KR101462967B1 - Method for preparing flexible metal clad laminate and flexible metal clad laminate prepared from the same - Google Patents

Abstract

The method for fabricating a flexible metal foil laminate of the present invention includes the steps of: depositing a metal thin film on a polymer film to form a thin film layer; Electroplating the polymer film having the thin film layer formed thereon to form a metal conductive layer on the thin film layer; And heating the polymer film at a temperature not lower than the glass transition temperature of the polymer film. The method for producing a flexible metal foil laminate has excellent adhesion strength between the polymer film and the metal conductive layer and is suitable for high precision and high frequency applications.

Description

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a flexible metal foil laminates and a flexible metal foil laminates,

The present invention relates to a method of manufacturing a flexible metal foil laminates and a flexible metal foil laminates produced therefrom. More particularly, the present invention relates to a method for producing a flexible metal foil laminate having excellent adhesion strength between a polymer film and a metal conductive layer and suitable for high-precision and high-frequency applications, and a flexible metal foil laminate produced therefrom.

Printed Circuit Bard (PCB) is a wiring diagram that shows the electrical wiring to connect various parts according to the circuit design. It connects and supports various parts. In recent years, as electronic devices have become more sophisticated, more accurate, and have higher performance, it is required to increase the functionality of such wiring boards. Particularly, a flexible printed circuit board (FPCB) (hereinafter referred to as " flexible printed circuit board ") is required for a wiring board used for a portable device such as a cellular phone or a portable music apparatus, Development is progressing actively.

Typically, the wiring of the flexible substrate has a line space of 35 to 70 탆. The substrate base material (raw material) for manufacturing the flexible substrate is required to be highly accurate, and must be capable of coping with the miniaturization of the pattern in correspondence with high frequency, , Low dielectric constant, low water absorption, low unevenness, and the like. As a raw material for such a flexible substrate, a flexible copper clad laminate (FCCL) having a large bending property and favorable characteristics for light weight shortening has been widely used.

The flexible copper-clad laminate is a laminate of a polymer film (layer) and a metal conductive layer. The flexible copper-clad laminate is used for a part of electronic equipment or electronic equipment requiring flexibility and flexibility. Contributing.

As the polymer film, a polyimide film has been widely used. However, a film having low hygroscopicity and excellent insulation property has been developed and used in accordance with the demand for high functionality.

As a method of forming the metal conductive layer (copper thin film), a copper thin film including nickel, chromium, or the like is formed by a sputtering (vacuum deposition) method in order to ensure adhesion, and then electroplated A method of forming a metal conductive layer which is a copper plating layer is used. However, in the above method, since not only copper etching but also nickel, chromium, and the like must be etched in a pattern etching process for constituting a wiring circuit, there is a problem that a process is added. In particular, since nickel is a magnetic metal, it may interfere with high frequency applications.

As another method, a method of forming a metal conductive layer by a sputtering method without forming a thin film layer has been proposed. However, it takes a considerable time to form the metal conductive layer with a thickness of about 12 탆 or more by the sputtering method alone, which is not practical.

This problem can be solved to some extent by using electroless plating. That is, the electroless plating method can shorten the time, increase the efficiency of the process, and can directly form the metal plating layer on the polymer film. The electroless plating method is a method in which irregularities are formed on the surface of the polymer film through a pretreatment, and the plating layer is adhered through the so-called anchor effect. For example, in the case of a polyimide film, unevenness is formed on the film surface (surface roughening treatment) by using a pretreatment agent generally called a conditioner. However, irregularities on the surface of the polymer film may cause signal scattering in high frequency applications.

Generally, a polymer film has a structure having a benzene ring as a skeleton, and thus has a merit of exhibiting high insulating properties as a high frequency substrate. However, even if any method such as a dry method such as sputtering or a wet method such as plating is employed, the surface adhesion strength with the metal conductive layer It is difficult to prevent deterioration. In particular, since a flexible metal foil laminate using a liquid crystal polymer (LCP) is usually manufactured by attaching a metal foil to a polymer film by heat, LCP is difficult to thin a metal foil despite its excellent insulating properties There is a problem that the use range is limited. Therefore, there is a demand for a method of producing a flexible metal foil laminate capable of easily forming a metal conductive layer having excellent adhesion strength with a polymer film even when a polymer film is used as a substrate.

