Resin composition, prepreg comprising same, metal laminate, laminate, and printed circuit board

Abstract

The present invention relates to a resin composition comprising: a perfluoroalkoxy alkane (PFA); an elastomer selected from one or more selected from the group consisting of a styrene-based elastomer and a fluorine-based elastomer; and a hollow inorganic filler having a porosity of 60 to 90%; a prepreg comprising the same; a metal laminate; a laminate; and a printed circuit board.

Description

Technical Field

[0001] This invention relates to a resin composition having low thermal expansion, low dielectric properties and high heat resistance, as well as prepregs, metal laminates, laminates and printed circuit boards containing the same. Background Technology

[0002] Recently, with the advent of the era of hyper-connected intelligence, including artificial intelligence, big data, and autonomous vehicles, the development and popularization of various electronic devices such as smartphones have accelerated, leading to a shift from existing 4G LTE communication to next-generation (5G, 6G) communication capable of wirelessly transmitting high-speed, high-capacity data. In particular, with the widespread adoption of autonomous vehicles, smart cities, and smart factories, high-frequency or ultra-high-frequency communication is being used to achieve latency-free transmission and reception of large amounts of data. Current frequencies are gradually shifting from sub-6 GHz (4.5 GHz) to 28 and 40 GHz, and ultra-high frequencies above 100 GHz are expected to be used in the future. However, the higher the frequency band used in communication / electronic devices, the greater the transmission loss of electrical signals, potentially leading to problems such as overheating, signal attenuation, and latency.

[0003] To address this, materials with low dielectric constants and low dielectric loss tangents have been developed to reduce transmission losses. For example, polyphenylene ether, liquid crystal polymers (LCP), or modified polyimide (MPI) that can be used for high-frequency applications have been applied to printed circuit boards. However, these materials suffer from poor processability, such as low heat resistance or adhesion to copper foil, or difficulties in improving dielectric properties. Summary of the Invention

[0004] Technical issues

[0005] The present invention aims to provide a resin composition with a low coefficient of thermal expansion (CTE), low dielectric properties, excellent heat resistance and resin flowability, and capable of manufacturing prepregs through a roll-to-roll process.

[0006] Furthermore, the present invention aims to provide a prepreg, metal laminate, laminate, and printed circuit board that can be used in the high-frequency to ultra-high-frequency bands using the aforementioned resin composition.

[0007] Technical solution

[0008] To achieve the above objectives, the present invention provides a resin composition comprising: a perfluoroalkoxyalkane (PFA); one or more elastomers selected from the group consisting of styrene-based elastomers and fluorine-based elastomers; and a hollow inorganic filler having a porosity of 60 to 90%.

[0009] According to one example, the hollow inorganic filler can have a relative permittivity (D) in the range of 1 to 3 at 25°C and 10 GHz. k ).

[0010] According to another example, the average particle size (D50) of the hollow inorganic filler can be in the range of 0.5 to 50 μm.

[0011] According to yet another example, the hollow inorganic filler may contain hollow silica.

[0012] According to another example, the perfluoroalkoxyalkane may contain a tetrafluoroethylene repeating unit and a perfluoroether repeating unit, wherein the molar ratio of the tetrafluoroethylene repeating unit to the perfluoroether repeating unit may be in the range of 1:10 to 1:10000.

[0013] According to yet another example, the resin composition may further contain an organic solvent.

[0014] According to another example, based on the total amount of the resin composition, the resin composition may contain: 40 to 80% by weight of perfluoroalkoxyalkane; 0.1 to 10% by weight of elastomer; and 10 to 40% by weight of hollow inorganic filler.

[0015] According to yet another example, the cured resin composition can have a relative permittivity (Di) in the range of 1.5 to 2.0 at 25°C and 10 GHz. k ).

[0016] Furthermore, the present invention provides a prepreg comprising the aforementioned resin composition.

[0017] According to one example, the prepreg may have a coefficient of thermal expansion of less than 20 ppm / °C, and a relative permittivity (D0) at 25°C and 10 GHz. k () is below 2.0.

[0018] Furthermore, the present invention provides a method for manufacturing a roll of prepreg, comprising: coating a first film, which is supplied from a first supply roller wound with a first film and continuously travels, with the aforementioned resin composition applied and dried to continuously form a first insulating member comprising a resin layer and a first film; coating a second film, which is supplied from a second supply roller wound with a second film and continuously travels, with the aforementioned resin composition applied and dried to continuously form a second insulating member comprising a resin layer and a second film; and heating / pressurizing a fiber substrate, which is supplied from a third supply roller wound with a fiber substrate and continuously travels, on both sides of the fiber substrate, such that the resin layer of each insulating member is in contact with the surface of the fiber substrate, while using a pair of heating rollers.

[0019] Furthermore, the present invention provides a metal laminate comprising the aforementioned resin composition.

[0020] Furthermore, the present invention provides a method for manufacturing a rolled metal laminate, comprising: coating a first metal foil, which is supplied from a fourth supply roller wound with a first metal foil and continuously travels, with the aforementioned resin composition applied and dried to continuously form a first unit component comprising a resin layer and a first metal foil; coating a second metal foil, which is supplied from a fifth supply roller wound with a second metal foil and continuously travels, with the aforementioned resin composition applied and dried to continuously form a second unit component comprising a resin layer and a second metal foil; and heating / pressurizing a fiber substrate, which is supplied from a sixth supply roller wound with a fiber substrate and continuously travels, on both sides of the fiber substrate, such that the resin layer of each metal unit component is in contact with the surface of the fiber substrate, while simultaneously heating / pressurizing with a pair of heating rollers.

[0021] Furthermore, the present invention provides a printed circuit board comprising the aforementioned resin composition.

[0022] The effects of the invention

[0023] The resin composition of the present invention has excellent processability when applied to printed circuit boards due to its low coefficient of thermal expansion (CTE), high glass transition temperature (Tg), low dielectric constant, and excellent resin flowability. It can also improve the low dielectric loss, heat resistance, and low thermal expansion characteristics of printed circuit boards.

[0024] Furthermore, the resin composition of the present invention can be used to manufacture prepregs via a roll-to-roll process.

[0025] Therefore, the resin composition of the present invention can be advantageously used as a component of a printed circuit board for mobile communication devices or their base station devices, network-related electronic devices such as servers and routers, and various electrical and electronic devices such as large computers that process ultra-high frequency signals above 100 GHz. Detailed Implementation

[0026] The present invention will now be described.

[0027] Unless otherwise defined, all terms (including technical and scientific terms) used in this specification shall be used in the sense that would be commonly understood by one of ordinary skill in the art to which this invention pertains. Furthermore, unless explicitly defined otherwise, terms as defined in commonly used dictionaries should not be interpreted ideally or excessively.

[0028] Throughout the specification, when a part is referred to as "containing" a certain component, unless otherwise stated, it should be understood as an open-ended term implying that it may also contain other components, rather than excluding the possibility of other components.

[0029] Furthermore, throughout the instruction manual, "above" or "above" means not only the case of being directly above or below the object part, but also the case of being separated by other parts, and does not necessarily mean being above based on the direction of gravity.

[0030] In addition, the terms "first" and "second" used in this specification do not indicate any arbitrary order or importance, but are used to distinguish the constituent elements from each other.

[0031] <Resin Composition>

[0032] To minimize propagation loss in 5G-6G communication bands, prepregs have traditionally been manufactured by mixing inorganic fillers into fluoropolymers. However, even with a relatively high permittivity (D...), this process... k ) and dielectric loss tangent (D f The low relative permittivity (D) of fluoropolymers due to the inorganic fillers mixed with them... k While high dielectric constants still present limitations in achieving extremely low dielectric properties, insufficient inorganic fillers can lead to an increased coefficient of thermal expansion (CTE) and reduced environmental reliability. Therefore, a certain amount of inorganic fillers must be used.

