JP2019135329A - Plating part - Google Patents

Abstract

To provide a plating part having a plating film having high adhesion strength, and excellent in appearance characteristic, on a compact surface containing a polymer alloy.SOLUTION: In a plating part having a compact containing a polymer alloy containing 20-90 wt% polyamide and 10-80 wt% polyolefin, and an electroless plating film on a compact surface, a polyamide area and a polyolefin area exist inside the compact, and a width of a gap generated between the polyamide area and the polyolefin area is 1 μm or less.SELECTED DRAWING: Figure 2

Description

  The present invention relates to a plated part.

  The demands on the performance and function of polymer materials are becoming increasingly diverse and sophisticated, and it is almost difficult to meet with a single polymer. Therefore, in recent years, a polymer alloy method using a plurality of polymers has become the mainstream in the development of polymer materials. For example, Patent Document 1 discloses a polymer alloy of a thermoplastic resin (A) such as a polyamide resin or a polyester resin and a resin (B) having a reactive functional group. According to Patent Document 1, the polymer alloy is excellent in the balance between the conflicting characteristics of impact resistance and rigidity.

  In recent years, in the field of automobile parts and the like, resin parts in which a metal film is formed on the surface of a resin molded body have been actively used for the purpose of weight reduction. Electroless plating is known as a method for forming a metal film on a resin molded body at a low cost.

Japanese Patent Laid-Open No. 2005-187809

  However, when conventional electroless plating is performed on a molded body using a polymer alloy, various problems arise. For example, a polymer alloy may include a plurality of polymers having different heat resistance and water absorption. When conventional electroless plating is performed on such a polymer alloy, the adhesion strength of the plating film is low, and the appearance characteristics of the plating film may be inferior.

  The present invention solves these problems and provides a plated part having a plating film having high adhesion strength and excellent appearance characteristics on the surface of a molded article containing a polymer alloy.

  According to a reference aspect of the present invention, there is provided a method for producing a plated part, in which a polymer alloy containing 20% to 90% by weight of polyamide and 10% to 80% by weight of polyolefin is molded to obtain a molded body. And applying an electroless plating catalyst to the formed body, and contacting the formed body provided with the electroless plating catalyst with an acidic electroless nickel phosphorus plating solution at 50 ° C. to 80 ° C., There is provided a method for producing a plated part including forming an electroless plating film on the surface of the molded body.

  In a reference embodiment, the electroless plating catalyst may be palladium chloride, and palladium chloride may be imparted to the molded body by contacting the molded body with an electroless plating catalyst solution containing hydrochloric acid and palladium chloride. . The concentration of hydrochloric acid in the electroless plating catalyst solution may be 1.0N to 4.0N. The electroless nickel phosphorus plating solution may have a temperature of 50 ° C. to 70 ° C. and a pH of 4.0 to 6.0.

  In a reference embodiment, the polymer alloy may include 40% to 70% by weight of polyamide and 30% to 60% by weight of polyolefin, and the polymer alloy may further include 1% to 10% by weight of a compatibilizer. May be included. Further, the polyamide may be nylon 6 and the polyolefin may be polypropylene.

  The plated component has a first part where the electroless plating film is formed on the surface and a second part where the electroless plating film is not formed on the surface, and forms the molded body. The first thermoplastic resin containing the polymer alloy is plasticized and melted to obtain the first molten resin, and the second thermoplastic resin is plasticized and melted to obtain the second molten resin. And using the first molten resin and the second molten resin, the molded body having a first portion made of the first molten resin and a second portion made of the second molten resin. The electroless plating film may be formed on the surface of the first portion of the molded body. Further, the molded body may be molded by two-color molding.

  The molded body may further include a block copolymer having a hydrophilic segment, and the molded body may be molded by molding the polymer alloy and the block copolymer. The molded body further includes a block copolymer having a hydrophilic segment and metal fine particles, and molding the molded body produces a resin pellet including the block copolymer and the metal fine particles; And molding the polymer alloy and the resin pellet to obtain the molded body. Further, the production of the resin pellets may include contacting the block copolymer with pressurized carbon dioxide in which the metal fine particles are dissolved or dispersed, and allowing the metal fine particles to penetrate into the block copolymer. Good.

  According to the present invention, there is provided a molded part comprising a polymer alloy containing 20 to 90% by weight of polyamide and 10 to 80% by weight of polyolefin, and an electroless plating film on the surface of the molded body. In addition, there is provided a plated part characterized in that a polyamide region and a polyolefin region are present inside the molded body, and a width of a gap generated between the polyamide region and the polyolefin region is 1 μm or less. The

  The polyamide region and the polyolefin region may form a sea-island structure inside the molded body.

  The molded body has a first portion having the electroless plating film on the surface and a second portion not having the electroless plating film on the surface, and the first portion is the polymer. The alloy may be included, and the second portion may include the second thermoplastic resin. The water absorption rate of the first part when immersed in water at 23 ° C. for 24 hours is 0.5% by weight to 3.0% by weight, and the water absorption rate of the second part is 2.0% by weight. It may be the following. The second thermoplastic resin may include polypropylene. The molded body may be an integrally molded body of the first part and the second part.

  The plated component of the present invention has a molded body containing a polymer alloy containing polyamide and polyolefin in a specific range ratio, and an electroless plating film formed on the surface of the molded body. It has high adhesion strength and excellent appearance characteristics.

It is a flowchart explaining the manufacturing method of the plating components of 1st Embodiment. FIG. 2A is a schematic diagram showing a cross-sectional structure of the plated component of the first embodiment, and FIG. 2B is a schematic diagram showing only islands (domains) in FIG. 2A. It is a partially expanded view of the cross-sectional structure of the plated component of the first embodiment in FIG. It is the schematic of the plated component of 2nd Embodiment. It is a flowchart explaining the manufacturing method of the plating components of 2nd Embodiment. (A)-(e) is a figure explaining the two-color shaping | molding of the molded object of 2nd Embodiment. 2 is a cross-sectional TEM photograph of a plated part manufactured in Example 1. FIG. 4 is a cross-sectional TEM photograph of a plated part manufactured in Comparative Example 1.

[First Embodiment]
(1) Manufacturing method of plated parts <Molding of molded body>
A method for manufacturing a plated component according to this embodiment will be described with reference to the flowchart shown in FIG. First, a molded body containing a polymer alloy of polyamide (PA) and polyolefin (PO) (hereinafter simply referred to as “PA / PO polymer alloy” as appropriate) is molded (step S1 in FIG. 1). The polyamide contained in the PA / PO polymer alloy is not particularly limited, and nylon 6 (PA6), nylon 66 (PA66), nylon 12 (PA12), nylon 11 (PA11), nylon 6T (PA6T), nylon MXD6 ( PAMXD6: polyamide using meta-xylenediamine (MXDA)), nylon 6.66 copolymer, and the like can be used. Of these, nylon 6 (PA6) is preferred because it has high water absorption and easily swells, and therefore has high plating reactivity. As the polyamide, only one type may be used, or two or more types may be mixed and used.

  The polyolefin contained in the PA / PO polymer alloy is not particularly limited, but polyethylene, polypropylene, polybutene, ethylene-propylene copolymer, ethylene-butene copolymer, ethylene-hexene copolymer, ethylene-octene copolymer. Etc. can be used. Among these, polypropylene (PP) is preferable from the viewpoints of improving the chemical resistance of the molded product, reducing the weight and reducing the cost. As polyolefin, only 1 type may be used and 2 or more types may be mixed and used.

  The PA / PO polymer alloy contains 20 to 90% by weight of polyamide and 10 to 80% by weight of polyolefin. Furthermore, it is preferable to contain 40 to 70% by weight of polyamide and 30 to 60% by weight of polyolefin. In the present embodiment, in the subsequent electroless plating step (step S3 in FIG. 1), the electroless plating film selectively grows in the polyamide region in the molded body. For this reason, by setting the ratio of the polyamide in the PA / PO polymer alloy within the above range, the plated film is sufficiently formed on the molded body, and the adhesion between the plated film and the molded body can be sufficiently secured. In addition, by setting the ratio of the polyolefin in the PA / PO polymer alloy within the above range, characteristics such as flexibility of the polyolefin can be imparted to the molded body without impairing the characteristics of the polyamide such as high plating reactivity and heat resistance.

  The PA / PO polymer alloy may be a non-reinforced resin that does not contain fillers such as minerals and glass fibers, or may contain mineral-reinforced resins containing minerals, glass fibers (GF), carbon fibers, etc. It may be a fiber reinforced resin. In order to enhance the designability, it is preferable to use a mineral reinforced resin having a spherical particle shape and inconspicuous filler, and in the case where it is necessary to increase the rigidity, it is preferable to use a glass fiber reinforced resin. Further, when the molded body is thick, it is preferable to use a fiber reinforced resin because the movement of the resin is increased in the thermal shock test and the plating film may be broken. The content of the filler contained in the PA / PO polymer alloy can be appropriately determined according to the use of the plated part and the required strength. For example, the filler is preferably contained in the PA / PO polymer alloy in an amount of 5 to 80% by weight, and more preferably 10 to 60% by weight.

  The PA / PO polymer alloy may further contain a compatibilizing agent in order to improve the compatibility between the polyamide and the polyolefin. The compatibilizer is not particularly limited as long as it is a polyolefin resin containing a reactive functional group that reacts with a functional group present in the polyamide. Examples of reactive functional groups include amino groups, carboxyl groups, hydroxyl groups, acid anhydride groups, epoxy groups, isocyanate groups, mercapto groups, oxazoline groups, sulfonic acid groups, and the like. Among them, an epoxy group, an acid anhydride group, an isocyanate group, and an oxazoline group are preferable because of high reactivity and few side reactions such as decomposition and crosslinking. Examples of the acid anhydride in the acid anhydride group include maleic anhydride, itaconic anhydride, endic acid anhydride, citraconic anhydride, 1-butene-3,4-dicarboxylic acid anhydride, and the like. Of these, maleic anhydride and itaconic anhydride are preferred. The compatibilizer may contain only one type of reactive functional group or two or more types. The compatibilizing agent can be appropriately selected according to the type of polyamide and polyolefin, and specific compatibilizing agents include maleic anhydride-modified polypropylene (PP-MAH). The compatibilizer is contained in the PA / PO polymer alloy in an amount of, for example, 1% by weight to 10% by weight, and preferably 3% by weight to 5% by weight. By making the content of the compatibilizing agent within this range, the compatibility between the polyamide and the polyolefin is improved, and the two materials are not separated at the time of molding. (Matrix-domain structure) can be formed.

