Resin composition and article thereof

Abstract

This invention discloses a resin composition comprising 50 parts by weight of a vinyl polyphenylene ether resin, 1 to 30 parts by weight of a styrene-butadiene-styrene block copolymer, and 0.5 to 30 parts by weight of zinc molybdate-coated silica, wherein the mass ratio of zinc molybdate to silica in the zinc molybdate-coated silica is between 1:9 and 2:8. The aforementioned resin composition can be formulated into prepregs, resin films, laminates, or printed circuit boards, and exhibits improvements in at least one of the following properties: gel time stability, copper foil tensile strength, dielectric loss variation rate, and conductivity anode wire test.

Description

Technical Field

[0001] This invention relates to a resin composition, and more particularly to a resin composition that can be used to prepare prepregs, resin films, laminates or printed circuit boards. Background Technology

[0002] In recent years, with the development of electronic signal transmission methods towards fifth-generation mobile communication technology (5G), and the increasing functionality and miniaturization of electronic devices, communication devices, and personal computers, the circuit boards used are also developing towards multi-layering, high-density wiring, and high-speed signal transmission, placing higher demands on the overall performance of circuit boards such as copper foil substrates. When 5G communication transmission equipment operates at high frequency and high speed, it generates a large amount of heat. As the operating temperature of the device rises, firstly, if the dielectric loss of the substrate material continues to deteriorate with the increase in temperature, it will reduce the quality of signal transmission; secondly, if the adhesion of the copper foil lines decreases due to the increased temperature, it may cause short circuits, leading to equipment failure.

[0003] Furthermore, in high-temperature and high-humidity environments, if copper traces in the substrate material cause metal ion migration, it will degrade the insulation of the substrate material, and in severe cases, it may even cause short circuits and equipment failure. Therefore, solving one or more of the above problems is a direction that the industry is currently actively working towards. Summary of the Invention

[0004] In view of the problems encountered in the prior art, especially the inability of existing materials to meet one or more of the above-mentioned technical problems, the main objective of the present invention is to provide a resin composition that can overcome at least one of the above-mentioned technical problems and articles made using the resin composition.

[0005] To achieve the above objectives, the present invention discloses a resin composition comprising 50 parts by weight of a vinyl polyphenylene ether resin, 1 to 30 parts by weight of a styrene-butadiene-styrene block copolymer, and 0.5 to 30 parts by weight of zinc molybdate-coated silica, wherein the mass ratio of zinc molybdate to silica in the zinc molybdate-coated silica is between 1:9 and 2:8.

[0006] For example, in one embodiment, the vinyl-containing polyphenylene ether resin includes vinyl benzyl biphenyl polyphenylene ether resin, methacrylate polyphenylene ether resin, or a combination thereof.

[0007] For example, in one embodiment, the styrene-butadiene-styrene block copolymer comprises a polymer with butadiene as the core (e.g., a polymer of multiple butadiene units), and each end of this polymer is capped with a styrene end-cap, or each end of this polymer is capped with multiple styrene end-caps. For example, but not limited to, the styrene-butadiene-styrene block copolymer may include (styrene) a -(butadiene) b -(Styrene) c The polymer is configured such that a, b, and c represent the number of repeating units of styrene at the first end, the number of repeating units of butadiene in the middle, and the number of repeating units of styrene at the second end, respectively, and their values ​​are not particularly limited. The relationship between a, b, and c can be represented by the mass ratio of styrene units to butadiene units. For example, but not limited to, the mass ratio (wt%) of styrene units to butadiene units in the styrene-butadiene-styrene block copolymer is between 20:80 and 50:50, preferably between 30:70 and 45:55. For example, in one embodiment, the styrene-butadiene-styrene block copolymer includes copolymers of styrene-butadiene-butadiene-butadiene-butadiene-butadiene-styrene, copolymers of styrene-butadiene-butadiene-butadiene-butadiene-butadiene-styrene-styrene, copolymers of styrene-butadiene-butadiene-butadiene-butadiene-butadiene-butadiene-styrene, or combinations thereof. The styrene-butadiene-styrene block copolymer may include 1,2-vinyl, 1,4-vinyl, or combinations thereof; that is, the styrene-butadiene-styrene block copolymer has reactive vinyl groups that can be further crosslinked with other crosslinking agents.

[0008] For example, in one embodiment, the particle size distribution D50 of the zinc molybdate-coated silica is between 2 micrometers and 4 micrometers, preferably between 2 micrometers and 3 micrometers, more preferably between 2 micrometers and 2.5 micrometers, but is not limited thereto. The aforementioned particle size distribution D50 refers to the particle size value corresponding to when the cumulative volume distribution of the filler (such as zinc molybdate-coated silica) reaches 50% as determined by laser scattering. Its physical meaning is that the cumulative volume ratio of filler particles with a particle size less than or equal to the particle size value is 50%.

[0009] For example, in one embodiment, the resin composition further comprises a bifunctional aliphatic long-chain acrylate. For example, in one embodiment, the bifunctional aliphatic long-chain acrylate comprises 1,6-hexanediacrylate.

[0010] For example, in one embodiment, the resin composition further comprises triallyl isocyanurate, triallyl cyanurate, maleimide resin, polyolefin different from the styrene-butadiene-styrene block copolymer, small molecule vinyl compound, epoxy resin, cyanate resin, phenolic resin, styrene maleic anhydride, polyester resin, amine curing agent, polyamide resin, polyimide resin, or a combination thereof.

[0011] For example, in one embodiment, the resin composition further includes inorganic fillers, flame retardants, curing accelerators, polymerization inhibitors, solvents, silane coupling agents, colorants, toughening agents, or combinations thereof.

[0012] To achieve the above objectives, the present invention also discloses an article made from the aforementioned resin composition, the article comprising a prepreg, a resin film, a laminate, or a printed circuit board.

[0013] For example, in one embodiment, the aforementioned article has at least one, more, or all of the following characteristics:

[0014] The gel time stability calculated from the gel time measured according to the method described in IPC-TM-650 2.3.18 is less than or equal to 32 seconds;

[0015] The tensile force on the copper foil measured according to the method described in IPC-TM-650 2.4.8 is greater than or equal to 3.5 lb / in;

[0016] The dielectric loss variation rate calculated from the dielectric loss measured at a frequency of 10 GHz according to the method described in JIS C2565 is less than or equal to 40%.

[0017] The method described in IPC-TM-650 2.6.25 was tested for 250 hours at 1000V, and the conductivity of the anode wire was verified; and

[0018] The method described in IPC-TM-650 2.6.25 was tested for 1000 hours at 100V, and the conductive anode wire was tested. Detailed Implementation

[0019] To enable those skilled in the art to understand the features and effects of this invention, the terms and expressions mentioned in the specification and claims are explained and defined in general below. Unless otherwise specified, all technical and scientific terms used herein have the ordinary meaning understood by those skilled in the art regarding this invention, and in the event of any conflict, the definitions in this specification shall prevail.

[0020] In this document, the terms “comprising,” “including,” “having,” “containing,” or any similar terms are open-ended transitional phrases intended to encompass non-exclusive inclusions. For example, a composition or article containing a plurality of elements is not limited to those listed herein, but may also include other elements not explicitly listed but typically inherent to the composition or article. Furthermore, unless explicitly stated to the contrary, the term “or” is inclusive, not exclusive. For example, the condition “A or B” is satisfied in any of the following cases: A is true (or exists) and B is false (or does not exist); A is false (or does not exist) and B is true (or exists); A and B are both true (or exist). Moreover, in this document, the terms “comprising,” “including,” “having,” and “containing” are to be interpreted as specifically disclosed and simultaneously encompass conjunctions such as “composed of” and “substantially composed of.”

[0021] In this document, all features or conditions defined in the form of numerical ranges or percentage ranges are for the sake of brevity and convenience only. Accordingly, descriptions of numerical ranges or percentage ranges should be considered as covering and specifically disclosing all possible subranges and individual values ​​within those ranges, particularly integer values. For example, a range description of "1 to 8" should be considered as specifically disclosing all subranges such as 1 to 7, 2 to 8, 2 to 6, 3 to 6, 4 to 8, 3 to 8, etc., particularly subranges defined by all integer values, and should be considered as specifically disclosing individual values ​​within those ranges such as 1, 2, 3, 4, 5, 6, 7, 8, etc. Similarly, a range description of "between 1 and 8" should be considered as specifically disclosing all ranges such as 1 to 8, 1 to 7, 2 to 8, 2 to 6, 3 to 6, 4 to 8, 3 to 8, etc., including endpoint values. Unless otherwise specified, the foregoing interpretation applies to all content throughout this invention, regardless of its scope.

[0022] If a quantity or other numerical value or parameter is expressed as a range, preferred range, or a series of upper and lower limits, it should be understood that this document has specifically disclosed all ranges consisting of any upper or preferred value of that range and the lower or preferred value of that range, regardless of whether such ranges are disclosed separately. Furthermore, when a range of numerical values ​​is mentioned herein, unless otherwise stated, the range should include its endpoints and all integers and fractions within the range.

