KR102374540B1 - low dielectric composite film for high speed communication, manufacturing method thereof and copper clad laminate containing the same - Google Patents

Abstract

The present invention relates to a low-dielectric composite film for high-speed communication, a manufacturing method thereof, and a copper-clad laminate comprising the same, and more specifically, to a low-dielectric composite film for high-speed communication which has low moisture absorption, excellent dielectric constant and dielectric loss properties in a high-speed communication system using high frequency (3 GHz or higher), and the excellent dielectric constant and dielectric loss properties in both dry and humid environments, a manufacturing method thereof, and a copper-clad laminate comprising the same.

Description

Low dielectric composite film for high speed communication, manufacturing method thereof, and copper clad laminate containing the same

The present invention relates to a low-dielectric composite film for high-speed communication, a manufacturing method thereof, and a copper clad laminate including the same, and more particularly, not only has a low moisture absorption rate, but also uses a high frequency (3 GHz or more, preferably 3 to 30 GHz) It has excellent dielectric constant and dielectric loss characteristics in a high-speed communication system, and has excellent dielectric constant and dielectric loss characteristics in both dry and humid environments, to a low-dielectric composite film for high-speed communication, a manufacturing method thereof, and a copper clad laminate including the same.

The era of downloading 1GB in 10 seconds, that is, the era of 5G networks, is opening. At the International Consumer Electronics Show 2017 (CES 2017), as Intel announced the world's first 5G modem and predicted that innovation would occur in various fields such as autonomous vehicles, the Internet of Things, and wireless broadband based on gigabit speed, mobile communication companies is already moving to 5G mobile communication. The International Telecommunication Union (ITU) held a radio communication assembly in October 2015 and set the official technology name for 5G as 'IMT (International Mobile Telecommunication)-2020'. 5G stands for '5th generation mobile communications'.

According to the definition given by the International Telecommunication Union (ITU), 5G is a mobile communication technology with a maximum download speed of 20 Gbps and a minimum download speed of 100 Mbps. In addition, it should be able to provide Internet of Things (IoT) services to 1 million devices within a radius of 1 km2, and free communication should be possible even on high-speed trains at a speed of 500 km/h. 5G download speed is more than 70 times faster than the current mobile communication speed of 300Mbps and 280 times faster than general LTE. This is the speed at which a 1GB movie can be downloaded in 10 seconds. 5G doesn't just care about transmission speed. The response speed is noticeably improved as well as the transmission speed.

If data transfer speed is an indicator of how much data can pass at a time, response speed measures the time it takes for small data to pass through. In 4G, the response speed has been increased to 10-50ms (milliseconds, thousandths of a second). In 5G, this response speed will be about 10 times faster. Thanks to this, 5G will be actively introduced in the field of autonomous vehicles and Internet of Things (IoT), where large amounts of data must be exchanged seamlessly with a central server.

On the other hand, unlike 4G, which uses a frequency of 2 GHz or less, 5G uses an ultra-high band frequency of 3 GHz or more, preferably 3 to 30 GHz. Signals transmitted and received in the mobile communication system are radio waves, and 5G, which is currently under construction, uses high frequency bands of 3.5 GHz and 28 GHz, and uses a significantly higher high frequency band compared to 4G. strong) and short radio wave reach, the installation of more base stations or repeaters than 4G is required.

As the frequency of the electric signal increases, the transmission loss increases. In the case of conventional low-k films and copper clad laminates, low dielectric constant and dielectric loss could not be achieved at the desired level, so it was not possible to minimize or prevent signal interference in high frequency bands, and even if a predetermined low dielectric constant was expressed, mechanical properties were not There was a problem of lowering or a high coefficient of thermal expansion.

In addition, in the case of the conventional low-k film and copper clad laminate, there was a problem in that it was not possible to achieve low dielectric constant and dielectric loss at desired levels in both dry and humid environments.

Registered Patent Publication No. 10-0536064 (Announcement Date: 2005.12.14)

The present invention has been devised in view of the above points, and has a low moisture absorption rate and excellent dielectric constant and dielectric loss characteristics in a high-speed communication system using a high frequency (3 GHz or more, preferably 3 to 30 GHz), An object of the present invention is to provide a low-dielectric composite film for high-speed communication having excellent dielectric constant and dielectric loss characteristics in both dry and humid environments, a manufacturing method thereof, and a copper clad laminate including the same.

In order to solve the above problems, the low-k composite film for high-speed communication of the present invention includes a porous support and a polyimide-based matrix formed on the surface of the porous support.

In a preferred embodiment of the present invention, the composite film of the present invention may have a water absorption rate of 1.0% or less as measured by the following relational formula (1).

[Relational Expression 1]

In the above relation 1, A represents the weight of the composite film measured after drying the composite film at a temperature of 80 to 120 ° C. for 30 to 90 minutes, and B is the composite film at a temperature of 80 to 120 ° C. for 30 to 90 minutes. After drying for a while, it shows the weight of the composite film measured after being impregnated in distilled water at 20 to 25° C. for 12 to 36 hours.

In a preferred embodiment of the present invention, the composite film of the present invention may satisfy all of the following conditions (1) and (2).

(1) D ₁ ≤ 0.01

(2) D ₂ ≤ 0.01

In the above condition (1), D ₁ represents the dielectric loss of the composite film measured at a frequency of 28 GHz after drying the composite film at a temperature of 80 to 120° C. for 30 to 90 minutes.

In the above condition (2), D ₂ is measured at a frequency of 28 GHz after drying the composite film at a temperature of 80 to 120 ° C. for 30 to 90 minutes, and then immersing it in distilled water at 20 to 25 ° C. for 12 to 36 hours. It represents the dielectric loss of the composite film.

In a preferred embodiment of the present invention, the composite film of the present invention may satisfy all of the following conditions (3) and (4).

(3) P ₁ ≤ 2.9

(4) P ₂ ≤ 2.9

In the above condition (3), P ₁ represents the permittivity of the composite film measured at a frequency of 28 GHz after drying the composite film at a temperature of 80 to 120° C. for 30 to 90 minutes.

