KR20230034687A - Copper clad laminate film, electronic device including the same - Google Patents

Abstract

Disclosed are a copper foil laminate film and an electronic element comprising the same. The copper foil laminate film comprises: a polyimide-group base; a primer layer positioned on at least one surface of the polyimide-group base; a copper-containing seed layer positioned on the primer layer; and a copper plating layer positioned on the copper-containing seed layer, wherein the copper plating layer is formed with an adhesion amount per unit time of 600-800 μg/dm^2·s, the number of pinholes per 156 x 300 mm^2 area on a surface of the copper plating layer is 10 or less, and a crack may occur at 50 or more times during MIT measurement according to a JIS C 6471 method.

Description

Copper clad laminate film and electronic device including the same {Copper clad laminate film, electronic device including the same}

It relates to a copper clad laminated film and an electronic device including the same.

The copper clad laminated film is a laminate of a substrate and a conductive copper foil. The use of copper clad laminated film is increasing along with the trend of miniaturization and weight reduction of electronic devices. Due to the recent development of 5G mobile communication devices, signal transmission rates in the GHz band are becoming common. It is necessary to improve the dielectric properties of substrates used for printed circuits or antenna elements according to the trend of high-frequency signals. At the same time, the copper clad laminate film is required to have physical properties such as low defectivity, high bendability, and excellent adhesion. Therefore, there is still a need for a copper clad laminated film having low dielectric constant and low dielectric loss at high frequencies, low defects, high bendability, and excellent adhesion, and an electronic device including the same.

One aspect provides a copper clad laminated film having low permittivity and low dielectric loss at high frequencies, low defects, high bendability, and excellent adhesion, as well as chemical resistance.

Another aspect is provided with an electronic device including the copper clad laminated film.

According to one aspect,

polyimide base material;

a primer layer located on at least one surface of the polyimide-based substrate;

a copper-containing seed layer positioned on the primer layer; and

A copper plating layer located on the copper-containing seed layer; includes,

The copper plating layer is formed with an adhesion amount per unit time of 600 to 800 μg/dm ² ·s,

Provided is a copper clad laminated film in which the number of pinholes per area of 156 x 300 mm 2 is 10 or less on the surface of the copper plating layer, and cracks occur more than 50 times when measured by MIT according to the JIS C 6471 method.

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 thickness of the polyimide-based substrate may be 12.5 μm to 50 μm.

The primer layer may include a silane coupling agent.

The primer layer may include a silane coupling agent represented by Formula 1 below:

<Formula 1>

RC _m H _2m Si(OC _n H _2n ) ₃

during the ceremony,

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, substituted or unsubstituted C1-C10 alkyl group, substituted or unsubstituted C2-C10 alkenyl group, substituted or unsubstituted C2-C10 alkynyl group, substituted or unsubstituted C3-C20 cycloalkyl group, 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 a number from 0 to 10;

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

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

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

The copper-containing seed layer may be a sputter layer.

The copper-containing seed layer is a seed layer of copper and one or more alloys selected from nickel, zinc, beryllium, and chromium, and a core portion of the copper-containing seed layer may have a greater nickel element content than a surface portion.

The copper plating layer may have a thickness of 12 μm or less.

When the copper-containing seed layer and the copper plating layer are peeled off from the copper-clad laminated film and XPS analysis of the surface of the copper-containing seed layer is performed, the peak intensity ratio of Equation 1 below may be satisfied in a binding energy range of 933.58 eV to 953.98 eV:

<Equation 1>

I _Cu+Ni /I _Cu ≤ 0.9

during the ceremony,

I _Cu+Ni may be a peak intensity in a binding energy range of 933.58 eV to 953.98 eV when the copper-containing seed layer is a seed layer of copper and one or more alloys selected from nickel, zinc, beryllium, and chromium,

I _Cu may be a peak intensity in a binding energy range of 933.58 eV to 953.98 eV when the copper-containing seed layer is a copper seed layer.

According to other aspects,

An electronic device including the above-described flexible copper foil laminated film is provided.

The electronic element may include an antenna element or an antenna cable.

