Resin composition, prepreg comprising same, metal laminated sheet, laminated sheet, and printed circuit board

Abstract

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

Description

Resin composition, prepreg containing the same, metal laminate sheet, laminate sheet and printed circuit board

[0001] The present invention relates to a resin composition having low thermal expansion characteristics, low dielectric characteristics and high heat resistance characteristics, and a prepreg, a metal laminated sheet, a laminated sheet and a printed circuit board comprising the same.

[0002] With the advent of hyper-connected intelligence driven by artificial intelligence, big data, and autonomous vehicles, the development and proliferation of various electronic devices, such as smartphones, has accelerated. This has led to the evolution of next-generation (5G, 6G) communications, enabling high-speed, high-capacity data wireless transmission, from existing 4G LTE communications. In particular, the proliferation of autonomous vehicles, smart cities, and smart factories is driving the adoption of high-frequency and ultra-high frequencies to transmit and receive large amounts of data without delay. Currently, the frequency used is shifting from sub-6 (4.5 GHz) to 28 and 40 GHz, with ultra-high frequencies exceeding 100 GHz expected in the future. However, as the frequency band used in communication and electronic devices increases, transmission loss of electrical signals increases, which can lead to issues such as heat generation, signal attenuation, and delays.

[0003] Accordingly, materials with low permittivity and dielectric constant have been developed to reduce transmission loss. For example, polyphenylene oxide (PPO), liquid crystal polymer (LCP), and modified polyimide (MPI), which can be used at high frequencies, have been applied to printed circuit boards. However, these materials have suffered from poor processability, such as heat resistance and adhesion to copper foil, and difficulties in improving dielectric properties.

[0004] The present invention aims to provide a resin composition having a low coefficient of thermal expansion (CTE), excellent low dielectric properties, heat resistance and resin flowability, and capable of manufacturing a prepreg through a roll-to-roll process.

[0005] In addition, the present invention seeks to provide a prepreg, a metal laminated sheet, a laminated sheet, and a printed circuit board usable in a high-frequency to ultra-high-frequency band using the above-described resin composition.

[0006] To achieve the above-mentioned object, the present invention provides a resin composition comprising: perfluoroalkoxy alkane (PFA); at least one elastomer 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%.

[0007] According to an example, the hollow inorganic filler has a dielectric constant (D) in the range of 1 to 3 at 25°C and 10 GHz. k ) can have.

[0008] According to another example, the hollow inorganic filler may have an average particle diameter (D50) in the range of 0.5 to 50 μm.

[0009] According to another example, the hollow inorganic filler may contain hollow silica.

[0010] According to another example, the perfluoroalkoxy alkane may include tetrafluoroethylene repeating units and perfluoroether repeating units, and the tetrafluoroethylene repeating units and perfluoroether repeating units may be included in a molar ratio range of 1:10 to 1:10000.

[0011] According to another example, the resin composition may additionally contain an organic solvent.

[0012] According to another example, the resin composition may include 40 to 80 wt% of a perfluoroalkoxy alkane; 0.1 to 10 wt% of an elastomer; and 10 to 40 wt% of a hollow inorganic filler, based on the total amount of the resin composition.

[0013] According to another example, the cured product of the resin composition may have a dielectric constant (Dk) in the range of 1.5 to 2.0 at 25°C and 10 GHz.

[0014] In addition, the present invention provides a prepreg comprising the above-described resin composition.

[0015] In one example, the prepreg may have a coefficient of thermal expansion of 20 ppm / ℃ or less and a dielectric constant (Dk) of 2.0 or less at 25 ℃ and 10 GHz.

[0016] In addition, the present invention provides a method for manufacturing a roll-type prepreg, comprising: a step of applying the above-described resin composition onto a first film supplied from a first supply roller on which a first film is wound and continuously travels, and drying the same to continuously form a first insulating member comprising a resin layer and a first film; a step of applying the above-described resin composition onto a second film supplied from a second supply roller on which a second film is wound and continuously travels, and drying the same to continuously form a second insulating member comprising a resin layer and a second film; and a step of laminating the first and second insulating members on both sides of a fiber substrate supplied from a third supply roller on which a fiber substrate is wound and continuously travels, while heating and pressurizing with a pair of heating rollers so that the resin layer of each insulating member is in contact with the surface of the fiber substrate.

[0017] In addition, the present invention provides a metal laminate sheet comprising the above-described resin composition.

[0018] In addition, the present invention provides a method for manufacturing a roll-type metal laminated sheet, comprising: a step of applying the above-described resin composition on a first metal foil supplied from a fourth supply roller on which a first metal foil is wound and continuously travels, and drying the same to continuously form a first unit member including a resin layer and the first metal foil; a step of applying the above-described resin composition on a second metal foil supplied from a fifth supply roller on which a second metal foil is wound and continuously travels, and drying the same to continuously form a second unit member including a resin layer and the second metal foil; and a step of laminating the first and second unit members on both sides of a fiber substrate supplied from a sixth supply roller on which a fiber substrate is wound and continuously travels, while laminating the resin layers of each metal unit member so that they come into contact with the surface of the fiber substrate, and heating and pressurizing the same with a pair of heating rollers.

[0019] In addition, the present invention provides a printed circuit board comprising the above-described resin composition.

[0020] The resin composition according to the present invention has a low coefficient of thermal expansion (CTE), a high glass transition temperature (Tg), a low dielectric constant, and excellent resin flowability, so that it has excellent processability when applied to a printed circuit board, and can improve the low dielectric loss, heat resistance, and low thermal expansion characteristics of the printed circuit board.

[0021] In addition, the resin composition according to the present invention can be used to manufacture a prepreg through a roll-to-roll process.

[0022] Therefore, the resin composition of the present invention can be usefully used as a component of a printed circuit board used in various electrical and electronic devices such as mobile communication devices handling ultra-high frequency signals of 100 GHz or higher, base station devices thereof, network-related electronic devices such as servers and routers, and large computers.

[0023] Hereinafter, the present invention will be described.

[0024] All terms (including technical and scientific terms) used in this specification, unless otherwise defined, may be used in their common sense by those of ordinary skill in the art to which the present invention pertains. Furthermore, terms defined in commonly used dictionaries are not to be interpreted ideally or excessively unless explicitly and specifically defined otherwise.

[0025] Throughout this specification, whenever a part is said to "include" a component, this should be understood as an open-ended term implying the possibility of including other components, rather than excluding other components, unless otherwise stated.

[0026] Additionally, throughout the specification, “above” or “on” means not only the case where the target part is located directly above or directly below it, but also the case where there is another part in between, and does not necessarily mean the position above with respect to the direction of gravity.

[0027] In addition, the terms “first”, “second”, etc. in this specification are not used to indicate any order or importance, but are used to distinguish components from each other.

[0028]

[0029] Resin composition

[0030] In order to minimize propagation loss in the frequency band for 5G~6G communication, prepreg was manufactured by mixing inorganic filler with fluorine resin. In this case, the relative permittivity (D k ) and low dielectric constant (Df) of the inorganic filler mixed with the fluororesin, even when using a fluororesin. k) had high dielectric constant, which limited the implementation of ultra-low dielectric properties. However, if too little inorganic filler was used, the coefficient of thermal expansion (CTE) would increase, lowering environmental reliability, so a certain amount of inorganic filler had to be used.

[0031] In order to solve the above-mentioned problem, the present invention attempted to use a resin composition comprising at least one elastomer selected from the group consisting of a styrene-based elastomer and a fluorine-based elastomer, in addition to a perfluoroalkoxy alkane (PFA) and an inorganic filler. However, since PFA has a dielectric constant (Dk) of 2.1, whereas the dielectric constant (Dk) of inorganic fillers commonly used in the art is higher than that of PFA, there was a limit to lowering the dielectric constant of the resin layer to about 2.0 or less.

