A resin composition and an article thereof

Abstract

A resin composition includes a polyphenylene ether resin having a structure represented by Formula (1) and an additive. The additive can include a maleimide resin, a crosslinking agent containing an unsaturated carbon-carbon double bond, a polyolefin, a flame retardant, a filler, a hardening accelerator, or a combination thereof. In addition, an article made from the resin composition is disclosed. The aforementioned article includes a prepreg, a resin film, a laminate, or a printed circuit board, and can be improved in one or more of a relative tracking index, a breakdown voltage, a dielectric loss, and a copper foil pull strength.

Description

Technical Field

[0001] This invention relates primarily to a resin composition and articles made therefrom, particularly to a resin composition applicable to prepregs, resin films, laminates (e.g., copper foil substrates) and printed circuit boards, and articles made therefrom. Background Technology

[0002] In recent years, electronic technology has been developing towards higher integration, lower power consumption, and higher performance, thus placing higher demands on high-performance electronic materials. When the surface of insulating materials in high-performance electronic materials is contaminated by positive and negative ion pollutants, leakage current is easily generated on the surface of the insulating layer under the action of a certain voltage, which in turn leads to flashover discharge. The heat and electric sparks generated by the discharge arc can cause the surface of the insulating layer to ignite and carbonize, forming leakage channels and traces. This phenomenon is called tracking.

[0003] For printed circuit boards, the occurrence of tracking will lead to a decrease in insulation or even failure, which seriously affects the insulation safety and reliability of electronic products. Therefore, substrate materials with high comparative tracking index (CTI) are widely used in printed circuit boards used in humid and easily polluted environments.

[0004] However, with the development of technology, electronic and electrical products are becoming increasingly multifunctional and high-performance, and the circuits of printed circuit boards are becoming more complex and dense, with the number of layers trending towards multi-layer. Therefore, higher requirements are placed on the dielectric properties of the substrate.

[0005] Traditional high CTI FR-4 substrates use an epoxy resin and dicyandiamide curing system, resulting in extremely high dielectric loss. To maintain lower dielectric loss, vinyl polyphenylene ether resins are typically used, but the substrates made from these resins exhibit poor insulation performance. Therefore, there is an urgent need in the field to develop novel resin materials with high relative tracking index, especially those that can also achieve one or more of the following properties: breakdown voltage, copper foil tensile strength, and dielectric loss. Summary of the Invention

[0006] In view of the problems encountered in the prior art, especially the inability of existing materials to meet one or more of the above-mentioned technical requirements, the main objective of the present invention is to provide a resin composition that can overcome at least one of the above-mentioned technical problems. Furthermore, the present invention also provides an article made using this resin composition.

[0007] On one hand, the present invention provides a resin composition comprising a polyphenylene ether resin having the structure shown in formula (1) and additives;

[0008]

[0009] In equation (1), n ​​is an integer from 1 to 10, A1 has the structure shown in equation (2), and A2 each has the structure shown in equation (6), equation (7) or equation (8) independently;

[0010]

[0011] In equation (2), a and b are each independent integers from 0 to 100, and a and b are not both 0; -OXO- has the structure shown in equation (3) or equation (4); Y has the structure shown in equation (5);

[0012]

[0013] In formula (3), R1, R2, R7 and R8 are the same or different from each other, and each is independently a C1 to C6 alkyl group; R3, R4, R5 and R6 are the same or different from each other, and each is independently a hydrogen atom or a C1 to C6 alkyl group.

[0014]

[0015] In equation (4), R9, R 10 R 11 R 12 R 13 R 14 R 15 and R 16 They may be the same or different from each other, and each is independently a C1 to C6 alkyl or hydrogen atom; A is a C1 to C6 divalent hydrocarbon group;

[0016]

[0017] In equation (5), R 17 R 18 R 19 and R 20 They may be the same or different from each other, and each is independently a hydrogen atom or a C1 to C6 alkyl group;

[0018]

[0019] In equation (6), R 21 R 22 and R 23 Each is an independent hydrogen atom or a C1-C6 alkyl group; Q6 is a C1-C6 divalent alkyl group or does not exist;

[0020]

[0021] In equation (7), R 24R25 and R26 are each independently hydrogen atoms or C1-C6 alkyl groups; Q7 is a C1-C6 divalent alkyl group or does not exist.

[0022]

[0023] In equation (8), R 27 R 28 and R 29 Each atom is a hydrogen atom or a C1 to C6 alkyl group.

[0024] In one embodiment, for example, in formula (1), A2 each independently includes vinyl, (meth)acryloyl, allyl or vinylbenzyl.

[0025] In one embodiment, for example, the polyphenylene ether resin having the structure shown in formula (1) comprises: a polyphenylene ether resin having the structure shown in formula (9), a polyphenylene ether resin having the structure shown in formula (10), a polyphenylene ether resin having the structure shown in formula (11), a polyphenylene ether resin having the structure shown in formula (12), a polyphenylene ether resin having the structure shown in formula (13), a polyphenylene ether resin having the structure shown in formula (14), or a combination thereof:

[0026]

[0027]

[0028] In one embodiment, for example, the additive includes maleimide resin, crosslinking agent containing unsaturated carbon-carbon double bonds, polyolefin, flame retardant, filler, curing accelerator, or a combination thereof.

[0029] In one embodiment, for example, the resin composition comprises 100 parts by weight of the polyphenylene ether resin having the structure shown in formula (1) and 0.1 to 350 parts by weight of the additive.

[0030] In one embodiment, for example, the additive comprises 5 to 30 parts by weight of maleimide resin, 15 to 50 parts by weight of a crosslinking agent containing unsaturated carbon-carbon double bonds, 15 to 30 parts by weight of polyolefin or a combination thereof.

[0031] In one embodiment, for example, the resin composition may further optionally include benzoxazine resin, epoxy resin, silicone resin, cyanate ester resin, reactive ester, phenolic resin, styrene-maleic anhydride, amine curing agent, polyamide, polyimide, polymerization inhibitor, silane coupling agent, surfactant, dye, toughening agent, solvent, or a combination thereof.

[0032] On the other hand, the present invention provides an article made from the aforementioned resin composition, comprising a prepreg, a resin film, a laminate, or a printed circuit board.

[0033] In one embodiment, for example, the aforementioned article has one, more, or all of the following characteristics:

[0034] The relative tracking index of the product, measured according to the method described in ASTM D3638, is greater than or equal to 300V.

[0035] The breakdown voltage of the product measured according to the method described in IPC-TM-650 2.5.6.3 is greater than or equal to 40kV;

[0036] The dielectric loss of the product, measured at a frequency of 10 GHz according to the method described in JIS C2565, is less than or equal to 0.0047; and

[0037] The copper foil tensile strength of the product, measured according to the method described in IPC-TM-650 2.4.8, is greater than or equal to 2.80 lb / in. Detailed Implementation

[0038] To enable those skilled in the art to understand the features and effects of this application, the terms and expressions used in the specification and claims are explained and defined in general below. Unless otherwise specified, all technical and scientific terms used herein have the ordinary meaning understood by those skilled in the art in this application, and in case of conflict, the definitions in this specification shall prevail.

[0039] The theories or mechanisms described and disclosed herein, whether right or wrong, shall not in any way limit the scope of this application, that is, the content of this application may be implemented without being limited by any particular theory or mechanism.

[0040] In this document, "this application" means "this invention" or "this disclosure".

