U.S. patent application number 15/910499 was filed with the patent office on 2018-09-27 for surface-treated copper foil, copper foil with carrier, substrate, resin substrate, printed wiring board, copper clad laminate and method for producing printed wiring board.
This patent application is currently assigned to JX Nippon Mining & Metals Corporation. The applicant listed for this patent is JX Nippon Mining & Metals Corporation. Invention is credited to Misato HONDA, Masafumi ISHII, Nobuaki MIYAMOTO.
Application Number | 20180279482 15/910499 |
Document ID | / |
Family ID | 53186921 |
Filed Date | 2018-09-27 |
United States Patent
Application |
20180279482 |
Kind Code |
A1 |
ISHII; Masafumi ; et
al. |
September 27, 2018 |
SURFACE-TREATED COPPER FOIL, COPPER FOIL WITH CARRIER, SUBSTRATE,
RESIN SUBSTRATE, PRINTED WIRING BOARD, COPPER CLAD LAMINATE AND
METHOD FOR PRODUCING PRINTED WIRING BOARD
Abstract
A surface-treated copper foil is capable of imparting the
profile shape of the substrate surface after removal of the copper
foil, the profile shape maintaining fine wiring formability and
achieving satisfactory adhesion of electroless copper plating
coating. A resin substrate is provided with a profile shape of the
surface maintaining fine wiring formability and achieving
satisfactory adhesion of electroless copper plating coating. The
surface-treated copper foil has a surface-treated layer formed on a
copper foil, and the surface roughness Sz of the surface of the
surface-treated layer is 2 to 6 .mu.m.
Inventors: |
ISHII; Masafumi; (Ibaraki,
JP) ; HONDA; Misato; (Ibaraki, JP) ; MIYAMOTO;
Nobuaki; (Ibaraki, JP) |
|
Applicant: |
Name |
City |
State |
Country |
Type |
JX Nippon Mining & Metals Corporation |
Tokyo |
|
JP |
|
|
Assignee: |
JX Nippon Mining & Metals
Corporation
Tokyo
JP
|
Family ID: |
53186921 |
Appl. No.: |
15/910499 |
Filed: |
March 2, 2018 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
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14907478 |
Jan 25, 2016 |
9955583 |
|
|
PCT/JP2014/069489 |
Jul 23, 2014 |
|
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15910499 |
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Current U.S.
Class: |
1/1 |
Current CPC
Class: |
C25D 5/10 20130101; C25D
3/562 20130101; C25D 3/38 20130101; C25D 3/58 20130101; H05K 3/025
20130101; H05K 2203/0307 20130101; H05K 2203/1152 20130101; H05K
2203/0726 20130101; B32B 3/26 20130101; C23C 18/405 20130101; C25D
5/48 20130101; H05K 2201/0355 20130101; C25D 5/022 20130101; H05K
1/09 20130101; H05K 2203/072 20130101; H05K 3/205 20130101; B32B
2457/08 20130101; H05K 3/384 20130101; H05K 3/388 20130101; C25D
5/18 20130101; C25D 7/0614 20130101; C25D 5/34 20130101; H05K 3/389
20130101; H05K 3/427 20130101; C23C 18/1653 20130101; C25D 7/0671
20130101; B32B 15/20 20130101; C25D 1/04 20130101; B32B 15/08
20130101 |
International
Class: |
H05K 3/02 20060101
H05K003/02; B32B 3/26 20060101 B32B003/26; B32B 15/08 20060101
B32B015/08; B32B 15/20 20060101 B32B015/20; C25D 7/06 20060101
C25D007/06; H05K 3/20 20060101 H05K003/20; H05K 3/38 20060101
H05K003/38 |
Foreign Application Data
Date |
Code |
Application Number |
Jul 23, 2013 |
JP |
2013-153010 |
Jul 23, 2013 |
JP |
2013-153014 |
Aug 1, 2013 |
JP |
2013-160827 |
Aug 1, 2013 |
JP |
2013-160828 |
Claims
1. A substrate prepared by bonding a surface-treated copper foil
wherein a surface treated layer is formed on a copper foil, wherein
the surface roughness Sz of the surface of the surface-treated
layer is 2 to 6 .mu.m, the surface-treated copper foil optionally
having a resin layer on the surface-treated layer, via the
surface-treated layer side thereof, to a substrate, and by removing
the surface-treated copper foil, or a substrate prepared by bonding
a copper foil with carrier, the copper foil with carrier comprising
a carrier, an intermediate layer and an ultra-thin copper layer in
this order, the ultra-thin copper layer being a surface-treated
copper foil wherein a surface treated layer is formed on a copper
foil, wherein the surface roughness Sz of the surface of the
surface-treated layer is 2 to 6 .mu.m and optionally having a resin
layer, via the ultra-thin copper layer side thereof, to a
substrate, and by removing the carrier from the copper foil with
carrier and removing the ultra-thin copper layer which is the
surface-treated copper foil, wherein at least one of the following
(1) to (3) is satisfied: (1) the surface roughness Sz of the
surface, on the copper foil removal side, of the substrate is 1 to
5 .mu.m, (2) the ratio B/A of the three-dimensional surface area B
to the two-dimensional surface area A of surface, on the copper
foil removal side of the substrate, is 1.01 to 1.5, or (3) the
black area rate of the surface, on the copper foil removal side, of
the substrate is 10 to 50%, and the average value of the diameters
of the holes of the surface, on the copper foil removal side of the
substrate, is 0.03 to 1.0 .mu.m.
2. A resin substrate wherein at least one of the following (1) to
(3) is satisfied: (1) a surface roughness Sz of the surface of the
resin substrate is 1 to 5 .mu.m, (2) the ratio B/A of the
three-dimensional surface area B to the two-dimensional surface
area A of the surface of the resin substrate is 1.01 to 1.5, or (3)
the black area rate of the surface of the resin substrate is 10 to
50%, and the average value of the diameters of the holes of the
surface of the resin substrate is 0.03 to 1.0 .mu.m.
3. A method for producing a printed wiring board comprising: a step
of preparing the resin substrate according to claim 2, and a step
of forming a circuit on the surface of the resin substrate.
4. A method for producing a printed wiring board comprising: a step
of preparing the resin substrate according to claim 2, and a step
of producing a printed wiring board with the resin substrate.
5. A copper clad laminate comprising the resin substrate according
to claim 2.
6. A method for producing a printed wiring board, comprising: a
step of preparing a surface-treated copper foil, or a copper foil
with carrier comprising a carrier, an intermediate layer and an
ultra-thin copper layer in this order, and a resin substrate; a
step of laminating the surface-treated copper foil, via the
surface-treated layer side thereof, on the resin substrate, or a
step of laminating the copper foil with carrier, via the ultra-thin
copper layer side thereof, on the resin substrate, and then peeling
the carrier of the copper foil with carrier; a step of obtaining
the resin substrate according to claim 2 by removing the
surface-treated copper foil or removing the ultra-thin copper layer
on the resin substrate; and a step of forming a circuit on the
surface of the resin substrate with the surface-treated copper foil
or the ultra-thin copper layer removed therefrom.
7. A method for producing a printed wiring board, comprising: a
step of forming a copper clad laminate by laminating a
surface-treated copper foil via the surface-treated layer side
thereof, on the resin substrate according to claim 2, or by
laminating a copper foil with carrier comprising a carrier, an
intermediate layer and an ultra-thin copper layer in this order,
via the ultra-thin copper layer side thereof, on the resin
substrate according to claim 42, and then, peeling the carrier of
the copper foil with carrier; and a step of subsequently forming a
circuit by a semi-additive method, a subtractive method, a partly
additive method or a modified semi-additive method.
8. A method for producing a printed wiring board, comprising: a
step of preparing a metal foil with circuit formed on the surface
thereof, or a step of forming a circuit on the surface on the
ultra-thin copper layer side of a copper foil with carrier
constituted by laminating a carrier, an intermediate layer and an
ultra-thin copper layer in this order; a step of forming the resin
substrate according to claim 2 on the surface of the metal foil, or
on the surface on the ultra-thin copper layer side of a copper foil
with carrier, so as for the circuit to be embedded; a step of
forming a circuit on the resin layer; and a step of exposing the
circuit formed on the surface of the metal foil or on the surface
of the copper foil with carrier and embedded in the resin substrate
by removing the metal foil or the copper foil with carrier.
9. A surface-treated copper foil, wherein at least one of the
following (1) to (3) is satisfied: (1) when the surface-treated
copper foil is bonded, via the surface-treated layer side thereof,
to a resin substrate and the surface-treated copper foil is
removed, the surface roughness Sz of the surface on the copper foil
removal side of the resin substrate is 1 to 3 .mu.m, (2) when the
surface-treated copper foil is bonded, via the surface-treated
layer side thereof, to a resin substrate and the surface-treated
copper foil is removed, the black area rate of the surface on the
copper foil removal side of the resin substrate is 10 to 45%, (3)
when the surface-treated copper foil is bonded, via the
surface-treated layer side thereof, to a resin substrate and the
surface-treated copper foil is removed, the average value of the
diameters of holes of the surface on the copper foil removal side
of the resin substrate is 0.03 to 0.7 .mu.m.
Description
CROSS-REFERENCE TO RELATED APPLICATION
[0001] This Application is a divisional of application Ser. No.
14/907,478, filed on 25 Jan. 2016 by Ishii et al., now U.S. Pat.
No. ______, which is a national stage of PCT/JP 2014/069489, filed
on 23 Jul. 2014. The whole content of those applications is
incorporated herein by reference as if set forth explicitly herein.
This application claims benefit of Japanese Applications Nos.
2013-153010 and 2013-153014, filed on 23 Jul. 2013, and 2013-160827
and 2013-160828, filed on 1 Aug. 2013.
TECHNICAL FIELD
[0002] The present invention relates to a surface-treated copper
foil, a copper foil with carrier, a substrate, a resin substrate, a
printed wiring board, a copper clad laminate and a method for
producing a printed wiring board.
[0003] As the method for forming circuits of a semiconductor
package substrate and a printed wiring board, a subtractive method
is predominantly used. However, recently, due to high integration
of semiconductors, miniaturization has been advanced in the
circuits of semiconductor package substrates and printed wiring
boards used for highly integrated semiconductors, and accordingly
it has been becoming difficult to form fine circuits on the basis
of subtractive methods.
[0004] As measures for forming further finer wirings, the following
methods have been attracting attention: a circuit forming method
(1) in which pattern copper plating is performed by using an
ultra-thin copper foil as a power feeding layer, and finally the
ultra-thin copper layer is removed by flash etching to form
wirings; a circuit forming method (2) in which a prepreg or a
build-up film is cured by vacuum pressing or the like, the surface
of the cured material is roughened to form appropriate asperities
on the surface of a substrate, and thus reliable fine wirings are
formed on the substrate surface; and a circuit forming method (3)
in which a surface profile of a copper foil is transferred to the
surface of a substrate to form appropriate asperities on the
substrate surface, and thus reliable fine airings are formed on the
substrate surface. These methods are each generally referred to as
a SAP (semi-additive process).
[0005] A SAP using the surface profile of a copper foil is
described in, for example, Patent Literature 1. Examples of a
typical SAP using such a surface profile of a copper foil includes
the following. Specifically, here is quoted a method in which a
copper foil laminated on a resin is subjected to an entire-surface
etching, the etched surface of a substrate is subjected to hole
opening, the hole-opening portions and the entire surface or part
of the surface of the substrate are subjected to desmear treatment,
a dry film is bonded to the etched surface of the hole opening
portions, the dry film on the portions in which no circuit is
formed is exposed and developed, the unnecessary portion of the dry
film is removed with a chemical solution, electroless copper
plating and electric copper plating are applied to the etched
substrate surface having no coating dry film and having the copper
foil surface profile transferred thereto, and finally the
electroless copper plating layer is removed by flash etching to
form fine wirings.
CITATION LIST
Patent Literature
[0006] Japanese Patent Laid-Open No. 2006-196863
SUMMARY OF INVENTION
Technical Problem
[0007] For forming fine wirings, it is preferable that the profile
of the substrate surface be small and smooth; however, in such a
case, the adhesion of the electroless copper plating coating is
weak, and the reliability demanded for semiconductor package
substrates or printed wiring boards is liable to be impaired. On
the other hand, in order to ensure the adhesion of the electroless
copper plating coating, it is preferable that the profile of the
substrate surface be large; however, in such a case, fine wiring
formability is liable to be impaired.
[0008] With these respects, the conventional technology has not yet
performed sufficient investigation, to leave room for improvement.
Accordingly, the present invention takes it as its object to
provide a surface-treated copper foil capable of imparting the
profile shape of the substrate surface after removal of the copper
foil, the profile shape maintaining fine wiring formability and
achieving satisfactory adhesion of electroless copper plating
coating, and/or a resin substrate provided with such a profile
shape of the surface thereof.
Solution to Problem
[0009] In order to achieve the above-described object, the present
inventors continuously made a diligent study, and have consequently
discovered that a surface-treated copper foil in which the surface
roughness (the maximum height of the surface) Sz of the surface of
a surface-treated layer is controlled so as to fall within a
predetermined range is used, the surface-treated copper foil
concerned is bonded to a substrate on which circuits are to be
formed, then the surface-treated copper foil is removed, and thus,
it is possible to provide a profile shape of the substrate surface
after removal of the copper foil, the profile shape maintaining the
fine wiring formability and achieving satisfactory adhesion of
electroless copper plating coating. In addition, the present
inventors have discovered that by using a resin substrate in which
the surface roughness (the maximum height of the surface) Sz of the
surface is controlled so as to fall within a predetermined range,
the fine wiring formability can be maintained and the satisfactory
adhesion of the electroless copper plating coating can be achieved,
during forming circuits on the resin substrate surface.
[0010] The present invention has been perfected on the basis of the
above-described discovery, and an aspect of the present invention
is a surface-treated copper foil, wherein a surface treated layer
is formed on a copper foil, and the surface roughness Sz of the
surface of the surface-treated layer is 2 to 6 .mu.m.
[0011] In an embodiment, the surface-treated copper foil of the
present invention is a surface-treated copper foil, wherein a
surface-treated layer is formed on a copper foil, and the ratio B/A
of the three-dimensional surface area B to the two-dimensional
surface area A of the surface of the surface-treated layer is 1.05
to 1.8.
[0012] In another embodiment, in the surface-treated copper foil of
the present invention, when the surface-treated copper foil is
bonded, via the surface-treated layer side thereof, to a resin
substrate and the surface-treated copper foil is removed, the
surface roughness Sz of the surface, on the copper foil removal
side, of the resin substrate is 1 to 5 .mu.m.
[0013] In yet another embodiment, in the surface-treated copper
foil of the present invention, when the surface-treated copper foil
is bonded, via the surface-treated layer side thereof, to a resin
substrate and the surface-treated copper foil is removed, the ratio
B/A of the three-dimensional surface area B to the two-dimensional
surface area A of the surface, on the copper foil removal side, of
the resin substrate is 1.01 to 1.5.
[0014] In yet another embodiment, in the surface-treated copper
foil of the present invention, when the surface-treated copper foil
is bonded, via the surface-treated layer side thereof, to a resin
substrate and the surface-treated copper foil is removed, the black
area rate of the surface, on the copper foil removal side, of the
resin substrate is 10 to 50%, and the average value of the
diameters of the holes of the surface, on the copper foil removal
side, of the resin substrate is 0.03 to 1.0 .mu.m.
[0015] In another embodiment, the surface-treated copper foil of
the present invention is a surface-treated copper foil having a
surface-treated layer formed on a copper foil, wherein the ratio
B/A of the three-dimensional surface area B to the two-dimensional
surface area A of the surface of the surface-treated layer is 1.05
to 1.8.
[0016] In yet another embodiment, in the surface-treated copper
foil of the present invention, when the surface-treated copper foil
is bonded, via the surface-treated layer side thereof, to a resin
substrate and the surface-treated copper foil is removed, the
surface roughness Sz of the surface, on the copper foil removal
side, of the resin substrate is 1 to 5 .mu.m.
[0017] In yet another embodiment, in the surface-treated copper
foil of the present invention, when the surface-treated copper foil
is bonded, via the surface-treated layer side thereof, to a resin
substrate and the surface-treated copper foil is removed, the ratio
B/A of the three-dimensional surface area B to the two-dimensional
surface area A of the surface, on the copper foil removal side, of
the resin substrate is 1.01 to 1.5.
[0018] In yet another embodiment, in the surface-treated copper
foil of the present invention, when the surface-treated copper foil
is bonded, via the surface-treated layer side thereof, to the resin
substrate and the surface-treated copper foil is removed, the black
area rate of the surface, on the copper foil removal side, of the
resin substrate is 10 to 50%, and the average value of the
diameters of the holes of the surface, on the copper foil removal
side, of the resin substrate is 0.03 to 1.0 .mu.m.
[0019] In yet another aspect, the surface-treated copper foil of
the present invention is a surface-treated copper foil, wherein
when the surface-treated copper foil is bonded, via the
surface-treated layer side thereof, to a resin substrate and the
surface-treated copper foil is removed, the surface roughness Sz of
the surface, on the copper foil removal side, of the resin
substrate is 1 to 5 .mu.m.
[0020] In yet another embodiment, in the surface-treated copper
foil of the present invention, when the surface-treated copper foil
is bonded, via the surface-treated layer side thereof, to a resin
substrate and the surface-treated copper foil is removed, the ratio
B/A of the three-dimensional surface area B to the two-dimensional
surface area A of the surface, on the copper foil removal side, of
the resin substrate is 1.01 to 1.5.
[0021] In yet another embodiment, in the surface-treated copper
foil of the present invention, when the surface-treated copper foil
is bonded, via the surface-treated layer side thereof, to a resin
substrate and the surface-treated copper foil is removed, the black
area rate of the surface, on the copper foil removal side, of the
resin substrate is 10 to 50%, and the average value of the
diameters of the holes of the surface, on the copper foil removal
side, of the resin substrate is 0.03 to 1.0 .mu.m.
[0022] In yet another aspect, the present invention is a
surface-treated copper foil, wherein when the surface-treated
copper foil is bonded, via the surface-treated layer side thereof,
to a resin substrate and the surface-treated copper foil is
removed, the ratio B/A of the three-dimensional surface area B to
the two-dimensional surface area A of the surface, on the copper
foil removal side, of the resin substrate is 1.01 to 1.5.
[0023] In yet another embodiment in the present invention, when the
surface-treated copper foil is bonded, via the surface-treated
layer side thereof, to a resin substrate and the surface-treated
copper foil is removed, the black area rate of the surface, on the
copper foil removal side, of the resin substrate is 10 to 50%, and
the average value of the diameters of the holes of the surface, on
the copper foil removal side, of the resin substrate is 0.03 to 1.0
.mu.m.
[0024] In yet another aspect, the present invention is a
surface-treated copper foil, wherein when the surface-treated
copper foil is bonded, via the surface-treated layer side thereof,
to a resin substrate and the surface-treated copper foil is
removed, the black area rate of the surface, on the copper foil
removal side, of the resin substrate is 10 to 50%, and the average
value of the diameters of the holes of the surface, on the copper
foil removal side, of the resin substrate is 0.03 to 1.0 .mu.m.
[0025] In yet another embodiment, in the surface-treated copper
foil of the present invention, the surface-treated layer is a
roughening-treated layer.
[0026] In yet another embodiment, in the surface-treated copper
foil of the present invention, the roughening-treated layer is a
layer composed of a single substance selected from or an alloy
including one or more selected from the group consisting of copper,
nickel, cobalt, phosphorus, tungsten, arsenic, molybdenum, chromium
and zinc.
[0027] In yet another embodiment, the surface-treated copper foil
of the present invention has, on the surface of the
roughening-treated layer, one or more layers selected from the
group consisting of a heat resistant layer, a rust-preventing
layer, a chromate-treated layer and a silane coupling treated
layer.
[0028] In a yet another embodiment, in the surface-treated copper
foil of the present invention, the surface-treated layer is one or
more layers selected from the group consisting of a
roughening-treated layer, a heat resistant layer, a rust-preventing
layer, a chromate-treated layer and a silane coupling treated
layer.
[0029] In a yet another embodiment, the surface-treated copper foil
of the present invention is provided with a resin layer on the
surface-treated layer.
[0030] In yet another aspect, the present invention is a copper
foil with carrier, including a carrier, an intermediate layer and
an ultra-thin copper layer in this order, wherein the ultra-thin
copper layer is the surface-treated copper foil of the present
invention.
[0031] In an embodiment, the copper foil with carrier of the
present invention includes the ultra-thin copper layer on each of
both surfaces of the carrier.
[0032] In another embodiment, the copper foil with carrier of the
present invention includes a roughening-treated layer on the side
opposite to the ultra-thin copper layer of the carrier.
[0033] In yet another aspect, the present invention is a substrate
prepared by bonding the surface-treated copper foil of the present
invention, via the surface-treated layer side thereof, to a
substrate, and by removing the surface-treated copper foil, wherein
the surface roughness Sz of the surface, on the copper foil removal
side, of the substrate is 1 to 5 .mu.m.
[0034] In yet another aspect, the present invention is a substrate
prepared by bonding the copper foil with carrier of the present
invention, via the ultra-thin copper layer side thereof, to a
substrate, by removing the carrier from the copper foil with
carrier, and by then removing the ultra-thin copper layer, being
the surface-treated copper foil, wherein the surface roughness Sz
of the surface, on the copper foil removal side, of the substrate
is 1 to 5 pin.
[0035] In yet another aspect, the present invention is a substrate
prepared by bonding the surface-treated copper foil of the present
invention, via the surface-treated layer side thereof, to a
substrate, and by removing the surface-treated copper foil, wherein
the ratio B/A of the three-dimensional surface area B to the
two-dimensional surface area A of surface, on the copper foil
removal side, of the substrate is 1.01 to 1.5.
[0036] In yet another aspect, the present invention is a substrate
prepared by bonding the copper foil with carrier of the present
invention, via the ultra-thin copper layer side thereof, to a
substrate, by removing the carrier from the copper foil with
carrier, and by then removing the ultra-thin copper layer, being
the surface-treated copper foil, wherein the ratio B/A of the
three-dimensional surface area B to the two-dimensional surface
area A of surface, on the copper foil removal side, of the
substrate is 1.01 to 1.5.
[0037] In yet another aspect, the present invention is a substrate
prepared by bonding the surface-treated copper foil of the present
invention, via the surface-treated layer side thereof, to a
substrate, and by removing the surface-treated copper foil, wherein
the black area rate of the surface, on the copper foil removal
side, of the substrate is 10 to 50%/o, and the average value of the
diameters of the holes of the surface, on the copper foil removal
side, of the substrate is 0.03 to 1.0 .mu.m.
[0038] In yet another aspect, the present invention is a substrate
prepared by bonding the copper foil with carrier of the present
invention, via the ultra-thin copper layer side thereof, to a
substrate, by removing the carrier from the copper foil with
carrier, and by then removing the ultra-thin copper layer, being
the surface-treated copper foil, wherein the black area rate of the
surface, on the copper foil removal side, of the substrate is 10 to
50%, and the average value of the diameters of the holes of the
surface, on the copper foil removal side, of the substrate is 0.03
to 1.0 .mu.m.
[0039] In yet another aspect, the present invention is a copper
clad laminate produced by using the surface-treated copper foil of
the present invention, or the copper foil with carrier of the
present invention.
[0040] In yet another aspect, the present invention is a printed
wiring board produced by using the surface-treated copper foil of
the present invention, or the copper foil with carrier of the
present invention.
[0041] In yet another aspect, the present invention is an
electronic device using the printed wiring board of the present
invention.
[0042] In yet another aspect, the present invention is a method for
producing a printed wiring board, including: [0043] a step of
preparing the surface-treated copper foil of the present invention
and an insulating substrate; [0044] a step of laminating the
surface-treated copper foil, via the surface-treated layer side
thereof, on the insulating substrate; [0045] a step of removing the
surface-treated copper foil on the insulating substrate; and [0046]
a step of forming a circuit on the surface of the insulating
substrate with the surface-treated copper foil removed
therefrom.
[0047] In yet another aspect, the present invention is a method for
producing a printed wiring board, including: [0048] a step of
preparing the copper foil with carrier of the present invention and
an insulating substrate; [0049] a step of laminating the copper
foil with carrier, via the ultra-thin copper layer side thereof, on
the insulating substrate; [0050] a step of peeling the carrier of
the copper foil with carrier after laminating the copper foil with
carrier and the insulating substrate on each other; [0051] a step
of removing the ultra-thin copper layer on the insulating substrate
after peeling the carrier; and [0052] a step of forming a circuit
on the surface of the insulating substrate with the ultra-thin
copper layer removed therefrom.
[0053] In yet another aspect, the present invention is a method for
producing a printed wiring board, including: [0054] a step of
preparing the surface-treated copper foil of the present invention
and an insulating substrate; [0055] a step of forming a copper clad
laminate by laminating the surface-treated copper foil, via the
surface-treated layer side thereof, on the insulating substrate;
and [0056] a step of subsequently forming a circuit by a
semi-additive method, a subtractive method, a partly additive
method or a modified semi-additive method.
[0057] In yet another aspect, the present invention is a method for
producing a printed wiring board, including: [0058] a step of
preparing the copper foil with carrier of the present invention and
an insulating substrate; [0059] a step of laminating the copper
foil with carrier, via the ultra-thin copper layer side thereof, on
the insulating substrate; [0060] a step of forming a copper clad
laminate by passing through a step of peeling the carrier of the
copper foil with carrier after laminating the copper foil with
carrier and the insulating substrate on each other; and [0061] a
step of subsequently forming a circuit by a semi-additive method, a
subtractive method, a partly additive method or a modified
semi-additive method.
