JPS6067675A - Pretreatment of plastic material for metal plating - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method of conditioning plastic materials and plastic articles to be metal plated using conventional electroless W plating and electroplating techniques. More particularly, the present invention relates to an improved method of surface conditioning such plastic materials and articles to render their surfaces hydrophilic.

With this conditioning, +? The article can be electroless plated and electroplated to yield a metal plated surface with superior adhesion compared to a metal surface plated onto an untreated surface. Also,
The present invention relates to products manufactured by the method of the present invention.

In recent times, electroplating and metallization of plastics has been of ever-increasing importance.

To produce a plastic with a tightly bonded metal coating, the plastic is subjected to a pretreatment step during which the surface of the plastic is warped and treated to increase the adhesion of the overlying metal surface. . In the past, various methods have been used in such pretreatment steps. For example, in such prior art methods, the surface of the plastic is treated with a mixture of chromium trioxide, sulfuric acid and water, or a mixture of such components and phosphoric acid. Although this method is relatively effective, it suffers from certain drawbacks. For example, the efficiency of this method is highly dependent on the type of plastic to be treated. It is therefore primarily restricted to use in the pretreatment of a narrow class of plastics. Thus, this method does not have the universal reactivity of a wide range of commonly purchased plastics.

Another disadvantage of this method is that the relative amounts of the components in the chromium trioxide-containing pretreatment solution must be maintained within a predetermined, fairly narrow range of concentrations. Only percentage deviations within these optimal quantities are allowed. Otherwise, during the subsequent chemical deposition of the metal, the plastic surface will not be completely coated with the metal and/or
Or the entire coating does not have a sufficiently high peel strength. Moreover, in this known method, the pretreatment solution becomes useless as soon as the concentration level of plastic decomposition products and trivalent chromium compounds in the solution reaches a certain level. Thus, while carrying out this known pretreatment, it is necessary to constantly analytically control and administer the chemicals consumed and to constantly monitor the decomposition products. The continuous control of this method is
Makes its implementation quite complex.

Still other disadvantages of this known pretreatment method arise from the difficulties associated with the disposal of the compositions used. In order to eliminate the pretreatment composition used, it is necessary to reduce the hexavalent chromium compounds and then neutralize the reduction products. In mesophase procedures, large volumes of chromium hydroxide are formed, the removal of which considerably hinders the disposal of the used composition.

Thus, the waste of the pretreatment composition used also complicates the implementation of the method and consumes considerable time, capital investment, technical equipment and plant.

Currently, the pretreatment composition of this method is highly edible and requires extensive washing with water to completely remove it from the plastic surface being pretreated. This further increases the time and expense of this method.

Other prior art methods of pretreating plastic surfaces to increase the peel strength of electroless or electroplated metal surfaces are described in U.S. Pat. No. 4,039,714.
Disclosed in the issue. In this method, the surface of the plastic to be electroplated is pretreated by exposure to an atmosphere containing sulfur trioxide. This well-known method also has some inherent drawbacks. For example, sulfur trioxide is an extremely toxic substance that reacts with atmospheric moisture to form acetic acid, which is an extremely corrosive and dangerous substance.Thus, when using sulfur trioxide, extreme care must be taken to prevent contact with human skin debris.Furthermore, sulfur trioxide Sulfur trioxide reacts violently with some organic materials to produce heat, thereby posing an additional risk to those using this method.The hazardous nature of sulfur trioxide adds to the time, cost, and Recently, the cumbersome and costly neutralization of sulfur trioxide with ammonia, including the disposal of the ammonium sulfate by-product, is also inherent in this etching process.