[0041] The terms “a,” “an,” “a,” or similar expressions are used herein to describe the components and technical features described in this application. Such descriptions are merely for convenience and to provide a general meaning for the scope of this application. Therefore, such descriptions should be understood to include one or at least one, and the singular includes the plural, unless clearly otherwise indicated.

[0042] In this article, "or a combination thereof" means "or any combination thereof", and "any one", "any kind", "any one" means "any one", "any kind", "any one".

[0043] 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 thereof containing multiple elements is not limited to the elements listed herein, but may also include other elements not explicitly listed but typically inherent to the composition or article thereof. Furthermore, unless explicitly stated to the contrary, the term “or” is an inclusive “or,” not an exclusive “or.” For example, the condition “A or B” is satisfied in any of the following cases: A is true (or exists) and B is false (or does not exist); A is false (or does not exist) and B is true (or exists); or both A and B are true (or exist). Furthermore, in this article, the interpretation of the terms “contains,” “includes,” “has,” and “contains” should be considered as having been specifically disclosed and simultaneously covering closed conjunctions such as “composed of,” “consisting of,” and “remaining as,” as well as conjunctions such as “essentially composed of,” “mainly composed of,” “mainly composed of,” “basically containing,” “basically composed of,” “basically composed of,” and “essentially containing.”

[0044] In this document, all features or conditions defined in the form of numerical ranges or percentage ranges, such as numerical values, quantities, contents, and concentrations, are for the sake of brevity and convenience only. Accordingly, descriptions of numerical ranges or percentage ranges should be considered as covering and specifically disclosing all possible subranges and individual numerical values ​​(including integers and fractions) within the ranges, especially integer values. For example, range descriptions such as "1.0 to 8.0," "between 1.0 and 8.0," or "between 1.0 and 8.0" should be considered as specifically disclosing all subranges such as 1.0 to 8.0, 1.0 to 7.0, 2.0 to 8.0, 2.0 to 6.0, 3.0 to 6.0, 4.0 to 8.0, 3.0 to 8.0, etc., and should be considered as covering endpoint values, especially subranges defined by integer values, and should be considered as specifically disclosing individual numerical values ​​within the ranges such as 1.0, 2.0, 3.0, 4.0, 5.0, 6.0, 7.0, 8.0, etc. Unless otherwise specified, the foregoing interpretation applies to all contents of this application, whether extensive or not.

[0045] If a quantity, concentration, or other numerical value or parameter is expressed as a range, preferred range (or better range), or a series of upper and lower limits, it should be understood that this document has specifically disclosed all ranges consisting of any pair of upper or preferred values ​​(or better values) and lower or preferred values ​​(or better values) of that range, regardless of whether such ranges are separately disclosed. Furthermore, when referring to ranges of numerical values ​​herein, unless otherwise stated, the range should include its endpoints and all integers and fractions within the range.

[0046] In this document, numerical values ​​are to be understood as having a precision with significant digits, provided that the purpose of the invention can be achieved. For example, the number 40.0 should be understood to cover the range of 39.50 to 40.49.

[0047] In this document, when Markush groups or alternative terms are used to describe features or instances of this application, those skilled in the art should understand that subgroups or any individual elements within a Markush group or option list can also be used to describe this application. For example, if X is described as "selected from the group consisting of X1, X2, and X3," it also indicates that claims that X is X1 and claims 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 instances of this application, those skilled in the art should understand that any combination of subgroups or individual members within a Markush group or option list can also be used to describe this application. 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 and / or X2 and / or X3 and Y is Y1 and / or Y2 and / or Y3 has been fully described.

[0048] Unless otherwise specified, in this application, a compound refers to a chemical substance formed by two or more elements linked by chemical bonds, including, but not limited to, small molecule compounds and macromolecules. The term "compound" in this document is not limited to a single chemical substance, but can also be interpreted as a class of chemical substances having the same composition or the same properties.

[0049] Unless otherwise specified, in this application, a polymer refers to the 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 can include homopolymers, copolymers, prepolymers, etc., but are not limited to these. A homopolymer is a polymer polymerized from a single monomer. Copolymers 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. For example, the styrene-butadiene copolymer in this application can be interpreted as a styrene-butadiene random copolymer, a styrene-butadiene alternating copolymer, a styrene-butadiene graft copolymer, or a styrene-butadiene block copolymer. Prepolymers are polymers with lower molecular weights, falling between those of monomers and the final polymer. Prepolymers contain reactive functional groups that allow for further polymerization to yield fully cross-linked or hardened products with higher molecular weights. Polymers include, but are not limited to, oligomers. Oligomers, also known as low-molecular-weight polymers, are polymers composed of 2 to 20 repeating units, typically 2 to 5 repeating units.

[0050] Unless otherwise specified, "resin" in this application is a common name for a synthetic polymer, and in interpretation, 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.

[0051] Unless otherwise specified, in this application, modified products include products after modification of the reactive functional groups of each resin, products after prepolymerization of each resin with other resins, products after crosslinking of each resin with other resins, products after copolymerization of each resin with other resins, etc.

[0052] Unless otherwise specified, the unsaturated bond referred to in this application refers to a reactive unsaturated bond, such as, but not limited to, an unsaturated double bond that can undergo cross-linking reactions with other functional groups, such as, but not limited to, an unsaturated carbon-carbon double bond that can undergo cross-linking reactions with other functional groups.

[0053] The unsaturated carbon-carbon double bonds described in this application are preferably, but are not limited to, vinyl, vinylbenzyl, (meth)acryloyl, allyl, or combinations thereof. When interpreting vinyl, it should include both vinyl and vinylidene. When interpreting (meth)acryloyl, it should include both acryloyl and methacryloyl.

[0054] Unless otherwise specified, the hydrocarbon groups described in this application include, but are not limited to, alkyl, alkenyl, or alkynyl groups, and are interpreted to include their various isomers. For example, C1-C6 divalent hydrocarbon groups are interpreted to include C1-C6 divalent straight-chain hydrocarbon groups, C2-C6 divalent branched hydrocarbon groups, or C3-C6 divalent cyclic hydrocarbon groups. As another example, propyl should be interpreted to include n-propyl and isopropyl.

[0055] Unless otherwise specified, in this application, parts by weight represent the relative number of parts by weight in the composition, and can be any unit of weight, such as, but not limited to, kilograms, grams, pounds, etc. For example, 100 parts by weight of polyphenylene ether resin means that it can be 100 kilograms of polyphenylene ether resin or 100 pounds of polyphenylene ether resin.

[0056] It should be understood that the features disclosed in the various embodiments herein can be arbitrarily combined to form the technical solution of this application, as long as there is no contradiction in the combination of these features.

[0057] The present application will be described below with reference to specific embodiments and examples. It should be understood that these specific embodiments and examples are merely illustrative and are not intended to limit the scope or use of the present application. Unless otherwise stated, the methods, reagents, and conditions used in the examples are conventional methods, reagents, and conditions in the art.

[0058] This application discloses a resin composition comprising a polyphenylene ether resin having the structure shown in formula (1) and an additive;

[0059]

[0060] In equation (1), n ​​is an integer from 1 to 10 (e.g., 1, 2, 3, 4, 5, 6, 7, 8, 9 or 10), A1 has the structure shown in equation (2), and A2 each has the structure shown in equation (6), equation (7) or equation (8).

