A resin composition and an article thereof

Abstract

The application discloses a resin composition and an article thereof, and belongs to the technical field of resin compositions.The resin composition comprises a polyphenyl ether, a modified unsaturated hydrocarbon block copolymer, an oligomeric hydrocarbon resin and a filler, wherein the modified unsaturated hydrocarbon block copolymer has a branching degree of 20%-70%, the modified groups in the modified unsaturated hydrocarbon block copolymer are formed by polymerization of unsaturated hydrocarbon monomers, the number of repeating units of the unsaturated hydrocarbon monomers in the modified groups is 10-60, and both side end groups of the unsaturated hydrocarbon monomers are carbon-carbon double bonds.The resin composition provided by the application can be applied to a circuit substrate, can reduce the thermal expansion coefficient of the circuit substrate, and can improve the heat resistance and mechanical properties of the circuit substrate.

Description

Technical Field

[0001] This invention relates to the field of electronic materials technology, and more particularly to a resin composition and its products. Background Technology

[0002] Hydrocarbon resins are widely used in the field of circuit boards due to their good dielectric properties. However, circuit boards made from them often have problems such as a large coefficient of thermal expansion, poor heat resistance, and poor mechanical properties, resulting in poor reliability of printed circuit boards.

[0003] Existing technologies typically use hydrocarbon resins and polyphenylene ethers as resin compositions. The addition of polyphenylene ethers can improve the heat resistance of the resin composition, but it still cannot meet the higher heat resistance requirements. At the same time, the 3D network structure formed by this resin composition has strong uncertainty. The 3D network structure is disordered, with poor uniformity and cross-linking, which results in the thermal expansion coefficient and mechanical properties of the circuit board still failing to meet the application requirements. Summary of the Invention

[0004] Therefore, it is necessary to provide a resin composition and its articles to address the above problems, wherein the circuit board made of the resin composition has a low coefficient of thermal expansion, high heat resistance and high mechanical properties.

[0005] To achieve the above objectives, the present invention adopts the following technical solution:

[0006] The first aspect of this application provides a resin composition comprising polyphenylene ether, a modified unsaturated hydrocarbon block copolymer, an oligomeric hydrocarbon resin, and a filler, wherein the degree of branching of the modified unsaturated hydrocarbon block copolymer is 20%-70%, the modifying groups in the modified unsaturated hydrocarbon block copolymer are formed by polymerization of unsaturated hydrocarbon monomers, the number of repeating units of the unsaturated hydrocarbon monomers in the modified groups is 10-60, and both end groups of the unsaturated hydrocarbon monomers are carbon-carbon double bonds.

[0007] Preferably, the modified unsaturated hydrocarbon block copolymer satisfies at least one of the following conditions:

[0008] 1) The weight-average molecular weight of the modified unsaturated hydrocarbon block copolymer is 3000 g / mol to 30000 g / mol;

[0009] 2) The degree of branching of the modified unsaturated hydrocarbon block copolymer is 30%-50%.

[0010] Preferably, the modified group satisfies at least one of the following conditions:

[0011] 1) The weight-average molecular weight of the unsaturated hydrocarbon monomers of the modified group is 50 g / mol to 500 g / mol;

[0012] 2) The unsaturated hydrocarbon monomer of the modified group contains a benzene ring structure;

[0013] 3) The number of repeating units of the unsaturated hydrocarbon monomer of the modified group is 20-40.

[0014] Preferably, the unsaturated hydrocarbon monomer of the modified group is selected from at least one of divinylbenzene, stilbene ethane, stilbene naphthalene, and stilbene anthracene.

[0015] Preferably, the unsaturated hydrocarbon block copolymer in the modified unsaturated hydrocarbon block copolymer satisfies at least one of the following conditions:

[0016] 1) The unsaturated hydrocarbon block copolymer contains a benzene ring structure;

[0017] 2) The unsaturated hydrocarbon block copolymer contains hydrocarbon units formed from C4-C8 linear olefins;

[0018] 3) In the unsaturated hydrocarbon block copolymer, based on the total weight of the unsaturated hydrocarbon block copolymer, the content of carbon-carbon double bonds other than the benzene ring is 20wt% to 40wt%;

[0019] 4) The weight-average molecular weight of the unsaturated hydrocarbon block copolymer is 2000 g / mol to 25000 g / mol.

[0020] Preferably, the unsaturated hydrocarbon block copolymer is selected from at least one of styrene-butadiene block copolymer, partially hydrogenated styrene-butadiene block copolymer, styrene-butadiene-styrene triblock copolymer, partially hydrogenated styrene-butadiene-styrene triblock copolymer, and styrene-isoprene-styrene block copolymer.

[0021] Preferably, the weight-average molecular weight of the oligomeric hydrocarbon resin is 1000 g / mol to 3000 g / mol.

[0022] Preferably, in the resin composition, based on 100 parts by weight of the polyphenylene ether resin, the amount of the modified unsaturated hydrocarbon block copolymer is 50-70 parts by weight, and the amount of the oligomeric hydrocarbon resin is 20-40 parts by weight.

[0023] A second aspect of this application provides an article made using the resin composition described above, the article comprising a prepreg, a circuit board, and a printed circuit board.

[0024] Preferably, the specific surface area of ​​the prepreg is 200 m². 2 / g-400m 2 / g, with a pore size of 300nm-500nm. The circuit board typically includes an insulating layer and a conductive layer disposed on at least one surface of the insulating layer, wherein the insulating layer is formed by pressing one or more laminated prepregs as described above. The printed circuit board is made using the circuit board as described above.

[0025] The present invention, by adopting the above technical solution, has the following beneficial effects:

[0026] This invention provides a resin composition. By defining the components in the resin composition, and further defining the modified unsaturated hydrocarbon block copolymer, polyphenylene ether, and oligomeric hydrocarbon resin, the resin composition, when applied to a circuit board, can improve the heat resistance and mechanical properties of the circuit board while reducing its coefficient of thermal expansion. Detailed Implementation

[0027] The embodiments of this application are described in detail below. The described embodiments are exemplary and intended to explain the present invention, and should not be construed as limiting the present invention.

[0028] In this invention, except for the components specifically described for synthesis, all other components and reagents involved are conventional commercially available products or can be obtained through conventional technical means in the art. Unless otherwise stated, the materials, methods, and embodiments of this invention are exemplary only and not limiting.

