Copper-clad laminate film, article comprising same, and method for manufacturing copper-clad laminate film

Abstract

Disclosed are a copper-clad laminate film, an article comprising same, and a method for manufacturing the copper clad laminate film. The disclosed copper-clad laminate film comprises: a liquid crystal polymer substrate; an intermediate layer disposed on at least one surface of the liquid crystal polymer substrate; a tie layer disposed on the intermediate layer; and a copper layer disposed on the tie layer, wherein the intermediate layer is a cured layer of a composition containing a low dielectric constant polyimide-based resin, a silane coupling agent, and inorganic particles, the thickness of the intermediate layer is greater than the thickness of the tie layer, and the thickness of the intermediate layer and the thickness of the tie layer may satisfy expression 1 below. [Expression 1] 100 ≤ A / B < 500 In Expression 1, A is the thickness (nm) of the intermediate layer, and B is the thickness (nm) of the tie layer.

Description

Copper clad laminate film, an article including the same, and a method for manufacturing the copper clad laminate film

[0001] The present disclosure relates to a copper clad laminate film, an article comprising the same, and a method for manufacturing the copper clad laminate film.

[0002] Copper clad laminates are laminates of a substrate and a conductive copper foil. The usage of copper clad laminates is increasing along with the trend toward miniaturization and lightweighting of electronic devices. Recently, due to the development of 5G mobile communication devices, signal transmission speeds in the GHz band are becoming commonplace.

[0003] In response to the trend toward higher signal frequencies, research is being conducted to improve transmission loss at high frequencies for substrates used in printed circuits or antenna elements. To meet these demands, methods involving the use of low-dielectric constant substrates or the formation of a coating layer of low-dielectric constant material on the substrate surface are being utilized.

[0004] However, these low dielectric constant substrates and coating layers may result in reduced applicability to the surface of the low dielectric constant substrate and reduced room-temperature adhesion between the coating layer and the copper foil. Consequently, there is a tendency for pattern etchability to be compromised and for patterns to detach during the fabrication process of printed circuits or antenna devices.

[0005] Therefore, there is still a demand for copper clad laminates that possess improved transmission loss characteristics at high frequencies after room temperature and moisture absorption, along with coating properties on the surface of a low dielectric constant substrate and excellent room-temperature adhesion between the substrate and the copper foil.

[0006] One aspect is to provide a copper foil laminated film that has low transmission loss at high frequencies at room temperature and after moisture absorption, while simultaneously having improved coating properties on the substrate surface and improved room temperature adhesion between the substrate and the copper foil.

[0007] Another aspect is to provide an article comprising the copper clad laminate film described above.

[0008] Another aspect is to provide a method for manufacturing the copper clad laminated film described above.

[0009] Depending on one aspect,

[0010] Liquid crystal polymer substrate;

[0011] An intermediate layer disposed on at least one surface of the above liquid crystal polymer substrate;

[0012] A tie layer disposed on the above intermediate layer; and

[0013] A copper layer disposed on the above tie layer; comprising

[0014] The above intermediate layer is a cured layer of a composition comprising a low dielectric constant polyimide resin, a silane coupling agent, and inorganic particles, and

[0015] The thickness of the above intermediate layer is greater than the thickness of the above tie layer, and

[0016] A copper clad laminate is provided such that the thickness of the intermediate layer and the thickness of the tie layer satisfy the following Equation 1:

[0017] [Equation 1]

[0018] 100 ≤ A / B < 500

[0019] During the meal,

[0020] A can be the thickness (nm) of the intermediate layer, and

[0021] B can be the thickness of the tie layer (nm).

[0022] According to one embodiment, the liquid crystal polymer substrate has a dielectric constant (D) of 3.3 or less at a frequency of 20 GHz. k ) and dielectric loss of 0.0030 or less (D f It may have ).

[0023] According to one embodiment, the relationship between the weight of a liquid crystal polymer substrate after moisture absorption treatment by leaving it at 85°C and 85% relative humidity for 24 hours and the weight after drying at 120°C for 2 hours may satisfy the following Equation 2:

[0024] [Equation 2]

[0025]

[0026] During the meal,

[0027] w1 may be the weight (g) of the liquid crystal polymer substrate after being left at 85°C and 85% relative humidity for 24 hours and subjected to moisture absorption treatment, and

[0028] w2 may be the weight (g) of the liquid crystal polymer substrate after being left at 85°C and 85% relative humidity for 24 hours and then dried at 120°C for 2 hours.

[0029] According to one embodiment, the low dielectric constant polyimide resin of the intermediate layer may be a resin comprising one or more of bismaleimide, polyesterimide, polyamideimide, polyetherimide, and polyetherimide.

[0030] According to one embodiment, the low dielectric constant polyimide resin may be derived from a long-chain alkyl diamine compound, an aromatic phthalic anhydride, and an epoxy curing agent.

[0031] According to one embodiment, the silane coupling agent of the intermediate layer may include an amino-based silane compound.

[0032] According to one embodiment, the inorganic particles of the intermediate layer may contain a silane compound on their surface.

[0033] According to one embodiment, the content of the epoxy curing agent in the intermediate layer may be 6 to 30 parts by weight based on 100 parts by weight of the low dielectric constant polyimide resin.

[0034] According to one embodiment, the tie layer may be one or more metals or metal alloys selected from copper, tungsten, titanium, tin, chromium, and molybdenum.

[0035] According to one embodiment, the tie layer is a metal alloy containing nickel, and

[0036] The nickel content may be 50 weight% or less based on 100 weight% of the metal alloy.

[0037] According to one embodiment, the copper layer comprises a copper seed layer and a copper plating layer, and

[0038] The copper plating layer above may be an electroplated layer.

[0039] According to one embodiment, the transmission loss value measured by leaving the copper clad laminate film at room temperature (25°C) or at 85°C and 85% relative humidity for more than 24 hours and applying a signal up to 28 GHz frequency may be 3.0 dB / 5cm or less.

[0040] According to one embodiment, the peel strength of the copper layer on the substrate on which the intermediate layer is disposed, measured after leaving the copper clad laminate film at room temperature (25 ℃) for 3 days, may be 0.70 kgf / cm or more.

[0041] According to one embodiment, the peel strength of the copper layer on the substrate on which the intermediate layer is disposed, measured after heat-treating the copper clad laminate film at 150°C at least twice and leaving it for one day, may be 0.80 kgf / cm or more.

[0042] Depending on other aspects of work,

[0043] An article including the aforementioned copper clad laminate film is provided.

[0044] Depending on another aspect of work,

[0045] A step of providing a liquid crystal polymer substrate;

[0046] A step of forming an intermediate layer on at least one surface of the liquid crystal polymer substrate;

[0047] A step of forming a tie layer on the above intermediate layer; and

[0048] The step of forming a copper layer on the above tie layer;

[0049] The above intermediate layer is a cured layer of a composition comprising a low dielectric constant polyimide resin, a silane coupling agent, and inorganic particles, and

[0050] The thickness of the above intermediate layer is greater than the thickness of the above tie layer, and

[0051] A method for manufacturing a copper clad laminate is provided, wherein the thickness of the intermediate layer and the thickness of the tie layer satisfy the following Equation 1:

[0052] [Equation 1]

[0053] 100 ≤ A / B < 500

[0054] During the meal,

[0055] A can be the thickness (nm) of the intermediate layer, and

[0056] B can be the thickness of the tie layer (nm).

[0057] According to one embodiment, the method may further include the step of performing corona surface treatment or plasma surface treatment on one surface of a liquid crystal polymer substrate having an intermediate layer formed on at least one surface.

