JP2017137529A - Production method of composite resin material, production method of plated component, resin pellet and resin substrate - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a production method of a composite resin material capable of forming, on the surface, a uniform plating film having high adhesion strength and excellent also in an appearance characteristic.SOLUTION: A production method of a composite resin material includes steps for: producing a resin substrate containing, near the surface, a compound for fixing a metal; and bringing liquid containing a metal compound into contact with the resin substrate.SELECTED DRAWING: Figure 1

Description

  The present invention relates to a method for producing a composite resin material, a method for producing a plated component, a resin pellet, and a resin substrate.

  Electroless plating is known as a method for forming a metal film on a resin substrate at low cost. In electroless plating, in order to secure the adhesion of the metal film to the resin substrate, a pretreatment is performed to roughen the resin substrate surface using an etchant containing an oxidizing agent such as hexavalent chromic acid or permanganic acid. . Therefore, an ABS resin (acrylonitrile / butadiene / styrene copolymer synthetic resin) that is eroded by an etching solution has been mainly used for electroless plating. In the ABS resin, the butadiene rubber component is selectively eroded by the etching solution, and irregularities are formed on the surface. On the other hand, for a resin other than the ABS resin, for example, polycarbonate, a plating grade in which a component that is selectively oxidized to an etching solution such as an ABS resin or an elastomer is mixed in order to enable electroless plating. However, such a pretreatment of electroless plating has a problem of high environmental load because hexavalent chromic acid or the like is used.

  An electroless plating catalyst is applied to the roughened surface of the resin substrate. As the electroless plating catalyst application to the resin substrate, two kinds of methods are mainly used. Sensitizer-activating method in which tin colloid is adsorbed on the substrate (sensitizer), immersed in 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 (accelerator). These conventional catalyst application treatments actually require more steps. For example, in the catalyst accelerator method, post-etching for improving the surface property of a resin base material and post-accelerator for removing tin that cannot be removed by the accelerator are performed.

  In order to reduce the number of steps in the plating pretreatment, Patent Document 1 discloses that a resin base is used in one solution containing an inorganic acid-containing corrosive agent such as hydrochloric acid, an ionogenic activator such as palladium ion, and an organic acid such as acetic acid. A method of processing the material has been proposed. According to Patent Document 1, a good plating film can be obtained by pre-processing a polyamide substrate with the above-described one solution. Moreover, according to this method, it is not necessary to use hexavalent chromic acid or the like that has a high environmental load.

Japanese Patent No. 4109615

  However, in recent years, higher adhesion strength and better appearance characteristics may be required for a plating film formed on a resin substrate. For this reason, a resin material capable of forming a plating film that is superior in appearance characteristics and adhesion strength is required.

  The present invention solves these problems and provides a method for producing a composite resin material capable of forming a uniform plating film having high adhesion strength and excellent appearance characteristics.

  According to the first aspect of the present invention, there is provided a method for producing a composite resin material, comprising producing a resin base material containing a compound for fixing a metal in the vicinity of a surface, and adding a metal compound to the resin base material. There is provided a method for producing a composite resin material comprising contacting a liquid to be contained.

  In this aspect, manufacturing the resin base material includes manufacturing a resin pellet containing the compound for fixing the metal and a first thermoplastic resin, the resin pellet, and a second thermoplastic resin. Mixing the resin and molding to obtain the resin base material, or producing the resin base material is brought into contact with a liquid containing a compound for fixing the metal to the resin molded body. Thus, the resin base material may be obtained.

  In this embodiment, the compound for fixing the metal may be at least one selected from the group consisting of a reducing compound and a compound having an amide group or an amine group having a molecular weight of 60 to 2,000. In 1 g of the compound having an amide group or an amine group, an amide group or an amine group may be contained in an amount of 1 mmol / g to 20 mmol / g. The reducing compound may be at least one selected from the group consisting of calcium hypophosphite, sodium hypophosphite, and sodium borohydride.

  The metal compound may be a metal salt, and the metal contained in the metal compound may be Pd or Ag. Further, the compound for fixing the metal is a compound having an amide group or an amine group having a molecular weight of 60 to 2000, and the concentration of the amide group or the amine group in the vicinity of the surface of the resin substrate is the compound resin substrate. It may be higher than the concentration of the amide group or amine group in the part other than the vicinity of the surface of the surface.

  According to the second aspect of the present invention, there is provided a method for producing a composite resin material, wherein a liquid containing a compound for fixing a metal is brought into contact with a resin molded body, and a metal compound is contained in the resin molded body. There is provided a method for producing a composite resin material comprising contacting a liquid.

  According to a third aspect of the present invention, there is provided a method for producing a plated component, wherein a composite resin material is produced by the method for producing a composite resin material according to the first aspect or the second aspect, and the composite resin material In addition, a method for producing a plated part is provided, which includes contacting an electroless plating solution to form an electroless plating film on the surface of the composite resin material.

  According to the 4th aspect of this invention, it is a resin pellet, Comprising: The resin pellet characterized by including the compound which fixes a metal, and a thermoplastic resin is provided.

  According to a fifth aspect of the present invention, there is provided a resin base material comprising a compound for fixing a metal, a first thermoplastic resin, and a second thermoplastic resin. Is provided.

  In the present invention, a compound having a relatively low molecular weight amide group or amine group contained in the vicinity of the surface of the resin base material, a compound for fixing a metal such as a reducing compound allows the penetration of the metal compound into the resin base material. Promoted. The resin base material infiltrated with the metal compound, that is, the composite resin material produced by the production method of the present invention, exhibits a function derived from the metal in the metal compound. For example, when a metal having electroless plating catalytic ability is used as the metal of the metal compound, the composite resin material functions as a body to be electrolessly plated. In this case, the composite resin material does not require plating pretreatment with a high environmental load, and can form a uniform plating film having high adhesion strength on the surface and excellent appearance characteristics.

FIG. 1 is a flowchart showing a method for manufacturing a composite resin material manufactured in the first and second embodiments. FIG. 2 is a flowchart showing a method for manufacturing the composite resin material manufactured in the third and fourth embodiments. FIG. 3 is a flowchart showing a method of manufacturing a composite resin material (plated component) having a plating film manufactured in the fifth embodiment. FIG. 4 shows a manufacturing apparatus used for manufacturing resin pellets in Example 1. FIG. 5 is an enlarged view of a downstream seal mechanism that is a part of the manufacturing apparatus shown in FIG. 4.

[First Embodiment]
As a first embodiment, a method for manufacturing the composite resin material shown in FIG. 1 will be described. In the present embodiment, a resin base material containing a compound for fixing a metal in the vicinity of the surface is produced by molding. Although the molding method of the resin base material which contains the compound which fixes a metal in the surface vicinity is arbitrary, in this embodiment, the resin pellet containing the compound which fixes a metal, and the 1st thermoplastic resin is manufactured ( Step S1 in FIG. 1 and the produced resin pellets and the second thermoplastic resin are mixed and molded to obtain a resin base material (step S2 in FIG. 1). In the present embodiment, the “metal-fixing compound” is a compound having a property of adsorbing or reducing a metal, for example, a compound having an amide group or an amine group having a property of adsorbing (trapping) a metal, a metal Examples thereof include reducing compounds that reduce and fix ions to fix them. In the present embodiment, a compound having an amide group or an amine group having a molecular weight of 60 to 2000 (hereinafter referred to as “containing compound such as amide group”) is used as the compound for fixing the metal.

<Resin pellets>
The resin pellet of the present embodiment includes an amide group-containing compound having a molecular weight of 60 to 2000 and a first thermoplastic resin. 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. In this embodiment, the resin pellet containing the amide group-containing compound corresponds to a master batch, and the second thermoplastic resin, which is the main component of the resin base material, corresponds to a base resin in which the master batch is blended. To do. 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 a compound containing an amide group or the like which is a functional material directly to the base resin. Moreover, when a masterbatch is used, there also exists an advantage that the molded object containing a functional material can be easily manufactured using a general purpose molding machine.

  The molecular weight of the compound containing an amide group or the like used in the present embodiment is 60 to 2000, preferably 60 to 500, and more preferably 60 to 200. If the molecular weight of the amide group-containing compound is within the above range, the molecular weight of the amide group-containing compound is sufficiently smaller than that of the second thermoplastic resin that is the main component of the resin substrate. For this reason, the amide group-containing compound bleeds near the surface of the resin base material, and the concentration of the amide group or amine group near the resin base material surface can be increased. On the other hand, if the molecular weight of the amide group-containing compound is smaller than the above range, the amide group-containing compound is likely to fall off from the surface of the resin base material, which may contaminate the mold used for molding the resin base material. There is. Moreover, if the molecular weight of the compound containing an amide group or the like is larger than the above range, bleeding near the resin substrate surface becomes difficult. Furthermore, it becomes easy to phase-separate with the 2nd thermoplastic resin which is a main component of a resin base material, As a result, it becomes difficult to disperse | distribute uniformly in the surface vicinity of the resin base material.

  The amide group-containing compound used in this embodiment is preferably a solid at normal temperature from the viewpoint of not reducing the mechanical strength of the resin base material, and the amide group-containing compound has a melting point of 10 ° C. or higher. Are preferred, and those at 25 ° C. or higher are more preferred. Although the upper limit of melting | fusing point of amide group etc. containing compounds is not specifically limited, For example, it is 200 degrees C or less. In addition, the compound containing amide groups or the like used in the present embodiment has a larger number of amide groups or amine groups per unit weight so that the concentration of amide groups or amine groups in the vicinity of the surface of the resin substrate can be efficiently increased. Is preferred. For example, in 1 g of the compound containing an amide group or the like, the amide group or the amine group is preferably contained in an amount of 1 mmol / g or more, and more preferably 3 mmol / g or more. The upper limit of the number of moles of the amide group or amine group contained in 1 g of the amide group-containing compound is not particularly limited, but is, for example, 20 mmol / g or less.

