U.S. patent application number 16/617226 was filed with the patent office on 2020-03-19 for multi-stage resin surface etching method, and plating method on resin using same.
This patent application is currently assigned to JCU CORPORATION. The applicant listed for this patent is JCU CORPORATION. Invention is credited to Hiroshi ISHIZUKA, Miyoko IZUMITANI, Yasuyuki KURAMOCHI.
Application Number | 20200087791 16/617226 |
Document ID | / |
Family ID | 64455472 |
Filed Date | 2020-03-19 |
United States Patent
Application |
20200087791 |
Kind Code |
A1 |
KURAMOCHI; Yasuyuki ; et
al. |
March 19, 2020 |
MULTI-STAGE RESIN SURFACE ETCHING METHOD, AND PLATING METHOD ON
RESIN USING SAME
Abstract
A novel technique that is a resin etching technique without
using chromic acid and can be operated at an industrial level is
provided by a resin surface etching method characterized in that,
in etching a resin surface, one set of the following steps (a) and
(b) is performed two or more times without performing a resin
swelling step: (a) a step of treating the resin surface with a
solution containing an oxidizing agent and adsorbing the oxidizing
agent on the resin surface, and (b) a step of activating the
oxidizing agent adsorbed on the resin surface in the step (a).
Inventors: |
KURAMOCHI; Yasuyuki; (Wixom,
MI) ; ISHIZUKA; Hiroshi; (Kawasaki-shi, JP) ;
IZUMITANI; Miyoko; (Kawasaki-shi, JP) |
|
Applicant: |
Name |
City |
State |
Country |
Type |
JCU CORPORATION |
Taito-ku |
|
JP |
|
|
Assignee: |
JCU CORPORATION
Talto-ku
JP
|
Family ID: |
64455472 |
Appl. No.: |
16/617226 |
Filed: |
March 15, 2018 |
PCT Filed: |
March 15, 2018 |
PCT NO: |
PCT/JP2018/010095 |
371 Date: |
November 26, 2019 |
Current U.S.
Class: |
1/1 |
Current CPC
Class: |
C23C 18/24 20130101;
C23C 18/30 20130101; C23C 18/32 20130101 |
International
Class: |
C23C 18/24 20060101
C23C018/24; C23C 18/32 20060101 C23C018/32 |
Foreign Application Data
Date |
Code |
Application Number |
Jun 1, 2017 |
JP |
PCT/JP2017/020426 |
Claims
1: A resin surface etching method, wherein, in etching a resin
surface, one of steps (a) and (b) is performed two or more times
without performing a resin swelling step: (a) a step of treating
the resin surface with a solution comprising an oxidizing agent and
adsorbing the oxidizing agent on the resin surface; and (b) a step
of activating the oxidizing agent adsorbed on the resin surface in
the step (a).
2: The resin surface etching method according to claim 1, wherein
each of the steps (a) and (b) is performed for 30 seconds or
more.
3: The resin surface etching method according to claim 1, wherein
the oxidizing agent used in the step (a) is permanganic acid or a
salt thereof.
4: The resin surface etching method according to claim 1, wherein
the activation of the oxidizing agent in the step (b) is performed
by a treatment with a solution comprising one or more types of
activating agents selected from the group consisting of an
inorganic acid, an organic acid, hydrogen peroxide, a halogen
oxoacid, a halogen oxoacid salt, and a persulfate.
5: The resin surface etching method according to claim 1, wherein
the activation of the oxidizing agent in the step (b) is performed
by a treatment with a solution comprising one or more types of
activating agents selected from the group consisting of sulfuric
acid, phosphoric acid, hydrochloric acid, nitric acid,
methanesulfonic acid, hydrogen peroxide, peroxodisulfate, periodic
acid, perchloric acid, and perbromic acid.
6: A plating method on a resin, wherein, in plating a resin, the
plating is performed after the resin is etched by the resin surface
etching method according to claim 1 without performing a resin
swelling step.
Description
TECHNICAL FIELD
[0001] The present invention relates to a multi-stage resin surface
etching method, and a plating method on a resin using the same.