The copper clad laminate film according to one aspect includes a polyimide-based substrate, a primer layer positioned on at least one surface of the polyimide-based substrate, a copper-containing seed layer positioned on the primer layer, and a copper plating layer positioned on the copper-containing seed layer. The copper plating layer is formed with an adhesion amount per unit time of 600 to 800 μg/dm ² ·s, the number of pinholes per 156 x 300 ㎟ area is 10 or less on the surface of the copper plating layer, and MIT according to the JIS C 6471 method Cracks occur more than 50 times during measurement. The copper-clad laminate film may have low dielectric constant and low dielectric loss at high frequencies, low defects, high bendability, and excellent adhesion, as well as chemical resistance.

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 laminate according to another embodiment.
3A to 3C are EDAX results showing the content distribution of elemental nickel from the entire copper-clad laminate film and the polyimide substrate to the copper-containing seed layer according to Example 2, respectively.
4 is XPS on the surface of the copper-containing seed layer when the copper-containing seed layer and the copper plating layer are peeled after forming a circuit pattern on the surface of the copper-clad laminate film according to Examples 1 and 2 and performing heat treatment is the analysis result.

Hereinafter, a copper clad laminated film and an electronic device including the same will be described in detail with reference to the embodiments and drawings of the present invention. These examples are only presented as examples to explain the present invention in more detail, and it will be apparent to those skilled in the art 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 this specification, the term "include" means that other components may be further included without excluding other components unless otherwise stated.

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

In the present specification, "polyimide-based substrate" means to include "polyimide substrate" and "derivatives thereof".

In this specification, when an element is referred to as being disposed “on” another element, one element may be directly disposed on the other element, or there may be elements interposed between the elements. there is. On the other hand, when an element is referred to as being disposed “directly on” another element, intervening elements may not be present.

Among electronic devices, an antenna device is typically manufactured by laminating a metal layer, for example, copper foil, on which an electrical flow by a radio signal is made, on a base film.

Loss that occurs in relation to signal reception of the antenna includes loss due to the permittivity of the base film and signal loss physically caused by electrical resistance when a radio signal, that is, an electrical signal flows through a metal layer. Compared to radio signals having a relatively low frequency band, a radio signal having a high frequency band causes an electrical flow to be more concentrated on the surface of the metal layer. In addition, in the copper clad laminated film of the laminate method, physical stress is generated in the copper foil in the curved area of the antenna element, and defects or cracks occur on the surface thereof. As a result, transmission loss may occur. In addition, it is necessary to improve the adhesion between the substrate and the conductive copper foil.

In order to solve this problem, the inventors of the present invention propose the following copper clad laminated film.

The copper clad laminate film according to one embodiment includes a polyimide-based substrate; a primer layer located on at least one surface of the polyimide-based substrate; a copper-containing seed layer positioned on the primer layer; and a copper plating layer located on the copper-containing seed layer, wherein the copper plating layer is formed with an adhesion amount per unit time of 600 to 800 μg/dm ² ·s, and the number of pinholes per 156 x 300 mm2 area on the surface of the copper plating layer is less than 10, and cracks may occur more than 50 times during MIT measurement according to the JIS C 6471 method. The copper-clad laminate film may have low dielectric constant and low dielectric loss at high frequencies, low defects, high bendability, and excellent adhesion, as well as chemical resistance.

1 is a schematic cross-sectional view of a copper clad laminated film 10 according to an embodiment. 2 is a schematic cross-sectional view of a double-sided copper clad laminate according to another embodiment.

Referring to FIG. 1, in the copper clad laminated film 10 according to one embodiment, a polyimide-based substrate 1, a primer layer 2 are positioned on one side of the polyimide-based substrate 1, and the primer layer ( 2) A copper-containing seed layer 3 is positioned on the copper-containing seed layer 3, and a copper plating layer 4 is positioned on the copper-containing seed layer 3. Referring to FIG. 2, a copper clad laminated film 20 according to another embodiment includes primer layers 12 and 12' and copper-containing seed layers 13 and 13' on one side and the other side of a polyimide-based substrate 11, respectively. ), and the copper plating layers 14 and 14' are located in this order.

Hereinafter, the polyimide-based substrates 1 and 11 constituting the copper clad laminated films 10 and 20, the primer layers 2, 12 and 12', the copper-containing seed layers 3, 13 and 13', and the copper plating layer (4, 14, 14') is described.

