JP2004131804A - Pretreatment method for electroless plating workpiece and method for manufacturing plating coated member - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To form a plating film having excellent adhesiveness without roughening the surface of a resin workpiece by eliminating the need for etching treatment or gaseous ozone treatment. <P>SOLUTION: The plating workpiece consisting of a resin containing a graft copolymer using silicone reinforced acrylic rubber which does not contain a diene rubber component or of which the amount of the diene rubber component contained therein is ≤10mass% is used and after the plating workpiece is brought into contact with an ozone solution, a solution containing at least either of an ionic surfactant and nonionic surfactant and an alkaline component is brought into contact therewith. The deterioration of the diene rubber component by the ozone and the degradation in the strength of adhesion of the plating film are prevented. <P>COPYRIGHT: (C)2004,JPO

Description

【００６２】
【表２】

【００６３】
表１，２より、シリコーン強化されたアクリルゴムを使用したグラフト重合体を含有する樹脂をめっき素材とすることで、ジエンゴム成分濃が１５質量％のＡＢＳ樹脂に比べてめっき被膜の付着性が大きく向上していることがわかる。
【００６４】
そしてシリコーン強化されたアクリルゴムを使用したグラフト重合体を含有する樹脂をめっき素材とした場合には、オゾン処理時間が２分以下と短いと、めっき被膜が形成されないか付着強度が小さく、２０分を超えると樹脂自体の劣化によって付着強度が低下している。したがってオゾン処理時間は４〜２０分とするのが好ましいことが明らかである。
【００６５】
またシリコーン強化されたアクリルゴムを使用したグラフト重合体を含有する樹脂をめっき素材とした場合には、オゾン処理濃度が　５０ｐｐｍ以下では樹脂が活性化されないために付着強度が小さく、１００ｐｐｍ以上のオゾン濃度とするのが好ましいことが明らかである。
【００６６】
【発明の効果】
すなわち本発明の無電解めっき素材の前処理方法によれば、付着強度に優れためっき被膜を容易に形成することができる。また樹脂素材表面を粗面化する必要がないので、高い金属光沢を有するめっき被膜を薄い膜厚で形成することができ、かつクロム酸などが不要となるので廃液処理も容易である。
【図面の簡単な説明】
【図１】本発明の推定される作用を示す説明図である。
【符号の説明】
１：界面活性剤　　　　　　２：触媒[0001]
TECHNICAL FIELD OF THE INVENTION
The present invention relates to a pretreatment method performed to improve the adhesion of a plating film when a plating film is formed by performing an electroless plating process on a resin material surface, and a plating material subjected to the pretreatment method. The present invention relates to a method for manufacturing a plating-coated member used.
[0002]
[Prior art]
As a method for imparting conductivity or metallic luster to a resin material, electroless plating is known. This electroless plating is a method in which metal ions in a solution are chemically reduced and deposited to form a metal film on the surface of the material. A coating can be formed. Electroplating can also be performed on the resin material on which the metal film is formed, thereby expanding the applications. For this reason, electroless plating is widely used as a method for imparting metallic luster or imparting conductivity to resin materials used in fields such as automobile parts and home appliances.
[0003]
However, the plating film formed by the electroless plating process has a problem that it takes a long time to form the film and that the film has insufficient adhesion to a resin material. For this reason, a process of first performing a chemical etching process on a resin material to roughen the surface thereof and then performing an electroless plating process is generally performed.
[0004]
For example, Japanese Patent Application Laid-Open No. 01-092377 discloses a method in which a resin material is pre-treated with ozone gas and then subjected to electroless plating. According to the publication, the unsaturated bond of the resin material is cleaved by the ozone gas to reduce the molecular weight, and molecules having different chemical compositions coexist on the surface, so that smoothness is lost and the surface is roughened. Therefore, it is described that the film formed by the electroless plating firmly enters the rough surface and does not easily peel off.