[0058] According to one aspect, the copper clad laminate film has low transmission loss at room temperature and high frequency after moisture absorption, while simultaneously improving the coating properties of the substrate and having improved room temperature adhesion between the substrate and the copper clad.

[0059] FIG. 1 is a schematic cross-sectional view of a copper clad laminate film according to one embodiment.

[0060] FIG. 2 is a schematic cross-sectional view of a copper clad laminate film according to another embodiment.

[0061] Hereinafter, a copper clad laminate film, an article including the same, and a method for manufacturing the copper clad laminate film will be described in detail with reference to the embodiments and drawings of the present invention. These embodiments are presented merely as examples to explain the present invention more specifically, and it will be obvious to those skilled in the art that the scope of the present invention is not limited by these embodiments.

[0062] Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by those skilled in the art to which the present invention pertains. In the event of a conflict, the present specification, including definitions, shall prevail. Although methods and materials similar or equivalent to those described herein may be used in the practice or testing of the present invention, suitable methods and materials are described herein.

[0063] In this specification, the term "includes" means that, unless specifically stated otherwise, it does not exclude other components but may include additional components.

[0064] In this specification, the term "combination" includes mixtures, alloys, reaction products, etc., unless specifically stated otherwise.

[0065] In this specification, the term “and / or” means any combination of one or more items described in relation and all combinations thereof. In this specification, the term “or” means “and / or”.

[0066] In this specification, expressions such as “at least one,” “one or more,” or “one or more” preceding the components are not intended to supplement the list of all components and are not intended to supplement the individual components described above. For example, “at least one of A, B, and C” and similar phrases (e.g., “at least one selected from the group consisting of A, B, and C” or “one or more selected from A, B, and C”) are interpreted as A alone, B alone, C alone, or a combination of at least two of A, B, and C, such as ABC, AB, BC, and AC.

[0067] In this specification, components referred to as "on," "upper," "above," or "upper" of another component may be located in direct contact with the other component, or there may be components interposed between said components. On the other hand, where one component is described as being placed "directly on" or "directly on" another component, there may be no interposed components.

[0068] In this specification, terms such as "first," "second," etc., are used to distinguish one element from another without indicating order, quantity, or importance. Unless otherwise indicated in this specification or clearly contradicted by the context, they should be interpreted to include both singular and plural forms.

[0069] Throughout this specification, terms such as “one embodiment,” “an embodiment,” etc., mean that specific elements described in relation to an embodiment are included in at least one embodiment described herein and may or may not be present in other embodiments. Additionally, it should be understood that the described elements may be combined in any appropriate manner in various embodiments.

[0070] Exemplary embodiments are described herein with reference to cross-sectional views, which are schematic diagrams of idealized embodiments. Accordingly, the shape of the examples may vary, for example, as a result of manufacturing techniques and / or tolerances. Accordingly, the embodiments described herein should not be interpreted as being limited to the specific shape of the regions described herein and should include variations in shape that occur, for example, during the manufacturing process. For example, regions that are exemplified or described as flat may generally have rough and / or non-linear features. Also, exemplified acute angles may be rounded. Accordingly, regions exemplified in the drawings are by nature schematic, and their shapes are not intended to exemplify the exact shape of the regions or to limit the scope of the claims.

[0071] Unless otherwise stated, all percentages, parts, ratios, etc. are based on weight. Also, if a quantity, concentration, or other value or parameter is given as a range, a preferred range, or a list of preferred upper and lower limits, this should be understood as specifically disclosing any range formed from any pair of any upper limit or preferred value and any lower limit or preferred value, regardless of whether the range is disclosed separately.

[0072] Where a range of numerical values ​​is mentioned in this specification, unless otherwise stated, the range is intended to include its endpoint and all integers and fractions within that range. The scope of the invention is not intended to be limited to the specific values ​​mentioned when defining the range.

[0073] Unless otherwise specified, the unit “parts by weight” refers to the weight ratio between each component, and the unit “parts by mass” refers to the value obtained by converting the weight ratio between each component into solid content.

[0074] The terms “about” or “substantially” as used herein mean within an acceptable range of deviation from a specific value determined by a person skilled in the art, taking into account errors associated with the measurement and the measurement of a specific amount, including the mentioned value (i.e., the limits of the measurement system). For example, “about” or “substantially” may mean within one or more standard deviations, or within ± 30%, 20%, 10%, or 5% of the specified value.

[0075] As used herein, "~-type polymer (resin)" or "~-type copolymer (resin)" is a broad concept that includes all of "~-type polymer (resin)," "~-type copolymer (resin)," or / and "derivatives of ~-type polymer (resin) or copolymer (resin)."

[0076] As used herein, “~-type resin (or compound)” means including “~-type resin (or compound)” and “~--containing derivative resin (or compound)”.

[0077] Among electronic components, antenna elements are typically manufactured by laminating a metal layer, such as copper foil, onto a substrate through which electrical flow by wireless signals takes place.

[0078] Losses occurring in relation to antenna signal reception include losses due to the dielectric constant of the substrate and physical signal losses caused by electrical resistance when wireless signals—i.e., electrical signals—flow through a metal layer. Compared to wireless signals in the relatively low-frequency band, wireless signals in the high-frequency band exhibit a phenomenon where the electrical flow caused by the wireless signal is more concentrated on the surface of the metal layer. Furthermore, in laminated copper foil films, physical stress is generated in the copper foil in the curved regions of the antenna element, causing cracks to form on the surface. As a result, transmission loss may occur. To solve these problems, a method of applying a material that improves dielectric properties to the surface of the substrate is being practiced. However, this method has issues such as reduced coating performance on the substrate surface and decreased adhesion between the substrate and the copper foil.

[0079] Based on these points, the inventors of the present invention propose the following copper clad laminate film.

[0080] FIG. 1 is a schematic cross-sectional view of a copper clad laminate film (10) according to one embodiment. FIG. 2 is a schematic cross-sectional view of a double-sided copper clad laminate film (20) according to another embodiment.

[0081] The copper clad laminate film (10) of FIG. 1 has a substrate (1), an intermediate layer (5), a tie layer (2), and a copper layer (6) composed of a copper seed layer (3) and a copper plating layer (4) arranged in order. Referring to FIG. 2, the copper clad laminate film (20) of FIG. 2 is composed of a first surface (21) in which an intermediate layer (15), a tie layer (12), and a copper layer (16) composed of a copper seed layer (13) and a copper plating layer (14) are arranged in order on the upper surface of the substrate (11), and a second surface (22) in which an intermediate layer (15'), a tie layer (12'), and a copper layer (16') composed of a copper seed layer (13') and a copper plating layer (14') are arranged in order on the lower surface of the substrate (11).

[0082]

[0083] Hereinafter, the copper clad laminate film, the article including the same, and the method for manufacturing the copper clad laminate film will be described in detail.

[0084]

[0085] [Material (11), intermediate layer (5, 15, 15')]

[0086] Generally, when a wireless signal is passed through a circuit, a change occurs in the electric field around the circuit. However, when the change in the electric field approaches the relaxation time of the internal polarization of the resin substrate, a delay occurs in the electric displacement. At this time, molecular friction occurs inside the resin substrate, generating heat, and the generated heat affects the dielectric properties.

[0087] To solve these problems, the substrate (1, 11) according to one embodiment uses a liquid crystal polymer substrate, which is an insulating substrate and has reduced polarity substituents. The liquid crystal polymer substrate has excellent mechanical properties such as heat resistance and rigidity, chemical resistance and dimensional accuracy, and has excellent moldability and can be used in the form of fibers or films. The liquid crystal polymer substrate can be used as a substrate for circuit boards in the field of electronic components and devices where high integration, miniaturization, and thin film formation are required, as it has good fluidity and does not produce burrs.