[0023] In this document, numerical values ​​are to be understood as having a precision with significant digits, provided that the purpose of the invention is achieved. For example, the number 40.0 should be understood to cover a range from 39.50 to 40.49.

[0024] In this document, when Markush groups or alternative terms are used to describe features or examples of the invention, those skilled in the art should understand that subgroups of all members within a Markush group or option list, or any individual member, can also be used to describe the invention. For example, if X is described as "selected from the group consisting of X1, X2, and X3," it also indicates that the claim that X is X1 and the claim that X is X1 and / or X2 and / or X3 have been fully described. Furthermore, when Markush groups or alternative terms are used to describe features or examples of the invention, those skilled in the art should understand that any combination of subgroups of all members within a Markush group or option list, or any individual member, can also be used to describe the invention. Accordingly, for example, if X is described as "selected from the group consisting of X1, X2, and X3," and Y is described as "selected from the group consisting of Y1, Y2, and Y3," it indicates that the claim that X is X1 or X2 or X3 and Y is Y1 or Y2 or Y3 has been fully described.

[0025] Unless otherwise specified, in this invention, a compound refers to a chemical substance formed by two or more elements linked by chemical bonds, including, but not limited to, small molecule compounds and macromolecules. The term "compound" in this document is not limited to a single chemical substance, but can also be interpreted as a class of chemical substances having the same component or the same properties. Furthermore, in this invention, a mixture refers to a combination of two or more compounds.

[0026] Unless otherwise specified, "resin" can generally be a common name for a synthetic polymer. However, in this invention, "resin" can be interpreted as monomers, polymers thereof, combinations of monomers, combinations of polymers thereof, or combinations of monomers and their polymers, etc., and is not limited thereto. For example, in this invention, "maleimide resin" can be interpreted as maleimide monomers, maleimide polymers, combinations of maleimide monomers, combinations of maleimide polymers, or combinations of maleimide monomers and maleimide polymers.

[0027] Unless otherwise specified, in this invention, a polymer refers to a product formed by the polymerization reaction of monomers, often comprising an aggregate of many high molecules, each of which is composed of many simple structural units repeatedly linked by covalent bonds. The monomer is the compound that synthesizes the polymer. Polymers can include homopolymers (also known as self-polymers), copolymers, prepolymers, oligomers (also known as oligomers), etc., and are not limited thereto. Unless otherwise specified, in this invention, a homopolymer refers to a polymer formed by the polymerization of one type of monomer. Unless otherwise specified, in this invention, a copolymer refers to a product formed by the polymerization reaction of two or more different monomers. For example, copolymers can include random copolymers (structures such as -AABABBBAAABBA-), alternating copolymers (structures such as -ABABABAB-), graft copolymers (structures such as -AA(A-BBBB)AA(A-BBBB)AAA-), and block copolymers (structures such as -AAAAA-BBBBBB-AAAAA-), etc. Unless otherwise specified, the styrene-butadiene-styrene block copolymer in this invention refers to a polymer obtained by copolymerizing styrene and butadiene monomers. In this invention, any block copolymer with this structure (terminal styrene units and intermediate butadiene units) is acceptable. Modification or alteration of the polymer backbone and side chain units is not particularly limited. In other words, the styrene-butadiene-styrene block copolymer can be modified or altered, for example, by maleic anhydride. Unless otherwise specified, in this invention, a prepolymer refers to a polymer with a lower molecular weight, between that of the monomer and the final polymer, and the prepolymer contains reactive functional groups that can undergo further polymerization to obtain a fully cross-linked or hardened product with a higher molecular weight. Polymers include, but are not limited to, oligomers. Oligomers, also known as low-molecular-weight polymers, are polymers composed of 2 to 20 repeating units, typically 2 to 5 repeating units.

[0028] Unless otherwise specified, in this invention, modified products (also called modified materials) include: products after modification of the reactive functional groups of each resin, products after crosslinking of each resin with other resins, products after homopolymerization of each resin, products after copolymerization of each resin with other resins, etc. For example, but not limited to, modification may involve replacing the original hydroxyl groups with vinyl groups through a chemical reaction, or obtaining terminal hydroxyl groups by chemically reacting the original terminal vinyl groups with p-aminophenol.

[0029] In this document, "vinyl-containing" refers to a compound structure containing an vinyl carbon-carbon double bond (C=C) or a derivative functional group thereof. Therefore, examples of vinyl-containing compounds include, but are not limited to, compounds containing vinyl, allyl, vinyl benzyl, or methacrylate functional groups. Unless otherwise specified, the position of the aforementioned functional groups is not particularly limited; for example, they may be located at the end of a long chain structure. Thus, for example, "vinyl-containing polyphenylene ether resin" represents, but is not limited to, polyphenylene ether resins containing vinyl, allyl, vinyl benzyl, or methacrylate functional groups.

[0030] Unless otherwise specified, parts by weight in this document refer to the number of parts by weight, which can be any unit of weight, such as, but not limited to, kilograms, grams, pounds, etc. For example, 100 parts by weight of maleimide resin means that it can be 100 kilograms of maleimide resin or 100 pounds of maleimide resin. If the resin solution contains both solvent and resin, then generally, parts by weight of (solid or liquid) resin refers to the weight of that (solid or liquid) resin and does not include the weight of the solvent in the solution, while parts by weight of solvent refers to the weight of that solvent.

[0031] The following detailed embodiments are merely illustrative in nature and are not intended to limit the invention or its uses. Furthermore, this document is not limited to the foregoing prior art or the invention itself, or to any theory described in the following detailed embodiments or examples.

[0032] As mentioned above, the main objective of this invention is to provide a resin composition comprising 50 parts by weight of a vinyl polyphenylene ether resin, 1 to 30 parts by weight of a styrene-butadiene-styrene block copolymer, and 0.5 to 30 parts by weight of zinc molybdate-coated silica, wherein the mass ratio of zinc molybdate to silica in the zinc molybdate-coated silica is between 1:9 and 2:8.

[0033] For example, in the resin composition, the content of styrene-butadiene-styrene block copolymer is from 1 part by weight to 30 parts by weight relative to 50 parts by weight of vinyl polyphenylene ether resin, such as, but not limited to, 1 part by weight, 2 parts by weight, 3 parts by weight, 5 parts by weight, 10 parts by weight, 20 parts by weight, or 30 parts by weight of styrene-butadiene-styrene block copolymer. Another example is that the resin composition includes 50 parts by weight of vinyl polyphenylene ether resin and 6 parts by weight of styrene-butadiene-styrene block copolymer.

[0034] For example, in the resin composition, the content of zinc molybdate-coated silica is from 0.5 parts by weight to 30 parts by weight relative to 50 parts by weight of vinyl polyphenylene ether resin, such as, but not limited to, 0.5 parts by weight, 0.6 parts by weight, 1 part by weight, 2 parts by weight, 3 parts by weight, 5 parts by weight, 10 parts by weight, 20 parts by weight, or 30 parts by weight of zinc molybdate-coated silica. Another example is that the resin composition includes 50 parts by weight of vinyl polyphenylene ether resin and 10 parts by weight of zinc molybdate-coated silica.

[0035] In other words, in the resin composition of the present invention, the content of styrene-butadiene-styrene block copolymer is from 1 part by weight to 30 parts by weight, and the content of zinc molybdate-coated silica is from 0.5 parts by weight to 30 parts by weight, compared to 50 parts by weight of vinyl polyphenylene ether resin.

[0036] For example, in one embodiment, the aforementioned vinyl-containing polyphenylene ether resin may include various vinyl-containing polyphenylene ether resins known in the art. The vinyl-containing polyphenylene ether resins suitable for use in this invention are not particularly limited and may be any one or more commercially available products, homemade products, or combinations thereof. Examples of vinyl-containing polyphenylene ether resins may include, but are not limited to, polyphenylene ether resins containing vinyl, allyl, vinyl benzyl, or methacrylate. For example, in one embodiment, the aforementioned vinyl-containing polyphenylene ether resin includes vinyl benzyl biphenyl polyphenylene ether resin, methacrylate polyphenylene ether resin (i.e., methacryloyl polyphenylene ether resin), allyl polyphenylene ether resin, vinyl benzyl bisphenol A polyphenylene ether resin, vinyl chain-extended polyphenylene ether resin, or combinations thereof. For example, the aforementioned vinyl-containing polyphenylene ether resin may be a vinylbenzyl biphenyl polyphenylene ether resin with a number average molecular weight of about 1200 (e.g., OPE-2st 1200, available from Mitsubishi Gas Chemical Company), a vinylbenzyl biphenyl polyphenylene ether resin with a number average molecular weight of about 2200 (e.g., OPE-2st 2200, available from Mitsubishi Gas Chemical Company), a methacrylate polyphenylene ether resin with a number average molecular weight of about 1900 to 2300 (e.g., SA9000, available from Sabic Company), a vinylbenzyl bisphenol A polyphenylene ether resin with a number average molecular weight of about 2400 to 2800, a vinyl chain-extended polyphenylene ether resin with a number average molecular weight of about 2200 to 3000, or a combination thereof. The aforementioned vinyl chain-extended polyphenylene ether resin may include various polyphenylene ether resins disclosed in U.S. Patent Application Publication No. 2016 / 0185904A1, all of which are incorporated herein by reference.

