Resin compositions and products thereof

Abstract

This invention discloses a resin composition comprising a copolymer and a phosphorus-containing flame retardant, wherein the copolymer is obtained by copolymerization of a mixture comprising maleimide resin and a diamine compound, the maleimide resin comprising aromatic maleimide resin and aliphatic maleimide resin, and the phosphorus-containing flame retardant having the structure shown in formula (1). This resin composition can be made into various articles, including prepregs, resin films, laminates, or printed circuit boards, and improves one or more of the following properties: glass transition temperature, Z-axis coefficient of thermal expansion, dielectric constant, dielectric loss, tensile strength to copper foil, and flame retardancy.

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. [Previous Technology]

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

[0003] Accordingly, there is a need to propose a novel material that can meet the current requirements of circuit board characteristics. [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 property requirements, the main object of the present invention is to provide a resin composition and articles made therefrom, thereby improving at least one or more properties such as glass transition temperature, Z-axis coefficient of thermal expansion, dielectric constant, dielectric loss, tensile strength to copper foil and flame retardancy.

[0005] To achieve the above objectives, the present invention discloses a resin composition comprising: a copolymer obtained by copolymerization of a mixture comprising maleimide resin and a diamine compound, wherein the maleimide resin comprises aromatic maleimide resin and aliphatic maleimide resin; and a phosphorus-containing flame retardant having the structure shown in formula (1): Formula (1) Wherein, G independently represents a group having the structure shown in formula (2) or a group having the structure shown in formula (3): Formula (2) Formula (3) Wherein, * represents the bonding position to a carbon atom.

[0006] For example, in one embodiment, the resin composition of the present invention includes 100 parts by weight of the copolymer and 20 to 60 parts by weight of the phosphorus-containing flame retardant.

[0007] For example, in one embodiment, the molar ratio of the aromatic maleimide resin, the aliphatic maleimide resin and the diamine compound in the mixture is between 2:0.5:0.1 and 5:2:1.

[0008] For example, in one embodiment, the phosphorus-containing flame retardant has the structure shown in Formula (1-1): Formula (1-1).

[0009] For example, in one embodiment, the phosphorus-containing flame retardant has the structure shown in formula (1-2): Formula (1-2).

[0010] For example, in one embodiment, the aromatic maleimide resin includes 4,4'-diphenylmethane bismaleimide, polyphenylmethane maleimide, bisphenol A diphenyl ether bismaleimide, 3,3'-dimethyl-5,5'-diethyl-4,4'-diphenylmethane bismaleimide, and 3,3'-dimethyl-5,5'-dipropyl-4,4'-diphenylmethane bismaleimide. Maleimide, m-phenylene bismaleimide, 4-methyl-1,3-phenylene bismaleimide, N-2,3-dimethylphenylmaleimide, N-2,6-dimethylphenylmaleimide, N-phenylmaleimide, vinylbenzylmaleimide, maleimide containing a biphenyl structure, maleimide containing an indane structure, maleimide containing isopropylidene and m-phenylene structures, or combinations thereof.

[0011] For example, in one embodiment, the aliphatic maleimide resin includes 1,6-bismaleimide-(2,2,4-trimethyl)hexane, maleimides containing a C10 to C50 aliphatic long-chain structure, or combinations thereof.

[0012] For example, in one embodiment, the diamine compound includes 4,4'-(1,4-phenylene diisopropylidene)diphenylamine, a diamine compound containing a siloxane structure, or a combination thereof.

[0013] For example, in one embodiment, the resin composition of the present invention further includes an additive, wherein the additive includes a vinyl polyphenylene ether resin, a polyimide resin, benzocyclobutene, diallyl ether compounds or combinations thereof.

[0014] For example, in one embodiment, the resin composition of the present invention further includes inorganic fillers, curing accelerators, polymerization inhibitors, solvents, silane coupling agents, dyes, toughening agents, or combinations thereof.

[0015] In addition, the present invention also provides an article (or product) made of the aforementioned resin composition, comprising 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: a glass transition temperature greater than or equal to 211 °C as measured by the method described in IPC-TM-650 2.4.24.5; a Z-axis coefficient of thermal expansion less than or equal to 47 ppm / °C as measured by the method described in IPC-TM-650 2.4.24.5; a dielectric constant less than or equal to 3.49 as measured by the method described in JIS C2565 at a frequency of 10 GHz; a dielectric loss less than or equal to 0.0046 as measured by the method described in JIS C2565 at a frequency of 10 GHz; a copper foil tensile strength greater than or equal to 4.01 lb / in as measured by the method described in UL94; and a flame retardancy rating of V-0 as measured by the method described in UL94.

Implementation Method

[0017] 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 as understood by those skilled in the art regarding this invention, and in case of conflict, the definitions in this specification shall prevail.

[0018] The theories or mechanisms described and disclosed herein, whether right or wrong, should not limit the scope of the invention in any way, that is, the contents of the invention can be implemented without being limited by any particular theory or mechanism.

[0019] The terms "a," "an," "an," or similar expressions are used herein to describe the components and technical features described herein. Such descriptions are merely for convenience of expression and to provide a general meaning regarding the scope of the invention. Therefore, such descriptions should be understood to include one or at least one, and the singular also includes the plural, unless clearly otherwise indicated.

[0020] In this document, "or a combination thereof" means "or any combination thereof", and "any one", "any kind", "any one" means "any one", "any kind", "any one".

[0021] In this document, the terms “comprising,” “including,” “having,” “containing,” or any other similar terms are open-ended transitional phrases intended to encompass non-exclusive inclusions. For example, a composition or article containing plural elements is not limited to those listed herein, but may also include other elements not explicitly listed but typically inherent to that composition or article. Furthermore, unless explicitly stated otherwise, the term “or” refers to an inclusive “or,” not an exclusive “or.” For example, any of the following satisfy 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); A and B are both true (or exist). Moreover, in this document, the terms “comprising,” “including,” “having,” and “containing” should be interpreted as specifically revealing and simultaneously encompassing closed or semi-closed transitional phrases such as “composed of” and “substantially composed of.”

[0022] In this article, the terms “and”, “with”, “and”, “as well as” or other similar terms are used to connect parallel sentence components, and there is no distinction between primary and secondary components. The parallel sentence components do not change in meaning when their positions are interchanged.

[0023] Throughout this document, all features or conditions defined as 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 encompassing and specifically revealing 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 revealing 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 revealing 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 revealing 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.

[0024] If a quantity or other numerical value or parameter is expressed as a range, a preferred range, or a series of upper and lower limits, it shall 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, whether such ranges are disclosed separately or not. Furthermore, when a range of numerical values ​​is mentioned herein, unless otherwise stated, the range shall include its endpoints and all integers and fractions within the range.

[0025] In this document, numerical values ​​should be understood to have a precision of significant digits, provided that the purpose of the invention can be achieved. For example, the number 40.0 should be understood to cover a range from 39.95 to 40.04.

[0026] In this document, when Markush groups or alternative terms are used to describe features or examples of the present 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 present 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 present 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 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", then the claim that X is X1 or X2 or X3 and Y is Y1 or Y2 or Y3 has been fully described.