  Among the amide group-containing compounds, examples of the compound having an amide group include primary amides such as urea, acetamide, propionamide, methacrylamide and nicotinamide; N-methylacetamide, N-methylpropionamide, N-ethyl Secondary amides such as acetamide, 2-acetamidoethanol and 1,3-dimethylurea; 2-pyrrolidone, 2-piperidone, ε-caprolactam, ω-heptalactam, 5-methyl-2-pyrrolidone, glycine anhydride, glutarimide , 2,4-piperidinedione, hydantoin, 3-morpholinone, 2-imidazolidinone, cyclic secondary amides such as isocyanuric acid and barbituric acid; N, N-dimethylacetamide, N, N-dimethylpropionamide, N, N -Diethylacetamide, N, N-dimethyla Tertiary amides such as rilamide, N, N-diethylacrylamide, 1-acetylpyrrolidine, 1-acetylpiperidine, N-methylacetanilide and 4-acetylmorpholine; 1-methyl-2-pyrrolidone, N-methyl-ε-caprolactam, Cyclic tertiary amides such as 1- (2-hydroxyethyl) -2-pyrrolidone, N-vinyl-ε-caprolactam and 1,3-dimethyl-2-imidazolidinone can be used. Among the amide group-containing compounds, as the compound having an amine group, polyethyleneimine or the like can be used. These amide group-containing compounds may be used alone or in combination of two or more.

  The content of the compound containing an amide group or the like in the resin pellet is, for example, from 0.1% by weight to 50% by weight from the viewpoint of both the ability to adsorb the metal compound and the mechanical strength of the resin pellet, 1% to 30% by weight.

  The first thermoplastic resin used in the present embodiment is arbitrary as long as it is a thermoplastic resin that can be mixed or compatible with the base resin (second thermoplastic resin) into which the resin pellets are mixed. Thermoplastic resins having amine or amide groups that tend to trap, such as polyamides, are preferred. As the polyamide, for example, nylon 6 (PA6), nylon 66 (PA66), nylon 12 (PA12), nylon 11 (PA11), nylon 6T (PA6T), nylon MXD6 (PAMXD6: metaxylenediamine (MXDA)) was used. Polyamide), 6/66 copolymer nylon (PA 6/66), amorphous nylon, and the like. Among them, amorphous nylon and 6/66 copolymer nylon, which tend to bleed near the surface of the resin base material during molding of the resin base material due to low crystallinity and low solidification rate, are the first heat Preferred as a plastic resin. Moreover, the block copolymer of polyamide and hydrophilic property imparting agents, such as a polyether used as an antistatic agent with high concentrating property to the resin base material surface, can also be used. In addition, these 1st thermoplastic resins may be used independently, or 2 or more types may be mixed and used for them.

  The content of the first thermoplastic resin in the resin pellet is, for example, 30% by weight to 99.9% by weight from the viewpoint of both the ability to adsorb the metal compound and the mechanical strength of the resin pellet, preferably 50% by weight to 99% by weight. The resin pellet of the present embodiment may further contain various inorganic fillers such as glass fiber, talc, and carbon fiber and other various additives.

<Production method of resin pellet>
The resin pellet of this embodiment is manufactured by, for example, extruding an amide group-containing compound and a first thermoplastic resin and then cutting the molded product (step S1 in FIG. 1). The amide group-containing compound and the first thermoplastic resin may be mixed (dry blended) and then introduced into the plasticizing cylinder of the extrusion molding machine, or the first thermoplastic resin may be introduced into the plasticizing cylinder first. The resin may be plasticized and melted, and then a compound containing an amide group or the like may be introduced into the plasticizing cylinder and mixed with the molten resin. When the amide group-containing compound is mixed with the molten resin later, the amide group-containing compound may be directly mixed with the molten resin, or a solution in which the amide group-containing compound is dissolved in the solvent is mixed with the molten resin. May be.

  In the present embodiment, the first thermoplastic resin is first plasticized and melted in a plasticizing cylinder, and then a solution of an amide group-containing compound is introduced into the plasticizing cylinder and mixed with the molten resin. When the melting point of the amide group-containing compound is low, if it is directly introduced into a high-temperature plasticizing cylinder, the amide group-containing compound is melted and fixed in the plasticizing cylinder, and it may be difficult to uniformly disperse it. Therefore, when the melting point of the amide group-containing compound is lower than the molding temperature of the thermoplastic resin, it is preferable to dissolve the amide group-containing compound in a solvent and mix it with the molten resin as a solution. Thereby, even an amide group-containing compound having a low melting point can be uniformly dispersed in the molten resin.

  The solvent that dissolves the amide group-containing compound is not particularly limited as long as it is a solvent that can dissolve the amide group-containing compound, and can be appropriately selected based on the type of the amide group-containing compound. A solvent having a certain degree of volatility is preferable so that it does not remain inside. From this point of view, preferred solvents include water; organic solvents such as ethanol, propanol, isopropanol, butanol, isobutanol, acetone, and ethyl methyl ketone; and pressurized carbon dioxide such as liquid carbon dioxide and supercritical carbon dioxide. It is done. These solvents may be used alone or in combination of two or more.

  The concentration of the amide group-containing compound in the solution, the amount of the amide group-containing compound introduced into the first thermoplastic resin, and the like can be determined as appropriate based on the composition of the resin pellets to be produced. In a plasticizing cylinder of an extruder, the first thermoplastic resin that has been plasticized and melted and a solution of an amide group-containing compound are mixed, and then the mixture is extruded into a string shape. After cooling the string-shaped molded product, a resin pellet is manufactured by cutting using a general-purpose cutting device such as a strand cutting device. Extrusion molding, cooling and cutting are preferably performed continuously from the viewpoint of productivity of resin pellets.

  In the production of resin pellets, when using a compound having a relatively low melting point such as an amide group (for example, ε-caprolactam, melting point: 69 ° C.), the compound containing the amide group or the like is dissolved in a solvent as described above, It is preferable to mix with molten resin as a solution. However, the present embodiment is not limited to this, and when a compound such as an amide group having a relatively high melting point (for example, hydantoin, melting point: 218 ° C.) is used, the first compound is obtained by dry blending without using a solvent. The resin pellets may be produced by directly mixing and molding the thermoplastic resin and the amide group-containing compound.

<Molding of resin base material>
Next, the manufactured resin pellets and the second thermoplastic resin are mixed and plasticized and melted to form a resin base material (step S2 in FIG. 1). A 2nd thermoplastic resin is a main component of the composite resin material manufactured from a resin base material and a resin base material, and is equivalent to the base resin with which a masterbatch is mix | blended. The 2nd thermoplastic resin used by this embodiment is not specifically limited, According to the use of the target composite resin material, it can select suitably. For example, as the second thermoplastic resin, polypropylene, polymethyl methacrylate, polyamide, polycarbonate, amorphous polyolefin, polyether imide, polyethylene terephthalate, polyether ether ketone, ABS resin (acrylonitrile / butadiene / styrene copolymer synthetic resin), Polyphenylene sulfide, polyamideimide, polylactic acid, polycaprolactone and the like can be used. Of these, versatile polyamide and ABS resin are preferable as the second thermoplastic resin. In addition, the second thermoplastic resin is a glass fiber, talc, carbon fiber, or the like similar to the first thermoplastic resin for the purpose of improving the surface property (appearance), mechanical strength, and dimensional stability of the resin base material. An inorganic filler and other various additives may be included, and a commercially available mineral reinforced resin may be used. In addition, these 2nd thermoplastic resins may be used independently, or 2 or more types may be mixed and used for them.

  The mixing ratio of the second thermoplastic resin (base resin) and the resin pellets (master batch) can be appropriately determined based on the composition of the resin base material to be manufactured. For example, the content of the resin pellet (master batch) is preferably 0.1% by weight to 30% by weight and more preferably 0.5% by weight to 20% by weight in the resin base material. When the content of the resin pellet (master batch) is within the above range, a sufficient amount of amide group or amino group can be contained in the vicinity of the surface of the resin substrate. The content of the second thermoplastic resin that is the main component of the resin base material is, for example, preferably 30% to 99% by weight, and more preferably 50% to 99% by weight in the resin base material. Moreover, when the resin base material contains an inorganic filler, the content of the inorganic filler in the resin base material is 10% by weight or more from the viewpoint of the mechanical strength of the resin base material, moldability (ease of molding), and the like. 70 weight% is preferable and 20 weight%-60 weight% is more preferable.

  The molding method of the resin base material of the present embodiment is not particularly limited. For example, a resin pellet containing a compound containing an amide group or the like, a second thermoplastic resin, and, if necessary, other general-purpose additives are dry-blended in a desired ratio, and a general-purpose injection molding machine or extrusion molding machine It can be molded by a general-purpose molding method using a molding machine such as

  Since the molecular weight of the amide group-containing compound is sufficiently smaller than that of the second thermoplastic resin, the amide group-containing compound is likely to bleed in the vicinity of the surface of the resin substrate in the molding of the resin substrate. Thereby, the density | concentration of the amide group or amine group of the resin base-material surface vicinity can be raised. Further, when a thermoplastic resin having a crystallinity lower than that of the second thermoplastic resin is used as the first thermoplastic resin, the first thermoplastic resin is accompanied by a compound containing an amide group or the like. Bleed in the vicinity of the surface, and further the concentration of amide groups or amine groups in the vicinity of the resin substrate surface can be increased. In addition, the amide group-containing compound may be polymerized by heat or pressure in the molding process, but even when the molecular weight is increased by polymerization, the crystallinity is lower than that of the base resin. Easy to bleed on the surface. In addition, since the first thermoplastic resin having a low crystallinity bleeds in the vicinity of the surface of the resin base material, a further effect that a metal compound described later easily penetrates into the resin base material also occurs. As a combination of the first thermoplastic resin and the second thermoplastic resin that provides such an effect, for example, amorphous nylon, 6/66 copolymer nylon, or the like is used as the first thermoplastic resin. Examples of the thermoplastic resin 2 include the use of crystalline nylon such as nylon 6 and nylon 66.

  In the present specification, “near the surface” of the resin base material means a region inside the resin base material and close to the surface. To what extent the “near surface” of the resin substrate means the region from the surface of the resin substrate depends on the type of thermoplastic resin used for the resin substrate. A region having a depth of 0.1 to 10 μm from the surface of the material is preferable.