[0037] For example, in one embodiment, the aforementioned styrene-butadiene-styrene block copolymer may include various styrene-butadiene-styrene block copolymers known in the art, and their definitions are as described above. The styrene-butadiene-styrene block copolymers applicable to the present invention are not particularly limited and may be any one or more commercially available products, homemade products, or combinations thereof. For example, in one embodiment, the styrene-butadiene-styrene block copolymer may be a styrene-butadiene-styrene block copolymer produced by Asahi KASEI under trade names such as T-411, T-432, T-437, T-438, T-439, or a styrene-butadiene-styrene block copolymer produced by KRATON under trade names such as D1101, D1102, D1116, D1118, D1152, D1153, D1184, D1192.

[0038] In this invention, zinc molybdate-coated silica refers to silica whose surface is at least partially covered by zinc molybdate. The shape and size of the silica are not particularly limited, nor is the method of coating the silica surface with zinc molybdate particularly limited. For example, in one embodiment, the aforementioned zinc molybdate-coated silica refers to zinc molybdate particles adhering to the surface of silica particles. Multiple zinc molybdate particles may be adhered to the surface of the silica particles, forming a coating layer on the surface of the silica particles. The adhesion method can use well-known techniques for attaching one inorganic filler to the surface of another inorganic filler, or it can be a specific technique for coating the silica surface with zinc molybdate.

[0039] In the zinc molybdate-coated silica of the present invention, the mass ratio of zinc molybdate to silica is between 1:9 and 2:8.

[0040] In this invention, the size of the zinc molybdate-coated silica is not particularly limited. For example, in one embodiment, the particle size distribution D50 of the zinc molybdate-coated silica is between 2 micrometers and 4 micrometers, preferably between 2 micrometers and 3 micrometers, more preferably between 2 micrometers and 2.5 micrometers, but is not limited thereto.

[0041] For example, in one embodiment, zinc molybdate-coated silica may comprise zinc molybdate-coated silica manufactured by Jinyi Company.

[0042] For example, in one embodiment, the resin composition of the present invention may further comprise a bifunctional aliphatic long-chain acrylate. For example, the aforementioned bifunctional aliphatic long-chain acrylate may be, for instance, an acrylate having an aliphatic long chain with 5 or more carbon atoms and having two acrylate groups.

[0043] In one embodiment, the aforementioned bifunctional aliphatic long-chain acrylate has the following structure:

[0044]

[0045] Where n is an integer greater than or equal to 5, and R is hydrogen or methyl.

[0046] For example, n can be an integer greater than or equal to 5 and less than or equal to 20, or preferably an integer greater than or equal to 6 and less than or equal to 12. In one embodiment, the n value of the aforementioned bifunctional aliphatic long-chain acrylate can be, but is not limited to, 6, 8, 10, 12, 14, 16, 18, or 20. Unless otherwise specified, in this invention, long-chain refers to an n value greater than or equal to 5, and bifunctional means the presence of two acrylate groups.

[0047] Specifically, the aforementioned bifunctional aliphatic long-chain acrylates may be compounds or combinations thereof represented by any of the following formulas (I) to (III):

[0048]

[0049] For example, the bifunctional aliphatic long-chain acrylates used in this invention may include, but are not limited to, 1,6-hexanediacrylate, 1,6-hexanedi (methacrylate), 1,12-dodecanedi (methacrylate), or combinations thereof. For example, in one embodiment, the bifunctional aliphatic long-chain acrylate may be a bifunctional aliphatic long-chain acrylate manufactured by Sartomer under trade names such as SR238, SR239, and SR262, but is not limited thereto.

[0050] In addition to the aforementioned vinyl polyphenylene ether resin, styrene-butadiene-styrene block copolymer, and zinc molybdate-coated silica, the resin composition of the present invention may further include a crosslinking agent. For example, in one embodiment, the resin composition of the present invention may further include 1 to 60 parts by weight of a crosslinking agent, preferably 5 to 50 parts by weight, compared to 50 parts by weight of the vinyl polyphenylene ether resin.

[0051] For example, in one embodiment, the aforementioned crosslinking agent includes triallyl isocyanurate, triallyl cyanurate, maleimide resin, polyolefins other than the styrene-butadiene-styrene block copolymer, small molecule vinyl compounds, epoxy resins, cyanate resins, phenolic resins, styrene-maleic anhydride, polyester resins, amine curing agents, polyamide resins, polyimide resins, or combinations thereof. For example, in one embodiment, the resin composition of the present invention may further include 10 parts by weight of triallyl isocyanurate and 30 parts by weight of maleimide resin, compared to 50 parts by weight of vinyl-containing polyphenylene ether resin.

[0052] For example, in one embodiment, the resin composition of the present invention may further include triallyl isocyanurate as needed. Due to its low boiling point, triallyl isocyanurate will completely evaporate or leave only a small amount (like a solvent) during the B-stage process of making the resin composition into articles (e.g., prepregs, resin films). The amount of triallyl isocyanurate used is not particularly limited. For example, in one embodiment, the resin composition of the present invention may contain 1 to 20 parts by weight of triallyl isocyanurate, for example, 5 to 15 parts by weight of triallyl isocyanurate, compared to 50 parts by weight of vinyl polyphenylene ether resin, and is not limited thereto.

[0053] For example, in one embodiment, the aforementioned maleimide resin includes monomers or combinations thereof having one or more maleimide functional groups in their molecules. Unless otherwise specified, the maleimide resin used in this invention is not particularly limited and may be any one or more maleimide resins suitable for the manufacture of prepregs, resin films, laminates, or printed circuit boards. In some embodiments, one or more of the following maleimide resins may be used: 4,4'-diphenylmethane bismaleimide, oligomer of phenylmethane maleimide (or polyphenylmethane maleimide), bisphenol A diphenyl ether bismaleimide, and 3,3'-dimethyl-5,5'-diethyl-4,4'-diphenylmethane bismaleimide. Bismaleimide (also known as bis(3-ethyl-5-methyl-4-maleimidephenyl)methane), 3,3'-dimethyl-5,5'-dipropyl-4,4'-diphenylmethane bismaleimide, biphenylmaleimide, m-phenylene bismaleimide

[0054] bismaleimide), 4-methyl-1,3-phenylene bismaleimide

[0055] bismaleimide), 1,6-bismaleimide-(2,2,4-trimethyl)hexane, 2,3-dimethylbenzylmaleimide (N-2,3-xylylmaleimide), 2,6-dimethylbenzylmaleimide (N-2,6-xylylmaleimide), N-phenylmaleimide, diethyl bismaleimidotoluene, vinylbenzyl maleimide (VBM), maleimide resins containing aliphatic long-chain structures, or combinations thereof. Unless otherwise specified, the aforementioned maleimide resins also include modified versions of these components.

[0056] For example, maleimide resins may be those manufactured by Daiwakasei Industry Co., Ltd. under trade names such as BMI-1000, BMI-1000H, BMI-1100, BMI-1100H, BMI-2000, BMI-2300, BMI-3000, BMI-3000H, BMI-4000, BMI-5000, BMI-5100, BMI-TMH, BMI-7000 and BMI-7000H; or those manufactured by KI Chemical Co., Ltd. under trade names such as BMI-70 and BMI-80; or those manufactured by Nippon Kayaku Co., Ltd. under trade names such as MIR-3000 and MIR-5000; or those manufactured by Evonik Chemical Co., Ltd. under trade names such as DE-TDAB.

[0057] For example, maleimide resins containing aliphatic long-chain structures can be maleimide resins produced by the designer's subsidiary under trade names such as BMI-689, BMI-1400, BMI-1500, BMI-1700, BMI-2500, BMI-3000, BMI-5000 and BMI-6000.

[0058] In addition to the styrene-butadiene-styrene block copolymer, the resin composition of the present invention may further include other polyolefins. Examples of these other polyolefins include, but are not limited to: styrene-butadiene-divinylbenzene terpolymer, styrene-butadiene-maleic anhydride terpolymer, vinyl-polybutadiene-urethane oligomer, styrene-butadiene copolymer, hydrogenated styrene-butadiene copolymer (or styrene-ethylene-butene-styrene block polymer), styrene-isoprene copolymer, hydrogenated styrene-isoprene copolymer, hydrogenated styrene-butadiene-divinylbenzene terpolymer, polybutadiene (i.e., butadiene homopolymer), maleic anhydride-butadiene copolymer, methylstyrene copolymer, or combinations thereof. Preferably, the other polyolefins are styrene-butadiene copolymer, hydrogenated styrene-butadiene copolymer, polybutadiene, styrene-butadiene-maleic anhydride terpolymer, or maleic anhydride-butadiene copolymer. For example, the polybutadiene may include polybutadiene without reactive functional groups, hydrogenated polybutadiene, hydroxyl-containing polybutadiene, polybutadiene containing phenolic hydroxyl groups (having a polybutadiene structure and phenolic hydroxyl groups), carboxyl-containing polybutadiene, acid anhydride-containing polybutadiene, epoxy-containing polybutadiene, isocyanate-containing polybutadiene, urethane-containing polybutadiene, hydrogenated polybutadiene with vinylated terminal hydroxyl groups (no longer having hydroxyl groups), or combinations thereof. For example, the polybutadiene may include epoxy-containing polybutadiene.

