JP2019157142A - Plated resin molding and method for manufacturing the same - Google Patents

Abstract

To provide a plated resin molding manufactured with a less load to the environment and capable of using even a resin except an ABS resin, and a method for manufacturing the same.SOLUTION: A plated resin molding 1 includes a resin containing base 3 and an electroless plating layer 5 formed on the surface of the base 3. A structure unit derived from a silane coupling agent is fixed to the surface of the base 3 by a covalent bond; the silane coupling agent has a functional group capable of capturing catalytic metal; the catalytic metal captured by the functional group bonds with the electroless plating layer; and 3-aminopropyl ethoxy silane is preferably used as a silane coupling agent.SELECTED DRAWING: Figure 2

Description

  The present disclosure relates to a plated resin molded article and a method for producing a plated resin molded article.

Conventionally, articles having a plating layer have been widely developed. For example, Patent Document 1 discloses a material in which a nickel-chromium plating layer having corrosion resistance and antibacterial properties is formed by performing a nickel plating process including inorganic antibacterial agent particles on a substrate surface and further performing a chromium plating process. Has been.
Various plated resin molded products have also been developed. For example, a molded product obtained by etching an ABS resin with hexavalent chromium and supporting a catalyst metal necessary for electroless plating has been developed. In this, butadiene is oxidized and dissolved by etching, and the resin and the plating layer are joined together by an anchor effect.

Japanese Patent Laid-Open No. 10-68100

However, hexavalent chromium is a chemical substance with a high environmental load. Hexavalent chromium is also required to be converted to a process with a low environmental impact due to the trend of tightening regulations in Europe such as RoHS.
Conventionally, most of the resins on which a plating layer is practically used are ABS resins that can be etched with hexavalent chromium.
The present invention has been made in view of the above circumstances, and an object of the present invention is to provide a plated resin molded product that can be manufactured with less environmental burden and that can also use a resin other than an ABS resin, and a method for manufacturing the same. And The present invention can be realized as the following forms.

[1] a substrate containing a resin;
An electroless plating layer formed on the surface of the substrate,
A structural unit derived from a silane coupling agent is fixed to the surface of the substrate by a covalent bond,
The silane coupling agent has a functional group capable of capturing a catalytic metal,
A plated resin molded product, wherein the catalytic metal captured by the functional group is bonded to the electroless plating layer.

  [2] A structural unit derived from the silane coupling agent is fixed to the surface of the substrate by a reaction between a hydroxyl group and / or a carboxyl group on the surface side of the substrate and a hydroxyl group on the silane coupling agent side. The plated resin molded product according to [1], wherein

  [3] The plated resin molded product according to [1] or [2], wherein the functional group capable of capturing the catalytic metal is an amino group.

  [4] The silane coupling agent includes 3-aminopropyltriethoxysilane, 3-aminopropyltrimethoxysilane, N- (2-aminoethyl) -3-aminopropyltrimethoxysilane, N- (2-aminoethyl). ) -3-aminopropylmethyldimethoxysilane, N, N-bis [3- (trimethoxysilyl) propyl] ethylenediamine, and p- [N- (2-aminoethyl) aminomethyl] phenethyltrimethoxysilane The plated resin molded article according to any one of claims [1] to [3], wherein the plated resin molded article is one or more selected.

  [5] The resin is ABS, PP, PE, PVC, PS, PMMA, PBT, PA66, PA6, m-PPE, PC, PET, SPS, POM, PEEK, PPA, PAI, PPS, LPC, PEI, PAR. The plated resin molded article according to any one of claims [1] to [4], wherein the plated resin molded article is one or more selected from the group consisting of PSU, PSU, and PES.

[6] A modification step of modifying the surface of the substrate containing the resin with an oxidizing agent;
A coupling reaction step in which a silane coupling agent is reacted with the surface of the substrate after the modification step;
A catalyst metal supporting step for supporting the catalyst metal by contacting a liquid containing the catalyst metal with the surface of the substrate after the coupling reaction step;
An electroless plating step of forming an electroless plating layer on the surface of the substrate after the catalyst metal supporting step, and a method for producing a plated resin molded product.

  [7] The method according to [6], further comprising an alkali immersing step of immersing the surface of the substrate in an alkali solution between the modifying step and the coupling reaction step. Manufacturing method of plated resin molded product.

