JP2008190041A - Method for producing metallized film - Google Patents

Abstract

A method for producing a metallized film capable of forming a metal layer having a uniform thickness and excellent surface properties by covering the inside of a defect hole is provided.
A method of manufacturing a metallized film in which a metal layer 4 is formed on the surface of an insulator 1, the step of forming a base metal film 4 on the surface of the insulator 1 by a dry plating method, 1 By contacting an organic monomer-containing liquid with the surface on which the base metal film 4 is formed, and selectively forming a conductive organic polymer film on the surface of the insulator 1 in the defect hole of the base metal film 4, And a coating step.
[Selection] Figure 3

Description

  The present invention relates to a method for manufacturing a metallized film in which a metal layer with few defects is formed on the surface of an insulator.

  In recent years, there has been an increasing demand for circuit boards using TAB (Tape Automated Bonding), FPC (Flexible Prnt Circuit), etc. as circuit boards that are advantageous for reducing the size and weight of electronic devices. Conventionally, this type of circuit board has been obtained by bonding a copper foil to an adhesive such as an epoxy-based adhesive on a flexible plastic substrate. However, in order to achieve high-density mounting of electronic devices, it is desired to further reduce the thickness of this type of circuit board. As described above, the structure in which the copper foil is bonded sufficiently meets the demand for thinning. I couldn't.

  Therefore, a technique for forming a metallized film without using an adhesive has been studied. For example, after forming a base metal film directly on a plastic substrate by thin film formation technology such as vacuum evaporation, sputtering, ion plating, etc., a metal plating layer is deposited on this base metal film by electrolytic plating or the like The method of making is known.

  However, in the above manufacturing method, it is inevitable that a large number of defect holes with a size of several μm to several hundred μm are generated in the base metal layer formed by the dry plating method. When a metal plating layer is formed on a base metal layer having such a defect hole, even if the metal plating layer can close the defect hole, the plating solution remains inside the defect hole and the metal film is peeled off. If the wiring pattern is a cause or a thin wiring pattern is formed on the defect hole, the wiring pattern may be disconnected.

Japanese Patent Application Laid-Open No. 10-256700 discloses that a base metal layer is formed on an insulator film by a dry plating method, and then a primary electrolytic copper plating film layer is formed on the base metal layer. A method is proposed in which an electroless copper plating film layer is formed as an intermediate metal layer on the primary electrolytic copper plating film layer, and a secondary electrolytic copper plating film layer is finally formed on the intermediate metal layer. ing. (See Patent Document 1)
JP-A-10-256700

  However, in the above method, the base metal layer, the primary electrolytic copper plating coating layer, the electroless copper plating coating layer, and the secondary electrolytic copper plating coating layer are sequentially formed on the insulator film, so that the process is complicated. It was expensive.

  Further, when forming the electroless plating coating layer, it is necessary to first attach the catalyst nucleus on the surface to be plated, but the catalyst nucleus tends to adhere more on the metal than the exposed surface of the insulator. Therefore, the thickness of the electroless plating layer formed in the defect hole becomes thinner than that on the metal surface, and the defect hole cannot be completely filled. Accordingly, it is inevitable that the surface of the metal layer is recessed at the position where the defect hole is present, and it is difficult to form a metal layer having a uniform thickness.

  Furthermore, the electroless plating method does not form a dense film as much as the electrolytic plating method. For this reason, the surface of the electroless plating layer has a rough structure with many irregularities, and the secondary electrolytic copper plating film layer formed on the electroless plating layer also has a rough surface reflecting the surface properties of the electroless plating layer. Therefore, there is also a problem that the surface of the finally obtained metal layer is not flat and dense.

  The present invention has been made in view of the above circumstances, and it is possible to selectively coat only defective holes of a base metal film formed by a dry plating method with a conductor, thereby forming a metal layer having excellent surface properties. The challenge is to provide a method.

  In order to solve the above problems, a method for producing a metallized film according to the present invention is a method for producing a metallized film in which a metal layer is formed on the surface of an insulator, and the surface of the insulator is subjected to a dry plating method. A step of forming a base metal film, an organic monomer-containing liquid is brought into contact with the surface of the insulator on which the base metal film is formed, and a conductive organic polymer film is formed on the surface of the insulator in the defect hole of the base metal film And a step of covering the inside of the defect hole by selective formation.