[0027] 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 polymeric compounds. The term "compound" as used herein is not limited to a single chemical substance, but can also be interpreted as a class of chemical substances having the same composition or the same properties. Furthermore, in this invention, a mixture refers to a combination of two or more compounds.

[0028] Unless otherwise specified, in this invention, a polymer refers to a product formed by the polymerization reaction of monomers, often including 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 may include homopolymers, copolymers, prepolymers, etc., but are not limited thereto. A homopolymer is a polymer formed by the polymerization of one monomer. A copolymer is a polymer formed by the polymerization of two or more monomers. For example, copolymers may 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. Polymers certainly include oligomers, but are not limited thereto. Oligomers, also known as low-molecular-weight polymers, are polymers composed of 2 to 20 repeating units, usually polymers composed of 2 to 5 repeating units.

[0029] Unless otherwise specified, "resin" in this invention is a common name for a synthetic polymer. When interpreted, it may include monomers, polymers thereof, combinations of monomers, combinations of polymers thereof, or combinations of monomers and their polymers, etc., and is not limited thereto.

[0030] Unless otherwise specified, in this invention, the modified product (also known as the modified material) includes: the product after the reactive functional groups of each resin are modified, the product after the prepolymerization reaction of each resin with other resins, the product after the crosslinking of each resin with other resins, the product after the homopolymerization of each resin, the product after the copolymerization of each resin with other resins, etc.

[0031] In this document, "vinyl-containing" means that the compound structure contains an vinyl carbon-carbon double bond (C=C) or a derivative functional group thereof. Therefore, examples of vinyl-containing compounds may include, but are not limited to, compounds containing vinyl, styrene, allyl, vinyl benzyl, methacrylate, or other functional groups in their structure. 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. Therefore, for example, a vinyl-containing resin may represent, but is not limited to, a resin containing vinyl, styrene, allyl, vinyl benzyl, or methacrylate functional groups.

[0032] In this document, parts by weight represent the number of parts by weight, which can be any unit of weight, such as, but not limited to, grams, kilograms, pounds, etc. For example, 100 parts by weight of copolymer can represent 100 grams of copolymer, 100 kilograms of copolymer, or 100 pounds of copolymer, and is not limited thereto. In this document, if the amounts of different components are presented in a proportional relationship, the actual amount used can be any amount that conforms to that proportional relationship.

[0033] The following specific 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 content of the invention or any theory described in the following specific embodiments or examples.

[0034] As mentioned above, the main objective of this invention is to provide a resin composition comprising: a copolymer obtained by copolymerization of a mixture comprising maleimide resin and a diamine compound, wherein the maleimide resin comprises aromatic maleimide resin and aliphatic maleimide resin; and a phosphorus-containing flame retardant having the structure shown in formula (1): Formula (1) Wherein, each G independently represents a group having the structure shown in formula (2) or a group having the structure shown in formula (3): Formula (2) Formula (3) Wherein, * represents the bonding position to a carbon atom.

[0035] For example, in one embodiment, the amounts of the copolymer and the phosphorus-containing flame retardant are not particularly limited. For example, the resin composition of the present invention may include 100 parts by weight of the copolymer and 20 to 60 parts by weight of the phosphorus-containing flame retardant. For example, relative to 100 parts by weight of the copolymer, the resin composition of the present invention may include 20, 25, 30, 35, 40, 45, 50, 55, or 60 parts by weight of the phosphorus-containing flame retardant, and is not limited thereto.

[0036] For example, in one embodiment, the conditions for the aforementioned copolymerization reaction are not particularly limited. For example, a mixture comprising a maleimide resin (maleimide resins include aromatic maleimide resins and aliphatic maleimide resins) and a diamine compound may be subjected to the aforementioned copolymerization reaction under high temperature conditions (e.g., but not limited to, between 100 °C and 150 °C). For example, in one embodiment, the aforementioned mixture may also contain other components. For example, the aforementioned mixture may contain a catalyst (e.g., a synthesis catalyst), and the aforementioned copolymerization reaction may be carried out in the presence of the catalyst; the type of catalyst is not particularly limited, for example, it may include ethylenediamine. For example, the aforementioned mixture may contain a solvent, and the aforementioned copolymerization reaction may be carried out in a solvent; the type of solvent is not particularly limited, for example, it may include propylene glycol methyl ether acetate, dimethyl acetylamine, or combinations thereof.

[0037] As mentioned above, the reactants (i.e., monomers) participating in the copolymerization reaction may include, but are not limited to, aromatic maleimide resins, aliphatic maleimide resins, and diamine compounds, and the amounts of the three reactants are not particularly limited. For example, in one embodiment, the molar ratio of aromatic maleimide resin, aliphatic maleimide resin, and diamine compound is between 2:0.5:0.1 and 5:2:1. For example, in one embodiment, the molar ratio of aromatic maleimide resin, aliphatic maleimide resin, and diamine compound is 3:1:1, but is not limited thereto.

[0038] In addition, the time of the aforementioned copolymerization reaction is not particularly limited, for example, it can be between 1 hour and 10 hours.

[0039] For example, in one embodiment, the weight-average molecular weight of the aforementioned copolymer can be adjusted by changing the conditions of the copolymerization reaction. For example, in one embodiment, the weight-average molecular weight of the aforementioned copolymer is between 1500 and 5000.

[0040] For example, in one embodiment, the aromatic maleimide resin includes 4,4'-diphenylmethane bismaleimide, polyphenylmethane maleimide, bisphenol A diphenyl ether bismaleimide, 3,3'-dimethyl-5,5'-diethyl-4,4'-diphenylmethane bismaleimide, and 3,3'-dimethyl-5,5'-dipropyl-4,4'-diphenylmethane bismaleimide. Maleimide, m-phenylene bismaleimide, 4-methyl-1,3-phenylene bismaleimide, N-2,3-dimethylphenylmaleimide, N-2,6-dimethylphenylmaleimide, N-phenylmaleimide, vinylbenzylmaleimide, maleimide containing a biphenyl structure, maleimide containing an indane structure, maleimide containing isopropylidene and m-phenylene structures, or combinations thereof. For example, in one embodiment, the aromatic maleimide resin includes, but is not limited to, bisphenol A diphenyl ether bismaleimide resin (such as BMI-80, purchased from KI Chemical), 3,3'-dimethyl-5,5'-diethyl-4,4'-diphenylmethane bismaleimide resin (such as BMI-70, purchased from KI Chemical), maleimides containing isopropylidene and metaphenyl structures (such as MIR-5000, purchased from Nippon Kayaku), or combinations thereof.

[0041] For example, in one embodiment, the aliphatic maleimide resin comprises 1,6-bismaleimide-(2,2,4-trimethyl)hexane, maleimides containing a C10 to C50 aliphatic long-chain structure, or combinations thereof. For example, in one embodiment, the aliphatic maleimide resin includes, but is not limited to, 1,6-bismaleimide-(2,2,4-trimethyl)hexane (such as BMI-TMH, purchased from Sichuan Dongcai Technology Co., Ltd.).

