JP3880061B2 - Method and apparatus for manufacturing molded article - Google Patents

Description

  The present invention relates to surface modification of a molded product made of a thermoplastic resin (or molten resin).

  There are many plastic molded products produced by injection molding, but their physical properties are determined by the resin material to be plasticized and melted. In addition, depending on the application, the plastic molded product may be subjected to various types of printing, painting, formation of a conductor or metal film, joining between molded products, and other post-processing. When it is necessary to perform such post-processing, generally, the surface of a plastic molded product is activated to improve the surface in order to improve processability.

  On the other hand, electroless plating is widely adopted as a means for forming a metal conductive film on the surface of an electronic device made of a plastic molded product. The plastic electroless plating process differs slightly depending on the material and the like, but is generally performed according to the flow shown in FIG.

  First, oil on the surface is removed by “degreasing” the molded product, and then the surface is roughened by “etching”. Etching uses a chromic acid solution or an alkali metal hydroxide solution, but these etching solutions require post-treatment such as "neutralization", which is a costly factor and requires a highly toxic etchant. There is a problem in handling due to use. Next, after improving wettability by “wetting” by treating with an aqueous surfactant solution, a catalyst is attached to the plastic surface by “catalyst (catalyst imparting)”. In the “catalyst” process, for example, in the case of a palladium catalyst, the plastic is impregnated with an aqueous hydrochloric acid solution of tin chloride and palladium chloride. After the “catalyst”, an “accelerator (catalyst activation)” is brought into contact with an acid such as sulfuric acid or hydrochloric acid to activate the plating catalyst. Only after the above process, “electroless plating” becomes possible.

  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. Further, a technique for modifying a plastic surface by irradiating an ultraviolet laser in a gas atmosphere such as an amine compound has been proposed (for example, Patent Document 3). Other than this, a modification technique by corona discharge treatment, plasma treatment, ultraviolet treatment or the like is conventionally known.

  On the other hand, a semi-additive method is known as a method of forming wiring on a circuit board by electroless plating or electrolytic plating. This flow is shown in FIG. In this method, first, a 1-2 μm plating layer is formed on the entire substrate by “electroless plating” in the same process as described above. Next, after forming a “photosensitive film or resist”, masking and performing “exposure and development” form a film or resist layer provided with a wiring pattern. Further, electrolytic plating is formed on the electroless plating layer exposed by the patterning by an “electrolytic plating” process. Next, after removing the film and the resist, the plated wiring is completed by removing the electroless plating layer other than the wiring portion by soft etching. In the case of copper plating, since the adhesiveness to the resin is poor, a post-treatment called “blackening treatment” is sometimes performed to form fine protrusions on (oxidized) copper and strengthen the anchor action with the resin.

  A method of providing a three-dimensional circuit in a molded product has also been conventionally proposed (for example, Patent Documents 4 and 5). In such a method, a three-dimensional circuit board plastic is first 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 to the entire surface. Then, it is exposed after being covered with a photomask, and then developed 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. It is difficult to form a uniform photoresist on the three-dimensional structure. Patent Document 4 proposes to use an electrodeposition resist, but such a resist has a drawback of low alkali resistance.

As a circuit formation method using injection molding, the following method is disclosed (for example, Patent Document 6). According to 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 after attaching the catalyst core to the entire surface of the mold before injection molding, the circuit board is mounted. The catalyst core is entirely transferred by forming by injection molding. Electroless plating strongly adheres only to the roughened molding surface where the adhesion of the catalyst core is strong, and other parts that are not roughened are weakly adherent. It can be removed together with the nuclear catalyst during the etching to remove the plating layer.
JP-A-9-59778 JP 2001-303255 A JP-A-6-87964 JP-A-4-76985 JP-A-1-206692 JP-A-6-196840

  However, a technique with a wide range of application that can simultaneously modify the surface during the molding process of injection molding has not been proposed. Further, the conventional electroless plating process for plastics is complicated and expensive, and a lot of harmful substances must be used, which causes a problem in the treatment of waste liquid.

  Accordingly, an object of the present invention is to provide a method and an apparatus for manufacturing a molded product whose surface is entirely or selectively modified during molding.

  A method for producing a molded product as one aspect of the present invention is a method for producing a molded product from a thermoplastic resin, wherein the thermoplastic resin is introduced as a molten resin into a molded part for molding the molded product. A first introduction step, a second introduction step of introducing a supercritical fluid in which an organometallic complex is dissolved into the molded part, and a step of solidifying the molten resin and disposing a metal element on the surface of the molded product. It is characterized by having.

  The molded article is a molded article made of a thermoplastic resin, and the molded article contains an organic substance or a metal element different from the thermoplastic resin, and the organic substance or the metal element is a surface of the molded article. You may arrange | position to the surface from the vicinity (namely, segregation, existing locally). Since such a molded article contains an organic substance or the like inside and on the surface, the molded article has high stability such as being less likely to be peeled off from the surface than formed by lithography or the like. The organic substance or the like may be formed on the entire surface or at a specific position. The range of “near the surface” can be appropriately selected depending on the purpose of the surface modification and the material to be used, but preferably refers to a range of 100 μm or less from the surface, more preferably 10 μm or less from the surface. In addition, depending on the purpose of surface modification and the material used, the nanoscale thickness can be modified from the surface. The molded article may further include a plating layer formed using the metal element as a nucleus. The plating layer may form an electric wiring pattern. The molded article may further have a foam inside the thermoplastic resin.

  For example, the organic substance is an organometallic complex. The metal element may be metal particles or metal fine particles. Furthermore, the metal element may be a metal element generated by removing some or all of the ligands of the organometallic complex. By arranging the organometallic complex or the metal element entirely or selectively on the resin surface, conductivity can be imparted or the magnetism can be enhanced entirely or locally. For example, a biochip can be easily sealed using a resin. In other words, it is possible to easily seal the glass substrate and the plastic by laminating a plastic having fine irregularities to be a fluid flow path with a glass substrate and generating a magnetic force from the back surface of the glass substrate. Become. Moreover, it is also possible to make a molded article having different mechanical properties by segregating the metal element entirely or partially on the surface. The part where the metal element is segregated has improved sliding resistance, hardness and the like compared to other parts. Further, a magnetic circuit pattern can be formed using a metal having magnetism. If a fluorescent material such as a rare earth complex is used as the metal complex, a molded product having a fluorescent pattern on the surface can also be molded. This can be applied as a display element.