The present invention relates to a method for treating a plastic surface composed of a polymeric material in order to improve the adhesion of a metal coating deposited from a C(F electrolytic bath), the method comprising: exposure to an atmosphere consisting of ozone and then contacting said surface with an effective amount of a "conditioning solvent".The polymeric material treated by the method of the invention is useful as a polymeric support in a Fa-free deplating process. These benefits can be achieved by electroless plating immediately after pretreatment or at any time after pretreatment, compared to metallized plastic surfaces where the polymer support is not pretreated. After the electroless plating procedure, additional metal is deposited onto the resulting metal-plated surface using conventional electroplating techniques. Can be plated.

One unique advantage of this ozone etching method over the conventional chromium trioxide etching method is that it eliminates the possibility of contamination, a disadvantage experienced in conventional systems. Is this electroless nickel with only 5 pprn of hexavalent chromium? It is important in electroless systems because it inhibits t14 fluid. Moreover, unlike the conventional chromic acid method, the method of the present invention is ideal for single foam plastics because the ozone etching reaction is self-terminating. Furthermore, due to the diffusion effect, only the surface of the returned bubbles is attacked by the maison, thereby minimizing the development of deep open cells. A further advantage of the method of the invention is that 7-1
Elimination of interspecies emission problems and undesirable contamination problems experienced in chromium systems that require as many as zero water washes after the hexavalent chromium etching step.

Such monthly charges pretreated and plated according to the present invention are useful for many purposes. For example, such metal-plated plastics have an EMI/1 (F
Can be used for I-blocking applications, decorative purposes and/or protective purposes. Such metallized plastics can also be used in the fabrication of printed circuit boards and to increase the strength and surface conductivity of plastics. The present invention is also significantly lighter than solid metal parts, yet has the conductivity of a metal, the surface properties of a metal, and other similar metal properties.

The method of the invention includes two essential steps. In a first essential step 8, the surface of the plastic phase to be pretreated is exposed to an atmosphere containing an "effective amount of ozone".

As used herein, "an effective amount of ozone", when in contact with the surface of a plastic material, conditions such surface so that it subsequently conforms to Table 11B above.
contact with an effective amount of a conditioning solvent (as defined below), and electrolessly plate a metal onto the surface thereof,
The amount is effective to form a metal coating with increased adhesion compared to the adhesion of metal coated on an untreated surface. Without wishing to limit the scope of the invention in any way, it is believed that the ozone functions to etch the treated surface, rendering it hydrophilic. Generally, it is believed that as the weight percent of ozone in the exposure atmosphere increases, the degree of etching increases and the hydrophilicity of the treated surface increases. Conversely, as the amount of ozone in the exposure atmosphere decreases, the degree of etching decreases and the hydrophilicity of the treated surface q! The number of f cases increases.

The 1"+1 of ozone used in a particular case will depend on a number of factors, such as the temperature of exposure, the phase of the moon on the particular plastic attacked by the ozone, and the duration of exposure. Thus, the variables in these parameters , the rate and/or extent of etching and the degree to which the hydrophilic properties of the plastic surface are modified can be greatly increased or decreased, thus depending on whether these operating parameters are maximized or minimized. Depending on the condition, smaller or larger amounts of ozone can be used. Generally, however, when using the preferred operating parameters, the amount of ozone will be at least Excellent results are achieved when the amount of ozone is at least about 0.5 -1 fi' based on the total weight of gases in the atmosphere. %, and according to particularly preferred embodiments of the invention, the ozone sleeve is at least about i, o, i% on the same basis. In these particularly preferred embodiments, the amount of ozone is Most preferably at least about 2.5% by weight based on the total weight of.

The upper tt percent of ozone is not critical, but 10
Best results will be achieved when using an atmosphere consisting of 0% ozone. 17 However, because of the economics of ozone generation and/or the inherent difficulties in generating atmospheres composed of more than about 6% ozone by weight, atmospheres composed of greater amounts of ozone are not typically used. Not used.

As is clear from the above, the daytime air containing ozone is 100%.
Rather than ozone, it will often also contain one or more carrier gases.

Preferably the carrier gas is oxygen.