<Granting metal compounds>
Next, a liquid containing a metal compound (hereinafter referred to as “metal compound liquid”) is brought into contact with the obtained resin base (step S3 in FIG. 1). Thereby, the metal compound in a metal compound liquid adsorb | sucks and / or osmose | permeates a resin base material, and the composite resin material of this embodiment is obtained.

  The kind of metal contained in the metal compound is not particularly limited, and can be appropriately selected according to the intended use of the composite resin material. For example, when the composite resin material functions as a body to be electrolessly plated, a metal compound having electroless plating catalytic ability such as Pd, Pt, Cu, Ni, etc. can be used. In the case of functioning as an antibacterial material, a metal compound having an antibacterial action such as Ag can be used. From the viewpoint of easy penetration into the resin substrate, it is preferable that the metal compound is dissolved and exists as metal ions in the metal compound solution. Therefore, the metal compound is preferably a metal salt that can be dissolved in a liquid. Examples of such metal compounds include palladium chloride and silver chloride.

  The concentration of the metal compound in the metal compound liquid can be appropriately adjusted based on conditions such as the intended use of the composite resin material, the temperature of the metal compound liquid, the contact time between the metal compound liquid and the resin substrate, 0.05 mg / L to 100 g / L, preferably 1 mg / L to 20 g / L, more preferably 5 mg / L to 10 g / L. If the concentration of the metal compound is lower than the above range, the amount of the metal compound adsorbed on the resin substrate may be uneven. For example, when the metal compound functions as an electroless plating catalyst, there is a possibility that a plating film may be defective. On the other hand, if the concentration of the metal compound exceeds the above range, the amount of the metal compound adsorbed on the surface of the resin base material may increase, resulting in inconvenience. For example, when a metal compound functions as an electroless plating catalyst, the plating reaction on the outermost surface of the composite resin material becomes dominant, and the adhesion strength of the plating film may be reduced.

  The solvent for dissolving or dispersing the metal compound is not particularly limited, and can be selected according to the type of the metal compound. For example, water; organic solvents such as ethanol, propanol, isopropanol, butanol, isobutanol, acetone, and ethyl methyl ketone These mixed solvents may be mentioned. Furthermore, in order to increase the solubility of the metal compound, the pH of the liquid may be adjusted by adding hydrochloric acid, nitric acid, ammonia, sodium hydroxide, or the like. Also, when the resin base material contains minerals that can be dissolved in acids such as calcium carbonate and calcium silicate, by using acid in the metal compound solution, the mineral in the resin base material is dissolved and the surface of the resin base material is uneven. And the penetration of the metal compound into the resin base material can be promoted.

  The metal compound liquid of the present embodiment may be composed only of a metal compound and a liquid that is a solvent or a dispersion medium thereof, and may contain other additives as necessary. The metal compound liquid may contain a surfactant, for example. By containing the surfactant, the surface tension of the metal compound liquid is reduced, the wettability to the surface of the resin base material is improved, and the metal compound easily penetrates into the resin base material. 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 metal compound solution into contact with the resin base material is arbitrary, and various methods can be used depending on the purpose. For example, the entire resin base material may be immersed in the metal compound liquid, or only a part of the resin base material may be brought into contact with the metal compound liquid.

  The time for bringing the metal compound liquid into contact with the resin substrate is preferably, for example, 5 seconds to 15 minutes. If it is less than 5 seconds, there is a possibility that the amount of adsorption of the metal compound on the resin substrate may be uneven. Moreover, when it exceeds 15 minutes, there exists a possibility of deterioration of the resin base material by the metal compound liquid which osmose | permeated the resin base material.

  As described above, the resin base material of the present embodiment contains an amide group-containing compound having a relatively low molecular weight of 60 to 2000 in the vicinity of the surface. And an amide group or an amine group has a property which is easy to adsorb | suck a metal compound. Adsorption and permeation of the metal compound to the resin base material are promoted by the amide group or amine group in the resin base material, and a composite resin material having a function derived from these metals is obtained. For example, if a metal having electroless plating catalytic ability such as Pd, Pt, Cu, Ni is used as the metal of the metal compound, the composite resin material of this embodiment has already been provided with an electroless plating catalyst. Functions as a body to be electrolessly plated. Usually, in order to give an electroless plating catalyst to a body to be plated, it is necessary to etch the body to be plated using a solvent with a high environmental load, but the composite resin material of the present embodiment has such a treatment. Is unnecessary. For example, when a metal having an antibacterial action such as Ag is used as the metal of the metal compound, the composite resin material of the present embodiment functions as an antibacterial material.

  In the present embodiment, for example, when polyamide is used as the base resin (second thermoplasticity) of the resin substrate, the resin substrate already has an amide group without containing a compound containing an amide group or the like. However, it contains a relatively low molecular weight compound such as an amide group, and it bleeds to the vicinity of the surface, so that the concentration of the amide group or amine group in the vicinity of the resin substrate surface can be further increased. Penetration into the material is promoted. In addition, the amide group-containing compound has a lower molecular weight than the base resin (second thermoplastic), so it has a high degree of freedom in the resin substrate, and captures metal compounds more than the base resin having an amide group. It is thought that it is easy to do. In addition, for example, even when the base resin (second thermoplastic) of the resin base material is a resin that does not have an amide group and an amine group such as an ABS resin, it contains an amide group-containing compound in the vicinity of the surface. The penetration of the metal compound into the resin base material is promoted, and the composite resin material of this embodiment can be manufactured. Thus, the manufacturing method of this embodiment has a wide range of selection of the base resin of the resin base material, and can manufacture composite resin materials using various base resins depending on the application.

  Moreover, in this embodiment, you may further provide the etching process of a resin base material before making a metal compound liquid contact a resin base material. By etching the surface of the resin substrate, it is possible to further promote the penetration of the metal compound into the resin substrate. For example, when an ABS resin is used as the second thermoplastic resin, ethylene glycol monobutyl ether, diethylene glycol monohexyl ether, dipropylene glycol monomethyl ether, diethylene glycol diethyl ether, diethylene glycol dimethyl ether, diethylene glycol monoethyl ether, diethylene glycol monomethyl ether and triethylene By immersing the resin substrate in a solvent such as glycol monobutyl ether, micropores can be formed on the surface of the resin substrate.

  In the embodiment described above, in the method for producing a resin base material, resin pellets (master batch) containing a compound containing an amide group or the like and a second thermoplastic resin (base resin) are mixed and molded. Although the method for obtaining the resin base material has been described, the present embodiment is not limited to this. For example, a resin base material may be obtained by directly mixing a compound containing an amide group or the like with a second thermoplastic resin without molding resin pellets and molding.

[Second Embodiment]
In this embodiment, a reducing compound is used as the compound for fixing the metal. A composite resin material is produced by the same method as in the first embodiment except that a reducing compound is used as the compound for fixing the metal.

<Production method of resin pellet>
First, resin pellets containing a reducing compound and a first thermoplastic resin are manufactured (step S1 in FIG. 1). The reducing compound used in the present embodiment is preferably an inorganic compound that is not thermally decomposed in the molding process, and examples thereof include sodium hypophosphite, potassium hypophosphite, and calcium hypophosphite. These reducing compounds may be used alone or in combination of two or more. The content of the reducing compound in the resin pellet is, for example, 0.1% by weight to 50% by weight from the viewpoint of achieving both the ability to reduce the metal compound and the mechanical properties of the resin pellet, and preferably 1 % By weight to 30% by weight.

  The first thermoplastic resin used in the present embodiment is a thermoplastic resin that can be mixed or compatible with the base resin (second thermoplastic resin) into which the resin pellets are mixed, and is the same as in the first embodiment. Things can be used with similar contents. The resin pellet of the present embodiment may further contain various inorganic fillers such as glass fiber, talc, and carbon fiber and other various additives.

  The resin pellets of this embodiment are manufactured by extruding the reducing compound and the first thermoplastic resin and then cutting the molded product (step S1 in FIG. 1), as in the first embodiment.

<Molding of resin base material>
Next, the manufactured resin pellets and the second thermoplastic resin are mixed and plasticized and melted to form a resin base material (step S2 in FIG. 1). In this embodiment, the resin pellet containing a reducing compound corresponds to a master batch, and the second thermoplastic resin that is a main component of the resin base material corresponds to a base resin into which the master batch is blended. The 2nd thermoplastic resin used by this embodiment can use the thing similar to 1st Embodiment.

  The molding method of the resin base material of the present embodiment is not particularly limited. Similarly to the first embodiment, based on the composition of the resin base material to be manufactured, the mixing ratio of the second thermoplastic resin (base resin) and the resin pellet (masterbatch) is appropriately determined and mixed. It can be molded by a molding method.

  The molecular weight of the reducing compound is sufficiently smaller than that of the second thermoplastic resin. For this reason, in the molding of the resin base material, the reducing compound tends to bleed near the surface of the resin base material. Thereby, the density | concentration of the reducing compound of the resin base-material surface vicinity can be raised. Similarly to the first embodiment, when a thermoplastic resin having a crystallinity lower than that of the second thermoplastic resin is used as the first thermoplastic resin, the first thermoplastic resin is a reducing compound. In the vicinity of the surface of the resin base material, the concentration of the reducing compound near the surface of the resin base material can be increased, and the metal compound described later can easily penetrate into the resin base material. .

<Granting metal compounds>
Next, a liquid (metal compound liquid) containing a metal compound is brought into contact with the obtained resin base material (step S3 in FIG. 1). As the metal compound and the metal compound liquid, those similar to those in the first embodiment can be used. The method similar to 1st Embodiment can be used also for the method of making a metal compound liquid contact a resin base material.

  As described above, the resin base material of the present embodiment contains a reducing compound near the surface. The reducing compound can reduce the metal compound to insolubilize and fix the metal on the surface of the substrate. Thereby, the composite resin material which has a function derived from the metal fix | immobilized on the resin base-material surface is obtained. The composite resin material of this embodiment has the same effect as the composite resin material of the first embodiment.