  The PA / PO polymer alloy may be a commercially available product, or may be produced using the polyamide and polyolefin described above. Examples of commercially available products include PA / PO polymer alloy resin pellets such as Amilan (registered trademark) S133 and Amilan (registered trademark) U141 manufactured by Toray. Further, the production method of the PA / PO polymer alloy is not particularly limited. For example, polyamide, polyolefin, if necessary, a compatibilizing agent, a filler and the like are mixed and extruded, and the extruded product is pulverized to obtain PA / PO polymer alloy resin pellets may be produced.

  In the present embodiment, the molded product may be molded only from the PA / PO polymer alloy, or in addition to the PA / PO polymer alloy, a block copolymer having a hydrophilic segment described later, and other general-purpose additives. You may shape | mold by adding. The content of the PA / PO polymer alloy in the molded body is arbitrary and can be determined as appropriate based on the use of the plated part. For example, the PA / PO polymer alloy is preferably contained in the molded body in an amount of 70 to 100% by weight, more preferably 85 to 100% by weight.

  In the present embodiment, in addition to the PA / PO polymer alloy, a molded body may be molded by adding a block copolymer having a hydrophilic segment (hereinafter referred to as “block copolymer” as appropriate). The block copolymer has a hydrophilic segment and another segment different from the hydrophilic segment (hereinafter referred to as “other segment” as appropriate). The block copolymer tends to segregate in the vicinity of the surface of the molded body during or after the molding process. As a result, the surface of the molded body becomes hydrophilic, and the electroless plating reactivity is improved.

  An anionic segment, a cationic segment, and a nonionic segment can be used for the hydrophilic segment of the block copolymer of this embodiment. Examples of anionic segments include polystyrene sulfonic acid, cationic segments include quaternary ammonium base-containing acrylate polymer systems, and nonionic segments include polyether ester amide systems, polyethylene oxide-epichlorohydrin systems, and polyether ester systems. Can be mentioned.

  As the block copolymer of the present embodiment, it is preferable that the hydrophilic segment is a nonionic segment having a polyether structure because the heat resistance of the molded product is easily secured. Examples of the polyether structure include oxyalkylene groups having 2 to 4 carbon atoms, polyether diols, polyether diamines, and modified products thereof, and polyether-containing hydrophilic polymers, and polyethylene oxide is particularly preferable.

  The other segment of the block copolymer of this embodiment is arbitrary as long as it is a hydrophobic segment rather than a hydrophilic segment, and the kind according to the objective can be selected. For example, polyamides such as nylon 6 and nylon 12, polyolefin, polylactic acid, polyethylene and the like can be used.

  In this embodiment, a commercial item may be used for a block copolymer. The block copolymer of this embodiment may be commercially available as a resin-kneaded polymer type antistatic agent because it segregates (orients) near the surface of the molded body. For example, Pelestat (registered trademark) or Peletron (registered trademark) manufactured by Sanyo Chemical Industries, Ltd. can be used as the block copolymer of this embodiment.

  The content of the block copolymer in the molded body is arbitrary, and can be appropriately determined based on the type of PA / PO polymer alloy, the type of block copolymer, the use of the plated part, and the like. For example, the block copolymer is preferably contained in an amount of 1 to 30% by weight, more preferably 1 to 20% by weight, and even more preferably 3 to 15% by weight. When the content of the block copolymer in the molded product is 1% by weight or more, the permeability of the plating solution can be sufficiently increased, and when it is 30% by weight or less, physical properties such as heat resistance and mechanical strength of the molded product. Is not greatly impaired.

  The molding method of the molded body of this embodiment is not particularly limited. For example, a material obtained by adding a block copolymer or other general-purpose additives to a PA / PO polymer alloy as necessary may be formed by general-purpose injection molding, extrusion molding, or the like to obtain a molded body.

<Plating pretreatment>
Next, an electroless plating catalyst is applied to the compact (step S2 in FIG. 1). In this embodiment, the molded body is brought into contact with an electroless plating catalyst solution in which palladium chloride is dissolved in hydrochloric acid. In the present embodiment, the step of bringing the electroless plating catalyst solution into contact with the molded body corresponds to a pre-plating process for forming a plating film on the molded body.

  The concentration of hydrochloric acid in the electroless plating catalyst solution of the present embodiment is, for example, 0.1 to 12N, preferably 0.1 to 5N, and more preferably 1.0 to 4.0N. . Palladium chloride may precipitate when the concentration of hydrochloric acid decreases. Therefore, the state of palladium ions dissolved in hydrochloric acid can be stably maintained by setting the hydrochloric acid concentration to 0.1 N or more. On the other hand, if the concentration of hydrochloric acid exceeds 12N, the appearance characteristics of the plating and the mechanical strength of the molded body may be affected by dissolution of the molded body.

  Palladium chloride functions as an electroless plating catalyst in an electroless plating process (step S3 in FIG. 1) described later. Palladium chloride is contained in the electroless plating catalyst solution, for example, 1 to 100 ppm by weight, preferably 25 to 75 ppm by weight. If the palladium chloride concentration is less than 1 ppm by weight, the amount of palladium chloride adsorbed on the surface of the molded product may be uneven, which may cause defects in the plating film. Further, when the palladium chloride concentration exceeds 100 ppm by weight, the amount of palladium chloride adsorbed on the surface of the molded body increases, the plating reaction on the outermost surface of the molded body becomes dominant, and the adhesion strength of the plating film may be reduced. There is.

  The time during which the electroless plating catalyst solution is in contact with the formed body (plating pretreatment time) is preferably 5 seconds to 15 minutes. If it is less than 5 seconds, the amount of metal ions adsorbed on the surface of the molded article may be uneven, and the electroless plating reaction may not be started uniformly. Moreover, when it exceeds 15 minutes, there exists a possibility of deterioration of the molded object by the hydrochloric acid which osmose | permeated the molded object, and corrosion of a plating film.

  Further, the temperature of the electroless plating catalyst solution brought into contact with the molded body is preferably 10 ° C to 50 ° C. When the temperature is less than 10 ° C., the amount of palladium ions adsorbed on the surface of the formed body may be uneven, and the electroless plating reaction may not be started uniformly. In addition, when the plating pretreatment is performed at less than 10 ° C., the temperature of the molded body also becomes low. For this reason, when the molded body after the pre-plating treatment is brought into contact with the electroless plating solution, the temperature of the plating solution is drastically lowered and the initial reaction of the plating becomes unstable, the covering property of the plating film is deteriorated, and the appearance is poor. May occur. On the other hand, when the temperature of the electroless plating catalyst solution exceeds 50 ° C., the amount of palladium ions adsorbed on the surface of the molded body increases, and there is a possibility that a plating reaction occurs only on the outermost surface of the molded body. Moreover, it may be difficult to stabilize the concentration of hydrochloric acid due to the generation of gas from hydrochloric acid or the evaporation of water.

  Furthermore, the electroless plating catalyst solution of this embodiment may contain a surfactant. By containing the surfactant, the surface tension of the electroless plating catalyst solution is lowered, the wettability to the surface of the molded body is improved, and palladium ions easily penetrate into the molded body. As the surfactant, a general-purpose surfactant such as an anionic surfactant, a cationic surfactant, a nonionic surfactant, and an amphoteric surfactant can be used.

  The method of bringing the electroless plating catalyst solution into contact with the molded body is arbitrary, and various methods can be used depending on the purpose. For example, the entire molded body may be immersed in an electroless plating catalyst solution. In addition, when only a part of the molded body is plated, only the part where the plating process is scheduled may be brought into contact with the electroless plating catalyst solution.

  Further, the molded body may be washed with water after contacting the molded body with the electroless plating catalyst solution. The washing temperature (water temperature) is preferably 50 ° C. or higher, which is the glass transition temperature of polyamide, and preferably 90 ° C. or lower from the viewpoint of suppressing thermal deformation of polyolefins such as polypropylene. By washing with water, palladium chloride adsorbed on the outermost surface of the molded body can be removed. When water at 50 ° C. or higher is used, the surface of the molded body can be swollen. As a result, the plating reaction on the outermost surface of the molded body is suppressed, and the electroless plating solution easily penetrates into the molded body, so that the growth of the plating film from the inside of the molded body is promoted. As a result, the adhesion strength of the plating film is improved.

  By the plating pretreatment described above, hydrochloric acid in the electroless plating catalyst solution etches the surface of the molded body, and palladium chloride is adsorbed on the surface of the molded body. According to the study by the present inventors, it was found that palladium chloride specifically adsorbs to the amide group of the polyamide in the PA / PO polymer alloy and hardly adsorbs to the polyolefin having no amide group. Furthermore, palladium chloride not only adsorbs to the outermost surface of the molded body, but also penetrates into the polyamide region existing in the vicinity of the surface of the molded body (for example, a region having a depth of 100 μm from the surface). The content of palladium contained in the molded body after the pre-plating treatment is, for example, 0.1 ppm to 20 ppm by weight, preferably 1 ppm to 10 ppm by weight in the vicinity of the surface of the molded product. In this embodiment, as will be described later, electroless plating is performed using an acidic electroless nickel phosphorus plating solution at 50 ° C. to 80 ° C. Since the electroless plating solution used in the present embodiment is at a certain high temperature, nickel sulfate ion precipitation (plating precipitation) is high, and the concentration of sodium hypophosphite as a reducing agent is high. For this reason, the electroless plating solution used in this embodiment has high plating reactivity. Since electroless plating is performed using an electroless nickel phosphorus plating solution having high plating reactivity, an electroless plating film can be formed even when the content of palladium is as low as 0.1 ppm by weight to 20 ppm by weight.

