U.S. patent application number 15/353200 was filed with the patent office on 2017-06-08 for resin article with plating film and method for manufacturing resin article.
The applicant listed for this patent is CANON COMPONENTS, INC.. Invention is credited to Taisuke IWASHITA.
Application Number | 20170159182 15/353200 |
Document ID | / |
Family ID | 58798167 |
Filed Date | 2017-06-08 |
United States Patent
Application |
20170159182 |
Kind Code |
A1 |
IWASHITA; Taisuke |
June 8, 2017 |
RESIN ARTICLE WITH PLATING FILM AND METHOD FOR MANUFACTURING RESIN
ARTICLE
Abstract
There is provided with a method for manufacturing a resin
article provided with a plating film. A resin article is irradiated
with ultraviolet rays. A catalyst is applied to the resin article,
while applying shock to the resin article that has been irradiated
with the ultraviolet rays. An electroless plating is performed on
the resin article.
Inventors: |
IWASHITA; Taisuke;
(Kodama-gun, JP) |
|
Applicant: |
Name |
City |
State |
Country |
Type |
CANON COMPONENTS, INC. |
Kodama-gun |
|
JP |
|
|
Family ID: |
58798167 |
Appl. No.: |
15/353200 |
Filed: |
November 16, 2016 |
Current U.S.
Class: |
1/1 |
Current CPC
Class: |
C23C 18/30 20130101;
C23C 18/1641 20130101; C23C 18/204 20130101; C23C 18/2006
20130101 |
International
Class: |
C23C 18/16 20060101
C23C018/16; C23C 18/20 20060101 C23C018/20; C23C 18/30 20060101
C23C018/30 |
Foreign Application Data
Date |
Code |
Application Number |
Dec 8, 2015 |
JP |
2015-239739 |
Claims
1. A method for manufacturing a resin article provided with a
plating film, comprising: irradiating the resin article with
ultraviolet rays; applying a catalyst to the resin article while
applying shock to the resin article that has been irradiated with
the ultraviolet rays; and performing electroless plating on the
resin article.
2. The method for manufacturing a resin article according to claim
1, wherein the shock is bubbles and/or pressure waves.
3. The method for manufacturing a resin article according to claim
2, wherein the shock is microbubbles or ultrasonic waves.
4. The method for manufacturing a resin article according to claim
1, wherein the applying includes: applying shock to the resin
article in a catalyst ion solution; and reducing catalyst ions
applied to the resin article to an electroless plating
catalyst.
5. The method for manufacturing a resin article according to claim
1, wherein in the irradiating, the resin article is irradiated with
the ultraviolet rays in an atmosphere including oxygen and/or
ozone.
6. The method for manufacturing a resin article according to claim
1, wherein a dominant wavelength of the ultraviolet rays is not
more than 243 nm.
7. The method for manufacturing a resin article according to claim
1, wherein in the irradiating, a portion of a surface of the resin
article is irradiated with ultraviolet rays, and plating is
selectively deposited on the portion of the surface of the resin
article.
8. The method for manufacturing a resin article according to claim
1, wherein the irradiating includes: irradiating a portion of a
surface of the resin article with an ultraviolet ray laser; and
irradiating a region including the portion of the surface of the
resin article with ultraviolet rays from an ultraviolet ray lamp or
an ultraviolet ray LED, and plating is selectively deposited on the
portion of the surface of the resin article.
9. The method for manufacturing a resin article according to claim
4, wherein the catalyst ions are palladium complexes of which at
least a portion has positive charge.
10. A resin article with a plating film manufactured according to
the method comprising: irradiating the resin article with
ultraviolet rays; applying a catalyst to the resin article while
applying shock to the resin article that has been irradiated with
the ultraviolet rays; and performing electroless plating on the
resin article.
11. A method for manufacturing a resin article, comprising:
irradiating the resin article with ultraviolet rays; and applying,
after the irradiating, the catalyst to a surface of the resin
article such that a plating film is deposited, while applying
bubbles and/or pressure waves against the resin article.
Description
BACKGROUND OF THE INVENTION
[0001] Field of the Invention
[0002] The present invention relates to a resin article with a
plating film and a method for manufacturing the resin article.
[0003] Description of the Related Art
[0004] A resin article with a plating film having a plating film
provided on the resin article is useful as a circuit board, a
conductive film, or the like. Also, the usage of a resin article
with a plating film is not limited to these, and for example, a
resin article with a plating film provided with a plating film of
zinc oxide or the like can be used as a functional film such as a
UV-cutting material or a photocatalyst.
[0005] Japanese Patent Laid-Open No. 2008-094923 describes a method
for manufacturing a printed circuit board with surface modification
by ultraviolet rays. Specifically, first, irradiating an entire
surface of a cycloolefin polymer material with an ultraviolet ray
lamp facilitates deposition of electroless plating. Then, a plating
film is formed by sequentially performing alkali treatment,
conditioning treatment, pre-dipping treatment, catalyst applying
treatment, activation treatment, electroless copper plating,
heating treatment, and copper electrolytic plating, and the formed
plating film is used as a material for a printed circuit board. The
obtained plating film is processed in a photolithography step and
an etching step so as to have a predetermined pattern, and thereby
the plating film having the predetermined pattern can be provided
on a cycloolefin polymer material.
SUMMARY OF THE INVENTION
[0006] According to an embodiment of the present invention, a
method for manufacturing a resin article provided with a plating
film comprises: irradiating the resin article with ultraviolet
rays; applying a catalyst to the resin article while applying shock
to the resin article that has been irradiated with the ultraviolet
rays; and performing electroless plating on the resin article.
