A fluorine-containing resin-based resin composition and use thereof

Abstract

This invention provides a fluoropolymer-based resin composition and its applications, more specifically relating to a fluoropolymer-based resin composition, a fluoropolymer-based dielectric sheet, a copper-clad laminate, and a method for preparing the copper-clad laminate. The fluoropolymer-based resin composition comprises, by weight of solids, the following components: 20-50 parts of polytetrafluoroethylene emulsion, 10-50 parts of high-melting-point organic powder, and 10-40 parts of boron nitride powder; wherein the high-melting-point organic powder has a melting point ≥340℃. By designing the specific composition of the fluoropolymer-based resin composition and through the synergistic effect of the high-melting-point organic powder and boron nitride powder, this invention achieves a resin composition with high thermal conductivity, dielectric properties, and adhesive properties with a relatively small amount of boron nitride, thereby preparing a copper-clad laminate with excellent overall performance.

Description

Technical Field

[0001] This invention belongs to the technical field of copper clad laminate materials, specifically relating to a fluorinated resin-based resin composition and its application, and more specifically to a fluorinated resin-based resin composition, a fluorinated resin-based dielectric sheet, a copper clad laminate, and a method for preparing the copper clad laminate. Background Technology

[0002] Copper clad laminates (CCLs) are widely used in mobile phones, computers, vending machines, communication base stations, satellites, wearable devices, autonomous vehicles, drones, and intelligent robots, and are one of the key basic materials in the electronics, communications, and information industries. Fluoropolymers, represented by polytetrafluoroethylene (PTFE), possess a variety of superior properties unmatched by other polymer resins, including low dielectric constant, low dielectric loss, high thermal stability, and chemical stability, making them an ideal matrix material for CCLs. Since the invention of PTFE-based CCLs in the 1950s, researchers have continuously optimized the formulation and parameters, gradually improving its manufacturing process. The high flexibility of the polymer chains of fluorinated resins often necessitates the introduction of reinforcing materials such as fiberglass cloth to improve the mechanical strength of fluorinated resin-based CCLs.

[0003] PTFE resin possesses excellent dielectric properties but poor thermal conductivity. The industry typically adds thermally conductive inorganic fillers, such as alumina and nitride fillers, to improve the thermal conductivity of the PTFE resin matrix. Among these, hexagonal boron nitride (BN) has become the preferred thermally conductive filler for high-thermal-conductivity PTFE sheets due to its high thermal conductivity and excellent electrical properties. However, adding large amounts of BN can lead to decreased adhesion and significantly increase material costs. Improving the thermal conductivity efficiency of BN fillers is a research hotspot in thermally conductive PTFE. Constructing thermally conductive pathways with less BN is the most direct way to address the cost issue.

[0004] Therefore, how to provide a resin composition with high thermal conductivity, dielectric properties, and adhesive properties with a relatively low amount of boron nitride has become an urgent technical problem to be solved. Summary of the Invention

[0005] To address the shortcomings of existing technologies, the present invention aims to provide a fluoropolymer-based resin composition and its applications, more specifically relating to a fluoropolymer-based resin composition, a fluoropolymer-based dielectric sheet, a copper-clad laminate, and a method for preparing the copper-clad laminate. By designing the specific composition of the fluoropolymer-based resin composition and utilizing the synergistic effect of high-melting-point organic powder and boron nitride powder, the present invention achieves a resin composition with high thermal conductivity, dielectric properties, and adhesive properties with a relatively small amount of boron nitride, thereby preparing a copper-clad laminate with excellent overall performance.

[0006] To achieve this objective, the present invention adopts the following technical solution:

[0007] In a first aspect, the present invention provides a fluoropolymer-based resin composition, said fluoropolymer-based resin composition comprising, by weight of solids, the following components:

[0008] 20-50 parts of polytetrafluoroethylene emulsion;

[0009] 10-50 parts of high-melting-point organic powder;

[0010] 10-40 parts of boron nitride powder;

[0011] The high-melting-point organic powder has a melting point ≥340℃.

[0012] This invention designs the specific composition of a fluorinated resin-based resin composition and further utilizes the combined effect of high-melting-point organic powder and boron nitride powder to prepare a resin composition with high thermal conductivity, dielectric properties, and adhesive properties with a relatively small amount of boron nitride, thereby preparing a copper-clad laminate with excellent overall performance.

