Low dielectric resin composition improving workability, prepreg and metal laminate

Abstract

To provide a low dielectric resin composition improving workability, and a prepreg and a metal laminate using the low dielectric resin composition.SOLUTION: A low dielectric resin composition contains a resin system, a halogen-free flame retardant, a hollow spherical silica, and a coupling agent. The resin system contains a polyphenylene ether resin added by specific wt.%, a crosslinking agent, and a vinyl group-containing elastomer. The specific gravity of the hollow spherical silica is 0.4 to 0.6 g / cm3, and the average particle diameter D50 of the hollow spherical silica is 2.0 μm to 3.0 μm. A relative dielectric constant (Dk) at 10 GHz after the low dielectric resin composition is cured is 2.75 to 3.05, and a dielectric loss tangent (Df) is less than 0.002.SELECTED DRAWING: Figure 1

Description

Technical Field

[0001] The present invention relates to a resin composition and its applications, and particularly to a low-dielectric resin composition for improving processability, and a prepreg and a metal laminate manufactured from the low-dielectric resin composition.

Background Art

[0002] With the advanced driver assistance system (ADAS), the driver can ensure sufficient time to take emergency measures to prevent accidents. With the improvement of the technical level and cost reduction of millimeter-wave radar (mmWave Radar), millimeter-wave radar has begun to be regarded as important in the field of ADAS sensors that detect the environment around the vehicle body at any time during driving.

[0003] Substrates used in conventional millimeter-wave radars are roughly classified into fluororesin substrates and thermosetting resin substrates. Here, fluororesin substrates have poor processability due to the properties of resins such as polytetrafluoroethylene (PTFE). When used in the manufacture of laminates, it is difficult to perform drilling and copper plating processes, etc., and special processing equipment is required, resulting in high costs. In addition, fluororesin is a thermoplastic resin, and it is difficult to co-mold electronic materials using fluororesin with electronic materials using general-purpose thermosetting resins (such as epoxy resins), and its practical application is limited. Thermosetting resin substrates mainly suppress the relative dielectric constant (Dk) of the substrate by introducing hollow glass beads. However, when hollow glass beads are introduced, not only does the uniformity of copper plating in the holes decrease, but it also leads to an increase in the dielectric tangent (Df) value.

Summary of the Invention

Problems to be Solved by the Invention

[0004] One of the objects of the present invention is to provide a low-dielectric resin composition for improving processability in view of the deficiencies of the prior art. The low-dielectric resin composition is advantageous for low transmission loss and processability of electronic materials so as to meet the application requirements of millimeter waves. The present invention further provides a prepreg and a metal laminate using the low-dielectric resin composition.

Means for Solving the Problem

[0005] In order to achieve the object of the present invention, one technical means adopted by the present invention is to improve processability and include (A) a resin system, (B) a halogen-free flame retardant, (C) hollow spherical silica having a specific gravity of 0.4 to 0.6 g / cm 3 and an average particle diameter D50 of 2.0 μm to 3.0 μm, and (D) a coupling agent, to provide a low dielectric resin composition. The (A) resin system includes 10% to 60% by weight of a polyphenylene ether resin, 5% to 30% by weight of a crosslinking agent, and 20% to 50% by weight of a vinyl group-containing elastomer based on the total weight of the resin system. In the low dielectric resin composition, the amount of the (B) halogen-free flame retardant used is 20 parts to 45 parts by weight, the amount of the (C) hollow spherical silica used is 1 part to 20 parts by weight, and the amount of the (D) coupling agent used is 0.1 part to 5 parts by weight with respect to 100 parts by weight of the (A) resin system. Further, the relative dielectric constant (Dk) at 10 GHz after curing of the low dielectric resin composition is 2.75 to 3.05, and the dielectric tangent (Df) is less than 0.002.

[0006] In one embodiment of the present invention, the vinyl group-containing elastomer is selected from the group consisting of polybutadiene, styrene-butadiene copolymer, styrene-butadiene-styrene block copolymer, and styrene-butadiene-divinylbenzene copolymer.

[0007] In one embodiment of the present invention, the vinyl group-containing elastomer is a styrene-butadiene-styrene block copolymer having a weight average molecular weight of 3500 g / mol to 5500 g / mol.