[0088] Liquid crystal polymer substrates possess low dielectric constant and low moisture absorption characteristics, and exhibit low transmission loss at high frequencies. Even when compared to polyimide substrates or modified polyimide substrates, liquid crystal polymer substrates have a dielectric constant (D) at high frequencies above 20 GHz. k ) and dielectric loss (D f ) is low.

[0089] A substrate (1, 11) according to an exemplary embodiment may have a dielectric constant (Dk) of 3.3 or less and a dielectric loss (Df) of 0.0030 or less at a frequency of 20 GHz. As a result, the transmission loss of the circuit fabricated on the copper clad laminate film (10, 20) at room temperature and after moisture absorption is low.

[0090] According to an exemplary embodiment, the relationship between the weight of the liquid crystal polymer substrate after being left at 85°C and 85% relative humidity for 24 hours and subjected to moisture absorption treatment, and the weight after being dried at 120°C for 2 hours, may satisfy the following Equation 2:

[0091] [Equation 2]

[0092]

[0093] During the meal,

[0094] w1 may be the weight (g) of the liquid crystal polymer substrate after being left at 85°C and 85% relative humidity for 24 hours and subjected to moisture absorption treatment, and

[0095] w2 may be the weight (g) of the liquid crystal polymer substrate after being left at 85°C and 85% relative humidity for 24 hours and then dried at 120°C for 2 hours.

[0096] The substrate (1, 11) may have the form of a film, sheet, or plate. For example, the substrate (1, 11) may be a film. The substrate (1, 11) may use a commercially available molded material or a material formed into a film shape from a resin solution, molten liquid, or dispersion. Additionally, a substrate formed by forming a resin material on a conductive material such as metal may be used.

[0097] The thickness of the substrate (1, 11) may be 5 μm to 100 μm. For example, the thickness of the substrate (1, 11) may be 10 μm to 90 μm, 20 μm to 80 μm, 30 μm to 70 μm, or 35 μm to 60 μm. If the thickness of the substrate (1, 11) is less than 5 μm, productivity may be reduced when manufacturing the copper clad laminate film (10, 20), and if it exceeds 100 μm, thin film formation may not occur.

[0098] However, when a liquid crystal polymer substrate is used as a substrate for a circuit board, the adhesion to the copper layer, which is a metal layer, tends to be low.

[0099] To solve this problem, an intermediate layer (5, 15, 15') may be disposed on at least one surface of a substrate (1, 11) according to one embodiment.

[0100] An intermediate layer (5, 15, 15') according to one embodiment may be a cured layer of a composition comprising a low dielectric constant polyimide resin, a silane coupling agent, and inorganic particles.

[0101] A low dielectric constant polyimide-based resin according to an exemplary embodiment may be a thermoplastic polyimide (TPI).

[0102] For example, a low dielectric constant polyimide resin may include a resin comprising one or more of bismaleimide, polyesterimide, polyamideimide, polyetherimide, and polyetherimide.

[0103] For example, low dielectric constant polyimide resins may be derived from long-chain alkyl diamine compounds, aromatic phthalic anhydrides, and epoxy curing agents. Among low dielectric constant polyimide resins, long-chain alkyl diamine compounds and aromatic phthalic anhydrides can lower the dielectric constant of the molecular structure.

[0104] Among low dielectric constant polyimide resins, epoxy curing agents can enable low-temperature curing and increase the strength of the molecular structure.

[0105] For example, the content of the epoxy curing agent may be 6 to less than 30 parts by weight based on 100 parts by weight of the low dielectric constant polyimide resin.

[0106] For example, the content of the silane coupling agent may be 8 to 28 parts by weight, 10 to 25 parts by weight, or 10 to 15 parts by weight based on 100 parts by weight of the low dielectric constant polyimide resin. If the content of the epoxy curing agent is within the above range, the copper clad laminate film (10, 20) containing it can reduce the occurrence of unreacted epoxy groups, thereby preventing an increase in transmission loss or a decrease in adhesion strength, and can prevent a decrease in the crosslinking strength of the intermediate layer (5, 15, 15'), thereby enabling excellent adhesion strength.

[0107] A silane coupling agent according to an exemplary embodiment may include an amino silane compound.

[0108] For example, amino silane compounds may include compounds represented by the following chemical formula 1:

[0109] <Chemical Formula 1>

[0110] XC m H 2m Si(OC n H 2n )3

[0111] During the meal,

[0112] X is a halogen atom, -SH, -OOC(CH2CH3), -CH=CH2, or -N(R1)(R2), where R1 and R2 are independently a hydrogen atom, a halogen atom, a substituted or unsubstituted 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-C20 cycloalkenyl group, a substituted or unsubstituted C6-C20 aryl group, or a substituted or unsubstituted C6-C20 heteroaryl group.

[0113] n can be an integer from 1 to 5, and

[0114] m can be 0 to 10.

[0115] The definition of the substituent (group) used in the above chemical formula 1 is as follows.

[0116] The "substitution" in "substituted" having the alkyl group, alkenyl group, alkynyl group, cycloalkyl group, cycloalkenyl group, aryl group, or heteroaryl group used in Chemical Formula 1 above refers to a halogen atom, a C1-C10 alkyl group substituted with a halogen atom (e.g., CCF3, CHCF2, CH2F, CCl3, etc.), a hydroxyl group, a nitro group, a cyano group, an amino group, an amidino group, a hydrazine, a hydrazone, a carboxyl group or its salt, a sulfonic acid group or its salt, a phosphoric acid or its salt, or a C1-C10 alkyl group, a C2-C10 alkenyl group, a C2-C10 alkynyl group, a C1-C20 heteroalkyl group, a C6-C20 aryl group, a C6-C20 arylalkyl group, a C6-C20 heteroaryl group, or a C6-C20 It means that it is substituted with a heteroarylalkyl group.

[0117] Specific examples of C1-C10 alkyl groups used in the above chemical formula 1 include methyl, ethyl, propyl, isobutyl, sec-butyl, ter-butyl, neo-butyl, iso-amyl, hexyl, etc., and one or more hydrogen atoms of the above alkyl groups can be substituted with substituents as defined in the "substitution" described above.

[0118] Specific examples of C2-C10 alkenyl groups used in the above chemical formula 1 include vinylene and allylene, and one or more hydrogen atoms of the above alkenyl groups can be substituted with substituents as defined in the "substitution" above.

[0119] Specific examples of C2-C10 alkynyl groups used in the above chemical formula 1 include acetylene, and one or more hydrogen atoms of the above alkynyl groups can be substituted with substituents as defined in the "substitution" above.

[0120] Specific examples of C3-C20 cycloalkyl groups used in the above chemical formula 1 include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, etc., and one or more hydrogen atoms of the cycloalkyl groups can be substituted with substituents as defined in the "substitution" above.

[0121] Specific examples of the C3-C20 cycloalkenyl group used in the above chemical formula 1 include cyclopropenyl, cyclobutenyl, cyclopentenyl, cyclohexenyl, etc., and one or more hydrogen atoms of the above cycloalkenyl group can be substituted with substituents as defined in the "substitution" above.

[0122] The C6-C20 aryl group used in the above chemical formula 1 is used alone or in combination and means an aromatic system containing one or more rings, such as phenyl, naphthyl, etc. In addition, one or more hydrogen atoms of the aryl group can be substituted with a substituent as defined in the "substitution" described above.

