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

Abstract

The present invention relates to a resin composition characterized by a low degree of thermal expansion, a low degree of dielectricity, and a high degree of thermal resistance, and a prepreg, a metal foil laminate, a laminated sheet, and a printed circuit board comprising same. The resin composition comprises a polyphenylene oxide-based resin, a hollow inorganic filler having a porosity of 60-90%, a fluorine resin filler, and a dispersant.

Description

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

[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 foil laminate, 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, fluoropolymers, liquid crystal polymers (LCPs), and modified polyimides (MPIs) capable of high-frequency operation 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 capable of manufacturing a prepreg having a low coefficient of thermal expansion (CTE), excellent low dielectric properties, heat resistance and resin flowability, and capable of a lamination process without a high-temperature molding process.

[0005] In addition, the present invention seeks to provide a prepreg, a metal foil laminate, 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 purpose, the present invention provides a resin composition comprising: a polyphenylene oxide-based resin; a hollow inorganic filler having a porosity of 60 to 90%; and a dispersant.

[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 resin composition may additionally include a fluororesin filler.

[0011] According to another example, the fluororesin filler has a dielectric constant (D) in the range of 2 to 3 at 25°C and 10 GHz. k ) can have.

[0012] According to another example, the fluororesin filler may contain at least one selected from the group consisting of polytetrafluoroethylene (PTFE), perfluoroalkoxy alkane (PFA), tetrafluoroethylene-hexafluoropropylene copolymer (FEP), polychlorotrifluoroethylene (PCTFE), ethylene-tetrafluoroethylene copolymer (ETFE), tetrafluoroethylene-chlorotrifluoro ethylene copolymer (TFE / CTFE), ethylene-chlorotrifluoroethylene copolymer (ECTFE), and polychlorotrifluoroethylene (PCTFE).

[0013] According to another example, the dispersant may contain a non-ionic dispersant.

[0014] According to another example, the dispersant may contain at least one selected from the group consisting of a polyoxyethylene glycol alkylphenol ether dispersant, a polysorbate dispersant, and a poly(oxyethylene) alkyl ether dispersant.

[0015] According to another example, the resin composition may additionally include at least one selected from the group consisting of a curing agent, a reaction initiator, a curing accelerator, an additive, and a solvent.

[0016] According to another example, the resin composition may include, based on the total amount of the resin composition, 10 to 70 wt% of a polyphenylene oxide-based resin; 5 to 40 wt% of a hollow inorganic filler; and 0.0001 to 5 wt% of a dispersant.

[0017] According to another example, the cured product of the resin composition has a dielectric constant (D) in the range of 1.5 to 2.2 at 25° C. and 10 GHz. k ) can have.

[0018] In addition, the present invention provides a prepreg comprising the above-described resin composition.

[0019] According to an example, the prepreg has a dielectric constant (D) at 25°C and 10 GHz k ) may be less than or equal to 2.5.

[0020] In addition, the present invention provides a metal foil laminate comprising the above-described resin composition.

[0021] In addition, the present invention provides a printed circuit board comprising the above-described resin composition.

[0022] 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.

[0023] In addition, the resin composition according to the present invention can produce a prepreg capable of a lamination process without a high-temperature molding process.

[0024] 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.

[0025] Hereinafter, the present invention will be described.

[0026] 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.

[0027] 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.

[0028] 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.

[0029] 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.

[0030]

[0031] Resin composition

[0032] In order to minimize propagation loss in the frequency band for 5G~6G communication, fluororesin was used as the matrix resin of prepreg. In this case, the dielectric constant (D) of the fluororesin k ) and genetic loss (D f ) is low, it was possible to implement a prepreg with low dielectric properties and low dielectric loss. However, the fluororesin is a thermoplastic resin and has a high melting point of about 300 ℃ or higher. For this reason, when manufacturing a prepreg containing a fluororesin, a high-temperature molding process had to be performed for a long time under high-temperature conditions of about 300 ℃ or higher, which caused problems of low productivity and increased manufacturing costs. In addition, the thermal expansion coefficient of the fluororesin is high. For this reason, when a prepreg containing a fluororesin is applied to a metal foil laminate (e.g., a copper foil laminate), the prepreg and the metal foil laminate may be partially separated due to the difference in thermal expansion coefficient between the prepreg and the metal foil.

