WO2022158831A1 - Copper clad laminate film, electronic element including same, and method for manufacturing copper clad laminate film - Google Patents

Abstract

Disclosed are a copper clad laminate film, an electronic element including same, and a method for manufacturing the copper clad laminate film. The copper clad laminate film includes a substrate structure in which a primer layer is disposed on at least one surface of a substrate; and a copper-containing layer disposed on the substrate structure, wherein the ratio (I[200]/I[311]) of the peak intensity of the [200] orientation plane to the peak intensity of the [311] orientation plane according to X-ray diffraction (XRD) analysis of the copper-containing layer may be at least 2.0. The copper clad-laminate film has low transmission loss at high frequency due to a low dielectric constant, a low dielectric loss, and a low surface roughness, and also has a high fatigue lifespan, and high room temperature adhesion and heat resistant adhesion between the substrate structure and the copper-containing layer. Accordingly, it is possible to prevent pattern peeling or deformation during a printed circuit process.

Description

Copper clad laminated film, electronic device including same, and method for manufacturing the copper clad laminated film

It relates to a copper-clad laminated film, an electronic device including the same, and a method for manufacturing the copper-clad laminated film.

Recently, due to the development of 5G mobile communication devices, the signal transmission speed of the GHz band has become common, and with the development of semiconductor integrated circuits, the trend of electronic products becoming smaller, lighter, thinner, denser, and highly curved is accelerating. According to the tendency of high frequency signals, electronic devices such as printed circuits or antenna devices have improved dielectric properties and there is a demand for materials with high integration.

For example, a printed circuit board (PCB) has a structure in which both upper and lower surfaces of an insulating base film are bonded with copper foil to form a circuit. In the above structure, a land (a place that can be soldered) may be formed on both upper and lower surfaces. For this reason, it is possible to increase the density of the parts at the same size when the parts are mounted. In general, a printed circuit board is manufactured by coating a polymer film substrate in a molten state on a copper foil, a method of electrolytic plating after sputtering on one side of the substrate film, and thermocompression bonding of a copper foil and a thermosetting substrate film It can be manufactured using a laminating method. However, the above three methods of manufacturing the printed circuit board cannot sufficiently solve the problem of pattern peeling or deformation in the printed circuit process.

Therefore, a copper-clad laminate film having sufficient adhesion between the base layer and the copper-containing layer to prevent pattern peeling or deformation in the printed circuit process, and at the same time having low transmission loss due to low dielectric constant, low dielectric loss, and low surface roughness at high frequencies, including the same There is a demand for an electronic device, and a method for manufacturing the copper clad laminate film.

One aspect is to provide a copper clad laminate film having low transmission loss due to low dielectric constant, low dielectric loss, and low surface roughness at high frequencies, and at the same time, high fatigue life, and high room temperature adhesion and heat resistance between the substrate structure and the copper-containing layer. will be.

Another aspect is to provide an electronic device including the copper clad laminate.

Another aspect is to provide a method of manufacturing the copper clad laminate.

According to one aspect,

a substrate structure having a primer layer disposed on at least one surface of the substrate; and

Including; a copper-containing layer disposed on the base structure;

The ratio of the peak intensity of the [200] orientation to the peak intensity of the [311] orientation by X-ray diffraction (XRD) analysis of the copper-containing layer (I _[200] /I _[311] ) 2.0 or more, a copper clad laminated film is provided.

The surface roughness (R _z ) of the surface of the copper-containing layer may be 0.1 μm or less.

The peel strength of the copper-containing layer with respect to the base structure at 25 ℃ may be 0.80 kgf / cm or more.

The peel strength of the copper-containing layer with respect to the base structure measured after two hours of heat treatment at 150° C., left for 30 minutes at room temperature, and additional heat treatment at 240° C. for 10 minutes may be 0.45 kgf/cm or more.

The copper-containing layer may include a copper seed layer or copper, and at least one copper alloy seed layer selected from nickel, zinc, beryllium, and chromium.

The copper-containing layer includes a copper alloy seed layer of copper and nickel,

The deep portion of the copper alloy seed layer may have a greater content of nickel than the surface portion.

In the XPS analysis of the surface of the copper seed layer or the copper alloy seed layer, the peak intensity ratio of Equation 1 below may be satisfied in the region of binding energy of 933.58 eV to 953.98 eV:

[Equation 1]

I _Cu+Ni /I _Cu ≤ 0.9

during the meal,

I _{Cu + Ni} is the peak strength of the copper alloy seed layer in the region of binding energy 933.58 eV to 953.98 eV,

I _Cu is the peak intensity of the copper seed layer in the region of binding energy 933.58 eV to 953.98 eV.

The copper seed layer or the copper alloy seed layer may be a sputter layer.

A metal plating layer may be further included on one surface of the copper seed layer or the copper alloy seed layer.

The thickness of the copper-containing layer may be 15 μm or less.

The thickness of the copper-containing layer may be 12.5 μm or less.

The substrate is a polyimide-based substrate,

The polyimide-based substrate may have a dielectric constant (D _k ) of 3.4 or less and a dielectric loss (D _f ) of 0.007 or less at a frequency of 20 GHz.

The polyimide-based substrate may have a dielectric constant (D _k ) of 3.3 or less and a dielectric loss (D _f ) of 0.005 or less at a frequency of 28 GHz.

The polyimide-based substrate may have a transmission loss of 0.8 dB/cm or less at a frequency of 28 GHz.

The thickness of the substrate may be 5 μm to 100 μm.

The primer layer may include a silane coupling agent represented by the following Chemical Formula 1:

[Formula 1]

RC _m H _2m Si(OC _n H _2n ) ₃

during the meal,

R is a substituted or unsubstituted C2-C20 alkenyl group, —N(R ₁ )(R ₂ ), or a combination thereof, wherein R ₁ and R ₂ are each independently a hydrogen atom, a halogen atom, a substituted or unsubstituted a C1-C10 alkyl group, a substituted or unsubstituted C2-C10 alkenyl group, a substituted or unsubstituted C2-C10 alkynyl group, a substituted or unsubstituted C3-C20 cycloalkyl group, a substituted or unsubstituted C3- a C20 cycloalkenyl group, a substituted or unsubstituted C6-C20 aryl group, or a substituted or unsubstituted C6-C20 heteroaryl group,

n is an integer from 1 to 5,

m is 0 to 10.

The primer layer may include an amino-based silane compound, a vinyl-based silane compound, or a mixture thereof.

The weight ratio of the amino-based silane compound to the vinyl-based silane compound may be 1:1 to 9:1.

The Si content by X-ray fluorescence spectrometry (XRF) analysis on the surface of the primer layer may be 10 cps to 120 cps.

The water contact angle of the surface of the primer layer may be 45° to 70°.

The thickness of the primer layer may be 500 nm or less.

The thickness of the primer layer may be 300 nm or less.

The thickness of the primer layer may be 20 nm or less.

The fatigue life by MIT measurement according to JIS C 6471 of the film may be 270 times or more.

According to another aspect,

An electronic device including the above-described copper clad laminate is provided.

According to another aspect,

preparing a substrate;

forming a primer layer by applying a composition for forming a primer layer on at least one surface of the substrate; and

Forming a copper-containing layer on the primer layer by sputtering to prepare the above-described copper-clad laminated film; comprising, a copper-clad laminated film manufacturing method is provided.

The method may further include performing plasma treatment after forming the primer layer.

A copper clad laminated film according to one aspect includes a substrate structure in which a primer layer is disposed on at least one surface of a substrate; and a copper-containing layer disposed on the substrate structure; a peak in the [200] orientation with respect to the peak intensity of the [311] orientation by X-ray diffraction (XRD) analysis of the copper-containing layer The intensity ratio (I _[200] /I _[311] ) is greater than or equal to 2.0. The copper clad laminate film has a low transmission loss due to a low dielectric constant, a low dielectric loss, and a low surface roughness at a high frequency, while at the same time having a high fatigue life, and high room temperature adhesion and heat resistance between the substrate structure and the copper-containing layer. It can have. Due to this, it is possible to prevent pattern peeling or deformation in the printed circuit process.