[0062] In yet another aspect, the present invention is a method for
producing a printed wiring board, including: [0063] a step of
preparing the surface-treated copper foil of the present invention,
with a circuit formed on the surface thereof on the surface-treated
layer formed side, or the copper foil with carrier of the present
invention, with a circuit formed on the surface thereof on the
ultra-thin copper layer side; [0064] a step of forming a resin
layer on the surface of the surface-treated copper foil or the
surface of the copper foil with carrier so as for the circuit to be
embedded; [0065] a step of forming a circuit on the surface of the
resin layer; and [0066] a step of exposing the circuit embedded in
the resin layer by removing the surface-treated copper foil or the
copper foil with carrier.
[0067] In yet another aspect, the present invention is a method for
producing a printed wiring board, including: [0068] a step of
preparing a metal foil with a circuit formed on the surface
thereof, or a first surface-treated copper foil being the
surface-treated copper foil of the present invention with a circuit
formed on the surface thereof on the surface-treated layer formed
side, or a metal foil with carrier with a circuit formed on the
surface thereof on the ultra-thin metal layer side, or a first
copper foil with carrier being the copper foil with carrier of the
present invention with a circuit formed on the surface thereof on
the ultra-thin copper layer side; [0069] a step of forming a resin
layer on the surface of the metal foil, the surface of the
surface-treated copper foil, the surface of the metal foil with
carrier, or the surface of the copper foil with carrier so as for
the circuit to be embedded; [0070] a step of laminating a second
surface-treated copper foil being the surface-treated copper foil
of the present invention, via the surface-treated layer side
thereof, on the resin layer, or a step of laminating a second
copper foil with carrier being the copper foil with carrier of the
present invention, via the ultra-thin copper layer side thereof, on
the resin layer; [0071] a step of peeling the carrier of the second
copper foil with carrier, in the case where the foil laminated on
the resin layer is the second copper foil with carrier; [0072] a
step of removing the surface-treated copper foil on the resin
layer, or the ultra-thin copper layer remaining after peeling the
carrier of the second copper foil with carrier; [0073] a step of
forming a circuit on the surface of the resin layer with the
surface-treated copper foil removed therefrom, or on the surface of
the resin layer with the ultra-thin copper layer removed therefrom;
and [0074] a step of exposing the circuit embedded in the resin
layer after forming the circuit on the resin layer, by removing the
metal foil or the first surface-treated copper foil, or by removing
the ultra-thin metal layer after peeling the carrier of the metal
foil with carrier, or by removing the ultra-thin copper layer after
peeling the carrier of the first copper foil with carrier.
[0075] In yet another aspect, the present invention is a method for
producing a printed wiring board, including: [0076] a step of
preparing the surface-treated copper foil of the present invention
with a circuit formed on the surface thereof on the surface-treated
layer formed side, or the copper foil with carrier of the present
invention with a circuit formed on the surface thereof on the
ultra-thin copper layer side; [0077] a step of forming a resin
layer on the surface of the surface-treated copper foil or the
surface of the copper foil with carrier so as for the circuit to be
embedded; [0078] a step of laminating a metal foil on the resin
layer, or a step of laminating a metal foil with carrier, via the
ultra-thin copper layer side thereof, on the resin layer; [0079] a
step of peeling the carrier of the metal foil with carrier, in the
case where the foil laminated on the resin layer is the metal foil
with carrier; [0080] a step of removing the metal foil on the resin
layer, or the ultra-thin metal layer remaining after peeling the
carrier of the metal foil with carrier; [0081] a step of forming a
circuit on the surface of the resin layer with the metal foil
removed therefrom, or the surface of the resin layer with the
ultra-thin copper layer removed therefrom; and [0082] a step of
exposing the circuit embedded in the resin layer circuit after
forming the circuit on the resin layer, by removing the
surface-treated copper foil, or by removing the ultra-thin copper
layer after peeling the carrier of the copper foil with
carrier.
[0083] In yet another aspect, the present invention is a method for
producing a printed wiring board, including: [0084] a step of
preparing a metal foil with a circuit formed on the surface
thereof, or a first surface-treated copper foil being the
surface-treated copper foil of the present invention with a circuit
formed on the surface thereof on the surface-treated layer formed
side, or a metal foil with carrier with a circuit formed on the
surface thereof on the ultra-thin metal layer side, or a first
copper foil with carrier being the copper foil with carrier of the
present invention with a circuit formed on the surface thereof on
the ultra-thin copper layer side; [0085] a step of forming a resin
layer on the surface of the metal foil, or the surface of the
surface-treated copper foil, or the surface of the metal foil with
carrier, or the surface of the copper foil with carrier so as for
the circuit to be embedded; [0086] a step of laminating a second
surface-treated copper foil being the surface-treated copper foil
of the present invention, via the surface-treated layer side
thereof, on the resin layer, or a step of laminating a second
copper foil with carrier being the copper foil with carrier of the
present invention, via the ultra-thin copper layer side thereof, on
the resin layer; [0087] a step of peeling the carrier of the second
copper foil with carrier, in the case where the foil laminated on
the resin layer is the second copper foil with carrier; [0088] a
step of forming a circuit on the resin layer, by using the
surface-treated copper foil on the resin layer, or the ultra-thin
copper layer remaining after peeling the carrier of the second
copper foil with carrier, by a semi-additive method, a subtractive
method, a partly additive method or a modified semi-additive
method; and [0089] a step of exposing the circuit embedded in the
resin layer after forming the circuit on the resin layer, by
removing the metal foil or by removing the first surface-treated
copper foil, or by removing the ultra-thin metal layer after
peeling the carrier of the metal foil with carrier, or by removing
the ultra-thin copper layer after peeling the carrier of the first
copper foil with carrier.
[0090] In yet another aspect, the present invention is a method for
producing a printed wiring board, including: [0091] a step of
preparing the surface-treated copper foil of the present invention
with a circuit formed on the surface thereof on the surface-treated
layer formed side, or the copper foil with carrier of the present
invention with a circuit formed on the surface thereof on the
ultra-thin copper layer side; [0092] a step of forming a resin
layer on the surface of the surface-treated copper foil or the
surface of the copper foil with carrier so as for the circuit to be
embedded; [0093] a step of laminating a metal foil on the resin
layer, or a step of laminating a metal foil with carrier, via the
ultra-thin copper layer side thereof, on the resin layer; [0094] a
step of peeling the carrier of the metal foil with carrier, in the
case where the foil laminated on the resin layer is the metal foil
with carrier; [0095] a step of forming a circuit on the resin layer
by using the metal foil on the resin layer, or the ultra-thin metal
layer remaining after peeling the carrier of the metal foil with
carrier, by a semi-additive method, a subtractive method, a partly
additive method or a modified semi-additive method; and [0096] a
step of exposing the circuit embedded in the resin layer after
forming the circuit on the resin layer, by removing the
surface-treated copper foil, or by removing the ultra-thin copper
layer after peeling the carrier of the copper foil with
carrier.
[0097] In yet another aspect, the present invention is a resin
substrate of the present invention having a surface roughness Sz of
1 to 5 .mu.m.
[0098] In an embodiment, in the resin substrate of the present
invention, the ratio B/A of the three-dimensional surface area B to
the two-dimensional surface area A of the surface is 1.01 to
1.5.
[0099] In another embodiment, in the resin substrate of the present
invention, the black area rate of the surface is 10 to 50%, and the
average value of the diameters of the holes of the surface is 0.03
to 1.0 .mu.m.
[0100] In yet another aspect, the present invention is a resin
substrate having the ratio B/A of the three-dimensional surface
area B to the two-dimensional surface area A of the surface of 1.01
to 1.5.
[0101] In yet another aspect, the present invention is a resin
substrate having the black area rate of the surface of 10 to 50%,
and the average value of the diameters of the holes of the surface
of 0.03 to 1.0 .mu.m.
[0102] In yet another embodiment, the resin substrate of present
invention has the black area rate of the surface of 10 to 50%, and
the average value of the diameters of the holes of the surface of
0.03 to 1.0 .mu.m.
[0103] In yet another embodiment, the resin substrate of present
invention is for use in the semi-additive method.
[0104] In yet another aspect, the present invention is a printed
wiring board produced by using the resin substrate of the present
invention.
[0105] In yet another aspect, the present invention is a copper
clad laminate produced by using the resin substrate of the present
invention.
[0106] In yet another aspect, the present invention is a method for
producing a printed wiring board, including: [0107] a step of
preparing a surface-treated copper foil and a resin substrate;
[0108] a step of laminating the surface-treated copper foil, via
the surface-treated layer side thereof, on the resin substrate;
[0109] a step of obtaining the resin substrate of the present
invention by removing the surface-treated copper foil on the resin
substrate; and [0110] a step of forming a circuit on the surface of
the resin substrate with the surface-treated copper foil removed
therefrom.
[0111] In yet another aspect, the present invention is a method for
producing a printed wiring board, including: [0112] a step of
preparing a copper foil with carrier constituted by laminating a
carrier, an intermediate layer and an ultra-thin copper layer in
this order, and a resin substrate; [0113] a step of laminating the
copper foil with carrier, via the ultra-thin copper layer side
thereof, on the resin substrate; [0114] a step of peeling the
carrier of the copper foil with carrier after laminating the copper
foil with carrier and the resin substrate on each other; [0115] a
step of obtaining the resin substrate of the present invention by
removing the ultra-thin copper layer on the resin substrate after
peeling the carrier; and [0116] a step of forming a circuit on the
surface of the resin substrate with the ultra-thin copper layer
removed therefrom.
[0117] In yet another aspect, the present invention is a method for
producing a printed wiring board, including: a step of forming a
circuit, after forming a copper clad laminate by laminating a
surface-treated copper foil via the surface-treated layer side
thereof, on the resin substrate of the present invention, by a
semi-additive method, a subtractive method, a partly additive
method or a modified semi-additive method.
[0118] In yet another aspect, the present invention is a method for
producing a printed wiring board, including: [0119] a step of
laminating a copper foil with carrier constituted by laminating a
carrier, an intermediate layer and an ultra-thin copper layer in
this order, via the ultra-thin copper layer side thereof, on the
resin substrate of the present invention; [0120] a step of forming
a copper clad laminate by passing through a step of peeling the
carrier of the copper foil with carrier after laminating the copper
foil with carrier and the resin substrate on each other; and [0121]
a step of subsequently forming a circuit by a semi-additive method,
a subtractive method, a partly additive method or a modified
semi-additive method.
[0122] In yet another aspect, the present invention is a method for
producing a printed wiring board, including: [0123] a step of
preparing a metal foil with a circuit formed on the surface
thereof; [0124] a step of forming a resin substrate on the surface
of the metal foil so as for the circuit to be embedded; [0125] a
step of laminating a surface-treated copper foil, via the
surface-treated layer side thereof, on the resin substrate; [0126]
a step of obtaining the resin substrate of the present invention by
removing the surface-treated copper foil on the resin substrate;
[0127] a step of forming a circuit on the surface of the resin
substrate with the surface-treated copper foil removed therefrom;
and [0128] a step of exposing the circuit formed on the surface of
the metal foil and embedded in the resin substrate by removing the
metal foil.
[0129] In yet another aspect, the present invention is a method for
producing a printed wiring board, including: [0130] a step of
forming a circuit on the surface on the ultra-thin copper layer
side of a first copper foil with carrier constituted by laminating
a carrier, an intermediate layer and an ultra-thin copper layer in
this order; [0131] a step of forming a resin substrate on the
surface on the ultra-thin copper layer side of the first copper
foil with carrier so as for the circuit to be embedded; [0132] a
step of preparing a second copper foil with carrier constituted by
laminating a carrier, an intermediate layer and an ultra-thin
copper layer in this order, and laminating the second copper foil
with carrier, via the ultra-thin copper layer side thereof, on the
resin substrate; [0133] a step of peeling the carrier of the second
copper foil with carrier after laminating the second copper foil
with carrier on the resin substrate; [0134] a step of obtaining the
resin substrate of the present invention by removing the ultra-thin
copper layer on the resin substrate after peeling the carrier of
the second copper foil with carrier, [0135] a step of forming a
circuit on the surface of the resin substrate with the ultra-thin
copper layer removed therefrom; [0136] a step of peeling the
carrier of the first copper foil with carrier after forming the
circuit on the resin substrate; and [0137] a step of exposing the
circuit formed on the surface on the ultra-thin copper layer side
of the first copper foil with carrier and embedded in the resin
substrate, by removing the ultra-thin copper layer of the first
copper foil with carrier after peeling the carrier of the first
copper foil with carrier.
[0138] In yet another aspect, the present invention is a method for
producing a printed wiring board, including: [0139] a step of
preparing a metal foil with a circuit formed on the surface
thereof; [0140] a step of forming the resin substrate of the
present invention on the surface of the metal foil so as for the
circuit to be embedded; [0141] a step of laminating a
surface-treated copper foil, via the surface-treated layer side
thereof, on the resin substrate, and forming a circuit on the resin
layer by a semi-additive method, a subtractive method, a partly
additive method or a modified semi-additive method; and [0142] a
step of exposing the circuit formed on the surface of the metal
foil and embedded in the resin substrate by removing the metal
foil.
[0143] In yet another aspect, the present invention is a method for
producing a printed wiring board, including: [0144] a step of
forming a circuit on the surface on the ultra-thin copper layer
side of a first copper foil with carrier constituted by laminating
a carrier, an intermediate layer and an ultra-thin copper layer in
this order; [0145] a step of forming the resin substrate of the
present invention on the surface on the ultra-thin copper layer
side of the first copper foil with carrier so as for the circuit to
be embedded; [0146] a step of preparing a second copper foil with
carrier constituted by laminating a carrier, an intermediate layer
and an ultra-thin copper layer in this order; laminating the second
copper foil with carrier, via the ultra-thin copper layer side
thereof, on the resin substrate and then peeling the carrier of the
second copper foil with carrier; and forming a circuit on the resin
substrate by a semi-additive method, a subtractive method, a partly
additive method or a modified semi-additive method; [0147] a step
of peeling the carrier of the first copper foil with carrier after
forming a circuit on the resin substrate; and [0148] a step of
exposing the circuit formed on the surface on the ultra-thin copper
layer side of the first copper foil with carrier and embedded in
the resin substrate, by removing the ultra-thin copper layer of the
first copper foil with carrier after peeling the carrier of the
first copper foil with carrier.
[0149] In yet another aspect, the present invention is a method for
producing a printed wiring board, including: [0150] a step of
preparing a metal foil with a circuit formed on the surface
thereof; [0151] a step of forming a resin substrate on the surface
of the metal foil so as for the circuit to be embedded; [0152] a
step of laminating a copper foil with carrier including a carrier,
an intermediate layer and an ultra-thin copper layer in this order,
via the surface thereof on the ultra-thin copper layer side, on the
resin substrate; [0153] a step of obtaining the resin substrate of
the present invention by removing the ultra-thin copper layer on
the resin substrate after peeling the carrier of the copper foil
with carrier; [0154] a step of forming a circuit on the surface of
the resin substrate with the ultra-thin copper layer removed
therefrom; and [0155] a step of exposing the circuit formed on the
surface of the metal foil and embedded in the resin substrate by
removing the metal foil.
[0156] In yet another aspect, the present invention is a method for
producing a printed wiring board, including: [0157] a step of
forming a circuit on the surface on the ultra-thin copper layer
side of a copper foil with carrier including a carrier, an
intermediate layer and an ultra-thin copper layer in this order;
[0158] a step of forming a resin substrate on the surface on the
ultra-thin copper layer side of the copper foil with carrier so as
for the circuit to be embedded; [0159] a step of laminating a
surface-treated copper foil, via the surface-treated layer side
thereof, on the resin substrate; [0160] a step of obtaining the
resin substrate of the present invention by removing the
surface-treated copper foil on the resin substrate; [0161] a step
of forming a circuit on the surface of the resin substrate with the
surface-treated copper foil having been removed therefrom; [0162] a
step of peeling the carrier of the copper foil with carrier after
forming a circuit on the resin substrate; and [0163] a step of
exposing the circuit formed on the surface on the ultra-thin copper
layer side of the copper foil with carrier by removing the
ultra-thin copper layer of the copper foil with carrier after
peeling the carrier of the copper foil with carrier.
[0164] In yet another aspect, the present invention is a method for
producing a printed wiring board, including: [0165] a step of
preparing a metal foil with a circuit formed on the surface
thereof; [0166] a step of forming the resin substrate of the
present invention so as for the circuit to be embedded; [0167] a
step of forming a circuit on the resin substrate; and [0168] a step
of exposing the circuit formed on the surface of the metal foil and
embedded in the resin substrate by removing the metal foil.
[0169] In yet another aspect, the present invention is a method for
producing a printed wiring board, including: [0170] a step of
forming a circuit on the surface on the ultra-thin copper layer
side of a copper foil with carrier including a carrier, an
intermediate layer and an ultra-thin copper layer in this order;
[0171] a step of forming the resin substrate of the present
invention on the surface on the ultra-thin copper layer side of the
copper foil with carrier so as for the circuit to be embedded;
[0172] a step of forming a circuit on the resin substrate; [0173] a
step of peeling the carrier of the copper foil with carrier after
forming the circuit on the resin substrate; and [0174] a step of
exposing the circuit formed on the surface on the ultra-thin copper
layer side of the copper foil with carrier and embedded in the
resin substrate by removing the ultra-thin copper layer of the
copper foil with carrier after peeling the carrier of the copper
foil with carrier.
Advantageous Effects of Invention
[0175] According to the present invention, it is possible to
provide a surface-treated copper foil capable of imparting a
profile shape of the substrate surface after removal of the copper
foil, capable of maintaining fine wiring formability and
implementing satisfactory adhesion of electroless copper plating
coating, and a resin substrate provided with the profile shape of
the surface.
BRIEF DESCRIPTION OF DRAWINGS
[0176] FIG. 1 illustrates a schematic example of a semi-additive
method using the profile of a copper foil.
[0177] FIG. 2 illustrates a production flow of samples for
obtaining the data of Examples and Comparative Examples.
[0178] FIGS. 3A, 3B, 3C, 3D and 3E show the SEM images
(.times.30000) of the copper foil-treated surfaces of Examples A1,
A2, A3, A5 and A6, respectively.
[0179] FIGS. 4A and 4B show the SEM images (.times.6000) of the
copper foil-treated surfaces of Comparative Examples A1 and A2.
[0180] FIGS. 5(A), 5(B), 5(C), 5(D) and 5(E) show the SEM images
(.times.30000) of the surfaces of the resin substrates of Examples
A1(B1), A2(B2), A3(B3), A5(B5) and A6(B6), respectively.
[0181] FIGS. 6(A) and 6(B) show the SEM images (.times.6000) of the
surfaces of the resin substrates of Comparative Examples A1(B1) and
A2(B2), respectively.
DESCRIPTION OF EMBODIMENTS
[0182] [Resin Substrate]
[0183] The resin substrate according to the present invention is
not particularly limited as long as the resin substrate allows the
below-described surface shape to be formed; the resin substrate
concerned can be formed with, for example, a prepreg (GHPL-830MBT
or the like) manufactured by Mitsubishi Gas Chemical Company, Inc.,
a prepreg (679-FG or the like) manufactured by Hitachi Chemical
Co., Ltd., and a prepreg (EI-6785TS-F or the like) manufactured by
Sumitomo Bakelite Co., Ltd. In the present invention, the prepreg
GHPL-830MBT manufactured by Mitsubishi Gas Chemical Company, Inc.
was prepared. As the temperature, pressure and time of a laminating
press, the conditions recommended by the substrate maker were
used.
[0184] The thickness of the resin substrate according to the
present invention is not particularly limited; however, the
thickness of the resin substrate can be, for example, 750 to 850
.mu.m, 100 to 200 .mu.m, or 30 to 100 .mu.m, and is typically 30 to
200 .mu.m (in the case of a double-sided plate).
[0185] [Surface Roughness Sz of Resin Substrate]
[0186] In the SAP method, as a method for quantifying the profile
shape of a substrate surface for forming a circuit thereon, the
roughness measurement using a contact type roughness meter has
hitherto been common. On the contrary, in the present invention, it
has been found that the profile shape of the substrate surface
having the surface roughness (the maximum height of the surface) Sz
as measured with a laser roughness meter, specified to fall within
an appropriate range maintains more satisfactorily the fine wiring
formability and achieves a satisfactory adhesion of the electroless
copper plating coating. From such a viewpoint, the surface
roughness Sz of the resin substrate according to the present
invention is controlled to be 1 to 5 .mu.m. When the surface
roughness Sz of the resin substrate surface is less than 1 .mu.m,
it is difficult to achieve a satisfactory adhesion of the
electroless copper plating coating. When the surface roughness Sz
of the resin substrate surface exceeds 5 .mu.m, the fine wiring
formability of the resin substrate surface is degraded. The surface
roughness Sz of the resin substrate surface is preferably 1 to 4
.mu.m, more preferably 1.5 to 3.5 .mu.m, and furthermore preferably
2 to 3 .mu.m.
[0187] [Area Ratio B/A of Resin Substrate Surface]
[0188] The profile shape of the surface of the resin substrate
having the ratio between the three-dimensional surface area and the
two-dimensional surface area falling within a predetermined range
is satisfactory in the fine wiring formability and achieves a
satisfactory adhesion of the electroless copper plating coating.
From such a viewpoint, the ratio B/A of the three-dimensional
surface area B to the two-dimensional surface area A of the surface
of the resin substrate according to the present invention is
preferably controlled to be 1.01 to 1.5. When the ratio B/A of the
three-dimensional surface area B to the two-dimensional surface
area A of the surface of the resin substrate is less than 1.01, it
is difficult to achieve a satisfactory adhesion of the electroless
copper plating coating. When the ratio B/A of the three-dimensional
surface area B to the two-dimensional surface area A of the surface
of the resin substrate exceeds 1.5, the fine wiring formability of
the surface of the resin substrate is degraded. The ratio B/A of
the three-dimensional surface area B to the two-dimensional surface
area A of the surface of the resin substrate according to the
present invention is preferably 1.03 to 1.4, more preferably 1.05
to 1.35 and furthermore preferably 1.1 to 1.3.
[0189] [Black Area Rate and Average Value of Diameters of Holes of
the Surface of Resin Substrate]
[0190] When the degree of asperity of the surface of the resin
substrate is represented by the black area rate obtained from the
SEM observation photograph, the profile shape of the surface of the
resin substrate having the black area rate concerned falling within
a predetermined range is satisfactory in fine wiring formability,
and achieves a satisfactory adhesion of the electroless copper
plating coating. From such a viewpoint, it is preferable that the
black area rate of the surface of the resin substrate according to
the present invention be controlled so as to be 10 to 50%. As the
black area rate, black-white image processing was applied to the
SEM image (magnification of 30 k) of the substrate surface, by
using Photo Shop 7.0 software, and thus, the area rate (%) of the
black region concerned was determined. The black area rate (%) was
determined as the rate at the threshold value of 128 by selecting
"Histogram" of "Image" found in Photo Shop 7.0. It is to be noted
that the black region indicates that the measurement surface is
concave, and the white region indicates that the measurement
surface is convex. When the black area rate concerned of the
substrate surface is less than 15%, it is difficult to achieve a
satisfactory adhesion of the electroless copper plating coating.
When the black area rate concerned of the substrate surface exceeds
50%, the fine wiring formability is degraded.
[0191] The profile shape of the surface of the resin substrate,
having the black area rate falling within the predetermined range
and at the same time having the average value of the diameters of
the holes of the surface falling within the predetermined range is
the necessary condition for achieving a satisfactory fine wiring
formability and a satisfactory adhesion of the electroless copper
plating coating. This is because only the black area rate does not
satisfy the size of the profile and the appropriate distribution of
the profile on the plane thereof. From such a viewpoint, it is
preferable that the average value of the diameters of the holes of
the surface of the resin substrate according to the present
invention be controlled so as to be 0.03 to 1.0 .mu.m. When the
average value of the diameters of the holes concerned of the
surface of the resin substrate is less than 0.03 .mu.m, it is
difficult to achieve a satisfactory adhesion of the electroless
copper plating coating. When the average value of the diameters of
the holes concerned of the surface of the resin substrate exceeds
1.0 .mu.m, the fine wiring formability is degraded.
[0192] As described above, in the resin substrate according to the
present invention, it is preferable that the black area rate
concerned of the substrate surface be 10 to 50% and the average
value of the diameters of the holes concerned of the substrate
surface be 0.03 to 1.0 .mu.m; it is more preferable that the black
area rate be 15 to 45% and the average value of the diameters of
the holes be 0.1 to 0.8 .mu.m; and it is furthermore preferable
that the black area rate be 20 to 40% and the average value of the
diameters of the holes be 0.15 to 0.7 .mu.m.
[0193] [Method for Forming Surface Profile of Resin Substrate]
[0194] The profile shape of the surface of the resin substrate
according to the present invention can be formed by laminating a
surface-treated copper foil on the resin substrate and by
subsequently removing the surface-treated copper foil concerned by
entire-surface etching or the like. The profile shape of the
surface of the resin substrate according to the present invention
can also be formed by treating the surface of the resin substrate
with a predetermined chemical solution.
[0195] In the method for forming the surface profile of the resin
substrate according to the present invention, using a
surface-treated copper foil, first there is prepared a
surface-treated copper foil controlled so as for the surface
roughness (the maximum height of the surface) Sz of the surface of
the surface-treated layer to be 2 to 6 .mu.m. Next, the
surface-treated copper foil concerned is bonded, via the
surface-treated layer side thereof, to the resin substrate, and
then the surface-treated copper foil is removed by entire-surface
etching or the like. In this way, the surface roughness Sz of the
surface of the resin substrate after removing the surface-treated
copper foil is 1 to 5 .mu.m.
[0196] In the present invention, "the surface of the
surface-treated layer" means the outermost surface on the
surface-treated side. Specifically, when surface-treated layers
such as a roughening-treated layer, a rust-preventing layer, a heat
resistant layer, a chromate-treated layer and a silane coupling
treated layer are provided on a copper foil, the surface of the
surface-treated layer means the surface obtained after providing
these surface-treated layers concerned on the copper foil.