BACKGROUND ART
[0002] Conventionally, it is known that when a plastic surface is
subjected to a metallization treatment by plating, in order to
enhance adhesion of the plastic surface to a plating film, an
etching treatment for roughening the plastic surface with a mixed
liquid of chromic acid and sulfuric acid is performed before a
plating treatment.
[0003] However, in the etching treatment, the operation is
performed at a high temperature of 60.degree. C. or higher using
harmful hexavalent chromium, and therefore, there was a problem
that the operation environment is deteriorated, and further,
attention is needed also for a waste water treatment thereof.
[0004] Further, recently, a technique for etching a plastic surface
using permanganic acid has also been reported (PTL 1), however,
permanganic acid may sometimes be promptly decomposed depending on
use conditions, and it was sometimes problematic for industrial
use.
[0005] Thereafter, in order to suppress decomposition of the
etching solution using permanganic acid described above, a
composition for an etching treatment containing permanganic acid, a
specific inorganic acid, and further one component selected from a
halogen oxoacid, a halogen oxoacid salt, a persulfate, and a
bismuthate has also been reported (PTL 2), however, the
above-mentioned component is used in a large amount, and therefore,
the cost is high, and this was also problematic for industrial
use.
[0006] Further, in order to suppress decomposition of the etching
solution using permanganic acid described above, a technique in
which a resin is swollen with an aqueous dispersion or an aqueous
solution containing a specific organic compound, and thereafter the
resin is brought into contact with an aqueous solution containing
permanganic acid, and further brought into contact with an aqueous
solution containing an acid or the like has also been reported (PTL
3), however, a swelling step is essential, adhesion of plating
after etching is sometimes low, etc., and this was also problematic
for industrial use.
CITATION LIST
Patent Literature
[0007] PTL 1: WO 2005/094394
[0008] PTL 2: Japanese Patent No. 5177426
[0009] PTL 3: JP-A-2007-100174
SUMMARY OF INVENTION
Technical Problem
[0010] An object of the present invention is to provide a novel
technique that is a resin etching technique without using chromic
acid and can be operated at an industrial level.
Solution to Problem
[0011] The present inventors made intensive studies for achieving
the above object, and as a result, they unexpectedly found that by
dividing an etching step using an oxidizing agent for a resin into
two stages and further repeatedly performing the step, a resin
surface can be sufficiently etched even without performing a resin
swelling step, and therefore, by the subsequent plating, high
adhesion is obtained, and thus completed the present invention.
[0012] That is, the present invention is directed to a resin
surface etching method, characterized in that, in etching a resin
surface, one set of the following steps (a) and (b) is performed
two or more times without performing a resin swelling step:
[0013] (a) a step of treating the resin surface with a solution
containing an oxidizing agent and adsorbing the oxidizing agent on
the resin surface; and
[0014] (b) a step of activating the oxidizing agent adsorbed on the
resin surface in the step (a).
[0015] Further, the present invention is directed to a plating
method on a resin, characterized in that, in plating a resin, the
plating is performed after the resin is etched by the
above-mentioned resin surface etching method without performing a
resin swelling step.
Advantageous Effects of Invention
[0016] The resin surface etching method of the present invention
can suppress decomposition of an oxidizing agent used for etching.
Further, in the resin surface etching method of the present
invention, the etching step is repeatedly performed, however,
etching can be more efficiently performed in a shorter time than
when the etching step is performed in one stage for a long time. In
addition, by the resin surface etching method of the present
invention, the resin surface can be sufficiently etched, and
therefore, it is not necessary to perform a resin swelling step
that was conventionally required.
[0017] Therefore, when a resin is plated after performing the
above-mentioned etching method, a plated product that has high
adhesion and can particularly withstand also a severe heat shock
test can be obtained.
DESCRIPTION OF EMBODIMENTS
[0018] In the resin surface etching method of the present invention
(hereinafter referred to as "method of the present invention"), one
set of the following steps (a) and (b) is performed two or more
times. Incidentally, even if sufficient etching cannot be achieved
by a certain number of sets, sufficient etching can be achieved by
increasing the number of sets.
