Resin composition and products thereof

Abstract

The present invention discloses a resin composition comprising 20 to 45 parts by weight of a phosphorus-containing bismaleimide and 100 parts by weight of a thermosetting resin, wherein the phosphorus-containing bismaleimide has a structure represented by formula (I); and the thermosetting resin is selected from the group consisting of vinyl-containing polyphenylene ether resins, maleimide resins, polyolefin resins, maleimide resin prepolymers, and combinations thereof. The resin composition disclosed herein can be formed into prepregs, resin films, laminates, or printed circuit boards, and exhibits improvements in at least one of flame retardancy, outgassing test performance, arc resistance, copper foil tensile strength, X-axis thermal expansion coefficient, glass transition temperature, and water absorption.

Description

Technical Field

[0001] The present invention relates to a resin composition, in particular to a resin composition which can be used to prepare a prepreg, a resin film, a laminate or a printed circuit board. Background Art

[0002] In recent years, with the development of electronic signal transmission methods towards 5G, and the high functionality and miniaturization of electronic equipment, communication devices, personal computers, etc., the circuit boards used are also developing towards multi-layering, high-density wiring, and high-speed signal transmission, which puts higher requirements on the comprehensive performance of circuit substrates such as copper foil substrates.

[0003] Traditional phosphorus-containing flame retardants are widely used in FR-4 copper-clad laminates, but they suffer from issues such as a low glass transition temperature and high water absorption. Furthermore, achieving V-0 flame retardancy typically requires a high phosphorus flame retardant dosage, which can degrade adhesion. Therefore, the industry is actively pursuing the development of a halogen-free, phosphorus-containing flame-retardant resin composition that exhibits good flame retardancy at relatively low phosphorus dosages, while also producing products with high glass transition temperatures and excellent adhesion. Furthermore, for substrate materials used in aerospace applications, it is also important to consider whether the substrate material meets properties such as low outgassing and arc resistance. Summary of the Invention

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

[0005] In order to achieve the above object, the present invention discloses a resin composition comprising 20 to 45 parts by weight of phosphorus-containing bismaleimide (DOPO-BMI) and 100 parts by weight of a thermosetting resin, wherein:

[0006] The phosphorus-containing bismaleimide has a structure shown in formula (I):

[0007]

[0008] wherein R1 is a hydrogen atom, a methyl group, or an ethyl group; R2 is a hydrogen atom or a methyl group; R3 is a hydrogen atom or a C1-C6 alkyl group; R4 is a hydrogen atom or a C1-C6 alkyl group; R5 is a hydrogen atom or a C1-C6 alkyl group; and R6 is a hydrogen atom or a C1-C6 alkyl group; and

[0009] The thermosetting resin is selected from the group consisting of vinyl polyphenylene ether resin, maleimide resin, polyolefin resin, maleimide resin prepolymer and combinations thereof.

[0010] For example, in one embodiment, the vinyl-containing polyphenylene ether resin includes vinyl-containing benzyl biphenyl polyphenylene ether resin, methacrylate-containing polyphenylene ether resin, vinyl-containing benzyl bisphenol A polyphenylene ether resin, vinyl-chain-extended polyphenylene ether resin, or a combination thereof.

[0011] For example, in one embodiment, the maleimide resin includes bisphenol A diphenyl ether bismaleimide resin, bis(3-ethyl-5-methyl-4-maleimidophenyl)methane, a maleimide resin having a structure represented by formula (IV) (as described later), 4,4'-diphenylmethane bismaleimide resin, or a combination thereof.

[0012] For example, in one embodiment, the polyolefin resin includes styrene-butadiene copolymer, polybutadiene resin, or a combination thereof.

[0013] For example, in one embodiment, the maleimide resin prepolymer includes a prepolymer of a diallyl compound (such as but not limited to diallyl bisphenol A) and a maleimide resin, a prepolymer of a diamine and a maleimide resin, a prepolymer of a polyfunctional amine and a maleimide resin, a prepolymer of an acidic phenol compound and a maleimide resin, or a combination thereof.

[0014] For example, in one embodiment, the resin composition further includes an inorganic filler, a flame retardant, a hardening accelerator, a polymerization inhibitor, a solvent, a silane coupling agent, a colorant, a toughening agent, or a combination thereof.

[0015] In order to achieve the above object, the present invention further discloses a product made from the above resin composition, wherein the product includes a prepreg, a resin film, a laminate or a printed circuit board.

[0016] For example, in one embodiment, the aforementioned article has one, more or all of the following characteristics:

[0017] The volatile condensable materials (CVCM) measured by outgassing testing (measured according to the method described in IPC-TM-650 2.6.4B) is less than or equal to 0.019%, and the total mass loss (TML) is less than or equal to 0.67%;

[0018] Arc resistance greater than or equal to 105 seconds as measured by the method described in IPC-TM-650 2.5.1B;

[0019] The copper foil tensile force measured according to the method described in IPC-TM-650 2.4.8 is greater than or equal to 4.05 lb / in;

[0020] The X-axis thermal expansion coefficient measured according to the method described in IPC-TM-650 2.4.24.5 is less than or equal to 13.2 ppm / °C;

[0021] The flame retardancy measured according to the method described in UL94 standard reaches V-0 grade;

[0022] A glass transition temperature greater than or equal to 201°C as measured by the method described in IPC-TM-650 2.4.24.5; and

[0023] The water absorption measured according to the method described in IPC-TM-650 2.6.2.1a is less than or equal to 0.39%. DETAILED DESCRIPTION

[0024] To facilitate understanding of the features and benefits of the present invention by those skilled in the art, the following provides a general description and definition of terms and expressions used in the specification and claims. Unless otherwise indicated, all technical and scientific terms used herein have the ordinary meanings as understood by those skilled in the art regarding the present invention. In the event of conflict, the definitions in this specification shall prevail.

[0025] As used herein, the terms "comprise," "include," "have," "contain," or any similar terms are open-ended transitional phrases that are intended to encompass non-exclusive inclusions. For example, a composition or article containing multiple elements is not limited to those elements listed herein, but may also include other elements not expressly listed but generally inherent to the composition or article. In addition, unless expressly stated to the contrary, the term "or" refers to an inclusive "or" rather than an exclusive "or." For example, any of the following situations satisfies the condition "A or B": 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), and both A and B are true (or exist). Furthermore, as used herein, the terms "comprise," "include," "have," and "contain" should be interpreted as specifically disclosing and encompassing transitional phrases such as "consisting of" and "consisting essentially of."

[0026] Herein, all features or conditions defined in the form of numerical ranges or percentage ranges are intended for simplicity and convenience only. Accordingly, descriptions of numerical ranges or percentage ranges should be considered to have encompassed and specifically disclosed all possible subranges and individual values ​​within the range, particularly integer values. For example, a range description of "1 to 8" should be considered to have specifically disclosed 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 to have specifically disclosed individual values ​​within the range such as 1, 2, 3, 4, 5, 6, 7, 8. Similarly, a range description of "between 1 and 8" should be considered to have specifically disclosed 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., and include the endpoints. Unless otherwise indicated, the above interpretation method applies to all contents of the present invention, regardless of whether the range is extensive or not.