An object of the present invention is to provide a method for producing a flexible metal foil laminate having excellent adhesion strength between a polymer film and a metal conductive layer and suitable for high precision and high frequency applications.

Another object of the present invention is to provide a flexible metal foil laminate produced by the above-mentioned production method.

The above and other objects of the present invention can be achieved by the present invention described below.

One aspect of the present invention relates to a method of manufacturing a flexible metal foil laminate. The method includes depositing a metal on a polymer film to form a thin film layer; Electroplating the polymer film having the thin film layer formed thereon to form a metal conductive layer on the thin film layer; And heating the polymer film at a temperature not lower than the glass transition temperature of the polymer film; The method comprising the steps of:

In embodiments, the deposition may be by a sputtering method.

In embodiments, the deposition may be performed from the glass transition temperature of the polymer film at a temperature ranging from -30 to 300 < 0 > C and a pressure of 1 Pa or less.

In an embodiment, the thin film layer may include at least one of copper, gold, silver, aluminum, titanium, zinc, vanadium, and manganese.

In an embodiment, the thickness of the thin film layer may be 0.05 to 1 占 퐉.

In an embodiment, the polymer film is one of polyimide, epoxy resin, Teflon, polyphenylene sulfide, polyamide, polyester, fluorinated polyolefin, polyimide ether, polyamideimide, aramid, polycarbonate, polyolefin and polycycloolefin. Or more species.

In a specific example, the thin film layer may be heated at 100 to 250 ° C for 3 minutes or more after formation.

In an embodiment, the thickness of the metal conductive layer may be 1 to 30 탆.

Another aspect of the present invention relates to a flexible metal foil laminate produced from the above production method.

INDUSTRIAL APPLICABILITY The present invention has the effect of providing a method for producing a flexible metal foil laminated board excellent in adhesion strength between a polymer film and a metal conductive layer and suitable for high precision and high frequency applications and a flexible metal foil laminate produced therefrom. The flexible metal foil-clad laminate is useful as a substrate for a printed circuit board (PCB), a touch panel, an electromagnetic wave shielding film, an antireflection film, and a transparent conductive film.

1 is a cross-sectional view of a flexible metal foil laminate according to an embodiment of the present invention.
2 is a schematic view of a magnetron sputtering apparatus for forming a thin film layer according to an embodiment of the present invention.

Hereinafter, the present invention will be described in detail with reference to the accompanying drawings.

1 is a cross-sectional view of a flexible metal foil laminate according to an embodiment of the present invention. As shown in FIG. 1, the flexible metal foil laminate of the present invention is a laminate of the polymer film 10, the thin film layer 20, and the metal conductive layer 30, and may include the same configuration as a conventional flexible metal foil laminate However, the adhesive strength between the polymer film 10 and the metal conductive layer 30 is very excellent through the thin film layer 20. The flexible metal foil laminates may be manufactured according to the method of manufacturing flexible metal foil laminates according to the present invention.

The method for fabricating a flexible metal foil laminate according to the present invention includes the steps of forming a thin film layer 20 by depositing a metal on a polymer film 10 and electroplating the polymer film 10 on which the thin film layer 20 is formed to form the thin film layer 20 ), And heating the polymer film (10) at a temperature not lower than the glass transition temperature of the polymer film (10).

As the polymer film 10 used in the present invention, a polymer film, a liquid crystal polymer (LCP) film and the like used in a conventional flexible metal foil laminate can be used without limitation. For example, the polymer film 10 may be formed of a material such as polyimide, epoxy resin, Teflon, polyphenylene sulfide, polyamide, polyester, fluorinated polyolefin, polyimide ether, polyamideimide, aramid, polycarbonate, Olefins, and the like, but is not limited thereto. The polyester or the like may be in the form of a known liquid crystal polymer such as a thermotropic liquid crystal. Specific examples of the polyolefin include polyethylene, polypropylene, poly-4-methylpentene-1, and the like.

In an embodiment, the polymer film 10 may be degreased to remove impurities on the surface. In general, it can be treated by immersing it in alcohols such as methyl alcohol, ethyl alcohol and isopropyl alcohol, ketones such as acetone, methyl ethyl ketone and isobutyl ketone, and degreasing treatment by wiping with paper, It is possible. In addition, it may be washed with an aqueous acid solution such as diluted hydrochloric acid or the like and a surfactant-containing aqueous solution, which are generally used for printed boards.