[0032] Accordingly, the present invention has found that when a perfluoroalkoxy alkane (PFA); and at least one elastomer selected from the group consisting of a styrenic elastomer and a fluorinated elastomer; and a hollow inorganic filler are used in combination, a low coefficient of thermal expansion (CTE) and low dielectric properties can be realized. However, the present invention has recognized that if the porosity of the hollow inorganic filler is too small, the effect of reducing the permittivity may be small, and on the other hand, if the porosity of the hollow inorganic filler is too large, the hollow inorganic filler may be crushed during the lamination process, causing an increase in the permittivity. Therefore, the present invention includes a hollow inorganic filler comprising a perfluoroalkoxy alkane (PFA); at least one elastomer selected from the group consisting of a styrenic elastomer and a fluorinated elastomer; and a hollow inorganic filler, wherein the porosity is controlled to be in the range of 60 to 90%.

[0033] Specifically, the relative permittivity (Dk) of the hollow inorganic filler itself is about 1 to 3. When such a hollow inorganic filler is mixed with PFA, it has a relative permittivity (Dk) of about 1.5 to 2.0. In general, signal transmission loss is proportional to not only the dielectric loss but also the permittivity. Therefore, excessive signal transmission loss occurring in the ultra-high frequency range of 100 GHz or more can be reduced by the ultra-low dielectric resin composition of the present invention including the hollow inorganic filler and PFA. In addition, a low permittivity has the advantage of increasing the ease of circuit design, such as antennas. PFA has a melting point of about 300°C or higher, and is a high thermoplastic material, requiring a high-temperature molding process. On the other hand, the hollow inorganic filler can replace the existing inorganic filler because the shell material is an inorganic material that is stable even at high temperatures and can maintain its phase even during a high-temperature molding process. Accordingly, the resin composition according to the present invention has a low coefficient of thermal expansion (CTE), a high glass transition temperature (Tg), a low dielectric constant, and excellent resin flowability, so that it has excellent processability when applied to a printed circuit board, and can improve the low dielectric loss, heat resistance, and low thermal expansion characteristics of the printed circuit board. In addition, the resin composition according to the present invention can produce a prepreg through a roll-to-roll process without a high-temperature molding process. Therefore, the resin composition of the present invention can be usefully used as a component of a printed circuit board used in various electrical and electronic devices such as mobile communication devices handling ultra-high frequency signals of 100 GHz or higher, base station devices thereof, network-related electronic devices such as servers and routers, and large-scale computers.

[0034] According to one example, a resin composition according to the present invention comprises (a) a perfluoroalkoxy alkane (PFA); (b) at least one elastomer selected from the group consisting of a styrenic elastomer and a fluorine-based elastomer; and (c) a hollow inorganic filler having a porosity of 60 to 90%.

[0035] According to another example, the resin composition according to the present invention may additionally include, in addition to the above-described components, at least one selected from the group consisting of a curing agent, an initiator, and a solvent.

[0036] Hereinafter, each component of the resin composition according to the present invention will be described.

[0037] (a) perfluoroalkoxy alkanes

[0038] In the resin composition of the present invention, perfluoroalkoxy alkane is a type of fluorine-containing fluorine (F)-based resin, and can implement low dielectric constant and low dielectric loss characteristics of the resin layer. Such perfluoroalkoxy alkane is a solid particle-shaped filler at room temperature, and is bound by an elastomer when the resin composition is dried and incorporated into the resin layer. In a hot press process at about 310°C or higher, it can be melted to form a matrix component of the resin layer together with the elastomer. In addition, since perfluoroalkoxy alkane does not contain a dispersant, unlike a fluorine resin dispersion, it can improve the heat resistance and adhesiveness of the metal laminate sheet.

[0039] For example, the perfluoroalkoxy alkane comprises a tetrafluoroethylene (C2F4) repeating unit and a perfluoroether (C2F3OR 1 , where R 1 Silver C1~C 12 It contains repeating units of perfluoroalkyl group.

[0040] At this time, the ratio of the tetrafluoroethylene repeating unit and the perfluoroether repeating unit is not particularly limited, and may be, for example, a molar ratio of 1:10 to 1:10,000. However, when the ratio of the tetrafluoroethylene repeating unit and the perfluoroether repeating unit is within the above-mentioned range, the perfluoroalkoxy alkane may have a dielectric constant (Dk) of about 2 to 3 and a dielectric loss tangent (Df) of about 0.0001 to 0.001 at 25°C and 10 ㎓. Here, the dielectric constant (D of the perfluoroalkoxy alkane k ) and dielectric constant (Df) were measured at 25℃ and 10 GHz using the SPDR method (IEC 61189-2-721).

[0041] The weight average molecular weight (Mw) of the above perfluoroalkoxy alkane may be about 1,000,000 to 10,000,000, but is not limited thereto.

[0042] The above perfluoroalkoxy alkane may have a melt flow rate (MFR) of about 1 to 30 g / 10 min measured under conditions of about 372°C and about 2 kg according to the ISO 1133-1 test method.

[0043] The more uniformly these perfluoroalkoxy alkanes are dispersed within the resin composition, the more they can improve the dielectric properties of the resin composition. In addition, they are suitable for manufacturing prepregs and metal laminated sheets through a simple coating process without high-temperature extrusion molding and high-temperature firing, and are also suitable for manufacturing prepregs and metal laminated sheets through a roll-to-roll process. Accordingly, in the present invention, it is preferable to control the shape, size (average particle diameter), and content of the perfluoroalkoxy alkanes within specific ranges.

[0044] Specifically, the shapes of perfluoroalkoxy alkanes include spherical, flake, dendrite, cone, pyramidal, and amorphous. Among these, when a spherical perfluoroalkoxy alkane is used, the surface area of ​​the filler is minimized, so the processing characteristics of the resin composition can be improved, and isotropic properties can be imparted to the resin layer.

[0045] In addition, the perfluoroalkoxy alkane may have an average particle diameter (D50) of about 0.1 to 100 μm, specifically about 1 to 70 μm, and more specifically about 5 to 50 μm. If the perfluoroalkoxy alkane has the above-described average particle diameter, the perfluoroalkoxy alkane is uniformly dispersed without aggregation in the resin composition, making it suitable for producing a resin layer for a printed circuit board. Here, the average particle diameter (D50) of the perfluoroalkoxy alkane can be measured according to ASTM D4464.

[0046] In the resin composition of the present invention, the content of perfluoroalkoxy alkane is not particularly limited. However, if the content of perfluoroalkoxy alkane is too low, the adhesive strength of the resin layer with other substrates (e.g., the fiber substrate of the prepreg, the metal foil of the metal laminate sheet) may decrease, resulting in peeling between the resin layer and other substrates. On the other hand, if the content of perfluoroalkoxy alkane is too high, the coefficient of thermal expansion (CTE) of the resin layer may increase because the content of the inorganic filler is relatively low. Therefore, the content of perfluoroalkoxy alkane is suitably adjusted to a range of about 40 to 80 wt%, specifically about 50 to 80 wt%, and more specifically about 60 to 80 wt%, based on the total amount (100 wt%) of the resin composition. In this case, the resin composition of the present invention can form a resin layer having excellent heat resistance and adhesiveness, as well as low permittivity and dielectric loss.

[0047] (b) elastomer

[0048] In the resin composition of the present invention, the elastomer is a binder resin capable of binding both the perfluoroalkoxy alkane and the hollow inorganic filler. For example, the resin composition may include a thermoplastic elastomer. In this case, the thermoplastic elastomer melts during high-temperature pressing, facilitating the formation of a resin layer.