[0061]

[0062] In equation (2), a and b are each independently an integer from 0 to 100 (e.g., 0, 10, 20, 30, 40, 50, 60, 70, 80, 90 or 100, preferably each independently an integer from 1 to 30, more preferably each independently an integer from 1 to 10), and a and b are not both 0; -OXO- has the structure shown in equation (3) or equation (4); Y each independently has the structure shown in equation (5);

[0063]

[0064] In formula (3), R1, R2, R7 and R8 are the same or different from each other, and each is independently a C1 to C6 alkyl (e.g., C1 to C3 alkyl, e.g., methyl); R3, R4, R5 and R6 are the same or different from each other, and each is independently a hydrogen atom or a C1 to C6 alkyl (e.g., C1 to C3 alkyl, e.g., methyl);

[0065]

[0066] In equation (4), R9, R 10 R 11 R 12 R 13 R 14 R 15 and R 16 They may be the same or different from each other, and each is independently a C1 to C6 alkyl group (e.g., C1 to C3 alkyl group, e.g., methyl) or a hydrogen atom; A is a C1 to C6 divalent hydrocarbon group (e.g., methylene, ethylene, propylene, etc., for example, A can be -CH2- or -C(CH3)2-);

[0067]

[0068] In equation (5), R 17 R 18 R 19 and R 20 They may be the same as or different from each other, and each is independently a hydrogen atom or a C1-C6 alkyl group (e.g., C1-C3 alkyl group, e.g., methyl).

[0069]

[0070] In equation (6), R 21 R 22 and R 23 Each is independently a hydrogen atom or a C1-C6 alkyl group (e.g., C1-C3 alkyl group, such as methyl); Q6 is a C1-C6 divalent alkyl group (e.g., methylene, ethylene, propylene, etc.) or is not present;

[0071]

[0072] In equation (7), R 24 R 25 and R 26 Each is independently a hydrogen atom or a C1-C6 alkyl group (e.g., C1-C3 alkyl group, such as methyl); Q7 is a C1-C6 divalent alkyl group (e.g., methylene, ethylene, propylene, etc.) or is not present;

[0073]

[0074] In equation (8), R 27 R 28 and R 29 Each is independently a hydrogen atom or a C1-C6 alkyl group (e.g., C1-C3 alkyl group, such as methyl).

[0075] In one embodiment, for example, in formula (1), A2 each independently includes vinyl, (meth)acryloyl, allyl or vinylbenzyl.

[0076] In one embodiment, for example, the polyphenylene ether resin having the structure shown in formula (1) comprises: a polyphenylene ether resin having the structure shown in formula (9), a polyphenylene ether resin having the structure shown in formula (10), a polyphenylene ether resin having the structure shown in formula (11), a polyphenylene ether resin having the structure shown in formula (12), a polyphenylene ether resin having the structure shown in formula (13), a polyphenylene ether resin having the structure shown in formula (14), or a combination thereof:

[0077]

[0078]

[0079] The number-average molecular weight (Mn) of the polyphenylene ether resin having the structure shown in formula (1) described in this application is preferably 3,000 to 25,000, more preferably 4,000 to 20,000, and even more preferably 4,000 to 5,000, but is not limited thereto.

[0080] The polyphenylene ether resin having the structure shown in Formula (1) described in this application can be prepared by the following method: (1) reacting a double-terminated amino polyphenylene ether resin (having the structure shown in Formula (15), where A1 is defined as described above), phthalaldehyde, and aminophenol at a controlled reaction temperature of 60 to 120°C and a reaction time of 1 to 8 hours to obtain an intermediate product; and (2) adding a halide containing an unsaturated carbon-carbon double bond (a halide having the structure shown in Formula (6), Formula (7), or Formula (8)) to the intermediate product and reacting it at a controlled reaction temperature of 60 to 120°C and a reaction time of 1 to 6 hours to obtain the polyphenylene ether resin having the structure shown in Formula (1).

[0081]

[0082] Optionally, an appropriate amount of solvent may be added in step (1) above, such as, but not limited to, ketone compounds (e.g., acetone or butanone), toluene or a combination thereof, preferably toluene.

[0083] Optionally, an alkaline solution may be further added in step (2) above, such as, but not limited to, sodium hydroxide solution, potassium hydroxide solution, triethylamine, potassium tert-butoxide or a combination thereof, preferably sodium hydroxide solution.

[0084] In the aforementioned steps, the molar ratio of the diamino-terminated polyphenylene ether resin (having the structure shown in formula (15), A1 as defined above), benzoxaldehyde, aminophenol, and halides containing unsaturated carbon-carbon double bonds (halides having the structure shown in formula (6), formula (7), or formula (8)) is not particularly limited. For example, but not limited to, the amount of benzoxaldehyde added is 1 to 5 moles, the amount of aminophenol added is 0.5 to 5.5 moles, and the amount of halides containing unsaturated carbon-carbon double bonds (halides having the structure shown in formula (6), formula (7), or formula (8)) added is 2 to 8 moles, compared to 1 mole of diamino-terminated polyphenylene ether resin (having the structure shown in formula (15), A1 as defined above). Preferably, compared to 1 mole of a diamino-terminated polyphenylene ether resin (having the structure shown in formula (15), where A1 is defined as described above), the amount of phthalaldehyde added is 2 to 4 moles, the amount of aminophenol added is 1.5 to 4.5 moles, and the amount of halide containing unsaturated carbon-carbon double bonds (halides having the structures shown in formula (6), formula (7), or formula (8)) added is 3 to 7 moles.

[0085] The aforementioned dual-amino-terminated polyphenylene ether resin (having the structure shown in formula (15), with A1 defined as described above) is not particularly limited and includes various commercially available or homemade products. For example, but not limited to those purchased from Sabic.

[0086] The aforementioned phthalaldehyde is not particularly limited and includes various commercially available products. For example, but not limited to terephthalaldehyde, o-phthalaldehyde, m-phthalaldehyde, or combinations thereof, with terephthalaldehyde being preferred.

[0087] The aforementioned aminophenol is not particularly limited and includes various commercially available products. For example, but not limited to, p-aminophenol, o-aminophenol, m-aminophenol, or combinations thereof, with p-aminophenol being preferred.

[0088] The aforementioned halides containing unsaturated carbon-carbon double bonds (halides having the structures shown in formula (6), (7), or (8)) are not particularly limited and include various commercially available products. Examples include, but are not limited to, chloromethylstyrene, vinyl chloride, allyl chloride, acryloxyl chloride, methacryloyl chloride, or combinations thereof. Chloromethylstyrene may include, for example, but not limited to, 4-chloro-methylstyrene, 3-chloro-methylstyrene, 2-chloro-methylstyrene, or combinations thereof.

[0089] Unless otherwise specified, the amount of each component added in the resin composition described in this application is calculated based on a total of 100 parts by weight of polyphenylene ether resin having the structure shown in formula (1), and the amount of additives added is not particularly limited. For example, but not limited to, the total amount of additives (which may be one or more) added may be from 0.1 parts by weight to 350 parts by weight, more preferably from 50 parts by weight to 300 parts by weight, and more preferably from 100 parts by weight to 230 parts by weight, compared to a total of 100 parts by weight of polyphenylene ether resin having the structure shown in formula (1). For example, the total amount of additives added can be 0.1, 0.3, 0.5, 1, 5, 10, 15, 20, 30, 40, 50, 60, 70, 80, 90, 100, 120, 150, 200, 250, 300, or 350 parts by weight relative to a total of 100 parts by weight of polyphenylene ether resin having the structure shown in formula (1). If more than two additives are used, the ratio between the additives can be adjusted as needed.

[0090] In one embodiment, for example, the resin composition comprises 100 parts by weight of the polyphenylene ether resin having the structure shown in formula (1) and 0.1 to 350 parts by weight of the additive.