Further, the polymer film 10 can be heat-treated in a vacuum state to remove impurities such as monomers adhering to the surface of the film during production of the film, moisture or gas contained in the film. The heat treatment temperature may be a glass transition temperature of the polymer film 10 to be used, and a thermosetting resin having no glass transition temperature, for example, an epoxy resin, a polyimide, a polyamide or the like, Normally, the heat treatment can be performed until the pressure of the vacuum device reaches 0.001 Pa or less.

The thickness of the polymer film 10 may be, for example, 3 to 100 占 퐉, but is not limited thereto.

The thin film layer 20 of the present invention may be formed by depositing a metal on the polymer film 10 by a sputtering method. Preferably, the deposition may be performed by a magnetron sputtering method.

2 is a schematic view of a sputtering apparatus for forming a thin film layer (a metal thin film) 20 according to an embodiment of the present invention. As shown in FIG. 2, the thin film layer 20 of the present invention can be performed using a conventional (magnetron) sputtering apparatus. For example, the polymer film 10 is fixed above the sputtering source (metal evaporation source) 13 using the fixing jig 114 of the sputtering apparatus. The fixing jig 114 may be connected to a temperature controller 112 for keeping the temperature of the polymer film 10 constant, and the temperature controlling medium may be circulated. In addition, the fixing jig 114 may be supplied with bias power from the magnetron power supply 115.

After the polymer film 10 is fixed to the fixing jig 114, the vacuum pump 118 is operated so that the pressure inside the sputtering apparatus measured by an exhaust vacuum meter (vacuum pressure gauge 19) is 1 Pa or less, Is equal to or less than 0.1 Pa, more preferably equal to or less than 0.001 Pa, for example, from 0.000001 to 0.001 Pa. The pressure can be confirmed through a vacuum system 119. The temperature of the fixed polymer film 10 may be varied depending on the polymer film 10 to be used, but the temperature of the fixed polymer film 10 may be changed from the glass transition temperature of the polymer film 10 to -30 to- Lt; RTI ID = 0.0 > 300 C. < / RTI > In the specific example, when the polymer film 10 is a thermoplastic resin, it can be maintained in a temperature range of -30 to 50 캜 from the glass transition temperature of the thermoplastic resin. In the case of a thermosetting resin, the glass transition temperature of the thermosetting resin is 100 Lt; 0 > C to 300 < 0 > C. The adhesion strength between the polymer film 10 and the thin film layer 20 during the deposition in the above range can be excellent.

When the pressure inside the sputtering apparatus reaches 1 Pa or less and the polymer film 10 reaches the set temperature, the magnetron power supply 115 is operated to apply power. At this time, the voltage applied to the magnetron power supply 115 may be 1 to 20 kV, preferably 5 to 15 kV. In this range, the adhesion between the metal thin film and the polymer film 10 can be improved, and the change in the surface of the polymer film 10 and the formation of the unevenness can be prevented, thereby preventing the high frequency signal from scattering during circuit formation. In addition, the mechanical properties of the film itself can be prevented from deteriorating, and a stable discharge can be obtained in sputtering.

Next, the valve of the external gas introduction pipe 117 is opened to adjust the internal pressure of the sputtering apparatus to 0.1 Pa or less while injecting an external gas such as argon or nitrogen. Then, when the power source 116 connected to the metal evaporation source 113 is turned on to start the discharge, the metal of the metal evaporation source 113 is deposited on the polymer film 10. At this time, the deposition rate of the metal thin film (thin film layer 20) deposited on the polymer film 10 may be 0.1 to 10 Å (angstrom) per second. After completion of the deposition, the exhaust is stopped, and the water leakage valve 120 is opened to return the internal pressure of the apparatus to normal pressure.

The metal of the metal evaporation source 113, that is, the thin film layer (metal thin film) 20 may be formed of one or more kinds of copper, gold, silver, aluminum, titanium, zinc, vanadium, manganese, It can include gold.

The thickness of the thin film layer 20 may be 0.05 to 1 占 퐉, preferably 0.1 to 0.5 占 퐉. The metal conductive layer 30 having no deterioration in function and film deformation and having an excellent bonding strength can be formed within the above range.