1 is a schematic cross-sectional view of a copper-clad laminated film according to an embodiment.

2 is a schematic cross-sectional view of a double-sided copper clad laminated film according to another embodiment.

3 is an XRD result showing a [111] orientation, a [200] orientation, a [220] orientation, a [311] orientation, and a [222] orientation for a copper-containing layer of a copper clad laminate film according to an embodiment; to be.

4a is a TEM/EDAX result showing the structure of the copper clad laminated film according to Example 3; 4b and 4c are TEM/EDAX results showing the content distribution of nickel elements from the polyimide film substrate of the copper clad laminate film according to Example 3 to the copper alloy seed layer, respectively.

5 shows the copper-clad laminated films according to Examples 2 to 3, after a circuit pattern is formed on the surface and heat treatment is performed, and after the copper-containing seed layer and the copper plating layer are peeled off from the copper-clad laminated film, the surface of the copper-containing seed layer XPS analysis results for

Hereinafter, a copper-clad laminated film, an electronic device including the same, and a method of manufacturing the copper-clad laminated film 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 only presented as examples 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.

In the present specification, the term "included" means that other components may be further included, rather than excluding other components, unless otherwise stated.

As used herein, the term “combination of these” means a mixture or combination with one or more of the described components.

As used herein, the term “and/or” is meant to include any and all combinations of one or more of the related listed items. As used herein, the term “or” means “and/or”. The expression "at least one" or "one or more" in front of elements in the present specification does not mean that it can modify the entire list of elements and can modify individual elements of the description.

In the present specification, when it is stated that one component is disposed “on” or “over” another component, one component may be disposed directly on the other component, or the components interposed between the components are may exist. On the other hand, when it is stated that an element is disposed "directly on" or "directly on" another element, intervening elements may not exist.

As used herein, "~-based polymer (resin)" or "~-based copolymer (resin)" means "~ polymer (resin)", "~ copolymer (resin)", or/and "~ polymer (resin) or copolymer" It is a concept in a broad sense including all of "derivatives of coalescing (resin)".

As used herein, "polyimide" means a polymer containing a repeating structural unit including an imide group. "Polyimide-based" refers to both a polyimide and a polymer containing a repeating structural unit containing an amide group in addition to an imide group. concept that includes Examples of the polymer containing a repeating structural unit containing both an imide group and an amide group include polyamideimide and the like.

As one method of manufacturing a printed circuit board (PCB) among electronic devices, a method of electroplating after sputtering on one surface of the base layer may be used. The method may result in low adhesion between the substrate layer and the deposited copper layer. If the adhesion between the base layer and the copper layer is low, the circuit pattern formed during the manufacture of the printed circuit board may be dropped or deformed. In order to solve this problem, a method of manufacturing a printed circuit board by disposing a bonding layer such as nickel or nickel-chromium alloy between the base layer and the copper layer is used. However, the manufacturing process including the bonding layer such as nickel or nickel-chromium alloy has problems of stability and environmental pollution due to the increase in the number of processes and the use of harmful substances. Also, in circuits using high-frequency signals, signal loss may occur due to bonding layers such as nickel or nickel-chromium alloys.

In view of this, the inventors of the present invention intend to propose a copper clad laminate film having a novel structure, an electronic device including the same, and a method for manufacturing the copper clad laminate film.

A copper clad laminated film according to an embodiment includes a substrate structure in which a primer layer is disposed on at least one surface of a substrate; and a copper-containing layer disposed on the substrate structure; a peak in the [200] orientation with respect to the peak intensity of the [311] orientation by X-ray diffraction (XRD) analysis of the copper-containing layer The intensity ratio (I _[200] /I _[311] ) may be greater than or equal to 2.0. The copper clad laminate film has a low transmission loss due to a low dielectric constant, a low dielectric loss, and a low surface roughness at a high frequency, while at the same time having a high fatigue life, and high room temperature adhesion and heat resistance between the substrate structure and the copper-containing layer. It can have. Due to this, it is possible to prevent pattern peeling or deformation in the printed circuit process.

1 and 2 are schematic cross-sectional views of a copper clad laminated film according to an embodiment, respectively.

1 and 2, in the copper clad laminated films 100 and 200 according to an embodiment, primer layers 21 and 22 are disposed on one or both sides of the substrate 11 as a substrate structure, and the primer layer ( Copper layers 31 and 32 as copper-containing layers 40 and 50 and metal plating layers 41 and 42 are sequentially disposed on the 21 and 22 .

Hereinafter, each base structure constituting the copper-clad laminated film, a copper-containing layer, a copper-clad laminated film, and an electronic device will be described in detail.

<Base structure>

according to one embodiment The substrate structure may have a primer layer disposed on at least one surface of the substrate.

The substrate according to one embodiment may be a film or a sheet. For example, the substrate may be a film. As the substrate, a film having excellent heat resistance can be used to withstand high temperatures when manufacturing a printed circuit board.

For example, the substrate may include polyimide, a modified polyimide having a low dielectric constant, polyphenylsulfide, polyamide, polyetherimide, polyethylene naphthalate, or a film containing fluorine. For example, the substrate may be a polyimide-based substrate.

As the polyimide-based substrate, a polyimide film or a modified polyimide film having a low dielectric constant may be used. The polyimide film used for the substrate may be manufactured by extruding polyamic acid, which is a polyimide precursor, to make a film, and heat-treating and drying the film for imidization of the polyamic acid. Moisture and residual gas may be removed through a drying process commonly used in the art. For example, the drying may be performed through a roll to roll type heat treatment under normal pressure or may be performed using an infrared (IR) heater under a vacuum atmosphere.

The moisture absorption rate is a ratio indicating the amount of moisture absorbed by the material. In general, it is known that when the moisture absorption rate is high, the permittivity and the dielectric loss increase.

Water, which exists in a vapor state other than the substrate, does not substantially affect the dielectric constant and dielectric loss of the substrate. However, when water vapor or the like is absorbed by the substrate, water exists in a liquid state, and in this case, the dielectric constant and dielectric loss of the substrate may dramatically increase. Therefore, lowering the moisture absorption of the substrate can be seen as a very important factor for the substrate as an insulating film. The moisture absorption of the substrate may be less than 5% by weight. For example, the moisture absorption of the substrate may be 4 wt% or less, 3 wt% or less, or 2 wt% or less. When the moisture absorption of the substrate is 5% by weight or more, signal loss in the high-frequency circuit may increase.

The substrate may be a polyimide-based substrate, and the polyimide-based substrate may have a dielectric constant (D _k ) of 3.4 or less and a dielectric loss (D _f ) of 0.007 or less at a frequency of 20 GHz. For example, the polyimide-based substrate may have a dielectric constant (D _k ) of 3.3 or less and a dielectric loss (D _f ) of 0.005 or less at a frequency of 28 GHz. For example, the polyimide-based substrate may have a transmission loss of 0.8 dB/cm or less at a frequency of 28 GHz.

The glass transition temperature (Tg) of the substrate may be 200 ℃ or more. The substrate may have sufficient heat resistance, so that physical-chemical changes may not occur within a high temperature range and for a long time. When the glass transition temperature (Tg) of the substrate is 200° C. or less, the substrate may be melted in the printed circuit board manufacturing process or the dimensional change of the substrate may occur after the high temperature process, causing the circuit board to warp.

The thickness of the substrate may be generally 5 μm to 100 μm. For example, the thickness of the substrate may be from 10 μm to 75 μm, from 12.5 μm to 70 μm, from 12.5 μm to 60 μm, from 12.5 μm to 50 μm, or from 12.5 μm to 40 μm. It is possible to suppress a wrinkle phenomenon caused by an external force within the thickness range of the substrate, maintain appropriate heat resistance, and facilitate handling.

The substrate may be subjected to plasma treatment on the surface. The plasma treatment may use RF plasma or an ion beam. The plasma treatment may be performed on one or both surfaces of the substrate. By the plasma treatment, chemical activity of the surface of the substrate may be enhanced, and surface roughness may be improved to further improve adhesion between the substrate and the copper-containing layer.

