JP2006131769A - Plastic structure and method for producing plastic structure - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a new plastic structure containing a high concentration of metallic microparticles in the inside near its surface. <P>SOLUTION: The plastic structure is one wherein a metallic element 202 (e.g., palladium) in the form of an organometallic complex or a modification thereof is present in an amount of at least 5 atomic% in the depth to 5 nm from the outermost surface of a desired part of the plastic structure 4, and amide groups are present in at least the region where the metallic element 202 is present. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention relates to a surface-modified plastic structure and a method for producing the plastic structure. More specifically, the present invention relates to a plastic structure having a surface modified conductivity and a method for manufacturing the plastic structure.

  Electroless plating is widely used as a means for forming a metal conductive film on the surface of an electronic device made of a plastic structure. The process of electroless plating of plastic differs slightly depending on the material, etc., but generally, as shown in the flowchart of FIG. 10, resin molding (S100), degreasing of the molded body (S101), etching (S102), neutralization and wetting (S103), catalyst application (S104), catalyst activation (S105), and electroless plating (S106).

  In addition, a chromic acid solution or an alkali metal hydroxide solution is used for etching, but these etching solutions require post-treatment such as neutralization, which is a cause of high cost and a highly toxic etchant. There is a problem of handling due to use.

  Several processes that do not require roughening by etching have been proposed (for example, Patent Documents 1 and 2). In these, a thin film containing a plating catalyst is formed on a plastic surface with an organic binder or an ultraviolet curable resin. In addition, a technique for modifying a plastic surface by irradiating an ultraviolet laser in a gas atmosphere such as an amine compound has already been proposed (for example, Patent Document 3). Further, reforming techniques such as corona discharge treatment, plasma treatment, and ultraviolet treatment have been proposed.

  On the other hand, a semi-additive method is well known as a method of forming wiring on a circuit board by electroless plating or electrolytic plating. A flow according to the semi-additive method is shown in FIG.

  According to this method, the wiring layer is formed by the following steps. First, the surface of the resin molded body is treated by the same process as that shown in FIG. 10 (S100 to S105). Next, a plating layer of 1 to 2 μm is formed on the entire substrate by electroless plating (S106). Subsequently, after forming a photosensitive film or resist (S107), a film or resist layer provided with a wiring pattern is formed by performing exposure and development by masking (S108). Further, electrolytic plating is formed on the electroless plating layer exposed by patterning by the electrolytic plating process (S109). Next, after removing the film and resist (S110), the plating wiring is completed by removing the electroless plating layer other than the wiring portion by soft etching (S111).

  Furthermore, in the case of copper plating, since the adhesion to the resin is poor, a post-treatment may be performed to form fine protrusions on (oxidized) copper and reinforce the anchoring action with the resin. This processing is usually called blackening processing.

  A method of providing a three-dimensional circuit on a molded body has also been conventionally proposed (for example, Patent Documents 4 and 5). First, a three-dimensional circuit board plastic is formed by resin molding. Next, after roughening the surface and applying a catalyst, electroless plating is formed on the entire surface, and a photoresist is applied over the entire surface. Then, after exposing with a photomask, development is performed to remove portions other than the circuit pattern forming portion.

  After electrolytic plating and further electroless plating of Ni or Au are formed thereon, the photoresist is peeled off and unnecessary portions of the electroless plating are removed by etching. Since it is difficult to form a uniform photoresist on the three-dimensional structure, it is proposed in Patent Document 4 to use an electrodeposition resist. However, such a resist has a drawback of low alkali resistance.

  A circuit formation method using injection molding has also been proposed (for example, Patent Document 6). According to the method described in Patent Document 6, first, a roughened surface of Ra 1 to 5 μm is provided on the circuit forming surface on the mold surface, and the catalyst core is adhered to the entire surface of the mold before injection molding. Thereafter, the catalyst core is entirely transferred by forming a circuit board by injection molding. The electroless plating strongly adheres only to the roughened molding surface where the adhesion of the catalyst core is strong, and the other non-roughened parts are weakly adherent, so that there is no other than the circuit after electrolytic plating. Patent Document 6 describes that it can be removed together with a nuclear catalyst during etching for removing the electrolytic plating layer.