  After the inside of the defect hole is covered with the conductive organic polymer film, a metal wet plating layer may be formed by depositing a metal on the base metal film by an electrolytic plating method. This metal plating layer also becomes a part of the metal layer.

  According to the method for producing a metallized film according to the present invention, a large number of defect holes generated in the base metal film due to the dry plating method can be selectively covered with the conductive organic polymer film, and the entire surface is covered. A conductive layer having high flatness and uniform electrical conductivity can be obtained.

  Next, an embodiment of a method for producing a metallized film according to the present invention will be described with reference to FIGS. Reference numeral 1 in the figure denotes an insulator, and in this embodiment, a plastic film 1 is used as an example. However, the present invention is not limited to the plastic film 1 and can be applied to a plastic such as a hard substrate that is not in the form of a film, or an insulator other than plastic, such as ceramics, glass, rubber, etc., can be used. Is possible.

  The material of the plastic film 1 may be a polyimide resin often used for applications such as TAB tape. A polyimide film has good heat and moisture absorption dimensional stability and rigidity, but has a low bonding strength with a metal thin film. The polyimide film 1 may be a single layer or a laminated film in which a plurality of types of polyimide resins are laminated.

  In this embodiment, the metal core adhering portion 2 is formed on the plastic film 1 and the base metal film 4 is formed. The metal core adhering portion 2 has an effect of increasing the bonding strength between the base metal film 4 and the plastic film 1. However, if the base metal film 4 can be formed on the plastic film 1 with high bonding strength, the metal nucleus adhesion part 2 can be omitted.

  In the example shown in the figure, the metal nucleus attaching part 2 and the base metal film 4 are formed only on one surface of the polyimide film 1, but they may be formed on both surfaces, or the metal core attaching part 2 and the base metal film 4 in advance. May be formed to have a desired pattern shape.

  As the material of the metal nucleus adhesion part 2, one or more selected from Mo, Cr, Ni, Si, Fe, Al, and an alloy substantially formed from two or more of these elements may be used. Is preferred. By attaching these elements as metal nuclei onto the plastic film 1, the bonding strength of the base metal film 4 can be increased. In particular, when the base metal film 4 is formed of copper or a copper alloy, the effect is remarkable.

  In order to form the metal nucleus attaching portion 2, the nucleating metal may be attached on the plastic film 1 by a dry film forming technique such as a vacuum deposition method, a sputtering method, or an ion plating method. Particularly preferable film forming methods for attaching the nucleating metal are a sputtering method and an ion plating method. The film forming conditions are not particularly limited, but it is preferable to reduce the partial pressure of oxygen and water in the film forming tank as much as possible in order to prevent oxidation of the nucleating metal.

The thickness of the metal nucleus adhering portion 2 is preferably in the range of 0.2 mg / m ² to 90 mg / m ² , and does not have to be a continuous dense film. When the metal adhesion amount in the metal nucleus adhesion part 2 is less than 0.2 mg / m ² , particularly when a polyimide film is used as the plastic film 1, it is difficult to increase the bonding strength of the base metal film 4. Further, the metal nucleus adhesion section 2 is larger than 90 mg / m ^2, a fear that adhesion strength of the base metal film 4 by oxidation of the deposited the nucleation metal decreases rather occurs.

  The material of the base metal film 4 is one or more selected from copper, copper alloy, aluminum, aluminum alloy, silver, gold, platinum and the like, and particularly preferably pure copper, nickel, zinc, or iron. It is a copper alloy containing etc. The thickness of the base metal film 4 is preferably 10 nm or more, more preferably 200 nm or more. If the base metal film 4 is too thin, it will be difficult to form the metal wet plating layer 10 on the base metal film 4 with a uniform thickness. On the other hand, if the base metal film 4 is too thick, the cost becomes too high.

  In order to form the base metal film 4, a metal is formed on the polyimide film 1 on which the metal core adhesion part 2 is formed by a dry plating method such as vacuum deposition, sputtering, or ion plating. Among these, the sputtering method and the ion plating method are preferable because the bonding strength is easily increased. The film forming conditions are not particularly limited, and may be conditions normally applied to this type of material.