In the above condition (4), P ₂ is measured at a frequency of 28 GHz after drying the composite film at a temperature of 80 to 120 ° C. for 30 to 90 minutes, and then immersing it in distilled water at 20 to 25 ° C. for 12 to 36 hours. It represents the permittivity of the composite film.

In a preferred embodiment of the present invention, the porous support of the present invention may include expanded polytetrafluoroethylene (ePTFE).

In a preferred embodiment of the present invention, the polyimide-based matrix of the present invention is BPDA (3,3′,4,4′-Biphenyltetracarboxylic dianhydride) monomer, PMDA (Pyromellitic dianhydride) monomer, ODPA (4,4′-oxydiphthalic) anhydride) monomer, BTDA (3,3',4,4'-benzophenonetetracarboxylic dianhydride) monomer, BPADA (2,2-Bis[4-(3,4-Dicarboxyphenoxy)Phenyl]Propane Dianhydride) monomer, TAHQ (Ditricarboxylic anhydride hydroquinone) ester) monomer, 6FDA (2,2-bis (3,4-anhydrodicarboxyphenyl) hexafluoropropane) monomer, CBDA (cyclobutane-1,2,3,4-tetracarboxylic dianhydride) monomer, CHDA (1,2,4,5-Cyclohexanetetracarboxylic) Dianhydride) monomer, pPDA (paraphenylene diamine) monomer, ODA (4,4'-Oxydianiline) monomer, TPE-R (1,3-Bis (4-aminophenoxy)benzene) monomer, TPE-Q (1,4-Bis ( 4-aminophenoxy)benzene) monomer, BAPP(2,2-Bis[4-(4-aminophenoxy)Phenyl]Propane) monomer, M-Tolidine (2,2'-Dimethyl-4,4'-diaminobiphenyl) monomer, O -Tolidine (3,3'-Dimethyl-4,4'-diaminobiphenyl) monomer, TFDB (2,2'-bis(trifluoromethyl)-[1,1'-biphenyl]-4,4'-diamine) monomer and HFBAPP (2,2-Bis[4-(4-aminophenoxy)phenyl] hexafluoropropane) When polymerizing two or more monomers selected from among monomers and an imidation reaction product of Kean polyamic acid.

In a preferred embodiment of the present invention, the polyimide-based matrix of the present invention may include an imidation reaction product of a polyamic acid obtained by polymerizing a pPDA monomer, an ODA monomer, and a BPDA monomer.

In a preferred embodiment of the present invention, the polyamic acid of the present invention may include 20.0 to 30.0 wt% of a pPDA monomer, 0.2 to 10 wt% of an ODA monomer, and 50.0 to 80.0 wt% of a BPDA monomer based on the total weight of the monomer. there is.

In a preferred embodiment of the present invention, the composite film of the present invention may include 40 to 90% by weight of the porous support, based on the total weight%.

In a preferred embodiment of the present invention, the composite film of the present invention may include the porous support in an amount of 30 to 80% by volume, based on the total volume%.

On the other hand, the copper clad laminate of the present invention includes the low-k dielectric composite film for high-speed communication of the present invention, an adhesive layer formed on one surface of the composite film, and a copper foil formed on one surface of the adhesive layer.

Furthermore, the method for manufacturing a low-k composite film for high-speed communication of the present invention includes a first step of preparing a polyamic acid solution and a porous support, respectively, a second step of impregnating the prepared porous support with a polyamic acid solution, and a porous polyamic acid solution impregnated with the polyamic acid solution and a third step of heat-treating the support to imidize the polyamic acid to form a polyimide-based matrix on the surface of the porous support to prepare a composite film, wherein the composite film has a water absorption rate measured by the following Relational Equation 1 It may be 1.0% or less.

[Relational Expression 1]

In the above relation 1, A represents the weight of the composite film measured after drying the composite film at a temperature of 80 to 120 ° C. for 30 to 90 minutes, and B is the composite film at a temperature of 80 to 120 ° C. for 30 to 90 minutes. After drying for a while, it shows the weight of the composite film measured after being impregnated in distilled water at 20 to 25° C. for 12 to 36 hours.

The low-dielectric composite film for high-speed communication according to the present invention, a manufacturing method thereof, and a copper clad laminate including the same have a low moisture absorption rate and excellent dielectric constant in a high-speed communication system using a high frequency (3 GHz or more, preferably 3 to 30 GHz) and dielectric loss characteristics, and excellent permittivity and dielectric loss characteristics in both dry and humid environments.

1 is a cross-sectional view of a low-k composite film for high-speed communication according to a preferred embodiment of the present invention.
2 is a cross-sectional view of a low-k composite film for high-speed communication according to another preferred embodiment of the present invention.
3 is a cross-sectional view of a copper clad laminate according to a preferred embodiment of the present invention.

Hereinafter, with reference to the accompanying drawings, embodiments of the present invention will be described in detail so that those of ordinary skill in the art can easily carry out the present invention. The present invention may be embodied in many different forms and is not limited to the embodiments described herein. In order to clearly explain the present invention in the drawings, parts irrelevant to the description are omitted, and the same reference numerals are added to the same or similar elements throughout the specification.

The low-dielectric composite film for high-speed communication of the present invention has excellent dielectric constant and dielectric loss characteristics in a high-speed communication system used in a frequency region of 3 GHz or more, preferably in a frequency region of 3 to 30 GHz, and more preferably in a frequency region of 25 to 30 GHz. It is a composite film.

As shown in FIGS. 1 and 2, the low-k composite film for high-speed communication of the present invention includes a porous support 10 and polyimide-based matrices 11 and 12 formed on the surface of the porous support 10. At this time, the polyimide-based matrices 11 and 12 are formed on the surface of the porous support 10 by curing the imidization reaction product of the polyamic acid. Also includes the surface on which it is located. Specifically, the porous support 10 is a support having pores on the outer surface and/or the inner surface, and the imidization reaction product of the polyamic acid forming the polyimide-based matrix 11 and 12 is the outside of the porous support 10 . As well as the surface, as it penetrates and hardens the inner surface of the porous support 10 through the pores, not only occludes all the pores of the porous support 10, but also the outer surface (one or both surfaces) of the porous support 10 is constant It can be cured to have a thickness to form the polyimide-based matrices 11 and 12 . In other words, the imidation reaction product of polyamic acid forming the polyimide-based matrix 11 and 12 penetrates into the inner surface through the pores of the porous support 10 and hardens, thereby occluding all the pores of the porous support 10 and , is cured to have a certain thickness on one surface of the porous support 10 as described in FIG. 1 to form a polyimide-based matrix 11, or has a certain thickness on both sides of the porous support 10 as described in FIG. It can be cured to form the polyimide-based matrices 11 and 12 .