[0027] If a quantity or other value or parameter is expressed as a range, a preferred range, or a series of upper and lower limits, it should be understood that all ranges consisting of any upper limit or preferred value of the range and any lower limit or preferred value of the range have been specifically disclosed herein, regardless of whether these ranges are disclosed separately. In addition, when a numerical range is mentioned herein, unless otherwise specified, the range is intended to include its endpoints and all integers and fractions within the range.

[0028] In this document, numerical values ​​should be understood to have the accuracy of the number of significant digits to which the invention is intended to be applied, for example, the number 40.0 should be understood to encompass a range from 39.50 to 40.49.

[0029] In this document, where Markush groups or optional terms are used to describe features or embodiments of the present invention, those skilled in the art will appreciate that any combination of subgroups or individual members of the Markush group or optional list can also be used to describe the present invention. For example, if X is described as "selected from the group consisting of X1, X2, and X3," this fully describes the claim that X is X1 and the claim that X is X1 and / or X2 and / or X3. Furthermore, where Markush groups or optional terms are used to describe features or embodiments of the present invention, those skilled in the art will appreciate that any combination of subgroups or individual members of the Markush group or optional list can also be used to describe the present 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," this fully describes the claim that X is X1, X2, or X3, and Y is Y1, Y2, or Y3.

[0030] Unless otherwise specified, in this disclosure, a compound refers to a chemical substance formed by two or more elements connected by chemical bonds, including, but not limited to, small molecule compounds and polymer compounds. The term "compound" as used herein is not limited to a single chemical substance but also encompasses chemical substances of the same type with the same composition or properties. Furthermore, in this disclosure, a mixture refers to a combination of two or more compounds.

[0031] In this article, prepolymer refers to a product that still contains reactive functional groups or has polymerization potential after a compound or mixture (monomer) undergoes prepolymerization (partial polymerization) reaction. For example, the molecular weight or viscosity can be used to assist in confirming whether the reaction degree of the prepolymerization reaction meets the requirements. The prepolymerization method used in this article, for example, but not limited to, using solvent heating to initiate the prepolymerization reaction, or using hot melt reaction to initiate the prepolymerization reaction. For example, solvent heating prepolymerization is to add raw materials to a solvent to dissolve, and optionally add a catalyst or inhibitor, and then heat the reaction until all raw materials are dissolved in the solvent, thereby initiating the prepolymerization reaction. Hot melt reaction prepolymerization is to directly heat and melt the raw materials to initiate the prepolymerization reaction. The prepolymerized product (prepolymer) has a larger molecular weight than the compound monomer or mixture monomer that has not been prepolymerized, and can be analyzed by gel permeation chromatography (GPC). The graph of the residence time (X-axis) and molecular weight (Y-axis) distribution results shows that the molecular weight distribution peak of the prepolymer is located at the front end (shorter residence time), while the molecular weight distribution peak of the monomer is located at the back end (longer residence time). Furthermore, the resulting prepolymer has a broader molecular weight distribution peak with multiple consecutive peaks, while the monomer has a narrower molecular weight distribution peak with only a single peak.

[0032] To those skilled in the art, a resin composition containing three compounds A, B, and C and an additive (comprising four components in total) and a resin composition containing a prepolymer formed by the three compounds A, B, and C and an additive (comprising two components in total) are different resin compositions, and the two are completely different in many aspects, such as the preparation method, the physical and chemical properties of the compounds themselves, and the properties of their products. For example, the former is formed by mixing A, B, C, and the additive to form a resin composition, while the latter requires first prepolymerizing the mixture including A, B, and C under appropriate conditions to form a prepolymer, and then mixing the prepolymer with the additive to produce the resin composition. For example, to those skilled in the art, the two resin compositions have completely different compositions, and because the function of the prepolymer formed by the three compounds A, B, and C in the resin composition is completely different from the function of A, B, and C individually or collectively in the resin composition, the two resin compositions should be considered to be completely different chemical substances with completely different chemical positions. For example, to those skilled in the art, because the two resin compositions are completely different chemical substances, their products will not have the same properties. For example, in a resin composition comprising a prepolymer formed by three compounds A, B, and C and a crosslinking agent, since A, B, and C have partially reacted or converted to form the prepolymer during the prepolymerization reaction, when the resin composition is subsequently heated at a high temperature to form a semi-cured state, a partial crosslinking reaction occurs between the prepolymer and the crosslinking agent, rather than a partial crosslinking reaction between A, B, and C and the crosslinking agent individually. Therefore, the products formed from the two resin compositions will be completely different and have completely different properties.

[0033] Unless otherwise specified, in the present invention, modified products (also referred to as modified products) include products obtained by modifying the reactive functional groups of each resin, products obtained by cross-linking each resin with another resin, products obtained by homopolymerization of each resin, products obtained by copolymerization of each resin with another resin, etc. For example, but not limited to, modification may involve chemically replacing the original hydroxyl group with a vinyl group, or chemically reacting the original terminal vinyl group with p-aminophenol to obtain a terminal hydroxyl group.

[0034] As used herein, "vinyl-containing" refers to compounds containing an ethylenic carbon-carbon double bond (C=C) or a functional group derived therefrom. Examples of vinyl-containing compounds include, but are not limited to, compounds containing functional groups such as vinyl, allyl, vinylbenzyl, and methacrylate groups. Unless otherwise specified, the location of these functional groups is not particularly limited and may, for example, be located at the end of a long chain structure. Thus, for example, a vinyl-containing polyphenylene ether resin refers to a polyphenylene ether resin containing functional groups such as vinyl, allyl, vinylbenzyl, and methacrylate groups, but is not limited thereto.

[0035] As used herein, parts by weight refers to parts by weight and can be any unit of weight, such as, but not limited to, grams, kilograms, or pounds. For example, 100 parts by weight of a prepolymer can refer to 100 grams, 100 kilograms, or 100 pounds of prepolymer, without limitation.

[0036] The following detailed description is merely illustrative in nature and is not intended to limit the present invention and its uses. In addition, this document is not bound by any theory described in the foregoing prior art or summary of the invention or in the following detailed description or examples.

[0037] As mentioned above, the main object of the present invention is to provide a resin composition comprising 20 to 45 parts by weight of phosphorus-containing bismaleimide and 100 parts by weight of a thermosetting resin, wherein:

[0038] The phosphorus-containing bismaleimide has a structure shown in formula (I):

[0039]

[0040] Wherein, R1 is a hydrogen atom, a methyl group or an ethyl group;

[0041] R2 is a hydrogen atom or a methyl group;

[0042] R3 is a hydrogen atom or a C1-C6 alkyl group (e.g., C1, C2, C3, C4, C5 or C6 alkyl group);

[0043] R4 is a hydrogen atom or a C1-C6 alkyl group (e.g., C1, C2, C3, C4, C5 or C6 alkyl group);

[0044] R5 is a hydrogen atom or a C1-C6 alkyl group (e.g., C1, C2, C3, C4, C5 or C6 alkyl group);

[0045] R6 is a hydrogen atom or a C1-C6 alkyl group (e.g., C1, C2, C3, C4, C5 or C6 alkyl group); and

[0046] The thermosetting resin is selected from the group consisting of vinyl polyphenylene ether resin, maleimide resin, polyolefin resin, maleimide resin prepolymer and combinations thereof.