[0005]
In the above-described conventional technique, the resin material is roughened, and the adhesion of the plating film is enhanced by a so-called anchor effect. However, the method of roughening lowers the surface smoothness of the resin material. Therefore, in order to obtain a metallic luster with a high design property, the plating film must be thickened, and there is a problem that the number of steps is increased.
[0006]
Japanese Patent Application Laid-Open No. 08-092752 discloses a method in which a polyolefin is used as a plating material, the surface is roughened by etching, and the surface is brought into contact with ozone water, followed by treatment with a solution containing a cationic surfactant. However, in the method of roughening by etching, toxic substances such as chromic acid and sulfuric acid need to be used, and there is a problem in waste liquid treatment. Further, the problem that the surface smoothness of the resin material is reduced cannot be solved.
[0007]
[Patent Document 1] Japanese Patent Application Laid-Open No. 01-092377 [Patent Document 2] Japanese Patent Application Laid-Open No. 08-092752
[Problems to be solved by the invention]
The present invention has been made in view of such circumstances, and it is an object of the present invention to form a plating film having excellent adhesion without the need for etching treatment or ozone gas treatment and roughening a resin material. And
[0009]
[Means for Solving the Problems]
The feature of the pretreatment method for an electroless plating material of the present invention that solves the above-mentioned problems is that a plating material made of a resin having an unsaturated bond is brought into contact with a first solution containing ozone to form a first treatment step of forming an ozone-treated material. And a second treatment step of contacting a second solution containing at least one of an ionic surfactant and a nonionic surfactant and an alkali component with an ozone-treated material. The plating material does not contain a diene rubber component or contains a diene rubber component in an amount of 10% by mass or less, and is made of a resin containing a graft copolymer using silicone-reinforced acrylic rubber.
[0010]
The time for bringing the plating material into contact with the first solution containing ozone is desirably 4 to 20 minutes. Further, it is desirable that the first solution contains 100 ppm or more of ozone.
[0011]
Further, a feature of the method for manufacturing a plating-coated member of the present invention is that an electroless plating process is performed on a plating material that has been subjected to the pretreatment method of the present invention. Further, it is also preferable to perform an electrolytic plating process.
[0012]
BEST MODE FOR CARRYING OUT THE INVENTION
In the pretreatment method for an electroless plating material according to the present invention, the graft copolymer containing no diene rubber component or containing 10% by mass or less of a diene rubber component as a plating material, and using a silicone-reinforced acrylic rubber is used. Is used. This is because in a resin having a diene rubber component content of more than 10% by mass, the diene rubber component is deteriorated by ozone, and the adhesion strength of the plating film is reduced due to the reduction in the strength of the plating material. Therefore, it must be left at room temperature for several days after plating before sufficient adhesion strength is exhibited, which causes a problem in workability. The amount of the diene rubber component can be calculated by an ozonolysis method using acetone and chloroform solvents.
[0013]
Silicone-reinforced acrylic rubber is a composite rubber in which the polymer segments of silicone rubber and acrylic rubber are condensed with each other to form a network structure.A core shell in which one rubber covers the other rubber A type of composite rubber, such as a composite acrylic rubber composed of a polyalkyl acrylate and a polyorganosiloxane.
[0014]
By using such an acrylic rubber and graft-polymerizing a vinyl cyanide monomer such as acrylonitrile and / or an aromatic vinyl monomer such as styrene and α-methylstyrene, the graft copolymer according to the present invention is obtained. A polymer is obtained. In the graft polymerization, other monomers may be contained as necessary.
[0015]
The plating material used in the present invention is also preferably a resin composition containing another polymer in addition to the above graft copolymer. Preferably, a resin composition comprising 5 to 80% by mass of the above graft copolymer and 20 to 95% by mass of the other polymer (the total amount of both is 100% by mass) is preferable.
[0016]
At this time, the other polymer to be used is not particularly limited, but a vinyl cyanide monomer as an essential component, and at least one monomer selected from an aromatic vinyl monomer and a maleimide monomer It is preferably a hard polymer obtained by copolymerizing a polymer.