[0033] To address the aforementioned problems, this invention aimed to utilize a resin composition comprising, in addition to perfluoroalkoxyalkane (PFA) and inorganic fillers, one or more elastomers selected from the group consisting of styrene-based elastomers and fluoroelastomers. However, the relative permittivity (D) of PFA... k The relative permittivity (D) of inorganic fillers commonly used in this field is 2.1, while the relative permittivity (D) is 2.1. k The relative permittivity (D) is higher than that of PFA. k Therefore, there are limitations when reducing the relative permittivity of the resin layer to below about 2.0.

[0034] In response, this invention has found that when perfluoroalkoxyalkane (PFA) and one or more elastomers selected from the group consisting of styrene-based and fluorine-based elastomers are used together with hollow inorganic fillers, a low coefficient of thermal expansion (CTE) and low dielectric properties can be achieved. However, this invention recognizes that if the porosity of the hollow inorganic filler is too small, the effect of reducing the dielectric constant may be small; while if the porosity of the hollow inorganic filler is too large, the hollow inorganic filler may break during the lamination process, leading to an increase in the dielectric constant. Therefore, this invention comprises perfluoroalkoxyalkane (PFA), one or more elastomers selected from the group consisting of styrene-based and fluorine-based elastomers, and hollow inorganic fillers, and includes hollow inorganic fillers with a porosity controlled in the range of 60% to 90%.

[0035] Specifically, the relative permittivity (D) of the aforementioned hollow inorganic filler itself... k The relative permittivity (D) is approximately 1 to 3. When such hollow inorganic fillers are mixed with PFA, they will have a relative permittivity (D) of approximately 1.5 to 2.0. kTypically, signal transmission loss is proportional not only to dielectric loss but also to dielectric constant. Therefore, excessive signal transmission loss occurring in the ultra-high frequency region above 100 GHz can be reduced by the extremely low dielectric resin composition of this invention, which combines the aforementioned hollow inorganic filler and PFA. Furthermore, a low dielectric constant offers the advantage of improved ease of design for circuits such as antennas. PFA has a melting point of approximately 300°C or higher, and as a high-melting-point thermoplastic material, it requires high-temperature molding processes. In contrast, the shell material of the hollow inorganic filler is an inorganic material that is stable even at high temperatures, maintaining its phase even during high-temperature molding processes, thus replacing existing inorganic fillers. Consequently, the resin composition of this invention, due to its low coefficient of thermal expansion (CTE), high glass transition temperature (Tg), low dielectric constant, and excellent resin flowability, exhibits excellent processability when applied to printed circuit boards, and can improve the low dielectric loss, heat resistance, and low thermal expansion characteristics of printed circuit boards. Furthermore, the resin composition of this invention can be used to manufacture prepregs even without a high-temperature molding process via a roll-to-roll process. Therefore, the resin composition of the present invention can be advantageously used as a component of a printed circuit board for mobile communication devices or their base station devices, network-related electronic devices such as servers and routers, and various electrical and electronic devices such as large computers that process ultra-high frequency signals above 100 GHz.

[0036] According to one example, the resin composition of the present invention comprises: (a) a perfluoroalkoxyalkane (PFA); (b) one or more elastomers selected from the group consisting of styrene-based elastomers and fluorine-based elastomers; and (c) a hollow inorganic filler having a porosity of 60 to 90%.

[0037] According to another example, in addition to the aforementioned components, the resin composition of the present invention may further comprise one or more components selected from the group consisting of curing agents, initiators and solvents.

[0038] The components of the resin composition of the present invention will be described below.

[0039] (a) Perfluoroalkoxyalkanes

[0040] In the resin composition of the present invention, the perfluoroalkoxyalkane is a type of fluorine-based resin containing fluorine (F), which enables the resin layer to achieve low dielectric constant and low dielectric loss characteristics. Such perfluoroalkoxyalkane is a solid particulate filler at room temperature, which can be incorporated into the resin layer by elastomer bonding during resin composition drying, and melted together with the elastomer in a hot pressing process at approximately 310°C or higher to form the matrix component of the resin layer. Furthermore, unlike fluororesin dispersions, perfluoroalkoxyalkane does not contain dispersants, thus improving the heat resistance and adhesion of the gold metal laminate.

[0041] According to one example, the aforementioned perfluoroalkoxyalkane contains a repeating tetrafluoroethylene (C2F4) unit and a perfluoroether (C2F3OR) unit. 1 , where R 1 C1~C 12 (perfluoroalkyl) repeating unit.

[0042] At this point, the ratio of the tetrafluoroethylene repeating unit to the perfluoroether repeating unit is not particularly limited; for example, the molar ratio can be 1:10 to 1:10,000. However, when the ratio of the tetrafluoroethylene repeating unit to the perfluoroether repeating unit is within the aforementioned range, the perfluoroalkoxyalkane can have a relative permittivity (D0) of about 2 to 3 at 25°C and 10 GHz. k and a dielectric loss tangent of approximately 0.0001 to 0.001 (D f Here, the relative permittivity (D) of perfluoroalkoxyalkanes is... k ) and dielectric loss tangent (D f The measurements were performed at 25°C and 10 GHz using the SPDR method (IEC 61189-2-721).

[0043] The weight-average molecular weight (Mw) of the aforementioned perfluoroalkoxyalkanes can be approximately 1,000,000 to 10,000,000, but is not limited to this.

[0044] The melt flow rate (MFR) of the above-mentioned perfluoroalkoxyalkanes, measured according to ISO 1133-1 test method at approximately 372°C and approximately 2 kg, can be approximately 1 to 30 g / 10 min.

[0045] The more uniformly such perfluoroalkoxyalkanes are dispersed in the resin composition, the better the dielectric properties of the resin composition are improved. Furthermore, it is suitable for manufacturing prepregs and metal laminates through a simple coating process without high-temperature extrusion molding and high-temperature sintering, and is also suitable for manufacturing prepregs and metal laminates through a roll-to-roll process. Therefore, in this invention, it is preferable to adjust the shape, size (average particle size), and content of the perfluoroalkoxyalkanes within specific ranges.

[0046] Specifically, perfluoroalkoxyalkanes can be spherical, plate-like, dendritic, conical, pyramidal, or amorphous. Among these, spherical perfluoroalkoxyalkanes have the smallest surface area, which improves the processing characteristics of the resin composition and imparts isotropic properties to the resin layer.

[0047] Furthermore, the average particle size (D50) of the perfluoroalkoxyalkane can range from about 0.1 to 100 μm, specifically from about 1 to 70 μm, and more specifically from about 5 to 50 μm. If the perfluoroalkoxyalkane has the aforementioned average particle size, it is uniformly dispersed in the resin composition without agglomeration, thus making it suitable for fabricating resin layers for printed circuit boards. Here, the average particle size (D50) of the perfluoroalkoxyalkane can be determined according to ASTM D4464.

[0048] In the resin composition of the present invention, the content of perfluoroalkoxyalkane is not particularly limited. However, if the content of perfluoroalkoxyalkane is too low, the adhesion between the resin layer and other substrates (e.g., fiber substrates of prepregs, metal foils of metal laminates) decreases, which may lead to delamination between the resin layer and other substrates. On the other hand, if the content of perfluoroalkoxyalkane is too high, the content of inorganic fillers is relatively low, which may lead to an increase in the coefficient of thermal expansion (CTE) of the resin layer. Therefore, it is appropriate to adjust the content of perfluoroalkoxyalkane to about 40 to 80% by weight, specifically to about 50 to 80% by weight, and more specifically to about 60 to 80% by weight, based on the total amount (100% by weight) of the resin composition. Under these conditions, the resin composition of the present invention can form a resin layer with excellent heat resistance and adhesion, and low dielectric constant and dielectric loss.

[0049] (b) Elastomers

[0050] In the resin composition of the present invention, the elastomer is an adhesive resin capable of bonding perfluoroalkoxyalkanes and hollow inorganic fillers. As an example, the resin composition may contain a thermoplastic elastomer. In this case, the thermoplastic elastomer melts under high temperature and pressure, thereby readily forming a resin layer.

