol and
1,5-pentanediol.
[0037] The present invention provides a process for etching a resin
layer, comprising the steps of forming a film-like resin layer
based on a polyimide having an imidation degree of from 50 to 98%,
providing a resist layer having an opening at a desired position on
a surface of the resin layer, and bringing an etching solution at
65.degree. C. or more into contact with the resin layer located at
a bottom of the opening to etch the resin layer, the etching
solution comprising an alcohol of from 3 to 65% by weight, an
alkali compound of from 10 to 55% by weight and water in a weight
of 0.75 to 3.0 times a weight of the alkali compound wherein the
alcohol is based on either one or both of a diol containing from 3
to 6 carbon atoms and a triol containing from 4 to 6 carbon atoms
and the alkali compound is based on either one or both of an alkali
metal hydroxide and a quaternary ammonium hydroxide.
[0038] The present invention provides a process for etching a resin
layer, comprising the steps of forming a film-like resin layer
based on a polyimide having an imidation degree of from 50 to 98%,
providing a resist layer having an opening at a desired position on
the surface of the resin layer, and bringing an etching solution at
65.degree. C. or more into contact with the resin layer located at
a bottom of the opening to etch the resin layer, the etching
solution comprising an alcohol of from 3 to 65% by weight, an
alkali compound of from 10 to 55% by weight and water in a weight
of from 0.85 to 2.5 times the weight of the alkali compound wherein
the alcohol is based on either one or both of a diol containing
from 3 to 6 carbon atoms and a triol containing from 4 to 6 carbon
atoms and the alkali compound is based on either one or both of an
alkali metal hydroxide and a quaternary ammonium hydroxide.
[0039] The present invention provides the process for etching a
resin layer, wherein the step of forming a film-like resin layer
comprises the step of heating a precursor layer based on a
polyimide resin having an imidation degree of less than 50%.
[0040] The present invention provides the process for etching a
resin layer, wherein the step of forming a film-like resin layer
comprises the step of applying and drying a coating solution
containing a polyimide having an imidation degree of from 50 to 98%
on a substrate.
[0041] The present invention provides a process for manufacturing a
flexible wiring board comprising the steps of applying and drying a
coating solution containing a polyimide precursor on a side of a
substrate having at least a metal wiring on which the metal wiring
is provided to form a precursor layer based on a polyimide having
an imidation degree of less than 50%, heating the precursor layer
to form a polyimide resin layer having an imidation degree of from
50 to 98%, applying and drying a resist layer coating solution on a
surface of the resin layer to form a resist layer, patterning the
resist layer in a desired shape to form an opening, preparing an
etching solution comprising an alcohol of from 3 to 65% by weight,
an alkali compound from 10 to 55% by weight and water in a weight
of from 0.75 to 3.0 times a weight of the alkali compound wherein
the alcohol is based on either one or both of a diol containing
from 3 to 6 carbon atoms and a triol containing from 4 to 6 carbon
atoms and the alkali compound is based on either one or both of an
alkali metal hydroxide and a quaternary ammonium hydroxide, and
bringing the etching solution at 65.degree. C. or more into contact
with the resin layer located at a bottom of the opening to etch the
resin layer.
[0042] The present invention provides a process for manufacturing a
flexible wiring board comprising the steps of applying and drying a
coating solution containing a polyimide precursor on a surface of a
metal foil to form a precursor layer based on a polyimide having an
imidation degree of less than 50%, heating the precursor layer to
form a polyimide resin layer having an imidation degree of from 50
to 98%, applying and drying a resist layer coating solution on the
surface of the resin layer to form a resist layer, patterning the
resist layer in a desired shape to form an opening, preparing an
etching solution comprising an alcohol from 3 to 65% by weight, an
alkali compound from 10 to 55% by weight and water in a weight of
from 0.75 to 3.0 times the weight of the alkali compound wherein
the alcohol is based on either one or both of a diol containing
from 3 to 6 carbon atoms and a triol containing from 4 to 6 carbon
atoms and the alkali compound is based on either one or both of an
alkali metal hydroxide and a quaternary ammonium hydroxide,
bringing the etching solution at 65.degree. C. or more into contact
with the resin layer located at a bottom of the opening to etch the
resin layer, and providing a resist layer having an opening at a
desired position on the opposite side to a side of the metal foil
on which the resin layer is formed to remove the metal foil exposed
at the bottom of the opening in the resist layer.
[0043] The present invention provides a process for manufacturing a
flexible wiring board comprising the steps of applying and drying a
coating solution containing a polyimide having an imidation degree
of from 50 to 98% on the side of a substrate having at least a
metal wiring on which the metal wiring is provided to form a resin
layer, applying and drying a resist layer coating solution on a
surface of the resin layer to form a resist layer, patterning the
resist layer in a desired shape to form an opening, preparing an
etching solution comprising an alcohol of from 3 to 65% by weight,
an alkali compound of from 10 to 55% by weight and water in a
weight of from 0.75 to 3.0 times a weight of the alkali compound
wherein the alcohol is based on either one or both of a diol
containing from 3 to 6 carbon atoms and a triol containing from 4
to 6 carbon atoms and the alkali compound is based on either one or
both of an alkali metal hydroxide and a quaternary ammonium
hydroxide, and bringing the etching solution at 65.degree. C. or
more into contact with the resin layer located at a bottom of the
opening to etch the resin layer.
