KR102337237B1 - Laminate structure, flexible copper clad laminate film including the same, method of manufacturing the laminate structure - Google Patents

Abstract

A laminated structure, a flexible copper clad laminate including the same, and a manufacturing method of the laminated structure are disclosed. The laminated structure may include a non-conductive polymer substrate; a nickel-containing plating layer disposed on at least one surface of the substrate; and a first copper plating layer disposed on the nickel-containing plating layer, wherein a [111] orientation plane by X-ray diffraction (XRD) analysis appears with respect to the first copper plating layer, and the non-conductivity ^{The peeling rate per 1 cm 2} unit area between the polymer substrate and the nickel-containing plating layer may be 1% or less.

Description

A laminate structure, a flexible copper clad laminate film including the same, and a method of manufacturing the laminate structure

It relates to a laminated structure, a flexible copper clad laminate including the same, and a method for manufacturing the laminated structure.

Recently, in accordance with the acceleration of the growth of the mobile market and the increase in demand for LCD TV monitors, the development of materials having characteristics of thin film, miniaturization, light weight, durability, and high quality in the fields of electronic products and semiconductor integrated circuits has been promoted. In the field of flexible copper clad laminate (FCCL) used in driver integrated circuits (ICs) for LCDs, fine patterning, thinning and durability are increasingly required.

The flexible copper clad laminated film (FCCL) has a structure in which a circuit pattern is formed on the surface and an electronic device such as a semiconductor chip is mounted on the circuit pattern. Recently, the number of products having a pitch of the circuit pattern of 23 μm or less is increasing, and the instability of dimensional change is a problem due to a downward trend in pitch and line width.

In order to solve this problem, the fine circuit pattern forming technology is also being developed. However, for fine circuit patterning, high adhesion between the substrate and the metal layer must be maintained, and the problem of peeling between them must be solved. A new laminate structure, a flexible copper clad laminate including the same, and a method for manufacturing the laminate is still there

In one aspect, by removing impurities such as organic matter, additives, and coagulation gas in the nickel-containing plating layer, the adhesion between the non-conductive polymer substrate and the nickel-containing plating layer can be improved, and the peeling rate per ^{1 cm 2 unit area therebetween can be reduced.} A laminate structure is provided.

In another aspect, there is provided a flexible copper clad laminate including the laminate structure.

Another aspect provides a method of manufacturing the laminate structure.

According to one aspect,

non-conductive polymer substrate;

a nickel-containing plating layer disposed on at least one surface of the substrate; and

a first copper plating layer disposed on the nickel-containing plating layer;

[111] azimuthal plane by X-ray diffraction (XRD) analysis appears with respect to the first copper plating layer,

Between the non-conductive polymer substrate and the nickel-containing plating layer, there is provided a laminate structure having a peeling rate of 1% or less per ^{1 cm 2 unit area.}

One or both of the [200] azimuth, [220] azimuth, and [311] azimuth plane by X-ray diffraction (XRD) analysis with respect to the first copper plating layer may additionally appear at the same time can

[111] azimuth, [200] azimuth, [220] azimuth, and [311] azimuth by X-ray diffraction (XRD) analysis with respect to the first copper plating layer may not appear at the same time .

For the first copper plating layer, the crystal orientation index of the [200] orientation with respect to the [111] orientation by X-ray diffraction (XRD) analysis according to Equation 1 below satisfies 0 to less than 25%. can:

[Equation 1]

Crystal orientation index (%) = I _[200] /I _[111] = {(X-ray diffraction peak intensity in [200] azimuth/X-ray diffraction peak intensity in [111] azimuth) × 100}

For the first copper plating layer, the crystal orientation index of the [220] orientation with respect to the [111] orientation by X-ray diffraction (XRD) analysis according to Equation 2 below satisfies 0 to less than 15%. can:

[Equation 2]

Crystal orientation index (%) = I _[220] /I _[111] = {(X-ray diffraction peak intensity in [220] orientation / X-ray diffraction peak intensity in [111] orientation) × 100}

For the first copper plating layer, the crystal orientation index of the [311] orientation with respect to the [111] orientation by X-ray diffraction (XRD) analysis according to Equation 3 below satisfies 0 to less than 14%. can:

[Equation 3]

Crystal orientation index (%) = I _[311] /I _[111] = {(X-ray diffraction peak intensity in [311] orientation/X-ray diffraction peak intensity in [111] orientation) × 100}

The non-conductive polymer substrate may include at least one selected from a phenol resin, a phenolaldehyde resin, an allyl resin, an epoxy resin, a polyethylene resin, a polypropylene resin, a polyester resin, and a polyimide resin.

The thickness of the non-conductive polymer substrate may be 7 μm to 50 μm.

The nickel-containing plating layer may be an electroless plating layer.

The nickel-containing plating layer may include nickel or a nickel alloy.

The thickness of the nickel-containing plating layer may be 40 nm to 250 nm.

The first copper plating layer may be an electroless plating layer.

The thickness of the first copper plating layer may be 40 nm to 200 nm.

A second copper plating layer may be further included on the first copper plating layer.

The second copper plating layer may be an electrolytic plating layer.

The thickness of the second copper plating layer may be 0.5 μm to 5.0 μm.