[0017]
In the pretreatment method of the present invention, a first treatment step of contacting a plating material made of a resin having an unsaturated bond with a first solution containing ozone is performed. In the first processing step, it is considered that the unsaturated bond on the surface of the plating material is partially cut by oxidation with ozone in the first solution, and a C—OH bond or a C ＝ O bond is generated and activated.
[0018]
In the first processing step, the plating material is brought into contact with the first solution. As a method of contact, the first solution may be sprayed on the plating material surface, or the plating material may be immersed in the first solution. The contact of the plating material with the first solution by immersion is preferable because ozone is hardly released from the first solution as compared with the contact of the plating material with the first solution by spraying.
[0019]
The ozone concentration in the first solution has a significant effect on the activation of the plating material surface, and the effect of activation can be seen in a long-time treatment from about 10 ppm. Increase. Also, if the concentration is low, the deterioration precedes, and therefore the ozone concentration is preferably high.
[0020]
In principle, the processing temperature in the first processing step is higher, the higher the reaction rate is, the higher the temperature is. However, the higher the temperature is, the lower the solubility of ozone in the first solution is. In order to make the ozone concentration 100 ppm or more, it is necessary to pressurize the processing atmosphere to a pressure higher than the atmospheric pressure, and the apparatus becomes large-scale. Therefore, if the processing temperature is not desired to be large, room temperature is sufficient.
[0021]
The time for bringing the plating material into contact with the first solution containing ozone is preferably 4 to 20 minutes. If the ozone concentration is less than 4 minutes, it is difficult to exhibit the effect of the ozone treatment even if the ozone concentration is 100 ppm, and if the ozone concentration exceeds 20 minutes, the resin material is deteriorated.
[0022]
Preferably, the first solution contains a polar solvent. By including a polar solvent, the activity of ozone in the first solution can be increased, and the processing time in the first processing step can be reduced. Water is particularly preferred as the polar solvent, but alcohol solvents, N, N-dimethylformamide, N, N-dimethylacetamide, dimethylsulfoxide, N-methylpyrrolidone, hexamethylphosphoramide, etc., alone or in water or alcohol It can be used by mixing with a system solvent.
[0023]
In the pretreatment method of the electroless plating material of the present invention, at least one of an anionic surfactant and a nonionic surfactant and an alkali component are added to the ozone-treated material treated with the first solution containing ozone. A second processing step of bringing a second solution containing
[0024]
It is considered that at least one functional group selected from C = O and C-OH exists on the surface of the plating material by the first treatment step. Therefore, in this second treatment step, as shown in FIGS. 1A and 1B, it is considered that the surfactant 1 has its hydrophobic group adsorbed on the above-mentioned functional group that is exposed. Further, the alkali component has a function of solubilizing the surface of the plating material in water at a molecular level, and removes an embrittlement layer on the surface of the plating material to allow more of the functional groups to be exposed. Therefore, the surfactant 1 is also adsorbed to a new functional group exposed by removing the embrittlement layer.
[0025]
As the surfactant, a surfactant in which a hydrophobic group is easily adsorbed to at least one functional group consisting of C ＝ O and C—OH is used, and at least one of an anionic surfactant and a nonionic surfactant is used. Is used. With a cationic surfactant and a neutral surfactant, a plating film cannot be formed, or it is difficult to exhibit effects. Examples of the anionic surfactant include sodium lauryl sulfate, potassium lauryl sulfate, sodium stearyl sulfate, and potassium stearyl sulfate. Examples of the nonionic surfactant include polyoxyethylene dodecyl ether.
[0026]
As the alkali component, one that can dissolve the surface of the plating material at the molecular level to remove the embrittlement layer can be used, and sodium hydroxide, potassium hydroxide, lithium hydroxide, and the like can be used.
[0027]
As the solvent of the second solution containing a surfactant and an alkali component, it is desirable to use a polar solvent, and water can be typically used. In some cases, an alcohol-based solvent or a water-alcohol mixed solvent is used. You may. Further, the second solution is brought into contact with the ozone-treated material by a method of dipping the ozone-treated material in the second solution, a method of applying the second solution to the surface of the ozone-treated material, and spraying the second solution on the surface of the ozone-treated material. It can be performed by such a method.