A primer layer according to an embodiment includes a silane coupling agent.

For example, the primer layer may include a silane coupling agent represented by the following Chemical Formula 1:

[Formula 1]

RC _m H _2m Si(OC _n H _2n ) ₃

during the meal,

R is a substituted or unsubstituted C2-C20 alkenyl group, —N(R ₁ )(R ₂ ), or a combination thereof, wherein R ₁ and R ₂ are each independently a hydrogen atom, a halogen atom, a substituted or unsubstituted a C1-C10 alkyl group, a substituted or unsubstituted C2-C10 alkenyl group, a substituted or unsubstituted C2-C10 alkynyl group, a substituted or unsubstituted C3-C20 cycloalkyl group, a substituted or unsubstituted C3- It may be a C20 cycloalkenyl group, a substituted or unsubstituted C6-C20 aryl group, or a substituted or unsubstituted C6-C20 heteroaryl group,

n may be an integer from 1 to 5,

m may be 0 to 10.

The primer layer may include an amino-based silane compound, a vinyl-based silane compound, or a mixture thereof. The content of the amino-based silane compound may be the same as or higher than the content of the vinyl-based silane compound.

The primer layer includes the silane coupling agent represented by Formula 1, and when the amino-based silane compound is contained in the same or higher content as the vinyl-based silane compound, room temperature adhesion and heat resistance between the substrate structure of the copper clad laminate and the copper-containing layer Adhesion is improved and pattern peeling or deformation prevention is possible in the printed circuit process, so it can be applied to printed circuit boards.

The weight ratio of the amino-based silane compound to the vinyl-based silane compound may be 1:1 to 9:1. For example, the weight ratio of the amino-based silane compound to the vinyl-based silane compound may be 1:1 to 8:1, 1:1 to 7:1, 1:1 to 6:1, or 1:1 to 5:1 or 1:1 to 4:1.

When the weight ratio of the vinyl-based silane compound to the amino-based silane compound is within the above range, the room temperature adhesion and heat-resistant adhesion between the base structure of the copper clad laminate and the copper-containing layer are further improved, thereby facilitating pattern peeling or deformation prevention in the printed circuit process. can

The Si content by X-ray fluorescence spectrometry (XRF) analysis on the surface of the primer layer may be 10 cps to 120 cps. For example, the Si content by X-ray fluorescence spectrometry (XRF) analysis on the surface of the primer layer may be 12 cps to 120 cps, 14 cps to 120 cps, 16 cps to 120 cps, or 18 cps It can be from 20 cps to 120 cps, from 22 cps to 120 cps, from 24 cps to 120 cps, from 26 cps to 120 cps, or from 28 cps to 120 cps. If the Si content by XRF (X-ray fluorescence spectrometry) analysis on the surface of the primer layer is more than 120 cps, room temperature adhesion and heat resistance adhesion between the base structure of the copper clad laminate and the copper-containing layer is low. For this reason, when a circuit pattern is formed on a copper clad laminate film and the circuit pattern is peeled from the copper clad laminate film after hydrochloric acid treatment at room temperature, some circuit patterns may be peeled off or all of the circuit patterns may be peeled off.

The water contact angle of the surface of the primer layer may be 45° to 70°. If the water contact angle of the surface of the primer layer is within the above range, room temperature adhesion and heat resistance adhesion between the base structure and the copper-containing layer are excellent, and the peeling phenomenon does not occur when the circuit pattern is peeled from the copper clad laminate after hydrochloric acid treatment at room temperature.

The silane coupling agent may be included in an amount of 0.01 to less than 10% by weight based on the total weight of the primer layer. For example, the primer layer may be formed by applying and drying a composition for forming a primer layer on a substrate using a solution application method.

The solvent used in the composition for forming the primer layer is not limited, but, for example, the solvent may be at least one selected from water, acetone, methanol, ethanol, and isopropanol. These solvents may be used alone or in combination.

The thickness of the primer layer may be 500 nm or less. For example, the thickness of the primer layer may be 450 nm or less, 400 nm or less, 350 nm or less, 300 nm or less, 250 nm or less, 200 nm or less, 150 nm or less, 100 nm or less, or It may be 80 nm or less, 60 nm or less, 40 nm or less, or 20 nm or less. For example, the thickness of the primer layer may be 18 nm or less, 16 nm or less, or 15 nm or less. Even when the thickness of the primer layer is a thin film as described above, room temperature adhesion and heat resistance adhesion between the base structure and the copper-containing layer may be improved.

<Copper-containing layer>

The copper-containing layer according to an exemplary embodiment has a face-centered cubic structure. The copper-containing layer of such a face-centered cubic structure has crystal orientation planes or orientation planes in various directions. The direction and/or position of the crystal orientation plane or orientation plane may be expressed by Miller Indices. For example, [111] azimuth, [200] azimuth, [220] azimuth, [311] azimuth, and [222] azimuth are the crystal orientation planes or azimuth planes in the [111] direction, [200], respectively. ] direction, the crystal orientation plane or orientation plane in the [220] direction, the crystal orientation plane or orientation plane in the [311] direction, and the Miller index of the crystal orientation plane or orientation plane in the [222] direction ( Miller indices). The crystal planes of these various directions can be specified by X-ray diffraction (XRD) analysis.

3 is an XRD result showing a [111] orientation, a [200] orientation, a [220] orientation, a [311] orientation, and a [222] orientation for a copper-containing layer of a copper clad laminate film according to an embodiment; to be.

Referring to FIG. 3 , the [111] orientation of the copper-containing layer of the copper clad laminated film according to an embodiment shows a peak at Bragg 2θ 43.4±0.5°, and the [200] orientation shows a peak at Bragg 2θ 50.5±0.5°. , the [220] azimuth shows a peak at Bragg 2θ 74.2 ±0.5°, the [311] azimuth shows a peak at Bragg 2θ 90.0±0.5°, and the [222] azimuth shows a peak at Bragg 2θ 95.2±0.5° indicates a peak.

The copper-containing layer according to an embodiment is a ratio of the peak intensity of the [200] orientation to the peak intensity of the [311] orientation by X-ray diffraction (XRD) analysis (I _[200] /I _{[ 311]} ) may be 2.0 or greater. If the ratio (I _[200] / I _[311] ) of the peak intensity of the copper-containing layer by XRD analysis is in the above range, the density is small and stable in order to resolve the internal stress of tensile stress and elastic energy generated between copper particles. Because it can be in a state of being, it can have a high fatigue life.

The surface roughness (R _z ) of the surface of the copper-containing layer may be 0.1 μm or less.

The peel strength of the copper-containing layer with respect to the base structure at 25 ℃ may be 0.80 kgf / cm or more.

The peel strength of the copper-containing layer with respect to the base structure measured after two hours of heat treatment at 150° C., left for 30 minutes at room temperature, and additional heat treatment at 240° C. for 10 minutes may be 0.45 kgf/cm or more.

The copper-containing layer according to an embodiment may include a copper seed layer or copper, and at least one copper alloy seed layer selected from nickel, zinc, beryllium, and chromium.

The copper-containing layer may include a copper alloy seed layer of copper and nickel.

For example, the copper and nickel weight (%) ratio of the copper alloy seed layer may be 60:40 to 95:5 or 60:40 to 90:10. For example, the copper alloy seed layer may be one or more alloy seed layers selected from zinc, beryllium, and chromium in addition to copper and nickel. The weight (%) ratio of one or more metals selected from zinc, beryllium, and chromium other than copper and nickel may be 60:35:5 to 90:5:5 or 60:35:5 to 80:15:5 can

The deep portion of the copper alloy seed layer may have a greater content of nickel than the surface portion. As used herein, the deep portion means an area from the substrate toward the copper-containing seed layer from about 0 to 60 mm, and the surface portion means an area greater than 60 mm from the substrate toward the copper-containing seed layer. Such a copper-containing seed layer can prevent moisture and air passing through the substrate from being oxidized in the copper-containing seed layer. For this reason, when chemical polishing (soft etching) is performed on the surface of the copper clad laminate including the same with an acid such as hydrochloric acid, formic acid, or sulfuric acid, peeling between the substrate structure and the copper-containing layer including the copper-containing seed layer can be prevented. have. The content of the nickel element in the copper-containing seed layer can be confirmed by TEM/EDAX of FIGS. 4A to 4C, which will be described later.