[0019] (a) a step of treating the resin surface with a solution
containing an oxidizing agent and adsorbing the oxidizing agent on
the resin surface
[0020] (b) a step of activating the oxidizing agent adsorbed on the
resin surface in the step (a)
[0021] Incidentally, the resin may be subjected to a treatment such
as degreasing, surface conditioning, and the like before performing
the method of the present invention. However, a swelling step for
facilitating resin etching is not performed. Water washing or hot
water washing may be performed before or after the treatment such
as degreasing, surface conditioning, and the like.
[0022] The resin that can be treated with the etching solution of
the present invention is not particularly limited, but examples
thereof include acrylonitrile-butadiene-styrene (ABS),
polycarbonate/acrylonitrile-butadiene-styrene (PC/ABS),
acrylonitrile-styrene-acrylate (ASA), silicon-based composite
rubber-acrylonitrile-styrene (SAS), NORYL, polypropylene,
polycarbonate (PC), acrylonitrile-styrene, polyacetate,
polystyrene, polyamide, aromatic polyamides, polyethylene,
polyether ketone, polyethylene terephthalate, polybutylene
terephthalate, polysulfone, polyether ether sulfone, polyether
imide, modified polyphenylene ether, polyphenylene sulfide,
polyamide, polyimide, epoxy resins, liquid crystal polymers, and
the like, and copolymers of the above-mentioned respective
polymers, and the like. Among these resins, particularly ABS and
PC/ABS are preferred. Further, the shape of the resin is also not
particularly limited.
[0023] The oxidizing agent used in the step (a) of the method of
the present invention is not particularly limited, however,
examples thereof include permanganates such as potassium
permanganate, sodium permanganate, and the like, and manganese
salts such as manganese sulfate, manganese nitrate, manganese
carbonate, manganese chloride, manganese acetate, manganese
dioxide, sodium manganate, potassium manganite, and the like. Among
these oxidizing agents, particularly permanganates are preferred.
Further, among these oxidizing agents, one type or two or more
types can be used.
[0024] As the solution containing the oxidizing agent, for example,
a solution obtained by dissolving the oxidizing agent in a solvent
such as water is exemplified. The content of the oxidizing agent in
this solution is not particularly limited, but is, for example,
0.0005 mol/L or more, preferably from 0.005 to 2.0 mol/L.
[0025] Further, in the solution containing the oxidizing agent, a
pH buffer agent or a surfactant may be incorporated in such an
amount that the performance of the pH buffer agent or the
surfactant is exhibited as long as the oxidizing action of this
solution is not impaired. Incidentally, the pH of the solution
containing the oxidizing agent is not particularly limited, but is
preferably from 3.0 to 10.0.
[0026] The pH buffer agent is not particularly limited, however,
examples thereof include phosphates, citrates, borates, carbonates,
acetates, diethylbarbiturates, tris(hydroxymethyl)aminomethane,
hydroxyethylpiperazine ethanesulfonic acid,
ethylenediaminetetraacetic acid, and the like. Among these pH
buffer agents, one type or two or more types can be used.
[0027] The surfactant is not particularly limited, however,
examples thereof include amine salt type surfactants, quaternary
amine salt type surfactants, amino acid type surfactants, betaine
type surfactants, carboxylate type surfactants, sulfonate type
surfactants, sulfuric acid ester salt type surfactants, phosphoric
acid ester salt type surfactants, ether type surfactants, ester
type surfactants, nitrogen-containing type surfactants,
fluorine-containing type surfactants, and the like. Among these
surfactants, one type or two or more types can be used. By using
the surfactant, the throwing power of plating can be improved.
[0028] A method for treating the resin with a solution containing
the oxidizing agent and adsorbing the oxidizing agent on the resin
surface is not particularly limited, and for example, the resin may
be immersed in the solution containing the oxidizing agent.