[0028]
The concentration of the surfactant in the second solution is preferably in the range of 0.01 to 10 g / L. If the concentration of the surfactant is lower than 0.01 g / L, the adhesion of the plating film is reduced, and if the concentration is higher than 10 g / L, the surfactant is brought into an associated state on the surface of the plating material, and excess surfactant is contaminated with impurities. , The adhesion of the plating film is reduced. In this case, after the pretreatment, the plating material may be washed with water to remove excess surfactant.
[0029]
Further, the concentration of the alkali component in the second solution is desirably 12 or more in terms of pH value. Although the effect can be obtained even if the pH value is less than 12, the time required for forming a plating film of a predetermined film thickness becomes long because the number of the above-described functional groups is small.
[0030]
The contact time between the second solution and the plating material is not particularly limited, but is preferably 1 minute or more at room temperature. If the contact time is too short, the amount of surfactant adsorbed on the functional group may be insufficient, and the adhesion of the plating film may be reduced. However, if the contact time is too long, there is a case where at least one functional group selected from CＣO and C-OH is dissolved to a layer where the electroless plating is exposed, and electroless plating may be difficult. About 1 to 5 minutes is sufficient. It is desirable that the temperature be higher. The higher the temperature, the shorter the contact time can be, but room temperature to about 60 ° C. is sufficient.
[0031]
In the second treatment step, the surfactant may be adsorbed after treatment with an aqueous solution containing only an alkali component, but the embrittlement layer may be formed again before the surfactant is adsorbed. The second treatment step is desirably performed in a state where at least one of an anionic surfactant and a nonionic surfactant and an alkali component coexist as in the present invention.
[0032]
Further, it is preferable that the second processing step is performed after the first processing step. However, in some cases, the first processing step and the second processing step can be performed simultaneously. In this case, a mixed solution of the first solution and the second solution is prepared, and the plating material is immersed in the mixed solution, or the mixed solution is sprayed on the surface of the plating material. In this case, since the reaction between ozone and the surface of the plating material is rate-determining, the treatment time is determined according to the ozone concentration in the mixed solution.
[0033]
After the second treatment step, a step of washing with water to remove alkali components may be performed. Since the surfactant is firmly adsorbed to the functional group, it has been found that the surfactant is not removed by washing with water and the adsorbed state is maintained. Therefore, the plating material pretreated according to the present invention does not lose its effect even if time elapses before the electroless plating step.
[0034]
Then, in the electroless plating step, the plating material on which the surfactant is adsorbed is brought into contact with the catalyst. Then, as shown in FIG. 1 (C), it is considered that the catalyst 2 is adsorbed on the hydrophilic group of the surfactant 1 adsorbed on the functional group.
[0035]
By subjecting the plating material on which the catalyst is sufficiently adsorbed to an electroless plating treatment, the surfactant is removed from the functional group, and the metal is considered to bind to the C—O group and / or the C ＝ O group. In addition, a plating film having excellent adhesion can be formed.
[0036]
As the catalyst, a catalyst such as Pd ²⁺ used for conventional electroless plating can be used. The catalyst can be adsorbed on the surface of the plating material by bringing the solution in which the catalyst ions are dissolved into contact with the surface of the adhered material, and can be carried out in the same manner as the contact with the second solution described above. The conditions such as the contact time and the temperature may be the same as those in the related art.
[0037]
In addition, the conditions of the electroless plating, the kind of metal to be deposited, and the like are not limited, and the electroless plating can be performed in the same manner as the conventional electroless plating.
[0038]
It is desirable to perform an electrolytic plating step of further performing electrolytic plating on the resin material after the electroless plating step. Thereby, a metallic luster can be imparted, and the design property is remarkably improved.
[0039]
【Example】
Hereinafter, the present invention will be described specifically with reference to test examples.