According to the other aspect,

There is provided a flexible copper clad laminate including the above-described laminate structure.

According to another aspect,

forming a nickel-containing plating layer on at least one surface of the non-conductive polymer substrate;

forming a first copper plating layer on the nickel-containing plating layer;

heat-treating the first copper plating layer; and

There is provided a method for manufacturing a laminated structure comprising; forming a second copper plating layer on the heat-treated first copper plating layer to prepare the above-described laminated structure.

Each of the nickel-containing plating layer and the first copper plating layer may be formed by an electroless plating method.

The heat treatment step may include a process of performing a heat treatment at a temperature of 100 ° C. to 180 ° C. for 1 minute to 30 minutes.

The second copper plating layer may be formed by an electrolytic plating method.

In the laminated structure according to one aspect, a [111] orientation plane by X-ray diffraction (XRD) analysis of the first copper plating layer appears, and 1 cm between the non-conductive polymer substrate and the nickel-containing plating layer ^{2 The} peeling rate per unit area may be 1% or less.

The method of manufacturing a laminate structure according to another aspect may include heat-treating the first copper plating layer to remove impurities such as organic substances, additives, and coagulation gas in the nickel-containing plating layer. ^{Due to this, the peeling rate per 1 cm 2} unit area between the non-conductive polymer substrate and the nickel-containing plating layer may be reduced.

1 is a schematic cross-sectional view of a laminated structure according to an embodiment.
Figure 2 (a) is a schematic diagram showing the crystal structure of the first copper plating layer; FIG. 2(b) is a schematic diagram showing the [111] orientation by X-ray diffraction (XRD) analysis in the crystal structure of the first copper plating layer.
3(a) shows the [111] orientation by X-ray diffraction (XRD) analysis in the crystal structure of the first copper plating layer; Fig. 3(b) shows the growth of copper particles (gray) constituting each corner of the [111] orientation plane of Fig. 3(a); Fig. 3(c) shows that the tensile stress and elastic energy generated between the grown copper particles (gray) of Fig. 3(b) increase; FIG. 3(d) shows X-ray diffraction (XRD) in a stable state with a small density in order to resolve the internal stress of tensile stress and elastic energy generated between the grown copper particles (gray) of FIG. 3(c). ) is a schematic diagram showing the process of growth in the [200] orientation by analysis.
4 is a result of XRD (X-ray diffraction) analysis of the first copper plating layer of the flexible copper clad laminated film prepared in Examples 1 to 6;
5 is a result of XRD analysis of the first copper plating layer of the flexible copper clad laminated film prepared in Examples 7 to 10.
6 is a result of XRD analysis of the first copper plating layer of the flexible copper clad laminated film prepared in Comparative Example 1. Referring to FIG.
7A and 7B show the first copper plating layer of the flexible copper clad laminate film prepared in Example 1, after heat treatment at a temperature of about 165° C. for about 3 minutes by hot air drying by convection heat, between the polyimide film and the nickel plating layer. Here are photographs and optical microscopy images to evaluate the rate of peeling per ^{1 cm 2 unit area.}
7c and 7d are, respectively, between the polyimide film and the nickel plated layer without heat treatment on the first copper plated layer of the flexible copper clad laminated film prepared in Comparative Example 1 1 cm ² Photographs for evaluating the rate of peeling per unit area and an optical microscope image.

Hereinafter, a laminated structure, a flexible copper clad laminate including the same, and a method of manufacturing the laminated structure will be described in detail with reference to embodiments and drawings of the present invention. It will be apparent to those of ordinary skill in the art that these examples are merely presented by way of example to explain the present invention in more detail, and that the scope of the present invention is not limited by these examples. .

Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. In case of conflict, the present specification, including definitions, will control.

Although methods and materials similar or equivalent to those described herein can be used in the practice or testing of the present invention, suitable methods and materials are described herein.

As used herein, the term “on (or on)” includes not only a case in which another part is located “directly on (or directly on)” but also a case in which another part is interposed therebetween. Conversely, the term “directly on (or directly on)” means without intervening other portions.

In general, in the field of copper clad laminated film (CCL), voids and internal stress may occur in the particles according to the change in the properties of the metal layer. In addition, when the post-plating process is performed, impurities such as organic matter, additives, and coagulant gas are ejected from the inside of the metal layer, which may cause quality defects on the surface of the copper clad laminate. Furthermore, the pattern peeling phenomenon may occur due to insufficient adhesion between the substrate and the metal layer during the etching process for the copper clad laminate film and the circuit pattern formation.

The inventors of the present invention intend to propose the following laminated structure in order to improve the above problems.

A laminate structure according to an embodiment includes a non-conductive polymer substrate; a nickel-containing plating layer disposed on at least one surface of the substrate; and a first copper plating layer disposed on the nickel-containing plating layer, wherein a [111] orientation plane by X-ray diffraction (XRD) analysis appears with respect to the first copper plating layer, and the Between the non-conductive polymer substrate and the nickel-containing plating layer, the ^{peeling rate per 1 cm 2} unit area may be 1% or less.