In one embodiment, the flexible metal foil laminate of the present invention is formed by forming the thin film layer 20 at a temperature of 100 to 250 ° C, preferably 150 to 200 ° C for 3 minutes or more, for example, 3 to 60 minutes, preferably 3 (Heat treatment) for 10 minutes to 10 minutes. In this case, the polymer film 10 and the thin film layer 20 are fused, and the thin film layer 20 is fused to improve the bonding strength.

The metal conductive layer 30 of the present invention can be formed by a conventional electroplating solution, for example, an electroplating method using a copper electroplating solution or a gold electroplating solution. For example, the polymer film 10 on which the thin film layer 20 is formed is coated with an additive such as bis [3-sulfopropylsulfonic acid] sodium salt to adjust the plating stress A metal electroconductive layer having a desired thickness can be formed by carrying out electroplating after dipping in an electroplating solution. The amount of the additive to be used may be 0.1 to 100 ppm, preferably 1 to 8 ppm, based on the total electroplating solution, but is not limited thereto.

In a specific example, as the copper electroplating solution, if necessary, in a high-slow type copper sulfate basic tank (copper sulfate: 75 g / L, sulfuric acid: 180 g / L, chlorine: 40 ppm) for a copper electroplating substrate, May be used to adjust the plating stress, but the present invention is not limited thereto.

In a specific example, a conventional gold electroplating solution containing 2.3 g / L of potassium cyanide (sodium chloride), 15 g / L of potassium cyanide (chlorination gray) and 4 g / L of sodium phosphate is used as the gold electroplating solution But is not limited thereto.

In addition, the electroplating may be performed at a temperature of 15 to 120 DEG C and a current density of 0.1 to 0.5 A / dm < ² >

The thickness of the metal conductive layer 30 may be 1 to 30 탆, preferably 5 to 25 탆. It is possible to obtain a metal conductive layer free from stress and bending in the above range and having an excellent adhesive layer.

The flexible metal foil laminate of the present invention preferably has a glass transition temperature higher than the glass transition temperature and the decomposition initiation temperature of the polymer film 10, for example, 100 to 300 占 폚, preferably 150 to 250 占 폚 Followed by heating (heat treatment).

The adhesive strength between the polymer film 10 and the metal electrode layer 30 is improved as compared with the conventional flexible metal foil laminate through the above process. This is because the microstructure (micron structure) of the polymer constituting the polymer film 10 is fused with the thin film layer 20 and the metal conductive layer 30 during the temperature change process by the heat treatment to form the polymer film 10, The interface is activated, and as a result, the binding force is enhanced.

The heating temperature may be appropriately selected depending on the kind of the polymer film 10 and may be generally performed at a higher temperature than the plating treatment temperature (15 to 120 ° C), and in one embodiment, at a temperature of 200 ° C 30 minutes. ≪ / RTI > If the heating temperature is lower than the glass transition temperature of the polymer film 10, there is a fear that the adhesive strength improving effect is not obtained. If the heating temperature is higher than the polymer decomposition starting temperature, the film may be decomposed. Generally, when the polymer film has a heat distortion temperature (decomposition initiation temperature) or lower, the microstructure (micron structure) changes, but there is no significant change such that the properties of the polymer film such as electrical property, water absorbability and dimensional stability are changed.

The flexible metal foil laminate of the present invention is excellent in adhesion strength between the polymer film 10 and the metal conductive layer 30 and is suitable for high precision and high frequency applications and thus can be used as a printed circuit board Shielding films, antireflection films, and transparent conductive films.

Hereinafter, the present invention will be described in more detail by way of examples, but these examples are for illustrative purposes only and should not be construed as limiting the present invention.