In the XPS analysis of the surface of the copper seed layer or the copper alloy seed layer, the peak intensity ratio of Equation 1 below may be satisfied in the region of binding energy of 933.58 eV to 953.98 eV:

[Equation 1]

I _Cu+Ni /I _Cu ≤ 0.9

during the meal,

I _{Cu + Ni} is the peak strength of the copper alloy seed layer in the region of binding energy 933.58 eV to 953.98 eV,

I _Cu is the peak intensity of the copper seed layer in the region of binding energy 933.58 eV to 953.98 eV.

In XPS analysis, a region of 933.58 eV to 953.98 eV of binding energy means a peak region of copper oxide (Cu _x O _y , 0 < x ≤ 5, 0 < y ≤ 5). The copper clad laminate film having the peak intensity ratio of Equation 1 in the copper oxide peak region has excellent chemical resistance. The XPS analysis result can be confirmed in FIG. 5 to be described later.

The copper seed layer or the copper alloy seed layer may be a sputter layer.

The copper seed layer or the copper alloy seed layer may be deposited on one or both surfaces of the primer layer by sputtering in a vacuum tank under a reduced pressure of 10 ^-4 to 10 ^-2 torr. As the deposition method, any deposition method available in the art may be used, but for example, physical vapor deposition (PVD), chemical vapor deposition (CVD), low pressure chemical vapor deposition (LPCVD), or vacuum deposition may be used. have.

The copper-containing layer may further include a metal plating layer on one surface of the copper seed layer or the copper alloy seed layer.

For example, the metal plating layer is formed using an electrolytic plating method.

As the metal, an appropriate metal may be selected by a person skilled in the art according to the metal texture to be implemented. For example, the metal may be gold, silver, cobalt, aluminum, iron, nickel, chromium, or copper. For example, the metal may be copper.

The electroplating may be performed by a method commonly used in the art. The electrolytic plating is performed by, for example, performing electroplating using copper sulfate and sulfuric acid as basic materials to form a metal plating layer on the copper seed layer or the copper alloy seed layer.

The electrolytic plating may be performed using a plating solution containing copper at a concentration of 15 g/L to 40 g/L, for example, 15 g/L to 38 g/L, for example, 17 g/L to 36 g/L. In the electrolytic plating, the temperature of the plating solution may be maintained at 22°C to 37°C, for example, 25°C to 35°C, for example, 27°C to 34°C. It is easy to form a plating layer within the temperature range of the plating solution and can have excellent productivity.

The pH of the plating solution may be greater than 7. Optionally, one or more pH adjusting agents may be included in the plating solution to adjust the pH of the plating solution to an alkaline pH. The pH adjusting agent may include an organic acid, an inorganic acid, an organic base, an inorganic base, or a mixture thereof. For example, the inorganic acid may include phosphoric acid, nitric acid, sulfuric acid, hydrochloric acid, or a combination thereof. For example, the inorganic base may include ammonium hydroxide, sodium hydroxide, potassium hydroxide, or a combination thereof.

Meanwhile, well-known additives, for example, a brightener, a leveler, a correcting agent, a emollient, and the like, may be added to the plating solution for productivity and surface uniformity.

The electroplating may be performed under a current density of 0.1A/m² to 20A/m², for example, 0.1A/m² to 17A/m², for example, 0.3A/m² to 15A/m². Within the range of the current density, it is possible to easily form a metal plating layer and have excellent productivity.

The thickness of the copper-containing layer may be 15 μm or less. For example, the thickness of the copper-containing layer may be 12.5 μm or less.

The copper seed layer or the copper alloy seed layer may have a thickness of 50 nm to 150 nm. For example, the thickness of the copper seed layer or copper alloy seed layer may be 50 nm to 140 nm, may be 50 nm to 130 nm, or may be 50 nm to 120 nm. If the copper alloy layer has the thickness range, conductivity can be secured during film formation, and a copper clad laminate film having a low surface roughness (R _z ) can be provided.

The thickness of the metal plating layer may be 0.1 μm to 12 μm. For example, the thickness of the metal plating layer may be 0.2 μm to 12 μm or 0.7 μm to 12 μm. When the thickness of the metal plating layer is within the above range, it is easy to form the metal plating layer and excellent in productivity, and room temperature adhesion and heat resistance adhesion between the base structure and the copper-containing layer may be improved.

<Copper-clad laminated film and electronic device>

The fatigue life by MIT measurement according to JIS C 6471 of the copper clad laminated film according to an embodiment may be 270 or more. For example, the fatigue life measured by MIT according to JIS C 6471 of the copper clad laminate film may be 280 times or more.

An electronic device according to another embodiment may include the above-described copper clad laminate. For example, the electronic device may include an electronic circuit device or an electronic component. For example, the electronic circuit device may include a semiconductor, a printed circuit board, or a wiring board. For example, the electronic device may include a display device such as LCD or OLED.

<Manufacturing method of copper clad laminated film>

A method of manufacturing a copper clad laminated film according to another embodiment includes the steps of preparing a substrate; forming a primer layer by applying a composition for forming a primer layer on at least one surface of the substrate; and forming a copper-containing layer on the primer layer by sputtering to prepare the above-described copper clad laminate.

The manufacturing method of the copper clad laminate film can prevent pattern peeling or deformation in the printed circuit process. The method of manufacturing the copper clad laminate can reduce signal loss in a high-frequency circuit.

The method may further include performing plasma treatment after forming the primer layer.

The definition of the substituent (group) used in Formula 1 is as follows.

“Substitution” in “substituted” of an alkyl group, alkenyl group, alkynyl group, cycloalkyl group, cycloalkenyl group, aryl group, or heteroaryl group used in Formula 1 is a halogen atom or a C1-C10 alkyl group substituted with a halogen atom. (Example: CCF ₃ , CHCF ₂ , CH ₂ F, CCl ₃ etc.), hydroxy group, nitro group, cyano group, amino group, amidino group, hydrazine, hydrazone, carboxyl group or its salt, sulfonic acid group or its salt, phosphoric acid or its salt Salt or C1-C10 alkyl group, C2-C10 alkenyl group, C2-C10 alkynyl group, C1-C20 heteroalkyl group, C6-C20 aryl group, C6-C20 arylalkyl group, C6-C20 heteroaryl group group, or means substituted with a C6-C20 heteroarylalkyl group.

Specific examples of the C1-C10 alkyl group used in Formula 1 include methyl, ethyl, propyl, isobutyl, sec-butyl, ter-butyl, neo-butyl, iso-amyl, and hexyl, among the alkyl groups One or more hydrogen atoms may be substituted with a substituent as defined in "substitution" above.

Specific examples of the C2-C10 alkenyl group used in Formula 1 include vinylene and allylene, and at least one hydrogen atom of the alkenyl group may be substituted with a substituent as defined in the above-mentioned "substitution" .

Specific examples of the C2-C20 alkynyl group used in Formula 1 may include acetylene, and at least one hydrogen atom of the alkynyl group may be substituted with a substituent as defined in “Substitution” above.

Specific examples of the C3-C20 cycloalkyl group used in Formula 1 include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, and the like, and at least one hydrogen atom of the cycloalkyl group is as defined in the above-mentioned "substitution". It can be substituted with the same substituent.

Specific examples of the C3-C20 cycloalkenyl group used in Formula 1 include cyclopropenyl, cyclobutenyl, cyclopentenyl, cyclohexenyl, and the like, and at least one hydrogen atom among the cycloalkenyl groups is It may be substituted with a substituent as defined in "substituting".

