JP2004026986A - Method for modifying surface of organic polymeric substrate - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To establish a temperature and pressure condition which allows a catalyst for electroless plating to be present in the vicinity of the surface of an organic polymeric substrate when the catalyst for electroless plating is fixed to an organic polymeric substrate by a high spressure fluid, without damaging the organic polymeric substrate and wasting the catalyst. <P>SOLUTION: In a method for fixing an organometal compound to the surface of the organic polymeric substrate by bringing the organic polymeric substrate into contact with the high pressure fluid containing the organometal compound batchwise in a high pressure container, either one of carbon dioxide, nitrogen and a 4C or less hydrocarbon is used as the high pressure fluid. When the critical pressure of the high pressure fluid is Pc<SB>1</SB>(MPa), the temperature T<SB>1</SB>(K) and pressure P<SB>1</SB>(MPa) of the high pressure fluid are controlled so as to satisfy formulas (1) and (2) : 313 ≤T<SB>1</SB>≤ 473 (1) and 0.8Pc<SB>1</SB>≤ P<SB>1</SB>≤ 5.0Pc<SB>1</SB><SP></SP>(2) to perform the above fixing process. <P>COPYRIGHT: (C)2004,JPO

Description

[0001]
TECHNICAL FIELD OF THE INVENTION
In the present invention, when plating an organic polymer substrate such as a plastic (resin molded article) or a rubber or a thermoplastic elastomer by an electroless plating method, the pretreatment includes degreasing, washing, and etching in a usual plating pretreatment. The present invention relates to a method for modifying the surface of an organic polymer substrate so that plating can be performed in a simple process without the need for such a process. The surface of an organic polymer substrate is subjected to a catalyst application step under high pressure.
[0002]
[Prior art]
Electroless plating is performed by the reduction action of a catalyst on the surface of a material, and can be plated on various materials from metals to nonmetals. Conventionally, it has been used for metallizing organic polymer substrates such as plastics. It is used as a plating method. When performing electroless plating on an organic polymer substrate, a plating catalyst must be applied to the surface of the organic polymer substrate by a method such as adsorption in order to deposit a plating metal on the surface of the organic polymer substrate. . For this catalyst application, a mixed colloidal solution of palladium ion and tin ion called a catalyst is often used. Simply coating and drying the colloid solution on the surface of the organic polymer substrate does not exhibit catalytic activity because the tin surrounds the palladium, and therefore, after the catalyst is applied, an accelerator step of removing the tin with sulfuric acid, hydrochloric acid or the like is performed.
[0003]
Various pretreatments are performed in addition to the catalyst application and the accelerator process in order to improve the adhesion of the plating layer. For example, chemical pretreatment such as degreasing / cleaning treatment and application / drying of an anchor coat agent. In addition, in the electroless plating method, since a plating layer is formed evenly particularly on an uneven surface, chemical etching with an acid or an alkali is often performed. Further, the surface is roughened by an electrical method such as corona discharge or plasma discharge, or a physical method such as sand blast.
[0004]
However, in the case of the above pretreatment method, for example, if it is a chemical method, it is necessary to recover an organic solvent, an acid, an alkali, and the like. In addition, a washing and neutralizing treatment for removing these solutions from the organic polymer substrate Is required. In the case of an electrical method, expensive equipment is required. Further, the physical method is inexpensive in terms of cost, but there is a problem that sand or the like is inevitably mixed into the organic polymer substrate.
[0005]
Since the pretreatment process of the electroless plating as described above is complicated and environmentally unfavorable, Japanese Patent Application Laid-Open No. 2001-316832 discloses an attempt to etch a plastic and provide a plating catalyst with a supercritical fluid. Has been described. According to this technique, the plating catalyst is injected and fixed to the vicinity of the plastic surface in combination with the etching effect of the supercritical fluid on the plastic surface.
[0006]
However, in the method described in the examples of this publication, since supercritical carbon dioxide is passed through the high-pressure vessel loaded with the organometallic compound and the organic polymer substrate, it was not able to adhere to the organic polymer substrate well. Plating catalysts are discharged to the outside of the high-pressure vessel together with carbon dioxide, leaving a problem that expensive plating catalysts are wasted. Further, the activation of the catalyst is performed by contact with an acid solution such as sulfuric acid or hydrochloric acid, and the problem that the above-mentioned washing / neutralization process is required still remains.