[0040]
(Test Example 1)
98 parts of octamethylcyclotetrahexane and 2 parts of γ-methacryloyloxypropyldimethoxymethylsilane were mixed to obtain 100 parts of a siloxane-based mixture. To this, 300 parts of an aqueous solution obtained by dissolving 0.56 part of sodium dodecylbenzenesulfonate in distilled water was added, and the mixture was stirred with a homomixer at 9000 rpm for 2 minutes, and then passed once through a homogenizer at a pressure of 30 MPa to be stable. A premixed organosiloxane latex was obtained.
[0041]
On the other hand, 10 parts of dodecylbenzenesulfonic acid and 90 parts of distilled water were injected into a reactor equipped with a reagent injection container, a cooling pipe, a jacket heater and a stirrer to prepare a 10% aqueous solution of dodecylbenzenesulfonic acid. .
[0042]
While the aqueous solution was heated to 85 ° C., the premixed organosiloxane latex was added dropwise over 4 hours, and after the addition was completed, the temperature was maintained for 1 hour and then cooled. Then, the reaction product was neutralized with an aqueous solution of sodium hydroxide to obtain a latex. The obtained latex was dried at 170 ° C. for 30 minutes and the solid content was determined to be 18.0%.
[0043]
In a reactor equipped with a reagent injection vessel, a cooling pipe, a jacket heater and a stirrer, 45.2 parts of the polyorganosiloxane latex obtained above and polyoxyethylene alkylphenyl ether sulfate (“Emal NC-35” Kao) 0.18 parts were added, and 148.5 parts of distilled water were added and mixed, and then the following mixture was added.
[0044]
42 parts of butyl acrylate 0.3 part of allyl methacrylate 0.1 part of 1,3-butylene glycol dimethacrylate 0.1 part of t-butyl hydroperoxide 0.11 part After the inside of the reactor was replaced with nitrogen, the temperature was raised to 60 ° C. When the internal liquid temperature reached 60 ° C., an aqueous solution in which 0.000075 parts of ferrous sulfate, 0.000225 parts of disodium ethylenediaminetetraacetate and 0.2 parts of Rongalite were dissolved in 10 parts of distilled water was added. Then, radical polymerization was started. The liquid temperature rose to 78 ° C. due to the polymerization of the acrylate component. This state was maintained for 1 hour to complete the polymerization of the acrylate component to obtain a composite rubber latex of polyorganosiloxane and butyl acrylate rubber.
[0045]
After the liquid temperature of the composite rubber latex has dropped to 70 ° C., an aqueous solution obtained by dissolving 0.25 part of Rongalite in 10 parts of distilled water is added, and then 2.5 parts of acrylonitrile, 7.5 parts of styrene monomer and t-butyl A mixed solution containing 0.05 part of hydroperoxide was dropped and polymerized over 2 hours. After completion of the dropwise addition, the temperature of 60 ° C. was maintained for 1 hour, and then 0.001 part of ferrous sulfate, 0.003 part of disodium ethylenediaminetetraacetate, 0.2 part of Rongalit and “Emal NC-35” (Kao An aqueous solution obtained by dissolving 0.18 part in 10 parts of distilled water was added, and then a mixture of 10 parts of acrylonitrile, 30 parts of styrene monomer and 0.2 part of t-butyl hydroperoxide was added for 2 hours. And polymerized. After completion of the dropwise addition, the temperature of 60 ° C. was maintained for 0.5 hour, 0.05 part of cumene hydroperoxide was added, and the temperature of 60 ° C. was further maintained for 0.5 hour, followed by cooling. The obtained graft copolymer latex was coagulated with an aqueous calcium acetate solution, subjected to liquid removal and washing by a centrifugal separator, and dried to obtain a dry powder of the graft copolymer (A-1).
[0046]
Acrylonitrile 30 parts Styrene monomer 70 parts Azobisisobutyronitrile 0.15 parts t-dodecylmercaptan 0.40 parts Calcium phosphate 0.50 parts Distilled water 150 parts The above composition was charged into a 100-liter autoclave and stirred vigorously. After confirming the dispersion in the system, the temperature was raised to 75 ° C. and polymerization was carried out for 3 hours. Thereafter, the temperature was raised to 110 ° C. and ripened for 30 minutes. After cooling, dehydration, washing, and drying were performed to obtain a powdery hard copolymer.
