U.S. patent application number 14/962504 was filed with the patent office on 2016-06-23 for modification method, method for manufacturing resin article having plating layer, and resin article having plating layer.
The applicant listed for this patent is CANON COMPONENTS, INC.. Invention is credited to Taisuke IWASHITA.
Application Number | 20160177452 14/962504 |
Document ID | / |
Family ID | 55269212 |
Filed Date | 2016-06-23 |
United States Patent
Application |
20160177452 |
Kind Code |
A1 |
IWASHITA; Taisuke |
June 23, 2016 |
MODIFICATION METHOD, METHOD FOR MANUFACTURING RESIN ARTICLE HAVING
PLATING LAYER, AND RESIN ARTICLE HAVING PLATING LAYER
Abstract
There is provided with a modification method. Ultraviolet rays
are irradiated on part of a surface of a resin article, so as to
selectively modify the part of the surface of the resin article
such that an electroless plating layer will be deposited. The
ultraviolet rays are irradiated such that an interference pattern
by the ultraviolet rays is formed on the surface of the resin
article.
Inventors: |
IWASHITA; Taisuke;
(Saitama-ken, JP) |
|
Applicant: |
Name |
City |
State |
Country |
Type |
CANON COMPONENTS, INC. |
Saitama-ken |
|
JP |
|
|
Family ID: |
55269212 |
Appl. No.: |
14/962504 |
Filed: |
December 8, 2015 |
Current U.S.
Class: |
428/201 ;
427/595; 427/596 |
Current CPC
Class: |
C23C 18/48 20130101;
C23C 18/30 20130101; C23C 18/2086 20130101; C23C 18/1612 20130101;
C23C 18/204 20130101; C23C 18/1608 20130101; C23C 18/1641
20130101 |
International
Class: |
C23C 18/16 20060101
C23C018/16 |
Foreign Application Data
Date |
Code |
Application Number |
Dec 17, 2014 |
JP |
2014-255413 |
Claims
1. A modification method comprising: irradiating ultraviolet rays
on part of a surface of a resin article, so as to selectively
modify the part of the surface of the resin article such that an
electroless plating layer will be deposited, wherein the
ultraviolet rays are irradiated such that an interference pattern
by the ultraviolet rays is formed on the surface of the resin
article.
2. The modification method according to claim 1, wherein in the
irradiating, the ultraviolet rays are irradiated on the part of the
surface of the resin article through a shielding member having a
UV-transmissive portion, and the interference pattern is formed by
ultraviolet rays which come through the UV-transmissive
portion.
3. A modification method comprising: irradiating ultraviolet rays
on part of a surface of a resin article through a shielding member
having a UV-transmissive portion so as to selectively modify the
part of the surface of the resin article such that an electroless
plating layer is deposited, wherein the shielding member condenses
ultraviolet rays which go through the shielding member.
4. The modification method according to claim 2, wherein the
UV-transmissive portion is a slit.
5. The modification method according to claim 4, wherein the width
of the slit is larger than the width of the part of the surface of
the resin article to be modified such that an electroless plating
layer is deposited.
6. The modification method according to claim 4, wherein an region
on the surface of the resin article irradiated by ultraviolet rays
which come through the slit has a striped pattern.
7. The modification method according to claim 2, wherein the
UV-transmissive portion is a diffraction grating.
8. The modification method according to claim 2, wherein the
ultraviolet rays are irradiated on the surface of the resin article
by scanning the surface of the resin article with ultraviolet rays
having a linear irradiation area through the shielding member.
9. The modification method according to claim 1, wherein
irradiation of the ultraviolet rays is performed in an atmosphere
that contains at least one of oxygen or ozone.
10. The modification method according to claim 1, wherein the
ultraviolet rays are an ultraviolet ray laser beam having a
wavelength of 243 nm or less.
11. The modification method according to claim 10, wherein in the
irradiating, after irradiating the ultraviolet ray laser beam, a
further modifying treatment is performed on a region encompassing
the part of the surface of the resin article.
12. The modification method according to claim 11, wherein the
further modifying treatment is to irradiate ultraviolet rays having
a wavelength of 243 nm or less on a region encompassing the part of
the surface of the resin article using an ultraviolet ray lamp or
an ultraviolet ray LED, in an atmosphere that contains at least one
of oxygen or ozone.
13. The modification method according to claim 1, wherein the
surface of the resin article includes at least one of polyolefin,
polyester, polyvinyl, polycarbonate, or polyimide.
14. A method for manufacturing a resin article having a plating
layer, the method comprising: selectively modifying part of a
surface of a resin article by irradiating ultraviolet rays on the
part of the surface of the resin article, the ultraviolet rays
being irradiated such that an interference pattern by the
ultraviolet rays is formed on the surface of the resin article; and
forming a plating layer on the part of the surface of the resin
article by electroless plating.
15. A resin article having a plating layer that was manufactured
according to a method comprising: selectively modifying part of a
surface of a resin article by irradiating ultraviolet rays on the
part of the surface of the resin article, the ultraviolet rays
being irradiated such that an interference pattern by the
ultraviolet rays is formed on the surface of the resin article; and
forming a plating layer on the part of the surface of the resin
article by electroless plating.
Description
BACKGROUND OF THE INVENTION
[0001] 1. Field of the Invention
[0002] The present invention relates to a modification method, a
method for manufacturing resin article having a plating layer, and
a resin article having a plating layer.
[0003] 2. Description of the Related Art
[0004] A resin article having a plating layer that has a
predetermined pattern formed on the resin article is useful as a
circuit board or a conductive film or the like. Also, the uses of a
resin article having a plating layer are not limited to these; for
example, a resin article having a plating layer of zinc oxide or
the like can be used as a functional film such as a UV-cutting
material or a photocatalyst.
[0005] Consequently, methods for providing a plating layer having a
predetermined pattern on a resin article have been investigated.
For example, Japanese Patent Laid-Open No. 2008-094923 describes a
method for manufacturing a printed circuit board using surface
modification by ultraviolet rays. Specifically, first, an
ultraviolet ray lamp is irradiated on an entire surface of a
cyclo-olefin polymer material, to perform surface modification
necessary for electroless plating. Then, a plating layer is formed
by performing electroless plating on the entire modified surface of
the cyclo-olefin polymer material, and the result is used as
material of a printed circuit board. By using a photolithography
step and an etching step to process the obtained plating layer so
as to have a predetermined pattern, it is possible to provide a
plating layer having a predetermined pattern on the cyclo-olefin
polymer material.
[0006] Technology is also known in which conductive line having a
predetermined pattern is formed by irradiating ultraviolet rays
according to a predetermined pattern on a resin article. For
example, Japanese Patent Laid-Open No. 7-192790 describes
irradiating ultraviolet rays on a conductive polymer through a mask
that has an ultraviolet ray shielding portion according to a
predetermined pattern. The conductive polymer degenerates and
becomes insulated in portions where the ultraviolet rays have been
irradiated, and portions where the ultraviolet rays were not
irradiated due to being shielded by the ultraviolet ray shielding
portion function as conductive line.
SUMMARY OF THE INVENTION
[0007] According to an embodiment of the present invention, a
modification method comprises: irradiating ultraviolet rays on part
of a surface of a resin article, so as to selectively modify the
part of the surface of the resin article such that an electroless
plating layer will be deposited, wherein the ultraviolet rays are
irradiated such that an interference pattern by the ultraviolet
rays is formed on the surface of the resin article.