<Polyimide base material (1, 11)>

The polyimide-based substrates 1 and 11 may be modified polyimide (m-PI) substrates. The modified-polyimide substrate is a resin substrate in which highly polar substituents are reduced. When a radio signal flows through a circuit, a change occurs in the electric field around the circuit. When the electric field change approaches the relaxation time of the internal polarization of the resin substrate, the electric displacement is delayed. At this time, molecular friction occurs inside the resin substrate to generate heat, and the generated heat affects dielectric properties. Therefore, as the substrate, a modified-polyimide substrate in which substituents having high polarity are reduced is used. The polyimide-based substrate 1 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 thickness of the polyimide-based substrates 1 and 11 may be 12.5 μm to 50 μm. For example, the thickness of the polyimide-based substrates 1 and 11 may be 12.5 μm to 50 μm or 12.5 μm to 40 μm. If the thickness of the polyimide-based substrates 1 and 11 is less than 12.5 μm, productivity may decrease during the manufacture of the copper clad laminated films 10 and 20, and if the thickness exceeds 50 μm, thinning may not be achieved.

<Primer layer (2, 12, 12')>

Primer layers 2, 12, and 12' are positioned on at least one surface of the polyimide-based substrates 1 and 11. The primer layers 2, 12 and 12' contain a silane coupling agent. As the silane coupling agent, epoxy-based silane, amino-based silane, methacryloxy-based silane, mercapto-based silane, vinyl-based silane, imidazole-based silane, or triazine-based silane may be used. The silane coupling agent may be used alone or in combination of two or more.

The primer layers 2, 12, and 12' may include a silane coupling agent represented by Formula 1 below:

<Formula 1>

RC _m H _2m Si(OC _n H _2n ) ₃

during the ceremony,

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, substituted or unsubstituted C1-C10 alkyl group, substituted or unsubstituted C2-C10 alkenyl group, substituted or unsubstituted C2-C10 alkynyl group, substituted or unsubstituted C3-C20 cycloalkyl group, 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 a number from 0 to 10.

For example, a mixture of a vinyl-based silane compound and an amino-based silane compound may be used as the silane coupling agent. The silane coupling agent may have a higher content of the amino-based silane compound than that of the vinyl-based silane compound.

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

If the weight ratio of the vinyl-based silane compound and the amino-based silane compound is within the above range, the polyimide-based substrates 1 and 11 of the copper clad laminated films 10 and 20, the copper seed layers 3, 13, and 13' and the copper Peel strength between the plating layers 4, 14, and 14' at room temperature may be improved. The copper clad laminated films 10 and 20 do not generate fine cracks on their surfaces, and when applied to small electronic devices, the possibility of circuit disconnection may be reduced. As a result, the copper clad laminated films 10 and 20 having high bendability, that is, high fatigue life in a thin film form can be implemented.

The thickness of the primer layers 2, 12, and 12' may be 500 nm or less. For example, the thickness of the primer layers 2, 12, and 12' may be 0.1 nm to 500 nm. For example, the thickness of the primer layers 2, 12, 12' may be 1 nm to 300 nm, may be 1 nm to 200 nm, may be 1 nm to 100 nm, or may be 1 nm to 50 nm. Even when the thickness of the primer layers (2, 12, 12') is in the above thin film range, the polyimide-based substrates (1, 11), the copper seed layers (3, 13, 13') and the copper plating layers (4, 14, 14') ), the peel strength can be improved, and the copper clad laminated films 10 and 20 including the same can have high bendability, that is, high fatigue life.

The primer layers 2, 12, and 12' may be formed by applying a composition for forming a primer layer on the polyimide-based substrates 1 and 11 using a solution application method and drying the composition.