  Although the kind of metal complex is arbitrary, Pd complex, Ni complex, Co complex, Pt complex, etc. are desirable. More specifically, platinum dimethyl (cyclooctadiene), bis (cyclopentadienyl) nickel, bis (acetylacetonate) palladium and the like are desirable. You may further have an electroless-plating layer formed using the said metal element as a nucleus. Thereby, a plating layer can be easily formed in a selection position. The plating layer constitutes an electric wiring pattern, for example. That is, the molded body of the present invention can be used as an electric wiring board. The plastic molded product may further include a foam cell. Thereby, a plastic molded product can be reduced in weight, the heat insulation effect can be improved, and the rigidity to weight ratio can be increased.

  Of course, the organic substance is not limited to the organometallic complex. By using polypropylene glycol as the organic material, the surface of a hydrophobic plastic such as polyethylene terephthalate can be selectively hydrophilized. Similarly, a selective water repellent treatment and a reduction in refractive index can be achieved by using a fluorine compound.

  A manufacturing method according to another aspect of the present invention is a method of manufacturing a molded article by injection molding a thermoplastic resin, wherein the thermoplastic resin, the supercritical fluid, and the supercritical fluid are placed in a mold. And a step of injecting a dissolved substance, wherein the surface of the molded article is modified. Such a manufacturing method can infiltrate the material into the surface and the inside of the thermoplastic resin using a supercritical fluid, and as described above, the material has better stability than that formed on the surface by etching or the like. Molded articles can be manufactured.

The supercritical fluid that can be used is arbitrary, such as air, CO ₂ , butane, pentane, methanol, etc., but has the same solubility as n-hexane and acts as a plasticizer for certain thermoplastic resin materials. CO _{2, which} has a proven track record in extrusion molding, is desirable. The substance to be dissolved in the supercritical fluid is not particularly limited. For example, a metal complex (platinum dimethyl (cyclooctadiene), bis (cyclopentadienyl) nickel, bis (acetylacetonate) palladium), Examples thereof include polypropylene glycol. In particular, the adhesion of electroless plating of plastic can be selectively improved by using a metal complex.

  Further, the thermoplastic resin is not particularly limited, and polycarbonate, polymethyl methacrylate, polyetherimide, polymethylpentene, amorphous polyolefin, polytetrafluoroethylene, liquid crystal polymer, styrene resin, polymethylpentene, Polyacetal and the like, those obtained by mixing them together, polymer alloys containing these as main components, and those obtained by blending various fillers with these can be used.

The injection step may include a step of introducing the supercritical fluid and the substance into a flow front as a flow front portion of the thermoplastic resin during injection filling. According to such a method, due to the fountain flow phenomenon (fountain effect) of the fluid resin in the mold, the thermoplastic resin in the flow front part forms a surface layer while being pulled on the mold surface. A substance dissolved and permeating into the flow front in the resin is placed in a layer near the surface in contact with the mold. Any substance having a certain degree of solubility in the supercritical fluid can be uniformly distributed only on the surface of the molded product. Therefore, application to various plastic surface modification technologies can be expected. If CO ₂ is used as the supercritical fluid, it functions as a plasticizer as described above, so that it is possible to improve the fluidity of the thermoplastic resin and to suppress the growth of the solidified layer on the surface in contact with the mold. In the injection step, the supercritical fluid and the substance may be included in a filling start portion of the thermoplastic resin.

In the injection step, the supercritical fluid and the substance may be introduced into the mold at the time of injection filling as counter pressure for applying a pressure opposite to the flow direction of the injected thermoplastic resin. The dissolved substance can be arranged near the surface of the molded article by the counter pressure. The counter pressure is that when the supercritical fluid CO ₂ or N ₂ gas is kneaded in the thermoplastic resin as a foaming agent, the internal pressure of the thermoplastic resin is suddenly reduced in the mold at the time of injection, and the foam cell diameter is expanded. In addition, it is possible to prevent the surface property from being deteriorated due to the formation of a pattern called a swirl mark on the surface. At the same time, as described above, the supercritical fluid and the dissolved substance can be arranged only on the surface by the fountain flow phenomenon.

  The injection step includes a step of introducing the supercritical fluid into which the substance does not dissolve other than a flow front as a flow front portion of the thermoplastic resin into the thermoplastic resin, and the gold using the supercritical fluid. And forming a foam inside the thermoplastic resin injected into the mold. According to such a method, it is possible to reduce the dielectric of the material by modifying the resin surface and at the same time forming fine foam cells inside. It is suitable for a high-frequency electric circuit board, a MID (Mold Interconnect Device), a planar antenna such as a millimeter wave antenna.

  The injection step may include a step of filling the mold with the thermoplastic resin and a step of introducing the supercritical fluid and the substance into a specific position in the mold. By dispersing the substance in the vicinity of a specific position on the surface of the resin and in the vicinity thereof, the surface of the resin molded product can be locally modified. You may further have the process of arrange | positioning the said substance in the said thermoplastic resin in the said specific position by adjusting the pressure and / or temperature of the said metal mold | die. Thereby, partial surface modification | reformation of the molded article surface without an unevenness | corrugation is attained.

  The substance is, for example, an organic substance or a metal element. The organic substance is an organometallic complex, and the metal element is a metal particle excluding the ligand of the organometallic complex. Since the metal complex is dissolved to some extent in the supercritical fluid, it can be arranged on the surface of the molded article without deteriorating the surface property. Further, by removing the organic part of the metal complex and precipitating the metal element, it can work with the catalyst core of electroless plating, so that the plating adhesion on the resin surface is improved without pretreatment.

  The substance may be a metal element excluding a ligand of an organometallic complex, and the method further includes a step of forming a pattern including a plating layer on a portion where the metal element is deposited by electroless plating. You may have. A metal conductive film can be easily formed by electroless plating. The pattern may include unevenness, and may further include a step of removing the convex portion of the pattern after the forming step. Moreover, the said site | part contains an unevenness | corrugation, You may further have the process of removing the convex part of the said site | part before the said formation process. Any method can form a desired pattern.

  The method further includes a step of compressing the thermoplastic resin after the injection step, and a step of foaming the thermoplastic resin by increasing a volume of the cavity of the mold after the compression step. Good. According to such a method, it is possible to reduce the dielectric material by selectively modifying the plastic surface and at the same time forming fine foam cells inside. It is suitable for a high-frequency electric circuit board, a MID (Mold Interconnect Device), a planar antenna such as a millimeter wave antenna.