[0013] This invention prepares a resin composition with excellent comprehensive performance by controlling the amount of high-melting-point organic powder within a specific range, and then prepares a copper-clad laminate with excellent comprehensive performance. If the amount of high-melting-point organic powder is too small, the thermal conductivity is not obvious; if the amount of high-melting-point organic powder is too large, the fluorinated resin-based resin cannot form a film, and voids or cracks are prone to appear.

[0014] This invention, by controlling the amount of boron nitride powder within a specific range, prepares a resin composition with high thermal conductivity, dielectric properties, and adhesive properties, thereby producing a copper-clad laminate with excellent overall performance. If the amount of boron nitride powder is too small, the resulting resin composition has poor thermal conductivity; if the amount of boron nitride powder is too large, the resulting resin composition has poor adhesive properties and increases the production cost.

[0015] This invention, by controlling the melting point of the organic powder to be above a specific value, prepares a resin composition with high thermal conductivity, dielectric properties, and adhesive properties, thereby producing a copper-clad laminate with excellent overall performance. If the melting point of the organic powder is below 340°C, the organic powder will melt together with the polytetrafluoroethylene (PTFE) melt, and the powder will flow and mix with the organic powder, resulting in a resin composition with poor thermal conductivity.

[0016] In this invention, the fluorinated resin-based resin composition, by weight of solids, may contain 20, 23, 26, 29, 32, 35, 38, 41, 44, 47, or 50 parts of polytetrafluoroethylene emulsion, etc.

[0017] It should be noted that this invention does not impose any special restrictions on the solid content of the polytetrafluoroethylene (PTFE) emulsion. PTFE emulsions with commonly used solid contents in the art are applicable. The solid content of the PTFE emulsion is exemplary but not limited to: 30-60 wt%, for example, 30 wt%, 35 wt%, 40 wt%, 45 wt%, 50 wt%, 51 wt%, 52 wt%, 53 wt%, 54 wt%, 55 wt%, 56 wt%, 57 wt%, 58 wt%, 59 wt%, or 60 wt%. In this invention, the fluoropolymer-based resin composition, based on solid parts by weight, includes 20-50 parts of PTFE emulsion. This means that the PTFE resin is added in emulsion form, but the amount added refers to 20-50 parts by weight of PTFE resin excluding the solvent in the emulsion.

[0018] The fluorinated resin-based resin composition, by solid weight, may contain 10, 14, 18, 22, 26, 30, 34, 38, 42, 46, or 50 parts of high-melting-point organic powder, etc.

[0019] The fluorinated resin-based resin composition may contain boron nitride in solid parts by weight of 10, 13, 16, 19, 22, 25, 28, 31, 34, 37, or 40 parts, etc.

[0020] The melting point of the high-melting-point organic powder can be 340℃, 345℃, 350℃, 355℃, 360℃, 365℃, 370℃, 375℃, 380℃, 385℃, 390℃, 395℃, or 400℃, etc.

[0021] The following are preferred technical solutions of the present invention, but are not intended to limit the technical solutions provided by the present invention. The purpose and beneficial effects of the present invention can be better achieved and realized through the following preferred technical solutions.

[0022] As a preferred embodiment of the present invention, the high melting point organic powder is selected from PEEK powder and / or PI powder.

[0023] Preferably, the high-melting-point organic powder D 50 Particle size is 10-20 μm (e.g., 10 μm, 11 μm, 12 μm, 13 μm, 14 μm, 15 μm, 16 μm, 17 μm, 18 μm, 19 μm, or 20 μm, etc.), D 100 Particle size ≤100μm (e.g., 30μm, 40μm, 50μm, 60μm, 70μm, 80μm, 90μm or 100μm, etc.).

[0024] In this invention, the overall performance of the fluorinated resin-based resin composition is further optimized by using high-melting-point organic powders with specific particle sizes.

[0025] As a preferred technical solution of the present invention, the boron nitride powder D 50 Particle size is 15-30 μm (e.g., it can be 15 μm, 16 μm, 17 μm, 18 μm, 19 μm, 20 μm, 21 μm, 22 μm, 23 μm, 24 μm, 25 μm, 26 μm, 27 μm, 28 μm, 29 μm, or 30 μm, etc.), D 100 Particle size ≤100μm (e.g., 30μm, 40μm, 50μm, 60μm, 70μm, 80μm, 90μm or 100μm, etc.).