[0049] The elastomer according to the present invention comprises at least one selected from the group consisting of a fluorine-based elastomer and a styrene-based elastomer. The fluorine-based elastomer and the styrene-based elastomer can easily bind a hollow inorganic filler and a perfluoroalkoxy alkane, and have low dielectric properties. Specifically, the elastomer of the present invention has a dielectric loss tangent (Df) of 0.0005 to 0.0020 at 25°C and 10 ㎓. In addition, the elastomer of the present invention has a relative permittivity (Dk) of 2.0 to 3.0 at 25°C and 10 ㎓. Here, the relative permittivity (D) of the elastomer k ) and dielectric constant (Df) were measured at 25℃ and 10 GHz using the SPDR method (IEC 61189-2-721).

[0050] In this way, when the elastomer of the present invention having a low dielectric constant and a low dielectric tangent is used as a binder, a resin layer having a low dielectric loss can be easily formed by directly coating and drying the resin composition on a film or metal foil without a high-temperature extrusion molding process and a high-temperature firing process.

[0051] The fluorine-based elastomer of the present invention is a type of thermoplastic elastomer, an elastomer containing one or more fluorine (F) atoms in at least one repeating unit, and can be dissolved in an organic solvent (e.g., MEK, etc.).

[0052] These fluorinated elastomers have a dielectric constant (Dk) of 2.0 to 3.0 and a dielectric loss factor (Df) of 0.0005 to 0.0020 at 25 ℃ and 10 ㎓, as well as a low modulus. Here, the dielectric constant (D) of the fluorinated elastomer k ) and dielectric constant (Df) were measured at 25℃ and 10 GHz using the SPDR method (IEC 61189-2-721).

[0053] Fluorine-based elastomers usable in the present invention include fluoroelastomers (FKM), specifically copolymers containing two or more of vinylidene fluoride (VDF), hexafluoropropylene (HFP), and tetrafluoroethylene (TFE). Depending on the number of monomers, they may be binary or ternary copolymers, and examples thereof include, but are not limited to, VDF-HFP copolymers and VDF-HFP-TFE copolymers. These may be used alone, or two or more may be mixed and used.

[0054] The fluorine (F) content in the fluorine-based elastomer of the present invention is not particularly limited, but when it is in the range of about 60 to 80 wt% per molecule of the fluorine-based elastomer, the fluorine-based elastomer may have a dielectric constant (Df) of about 0.0005 to 0.0020 at 25°C and 10 ㎓.

[0055] The styrene-based elastomer of the present invention is a type of thermoplastic elastomer, and is an elastomer containing one or more styrene groups in at least one repeating unit. Such a styrene-based elastomer may have a dielectric constant (Df) of 0.0005 to 0.0020 and a dielectric constant (Dk) of 2.0 to 3.0 at 25°C and 10 ㎓. Here, the dielectric constant (D) of the styrene-based elastomer k ) and dielectric constant (Df) were measured at 25℃ and 10 GHz using the SPDR method (IEC 61189-2-721).

[0056] The styrene-based elastomer usable in the present invention is styrene and C2~C 10 It may be a copolymer elastomer of an aliphatic unsaturated hydrocarbon. Specifically, examples of styrenic elastomers include, but are not limited to, styrene-butadiene-styrene binary copolymer (SBS), styrene-ethylene-butylene-styrene terpolymer (SEBS), styrene-ethylene-ethylene-propylene-styrene terpolymer (SEEPS), styrene-isoprene-styrene binary copolymer, and styrene-ethylene-propylene-styrene terpolymer. These may be used alone or as a mixture of two or more.

[0057] The styrene group content in the styrene-based elastomer of the present invention is not particularly limited, but when it is in the range of about 10 to 40 wt% per molecule of the styrene-based elastomer, the styrene-based elastomer may have a dielectric loss tangent (Df) at 25°C and 10 GHz in the range of about 0.0005 to 0.0020.

[0058] The elastomer of the present invention may have a melt flow rate (MFR) of about 0.1 g / 10 min or less, measured under conditions of 230°C and 2 kg according to the ISO 1133-1 test method.

[0059] In addition, the viscosity of a solution containing 5 wt% of the elastomer of the present invention dissolved in toluene is about 50 to 100 cps. Therefore, the viscosity of the resin composition of the present invention can be controlled within a range of about 150 to 500 cps, thereby improving processability when producing prepregs or metal laminated sheets.

[0060] The elastomer of the present invention has a high thermal decomposition temperature (Td) of about 350°C or higher. Therefore, the resin composition of the present invention can form a resin layer having excellent thermal stability at high temperatures.

[0061] In the resin composition of the present invention, the content of the elastomer is not particularly limited, and may be, for example, in a range of about 0.1 to 10 wt%, specifically in a range of about 1 to 8 wt%, and more specifically in a range of about 1 to 5 wt%, based on the total amount of the resin composition. If the content of the elastomer is less than about 0.1 wt%, the binding effect of the hollow inorganic filler and the perfluoroalkoxy alkane may be reduced, and on the other hand, if the content of the elastomer exceeds about 10 wt%, the adhesion between the resin layer and other substrates (e.g., fiber substrates, metal foils) may be reduced, and the resin layer and other substrates may be separated (peeled) from each other during the manufacture and use of prepregs and metal laminated sheets.

[0062] (c) Hollow weapon filler

[0063] In the resin composition according to the present invention, the hollow inorganic filler is a filler having empty spaces (pores) within the particle. Like conventional inorganic fillers, this hollow inorganic filler 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 (toughness), and low stress of the final product.

[0064] However, since hollow inorganic fillers have air in the empty space inside the particles, the size of the internal air layer can affect the dielectric constant of the resin layer. Accordingly, as described above, the present invention includes a hollow inorganic filler having a porosity in the range of 60 to 90%. Here, the porosity is (d / D). 3× 100 (%) (wherein, D is the total diameter (outer diameter) of the particle, measured with a particle sizer, and d is the diameter (inner diameter) of the internal air layer, calculated by measuring the thickness of the shell by observing the cross-section of the hollow inorganic filler with an electron microscope). If the porosity of the hollow inorganic filler is less than 60%, the effect of reducing the dielectric constant may be small, and on the other hand, if the porosity of the hollow inorganic filler exceeds 90%, the hollow inorganic filler may be crushed during the lamination process, which may cause an increase in the dielectric constant.

[0065] These hollow inorganic fillers may have an average particle diameter (D50) in the range of about 0.5 to 50 μm, specifically in the range of about 1 to 25 μm. Here, the average particle diameter (D50) of the hollow inorganic filler may be measured according to ASTM D4464.

[0066] Additionally, the hollow inorganic filler has a dielectric constant (D) in the range of 1 to 3 at 25 ℃ and 10 GHz. k ) can have. Here, the dielectric constant (D) of the hollow inorganic filler k ) was measured at 25℃, 10 GHz using SPDR method (IEC 61189-2-721).

[0067] The components of the above hollow inorganic filler may be silica, alumina, calcium carbonate, magnesium carbonate, magnesia, 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., and among these, silica having high physical strength and low thermal expansion coefficient is preferable.

[0068] In one example, the hollow inorganic filler may be hollow silica. The hollow silica may include other metal elements (e.g., boron, sodium, calcium, aluminum, etc.) in addition to the silica (SiO2) component, and may be specifically composed of a borosilicate component, and more specifically, may include about 75 to 85 wt% of silica, about 10 to 15 wt% of boron oxide, about 1 to 6 wt% of sodium oxide, and about 1 to 3 wt% of aluminum oxide.

[0069] The shape of the above hollow inorganic filler may be a spherical particle, but may also be an irregular particle.

[0070] In addition, the hollow inorganic filler may be surface-treated with a surface treatment agent. The surface treatment agent is not particularly limited as long as it is generally known in the art, and examples thereof include a silane coupling agent. In this case, the content of the silane coupling agent may be about 0.01 to 20 parts by weight, specifically about 0.1 to 10 parts by weight, and more specifically about 0.1 to 5 parts by weight, based on 100 parts by weight of the hollow inorganic filler.

[0071] The silane coupling agent usable in the present invention is not particularly limited as long as it is one commonly known in the art, and examples thereof include phenyl-based, vinyl-based, epoxy-based, methacryloxy-based, amino-based, mercapto-sulfide-based, and ureide-based silane coupling agents, and may 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 curing of the resin composition.