<Electroless plating>
Next, an acidic electroless nickel phosphorus plating solution at 50 ° C. to 80 ° C. is brought into contact with the molded body provided with the electroless plating catalyst to form an electroless plating film on the surface of the molded body (step S3 in FIG. 1). ). The treatment temperature of electroless plating (temperature of electroless plating solution) is preferably 50 ° C to 70 ° C. Moreover, pH of acidic electroless nickel phosphorus plating liquid is 4.0-6.0, for example, Preferably, it is 4.5-5.0.

  Conventionally, two types of methods have been mainly used as a treatment for applying a catalyst for electroless plating to a plastic substrate. A sensitizer-activating method in which a tin colloid is adsorbed on a substrate (sensitizer), immersed in a palladium chloride solution (activating), and palladium chloride is reduced and precipitated with stannous chloride, and palladium tin This is a catalyst-accelerator method in which a colloid is adsorbed on a substrate (catalyst) and then reduced with concentrated sulfuric acid or the like (accelerator). The electroless plating catalyst usually exhibits catalytic activity in a metal state having an oxidation number of 0 (zero). For this reason, in both the sensitizer-activating method and the catalyst-accelerator method, palladium is reduced while adsorbed on the substrate. Therefore, conventionally, even if palladium chloride that is not in a metallic state is applied to a substrate, it does not exhibit catalytic activity, and it has been difficult to use it as an electroless plating catalyst. In addition, palladium chloride has a problem that it is difficult to adsorb on the surface of the plastic substrate. However, the present inventors have found that an electroless plating reaction occurs without reducing palladium chloride by using a molded body containing polyamide as a base material and using an acidic electroless nickel phosphorus plating solution. It was. The cause of this is not clear, but using polyamide as the base material makes it easier for palladium chloride to adsorb on the base material, and sodium hypophosphite contained as a reducing agent in the electroless plating solution reduces palladium chloride. It is estimated that there is an effect. In the present embodiment, the reduction treatment of the electroless plating catalyst can be omitted, so that the manufacturing cost can be reduced and the throughput of the entire plated component manufacturing can be improved.

  Thus, in this embodiment, an electroless plating film can be formed on a molded object, without performing a palladium chloride reduction process, by using an acidic electroless nickel phosphorus plating solution. Therefore, when an alkaline electroless nickel phosphorus plating solution used for conventional plastic plating is used instead of the acidic electroless nickel phosphorus plating solution, it is difficult to form a plating film. For example, when an alkaline electroless nickel plating solution (chemical nickel plating solution) is used, it is difficult to form a plating film. Since the alkaline electroless nickel plating solution has a low sodium hypophosphite concentration and the temperature of the plating solution is as low as about 40 ° C., the phosphorus concentration in the formed plating film is as low as about 1 to 4% by weight. It is a plating solution. In the present embodiment, a medium to high phosphorus type acidic nickel phosphorus plating solution in which the concentration of sodium hypophosphite and the temperature of the plating solution is high and the phosphorus concentration in the formed plating film is about 7 to 12% by weight is used. It is preferable to use it. Since such nickel phosphorus plating solution has high permeability into polyamide, electroless plating reaction in polyamide while reducing palladium chloride even when the content of palladium chloride in the molded body is low Is presumed to progress.

  Moreover, the reducing power of hypophosphite decreases as the temperature decreases. The use temperature of a medium to high phosphorus electroless nickel phosphorus plating solution having a high concentration of a reducing agent on the market is often as high as 85 ° C to 90 ° C. However, when the molded body is plated at a processing temperature of 85 ° C. to 90 ° C., the molded body itself may be deformed. In addition, since electroless plating is performed in a state where the molded body is expanded and the molded body is contracted by being cooled after electroless plating, the plated film that cannot cope with the shrinkage of the molded body may be cracked. This problem is particularly noticeable in polyolefins such as polypropylene having low heat resistance. In the present embodiment, the plating pretreatment using the electroless plating catalyst solution described above (step S2 in FIG. 1) allows the electroless plating catalyst to penetrate not only the surface of the molded body but also the polyamide region near the surface. Yes. Further, the polyamide region into which the electroless plating catalyst has permeated has a higher water absorption rate than the polyolefin region, and the electroless plating solution is likely to permeate therethrough. In this embodiment, by using an acidic electroless plating solution having a high reducing power for such a molded body having a high plating reactivity, a plating film having a high adhesion strength even when the plating temperature is 80 ° C. or lower. Can be formed. And since the electroless plating solution temperature can be 80 ° C or less, even though the molded body contains polyolefin such as polypropylene, it prevents deformation of the molded body and cracking of the plated film, and forms a plated film with excellent appearance characteristics. it can.

  A plurality of different types of electroless plating films may be formed on the molded body on which the electroless nickel phosphorus plating film is formed, for the purpose of improving the use and design of the plated parts, or by electroplating. A plating film may be formed. Moreover, the molded body on which the electroless plating film is formed may be annealed after the electroless plating, or may be left to stand at room temperature to be naturally dried. Moreover, you may perform the following processes, such as forming an electrolytic plating film | membrane continuously, without performing annealing treatment and natural drying.

(2) Plating component Next, the plating component manufactured by the manufacturing method demonstrated above is demonstrated. As shown in FIG. 2 (a), the plated component 300 includes a molded body 10 containing a PA / PO polymer alloy of polyamide and polyolefin, and an electroless plated film 20, and inside the molded body 10, The polyamide region 11 and the polyolefin region 12 are mixed. That is, the PA / PO polymer alloy is not a one-phase system in which the polyamide and the polyolefin are completely compatible, but a two-phase system in which the polyamide region 11 and the polyolefin region 12 are mixed. The polyamide region 11 and the polyolefin region 12 form a sea-island structure (matrix-domain structure). The plated component 300 shown in FIG. 2A has a structure in which islands (domains) of the polyolefin region 12 are formed in the sea (matrix) of the polyamide region 11, but this embodiment is not limited to this. . Contrary to the structure shown in FIG. 2A, a structure in which islands (domains) of polyamide regions are formed in a sea (matrix) of polyolefin regions may be used. Which of the polyamide region 11 and the polyolefin region 12 becomes the sea (matrix) and which becomes the island (domain) largely depends on the volume ratio of each polymer in the PA / PO polymer alloy. A polymer having a large volume ratio in the PA / PO polymer alloy is mainly a sea (matrix), and a polymer having a small volume ratio is mainly an island (domain).

  In FIGS. 2A and 2B, the direction in which the molten resin flows during molding of the molded body 300 is indicated by an arrow as “flow direction”. The direction parallel to the flow direction is the “Y direction”, the direction perpendicular to the Y direction and parallel to the surface of the electroless plating film 20 is the “X direction”, and the direction perpendicular to the X direction and the Y direction is the “Z direction”. Is shown in FIG. 2 (a). 2A is defined as an “XZ cross section”, and a cross section substantially parallel to the flow direction is defined as a “YZ cross section”.

  As shown in the XZ cross section and the YZ cross section of FIG. 2A, and further shown in FIG. 2B, the polyolefin region 12 that is an island (domain) is stretched in the flow direction (Y direction), and as a result, the Z direction. It becomes a flat shape crushed at. In particular, in the vicinity of the surface of the molded body, that is, the portion adjacent to the mold wall surface during molding, the polyolefin region 12 is stretched in a direction substantially parallel to the surface of the molded body (X direction or Y direction) due to shear stress. (Striped). The shape of the polyolefin region 12 in the XZ cross section is striped (striped) in the vicinity of the surface of the molded body, and approaches a circular shape toward the center of the molded body.

  The polyamide region 11 and the polyolefin region 12 are ideally in close contact with each other, and it is desirable that no void (gap) is generated between them. However, as shown in FIG. 3, a gap (gap) 13 may be generated between the polyamide region 11 and the polyolefin region 12. When such a gap 13 is generated, peeling between the two materials occurs starting from the gap, and the quality of the plated component is deteriorated. One of the causes of the generation of such voids 13 is presumed to be heating of the molded body during electroless plating. It is presumed that voids 13 are likely to be generated between the polyamide region 11 and the polyolefin region 12 due to the stress due to the difference in thermal shrinkage between the polyamide region 11 and the polyolefin region 12. In the present embodiment, by performing electroless plating at a relatively low temperature, the width W of the gap 13 between the polyamide region 11 and the polyolefin region 12 can be set to 1 μm or less, for example. If the width W of the gap 13 is 1 μm or less, it is possible to obtain a plating film that suppresses the deterioration of the quality of the plated parts, has excellent appearance characteristics, and has high adhesion strength.

  Here, the “width W of the gap 13” between the polyamide region 11 and the polyolefin region 12 is the interface between the polyamide region 11 and the polyolefin region 12 of the gap 13 observed in the vicinity of the surface of the molded body in the cross-sectional observation of the molded body. It is defined as the distance of the part that is farthest from the interface. Although the cross section for observation is not particularly limited, for example, it is a cross section of 60 ° to 120 ° with respect to the surface on which the plating film is formed, preferably a cross section of 80 ° to 100 °, more preferably. It is a substantially vertical cross section. Here, “near the surface” of the molded body means, for example, a region having a depth of 100 μm from the surface of the molded body.

  Further, if the island (domain) in the sea-island structure (matrix-domain structure) is large, the gap 13 is formed at the interface between the polyamide region 11 and the polyolefin region 12 due to the stress due to the thermal shrinkage difference between the polyamide region 11 and the polyolefin region 12. Is likely to occur. Therefore, the island (domain) in the sea-island structure (matrix-domain structure) is preferably small, and the island size (domain size) is, for example, 0.1 μm to 30 μm, preferably 0.1 μm to 10 μm. More preferably, it is 0.1 μm to 5 μm. Further, when the size of the island (domain) is nano-order, the free deposition that can swell the polyamide region 11 during electroless plating increases, so that the plating reactivity is improved and the adhesion strength of the plating film is improved.