[0008] According to another embodiment of the present invention, a
modification method comprises: irradiating ultraviolet rays on part
of a surface of a resin article through a shielding member having a
UV-transmissive portion so as to selectively modify the part of the
surface of the resin article such that an electroless plating layer
is deposited, wherein the shielding member condenses ultraviolet
rays which go through the shielding member.
[0009] According to still another embodiment of the present
invention, a method for manufacturing a resin article having a
plating layer comprises: selectively modifying part of a surface of
a resin article by irradiating ultraviolet rays on the part of the
surface of the resin article, the ultraviolet rays being irradiated
such that an interference pattern by the ultraviolet rays is formed
on the surface of the resin article; and forming a plating layer on
the part of the surface of the resin article by electroless
plating.
[0010] According to yet another embodiment of the present
invention, a resin article having a plating layer is manufactured
according to a method comprising: selectively modifying part of a
surface of a resin article by irradiating ultraviolet rays on the
part of the surface of the resin article, the ultraviolet rays
being irradiated such that an interference pattern by the
ultraviolet rays is formed on the surface of the resin article; and
forming a plating layer on the part of the surface of the resin
article by electroless plating.
[0011] Further features of the present invention will become
apparent from the following description of exemplary embodiments
(with reference to the attached drawings).
BRIEF DESCRIPTION OF THE DRAWINGS
[0012] FIG. 1 shows a method for irradiating ultraviolet rays
according to one embodiment.
[0013] FIG. 2 is a flowchart of treatment according to one
embodiment.
[0014] FIG. 3 shows ultraviolet ray irradiation through a single
slit.
[0015] FIG. 4 shows ultraviolet ray irradiation through two
slits.
[0016] FIG. 5 shows ultraviolet ray irradiation through a
diffraction grating.
[0017] FIGS. 6A to 6C illustrate a method for manufacturing a resin
article having a plating layer according to one embodiment.
[0018] FIG. 7 shows a resin article having a plating layer obtained
in Example 1.
DESCRIPTION OF THE EMBODIMENTS
[0019] When manufacturing a printed circuit board with the method
described in Japanese Patent Laid-Open No. 2008-094923, a
photolithography step and an etching step are necessary. Therefore,
there are the problems that cost increases, and a large amount of
waste liquid is produced so the environmental burden is high. On
the other hand, the method described in Japanese Patent Laid-Open
No. 7-192790 is only applicable to a special conductive
polymer.
[0020] According to an embodiment of the present invention, a fine
plating pattern can easily be formed on a resin article.
[0021] The inventors of the present application investigated
modifying part of a resin article such that electroless plating is
deposited by irradiating ultraviolet rays on only a portion where a
plating layer is intended to be provided, in order to provide a
plating layer having a predetermined pattern on the resin article.
First, ultraviolet rays were irradiated on the resin article
through a photomask where a UV-transmissive portion has been
provided according to the predetermined pattern. When electroless
plating was performed on the resin article after irradiation, it
was confirmed that a plating layer was deposited in the portion
where ultraviolet rays were irradiated. However, when a photomask
having a fine UV-transmissive portion, for example an opening with
a width of 5 .mu.m, was used in order to provide a plating layer
having a fine pattern, it was discovered that despite performing
electroless plating, a complete plating layer with a width of 5
.mu.m was not deposited, and disconnections occurred in some
places.
[0022] The inventors of the present application presume that the
reason for this is as follows. First, it is conceivable that when
the UV-transmissive portion is fine, light scatters and is
attenuated due to the operation of light diffraction, so the resin
article cannot be sufficiently modified. Second, it is conceivable
that the amount of ozone generated becomes small. When ultraviolet
rays are irradiated in oxygen, ozone is generated in the vicinity
of the resin article, and it is conceivable that the generated
ozone promotes modification of the surface of the resin article.
However, when the UV-transmissive portion is fine, the contact
volume of ultraviolet rays and ozone decreases, so it is
conceivable that the amount of ozone generated becomes small.
[0023] After carrying out various investigations in consideration
of these problems, the inventors of the present application
discovered that a resin article can be modified according to a fine
pattern by irradiating the surface of the resin article with
ultraviolet rays through a shielding member described below.
[0024] Following is a description of embodiments in which the
present invention is applicable, with reference to drawings.
However, the scope of the present invention is not limited by the
below embodiments.
[0025] According to the modification method of the present
embodiment, part of the surface of a resin article is selectively
modified such that electroless plating is deposited. Specifically,
the modification method according to the present embodiment
includes a modifying step of irradiating ultraviolet rays on a
portion of the surface of the resin article. Also, by performing
electroless plating on a resin article that has been modified in
this way, a plating layer is formed on a portion of the surface of
the resin article that has been modified. This step is referred to
hereinafter as a plating step. With a method that includes the
modifying step and the plating step, it is possible to manufacture
a resin article having a plating layer. Below, these steps are
described in detail with reference to FIG. 2, which shows a
flowchart of treatment according to one embodiment, and FIGS. 6A to
6C, which illustrate treatment.
[0026] (Modifying Step)
[0027] In a modifying step (S210), ultraviolet rays are irradiated
on a portion of the surface of a resin article. In this modifying
step, ultraviolet rays are irradiated such that an interference
pattern by at least two bundles of ultraviolet light is formed on
the surface of the resin article. As a result of this step, a
portion of the surface of the resin article is selectively modified
such that electroless plating is deposited. For example, a portion
of a resin article 110 shown in FIG. 6A is modified. As shown in
FIG. 6B, a modified portion 160 is generated in the portion that
was modified. As described later, in one embodiment, modification
is performed using an ultraviolet ray laser, so by a laser beam
ablation effect, a recess is formed in a laser beam irradiation
portion of the resin article 110, and the modified portion 160 is
formed in this recess.
[0028] FIG. 1 shows an example of the modifying step in the present
embodiment. As shown in FIG. 1, ultraviolet rays are irradiated on
the surface of the resin article 110 through a shielding member
120. The shielding member 120 has a transmitting portion that
transmits ultraviolet rays such that ultraviolet rays are
irradiated on a portion where a plating layer 170 is to be
deposited by electroless plating. In one embodiment, the shielding
member 120 is a plane-like member and includes an ultraviolet ray
shielding portion 130 that shields from ultraviolet rays, and a
UV-transmissive portion 140 that transmits ultraviolet rays. The
specific configuration of the shielding member 120 is not
particularly limited. For example, the shielding member 120 may be
a quartz chrome mask, and in this case, the transmissive portion
140 is configured with quartz and the shielding portion 130 is a
chrome film that has been formed on the transmissive portion
140.
[0029] In FIG. 1, the resin article 110 and the shielding member
120 are shown separated for the sake of description. However, the
shielding member 120 may be in contact with the surface of the
resin article 110, or the shielding member 120 may be disposed
separated from the resin article 110 with a space or another
holding member, for example. In this case, it is possible to
dispose the resin article 110 and the shielding member 120 such
that the surface of the resin article 110 to be modified and the
surface of the shielding member 120 are parallel. As described
later, the distance between the shielding portion 130 and the
surface of the resin article 110 is controlled such that an
appropriate irradiated region of ultraviolet rays is obtained.
[0030] In FIG. 1, an irradiated region 150 of ultraviolet rays is
shown. As shown in the example in FIG. 1, ultraviolet rays having a
linear irradiated region 150 are irradiated. Also, by movement of
the resin article 110 and the shielding member 120, the surface of
the resin article 110 is scanned by ultraviolet rays through the
shielding member 120. As a result, ultraviolet rays are irradiated
on the surface of the resin article 110 along the transmissive
portion 140, and by an irradiated portion 155 being modified, the
modified portion 160 is formed.