[0051] The elastomer of the present invention comprises one or more selected from the group consisting of fluorinated elastomers and styrene elastomers. The fluorinated and styrene elastomers not only readily bond hollow inorganic fillers and perfluoroalkoxyalkanes, but also exhibit low dielectric properties. Specifically, the elastomer of the present invention has a dielectric loss tangent (D0) of 0.0005 to 0.0020 at 25°C and 10 GHz. f Furthermore, the elastomer of the present invention has a relative permittivity (D) of 2.0 to 3.0 at 25°C and 10 GHz. k Here, the relative permittivity (D) of the elastomer is... k ) and dielectric loss tangent (D f The measurements were performed at 25°C and 10GHz according to the SPDR method (IEC61189-2-721).

[0052] When the elastomer of the present invention, which has a low dielectric loss tangent and a low dielectric constant, is used as an adhesive, a resin layer with low dielectric loss can be easily formed by directly coating the resin composition onto a film or metal foil and drying it without a high-temperature extrusion molding process or a high-temperature firing process.

[0053] The fluorinated elastomer of the present invention is a type of thermoplastic elastomer, which contains more than one fluorine (F) in at least one repeating unit and can be dissolved in organic solvents (e.g., MEK).

[0054] Such fluorinated elastomers exhibit dielectric loss tangents of 0.0005 to 0.0020 at 25°C and 10 GHz. f and a relative permittivity (D) of 2.0 to 3.0. k Furthermore, it possesses a low modulus. Here, the relative permittivity (D0) of fluorine-based elastomers is... k ) and dielectric loss tangent (D f The measurements were performed at 25°C and 10 GHz using the SPDR method (IEC 61189-2-721).

[0055] The fluoroelastomers that can be used in this invention are fluororubbers (FKM), specifically copolymers containing two or more of vinylidene fluoride (VDF), hexafluoropropylene (HFP), and tetrafluoroethylene (TFE). Depending on the number of monomers, they can be binary or ternary copolymers, such as VDF-HFP copolymers, VDF-HFP-TFE copolymers, etc., but are not limited to these. They can be used alone or in combination of two or more.

[0056] The fluorine (F) content in the fluorinated elastomer of the present invention is not particularly limited, but when the fluorine content per molecule of the fluorinated elastomer is in the range of about 60 to 80% by weight, the dielectric loss tangent (Dt) of the fluorinated elastomer at 25°C and 10 GHz is [value missing]. f It can be in the range of approximately 0.0005 to 0.0020.

[0057] The styrene-based elastomer of the present invention, as a thermoplastic elastomer, is an elastomer containing one or more styrene groups within at least one repeating unit. Such a styrene-based elastomer can exhibit a dielectric loss tangent (Dt) of 0.0005 to 0.0020 at 25°C and 10 GHz. f and a relative permittivity (D) of 2.0 to 3.0. k Here, the relative permittivity (D) of styrene-based elastomers... k ) and dielectric loss tangent (D f The measurements were performed at 25°C and 10 GHz using the SPDR method (IEC 61189-2-721).

[0058] The styrene-based elastomers that can be used in this invention can be styrene mixed with C2~C364. 10 These are copolymer elastomers of aliphatic unsaturated hydrocarbons. Specifically, examples of styrene-based elastomers include styrene-butadiene-styrene binary copolymers (SBS), styrene-ethylene-butene-styrene terpolymers (SEBS), styrene-ethylene-ethylene-propylene-styrene terpolymers (SEEPS), styrene-isoprene-styrene binary copolymers, and styrene-ethylene-propylene-styrene terpolymers, but are not limited to these. They can be used alone or in combination of two or more.

[0059] The styrene content in the styrene-based elastomer of the present invention is not particularly limited, but when the styrene content per molecule of the styrene-based elastomer is in the range of about 10 to 40% by weight, the dielectric loss tangent (Dt) of the styrene-based elastomer at 25°C and 10 GHz is [value missing]. f It can be in the range of approximately 0.0005 to 0.0020.

[0060] The melt flow rate (MFR) of the elastomer of the present invention, measured according to ISO 1133-1 test method at 230°C and 2 kg, can be less than about 0.1 g / 10 min.

[0061] Furthermore, the viscosity of the solution in which 5 wt% of the elastomer of the present invention is dissolved in toluene is about 50 to 100 cps. Therefore, the viscosity of the resin composition of the present invention is adjusted to be in the range of about 150 to 500 cps, thereby improving processability when manufacturing prepregs or metal laminates.

[0062] The elastomer of the present invention has a thermal decomposition temperature (Td) of up to about 350°C. Therefore, the resin composition of the present invention can form a resin layer with excellent thermal stability at high temperatures.

[0063] In the resin composition of the present invention, the content of the elastomer is not particularly limited, but may range from about 0.1% to 10% by weight, specifically from about 1% to 8% by weight, and more specifically from about 1% to 5% by weight, based on the total amount of the resin composition. When the content of the elastomer is less than about 0.1% by weight, the effect of bonding the hollow inorganic filler and the perfluoroalkoxyalkane may be reduced; while when the content of the elastomer is greater than about 10% by weight, the adhesion of the resin layer to other substrates (e.g., fiber substrates, metal foils) may be reduced, which may lead to the resin layer separating (peeling off) from other substrates during the manufacture and use of prepregs and metal laminates.

[0064] (c) Hollow inorganic packing

[0065] In the resin composition of the present invention, the hollow inorganic filler is a filler having empty spaces (pores) inside the particles. Like conventional inorganic fillers, such hollow inorganic fillers can reduce the difference in coefficient of thermal expansion (CTE) between the resin layer and other layers, thereby improving the warpage characteristics, low expansion, mechanical strength, and low stress of the final product.

[0066] However, because hollow inorganic fillers contain air within the particles, the size of the internal air layer can affect the dielectric constant of the resin layer. Therefore, as mentioned above, this invention comprises hollow inorganic fillers with a porosity in the range of 60% to 90%. Here, porosity can be calculated as (d / D). 3 × 100 (%) (where D is the overall diameter (outer diameter) of the particle, measured using a particle size analyzer; d is the diameter (inner diameter) of the internal air layer, calculated by observing the cross-section of the hollow inorganic filler with an electron microscope and measuring the shell thickness). If the porosity of the hollow inorganic filler is less than 60%, the effect of reducing the dielectric constant may be small; while if the porosity of the hollow inorganic filler is greater than 90%, the hollow inorganic filler may break during the lamination process, which may lead to an increase in the dielectric constant.

[0067] The average particle size (D50) of such hollow inorganic fillers can range from approximately 0.5 to 50 μm, specifically from approximately 1 to 25 μm. Here, the average particle size (D50) of the hollow inorganic fillers can be determined according to ASTM D4464.

[0068] Furthermore, hollow inorganic fillers can exhibit a relative permittivity (Di) in the range of 1 to 3 at 25°C and 10 GHz. k Here, the relative permittivity (D) of the hollow inorganic filler is... k The measurements were performed at 25°C and 10 GHz using the SPDR method (IEC 61189-2-721).

[0069] The composition of the above-mentioned hollow inorganic filler can be silicon dioxide, aluminum oxide, calcium carbonate, magnesium carbonate, magnesium oxide, calcium silicate, titanium oxide, antimony oxide, aluminum borate, barium titanate, strontium titanate, calcium titanate, magnesium titanate, bismuth titanate, titanium oxide, barium zirconate, calcium zirconate, boron nitride, silicon nitride, etc., among which silicon dioxide with high physical strength and low coefficient of thermal expansion is preferred.

[0070] According to one example, the aforementioned hollow inorganic filler can be hollow silica. In addition to silica (SiO2), such hollow silica can also contain metallic elements (e.g., boron, sodium, calcium, aluminum, etc.), specifically composed of borosilicates, and more specifically containing approximately 75-85% by weight of silica, approximately 10-15% by weight of boron oxide, approximately 1-6% by weight of sodium oxide, and approximately 1-3% by weight of aluminum oxide.