[0007]
Further, in the above publication, although the compound used as a supercritical fluid is too wide, the temperature and pressure conditions suitable for the treatment are described only in the case of carbon dioxide and very widely (see the above publication [ 0014]), it was necessary to find optimal conditions for more efficient processing.
[0008]
[Problems to be solved by the invention]
Therefore, the present inventors have conducted intensive studies and found that when carbon dioxide was used as a supercritical fluid, the temperature and pressure conditions described in the above-mentioned gazettes caused too much damage to plastics and caused hydrolysis. Have been found to include conditions that would cause them to be compromised.
[0009]
Therefore, in the present invention, when the catalyst for electroless plating is fixed to the organic polymer substrate using a high-pressure fluid, the catalyst is not damaged and the surface of the organic polymer substrate is not wasted without damaging the organic polymer substrate. The task was to establish temperature and pressure conditions that can exist in the vicinity.
[0010]
[Means to solve the problem]
The first embodiment of the present invention fixes an organometallic compound on the surface of an organic polymer substrate by bringing an organic polymer substrate and a high-pressure fluid containing an organometallic compound into contact in a batch system in a high-pressure vessel. In the method,
As the organometallic compound, an organometallic complex containing one or more metals selected from the group consisting of Ni, Cu, Cr, Pt, Au, Ag, Pd and Fe is used,
As a high-pressure fluid, while using any of carbon dioxide, nitrogen and hydrocarbons having 4 or less carbon atoms,
When the critical pressure of the high-pressure fluid is Pc ₁ (MPa), the temperature T ₁ (K) and the pressure P ₁ (MPa) of the high-pressure fluid are controlled so as to satisfy the following equations (1) and (2), respectively. Then, the contact step is performed.
313 ≦ T ₁ ≦ 473 (1)
0.8Pc ₁ ≦ P ₁ ≦ 5.0Pc ₁ (2)
[0011]
Since carbon dioxide, nitrogen and hydrocarbons having 4 or less carbon atoms do not damage the organic polymer substrate very much, the use of a high-pressure fluid that satisfies the above (1) and (2) allows the organic polymer substrate to be used. The surface modification of the substrate can be performed efficiently. Further, by performing the surface modification in a batch system, it was possible to fix a necessary and sufficient amount to the organic polymer substrate for the electroless plating in the subsequent step without using a large amount of expensive organometallic compounds.
[0012]
In the second embodiment of the present invention, the organometallic compound is the same as above, but using water or alcohol as the high-pressure fluid,
When the critical temperature of the high-pressure fluid is Tc (K) and the critical pressure of the high-pressure fluid is Pc ₂ (MPa), the temperature T ₂ (K) and the pressure P ₂ (MPa) of the high-pressure fluid are expressed by the following equation (3), respectively. The contact step is performed while controlling so as to satisfy the conditions (4) and (4).
0.6Tc ≦ T ₂ ≦ 1.1Tc (3)
0.05Pc ₂ ≦ P ₂ ≦ 1.5Pc ₂ (4)
[0013]
Water or alcohol is liable to damage the organic polymer substrate, such as hydrolysis, so that the surface modification is performed under temperature and pressure conditions satisfying the above (3) and (4).
[0014]
In any of the above methods, after the contacting step, a step of heating the organic polymer substrate to which the organometallic complex is fixed on the surface to decompose the organometallic complex to generate an active metal simple substance on the surface of the organic polymer substrate. Alternatively, the high-pressure fluid is discharged after the contacting step, and in the presence of a reducing gas, the organic polymer substrate on which the organometallic complex is fixed is heated to decompose the organometallic complex, thereby decomposing the organometallic complex. It is preferable to include a step of generating a single active metal. This step activates the plating catalyst.