  When the metal nucleus adhesion part 2 and the base metal film 4 are formed by the dry plating method as described above, defect holes 6 are generated in the metal nucleus adhesion part 2 and the base metal film 4. These defect holes 6 reach the surface of the plastic film 1, so that the plastic film 1 is exposed inside the defect holes 6. In many cases, the size of the defect hole 6 is about several μm to several hundred μm, but there are also those exceeding this range. The shape of the defect hole 6 is not limited to a circle, and may be various shapes such as a slit shape.

  In order to fill these defect holes 6, an organic monomer-containing liquid is then brought into contact with the base metal film 4 to selectively form a conductive organic polymer film on the insulator surface in the defect holes of the base metal film. The organic monomer-containing liquid is a solution or an emulsion containing an organic monomer.

  In the present invention, as the organic monomer, an aniline, pyrrole, or thiophene compound that can form a polyacetylene-based conductive polymer having continuous double bonds by polymerization can be used.

  The organic monomer is polymerized by a reaction with an oxidizing agent and an acid to form a conductive organic polymer. Therefore, the conductive organic polymer can be selectively formed on the insulator surface by precipitating the oxidizing agent on the insulator surface in the defect hole 6 of the base metal. Since the conductive organic polymer is not formed on the metal surface, the smoothness and specularity of the base metal film 4 can be maintained. Moreover, since the thickness of the conductive organic polymer film is small, the surface roughness is small and the smoothness of the surface of the defect hole 6 can be maintained.

  The procedure for selectively forming a conductive organic polymer on the insulator surface using the organic monomer is as follows. Specifically, it is possible to use “Empione DMS-E-System” (trademark of Direct Metallization System, former name “Monopole DMS-E-System”) sold by Enson.

  First, the plastic film 1 on which the base metal film 4 is formed is degreased as necessary to remove stains mainly due to organic substances on the surface, and then immersed in an acidic oxidant (etching) solution to form the surface of the base metal film 4 The metal oxide film is removed. A variety of surfactant solutions can be used for degreasing, and a sulfuric acid / persulfate mixed solution, a sulfuric acid / hydrogen peroxide mixed solution, or the like can be used for etching.

  Subsequently, a surfactant is adsorbed on the surface of the insulator in the underlying metal film defect hole 6 by conditioning to impart polarity. At this time, in the case where the substrate is a non-organic material such as ceramics or glass, the surface is made organic by being coated with the organic material. As a result, the entire surface of the insulator is uniformly and effectively oxidized by the oxidation treatment shown in the next section. Depending on the plastic material, an alkali treatment and / or a swelling treatment with a surfactant or a solvent may be further performed before and after conditioning, if necessary.

Next, oxidation treatment is performed. For the oxidation treatment, for example, the plastic film 1 is immersed in a solution in which 40 to 100 g / L of permanganate is dissolved. By this oxidation treatment, the organic insulator exposed in the defect hole 6 portion of the base metal film 4 distributed on the plastic film 1 and the organic matter adsorbed by the conditioning are selectively oxidized, and at the same time, the permanganate is reduced. Then, manganese dioxide is deposited on the surface of the insulator.
This manganese dioxide acts as an oxidizing agent in the oxidative polymerization of the organic monomer shown in the next section.

  Next, the plastic film 1 is immersed in an organic monomer-containing liquid to form a conductive organic polymer film 8 in the defect hole 6. In order to form the conductive organic polymer film 8, the plastic film 1 may be immersed in a mixed solution of an organic monomer and an acid, or may be immersed in an acid after being immersed in an organic monomer-containing solution. For example, Enson's “Envision DMS-E System” (Trademark of Enson Corporation) uses “Envision DMS-E Catalyst 7050A” (Trademark of Enson Corporation) and “Envision DMS-E Catalyst 7050B” (Trademark of Enson Corporation). Immerse in a mixed solution containing 10 to 20 mL / L and 40 to 60 mL / L, respectively, or contain “Envision DMS-E Catalyst 7030” (trademark of Enson) at a concentration of 100 to 140 mL / L. A conductive organic polymer film can be formed by dipping in an acid after dipping in a solution.