[0033] In order to solve the above-mentioned problems, the present invention attempted to use a resin composition including a polyphenylene oxide-based resin, a hollow inorganic filler, and a dispersant. In general, since transmission loss is proportional to the relative permittivity (Dk) and dielectric loss (Df) of an insulator, the present invention uses a hollow inorganic filler containing air inside in order to implement a permittivity lower than the intrinsic relative permittivity (Dk) of the polyphenylene oxide-based resin. However, if the porosity of the hollow inorganic filler is too small, the permittivity reduction effect 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 broken during the lamination process, which may increase the permittivity.

[0034] Accordingly, the present invention includes a polyphenylene oxide-based resin, a hollow inorganic filler, and a dispersant, wherein the hollow inorganic filler has a void ratio controlled to a range of 60 to 90%. 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 that can be laminated 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.

[0035] According to an example, a resin composition according to the present invention comprises (a) a polyphenylene oxide-based resin; (b) a hollow inorganic filler having a porosity of 60 to 90%; and (c) a dispersant.

[0036] According to another example, the resin composition according to the present invention may additionally include a fluorine resin filler in addition to the above-described components.

[0037] 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, an additive, and a solvent.

[0038] Hereinafter, each component of the resin composition according to the present invention will be described.

[0039] (a) Polyphenylene oxide resin

[0040] In the resin composition according to the present invention, polyphenylene oxide resin [poly(phenylene oxide), PPO] is a base resin, which has excellent electrical insulation properties, heat resistance, water resistance, dimensional stability, and low dielectric properties, does not contain environmentally harmful components such as halogen, and is self-extinguishing, making it easy to secure flame retardancy.

[0041] Non-limiting examples of such polyphenylene oxide resins include poly(2,3-dimethyl-6-ethyl-1,4-phenylene ether), poly(2-methyl-6-chloromethyl-1,4-phenylene ether), poly(2-methyl-6-hydroxyethyl-1,4-perene ether), poly(2-methyl-6-n-butyl-1,4-phenylene ether), poly(2-ethyl-6-isopropyl-1,4-phenylene ether), poly(2-ethyl-n-propyl-1,4-phenylene ether), poly(2,3,6-trimethyl-1,4-phenylene ether), poly(2-ethyl(4'-methylphenyl)-1,4-phenylene ether), poly(2-bromo-6-phenyl-1,4-phenylene ether), poly(2-methyl-6-phenyl-1,4-phenylene ether), poly(2-phenyl-1,4-phenylene ether), Poly(2-chloro-1,4-phenylene ether), poly(2-methyl-1,4-phenylene ether), poly(2-chloro-6-ethyl-1,4-phenylene ether), poly(2-chloro-6-bromo-1,4-phenylene ether), poly(2,6-di-n-propyl-1,4-phenylene ether), poly(2-methyl-6-isopropyl-1,4-phenylene ether), poly(2-chloro-6-methyl-1,4-phenylene ether), poly(2-methyl-6-ethyl-1,4-phenylene ether), poly(2,6-dichloro-1,4-phenylene ether), poly(2,6-diethyl-1,4-phenylene ether), poly(2,6-dimethyl-1,4-phenylene ether), poly(2,6-dibromo-1,4-phenylene ether), Examples include poly(2,6-dichloro-1,4-phenylene ether), and copolymers such as copolymers of 2,6-dimethylphenol and other phenols (e.g., 2,3,6-trimethylphenol). In addition, those modified with maleic anhydride, fumaric acid, etc. are also possible.

[0042] In the resin composition of the present invention, the content of the polyphenylene oxide-based resin may be in the range of about 10 to 70 wt%, specifically about 30 to 70 wt%, and more specifically about 40 to 70 wt%, based on the total amount (100 wt%) of the resin composition. If the content of the polyphenylene oxide-based resin is less than 10 wt%, the dielectric constant or rigidity of the entire resin composition may be reduced, and on the other hand, if the content of the polyphenylene oxide-based resin exceeds 70 wt%, the heat resistance may be reduced.

[0043] (b) Hollow weapon filler

[0044] 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, and mechanical strength (toughness) of the final product.

[0045] 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, observed by an electron microscope across the cross-section of the hollow inorganic filler and calculated by measuring the thickness of the shell). If the porosity of the hollow inorganic filler is less than 60%, the proportion of air may be relatively reduced, resulting in a small dielectric constant reduction effect. 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 result in an increase in dielectric constant.