[0197] When as the surface-treated copper foil, a surface-treated
copper foil with the ratio B/A of the three-dimensional surface
area B to the two-dimensional surface area A of the surface of the
surface-treated layer controlled to be 1.05 to 1.8 is used and
bonded to the resin substrate in the same manner as described
above, and the surface-treated copper foil concerned is removed by
entire-surface etching or the like, the ratio B/A of the
three-dimensional surface area B to the two-dimensional surface
area A of the surface of the resin substrate after removing the
surface-treated copper foil is 1.01 to 1.5.
[0198] When as the surface-treated copper foil, a surface-treated
copper foil having a surface roughness Sz as measured with a laser
roughness meter of 2 to 6 .mu.m and having the ratio B/A between
the three-dimensional surface area B and the two-dimensional
surface area A controlled to be 1.05 to 1.8 is used and bonded to
the resin substrate in the same manner as described above, and the
surface-treated copper foil concerned is removed by entire-surface
etching or the like, the black area rate of the surface of the
resin substrate can be controlled to be 10 to 50%, and the average
value of the diameters of the holes of the surface of the resin
substrate can be controlled to be 0.03 to 1.0 .mu.m.
[0199] By controlling the current density for surface treatment
during the surface treatment such as during the formation of
roughened particles and the immersion time in a plating solution
after the completion of the surface treatment, the surface state of
the copper foil and the form and the formation density of roughened
particles, after the surface treatment are determined, and
accordingly, the surface roughness Sz, the area ratio B/A, the
black area rate and the average value of the diameters of the holes
of the surface-treated copper foil can be controlled.
[0200] Specifically, during the surface treatment such as during
the formation of roughened particles, by performing the surface
treatment with the current density of the surface treatment
controlled to be high, and successively performing the surface
treatment with the current density of the surface treatment
controlled to be low, the surface state of the copper foil and the
form and the formation density of roughened particles, after the
surface treatment are determined, and the above-described surface
roughness Sz, area ratio B/A, black area rate and average value of
the diameters of the holes can be controlled. In addition, it is
also effective to repeatedly perform the operation that the surface
treatment is performed with the current density of the surface
treatment controlled to be high, and successively the surface
treatment is performed with the current density of the surface
treatment controlled to be low.
[0201] Here, when the current density is allowed to be high during
the surface treatment such as during the formation of roughened
particles, the deposited metal particles tend to grow in a
direction perpendicular to the surface of the copper foil. In
addition, when the current density is allowed to be low during the
surface treatment such as during the formation of roughened
particles, the surface of the copper foil tends to be smooth
(asperities tend to occur to a low degree).
[0202] Accordingly, the operation that the surface treatment is
performed with the current density of the surface treatment
controlled to be high, and successively the surface treatment is
performed with the current density of the surface treatment
controlled to be low is regarded as the surface state control such
that metal particles are allowed to grow in the direction
perpendicular to the surface of the copper foil, and subsequently
the asperities due to the metal particles and the surface of the
cooper foil are embedded so as to form a smooth surface.
[0203] In addition, when the surface-treated layer of the copper
foil is easily dissolved in a plating solution, the effect of the
immersion time in the plating solution after the completion of the
surface treatment on the surface form of the surface treated copper
foil tends to be more profound.
[0204] In the method for forming the surface profile (the
above-described surface roughness Sz, area ratio B/A, black area
rate and average value of the diameters of the holes) of the resin
substrate according to the present invention, based on a treatment
using a chemical solution, the surface profile can be formed by
applying a desmear treatment to the resin substrate under the
following immersion treatment conditions A or B, and by
subsequently performing a neutralization treatment.
(Desmear Treatment Conditions A)
[0205] Desmear treatment solution: 40 g/L KMnO.sub.4, 20 g/L NaOH
[0206] Treatment temperature: Room temperature [0207] Immersion
time: 20 minutes [0208] Number of rotations of stirrer: 300 rpm
(Desmear Treatment Conditions B)
[0208] [0209] Desmear treatment solution: 90 g/L KMnO.sub.4, 5 g/L
HCl [0210] Treatment temperature: 49.degree. C. [0211] Immersion
time: 20 minutes [0212] Number of rotations of stirrer: 300 rpm
(Neutralization Treatment Conditions)
[0212] [0213] Neutralization treatment solution: L-Ascorbic acid 80
g/L [0214] Treatment temperature: Room temperature [0215] Immersion
time: 3 minutes [0216] No stirring
[0217] The remainders of the treatment solutions used in the
desmear treatment, electrolysis, surface treatment, plating or the
like used in the present invention are water unless otherwise
specified.
[0218] In addition to the above-described immersion treatment, by
performing shower treatments A and B, and a neutralization
treatment on the surface of the resin substrate, under the
following treatment conditions, it is possible to perform the
formation of the surface profile (the surface roughness Sz, area
ratio B/A, black area rate, and average value of diameters of
holes) of the resin substrate in the same manner as described
above.
(Shower Treatment Conditions A)
[0219] Desmear treatment solution: 40 g/L KMnO.sub.4, 20 g/L NaOH
[0220] Treatment temperature: Room temperature [0221] Treatment
time: 20 minutes [0222] Shower pressure: 0.2 MPa
(Shower Treatment Conditions B)
[0222] [0223] Desmear treatment solution: 90 g/L KMnO.sub.4, 5 g/L
HCl [0224] Treatment temperature: 49.degree. C. [0225] Treatment
time: 20 minutes [0226] Shower pressure: 0.2 MPa
(Neutralization Treatment Conditions)
[0226] [0227] Neutralization treatment solution: L-Ascorbic acid 80
g/L [0228] Treatment temperature: Room temperature [0229] Immersion
time: 3 minutes [0230] No stirring
[0231] [Surface-Treated Copper Foil]
[0232] The surface-treated copper foil of the present invention can
be used for forming the surface profile of the resin substrate. The
copper foil used in the surface-treated copper foil concerned may
either be an electrolytic copper foil or a rolled copper foil. The
thickness of the copper foil concerned is not particularly required
to be limited; however, the thickness of the copper foil is, for
example, 1 .mu.m or more, 2 .mu.m or more, 3 .mu.m or more, or 5
.mu.m or more, and for example, 3000 .mu.m or less, 1500 .mu.m or
less, 800 .mu.m or less, 300 .mu.m or less, 150 .mu.m or less, 100
.mu.m or less, 70 .mu.m or less, 50 .mu.m or less, or 40 .mu.m or
less.
[0233] Examples of the rolled copper foil used in the present
invention include copper alloy foils including one or more elements
such as Ag, Sn, In, Ti, Zn, Zr, Fe, P, Ni, Si, Te, Cr, Nb, V, B,
and Co. When the concentration of the above-described elements is
high (for example, 10% by mass or more in total), the conductivity
is sometimes degraded. The conductivity of the rolled copper foil
is preferably 50% IACS or more, more preferably 60% IACS or more,
and furthermore preferably 80% IACS or more. Examples of the rolled
copper foil include the copper foils produced by using tough pitch
copper (JIS H3100 C1100) or oxygen-free copper (JIS H3100 C1020).
It is to be noted that when the term "copper foil" is used alone in
the present specification, the term "copper foil" also includes
copper alloy foils.
[0234] The electrolytic copper foil usable in the present invention
can be prepared with the following electrolyte composition and the
following production conditions.
[0235] Common Electrolytic Raw Foil:
[0236] <Electrolyte Composition> [0237] Copper: 80 to 120 g/L
[0238] Sulfuric acid: 80 to 120 g/L [0239] Chlorine: 30 to 100 ppm
[0240] Leveling agent (glue): 0.1 to 10 ppm
[0241] Double-Sided Flat Electrolytic Raw Foil, and Ultra-Thin
Copper Foil with Carrier:
[0242] <Electrolyte Composition> [0243] Copper: 80 to 120 g/L
[0244] Sulfuric acid: 80 to 120 g/L [0245] Chlorine: 30 to 100 ppm
[0246] Leveling agent 1 (bis(3-sulfopropyl) disulfide): 10 to 30
ppm [0247] Leveling agent 2 (amine compound): 10 to 30 ppm
[0248] As the amine compound, an amine compound of the following
chemical formula can be used.
##STR00001##
(wherein, in the chemical formula, R.sub.1 and R.sub.2 are each a
group selected from the group consisting of a hydroxyalkyl group,
an ether group, an aryl group, an aromatic-substituted alkyl group,
an unsaturated hydrocarbon group, and an alkyl group.)
[0249] <Production Conditions> [0250] Current density: 70 to
100 A/dm.sup.2 [0251] Electrolyte temperature: 50 to 65.degree. C.
[0252] Linear speed of electrolyte: 1.5 to 5 m/sec [0253]
Electrolysis time: 0.5 to 10 minutes (regulated according to
deposited copper thickness and current density)
[0254] As roughening treatment, there can be used alloy platings
such as copper-cobalt-nickel plating, copper-nickel-phosphorus
alloy plating, copper-nickel-tungsten alloy plating, and
copper-cobalt-tungsten alloy plating; more preferably copper alloy
plating can be used. The copper-cobalt-nickel alloy plating as the
roughening treatment can be implemented in such a way that ternary
alloy layers are formed by electroplating so as to have the
following deposition amounts: 15 to 40 mg/dm.sup.2 of copper, 100
to 3000 .mu.g/dm.sup.2 of cobalt, and 100 to 1500 .mu.g/dm.sup.2 of
nickel. When the deposition amount of Co is less than 100
.mu.g/dm.sup.2, sometimes the heat resistance is degraded and the
etching property is also degraded. When the deposition amount of Co
exceeds 3000 .mu.g/dm.sup.2, such a deposition amount is not
favorable in the case where magnetic effect is required to be
considered, sometimes causes etching stain, and sometimes degrades
acid resistance and chemical resistance. When the deposition amount
of Ni is less than 100 .mu.g/dm.sup.2, sometimes heat resistance is
degraded. On the other hand, when the deposition amount of Ni
exceeds 1500 .mu.g/dm.sup.2, sometimes etching residue grows. A
preferable deposition amount of Co is 1000 to 2500 .mu.g/dm.sup.2,
and a preferable deposition amount of nickel is 500 to 1200
.mu.g/dm.sup.2. Here, the etching stain means that Co remains
undissolved in etching with copper chloride, and the etching
residue means that Ni remains undissolved in alkaline etching with
ammonium chloride.
[0255] The plating bath and plating conditions for forming such a
ternary copper-cobalt-nickel alloy plating are as follows:
[0256] Plating bath composition: Cu 10 to 20 g/L, Co 1 to 10 g/L,
Ni 1 to 10 g/L
[0257] pH: 1 to 4
[0258] Temperature: 30 to 50.degree. C.
[0259] Current density D.sub.k: 20 to 30 A/dm.sup.2
[0260] Plating time: 1 to 5 seconds
[0261] Immersion time in the same plating solution after completion
of plating: 20 seconds or less (because immersion longer than 20
seconds disturbs particle shapes), preferably 10 seconds or less,
more preferably 5 seconds or less
[0262] After completion of the plating, usually the plated product
is not taken out from the plating solution particularly in haste;
however, in the present invention, after the completion of the
plating concerned, it is necessary to take out the plated product
from the plating solution within a predetermined time. Accordingly,
as described above, the immersion time in the same plating solution
after the completion of the plating is set at 20 seconds or less.
When the plated product is immersed for the immersion time
concerned exceeding 20 seconds, the roughened particles are
possibly partially dissolved by the plating solution. The partial
dissolution of the roughened particles is considered to give a
cause for disturbing the particle shapes.
[0263] By setting the immersion time in the same plating solution
after the completion of plating to be as short as 10 seconds or
less, or 5 seconds or less, the particle shapes can be less
disturbed in an effective manner.
[0264] In the same manner as in the case of the
copper-cobalt-nickel alloy plating, in the case of the alloy
plating other than the copper-cobalt-nickel alloy plating, it is
important to control the immersion time in the same plating
solution after the completion of the plating so as to be 20 seconds
or less (because immersion longer than 20 seconds disturbs particle
shapes), preferably 10 seconds or less and more preferably 5
seconds or less. With the immersion exceeding 20 seconds in the
immersion time concerned, the plating solution possibly partially
dissolves the roughened particles. Such a partial dissolution of
the roughened particles is considered to be a cause for the
disturbance of the particle shapes. Heretofore known conditions can
be used for the pH, temperature, current density, and plating time
of the alloy plating other than the copper-cobalt-nickel alloy
plating.
[0265] By setting the immersion time in the same plating solution
after the completion of plating to be as short as 10 seconds or
less, or 5 seconds or less, the particle shapes can be less
disturbed in an effective manner.
[0266] In addition, a copper plating as the following roughening
treatment may also be performed as a surface treatment. The
surface-treated layer formed by the following copper plating as the
roughening treatment is high in the copper concentration, and the
surface-treated layer becomes a roughening-treated layer (plating
layer) mostly constituted with copper. The roughening-treated layer
(plating layer) high in copper concentration is characterized by
being hardly dissolved in the plating solution. The following
copper plating as the roughening treatment is performed in the
order of the copper plating 1 and the copper plating 2.
[0267] Copper Plating 1
[0268] (Solution Composition 1) [0269] Cu concentration: 10 to 30
g/L [0270] H.sub.2SO.sub.4 concentration: 50 to 150 g/L [0271]
Tungsten concentration: 0.5 to 50 mg/L [0272] Sodium dodecyl
sulfate: 0.5 to 50 mg/L
[0273] (Electroplating Conditions 1) [0274] Temperature: 30 to
70.degree. C.
[0275] (First Stage Current Conditions) [0276] Current density: 18
to 70 A/dm.sup.2 [0277] Roughening coulomb quantity: 1.8 to 1000
A/dm.sup.2, preferably 1.8 to 500 A/dm.sup.2 [0278] Plating time:
0.1 to 20 seconds
[0279] (Second Stage Current Conditions) [0280] Current density:
0.5 to 13 A/dm.sup.2 [0281] Roughening coulomb quantity: 0.05 to
1000 A/dm.sup.2, preferably 0.05 to 500 A/dm.sup.2 [0282] Plating
time: 0.1 to 20 seconds
[0283] The first stage and the second stage may be repeated. In
addition, after the first stage is performed once or a plurality of
times, the second stage may also be performed once or a plurality
of times. Alternatively, the following operations may also be
repeated: after the first stage is performed once or a plurality of
times, the second stage is performed once or a plurality of
times.
[0284] Copper Plating 2
[0285] (Solution Composition 2) [0286] Cu concentration: 20 to 80
g/L [0287] H.sub.2SO.sub.4 concentration: 50 to 200 g/L
[0288] (Electroplating Conditions 2) [0289] Temperature: 30 to
70.degree. C.
[0290] (Current Conditions) [0291] Current density: 5 to 50
A/dm.sup.2 [0292] Roughening coulomb quantity: 50 to 300 A/dm.sup.2
[0293] Plating time: 1 to 60 seconds
[0294] Alternatively, on the copper foil, an alloy plating such as
the above-described copper-cobalt-nickel alloy plating and the
above-described copper plating may be performed in combination. It
is preferable to perform the above described alloy plating after
the above-described copper plating is performed.
[0295] In the present invention, the surface-treated layer formed
on the copper foil may be a roughening-treated layer. The
roughening treatment usually means a treatment in which nodular
electrodeposition is formed on the surface of a copper foil after
degreasing, specifically on the copper foil surface adhering to the
resin substrate, namely, the surface on the surface-treated side of
the copper foil, for the purpose of improving the peel strength of
the copper foil after lamination. An electrolytic copper foil has
asperities at the time of production; however, by augmenting the
protrusions of the electrolytic copper foil by roughening
treatment, the asperities can be further grown. The roughening
treatment can be performed, for example, by forming roughened
particles with copper or a copper alloy. The roughening treatment
may be a refined treatment. The roughening-treated layer may be a
layer composed of a single substance selected from or an alloy
including one or more selected from the group consisting of copper,
nickel, cobalt, phosphorus, tungsten, arsenic, molybdenum, chromium
and zinc. Additionally, after the roughened particles are formed
with copper or a copper alloy, it is also possible to further
perform a roughening treatment in which secondary particles or
tertiary particles are provided with a single substance or an alloy
of nickel, cobalt, copper or zinc. Additionally, on the surface of
the roughening-treated layer, one or more layers selected from the
group consisting of a heat resistant layer, a rust-preventing
layer, a chromate-treated layer and a silane coupling treated layer
may be formed.
[0296] In the present invention, the surface-treated layer formed
on the copper foil may be one or more selected from the group
consisting of a roughening-treated layer, a heat resistant layer, a
rust-preventing layer, a chromate-treated layer and a silane
coupling treated layer.
[0297] As the heat resistant layer and the rust-preventing layer,
heretofore known heat resistant layers and rust-preventing layers
can be used. For example, the heat resistant layer and/or the
rust-preventing layer may be a layer including one or more elements
selected from the group consisting of nickel, zinc, tin, cobalt,
molybdenum, copper, tungsten, phosphorus, arsenic, chromium,
vanadium, titanium, aluminum, gold, silver, platinum group
elements, iron and tantalum; or a metal layer or an alloy layer
composed of one or more elements selected from the group consisting
of nickel, zinc, tin, cobalt, molybdenum, copper, tungsten,
phosphorus, arsenic, chromium, vanadium, titanium, aluminum, gold,
silver, platinum group elements, iron and tantalum. The heat
resistant layer and/or the rust-preventing layer may also include
an oxide, a nitride and a silicide including one or more elements
selected from the group consisting of nickel, zinc, tin, cobalt,
molybdenum, copper, tungsten, phosphorus, arsenic, chromium,
vanadium, titanium, aluminum, gold, silver, platinum group
elements, iron and tantalum. The heat resistant layer and/or the
rust-preventing layer may also be a layer including a nickel-zinc
alloy. The heat resistant layer and/or the rust-preventing layer
may also be a nickel-zinc alloy layer. The nickel-zinc alloy layer
may be a layer containing 50 wt % to 99 wt % of nickel and 50 wt %
to 1 wt % of zinc, zinc, except for inevitable impurities. The
total deposition amount of zinc and nickel in the nickel-zinc alloy
layer may be 5 to 1000 mg/m.sup.2, preferably 10 to 500 mg/m.sup.2,
and preferably 20 to 100 mg/m.sup.2. The ratio (=deposition amount
of nickel/deposition amount of zinc) between the deposition amount
of nickel and the deposition amount of zinc in the nickel-zinc
alloy-containing layer or the nickel-zinc alloy layer is preferably
1.5 to 10. The deposition amount of nickel in the layer including a
nickel-zinc alloy or the nickel-zinc alloy layer is preferably 0.5
mg/m.sup.2 to 500 mg/m.sup.2, and more preferably 1 mg/m.sup.2 to
50 mg/m.sup.2. In the case where the heat resistant layer and/or
the rust-preventing layer is a layer including a nickel-zinc alloy,
when the inner wall portion of the through-holes, the via holes or
the like is brought into contact with the desmear solution, the
interface between the copper foil and the resin substrate is hardly
corroded by the desmear solution, and the adhesion between the
copper foil and the resin substrate is improved.
[0298] For example, the heat resistant layer and/or the
rust-preventing layer may be a layer formed by sequentially
laminating a nickel or nickel alloy layer having a deposition
amount of 1 mg/m.sup.2 to 100 mg/m.sup.2, preferably 5 mg/m.sup.2
to 50 mg/m.sup.2 and a tin layer having a deposition amount of 1
mg/m.sup.2 to 80 mg/m.sup.2, preferably 5 mg/m.sup.2 to 40
mg/m.sup.2, and the nickel alloy layer may be constituted with any
one of a nickel-molybdenum alloy, a nickel-zinc alloy, and a
nickel-molybdenum-cobalt alloy. In the heat resistant layer and/or
the rust-preventing layer, the total deposition amount of nickel or
a nickel alloy and tin is preferably 2 mg/m.sup.2 to 150 mg/m.sup.2
and more preferably 10 mg/m.sup.2 to 70 mg/m.sup.2. In the heat
resistant layer and/or the rust-preventing layer, [nickel
deposition amount in the nickel or the nickel alloy]/[tin
deposition amount] is preferably 0.25 to 10 and more preferably
0.33 to 3. By using the heat resistant layer concerned and/or the
rust-preventing layer, after the processing of the copper foil with
carrier into a printed wiring board, the peel strength of the
circuit, the degradation rate of the chemical resistance of the
peel strength concerned and the like are made satisfactory.
[0299] For the silane coupling agent used in the silane coupling
treatment, heretofore known silane coupling agents may be used; for
example, an amino silane coupling agent, an epoxy silane coupling
agent, or a mercapto silane coupling agent may also be used. As the
silane coupling agent, for example, the following compounds may be
used: vinyltrimethoxysilane, vinylphenyltrimethoxysilane,
.gamma.-methacryloxypropyltrimethoxysilane,
.gamma.-glycidoxypropyltrimethoxysilane,
4-glycidylbutyltrimethoxysilane,
.gamma.-aminopropyltriethoxysilane,
N-.beta.(aminoethyl)-.gamma.-aminopropyltrimethoxysilane,
N-3-(4-(3-aminopropoxy)butoxy)propyl-3-aminopropyltrimethoxysilane,
imidazolesilane, triazinesilane, and
.gamma.-mercaptopropyltrimethoxysilane.
[0300] The silane coupling treated layer may be formed by using,
for example, a silane coupling agent such as an epoxy silane, an
amino silane, a methacryloxy silane and a mercapto silane. Such
silane coupling agents may also be used as mixtures of two or more
thereof. The silane coupling treated layer is preferably a layer
formed by using, among these, an amino silane coupling agent or an
epoxy silane coupling agent.
[0301] The amino silane coupling agent as referred to herein may be
an amino silane coupling agent selected from the group consisting
of N-(2-aminoethyl)-3-aminopropyltrimethoxysilane,
3-(N-styrylmethyl-2-aminoethylamino)propyltrimethoxysilane,
3-aminopropyltriethoxysilane,
bis(2-hydroxyethyl)-3-aminopropyltriethoxysilane,
aminopropyltrimethoxysilane, N-methylaminopropyltrimethoxysilane,
N-phenylaminopropyltrimethoxysilane,
N-(3-acryloxy-2-hydroxypropyl)-3-aminopropyltriethoxysilane,
4-aminobutyltriethoxysilane,
(aminoethylaminomethyl)phenetyltrimethoxysilane,
N-(2-aminoethyl-3-aminopropyl)trimethoxysilane,
N-(2-aminoethyl-3-aminopropyl)tris(2-ethylhexoxy)silane,
6-(aminohexylaminopropyl)trimethoxysilane,
aminophenyltrimethoxysilane,
3-(l-aminopropoxy)-3,3-dimethyl-1-propenyltrimethoxysilane,
3-aminopropyltris(methoxyethoxy)silane,
3-aminopropyltriethoxysilane, 3-aminopropyltrimethoxysilane,
.omega.-aminoundecyltrimethoxysilane,
3-(2-N-benzylaminoethylaminopropyl)trimethoxysilane,
bis(2-hydroxyethyl)-3-aminopropyltriethoxysilane,
(N,N-diethyl-3-aminopropyl)trimethoxysilane,
(N,N-dimethyl-3-aminopropyl)trimethoxysilane,
N-methylaminopropyltrimethoxysilane,
N-phenylaminopropyltrimethoxysilane,
3-(N-styrylmethyl-2-aminoethylamino)propyltrimethoxysilane,
.gamma.-aminopropyltriethoxysilane,
N-.beta.(aminoethyl)-.gamma.-aminopropyltrimethoxysilane, and
N-3-(4-(3-aminopropoxy)butoxy)propyl-3-aminopropyltrimethoxysilane.
[0302] It is desirable that the silane coupling treated layer be
formed with an area density falling in the following ranges, in
terms of silicon atom: a range from 0.05 mg/m.sup.2 to 200
mg/m.sup.2, preferably a range from 0.15 mg/m.sup.2 to 20
mg/m.sup.2, and preferably a range from 0.3 mg/m.sup.2 to 2.0
mg/m.sup.2. In the case of the foregoing ranges, the adhesion
between the substrate and the surface-treated copper foil can be
more improved.
[0303] [Surface Roughness Sz of Surface-Treated Copper Foil]
[0304] In the SAP method, as a method for quantifying the profile
shape of a substrate surface for forming a circuit thereon, the
roughness measurement using a contact type roughness meter has
hitherto been common. On the contrary, in the present invention, it
has been found that the profile shape of the substrate surface
having the surface roughness (the maximum height of the surface) Sz
as measured with a laser roughness meter, specified to fall within
an appropriate range maintains more satisfactorily the fine wiring
formability and achieves a satisfactory adhesion of the electroless
copper plating coating. From such a viewpoint, in the
surface-treated copper foil according to the present invention, the
surface roughness Sz of the surface of the surface-treated layer is
controlled to be 2 to 6 .mu.m. Due to the surface roughness Sz of
the surface of the surface-treated layer controlled to be 2 to 6
.mu.m, after the surface-treated copper foil concerned is bonded,
via the surface-treated layer side thereof, to the substrate, and
then the surface-treated copper foil is removed from the substrate,
the surface roughness Sz of the surface, on the copper foil removal
side, of the substrate is 1 to 5 .mu.m. When the surface roughness
Sz of the surface of the surface-treated layer of the
surface-treated copper foil is less than 2 .mu.m, after the
surface-treated copper foil concerned is bonded, via the
surface-treated layer side thereof, to substrate, and then the
surface-treated copper foil is removed from the substrate, the
surface roughness Sz of the surface, on the copper foil removal
side, of the substrate is less than 1 .mu.m, and it is difficult to
achieve the satisfactory adhesion of the electroless copper plating
coating. When the surface roughness Sz of the surface of the
surface-treated layer of the surface-treated copper foil exceeds 6
.mu.m, after the surface-treated copper foil concerned is bonded,
via the surface-treated layer side thereof, to substrate, and then
the surface-treated copper foil is removed from the substrate, the
surface roughness Sz of the surface, on the copper foil removal
side, of the substrate exceeds 5 .mu.m, and the fine wiring
formability is degraded. The surface roughness Sz of the surface of
the surface-treated layer of the surface-treated copper foil
according to the present invention is preferably 2 to 5.5 .mu.m,
more preferably 2.5 to 5.5 .mu.m and furthermore preferably 3 to 5
.mu.m. The surface roughness Sz of the substrate surface after the
removal of the surface-treated copper foil according to the present
invention is preferably 1 to 4 .mu.m, more preferably 1.5 to 3.5
.mu.m and furthermore preferably 2 to 3 .mu.m.