Conditions for immersing the resin are also not particularly
limited, and for example, the resin may be immersed in the solution
at 0 to 100.degree. C., preferably at 60 to 70.degree. C. for 30
seconds or more, preferably for 1 to 5 minutes.
[0029] After adsorbing the oxidizing agent on the resin surface in
the step (a), water washing may be performed as needed. Thereafter,
the oxidizing agent adsorbed on the resin surface is activated in
the step (b).
[0030] A method for activating the oxidizing agent is not
particularly limited, and for example, the resin may be immersed in
a solution containing one type or two or more types of activating
agents selected from the group consisting of an inorganic acid, an
organic acid, hydrogen peroxide, a halogen oxoacid, a halogen
oxoacid salt, and a persulfate.
[0031] Among the activating agents, as the inorganic acid, for
example, sulfuric acid, hydrochloric acid, nitric acid, phosphoric
acid, hydrofluoric acid, and the like are exemplified, as the
organic acid, for example, acetic acid, methanesulfonic acid, and
the like are exemplified, as the halogen oxoacid and the halogen
oxoacid salt, for example, potassium perchlorate, sodium periodate,
perbromic acid, and the like are exemplified, and as the
persulfate, for example, sodium peroxodisulfate, ammonium
peroxodisulfate, and the like are exemplified. Among these
activating agents, hydrogen peroxide, phosphoric acid, and sulfuric
acid are preferred. Such an activating agent is prepared as a
solution by being dissolved in a solvent such as water. The content
of the activating agent in this solution is not particularly
limited, but is, for example, 0.05 mol/L or more, preferably from
0.5 to 17 mol/L.
[0032] Further, in the solution containing the activating agent, a
surfactant may be incorporated in such an amount that the
performance of the surfactant is exhibited as long as the
activating action of this solution is not impaired. The surfactant
is not particularly limited, however, examples thereof include
amine salt type surfactants, quaternary amine salt type
surfactants, amino acid type surfactants, betaine type surfactants,
carboxylate type surfactants, sulfonate type surfactants, sulfuric
acid ester salt type surfactants, phosphoric acid ester salt type
surfactants, ether type surfactants, ester type surfactants,
nitrogen-containing type surfactants, and fluorine-containing type
surfactants. Among these surfactants, one type or two or more types
can be used. By using the surfactant, the throwing power of plating
can be improved.
[0033] A method for activating the oxidizing agent adsorbed on the
resin surface is not particularly limited, and for example, when a
solution containing the activating agent is used, the resin may be
immersed in the solution at, for example, 0 to 100.degree. C., more
preferably at 60 to 70.degree. C. for 30 seconds or more, more
preferably for 1 to 5 minutes.
[0034] The above-mentioned steps (a) and (b) constitute one set,
however, after this step (b), a neutralization and reduction
treatment, a conditioner treatment, or the like may be performed as
needed. Further, each of the steps (a) and (b) is performed for
preferably 30 seconds or more, more preferably 1 to 5 minutes.
[0035] By the method of the present invention described above, a
resin surface can be etched. Incidentally, the method of the
present invention can be used for etching a resin surface in a
conventionally known plating method on a resin, and in the other
steps, a conventionally known plating method on a resin can be
used.
[0036] Examples of the conventionally known plating method on a
resin include an electroless plating method and a direct plating
method.
[0037] Hereinafter, a plating method on a resin using the method of
the present invention will be described.
[0038] To a resin etched by the method of the present invention,
subsequently, a catalyst is imparted using a catalyst imparting
treatment solution. This catalyst imparting treatment solution is
not particularly limited as long as it is generally used for
imparting a catalyst in a plating step, but is preferably a
solution containing a noble metal, more preferably a solution
containing palladium, and particularly preferably a palladium/tin
mixed colloidal catalyst solution. In order to impart such a
catalyst to the resin surface, the treatment may be performed by
setting the temperature of the catalyst imparting treatment
solution to 10 to 60.degree. C., preferably 20 to 50.degree. C. and
immersing the resin therein for 1 to 20 minutes, preferably 2 to 5
minutes.