However, other gases can also be used for this purpose, such as air, nitrogen, carbon dioxide, noble gases, mixtures of said gases and other gases that meet the requirement of non-reactivity with ozone.

The process temperature is not critical and can be varied as needed, but the humidity is low enough to prevent plastic conditioning from sagging, and the temperature is low enough to prevent plastic conditioning. iA should be sufficiently large to cause ozone to undergo the reaction kinetics of . Furthermore, excessively high temperatures are preferably avoided in order to prevent an unacceptably high inversion of ozone to oxygen or to increase the rate at which these interact. For development, a relationship exists between ozonization temperature, ozone concentration, and exposure time. When operated under preferred conditions, this method etches at temperatures as low as about -60°C or less and up to about 150°C. Depending on the particular plastic material to be used, the method may be suitably carried out at temperatures between about 45°C and 45°C.
It is carried out at a temperature of about 100<0>C, preferably about 50<0>C to about 90<0>C.

The process pressure is not critical for the material and can be varied widely. This process can be carried out at reduced, atmospheric and superatmospheric pressures. Based on Le Chatelier's principle, it is recognized that beneficial reaction properties can be generated at overpressure. However, this process is usually conveniently carried out at atmospheric or autogenous pressure.

In the first step of the method of the invention, plastic materials are exposed to an ozone atmosphere for a sufficient period of time to etch and render the surface of such materials hydrophilic, thereby allowing subsequent treatment with a strong base and removing the metal from its surface. When electroless plated thereon, it improves the adhesion of the metal coating to the desired degree. As indicated above, the duration of exposure will depend on a number of factors, such as the exposure temperature, the presence of ozone in the exposure atmosphere. The exposure time is critical and can be varied over a wide range as long as the aforementioned results are obtained. For example, exposure times could vary from V seconds to about 24 hours or more. However, in most cases, exposure +1. The time range varies from about 1 to about 5 seconds to about 1 to about 2 hours under preferred conditions, and these values represent a preferred range of exposure times.

The explosion temperature and the concentration of ozone in the exposure atmosphere for a particular application will depend on the type of plastic material used in the process of the present invention. Thus, a preferred set of method parameters for a particular application will be based on the chemical structure of the plastic material and Selected according to reactivity.

A critical aspect of the process of the invention is that the plastic material has a functional group that does not react with ozone, preferably 1
or more, it should contain functional groups containing unsaturated chemical bonds. Such materials include naturally occurring polymers and plastics and other synthetic polymeric materials which can be thermoplastic, thermosetting and elastomeric polymers.

Examples of useful thermoplastic polymers are: polyolefins such as high or low density polyethylene, polypropylene, polyfluoroethylene, ethylene-propylene copolymers (N +) sulfides; polyacetals; polyvinyl chloride and polystyrene. Copolymers of vinyl chloride; such as polyvinyl acetate; polysulfones; such as polystyrene and acrylonitrile-butadiene-styrene copolymers; polyphenylene oxides; saturated polyesters, such as polyalcalcine terephthalates; polycarbonates; polyacrylic polymers, such as poly(methacrylate), polyacrylic acid, polyacrylonitrile, etc.; cellulose esters; and polyurethanes or polyamides. Imides. Examples of useful thermosetting polymers suitable for use in the present invention are phenolic resins; aminosilastics; unsaturated polyesters; polyepoxides, and polyimides, and useful elastomers include natural or synthetic rubbers, silicone rubbers, Polyurethane elastomer, etc.