A novel plastic electroless plating method using a supercritical fluid has been proposed (for example, non-patented) in order to overcome the problems of the conventional technology for forming an electroless plating film and plating film wiring of plastic. Reference 1). According to the method described in Non-Patent Document 1, the metal complex can be injected onto the polymer surface by dissolving the organometallic complex in supercritical carbon dioxide and bringing it into contact with various polymers. Then, metal fine particles are deposited by reduction by heating, chemical reduction treatment or the like. This allows electroless plating over the entire polymer surface. According to this process, waste liquid treatment is unnecessary, and an electroless plating process of plastic with good surface roughness can be achieved.
JP-A-9-59778 JP 2001-303255 A JP-A-6-87964 JP-A-4-76985 JP-A-1-206692 JP-A-6-196840 Teruo Hori, “Latest Application Technology for Supercritical Fluids”, NTS Publishing, p.250-255 (2004)

  Non-Patent Document 1 discloses polypropylene (PP), polycarbonate (PC), PBT (polybutyl terephthalate), polytetrafluoroethylene (PTFE), nylon 6 (PA6), and the like as polymers that can be plated. ing. And as a metal complex that dissolves in supercritical carbon dioxide and penetrates into the polymer and becomes the plating nucleus, bis (cyclopentadienyl) nickel, bis (acetylacetonato) palladium (II), dimethyl (cyclooctadienyl) ) Platinum (II) is disclosed, but the metal complex is disclosed only in the form of islands penetrating from the polymer surface to the inside. And in order to provide electroconductivity to the polymer surface, formation of an electroless plating film was essential as described above after permeation and reduction of the metal complex.

  As a result of intensive studies by the present inventors, the metal complex dissolved in the supercritical fluid has a permeation amount on the outermost surface of most polymers of at most 2 to 3 atomic% (atomic percent) or less, It was found that it penetrated into islands. Furthermore, it was found that the permeated metal complex is hardly reduced efficiently to become metal fine particles, that is, the reduction rate is not necessarily high.

  Accordingly, an object of the present invention is to solve the above-mentioned problems and to allow a metal complex to penetrate from the plastic surface to a high concentration in a plastic surface modification method using a supercritical fluid as a solvent. Furthermore, the object is to form a conductive film made of metal fine particles without an electroless plating process by reducing a metal complex that has penetrated at a high concentration to metal fine particles at a high reduction rate.

  In addition, the metal complex dissolved in the supercritical fluid can be selectively penetrated into the plastic surface at a high concentration and reduced during the molding process, without roughening the surface and without electroless plating process. It was aimed to form an electrical wiring pattern having. Alternatively, the object is to form metal fine particles, which serve as catalyst nuclei for electroless plating, on a plastic surface with high efficiency.

  In order to solve the above-mentioned problems, the plastic structure according to the present invention has a metal element composed of an organometallic complex or a modified product thereof at 5 atomic% or more at a depth of 5 nm or less from the outermost surface of a desired portion of the plastic structure. In addition, an amide group exists at least in a region where the metal element exists. According to the present invention, a metal complex or a metal element derived therefrom permeates at a high concentration on the outermost surface of the plastic and the plastic structure, so that a high-quality electroless plating film can be formed. In addition, conductivity can be obtained without performing electroless plating. The plastic structure according to the present invention includes both a plastic and a plastic molded body (molded product).

  FIG. 4 shows a schematic diagram of a cross-sectional structure of a plastic according to the present invention. As shown in the figure, a metal complex or metal element cluster 202 penetrates into the plastic surface region 201. In particular, more clusters 202 penetrate the outermost surface 200.

  Here, as a plastic analysis method, for example, the following method can be used. First, the distribution of the metal complex or metal element in the thickness direction from the outermost surface of the plastic is obtained by exposing a cross section of the plastic with a focused ion beam processing observation apparatus (FIB) and then transmitting a transmission electron microscope (TEM). It can be identified by observing the cross section with a transmission electron microscope. Further, the distribution of metal fine particles can be mapped in the thickness direction by an electron beam microprobe analyzer (EPMA).

  X-ray photoelectron spectroscopy (XPS: X-ray Photoelectron Spectroscopy, ESCA: Electron Spectroscopy for Chemical Analysis) is used for state analysis such as the element ratio of the metal complex on the outermost surface and the metal fine particles derived therefrom and the reduction rate of the metal complex. be able to. In X-ray photoelectron spectroscopy, the type of element can be determined from the detected binding energy of electrons, and the element ratio can be determined from signal intensity. In addition, when a plastic in which the metal complex that has penetrated inside is not completely reduced to a metal element is analyzed, the detected waveform has a broad shape shifted to a higher energy side than the binding energy of the metal element. In this case, by analyzing the state of the ratio of the metal and its oxide or metal complex, the ratio of the metal element present as the metal can be obtained. Although it is necessary to investigate in advance the binding energy of a single metal complex, the metal complex present in the plastic can be extracted from the plastic with supercritical carbon dioxide and taken out for analysis.