[0031] By condensing the ultraviolet rays from a ultraviolet ray
lamp, an ultraviolet ray laser, or the like using a condenser lens
(not shown), it is possible to irradiate the ultraviolet rays to
the irradiated region 150. This sort of configuration is useful
because, in comparison to a configuration in which light that has
passed through a photomask is condensed with a condenser lens then
irradiated on the surface of the resin article 110, the surface of
the resin article 110 can more easily be modified according to a
pattern having a large area. Also, the condensed ultraviolet rays
having a linear irradiated region as shown in FIG. 1 have a
comparatively high intensity, so this configuration is advantageous
for modification efficiency. However, the irradiation method is not
particularly limited, as long as ultraviolet rays are irradiated on
the resin article through a shielding member.
[0032] In the present embodiment, the resin article 110 and the
shielding member 120 are disposed such that an interference pattern
by at least two bundles of ultraviolet light is formed on the
surface of the resin article. The interference pattern can be
formed, for example, using a slit, including a single slit and a
plurality of slits, and a diffraction grating, including a
transmissive diffraction grating and a reflective diffraction
grating, and the like. In one example, ultraviolet rays are
irradiated on a portion of the surface of the resin article 110
through the shielding member 120 provided with the transmissive
portion 140. That is, the resin article 110 and the shielding
member 120 are disposed such that an interference pattern by at
least two bundles of ultraviolet light that were transmitted
through the transmissive portion 140 is formed on the surface of
the resin article 110. In one embodiment, the transmissive portion
140 is a single slit. That is, an interference stripe by a bundle
of ultraviolet light that was transmitted through the vicinity of
one end of the transmissive portion 140, and a bundle of
ultraviolet light that was transmitted through the vicinity of the
other end of the same transmissive portion 140, is formed on the
surface of the resin article 110.
[0033] The interference pattern will be described with reference to
FIG. 3. In FIG. 3, the surface of the resin article 110 is disposed
parallel to the shielding member 120, and parallel ultraviolet rays
310 are incident on the shielding member 120 from the opposite side
as the resin article 110. In this case, due to light diffraction at
the slit, interference occurs between the bundles of ultraviolet
light that passed through each position of the transmissive portion
140. Where the slit width is represented by d, the distance between
the surface of the resin article 110 and the shielding member 120
is represented by l, and the wavelength of the ultraviolet rays is
represented by .lamda., a bright line position and a dark line
position .DELTA.x on the surface of the resin article 110 are known
to be obtained as described below. The bright line position is a
position where light bundles interfere constructively and the dark
line position is a position where light bundles interfere
destructively. Here, the distance l between the surface of the
resin article 110 and the shielding member 120 is more specifically
the distance between the surface of the resin article 110 and the
shielding portion 130. For example, in a case where the shielding
member 120 is a quartz mask having a plating layer, the distance l
is the distance between the surface of the resin article 110 and
the plating layer.
.DELTA.x=0,(m+0.5).DELTA.l/d
(bright line position)
.DELTA.x=m.lamda.l/d
(dark line position)
[0034] In the above expressions, the bright line position and the
dark line position .DELTA.x indicate the distance from a center
point O, and the center point O is a point where ultraviolet rays
transmitted through the center of the slit are incident on the
surface of the resin article 110, when assuming that there is no
diffraction. Also, m represents an integer of at least 1.
[0035] Thus, with ultraviolet rays it is possible to modify a
region having a desired width on the surface of the resin article
110 by adjusting the slit width d, the distance l between the resin
article 110 and the shielding member 120, and the wavelength
.lamda. of the ultraviolet rays. As a specific example, for example
when the slit width d is set to 15 .mu.m, the distance l between
the surface of the resin article 110 and the shielding member 120
is set to 193 .mu.m, and the wavelength .lamda. of the ultraviolet
rays is set to 193 nm, the dark line position .DELTA.x=2.48 .mu.m
(m=1). Because ultraviolet rays are not irradiated at the dark line
position, the plating layer 170 is not deposited in the plating
step described later. Accordingly, in this example, a fine plating
layer 170 of 4.96 .mu.m or less is formed at the position of the
center point O by the plating step described later.
[0036] Thus, in one embodiment, the slit width (15 .mu.m) is larger
than the width (4.96 .mu.m or less) of the portion of the surface
of the resin article 110 to be modified such that electroless
plating is deposited by ultraviolet rays that have been transmitted
through the slit. According to such a configuration, when
ultraviolet rays are irradiated in oxygen-containing atmosphere, a
sufficient amount of ozone is generated in the vicinity of the slit
having a large opening, so it is expected that modification of the
surface of the resin article 110 is promoted. Compared to the slit
width, the width of the plating layer 170 deposited as a result of
the resin article being modified by the ultraviolet rays that were
transmitted through the slit is 80% or less in one embodiment, is
50% or less in another embodiment, and is 35% or less in still
another embodiment.
[0037] As described later, the plating layer 170 is deposited in
the plating step described later if the amount of irradiation of
ultraviolet rays is sufficiently large, but the plating layer 170
is not deposited in the plating step described later in a case
where the amount of irradiation of ultraviolet rays is
comparatively small. Accordingly, by adjusting the amount of
irradiation of ultraviolet rays, it is possible to deposit the
plating layer 170 at only one location or at a plurality of
locations. For example, it is possible to deposit the plating layer
170 at only the position of the center point O, and it is possible
to deposit the plating layer 170 at a total of three locations
including the positions .DELTA.x=1.5.lamda.l/d in addition to the
position of the center point O.
[0038] In another embodiment, an interference pattern is formed
using a plurality of slits. FIG. 4 shows an example case of using
two slits. In this case, due to light diffraction at the slits,
interference occurs between a bundle of ultraviolet light that was
transmitted through a slit 401, which is part of the transmissive
portion, and a bundle of ultraviolet light that was transmitted
through a slit 402, which is part of the transmissive portion.
Where the distance between the slit 401 and the slit 402 is
represented by d, a bright line position and a dark line position
.DELTA.x of the surface of the resin article 110 are known to be
obtained as described below.
.DELTA.x=0,m.lamda.l/d
(bright line position)
.DELTA.x=(m-0.5).lamda.l/d
(dark line position)
[0039] Also, in still another embodiment, as shown in FIG. 5, an
interference pattern is formed using a diffraction grating that has
been provided in the shielding member 120. In this case, the
diffraction grating acts as the transmissive portion 140. That is,
interference occurs between a bundle of ultraviolet light that was
transmitted through a first position of the diffraction grating,
and a bundle of ultraviolet light that was transmitted through a
second position of the diffraction grating. Where a grating
constant of the diffraction grating is represented by d, a bright
line position and a dark line position .DELTA.x of the surface of
the resin article 110 are known to be obtained as described
below.
.DELTA.x=0,m.lamda.l/d
(bright line position)
.DELTA.x=(m-0.5).lamda.l/d
(dark line position)
[0040] As described above, different interference patterns are
formed in a case where a single slit is used, a case where a
plurality of slits are used, and a case where a diffraction grating
is used. Specifically, by increasing the number of slits, it is
possible to narrow the region where ultraviolet rays are
irradiated. Thus, it is possible to select an appropriate slit
configuration or diffraction grating according to the shape of the
plating layer 170 intended to be formed.
[0041] As described above, by using a slit, it is possible to
control the irradiated region of ultraviolet rays on the resin
article 110. In one embodiment, the irradiated region on the
surface of the resin article 110, of ultraviolet rays that have
been transmitted through the slit, is striped. Also, in one
embodiment, the shape of the transmissive portion 140 differs from
the irradiated region on the resin article 110 of ultraviolet rays
that have been transmitted through the transmissive portion 140.