Polymers containing carbon-oxygen double bonds, carbon/carbon triple bonds and carbon/carbon double bonds are preferred for use in the method of the invention. Examples of such polymers are
They are: nylon 66 (poly(hexamethylene adipamide)), nylon 6 (polycaprolaccum)
etc; polyacetylene; polyisoprene; butadiene/
Styrene copolymers; polychloroprene: unsaturated polyesters; ABS (acryloni, block copolymers of butadiene and styrene); polybutadiene: and polyesters, such as poly(ethylene terephthalate). Preferred polymers for use are also, for example, polysulfite 8, polyacecool, polysulfone, polyphenylene oxide, and the like. Particularly preferred for use in the method of the invention are repeating carbon/
Homopolymers and random, containing carbon double bonds
block and/or graft copolymers, such as acrylonitrile-tsukudiene-styrene copolymers,
Polybutadiene, polyisoprene, butadiene/styrene copolymers, unsaturated polyesters, and similar plastics with carbon/carbon double bonds in the polymer chain and polysulfides, polysulfones, polyacetals and polyphenylene oxides9.

The method of producing the ozone-containing atmosphere used in the method of the invention is not critical and conventional procedures can be used. For example, the ozone component can be generated from air to form a useful atmosphere comprised of ozone and air. Ozone generators are commercially available in sizes ranging from small and compact laboratory models to very large generators used in water treatment. Any of these common types of generators may be used in the practice of the present invention.

Ozone generators are particularly useful in the present invention.

That is, the ozone generator can easily open and close the switch to generate ozone as needed, thereby preventing the generation of a large amount of excess ozone. Ozone has been reported to have long-term toxic effects, and 0
．． Concentration as low as 1%: 1 pprn. Although detectable by odor in Ll, it is preferred not to produce large excess amounts of the chemical. Large excess: If a large excess is produced, the unused ozone can be catalytically replaced with manganese dioxide or alumina to prevent potential contamination problems.

In the second essential step of the method of the invention, contact the treated plastic surface with a conditioning solvent. When used here, ``
An effective amount of conditioning solvent is an amount that, when contacted with a plastic surface previously exposed to an effective amount of ozone, is capable of removing ozone/plastic degradation products from the ozone-contacting surface to provide a treated surface. of the solvent, and on this treated surface, an improved
Metallic strips with peel strength can be deposited by conventional electroless plating techniques. An example of a useful conditioning solvent is a solution of a "strong base." As used herein, at least about 8, preferably at least about 1
It is a base that can form a water bath solution with a pH of 0. Examples of useful base baths include hydroxides and alkoxides of alkali metals, alkaline earth metals, such as sodium hydroxide, potassium hydroxide, lithium hydroxide, sodium methoxide, sodium methoxide, and nonmetallic hydroxides, such as ammonium hydroxide,
A solution in a solvent that is capable of solvating the base and is non-reactive with such solutions. Examples of useful non-reactive solvents are water and polar organic solvents such as ethyl acetate, ethanol, methanol, dimethylformamide, dimethyl sulfoxide, and the like. Particularly preferred embodiments of the invention include (1) strong inorganic bases such as sodium hydroxide, lithium hydroxide, 1jium hydroxide,
Use an aqueous solution such as ammonium hydroxide. The concentration of base in the medium is preferably at least about 0.001% by weight, based on the total amount of solvent, and in particularly preferred embodiments from about 2 to about 3% by weight.
It is. Among these preferred embodiments, a base content of about 5 to about 91% based on the same criteria is most preferred.

After being subjected to the method of the present invention, the total flexural surface is rinsed with light or water to remove conditioning solvents that may have accreted onto the treated plastic surface. Next, the surface was plated with a 11° angle r (I!/) by the usual procedure, and then the surface was plated with a 11 degree pneumatic plating by the same ordinary means at . Brass, strength 1'mium, chromium.

Metal surface such as nickel-gold, complex, platinum, zinc alloy etc.
Polymer materials and articles of 1 m can be obtained.

Polymeric materials treated by the method of the invention and then electrolessly plated using the Hatake process and optionally electroplated can have many uses. For example, such plated surfaces can be used for EMI/RFI shielding on electronic housings as well as for decorative purposes. The metal surface also provides a protective coating against wear and the like.

Additionally, plastic materials plated according to the method of the invention can be used to fabricate printed circuit boards.