[0008] In one embodiment of the present invention, the styrene-butadiene-styrene block copolymer contains 5 mol% to 40 mol% of styrene units. Taking the total of vinyl groups in the styrene-butadiene-styrene block copolymer as 100%, the content of 1,2-vinyl in the styrene-butadiene-styrene block copolymer is 60% to 90%, and the content of 1,4-vinyl is 10% to 40%.

[0009] In one embodiment of the present invention, the hollow spherical silica is surface-modified with at least one functional group among acrylic groups and vinyl groups.

[0010] In one embodiment of the present invention, the crosslinking agent is selected from the group consisting of 1,3,5-triallyl cyanurate (TAC), triallyl isocyanurate (TAIC), trimethallyl isocyanurate (TMAIC), diallyl phthalate, divinylbenzene, and 1,2,4-triallyl trimellitate.

[0011] In one embodiment of the present invention, the low dielectric resin composition further contains (E) general spherical silica having a specific gravity of 2.0 to 2.5 g / cm 3 For 100 parts by weight of the (A) resin system, the amount of the (E) general spherical silica used is 50 parts by weight to 95 parts by weight, preferably 85 parts by weight to 95 parts by weight.

[0012] In one embodiment of the present invention, the average particle diameter D50 of the (E) general spherical silica is 2.0 μm to 3.0 μm.

[0013] In one embodiment of the present invention, the halogen-free flame retardant is a compound having a structure represented by the following formula (I). [Chemistry] Here, R1 is a covalent bond, -CH2-, [Chemistry] , [Chemistry] , [Chemistry] , or [Chemistry] and Here, R2, R3, R4, and R5 are independently H, an alkyl group, or [Chemistry] .

[0014] Another object of the present invention is to provide a prepreg. The prepreg is obtained by applying or impregnating the low dielectric constant resin composition to the reinforcing material.

[0015] Another object of the present invention is to provide a metal laminate. The metal laminate is manufactured by laminating the prepreg and a metal layer, or by applying the low dielectric resin composition to a metal layer. [Advantages of the Invention]

[0016] Overall, the low dielectric resin composition according to the present invention is "the resin system contains 10% to 60% by weight of a polyphenylene ether resin, 5% to 30% by weight of a crosslinking agent, and 20% to 50% by weight of a vinyl group-containing elastomer based on the total weight of the resin system", "the amount of the hollow spherical silica used is 1 part to 20 parts by weight with respect to 100 parts by weight of the resin system", and "the hollow spherical silica has a specific gravity of 0.4 to 0.6 g / cm 3With technical features such as "and the average particle diameter D50 is 2.0 μm to 3.0 μm", on the premise of meeting the environmental protection requirement of halogen-free, excellent electrical properties (Low Dk / Low Df), hygroscopicity and heat resistance can be achieved so that transmission loss is small and stable performance can be maintained for a long time. When manufacturing a laminate, good fluidity and filling properties are shown, and the drillability and copper plating quality can be improved.

Brief Description of the Drawings

[0017]

Figure 1

Figure 2

Figure 3

Figure 4

Figure 5

Embodiments for Carrying Out the Invention

[0018] For a better understanding of the features and technical content of the present invention, please refer to the following detailed description of the present invention and the accompanying drawings. However, the provided accompanying drawings are only for reference and explanation, and are not for limiting the scope of the claims of the present invention.

[0019] Hereinafter, the "low dielectric resin composition, prepreg, and metal laminate for improving processability" according to the embodiments of the present invention will be described according to specific embodiments. Those skilled in the art can understand the advantages and effects of the present invention based on the content disclosed herein. The present invention can be implemented or applied according to other different specific embodiments, and for each detail in this specification, various modifications and changes can be made based on different viewpoints and applications without departing from the concept of the present invention. Also, as described in advance, the accompanying drawings of the present invention are simple schematic explanations and are not drawn based on actual sizes. The technical content of the present invention will be described in more detail based on the following embodiments, but the disclosed content does not limit the protection scope of the present invention.

[0020] Unless otherwise specified, the terms used in the present invention have meanings generally understood by those skilled in the art. The materials used in the following embodiments are commercially available materials unless otherwise specified. The operations or apparatuses used in the following examples are common operations or apparatuses in the technical field unless otherwise specified.