  The plastic structure according to the present invention is made of a plastic material having an amide group (—CONH). According to the study by the present inventors, for example, a polyamide (PA) -based material having the following structure is penetrated with a high concentration, and a high reduction rate can be obtained. For PA, nylon polymers represented by the following chemical structural formulas (1) and (2) can be used. In addition, a high heat resistant super engineering plastic or aromatic nylon having a benzene ring such as polyamideimide (PAI) can be used. Various plastic materials may contain an inorganic filler or the like.

Furthermore, the plastic structure according to the present invention has conductivity due to a metal element whose surface has penetrated inside. Compared to other plastics, the polyamide complex penetrates the polyamide complex at a higher concentration, and a metal conductive film can be formed without an electroless plating process. The mechanism is attributed to having a hydrophilic amide group, and is considered to have good affinity for supercritical carbon dioxide and metal complexes, and serve as a reduction site for metal complexes.

  In addition, by bringing the organometallic complex dissolved in the supercritical fluid into contact with a plastic having an amide group, it is possible to form a conductive film composed of the metal element contained in the organometallic complex on the surface of the plastic. It is. The organometallic complex that can be used in the present invention is arbitrary as long as it has a certain degree of solubility in supercritical carbon dioxide. For example, bis (cyclopentadienyl) nickel, bis (acetylacetonato) palladium (II), dimethyl (cyclooctadienyl) platinum (II), hexafluoroacetylacetonatopalladium (II), hexafluoroacetylacetonatohydrate copper (II), hexafluoroacetylacetonatoplatinum (II), hexafluoroacetyl Examples include acetonato (trimethylphosphine) silver (I), dimethyl (heptafluorooctaneoneate) silver (AgFOD), and the like. After these metal complexes are dissolved in a supercritical fluid and infiltrated into the plastic, the reduction efficiency may be improved by heat treatment or chemical reduction treatment.

In the present invention, a cosolvent such as acetone or alcohol may be used in order to improve the solubility of the metal complex in the supercritical fluid.
In addition, it is preferable to include glass fibers in a region where at least the metal element exists in the plastic structure. Thereby, the intensity | strength of a plastic structure can be raised.

  In the embodiment of the present invention, the metal complex and the metal fine particles can be permeated into the surface of the plastic and the interior thereof at a high concentration during molding, for example, a plastic structure having conductivity can be obtained. In particular, according to the present invention, a metal film with high adhesion can be obtained, and can also be used as wiring. In order to reduce the surface electrical resistance, an electroless plating film may be further formed.

  A method of bringing the plastic having an amide group into contact with the supercritical fluid in which the metal complex is dissolved is arbitrary, but the molten plastic may be mixed with the supercritical fluid in a plasticizing cylinder, for example. Further, after injection-filling the mold with plastic, a gap may be formed between the mold and the plastic, and the supercritical fluid and the metal complex may be introduced.

Supercritical fluids that can be used in the present invention are air, CO, CO ₂ , O ₂ , N ₂ , H ₂ O, methane, ethane, propane, butane, pentane, hexane, methanol, ethyl alcohol, acetone, diethyl Ethers and the like. The critical temperature of N ₂ is −147 ° C. and the critical pressure is 34 atm. The critical temperature of H ₂ O is 374 ° C. and the critical pressure is 218 atm, whereas the critical temperature of CO ₂ is 31 ° C. The pressure is 73 atmospheres, CO ₂ is particularly desirable in that it has a solubility comparable to that of n-hexane and works as a plasticizer for certain thermoplastic resin materials and has a proven track record in injection molding and extrusion molding. These may be used individually by 1 type and may mix 2 or more types.

  Another aspect of the present invention is a method for producing a plastic structure having a metal element pattern for forming a conductive film on the surface of the plastic structure, wherein the amide group is placed in a mold of an injection molding apparatus or a press apparatus. A step of injecting or holding a thermoplastic resin made of plastic having a surface thereof, and a step of selectively bringing a supercritical fluid in which an organometallic complex is dissolved into contact with the surface of the thermoplastic resin. The metal fine particles produced by being reduced to the organometallic complex are present at a ratio of 5 atomic% and have conductivity.

  A schematic diagram of the cross-sectional structure of the plastic in the present invention is shown in FIG. Has penetrated. According to the aspect of the present invention, the metal fine particles permeate selectively into the plastic in a state of being densely patterned while forming nano-scale clusters, so that the electricity excellent in adhesion and surface smoothness can be obtained. Wiring can be obtained. Furthermore, the film thickness of the conductive film may be increased by electroless plating or the like to reduce the surface electrical resistance.