Such plates are flat plastic plates plated with a metal such as copper or the like by conventional techniques.

Example 1-XV 0,05 raX O,10#lXO,0 constructed from acrylonitrile/butadiene/styrene copolymer
02WL black into a 21 volume glass resin bottle containing a gas inlet orifice and a gas outlet orifice. Ozone generator (Wels) to glass inlet orifice
Made by Bach Gor, Porat, on, product name: W
elsbach Lahoratory 0zonat
or, T'-26 type). A mixture containing about 2% by weight ozone and the balance acid is generated by an ozone generator and fed into the resin bottle at a speed of about 0.0017 m/min. Each black is heated in an ozone atmosphere at varying temperatures and for varying times. After exposure, each black was removed and a portion was hydroxylated to approximately 1% by weight).
Treat with IIum solution.

Table 1 ABS (acetonitrile, butadiene styrene, IF +17-) treatment Before etching using D etching] Ozone treatment Temperature ■
Yes Yes 2 70 ■ No Yes 2 70 ■ Yes Yes 5 70 ■ No Yes 5 70 ■ Yes Yes 7 70 ■ Yes Yes 10 70 ■1 Yes Yes 2 80 No Yes 2 80 X Yes Yes 5 80 XI No Yes 5 80 ■ Yes Yes 7 80 xiu Yes Yes 10 80 x ■ Yes Yes 15 80 Example Active agent solution (MacDernict Inc.)

Obtained from Macwpltx Activator'
Ll-34,/e (aqueous solution containing radium, stannous, stannic, and hydrogen chloride) at 28° C. for 2 minutes, and washed in water for 1 minute. It was then treated with an accelerator solution of HO2, stannic chloride and water (Macupl, tx
D-45 Accelerator, MacDerr
nLcLXnc,) [soaked at 50°C and again 1
Wash in water for minutes. Each black is then placed in an electroless plating bath. The nickel plating bath was a 4'40-Enplate Nz-4i 4A (Ey
+f! AO+zg IlC,) was mixed with 81 DI water, then 400 ml of Emplaid Ni-414B (I
j;+LtAOILg It+, C1) Prepared by slowly adding the solution while stirring. The resulting solution contains nickel chloride or nickel sulfide, ammonium hydroxide, sodium hypophosphite and water.

This solution's 7)H ammonium hydroxide is about 8.8 to 9
Adjust to ff. The black is left in this bath for 7-10 minutes at room temperature and then washed with water for 1 minute. The black is then fixed on a plating rack, immersed in a 5% H2SO4 solution, and placed in a copper plating bath without cleaning.

A copper plating bath is prepared as follows: anhydrous C/So;
Dissolve i (7,5K9) in 451 distilled water. Add 1775m/concentrated H2So4 to this marsh, then add 1
6 m(4) of concentrated HCl3 is added. This solution is then sequentially injected with 300 m/!
, te) CtLi Q 256 W (KntA,
on, e■71. c), 10'ml of 10256 L
(Enthone Inc). This black is plated for about 90 minutes at a current density of 0.06 to 0.05 amperes/2 of solder. During electroless plating, this solution was circulated by a Sethco pump equipped with a filter.
? Let me have sex.

After plating each black using the above procedure, the peel strength of each plating film was evaluated and
− is listed in the table ■ below.

Table ■ XV I O, 45 XVI II O, 14 X ■ III O, 11 XXIvX O, 30 XXV XI O, 10 XXVI Xll O, 25 XX■ X1ll O, 30 XX■ was etched by treatment with a chromic acid solution for about 7 minutes at a temperature of 66°C. Next is this pu? Wash the tubes with DI water and place in the neutralizing solution for 2 minutes at 49°C. Wash the black again with DI water for 2 minutes and
Plating was carried out according to the procedure of v~XN■. The peel strength of the metal coating was about 0.64 to about 0.426 to 9/rIL.