  In the injection step, the filled thermoplastic resin is pressed, a predetermined pattern is formed on the first surface pressed by the thermoplastic resin, and the second surface is opposed to the first surface. A stamper in which a hole communicating with the pattern is provided at the specific position may be used. By making the pattern a stamper, the wiring circuit can be easily changed. Moreover, a desired circuit pattern can be formed by forming a pattern at a specific position.

  The mold is a mold used for producing a molded product by injection molding of a thermoplastic resin, and a counter pressure is applied to the supercritical fluid and a substance dissolved in the supercritical fluid in the mold. You may have a mechanism to introduce as. Since such a mold uses a supercritical fluid and a substance as counter pressure, the same effect as the above-described method is achieved.

  The mold is a mold used for producing a molded product by injection molding of a thermoplastic resin, and a concave or convex portion is formed at a specific position on the cavity forming surface of the mold. In addition, an introduction path for injecting a supercritical fluid and a substance dissolved in the supercritical fluid from the outside may be connected to the concave portion or the convex portion. The concave or convex shape can enhance the local adhesion of the substance.

  The injection molding apparatus includes a mold that forms a cavity for filling a thermoplastic resin, a plasticizing cylinder that introduces the thermoplastic resin into the cavity of the mold, and a plastic cylinder. The supercritical fluid and a substance dissolved in the supercritical fluid may be introduced, and a flow front serving as a flow front portion of the thermoplastic resin may include the supercritical fluid and the substance. Such an injection molding apparatus includes the supercritical fluid and the substance in the resin flow front, and thus has the same effect as the above-described method.

  The injection molding apparatus includes a mold for forming a cavity for filling a thermoplastic resin, a plasticizing cylinder for introducing the thermoplastic resin into the cavity of the mold, and an inside of the plasticizing cylinder. And a mechanism for introducing a supercritical fluid into a portion other than the flow front as the flow front portion of the thermoplastic resin. Such an injection molding apparatus has the same effect as the above-described method because the supercritical fluid can be contained in a portion other than the flow front of the resin to obtain the effect of the internal foam.

  The injection molding apparatus also has a mold for forming a cavity for filling a thermoplastic resin, and a mechanism for introducing a supercritical fluid and a substance dissolved in the supercritical fluid into the mold as a counter pressure. May be. Since such an injection molding apparatus uses a supercritical fluid and a substance as a counter pressure, the same operation as the above-described method is achieved.

  The injection molding device forms a cavity filled with a thermoplastic resin, has a mold having an introduction path communicating with a specific position of the cavity, a supercritical fluid, and a substance dissolved in the supercritical fluid. You may have a mechanism introduced into the said cavity via an introduction path. Such an injection molding apparatus can locally modify the surface of a resin molded product by dispersing the substance in the vicinity of a specific position on the surface of the resin and in the vicinity thereof.

  Further, the injection molding apparatus has a predetermined surface on a mold that forms a cavity filled with a thermoplastic resin and a first surface that is pressed by the thermoplastic resin filled in the cavity and pressed by the thermoplastic resin. A stamper in which a pattern is formed and a hole communicating with the pattern on the first surface is provided at a specific position on the second surface facing the first surface, and an organic dissolved in a supercritical fluid A mechanism for introducing a substance into the cavity through the hole of the stamper. By making the pattern a stamper, the wiring circuit can be easily changed. Moreover, a desired circuit pattern can be formed by forming a pattern at a specific position.

  Other objects and further features of the present invention will be made clear by embodiments described below with reference to the accompanying drawings.

  According to the present invention, it is possible to provide a method for producing a molded product whose surface is entirely or selectively modified during molding.

  FIG. 2 shows a flow of plastic electroless plating wiring as one embodiment of the present invention. According to the electroless plating method of the present embodiment, first, the surface of the molded product is entirely or selectively modified by injection molding (step 1100).

  In an embodiment, a molten resin, a supercritical fluid, and a substance dissolved therein (organic substance or metal element, here, an organometallic complex) are filled in a mold as a flow front as a flow front and counter pressure is filled. And introducing the supercritical fluid and the substance. Here, the counter pressure is a gas to which pressure is applied in the mold in the opposite direction to the flow direction of the injected molten resin.

  Due to the fountain flow phenomenon (fountain effect) of the flowable resin in the mold, the molten resin in the flow front part forms a surface layer while being pulled to the mold surface, so it dissolves in the supercritical fluid and flows into the resin in the flow front. The substance that has penetrated into the mold is disposed in a layer near the surface in contact with the mold. Any substance having a certain degree of solubility in the supercritical fluid can be uniformly distributed only on the surface of the molded product. Therefore, application to various plastic surface modification technologies can be expected.

  The thermoplastic resin is not particularly limited, and polycarbonate, polymethyl methacrylate, polyetherimide, polymethylpentene, amorphous polyolefin, polytetrafluoroethylene, liquid crystal polymer, styrenic resin, polymethylpentene, polyacetal, etc. It is possible to use a mixture of them in combination, a polymer alloy containing these as a main component, or a mixture of these with various fillers.

The supercritical fluid that can be used is arbitrary, such as air, CO ₂ , butane, pentane, methanol, etc., but has the same solubility as n-hexane and acts as a plasticizer for certain thermoplastic resin materials. CO _{2, which} has a proven track record in extrusion molding, is desirable.

  Next, the ligand of the organometallic complex arranged on the convex portion of the plastic molded product is removed by heating or a reduction reaction, thereby depositing metal fine particles (step 1200). Thereafter, electroless plating is performed (step 1300), and electroless plating is formed only on the convex portions.

  In the electroless plated wiring of the present embodiment, after the injection molding, since the bond between the organic part and the metal part of the metal complex is cut, a post-treatment by a reduction reaction or heating may be necessary. However, certain metal complexes break the bond by the heat of the resin while in contact with a high-temperature molten resin, and metal fine particles of several nm to several tens of μm are automatically deposited, so that no post-treatment is required. Although the kind of metal complex is arbitrary, Pd complex, Ni complex, Co complex, Pt complex, etc. are desirable. More specifically, platinum dimethyl (cyclooctadiene), bis (cyclopentadienyl) nickel, bis (acetylacetonate) palladium and the like are desirable. From the viewpoint that a reduction reaction is unnecessary, a Pd complex and a Pt complex are desirable. After the metal fine particles are deposited on the surface of the injection-molded product, any known technique can be used for the electroless plating (step 1300), so a detailed description is omitted here. For example, an electric wiring pattern can be configured using the electroless plating layer.

