U.S. patent application number 14/973804 was filed with the patent office on 2016-06-30 for resin article and method of manufacturing resin article.
The applicant listed for this patent is CANON COMPONENTS, INC.. Invention is credited to Taisuke IWASHITA.
Application Number | 20160186324 14/973804 |
Document ID | / |
Family ID | 54784389 |
Filed Date | 2016-06-30 |
United States Patent
Application |
20160186324 |
Kind Code |
A1 |
IWASHITA; Taisuke |
June 30, 2016 |
RESIN ARTICLE AND METHOD OF MANUFACTURING RESIN ARTICLE
Abstract
There is provided with a method of manufacturing a resin
article. A surface of a resin article is modified such that a
plating layer can be deposited. In the modification, ultraviolet
light is irradiated on the resin article, and shock is applied to
the resin article after the ultraviolet light is irradiated.
Inventors: |
IWASHITA; Taisuke;
(Saitama-ken, JP) |
|
Applicant: |
Name |
City |
State |
Country |
Type |
CANON COMPONENTS, INC. |
Saitama-ken |
|
JP |
|
|
Family ID: |
54784389 |
Appl. No.: |
14/973804 |
Filed: |
December 18, 2015 |
Current U.S.
Class: |
428/457 ;
427/553; 427/554 |
Current CPC
Class: |
H05K 3/00 20130101; H05K
2203/0285 20130101; C23C 18/2086 20130101; H05K 3/185 20130101;
C23C 18/204 20130101; C23C 18/2013 20130101; C23C 18/30 20130101;
C23C 18/2006 20130101; C23C 18/1605 20130101 |
International
Class: |
C23C 18/18 20060101
C23C018/18; C23C 18/16 20060101 C23C018/16 |
Foreign Application Data
Date |
Code |
Application Number |
Dec 25, 2014 |
JP |
2014-263304 |
Claims
1. A method of manufacturing a resin article, comprising: modifying
a surface of a resin article such that a plating layer can be
deposited, the modifying comprises: irradiating ultraviolet light
on the resin article, and applying shock to the resin article after
the ultraviolet light is irradiated.
2. The method according to claim 1, wherein in applying the shock,
a pressure wave is applied to the resin article.
3. The method according to claim 2, wherein the pressure wave is an
ultrasonic wave.
4. The method according to claim 1, wherein in applying the shock,
an air bubble is applied to the resin article.
5. The method according to claim 4, wherein the air bubble is a
microbubble.
6. The method according to claim 2, wherein the shock is applied in
an alkaline solution.
7. The method according to claim 2, wherein the shock is applied in
a solution containing a surfactant.
8. The method according to claim 1, wherein in applying the shock,
a shock applying member is put in contact with the resin
article.
9. The method according to claim 1, wherein in the irradiating, the
ultraviolet light is irradiated in an atmosphere that contains at
least one of oxygen or ozone.
10. The method according to claim 1, wherein a primary wavelength
of the ultraviolet light is 243 nm or less.
11. The method according to claim 1, wherein in the irradiating,
ultraviolet light is irradiated on a portion of the surface of the
resin article such that a plating layer can be selectively
deposited in the portion of the surface of the resin article.
12. The method according to claim 1, wherein the irradiating
includes irradiating an ultraviolet light laser beam on a portion
of the surface of the resin article, and irradiating ultraviolet
light from an ultraviolet light lamp or an ultraviolet light LED on
a region that includes the portion of the surface of the resin
article, such that a plating layer can be selectively deposited in
the portion of the surface of the resin article.
13. The method according to claim 1, further comprising: performing
electroless plating on the resin article that has been
modified.
14. A resin article comprising: a resin article; and a plating
layer, wherein the plating layer is manufactured according to a
method comprising: irradiating ultraviolet light on the resin
article; applying shock to the resin article after the ultraviolet
light is irradiated; and performing electroless plating on the
resin article to which the shock has been applied.
15. A resin article, comprising: a resin article having a modified
portion that was modified by irradiating ultraviolet light and
applying a shock; and a plating layer that was formed on the
modified portion.
Description
BACKGROUND OF THE INVENTION
[0001] 1. Field of the Invention
[0002] The present invention relates to a resin article and a
method of manufacturing a resin article.
[0003] 2. Description of the Related Art
[0004] A resin article having a plating layer that has a plating
layer 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] Japanese Patent Laid-Open No. 2008-094923 describes a method
of manufacturing a printed circuit board using surface modification
by ultraviolet light. Specifically, first, an ultraviolet light
lamp is irradiated on an entire surface of a cyclo-olefin polymer
material, to enable easier depositing of electroless plating. Then,
a plating layer is formed by successively performing alkali
treatment, conditioning treatment, pre-dipping treatment, catalyst
providing treatment, activation treatment, electroless copper
plating, heat treatment, and electroless copper plating, 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.
SUMMARY OF THE INVENTION
[0006] According to an embodiment of the present invention, a
method of manufacturing a resin article comprises: modifying a
surface of a resin article such that a plating layer can be
deposited, the modifying comprises: irradiating ultraviolet light
on the resin article, and applying shock to the resin article after
the ultraviolet light is irradiated.
[0007] According to another embodiment of the present invention, a
resin article comprises: a resin article; and a plating layer,
wherein the plating layer is manufactured according to a method
comprising: irradiating ultraviolet light on the resin article;
applying shock to the resin article after the ultraviolet light is
irradiated; and performing electroless plating on the resin article
to which the shock has been applied.
[0008] According to still another embodiment of the present
invention, a resin article having a plating layer comprises: a
resin article having a modified portion that was modified by
irradiating ultraviolet light and applying a shock; and a plating
layer that was formed on the modified portion.
