KR100656246B1 - Manufacturing method of flexible copper clad laminate using surface modification of polyimide film and its product thereby - Google Patents

Abstract

The present invention is a method of modifying the surface of a polyimide film by immersing a polyimide film in a solution containing a diamine compound represented by the following formula (1), a method for producing a flexible copper foil laminated film of a two-layer structure using the same and the production It relates to a flexible copper foil laminated film.

The surface modification method of the polyimide film of the present invention simplifies the method of modifying the surface of a conventional polyimide film by simply immersing the polyimide film in a solution containing a specific diamine compound, and the surface of the modified polyimide film. Two-layer flexible copper foil laminated film manufactured by copper sputtering and electrolytic copper plating method has excellent adhesive strength between copper foil and polyimide film, so it can be used for flexible printed circuit board, TCP (Tape Carrier Package), and COF (Chip On Film). It is useful for board | substrate material use of electronic components, such as these.

(Wherein R is as defined in the specification).

Copper Clad Laminated Film, Polyimide, Diamine, Sputtering, Electroplating

Description

MANUFACTURING METHOD OF FLEXIBLE COPPER CLAD LAMINATE USING SURFACE MODIFICATION OF POLYIMIDE FILM AND ITS PRODUCT THEREBY}

1 is an SEM photograph of the surface of a polyimide film according to Example 1 of the present invention,

2 is an AFM photograph of the surface of a polyimide film according to Example 1 of the present invention,

3 is a SEM photograph of the surface of the polyimide film according to Example 6 of the present invention,

4 is an AFM photograph of the surface of a polyimide film according to Example 6 of the present invention,

5 is an FT-IR spectrum analysis result of the surface-modified polyimide film according to the present invention,

6 is a result showing the peel strength of the copper-clad laminated film prepared according to the production method of the present invention,

7 is a schematic diagram of a pulsed DC spatter device used in the present invention.

<Brief Description of Drawings>

10: pulsed DC spatter device 1: argon gas inlet

2: Vacuum chamber 3: Cooling water inlet

4: height adjuster 5: cooling water outlet

6: cooling plate 7: polyimide film

8: Vacuum measuring gauge 9: Copper target

The present invention relates to a flexible copper clad laminated film and a method for manufacturing the same, and more particularly, to immerse a polyimide film in a solution containing a diamine compound, to modify the surface of the polyimide film, and to be carried out after the sputtering and electroplating. The present invention relates to a method for producing a polyimide copper clad laminated film having a two-layer structure under the optimum conditions of the present invention, and to an improved polyimide copper clad laminated film produced therefrom.

Polyimide film has excellent heat resistance, electrical properties, chemical resistance and flex resistance compared to other polymer materials, and is used for electronic parts such as flexible printed circuit boards, auto bonding (TAB) tape, and chip on film (COF). It is variously used as an insulating substrate material. The copper foil laminated film used in the flexible printed circuit board is a three-layer copper foil laminated film using an epoxy adhesive, but the dimensional stability is poor due to the problem that the heat resistance of the adhesive is lowered, it is pointed out that it is not suitable for fine patterning applications have.

Therefore, the trend of changing from a three-layer (layer), which has been mainstream in recent years, to a two-layer structure product is accelerating. This two-layer structure directly diecasts or hot-bonds the polyimide film to the copper foil to eliminate the adhesive layer, thus providing the advantage of easy formation of fine patterns and excellent flexibility. In addition, due to these advantages, the copper foil laminated film having a two-layer structure can broaden the marketability of display products such as cellular phone folders, LCDs, and PDP modules.

In particular, domestic substrate materials for electronic components depend mostly on imports, and there is an urgent need for research on flexible copper clad laminate (FCCL) applied a new method.

In the two-layer FCCL manufacturing method, a technique of laminating a polyimide film and a copper foil instead of an adhesive has been reported.