[Third Embodiment]
As a third embodiment, a method for producing the composite resin material shown in FIG. 2 will be described. In this embodiment, the manufacturing method of the resin base material containing the compound which fixes a metal near the surface is different from the first and second embodiments. In the present embodiment, first, a resin molded body is prepared, and the resin molded body is brought into contact with a liquid containing a compound for fixing a metal (step S21 in FIG. 2). Thereby, the compound which fixes the metal in the liquid containing the compound for fixing the metal is adsorbed and / or penetrates into the resin molded body, and a resin base material containing the compound for fixing the metal in the vicinity of the surface is obtained. In the present embodiment, a compound having an amide group or an amine group having a molecular weight of 60 to 2000 (a compound containing an amide group or the like) similar to that used in the first embodiment is used as the metal fixing compound.

<Resin molding>
The resin molded body used in the present embodiment is mainly composed of a thermoplastic resin (base resin). The thermoplastic resin used for the resin molded body is not particularly limited, and for example, the same thermoplastic resin as the second thermoplastic resin used in the first embodiment can be used. Among them, the thermoplastic resin used in the present embodiment is preferably polyamide because of the ease of penetration of the amide group-containing compound. The thermoplastic resin used in the present embodiment is the same as the second thermoplastic resin used in the first embodiment for the purpose of improving the surface properties (appearance), mechanical strength, and dimensional stability of the resin molded body. Further, various inorganic fillers such as glass fiber, talc and carbon fiber and other various additives may be contained, and commercially available mineral reinforced resins may be used. In addition, a thermoplastic resin may be used individually by 1 type, or 2 or more types may be mixed and used for it. In addition, the resin molded body used in the present embodiment may be obtained by molding the above-described thermoplastic resin by a general-purpose molding method, or a commercially available molded body may be used.

<Granting of amide group-containing compounds>
Next, the resin molded body is brought into contact with a liquid containing an amide group-containing compound (hereinafter referred to as “amide group-containing compound liquid”) to give the amide group-containing compound to the resin molded body (step S21 in FIG. 2). ). In the present embodiment, the amide group-containing compound may be the same as that described in the first embodiment. However, in the first embodiment, from the viewpoint of easy manufacture of resin pellets, the compound containing an amide group or the like is preferably solid at room temperature, but since this embodiment does not manufacture resin pellets, It may be a liquid.

  The solvent for dissolving or dispersing the amide group-containing compound is not particularly limited and may be appropriately selected based on the type of the amide group-containing compound, but a solvent that can dissolve the amide group-containing compound is preferable. For example, for example, water; organic solvents such as ethanol, propanol, isopropanol, butanol, isobutanol, acetone, ethyl methyl ketone, and the like. These liquids may be used alone or in combination of two or more. Further, when the compound containing an amide group or the like is in a liquid state, the liquid may not be used for dilution. In this case, the amide group-containing compound liquid is composed only of the amide group-containing compound liquid.

  The concentration of the amide group-containing compound in the amide group-containing compound liquid includes the intended use of the composite resin material, the temperature of the amide group-containing compound liquid, the contact time between the amide group-containing compound liquid and the resin molding, etc. Although it can adjust suitably based on these conditions, it is 0.1 to 50 weight%, for example, Preferably, it is 1 to 20 weight%. When the concentration of the amide group-containing compound is within the above range, a sufficient amount of the amide group-containing compound can be adsorbed and / or permeated without unevenness in the resin molding.

  The amide group-containing compound liquid of the present embodiment may be composed only of the amide group-containing compound and a liquid that is a solvent or dispersion medium thereof, and may contain other additives as necessary. The amide group-containing compound liquid can be prepared by uniformly mixing an amide group-containing compound, a liquid, and, if necessary, other additives by a general-purpose method.

  The method of bringing the compound liquid containing an amide group into contact with the resin molded body is arbitrary, and various methods can be used depending on the purpose. For example, the entire resin molded body may be immersed in an amide group-containing compound liquid, or only a part of the resin molded body may be brought into contact with the amide group-containing compound liquid. By bringing the amide group-containing compound liquid into contact with the resin molded body, the amide group-containing compound penetrates into the resin molded body, and a resin base material containing the amide group-containing compound in the vicinity of the surface is obtained.

  The time for bringing the compound liquid containing the amide group into contact with the resin molding and the temperature of the compound liquid containing the amide group, etc. are appropriately determined based on the intended use of the composite resin material, the type of the compound containing the amide group and the liquid, and the like. Can be adjusted. For example, the time for bringing the amide group-containing compound liquid into contact with the resin molding can be 5 seconds to 15 minutes, and the temperature of the amide group-containing compound liquid can be 5 ° C. to 80 ° C. If the time for bringing the compound liquid containing the amide group into contact with the resin molded body and / or the temperature of the compound liquid containing the amide group is within the above range, a sufficient amount of the compound containing the amide group is adsorbed to the resin molded body without unevenness. And / or can penetrate. Moreover, when the resin molding is swollen by the solvent (liquid) of the amide group-containing compound liquid, introduction of the amide group-containing compound into the resin molding is further promoted.

<Granting metal compounds>
Next, a liquid (metal compound liquid) containing a metal compound is brought into contact with the obtained resin base material by the same method as in the first embodiment (step S3 in FIG. 2). Adsorption and permeation of the metal compound are promoted by the amide group or amine group contained in the vicinity of the surface of the resin base material, and a composite resin material having a function derived from these metals is obtained. The composite resin material of this embodiment has the same effect as the composite resin material of the first embodiment.

[Fourth Embodiment]
In this embodiment, a reducing compound is used as the compound for fixing the metal. A composite resin material is produced by the same method as in the third embodiment except that a reducing compound is used as the compound for fixing the metal.

<Granting of reducing compound>
First, in the present embodiment, a liquid containing a reducing compound (hereinafter referred to as “reducing compound liquid”) is brought into contact with the resin molded body, and the reducing compound is imparted to the resin molded body (step S21 in FIG. 2). As a resin molding, the thing similar to 3rd Embodiment can be used.

  In the present embodiment, the same reducing compound as in the second embodiment can be used. However, in the second embodiment, in order to prevent alteration of the reducing compound in the resin pellet manufacturing process, the reducing compound is preferably an inorganic compound having heat resistance. However, since the resin pellet is not manufactured in the present embodiment, the reducing compound may be a compound that decomposes at a high temperature. For example, in this embodiment, the reducing compound may be sodium borohydride, formaldehyde, oxalic acid, or the like. These reducing agents may be used alone or in combination of two or more.

  The reducing compound solution uses the same solvent (liquid that dissolves or disperses the reducing compound) as the amide group containing compound of the third embodiment, except that the reducing compound is used instead of the amide group containing compound. Can be prepared by the same method. Further, the reducing compound liquid can be brought into contact with the resin molded body by the same method as in the third embodiment. Thereby, the reducing compound penetrates into the resin molded body, and a resin base material containing the reducing compound in the vicinity of the surface is obtained.

<Granting metal compounds>
Next, a liquid (metal compound liquid) containing a metal compound is brought into contact with the obtained resin base material by the same method as in the third embodiment (step S3 in FIG. 2). By the reducing compound contained in the vicinity of the surface of the resin substrate, the metal in the metal compound is reduced and fixed to the surface of the resin substrate. Thereby, the composite resin material which has a function derived from this metal is obtained. The composite resin material of this embodiment has the same effect as the composite resin material of the first embodiment.

  In the first embodiment and the third embodiment described above, different manufacturing methods have been described for the method of manufacturing the resin base material including the compound for fixing the metal in the vicinity of the surface. Is not limited to these. For example, the resin base material may be manufactured by combining the method of the first embodiment and the method of the third embodiment. That is, first, by the method described in the first embodiment, resin pellets (masterbatch) containing an amide group-containing compound and a second thermoplastic resin (base resin) are mixed and molded to form a resin group. Get the material. Then, the obtained resin base material may be further brought into contact with an amide group-containing compound solution by the method described in the third embodiment. By combining the method of the first embodiment and the method of the third embodiment, a sufficient amount of a compound containing an amide group or the like can be contained in the vicinity of the surface of the resin substrate. Similarly, a resin base material may be manufactured by combining the method of the second embodiment and the method of the fourth embodiment. That is, first, by the method described in the second embodiment, resin pellets (masterbatch) containing a reducing compound and a second thermoplastic resin (base resin) are mixed and molded to form a resin base material. obtain. Then, the obtained resin base material may be further brought into contact with the reducing compound liquid by the method described in the fourth embodiment.

  In the third and fourth embodiments, a step of bringing a liquid containing a compound for fixing a metal into contact with a resin molded body (step S21 in FIG. 2) and a step of bringing a liquid containing a metal compound into contact (steps in the same). S3) is performed in this order, but the present invention is not limited to this. In the present invention, after performing the step of contacting the liquid containing the metal compound (step S3), the step of contacting the liquid containing the compound fixing metal (step S21) may be performed. Thus, even if the order of steps is reversed, a composite resin material containing a metal compound in the vicinity of the surface can be produced. Further, the order of the steps described in the third and fourth embodiments, that is, the step of contacting a liquid containing a compound that fixes a metal to the resin molded body (step S21 in FIG. 2) and the liquid containing the metal compound are brought into contact. If the process (step S3) is performed in this order, the compound that fixes the metal used in the previous process is mixed into the liquid containing the metal compound used in the subsequent process, and the metal compound is precipitated in the liquid. May occur. On the other hand, if the process order is reversed, there is an advantage that such inconvenience does not occur.

  As the compound for fixing the metal, a compound containing an amide group or the like is used in the first and third embodiments, and a reducing compound is used in the second and fourth embodiments. However, the present invention is not limited to this, and a compound containing an amide group or the like and a reducing compound may be used as a compound for fixing a metal.

[Fifth Embodiment]
As a fifth embodiment, a method for manufacturing a plated component (a composite resin material having an electroless plating film) shown in FIG. 3 will be described.

  First, a composite resin material provided with a metal compound is manufactured by the method described in the first embodiment (step S31 in FIG. 3). However, in this embodiment, a metal compound having electroless plating catalytic ability such as Pd, Pt, Cu, and Ni is used as the metal compound. Among them, palladium chloride, which has high catalytic ability and is easily adsorbed to an amide group or an amine group, is preferable as the metal compound.