[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] FIGS. 1A to 1D illustrate a method of manufacturing a resin
article having a plating layer according to one embodiment.
[0011] FIG. 2 is a flowchart of a method of manufacturing a resin
article having a plating layer according to one embodiment.
DESCRIPTION OF THE EMBODIMENTS
[0012] Alkali treatment is performed using a strong alkaline
solution such as a sodium hydroxide aqueous solution or the like
having a concentration of approximately 50 g/L. This sort of strong
alkaline solution is not easy to handle, and therefore has problems
in that operation is complicated and requires careful attention,
and also has problems in that a strong alkaline solution has a high
environmental burden and disposal costs. Also, it is not easy to
apply a plating method using alkali treatment to a resin article
having low resistance to strong alkali. On the other hand,
according to investigations by the inventors of the present
application, it was found that when alkali treatment is omitted,
the plating layer may not be uniformly deposited, and there is a
reduction in adhesiveness of the deposited plating layer to the
resin article.
[0013] According to an embodiment of the present invention, a
plating layer can be formed on a resin article by a simple
method.
[0014] Below 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.
[0015] According to a modification method according to the present
embodiment, the surface of a resin article is modified such that
electroless plating will be deposited. By using this modification
method, it is possible to manufacture a resin article whose surface
has been modified such that a plating layer will be deposited. The
modification method according to the present embodiment includes an
irradiation step and a shock applying step. Also, a method of
manufacturing a resin article having a plating layer according to
the present embodiment includes a modification step of modifying
the surface of a resin article using the modification method
according to the present embodiment, and a plating step. Below,
these steps will be described in detail with reference to FIGS. 1A
to 1D and FIG. 2.
[0016] (Irradiation Step)
[0017] In an irradiation step (S210), ultraviolet light is
irradiated on the surface of a resin article. For example, when
ultraviolet light 180 is irradiated on a resin article 110 shown in
FIG. 1A, a modified portion 120 is formed at a location where the
ultraviolet light was irradiated, as shown in FIG. 1B.
[0018] Ultraviolet light may be irradiated on the entire surface of
the resin article 110, or may be irradiated on only a portion of
the surface of the resin article 110. For example, in a case where
a plating layer 130 is intended to be formed in a portion of the
surface of the resin article 110, ultraviolet light can be
irradiated on the portion where the plating layer 130 is intended
to be formed. Specifically, by arranging a mask that has a
UV-transmissive portion corresponding to the shape of a portion
where ultraviolet light will be irradiated among the surface of the
resin article 110, and irradiating ultraviolet light via this mask,
it is possible to selectively modify a desired portion. Thus, such
that an electroless plating layer will be selectively deposited in
a portion where the plating layer 130 is intended to be formed, the
modified portion 120 is formed in a portion of the surface of the
resin article 110 where the plating layer 130 is intended to be
formed.
[0019] Irradiation of ultraviolet light is performed under
conditions in which modification of the surface of the resin
article 110 will proceed. For example, in one embodiment,
ultraviolet light is irradiated on the resin article 110 in an
atmosphere containing at least one of oxygen and ozone. Also, in
one embodiment, such that generation of active oxygen is promoted,
ultraviolet light having a wavelength of 243 nm or less is
irradiated. In one embodiment, such that generation of active
oxygen is further promoted, ultraviolet light having a primary
wavelength of 243 nm or less is irradiated. In the present
specification, 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.
[0020] When ultraviolet light is irradiated, oxygen in the
atmosphere is decomposed, generating ozone. Further, active oxygen
is generated in the course of ozone decomposing. 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 adhesiveness of the resin article 110 and the plating
layer 130. 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 a shock applying step (S220) for example, a fine rough face is
formed in a portion where ultraviolet light has been irradiated.
Because of this rough face, physical adhesiveness of the plating
layer 130 to the resin article 110 increases due to an anchoring
effect. Further, a portion that has been modified can selectively
adsorb catalyst ions when performing electroless plating.
[0021] 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.23 mol.sup.-1 (Avogadro's constant)
h=6.626.times.10.sup.-37 KJs (Plank's constant)
c=2.988.times.10.sup.8 ms.sup.-1 (speed of light)
.lamda.=light wavelength (nm)
[0022] 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
light 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 is
ultraviolet light with a wavelength of 310 nm or less, ozone is
efficiently decomposed, and active oxygen is generated. Further,
ultraviolet light with a wavelength of 254 nm decomposes ozone most
efficiently.
[0023] O.sub.2+h.nu. (243 nm or less).fwdarw.O(3P)+O(3P)
[0024] O.sub.2+O (3P).fwdarw.O.sub.3 (ozone)
[0025] O.sub.3+h.nu. (310 nm or less).fwdarw.O.sub.2+O(1D) (active
oxygen)
[0026] O(3P): ground state oxygen atom
[0027] O(1D): excited oxygen atom (active oxygen)
[0028] Such ultraviolet light can be irradiated using an
ultraviolet light lamp or an ultraviolet light LED or the like that
continuously radiates ultraviolet light. Examples of an ultraviolet
light lamp include a low pressure mercury lamp, an excimer lamp,
and the like. A low pressure mercury lamp can irradiate ultraviolet
light 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. Ordinarily an Xe.sub.2 excimer lamp is used as an
excimer lamp.