[0091] In one embodiment, for example, the additive includes maleimide resin, crosslinking agent containing unsaturated carbon-carbon double bonds, polyolefin, flame retardant, filler, curing accelerator, or a combination thereof.

[0092] In one embodiment, for example, the additive includes fillers and hardening accelerators.

[0093] In one embodiment, for example, the additive includes maleimide resin, a crosslinking agent containing unsaturated carbon-carbon double bonds, a filler, and a curing accelerator.

[0094] In one embodiment, for example, the additive includes maleimide resin, crosslinking agent containing unsaturated carbon-carbon double bonds, polyolefin, flame retardant, filler, and curing accelerator.

[0095] For example, unless otherwise specified, the amount of maleimide resin added may be from 1 part to 40 parts by weight relative to a total of 100 parts by weight of polyphenylene ether resin having the structure shown in formula (1), preferably from 5 parts to 30 parts by weight.

[0096] The maleimide resin used in the resin composition described in this application is not particularly limited and may be any one or more maleimide resins suitable for the manufacture of prepregs, resin films, laminates or printed circuit boards. In some embodiments, the maleimide resin includes, but is not limited to, 4,4'-diphenylmethane bismaleimide, polyphenylmethanemaleimide (or oligomer of phenylmethane 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. bismaleimide, m-phenylene bismaleimide, 4-methyl-1,3-phenylene bismaleimide, 1,6-bismaleimide-(2,2,4-trimethyl)hexane, N-2,3-xylylmaleimide, N-2,6-xylylmaleimide, N-phenylmaleimide, vinyl benzyl maleimide Maleimide (VBM), maleimides containing biphenyl structures, maleimide resins containing aliphatic long-chain structures, prepolymers of diallyl compounds and maleimide resins, prepolymers of diamines and maleimide resins, prepolymers of polyfunctional amines and maleimide resins, prepolymers of acidic phenolic compounds and maleimide resins, or combinations thereof. Modifications of these components are also included in the interpretation.

[0097] For example, maleimide resins such as, but not limited to, those with trade names 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 manufactured by Daiwakasei Industry Co., Ltd., or those with trade names BMI-70, BMI-80 and others manufactured by KI Chemical Co., Ltd., or those with trade names MIR-3000 or MIR-5000 manufactured by Nippon Kayaku Co., Ltd.

[0098] For example, maleimide resins containing aliphatic long-chain structures, or imide-elongated maleimide resins, may include various imide-elongated maleimide resins disclosed in Taiwan Patent Application Publication No. TW200508284A, all of which are incorporated herein by reference. Maleimide resins containing aliphatic long-chain structures applicable to this application include, but are not limited to, maleimide resins manufactured by the designer's subsidiaries under trade names such as BMI-689, BMI-1400, BMI-1500, BMI-1700, BMI-2500, BMI-3000, BMI-5000, and BMI-6000.

[0099] For example, unless otherwise specified, the amount of the crosslinking agent containing unsaturated carbon-carbon double bonds added may be from 1 part to 60 parts by weight relative to a total of 100 parts by weight of polyphenylene ether resin having the structure shown in formula (1), preferably from 15 parts by weight to 50 parts by weight.

[0100] For example, the crosslinking agent containing unsaturated carbon-carbon double bonds is 1,2-bis(vinylphenyl)ethane, divinylbenzyl ether, divinylbenzene, divinylnaphthalene, divinylbiphenyl, tert-butylstyrene, triallyl isocyanurate, triallyl cyanurate, 1,2,4-trivinylcyclohexane, diallyl bisphenol A, styrene, butadiene, decanadiene, octadiene, vinylcarbazole, acrylates, or combinations thereof. Isomers or polymers of these components are also included in the interpretation.

[0101] For example, unless otherwise specified, the amount of polyolefin added may be from 1 part to 40 parts by weight relative to a total of 100 parts by weight of polyphenylene ether resin having the structure shown in formula (1), preferably from 15 parts by weight to 30 parts by weight.

[0102] The types of polyolefins applicable to this application are not particularly limited, and may be any one or more olefin polymers suitable for the manufacture of prepregs, resin films, laminates or printed circuit boards, and may be any one or more commercially available products, homemade products or combinations thereof.

[0103] For example, polyolefins may include, but are not limited to, diene polymers, monoene polymers, hydrogenated diene polymers, or combinations thereof. The diene is a hydrocarbon compound containing two unsaturated carbon-carbon double bonds, and the monoene is a hydrocarbon compound containing one unsaturated carbon-carbon double bond. The number-average molecular weight of polyolefins is typically between 1,000 and 150,000. Due to their large molecular weight and the regular, repeating arrangement of carbon-carbon bonds in their main chain, polyolefins have low molecular polarity, which can improve the dielectric properties of the cured product.

[0104] In some embodiments, specific examples of polyolefins include, but are not limited to: polybutadiene, polyisoprene, styrene-butadiene copolymer, styrene-isoprene copolymer, styrene-butadiene-divinylbenzene terpolymer, styrene-butadiene-maleic anhydride terpolymer, vinyl-polybutadiene-urea oligomer, maleic anhydride-butadiene copolymer, polymethylstyrene, hydrogenated polybutadiene, hydrogenated styrene-butadiene-divinylbenzene terpolymer, hydrogenated styrene-butadiene-maleic anhydride terpolymer, hydrogenated styrene-butadiene copolymer, hydrogenated styrene-isoprene copolymer, or combinations thereof. Modifications of these components are also included in the interpretation.

[0105] In some embodiments, the polyolefin is preferably a butadiene-based or isoprene-based diene polymer, a hydrogenated butadiene-based or hydrogenated isoprene-based hydrogenated diene polymer, or a combination thereof. Specific examples include, but are not limited to: polybutadiene, hydrogenated polybutadiene, polyisoprene, styrene-butadiene copolymer, hydrogenated styrene-butadiene copolymer, styrene-isoprene copolymer, hydrogenated styrene-isoprene copolymer, styrene-butadiene-divinylbenzene terpolymer, styrene-butadiene-maleic anhydride terpolymer, hydrogenated styrene-butadiene-divinylbenzene terpolymer, hydrogenated styrene-butadiene-maleic anhydride terpolymer, vinyl-polybutadiene-urea oligomer, maleic anhydride-butadiene copolymer, or a combination thereof.

[0106] For example, unless otherwise specified, the amount of the flame retardant added may be from 1 part to 65 parts by weight relative to a total of 100 parts by weight of polyphenylene ether resin having the structure shown in formula (1), preferably from 10 parts by weight to 55 parts by weight.

[0107] The flame retardant suitable for the resin composition described in this application may be any one or more flame retardants suitable for the manufacture of prepregs, resin films, laminates, or printed circuit boards, such as, but not limited to, bromine-containing flame retardants or phosphorus-containing flame retardants. Bromine-containing flame retardants preferably include decabromodiphenyl ethane, and phosphorus-containing flame retardants preferably include ammonium polyphosphate, p-hydroquinone bis-(diphenyl phosphate), bisphenol A bis-(diphenyl phosphate), tri(2-carboxyethyl) phosphine (TCEP), trichloroisopropyl phosphate, trimethyl phosphate (TMP), dimethyl methyl phosphonate (DMMP), resorcinol bis(dixylenyl phosphate), and RDXP (such as PX-200). Commercially available products such as PX-201 and PX-202), phosphazene compounds (such as SPB-100, SPH-100, and SPV-100), melamine polyphosphate, 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (DOPO) and its derivatives or resins, diphenylphosphine oxide (DPPO) and its derivatives or resins, melamine cyanurate and tri-hydroxyethylisocyanurate, aluminum phosphonates (such as OP-930 and OP-935), or combinations thereof.