In addition, as a sputtering-electroplating method, a method of forming a thin seed metal layer (nickel, chromium, etc.) in advance by sputtering and then forming a copper layer having a desired thickness by electroplating has been proposed. The surface modification process must be preceded by the above, and in this process, a special seed layer is required, and in particular, when manufacturing the double-sided copper-clad laminated film, a special manufacturing facility is required. In addition, in the high temperature and high humidity environment, the adhesive strength of the copper foil laminate is unstable, and thus the reliability is low, and there is a disadvantage of environmental pollution due to the drill work on the PCB (Printed Circuit Board) post-treatment process.

Accordingly, the present inventors have tried to solve the conventional problems and obtain a flexible copper foil laminated film having a two-layer structure, and as a result of simply immersing the polyimide film in a solution containing a specific diamine compound, the surface of the polyimide film The present invention provides a method for manufacturing a flexible copper foil laminated film having a two-layer structure that is modified to be optimized as conditions for copper sputtering and electrolytic copper plating, and the flexible copper foil laminated film thus prepared is easy to manufacture double-sided flexible copper foil laminated film. The present invention was completed by confirming the excellent adhesive force, which is a required characteristic.

It is an object of the present invention to provide a method of surface modification of a polyimide film.

Another object of the present invention is to provide a method for producing a flexible copper foil laminated film having a two-layer structure using the surface modification method of the polyimide film and performing optimization conditions of copper sputtering and electrolytic copper plating.

Still another object of the present invention is to provide a flexible copper foil laminated film of one side or both sides manufactured by the manufacturing method.

In order to achieve the above object, the present invention provides a surface modification method of a polyimide film, immersing one or both sides of the polyimide film in a solution containing a diamine compound represented by the formula (1).

Formula 1

More specifically, the diamine compound is ethylenediamine, triethylenediamine, tetramethylenediamine, pentamethylenediamine, hexamethylenediamine, diethylenetriamine, triethylenetetraamine, 1,3-phenylenediamine , 1,4-phenylene diamine, 4,4'-diaminodiphenyl methane, 4,4'-diamino diphenylether, 3,3-diamino benzophenone, 4,4-diamino benzophenone, 1,3-bis (aminophenoxy) benzene, 1,4-bis (aminophenoxy) benzene, bis (3-aminophenyl) sulfone and bis (4-aminophenyl sulfone), 3,3-diamino benzidine, Any one selected from the group consisting of 4,4- (hexafluoroisopropylidine) dianiline and 3,3- (hexafluoroisopropylidine) dianiline is used.

The present invention uses a solution containing a diamine compound prepared by dissolving the diamine compound at 0.5-20 M concentration in at least one solvent selected from the group consisting of water, acetone, methanol, ethanol and isopropanol.

In addition, the present invention provides a method for producing a copper-clad laminated film using the method for modifying the surface of the polyimide film. More specifically, the preparation method of the present invention comprises the steps of modifying the surface of the polyimide film by immersing one or both sides of the polyimide film in a solution containing the diamine compound represented by the formula (1); Washing and drying the surface modified polyimide film; Step 3 of copper sputtering the polyimide film dried in the step at 0.5 to 30 mA and 50 to 500 W for 1 to 10 hours to form a copper sputtering layer; And electroplating the copper sputtering layer to form an electrocopper plating layer.

Preferred immersion conditions for modifying the surface of the polyimide film in step 1 is to perform for 30 seconds to 2 hours at a temperature of 40 ~ 100 ℃.

The thickness of the copper sputtering layer prepared in step 3 is 500 to 5,000 mm 3, and the thickness of the electroplated layer prepared in step 4 is 1 to 50 μm. Therefore, the copper foil laminated film of the present invention is a two-layer structure consisting of the electroplated layer formed by electroplating on the copper surface of the polyimide film formed by sputtering.

In addition, the present invention is copper sputtering layer formed to a thickness of 500 ~ 5,000Å on one side or both sides of the polyimide film surface-treated by immersing in the solution containing the diamine compound; And

It provides a single-sided or double-sided polyimide copper foil laminated film formed of an electroplating layer of 1 ~ 50㎛ thickness formed by electroplating on the copper sputtering layer.