[0015]
The present invention includes a plating layer-containing organic polymer substrate obtained by forming an electroless plating layer on the surface of the organic polymer substrate to which the simple active metal is fixed. The high-pressure apparatus for performing the surface modification method of the present invention includes a high-pressure vessel, high-pressure fluid supply means for supplying a high-pressure fluid to the high-pressure vessel, and stirring means for stirring the inside of the high-pressure vessel. High pressure devices are also included in the present invention.
[0016]
BEST MODE FOR CARRYING OUT THE INVENTION
In the first embodiment of the present invention, any one of carbon dioxide, nitrogen, and a hydrocarbon having 4 or less carbon atoms is used as the high-pressure fluid,
When the critical pressure of the high-pressure fluid is Pc ₁ (MPa), the temperature T ₁ (K) and the pressure P ₁ (MPa) of the high-pressure fluid are controlled so as to satisfy the following equations (1) and (2), respectively. .
313 ≦ T ₁ ≦ 473 (1)
0.8Pc ₁ ≦ P ₁ ≦ 5.0Pc ₁ (2)
[0017]
Since carbon dioxide, nitrogen and hydrocarbons having 4 or less carbon atoms do not damage the organic polymer substrate very much, the temperature range is from 313 K (40 ° C.) to 473 K (200 ° C.) and critical in 5.0Pc ₁ things pressure range from 0.8Pc ₁ pressure Pc ₁ near, it is possible to perform surface modification treatment of the organic polymer base. When the temperature and pressure are below the lower limits, the etching effect is not sufficiently exhibited, and a necessary and sufficient amount of the organometallic compound (organometallic complex) is not injected into the organic polymer substrate. On the other hand, when the temperature and the pressure exceed the above upper limits, a hydrolysis reaction and a deterioration reaction of the organic polymer substrate occur, and the strength and the like of the organic polymer substrate decrease, which is not preferable.
[0018]
In the first embodiment, carbon dioxide, nitrogen, or a hydrocarbon having 4 or less carbon atoms is used as the high-pressure fluid. Here, the critical temperature of carbon dioxide is 304 K, the critical pressure is 7.3 MPa, the critical temperature of nitrogen is 126 K, and the critical pressure is 3.4 MPa. In addition, those usable as hydrocarbons having 4 or less carbon atoms include ethylene (critical temperature 282 K, critical pressure 5.0 MPa), propylene (critical temperature 365 K, critical pressure 4.6 MPa), methane (critical temperature 191 K, critical pressure 4.6 MPa), ethane (critical temperature 305 K, critical pressure 4.9 MPa), propane (critical temperature 370 K, critical pressure 4.2 MPa) and the like.
[0019]
As the organometallic compound, in both the first embodiment and the second embodiment, those useful as a catalyst for electroless plating are preferable, and are selected from the group consisting of Ni, Cu, Cr, Pt, Au, Ag, Pd and Fe. Organometallic complexes containing one or more metals. Specifically, dibenzene chromium, nickelocene (biscyclopentadienyl nickel), vanadium acetylacetonate, C ₁₀ H ₁₈ Pt and the like can be mentioned.
[0020]
As the organic polymer substrate, in addition to so-called plastics, rubbers and thermoplastic elastomers are used. The shapes of the organic polymer substrates are not limited to various shapes as they are (plate-like, container-like), but also fibrous, powdery, Any material having a certain shape such as a particle shape can be used. The molding method, spinning method, and granulation method are not particularly limited.
[0021]
Specific examples of the organic polymer include general-purpose resins such as polyolefin resins such as polyethylene, polypropylene and polymethylpentene; styrene resins such as polystyrene and ABS; polyester resins such as polyethylene terephthalate; and halogen-containing resins such as polyvinyl chloride. Thermoplastic resins; special resins such as liquid crystal polymers; engineering plastics such as polyacetal, polycarbonate, aliphatic or aromatic polyamide, and polyphenylene ether can be used. Further, a cured product of a curable resin known as a molding material such as an epoxy resin, a phenol resin, a polyurethane resin, an unsaturated polyester resin, and an oligoacrylate can also be used.
[0022]
Examples of the rubber include natural rubber and synthetic rubbers such as SBR, NBR, EPM, and EPDM. Examples of the thermoplastic elastomer include styrene-based elastomers such as SEPS, and known thermoplastic elastomers such as olefin-based, polyester-based, and urethane-based elastomers.