[0044] The present invention provides a process for manufacturing a
flexible wiring board comprising the steps of applying and drying a
coating solution containing a polyimide having an imidation degree
of from 50 to 98% on a surface of a metal foil to form a resin
layer, applying and drying a resist layer coating solution on a
surface of the resin layer to form a resist layer, patterning the
resist layer in a desired shape to form an opening, preparing an
etching solution comprising an alcohol of from 3 to 65% by weight,
an alkali compound of from 10 to 55% by weight and water in a
weight of from 0.75 to 3.0 times a weight of the alkali compound
wherein the alcohol is based on either one or both of a diol
containing from 3 to 6 carbon atoms and a triol containing from 4
to 6 carbon atoms and the alkali compound is based on either one or
both of an alkali metal hydroxide and a quaternary ammonium
hydroxide, bringing the etching solution at 65.degree. C. or more
into contact with the resin layer located at the bottom of the
opening to etch the resin layer, and providing a resist layer
having an opening at a desired position on the opposite side to a
side of the metal foil on which the resin layer is formed to remove
the metal foil exposed at a bottom of the opening in the resist
layer.
[0045] As defined above, etching solutions of the present invention
contain water in a range of 0.75-3 times the amount of the alkali
compound. When the alkali compound is present at said mixing ratio,
polyimides having an imidation degree of 50% or more can be rapidly
etched without adding an amine into the etching solution.
[0046] Even when the alkali compound is contained at 55% by weight
based on the total weight of etching solution, for example, etching
solutions of the present invention may contain a minimum amount of
water (0.75 times or more of the alkali compound and 41.25% by
weight of the total weight of etching solution) because they may
contain 3% by weight or more of an alcohol based on the total
weight of etching solution.
[0047] Etching solutions of the present invention containing either
one or both of a diol containing 3 to 6 carbon atoms and a triol
containing 4 to 6 carbon atoms as an alcohol can be used even at a
high temperature of 75.degree. C. or more to safely perform etching
operation because said alcohol containing 2 or less of carbon atoms
has a higher flash point than lower alcohols.
[0048] Resin layers containing a polyamic acid can be etched
without being contaminated with impurity ions such as ammonium ion
or potassium ion even when they are contained in etching solutions
because said alcohol prevents unnecessary ions from binding the
polar group of the polyamic acid.
[0049] Said etching solutions can be used to etch a resin layer
having an imidation degree of 50% or more without deforming the
pattern of the opening in the final resin layer because the degree
of shrink of the resin layer caused by complete imidation after
etching is reduced by half as compared with the degree of shrink
obtained with an imidation degree of 15% or less.
[0050] Etching solutions of the present invention can be used for
etching at 65.degree. C. or more, more preferably 75.degree. C. or
more with a shortened etching period.
[0051] After completion of etching of a resin layer, the resin
layer can be heated to completely imidate the polyimide in the
resin layer.
[0052] When a resin layer having an imidation degree of more than
90% is to be etched, it may not be completely imidated after
etching but should preferably be completely imidated in order to
prepare a more reliable flexible wiring board.
BRIEF DESCRIPTION OF THE DRAWINGS
[0053] FIG. 1(a)-(i) is a flow sheet illustrating a process for
manufacturing a first example of flexible wiring board of the
present invention.
[0054] FIG. 2(a)-(g) is a flow sheet illustrating a process for
manufacturing a second example of flexible wiring board of the
present invention.
[0055] FIG. 3(a), (b) illustrates the structure of polyimide and
polyimidic acid.
[0056] FIG. 4(a), (b) is a flow sheet illustrating a process for
manufacturing an example of flexible wiring board of multilayer
structure using a flexible wiring board of the present
invention.
[0057] FIG. 5 illustrates another example of flexible wiring board
of multilayer structure.
[0058] FIG. 6 illustrates a third example of flexible wiring board
of the present invention.
[0059] FIG. 7 illustrates a fourth example of flexible wiring board
of the present invention.
[0060] FIG. 8(a)-(e) is a flow sheet illustrating a process for
manufacturing a flexible wiring board of the prior art.
THE MOST PREFERRED EMBODIMENTS OF THE INVENTION
Example 1
[0061] First, etching solutions of the present invention and an
example of process for manufacturing a flexible wiring board of the
present invention are described with reference to FIG.
1(a)-(i).
[0062] Reference numeral 31 in FIG. 1(a) represents a metal foil.
On at least one surface of this metal foil 31 is formed a rough
surface (matte surface) 32 by roughening.
[0063] A polyamic acid consisting of biphenyltetracarboxylic acid
and two aromatic diamines (p-phenylenediamine and
4,4'-diaminodiphenyl ether) is dissolved in N-methylpyrrolidone
(hereinafter abbreviated as NMP) to prepare a polyamic acid coating
solution containing 15% by weight of the polyamic acid.