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

<Copper-containing seed layer (3, 13, 13')>

Copper-containing seed layers 3, 13, and 13' are positioned on the primer layers 2, 12, and 12'. If necessary, plasma treatment may be performed on the primer layers 2 , 12 , and 12 ′ to improve surface roughness R _z . For example, the plasma treatment may use RF plasma treatment. The RF plasma treatment may be performed using an inert gas and oxygen gas at a volume ratio of 1:1 to 4:1 and using a power of about 500 W or more. The copper-containing seed layers 3, 13, and 13' may be sputtered layers. The copper-containing sputter seed layer can maintain the surface roughness of the polyimide-based substrates 1 and 11 themselves, and thus can reduce transmission loss while having a low surface roughness (R _z ). As the sputtering method, methods such as physical vapor deposition (PVD), chemical vapor deposition (CVD), low pressure chemical vapor deposition (LPCVD), and vacuum deposition may be used. For example, a physical vapor deposition (PVD) method may be used as a sputtering method.

The copper-containing seed layers 3, 13, and 13' may be a copper seed layer or a seed layer of copper and one or more alloys selected from nickel, zinc, beryllium, and chromium. For example, the copper-containing seed layer 3, 13, 13' may be a copper and nickel alloy seed layer. The copper-nickel alloy seed layer may have a copper-nickel weight (%) ratio of 60:40 to 95:5. For example, the copper-containing seed layers 3, 13, and 13' may have a weight (%) ratio of copper to nickel in a range of 60:40 to 90:10. For example, the copper-containing seed layers 3, 13, and 13' may be one or more alloy seed layers selected from zinc, beryllium, and chromium in addition to copper and nickel. In addition to copper and nickel, the weight (%) ratio of one or more metals selected from zinc, beryllium, and chromium may be 60:35:5 to 90:5:5 or 60:35:5 to 80:15:5 can

The copper-containing seed layers 3, 13, and 13' may have a thickness of 800 Å to 4000 Å. For example, the copper-containing seed layer 3 may have a thickness of 850 Å to 3500 Å, or 900 Å to 3000 Å, or 950 Å to 2500 Å, or 1000 Å to 2000 Å, or 1000 Å to 1500 Å. Å. If the copper-containing seed layers (3, 13, 13') have the above thickness range, conductivity can be secured during film formation, and copper clad laminated films (10, 20) having low surface roughness (R _z ) and low transmission loss can provide.

The copper-containing seed layers 3, 13, and 13' are seed layers of copper and one or more alloys selected from nickel, zinc, beryllium, and chromium, and the core portion of the copper-containing seed layers 3, 13, 13' is the surface portion. The nickel element content may be higher. In the present specification, the deep portion means an area from the polyimide-based substrates 1 and 11 toward the copper-containing seed layers 3, 13, and 13' from about 0 to 60 mm, and the surface portion refers to a region extending from the polyimide-based substrates 1 and 11 toward the copper-containing seed layers 3, 13, and 13'. , 11) toward the copper-containing seed layers 3, 13, and 13'. The copper-containing seed layers 3, 13, and 13' can prevent moisture and air passing through the polyimide-based substrates 1 and 11 from being oxidized in the copper-containing seed layers 3, 13, and 13'. For this reason, when chemical polishing (soft etching) is performed on the surfaces of the copper clad laminated films 10 and 20 including the same with acids such as hydrochloric acid, formic acid, and sulfuric acid, the polyimide-based substrates 1 and 11 and the copper-containing seed Peeling of the layers 3, 13, and 13' and the copper plating layers 4, 14, and 14' can be prevented. The nickel element content of the copper-containing seed layers 3, 13, and 13' can be confirmed in EDAX of FIGS. 3A to 3C to be described later.

<Copper plating layer (4, 14, 14')>

Copper plating layers 4, 14, and 14' are positioned on the copper seed layers 3, 13, and 13'. As a method of forming the copper plating layers 4, 14, and 14', an electroless plating method or an electrolytic plating method may be used. For example, an electrolytic plating method may be used for the copper plating layers 4, 14, and 14'.

As a method of forming the copper electrolytic plating layer, all methods usable in the art may be used. For example, a copper electrolytic plating layer may be formed on one surface of the copper seed layers 3, 13, and 13' by performing electroplating with an electrolytic plating solution containing copper sulfate and sulfuric acid as a basic material. In addition, additives such as brighteners, levelers, correctors, or softeners may be added to the electrolytic plating solution for productivity and surface uniformity.