[0047]
30 parts by weight of the graft copolymer (A-1) and 70 parts of the hard copolymer were blended, and
Antioxidant 0.2 part Metal soap 0.2 part EBS 0.4 part Silicone oil 0.05 part was added and mixed for 5 minutes (3000 rpm) with a Henschel mixer, and extruded at a cylinder temperature of 230 ° C. to pelletize. Using the pellets as a molding material, a flat plate was molded using a screw-type injection molding machine (cylinder temperature 230 ° C., mold temperature 60 ° C.), and this was used as a plating material.
[0048]
Using this plating material, a first treatment step of immersing in an ozone aqueous solution containing 150 ppm of ozone at room temperature for 1 to 30 minutes was performed to obtain an ozone-treated material. The immersion time was set at 7 levels of 1 minute, 2 minutes, 4 minutes, 8 minutes, 12 minutes, 20 minutes, and 30 minutes, and each ozone-treated material was prepared.
[0049]
Next, a mixed aqueous solution in which NaOH was dissolved at 50 g / L and sodium lauryl sulfate was dissolved at 1 g / L was heated to 60 ° C., and each ozone-treated material was immersed therein for 2 minutes to remove the anionic surfactant (lauryl). Sodium sulfate) was adsorbed (second treatment step).
[0050]
Each ozone-treated material to which the surfactant is adsorbed is pulled up, washed with water, dried, and then dissolved in 0.1% by weight of palladium chloride in a 3N hydrochloric acid aqueous solution and 5% by weight of tin chloride in a catalyst solution heated to 50 ° C. For 3 minutes, and then for 3 minutes in a 1N aqueous hydrochloric acid solution to activate the palladium. As a result, each adsorbing material on which the catalyst was adsorbed was obtained.
[0051]
Thereafter, each adsorption material was immersed in a Ni-P chemical plating bath kept at 40 ° C to deposit a Ni-P plating film for 10 minutes. The thickness of each of the deposited Ni-P plating films is 0.5 μm. Further, in a copper sulfate-based Cu electroplating bath, 100 μm of copper plating was deposited on the surface of each Ni—P plating film.
[0052]
After forming the plating film, the coating film was dried at 70 ° C. for 2 hours, and a cut reaching the plating material was made in a width of 1 cm in the obtained plating film, and the adhesion strength of the plating film was measured by a tensile tester. Table 1 shows the results.
[0053]
(Test Example 2)
Using the same plating material as in Test Example 1, a first treatment step of immersing in an ozone aqueous solution containing 10 to 200 ppm of ozone at room temperature for 4 minutes was performed to obtain an ozone-treated material. The ozone concentration of the ozone aqueous solution was set to six levels of 10 ppm, 20 ppm, 50 ppm, 100 ppm, 150 ppm, and 200 ppm, and each ozone-treated material was prepared.
[0054]
Thereafter, pretreatment was performed in the same manner as in Test Example 1, and catalyst adsorption, electroless plating, and copper plating were similarly performed, and the adhesion strength of the plating film was measured. Table 2 shows the results.
[0055]
(Test Example 3)
50 parts (solid content) of a polybutadiene rubber latex having a solid content of 35% and an average particle size of 0.28 μm are charged into a reaction vessel, and further, disproportionated potassium rosinate 2.0 parts sodium pyrophosphate 0.2 parts sulfuric acid One part of iron: 0.01 part: Dextrose: 0.35 part: 200 parts of water (including those coming from latex) was added, the polymerization initiation temperature was adjusted to 40 ° C., and the following monomer mixture was added dropwise over 120 minutes, followed by 1 hour By holding, graft polymerization was performed.