[0026] As a preferred embodiment of the present invention, the number average molecular weight of polytetrafluoroethylene in the polytetrafluoroethylene emulsion is 1 million to 10 million, for example, it can be 1 million, 2 million, 3 million, 4 million, 5 million, 6 million, 7 million, 8 million, 9 million or 10 million, etc.

[0027] In this invention, particle size (including D) 50 D 100 The molecular weight was obtained by testing with a Malvern 3000 laser particle size analyzer; the number-average molecular weight was obtained by differential scanning calorimetry (DSC).

[0028] As a preferred embodiment of the present invention, the fluorinated resin-based resin composition further includes 3-7 parts by weight of other fluorinated resins in solid parts, for example, 3 parts by weight, 3.5 parts by weight, 4 parts by weight, 4.5 parts by weight, 5 parts by weight, 5.5 parts by weight, 6 parts by weight, 6.5 parts by weight, or 7 parts by weight.

[0029] Preferably, the other fluorinated resins are selected from any one or a combination of at least two of the following: perfluoroethylene propylene, tetrafluoroethylene-perfluoroalkoxy vinyl ether copolymer, ethylene-tetrafluoroethylene copolymer, polychlorotrifluoroethylene, or ethylene-chlorotrifluoroethylene copolymer.

[0030] It should be noted that in this invention, other fluorinated resins can be mixed with other components (polytetrafluoroethylene resin, high-melting-point organic powder, boron nitride powder, optional other inorganic fillers, etc.) in the form of other fluorinated resin emulsions to prepare fluorinated resin-based resin compositions. This invention has no restrictions on the solid content of other fluorinated resin emulsions, and exemplary embodiments include, but are not limited to, 30-60 wt%, such as 30 wt%, 35 wt%, 40 wt%, 45 wt%, 50 wt%, 51 wt%, 52 wt%, 53 wt%, 54 wt%, 55 wt%, 56 wt%, 57 wt%, 58 wt%, 59 wt%, or 60 wt%, etc.

[0031] As a preferred embodiment of the present invention, the fluorinated resin-based resin composition further includes 5-40 parts by weight of other inorganic fillers in solid weight, for example, 5 parts by weight, 8 parts by weight, 10 parts by weight, 12 parts by weight, 15 parts by weight, 18 parts by weight, 20 parts by weight, 23 parts by weight, 25 parts by weight, 27 parts by weight, 30 parts by weight, 33 parts by weight, 36 parts by weight, or 40 parts by weight.

[0032] Preferably, the other inorganic fillers are selected from any one or a combination of at least two of the following: silica, hollow glass microspheres, titanium dioxide, alumina, boehmite, boron nitride, silicon nitride, aluminum nitride, strontium titanate, or barium titanate.

[0033] It should be noted that in this invention, other inorganic fillers can be unmodified or modified. The modifier can be selected from any one or a combination of at least two of fluorosilane coupling agents, epoxy silane coupling agents, vinyl silane coupling agents or alkyl silane coupling agents.

[0034] Preferably, in the modified other inorganic fillers, based on the mass percentage of the other inorganic fillers being 100%, the mass percentage of the modifier is 0.01-1.0%, for example, it can be 0.01%, 0.05%, 0.1%, 0.01%, 0.2%, 0.3%, 0.4%, 0.5%, 0.6%, 0.7%, 0.8%, 0.9%, or 1.0%.

[0035] It should be noted that there are no special restrictions on the source of the modified inorganic filler in this invention; it can be a commercially available product or a self-made product. If it is a self-made product, there are no special restrictions in the art on the preparation method of the modified inorganic filler; commonly used methods for modifying inorganic fillers in the art are applicable, including but not limited to:

[0036] Other inorganic fillers, solvents, and modifiers are mixed, a modification reaction is carried out, and the mixture is filtered and dried to obtain the modified inorganic fillers.

[0037] As a preferred embodiment of the present invention, the fluoropolymer-based resin composition further includes a thickener. The thickener is used to adjust the viscosity of the adhesive to 250-300 mPa·s. The amount of thickener is not specifically limited, but is 1-5 parts by weight, for example, 1 part by weight, 1.5 parts by weight, 2 parts by weight, 2.5 parts by weight, 3 parts by weight, 3.5 parts by weight, 4 parts by weight, 4.5 parts by weight, or 5 parts by weight, etc.