[0108] For example, DPPO compounds can be bisDPPO compounds. DOPO compounds can be bisDOPO compounds, DOPO-HQ, DOPO-NQ, or vinyl-containing DOPO compounds. DOPO resins include, but are not limited to, DOPO-bonded phenolic resins or DOPO-bonded epoxy resins, wherein DOPO-bonded phenolic resins include, but are not limited to, DOPO-phenolic resins (DOPO-PN), DOPO-bisphenol A phenolic resins (DOPO-bisphenol A novolac, DOPO-BPAN), DOPO-bisphenol F phenolic resins (DOPO-bisphenol F novolac, DOPO-BPFN), or DOPO-bisphenol S phenolic resins (DOPO-bisphenol Snovolac, DOPO-BPSN), etc., and other bisphenolic resins.

[0109] Preferably, the flame retardant is a DOPO compound or its derivatives, or a resin, phosphate ester, or a combination thereof.

[0110] For example, unless otherwise specified, the amount of filler added may be from 10 parts by weight to 210 parts by weight relative to a total of 100 parts by weight of polyphenylene ether resin having the structure shown in formula (1), preferably from 20 parts by weight to 200 parts by weight.

[0111] The fillers used in this application may be any one or more inorganic or organic fillers suitable for the fabrication of prepregs, resin films, laminates, or printed circuit boards. Specific examples of inorganic fillers include, but are not limited to: silica (molten, non-molten, porous, or hollow), alumina, aluminum hydroxide, magnesium oxide, magnesium hydroxide, calcium carbonate, aluminum nitride, boron nitride, silicon aluminum carbide, silicon carbide, titanium dioxide, barium titanate, lead titanate, strontium titanate, calcium titanate, magnesium titanate, barium zirconate, lead zirconate, magnesium zirconate, lead zirconate titanate, zinc molybdate, calcium molybdate, magnesium molybdate, zinc molybdate-modified talc, zinc oxide, zirconium oxide, mica, boehmite (AlOOH), calcined talc, talc, silicon nitride, calcined kaolin, or combinations thereof. Furthermore, inorganic fillers may be spherical (including solid or hollow spheres), fibrous, plate-like, granular, flake-like, or needle-like, and may be selectively pretreated with a silane coupling agent. Specific examples of organic fillers include, but are not limited to: polytetrafluoroethylene, polyphenylene sulfide, polyethersulfone, or combinations thereof.

[0112] For example, unless otherwise specified, the amount of the curing accelerator added may be from 0.1 parts by weight to 2.0 parts by weight relative to a total of 100 parts by weight of polyphenylene ether resin having the structure shown in formula (1), preferably from 0.5 parts by weight to 1.8 parts by weight.

[0113] The curing accelerators applicable to this application may include catalysts such as Lewis bases or Lewis acids. Lewis bases may include imidazole, boron trifluoride amine complexes, ethyltriphenylphosphonium chloride, 2-methylimidazole (2MI), 2-phenyl-1H-imidazole (2PZ), 2-ethyl-4-methylimidazole (2E4MI), triphenylphosphine (TPP), and 4-dimethylaminopyridine (DMAP), or combinations thereof. Lewis acids may include metal salt compounds, such as manganese, iron, cobalt, nickel, copper, zinc, etc., and metal catalysts such as zinc octanoate and cobalt octanoate. Curing accelerators also include curing initiators, which include various compounds that can generate free radicals, such as peroxides. Curing initiators include, but are not limited to: dibenzoyl peroxide (BPO), dicumyl peroxide, 2,5-dimethyl-2,5-di(tert-butylperoxy)hexane, 2,5-dimethyl-2,5-di(tert-butylperoxy)-3-hexyne (25B), di-tert-butyl peroxide, di(tert-butylperoxyisopropyl)benzene, di(tert-butylperoxy)phthalate, di(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, lauroyl peroxide, tert-hexyl peroxypentanoate, dibutyl peroxyisopropylbenzene, bis(4-tert-butylcyclohexyl) peroxydicarbonate, or combinations thereof.

[0114] For example, in one embodiment, the resin composition of the present invention, in addition to comprising 100 parts by weight of a polyphenylene ether resin having the structure shown in formula (1), also comprises 5 to 30 parts by weight of a maleimide resin, 15 to 50 parts by weight of a crosslinking agent containing unsaturated carbon-carbon double bonds, 15 to 30 parts by weight of a polyolefin or a combination thereof.

[0115] For example, in one embodiment, the resin composition of the present invention further comprises benzoxazine resin, epoxy resin, silicone resin, cyanate ester resin, reactive ester, phenolic resin, styrene-maleic anhydride, amine curing agent, polyamide, polyimide, polymerization inhibitor, silane coupling agent, surfactant, dye, toughening agent, solvent, or combination thereof. Modifications of these components are also included in the interpretation.

[0116] For example, unless otherwise specified, the amount of any one of the following components added, relative to a total of 100 parts by weight of polyphenylene ether resin having the structure shown in formula (1), may be from 1 part by weight to 200 parts by weight (e.g., but not limited to 1, 5, 10, 15, 20, 30, 40, 50, 60, 70, 80, 90, 100, 120, 150 or 200 parts by weight), and the ratio between them may be adjusted as needed. Unless otherwise specified, the amount of any one of the following components, such as the polymerization inhibitor, silane coupling agent, surfactant, dye and toughening agent, may be from 1 part by weight to 20 parts by weight (e.g., but not limited to 1, 5, 10, 15 or 20 parts by weight) relative to a total of 100 parts by weight of polyphenylene ether resin having the structure shown in formula (1), and the ratio between them may be adjusted as needed.

[0117] Examples of benzoxazine resins suitable for the resin compositions described in this application are not particularly limited and may include various benzoxazine resins known in the art, including but not limited to bisphenol A type benzoxazine resins, bisphenol F type benzoxazine resins, phenolphthalein type benzoxazine resins, dicyclopentadiene type benzoxazine resins, phosphorus-containing benzoxazine resins, diamine type benzoxazine resins, vinyl-containing benzoxazine resins, or combinations thereof. The diamine type benzoxazine resins include diaminodiphenyl ether type benzoxazine resins, diaminobisphenol F type benzoxazine resins, diaminobiphenyl type benzoxazine resins, or combinations thereof. For example, the benzoxazine resin may include, but is not limited to, benzoxazine resins manufactured by Huntsman under the trade names LZ-8260, LZ-8270, LZ-8280, LZ-8290 or LPY 11051, benzoxazine resins manufactured by Changchun Resin under the trade name PF-3500, or benzoxazine resins manufactured by Showa Polymer Co., Ltd. under the trade name HFB-2006M.