[0071] The shape of the hollow inorganic filler can be spherical particles, but it can also be an amorphous particle.

[0072] Furthermore, the aforementioned hollow inorganic filler can be surface-treated with a surface treatment agent. There are no particular limitations on the surface treatment agent, as long as it is generally known in the art, such as silane coupling agents. In this case, based on 100 parts by weight of the hollow inorganic filler, the content of the silane coupling agent can be approximately 0.01 to 20 parts by weight, specifically approximately 0.1 to 10 parts by weight, and more specifically approximately 0.1 to 5 parts by weight.

[0073] The silane coupling agents that can be used in this invention are not particularly limited as long as they are generally known in the art, such as phenyl-based, vinyl-based, epoxy-based, methacryloxy-based, amino-based, mercapto / sulfide-based, and urea-based silane coupling agents, which can be used alone or in combination of two or more. Such silane coupling agents can improve the adhesion between the hollow inorganic filler and other components during the curing of the resin composition.

[0074] As an example, the silane coupling agent can be a phenyl-based silane coupling agent, specifically phenylsilane, trimethylphenylsilane, triethoxyphenylsilane, methoxydimethylphenylsilane, isopropylphenylsilane, etc., which can be used alone or in combination of two or more. In this case, due to its excellent compatibility with non-functional fluoropolymers, it is possible to further improve moisture absorption, heat resistance, and processability while reducing the dielectric constant and dielectric loss tangent.

[0075] The aforementioned silane coupling agent can not only be used for surface treatment of hollow inorganic fillers, but can also be further added as a component of a resin composition. In this case, based on the total amount of the resin composition, the content of the silane coupling agent can be approximately 0.0001 to 10% by weight, specifically approximately 0.01 to 5% by weight, and more specifically approximately 0.1 to 3% by weight. In this situation, the silane coupling agent improves the dispersibility of the inorganic filler, thereby improving the dielectric properties of the cured resin composition (e.g., a resin layer) or the prepreg using the resin composition.

[0076] In the resin composition of the present invention, the content of the hollow inorganic filler can be in the range of about 10 to 40% by weight, specifically in the range of about 15 to 30% by weight, based on the total amount of the resin composition. If the content of the hollow inorganic filler is less than about 10% by weight, the effect of reducing the dielectric constant may not be significant; while if the content of the hollow inorganic filler is greater than about 40% by weight, the moldability of the resin composition may decrease.

[0077] (d) Organic solvents

[0078] The resin composition of the present invention may further comprise an organic solvent. In this case, the resin composition may be in the form of a resin varnish. In this case, the resin composition may be dissolved or dispersed in an organic solvent.

[0079] The organic solvents that can be used in this invention are not particularly limited as long as they can dissolve the aforementioned elastomer. Examples of such organic solvents include: aromatic compounds such as toluene, xylene, and ethylbenzene; alcohol compounds such as methanol, ethanol, butanol, and isobutanol; ketone compounds such as acetone, methyl isobutyl ketone, methyl pentyl ketone, cyclohexanone, isophorone, and N-methylpyrrolidone; and ester compounds such as ethyl acetate, butyl acetate, and methyl cellolytic acetate, but are not limited thereto. They can be used alone or in combination.

[0080] The content of the organic solvent can be used in accordance with the content known in the art, and can be adjusted so that the total amount of the resin composition is 100% by weight. As an example, based on 100 parts by weight of the resin composition (wherein excluding the organic solvent), it can be in the range of about 20 to 80 parts by weight, specifically in the range of about 30 to 70 parts by weight.

[0081] On the other hand, in addition to the aforementioned perfluoroalkoxyalkanes, elastomers, and hollow inorganic fillers, the resin composition of the present invention may, as needed and without impairing the physical properties of the composition, further contain additives known in the art, such as flame retardants, other thermosetting or thermoplastic resins, ultraviolet absorbers, antioxidants, polymerization initiators, dyes, pigments, dispersants, thickeners, leveling agents, colorants, etc. The content of the additives may be used in accordance with the contents known in the art, for example, based on the total amount of the resin composition, it may be from about 0.0001 to 10% by weight.

[0082] The viscosity of the resin composition of the present invention can be adjusted according to the type or content of perfluoroalkoxyalkane, elastomer and hollow inorganic filler in the composition, for example, it can be about 150 to 500 cps. According to one example, when the resin composition has the aforementioned viscosity, the resin layer can be directly formed on a film or metal foil by roll-to-roll coating.

[0083] As described above, the resin composition of the present invention contains perfluoroalkoxyalkanes, elastomers, and hollow inorganic fillers with excellent electrical properties in the high-frequency to ultra-high-frequency bands, thus providing a high-frequency, low-dielectric-constant / low-dielectric-loss resin composition suitable for manufacturing prepregs, sheets, films, tapes, laminates, or printed wiring substrates. Furthermore, the resin composition of the present invention exhibits excellent coefficient of thermal expansion (CTE), heat resistance, and resin flowability. Moreover, when manufacturing prepregs and metal laminates, the resin composition of the present invention can easily form prepregs and metal laminates containing a resin layer with low dielectric constant, low dielectric loss, and excellent stability in signal transmission loss by directly coating and drying a metal foil, without the need for film-forming processes (paste extrusion, calendering) and high-temperature sintering processes. Furthermore, the resin composition of the present invention can be applied to substrates made of various materials, such as polyimide (PI) substrates, to manufacture flexible metal laminates.

[0084] According to one example, the cured resin composition (resin layer) of the present invention can have a relative permittivity (Dk) in the range of about 1.5 to 2.0 at 25°C and 10 GHz. k Here, the relative permittivity (D) of the cured material is... kThe measurements were performed at 25°C and 10 GHz using the SPDR method (IEC61189-2-721).

[0085] <Prepregs and their manufacturing methods>

[0086] On the other hand, the present invention provides a prepreg comprising the aforementioned resin composition.

[0087] The prepreg of the present invention is a fiber-reinforced composite material, which, according to one example, may comprise: a fiber substrate; and a semi-cured product of the aforementioned resin composition impregnated in the fiber substrate. Here, the semi-cured product of the resin composition is a state in which the resin composition is not fully cured, for example, it may be a B-stage state in the resin curing process.

[0088] According to another example, the prepreg of the present invention comprises: a plurality of resin layers (e.g., a first resin layer and a second resin layer); and a fiber substrate between the plurality of resin layers, wherein at least one of the plurality of resin layers is semi-cured from the aforementioned resin composition.

[0089] The above-described resin composition can be a resin varnish dissolved or dispersed in an organic solvent. After being coated or impregnated into a fibrous substrate, such a resin composition can be cured to a semi-cured state by heating, thus becoming a sheet-like insulating substrate. The description of such a resin composition is the same as described above and is therefore omitted.

[0090] The aforementioned fiber-based substrate is a fiber-containing substrate, a flexible assembly of fibers that can be bent at will. Such a fiber-based substrate can support prepregs, metal laminates, or printed circuit boards. Because it contains fibers, this fiber-based substrate can reduce the dielectric constant and dielectric loss tangent of the prepreg, metal laminate, or printed circuit board, thereby improving its low dielectric loss characteristics. Furthermore, the fiber-based substrate is tightly bonded to the resin composition during manufacturing, thus exhibiting excellent flexibility, heat resistance, and adhesion.

[0091] The fiber substrate can be multiple fibers, or a substrate (component) composed of fibers, such as yarn, woven fabric, non-woven fabric, knitting, braid, etc.

[0092] Non-limiting examples of the aforementioned fibers include: plant fibers such as cotton and linen; animal fibers such as wool and silk; regenerated fibers such as rayon; synthetic fibers such as polyester, acrylic, nylon, and polyurethane; inorganic fibers such as glass fiber and carbon fiber; and metal fibers, which can be used alone or in combination of two or more. In the case of inorganic fibers such as glass fiber and carbon fiber, due to their low moisture content, no pores are formed within the fiber matrix during subsequent curing, and they also exhibit excellent thermal stability.