[0029] This application provides a resin composition comprising polyphenylene ether, a modified unsaturated hydrocarbon block copolymer, an oligomeric hydrocarbon resin, and a filler, wherein the degree of branching of the modified unsaturated hydrocarbon block copolymer is 20%-70%, the modifying groups in the modified unsaturated hydrocarbon block copolymer are formed by polymerization of unsaturated hydrocarbon monomers, the number of repeating units of the unsaturated hydrocarbon monomers in the modified groups is 10-60, and both end groups of the unsaturated hydrocarbon monomers are carbon-carbon double bonds.

[0030] In this invention, the modified groups are mainly formed by in-situ graft polymerization of unsaturated hydrocarbon monomers onto unsaturated hydrocarbon block copolymers. That is, the unsaturated hydrocarbon monomers use the unsaturated hydrocarbon block copolymers as the starting active sites and carry out chain growth reactions sequentially. Alternatively, the modified groups can also be formed by grafting unsaturated hydrocarbon monomers onto unsaturated hydrocarbon block copolymers after self-polymerization.

[0031] Branching degree refers to the ratio of the number of modified groups to the main chain groups. In this scheme, by introducing a modified unsaturated hydrocarbon block copolymer into the resin composition, and limiting the branching degree of the modified unsaturated hydrocarbon block copolymer, the number of repeating units and end group structure of the unsaturated hydrocarbon monomers in the modified groups, the double network 3D structure formed by the modified unsaturated hydrocarbon block copolymer and polyphenylene ether has good uniformity and crosslinking degree. This reduces the thermal expansion coefficient of the circuit board while improving the heat resistance and mechanical properties of the circuit board.

[0032] The unsaturated hydrocarbon monomers of the modifying group have unsaturated double bonds on both sides, allowing the modifying group to not only graft onto the unsaturated hydrocarbon block copolymer but also undergo crosslinking reactions with polyphenylene ether. A suitable number of repeating units in the unsaturated hydrocarbon monomers of the modifying group and a suitable degree of branching in the modified unsaturated hydrocarbon block copolymer contribute to the formation of more crosslinking and entanglement points. This results in a network structure within the main chain of the modified unsaturated hydrocarbon block copolymer, with polyphenylene ether interpenetrating within and crosslinking with the modifying groups of the copolymer. The resulting double-network 3D structure formed by the polyphenylene ether and the modified unsaturated hydrocarbon block copolymer exhibits excellent uniformity, thereby enhancing the rigidity of the molecular chain, reducing the coefficient of thermal expansion of the circuit board made from this resin composition, and improving the heat resistance and mechanical properties of the circuit board made from this resin composition. If the number of repeating units of the unsaturated hydrocarbon monomer in the modified group is less than 10, or the branching degree of the modified unsaturated hydrocarbon block copolymer is less than 20%, the molecular chains of the modified group cannot form effective crosslinking points. This makes it difficult for the modified group to crosslink with polyphenylene ether to form a network structure, resulting in low crosslinking strength of the double-network 3D structure, increased thermal motion in the soft phase region, and an increase in the coefficient of thermal expansion of the circuit board made of the resin composition, thus reducing the heat resistance and mechanical properties of the circuit board. However, if the branching degree of the modified unsaturated hydrocarbon block copolymer is greater than 50%, or the number of repeating units of the unsaturated hydrocarbon monomer in the modified group is greater than 100, the chain segments of the modified group are too long or the number of side chains is too large. The molecular chains of the modified group undergo self-crosslinking and cannot crosslink with polyphenylene ether to form a network structure, thereby increasing the coefficient of thermal expansion of the circuit board made of the resin composition and reducing the heat resistance and mechanical properties of the circuit board.

[0033] Furthermore, the modified unsaturated hydrocarbon block copolymer has a weight-average molecular weight of 3000 g / mol to 30000 g / mol, enabling it to be compatible with polyphenylene ether to form a uniform and ordered dual-network 3D structure. This further reduces the coefficient of thermal expansion of the circuit board made from the resin composition, improving its heat resistance and mechanical properties. More preferably, the modified unsaturated hydrocarbon block copolymer has a weight-average molecular weight of 4500 g / mol to 20000 g / mol.

[0034] To further reduce the coefficient of thermal expansion of the circuit board made of the resin composition and improve its heat resistance and mechanical properties, the branching degree of the modified unsaturated hydrocarbon block copolymer is preferably 30%-50%.

[0035] Furthermore, the modified group satisfies at least one of the following conditions:

[0036] 1) The weight-average molecular weight of the unsaturated hydrocarbon monomers of the modified group is 50 g / mol to 500 g / mol;

[0037] 2) The unsaturated hydrocarbon monomer of the modified group contains a benzene ring structure;

[0038] 3) The number of repeating units of the unsaturated hydrocarbon monomer of the modified group is further preferably 20-40.

[0039] By limiting the weight-average molecular weight of the unsaturated hydrocarbon monomers of the modified groups, the length of the modified groups is further improved, the crosslinking strength between the modified groups and polyphenylene ether is increased, the coefficient of thermal expansion of the circuit board made of the resin composition is further reduced, and the heat resistance and mechanical properties of the circuit board are improved.

[0040] The unsaturated hydrocarbon monomers of the modified group contain benzene ring structures, which can increase the rigidity of the modified group molecular chain, thereby further reducing the coefficient of thermal expansion of the circuit board made of the resin composition and improving the heat resistance and mechanical properties of the circuit board.

[0041] Specifically, in some embodiments, the unsaturated hydrocarbon monomer of the modified group is selected from at least one of divinylbenzene, stilbene ethane, stilbene naphthalene, and stilbene anthracene.

[0042] Furthermore, the unsaturated hydrocarbon block copolymer in the modified unsaturated hydrocarbon block copolymer satisfies at least one of the following conditions:

[0043] 1) The unsaturated hydrocarbon block copolymer contains a benzene ring structure;

[0044] 2) The unsaturated hydrocarbon block copolymer contains hydrocarbon units formed from C4-C8 linear olefins;

[0045] 3) In the unsaturated hydrocarbon block copolymer, based on the total weight of the unsaturated hydrocarbon block copolymer, the content of carbon-carbon double bonds other than the benzene ring is 20wt%-40wt%;

[0046] 4) The weight-average molecular weight of the unsaturated hydrocarbon block copolymer is 2000 g / mol to 25000 g / mol.

[0047] The benzene ring structure in the unsaturated hydrocarbon block copolymer can increase the rigidity of the unsaturated hydrocarbon block copolymer, thereby further reducing the coefficient of thermal expansion of the circuit board made of the resin composition and improving the heat resistance and mechanical properties of the circuit board.