[0029] Xe.sub.2 excimer lamp: wavelength 172 nm
[0030] KrBr excimer lamp: wavelength 206 nm
[0031] KrCl excimer lamp: wavelength 222 nm
[0032] On the other hand, in another embodiment, irradiation of
ultraviolet light 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 adhesiveness 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 light in an altered pressure or under compound gas
after isolating the item to be processed from an atmosphere at
normal pressure it is possible to suitably select a wavelength
appropriate for the reaction. On the other hand, irradiating
ultraviolet light having a wavelength of 243 nm or less in air
including oxygen is advantageous because modification can be
performed with low cost.
[0033] When irradiating ultraviolet light on the resin article 110,
ultraviolet light irradiation conditions are controlled such that
the irradiation amount becomes a desired value. The irradiation
amount of ultraviolet light is selected such that the plating layer
130 will be deposited in the modified portion 120 in a plating step
(S230) described later. Specifically, the irradiation amount of
ultraviolet light can be controlled by changing the irradiation
time, or by changing the output, lamp quantity, irradiation
distance, or the like of the ultraviolet light lamp.
[0034] In one embodiment, from the viewpoint of adequately causing
plating to be deposited in a shorter time period, the irradiation
amount of ultraviolet light in the irradiation step is set to at
least 400 mJ/cm.sup.2 and not more than 1,600 mJ/cm.sup.2 at the
primary wavelength. For example, in one embodiment in which the
irradiation intensity of ultraviolet light at the primary
wavelength is 1.35 mW/cm.sup.2, the irradiation time of ultraviolet
light is set to at least 5 minutes and not more than 20 minutes.
Also, the irradiation intensity of ultraviolet light, in order to
promote modification of the resin article 110, in one embodiment is
set to at least 0.1 mW/cm.sup.2, and in another embodiment is set
to at least 0.3 mW/cm.sup.2, and in still another embodiment is set
to at least 1.0 mW/cm.sup.2. On the other hand, the irradiation
intensity of ultraviolet light, in order to prevent the surface of
the resin article 110 from being greatly roughened, in one
embodiment is set to not more than 30 mW/cm.sup.2, and in another
embodiment is set to not more than 5.0 mW/cm.sup.2, and in still
another embodiment is set to not more than 3.0 mW/cm.sup.2. Below,
unless specifically stated otherwise, the irradiation amount and
irradiation intensity of ultraviolet light refer to values on the
surface of the resin article 110 at the primary wavelength.
[0035] Also, in still another embodiment, after performing
irradiation of ultraviolet light using a first method (first
irradiation) in a portion of the surface of the resin article 110,
ultraviolet light is irradiated using a second method (second
irradiation) in a region that includes a portion of the surface of
the resin article 110. For example, it is possible to irradiate
intense ultraviolet light in the first method, and possible to
irradiate weaker ultraviolet light than in the first method in the
second method.
[0036] For example, in one embodiment, after irradiating (first
irradiation) an ultraviolet light laser beam in a portion of the
surface of the resin article 110, ultraviolet light is irradiated
(second irradiation) from an ultraviolet light lamp or an
ultraviolet light LED in a region that includes a portion of the
surface of the resin article 110. As a specific example, first, an
ultraviolet light laser beam is irradiated in a portion of the
surface of the resin article 110 where the plating layer 130 is
intended to be formed. Next, ultraviolet light is irradiated from
an ultraviolet light lamp or an ultraviolet light LED in a region
that includes the portion of the surface of the resin article 110
where the plating layer 130 is intended to be formed. The
ultraviolet light from an ultraviolet light lamp or an ultraviolet
light LED may be irradiated in a larger region that encompasses the
portion where the plating layer 130 is intended to be caused to be
deposited, and for example may be irradiated on the entire resin
article 110. On the other hand, the ultraviolet light from an
ultraviolet light lamp or an ultraviolet light LED may be
selectively irradiated in the portion of the surface of the resin
article 110 where the plating layer 130 is intended to be formed.
With this sort of method as well, it is possible to form the
modified portion 120 in a portion where an ultraviolet light laser
beam has been irradiated, which is a portion of the surface of the
resin article 110, such that the plating layer 130 will be
selectively deposited in the portion of the surface where an
ultraviolet light laser beam has been irradiated.
[0037] This method is advantageous for being able to precisely
control the shape of the plating layer 130 to be obtained, in order
to selectively perform irradiation using a laser beam having a high
degree of rectilinearity. Also, the temperature of the resin
article 110 increases less easily when using a laser than when
using a lamp. Therefore, it is possible to suppress a shift in the
position of ultraviolet light irradiation due to differences in the
thermal expansion coefficient between the photomask and the resin
article 110.
[0038] On the other hand, there are cases where plating is not
deposited in a portion where ultraviolet light was irradiated by
merely irradiating ultraviolet light having a high energy density,
such as with an ultraviolet light laser beam, on the surface of the
resin article 110. The surface of the resin article 110 is modified
by irradiating an ultraviolet light laser beam, but the modified
layer is eliminated due to the ablation effect in an ultraviolet
light laser beam. Therefore, it is possible that only a certain
amount of modification is obtained, and an amount of modification
sufficient for plating to be deposited cannot be obtained. Ablation
is a phenomenon where the surface of material is removed by
evaporation. By using ultraviolet light from an ultraviolet light
lamp or an ultraviolet light LED, which can easily introduce oxygen
atoms to the resin article 110, it is possible to more strongly
modify a portion where the plating layer 130 is intended to be
formed, such that the plating layer 130 will be deposited on the
resin article 110.
[0039] In one embodiment, the wavelength of the ultraviolet light
laser beam is not more than 243 nm, such that generation of active
oxygen is promoted. Likewise, in one embodiment, the wavelength of
ultraviolet light from an ultraviolet light lamp or an ultraviolet
light LED also is not more than 243 nm, such that generation of
active oxygen is promoted.