[0038] Preferably, the thickener is selected from any one or a combination of at least two of polyoxyethylene distyrene phenyl ether, sodium dodecylbenzene sulfonate, nonylphenol polyoxyethylene ether, sodium dodecyl sulfate, or polydimethylsilane.

[0039] In this invention, there are no special limitations on the preparation method of the fluorinated resin-based resin composition. Commonly used preparation methods in the art are applicable, including but not limited to: casting coating method, paste extrusion rolling method and cutting method.

[0040] All components of the fluorinated resin-based resin composition are mixed to obtain the fluorinated resin-based resin composition.

[0041] Secondly, the present invention provides a fluorinated resin-based dielectric sheet, which is prepared by the following method, the method comprising the following steps:

[0042] The fluorinated resin-based resin composition as described in the first aspect is coated onto a base film, dried, sintered, and the substrate is peeled off to obtain the fluorinated resin-based dielectric sheet.

[0043] Preferably, the drying temperature is 100-260℃, for example, it can be 100℃, 120℃, 140℃, 160℃, 180℃, 200℃, 220℃, 240℃ or 260℃, etc.

[0044] Preferably, the drying time is 10-120 min, for example, it can be 10 min, 20 min, 30 min, 40 min, 50 min, 60 min, 70 min, 80 min, 90 min, 100 min, 110 min or 120 min.

[0045] Preferably, the sintering temperature is 200-400℃, for example, it can be 200℃, 220℃, 240℃, 260℃, 280℃, 300℃, 320℃, 340℃, 360℃, 380℃ or 400℃, etc.

[0046] Preferably, the sintering time is 2-12 hours, for example, 2 hours, 3 hours, 4 hours, 5 hours, 6 hours, 7 hours, 8 hours, 9 hours, 10 hours, 11 hours, or 12 hours.

[0047] Preferably, the sintering atmosphere is an inert gas atmosphere (such as nitrogen or argon).

[0048] Preferably, the thickness of the fluorinated resin-based dielectric sheet is 0.01-10 mm, for example, it can be 0.01 mm, 0.02 mm, 0.05 mm, 0.1 mm, 0.5 mm, 1 mm, 2 mm, 3 mm, 4 mm, 5 mm, 6 mm, 7 mm, 8 mm, 9 mm or 10 mm, etc.

[0049] Thirdly, the present invention provides a copper-clad laminate, the copper-clad laminate comprising at least one fluorinated resin-based dielectric sheet as described in the second aspect and copper foil coated on at least one side of the laminated fluorinated resin-based dielectric sheet.

[0050] Fourthly, the present invention provides a method for preparing a copper-clad laminate as described in the third aspect, the method comprising the following steps:

[0051] The copper-clad laminate is obtained by laminating at least one fluorinated resin-based dielectric sheet as described in the second invention and a copper foil covering at least one side of the laminated fluorinated resin-based dielectric sheet.

[0052] As a preferred embodiment of the present invention, the lamination temperature is 200-400℃, for example, it can be 200℃, 220℃, 240℃, 260℃, 280℃, 300℃, 320℃, 340℃, 360℃, 380℃ or 400℃, etc.

[0053] Preferably, the lamination pressure is 70-250 kg / cm². 2 For example, it could be 70 kg / cm 2 80kg / cm 2 100kg / cm 2 120kg / cm 2 140kg / cm 2 160kg / cm 2 180kg / cm 2 200kg / cm 2 220kg / cm 2 240kg / cm 2 Or 250kg / cm 2 wait.

[0054] Preferably, the lamination time is 2-12 hours, for example, it can be 2 hours, 3 hours, 4 hours, 5 hours, 6 hours, 7 hours, 8 hours, 9 hours, 10 hours, 11 hours or 12 hours.

[0055] Fifthly, the present invention provides a printed circuit board comprising at least one of a fluorinated resin-based dielectric sheet as described in the second aspect or a copper-clad laminate as described in the third aspect.

[0056] Compared with the prior art, the present invention has the following beneficial effects:

[0057] (1) By designing the specific composition of the fluorinated resin-based resin composition, and further by combining high-melting-point organic powder and boron nitride powder, and controlling the amount of each within a specific range, the present invention prepares a resin composition with high thermal conductivity, high dielectric properties and high adhesive properties with a small amount of boron nitride, thereby preparing a copper-clad laminate with excellent comprehensive performance.