[0046] 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.

[0047] Additionally, the hollow inorganic filler has a dielectric constant (D) in the range of about 1 to 3 at 25°C 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).

[0048] The components of the above hollow inorganic filler may be, but are not limited to, 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, borosilicate, etc. These may be used alone or in combination of two or more. Among these, silica having high physical strength and low thermal expansion coefficient is preferable.

[0049] In one example, the hollow inorganic filler may be hollow silica. This hollow silica may further 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 1 to 3 wt% of aluminum oxide.

[0050] The shape of the above hollow inorganic filler may be a spherical particle, but may also be an irregular particle.

[0051] 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.

[0052] 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 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.

[0053] For example, the silane coupling agent may be a vinyl-based silane coupling agent (e.g., vinyltriethoxysilane, vinyltripropoxysilane, vinyltriisopropoxysilane, vinyltributoxysilane, etc.). In this case, since the compatibility with the modified polyphenylene ether containing unsaturated functional groups (e.g., vinyl group and / or allyl group) at both terminals is excellent, the dielectric constant and dielectric loss tangent can be lowered, and the moisture absorption heat resistance and processability can be further improved.

[0054] 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 the cured product of the resin composition (e.g., resin layer) or the prepreg to which the resin composition is applied.

[0055] In the resin composition of the present invention, the content of the hollow inorganic filler may be in the range of about 5 to 40 wt%, specifically about 15 to 40 wt%, and more specifically 25 to 35 wt%, based on the total weight of the resin composition. If the content of the hollow inorganic filler is less than about 5 wt%, the effect of reducing the dielectric constant may be insignificant. On the other hand, if the content of the hollow inorganic filler exceeds about 40 wt%, the moldability of the resin composition may deteriorate.

[0056] (c) dispersant

[0057] In the resin composition according to the present invention, the dispersant can prevent the hollow inorganic filler or the fluororesin filler from agglomerating, and the resin flowability of the resin composition can be improved.

[0058] In one example, the dispersant may include a nonionic dispersant (nonionic surfactant).

[0059] Examples of the above dispersant include, but are not limited to, polyoxyethylene glycol alkylphenol ether dispersants such as Triton X-100 (Polyoxyethylene glycol octyl phenol ether); polysorbate dispersants such as Tween 20 (Polysorbate 20), Tween 80 (Polysorbate 80); and poly(oxyethylene) alkyl ether dispersants such as Brij L23. These may be used alone or in combination of two or more.

[0060] In the resin composition of the present invention, if the content of the dispersant is too high, the dielectric constant and heat resistance may deteriorate, and if it is too low, the dispersing effect may be insufficient. Therefore, the content of the dispersant may be adjusted to a range of about 0.0001 to 5 wt% based on the total amount of the resin composition. However, when the resin composition of the present invention includes a fluororesin filler, the content of the dispersant 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 100 wt% of the fluororesin filler.

[0061] (d) Fluorine resin filler

[0062] The resin composition according to the present invention may additionally include a fluororesin filler. The fluororesin filler is a fluororesin particle containing fluorine (F), and is a particle-shaped organic filler such as powder or fiber in a solid state at room temperature (about 20±5°C). When the resin composition is dried or semi-cured, the fluororesin filler is dispersed in the polyphenylene oxide resin by a dispersing agent together with the hollow inorganic filler while maintaining the particle shape, and is subsequently melted by high-temperature pressing and incorporated into the cured resin as a polymer matrix component. Therefore, the fluororesin filler not only implements low dielectric constant and low dielectric loss characteristics of the cured resin, but also can improve heat resistance and improve adhesion between the fiber-containing substrate of the prepreg or the metal foil.

[0063] In addition, the fluororesin filler can have a dielectric constant (Dk) of approximately 2 to 3 at 25°C and 10 GHz. Thus, since the fluororesin filler has a low dielectric constant and a low dielectric tangent, the cured product of the resin composition can have low dielectric constant and low dielectric loss characteristics. Here, the dielectric constant (Dk) of the fluororesin filler was measured at 25°C and 10 GHz using the SPDR method (IEC 61189-2-721).

[0064] The above fluorine resin filler may have a melting point (Tm) in the range of about 280 to 340°C. At this time, the fluorine resin filler, like the hollow inorganic filler, exists in a solid phase within the resin composition and acts to lower the dielectric constant.