The copper plating layers 4, 14, and 14' may be formed with an adhesion amount per unit time of 600 to 800 μg/dm ² ·s. The copper plating layers 4, 14, and 14' have 10 or less pinholes per area of 156 x 300 mm2 on the surface, and cracks may occur more than 50 times when measured by MIT according to the JIS C 6471 method.

The copper plating layers 4, 14, and 14' may have a thickness of 12 μm or less. For example, the thickness of the copper plating layers 4, 14, and 14' may be 0.1 μm to 12.0 μm, 1.0 μm to 12.0 μm, 2.0 μm to 12.0 μm, or 3.0 μm to 12.0 μm.

<Copper clad laminated film (10, 20)>

The copper-clad laminate films 10 and 20 have low resistivity and magnetic permeability by including the copper-containing seed layers 3, 13, and 13' instead of the commonly used Ni-Cr tie layer, and thus have low surface resistance. In addition, when the copper-containing seed layers 3 , 13 , and 13 ′ are sputter layers, copper plating layers 4 , 14 , and 14 ′ having a lower roughness than a laminate method may be deposited. Due to this, the copper clad laminated films 10 and 20 have a reduced surface resistance as the transmission line is shortened when current flows.

The copper-containing seed layer is obtained by peeling the polyimide-based substrate (1, 11), the copper-containing seed layer (3, 13, 13') and the copper plating layer (4, 14, 14') from the copper clad laminated film (10, 20). (3, 13, 13 ') In the case of XPS analysis of the surface, the peak intensity ratio of Equation 1 below may be satisfied in the region of binding energy 933.58 eV to 953.98 eV:

<Equation 1>

I _Cu+Ni /I _Cu ≤ 0.9

during the ceremony,

I _Cu+Ni is the peak intensity in the binding energy 933.58 eV to 953.98 eV region when the copper-containing seed layer is a seed layer of copper and at least one alloy selected from nickel, zinc, beryllium, and chromium,

I _Cu is a peak intensity in a binding energy range of 933.58 eV to 953.98 eV when the copper-containing seed layer is a copper seed layer.

The binding energy 933.58 eV to 953.98 eV region during XPS analysis refers to the peak region of copper oxide (Cu _x O _y , 0 < x ≤ 5, 0 < y ≤ 5) . The copper clad laminated films 10 and 20 having the peak intensity ratio of Equation 1 in the copper oxide peak region have excellent chemical resistance. The XPS analysis result can be confirmed in FIG. 4 described later.

If necessary, heat treatment may be performed on the copper clad laminated films 10 and 20 at a temperature of 100 to 200 ° C for 10 to 20 hours. The copper clad laminated films 10 and 20 may have excellent chemical resistance even under such heat treatment conditions.

<Electronic device>

An electronic device according to another embodiment may include the copper clad laminated films 10 and 20 .

The electronic element may include an antenna element or an antenna cable. For example, the antenna element may be an antenna element for a mobile phone or a display. In addition, the electric element may include a circuit board such as a network server, an Internet of Things (IoT) home appliance for 5G, a radar, and a USB.

The definition of the substitution (group) used in Formula 1 described herein is as follows.

"Substitution" in "substituted" of an alkyl group, an alkenyl group, an alkynyl group, a cycloalkyl group, a cycloalkenyl group, an aryl group, and a heteroaryl group used in Formula 1 refers to a halogen atom, a C1-C10 alkyl group substituted with a halogen atom (eg 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, or 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, hexyl, and the like. One or more hydrogen atoms may be substituted with a substituent as defined in "substitution" above.

Specific examples of the C2-C20 alkenyl group used in Formula 1 include vinylene, allylene, and the like, and one or more hydrogen atoms in the alkenyl group may be substituted with a substituent as defined in the above-mentioned "substitution". .

Specific examples of the C2-C10 alkynyl group used in Formula 1 include acetylene, and one or more hydrogen atoms in the alkynyl group may be substituted with a substituent as defined in the above-mentioned “substitution”.

Specific examples of the C3-C20 cycloalkyl group used in Formula 1 include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, and the like, and one or more hydrogen atoms in the cycloalkyl group are as defined in the above-mentioned "substitution" may be substituted with the same substituent.