[0042] For example, in one embodiment, the diamine compound includes 4,4'-(1,4-phenylene diisopropylidene)diphenylamine, a siloxane-containing diamine compound, or a combination thereof. For example, in one embodiment, the diamine compound includes, but is not limited to, 4,4'-(1,4-phenylene diisopropylidene)diphenylamine (Bisaniline P, purchased from Mitsui Chemicals), a siloxane-containing diamine compound (X-22-9409, purchased from Shinkotsu Chemicals), or a combination thereof.

[0043] In the resin composition of the present invention, the phosphorus-containing flame retardant has the structure shown in formula (1): Formula (1) Wherein, each G independently represents a group having the structure shown in formula (2) or a group having the structure shown in formula (3): Formula (2) Formula (3) Wherein, * represents the bonding position to a carbon atom.

[0044] For example, in one embodiment, the phosphorus-containing flame retardant has the structure shown in Formula (1-1): Formula (1-1).

[0045] For example, in one embodiment, the phosphorus-containing flame retardant has the structure shown in formula (1-2): Formula (1-2).

[0046] In addition to the aforementioned copolymer and phosphorus-containing flame retardant, the resin composition of the present invention may also include additives as needed. The type of additive is not particularly limited and can be any additive commonly used in the art. For example, in one embodiment, the additive includes a vinyl polyphenylene ether resin, a polyimide resin, benzocyclobutene, diallyl ether compounds, or combinations thereof. Unless otherwise specified, the content of any of the aforementioned components may be 5 to 50 parts by weight relative to 100 parts by weight of the copolymer, for example, 5, 10, 15, 20, 25, 30, 35, 40, 45, or 50 parts by weight, and is not limited thereto. For example, in one embodiment, by adding additives to the resin composition, such as, but not limited to, polyimide resin, the properties of the product of the resin composition can be further adjusted or improved, for example, but not limited to, the tensile strength of copper foil.

[0047] For example, the aforementioned vinyl-containing polyphenylene ether resin may include, but is 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., methacrylic polyphenylene ether resin), allyl polyphenylene ether resin, vinyl benzyl modified 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 terminal vinyl benzyl polyphenylene ether resin with a number average molecular weight of about 1200 (e.g., OPE-2st 1200, available from Mitsubishi Gas Chemical Company), a terminal vinyl benzyl 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-containing polyphenylene ether resin with a number average molecular weight of about 1900 to 2300 (e.g., SA9000, available from Sabic Company), a vinyl benzyl-modified 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 / 0185904 A1, the entirety of which is incorporated herein by reference.

[0048] For example, in one embodiment, the polyimide resin of the present invention may be any type of polyimide resin known in the art, including but not limited to various commercially available polyimide resin products.

[0049] In one embodiment, for example, the resin composition of the present invention may further comprise, as needed, inorganic fillers, curing accelerators, polymerization inhibitors, solvents, silane coupling agents, colorants, toughening agents, or combinations thereof. Unless otherwise specified, the content of any of the foregoing components may be from 0.001 to 300 parts by weight relative to 100 parts by weight of the copolymer, for example, 0.001, 0.01, 0.1, 1, 5, 10, 20, 30, 40, 50, 60, 70, 80, 90, 100, 150, 200, 250, or 300 parts by weight, for example, 30 to 150 parts by weight, or for example, 200 to 300 parts by weight.

[0050] The aforementioned inorganic filler may 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: silicon dioxide (molten, non-molten, porous, or hollow), alumina, aluminum hydroxide, magnesium oxide, magnesium hydroxide, calcium carbonate, aluminum nitride, boron nitride, sintered bodies formed by aluminum nitride and boron nitride, aluminum silicate, silicon carbide, titanium dioxide, zinc oxide, zirconium oxide, mica, boehmite (AlOOH), calcined talc, talc, silicon nitride, calcined kaolin, hollow porous particles, or combinations thereof. Furthermore, the inorganic filler may be spherical, fibrous, plate-like, granular, flake-like, needle-like, or combinations thereof, and may be selectively pretreated with a silane coupling agent. For example, the amount of inorganic filler used in this invention is not particularly limited compared to 100 parts by weight of copolymer, for example, it can be 10 to 200 parts by weight, or 100 to 300 parts by weight.

[0051] The aforementioned curing accelerator (including curing initiator) may contain Lewis bases or Lewis acids as catalysts. The Lewis base may contain 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), 4-dimethylaminopyridine (DMAP), and tetraphenylboron tetraphenylphosphine. The Lewis acid may contain metal salt compounds, such as manganese, iron, cobalt, nickel, copper, zinc, etc., or metal catalysts such as zinc octoate and cobalt octoate.

[0052] The curing accelerator may also include a curing initiator, such as a peroxide that can generate free radicals. The curing initiator includes, but is not limited to: benzoyl peroxide, dicumyl peroxide, 2,5-dimethyl-2,5-di(tert-butylperoxy)hexane, 2,5-dimethyl-2,5-di(tert-butylperoxy)-3-hexyne, di-tert-butyl peroxide, di(tert-butylperoxyisopropyl)benzene, di(tert-butylperoxy)hexane, etc. Phthalate (tert-butylperoxy)isophthalate, tert-butyl peroxybenzoate, 2,2-bis(tert-butylperoxy)butane, 2,2-bis(tert-butylperoxy)octane, 2,5-dimethyl-2,5-di(benzoylperoxy)hexane, lauryl peroxide, tert-hexyl pervalerate, dibutyl peroxyisopropylbenzene, bis(4-tert-butylcyclohexyl)dicarbonate peroxide, or combinations thereof. For example, the content of the curing accelerator used in this invention is 0.01 to 5 parts by weight, preferably 0.1 to 1.0 parts by weight, and more preferably 0.3 to 0.8 parts by weight, relative to 100 parts by weight of the copolymer.

[0053] In one embodiment, for example, the polymerization inhibitor described in this invention is not particularly limited, and may be any type of polymerization inhibitor known in the art, including but not limited to various commercially available polymerization inhibitor products. For example, the above-mentioned polymerization inhibitor may include, but is not limited to, 1,1-diphenyl-2-trinitrophenylhydrazine, methacrylonitrile, disulfide, nitric oxide-stabilized free radical, triphenylmethyl free radical, metal ion free radical, sulfur free radical, hydroquinone, p-methoxyphenol, p-benzoquinone, phenthiazide, β-phenylnaphthylamine, p-tert-butylcatechol, methylene blue, 4,4'-butylenebis(6-tert-butyl-3-methylphenol), 2,2'-methylenebis(4-ethyl-6-tert-butylphenol) or combinations thereof. For example, the above-mentioned nitric oxide-stabilized free radical may include, but is not limited to, 2,2,6,6-substituted-1-piperidinoxy free radical or 2,2,5,5-substituted-1-pyrrolidineoxy free radical, etc., nitric oxide free radicals derived from cyclic hydroxylamines. As substituents, alkyl groups with 4 or fewer carbon atoms, such as methyl or ethyl, are preferred. Specific examples of nitroxide free radical compounds include 2,2,6,6-tetramethyl-1-piperidinoxy radical, 2,2,6,6-tetraethyl-1-piperidinoxy radical, 2,2,6,6-tetramethyl-4-oxo-1-piperidinoxy radical, 2,2,5,5-tetramethyl-1-pyrrolidineoxy radical, 1,1,3,3-tetramethyl-2-isodihydroindoleoxy radical, and N,N-di-tert-butylamineoxy radical. Stable free radicals such as galvinoxyl radicals can also be used instead of nitroxide free radicals. The polymerization inhibitor suitable for the resin compositions of the present invention can also be a product 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 amine, hydroxyl, or ketone carbonyl groups.