[0007] According to another embodiment of the present invention, a
resin article with a plating film manufactured according to the
method comprises: irradiating the resin article with ultraviolet
rays; applying a catalyst to the resin article while applying shock
to the resin article that has been irradiated with the ultraviolet
rays; and performing electroless plating on the resin article.
[0008] According to still another embodiment of the present
invention, a method for manufacturing a resin article comprises:
irradiating the resin article with ultraviolet rays; and applying,
after the irradiating, the catalyst to a surface of the resin
article such that a plating film is deposited, while applying
bubbles and/or pressure waves against the resin article.
[0009] 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
[0010] FIG. 1 is a diagram illustrating a method for manufacturing
a resin article with a plating film according to one
embodiment.
[0011] FIG. 2 is a flowchart of a method for manufacturing a resin
article with a plating film according to one embodiment.
DESCRIPTION OF THE EMBODIMENTS
[0012] The alkali treatment is performed using a strong alkali
solution such as an aqueous solution of sodium hydroxide having a
concentration of about 50 g/L. There are issues in that complicated
and careful operations are required due to difficulty in handling
of such an alkali solution, and in that the alkali solution has a
high environmental load and its disposal cost is high. Also, it has
not been easy to apply a plating method in which alkali treatment
is used for a resin article that has low resistance to alkali.
Also, the conditioning treatment is performed using a conditioner
liquid containing a binder for the resin article and a catalyst,
such as an ion polymer. However, performing the conditioning
treatment is also a factor that complicates the plating step and
increases costs.
[0013] Incidentally, according to studies by the inventor of this
invention, it was found that if the alkali treatment and the
conditioning treatment are omitted, a plating film is not uniformly
deposited, and that the adhesion of the deposited plating film to
the resin article decreases.
[0014] According to one embodiment of the present invention, it is
possible to provide a new treatment method that facilitates
deposition of a plating film on the resin article.
[0015] Hereinafter, embodiments to which the present invention can
be applied will be described with reference to the drawings.
However, the scope of the present invention is not limited to the
following embodiments.
[0016] According to a manufacturing method according to this
embodiment, electroless plating is deposited on a surface of a
resin article. The manufacturing method according to this
embodiment includes an irradiating step, an applying step, and a
plating step. Hereinafter, these steps will be described in detail
with reference to FIGS. 1 and 2.
[0017] Irradiating Step
[0018] In an irradiating step (step S210), the surface of the resin
article is irradiated with ultraviolet rays. For example, when a
resin article 110 shown in FIG. 1a is irradiated with ultraviolet
rays 180, as shown in FIG. 1b, a modification portion 120 is formed
on a site that is irradiated with ultraviolet rays.
[0019] The entire surface of the resin article 110 may be
irradiated with ultraviolet rays, or a portion of the surface of
the resin article 110 may be irradiated with ultraviolet rays. For
example, if a plating film 130 is to be formed on a portion of the
surface of the resin article 110, the portion on which the plating
film 130 is to be formed can be irradiated with ultraviolet rays.
Specifically, a mask having an ultraviolet ray transmitting portion
corresponding to the shape of the portion of the surface of the
resin article 110 that is to be irradiated with ultraviolet rays is
disposed on the resin article, and the portion is irradiated with
ultraviolet rays via this mask, thereby enabling a desirable
portion to be selectively modified. In this manner, the
modification portion 120 is formed on the portion of the surface of
the resin article 110 on which the plating film 130 is to be
formed, such that an electroless plating film is selectively
deposited on the portion on which the plating film 130 is to be
formed.
[0020] Irradiation of the ultraviolet rays is performed under
conditions in which modification of the surface of the resin
article 110 proceeds. For example, in one embodiment, the resin
article 110 is irradiated with ultraviolet rays in an atmosphere
including at least one of oxygen and ozone. Also, in one
embodiment, ultraviolet rays having a wavelength of 243 nm or less
are emitted such that generation of active oxygen is promoted. In
one embodiment, ultraviolet rays having a dominant wavelength of
243 nm or less are emitted such that generation of active oxygen is
further promoted. In this specification, the dominant wavelength
indicates a wavelength at which the intensity of the ultraviolet
rays is highest in a region having a wavelength of 250 nm or less.
Specifically, in the case of a low pressure mercury vapor lamp, the
dominant wavelength is 185 nm.
[0021] When ultraviolet rays are emitted, oxygen in the atmosphere
is decomposed into ozone. Moreover, active oxygen is generated in
the process in which ozone undergoes decomposition. Bonds in
molecules that constitute the resin article 110 also are cleaved on
the surface of the resin article 110. At this time, the molecules
that constitute the resin article 110 react with the active oxygen,
and the surface of the resin article 110 is oxidized, that is, a
C--O bonds, a C.dbd.O bonds, a C(.dbd.O)--O bonds (carboxyl group
skeletal structure portion), and the like are formed on the surface
of the resin article 110. Such a hydrophilic group increases
chemical absorption between the resin article 110 and the plating
film 130. Also, a minute rough surface is formed on the portion
that has been irradiated with ultraviolet rays, due to a portion
that has been embrittled by oxidation of the surface of the resin
article 110 separating therefrom in the subsequent step such as an
applying step (step S220), for example. Physical absorption between
the resin article 110 and the plating film 130 increases due to an
anchoring effect of this rough surface. Furthermore, catalyst ions
can be selectively absorbed by the modified portion when
electroless plating is performed.
[0022] The energy of photons having a specific wavelength is
expressed with the following equations.