That is, the irradiated region on the resin article 110 of
ultraviolet rays that have been transmitted through the
transmissive portion 140 differs substantially from the irradiated
region on the resin article 110 of ultraviolet rays that have been
transmitted through the transmissive portion 140 in a case where it
is assumed there is no diffraction. In one embodiment, the shape of
the transmissive portion 140 is larger than the region on the resin
article 110 to be modified such that the plating layer 170 is
deposited by ultraviolet rays that have been transmitted through
the transmissive portion 140.
[0042] According to the above sort of configuration, modification
of the surface of the resin article 110 is performed while
considering the action of light diffraction. Accordingly, it is
conceivable that this configuration is less likely to be affected
by a reduction in the amount of irradiation caused by diffraction
of ultraviolet rays in a case of using a shielding member having a
fine transmissive portion. Also, in an embodiment in which the
shape of the transmissive portion 140 is larger than the irradiated
region of ultraviolet rays that have been transmitted through the
transmissive portion 140, the ultraviolet rays that have been
transmitted through the transmissive portion 140 are condensed to
the irradiated region on the resin article 110 by operation of the
slit. Therefore, a greater amount of irradiation of ultraviolet
rays on the resin article 110 occurs than in a case where
ultraviolet rays are irradiated through a mask having a
transmissive portion with the same size as the irradiated region.
Therefore, it is conceivable that the surface of the resin article
110 can be more greatly modified than with a lesser amount of
irradiation. On the other hand, also in an embodiment in which the
shape of the transmissive portion 140 is smaller than the
irradiated region of ultraviolet rays that have been transmitted
through the transmissive portion 140, modification is performed
while considering the action of light diffraction, so it is
conceivable that a shift in the position of the irradiated region
caused by diffraction of ultraviolet rays is suppressed.
[0043] The slit width can be appropriately selected according to
the pattern of the plating layer 170 intended to be provided, if an
interference pattern by diffraction of ultraviolet light occurs on
the surface of the resin article 110. The slit width is 50 .mu.m or
less in one embodiment, and is 25 .mu.m or less in still another
embodiment. On the other hand, in order for the ultraviolet ray
transmission amount to be sufficiently large, the slit width is at
least 5 .mu.m in one embodiment, and at least 10 .mu.m in still
another embodiment.
[0044] Thus, the shielding member 120 has a function of controlling
an incidence position of transmitted ultraviolet rays on the resin
article 110. Ultraviolet light bundles that have passed through the
slits or the diffraction grating, due to interfering destructively
or constructively, form a pattern of differing irradiation
intensity on the resin article 110. Said another way, the shielding
member 120 has a condensing portion that condenses transmitted
ultraviolet rays. In one embodiment, a slit configured to be formed
by the shielding portion 130 and the transmissive portion 140 acts
as this condensing portion. Also, in another embodiment, a
diffraction grating that acts as the transmissive portion 140 acts
as this condensing portion. On the other hand, in another
embodiment, the shielding member 120 may be provided with a lens
such as a microlens that has been provided in the transmissive
portion 140 as the condensing portion. In this case as well, an
interference pattern does not occur on the resin article 110, but
it is possible to suppress a reduction in the amount of ozone due
to attenuation of the amount of irradiation due to diffraction, or
due to the mask opening being small.
[0045] In one embodiment, irradiation of ultraviolet rays is
performed in an atmosphere that includes at least one of oxygen and
ozone. As a specific example, irradiation of an ultraviolet ray
laser beam on a resin article can be performed in air. In another
embodiment, in order to further promote modification, irradiation
is performed in an atmosphere that includes ozone.
[0046] When ultraviolet rays are irradiated, oxygen in the
atmosphere is decomposed, generating ozone. Further, active oxygen
is generated in the course of ozone decomposing. Even if the resin
article 110 and the shielding member 120 were in contact, a small
amount of oxygen exists between the resin article 110 and the
shielding member 120, so ozone is generated in the vicinity of the
resin article 110. Also, at the surface of the resin article 110,
bonds in the molecules that constitute the resin article 110 are
broken. At this time, molecules that constitute the resin article
110 react with active oxygen, and the surface of the resin article
110 oxidizes, that is, at the surface of the resin article 110,
bonds such as C--O bonds, C.dbd.O bonds, and C(.dbd.O)--O bonds
(carboxyl group skeletal structure portion) are formed. Such a
hydrophilic group increases the chemical adsorption of the resin
article 110 and the plating layer 170. Also, since a portion made
brittle by oxidation of the surface of the resin article 110 will
come off in a later step such as an alkali treatment step for
example, a fine rough surface is formed in a portion where
ultraviolet rays have been irradiated. Because of this rough
surface, physical adsorption of the resin article 110 and the
plating layer 170 increases due to an anchoring effect. Further, in
a portion that has been modified, it is possible to selectively
cause adsorption of catalyst ions when performing electroless
plating.
[0047] Energy of photons of a specific wavelength is expressed by
the following formulas.
E=Nhc/.lamda.(KJmol.sup.-1)
N=6.022.times.10.sup.23mol.sup.-1
(Avogadro's constant)
h=6.626.times.10.sup.-37KJs
(Plank's constant)
c=2.988.times.10.sup.8ms.sup.-1
(speed of light)
.lamda.=light wavelength (nm)
[0048] Here, the bond energy of oxygen molecules is 490.4
KJmol.sup.-1. From the photon energy formula, this bond energy is
about 243 nm when converted to light wavelength. This indicates
that oxygen molecules in the atmosphere will absorb ultraviolet
rays with a wavelength of 243 nm or less and decompose. Thus, ozone
O.sub.3 is generated. Further, active oxygen is generated in the
course of ozone decomposing. At this time, when there are
ultraviolet rays with a wavelength of 310 nm or less, ozone is
efficiently decomposed, and active oxygen is generated. Further,
ultraviolet rays with a wavelength of 254 nm decompose ozone most
efficiently.
O.sub.2+h.nu.(243 nm or less).fwdarw.O(3P)+O(3P)
O.sub.2+O(3P).fwdarw.O.sub.3(ozone)
O.sub.3+h.nu.(310 nm or less).fwdarw.O.sub.2+O(1D)(active oxygen)
[0049] O(3P): ground state oxygen atom [0050] O(1D): excited oxygen
atom (active oxygen)
[0051] On the other hand, in another embodiment, irradiation of
ultraviolet rays on the resin article 110 can be performed in
another gas atmosphere, for example, such as an amine compound gas
atmosphere like ammonia or an amide compound gas atmosphere. By
performing irradiation in an amine compound gas atmosphere or an
amide compound gas atmosphere, it is possible to oxidize the
surface of the resin article 110, that is, possible to generate
bonds including nitrogen atoms at the surface of the resin article
110. That is, the surface of the resin article 110 is modified so
as to include nitrogen atoms, so adsorption with the plating layer
improves, so it is possible to perform selective plating in an
irradiated portion. In a case where modification is performed by
ultraviolet rays after isolating the item to be processed from an
atmosphere at normal pressure, and then changing pressure or
enveloping in compound gas, it is possible to suitably select a
wavelength appropriate for the reaction. On the other hand,
irradiating ultraviolet rays having a wavelength of 243 nm or less
in air including oxygen is advantageous because modification can be
performed with low cost.
[0052] Also, it is not necessary to perform irradiation of
ultraviolet rays on the resin article 110 in an air atmosphere. For
example, by irradiating ultraviolet rays with a wavelength that
causes a chemical change of the resin article 110, it is possible
to modify the surface of the resin article 110 even in a
vacuum.