[0064] This polyamic acid coating solution is applied on rough
surface 32 of metal foil 31 shown in FIG. 1(a), and then the
assembly is heated to dryness in a drying oven at 100.degree. C.
for 4 minutes to form a precursor layer 41 (FIG. 1(b)).
[0065] Then, the assembly is calcined at 160.degree. C. for 3
minutes to imidate the polyamic acid contained in precursor layer
41.
[0066] Reference numeral 42 in FIG. 1(c) represents a resin layer
42 obtained by imidating precursor layer 41.
[0067] The ratio of absorption intensities
(PI.sub.1770/PI.sub.1500) of resin layer 42 in the state shown in
FIG. 1(c) determined by Fourier transform infrared spectroscopy was
0.27.
[0068] Separately, the precursor layer 41 in the state shown in
FIG. 1(b) is calcined at 350.degree. C. for 15 minutes into a
completely imidated resin layer. The ratio of absorption
intensities (PS.sub.1770/PS.sub.1500) of this precursor layer
determined by Fourier transform infrared spectroscopy was 0.45.
[0069] These values of ratios (PS.sub.1770/PS.sub.1500 and
PI.sub.1770/PI.sub.1500) were substituted into equation (1) above
to determine the imidation degree of resin layer 42 in the state
shown in FIG. 1(c) to be 60%. The thickness of resin layer 42 here
was about 22 .mu.m.
[0070] Again separately, the ratio of absorption intensities of
precursor layer 41 in the state shown in FIG. 1(b) were determined
by the same method as described above to be 0.07, from which the
imidation degree was calculated as about 15%.
[0071] Then, a carrier film 33 is applied on the surface of the
side of metal foil 31 in the state shown in FIG. 1(c) on which
resin layer 42 is not formed, and a resist layer coating solution
is applied on the surface of resin layer 42 to form a resist layer
45 (FIG. 1(d)).
[0072] Then, resist layer 45 in this state is patterned by exposure
and development through two negative patterns in the form of a
circle having a diameter of 75 .mu.m and a square having a side of
100 .mu.m, respectively, to form 14 openings having different
shapes and bottom sizes.
[0073] Reference numeral 49 in FIG. 1(e) represents an opening 49
formed in resist layer 45 by patterning, and resin layer 42 is
exposed at the bottom of said opening 49.
[0074] Then, 33 parts by weight of 1,3-propanediol as an alcohol is
added to a mixture of 33 parts by weight of high-purity potassium
hydroxide available from Wako Pure Chemical Industries Ltd. as an
alkali compound and 34 parts by weight of pure water to prepare an
amine-free etching solution.
[0075] Then, said etching solution is warmed to 65.degree. C., and
resin layer 42 in the state shown in FIG. 1(e) is wholly immersed
in said etching solution maintained at a temperature of 65.degree.
C. with gentle stirring to remove resin layer 42 exposed at the
bottom of opening 49 in resist layer 45.
[0076] When resin layer 42 at the bottom of opening 49 is removed
and metal foil 31 is exposed at the bottom of opening 49 as shown
in FIG. 1(f), the assembly is removed from the etching solution and
washed with warm water at 60.degree. C.
[0077] Then, resist layer 45 and carrier film 33 are separated
(FIG. 1(g)) and the assembly is heated at 350.degree. C. for 15
minutes to completely imidate the polyimide in resin layer 42.
[0078] Reference numeral 43 in FIG. 1(h) represents the resin layer
completely imidated. Then, a resist layer patterned in a desired
shape is formed on the surface of metal foil 31 on which resin
layer 43 is not formed, and metal foil 31 exposed at the bottom of
the opening in this resist layer is etched to pattern metal foil
31.
[0079] FIG. 1(h) shows the state in which metal foil 31 has been
patterned and the resist layer used for this patterning has been
separated, and reference numeral 35 in the same figure represents a
metal wiring obtained by patterning metal foil 31.
[0080] Then, a base film coating solution is applied and dried on
the surface of metal wiring 35 on which resin layer 43 is not
formed to form a base film 40. Reference numeral 30 in FIG. 1(i)
represents a first example of flexible wiring board of the present
invention having base film 40.
[0081] This flexible wiring board 30 has opening 49 in resin layer
43, and metal wiring 35 is exposed at the bottom of this opening
49.
[0082] During the process in which said flexible wiring board 30
was formed, the "etching speed" and "appearance evaluation" tests
described below were performed.
[Etching Speed]
[0083] The time (minutes) required for etching resin layer 42 shown
in FIG. 1(e)-(f) was determined.
[Appearance Evaluation]
[0084] The appearance of completely imidated resin layer 43 in the
state shown in FIG. 1(h) as described above was observed under an
optical microscope at a magnification of 200.
[0085] Here, the appearance of each opening 49 in resin layer 42
formed with a negative pattern in the form of a circle having a
diameter of 75 .mu.m and a negative pattern in the form of a square
having a side of 100 .mu.m was observed and evaluated as follows.
If any of these openings 49 falls under any of the following
conditions 1) to 3), the appearance was assessed as "poor". If none
of openings 49 falls under any of these conditions, the appearance
was assessed as "good". 1) The diameter or side at the bottom of
opening 49 in resin layer 42 is a half or less of the diameter or
side of each negative pattern. 2) Opening 49 is deformed. 3) A
complete opening was not formed.