[0065] Additionally, the fluororesin filler may have a melt flow rate (MFR) of about 0.0001 to 50 g / 10 min at about 372°C and about 5 kg according to the ISO 1133-1 test method.

[0066] The fluororesin filler usable in the present invention is not particularly limited as long as it is a particle formed of a fluorine-containing resin known in the art. Examples of the fluororesin filler include, but are not limited to, polytetrafluoroethylene (PTFE), perfluoroalkoxy alkane (PFA), tetrafluoroethylene-hexafluoropropylene copolymer (FEP), polychlorotrifluoroethylene (PCTFE), ethylene-tetrafluoroethylene copolymer (ETFE), tetrafluoroethylene-chlorotrifluoroethylene copolymer (TFE / CTFE), ethylene-chlorotrifluoroethylene copolymer (ECTFE), polychlorotrifluoroethylene (PCTFE), and the like. Among these, PFA and PTFE are preferable because they have a low Df of 0.0002 or less.

[0067] These fluororesin fillers have an average particle size (D50 ) This may be in the range of about 1 to 50 μm. In this case, the fluororesin filler can be uniformly dispersed within the resin composition without agglomeration, and the handling properties of the resin composition after coating can be improved. However, in the present invention, one type of fluororesin filler having the same average particle diameter can be used alone, or two or more types of fluororesin fillers having different average particle diameters can be used in combination. Here, the average particle diameter (D50) of the fluororesin filler can be measured according to ASTM D4464.

[0068] In addition, the shape of the fluororesin filler is not particularly limited, and includes, for example, spherical, flake, dendrite, conical, pyramidal, and amorphous shapes, and these may be used alone or in combination of two or more. For example, the shape of the fluororesin filler may be spherical. In this case, since the surface area of ​​the fluororesin filler is minimized, the processing characteristics of the resin composition can be improved, and isotropic characteristics can be imparted to the resin layer.

[0069] In the resin composition of the present invention, the content of the fluororesin filler may be in the range of more than 0 wt% to 50 wt%, specifically in the range of about 10 to 50 wt%, and more specifically in the range of about 10 to 30 wt%, based on the total amount of the resin composition. By adjusting the content of the fluororesin filler within the above-described range, the resin composition can form a resin layer or prepreg having a low dielectric constant.

[0070] (e) hardener

[0071] The resin composition according to the present invention may additionally contain a curing agent as needed.

[0072] The curing agent is a cross-linking curing agent that can form a network structure by three-dimensionally cross-linking the polyphenylene oxide resin, thereby improving the heat resistance and fluidity of the resin composition, and further improving the peel strength between the resin layer and other substrates.

[0073] Examples of curing agents usable in the present invention include allyl oxide compounds prepared by reacting vinylbenzyl oxide compounds such as divinylbenzene, divinylnaphthalene, divinyldiphenyl, styrene monomer, phenol, and allyl chloride; diene compounds such as triallyl isocyanurate (TAIC), triallylicyanurate (TAC), 1,2,4-trivinyl cyclohexane, 1,7-octadiene, and 1,9-decadiene; and di-4-vinylbenzyl oxide. The above-mentioned curing agents may be used alone or in combination of two or more. These are preferable because they not only have excellent compatibility, but also excellent formability, a low dielectric constant value, excellent heat resistance, and reliability.

[0074] In the resin composition of the present invention, the content of the curing agent may be in the range of about 5 to 50 parts by weight, specifically about 10 to 40 parts by weight, based on 100 parts by weight of the polyphenylene oxide-based resin. If the content of the curing agent falls within the above-mentioned range, the resin composition has good curability, moldability, and adhesive strength.

[0075] (f) reaction initiator

[0076] The resin composition according to the present invention may further include a reaction initiator, if necessary. The reaction initiator generates radicals through heat or the like, and can further accelerate the curing of the polyphenylene oxide resin or curing agent, thereby improving the heat resistance of the resin layer.

[0077] Non-limiting examples of reaction initiators usable in the present invention include α,α′-bis(t-butylperoxy-m-isopropyl)benzene, 2,5-dimethyl-2,5-di(t-butylperoxy)-3-hexyne, benzoyl peroxide, 3,3′,5,5′-tetramethyl-1,4-diphenoxyquinone, chloranil, 2,4,6-tri-t-butylphenoxyl, t-butylperoxyisopropyl monocarbonate, azobisisobutylonitrile, and the like. Additionally, metal carboxylate salts may be further used.