[0048] By limiting the length of the hydrocarbon unit blocks formed by the linear olefins in the unsaturated hydrocarbon block copolymer, it is beneficial to graft modified groups onto the unsaturated hydrocarbon block copolymer, further improving the stiffness of the 3D network structure constructed between the modified groups and polyphenylene ether. This can further reduce the coefficient of thermal expansion of the circuit board made of the resin composition and improve the heat resistance and mechanical properties of the circuit board.

[0049] In the unsaturated hydrocarbon block copolymer, based on the total weight of the unsaturated hydrocarbon block copolymer, the content of carbon-carbon double bonds other than the benzene ring is 20wt% to 40wt%. In this way, the double bonds in the unsaturated hydrocarbon block copolymer can provide an appropriate amount of grafting sites. After the modified unsaturated hydrocarbon block copolymer is crosslinked with the polyphenylene ether network, a double network 3D structure with moderate crosslinking density and uniform network can be formed, thereby further reducing the coefficient of thermal expansion of the circuit board made of the resin composition and improving the heat resistance and mechanical properties of the circuit board.

[0050] By limiting the weight-average molecular weight of the unsaturated hydrocarbon block copolymer, a denser 3D network can be formed between the modified unsaturated hydrocarbon block copolymer and polyphenylene ether, further reducing the coefficient of thermal expansion of the circuit board made from this resin composition and improving the heat resistance and mechanical properties of the circuit board. More preferably, the weight-average molecular weight of the unsaturated hydrocarbon block copolymer is 4000 g / mol to 10000 g / mol.

[0051] Specifically, in some embodiments, the unsaturated hydrocarbon block copolymer is selected from at least one of styrene-butadiene block copolymer, partially hydrogenated styrene-butadiene block copolymer, styrene-butadiene-styrene triblock copolymer, partially hydrogenated styrene-butadiene-styrene triblock copolymer, and styrene-isoprene-styrene block copolymer.

[0052] This application also discloses a method for preparing a modified unsaturated hydrocarbon block copolymer: styrene-butadiene-styrene triblock copolymer (SBS) and toluene / xylene are added to a container, and after dissolution and clarification, stilbene ethane is added to dissolve and clarify, followed by the addition of the initiator azobisisobutyronitrile (AIB), and the mixture is heated to 60-90℃ and kept at that temperature for 1-5 hours. Subsequently, anhydrous ethanol is added, and after the flocculent precipitate, the solid obtained by multiple filtrations with anhydrous ethanol is dried to obtain the modified styrene-butadiene-styrene triblock copolymer.

[0053] The styrene-butadiene-styrene triblock copolymer (SBS), stilbene ethane, initiator, and reaction conditions in the above steps can be adjusted according to the actual modified unsaturated hydrocarbon block copolymer to be prepared.

[0054] The weight-average molecular weight of the oligomeric hydrocarbon resin is 1000 g / mol to 3000 g / mol. Specifically, in some embodiments, the oligomeric hydrocarbon resin is selected from at least one of polybutadiene, polybutene, and polystyrene-butadiene.

[0055] The filler includes, but is not limited to, at least one of spherical silica, aluminum hydroxide, alumina, talc, aluminum nitride, boron nitride, silicon carbide, barium sulfate, barium titanate, strontium titanate, calcium carbonate, calcium silicate, mica, and glass fiber powder. Further, the filler is more preferably spherical silica with a particle size range of 0.5-4 μm, thereby further reducing the coefficient of thermal expansion of the circuit board.

[0056] Specifically, in the resin composition, based on 100 parts by weight of the polyphenylene ether, the amount of the modified unsaturated hydrocarbon block copolymer is 50-70 parts by weight, for example, 50 parts by weight, 55 parts by weight, 60 parts by weight, 65 parts by weight, or 70 parts by weight. The amount of the oligomeric hydrocarbon resin is 20-40 parts by weight, for example, 20 parts by weight, 25 parts by weight, 30 parts by weight, 35 parts by weight, or 40 parts by weight. Based on 100 parts by weight of polyphenylene ether, the amount of the filler is 100-120 parts by weight, for example, 100 parts by weight, 105 parts by weight, 110 parts by weight, 115 parts by weight, or 120 parts by weight. Furthermore, by controlling the amount of each component, the coefficient of thermal expansion of the circuit board can be further reduced.

[0057] The resin composition may also include solvents, initiators, etc.

[0058] This application also provides an article made using the resin composition described above, the article comprising a prepreg, a circuit board, and a printed circuit board.

[0059] This application does not limit the specific preparation method of the prepreg using the resin composition. Preferably, the prepreg is obtained by impregnating or coating a reinforcing material with the resin composition and then drying it. The reinforcing material is preferably at least one of glass fiber cloth and quartz fiber cloth. The specific surface area of ​​the prepreg is 200 m². 2 / g-400m 2 / g, with a pore size of 300nm-500nm, and moderate specific surface area and average pore size, indicate that the modified unsaturated hydrocarbon block copolymer can crosslink with polyphenylene ether to form a dual-network 3D structure with good uniformity and crosslinking degree. This can improve the heat resistance and mechanical properties of the circuit board while reducing the thermal expansion coefficient of the circuit board.

[0060] This application also provides a circuit board made using the aforementioned prepreg, comprising an insulating layer and a conductive layer disposed on at least one surface of the insulating layer, wherein the insulating layer is formed by pressing one or more laminated prepregs as described above, and the conductive layer may be copper foil, aluminum foil, nickel foil, silver foil, or an alloy foil thereof. This application does not limit the type of material, but copper foil is preferred.

[0061] Specifically, the printed circuit board is made using the circuit board as described above.

[0062] Specifically, the printed circuit board is mainly made of the circuit substrate through processes such as drilling, hole filling, micro-etching, pre-dip, activation, acceleration, chemical copper plating, and copper thickening.

[0063] The effects of the technical solution of this application will be further illustrated below through several specific application examples.

[0064] Example 1:

[0065] A resin composition comprising the following components in parts by weight:

[0066] Polyphenylene oxide (brand name OPE-2St): 100 parts by weight;

[0067] Modified unsaturated hydrocarbon block copolymer (specifically, modified styrene-butadiene-styrene triblock copolymer A): 60 parts by weight;

[0068] Low-molecular-weight hydrocarbon resin (specifically, polystyrene-butadiene resin RICON 100, weight-average molecular weight 3000 g / mol): 30 parts by weight;

[0069] Filler (specifically spherical silica): 100 parts by weight.