[0058] (2) In this invention, the comprehensive performance of the fluorinated resin-based resin composition is further optimized by using high-melting-point organic powder with a specific particle size. Detailed Implementation

[0059] To facilitate understanding of the present invention, the following embodiments are provided. Those skilled in the art should understand that these embodiments are merely illustrative and should not be construed as limiting the scope of the invention.

[0060] The sources of some components in the examples and comparative examples are shown in Table 1 below:

[0061] Table 1

[0062]

[0063]

[0064] Examples 1-11, Comparative Examples 1-5

[0065] Examples 1-11 and Comparative Examples 1-5 each provide a fluorinated resin-based resin composition. The specific composition of the fluorinated resin-based resin composition is shown in Tables 2-3 below. The amounts of each component in Tables 2-3 are all by weight. In Tables 2-3, PTFE emulsion actually represents the weight of PTFE in the PTFE emulsion; other fluorinated resins actually represent the weight of other fluorinated resins in other fluorinated resin dispersions.

[0066] The preparation method of the fluorinated resin-based resin composition is as follows:

[0067] The fluorinated resin-based resin composition was mixed, and a thickener (polyoxyethylene distyryl phenyl ether, purchased from Kao Corporation, brand name: EMULGEN A-60) was added to it under stirring until the viscosity reached 270 mPa·s. The mixture was stirred for 2 hours to obtain the fluorinated resin-based resin composition.

[0068] Fluoropolymer-based dielectric sheets were prepared using the fluoropolymer-based resin compositions provided in the examples and comparative examples, respectively. The specific preparation methods are as follows:

[0069] A fluoropolymer-based resin composition was coated onto one side surface of a PI film using a coating machine to obtain a resin layer with a coating thickness of 129 μm, thus obtaining a coated PI film. The coated PI film was placed in a vacuum oven at 100°C and baked for 1 hour to remove moisture. It was then baked at 260°C for 1 hour to remove the thickener and at 350°C for 10 minutes. After cooling, the resin layer was peeled off from the PI film to obtain a fluoropolymer-based dielectric sheet with uniform thickness.

[0070] Copper-clad laminates are further prepared using the fluorinated resin-based dielectric sheets obtained from the fluorinated resin-based resin compositions provided in the above examples and comparative examples, as follows:

[0071] Two 129μm thick fluorinated resin-based dielectric sheets are stacked together, with a size of 250×250mm. A 1OZ thick copper foil (purchased from Suzhou Futian) is then placed on both sides of the stacked resin layer for lamination. A pressure of 400PSI is applied, and the maximum temperature and holding time are 380℃ / 60min to obtain the copper-clad laminate.

[0072] The performance of copper-clad laminates is evaluated using the following specific methods:

[0073] Film-forming properties: Visually inspect the film-forming properties of the fluorinated resin-based dielectric sheet. Observe whether there are cracks in the fluorinated resin-based dielectric sheet. No cracks are "good". A few cracks that do not affect the peeling and film formation are "good". Many cracks that prevent the peeling of a complete film are "poor".

[0074] Thermal conductivity: tested according to ASTM D5470-2017 method.

[0075] Peel strength: The test was conducted using a JFM012 copper foil peel strength tester under the following conditions: state A, foil width of 3 mm, and tensile angle of 90°±5° with respect to the dielectric layer plane.

[0076] The performance test results are shown in Tables 2 and 3 below:

[0077] Table 2

[0078]

[0079] Table 3

[0080]

[0081]

[0082] As can be seen from the above, this invention, through the design of the specific composition of the fluorinated resin-based resin composition, and further through the synergistic effect of high-melting-point organic powder and boron nitride powder, and by controlling the amount of each within a specific range, has prepared a resin composition with high thermal conductivity, dielectric properties, high adhesion, and good film-forming properties with a relatively small amount of boron nitride. This results in the preparation of a copper-clad laminate with excellent overall performance, exhibiting a thermal conductivity of 1.2-2.2 W / mK and a peel strength ≥0.6 N / mm, specifically 0.6-1.2 N / mm.

[0083] As can be seen from Examples 3-7, in this invention, the comprehensive performance of the fluorinated resin-based resin composition is further optimized by using high-melting-point organic powder with a specific particle size. Its thermal conductivity is 1.7-2.2 W / mK and its peel strength is ≥0.6 N / mm.