[0086] The results of these measurement and evaluation are shown as
Example 1 in Table 1 below. TABLE-US-00001 TABLE 1 Etching speed
imidation Solution Etching Solvent for degree temper- speed Appear-
etching solution (%) ature (min.) ance Example 1 1,3-Propanediol 60
65.degree. C. 2.2 good Example 2 75.degree. C. 1.8 good Example 3
80 65.degree. C. 8.2 good Example 4 75.degree. C. 4.1 good Example
5 85.degree. C. 2.2 good Comparative 100 85.degree. C. 13.0 good
example 1 Example 6 1,4-Butanediol 60 65.degree. C. 1.7 good
Example 7 75.degree. C. 1.2 good Example 8 80 65.degree. C. 8.4
good Example 9 75.degree. C. 4.0 good Example 10 85.degree. C. 2.2
good Comparative 100 85.degree. C. 12.0 good example 2 Comparative
Ethylene glycol 80 75.degree. C. 7.0 poor example 3 Comparative 100
85.degree. C. >25.0 poor example 4
Example 2
[0087] The same resin layer 42 as used in Example 1 having a
patterned resist layer 45 in the state shown in FIG. 1(e) was
immersed into the same etching solution as used in Example 1 at
75.degree. C. to etch resin layer 42 under the same conditions as
in Example 1 and subjected to the "etching speed" test. Then,
etched resin layer 42 was washed, and resist layer 45 and carrier
film 33 were separated and resin layer 42 was completely imidated
under the same conditions as in Example 1.
[0088] Resin layer 43 obtained by complete imidation of resin layer
42 was subjected to the "appearance evaluation" test under the same
conditions as in Example 1.
[0089] The results of these "etching speed" and "appearance
evaluation" tests are shown as Example 2 in Table 1 above.
Examples 3-5
[0090] Precursor layer 41 shown in FIG. 1(b) was calcined under the
same conditions as in Example 1 and calcined again at 20.degree. C.
for 3 minutes to form resin layer 42 in the state shown in FIG.
1(c).
[0091] The imidation degree of the polyimide in resin layer 42 in
this state was determined under the same conditions as in Example 1
to be about 80%. The film thickness was about 19 .mu.m.
[0092] Then, a patterned resist layer 45 was formed on the surface
of this resin layer 42 by the same process as in Example 1.
[0093] Resin layer 42 in this state was immersed in each of three
etching solutions (the same etching solution as used in Example 1
kept at 65.degree. C., 75.degree. C. and 85.degree. C.) and
subjected to the "etching speed" test under the same conditions as
in Example 1.
[0094] After completion of etching, etched resin layer 42 was
washed, resist layer 45 and carrier film 33 were separated and
resin layer 42 was completely imidated under the same conditions as
in Example 1.
[0095] Resin layer 43 obtained by complete imidation of resin layer
42 was subjected to the "appearance evaluation" test under the same
conditions as in Example 1.
[0096] The results of these "etching speed" and "appearance
evaluation" tests with etching solutions at different temperatures
are shown as Examples 3-5 in Table 1 above.
Examples 6, 7
[0097] An etching solution was prepared in the same manner as in
Example 1 except that 1,4-propanediol was used as an alcohol in
place of 1,3-propanediol used in Example 1 and mixed with the same
water and potassium hydroxide in the same weight ratio as used in
Example 1.
[0098] The same resin layer 42 as used in Example 1 in the state
shown in FIG. 1(e) was immersed in said etching solution at
65.degree. C. or 75.degree. C. and subjected to the "etching speed"
test under the same conditions as in Example 1.
[0099] After completion of etching of this resin layer 42, resin
layer 42 was washed, resist layer 45 and carrier film 33 were
separated and resin layer 42 was completely imidated under the same
conditions as in Example 1, and the resulting resin layer 43 was
subjected to the "appearance evaluation" test under the same
conditions as in Example 1.
[0100] The results of these "etching speed" and "appearance
evaluation" tests with etching solutions at different temperatures
are shown as Examples 6, 7 in Table 1 above.
Examples 8-10
[0101] Precursor layer 41 in the state shown in FIG. 1(b) was
calcined twice under the same conditions as in Examples 3-5 and a
patterned resist layer 45 was formed on the surface of the
resulting resin layer 42 by the same process as in Example 1.
[0102] Resin layer 42 in this state was immersed in the same
etching solution as in Examples 6 and 7 at 65.degree. C.,
75.degree. C. or 85.degree. C. and subjected to the "etching speed"
test under the same conditions as in Example 1.
[0103] After completion of etching of resin layer 42, the resin
layer was washed, resist layer 45 and carrier film 33 were
separated and resin layer 42 was completely imidated under the same
conditions as in Example 1, and the resulting resin layer 43 was
subjected to the "appearance evaluation" test under the same
conditions as in Example 1.
[0104] The results of these "etching speed" and "appearance
evaluation" tests with etching solutions at different temperatures
are shown as Examples 8-10 in Table 1 above.