[0070] Among them, the modified styrene-butadiene-styrene triblock copolymer A has a weight-average molecular weight of 11743 g / mol and a branching degree of 35%. The unsaturated hydrocarbon monomer of the modified group is stilbene ethane. The number of repeating units of the unsaturated hydrocarbon monomer in the modified group is 30. The weight-average molecular weight of the unsaturated hydrocarbon monomer in the modified group is 234 g / mol. The weight-average molecular weight of the styrene-butadiene-styrene triblock copolymer (brand name 1,2-SBS-L42-1) is 4359 g / mol. The content of carbon-carbon double bonds other than benzene rings in the styrene-butadiene-styrene triblock copolymer is 30%.

[0071] The above-mentioned polyphenylene ether, modified unsaturated hydrocarbon block copolymer, and oligomeric hydrocarbon resin were mixed in proportion and dissolved in a mixed solvent of toluene and methyl ethyl ketone (mass ratio 5:1). After uniform dissolution, filler was added in proportion. After stirring evenly, the resin composition was mixed with toluene to prepare a resin solution with a solid content of 65%. Fiberglass cloth was impregnated with the resin solution and baked at 130°C for 2 minutes to obtain a prepreg. Sixteen prepregs were stacked together, and copper foil was placed on both sides. They were then placed in a vacuum press and heated at 215°C and 45 kg / cm². 2 After curing for 5 hours, a copper-clad laminate is obtained.

[0072] The specific surface area of ​​the prepreg was determined to be 263.29 m² using the BET surface area test method. 2 / g, with an average pore size of 431.78nm.

[0073] Specifically, the modified styrene-butadiene-styrene triblock copolymer A includes the following steps:

[0074] 100 parts by weight of styrene-butadiene-styrene triblock copolymer and 500 parts by weight of toluene / xylene were added to a container. After dissolving and clarifying, 100 parts by weight of stilbene ethane were added and dissolved and clarified. Then, azobisisobutyronitrile (AIBN) was added as an initiator. The mixture was heated to 70°C and kept at that temperature for 4 hours. The temperature was then lowered to room temperature, and anhydrous ethanol was added. After the flocculent material precipitated, the solid obtained by multiple filtrations with anhydrous ethanol was dried to obtain modified styrene-butadiene-styrene triblock copolymer A.

[0075] It should be noted that the preparation methods of different types of modified unsaturated hydrocarbon block copolymers in the following other examples and comparative examples are similar to the preparation method of modified styrene-butadiene-styrene triblock copolymer A in Example 1. They can be achieved by adjusting the types and proportions of raw materials and reaction conditions, and will not be described in detail here.

[0076] Example 2:

[0077] A resin composition comprising the following components in parts by weight:

[0078] Polyphenylene oxide (brand name OPE-2St): 100 parts by weight;

[0079] Modified unsaturated hydrocarbon block copolymer (specifically, modified styrene-isoprene-styrene block copolymer): 60 parts by weight;

[0080] Low-polymer hydrocarbon resin (specifically polybutadiene B1000, weight-average molecular weight 1000 g / mol): 30 parts by weight;

[0081] Filler (specifically alumina): 100 parts by weight.

[0082] The modified styrene-isoprene-styrene block copolymer has a weight-average molecular weight of 19896 g / mol and a branching degree of 50%. The unsaturated hydrocarbon monomer of the modified group is divinylbenzene. The number of repeating units of the unsaturated hydrocarbon monomer in the modified group is 40, and the weight-average molecular weight of the unsaturated hydrocarbon monomer in the modified group is 180 g / mol. The weight-average molecular weight of the styrene-isoprene-styrene block copolymer (brand name D1111) is 9819 g / mol, and the content of carbon-carbon double bonds other than benzene rings in the styrene-isoprene-styrene block copolymer is 35%.

[0083] The preparation methods of the prepreg and copper-clad laminate in this embodiment are the same as in Example 1. In this embodiment, the specific surface area of ​​the prepreg, measured by the BET surface area test, is 362.19 m². 2 / g, with an average pore size of 328.42nm.

[0084] Example 3:

[0085] A resin composition comprising the following components in parts by weight:

[0086] Polyphenylene oxide (brand name OPE-2St): 100 parts by weight;

[0087] Modified unsaturated hydrocarbon block copolymer (specifically modified styrene-butadiene-styrene triblock copolymer B): 60 parts by weight;

[0088] Low-molecular-weight hydrocarbon resin (specifically, polystyrene-butadiene resin RICON 100, weight-average molecular weight 3000 g / mol): 30 parts by weight;

[0089] Filler (specifically spherical silica): 100 parts by weight.

[0090] Among them, the modified styrene-butadiene-styrene triblock copolymer B has a weight-average molecular weight of 9818 g / mol and a branching degree of 30%. The unsaturated hydrocarbon monomer of the modifying group is stilbene ethane. The number of repeating units of the unsaturated hydrocarbon monomer in the modifying group is 20. The weight-average molecular weight of the unsaturated hydrocarbon monomer in the modifying group is 234 g / mol. The weight-average molecular weight of the styrene-butadiene-styrene triblock copolymer (brand name 1,2-SBS-L42-1) is 4359 g / mol. The content of carbon-carbon double bonds other than benzene rings in the styrene-butadiene-styrene triblock copolymer is 30%.

[0091] The preparation methods of the prepreg and copper-clad laminate in this embodiment are the same as in Example 1. In this embodiment, the specific surface area of ​​the prepreg, measured by the BET surface area test, is 203.82 m². 2 / g, with an average pore size of 508.31nm.

[0092] Example 4:

[0093] A resin composition comprising the following components in parts by weight:

[0094] Polyphenylene oxide (brand name OPE-2St): 100 parts by weight;

[0095] Modified unsaturated hydrocarbon block copolymer (specifically, modified styrene-butadiene-styrene triblock copolymer C): 60 parts by weight;

[0096] Low-molecular-weight hydrocarbon resin (specifically, polystyrene-butadiene resin RICON 100, weight-average molecular weight 3000 g / mol): 30 parts by weight;

[0097] Filler (specifically spherical silica): 100 parts by weight.

[0098] Among them, the modified styrene-butadiene-styrene triblock copolymer C has a weight-average molecular weight of 9885 g / mol, a branching degree of 20%, an unsaturated hydrocarbon monomer of the modifying group as divinylbenzene, a repeating unit number of the unsaturated hydrocarbon monomer in the modifying group of 40, a weight-average molecular weight of the unsaturated hydrocarbon monomer in the modifying group of 180 g / mol, a weight-average molecular weight of styrene-butadiene-styrene triblock copolymer (brand name 1,2-SBS-L42-1) of 4359 g / mol, and a carbon-carbon double bond content other than benzene ring in the styrene-butadiene-styrene triblock copolymer of 30%.