The C6-C20 aryl group used in Formula 1 is used alone or in combination to mean an aromatic system including one or more rings, and examples thereof include phenyl and naphthyl. In addition, one or more hydrogen atoms in the aryl group may be substituted with a substituent as defined in the above-mentioned "substitution".

The C6-C20 heteroaryl group used in Formula 1 means an organic compound containing one or more heteroatoms selected from N, O, P or S, and the remaining ring atoms are carbon, for example, pyridyl, etc. can In addition, one or more hydrogen atoms in the heteroaryl group may be substituted with a substituent as defined in the above-mentioned "substitution".

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 the scope of the present invention is not limited to these examples.

[Example]

Example 1: Copper clad laminated film

A polyimide film (manufactured by PI Advanced Materials, dielectric constant (D _k ): 3.3, dielectric loss (D _f ): 0.005 @28 GHz) was prepared as a substrate as a base material.

Separately, as a silane coupling agent, N-2-(aminoethyl)-8-aminooctyl-trimethoxysilane (N-2-(aminoethyl)-8-aminooctyl-trimethoxysilane) and 7-octenyltrimethoxysilane ( 7-octenyltrimethoxysilane) was mixed and stirred in 10 g of distilled water at a weight ratio of 1:0.5 to obtain a mixed aqueous solution. A composition for forming a primer layer was prepared by dissolving 50 g of ethanol and 50 g of isopropyl alcohol in the mixed aqueous solution and stirring for 1 hour. The composition for forming the primer layer was applied to the upper surface of the polyimide film using a bar coater and dried at 150° C. for about 2 minutes to form a primer layer with a thickness of about 300 nm. RF plasma treatment was performed on the primer layer. RF plasma treatment was performed with about 1000 W of power by introducing argon gas and oxygen gas in a volume ratio of 4:1. A copper seed layer to a thickness of 1200 Å was formed on the upper surface of the primer layer using copper having a purity of 99.995% by physical vapor deposition (PVD). A copper clad laminate was prepared by forming a copper plating layer with a thickness of about 12 μm on the copper seed layer by an electrolytic copper plating method.

The electrolytic copper plating solution used was a solution of Cu ²⁺ concentration of 28 g/L and sulfuric acid 180 g/L, and was further calibrated with 3-N,N-dimethylaminodithiocarbamoyl-1-propanesulfonic acid 0.01 g/L as a brightener. (manufactured by Atotech) was used. Electrolytic plating was performed at 30°C, and was manufactured by applying a current at a current density of 1 A/m².

Example 2: Copper clad laminated film

Copper clad laminate in the same manner as in Example 1, except that a 50 μm thick polyimide film (manufactured by PI Advanced Materials, dielectric constant (D _k ): 3.3, dielectric loss (D _f ): 0.005 @28GHz) was prepared as a substrate. A film was made.

Example 3: Copper clad laminated film

A copper alloy seed layer of 1200 Å thick copper and nickel was formed on the upper surface of the primer layer using a copper and nickel alloy having a weight (%) ratio of copper and nickel of 90:10 by physical vapor deposition (PVD). Except that, a copper clad laminated film was prepared in the same manner as in Example 1.

Example 4: Copper clad laminated film

A polyimide film with a thickness of about 50 μm (dielectric constant (D _k ): 3.4, dielectric loss (D _f ): 0.007 @ 20 GHz) was prepared as a substrate, and 1 g of aminopropyltriethoxysilane was used as a silane coupling agent. A copper clad laminate was prepared in the same manner as in Example 1, except that a primer layer having a thickness of about 5 nm was formed.

Example 5: Copper clad laminated film

A copper clad laminate was prepared in the same manner as in Example 4, except that a primer layer having a thickness of about 15 nm was formed using 5 g of aminopropyltriethoxysilane as a silane coupling agent.

Example 6: Copper-clad laminated film

A copper clad laminate was prepared in the same manner as in Example 4, except that a primer layer having a thickness of about 10 nm was formed using 3 g of aminopropyltriethoxysilane as a silane coupling agent.

Example 7: Copper-clad laminated film

The same method as in Example 4, except that a primer layer having a thickness of about 5 nm was formed using 0.2 g of vinyltriethoxysilane and 0.8 g of aminopropyltriethoxysilane as a silane coupling agent. to prepare a copper-clad laminated film.

Example 8: Copper clad laminated film

As a silane coupling agent, 0.2 g of vinyltriethoxysilane and 0.8 g of aminopropyltriethoxysilane were used to form a primer layer with a thickness of about 5 nm, and a physical vapor deposition method ( PVD) in the same manner as in Example 4, except that a copper and nickel alloy seed layer having a thickness of 1200 Å was formed using a copper and nickel alloy having a weight (%) ratio of 90:10 to copper and nickel. A copper-clad laminated film was prepared.

Example 9: Copper-clad laminated film

The same method as in Example 4, except that a primer layer having a thickness of about 15 nm was formed using 2.5 g of vinyltriethoxysilane and 2.5 g of aminopropyltriethoxysilane as a silane coupling agent. to prepare a copper-clad laminated film.

Example 10: Copper-clad laminated film

A low-dielectric constant polyimide film (D _k : 3.2, D _f : 0.004 @20GHz) with a thickness of about 50 μm was prepared as a substrate, and 0.6 g of vinyltriethoxysilane and aminopropyltriethoxysilane as a silane coupling agent. A copper clad laminate was prepared in the same manner as in Example 4, except that a primer layer having a thickness of about 10 nm was formed using 2.4 g of (aminopropyltriethoxysilane).

Example 11: Copper clad laminated film

A low-dielectric constant polyimide film (D _k : 3.2, D _f : 0.004 @20GHz) of about 50 μm thick was prepared as a base material, and copper and nickel were coated with 90:10 on the upper surface of the primer layer by physical vapor deposition (PVD). A copper clad laminate was prepared in the same manner as in Example 4, except that a copper alloy seed layer of copper and nickel having a thickness of 1200 Å was formed using a copper and nickel alloy having a weight (%) ratio.

Comparative Example 1: Copper-clad laminated film

As a substrate, a liquid crystal polymer (LCP) film (manufactured by Kaneka, dielectric constant (D _k ): 3.1, dielectric loss (D _f ): 0.0022 @28 GHz) having a thickness of about 25 µm was prepared.

Separately, a solution of polydiacetylene (PDA)-4, 4'-oxydianiline (ODA) in a dimethylacetamide (DMAC) solvent having a viscosity of about 5000 cP, 3, 3 ', 4, 4'-biphenyltetracarboxylic acid dianhydride (3,3',4,4'-biphenyltetracarboxylic acid dianhydride, BPDA) was added and stirred for about 1 hour to prepare a composition for forming an adhesive layer of a polyamic acid solution . The composition for forming the adhesive layer was applied to the upper surface of the liquid crystal polymer (LCP) film using a bar coater, and a 12 μm thick copper foil was passed between two rotating nip rollers to prepare a laminated copper clad laminate.

Comparative Example 2: Copper-clad laminated film

As a substrate, a modified PI (m-PI) film (manufactured by Kaneka, dielectric constant (D _k ): 3.1, dielectric loss (D _f ): 0.006 @28GHz) having a thickness of about 25 μm was prepared.

Separately, a solution of polydiacetylene (PDA)-4, 4'-oxydianiline (ODA) in a dimethylacetamide (DMAC) solvent having a viscosity of about 5000 cP, 3, A solution of 3',4,4'-benzophenonetetracarboxylic dianhydride (3,3',4,4'-benzophenonetetracarboxylic dianhydride; BTDA)-pyromellitic dianhydride (PMDA) was added and the mixture was stirred for about 1 hour. A composition for forming an adhesive layer of a polyamic acid solution was prepared by stirring. The composition for forming an adhesive layer was applied to the upper surface of the modified-polyimide film by using a bar coater, and a 12 μm thick copper foil was passed between two rotating nip rollers to prepare a laminated copper clad laminate.

Comparative Example 3: Copper clad laminated film

Except for preparing a polyimide film (dielectric constant (D _k ): 3.4, dielectric loss (D _f ): 0.007 @ 20 GHz) of about 50 μm thickness without applying the composition for forming a primer layer on the upper surface, Example 4 and A copper-clad laminated film was prepared in the same manner.