[0084] As can be seen from Examples 3, 8-11, and Comparative Examples 1-4, the present invention obtains a resin composition with excellent comprehensive performance by controlling the amount of high melting point organic powder and boron nitride powder within a specific range, and then obtains a copper clad laminate with excellent comprehensive performance.

[0085] As can be seen from Example 3 and Comparative Example 5, the present invention uses high-melting-point organic powder to prepare a resin composition with excellent comprehensive performance, and then prepares a copper-clad laminate with excellent comprehensive performance.

[0086] In summary, by designing the specific composition of the fluorinated resin-based resin composition, this invention has prepared a resin composition with high thermal conductivity, dielectric properties, high adhesion, and good film-forming properties with a relatively small amount of boron nitride, thereby obtaining a copper-clad laminate with excellent overall performance.

[0087] The applicant declares that the detailed process flow of this invention is illustrated by the above embodiments, but this invention is not limited to the above detailed process flow, that is, it does not mean that this invention must rely on the above detailed process flow to be implemented. Those skilled in the art should understand that any improvements to this invention, equivalent substitutions of raw materials for the product of this invention, addition of auxiliary components, and selection of specific methods, etc., all fall within the protection scope and disclosure scope of this invention.

Claims

1. A fluorinated resin-based resin composition, characterized in that, The fluoropolymer-based resin composition comprises the following components in parts by weight of solids: 20-50 parts of polytetrafluoroethylene emulsion; 10-50 parts of high-melting-point organic powder; 10-40 parts of boron nitride powder; The high-melting-point organic powder has a melting point ≥340℃.

2. The fluorinated resin-based resin composition according to claim 1, characterized in that, The high-melting-point organic powder is selected from PEEK powder and / or PI powder; Preferably, the high-melting organic powder has a D 50 Particle size 10-20 μm, D 100 Particle size < 100 μm.

3. The fluorinated resin-based resin composition according to claim 1 or 2, characterized in that, The boron nitride powder has a D 50 The particle size is 15-30 μm, D 100 The particle size is ≤ 100 μm.

4. The fluorinated resin-based resin composition according to any one of claims 1-3, characterized in that, The polytetrafluoroethylene in the polytetrafluoroethylene emulsion has a number-average molecular weight of 1 million to 10 million.

5. The fluorinated resin-based resin composition according to any one of claims 1-4, characterized in that, The fluorinated resin-based resin composition further includes 3-7 parts by weight of other fluorinated resins based on solid weight; Preferably, the other fluorinated resins are selected from any one or a combination of at least two of the following: perfluoroethylene propylene, tetrafluoroethylene-perfluoroalkoxy vinyl ether copolymer, ethylene-tetrafluoroethylene copolymer, polychlorotrifluoroethylene, or ethylene-chlorotrifluoroethylene copolymer.

6. The fluorinated resin-based resin composition according to any one of claims 1-5, characterized in that, The fluorinated resin-based resin composition further includes 5-40 parts by weight of other inorganic fillers based on solid weight; Preferably, the other inorganic fillers are selected from any one or a combination of at least two of the following: silica, hollow glass microspheres, titanium dioxide, alumina, boehmite, boron nitride, silicon nitride, aluminum nitride, strontium titanate, or barium titanate.

7. A fluoropolymer-based dielectric sheet, characterized in that, The fluorinated resin-based dielectric sheet is prepared by the following method, which includes the following steps: The fluorinated resin-based resin composition as described in any one of claims 1-6 is coated onto a base film, dried, sintered, and the substrate is peeled off to obtain the fluorinated resin-based dielectric sheet. Preferably, the thickness of the fluorinated resin-based dielectric sheet is 0.01-10 mm.

8. A copper-clad laminate, characterized in that, The copper-clad laminate includes at least one fluorinated resin-based dielectric sheet as described in claim 7, and copper foil covering at least one side of the laminated fluorinated resin-based dielectric sheet.

9. A method for preparing a copper-clad laminate as described in claim 8, characterized in that, The preparation method includes the following steps: The copper-clad laminate is obtained by laminating at least one fluorinated resin-based dielectric sheet as described in claim 7 and a copper foil covering at least one side of the laminated fluorinated resin-based dielectric sheet.

10. A printed circuit board, characterized in that, The printed circuit board includes at least one of the fluoropolymer-based dielectric sheet as described in claim 7 or the copper-clad laminate as described in claim 8.

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