[0021] Due to the characteristics of the fluororesin substrate, it is difficult to perform processing such as drilling and copper plating during the production of laminates, and special manufacturing and processing equipment is required, resulting in high costs. In addition, since the fluororesin is a thermoplastic resin, it is difficult to co-mold electronic materials using fluororesin with electronic materials using general-purpose thermosetting resins (such as epoxy resins), and its practical application is limited, and it is insufficient to meet the requirements of electronic materials for applications such as the fifth-generation mobile communication system (5G), advanced driver assistance system (ADAS), and artificial intelligence (AI). Therefore, in the present invention, by combining a polyphenylene ether resin, which is a thermosetting resin, with a vinyl group-containing elastomer (preferably, a styrene-butadiene-styrene block copolymer) and introducing hollow spherical silica (hollow silica) having a specific specific gravity and particle diameter, low dielectric characteristics are achieved without sacrificing desired characteristics in practical use (such as processability, moisture absorption and heat resistance, fluidity, and filling properties).

[0022] Specifically, in the embodiments of the present invention, a low-dielectric resin composition is provided that realizes the concept of the invention and improves processability. The low-dielectric resin composition includes (A) a resin system, (B) a halogen-free flame retardant, (C) hollow spherical silica, and (D) a coupling agent. Each component will be described in detail below.

[0023] [(A) Resin system] The resin system constituting the low-dielectric resin composition according to the present invention includes 10% to 60% by weight of a polyphenylene ether resin, 5% to 30% by weight of a crosslinking agent, and 20% to 50% by weight of a vinyl group-containing elastomer, based on the total weight of the resin system.

[0024] In the embodiments of the present invention, the molecular structure of the polyphenylene ether resin contains an unsaturated functional group at its end. Examples of the unsaturated functional group include a hydroxyl group, a vinyl group, a styrene group, a vinylbenzyl group, an allyl group, an acryloyl group, a methacrylate group, an epoxy group, and a maleimide group, but the present invention is not limited thereto. The unsaturated functional group is a group capable of undergoing an addition polymerization reaction with a component having another unsaturated functional group. The addition polymerization reaction can be caused by light or heat in the presence of a polymerization initiator.

[0025] Specifically, the polyphenylene ether resin in the (A) resin system may be selected from the group consisting of a polyphenylene ether resin having a hydroxyl group at its end, a polyphenylene ether resin having a vinyl group at its end, a polyphenylene ether resin having a styrene group at its end, a polyphenylene ether resin having a vinylbenzyl group at its end, a polyphenylene ether resin having an allyl group at its end, a polyphenylene ether resin having an acryloyl group at its end, a polyphenylene ether resin having a methacrylate group at its end, a polyphenylene ether resin having an epoxy group at its end, and a polyphenylene ether resin having a maleimide group at its end. The polyphenylene ether resins may be used alone or in combination.

[0026] Assuming the total weight of the resin system is 100% by weight, the content of the polyphenylene ether resin may be 10% by weight, 15% by weight, 20% by weight, 25% by weight, 30% by weight, 35% by weight, 40% by weight, 45% by weight, 50% by weight, 55% by weight, or 60% by weight. The weight average molecular weight of the polyphenylene ether resin is from 1000 g / mol to 20000 g / mol, preferably from 1000 g / mol to 10000 g / mol. If the molecular weight of the polyphenylene ether resin is too large, the fluidity of the polyphenylene ether resin and the solubility in the solvent may deteriorate. If the molecular weight of the polyphenylene ether resin is too small, it may adversely affect the electrical properties and thermal stability of the resin composition.

[0027] In actual application, two kinds of polyphenylene ether resins may be used in combination in the (A) resin system. For example, a polyphenylene ether resin having a bismaleimide group at the end of the molecular main chain and a polyphenylene ether resin having a hydroxyl group, a styrene group, a methacrylate group, or an epoxy group at the end of the molecular main chain may be used in combination, but the present invention is not limited thereto. Alternatively, three kinds of polyphenylene ether resins may be used in combination in the (A) resin system. For example, a polyphenylene ether resin having a bismaleimide group at the end of the molecular main chain, a polyphenylene ether resin having a styrene group at the end of the molecular main chain, and a polyphenylene ether resin having a methacrylate group at the end of the molecular main chain may be used in combination, but the present invention is not limited thereto.