  In the present embodiment, fine wiring by electroless plating can be formed inexpensively and cleanly by applying a plastic surface modification technique in injection molding. The flow is shown in FIG. In the present invention, the above-described injection molding method is applied and the unevenness forming the wiring is transferred to the surface of the molded product, and the plated wiring is formed using the unevenness. For example, the flow of FIG. Two types of methods can be provided as shown in FIG. These two types of methods will be further described with reference to FIGS.

  FIG. 8 shows a conceptual diagram of an example of the plated wiring method in the present invention. According to this method, after the metal fine particles 104 acting as catalyst nuclei are deposited on the entire surface of the molded product 136 as shown in FIG. 8A, the electroless plating 138 is laminated on the surface of the molded product as shown in FIG. 8B. Then, as shown in FIG. 8C, by removing the electroless plating portion of the convex portion by polishing or the like, a wiring pattern in which the electroless plating remains only in the concave portion can be formed. The method for removing the pattern protrusions in the present invention is arbitrary, but it can be removed by polishing, lapping, or the like.

  FIG. 9 shows a conceptual diagram of another example of the plated wiring method according to the present invention. First, after the metal complex or metal fine particles are arranged in the vicinity of the surface by the above injection molding method and a molded product in which the unevenness of the mold or stamper surface is transferred is produced, in some cases, an organic substance of the metal complex is removed by heat treatment or reduction reaction Remove completely. Furthermore, after removing the convex portions on the surface of the molded product, the metal fine particles 104 acting as the catalyst nuclei for plating are disposed only in the concave portions as shown in FIG. By plating, the electroless plating 138 is selectively laminated as shown in FIG. By the methods shown in FIGS. 8 and 9, the object of forming fine wiring by electroless plating on the plastic surface at low cost can be achieved.

  Step 1100, in another embodiment, dissolves the supercritical fluid and material in the mold recess after filling the mold with molten resin. The viscosity of the resin in contact with the supercritical fluid decreases, and organic matter dissolved in the supercritical fluid penetrates from the resin surface.

Thereafter, the resin internal pressure is increased by holding pressure, clamping pressure, or the like, so that the resin spreads in the concave portions, and convex portions where organic substances are arranged are formed on the surface of the molded body. According to such a method, an organic substance having a certain degree of solubility in the supercritical fluid can be uniformly distributed only on the convex portion of the surface of the molded product. Therefore, application to various plastic surface modification technologies can be expected. If CO ₂ is used as the supercritical fluid, it functions as a plasticizer as described above, so that fine transfer can be easily performed even if the pitch of the unevenness is as fine as a submicron order.

  After injecting the supercritical fluid and the organometallic complex dissolved in the supercritical fluid, at least one of the metal complex or the metal fine particles with the ligand of the metal complex removed from the molten resin surface is infiltrated through the mold recess. As a result, the metal complex or the metal fine particles are selectively disposed only in the portions filled in the concave portions in the mold, that is, only the convex portions of the plastic molded product. According to this method, it is not necessary to roughen the mold surface, and a metal complex or the like can be selectively disposed in a fine region.

  Even if the resin does not have a polar group and it is difficult to form a strong electroless plating layer, it is possible to easily embed metal fine particles as a catalyst core into the material, so that adhesion can be made only at any selected location. An excellent high-quality electroless plating film can be formed. The electroless plating wiring process of this embodiment is harmless compared to the conventional method and requires significantly fewer pretreatment steps.

  The present invention is not limited to the electroless plating method as described above. That is, the present invention can produce a sufficiently useful molded article only by the injection molding method (step 1100). For example, by arranging the metal fine particles on the plastic surface entirely or selectively, conductivity can be imparted entirely or locally, and adhesion with magnetic force can be enhanced. Using such a plastic, for example, the biochip can be easily sealed. That is, it is possible to easily seal the glass substrate and the plastic by bonding a plastic having fine unevenness to be a fluid flow path to a glass substrate or the like and generating a magnetic force from the back surface of the glass substrate.

  Of course, the organic substance used in the injection molding method (step 1100) is not limited to the organometallic complex. For example, the surface of a hydrophobic plastic such as polyethylene terephthalate can be selectively hydrophilized by using polypropylene glycol as the organic substance. By making the flow channel surface of a biochip made of plastics hydrophilic or water-repellent as a whole or locally, the laminar flow state of the mixed fluid in the chip can be made more efficient, and the protein Analysis or the like can be performed by trapping at a location. Similarly, by using a fluorine compound, overall or selective water-repellent treatment or reduction of the refractive index can be achieved.

  Furthermore, the present invention may further include a step of foaming the molten resin by increasing the volume of the cavity after compressing the molten resin by holding pressure, clamping, or the like. As a result, the plastic surface can be selectively modified, and at the same time, a fine foam cell can be formed in the interior to reduce the dielectric material. In this case, a foamed state having an average cell diameter of 30 μm or less and a foaming ratio of 1.5 times or more is desirable. Thereby, a plastic molded product can be made lightweight, the heat insulation effect can be improved, and the rigidity-weight ratio can be increased. Such a molded article is suitable for a planar antenna such as a high-frequency electric circuit board, MID (Mold Interconnect Device), and a millimeter wave antenna.

  Examples of the present invention will be described below.

FIG. 1 shows a cross-sectional view of main parts of a mold and an injection molding apparatus used in the first embodiment of the present invention. The supercritical fluid in the present invention is arbitrary, but CO ₂ was used in this example. In the present invention, any substance can be dissolved in the supercritical fluid. In this example, platinum dimethyl (cyclooctadiene) which is a Pt complex was used.

After the method of dissolving the substance in the supercritical fluid is optional, that is the supercritical state of CO ₂ supplied from the CO ₂ cylinder 137 at a supercritical fluid generator 101 in the present embodiment, in mixing vessel 103 The substance supplied from the storage container 102 was dissolved in the supercritical fluid.