  According to the present invention, it is possible to provide a novel plastic in which metal fine particles permeate at a high concentration inside the vicinity of the surface. Since the metal fine particles can be permeated selectively, a plastic structure having an electric circuit can also be obtained.

[Example 1]
FIG. 1 shows a schematic configuration of a plastic structure manufacturing apparatus used in this example. In this example, the metal complex was injected over the entire surface of the nylon resin using the manufacturing apparatus shown in FIG. Carbon dioxide was used as the type of supercritical fluid. A heater (not shown) is wound around the entire piping surface of the apparatus. The piping heater was set at 55 ° C.

  In this example, a known syringe pump (SFX260D manufactured by ISCO) was used as a supercritical fluid generator. The cylinder 1 storing liquefied carbon dioxide of 3 to 7 MPa passes through the filter 41 and the backflow prevention valve 37 by manual opening of the ball valve 35, is introduced into the syringe pump 2, and is pressurized. Note that the pressure of the liquefied carbon dioxide is measured by the pressure gauge 40. On the other hand, an entrainer such as ethanol or acetone as a cosolvent is stored in the container 31. When the ball valve 36 is opened, the entrainer stored in the container 31 is introduced into the entrainer syringe pump 3 via the backflow prevention valve 37 and is pressurized.

  In this example, the mixed fluid of carbon dioxide and entrainer was controlled so that the pressure of the pressure gauge 39 was 20 MPa while controlling the volume ratio concentration of the entrainer with respect to carbon dioxide at an arbitrary value. In this example, ethanol was used as the entrainer, and the concentration relative to carbon dioxide was 2%. A safety valve 42 is provided so that the pressure of the pressure gauge 39 does not rise excessively.

  The supercritical carbon dioxide mixed with ethanol synthesized by the above method was introduced into the high-pressure vessel 6 through the inlet 46 when the ball valve 43 was opened.

  In the high-pressure vessel 6, the plastic 4 and the metal complex 8 were previously separated by a filter 44 and installed. The inside of the high-pressure vessel 6 is agitated by the agitator 7 and can be made uniform in concentration.

  In this example, the plastic 4 was a PA6 film (6432-02 6N 6 nylon manufactured by Aram Co., Ltd.) having a plate thickness of 0.3 mm. As the metal complex 8, bis (acetylacetonato) palladium (II) was used.

  In the present invention, the batch method is used as in this embodiment, and in order to inject the metal complex at a high concentration onto the surface of the nylon resin, it is necessary to increase the amount of the metal complex charged to the target plastic to some extent. . The charge amount of the metal complex to the plastic is preferably 0.5 wt% (weight percent) or more. This is because if the charging amount is small, it is injected only in an island shape, and it may not be possible to obtain conductivity. In this example, 60 mg (2 wt%) of the metal complex was used with respect to 3 g (gram) of PA6.

  The supercritical carbon dioxide introduced into the high-pressure vessel 6 dissolves the metal complex 8 and diffuses throughout the vessel. A part of the surface of the plastic 4 penetrates. Although the temperature of the high-pressure vessel 6 can be controlled by a heater (not shown), in this embodiment, the temperature was set to 120 ° C. and kept at this temperature for 1 hour. Thereafter, the container 6 was cooled to 40 ° C.

Then, the ball valve 69 is opened, and the powder of carbon dioxide, ethanol, and excess metal complex decompressed to the atmospheric pressure is extracted into the extraction container 32 while controlling the pressure 33 so that the pressure 33 is not suddenly reduced by the pressure holding valve 34. did.
The inside of the high-pressure vessel 6 was evacuated, and the plastic of PA6 was taken out. The surface had a metallic luster and was electrically conductive.

  Table 3 shows the results of measuring the element ratio of the plastic surface of this example using an X-ray photoelectron spectrometer (XPS). The element derived from Pd was found to be contained at 11.6 atomic%.

Next, the abundance ratio of Pd metal, that is, the reduction ratio of the metal complex was calculated from the narrow band waveform of the binding energy of Pd3d measured by XPS. Shows a narrowband waveform binding energy of Pd3d of this embodiment in FIG. 8, but the peak of Pd3d ₅ and Pd3d ₃ was detected broad. From this, it was found that components other than the metal component were included. The chemical bond state of Pd, that is, the peak bond energy of Pd3d was previously identified with a metal complex alone. Then, the original waveform of Figure 8, the peak energy of Pd3d ₅ chemical bonds, Pd metal 335.1EV, PdO 2 and of the metal complex 337.9～338.2EV, 3 kinds attributed to each 336.3eV of PdO It was confirmed that it can be separated into waveforms. The area ratio of the separated waveforms was calculated so that the synthesized waveform of each separated waveform completely overlapped with the original waveform. From this, it was found that the abundance ratio of Pd metal was 76%.