[0093] According to one example, the aforementioned fiber substrate can be multiple glass fibers (e.g., E-glass, D-glass, S-glass, NE-glass, T-glass, and Q-glass), cellophane, glass roving, glass yarn, woven fabric, glass chopped strands mat, glass roving cloth, glass surfacing mat, etc. However, it is not limited to these.

[0094] The thickness of the aforementioned fiber substrate is not particularly limited, for example it can be about 10 to 300 μm, specifically about 10 to 100 μm, more specifically about 10 to 50 μm.

[0095] On the other hand, the surface of the aforementioned fiber substrate can be treated with a silane coupling agent. In this case, the method of treatment with the silane coupling agent can be a conventional method known in the art. The description of the silane coupling agent is the same as that described in the aforementioned resin composition, and therefore is omitted.

[0096] According to one example, the surface of the fiber substrate can be treated with the same silane coupling agent used in hollow inorganic fillers, specifically a vinyl silane coupling agent. In this case, not only can the adhesion between the fiber substrate and the (semi)cured resin composition be further improved, but the metal foil of the metal laminate is also more firmly bonded to the prepreg, thereby suppressing foil peeling.

[0097] The prepreg 110 of the present invention has a coefficient of thermal expansion of less than 20 ppm / °C, and can have a relative permittivity (Di) of less than 2.0, specifically about 1.5 to 2.0, at 25°C and 10 GHz. k Here, the relative permittivity (D) of the prepreg is... kThe measurements were performed at 25°C and 10 GHz using the SPDR method (IEC 61189-2-721).

[0098] The prepreg of the present invention can be manufactured by methods known in the art, such as hot-melt methods and solvent methods. For example, the prepreg can be manufactured by directly coating or impregnating a resin composition into a glass fabric and then heating and curing it to a semi-cured state (stage B). In this case, the curing temperature can be in the range of about 50 to 150°C, and the curing time can be about 1 minute to 10 minutes. However, it is appropriate to adjust the curing temperature and time according to the curing conditions of the resin composition.

[0099] According to one example, the prepreg of the present invention can be manufactured by a roll-to-roll apparatus, for example by a method including the following steps: (S10) coating the aforementioned resin composition onto a first film supplied from a first supply roller wound with a first film and continuously traveling, and drying it to continuously form a first insulating member comprising a first resin composition film and a first film; (S20) coating the aforementioned resin composition onto a second film supplied from a second supply roller wound with a second film and continuously traveling, and drying it to continuously form a second insulating member comprising a second resin composition film and a second film; and (S30) while the first insulating member and the second insulating member are respectively stacked on both sides of a fiber substrate supplied from a third supply roller wound with a fiber substrate and continuously traveling, and while stacking in such a way that the resin composition film of each insulating member is in contact with the surface of the fiber substrate, heating / pressurizing is performed using a pair of heating rollers.

[0100] The steps for manufacturing the prepreg of the present invention will be described below.

[0101] Step S10: Formation of the first insulating component

[0102] Step S10 is the step of forming the first insulating component. The aforementioned resin composition is directly coated onto one side of the first film, which is supplied from a first supply roller wound with the first film and continuously travels. Then, it is dried at approximately 50-150°C to obtain a first insulating component with a first resin composition film formed on one side of the first film. At this time, the formed first insulating component can be continuously conveyed to the bonding area with the fiber substrate by the travel roller and bonded to the fiber substrate by a pair of heated rollers. Of course, after the formed first insulating component is wound onto the take-up roller, it can be unwound from the bonding area with the fiber substrate and bonded to the fiber substrate. In this case, step S20 can be omitted, and only step S10 can be performed to manufacture two insulating components for use. Thus, the first insulating component can be manufactured without a paste extrusion process (or calendering) and a high-temperature sintering process, by directly coating the aforementioned resin composition onto the first film and drying it. At this time, the first resin composition film has excellent adhesion to the first film, thereby improving the durability of the final prepreg.

[0103] In this invention, the first film may be a first release film. The first release film is a portion disposed on the first resin layer until the prepreg is applied to the printed circuit board to prevent the first resin layer from being contaminated by foreign matter from the external environment. The prepreg is peeled off before being applied to the printed circuit board.

[0104] Such a first release film can be a conventional release film known in the art, as long as it can be peeled off without damaging the first resin layer. For example, it can be a fluorine release film, specifically a release film coated with a fluorine-based silicone release agent containing a platinum catalyst, or coated with a fluorine release agent mixed with a fluorine curing agent and adhesive additives.

[0105] Examples of the aforementioned base films include polyester films such as polyethylene terephthalate (PET), polybutylene terephthalate, and polyethylene naphthalate, polyethylene films, polypropylene films, cellophane, diacetyl cellulose films, triacetyl cellulose films, acetyl cellulose butyrate films, polyvinyl chloride films, polyvinylidene chloride films, polyvinyl alcohol films, ethylene-vinyl acetate copolymer films, polystyrene films, polycarbonate films, polymethylpentene films, polysulfone films, polyetheretherketone films, polyethersulfone films, polyetherimide films, polyimide films, fluoropolymer films, polyamide films, acrylic resin films, norbornene resin films, and cycloolefin resin films, but are not limited to these.

[0106] The thickness of the first release film is not particularly limited. As an example, the ratio (T2 / T1) of the thickness of the release film (T2) to the thickness of the resin layer (T1) can be about 3 to 5.

[0107] The above-mentioned direct coating (coating) methods are not particularly limited. For example, there are roll-to-roll coating methods, specifically comma coating, slot die coating, curtain coating, and spraying.

[0108] The drying step of the above-mentioned resin composition is used to dry and remove organic solvents from the resin composition, and is carried out at a temperature of about 50 to 150°C for about 1 to 10 minutes, thereby forming a first resin composition film on the first film. Thus, the present invention dries the resin composition only before the bonding step with the fiber substrate, without performing a high-temperature sintering step of 350°C or higher.

[0109] The first insulating component manufactured by the aforementioned step S10 includes a first film and a first resin composition film disposed on one side of the first film.

[0110] Step S20: Formation of the second insulating component

[0111] Step S20 is the step of forming the second insulating component. The aforementioned resin composition is directly coated onto one side of the second film, which is supplied from a second supply roller wound with the second film and continuously travels. Then, it is dried at approximately 50-150°C to obtain a second insulating component with a second resin composition film formed on one side of the second film. At this time, the formed second insulating component can be continuously conveyed by the travel roller to the bonding area with the fiber substrate and bonded to the fiber substrate by a pair of heated rollers. Of course, after being wound onto the take-up roller, the formed second insulating component can be unwound from the bonding area with the fiber substrate and bonded to the fiber substrate. Thus, the second insulating component can be the same as or different from the first insulating component. Like the first insulating component, it can be manufactured by directly coating the aforementioned resin composition onto the second film and drying it without a film-forming process (paste extrusion, calendering) and a high-temperature sintering process. In this case, the second resin composition film has excellent adhesion to the second film, thus improving the durability of the final prepreg.

[0112] In this invention, the second film is a second release film, which may be the same as or different from the first release film. The description of such a second release film is the same as that of the first release film, and therefore is omitted.

[0113] Furthermore, the description of the coating method and drying process of the resin composition is the same as that described in step S10, and therefore is omitted.

[0114] The second insulating component manufactured by the aforementioned step S20 includes a second membrane and a second resin composition membrane disposed on one side of the second membrane.

[0115] Step S30: Bonding process between the first insulating component, the fiber substrate, and the second insulating component.

[0116] The first insulating component and the second insulating component manufactured in steps S10 and S20 are respectively stacked on both sides of the fiber substrate, which is supplied from the third supply roller wound with the fiber substrate and continuously travels. Then, a pair of heating rollers are used to heat / pressurize the substrate. The first insulating component and the second insulating component are stacked with the fiber substrate in such a way that the resin composition film of each insulating component is in contact with the fiber substrate.