[0123] The C6-C20 heteroaryl group used in the above chemical formula 1 refers to an organic compound comprising one or more heteroatoms selected from N, O, P, or S, and having the remaining ring atom as carbon, such as pyridyl. Additionally, one or more hydrogen atoms of the above heteroaryl group may be substituted with substituents as defined in the "substitution" described above.

[0124] A silane coupling agent according to an exemplary embodiment may be a layer derived from an amino-based silane compound alone or from a mixture of two or more, or a layer derived from a composition mixed with an amino-based silane compound or a silane compound having other functional groups, such as vinyl groups.

[0125] According to an exemplary embodiment, the content of the silane coupling agent may be 10 parts by weight or less based on 100 parts by weight of the low dielectric constant polyimide resin. For example, the content of the silane coupling agent may be 0.1 to 10 parts by weight, 0.1 to 9 parts by weight, 0.1 to 8 parts by weight, 0.1 to 7 parts by weight, 0.1 to 6 parts by weight, or 0.1 to 5 parts by weight based on 100 parts by weight of the low dielectric constant polyimide resin. If the content of the silane coupling agent is within the above range, the adhesion of the circuit made of the copper clad laminate film (10, 20) containing it can be maintained, and the room temperature and high temperature adhesion between the substrate (1, 11) and the copper layer (6, 16, 16') can be improved.

[0126] Inorganic particles according to an exemplary embodiment may comprise one or more inorganic particles selected from silica (SiO2), alumina (Al2O3), boehmite (γ-AlO(OH)), barium titanium oxide, titanium oxide, magnesium oxide, boron nitride, calcium carbonate, calcium phosphate, and aluminum nitride. For example, the inorganic particles may comprise a silane compound on their surface.

[0127] According to an exemplary embodiment, the average particle size of the inorganic particles may be 5 nm to less than 3000 nm. For example, the average particle size of the inorganic particles may be 5 nm to 2000 nm or 10 nm to 1000 nm. In this specification, the average particle size refers to D50. D50 refers to the particle size at which the cumulative fraction from the smallest particle in the measured particle size distribution reaches 50% when the particle size distribution is measured using a particle size analysis device based on light scattering. D50 may be measured by laser diffraction, SEM, or TEM image analysis, etc., in addition to light scattering.

[0128] If the average particle size of the inorganic particles is less than 5 nm, the surface roughness of the intermediate layer is low, which may result in low adhesion with the tie layer. If the average particle size of the inorganic particles is 3000 nm or more, thickness non-uniformity or transmission loss caused by the inorganic particles may increase.

[0129] According to an exemplary embodiment, the content of inorganic particles may be 20 to 60 parts by weight, 25 to 55 parts by weight, or 30 to 50 parts by weight based on 100 parts by weight of a low dielectric constant polyimide resin. If the content of inorganic particles is within the above range, the copper clad laminate film (10, 20) containing the same can maintain excellent adhesion between the substrate (1, 11) and the tie layer (2, 12, 12'), prevent an increase in moisture absorption, and maintain the coefficient of thermal expansion (CTE) of the substrate (1, 11) on which the intermediate layer (5, 15, 15') is disposed within an appropriate range.

[0130] According to an exemplary embodiment, the coefficient of thermal expansion (CTE) of the substrate (1, 11) having an intermediate layer (5, 15, 15') may be 50 ppm / ℃ or less. For example, the coefficient of thermal expansion (CTE) of the substrate (1, 11) having an intermediate layer (5, 15, 15') may be 0.01 ppm / ℃ to 50 ppm / ℃. When manufacturing a copper clad laminate film (10, 20), the difference between the CTE (16~20 ppm) of the copper layer (6, 16, 16') and the coefficient of thermal expansion (CTE) of the substrate (1, 11) is not large, so the amount of residual stress generated is small, preventing bending and preventing warping or bending problems caused by shrinkage.

[0131] The thickness of the intermediate layer (5, 15, 15') may be 50% or less based on the total thickness of the substrate ((1, 11)). The thickness of the intermediate layer (5, 15, 15') may be 0.5 μm to 3 μm. If the thickness of the adhesion-enhancing layer (5, 15, 15') is within the above range, the room temperature and high temperature adhesion between the substrate (1, 11) and the copper layer (6, 16, 16') may be further improved.

[0132] The thickness of the intermediate layer (5, 15, 15') may be greater than the thickness of the tie layer (2, 12, 12') described later.

[0133] In addition, before placing the tie layer (2, 12, 12') described later, surface treatment can be performed on the substrate (1, 11) on which the intermediate layer (5, 15, 15') is placed. As a result, functional groups such as -OH, -CHO, and -COOH are created on the surface of the intermediate layer (5, 15, 15'), thereby providing a copper clad laminate film (10, 20) with excellent adhesion to the substrate (1, 11) and the copper seed layer (3, 13, 13') and copper plating layer (4, 14, 14') described later at room temperature and high temperature.

[0134]

[0135] [Taichung(2, 12, 12')]

[0136] According to one embodiment, a copper clad laminate film may have a tie layer (2, 12, 12') disposed on a substrate (1, 11) on which an intermediate layer (5, 15, 15') is disposed.

[0137] According to an exemplary embodiment, the tie layer (2, 12, 12') may be one or more metals or metal alloys selected from copper, tungsten, titanium, tin, chromium, and molybdenum. The tie layer (2, 12, 12') has a relatively stable bond with oxygen (O2) and may have a low transmission loss compared to a Ni-only metal tie layer that exhibits ferromagnetic properties. Thus, the electrical conductivity of the surface of the tie layer (2, 12, 12') may be improved.

[0138] According to an exemplary embodiment, the tie layer (2, 12, 12') may be a metal alloy containing nickel. The nickel content may be 50 weight% or less based on 100 weight% of the metal alloy. If the nickel content is within the above range, the tie layer (2, 12, 12') not only improves the room temperature and high temperature adhesion between the substrate (1, 11) and the copper layer (6, 16, 16'), but also the circuit made of the copper clad laminate film (10, 20) containing such tie layer (2, 12, 12') has very low transmission loss at room temperature.

[0139] The thickness of the tie layer (2, 12, 12') may be 10 nm to 100 nm. For example, the thickness of the tie layer (2, 12, 12') may be 12 nm to 50 nm or 12 nm to 40 nm. If the thickness of the tie layer (2, 12, 12') is less than 10 nm, the thickness of the tie layer (2, 12, 12') is thin, so it may be difficult to form a sufficient metal oxide or alloy oxide at the interface with the substrate (1, 11), making it difficult to secure room temperature and high temperature adhesion. If the thickness of the tie layer (2, 12, 12') is greater than 100 nm, the tie layer (2, 12, 12') may not be properly etched during the etching process for forming the circuit, resulting in residue that may cause circuit defects and may also reduce room temperature adhesion.

[0140] The thickness of the aforementioned intermediate layer (5, 15, 15') and the thickness of the tie layer (2, 12, 12') may satisfy the following Equation 1:

[0141] [Equation 1]

[0142] 100 ≤ A / B < 500

[0143] During the meal,

[0144] A can be the thickness (nm) of the intermediate layer, and

[0145] B can be the thickness of the tie layer (nm).

[0146] If the thickness (A) of the intermediate layer (5, 15, 15') / the thickness (B) of the tie layer (2, 12, 12') is less than 100, the room temperature adhesive strength is reduced, and if the thickness (A) of the intermediate layer (5, 15, 15') / the thickness (B) of the tie layer (2, 12, 12') is 500 or more, the moisture absorption rate of the substrate (1, 11) may be increased.