[0054] The main function of adding solvents is to change the solid content of the resin composition and adjust its viscosity. For example, solvents may include, but are 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, and other solvents or mixtures thereof. The amount of the aforementioned solvents is not particularly limited; the amount added can be adjusted according to the required viscosity of the resin composition.

[0055] The aforementioned silane coupling agent may include various silane compounds (such as, but not limited to, siloxane compounds) and combinations thereof. Silane compounds may be further classified according to the type of functional group as amino silane compounds, epoxide silane compounds, vinyl silane compounds, acrylate silane compounds, methacrylate silane compounds, hydroxy silane compounds, isocyanate silane compounds, methacryloxy silane compounds, and acryloxy silane compounds.

[0056] The dyeing agents applicable to the present invention may include, but are not limited to, dyes or pigments.

[0057] The main function of adding toughening agents is to improve the toughness of the resin composition. The toughening agents may include, but are not limited to, rubber resin, carboxyl-terminated butadiene acrylonitrile rubber (CTBN), core-shell rubber, or combinations thereof.

[0058] In addition to the aforementioned resin composition, the present invention also provides an article made from the above-mentioned resin composition, such as a component suitable for use in various electronic products, including but not limited to prepreg, resin film, laminate or printed circuit board.

[0059] For example, the resin composition 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 80 °C and 160 °C, preferably between 100 °C and 140 °C. The reinforcing material can be any of a fibrous material, woven fabric, or non-woven fabric, and the woven fabric preferably includes glass fiber cloth. There is no particular limitation on the type of glass fiber cloth, and it can be various glass fiber cloths that can be used 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, Q-type glass fiber cloth, or QL-type glass fiber cloth (a glass fiber cloth with a mixed structure made of Q glass and L glass). The types of glass fibers include yarn and roving, and the forms include open fibers or closed fibers, and the end face shapes include round or flat shapes. 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 can increase 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 forms an insulating layer after subsequent heating and curing (C-stage).

[0060] For example, the resin composition of the present invention can be made into a resin film, which is obtained by baking and heating the aforementioned resin composition to form a semi-cured state. The resin composition can be selectively coated on a support material, including but not limited to liquid crystal resin film, polytetrafluoroethylene film, polyethylene terephthalate film (PET film), polyimide film (PI film), metal foil or resin-coated copper (RCC) foil, and then baked and heated to form a semi-cured state, so that the resin composition forms a resin film.

[0061] For example, the resin composition of the present invention can be used to form various laminates comprising at least two metal foils and at least one insulating layer disposed between the two metal foils. The insulating layer can be formed by curing the aforementioned resin composition under high temperature and high pressure (C-stage). Applicable curing temperatures are, for example, between 180 °C and 240 °C, preferably between 200 °C and 220 °C, with a curing time of 90 to 150 minutes, preferably 90 to 120 minutes. Applicable pressing pressures are, for example, between 200 psi and 650 psi, preferably between 250 psi and 600 psi. The aforementioned insulating layer can be obtained by curing the aforementioned prepreg or resin film. The aforementioned metal foils can be made of copper, aluminum, nickel, platinum, silver, gold, or alloys thereof, such as copper foil. In a preferred embodiment, the laminate is a copper foil substrate.

[0062] In one embodiment, the aforementioned multilayer board can be further processed by a circuit process to form a circuit board, such as a printed circuit board.

[0063] For example, in one embodiment, the article made from the resin composition of the foregoing embodiments contains a reinforcing material or a supporting material and a semi-cured or cured product obtained by heating and chemically crosslinking the resin composition.

[0064] In one or more embodiments, the article prepared from the resin composition of the present invention satisfies at least one of the following properties, preferably at least two, more, or all of the following properties: a glass transition temperature greater than or equal to 211 °C as measured by the method described in IPC-TM-650 2.4.24.5; a Z-axis coefficient of thermal expansion less than or equal to 47 ppm / °C as measured by the method described in IPC-TM-650 2.4.24.5; a dielectric constant less than or equal to 3.49 as measured by the method described in JIS C2565 at a frequency of 10 GHz; a dielectric loss less than or equal to 0.0046 as measured by the method described in JIS C2565 at a frequency of 10 GHz; a copper foil tensile strength greater than or equal to 4.01 lb / in as measured by the method described in IPC-TM-650 2.4.8; and a flame retardancy rating of V-0 as measured by the method described in UL94 specification.

[0065] The measurement methods for the aforementioned characteristics will be described in detail at the end of this document.

[0066] The resin compositions of the embodiments and comparative examples of the present invention were prepared according to the amounts specified in Tables 1 to 5 using various raw materials from the following sources, and were further prepared into various test samples.

[0067] The chemical raw materials used in the synthesis examples, embodiments, and comparative examples of the present invention are as follows: Copolymers: CP1 to CP5, as described in synthesis examples 1 to 5. Formula (1-1): A phosphorus-containing flame retardant having the structure shown in Formula (1-1), purchased from Hoshin Chemical. Formula (1-1) Formula (1-2): A phosphorus-containing flame retardant having the structure shown in Formula (1-2), purchased from Keyi Polymer. Formula (1-2) BMI-80: Aromatic maleimide resin, purchased from KI Chemical. BMI-TMH: Aliphatic maleimide resin, purchased from Sichuan Dongcai Technology Co., Ltd. BMI-70: Aromatic maleimide resin, purchased from KI Chemical. MIR-5000: Aromatic maleimide resin, purchased from Nippon Kayaku. Bisaniline P: Diamine compound, purchased from Mitsui Chemicals. X-22-9409: Diamine compound, purchased from Shin-Etsu Chemical. AF-217: Polyimide resin, purchased from Jin Yi Chemical. FBCB: Benzocyclobutene containing fluorenyl structure, purchased from Shandong Xingshun New Materials Co., Ltd. HMPS: Diallyl ether compound having the structure shown in formula (4), purchased from Changchun Artificial Resin Factory Co., Ltd. Formula (4) OPE-2st 2200: Polyphenylene ether resin containing vinylbenzyl biphenyl, purchased from Mitsubishi Gas Chemical. SA9000: Polyphenylene ether resin containing methacrylate, purchased from Sabic. PX-200: Resorcinol bis[di(2,6-dimethylphenyl) phosphate], purchased from Daihachi Chemical. PQ-60: p-xylylbis(diphenylphosphine oxide), purchased from Jin Yi Chemical. Di-DOPO: Flame retardant having the structure shown in formula (5), commercially available. Formula (5) SPV-100: Allyl phosphazene compound, purchased from Otsuka Chemical. TPPK: Tetraphenylboron tetraphenylphosphine, commercially available. ABN: Sintered body formed from aluminum nitride and boron nitride, purchased from Jinyi New Materials Co., Ltd. In the table, the inorganic filler content code "R" represents the ratio of the inorganic filler content to the total amount of all other components in the resin composition except for the inorganic filler, curing accelerator, and solvent in each example or comparative example. "R*100%" in the table represents that the inorganic filler content is 1 times the total amount of all other components mentioned above. For example, R*100% in Example E1 represents an addition of 135 parts by weight (the total amount of all other components in E1 except for the inorganic filler, curing accelerator, and solvent is 135 parts by weight, therefore the inorganic filler content is 135 parts by weight multiplied by 100%, hence 135 parts by weight). Anisole: Commercially available. The solvent content in the table is expressed as "appropriate amount," meaning the solvent content is adjusted to achieve a total solid content (S / C = 60%–68%) in the resin composition. Propylene glycol methyl ether acetate: commercially available. Ethylenediamine: commercially available.