[0028] The presence of the polyphenylene ether having an unsaturated functional group can improve the compatibility of the vinyl group-containing elastomer in the resin composition and improve the upper limit of the addition amount of the vinyl group-containing elastomer. Preferably, in the (A) resin system, the amount of the polyphenylene ether resin used is more than the amount of the vinyl group-containing elastomer used. The production method of the polyphenylene ether resin having an unsaturated functional group is not the core technology of the present invention and can be obtained or completed by those skilled in the art based on the disclosure content of this specification and the general knowledge they possess.

[0029] In an embodiment of the present invention, the vinyl group-containing elastomer can form a bond by the reaction between the double bond of the vinyl group and the unsaturated functional group of the polyphenylene ether resin so that the resin composition has good low dielectric properties, heat resistance, and processability even after curing. It should be noted that, compared with the conventional low dielectric resin composition combining a liquid rubber and a polyphenylene ether resin, in the low dielectric resin composition according to the present invention, the phenomenon of phase separation can be prevented by using a combination of a vinyl group-containing elastomer and a polyphenylene ether resin.

[0030] Specifically, the vinyl group-containing elastomer in the (A) resin system may be selected from the group consisting of polybutadiene, styrene-butadiene copolymer (SBR), styrene-butadiene-styrene block copolymer (SBS), and styrene-butadiene-divinylbenzene copolymer. The vinyl group-containing elastomer may be used alone or in combination.

[0031] Assuming the total weight of the resin system is 100% by weight, the content of the vinyl group-containing elastomer may be 20% by weight, 25% by weight, 30% by weight, 35% by weight, 40% by weight, 45% by weight, or 50% by weight. If the content of the vinyl group-containing elastomer is less than 20% by weight, the resin composition cannot achieve the desired electrical properties (e.g., low Dk, low Df) and physicochemical properties (e.g., high glass transition temperature, low water absorption, good heat resistance). If the content of the vinyl group-containing elastomer exceeds 50% by weight, the functions and actions of other components in the resin composition will be suppressed, and some properties of the resin composition (e.g., flame retardancy) will deteriorate.

[0032] Preferably, the vinyl group-containing elastomer is a styrene-butadiene-styrene block copolymer, and its weight average molecular weight is 3500 g / mol to 5500 g / mol, and may be, for example, 3500 g / mol, 4000 g / mol, 4500 g / mol, 5000 g / mol or 5500 g / mol. Considering the physical properties of the resin composition after curing, the styrene-butadiene-styrene block copolymer contains 5 mol% to 40 mol% of styrene units (assuming all monomer units of the styrene-butadiene-styrene block copolymer are 100 mol%). Also, taking the total amount of vinyl groups in the styrene-butadiene-styrene block copolymer as 100%, the content of 1,2-vinyl in the styrene-butadiene-styrene block copolymer is 60% to 90%, and the content of 1,4-vinyl is 10% to 40%. If the content of 1,2-vinyl in the styrene-butadiene-styrene block copolymer is less than 60%, the physicochemical properties (such as high glass transition temperature, heat resistance, etc.) of the resin composition after curing may deteriorate.

[0033] In an embodiment of the present invention, the crosslinking agent has an unsaturated functional group containing a double bond or a triple bond, and is a component capable of crosslinking with the polyphenylene ether resin and the vinyl group-containing elastomer to form a three-dimensional network structure. For example, a monofunctional crosslinking agent (having only one unsaturated functional group in the molecule) or a polyfunctional crosslinking agent (having two or more unsaturated functional groups in the molecule) can be mentioned, but the present invention is not limited thereto. The type of the crosslinking agent is not particularly limited, and preferably has good compatibility with the polyphenylene ether resin and the vinyl group-containing elastomer.

[0034] Specifically, the crosslinking agent in the resin system may be selected from the group consisting of 1,3,5-triallyl cyanurate (TAC), triallyl isocyanurate (TAIC), trimethallyl isocyanurate (TMAIC), diallyl phthalate, 1,2,4-triallyl trimellitate, and divinylbenzene. The crosslinking agent may be used alone or in combination.

[0035] Taking the total weight of the resin composition as 100% by weight, the content of the crosslinking agent may be 5% by weight, 10% by weight, 15% by weight, 20% by weight, 25% by weight, or 30% by weight.