  Furthermore, by washing with water and drying, a metallized plastic film in which the inside of the defect hole 6 is covered with the conductive organic polymer film 8 is obtained. Since the conductive organic polymer film 8 is not formed on the surface of the base metal film 4, the mirror property of the base metal film 4 formed by the dry plating method is maintained.

  Next, a metal wet plating layer 10 is formed on the conductive layer (2 + 4 + 8) by a wet plating method. As the wet plating method, an electrolytic plating method and an electroless plating method can be used. However, the electrolytic plating method is preferable because it has a high film formation rate, low film formation cost, and high surface smoothness. When the electrolytic plating method is used, the plastic film 1 is immersed in a wet plating solution, a power source cathode is connected to the conductive layer (2 + 4 + 8), current is passed between the anode immersed in the wet plating solution, and the conductive layer (2 + 4 + 8). ) A metal wet plating layer 10 is deposited thereon. In the case of using the electroless plating method, first, after depositing nuclei on the conductive layer (2 + 4 + 8) with a palladium salt solution or the like, the plastic film 1 may be immersed in the electroless plating solution.

  As the material of the metal wet plating layer 10, copper or a copper alloy is preferable from the viewpoint of electric conductivity, but other metals may be used.

  According to the manufacturing method of the metallized film comprising the above steps, the conductive organic polymer film 8 is selected while maintaining the surface roughness of the plastic film substrate 1 in the numerous defect holes 6 generated in the base metal film 4. Thus, a metal layer having no defects (24,810) can be formed by plating in a later step.

  Moreover, since the conductive organic polymer film is not formed on the surface of the base metal film 4 formed by the dry plating method and maintains a mirror surface, the metal wet plating layer 10 formed thereon reflects the mirror surface. And a dense layer with high flatness. Furthermore, compared with the prior art, there are also advantages that the number of steps is small and the cost is low.

Next, an example is given and the effect of the present invention is proved.
Molybdenum was deposited on the polyimide film in an amount of 30 mg / m ² , and then copper was deposited to a thickness of 300 nm by sputtering. A through-hole having a diameter of 200 μm was formed in this copper film by etching treatment, and assumed to be a pinhole. The polyimide film was subjected to alkali treatment and polymer formation treatment to form a conductive organic polymer film inside the pinhole. Furthermore, copper sulfate plating was performed to deposit a copper layer on the conductive organic polymer film. The polymer formation treatment was performed according to the following procedure and conditions.

(1) Degreasing The alkali-treated film was degreased with an acidic degreasing solution. The acidic degreasing solution was an aqueous solution of “Actu Pure AS” (trademark of Enson) 50 mL / L and sulfuric acid 50 mL / L, and the film was immersed in this acidic degreasing solution for 60 seconds at room temperature and washed with water.

(2) Conditioning The degreased film was immersed in an 20 mL / L aqueous solution of “Envision DMS-E Conditioner 7015A” (trademark of Enson) at 40 ° C. for 120 seconds and washed with water.
(3) Oxidation treatment The conditioned film was immersed in an aqueous solution of 65 g / L potassium permanganate and 10 g / L boric acid at 70 ° C. for 180 seconds and washed with water.

(4) Catalyst treatment The oxidized film was subjected to “Envision DMS-E” (trademark of Enson), “Envision DMS-E Catalyst 7050A” (trademark of Enson) 20 mL / L and “Envision DMS-E Catalyzer”. It was immersed in an aqueous solution containing “List 7050B” (trademark of Enson) 45 mL / L at room temperature for 240 seconds and washed with water. A photomicrograph taken in this state is shown in FIG. It can be seen that the dark colored portion corresponds to a pinhole, and a conductive organic polymer film is formed inside.

(5) Copper sulfate plating The film on which the polymer is formed is immersed in an aqueous solution of copper sulfate 100 g / L and sulfuric acid 200 g / L, and electroplating is performed at a liquid temperature of 25 ° C. and a current density of 2 A / dm ² while stirring with air. A copper plating layer was formed on the conductive polymer film. A photomicrograph taken in this state is shown in FIG. It can be seen that a copper plating layer having the same surface properties as the copper plating layer formed outside the pinhole is also formed inside the pinhole.