The porous support 10 may include expanded polytetrafluoroethylene (ePTFE). Expanded polytetrafluoroethylene is a support having porosity by performing a stretching process on polytetrafluoroethylene.

The porous support 10 may have a ratio of tensile strength in the MD direction and tensile strength in the TD direction of 1: 0.4 to 2.5, preferably, the ratio of tensile strength in the MD direction and tensile strength in the TD direction is 1: 0.8 to 1.7 days. can If the ratio of the tensile strength in the MD direction to the tensile strength in the TD direction is less than 1:0.4 or exceeds 1:2.5, deformation may occur in the low-k composite film due to the difference in shrinkage and stress in each direction.

In addition, the porous support 10 may have a thickness of 10 to 100 μm, preferably 30 to 50 μm, but is not limited thereto.

On the other hand, as an example of manufacturing an expanded polytetrafluoroethylene, step 1-1 of preparing a paste by mixing and stirring polytetrafluoroethylene (PTFE) powder and a lubricant; Step 1-2 of aging the paste; Steps 1-3 of extruding and rolling the aged paste to prepare an unbaked tape; Steps 1-4 of removing the liquid lubricant after drying the unbaked tape; Steps 1-5 of uniaxially stretching the unbaked tape from which the lubricant has been removed; Steps 1-6 of biaxially stretching the uniaxially stretched unbaked tape; and steps 1-7 of calcining.

In step 1-1, the paste may contain 15 to 35 parts by weight of a lubricant, preferably 15 to 30 parts by weight, more preferably 15 to 25 parts by weight based on 100 parts by weight of the PTFE powder. The average particle diameter of the PTFE powder is 300㎛ ~ 800㎛. Preferably, it may be 450 μm to 700 μm, but is not limited thereto. The lubricant is a liquid lubricant, and in addition to hydrocarbon oils such as liquid paraffin, naphtha, white oil, toluene, and xylene, various alcohols, ketones, esters, etc. may be used, and preferably liquid paraffin, naphtha and white oil One or more types may be used.

Next, the aging of step 1-2 is a preforming process, and the paste may be aged for 12 to 24 hours at a temperature of 30° C. to 70° C., preferably 16 to at a temperature of 35° C. to 60° C. It can be aged for 20 hours.

Next, in the extrusion of steps 1-3, a PTFE block is prepared by compressing the aged paste in a compressor, and then the PTFE block is pressed at a pressure of 0.069 to 0.200 Ton/cm ² , preferably 0.090 to 0.175 Ton/cm It can be carried out by pressurized extrusion at a pressure of ² . In addition, the rolling of steps 1-3 may be performed by a calendering process under 50 to 100° C. with a hydraulic pressure of 5 to 10 MPa.

Next, the drying of steps 1-4 can be performed through a general drying method used in the art, for example, the unbaked tape prepared by rolling at a temperature of 100 ℃ ~ 200 ℃ 1 ~ 5M / While conveying to the conveyor belt at a speed of min, it can be carried out while conveying at a temperature of preferably 140 ℃ ~ 190 ℃ 2 ~ 4M / min at a speed.

Next, the uniaxial stretching of steps 1-5 is a process of stretching the unbaked tape from which the lubricant has been removed in the longitudinal direction. When transported through rollers, the uniaxial stretching is performed using the speed difference between the rollers. . And, the uniaxial stretching is 3 to 10 times, preferably 6 to 9.5 times, more preferably 6.2 to 9 times, even more preferably 6.3 to 8.2 times the stretching of the unbaked tape from which the lubricant is removed in the longitudinal direction. It is good to do In addition, the uniaxial stretching is performed at a stretching temperature of 260 ° C. to 350 ° C. and a stretching speed of 6 to 12 M/min, preferably at a stretching temperature of 270 ° C. to 330 ° C. and a stretching speed of 8 to 11.5 M/min. good night.

Next, in the biaxial stretching of steps 1-6, stretching is performed in the width direction (direction perpendicular to the uniaxial stretching) of the uniaxially stretched unbaked tape, and the width is widened in the lateral direction while the end is fixed. can be stretched However, the present invention is not limited thereto, and may be stretched according to a stretching method commonly used in the art. In the present invention, the biaxial stretching may be performed at 15 to 50 times in the width direction, preferably 25 to 45 times, more preferably 28 to 45 times, still more preferably 29 to 42 times. there is. In addition, biaxial stretching is carried out at a stretching rate of 10 to 20 M/min under a stretching temperature of 150° C. to 260° C., preferably at a stretching rate of 11 to 18 M/min under a stretching temperature of 200° C. to 250° C. can do.

Finally, the firing of steps 1-7 moves the stretched porous support on a conveyor belt at a speed of 10 to 18 M/min, preferably at a speed of 13 to 17 M/min, at 350° C. to 450° C., Preferably, a temperature of 380°C to 440°C, more preferably 400°C to 435°C, may be performed by applying a temperature.

In addition, the expanded polytetrafluoroethylene prepared by performing the process of steps 1-7 has a stretch ratio (or aspect ratio) in the uniaxial direction (length direction) and biaxial direction (width direction) of 1:3.00 to 8.5, preferably Preferably it may be 1: 4.0 to 7.0, more preferably 1: 4.00 to 5.50, and even more preferably 1: 4.20 to 5.00.

The prepared expanded polytetrafluoroethylene may have an average pore size of 0.080 μm to 0.200 μm, preferably 0.090 μm to 0.180 μm, more preferably 0.095 μm to 0.150 μm, even more preferably 0.100 to 0.140 μm. . In addition, the prepared expanded polytetrafluoroethylene may have an average porosity of 60% to 90%, more preferably 60% to 79.6%.