[0023]
The organic polymer substrate may be a composite of different materials, for example, a material containing a reinforcing fiber or an inorganic filler, or a material other than a polymer material partially laminated. Various laminated structures and the like can be used.
[0024]
In the second embodiment of the present invention, when water or alcohol is used as the high-pressure fluid and the critical temperature of the high-pressure fluid is Tc (K) and the critical pressure of the high-pressure fluid is Pc ₂ (MPa), the temperature of the high-pressure fluid is The contacting step is performed by controlling T ₂ (K) and pressure P ₂ (MPa) so as to satisfy the following expressions (3) and (4), respectively.
0.6Tc ≦ T ₂ ≦ 1.1Tc (3)
0.05Pc ₂ ≦ P ₂ ≦ 1.5Pc ₂ (4)
[0025]
Water and alcohol cause large damage to the organic polymer substrate. The temperature and pressure conditions exceeding 1.1Tc and 1.5Pc _2, there is a possibility that the organic polymer substrate is deteriorated decomposition, it is necessary to perform surface modification at low temperature and low pressure conditions than the upper limit. However, if the temperature is too low and the pressure is too low, the effect of etching the organic polymer substrate and the effect of fixing the organic metal compound are not exhibited.
[0026]
The critical temperature of water is 647K and the critical pressure is 22 MPa. Alcohols that can be used include methanol (critical temperature 513 K, critical pressure 8 MPa), ethanol (critical temperature 516 K, critical pressure 6 MPa), and the like.
[0027]
Next, specific embodiments of the first and second surface modification methods of the present invention will be described with reference to the drawings. FIG. 1 shows an embodiment of a high-pressure processing apparatus for performing the surface modification method of the present invention. A high-pressure fluid supply unit 1 includes a high-pressure fluid medium storage tank 10 and a pressure pump 11 which are essential components. In addition, if necessary, a supercooler or a heater may be added. When liquefied or supercritical carbon dioxide is used as the high-pressure fluid, a high-pressure liquefied carbon dioxide can be obtained by using a reservoir in which the liquefied carbon dioxide is stored as the storage tank 10 and pressurizing with the pressurizing pump 11. In the case where another fluid is used as the high-pressure fluid, a known method such as supplying a liquefied material directly from a cylinder or supplying a gas via a subcooler can be adopted.
[0028]
The surface modification method of the present invention is performed by the following method. First, an organic polymer substrate and an appropriate amount of an organometallic compound are placed in a container (high-pressure container) 3 having a stirrer 4 shown in FIG. Seal. The high pressure valve 6 is closed. The high-pressure valve 2 is opened, high-pressure fluid is fed by the pressure pump 11, and when the pressure in the container 3 reaches a predetermined pressure, the high-pressure valve 2 is closed to perform surface modification. By stirring the inside of the container 3 with the stirrer 4, the organometallic compound is efficiently fixedly impregnated into the organic polymer substrate. Temperature control during the surface modification is performed in the constant temperature bath 5. By performing the batch method, it is possible to fix a necessary and sufficient amount to the organic polymer substrate for electroless plating in a later step without using a large amount of expensive organometallic compounds.
[0029]
The time required for the surface modification treatment should be appropriately changed according to the surface area of the organic polymer substrate. However, the longer the time, the greater the damage to the organic polymer substrate. It is more preferably within 1 hour, most preferably 5 to 40 minutes.
[0030]
After the surface modification treatment, the high-pressure valve 6 is opened, and the pressure inside the container 3 is reduced. If necessary, the organometallic compound and the fluid can be separated by the post-treatment means 7. In the illustrated example, the post-processing means 7 including the high-pressure valve 71 and the recovery tank 72 is shown. As the post-processing means 7, for example, a flash tank, a distillation column, a filtering device, a cyclone, or the like can be used. When the pressure inside the container 3 is reduced to the atmospheric pressure, the organic polymer substrate may be taken out.