[0305] [Area Ratio B/A of Surface-Treated Copper Foil]
[0306] The ratio B/A of the three-dimensional surface area B to the
two-dimensional surface area A of the surface on the
surface-treated side of the surface-treated copper foil
significantly affects the profile shape of the surface of the
substrate after the surface-treated copper foil concerned is
bonded, via the surface-treated layer side thereof, to the
substrate, and the surface-treated copper foil is removed. From
such a viewpoint, it is preferable that in the surface-treated
copper foil according to the present invention, the ratio B/A of
the three-dimensional surface area B to the two-dimensional surface
area A of the surface of the surface-treated layer be controlled to
be 1.05 to 1.8. The ratio B/A of the three-dimensional surface area
B to the two-dimensional surface area A of the surface on the
surface-treated side can also be said, for example in the case
where the surface concerned is roughening-treated, as the ratio B/A
of the surface area B of the roughened particles to the area A
obtained when the copper foil is plan-viewed from the copper foil
surface side. Due to the ratio B/A of the three-dimensional surface
area B to the two-dimensional surface area A of the surface on the
surface-treated side of the surface-treated copper foil controlled
to be 1.05 to 1.8, after the surface-treated copper foil concerned
is bonded, via the surface-treated layer side thereof, to the
substrate, and then the surface-treated copper foil is removed from
the substrate, the ratio B/A of the three-dimensional surface area
B to the two-dimensional surface area A of the surface, on the
copper foil removal side, of the substrate is 1.01 to 1.5. When the
ratio B/A of the three-dimensional surface area B to the
two-dimensional surface area A of the surface on the
surface-treated side of the surface-treated copper foil is less
than 1.05, after the surface-treated copper foil concerned is
bonded, via the surface-treated layer side thereof, to the
substrate, and then the surface-treated copper foil is removed from
the substrate, the ratio B/A of the three-dimensional surface area
B to the two-dimensional surface area A of the surface, on the
copper foil removal side, of the substrate is less than 1.01, and
it is difficult to achieve the satisfactory adhesion of the
electroless copper plating coating. When the ratio B/A of the
three-dimensional surface area B to the two-dimensional surface
area A of the surface on the surface-treated side of the
surface-treated copper foil exceeds 1.8, after the surface-treated
copper foil concerned is bonded, via the surface-treated layer side
thereof, to substrate, and then the surface-treated copper foil is
removed from the substrate, the ratio B/A of the three-dimensional
surface area B to the two-dimensional surface area A of the
surface, on the copper foil removal side, of the substrate exceeds
1.5, and the fine wiring formability is degraded. The ratio B/A of
the three-dimensional surface area B to the two-dimensional surface
area A of the surface on the surface-treated side of the
surface-treated copper foil according to the present invention is
preferably 1.10 to 1.75, more preferably 1.14 to 1.71 and
furthermore preferably 1.18 to 1.67. The ratio B/A of the
three-dimensional surface area B to the two-dimensional surface
area A of the substrate surface after removal of the
surface-treated copper foil according to the present invention is
preferably 1.03 to 1.4, more preferably 1.05 to 1.35 and
furthermore preferably 1.1 to 1.3.
[0307] [Black Area Rate and Average Value of Diameters of Holes of
Surface-Treated Copper Foil]
[0308] When the degree of asperity of the substrate surface is
represented by the black area rate obtained from the SEM
observation photograph, the profile shape of the surface of the
substrate having the black area rate concerned falling within a
predetermined range is satisfactory in fine wiring formability, and
achieves a satisfactory adhesion of the electroless copper plating
coating. From such a viewpoint, it is preferable that in the
surface-treated copper foil according to the present invention,
when the surface-treated copper foil is bonded, via the
surface-treated layer side thereof, to the substrate, and then the
surface-treated copper foil is removed, the black area rate of the
surface, on the copper foil removal side, of the substrate be
controlled to be 10 to 50%. As the black area rate, black-white
image processing was applied to the SEM image (magnification of 30
k) of the substrate surface, by using Photo Shop 7.0 software, and
thus, the area rate (%) of the black region concerned was
determined. The black area rate (%) was determined as the rate at
the threshold value of 128 by selecting "Histogram" of "Image"
found in Photo Shop 7.0. It is to be noted that the black region
indicates that the measurement surface is concave, and the white
region indicates that the measurement surface is convex. When the
black area rate concerned of the substrate surface is less than
10%, it is difficult to achieve a satisfactory adhesion of the
electroless copper plating coating. When the black area rate
concerned of the substrate surface exceeds 50%, the fine wiring
formability is degraded.
[0309] The profile shape of the surface of the resin substrate,
having the black area rate falling within the predetermined range
and at the same time having the average value of the diameters of
the holes of the surface falling within the predetermined range is
the necessary condition for achieving a satisfactory fine wiring
formability and a satisfactory adhesion of the electroless copper
plating coating. This is because only the black area rate does not
satisfy the size of the profile and the appropriate distribution of
the profile on the plane thereof. From such a viewpoint, the
average value of the diameters of the holes of the surface of the
resin substrate according to the present invention is controlled so
as to be 0.03 to 1.0 .mu.m. When the average value of the diameters
of the holes concerned of the surface of the resin substrate is
less than 0.03 .mu.m, it is difficult to achieve a satisfactory
adhesion of the electroless copper plating coating. When the
average value of the diameters of the holes concerned of the
surface of the resin substrate exceeds 1.0 .mu.m, the fine wiring
formability is degraded.
[0310] As described above, in the resin substrate according to the
present invention, it is preferable that the black area rate
concerned of the substrate surface be 10 to 50% and the average
value of the diameters of the holes concerned of the substrate
surface be 0.03 to 1.0 .mu.m; it is more preferable that the black
area rate be 15 to 45% and the average value of the diameters of
the holes be 0.1 to 0.8 .mu.m; and it is furthermore preferable
that the black area rate be 20 to 40% and the average value of the
diameters of the holes be 0.15 to 0.7 .mu.m.
[0311] By controlling the current density for surface treatment
during the surface treatment such as during the formation of
roughened particles and the immersion time in a plating solution
after the completion of the surface treatment, the surface state of
the copper foil and the form and the formation density of roughened
particles, after the surface treatment are determined, and the
surface roughness Sz, the area ratio B/A, the black area rate and
the average value of the diameters of the holes of the
surface-treated copper foil can be controlled.
[0312] Specifically, during the surface treatment such as during
the formation of roughened particles, by performing the surface
treatment with the current density of the surface treatment
controlled to be high, and successively performing the surface
treatment with the current density of the surface treatment
controlled to be low, the surface state of the copper foil and the
form and the formation density of roughened particles, after the
surface treatment are determined, and the above-described surface
roughness Sz, area ratio B/A, black area rate and average value of
the diameters of the holes can be controlled. In addition, it is
also effective to repeatedly perform the operation that the surface
treatment is performed with the current density of the surface
treatment controlled to be high, and successively the surface
treatment is performed with the current density of the surface
treatment controlled to be low.
[0313] Here, when the current density is allowed to be high during
the surface treatment such as during the formation of roughened
particles, the deposited metal particles tend to grow in a
direction perpendicular to the surface of the copper foil. In
addition, when the current density is allowed to be low during the
surface treatment such as during the formation of roughened
particles, the surface of the copper foil tends to be smooth
(asperities tend to occur to a low degree).
[0314] Accordingly, the operation that the surface treatment is
performed with the current density of the surface treatment
controlled to be high, and successively the surface treatment is
performed with the current density of the surface treatment
controlled to be low is regarded as the surface state control such
that metal particles are allowed to grow in the direction
perpendicular to the surface of the copper foil, and subsequently
the asperities due to the metal particles and the surface of the
cooper foil are embedded so as to form a smooth surface.
[0315] In addition, when the surface-treated layer of the copper
foil is easily dissolved in a plating solution, the effect of the
immersion time in the plating solution after the completion of the
surface treatment on the surface form of the surface treated copper
foil tends to be more profound.
[0316] [Copper Foil with Carrier]
[0317] As the surface-treated copper foil according to the present
invention, a copper foil with carrier may also be used. The copper
foil with carrier includes a carrier, an intermediate layer
laminated on the carrier, and an ultra-thin copper layer laminated
on the intermediate layer. Alternatively, the copper foil with
carrier may include a carrier, an intermediate layer and an
ultra-thin copper layer, in this order. The copper foil with
carrier may have a surface-treated layer such as a
roughening-treated layer on one of or each of both of the surface
on the carrier side and the surface on the ultra-thin copper layer
side.
[0318] In the case where a roughening-treated layer is provided on
the surface on the carrier side of the copper foil with carrier,
when the copper foil with carrier is laminated, via the surface
side thereof on the carrier side concerned, on s support such as a
resin substrate, the copper foil with carrier has an advantage that
the carrier and the support such as a substrate are hardly peeled
from each other.
[0319] <Carrier>
[0320] In the present invention, a metal foil can be used as a
carrier. As the metal foil, copper foil, copper alloy foil, nickel
foil, nickel alloy foil, aluminum foil, aluminum alloy foil, iron
foil, iron alloy foil, stainless steel foil, zinc foil, zinc alloy
foil and the like can be used. Among these, as the carrier, from
the viewpoint of the easiness in forming a release layer, it is
particularly preferable to use copper foil. The carrier is
typically provided in the form of a rolled copper foil or an
electrolytic copper foil. In general, electrolytic copper foil is
produced by electrolytically depositing copper on a titanium or
stainless steel drum from a copper sulfate plating bath, and rolled
copper foil is produced by repeating plastic working and heat
treatment with a rolling roll. As the material for the copper foil,
there can be used, in addition to high purity copper such as tough
pitch copper and oxygen-free copper, for example, Sn-containing
copper, Ag-containing copper, copper alloy with Cr, Zr, Mg or the
like added thereto, and copper alloys such as Corson alloys with
Ni, Si and the like added thereto.
[0321] The thickness of the carrier usable in the present invention
is not particularly limited; the thickness concerned can be
appropriately regulated to be a thickness suitable for achieving
the role as the carrier, and the thickness concerned is allowed to
be 12 .mu.m or more. However, the thickness concerned is too thick,
the production cost is increased, and hence, in general, it is
preferable to set the thickness to be 35 .mu.m or less.
Accordingly, the thickness of the carrier is typically 12 to 70
.mu.m, and more typically 18 to 35 .mu.m.
[0322] <Intermediate Layer>
[0323] On the carrier, the intermediate layer is provided. Between
the carrier and the intermediate layer, another layer may be
provided. The intermediate layer used in the present invention is
not particularly limited as long as the intermediate layer has a
constitution such that the ultra-thin copper layer is hardly peeled
from the carrier before the step of laminating the copper foil with
carrier on the insulating substrate, and on the other hand, after
the step of laminating on the insulating substrate, the ultra-thin
copper layer is allowed to be peeled from the carrier. For example,
the intermediate layer of the copper foil with carrier of the
present invention may include one or two or more selected from the
group consisting of Cr, Ni, Co, Fe, Mo, Ti, W, P, Cu, Al, Zn,
alloys of these, hydrates of these, oxides of these and organic
substances. In addition, the intermediate layer maybe composed of
two or more layers.
[0324] For example, the intermediate layer can be constituted by
forming, from the carrier side, a single metal layer composed of
one element selected from the element group constituted with one
element selected from the group consisting of Cr, Ni, Co, Fe, Mo,
Ti, W, P, Cu, Al and Zn, or an alloy layer composed of one or two
or more elements selected from the element group consisting of Cr,
Ni, Co, Fe, Mo, Ti, W, P, Cu, Al and Zn, and by forming, on the
single metal layer of the alloy layer, a layer composed of hydrates
or oxides of one or two or more elements selected from the element
group consisting of Cr, Ni, Co, Fe, Mo, Ti, W, P, Cu, Al and
Zn.
[0325] In addition, for example, the intermediate layer can be
constituted by laminating, on the carrier, nickel, a
nickel-phosphorus alloy or a nickel-cobalt alloy, and chromium in
this order. The adhesion between nickel and copper is higher than
the adhesion between chromium and copper, and hence, when the
ultra-thin copper layer is peeled, peeling occurs between the
ultra-thin copper layer and chromium. For the nickel in the
intermediate layer, the barrier effect to prevent the diffusion of
the copper component from the carrier to the ultra-thin copper
layer is expected. The deposition amount of nickel in the
intermediate layer is preferably 100 .mu.g/dm.sup.2 or more and
40000 .mu.g/dm.sup.2 or less, more preferably 100 .mu.g/dm.sup.2 or
more and 4000 .mu.g/dm.sup.2 or less, more preferably 100
.mu.g/dm.sup.2 or more and 2500 .mu.g/dm.sup.2 or less, and more
preferably 100 .mu.g/dm.sup.2 or more and 1000 g/dm.sup.2 or less;
the deposition amount of chromium in the intermediate layer is
preferably 5 .mu.g/dm.sup.2 or more and 100 .mu.g/dm.sup.2 or less.
When the intermediate layer is provided only on one side, it is
preferable to provide a rust-preventing layer such as a Ni plating
layer carrier on the opposite side of the carrier. On both sides of
the carrier, the intermediate layers may also be provided.
[0326] <Ultra-Thin Copper Layer>
[0327] On the intermediate layer, the ultra-thin copper layer is
provided. Another layer may also be provided between the
intermediate layer and the ultra-thin copper layer. The ultra-thin
copper layer concerned is the surface-treated copper foil of the
present invention. The thickness of the ultra-thin copper layer is
not particularly limited, but is generally thinner than the
carrier, and for example, 12 .mu.m or less. The thickness of the
ultra-thin copper layer is typically 0.5 to 12 .mu.m and more
typically 1.5 to 5 .mu.m. In addition, before the ultra-thin copper
layer is provided on the intermediate layer, a strike plating using
a copper-phosphorus alloy may be performed in order to reduce the
pin-holes of the ultra-thin copper layer. For the strike plating,
for example, a copper pyrophosphate plating solution may be cited.
On both sides of the carrier, ultra-thin copper layers may also be
provided.
[0328] [Resin Layer on Surface-Treated Layer]
[0329] A resin layer may also be provided on the surface-treated
layer of the surface-treated copper foil of the present invention.
The resin layer may be an insulating resin layer.
[0330] The resin layer may be an adhesive, or an insulating resin
layer of a semi-cured state (B stage state) for adhesion. The
semi-cured state (B stage state) includes a state in which no
sticky feeling is sensed when the finger is in contact with the
surface, the insulating resin layer can be stored in a state of
being superposed, and moreover, curing reaction occurs when
undergoing heat treatment.
[0331] The resin layer may include a thermocuring resin or may be a
thermoplastic resin. The resin layer may include a thermoplastic
resin. The type of the above-described resin is not particularly
limited; examples of the suitable resins include: epoxy resin,
polyimide resin, multifunctional cyanic acid ester compound,
maleimide compound, maleimide-based resin, polyvinylacetal resin,
urethane resin, polyether sulfone, polyether sulfone resin,
aromatic polyamide resin, polyamideimide resin, rubber-modified
epoxy resin, phenoxy resin, carboxyl group-modified
acrylonitrile-butadiene resin, polyphenylene oxide, bismaleimide
triazine resin, thermocuring polyphenylene oxide resin, cyanate
ester-based resin, and polybasic carboxylic acid
anhydride-containing resin. The resin layer may be a resin layer
including a block copolymerized polyimide resin layer, or a resin
layer including a block copolymerized polyimide resin and a
polymaleimide compound. The epoxy resin can be used without causing
any particular problem as long as the epoxy resin has two or more
epoxy groups in the molecule thereof, and can be used for the
application to electric-electronic material. The epoxy resin is
preferably an epoxy resin obtained by epoxidation by using a
compound having two or more glycidyl groups in the molecule of the
compound. As the epoxy resin, one or mixtures of two or more
selected from the group consisting of bisphenol A-type epoxy resin,
bisphenol F-type epoxy resin, bisphenol S-type epoxy resin,
bisphenol AD-type epoxy resin, novolac type epoxy resin, cresol
novolac type epoxy resin, alicyclic epoxy resin, brominated epoxy
resin, glycidylamine-type epoxy resin, triglycidyl isocyanurate,
glycidylamine compounds such as N,N-diglycidylaniline, glycidyl
ester compounds such as tetrahydrophthalic acid diglycidyl ester,
phosphorus-containing epoxy resin, biphenyl-type epoxy resin,
biphenyl novolac type epoxy resin, tris-hydroxyphenylmethane-type
epoxy resin, and tetraphenyl methane-type epoxy resin; or
alternatively, the hydrogenated products or the halogenated
products of the above-described epoxy resins can also be used.
[0332] The resin layer may include heretofore known resins, resin
curing agents, compounds, curing promoters, dielectrics (any
dielectrics such as dielectrics including inorganic compounds
and/or organic compounds, or dielectrics including metal oxides may
be used), reaction catalysts, cross-linking agents, polymers,
prepregs, skeletal materials and the like. The resin layer may be
formed by using the substances (resins, resin curing agents,
compounds, curing promoters, dielectrics, reaction catalysts,
cross-linking agents, polymers, prepregs, skeletal materials and
the like) and/or the methods for forming resin layers, and the
apparatuses for forming resin layers described in the following
documents: International Publication No. WO 2008/004399,
International Publication No. WO 2008/053878, International
Publication No. WO 2009/084533, Japanese Patent Laid-Open No.
11-5828, Japanese Patent Laid-Open No. 11-140281, Japanese Patent
No. 3184485, International Publication No. WO 97/02728, Japanese
Patent No. 3676375, Japanese Patent Laid-Open No. 2000-43188,
Japanese Patent No. 3612594, Japanese Patent Laid-Open No.
2002-179772, Japanese Patent Laid-Open No. 2002-359444, Japanese
Patent Laid-Open No. 2003-304068, Japanese Patent No. 3992225,
Japanese Patent Laid-Open No. 2003-249739, Japanese Patent No.
4136509, Japanese Patent Laid-Open No. 2004-82687, Japanese Patent
No. 4025177, Japanese Patent Laid-Open No. 2004-349654, Japanese
Patent No. 4286060, Japanese Patent Laid-Open No. 2005-262506,
Japanese Patent No. 4570070, Japanese Patent Laid-Open No.
2005-53218, Japanese Patent No. 3949676, Japanese Patent No.
4178415, International Publication No. WO 2004/005588, Japanese
Patent Laid-Open No. 2006-257153, Japanese Patent Laid-Open No.
2007-326923, Japanese Patent Laid-Open No. 2008-111169, Japanese
Patent No. 5024930, International Publication No. WO 2006/028207,
Japanese Patent No. 4828427, Japanese Patent Laid-Open No.
2009-67029, International Publication No. WO 2006/134868, Japanese
Patent No. 5046927, Japanese Patent Laid-Open No. 2009-173017,
International Publication No. WO 2007/105635, Japanese Patent No.
5180815, International Publication No. WO 2008/114858,
International Publication No. WO 2009/008471, Japanese Patent
Laid-Open No. 2011-14727, International Publication No. WO
2009/001850, International Publication No. WO 2009/145179,
International Publication No. WO 2011/068157, Japanese Patent
Laid-Open No. 2013-19056.
[0333] Resin solutions are prepared by dissolving these resins in
the solvents such as methyl ethyl ketone (MEK), cyclopentanone,
dimethyl formamide, dimethyl acetamide, N-methylpyrrolidone,
toluene, methanol, ethanol, propylene glycol monomethyl ether,
dimethyl formamide, dimethyl acetamide, cyclohexanone, ethyl
cellosolve, N-methyl-2-pyrrolidone, N,N-dimethyl acetamide, and
N,N-dimethyl formamide; these resin solutions are applied to the
ultra-thin copper layer, or the heat resistant layer, the
rust-preventing layer, the chromate-treated layer, or the silane
coupling agent layer by, for example, a roll coater method,
successively heat-dried, if necessary, to remove the solvent to
form a B-stage state. For the drying, for example, a hot air drying
furnace may be used, and the drying temperature may be 100 to
250.degree. C., and preferably 130 to 200.degree. C. The
composition of the resin layer may be dissolve by using a solvent,
to prepare a resin solution having a resin solid content of 3 wt %
to 60 wt %, preferably 10 wt % to 40 wt %, and more preferably 25
wt % to 40 wt %. The dissolution by using a mixed solvent composed
of methyl ethyl ketone and cyclopentanone is mot preferable at the
present stage from an environmental viewpoint.
[0334] The surface-treated copper foil provided with the resin
layer (surface-treated copper foil with resin) is used in a mode in
which the resin layer of the copper foil is superposed on the
substrate, then the whole is thermally compression bonded to
thermally cure the resin layer, and successively a predetermined
wiring pattern is formed on the copper foil. For the copper foil
with carrier using the surface-treated copper foil concerned as the
ultra-thin copper layer, the copper foil with carrier provided with
the resin layer (copper foil with carrier with resin) is used in a
mode in which the resin layer of the copper foil is superposed on
the substrate, then the whole is thermally compression bonded to
thermally cure the resin layer, successively the carrier is peeled
to expose the ultra-thin copper layer (naturally, the exposed face
is the surface on the intermediate layer side of the ultra-thin
copper layer), and a predetermined wiring patter is formed on the
exposed ultra-thin copper layer.
[0335] When the surface-treated copper foil with resin or the
copper foil with resin and carrier is used, it is possible to
reduce the number of sheets of prepreg material used during the
production of a multilayer printed wiring board. Moreover, it is
possible to produce a copper clad laminate when the thickness of
the resin layer is allowed to be a thickness capable of ensuring
interlayer insulation, or even when no prepreg material is used at
all. In this case, it is also possible to further improve the
smoothness of the surface of the substrate by undercoating an
insulating resin on the surface of the substrate.
[0336] When no prepreg material is used, the material cost for the
prepreg material can be saved, the laminating step is made simple,
thus, economic advantage is provided, the thickness of the produced
multilayer printed wiring board is made thinner by the thickness of
the prepreg material, and in particular, in the case of a copper
foil with resin and carrier, there is provided an advantage that an
ultra-thin multilayer printed wiring board having a thickness of
one layer of 100 .mu.m or less can be produced. The thickness of
the resin layer concerned is preferably 0.1 to 120 .mu.m.
[0337] When the thickness of the resin layer is thinner than 0.1
.mu.m, the adhesion is degraded; when the surface-treated copper
foil with resin or the copper foil with resin and carrier is
laminated on a substrate having an inner layer material, it is
sometimes difficult to ensure the inter layer insulation with the
circuit of the inner layer material. The total resin layer
thickness of the cured resin layer and the semi-cured resin layer
is preferably 0.1 .mu.m to 120 .mu.m and practically preferably 35
.mu.m to 120 .mu.m. In such a case, it is preferable that the
thickness of the cured resin layer be 5 to 20 .mu.m, and the
thickness of the semi-cured resin layer be 15 to 115 .mu.m. This is
because when the total resin layer thickness exceeds 120 .mu.m, it
is sometimes difficult to produce a thin multilayer printed wiring
board; and when the total resin layer thickness is less than 35
.mu.m, although it is easy to form a thin multilayer printed wiring
board, the resin layer as the insulating layer between the circuits
in the inner layers is too thin, and the insulation between the
circuits of the inner layers sometimes tends to be made unstable.
When the thickness of the cured resin layer is less than 5 .mu.m,
it is sometimes necessary to consider the surface roughness degree
of the roughened surface of the copper foil. On the contrary, when
the thickness of the cured resin layer exceeds 20 .mu.m, the effect
due to the cured resin layer is sometimes not particularly
improved, and the total thickness is thick. The cured resin layer
may be 3 .mu.m to 30 .mu.m in thickness. The semi-cured resin layer
may be 7 .mu.m to 55 .mu.m in thickness. The total thickness of the
cured resin layer and the semi-cured resin layer may be 10 .mu.m to
60 .mu.m.
[0338] When the surface-treated copper foil with resin or the
copper foil with resin and carrier is used in the production of an
ultra-thin multilayer printed wiring board, it is preferable for
the purpose of reducing the thickness of the multilayer printed
wiring board that the thickness of the resin layer be set to be 0.1
.mu.m to 5 .mu.m, more preferably 0.5 .mu.m to 5 .mu.m, and more
preferably 1 .mu.m to 5 .mu.m. When the thickness of the resin
layer is set to be 0.1 .mu.m to 5 .mu.m, in order to improve the
adhesion between the resin layer and the copper foil, after a heat
resistant layer and/or a rust-preventing layer and/or a
chromate-treated layer and/or a silane coupling treated layer is
provided on the surface-treated layer, it is preferable to form a
resin layer on the heat resistant layer or the rust-preventing
layer or the chromate-treated layer or the silane coupling treated
layer.
[0339] When the resin layer includes a dielectric, the thickness of
the resin layer is preferably 0.1 to 50 .mu.m, preferably 0.5 .mu.m
to 25 .mu.m, and more preferably 1.0 .mu.m to 15 .mu.m. The
thickness of the resin layer means an average value of the
thickness values measured at optional 10 points by cross-sectional
observation.