E=Nhc/.lamda. (KJmol.sup.-1)
N=6.022.times.10.sup.23 mol.sup.-1 (Avogadro's number)
h=6.626.times.10.sup.-37 KJs (Planck constant)
c=2.988.times.10.sup.8 ms.sup.-1 (light velocity)
.lamda.=wavelength of light (nm)
[0023] Here, the binding energy of an oxygen molecule is 490.4
KJmol.sup.-1. When this binding energy is converted to the
wavelength of light with the equations of the energy of photons,
the wavelength of light is approximately 243 nm. This indicates
that the oxygen molecules in the atmosphere absorb ultraviolet rays
having a wavelength of 243 nm or less and are decomposed.
Accordingly, ozone O.sub.3 is generated. Moreover, in the process
of decomposition of ozone, active oxygen is generated. At this
time, if ultraviolet rays having a wavelength of 310 nm or less are
present, the ozone is efficiently decomposed, and active oxygen is
generated. Furthermore, ultraviolet rays having a wavelength of 254
nm most efficiently decompose ozone.
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)
O(3P): oxygen atom in ground state
O(1D): excited oxygen atom (active oxygen)
[0024] Such ultraviolet rays can be emitted using an ultraviolet
ray lamp, an ultraviolet ray LED, or the like for emitting
ultraviolet rays continuously. Examples of the ultraviolet ray lamp
include a low pressure mercury vapor lamp and an excimer lamp. The
low pressure mercury vapor lamp can emit ultraviolet rays having
wavelengths of 185 nm and 254 nm. Also, as a reference, examples of
the excimer lamp that can be used in an air atmosphere are listed
below. In general, a Xe.sub.2 excimer lamp is used as the excimer
lamp.
[0025] Xe.sub.2 excimer lamp: wavelength 172 nm
[0026] KrBr excimer lamp: wavelength 206 nm
[0027] KrCl excimer lamp: wavelength 222 nm
[0028] On the other hand, in another embodiment, the resin article
110 can be irradiated with ultraviolet rays in an atmosphere of
another gas, such as an atmosphere of a gaseous amine compound such
as ammonia, or an atmosphere of a gaseous amide compound.
Irradiation in the atmosphere of the gaseous amine compound or the
atmosphere of the gaseous amide compound makes it possible to
oxidize the surface of the resin article 110, that is, to generate
bonds including nitrogen atoms on the surface of the resin article
110. That is, since the surface of the resin article 110 is
modified to include the nitrogen atoms, and absorption with a
plating layer is improved, an irradiated portion can be selectively
plated. If a processing object is separated from an air atmosphere
having the normal pressure, and is modified by ultraviolet rays by
changing the pressure and enclosing compound gas, a wavelength that
is suitable for a reaction can be selected as appropriate. On the
other hand, emission of ultraviolet rays having a wavelength of 243
nm or less in an air atmosphere including oxygen is advantageous in
that modification can be performed at low cost.
[0029] When the resin article 110 is irradiated with the
ultraviolet rays, the conditions for irradiation of the ultraviolet
rays are controlled such that the irradiation dose is a desirable
value. The irradiation dose of the ultraviolet rays is selected
such that the plating film 130 is deposited on the modification
portion 120 in a plating step (step S230), which will be described
later. Specifically, the irradiation dose of ultraviolet rays can
also be controlled by changing the irradiation time, the output of
the ultraviolet ray lamp, the number of ultraviolet ray lamps, the
irradiation distance, or the like.
[0030] In one embodiment, from the viewpoint of allowing plating to
be sufficiently deposited in a shorter time period, the irradiation
dose of ultraviolet rays in the irradiating step is not less than
400 mJ/cm.sup.2 and not more than 1600 mJ/cm.sup.2 at the dominant
wavelength. For example, in one embodiment in which the irradiation
intensity of the ultraviolet rays in the dominant wavelength is
1.35 mW/cm.sup.2, the irradiation time of the ultraviolet rays is
not less than 15 minutes and not more than 20 minutes. Also, in
order to promote the modification of the resin article 110, the
irradiation intensity of the ultraviolet rays is not less than 0.1
mW/cm.sup.2 in one embodiment, not less than 0.3 mW/cm.sup.2 in
another embodiment, and not less than 1.0 mW/cm.sup.2 in still
another embodiment. On the other hand, in order to prevent the
surface of the resin article 110 from becoming rough, the
irradiation intensity of the ultraviolet rays is not more than 30
mW/cm.sup.2 in one embodiment, not more than 5.0 mW/cm.sup.2 in
another embodiment, and not more than 3.0 mW/cm.sup.2 in still
another embodiment. Hereinafter, unless otherwise stated, the
irradiation dose and intensity of the ultraviolet rays indicate
values on the surface of the resin article 110 in the resin
article.
[0031] Also, in still another embodiment, after a portion of the
surface of the resin article 110 is irradiated with ultraviolet
rays using a first method (first irradiation), a region including
the portion of the surface of the resin article 110 is irradiated
with ultraviolet rays using a second method (second irradiation).
For example, strong ultraviolet rays can be emitted in the first
method, and ultraviolet rays weaker than in the first method can be
emitted in the second method.