  From the above, in the plastic of this example, it was found that the amount of Pd metal on the outermost surface was 11.6 (atomic%) * 76 (%) = about 8.8 (atomic%).

  From this, it was found that the Pd complex was reduced to a metal at a high reduction rate and present in a high concentration on the outermost surface (usually a depth of 5 nm or less because it depends on the XPS analytical ability).

  Furthermore, the cross section of the plastic of this example was exposed with FIB, and the results of observation with TEM are shown in FIGS. 6 and 7, the arrow portion is the outermost surface portion of the plastic. From these, it can be seen that a layer 200 in which Pd metal elements are concentrated at a high concentration is formed on the outermost surface with a thickness of about 40 nm. Further, FIG. 6 shows that the depth of penetration of the Pd element is at least 2 μm or more.

  As described above, in the nylon resin in this example, the Pd metal component reduced from the metal complex penetrated at a high concentration, and a conductive metal film was formed on the outermost surface.

[Example 2]
The metal complex was injected into PA6 in the same manner as in Example 1 except that hexafluoroacetylacetonato palladium (II) was used as the metal complex and the amount charged to the plastic was 15 wt%. The pressure 39 was controlled to be 15 MPa. The temperature of the high-pressure vessel was set to 150 ° C. and kept at this temperature for 1 hour. In this example, no entrainer was used. Otherwise, the metal complex was allowed to penetrate the entire plastic surface in the same manner as in Example 1.

  The treated plastic surface had a metallic luster and was electrically conductive. Table 4 shows the results of measuring the element ratio of the plastic surface of this example using an X-ray photoelectron spectrometer (XPS). The element derived from Pd was found to be contained at 15.0 atomic%.

  Next, the abundance of Pd metal was calculated from the narrow band waveform of the binding energy of Pd3d measured by XPS. From this, it was found that the abundance ratio of Pd metal was 77%.

  From the above, it was found that in the plastic of this example, the amount of Pd metal on the outermost surface was 15.0 (atomic%) * 77 (%) = about 11.6 (atomic%).

  Furthermore, the cross section of the plastic of this example was exposed with FIB, and the results of observation with TEM are shown in FIGS. From this, it was found that a layer in which Pd metal elements were densely formed at a high concentration was not clearly formed on the outermost surface, but penetrated at a high concentration even in the depth direction. It was also found that the depth of penetration of the Pd element was at least 5 μm.

[Example 3]
A PA66 film (6435-02 66N manufactured by Aram Co., Ltd.) having a plate thickness of 0.5 mm was used as the plastic, and the pressure of the pressure gauge 39 was controlled to 20 MPa. The temperature of the high-pressure vessel was set to 150 ° C. and kept at this temperature for 5 hours. Other than that, the metal complex was infiltrated into the entire plastic surface with the same metal complex and charge as in Example 2.

  The treated plastic surface had a metallic luster and was electrically conductive. Table 5 shows the results of measuring the element ratio of the plastic surface of this example using an X-ray photoelectron spectrometer (XPS). The element derived from Pd was found to be contained at 18.2 atomic%.

  Next, the abundance of Pd metal was calculated from the narrow band waveform of the binding energy of Pd3d measured by XPS. From this, it was found that the abundance ratio of Pd metal was 81%.

  From the above, it was found that in the plastic of the present example, the amount of Pd metal on the outermost surface was 18.2 (atomic%) * 81 (%) = about 14.7 (atomic%).

  Furthermore, the cross section of the plastic of this example was exposed with FIB, and the results of observation with TEM are shown in FIGS. From this, it was found that a layer having a high concentration of Pd metal elements was formed on the outermost surface with a thickness of about 60 nm.

[Example 4]
A PAI film having a plate thickness of 0.3 mm (6448-01, manufactured by Aram Co., Ltd.) was used as the plastic, and the amount of metal complex charged to the plastic was 10 wt%. The pressure gauge pressure 39 was controlled to 20 MPa. Other than that, the metal complex was made to osmose | permeate the whole plastic surface like Example 2. FIG.

  The treated plastic surface had a metallic luster and was electrically conductive. Table 6 shows the results of measuring the element ratio of the plastic surface of this example using an X-ray photoelectron spectrometer (XPS). It was found that the element derived from Pd contained 17.9 atomic%.

  Next, the abundance of Pd metal was calculated from the narrow band waveform of the binding energy of Pd3d measured by XPS. From this, it was found that the abundance ratio of Pd metal was 75%.