  About the copper plating polyimide film obtained by the said manufacturing method, the peeling strength of the copper plating layer was measured. Three strip test pieces having a width of 10 mm and a length of 150 mm were cut out from the polyimide film. Of these, the first sheet was not heat-treated, the second sheet was heat-treated at 150 ° C. × 168 hours, and the third sheet was heat-treated in a high humidity state (PCT process) (relative humidity 98%, 121 ° C x 24 hours). Separately, a copper-plated polyimide film different from the above three sheets was produced only in that the conductive polymer formation treatment was not performed.

  About these 6 types of copper plating polyimide films, the peeling strength between a film base material and a metal film was measured by the method by IPC-TM-650 (American Printed Circuit Industry Association Standard Test Method). In this test method, the polyimide film side of the strip-shaped test piece was adhered and fixed to the outer periphery of a 6 inch diameter drum in the circumferential direction, and one end of the metal film was peeled off from the polyimide film at 5 cm / min with a jig. It is a method of measuring the load required for pulling while pulling. FIG. 6 shows the test results.

  As shown in FIG. 6, the peel strength (peel strength) of the copper plating layer in the copper plating polyimide film having the conductive organic polymer film formed is also higher than that of the copper plating polyimide film in which the conductive organic polymer film is not formed. ) Was not fading.

In one Embodiment of this invention, it is a cross-sectional enlarged view which shows the state which the defect hole produced in the base metal film. In one Embodiment of this invention, it is a cross-sectional enlarged view which shows the state which formed the electroconductive organic polymer membrane | film | coat in the defect hole. In one Embodiment of this invention, it is a cross-sectional enlarged view which shows the state which formed the metal wet-plating layer on the base metal film which coat | covered the inside of a defect hole. It is a microscope picture which shows the state which formed the electroconductive organic polymer membrane | film | coat in the pinhole. It is a microscope picture which shows the state which formed the copper plating layer on the electroconductive organic polymer membrane | film | coat in a pinhole. It is the case where it is not set as the case where the conductive organic polymer membrane | film | coat is formed, and is the graph which compared the peeling strength of the copper plating layer.

Explanation of symbols

1 Plastic film (insulator)
2 Metal core adhesion part
4 Underlying metal film
6 Defect holes
8 Conductive organic polymer film
10 Metal wet plating layer

Claims (11)

A method for producing a metallized film in which a metal layer is formed on the surface of an insulator,
Forming a base metal film on the surface of the insulator by dry plating;
By contacting an organic monomer-containing liquid with the surface of the insulator on which the base metal film is formed, and selectively forming a conductive organic polymer film on the insulator surface in the defect hole of the base metal film, And a step of coating the inside of the defect hole.   2. The metal wet plating layer is formed according to claim 1, wherein after the inside of the defect hole is covered with the conductive organic polymer film, a metal is formed on the base metal film by electrolytic plating to form a metal wet plating layer. A method for producing a metallized film.   2. The metal wet plating layer is formed by depositing a metal on the base metal film by an electroless plating method after coating the inside of the defect hole with the conductive organic polymer film. Method for producing metallized film.   2. The method for producing a metallized film according to claim 1, wherein the dry plating method is any one of a sputtering method, a vacuum deposition method, and an ion plating method.   2. The method of manufacturing a metallized film according to claim 1, wherein the insulator is a plastic film. Before the step of forming the base metal film, one or two selected from Mo, Cr, Ni, Si, Fe, Al, and an alloy substantially formed from two or more of these elements. The method for producing a metallized film according to claim 1, further comprising a step of forming the above in a thickness of 0.2 mg / m ² or more and 90 mg / m ² or less.   2. The method for producing a metallized film according to claim 1, wherein the conductive organic polymer has a polyacetylene structure.   2. The method for producing a metallized film according to claim 1, wherein the conductive organic polymer film is formed by an oxidative polymerization reaction of an organic monomer.   The method for producing a metallized film according to claim 1, wherein the organic monomer is aniline, pyrrole, or a thiophene compound.   The method for producing a metallized film according to claim 1, wherein the surface resistance of the conductive organic polymer film is 10 Ω / cm to 1 MΩ / cm.   2. The method for producing a metallized film according to claim 1, wherein the conductive organic polymer film has a thickness of 0.2 [mu] m or less.

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