[0053] When modifying the surface of the resin article 110 using an
interference pattern, it is possible to irradiate coherent
ultraviolet rays such that interference occurs easily. Coherent
ultraviolet rays can be irradiated using an ultraviolet ray laser,
for example.
[0054] As an ultraviolet ray laser, it is possible to use an
excimer laser, which is one type of gas laser. In an excimer laser,
an excited state is produced by momentarily applying a high voltage
to a gas mixture of inactive gas and halogen gas, and high output
pulse oscillation is performed.
[0055] The laser beam wavelength changes depending on the
combination of the inactive gas and the halogen gas used to
generate the excimer laser beam. The relationship between the gas
combination and the laser beam wavelength is shown below.
[0056] F.sub.2 excimer laser: wavelength 157 nm
[0057] ArF excimer laser: wavelength 193 nm
[0058] KrCl excimer laser: wavelength 222 nm
[0059] KrF excimer laser: wavelength 248 nm
[0060] In one embodiment, an ArF excimer laser is used as the
ultraviolet ray laser. An ArF excimer laser has a comparatively
short wavelength, so modification is performed more efficiently.
Also, compared to an F.sub.2 excimer laser, an ArF excimer laser
has less absorption by oxygen in air and therefore is easier to
manage.
[0061] A KrCl excimer laser or a KrF excimer laser may also be used
as the ultraviolet ray laser. These lasers have less absorption by
oxygen in air than an ArF excimer laser and therefore are easier to
manage.
[0062] A laser beam from an excimer laser can have a shape
reflecting the shape of a discharge region, for example a
rectangular beam shape of about 20.times.10 mm. Because the laser
beam from an excimer laser is thick and has high pulse energy, in a
case of using an excimer laser, it is possible to treat a
comparatively large area at one time with a comparatively high
irradiation intensity. Also, by using an appropriate lens, the
laser beam can be modified to a linear shape, as shown in FIG.
1.
[0063] On the other hand, there are cases where plating is not
deposited in a portion where ultraviolet rays were irradiated by
merely irradiating ultraviolet rays having a high energy density,
such as with an ultraviolet ray laser, on the surface of the resin
article 110. The surface of the resin article 110 is modified by
irradiating an ultraviolet ray laser beam, but the modified layer
is eliminated due to the ablation effect by an ultraviolet laser
beam. Therefore, it is possible that at least a fixed amount of
modification will not be obtained, and so an amount of modification
sufficient for plating to be deposited cannot be performed.
Ablation is a phenomenon where the surface of material is removed
by evaporation.
[0064] Consequently, in one embodiment, after irradiating an
ultraviolet ray laser beam on the surface of the resin article 110,
further modifying treatment is performed. This modifying treatment
may be selectively performed on a portion of the resin article 110,
for example, a portion where the plating layer 170 is intended to
be deposited. However, this modifying treatment may also be
performed on a larger region that encompasses the portion where the
plating layer 170 is intended to be deposited, and for example may
also be performed on the entire resin article 110. In this case,
the modifying treatment is performed such that the plating layer
170 will not be deposited in a portion where the plating layer 170
is not to be deposited. In a portion where the laser beam is being
intensely irradiated, modification is already progressing, so
modification such that the plating layer 170 will be deposited is
possible even with weak modifying treatment. On the other hand, in
a portion where the laser beam has not been irradiated or has only
been irradiated weakly, modification has not progressed much, so
the plating layer 170 will not be deposited with weak modifying
treatment. Accordingly, even in a case where modifying treatment is
performed uniformly on the entire resin article 110, in the plating
step described later, it is possible to selectively cause the
plating layer 170 to be deposited in a desired portion where the
laser beam is being intensely irradiated.
[0065] As the modifying treatment, it is possible to use a plasma
treatment, an acid treatment, an alkali treatment, or the like, and
in the present embodiment, an ultraviolet ray irradiation treatment
is used. For example, the surface of the resin article 110 is
further modified by irradiating ultraviolet rays using an
ultraviolet ray lamp or an ultraviolet ray LED or the like that
continuously radiates ultraviolet rays. Irradiation of ultraviolet
rays can be performed in a similar atmosphere as irradiation by an
ultraviolet ray laser beam, described above. For example,
ultraviolet rays can be irradiated in an atmosphere including at
least one of oxygen and ozone. In order to improve modification
efficiency, in one embodiment, ultraviolet rays having a wavelength
of 243 nm or less are irradiated.
[0066] Examples of an ultraviolet ray lamp include a low pressure
mercury lamp, an excimer lamp, and the like. A low pressure mercury
lamp can irradiate ultraviolet rays having a wavelength of 185 nm
and 254 nm. Also, for reference, an example of an excimer lamp that
can be used in air is given below. An Xe.sub.2 excimer lamp is
commonly used as an excimer lamp.
[0067] Xe.sub.2 excimer lamp: wavelength 172 nm
[0068] KrBr excimer lamp: wavelength 206 nm
[0069] KrCl excimer lamp: wavelength 222 nm
[0070] When irradiating ultraviolet rays on the resin article 110,
irradiation of ultraviolet rays is controlled such that the
irradiation amount becomes a desired value. The irradiation amount
can be controlled by changing the irradiation time. Also, the
irradiation amount can be controlled by changing the output, lamp
quantity, irradiation distance, or the like of the ultraviolet ray
lamp.
[0071] In one embodiment, energy density is at least
1.0.times.10.sup.5 W/cm.sup.2 for the primary wavelength of the
ultraviolet ray laser beam irradiated on the resin article 110. The
upper limit of energy density is not particularly limited, and for
example, can be 1.0.times.10.sup.15 W/cm.sup.2 or less. In the
present specification, unless specifically stated otherwise, the
irradiation amount and irradiation intensity of ultraviolet rays
refer to values for the primary wavelength. In the present
specification the primary wavelength refers to a wavelength having
the highest intensity in a region of 243 nm or less. Specifically,
in the case of a low pressure mercury lamp the primary wavelength
is 185 nm. When a single wavelength laser is used as the
ultraviolet ray laser, the wavelength of the laser beam is the
primary wavelength.
[0072] In one embodiment, the ultraviolet ray laser beam is
irradiated in pulses. By irradiating the laser beam in pulses for a
short time, it is possible to avoid an increase in the temperature
of the resin article 110 and the shielding member 120. Therefore,
it is possible to suppress shifting of the position of the modified
portion caused by differences in the thermal expansion coefficient
between the resin article 110 and the shielding member 120. In one
embodiment, the pulse width is at least 10 ns and not more than 100
ns.
[0073] The irradiation amount and the number of pulses of the laser
beam can be appropriately selected according to the type or the
like of the resin article 110. In one embodiment, a laser beam
having an energy density per pulse of at least 50 mJ/cm.sup.2 and
not more than 5000 mJ/cm.sup.2 is irradiated. Also, in one
embodiment, a laser beam is irradiated such that a total
irradiation amount is at least 100 mJ/cm.sup.2 and not more than
50,000 mJ/cm.sup.2.
[0074] The irradiation amount of ultraviolet rays when performing
further modification after the ultraviolet ray laser beam was
irradiated can be appropriately adjusted such that the plating
layer 170 is selectively deposited in a desired portion where the
laser beam is being intensely irradiated. In one embodiment, the
total irradiation amount of ultraviolet rays for the primary
wavelength is not more than 400 mJ/cm.sup.2. Also, in one
embodiment, the total irradiation amount of ultraviolet rays for
the primary wavelength is at least 50 mJ/cm.sup.2.