Polyimide matrix (11, 12) is BPDA (3,3′,4,4′-Biphenyltetracarboxylic dianhydride) monomer, PMDA (Pyromellitic dianhydride) monomer, ODPA (4,4′-oxydiphthalic anhydride) monomer, BTDA (3, 3',4,4'-benzophenonetetracarboxylic dianhydride) monomer, BPADA(2,2-Bis[4-(3,4-Dicarboxyphenoxy)Phenyl]Propane Dianhydride) monomer, TAHQ(Ditricarboxylic anhydride hydroquinone ester) monomer, 6FDA(2, 2-bis (3,4-anhydrodicarboxyphenyl) hexafluoropropane) monomer, CBDA (cyclobutane-1,2,3,4-tetracarboxylic dianhydride) monomer, CHDA (1,2,4,5-Cyclohexanetetracarboxylic Dianhydride) monomer, pPDA (paraphenylene diamine) ) monomer, ODA(4,4'-Oxydianiline) monomer, TPE-R(1,3-Bis(4-aminophenoxy)benzene) monomer, TPE-Q(1,4-Bis(4-aminophenoxy)benzene) monomer, BAPP(2,2-Bis[4-(4-aminophenoxy)Phenyl]Propane) Monomer, M-Tolidine(2,2'-Dimethyl-4,4'-diaminobiphenyl) Monomer, O-Tolidine(3,3'- Dimethyl-4,4'-diaminobiphenyl) monomer, TFDB (2,2'-bis(trifluoromethyl)-[1,1'-biphenyl]-4,4'-diamine) monomer and HFBAPP (2,2-Bis[4) -(4-aminophenoxy)phenyl] hexafluoropropane) imidization reaction product of polyamic acid obtained by polymerizing two or more monomers selected from among monomers Preferably, it may include an imidation reaction product of a polyamic acid obtained by polymerizing a pPDA monomer, an ODA monomer, and a BPDA monomer.

On the other hand, the polyamic acid may include 20.0 to 30.0 wt% of pPDA monomer, preferably 24.0 to 28.0 wt%, more preferably 25.0 to 27.0 wt%, based on the total weight of the monomer, and if the pPDA monomer is 20 wt% If it is less than %, there may be a problem in dimensional stability, and if it exceeds 30% by weight, there may be a problem in that fairness is lowered.

In addition, the polyamic acid may include 0.2 to 10% by weight of ODA monomer, preferably 0.3 to 8.0% by weight, more preferably 0.3 to 4.0% by weight, based on the total weight% of the monomer, and if the ODA monomer is 0.2% by weight If it is less than %, there may be a problem in moisture absorption, and if it exceeds 10 wt%, there may be a problem in that dimensional stability is lowered.

In addition, the polyamic acid may be contained in an amount of 50.0 to 80.0 wt%, preferably 60.0 to 77.0 wt%, more preferably 68.0 to 75.0 wt%, based on the total weight of the monomer, and if the BPDA monomer is 50 wt% If it is less than, there may be a problem of moisture absorption, and if it exceeds 80% by weight, there may be a problem in that the degree of polymerization is lowered.

On the other hand, the low-k composite film for high-speed communication of the present invention contains the porous support 10 in an amount of 40 to 90% by weight, preferably 55 to 90% by weight, more preferably 65 to 85% by weight, based on the total weight%. can, and if the porous support 10 is included in less than 40% by weight, there may be a problem that the dielectric properties are lowered, and if it contains more than 90% by weight, the difficulty of manufacturing the composite material as well as the problem of lowering the mechanical strength there may be

In addition, the low-k composite film for high-speed communication of the present invention contains the porous support 10 in an amount of 30 to 80% by volume, preferably 45 to 80% by volume, more preferably 55 to 80% by volume, based on the total volume%. It can be, and if the porous support 10 is included in less than 30% by volume, there may be a problem that the dielectric properties are lowered, and if it contains more than 80% by volume, the difficulty of manufacturing the composite material as well as the problem of lowering the mechanical strength there may be

Furthermore, the low-k composite film for high-speed communication of the present invention may have a water absorption rate of 1.0% or less, preferably 0.1-0.5%, more preferably 0.1-0.3%, as measured by the following relational formula (1).

[Relational Expression 1]

In Relation 1, A represents the weight of the composite film measured after drying the composite film at a temperature of 80 to 120° C., preferably 90 to 110° C. for 30 to 90 minutes, preferably 45 to 75 minutes, B is 80 ~ 120 ℃, preferably after drying the composite film at a temperature of 90 ~ 110 ℃ 30 ~ 90, preferably 45 ~ 75 minutes, 20 ~ 25 ℃ distilled water for 12 to 36 hours, preferably Shows the weight of the composite film measured after being impregnated for 18 to 30 hours.

In addition, the low-k composite film for high-speed communication of the present invention may satisfy all of the following conditions (1) and (2).

(1) D ₁ ≤ 0.01, preferably 0.0001 ≤ D ₁ ≤ 0.002, more preferably 0.0005 ≤ D ₁ ≤ 0.0013

(2) D ₂ ≤ 0.01, preferably 0.001 ≤ D ₂ ≤ 0.007, more preferably 0.001 ≤ D ₂ ≤ 0.004

In the above condition (1), D ₁ is measured at a frequency of 28 GHz after drying the composite film for 30 to 90 minutes, preferably 45 to 75 minutes at a temperature of 80 to 120 ° C., preferably 90 to 110 ° C. Represents the dielectric loss of the composite film,

In the above condition (2), D ₂ is 80 ~ 120 ℃, preferably after drying the composite film at a temperature of 90 ~ 110 ℃ 30 ~ 90 minutes, preferably 45 ~ 75 minutes, 20 ~ 25 ℃ of Shows the dielectric loss of the composite film measured at a frequency of 28 GHz after being immersed in distilled water for 12 to 36 hours, preferably 18 to 30 hours.

In addition, the low-k composite film for high-speed communication of the present invention may satisfy all of the following conditions (3) and (4).