[0340] On the other hand, when the thickness of the resin layer is
made thicker than 120 .mu.m, it is difficult to form a resin layer
having the intended thickness by one step of application, and thus
extraneous material cost and extraneous number of steps are needed
to be economically disadvantageous. Moreover, the formed resin
layer is poor in flexibility, cracks or the like tend to occur
during handling the resin layer, and smooth lamination is sometimes
made difficult due to the occurrence of excessive resin flow during
the thermal compression bonding to the inner layer material.
[0341] Moreover, as another product form of the copper foil with
resin and carrier, it is also possible to produce in a form of a
copper foil with resin, without including the carrier, by coating a
resin layer on the ultra-thin copper layer, or the heat resistant
layer, or the rust-preventing layer, or the chromate-treated layer,
or the silane coupling treated layer, by converting the resin layer
into a semi-cured state, and by successively peeling the
carrier.
[0342] Hereinafter, several examples of the production process of
the printed wiring board using the resin substrate according to the
present invention. A printed circuit board is completed by mounting
electronic components on the printed wiring board.
[0343] An embodiment of the method for producing a printed wiring
board according to the present invention, using a semi-additive
method includes: a step of preparing a surface-treated copper foil
and a resin substrate; a step of laminating the surface-treated
copper foil, via the surface-treated layer side thereof, on the
resin substrate; a step of obtaining the resin substrate of the
present invention by removing the surface-treated copper foil on
the resin substrate; and a step of forming a circuit on the surface
of the resin substrate with the surface-treated copper foil removed
therefrom.
[0344] FIG. 1 illustrates a schematic example of a semi-additive
method using the profile of a copper foil. In the method concerned,
the surface profile of the copper foil is used for the formation of
the surface profile of the resin substrate. Specifically, first, a
copper clad laminate is prepared by laminating the copper foil of
the present invention on the resin substrate. Next, the copper foil
of the copper clad laminate is subjected to entire-surface etching.
Next, electroless copper plating is applied to the surface of the
resin substrate (entire-surface etched substrate) with the surface
profile of the copper foil transferred thereon. Then, the portion,
free from formation of circuit, of the resin substrate
(entire-surface etched substrate) is coated with a dry film or the
like, and electro (electrolytic) copper plating is applied to the
surface, not coated with the dry film, of the electroless copper
plating layer. Subsequently, after the dry film is removed, the
electroless copper plating formed on the portion free from
formation of circuit is removed to form a fine circuit. The fine
circuit formed in the present invention adheres to the etched
surface of the resin substrate (entire-surface etched substrate)
with the surface profile of the copper foil of the present
invention transferred thereon, and hence the adhesion (peel
strength) of the fine circuit is made satisfactory.
[0345] The resin substrate can be a resin substrate incorporating
an inner layer circuit. In the present invention, the semi-additive
method means a method in which thin electroless plating and/or
electrolytic plating is applied on a resin substrate or a copper
foil seed layer, and after the formation of a pattern, a conductor
pattern is formed by using electroplating or etching. For
electroless plating and/or electrolytic plating, copper plating can
be used. As the method for forming copper plating, heretofore known
methods can be used.
[0346] An embodiment of the method for producing a printed wiring
board according to the present invention, using the semi-additive
method includes: a step of preparing a copper foil with carrier and
a resin substrate; a step of laminating the copper foil with
carrier, via the ultra-thin copper layer side thereof, to the resin
substrate; a step of peeling the carrier of the copper foil with
carrier after the copper foil with carrier and the resin substrate
are laminated on each other; a step of obtaining the resin
substrate of the present invention by removing the ultra-thin
copper layer on the resin substrate after peeling the carrier; and
a step of forming a circuit on the surface of the resin substrate
with the ultra-thin copper layer removed therefrom.
[0347] In the present invention, the semi-additive method means a
method in which thin electroless plating is applied on an
insulating substrate or a copper foil seed layer, subsequently
electrolytic plating is performed if necessary, further
subsequently, after formation of a pattern, a conductor pattern is
formed by using electroplating and etching.
[0348] An embodiment of the method for producing a printed wiring
board according to the present invention, using a semi-additive
method includes: a step of preparing a copper foil with carrier and
an insulating substrate; a step of laminating the copper foil with
carrier, via the ultra-thin copper layer side thereof, on the
insulating substrate; a step of peeling the carrier of the copper
foil with carrier after laminating the copper foil with carrier and
the insulating substrate on each other; a step of removing the
ultra-thin copper layer on the insulating substrate after peeling
the carrier; and a step of forming a circuit on the surface of the
insulating substrate with the ultra-thin copper layer removed
therefrom.
[0349] An embodiment of the method for producing a printed wiring
board according to the present invention includes a step of
laminating a surface-treated copper foil, via the surface-treated
layer side thereof, on the resin substrate of the present invention
to form a copper clad laminate, and then forming a circuit by a
semi-additive method, a subtractive method, a partly additive
method or a modified semi-additive method.
[0350] An embodiment of the method for producing a printed wiring
board according to the present invention includes: a step of
preparing the surface-treated copper foil and an insulating
substrate; and a step of laminating the surface-treated copper
foil. via the surface-treated layer side thereof, on the insulating
substrate to form a copper clad laminate, and then forming a
circuit by a semi-additive method, a subtractive method, a partly
additive method or a modified semi-additive method.
[0351] In the present invention, the subtractive method means a
method in which the unnecessary portion of the copper foil on the
copper clad laminate is selectively removed by etching or the like
to form a conductor pattern.
[0352] In the present invention, the partly additive method means a
method in which catalyst nuclei are imparted on a substrate
including a conductor layer, and including, if necessary, pierced
holes for through-holes or via holes, and the substrate is etched
to form a conductor circuit; and after a solder resist or a plating
resist is provided if necessary, plating up is applied to the
through-holes, via holes or the like on the conductor circuit by
electroless plating treatment to produce a printed wiring
board.
[0353] In the present invention, the modified semi-additive method
means a method in which a metal foil is laminated on a resin
substrate; the non-circuit-formation portion is protected with a
plating resist, and the circuit-formation portion is subjected to
copper plating up; and then, the resist is removed and the metal
foil on the portion other than the circuit-formation portion is
removed by (flash) etching to form a circuit on the resin
substrate.
[0354] An embodiment of the method for producing a printed wiring
board according to the present invention includes: a step of
laminating a copper foil with carrier, via the ultra-thin copper
layer side thereof, on the resin substrate of the present
invention; and a step of laminating the copper foil with carrier
and the resin substrate on each other, then forming a copper clad
laminate by passing through a step of peeling the carrier of the
copper foil with carrier, and then forming a circuit by a
semi-additive method, a subtractive method, a partly additive
method or a modified semi-additive method.
[0355] An embodiment of the method for producing a printed wiring
board according to the present invention includes: a step of
preparing the copper foil with carrier and the insulating substrate
of the present invention; a step of laminating the copper foil with
carrier, via the ultra-thin copper layer side thereof, on the
insulating substrate; and a step of laminating the copper foil with
carrier and the insulating substrate on each other, then forming a
copper clad laminate by passing through a step of peeling the
carrier of the copper foil with carrier, and then forming a circuit
by a semi-additive method, a subtractive method, a partly additive
method or a modified semi-additive method.
[0356] An embodiment of the method for producing a printed wiring
board according to the present invention, using the semi-additive
method, includes: a step of preparing a metal foil with a circuit
formed on the surface thereof; a step of forming a resin substrate
on the surface of the metal foil so as for the circuit to be
embedded; a step of laminating a surface-treated copper foil or a
copper foil with carrier, via the surface-treated layer side
thereof or the ultra-thin copper layer side, respectively, on the
resin substrate; a step of obtaining the resin substrate of the
present invention by removing the surface-treated copper foil or
the copper foil with carrier on the resin substrate; a step of
forming a circuit on the surface of the resin substrate with the
surface-treated copper foil or the copper foil with carrier removed
therefrom; and a step of exposing the circuit formed on the surface
of the metal foil and embedded in the resin substrate by removing
the metal foil.
[0357] An embodiment of the method for producing printed wiring
board according to the present invention using the semi-additive
method, includes: a step of preparing a metal foil with a circuit
formed on the surface thereof; a step of forming a resin layer on
the surface of the metal foil so as for the circuit to be embedded;
a step of laminating the surface-treated copper foil of the present
invention, via the surface-treated layer side thereof, on the resin
layer; a step of removing the surface-treated copper foil on the
resin layer; a step of forming a circuit on the resin layer with
the surface-treated copper foil removed therefrom; and a step of
exposing the circuit formed on the surface of the metal foil and
embedded in the resin layer by removing the metal foil.
[0358] An embodiment of the method for producing a printed wiring
board according to the present invention, using the semi-additive
method, includes: a step of forming a circuit on the surface on the
ultra-thin copper layer side of a first copper foil with carrier; a
step of forming a resin substrate on the surface on the ultra-thin
copper layer side of the first copper foil with carrier so as for
the circuit to be embedded; a step of preparing a second copper
foil with carrier or a surface-treated copper foil, and laminating
the second copper foil with carrier or the surface-treated copper
foil, via the ultra-thin copper layer side thereof or the
surface-treated layer side, respectively, on the resin substrate; a
step of peeling the carrier of the second copper foil with carrier
after laminating the second copper foil with carrier or the
surface-treated copper foil on the resin substrate; a step of
obtaining the resin substrate of the present invention by removing
the ultra-thin copper layer or the surface-treated copper foil on
the resin substrate after peeling the carrier of the second copper
foil with carrier; a step of forming a circuit on the surface of
the resin substrate with the ultra-thin copper layer or the
surface-treated copper foil removed therefrom; a step of peeling
the carrier of the first copper foil with carrier after forming the
circuit on the resin substrate; and a step of exposing the circuit
formed on the surface on the ultra-thin copper layer side of the
first copper foil with carrier and embedded in the resin substrate,
by removing the ultra-thin copper layer of the first copper foil
with carrier, after peeling the carrier of the first copper foil
with carrier.
[0359] An embodiment of the method for producing a printed wiring
board according to the present invention, using the semi-additive
method, includes: a step of adopting the copper foil with carrier
of the present invention as a first copper foil with carrier and
forming a circuit on the surface on the ultra-thin copper layer
side of the first copper foil with carrier; a step of forming a
resin layer on the surface on the ultra-thin copper layer side of
the first copper foil with carrier so as for the circuit to be
embedded; a step of preparing a second copper foil with carrier,
and laminating the second copper foil with carrier, via the
ultra-thin copper layer side thereof of the second copper foil with
carrier, on the resin layer; a step of peeling the carrier of the
second copper foil with carrier, a step of removing the ultra-thin
copper layer on the resin layer after the peeling of the carrier of
the second copper foil with carrier; a step of forming a circuit on
the surface of the resin layer with the ultra-thin copper layer
removed therefrom; a step of peeling the carrier of the first
copper foil with carrier after forming the circuit on the resin
layer; and a step of exposing the circuit formed on the surface on
the ultra-thin copper layer side of the first copper foil with
carrier and embedded in the resin layer, by removing the ultra-thin
copper layer of the first copper foil with carrier after peeling
the carrier of the first copper foil with carrier.
[0360] An embodiment of the method for producing a printed wiring
board according to the present invention includes: a step of
preparing a metal foil with a circuit formed on the surface
thereof, a step of forming the resin substrate of the present
invention on the surface of the metal foil so as for the circuit to
be embedded, a step of laminating the surface-treated copper foil
or the copper foil with carrier, via the surface-treated layer side
thereof or the ultra-thin copper layer side, respectively, on the
resin substrate, and forming a circuit on the resin layer by a
semi-additive method, a subtractive method, a partly additive
method or a modified semi-additive method; and a step of exposing
the circuit formed on the surface of the metal foil and embedded in
the resin substrate by removing the metal foil.
[0361] An embodiment of the method for producing a printed wiring
board according to the present invention includes: a step of
preparing a metal foil with a circuit formed on the surface
thereof; a step of forming a resin layer on the surface of the
metal foil so as for the circuit to be embedded; a step of
laminating the surface-treated copper foil of the present
invention, via the surface-treated layer side thereof, on the resin
layer, and forming a circuit on the resin layer by a subtractive
method, a semi-additive method, a subtractive method, a partly
additive method or a modified semi-additive method; and a step of
exposing the circuit formed on the surface of the metal foil and
embedded in the resin layer by removing the metal foil.
[0362] An embodiment of the method for producing a printed wiring
board according to the present invention includes: a step of
forming a circuit on the surface on the ultra-thin copper layer
side of a first copper foil with carrier; a step of forming the
resin substrate of the present invention on the surface on the
surface on the ultra-thin copper layer side of the first copper
foil with carrier so as for the circuit to be embedded; a step of
preparing a second copper foil with carrier or a surface-treated
copper foil, laminating the second copper foil with carrier or the
surface-treated copper foil, via the ultra-thin copper layer side
thereof of the second copper foil with carrier or via the
surface-treated layer side thereof of the surface-treated copper
foil, respectively, on the resin substrate, peeling the carrier of
the second copper foil with carrier in the case where the second
copper foil with carrier on the resin substrate, and forming a
circuit on the resin substrate by a semi-additive method, a
subtractive method, a partly additive method/process or a modified
semi-additive method; a step of peeling the carrier of the first
copper foil with carrier after forming the circuit on the resin
substrate; and a step of exposing the circuit formed on the surface
on the ultra-thin copper layer side of the first copper foil with
carrier and embedded in the resin substrate by removing the
ultra-thin copper layer of the first copper foil with carrier after
peeling the carrier of the first copper foil with carrier.
[0363] An embodiment of the method for producing a printed wiring
board according to the present invention includes: a step of
adopting the copper foil with carrier of the present invention as a
first copper foil with carrier and forming a circuit on the surface
on the ultra-thin copper layer side of the first copper foil with
carrier; a step of forming a resin layer on the surface on the
ultra-thin copper layer side of the first copper foil with carrier
so as for the circuit to be embedded; a step of preparing a second
copper foil with carrier, laminating the second copper foil with
carrier, via the ultra-thin copper layer side thereof of the second
copper foil with carrier, on the resin layer, peeling the carrier
of the second copper foil with carrier, and forming a circuit on
the resin layer by a semi-additive method, a subtractive method, a
partly additive method or a modified semi-additive method; and a
step of exposing the circuit formed on the surface on the
ultra-thin copper layer side of the first copper foil with carrier
and embedded in the resin layer by removing the ultra-thin copper
layer of the first copper foil with carrier after peeling the
carrier of the first copper foil with carrier.
[0364] An embodiment of the method for producing a printed wiring
board according to the present invention includes: [0365] a step of
preparing a metal foil with a circuit formed on the surface
thereof; [0366] a step of forming a resin substrate on the surface
of the metal foil so as for the circuit to be embedded; [0367] a
step of laminating a copper foil with carrier including a carrier,
an intermediate layer and an ultra-thin copper layer in this order,
via the surface thereof on the ultra-thin copper layer side, on the
resin substrate; [0368] a step of obtaining the resin substrate of
the present invention by removing the ultra-thin copper layer on
the resin substrate after peeling the carrier of the copper foil
with carrier; [0369] a step of forming a circuit on the surface of
the resin substrate with the ultra-thin copper layer removed
therefrom; and [0370] a step of exposing the circuit formed on the
surface of the metal foil and embedded in the resin substrate by
removing the metal foil.
[0371] An embodiment of the method for producing a printed wiring
board according to the present invention includes: [0372] a step of
forming a circuit on the surface on the ultra-thin copper layer
side of a copper foil with carrier including a carrier, an
intermediate layer and an ultra-thin copper layer in this order;
[0373] a step of forming a resin substrate on the surface on the
ultra-thin copper layer side of the copper foil with carrier so as
for the circuit to be embedded; [0374] a step of laminating the
surface-treated copper foil, via the surface-treated layer side
thereof, on the resin substrate; [0375] a step of obtaining the
resin substrate of the present invention by removing the
surface-treated copper foil on the resin substrate; [0376] a step
of forming a circuit on the surface of the resin substrate with the
surface-treated copper foil removed therefrom; [0377] a step of
peeling the carrier of the copper foil with carrier after forming
the circuit on the resin substrate; and [0378] a step of exposing
the circuit formed on the surface on the ultra-thin copper layer
side of the copper foil with carrier and embedded in the resin
substrate by removing the ultra-thin copper layer of the copper
foil with carrier after peeling the carrier of the copper foil with
carrier.
[0379] An embodiment of the method for producing a printed wiring
board according to the present invention includes: [0380] a step of
preparing a metal foil with a circuit formed on the surface
thereof; [0381] a step of forming the resin substrate of the
present invention on the surface of the metal foil so as for the
circuit to be embedded; [0382] a step of preparing a copper foil
with carrier including a carrier, an intermediate layer and an
ultra-thin copper layer in this order, laminating the copper foil
with carrier, via the ultra-thin copper layer side thereof, on the
resin substrate, then peeling the carrier of the copper foil with
carrier, and then forming a circuit on the resin substrate; and
[0383] a step of exposing the circuit formed on the surface of the
metal foil and embedded in the resin substrate by removing the
metal foil.
[0384] An embodiment of the method for producing a printed wiring
board according to the present invention includes: [0385] a step of
forming a circuit on the surface on the ultra-thin copper layer
side of the copper foil with carrier including a carrier, an
intermediate layer and an ultra-thin copper layer in this order;
[0386] a step of forming the resin substrate of the present
invention on the surface on the ultra-thin copper layer side of the
copper foil with carrier so as for the circuit to be embedded;
[0387] a step of laminating a surface-treated copper foil, via the
surface-treated layer side thereof, on the resin substrate, and
then forming a circuit on the resin substrate; [0388] a step of
peeling the carrier of the copper foil with carrier after forming a
circuit on the resin substrate; and [0389] a step of exposing the
circuit formed on the surface on the ultra-thin copper layer side
of the copper foil with carrier and embedded in the resin substrate
by removing the ultra-thin copper layer of the copper foil with
carrier after peeling the carrier of the copper foil with
carrier.
[0390] An embodiment of the method for producing a printed wiring
board according to the present invention, using the semi-additive
method, includes: a step of preparing a copper foil with carrier
and a resin substrate; a step of laminating the copper foil with
carrier and the resin substrate on each other; a step of peeling
the carrier of the copper foil with carrier after laminating the
copper foil with carrier and the resin substrate on each other, a
step of obtaining the resin substrate of the present invention by
completely removing the ultra-thin copper layer exposed by peeling
the carrier, by a method such as etching with a corrosive solution
such as an acid or etching with plasma; a step of providing
through-holes or/and blind vias in the resin exposed by removing
the ultra-thin copper layer by etching; a step of performing
desmear treatment in the region including the through-holes or/and
blind vias; a step of providing an electroless plating layer in the
region including the resin and the through-holes or/and the blind
vias; a step of providing a plating resist on the electroless
plating layer; a step of exposing the plating resist, and then
removing the plating resist in the region where a circuit is to be
formed; a step of providing an electrolytic layer in the region
where the plating resist is removed and the circuit is to be
formed; a step of removing the plating resist; and a step of
removing the electroless plating layer in the region other than the
region where the circuit is to be formed by flash etching or the
like.
[0391] In an embodiment, the method for producing a printed wiring
board of the present invention includes:
[0392] a step of preparing the surface-treated copper foil of the
present invention with a circuit formed on the surface thereof on
the surface-treated layer formed side, or the copper foil with
carrier of the present invention, with a circuit formed on the
surface thereof on the ultra-thin copper layer side; [0393] a step
of forming a resin layer on the surface of the surface-treated
copper foil or the surface of the copper foil with carrier so as
for the circuit to be embedded; [0394] a step of forming a circuit
on the surface of the resin layer; and [0395] a step of exposing
the circuit embedded in the resin layer by removing the
surface-treated copper foil or the copper foil with carrier.
[0396] In an embodiment, the method for producing a printed wiring
board of the present invention includes: [0397] a step of preparing
a metal foil with a circuit formed on the surface thereof, or a
first surface-treated copper foil being the surface-treated copper
foil of the present invention with a circuit formed on the surface
thereof on the surface-treated layer formed side, or a metal foil
with carrier with a circuit formed on the surface thereof on the
ultra-thin metal layer side, or a first copper foil with carrier
being the copper foil with carrier of the present invention with a
circuit formed on the surface thereof on the ultra-thin copper
layer side; [0398] a step of forming a resin layer on the surface
of the metal foil, or the surface of the surface-treated copper
foil, or the surface of the metal foil with carrier, or the surface
of the copper foil with carrier so as for the circuit to be
embedded; [0399] a step of laminating the second surface-treated
copper foil being the surface-treated copper foil of the present
invention, via the surface-treated layer side thereof, on the resin
layer, or a step of laminating the second copper foil with carrier
being the copper foil with carrier of the present invention, via
the ultra-thin copper layer side thereof, on the resin layer;
[0400] a step of peeling the carrier of the second copper foil with
carrier, in the case where the foil laminated on the resin layer is
the second copper foil with carrier; [0401] a step of removing the
surface-treated copper foil on the resin layer, or the ultra-thin
copper layer remaining as a result of peeling the carrier of the
second copper foil with carrier, [0402] a step of forming a circuit
on the surface of the resin layer with the surface-treated copper
foil removed therefrom, or the surface of the resin layer with the
ultra-thin copper layer removed therefrom; and [0403] a step of
exposing the circuit embedded in the resin layer after forming the
circuit on the resin layer by removing the metal foil, or by
removing the first surface-treated copper foil, or by removing the
ultra-thin metal layer after peeling the carrier of the metal foil
with carrier, or by removing the ultra-thin copper layer after
peeling the carrier of the first copper foil with carrier.
[0404] In the present invention, the metal foil with carrier
includes at least a carrier and an ultra-thin metal layer in this
order. As the carrier of the metal foil with carrier, a metal foil
can be used. As the metal foil, there can be used copper foil,
copper alloy foil, nickel foil, nickel alloy foil, aluminum foil,
aluminum alloy foil, iron foil, iron alloy foil, stainless steel
foil, zinc foil and zinc alloy foil. The thickness of the metal
foil can be set to be 1 to 10000 .mu.m, preferably 2 to 5000 .mu.m,
preferably 10 to 1000 .mu.m, preferably 18 to 500 .mu.m, and
preferably 35 to 300 .mu.m. As the carrier, a resin substrate, or
an plate of an inorganic substance or an organic substance can also
be used. The thickness of the resin substrate or the plate of an
inorganic substance or an organic substance can be made the same as
the above-described thickness of the metal foil.
[0405] The carrier and the metal foil may be laminated on each
other through the intermediary of an adhesive or a release agent,
or an intermediate layer, in a peelable manner. Alternatively, the
carrier and the metal foil may be joined to each other by welding,
deposition or the like in a peelable manner. When it is difficult
to peel the carrier and the metal foil from each other, the joined
portion between the carrier and the metal foil is removed by
cutting or the like, and then the carrier and the metal foil may be
peeled from each other.
[0406] The ultra-thin metal layer may be formed of copper, copper
alloy, nickel, nickel alloy, aluminum, aluminum alloy, iron, iron
alloy, stainless steel, zinc, or zinc alloy. The thickness of the
ultra-thin metal layer is allowed to fall within the same range as
the thickness range of the ultra-thin copper layer of the copper
foil with carrier. The ultra-thin metal layer is preferably an
ultra-thin copper layer from the viewpoint of the conductivity of
the circuit formed therefrom.
[0407] In an embodiment, the method for producing a printed wiring
board of the present invention includes: [0408] a step of preparing
the surface-treated copper foil of the present invention, with a
circuit formed on the surface thereof on the surface-treated layer
formed side, or the copper foil with carrier of the present
invention, with a circuit formed on the surface thereof on the
ultra-thin copper layer side; [0409] a step of forming a resin
layer on the surface of the surface-treated copper foil or the
surface of the copper foil with carrier so as for the circuit to be
embedded; [0410] a step of laminating a metal foil on the resin
layer, or a step of laminating a metal foil with carrier, via the
ultra-thin metal layer side thereof, on the resin layer; [0411] a
step of peeling the metal foil with carrier, in the case where the
foil laminated on the resin layer is the metal foil with carrier;
[0412] a step of removing the metal foil on the resin layer, or the
ultra-thin metal layer remaining as a result of peeling the carrier
of the metal foil with carrier; [0413] a step of forming a circuit
on the surface of the resin layer with the metal foil removed
therefrom, or the surface of the resin layer with the ultra-thin
copper layer removed therefrom; and [0414] a step of exposing the
circuit embedded in the resin layer by removing the surface-treated
copper foil after forming the circuit on the resin layer, or by
removing the ultra-thin copper layer after peeling the carrier of
the copper foil with carrier.
[0415] In an embodiment, the method for producing a printed wiring
board of the present invention includes: [0416] a step of preparing
a metal foil with a circuit formed on the surface thereof, or a
first surface-treated copper foil being the surface-treated copper
foil of the present invention with a circuit formed on the surface
thereof on the surface-treated layer formed side, or a metal foil
with carrier with a circuit formed on the surface thereof on the
ultra-thin metal layer side, or a first copper foil with carrier
being the copper foil with carrier of the present invention with a
circuit formed on the surface thereof on the ultra-thin copper
layer side; [0417] a step of forming a resin layer on the surface
of the metal foil, or the surface of the surface-treated copper
foil, or the surface of the metal foil with carrier, or the surface
of the copper foil with carrier so as for the circuit to be
embedded; [0418] a step of laminating the second surface-treated
copper foil being the surface-treated copper foil of the present
invention, via the surface-treated layer side thereof, on the resin
layer, or a step of laminating the second copper foil with carrier
being the copper foil with carrier of the present invention, via
the ultra-thin copper layer side thereof, on the resin layer;
[0419] a step of peeling the carrier of the second copper foil with
carrier, in the case where the foil laminated on the resin layer is
the second copper foil with carrier; [0420] a step of forming a
circuit on the resin layer, by using the surface-treated copper
foil on the resin layer, or the ultra-thin copper layer remaining
as a result of peeling the carrier of the second copper foil with
carrier, by a semi-additive method, a subtractive method, a partly
additive method or a modified semi-additive method; and [0421] a
step of exposing the circuit embedded in the resin layer by
removing the metal foil after forming a circuit on the resin layer,
or by removing the first surface-treated copper foil, or by
removing the ultra-thin metal layer after peeling the carrier of
the metal foil with carrier, or by removing the ultra-thin copper
layer after peeling the carrier of the first copper foil with
carrier.