Comparative Examples 1, 2
[0105] The precursor layer in the state shown in FIG. 1(b) was
calcined twice under the same conditions as in Examples 3-5 and
further subjected to a third calcination at 350.degree. C. for 15
minutes, and the imidation degree of the resulting resin layer
determined under the same conditions as in Example 1 was about
100%. The film thickness of the resin layer was about 17 .mu.m.
[0106] A patterned resist layer was formed on the surface of the
resin layer in this state by the same process as in Example 1, and
then the resin layer was immersed in each of two etching solutions
at 85.degree. C. (the same etching solution as in Examples 1-5 and
the same etching solution as in Examples 6-10) and subjected to the
"etching speed" test under the same conditions as in Example 1.
[0107] After completion of etching, the resin layer was washed, the
resist layer and the carrier film were separated and the resin
layer was completely imidated under the same conditions as in
Example 1, and the resulting resin layer was subjected to the
"appearance evaluation" test under the same conditions as in
Example 1.
[0108] The results of these "etching speed" and "appearance
evaluation" tests with two etching solutions are shown as
Comparative examples 1, 2 in Table 1 above.
Comparative Example 3
[0109] An etching solution was prepared in the same manner as in
Example 1 except that ethylene glycol was used as an alcohol in
place of 1,3-propanediol used in Example 1 and mixed with the same
water and potassium hydroxide in the same weight ratio as used in
Example 1.
[0110] Then, the precursor layer in the state shown in FIG. 1(b)
was calcined twice under the same conditions as in Examples 3-5 and
a patterned resist layer was formed on the surface of the resulting
resin layer by the same process as in Example 1.
[0111] The resin layer in this state was immersed in said etching
solution at 75.degree. C. and subjected to the "etching speed" test
under the same conditions as in Example 1.
[0112] After completion of etching, the resin layer was washed, the
resist layer and the carrier film were separated and the resin
layer was completely imidated under the same conditions as in
Example 1, and the resulting resin layer was subjected to the
"appearance evaluation" test under the same conditions as in
Example 1.
[0113] The results of these "etching speed" and "appearance
evaluation" tests are shown as Comparative example 3 in Table 1
above.
Comparative Example 4
[0114] The precursor layer in the state shown in FIG. 1(b) was
calcined three times under the same conditions as in Comparative
examples 1, 2 and a patterned resist layer was formed on the
surface of the resulting resin layer by the same process as in
Example 1.
[0115] The resin layer in this state was immersed in the same
etching solution as in Comparative example 3 at 85.degree. C. and
subjected to the "etching speed" test under the same conditions as
in Example 1.
[0116] After completion of etching, the resin layer was washed, the
resist layer and the carrier film were separated and the resin
layer was completely imidated under the same conditions as in
Example 1, and the resulting resin layer subjected to the
"appearance evaluation" test under the same conditions as in
Example 1.
[0117] The results of these "etching speed" and "appearance
evaluation" tests are shown as Comparative example 4 in Table 1
above.
[0118] As shown in Table 1 above, Examples 1-5 and Examples 6-10
using a diol as an alcohol required a period of 10 minutes or less
for etching a resin layer calcined once or twice (resin layers 42
having a polyimide at an imidation degree in a range of 60-85%)
(etching speed) and showed good appearance.
[0119] Especially, Examples 2, 4, 5, 7, 9 and 10 using an etching
solution at 75.degree. C. or more required a period of less than 5
minutes for etching.
[0120] Even when an etching solution containing said diol was used,
a period of 10 minutes or more was required for etching a resin
layer calcined three times (imidation degree of about 100%) as in
Comparative examples 1, 2.
[0121] In Comparative examples 3 using an etching solution
containing ethylene glycol, the imidation degree was about 80% so
that a period of 5 minutes or more was required for etching even
when the temperature of the etching solution was 75.degree. C. or
more, and the appearance evaluation result was also poor.
[0122] Especially in Comparative example 4 wherein the imidation
degree of the polyimide in the resin layer is 100%, the resin layer
exposed at the bottom of the opening in the resist layer could not
be completely removed even when it was etched with an etching
solution at 85.degree. C. for 25 minutes, and the resist layer was
separated from the surface of the resin layer before the resin
layer was removed.
[0123] Resin layers 43 in the state shown in FIG. 1(h) obtained in
Examples 2, 4 above were further subjected to "impurity ion
analysis" by the method shown below.
[Impurity Ion Analysis]
[0124] Resin layers 43 completely imidated in Examples 2, 4 above
were measured for the contents (ppm) of chlorine ion, ammonium ion
and potassium ion per 1 g of each resin layer 43 by ion exchange
chromatography. These measurement results are shown in Table 2
below. TABLE-US-00002 TABLE 2 Results of impurity ion analysis
Imidation Chlorine ion Ammonium ion Potassium ion degree (ppm)
(ppm) (ppm) Example 2 60% 3.2 3.5 0.3 Example 4 80% 2.1 3.1 0.1
Comparative about 15% 28.8 8.1 0.4 example 14
Comparative Example 14
[0125] The same resist layer as in Example 1 was formed on the
surface of the precursor layer before calcination in the state
shown in FIG. 1(b), and this resist layer was patterned by the
process of Example 1. The substrate in this state was etched by
immersing it in an etching solution (a 2 wt % aqueous
tetramethylammonium hydroxide solution) at 40.degree. C. under the
same conditions as in Example 1.