[0032] For example, in one embodiment, after a portion of the
surface of the resin article 110 is irradiated with ultraviolet ray
laser (first irradiation), a region including the portion of the
surface of the resin article 110 is irradiated with ultraviolet
rays from an ultraviolet ray lamp or an ultraviolet ray LED (second
irradiation). As a specific example, first, a portion of the
surface of the resin article 110 on which the plating film 130 is
to be formed is irradiated with the ultraviolet ray laser. Next, a
region including the portion of the surface of the resin article
110 on which the plating film 130 is to be formed is irradiated
with ultraviolet rays from the ultraviolet ray lamp or the
ultraviolet ray LED. A region wider than the region that includes
the portion on which the plating film 130 is to be deposited may be
irradiated with ultraviolet rays from the ultraviolet ray lamp or
the ultraviolet ray LED, or the entire resin article 110 may be
irradiated with ultraviolet rays, for example. On the other hand,
the portion of the surface of the resin article 110 on which the
plating film 130 is to be formed may be selectively irradiated with
ultraviolet rays from the ultraviolet ray lamp or the ultraviolet
ray LED. Even with such a method, the modification portion 120 can
be formed on the portion that has been irradiated with the
ultraviolet ray laser, the portion being a portion of the surface
of the resin article 110, such that the plating film 130 is
selectively deposited on the portion of the surface that has been
irradiated the ultraviolet ray laser.
[0033] This method allows selective irradiation using the laser
whose beam has high straightness, and is thus advantageous in
precisely controlling the shape of the plating film 130 that is
obtained. Also, in the case where the laser is used, it takes a
shorter time to modify the surface of the resin article 110,
compared to the case where a lamp is used, and thus the degree of
temperature rise of the resin article 110 is low, and the degree of
expansion of the resin article 110 is also suppressed. Thus, it is
possible to suppress a shift in the irradiation position of the
ultraviolet rays, the shift being caused by a difference in thermal
expansion coefficient between the photomask and the resin article
110 that may possibly occur in the case where ultraviolet rays from
a lamp are emitted via the photomask. Also, though a
nanometer-order minute rough surface, laser irradiation makes it
possible to form the modification portion 120 having a larger
surface roughness than in the case where only an ultraviolet ray
lamp or the like is used. This makes it possible to improve a
bonding strength between the modification portion 120 and the
plating film 130.
[0034] On the other hand, in some cases, only irradiating the
surface of the resin article 110 with ultraviolet rays having a
large energy density such as an ultraviolet ray laser does not
cause deposition of plating on the portion that has been irradiated
with ultraviolet rays. Although the surface of the resin article
110 is modified by being irradiated with the ultraviolet ray laser,
the ultraviolet ray laser has an abrasion effect, and thus the
modified layer is removed. Thus, there is a possibility that a
given modification amount or more will not be obtained, and that
modification will not be sufficiently performed to an extent such
that plating is deposited. Abrasion refers to a phenomenon where
the surface of a material is removed due to evaporation. Usage of
ultraviolet rays emitted from an ultraviolet ray lamp or an
ultraviolet ray LED for easily introducing oxygen atoms into the
resin article 110 makes it possible to strongly modify the portion
on which the plating film 130 is to be formed such that the plating
film 130 is deposited on the resin article 110.
[0035] In one embodiment, the wavelength of the ultraviolet ray
laser is not more than 243 nm such that the generation of active
oxygen is promoted. Similarly, in one embodiment, the wavelength of
ultraviolet rays emitted from the ultraviolet ray lamp or the
ultraviolet ray LED is also not more than 243 nm such that the
generation of active oxygen is promoted.
[0036] In this case, the irradiation dose of ultraviolet rays is
adjusted such that the plating film 130 is deposited on the portion
that has been modified by both the ultraviolet ray laser and the
ultraviolet ray lamp or the ultraviolet ray LED in the plating step
(step S230), which will be described later. On the other hand, the
irradiation dose of ultraviolet rays is adjusted such that the
plating film 130 is not deposited on the portion that is irradiated
with only the ultraviolet ray lamp. Since the portion irradiated
with the laser has already modified, this portion is modified such
that the plating film 130 is deposited by weak modification
treatment with irradiation of the ultraviolet rays emitted from the
ultraviolet ray lamp, the ultraviolet ray LED, or the like for a
short time period, for example. On the other hand, a portion that
has not been irradiated with the laser is unlikely to be modified
with weak modification treatment that is additionally performed,
and thus the plating film 130 is not deposited. Therefore, even if
modification treatment is performed evenly on the entire resin
article 110, the plating film 130 can be selectively deposited on
the modification portion 120 that is irradiated with the laser, in
the plating step (step S230), which will be described later.
[0037] In order to prevent the surface of the resin article 110
from becoming rough, the irradiation intensity of the ultraviolet
ray laser for irradiation is not more than 1.0.times.10.sup.15
W/cm.sup.2 in one embodiment. Also, in order to promote
modification of the surface of the resin article 110, the
irradiation intensity of the ultraviolet ray laser for irradiation
is not less than 1.0.times.10.sup.5 W/cm.sup.2 in one embodiment.
Also, the irradiation intensity of the ultraviolet ray laser per
pulse is not less than 10 mJ/cm.sup.2 in one embodiment, and not
less than 10000 mJ/cm.sup.2 in one embodiment. For a similar
purpose, the irradiation intensity of the ultraviolet rays from the
ultraviolet ray lamp or the ultraviolet ray LED is not less than
0.1 mW/cm.sup.2 in one embodiment, not less than 0.3 mW/cm.sup.2 in
another embodiment, and not less than 1.0 mW/cm.sup.2 in still
another embodiment. On the other hand, the irradiation intensity is
not more than 30 mW/cm.sup.2 in one embodiment, not more than 5.0
mW/cm.sup.2 in another embodiment, and not more than 3.0
mW/cm.sup.2 in still another embodiment.