[0099] The preparation methods of the prepreg and copper-clad laminate in this embodiment are the same as in Example 1. In this embodiment, the specific surface area of ​​the prepreg, measured by the BET surface area test, is 341.21 m². 2 / g, with an average pore size of 364.32nm.

[0100] Example 5:

[0101] A resin composition comprising the following components in parts by weight:

[0102] Polyphenylene oxide (brand name OPE-2St): 100 parts by weight;

[0103] Modified unsaturated hydrocarbon block copolymer (specifically, modified styrene-butadiene-styrene triblock copolymer D): 60 parts by weight;

[0104] Low-molecular-weight hydrocarbon resin (specifically, polystyrene-butadiene resin RICON 100, weight-average molecular weight 3000 g / mol): 30 parts by weight;

[0105] Filler (specifically spherical silica): 100 parts by weight.

[0106] Among them, the modified styrene-butadiene-styrene triblock copolymer D has a weight-average molecular weight of 7554 g / mol, a branching degree of 35%, an unsaturated hydrocarbon monomer of the modifying group of 2-methyl-1,4-pentadiene, a repeating unit number of the unsaturated hydrocarbon monomer of the modifying group of 30, a weight-average molecular weight of 82 g / mol, a weight-average molecular weight of styrene-butadiene-styrene triblock copolymer (brand name 1,2-SBS-L42-1) of 4359 g / mol, and a carbon-carbon double bond content other than benzene ring in the styrene-butadiene-styrene triblock copolymer of 30%.

[0107] The preparation methods of the prepreg and copper-clad laminate in this embodiment are the same as in Example 1. In this embodiment, the specific surface area of ​​the prepreg, measured by the BET surface area test, is 281.98 m². 2 / g, with an average pore size of 365.01nm.

[0108] Example 6:

[0109] A resin composition comprising the following components in parts by weight:

[0110] Polyphenylene oxide (brand name OPE-2St): 100 parts by weight;

[0111] Modified unsaturated hydrocarbon block copolymer (specifically, modified styrene-butadiene-styrene triblock copolymer E): 60 parts by weight;

[0112] Low-molecular-weight hydrocarbon resin (specifically, polystyrene-butadiene resin RICON 100, weight-average molecular weight 3000 g / mol): 30 parts by weight;

[0113] Filler (specifically spherical silica): 100 parts by weight.

[0114] Among them, the modified styrene-butadiene-styrene triblock copolymer E has a weight-average molecular weight of 10120 g / mol and a branching degree of 35%. The unsaturated hydrocarbon monomer of the modifying group is stilbene ethane. The number of repeating units of the unsaturated hydrocarbon monomer in the modifying group is 30. The weight-average molecular weight of the unsaturated hydrocarbon monomer in the modifying group is 234 g / mol. The weight-average molecular weight of the styrene-butadiene-styrene triblock copolymer (brand name 1,2-SBS-L42-2) is 4162 g / mol. The content of carbon-carbon double bonds other than benzene rings in the styrene-butadiene-styrene triblock copolymer is 45%.

[0115] The preparation methods of the prepreg and copper-clad laminate in this embodiment are the same as in Example 1. In this embodiment, the specific surface area of ​​the prepreg, measured by the BET surface area test, is 232.99 m². 2 / g, with an average pore size of 463.27nm.

[0116] Example 7:

[0117] A resin composition comprising the following components in parts by weight:

[0118] Polyphenylene oxide (brand name OPE-2St): 100 parts by weight;

[0119] Modified unsaturated hydrocarbon block copolymer (specifically, modified styrene-isoprene / butadiene-styrene block copolymer): 60 parts by weight;

[0120] Low-molecular-weight hydrocarbon resin (specifically, polystyrene-butadiene resin RICON 100, weight-average molecular weight 3000 g / mol): 30 parts by weight;

[0121] Filler (specifically spherical silica): 100 parts by weight.

[0122] The modified styrene-isoprene / butadiene-styrene block copolymer has a weight-average molecular weight of 29091 g / mol and a branching degree of 35%. The unsaturated hydrocarbon monomer in the modified group is stilbene ethane. The number of repeating units in the unsaturated hydrocarbon monomer in the modified group is 30. The weight-average molecular weight of the unsaturated hydrocarbon monomer in the modified group is 234 g / mol. The weight-average molecular weight of the styrene-isoprene / butadiene-styrene block copolymer (brand name D1171) is 20879 g / mol. The content of carbon-carbon double bonds other than benzene rings in the styrene-butadiene-styrene triblock copolymer is 40%.

[0123] The preparation methods of the prepreg and copper-clad laminate in this embodiment are the same as in Example 1. In this embodiment, the specific surface area of ​​the prepreg, measured by the BET surface area test, is 246.13 m². 2 / g, with an average pore size of 462.65nm.

[0124] Example 8:

[0125] A resin composition comprising the following components in parts by weight:

[0126] Polyphenylene oxide (brand name OPE-2St): 100 parts by weight;

[0127] Modified unsaturated hydrocarbon block copolymer (specifically, modified styrene-butadiene-styrene triblock copolymer F): 60 parts by weight;

[0128] Low-molecular-weight hydrocarbon resin (specifically, polystyrene-butadiene resin RICON 100, weight-average molecular weight 3000 g / mol): 30 parts by weight;

[0129] Filler (specifically spherical silica): 100 parts by weight.

[0130] Among them, the modified styrene-butadiene-styrene triblock copolymer F has a weight-average molecular weight of 9920 g / mol and a branching degree of 35%. The unsaturated hydrocarbon monomer of the modifying group is stilbene ethane. The number of repeating units of the unsaturated hydrocarbon monomer in the modifying group is 10. The weight-average molecular weight of the unsaturated hydrocarbon monomer in the modifying group is 234 g / mol. The weight-average molecular weight of the styrene-butadiene-styrene triblock copolymer (brand name 1,2-SBS-L42-1) is 4359 g / mol. The content of carbon-carbon double bonds other than benzene rings in the styrene-butadiene-styrene triblock copolymer is 30%.

[0131] The preparation methods of the prepreg and copper-clad laminate in this embodiment are the same as in Example 1. In this embodiment, the specific surface area of ​​the prepreg, measured by the BET surface area test, is 356.88 m². 2 / g, with an average pore size of 330.52nm.