[0068] Synthesis example 1

[0069] Add 3 moles of BMI-80, 1 mole of BMI-TMH, 1 mole of Bisaniline P, 100 parts by weight (about 0.76 moles) of propylene glycol methyl ether acetate and 0.5 parts by weight (about 0.008 moles) of ethylenediamine to a reaction vessel, stir continuously and heat to dissolve, and react at 120 °C for 4 hours. Cool down to room temperature to obtain copolymer CP1, which is the copolymer of the present invention.

[0070] Synthesis Example 2

[0071] Add 3 moles of BMI-80, 1 mole of BMI-TMH, 1 mole of X-22-9409, 100 parts by weight (about 0.76 moles) of propylene glycol methyl ether acetate and 0.5 parts by weight (about 0.008 moles) of ethylenediamine to a reaction vessel, stir continuously and heat to dissolve, and then react at 120 °C for 4 hours. Cool down to room temperature to obtain copolymer CP2, which is the copolymer of the present invention.

[0072] Synthesis Example 3

[0073] Add 1 mole of BMI-TMH, 1 mole of Bisaniline P, 100 parts by weight (about 0.76 moles) of propylene glycol methyl ether acetate and 0.5 parts by weight (about 0.008 moles) of ethylenediamine to a reaction vessel, stir continuously and heat to dissolve, and then react at 120 °C for 4 hours. Cool down to room temperature to obtain copolymer CP3.

[0074] Synthesis Example 4

[0075] Add 3 moles of BMI-80, 1 mole of Bisaniline P, 100 parts by weight (about 0.76 moles) of propylene glycol methyl ether acetate and 0.5 parts by weight (about 0.008 moles) of ethylenediamine to a reaction vessel, stir continuously and heat to dissolve, and then react at 120 °C for 4 hours. Cool down to room temperature to obtain copolymer CP4.

[0076] Synthesis example 5

[0077] Add 3 moles of BMI-80, 1 mole of BMI-TMH, 100 parts by weight (about 0.76 moles) of propylene glycol methyl ether acetate and 0.5 parts by weight (about 0.008 moles) of ethylenediamine to a reaction vessel, stir continuously and heat to dissolve, and then react at 120 °C for 4 hours. Cool down to room temperature to obtain copolymer CP5.

[0078] The resin composition (all units are parts by weight) and characteristic test results of the examples and comparative examples are shown below, where parts by weight refer to the number of parts by weight when the solid content of each component added in each example or comparative example is 100%. For example, Example E1 uses 35 parts by weight of phosphorus-containing flame retardant, which means that it uses 35 parts by weight of phosphorus-containing flame retardant with a solid content of 100%.

[0079] The composition (parts by weight) and characteristic tests of the resin compositions of the Examples and Comparative Examples are shown below. [Table 1] Composition (parts by weight) and characteristic tests of the resin compositions of the Examples Element name E1 E2 E3 E4 E5 copolymer CP1 100 100 100 100 100 CP2 CP3 CP4 CP5 Phosphorus-containing flame retardants Equation (1-1) 35 20 60 Equation (1-2) 35 60 Maleimide resin BMI-80 BMI-TMH BMI-70 MIR-5000 diamine compounds Bisaniline P additive AF-217 FBCB HMPS OPE-2st 2200 SA9000 Other flame retardants PX-200 PQ-60 Di-DOPO SPV-100 hardening accelerator TPPK 0.5 0.5 0.5 0.5 0.5 Inorganic fillers ABN R * 100% R * 100% R * 100% R * 100% R * 100% solvent aniline Appropriate amount Appropriate amount Appropriate amount Appropriate amount Appropriate amount characteristic unit E1 E2 E3 E4 E5 TMA-Tg o C 225 219 239 218 229 Z-CTE ppm / o C 45 47 35 47 41 Dk (10GHz) none 3.45 3.49 3.37 3.36 3.35 Df (10GHz) none 0.0045 0.0042 0.0033 0.0042 0.0046 P / S lb / in 4.65 4.83 4.38 4.33 4.01 Flame retardancy none V-0 V-0 V-0 V-0 V-0 [Table 2] Composition (parts by weight) and property tests of resin compositions in the examples Element name E6 E7 E8 E9 E10 copolymer CP1 100 100 CP2 100 100 100 CP3 CP4 CP5 Phosphorus-containing flame retardants Equation (1-1) 35 35 35 Equation (1-2) 35 35 Maleimide resin BMI-80 BMI-TMH BMI-70 MIR-5000 diamine compounds Bisaniline P additive AF-217 FBCB HMPS OPE-2st 2200 5 15 20 SA9000 20 10 5 Other flame retardants PX-200 PQ-60 Di-DOPO SPV-100 hardening accelerator TPPK 0.5 0.5 0.5 0.5 0.5 Inorganic fillers ABN R * 100% R * 100% R * 100% R * 100% R * 100% solvent aniline Appropriate amount Appropriate amount Appropriate amount Appropriate amount Appropriate amount characteristic unit E6 E7 E8 E9 E10 TMA-Tg o C 231 234 232 235 230 Z-CTE ppm / o C 31 33 37 35 39 Dk (10GHz) none 3.11 3.18 3.29 3.25 3.21 Df (10GHz) none 0.0043 0.0041 0.0041 0.0039 0.0039 P / S lb / in 4.13 4.01 4.41 4.43 4.46 Flame retardancy none V-0 V-0 V-0 V-0 V-0 [Table 3] Composition (parts by weight) and property tests of resin compositions in the examples Element name E11 E12 E13 E14 copolymer CP1 100 100 100 100 CP2 CP3 CP4 CP5 Phosphorus-containing flame retardants Equation (1-1) 35 35 35 15 Equation (1-2) 15 Maleimide resin BMI-80 30 BMI-TMH 10 BMI-70 MIR-5000 5 diamine compounds Bisaniline P additive AF-217 5 20 10 FBCB 15 20 HMPS 10 5 OPE-2st 2200 SA9000 Other flame retardants PX-200 PQ-60 Di-DOPO SPV-100 hardening accelerator TPPK 0.5 0.5 0.8 0.3 Inorganic fillers ABN R * 100% R * 100% R * 120% R * 80% solvent aniline Appropriate amount Appropriate amount Appropriate amount Appropriate amount characteristic unit E11 E12 E13 E14 TMA-Tg o C 211 218 228 235 Z-CTE ppm / o C 43 47 42 39 Dk (10GHz) none 3.37 3.42 3.31 3.26 Df (10GHz) none 0.0044 0.0043 0.0036 0.0033 P / S lb / in 4.49 5.15 5.41 5.27 Flame retardancy none V-0 V-0 V-0 V-0 [Table 4] Composition (parts by weight) and property tests of comparative example resin compositions Element name C1 C2 C3 C4 C5 copolymer CP1 100 CP2 CP3 100 CP4 100 CP5 100 Phosphorus-containing flame retardants Equation (1-1) 35 35 35 35 Equation (1-2) Maleimide resin BMI-80 BMI-TMH BMI-70 100 MIR-5000 diamine compounds Bisaniline P additive AF-217 FBCB HMPS OPE-2st 2200 SA9000 Other flame retardants PX-200 PQ-60 Di-DOPO SPV-100 hardening accelerator TPPK 0.5 0.5 0.5 0.5 0.5 Inorganic fillers ABN R * 100% R * 100% R * 100% R * 100% R * 100% solvent aniline Appropriate amount Appropriate amount Appropriate amount Appropriate amount Appropriate amount characteristic unit C1 C2 C3 C4 C5 TMA-Tg o C 170 243 232 206 150 Z-CTE ppm / o C 55 38 33 51 110 Dk (10GHz) none 3.39 3.74 3.75 3.51 3.80 Df (10GHz) none 0.0051 0.0068 0.0075 0.0053 0.0083 P / S lb / in 3.57 3.86 3.54 5.01 3.25 Flame retardancy none V-0 V-0 V-0 Burned out V-0 [Table 5] Composition (parts by weight) and property tests of comparative example resin compositions Element name C6 C7 C8 C9 C10 copolymer CP1 100 100 100 100 CP2 CP3 CP4 CP5 Phosphorus-containing flame retardants Equation (1-1) 35 Equation (1-2) Maleimide resin BMI-80 73 BMI-TMH 13 BMI-70 MIR-5000 diamine compounds Bisaniline P 14 additive AF-217 FBCB HMPS OPE-2st 2200 SA9000 Other flame retardants PX-200 35 PQ-60 35 Di-DOPO 35 SPV-100 35 hardening accelerator TPPK 0.5 0.5 0.5 0.5 0.5 Inorganic fillers ABN R * 100% R * 100% R * 100% R * 100% R * 100% solvent aniline Appropriate amount Appropriate amount Appropriate amount Appropriate amount Appropriate amount characteristic unit C6 C7 C8 C9 C10 TMA-Tg o C 184 153 176 180 164 Z-CTE ppm / o C 62 82 55 52 88 Dk (10GHz) none 3.66 3.47 3.63 3.69 3.89 Df (10GHz) none 0.0075 0.0046 0.0047 0.0049 0.0065 P / S lb / in 3.77 4.43 3.01 3.99 4.17 Flame retardancy none V-0 V-1 V-0 V-0 V-1