  [8] The method for producing a plated resin molded article according to [6] or [7], wherein the oxidizing agent is persulfuric acid.

Since the plating resin molded product of the present invention does not require etching with hexavalent chromium, it can be manufactured with less environmental burden. In the plated resin molded article of the present invention, etching with hexavalent chromium is unnecessary, and therefore various resins other than ABS resin can be used.
According to the method for producing a plated resin molded article of the present invention, since etching with hexavalent chromium is not performed, the burden on the environment can be reduced.

The invention will be further described in the following detailed description, given by way of non-limiting example of exemplary embodiments according to the invention, with reference to the mentioned drawings.
It is sectional drawing which shows an example of a plating resin molded product typically. It is explanatory drawing which shows an example of a plating resin molded product typically. It is explanatory drawing which shows an example of a manufacturing method. It is explanatory drawing which shows an example of a manufacturing method. It is a SEM image (image by a scanning electron microscope) of the substrate surface before a modification process. It is a SEM image of the substrate surface after a modification process. It is a SEM image of the substrate surface after etching with hexavalent chromium. It is the external appearance photograph of the board | substrate of ABS resin before plating. It is an external appearance photograph of Experimental example 12. 2 is an appearance photograph of Experimental Example 1. 14 is a SEM image of a substrate-side release surface of Experimental Example 6. 10 is a SEM image of a plating layer side peeling surface of Experimental Example 6. It is a SEM image of the board | substrate side peeling surface of Experimental example 8. 10 is a SEM image of a plating layer side release surface of Experimental Example 8. It is a SEM image of the board | substrate side peeling surface of Experimental example 11. FIG. 14 is a SEM image of a plating layer side peeling surface of Experimental Example 11.

  Hereinafter, embodiments of the present invention will be described in detail. In addition, in this specification, in the description using "-" about a numerical range, unless there is particular notice, a lower limit and an upper limit shall be included. For example, the description “10 to 20” includes both “10” as the lower limit and “20” as the upper limit. That is, “10 to 20” has the same meaning as “10 to 20”.

1. Plating Resin Molded Article 1 As shown in FIG. 1, the plated resin molded article 1 of the present invention includes a base 3 containing a resin, an electroless plating layer 5 formed on the surface of the base 3, and a non-conductive as needed. An electroplating layer 7 formed on the electroplating layer 5. In the present invention, the electroplating layer 7 is not an essential requirement but an optional requirement.
And the structural unit derived from a silane coupling agent is being fixed to the surface of the base | substrate 3 by the covalent bond. The silane coupling agent has a functional group capable of capturing the catalytic metal. The catalytic metal captured by this functional group is bonded to the electroless plating layer 5.

(1) Substrate “Substrate 3” contains a resin. The resin is not particularly limited. The resins are ABS, PP (polypropylene), PE (polyethylene), PVC (polyvinyl chloride), PS (polystyrene), PMMA (polymethyl methacrylate), PBT (polybutylene terephthalate), PA66 (polyamide 66), PA6 (polyamide) 6), m-PPE (modified polyphenylene ether), PC (polycarbonate), PET (polyethylene terephthalate), SPS (syndiotactic polystyrene), POM (polyacetal), PEEK (polyether ether ketone), PPA (polyphthalamide) , PAI (polyamideimide), PPS (polyphenylene sulfide), LPC (liquid crystal polymer), PEI (polyetherimide), PAR (polyarylate), PSU (polysulfone), and PES (polysulfone) Is preferably at least one selected from the group consisting of Terusaruhon).
Components other than the resin can be added to the substrate 3. Other components are not particularly limited. For example, inorganic fillers, antioxidants, heat stabilizers (hindered phenols, hydroquinones, phosphites, and their substitutes), weathering agents (resorcinols, salicylates, benzotriazoles, benzophenones, hindered amines) Etc.), mold release agents, lubricants (montanic acid and its metal salts, its esters, their half esters, stearyl alcohol, stearamide, various bisamides, bisureas, polyethylene waxes, etc.), pigments (cadmium sulfide, phthalocyanine, carbon for coloring) Black, etc.), dye (Nigrosine, etc.), crystal nucleating agent (talc, silica, kaolin, clay, etc.), plasticizer (octyl p-oxybenzoate, N-butylbenzenesulfonamide, etc.), antistatic agent (alkyl sulfate type) Anionic antistatic agent, grade 4 Ammonium salt type cationic antistatic agent, nonionic antistatic agent, betaine amphoteric antistatic agent, etc.), flame retardant (eg red phosphorus, phosphate ester, melamine cyanurate, magnesium hydroxide, aluminum hydroxide, etc. water) Oxides, ammonium polyphosphate, brominated polystyrene, brominated polyphenylene ether, brominated polycarbonate, brominated epoxy resins or combinations of these brominated flame retardants and antimony trioxide), thermal stabilizers, lubricants (aluminum stearate) , Lithium stearate, etc.), UV inhibitors, colorants, flame retardants, foaming agents and the like can be added.