Example XXX - A series of experiments was carried out to better elucidate the 37i nature of the treatment of J remer material with base after treatment with ozone. In these examples, four blacks constructed from ABS plastic were exposed to an atmosphere containing 1% ozone by weight at 70"C for 10 minutes. After various treatments, the blacks were tested as described in Examples XV-XX■. Electroless plating was performed according to the procedure.

The procedures and peel strength used in each treatment and plating are listed in Table 1 below.

Table ■ Black plating and 1 Not treated Not plated 2 Washed with water Not plated 6 Washed with 1% HGl Not plated 4 Washed with 1% NaOH Very good peel strength and peel strength Examples XXX Plastic materials and other With appropriate selection of process parameters, a wide variety of such materials can be processed and electrolessly plated according to the method of the present invention to form metal plated surfaces with increased peel strength. Process parameters for these exemplary embodiments are listed in Table 1 below.

Table ■ Weight % Ozone treatment Ozone Temperature release polypropy
10%NH4OH902,060” polyimprene
20% Lt, OH, 1803,550" polyvinyl chloride 10% NaOH 15,640" butadiene/styrene
5% KOH200, 885 Copolymer Polycaprolactam 60% LLOH2401,010
0〃Poly(untechamide) 5%NHOH360,151
5” Polybutadiene 25%NαOFi 10 22
25 “ABS 15%KOH153,840”Polytutadiene 2%NaOH903,585”ABS 19
%NHoH600,0550"Polyacetylene 25%
NcLOH100,890"ABS 35%KO) 1
120. 91 110” Polyisoprene 60%N
HO) 1 150 1. Ll 121J Polychloroprene 25%KOH1oo 6. o 15 Acrylonitrile/1% NaOH 504,50" Butadiene copolymer ABS 6% NaOH 903,25" Polycitadiene 2% KOH 1204,065" The remainder of the bath liquid is water.

Example xxx t Acrylonitrile/butadiene/styrene copolymer
(manufactured and sold by Borg WarrLer, Inc., trade name: Gycolac IR) KJB) (1) Place the sample into a sealed reaction chamber. This chamber has direct contact heating and circulation equipment. A gas port and exit orifice is provided through which a carrier gas capable of etching the copolymer can be passed. The etching agent used in this reaction is ozone. Ozone is produced by a generator (Wels).
h, ach Manufactured by Corporation, product name: We
lshαch Gorporatt, oILOzona
tor, T-23 type). The carrier gas is flowed through the chamber at a constant rate of about 80 Dec/min. Begin heating and cycling to rapidly raise the reaction temperature to the desired level, eg, 90°C. When the reaction temperature reaches 4i (Ii), the circulation is stopped and ozone is introduced. This is the beginning of the reaction, and the concentration of ozone in one reactor is essentially zero. The reaction is approximately 18 The circulation of the reactant gas is then restarted, thus forming a homogeneous ozone atmosphere with a final concentration of about 2.2% by weight. O
Zone Corp, ); Monitored by f Shear 7 Analyzer. The reaction is complete after a time of about 20 minutes of synthesis H1.

Following the ozone exposure procedure, the sample was exposed to paddy α at a concentration of approximately 1% subtype.
Treat with OH water bath.

Subsequent processing involves the Muichigi technique described below:
atoγD-34, MacDerrntd, Inc.
, immersed in an aqueous solution i) containing palladium, stannous, stannic and hydrogen chloride for 2 minutes at 28°C,
Rinse with water for 1 minute.