[0036] [(B) Halogen-free flame retardant] The halogen-free flame retardant constituting the low dielectric resin composition of the present invention may employ a phosphorus-based flame retardant so as to improve the flame retardancy of the manufactured electronic material and meet the requirement of being halogen-free. In actual application, the phosphorus-based flame retardant may be selected from the group consisting of phosphate ester-based flame retardants, phosphazene-based flame retardants, phosphine oxide-based flame retardants, ammonium polyphosphate, melamine polyphosphate, melamine phosphate, and 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (DOPO). The halogen-free flame retardant may be used alone or in combination, but the present invention is not limited thereto.

[0037] Specific examples of phosphate-based halogen-free flame retardants include triphenyl phosphate (TPP), tetraphenyl resorcinol bis(diphenylphosphate) (RDP), bisphenol A bis(diphenyl phosphate) (BDP), and Resorcinol bis(di-2,6-xylyl phosphate) (RXP).

[0038] Specific examples of phosphazene-based halogen-free flame retardants include cyclic phosphazene compounds and linear phosphazene compounds.

[0039] Specific examples of phosphine oxide-based halogen-free flame retardants include tris(4-methoxyphenyl)phosphine oxide, diphenylphosphine oxide, triphenylphosphine oxide, and the phosphine oxide compound represented by the following formula (I) (PQ-60 manufactured by Shinichi Chemical Industry). It should be noted that the phosphine oxide compound having the structure represented by formula (I) has well-known flame retardancy and gives low dielectric properties to the resin composition, which is advantageous for applications in the high-frequency field. [Chemical formula] Here, R1 is a covalent bond, -CH2-, [Chemical formula] , [Chemical formula] , [Chemical formula] or [Chem.] and wherein R2, R3, R4, and R5 are independently H, an alkyl group, or [Chem.] .

[0040] (A) With respect to 100 parts by weight of the resin-based material, the usage amount of (B) the halogen-free flame retardant is 20 to 45 parts by weight. For example, it may be 20 parts by weight, 25 parts by weight, 30 parts by weight, 35 parts by weight, 40 parts by weight, or 45 parts by weight, but the present invention is not limited thereto. If the usage amount of the halogen-free flame retardant is less than 20 parts by weight, the electronic material produced from the resin composition cannot achieve the desired flame retardancy. If the usage amount of the halogen-free flame retardant exceeds 45 parts by weight, it may adversely affect the desired properties such as electrical characteristics, water absorption, and tear strength.

[0041] [(C) Hollow spherical silica] The hollow spherical silica (hollow silica) constituting the low dielectric resin composition according to the present invention imparts good fluidity and filling properties (the ability to fill gaps and voids) to the resin composition, and has specific gravity and particle diameter such that it also has good low dielectric characteristics and workability (drilling workability) even after curing. Based on this, the low dielectric resin composition of the present invention can achieve the characteristics required for a laminated substrate, such as high-frequency high-speed transmission characteristics and copper plating quality.

[0042] Specifically, the purity of (C) the hollow spherical silica is about 99% or more, the specific gravity is 0.4 to 0.6 g / cm 3 and the average particle diameter D50 is 2.0 to 3.0 μm. The specific gravity of the hollow spherical silica is 0.5 g / cm 3It is preferable that it is. Further, (C) hollow spherical silica is surface-modified with at least one functional group among an acrylic group and a vinyl group so as to give better compatibility with (A) the resin system, not impairing the desired properties in practical use, and being added to the resin composition in a larger amount.

[0043] With respect to 100 parts by weight of (A) the resin system, the amount of (C) hollow spherical silica used may be 1 part by weight to 20 parts by weight, and preferably 5 parts by weight to 15 parts by weight. For example, it may be 1 part by weight, 2 parts by weight, 3 parts by weight, 4 parts by weight, 5 parts by weight, 6 parts by weight, 7 parts by weight, 8 parts by weight, 9 parts by weight, 10 parts by weight, 11 parts by weight, 12 parts by weight, 13 parts by weight, 14 parts by weight, 15 parts by weight, 16 parts by weight, 17 parts by weight, 18 parts by weight, 19 parts by weight, or 20 parts by weight, but the present invention is not limited thereto.

[0044] [(D) Coupling agent] The coupling agent constituting the low dielectric resin composition according to the present invention may employ at least one selected from a silane compound and a siloxane compound so as to improve the interfacial bonding strength between the resin and the reinforcing material (for example, fiber cloth) and to improve the compatibility between the resin and the reinforcing material (for example, fiber cloth) and the inorganic powder.