[0072] For example, the silane coupling agent may be a phenyl-based silane coupling agent, specifically phenylsilane, trimethylphenylsilane, triethoxyphenylsilane, methoxydimethylphenylsilane, isopropylphenylsilane, etc., and these may be used alone or in combination of two or more. In this case, since the compatibility with a fluororesin without a functional group is excellent, the dielectric constant and dielectric loss tangent can be lowered, and the moisture absorption heat resistance and processability can be further improved.

[0073] The aforementioned silane coupling agent not only surface-treats the hollow inorganic filler, but may also be added as a component of the resin composition. At this time, the content of the silane coupling agent may be about 0.0001 to 10 wt%, specifically about 0.01 to 5 wt%, and more specifically about 0.1 to 3 wt%, based on the total amount of the resin composition. In this case, the dispersibility of the inorganic filler is improved by the silane coupling agent, thereby improving the dielectric properties of a cured product of the resin composition (e.g., a resin layer) or a prepreg to which the resin composition is applied.

[0074] In the resin composition of the present invention, the content of the hollow inorganic filler may be in the range of about 10 to 40 wt%, specifically about 15 to 30 wt%, based on the total weight of the resin composition. If the content of the hollow inorganic filler is less than about 10 wt%, the effect of reducing the dielectric constant may be insignificant, and on the other hand, if the content of the hollow inorganic filler exceeds about 40 wt%, the moldability of the resin composition may be reduced.

[0075] (d) organic solvent

[0076] 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 the organic solvent.

[0077] The organic solvent usable in the present invention is not particularly limited as long as it can dissolve the above-mentioned elastomer. Examples of such organic solvents include, but are not limited to, 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 amyl ketone, cyclohexanone, isophorone, and N-methylpyrrolidone; and ester compounds such as ethyl acetate, butyl acetate, and methyl cellosolve acetate. These may be used alone, or two or more may be mixed and used.

[0078] The content of the organic solvent may be used as a content known in the art, and may be a remainder that adjusts the total amount of the resin composition to 100 wt%. For example, the content may be in the range of about 20 to 80 wt%, specifically in the range of about 30 to 70 wt%, based on 100 wt% of the resin composition (excluding the organic solvent).

[0079] Meanwhile, the resin composition of the present invention may further include additives such as flame retardants, other thermosetting resins or thermoplastic resins, ultraviolet absorbers, antioxidants, polymerization initiators, dyes, pigments, dispersants, thickeners, leveling agents, colorants, etc. known in the art, in addition to the aforementioned perfluoroalkoxy alkanes, elastomers, and hollow inorganic fillers, as needed, within a range that does not impair the physical properties thereof. The content of the additives may be used as known in the art, and may be, for example, about 0.0001 to 10 wt% based on the total amount of the resin composition.

[0080] The viscosity of the resin composition according to the present invention can be adjusted depending on the type or content of the perfluoroalkoxy alkane, elastomer, and hollow inorganic filler in the composition, and may be, for example, about 150 to 500 cps. In one example, when the resin composition has the viscosity described above, a resin layer can be directly formed on a film or metal foil by a roll-to-roll coating method.

[0081] As described above, the resin composition of the present invention is a high-frequency low-k, low-dielectric-loss resin composition that can be used to manufacture prepregs, sheets, films, tapes, laminates, or printed wiring boards, by including a perfluoroalkoxy alkane, an elastomer, and a hollow inorganic filler having excellent electrical properties in a high-frequency to ultra-high-frequency band. In addition, the resin composition of the present invention has a low coefficient of thermal expansion (CTE) and excellent heat resistance and resin flowability. In addition, the resin composition of the present invention can easily form prepregs and metal laminated sheets that include a resin layer having a low k, low dielectric loss, and excellent stability of signal transmission loss by directly coating and drying the prepreg on a metal foil without a film forming process (paste extrusion, calendering) and a high-temperature firing process when manufacturing prepregs and metal laminated sheets. In addition, the resin composition of the present invention can be applied to substrates of various materials, and for example, can be applied to a polyimide (PI) substrate material to produce a flexible metal laminate sheet.

[0082] According to an example, the cured product (resin layer) of the resin composition according to the present invention has a dielectric constant (D) in the range of about 1.5 to 2.0 at 25° C. and 10 GHz. k ) can have. Here, the dielectric constant (D) of the cured product k ) was measured at 25℃, 10 GHz using SPDR method (IEC 61189-2-721).

[0083]

[0084] <Prepreg and its manufacturing method>

[0085] Meanwhile, the present invention provides a prepreg comprising the above-described resin composition.

[0086] The prepreg according to the present invention is a fiber-reinforced composite material, and may include, for example, a fiber substrate; and a semi-cured resin composition impregnated into the fiber substrate. Here, the semi-cured resin composition may be in a state where the resin composition is not fully cured, for example, in a B-stage state during the resin curing step.

[0087] According to another example, the prepreg of the present invention comprises a plurality of resin layers (e.g., first and second resin layers); and a fiber substrate interposed between the plurality of resin layers, wherein at least one resin layer of the plurality of resin layers is a semi-cured resin composition as described above.

[0088] The above resin composition may be a resin varnish dissolved or dispersed in an organic solvent. This resin composition may be coated or impregnated onto a fiber substrate, then cured to a semi-hardened state by heating to form a sheet-shaped insulating substrate. Since the description of this resin composition is identical to that described above, further details will be omitted.

[0089] The above-mentioned fiber substrate is a fiber-containing substrate, and is a flexible fiber assembly that can be arbitrarily folded. This fiber substrate can support a prepreg, a metal laminate sheet, or a printed circuit board. Since this fiber substrate contains fibers, it can lower the permittivity and dielectric loss tangent of the prepreg, metal laminate sheet, or printed circuit board, thereby improving low-dielectric loss characteristics. In addition, the fiber substrate can be in close contact with the resin composition during manufacturing, thereby exhibiting excellent flexibility, heat resistance, and adhesive strength.

[0090] The above fiber substrate may be a plurality of fibers, or a substrate (member) made of fibers such as yarn, woven fabric, non-woven fabric, knitting, braid, etc.

[0091] Non-limiting examples of the above fibers include vegetable fibers such as cotton and hemp; animal fibers such as wool and silk; regenerated fibers such as rayon; synthetic fibers such as polyester, acrylic, nylon, polyurethane, etc.; inorganic fibers such as glass fiber and carbon fiber; and metal fibers, and these may be used alone or in combination of two or more. Among these, inorganic fibers such as glass fiber and carbon fiber have low moisture content, so pores do not form in the fiber base material during subsequent curing, and they also have excellent thermal stability.

[0092] In one example, the fiber substrate may be a plurality of glass fibers (e.g., E-glass, D-glass, S-glass, NE-glass, T-glass, and Q-glass, etc.), glass paper, glass roving, glass yarn, woven fabric, glass chopped strands, glass chopped strands mat, glass roving cloth, glass surfacing mat, etc., but is not limited thereto.

[0093] The thickness of the above fiber substrate is not particularly limited, and may be, for example, about 10 to 300 μm, specifically about 10 to 100 μm, and more specifically about 10 to 50 μm.

[0094] Meanwhile, the surface of the fiber substrate may be treated with a silane coupling agent. The method for treating with the silane coupling agent may be any conventional method known in the art. Since the description of the silane coupling agent is the same as that mentioned in the aforementioned resin composition, a detailed description thereof will be omitted.

[0095] For example, the surface of the fiber substrate can be treated with the same silane coupling agent as the silane coupling agent used in the hollow inorganic filler, specifically, with a vinyl group-containing silane coupling agent. In this case, not only is the adhesion between the fiber substrate and the (semi)cured product of the resin composition further improved, but the metal foil of the metal laminate sheet and the prepreg are more firmly bonded, thereby suppressing delamination of the metal foil.