(2) Electroless Plating Layer An electroless plating layer 5 is formed on the surface of the substrate 3. The metal constituting the electroless plating layer 5 is not particularly limited. As an electroless plating solution for forming the electroless plating layer 5, an autocatalytic electroless plating solution, for example, an electroless Ni-P plating solution, an electroless Ni-B plating solution, or an electroless Ni-P- B plating solution, electroless Ni—Cu—P plating solution, electroless copper plating solution and the like can be preferably used.
The thickness of the electroless plating layer 5 is not particularly limited. The thickness is preferably 0.1 to 10 μm, more preferably 0.1 to 5 μm, and still more preferably 0.1 to 1 μm, from the viewpoints of adhesion strength, plating time, and the like.

(3) Electroplating layer On the electroless plating layer 5, the electroplating layer 7 is formed as needed. The metal which comprises the electroplating layer 7 is not specifically limited. The metal constituting the electroplating layer 7 is Cu (copper), Ni (nickel), Cr (chromium), Au (gold), Zn (zinc), Sn (tin), Cd (cadmium), Ag (silver), One or more selected from the group consisting of Rh (rhodium), Pd (palladium), Pt (platinum) and the like are preferably used.
The thickness of the electroplating layer 7 is selected according to the purpose and is not particularly limited.

(4) Relationship between the surface of the substrate and the electroless plating layer The structural unit derived from the silane coupling agent is fixed to the surface of the substrate 3 by a covalent bond. The silane coupling agent is not particularly limited, but 3-aminopropyltriethoxysilane, 3-aminopropyltrimethoxysilane, N- (2-aminoethyl) -3-aminopropyltrimethoxysilane, N- (2- Aminoethyl) -3-aminopropylmethyldimethoxysilane, N, N-bis [3- (trimethoxysilyl) propyl] ethylenediamine, and p- [N- (2-aminoethyl) aminomethyl] phenethyltrimethoxysilane. One or more selected from the group can be suitably used. In these silane coupling agents, the functional group capable of capturing the catalytic metal is an amino group.
It is preferable that the structural unit derived from the silane coupling agent is fixed on the surface of the substrate 3 by the reaction between the hydroxyl group and / or carboxyl group on the surface side of the substrate 3 and the hydroxyl group on the silane coupling agent side.
The catalytic metal captured by the functional group capable of capturing the catalytic metal is bonded to the electroless plating layer. The catalyst metal is not particularly limited, but at least one selected from the group consisting of Pd (palladium) and Au (gold) can be suitably used.
FIG. 2 illustrates a case where 3-aminopropylethoxysilane is used as the silane coupling agent and Pd is used as the catalyst metal.
Note that the structural unit derived from the silane coupling agent preferably has a structure represented by the following general formula (1), for example. The structural unit derived from the silane coupling agent particularly preferably has a structure represented by the following formula (2).

(However, n is an integer of 1-10.)

2. Manufacturing method of plated resin molded product The manufacturing method of the plated resin molded product of the present invention includes the following steps.
(1) a modification step of modifying the surface of the substrate containing the resin with an oxidizing agent; and (2) a coupling reaction step of reacting the silane coupling agent with the surface of the substrate after the modification step;
(3) a catalyst metal supporting step for supporting the catalyst metal by contacting the surface of the substrate after the coupling reaction step with a liquid containing the catalyst metal;
(4) An electroless plating step of forming an electroless plating layer on the surface of the substrate after the catalyst metal supporting step.
Further, (5) after the electroless plating step, an electroplating step of forming an electroplating layer on the electroless plating layer may be provided.
3 and 4 illustrate the case where 3-aminopropylethoxysilane is used as the silane coupling agent and Pd (palladium) is used as the catalyst metal.