(3) P ₁ ≤ 2.9, preferably 2.0 ≤ P ₁ ≤ 2.8, more preferably 2.0 ≤ P ₁ ≤ 2.5

(4) P ₂ ≤ 2.9, preferably 2.0 ≤ P ₂ ≤ 2.8, more preferably 2.0 ≤ P ₂ ≤ 2.55

In the above condition (3), P ₁ is measured at a frequency of 28 GHz after drying the composite film at a temperature of 80 to 120 ° C., preferably 90 to 110 ° C. for 30 to 90 minutes, preferably 45 to 75 minutes. represents the permittivity of the composite film,

In the above condition (4), P ₂ is 80 ~ 120 ℃, preferably after drying the composite film at a temperature of 90 ~ 110 ℃ 30 ~ 90 minutes, preferably 45 ~ 75 minutes, 20 ~ 25 ℃ of Shows the permittivity of the composite film measured at a frequency of 28 GHz after being immersed in distilled water for 12 to 36 hours, preferably 18 to 30 hours.

In addition, the low-k composite film for high-speed communication of the present invention may have a thickness of 20 to 150 μm, preferably 40 to 650 μm, but is not limited thereto.

On the other hand, as shown in FIG. 3, the copper clad laminate (CCL) of the present invention has a low-k dielectric composite film 100 for high-speed communication of the present invention, an adhesive layer 200 formed on one surface of the composite film, and the adhesive layer It may include a copper foil 300 formed on one surface.

The adhesive layer 200 performs a function of fixing the copper foil 300 included in the copper clad laminate of the present invention to the low-k dielectric composite film 100 for high-speed communication of the present invention. At this time, the adhesive layer 200 can be applied without limitation as long as it is an adhesive layer formed of an adhesive layer material commonly used in the art, and preferably an epoxy-based adhesive layer, a thermoplastic polyimide-based adhesive layer, a silicone-based adhesive layer, and an acrylic adhesive layer. It may be one or more adhesive layers selected from.

In addition, the copper foil 300 may be a copper foil having a known specification that can be commonly used in the art, and the present invention is not particularly limited thereto.

Furthermore, the manufacturing method of the low-k composite film for high-speed communication of the present invention includes the first to third steps.

First, in the first step of the method of manufacturing a low-k composite film for high-speed communication of the present invention, a polyamic acid solution and a porous support may be prepared, respectively. At this time, the porous support is as described above.

In addition, the polyamic acid solution can be prepared by adding and reacting at least two or more monomers in a solvent under a nitrogen atmosphere and a temperature of 10 to 80°C, preferably 30 to 60°C. At this time, the solvent is DMF (N,N-dimethylformamide), DMAc (N,Ndimethylacetamide), NMP (1-methyl-2-pyrrolidone), NEP (N-ethyl-2-pyrrolidone), GBL (γ-butyrolactone), GVL (γ-valerolactone), DVL (δ-valerolactone), ethylene carbonate, propylene carbonate, m-cresol, p-cresol, acetophenone, THF (TetraHydroFuran), dimethoxyethane, diethoxyethane, dibutyl ether, diethylene glycol dimethyl ether, methyl isobutyl ketone, diisobutyl ketone, cyclohexanone, methyl ethyl ketone, acetone, butanol, ethanol, xylene, toluene And may include at least one selected from the group consisting of chlorobenzene, the monomer is BPDA (3,3′,4,4′-Biphenyltetracarboxylic dianhydride) monomer, PMDA (Pyromellitic dianhydride) monomer, ODPA (4,4'- oxydiphthalic anhydride) monomer, BTDA (3,3',4,4'-benzophenonetetracarboxylic dianhydride) monomer, BPADA (2,2-Bis[4-(3,4-Dicarboxyphenoxy)Phenyl]Propane Dianhydride) monomer, TAHQ (Ditricarboxylic anhydride) hydroquinone ester) monomer, 6FDA (2,2-bis (3,4-anhydrodicarboxyphenyl) hexafluoropropane) monomer, CBDA (cyclobutane-1,2,3,4-tetracarboxylic dianhydride) monomer, CHDA (1,2,4,5- Cyclohexanetetracarboxylic Dianhydride) Monomer, pPDA (paraphenylene diamine) Monomer Sieve, ODA(4,4'-Oxydianiline) monomer, TPE-R(1,3-Bis(4-aminophenoxy)benzene) monomer, TPE-Q(1,4-Bis(4-aminophenoxy)benzene) monomer, BAPP (2,2-Bis[4-(4-aminophenoxy)Phenyl]Propane) Monomer, M-Tolidine(2,2'-Dimethyl-4,4'-diaminobiphenyl) Monomer, O-Tolidine(3,3'-Dimethyl) -4,4'-diaminobiphenyl) monomer, TFDB (2,2'-bis(trifluoromethyl)-[1,1'-biphenyl]-4,4'-diamine) monomer and HFBAPP (2,2-Bis[4- (4-aminophenoxy)phenyl] hexafluoropropane) may include two or more selected from monomers, and preferably include a pPDA monomer, an ODA monomer, and a BPDA monomer.

Specifically, the polyamic acid solution is prepared by dissolving the pPDA monomer and the ODA monomer in a solvent under a nitrogen atmosphere and a temperature of 10 to 80 ° C, preferably 30 to 60 ° C, and then dissolving, , The BPDA monomer is added to the prepared first mixture over 10 to 60 minutes, preferably 20 to 40 minutes to prepare a second mixture, and then the prepared second mixture is heated to 80° C. or less, preferably 30 to 60 The solid content is 10 to 20% by weight, preferably 13 to 17% by weight by reacting at a temperature of ℃ 8 to 24 hours, preferably 12 to 20 hours, and a viscosity of 2,500 to 4,500 cps at a temperature of 25℃, Preferably, a polyamic acid solution of 3,000 to 4,000 cps can be prepared. At this time, the prepared polyamic acid solution may be subjected to a filtering process.

Next, in the second step of the method for manufacturing a low-k composite film for high-speed communication of the present invention, the porous support prepared in the first step may be impregnated with the polyamic acid solution prepared in the first step. In addition, after the impregnation, a drying process for removing the solvent contained in the polyamic acid solution may be performed. Specifically, in the drying process, the porous support impregnated in the polyamic acid solution is first dried at a temperature of 60 to 100° C., preferably 70 to 90° C. for 1 to 10 minutes, preferably 3 to 7 minutes, and then 100 to Secondary drying may be performed at 140 ° C., preferably at a temperature of 110 to 130 ° C. for 5 to 20 minutes, preferably for 7 to 15 minutes.