In the present invention, the pressure and temperature of the supercritical fluid in which the substance is dissolved and the method of introducing the molten resin into the flow front part are arbitrary, but in this embodiment, the supercritical CO ₂ at 120 ° C. and 10 Mpa is dissolved. At the same time, it is introduced into the cavity as a counter pressure for applying a pressure opposite to the flow direction of the injected thermoplastic resin, and the flow front portion of the molten resin is impregnated in the plasticizing cylinder 140. The pressure of the counter pressure is lower than the resin pressure at the time of filling with respect to the resin entering from the spool. The resin pressure in this case means an actual resin pressure in the mold, but is not usually monitored. Usually, the resin pressure refers to the pressure of a molding machine that extrudes a screw. The latter is about 100 to 200 MPa, which is a much larger force than the counter pressure, and the former is about 20 MPa. If the pressure of the counter pressure is defined, the pressure when the gas actually enters the mold only needs to be in a supercritical state (about 7 MPa or more for CO ₂ ). Also, the upper limit is below the pressure at which the resin can be filled, which depends on the material and molding conditions. In the present invention, the method of introducing the supercritical fluid and the substance dissolved therein as a counter pressure into the mold cavity 117 is arbitrary, but in this embodiment, the solenoid valve 111 is closed simultaneously with the start of injection filling after the cavity 117 is closed. Was introduced from the mixing tank 103 via the flow path 112.

  The method of allowing the supercritical fluid and the substance dissolved therein to penetrate into the flow front portion of the molten resin after plasticization measurement in the plasticizing cylinder 140 in the present invention is arbitrary. This will be described with reference to FIG. The plasticizing metering is a step of plasticizing resin pellets in a short time by rotating the screw, and keeping the amount filled and injected in the next shot at a fixed volume before the screw.

  First, as the screw 107 rotates in the direction of the arrow in FIG. 7A in the plasticizing cylinder 140 controlled in temperature by the band heater 139, thermoplastic resin pellets 135 are supplied from the hopper 121 and plasticized. However, since the screw 107 is pushed forward, the screw 107 moves backward. When the backward movement of the screw 107 stops at the measuring position, the molten resin 116 is plasticized and measured between the screw 107 and the shut-off nozzle 105. The shut-off nozzle 105 is a mechanism that opens and closes the flow path between the mold and the cylinder that prevents the molten resin from being mixed into the mold even when the internal pressure of the cylinder increases. The screw 107 has a function of plasticizing and melting the pellet and a function of injecting the pellet (also referred to as an in-line screw). After the plasticization measurement is completed, as shown in FIG. 7B, the screw 107 is moved backward by suck back to bring the front portion of the molten resin into a reduced pressure state, and between the shut-off nozzle 105 and the screw 107. The supercritical fluid and its lysate were introduced by opening the electromagnetic valve 108 from the supply port 106 of the provided mixture. Further, after closing the solenoid valve, the screw 107 was pressurized and advanced at a pressure of 10 Mpa to infiltrate the supercritical fluid and its melt into the flow front portion of the molten resin. Immediately after that, injection filling was performed.

  In the present invention, a thermoplastic resin that can be used is arbitrary, but in this example, polyetherimide (ULTEM 1010 manufactured by GE Plastics) having a glass transition temperature of about 230 ° C. was used. The temperature of the plasticizing cylinder was 380 ° C.

  In the injection molding method according to the present invention, there is no restriction other than impregnating the flow front as the flow front portion of the molten resin with the supercritical fluid and its melt. Injection compression molding was used in which mold clamping compression was performed immediately after opening filling. A mold seal mechanism was devised that prevents the supercritical fluid from leaking even if the cavity is opened with the supercritical fluid introduced as counter pressure. Due to the molding method and mold structure, fine transfer is possible even for difficult-to-mold materials with high glass transition temperatures and thin-walled products in which the resin does not flow easily.

  Next, the molding method in the present embodiment will be described in detail with reference to FIGS. The principal part enlarged view of the metal mold | die in the A section of FIG. 1 was shown to FIG. 4, FIG. In this example, two plate-shaped products having a product shape of 50 mm long × 60 mm wide × 0.5 mm thick were molded. The temperature of the fixed mold 143 and the movable mold 129 of the mold 142 is controlled by cooling water flowing through a temperature control circuit (not shown). In this embodiment, the temperature is controlled at 140 ° C.

  As shown in FIG. 1, the cavities 117 in the mold 142 are divided into upper and lower parts around a spool 119, and rectangular stampers 118 corresponding to the cavities 117 are installed on the fixed mold 143. A line-and-space uneven pattern is provided on the surface of the stamper 118. The stamper was produced as follows. First, concavo-convex portions were formed with a resist on a silicon substrate using photolithography, and then Ni having a thickness of 0.4 mm was formed on the resist pattern by electroless plating and electrolytic plating. Then, Ni was removed from the resist and processed into a stamper shape.

  As shown in FIG. 4, one side of the stamper 118 on the spool 119 side is mechanically fixed to the fixed mold 143 by a stamper pressing claw 141, and the other three sides are fixed by a vacuum suction from the vacuum groove 131. 143 is adsorbed on 143. On the stamper presser claw 141, a runner groove 130 connected to the spool 119 and through which the molten resin passes is provided. On the movable mold 129 facing the runner groove 130, a convex portion 131 that fits inside the groove 130 is provided, and the filling resin does not protrude from the runner groove 130 even if the cavity 117 is opened to some extent.

  On the movable mold 129 facing the stamper 118, an outer peripheral frame 123 for regulating the outer peripheral portion of the product is installed in a state that can be independently driven in the cavity opening / closing direction. The outer peripheral frame 123 is stepped, and the edge 123A regulates the outer peripheral part of the product. A groove 132 connected to the runner groove 130 is provided on one side of the outer peripheral frame 123 on the spool side, which is the filling start direction, and the molten resin is filled into the cavity 117 from the groove 132 after passing through the gate 144.

  In this embodiment, when the molten resin is filled, the mold clamping pressure is controlled so that the cavity thickness T is 3.0 mm as shown in FIG. Simultaneously with the start of filling, as described above, the supercritical fluid and its melt were introduced from the flow path 112 into the mold and cavity 117 by the pressure of the arrow 125 in FIG. At the same time, the solenoid valve 113 in FIG. 1 is opened, and only the supercritical fluid is introduced into the mold through the flow path 114, so that the movable abutting ring 122 and the back surface of the outer peripheral frame 123 are pressed by the pressure of the arrow 126 in FIG. And the supercritical fluid pressures 125 and 126 were brought into equilibrium. Further, since the springs 128 and 127 are provided on the back surfaces of the movable butting ring 122 and the outer peripheral frame 123, the components are abutted against the fixed mold 143 side by the spring force. Since the sealing performance is maintained even when the mold is opened by this mechanism, the high-pressure supercritical fluid does not leak from the mold, and the filling resin does not protrude from the outer peripheral frame 123 that regulates the outer periphery of the product.