2.1 Modification Step In the modification step, the surface of the substrate containing the resin is modified with an oxidizing agent. A hydroxyl group and / or a carboxyl group is formed on the surface of the substrate by the oxidizing agent. The oxidizing agent is not particularly limited, but persulfuric acid is preferable, and specifically, persulfates are preferably used. As the persulfates, one or more selected from the group consisting of ammonium persulfate, sodium persulfate, and potassium persulfate can be suitably used.
The concentration of the oxidizing agent is not particularly limited. The density | concentration of an oxidizing agent becomes like this. Preferably it is 0.1-10M, More preferably, it is 0.1-5M, More preferably, it is 1-5M. Within this range, it is possible to form hydroxyl groups and / or carboxyl groups without undue damage to the surface of the substrate.
The reaction temperature and reaction time when using an oxidizing agent are not particularly limited. Reaction temperature becomes like this. Preferably it is 30-80 degreeC, More preferably, it is 40-80 degreeC, More preferably, it is 50-70 degreeC. The reaction time is preferably 1 to 60 minutes, more preferably 2 to 30 minutes, and further preferably 5 to 20 minutes. Within this range, it is possible to form hydroxyl groups and / or carboxyl groups without undue damage to the surface of the substrate.
In addition, after completion | finish of a modification | reformation process, it is preferable to wash a base | substrate with water. This is for removing the remaining oxidizing agent.

2.2 Coupling reaction step In the coupling reaction step, a silane coupling agent is reacted with the surface of the substrate after the modifying step.
The silane coupling agent is: The silane coupling agent described in (4) can be preferably used.
In this step, it is preferable to use an aqueous solution of a silane coupling agent.
The concentration of this aqueous solution is not particularly limited. The concentration is preferably 0.01 to 10 wt%, more preferably 0.01 to 5 wt%, and still more preferably 0.01 to 1.0 wt%. This is because the silane coupling reaction is sufficiently performed when the concentration of the aqueous solution is within this range.

In this step, it is preferable to perform a silane coupling reaction after the substrate is immersed in an aqueous solution of a silane coupling agent.
The temperature of the aqueous solution of the silane coupling agent during immersion is not particularly limited. The temperature is preferably 10 to 50 ° C, more preferably 10 to 40 ° C, and still more preferably 10 to 30 ° C.
The immersion time is not particularly limited. The immersion time is preferably 5 to 60 minutes, more preferably 5 to 30 minutes, and still more preferably 5 to 15 minutes.
When the temperature and immersion time are within these ranges, the silane coupling agent can be sufficiently adhered to the surface of the substrate.

The reaction temperature when performing the silane coupling reaction is not particularly limited. Reaction temperature becomes like this. Preferably it is 30-200 degreeC, More preferably, it is 30-160 degreeC, More preferably, it is 60-120 degreeC.
The reaction time is not particularly limited. The reaction time is preferably 0.5 to 5 hours, more preferably 0.5 to 3 hours, and further preferably 1 to 3 hours.
When the reaction temperature and reaction time are within these ranges, the silane coupling reaction is sufficiently performed, and the structural unit derived from the silane coupling agent is fixed on the surface of the substrate.

In addition, before immersing the substrate in the aqueous solution of the silane coupling agent, that is, between the reforming step and the coupling reaction step, in order to promote the formation of the hydroxyl group required for the reaction with the silane coupling agent, You may perform the pretreatment (equivalent to an "alkali immersion process") immersed in a solution (alkaline aqueous solution). The alkali agent used for the alkaline solution is not particularly limited. As the alkali agent, for example, one or more selected from the group consisting of NaOH, KOH, LiOH, CaO, and Ca (OH) ₂ is preferably used. The concentration of the alkaline agent in the alkaline solution is not particularly limited. The concentration of the alkali agent is preferably adjusted so that the total amount of the alkali agents contained in 1 L is 0.1 to 10 mol, more preferably 0.1 to 5 mol. It is particularly preferred that the amount be prepared to be 5 to 1.5 mol.