[0118] The epoxy resin suitable for the resin composition described in this application may be any type of epoxy resin known in the art, including but not limited to bisphenol A epoxy resin, bisphenol F epoxy resin, bisphenol S epoxy resin, bisphenol AD ​​epoxy resin, phenolic (novolac) epoxy resin, trifunctional epoxy resin, tetrafunctional epoxy resin, multifunctional epoxy resin, dicyclopentadiene (DCPD) epoxy resin, phosphorus-containing epoxy resin, p-xylene epoxy resin, naphthalene-type epoxy resin (e.g., naphthol-type epoxy resin), benzofuran-type epoxy resin, and isocyanate-modified epoxy resin. Among them, the phenolic epoxy resin may be phenol novolac epoxy resin, bisphenol A novolac epoxy resin, bisphenol F novolac epoxy resin, biphenyl novolac epoxy resin, phenol benzaldehyde epoxy resin, phenol aralkyl novolac epoxy resin, or o-cresol novolac epoxy resin; among them, the phosphorus-containing epoxy resin may be DOPO epoxy resin, DOPO-HQ epoxy resin, or a combination thereof. The aforementioned DOPO epoxy resin may include DOPO-containing phenol novolac epoxyresin, DOPO-containing o-cresol novolac epoxyresin, DOPO-containing bisphenol-A novolac epoxyresin, or combinations thereof; the aforementioned DOPO-HQ epoxy resin may include DOPO-HQ-containing phenol novolac epoxy resin, DOPO-HQ-containing o-cresol novolac epoxy resin, DOPO-HQ-containing bisphenol-A novolac epoxy resin, or combinations thereof.

[0119] The silicone resin suitable for the resin composition described in this application may be any type of silicone resin known in the art, including but not limited to polyalkyl silicone resin, polyaryl silicone resin, polyalkylaryl silicone resin, modified silicone resin or a combination thereof. Preferably, the silicone resin applicable to this application is an amino-modified silicone resin, such as, but not limited to, amino-modified silicone resins produced by Shin-Etsu Chemical Industry Co., Ltd. under trade names KF-8010, X-22-161A, X-22-161B, KF-8012, KF-8008, X-22-9409, X-22-1660B-3, etc.; amino-modified silicone resins produced by Toray-Dow Coming Co., Ltd. under trade names BY-16-853U, BY-16-853, BY-16-853B, etc.; amino-modified silicone resins produced by Momentive Performance Materials JAPAN Co., Ltd. under trade names XF42-C5742, XF42-C6252, XF42-C5379, etc., or combinations thereof.

[0120] There are no particular limitations on the cyanate resins suitable for the resin compositions described in this application; any cyanate resin having an Ar-OC≡N structure is acceptable, wherein Ar can be a substituted or unsubstituted aromatic group. The cyanate resins of this application include, but are not limited to, phenolic cyanate resins, bisphenol A cyanate resins, bisphenol F cyanate resins, cyanate resins containing a dicyclopentadiene structure, cyanate resins containing a naphthalene ring structure, phenolphthalein cyanate resins, adamantane cyanate resins, fluorene cyanate resins, or combinations thereof. Among these, phenolic cyanate resins may include bisphenol A phenolic cyanate resins, bisphenol F phenolic cyanate resins, phenolic cyanate resins, or combinations thereof. The aforementioned cyanate ester resins include, but are not limited to, cyanate ester resins produced by Arxada AG under trade names such as primaset PT-15, PT-30S, PT-60S, BA-200, BA-230S, BA-3000S, BTP-2500, BTP-6020S, DT-4000, DT-7000, ULL-950S, HTL-300, CE-320, LVT-50, and LeCy.

[0121] The active ester suitable for the resin composition described in this application can be any type of active polyester resin known in the art, including but not limited to various commercially available active polyester resin products. For example, but not limited to, active polyester resins manufactured by Dai Nippon Ink Chemical under the trade names HPC-8000 and HPC-8150.

[0122] The phenolic resins suitable for the resin compositions described in this application include, but are not limited to, monofunctional, difunctional, or polyfunctional phenolic resins, including all phenolic resins known to be used in resin compositions for making prepregs, such as phenolic resins, phenoloxy resins, phenolic resins, etc. Phenolic resins include phenolic resins, o-methylphenolic resins, or bisphenol A resins.

[0123] The styrene-maleic anhydride suitable for the resin composition described in this application can be any type of styrene-maleic anhydride known in the art, wherein the ratio of styrene (S) to maleic anhydride (MA) can be 1:1, 2:1, 3:1, 4:1, 6:1, 8:1, or 12:1. For example, the styrene-maleic anhydride suitable for this application is, but is not limited to, styrene-maleic anhydrides produced by Cray Valley under trade names such as SMA-1000, SMA-2000, SMA-3000, EF-30, EF-40, EF-60, and EF-80, or styrene-maleic anhydrides produced by Polyscope under trade names such as C400, C500, C700, and C900.

[0124] Amine curing agents suitable for the resin compositions described in this application include, but are not limited to, diaminodiphenyl sulfone, diaminodiphenylmethane, diaminodiphenyl ether, diaminodiphenyl sulfide, dicyandiamide, or combinations thereof.

[0125] The polyamide used in the resin composition described in this application may be any type of polyamide resin known in the art, including but not limited to various commercially available polyamide resin products.

[0126] The polyimide suitable for the resin composition described in this application may be any type of polyimide resin known in the art, including but not limited to various commercially available polyimide resin products.

[0127] The polymerization inhibitors suitable for the resin compositions described in this application serve to suppress the polymerization reaction. Specific examples are not particularly limited, and may include various molecular-type polymerization inhibitors, stable free radical-type polymerization inhibitors, or combinations thereof known in the art. For example, molecular-type polymerization inhibitors suitable for this application include, but are not limited to, phenolic compounds, quinone compounds, aromatic amine compounds, aromatic nitro compounds, sulfur-containing compounds, variable-valence metal chlorides, or combinations thereof. More specifically, molecular-type polymerization inhibitors suitable for this application include, but are not limited to, phenol, hydroquinone, 4-tert-butylcatechol, benzoquinone, chloroquinone, 1,4-naphthoquinone, trimethylquinone, aniline, nitrobenzene, Na₂S, FeCl₃, CuCl₂, or combinations thereof. For example, stable free radical-type polymerization inhibitors suitable for this application include, but are not limited to, 1,1-diphenyl-2-trinitrophenylhydrazine (DPPH), triphenylmethyl, or combinations thereof.

[0128] Silane coupling agents suitable for the resin compositions described in this application may include silane compounds (such as, but not limited to, siloxane compounds), specific examples including but not limited to aminosilane compounds, epoxide silane compounds, vinyl silane compounds, ester silane compounds, hydroxy silane compounds, isocyanate silane compounds, methacryloxy silane compounds, acryloyloxy silane compounds, or combinations thereof.

[0129] The types of surfactants suitable for use in the resin compositions described in this application are not particularly limited. The main function of adding surfactants in this application is to enable the filler to be uniformly dispersed in the resin composition.

[0130] Dyeing agents suitable for the resin compositions described in this application may include, but are not limited to, dyes or pigments.

[0131] The main function of adding toughening agents in this application is to improve the toughness of the resin composition. The types of toughening agents suitable for the resin compositions described in this application are not particularly limited. For example, toughening agents may include, but are not limited to, carboxyl-terminated butadiene acrylonitrile rubber (CTBN), core-shell rubber, etc.

[0132] The main function of adding solvents to the resin compositions of this application is to dissolve the various components in the resin composition, change the solid content of the resin composition, and adjust the viscosity of the resin composition. The types of solvents suitable for the resin compositions described in this application are not particularly limited. 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, propylene glycol methyl ether, dimethylformamide, dimethylacetamide, N-methylpyrrolidone, and other solvents or mixtures thereof.

[0133] The resin compositions of the various embodiments of this application can be processed into various articles, including but not limited to prepregs, resin films, laminates, or printed circuit boards, through various processing methods.

[0134] For example, the resin composition described in this application can be made into a prepreg.