[0047] For example, in one embodiment, the phosphorus-containing bismaleimide may be a structure represented by formula (II):

[0048]

[0049] For example, in one embodiment, the aforementioned vinyl-containing polyphenylene ether resin may include various types of vinyl-containing polyphenylene ether resins known in the art. The vinyl-containing polyphenylene ether resins suitable for the present invention are not particularly limited and may be any one or more commercially available products, homemade products, or a combination thereof. Examples thereof may include, but are not limited to, polyphenylene ether resins containing vinyl, allyl, vinylbenzyl, or methacrylate. For example, in one embodiment, the aforementioned vinyl-containing polyphenylene ether resin includes vinylbenzyl biphenyl polyphenylene ether resin, methacrylate-containing polyphenylene ether resin (i.e., methacryloyl-containing polyphenylene ether resin), allyl polyphenylene ether resin, vinylbenzyl bisphenol A polyphenylene ether resin, vinyl chain-extended polyphenylene ether resin, or a combination thereof. For example, the vinyl-containing polyphenylene ether resin may be a vinyl benzyl biphenyl polyphenylene ether resin having a number average molecular weight of approximately 1200 (e.g., OPE-2st 1200, available from Mitsubishi Gas Chemical Co., Ltd.), a vinyl benzyl biphenyl polyphenylene ether resin having a number average molecular weight of approximately 2200 (e.g., OPE-2st 2200, available from Mitsubishi Gas Chemical Co., Ltd.), a methacrylate-containing polyphenylene ether resin having a number average molecular weight of approximately 1900 to 2300 (e.g., SA9000, available from Sabic Corporation), a vinyl benzyl bisphenol A-containing polyphenylene ether resin having a number average molecular weight of approximately 2400 to 2800, a vinyl chain-extended polyphenylene ether resin having a number average molecular weight of approximately 2200 to 3000, or a combination thereof. The vinyl chain-extended polyphenylene ether resin may include various polyphenylene ether resins disclosed in U.S. Patent Application Publication No. 2016 / 0185904 A1, which is incorporated herein by reference in its entirety.

[0050] For example, in one embodiment, the maleimide resin comprises monomers or combinations thereof having one or more maleimide functional groups in the molecule. Unless otherwise specified, the maleimide resin employed in the present invention is not particularly limited and may be any one or more maleimide resins suitable for use in the production of prepregs (also known as prepregs), resin films, laminates, or printed circuit boards.In certain embodiments, any one or more of the following maleimide resins may be used: 4,4'-diphenylmethane bismaleimide resin, oligomer of phenylmethane maleimide (or polyphenylmethane maleimide), bisphenol A diphenyl ether bismaleimide resin, 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, 4-methyl-1,3-phenylene bismaleimide bismaleimide), 1,6-bismaleimide-(2,2,4-trimethyl)hexane, 2,3-dimethylphenylmaleimide (N-2,3-xylylmaleimide), 2,6-dimethylphenylmaleimide (N-2,6-xylylmaleimide), N-phenylmaleimide, diethylbismaleimidotoluene, vinyl benzyl 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.

[0051] For example, in one embodiment, the maleimide resin has a structure shown in formula (IV):

[0052] Where 1≤n≤5.

[0053] For example, the maleimide resin may be a maleimide resin produced by Daiwakasei Industry Co., Ltd. under the trade names of 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 a maleimide resin produced by KI Chemical Co., Ltd. under the trade names of BMI-70 and BMI-80, or a maleimide resin produced by Nippon Kayaku Co., Ltd. under the trade names of MIR-3000 and MIR-5000, or a maleimide resin produced by Evonik Chemical Co., Ltd. under the trade name of DE-TDAB.

[0054] For example, the maleimide resin containing an aliphatic long chain structure may be a maleimide resin produced by a designer molecular company under the trade names of BMI-689, BMI-1400, BMI-1500, BMI-1700, BMI-2500, BMI-3000, BMI-5000, and BMI-6000.

[0055] For example, in one embodiment, the polyolefin resin of the present invention may include, but is 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-butylene-styrene block polymer), styrene-isoprene copolymer, hydrogenated styrene-isoprene copolymer, hydrogenated styrene-butadiene-divinylbenzene terpolymer, polybutadiene (i.e., butadiene homopolymer), maleic anhydride-butadiene copolymer, methyl styrene copolymer, or a combination thereof. Preferably, the polyolefin resin may include styrene-butadiene copolymer, hydrogenated styrene-butadiene copolymer, polybutadiene, styrene-butadiene-maleic anhydride terpolymer, maleic anhydride-butadiene copolymer, or a combination thereof. For example, the polybutadiene may include polybutadiene without reactive functional groups, hydrogenated polybutadiene, polybutadiene containing hydroxyl groups, polybutadiene containing phenolic hydroxyl groups (having a polybutadiene structure and phenolic hydroxyl groups), polybutadiene containing carboxyl groups, polybutadiene containing acid anhydride groups, polybutadiene containing epoxy groups, polybutadiene containing isocyanate groups, polybutadiene containing urethane groups, hydrogenated polybutadiene with terminal hydroxyl groups vinylized (no longer containing hydroxyl groups), or combinations thereof. For example, the polybutadiene may include polybutadiene containing epoxy groups.

[0056] For example, in one embodiment, the maleimide resin prepolymer described in the present invention may include, but is not limited to, a prepolymer of a diallyl compound (such as, but not limited to, diallyl bisphenol A) and a maleimide resin, a prepolymer of a diamine and a maleimide resin, a prepolymer of a polyfunctional amine and a maleimide resin, a prepolymer of an acidic phenol compound and a maleimide resin, or a combination thereof. For example, the acidic phenol compound may be p-aminophenol. For example, the maleimide resin prepolymer may be a maleimide resin prepolymer manufactured by HOS-Technik under the trade name Homide 801, for example.

[0057] In addition to the aforementioned components, the resin composition of the present invention may further include an inorganic filler, a flame retardant, a hardening accelerator, a polymerization inhibitor, a solvent, a silane coupling agent, a colorant, a toughening agent, or a combination thereof as needed.

[0058] For example, the inorganic filler can be any one or more inorganic fillers suitable for use in the production of prepregs, resin films, laminates, or printed circuit boards. Specific examples include, but are not limited to, silicon dioxide (molten, non-molten, porous, or hollow), aluminum oxide, aluminum hydroxide, magnesium oxide, magnesium hydroxide, calcium carbonate, aluminum nitride, boron nitride, aluminum silicon 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, petalite, calcined kaolin, or combinations thereof. Furthermore, the inorganic filler can be spherical, fibrous, plate-like, granular, flaky, or needle-like, and can optionally be pretreated with a silane coupling agent.