[0040] In this case, the irradiation amount of ultraviolet light is
adjusted such that the plating layer 130 will be deposited in a
portion that has been modified using both the ultraviolet light
laser and the ultraviolet light lamp or the ultraviolet light LED
in a plating step (S230) described later. On the other hand, the
irradiation amount of ultraviolet light is adjusted such that the
plating layer 130 will not be deposited in a portion where only the
ultraviolet light lamp was irradiated. In a portion where the laser
beam is being intensely irradiated, modification is already
progressing, so modification such that the plating layer 130 will
be deposited is performed with weak modifying treatment, for
example treatment in which ultraviolet light is irradiated for a
short time from an ultraviolet light lamp or an ultraviolet light
LED or the like. On the other hand, in a portion where the laser
beam has not been irradiated, modification does not progress much
with only weak modifying treatment performed additionally, and so
the plating layer 130 will not be deposited. Accordingly, even in a
case where modifying treatment is performed uniformly on the entire
resin article 110, in the plating step (S230) described later, it
is possible to selectively cause the plating layer 130 to be
deposited in the modified portion 120 where the laser beam has been
irradiated.
[0041] The irradiation intensity of the irradiated ultraviolet
light laser beam, in order to prevent the surface of the resin
article 110 from being greatly roughened, in one embodiment is set
to not more than 1.0.times.10.sup.15 W/cm.sup.2. Also, in order to
promote modification of the surface of the resin article 110, the
irradiation intensity of the irradiated ultraviolet light laser
beam, in one embodiment is set to at least 1.0.times.10.sup.5
W/cm.sup.2. Also, the irradiation intensity of the ultraviolet
light laser beam per pulse, in one embodiment is set to at least 10
mJ/cm.sup.2, and in one embodiment is set to not more than 10,000
mJ/cm.sup.2. For the same reason, the irradiation intensity of
ultraviolet light from the ultraviolet light lamp or the
ultraviolet light LED, in one embodiment is set to at least 0.1
mW/cm.sup.2, and in another embodiment is set to at least 0.3
mW/cm.sup.2, and in still another embodiment is set to at least 1.0
mW/cm.sup.2. On the other hand, the irradiation intensity of
ultraviolet light from the ultraviolet light lamp or the
ultraviolet light LED, in one embodiment is set to not more than 30
mW/cm.sup.2, and in another embodiment is set to not more than 5.0
mW/cm.sup.2, and in still another embodiment is set to not more
than 3.0 mW/cm.sup.2.
[0042] 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
light lamp, focus shift of the ultraviolet light laser, and the
like. Accordingly, the irradiation amount of ultraviolet light can
be determined such that plating is selectively deposited only in a
portion where the plating layer 130 is intended to be formed.
[0043] In another embodiment, after irradiating (first irradiation)
ultraviolet light from an excimer lamp in a portion of the surface
of the resin article 110, ultraviolet light is irradiated (second
irradiation) from an ultraviolet light lamp or an ultraviolet light
LED in a region that includes a portion of the surface of the resin
article 110. For example, after irradiating ultraviolet light for a
short time from the excimer lamp via a photomask, it is possible to
irradiate ultraviolet light from an ultraviolet light lamp or an
ultraviolet light LED, not via a photomask, in a region that
includes the portion where ultraviolet light was irradiated from
the excimer lamp. Thus, it is possible to modify the surface of the
resin article 110 such that the plating layer 130 will be deposited
in the portion where ultraviolet light was irradiated from the
excimer lamp. The excimer lamp has properties such that the surface
of the resin article 110 can be modified in a short time, but a
chemical adsorption group is difficult to generate in some of the
surface. Accordingly, according to this sort of embodiment, it is
possible to suppress a shift in the position of ultraviolet light
irradiation due to differences in the 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 lamp having wavelengths of 185 nm and 254 nm is used as the
above-described ultraviolet light lamp.
[0044] The resin article 110 used in the present embodiment is not
particularly limited, as long as the resin article 110 has a
surface formed with resin material that can be modified by
ultraviolet light. Examples of the resin material include 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. In a
case of using a resin material having a low alkali resistance such
as a polycarbonate or polyimide, when performing alkali treatment
using a strong alkali, it is possible that the material will be
damaged. Also, in a case of using a resin material having a low
alkali resistance, when performing alkali treatment using a strong
alkali, it is possible that a portion where ultraviolet light has
not been irradiated will also be damaged, and so the plating layer
130 will easily be deposited there. On the other hand, as described
later, in the present embodiment it is not necessary to use a
strong alkali, and in fact it is not necessary to use alkali
treatment itself, so this embodiment is also applicable to a resin
material having a low alkali resistance, and the plating layer 130
can be selectively caused to be deposited in a desired portion.
[0045] 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.
[0046] 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 130 is formed by plating. By using such
a smooth plating layer 130 as conductive wiring, it is possible to
reduce high frequency signal loss. According to a method of
modifying the surface of the resin article 110 using ultraviolet
light as in the present embodiment, nanometer-order fine roughness
is formed in the surface of the resin article 110. In one
embodiment, surface roughness of the modified portion 120
immediately before performing electroless plating is 10 nm or less.
Also, in a resin article 100 having a plating layer according to
the present embodiment, surface roughness of the resin article 110
surface at the interface of the resin article 110 and the plating
layer 130 is 10 nm or less. Roughness formed in this way is
expected to be remarkably small compared to micrometer-order
roughness 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,
and so a high degree of surface smoothness is expected. In the
present specification, surface roughness refers to arithmetic mean
roughness Ra defined by JIS B0601: 2001.