  The supercritical fluid introduced by the pressure 125 as a counter pressure and the dissolved product thereof are filled in the cavity 117 through the passage hole 124 in the outer peripheral frame 123 and the clearance t between the stamper 118 and the outer peripheral frame 123. In this example, the clearance t was 10 μm.

  The melt resin impregnated with the supercritical fluid and its melt in the flow front part is a cavity opened as shown in FIG. 5 through the spool 119 as the screw 107 advances immediately after the shut-off nozzle 105 in FIG. 1 is opened. 117 is filled. FIG. 6 schematically shows the state of the resin being filled. In the flow front 133 of the molten resin 116 flowing in the direction of the arrow 134, the supercritical fluid and the substance 115 dissolved therein are caused by the fountain flow phenomenon, and the stamper 118 and the movable mold 129 Place it on the wall. The dissolved substance of the supercritical fluid previously impregnated in the resin and the same substance introduced as counter pressure are selectively arranged on the surface of the molded product with the same effect.

When the supercritical fluid is preliminarily permeated into the filled resin, the supercritical fluid or pressurized CO ₂ is introduced as a counter pressure, so that depressurization of the supercritical fluid inside the resin and accompanying foaming can be suppressed. Therefore, even when only the front part of the molten resin is impregnated with the supercritical fluid and the dissolved substance thereof at the time of plasticization, it is desirable to introduce the counter pressure of only the supercritical fluid into the cavity. In addition, when counter pressure is not used, heat insulation by forming a low thermal conductive material such as polyimide on the mold surface or stamper separation surface can also suppress the rise in resin viscosity and the pressure drop in supercritical fluid. desirable.

  In this embodiment, the uneven pattern of the stamper 118 schematically shown in FIG. 6 has a width W; 2 μm, W2: 5 μm, and a depth D: 30 μm. In this example, during injection filling, it seems that the pattern of high aspect ratio is not sufficiently transferred as shown in FIG. 6, but immediately after filling, the cavity opening amount T3.0 mm is reduced to 0.5 mm which is the product thickness. It was possible to transfer completely by compressing with a clamping pressure of 40 tons.

  In the molding method of the present embodiment, by opening the cavity at the time of filling, the flow resistance of the molten resin in the mold can be reduced, and the flow length in the cavity can be shortened. Furthermore, by compressing the volume of the cavity immediately after filling, the pressure of the supercritical fluid decompressed during injection filling can be increased again, and thereby the surface viscosity of the resin can be kept low. Furthermore, the supercritical fluid introduced by the counter pressure that tends to remain in the fine pattern can be penetrated into the molten resin. By these methods, even a difficult-to-mold material or a difficult-to-mold structure can be finely transferred, and the pressure distribution in the cavity becomes uniform.

In this embodiment, after injection compression, the solenoid valves 145 and 136 in FIG. 1 are opened to leak the CO ₂ inside the cavity and the resin, and further inside the mold, and solidify the molten resin in the mold. Then, the mold was opened and the product was taken out. It was confirmed that Pt complexes that were dissolved in the supercritical fluid and Pt fine particles from which organic substances were removed from the complex were arranged on the surface of the molded article produced in this example. It was also confirmed that the melt was hardly contained in the center of the molded product.

  In the present invention, after disposing a supercritical fluid solution such as a metal complex on the surface of the molded article by the above method, post-treatment such as heating or reduction reaction may be performed. No post-processing was performed before.

  In this example, electroless copper plating was performed on the molded product produced by the injection molding method by the following method. First, it was placed in a container containing an aqueous solution for electroless copper plating ("OPC700A" manufactured by Okuno Pharmaceutical Co., Ltd., 100 ml / liter + "OPC700B" manufactured by Okuno Pharmaceutical Co., Ltd., 100 ml / liter) and stirred for 60 minutes at room temperature to perform copper plating. After washing, electroless copper plating aqueous solution ("OPC Copper T1" manufactured by Okuno Pharmaceutical Co., Ltd. 60ml / liter + "OPC Copper T2" manufactured by Okuno Pharmaceutical Co., Ltd. 12ml / liter + "OPC Copper T3" manufactured by Okuno Pharmaceutical Co., Ltd. 100ml / Liter) was placed in a container with 60 ° C. and 120 minutes of stirring and air stirring to perform copper plating. After ultrasonic cleaning with pure water and methanol, a copper plating film having a thickness of 10 μm was formed on the entire surface of the molded product. Further, it was confirmed that the plating film had a uniform film thickness, no blistering, and an adhesion strength having no practical problem was obtained in the peel test.

  Further, as shown in the schematic diagram of FIG. 8, the surface on the pattern forming surface of the molded product shown in FIG. 8B is polished by 20 μm, and the convex portions are removed as shown in FIG. The remaining wiring pattern was formed. In the molded product in this example, it was confirmed that the wiring of electroless copper plating having a width of 2 μm was formed without omission. It was also confirmed that the insulation between adjacent wirings was good.

  Wiring by injection molding and electroless plating was performed in the same manner as in Example 1 except that the electroless plating after forming the molded product was performed as shown in FIG. In the molded product in this example, it was confirmed that the wiring of electroless copper plating having a width of 2 μm was formed without omission. It was also confirmed that the insulation between adjacent wirings was good.

Injection molding was carried out in the same manner as in Example 1 except that supercritical CO ₂ was impregnated in the molten resin other than the flow front part and the inside of the molded product was made into a foam. In this example, an internal foam was produced as follows.

First, the supercritical CO ₂ is introduced into the vents 120 of the screw 107 by opening the solenoid valve 110 from the inlet 109 of the supercritical fluid illustrated in FIG. 1, except the front portion does not dissolve a metal complex supercritical CO ₂ Was impregnated into the molten resin. The transfer by injection filling and injection compression was carried out in the same manner as in Example 1, and then the high pressure clamping force was reduced to 5 tons and the inside was foamed without opening the CO ₂ in the cavity to the atmosphere to obtain a molded product. The supercritical fluid introduced into the mold was released to the atmosphere by opening the solenoid valve 136 simultaneously with foaming.