[0039] The resin surface to which the catalyst is imparted in this
manner is subsequently subjected to metal plating such as
electroless metal plating or metal electroplating (direct plating),
thereby metallizing the resin surface.
[0040] When electroless metal plating is used for metallization of
the resin surface, after the catalyst is imparted using the
catalyst imparting treatment solution, a treatment may be further
performed using an activation treatment solution containing
hydrochloric acid or sulfuric acid. The concentration of
hydrochloric acid or sulfuric acid in this activation treatment
solution is 0.5 mol/L or more, preferably from 1 to 4 mol/L. In
order to treat the resin surface with such an activation treatment
solution, the treatment may be performed by setting the temperature
of the activation treatment solution to 0 to 60.degree. C.,
preferably 30 to 45.degree. C. and immersing the resin therein for
1 to 20 minutes, preferably 2 to 5 minutes.
[0041] The resin subjected to the catalyst impartment and
activation treatments as described above is subsequently subjected
to an electroless metal plating treatment. The electroless metal
plating treatment can be performed according to a usual method
using a known electroless metal plating solution such as an
electroless nickel plating solution, an electroless copper plating
solution, or an electroless cobalt plating solution. Specifically,
when the resin surface is subjected to a plating treatment with an
electroless nickel plating solution, the treatment may be performed
by immersing the resin in the electroless nickel plating solution
at pH 8 to 10 and at a liquid temperature of 30 to 50.degree. C.
for 5 to 15 minutes.
[0042] Further, when metal electroplating (direct plating) is used
for metallization of the resin surface, after imparting a catalyst
using a catalyst imparting treatment solution, a treatment may be
further performed using an activation treatment solution containing
copper ions at pH 7 or higher, preferably 12 or higher. A source of
the copper ions contained in this activation treatment solution is
not particularly limited, and for example, copper sulfate is
exemplified. In order to treat the resin surface with the
activation treatment solution, the treatment may be performed by
setting the temperature of the activation treatment solution to 0
to 60.degree. C., preferably 30 to 50.degree. C. and immersing the
resin therein for 1 to 20 minutes, preferably 2 to 50 minutes.
[0043] The resin subjected to the catalyst impartment and
activation treatments as described above is subsequently immersed
in a widely used copper electroplating bath such as a copper
sulfate bath, and may be subjected to a treatment under usual
conditions, for example, at 1 to 5 A/dm.sup.2 for 2 to 10
minutes.
[0044] Further, the plastic surface metallized by subjecting the
resin surface to metal plating such as electroless plating or metal
electroplating as described above can also be additionally
subjected to various types of copper electroplating or nickel
electroplating or chromium electroplating according to need.
[0045] Incidentally, after performing the method of the present
invention, water washing or hot water washing may be performed
between respective steps.
[0046] The thus obtained resin plating has high adhesion.
EXAMPLES
[0047] Hereinafter, the present invention will be more specifically
described by showing Examples and Comparative Examples. However,
the invention is by no means limited to the description
thereof.
Example 1
<Formation of Electroless Nickel Plating>
[0048] As a sample, a test piece (3001M, manufactured by UMG ABS,
Ltd.) of an ABS resin of 50.times.100.times.3 mm was used. This
sample was immersed in degreasing washing solutions PC-1 and PC-2
(manufactured by JCU Corporation) at 60.degree. C. for 10 minutes,
and subsequently immersed in a surface conditioning solution at
50.degree. C. containing 10 ml/L ENILEX WE (manufactured by JCU
Corporation) for 10 minutes.
[0049] The sample subjected to degreasing and surface conditioning
was treated in an etching step shown in Table 1, and further
immersed in a conditioner (catalyst impartment enhancing) treatment
solution D-POP CDV (manufactured by JCU Corporation) at 25.degree.
C. for 1 minute.
[0050] Incidentally, the etching solution used in the etching step
shown in Table 1 is as follows.
[0051] Chromic Acid Etching (Conventional Method) [0052] anhydrous
chromic acid: 3.8 mol/L [0053] sulfuric acid: 3.8 mol/L [0054]
liquid temperature: 68.degree. C.