[0059] For example, the aforementioned small molecule vinyl compounds refer to vinyl compounds with a molecular weight less than or equal to 1000, preferably with a molecular weight between 100 and 900, and more preferably with a molecular weight between 100 and 800. In this invention, the small molecule vinyl compound can be, but is not limited to, any or a combination of divinylbenzene (DVB), bis(vinylbenzyl)ether (BVBE), 1,2,4-trivinylcyclohexane (TVCH), diallyl isophthalate (DAIP), and diallyl bisphenol A (DABPA).

[0060] For example, the epoxy resins mentioned above can be various epoxy resins known in the art, including but not limited to bisphenol A epoxy resin, bisphenol F epoxy resin, bisphenol S epoxy resin, bisphenol AD ​​epoxy resin, phenolic (novolac) epoxy resin, trifunctional epoxy resin, tetrafunctional epoxy resin, multifunctional phenolic epoxy resin, dicyclopentadiene (DCPD) epoxy resin, phosphorus-containing epoxy resin, p-xylene epoxy resin, naphthalene-type epoxy resin (e.g., naphthol-type epoxy resin, naphthyl ether-type epoxy resin), benzofuran-type epoxy resin, and isocyanate-modified epoxy resin. Among them, the phenolic epoxy resin may be phenol novolac epoxy resin, bisphenol A novolac epoxy resin, bisphenol F novolac epoxy resin, biphenyl novolac epoxy resin, phenol benzaldehyde epoxy resin, phenol aralkyl novolac epoxy resin, or o-cresolnovolac epoxy resin; among them, the phosphorus-containing epoxy resin may be DOPO (9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide) epoxy resin, DOPO-HQ epoxy resin, or a combination thereof.The aforementioned DOPO epoxy resin may be selected from one or more of the following: DOPO-containing phenolic novolac epoxy resin, DOPO-containing cresol novolac epoxy resin, and DOPO-containing bisphenol-A novolac epoxy resin; the aforementioned DOPO-HQ epoxy resin may be selected from one or more of the following: DOPO-containing phenolic novolac epoxy resin, DOPO-containing cresol novolac epoxy resin, and DOPO-containing bisphenol-A novolac epoxy resin.

[0061] For example, the aforementioned cyanate ester resin can be any one or more cyanate ester resins suitable for manufacturing prepregs, resin films, laminates, or printed circuit boards, such as compounds having an Ar-OC≡N structure, wherein Ar can be a substituted or unsubstituted aromatic group. Specific examples of cyanate ester resins include, but are not limited to, phenolic cyanate ester resins, bisphenol A cyanate ester resins, bisphenol F cyanate ester resins, cyanate ester resins containing a dicyclopentadiene structure, cyanate ester resins containing a naphthalene ring structure, phenolphthalein cyanate ester resins, adamantane cyanate ester resins, fluorene cyanate ester resins, or combinations thereof. Among these, phenolic cyanate ester resins can be phenolic cyanate ester resins, bisphenol A phenolic cyanate ester resins, bisphenol F phenolic cyanate ester resins, or combinations thereof. For example, cyanate ester resins may be cyanate ester resins manufactured by Lonza under trade names such as Primaset PT-15, PT-30S, PT-60S, BA-200, BA-230S, BA-3000S, BTP-2500, BTP-6020S, DT-4000, DT-7000, ULL950S, HTL-300, CE-320, LVT-50, and LeCy.

[0062] For example, the aforementioned phenolic resins include, but are not limited to, monofunctional, difunctional, or polyfunctional phenolic resins, including phenolic resins well known for use in resin compositions for manufacturing prepregs, such as phenolic oxy resins, phenolic resins, and so on.

[0063] For example, in the above-mentioned styrene-maleic anhydride, the ratio of styrene (S) to maleic anhydride (MA) can be 1 / 1, 2 / 1, 3 / 1, 4 / 1, 6 / 1, 8 / 1, or 12 / 1, such as the styrene-maleic anhydride copolymers sold by Cray Valley under the trade names SMA-1000, SMA-2000, SMA-3000, EF-30, EF-40, EF-60, and EF-80, or the styrene-maleic anhydride copolymers sold by Polyscope under the trade names C400, C500, C700, and C900.

[0064] For example, the aforementioned polyester resin can be obtained by esterification of an aromatic compound with a dicarboxylic acid group and an aromatic compound with a dihydroxy group. The polyester resin may include, but is not limited to, products sold by Dai Nippon Ink Chemical under the trade names HPC-8000, HPC-8150, or HPC-8200.

[0065] For example, the aforementioned amine curing agents may include, but are not limited to, at least one or a combination of diaminodiphenyl sulfone, diaminodiphenylmethane, diaminodiphenyl ether, diaminodiphenyl sulfide and dicyandiamide.

[0066] For example, the polyamide resin mentioned above can be any type of polyamide resin known in the art, including but not limited to various commercially available polyamide resin products.

[0067] For example, the aforementioned polyimide resin may be any type of polyimide resin known in the art, including but not limited to various commercially available polyimide resin products.

[0068] In addition to the aforementioned components, the resin composition of the present invention may further include, as needed, inorganic fillers, flame retardants, curing accelerators, polymerization inhibitors, solvents, silane coupling agents, dyes, toughening agents, or combinations thereof.

[0069] For example, the aforementioned inorganic fillers can be any one or more inorganic fillers suitable for the manufacture of prepregs, resin films, laminates, or printed circuit boards. Specific examples include, but are not limited to: silica (molten, non-molten, porous, or hollow), alumina, aluminum hydroxide, magnesium oxide, magnesium hydroxide, calcium carbonate, aluminum nitride, boron nitride, silicon aluminum carbide, silicon carbide, titanium dioxide, barium titanate, lead titanate, strontium titanate, calcium titanate, magnesium titanate, barium zirconate, lead zirconate, magnesium zirconate, lead zirconate titanate, zinc molybdate, calcium molybdate, magnesium molybdate, ammonium molybdate, zinc molybdate-modified talc, zinc oxide, zirconium oxide, mica, boehmite (AlOOH), calcined talc, talc, silicon nitride, zirconium tungstate, litharge, calcined kaolin, or combinations thereof. Furthermore, the inorganic fillers can be spherical, fibrous, plate-like, granular, flake-like, or needle-like, and can be selectively pretreated with a silane coupling agent. For example, in one embodiment, the resin composition of the present invention may further include 10 to 200 parts by weight of inorganic filler, preferably 50 to 150 parts by weight of inorganic filler, but not limited thereto, in addition to 50 parts by weight of vinyl polyphenylene ether resin.

[0070] For example, the aforementioned flame retardant can be any one or more flame retardants suitable for manufacturing prepregs, resin films, laminates, or printed circuit boards, such as, but not limited to, phosphorus-containing flame retardants, preferably including: ammonium polyphosphate, hydroquinone bis-(diphenylphosphate), bisphenol A bis-(diphenylphosphate), tri(2-carboxyethyl)phosphine (TCEP), trichloroisopropyl phosphate, trimethyl phosphate (TMP), dimethyl methyl phosphonate (DMMP), resorcinol bis-(dixylenyl)phosphate. phosphate), RDXP (such as commercially available products like PX-200, PX-201, PX-202, etc.), phosphazene compounds (such as commercially available products like SPB-100, SPH-100, SPV-100, etc.), melamine polyphosphate, DOPO

[0071] (9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide) and their derivatives or resins, DPPO (diphenylphosphine oxide) and its derivatives or resins, melamine cyanurate, tri-hydroxyethyl isocyanurate, aluminum phosphonates (e.g., OP-930, OP-935, etc.) or combinations thereof.

[0072] For example, the aforementioned flame retardant may be a DPPO compound (such as a bisDPPO compound, such as commercially available products like PQ-60), a DOPO compound (such as a bisDOPO compound), a DOPO resin (such as DOPO-HQ, DOPO-NQ, DOPO-PN, DOPO-BPN), or a DOPO-bonded epoxy resin, etc., wherein DOPO-PN is a DOPO phenolic compound, and DOPO-BPN may be a bisphenolic compound such as DOPO-BPAN (DOPO-bisphenol A novolac), DOPO-BPFN (DOPO-bisphenol F novolac), or DOPO-BPSN (DOPO-bisphenol S novolac). For example, in one embodiment, compared to 50 parts by weight of the vinyl polyphenylene ether resin, the resin composition of the present invention may further include 10 to 100 parts by weight of a flame retardant, preferably 20 to 80 parts by weight of a flame retardant, but is not limited thereto.