[0080] The aforementioned characteristics were obtained by preparing the test samples according to the following method, and then performing characteristic analysis according to specific conditions. 1. Prepreg 1 (PP 1): Using the resin compositions of the Examples and Comparative Examples (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., L-glass fiber fabric of specification 2116, purchased from Asahi Corporation) was immersed in the impregnation tank to allow the resin composition to adhere to the glass fiber cloth. Then, it was heated at 100 °C to 140 °C to form a semi-cured state (B-Stage) to obtain prepreg 1, which has a resin content of approximately 70%. 2. Prepreg 2 (PP 2): Using the resin compositions of the Examples and Comparative Examples (parts by weight), the components of the resin compositions were added to a mixing tank and mixed evenly to form a varnish. The adhesive solution is placed in an impregnation tank, and then glass fiber cloth (e.g., L-glass fiber fabric of specification 1078, purchased from Asahi Corporation) is immersed in the impregnation tank to allow the resin composition to adhere to the glass fiber cloth. Then, it is heated at 100 °C to 140 °C to form a semi-cured state (B-Stage) to obtain a semi-cured sheet 2 with a resin content of approximately 70%. 3. Copper substrate 1 (made by pressing two semi-cured sheets 1 together) Two 0.5 oz thick reverse treatment foil (RTF) copper foils and two L-glass fiber fabrics of specification 2116 are prepared to impregnate each test sample (each set of examples or each set of comparative examples) to form a semi-cured sheet 1. The copper foil, two prepreg sheets 1, and copper foil are stacked in sequence and pressed under vacuum conditions at a pressure of 250 psi to 600 psi and a temperature of 200°C to 220°C for 90 to 120 minutes to form a copper-containing substrate 1. The two prepreg sheets 1 are cured to form an insulating layer between the two copper foils, and the resin content of the insulating layer is approximately 70%. 4. Copper-containing substrate 2 (formed by pressing eight prepreg sheets 1 together) Two 0.5 oz Reverse Treatment Foil (RTF) copper foils and eight L-glass fiber cloths of specification 2116 are prepared to impregnate each test sample (each set of examples or each set of comparative examples) with prepreg sheets 1. The copper foil, eight prepreg sheets 1, and copper foil are stacked in sequence and pressed under vacuum conditions at a pressure of 250 psi to 600 psi and a temperature of 200°C to 220°C for 90 to 120 minutes to form a copper-containing substrate 2. The eight prepreg sheets 1 are cured to form an insulating layer between the two copper foils, and the resin content of the insulating layer is approximately 70%.5. Copper-containing substrate 3 (formed by laminating two prepreg sheets 2): Prepare two 0.5 oz Reverse Treatment Foil (RTF) copper foils and two L-fiberglass cloths of specification 1078 impregnated with the prepreg sheets 2 of each test sample (each set of examples or each set of comparative examples). Lay the copper foil, the two prepreg sheets 2, and the copper foil in that order, and press under vacuum conditions at a pressure of 250 psi to 600 psi and a temperature of 200°C to 220°C for 90 to 120 minutes to form the copper-containing substrate 3. The two prepreg sheets 2 are cured to form an insulating layer between the two copper foils, and the resin content of the insulating layer is approximately 70%. 6. Copper-containing substrate 4 (formed by laminating eight prepreg sheets 2): Prepare two 0.5 oz Reverse Treatment Foil (RTF) copper foils and eight L-fiberglass cloths of specification 1078 impregnated with the test samples (each set of examples or each set of comparative examples). Lay the copper foil, eight prepreg sheets 2, and copper foil in that order, and press under vacuum conditions at a pressing pressure of 250 psi to 600 psi and a temperature of 200°C to 220°C for 90 to 120 minutes to form the copper-containing substrate 4. The eight prepreg sheets 2 are cured to form an insulating layer between the two copper foils, with a resin content of approximately 70%. 7. Copper-free substrate 1 (formed by laminating two prepreg sheets 1): Etch the copper foils on both sides of the copper-containing substrate 1 to obtain the copper-free substrate 1. 8. Copper-free substrate 2 (formed by laminating eight prepreg sheets 1): The copper foil on both sides of the copper-containing substrate 2 is etched away to obtain the copper-free substrate 2. 9. Copper-free substrate 3 (formed by laminating two prepreg sheets 2): The copper foil on both sides of the copper-containing substrate 3 is etched away to obtain the copper-free substrate 3. 10. Copper-free substrate 4 (formed by laminating eight prepreg sheets 2): The copper foil on both sides of the copper-containing substrate 4 is etched away to obtain the copper-free substrate 4.