[0055] Method of the Present Invention
[0056] Step (a) [0057] potassium permanganate: 0.3 mol/L [0058]
fluorine-containing type surfactant MISTSHUT PF (manufactured by
JCU Corporation): 2 ml/L [0059] boric acid/sodium tetraborate
buffer solution: 10 ml/L [0060] liquid temperature: 68.degree. C.,
pH: 6.5
[0061] Step (b) [0062] sulfuric acid: 10 mol/L [0063]
fluorine-containing type surfactant MISTSHUT PF (manufactured by
JCU Corporation): 2 ml/L [0064] liquid temperature: 68.degree. C.,
pH: 1.0 or lower
[0065] Subsequently, the sample was immersed in a palladium/tin
mixed colloidal catalyst solution at 35.degree. C. containing 20
ml/L CT-580 (manufactured by JCU Corporation) and 2.5 mol/L
hydrochloric acid for 4 minutes, thereby imparting the catalyst on
the ABS resin. The sample to which the catalyst was imparted was
immersed in an activation treatment solution at 35.degree. C.
composed of 1.2 mol/L hydrochloric acid for 4 minutes, thereby
activating the catalyst, and subsequently immersed in an
electroless nickel plating solution ENILEX NI-100 (manufactured by
JCU Corporation) at pH 8.8 and 35.degree. C. for 10 minutes,
thereby performing electroless nickel plating until the film
thickness reached 0.5 .mu.m on the ABS resin.
<Peel Strength Measurement and Sample Preparation Method>
(JIS H 8630 Appendix 6)
[0066] After the sample subjected to electroless nickel plating was
sufficiently washed by water washing or hot water washing, the
sample was immersed in an acid active solution V-345 (manufactured
by JCU Corporation) at room temperature for 1 minute. Subsequently,
according to JIS H 8630 Appendix 6, copper sulfate plating EP-30
(manufactured by JCU Corporation) was performed until the film
thickness reached 20 .mu.m. Thereafter, the resulting material was
annealed at 70.degree. C. for 1 hour, and an adhesion strength was
measured using a tensile strength tester AGS-H 500N (manufactured
by Shimadzu Corporation).
<Heat Shock Test and Sample Preparation Method>
[0067] After the sample subjected to electroless nickel plating was
sufficiently washed by water washing or hot water washing, the
sample was immersed in an acid active solution V-345 (manufactured
by JCU Corporation) at room temperature for 1 minute. Subsequently,
copper sulfate plating CU-BRITE EP-30 (manufactured by JCU
Corporation) was performed until the film thickness reached 20
.mu.m by an electroplating method. Further, semi-glossy nickel
plating CF-24T (manufactured by JCU Corporation) was performed
until the film thickness reached 10 .mu.m, and further, glossy
nickel plating #88 (manufactured by JCU Corporation) was performed
until the film thickness reached 10 .mu.m, and further, microporous
nickel plating MP-309 (manufactured by JCU Corporation) was
performed until the film thickness reached 1 .mu.m. Finally, glossy
chromium plating EBACHROM E-300 (manufactured by JCU Corporation)
was performed until the film thickness reached 0.2 .mu.m, whereby
respective plating films were sequentially formed. Thereafter, the
resulting material was annealed at 70.degree. C. for 1 hour.
[0068] The above sample was subjected to a 40-cycle (cyc) or
80-cycle heat shock test in which a step of maintaining the sample
at -30.degree. C. for 30 minutes and maintaining the sample at
70.degree. C. for 30 minutes was regarded as one cycle. The sample
in which swelling did not occur in the plating film was evaluated
as "A", and the sample in which swelling occurred was evaluated as
"B".