Finally, in the third step of the method for manufacturing a low-k composite film for high-speed communication of the present invention, a polyimide-based matrix is formed on the surface of the porous support by heat-treating the porous support impregnated with a polyamic acid solution to imidize the polyamic acid. can be formed to produce a composite film.

At this time, the heat treatment is a primary heat treatment of the porous support at a temperature of 200 ~ 300 ℃, preferably 230 ~ 270 ℃ 1 ~ 20 minutes, preferably 5 ~ 15 minutes, then 300 ~ 400 ℃, preferably It can be carried out by secondary heat treatment at a temperature of 330 to 370° C. for 1 to 10 minutes, preferably 3 to 7 minutes.

On the other hand, the composite film produced by the method for manufacturing a low-k composite film for high-speed communication of the present invention has a water absorption rate of 1.0% or less, preferably 0.1 to 0.5%, more preferably 0.1 to 0.3%, as measured by the following relational formula 1 can

[Relational Expression 1]

In Relation 1, A represents the weight of the composite film measured after drying the composite film at a temperature of 80 to 120° C., preferably 90 to 110° C. for 30 to 90 minutes, preferably 45 to 75 minutes, B is 80 ~ 120 ℃, preferably after drying the composite film at a temperature of 90 ~ 110 ℃ 30 ~ 90, preferably 45 ~ 75 minutes, 20 ~ 25 ℃ distilled water for 12 to 36 hours, preferably Shows the weight of the composite film measured after being impregnated for 18 to 30 hours.

In addition, the composite film prepared by the method for manufacturing a low-k composite film for high-speed communication of the present invention may satisfy both the following conditions (1) and (2).

(1) D ₁ ≤ 0.01, preferably 0.0001 ≤ D ₁ ≤ 0.002, more preferably 0.0005 ≤ D ₁ ≤ 0.0013

(2) D ₂ ≤ 0.01, preferably 0.001 ≤ D ₂ ≤ 0.007, more preferably 0.001 ≤ D ₂ ≤ 0.004

In the above condition (1), D ₁ is measured at a frequency of 28 GHz after drying the composite film for 30 to 90 minutes, preferably 45 to 75 minutes at a temperature of 80 to 120 ° C., preferably 90 to 110 ° C. Represents the dielectric loss of the composite film,

In the above condition (2), D ₂ is 80 ~ 120 ℃, preferably after drying the composite film at a temperature of 90 ~ 110 ℃ 30 ~ 90 minutes, preferably 45 ~ 75 minutes, 20 ~ 25 ℃ of Shows the dielectric loss of the composite film measured at a frequency of 28 GHz after being immersed in distilled water for 12 to 36 hours, preferably 18 to 30 hours.

In addition, the composite film produced by the method for manufacturing the low-k dielectric composite film for high-speed communication of the present invention may satisfy all of the following conditions (3) and (4).

(3) P ₁ ≤ 2.9, preferably 2.0 ≤ P ₁ ≤ 2.8, more preferably 2.0 ≤ P ₁ ≤ 2.5

(4) P ₂ ≤ 2.9, preferably 2.0 ≤ P ₂ ≤ 2.8, more preferably 2.0 ≤ P ₂ ≤ 2.55

In the above condition (3), P ₁ is measured at a frequency of 28 GHz after drying the composite film at a temperature of 80 to 120 ° C., preferably 90 to 110 ° C. for 30 to 90 minutes, preferably 45 to 75 minutes. represents the permittivity of the composite film,

In the above condition (4), P ₂ is 80 ~ 120 ℃, preferably after drying the composite film at a temperature of 90 ~ 110 ℃ 30 ~ 90 minutes, preferably 45 ~ 75 minutes, 20 ~ 25 ℃ of Shows the permittivity of the composite film measured at a frequency of 28 GHz after being immersed in distilled water for 12 to 36 hours, preferably 18 to 30 hours.

In the above, the present invention has been mainly described with respect to the embodiment, but this is only an example and does not limit the embodiment of the present invention. It can be seen that various modifications and applications not exemplified above are possible without departing from the scope. For example, each component specifically shown in the embodiment of the present invention can be implemented by modification. And differences related to such modifications and applications should be construed as being included in the scope of the present invention defined in the appended claims.

Example 1: Preparation of low-k composite film for high-speed communication

(1) pPDA monomer and ODA monomer were added to a solvent (using DMAc) under a nitrogen atmosphere and a temperature of 50° C., and then completely dissolved to prepare a first mixture. The BPDA monomer was added to the prepared first mixture over 30 minutes to prepare a second mixture. The prepared second mixture was reacted at a temperature of 50°C for 16 hours to prepare a polyamic acid solution having a solid content of 15% by weight and a viscosity of 3,500 cps at 25°C. At this time, with respect to the total weight % of the monomers used to prepare the polyamic acid solution, the weight % of each monomer is shown in Table 1 below. After the prepared polyamic acid solution was filtered with a MINIFLOW filter (CTS-CAP10 A grade) of Cheongsu Technopil, a polyamic acid solution having a solid content of 15 wt% was finally prepared.

(2) As a porous support, expanded polytetrafluoroethylene having an average pore size of 0.114 μm and a thickness of 40 μm (= the tensile strength in the MD direction was 30 MPa and the tensile strength in the TD direction was 25 MPa, the tensile strength in the MD direction and The ratio of tensile strength in the TD direction is 1: 0.8), the prepared ePTFE is impregnated in the polyamic acid solution, and the porous support impregnated in the polyamic acid solution is first dried at a temperature of 80 ° C. for 5 minutes. Next, secondary drying was performed at a temperature of 120° C. for 10 minutes to remove the solvent contained in the polyamic acid solution.

(3) The porous support from which the solvent has been removed is subjected to primary heat treatment at a temperature of 250° C. for 10 minutes, and then secondary heat treatment at a temperature of 350° C. for 5 minutes to imidize the polyamic acid, thereby forming a polyimide on the surface of the porous support. By forming the matrix based on the total weight, 85% by weight of the porous support, 15% by weight of the polyimide-based matrix, 79% by volume of the porous support, and 21% by volume of the polyimide-based matrix with respect to the total volume% A low-k composite film for high-speed communication having a thickness of 50 μm was prepared. At this time, in order to minimize the construction of the composite film and the occurrence of curl, heat treatment was performed under the transverse direction (TD) stretching condition through a tenter (roll stretching machine) facility.