  From the above, in the plastic of this example, it was found that the amount of Pd metal on the outermost surface was 17.9 (atomic%) * 75 (%) = 13.4 (atomic%).

  Furthermore, the cross section of the plastic of this example was exposed with FIB, and the results of observation with TEM are shown in FIGS. From this, it was found that a layer having a high concentration of Pd metal elements was formed on the outermost surface with a thickness of about 20 nm. When the outermost surface portion 200 was subjected to elemental analysis by EDS (Energy Dispersive X-Ray Spectroscopy energy dispersive spectroscopy), 30 atomic% of Pd element was detected.

  In this sample, penetration of the metal complex in the depth direction was not observed. As this factor, it is presumed that the glass transition temperature of the material was high (about 250 ° C.), and the polymer did not swell sufficiently due to the processing conditions (150 ° C., 20 MPa). However, on the outermost surface, the metal complex is adsorbed at a high concentration, which suggests that the affinity of the present polymer with the metal complex and carbon dioxide is high.

[Example 5]
A substrate of PA6 (Novamid 1015G33 made by Mitsubishi Engineering ring plastic) having a thickness of 2.0 mm and containing 33% glass fiber produced by injection molding in plastic was used. The amount of metal complex charged to the plastic was 25% by weight. The pressure gauge pressure 39 was controlled to 20 MPa. Other than that, the metal complex was made to osmose | permeate the whole plastic surface like Example 2. FIG.

  The treated plastic surface had a metallic luster and was electrically conductive. Table 7 shows the results of measuring the element ratio of the plastic surface of this example using an X-ray photoelectron spectrometer (XPS). It turned out that the element derived from Pd is contained 8.6 atomic%.

  Next, the abundance of Pd metal was calculated from the narrow band waveform of the binding energy of Pd3d measured by XPS. From this, it was found that the abundance of Pd metal was 80%.

  From the above, in the plastic of this example, it was found that the amount of Pd metal on the outermost surface was 8.6 (atomic%) * 80 (%) = about 6.9 (atomic%).

  Furthermore, the cross section of the plastic of this example was exposed with FIB, and the results of observation with TEM are shown in FIGS. From this, it was found that a layer in which Pd metal elements were densely concentrated at the outermost surface was not clearly formed. However, it was found that Pd element penetrates at a high concentration at a depth of at least 2 μm. In this depth range, no glass fiber was observed. This is considered to be due to the fact that glass fibers having a high specific gravity are concentrated on the center of the molded body during injection molding and hardly float on the outermost surface.

[Example 6]
In the present embodiment, the syringe pump and the like use the same device as in the first embodiment, and the device configuration up to the ball valve 43 is the same as that in the first embodiment. A part of the apparatus according to this example is shown in FIG. A mixed solvent of supercritical carbon dioxide and ethanol was introduced into the high-pressure vessel 6 in which the metal complex 8 was dissolved through the ball valve 43 and the valve 47. The mixing ratio and pressure of ethanol and carbon dioxide were the same as in Example 1. The pressure was adjusted so that the pressure gauge 51 became 20 MPa.
In the high-pressure vessel 6, the same metal complex bis (acetylacetonato) palladium (II) as in Example 1 was dissolved in supercritical carbon dioxide using the stirring device 7.

  In this example, a plastic plate made of nylon resin previously injection-molded by the following method was press-molded. In this example, PA6 (Novamid 1010C2 manufactured by Mitsubishi Engineering Plastics) was used as the nylon resin. First, a plastic plate 4 having a thickness of 1.0 mm is set on the press piston 15, and a supercritical fluid adjusted by the pressure reducing valve 49 so that the pressure gauge becomes 15 MPa is introduced from the lower surface of the press piston 15 by opening the valve 48. Then, the piston 15 was raised. The temperature of the press piston 15 is controlled by 100 ° C. temperature control water introduced by the temperature control hose 52.

  The plastic plate 4 is pressed against the Ni stamper 14 by pressing. The stamper 14 has a thickness of 0.6 mm and is held on the upper mold 21 by a stamper holder 19. The temperature of the upper mold 21 is controlled to 100 ° C. by temperature control water flowing in the temperature control circuit 56. The upper mold 21 and the lower mold are sealed inside the O-ring 67.

  On the stamper 14, several rectangular grooves 22 shown in FIG. As shown in FIG. 3, the groove 22 on the stamper has a groove width 9 of 100 μm and a pitch 10 of 100 μm. The depth of each groove is 100 μm. Each groove 9 is connected to a cylindrical hole 18 for introducing a supercritical fluid and a discharge hole 17. At the center of each of the introduction hole 18 and the discharge hole 17, through holes 11 and 12 having a diameter of 30 μm that penetrate the stamper are provided.