A laminate structure according to an embodiment includes a non-conductive polymer substrate; a nickel-containing plating layer disposed on one or both surfaces of the substrate; and a first copper plating layer disposed on the nickel-containing plating layer.

1 is a schematic cross-sectional view of a laminated structure according to an embodiment.

Referring to FIG. 1 , a laminate structure according to an embodiment includes, for example, nickel-containing plating layers 2 and 2 ′ disposed on both surfaces of a non-conductive polymer substrate 1 ; and a first copper plating layer (3, 3') respectively disposed on the nickel-containing plating layer (2, 2'); And it may be a laminated structure 10 having a second surface 6 in the downward direction.

2(a) is a schematic diagram showing a crystal structure of a first copper plating layer. FIG. 2(b) is a schematic diagram showing the [111] orientation plane in the crystal structure of the first copper plating layer.

Referring to FIG. 2( a ), the crystal structure of the first copper plating layers 3 and 3 ′ represents a face-centered cubic structure. Referring to FIG. 2(b) , the [111] orientation plane, which is the most stable orientation plane in the crystal structure of the first copper plating layers 3 and 3', is shown. The [111] orientation can be confirmed by X-ray diffraction (XRD) analysis.

^{The peeling rate per 1 cm 2} unit area between the non-conductive polymer substrate 1 and the nickel-containing plating layers 2 and 2' may be 1% or less. In the laminated structure 10 having such a peeling rate, excellent adhesion between the non-conductive polymer substrate 1 and the nickel-containing plating layers 2 and 2' is maintained even when a fine pattern is formed on the laminated structure 10. can

One or two orientations of the [200] orientation, [220] orientation, and [311] orientation by X-ray diffraction (XRD) analysis with respect to the first copper plating layers 3 and 3' Additional faces may appear at the same time.

3(a) shows the [111] orientation by X-ray diffraction (XRD) analysis in the crystal structure of the first copper plating layer; Fig. 3(b) shows the growth of copper particles (gray) constituting each corner of the [111] orientation plane of Fig. 3(a); Fig. 3(c) shows that the tensile stress and elastic energy generated between the grown copper particles (gray) of Fig. 3(b) increase; FIG. 3(d) shows X-ray diffraction (XRD) in a stable state with a small density in order to resolve the internal stress of tensile stress and elastic energy generated between the grown copper particles (gray) of FIG. 3(c). ) is a schematic diagram showing the process of growth in the [200] orientation by analysis.

Referring to FIG. 3( a ), the first copper plating layers 3 and 3 ′ have a face-centered cubic structure in which copper particles (gray) are arranged at the vertices of each corner, and are cast to reduce grain boundaries. As a scene, the [111] azimuth by X-ray diffraction (XRD) analysis is shown. Referring to FIG. 3(b), in the first copper plating layers 3 and 3', copper particles (gray) constituting each corner of the [111] orientation of FIG. 3(a) grow and the grain boundary area decreases. This indicates that tensile stress is generated between them. Referring to FIG. 3 ( c ), the first copper plating layers 3 and 3 ′ show that the tensile stress increases between the grown copper particles (gray) of FIG. 3 ( b ) and, accordingly, the elastic energy increases. . Referring to FIG. 3(d), the first copper plating layers 3 and 3' have a density in order to resolve the internal stress of tensile stress and elastic energy generated between the grown copper particles (gray) of FIG. 3(c). It shows the process of growth in the [200] orientation by X-ray diffraction (XRD) analysis in a small and stable state.

[111] azimuth, [200] azimuth, [220] azimuth, and [311] azimuth by X-ray diffraction (XRD) analysis with respect to the first copper plating layers 3 and 3' may not appear at the same time. The first copper plating layers 3 and 3 ′ may block thermal damage, and a uniform plating layer may be formed.

The crystal orientation index of the [200] orientation with respect to the [111] orientation by X-ray diffraction (XRD) analysis according to Equation 1 for the first copper plating layers 3 and 3' is 0 to less than 25% may be satisfied:

[Equation 1]

Crystal orientation index (%) = I _[200] /I _[111] = {(X-ray diffraction peak intensity in [200] azimuth/X-ray diffraction peak intensity in [111] azimuth) × 100}

For example, the crystal orientation of the [200] orientation with respect to the [111] orientation by X-ray diffraction (XRD) analysis according to Equation 1 for the first copper plating layers 3 and 3' The index may satisfy 0.01 to less than 25%.

The crystal orientation index of the [220] orientation with respect to the [111] orientation by X-ray diffraction (XRD) analysis according to Equation 2 for the first copper plating layers 3 and 3' is 0 to less than 15% may be satisfied:

[Equation 2]

Crystal orientation index (%) = I _[220] /I _[111] = {(X-ray diffraction peak intensity in [220] orientation / X-ray diffraction peak intensity in [111] orientation) × 100}

For example, determination of the [220] orientation with respect to the [111] orientation by X-ray diffraction (XRD) analysis according to Equation 2 below with respect to the first copper plating layers 3 and 3' The orientation index may satisfy 0.01 to less than 15%.