Example 2: Preparation of low-k composite film for high-speed communication

A low-k composite film for high-speed communication was prepared in the same manner as in Example 1. However, unlike in Example 1, by changing the basis weight of the porous support used, finally, based on the total weight, 79% by weight of the porous support, 21% by weight of the polyimide-based matrix, and the porous support with respect to the total volume% A low-k composite film for high-speed communication was prepared including 71% by volume and 29% by volume of a polyimide-based matrix, and having a thickness of 50 μm.

Example 3: Preparation of low-k composite film for high-speed communication

A low-k composite film for high-speed communication was prepared in the same manner as in Example 1. However, unlike Example 1, by changing the basis weight of the porous support used, finally, with respect to the total weight%, 68% by weight of the porous support, 32% by weight of the polyimide-based matrix, and the porous support with respect to the total volume% 59% by volume and 41% by volume of a polyimide-based matrix, a low-k composite film for high-speed communication having a thickness of 50 μm was prepared.

Example 4: Preparation of low-k composite film for high-speed communication

A low-k composite film for high-speed communication was prepared in the same manner as in Example 1. However, unlike Example 1, by changing the basis weight of the porous support to be used, finally, based on the total weight%, the porous support is 60% by weight, the polyimide-based matrix is 40% by weight, and the porous support is used in the total volume%. 50% by volume and 50% by volume of a polyimide-based matrix, and a low dielectric composite film for high-speed communication having a thickness of 50㎛ was prepared.

Example 5: Preparation of low-k composite film for high-speed communication

A low-k composite film for high-speed communication was prepared in the same manner as in Example 1. However, unlike in Example 1, by changing the basis weight of the porous support used, finally, with respect to the total weight%, the porous support was 51% by weight, the polyimide-based matrix was 49% by weight, and the porous support was prepared for the total volume%. 41% by volume and 59% by volume of a polyimide-based matrix, a low-k composite film for high-speed communication having a thickness of 50㎛ was prepared.

Comparative Example 1: Preparation of low-k composite film for high-speed communication

A low-k composite film for high-speed communication was prepared in the same manner as in Example 1. However, unlike Example 1, by changing the basis weight of the porous support used, finally, based on the total weight%, the porous support was 39% by weight, the polyimide-based matrix was 62% by weight, and the porous support was added to the total volume%. 30% by volume and 70% by volume of a polyimide-based matrix, a low-k composite film for high-speed communication having a thickness of 50 μm was prepared.

Comparative Example 2: Preparation of low-k composite film for high-speed communication

A low-k composite film for high-speed communication was prepared in the same manner as in Example 1. However, unlike Example 1, by changing the basis weight of the porous support used, finally, with respect to the total weight%, the porous support is 30% by weight, the polyimide-based matrix is 70% by weight, and the porous support is used in the total volume%. A low-k composite film for high-speed communication containing 22 vol% and 78 vol% of a polyimide-based matrix and having a thickness of 50 μm was prepared.

Comparative Example 3: Preparation of low-k composite film for high-speed communication

A low-k composite film for high-speed communication was prepared in the same manner as in Example 5. However, unlike Example 5, in preparing the polyamic acid solution, the BPDA monomer was added to the first mixture over 30 minutes, stirred for 10 minutes, and then the PMDA monomer was added over 30 minutes to prepare a second mixture. , A polyamic acid was prepared by using the weight% of the monomer as the weight% described in Table 2 below.

Comparative Example 4: Preparation of low-k composite film for high-speed communication

A low-k composite film for high-speed communication was prepared in the same manner as in Example 5. However, unlike Example 5, in preparing the polyamic acid solution, the BPDA monomer was added to the first mixture over 30 minutes, stirred for 10 minutes, and then the PMDA monomer was added over 30 minutes to prepare a second mixture. , A polyamic acid was prepared by using the weight% of the monomer as the weight% described in Table 3 below.

Experimental Example 1: Measurement of water absorption rate of low-k composite film for high-speed communication

Each of the low-k composite films for high-speed communication prepared in Examples 1 to 5 and Comparative Examples 1 to 4 were cut to a size of 10 cm×10 cm (width×length) to prepare a test piece, and the prepared test piece was heated at a temperature of 100° C. for 60 minutes. After drying for a while, the weight of the test piece was measured. Thereafter, the dried test piece was impregnated in distilled water at 23° C. for 24 hours, and then the weight of the test piece was measured. Moisture absorption was measured by the following relational formula 1-1 using the measured values, and the results are shown in Table 4 below.

[Relational Expression 1-1]

In Relation 1-1, A represents the weight of the composite film measured after drying the composite film at a temperature of 100° C. for 60 minutes, and B is after drying the composite film at a temperature of 100° C. for 60 minutes, 23° C. Shows the weight of the composite film measured after being immersed in distilled water for 24 hours.

Experimental Example 2: Measurement of dielectric constant and dielectric loss of low-k composite film for high-speed communication

Each of the low-k composite films for high-speed communication prepared in Examples 1 to 5 and Comparative Examples 1 to 4 were cut to a size of 10 cm×10 cm (width×length) to prepare a test piece, and the prepared test piece was heated at a temperature of 100° C. for 60 minutes. After drying for a while, the dielectric constant (P ₁ ) and dielectric loss (D ₁ ) were respectively measured at a frequency of 28 GHz through a resonant cavity using a network analyzer (E8364A (45 MHz to 50 GHz), Agilent Technologies) in the table below. 4 is shown.

In addition, after immersing the dried specimen in distilled water at 23° C. for 24 hours, the dielectric constant (P ₂ ) at a frequency of 28 GHz through a resonant cavity using a network analyzer (E8364A (45 MHz to 50 GHz), Agilent Technologies) and dielectric loss (D ₂ ) were respectively measured and shown in Table 4 below.

As shown in Table 4, it was confirmed that the low-k composite film for high-speed communication prepared in Example 1 had a low water absorption rate as well as excellent dielectric constant and dielectric loss characteristics in both a dry environment and a humid environment.