[0075] However, the plating deposit conditions are variable
depending on the type of plating solution, the type of the resin
article 110, the degree of contamination of the surface of the
resin article 110, the concentration, temperature, pH, and
age-related degradation of the plating solution, fluctuation in
output of the ultraviolet ray lamp, focus shift of the ultraviolet
ray laser, and the like. In this case, the irradiation amount from
the ultraviolet ray laser, the ultraviolet ray lamp, and the like
is appropriately determined with reference to the numerical values
stated above, such that plating is selectively deposited in a
desired portion. The irradiation amount can be controlled by
changing the output, lamp quantity, irradiation distance, or the
like of the ultraviolet ray lamp.
[0076] According to the investigations by the inventors of the
present application, the ease of depositing the plating layer 170
in the plating step depends on an oxygen atom existence ratio at
the surface of the resin article 110. It is conceivable that the
oxygen atom existence ratio increases as modification by
ultraviolet rays or the like proceeds. In one embodiment, the
irradiation amount of the ultraviolet ray laser beam is adjusted
such that in a portion where the plating layer 170 is to be
deposited, after irradiating the ultraviolet ray laser beam, the
oxygen atom existence ratio of the surface of the resin article 110
is at least 3.0%, or at least 3.8%. Also, the irradiation amount of
the ultraviolet rays is adjusted such that in a portion where the
plating layer 170 is to be deposited, after performing further
modification, the oxygen atom existence ratio is at least 18%, or
at least 20.1%. There is not an upper limit to the oxygen atom
existence ratio, and the oxygen atom existence ratio is not
particularly limited as long as plating is deposited. On the other
hand, the irradiation amount of the ultraviolet rays is adjusted
such that in a portion where the plating layer 170 is not to be
deposited, after performing further modification, the oxygen atom
existence ratio is no more than 15%, or no more than 12.6%. There
is not a lower limit to the oxygen atom existence ratio, and the
oxygen atom existence ratio is not particularly limited as long as
plating is not deposited.
[0077] In the present specification, the oxygen atom existence
ratio refers to an existence ratio (atom %) of oxygen atoms
relative to all atoms at the surface of the resin article 110,
which has been calculated by XPS measurement. However, because it
is conceivable that hydrophilicity of the surface of the resin
article 110 is greatly affected by the ratio of carbon atoms and
oxygen atoms, and because hydrogen atoms cannot be detected by XPS
measurement, the number of hydrogen atoms is not included in
calculations. Here, also, there are cases where the oxygen atom
existence ratio changes somewhat due to measurement conditions,
detection error of each apparatus, or the like.
[0078] The resin article 110 used in the present embodiment is not
particularly limited, as long as the resin article 110 has a resin
material on the surface that can be modified by ultraviolet rays.
Examples of the resin material include a polyolefin including
cyclopolyolefin, i.e., a cyclo-olefin polymer or a polyolefin such
as polystyrene, a polyester such as polyethylene terephthalate, a
polyvinyl such as polyvinyl chloride, a polycarbonate, a polyimide,
or the like.
[0079] The shape of the resin article 110 also is not particularly
limited. For example, the resin article 110 may have a film-like
shape or may have a plate-like shape. Further, the thickness of the
resin article 110 also is not particularly limited. Also, it is not
necessary to configure the resin article 110 with only resin. That
is, in one embodiment, the resin article 110 is a composite
material article having a coated structure obtained by coating the
surface of another material article with resin material. As a
specific example of a composite material article, there is a
composite material article in which the surface of a metal material
article has been coated with a resin material.
[0080] In one embodiment, the resin article 110 has a smooth
surface. Due to the resin article 110 having a smoother surface, a
more uniform plating layer 170 is formed by plating. By using such
a smooth plating layer 170 as conductive wiring, it is possible to
suppress high frequency signal loss. In the present specification,
arithmetic mean roughness Ra is defined by JIS B0601: 2001.
According to a method for modifying the surface of the resin
article 110 using ultraviolet rays as in the present embodiment,
nanometer-order fine unevenness is formed in the surface of the
resin article 110. In one embodiment, arithmetic mean roughness Ra
of the resin article surface is 10 nm or less. Unevenness formed in
this way is expected to be remarkably small compared to
micrometer-order unevenness that, for example, is obtained by
irradiating a high-intensity visible laser beam on the surface of a
resin article, or is formed by treatment with chromic acid or the
like.
[0081] (Plating Step)
[0082] In a plating step (S220), as shown in FIG. 6C, the plating
layer 170 is formed on the surface of the resin article 110 whose
surface has been modified in the modifying step. Thus, a resin
article 190 having a plating layer is manufactured. In the
modifying step, selective modification has been performed such that
the plating layer 170 is deposited in a desired modified portion
160. Accordingly, even in a case where, for example, the entire
resin article 110 has been immersed in a plating solution, the
plating layer 170 is selectively deposited in a desired modified
portion 160. Also, plating is not deposited in a portion adjacent
to the desired portion. Accordingly, it is not necessary to perform
patterning on the plating layer by a method such as
photolithography and etching after forming the plating layer
170.
[0083] In one embodiment, the plating layer 170 is formed by an
electroless plating method. The specific electroless plating method
is not particularly limited. Examples of electroless plating
methods that can be adopted include an electroless plating method
employing a formalin-containing electroless plating bath, and an
electroless plating method in which hypophosphorous acid is used as
a reducing agent, which leads to a slow deposit speed but is easily
managed. As more specific examples of the electroless plating
method, there are electroless nickel plating, electroless copper
plating, electroless copper-nickel plating, electroless zinc oxide
plating, and the like. The plating layer 170 to be formed, in one
embodiment, is a metal film, and may also be a ceramic film such as
a zinc oxide plating layer. By modifying the resin article 110 as
described above, adhesion of the modified portion 160 and the
deposited plating layer improves.
[0084] In one embodiment, the electroless plating can be performed
by the below method.
[0085] 1. (Alkali Treatment) The resin article 110 is immersed in
an alkali solution and oil is removed to improve hydrophilicity.
Examples of the alkali solution include a sodium hydroxide aqueous
solution or the like.
[0086] 2. (Conditioner Treatment) The resin article 110 is immersed
in a solution containing a binder of the resin article 110 and
catalyst ions. Examples of the binder include a cationic polymer or
the like.
[0087] 3. (Activator Treatment) The resin article 110 is immersed
in a solution including catalyst ions. Examples of catalyst ions
include a palladium complex such as hydrochloric acid palladium
complex, or the like.
[0088] 4. (Accelerator Treatment) The resin article 110 is immersed
in a solution containing a reducing agent, causing reduction and
depositing of catalyst ions. Examples of the reducing agent include
hydrogen gas, dimethylamine borane, sodium borohydride, and the
like.
[0089] 5. (Electroless Plating Treatment) The plating layer 170 is
deposited on the deposited catalyst.
[0090] Electroless plating according to this sort of method can be
performed using, for example, an electroless plating solution set,
such as a Cu--Ni plating solution set "AISL" made by JCU Co.
[0091] In another embodiment, as catalyst ions, a palladium complex
is used that easily adheres to the modified portion 160 and at
least partially has a positive charge. In order to improve adhesion
to the modified portion 160, in one embodiment, a solution is used
that includes palladium complex ions having a positive charge in
the solution. An example of a palladium complex that at least
partially has a positive charge is a complex in which amine ligands
are in coordination bonds. Also, another example of a palladium
complex that at least partially has a positive charge is a
palladium basic amino acid complex.