[0096] The prepreg (110) of the present invention described above has a thermal expansion coefficient of 20 ppm / ℃ or less, and a dielectric constant (D) of about 2.0 or less, specifically about 1.5 to 2.0, at 25 ℃ and 10 GHz. k ) can have. Here, the dielectric constant (D) of the prepreg k ) was measured at 25℃, 10 GHz using SPDR method (IEC 61189-2-721).

[0097] The prepreg of the present invention can be manufactured using a hot melt method, solvent method, or other methods known in the art. For example, the prepreg can be manufactured by directly coating or impregnating a glass fabric with a resin composition, then heating and curing to a semi-cured (B-stage) state. At this time, the curing temperature may be in the range of about 50 to 150°C, and the curing time may be about 1 to 10 minutes. However, the curing temperature and time may be appropriately adjusted depending on the curing conditions of the resin composition.

[0098] According to an example, the prepreg of the present invention can be manufactured by a roll-to-roll device, and can be manufactured by a method including, for example, the steps of (S10) applying the above-described resin composition onto a first film supplied from a first supply roller on which a first film is wound and continuously running, and drying the same to continuously form a first insulating member including a first resin composition film and the first film; (S20) applying the above-described resin composition onto a second film supplied from a second supply roller on which a second film is wound and continuously running, and drying the same to continuously form a second insulating member including a second resin composition film and the second film; and (S30) laminating the first and second insulating members on both sides of a fiber substrate supplied from a third supply roller on which a fiber substrate is wound and continuously running, respectively, while heating and pressurizing the first and second insulating members with a pair of heating rollers so that the resin composition films of each insulating member are in contact with the surface of the fiber substrate.

[0099] Hereinafter, each step of manufacturing the prepreg of the present invention will be described.

[0100] (S10) Step: Formation step of the first insulating member

[0101] (S10) Step is a step for forming a first insulating member, in which the first film is supplied from a first supply roller on which the first film is wound and the resin composition described above is directly applied (coated) onto one side of the continuously running first film, and then dried at about 50 to 150°C, thereby obtaining a first insulating member on which a film of the first resin composition is formed on one side of the first film. At this time, the first insulating member to be formed can be continuously transported to a bonding area with the fiber substrate by the traveling roller and bonded to the fiber substrate by a pair of heating rollers. Of course, the first insulating member to be formed can be wound on a winding roller and then unwound again from the bonding area with the fiber substrate and bonded to the fiber substrate. In this case, the following (S20) step can be omitted, and only the above-described (S10) step can be performed to manufacture two insulating members, which can then be used. In this way, the first insulating member can be manufactured by directly coating and drying the resin composition on the first film without a film forming process (paste extrusion, calendering) and a high-temperature firing process. In this case, since the first resin composition film has excellent adhesion to the first film, the durability of the final prepreg can be improved.

[0102] In the present invention, the first film may be a first release film. The first release film is disposed on the first resin layer before applying the prepreg to the printed circuit board to prevent the first resin layer from being contaminated by foreign substances in the external environment, and is peeled off and removed before the prepreg is applied to the printed circuit board.

[0103] The first release film is not particularly limited as long as it is a conventional film known in the art and can be peeled off without damaging the first resin layer, and for example, it may be a fluorine release film, and specifically, a fluorine release film may be coated on a base film, such as a fluorine silicone release agent containing a platinum catalyst itself, or a fluorine release agent mixed with a fluorine curing agent and an adhesive additive.

[0104] Examples of the above base film include, but are not limited to, polyester films such as polyethylene terephthalate (PET), polybutylene terephthalate, and polyethylene naphthalate, polyethylene films, polypropylene films, cellophane, diacetylcellulose films, triacetylcellulose films, acetylcellulose 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, fluororesin films, polyamide films, acrylic resin films, norbornene-based resin films, and cycloolefin resin films.

[0105] The thickness of the first release film is not particularly limited. For example, the ratio (T2 / T1) of the thickness of the release film (T2) to the thickness of the resin layer (T1) may be about 3 to 5.

[0106] The above direct application (coating) method is not particularly limited, and includes, for example, a roll-to-roll coating method, and specifically, comma coating, slot die coating, curtain coating, and spray coating.

[0107] The drying process of the above resin composition is performed to dry and remove the organic solvent in the resin composition, and is performed 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. In this way, the present invention only dries the resin composition before the laminating process with the fiber substrate, and does not perform a high-temperature firing process of 350°C or higher.

[0108] The first insulating member manufactured through the aforementioned step (S10) includes a first film and a first resin composition film disposed on one surface of the first film.

[0109] (S20) Step: Formation step of the second insulating member

[0110] (S20) Step is a step for forming a second insulating member, in which the second film is supplied from a second supply roller on which the second film is wound and the resin composition described above is directly applied (coated) onto one side of the continuously running second film, and then dried at about 50 to 150°C, thereby obtaining a second insulating member on which a film of the second resin composition is formed on one side of the second film. At this time, the second insulating member to be formed may be continuously transported to a lamination area with a fiber substrate by a running roller and laminated with the fiber substrate by a pair of heating rollers. Of course, the second insulating member to be formed may be wound on a winding roller and then unwound again from the lamination area with the fiber substrate and laminated with the fiber substrate. In this way, the second insulating member may be the same as or different from the first insulating member, and, like the first insulating member, may be manufactured by directly coating and drying the resin composition on the second film without a film forming process (paste extrusion, calendering) and a high-temperature firing process. At this time, since the second resin composition film has excellent adhesion to the second film, the durability of the final prepreg can be improved.

[0111] In the present 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 this second release film is the same as that of the first release film, and therefore is omitted.

[0112] In addition, the description of the coating method and drying process of the resin composition is omitted because it is the same as that described in step (S10).

[0113] The second insulating member manufactured through the aforementioned step (S20) includes a second film and a second resin composition film disposed on one surface of the second film.

[0114] (S30) Step: Lamination step between first insulating member-fiber substrate-second insulating member

[0115] The first and second insulating members manufactured in the above steps (S10) and (S20), respectively, are laminated on both sides of a continuously running fiber substrate supplied from a third supply roller on which a fiber substrate is wound, and then heated and pressurized by a pair of heating rollers. However, when laminating the first and second insulating members with the fiber substrate, the resin composition film of each insulating member is laminated so that it comes into contact with the fiber substrate.

[0116] Specifically, in step (S30), a first insulating member formed in step (S10) and continuously supplied (transported) by a running roller is laminated on one side of a fiber substrate supplied from a third supply roller on which a fiber substrate is wound, and a second insulating member formed in step (S20) and continuously supplied (transported) is laminated on the other side of the fiber substrate, and then a laminate of the first insulating member-fiber substrate-second insulating member can be thermally compressed by a pair of heating rollers facing each other on both sides of the fiber substrate. At this time, each insulating member is continuously supplied and laminated and thermally compressed so that a resin composition film of each insulating member is in contact with the fiber substrate.

[0117] Since the description of the above fiber material is the same as that described above, it is omitted.

[0118] The above-described thermocompression process can be performed by heating and pressing at a pressure of about 10 to 80 kgf / ㎠ per meter of the fiber substrate and a temperature of about 300 to 400°C for about 0.1 minute to 1 hour. In one example, a roll-to-roll device having a pair of heating rollers can be used to thermocompression-bond a laminate in the order of the first insulating member / fiber substrate / second insulating member at a pressure of about 10 to 50 kfg / ㎠ for about 0.1 minute to 1 hour. At this time, even if the thermocompression time is short or the thermocompression temperature is low, the elastomer and PFA in each resin composition film can easily melt and bind the hollow inorganic filler while diffusing (moving) into the fiber substrate and hardening into a polymer matrix. As a result, the first and second resin layers in which each resin composition film is semi-cured (B-staged) can be formed in close contact with the fiber substrate. Accordingly, the present invention can manufacture a prepreg in which a first film / first resin layer / fiber substrate / second resin layer / second film are integrated with each other. The manufactured prepreg can be wound around a take-up roller in a long form with a length of 10 m or more.