Example

Example  One

The surface of a 25 μm thick liquid crystal polymer (LCP) film (manufactured by Kuraray Co., Ltd., product name: Vecstar) was degreased by rubbing with a nonwoven fabric impregnated with alcohol for disinfection. The degreased LCP film was fixed to a fixing jig (plate) of a magnetron sputtering apparatus (vacuum vapor deposition apparatus), and then a vacuum pump was operated. At the same time, the temperature controlling medium was circulated in the fixing jig, . After the temperature of the LCP film reached 150 캜 and the inner pressure of the magnetron sputtering apparatus reached 0.0001 Pa, a magnetron power was turned on and a voltage of 5 kV was applied. Next, argon gas was introduced into the magnetron sputtering apparatus through an external gas inlet, and the internal pressure was adjusted to 0.1 Pa. Subsequently, a power source of a magnetron sputtering apparatus connected to a metal (copper) evaporation source was operated to start film formation (copper deposition). When the thickness of the thin film layer (copper deposited film) was 0.8 탆, the film formation was terminated and the supply of argon gas was stopped. Next, the LCP film on which the thin film layer was formed was cooled to 50 DEG C or less, the evacuation of the vacuum pump was stopped, and the leak valve was opened to return the pressure inside the magnetron sputtering apparatus to normal pressure. Subsequently, the LCP film on which the thin film layer was formed was immersed in a high-slow-type copper sulfate solution containing 1 to 8 ppm of bis [3-sulfo propyl sulfonic acid] sodium salt as a commercially available additive And immersed in a basic tank (copper sulfate: 75 g / L, sulfuric acid: 180 g / L, chlorine: 40 ppm) and electroplated to form a metal (copper) conductive layer having a thickness of 18 μm. Next, the LCP film on which the metal conductive layer 30 was formed was heat-treated at 150 DEG C for 30 minutes in a nitrogen atmosphere to produce a flexible metal foil-clad laminate.

Example  2

The surface of the polyimide film (manufactured by Ube, product name: UFIREX (R)) having a thickness of 25 mu m was degreased by rubbing with a nonwoven fabric impregnated with alcohol for disinfection. After the degreased polyimide film is fixed to a fixing jig (plate) of a magnetron sputtering apparatus (vacuum vapor deposition apparatus), a vacuum pump is operated, and at the same time, a temperature controlling medium is circulated in the fixing jig, Lt; / RTI > After the temperature of the polyimide film reached 200 占 폚 and the pressure inside the magnetron sputtering apparatus reached 0.00003 Pa, a magnetron power source was turned on and a voltage of 8 kV was applied. Next, argon gas was introduced into the magnetron sputtering apparatus through an external gas inlet, and the internal pressure was adjusted to 0.1 Pa. Subsequently, a power source of a magnetron sputtering apparatus connected to a metal (copper) evaporation source was operated to start film formation (copper deposition). When the thickness of the thin film layer (copper deposited film) became 1.0 탆, the film formation was terminated and the supply of argon gas was stopped. Next, the polyimide film having the thin film layer formed was cooled to 50 DEG C or lower, the evacuation of the vacuum pump was stopped, and the leak valve was opened to return the pressure inside the magnetron sputtering apparatus to normal pressure. Then, the polyimide film on which the thin film layer was formed was immersed in a solution of a high-speed type of bis (3-sulfopropylsulfonic acid) sodium salt (bis (3-sulfopropylsulfonic acid) sodium salt) (Copper sulfate) 75 g / L, sulfuric acid: 180 g / L, chlorine: 40 ppm) and electroplated to form a metal (copper) conductive layer having a thickness of 12 탆. Next, the polyimide film having the metal conductive layer formed thereon was heat-treated at 150 占 폚 for 30 minutes in a nitrogen atmosphere to prepare a flexible metal foil-clad laminate.

Example  3

A surface of a polyphenylene sulfide (PPS) film (manufactured by Toray Industries, Inc.) having a thickness of 25 탆 was degreased by rubbing with a nonwoven fabric impregnated with alcohol for disinfection, and then a thin film layer was formed in the same manner as in Example 2. A high-slow type copper sulfate basic tank (copper sulfate: 75 g / L (1 g / L)) containing 1 to 8 ppm of bis [3-sulfo propyl sulfonic acid] sodium salt as a commercially available additive , Sulfuric acid: 180 g / L, chlorine: 40 ppm) and electroplated to form a metal (copper) conductive layer having a thickness of 18 탆. Next, the polyimide film having the metal conductive layer formed thereon was heat-treated at 150 占 폚 for 30 minutes in a nitrogen atmosphere to prepare a flexible metal foil-clad laminate.