[0081] The test methods and their characteristic analysis items for the aforementioned samples are described below:

[0082] Glass transition temperature (TMA-Tg)

[0083] In the measurement of glass transition temperature, a copper-free substrate 2 (composed of eight prepreg sheets 1 laminated together) was selected as the test sample for thermomechanical analysis (TMA). The sample was heated at a temperature rise rate of 10 °C per minute, from 35 °C to 350 °C. The glass transition temperature of each test sample was measured according to the method described in IPC-TM-650 2.4.24.5, and the unit is °C.

[0084] In this art, a higher glass transition temperature is preferred. A glass transition temperature difference greater than or equal to 5 °C indicates a significant difference in glass transition temperatures between different substrates (presenting significant technical difficulty). For example, an article made from the resin composition disclosed in this invention has a glass transition temperature greater than or equal to 211 °C, for example, between 211 °C and 239 °C, as measured with reference to the method described in IPC-TM-650 2.4.24.5.

[0085] Z-axis coefficient of thermal expansion (Z-CTE)

[0086] In the measurement of the Z-axis thermal expansion coefficient, the copper-free substrate 4 (composed of eight prepreg sheets 2 laminated together) was selected as the test sample for thermomechanical analysis (TMA). The copper-free substrate 4 was cut into samples with a length of 10 mm and a width of 10 mm. The samples were heated at a heating rate of 10 °C per minute, from 35 °C to 300 °C. The Z-axis thermal expansion coefficient of each test sample in the temperature range (α1) from 50 °C to 110 °C was measured according to the method described in IPC-TM-650 2.4.24.5, and the unit was ppm / °C.

[0087] In this art, a lower Z-axis coefficient of thermal expansion is preferred. A difference in Z-axis coefficient of thermal expansion greater than or equal to 5 ppm / °C indicates a significant difference in the Z-axis coefficient of thermal expansion between different substrates (presenting significant technical difficulty). For example, an article made from the resin composition disclosed in this invention has a Z-axis coefficient of thermal expansion less than or equal to 47 ppm / °C, measured according to the method described in IPC-TM-650 2.4.24.5, for example, between 31 ppm / °C and 47 ppm / °C.

[0088] Dielectric constant (Dk)

[0089] In the measurement of dielectric constant, the copper-free substrate 3 (formed by laminating two prepreg sheets 2) was selected as the test sample. The dielectric constant of each test sample was obtained by using a microwave dielectrometer (purchased from AET Corporation, Japan) at room temperature (approximately 25°C) and a frequency of 10 GHz, in accordance with the method described in JIS C2565.

[0090] In this art, a lower dielectric constant indicates better dielectric properties of the sample under test. A difference in dielectric constant greater than or equal to 0.20 indicates a significant difference in dielectric constant between different substrates (significant technical difficulty). For example, an article made from the resin composition disclosed in this invention has a dielectric constant less than or equal to 3.49 when measured at a frequency of 10 GHz according to the method described in JIS C2565, for example, between 3.11 and 3.49.

[0091] Dielectric loss (dissipation factor, Df)

[0092] In the measurement of dielectric loss, the copper-free substrate 1 (formed by laminating two prepreg sheets 1) was selected as the test sample. The dielectric loss of each test sample was measured at room temperature (approximately 25°C) and at a frequency of 10 GHz, according to the method described in JIS C2565, using a microwave dielectrometer (purchased from AET Corporation, Japan).

[0093] In this field, lower dielectric loss indicates better dielectric properties of the sample under test. A dielectric loss difference greater than or equal to 0.0005 indicates a significant difference in dielectric loss between different substrates (representing significant technical difficulty). For example, an article made from the resin composition disclosed in this invention has a dielectric loss less than or equal to 0.0046 when measured at a frequency of 10 GHz according to the method described in JIS C2565, for example, between 0.0033 and 0.0046.

[0094] Copper foil peeling strength (Hoz peeling strength, Hoz P / S)

[0095] In the measurement of the tensile strength of the copper foil, the above-mentioned copper substrate 2 (made by pressing eight prepreg sheets 1 together) was cut into a rectangular sample with a width of 24 mm and a length greater than 60 mm. The copper foil on the surface was etched, leaving only a strip copper foil with a width of 3.18 mm and a length greater than 60 mm. The tensile strength was measured using a universal tensile strength tester at room temperature (about 25°C) 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, and the unit was lb / in.

[0096] In the art, higher copper foil tensile strength is preferred. A difference in copper foil tensile strength greater than or equal to 0.1 lb / in indicates a significant difference in copper foil tensile strength between different substrates (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 4.01 lb / in, for example, between 4.01 lb / in and 5.41 lb / in, as measured with reference to the method described in IPC-TM-650 2.4.8.

[0097] Flame retardancy

[0098] In the flame retardancy measurement, a 125 mm × 13 mm copper-free substrate 2 (made of eight prepreg sheets 1 laminated together) was used as the test sample. Measurements were performed according to the method described in UL94, and the flame retardancy analysis results were expressed as V-0, V-1, and V-2 grades, where V-0 has better flame retardancy than V-1, V-1 has better flame retardancy than V-2, and the worst result is when the sample burns out completely. For example, an article made of the resin composition disclosed in this invention has a flame retardancy test result of V-0 obtained by measuring with reference to the method described in UL94.

[0099] Based on the test results in Tables 1 to 5, the following phenomena can be clearly observed.

[0100] If the resin composition comprises a copolymer and a phosphorus-containing flame retardant, the copolymer being prepared by copolymerization of a mixture comprising maleimide resin and a diamine compound, the maleimide resin comprising aromatic maleimide resin and aliphatic maleimide resin, and the phosphorus-containing flame retardant having the structure shown in formula (1), as in Examples E1 to E14, all achieving a glass transition temperature greater than or equal to 211 °C, a Z-axis thermal expansion coefficient less than or equal to 47 ppm / °C, a dielectric constant less than or equal to 3.49, a dielectric loss less than or equal to 0.0046, a copper foil tensile strength greater than or equal to 4.01 lb / in, and a flame retardancy rating of V-0. In contrast, Comparative Examples C1 to C10 fail to meet the requirements for at least one of these properties.

[0101] Comparative Example C1, which did not use aromatic maleimide resin in the copolymer preparation process, failed to meet the requirements in terms of glass transition temperature, Z-axis thermal expansion coefficient, dielectric loss and copper foil tensile strength compared to Example E1.

[0102] Compared to Example E1, Comparative Example C2, which did not use aliphatic maleimide resin in the copolymer preparation process, failed to meet the requirements in terms of dielectric constant, dielectric loss and copper foil tensile strength.