Hereinafter, the present invention will be described in detail.

The present invention provides a method for surface modification of a polyimide film, in which one or both sides of a polyimide film are immersed in a solution containing a diamine compound represented by the formula (1).

The surface modification method of the polyimide film of this invention reacts with the acid component of a polyimide film surface, and a diamine compound, and introduce | transforms an amide amine group in a polyimide film, and a surface is modified.

The diamine compound of the present invention is represented by the following formula (1).

Formula 1

More specifically, the diamine compound of the present invention, the diamine compound is ethylenediamine, triethylenediamine, tetramethylenediamine, pentamethylenediamine, hexamethylenediamine, diethylenetriamine, triethylenetetraamine, 1 , 3-phenylenediamine, 1,4-phenylene diamine, 4,4'-diaminodiphenyl methane, 4,4'-diamino diphenylether, 3,3-diamino benzophenone, 4, 4-diamino benzophenone, 1,3-bis (aminophenoxy) benzene, 1,4-bis (aminophenoxy) benzene, bis (3-aminophenyl) sulfone and bis (4-aminophenyl sulfone), 3 It is any one selected from the group consisting of, 3-diamino benzidine, 4,4- (hexafluoroisopropylidine) dianiline, and 3,3- (hexafluoroisopropylidine) dianiline.

The diamine compound is dissolved in one or more solvents selected from the group consisting of water, acetone, methanol, ethanol and isopropanol, to prepare a diamine solution having a concentration of 0.5 to 20 M.

In addition, the polyimide film that can be used in the present invention is not particularly limited as long as the polyimide film has a thickness of 10 to 100 μm, even if it is synthetic or commercially available. ), Japan Upbex-S from Ube, or Apical from Kaneka, Japan Use film.

1 and 2 are the results of measuring the surface of the surface-modified polyimide film in Example 1 of the present invention using SEM and AFM, Figure 3 and Figure 4 is a surface-modified polyimide film of Example 6 The surface was measured using SEM and AFM. From the above results, it was confirmed that the surface roughness was increased by immersing the polyimide film in the solution containing the diamine compound of the present invention. From the results of the SEM photographs, it can be seen that the surface of the polyimide film of Example 1 was modified from fine projections, and the AFM results showed a distinct surface roughness through roughness, thereby confirming surface modification. Can be.

In addition, Figure 5 is a result of the FT-IR spectrum analysis of the polyimide film according to the surface modification method according to the present invention, the present invention is immersed in a solution containing a diamine in the polyimide film, 2700 ~ 2250 cm ^-1 region While the amide amine group of was identified, the comparative example surface-modified using potassium hydroxide showed a hydroxyl group in the 3600-2700 cm ^-1 region.

In addition, the present invention provides a method for producing a copper-clad laminated film using the method for modifying the surface of the polyimide film. More specifically, the manufacturing method of the present invention
1) modifying the surface of the polyimide film by immersing one or both sides of the polyimide film in a solution containing the diamine compound represented by Formula 1;
2) washing and drying the surface modified polyimide film;

3) copper sputtering the polyimide film dried in the step at 0.5 to 30 mA and 50 to 500 W for 1 to 10 hours to form a copper sputtering layer; And

4) electroplating the copper sputtering layer to form an electrocopper plating layer.

Preferred immersion conditions for modifying the surface of the polyimide film in step 1 is preferably immersed in a temperature range from room temperature to the boiling point of the selected solvent, more preferably 40 to 100 ℃. In addition, the immersion time may vary depending on the temperature, but is carried out for 30 seconds to 2 hours, if the treatment time is too short, the surface modification rate is low and the surface modification hardly occurs, while if the treatment time is long surface modification Is smooth but unfavorable because it affects the physical properties.

Step 2 is a step of washing the surface-modified polyimide film with distilled water and an alcohol solvent in the step, remove the unreacted diamine solution, and sufficiently dry the surface using a hot air dryer to the copper sputtering process Optimize to suit.