The sample was then soaked in accelerator solution 7fi (Macutex Ac
celeratoγD-45, MacDermcdX
The HC71 paralyzed knitted body manufactured by N.C., Inc. was immersed in 1 rlu of filtrated water containing secondary soot for 2 minutes at 5LI DEG C., and then left in water for 1 minute again. Place the sample into the electroless plating bath while keeping the temperature low. This copper bath contains 6 W iii% Emplaid (Knpla).
te) Qu, -75Q A (3nthoneIn
c, ), 5% by weight each of Enzolate GLL-7508 (E
Enthone Inc.) 2.25% by volume of Enthone C-Door 500 (Enthone Inc.) 0.5 volume of 67% formaldehyde. The sample is immersed in this bath for 15 minutes at 25°C and then rinsed with water for 1 minute. Next, the sample was mixed with 1.5% by volume of Enplaid 440 (Wntho
neFLC0) and 1% by volume of concentrated f-101. This is completed in about 5 minutes at 25°C, and then washed with water for 1 minute. Finally, put the sample into the electroless nickel plating bath. This bath consisted of 6% by volume Niblate tb-419A and 9% by volume Enpraid"-419B (EnthorLeInc,
) is prepared by mixing. The pH of this bath solution is adjusted to about 8 to 8.9 using ammonium water. The sample is immersed in this bath for approximately 10 minutes at 25°C and then rinsed with water for 1 minute.

The adhesion properties of the electroless plating on the sample are then measured.

Severe adhesion testing, particularly for EMi/HFI applications, involves thermal cycling of the plated plastic. Under these tests, the plated plastic must withstand at least six temperature cycles from 140°C to +80°C without blistering, cracking, peeling or other physical deterioration. . Additionally, the plated plastic was subjected to a quantitative tape peel test. Cut the plating crosswise with a razor blade and apply adhesive tape (ScotchM
Apply agmu CTαpg810) crosswise to the surface of the ψJ joint.The tape is peeled off rapidly and any peelings are recorded.Plastics with an acceptable lubricant are tested for this test: J Also, the i2 genus must not come off.

EXAMPLE X X
Produced by rntr In, c, and set by B(j
A replicate sample (commercially available as Yanagi CycoLαC KJB) was etched in ozone for 5 minutes, then Nα
Treatment with 19'o aqueous solution of OH 1-filter. The result is an electroless nickel plated and acceptable lubricated plastic.

Example XXXm Using the procedure of Example XXX I, polysulfone (IJn
t, orLGarbtd, g GorporαttoB
A replicate sample (manufactured by MLnctel M, Inc. and commercially available under the trademark MLnctel M) was similarly etched with ozone and then treated with a 1% water bath of NaOH.

Subsequently, electroless plating and an acceptable gloss-plated plastic are obtained.

Example XXXtv Using the procedure of Example XXX I, polyenylene sulfide (Phtlltps Petrolewm Inc.
A replicate sample (manufactured by Co., Ltd. and commercially available under the trademark Hy, ton -10) was similarly etched with ozone and then treated with a 1% water bath of NαO)l.

Subsequently, with electroless nickel plating, an acceptable plated plastic is obtained.

Example xxxv Using the procedure of Example XXXl, a homopolymer of formaldehyde 9 (manufactured by Dtbpor Lt,
and commercially available under the trade mark IJtlrLn)) were similarly etched with ozone and then Nα
Treat with a 1% aqueous solution of OH. Electroless nickel plating and acceptable wet-plated plastics are obtained.

Example xxxv+ Using the procedure of Example XXX I, a copolymer of trioxane and ethylene oxide (Celanese Inc.
A replicate sample (manufactured by Co., Ltd. and sold under the trademark Crelton ■) was similarly etched with Maison and then treated with a 1% aqueous solution of Leopard α (JH).

Subsequently, electroless nickel plating and an acceptable plated plastic are obtained.

Example XXX ■ A copolymer of polyphenylene oxide 9 and polystyrene ~(Crene?''a
(manufactured by IELec'trtc Xnc, and marketed under the trademark Noryl 225)
Repeat samples were similarly etched with ozone and then N
Treat with a 1% water bath solution of αOH. An acceptable plated plastic is obtained with a C1 electroless nickel plating.