2.3 Catalytic metal loading process In the catalytic metal loading process, the liquid containing the catalytic metal is brought into contact with the surface of the substrate after the coupling reaction process to carry the catalytic metal.
The liquid containing the catalyst metal is not particularly limited as long as it is a liquid containing the catalyst metal. For example, a palladium chloride solution (aqueous solution) or a tetrachloroauric acid solution (aqueous solution) is used.
The liquid composition can be changed depending on the type of catalyst metal to be supported. For example, when palladium and gold are used for the catalyst, the Pd mole fraction of the Pd / Au catalyst is preferably 0.2 to 0.8, more preferably 0.3 to 0.7, still more preferably 0.4. Adjust to ~ 0.6. Of course, palladium alone or gold alone may be used.
The concentration of the catalyst metal in the liquid containing the catalyst metal is preferably 0.0001 to 0.02M, more preferably 0.0001 to 0.01M, still more preferably 0.001 to 0.01M. is there. Within this range, the catalyst metal can be sufficiently supported. Here, the concentration of the catalyst metal means the total concentration when a plurality of types of catalyst metals are used.

2.4 Electroless plating process (chemical plating process)
In the electroless plating step, an electroless plating layer is formed on the surface of the substrate after the catalyst metal supporting step.
The electroless plating step is a step of forming a metal film by reducing and precipitating metal ions on the surface of a substrate carrying a catalytic metal. The method of electroless plating is not particularly limited, and any conventional or known method can be widely employed in the resin plating process. As an electroless plating solution, an autocatalytic electroless plating solution, for example, an electroless Ni-P plating solution, an electroless Ni-B plating solution, an electroless Ni-P-B plating solution, or an electroless Ni-Cu-P. A method using a plating solution, an electroless copper plating solution or the like is preferably used.

2.5 Electroplating process (optional process)
In the electroplating process, an electroplating layer is formed on the electroless plating layer after the electroless plating process.
The electroplating film may be a single metal film or a multilayer film composed of a plurality of metal films.
The electroplating layer is formed to provide a specific function. The electroplating layer is intended for, for example, decoration, increasing hardness, water repellency, and the like. The type of electroplating layer is not particularly limited. Preferable examples of the electroplating layer include a chromium plating film, a copper plating film, and a nickel plating film.
The method of electroplating is not particularly limited, and any conventional or publicly known method can be widely used in the resin plating process.

  Hereinafter, the present invention will be described more specifically with reference to examples. Experimental examples 1 to 11 correspond to examples, and experimental example 12 corresponds to a comparative example.

1. Preparation of Samples of Experimental Examples 1 to 11 (1) Substrate Cleaning An ABS resin substrate (corresponding to “base”, size 50 mm × 100 mm) was subjected to ultrasonic cleaning with IPA (isopropyl alcohol). The washing conditions were 10 minutes at room temperature. Thereafter, the substrate was dried with a dryer.
(2) Modification process A 2.0 M ammonium persulfate aqueous solution was used for the modification process of the substrate surface. As shown in Table 1, the conditions for the reforming treatment were 60 ° C. and 10 minutes, or 70 ° C. and 10 minutes. After the modification treatment, the substrate was washed with water.
In FIG. 5, the SEM image (image by a scanning electron microscope) of the substrate surface before a modification process is shown. FIG. 6 shows an SEM image of the substrate surface after a modification treatment for 10 minutes using a 2.0 M ammonium persulfate aqueous solution. FIG. 7 shows an SEM image of the substrate surface etched with hexavalent chromium.
5 to 7, it can be seen that the modification treatment with the ammonium persulfate aqueous solution causes less damage to the substrate surface than the etching with hexavalent chromium. That is, as shown in FIG. 6, in the modification treatment with the ammonium persulfate aqueous solution, it is understood that when the SEM is observed with a magnification capable of distinguishing 5 μm, unevenness is hardly observed on the substrate surface. On the other hand, as shown in FIG. 7, in etching with hexavalent chromium, unevenness is clearly observed on the surface of the substrate when observed with a SEM at a magnification capable of distinguishing 5 μm.
The contact angle with respect to water on the substrate surface before the modification treatment was 76.6 °, but the contact angle with respect to water after the modification treatment for 10 minutes using a 2.0 M aqueous ammonium persulfate solution was 58. It was 8 °. Thus, it was found that the wettability to water was improved by the modification treatment.