  Here, the “island size (domain size)” means the average of the major axis and minor axis of the island (domain) observed in the vicinity of the surface of the molded body in cross-sectional observation of the molded body, and the major axis and minor axis are calculated. Mean particle diameter calculated as an average value of.

  The above-described confirmation of the sea-island structure (matrix-domain structure) of the polyamide region 11 and the polyolefin region 12, the measurement of the width W of the void 13 and the measurement of the island size (domain size) are performed by, for example, dyeing a cross section of the molded body Then, it can be performed by cross-sectional observation with a transmission microscope (TEM). The cross-section processing method for TEM observation is not particularly limited, and examples thereof include a frozen ultrathin film section method (cryomicrotome method), a focused ion beam method (FIB method), an ion milling method, and a microtome method. The dyeing method is not particularly limited as long as it is a method in which a contrast between a polyamide and a polyolefin is provided at the time of cross-sectional observation and a sea-island structure (matrix-domain structure) can be confirmed. A heavy metal staining method using ruthenium tetroxide or the like can be used. When the PA / PO polymer alloy is observed by TEM without dyeing treatment, both the polyamide and the polyolefin are composed of light elements, so that most of the electron beams are transmitted and the contrast between the two materials cannot be obtained. When a PA / PO polymer alloy is reacted with a heavy metal by a heavy metal dyeing method or the like, the transmission state of the two electron beams differs depending on the degree of bonding between the polyamide and the heavy metal of the polyolefin. Thereby, the contrast of polyamide and polyolefin becomes high, and can confirm a sea-island structure (matrix-domain structure).

[Second Embodiment]
In the present embodiment, a plated part in which a plating film is partially formed and a manufacturing method thereof will be described. As shown in FIG. 4, the molded body 100 manufactured in the present embodiment includes a first portion 101 where the electroless plating film 103 is formed on the surface and a second portion where the electroless plating film is not formed on the surface. The first part 101 and the second part 102 are integrally molded (integrated molding). That is, the molded body 100 is an integrally molded body of the first portion 101 and the second portion 102. The 1st site | part 101 contains PA / PO polymer alloy similarly to the molded object 10 manufactured in 1st Embodiment.

(1) Manufacturing method of plated parts <Molding of molded body>
In the present embodiment, a molded body having a first part 101 and a second part 102 is formed by a two-color molding method using a general-purpose two-color molding machine 200 shown in FIG. Hereinafter, the manufacturing method of this embodiment will be described with reference to the flowchart shown in FIG. 5 and FIG. 6.

  First, the first thermoplastic resin containing the PA / PO polymer alloy is plasticized and melted in the first plasticizing cylinder 204 of the two-color molding machine 200 shown in FIG. (Step S11 in FIG. 5). As the PA / PO polymer alloy, the same one as used in the first embodiment can be used.

  In the second plasticizing cylinder 205, the second thermoplastic resin is plasticized and melted to form the second molten resin (step S12). The second thermoplastic resin is not particularly limited and can be selected according to the use of the molded body, but a resin other than polyamide is preferable. This is because the second thermoplastic resin constitutes the second portion 102 where electroless plating is not formed, but polyamide is easy to form an electroless plating film. When it is desired to add a matte decoration to the second portion where the plating film is not formed, the second thermoplastic resin is preferably a crystalline resin. Examples of the crystalline resin that can be used include resins such as polyethylene, polypropylene (PP), polyacetal, polyphthalamide, polyphenylene sulfide, polybutylene terephthalate, and polyethylene terephthalate. Moreover, it is preferable that a 2nd thermoplastic resin contains a polypropylene from a viewpoint of the chemical-resistant improvement of a molded object, weight reduction, and cost reduction. Polypropylene has the advantages of low specific gravity, high chemical resistance, and low cost, so it has been widely used as an automotive part. However, it is chemically stable and has high adhesion. It was difficult to form a plating film. In the present embodiment, the plating film can be formed on a part of the polypropylene molded body by using polyamide or the like for the part (first part) where the plating film is formed.

  Similarly to the first thermoplastic resin, the second thermoplastic resin may be a non-reinforced resin or a reinforced resin. In addition, various compatibilizers and adhesive materials may be mixed in order to improve the adhesion between the first part and the second part.

  As the second thermoplastic resin, one kind of resin may be used alone, or two or more kinds of resins may be mixed and used. Moreover, it is preferable that a 2nd thermoplastic resin contains the resin component common to a 1st thermoplastic resin from a viewpoint of the adhesive improvement of a 1st site | part and a 2nd site | part. For example, the second thermoplastic resin preferably contains the same olefin as the polyolefin of the PA / PO polymer alloy of the first thermoplastic resin. For example, it is preferable that the polyolefin of the PA / PO polymer alloy of the first thermoplastic resin is polypropylene, and the second thermoplastic resin contains polypropylene.

  Next, as shown in FIG. 6B, the first molten resin is injected from the first plasticizing cylinder 204 into the cavity 202 formed in the mold 201 shown in FIG. 1 part 101 is formed.

  A core back is performed on the mold 201 by a hydraulic drive mechanism (not shown), and the cavity 202 in the mold 201 is widened to form a new space 203 as shown in FIG. Then, as shown in FIG. 6 (d), the second molten resin is transferred from the second plasticizing cylinder 205 to a new space 203 in the cavity 202 with the first portion 101 held in the cavity 202. Inject. Thereby, the 2nd site | part 102 connected to a 1st site | part is shape | molded in the metal mold | die 201, and the molded object of this embodiment is obtained (step S13 of FIG. 5). As shown in FIG. 6E, by opening the mold 201, the molded body formed from the first part 101 and the second part 102 can be taken out.

  In the two-color molding method of the present embodiment, a method of performing core back (core back method) in the cavity 201 was used, but other known methods, for example, a first molten resin was injection molded into the cavity. Thereafter, a method may be used in which the cavity is inverted and the second molten resin is injected and filled into the cavity (inversion method). Furthermore, as long as it is a molding method (integral molding) for integrating parts made of different materials, other known molding methods other than two-color molding, such as insert molding, may be used. In the present specification, “integral molding” means that the product is integrally molded simultaneously with the joining of the members without using secondary bonding or mechanical joining.

<Plating pretreatment and electroless plating>
The plated film 103 is formed only on the surface of the first member 101 of the molded body obtained by the above molding method, and the molded body 100 shown in FIG. 4 is obtained.

  The plating pretreatment and the electroless plating are performed in the same manner as in the first embodiment. First, a pre-plating treatment is performed in which the molded body is contacted with an electroless plating catalyst solution containing hydrochloric acid and palladium chloride (step S2 in FIG. 5), and then an acidic electroless nickel phosphor plating of 50 ° C. to 80 ° C. The liquid is brought into contact (step S3).

  By performing the plating pretreatment, palladium chloride functioning as an electroless plating catalyst is selectively adsorbed and permeated into the first member 101 containing polyamide. Thus, after the pre-plating treatment, for example, even if the entire molded body is immersed in an electroless plating solution, a plating film is formed only on the surface of the first member, and no plating film is formed on the second portion 102. . In the present embodiment, the partial plating film 103 having a clear contrast with and without the plating film can be formed on the surface of the molded body 100 at a low cost without using a masking process. For this reason, the manufacturing cost of plated components can be kept low. As in the first embodiment, electrolytic copper plating, electrolytic nickel plating, and electrolytic trivalent chromium plating are further provided on the plating film formed by electroless plating for the purpose of improving the use and design of the molded body. A plating film such as the above may be laminated.

(2) Plating component As shown in FIG. 4, the plating component 100 manufactured in this embodiment includes a first portion 101 having an electroless plating film 103 formed on the surface and an electroless plating film formed on the surface. The first part 101 and the second part 102 are integrally molded (integrated molding).

  In the interior of the first part 101 of the plated component 100, the polyamide region 11 and the polyolefin region 12 are mixed, as in the plated component 300 of the first embodiment shown in FIG. A structure (matrix-domain structure) is formed. In this embodiment, by performing electroless plating at a low temperature, the width W of the gap 13 at the interface between the polyamide region 11 and the polyolefin region 12 can be set to 1 μm or less, for example. As a result, it is possible to obtain a plated film that suppresses deterioration of the quality of the plated part, has excellent appearance characteristics, and has high adhesion strength.

  In the present embodiment, the water absorption rate of the first part when immersed in water at 23 ° C. for 24 hours is 0.5% by weight or more and 3.0% by weight or less, and the water absorption rate of the second part is It is preferably 2.0% by weight or less. The said water absorption of a 1st site | part and a 2nd site | part can be measured by the method described in the Example mentioned later, for example. When the first portion has a water absorption rate of less than 0.5% by weight when immersed in water at 23 ° C. for 24 hours, the plating reactivity decreases, and the water absorption rate exceeds 3.0% by weight. The difference between the swelling of the resin during plating and the shrinkage of the resin after plating increases, and there is a possibility that problems such as cracking of the plating film may occur. Also, if the water absorption rate of the first part exceeds 3.0% by weight, the plating solution may accumulate at the interface between the first part and the second part during electroless plating, and peeling may occur at the interface between the two resins. There is also. On the other hand, in the second part, when the water absorption rate after being immersed in water at 23 ° C. for 24 hours exceeds 2.0% by weight, water is immersed from the second part to the first part, and the plating film interface May occur. Moreover, if the water absorption rate of the second part is large, the dimensional accuracy of the molded body also decreases due to water absorption. As described above, as a result of intensive studies by the present inventors, when performing electroless plating on a molded body composed of the first part and the second part, the water absorption rate of both parts must be optimized, It has been found that there is a problem in the reliability of parts using the molded body. The water absorption rate of the first part when immersed in water at 23 ° C. for 24 hours is 0.5% by weight or more and 3.0% by weight or less, and the water absorption rate of the second part is 2.0% by weight or less. By doing so, long-term reliability of parts using plated parts can be ensured.