  Next, an electroless plating film is formed on the composite resin material by the method described below (step S4 in FIG. 3).

  First, before bringing the electroless plating solution into contact with the composite resin material, the composite resin material may be swelled by bringing water, an organic solvent, or the like into contact with the surface of the composite resin material as a pretreatment for plating. Due to the swelling treatment, unevenness in the surface properties of the composite resin material may be alleviated, and the electroless plating reaction may easily occur uniformly. Thereby, a uniform plating film having excellent appearance characteristics can be formed. Further, since the composite resin material swells, the electroless plating solution easily penetrates into the composite resin material. Thereby, the growth of the plating film from the inside of the composite resin material is promoted, and a plating film having high adhesion strength can be formed.

  Next, an electroless plating solution is brought into contact with the composite resin material that has been subjected to the plating pretreatment to form a plating film. As the electroless plating solution, any general-purpose electroless plating solution can be used according to the purpose. For example, an electroless nickel phosphorus plating solution and an electroless copper plating solution can be used.

  The composite resin material used in the present embodiment can contain a uniform and sufficient amount of a metal compound that becomes an electroless plating catalyst in the vicinity of the surface without depending on the type of the base resin due to the amide group-containing compound contained therein. . Thereby, a plating film having good appearance characteristics can be formed on the surface of the composite resin material. Further, since the metal compound penetrates into the composite resin material, the plating film grows from the inside, and the adhesion strength of the plating film can be improved. Moreover, since the composite resin material used in the present embodiment already contains a metal compound that acts as an electroless plating catalyst in the vicinity of the surface, it is not necessary to perform plating pretreatment with a high environmental load.

  On the composite resin material on which the electroless plating film is formed, a plurality of different types of electroless plating films may be formed for the purpose of improving the use and design of the composite resin material. A plating film may be formed. Further, the composite resin material on which the electroless plating film is formed may be annealed after electroless plating, or may be naturally dried by being left at room temperature. Moreover, you may perform the following processes, such as forming an electrolytic plating film | membrane continuously, without performing annealing treatment and natural drying.

  In this embodiment, the electroless plating film is formed on the composite resin material manufactured by the method described in the first embodiment, but this embodiment is not limited to this. For example, an electroless plating film may be formed on the composite resin material manufactured by the method described in the second to fourth embodiments.

  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, resin pellets containing an amide group-containing compound and a first thermoplastic resin are manufactured, and then the manufactured resin pellets and a second thermoplastic resin are mixed and molded. Thus, a resin base material was obtained. And the metal compound was provided to the obtained resin base material, and the composite resin material of the present Example was obtained.

<Resin pellet manufacturing equipment>
First, the manufacturing apparatus 1000 used for manufacturing resin pellets in the present embodiment will be described. As shown in FIG. 4, the manufacturing apparatus 1000 includes an extrusion molding machine 200 having a plasticizing cylinder 210 and an amide group-containing compound supply for supplying a solution (solution A) of an amide group-containing compound to the plasticizing cylinder 210. A mechanism 100, a pressurized carbon dioxide supply mechanism 300 for supplying pressurized carbon dioxide to the plasticizing cylinder 210, and a control device (not shown) are provided. The control device controls operations of the extrusion molding machine 200, the amide group-containing compound supply mechanism 100, and the pressurized carbon dioxide supply mechanism 300.

(A) Extruder Machine The extruder 200 shown in FIG. 4 includes a plasticizing cylinder 210, a die 29 provided at the tip of the plasticizing cylinder 210, and a screw 20 rotatably disposed in the plasticizing cylinder 210. A screw drive mechanism 27 for driving the screw 20, an upstream side seal mechanism S <b> 1 and a downstream side seal mechanism S <b> 2 disposed in the plasticizing cylinder 210, and a vacuum pump P connected to the plasticizing cylinder 210. In the present embodiment, in the plasticizing cylinder 210, the plasticized and melted molten resin flows from the right hand to the left hand in FIG. Therefore, in the plasticizing cylinder 210 of this embodiment, the right hand in FIG. 4 is defined as “upstream” or “rear”, and the left hand is defined as “downstream” or “front”. Note that the extruder 200 of the present embodiment, like the configuration of a conventionally known extruder, rotates the screw 20 counterclockwise when viewed from the rear side of the plasticizing cylinder 210. It is configured to perform forward rotation sent forward (nozzle side) and reverse rotation when rotated clockwise.

  In order to introduce a resin supply port 201 for supplying a thermoplastic resin to the plasticizing cylinder 210, a solution A, and pressurized carbon dioxide into the plasticizing cylinder 210 in order from the upstream side on the upper side surface of the plasticizing cylinder 210. And a vent 203 for exhausting the solvent of the solution A gasified and pressurized carbon dioxide from the plasticizing cylinder 210 as necessary. The resin supply port 201 and the introduction port 202 are provided with a resin supply hopper 211 and an introduction valve 212, respectively, and a vacuum pump P is connected to the vent 203. The introduction valve 212 is connected to an amide group-containing compound supply mechanism 100 and a pressurized carbon dioxide supply mechanism 300 provided outside the extruder 200.

  A band heater 220 is disposed on the outer wall surface of the plasticizing cylinder 210, whereby the plasticizing cylinder 210 is heated and the thermoplastic resin is plasticized. Further, a sensor (not shown) for monitoring pressure and temperature is provided at a position facing the inlet 202 on the lower side surface of the plasticizing cylinder 210 and a position facing the vent 203, respectively.

  In the extruder 200 having such a structure, thermoplastic resin is supplied from the resin supply port 201 into the plasticizing cylinder 210, and the thermoplastic resin is plasticized by the band heater 220 to become molten resin, so that the screw 20 rotates in the forward direction. Is sent downstream. The molten resin sent to the vicinity of the inlet 202 is contact-kneaded with the introduced solution A and pressurized carbon dioxide under high pressure. Next, by reducing the resin internal pressure of the molten resin that has been contact-kneaded with the solution A and pressurized carbon dioxide, the solvent of the gasified solution A and the pressurized carbon dioxide are separated from the molten resin and exhausted from the vent 203. . Then, the molten resin sent further forward is pushed out from the die 29. As a result, in the plasticizing cylinder 210, in order from the upstream side, the plasticizing zone 21 that plasticizes the thermoplastic resin into the molten resin, the molten resin, the solution A introduced from the inlet 202, and the pressurized carbon dioxide are pressurized. Below, a high pressure kneading zone 22 for contact kneading and a reduced pressure zone 23 for exhausting the solvent of the solution A separated from the molten resin and pressurized carbon dioxide from the vent 203 are formed by reducing the internal pressure of the molten resin. . Further, a replasticization zone 24 is provided downstream of the decompression zone 23. In order to efficiently perform the kneading of the molten resin with the solution A and pressurized carbon dioxide, the plasticizing cylinder 210 is provided with a plurality of inlets 202 and vents 203, and the plasticizing cylinder 210 has a high-pressure kneading zone 22 and a reduced pressure. A plurality of zones 23 may be formed.

  An upstream seal mechanism S1 and a downstream seal mechanism S2 are disposed between the plasticizing zone 21, the high-pressure kneading zone 22, and the decompression zone 23, respectively. As the upstream seal mechanism S1, any seal mechanism can be used as long as the backflow of the resin to the upstream side can be suppressed. In this embodiment, a seal ring used for conventional foam molding or the like is employed. The downstream seal mechanism S2 is melted into the decompression zone 23 on the downstream side of the downstream seal mechanism S2 in a state where the pressure of the molten resin is adjusted to 3 MPa to 40 MPa in the high pressure kneading zone 22 on the upstream side of the downstream seal mechanism S2. A sealing mechanism that can flow the resin is used. In the present embodiment, a seal mechanism including a seal ring 60 provided on the outer peripheral surface of the screw 20 via a spring shown in FIG. 5 is used as the downstream seal mechanism S2. The detailed structure and function of the downstream side seal mechanism S2 will be described later.

(B) Amide group-containing compound supply mechanism and pressurized carbon dioxide supply mechanism Next, the amide group-containing compound supply mechanism 100 and the pressurized carbon dioxide supply mechanism 300 shown in FIG. 4 will be described. The amide group-containing compound supply mechanism 100 and the pressurized carbon dioxide supply mechanism 300 are connected to the introduction valve 212 of the extrusion molding machine 200 via the back pressure valve 250, and the solution A and the pressurized carbon dioxide are respectively molded into the molding machine. 200. The amide group-containing compound supply mechanism 100 includes a storage container 10 for the solution A and two syringe pumps 11 and 12 that can suck the solution A from the storage container 10 and then increase the pressure to a predetermined pressure and feed the liquid at a constant flow rate. And two automatic air valves for suction 13 and 14 arranged in the pipe, and two automatic air valves for liquid feeding 15 and 16.

  The pressurized carbon dioxide supply mechanism 300 includes a carbon dioxide cylinder 37, a storage tank 30 connected to the carbon dioxide cylinder 37 via a Coriolis flow meter 38, and a differential pressure type liquid that monitors the amount of liquid carbon dioxide in the storage tank 30. Two syringe pumps 31 and 32 connected to the storage tank 30 via a face meter 40, a valve 41, two suction air automatic valves 33 and 34 arranged in a pipe, and two liquid feed air automatic valves 35, 36. The pressurized carbon dioxide is stored in the storage tank 30, sucked from the storage tank 30 by the two syringe pumps 31, 32, then pressurized to a predetermined pressure, and further sent to the extruder 200 at a constant flow rate. . The storage tank 30 has an internal volume of 100 L, and supplies liquid carbon dioxide having a capacity higher than that of the 40 L carbon dioxide cylinder 37 in a stable density.

  In the pressurized carbon dioxide supply mechanism 300, the carbon dioxide cylinder 37 includes a heater (not shown), pressurizes the carbon dioxide in the cylinder by heating with the heater, and supplies the carbon dioxide to the storage tank 30. The amount of carbon dioxide supplied to the storage tank 30 is monitored by a Coriolis flow meter 38, and when a predetermined amount of carbon dioxide is supplied to the storage tank 30, an automatic valve (not shown) is closed to the carbon dioxide storage tank 30. Stop supplying.