Comparative Example 4: Copper-clad laminated film

A copper clad laminate was laminated in the same manner as in Example 4, except that a low-k polyimide film (D _k : 3.2, D _f : 0.004 @20GHz) having a thickness of about 50 μm was prepared on the upper surface of which the composition for forming a primer layer was not applied. A film was prepared.

Comparative Example 5: Copper-clad laminated film

A low-dielectric constant polyimide film (D _k : 3.2, D _f : 0.004 @20GHz) with a thickness of about 50 μm was prepared as a substrate, and 10.5 g of vinyltriethoxysilane (Shin-Etsu, KBE-1003) as a silane coupling agent and A copper clad laminate was prepared in the same manner as in Example 4, except that a primer layer having a thickness of 65 nm was formed using 4.5 g of aminopropyltriethoxysilane (Dow Chemical, OFS-6011).

Comparative Example 6: Copper-clad laminated film

A low-dielectric constant polyimide film (D _k : 3.2, D _f : 0.004 @20GHz) with a thickness of about 50 μm was prepared as a substrate, and 9.0 g of vinyltriethoxysilane (Shin-Etsu, KBE-1003) as a silane coupling agent and A copper clad laminate was prepared in the same manner as in Example 4, except that a primer layer having a thickness of 43 nm was formed using 1.0 g of aminopropyltriethoxysilane (Dow Chemical, OFS-6011).

Comparative Example 7: Copper-clad laminated film

About 50 μm thick as a substrate A low-k polyimide film (D _k : 3.2, D _f : 0.004 @20 GHz) was prepared, and a 45 nm-thick primer layer was formed using 6.0 g of aminopropyltriethoxysilane as a silane coupling agent. Except that, a copper clad laminated film was prepared in the same manner as in Example 10.

Comparative Example 8: Copper-clad laminated film

About 50 μm thick as a substrate A low-k polyimide film (D _k : 3.2, D _f : 0.004 @20GHz) was prepared, and 6.0 g of vinyltriethoxysilane as a silane coupling agent was used to form a 30 nm-thick primer layer except that Then, a copper clad laminated film was prepared in the same manner as in Example 10.

Evaluation Example 1: Physical property evaluation

The physical properties of each of the copper-clad laminated films prepared in Examples 1 to 11 and Comparative Examples 1 to 8 were evaluated as follows. Some of the results are shown in Tables 1 to 4, Figs. 4a to 4c, and Fig. 5, respectively.

(1) permittivity (D _k ) and dielectric loss (D _f )

For the substrate of each copper clad laminate, a sample of 4 cm x 4 cm was made, and the dielectric constant (D _k ) and dielectric loss (D _f ) were measured. The results are shown in Tables 1 to 4.

(2) Primer layer thickness (nm)

The thickness of the primer layer of each copper clad laminate was measured using a FIB (Focused Ion Beam)-TEM equipment. Some of the results are shown in Tables 3 and 4.

(3) Transmission loss (dB/cm)

With respect to the substrate of the copper clad laminated films of Example 1 and Comparative Examples 1 and 2, 10 straight circuits were formed at intervals of 100 µm in width, 100 mm in length, and 40 mm in the longitudinal direction by etching. Then, each signal conductor and the ground conductor of the transmission path in which the straight circuit is formed are respectively connected to a measurement port of a vector network analyzer, and a signal is applied up to a frequency of 28 GHz using the measurement method disclosed in International Patent Application Publication No. WO2005-101034. The transmission loss was calculated. The results are shown in Table 1.

(4) XRD analysis (I _[200]/ I _[311] )

XRD (X-ray diffraction) analysis was performed on the peak intensities of the [311] azimuth and [200] azimuth planes of the copper-containing layer or copper foil of the copper clad laminated films of Example 1 and Comparative Examples 1-2. XRD analysis was performed using a Rigaku RINT2200HF+ diffractometer using CuKα radiation (1.540598 Å), [200] a peak at Bragg 2θ 50.5 ± 0.5°, and [311] Azimuth, Bragg 2θ 90.0± Peak intensity in the [200] orientation for the peak intensity in the [311] orientation from the peak intensity in the [311] orientation and [200] orientation of the copper-containing layer of the copper-clad laminated film or copper foil was calculated, and the results are shown in Table 1.

(5) Surface roughness (R _z )

The surface roughness (R _z ) of the copper-clad laminated films of Example 1 and Comparative Examples 1 and 2 was measured with an atomic force microscope (AFM). The surface roughness (R _z ) was obtained by dividing the entire measurement section into 5 equal parts, obtaining the maximum value for each equal segment, and dividing the sum of the obtained values by 5. The results are shown in Table 1.

(6) MIT (fatigue life, times)

The copper-clad laminated films of Example 1 and Comparative Examples 1 and 2 were subjected to fatigue life by MIT in accordance with JIS C 6471. For MIT measurement, each copper clad laminate was cut into 15 mm x 170 mm size, and the pattern (width: 1000 μm) was etched, stored for 24 hours, and a sample stored for 1 hour at 80 °C in an oven was prepared. MIT was measured by applying (+) and (-) electrodes to both ends of the sample. The results are shown in Table 1.

SFT-9250 and TOYO SEIKI were used as MIT measuring equipment.

(7) Surface contact angle (°)

With respect to the surface of the primer layer of the copper clad laminated films of Examples 4 to 6, 8, and Comparative Examples 3 to 4, the surface contact angle was measured with 3 uL of water and 1 uL of diiodomethane using a contact angle measuring device (manufactured by KYOUWA). The results are shown in Table 3.

(8) TEM/EDAX analysis - content distribution of nickel element

For the copper clad laminate of Example 3, a depth profile and a content distribution of nickel elements were analyzed using TEM/EDAX. The results are shown in Figs. 4a to 4c.

TEM/EDAX used for the analysis was Titan G2 ChemiSTEM Cs Probe, FEI Company's equipment was used.

(9) XPS analysis

For the copper clad laminated films of Examples 2 to 3, a circuit pattern with a width of 1 mm was formed on the surface, and the entire opposite surface of the copper clad laminate on which the circuit pattern was formed was etched, and then the copper clad laminate on which the circuit pattern was formed was heated in an oven. Heat treatment was carried out at 150 °C for 12 hours. Then, the copper-containing seed layer and the copper plating layer as copper-containing layers from the copper-clad laminate were peeled off at an angle of 180° and a speed of 50 m/min, and then XPS on the surface of the copper-containing seed layer was analyzed. The results are shown in Table 2 and FIG. 5 .

XPS used for analysis was K-Alpha, ThermoFisher's equipment.

(10) XRF analysis - Si content (cps)

For the primer layer surface of the copper-clad laminated films of Examples 7, 9-11, and Comparative Examples 5-8, XRF (X-ray fluorescence spectrometry, Minipal4, Panalytical) was used to analyze the Si content was measured under the analysis conditions of s. The results are shown in Table 4.

(11) Adhesive force of the copper-containing layer to the base structure (or peel strength, kgf/cm)

1) Adhesion evaluation 1

For the copper clad laminated films of Examples 1 to 3 and Comparative Examples 1 to 2, a 3 mm width perforated line was put to prepare a sample. The samples were peeled at a tensile speed of 50 mm/min and a 180° angle using a peel strength tester (manufactured by Shimazu, AG-50NIS) to measure the peel strength (kgf/cm) of the copper-containing layer with respect to the substrate structure. . The results are shown in Tables 1 and 2.

2) Adhesion evaluation 2

For the copper-clad laminated films of Examples 4 to 11 and Comparative Examples 3 to 8, a sample having a circuit pattern having a width of about 3 mm was prepared. For each sample, using an adhesive force meter (TA.XT.plus, Texture Analyzer, Inc.) at 25 ℃ at a rate of 50 mm/min ('room temperature adhesive force') and 140 ℃ ~ 160 ℃ 160 ~ 180 hours After standing ('heat-resistant adhesive strength'), the peel strength (kgf/cm) when the copper-containing layer was separated from the base structure was measured. The results are shown in Tables 3 and 4.