  Furthermore, the water absorption rate of the first part when immersed in water at 23 ° C. for 24 hours is preferably 0.5 wt% or more and 2.0 wt% or less. The lower limit of the water absorption rate of the second part is not particularly limited and is preferably as low as possible. However, from the viewpoint of suppressing peeling due to a difference in water absorption rate with the first resin, 0.1% by weight or more is preferable. preferable.

  In the plated component of the present embodiment, the first part and the second part have the water absorption rate in the specific range described above, and the difference in the water absorption rate between the two parts is 2.9% by weight or less. It is preferable that it is 2.5 wt% or less. If the difference in water absorption between the two parts is 2.9% by weight or less, the difference in expansion coefficient between the two parts due to water absorption is also small, so that the plating film is peeled off and the first part and the second part are separated. Can be suppressed. The water absorption rate of the first part and the second part may be larger than the first part as long as the water absorption rate of the second part is within the specific range described above. Conversely, the water absorption rate of the first part may be larger than that of the second part. The “difference between the water absorption rates of the two parts” is a difference obtained by subtracting a small value from a large value of the water absorption rate of the first part and the water absorption rate of the second part.

  Further, the second part may be a foamed molded body. By foaming the second part, a plated part having heat insulation, strength and dimensional accuracy can be obtained. Plated parts with foamed second part are used for automobile parts such as building material parts such as resin sashes, high-rigidity automobile parts such as door knobs, shift levers, paddle shifts, air conditioner blades, front grills, garnishes, and inner door handles. It can be used as a design plated part, a camera casing, a lens barrel of an interchangeable lens or a part thereof, a home appliance part such as a flat-screen TV, a personal computer, an air conditioner, and a refrigerator.

[Third Embodiment]
In the present embodiment, a method for producing a plated part in which the molded body further includes a block copolymer having a hydrophilic segment in addition to the PA / PO polymer alloy and metal fine particles will be described.

(1) Method for Manufacturing Plated Part Hereinafter, the method for manufacturing the present embodiment will be described with reference to the flowchart shown in FIG. In this embodiment, first, resin pellets including a block copolymer and metal fine particles are manufactured, and a molded body is formed from the manufactured resin pellets and PA / PO polymer alloy (step S1 in FIG. 1).

<Production of resin pellet containing block copolymer and metal fine particles>
In the present specification, the “resin pellet” means a small lump (pellet) so that the resin can be easily processed, and the size and shape vary depending on the use of the pellet, for example, about 3 to 5 mm. It is a small piece of particulate and columnar resin. Moreover, in this embodiment, the resin pellet containing a block copolymer and metal fine particles corresponds to a master batch, and the PA / PO polymer alloy corresponds to a base resin into which the master batch is blended. A masterbatch is a resin pellet containing functional materials such as dyes, pigments, and other additives at a high concentration, and is mixed with a base resin not containing a functional material and molded together with the base resin. When the master batch is used, the handling of the material is easy and the weighing accuracy is improved as compared with molding by adding metal fine particles, which are functional materials, directly to the base resin. Moreover, when a masterbatch is used, it has the advantage that the molded object containing a metal microparticle can be manufactured using a general purpose molding machine. Hereinafter, in the present specification, a resin pellet containing a block copolymer and metal fine particles is referred to as a “master batch pellet”.

  As the block copolymer contained in the master batch pellet of the present embodiment, the same block copolymer as used in the first embodiment can be used. The metal fine particles contained in the master batch pellet are not particularly limited as long as they function as a metal catalyst for electroless plating. For example, fine particles such as Pd, Ni, Pt, and Cu are preferable. From the viewpoint of stability, fine particles of palladium (Pd) are more preferable. As will be described later, when pressurized carbon dioxide is used in the production of master batch pellets, the metal fine particles used in this embodiment are preferably dissolved in pressurized carbon dioxide, for example, dissolved in pressurized carbon dioxide. A metal complex such as hexafluoroacetylacetonatopalladium (II) metal complex, platinum dimethyl (cyclooctadiene), bis (cyclopentadienyl) nickel, bis (acetylacetonate) palladium and the like having high properties is preferable.

  The method for producing the master batch pellet is arbitrary, and for example, it can be produced by the production method disclosed in International Publication No. 2013/129659. However, the pressurized carbon dioxide in which metal fine particles are dissolved or dispersed (hereinafter referred to as “ It is preferable to include a step of allowing metal fine particles to permeate into the block copolymer by bringing the mixed pressurized fluid into the block copolymer. Since the method using pressurized carbon dioxide does not require an organic solvent, the environmental load is low. Further, the pressurized carbon dioxide promotes uniform dispersion of the metal fine particles in the block copolymer, and can significantly reduce the particle size of the metal fine particles. It is considered that when the metal fine particles are uniformly dispersed without being aggregated, the metal fine particles easily move to the surface of the molded body along with the block copolymer. As a result, when a molded body having a plating film is manufactured using master batch pellets manufactured using pressurized carbon dioxide, a uniform and high-quality plating film can be obtained. Although master batch pellets can be produced by mixing only the block copolymer and metal fine particles without using pressurized carbon dioxide, it is preferable to use pressurized carbon dioxide for the above reasons.

  In the present embodiment, master batch pellets are manufactured by batch processing using a high-pressure vessel. First, a pellet-shaped block copolymer (raw material pellet) and a metal complex are accommodated in a high-pressure vessel, and pressurized carbon dioxide is introduced therein. After the introduction of the pressurized carbon dioxide, the inside of the high-pressure vessel is kept in a pressurized state for a certain time. The metal fine particles are dissolved in the pressurized carbon dioxide, the pressurized carbon dioxide in which the metal fine particles are dissolved contacts the block copolymer, and the metal fine particles penetrate into the block copolymer together with the pressurized carbon dioxide. Thereby, a master batch pellet in which metal fine particles are dispersed in the block copolymer is obtained. After a certain period of time, the pressurized carbon dioxide inside the high-pressure vessel is exhausted outside the vessel, and the master batch pellet is taken out from the high-pressure vessel. Although depending on various conditions of the batch processing, in this embodiment, the amount of the metal fine particles accommodated in the metal container permeating into the block copolymer (raw material pellet) is 20 to 80 of the charged amount. %, Not all metal fine particles penetrate into the block copolymer. However, the metal fine particles that do not penetrate into the block copolymer can be recovered by being discharged out of the high-pressure vessel together with the pressurized carbon dioxide and separated from the pressurized carbon dioxide.

  As the pressurized carbon dioxide used for producing the master batch pellets, pressurized carbon dioxide in a liquid state, a gas state, or a supercritical state can be used. These pressurized carbon dioxides are harmless to the human body, are excellent in diffusibility into the block copolymer, and can be easily removed from the block copolymer. The pressure and temperature of the pressurized carbon dioxide introduced into the high-pressure vessel are arbitrary, but liquid carbon dioxide or supercritical carbon dioxide is preferably used because of its high density and stability. The temperature of the pressurized carbon dioxide is preferably in the range of 5 ° C to 50 ° C. The lower the temperature of the pressurized carbon dioxide, the higher the density and the higher the solvent effect, which is preferable, but 5 ° C. or higher is preferable from the viewpoint of easy cooling control. Moreover, since there exists a possibility that a density may become low and liquid feeding may become unstable when the temperature of pressurized carbon dioxide becomes high, 50 degreeC or less is preferable from a viewpoint of liquid feeding stably. The pressure of the pressurized carbon dioxide is desirably in the range of 4 to 25 MPa. From the viewpoint of obtaining an appropriate solvent effect because the solvent effect is difficult to be expressed when the pressure is low, 4 MPa or more is preferable, and from the viewpoint of suppressing the cost because the high pressure equipment is costly when the pressure is high. 25 MPa or less is preferable. Note that the pressure and carbon dioxide in which metal fine particles are dissolved or dispersed tend to fluctuate in temperature and pressure. Therefore, the above-mentioned state, temperature, and pressure of pressurized carbon dioxide are values of the state, pressure, and temperature of pressurized carbon dioxide in a stable state before being introduced into the high-pressure vessel.

  In this embodiment, after the introduction of the pressurized fluid, the time for maintaining the inside of the high-pressure vessel in a pressurized state can be arbitrarily determined in consideration of the type of block copolymer, the type of metal fine particles, etc. Minutes to 120 minutes are preferred.

  The content of the metal fine particles in the master batch pellet is arbitrary, and can be appropriately determined in consideration of the type of metal fine particles, the type of block copolymer, the intended use of resin parts, etc., but from the viewpoint of cost and plating reactivity For example, 10 to 2000 ppm by weight is preferable, and 50 to 500 ppm by weight is more preferable.

  As described above, in this embodiment, master batch pellets are manufactured by batch processing using a pressurized container, but the master batch pellets may be manufactured by other methods using pressurized carbon dioxide. Examples of other methods using pressurized carbon dioxide include the following methods. First, the block copolymer is plasticized and melted in a plasticizing cylinder of an extruder, and pressurized carbon dioxide (mixed pressurized fluid) in which metal fine particles are dissolved is introduced into the plasticizing cylinder. The block copolymer is brought into contact with the mixed pressurized fluid. Then, the block copolymer mixed with the metal fine particles is extruded and then pulverized to obtain master batch pellets formed from the block copolymer mixed with the metal fine particles.

<Molding of molded body>
Next, a molded body is molded from the produced master batch pellet and PA / PO polymer alloy. As the PA / PO polymer alloy, the same one as used in the first embodiment can be used.

  The mixing ratio of the PA / PO polymer alloy (base resin) and the master batch pellet can be appropriately determined in consideration of the content of metal fine particles in the master batch pellet. For example, the ratio of the master batch pellet is preferably 1 to 30% by weight based on the total amount of the master batch pellet and the PA / PO polymer alloy (base resin), that is, based on the total weight of the molded body. 1 to 15% by weight is more preferable. When the ratio of the master batch pellet is 1% by weight or more, the permeability and plating reactivity of the plating solution can be sufficiently increased. If the ratio is 30% by weight or less, the physical properties such as heat resistance and mechanical strength of the molded body can be obtained. There is no significant loss.