[0047] (Shock Applying Step)
[0048] In a shock applying step (S220), as shown in FIG. 1C, a
shock 190 is applied to the resin article 110 that has been
irradiated with ultraviolet light. By applying a shock to the resin
article 110, the plating layer 130 becomes more easily deposited in
the modified portion 120. It is conceivable that a reason for this
is that a fine rough face is formed by loss of the surface of the
modified portion 120 made brittle by irradiation of ultraviolet
light. It is presumed that because of this fine rough face,
physical adhesiveness of the modified portion 120 and the plating
layer 130 increases due to an anchoring effect. In one embodiment,
a shock is applied directly to the modified portion 120. However,
as long as the plating layer 130 becomes easily deposited in the
modified portion 120, a shock may be applied directly to a portion
other than the modified portion 120 such that a shock is also
applied to the modified portion 120 via the resin article 110.
[0049] The type of shock applied to the resin article 110 is not
particularly limited as long as the plating layer 130 becomes
easily deposited. In one embodiment, a physical shock is applied as
the shock. An example of a physical shock is a mechanical shock.
Examples of a mechanical shock include applying a pressure wave to
the resin article 110 or placing a shock applying body in contact
with the resin article 110. Examples of a shock applying body
include an air bubble or a shock applying member. Below, these
shocks will be described in detail.
[0050] In one embodiment, a pressure wave treatment that applies a
pressure wave to the resin article 110 is performed. An example of
a pressure wave is a sound wave. In one embodiment, an ultrasonic
wave treatment that irradiates an ultrasonic wave on the resin
article 110 is performed such that the plating layer 130 will be
more easily deposited. The pressure wave can be irradiated on the
resin article 110 in an arbitrary medium. For example, it is
possible to irradiate an ultrasonic wave on the resin article 110
in water or an aqueous solution using an ultrasonic wave
irradiation device.
[0051] The irradiation time of the pressure wave is not
particularly limited as long as the plating layer 130 becomes
easily deposited. In one embodiment the irradiation time of the
pressure wave is set to at least 2 minutes, such that the plating
layer 130 becomes easily deposited. Also, such that adhesiveness of
the plating layer 130 and the resin article 110 improves, in one
embodiment the irradiation time of the pressure wave is set to at
least 5 minutes, and in still another embodiment the irradiation
time of the pressure wave is set to at least 10 minutes. The
irradiation time does not particularly have an upper limit, and for
example may be set to 60 minutes or less.
[0052] In one embodiment, air bubble treatment that places an air
bubble in contact with the resin article 110 is performed. The type
of air bubble is not particularly limited, but in one embodiment a
microbubble treatment using microbubbles is used in order to
perform uniform treatment. Microbubbles have properties of
producing a shock wave when the bubbles are broken, so by using
microbubble treatment it is expected that a large shock will be
applied. Microbubbles refers to air bubbles having a diameter of
approximately at least 1 .mu.m and not more than 1,000 .mu.m. In
order to perform uniform treatment, the diameter of microbubbles in
one embodiment is not more than 300 .mu.m, and in still another
embodiment is not more than 100 .mu.m. On the other hand, in order
to increase the shock and improve treatment efficiency, the
diameter of microbubbles in one embodiment is at least 3 .mu.m, and
in still another embodiment is at least 10 .mu.m.
[0053] Air bubbles can be generated using an ordinary air bubble
generating apparatus. For example, microbubbles can be generated
using an ordinary microbubble generating apparatus. Air bubble
treatment can be performed in a liquid, by using an air bubble
generating apparatus whose position has been adjusted such that air
bubbles are applied to the resin article 110 that has been immersed
in the liquid. The type of liquid is not particularly limited, and
for example can be water or an aqueous solution. The type of air
bubbles is not particularly limited, and for example air, oxygen,
or nitrogen bubbles can be used. Also, with the expectation of
further modifying a portion where ultraviolet light has been
irradiated, it is also possible to use ozone bubbles.
[0054] The air bubble treatment time is not particularly limited as
long as the plating layer 130 becomes easily deposited. In one
embodiment the air bubble treatment time is set to at least 0.5
minutes, such that the plating layer 130 becomes easily deposited.
Also, such that adhesiveness of the plating layer 130 and the resin
article 110 improves, in one embodiment the air bubble treatment
time is set to at least 1 minute, and in still another embodiment
the air bubble treatment time is set to at least 2 minutes. The air
bubble treatment time does not particularly have an upper limit,
and for example may be set to 60 minutes or less.
[0055] Nanobubbles, which are even finer bubbles than microbubbles,
may also be used, and nanobubbles refers to air bubbles having a
diameter of approximately at least 1 nm and not more than 1,000 nm.
The diameter of nanobubbles in one embodiment is not more than 300
nm, and in still another embodiment is not more than 100 nm.
[0056] In one embodiment, a shock applying member is placed in
contact with the resin article 110. By contact of the shock
applying member, a shock is applied to the portion where
ultraviolet light has been irradiated. For example, by rubbing the
modified portion 120 of the resin article 110 using the shock
applying member, a friction force can be applied to the portion of
the resin article 110 where ultraviolet light was irradiated. Also,
by projecting the shock applying member to the modified portion 120
of the resin article 110, it is possible to apply a compressive
force to the portion of the resin article 110 where ultraviolet
light was irradiated. Further, by affixing then removing the shock
applying member from the modified portion 120 of the resin article
110, it is possible to apply a tensile force to the portion of the
resin article 110 where ultraviolet light was irradiated. Examples
of a specific embodiment include brush treatment in which the
modified portion 120 is rubbed with a brush, tape treatment in
which tape is applied then peeled away from the modified portion
120, and the like.