Simple modifications or changes of the present invention can be easily carried out by those skilled in the art, and all such modifications or changes can be considered to be included in the scope of the present invention.

10: porous support
11, 12: polyimide-based matrix
100: low dielectric composite film for high-speed communication
200: adhesive layer
300: copper foil

Claims (10)

porous support; and a polyimide-based matrix formed on the surface of the porous support. As a composite film comprising a,
The composite film contains 40 to 90% by weight of the porous support with respect to the total weight%,
The composite film contains 41 to 80% by volume of the porous support with respect to the total volume%,
The composite film is a low dielectric composite film for high-speed communication, characterized in that the water absorption rate measured by the following relation 1 is 0.1 to 0.5%.
[Relational Expression 1]

In the above relation 1, A represents the weight of the composite film measured after drying the composite film at a temperature of 80 to 120 ° C. for 30 to 90 minutes, and B is the composite film at a temperature of 80 to 120 ° C. for 30 to 90 minutes. After drying for a while, it shows the weight of the composite film measured after being impregnated in distilled water at 20 to 25° C. for 12 to 36 hours.
According to claim 1,
The composite film is a low dielectric composite film for high-speed communication, characterized in that it satisfies all of the following conditions (1) and (2).
(1) D ₁ ≤ 0.01
(2) D ₂ ≤ 0.01
In the above condition (1), D ₁ represents the dielectric loss of the composite film measured at a frequency of 28 GHz after drying the composite film at a temperature of 80 to 120 ° C. for 30 to 90 minutes,
In the above condition (2), D ₂ is measured at a frequency of 28 GHz after drying the composite film at a temperature of 80 to 120 ° C. for 30 to 90 minutes, and then immersing it in distilled water at 20 to 25 ° C. for 12 to 36 hours. It represents the dielectric loss of the composite film.
3. The method of claim 2,
The composite film is a low-k composite film for high-speed communication, characterized in that it satisfies all of the following conditions (3) and (4).
(3) P ₁ ≤ 2.9
(4) P ₂ ≤ 2.9
In the above condition (3), P ₁ represents the permittivity of the composite film measured at a frequency of 28 GHz after drying the composite film at a temperature of 80 to 120° C. for 30 to 90 minutes,
In the above condition (4), P ₂ is measured at a frequency of 28 GHz after drying the composite film at a temperature of 80 to 120 ° C. for 30 to 90 minutes, and then immersing it in distilled water at 20 to 25 ° C. for 12 to 36 hours. It represents the permittivity of the composite film.
According to claim 1,
The porous support includes expanded polytetrafluoroethylene (ePTFE),
The polyimide-based matrix is a BPDA (3,3′,4,4′-Biphenyltetracarboxylic dianhydride) monomer, PMDA (Pyromellitic dianhydride) monomer, ODPA (4,4′-oxydiphthalic anhydride) monomer, BTDA (3,3′,4) ,4'-benzophenonetetracarboxylic dianhydride) monomer, BPADA(2,2-Bis[4-(3,4-Dicarboxyphenoxy)Phenyl]Propane Dianhydride) monomer, TAHQ(Ditricarboxylic anhydride hydroquinone ester) monomer, 6FDA(2,2-bis( 3,4-anhydrodicarboxyphenyl)hexafluoropropane) monomer, CBDA (cyclobutane-1,2,3,4-tetracarboxylic dianhydride) monomer, CHDA (1,2,4,5-Cyclohexanetetracarboxylic Dianhydride) monomer, pPDA (paraphenylene diamine) monomer, ODA (4,4'-Oxydianiline) monomer, TPE-R(1,3-Bis(4-aminophenoxy)benzene) monomer, TPE-Q(1,4-Bis(4-aminophenoxy)benzene) monomer, BAPP(2, 2-Bis[4-(4-aminophenoxy)Phenyl]Propane) monomer, M-Tolidine (2,2'-Dimethyl-4,4'-diaminobiphenyl) monomer, O-Tolidine (3,3'-Dimethyl-4, 4'-diaminobiphenyl) monomer, TFDB (2,2'-bis(trifluoromethyl)-[1,1'-biphenyl]-4,4'-diamine) monomer and HFBAPP (2,2-Bis[4-(4- aminophenoxy)phenyl] hexafluoropropane) containing an imidation reaction product of polyamic acid obtained by polymerizing two or more monomers selected from among monomers A low-k composite film for high-speed communication, characterized in that
5. The method of claim 4,
The polyimide-based matrix comprises an imidization reaction product of polyamic acid obtained by polymerizing pPDA monomer, ODA monomer and BPDA monomer.
6. The method of claim 5,
The polyamic acid is based on the total weight of the monomer, pPDA monomer 20.0 ~ 30.0% by weight, ODA monomer 0.2 ~ 10% by weight, and BPDA monomer 50.0 ~ 80.0% by weight of the low dielectric composite film for high-speed communication, characterized in that it comprises.
delete delete The low-k composite film for high-speed communication of claim 1;
an adhesive layer formed on one surface of the composite film; and
a copper foil formed on one surface of the adhesive layer; A copper clad laminate comprising a.
A first step of preparing a polyamic acid solution and a porous support, respectively;
a second step of impregnating the prepared porous support in a polyamic acid solution; and
a third step of heat-treating the porous support impregnated with the polyamic acid solution, imidizing the polyamic acid, and forming a polyimide-based matrix on the surface of the porous support to prepare a composite film; including,
The composite film comprises 40 to 90% by weight of the porous support with respect to the total weight%,
The composite film contains 41 to 80% by volume of the porous support with respect to the total volume%,
The composite film is a method of manufacturing a low-k dielectric composite film for high-speed communication, characterized in that the moisture absorption rate measured by the following relation 1 to 0.1 to 0.5%.
[Relational Expression 1]

In the above relation 1, A represents the weight of the composite film measured after drying the composite film at a temperature of 80 to 120 ° C. for 30 to 90 minutes, and B is the composite film at a temperature of 80 to 120 ° C. for 30 to 90 minutes. After drying for a while, it shows the weight of the composite film measured after being impregnated in distilled water at 20 to 25° C. for 12 to 36 hours.

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