  In this embodiment, the supercritical fluid and the dissolved metal complex flow through the fine space formed between the groove 22 on the stamper that is in close contact with the plastic 4 via the through hole 11 and the introduction hole 18, and are discharged. The holes 17 and the through holes 12 are discharged.

  In this example, the ball valve 47 was opened on the surface portion of the plastic 4 facing the groove 22 while being pressed by the above method, and the metal complex dissolved in the supercritical fluid was brought into contact therewith. After the supercritical fluid was allowed to stay for 5 minutes, the ball valve 53 was opened only for 0.5 seconds, and a part of the supercritical fluid and the like was discharged to the collection tank 13. And the valve | bulb 54 was opened and the collection tank was pressure-reduced to atmospheric pressure.

  After the supercritical fluid returned to high pressure was brought into contact with the surface of the plastic 4, the operation of discharging was repeated four times. Then, after closing the ball valve 47, the valves 53 and 54 were opened, and the inside of the mold was decompressed to the atmosphere.

By the above method, only the portion corresponding to the groove 22 was infiltrated with the metal complex in which the supercritical fluid was dissolved. Furthermore, the temperature of the temperature control water of the upper mold 21 and the lower mold 20 was increased to 170 ° C., and the metal complex was thermally reduced.
Then, after cooling the mold temperature to 50 ° C., the plastic was taken out.

  The plastic surface in this example was deformed into a convex shape only at the portion corresponding to the groove 22 of the stamper, and only the convex portion had metallic luster and conductivity. When the cross section was observed, as shown in FIG. 5, a cluster of metal elements 202 formed a dense layer on the surface, and penetrated to a depth of 50 μm.

Comparative example

[Comparative Example 1]
The metal complex was infiltrated into the entire plastic surface in the same manner as in Example 1 except that an alicyclic olefin resin having a glass transition temperature of about 150 ° C. (ZEONEX 480R manufactured by Nippon Zeon Co., Ltd.) was used as the plastic. The treated plastic surface did not have metallic luster or conductivity. Table 8 shows the results of measuring the element ratio of the plastic surface of this comparative example with an X-ray photoelectron spectrometer (XPS). As a result, it was found that the element derived from Pd contained 2.2 atomic%.

  Next, the abundance of Pd metal was calculated from the narrow band waveform of the binding energy of Pd3d measured by XPS. The waveform is shown in FIG. From this, it was found that the abundance ratio of Pd metal was 60%.

  From the above, in the plastic of this comparative example, it was found that the amount of Pd metal on the outermost surface was 2.2 (atomic%) * 60 (%) = about 1.3 (atomic%).

[Comparative Example 2]
A PEI (Polyetherimide GE Plastics Ultem) substrate with a plate thickness of 2.0 mm was used as the plastic, and the amount of metal complex charged to the plastic was 1% by weight. The temperature of the high-pressure vessel was set to 150 ° C. and kept at this temperature for 30 minutes. Other than that, the metal complex was made to osmose | permeate the whole plastic surface like Example 2. FIG.

  The treated plastic surface did not have metallic luster or conductivity. Table 9 shows the results of measuring the element ratio of the plastic surface of this comparative example using an X-ray photoelectron spectrometer (XPS). It was found that the element derived from Pd contained 3.7 atomic%.

  Next, the abundance of Pd metal was calculated from the narrow band waveform of the binding energy of Pd3d measured by XPS. From this, it was found that the abundance ratio of Pd metal was 6%.

  From the above, in the plastic of this comparative example, it was found that the amount of Pd metal on the outermost surface was 3.7 (atomic%) * 6 (%) = about 0.2 (atomic%).

[Comparative Example 3]
A PET film having a thickness of 0.1 mm was used as the plastic, and dimethylcyclooctadiene platinum (II) was used as the metal complex. The amount of metal complex charged to the plastic was 1% by weight. The temperature of the high-pressure vessel was set to 120 ° C. and kept at this temperature for 1 hour. Other than that, the metal complex was made to osmose | permeate the whole plastic surface like the comparative example 2. FIG.

  The treated plastic surface did not have metallic luster or conductivity. Table 10 shows the results of measuring the element ratio of the plastic surface of this comparative example using an X-ray photoelectron spectrometer (XPS). The element derived from Pt was found to be contained at 1.0 atomic%.

  Next, the abundance of Pt metal was calculated from the narrow band waveform of the binding energy of Pt4f measured by XPS. From this, it was found that the abundance ratio of Pt metal was 26%.