Example  4

The surface of a polyethylene terephthalate (PET) film (manufactured by Toray Industries, Inc.) having a thickness of 25 mu m was degreased by rubbing with a nonwoven fabric impregnated with alcohol for disinfection. The degreased PET film was fixed to a fixing jig (plate) of a magnetron sputtering apparatus (vacuum vapor deposition apparatus), and then a vacuum pump was operated. At the same time, the temperature controlling medium was circulated in the fixing jig, . When the temperature of the PET film reached 105 占 폚 and the inner pressure of the magnetron sputtering apparatus became 0.0001 Pa or less, a magnetron power source was turned on and a voltage of 5 kV was applied. Next, argon gas was introduced into the magnetron sputtering apparatus through an external gas inlet, and the internal pressure was adjusted to 0.1 Pa. Subsequently, a power source of a magnetron sputtering apparatus connected to a metal (copper) evaporation source was operated to start film formation (copper deposition). When the thickness of the thin film layer (copper deposited film) became 0.8 탆, the film formation was terminated and the supply of argon (Ar) gas was stopped. Next, the PET film on which the thin film layer was formed was cooled to 50 DEG C or less, the evacuation of the vacuum pump was stopped, and the leak valve was opened to return the pressure inside the magnetron sputtering apparatus to normal pressure. Subsequently, the PET film on which the thin film layer was formed was immersed in a high-slow type copper sulfate solution containing 1 to 8 ppm of bis [3-sulfo propyl sulfonic acid] sodium salt as a commercially available additive And immersed in a basic tank (copper sulfate: 75 g / L, sulfuric acid: 180 g / L, chlorine: 40 ppm) and electroplated to form a metal (copper) conductive layer having a thickness of 25 μm. Next, the PET film on which the metal conductive layer was formed was heat-treated at 150 占 폚 for 30 minutes in a nitrogen atmosphere to prepare a flexible metal foil-clad laminate.

Example  5

The surface of the poly 4-methylpentene-1 (TPX) film (manufacturer: Mitsui Chemicals) having a thickness of 25 탆 was degreased by rubbing with a nonwoven fabric impregnated with alcohol for disinfection. After the degreased TPX film was fixed to a fixing jig (plate) of a magnetron sputtering apparatus (vacuum vapor deposition apparatus), a vacuum pump was operated and at the same time, the temperature controlling medium was circulated in the fixing jig . After the temperature of the TPX film reached 120 占 폚 and the pressure inside the magnetron sputtering apparatus reached 0.0001 Pa, a magnetron power source was turned on and a voltage of 1 kV was applied. Next, argon gas was introduced into the magnetron sputtering apparatus through an external gas inlet, and the internal pressure was adjusted to 0.1 Pa. Subsequently, a power source of a magnetron sputtering apparatus connected to a metal (copper) evaporation source was operated to start film formation (copper deposition). When the thickness of the thin film layer (copper vapor-deposited film) reached 0.9 mu m, the film formation was terminated and the supply of argon gas was stopped. Next, the TPX film having the thin film layer formed was cooled to 50 DEG C or less, the evacuation of the vacuum pump was stopped, and the leak valve was opened to return the pressure inside the magnetron sputtering apparatus to atmospheric pressure. Subsequently, the TPX film on which the thin film layer was formed was immersed in a high-slow type copper sulfate solution containing 1 to 8 ppm of bis [3-sulfo propyl sulfonic acid] sodium salt as a commercially available additive And immersed in a basic tank (copper sulfate: 75 g / L, sulfuric acid: 180 g / L, chlorine: 40 ppm) and electroplated to form a metal (copper) conductive layer having a thickness of 18 μm. Next, the TPX film on which the metal conductive layer was formed was heat-treated at 150 占 폚 for 30 minutes under a nitrogen atmosphere to prepare a flexible metal foil-clad laminate.

Comparative Example  One

The surface of the polyimide film (manufactured by Ube, product name: UFIREX (R)) having a thickness of 25 mu m was degreased by rubbing with a nonwoven fabric impregnated with alcohol for disinfection. The degreased polyimide film was fixed to a fixing jig (plate) of a magnetron sputtering apparatus (vacuum vapor deposition apparatus), and then a vacuum pump was operated. At the same time, a temperature controlling medium was circulated in the fixing jig to adjust the temperature of the polyimide film to 25 deg. Lt; / RTI > After the temperature of the polyimide film reached 25 占 폚 and the pressure inside the magnetron sputtering apparatus reached 0.001 Pa, a magnetron power source was turned on and a voltage of 1 kV was applied. Next, argon gas was introduced into the magnetron sputtering apparatus through an external gas inlet, and the internal pressure was adjusted to 0.1 Pa. Subsequently, a power source of a magnetron sputtering apparatus connected to a metal (copper) evaporation source was operated to start film formation (copper deposition). When the thickness of the thin film layer (copper deposited film) became 1.0 탆, the film formation was terminated and the supply of argon gas was stopped. Next, the polyimide film having the thin film layer formed was cooled to 50 DEG C or lower, the evacuation of the vacuum pump was stopped, and the leak valve was opened to return the pressure inside the magnetron sputtering apparatus to normal pressure. Then, the polyimide film on which the thin film layer was formed was immersed in a solution of a high-speed type of bis (3-sulfopropylsulfonic acid) sodium salt (bis (3-sulfopropylsulfonic acid) sodium salt) (Copper sulfate) 75 g / L, sulfuric acid: 180 g / L, chlorine: 40 ppm) and electroplated to form a metal (copper) conductive layer having a thickness of 12 탆. Next, the polyimide film having the metal conductive layer formed thereon was heat-treated at 80 캜 for 30 minutes under a nitrogen atmosphere and below the glass transition temperature of the polyimide film to prepare a flexible metal foil-clad laminate.