[0031]
After the surface modification treatment, the activation treatment of the organometallic compound can be performed using the high-pressure vessel 3. In the activation treatment, a method of performing thermal decomposition of the organometallic compound by heating the inside of the container 3 without decompressing the inside of the high-pressure fluid while enclosing the inside, and reducing the pressure inside the high-pressure container 3 to such an extent that the fluid can maintain a fluid state. Then, a method of thermally decomposing the organometallic compound by heating in the presence of the low-pressure fluid, completely removing the high-pressure fluid by depressurization, subsequently introducing a reducing gas into the vessel 3, and then heating the organometallic compound. Any of the methods for thermally decomposing a compound can be adopted as a preferable method. Heating in the presence of a high-pressure or low-pressure fluid is not preferable because an oxidizing atmosphere oxidizes the metal, which is not preferable. Therefore, the introduction of a reducing gas is performed depending on the type of organometallic compound. However, this is because thermal decomposition easily proceeds. By thermally decomposing the organometallic compound by any of the above methods, only the metal is fixed on the surface of the organic polymer substrate, and the catalytic activity for electroless plating is developed. After the activation treatment, electroless plating may be performed by a known method. As the metal for plating, Cu, Ni, Co, etc. and alloys thereof can be used.
[0032]
FIG. 2 shows an example of an apparatus provided with high-pressure fluid circulation means 8 as stirring means outside the high-pressure vessel 3. The high-pressure fluid circulating means 8 includes a high-pressure valve 81, a tank 82 and a pump 84, a connecting pipe 83 connecting the tank 82 and the pump 84, and a connecting pipe 85 connecting the pump 84 and the high-pressure container 3. . A circulating means such as circulating a fluid without using the pump 84 by cooling or heating the tank 82 and the connecting pipes 83 and 85 with a cooler or a heater (not shown) may be adopted.
[0033]
The batch operation is performed by the high-pressure vessel 3 and the circulating means 8, and by circulating the high-pressure fluid from the bottom of the high-pressure vessel 3, the high-pressure fluid exerts a stirring action in the vessel 3 and also circulates the organometallic compound. Therefore, a small amount of the organometallic compound can be effectively used.
[0034]
In addition, the tank 82 can prevent an excessive amount of the organometallic compound from being introduced into the high-pressure container 3 by keeping the organometallic compound mixed without being dissolved in the high-pressure fluid in the tank 82. . Further, in a normal surface modification treatment operation, in view of safety, the organic metal compound is used in a larger amount than the amount to be fixed to the polymer substrate, but the high pressure fluid in which the excess organic metal compound is dissolved in the tank 82 is used. By storing, the organometallic compound can be effectively used at the time of the next batch operation, waste is eliminated, and the operation of recovering the organometallic compound from the high-pressure fluid for each batch operation becomes unnecessary.
[0035]
In the case of the batch operation using any one of the devices shown in FIGS. 1 and 2, when the pressure inside the container 3 decreases below a predetermined pressure, a high-pressure fluid may be additionally supplied as appropriate.
[0036]
【Example】
Hereinafter, the present invention will be described in more detail with reference to the following examples. However, the following examples do not limit the present invention, and modifications that do not depart from the gist of the present invention are included in the present invention.
[0037]
Experimental example 1
Using the apparatus shown in FIG. 1, 0.2 g of an organoplatinum complex (C ₁₀ H ₁₈ Pt) was put in the container 3 together with a polypropylene plate (50 mm × 15 mm × 3 mmt), and the container 3 was sealed. Carbon dioxide was supplied from the storage tank 12 to the inside of the container 3 by the pump 11, and the temperature was set to 120 ° C. and the pressure was set to 30 MPa. Thereafter, the liquid supply by the pump 11 was stopped, and the experiment conditions were maintained for 1 hour while stirring with the stirrer 4 in a batch system. Thereafter, the pressure inside the container 3 was reduced to the atmospheric pressure by releasing carbon dioxide through the high-pressure valve 6, and the polypropylene plate was taken out. As a result of analyzing the surface of the polypropylene plate using EPMA, it was confirmed that the organoplatinum complex was uniformly and densely distributed on the surface layer of the polypropylene plate.