  The storage tank 30 includes a heater for heating and a heat exchanger connected to a chiller as a temperature control mechanism (not shown), and the carbon dioxide in the storage tank 30 is maintained by maintaining the storage tank 30 at a predetermined temperature. Is kept in a vapor-liquid equilibrium state, and the density of liquid carbon dioxide is kept constant. In the storage tank 30, the liquid phase of carbon dioxide is heated by a heater provided in the lower part of the storage tank 30, and the gas phase is cooled by a heat exchanger provided in the upper part of the storage tank 30. The amount of liquid carbon dioxide is monitored by a differential pressure type level gauge 40.

  Since the amide group-containing compound supply mechanism 100 and the pressurized carbon dioxide supply mechanism 300 have syringe pumps 11, 12, 31, and 32 capable of controlling the flow rate and pressure, the solution A in which the flow rate and pressure are controlled to a predetermined amount. And pressurized carbon dioxide can be sent to the extrusion molding machine 200. The syringe pumps 11, 12, 31, and 32 open the suction air automatic valves 13, 14, 33, and 34, suck the solution A and pressurized carbon dioxide into the syringe pump, and then close the valve to apply the pressure. To maintain a predetermined pressure. When liquid is fed, the liquid automatic air valves 15, 16, 35, and 36 are opened, and liquid can be fed at a constant flow rate by pushing the syringe of the syringe pump at a constant speed. The pressure of the solution A and the pressurized carbon dioxide introduced into the plasticizing cylinder 210 of the extruder 200 is adjusted by the set pressure of the back pressure valve 250.

  In each of the amide group-containing compound supply mechanism 100 and the pressurized carbon dioxide supply mechanism 300, when one pump (for example, the syringe pumps 11, 31) is feeding liquid, the other pump (syringe pumps 12, 32) Aspirates the solution and waits. When the pressurized solution in one of the pumps (syringe pumps 11 and 31) being pumped becomes empty, the pump is switched, and this time, the other pumps (syringe pumps 12 and 32) are used to feed the liquid. Start. Thus, the solution A and the pressurized carbon dioxide are fed (supplied) from the amide group-containing compound supply mechanism 100 and the pressurized carbon dioxide supply mechanism 300 to the extrusion molding machine 200 with the pressure and the flow rate kept constant. Thus, the extrusion molding machine 200 can continuously form an extrusion molded product in which a compound containing an amide group or the like is finely dispersed.

(C) Downstream side sealing mechanism The downstream side sealing mechanism S2 provided in the extrusion molding machine 200 will be described. In the present embodiment, as the downstream seal mechanism S2, a seal mechanism including a seal ring 60 provided on the outer peripheral surface of the screw 20 via a spring described below is used.

  As shown in FIG. 5, the screw 20 of the present embodiment has a reduced diameter portion 50 that is reduced in diameter in the boundary region between the high-pressure kneading zone 22 and the decompression zone 23 as compared with a region adjacent to the boundary region. ing. The downstream seal ring 60 is externally fitted to the reduced diameter portion 50 so as to be movable in the axial direction (front-rear direction) within the range of the reduced diameter portion 50. The reduced diameter portion 50 and the downstream seal ring 60 constitute a downstream seal mechanism S2.

  In the screw 20, a downstream screw portion 51 located in the decompression zone 23 is provided adjacent to the downstream side of the reduced diameter portion 50, and the downstream screw portion 51 has a diameter larger than that of the reduced diameter portion 50, and thus the reduced diameter. It has an end surface 51 a continuous with the portion 50. Four holes 51b are formed in the end surface 51a, and a spring piston 61 is disposed in each hole 51b. The spring piston 61 includes a plurality of disc springs 63 disposed in the hole 51b, a ring 64 disposed in contact with the disc spring 63 in the hole 51b, and a part protruding from the hole 51b, A disc spring 63 and a shaft 62 penetrating the ring 64 are formed. As shown in FIG. 5A, the ring 64 of the spring piston 61 is in contact with the downstream seal ring 60 and urges the downstream seal ring 60 in the upstream direction. As a result, the inner wall 60a of the seal ring 60 and the outer peripheral surface 50a of the reduced diameter portion 50 come into contact with each other, and communication between the high pressure kneading zone 22 and the decompression zone 23 is blocked.

  Next, the operation of the downstream seal mechanism S2 will be described. As the screw 20 rotates forward, the molten resin flows from upstream to downstream. As a result, the molten resin staying in the high-pressure kneading zone 22 pushes the downstream seal ring 60 in the downstream direction. However, as shown in FIG. 5A, the downstream seal ring 60 is urged in the upstream direction by the spring piston 61 and the communication between the high-pressure kneading zone 22 and the decompression zone 23 is cut off, so that the molten resin has a high pressure. It cannot flow from the kneading zone 22 to the decompression zone 23.

  Further, when the screw 20 rotates in the forward direction, the molten resin continues to flow from the plasticizing zone 21 to the high pressure kneading zone 22 while the communication between the high pressure kneading zone 22 and the decompression zone 23 is blocked. Pressure increases. When the pressure in the high-pressure kneading zone 22 becomes equal to or higher than a predetermined pressure, the downstream seal ring 60 is pushed by the molten resin in the downstream direction and starts to move. As a result, as shown in FIG. 5B, the inner wall 60a of the downstream seal ring 60 and the outer peripheral surface 50a of the reduced diameter portion 50 are separated from each other, the gap G is opened, and the molten resin is pressurized through the gap G. It becomes possible to move from the kneading zone 22 to the decompression zone 23.

  The downstream-side seal mechanism S2 can increase the pressure of the molten resin in the high-pressure kneading zone 22 upstream of the downstream-side seal mechanism S2, and can maintain a high pressure with little pressure fluctuation. Hereinafter, a method for adjusting the pressure of the molten resin using the downstream-side seal mechanism S2 will be described. First, the screw 20 is rotated forward in a state where the communication between the high-pressure kneading zone 22 and the decompression zone 23 is blocked by the downstream seal mechanism S2. Since the upstream side seal mechanism S1 suppresses the back flow from the high pressure kneading zone 22 to the plasticizing zone 21, the molten resin continues to flow from the plasticizing zone 21 to the high pressure kneading zone 22, and the pressure in the high pressure kneading zone 22 increases. To do. When the pressure of the molten resin in the high-pressure kneading zone 22 is further increased to a predetermined pressure or higher by rotating the screw in the forward direction, the high-pressure kneading zone 22 and the decompression zone 23 are communicated with each other by the downstream seal mechanism S2. The resin flows to the downstream decompression zone 23. When the molten resin flows to the downstream decompression zone 23, the pressure in the high-pressure kneading zone 22 begins to decrease, and when the pressure in the high-pressure kneading zone 22 falls below a predetermined pressure, the downstream-side seal mechanism S2 again causes the high-pressure kneading zone 22 to Communication between 22 and the decompression zone 23 is blocked. Since the screw rotates in the forward direction, the pressure in the high-pressure kneading zone 22 rises again, and when the pressure exceeds a predetermined pressure, the high-pressure kneading zone 22 and the decompression zone 23 communicate with each other again by the downstream seal mechanism S2, and the molten resin Flows to the downstream decompression zone 23. As described above, the downstream seal mechanism S2 repeats communication and blocking between the high-pressure kneading zone 22 and the decompression zone 23 in accordance with the pressure in the high-pressure kneading zone 22. As a result, the pressure of the molten resin in the high-pressure kneading zone 22 can be maintained at a high pressure with little pressure fluctuation.

(1) Manufacture of resin pellets Using the manufacturing apparatus 1000 shown in Fig. 4 described above, resin pellets containing an amide group-containing compound and a first thermoplastic resin were manufactured. In this example, 6/66 copolymer nylon (Amilan CM6001 manufactured by Toray, Inc.) is used as the first thermoplastic resin, and ε-caprolactam (molecular weight: 113.2, melting point: 69 ° C., 1 g) The number of moles of the amide group was 8.8 mmol / g).

  First, ε-caprolactam was dissolved in ethanol to prepare an ethanol solution (solution A) having an ε-caprolactam concentration of 50% by weight and stored in the storage container 10. Then, in the amide group-containing compound supply mechanism 100, the pressure was increased after the solution A was sucked by the syringe pump 11. On the other hand, in the pressurized carbon dioxide supply mechanism 300, the pressure was increased after the valve 41 was opened and the pressurized carbon dioxide was sucked by the syringe pump 31.

  After increasing the pressure of the solution A and the pressurized carbon dioxide, the syringe pumps 11 and 31 were switched from the pressure control to the flow rate control, and the solution A and the pressurized carbon dioxide were caused to flow at a predetermined flow rate ratio. Thereby, the solution A and the pressurized carbon dioxide were mixed in the pipe, and the system up to the introduction valve 212 was pressurized.

  On the other hand, in the extrusion molding machine 200, the plasticizing zone 21 was adjusted to 240 ° C, the high pressure kneading zone 22 to 220 ° C, the decompression zone 23 to 200 ° C, and the replasticizing zone 24 to 230 ° C by the band heater 220. Then, in the extrusion molding machine 200, the first thermoplastic resin was supplied from the resin supply hopper 211 while controlling the input amount with a feeder screw (not shown), and the screw 20 was rotated forward. Thus, the thermoplastic resin was heated and kneaded to obtain a molten resin. By rotating the screw 20 forward, the molten resin was caused to flow from the plasticizing zone 21 to the high-pressure kneading zone 22. In the high pressure kneading zone 22 in which the upstream side sealing mechanism S1 is provided on the upstream side and the downstream side sealing mechanism S2 is provided on the downstream side, the pressure of the molten resin before the mixed fluid of the solution A and the pressurized carbon dioxide is introduced. The pressure was adjusted to 14 ± 1 MPa.