[0059] For example, the flame retardant may be any one or more flame retardants suitable for use in the production of 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), tris(chloroisopropyl)phosphate, trimethyl phosphate (TMP), dimethyl methyl phosphonate (DMMP), resorcinol bis(dixylenyl phosphate), tris ...2-carboxyethyl)phosphine (TCEP), tris(2-carboxyethyl)phosphine (TCEP), tris(2-carboxyethyl)phosphine (TCEP), tris(2-carboxyethyl)phosphine (TCEP), tris(2-carboxyethyl)phosphine (TCEP), tris(2-carboxyethyl)phosphine (TCEP), tris(2-carboxyethyl)phosphine (TCEP), tri phosphate), RDXP, such as commercial products such as PX-200, PX-201, and PX-202, phosphazene compounds (such as commercial products such as SPB-100, SPH-100, and SPV-100), melamine polyphosphate, DOPO (9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide) and its derivatives or resins, DPPO (diphenylphosphine oxide) and its derivatives or resins, melamine cyanurate, tri-hydroxy ethyl isocyanurate, aluminum phosphinate (such as products such as OP-930 and OP-935), or combinations thereof.

[0060] For example, the flame retardant may be a DPPO compound (e.g., a bis-DPPO compound, such as commercially available products such as PQ-60), a DOPO compound (e.g., a bis-DOPO compound), a DOPO resin (e.g., DOPO-HQ, DOPO-NQ, DOPO-PN, DOPO-BPN), or a DOPO-bonded epoxy resin. DOPO-PN is a DOPO phenol novolac compound, and DOPO-BPN may be a bisphenol novolac compound such as DOPO-BPAN (DOPO-bisphenol A novolac), DOPO-BPFN (DOPO-bisphenol F novolac), or DOPO-BPSN (DOPO-bisphenol S novolac).

[0061] For example, the hardening accelerator (including the hardening initiator) may include a catalyst such as a Lewis base or a Lewis acid. The Lewis base may include one or more of imidazole, boron trifluoride amine complex, ethyltriphenylphosphonium chloride, 2-methylimidazole (2MI), 2-phenyl-1H-imidazole (2PZ), 2-ethyl-4-methylimidazole (2E4MI), triphenylphosphine (TPP), and 4-dimethylaminopyridine (DMAP). The Lewis acid may include a metal salt compound, such as a metal salt compound of manganese, iron, cobalt, nickel, copper, or zinc, or a metal catalyst such as zinc octoate or cobalt octoate. The hardening accelerator also includes a hardening initiator, such as a peroxide that can generate free radicals. The hardening initiator includes but is not limited to: diisopropyl benzene peroxide, tert-butyl perbenzoate, dibenzoyl peroxide (BPO), 2,5-dimethyl-2,5-di(tert-butylperoxy)-3-hexyne (25B) and bis(tert-butylperoxyisopropyl)benzene or a combination thereof.

[0062] For example, the polymerization inhibitor may include, but is not limited to, 1,1-diphenyl-2-trinitrophenylhydrazine, methacrylonitrile, 2,2,6,6-tetramethyl-1-oxy-piperidine, dithioesters, nitroxide-stabilized free radicals, triphenylmethyl free radicals, metal ion free radicals, sulfhydryl free radicals, hydroquinone, p-methoxyphenol, p-benzoquinone, phenothiazine, 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 nitroxide-stabilized free radical may include, but is not limited to, nitroxide free radicals derived from cyclic hydroxylamines, such as 2,2,6,6-substituted-1-piperidinyloxy free radicals or 2,2,5,5-substituted-1-pyrrolidinyloxy free radicals. The substituent is preferably an alkyl group with four or fewer carbon atoms, such as a methyl or ethyl group. Specific nitrogen oxide free radical compounds are not limited, and examples include but are not limited to 2,2,6,6-tetramethyl-1-piperidinyloxy free radical, 2,2,6,6-tetraethyl-1-piperidinyloxy free radical, 2,2,6,6-tetramethyl-4-oxo-1-piperidinyloxy free radical, 2,2,5,5-tetramethyl-1-pyrrolidinyloxy free radical, 1,1,3,3-tetramethyl-2-isoindolinyloxy free radical, N,N-di-tert-butylamineoxy free radical, etc. Stable free radicals such as galvinoxyl free radical can also be used to replace the nitrogen oxide free radical. The polymerization inhibitor suitable for the resin composition of the present invention can also be a product derived from the hydrogen atom or atomic group in the polymerization inhibitor being replaced by other atoms or atomic groups. For example, the hydrogen atom in the polymerization inhibitor is replaced by an atomic group such as an amino group, a hydroxyl group, or a ketocarbonyl group.

[0063] 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 the like solvents or mixed solvents thereof.

[0064] For example, the silane coupling agent may include a silane compound (such as, but not limited to, a siloxane compound), which can be further classified into aminosilane compounds, epoxide silane compounds, vinylsilane compounds, acrylate silane compounds, methacrylate silane compounds, hydroxy silane compounds, isocyanate silane compounds, methacryloxy silane compounds, and acryloxy silane compounds based on the type of functional group.

[0065] For example, the coloring agent may include but is not limited to dye or pigment.

[0066] In the present invention, the addition of a toughening agent primarily improves the toughness of the resin composition. For example, such toughening agents may include, but are not limited to, carboxyl-terminated butadiene acrylonitrile rubber (CTBN), core-shell rubber, and other compounds, or combinations thereof.

[0067] The resin compositions of the aforementioned embodiments can be made into various products, such as components suitable for use in various electronic products, including but not limited to prepregs, resin films, laminates, or printed circuit boards.

[0068] For example, the resin composition of each embodiment of the present invention can be made into a semi-cured sheet, which includes a reinforcing material and a layered material disposed on the reinforcing material. The layered material 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 semi-cured sheet is between 120°C and 180°C, preferably between 120°C and 160°C. The reinforcing material can be any one of a fiber material, a woven fabric, and a non-woven fabric, and the woven fabric preferably includes a glass fiber cloth. The type of glass fiber cloth is not particularly limited, and can be various commercially available glass fiber cloths that can be used for printed circuit boards, such as E-type glass cloth, D-type glass cloth, S-type glass cloth, T-type glass cloth, L-type glass cloth or Q-type glass cloth, wherein the types of fibers include yarns and rovings, and the forms can include open fibers or unopen fibers. The aforementioned non-woven fabric preferably includes a liquid crystal resin non-woven fabric, such as a polyester non-woven fabric, a polyurethane non-woven fabric, etc., and is not limited thereto. The aforementioned woven fabric can also include a liquid crystal resin woven fabric, such as a polyester woven fabric or a polyurethane woven fabric, etc., and is not limited thereto. This reinforcing material can increase the mechanical strength of the prepreg. In a preferred embodiment, the reinforcing material can also be optionally pre-treated with a silane coupling agent. The prepreg is subsequently heated and cured (C-stage) to form an insulating layer.