(3) Coupling reaction 0.05 wt% of 3-aminopropylethoxysilane was used for the coupling reaction. First, the substrate after the modification treatment was immersed in a 0.05 wt% 3-aminopropylethoxysilane solution at pH = 3.0 and room temperature for 10 minutes. Thereafter, the substrate was heated at 80 ° C. for 2 hours to carry out a silane coupling reaction. Thereafter, the substrate was naturally cooled to room temperature.
(4) Catalyst metal support Next, the substrate was immersed in a catalyst metal-containing liquid to support the catalyst metal. As this liquid, the liquid (aqueous solution) shown in Table 1 was used. Thereafter, the substrate was washed with water.
In addition, palladium chloride and tetrachloroauric acid were used as the compound containing the catalyst metal.
(5) Electroless plating Electroless Ni-P plating bath comprising nickel (II) sulfate hexahydrate 0.1 mol / L, sodium phosphinate monohydrate 0.2 mol / L, glycine 0.2 mol / L ( Electroless plating was performed for the time shown in Table 1 using pH = 5.0, 70 ° C.).
(6) Electroplating For Experimental Examples 6, 8, and 11, electro Cu plating was further performed by 30 μm.

2. Preparation of Sample of Experimental Example 12 A sample was manufactured in the same manner as in Experimental Example 1 except that the modification treatment was not performed.

3. Evaluation Method (1) Evaluation of Plating Deposition For each sample, the surface of the substrate after electroless plating was visually observed. Evaluation was performed as follows.

A: Plating was deposited on the entire surface of the substrate.
○: Plating was deposited. However, there are some undeposited parts.
X: Plating does not precipitate.

(2) Measurement of peel strength JIS H 8630 Annex 1 Based on the adhesion test method, incisions with a width of about 10 mm are made in the plating layers of the samples of Experimental Examples 6, 8, and 11 and the peeling is performed at a speed of 25 mm / min. The load when measured was measured. The n number was 3. In this way, the peel strength of the samples of Experimental Examples 6, 8, and 11 was measured. Furthermore, the state of the peeling surface of each sample after the measurement was observed. As the peeling surface, both the substrate side and the plating layer side were observed by SEM.

4). Results The results of plating deposition evaluation are shown in Table 1. In any samples of Experimental Examples 1 to 11, plating was deposited on the surface. On the other hand, in Experimental Example 12, no plating was deposited. This is illustrated in FIGS. FIG. 8 shows an appearance photograph of the ABS resin substrate before plating. In FIG. 9, the external appearance photograph of the sample of Experimental example 12 is shown. In FIG. 10, the external appearance photograph of the sample of Experimental example 1 is shown. The sample of Experimental Example 12 in FIG. 9 is the same as the substrate before plating in FIG. 8, and it can be seen that no plating is deposited. In the sample of Experimental Example 1 in FIG. 10, it can be seen that plating is deposited on the entire surface of the substrate. The size of the substrate (sample) shown in FIGS. 8 to 10 is 50 mm × 50 mm.

  Next, Table 2 shows the measurement results of peel strength. From the results in Table 2, it was confirmed that sufficient peel strength was obtained in any of the samples of Experimental Examples 6, 8, and 11. In addition, it was found that the plating was uniformly deposited on the substrate because there was little variation in peel strength in any sample.