[0045] Specific examples of the silane compound include amino silane, vinyl silane, acrylic silane, and epoxy silane. Specific examples of the siloxane compound include amino siloxane, vinyl siloxane, acrylic siloxane, and epoxy siloxane.

[0046] (A) For 100 parts by weight of the resin system, the amount of (D) coupling agent used may be 0.1 part by weight to 5 parts by weight. For example, it may be 0.1 part by weight, 0.5 part by weight, 1 part by weight, 1.5 parts by weight, 2 parts by weight, 2.5 parts by weight, 3 parts by weight, 3.5 parts by weight, 4 parts by weight, 4.5 parts by weight or 5 parts by weight, but the present invention is not limited thereto.

[0047] [(E) Inorganic filler] The low dielectric resin composition according to the present invention may further contain (E) inorganic filler as necessary so as to improve characteristics such as mechanical strength, thermal conductivity, heat resistance, etc. of the resin composition. In order to maintain the relative permittivity and dielectric tangent at a low level, the (E) inorganic filler may be general spherical silica different from hollow spherical silica, aluminum oxide, zinc oxide, titanium oxide, magnesium oxide, antimony oxide, beryllium oxide, aluminum nitride, boron nitride, calcium carbonate, potassium titanate, glass fiber, barium titanate, barium sulfate, aluminum hydroxide, and magnesium hydroxide. The inorganic filler may be used alone or in combination, but the present invention is not limited thereto.

[0048] (A) For 100 parts by weight of the resin system, the amount of (E) inorganic filler used may be 50 parts by weight to 120 parts by weight. For example, it may be 50 parts by weight, 55 parts by weight, 60 parts by weight, 65 parts by weight, 70 parts by weight, 75 parts by weight, 80 parts by weight, 85 parts by weight, 90 parts by weight, 95 parts by weight, 100 parts by weight, 105 parts by weight, 110 parts by weight, 115 parts by weight or 120 parts by weight, but the present invention is not limited thereto.

[0049] Preferably, the (E) inorganic filler is general spherical silica. General spherical silica may be produced by a synthetic method. Also, the specific gravity of general spherical silica may be 2.0 to 2.5 g / cm 3 and may be 2.2 g / cm 3It is preferably so. Also, the average particle diameter D50 of the general spherical silica is preferably 2.0 μm to 3.0 μm. With respect to 100 parts by weight of the resin system (A), the amount of the general spherical silica (E) used is 50 parts by weight to 95 parts by weight, and preferably 85 parts by weight to 95 parts by weight.

[0050] [Prepreg and Metal Laminate] As shown in FIGS. 1 and 2, the present invention further provides a prepreg 1 (prepreg) and a metal laminate using the low dielectric resin composition. Specifically described, the prepreg 1 is obtained by applying or impregnating the low dielectric resin composition 12 to the reinforcing material 11, attaching the low dielectric resin composition 12 to the reinforcing material 11, and further heating at a high temperature to a semi-cured state. The reinforcing material 11 may be, for example, an electronic grade glass fiber cloth, but the present invention is not limited thereto.

[0051] As shown in FIGS. 3 to 5, the metal laminate may be manufactured by the following method. That is, the prepreg 1 and at least one metal layer 2 (for example, a copper foil layer) are laminated and bonded by hot pressing, or the low dielectric resin composition 12 is applied to the metal layer 2 and sufficiently dried and cured. In a specific example of laminating the prepreg 1 and at least one metal layer 2 (for example, a copper foil layer), a predetermined number of prepregs 1 may be laminated, and the metal layer 2 may be laminated on at least one outer side of the formed laminate 1'.

[0052] In actual application, by a conventional process step, the metal layer 2 on the outside of the metal laminate can be patterned to manufacture a printed circuit board.

[0053] [Characteristic Evaluation] Using toluene, the resin compositions shown in Tables 1 and 2 were used to prepare a thermosetting resin varnish. Next, using a glass fiber cloth manufactured by Nanya Plastics Corporation (NE1078 manufactured by Nanya Plastics) as a reinforcing material, the thermosetting varnish was impregnated at room temperature and dried at 130°C for several minutes to obtain a prepreg with a resin content of 70% by weight. Next, four prepregs were sandwiched between two copper foils with a thickness of 35 μm, and hot pressing was performed to obtain a sample of a copper foil substrate with a thickness of 0.4 mm. The hot pressing was first held at a temperature of 85°C and a pressure of 25 kg / cm 2 for 20 minutes, then heated to 210°C at a heating rate of 3°C / min, held for 120 minutes, and then slowly cooled to 130°C. The obtained samples of the copper foil substrate were evaluated for their properties as described below.