[0119] The first and second resin layers may have a dielectric constant (Dk) in the range of 1.5 to 2.0 at 25°C and 10 GHz. Here, the dielectric constant (D) of the first and second resin layers k ) was measured at 25℃, 10 GHz using SPDR method (IEC 61189-2-721).

[0120] The prepreg of the present invention including these resin layers may have a coefficient of thermal expansion of 20 ppm / ℃ or less and a dielectric constant (Dk) of 2.0 or less at 25 ℃ and 10 GHz. Here, the dielectric constant (D) of the prepreg k ) was measured at 25℃, 10 GHz using SPDR method (IEC 61189-2-721).

[0121]

[0122] <Metal laminated sheet and manufacturing method thereof>

[0123] A metal laminate sheet comprising the above-described resin composition according to the present invention is provided.

[0124] According to an example, a metal laminate sheet according to the present invention comprises a metal foil; and a resin layer formed of the resin composition and disposed on one or both sides of the metal foil.

[0125] According to another example, a metal laminate sheet according to the present invention comprises: a first metal foil; a resin layer formed of the resin composition and disposed on one surface of the first metal foil; and a second metal foil disposed on the resin layer. Here, the first metal foil and the second metal foil may be the same or different from each other.

[0126] According to another example, a metal laminate sheet according to the present invention comprises a metal foil; and a prepreg disposed on one or both sides of the metal foil and comprising the resin composition. The prepreg may be one-layer or multiple-layer.

[0127] According to another example, a metal laminate sheet according to the present invention comprises: a first metal foil; a prepreg disposed on one surface of the first metal foil and comprising the resin composition; and a second metal foil disposed on the prepreg. Here, the first metal foil and the second metal foil may be the same or different from each other.

[0128] Here, the metal laminate sheet may be a roll-type metal laminate sheet manufactured by roll-to-roll.

[0129] The above metal foil and the first and second metal foils may be made of any metal or alloy known in the art without limitation, and may be, for example, one type of metal foil selected from the group consisting of copper (Cu), iron (Fe), nickel (Ni), titanium (Ti), aluminum (Al), silver (Ag), and gold (Au), or two or more types of alloy foils. For example, the metal foil and the first and second metal foils may be copper foil having excellent electrical conductivity and being inexpensive. At this time, the copper foil may be any copper foil known in the art without limitation, and may be manufactured by a rolling method or an electrolytic method, and may also be subjected to a rust prevention treatment to prevent the surface from being oxidized and corroded.

[0130] The surface roughness (Rz) of the matte side of the metal foil and the first and second metal foils may be, for example, 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 may be the same as or different from each other.

[0131] The thickness of the above metal foil and the first and second metal foils is not particularly limited, but may be in the range of about 9 to 70 ㎛ in consideration of the thickness or mechanical properties of the final product.

[0132] The aforementioned metal laminate sheet can be manufactured by a method known in the art. For example, a prepreg is laminated on one side of a first metal foil (e.g., a first copper foil), a second metal foil (e.g., a second copper foil) is laminated thereon, and then heating and pressurizing are performed to obtain a metal laminate sheet.

[0133] According to an example, the metal laminated sheet of the present invention can be manufactured by a roll-to-roll device, and can be manufactured by a method including, for example, the steps of (S100) applying the above-described resin composition onto a first metal foil supplied from a fourth supply roller on which a first metal foil is wound and continuously traveling, and drying the same to continuously form a first unit member including a first resin composition film and the first metal foil; (S200) applying the above-described resin composition onto a second metal foil supplied from a fifth supply roller on which a second metal foil is wound and continuously traveling, and drying the same to continuously form a second unit member including a second resin composition and the second metal foil; and (S300) laminating the first and second unit members on both sides of a fiber substrate supplied from a sixth supply roller on which a fiber substrate is wound and continuously traveling, while heating and pressurizing the first and second unit members with a pair of heating rollers so that the resin composition film of each unit member comes into contact with the surface of the fiber substrate.

[0134] Hereinafter, each step of manufacturing the metal laminate sheet of the present invention will be described.

[0135] (S100) Step: Formation step of the first unit member

[0136] Step (S100) is a step for forming a first unit member, in which the first metal foil is supplied from the fourth supply roller on which the first metal foil is wound, and the above-described resin composition is directly applied (coated) onto one surface of the continuously running first metal foil, and then dried at about 50 to 150° C., thereby obtaining a first unit member on which a film of the first resin composition is formed on one surface of the first metal foil. At this time, the first unit member to be formed can be continuously transported to a bonding area with the fiber substrate by the traveling roller and bonded to the fiber substrate by a pair of heating rollers. Of course, the first unit member to be formed can be wound on the winding roller, then unwound again from the bonding area with the fiber substrate, and bonded to the fiber substrate. In this case, the following step (S200) is omitted, and only the above-described step (S100) is performed to manufacture two unit members, which can then be used. In this way, the first unit member can be manufactured by directly coating and drying the resin composition on the first metal foil without a film forming process (paste extrusion, calendering) and a high-temperature firing process. In this case, since the first resin composition film has excellent adhesion to the first metal foil, the durability of the final metal laminate sheet can be improved.

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

[0138] The above direct application (coating) method is not particularly limited, and includes, for example, a roll-to-roll coating method, and specifically, comma coating, slot die coating, curtain coating, and spray coating.

[0139] The drying process of the above resin composition is for drying and removing the organic solvent in the resin composition, and is performed at a temperature of about 50 to 150°C for about 1 to 10 minutes, thereby forming a film of the first resin composition on the first metal foil. In this way, the present invention only dries the resin composition before the bonding process with the fiber substrate, and does not perform a high-temperature firing process of 350°C or higher.

[0140] The first unit member manufactured through the aforementioned step (S100) includes a first metal foil and a first resin composition film disposed on one surface of the first metal foil.

[0141] (S200) Step: Formation step of the second unit member

[0142] (S200) Step is a step for forming a second unit member, in which the second metal foil is supplied from the fifth supply roller on which the second metal foil is wound, and the above-described resin composition is directly applied (coated) onto one side of the continuously running second metal foil, and then dried at about 50 to 150°C, thereby obtaining a second unit member on which a film of the second resin composition is formed on one side of the second film. At this time, the second unit member to be formed may be continuously transported to a lamination area with a fiber substrate by a running roller and laminated with the fiber substrate by a pair of heating rollers. Of course, the second unit member to be formed may be wound on a winding roller and then unwound again from the lamination area with the fiber substrate and laminated with the fiber substrate. In this way, the second unit member may be the same as or different from the first unit member, and, like the first unit member, may be manufactured by directly coating and drying the resin composition on the second metal foil without a film forming process (paste extrusion, calendering) and a high-temperature firing process. At this time, since the second resin composition film has excellent adhesion to the second metal foil, the durability of the final metal laminate sheet can be improved.

[0143] In the present invention, the second metal foil may be the same as or different from the first metal foil. The description of the second metal foil is the same as the description of the first metal foil, and thus is omitted.

[0144] In addition, the description of the coating method and drying process of the resin composition is omitted because it is the same as that described in step (S100).

[0145] The second insulating member manufactured through the aforementioned step (S200) includes a second metal foil and a second resin composition film disposed on one surface of the second metal foil.

[0146] (S300) Step: Lamination step between first unit member-fiber substrate-second unit member

[0147] The first and second unit members manufactured in the above steps (S100) and (S200), respectively, are laminated on both sides of a continuously running fiber substrate supplied from a sixth supply roller on which a fiber substrate is wound, and then heated and pressurized by a pair of heating rollers. However, when laminating the first and second unit members with the fiber substrate, the resin composition film of each unit member is laminated so that it comes into contact with the fiber substrate.