[0057] The shock applying treatment can be performed in an
arbitrary medium such as pure water, and in one embodiment, the
shock applying treatment can be performed in a medium that promotes
deposition of the plating layer 130. For example, pressure wave
treatment or air bubble treatment can be performed in a treatment
solution that promotes deposition of the plating layer 130. By
using this sort of treatment solution, deposition of the plating
layer 130 is further promoted, so it is possible to shorten the
time of shock applying treatment. Also, it is possible to improve
adhesiveness of the plating layer 130 and the resin article 110. A
method of performing shock applying treatment in a treatment
solution in this way is particularly advantageous for a resin
article 110 in which it is difficult to form roughness by shock
applying treatment because a polyimide or the like has high
mechanical strength.
[0058] For example, by performing shock applying treatment in an
alkaline treatment solution, in which it is possible to perform
shock applying treatment in the alkaline treatment solution,
particularly pressure wave treatment or air bubble treatment,
deposition of the plating layer 130 is promoted. The composition of
the alkaline treatment solution is not particularly limited, but in
one embodiment, an easily handled alkaline treatment solution
having a pH of less than 13 is used, and in still another
embodiment an alkaline treatment solution having a pH of less than
12.5 is used. Thus, in the shock applying treatment, it is not
necessary to use a strong alkaline such as a sodium hydroxide
aqueous solution having a concentration of approximately 50
g/L.
[0059] The shock applying treatment can also be performed in a
treatment solution that contains a surfactant. The type of
surfactant is not particularly limited. By performing shock
applying treatment in a treatment solution that contains a
surfactant, particularly pressure wave treatment or air bubble
treatment, deposition of the plating layer 130 is promoted. In
still another embodiment, shock applying treatment is performed in
an alkaline treatment solution that contains a surfactant. An
example of such an alkaline treatment solution that contains a
surfactant is a conditioner solution used in electroless plating.
When shock applying treatment is performed in a conditioner
solution (when performing ultrasonic wave conditioner treatment),
by omitting conditioner treatment in a plating step (S230)
described later, it is possible to reduce the number of treatment
steps.
[0060] (Plating Step)
[0061] In a plating step (S230), electroless plating is performed
on the resin article 110 that has been modified. As a result, as
shown in FIG. 1D, the plating layer 130 is formed in the modified
portion 120 of the surface of the resin article 110 that was
produced in the modifying step (S210) and the shock applying step
(S220). Thus, a resin article 100 having a plating layer is
manufactured. In the modifying step (S210) and the shock applying
step (S220), selective modification has been performed such that
the plating layer 130 is deposited in a desired modified portion
120. Accordingly, even in a case where, for example, the entire
resin article 110 has been immersed in a plating solution, the
plating layer 130 is selectively deposited in a desired modified
portion 120. Also, a plating layer 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
130.
[0062] In one embodiment, the plating layer 130 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 electroless plating bath, and an electroless
plating method in which hypophosphorous acid, which has a slow
deposit speed but is easily managed, is used as a reducing agent.
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 130 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, adhesiveness of the modified portion 120 and the
deposited plating layer 130 improves.
[0063] In one embodiment, the electroless plating can be performed
by the below method.
[0064] 1. (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 cation polymer or
the like.
[0065] 2. (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.
[0066] 3. (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.
[0067] 4. (Electroless Plating Treatment) The plating layer 130 is
deposited on the deposited catalyst.
[0068] 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.
[0069] In another embodiment, as catalyst ions, a palladium complex
is used that easily adheres to the modified portion 120 and at
least partially has a positive charge. In order to improve
adhesiveness to the modified portion 120, 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.
[0070] In this case, because a palladium complex that partially has
a positive charge directly affixes to the modified portion of the
resin article 110, 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. Also, because the binder is easily
left in a portion where ultraviolet light has not been irradiated,
sometimes a plating layer may be deposited in an unintended
portion. Thus, as the catalyst ions, it is advantageous for ease of
selectively depositing the plating layer 130 to use a palladium
complex at least partially having a positive charge. That is, when
using this sort of catalyst, unintended deposition of the plating
layer 130 is reduced in a portion where the plating layer 130 is
not intended to be provided.
[0071] In another embodiment, the plating layer 130 may also 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 130 that has been formed by electroless plating, plating is
caused to be deposited by additionally using an electroplating
method. According to this method, it is possible to form a still
thicker plating layer 130. The specific method of electroplating is
not particularly limited.
[0072] There is no special limitation on the thickness of the
plating layer 130 to be obtained. A plating layer 130 of an
appropriate thickness is formed according to the application of the
resin article 100 having a plating layer to be obtained.
[0073] The resin article 100 having a plating layer obtained in
this way includes the resin article 110 having the modified portion
120 that was modified by irradiating ultraviolet light and applying
a shock, and the plating layer 130 that was formed on the modified
portion 120. The resin article 100 having a plating layer obtained
in this way can be used in various applications such as a wiring
board, a conductive film, UV-cutting material, or a
photocatalyst.
[0074] As in the present embodiment, in an embodiment in which a
shock applying step is used, it is not necessary to perform alkali
treatment using a strong alkali, and in fact it is not necessary to
perform alkali treatment at all. Therefore, it is possible to
manufacture the resin article 100 having a plating layer with a
simpler method. Also, the present embodiment, in which it is not
necessary to perform alkali treatment using a strong alkali, is
also applicable to the resin article 110 having low alkali
resistance. In one embodiment, between the irradiation step (S210)
and the plating step (S230), that is, after formation of the
modified portion 120 by irradiating ultraviolet light and before
formation the plating layer 130, alkali treatment using an alkali
solution having a pH of 13 or greater is not performed.