  The molding method of the molded body of this embodiment is not particularly limited. For example, a material obtained by adding other general-purpose additives as necessary to PA / PO polymer alloy and master batch pellets may be molded by general-purpose injection molding, extrusion molding, or the like to obtain a molded body.

  The metal fine particles in the obtained molded body are preferably nanoparticles having a particle size of 10 nm or less. Since nanoparticles having a particle size of 10 nm or less have a large surface area and high catalytic activity, a plating film can be stably formed with a low concentration of catalyst, and the cost can be reduced. Moreover, it is preferable that 1-50 weight ppm is contained in a molded object, and it is still more preferable that 5-20 weight ppm is contained. The content of the metal fine particles in the molded body is obtained by dissolving a part of the molded body in an organic solvent and measuring the amount of metal such as Pt using ICP (Inductively Coupled Plasma) emission spectrometry. It is done. When the content of the metal fine particles is small, the amount of metal such as Pt can be measured using ICP-MS (inductively coupled plasma mass spectrometer).

<Plating pretreatment and electroless plating>
Electroless plating is performed in the same manner as in the first embodiment. First, a pre-plating treatment is performed in which the molded body is brought into contact with an electroless plating catalyst solution containing hydrochloric acid and palladium chloride (step S2 in FIG. 1), and then an acidic electroless nickel phosphor plating of 50 to 80 ° C. The liquid is brought into contact (step S3). Further, in the same manner as in the first embodiment, for the purpose of improving the use of the molded product and the design, etc., electrolytic copper plating, electrolytic nickel plating and electrolytic trivalent chromium plating are further applied on the plating film formed by electroless plating. A plating film such as the above may be laminated.

  The block copolymer contained in the molded body of the present embodiment moves with the metal fine particles toward the surface of the molded body during the molding process or after molding, and segregates near the surface of the molded body together with the metal fine particles. Tend to. In this embodiment, palladium chloride, which is an electroless plating catalyst, is applied from the outside of the molded body. By containing metal fine particles that function as an electroless plating catalyst near the surface of the molded body, the plating reaction of the molded body is performed. The plating film is further improved, the adhesion strength is higher, and the appearance characteristics are excellent. In particular, when the shape of the molded body is complicated, there is a possibility that the amount of palladium chloride adsorbed from the outside may be uneven. Even in such a case, in the present embodiment, since the metal fine particles exist in the vicinity of the surface of the molded body, the plating film can be uniformly formed without causing unevenness in the plating reaction.

  The master batch pellet used in the present embodiment can also be used in the manufacture of a plated part in which a plating film is partially formed in the second embodiment. That is, the first thermoplastic resin including the PA / PO polymer alloy and the master batch pellet is plasticized and melted to form the first molten resin, and the first molten resin is used to form the first plated component 100 shown in FIG. A portion 101 is formed. The plating reactivity of the first portion 101 including the master batch pellet is further increased, and a plating film having a higher adhesion strength and excellent appearance characteristics can be obtained.

(2) Plating component As in the plating component 300 of the first embodiment shown in FIG. 2A, the polyamide region 11 and the polyolefin region 12 are mixed in the plating component manufactured in the present embodiment. A sea-island structure (matrix-domain structure) is formed. In this embodiment, by performing electroless plating at a low temperature, the width W of the gap 13 at the interface between the polyamide region 11 and the polyolefin region 12 can be set to 1 μm or less, for example. As a result, it is possible to obtain a plated film that suppresses deterioration of the quality of the plated part, has excellent appearance characteristics, and has high adhesion strength.

  EXAMPLES Hereinafter, although an Example and a comparative example demonstrate this invention concretely, this invention is not restrict | limited by the following Example and comparative example.

[Example 1]
In this example, first, a PA / PO polymer alloy pellet containing nylon, polyolefin and a compatibilizer is produced, and a molded body is molded using only the PA / PO polymer alloy pellet. A plating film was formed.

(1) Molding of molded body As polyamide, 75 parts by weight of non-reinforced nylon 6 (manufactured by Ube Industries, UBE nylon 1013B), as polyolefin, 20 parts by weight of non-reinforced polypropylene (manufactured by Prime Polymer, Prime Polypro J105G), as a compatibilizing agent Then, 5 parts by weight of acid-modified polypropylene (manufactured by Sanyo Chemical Co., Ltd., Yumex 1001) was mixed, extruded using a twin-screw kneading extruder (manufactured by Imoto Seisakusho), and then pulverized to obtain PA / PO polymer alloy pellets. . The obtained PA / PO polymer alloy pellets were injection-molded to obtain a 6 cm × 4 cm × 0.2 mm flat molded body.

(2) Pre-plating treatment and electroless plating First, as a pre-plating treatment, the molded body was immersed in an electroless plating catalyst solution at 30 ° C for 1 minute, and then immersed in pure water at 70 ° C for 5 minutes. The electroless plating catalyst solution used in this example was a solution in which 50 ppm by weight of palladium chloride was contained in 2.7 N hydrochloric acid. Moreover, when the density | concentration of the palladium in the molded object after a plating pretreatment was measured by ICP-MS, the palladium density | concentration was 10 weight ppm or less.

  After the plating pretreatment, the molded body was immersed for 12 minutes in an acidic electroless nickel phosphorus plating solution (Okuno Pharmaceutical Co., Ltd., Top Nicolon HMB) at 70 ° C. to form an electroless nickel phosphorus plating film. A plated part was obtained.

[Example 2]
In this example, the PA / PO polymer alloy pellets produced in Example 1 were mixed with a block copolymer to form a molded product, and an electroless plating film was formed on the molded product.

(1) Molding of molded body By mixing 95 parts by weight of the PA / PO polymer alloy pellets produced in Example 1 and 5 parts by weight of a block copolymer containing a hydrophilic segment (manufactured by Sanyo Kasei, Pelestat PL1251) The molded body having the same size as in Example 1 was molded by injection molding.

(2) Pre-plating treatment and electroless plating In the same manner as in Example 1, pre-plating treatment and electroless plating were performed to obtain a plated part of this example. In addition, when the density | concentration of the palladium in the molded object after a pre-plating process was measured by ICP-MS, the palladium density | concentration was 10 weight ppm or less.

[Example 3]
In this example, first, resin pellets (master batch pellets) containing a block copolymer and metal fine particles were produced, and a molded product was formed from the produced resin pellets and the PA / PO polymer alloy produced in Example 1, An electroless plating film was formed on the molded body.

(1) Master batch pellet manufacturing method In this example, master batch pellets were manufactured by batch processing using a high-pressure vessel. First, in a high-pressure vessel adjusted to 40 ° C., pelletized block copolymer (raw material pellet) made by Sanyo Chemical Industries, Pelestat (registered trademark) PL1251, and metal complex hexafluoroacetylacetonato palladium (II) ) The complex was accommodated. The ratio of the metal complex to the block copolymer (raw material pellet) was 2000 ppm by weight. The ratio (concentration) of palladium in the metal complex to the block copolymer (raw material pellet) was about 400 ppm by weight.

  Liquid carbon dioxide having a pressure of 15 MPa was introduced as pressurized carbon dioxide into the high-pressure vessel in which the block copolymer and the metal complex were accommodated. After the introduction, the inside of the high-pressure vessel was maintained in a pressurized state for 1 hour. Thereafter, the pressurized carbon dioxide inside the high-pressure vessel was exhausted outside the vessel and the pressure was reduced, and the resin pellet (master batch) was taken out from the high-pressure vessel. The resin pellets changed from the white color of the raw material pellets to yellow, which is the color of the metal complex.

  The obtained resin pellet was dissolved in concentrated hydrochloric acid using a microwave dissolving apparatus, and the amount of palladium in the resin pellet was measured with an ICP emission spectrometer. The content of palladium in the resin pellets was 190 ppm by weight. From this result, it was found that less than 50% by weight of palladium contained in the metal complex introduced into the high-pressure vessel penetrated into the raw material pellets. Next, the cross section of the resin pellet was observed using TEM. In TEM, palladium could not be detected in the cross section of the resin pellet. From this result, it is presumed that the palladium in the resin pellet is present at an atomic level below the detection limit of TEM.

(2) Molding of molded body 95 parts by weight of the PA / PO polymer alloy pellets produced in Example 1 and 5 parts by weight of the master batch pellets produced in this example were mixed and injection molded. A molded body having the same size was molded.

(3) Pre-plating treatment and electroless plating In the same manner as in Example 1, pre-plating treatment and electroless plating were performed to obtain a plated part of this example. In addition, when the density | concentration of the palladium in the molded object after a pre-plating process was measured by ICP-MS, the palladium density | concentration was 20 weight ppm or less.

[Example 4]
In this example, a molded body was molded using only a commercially available PA / PO polymer alloy, and an electroless plating film was formed on the molded body.

(1) Molding of molded body Nylon 6 is used as a polyamide, and a commercially available PA / PO polymer alloy (made by Toray, Amilan S133) containing a reactive polyolefin is injection molded as a polyamide. A shaped body was formed. The commercially available PA / PO polymer alloy used in this example has a structure in which islands (domains) of a refined polyolefin region having a nano-order domain size are formed in a sea (matrix) of a polyamide region. It is known that the material has a high shock absorption characteristic.

(2) Pre-plating treatment and electroless plating In the same manner as in Example 1, pre-plating treatment and electroless plating were performed to obtain a plated part of this example. In addition, when the density | concentration of the palladium in the molded object after a pre-plating process was measured by ICP-MS, the palladium density | concentration was 10 weight ppm or less.

[Example 5]
In this example, a molded body was molded using only a commercially available PA / PO polymer alloy different from that used in Example 4, and an electroless plating film was formed on the molded body.