[0054] Glass transition temperature (°C): The glass transition temperature was measured using a Dynamic Mechanical Analyzer (DMA).

[0055] Water absorption rate (%): The sample was heated in a pressure cooker at 2 atm for 120°C for 120 minutes, and then the weight change before and after heating was determined.

[0056] T288 solder resistance test (heat resistance): After the sample was heated in a pressure cooker at 2 atm for 120°C for 120 minutes, it was immersed in a solder bath at 288°C and observed for 1 / 2 hour and 2 hours respectively. If popcorn phenomenon or delamination occurred on the sample substrate, it was rated as "NG". On the other hand, if no popcorn phenomenon or delamination occurred on the sample substrate, it was rated as "PASS".

[0057] Relative dielectric constant (Dk) and dielectric loss tangent (Df): After removing the copper foil from the sample, it was baked in an oven at 105°C for 30 minutes, and the relative dielectric constant and dielectric loss tangent at 10 GHz were measured using an analyzer (E4991A) manufactured by Agilent.

[0058] Uniformity of Copper Plating in Holes: After performing the PCB hole-making copper plating process, cross-section analysis of the samples was carried out, and the uniformity of copper plating was observed with an electron microscope (SEM).

[0059] The detailed information of each component in Table 1 and Table 2 is as follows. Polyphenylene Ether Resin: NORYL SA9000 manufactured by SABIC. SBS Resin: SBS-Ctype manufactured by Nippon Soda Co., Ltd. Crosslinking Agent: TAIC manufactured by Evonik. Flame Retardant: PQ-60 manufactured by Jin-yi Chemical Industry Co., Ltd. Hollow Spherical Silica: HS-200 manufactured by AGC Japan Co., Ltd. General Spherical Silica: Silica prepared by a synthetic method, EQ2410-SMC manufactured by China Sanshiji Co., Ltd. Hollow Glass Beads: im16K manufactured by 3M. Coupling Agent: Z-6030 manufactured by Dow Corning. Peroxide: Luperox F manufactured by ARKEMA.

[0060]

Table 1

[0061]

Table 2

[0062] As is clear from Table 1 and Table 2 above, the resin composition according to Comparative Example 1 did not add hollow spherical silica, but only added general spherical silica. As a result, the Dk of the manufactured electronic material exceeded the desired range (2.75 to 3.05), that is, the desired electrical properties could not be achieved. In the resin compositions according to Comparative Examples 2 and 3, by adding hollow glass beads in addition, the Dk of the manufactured electronic material was within the desired range, but the uniformity of the copper plating in the holes was poor, and it led to an increase in Df. In comparison, the resin compositions according to Examples 1 to 4 adopted hollow spherical silica having a specific specific gravity and particle size instead of hollow glass beads, and further combined polyphenylene ether resin and SBS resin, so that the processing quality of the laminate (the quality of the copper plating in the holes), water absorption, heat resistance, and other practical properties were not impaired, and the low dielectric properties required for millimeter wave applications could be realized.

[0063] [Advantageous effects according to the embodiment] The low dielectric resin composition according to the present invention has the technical features that "the resin system contains 10% to 60% by weight of polyphenylene ether, 5% to 30% by weight of a crosslinking agent, and 20% to 50% by weight of a vinyl group-containing elastomer based on the total weight of the resin system", "the amount of the hollow spherical silica used is 1 part by weight to 20 parts by weight with respect to 100 parts by weight of the resin system", and "the hollow spherical silica has a specific gravity of 0.4 to 0.6 g / cm 3 and an average particle size D50 of 2.0 μm to 3.0 μm". On the premise of meeting the environmental protection requirement of being halogen-free, excellent electrical properties (Low Dk / Low Df), hygroscopicity, and heat resistance can be achieved so that there is less transmission loss and stable performance can be maintained for a long time. When manufacturing a laminate, it shows good fluidity and filling properties, and can improve the drillability and copper plating quality.