[0422] In an embodiment, the method for producing a printed wiring
board of the present invention includes: [0423] a step of preparing
the surface-treated copper foil of the present invention with a
circuit formed on the surface thereof on the surface-treated layer
formed side, or the copper foil with carrier of the present
invention with a circuit formed on the surface thereof on the
ultra-thin copper layer side; [0424] a step of forming a resin
layer on the surface of the surface-treated copper foil or the
surface of the copper foil with carrier so as for the circuit to be
embedded; [0425] a step of laminating a metal foil on the resin
layer, of a step of laminating a metal foil with carrier, via the
ultra-thin copper layer side thereof, on the resin layer; [0426] a
step of peeling the carrier of the metal foil with carrier, in the
case where the foil laminated on the resin layer is the metal foil
with carrier; [0427] a step of forming a circuit on the resin
layer, by using the metal foil on the resin layer, or the
ultra-thin metal layer remaining as a result of peeling the carrier
of the metal foil with carrier, by a semi-additive method, a
subtractive method, a partly additive method or a modified
semi-additive method; and [0428] a step of exposing the circuit
embedded in the resin layer, by removing the surface-treated copper
foil after forming a circuit on the resin layer, or by removing the
ultra-thin copper layer after peeling the carrier of the copper
foil with carrier.
[0429] In an embodiment of the method for producing a printed
wiring board according to the present invention, using a
semi-additive method, includes: a step of preparing the copper foil
with carrier and the insulating substrate according to the present
invention; a step of laminating the copper foil with carrier and
the insulating substrate on each other; a step of peeling the
carrier of the copper foil with carrier after laminating the copper
foil with carrier and the insulating substrate; a step of
completely removing the ultra-thin copper layer exposed by peeling
the carrier, by a method such as etching with a corrosive solution
such as an acid or a method using plasma; a step of providing
through-holes or/and blind vias in the resin exposed by removing
the ultra-thin copper layer by etching; a step of performing
desmear treatment in the region including the through-holes or/and
blind vias; a step of providing an electroless plating layer in the
region including the resin and the through-holes or/and the blind
vias; a step of providing a plating resist on the electroless
plating layer; a step of exposing the plating resist, and then
removing the plating resist in the region where a circuit is to be
formed; a step of providing an electrolytic plating layer in the
region where the plating resist is removed and the circuit is to be
formed; a step of removing the plating resist; and a step of
removing the electroless plating layer in the region other than the
region where the circuit is to be formed by flash etching or the
like.
[0430] Another embodiment of the method for producing a printed
wiring board according to the present invention, using a
semi-additive method, includes: a step of preparing a copper foil
with carrier and a resin substrate; a step of laminating the copper
foil with carrier and the resin substrate on each other; a step of
peeling the carrier of the copper foil with carrier after
laminating the copper foil with carrier and the resin substrate on
each other; a step of obtaining the resin substrate of the present
invention by completely removing the ultra-thin copper layer
exposed by peeling the carrier, by a method such as etching with a
corrosive solution such as an acid or a method using plasma; a step
of providing an electroless plating layer on the surface of the
resin exposed by removing the ultra-thin copper layer by etching; a
step of providing a plating resist on the electroless plating
layer, a step of exposing the plating resist, and then removing the
plating resist in the region where a circuit is to be formed; a
step of providing an electrolytic plating layer in the region where
the plating resist is removed and the circuit is to be formed; a
step of removing the plating resist; and a step of removing, by
flash etching or the like, the electroless plating layer and the
ultra-thin copper layer in the region other than the region where
the circuit is to be formed.
[0431] Another embodiment of the method for producing a printed
wiring board according to the present invention, using a
semi-additive method, includes: a step of preparing the copper foil
with carrier and the insulating substrate according to the present
invention; a step of laminating the copper foil with carrier and
the insulating substrate on each other; a step of peeling the
carrier of the copper foil with carrier after laminating the copper
foil with carrier and the insulating substrate on each other; a
step of completely removing the ultra-thin copper layer exposed by
peeling the carrier, by a method such as etching with a corrosive
solution such as an acid or etching with plasma; a step of
providing an electroless plating layer on the surface of the resin
exposed by removing the ultra-thin copper layer by etching; a step
of providing a plating resist on the electroless plating layer; a
step of exposing the plating resist, and then removing the plating
resist in the region where a circuit is to be formed; a step of
providing an electrolytic plating layer in the region where the
plating resist is removed and the circuit is to be formed; a step
of removing the plating resist; and a step of removing the
electroless plating layer and the ultra-thin copper layer in the
region other than the region where the circuit is to be formed, by
flash etching or the like.
[0432] An embodiment of the method for producing a printed wiring
board according to the present invention, using a modified
semi-additive method, includes: a step of preparing a copper foil
with carrier and a resin substrate; a step of laminating the copper
foil with carrier and the resin substrate on each other; a step of
peeling the carrier of the copper foil with carrier after
laminating the copper foil with carrier and the resin substrate on
each other; a step of providing through-holes or/and blind vias in
the ultra-thin copper layer exposed by peeling the carrier and the
resin substrate; a step of obtaining the surface profile of the
resin substrate of the present invention by performing desmear
treatment in the region including the through-holes or/and blind
vias; a step of providing an electroless plating layer in the
region including the through-holes or/and blind vias; a step of
providing a plating resist on the surface of the ultra-thin copper
layer exposed by peeling the carrier; a step of forming a circuit
by electrolytic plating after providing the plating resist; a step
of removing the plating resist; and a step of removing, by flash
etching, the ultra-thin copper layer exposed by removing the
plating resist.
[0433] An embodiment of the method for producing a printed wiring
board according to the present invention, using a modified
semi-additive method, includes: a step of preparing the copper foil
with carrier and the insulating substrate according to the present
invention; a step of laminating the copper foil with carrier and
the insulating substrate on each other; a step of peeling the
carrier of the copper foil with carrier after laminating the copper
foil with carrier and the insulating substrate on each other; a
step of providing through-holes or/and blind vias in the ultra-thin
copper layer exposed by peeling the carrier and the insulating
substrate; a step of performing a desmear treatment in the region
including the through-holes or/and blind vias; a step of providing
an electroless plating layer in the region including the
through-holes or/and blind vias; a step of providing a plating
resist on the surface of the ultra-thin copper layer exposed by
peeling the carrier; a step of forming a circuit by electrolytic
plating after providing the plating resist; a step of removing the
plating resist; and a step of removing the ultra-thin copper layer
exposed by removing the plating resist, by flash etching.
[0434] Another embodiment of the method for producing a printed
wiring board according to the present invention, using a modified
semi-additive method, includes: a step of preparing a copper foil
with carrier and a resin substrate; a step of laminating the copper
foil with carrier and the resin substrate on each other; a step of
peeling the carrier of the copper foil with carrier after
laminating the copper foil with carrier and the resin substrate on
each other; a step of providing a plating resist on the ultra-thin
copper layer exposed by peeling the carrier; a step of exposing the
plating resist, and then removing the plating resist in the region
where a circuit is to be formed; a step of providing an
electrolytic plating layer in the region where the plating resist
is removed and the circuit is to be formed; a step of removing the
plating resist; and a step of obtaining the surface profile of the
resin substrate of the present invention by removing, by flash
etching or the like, the electroless plating layer and the
ultra-thin copper layer in the region other than the region where
the circuit is to be formed.
[0435] Another embodiment of the method for producing a printed
wiring board according to the present invention, using a modified
semi-additive method, includes: a step of preparing the copper foil
with carrier and the insulating substrate according to the present
invention; a step of laminating the copper foil with carrier and
the insulating substrate on each other; a step of peeling the
carrier of the copper foil with carrier after laminating the copper
foil with carrier and the insulating substrate on each other; a
step of providing a plating resist on the ultra-thin copper layer
exposed by peeling the carrier; a step of exposing the plating
resist, and then removing the plating resist in the region where a
circuit is to be formed; a step of providing an electrolytic
plating layer in the region where the plating resist is removed and
the circuit is to be formed; and a step of removing, by flash
etching or the like, the electroless plating layer and the
ultra-thin copper layer in the region other than the region where
the circuit is to be formed.
[0436] An embodiment of the method for producing a printed wiring
board according to the present invention, using a partly additive
method, includes: a step of preparing a copper foil with carrier
and a resin substrate; a step of laminating the copper foil with
carrier and the resin substrate on each other; a step of peeling
the carrier of the copper foil with carrier after laminating the
copper foil with carrier and the resin substrate on each other; a
step of providing through-holes or/and blind vias in the ultra-thin
copper layer exposed by peeling the carrier and the resin
substrate; a step of obtaining the surface profile of the resin
substrate of the present invention by performing a desmear
treatment in the region including the through-holes or/and blind
vias; a step of imparting catalyst nuclei to the region including
the through-holes or/and the blind vias; a step of providing an
etching resist on the surface of the ultra-thin copper layer
exposed by peeling the carrier; a step of forming a circuit pattern
by exposing the etching resist; a step of forming a circuit by
removing the ultra-thin copper layer and the catalyst nuclei by a
method such as etching with a corrosive solution such as an acid or
by etching with plasma; a step of removing the etching resist; a
step of providing a solder resist or a plating resist on the
surface of the resin substrate exposed by removing the ultra-thin
copper layer and the catalyst nuclei by a method such as etching
with a corrosive solution such as an acid or etching with plasma;
and a step of providing an electroless plating layer in the region
where neither a solder resist nor a plating resist is provided.
[0437] An embodiment of the method for producing a printed wiring
board according to the present invention, using a partly additive
method, includes: a step of preparing the copper foil with carrier
and the insulating substrate according to the present invention; a
step of laminating the copper foil with carrier and the insulating
substrate on each other; a step of peeling the carrier of the
copper foil with carrier after laminating the copper foil with
carrier and the insulating substrate on each other; a step of
providing through-holes or/and blind vias in the ultra-thin copper
layer exposed by peeling the carrier and the insulating substrate;
a step of performing a desmear treatment in the region including
the through-holes or/and the blind vias; a step of imparting
catalyst nuclei to the region including the through-holes or/and
the blind vias; a step of providing an etching resist on the
surface of the ultra-thin copper layer exposed by peeling the
carrier: a step of forming a circuit pattern by exposing the
etching resist; a step of forming a circuit by removing the
ultra-thin copper layer and the catalyst nuclei by a method such as
etching with a corrosive solution such as an acid or by etching
with plasma; a step of removing the etching resist; a step of
providing a solder resist or a plating resist on the surface of the
insulating substrate exposed by removing the ultra-thin copper
layer and the catalyst nuclei by a method such as etching with a
corrosive solution such as an acid or etching with plasma; and a
step of providing an electroless plating layer in the region where
neither a solder resist nor a plating resist is provided.
[0438] An embodiment of the method for producing a printed wiring
board according to the present invention, using a subtractive
method, includes: a step of preparing a copper foil with carrier
and a resin substrate; a step of laminating the copper foil with
carrier and the resin substrate on each other; a step of peeling
the carrier of the copper foil with carrier after laminating the
copper foil with carrier and the resin substrate; a step of
providing through-holes or/and blind vias in the ultra-thin copper
layer exposed by peeling the carrier and the resin substrate; a
step of obtaining the surface profile of the resin substrate of the
present invention by performing a desmear treatment in the region
including the through-holes or/and the blind vias; a step of
providing an electroless plating layer in the region including the
through-holes or/and the blind vias; a step of providing an
electrolytic plating layer on the surface of the electroless
plating layer; a step of providing an etching resist on the surface
of the electrolytic plating layer or/and the surface of the
ultra-thin copper layer; a step of forming a circuit pattern by
exposing the etching resist; a step of forming a circuit by
removing the ultra-thin copper layer, and the electroless plating
layer and the electrolytic plating layer, by a method such as
etching with a corrosive solution such as an acid or etching with
plasma; and a step of removing the etching resist.
[0439] An embodiment of the method for producing a printed wiring
board according to the present invention, using a subtractive
method, includes: a step of preparing the copper foil with carrier
and the insulating substrate according to the present invention; a
step of laminating the copper foil with carrier and the insulating
substrate on each other; a step of peeling the carrier of the
copper foil with carrier after laminating the copper foil with
carrier and the insulating substrate on each other; a step of
providing through-holes or/and blind vias in the ultra-thin copper
layer exposed by peeling the carrier and the insulating substrate;
a step of performing a desmear treatment in the region including
the through-holes or/and the blind vias; a step of providing an
electroless plating layer in the region including the through-holes
or/and the blind vias; a step of providing an electrolytic plating
layer on the surface of the electroless plating layer; a step of
providing an etching resist on the surface of the electrolytic
plating layer or/and the surface of the ultra-thin copper layer; a
step of forming a circuit pattern by exposing the etching resist; a
step of forming a circuit by removing the ultra-thin copper layer,
and the electroless plating layer and the electrolytic plating
layer, by a method such as etching with a corrosive solution such
as an acid or etching with plasma; and a step of removing the
etching resist.
[0440] Another embodiment of the method for producing a printed
wiring board according to the present invention, using a
subtractive method, includes: a step of preparing a copper foil
with carrier and a resin substrate; a step of laminating the copper
foil with carrier and the resin substrate on each other; a step of
peeling the carrier of the copper foil with carrier after
laminating the copper foil with carrier and the resin substrate on
each other, a step of providing through-holes or/and blind vias in
the ultra-thin copper layer exposed by peeling the carrier and the
resin substrate; a step of obtaining the surface profile of the
resin substrate of the present invention by performing a desmear
treatment in the region including the through-holes or/and the
blind vias; a step of providing an electroless plating layer in the
region including the through-holes or/and the blind vias; a step of
forming a mask on the surface of the electroless plating layer; a
step of providing an electrolytic plating layer on the surface of
the electroless plating layer with no mask formed thereon; a step
of providing an etching resist on the surface of the electrolytic
plating layer or/and the surface of the ultra-thin copper layer; a
step of forming a circuit pattern by exposing the etching resist; a
step of forming a circuit by removing the ultra-thin copper layer
and the electroless plating layer by a method such as etching with
a corrosive solution such as an acid or etching with plasma; and a
step of removing the etching resist.
[0441] Another embodiment of the method for producing a printed
wiring board according to the present invention, using a
subtractive method, includes: a step of preparing the copper foil
with carrier and the insulating substrate according to the present
invention; a step of laminating the copper foil with carrier and
the insulating substrate on each other; a step of peeling the
carrier of the copper foil with carrier after laminating the copper
foil with carrier and the insulating substrate on each other; a
step of providing through-holes or/and blind vias in the ultra-thin
copper layer exposed by peeling the carrier and the insulating
substrate; a step of performing a desmear treatment in the region
including the through-holes or/and the blind vias; a step of
providing an electroless plating layer in the region including the
through-holes or/and the blind vias; a step of forming a mask on
the surface of the electroless plating layer; a step of providing
an electrolytic plating layer on the surface of the electroless
plating layer with no mask formed thereon; a step of providing an
etching resist on the surface of the electrolytic plating layer
or/and the surface of the ultra-thin copper layer; a step of
forming a circuit pattern by exposing the etching resist; a step of
forming a circuit by removing the ultra-thin copper layer and the
electroless plating layer by a method such as etching with a
corrosive solution such as an acid or etching with plasma; and a
step of removing the etching resist.
[0442] The step of providing through-holes or/and blind vias, and
the subsequent desmear step may be omitted.
[0443] Here, a specific example of the method for producing a
printed wiring board, using the copper foil with carrier of the
present invention is described in detail. [0444] Step 1: First, a
copper foil with carrier (first layer) having an ultra-thin copper
layer with a roughening-treated layer on the surface thereof is
prepared. [0445] Step 2: Next, a resist is applied on the
roughening-treated layer of the ultra-thin copper layer, exposure
and development are performed to etch the resist into a
predetermined shape. [0446] Step 3: Next, after forming a plating
for a circuit, the resist is removed, and thus a circuit plating
having a predetermined shape is formed. [0447] Step 4: Next, a
resin layer is laminated on the ultra-thin copper layer by
providing embedding resin so as for the circuit plating to be
covered (so as for the circuit plating to be embedded), and
successively another copper foil with carrier (second layer) is
made to adhere to the ultra-thin copper layer side. [0448] Step 5:
Next, from the copper foil with carrier as the second layer, the
carrier is peeled. Alternatively, as the second layer, a copper
foil having no carrier may also be used. [0449] Step 6: Next, laser
drilling is performed at the predetermined positions of the
ultra-thin copper layer as the second layer, or the copper foil and
the resin layer, and thus the circuit plating is exposed to form a
blind via. [0450] Step 7: Next, copper is implanted into the blind
via to form a via fill. [0451] Step 8: Next, on the via fill, a
circuit plating is formed in the same manner as in above-described
Steps 2 and 3. [0452] Step 9: Next, from the copper foil with
carrier as the first layer, the carrier is peeled. [0453] Step 10:
Next, by flash etching, the ultra-thin copper layers on both
surfaces (in the case where as the second layer, a copper foil is
provided, the copper foil is removed) are removed, to expose the
surface of the circuit plating in the resin layer. [0454] Step 11:
Next, a bump is formed on the circuit plating in the resin layer,
and a copper pillar is formed on the solder concerned. In this way,
a printed wiring board using the copper foil with carrier of the
present invention is prepared.
[0455] As the added copper foil with carrier (second layer), the
copper foil with carrier of the present invention may be used, a
conventional copper foil with carrier may also be used, and
moreover, a common copper foil may also be used. In addition, on
the circuit on the second layer in Step 8, a layer of a circuit or
a plurality of layers of circuits may be formed, and the formation
of these circuits may also be performed by a semi-additive method,
a subtractive method, a partly additive method or a modified
semi-additive method.
[0456] According to such a method for producing a printed wiring
board as described above, because of the constitution allowing the
circuit plating to be embedded in the resin layer, during removing
the ultra-thin copper layer by flash etching as in, for example,
the step 10, the circuit plating is protected by the resin layer,
the shape of the circuit plating is maintained, and accordingly the
formation of a fine circuit is facilitated. In addition, because
the circuit plating is protected by the resin layer, the migration
resistance is improved and the conduction of the circuit wiring is
suppressed satisfactorily. Accordingly, the formation of a fine
circuit is facilitated. As shown in the step 10 and the step 11,
when the ultra-thin copper layer is removed by flash etching, the
exposed surface of the circuit plating takes a shape recessed from
the resin layer, and hence the formation of a bump on the circuit
plating concerned, and moreover the formation of a copper pillar
thereon are facilitated to improve the production efficiency.
[0457] As the embedding resin (resin, heretofore known resins and
prepregs can be used. For example, there can be used BT
(bismaleimide triazine) resin, a prepreg being a glass cloth
impregnated with BT resin, and the ABF film and ABF manufactured by
Ajinomoto Fine-Techno Co., Ltd. As the embedding resin (resin), the
resin layer and/or the resin and/or the prepreg described in the
present description can also be used.
[0458] The copper foil with carrier used as the first layer may
have a substrate or a resin layer on the surface of the copper foil
with carrier concerned. Because of having the substrate concerned
of the resin layer concerned, the copper foil with carrier used as
the first layer is supported and hardly undergoes wrinkles to offer
an advantage that the productivity is improved. As the substrate or
the resin layer, any substrate or any resin layer that has an
effect to support the copper foil with carrier used as the first
layer can be used. For example, as the substrate or the resin
layer, the carriers, prepregs, and resin layers described in the
description of the present application, and heretofore known
carriers, prepregs, resin layers, metal plates, metal foils, plates
of inorganic compounds, foils of inorganic compounds, plates of
organic compounds and foils of organic compounds can be used.
[0459] In addition, by mounting electronic components and the like
on the printed wiring board, a printed circuit board is completed.
In the present invention, the "printed wiring board" is defined to
include such a printed wiring board with electronic components
mounted thereon, a printed circuit board, and a printed
substrate.
[0460] Additionally, electronic devices may also be fabricated by
using the printed wiring board concerned, electronic devices may
also be fabricated by using the printed wiring board concerned with
electronic components mounted thereon, or electronic devices may
also be fabricated by using the printed substrate concerned with
electronic components mounted thereon.
EXAMPLES
[0461] Hereinafter, Examples of the present invention are
described; these Examples are presented for the purpose of better
understanding of the present invention and the advantages thereof,
and are not intended to limit the present invention.
[0462] In present Example, as described below, the surface profile
of the resin substrate formed by using a copper foil and the
surface profile of the resin substrate formed by using a chemical
solution were produced.
[0463] 1. Formation of Surface Profile of Resin Substrate Using
Copper Foil
[0464] FIG. 2 illustrates a production flow of samples for
obtaining the data of Examples and Comparative Examples.
[0465] As Examples A1 to A11 and Comparative Examples A1 to A4, and
as the copper foils for producing the substrate surface profiles of
Examples B1 to B8, Examples B10 to B12 and Comparative Examples B1
to B4, the following copper foil bulk layers (raw foils) were
prepared.
[0466] Common Electrolytic Raw Foil
[0467] A copper sulfate electrolyte having a copper concentration
of 80 to 120 g/L, a sulfuric acid concentration of 80 to 120 g/L, a
chloride ion concentration of 30 to 100 ppm and a glue
concentration of 1 to 5 ppm, and a electrolyte temperature of 57 to
62.degree. C. was used as an electrolytic copper plating bath, a
linear speed of the electrolyte flowing between the anode and the
cathode (a metal drum for electrodeposition for copper foil) was
set at 1.5 to 2.5 m/sec, and a current density was set at 70
A/dm.sup.2, and thus, a common electrolytic raw foil having a
thickness of 12 .mu.m (thickness in terms of weight per unit area:
95 g/m.sup.2) was produced.
[0468] Double-Sided Flat Electrolytic Raw Foils
[0469] A copper sulfate electrolyte having a copper concentration
of 80 to 120 g/L, a sulfuric acid concentration of 80 to 120 g/L, a
chloride ion concentration of 30 to 100 ppm, a leveling agent 1
(bis(3-sulfopropyl) disulfide) concentration of 10 to 30 ppm and a
leveling agent 2 (an amine compound) concentration of 10 to 30 ppm
and a electrolyte temperature of 57 to 62.degree. C. was used as an
electrolytic copper plating bath, a linear speed of the electrolyte
flowing between the anode and the cathode (a metal drum for
electrodeposition for copper foil) was set at 1.5 to 2.5 m/sec, and
a current density was set at 70 A/dm.sup.2, and thus, a double flat
sided electrolytic raw foil having a thickness of 12 .mu.m
(thickness in terms of weight per unit area: 95 g/m.sup.2) was
produced. As the amine compound, an amine compound represented by
the following chemical formula was used.
##STR00002##
(wherein, in the chemical formula, R.sub.1 and R.sub.2 are each a
group selected from the group consisting of a hydroxyalkyl group,
an ether group, an aryl group, an aromatic-substituted alkyl group,
an unsaturated hydrocarbon group and an alkyl group.)
[0470] Ultra-Thin Raw Copper Foil with Carrier
[0471] Under the above-described production conditions of the
double flat sided electrolytic raw foil, a double flat sided
electrolytic raw foil having a thickness of 18 .mu.m was produced.
By using this as a copper foil carrier, a release layer and an
ultra-thin copper layer were formed by the following methods, and
thus ultra-thin copper foils with carrier having thicknesses of
1.5, 2, 3 and 5 .mu.m were obtained.
[0472] (1) Ni Layer (Release Layer: Base Plating 1)
[0473] On the S surface of the copper foil carrier, a Ni layer
having a deposition amount of 1000 .mu.g/dm.sup.2 was formed by
performing electroplating with a roll-to-roll type continuous
plating line under the following conditions. The specific plating
conditions are shown below.
[0474] Nickel sulfate: 270 to 280 g/L
[0475] Nickel chloride: 35 to 45 g/L
[0476] Nickel acetate: 10 to 20 g/L
[0477] Boric acid: 30 to 40 g/L
[0478] Gloss agent: Saccharin, butynediol and the like
[0479] Sodium dodecyl sulfate: 55 to 75 ppm
[0480] pH: 4 to 6
[0481] Bath temperature: 55 to 65.degree. C.
[0482] Current density: 10 A/dm.sup.2
[0483] (2) Cr Layer (Release Layer: Base Plating 2)
[0484] Next, after the surface of the Ni layer formed in (1) was
washed with water and washed with an acid, successively on the
roll-to-roll type continuous plating line, on the Ni layer, a Cr
layer having a deposition amount of 11 .mu.g/dm.sup.2 was attached
by performing an electrolytic chromate treatment under the
following conditions.
[0485] Potassium bichromate: 1 to 10 g/L, zinc: 0 g/L
[0486] pH: 7 to 10
[0487] Solution temperature: 40 to 60.degree. C.
[0488] Current density: 2 A/dm.sup.2
[0489] (3) Ultra-Thin Copper Layer
[0490] Next, after the surface of the Cr layer formed in (2) was
washed with water and washed with an acid, successively on the
roll-to-roll type continuous plating line, on the Cr layer,
ultra-thin copper layers having thicknesses of 1.5, 2, 3 and 5
.mu.m were formed by performing electroplating under the following
conditions, and thus ultra-thin copper foils with carrier were
produced. [0491] Copper concentration: 80 to 120 g/L [0492]
Sulfuric acid concentration: 80 to 120 g/L [0493] Chloride ion
concentration: 30 to 100 ppm [0494] Leveling agent 1
(bis(3-sulfopropyl) disulfide): 10 to 30 ppm [0495] Leveling agent
2 (amine compound): 10 to 30 ppm
[0496] As the leveling agent 2, the following amine compound was
used. As the amine compound, an amine compound represented by the
following chemical formula was used.