[0038] The conditions under which the plating is deposited may
change depending on the type of plating liquid, the type of resin
article 110, the degree of contamination of the surface of the
resin article 110, and the concentration, temperature, pH, and
time-dependent degradation of the plating liquid, fluctuation in
the output of the ultraviolet ray lamp, shifting in focus of the
ultraviolet ray laser, and the like. Therefore, it is sufficient
that the irradiation dose of ultraviolet rays is determined such
that plating is selectively deposited on only the portion on which
the plating film 130 is to be formed.
[0039] In another embodiment, after a portion of the surface of the
resin article 110 is irradiated with the ultraviolet rays from an
excimer lamp (first irradiation), a region including the portion of
the surface of the resin article 110 is irradiated with ultraviolet
rays from the ultraviolet ray lamp or the ultraviolet ray LED
(second irradiation). For example, after the portion is irradiated
with ultraviolet rays emitted from the excimer lamp via the
photomask for a short time, a region including the portion that has
been irradiated with ultraviolet rays emitted from the excimer lamp
can be irradiated with ultraviolet rays emitted from the
ultraviolet ray lamp or the ultraviolet ray LED without the
photomask. In this manner, the surface of the resin article 110 can
be modified such that the plating film 130 is deposited on the
portion that has been irradiated with ultraviolet rays from the
excimer lamp. The excimer lamp can modify the surface of the resin
article 110 in a short time period, but has the property of
inhibiting generation of some chemically-absorptive groups.
Therefore, according to such an embodiment, a shift in the
irradiation position of the ultraviolet rays can be suppressed, the
shift being caused by a difference in thermal expansion coefficient
between the photomask and the resin article 110. For example, in
one embodiment, an Xe.sub.2 excimer lamp having a wavelength of 172
nm is used as the above-described excimer lamp, and a low pressure
mercury vapor lamp having wavelengths of 185 nm and 254 nm is used
as the above-described ultraviolet ray lamp.
[0040] There is no particular limitation on the resin article 110
used in the present embodiment as long as the surface is made of a
resin material that is modifiable by ultraviolet rays. Examples of
the resin material include polyolefin such as cycloolefin polymer
or polystyrene, polyester such as polyethylene terephthalate,
polyvinyl such as polyvinyl chloride, polycarbonate, and polyimide.
If a resin material having a low alkali resistance, such as
polycarbonate or polyimide, is used, performing alkali treatment
may damage the material. Also, if a resin material having a low
alkali resistance is used and alkali treatment is performed, there
is a possibility that a portion that has not been irradiated with
ultraviolet rays will also be damaged, and the plating film 130
will be deposited easily. On the other hand, because alkali
treatment needs not to be performed in the present embodiment as
described later, the present embodiment can also be applied to a
resin material having a low alkali resistance, and the plating film
130 can be selectively deposited on a desirable portion.
[0041] There is no particular limitation on the shape of the resin
article 110. For example, the resin article 110 may be film-like or
plate-like. Furthermore, there is no particular limitation on the
thickness of the resin article 110. Also, the resin article 110
needs not to be made of only a resin. That is, in one embodiment,
the resin article 110 is a composite material having a covering
structure obtained by the surface of another material being covered
with a resin material. A specific example of the composite material
is a composite material obtained by a surface of a metal material
being covered with a resin material.
[0042] The resin article 110 has a smooth surface in one
embodiment. A more uniform plating film 130 is formed by plating
due to a smoother surface of the resin article 110. Usage of such a
smooth plating film 130 as a lead wire makes it possible to
suppress loss in a high frequency signal. According to a method for
modifying the surface of the resin article 110 with ultraviolet
rays as in the present embodiment, nanometer-order minute
unevenness is formed on the surface of the resin article 110. In
one embodiment, the surface roughness of the modification portion
120 immediately before electroless plating is performed is not more
than 10 nm. Also, in the resin article with plating film 100
according to one embodiment, the surface roughness of the surface
of the resin article 110 on the interface between the resin article
110 and the plating film 130 is not more than 10 nm. Unevenness
that is formed in this manner is expected to be much smaller than
micrometer-order unevenness that is obtained by irradiating the
surface of the resin article with a visible laser having a higher
intensity or that is formed by treatment with chromic acid or the
like, for example, and is expected to have high surface smoothness.
In this specification, the surface roughness indicates an
arithmetic average roughness Ra defined by JIS B 0601:2001.
[0043] Applying Step
[0044] As shown in FIG. 1c, in the applying step (step S220), a
catalyst is applied to the modification portion 120 while a shock
190 is applied to the resin article 110 that has been irradiated
with ultraviolet rays. Applying the catalyst while applying the
shock 190 to the resin article 110 makes it possible to easily
deposit the plating film 130 on the modification portion 120. It is
thought that the reason for this is because attachment of the
catalyst to the modification portion 120 is promoted by the shock
190 and a minute rough surface is formed due to the surface of the
modification portion 120 that has been embrittled by irradiation of
the ultraviolet rays separating therefrom. It is estimated that
physical absorption between the modification portion 120 and the
plating film 130 increases due to an anchoring effect of this
minute rough surface.
[0045] In order to facilitate deposition of the plating film, in
some cases, alkali treatment and conditioning treatment are
performed as pretreatment for electroless plating. However, as in
the present embodiment, according to the method for applying the
catalyst to the modification portion 120 while the shock 190 is
applied, the plating film 130 is easily deposited on the
modification portion 120, and thus it is not necessary to perform
alkali treatment or conditioning treatment. Of course, in order to
further facilitate deposition of the plating film 130, alkali
treatment or conditioning treatment may be further performed before
the applying step.