[0064] More specifically, the low-dielectric resin composition according to the present invention is an electronic material that employs a polyphenylene ether resin. It can be molded simultaneously with an electronic material using other thermosetting resins (such as epoxy resins), and conventional manufacturing and processing equipment can be used, so the cost can be reduced.

[0065] The content disclosed above is merely a preferred feasible embodiment of the present invention, and the scope of the claims of the present invention is not limited thereto. Therefore, all equivalent technical modifications made using the content of the specification and drawings of the present invention are included in the scope of the claims of the present invention.

Description of Reference Numerals

[0066] 1... prepreg 11... reinforcing material 12... low-dielectric resin composition 2... metal layer

Claims

1. (A) Resin system, (B) halogen-free flame retardant, (C) hollow spherical silica with a specific gravity of 0.4 to 0.6 g / cm ３ and an average particle diameter D50 of 2.0 μm to 3.0 μm, and (D) a coupling agent, and is a low dielectric resin composition comprising The resin system (A) contains 10% to 60% by weight of polyphenylene ether resin, 5% to 30% by weight of crosslinking agent, and 20% to 50% by weight of vinyl group-containing elastomer, based on the total weight of the resin system. In the low dielectric resin composition, the amount of the halogen-free flame retardant (B) used is 20 to 45 parts by weight, the amount of the hollow spherical silica (C) used is 1 to 20 parts by weight, and the amount of the coupling agent (D) used is 0.1 to 5 parts by weight, based on 100 parts by weight of the resin system (A). The low dielectric resin composition is characterized in that the relative dielectric constant (Dk) at 10 GHz after curing of the low dielectric resin composition is 2.75 to 3.05, and the dielectric loss tangent (Df) is less than 0.

002.

2. The low dielectric resin composition according to claim 1, wherein the vinyl group-containing elastomer is selected from the group consisting of polybutadiene, styrene-butadiene copolymer, styrene-butadiene-styrene block copolymer, and styrene-butadiene-divinylbenzene copolymer.

3. The low dielectric resin composition according to claim 2, wherein the vinyl group-containing elastomer is a styrene-butadiene-styrene block copolymer having a weight average molecular weight of 3500 g / mol to 5500 g / mol.

4. The styrene-butadiene-styrene block copolymer contains 5 mol% to 40 mol% of styrene units. Taking the total amount of vinyl groups in the styrene-butadiene-styrene block copolymer as 100%, the content of 1,2-vinyl in the styrene-butadiene-styrene block copolymer is 60% to 90%, and the content of 1,4-vinyl is 10% to 40%. The low dielectric resin composition according to claim 3.

5. The low dielectric resin composition according to claim 1, wherein the hollow spherical silica is surface-modified with at least one functional group selected from an acrylic group and a vinyl group.

6. The crosslinking agent is selected from the group consisting of 1,3,5 - triallyl cyanurate (TAC), triallyl isocyanurate (TAIC), trimethylallyl isocyanurate (TMAIC), diallyl phthalate, divinylbenzene, and 1,2,4 - triallyl trimellitate, the low dielectric resin composition according to claim 1.

7. (E) having a specific gravity of 2.0 g / cm ３ to 2.5 g / cm ３ and further containing general spherical silica, wherein the amount of the general spherical silica (E) used is 50 to 95 parts by weight based on 100 parts by weight of the resin (A). The low dielectric resin composition according to claim 1.

8. The average particle diameter D50 of the general spherical silica (E) is 2.0 μm to 3.0 μm, the low dielectric resin composition according to claim 1.

9. The halogen - free flame retardant is a compound having a structure represented by the following formula (I), the low dielectric resin composition according to claim 1. 【Chemical 1】 Here, R １ is a covalent bond, -CH ２ -, 【Chemical 2】 、 【Chemical Formula 3】 、 【Chemical Formula 4】 or 【Chemical Formula 5】 is, Here, R ２ , R ３ , R ４ , R ５ are independently H, an alkyl group or 【Chemical Formula 6】 is.

10. A prepreg, characterized in that the low - dielectric - constant resin composition according to claim 1 is applied to or impregnated in the reinforcing material.

11. A metal - clad laminate, characterized in that it is manufactured by laminating the prepreg according to claim 9 and a metal layer, or by applying the low dielectric resin composition according to claim 1 to a metal layer.

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