[0069] For example, the resin compositions of various embodiments of the present invention can be formed into a resin film by semi-curing the resin composition through baking and heating. The resin composition can be selectively coated onto a polyethylene terephthalate film (PET film), a polyimide film (PI film), a copper foil, or a self-adhesive copper foil, and then semi-cured through baking and heating to form a resin film.

[0070] For example, the resin composition of each embodiment 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 resin composition under high temperature and high pressure conditions (C-stage), wherein a suitable curing temperature can be between 180°C and 240°C, preferably between 200°C and 230°C, and a curing time can be between 90 and 180 minutes, preferably between 120 and 150 minutes. The insulating layer can be formed by curing the prepreg or resin film (C-stage). The metal foil can include copper, aluminum, nickel, platinum, silver, gold, or alloys thereof. For example, the metal foil can be copper foil. In one embodiment, the laminate is a copper clad laminate (CCL).

[0071] In addition, the aforementioned laminate can be further processed through a circuit manufacturing process to form a circuit board, such as a printed circuit board.

[0072] In one embodiment, the resin composition provided by the present invention can improve at least one of the following properties: flame retardancy, outgassing test, arc resistance, copper foil tensile strength, X-axis thermal expansion coefficient, glass transition temperature, and water absorption.

[0073] For example, the resin composition provided by the present invention or the product made therefrom may satisfy one, more or all of the following characteristics:

[0074] The volatile condensate is less than or equal to 0.019% and the total mass loss is less than or equal to 0.67% as measured by the outgassing test method described in IPC-TM-650 2.6.4B, e.g., the volatile condensate is between 0.010% and 0.019%, e.g., the total mass loss is between 0.41% and 0.67%;

[0075] An arc resistance of greater than or equal to 105 seconds, e.g., between 105 seconds and 136 seconds, as measured by the method described in IPC-TM-650 2.5.1B;

[0076] The copper foil tensile force measured according to the method described in IPC-TM-650 2.4.8 is greater than or equal to 4.05 lb / in, such as between 4.05 lb / in and 5.80 lb / in;

[0077] The X-axis thermal expansion coefficient measured according to the method described in IPC-TM-650 2.4.24.5 is less than or equal to 13.2 ppm / °C, for example, between 10.6 ppm / °C and 13.2 ppm / °C;

[0078] The flame retardancy measured according to the method described in the UL94 specification reaches a V-0 rating (in one embodiment, when the phosphorus content of the resin composition is between 0.75% and 2.00%);

[0079] A glass transition temperature greater than or equal to 201°C, such as between 201°C and 288°C, as measured according to the method described in IPC-TM-650 2.4.24.5; and

[0080] The water absorption measured according to the method described in IPC-TM-650 2.6.2.1a is less than or equal to 0.39%, for example, between 0.18% and 0.39%.

[0081] The resin compositions of the examples and comparative examples of the present invention were prepared using the following raw materials in the amounts shown in Tables 1 to 6, and were further prepared into various test samples.

[0082] The chemical raw materials used in the examples and comparative examples of the present invention are as follows:

[0083] SA9000: polyphenylene ether resin containing methacrylate, purchased from Sabic.

[0084] OPE-2st 1200: vinylbenzyl biphenyl polyphenylene ether resin, purchased from Mitsubishi Gas Chemical.

[0085] BMI-70: bis(3-ethyl-5-methyl-4-maleimidophenyl)methane, purchased from KI Chemicals.

[0086] MIR-5000: maleimide resin with the structure shown in formula (IV), purchased from Nippon Kayaku Co., Ltd.

[0087] Where 1≤n≤5.

[0088] BMI-80: bisphenol A diphenyl ether bismaleimide resin, purchased from KI Chemicals.

[0089] Ricon 100: styrene-butadiene copolymer, available from Cray Valley.

[0090] B-1000: polybutadiene resin, purchased from Japan Soda.

[0091] Homide 801: a prepolymer of 4,4'-diphenylmethanebismaleimide and diallyl bisphenol A in a ratio of 40:60, purchased from HOS-Technik.

[0092] TM-124: diallyl bisphenol A, available from Evonik.

[0093] Phosphorus-containing bismaleimide of the structure shown in formula (II): purchased from Liuhe Chemical, with a phosphorus content of 4.5%.

[0094] The compound represented by the structure of formula (III) was synthesized by itself as described in the synthesis example, with a phosphorus content of 6%.

[0095]

[0096] Di-DOPO: a compound having a structure shown in formula (V), synthesized independently with reference to Chinese patent CN105936745B, with a phosphorus content of 12%.

[0097]

[0098] Di-DPPO: a compound having a structure shown in formula (VI), synthesized independently with reference to Chinese patent CN105440645B, with a phosphorus content of 12%.

[0099]

[0100] SPV-100: allylphosphazene, purchased from Otsuka Chemical, phosphorus content 13%.

[0101] PX-200: resorcinol bis[di(2,6-dimethylphenyl) phosphate], purchased from Daba Chemical, phosphorus content 9%.

[0102] OP-945: aluminum diethylphosphinate, available from Clariant, phosphorus content 23%.

[0103] MC-4: (methacryloyloxymethyl)diphenylphosphine oxide, purchased from Katayama Chemical, phosphorus content 8%.

[0104] MP-200 (Melapur 200): melamine polyphosphate, purchased from BASF, phosphorus content 13%. SC-001: a compound having the structure represented by formula (VII), purchased from Osaka Gas Chemical.

[0105]

[0106] 25B: 2,5-dimethyl-2,5-di(tert-butylperoxy)-3-hexyne, purchased from NOF Corporation.

[0107] SiO2: spherical silica with surface treated with a silane coupling agent, trade name SC2500 SXJ, purchased from Admatechs.

[0108] WZr: zirconium tungstate (Zr(WO4)2), purchased from Shenghe Resources.

[0109] LAS: petalite, purchased from Liuhe Chemical.

[0110] MEK: butanone, commercially available.

[0111] PMA: propylene glycol methyl ether acetate, commercially available.

[0112] Toluene: commercially available.

[0113] Mixed solvent: a mixed solvent of butanone (MEK), propylene glycol methyl ether acetate (PMA) and toluene, wherein the weight ratio of MEK, PMA and toluene is 3:1:1, which can be prepared by yourself.

[0114] Synthesis Example: Preparation of a compound represented by formula (III)

[0115] 15 parts by weight of DOPO (purchased from Hexin Chemical) and 65 parts by weight of BMI-H (purchased from Dongxin Chemical) were placed in a container. 65 parts by weight of DMF solution was then added to the container. Continuous heating was started under N2 conditions. The heating process was divided into the following three stages:

[0116] 1. Continuously heat from room temperature to 70°C to 80°C over 50 minutes, and slowly add 20 parts by weight of toluene solution dropwise to the container during this period;

[0117] 2. Continuously heating from 70°C to 80°C to 100°C to 110°C within 45 minutes; and

[0118] 3. Keep warm at 100℃ to 110℃ for 45 minutes.