[0126] After completion of etching, the precursor layer was washed,
the resist layer and carrier film were separated and the precursor
layer was completely imidated under the same conditions as in
Example 1 to give a resin layer. The resin layer in this state was
subjected to "impurity ion analysis" under the same conditions as
in Examples 2, 4. The results are shown in Table 2 above.
[0127] As shown in Table 2 above, Examples 2, 4 using an etching
solution containing 1,3-propanediol had low contents of all of
remaining impurity ions such as chlorine ion, ammonium ion and
potassium ion, confirming that etching solutions of the present
invention even containing potassium hydroxide cause no
contamination by potassium ion.
[0128] In Comparative example 14 using a tetramethylammonium
hydroxide solution for etching the precursor layer before
imidation, all of the impurity ions were determined at high
contents.
[0129] This is probably because the precursor layer has a low
imidation degree and a high polyamic acid content and the etching
solution does not contain a diol which protects the polar group of
the polyamic acid so that much of these impurity ions are bound to
the polar group of the polyamic acid during etching.
Examples 11-20
[0130] Any one of 1,3-propanediol used in Examples 1-5,
1,4-butanediol used in Examples 6-10 or other types of diols than
said diols (2, 3-butanediol and 1, 5-pentanediol), and the water
and potassium hydroxide used in Example 1 were mixed in the ratios
shown in Table 3 below to prepare 10 etching solutions.
[0131] Then, a resist layer 45 patterned under the same conditions
as in Example 1 was formed on the surface of the same resin layer
42 as used in Examples 3, 4 and 8-10 having an imidation degree of
80%.
[0132] These resin layers 42 were immersed in each of said 10
etching solutions at 75.degree. C. and subjected to the "etching
speed" test under the same conditions as in Example 1.
[0133] After completion of etching, resin layer 42 was washed,
resist layer 45 and carrier film 33 were separated and resin layer
42 was completely imidated under the same conditions as in Example
1, and the resulting resin layer 43 was subjected to the
"appearance evaluation" test under the same conditions as in
Example 1.
[0134] The results of these "etching speed" and "appearance
evaluation" tests with 10 etching solutions are shown as Examples
11-20 in Table 3 below. TABLE-US-00003 TABLE 3 Effects of solvent
type and mixing ratio on etching performance Mixing ratio (% by
weight) Etching Solvent Solvent Water KOH Water/KOH speed (min.)
Appearance Example 11 1,4-Butanediol 3 46 51 0.90 5.0 good Example
12 57 22 21 1.05 4.5 good Example 13 51 34 15 2.27 4.0 good Example
14 1,3-Propanediol 15 40 45 0.89 4.1 good Example 15 51 25 24 1.04
47 good Example 16 2,3-Butanediol 15 40 45 0.89 4.5 good Example 17
33 34 33 1.04 4.0 good Example 18 1,5-Pentanediol 13 50 37 1.35 4.9
good Example 19 31 38 31 1.23 5.0 good Example 20 51 25 24 1.04 5.7
good Comparative 1,4-Butanediol 3 82 15 5.47 10.5 poor example 5
Comparative 3 76 21 3.62 7.0 poor example 6 Comparative 3 40 57
0.70 >20 N.A. example 7 Comparative 39 22 39 0.56 >20 N.A.
example 8 Comparative 51 16 33 0.48 >20 N.A. example 9
Comparative 69 10 21 0.48 >20 N.A. example 10 Comparative 0 47
53 0.89 7.8 poor example 11 Comparative 69 16 15 1.07 8.0 poor
example 12 Comparative 65 26 9 2.89 8.0 poor example 13
Comparative Examples 5-13
[0135] The same alcohol (1,4-butanediol), water and potassium
hydroxide as used in Examples 6-10 were mixed in the ratios (% by
weight) shown in Table 3 above to prepare 9 etching solutions.
[0136] Then, a resist layer patterned under the same conditions as
in Example 1 was formed on the surface of the same resin layer as
used in Examples 3, 4 and 8-10 having an imidation degree of 80%.
The resin layer in this state was immersed in each of said 9
etching solutions at 75.degree. C. and subjected to the "etching
speed" test under the same conditions as in Example 1.
[0137] After completion of etching, the resin layer was washed, the
resist layer and the carrier film were separated and the resin
layer was completely imidated under the same conditions as in
Example 1, and the resulting resin layer was subjected to the
"appearance evaluation" test under the same conditions as in
Example 1.
[0138] The results of these "etching speed" and "appearance
evaluation" tests with 9 etching solutions are shown as Comparative
examples 5-13 in Table 3 above.
[0139] As shown in Table 3 above, etching speed was always less
than 6 minutes and opening 49 in etched resin layer 43 showed a
good shape when etching solutions of Examples 11-20 were used.