[0038]
Experimental example 2
Using the same polypropylene plate and organic platinum complex as in Experimental Example 1, a surface modification treatment was performed in the same manner as in Experimental Example 1 at a temperature of 120 ° C. and a pressure of 30 MPa. After performing the batch treatment for 3 hours, the temperature of the high-pressure vessel 3 was increased to 180 ° C., and the organoplatinum complex was thermally decomposed. Thereafter, the pressure inside the container 3 was reduced to the atmospheric pressure, and the polypropylene plate was taken out. As a result of analyzing the polypropylene plate surface using EPMA, it was confirmed that Pt was distributed at a high density in the polypropylene plate surface layer.
[0039]
Experimental example 3
Using carbon dioxide as the high-pressure fluid and dibenzenechromium as the organometallic compound, the same experiment as in Experimental Example 1 was performed on various organic polymer plates. The conditions for the surface modification treatment were set within a range satisfying the above-mentioned expressions (1) and (2). As a result of analysis by EPMA, all organic polymer substrates used in the experiments, namely, polypropylene, polyethylene terephthalate, nylon 6, polycarbonate, polyacetal, polyacrylonitrile, polymethyl methacrylate, polyvinyl acetate, epoxy resin, It was confirmed that dibenzenechromium was fixed.
[0040]
Experimental example 4
Various organic polymer substrate surface modification experiments were performed in the same manner as in Experimental Example 3 except that an organic nickel complex (nickelocene) was used as the organometallic compound. As a result of the analysis by EPMA, the surface of all the organic polymer substrates used in the experiments, ie, polyethylene, polybutylene terephthalate, nylon 6, polycarbonate, polyacetal, polytetrafluoroethylene, polymethyl methacrylate, and polyvinyl acetate, were observed. It was confirmed that nickelocene was fixed.
[0041]
Experimental example 4
A surface modification experiment of a polypropylene plate was performed in the same manner as in Experimental Example 1 except that various organic complexes each containing Cu, Pt, Au, Ag, Pd, and Fe were used as the organometallic compound. As a result of analysis by EPMA, it was confirmed that all the organometallic compounds used in the experiment were fixed on the surface of the polypropylene plate.
[0042]
Experimental example 5
The same treatment as in Experimental Example 4 was performed using nitrogen and a hydrocarbon (ethane, ethylene, propane, propylene) as the high-pressure fluid and using nickelocene as the organometallic compound. It was confirmed that nickelocene was fixed on the surfaces of all the organic polymer substrates used in Experimental Example 4.
[0043]
Experimental example 6
Using water or methanol as the high-pressure fluid, surface modification of the polyimide plate with nickelocene was performed. The temperature and pressure conditions were set so as to satisfy the above-mentioned equations (3) and (4). The reaction time was 5 minutes to 1 hour. In each case of water and methanol, it was confirmed that nickelocene was fixed on the surface of the polyimide plate.
[0044]
Experimental example 7
Using carbon dioxide as the high-pressure fluid, surface modification of the polytetrafluoroethylene plate with nickelocene was performed in the same manner as in Experimental Example 1. The experiment was continued for 1 hour at a temperature of 120 ° C. and a pressure of 20 MPa. Thereafter, the pressure was reduced to atmospheric pressure, carbon dioxide was released from the container 3, hydrogen was supplied, the temperature was raised to 180 ° C. in a state where the inside of the container 3 was in a reducing atmosphere, and the temperature was maintained for about 10 minutes. Thereafter, the container was opened, and the polytetrafluoroethylene to which nickel had been fixed was taken out.
[0045]
Subsequently, electroless plating was performed. After using “C200LT” as a Cu plating solution and plating at about 40 ° C. for 10 minutes, washing and drying were performed. A glossy Cu plating film was formed on the polytetrafluoroethylene surface.
[0046]
Comparative Experimental Example Surface modification of a polyurethane plate with nickelocene was performed using carbon dioxide as a high-pressure fluid. The conditions were 450 ° C. and 30 MPa. After continuing the experiment for one hour, the pressure was reduced and the polyurethane plate was taken out, and the polyurethane was decomposed.