(1) Molding of molded body Nylon 6 is used as a polyamide, and a commercially available PA / PO polymer alloy (Amilan U141, manufactured by Toray Industries, Inc.) containing polyolefin elastomer is used as a polyolefin. The molded body was molded. The commercially available PA / PO polymer alloy used in this example has a structure in which an island (domain) of a polyolefin region is formed in a sea (matrix) of a polyamide region, and the commercially available PA / PO polymer alloy used in Example 4 is used. Unlike PA / PO polymer alloy, the domain size is not nano-order, but it is a flexible material.

(2) Pre-plating treatment and electroless plating In the same manner as in Example 1, pre-plating treatment and electroless plating were performed to obtain a plated part of this example. In addition, when the density | concentration of the palladium in the molded object after a pre-plating process was measured by ICP-MS, the palladium density | concentration was 10 weight ppm or less.

[Example 6]
In this example, a molded body having the first portion 101 and the second portion 102 shown in FIG. 4 was molded, and the electroless plating film 103 was formed on the first portion 101 of the molded body. As the first thermoplastic resin forming the first part 101, the PA / PO polymer alloy produced in Example 1 is used, and as the second thermoplastic resin forming the second part, polypropylene is used. It was.

(1) Molding of molded body Using a two-color molding machine manufactured by Nippon Steel, J180AD-2M, the two-color molding method of the core back method shown in FIGS. A molded body having the first portion 101 and the second portion 102 was molded. The PA / PO polymer alloy produced in Example 1 was used as the first thermoplastic resin forming the first portion 101. As the second thermoplastic resin forming the second portion, 80 parts by weight of polypropylene (made by Prime Polymer, Prime Polypro J105G) and a master batch for polypropylene containing 80% by weight of talc (made by Idemitsu Lion Composite, MP480-2) ) 20 parts by weight were mixed and used.

(2) Pre-plating treatment and electroless plating In the same manner as in Example 1, pre-plating treatment and electroless plating were performed to obtain a plated part of this example. In addition, when the density | concentration of the palladium in the 1st site | part of the molded object after a plating pretreatment was measured by ICP-MS, the palladium density | concentration was 10 weight ppm or less.

[Comparative Example 1]
In this comparative example, a plated part was formed by the same method as in Example 1 except that electroless plating was performed using an alkaline electroless nickel plating solution.

  First, a molded body was molded by the same method as in Example 1, and pre-plating treatment was performed. The molded body subjected to the plating pretreatment was immersed in an alkaline (pH = 9.0) electroless nickel plating solution (Okuno Pharmaceutical Co., Ltd., product name: chemical nickel) at 35 ° C. for 10 minutes. However, in this comparative example, the plating reaction did not occur even after immersion for 10 minutes, and no plating film was formed on the surface. That is, a plated part could not be obtained in this comparative example.

[Comparative Example 2]
In this comparative example, a PA / PO polymer alloy pellet having a composition ratio different from that of Example 1 was produced, and a molded body was molded using only the PA / PO polymer alloy pellet, and an electroless plating film was formed on the molded body. Formed.

(1) Molding of molded body PA / PO polymer alloy resin pellets of PA / PO polymer alloy by the same method as in Example 1 except that the same materials as in Example 1 were used and the mixing ratio was changed as follows. Manufactured. 95 parts by weight of polyamide, 4.5 parts by weight of polyolefin, 0.5 parts by weight of compatibilizer. The obtained PA / PO polymer alloy pellets were injection molded to obtain a molded body having the same size as in Example 1.

(2) Pre-plating treatment and electroless plating First, as a pre-plating treatment, the molded body was immersed in an electroless plating catalyst solution at 30 ° C for 1 minute, and then immersed in pure water at 95 ° C for 5 minutes. The electroless plating catalyst solution used in this comparative example was a solution in which 150 ppm by weight of palladium chloride was contained in 5.0 N hydrochloric acid.

  After the plating pretreatment, the molded body was immersed in an acidic electroless nickel phosphorus plating solution (Okuno Pharmaceutical Co., Ltd., Top Nicolon HMA) at 85 ° C. for 3 minutes to form an electroless nickel phosphorus plating film. A plated part was obtained.

[Comparative Example 3]
In this comparative example, a molded body having the first part 101 and the second part 102 shown in FIG. 4 was molded, and the electroless plating film 103 was formed on the first part 101 of the molded body. As the first thermoplastic resin forming the first portion 101, a PA / PO polymer alloy having a composition ratio different from that of Example 1 is used, and as the second thermoplastic resin forming the second portion, Nylon 6 (PA6) was used.

(1) Molding of molded body First, the same material as in Example 1 was used as the material of the PA / PO polymer alloy, and the PA / PO polymer alloy was made by the same method as in Example 1 except that the mixing ratio was changed as follows. Pellets were produced. 19 parts by weight of polyamide, 70 parts by weight of polyolefin, 11 parts by weight of compatibilizer. The obtained PA / PO polymer alloy pellets were used as the first thermoplastic resin forming the first part. As a 2nd thermoplastic resin which forms a 2nd site | part, the non-reinforced PA6 resin (Toyobo's GLAMIDE T-802) was used. Using the first and second thermoplastic resins described above, a molded body having the first part 101 and the second part 102 was molded by the same method as in Example 6.

(2) Pre-plating treatment and electroless plating First, as a pre-plating treatment, the molded body was immersed in an electroless plating catalyst solution at 30 ° C for 1 minute, and then immersed in pure water at 95 ° C for 5 minutes. The electroless plating catalyst solution used in this comparative example was a solution in which 0.5 ppm by weight of palladium chloride was contained in 5.0 N hydrochloric acid.

  After the plating pretreatment, the molded body was immersed in an acidic electroless nickel phosphorus plating solution (Okuno Pharmaceutical Co., Ltd., Top Nicolon HMA) at 90 ° C. for 20 minutes to form an electroless nickel phosphorus plating film. A plated part was obtained.

[Evaluation of plated parts]
The following evaluations (1) to (5) were performed on the plated parts manufactured in Examples 1 to 6 and Comparative Examples 1 to 3. Table 1 shows the molded body materials and electroless plating solutions used in Examples 1 to 6 and Comparative Examples 1 to 3, and Table 2 shows the results of evaluations (1) to (3) and (5). In Table 1, for Example 6 and Comparative Example 3, the material constituting the first part of the molded body was described as the molded body material.

(1) Evaluation of appearance of plating film The appearance of the plating film of the plated part was visually observed and evaluated according to the following evaluation criteria.

Evaluation criteria for plating film appearance:
◯: Neither swelling, cracking nor film loss of the electroless plating film occurred.
X: Swelling, cracking or missing of the electroless plating film occurred.

(2) Adhesion strength of plating film On the electroless nickel phosphorous plating film, an electrolytic copper plating film is formed to 40 μm by a general-purpose method to prepare a measurement sample, and the adhesion strength of the plating film is increased using the measurement sample. It was measured.

(3) Plating film formation time The time from when the molded body was immersed in the electroless nickel phosphorus plating solution until the electroless nickel phosphorus plating film covered the entire surface of the molded body was measured. Whether or not the plating film covered the entire surface of the molded body was judged by visual observation. In Example 6 and Comparative Example 3, the time until the electroless nickel phosphorus plating film covered the entire first portion was measured.

(4) Observation of the cross section of the plated part Using a diamond knife, a surface near the surface of the molded body (100 μm from the surface of the molded body) so that a cross section of about 90 ° (substantially perpendicular) to the surface on which the plated film is formed is obtained A sample for cross-sectional observation of a 5 mm × 5 mm × 2 mm vertical body including a region of a depth of up to 5 mm) was cut out from the molded body. The sample for cross-sectional observation was processed by the frozen ultrathin section method, dyed by a heavy metal staining method using ruthenium tetroxide, and then subjected to cross-sectional observation by TEM (Hitachi High-Tech, H-7650).

(5) Evaluation of the width of the gap (gap) In cross-sectional observation of the plated part, any 10 locations within the 10 μm × 10 μm region in the vicinity of the surface of the molded body (region having a depth from the molded body surface to 100 μm) The width of the gap between the polyamide region and the polyolefin region was measured to obtain an average value, and evaluated according to the following evaluation criteria.

Criteria for evaluating the width of the gap (gap):
○: The average width (gap) width is 0 to 1 μm
X: The average value of the width of the gap (gap) exceeds 1 μm

  As shown in Table 2, in the plated parts produced in Examples 1 to 6, none of the electroless plating film was swollen, cracked or missing, and the adhesion strength of the plating film was as high as 10 N / m or higher. It was. As shown in the TEM photograph of FIG. 7, in the vicinity of the surface of the plated parts manufactured in Examples 1 to 6, striped (striped) polyolefin region islands (domains) in the polyamide region sea (matrix). ) Was formed, and a sea-island structure (matrix-domain structure) was confirmed. In the TEM photograph of FIG. 7, the high luminance (white) region is a polyolefin region, and the low luminance (gray) region is polyamide. The average value of the width of the gap (gap) was 1 μm or less, and the evaluation result of the width of the gap (gap) was good. Further, in the vicinity of the surface of the molded body, the electroless plating film grew mainly in the polyamide region.

  When the plating film formation times of Examples 1 to 3 were compared, the plating film formation time was shorter in the order of Example 3 (7 minutes), Example 2 (10 minutes), and Example 1 (12 minutes). The reason is presumed as follows. Since Examples 2 and 3 contained a block copolymer, the hydrophilicity of the molded body was higher than that of Example 1 and the plating reactivity was improved. Since Example 3 contained fine metal particles that function as an electroless plating catalyst in addition to the block copolymer, the plating reactivity was further improved. Thereby, it is estimated that the plating reactivity of a molded object became high in order of Example 3, Example 2, and Example 1, and the plating film formation time became short.

  In Example 4, the adhesion strength of the plating film was higher than in Examples 1 to 3, and the plating film formation time was shorter than that in Example 1 and was comparable to that in Example 2. In Example 4, since the island size (domain size) in the sea-island structure (matrix-domain structure) of the molded body is as small as nano-order, the stress generated at the interface between the polyamide region and the polyolefin region is reduced, It is estimated that the adhesion strength of the plating film has been improved. In addition, it is presumed that the plating reactivity is improved because the free deposition capable of swelling the polyamide region during electroless plating is improved, and the plating film formation time is shortened. The plated parts manufactured in Example 4 have both metal performance, resin flexibility, and shock absorption, so they can be applied to various fields such as home appliances, wearable devices, and automobiles that require impact resistance when dropped. Can be expected to do.