[0135] In one embodiment, the prepreg of this application has a reinforcing material and a layer disposed on the reinforcing material, the layer being formed by heating the aforementioned resin composition to a semi-cured state (B-stage) at high temperature. The baking temperature for producing the prepreg is, for example, between 120°C and 180°C. The reinforcing material can be any of a fiber material, woven fabric, or nonwoven fabric, and the woven fabric is preferably glass fiber cloth. There are no particular limitations on the type of glass fiber cloth; it can be commercially available glass fiber cloth suitable for various printed circuit boards, such as E-type glass fiber cloth, D-type glass fiber cloth, S-type glass fiber cloth, T-type glass fiber cloth, L-type glass fiber cloth, or Q-type glass fiber cloth, wherein the fiber type includes yarn and roving, and the form can include open or closed fibers. The aforementioned nonwoven fabric preferably includes liquid crystal resin nonwoven fabric, such as, but not limited to, polyester nonwoven fabric, polyurethane nonwoven fabric, etc. The aforementioned woven fabric may also include liquid crystal resin woven fabric, such as, but not limited to, polyester woven fabric or polyurethane woven fabric, etc. 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 then undergoes subsequent heating and curing (C-stage) to form an insulating layer.

[0136] In one embodiment, the resin compositions are uniformly mixed to form a varnish, which is then placed in an impregnation tank. Fiberglass cloth is then immersed in the impregnation tank to allow the resin compositions to adhere to the fiberglass cloth. Finally, the cloth is heated and baked at an appropriate temperature until it reaches a semi-cured state, thus obtaining a semi-cured sheet.

[0137] For example, the resin composition article described in this application can also be a resin film, which is formed by baking and heating the resin composition to a semi-cured state. For example, the resin composition can be selectively coated onto a liquid crystal resin film, a polyethylene terephthalate film (PET film), or a polyimide film, and then baked at an appropriate temperature to a semi-cured state to form a resin film. Alternatively, the resin compositions of various embodiments of this application can be coated onto copper foil to ensure uniform adhesion, and then baked at an appropriate temperature to a semi-cured state to obtain a resin film.

[0138] For example, the resin composition described in this application 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 190°C and 220°C, preferably between 200°C and 210°C, and the curing time is 90 to 180 minutes, preferably 120 to 150 minutes. 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.

[0139] In one embodiment, the aforementioned multilayer board can be further processed into a printed circuit board.

[0140] One method for manufacturing the printed circuit board according to this application involves using a double-sided copper-clad laminate (e.g., product EM-827, available from Taikoo Electronics Materials) with a thickness of 28 mils and 1 ounce HTE (High Temperature Elongation) copper foil. After drilling, electroplating is performed to create electrical conductivity between the upper and lower copper foil layers. The upper and lower copper foil layers are then etched to form the inner layer circuitry. Next, the inner layer circuitry undergoes a browning roughening treatment to create a surface texture. Then, the copper foil, the aforementioned prepreg, the aforementioned inner layer circuit board, the aforementioned prepreg, and the copper foil are stacked sequentially, and heated in a vacuum lamination apparatus at a temperature of 190°C to 220°C for 90 to 180 minutes to cure the insulating layer material of the prepreg. Finally, various circuit board processes known in the art, such as blackening, drilling, and copper plating, are performed on the outermost copper foil to obtain the printed circuit board.

[0141] In one or more embodiments, the resin compositions disclosed in this application and various articles prepared therefrom preferably have one, more, or all of the following characteristics:

[0142] The relative tracking index, measured according to the method described in ASTM D3638, is greater than or equal to 300V, for example, the relative tracking index is between 300V and 400V.

[0143] The breakdown voltage measured according to the method described in IPC-TM-650 2.5.6.3 is greater than or equal to 40 kV, for example, the breakdown voltage is between 40 kV and 50 kV;

[0144] The dielectric loss measured at a frequency of 10 GHz according to the method described in JIS C2565 is less than or equal to 0.0047, for example, the dielectric loss is between 0.0038 and 0.0047; and

[0145] The copper foil tensile strength measured according to the method described in IPC-TM-650 2.4.8 is greater than or equal to 2.80 lb / in, for example, the copper foil tensile strength is between 2.80 lb / in and 3.80 lb / in.

[0146] This application prepares resin compositions of the examples according to the dosages in Tables 1 and 2, and resin compositions of the comparative examples according to the dosages in Table 3, and further prepares them into various test samples or articles.

[0147] The chemical reagents used in the following examples and comparative examples are as follows:

[0148] Polyphenylene ether resin having the structure shown in formula (1): Synthesis Examples 1 to 4, prepared by the applicant.

[0149] Other polyphenylene ether resins: Methacrylamide polyphenylene ether resin, trade name SA9000, purchased from Sabic.

[0150] Other polyphenylene ether resins: Vinyl benzyl polyphenylene ether resin, trade name OPE-2st, purchased from Mitsubishi Gas Chemical Company.

[0151] Other polyphenylene ether resins: diamino-PPO resin, having the structure shown in formula (16), where a and b are each an integer from 1 to 10, purchased from Sabic Corporation.

[0152]

[0153] Terephthalaldehyde: Trade name P837166, purchased from Maclean's.

[0154] p-Aminophenol: Trade name A800865, purchased from Maclean's.

[0155] 4-Chloro-methylstyrene: Trade name V875828, purchased from Maclean's.

[0156] Maleimide resin: 3,3'-dimethyl-5,5'-diethyl-4,4'-diphenylmethane bismaleimide, trade name BMI-70, purchased from KI Chemicals.

[0157] Maleimide resin: Bisphenol A diphenyl ether bismaleimide, trade name BMI-80, purchased from KI Chemicals.

[0158] Crosslinking agent containing unsaturated carbon-carbon double bonds: triallyl isocyanurate, trade name TAIC, purchased from Chin Yu Enterprise Co., Ltd.

[0159] Polyolefin: styrene-butadiene copolymer, trade name Ricon 100, purchased from Cray Valley.

[0160] Polyolefin: Polybutadiene, trade name B-3000, purchased from Japan Soda.

[0161] Polyolefin: Hydrogenated styrene-butadiene block copolymer, trade name H1052, purchased from Asahi Kasei.

[0162] Flame retardant: resorcinol bis-(xylyl phosphate), trade name PX-200, purchased from Daihachi Chemical, Japan.

[0163] Flame retardant: Vinyl-DOPO flame retardant with two-terminal vinyl benzyl groups, the structural formula of which is shown in formula (17), wherein Q1 to Q5 are each a hydrogen atom or a methyl group, and it was purchased from Jinyi Chemical.

[0164]

[0165] Filler: Spherical silica, trade name SC-2050 SXJ, purchased from Admatechs.

[0166] Packing material: Hexagonal boron nitride (h-BN), trade name CFP007ST, purchased from 3M.

[0167] Filler: Monocrystalline alumina, trade name AA5, purchased from Sumitomo Chemical.

[0168] Filler: Titanium dioxide, trade name HT0210, purchased from Suiye Industrial Co., Ltd.

[0169] Hardening accelerator: 2,5-dimethyl-2,5-di(tert-butylperoxy)-3-hexyne, trade name 25B, purchased from Nippon Oils & Fats Co., Ltd.

[0170] Hardening accelerator: dicumyl peroxide, trade name DCP, purchased from Xibao Biotechnology.

[0171] Solvents: Toluene and methyl ethyl ketone, both purchased from Sinopec.