[0092] In this case, by immersing the resin article 110 in a binder
solution, it is not necessary to increase the affinity of the resin
article 110 and catalyst ions. A palladium basic amino acid complex
is a complex of palladium ions and a basic amino acid. The
palladium ions are not limited, but divalent palladium ions are
often used. The basic amino acid may be a natural amino acid or an
artificial amino acid. In one embodiment, the amino acid is an
.alpha.-amino acid. Basic amino acids include amino acids having a
basic substituted group such as an amino group or a guanidyl group
or the like in a side chain. Examples of a basic amino acid include
lysine, arginine, ornithine, or the like.
[0093] As the catalyst ions, it is advantageous for ease of
selectively depositing the plating layer 170 to use a palladium
complex at least partially having a positive charge. That is, when
using this sort of catalyst, it is more difficult to deposit the
plating layer 170 in a portion where the plating layer 170 is not
to be provided, that is, in a portion that has not been
sufficiently modified in the modifying step.
[0094] A specific example of a palladium basic amino acid complex
is expressed by below Formula (I).
##STR00001##
[0095] In above Formula (I), L.sub.1 and L.sub.2 each independently
represent an alkylene group having a carbon number of at least 1
and not more than 10, and R.sub.3 and R.sub.4 each independently
represent an amino group or a guanidyl group. Examples of an
alkylene group having a carbon number of at least 1 and not more
than 10 include straight-chain alkylene groups such as a methylene
group, 1,2-ethanediyl group, 1,3-propanediyl group,
n-butane-1,4-diyl group, or the like. In above Formula (I), two
amino groups are coordinated in trans position, but two amino
groups may also be coordinated in cis position. Also, the palladium
basic amino acid complex may have a mixture of groups in cis
position and trans position.
[0096] In another embodiment, the plating layer 170 can be formed
by a high speed electroless plating method. According to a high
speed electroless plating method, it is possible to form a thicker
plating layer. In still another embodiment, on the plating layer
170 that has been formed by electroless plating, it is possible to
deposit plating by additionally using electroplating. According to
this method, it is possible to form a still thicker plating layer
170. The specific method of electroplating is not particularly
limited.
[0097] There is no special limitation on the thickness of the
plating layer 170 to be obtained. A plating layer 170 of an
appropriate thickness is formed according to the application of the
resin article 190 having a plating layer to be obtained. Also,
there is no special limitation on the material of the plating layer
170. An appropriate material is selected according to the
application of the resin article 190 having a plating layer to be
obtained.
[0098] The resin article 190 having a plating layer that has been
obtained in this way can be used in various applications.
Specifically, according to the present embodiment, it is possible
to easily manufacture a resin article having fine wiring. Such a
resin article having fine wiring can be used as a circuit board,
for example. By adopting finer wiring, it is possible to increase
wiring density and reduce the size of the circuit board, so
electronic devices having the circuit board can be made smaller.
Also, as one example, a resin article having fine wiring arranged
in a mesh-like manner on its surface can be used as a conductive
film, for example. Specifically, in a transparent conductive film
where wiring has been provided on a transparent resin article, by
adopting finer wiring, it is possible to improve visibility through
the transparent conductive film.
EXAMPLES
Experiment 1
(Substrate Treatment)
[0099] In Experiment 1, a cyclo-olefin polymer material (made by
Zeon Corp., ZeonorFilm ZF-16, thickness 100 .mu.m), which is a
resin material, was used as the substrate for electroless
plating.
[0100] First, before performing surface modification, the below
treatment was performed to clean the substrate surface.
1. Ultrasonic cleaning for 3 minutes in pure water at 50.degree. C.
2. Immersion for 3 minutes in alkali cleaning solution (containing
3.7% sodium hydroxide) at 50.degree. C. 3. Ultrasonic cleaning for
3 minutes in pure water at 50.degree. C.
4. Drying
[0101] (Modifying Step)
[0102] Next, an ultraviolet ray laser beam was irradiated on a
desired portion of the substrate. Details of the ultraviolet ray
laser used in Experiment 1 are given below.
[0103] Ultraviolet ray laser: ArF excimer laser (primary wavelength
193 nm)
[0104] Ultraviolet ray laser irradiation device: LPXpro305 made by
Coherent Co.
[0105] Irradiation conditions: frequency 50 Hz, pulse width 25 ns,
200 pulses
[0106] Energy density at the irradiated surface per pulse: 100
mJ/cm.sup.2
[0107] The oxygen atom existence ratio for the substrate irradiated
by the ultraviolet ray laser beam in this way was measured to be
8.8% by XPS measurement. Here, the XPS measurement apparatus is
unable to measure hydrogen atoms. Therefore, the existence ratio of
atoms at the surface of the cyclo-olefin polymer material in
Experiment 1 was calculated based on only carbon atoms and oxygen
atoms.
[0108] Also, after irradiating the ArF excimer laser beam for 200
pulses on the cyclo-olefin polymer material, the shape of the
substrate surface was checked using an SEM (scanning electron
microscope), and the results of this check showed that a recess was
formed in the laser beam irradiated portion, with a depth of about
0.2 .mu.m. Also, it was possible to adjust the depth by increasing
or decreasing the number of laser beam pulses.
[0109] Next, further modification was performed by irradiating an
ultraviolet ray lamp on a desired portion of the substrate after
laser beam irradiation. Details of the ultraviolet ray lamp (low
pressure mercury lamp) used in Experiment 1 are given below.
[0110] Low pressure mercury lamp: UV-300 made by Samco Corp.
(primary wavelengths 185 nm, 254 nm)
[0111] Illuminance at irradiation distance 3.5 cm: [0112] 5.40
mW/cm.sup.2 (254 nm) [0113] 1.35 mW/cm.sup.2 (185 nm)
[0114] Specifically, on the substrate after irradiating the ArF
excimer laser beam for 200 pulses on the cyclo-olefin polymer
material, further using the above ultraviolet ray lamp, ultraviolet
rays of 1.35 mW/cm.sup.2 (185 nm) were irradiated for 1 minute at a
distance of 3.5 cm from the ultraviolet ray lamp. In this case, the
total amount of exposure was 1.35 mW/cm.sup.2.times.60 seconds=81
mJ/cm.sup.2.
[0115] The status of surface modification for the substrate
irradiated with ultraviolet rays in this way was analyzed by XPS
measurement. For a portion on the substrate that was irradiated by
the laser beam, the oxygen atom existence ratio after performing
irradiation by the ultraviolet ray lamp was 20.1%. Also, for a
portion on the substrate that was not irradiated by the laser beam,
the oxygen atom existence ratio after performing irradiation by the
ultraviolet ray lamp was 12.6%. Thus, in Experiment 1, the oxygen
atom existence ratio of a portion on the substrate that was not
irradiated by the laser beam was suppressed to no more than 15%.
Therefore, as described later, it was possible to selectively
deposit plating in a portion where the laser beam was
irradiated.
[0116] (Plating Step)
[0117] Next, the plating step in which electroless plating is
performed was performed on the substrate that was irradiated with
ultraviolet rays in the modifying step. A Cu--Ni plating solution
set "AISL" made by JCU Co. was used as an electroless plating
solution. Specific treatment in the plating step is shown in Table
1.
TABLE-US-00001 TABLE 1 Treatment Step Conditions Remarks Alkali
treatment 50.degree. C., 2 min. Oil removal, wettability improved
Water rinse + dry (air blow) Conditioner step 50.degree. C., 2 min.
Binder of catalyst ions and substrate provided Warm water rinse +
water rinse + dry (air blow) Activator 50.degree. C., 2 min.