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

The C6-C20 aryl group used in Formula 1, used alone or in combination, means an aromatic system containing one or more rings, and examples thereof include phenyl and naphthyl. In addition, one or more hydrogen atoms of 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 refers to an organic compound containing at least one heteroatom selected from N, O, P, or S, and the remaining ring atoms being carbon. Examples include pyridyl and the like. can In addition, one or more hydrogen atoms of 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, these examples are intended to explain the present invention in more detail, and it will be obvious that the scope of the present invention is not limited to these examples.

[Example]

Example 1: Copper clad laminated film

As a substrate, a polyimide film (manufactured by PI Advanced Materials) having a thickness of 50 μm (dielectric constant (D _k ): 3.3, dielectric loss (D _f ): 0.005 at a frequency of 28 GHz) was prepared.

Separately, N-2- (aminoethyl) -8-aminooctyl-trimethoxysilane (N-2- (aminoethyl) -8-aminooctyl-trimethoxysilane) and 7-octenyltrimethoxysilane (7- octenyltrimethoxysilane) was mixed in a weight ratio of 1:0.5 to prepare a composition for forming a primer layer. The composition for forming a primer layer was applied on the substrate to a thickness of about 300 nm using a bar coater and dried to form a primer layer.

RF plasma treatment was performed on both sides of the primer layer. RF plasma treatment was performed at about 1000 W power by introducing argon gas and oxygen gas at a volume ratio of 4:1. Then, a copper seed layer was formed to a thickness of 1200 Å using copper having a purity of 99.995% by physical vapor deposition (PVD) on the surface of the primer layer treated with RF plasma.

A double-sided copper clad laminated film as shown in FIG. 2 was manufactured by forming a copper plating layer having a thickness of about 12 μm on each of the copper seed layers by an electrolytic copper plating method.

The ^electrolytic copper plating solution contained 0.01 g/L of 3-N,N-dimethylaminodithiocarbamoyl-1-propanesulfonic acid as a brightener and a corrector ( Atotech product) was used. Electrolytic copper plating was performed at 30° C. with an applied amount of about 700 μg/dm ² ·s per unit time while applying a current of about 160 A.

Example 2: Copper clad laminated film

Using copper with a purity of 99.995% by physical vapor deposition (PVD), instead of a copper seed layer with a thickness of 1200 Å, a copper and nickel alloy having a weight (%) ratio of copper and nickel of 90:10 is formed by physical vapor deposition (PVD). A double-sided copper clad laminated film was produced in the same manner as in Example 1, except that a copper and nickel alloy seed layer having a thickness of 1200 Å was used.

Comparative Example 1: Copper clad laminated film

Electrolytic copper plating was applied to a current of about 120 A at 30 ° C., but a double-sided copper clad laminated film was produced in the same manner as in Example 1, except that the deposition amount per unit time of about 490 μg/dm ² ·s was applied.

Comparative Example 2: Copper clad laminated film

Electrolytic copper plating was applied to a current of about 140 A at 30 ° C., but a double-sided copper clad laminated film was produced in the same manner as in Example 1, except that it was performed at an adhesion amount per unit time of about 590 μg/dm ² ·s.

Comparative Example 3: Copper clad laminated film

A double-sided copper clad laminated film was manufactured in the same manner as in Example 1, except that a copper seed layer and a copper plating layer were sequentially formed on the substrate without forming a primer layer.

Evaluation Example 1: Evaluation of physical properties

The physical properties of the copper clad laminated films prepared in Examples 1 to 2 and Comparative Examples 1 to 3 were evaluated using the following measurement methods. The results are shown in Table 1, FIG. 3, FIG. 4a, FIG. 4b, FIG. 4c, and FIG. 5 below.

(1) Pinhole measurement

After making a sample by cutting each copper clad laminated film into a size of 156 mm x 300 mm, the opposite side of the measurement side (ie, the side corresponding to 12', 13', and 14' in FIG. 2) ) was completely etched, and the number of pinholes was measured by visually observing pinholes penetrating the film using a pinhole measuring device (manufactured by Toray Advanced Materials) using a halogen lamp. The results are shown in Table 1.