[0046] There is no particular limitation on the type of catalyst
that is applied to the resin article 110. In one embodiment, the
catalyst is applied to the resin article 110 by applying catalyst
ions to the surface of the resin article 110 and reducing the
catalyst ions. In this case, it is not necessary to continuously
apply shock in the series of steps including application and
reduction of catalyst ions, and shock can be applied in some of the
series of steps. For example, when the catalyst ions are applied,
shock can be applied to the resin article 110. On the other hand,
instead of using the catalyst ions, a colloidal catalyst or the
like can also be applied to the surface of the resin article
110.
[0047] Examples of the catalyst ions include a palladium complex
such as an HCl-acidic palladium complex. Also, another example of
the catalyst ion is a palladium complex in which at least a portion
of its structure has positive charge. A solution containing
palladium complex ions having positive charge in the solution is
used in one embodiment such that adherence to the modification
portion 120 is improved. An example of the palladium complex of
which at least a portion has positive charge is a complex in which
amine-based ligands are coordinately bonded. Also, another example
of the palladium complex of which at least the portion has positive
charge is a basic amino acid complex of palladium.
[0048] A specific example of the palladium complex in which at
least a portion of its structure has positive charge is a palladium
(II) basic amino acid complex included in an activator liquid (JCU
Corporation, product name: ELFSEED ES-300). Another example is a
basic amino acid complex of palladium described in WO
2007/066460.
[0049] In one embodiment in which conditioning treatment is not
performed, in order to facilitate deposition of the plating film
130, a palladium complex that partially has positive charge is used
as the catalyst. The palladium complex that partially has positive
charge easily attaches to the modification portion 120 even in the
case where the conditioning treatment is not performed. Also, a
binder that is contained in a conditioner liquid is likely to
remain on a portion that is not irradiated with ultraviolet rays,
and thus if the conditioning treatment is performed, a plating film
is deposited on an unintended portion in some cases. Thus, omission
of the conditioning treatment makes it easy to selectively deposit
the plating film 130.
[0050] There is no particular limitation on the type of shock
applied to the resin article 110 as long as the plating film 130 is
deposited easily. In one embodiment, physical shock is applied as
the shock. An example of the physical shock is mechanical shock.
Examples of the mechanical shock include applying pressure waves
against the resin article 110 and bringing a shock applying object
into contact with the resin article 110. Examples of the shock
applying object include bubbles and a shock applying member.
Hereinafter, these types of shock will be described in detail.
[0051] Direct shock is applied to the modification portion 120 in
one embodiment. However, if the plating film 130 is easily
deposited on the modification portion 120, direct shock may be
applied to a portion other than the modification portion 120 so as
to also apply shock to the modification portion 120 via the resin
article 110.
[0052] In one embodiment, pressure wave treatment for applying
pressure waves against the resin article 110 is performed. For
example, applying pressure waves to the resin article 110 in a
catalyst ion solution makes it possible to apply the catalyst to
the surface of the resin article 110. An example of the pressure
waves is a sound wave. In one embodiment, in order to facilitate
deposition of the plating film 130, ultrasonic wave treatment for
irradiating the resin article 110 with ultrasonic waves is
performed. The resin article 110 in any medium can be irradiated
with the pressure waves. For example, the resin article 110 in
water or in an aqueous solution can be irradiated with the
ultrasonic waves using an ultrasonic wave emission device.
[0053] There is no particular limitation on the irradiation time of
the pressure waves as long as the plating film 130 is deposited
easily. The irradiation time of the pressure waves is not less than
5 minutes in one embodiment such that the plating film 130 is
deposited easily. Also, the irradiation time of the pressure waves
is not less than 10 minutes in one embodiment such that the
adherence between the plating film 130 and the resin article 110 is
improved. There is no particular upper limit of the irradiation
time, and the irradiation time may be not more than 60 minutes, not
more than 30 minutes, or not more than 20 minutes, for example.
[0054] In one embodiment, bubble treatment for bringing bubbles
into contact with the resin article 110 is performed. For example,
bringing bubbles into contact with the resin article 110 in a
catalyst ion solution makes it possible to apply the catalyst to
the surface of the resin article 110. Although there is no
particular limitation on the type of bubbles, microbubble treatment
in which microbubbles are used is used to perform uniform treatment
in one embodiment. Because the microbubbles have characteristics of
generating shock waves when they collapse, it is expected that a
large shock can be applied with the microbubble treatment. The
microbubbles indicate bubbles having a diameter of about 1 .mu.m or
more and 1000 .mu.m or less. In order to perform uniform treatment,
the diameter of the microbubbles is not more than 300 .mu.m in one
embodiment, and not more than 100 .mu.m in another embodiment. On
the other hand, in order to improve the treatment efficiency with a
large shock, the diameter of the microbubbles is not less than 3
.mu.m in one embodiment, and not less than 10 .mu.m in another
embodiment.
[0055] Bubbles can be generated using a regular bubble generator.
For example, the microbubbles can be generated using a regular
microbubble generator. The bubble treatment can be performed in a
liquid using a bubble generator whose position is adjusted such
that bubbles hit the resin article 110 that is immersed in the
liquid. There is no particular limitation on the type of liquid,
and water or an aqueous solution may be used, for example. There is
no particular limitation on the bubbles, and air, oxygen, or
nitrogen can be used, for example. Also, bubbles of ozone can also
be used, expecting that the portion that has been irradiated with
ultraviolet rays is further modified.