[0147] Accordingly, when the thickness (A) of the intermediate layer (5, 15, 15') / the thickness (B) of the tie layer (2, 12, 12') satisfies Equation 1, a copper foil laminated film can be provided that has improved coating properties on the surface of the substrate (1, 11) and improved room temperature adhesion between the substrate (1, 11) and the copper foil.

[0148] [Copper seed layer (3, 13, 13'), copper plating layer (4, 14, 14'), copper layer (6, 16, 16')]

[0149] In one embodiment, a copper clad laminate film may have a copper layer (6, 16, 16') composed of a copper seed layer (3, 13, 13') and a copper plating layer (4, 14, 14') disposed on a tie layer (2, 12, 12').

[0150] The copper seed layer (3, 13, 13') may be a sputtered layer. The copper seed layer (3, 13, 13') can have low transmission loss while maintaining the surface roughness of the substrate (1, 11) itself on which the intermediate layer (5, 15, 15') is disposed. For sputtering, methods such as physical vapor deposition (PVD), chemical vapor deposition (CVD), low-pressure chemical vapor deposition (LPCVD), or vacuum deposition may be used, but are not limited thereto, and any sputtering method that can be used for said sputtering may be used. For example, physical vapor deposition (PVD) may be used for sputtering.

[0151] The thickness of the copper seed layer (3, 13, 13') may be 800 Å to 4000 Å. For example, the thickness of the copper seed layer (3, 13, 13') may be 850 Å to 3500 Å, 900 Å to 3000 Å, 950 Å to 2500 Å, 1000 Å to 2000 Å, or 1000 Å to 1500 Å. If the copper seed layer (3, 13, 13') has the above thickness range, conductivity can be secured during film formation and low surface roughness (R zA copper clad laminate film (10, 20) having low transmission loss can be provided.

[0152] A copper plating layer (4, 14, 14') is disposed on a copper seed layer (3, 13, 13'). The copper plating layer (4, 14, 14') can be formed using an electroless plating method or an electrolytic plating method. For example, the copper plating layer (4, 14, 14') can be formed using an electrolytic plating method.

[0153] The copper electroplating layer can be formed using any method available in the relevant technical field. For example, a copper electroplating layer can be formed on one side of a copper seed layer (3, 13, 13') by performing electroplating with an electroplating solution having copper sulfate and sulfuric acid as base materials. Additionally, additives such as brighteners, levelers, correctors, or relaxants may be added to the electroplating solution to improve productivity and surface uniformity.

[0154] The thickness of the copper plating layer (4, 14, 14') may be 12 μm or less. For example, the thickness of the copper plating layer (4, 14, 14') may be 0.1 μm to 12 μm, 1.0 μm to 12 μm, 2 μm to 12 μm, 4 μm to 12 μm, or 6.0 μm to 12 μm.

[0155]

[0156] [Copper clad laminate film (10, 20)]

[0157] According to one embodiment, the copper clad laminate film (10, 20) can be left at room temperature (25°C) or at 85°C and 85% relative humidity for 24 hours or more, and the transmission loss value measured by applying a signal up to 28 GHz frequency can be 3.0 dB / 5cm or less.

[0158] The peel strength of the copper layer (6, 16, 16') on the substrate (1, 11) on which the intermediate layer is disposed, measured after leaving the copper clad laminate film (10, 20) according to one embodiment at room temperature (25 ℃) for 3 days, may be 0.70 kgf / cm or more, for example 0.80 kgf / cm or more.

[0159] The peel strength of the copper layer on the substrate (1, 11) on which the intermediate layer is disposed, measured after heat-treating the copper clad laminate film (10, 20) according to one embodiment at least twice at 150°C and leaving it for one day, may be 0.80 kgf / cm or more.

[0160]

[0161] [article]

[0162] A component according to another embodiment may include the copper clad laminate film (10, 20) described above. A component according to an exemplary embodiment may include an antenna element and a circuit board.

[0163] A device according to another embodiment may include a copper clad laminate film (10, 20). A device according to an exemplary embodiment may include a network server, an Internet of Things (IOT) for 5G, radar, a USB, and a home appliance.

[0164]

[0165] [Method for manufacturing copper clad laminate film (10, 20)]

[0166] A method for manufacturing a copper clad laminate according to another embodiment comprises the steps of: providing a liquid crystal polymer substrate (1, 11); forming an intermediate layer (5, 15, 15') on at least one surface of the liquid crystal polymer substrate (1, 11); and forming a tie layer (2, 12, 12') on the intermediate layer (5, 15, 15'). and forming a copper layer (6, 16, 16') on the tie layer (2, 12, 12'); wherein the intermediate layer (5, 15, 15') is a cured layer of a composition comprising a low dielectric constant polyimide resin, a silane coupling agent, and inorganic particles, and the thickness of the intermediate layer (5, 15, 15') is greater than the thickness of the tie layer (2, 12, 12'), and the thickness of the intermediate layer (5, 15, 15') and the thickness of the tie layer (2, 12, 12') may satisfy the following Formula 1:

[0167] [Equation 1]

[0168] 100 ≤ A / B < 500

[0169] During the meal,

[0170] A can be the thickness (nm) of the intermediate layer, and

[0171] B can be the thickness of the tie layer (nm).

[0172] A copper clad laminate manufactured by the method for manufacturing a copper clad laminate according to one embodiment may have low transmission loss at room temperature and high frequency after moisture absorption, while simultaneously improving the coating properties of the substrate (1, 11) and having improved room temperature adhesion between the substrate (1, 11) and the copper clad.

[0173] A method for manufacturing a copper clad laminate according to an exemplary embodiment may further include the step of performing corona surface treatment or plasma surface treatment on one surface of a liquid crystal polymer substrate (1, 11) having an intermediate layer formed on at least one surface.

[0174] Surface treatment can utilize RF plasma or an ion beam. For example, surface treatment may use a reaction gas comprising one or more selected from nitrogen (N2), oxygen (O2), argon (Ar), xenon (Xe), and helium (He). Examples of reaction gases may include oxygen (O2) alone, or a mixed gas of argon-oxygen (Ar-O2) or argon-nitrogen (Ar-N2). In this case, the adhesion between the substrate (1, 11) and the copper layer (6, 16, 16') described later can be significantly improved at room temperature and high temperature.

[0175] For example, when argon (Ar) is mixed and used as a reaction gas, argon (Ar) may be included in an amount of 0.1 volume% to 50 volume% based on the total volume of the reaction gas, or in an amount of 0.1 volume% to 30 volume%, or in an amount of 0.1 volume% to 25 volume%. If argon (Ar) is mixed and used within the above volume range, the adhesion between the substrate (1, 11) and the copper layer (6, 16, 16') described later can be greatly improved at room temperature and high temperature.

[0176] The irradiation time of the RF plasma or ion beam is not limited and can be appropriately adjusted according to the purpose.

[0177] The surface treatment method can be performed through a roll-to-roll process. For example, in the roll-to-roll process, RF plasma or an ion beam can be irradiated for 1 to 50 seconds in the MD (Machine Direction) direction onto the surface of an intermediate layer (5, 15, 15') that is supplied continuously at 2 to 10 mpm (meters per minute). Within this range, improved room temperature adhesion and high temperature adhesion can be efficiently achieved between the substrate (1, 11) of the copper clad laminate (10, 20) and the copper layer (6, 16, 16').

[0178] The power for applying the RF plasma or ion beam may be 0.1 kW to 10 kW, 0.1 kW to 5 kW, or 0.5 kW to 3 kW. Within this range, the adhesion between the substrate (1, 11) on which the intermediate layer (5, 15, 15') is disposed and the copper layer (6, 16, 16') can be significantly improved at room temperature and high temperature.