[0117] Specifically, in step S30, while the first insulating component formed in step S10 and continuously supplied (conveyed) by the traveling roller is being stacked on one side of the fiber substrate, which is supplied and continuously traveled from the third supply roller wound with the fiber substrate, the second insulating component formed in step S20 and continuously supplied (conveyed) is being stacked on the other side of the fiber substrate. Then, the laminate of the first insulating component-fiber substrate-second insulating component is hot-pressed by a pair of heating rollers, each facing both sides of the fiber substrate. At this time, each insulating component is continuously supplied in such a way that the resin composition film of each insulating component is in contact with the fiber substrate, and the lamination and hot pressing are performed.

[0118] The description of the fiber substrate is the same as above, so it is omitted.

[0119] The above-mentioned hot pressing process can achieve a yield of approximately 10 to 80 kgf / cm² per 1m of fiber substrate. 2 The pressure and temperature of approximately 300 to 400°C are applied for heating / pressurization for approximately 0.1 minutes to 1 hour. According to one example, a roll-to-roll device equipped with a pair of heated rollers can be used to heat a laminated body in the order of first insulating component / fiber substrate / second insulating component at a pressure of approximately 10 to 50 kfg / cm³. 2 Under pressure, the hot-pressing process lasts for approximately 0.1 minutes to 1 hour. During this time, even with a short hot-pressing time or low hot-pressing temperature, the elastomers and PFA in each resin composition film readily melt and bond the hollow inorganic fillers while simultaneously diffusing (migrating) into the fiber substrate and solidifying into a polymer matrix. Therefore, the first and second resin layers after the semi-cured (stage B) resin composition films can be tightly bonded to the fiber substrate. Thus, this invention can manufacture a prepreg that is integrally formed from the first film / first resin layer / fiber substrate / second resin layer / second film. The manufactured prepreg is then in the form of a length of 10 m or more and can be wound onto a take-up roller.

[0120] The first and second resin layers described above can have a relative permittivity (Di) in the range of 1.5 to 2.0 at 25°C and 10 GHz. k Here, the relative permittivity (D) of the first resin layer and the second resin layer is... k The measurements were performed at 25°C and 10 GHz using the SPDR method (IEC61189-2-721).

[0121] The prepreg of the present invention, comprising such a resin layer, can have a coefficient of thermal expansion of less than 20 ppm / °C and a relative permittivity (D0) at 25°C and 10 GHz. k The relative permittivity (D) of the prepreg can be below 2.0. Here, the relative permittivity (D) of the prepreg is... k The measurements were performed at 25°C and 10 GHz using the SPDR method (IEC 61189-2-721).

[0122] <Metal Laminates and Their Manufacturing Methods>

[0123] A metal laminate comprising the aforementioned resin composition of the present invention is provided.

[0124] According to one example, the metal laminate of the present invention comprises: a metal foil; and a resin layer disposed on one or both sides of the metal foil and made of the above-described resin composition.

[0125] According to another example, the metal laminate of the present invention comprises: a first metal foil; a resin layer disposed on one side of the first metal foil and made of the above-described resin composition; and a second metal foil disposed on the resin layer. In this case, the first metal foil and the second metal foil may be the same as or different from each other.

[0126] According to yet another example, the metal laminate of the present invention comprises: a metal foil; and a prepreg disposed on one or both sides of the metal foil and comprising the above-described resin composition. In this case, the prepreg may be one or more layers.

[0127] According to yet another example, the metal laminate of the present invention comprises: a first metal foil; a prepreg disposed on one side of the first metal foil and comprising the above-described resin composition; and a second metal foil disposed on the prepreg. In this case, the first metal foil and the second metal foil may be the same as or different from each other.

[0128] Here, the metal laminate can be a rolled metal laminate manufactured by roll-to-roll.

[0129] The aforementioned metal foil, the first metal foil, and the second metal foil can be made of any metal or alloy known in the art, without limitation. For example, it can be a metal film or two or more alloy films selected from the group consisting of copper (Cu), iron (Fe), nickel (Ni), titanium (Ti), aluminum (Al), silver (Ag), and gold (Au). As an example, the metal foil, the first metal foil, and the second metal foil can be copper foil, which has excellent conductivity and is inexpensive. In this case, the copper foil can be any copper foil known in the art, manufactured by rolling and electrolysis, and can have undergone rust-preventive treatment to prevent surface oxidation and corrosion.

[0130] The surface roughness (Rz) of the matte side of the aforementioned metal foil and the first and second metal foils can, for example, be in the range of about 0.1 to 10 μm. In this case, the surface roughness (Rz) of the matte side of the first metal foil and the surface roughness (Rz) of the matte side of the second metal foil can be the same as or different from each other.

[0131] There are no particular limitations on the thickness of the aforementioned metal foil, the first metal foil, and the second metal foil, but considering the thickness or mechanical properties of the final product, it can be in the range of approximately 9 to 70 μm.

[0132] The aforementioned metal laminate can be manufactured by methods known in the art. For example, a metal laminate can be obtained by stacking a prepreg on one side of a first metal foil (e.g., a first copper foil) and then stacking a second metal foil (e.g., a second copper foil) on it, followed by heating and pressurization.

[0133] According to one example, the metal laminate of the present invention can be manufactured by a roll-to-roll apparatus, for example by a method comprising the following steps: (S100) coating the aforementioned resin composition onto a first metal foil supplied from a fourth supply roller wound with a first metal foil and continuously traveling, and drying it to continuously form a first unit component comprising a first resin composition film and a first metal foil; (S200) coating the aforementioned resin composition onto a second metal foil supplied from a fifth supply roller wound with a second metal foil and continuously traveling, and drying it to continuously form a second unit component comprising a second resin composition and a second metal foil; and (S300) while the first unit component and the second unit component are respectively stacked on both sides of a fiber substrate supplied from a sixth supply roller wound with a fiber substrate and continuously traveling, and while stacking in such a way that the resin composition film of each unit component is in contact with the surface of the fiber substrate, heating / pressurizing is performed using a pair of heating rollers.

[0134] The following describes each step in manufacturing the metal laminate of the present invention.

[0135] Step S100: Formation step of the first unit component

[0136] Step S100 is the step of forming the first unit component. The aforementioned resin composition is directly coated onto one side of the first metal foil, which is supplied from a fourth supply roller wound with the first metal foil and continuously travels. Then, it is dried at approximately 50-150°C to obtain a first unit component with a film of the first resin composition formed on one side of the first metal foil. At this time, the formed first unit component can be continuously conveyed by a travel roller to the bonding area with the fiber substrate and bonded to the fiber substrate by a pair of heated rollers. Of course, after the formed first unit component is wound onto the take-up roller, it can be unwound from the bonding area with the fiber substrate and bonded to the fiber substrate. In this case, step S200 can be omitted, and only step S100 can be performed to manufacture two unit components for use. Thus, the first unit component can be manufactured without a film-forming process (paste extrusion, calendering) and a high-temperature sintering process, by directly coating the aforementioned resin composition onto the first metal foil and then drying it. At this point, the first resin composition film has excellent adhesion to the first metal foil, which improves the durability of the final metal laminate.

[0137] The description of the first metal foil is the same as above, so it is omitted.

[0138] The above-mentioned direct coating (coating) methods are not particularly limited. For example, there are roll-to-roll coating methods, specifically comma coating, slot die coating, curtain coating, and spraying.

[0139] The drying step of the above-mentioned resin composition is used to dry and remove organic solvents from the resin composition, and is carried out at a temperature of about 50 to 150°C for about 1 to 10 minutes, thereby forming a first resin composition film on the first metal foil. Thus, the present invention dries the resin composition only before the bonding step with the fiber substrate, without performing a high-temperature sintering step above 350°C.

[0140] The first unit component manufactured by the aforementioned step S100 includes a first metal foil and a first resin composition film disposed on one side of the first metal foil.