(2) MIT (fatigue life) measurement

Fatigue life was performed by MIT according to the JIS C 6471 method for each copper clad laminated film. For the MIT measurement, each copper clad laminated film was cut into a size of 15 mm x 170 mm, a pattern (width: 1000 μm) was etched, stored for 24 hours, and a sample stored in an oven at 80 ° C. for 1 hour was prepared. MIT was measured by hanging (+) and (-) electrodes on both ends of the sample. As the MIT measuring equipment, SFT-9250 and TOYO SEIKI were used. The results are shown in Table 1.

(3) Content distribution of nickel element - TEM/EDAX analysis

For the copper clad laminated film produced in Example 2, a depth profile and nickel element content distribution were analyzed using TEM/EDAX. The results are shown in FIGS. 3, 4a, 4b, and 4c. TEM/EDAX used for analysis was a Titan G2 ChemiSTEM Cs Probe, FEI Company's equipment.

(4) Chemical resistance (exfoliation)

A circuit pattern having a width of 1 mm was formed on the surface of the copper clad laminate film prepared in Example 1 and Example 2, and the entire reverse side of the copper clad laminate film on which the circuit pattern was formed was entirely etched, and then the copper clad laminate on which the circuit pattern was formed was formed. The film was heat treated in an oven at 150 °C for 12 hours. Then, the heat-treated copper clad laminated film was immersed in a 10% hydrochloric acid (HCl) solution for 3 minutes, and the chemical resistance (exfoliation) of the circuit pattern was judged.

(5) XPS analysis

A circuit pattern having a width of 1 mm was formed on the surface of the copper-clad laminate films prepared in Example 1 and Example 2, and the entire reverse side of the copper-clad laminate film on which the circuit pattern was formed was entirely etched, and then the copper foil with the circuit pattern was formed. The laminated film was heat-treated in an oven at 150 °C for 12 hours. Then, after peeling the copper-containing seed layer and the copper plating layer from the copper-clad laminate film at an angle of 180 ° and a speed of 50 m/min, XPS analysis of the surface of the copper-containing seed layer is shown in FIG. 5 . XPS used for analysis was K-Alpha, ThermoFisher equipment.

(5) Adhesion (kgf/mm)

Samples were prepared by inserting perforated lines with a width of 3 mm for each copper clad laminated film. The samples were peeled at a tensile speed of 50 mm/min and an angle of 180 ° using a peel strength tester (manufactured by Shimazu, AG-50NIS), and the peel strength (kgf/cm) of the copper seed layer and the base film of the copper layer ) was evaluated by measuring.

division Base (@ 28 GHz) number of pinholes
(dog) fatigue life
(episode) chemical resistance
(exfoliation) adhesion
(kgf/mm) permittivity
(D _k ) dielectric loss
(D _f ) Example 1 3.3 0.005 ≤ 10 60 exfoliation 0.85 Example 2 3.3 0.005 ≤ 10 60 unpeeled 0.85 Comparative Example 1 3.3 0.005 ≥ 500 35 exfoliation 0.85 Comparative Example 2 3.3 0.005 ≥ 500 40 exfoliation 0.85 Comparative Example 3 3.3 0.005 ≤10 60 unpeeled 0.60

As shown in Table 1, the number of pinholes in the copper-clad laminate film prepared in Example 1 is reduced by using a substrate having a low permittivity and low dielectric loss at high frequencies compared to the copper-clad laminate film manufactured in Comparative Examples 1 to 3. It can be confirmed that the number of times of fatigue life is increased as well as less. It can be confirmed that the copper clad laminate film prepared in Example 2 has excellent chemical resistance compared to the copper clad laminate film manufactured in Example 1. In addition, it can be confirmed that the copper clad laminate film prepared in Examples 1 and 2 has excellent adhesive strength compared to the copper clad laminate film manufactured in Comparative Example 3.

From this, it can be seen that the copper clad laminated films produced in Examples 1 and 2 have almost no defects and have excellent bendability and adhesive strength, thereby reducing the possibility of micro-cracks and disconnection. Therefore, the copper clad laminated film prepared in Examples 1 and 2 can be applied inside miniaturized electronic products. Among them, the copper clad laminated film prepared in Example 2 was improved in terms of chemical resistance.