[0179]

[0180] Hereinafter, the structure of the present invention and the resulting effects are to be explained in more detail through examples and comparative examples. However, it will be obvious that these examples are intended to explain the present invention more specifically and that the scope of the present invention is not limited to these examples.

[0181]

[0182] [Example]

[0183]

[0184] Example 1: Copper clad laminate film

[0185] A copper clad laminate film (200) having the structure of Fig. 2 was manufactured as follows.

[0186] First, a liquid crystal polymer film with a thickness of about 50 μm (11, manufactured by Bready) was prepared as a substrate.

[0187] Separately, a low dielectric constant polyimide resin was prepared by synthesizing 2,2-bis[4-(3,4-dicarboxyphenoxy)phenyl]propane dianhydride (BPADA) (manufactured by Sigma Aldrich) as an aromatic phthalic anhydride and dimer diamine (manufactured by Cargill Industrial Specialties) as a long-chain alkyl diamine compound. A composition for forming an intermediate layer was prepared by adding and stirring 10 parts by weight of epoxy resin (YD128, manufactured by Kookdo Chemical) as an epoxy curing agent, 35 parts by weight of silica particles surface-treated with a silane compound (average particle size: 50 nm, manufactured by LX, Luxon) as inorganic particles, and 3 parts by weight of aminopropyltriethoxysilane (OFS-6011, manufactured by Dow Chemical) as a silane coupling agent in an N-methyl-2-pyrrolidone solvent, based on 100 parts by weight of low dielectric constant polyimide resin.

[0188] An intermediate layer forming composition was applied to the first surface (21) of a liquid crystal polymer film (11) using a bar coater and dried at 180°C for 5 minutes to form an intermediate layer (15) with a thickness of about 1 μm.

[0189] Surface treatment was performed on the upper surface of the intermediate layer (15) using RF plasma in a roll-to-roll type sputtering device. On the upper surface of the surface-treated intermediate layer (15), a tie layer (12) with a thickness of about 20 nm was formed by physical vapor deposition (PVD) with a weight ratio of copper (Cu) and nickel (Ni) of 65:35 (purity: 99.9% or higher).

[0190] A copper seed layer (13) with a thickness of about 100 nm was formed on the upper surface of the tie layer (12) using copper with a purity of 99.995% by physical vapor deposition (PVD).

[0191] In addition, an intermediate layer (15') was formed on the second surface (22) of the liquid crystal polymer film (11) in the same manner as described above, and RF plasma surface treatment was performed on the lower surface of the intermediate layer (15'). A tie layer (12') and a copper seed layer (13') were formed on the lower surface of the surface-treated intermediate layer (15'), respectively.

[0192] Subsequently, a copper plating layer (14, 14') with a thickness of about 12 μm was formed on the upper and lower surfaces of the copper seed layer (13, 13') respectively using an electrolytic copper plating method to manufacture a double-sided copper clad laminate film (20).

[0193] The electrolytic copper plating solution used for electrolytic copper plating is Cu 2+ The solution was prepared with a concentration of 28 g / L and 195 g / L of sulfuric acid; to this solution, 0.01 g / L of 3-N,N-dimethylaminodithiocarbamoyl-1-propanesulfonic acid and a corrector (Atotech product) were added as a brightener. Electrolytic copper plating was performed at 34 ℃ with a current density of 1.0 A / dm². 2 Starting from and gradually increasing to 2.86 A / dm 2 The current was applied in stages up to.

[0194]

[0195] Example 2: Copper clad laminate film

[0196] A double-sided copper clad laminate film (20) was prepared in the same manner as in Example 1, except that, based on 100 parts by weight of a low dielectric constant polyimide resin, 15 parts by weight of an epoxy resin (YD128, manufactured by Kukdo Chemical) as an epoxy curing agent, 50 parts by weight of silica particles surface-treated with a silane compound (average particle size: 50 nm, manufactured by LX, Luxon) as inorganic particles, and 3 parts by weight of aminopropyltriethoxysilane (OFS-6011, manufactured by Dow Chemical) as a silane coupling agent were added to and stirred in an N-methyl-2-pyrrolidone solvent to prepare a composition for forming an intermediate layer, and the composition for forming an intermediate layer was applied to the first surface (21) and the second surface (22) of a liquid crystal polymer film (11) using a bar coater and dried at 180°C for 5 minutes to form an intermediate layer (15, 15') with a thickness of about 3 μm.

[0197]

[0198] Example 3: Copper clad laminate film

[0199] Based on 100 parts by weight of low dielectric constant polyimide resin, a composition for forming an intermediate layer is prepared by adding and stirring 15 parts by weight of epoxy resin (YD128, manufactured by Kukdo Chemical) as an epoxy curing agent, 50 parts by weight of silica particles surface-treated with a silane compound (average particle size: 50 nm, manufactured by LX, Luxon) as inorganic particles, and 3 parts by weight of aminopropyltriethoxysilane (OFS-6011, manufactured by Dow Chemical) as a silane coupling agent in an N-methyl-2-pyrrolidone solvent; the composition for forming an intermediate layer is applied to the first surface (21) and the second surface (22) of a liquid crystal polymer film (11) substrate using a bar coater and dried at 180°C for 5 minutes to form an intermediate layer (15, 15') with a thickness of about 3 μm, and on the upper and lower surfaces of the surface-treated intermediate layer (15, 15') A double-sided copper clad laminate film (20) was manufactured in the same manner as in Example 1, except that a tie layer (12, 12') with a thickness of about 30 nm was formed by physical vapor deposition (PVD) with a weight ratio of copper (Cu) and nickel (Ni) of 65:35 (purity: 99.9% or higher).

[0200]

[0201] Comparative Example 1: Copper clad laminate film

[0202] A polyimide resin is prepared by synthesizing pyromellitic acid dianhydride (PMDA, manufactured by Daken Chemical) as an anhydride and oxydianiline (ODA, manufactured by Sigma Aldrich) as a diamine compound; a composition for forming an intermediate layer is prepared by adding and stirring 35 parts by weight of silica particles (average particle size: 3 μm, FB grade, manufactured by Denka) as inorganic particles into an N-methyl-2-pyrrolidone solvent based on 100 parts by weight of the polyimide resin; the composition for forming an intermediate layer is applied to the first surface (21) and second surface (22) of a liquid crystal polymer film (11) substrate using a bar coater and dried at 180°C for 5 minutes to form an intermediate layer (15, 15') with a thickness of about 5 μm; and on the upper and lower surfaces of the surface-treated intermediate layer (15, 15'), a weight ratio of copper (Cu) and nickel (Ni) of 65: A double-sided copper clad laminate film (20) was manufactured in the same manner as in Example 1, except that a tie layer (12, 12') with a thickness of about 10 nm was formed with 35 (purity: 99.9% or higher).

[0203]

[0204] Comparative Example 2: Copper clad laminate film

[0205] A polyimide resin is prepared by synthesizing biphenyltetracarboxylic acid dianhydride (BPDA, manufactured by Sigma Aldrich) as an anhydride and ρ-phenylenediamine (ρ-PDA, manufactured by Sigma Aldrich) as a diamine compound; a composition for forming an intermediate layer is prepared by adding and stirring 3 parts by weight of 3-glycidoxypropyltrimethoxysilane (KBM-403, manufactured by Shin-Etsu) as a silane coupling agent into an N-methyl-2-pyrrolidone solvent based on 100 parts by weight of the polyimide resin; the composition for forming an intermediate layer is applied to the first surface (21) and second surface (22) of a liquid crystal polymer film (11) substrate using a bar coater and dried at 180°C for 5 minutes to form an intermediate layer (15, 15') with a thickness of about 1 μm; and on the upper and lower surfaces of the surface-treated intermediate layer (15, 15') by physical vapor deposition (PVD) A double-sided copper clad laminate film (20) was manufactured in the same manner as in Example 1, except that a tie layer (12, 12') with a thickness of about 30 nm was formed with a weight ratio of copper (Cu) and nickel (Ni) of 65:35 (purity: 99.9% or higher).