[0078] The content of the above reaction initiator may be about 1 to 5 wt%, specifically about 0.1 to 2 wt%, based on the total amount of the resin composition.

[0079] (g) additives

[0080] In addition to the components described above, the resin composition of the present invention may further include additives such as various polymers (e.g., phenoxy resin, polyvinyl acetal resin, polyimide, polyamideimide, polyethersulfone, polysulfone, etc.), solid rubber particles, or ultraviolet absorbers, antistatic agents, flame retardants, antioxidants, polymerization initiators, dyes, pigments, thickeners, leveling agents, stress relievers, etc., commonly known in the art, as long as the inherent properties of the resin composition are not impaired.

[0081] For example, the additives include organic fillers such as silicone powder, nylon powder, and fluororesin powder; thickeners such as Orben and Benton; polymer-based defoaming agents or leveling agents such as silicone and fluororesin; adhesion-imparting agents such as imidazole-based, thiazole-based, triazole-based, and silane-based coupling agents (e.g., epoxysilane, aminosilane, vinylsilane, etc.); colorants such as phthalocyanine and carbon black; release agents such as higher fatty acids, higher fatty acid metal salts, and ester-based waxes; stress-relieving agents such as modified silicone oil, silicone powder, and silicone resin; flame retardants such as A, B, C, etc. In addition, the additives may be commonly used in resin compositions used in the production of electronic devices (particularly, printed wiring boards).

[0082] The content of such additives may be about 0.001 to 20 wt%, specifically about 0.01 to 5 wt%, and more specifically about 0.01 to 1 wt%, based on the total amount of the resin composition.

[0083] (h) organic solvents

[0084] The resin composition of the present invention described above may be in the form of a resin varnish containing an organic solvent. In this case, the resin composition may be dissolved or dispersed in the organic solvent.

[0085] The organic solvent usable in the present invention may be any conventional organic solvent known in the art without limitation, and examples thereof include acetone, cyclohexanone, methyl ethyl ketone, toluene, xylene, tetrahydrofuran, etc., and these may be used alone or in a mixture of two or more.

[0086] The content of the organic solvent may be in the range of the remaining amount satisfying 100 parts by weight of the total varnish using the composition ratio of the above-mentioned composition, and is not particularly limited.

[0087] As described above, the resin composition of the present invention is characterized by including a polyphenylene oxide-based resin having excellent electrical properties in a high frequency to ultra-high frequency band, a hollow inorganic filler having a specific porosity, a fluororesin filler, and a dispersant, and is a high frequency low-dielectric constant low-loss resin composition that can be used for manufacturing prepregs, sheets, films, tapes, laminates, or printed wiring boards. In addition, the resin composition of the present invention has a low coefficient of thermal expansion (CTE) and excellent heat resistance and resin flowability.

[0088] 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 2.2 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).

[0089] The resin composition of the present invention can be used as a substrate material, sheet, laminate, resin-attached copper foil, copper-clad laminate, TAB tape, printed circuit board, prepreg, adhesive sheet, etc., by dissolving it in a suitable organic solvent or by forming it into a film and processing it to form a core layer or a build-up layer of a multilayer substrate.

[0090]

[0091] Prepreg

[0092] Meanwhile, the present invention provides a prepreg comprising the above-described resin composition.

[0093] The prepreg according to the present invention is a fiber-reinforced composite material, comprising a fiber-containing substrate; and the above-described resin composition impregnated into the fiber-containing substrate.

[0094] The above resin composition may be a resin varnish dissolved or dispersed in an organic solvent. This resin composition may be coated on or impregnated into a fiber-containing substrate, and then cured to a B-stage (semi-cured state) by heating to form a sheet-shaped insulating substrate.

[0095] The fiber-containing substrate is a flexible, arbitrarily bendable fiber assembly that supports a metal foil laminate or a printed circuit board. This fiber-containing substrate, containing fibers, can lower the permittivity and dielectric loss tangent of the metal foil laminate or the printed circuit board, thereby improving low-dielectric loss characteristics. Furthermore, the fiber-containing substrate can adhere closely to the resin composition during manufacturing, thereby exhibiting excellent flexibility, heat resistance, and adhesive strength.

[0096] The fiber-containing 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.

[0097] 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, which 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-containing substrate during subsequent curing, and they also have excellent thermal stability.