##STR00003##
(wherein, in the chemical formula, R.sub.1 and R.sub.2 are each a
group selected from the group consisting of a hydroxyalkyl group,
an ether group, an aryl group, an aromatic-substituted alkyl group,
an unsaturated hydrocarbon group and an alkyl group.) [0497]
Electrolyte temperature: 50 to 80.degree. C. [0498] Current
density: 100 A/dm.sup.2
[0499] Next, on the M surface (matte surface), namely, the surface,
on the side adhering to the resin substrate, of the raw foil resin
substrate or the S surface (shiny surface) of the raw foil, the
surface treatments, namely, a roughening treatment, a barrier
treatment, a rust-preventing treatment and an application of a
silane coupling agent were applied in this order. The treatment
conditions are shown below.
[0500] [Roughening Treatment]
[0501] Spherical Roughening (Ordinary):
[0502] The M surface or the S surface of each of the
above-described various raw foils were subjected to the roughening
treatment under the following conditions.
[0503] (Electrolyte Composition) [0504] Cu: 20 to 30 g/L (added as
copper sulfate pentahydrate, the same applies hereinafter) [0505]
H.sub.2SO.sub.4: 80 to 120 g/L [0506] Arsenic: 1.0 to 2.0 g/L
[0507] (Electrolyte Temperature) [0508] 35 to 40.degree. C.
[0509] (Current Condition) [0510] Current density: 70
A/dm.sup.2
[0511] On the M surface of each of the various copper foils and the
surface of each of the ultra-thin copper foils with carrier,
subjected to the roughening treatment under the above-described
conditions, a covering plating was performed in a copper
electrolyte bath composed of sulfuric acid and copper sulfate, in
order to prevent the dropout of roughened particles and improving
the peel strength. The covering plating conditions are shown
below.
[0512] (Electrolyte Composition) [0513] Cu: 40 to 50 g/L [0514]
H.sub.2SO.sub.4: 80 to 120 g/L
[0515] (Electrolyte Temperature) [0516] 43 to 47.degree. C.
[0517] (Current Condition) [0518] Current density: 29
A/dm.sup.2
[0519] Fine roughening (1):
[0520] The M surface of each of the above-described various raw
foil and the surface of each of the above-described various
ultra-thin raw copper foils with carrier were subjected to a
roughening treatment under the following conditions.
[0521] (Electrolyte Composition) [0522] Cu concentration: 10 to 20
g/L [0523] H.sub.2SO.sub.4 concentration: 80 to 120 g/L [0524]
Tungsten concentration: 1 to 10 mg/L (added as sodium tungstate
dihydrate) [0525] Sodium dodecyl sulfate concentration: 1 to 10
mg/L
[0526] (Electrolyte Temperature) [0527] 35 to 45.degree. C.
[0528] (Current Conditions)
[0529] In order to obtain the predetermined hole shapes, current
was imparted in four stages. The current densities were set as
follows. [0530] First stage: 30 A/dm.sup.2 [0531] Second stage: 10
A/dm.sup.2 [0532] Third stage: 30 A/dm.sup.2 [0533] Fourth stage:
10 A/dm.sup.2
[0534] On the M surface of each of the various copper foils and the
surface of each of the ultra-thin copper foils with carrier,
subjected to the roughening treatment under the above-described
conditions, a covering plating was performed in a copper
electrolyte bath composed of sulfuric acid and copper sulfate, in
order to prevent the dropout of roughened particles and improving
the peel strength. The covering plating conditions are described
below.
[0535] (Electrolyte Composition) [0536] Cu: 40 to 50 g/L [0537]
H.sub.2SO.sub.4: 80 to 120 g/L
[0538] (Electrolyte Temperature) [0539] 43 to 47.degree. C.
[0540] (Current Condition) [0541] Current density: 41
A/dm.sup.2
[0542] Fine Roughening (2):
[0543] The surface of each of the above-described ultra-thin raw
copper foils with carrier were subjected to a roughening treatment
under the following conditions.
[0544] (Electrolyte Composition) [0545] Cu concentration: 10 to 20
g/L [0546] H.sub.2SO.sub.4 concentration: 80 to 120 g/L [0547]
Tungsten concentration: 1 to 10 mg/L (added as sodium tungstate
dihydrate) [0548] Sodium dodecyl sulfate concentration: 1 to 10
mg/L
[0549] (Electrolyte Temperature) [0550] 35 to 45.degree. C.
[0551] (Current Conditions)
[0552] In order to obtain the predetermined hole shapes, a
two-stage process was applied. The current densities were set as
follows. [0553] First stage: 50 A/dm.sup.2 [0554] Second stage: 10
A/dm.sup.2
[0555] On the M surface of each of the various copper foils and the
surface of each of the ultra-thin copper foils with carrier,
subjected to the roughening treatment under the above-described
conditions, a covering plating was performed in a copper
electrolyte bath composed of sulfuric acid and copper sulfate, in
order to prevent the dropout of roughened particles and improving
the peel strength. The covering plating conditions are described
below.
[0556] (Electrolyte Composition) [0557] Cu: 40 to 50 g/L [0558]
H.sub.2SO.sub.4: 80 to 120 g/L
[0559] (Electrolyte Temperature) [0560] 43 to 47.degree. C.
[0561] (Current Condition) [0562] Current density: 41
A/dm.sup.2
[0563] Fine Roughening (3):
[0564] The M surface of each of the above-described double flat
sided electrolytic raw foils, and the surface of each of the
above-described various ultra-thin raw copper foils with carrier
were subjected to a roughening treatment under the following
conditions.
[0565] (Electrolyte Composition) [0566] Cu: 10 to 20 g/L [0567] Co:
1 to 10 g/L [0568] Ni: 1 to 10 g/L [0569] pH: 1 to 4
[0570] (Electrolyte Temperature) [0571] 40 to 50.degree. C.
[0572] (Current Condition) [0573] Current density: 25
A/dm.sup.2
[0574] (Immersion Time in Plating Solution after Completion of
Plating)
[0575] In order to obtain a predetermined hole shape, the immersion
time was set within 5 seconds.
[0576] The M surface of each of the double flat sided copper foils
and the surface of each of the ultra-thin copper foils with
carrier, subjected to the roughening treatment under the
above-described conditions, were subjected to a covering Co--Ni
plating. The covering plating conditions are described below.
[0577] (Electrolyte Composition) [0578] Co: 1 to 30 g/L [0579] Ni:
1 to 30 g/L [0580] pH: 1.0 to 3.5
[0581] (Electrolyte Temperature) [0582] 30 to 80.degree. C.
[0583] (Current Condition) [0584] Current density: 5.0
A/dm.sup.2
[0585] Fine Roughening (4):
[0586] The surface of each of the above-described ultra-thin raw
copper foils with carrier was subjected to a roughening treatment
to form primary particles and secondary particles under the
following conditions.
[0587] Formation of primary particles:
[0588] (Electrolyte Composition) [0589] Cu concentration: 10 to 20
g/L [0590] H.sub.2SO.sub.4 concentration: 80 to 120 g/L [0591]
Tungsten concentration: 1 to 10 mg/L (added as sodium tungstate
dihydrate) [0592] Sodium dodecyl sulfate concentration: 1 to 10
mg/L
[0593] (Electrolyte Temperature) [0594] 35 to 45.degree. C.
[0595] (Current Conditions)
[0596] In order to obtain the predetermined hole shapes, a
two-stage process was applied. The current densities were set as
follows. [0597] First stage: 50 A/dm.sup.2 [0598] Second stage: 10
A/dm.sup.2
[0599] On the surface of each of the ultra-thin copper foils with
carrier, subjected to the formation of primary roughened particles
under the above-described conditions, a covering plating was
performed in a copper electrolyte bath composed of sulfuric acid
and copper sulfate, in order to prevent the dropout of the primary
roughened particles and improving the peel strength. The covering
plating conditions are described below.
[0600] (Electrolyte Composition) [0601] Cu: 40 to 50 g/L [0602]
H.sub.2SO.sub.4: 80 to 120 g/L
[0603] (Electrolyte Temperature) [0604] 43 to 47.degree. C.
[0605] (Current Condition) [0606] Current density: 41
A/dm.sup.2
[0607] Formation of Secondary Particles:
[0608] Next, a roughening treatment to form secondary roughened
particles on the primary roughened particles of each of the
ultra-thin copper foils with carrier was performed.
[0609] (Electrolyte Composition) [0610] Cu: 10 to 20 g/L [0611] Co:
1 to 10 g/L [0612] Ni: 1 to 10 g/L [0613] pH: 1 to 4
[0614] (Electrolyte Temperature) [0615] 40 to 50.degree. C.
[0616] (Current Condition) [0617] Current density: 25
A/dm.sup.2
[0618] (Immersion Time in Plating Solution after Completion of
Plating)
[0619] In order to obtain a predetermined hole shape, the immersion
time was set within 5 seconds.
[0620] The surface of each of the ultra-thin copper foils with
carrier, subjected to the secondary particle roughening treatment
under the above-described conditions, were subjected to a covering
Co--Ni plating. The covering plating conditions are described
below.
[0621] (Electrolyte Composition) [0622] Co: 1 to 30 g/L [0623] Ni:
1 to 30 g/L [0624] pH: 1.0 to 3.5
[0625] (Electrolyte Temperature) [0626] 30 to 80.degree. C.
[0627] (Current Condition) [0628] Current density: 5.0
A/dm.sup.2
[0629] Fine Roughening (5):
[0630] A roughening treatment to form the primary particles and the
secondary particles on the surface of each of the above-described
ultra-thin raw copper foils with carrier was performed.
[0631] Formation of Primary Particles:
[0632] (Electrolyte Composition) [0633] Cu concentration: 10 to 20
g/L [0634] H.sub.2SO.sub.4 concentration: 80 to 120 g/L [0635]
Tungsten concentration: 1 to 10 mg/L (added as sodium tungstate
dihydrate) [0636] Sodium dodecyl sulfate concentration: 1 to 10
mg/L
[0637] (Electrolyte Temperature) [0638] 35 to 45.degree. C.
[0639] (Current Conditions)
[0640] In order to obtain the predetermined hole shapes, a
two-stage process was applied. The current densities were set as
follows. [0641] First stage: 20 A/dm.sup.2 [0642] Second stage: 10
A/dm.sup.2
[0643] On the surface of each of the ultra-thin copper foils with
carrier, subjected to the formation of primary roughened particles
under the above-described conditions, a covering plating was
performed in a copper electrolyte bath composed of sulfuric acid
and copper sulfate, in order to prevent the dropout of the primary
roughened particles and improving the peel strength. The covering
plating conditions are described below.
[0644] (Electrolyte Composition) [0645] Cu: 40 to 50 g/L [0646]
H.sub.2SO.sub.4: 80 to 120 g/L
[0647] (Electrolyte Temperature) [0648] 43 to 47.degree. C.
[0649] (Current Condition) [0650] Current density: 41
A/dm.sup.2
[0651] Formation of Secondary Particles:
[0652] Next, a roughening treatment to form secondary roughened
particles on the primary roughened particles of each of the
ultra-thin copper foils with carrier was performed.
[0653] (Electrolyte Composition) [0654] Cu: 10 to 20 g/L [0655] Co:
1 to 10 g/L [0656] Ni: 1 to 10 g/L [0657] pH: 1 to 4
[0658] (Electrolyte Temperature) [0659] 40 to 50.degree. C.
[0660] (Current Condition) [0661] Current density: 25
A/dm.sup.2
[0662] (Immersion Time in Plating Solution after Completion of
Plating)
[0663] In order to obtain a predetermined hole shape, the immersion
time was set to be 15 to 20 seconds.
[0664] The surface of each of the ultra-thin copper foils with
carrier, subjected to the secondary particle roughening treatment
under the above-described conditions, were subjected to a covering
Co--Ni plating. The covering plating conditions are described
below.
[0665] (Electrolyte Composition) [0666] Co: 1 to 30 g/L [0667] Ni:
1 to 30 g/L [0668] pH: 1.0 to 3.5
[0669] (Electrolyte Temperature) [0670] 30 to 80.degree. C.
[0671] (Current Condition) [0672] Current density: 5.0
A/dm.sup.2
[0673] Fine Roughening (6):
[0674] The surface of each of the above-described ultra-thin raw
copper foil with carrier was subjected to a roughening treatment
under the following conditions.
[0675] (Electrolyte Composition) [0676] Cu concentration: 10 to 20
g/L [0677] H.sub.2SO.sub.4 concentration: 80 to 120 g/L [0678]
Tungsten concentration: 1 to 10 mg/L (added as sodium tungstate
dihydrate) [0679] Sodium dodecyl sulfate concentration: 1 to 10
mg/L
[0680] (Electrolyte Temperature) [0681] 35 to 45.degree. C.
[0682] (Current Conditions)
[0683] In order to obtain the predetermined hole shapes, a
four-stage process was applied. The current densities were set as
follows. [0684] First stage: 50 A/dm.sup.2 [0685] Second stage: 10
A/dm.sup.2 [0686] Third stage: 50 A/dm.sup.2 [0687] Fourth stage:
10 A/dm.sup.2
[0688] On the M surface of each of the various copper foils and the
surface of each of the ultra-thin copper foils with carrier,
subjected to the roughening treatment under the above-described
conditions, a covering plating was performed in a copper
electrolyte bath composed of sulfuric acid and copper sulfate, in
order to prevent the dropout of roughened particles and improving
the peel strength. The covering plating conditions are described
below.
[0689] (Electrolyte Composition) [0690] Cu: 40 to 50 g/L [0691]
H.sub.2SO.sub.4: 80 to 120 g/L
[0692] (Electrolyte Temperature) [0693] 43 to 47.degree. C.
[0694] (Current Condition) [0695] Current density: 41 A/dm.sup.2
[0696] Fine Roughening (7):
[0697] A roughening treatment to form the primary particles and the
secondary particles on the surface of each of the above-described
ultra-thin raw copper foils with carrier was performed.
[0698] Formation of Primary Particles:
[0699] (Electrolyte Composition) [0700] Cu concentration: 10 to 20
g/L [0701] H.sub.2SO.sub.4 concentration: 80 to 120 g/L [0702]
Tungsten concentration: 1 to 10 mg/L (added as sodium tungstate
dihydrate) [0703] Sodium dodecyl sulfate concentration: 1 to 10
mg/L
[0704] (Electrolyte Temperature) [0705] 35 to 45.degree. C.
[0706] (Current Conditions)
[0707] In order to obtain the predetermined hole shapes, a
three-stage process was applied. The current densities were set as
follows. [0708] First stage: 25 A/dm.sup.2 [0709] Second stage: 10
A/dm.sup.2 [0710] Third stage: 5 A/dm.sup.2
[0711] On the surface of each of the ultra-thin copper foils with
carrier, subjected to the formation of primary roughened particles
under the above-described conditions, a covering plating was
performed in a copper electrolyte bath composed of sulfuric acid
and copper sulfate, in order to prevent the dropout of the primary
roughened particles and improving the peel strength. The covering
plating conditions are described below.
[0712] (Electrolyte Composition) [0713] Cu: 40 to 50 g/L [0714]
H.sub.2SO.sub.4: 80 to 120 g/L
[0715] (Electrolyte Temperature) [0716] 43 to 47.degree. C.
[0717] (Current Condition) [0718] Current density: 41
A/dm.sup.2
[0719] Formation of Secondary Particles:
[0720] Next, a roughening treatment to form secondary roughened
particles on the primary roughened particles of each of the
ultra-thin copper foils with carrier was performed.
[0721] (Electrolyte Composition) [0722] Cu: 10 to 20 g/L [0723] Co:
1 to 10 g/L [0724] Ni: 1 to 10 g/L [0725] pH: 1 to 4
[0726] (Electrolyte Temperature) [0727] 40 to 50.degree. C.
[0728] (Current Condition) [0729] Current density: 25
A/dm.sup.2
[0730] (Immersion Time in Plating Solution after Completion of
Plating)
[0731] In order to obtain a predetermined hole shape, the immersion
time was set to be 5 to 10 seconds.
[0732] The surface of each of the ultra-thin copper foils with
carrier, subjected to the secondary particle roughening treatment
under the above-described conditions, were subjected to a covering
Co--Ni plating. The covering plating conditions are described
below.
[0733] (Electrolyte Composition) [0734] Co: 1 to 30 g/L [0735] Ni:
1 to 30 g/L [0736] pH: 1.0 to 3.5
[0737] (Electrolyte Temperature) [0738] 30 to 80.degree. C.
[0739] (Current Condition) [0740] Current density: 5.0
A/dm.sup.2
[0741] [Barrier (Heat Resistance) Treatment]
[0742] A barrier (heat resistance) treatment was performed under
the following conditions, to form a brass plating layer or a
zinc-nickel alloy plating layer.
[0743] Formation conditions of barrier layers (brass plating) of
Example A6, comparative Examples A2 and A3, Example B6, and
Comparative Examples B2 and B3:
[0744] By using a brass plating bath having a copper concentration
of 50 to 80 g/L, a zinc concentration of 2 to 10 g/L, a sodium
hydroxide concentration of 50 to 80 g/L, a sodium cyanate
concentration of 5 to 30 g/L, and being set at a temperature of 60
to 90.degree. C., a plating electric quantity of 30 As/dm.sup.2 was
imparted to the M surface having a roughening-treated layer formed
thereon, at a current density of 5 to 10 A/dm.sup.2 (multistage
treatment).
[0745] Formation conditions of barrier layers (zinc-nickel plating)
of Example A3, Comparative Example A1, Example B3 and Comparative
Example B1:
[0746] By using a plating bath containing, as added therein, Ni: 10
g/L to 30 g/L, Zn: 1 g/L to 15 g/L, sulfuric acid
(H.sub.2SO.sub.4): 1 g/L to 12 g/L, and chloride ion: 0 g/L to 5
g/L, a plating electric quantity of 5.5 As/dm.sup.2 was imparted to
the M surface having a roughening-treated layer formed thereon, at
a current density of 1.3 A/dm.sup.2.
[0747] [Rust-Preventing Treatment]
[0748] A rust-preventing treatment (chromate treatment) was
performed under the following conditions to form a rust-preventing
layer.
[0749] (Chromate conditions) In a chromate bath containing
CrO.sub.3: 2.5 g/L, Zn: 0.7 g/L, and Na.sub.2SO.sub.4: 10 g/L,
having a pH 4.8, and being set at 54.degree. C., an electric
quantity of 0.7 As/dm.sup.2 was added. Moreover, immediately after
the completion of the rust-preventing treatment in the chromate
bath, by using a liquid shower pipe, the whole roughening-treated
surface was subjected to a showering by using the same chromate
bath.
[0750] [Application of Silane Coupling Agent]
[0751] A silane coupling agent application treatment was performed
by spraying a solution containing 0.2 to 2% of an alkoxysilane and
having a pH of 7 to 8 to the roughening-treated surface of a copper
foil.
[0752] Moreover, in each of Examples A8 and B8, after the
rust-preventing treatment and the application of a silane coupling
agent, a resin layer was formed under the following conditions.
[0753] (Example of Resin Synthesis)
[0754] In a 2-liter three-necked flask equipped with a stainless
steel anchor-type stirring rod, a nitrogen introduction tube and a
reflux condenser equipped with a bulb condenser equipped on the top
of a trap with stopcock, 117.68 g (400 mmol) of
3,4,3',4'-biphenyltetracarboxylic acid dihydrate, 87.7 g (300 mmol)
of 1,3-bis(3-aminophenoxy)benzene, 4.0 g (40 mmol) of
.gamma.-valerolactone, 4.8 g (60 mmol) of pyridine, 300 g of
N-methyl-2-pyrrolidone (hereinafter denoted as NMP), and 20 g of
toluene were added, the resulting mixture was heated at 180.degree.
C. for 1 hour and then cooled to around room temperature,
subsequently 29.42 g (100 mmol) of
3,4,3',4'-biphenyltetracarboxylic acid dihydrate, 82.12 g (200
mmol) of 2,2-bis[4-(4-aminophenoxy)phenyl]propane, 200 g of NMP and
40 g of toluene were added to the mixture, the resulting mixture
was mixed at room temperature for 1 hour and then heated at
180.degree. C. for 3 hours, and thus a block copolymerized
polyimide having a solid content of 38%. This block copolymerized
polyimide had a ratio between the following general formulas (1)
and (2), the general formula (1): the general formula (2)=3:2, a
number average molecular weight of 70000, and a weight average
molecular weight of 150000.
##STR00004##
[0755] The block copolymerized polyimide solution obtained in the
synthesis example was further diluted with NMP into a block
copolymerized polyimide solution having a solid content of 10%. To
this block copolymerized polyimide solution,
bis(4-maleimidephenyl)methane (BMI-H, K I Chemical Industry Co.,
Ltd.) was added so as to have a solid content proportion of 35 in
relation to a solid content proportion of the block copolymerized
polyimide of 65 (specifically, the solid content weight of the
bis(4-maleimidephenyl)methane contained in the resin solution: the
solid content weight of the block copolymerized polyimide=35:65),
and the resulting solution was dissolved and mixed at 60.degree. C.
for 20 minutes to yield a resin solution. Subsequently, in each of
Example A8 and Example B8, to the surface of the ultra-thin copper
foil, the resin solution was applied by using a reverse roll
coating machine, dried in an nitrogen atmosphere, at 120.degree. C.
for 3 minutes and a 160.degree. C. for 3 minutes, and then finally
heat treated at 300.degree. C. for 2 minutes, and thus, a copper
foil provided with a resin layer was produced. The thickness of the
resin layer was set to be 2 .mu.m.
[0756] (Various Evaluations of Surface-Treated Copper Foil and
Copper Foil with Carrier)
[0757] The surface-treated copper foils and the copper foils with
carrier obtained as described above were subjected to various
evaluations on the basis of the following methods.
[0758] <Linear Roughness Rz>
[0759] For each of the surface-treated copper foils and the copper
foils with carrier of Examples and Comparative Examples, the
ten-point average roughness of the surface-treated surface was
measured according to JIS B0601-1994 by using the contact surface
roughness meter Surfcorder SE-3C manufactured by Kosaka Laboratory
Ltd. The values of three times measurements were determined by
performing the measurement three times under the conditions of a
measurement reference length of 0.8 mm, an evaluation length of 4
mm, a cut-off value of 0.25 mm, a feed speed of 0.1 mm/sec, while
in the case of a rolled copper foil, the measurement position is
being varied in the direction (TD) perpendicular to the rolling
direction, or in the case of an electrolytic copper foil, the
measurement position is being varied in the direction (TD)
perpendicular to the traveling direction of the electrolytic copper
foil in the production apparatus of the electrolytic copper
foil.
[0760] <Surface Roughness Sz>
[0761] The surface roughness (the maximum height of the surface) Sz
of the surface on the surface-treated layer side of each of the
surface-treated copper foils and the copper foils with carrier was
measured according to ISO25178, by using a laser microscope
(testing apparatus: OLYMPUS LEXT OLS 4000, resolution: XY-0.12
.mu.m, Z-0.0 .mu.m, cut-off: none) manufactured by Olympus Corp.
The measurement area of the observation section was set to be 66524
.mu.m.sup.2.
[0762] <Area Ratio (B/A)>
[0763] For each of the surface-treated copper foils and the copper
foils with carrier of Examples and Comparative Examples, the area
of the surface on the surface-treated layer side was measured by a
measurement method based on a laser microscope. For each of the
copper foils, after the surface treatment, of Examples and
Comparative Examples, by using a laser microscope (testing
apparatus: OLYMPUS LEXT OLS 4000, resolution: XY-0.12 .mu.m, Z-0.0
.mu.m, cut-off: none) manufactured by Olympus Corp., the
three-dimensional area B in an area A (the surface area obtained in
plan view) corresponding to 256 .mu.m.times.256 .mu.m (in the
actual data, 66524 .mu.m.sup.2) was measured, and the area ratio
was calculated by a technique adopting the relation, the
three-dimensional area B divided by the two-dimensional area A=the
area ratio (B/A). The measurement environment temperature for the
three-dimensional area B with the laser microscope was set at 23 to
25.degree. C.
[0764] For each of the surface-treated copper foils and the copper
foils with carrier of Examples and Comparative Examples, a 20-cm
square size of the following resin substrate was prepared, and the
resin substrate were laminated and pressed to each other in such a
way that the surface of the copper foil, having the surface-treated
layer was brought into contact with the resin substrate. The
recommended conditions of the substrate maker were adopted for the
temperature, the pressure and the time in the lamination press.
[0765] Resin used: GHPL-830MBT of Mitsubishi Gas Chemical Company,
Inc.
[0766] Next, the surface-treated copper foil on the resin substrate
was removed by entire-surface etching under the following etching
conditions. For the copper foil with carrier on the resin
substrate, after peeling the carrier, the ultra-thin copper layer
was removed by entire-surface etching under the following etching
conditions. The "entire-surface etching" as referred to herein
means an etching performed until the full thickness of the copper
foil is removed, and the resin is exposed all over the surface.
[0767] (Etching conditions) Etching solutions: cupric chloride
solution, HCl concentration: 3.5 mol/L, temperature: 50.degree. C.,
CuCl.sub.2 concentration: regulated so as to give a specific
gravity of 1.26.