  Next, the introduction valve 212 was opened, and the fluid mixture of the solution A and the pressurized carbon dioxide was introduced into the high-pressure kneading zone 22 at a constant flow rate by the syringe pumps 11 and 31. The introduction pressure was adjusted to 15 MPa by the back pressure valve 250. The flow rate of solution A was 10 mL / min, and the flow rate of pressurized carbon dioxide was 2 ml / min. By mixing the pressurized carbon dioxide, the pressure in the plasticizing cylinder 210 was stabilized, and the diffusion of the solution A into the resin could be promoted.

  By rotating the screw 20 in the forward direction, a mixed fluid of the solution A and pressurized carbon dioxide was mixed with the molten resin in the high-pressure kneading zone 22. The pressure inside the plasticizing cylinder 210 monitored by a pressure sensor (not shown) provided immediately below the introduction valve 212 was stable at 9.0 ± 1.5 MPa after the introduction of the fluid.

  Further, by rotating the screw 20 in the forward direction, the molten resin was caused to flow into the decompression zone 23 while the high-pressure kneading zone 22 was maintained at 9.0 ± 1.5 MPa. The decompression zone 23 was set to atmospheric pressure, and ethanol and carbon dioxide in the solution A flowing to the decompression zone 23 were gasified and separated. The gasified solvent was sucked by the vacuum pump P, discharged from the vent 203 to the outside of the plasticizing cylinder 210, and recovered in a recovery container (not shown) connected to the vacuum pump P.

  By rotating the screw 20, the molten resin is further flowed to the downstream replasticization zone 24, and then extruded from a die 29 provided at the tip of the plasticizing cylinder 210 to obtain a string-like molded body. It was.

  The obtained string-like extrudate was passed through a water tank (not shown), and then continuously cut with a strand cutting device (not shown) to produce resin pellets. Hereinafter, the resin pellet produced in this example is referred to as “pellet 1” as appropriate.

In the present embodiment, the number of rotations of the plasticizing screw 20 was 100 rpm, and the amount of molten resin discharged from the die 29 was 5 kg / hr. Since solution A (50 wt% ethanol solution of ε-caprolactam, specific gravity 0.97 g / cm ³ at the introduction pressure in this example) was supplied to the molten resin at 10 mL / min, ε-caprolactam in the resin pellets The set value of the content is about 6% by weight.

(2) Molding of resin base material Next, the produced pellet 1 and the second thermoplastic resin were mixed and plasticized and melted to form a resin base material. In the molding of the resin base material of this example, the resin pellets correspond to a master batch, and the second thermoplastic resin corresponds to a base resin. As the second thermoplastic resin (base resin), mineral-reinforced nylon 6 (produced by Toyobo, Gramide T777-02), which is an aliphatic polyamide, was used. 90% by weight of the second thermoplastic resin and 10% by weight of the pellet 1 are dry blended and injection molded using a general-purpose injection molding machine to obtain a flat resin substrate of 80 mm × 80 mm × 2 mm It was. The resin temperature during molding was 230 to 250 ° C., the mold temperature was 90 ° C., and the clamping pressure was 100 t.

(3) Application of metal compound Next, a liquid (metal compound liquid) containing a metal compound was brought into contact with the obtained resin base material. Palladium chloride was used as the metal compound, and hydrochloric acid was used as the solvent for dissolving the metal compound.

  First, 2.0N hydrochloric acid (metal compound solution) containing 50 ppm of palladium chloride was prepared. The metal compound solution was adjusted to 30 ° C., and the resin substrate was immersed in the metal compound solution for 1 minute. After soaking, it was washed with pure water to obtain a composite resin material of this example.

[Example 2]
In this example, after the resin substrate was produced by the same method as in Example 1, the resin substrate was further brought into contact with a liquid containing an amide group-containing compound (amide group-containing compound solution). Then, the metal compound was provided to the resin base material by the method similar to Example 1, and the composite resin material of the present Example was obtained.

(1) Immersion in amide group-containing compound solution 1,3-dimethylurea (molecular weight: 88.1, melting point: 104 ° C., mole number of amide groups in 1 g: 11.3 mmol / g) ) And water as a solvent to prepare a 1,3-dimethylurea solution (amide group-containing compound solution) having a concentration of 10% by weight. The prepared amide group-containing compound solution was adjusted to 70 ° C., and the resin substrate produced by the same method as in Example 1 was immersed in the amide group-containing compound solution for 10 minutes, and then washed pure.

(2) Application of metal compound Next, the resin base material was immersed in a metal compound solution in the same manner as in Example 1. After soaking, it was washed with pure water to obtain a composite resin material of this example.

[Example 3]
In this example, first, resin pellets containing a reducing compound and a first thermoplastic resin were produced by the method described below. Next, in place of the resin pellet (pellet 1) used in Example 1, the composite resin material of this example was prepared in the same manner as in Example 1 except that the resin pellet produced in this example was used. Manufactured.

(1) Manufacture of resin pellets In this example, a block copolymer of polyamide and polyether (manufactured by Sanyo Chemical Industries, Peletron AS) is used as the first thermoplastic resin, and calcium hypophosphite powder is used as the reducing compound. It was. The first thermoplastic resin and the reducing compound were mixed at a weight ratio of 95: 5, and the mixture was extruded into a string using a general-purpose single-screw extruder to obtain a string-shaped molded body. The obtained string-like extrudate was passed through a water tank, and then continuously cut with a strand cutting device to produce resin pellets. Hereinafter, the resin pellet produced in this example is referred to as “pellet 2” as appropriate. Therefore, the content of calcium hypophosphite in the pellet 2 is 5% by weight.

(2) Molding of resin substrate and application of metal compound A resin substrate was molded in the same manner as in Example 1 except that pellet 2 was used instead of pellet 1. Next, the resin base material was immersed in the metal compound solution by the same method as in Example 1. After soaking, it was washed with pure water to obtain a composite resin material of this example.

[Example 4]
In this example, a resin base material was produced by a method different from Example 1 described below. Then, the metal compound was provided to the resin base material by the method similar to Example 1, and the composite resin material of the present Example was obtained.

(1) Molding of resin molded body Using mineral reinforced nylon 6 (Toyobo, Gramide T777-02) used as the second thermoplastic resin in Example 1, the same molding of the resin base material of Example 1 By the method, a plate-like molded body having the same size (80 mm × 80 mm × 2 mm) was formed.

(2) Immersion in amide group-containing compound solution Prepare ε-caprolactam solution (amide group-containing compound solution) with a concentration of 30% by weight using ε-caprolactam as the amide group-containing compound and water as the solvent. did. The prepared amide group-containing compound solution was adjusted to 70 ° C., and the resin molded body was immersed in the amide group-containing compound solution for 10 minutes. Through the above steps, a resin base material containing an amide group-containing compound was obtained.

(3) Application of Metal Compound Next, a resin base material (resin molded body immersed in an amide group-containing compound solution) was immersed in the metal compound solution in the same manner as in Example 1. After soaking, it was washed with pure water to obtain a composite resin material of this example.

[Example 5]
In this example, a composite resin material was produced by the same method as in Example 4 except that the resin molded body was dipped in a reducing compound solution instead of dipping in a compound solution containing an amide group or the like.

(1) Molding of resin molded body and immersion in reducing compound solution First, a resin molded body was molded by the same method as in Example 4. Next, using sodium borohydride as the reducing compound and using 0.03N sodium hydroxide solution as the solvent, a sodium borohydride solution having a concentration of 0.1 mol / L and pH = 12.3 (reducing compound solution). ) Was adjusted. The adjusted reducing compound solution was adjusted to 70 ° C., and the resin molding was immersed in the reducing compound solution for 10 minutes, and then washed with pure water. Through the above steps, a resin substrate containing a reducing compound was obtained.

(2) Application of metal compound Next, by the same method as in Example 1, the resin base material (resin molded body immersed in the reducing compound solution) was immersed in the metal compound solution. After soaking, it was washed with pure water to obtain a composite resin material of this example.

[Example 6]
In this example, amorphous polyamide was used instead of 6/66 copolymer nylon as the first thermoplastic resin, and ABS resin was used instead of mineral reinforced nylon 6 as the second thermoplastic resin. A resin base material was produced by the same method as in Example 1, and the resin base material was further brought into contact with a liquid containing an amide group-containing compound (an amide group-containing compound liquid). Then, the metal compound was provided to the resin base material by the method similar to Example 1, and the composite resin material of the present Example was obtained.

(1) Production of resin pellets Resin pellets were produced in the same manner as in Example 1 except that amorphous polyamide (Unitika, CM 2500) was used instead of 6/66 copolymer nylon as the first thermoplastic resin. Manufactured. The set value of the content of ε-caprolactam in the resin pellets was set to about 6% by weight as in Example 1. Hereinafter, the resin pellet produced in this example is referred to as “pellet 3” as appropriate.

(2) Molding of resin base material Next, 20% by weight of the produced pellets 3 and dry blending 80% by weight of ABS resin (Toyolac manufactured by Toray) as the second thermoplastic resin (base resin) were carried out. A flat resin substrate (80 mm × 80 mm × 2 mm) was molded in the same manner as in Example 1.

(3) Etching of resin base material The obtained resin base material was immersed for 5 minutes in the processing liquid (ethylene glycol monobutyl ether, 100 weight%) which consists only of 80 degreeC ethylene glycol monobutyl ether.

(4) Immersion in amide group-containing compound solution In the same manner as in Example 2, the resin substrate was immersed in the amide group-containing compound solution, and then washed with pure water.

(5) Application of metal compound Next, the resin base material was immersed in a metal compound solution in the same manner as in Example 1. After soaking, it was washed with pure water to obtain a composite resin material of this example.

[Example 7]
In this example, a composite resin material was produced in the same manner as in Example 1 except that polyethyleneimine (manufactured by Wako Pure Chemicals, molecular weight = 1000) was used as the amide group-containing compound instead of ε-caprolactam. .

(1) Production of resin pellets Resin pellets were produced in the same manner as in Example 1 except that polyethyleneimine (molecular weight: 1000) was used instead of ε-caprolactam as the amide group-containing compound. The set value of the content of polyethyleneimine in the resin pellets was about 6% by weight as in Example 1. Hereinafter, the resin pellet produced in this example is referred to as “pellet 4” as appropriate.