[0206]

[0207] Comparative Example 3: Copper clad laminate film

[0208] Based on 100 parts by weight of low dielectric constant polyimide resin, a composition for forming an intermediate layer is prepared by adding and stirring 5 parts by weight of epoxy resin (YD128, manufactured by Kukdo Chemical) as an epoxy curing agent and 35 parts by weight of silica particles (average particle size: 3 μm, FB grade, manufactured by Denka) as inorganic particles into an N-methyl-2-pyrrolidone solvent. The composition for forming an intermediate layer is applied to the first surface (21) and the second surface (22) of a liquid crystal polymer film (11) substrate using a bar coater and dried at 180°C for 5 minutes to form an intermediate layer (15, 15') with a thickness of about 0.1 μm. A tie layer (12, approximately 20 nm thick) is formed on the upper and lower surfaces of the surface-treated intermediate layer (15, 15') by physical vapor deposition (PVD) with a weight ratio of copper (Cu) and nickel (Ni) of 65:35 (purity: 99.9% or higher). A double-sided copper clad laminate film (20) was manufactured in the same manner as in Example 1, except that the 12') was formed.

[0209]

[0210] Comparative Example 4: Copper clad laminate film

[0211] Based on 100 parts by weight of low dielectric constant polyimide resin, a composition for forming an intermediate layer is prepared by adding and stirring 25 parts by weight of epoxy resin (YD128, manufactured by Kukdo Chemical) as an epoxy curing agent and 3 parts by weight of vinyltrimethoxysilane (KBM-503, manufactured by Shin-Etsu) as a silane coupling agent into an N-methyl-2-pyrrolidone solvent, and the composition for forming an intermediate layer is applied to the first surface (21) and the second surface (22) of a liquid crystal polymer film (11) substrate using a bar coater and dried at 180°C for 5 minutes to form an intermediate layer (15, 15') with a thickness of about 1 μm, and a tie layer (12, with a thickness of about 20 nm) is formed on the upper and lower surfaces of the surface-treated intermediate layer (15, 15') by physical vapor deposition (PVD) with a weight ratio of copper (Cu) and nickel (Ni) of 65:35 (purity: 99.9% or higher). A double-sided copper clad laminate film (20) was manufactured in the same manner as in Example 1, except that the 12') was formed.

[0212]

[0213] Comparative Example 5: Copper clad laminate film

[0214] A modified polyimide film (11, manufactured by Kaneka) with a thickness of about 50 μm is prepared as a substrate, a polyimide resin is prepared by synthesizing biphenyltetracarboxylic acid dianhydride (BPDA, manufactured by Sigma Aldrich) as an anhydride and ρ-phenylenediamine (ρ-PDA, manufactured by Sigma Aldrich) as a diamine compound, and a composition for forming an intermediate layer is prepared by adding and stirring 35 parts by weight of silica particles (average particle size: 3 μm, FB grade, manufactured by Denka) as inorganic particles into an N-methyl-2-pyrrolidone solvent based on 100 parts by weight of the polyimide resin, and the composition for forming an intermediate layer is applied to the first surface (21) and second surface (22) of the modified polyimide film (11) substrate using a bar coater and dried at 180°C for 5 minutes to form an intermediate layer (15, 15') with a thickness of about 1 μm, and the surface-treated intermediate layer (15, A double-sided copper clad laminate film (20) was manufactured in the same manner as in Example 1, except that a tie layer (12, 12') with a thickness of about 20 nm was formed on the upper and lower surfaces of the film by physical vapor deposition (PVD) with a weight ratio of copper (Cu) and nickel (Ni) of 35:65 (purity: 99.9% or higher).

[0215]

[0216] Evaluation Example 1: Physical Property Evaluation

[0217] The physical properties of each copper clad laminate film prepared according to Examples 1 to 3 and Comparative Examples 1 to 5 were evaluated as follows. The results are shown in Table 1 below.

[0218]

[0219] (1) Permittivity (D k ) and dielectric loss (D f ) (@ 20 GHz)

[0220] The substrate film of each copper clad laminate was prepared as a 4cm x 4cm sample, and the dielectric constant (D) was determined using a network analyzer (manufactured by Anritsu) and a 20 GHz cavity resonator (manufactured by AET). k ) and dielectric loss (D f ) was measured.

[0221]

[0222] (2) Moisture absorption rate (%)

[0223] Each copper clad laminate substrate film was prepared as a sample of 10 cm x 10 cm and left at 85°C and 85% relative humidity for 24 hours. The weight (W1) after moisture absorption treatment and the weight (W2) after drying at 120°C for 2 hours were measured, respectively. Each measured value was substituted into Equation 2-1 below to calculate the weight change rate, which was defined as the moisture absorption rate.

[0224] [Equation 2-1]

[0225] Moisture absorption rate (%) =

[0226] During the meal,

[0227] w1 is the weight of the above-mentioned substrate film after being left at 85°C and 85% relative humidity for 24 hours and subjected to moisture absorption treatment, and

[0228] w2 is the weight of the above-mentioned substrate film after being left at 85°C and 85% relative humidity for 24 hours and then dried at 120°C for 2 hours.

[0229]

[0230] (3) Intermediate layer thickness (A, μm), Tie layer thickness (B, nm)

[0231] The intermediate layer thickness and tie layer thickness of each copper clad laminate were measured using a Focused Ion Beam (FIB)-TEM instrument. The measured intermediate layer thickness (A) was divided by the tie layer thickness (B) to calculate A / B.

[0232]

[0233] (4) Transmission loss at room temperature (dB / 5cm @ 28 GHz)

[0234] For each copper clad laminate, five linear circuits were formed by etching with a width of 100 μm, a length of 50 mm, and a longitudinal spacing of 40 mm. After leaving each sample at room temperature (25°C) for more than 24 hours, each signal conductor and ground conductor of the transmission path in which the linear circuits were formed were connected to the measurement port of a Vector Network Analyzer, and a signal up to a frequency of 28 GHz was applied to measure the transmission loss. At this time, the transmission loss was evaluated as follows.

[0235] ○: When transmission loss is greater than -0.5 dB / 5cm or 0 dB / 5cm

[0236] △: When transmission loss is -0.5 dB / 5cm to -1.0 dB / 5cm

[0237] X: When transmission loss is less than -1.0 dB / 5cm

[0238]

[0239] (5) Transmission loss after moisture absorption (dB / 5cm @ 28 GHz)

[0240] For each copper clad laminate, five linear circuits were formed by etching with a width of 100 μm, a length of 50 mm, and a longitudinal spacing of 40 mm. After leaving each sample at 85°C and 80% relative humidity for more than 24 hours, each signal conductor and ground conductor of the transmission path formed with the linear circuits were connected to the measurement port of a Vector Network Analyzer, respectively, and a signal up to 28 GHz was applied to measure the transmission loss. At this time, the transmission loss was evaluated as follows.

[0241] ○: When transmission loss is greater than -0.5 dB / 5cm or 0 dB / 5cm

[0242] △: When transmission loss is -0.5 dB / 5cm to -1.0 dB / 5cm

[0243] X: When transmission loss is less than -1.0 dB / 5cm

[0244]

[0245] (6) Room temperature adhesion (kgf / cm)

[0246] For each copper clad laminate, a sample with a circuit pattern of 3 mm width was prepared. For each sample, the peel strength (kgf / cm) of the copper layer on the substrate film with the intermediate layer was measured by peeling at a tensile speed of 50 mm / min and an angle of 180° using a peel strength tester (manufactured by TA.XT.plus, Texture Analyser) at room temperature (25 ℃).