[0119] The mixture is then cooled to room temperature naturally, and placed in an electric constant temperature forced air drying oven to evaporate the solvent to dryness, thereby obtaining a compound with the structure represented by formula (III) as a solid.

[0120] The compositions of the resin compositions of the Examples and Comparative Examples (all in parts by weight) and the test results of their properties are shown in the following table:

[0121] [Table 1] Composition of the resin composition of the embodiment (unit: weight parts) and characteristic test results

[0122]

[0123] [Table 2] Composition of the resin composition of the embodiment (unit: weight parts) and characteristic test results

[0124]

[0125]

[0126] [Table 3] Composition of the resin composition of the embodiment (unit: weight parts) and characteristic test results

[0127]

[0128]

[0129] [Table 4] Composition of comparative resin composition (unit: parts by weight) and property test results

[0130]

[0131]

[0132] [Table 5] Composition of comparative resin composition (unit: parts by weight) and property test results

[0133]

[0134]

[0135] [Table 6] Composition of comparative resin composition (unit: parts by weight) and property test results

[0136]

[0137]

[0138] The aforementioned characteristics are prepared by referring to the following method to prepare the object to be tested (sample), and then the characteristics are analyzed according to specific conditions.

[0139] 1. Prepreg: The resin compositions of Examples E1-E15 and Comparative Examples C1-C15 (units are parts by weight) were selected and added to a stirring tank. The components were mixed thoroughly to form a varnish. The varnish was placed in an impregnation tank. Glass fiber cloth (e.g., 2116 E-glass fiber fabric, available from Asahi) was then immersed in the impregnation tank to adhere the resin composition to the cloth. The varnish was then heated and baked at 140-160°C for approximately 3 minutes to produce a prepreg. The prepreg produced using the 2116 E-glass fiber cloth had a resin content of approximately 55%.

[0140] 2. Copper-containing substrate 1 (a copper-containing substrate can also be called a copper foil substrate, and is formed by laminating two prepregs): Prepare two 35-micron thick reverse treatment foils (RTF) and two 2116 gauge E-glass fiber cloths impregnated with the prepregs made from each sample to be tested (each set of examples or each set of comparative examples). The resin content of each prepreg is approximately 55%. The copper foil, two prepregs, and copper foil are laminated in this order and placed under vacuum at a pressure of 46 kgf / cm. 2 , and pressing at 230° C. for 120 minutes to form a copper-containing substrate 1. The two superimposed prepregs are cured to form an insulating layer between the two copper foils, and the resin content of the insulating layer is about 55%.

[0141] 3. Copper-containing substrate 2 (composed of eight prepregs laminated together): Prepare two 35-micron thick reverse treatment foils (RTF) and eight 2116 gauge E-glass fiber cloths impregnated with prepregs made from each sample to be tested (each set of examples or each set of comparative examples). The resin content of each prepreg is approximately 55%. The copper foil, eight prepregs, and copper foil are laminated in this order. The laminate is then placed under vacuum at a pressure of 46 kgf / cm. 2 , and pressing at 230° C. for 120 minutes to form a copper-containing substrate 2. The eight overlapping prepregs are cured to form an insulating layer between the two copper foils, and the resin content of the insulating layer is about 55%.

[0142] 4. Copper-containing substrate 3 (made from 16 prepreg sheets laminated together): Prepare two 35-micron thick reverse treatment foils (RTF) and 16 2116 gauge E-glass fiber cloths impregnated with prepreg sheets made from each sample to be tested (each set of examples or each set of comparative examples). The resin content of each prepreg sheet is approximately 55%. The copper foil, the 16 prepreg sheets, and the copper foil are laminated in this order. The laminate is then placed under vacuum at a pressure of 46 kgf / cm. 2 , and pressing at 230° C. for 120 minutes to form a copper-containing substrate 3. The sixteen overlapping prepregs are cured to form an insulating layer between the two copper foils, and the resin content of the insulating layer is about 55%.

[0143] 5. Copper-containing substrate 4 (composed of 32 prepreg sheets laminated together): Prepare two 35-micron thick reverse treatment foils (RTF) and 32 2116 gauge E-glass fiber cloths impregnated with prepreg sheets made from each sample to be tested (each set of Examples or each set of Comparative Examples). The resin content of each prepreg sheet is approximately 55%. The copper foil, 32 prepreg sheets, and copper foil are laminated in this order. The laminate is then placed under vacuum at a pressure of 46 kgf / cm. 2 , and pressing at 230° C. for 120 minutes to form a copper-containing substrate 4. The 32 overlapping prepregs are cured to form an insulating layer between the two copper foils, and the resin content of the insulating layer is about 55%.

[0144] 6. Copper-free substrate 1 (formed by pressing two prepregs together): The copper-containing substrate 1 (formed by pressing two prepregs together) was etched to remove the copper foil on both sides to obtain a copper-free substrate 1 (formed by pressing two prepregs together). The resin content of the copper-free substrate 1 was approximately 55%.

[0145] 7. Copper-free substrate 2 (formed by pressing eight prepregs): The copper-containing substrate 2 (formed by pressing eight prepregs) was etched to remove the copper foil on both sides to obtain a copper-free substrate 2 (formed by pressing eight prepregs). The resin content of the copper-free substrate 2 was approximately 55%.

[0146] 8. Copper-free substrate 3 (formed by pressing sixteen prepregs): The copper-containing substrate 3 (formed by pressing sixteen prepregs) was etched to remove the copper foil on both sides to obtain a copper-free substrate 3 (formed by pressing sixteen prepregs). The resin content of the copper-free substrate 3 was approximately 55%.

[0147] 9. Copper-free substrate 4 (composed of 32 prepregs laminated together): The copper-containing substrate 4 (composed of 32 prepregs laminated together) is etched to remove the copper foil on both sides to obtain a copper-free substrate 4 (composed of 32 prepregs laminated together). The resin content of the copper-free substrate 4 is approximately 55%.

[0148] The descriptions of each test method and its characteristic analysis items are as follows:

[0149] Flame retardancy

[0150] In the flame retardancy test, a 125 mm x 13 mm copper-free substrate 3 (made from sixteen prepreg sheets laminated together, with a resin content of approximately 55%) was used as the test sample. Measurements were conducted according to the UL94 standard, and the flame retardancy analysis results were expressed as V-0, V-1, and V-2 grades, with V-0 indicating superior flame retardancy to V-1, V-1 superior to V-2, and complete burnout being the worst. For example, a product made from the resin composition disclosed herein received a V-0 flame retardancy rating when measured according to the UL94 standard.

[0151] Outgassing properties

[0152] For the outgassing test, samples were cut into small pieces (approximately 200 mg) of copper-free substrate 2 (made by laminating eight prepreg sheets, with a resin content of approximately 55%) as the test samples. The test was performed according to the method described in IPC-TM-650 2.6.4B. The test samples were preconditioned at 50% relative humidity and 23 ± 2°C for 24 hours and then weighed. After weighing, the test samples were placed in a test chamber set to 125°C and a vacuum of at least 5x10 -5 The test was conducted at 100 torr for 24 hours. During the time the sample was in the test chamber, volatiles released from the sample escaped through a port in the test chamber and condensed on a cooled collection plate (25±1°C). After 24 hours, the sample was cooled to room temperature, and the sample and volatile condensate were weighed to determine the total mass loss of the sample and the amount of volatile condensate collected on the collection plate.