Meanwhile, referring to FIG. 3A , it can be confirmed that the polyimide film, the primer layer, and the copper and nickel alloy seed layer are sequentially arranged from bottom to top. Referring to FIGS. 3B and 3C , a region from about 0 to 60 mm from the polyimide-based substrates 1 and 11 toward the copper-containing seed layers 3, 13, and 13', that is, the deep portion, the polyimide-based substrate From (1, 11), toward the copper-containing seed layers (3, 13, and 13'), it can be confirmed that the region of more than 60 mm, that is, the content of the nickel element is greater than that of the surface portion.

Referring to FIG. 4, the peak intensity (I _Cu ) of the copper seed layer of the copper-clad laminate film prepared in Example 1 in the region of 933.58 eV to 953.98 eV binding energy The ratio (I _{Cu+Ni /I Cu )} of the peak intensity (I _Cu+Ni ) was 0.87 in the region of binding energy of 933.58 eV to 953.98 eV of the and nickel alloy seed layer.

1, 11: polyimide base material, 2, 12, 12': primer layer,
3, 13, 13': copper-containing seed layer, 4, 14, 14': copper plating layer,
10, 20: copper clad laminated film

Claims (14)

polyimide-based substrate;
a primer layer located on at least one surface of the polyimide-based substrate;
a copper-containing seed layer positioned on the primer layer; and
A copper plating layer located on the copper-containing seed layer; includes,
The copper plating layer is formed with an adhesion amount per unit time of 600 to 800 μg/dm ² ·s,
The number of pinholes per area of 156 x 300 mm 2 on the surface of the copper plating layer is 10 or less, and cracks occur more than 50 times when measured by MIT according to the JIS C 6471 method. According to claim 1,
Wherein 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. According to claim 1,
A copper clad laminated film wherein the polyimide-based substrate has a thickness of 12.5 μm to 50 μm. According to claim 1,
The copper clad laminated film in which the primer layer contains a silane coupling agent. According to claim 1,
A copper clad laminate film in which the primer layer includes a silane coupling agent represented by Formula 1 below:
<Formula 1>
RC _m H _2m Si(OC _n H _2n ) ₃
during the ceremony,
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, substituted or unsubstituted C1-C10 alkyl group, substituted or unsubstituted C2-C10 alkenyl group, substituted or unsubstituted C2-C10 alkynyl group, substituted or unsubstituted C3-C20 cycloalkyl group, 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 a number from 0 to 10; According to claim 1,
A copper clad laminated film wherein the weight ratio of the vinyl-based silane compound to the amino-based silane compound is 1:1 to 1:9. According to claim 1,
A copper clad laminated film in which the thickness of the primer layer is 500 nm or less. According to claim 1,
The copper-clad laminate film, wherein the copper-containing seed layer is a copper seed layer or a seed layer of copper and one or more alloys selected from nickel, zinc, beryllium, and chromium. According to claim 1,
The copper-clad laminate film wherein the copper-containing seed layer is a sputter layer. According to claim 1,
The copper-containing seed layer is a seed layer of copper and at least one alloy selected from nickel, zinc, beryllium, and chromium;
The copper-clad laminate film, wherein the core portion of the copper-containing seed layer has a higher nickel element content than the surface portion. According to claim 1,
A copper clad laminated film in which the thickness of the copper plating layer is 12 μm or less. According to claim 1,
The copper-clad laminate film that satisfies the peak intensity ratio of Equation 1 below in the binding energy range of 933.58 eV to 953.98 eV when the copper-containing seed layer and the copper plating layer were peeled off from the copper-clad laminate film and XPS analysis of the surface of the copper-containing seed layer:
<Equation 1>
I _Cu+Ni /I _Cu ≤ 0.9
during the ceremony,
I _Cu+Ni is the peak intensity in the binding energy 933.58 eV to 953.98 eV region when the copper-containing seed layer is a seed layer of copper and at least one alloy selected from nickel, zinc, beryllium, and chromium,
I _Cu is a peak intensity in a binding energy range of 933.58 eV to 953.98 eV when the copper-containing seed layer is a copper seed layer. An electronic device comprising the copper clad laminated film according to any one of claims 1 to 12. According to claim 13,
The electronic device includes an antenna element or an antenna cable.

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