[0141] Step S200: Formation step of the second unit component

[0142] Step S200 is the step of forming the second unit component. The aforementioned resin composition is directly coated onto one side of the second metal foil, which is supplied from a fifth supply roller wound with the second metal foil and continuously travels. Then, it is dried at approximately 50-150°C to obtain a second unit component with a second resin composition film formed on one side of the second film. At this time, the formed second unit component can be continuously conveyed to the bonding area with the fiber substrate by a traveling roller and bonded to the fiber substrate by a pair of heated rollers. Of course, after being wound onto a take-up roller, the formed second unit component can be unwound in the bonding area with the fiber substrate and bonded to the fiber substrate. Thus, the second unit component can be the same as or different from the first unit component. Like the first unit component, it can be manufactured by directly coating the aforementioned resin composition onto the second metal foil and drying it without a film-forming process (paste extrusion, calendering) and a high-temperature sintering process. In this case, the second resin composition film has excellent adhesion to the second metal foil, thus improving the durability of the final metal laminate.

[0143] In this invention, the second metal foil may be the same as or different from the first metal foil. The description of such a second metal foil is the same as that of the first metal foil, and therefore is omitted.

[0144] Furthermore, the description of the coating method and drying process of the resin composition is the same as that described in step S100, and therefore is omitted.

[0145] The second insulating component manufactured by the aforementioned step S200 includes a second metal foil and a second resin composition film disposed on one side of the second metal foil.

[0146] Step S300: Bonding step between the first unit component, the fiber substrate, and the second unit component.

[0147] The first unit component and the second unit component manufactured in steps S100 and S200 are respectively stacked on both sides of the fiber substrate, which is supplied from the sixth supply roller wound with the fiber substrate and travels continuously, and then heated / pressurized by a pair of heating rollers. The stacking is measured in such a way that the resin composition film of each unit component is in contact with the fiber substrate during the stacking process.

[0148] Specifically, in step S300, while a first unit component, formed in step S100 and continuously supplied (conveyed) by a traveling roller, is stacked on one side of the fiber substrate, which is supplied and continuously traveled from a sixth supply roller wound with the fiber substrate, a second unit component, formed in step S200 and continuously supplied (conveyed) by a traveling roller, is stacked on the other side of the fiber substrate. Then, the laminate of the first unit component-fiber substrate-second unit component is hot-pressed by a pair of heating rollers, each facing both sides of the fiber substrate. At this time, each unit component is continuously supplied in such a way that the resin composition film of each unit component is in contact with the fiber substrate, and the stacking and hot pressing are performed.

[0149] The description of the fiber substrate is the same as that in the prepreg section, so it is omitted.

[0150] The above-mentioned hot pressing process can achieve approximately 10 to 80 gf / cm² per 1m of fiber substrate. 2 The material is heated / pressurized at pressure and a temperature of approximately 300 to 400°C for approximately 0.1 minutes to 1 hour. According to one example, a roll-to-roll device equipped with a pair of heated rollers can be used to heat a laminated body stacked in the order of first unit component / fiber substrate / second unit component at approximately 10 to 50 kgf / cm². 2 Under pressure, the hot-pressing process lasts for approximately 0.1 minutes to 1 hour. During this time, even with a short hot-pressing time or low hot-pressing temperature, the elastomers and PFA in each resin composition film readily melt and bond the hollow inorganic fillers while simultaneously diffusing (migrating) into the fiber substrate and solidifying into a polymer matrix. Therefore, the first and second resin layers after the semi-cured (stage B) resin composition films can be tightly bonded to the fiber substrate. Thus, this invention can manufacture a metal laminate consisting of a first metal foil, a first resin layer, a fiber substrate, a second resin layer, and a second metal foil integrated together. The manufactured metal laminate is then in the form of a length exceeding 10 meters and can be wound onto a take-up roller.

[0151] The first and second resin layers described above can have a relative permittivity (Di) in the range of 1.5 to 2.0 at 25°C and 10 GHz. k Here, the relative permittivity (D) of the first resin layer and the second resin layer is... k The measurements were performed at 25°C and 10 GHz using the SPDR method (IEC61189-2-721).

[0152] Printed Circuit Boards

[0153] On the other hand, the present invention provides a printed circuit board comprising the aforementioned resin composition.

[0154] The printed circuit board of the present invention refers to a circuit board obtained by stacking one or more layers through a plated through-hole method or a layering method, and can be obtained by stacking the aforementioned prepreg or laminate on an inner wiring board and then heating / pressurizing it.

[0155] As an example, the printed circuit board of the present invention includes the aforementioned metal laminate. In this case, a circuit pattern can be formed on the metal foil (first metal foil and / or second metal foil) included in the metal laminate. Furthermore, the resin layer or prepreg included in the metal laminate serves as an insulating support component.

[0156] The aforementioned printed circuit board can be manufactured using conventional methods known in the art. For example, it can be manufactured by continuously feeding a roll of metal laminate using a roll-to-roll device, creating holes in the flexible metal laminate to perform through-hole plating, and then etching a metal foil (e.g., copper foil) containing the plating to form a circuit.

[0157] As explained above, the aforementioned resin composition exhibits low dielectric constant and dielectric loss tangent in the frequency band above approximately 10 GHz, and also possesses excellent heat resistance and processability. Therefore, the printed circuit board using the aforementioned resin composition also exhibits low dielectric loss in the frequency band above approximately 10 GHz, thereby reducing transmission losses in electrical / electronic / communication devices, and also demonstrates excellent heat resistance. Consequently, the printed circuit board of the present invention can be advantageously applied to various electrical / electronic / communication devices such as mobile communication devices or their base station devices that process high-frequency to ultra-high-frequency signals, network-related electronic equipment such as servers and routers, mainframe computers, and automotive radar equipment.

[0158] The present invention will be specifically described below through embodiments, but the following embodiments and experimental examples are only illustrative of one aspect of the present invention, and the scope of the present invention is not limited to the following embodiments and experimental examples.

[0159] <Example 1>

[0160] 1-1. Preparation of the resin composition

[0161] The resin composition is prepared by mixing the components according to the composition described in Table 1 below. In this case, the content (amount used) of each component in Table 1 is in weight %, based on the total amount (100 weight %) of the resin composition.

[0162] 1-2. Prepreg Manufacturing

[0163] The resin composition manufactured in Examples 1-1 is coated (thickness: 100 μm) onto one side of a first PI film (thickness: 50 μm) continuously supplied from a polyimide (PI) film supply roller using a pair of coating rollers. The coated resin composition is then dried at approximately 140°C for approximately 3 minutes, thereby manufacturing a roll-shaped first insulating member having a first resin composition film formed on one side of the first PI film. On the other hand, a roll-shaped second insulating member having a second resin composition film formed on one side of the second PI film is manufactured using the same process as the manufacturing of the first insulating member.

[0164] Separately manufactured rolls of first and second insulating components are stacked on both sides of glass fabric continuously fed from glass fabric supply rollers, and then pressed using a pair of high-temperature roller presses at a temperature above 320°C with a pressure of 30 kgf / cm². 2 The prepreg is wound onto a roller by hot pressing under pressure, thereby producing a roll of prepreg. When stacking the above-mentioned unit components, the stacking is performed in such a way that the resin composition film in each insulating component comes into contact with the surface of the glass fabric.

[0165] 1-3. Manufacturing of Copper Foil Laminates

[0166] The resin composition prepared in Example 1-1 is coated (thickness: 100 μm) onto one side of a first copper foil (thickness: 18 μm, roughness (Rz): 3 μm or less) continuously fed from a copper foil supply roller using a pair of coating rollers. The coated resin composition is then dried at approximately 140°C for approximately 3 minutes, thereby producing a roll-shaped first unit component with a first resin composition film formed on one side of the first copper foil. On the other hand, a roll-shaped second unit component with a second resin composition film formed on one side of a second copper foil is produced by performing the same process as the first unit component.