  From the above, in the plastic of this comparative example, it was found that the amount of Pt metal on the outermost surface was 1.0 (atomic%) * 26 (%) = about 0.3 (atomic%).

In addition to the present comparative example, similar experiments were performed using PMMA and PC, but a conductive film having a metallic luster as in the present invention could not be formed. Further, the amount of metal present on the outermost surface by XPS analysis was 3 atomic% or less, and the reduction rate was 65% at the maximum.
Table 11 shows the injection conditions of the metal complexes of Examples 1 to 5 and Comparative Examples 1 to 3, and Table 12 shows the XPS analysis results after injection of the metal complexes.

It is a schematic block diagram which shows the manufacturing apparatus of the plastic structure concerning this invention. It is a schematic block diagram which shows a part of manufacturing apparatus of the plastic structure concerning this invention. It is a top view which shows the structure of the groove | channel on the stamper integrated in the manufacturing apparatus of the plastic structure concerning this invention. It is a schematic diagram of the cross-sectional structure of the plastic structure concerning this invention. It is a schematic diagram of the cross-sectional structure of the plastic structure concerning this invention. It is a cross-sectional photograph by TEM of the plastic structure concerning this invention. It is a cross-sectional photograph by TEM of the plastic structure concerning this invention. It is a graph which shows the narrow band waveform of the binding energy of PD3d in the plastic concerning this invention. It is a graph which shows the narrow band waveform of the binding energy of PD3d in the plastic concerning this invention. 3 is a flowchart showing a general plastic electroless plating process. It is a flowchart which shows the manufacturing process of a general wiring layer. It is the figure which observed the cross section of the plastic concerning Example 2 by TEM. It is the figure which observed the cross section of the plastic concerning Example 2 by TEM. It is the figure which observed the cross section of the plastic concerning Example 3 by TEM. It is the figure which observed the cross section of the plastic concerning Example 3 by TEM. It is the figure which observed the cross section of the plastic concerning Example 4 by TEM. It is the figure which observed the cross section of the plastic concerning Example 4 by TEM. It is the figure which observed the cross section of the plastic concerning Example 5 by TEM. It is the figure which observed the cross section of the plastic concerning Example 5 by TEM.

Explanation of symbols

4 Plastic structure 202 Cluster

Claims (12)

  A plastic in which a metal element composed of an organometallic complex or a modified product thereof is present at 5 atomic% or more at a depth of 5 nm or less from the outermost surface of the desired portion of the plastic structure, and an amide group is present at least in the region where the metal element is present. Structure.   The plastic structure according to claim 1, wherein a reduction rate of the metal element is 60% or more.   The plastic structure according to claim 1 or 2, wherein the metal element is a palladium complex or a modified product thereof.   4. The plastic structure according to claim 1, 2 or 3, wherein the surface of the plastic structure has conductivity by a metal element penetrating inside.   5. The plastic structure according to claim 1, wherein a region where at least the metal element is present in the plastic structure includes glass fibers. 6. A method of forming a conductive film on a plastic surface,
Dissolving an organometallic complex in a supercritical fluid;
A method for forming a conductive film, comprising the step of bringing the organometallic complex into contact with a plastic surface having an amide group, and forming a conductive film on the surface of the plastic with a metal element contained in the organometallic complex.   The method for forming a conductive film according to claim 6, wherein the metal element is a palladium complex or a modified product thereof.   The method for forming a conductive film according to claim 6 or 7, wherein the plastic contains glass fiber. A method of manufacturing a plastic structure,
Dissolving an organometallic complex in a supercritical fluid;
A step of obtaining a plastic structure by contacting a plastic having an amide group injected and filled in a mold of an injection molding apparatus with a supercritical fluid in which the organometallic complex is dissolved, and
A method for producing a plastic structure, wherein metal fine particles contained in the organometallic complex are present at a ratio of 5 atomic% or more at a depth of 5 nm or less from the outermost surface of a desired portion of the plastic structure. A method for producing a plastic structure having a metal element pattern for forming a conductive film on the surface of the plastic structure,
Injection filling or holding a thermoplastic resin made of plastic having an amide group on its surface in a mold of an injection molding device or a press device; and
A step of selectively contacting the surface of the thermoplastic resin with the supercritical fluid in which the organometallic complex is dissolved,
A method for producing a plastic structure, characterized in that metal fine particles produced by reduction to the organometallic complex are present at a ratio of 5 atomic% on the surface of the plastic structure and have electrical conductivity.   The method for producing a plastic structure according to claim 9 or 10, wherein the metal element is a palladium complex or a modified product thereof.   12. The method for producing a plastic structure according to claim 9, 10 or 11, wherein the plastic contains glass fiber.