(2) Molding of resin base material Next, a flat resin base material (80 mm × 80 mm × 2 mm) was molded by the same method as in Example 1 except that pellet 4 was used instead of pellet 1.

(3) Application of Metal Compound Next, the resin base material was immersed in the metal compound solution by the same method as in Example 1. After soaking, it was washed with pure water to obtain a composite resin material of this example.

[Example 8]
In this example, amorphous polyamide was used instead of 6/66 copolymer nylon as the first thermoplastic resin, ABS resin was used instead of mineral-reinforced nylon 6 as the second thermoplastic resin, and the metal compound was A composite resin material of this example was obtained in the same manner as in Example 1 except that silver chloride was used instead of palladium chloride.

(1) Molding of resin base material 10% by weight of the pellet 3 produced in Example 6 and dry blending ABS resin (Toyolac 500, Torayac 500) as the second thermoplastic resin (base resin) at a ratio of 90% by weight Then, a flat resin substrate (80 mm × 80 mm × 2 mm) was molded by the same method as in Example 1.

(2) Application of metal compound An aqueous solution (metal compound solution) containing 1% by weight of silver nitrate was prepared using silver nitrate as a metal compound and water as a solvent for dissolving the metal compound. The metal compound solution was adjusted to 30 ° C., and the resin substrate was immersed in the metal compound solution for 1 minute. After soaking, it was washed with pure water to obtain a composite resin material of this example.

[Comparative Example 1]
In this comparative example, the composite of this comparative example was made in the same manner as in Example 1 except that the resin base material was molded only from the second thermoplastic resin (mineral reinforced nylon 6) without using resin pellets. A resin material was obtained.

[Comparative Example 2]
In this comparative example, resin pellets are not used, and the resin base material is formed from only the second thermoplastic resin by using ABS resin (Toyolac, Torayac Co., Ltd.) instead of mineral reinforced nylon 6 as the second thermoplastic resin. A composite resin material of this comparative example was obtained in the same manner as in Example 1 except that was molded.

[Evaluation of composite resin materials]
About the composite resin material manufactured in Examples 1-8 and Comparative Examples 1 and 2, the following evaluation items were evaluated.

(1) Evaluation as an object to be plated (a) Evaluation of appearance of plating film An electroless plating film is formed on the surface of the composite resin material obtained in Examples 1 to 7 and Comparative Examples 1 and 2 by the following method. did. First, as a pretreatment for plating, the composite resin materials obtained in Examples 1 to 7 and Comparative Examples 1 and 2 were immersed in pure water at 70 ° C. for 5 minutes to perform a swelling treatment. The composite resin material subjected to the plating pretreatment was immersed in an electroless nickel phosphorus plating solution (Okuno Pharmaceutical Co., Ltd., Top Nicolon RCH) at 70 ° C. for 10 minutes to form an electroless nickel phosphorus plating film having a thickness of 1 μm. . In addition, the formation process of the electroless plating film | membrane demonstrated above was continuously performed without providing the drying process of a composite material on the way. The appearance of the formed electroless plating film was visually observed and evaluated according to the following evaluation criteria. The results are shown in Table 1.

<Evaluation criteria for appearance of plating film>
A: A plating film was formed on the entire surface of the resin base material, and no swelling, cracking, pinholes, or film loss occurred in the plating film.
Δ: A plating film was entirely formed on the surface of the resin base material, but any of swelling, cracking, pinholes, and film loss occurred.
X: Reactivity of electroless plating was poor, and a plating film was not formed on the entire surface of the resin substrate.

(B) Adhesion strength of plating film In Examples 1 to 7 and Comparative Examples 1 and 2, an electrolytic copper plating film was formed to 40 μm by a general-purpose method on the electroless plating film of the sample for which the appearance evaluation of the plating film was performed. A sample for measurement of adhesion strength was formed. Using a tensile tester (AGS-100N, manufactured by Shimadzu Corporation), the plating film was removed from the sample over a length of 40 mm on the sample surface at an angle of 90 ° and a speed of 25 mm / min in accordance with JIS H8630. The force at the time of peeling was measured to determine the adhesion strength. The measured adhesion strength was evaluated according to the following evaluation criteria. The results are shown in Table 1. Also, the actual measurement values are shown in Table 1.

<Evaluation criteria for adhesion strength of plating film>
○: The adhesion strength of the plating film is 10 N / cm or more.
Δ: The adhesion strength of the plating film is 5 N / cm or more and less than 10 N / cm, and there is no practical problem.
X: The adhesion strength of the plating film is less than 5 N / cm, which is problematic in practical use.

(2) Antibacterial evaluation In Example 8, the composite resin material was evaluated for antibacterial properties. As the antibacterial test method, JIS Z 2801 (2010) film adhesion method was used to examine the change before and after the test of E. coli on the composite resin material. E. coli before the test was 1.48 × 10 ⁴ and decreased to 0.63 or less after the test. The antibacterial activity value calculated | required by this was 3.4, and satisfy | filled the standard of the antibacterial activity value of "higher than 2.0" which is JIS specification.

  As shown in Table 1, in Examples 1 to 7 including a compound that fixes a metal near the surface of the resin base material and using palladium chloride as the metal compound, the evaluation result of the appearance of the plated film is good (evaluation) Results: ○), the adhesion strength of the plating film was also as high as 5 N / cm or more. On the other hand, Comparative Examples 1 and 2, which do not contain a compound for fixing a metal near the surface of the resin substrate, were subjected to the same metal compound (palladium chloride) application treatment as in Examples 1 to 7, but were plated films. The appearance was poor (evaluation result: Δ or x), and the adhesion strength of the plating film was also low, less than 5 N / cm. Comparing Comparative Examples 1 and 2, Comparative Example 2 has a poorer evaluation result of the appearance of the plating film (Evaluation result: ×). In Comparative Example 2, a plating film having a sufficient area is obtained. Since it could not be formed, the adhesion strength could not be measured. The second thermoplastic resin (base resin) used in Comparative Example 1 was nylon 6 having an amide group and a certain level of water absorption, whereas the second thermoplastic resin used in Comparative Example 2 (Base resin) was an ABS resin having neither an amide group nor an amine group and low water absorption. For this reason, it is presumed that the evaluation result of the appearance of the plating film was worse in Comparative Example 2 using the ABS resin in which the plating film was harder to form than in Comparative Example 1. However, as shown in the results of Example 6, even when an ABS resin is used as the base resin, a plating film excellent in appearance and adhesion strength can be obtained by including a compound (an amide group-containing compound) that fixes the metal. A formable composite resin substrate is obtained.

  Moreover, it was confirmed that the composite resin material produced had a high antibacterial action in Example 8 which contained a compound for fixing a metal near the surface of the resin substrate and used silver chloride as the metal compound.

  The composite resin material produced by the method of the present invention exhibits a function derived from the metal in the metal compound used for production. For example, when a metal having electroless plating catalytic ability is used, the composite resin material functions as a body to be electroless plated. In this case, the composite resin material of the present invention does not require plating pretreatment with high environmental load, and can form a uniform plating film having high adhesion strength and excellent appearance characteristics on the surface thereof. When a metal having an antibacterial action such as Ag is used, the composite resin material of the present invention functions as an antibacterial material.

Claims (15)

A method for producing a composite resin material, comprising:
Producing a resin substrate containing a compound for fixing a metal in the vicinity of the surface;
The manufacturing method of the composite resin material including making the liquid containing a metal compound contact the said resin base material. Producing the resin substrate,
Producing a resin pellet comprising a compound for fixing the metal and a first thermoplastic resin;
The manufacturing method of the composite resin material of Claim 1 including mixing the said resin pellet and 2nd thermoplastic resin, shape | molding, and obtaining the said resin base material. Producing the resin substrate,
The method for producing a composite resin material according to claim 1, wherein the resin base material is obtained by bringing a liquid containing a compound for fixing the metal into contact with a resin molded body. A method for producing a composite resin material, comprising:
Contacting the resin molding with a liquid containing a compound for fixing metal;
The manufacturing method of the composite resin material including making the liquid containing a metal compound contact the said resin molding.   The compound for fixing the metal is at least one selected from the group consisting of a reducing compound and a compound having an amide group or an amine group having a molecular weight of 60 to 2,000. The manufacturing method of the composite resin material as described in any one of Claims.   6. The method for producing a composite resin material according to claim 5, wherein 1 g / g to 20 mmol / g of an amide group or an amine group is contained in 1 g of the compound having an amide group or an amine group.   6. The method for producing a composite resin material according to claim 5, wherein the reducing compound is at least one selected from the group consisting of calcium hypophosphite, sodium hypophosphite, and sodium borohydride.   The method for producing a composite resin material according to any one of claims 1 to 7, wherein the metal compound is a metal salt.   The method for producing a composite resin material according to any one of claims 1 to 8, wherein the metal contained in the metal compound is Pd or Ag. The compound for fixing the metal is a compound having an amide group or an amine group having a molecular weight of 60 to 2000,
The concentration of an amide group or an amine group in the vicinity of the surface of the resin base material is higher than a concentration of an amide group or an amine group in a portion other than the vicinity of the surface of the resin base material. A method for producing a composite resin material according to one item. A method of manufacturing a plated part,
Producing a composite resin material by the method for producing a composite resin material according to any one of claims 1 to 10,
A method of manufacturing a plated component, comprising: bringing an electroless plating solution into contact with the composite resin material to form an electroless plating film on a surface of the composite resin material. Resin pellets,
A compound for fixing metal;
A resin pellet comprising a thermoplastic resin. A resin base material,
A resin base material comprising a compound for fixing a metal, a first thermoplastic resin, and a second thermoplastic resin.   The compound for fixing the metal is at least one selected from the group consisting of a reducing compound and a compound having an amide group or an amine group having a molecular weight of 60 to 2,000. Resin base material. The resin base material according to claim 13 or 14, wherein the reducing compound is at least one selected from the group consisting of calcium hypophosphite, sodium hypophosphite, and sodium borohydride.

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