[0132] Example 9:

[0133] A resin composition comprising the following components in parts by weight:

[0134] Polyphenylene oxide (brand name OPE-2St): 100 parts by weight;

[0135] Modified unsaturated hydrocarbon block copolymer (specifically, modified styrene-butadiene-styrene triblock copolymer A): 40 parts by weight;

[0136] Low-molecular-weight hydrocarbon resin (specifically, polystyrene-butadiene resin RICON 100, weight-average molecular weight 3000 g / mol): 30 parts by weight;

[0137] Filler (specifically spherical silica): 90 parts by weight.

[0138] The preparation methods of the prepreg and copper-clad laminate in this embodiment are the same as in Example 1. In this embodiment, the specific surface area of ​​the prepreg, measured by the BET surface area test, is 191.09 m². 2 / g, with an average pore size of 520.17nm.

[0139] Example 10:

[0140] A resin composition comprising the following components in parts by weight:

[0141] Polyphenylene oxide (brand name OPE-2St): 100 parts by weight;

[0142] Modified unsaturated hydrocarbon block copolymer (specifically modified styrene-butadiene-styrene triblock copolymer A): 70 parts by weight;

[0143] Low-molecular-weight hydrocarbon resin (specifically, polystyrene-butadiene resin RICON 100, weight-average molecular weight 3000 g / mol): 30 parts by weight;

[0144] Filler (specifically spherical silica): 110 parts by weight.

[0145] The preparation methods of the prepreg and copper-clad laminate in this embodiment are the same as in Example 1. In this embodiment, the specific surface area of ​​the prepreg, measured by the BET surface area test, is 433.61 m². 2 / g, with an average pore size of 293.86nm.

[0146] Comparative Example 1:

[0147] A resin composition comprising the following components in parts by weight:

[0148] Polyphenylene oxide (brand name OPE-2St): 100 parts by weight;

[0149] Modified unsaturated hydrocarbon block copolymer (specifically, modified styrene-butadiene-styrene triblock copolymer G): 60 parts by weight;

[0150] Low-molecular-weight hydrocarbon resin (specifically, polystyrene-butadiene resin RICON 100, weight-average molecular weight 3000 g / mol): 30 parts by weight;

[0151] Filler (specifically spherical silica): 100 parts by weight.

[0152] Among them, the modified styrene-butadiene-styrene triblock copolymer G has a weight-average molecular weight of 9019 g / mol, a branching degree of 10%, and the unsaturated hydrocarbon monomer of the modifying group is stilbene ethane. The number of repeating units of the unsaturated hydrocarbon monomer in the modifying group is 30, and the weight-average molecular weight of the unsaturated hydrocarbon monomer in the modifying group is 234 g / mol. The weight-average molecular weight of the styrene-butadiene-styrene triblock copolymer (brand name 1,2-SBS-L42-1) is 4359 g / mol, and the content of carbon-carbon double bonds other than benzene rings in the styrene-butadiene-styrene triblock copolymer is 30%.

[0153] The preparation methods for the prepreg and copper-clad laminate in this comparative example are the same as in Example 1. In this comparative example, the specific surface area of ​​the prepreg, measured by the BET surface area test, is 170.29 m². 2 / g, with an average pore size of 634.88nm.

[0154] Comparative Example 2:

[0155] A resin composition comprising the following components in parts by weight:

[0156] Polyphenylene oxide (brand name OPE-2St): 100 parts by weight;

[0157] Modified unsaturated hydrocarbon block copolymer (specifically, modified styrene-butadiene-styrene triblock copolymer H): 60 parts by weight;

[0158] Low-molecular-weight hydrocarbon resin (specifically, polystyrene-butadiene resin RICON 100, weight-average molecular weight 3000 g / mol): 30 parts by weight;

[0159] Filler (specifically spherical silica): 100 parts by weight.

[0160] Among them, the weight-average molecular weight of the modified styrene-butadiene-styrene triblock copolymer H is 8183 g / mol, the degree of branching is 35%, the unsaturated hydrocarbon monomer of the modifying group is styrene, the number of repeating units of the unsaturated hydrocarbon monomer in the modifying group is 1, the weight-average molecular weight of the unsaturated hydrocarbon monomer in the modifying group is 104 g / mol, the weight-average molecular weight of the styrene-butadiene-styrene triblock copolymer (brand name 1,2-SBS-L42-1) is 4359 g / mol, and the content of carbon-carbon double bonds other than benzene rings in the styrene-butadiene-styrene triblock copolymer is 30%.

[0161] The preparation methods for the prepreg and copper-clad laminate in this comparative example are the same as in Example 1. In this comparative example, the specific surface area of ​​the prepreg, measured by the BET surface area test, is 130.09 m². 2 / g, with an average pore size of 728.77nm.

[0162] Comparative Example 3:

[0163] A resin composition comprising the following components in parts by weight:

[0164] Polyphenylene oxide (brand name OPE-2St): 100 parts by weight;

[0165] Modified unsaturated hydrocarbon block copolymer (specifically, modified styrene-butadiene-styrene triblock copolymer I): 60 parts by weight;

[0166] Low-molecular-weight hydrocarbon resin (specifically, polystyrene-butadiene resin RICON 100, weight-average molecular weight 3000 g / mol): 30 parts by weight;

[0167] Filler (specifically spherical silica): 100 parts by weight.

[0168] Among them, the modified styrene-butadiene-styrene triblock copolymer I has a weight-average molecular weight of 8875 g / mol and a branching degree of 35%. The unsaturated hydrocarbon monomer of the modified group is stilbene ethane. The number of repeating units of the unsaturated hydrocarbon monomer in the modified group is 5. The weight-average molecular weight of the unsaturated hydrocarbon monomer in the modified group is 234 g / mol. The weight-average molecular weight of the styrene-butadiene-styrene triblock copolymer (brand name 1,2-SBS-L42-1) is 4359 g / mol. The content of carbon-carbon double bonds other than benzene rings in the styrene-butadiene-styrene triblock copolymer is 30%.

[0169] The preparation methods for the prepreg and copper-clad laminate in this comparative example are the same as in Example 1. In this comparative example, the specific surface area of ​​the prepreg, measured by the BET surface area test, is 187.53 m². 2 / g, with an average pore size of 553.08nm.

[0170] Comparative Example 4:

[0171] A resin composition comprising the following components in parts by weight:

[0172] Polyphenylene oxide (brand name OPE-2St): 100 parts by weight;

[0173] Modified unsaturated hydrocarbon block copolymer (specifically, modified styrene-butadiene-styrene triblock copolymer J): 60 parts by weight;

[0174] Low-molecular-weight hydrocarbon resin (specifically, polystyrene-butadiene resin RICON 100, weight-average molecular weight 3000 g / mol): 30 parts by weight;

[0175] Filler (specifically spherical silica): 100 parts by weight.