Step 3 is a sputtering step of washing and drying to form a film by colliding a copper atom to the surface-modified polyimide film.

A sputtering step of the present invention is performed by using the pulse (pulse) DC spa emitter device 10 shown in FIG. The surface-modified polyimide film 7 was raised on the cooling plate 6 in the above step, and argon 5 to 30 sccm in the vacuum chamber 2 maintained at 1 × 10 ⁻³ to 1 × 10 ⁻⁵ torr. The gas is introduced (1) to form an atmosphere, and the sputtering process is performed for 1 to 10 hours while controlling the 0.5 to 30 mA current to a power of 50 to 500 W, and maintained at a thickness of 500 to 5,000 mW. At this time, when the thickness of the copper sputtering layer due to spattering is less than 500 μs, pinholes may occur or electricity may not be applied during electroplating, or the adhesion of plating may be weak. Many and too thick are undesirable for use as substrate materials.

Subsequently, step 4 is a step of forming an electric copper plating layer by electroplating the prepared copper sputtering layer, electrolytic copper plating on copper foil of a controlled thickness in the sputtering step to directly deposit copper to a certain thickness, the preferred copper foil thickness Is 1-50 micrometers. At this time, when the electric copper plating layer exceeds 50 µm, the precision of the line width in the high-density wiring is lowered or unfavorable in terms of light weight and miniaturization in component mounting.

6 is a result showing the peel strength of the copper foil laminated film prepared according to the production method of the present invention, the present invention is 2 ~ than the case of the copper foil film prepared by immersing the polyimide film in an alkaline solution used in the conventional surface treatment It shows three times better peel strength.

Therefore, the present invention is to modify the surface of the polyimide film from the step of immersing one or both sides of the polyimide film in the solution containing the diamine compound, and directly on the modified surface using a copper spattering and electroplating method By laminating copper to a certain thickness, it provides a flexible copper foil laminated film with improved adhesion between the copper foil and the polyimide film.

The copper foil laminated film of the two-layer structure of the present invention forms a mask having a pattern, selectively exposes and removes the exposed copper thin film portion with a copper etching solution, and applies it to a method of forming a copper circuit pattern, thereby providing a flexible printed circuit board. Or it is useful for substrate materials of electronic components such as Tape Carrier Package (TCP), Chip On Film (COF).

Hereinafter, the present invention will be described in detail by way of examples.

The following examples are merely illustrative of the present invention, but the scope of the present invention is not limited to the following examples.

<Example 1>

The polyimide film was immersed in 10M aqueous solution of ethylenediamine at 80 ° C. for 3 minutes, and then washed 5 times for 10 minutes using distilled water and isopropyl alcohol. After washing, it was sufficiently dried in a warm air dryer, set in a copper sputtering apparatus, and then sputtered at 20 mA for 1 hour to uniformly adjust the copper thickness to 2,000 kPa. Then, it was mounted in a copper sulfate plating bath and subjected to electroplating at room temperature for 1 hour to prepare a 10 μm polyimide copper foil laminated film.

<Example 2>

A polyimide copper foil laminated film was prepared in the same manner as in Example 1 except that the polyimide film was immersed in 10M aqueous solution of ethylenediamine for 10 minutes at 80 ° C.

<Example 3>

A polyimide copper-clad laminated film was prepared in the same manner as in Example 1 except that the polyimide film was immersed in 10M aqueous solution of ethylenediamine for 10 minutes at room temperature.

<Example 4>

A polyimide copper-clad laminated film was prepared in the same manner as in Example 1 except that the polyimide film was immersed in 10M aqueous solution of ethylenediamine at 100 ° C. for 3 minutes.