[0056] Nanobubbles, which are bubbles smaller than the
microbubbles, can also be used as the bubbles. Because the
nanobubbles also have characteristics of generating shock waves
when they collapse, it is expected that a large shock can be
applied with the nanobubble treatment. The nanobubbles indicate
bubbles having a diameter of about 1 nm or more and 1000 nm or
less. The diameter is not more than 300 nm in one embodiment, and
not more than 100 nm in another embodiment.
[0057] There is no particular limitation on the time for bubble
treatment as long as the plating film 130 is deposited easily. The
time for bubble treatment is not less than 0.5 minutes in one
embodiment such that the plating film 130 is deposited easily.
Also, the time for bubble treatment is not less than 1 minute in
one embodiment, and not less than 2 minutes in another embodiment,
such that the adherence between the plating film 130 and the resin
article 110 is improved. There is no particular limitation on the
time for bubble treatment, and the time may be not more than 60
minutes, for example.
[0058] In one embodiment, a shock applying member is brought into
contact with the resin article 110. Shock is applied to the portion
that has been irradiated with ultraviolet rays due to contact with
the shock applying member. For example, a frictional force can be
applied to the portion of the resin article 110 that has been
irradiated with ultraviolet rays by the modification portion 120 of
the resin article 110 being rubbed using the shock applying member.
Also, a compressive force can be applied to the portion of the
resin article 110 that has been irradiated with ultraviolet rays by
projecting the shock applying member against the modification
portion 120 of the resin article 110. A specific example of one
embodiment is brushing for rubbing the modification portion 120
with a brush.
[0059] For example, the catalyst can be applied to the surface of
the resin article 110 by rubbing the resin article 110 with a brush
in a catalyst ion solution or rubbing the resin article 110
moistened with the catalyst ion solution with a brush.
[0060] As described above, applying the catalyst to the surface of
the resin article 110 can be performed by bringing the catalyst ion
solution into contact with the resin article 110 while applying the
shock 190 to the resin article 110.
[0061] If the catalyst ions are applied to the surface of the resin
article 110, applying the catalyst to the surface of the resin
article 110 is completed by reducing the catalyst ions. There is no
particular limitation on a method for reducing the catalyst ions,
and a reducing agent such as hydrogen gas, dimethylamine borane, or
sodium borohydride can be used. As a specific method, the catalyst
ions can be reduced and deposited by immersing the resin article
110 in a solution containing a reducing agent. A specific example
of the reducing agent is a cationic detergent such as an
accelerator liquid (JCU Corporation, product name: ELFSEED ES-400).
It is not essential to apply shock to the resin article 110 when
the catalyst ions are reduced.
[0062] Plating Step
[0063] In the plating step (step S230), electroless plating is
performed on the resin article 110 to which the catalyst has been
applied. As a result, as shown in FIG. 1d, the plating film 130 is
formed. In this manner, the resin article with plating film 100 is
manufactured. In the irradiating step (step S210) and the applying
step (step S220), modification and application of the catalyst are
selectively performed such that the plating film 130 is deposited
on a desirable modification portion 120. Therefore, even if the
entire resin article 110 is immersed in a plating liquid, for
example, the plating film 130 is selectively deposited on a
desirable modification portion 120. Also, the plating film is not
deposited on portions that are adjacent to the desirable portion.
Therefore, it is not essential to form a pattern of the plating
film with photolithography and etching after the formation of the
plating film 130.
[0064] In one embodiment, the plating film 130 is formed with an
electroless plating method. There is no particular limitation on a
specific electroless plating method. Examples of the electroless
plating method that can be adopted include an electroless plating
method in which a formalin-based electroless plating bath is used,
and an electroless plating method in which hypophosphorous acid,
which has a slow deposition speed but can be easily handled, is
used as the reducing agent. Specific examples of the electroless
plating method include electroless nickel plating, electroless
copper plating, electroless copper/nickel plating, zinc oxide
electroless plating, or the like. The plating film 130 that is to
be formed is a metal film in one embodiment, and may be a ceramic
film such as a zinc oxide plating film. The adherence between the
modification portion 120 and the deposited plating film 130 is
improved by modifying the resin article 110 as described above.
[0065] The electroless plating can be performed using an
electroless plating liquid set such as Cu--Ni plating liquid set
"AISL" produced by JCU Corporation, for example.
[0066] In another embodiment, the plating film 130 may be formed
with a high-speed electroless plating method. According to the
high-speed electroless plating method, a thicker plating film can
be formed. In still another embodiment, plating is deposited with
an electrolytic plating method on the plating film 130 that has
been formed with electroless plating. According to this method, a
much thicker plating film 130 can be formed. There is no particular
limitation on a specific electrolytic plating method.
[0067] There is no particular limitation on the thickness of the
obtaining plating film 130. The plating film 130 having an
appropriate thickness is formed in accordance with a usage of the
resin article with plating film 100 that is to be obtained.
[0068] The resin article with plating film 100 that has been
obtained in this manner includes the resin article 110 having the
modification portion 120 that has been modified by irradiation of
the ultraviolet rays and application of shock, and the plating film
130 that has been formed on the modification portion 120. The resin
article with plating film 100 that has been obtained in this manner
can be used as various applications such as a circuit board, a
conductive film, a UV-cutting material, and a photocatalyst.