In the molded product of this example, the pressure distribution in the cavity was made uniform due to the effect of the above-described injection compression, so that a fine foam that was uniform over the entire surface was obtained. Further, when the molded product in this example was subjected to electroless plating in the same manner as in Example 1 to produce a wiring pattern, it was confirmed that the wiring was formed without omission. It was also confirmed that the insulation between adjacent wirings was good.
(Comparative example)
Injection molding and electroless plating were performed in the same manner as in Example 1 except that the Pt complex, which was a dissolved material, was not dissolved in the supercritical fluid. In the molded product of this comparative example, electroless plating could not be performed.

FIG. 10 shows a cross-sectional structural view of the main part of the mold and molding apparatus used in this example. The supercritical fluid in the present invention is arbitrary, but CO ₂ was used in this example. In the present invention, any substance can be dissolved in the supercritical fluid. In this example, bis (acetylacetonate) palladium, which is a Pd complex, was used.

Method of dissolving the substance in the supercritical fluid is arbitrary, in the present embodiment, after the supercritical state of CO ₂ supplied from the CO ₂ cylinder 201 at a supercritical fluid generating device 202, mixing tank 203 The organic substance to be dissolved in the supercritical fluid supplied from the storage container 204 was dissolved to a predetermined concentration. In this embodiment, the mixing tank 203 was maintained in an atmosphere of 100 ° C. and 12 MPa.

  In the present invention, the method for introducing the supercritical fluid in which the organic substance is dissolved into the mold is arbitrary, but in the present embodiment, the fine flow in the fixed mold 214 passes through the flow path 216 by opening the electromagnetic valve 207. The solution was injected from the passage 206 into the cavity 205 formed by the fixed mold 214 and the movable mold 215. In this embodiment, the diameter of the fine channel 206 in the fixed mold 214 is Φ0.3 mm.

  Next, the injection molding method in the present embodiment will be described in detail with reference to FIGS. First, a known method is used for plasticizing and filling. In FIG. 10, resin pellets (not shown) filled in the plasticizing cylinder 220 from the hopper 217 via the band heater 218 by the rotation of the screw 219 are plasticized and melted and measured in front of the screw 219. As the internal pressure in front of the screw 219 increases, the screw 219 moves backward. At the time of injection, the molten resin measured by the advancement of the screw 219 is filled in the cavity 205 of the mold. The cavity 205 is formed by a fixed mold 214 and a movable mold 215 whose temperatures are controlled by a temperature control circuit (not shown), and the molten resin is filled through the nozzle 221 and the mold spool 222.

  In the present invention, usable thermoplastic resins are arbitrary, but in this example, polyether imide (Ultem 1010 manufactured by GE Plastics) having a glass transition temperature of about 230 ° C. was used. In this example, the temperature of the plasticizing cylinder was 380 ° C. The medium temperature in the temperature control circuit flowing in the mold was set to 125 ° C.

  The surface of the fixed mold 214 in this embodiment is provided with irregularities that lead to the flow path 206. In the present invention, the uneven shape of the mold surface and its pitch and depth are arbitrary, but in this embodiment, a line and space groove pattern 209 having a constant depth and random pitch and width is provided. The depth of the groove was 2 mm, the width was 0.9 mm, and the pitch was a minimum of 0.6 mm.

FIG. 11 shows an enlarged view of a portion C in FIG. 10 of the mold cavity 205 provided with the groove pattern 209. Hereinafter, a method of filling the groove 209 with resin will be described with reference to FIG. The cavity 205 before filling in FIG. 11A is filled with the molten resin 212 as shown in FIG. 11B. At this time, since the internal pressure of the resin is not sufficiently high in the primary filling, the mold groove 209 cannot be sufficiently filled and the convex portion 210 is formed. In this unfilled state, the supercritical fluid 208 in which the organometallic complex was dissolved was injected into the groove 209. At this time, the supercritical fluid and its melt were controlled so as not to leak from the groove 209 by the resin internal pressure and the mold clamping pressure. Since the supercritical CO ₂ comes into contact with the molten resin, the resin protrusion 210 in the groove 209 is softened, so that the metal complex 213 more easily penetrates into the resin. Further, as shown in FIG. 11D, the groove 209 is almost completely filled with the resin by increasing the holding pressure and the mold clamping pressure. Thereby, the organometallic complex 213 is arranged only on the surface of the convex portion 210 of the molded body.

  In the present invention, after a supercritical fluid solution such as a metal complex is placed on the surface of the molded article by the above method, post-treatment such as heating or reduction reaction may be performed. The ligand of the organometallic complex was completely removed by allowing it to stand for 1 hour. In this example, electroless copper plating was performed on the molded product produced by the injection molding method by the following method. First, it was placed in a container containing an aqueous solution for electroless copper plating ("OPC700A" manufactured by Okuno Pharmaceutical Co., Ltd., 100 ml / liter + "OPC700B" manufactured by Okuno Pharmaceutical Co., Ltd., 100 ml / liter) and stirred for 60 minutes at room temperature to perform copper plating. After washing, electroless copper plating aqueous solution ("OPC Copper T1" manufactured by Okuno Pharmaceutical Co., Ltd. 60ml / liter + "OPC Copper T2" manufactured by Okuno Pharmaceutical Co., Ltd. 12ml / liter + "OPC Copper T3" manufactured by Okuno Pharmaceutical Co., Ltd. 100ml / Liter) was placed in a container with 60 ° C. and 120 minutes of stirring and air stirring to perform copper plating. After ultrasonic cleaning with pure water and methanol, a copper plating film having a thickness of 10 μm was formed on the entire surface of the molded product. Further, it was confirmed that the plating film had a uniform film thickness, no blistering, and an adhesion strength having no practical problem was obtained in the peel test. Moreover, it was confirmed by the resistance measurement conducted to the wiring that the low resistance wiring was formed without disconnection. It was confirmed that the insulation between adjacent wirings was also good.

  In this example, injection molding was performed using the same molding apparatus as in Example 4 except that the mold shown in FIG. 12 in which the uneven pattern in the mold was provided on the Ni stamper was used. The mold is formed of a fixed mold 214 and a movable mold 215, and a Ni stamper 228 is held on the movable mold 215 by a stamper holding frame 225. The stamper pressing frame 225 has a frame shape, and is sealed by a fixed mold 214 and mold clamping to form a plate-like cavity 205.