[0140] In Comparative examples 5 and 6 using an etching solution
containing water in an amount (weight) of three times or more the
amount (weight) of potassium hydroxide, however, not only etching
speed was 7 minutes or more but also the opening formed by etching
had an undulated edge.
[0141] In Comparative examples 7-10 using an etching solution
containing water in an amount (weight) of 0.7 times or less the
amount (weight) of potassium hydroxide, the resist layer was
separated when the etching period passed 20 minutes before the
resin layer was completely removed and etching could not be
completed.
[0142] In Comparative example 11 using an etching solution
containing no alcohol, not only etching speed was low but also the
shape of the etched pattern was poor.
[0143] In Comparative examples 12 and 13 using an etching solution
containing 65% by weight or more of an alcohol, etching speed was
further lower than Comparative example 11.
[0144] Next, a process for manufacturing another example of
flexible wiring board of the present invention is explained with
reference to FIG. 2(a)-2(f).
Example
[0145] Reference numeral 19 in FIG. 2(a) represents a substrate
having a base film 11 and a metal wiring 15 provided on the surface
of base film 11.
[0146] On the side of substrate 19 on which metal wiring 15 is
provided, a polyamic acid coating solution is initially applied and
heated to dryness in a drying oven at 100.degree. C. for 4 minutes
to form a layer of a polyimide precursor (polyamic acid). Reference
numeral 21 in FIG. 2(b) represents thus formed precursor layer.
[0147] Then, the assembly is further heated at 160.degree. C. for 3
minutes to imidate the polyamic acid contained in precursor layer
21.
[0148] Reference numeral 22 in FIG. 2(c) represents a resin layer
obtained by imidating precursor layer 21, and the imidation degree
of the polyimide contained in this resin layer 22 is in the range
of 50-98%.
[0149] Then, a resist layer coating solution is applied and dried
on the surface of resin layer 22 in this state to form a resist
layer 25 (FIG. 2(d)). Then, this resist layer 25 is patterned by
exposure and development.
[0150] Reference numeral 29 in FIG. 2(e) represents an opening
formed in resist layer 25 by patterning, and resin layer 22 is
exposed at the bottom of this opening 29.
[0151] Then, the same etching solution as used in Example 1 above
is warmed to 65.degree. C. or more, and resin layer 22 in the state
shown in FIG. 2(e) is wholly immersed in the etching solution at
65.degree. C. or more with gentle stirring to remove resin layer 22
exposed at the bottom of opening 29 (etching).
[0152] When resin layer 22 at the bottom of opening 29 is
completely removed and the surface of metal wiring 15 is exposed at
the bottom of opening 29, the assembly is removed from the etching
solution and the etching solution is washed off the assembly with
warm water at 60.degree. C. to complete etching.
[0153] FIG. 2(f) shows the state in which etching has been
completed and opening 29 is formed in resin layer 22 and metal
wiring 15 is exposed at the bottom of opening 29.
[0154] Then, resist layer 25 is separated and the assembly is
heated at 350.degree. C. for 15 minutes to completely imidate the
polyimide in resin layer 22 into a second example of flexible
wiring board as shown by reference numeral 10 in FIG. 2(g).
[0155] Next, a process for connecting a flexible wiring board 10,
30 of the present invention to another flexible wiring board is
explained.
[0156] Reference numeral 70 in FIG. 4(a) represents another
flexible wiring board to be laminated to a flexible wiring board 10
of the present invention. This flexible wiring board 70 has a base
film 71, a metal wiring 72 provided on the surface of base film 71,
and a cover film 73 provided on the side of base film 71 on which
metal wiring 72 is provided.
[0157] Cover film 73 has openings 76 at positions where metal
wiring 72 is located. Bumps 77 formed to stand in perpendicular
direction on the surface of metal wiring 72 are received in
openings 76 in cover film 73, with the tops of bumps 77 projecting
over the surface of cover film 73.
[0158] In order to connect this flexible wiring board 70 to a
flexible wiring board shown by reference numeral 10, resin layer 23
of flexible wiring board 10 and cover film 73 of another flexible
wiring board 70 are faced each other so that openings 29 in resin
layer 23 are aligned with bumps 77 projecting over the surface of
cover film 73.
[0159] Then, flexible wiring board 70 is pressed against flexible
wiring board 10 of the present invention so that the tops of bumps
77 come into contact with metal wiring 15 via openings 29 in resin
layer 23 (FIG. 4(b)).
[0160] Cover film 73 of flexible wiring board 70 consists of a
resin developing adhesiveness upon heating so that flexible wiring
board 70 in the state shown in FIG. 4(b) is heated under pressure
to mechanically connect two flexible wiring boards 10, 70 via cover
film 73.
[0161] Reference numeral 5 in FIG. 4(b) represents a flexible
wiring board of multilayer structure consisting of mechanically
connected flexible wiring boards 10, 70, and these flexible wiring
boards 10, 70 are electrically connected via bumps 77.
[0162] Although flexible wiring board 10 shown in FIG. 2(g) is used
in the foregoing embodiment, the present invention is not limited
to this embodiment but a multilayer flexible wiring board as shown
by reference numeral 6 in FIG. 5 can also be prepared by connecting
a flexible wiring board shown by reference numeral 30 in FIG. 1(i)
and a flexible wiring board 70 having bumps 77.