[0247]

[0248]

[0249] LCP is a liquid crystal polymer film

[0250] MPI is a modified polyimide film

[0251] The epoxy curing agent content is based on 100 parts by weight of low dielectric constant polyimide resin.

[0252]

[0253] Referring to Table 1, the dielectric constant (D) of the substrate of the copper clad laminate film prepared according to Examples 1 to 3 k ) is 3.3 or less and dielectric loss (D f ) was 0.0027 or less. The copper clad laminate films prepared according to Examples 1 to 3 had a dielectric constant (D) with respect to the substrate of the copper clad laminate films prepared according to Comparative Examples 1, 2, and 5. k ) and / or dielectric loss (D f It was lower than ).

[0254] The transmission loss of the circuit made with the copper clad laminate film prepared according to Examples 1 to 3 was greater than -0.50 dB / 5cm at room temperature and after moisture absorption, whereas the transmission loss of the circuit made with the copper clad laminate film prepared according to Comparative Examples 1, 2, and 5 was greater than -1.0 dB / 5cm after moisture absorption due to the polyimide substrate. This is attributed to the moisture absorption of the polyimide substrate.

[0255] The room temperature adhesion strength of the copper clad laminates prepared according to Examples 1 to 3 was 0.81 kgf / cm or higher. In comparison, the copper clad laminates prepared according to Comparative Examples 1 and 5, which did not add a silane coupling agent, and the copper clad laminates prepared according to Comparative Examples 2 and 4, which added a silane coupling agent having epoxy and vinyl groups, all had low room temperature adhesion strength. The copper clad laminates prepared according to Comparative Examples 2 and 4, which did not contain inorganic particles, had low room temperature adhesion strength because the adhesion strength between the tie layer and the intermediate layer was low. The copper clad laminate prepared according to Comparative Example 1, in which the thickness (A) of the intermediate layer was 5 μm and A / B was 500, had the highest moisture absorption rate of the substrate, and the copper clad laminate prepared according to Comparative Example 3, in which the thickness (A) of the intermediate layer was 0.1 μm and A / B was 5, had the lowest room temperature adhesion strength. The copper clad laminate film prepared according to Comparative Example 5, where A / B is 50, has a dielectric constant (D) of the substrate k ), dielectric loss (D f ) and moisture absorption rate were the highest.

[0256] [Explanation of the symbol]

[0257] 1, 11: Base layer, 2, 12, 12': Tie layer, 3, 13, 13': Copper seed layer,

[0258] 4, 14, 14': Copper plating layer, 5, 15, 15': Intermediate layer,

[0259] 6, 16, 16': copper layer,

[0260] 10, 20: Copper clad laminate film, 21: First surface, 22: Second surface

Claims

Liquid crystal polymer substrate; An intermediate layer disposed on at least one surface of the above liquid crystal polymer substrate; A tie layer disposed on the above intermediate layer; and A copper layer disposed on the above tie layer; comprising The above intermediate layer is a cured layer of a composition comprising a low dielectric constant polyimide resin, a silane coupling agent, and inorganic particles, and The thickness of the above intermediate layer is greater than the thickness of the above tie layer, and A copper clad laminate film in which the thickness of the intermediate layer and the thickness of the tie layer satisfy the following Equation 1: [Equation 1] 100 ≤ A / B < 500 During the meal, A is the thickness of the intermediate layer (nm), and B is the thickness of the tie layer (nm). In paragraph 1, The above liquid crystal polymer substrate has a dielectric constant (D) of 3.3 or less at a frequency of 20 GHz. k ) and dielectric loss of 0.0030 or less (D f A copper clad laminate film having ). In paragraph 1, A copper clad laminate, wherein the relationship between the weight after moisture absorption treatment by leaving the above liquid crystal polymer substrate at 85°C and 85% relative humidity for 24 hours and the weight after drying at 120°C for 2 hours satisfies the following Equation 2: [Equation 2] During the meal, w1 is the weight (g) of the liquid crystal polymer substrate after being left at 85°C and 85% relative humidity for 24 hours and subjected to moisture absorption treatment, and w2 is the weight (g) of the liquid crystal polymer substrate after being left at 85°C and 85% relative humidity for 24 hours and then dried at 120°C for 2 hours. In paragraph 1, A copper clad laminate film wherein the low dielectric constant polyimide resin of the above intermediate layer comprises one or more of bismaleimide, polyesterimide, polyamideimide, polyetherimide, and polyetherimide. In paragraph 1, A copper clad laminate film in which the low dielectric constant polyimide resin of the above intermediate layer is derived from a long-chain alkyl diamine compound, an aromatic phthalic anhydride, and an epoxy curing agent. In paragraph 1, A copper clad laminate film wherein the silane coupling agent of the intermediate layer comprises an amino-based silane compound. In paragraph 1, A copper clad laminate film in which the inorganic particles of the above intermediate layer contain a silane compound on their surface. In paragraph 1, A copper clad laminate film in which the above intermediate layer has a content of epoxy curing agent of 6 to less than 30 parts by weight based on 100 parts by weight of the low dielectric constant polyimide-based resin. In paragraph 1, A copper clad laminate film in which the above tie layer is one or more metals or metal alloys selected from copper, tungsten, titanium, tin, chromium, and molybdenum. In Paragraph 9, The above tie layer is a metal alloy containing nickel, and A copper clad laminate film having a nickel content of 50 weight% or less based on 100 weight% of the metal alloy. In paragraph 1, The above copper layer includes a copper seed layer and a copper plating layer, and A copper clad laminate film in which the copper plating layer is an electroplated layer. In paragraph 1, A copper clad laminate film having a transmission loss value of 3.0 dB / 5cm or less, measured by leaving the copper clad laminate film at room temperature (25℃) or at 85℃ and 85% relative humidity for 24 hours or more and applying a signal up to 28 GHz. In paragraph 1, A copper clad laminate film having a peel strength of the copper layer on a substrate having the intermediate layer, measured after leaving the copper clad laminate film at room temperature (25 ℃) for 3 days, of 0.70 kgf / cm or more. In paragraph 1, A copper clad laminate film having a peel strength of the copper layer on a substrate having the intermediate layer, measured after heat-treating the copper clad laminate film at 150°C at least twice and leaving it for one day, of 0.80 kgf / cm or more. An article comprising a copper clad laminate film according to any one of claims 1 to 14. A step of providing a liquid crystal polymer substrate; A step of forming an intermediate layer on at least one surface of the liquid crystal polymer substrate; A step of forming a tie layer on the above intermediate layer; and The step of forming a copper layer on the above tie layer; The above intermediate layer is a cured layer of a composition comprising a low dielectric constant polyimide resin, a silane coupling agent, and inorganic particles, and The thickness of the above intermediate layer is greater than the thickness of the above tie layer, and A method for manufacturing a copper clad laminate film, wherein the thickness of the intermediate layer and the thickness of the tie layer satisfy the following Equation 1: [Equation 1] 100 ≤ A / B < 500 During the meal, A is the thickness of the intermediate layer (nm), and B is the thickness of the tie layer (nm). In Paragraph 16, A method for manufacturing a copper clad laminate, further comprising the step of performing corona surface treatment or plasma surface treatment on one surface of a liquid crystal polymer substrate having an intermediate layer formed on at least one surface.

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