The crystal orientation index of the [311] orientation with respect to the [111] orientation by X-ray diffraction (XRD) analysis according to Equation 3 for the first copper plating layers 3 and 3' is 0 to less than 14% may be satisfied:

[Equation 3]

Crystal orientation index (%) = I _[311] /I _[111] = {(X-ray diffraction peak intensity in [311] orientation/X-ray diffraction peak intensity in [111] orientation) × 100}

For example, determination of the [311] orientation with respect to the [111] orientation by X-ray diffraction (XRD) analysis according to Equation 3 for the first copper plating layers 3 and 3' The orientation index may satisfy 0.01 to less than 14%:

[200] for the [111] orientation by X-ray diffraction (XRD) analysis according to Equation 1, Equation 2, or/and Equation 3 for the first copper plating layers 3 and 3' If the crystal orientation index of the orientation plane, the [220] orientation plane, or / and the [311] orientation plane is satisfied, the ^{peeling rate per 1 cm 2} unit area between the non-conductive polymer substrate and the nickel-containing plating layer can be greatly reduced. .

The non-conductive polymer substrate 1 may include at least one selected from a phenol resin, a phenolaldehyde resin, an allyl resin, an epoxy resin, a polyethylene resin, a polypropylene resin, a polyester resin, and a polyimide resin. For example, the non-conductive polymer substrate 1 may include at least one selected from a polyester resin and a polyimide resin. For example, the non-conductive polymer substrate 1 may be a polyimide resin.

The thickness of the non-conductive polymer substrate 1 may be 7 μm to 50 μm. For example, the non-conductive polymer substrate 1 may have a thickness of 7 μm to 40 μm. For example, the non-conductive polymer substrate 1 may have a thickness of 7 μm to 30 μm. For example, the non-conductive polymer substrate 1 may have a thickness of 7 μm to 25 μm. If the thickness of the non-conductive polymer substrate 1 is less than 7 μm, productivity may decrease when manufacturing the laminated film, and if it exceeds 50 μm, thinning may not be achieved.

In addition, the non-conductive polymer substrate 1 may be subjected to a surface treatment such as plasma treatment on the substrate 1 . The surface treatment may improve the chemical activity and roughness of the surface of the substrate 1 to easily secure excellent adhesion to the metal layer.

The nickel-containing plating layers 2 and 2' may be an electroless plating layer. Plasma surface treatment of the general sputtering method for the nickel-containing plating layer (2, 2') can secure the adhesion to the non-conductive polymer substrate, but when processing the thin film non-conductive polymer substrate (1) with a thickness of 25 μm or less, thermal damage may occur. In order to overcome such thermal damage, the nickel-containing plating layers 2 and 2 ′ improve adhesion to the substrate 1 by forming an electroless nickel-containing plating layer using an electroless plating method of depositing a metal in an aqueous solution state, thereby improving the adhesion and thermal damage. can prevent

The nickel-containing plating layers 2 and 2' may include nickel or a nickel alloy. The nickel alloy may include Ni and at least one selected from Cr, Mo, and Nb.

The thickness of the nickel-containing plating layers 2 and 2' may be 40 nm to 250 nm. For example, the thickness of the nickel-containing plating layers 2 and 2' may be 50 nm to 250 nm. For example, the thickness of the nickel-containing plating layers 2 and 2' may be 60 nm to 250 nm. For example, the thickness of the nickel-containing plating layers 2 and 2' may be 70 nm to 250 nm. For example, the thickness of the nickel-containing plating layers 2 and 2' may be 80 nm to 250 nm. For example, the thickness of the nickel-containing plating layers 2 and 2' may be 90 nm to 250 nm. For example, the thickness of the nickel-containing plating layer (2, 2') may be 100 nm to 250 nm. When the nickel-containing plating layers 2 and 2' have a thickness within the above range, the characteristics of the nickel-containing plating layers 2 and 2' may be improved as impurities such as organic matter, additives, and coagulant gas are reduced.

The first copper plating layers 3 and 3' may be an electroless plating layer. As the aqueous solution used for forming the electroless plating layer, any aqueous solution for forming the electroless plating layer that can be used in the art may be used.

The thickness of the first copper plating layers 3 and 3' may be 40 nm to 200 nm. For example, the thickness of the first copper plating layers 3 and 3' may be 50 nm to 250 nm. For example, the thickness of the first copper plating layers 3 and 3' may be 60 nm to 250 nm. For example, the thickness of the first copper plating layers 3 and 3' may be 70 nm to 250 nm. For example, the thickness of the first copper plating layers 3 and 3' may be 80 nm to 250 nm. For example, the thickness of the first copper plating layers 3 and 3 ′ may be 90 nm to 250 nm. For example, the thickness of the first copper plating layers 3 and 3' may be 100 nm to 250 nm.

As shown in FIG. 1 , second copper plating layers 4 and 4 ′ may be further included on the first copper plating layers 3 and 3 ′.

The second copper plating layers 4 and 4' may be an electrolytic plating layer. As the method for forming the electrolytic plating layer, any method available in the art may be used. For example, an electrolytic plating may be performed using copper sulfate and sulfuric acid as basic materials to form an electrolytic plating layer on the first copper plating layers 3 and 3'.