[0073] For example, the aforementioned curing accelerators (including curing initiators) may include catalysts such as Lewis bases or Lewis acids. Lewis bases may include one or more of the following: imidazole, boron trifluoride amine complex, ethyltriphenyl phosphonium chloride, 2-methylimidazole (2MI), 2-phenyl-1H-imidazole (2PZ), 2-ethyl-4-methylimidazole (2E4MI), triphenylphosphine (TPP), and 4-dimethylaminopyridine (DMAP). Lewis acids may include metal salt compounds, such as manganese, iron, cobalt, nickel, copper, zinc, etc., and metal catalysts such as zinc octanoate and cobalt octanoate. Curing accelerators also include curing initiators, such as peroxides that can generate free radicals. Curing initiators include, but are not limited to, diisopropylbenzene peroxide, tert-butyl peroxybenzoate, dibenzoyl peroxide (BPO), 2,5-dimethyl-2,5-di(tert-butylperoxy)-3-hexyne (25B), and bis(tert-butylperoxyisopropyl)benzene or combinations thereof. For example, in one embodiment, the resin composition of the present invention may further include 0.001 parts by weight to 2 parts by weight of curing accelerator, preferably 0.01 parts by weight to 1.5 parts by weight of curing accelerator, but is not limited thereto, compared to 50 parts by weight of vinyl-containing polyphenylene ether resin.

[0074] For example, the aforementioned polymerization inhibitors may include, but are not limited to, 1,1-diphenyl-2-trinitrophenylhydrazine, methacrylonitrile, 2,2,6,6-tetramethyl-1-oxy-piperidine, disulfides, nitroxide-stabilized free radicals, triphenylmethyl free radicals, metal ion free radicals, sulfur free radicals, hydroquinone, p-methoxyphenol, p-benzoquinone, phenthiazide, β-phenylnaphthylamine, p-tert-butylcatechol, methylene blue, 4,4'-butylenebis(6-tert-butyl-3-methylphenol), and 2,2'-methylenebis(4-ethyl-6-tert-butylphenol), or combinations thereof. For example, the aforementioned nitroxide-stabilized free radicals may include, but are not limited to, 2,2,6,6-substituted-1-piperidinoxy free radicals or 2,2,5,5-substituted-1-pyrrolidineoxy free radicals derived from cyclic hydroxylamines. As substituents, preferably alkyl groups with four or fewer carbon atoms, such as methyl or ethyl. The specific nitroxide free radical compounds are not limited, and examples include, but are not limited to, 2,2,6,6-tetramethyl-1-piperidineoxy radical, 2,2,6,6-tetraethyl-1-piperidineoxy radical, 2,2,6,6-tetramethyl-4-oxo-1-piperidineoxy radical, 2,2,5,5-tetramethyl-1-pyrrolidineoxy radical, 1,1,3,3-tetramethyl-2-isodihydroindoleoxy radical, N,N-di-tert-butylamineoxy radical, etc. Stable free radicals such as galvinoxyl radicals can also be used instead of nitroxide free radicals. The polymerization inhibitors suitable for the resin compositions of the present invention can also be products derived from the substitution of hydrogen atoms or groups in the inhibitor by other atoms or groups. For example, products derived from the substitution of hydrogen atoms in the inhibitor by groups such as amino, hydroxyl, or ketone carbonyl groups. For example, in one embodiment, the resin composition of the present invention may further include 0.001 to 5 parts by weight of a polymerization inhibitor, preferably 0.01 to 3 parts by weight, but not limited thereto, compared to 50 parts by weight of the vinyl polyphenylene ether resin.

[0075] For example, the solvent suitable for the resin composition of the present invention is not particularly limited, and can be any solvent suitable for dissolving the resin composition of the present invention, including but not limited to: methanol, ethanol, ethylene glycol monomethyl ether, acetone, butanone (also known as methyl ethyl ketone), methyl isobutyl ketone, cyclohexanone, toluene, xylene, methoxyethyl acetate, ethoxyethyl acetate, propoxyethyl acetate, ethyl acetate, dimethylformamide, dimethylacetamide, propylene glycol methyl ether acetate, and other solvents or mixtures thereof. For example, in one embodiment, the resin composition of the present invention may further include 20 to 200 parts by weight of solvent, preferably 70 to 180 parts by weight of solvent, or 140 to 170 parts by weight of solvent, but is not limited thereto, compared to 50 parts by weight of vinyl polyphenylene ether resin.

[0076] For example, the aforementioned silane coupling agent may include silane compounds (such as, but not limited to, siloxane compounds), which, depending on the functional group, may be classified as amino silane compounds, epoxy silane compounds, vinyl silane compounds, acrylate silane compounds, methacrylate silane compounds, hydroxy silane compounds, isocyanate silane compounds, methacryloxy silane compounds, and acryloyloxy silane compounds. For example, in one embodiment, compared to 50 parts by weight of vinyl-containing polyphenylene ether resin, the resin composition of the present invention may further include 0.001 parts by weight to 2 parts by weight of silane coupling agent, preferably 0.01 parts by weight to 1 part by weight of silane coupling agent, but not limited thereto.

[0077] For example, the aforementioned dyeing agents may include, but are not limited to, dyes or pigments.

[0078] In this invention, the main function of adding a toughening agent is to improve the toughness of the resin composition. For example, the toughening agent may include, but is not limited to, carboxyl-terminated butadiene acrylonitrile rubber (CTBN), core-shell rubber, or combinations thereof. For example, in one embodiment, compared to 50 parts by weight of vinyl polyphenylene ether resin, the resin composition of this invention may further include 1 to 20 parts by weight of toughening agent, preferably 3 to 10 parts by weight of toughening agent, but is not limited thereto.

[0079] The resin compositions of the foregoing embodiments can be made into various articles, such as components for various electronic products, including but not limited to prepregs, resin films, laminates or printed circuit boards.

[0080] For example, the resin compositions of various embodiments of the present invention can be made into a prepreg, which includes a reinforcing material and a layer disposed on the reinforcing material. The layer is obtained by heating the aforementioned resin composition at a high temperature to form a semi-cured state (B-stage). The baking temperature for making the prepreg is between 120°C and 180°C, preferably between 120°C and 160°C. The reinforcing material can be any of a fiber material, woven fabric, or nonwoven fabric, and the woven fabric preferably includes glass fiber cloth. There is no particular limitation on the type of glass fiber cloth; it can be any commercially available glass fiber cloth suitable for printed circuit boards, such as E-type glass fiber cloth, D-type glass fiber cloth, S-type glass fiber cloth, T-type glass fiber cloth, L-type glass fiber cloth, or Q-type glass fiber cloth. The fiber types include yarn and roving, and the form can include open or closed fibers. The aforementioned nonwoven fabric preferably includes liquid crystal resin nonwoven fabric, such as polyester nonwoven fabric, polyurethane nonwoven fabric, etc., but is not limited thereto. The aforementioned woven fabric may also include liquid crystal resin woven fabric, such as polyester woven fabric or polyurethane woven fabric, etc., but is not limited thereto. This reinforcing material increases the mechanical strength of the prepreg. In a preferred embodiment, the reinforcing material may also be selectively pretreated with a silane coupling agent. The prepreg subsequently undergoes heat curing (C-stage) to form an insulating layer.

[0081] For example, the resin compositions of various embodiments of the present invention can be made into resin films, which are obtained by baking and heating the aforementioned resin compositions to achieve semi-curing. The resin compositions can be selectively coated onto polyethylene terephthalate (PET) films, polyimide (PI) films, copper foils, or adhesive-backed copper foils, and then baked and heated to form a semi-cured state, thereby forming a resin film.

[0082] For example, the resin compositions of various embodiments of the present invention can be made into a laminate comprising two metal foils and an insulating layer disposed between the metal foils. The insulating layer can be obtained by curing the aforementioned resin composition under high temperature and high pressure conditions (C-stage), wherein a suitable curing temperature is between 180°C and 240°C, preferably between 200°C and 230°C, and the curing time is 90 to 180 minutes. The insulating layer can be formed by curing the aforementioned prepreg or resin film (C-stage). The metal foils may include copper, aluminum, nickel, platinum, silver, gold, or alloys thereof; for example, the metal foil may be copper foil. In one embodiment, the aforementioned laminate is a copper clad laminate (CCL).

[0083] Furthermore, the aforementioned multilayer board can be further processed through circuit manufacturing processes to form a circuit board, such as a printed circuit board.

[0084] In one embodiment, the resin composition provided by the present invention can improve at least one of the following properties: gel time stability, tensile strength to copper foil, dielectric loss variation rate, conductive anode wire test, tensile strength between the prepreg and the core substrate, and dielectric constant variation rate.