  In Example 5, the adhesion strength of the plating film and the plating film formation time were the same as in Example 1. However, compared with Example 4, the adhesion strength of the plating film was low and the plating film formation time was long. This is presumably because the island size (domain size) of Example 5 was larger than that of Example 4.

  On the other hand, in Comparative Example 1 in which electroless plating was performed using an alkaline electroless nickel plating solution, no electroless plating reaction occurred. In Comparative Example 1, a plated part was not obtained, and therefore the plated part was not evaluated. Since the alkaline electroless nickel plating solution used in Comparative Example 1 has a low electroless plating treatment temperature (electroless plating solution temperature) and a reducing agent concentration, it is compared with an acidic electroless nickel phosphorous plating solution. Low plating depositability. For this reason, it is presumed that the palladium chloride imparted to the molded body by the pretreatment for plating did not exhibit catalytic ability and electroless plating reaction did not occur.

  In the plated part produced in Comparative Example 2 in which the ratio of polyamide in the PA / PO polymer alloy was high (95 parts by weight), swelling and cracks of the electroless plating film were observed. Compared to Example 1, the plating film formation time was short, but the adhesion strength of the plating film was as low as 2 N / m. As a result of cross-sectional observation of the plated parts, a sea-island structure in which islands (domains) of striped (striped) polyolefin regions are formed in the surface (matrix) of the polyamide region in the surface region of the molded body ( Matrix-domain structure) was confirmed. However, the polyolefin region has a very large domain size and has a layered shape extending in a direction substantially parallel to the surface of the molded body. Moreover, as shown in the TEM photograph of FIG. 8, a portion where a large separation 14 occurred at the interface between the polyamide region and the polyolefin region was also observed. In the TEM photograph of FIG. 8, the high luminance (white) region is a polyolefin region, and the low luminance (gray) region is polyamide. The evaluation result of the width of the gap (gap) was poor. In Comparative Example 2, since the ratio of polyamide in the PA / PO polymer alloy is high and the ratio of the compatibilizer is also low, the polyamide region and the polyolefin region are easily phase-separated, and it is assumed that the polyolefin region is enlarged. . Further, in Comparative Example 2, the temperature of the electroless plating solution is high (85 ° C.), and the temperature of water used for washing in the plating pretreatment is also high (95 ° C.), so that it occurs at the interface between the polyamide region and the polyolefin region. It is estimated that the stress has increased. Furthermore, in Comparative Example 2, since the concentration of hydrochloric acid in the electroless plating catalyst solution was high (5N), it is presumed that the polyamide region was excessively eroded and weakened during the pretreatment for plating. As a result, separation between the polyamide region and the polyolefin region is likely to occur, and it is presumed that the quality of the plating film has deteriorated, such as swelling and cracking of the plating film and a decrease in adhesion strength.

  In the plated part manufactured in Comparative Example 3 in which the ratio of polyamide in the PA / PO polymer alloy is low (19 parts by weight), the plated film remains on the first part even if the molded body is immersed in an electroless plating solution for 20 minutes or more. There was no covering of the film, resulting in film loss. For this reason, in Comparative Example 3, the adhesion strength of the plating film was not measured. This is because the ratio of polyamide in the PA / PO polymer alloy is low (19 parts by weight), and the concentration of palladium chloride in the electroless plating catalyst solution is low (0.5 ppm by weight). It is presumed that palladium could not be adsorbed on the first part of the molded body, and the plating reactivity of the molded body was low. In addition, as a result of cross-sectional observation of the plated part, striped (striped) islands (domains) of polyolefin regions are formed in the surface region of the first part of the molded body within the sea (matrix) of the polyamide region. The confirmed sea-island structure (matrix-domain structure) was confirmed. However, as in Example 2 described above, the average value of the width of the gap (gap) was 5 μm or more, and the evaluation result of the width of the gap (gap) was poor.

  Furthermore, the following evaluations (6) to (8) were performed on Example 6 and Comparative Example 3. Table 3 shows the results of evaluations (6) to (8).

(6) Water Absorption Rate of First and Second Part A first evaluation molded body having the same composition as the first part 101 and a second evaluation molded body having the same composition as the second part 102 were molded. The size of the first and second evaluation molded bodies was 8 cm × 8 cm × 0.2 cm. Next, the molded body for first and second evaluation was immersed in water at 23 ° C. for 24 hours, and the weight increase rate after immersion was determined, and these were each immersed in water at 23 ° C. for 24 hours. It was set as the water absorption rate of the 1st and 2nd site | parts.

(7) Warm water test The manufactured molded object 100 was immersed in 40 degreeC water for 200 hours. The molded body 100 after immersion was visually observed and evaluated based on the following evaluation criteria.

Evaluation criteria for hot water test:
○: No peeling between the first part 101 and the second part 102.
X: There is peeling between the first portion 101 and the second portion 102.

(8) Thermal shock test (heat shock test)
A heat shock test in which the produced molded body 100 was alternately exposed to an atmosphere of −40 ° C. and an atmosphere of 80 ° C. was performed 50 cycles. The molded body 100 after the thermal shock test was visually observed and evaluated based on the following evaluation criteria.

Thermal shock test evaluation criteria:
○: No swelling, cracking, peeling or the like occurs in the plating film 103.
X: Swelling, cracking, peeling, or the like has occurred in the plating film 103.

実施例６のメッキ部品は、第１の部位１０１のみにメッキ膜が形成され、第２の部位１０２にメッキ膜の析出は見られなかった。メッキ膜の有無のコントラストが明確であり意匠性に優れていた。上述したように、本発明者らの検討により、塩化パラジウムは、ＰＡ／ＰＯポリマーアロイ中のポリアミドに特異的に吸着し、アミド基を有さないポリオレフィンには吸着しないことがわかっている。実施例６では、ポリアミドを含む第１の部位のみに無電解メッキ触媒である塩化パラジウムが吸着したため、第１の部位のみにメッキ膜が形成されたと推測される。温水試験及び熱衝撃試験の評価結果も良好であった。

In the plated component of Example 6, a plating film was formed only at the first portion 101, and no deposition of the plating film was observed at the second portion 102. The contrast with and without the plating film was clear and the design was excellent. As described above, the inventors' investigation has shown that palladium chloride specifically adsorbs to the polyamide in the PA / PO polymer alloy and does not adsorb to the polyolefin having no amide group. In Example 6, since palladium chloride as an electroless plating catalyst was adsorbed only in the first part containing polyamide, it is presumed that the plating film was formed only in the first part. The evaluation results of the hot water test and thermal shock test were also good.

  On the other hand, in the plated part of Comparative Example 3, film loss occurs in the plating film of the first part 101, and the plating film is deposited in the second part 102, and the contrast of the presence or absence of the plating film is unclear. There was poor design. The reason for the film loss in the plating film at the first site is presumed to be due to the low ratio of polyamide in the PA / PO polymer alloy as described above. Since the ratio of polyamide was low, the water absorption rate of the first portion 101 was also low (0.4% by weight). In addition, since polyamide is used for the second portion 102, it is presumed that palladium chloride was also adsorbed to the second portion 102 in the pretreatment for plating, and a plating film was deposited. Moreover, in this comparative example, the evaluation results of the hot water test and the thermal shock test were poor. In this comparative example, since the water absorption rate of the second part 102 is as high as 2.6% by weight, water easily collects between the first part 101 and the second part 102. Therefore, in the hot water test, It is presumed that peeling occurred between the part 101 and the second part 102, and swelling or the like occurred in the plating film 103 in the thermal shock test.

  In the plated component of the present invention, a plated film having high adhesion strength and excellent appearance characteristics is formed on the surface of a molded body containing a PA / PO polymer alloy. Therefore, the plated component of the present invention is suitable for automobile interior / exterior components, building material components, home appliance components, and the like.

10 Molded body 11 Polyamide region 12 Polyolefin region 13 Air gap (gap)
101 First part 102 Second part 103 Plating film 100, 300 Plating component

Claims (12)

Plated parts,
A molded body containing a polymer alloy containing 20 to 90% by weight of polyamide and 10 to 80% by weight of polyolefin;
An electroless plating film on the surface of the molded body,
Inside the molded body is a polyamide region and a polyolefin region,
A plated part, wherein a width of a gap generated between the polyamide region and the polyolefin region is 1 μm or less.   2. The plated part according to claim 1, wherein the polyamide region and the polyolefin region form a sea-island structure inside the molded body.   The plated component according to claim 1 or 2, wherein the polymer alloy contains 40 to 70% by weight of polyamide and 30 to 60% by weight of polyolefin.   The plated part according to any one of claims 1 to 3, wherein the polymer alloy further contains 1% by weight to 10% by weight of a compatibilizing agent.   The plated part according to claim 1, wherein the polyamide is nylon 6.   The plated component according to claim 1, wherein the polyolefin is polypropylene.   The plated part according to any one of claims 1 to 6, wherein the molded body further includes a block copolymer having a hydrophilic segment.   The plated part according to claim 7, wherein the molded body further includes metal fine particles having a particle diameter of 10 nm or less. The molded body has a first portion having the electroless plating film on the surface, and a second portion not having the electroless plating film on the surface,
The first portion includes the polymer alloy,
The plated part according to claim 1, wherein the second portion includes a second thermoplastic resin.   The water absorption rate of the first part when immersed in water at 23 ° C. for 24 hours is 0.5% by weight to 3.0% by weight, and the water absorption rate of the second part is 2.0% by weight. The plated component according to claim 9, wherein:   The plated component according to claim 9 or 10, wherein the second thermoplastic resin contains polypropylene.   The plated part according to any one of claims 9 to 11, wherein the molded body is an integrally molded body of a first part and a second part.

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