Catalyst ions provided Water rinse + dry (air blow) Accelerator
40.degree. C., 2 min. Catalyst ions reduction, conversion to metal
Water rinse + dry (air blow) Electroless Cu--Ni 60.degree. C., 5
min. Electroless plating plating deposited Water rinse + dry (air
blow)
[0118] When electroless plating according to the steps shown in
Table 1 was finished, a plating layer by electroless plating had
been formed only at a location where the laser beam was
irradiated.
Experiment 2
[0119] Except for changing the number of times of irradiating the
laser beam in the irradiating step, the same modifying step and
plating step as in Experiment 1 were performed, and it was observed
whether or not a plating layer was formed at a location where the
laser beam was irradiated. The results are shown in Table 2. In
Table 2, `YES` indicates that plating was deposited, and `NO`
indicates that plating was not deposited.
TABLE-US-00002 TABLE 2 Ultraviolet ray irradiation amount Oxygen
atom existence ratio in further modifying treatment after laser
beam irradiation 81 mJ/cm.sup.2 (1 min. irradiation) 0.0% NO 3.8%
NO 4.2% NO 7.1% YES 8.8% YES
[0120] As shown in Table 2, when ultraviolet rays of 81 mJ/cm.sup.2
are irradiated in further modifying treatment, by adjusting the
oxygen atom existence ratio of a laser beam-irradiated portion to
be equal to or more than 6.5%, plating will be deposited in the
laser beam-irradiated portion. Specifically, in Experiment 2, in
which an ArF excimer laser beam with an energy density of 100
mJ/cm.sup.2 is irradiated, when the number of pulses is at least
20, the oxygen atom existence ratio is at least 6.5%. It is
conceivable that the oxygen atom existence ratio will not decrease
even if the number of pulses is increased, so it is conceivable
that there is no particular upper limit for the number of pulses,
for a case where the number of pulses is 200 or less, it was
confirmed that the oxygen atom existence ratio is at least
6.5%.
Experiment 3
[0121] Except for changing the number of times of irradiating the
laser beam in the modifying step, and irradiating ultraviolet rays
for 3 minutes in the further modifying treatment, the same
modifying step and plating step as in Experiment 1 were performed,
and it was observed whether or not a plating layer was formed at a
location where the laser beam was irradiated. The results are shown
in Table 3. In Table 3, `YES` indicates that plating was deposited,
and `NO` indicates that plating was not deposited.
TABLE-US-00003 TABLE 3 Ultraviolet ray irradiation amount Oxygen
atom existence ratio in further modifying treatment after laser
beam irradiation 243 mJ/cm.sup.2 (3 min. irradiation) 0.0% NO 3.8%
YES 4.2% YES 7.1% YES 8.8% YES
[0122] As shown in Table 3, when ultraviolet rays of 243
mJ/cm.sup.2 are irradiated in further modifying treatment, the
oxygen atom existence ratio of a laser beam-irradiated portion is
at least 3.0%, so it is clear that plating will be deposited in the
laser beam-irradiated portion.
Example 1
[0123] A cyclo-olefin polymer material (made by Zeon Corp.,
ZeonorFilm ZF-16, thickness 100 .mu.m), which is a resin material,
was used as the substrate.
[0124] First, before performing surface modification, the below
treatment was performed to clean the substrate surface.
1. Ultrasonic cleaning for 3 minutes in pure water at 50.degree. C.
2. Immersion for 3 minutes in alkali cleaning solution (containing
3.7% sodium hydroxide) at 50.degree. C. 3. Ultrasonic cleaning for
3 minutes in pure water at 50.degree. C.
4. Drying
[0125] Next, in air, an ultraviolet ray laser beam was irradiated
on the substrate through a quartz chrome mask placed on the
substrate. Details of the ultraviolet ray laser used in this
example are given below.
[0126] Ultraviolet ray laser: ArF excimer laser (primary wavelength
193 nm)
[0127] Ultraviolet ray laser irradiation device: LPXpro305 made by
Coherent Co.
[0128] Irradiation conditions: frequency 50 Hz, pulse width 25 ns,
40 pulses
[0129] Energy density at the irradiated surface per pulse: 100
mJ/cm.sup.2
[0130] From the ultraviolet ray laser irradiation device, with an
optical system, a 4.5 cm.times.1.5 mm plane-like ultraviolet ray
laser beam was irradiated on the quartz chrome mask. As shown in
FIG. 1, by scanning on the quartz chrome mask with this ultraviolet
ray laser beam, modification of the substrate surface was
performed. The scanning was performed such that 40 pulses of the
laser beam were irradiated at each location on the quartz chrome
mask.
[0131] Also, as shown in FIG. 1, the quartz chrome mask had a slit
perpendicular to the longitudinal direction of the irradiated
region of the ultraviolet ray laser beam. The slit width was 15
.mu.m. Further, a distance between a chrome film of the quartz
chrome mask and the surface of the resin article was 194 .mu.m.
[0132] Next, in air, ultraviolet rays from an ultraviolet ray lamp
were irradiated on the entire surface of the resin article after
the ultraviolet ray laser beam was irradiated. Details of the
ultraviolet ray lamp (low pressure mercury lamp) used in this
example are given below.
[0133] Low pressure mercury lamp: UV-300 made by Samco Corp.
(primary wavelengths 185 nm, 254 nm)
[0134] Irradiation distance: 3.5 cm
[0135] Irradiation time: 2 min. 30 sec.
[0136] Illuminance at irradiation distance 3.5 cm: [0137] 5.40
mW/cm.sup.2 (254 nm) [0138] 1.35 mW/cm.sup.2 (185 nm)
[0139] (Plating Step)
[0140] Next, the plating step in which electroless plating is
performed was performed on the substrate that was irradiated with
ultraviolet rays in the modifying step. Specifically, first, alkali
treatment was performed on the substrate. That is, an alkali
treatment solution used in a Cu--Ni plating solution set "AISL"
made by JCU Co. was heated to 50.degree. C., and the substrate was
immersed for three minutes. Afterward, the substrate was rinsed
with pure water.
[0141] Next, a catalyst ion providing treatment was performed on
the substrate. Specifically, an activator solution (made by JCU
Co., product name ELFSEED ES-300) containing a palladium (II) basic
amino acid complex was heated to 50.degree. C., and the substrate
was immersed for five minutes. Afterward, the substrate was rinsed
in pure water.
[0142] Next, a reducing treatment was performed on the substrate.
Specifically, an accelerator solution (made by JCU Co., product
name ELFSEED ES-400) was heated to 40.degree. C., and the substrate
was immersed for four minutes. Afterward, the substrate was rinsed
in pure water.
[0143] Next, electroless copper-nickel plating was performed on the
substrate. Specifically, an electroless Cu--Ni plating solution
used in a Cu--Ni plating solution set "AISL" made by JCU Co. was
heated to 60.degree. C., and the substrate was immersed for five
minutes. Afterward, the substrate was rinsed in pure water, and
dried. Thus, a resin article having a plating layer was
manufactured.
[0144] When the obtained resin article having a plating layer was
observed, as shown in FIG. 7, three band-like plating layers were
observed to be striped corresponding to the ultraviolet rays that
were transmitted through one slit. The widths of the respective
plating layers were 3.0 .mu.m, 5.0 .mu.m, and 3.0 .mu.m. The
respective plating layers were separated well, and disconnections
were not seen.
[0145] While the present invention has been described with
reference to exemplary embodiments, it is to be understood that the
invention is not limited to the disclosed exemplary embodiments.
The scope of the following claims is to be accorded the broadest
interpretation so as to encompass all such modifications and
equivalent structures and functions.
[0146] This application claims the benefit of Japanese Patent
Application No. 2014-255413, filed Dec. 17, 2014, which is hereby
incorporated by reference herein in its entirety.
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