Example XXXx■1 1i Using the procedure of Example XXXI, a copolymer of polyphenylene oxide 9 and polystyrene (Cten,
A replicate sample (manufactured by Electrtc Inc. and sold under the trademark Noryl 225) is similarly etched with ozone. N17.
Eliminate treatment with 1% aqueous solution of OH at 25°C. Subsequently, electroless nickel plating and unacceptable plated plastics are considered.

Example XXXIX Using the procedure of Example XXXI, a copolymer of polyphenylene oxide and polystyrene (CTeneralEl
A replicate sample prepared by electrt, c' IrLc, and sold under the trademark Noγyt 225, is etched with ozone at a constant temperature of 120°C. The final m1 ship in ozone atmosphere is approximately 1.4% by car volume.
It is. Eliminate treatment with a 1% water bath of NIZOH. Consequently, electroless nickel plating and non-acceptable plated plastics are imprinted.

A copolymer of polyphenylene oxide and polystyrene ((xene
Replicate samples (manufactured by RαLE Electric Inc. and commercially available under the trademark NoryL 225) are etched with ozone at a constant temperature of 75°C. The final concentration (U-) of the ozone atmosphere is approximately 2.
It is 4% by weight. Treatment with a 1% water bath of N(ZOH) is excluded. Subsequently, electroless nickel plating and plated plastics are not acceptable.

Example XLI Using the procedure of Example XXXI, a copolymer of polyphenylene oxide and polystyrene (CreneralKt
Manufactured by ectτtc Inc, and trademark 1
A replicate sample (commercially available as ior y L 225) is etched with ozone at a constant temperature of 50°C. The final purity of the ozone atmosphere is 1. f12.
The amount is 5M%. Eliminate the treatment with a 1% N (ZOH) water bath.
Unacceptable plated plastic or obtained.

(4 others) Continued on page 1 Inventor Bruce Edward 2645 Carla Rus Road, New York, USA Invention
Goldhambhai φS United States of America New York Saral Patel Yasaid Lane 158 Inventor
Rustom Peston Boncha Ord Drive, New York, USA 23 Inventor Adam Lawrence 13918 Le Φ Road (no street address), Kobrinski, New York, USA. Marcellus, Huoc 13031. Camillas, Fike 13219. Sairakas, Gifuku 13112. Memphis, Kana

Claims (1)

Claims: 1. Conditioning a natural or synthetic resin material to improve metal adhesion and depositing a metal coating on the conditioned surface from an electroless plating bath. In a method of metal plating, exposing the strip to an atmosphere comprising an effective amount of ozone;
then contacting with an effective amount of a conditioning solvent;
A method comprising a conditioning step. 28 Said monthly rate is based on block copolymers and graft copolymers in which at least one type of monomer unit contains carbon/carbon unsaturation, polydiphenylene sulfones, polyacetals, polyphenylene sulfides and hyphophenylene oxides. The method of claim 1, wherein the plastic is selected from the group consisting of: 3. The method of claim 2, wherein the carbon/carbon unsaturation in the Zoroku copolymer and graft copolymer is a double bond. 4. The method according to claim 3, wherein the plastic is an ABS resin. 5. The method according to claim 2, wherein the material is selected from the group consisting of polydiphenylene sulfones, polyphenylene sulfides, polyacetals, and polyphenylene oxides. 6. The method of claim 1, wherein the amount of ozone in the atmosphere is small (approximately 0.1 m scale %) based on the total weight of the atmosphere. 7. The amount is at least about 0.80411 fl-%
The method according to claim 6, wherein the method is: 8. The conditioning solvent is a solution of a strong inorganic or organic base, 1 flit of claim 44
The method described in box 1. 9. The method of claim 8, wherein the base is selected from the group consisting of hydroxide, potassium hydroxide, lithium hydroxide, and ammonium hydroxide. 10. 10. The method of claim 9, wherein the concentration of base in the solution is at least about 0.51% based on the total weight of the bath liquid.