  The supercritical fluid and the organic substance dissolved in the supercritical fluid are introduced into the stamper separation surface through the channel 216.

  Next, a stamper shape and a molding method in the present embodiment will be described with reference to FIGS. 13A and 13B which are enlarged views of a portion D shown in FIG.

  The stamper 228 in this example was manufactured as follows. First, patterning was performed on a resist provided on a silicon substrate by photolithography, and dry etching was performed using the resist as a mask to produce a silicon mold having an uneven shape with a high aspect ratio. Next, a Ni stamper 228 having a thickness T of 0.3 mm was manufactured by electroforming in the same manner as the optical disk stamper manufacturing process. The pattern width L in the groove 209 in the stamper 228 was 0.05 mm, and the depth d was 0.1 mm. Then, a hole 226 having a diameter of 0.1 mm and a depth of 0.2 mm was provided at an appropriate material location by machining from the back surface of the stamper 228. The hole 226 was provided so as to communicate with the isolated portion of each groove 209. For example, in the groove group 229, each groove portion communicates with the same hole 226. The holes 226 can be formed with finer and deeper holes by laser processing, and can cope with pattern miniaturization. Even if the pattern width L is on the order of submicron, the depth of the hole 226 is the same, and the diameter can be formed to Φ10 μm or less.

  Molding was performed as follows. After injection in the same manner as in Example 4, a supercritical fluid in which the metal complex was dissolved was injected from the flow path 216 into the mold. As shown in FIG. 13B, the supercritical fluid pushes up the stamper 228 and the molten resin 212 having a high elastic modulus, creates a slight clearance 227 on the back surface of the stamper, and permeates from the resin protrusion 210 through the hole 226. A fine slit may be formed on the mold surface on the back of the stamper, and the slit may be used as a passage for the supercritical fluid. Thereafter, the supercritical fluid was depressurized and the holding pressure of the resin was increased in the same manner as in Example 1, thereby bringing the stamper 228 and the movable mold 215 into close contact with each other and completing the transfer at the convex portion 210 and the injection of the metal complex.

  According to the molding method of the present embodiment, the wiring circuit can be easily changed by stamping the wiring formation pattern. Further, by reducing the thickness of the stamper, the curved surface portion of the mold can also hold the stamper, and the formation of a three-dimensional circuit is facilitated. In addition, since a fine patterning technique such as photolithography can be used for patterning the stamper, a submicron order fine pattern can be formed.

  As mentioned above, although embodiment of this invention was described, various deformation | transformation and a change are possible for this invention within the range of the summary. For example, in FIG. 11, the groove portion 209 is filled with resin, and as a result, a convex portion is formed on the molded product, and the surface of the convex portion is modified, but as shown in FIG. It is possible to selectively modify the surface of the molded product without unevenness. Here, FIG. 14 is a modification of the embodiment shown in FIG. In FIG. 14, a groove portion 209a of a mold including a fixed mold 214a and a movable mold 215a is disposed at a specific position of a flat molten resin (or molded product) 212a. By introducing a supercritical fluid in which the metal complex is dissolved as indicated by the arrow of the groove 209a and adjusting (for example, reducing) the pressure and / or temperature during injection molding, the metal complex is locally applied to the surface of the molded product. Can be placed.

It is principal part sectional drawing of the injection molding apparatus of one Example of this invention. It is a flow of the electroless plating method on the plastic surface in the present invention. In the method shown in FIG. 2, it is the flow of the fine plating wiring method to the plastic surface. It is the A section enlarged view shown in FIG. It is sectional drawing for demonstrating operation | movement of the structure shown in FIG. It is an expansion schematic diagram for demonstrating the mode of the flow front at the time of injection filling of the B section shown in FIG. It is an expanded sectional view of the injection mechanism of the injection molding apparatus shown in FIG. It is a partial expanded sectional view of the metal mold | die for demonstrating an example of the electroless-plating method shown in FIG. It is a partial expanded sectional view of the metal mold | die for demonstrating another example of the electroless-plating method shown in FIG. It is sectional drawing of the injection molding apparatus of another Example of this invention. It is a partial expanded sectional view of the injection molding apparatus shown in FIG. It is a fragmentary sectional view of the injection molding device of another embodiment of the present invention. It is a partial expanded sectional view of the injection molding apparatus shown in FIG. It is a fragmentary sectional view of the metal mold | die which shows the modification of the Example shown in FIG. It is a flowchart which shows the conventional electroless plating method. It is a flowchart for demonstrating the conventional plating wiring method.

Explanation of symbols

101 Supercritical Fluid Generator 102 Storage Container 103 Mixing Tank 104 Metal Fine Particle 105 Shutoff Nozzle 112 Channel 115 Supercritical Fluid Dissolved Material 117 Cavity 133 Flow Front 138 Electroless Plating Layer 205 Cavity 206 Fine Channel 208 Supercritical Fluid 209 Groove 210 Projection 212 Molten resin 213 Organometallic complex 214 Fixed mold 215 Movable mold 220 Plasticizing cylinder 226 Hole 228 Stamper

Claims (8)

A method for producing a molded product from a thermoplastic resin,
A first introduction step of introducing the thermoplastic resin as a molten resin into a molding portion for molding the molded article;
A second introduction step of introducing a supercritical fluid in which the organometallic complex is dissolved into the molded portion;
Solidifying the molten resin and placing a metal element on the surface of the molded article.   2. The method according to claim 1, wherein the second introducing step introduces a supercritical fluid in which the organometallic complex is dissolved at a specific position in the molding portion.   3. The method according to claim 2, further comprising the step of adjusting the pressure and / or temperature of the molded part.   The method according to any one of claims 1 to 3, further comprising a step of forming a plating layer at a site where the surface of the molded article is modified with the metal element by electroless plating. The molded body includes an uneven portion on the surface,
The method according to claim 4, further comprising a step of removing the protrusion after the plating layer forming step. The molded body includes an uneven portion on the surface,
The method according to claim 4, further comprising a step of removing the convex portion of the portion before the plating layer forming step. Compressing the molten resin after the first and second introduction steps;
The method according to claim 1, further comprising the step of foaming the molten resin after the compression step. An apparatus for producing a molded article of a thermoplastic resin,
A molding part for molding the molded article;
A first introduction mechanism that introduces the thermoplastic resin as a molten resin into the molded part; and a second introduction mechanism that introduces a supercritical fluid in which an organometallic complex is dissolved into the molded part. Device to do.

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