EXAMPLES
Example 1-1
[0075] A cyclo-olefin polymer material (made by Zeon Corp.,
ZeonorFilm ZF-16, thickness 100 .mu.m, surface roughness Ra=0.47
nm), which is a resin material, was used as the substrate.
[0076] First, before performing surface modification, to clean the
substrate surface, ultrasonic cleaning was performed on the
substrate for 3 minutes in pure water at 50.degree. C., and then
the substrate was dried.
[0077] Next, in air, ultraviolet light from an ultraviolet light
lamp was irradiated on a portion of the substrate, via a quartz
chrome mask that was placed on the substrate. Details of the
ultraviolet light lamp (low pressure mercury lamp) used in this
example are given below. The surface roughness of the substrate
after irradiating ultraviolet light was 0.26 nm.
[0078] Low pressure mercury lamp: UV-300 made by Samco Corp.
(primary wavelengths 185 nm, 254 nm)
[0079] Irradiation distance: 3.5 cm
[0080] Irradiation time: 10 minutes
[0081] Illuminance at irradiation distance 3.5 cm: [0082] 5.40
mW/cm.sup.2 (254 nm) [0083] 1.35 mW/cm.sup.2 (185 nm)
[0084] Next, ultrasonic wave treatment was performed on the
substrate after ultraviolet light irradiation. Specifically, the
substrate was treated for 5 minutes in pure water at 50.degree. C.,
using an ultrasonic wave cleaning device (made by Sharp Corp.,
UT-206H, frequency 37 kHz, output 100%).
[0085] Next, a binder treatment was performed on the substrate.
Specifically, a conditioner solution used in a plating solution set
"AISL" made by JCU Co. was heated to 50.degree. C., and the
substrate was immersed for 2 minutes. Afterward, the substrate was
rinsed with pure water.
[0086] Next, a catalyst ion treatment was performed on the
substrate. Specifically, an activator solution used in a plating
solution set "AISL" made by JCU Co. was heated to 50.degree. C.,
and the substrate was immersed for 2 minutes. Afterward, the
substrate was rinsed with pure water.
[0087] Next, a reducing treatment was performed on the substrate.
Specifically, an accelerator solution used in a plating solution
set "AISL" made by JCU Co. was heated to 50.degree. C., and the
substrate was immersed for two minutes. Afterward, the substrate
was rinsed with pure water.
[0088] 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 5
minutes. Afterward, the substrate was rinsed in pure water, and
dried. Thus, a resin article having a plating layer was
manufactured.
[0089] When the obtained resin article having a plating layer was
observed, a plating layer was uniformly deposited in a location
where ultraviolet light was irradiated, and a plating layer had not
been deposited in a location where ultraviolet light was not
irradiated.
Examples 1-2, 1-3
[0090] Except for performing the ultrasonic wave treatment for 8
minutes in Example 1-2 and performing the ultrasonic wave treatment
for 10 minutes in Example 1-3, a resin article having a plating
layer was manufactured in the same manner as in Example 1-1. When
the obtained resin article having a plating layer was observed, a
plating layer was uniformly deposited in a location where
ultraviolet light was irradiated, and a plating layer had not been
deposited in a location where ultraviolet light was not
irradiated.
Comparative Example 1
[0091] Except for not performing the ultrasonic wave treatment, a
resin article having a plating layer was manufactured in the same
manner as in Example 1-1. When the obtained resin article having a
plating layer was observed, a plating layer was deposited in a
peripheral portion of a region where ultraviolet light was
irradiated, but a plating layer had not been deposited in a central
portion of the irradiated region.
[0092] In the resin article having a plating layer that was
manufactured in Examples 1-1 to 1-3 and Comparison Example 1,
adhesiveness of the plating layer to the substrate was evaluated. A
tape testing method according to JIS H 8504: 1996 was used for
evaluating adhesiveness. When tape was affixed to and peeled away
from the resin article having a plating layer that was manufactured
in Comparison Example 1, the plating layer was easily removed. When
tape was affixed to and peeled away from the resin article having a
plating layer that was manufactured in Examples 1-1 and 1-2,
partial removal of the plating layer was observed. On the other
hand, when tape was affixed to and peeled away from the resin
article having a plating layer that was manufactured in Example
1-3, removal of the plating layer was not observed. Thus, it was
confirmed that it is possible to cause plating to be sufficiently
deposited in a location where ultraviolet light was irradiated by
performing ultrasonic wave treatment, and adhesiveness of the
plating layer to the substrate improves by increasing the
ultrasonic wave treatment time.
Example 2-1
[0093] Except for performing microbubble treatment instead of the
ultrasonic wave treatment, a resin article having a plating layer
was manufactured in the same manner as in Example 1-1. In the
microbubble treatment, the substrate was immersed in pure water at
normal temperature such that microbubbles generated from a
microbubble generation apparatus (made by Kansai Automation Devices
Co., MBLL-11-102VS) were applied to the substrate. In this state,
the substrate was treated for 1 minute with microbubbles.
[0094] When the obtained resin article having a plating layer was
observed, a plating layer was uniformly deposited in a location
where ultraviolet light was irradiated, and a plating layer had not
been deposited in a location where ultraviolet light was not
irradiated.
Examples 2-2, 2-3, 2-4
[0095] Except for performing the microbubble treatment for 2
minutes in Example 2-2, performing the microbubble treatment for 10
minutes in Example 2-3, and performing the microbubble treatment
for 20 minutes in Example 2-4, a resin article having a plating
layer was manufactured in the same manner as in Example 2-1. When
the obtained resin article having a plating layer was observed, a
plating layer was uniformly deposited in a location where
ultraviolet light was irradiated, and a plating layer had not been
deposited in a location where ultraviolet light was not
irradiated.