[0056]
35 parts of styrene monomer 15 parts of acrylonitrile 0.15 part of cumene hydroperoxide 2 parts of butylated hydroxytoluene and 0.5 part of dilaurylthiopropionate as antioxidants are added to the obtained polymer latex, and a 5% sulfuric acid aqueous solution is added. , And washed and dried to obtain a dry powder of the graft copolymer (A-2) (a diene rubber component amount of 15% by mass).
[0057]
30 parts by weight of the graft copolymer (A-2) and 70 parts of the same hard copolymer as in Test Example 1 were blended, and
Antioxidant 0.2 part Metal soap 0.2 part EBS 0.4 part Silicone oil 0.05 part was added and mixed for 5 minutes (3000 rpm) with a Henschel mixer, and extruded at a cylinder temperature of 230 ° C. to pelletize. Using the pellets as a molding material, a flat plate was molded using a screw-type injection molding machine (cylinder temperature 230 ° C., mold temperature 60 ° C.), and this was used as a plating material.
[0058]
Pretreatment was performed in the same manner as in Test Example 1 except that this plating material was used, and similarly, catalyst adsorption, electroless plating, and copper plating were performed, and the adhesion strength of the plating film was measured. Table 1 shows the results.
[0059]
(Test Example 4)
Pretreatment was performed in the same manner as in Test Example 2 except that the same plating material as in Test Example 3 was used, and catalyst adsorption, electroless plating, and copper plating were similarly performed, and the adhesion strength of the plating film was measured. Table 2 shows the results.
[0060]
<Evaluation>
[0061]
[Table 1]

[0062]
[Table 2]

[0063]
From Tables 1 and 2, it can be seen that by using a resin containing a graft polymer that uses silicone-reinforced acrylic rubber as the plating material, the adhesion of the plating film is greater than that of an ABS resin having a diene rubber component concentration of 15% by mass. It can be seen that it has improved.
[0064]
When a resin containing a graft polymer using silicone-reinforced acrylic rubber is used as the plating material, if the ozone treatment time is as short as 2 minutes or less, no plating film is formed or the adhesion strength is low, and If it exceeds 300, the adhesive strength decreases due to the deterioration of the resin itself. Therefore, it is clear that the ozone treatment time is preferably set to 4 to 20 minutes.
[0065]
Also, when a resin containing a graft polymer using an acrylic rubber reinforced with silicone is used as a plating material, if the ozone treatment concentration is 50 ppm or less, the resin is not activated, so that the adhesive strength is small, and the ozone concentration of 100 ppm or more. It is clear that it is preferable to use
[0066]
【The invention's effect】
That is, according to the pretreatment method of the electroless plating material of the present invention, a plating film having excellent adhesion strength can be easily formed. Further, since it is not necessary to roughen the surface of the resin material, a plating film having high metallic luster can be formed with a small film thickness, and chromic acid or the like is not required, so that waste liquid treatment is easy.
[Brief description of the drawings]
FIG. 1 is an explanatory diagram showing an estimated operation of the present invention.
[Explanation of symbols]
1: Surfactant 2: Catalyst

Claims (5)

A first treatment step of bringing a plating material made of a resin having an unsaturated bond into contact with a first solution containing ozone to obtain an ozone-treated material; and at least one of an anionic surfactant and a nonionic surfactant, and an alkali And a second treatment step of bringing a second solution containing the component into contact with the ozone-treated material,
The plating material does not contain a diene rubber component or the amount of a diene rubber component contained is 10% by mass or less, and is made of a resin containing a graft copolymer using an acrylic rubber reinforced with silicone. Pretreatment method for electrolytic plating material. The pretreatment method for an electroless plating material according to claim 1, wherein a time for bringing the plating material into contact with the first solution containing ozone is 4 to 20 minutes. The pretreatment method for an electroless plating material according to claim 1 or 2, wherein the first solution contains at least 100 ppm of ozone. A method for producing a plating-coated member, comprising subjecting a plating material subjected to the pretreatment method according to any one of claims 1 to 3 to an electroless plating treatment. The method for manufacturing a plated member according to claim 4, wherein the electroless plating process is further performed on the plating material that has been subjected to the electroless plating process.

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