[0176] Among them, the modified styrene-butadiene-styrene triblock copolymer J has a weight-average molecular weight of 14671 g / mol and a branching degree of 35%. The unsaturated hydrocarbon monomer of the modifying group is stilbene ethane. The number of repeating units of the unsaturated hydrocarbon monomer in the modifying group is 65, and the weight-average molecular weight of the unsaturated hydrocarbon monomer in the modifying group is 234 g / mol. The weight-average molecular weight of the styrene-butadiene-styrene triblock copolymer (brand name 1,2-SBS-L42-1) is 4359 g / mol. The content of carbon-carbon double bonds other than benzene rings in the styrene-butadiene-styrene triblock copolymer is 30%.

[0177] The preparation methods for the prepreg and copper-clad laminate in this comparative example are the same as in Example 1. In this comparative example, the specific surface area of ​​the prepreg, measured by the BET surface area test, is 180.48 m². 2 / g, with an average pore size of 603.91nm.

[0178] Comparative Example 5:

[0179] A resin composition comprising the following components in parts by weight:

[0180] Polyphenylene oxide (brand name OPE-2St): 100 parts by weight;

[0181] Unsaturated hydrocarbon block copolymer (specifically styrene-butadiene-styrene triblock copolymer): 60 parts by weight;

[0182] Low-molecular-weight hydrocarbon resin (specifically, polystyrene-butadiene resin RICON 100, weight-average molecular weight 3000 g / mol): 30 parts by weight;

[0183] Filler (specifically spherical silica): 100 parts by weight.

[0184] The styrene-butadiene-styrene triblock copolymer (brand name 1,2-SBS-L42-1) has a weight-average molecular weight of 4359 g / mol and contains 30% carbon-carbon double bonds other than benzene rings.

[0185] The preparation methods for the prepreg and copper-clad laminate in this comparative example are the same as in Example 1. In this comparative example, the specific surface area of ​​the prepreg, measured by the BET surface area test, is 201.32 m². 2 / g, with an average pore size of 764.91nm.

[0186] Comparative Example 6:

[0187] A resin composition comprising the following components in parts by weight:

[0188] Modified unsaturated hydrocarbon block copolymer (specifically, modified styrene-butadiene-styrene triblock copolymer A): 60 parts by weight;

[0189] Low-molecular-weight hydrocarbon resin (specifically, polystyrene-butadiene resin RICON 100, weight-average molecular weight 3000 g / mol): 30 parts by weight;

[0190] Filler (specifically spherical silica): 100 parts by weight.

[0191] The preparation methods for the prepreg and copper-clad laminate in this comparative example are the same as in Example 1. In this comparative example, the specific surface area of ​​the prepreg, measured by the BET surface area test, is 159.89 m². 2 / g, with an average pore size of 620.17nm. The copper-clad laminate prepared in this comparative example has excessive adhesive flow, which cannot meet the requirements for use.

[0192] Comparative Example 7:

[0193] A resin composition comprising the following components in parts by weight:

[0194] Polyphenylene oxide (brand name OPE-2St): 100 parts by weight;

[0195] Modified unsaturated hydrocarbon block copolymer (specifically, modified styrene-butadiene-styrene triblock copolymer A): 60 parts by weight;

[0196] Filler (specifically spherical silica): 100 parts by weight.

[0197] The preparation methods for the prepreg and copper-clad laminate in this comparative example are the same as in Example 1. In this comparative example, the specific surface area of ​​the prepreg, measured by the BET surface area test, is 451.79 m². 2 / g, with an average pore size of 242.88nm. The copper-clad laminate prepared in this comparative example has poor flowability, resulting in dry board formation, and cannot meet the application requirements.

[0198] Comparative Example 8:

[0199] A resin composition comprising the following components in parts by weight:

[0200] Polyphenylene oxide (brand name OPE-2St): 100 parts by weight;

[0201] Modified unsaturated hydrocarbon block copolymer (specifically, modified styrene-butadiene-styrene triblock copolymer K): 60 parts by weight;

[0202] Low-molecular-weight hydrocarbon resin (specifically, polystyrene-butadiene resin RICON 100, weight-average molecular weight 3000 g / mol): 30 parts by weight;

[0203] Filler (specifically spherical silica): 100 parts by weight.

[0204] The modified styrene-butadiene-styrene triblock copolymer H has a weight-average molecular weight of 9925 g / mol and a branching degree of 35%. The unsaturated hydrocarbon monomer of the modified group is 1,4-diethynylbenzene. The number of repeating units of the unsaturated hydrocarbon monomer in the modified group is 30, and the weight-average molecular weight of the unsaturated hydrocarbon monomer in the modified group is 126 g / mol. The weight-average molecular weight of the styrene-butadiene-styrene triblock copolymer (brand name 1,2-SBS-L42-1) is 4359 g / mol. The content of carbon-carbon double bonds other than benzene rings in the styrene-butadiene-styrene triblock copolymer is 30%.

[0205] The preparation methods of the prepreg and copper-clad laminate in this comparative example are the same as in Example 1. In this comparative example, the specific surface area of ​​the prepreg, measured by the BET surface area test, is 591.53 m². 2 / g, with an average pore size of 230.88nm.

[0206] The copper-clad laminates prepared in Examples 1-10 and Comparative Examples 1-8 were subjected to performance tests, and the test methods are as follows:

[0207] Coefficient of thermal expansion (CTE): The coefficient of thermal expansion in the XY plane was tested using the TMA compression method in accordance with GB / T2572-2005 Test Method for Average Linear Expansion Coefficient of Fiber Reinforced Plastics.

[0208] Glass transition temperature Tg: Used to characterize heat resistance. The Tg of copper-clad laminate is determined according to the DMA method specified in IPC-TM-6502.4.24.4, based on dynamic thermomechanical analysis (DMA).

[0209] Elastic modulus: used to characterize mechanical properties, tested according to the method of standard IPC-TM650 2.4.4;

[0210] The copper-clad laminates prepared in Examples 1-10 and Comparative Examples 1-8 are shown in Table 1 below.