[0768] 2. Formation of Surface Profile of Resin Substrate Using
Chemical Solution
[0769] As Comparative Example B5, two 100-.mu.m-thick sheets of the
resin substrate GHPL-830MBT manufactured by Mitsubishi Gas Chemical
Company, Inc. were prepared. The two sheets of the substrate were
superposed on each other, and a release layer film was bonded to
each side of the set of the two sheets, and the set of the two
sheets was subjected to lamination pressing. The recommended
conditions of the substrate maker were adopted for the temperature,
the pressure and the time in the lamination press. After completion
of lamination pressing, the release layer films were removed from
the resin substrates, and desmear treatments A and B and a
neutralization treatment were performed under the following
immersion treatment conditions, to form the surface profile of the
resin substrate.
[0770] (Desmear Treatment Conditions A) [0771] Desmear treatment
solution: 40 g/L KMnO.sub.4, 20 g/L NaOH [0772] Treatment
temperature: Room temperature [0773] Immersion time: 20 minutes
[0774] Number of rotations of stirrer: 300 rpm
[0775] (Desmear Treatment Conditions B)
[0776] Desmear treatment solution: 90 g/L KMnO.sub.4, 5 g/L HCl
[0777] Treatment temperature: 49.degree. C. [0778] Immersion time:
20 minutes [0779] Number of rotations of stirrer: 300 rpm
[0780] (Neutralization Treatment Conditions) [0781] Neutralization
treatment solution: L-Ascorbic acid 80 g/L [0782] Treatment
temperature: Room temperature [0783] Immersion time: 3 minutes
[0784] No stirring
[0785] As Comparative Example B6, two 100-.mu.m-thick sheets of the
resin substrate GHPL-830MBT manufactured by Mitsubishi Gas Chemical
Company, Inc. were prepared. The two sheets of the substrate were
superposed on each other, and a release layer film was bonded to
each side of the set of the two sheets, and the set of the two
sheets was subjected to lamination pressing. The recommended
conditions of the substrate maker were adopted for the temperature,
the pressure and the time in the lamination press. After completion
of lamination pressing, the release layer films were removed from
the resin substrates, and desmear treatments A and B and a
neutralization treatment were performed under the following
immersion treatment conditions, to form the surface profile of the
resin substrate.
(Desmear Treatment Conditions A)
[0786] Desmear treatment solution: 40 g/L KMnO.sub.4, 20 g/L NaOH
[0787] Treatment temperature: Room temperature [0788] Immersion
time: 20 minutes [0789] Number of rotations of stirrer: 300 rpm
(Desmear Treatment Conditions B)
[0789] [0790] Desmear treatment solution: 90 g/L KMnO.sub.4, 5 g/L
HCl [0791] Treatment temperature: 49.degree. C. [0792] Immersion
time: 30 minutes [0793] Number of rotations of stirrer: 300 rpm
(Neutralization Treatment Conditions)
[0793] [0794] Neutralization treatment solution: L-Ascorbic acid 80
g/l [0795] Treatment temperature: Room temperature [0796] Immersion
time: 3 minutes [0797] No stirring
[0798] As Comparative Example B9, two 100-.mu.m-thick sheets of the
resin substrate GHPL-830MBT manufactured by Mitsubishi Gas Chemical
Company, Inc. were prepared. The two sheets of the substrate were
superposed on each other, and a release layer film was bonded to
each side of the set of the two sheets, and the set of the two
sheets was subjected to lamination pressing. The recommended
conditions of the substrate maker were adopted for the temperature,
the pressure and the time in the lamination press. After completion
of lamination pressing, the release layer films were removed from
the resin substrates, and on the surfaces of the resin substrate,
shower treatments A and B and a neutralization treatment were
performed under the following treatment conditions, to form the
surface profile of the resin substrate.
(Shower Treatment Conditions A)
[0799] Desmear treatment solution: 40 g/L KMnO.sub.4, 20 g/L NaOH
[0800] Treatment temperature: Room temperature [0801] Treatment
time: 20 minutes [0802] Shower pressure: 0.2 MPa
(Shower Conditions B)
[0802] [0803] Desmear treatment solution: 90 g/L KMnO.sub.4, 5 g/L
HCl [0804] Treatment temperature: 49.degree. C. [0805] Treatment
time: 20 minutes [0806] Shower pressure: 0.2 MPa
(Neutralization Conditions)
[0806] [0807] Neutralization treatment solution: L-Ascorbic acid 80
g/L [0808] Treatment temperature: Room temperature [0809] Immersion
time: 3 minutes [0810] No stirring
[0811] Thus, the formation of the surface profiles of the resin
substrates using chemical solutions was performed.
[0812] (Evaluations of Resin Substrates)
[0813] The resin substrates of Examples and Comparative Examples
having the surface profiles produced above were subjected to the
following evaluations.
[0814] <Linear Roughness Rz>
[0815] For each of the etched side surfaces of the resin substrates
of Examples and Comparative Examples, the ten-point average
roughness was measured according to JIS B0601-1994 by using the
contact surface roughness meter Surfcorder SE-3C manufactured by
Kosaka Laboratory Ltd. The values of three times measurements were
determined by performing the measurement three times under the
conditions of a measurement reference length of 0.8 mm, an
evaluation length of 4 mm, a cut-off value of 0.25 mm, a feed speed
of 0.1 mm/sec.
[0816] <Surface Roughness Sz>
[0817] For each of the etched side surfaces of the resin substrates
of Examples and Comparative Examples, by using a laser microscope
(testing apparatus: OLYMPUS LEXT OLS 4000, resolution: XY-0.12
.mu.m, Z-0.0 .mu.m, cut-off: none) manufactured by Olympus Corp.,
the surface roughness (the maximum height of the surface) Sz was
measured according to ISO25178. The measurement area of the
observation section was set to be 66524 .mu.m.sup.2.
[0818] <Area Ratio (B/A)>
[0819] For each of the etched side surfaces of the resin substrates
of Examples and Comparative Examples, by using a laser microscope
(testing apparatus: OLYMPUS LEXT OLS 4000, resolution: XY-0.12
.mu.m, Z-0.0 .mu.m, cut-off: none) manufactured by Olympus Corp.,
the three-dimensional area B in an area A (the surface area
obtained in plan view) corresponding to 256 .mu.m.times.256 .mu.m
(in the actual data, 66524 .mu.m.sup.2) was measured, and the area
ratio was calculated by a technique adopting the relation, the
three-dimensional area B divided by the two-dimensional area A=the
area ratio (B/A). The measurement environment temperature for the
three-dimensional area B with the laser microscope was set at 23 to
25.degree. C.
[0820] <Black Area Rate>
[0821] For each of the etched side surfaces of the resin substrates
of Examples and Comparative Examples, by using a scanning electron
microscope (SEM), photography was performed with an acceleration
voltage set at 15 kV. During photography, contrast and brightness
were regulated so as for the contours of the holes in the whole
observation field to be clearly seen. Photography was performed in
the state in which the contours of the holes were able to be
observed, but not in the state in which the entire photograph was
white or black. When photography is performed in a state in which
the contours of the holes can be observed, but not in the state in
which the entire photograph is white or black, the black area rates
(%) of the photographs concerned give nearly the same values. A
black-white image processing was applied to the taken photographs
(SEM images (magnification of 30 k (30000)), by using Photo Shop
7.0 software, and thus, the black area rates (%) were determined.
The black area rate (%) was determined as the rate of the black
area in relation to the observation area (the sum of the white area
and the black area) at the threshold value of 128 set by selecting
"Histogram" of "Image" found in Photo Shop 7.0.
[0822] <Average Value of Diameters of Holes>
[0823] For each of the etched side surfaces of the resin substrates
of Examples and Comparative Examples, from the SEM image
(.times.6000 to .times.30000), by the segment method, the diameters
of the holes were measured longitudinally, transversely and
obliquely, and the average value of N=3 of these values was
calculated.
[0824] <Peel Strength>
[0825] The etched surface of each of the resin substrates
(entire-surface etched substrates) was provided with a catalyst for
depositing electroless copper, and was subjected to an electroless
copper plating under the following conditions by using the KAP-8
bath manufactured by Kanto Kasei Co., Ltd. The thickness of the
obtained electroless copper plating was 0.5 .mu.m.
[0826] CuSO.sub.4 concentration: 0.06 mol/L, HCHO concentration:
0.5 mol/L, EDTA concentration: 0.12 mol/L, pH 12.5, additive:
2,2'-bipyridyl, additive concentration: 10 mg/L, surfactant:
REG-1000, surfactant concentration: 500 mg/L
[0827] Next, on the electroless copper plating, further
electrolytic plating was performed by using the following
electrolyte. The copper thickness (total thickness of electroless
plating and electrolytic plating) was 12 .mu.m.
[0828] Simple copper sulfate electrolyte: Cu concentration: 100
g/L, H.sub.2SO.sub.4 concentration: 80 g/L
[0829] A 10-mm-wide copper circuit was formed by wet etching on the
laminate with copper plating formed as described above by
subjecting the resin substrate (entire-surface etched substrate) to
electroless copper plating and electrolytic copper plating so as to
have a copper layer thickness of 12 .mu.m. According to JIS-C-6481,
the strength in the case of peeling this copper circuit at an angle
of 90 degrees was measured to be taken as the peel strength.
[0830] <Fine Wiring Formability>
[0831] On the laminate with copper plating formed as described
above by subjecting the resin substrate (entire-surface etched
substrate) to electroless copper plating and electrolytic copper
plating so as to have a copper layer thickness of 12 .mu.m,
circuits having L(line)/S(space)=15 .mu.m/15 .mu.m and 10 .mu.m/10
.mu.m, respectively, were formed by processing the plating copper
by etching. In this case, the fine wirings formed on the resin
substrate was visually observed, and the case where the detachment
of the circuit, the shortening between the circuits (abnormal
deposition of copper between circuits) and the deficit of the
circuit were not found was marked as acceptable (circle).
[0832] Tables 1 and 4 show the production conditions of the
above-described copper foils used to obtain the surface profiles of
the substrates by transferring the profiles of the surfaces of the
copper foils to the surfaces of the substrates, in Examples A1 to
A11, Comparative Examples A1 to A4, Examples B1 to B12, and
Comparative Examples B1 to B4.
[0833] Tables 2 and 5 show the above-described evaluation results
of the surface profiles of the substrates.
[0834] Tables 3 and 6 show the above-described evaluation results
of the surface profiles of the copper foils giving the surface
profiles of the substrates.
TABLE-US-00001 TABLE 1 Surface treatment Raw foil Rust- Application
of (corresponding to copper Treated side Roughening Barrier
preventing silane coupling Sample foil bulk layer) surface
treatment treatment treatment agent Example A1 Ultra-thin raw foil
with Ultra-thin Fine Not applied Applied Applied carrier copper
roughening (3) surface Example A2 Ultra-thin raw foil with
Ultra-thin Fine Not applied Applied Applied carrier copper
roughening (4) surface Example A3 Ultra-thin raw foil with
Ultra-thin Fine Zn.cndot.Ni Applied Applied carrier copper
roughening (1) surface Example A4 Ultra-thin raw foil with
Ultra-thin Fine Not applied Applied Applied carrier copper
roughening (2) surface Example A5 Double flat sided M surface Fine
Not applied Applied Applied electrolytic raw copper foil (high
gloss roughening (3) surface) Example A6 Double flat sided M
surface Fine Brass Applied Applied electrolytic raw copper foil
(high gloss roughening (1) surface) Example A7 Common electrolytic
raw S surface Not applied Not applied Applied Applied foil Example
A8 Ultra-thin raw foil with Ultra-thin Fine Not applied Applied
Applied carrier (with resin) copper roughening (4) surface Example
A9 Ultra-thin raw foil with Ultra-thin Fine Not applied Applied
Applied carrier copper roughening (5) surface Example Ultra-thin
raw foil with Ultra-thin Fine Not applied Applied Applied A10
carrier copper roughening (6) surface Example Ultra-thin raw foil
with Ultra-thin Fine Not applied Applied Applied A11 carrier copper
roughening (7) surface Comparative Common electrolytic raw M
surface Fine Zn.cndot.Ni Applied Applied Example A1 foil roughening
(1) Comparative Common electrolytic raw M surface Spherical Brass
Applied Applied Example A2 foil roughening (ordinary) Comparative
Common electrolytic raw S surface Spherical Brass Applied Applied
Example A3 foil roughening (ordinary) Comparative Ultra-thin raw
foil with Ultra-thin Not applied Not applied Applied Applied
Example A4 carrier copper surface
TABLE-US-00002 TABLE 2 Contact surface roughness meter Laser
roughness meter Average Linear Surface Observation Black value of
Fine wiring Thickness of roughness roughness section Measured
Surface area diameters formability copper foil Rz Sz surface area
surface area area ratio rate of holes Peel strength L/S = L/S =
(.mu.m) (.mu.m) (.mu.m) A (.mu.m2) B (.mu.m2) B/A (%) (.mu.m)
(kg/cm) Evaluation 15/15 10/10 Example A1 3 0.8 1.65 66524 67490
1.0145 19 0.09 0.64 .largecircle. .largecircle. .largecircle.
Example A2 3 1.1 2.24 66524 74186 1.1152 28 0.39 0.72 .largecircle.
.largecircle. .largecircle. Example A3 3 1.1 2.65 66524 78503
1.1801 38 0.18 0.78 .largecircle. .largecircle. .largecircle.
Example A4 3 1.6 3.39 66524 83369 1.2532 50 0.76 0.53 .largecircle.
.largecircle. X Example A5 12 1.2 1.83 66524 68101 1.0237 31 0.11
0.68 .largecircle. .largecircle. .largecircle. Example A6 12 1.0
2.95 66524 85124 1.2796 34 0.56 0.80 .largecircle. .largecircle.
.largecircle. Example A7 12 1.6 2.05 66524 68258 1.0261 25 0.03
0.50 .largecircle. .largecircle. .largecircle. Example A8 3 (with
1.1 2.32 66524 73698 1.1078 27 0.38 0.95 .largecircle.
.largecircle. .largecircle. resin) Example A9 1.5 0.8 0.97 66524
71846 1.0800 9 0.20 0.52 .largecircle. .largecircle. .largecircle.
Example A10 2 1.6 5.12 66524 100518 1.5110 49 0.89 0.81
.largecircle. .largecircle. X Example A11 5 0.8 1.05 66524 67123
1.0090 9 0.35 0.52 .largecircle. .largecircle. .largecircle.
Comparative 12 2.5 7.03 66524 117312 1.7635 54 3.40 0.83
.largecircle. X X Example A1 Comparative 12 2.4 8.53 66524 128211
1.9273 62 2.13 0.80 .largecircle. X X Example A2 Comparative 12 1.6
5.25 66524 101589 1.5271 58 1.82 0.40 X .largecircle. .largecircle.
Example A3 Comparative 3 0.3 0.78 66524 66590 1.0010 0 0.00 0.25 X
.largecircle. .largecircle. Example A4
TABLE-US-00003 TABLE 3 Contact surface Laser roughness meter
roughness meter Surface Observation Thickness of Linear roughness
roughness section surface Measured Surface area copper foil Rz Sz
area surface area ratio (.mu.m) (.mu.m) (.mu.m) A (.mu.m2) B
(.mu.m2) B/A Example A1 3 0.8 2.51 66524 77819 1.1698 Example A2 3
1.0 3.23 66524 79589 1.1964 Example A3 3 1.0 3.59 66524 82498
1.2401 Example A4 3 1.6 3.40 66524 87160 1.3102 Example A5 12 0.6
2.28 66524 75913 1.1411 Example A6 12 1.5 4.82 66524 110975 1.6682
Example A7 12 1.6 2.76 66524 72121 1.0841 Example A8 3 (with resin)
1.0 3.18 66524 78966 1.1870 Example A9 1.5 0.7 1.92 66524 74706
1.1230 Example A10 2 1.7 6.72 66524 107769 1.6200 Example A11 5 0.7
2.80 66524 68613 1.0314 Comparative 12 2.5 7.95 66524 144589 2.1735
Example A1 Comparative 12 3.6 9.79 66524 157818 2.3723 Example A2
Comparative 12 2.0 6.24 66524 134521 2.0221 Example A3 Comparative
3 0.8 1.20 66524 66925 1.0060 Example A4
TABLE-US-00004 TABLE 4 Surface treatment Raw foil Rust- Application
of (corresponding to copper Treated side Roughening Barrier
preventing silane coupling Sample foil bulk layer) surface
treatment treatment treatment agent Example B1 Ultra-thin raw foil
with Ultra-thin copper Fine roughening Not applied Applied Applied
carrier surface (3) Example B2 Ultra-thin raw foil with Ultra-thin
copper Fine roughening Not applied Applied Applied carrier surface
(4) Example B3 Ultra-thin raw foil with Ultra-thin copper Fine
roughening Zn.cndot.Ni Applied Applied carrier surface (1) Example
B4 Ultra-thin raw foil with Ultra-thin copper Fine roughening Not
applied Applied Applied carrier surface (2) Example B5 Double flat
sided M surface (high Fine roughening Not applied Applied Applied
electrolytic raw copper gloss surface) (3) foil Example B6 Double
flat sided M surface (high Fine roughening Brass Applied Applied
electrolytic raw copper gloss surface) (1) foil Example B7 Common
electrolytic S surface Not applied Not applied Applied Applied raw
foil Example B8 Ultra-thin raw foil with Ultra-thin copper Fine
roughening Not applied Applied Applied carrier (with resin) surface
(4) Example B10 Ultra-thin raw foil with Ultra-thin copper Fine
roughening Not applied Applied Applied carrier surface (5) Example
B11 Ultra-thin raw foil with Ultra-thin copper Fine roughening Not
applied Applied Applied carrier surface (6) Example B12 Ultra-thin
raw foil with Ultra-thin copper Fine roughening Not applied Applied
Applied carrier surface (7) Comparative Common electrolytic M
surface Fine roughening Zn.cndot.Ni Applied Applied Example B1 raw
foil (1) Comparative Common electrolytic M surface Spherical Brass
Applied Applied Example B2 raw foil roughening (ordinary)
Comparative Common electrolytic S surface Spherical Brass Applied
Applied Example B3 raw foil roughening (ordinary) Comparative
Ultra-thin raw foil with Ultra-thin copper Not applied Not applied
Not applied Applied Example B4 carrier surface
TABLE-US-00005 TABLE 5 Contact surface roughness meter Laser
roughness meter Average Linear Surface Observation Black value of
Fine wiring Thickness of roughness roughness section surface
Measured Surface area diameters formability copper foil Rz Sz area
surface area area ratio rate of holes Peel strength L/S = L/S =
(.mu.m) (.mu.m) (.mu.m) A (.mu.m.sup.2) B (.mu.m.sup.2) B/A (%)
(.mu.m) (kg/cm) Evaluation 15/15 10/10 Example B1 3 0.8 1.65 66524
67490 1.0145 19 0.09 0.64 .largecircle. .largecircle. .largecircle.
Example B2 3 1.1 2.24 66524 74186 1.1152 28 0.39 0.72 .largecircle.
.largecircle. .largecircle. Example B3 3 1.1 2.65 66524 78503
1.1801 38 0.18 0.78 .largecircle. .largecircle. .largecircle.
Example B4 3 1.6 3.39 66524 83369 1.2532 50 0.76 0.53 .largecircle.
.largecircle. X Example B5 12 1.2 1.83 66524 68101 1.0237 31 0.11
0.68 .largecircle. .largecircle. .largecircle. Example B6 12 1.0
2.95 66524 85124 1.2796 34 0.56 0.80 .largecircle. .largecircle.
.largecircle. Example B7 12 1.6 2.05 66524 68258 1.0261 25 0.03
0.50 .largecircle. .largecircle. .largecircle. Example B8 3 (with
1.1 2.32 66524 73698 1.1078 27 0.38 0.95 .largecircle.
.largecircle. .largecircle. resin) Example B9 (No use of 0.8 1.56
66524 67825 1.0196 20 0.07 0.58 .largecircle. .largecircle.
.largecircle. copper foil) Example 1.5 0.8 0.97 66524 71846 1.0800
9 0.20 0.52 .largecircle. .largecircle. .largecircle. B10 Example 2
1.6 5.12 66524 100518 1.5110 49 0.89 0.81 .largecircle.
.largecircle. X B11 Example 5 0.8 1.05 66524 67123 1.0090 9 0.35
0.52 .largecircle. .largecircle. .largecircle. B12 Comparative 12
2.5 7.03 66524 117312 1.7635 54 3.40 0.83 .largecircle. X X Example
B1 Comparative 12 2.4 8.53 66524 128211 1.9273 62 2.13 0.80
.largecircle. X X Example B2 Comparative 12 1.6 5.25 66524 101589
1.5271 58 1.82 0.40 X .largecircle. .largecircle. Example B3
Comparative 3 0.3 0.78 66524 66590 1.0010 0 0.00 0.25 X
.largecircle. .largecircle. Example B4 Comparative (No use of 0.8
0.96 66524 66829 1.0046 8 0.005 0.42 X .largecircle. .largecircle.
Example B5 copper foil) Comparative (No use of 0.8 0.91 66524 66721
1.0030 10 0.003 0.40 X .largecircle. .largecircle. Example B6
copper foil)
TABLE-US-00006 TABLE 6 Contact surface Laser roughness meter
roughness meter Surface Observation Measured Thickness of Linear
roughness section surface surface Surface copper foil roughness Rz
Sz area area area ratio (.mu.m) (.mu.m) (.mu.m) A (.mu.m.sup.2) B
(.mu.m.sup.2) B/A Example B1 3 0.8 2.51 66524 77819 1.1698 Example
B2 3 1.0 3.23 66524 79589 1.1964 Example B3 3 1.0 3.59 66524 82498
1.2401 Example B4 3 1.6 3.40 66524 87160 1.3102 Example B5 12 0.6
2.28 66524 75913 1.1411 Example B6 12 1.5 4.82 66524 110975 1.6682
Example B7 12 1.6 2.76 66524 72121 1.0841 Example B8 3 (with resin)
1.0 3.18 66524 78966 1.1870 Example B10 1.5 0.7 1.92 66524 74706
1.1230 Example B11 2 1.7 6.72 66524 107769 1.6200 Example B12 5 0.7
2.24 66524 68613 1.0314 Comparative 12 2.5 7.95 66524 144589 2.1735
Example B1 Comparative 12 3.6 9.79 66524 157818 2.3723 Example B2
Comparative 12 2.0 6.24 66524 134521 2.0221 Example B3 Comparative
3 0.8 1.20 66524 66925 1.0060 Example B4 Note: The data of the
roughness and the surface area ratio of the copper foil of Example
B8 are the data of the copper foil before application of the
resin.
[0835] (Evaluation Results)
[0836] Each of Examples A1 to A11 had a satisfactory fine wiring
formability, and moreover, exhibited a satisfactory peel
strength.
[0837] Each of the copper foils of Comparative Examples A1 to A4
had the surface roughness Sz of the surface of the surface-treated
layer falling outside the range from 2 to 6 .mu.m, and accordingly
had the surface roughness Sz in the surface profile of the
substrate falling outside the range from 1 to 5 .mu.m to result in
a poor fine wiring formability or a poor peel strength. Each of the
copper foils of Comparative Examples A1 to A4 had the ratio B/A of
the three-dimensional surface area B to the two-dimensional surface
area A of the surface of the surface-treated layer falling outside
the range from 1.05 to 1.8, and accordingly the ratio B/A concerned
in the surface profile of the substrate fell outside the range from
1.01 to 1.5 to result in a poor fine wiring formability or a poor
peel strength. Each of the surface profiles of the substrates of
Comparative Examples A1 to A4 had a black area rate of the surface
falling outside the range from 10 to 50%, and an average value of
the diameters of the holes of the surface falling outside the range
from 0.03 to 1.0 .mu.m, to result in a poor fine wiring formability
or a poor peel strength.
[0838] From the evaluation results of Examples and Comparative
Examples, it has been verified that the numerical values of Rz of
the surface of the copper foil and the surface of the substrate are
not particularly related to the combination of a satisfactory fine
wiring formability and a satisfactory peel strength.
[0839] Each of the substrates of Examples B1 to B12 had a
satisfactory fine wiring formability, and moreover exhibited a
satisfactory peel strength.
[0840] Each of the substrates of Comparative Examples B1 to B6 had
a surface roughness Sz of the surface falling outside the range
from 1 to 5 .mu.m, to result in a poor fine wiring formability or a
poor peel strength. Each of the substrates of Comparative Examples
B1 to B4 had the ratio B/A of the three-dimensional surface area B
to the two-dimensional surface area A of the surface ratio B/A of
the three-dimensional surface area B to the two-dimensional surface
area A of the surface falling outside the range from 1.01 to 1.5,
to result in a poor fine wiring formability or a poor peel
strength. Each of the substrates of Comparative Examples B1 to B6
had both or either of a black area rate of the surface falling
outside the range from 10 to 50% and the average value of the
diameters of the holes of the surface falling outside the range
from 0.03 to 1.0 .mu.m, to result in a poor fine wiring formability
or a poor peel strength.
[0841] From the evaluation results of Examples and Comparative
Examples, it has been verified that the numerical value of Rz of
the surface of the substrate is not particularly related to the
combination of a satisfactory fine wiring formability and a
satisfactory peel strength.
[0842] FIGS. 3A, 3B, 3C, 3D and 3E how the SEM images
(.times.30000) of the copper foil-treated surfaces of Examples A1,
A2, A3, A5 and A6, respectively.
[0843] FIGS. 4A and 4B show the SEM images (.times.6000) of the
copper foil-treated surfaces of Comparative Examples A1 and A2.
[0844] FIGS. 5(A), 5(B), 5(C), 5(D) and 5(E) show the SEM images
(.times.30000) of the surfaces of the resin substrates of Examples
A1(B1), A2(B2), A3(B3), A5(B5) and A6(B6), respectively.
[0845] FIGS. 6(A) and 6(B) show the SEM images (.times.6000) of the
surfaces of the resin substrates of Comparative Examples A1(B1) and
A2(B2), respectively.
* * * * *