[0153] In the art, lower total mass loss and volatile condensate are preferred. A difference in total mass loss greater than or equal to 0.10% and a difference in volatile condensate greater than or equal to 0.01% indicate significant differences in outgassing test results between different substrates (significant technical difficulty). For example, an article made from the resin composition disclosed herein, as measured in accordance with the method described in IPC-TM-650 2.6.4B, has a total mass loss of less than or equal to 0.67%, for example, between 0.41% and 0.67%, and a volatile condensate of less than or equal to 0.019%, for example, between 0.010% and 0.019%.

[0154] Arc resistance

[0155] In the arc resistance test, a 76mm x 50mm copper-free substrate 4 (made of 32 prepreg sheets laminated together, with a resin content of approximately 55%) was used as the test sample. The test was conducted according to the method described in IPC-TM-650 2.5.1B. The test sample was immersed in distilled water at 50±2°C for 48 hours, then immersed in distilled water at room temperature. After 1 hour, allow the sample to reach temperature equilibrium. Take out a piece of pre-treated sample from the room temperature distilled water, wipe it dry, and place it in the arc tester. Turn on the power to generate an arc. Observe the arc carefully. Stop the timer and record the moment the arc disappears and the sample shows signs of leakage. The unit is accurate to seconds.

[0156] In the art, a longer arc resistance is preferred. An arc resistance greater than or equal to 5 seconds indicates significant differences in arc resistance between different substrates (significant technical difficulty). For example, an article made from the resin composition disclosed herein may have an arc resistance greater than or equal to 105 seconds, for example, between 105 seconds and 136 seconds, as measured according to IPC-TM-650 2.5.1B.

[0157] Copper foil peeling strength (P / S)

[0158] In the copper foil tensile test, the copper-containing substrate 2 (composed of eight 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 then 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, measurements were performed at room temperature (approximately 25°C) according to the method described in IPC-TM-650 2.4.8. The force required to pull the copper foil away from the insulating surface of each test sample was measured (in lb / in).

[0159] In the art, a higher copper foil tensile strength is preferred. A copper foil tensile strength difference of 0.15 lb / in or greater indicates significant differences in copper foil tensile strength between different substrates (significant technical difficulty). For example, an article made from the resin composition disclosed herein may have a copper foil tensile strength greater than or equal to 4.05 lb / in, for example, between 4.05 lb / in and 5.80 lb / in, as measured according to IPC-TM-650 2.4.8.

[0160] X-axis coefficient of thermal expansion (X-CTE)

[0161] To measure the X-axis thermal expansion coefficient, the copper-free substrate 1 (composed of two prepreg sheets laminated together) was selected as the test sample for thermomechanical analysis (TMA). The copper-free substrate 1 was cut into samples with a length and width of 10 mm. The samples were heated at a rate of 10°C per minute from 35°C to 300°C. The X-axis thermal expansion coefficient (α1) of each test sample was measured over a temperature range of 40°C to 125°C (in ppm / °C) according to the method described in IPC-TM-650 2.4.24.5.

[0162] In the art, a lower X-axis CTE indicates better dimensional expansion and contraction characteristics. A difference in X-axis CTE greater than or equal to 0.5 ppm / °C indicates significant differences in X-axis CTE between different substrates (posing significant technical difficulties). For example, an article made from the resin composition disclosed herein has an X-axis CTE of less than or equal to 13.2 ppm / °C, for example, between 10.6 ppm / °C and 13.2 ppm / °C, as measured according to the method described in IPC-TM-650 2.4.24.5.

[0163] Glass transition temperature (Tg)

[0164] For the glass transition temperature test, a copper-free substrate 2 (composed of eight prepreg sheets laminated together) was selected as the sample for thermal mechanical analysis (TMA). The sample was heated at a rate of 10°C per minute from 35°C to 350°C. The glass transition temperature (Tg) of each sample was measured in °C according to the method described in IPC-TM-6502.4.24.5.

[0165] In this field, a higher glass transition temperature is preferred. A glass transition temperature difference of 5°C or greater indicates significant differences in glass transition temperature between different substrates (posing significant technical difficulties). For example, an article made from the resin composition disclosed herein may have a glass transition temperature greater than or equal to 201°C, for example, between 201°C and 288°C, as measured according to the method described in IPC-TM-6502.4.24.5.

[0166] Water absorption rate

[0167] In the water absorption test, a copper-free substrate 2 (made of eight prepregs pressed together) with a length of 2 inches and a width of 2 inches was selected as the sample to be tested. Each sample to be tested was placed in an oven at 105±10°C and baked for 1 hour, then taken out. After cooling at room temperature (about 23°C) for 10 minutes, the weight of the copper-free substrate 2 was weighed as W1. Then, the copper-free substrate 2 after weighing was soaked in pure water at room temperature for 24 hours, then taken out, and the water remaining on the surface of the substrate was wiped dry. The weight after wiping was weighed as the weight of the copper-free substrate 2 after water absorption, which was W2. The water absorption was calculated according to the formula: Water absorption W (%) = ((W2-W1) / W1) × 100%. The water absorption of each sample to be tested was measured with reference to the method described in IPC-TM-6502.6.2.1a, and the unit is %.

[0168] In this field, lower water absorption is preferred. A water absorption difference of 0.10% or greater indicates significant differences in water absorption between different substrates (posing significant technical difficulties). For example, an article made from the resin composition disclosed herein may have a water absorption of less than or equal to 0.39%, for example, between 0.18% and 0.39%, as measured according to IPC-TM-650 2.6.2.1a.

[0169] By referring to the test results in Tables 1 to 6, the following phenomena can be clearly observed.

[0170] Examples E1 to E15, in which the resin composition simultaneously includes 20 to 45 parts by weight of phosphorus-containing bismaleimide and 100 parts by weight of thermosetting resin, all simultaneously achieve the following properties: volatile condensate less than or equal to 0.019% in the outgassing test, total mass loss less than or equal to 0.67% in the outgassing test, arc resistance greater than or equal to 105 seconds, copper foil tensile strength greater than or equal to 4.05 lb / in, and X-axis thermal expansion coefficient less than or equal to 13.2 ppm / °C. In contrast, Comparative Examples C1 to C15 fail to meet the requirements for at least one of the following properties: outgassing test, arc resistance, copper foil tensile strength, and X-axis thermal expansion coefficient.

[0171] In a system where the thermosetting resin is a vinyl polyphenylene ether resin and a maleimide resin, it was found that compared to Examples E1 to E5, Comparative Example C1, which used a compound having a structure represented by Formula (III) different from the phosphorus-containing bismaleimide of the present invention in the resin composition, failed to meet the requirements in terms of outgassing test, arc resistance, X-axis thermal expansion coefficient, glass transition temperature, and water absorption.