[0211] Table 1: Performance test results of the copper-clad laminates prepared in Examples 1-10 and Comparative Examples 1-8:

[0212] Group CTE- X / Y (ppm / ℃) Tg (°C) Elastic modulus (GPa) Example 1 6 / 7 249 16.43 Example 2 9 / 10 225 14.62 Example 3 11 / 12 208 13.71 Example 4 10 / 11 217 14.71 Example 5 12 / 13 188 12.22 Example 6 10 / 12 207 13.91 Example 7 11 / 12 195 12.43 Example 8 9 / 11 216 12.32 Example 9 12 / 13 192 11.93 Example 10 12 / 12 206 12.77 Comparative Example 1 14 / 16 175 11.21 Comparative Example 2 16 / 17 168 10.55 Comparative Example 3 15 / 16 180 10.89 Comparative Example 4 14 / 16 185 11.19 Comparative Example 5 18 / 19 177 9.21 Comparative Example 6 / / / Comparative Example 7 / / / Comparative Example 8 16 / 16 181 10.43

[0213] As shown in Table 1 above, the circuit boards in the various embodiments of this application have a low coefficient of thermal expansion, a high glass transition temperature, and a high elastic modulus. This indicates that the resin composition in the various embodiments of this application improves the heat resistance and mechanical properties of the circuit board while reducing its coefficient of thermal expansion.

[0214] As can be seen from Example 1 and Comparative Examples 1-8, introducing modified unsaturated hydrocarbon block copolymers into polyphenylene ether, oligomeric hydrocarbon resins and fillers, and defining the degree of branching of the modified unsaturated hydrocarbon block copolymers, the number of repeating units of the unsaturated hydrocarbon monomers in the modified groups, and the structure of the unsaturated hydrocarbon monomers, enables the circuit board made of the resin composition to have a low coefficient of thermal expansion, a high glass transition temperature, and a high elastic modulus. This demonstrates that the circuit boards in the various embodiments of this application have high heat resistance and high mechanical properties. As can be seen from Examples 1-10, when the weight-average molecular weight of the modified unsaturated hydrocarbon block copolymer, or the weight-average molecular weight of the unsaturated hydrocarbon monomer of the modified group, or other structures in the unsaturated hydrocarbon monomer, or the structure of the unsaturated hydrocarbon block copolymer, or the weight-average molecular weight of the oligomeric hydrocarbon resin is not within the preferred range of this scheme, although the coefficient of thermal expansion, glass transition temperature, or elastic modulus of the circuit board made of the resin composition may be slightly deteriorated, the circuit board can still have a low coefficient of thermal expansion, a high glass transition temperature, and a high elastic modulus. While reducing the coefficient of thermal expansion of the circuit board, the heat resistance and mechanical properties of the circuit board are improved.

[0215] Although embodiments of the present invention have been shown and described above, it is understood that the above embodiments are exemplary and should not be construed as limiting the present invention. Those skilled in the art can make changes, modifications, substitutions, alterations, deletions of some features, additions of features, or recombinations of features to the above embodiments within the scope of the present invention without departing from the principles and spirit of the present invention. Any simple modifications, equivalent changes, and alterations made to the above embodiments based on the innovative principles of the present invention shall still fall within the scope of the technical solutions of the present invention.

Claims

1. A resin composition, characterized in that, The product comprises polyphenylene ether, modified unsaturated hydrocarbon block copolymer, oligomeric hydrocarbon resin, and filler, wherein the degree of branching of the modified unsaturated hydrocarbon block copolymer is 20%-70%, the modifying groups in the modified unsaturated hydrocarbon block copolymer are formed by polymerization of unsaturated hydrocarbon monomers, the number of repeating units of the unsaturated hydrocarbon monomers in the modified groups is 10-60, and both ends of the unsaturated hydrocarbon monomers are carbon-carbon double bonds.

2. The resin composition according to claim 1, characterized in that, The modified unsaturated hydrocarbon block copolymer must satisfy at least one of the following conditions: 1) The weight-average molecular weight of the modified unsaturated hydrocarbon block copolymer is 3000 g / mol to 30000 g / mol; 2) The degree of branching of the modified unsaturated hydrocarbon block copolymer is 30%-50%.

3. The resin composition according to claim 1, characterized in that, The modified group must satisfy at least one of the following conditions: 1) The weight-average molecular weight of the unsaturated hydrocarbon monomers of the modified group is 50 g / mol to 500 g / mol; 2) The unsaturated hydrocarbon monomer of the modified group contains a benzene ring structure; 3) The number of repeating units of the unsaturated hydrocarbon monomer of the modified group is 20-40.

4. The resin composition according to claim 3, characterized in that, The unsaturated hydrocarbon monomer of the modified group is selected from at least one of divinylbenzene, stilbene ethane, stilbene naphthalene, and stilbene anthracene.

5. The resin composition according to claim 1, characterized in that, The unsaturated hydrocarbon block copolymer in the modified unsaturated hydrocarbon block copolymer must satisfy at least one of the following conditions: 1) The unsaturated hydrocarbon block copolymer contains a benzene ring structure; 2) The unsaturated hydrocarbon block copolymer contains hydrocarbon units formed from C4-C8 linear olefins; 3) In the unsaturated hydrocarbon block copolymer, based on the total weight of the unsaturated hydrocarbon block copolymer, the content of carbon-carbon double bonds other than the benzene ring is 20wt%-40wt%; 4) The weight-average molecular weight of the unsaturated hydrocarbon block copolymer is 2000 g / mol to 25000 g / mol.

6. The resin composition according to claim 5, characterized in that, The unsaturated hydrocarbon block copolymer is selected from at least one of styrene-butadiene block copolymer, partially hydrogenated styrene-butadiene block copolymer, styrene-butadiene-styrene triblock copolymer, partially hydrogenated styrene-butadiene-styrene triblock copolymer, and styrene-isoprene-styrene block copolymer.

7. The resin composition according to claim 1, characterized in that, The weight-average molecular weight of the oligomeric hydrocarbon resin is 1000 g / mol to 3000 g / mol.

8. The resin composition according to claim 1, characterized in that, In the resin composition, based on 100 parts by weight of the polyphenylene ether resin, the amount of the modified unsaturated hydrocarbon block copolymer is 50-70 parts by weight, the amount of the oligomeric hydrocarbon resin is 20-40 parts by weight, and the amount of the filler is 100-120 parts by weight.

9. An article made using the resin composition as described in any one of claims 1-8, characterized in that, The products include prepreg, circuit board, and printed circuit board.

10. The article according to claim 9, characterized in that, The specific surface area of ​​the semi-cured sheet is 200 m². 2 / g-400m 2 / g, with a pore size of 300nm-500 nm.