[0148] Specifically, in step (S300), the first unit member formed in step (S100) and continuously supplied (transported) by the traveling roller is laminated on one side of the fiber substrate supplied from the sixth supply roller on which the fiber substrate is wound, and at the same time, the second unit member formed in step (S200) and continuously supplied (transported) is laminated on the other side of the fiber substrate, and then a laminate of the first unit member-fiber substrate-second unit member can be thermally compressed by a pair of heating rollers facing each other on both sides of the fiber substrate. At this time, the unit members are continuously supplied and laminated and thermally compressed so that the resin composition film of each unit member is in contact with the fiber substrate.

[0149] The description of the above fiber substrate is omitted because it is the same as that described in the prepreg section.

[0150] The above-described thermocompression process can be performed by heating and pressing at a pressure of about 10 to 80 kgf / ㎠ per m of the fiber substrate and a temperature of about 300 to 400°C for about 0.1 minute to 1 hour. In one example, a roll-to-roll device having a pair of heating rollers can be used to thermocompression-bond a laminate in the order of first unit member / fiber substrate / second unit member at a pressure of about 10 to 50 kgf / ㎠ for about 0.1 minute to 1 hour. At this time, even if the thermocompression time is short or the thermocompression temperature is low, the elastomer and PFA in each resin composition film can easily melt and bind the hollow inorganic filler while diffusing (moving) into the fiber substrate and hardening into a polymer matrix. As a result, the first and second resin layers in which each resin composition film is semi-cured (B-staged) can be formed in close contact with the fiber substrate. Accordingly, the present invention can manufacture a metal laminate sheet in which a first metal foil / first resin layer / fiber substrate / second resin layer / second metal foil are integrated with each other. The metal laminate sheet manufactured at this time can be wound around a winding roller in a long form with a length of 10 m or more.

[0151] The first and second resin layers may have a dielectric constant (Dk) in the range of 1.5 to 2.0 at 25°C and 10 GHz. Here, the dielectric constant (D) of the first and second resin layers k ) was measured at 25℃, 10 GHz using SPDR method (IEC 61189-2-721).

[0152]

[0153] Printed circuit board

[0154] Meanwhile, the present invention provides a printed circuit board comprising the above-described resin composition.

[0155] The printed circuit board of the present invention refers to one laminated in one or more layers by a plating through-hole method or a build-up method, and can be obtained by covering and fitting the above-mentioned prepreg or laminated sheet on an inner wiring board and then heat-pressuring and molding it.

[0156] For example, a printed circuit board according to the present invention includes the aforementioned metal laminate sheet. At this time, a circuit pattern may be formed on the metal foil (first metal foil and / or second metal foil) included in the metal laminate sheet. Furthermore, a resin layer or prepreg included in the metal laminate sheet serves as an insulating support member.

[0157] The above printed circuit board can be manufactured by a conventional method known in the art. For example, it can be manufactured by continuously supplying a roll-type metal laminate using a roll-to-roll device, opening a hole in the flexible metal laminate to perform through-hole plating, and then etching a metal foil (e.g., copper foil) containing a plating film to form a circuit.

[0158] As described above, the resin composition described above has a low dielectric constant and dielectric loss tangent in a frequency band of about 10 GHz or higher, and excellent heat resistance and moldability. Therefore, a printed circuit board to which the resin composition is applied also has a low dielectric loss in a frequency band of about 10 GHz or higher, which can reduce transmission loss of electrical, electronic, and communication devices, and also has excellent heat resistance. Therefore, the printed circuit board of the present invention can be usefully applied to various electrical, electronic, and communication devices, such as mobile communication devices that handle high-frequency or ultra-high-frequency signals, base station devices thereof, network-related electronic devices such as servers and routers, large computers, and automotive radar devices.

[0159]

[0160] Hereinafter, the present invention will be described in detail through examples, but the following examples and experimental examples are merely illustrative of one form of the present invention, and the scope of the present invention is not limited to the following examples and experimental examples.

[0161] <Example 1>

[0162] 1-1. Preparation of resin composition

[0163] A resin composition was prepared by mixing each component according to the composition described in Table 1 below. At this time, in Table 1 below, the unit of content (amount used) of each component is weight%, and is based on the total amount of the water composition (100 weight%).

[0164] 1-2. Preparation of prepreg

[0165] The resin composition manufactured in Example 1-1 was applied (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, and then the applied resin composition was dried at about 140°C for about 3 minutes to manufacture a roll-type first insulating member having a first resin composition film formed on one side of the first PI film. Meanwhile, a roll-type second insulating member having a second resin composition film formed on one side of a second PI film was manufactured by performing the same process as for manufacturing the first insulating member.

[0166] The first and second insulating members of the roll type, each manufactured, were laminated on both sides of a glass fabric continuously supplied from a glass fabric supply roller, and then a pair of high-temperature roll presses were used to thermally press the prepreg at a temperature of 320°C or higher and a pressure of 30 kgf / cm to wind the prepreg onto the roller, thereby manufacturing a roll-type prepreg. When laminating the unit members, the resin composition film within each insulating member was laminated so as to come into contact with the surface of the glass fabric.

[0167] 1-3. Manufacturing of copper-clad laminates

[0168] The resin composition prepared in Example 1-1 was applied (thickness: 100 ㎛) on one surface of a first copper foil (thickness: 18 ㎛, roughness (Rz): 3 ㎛ or less) continuously supplied from a copper foil supply roller using a pair of coating rollers, and then the applied resin composition was dried at about 140°C for about 3 minutes to manufacture a roll-type first unit member having a first resin composition film formed on one surface of the first copper foil. Meanwhile, a roll-type second unit member having a second resin composition film formed on one surface of a second copper foil was manufactured by performing the same process as for manufacturing the first unit member.

[0169] The first and second unit members of the roll type manufactured respectively were laminated on both sides of the prepreg continuously supplied from the prepreg supply roller manufactured in Example 1-2, and then a pair of high-temperature roll presses were used to thermally press the prepreg at a temperature of 300°C or higher and a pressure of 30 kgf / cm to wind the flexible copper-clad laminate onto the rollers, thereby manufacturing a roll-type flexible copper-clad laminate. When laminating the unit members, the resin composition film inside each unit member was laminated so that it was in contact with the surface of the prepreg. In addition, before using the prepreg, both PI films inside the prepreg were peeled and removed.

[0170] 1-4. Manufacturing of printed circuit boards

[0171] While continuously supplying the flexible copper-clad laminate manufactured in the above Examples 1-3, a photosensitive dry film was applied by applying heat and pressure to the flexible copper-clad laminate, and then light was irradiated and developed using a master film showing a circuit, thereby continuously manufacturing a flexible printed circuit board (FPCB). The copper foil including the unnecessary plating film on the surface of the completed printed circuit board was removed (etched) with a highly corrosive agent to form a circuit.

[0172] Example Comparative Example 12341234A7777777777775292B-120-----455B-2-20------B-3--2020----B-4----20---B-5-----20--C-1333-3333C-2---3----D-1505050-50505050D-2---50----

[0173]

[0174] Composition details specifications A Perfluoroalkoxy alkane (PFA) ACX-21 from Daikin (Df: 2.1, Dk: 0.0003, MFR: 7g / 10min, average particle size (d50): 25㎛, Tm: 310℃) B-1 Hollow silica with 60% porosity Average particle size (d50): 2.3㎛, Dk: 1.35, Df: 0.0005 B-2 Hollow silica with 75% porosity Average particle size (d50): 2㎛, Dk: 1.5, Df: 0.0010 B-3 Hollow silica with 88% porosity S32HS from 3M (Average particle size (d50): 22㎛, Dk: 1.35, Df: 0.0043) B-4 Silica (Porosity: 0%) SO-C2 from Admatechs (Average particle size (d50): 0.5 ㎛, Dk: 3.5, Df: 0.002) B-5 Hollow silica with a porosity of 38% Average particle size (d50): 0.6 ㎛, Dk: 2.8, Df: 0.003 C-1 Fluorine-based elastomer FKM (Fluoro elastomer copolymer) (Dk: 3.0, Df: 0.002, fluorine (F) content: 68 wt% per molecule, thermal decomposition temperature: about 390°C) C-2 Styrene-based elastomer SEEPS (Styrene-Ethylene-Ethylene-Propylene-Styrene) (Dk: 2.4, Df: 0.001, styrene content: per molecule) 30 wt%, thermal decomposition temperature: about 390℃, MFR: 0.1 g / 10 min or less D-1MEK(methylethylketone)D-2Toluene

[0175]

[0176] <Examples 2 to 4 and Comparative Examples 1 to 4>

[0177] A resin composition, prepreg, copper-clad laminate, and printed circuit board were each manufactured in the same manner as in Example 1, except that the compositions were changed as described in Table 1 above.