[0047]
【The invention's effect】
In the present invention, in performing the surface modification treatment for activating the organic polymer substrate with the organic metal compound performed before the electroless plating of the organic polymer substrate, the organic polymer substrate is not strongly damaged. We have succeeded in finding the optimum treatment conditions for carbon dioxide, nitrogen, and hydrocarbons having 4 or less carbon atoms, which are not to be given, and the optimum treatment conditions for water or alcohol that easily damages the organic polymer substrate such as hydrolysis. Therefore, the surface modification of the organic polymer substrate can be performed efficiently. Further, by performing the surface modification in a batch system, it was possible to fix a necessary and sufficient amount to the organic polymer substrate for the electroless plating in the subsequent step without using a large amount of expensive organometallic compounds.
[Brief description of the drawings]
FIG. 1 is a schematic explanatory view showing an example of an apparatus for performing a surface modification method of the present invention.
FIG. 2 is a schematic explanatory view showing another example of an apparatus for performing the surface modification method of the present invention.
[Explanation of symbols]
REFERENCE SIGNS LIST 1 high-pressure fluid supply means 11 high-pressure pump 3 high-pressure vessel 7 post-processing means 8 high-pressure fluid recirculation means

Claims (6)

In a high-pressure container, by contacting the organic polymer substrate and a high-pressure fluid containing an organometallic compound in a batch manner, a method of fixing the organometallic compound on the surface of the organic polymer substrate,
As the organometallic compound, an organometallic complex containing one or more metals selected from the group consisting of Ni, Cu, Cr, Pt, Au, Ag, Pd and Fe is used,
As a high-pressure fluid, while using any of carbon dioxide, nitrogen and hydrocarbons having 4 or less carbon atoms,
When the critical pressure of the high-pressure fluid is Pc ₁ (MPa), the temperature T ₁ (K) and the pressure P ₁ (MPa) of the high-pressure fluid are controlled so as to satisfy the following equations (1) and (2), respectively. And performing the contacting step.
313 ≦ T ₁ ≦ 473 (1)
0.8Pc ₁ ≦ P ₁ ≦ 5.0Pc ₁ (2) In a high-pressure container, by contacting the organic polymer substrate and a high-pressure fluid containing an organometallic compound in a batch manner, a method of fixing the organometallic compound on the surface of the organic polymer substrate,
As the organometallic compound, an organometallic complex containing one or more metals selected from the group consisting of Ni, Cu, Cr, Pt, Au, Ag, Pd and Fe is used,
Using water or alcohol as the high-pressure fluid,
When the critical temperature of the high-pressure fluid is Tc (K) and the critical pressure of the high-pressure fluid is Pc ₂ (MPa), the temperature T ₂ (K) and the pressure P ₂ (MPa) of the high-pressure fluid are expressed by the following equation (3), respectively. A method for modifying the surface of an organic polymer substrate, wherein the contacting step is performed while controlling to satisfy (4).
0.6Tc ≦ T ₂ ≦ 1.1Tc (3)
0.05Pc ₂ ≦ P ₂ ≦ 1.5Pc ₂ (4) 2. The method according to claim 1, further comprising, after the contacting step, heating the organic polymer substrate to which the organometallic complex is fixed on the surface to decompose the organometallic complex to form an active metal element on the surface of the organic polymer substrate. 3. The method for modifying the surface of an organic polymer substrate according to item 2. After the contacting step, in the presence of a reducing gas, the organic polymer substrate having the organometallic complex fixed to the surface is heated to decompose the organometallic complex, thereby generating a single active metal on the organic polymer substrate surface. 3. The method for modifying the surface of an organic polymer substrate according to claim 1, comprising a step. A plating layer-containing organic polymer substrate obtained by forming an electroless plating layer on a surface of an organic polymer substrate to which an active metal simple substance obtained by the method according to claim 3 is fixed. . A high-pressure apparatus for performing the surface modification method according to claim 1, wherein the high-pressure vessel, high-pressure fluid supply means for supplying a high-pressure fluid to the high-pressure vessel, and stirring means for stirring the inside of the high-pressure vessel. And a high-pressure device.

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