[0085] For example, the resin composition provided by the present invention or the articles made therefrom may satisfy one, more or all of the following characteristics:

[0086] The gel time stability calculated from the gel time measured according to the method described in IPC-TM-650 2.3.18 is less than or equal to 32 seconds, for example, between 7 seconds and 32 seconds;

[0087] The pull force on the copper foil measured according to the method described in IPC-TM-650 2.4.8 is greater than or equal to 3.5 lb / in, for example, between 3.5 lb / in and 4.5 lb / in;

[0088] The dielectric loss variation rate calculated from the dielectric loss measured at a frequency of 10 GHz according to the method described in JIS C2565 is less than or equal to 40%, for example, between 18% and 40%.

[0089] The method described in IPC-TM-650 2.6.25 was tested for 250 hours at 1000V, and the conductivity of the anode wire was verified; and

[0090] The method described in IPC-TM-650 2.6.25 was tested for 1000 hours at 100V, and the conductive anode wire was tested.

[0091] For example, the resin composition provided by the present invention or the articles made therefrom may satisfy one, more or all of the following characteristics:

[0092] The tensile force between the prepreg and the core substrate is greater than or equal to 3.0 lb / in, for example, the tensile force between the prepreg and the core substrate is between 3.0 lb / in and 4.8 lb / in; and

[0093] The dielectric constant variation rate calculated from the dielectric constant measured at a frequency of 10 GHz according to the method described in JIS C2565 is less than or equal to 5%, for example, between 1% and 5%.

[0094] The resin compositions of the embodiments and comparative examples of the present invention were prepared according to the amounts specified in Tables 1 to 3 using various raw materials from the following sources, and were further prepared into various test samples.

[0095] The chemical raw materials used in the embodiments and comparative examples of this invention are as follows:

[0096] OPE-2st: Polyphenylene ether resin containing ethylene benzyl biphenyl, OPE-2st 2200, purchased from Mitsubishi Gas Chemical.

[0097] SA9000: Contains methacrylate polyphenylene ether resin, purchased from Sabic.

[0098] T-439: Styrene-butadiene-styrene block copolymer (SBS), purchased from Asahi KASEI. The mass ratio of styrene units to butadiene units is 45:55.

[0099] D-1118: Styrene-butadiene-styrene block copolymer (SBS), purchased from KRATON. The mass ratio of styrene units to butadiene units is 30:70.

[0100] M1911: Hydrogenated styrene-butadiene-styrene block copolymer (SEBS), purchased from Asahi KASEI.

[0101] H1051: Hydrogenated styrene-butadiene-styrene block copolymer (SEBS), purchased from Asahi KASEI.

[0102] Zinc molybdate coated with silica: The mass ratio of zinc molybdate to silica is 2:8, and the particle size distribution D50 is 2 to 4 micrometers. It was purchased from Jinyi.

[0103] Zinc molybdate coated with silica: The mass ratio of zinc molybdate to silica is 1:9, and the particle size distribution D50 is 2 to 4 micrometers. It was purchased from Jinyi.

[0104] 911C: Zinc molybdate-coated talc, with a zinc molybdate to talc mass ratio of 2:8 and a particle size distribution D50 of 2 to 4 micrometers, purchased from Kemguard.

[0105] MZM: Zinc molybdate coated with magnesium hydroxide, with a zinc molybdate to magnesium hydroxide mass ratio of 2:8, and a particle size distribution D50 of 2 to 4 micrometers, purchased from Kemguard.

[0106] LB398: Zinc molybdate coated with aluminum hydroxide, with a zinc molybdate to aluminum hydroxide mass ratio of 2:8, and a particle size distribution D50 of 2 to 4 micrometers, purchased from Kemguard.

[0107] Zinc molybdate: purchased from Amex Biotechnology.

[0108] SC2050 SMJ: Spherical silica with acrylic silane coupling agent surface treatment, purchased from Admatechs.

[0109] SR238: 1,6-hexanediacrylate, purchased from Sartomer.

[0110] BMI-70: Bis(3-ethyl-5-methyl-4-maleimidebenzene)methane, purchased from KI Chemicals.

[0111] TAIC: Triallyl isocyanurate, commercially available.

[0112] SC2500 SVJ: Spherical silica with a silane coupling agent surface treatment, purchased from Admatechs.

[0113] 25B: 2,5-Dimethyl-2,5-bis(tert-butylperoxy)-3-hexyne, purchased from Nippon Oils & Fats Co., Ltd.

[0114] Toluene: Commercially available.

[0115] MEK: Butyl ketone, commercially available.

[0116] The resin compositions (all in parts by weight) and the results of property tests for the examples and comparative examples are shown in the table below:

[0117] [Table 1] Composition (parts by weight) and property test results of the resin compositions in the examples

[0118]

[0119] [Table 2] Composition (parts by weight) and property test results of the resin compositions in the examples

[0120]

[0121]

[0122] [Table 3] Composition (parts by weight) and property test results of comparative example resin compositions

[0123]

[0124] The aforementioned characteristics are based on the preparation of the analyte (sample) as described below, followed by characteristic analysis under specific conditions.

[0125] 1. Prepreg (PP): Using the resin compositions of Examples E1-E9 and Comparative Examples C1-C6 (parts by weight), the components of the resin compositions were added to a mixing tank and mixed evenly to form a varnish. The varnish was placed in an impregnation tank, and then glass fiber cloth (e.g., E-glass fiber fabric of specifications 1080 and 2116, purchased from Asahi Corporation) was immersed in the impregnation tank to allow the resin composition to adhere to the glass fiber cloth. The mixture was then heated and baked at 140 to 160°C for approximately 2 minutes to obtain a prepreg. The resin content of the prepreg made using 1080 E-glass fiber cloth was approximately 65%; the resin content of the prepreg made using 2116 E-glass fiber cloth was approximately 55%.

[0126] 2. Copper-containing substrate 1 (also known as copper foil substrate, formed by laminating two prepreg sheets): Prepare two 18-micron thick reverse treatment foils (RTF3) and two 1080 E-glass fiber cloths impregnated with prepreg sheets made from the samples to be tested (each set of examples or each set of comparative examples). The resin content of each prepreg sheet is approximately 65%. The copper foil, two prepreg sheets, and copper foil are laminated in that order, and the mixture is subjected to vacuum conditions and a pressure of 30 kgf / cm². 2 A copper-containing substrate 1 is formed by laminating at 215°C for 90 minutes. Two prepreg sheets are then cured to form an insulating layer between the two copper foils; the resin content of the insulating layer is approximately 65%.

[0127] 3. Copper-containing substrate 2 (composed of six prepreg sheets laminated together): Prepare two 18-micron thick reverse treatment foils (RTF3) and six 2116 E-glass fiber cloths impregnated with the prepreg sheets of each test sample (each set of examples or each set of comparative examples). The resin content of each prepreg sheet is approximately 55%. The prepreg sheets are laminated in the order of copper foil, six prepreg sheets, and copper foil, under vacuum conditions and a pressure of 30 kgf / cm². 2 A copper-containing substrate 2 is formed by laminating at 215℃ for 90 minutes. Six prepreg sheets are then cured to form an insulating layer between the two copper foils; the resin content of the insulating layer is approximately 55%.

[0128] 4. Copper-containing substrate 3 (composed of eight prepreg sheets laminated together): Prepare two 18-micron thick reverse treatment foils (RTF3) and eight 2116 E-glass fiber cloths impregnated with the prepreg sheets of each test sample (each set of examples or each set of comparative examples). The resin content of each prepreg sheet is approximately 55%. The prepreg sheets are laminated in the order of copper foil, eight prepreg sheets, and copper foil, under vacuum conditions and a pressure of 30 kgf / cm². 2 A copper-containing substrate 3 is formed by pressing at 215℃ for 90 minutes. Among them, eight prepregs are cured to form an insulating layer between two copper foils, and the resin content of the insulating layer is about 55%.

[0129] 5. Copper-free substrate 1 (made of two prepregs laminated together): The copper foil on both sides of the copper-containing substrate 1 is removed by etching to obtain copper-free substrate 1 (made of two prepregs laminated together), and the resin content of copper-free substrate 1 is about 65%.

[0130] 6. Copper-free substrate 2 (made of six prepregs laminated together): The copper foil on both sides of the copper-containing substrate 2 is removed by etching to obtain a copper-free substrate 2 (made of six prepregs laminated together), and the resin content of the copper-free substrate 2 is about 55%.

[0131] 7. Copper-free substrate 3 (made of eight prepregs laminated together): The copper foil on both sides of the copper-containing substrate 3 is removed by etching to obtain a copper-free substrate 3 (made of eight prepregs laminated together). The resin content of the copper-free substrate 3 is about 55%.

[0132] 8. Copper-containing substrate 4: Prepare two 35-micron thick reverse treatment foils (RTF3), two folded copper foils (the type of copper foil is not limited; here, the same reverse treatment foil as described above is used, with the bright side of the foil facing inwards when folded), and two 2116 E-glass fiber cloths impregnated with prepregs made from the samples to be tested (each set of examples or each set of comparative examples). The resin content of each prepreg is approximately 55%. Stack the following components in the order of one reverse treatment foil, one prepreg, one copper-free substrate 3 (as the core substrate), one prepreg, and one reverse treatment foil. Insert the two folded copper foils into the interface between the prepreg and the copper-free substrate 3, respectively, to a depth of 1 inch. That is, in the order of one reverse treatment foil, one prepreg, one folded copper foil inserted, one copper-free substrate 3 (as the core substrate), one folded copper foil inserted, one prepreg, and one reverse treatment foil, under vacuum conditions and a pressure of 30 kgf / cm². 2A copper-containing substrate 4 is formed by pressing at 215°C for 90 minutes. The folded copper foil is primarily used to clearly define the interface between the prepreg and the core substrate during tensile testing, facilitating the separation of this interface for the tensile test.