[0098] In one example, the fiber-containing 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, glass woven fabric, glass chopped strands, glass chopped strands mat, glass roving cloth, glass surfacing mat, etc., but is not limited thereto.

[0099] The thickness of the fiber-containing substrate is not particularly limited and may be, for example, in the range of about 0.01 to 0.3 mm.

[0100] Meanwhile, the surface of the fiber-containing 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.

[0101] For example, the surface of the fiber-containing 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-containing substrate and the (semi-)cured product of the resin composition further improved, but the metal foil of the metal foil laminate and the prepreg are more firmly bonded, thereby suppressing delamination of the metal foil.

[0102] 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 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 110 to 180°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.

[0103] The prepreg (110) of the present invention described above has a dielectric constant (D) of about 2.5 or less, specifically 1.5 to 2.2, at 25°C 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).

[0104]

[0105] <Metal foil laminate>

[0106] A metal foil laminate comprising the above-described resin composition according to the present invention is provided.

[0107] According to an example, a metal foil laminate 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.

[0108] According to another example, a metal foil laminate 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.

[0109] According to another example, a metal foil laminate 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 layers.

[0110] According to another example, a metal foil laminate 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.

[0111] Here, the metal foil laminate may be a roll-type metal foil laminate manufactured by roll-to-roll, or may be a sheet-type (non-roll type) metal foil laminate cut to a certain size.

[0112] 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.

[0113] 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.

[0114] 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.

[0115] The aforementioned metal foil laminate can be manufactured using a method known in the art. For example, a prepreg can be laminated on one side of a first copper foil, a second copper foil can be laminated thereon, and then a copper foil laminate can be obtained by heating and pressurizing.

[0116]

[0117] Printed circuit board

[0118] Meanwhile, the present invention provides a printed circuit board comprising the above-described resin composition.

[0119] 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.

[0120] For example, a printed circuit board according to the present invention includes the aforementioned metal foil laminate. In this case, a circuit pattern may be formed on the metal foil (first metal foil and / or second metal foil) included in the metal foil laminate. In addition, a resin layer or prepreg included in the metal foil laminate serves as an insulating support member.

[0121] 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.

[0122] As described above, the resin composition described above has low dielectric constant and dielectric loss tangent in a frequency band of about 3.5 to 300 GHz, and excellent heat resistance and molding processability. Therefore, a printed circuit board to which the resin composition is applied also has low dielectric loss in a frequency band of about 3.5 to 300 GHz, 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.

[0123]

[0124] 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.

[0125] <Example 1>

[0126] 1-1. Preparation of resin composition

[0127] 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 (100 weight%) of the water composition.

[0128] 1-2. Preparation of prepreg

[0129] After impregnating the above-manufactured resin composition into glass fiber, it was dried and heated at 150°C for 3 minutes to manufacture a prepreg in a semi-cured (B-stage) state.

[0130] 1-3. Manufacturing of copper-clad laminates

[0131] After laminating 1 ply of the prepreg manufactured in Example 1-2 on copper foil, a copper foil laminate having a thickness of 0.1 mm was manufactured by pressing at 200°C for 2 hours.

[0132] 1-4. Manufacturing of printed circuit boards

[0133] A photosensitive dry film was applied to the copper-clad laminate manufactured in the above Example 1-3 by applying heat and pressure, and then a master film showing the circuit was used to irradiate light and develop the film to manufacture a printed circuit board (PCB). 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.

[0134] Example 1 Example 2 Comparative Example 1 Comparative Example 2 Comparative Example 3 A5050505050B-130----B-2-30--30B-3--30--B-4---30-C0.20.20.20.2-D2020202020

[0135] Composition details Specification A Polyphenylene oxide resin Noryl SA90, SABICB-1 Hollow inorganic filler with 60% porosity Silica (D50=2.3㎛, Dk=1.35, Df=0.0005) B-2 Hollow inorganic filler with 88% porosity S32HS, 3M (D50=22㎛, Dk=1.35, Df=0.0043) B-3 General inorganic filler SO-C2, Admatechs (D50=0.5㎛, Dk=3.5, Df=0.002) B-4 Hollow inorganic filler with 38% porosity Silica (D50=0.6㎛, Dk=2.8, Df=0.003) C Dispersant Triton X-100, Dow corp D Fluorine resin Filler PFA (Perfluoroalkoxy) (Dk=2.1, Df=0.0003, Tm=310℃, MFR=7g / 10min, D50=25㎛)

[0136]

[0137] <Example 2 and Comparative Examples 1 to 3>

[0138] 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 composition was changed as described in Table 1 above.