Example 5

The polyimide film was treated with 3M triethylenetetraamine aqueous solution at 80 ° C. for 3 minutes, and then washed 5 times with distilled water and methanol for 10 minutes. After washing, it was sufficiently dried in a warm air dryer, set in a copper sputtering apparatus, and sputtered at 30 mA for 1 hour to adjust the copper thickness to maintain 2,000 kPa. Then, it was mounted in a copper sulfate plating bath and subjected to electroplating at room temperature for 1 hour to prepare a polyimide copper foil laminated film of 20 µm.

<Example 6>

A polyimide copper-clad laminated film was prepared in the same manner as in Example 5 except that the polyimide film was immersed in 3M aqueous triethylenetetraamine solution at 25 ° C. for 10 minutes.

<Example 7>

A polyimide copper foil laminate film was prepared in the same manner as in Example 5 except that the polyimide film was immersed in 3M aqueous triethylenetetraamine solution at 60 ° C. for 1 minute.

<Example 8>

A 3M 1,4-phenylene diamine solution was prepared using a mixed solvent having acetone: ethanol: distilled water in a volume ratio of 1: 1: 0.5.

Thereafter, the polyimide film was immersed in the 3M 1,4-phenylene diamine aqueous solution at 40 ° C. for 30 minutes, and then the sputtering and electroplating processes were performed in the same manner as in Example 5 to laminate the polyimide copper foil. A film was prepared.

Comparative Example 1

As a technique for improving the adhesion of polyimide film by alkali surface treatment is known [Korean Journal of Textile Science and Engineering, 34, 3, 178-185p], a polyimide film was added to 3M aqueous potassium hydroxide (KOH) solution. After immersion for 3 minutes at ° C., the sputtering and electroplating process was carried out in the same manner as in Example 1 to prepare a polyimide copper foil laminated film.

Comparative Example 2

The polyimide film was immersed in 3M aqueous potassium hydroxide (KOH) solution at 25 ° C. for 10 minutes, and then the sputtering and electroplating processes were performed in the same manner as in Example 1 to prepare a polyimide copper foil laminate film.

Comparative Example 3

The polyimide film was immersed in 3M aqueous potassium hydroxide (KOH) solution at 60 ° C. for 20 minutes, and then the sputtering and electroplating processes were performed in the same manner as in Example 1 to prepare a polyimide copper foil laminated film.

<Comparative Example 4>

The polyimide film was immersed in 3M aqueous potassium hydroxide (KOH) solution at 60 ° C. for 10 minutes, and then the sputtering and electroplating processes were performed in the same manner as in Example 1 to prepare a polyimide copper foil laminate film.

Experimental Example 1

In order to measure the adhesive strength of the polyimide copper foil laminated | multilayer film manufactured in the said Examples 1-8 and Comparative Examples 1-4, it measured as follows.

The copper foil film prepared after the electroplating process in Examples 1 to 8 and Comparative Examples 1 to 4 was patterned by using an acid paint or an acid resistant tape, and then etched using an etching solution made of sulfuric acid and copper sulfate solution. The physical properties of the 필 peel adhesive force were evaluated, and the results are shown in Table 1 .

division Solution Contact angle after surface treatment Adhesive force (kg / cm) Example 1 Ethylenediamine 32 0.95 Example 2 Ethylenediamine 30 0.81 Example 3 Ethylenediamine 35 0.92 Example 4 Ethylenediamine 30 1.20 Example 5 Triethylenetetraamine 33 0.88 Example 6 Triethylenetetraamine 34 0.80 Example 7 Triethylenetetraamine 34 0.92 Example 8 1,4-phenylenediamine 35 0.96 Comparative Example 1 Potassium hydroxide 30 0.43 Comparative Example 2 Potassium hydroxide 32 0.42 Comparative Example 3 Potassium hydroxide 27 0.43 Comparative Example 4 Potassium hydroxide 28 0.34

As shown in Table 1, the copper-clad laminated film prepared in Examples 1 to 8, in which the polyimide film was immersed in a diamine solution, has an adhesive strength of 0.8 kg / cm or more with a surface-modified polyimide film and copper. It showed, and showed excellent adhesive strength of 2-3 times than the copper foil film prepared in Comparative Examples 1-4.