The thickness of the second copper plating layers 4 and 4' may be 0.5 μm to 5.0 μm. For example, the thickness of the second copper plating layers 4 and 4 ′ may be 0.5 μm to 4.5 μm. For example, the thickness of the second copper plating layers 4 and 4 ′ may be 0.5 μm to 4.0 μm. For example, the thickness of the second copper plating layers 4 and 4 ′ may be 0.5 μm to 3.5 μm. For example, the thickness of the second copper plating layers 4 and 4' may be 0.5 μm to 3.0 μm. For example, the thickness of the second copper plating layers 4 and 4' may be 0.5 μm to 2.5 μm. For example, the thickness of the second copper plating layers 4 and 4 ′ may be 0.5 μm to 2.0 μm.

The flexible copper clad laminated film 10 according to another embodiment may include the above-described laminate structure. In the flexible copper clad laminate film 10 , impurities such as organic matter, additives, and coagulant gas in the nickel-containing plating layer may be removed. ^{Due to this, the peeling rate per 1 cm 2} unit area between the non-conductive polymer substrate 1 and the nickel-containing plating layers 2 and 2' may be reduced.

A method of manufacturing a laminate structure according to another embodiment includes: forming a nickel-containing plating layer on at least one surface of a non-conductive polymer substrate; forming a first copper plating layer on the nickel-containing plating layer; heat-treating the first copper plating layer; and forming a second copper plating layer on the heat-treated first copper plating layer to prepare the above-described laminated structure.

The manufacturing method of the laminated structure may include heat-treating the first copper plating layer to remove impurities such as organic matter, additives, and coagulation gas in the nickel-containing plating layer. ^{Due to this, the peeling rate per 1 cm 2} unit area between the non-conductive polymer substrate and the nickel-containing plating layer may be reduced.

Each of the nickel-containing plating layer and the first copper plating layer may be formed by an electroless plating method. As the aqueous solution used for forming the electroless plating layer, any aqueous solution for forming the electroless plating layer that can be used in the art may be used. For example, the aqueous solution for the electroless nickel-containing plating layer used for the nickel-containing plating layer may include a water-soluble nickel salt, a reducing agent, and a complexing agent.

The heat treatment step may include a process of performing a heat treatment at a temperature of 100 ° C. to 180 ° C. for 1 minute to 30 minutes. The process of performing the heat treatment may use a hot air drying method by convection heat, a radiant heat method by IR heater heat, or a mixture thereof. Impurities such as organic matter, additives, and coagulant gas in the nickel-containing plating layer are completely removed within the temperature and time range of the heat treatment step, so that lifting caused by insufficient adhesion between the non-conductive polymer substrate and the nickel-containing plating layer can be prevented. and 1 cm ^{2 between them} The rate of occurrence of peeling per unit area may be reduced.

The second copper plating layer may be formed by an electrolytic plating method. The plating solution used in the electrolytic plating method may include a plating solution containing copper at a concentration of 15 to 40 g/L, for example, 15 to 38 g/L, for example, 17 to 36 g/L. The temperature of the plating solution may be maintained at 22 to 37 °C, for example, 25 to 35 °C, for example, 27 to 34 °C. If the temperature is maintained within the above range, it is easy to form the second copper plating layer and the productivity is excellent. In addition, additives such as a brightener, a leveler, a corrector, or an emollient may be added to the plating solution for productivity and surface uniformity.

Hereinafter, the configuration of the present invention and its effects will be described in more detail through Examples and Comparative Examples. However, it will be apparent that these examples are for illustrating the present invention in more detail, and that the scope of the present invention is not limited to these examples.

[Example]

Example One: Flexible copper clad laminated film

non-conductive A 25 μm thick polyimide film (Kapton 100ENC, manufactured by TDC) was prepared as a polymer substrate. A nickel plating layer having a thickness of about 100 nm was respectively formed on both surfaces of the polyimide film by an electroless nickel plating method performed in a vertical or horizontal direction using the following electroless nickel plating solution. A first copper plating layer having a thickness of about 100 nm was respectively formed on the nickel plating layer by an electroless copper plating method using the following electroless copper plating solution. Heat treatment was performed for each of the first copper plating layers by hot air drying by convection heat at a temperature of about 165° C. for about 3 minutes. As shown in FIG. 1 , by forming a second copper plating layer with a thickness of about 2 μm by using an electrolytic plating method on the first copper plating layer that has been subjected to the heat treatment, the first surface and the first surface in an upward direction with respect to the polyimide film as shown in FIG. A flexible copper clad laminated film composed of the second surface in the downward direction was manufactured.

Compositions and conditions of the electroless nickel plating solution and the electroless copper plating solution used in the electroless nickel plating method and the electroless copper plating method, and the copper plating solution used in the electrolytic copper plating method are as follows, respectively.