[0167] The separately manufactured rolls of the first and second unit components are respectively stacked on both sides of the prepreg continuously fed from the prepreg supply rolls manufactured in Examples 1-2, and then pressed using a pair of high-temperature roll presses at a temperature above 300°C and a pressure of 30 kgf / cm². 2 The flexible copper foil laminate is wound onto a roller by hot pressing under pressure, thereby producing a roll of flexible copper foil laminate. When stacking the above-mentioned unit components, the resin composition film in each unit component is stacked in such a way that the surface of the prepreg is in contact with it. Furthermore, before using the prepreg, the two PI films within the prepreg are peeled off and removed.

[0168] 1-4. Manufacturing of Printed Circuit Boards

[0169] While continuously supplying the flexible copper foil laminates manufactured in Examples 1-3 above, a photosensitive dry film is coated onto the flexible copper foil laminates by heat and pressure bonding. The substrate, displaying the circuit, is then irradiated with light and developed to continuously manufacture a flexible printed circuit board (FPCB). On the surface of the completed printed circuit board, copper foil containing unnecessary coatings is removed (etched) using a highly corrosive chemical reagent, thereby forming a circuit.

[0170] [Table 1]

[0171]

[0172] [Table 2]

[0173]

[0174] <Examples 2-4 and Comparative Examples 1-4>

[0175] The composition was changed to that shown in Table 1 above. Except for the other parts, the resin composition, prepreg, copper foil laminate and printed circuit board were manufactured using the same method as in Example 1.

[0176] <Experimental Example 1> - Physical Property Evaluation

[0177] The physical properties of the cured resin compositions manufactured in Examples 1 to 4 and Comparative Examples 1 to 4 were evaluated using the following methods, and the results are shown in Table 3 below.

[0178] 1) Specific gravity of insulators

[0179] The copper foil of the copper foil laminates manufactured in Examples 1-4 and Comparative Examples 1-4 was wet-removed with an etching solution (hydrochloric acid: hydrogen peroxide = 1:2 volume ratio). The remaining insulator was then dried at 110°C for 2 hours to obtain samples. The specific gravity of the obtained samples was determined according to the water displacement method [ASTM D792 test method (temperature 23±2°C)].

[0180] 2) Relative permittivity (D) k ) and dielectric loss tangent (D f )

[0181] The copper foil of the copper foil laminates manufactured in Examples 1-4 and Comparative Examples 1-4 was wet-removed with an etching solution (hydrochloric acid: hydrogen peroxide = 1:2 volume ratio), and then dried at 110°C for 2 hours to obtain samples. For the obtained samples, the D at 25°C and 10GHz was measured using the SPDR method (IEC 61189-2-721). k and D f .

[0182] 3) Coefficient of thermal expansion (CTE)

[0183] The copper foil of the copper foil laminates manufactured in Examples 1-4 and Comparative Examples 1-4 was wet-removed with an etching solution (hydrochloric acid: hydrogen peroxide = 1:2 volume ratio), and then dried at 110°C for 2 hours to obtain samples. Subsequently, the CTE in the X / Y direction of the obtained samples was determined using a TMA (Thermomechanical Analyzer) according to the IPC-TM-650 2.4.41.2 test method.

[0184] 4) Resin flowability

[0185] The prepregs prepared in Examples 1-4 and Comparative Examples 1-4 were pressed at 350°C and 5700 lb for 5 minutes, and the degree of resin flow was visually confirmed. If it was confirmed that the resin flowed to the outside of the hot plate of the press, the resin flowability was marked as "○"; if the resin did not flow to the outside of the hot plate of the press, the resin flowability was marked as "×".

[0186] 5) Adhesion

[0187] The adhesion strength between the copper foil and the resin composition interface of the copper foil laminates manufactured in Examples 1-4 and Comparative Examples 1-4 was measured using IPC-TM-650 2.4.8. At this time, the adhesion strength at the point when the copper foil peeled off from the resin composition was 0.4 kgf / cm². 2 When the above is true, mark it with "○"; when the above adhesive force is less than 0.4 kgf / cm 2 When this happens, mark it as "×".

[0188] 6) Heat resistance

[0189] The copper foil laminates manufactured in Examples 1-2 and Comparative Examples 1-3 were tested according to the IPC-TM-650 2.3.13 test method (solder pot, 288°C, 30 seconds), and changes observed by the naked eye were confirmed. When no abnormalities such as copper foil bulging were observed by the naked eye, it was marked with "○"; when abnormalities were observed by the naked eye, it was marked with "×".

[0190] [Table 3]

[0191]

Claims

1. A resin composition comprising: Perfluoroalkoxyalkane (PFA); Elastomers selected from one or more of the group consisting of styrene-based elastomers and fluoropolymers; and Hollow inorganic fillers with a porosity of 60 to 90%.

2. The resin composition according to claim 1, wherein, The hollow inorganic filler has a relative permittivity D in the range of 1 to 3 at 25°C and 10 GHz. k .

3. The resin composition according to claim 2, wherein, The average particle size D50 of the hollow inorganic filler is in the range of 0.5 to 50 μm.

4. The resin composition according to claim 3, wherein, The hollow inorganic filler contains hollow silica.

5. The resin composition according to claim 1, wherein, The perfluoroalkoxyalkane comprises a tetrafluoroethylene repeating unit and a perfluoroether repeating unit. The molar ratio of the included tetrafluoroethylene repeating unit to the perfluoroether repeating unit ranges from 1:10 to 1:10000.

6. The resin composition according to claim 1, further comprising an organic solvent.

7. The resin composition according to claim 1, wherein, Based on the total amount of the resin composition, it comprises: 40 to 80% by weight of perfluoroalkoxyalkanes; 0.1 to 10% by weight of elastomer; and 10 to 40% by weight of hollow inorganic fillers.

8. The resin composition according to claim 1, wherein, The cured resin composition has a relative permittivity D in the range of 1.5 to 2.0 at 25°C and 10 GHz. k .

9. A prepreg comprising the resin composition of any one of claims 1 to 8.

10. The prepreg according to claim 9, having a coefficient of thermal expansion of less than 20 ppm / °C and a relative permittivity D at 25°C and 10 GHz. k It is below 2.

0.

11. A method for manufacturing a roll of prepreg, comprising: The step of coating a resin composition according to any one of claims 1 to 8 onto a first film that is supplied from a first supply roller wound with a first film and continuously traveled, and drying it, to continuously form a first insulating component comprising a resin layer and a first film. The steps of coating the resin composition of any one of claims 1 to 8 onto a second film supplied from a second supply roller wound with a second film and continuously traveling, and drying it to continuously form a second insulating component comprising a resin layer and a second film; and The first insulating component and the second insulating component are stacked on both sides of the fiber substrate, which is supplied from a third supply roller wound with fiber substrate and travels continuously, and the stacking is performed in such a way that the resin layer of each insulating component is in contact with the surface of the fiber substrate, while a pair of heating rollers are used to heat / pressurize.

12. A metal laminate comprising the resin composition of any one of claims 1 to 8.

13. A method for manufacturing a rolled metal laminate, comprising: The step of coating a resin composition according to any one of claims 1 to 8 onto a first metal foil that is supplied from a fourth supply roller wound with a first metal foil and continuously travels, and drying it, to continuously form a first unit component comprising a resin layer and a first metal foil. The steps of coating the resin composition of any one of claims 1 to 8 onto the second metal foil, which is supplied from a fifth supply roller wound with the second metal foil and continuously traveled, and drying it to continuously form a second unit component comprising a resin layer and a second metal foil; and The first unit component and the second unit component are stacked on both sides of the fiber substrate, which is supplied from the sixth supply roller wound with the fiber substrate and travels continuously, and the stacking is performed in such a way that the resin layer of each metal unit component is in contact with the surface of the fiber substrate, while a pair of heating rollers are used to heat / pressurize.

14. A printed circuit board comprising the resin composition according to any one of claims 1 to 8.

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