[0133] 9. Copper-containing substrate 5 (assembled from a prepreg): Prepare two 35-micron thick reverse treatment foils (RTF3) and a 2116 E-glass fiber cloth impregnated with prepregs made from each test sample (each set of examples or each set of comparative examples). Each prepreg has a resin content of approximately 55%. The prepregs are stacked in the order of copper foil, a prepreg, and copper foil, and then subjected to vacuum conditions and a pressure of 30 kgf / cm². 2 A copper-containing substrate 5 is formed by pressing at 215℃ for 90 minutes. A prepreg is cured to form an insulating layer between the two copper foils; the resin content of the insulating layer is approximately 55%.

[0134] 10. Copper-containing substrate 6: Prepare two 35-micron thick reverse treatment foils (RTF3) and eight 1080-size E-glass fiber cloths impregnated with prepregs made from the test samples (each set of examples or each set of comparative examples). The resin content of each prepreg is approximately 65%. The prepregs are stacked in the following order: copper foil, two prepregs, copper-containing substrate 5, two prepregs, copper-containing substrate 5, two prepregs, copper-containing substrate 5, two prepregs, and copper foil. The mixture is then subjected to vacuum conditions and a pressure of 30 kgf / cm². 2 A copper-containing substrate was formed by laminating at 215℃ for 90 minutes.

[0135] The test methods and their characteristic analysis items are described below:

[0136] Gel time stability

[0137] Resin compositions (parts by weight) from Examples E1 to E9 and Comparative Examples C1 to C6 were used respectively. Each component of the resin composition was added to a mixing tank and stirred until homogeneous to form a gel (also known as gel). The gel was used as the test sample. Measurement was performed according to the method described in IPC-TM-650 2.3.18. 50 ml of each test sample was placed on a heated plate (cure plate) at a temperature of 181±0.5℃. A pointed bamboo stick was used to draw from the center of the gel to the edge, and the diameter of the gel area was kept between 1.90 and 2.19 cm. The gel was stirred until each test sample began to clump together and continued to be stirred until the largest gel block broke. At the same time, the timer was stopped and the data was recorded. The unit was accurate to the second. This was the first gel time, which was defined as S / G1. After placing each sample at room temperature (25°C) for 7 days, the gel solution of each sample was first stirred and mixed evenly to prevent the inorganic filler in the resin composition from being uniformly dispersed rather than settling at the bottom of the sample. Then, the second gel time was measured according to the aforementioned gel time measurement method, which is defined here as S / G2. Gel time stability is defined as the change in the second gel time relative to the first gel time (ΔS / G). For example, gel time stability is equal to the second gel time minus the first gel time.

[0138] In this field, a lower gel time variation ΔS / G indicates better gel time stability. A difference in gel time stability greater than or equal to 10 seconds indicates a significant difference in gel time stability between different adhesive solutions (representing significant technical difficulty). For example, an article made from the resin composition disclosed in this invention has a gel time stability calculated from the gel time measured according to the method described in IPC-TM-650 2.3.18 that is less than or equal to 32 seconds, for example, between 7 seconds and 32 seconds.

[0139] Peeling strength (P / S) of copper foil

[0140] In the copper foil tensile test, the aforementioned copper substrate 2 (composed of six prepreg sheets laminated together, with a resin content of approximately 55%) was selected and cut into rectangular samples with a width of 24 mm and a length greater than 60 mm. The surface copper foil was etched, leaving only a strip of copper foil with a width of 3.18 mm and a length greater than 60 mm. Using a universal tensile strength tester at room temperature (approximately 25°C), the test was performed according to the method described in IPC-TM-650 2.4.8. The force required for each test sample to pull the copper foil away from the surface of the substrate insulation layer was measured, with the unit being lb / in.

[0141] In this field, higher copper foil tensile strength is preferred. A difference in copper foil tensile strength greater than or equal to 0.3 lb / in indicates a significant difference in copper foil tensile strength between different substrates (representing significant technical difficulty). For example, an article made from the resin composition disclosed in this invention has a copper foil tensile strength greater than or equal to 3.5 lb / in, for example, between 3.5 lb / in and 4.5 lb / in, as measured by the method described in IPC-TM-650 2.4.8.

[0142] Difference rate of dissipation factor

[0143] In calculating the dielectric loss variation rate, the copper-free substrate 1 (composed of two prepreg sheets laminated together, with a resin content of approximately 65%) was selected as the test sample. Following the method described in JIS C2565, each test sample was measured at room temperature (approximately 25°C) and a frequency of 10 GHz to obtain the first dielectric loss, defined as Df1. Furthermore, the same sample was placed at a constant temperature of 168°C for 7 days, and the second dielectric loss was measured after maintaining the first dielectric loss at 168°C for 7 days, defined as Df2. The dielectric loss variation rate is defined as the increase in the second dielectric loss relative to the first dielectric loss, expressed as a percentage (%). For example, the dielectric loss variation rate is equal to [(Df2 – Df1) / Df1] * 100%.

[0144] In this field, a lower dielectric loss variability is preferred. A difference in dielectric loss variability greater than or equal to 3% indicates a significant difference in dielectric loss variability between different substrates (presenting significant technical difficulty). For example, an article made from the resin composition disclosed in this invention has a dielectric loss variability calculated from the dielectric loss measured at a frequency of 10 GHz according to the method described in JIS C2565, which is less than or equal to 40%, for example, between 18% and 40%.

[0145] Conductivity of the anode wire test (1000V / 250 hours)

[0146] The conductive anode wire test (1000V / 250 hours), also known as the CAF (Conductive Anodic Filament) test (1000V / 250 hours), uses a copper-containing substrate 6 as the test sample. The circuit board is fabricated using well-known printed circuit board (PCB) processes. The circuitry consists of 50 vias spaced 1.6 mm apart, with an inner wall spacing of 2.1 mm and an inner diameter of 0.4 mm. The sample is subjected to a 1000-volt (V) voltage for 250 hours at 85°C and 85% RH. The conductive anode wire test is performed on each test sample according to the method described in IPC-TM-650 2.6.25. If the test does not fail after 1000V and 250 hours (not failing means no conductive anodic filaments are generated, i.e. no cation migration occurs), it is marked as "passed"; if the test fails after 1000V and 250 hours (failure means conductive anodic filaments are generated, i.e. cation migration occurs), it is marked as "failed".

[0147] Conductivity of the anode wire test (100V / 1000 hours)

[0148] The conductive anode wire test (100V / 1000 hours), also known as the CAF resistance test (100V / 1000 hours), uses a copper-containing substrate 6 as the test sample. The substrate is fabricated using a well-known printed circuit board (PCB) process. The circuitry consists of 50 vias spaced 0.2 mm apart, with an inner wall spacing of 0.3 mm and an inner diameter of 0.3 mm. The sample is subjected to a 100-volt (V) voltage at 85°C and 85% RH for 1000 hours. The conductive anode wire test is performed on each test sample according to the method described in IPC-TM-650 2.6.25. If the sample does not fail after the 100V, 1000-hour test, it is marked as "Pass"; if it fails after the 100V, 1000-hour test, it is marked as "Fail".

[0149] The tensile strength between the prepreg and the core substrate (i.e., the adhesion strength between the cured prepreg and the adjacent core substrate).

[0150] In measuring the tensile force between the prepreg and the core substrate, a copper-containing substrate 4 was selected. It was cut into a rectangle with a width of 0.5 inches and a length of 5 inches along the folded copper foil. After lifting and pulling apart the interface (also known as the interface) between the prepreg (PP) and the core substrate (core) along the folded copper foil, a universal tensile strength tester was used at room temperature (approximately 25°C) to test the force required to separate the two layers of the cured prepreg (i.e., the prepreg in the prepreg state (B-stage) before lamination) and its adjacent, prepreg-cured core substrate (C-stage) before lamination. The unit is lb / in.

[0151] The tension between the prepreg and the core substrate differs from the well-known tension on copper foil or interlayer tension. Copper foil tension is the force required to separate the insulating layer of the copper foil substrate from the adjacent outer copper foil layer. Interlayer tension is the force required to separate the interface between two adjacent prepreg layers (here referring to two adjacent prepreg layers before curing) within the inner insulating layer of the copper foil substrate. Both copper foil tension and interlayer tension arise when the prepreg in its semi-cured state undergoes high-temperature, high-pressure curing. During this process, the resin composition in the prepreg, which still possesses cross-linking ability (B-stage), cross-links with the copper foil or an adjacent prepreg (which also has cross-linking ability) during pressing, resulting in a relatively strong tension (requiring a larger force to separate the two). The aforementioned tension between the prepreg and the core substrate, however, is the force required to separate the prepreg from the core substrate (C-stage), which has lost its cross-linking ability, during high-temperature, high-pressure curing. Therefore, the tensile force on the copper foil and the interlayer tensile force of a typical copper foil substrate are higher than the tensile force between the prepreg and the core substrate. In other words, strong tensile force on the copper foil and strong interlayer tensile force do not necessarily have strong tensile force between the prepreg and the core substrate at the same time.