(12) Whether the circuit pattern is peeled off after hydrochloric acid treatment

With respect to the copper clad laminated films of Examples 2 to 6, 8 and Comparative Examples 3 to 4, a circuit pattern having a width of about 1 mm was formed on the surface, and the entire opposite surface of the copper clad laminate on which the circuit pattern was formed was etched, It was heat-treated in an oven at 150 °C for 12 hours. Then, the heat-treated copper clad laminate was immersed in a 10% hydrochloric acid (HCl) solution for 3 minutes, and peeling was visually observed. Whether or not the circuit pattern was peeled off was determined based on the following criteria. The results are shown in Tables 2 and 3.

X: The area where the circuit pattern is attached on the copper clad laminate film is 90% or more (or the circuit pattern is not peeled off)

△: The area where the circuit pattern is attached on the copper clad laminate film is 11% to 89% (or partial peeling of the circuit pattern)

○: The area where the circuit pattern is attached on the copper clad laminate film is 10% or less (or the entire circuit pattern is peeled off)

division	written type (thickness, μm)	write (@ 28 GHz)		send Loss (dB/cm)	I [200] /I [311]	surface illuminance (R z , μm)	fatigue life span (episode)	peeling burglar (kgf/cm)
		permittivity (D k )	heredity Loss (D f )
Example 1	polyimide film (25 μm)	3.3	0.005	0.7	9.4	0.01	280	0.87
Comparative Example 1	Liquid crystalline polymer (LCP) film (25 μm)	3.1	0.0022	0.9	-	0.6	265	0.80
Comparative Example 2	Modified-polyimide (m-PI) film (25 μm)	3.1	0.0060	1.1	1.2	0.3	225	1.2

As shown in Table 1, the polyimide film substrate of the copper-clad laminated film of Example 1 had a dielectric loss (Df) at a frequency of 28 GHz compared with the modified-polyimide (m-PI) film substrate of the copper-clad laminated film of Comparative Example 2 ) was low, and the transmission loss was low compared to the base material of the copper clad laminated films of Comparative Examples 1 and 2.

The copper clad laminate film comprising the polyimide film substrate of Example 1 and the primer layer containing a silane coupling agent was compared with the copper clad laminate film in which the modified-polyimide (m-PI) film substrate of Comparative Example 2 and the polyamic acid-containing adhesive layer were laminated Therefore, I _[200] /I _[311] by XRD analysis was low.

The polyimide film substrate of Example 1 and the silane coupling agent-containing copper clad laminate film were laminated with the liquid crystal polymer (LCP) film substrate or modified-polyimide (m-PI) film substrate of Comparative Examples 1 and 2, and an adhesive layer containing polyamic acid. Compared with the copper clad laminate film, the surface roughness was low and the fatigue life was high. The copper-clad laminated film of Example 1 had higher adhesion or peel strength of the copper-containing layer to the base structure compared with the copper-clad laminated film of Comparative Example 1.

From this, the copper-clad laminated film of Example 1 has low dielectric loss, low transmission loss, and low I _[200] /I _[311] by XRD analysis at a high frequency of 28 GHz while At the same time It can be confirmed that the copper-containing layer has a high fatigue life and high adhesion to the substrate structure.

division	written type (thickness, μm)	write (@ 28 GHz)		Peel strength (kgf/mm)	Whether the circuit pattern is peeled off after hydrochloric acid treatment
		permittivity (D k )	dielectric loss (D f )
Example 2	polyimide film (50 μm)	3.3	0.005	0.85	△
Example 3	polyimide film (50 μm)	3.3	0.005	0.85	X

As shown in Table 2, in the copper clad laminate film including the copper alloy seed layer of copper and nickel of Example 3, the circuit pattern peeling phenomenon did not occur after hydrochloric acid treatment. In comparison, in the copper clad laminate film including the copper seed layer of Example 2, the circuit pattern was partially peeled off after hydrochloric acid treatment.

Meanwhile, referring to FIG. 4A , in the copper clad laminate of Example 3, it can be confirmed that the polyimide film substrate, the primer layer, and the copper alloy seed layer of copper and nickel are sequentially arranged from the bottom. 4B and 4C, the copper clad laminated film of Example 3 has a region from the polyimide film substrate to the copper-containing layer, specifically, the copper alloy seed layer to about 0 to 60 mm, that is, the deep portion, the polyimide film substrate. It can be seen that the content of the nickel element is greater than the area of more than 60 mm toward the copper alloy seed layer, that is, the surface portion.

Referring to FIG. 5 , the copper alloy seed of copper and nickel of the copper clad laminate of Example 3 with respect to the peak strength (I _Cu ) in the region of 933.58 eV to 953.98 eV of binding energy of the copper seed layer of the copper clad laminate of Example 2 The ratio of the peak intensity (I _Cu+Ni ) (I _Cu+Ni /I _Cu ) was 0.87 in the layer binding energy 933.58 eV to 953.98 eV region.

division	written type (thickness, μm)	write (@ 20 GHz)		fry Murphym thickness (nm)	surface contact angle (°)		peel strength (kgf/cm)		Whether the circuit pattern is peeled off
		permittivity (D k )	heredity Loss (D f )		water	diiodo methane	25℃	140℃ ~ 160℃
Example 4	Poly imide film (50 μm)	3.4	0.007	5	60	33	0.81	0.45	X
Example 5	Poly imide film (50 μm)	3.4	0.007	15	48	56	0.85	0.60	X
Example 6	low dielectric constant Poly imide film (50 μm)	3.2	0.004	10	53	48	0.90	0.70	X
Example 8	low dielectric constant Poly imide film (50 μm)	3.2	0.004	5	69	33	0.92	0.81	X
comparative example 3	Poly imide film (50 μm)	3.4	0.007	0	78	16	0.60	0.31	△
comparative example 4	low dielectric constant Poly imide film (50 μm)	3.2	0.004	0	83	8	0.42	0.32	△

As shown in Table 3, the water contact angle of the primer layer surface of the copper clad laminated films of Examples 4 to 6 and 8 was 48° to 69°, and the diiodomethane contact angle was 33° to 56°. The peel strength ('room temperature adhesion') of the copper-containing layer to the base structure of the copper-clad laminated films of Examples 4 to 6 and 8 was 0.80 kgf/cm or more, and the peel strength at 140 °C to 160 °C ('heat-resistant adhesive strength') ) was 0.45 kgf/cm or more, and there was no peeling of the circuit pattern after hydrochloric acid treatment at room temperature.

As a result, as a base material of Examples 4 to 6 and 8, a (low dielectric constant) polyimide film, and an amino-based silane coupling agent or an amino-based silane coupling agent and a vinyl-based silane coupling agent as a primer layer were included in a thickness of 15 nm or less, , it can be confirmed that the copper clad laminate film including the copper (alloy) seed layer can be used in the printed circuit board manufacturing process.