[0096] In the resin article having a plating layer that was
manufactured in Examples 2-1 to 2-4, adhesiveness of the plating
layer to the substrate was evaluated using a tape testing method
according to JIS H 8504: 1996. For all of the resin articles having
a plating layer that were manufactured in Examples 2-1 to 2-4, even
when tape was affixed and peeled away, no removal of the plating
layer was observed. Thus, it was confirmed that it is possible to
cause plating having high adhesive strength to be sufficiently
deposited in a location where ultraviolet light was irradiated by
performing microbubble treatment.
Example 3
[0097] Except for performing tape treatment instead of the
ultrasonic wave treatment, a resin article having a plating layer
was manufactured in the same manner as in Example 1-1. In the tape
treatment, tape was affixed to a location of the substrate where
ultraviolet light was irradiated, and afterward the affixed tape
was peeled away.
[0098] When the obtained resin article having a plating layer was
observed, a plating layer was uniformly deposited in a location
where ultraviolet light was irradiated, and a plating layer had not
been deposited in a location where ultraviolet light was not
irradiated.
Example 4-1
[0099] Except for performing ultrasonic wave conditioner treatment
instead of performing ultrasonic wave treatment and conditioner
treatment, a resin article having a plating layer was manufactured
in the same manner as in Example 1-1. In the ultrasonic wave
conditioner treatment, using an ultrasonic wave cleaning device
(made by Sharp Corp., UT-206H, frequency 37 kHz, output 100%), the
substrate was treated for two minutes in a conditioner solution
used in a plating solution set "AISL" made by JCU Co. that was
heated to 50.degree. C. Afterward, the substrate was rinsed with
pure water.
[0100] When the obtained resin article having a plating layer was
observed, a plating layer was uniformly deposited in a location
where ultraviolet light was irradiated, and a plating layer had not
been deposited in a location where ultraviolet light was not
irradiated.
Examples 4-2, 4-3
[0101] Except for performing the ultrasonic wave conditioner
treatment for 5 minutes in Example 4-2, and performing the
ultrasonic wave conditioner treatment for 10 minutes in Example
4-3, a resin article having a plating layer was manufactured in the
same manner as in Example 4-1. When the obtained resin article
having a plating layer was observed, a plating layer was uniformly
deposited in a location where ultraviolet light was irradiated, and
a plating layer had not been deposited in a location where
ultraviolet light was not irradiated.
[0102] In the resin article having a plating layer that was
manufactured in Examples 4-1 to 4-3, adhesiveness of the plating
layer to the substrate was evaluated using a tape testing method
according to JIS H 8504: 1996. When tape was affixed to and peeled
away from the resin article having a plating layer that was
manufactured in Example 4-1, removal of the plating layer was
observed. When tape was affixed to and peeled away from the resin
article having a plating layer that was manufactured in Example
4-2, slight removal of the plating layer was observed. When tape
was affixed to and peeled away from the resin article having a
plating layer that was manufactured in Example 4-3, removal of the
plating layer was not observed. Thus, it was confirmed that it is
possible to cause plating to be sufficiently deposited in a
location where ultraviolet light was irradiated by performing
ultrasonic wave conditioner treatment, and adhesiveness of the
plating layer to the substrate improves by increasing the
ultrasonic wave conditioner treatment time. Further, by comparing
Examples 1-1 and 4-2, it is understood that adhesiveness of the
plating layer to the substrate improves more in a case where
ultrasonic wave conditioner treatment is performed than in a case
where ultrasonic wave treatment and conditioner treatment are
performed separately.
Example 5-1
[0103] Except for using a polyimide material (NEOPULIM L-3430, made
by Mitsubishi Gas Chemical Co.) instead of a cyclo-olefin polymer
material as the substrate, a resin article having a plating layer
was manufactured in the same manner as in Example 4-3.
[0104] When the obtained resin article having a plating layer was
observed, a plating layer was uniformly deposited in a location
where ultraviolet light was irradiated, and a plating layer had not
been deposited in a location where ultraviolet light was not
irradiated.
[0105] In the resin article having a plating layer that was
manufactured in Example 5-1, adhesiveness of the plating layer to
the substrate was evaluated using a tape testing method according
to JIS H 8504: 1996. Even when tape was affixed to and peeled away
from the resin article having a plating layer that was manufactured
in Example 5-1, removal of the plating layer was not observed.
Example 5-2
[0106] Except for using a polyimide material (NEOPULIM L-3430, made
by Mitsubishi Gas Chemical Co.) instead of a cyclo-olefin polymer
material as the substrate, a resin article having a plating layer
was manufactured in the same manner as in Example 1-3.
[0107] When the obtained resin article having a plating layer was
observed, a tendency was seen for a plating layer to be deposited
in a location where ultraviolet light was irradiated, but there was
low adhesiveness between the substrate and the plating layer, and
locations where the plating layer exfoliating away from the
substrate were seen in some places.
[0108] By comparing Example 5-1 and Example 5-2, it is understood
that adhesiveness of the plating layer to the substrate improves
more in a case where ultrasonic wave conditioner treatment is used
than in a case where ultrasonic wave treatment and conditioner
treatment are performed separately. Also, it is understood that
ultrasonic wave conditioner treatment is suitable for a case where
plating is performed on a polyimide.
[0109] 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.
[0110] This application claims the benefit of Japanese Patent
Application No. 2014-263304, filed Dec. 25, 2014, which is hereby
incorporated by reference herein in its entirety.
* * * * *