(electroless nickel plating solution)

·Plating solution: Nickel salt hydrate NiSO ₄ ·6H ₂ O The concentration of nickel ions is 5 g/L

· Bath temperature: about 60 ℃

· Nickel precipitation time: about 1 minute

· pH concentration: about 7.3

(electroless copper plating solution)

·Plating solution: copper sulfate hydrate CuSO ₄ ·6H ₂ O 16 mol/L as complex agent, sulfuric acid 3.25 mL/L

· Bath temperature: about 34 ℃

· Copper precipitation time: about 2 minutes and 30 seconds

Agitation: air agitation

(electrolytic copper plating solution)

Plating solution: copper sulfate 24 g/L, sulfuric acid 188 g/L, hydrochloric acid 60 ppm

· Bath temperature: 32 ℃

· Current density: 3.2 A/dm ²

· Copper precipitation time: about 31 minutes

Example 2: Flexible copper clad laminated film

A flexible copper clad laminate film was prepared in the same manner as in Example 1, except that heat treatment was performed for each of the first copper plating layers for about 4 minutes instead of about 3 minutes at a temperature of about 165° C. by hot air drying by convection heat. .

Example 3: Flexible copper clad laminated film

A flexible copper clad laminate film was prepared in the same manner as in Example 1, except that heat treatment was performed for each of the first copper plating layers for about 5 minutes instead of about 3 minutes at a temperature of about 165° C. by hot air drying by convection heat. .

Example 4: Flexible copper clad laminated film

A flexible copper clad laminate film was prepared in the same manner as in Example 1, except that heat treatment was performed for about 10 minutes instead of about 3 minutes at a temperature of about 165° C. by hot air drying by convection heat for each of the first copper plating layers. .

Example 5: Flexible copper clad laminated film

A flexible copper clad laminate film was prepared in the same manner as in Example 1, except that heat treatment was performed for each of the first copper plating layers for about 15 minutes instead of about 3 minutes at a temperature of about 165° C. by hot air drying by convection heat. .

Example 6: Flexible copper clad laminated film

A flexible copper clad laminate film was prepared in the same manner as in Example 1, except that heat treatment was performed for about 20 minutes instead of about 3 minutes at a temperature of about 165 ° C. by hot air drying by convection heat for each of the first copper plating layers. .

Example 7: Flexible copper clad laminated film

Using the electroless nickel plating method on both sides of the polyimide film to form about 200 nm nickel plating layers instead of about 100 nm thickness, respectively, and the nickel precipitation time in the electroless nickel plating solution was about 4 minutes instead of about 3 minutes Except that Then, a flexible copper clad laminated film was prepared in the same manner as in Example 1.

Example 8: Flexible copper clad laminated film

Using the electroless nickel plating method on both sides of the polyimide film to form about 250 nm nickel plating layers instead of about 100 nm thickness, respectively, and the nickel precipitation time in the electroless nickel plating solution was about 5 minutes instead of about 3 minutes Except that Then, a flexible copper clad laminated film was prepared in the same manner as in Example 1.

Example 9: Flexible copper clad laminated film

A flexible copper clad laminate was prepared in the same manner as in Example 1, except that an about 200 nm nickel plating layer was formed on both sides of the polyimide film using an electroless nickel plating method instead of about 100 nm thick.

Example 10: Flexible copper clad laminated film

A flexible copper clad laminate was prepared in the same manner as in Example 1, except that an about 250 nm nickel plating layer was formed on both sides of the polyimide film using an electroless nickel plating method instead of about 100 nm thick.

comparative example One: Flexible copper clad laminated film

Example 1 and the electroless nickel plating solution, except that the bath temperature was set to 65 °C instead of about 60 °C, the pH concentration was about 8.0 instead of about 7.3, and no heat treatment was performed on each of the first copper plating layers A flexible copper clad laminated film was prepared in the same way.

Analysis example 1: Crystal orientation index - XRD measurement

XRD (X-ray diffraction) analysis was performed on the first copper plating layer of the flexible copper clad laminated films prepared in Examples 1 to 10 and Comparative Example 1. XRD analysis was performed using a Rigaku RINT2200HF+ diffractometer using Cu Kα radiation (1.540598 Å). The results are shown in FIGS. 4 to 6 , respectively.

In addition, determination of the [200] azimuth, [220] azimuth, and [311] azimuth for the [111] azimuth based on X-ray diffraction (XRD) analysis according to FIGS. 4 to 6 . The results obtained by substituting the orientation index into Equations 1 to 3, respectively, are shown in Tables 1 to 3 below.

[Equation 1]

Crystal orientation index (%) = I _[200] /I _[111] = {(X-ray diffraction peak intensity in [200] azimuth/X-ray diffraction peak intensity in [111] azimuth) × 100}

[Equation 2]

Crystal orientation index (%) = I _[220] /I _[111] = {(X-ray diffraction peak intensity in [220] orientation / X-ray diffraction peak intensity in [111] orientation) × 100}

[Equation 3]

Crystal orientation index (%) = I _[311] /I _[111] = {(X-ray diffraction peak intensity in [311] orientation/X-ray diffraction peak intensity in [111] orientation) × 100}

Crystal orientation index (%)
Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 [111] for azimuth
[200] azimuth page 1 25.6 0 21.6 25.3 0 18.0 page 2 30.2 0 11.3 18.1 21.2 27.4 [111] for azimuth
[220] azimuth page 1 0 0 0 0 0 0 page 2 0 0 0 0 0 7.3 [111] for azimuth
[311] azimuth page 1 0 0 0 13.7 0 0 page 2 0 7.8 0 0 0 0