[0103] Compared to Example E1, Comparative Example C3, which did not use a diamine compound in the copolymer preparation process, failed to meet the requirements in terms of dielectric constant, dielectric loss and copper foil tensile strength.

[0104] Comparative Example C4, which did not use a phosphorus-containing flame retardant with the structure shown in Formula (1) in the resin composition, failed to meet the requirements in terms of glass transition temperature, Z-axis thermal expansion coefficient, dielectric constant, dielectric loss and flame retardancy.

[0105] Compared to Example E1, Comparative Example C5, which uses aromatic maleimide resin instead of the copolymer of the present invention in the resin composition, fails to meet the requirements in terms of glass transition temperature, Z-axis thermal expansion coefficient, dielectric constant, dielectric loss and copper foil tensile strength.

[0106] Compared to Example E1, Comparative Example C6, which did not use the copolymer of the present invention in the resin composition but instead used the monomer component of the added copolymer, could not meet the requirements in terms of glass transition temperature, Z-axis thermal expansion coefficient, dielectric constant, dielectric loss and copper foil tensile strength.

[0107] Comparative Example C7, which uses PX-200 instead of phosphorus-containing flame retardant with the structure shown in Formula (1) in the resin composition, failed to meet the requirements in terms of glass transition temperature, Z-axis thermal expansion coefficient and flame retardancy.

[0108] Comparative Example C8, which uses PQ-60 instead of a phosphorus-containing flame retardant having the structure shown in Formula (1) in the resin composition, failed to meet the requirements in terms of glass transition temperature, Z-axis thermal expansion coefficient, dielectric constant, dielectric loss and copper foil tensile strength.

[0109] Compared with Examples E1 and E4, the phosphorus-containing flame retardant having the structure shown in Formula (1) was not used in the resin composition. Instead, Comparative Example C9 with Di-DOPO was used, which could not meet the requirements in terms of glass transition temperature, Z-axis thermal expansion coefficient, dielectric constant, dielectric loss and copper foil tensile strength.

[0110] Compared with Examples E1 and E4, the phosphorus-containing flame retardant having the structure shown in Formula (1) was not used in the resin composition. Instead, Comparative Example C10 with SPV-100 was used, which could not meet the requirements in terms of glass transition temperature, Z-axis thermal expansion coefficient, dielectric constant, dielectric loss and flame retardancy.

[0111] In general, the resin composition of the present invention and the articles made therefrom, such as Examples E1 to E14, can simultaneously achieve ideal characteristics such as a glass transition temperature greater than or equal to 211 °C, a Z-axis thermal expansion coefficient less than or equal to 47 ppm / °C, a dielectric constant less than or equal to 3.49, a dielectric loss less than or equal to 0.0046, a copper foil tensile strength greater than or equal to 4.01 lb / in, and a flame retardancy rating of V-0.

[0112] The above embodiments and examples are merely illustrative in nature and are not intended to limit the embodiments of the present invention or the application or use of these embodiments. In this invention, terms such as "example" mean "as an instance, example, or illustration." Any exemplary embodiment herein should not necessarily be interpreted as a better or more advantageous situation than other embodiments, unless otherwise indicated.

[0113] 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 still possible with respect to the present invention. It should also be understood that the embodiments herein are not intended to limit the scope, use, or configuration of the claimed technical solutions in any way. Rather, the foregoing embodiments can provide a simple guide for those skilled in the art to implement one or more of the foregoing embodiments and their equivalents. Furthermore, the scope of the patent application includes known equivalents and all foreseeable equivalents at the time of filing of this patent application.

Claims

1. A resin composition comprising: 100 parts by weight of a copolymer, which is obtained by copolymerization of a mixture including maleimide resin and a diamine compound, wherein the maleimide resin includes aromatic maleimide resin and aliphatic maleimide resin, wherein the molar ratio of aromatic maleimide resin, aliphatic maleimide resin and diamine compound in the mixture is between 2:0.5:0.1 and 5:2:1; and 20 to 60 parts by weight of a phosphorus-containing flame retardant having the structure shown in formula (1): Formula (1) Wherein, G independently represents a group having the structure shown in formula (2) or a group having the structure shown in formula (3): Formula (2) Formula (3) Wherein, * indicates the bonding position to a carbon atom.

2. The resin composition as claimed in claim 1, wherein the phosphorus-containing flame retardant has the structure shown in formula (1-1): Formula (1-1).

3. The resin composition as claimed in claim 1, wherein the phosphorus-containing flame retardant has the structure shown in formula (1-2): Formula (1-2).

4. The resin composition as claimed in claim 1, wherein the aromatic maleimide resin comprises 4,4'-diphenylmethane bismaleimide, polyphenylmethane maleimide, bisphenol A diphenyl ether bismaleimide, 3,3'-dimethyl-5,5'-diethyl-4,4'-diphenylmethane bismaleimide, and 3,3'-dimethyl-5,5'-dipropyl-4,4'-diphenylmethane bismaleimide. Maleimide, m-phenylene bismaleimide, 4-methyl-1,3-phenylene bismaleimide, N-2,3-dimethylphenylmaleimide, N-2,6-dimethylphenylmaleimide, N-phenylmaleimide, vinylbenzylmaleimide, maleimide containing a biphenyl structure, maleimide containing an indane structure, maleimide containing isopropylidene and m-phenylene structures, or combinations thereof.

5. The resin composition as claimed in claim 1, wherein the aliphatic maleimide resin comprises 1,6-bismaleimide-(2,2,4-trimethyl)hexane, maleimides containing a C10 to C50 aliphatic long-chain structure, or combinations thereof.

6. The resin composition as claimed in claim 1, wherein the diamine compound comprises 4,4'-(1,4-phenylene diisopropylidene)diphenylamine, a diamine compound containing a siloxane structure, or a combination thereof.

7. The resin composition as claimed in claim 1, further comprising additives, wherein the additives include vinyl polyphenylene ether resins, polyimide resins, benzocyclobutene, diallyl ether compounds, or combinations thereof.

8. The resin composition as claimed in claim 1, further comprising inorganic fillers, curing accelerators, polymerization inhibitors, solvents, silane coupling agents, colorants, toughening agents, or combinations thereof.

9. An article made from the resin composition of claim 1, comprising a prepreg, a resin film, a laminate, or a printed circuit board.

10. The article as claimed in claim 9, having one, more, or all of the following characteristics: a glass transition temperature greater than or equal to 211°C as measured by the method described in IPC-TM-650 2.4.24.5; a Z-axis coefficient of thermal expansion less than or equal to 47 ppm / °C as measured by the method described in IPC-TM-650 2.4.24.5; a dielectric constant less than or equal to 3.49 as measured by the method described in JIS C2565 at a frequency of 10 GHz; a dielectric loss less than or equal to 0.0046 as measured by the method described in JIS C2565 at a frequency of 10 GHz; a copper foil tensile strength greater than or equal to 4.01 lb / in as measured by the method described in UL94; and a flame retardancy rating of V-0 as measured by the method described in UL94.