Next, the observation result of a peeling surface is demonstrated. If the adhesion strength between the plating layer and the substrate is low, peeling should occur between the plating layer and the substrate. In this case, the metal of the plating layer appears on the peeling surface on the plating layer side, and the resin of the substrate appears on the peeling surface on the substrate side. On the other hand, when the adhesion strength between the plating layer and the substrate is high, peeling does not occur between the plating layer and the substrate, and the substrate is ductile fractured. In this case, the resin of the substrate appears on the peeling surface on the plating layer side, and the resin of the substrate also appears on the peeling surface on the substrate side.
FIG. 11 shows a peeling surface on the substrate side of the sample of Experimental Example 6. FIG. 12 shows the peeling surface on the plating layer side of the sample of Experimental Example 6. It was confirmed that the resin appeared on any peeling surface. This result shows that ductile fracture occurred in the substrate without peeling between the plating layer and the substrate. That is, since the adhesion strength between the plating layer and the substrate is very high, no peeling occurred between the plating layer and the substrate, and ductile fracture occurred in the substrate.
FIG. 13 shows a peeling surface on the substrate side of the sample of Experimental Example 8. FIG. 14 shows a peeling surface on the plating layer side of the sample of Experimental Example 8. It was confirmed that the resin appeared on any peeling surface. Also in this case, since the adhesion strength between the plating layer and the substrate is very high, it can be seen that ductile fracture occurs in the substrate without peeling between the plating layer and the substrate.
FIG. 15 shows a peeling surface on the substrate side of the sample of Experimental Example 11. FIG. 16 shows a peeling surface on the plating layer side of the sample of Experimental Example 11. It was confirmed that the resin appeared on any peeling surface. Also in this case, since the adhesion strength between the plating layer and the substrate is very high, it can be seen that ductile fracture occurs in the substrate without peeling between the plating layer and the substrate.

5). Effects of Examples As described above, it was confirmed that the samples subjected to the modification treatment, the coupling reaction, the catalytic metal support, the electroless plating, and the electroplating in this order have high adhesion of the plating layer. Since the plated resin molded product manufactured in this way does not require etching with hexavalent chromium, it can be manufactured with less environmental burden.

6). Others When a substrate containing a polyphenylene sulfide resin is used, a plating layer with high adhesion can be formed as in the case of the ABS resin.

  The present invention is not limited to the embodiments described in detail above, and various modifications or changes can be made within the scope of the claims of the present invention.

  The present invention can be applied to a wide range of resin molded products.

DESCRIPTION OF SYMBOLS 1 ... Plating resin molding 3 ... Base | substrate 5 ... Electroless plating layer 7 ... Electroplating layer

Claims (8)

A substrate containing a resin;
An electroless plating layer formed on the surface of the substrate,
A structural unit derived from a silane coupling agent is fixed to the surface of the substrate by a covalent bond,
The silane coupling agent has a functional group capable of capturing a catalytic metal,
A plated resin molded product, wherein the catalytic metal captured by the functional group is bonded to the electroless plating layer.   A structural unit derived from the silane coupling agent is fixed to the surface of the substrate by a reaction between a hydroxyl group and / or a carboxyl group on the surface side of the substrate and a hydroxyl group on the silane coupling agent side. The plated resin molded product according to claim 1.   The plated resin molded product according to claim 1, wherein the functional group capable of capturing the catalytic metal is an amino group.   The silane coupling agent is 3-aminopropyltriethoxysilane, 3-aminopropyltrimethoxysilane, N- (2-aminoethyl) -3-aminopropyltrimethoxysilane, N- (2-aminoethyl) -3. Selected from the group consisting of -aminopropylmethyldimethoxysilane, N, N-bis [3- (trimethoxysilyl) propyl] ethylenediamine, and p- [N- (2-aminoethyl) aminomethyl] phenethyltrimethoxysilane. The plated resin molded article according to any one of claims 1 to 3, wherein the plated resin molded article is one or more kinds.   The resin is ABS, PP, PE, PVC, PS, PMMA, PBT, PA66, PA6, m-PPE, PC, PET, SPS, POM, PEEK, PPA, PAI, PPS, LPC, PEI, PAR, PSU, The plated resin molded article according to any one of claims 1 to 4, wherein the plated resin molded article is one or more selected from the group consisting of PES and PES. A modification step of modifying the surface of the substrate containing the resin with an oxidizing agent;
A coupling reaction step in which a silane coupling agent is reacted with the surface of the substrate after the modification step;
A catalyst metal supporting step for supporting the catalyst metal by contacting a liquid containing the catalyst metal with the surface of the substrate after the coupling reaction step;
An electroless plating step of forming an electroless plating layer on the surface of the substrate after the catalyst metal supporting step, and a method for producing a plated resin molded product.   The plating resin molding according to claim 6, further comprising an alkali immersing step of immersing the surface of the substrate in an alkaline solution between the modifying step and the coupling reaction step. Product manufacturing method.   The method for producing a plated resin molded article according to claim 6 or 7, wherein the oxidizing agent is persulfuric acid.