[0152] In this field, a higher pull strength between the prepreg and the core substrate is preferable, indicating a stronger adhesion between the cured prepreg (containing copper substrate 4) and the adjacent core substrate. A difference in pull strength between the prepreg and the core substrate greater than or equal to 0.2 lb / in indicates a significant difference in pull strength between the prepreg and the core substrate across different substrates (representing significant technical difficulty). For example, in articles made from the resin composition disclosed in this invention, the pull strength between the prepreg and the core substrate is greater than or equal to 3.0 lb / in, for example, between 3.0 lb / in and 4.8 lb / in.

[0153] Difference rate of dielectric constant

[0154] In calculating the dielectric constant variation rate, the copper-free substrate 1 (composed of two prepreg sheets laminated together, with a resin content of approximately 65%) was selected as the test sample. A microwave dielectric analyzer (purchased from AET Corporation, Japan) was used, following the method described in JIS C2565, to measure each test sample at room temperature (approximately 25°C) and a frequency of 10 GHz, obtaining the first dielectric constant, defined as Dk1. Furthermore, the same sample was placed at a constant temperature of 168°C for 7 days, and the second dielectric constant was measured again after maintaining the first dielectric constant at 168°C for 7 days, as described above, obtaining the second dielectric constant, defined as Dk2. The dielectric constant variation rate is defined as the increase in the second dielectric constant relative to the first dielectric constant, expressed as a percentage (%). For example, the dielectric constant variation rate is equal to [(Dk2 – Dk1) / Dk1] * 100%.

[0155] In this field, a lower dielectric constant variation rate is preferred. A difference in dielectric constant variation rate greater than or equal to 1% indicates a significant difference in dielectric constant variation rate between different substrates (representing significant technical difficulty). For example, the dielectric constant variation rate calculated from the dielectric constant measured at a frequency of 10 GHz according to the method described in JIS C2565 for articles made from the resin composition disclosed in this invention is less than or equal to 5%, for example, between 1% and 5%.

[0156] Based on the test results in Tables 1 to 3, the following phenomena can be clearly observed.

[0157] Examples E1 to E9, which contain 50 parts by weight of a vinyl polyphenylene ether resin, 1 to 30 parts by weight of a styrene-butadiene-styrene block copolymer, and 0.5 to 30 parts by weight of zinc molybdate-coated silica, all simultaneously achieve gel time stability of less than or equal to 32 seconds, copper foil tensile strength of greater than or equal to 3.5 lb / in, dielectric loss variation of less than or equal to 40%, and pass both the conductive anode wire test (1000V / 250 hours) and the conductive anode wire test (100V / 1000 hours). In contrast, Comparative Examples C1 to C6 fail to meet at least one of the following requirements: gel time stability, copper foil tensile strength, dielectric loss variation, conductive anode wire test (1000V / 250 hours), and conductive anode wire test (100V / 1000 hours).

[0158] Compared to Examples E1 to E9, Comparative Examples C1 and C2, which use other polyolefins such as hydrogenated styrene-butadiene-styrene block copolymers instead of the styrene-butadiene-styrene block copolymer of the present invention in the resin composition, cannot meet the requirements for the tensile strength between the prepreg and the core substrate and the tensile strength to the copper foil.

[0159] Compared to Examples E1 to E9, Comparative Example C3, which uses zinc molybdate to cover talc instead of zinc molybdate to cover silica in the resin composition according to the present invention, fails to meet the requirements for the tensile strength between the prepreg and the core substrate, the tensile strength to the copper foil, and the dielectric loss variation rate.

[0160] Compared to Examples E1 to E9, Comparative Example C4, which uses zinc molybdate to cover magnesium hydroxide instead of zinc molybdate to cover silica in the resin composition according to the present invention, fails to meet the requirements in terms of gel time stability, dielectric constant variation rate, conductive anode wire test (1000V / 250 hours), and conductive anode wire test (100V / 1000 hours).

[0161] Compared to Examples E1 to E9, Comparative Example C5, which uses zinc molybdate to cover aluminum hydroxide instead of zinc molybdate to cover silica in the resin composition according to the present invention, fails to meet the requirements in dielectric loss variation rate, conductive anode wire test (1000V / 250 hours), and conductive anode wire test (100V / 1000 hours).

[0162] Compared to Examples E1 to E9, Comparative Example C6, which uses zinc molybdate and silica as inorganic fillers instead of covering silica with the zinc molybdate of the present invention in the resin composition, failed to meet the requirements in terms of tensile strength between the prepreg and the core substrate, conductive anode wire test (1000V / 250 hours), and conductive anode wire test (100V / 1000 hours).

[0163] In general, the resin composition of the present invention can simultaneously achieve the following characteristics: gel time stability of less than or equal to 32 seconds, tensile strength to copper foil greater than or equal to 3.5 lb / in, dielectric loss variation rate of less than or equal to 40%, passing the conductive anode wire test (1000V / 250 hours), passing the conductive anode wire test (100V / 1000 hours), tensile strength between the prepreg and the core substrate greater than or equal to 3.0 lb / in, and dielectric constant variation rate of less than or equal to 5%.

[0164] The above embodiments are merely illustrative in nature and are not intended to limit the embodiments of the applicant or the application or use of such embodiments. In this document, the term "illustrative" means "as an example, illustration, or description." No illustrative embodiment herein should necessarily be construed as being better or more advantageous than other embodiments.

[0165] Furthermore, although at least one exemplary embodiment or comparative example has been presented in the foregoing embodiments, it should be understood that numerous variations are possible with respect to the invention. It should also be understood that the embodiments described herein are not intended to limit the scope, use, or configuration of the claimed subject matter in any way. Rather, the foregoing embodiments will provide a simple guide for those skilled in the art to implement one or more of the described embodiments. Moreover, various changes can be made to the function and arrangement of the components without departing from the scope defined by the claims, and the claims include known equivalents and all foreseeable equivalents at the time of filing of this patent application.

Claims

1. A resin composition, characterized by The mixture comprises 50 parts by weight of a vinyl polyphenylene ether resin, 1 to 30 parts by weight of a styrene-butadiene-styrene block copolymer, and 0.5 to 30 parts by weight of zinc molybdate-coated silica, wherein the mass ratio of zinc molybdate to silica in the zinc molybdate-coated silica is between 1:9 and 2:

8.

2. The resin composition according to claim 1, wherein, The vinyl-containing polyphenylene ether resin includes vinyl benzyl biphenyl polyphenylene ether resin, methacrylate polyphenylene ether resin, or a combination thereof.

3. The resin composition according to claim 1, wherein, The particle size distribution D50 of the zinc molybdate-coated silica is between 2 micrometers and 4 micrometers.

4. The resin composition according to claim 1, wherein the resin composition further comprises an acrylate having an aliphatic long chain having five or more carbon atoms and having two acrylate groups.

5. The resin composition according to claim 1, wherein the resin composition further comprises triallyl isocyanurate, triallyl cyanurate, maleimide resin, polyolefin different from the styrene-butadiene-styrene block copolymer, small molecule vinyl compound, epoxy resin, cyanate resin, phenolic resin, styrene maleic anhydride, polyester resin, amine curing agent, polyamide resin, polyimide resin or a combination thereof, wherein the small molecule vinyl compound is a vinyl compound with a molecular weight less than or equal to 1000.

6. The resin composition according to claim 1, wherein the resin composition further comprises inorganic fillers, flame retardants, curing accelerators, polymerization inhibitors, solvents, silane coupling agents, colorants, toughening agents, or combinations thereof.

7. An article made from the resin composition of claim 1, characterized by The products include prepregs, resin films, laminates, or printed circuit boards.

8. The article of claim 7, wherein the gel time stability of the article, calculated by referring to the gel time measured by the method of IPC-TM-650 2.3.18, is less than or equal to 32 seconds.

9. The article of claim 7, wherein the tensile strength to copper foil measured with reference to the method of IPC-TM-650 2.4.8 is greater than or equal to 3.5 lb / in.

10. The article of claim 7, wherein the dielectric loss variation rate calculated by measuring the dielectric loss at a frequency of 10 GHz according to the method of JIS C2565 is less than or equal to 40%.

11. The article of claim 7, wherein the article is tested for 250 hours at a voltage of 1000V according to the method described in IPC-TM-650 2.6.25, and can be tested by a conductive anode wire.

12. The article of claim 7, wherein the article is tested for 1000 hours at 100V according to the method described in IPC-TM-650 2.6.25, and can be tested by a conductive anode wire.

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