In comparison, the copper clad laminated films of Comparative Examples 3 to 4 not including the primer layer exhibited low room temperature adhesion and low heat resistance adhesion of the copper-containing layer to the base structure. For this reason, the circuit patterns formed on the copper clad laminated films of Comparative Examples 3 and 4 had some peeling phenomenon after hydrochloric acid treatment. In addition, the copper-clad laminated film of Comparative Example 4 using the low dielectric constant polyimide film substrate showed lower room temperature adhesion. It is considered that the low dielectric constant polyimide film substrate reduces the adhesive strength due to the small amount of reactive functional groups on the surface of the copper clad laminate film.

division	written type (thickness, μm)	write (@ 20 GHz)		primer layer thickness (nm)	Si content (cps)	peel strength (kgf/cm)
		permittivity (D k )	dielectric loss (D f )			25℃	140℃ ~ 160℃
Example 7	Poly imide film (50 μm)	3.4	0.007	5	28	0.81	0.55
Example 9	Poly imide film (50 μm)	3.4	0.007	15	105	0.88	0.70
Example 10	low dielectric constant Poly imide film (50 μm)	3.2	0.004	10	63	0.88	0.70
Example 11	low dielectric constant Poly imide film (50 μm)	3.2	0.004	5	25	0.92	0.81
Comparative Example 5	low dielectric constant Poly imide film (50 μm)	3.2	0.004	65	193	0.35	0.15
Comparative Example 6	low dielectric constant Poly imide film (50 μm)	3.2	0.004	43	160	0.52	0.45
Comparative Example 7	low dielectric constant Poly imide film (50 μm)	3.2	0.004	45	162	0.65	0.45
Comparative Example 8	low dielectric constant Poly imide film (50 μm)	3.2	0.004	30	123	0.70	0.38

As shown in Table 4, the Si content on the surface of the primer layer of the copper clad laminated films of Examples 7 and 9 to 11 was 28 cps to 105 cps. The peel strength ('room temperature adhesion') of the copper-containing layer to the base structure of the copper clad laminated films of Examples 7 and 9 to 11 was 0.80 kgf/cm or more, and the peel strength at 140 °C to 160 °C ('heat-resistant adhesive strength') ) was 0.50 kgf/cm or more. Room temperature adhesion and heat resistance of the copper-containing layer to the base structure of the copper clad laminated films of Examples 7 and 9 to 11 were higher than those of the copper clad laminated films of Comparative Examples 5 to 8.

As a result, the (low dielectric constant) polyimide film as a base material of Examples 7 and 9-11, and an amino-based silane coupling agent and a vinyl-based silane coupling agent as a primer layer were included in a thickness of 15 nm or less, and a copper (alloy) seed It can be confirmed that the copper-clad laminate film including the layer can be used in the printed circuit board manufacturing process.

In comparison, the copper-clad laminated films of Comparative Examples 5 to 6 using the low dielectric constant polyimide film substrate showed lower room temperature adhesion. It is considered that the low dielectric constant polyimide film substrate reduces adhesive strength due to the small number of reactive functional groups on the surface of the copper clad laminate film. Since the copper clad laminate film of Comparative Example 5 formed a gel by self-reaction including a thick primer layer, room temperature adhesion and heat resistance adhesion of the copper-containing layer to the substrate structure were low. The copper-clad laminated films prepared in Comparative Examples 7 to 8 formed a copper-containing layer and an electrolytic plating layer under the same conditions as in Example 11. However, due to the difference in the composition of the applied primer layer, room temperature adhesion and low heat resistance of the copper-containing layer to the substrate structure was low. Adhesion was shown, and the peeling strength of the copper-containing layer to the substrate structure was also low after hydrochloric acid treatment, so that the pattern was partially peeled off.

Claims (23)

1. a substrate structure having a primer layer disposed on at least one surface of the substrate; and

   Including; a copper-containing layer disposed on the base structure;

   The ratio of the peak intensity of the [200] orientation to the peak intensity of the [311] orientation by X-ray diffraction (XRD) analysis of the copper-containing layer (I _[200] /I _[311] ) 2.0 or more, copper clad laminated film.
2. According to claim 1,

   The surface roughness (R _z ) of the surface of the copper-containing layer is 0.1 μm or less, the copper-clad laminated film.
3. According to claim 1,

   The peeling strength of the copper-containing layer with respect to the base structure at 25 ° C. is 0.80 kgf / cm or more, the copper clad laminated film.
4. According to claim 1,

   After heat treatment at 150 ° C. for 2 hours, left twice at room temperature for 30 minutes, and after additional heat treatment at 240 ° C. for 10 minutes, the peel strength of the copper-containing layer with respect to the substrate structure is 0.45 kgf / cm or more, the copper clad laminated film.
5. According to claim 1,

   The copper-clad laminated film, wherein the copper-containing layer comprises a copper seed layer or a seed layer of at least one copper alloy selected from copper and nickel, zinc, beryllium, and chromium.
6. 6. The method of claim 5,

   The copper-containing layer includes a copper alloy seed layer of copper and nickel,

   The copper clad laminated film, wherein the core portion of the copper alloy seed layer contains more nickel than the surface portion.
7. 6. The method of claim 5,

   A copper clad laminate film that satisfies the peak intensity ratio of Equation 1 below in the region of binding energy 933.58 eV to 953.98 eV during XPS analysis of the surface of the copper seed layer or the copper alloy seed layer:

   [Equation 1]

   I _Cu+Ni /I _Cu ≤ 0.9

   during the meal,

   I _{Cu + Ni} is the peak strength of the copper alloy seed layer in the region of binding energy 933.58 eV to 953.98 eV,

   I _Cu is the peak intensity of the copper seed layer in the region of binding energy 933.58 eV to 953.98 eV.
8. 6. The method of claim 5,

   wherein the copper seed layer or the copper alloy seed layer is a sputtering layer.
9. 6. The method of claim 5,

   The copper clad laminate film further comprising a metal plating layer on one surface of the copper seed layer or the copper alloy seed layer.
10. According to claim 1,

    The substrate is a polyimide-based substrate,

    The polyimide-based substrate has a dielectric constant (D _k ) of 3.4 or less and a dielectric loss (D _f ) of 0.007 or less at a frequency of 20 GHz, a copper clad laminate film.
11. 11. The method of claim 10,

    The polyimide-based substrate has a dielectric constant (D _k ) of 3.3 or less and a dielectric loss (D _f ) of 0.005 or less at a frequency of 28 GHz, a copper clad laminate film.
12. 11. The method of claim 10,

    The polyimide-based substrate has a transmission loss of 0.8 dB/cm or less at a frequency of 28 GHz, a copper-clad laminated film.
13. According to claim 1,

    The thickness of the substrate is 5 μm to 100 μm, the copper clad laminated film.
14. According to claim 1,

    A copper-clad laminated film, wherein the primer layer includes a silane coupling agent represented by the following formula (1):

    [Formula 1]

    RC _m H _2m Si(OC _n H _2n ) ₃

    during the meal,

    R is a substituted or unsubstituted C2-C20 alkenyl group, —N(R ₁ )(R ₂ ), or a combination thereof, wherein R ₁ and R ₂ are each independently a hydrogen atom, a halogen atom, a substituted or unsubstituted a C1-C10 alkyl group, a substituted or unsubstituted C2-C10 alkenyl group, a substituted or unsubstituted C2-C10 alkynyl group, a substituted or unsubstituted C3-C20 cycloalkyl group, a substituted or unsubstituted C3- a C20 cycloalkenyl group, a substituted or unsubstituted C6-C20 aryl group, or a substituted or unsubstituted C6-C20 heteroaryl group,

    n is an integer from 1 to 5,

    m is 0 to 10.
15. According to claim 1,

    The primer layer comprising an amino-based silane compound, a vinyl-based silane compound, or a mixture thereof.
16. 16. The method of claim 15,

    The weight ratio of the amino-based silane compound to the vinyl-based silane compound is 1:1 to 9:1, the copper clad laminated film.
17. According to claim 1,

    The Si content by X-ray fluorescence spectrometry (XRF) analysis on the surface of the primer layer is 10 cps to 120 cps, the copper-clad laminated film.
18. According to claim 1,

    A copper clad laminate film having a water contact angle of 45° to 70° on the surface of the primer layer.
19. According to claim 1,

    The thickness of the primer layer is 500 nm or less, the copper clad laminated film.
20. According to claim 1,

    When the thickness of the substrate is 25㎛, the fatigue life of the film according to MIT measurement according to JIS C 6471 is 270 times or more, the copper clad laminated film.
21. An electronic device comprising the copper clad laminate according to any one of claims 1 to 20.
22. preparing a substrate;

    forming a primer layer by applying a composition for forming a primer layer on at least one surface of the substrate; and

    A method of manufacturing a copper-clad laminated film comprising a; forming a copper-containing layer on the primer layer by sputtering to prepare the copper-clad laminated film according to any one of claims 1 to 20.
23. 23. The method of claim 22,

    Further comprising the step of performing plasma treatment after the step of forming the primer layer, a method of manufacturing a copper clad laminate.

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