<Results>
TABLE-US-00001 [0069] TABLE 1 Number of Treatment time Peel
strength Heat shock test etching steps Step (a) Step (b) (kgf/cm)
40 cyc 80 cyc Comparative Method 1 chromic acid etching for 2 min
1.1 B B Comparative Method 2 chromic acid etching for 10 min 1.2 A
A Comparative Method 3 1 2 2 1.1 B B Comparative Method 4 1 10 20
1.0 B B Comparative Method 5 1 20 20 0.9 B B Example Method 1 2 2 2
1.2 A B Example Method 2 5 2 2 1.1 A A Example Method 3 10 2 2 1.2
A A
[0070] It was found that the adhesion is improved by extending the
treatment time in the case of chromic acid etching of the
conventional method, however, the adhesion is not improved even if
the treatment time is simply extended in the etching step of the
method of the present invention. It was found that the adhesion is
improved by repeatedly performing the etching step even in a short
treatment time. Incidentally, even in the case of Example Method 1,
by repeating the set of the steps (a) and (b) five times, "A" was
obtained in the severer 80-cycle heat shock test.
Example 2
[0071] Electroless nickel plating was performed in the same manner
as in Example 1 except that, in Example Method 1 of Example 1, the
pH of the etching solution used in the step (a) was changed as
shown in Table 2, and as the pH buffer solution, a buffer solution
shown in Table 3 was used according to the pH. Incidentally, in the
adjustment of the pH, sodium hydroxide and sulfuric acid were used.
Further, for the electroless nickel plating, peel strength
measurement and a heat shock test were performed in the same manner
as in Example 1. The results are shown in Table 2.
TABLE-US-00002 TABLE 2 Peel strength Heat shock test pH (kgf/cm)
(40 cyc) Example Method 4* 13.0 1.1 A Example Method 5 12.0 1.2 A
Example Method 6 9.0 1.1 A Example Method 7 6.5 1.2 A Example
Method 8 5.0 1.3 A Example Method 9 3.0 1.1 A Example Method 10 1.0
1.2 A *The set of the steps (a) and (b) was performed five
times.
TABLE-US-00003 TABLE 3 pH pH buffer solution 10.0 or higher
carbonate/bicarbonate buffer solution 5.5 to 10.0 boric acid/sodium
tetraborate buffer solution 2.5 to 5.5 acetic acid/sodium acetate
buffer solution 2.5 or lower phosphoric acid/sodium dihydrogen
phosphate buffer solution
[0072] In the method of the present invention, there was no problem
at any pH.
Example 3
[0073] Electroless nickel plating was performed in the same manner
as in Example 1 except that, in Example Method 1 of Example 1, the
pH buffer agent was removed from the solution used in the steps (a)
and (b). When this electroless nickel plating was subjected to peel
strength measurement and a heat shock test in the same manner as in
Example 1, the same results as in Example Method 1 were
obtained.
Example 4
[0074] Electroless nickel plating was performed in the same manner
as in Example 1 except that, in Example Method 1 of Example 1, a
test piece (3001M, manufactured by UMG ABS, Ltd.) of an ABS resin
of 50.times.180.times.3 mm in a three-dimensional shape (a shape
that makes air easy to remain) was used as the sample, and a
surfactant shown in Table 4 was used in the solution used in the
steps (a) and (b). The appearance of the electroless nickel plating
was evaluated by visual observation. The results are shown in Table
4.
TABLE-US-00004 TABLE 4 Appear- Surfactant ance Example Method 11*
non good Example Method 12 fluorine-containing type surfactant good
MISTSHUT PF (manufactured by JCU Corporation): 2 ml/L Example
Method 13 cationic surfactant PB-117 (manufac- good tured by JCU
Corporation): 2 ml/L Example Method 14 anionic surfactant #82
(manufactured good by JCU Corporation): 2 ml/L Example Method 15
nonionic surfactant CHT-111A good (manufactured by JCU
Corporation): 2 ml/L Example Method 16 amphoteric surfactant
Gulanlubu SE good (manufactured by JCU Corporation): 2 ml/L *The
set of the steps (a) and (b) was performed five times.
[0075] In the method of the present invention, plating was
performed on the resin in a three-dimensional shape with a small
number of times by using a surfactant.
INDUSTRIAL APPLICABILITY
[0076] According to the method of the present invention, a resin
surface can be etched, and therefore, the method can be used in a
conventionally known plating method on a resin.
* * * * *