[0172] In a system where the thermosetting resin is a vinyl polyphenylene ether resin and a maleimide resin, it was found that, compared to Examples E1 to E5, Comparative Examples C2 to C8, which omitted the phosphorus-containing bismaleimide of the present invention and instead added other flame retardants to the resin composition, failed to meet the requirements in outgassing testing, arc resistance, copper foil tensile strength, and X-axis thermal expansion coefficient. Furthermore, the flame retardancy of Comparative Examples C4, C5, and C7 failed to reach the V-0 rating.

[0173] In a system where the thermosetting resin is a vinyl polyphenylene ether resin and a polyolefin resin, it was found that compared to Examples E6 to E10, Comparative Example C9, which used a compound having a structure represented by Formula (III) different from the phosphorus-containing bismaleimide of the present invention in the resin composition, failed to meet the requirements in terms of outgassing test, arc resistance, copper foil tensile strength, X-axis thermal expansion coefficient, glass transition temperature, and water absorption.

[0174] In a system where the thermosetting resin is a vinyl-containing polyphenylene ether resin and a polyolefin resin, it can be found that compared with Examples E6 to E10, Comparative Example C10, which does not use the phosphorus-containing bismaleimide of the present invention in the resin composition and instead adds other flame retardants, fails to meet the requirements in outgassing test, arc resistance, copper foil tensile strength, X-axis thermal expansion coefficient, and glass transition temperature.

[0175] In a system where the thermosetting resin includes a prepolymer of a maleimide resin, it was found that, compared to Examples E11 to E15, Comparative Example C11, which used a compound having a structure represented by Formula (III) different from the phosphorus-containing bismaleimide of the present invention in the resin composition, failed to meet the requirements in terms of outgassing test, glass transition temperature, and water absorption.

[0176] In a system where the thermosetting resin includes a maleimide resin prepolymer, it was found that compared to Examples E11 to E15, Comparative Example C12, which omitted the phosphorus-containing bismaleimide of the present invention and instead added other flame retardants to the resin composition, failed to meet the requirements in terms of outgassing test, arc resistance, and water absorption.

[0177] Compared to Examples E11 to E15, Comparative Example C13, in which diallyl bisphenol A and maleimide resin prepolymers are not used in the resin composition and diallyl bisphenol A and maleimide resin are added externally, fails to meet the requirements in outgassing test, arc resistance, copper foil tensile strength, X-axis thermal expansion coefficient, glass transition temperature, and water absorption rate.

[0178] On the other hand, observing Comparative Examples C14 and C15, it can be found that when the amount of the phosphorus-containing bismaleimide of the present invention is 5 parts by weight and 70 parts by weight relative to 100 parts by weight of the thermosetting resin, satisfactory tensile strength on the copper foil cannot be achieved, and at least one of the flame retardancy, arc resistance, X-axis thermal expansion coefficient, and water absorption cannot meet the requirements.

[0179] In general, the resin composition of the present invention can simultaneously achieve the following properties: a volatile condensate of less than or equal to 0.019% in an outgassing test, a total mass loss of less than or equal to 0.67% in an outgassing test, an arc resistance of greater than or equal to 105 seconds, a copper foil tensile strength of greater than or equal to 4.05 lb / in, an X-axis thermal expansion coefficient of less than or equal to 13.2 ppm / °C, a flame retardancy of V-0, a glass transition temperature of greater than or equal to 201°C, and a water absorption of less than or equal to 0.39%.

[0180] The above embodiments are merely illustrative and are not intended to limit the embodiments of the subject application or their applications or uses. As used herein, the term "exemplary" means "serving as an example, instance, or illustration." The inclusion of any one exemplary embodiment herein is not necessarily to be construed as preferred or advantageous over other embodiments.

[0181] Furthermore, although at least one exemplary embodiment or comparative example has been presented in the foregoing detailed description, it should be understood that a large number of variations are possible. 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. On the contrary, the foregoing detailed description will provide those skilled in the art with a simple guide to implementing one or more of the described embodiments. Furthermore, various changes may be made to the function and arrangement of components without departing from the scope defined by the claims, and the claims encompass known equivalents and all foreseeable equivalents at the time of filing this patent application.

Claims

1. A resin composition, characterized in that The invention comprises 20 to 45 parts by weight of phosphorus-containing bismaleimide and 100 parts by weight of a thermosetting resin, wherein: The phosphorus-containing bismaleimide has a structure shown in formula (I): wherein R1 is a hydrogen atom, a methyl group, or an ethyl group; R2 is a hydrogen atom or a methyl group; R3 is a hydrogen atom or a C1-C6 alkyl group; R4 is a hydrogen atom or a C1-C6 alkyl group; R5 is a hydrogen atom or a C1-C6 alkyl group; and R6 is a hydrogen atom or a C1-C6 alkyl group; and The thermosetting resin is selected from the group consisting of vinyl polyphenylene ether resin, maleimide resin, polyolefin resin, maleimide resin prepolymer and combinations thereof.

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

3. The resin composition according to claim 1, wherein The maleimide resin includes bisphenol A diphenyl ether bismaleimide resin, bis(3-ethyl-5-methyl-4-maleimidophenyl)methane, a maleimide resin having a structure shown in formula (IV), 4,4'-diphenylmethane bismaleimide resin or a combination thereof. Where 1≤n≤5.

4. The resin composition according to claim 1, characterized in that The polyolefin resin includes styrene-butadiene copolymer, polybutadiene resin or a combination thereof.

5. The resin composition according to claim 1, wherein The maleimide resin prepolymer includes a prepolymer of a diallyl compound and a maleimide resin, a prepolymer of a diamine and a maleimide resin, a prepolymer of a multifunctional amine and a maleimide resin, a prepolymer of an acidic phenol compound and a maleimide resin, or a combination thereof.

6. The resin composition according to claim 1, characterized in that The resin composition further comprises an inorganic filler, a flame retardant, a hardening accelerator, a polymerization inhibitor, a solvent, a silane coupling agent, a dye, a toughening agent or a combination thereof.

7. A product made from the resin composition according to claim 1, characterized in that: The product includes a prepreg, a resin film, a laminate or a printed circuit board.

8. The product according to claim 7, characterized in that The product has a volatile condensate of less than or equal to 0.019% and a total mass loss of less than or equal to 0.67% in an outgassing test measured according to the method described in IPC-TM-6502.6.4B.

9. The product according to claim 7, characterized in that The arc resistance of the product measured according to the method described in IPC-TM-6502.5.1B is greater than or equal to 105 seconds.

10. The product according to claim 7, characterized in that The copper foil tensile strength of the product measured according to the method described in IPC-TM-6502.4.8 is greater than or equal to 4.05 lb / in.

11. The product according to claim 7, characterized in that The X-axis thermal expansion coefficient of the product measured according to the method described in IPC-TM-6502.4.24.5 is less than or equal to 13.2 ppm / °C.

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