[0139]

[0140] <Experimental Example 1> - Physical Property Evaluation

[0141] The properties of the resin compositions, prepregs, and copper-clad laminates manufactured in Examples 1 to 2 and Comparative Examples 1 to 3 were evaluated by the following methods, and the results are shown in Table 3 below.

[0142] 1) Specific gravity of the insulator

[0143] The copper foil of the copper-clad laminates manufactured in Examples 1 to 2 and Comparative Examples 1 to 3 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)].

[0144] 2) Dielectric constant (Dk) and dielectric loss (Df)

[0145] The copper foil of the copper-clad laminates manufactured in Examples 1 to 2 and Comparative Examples 1 to 3 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).

[0146] 3) Coefficient of thermal expansion (CTE)

[0147] The copper foil of the copper-clad laminates manufactured in Examples 1 to 2 and Comparative Examples 1 to 3 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.

[0148] 4) Resin flowability

[0149] The prepregs manufactured in Examples 1 to 2 and Comparative Examples 1 to 3 were pressed at a temperature of 170°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 "×".

[0150] 5) Peel Strength (P / S)

[0151] The adhesive strength of the interface between the copper foil and the resin composition of the copper-clad laminates manufactured in Examples 1 to 2 and Comparative Examples 1 to 3 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 “×”.

[0152] 6) Heat resistance

[0153] 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 "×".

[0154] Example 1 Example 2 Comparative Example 1 Comparative Example 2 Comparative Example 3 Filler vol% 55.5% 64.6% 20.3% 29.2% 64.7% Insulator specific gravity 0.82 0.65 1.46 1.30.65 Dk 1.79 1.68 2.53 2.44 1.68 Df 0.00 10.00 20.00 30.00 30.00 2 CTE (ppm / ℃) 50 30 60 50 30 Resin flowability ○○○○ × Adhesiveness ○○○○○ Heat resistance ○○○○ ×

Claims

1. Polyphenylene oxide resin; Hollow inorganic filler having a porosity of 60 to 90%; and Dispersant 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 ㎛.

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

5. In paragraph 1, A resin composition further comprising a fluorine resin filler.

6. In paragraph 5, The above fluororesin filler has a dielectric constant (D) in the range of 2 to 3 at 25°C and 10 GHz. k ) having a resin composition.

7. In paragraph 5, A resin composition wherein the fluorine resin filler contains at least one selected from the group consisting of polytetrafluoroethylene (PTFE), perfluoroalkoxy alkane (PFA), tetrafluoroethylene-hexafluoropropylene copolymer (FEP), polychlorotrifluoroethylene (PCTFE), ethylene-tetrafluoroethylene copolymer (ETFE), tetrafluoroethylene-chlorotrifluoro ethylene copolymer (TFE / CTFE), ethylene-chlorotrifluoroethylene copolymer (ECTFE), and polychlorotrifluoroethylene (PCTFE).

8. In paragraph 1, A resin composition wherein the dispersant contains a nonionic dispersant.

9. In paragraph 1, A resin composition, wherein the dispersant contains at least one selected from the group consisting of a polyoxyethylene glycol alkylphenol ether dispersant, a polysorbate dispersant, and a poly(oxyethylene) alkyl ether dispersant.

10. In paragraph 1, A resin composition further comprising at least one selected from the group consisting of a hardener, an initiator, an additive, and a solvent.

11. In paragraph 1, Based on the total amount of the resin composition, 10 to 70 wt% of polyphenylene oxide-based resin; 5 to 40 wt% of hollow inorganic filler; and 0.0001 to 5 wt% dispersant A resin composition comprising:

12. In paragraph 1, The cured product of the resin composition has a dielectric constant (D) in the range of 1.5 to 2.2 at 25° C. and 10 GHz. k ) having a resin composition.

13. A prepreg comprising a resin composition according to any one of claims 1 to 12.

14. In paragraph 13, Dielectric constant (D) at 25 ℃ and 10 GHz k ) Prepreg with a thickness of 2.5 or less.

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

16. A printed circuit board comprising a resin composition according to any one of claims 1 to 12.