Comparative Example  2

A flexible metal clad laminate was prepared in the same manner as in Comparative Example 1, except that the heat treatment was not performed after formation of the metal conductive layer.

Comparative Example  3

The polyimide film without the thin film layer was subjected to electroplating in the same manner as in Comparative Example 1, but the metal conductive layer was not formed.

Property evaluation method

In order to evaluate the bonding strength between the polymer film and the metal conductive layer of the flexible metal foil laminate prepared in Examples 1 to 5 and Comparative Examples 1 and 2, the following tape peel test was conducted and the results are shown in Table 1 below.

Tape peeling test: An adhesive tape having a width of 10 mm and a length of 40 mm was stuck on the surface of the metal conductive layer of the flexible metal foil laminate so that the bonding surface had a length of 20 mm and the other end of the adhesive tape was pulled to measure the strength required for peeling Respectively.

Example 1 Example 2 Example 3 Example 4 Example 5 Comparative Example 1 Comparative Example 2 Adhesive strength 12 N / cm 10 N / cm 10 N / cm 10 N / cm 9 N / cm 3 N / cm 1 N / cm

From the results shown in Table 1, it can be seen that the flexible metal foil-clad laminate (Example 1-5) according to the present invention has excellent adhesion strength between the polymer film and the metal conductive layer. Therefore, it can be understood that the flexible metal clad laminate having excellent adhesiveness can be produced even when a thin film layer containing no nickel, chromium, or the like is used, and the manufacturing process can be simplified.

On the other hand, in the case of Comparative Examples 1 and 2, the bonding strength was 3 N / cm and 1 N / cm, respectively, indicating low bonding strength.

It will be understood by those skilled in the art that various changes in form and details may be made therein without departing from the spirit and scope of the invention as defined by the appended claims.

Claims (9)

Depositing a metal on the polymer film to form a thin film layer;
Electroplating the polymer film having the thin film layer formed thereon to form a metal conductive layer on the thin film layer; And
Heating the polymer film at a temperature not lower than the glass transition temperature of the polymer film; ≪ / RTI >
When the polymer film is a thermoplastic resin, it is preferable that the glass transition temperature of the thermoplastic resin is in the range of -30 to 50 캜 and a pressure of 1 Pa or less Wherein when the polymer film is a thermosetting resin, it is performed at a temperature ranging from 100 to 300 ° C and a pressure of 1 Pa or less from the glass transition temperature of the thermosetting resin.
delete delete The method according to claim 1, wherein the thin film layer comprises at least one metal selected from the group consisting of copper, gold, silver, aluminum, titanium, zinc, vanadium and manganese.
The method of manufacturing a flexible metal-clad laminate according to claim 1, wherein the thickness of the thin film layer is 0.05 to 1 占 퐉.
The method according to claim 1, wherein the polymer film is at least one selected from the group consisting of polyimide, epoxy resin, Teflon, polyphenylene sulfide, polyamide, polyester, fluorinated polyolefin, polyimide ether, polyamideimide, aramid, polycarbonate, polyolefin and polycycloolefin Wherein the flexible metal foil laminate comprises at least one of the following materials.
The method of manufacturing a flexible metal film laminate according to claim 1, wherein the thin film layer is heated at 100 to 250 ° C for 3 minutes or more after forming the thin film layer.
The method of manufacturing a flexible metal-clad laminate according to claim 1, wherein the thickness of the metal conductive layer is 1 to 30 탆.
A flexible metal foil laminate produced from the manufacturing method according to any one of claims 1 to 8.

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