[0163] Although metal wiring 15, 35 is exposed at the bottom of
opening 29, 49 in resin layer 23, 43 in the foregoing embodiments,
the present invention is not limited to these embodiments.
[0164] Reference numeral 80 in FIG. 6 represents a third example of
flexible wiring board of the present invention. This flexible
wiring board 80 has the same base film 11, metal wiring 15 and
resin layer 23 as those of a flexible wiring board shown by
reference numeral 10 in FIG. 2(g). Bumps 27 formed to stand in
perpendicular direction on the surface of metal wiring 15 are
arranged in openings 29 in resin layer 23, with the tops of bumps
27 projecting over the surface of resin layer 23.
[0165] Reference numeral 90 in FIG. 7 represents a fourth example
of flexible wiring board of the present invention, which has the
same base film 40, metal wiring 35 and resin layer 43 as those of a
flexible wiring board shown by reference numeral 30 in FIG. 1(i).
Similarly to said third example of flexible wiring board 80, bumps
47 are received in openings 49 in resin layer 43.
[0166] Although an alkali metal hydroxide consisting of potassium
hydroxide is used as an alkali compound in the foregoing
embodiments, the present invention is not limited to these
embodiments, but sodium hydroxide can also be used, for
example.
[0167] When a less water-soluble compound such as lithium hydroxide
is used, it is preferably used in combination with a highly
water-soluble compound such as potassium hydroxide or sodium
hydroxide.
[0168] Organic alkali compounds such as quaternary ammonium
hydroxide can also be used, especially commercially readily
available aqueous solutions of tetramethylammonium hydroxide,
tetraethylammonium hydroxide or the like.
[0169] However, these aqueous quaternary ammonium hydroxide
solutions are normally commercially available as low concentration
aqueous solutions at 25% by weight or less so that these solutions
cannot be used as such for etching solutions of the present
invention (alkali compound:water=1:0.75-3.0) because the water
content becomes 4 times or more the content of the alkali compound,
quaternary ammonium hydroxide.
[0170] Therefore, commercially available aqueous quaternary
ammonium hydroxide solutions are preferably concentrated in advance
to a quaternary ammonium hydroxide content of 34% by weight or more
using a rotary evaporator or the like and then used for etching
solutions of the present invention.
[0171] When such an organic alkali compound is used in combination
with an inorganic alkali compound such as potassium hydroxide,
etching speed can be synergistically increased.
[0172] In the present invention, etching solutions having a high
etching speed can be obtained when the amount (weight) of water is
in the range of 0.75-3.0 times, more preferably 0.85-2.5 times the
amount of the alkali compound.
[0173] However, an optimal etching period desirably stretches over
a range because too high etching speed causes overetching.
[0174] The mixing ratio of the alkali compound to water should be
determined within the range defined above with due consideration
for the fact that the finishing appearance after etching is not
always proportional to etching speed.
[0175] Various classes of alcohol can be used in the present
invention so far as they belong to diols containing 3 to 6 carbon
atoms or triols containing 4 to 6 carbon atoms. For example, diols
containing less than 2 carbon atoms such as ethylene glycol or
triols containing less than 3 carbon atoms such as glycerin are not
suitable for etching solutions of the present invention because of
the low etching speed.
[0176] Etching solutions using a diol or triol containing more than
6 carbon atoms as an alcohol have a lower etching speed as compared
with etching solutions of the present invention.
[0177] Alcohols containing more than 6 carbon atoms are not
suitable for etching solutions of the present invention because
they have a low solubility for water to result in etching solutions
with low dispersibility.
[0178] The amount of an alcohol used in the present invention is in
the range of 3-65% by weight, but may be in the range of 5-55% by
weight to further increase etching speed.
[0179] However, etching precision and the appearance after etching
are influenced by resist layer 25 and the type and amount of the
alcohol used, so that the type and amount of the alcohol should be
determined with consideration for the type of resist layer 25 used
for etching and the etching precision required.
[0180] The type of the polyimide that can be used in the present
invention is not specifically limited, either, but various types
can be used.
[0181] Although precursor layer 21, 41 is initially formed and then
imidated into resin layer 22, 42 in the foregoing embodiments, the
present invention is not limited to these embodiments.
[0182] For example, a polyamic acid may be imidated to an imidation
degree of 50-98% during the synthesis, and the polyimide in this
state may be dissolved in a solvent and then applied and dried on
the surface of metal foil 31 or metal wiring 15 to directly form an
imidated resin layer.
[0183] In this case, the process is simplified by omitting
imidation (heating) before etching, but suitable polyimides are
limited to the solvent-soluble type.
[0184] Although a test piece is wholly immersed in an etching
solution to etch resin layer 22, 42 in the foregoing embodiments,
the present invention is not limited to these embodiments. For
example, an etching solution of the present invention may be
sprayed on the face having resist layer 25, 45 to etch resin layer
22, 42.
[0185] According to the present invention, resin layers can be
rapidly and precisely etched without using an amine or a lower
alcohol.
* * * * *