[0069] In the present embodiment in which a step of applying a
catalyst while applying shock is used, alkali treatment in which
alkali is used, and conditioning treatment in which a conditioner
liquid containing a binder for a resin article and a catalyst is
used are not required. Thus, the resin article with plating film
100 can be produced with a simpler method. Also, the present
embodiment in which alkali treatment is not required can also be
applied to the resin article 110 having a low alkali resistance. In
one embodiment, alkali treatment in which an alkali liquid having a
pH of 13 or more is used is not performed from the irradiating step
(step S210) to the plating step (step S230), that is, from when the
modification portion 120 is formed by irradiation of the
ultraviolet rays to when the plating film 130 is formed. In another
embodiment, alkali treatment is not performed from when the
modification portion 120 is formed by irradiation of the
ultraviolet rays to when the plating film 130 is formed.
EXAMPLES
Example 1
[0070] A cycloolefin polymer material (produced by Zeon
Corporation, ZeonorFilm ZF-16, film thickness 100 .mu.m, surface
roughness Ra=0.47 nm), which is the resin material, was used as a
substrate.
[0071] First, before the surface was modified, the substrate was
subjected to ultrasonic wave cleaning with pure water at 50.degree.
C. for 3 minutes for the purpose of cleaning the substrate surface,
and then the substrate was dried.
[0072] Next, a portion of the substrate was irradiated with
ultraviolet rays that were emitted from an ultraviolet ray lamp via
a quartz/chromium mask that was placed on the substrate in an air
atmosphere. The details of the ultraviolet ray lamp (low pressure
mercury vapor lamp) that was used in this example are described
below. A surface roughness Ra of the substrate after being
irradiated with ultraviolet rays was 0.26 nm.
[0073] Low pressure mercury vapor lamp: UV-300 (dominant wavelength
185 nm, 254 nm) produced by Samco Inc.:
[0074] Irradiation distance: 3.5 cm
[0075] Irradiation time: 15 minutes
[0076] Luminous intensity at an irradiation distance of 3.5 cm:
5.40 mW/cm.sup.2 (254 nm) [0077] 1.35 mW/cm.sup.2 (185 nm)
[0078] Next, catalyst applying treatment was performed on the
substrate while ultrasonic wave treatment was performed on the
substrate that had been irradiated with ultraviolet rays.
Specifically, the catalyst applying treatment was performed for 10
minutes on the substrate in an activator liquid (JCU Corporation,
product name ELFSEED ES-300) that had been heated to 50.degree. C.,
using an ultrasonic wave cleaning device (produced by Sharp
Corporation, UT-206H, frequency 37 kHz, output 100%). Thereafter,
the substrate was cleaned in pure water.
[0079] Next, reduction treatment was performed on the substrate.
Specifically, an accelerator liquid (JCU Corporation, product name
ELFSEED ES-400) was heated to 50.degree. C. and the substrate was
immersed in the heated accelerator liquid for 2 minutes.
Thereafter, the substrate was cleaned in pure water.
[0080] Next, electroless copper-nickel plating was performed on the
substrate. Specifically, an electroless Cu--Ni plating liquid that
is used in the plating liquid set "AISL" produced by JCU
Corporation was heated to 60.degree. C. and the substrate was
immersed in the heated plating liquid for 5 minutes. Thereafter,
the substrate was cleaned in pure water and dried. In this manner,
the resin article with plating film was produced.
[0081] When the obtained resin article with plating film was
observed, the plating film was evenly deposited on portions that
were irradiated with ultraviolet rays, and the plating film was not
deposited on portions that were not irradiated with ultraviolet
rays.
Example 2
[0082] A resin article with a plating film was produced similarly
to Example 1 except that the catalyst applying processing was
performed for 20 minutes in Example 2. When the obtained resin
article with the plating film was observed, the plating film was
evenly deposited on portions that were irradiated with ultraviolet
rays, and the plating film was not deposited on portions that were
not irradiated with ultraviolet rays.
Comparative Examples 1 and 2
[0083] Resin articles with plating films were produced similarly to
Examples 1 and 2 except that ultrasonic wave treatment was not
performed when the catalyst applying treatment was performed in
Comparative Examples 1 and 2. When the obtained resin articles with
plating films were observed, the plating film was deposited on the
circumferential edge portions of regions that were irradiated with
ultraviolet rays in all resin articles, but the plating film was
not deposited on a central portion of the region that was
irradiated with ultraviolet rays.
[0084] According to the results of the examples and the comparative
examples, it was confirmed that performing the catalyst applying
treatment while applying shock makes it possible to sufficiently
deposit plating on portions that were irradiated with ultraviolet
rays.
[0085] Regarding the resin articles with plating films that were
produced in Examples 1 and 2, the adherence of the plating films to
the substrates was evaluated. A tape testing method conforming to
JIS H 8504:1996 was used to evaluate the adherence. When tape was
attached to and peeled off from the resin articles with plating
films that were produced in Examples 1 and 2, separation of the
plating films was not observed. In this manner, it was confirmed
that performing the catalysts applying treatment while performing
the ultrasonic wave treatment makes it possible to sufficiently
deposit plating on the portions that were irradiated with
ultraviolet rays, and that the adherence of the plating film to the
substrate is favorable.
[0086] From the above-described results, it was found that
performing the catalyst applying treatment while applying shock
allows the plating film to be uniformly deposited on the resin
article even if alkali treatment and conditioning treatment are
omitted, and the adherence of the plating film to the resin article
is favorable. On the other hand, it was confirmed that in the case
where shock is not applied, if alkali treatment and conditioning
treatment are not performed, plating is not favorably deposited. It
was confirmed that plating is easily deposited by applying a
catalyst while applying shock.
[0087] 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.
[0088] This application claims the benefit of Japanese Patent
Application No. 2015-239739, filed Dec. 8, 2015, which is hereby
incorporated by reference herein in its entirety.
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