[0178]

[0179] <Experimental Example 1> - Physical Property Evaluation

[0180] The physical properties of the cured products of the resin compositions manufactured in Examples 1 to 4 and Comparative Examples 1 to 4 were evaluated by the following method, and the results are shown in Table 3 below.

[0181] 1) Specific gravity of the insulator

[0182] The copper foil of the copper-clad laminates manufactured in Examples 1 to 4 and Comparative Examples 1 to 4 was wet-removed with an etchant (hydrochloric acid:hydrogen peroxide = 1:2 volume ratio), and the remaining insulator was dried at 110°C for 2 hours to obtain a sample. The specific gravity of the obtained sample was measured according to the water displacement method [ASTM D792 test method (temperature of 23±2°C)].

[0183] 2) Dielectric constant (Dk) and dielectric loss tangent (Df)

[0184] The copper foil of the copper-clad laminates manufactured in Examples 1 to 4 and Comparative Examples 1 to 4 was wet-removed with an etchant (hydrochloric acid:hydrogen peroxide = 1:2 volume ratio), and then dried at 110°C for 2 hours to obtain a sample. For the obtained sample, Dk and Df at 25°C and 10 GHz were measured using the SPDR method (IEC 61189-2-721).

[0185] 3) Coefficient of thermal expansion (CTE)

[0186] The copper foil of the copper-clad laminates manufactured in Examples 1 to 4 and Comparative Examples 1 to 4 was wet-removed with an etchant (hydrochloric acid:hydrogen peroxide = 1:2 volume ratio), and then dried at a temperature of 110°C for 2 hours to obtain a sample. Thereafter, the CTE in the X / Y direction was measured for the obtained sample using a TMA (Thermomechanical Analyzer) according to the IPC-TM-650 2.4.41.2 test method.

[0187] 4) Resin flowability

[0188] The prepregs manufactured in Examples 1 to 4 and Comparative Examples 1 to 4 were pressed at a temperature of 350°C and a pressure of 5700 lb for 5 minutes, and the degree of resin flow was visually confirmed. If the resin was confirmed to flow outside the hot plate of the press, the resin flowability was marked with "○", and if the resin did not flow outside the hot plate of the press, the resin flowability was marked with "×".

[0189] 5) Adhesiveness

[0190] The adhesive strength of the interface between the copper foil and the resin composition of the copper-clad laminates manufactured in Examples 1 to 4 and Comparative Examples 1 to 4 was measured according to the IPC-TM-650 2.4.8 method. At this time, the adhesive strength at the point where the copper foil was peeled from the resin composition was 0.4 kgf / cm. 2 In case of abnormality, it is marked with “○” and the adhesive force is 0.4 kgf / cm 2 If it is less than that, it is marked as “×”.

[0191] 6) Heat resistance

[0192] The copper-clad laminates manufactured in Examples 1 to 2 and Comparative Examples 1 to 3 were measured according to the IPC-TM-650 2.3.13 test method (solder pot, 288 ℃, 30 sec), and changes were confirmed visually. At this time, if there were no visual abnormalities such as swelling of the copper foil, they were marked with "○", and if there were visual abnormalities, they were marked with "×".

[0193] Example Comparative Example 12341234 Insulator Specific Gravity 1.19 1.33 0.95 0.93 2.11 87 0.77 1.77 Dk (25℃, 10 GHz) 1.7 1.8 11 66 1.65 2.36 2.30 1.5 2 2.05 Df (25℃, 10 GHz) 0.00 10.00 10.00 30.00 30.00 10.00 20.00 10.00 1 CTE (ppm / ℃) 17 14 12 11 5 5 4 3 10 6 2 Resin Flowability ○○○○○○×○ Adhesiveness ○○○○○○×○ Heat Resistance ○○○○○○×○

Claims

1. Perfluoroalkoxy alkane (PFA); At least one elastomer selected from the group consisting of styrenic elastomers and fluorine-based elastomers; and Hollow inorganic filler having a porosity of 60 to 90%; A resin composition comprising:

2. In paragraph 1, The above hollow inorganic filler has a dielectric constant (D) in the range of 1 to 3 at 25°C and 10 GHz. k ) having a resin composition.

3. In paragraph 2, A resin composition wherein the hollow inorganic filler has an average particle diameter (D50) in the range of 0.5 to 50 μm.

4. In paragraph 3, A resin composition wherein the hollow inorganic filler contains hollow silica.

5. In paragraph 1, The above perfluoroalkoxy alkane contains a tetrafluoroethylene repeating unit and a perfluoroether repeating unit, A resin composition wherein the tetrafluoroethylene repeating unit and the perfluoroether repeating unit are included in a molar ratio range of 1:10 to 1:10000.

6. In paragraph 1, A resin composition further comprising an organic solvent.

7. In paragraph 1, Based on the total amount of the resin composition, 40 to 80 wt % of a perfluoroalkoxy alkane; 0.1 to 10 wt% elastomer; and 10 to 40 wt% hollow inorganic filler A resin composition comprising:

8. In paragraph 1, A resin composition, wherein a cured product of the resin composition has a dielectric constant (Dk) in the range of 1.5 to 2.0 at 25°C and 10 GHz.

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

10. In paragraph 9, A prepreg having a coefficient of thermal expansion of 20 ppm / ℃ or less and a dielectric constant (Dk) of 2.0 or less at 25℃ and 10 GHz.

11. A step of applying a resin composition according to any one of claims 1 to 8 onto a first film that is continuously run by being supplied from a first supply roller on which a first film is wound, and drying the same to continuously form a first insulating member including a resin layer and the first film; A step of applying a resin composition according to any one of claims 1 to 8 onto a second film continuously running from a second supply roller on which a second film is wound, and drying the same to continuously form a second insulating member including a resin layer and a second film; and A step of laminating the first and second insulating members on both sides of a continuously running fiber substrate supplied from a third supply roller on which the fiber substrate is wound, while heating and pressurizing with a pair of heating rollers while laminating the resin layer of each insulating member so that it comes into contact with the surface of the fiber substrate. A method for manufacturing a roll-type prepreg including:

12. A metal laminate sheet comprising a resin composition according to any one of claims 1 to 8.

13. A step of applying a resin composition according to any one of claims 1 to 8 onto a first metal foil continuously running from a fourth supply roller on which a first metal foil is wound, and drying the same to continuously form a first unit member including a resin layer and the first metal foil; A step of applying a resin composition according to any one of claims 1 to 8 on a second metal foil continuously running from a fifth supply roller on which a second metal foil is wound, and drying the same to continuously form a second unit member including a resin layer and a second metal foil; and A step of laminating the first and second unit members on both sides of a continuously running fiber substrate supplied from a sixth supply roller on which a fiber substrate is wound, while heating and pressurizing with a pair of heating rollers while laminating the resin layer of each metal unit member so that it comes into contact with the surface of the fiber substrate. A method for manufacturing a roll-type metal laminated sheet comprising:

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