Therefore, since the copper foil laminated film with improved adhesive strength can be obtained, by providing a polyimide copper foil laminated film having a two-layer structure without a separate adhesive layer, fine wiring is possible and is useful for a flexible printed circuit board with excellent adhesive strength.

As described above, the present invention

First, by modifying the surface of the polyimide film by immersing the solution containing the diamine compound in the polyimide film, it replaces the conventional surface treatment process by the ion beam, and does not use a special seed layer, heavy metals with cost reduction Can reduce environmental pollution, and at the same time, due to the simplicity of the process,

Secondly, using the modification method of the surface of the polyimide film of the present invention, and provided the optimum conditions when performing copper spattering and electroplating,

Third, it is possible to provide a polyimide copper foil laminated film having a two-layer structure, and in particular, by performing surface modification on one or both surfaces of the polyimide film, it is possible to provide a single-sided, double-sided polyimide copper foil laminated film.

Although the present invention has been described in detail only with respect to the embodiments described, it will be apparent to those skilled in the art that various modifications and variations are possible within the technical spirit of the present invention, and such modifications and variations belong to the appended claims. .

Claims (11)

delete delete delete delete 1) modifying the surface of the polyimide film by immersing one or both sides of the polyimide film in a solution containing the diamine compound represented by Formula 1 below; 2) washing and drying the surface modified polyimide film; 3) copper sputtering the polyimide film dried in the step at 0.5 to 30 mA and 50 to 500 W for 1 to 10 hours to form a copper sputtering layer; And 4) electroplating the copper sputtering layer to form an electrocopper plating layer; a method of manufacturing a flexible copper foil laminated film having a two-layer structure using a surface-modified polyimide film, characterized in that consisting of. Formula 1

The flexible copper foil of the two-layer structure according to claim 5, wherein the cross-section or both sides of the polyimide film is immersed in the solution containing the diamine compound in step 1 for 30 seconds to 2 hours at 40 to 100 ° C. Method of manufacturing laminated film. The method for producing a flexible copper foil laminated film according to claim 5, wherein the copper sputtering layer has a thickness of 500 to 5,000 kPa. The method for producing a flexible copper foil laminated film of the two-layer structure according to claim 5, wherein the electrocopper plating layer has a thickness of 1 to 50 µm. Copper sputtering layer formed to a thickness of 500 ~ 5,000Å on one or both surfaces of the polyimide film surface-treated by immersing in a solution containing a diamine compound in step 1 of claim 5; And An electro-copper plating layer having a thickness of 1 to 50 μm formed by electroplating on the copper sputtering layer. The flexible copper foil laminated film having a two-layer structure manufactured by the manufacturing method of claim 5. The diamine compound according to claim 5, wherein the diamine compound is ethylenediamine, triethylenediamine, tetramethylenediamine, pentamethylenediamine, hexamethylenediamine, diethylenetriamine, triethylenetetraamine, 1,3-phenyl Rendiamine, 1,4-phenylene diamine, 4,4'-diaminodiphenyl methane, 4,4'-diamino diphenylether, 3,3-diamino benzophenone, 4,4-diamino Benzophenone, 1,3-bis (aminophenoxy) benzene, 1,4-bis (aminophenoxy) benzene, bis (3-aminophenyl) sulfone and bis (4-aminophenyl sulfone), 3,3-dia Mino-benzidine, 4,4- (hexafluoroisopropylidine) dianiline, 3,3- (hexafluoroisopropylidine) dianiline any one selected from the group consisting of the soft copper foil of the said two-layer structure Method of manufacturing laminated film. The solution of claim 5, wherein the solution containing the diamine compound is prepared by dissolving the diamine compound at a concentration of 0.5 to 20 M in at least one solvent selected from the group consisting of water, acetone, methanol, ethanol and isopropanol. The method of manufacturing a flexible copper foil laminated film of the two-layer structure.

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