Crystal orientation index (%)
Example 7 Example 8 Example 9 Example 10 [111] for azimuth
[200] azimuth page 1 20.9 20.4 18.3 20.0 page 2 25.4 20.8 17.8 22.4 [111] for azimuth
[220] azimuth page 1 0 0 0 0 page 2 0 0 0 0 [111] for azimuth
[311] azimuth page 1 0 0 5.6 0 page 2 0 7.8 7.2 0

Crystal orientation index (%)
Comparative Example 1 [111] for azimuth
[200] azimuth page 1 27.6 page 2 29.6 [111] for azimuth
[220] azimuth page 1 10.1 page 2 15.0 [111] for azimuth
[311] azimuth page 1 12.7 page 2 14.2

4 and 5, with respect to the first copper plating layer of the flexible copper clad laminated film produced in Examples 1 to 10, in addition to the [111] orientation, [200] orientation, [220] orientation, and [311] ] You can see that one or two azimuths appear at the same time, and you can see that [111] azimuth, [200] azimuth, [220] azimuth, and [311] azimuth do not appear at the same time. have.

Referring to Tables 1 and 2, [111] by X-ray diffraction (XRD) analysis according to Equation 1 above for the first copper plating layer of the flexible copper clad laminated film prepared in Examples 1 to 10 ] The crystal orientation index of the [200] orientation for the orientation satisfies 0 to less than 25%, and the [111] orientation for the [111] orientation by X-ray diffraction (XRD) analysis according to Equation 2 above [220] The crystal orientation index of the azimuth satisfies 0 to less than 15%, and the [311] azimuth for the [111] azimuth by X-ray diffraction (XRD) analysis according to Equation 3 above. It can be seen that the crystal orientation index of 0 to less than 14% is satisfied.

In comparison, with reference to FIG. 6 , the [111] orientation, [200] orientation, [220] orientation, and [311] orientation for the first copper plated layer of the flexible copper clad laminated film produced in Comparative Example 1 It can be seen that both sides appear at the same time.

Referring to Table 3, for the [111] orientation by X-ray diffraction (XRD) analysis according to Equation 1 for the first copper plating layer of the flexible copper clad laminated film produced in Comparative Example 1 The crystal orientation index of the [200] orientation is 27% or more, and the crystal orientation index of the [220] orientation with respect to the [111] orientation by X-ray diffraction (XRD) analysis according to Equation 2 above. is 15% or more, and it can be confirmed that the crystal orientation index of the [311] orientation with respect to the [111] orientation by X-ray diffraction (XRD) analysis according to Equation 3 is 14% or more.

evaluation example 1: polyimide film and nickel plating layer per unit area between peeling rate evaluation

The peeling rate per ^{1 cm 2} unit area between the polyimide film and the nickel plating layer of the flexible copper clad laminated film prepared in Example 1 was evaluated. ^{The peeling rate per unit area of 1 cm 2} between the polyimide film and the nickel plating layer was evaluated using a photograph and an optical microscope with a magnification of 200 times. The results are shown in Table 4, FIGS. 7A and 7B, respectively.

Peeling rate per 1 cm ² unit area (%) Example 1 0

In addition, heat treatment at 150°C for 0.5 minutes, heat treatment at 150°C for 1.0 minutes, and heat treatment at 150°C for each side (first side, second side) of the second copper plating layer of the flexible copper clad laminate film produced in Example 1 After heat treatment at 180 degrees for 0.5 minutes, heat treatment at 180 degrees for 1.0 minutes, heat treatment at 180 degrees for 2.0 minutes, heat treatment at 220 degrees for 0.5 minutes, heat treatment at 220 degrees for 1.0 minutes, and heat treatment at 220 degrees for 2.0 minutes, the polyimide film ^{The rate of peeling per 1 cm 2} unit area between the nickel plating layer and the nickel plating layer was evaluated by taking pictures. The results are shown in Table 5 below.

Of the flexible copper clad laminated film produced in Example 1
Heat treatment conditions for the second copper plating layer Peeling rate per 1 cm ² unit area (%) 150 degrees 0.5 minutes
heat treatment page 1 0 page 2 0 150 degrees 1.0 min
heat treatment page 1 0 page 2 0 150 degrees 2.0 minutes
heat treatment page 1 0 page 2 0 180 degrees 0.5 minutes
heat treatment page 1 0 page 2 0 180 degrees 1.0 min
heat treatment page 1 0 page 2 0 180 degrees 2.0 minutes
heat treatment page 1 0 page 2 0 220 degrees 0.5 minutes
heat treatment page 1 0 page 2 0 220 degrees 1.0 min
heat treatment page 1 0 page 2 0 220 degrees 2.0 minutes
heat treatment page 1 0 page 2 0

^{Referring to Table 4, FIGS. 7A and 7B , the peeling rate per 1 cm 2} unit area between the polyimide film and the nickel plating layer of the flexible copper clad laminated film prepared in Example 1 was 0%.

Referring to Table 5, even after heat treatment at high temperature for each side (first side, second side) of the second copper plating layer of the flexible copper clad laminate film produced in Example 1, the polyimide film and the nickel plating layer In between, the ^{rate of peeling per 1 cm 2} unit area was 0%.

On the other hand, the peeling rate per ^{1 cm 2} unit area between the polyimide film and the nickel plating layer of the flexible copper clad laminated film prepared in Comparative Example 1 was evaluated. Between the polyimide film and the nickel plating layer, 1 cm ^{2 In} order to evaluate the rate of peeling per unit area, it was evaluated using a photograph and an optical microscope with a magnification of 200 times. The results are shown in FIGS. 7c and 7d, respectively.

^{7c and 7d, the peeling rate per 1 cm 2} unit area between the polyimide film and the nickel plating layer of the flexible copper clad laminated film produced by Comparative Example 1 was about 40-50%, indicating that it occurred over a large area. can be checked

Therefore, it was confirmed that the rate of peeling per ^{1 cm 2} unit area between the polyimide film and the nickel plating layer was significantly reduced in the flexible copper clad laminated film produced in Example 1 compared to the flexible copper clad laminated film produced in Comparative Example 1. can

From this, it can be seen that in the flexible copper clad laminated film prepared in Example 1, impurities such as organic matter, additives, and coagulant gas in the nickel-containing plating layer were almost removed.

1: Non-conductive polymer substrate (polyimide substrate),
2, 2': nickel-containing plating layer (electroless nickel plating layer),
3, 3': a first copper plating layer, 4, 4': a second copper plating layer,
5: 1st side, 6: 2nd side,
10: laminated structure (or flexible copper clad laminated film)

Claims (21)

non-conductive polymer substrate;
a nickel-containing electroless plating layer disposed on at least one surface of the substrate; and
a first copper electroless plating layer disposed on the nickel-containing electroless plating layer;
[111] azimuth by X-ray diffraction (XRD) analysis of the first copper electroless plating layer appears,
[200] azimuth, [200] azimuth and [220] azimuth, or [200] azimuth and [311] by X-ray diffraction (XRD) analysis for the first copper electroless plating layer ] azimuth appears,
For the first copper electroless plating layer, the crystal orientation index of the [200] orientation with respect to the [111] orientation by X-ray diffraction (XRD) analysis according to Equation 1 is 11% to 25% less than satisfied,
The first copper electroless plating layer is a plating layer formed by heat treatment at a temperature of 160 ℃ to 180 ℃,
A laminate structure having a peeling rate of 1% or less per ^{1 cm 2} unit area between the non-conductive polymer substrate and the nickel-containing electroless plating layer:
[Equation 1]
Crystal orientation index (%) = I[200]/I[111] = {(X-ray diffraction peak intensity in [200] azimuth/X-ray diffraction peak intensity in [111] azimuth) × 100} delete delete delete According to claim 1,
The crystal orientation index of the [220] orientation with respect to the [111] orientation by X-ray diffraction (XRD) analysis according to Equation 2 below for the first copper electroless plating layer is 0 to less than 15% A laminated structure that satisfies:
[Equation 2]
Crystal orientation index (%) = I _[220] /I _[111] = {(X-ray diffraction peak intensity in [220] orientation / X-ray diffraction peak intensity in [111] orientation) × 100} According to claim 1,
The crystal orientation index of the [311] orientation with respect to the [111] orientation by X-ray diffraction (XRD) analysis according to Equation 3 for the first copper electroless plating layer is 0 to less than 14% A laminated structure that satisfies:
[Equation 3]
Crystal orientation index (%) = I _[311] /I _[111] = {(X-ray diffraction peak intensity in [311] orientation/X-ray diffraction peak intensity in [111] orientation) × 100} According to claim 1,
The non-conductive polymer substrate comprises at least one selected from a phenol resin, a phenolaldehyde resin, an allyl resin, an epoxy resin, a polyethylene resin, a polypropylene resin, a polyester resin, and a polyimide resin. According to claim 1,
A laminate structure wherein the non-conductive polymer substrate has a thickness of 7 μm to 50 μm. delete According to claim 1,
A laminate structure in which the nickel-containing electroless plating layer includes nickel or a nickel alloy. According to claim 1,
A thickness of the nickel-containing electroless plating layer is 40 nm to 250 nm. delete According to claim 1,
The first copper electroless plating layer has a thickness of 40 nm to 200 nm. According to claim 1,
The laminate structure further comprising a second copper plating layer on the first copper electroless plating layer. 15. The method of claim 14,
The second copper plating layer is an electrolytic plating layer. 15. The method of claim 14,
The thickness of the second copper plating layer is 0.5 μm to 5.0 μm. A flexible copper clad laminated film comprising the laminate structure according to any one of claims 1, 5 to 8, 10, 11, and 13 to 16. forming a nickel-containing electroless plating layer on at least one surface of a non-conductive polymer substrate;
forming a first copper electroless plating layer on the nickel-containing electroless plating layer;
heat-treating the first copper electroless plating layer; and
A method of manufacturing a laminated structure comprising a; forming a second copper plating layer on the heat-treated first copper electroless plating layer to prepare the laminated structure according to claim 1 . delete 19. The method of claim 18,
The heat treatment step is a method of manufacturing a laminate structure for performing a process of performing a heat treatment for 1 minute to 30 minutes at a temperature of 160 ℃ to 180 ℃. 19. The method of claim 18,
The second copper plating layer is a method of manufacturing a laminate structure formed by an electrolytic plating method.

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