[0172] [Table 1] Composition (parts by weight) and property test results of the resin compositions in the examples

[0173]

[0174] [Table 2] Composition (parts by weight) and property test results of the resin compositions in the examples

[0175]

[0176]

[0177] [Table 3] Composition (parts by weight) and property test results of comparative example resin compositions

[0178]

[0179]

[0180] The homemade chemical reagents used in the examples were prepared using the following method:

[0181] Synthesis example 1

[0182] First, 125 g of diamino-terminated polyphenylene ether (as shown in formula (16), where a and b are each an integer from 1 to 10), 13.4 g of p-benzaldehyde, and 16.3 g of p-aminophenol were dissolved in 200 g of toluene and reacted at 90 °C for 1 hour. Then, 45.6 g of 4-chloro-methylstyrene and 100 g of 50% sodium hydroxide solution were added (compared to 1 mole of diamino-terminated polyphenylene ether, the amount of p-benzaldehyde was 2 moles, the amount of p-aminophenol was 3 moles, and the amount of 4-chloro-methylstyrene was 6.6 moles). The mixture was reacted at 90 °C for 1 hour. After the reaction was completed, it was cooled to room temperature and purified by washing with water to obtain polyphenylene ether resin with the structure shown in formula (9), with a number average molecular weight of about 4500, where n is an integer from 1 to 10, and A1 is shown in formula (18), where a and b are each an integer from 1 to 10.

[0183]

[0184] Synthesis example 2

[0185] First, 125 g of diamino-terminated polyphenylene ether (as shown in formula (16), where a and b are each an integer from 1 to 10), 13.4 g of p-benzaldehyde, and 16.3 g of p-aminophenol were dissolved in 200 g of toluene and reacted at 90 °C for 3.5 hours. Then, 45.6 g of 4-chloro-methylstyrene and 100 g of 50% sodium hydroxide solution were added (compared to 1 mole of diamino-terminated polyphenylene ether, the amount of p-benzaldehyde was 2 moles, the amount of p-aminophenol was 3 moles, and the amount of 4-chloro-methylstyrene was 6.6 moles). The mixture was reacted at 90 °C for 3.5 hours. After the reaction was completed, it was cooled to room temperature and purified by washing with water to obtain polyphenylene ether resin with the structure shown in formula (9), with a number average molecular weight of about 20,000, where n is an integer from 1 to 10, and A1 is shown in formula (18), where a and b are each an integer from 1 to 10.

[0186] Synthesis example 3

[0187] First, 125 g of diamino-terminated polyphenylene ether (as shown in formula (16), where a and b are each an integer from 1 to 10), 13.4 g of p-benzaldehyde, and 16.3 g of p-aminophenol were dissolved in 200 g of toluene and reacted at 90 °C for 1 hour. Then, 34.4 g of methacryloyl chloride and 100 g of 50% sodium hydroxide solution were added (compared to 1 mole of diamino-terminated polyphenylene ether, the amount of p-benzaldehyde was 2 moles, the amount of p-aminophenol was 3 moles, and the amount of methacryloyl chloride was 6.6 moles). The mixture was reacted at 90 °C for 1 hour. After the reaction was completed, it was cooled to room temperature and purified by washing with water to obtain polyphenylene ether resin with the structure shown in formula (10), with a number average molecular weight of about 4500, where n is an integer from 1 to 10, and A1 is shown in formula (18), where a and b are each an integer from 1 to 10.

[0188] Synthesis example 4

[0189] First, 125 g of diamino-terminated polyphenylene ether (as shown in formula (16), where a and b are each an integer from 1 to 10), 13.4 g of p-benzaldehyde, and 16.3 g of p-aminophenol were dissolved in 200 g of toluene and reacted at 90 °C for 1 hour. Then, 25.2 g of allyl chloride and 100 g of 50% sodium hydroxide solution were added (compared to 1 mole of diamino-terminated polyphenylene ether, the amount of p-benzaldehyde was 2 moles, the amount of p-aminophenol was 3 moles, and the amount of allyl chloride was 6.6 moles). The mixture was reacted at 90 °C for 1 hour. After the reaction was completed, it was cooled to room temperature and purified by washing with water to obtain polyphenylene ether resin with the structure shown in formula (11), with a number average molecular weight of about 4500, where n is an integer from 1 to 10, and A1 is shown in formula (18), where a and b are each an integer from 1 to 10.

[0190] The characteristic tests of Examples E1 to E10 and Comparative Examples C1 to C7 were conducted by preparing the test samples as follows and then performing the tests according to the specific test conditions. The results are listed in Tables 1 to 3.

[0191] 1. Precursor Sheet: The resin compositions of the examples (listed in Tables 1 and 2) and the resin compositions of the comparative examples (listed in Table 3) were selected respectively. The resin compositions were uniformly mixed to form a varnish. The varnish was placed in an impregnation tank. Then, glass fiber cloth (e.g., E-glass fiber fabric of specification 1078) purchased from Asahi Co., Ltd. was immersed in the impregnation tank to allow the resin composition to adhere to the glass fiber cloth. The mixture was heated at 130°C to 170°C to form a semi-cured state (B-Stage) to obtain a precursor sheet.

[0192] 2. Copper-containing substrate (8-ply, formed by laminating eight prepreg sheets): Prepare two 0.5 oz reverse copper foil (RTF) sheets and eight 1078 E-glass fiber cloth sheets impregnated with prepreg sheets prepared from each test sample (each set of examples or comparative examples). Each prepreg sheet has a resin content of approximately 62 wt%. The prepreg sheets are stacked in the order of one RTF copper foil, eight prepreg sheets and one RTF copper foil, and laminated under vacuum conditions, pressure of 420 psi and 200°C for 2 hours to form a copper-containing substrate (8-ply).

[0193] 3. Copper-free substrate (8-ply, formed by laminating eight prepreg sheets): The copper-containing substrate (8-ply, formed by laminating eight prepreg sheets) is etched to remove two copper foils to obtain a copper-free substrate (8-ply). The copper-free substrate is formed by laminating eight prepreg sheets and has a resin content of approximately 62 wt%.

[0194] 4. Copper-free substrate (18-ply, formed by laminating eighteen prepreg sheets): Two 0.5 oz reverse copper foil (RTF) sheets and eighteen 1078 E-glass fiber cloth sheets impregnated with prepreg sheets prepared from each test sample (each example or comparative example). Each prepreg sheet contains approximately 62 wt% resin. These are stacked in the order of one RTF copper foil, eighteen prepreg sheets, and one RTF copper foil, and then laminated under vacuum conditions, a pressure of 420 psi, and 200°C for 2 hours to form a copper-containing substrate. The copper-containing substrate is then etched to remove two copper foil sheets to obtain a copper-free substrate (18-ply), which is formed by laminating eighteen prepreg sheets and contains approximately 62 wt% resin.

[0195] 5. Copper-free substrate (2-ply, formed by laminating two prepreg sheets): Two 0.5 oz reverse copper foil (RTF) sheets and two 1078 E-glass fiber cloth sheets impregnated with prepreg sheets prepared from each test sample (each set of examples or comparative examples) were prepared. The prepreg sheets were then laminated in the order of copper foil, two prepreg sheets, and copper foil again, and pressed under vacuum conditions at 420 psi and 200°C for 2 hours to form a copper-containing substrate (2-ply, formed by laminating two prepreg sheets). Next, the copper foil on both sides of the copper-containing substrate was etched to obtain a copper-free substrate (2-ply), which is formed by laminating two prepreg sheets. The resin content of the copper-free substrate (2-ply) is approximately 62 wt%.

[0196] For the aforementioned test substance, the characteristics were analyzed in the following manner.

[0197] 1. Relative tracking index

[0198] The copper-free substrate (composed of eighteen prepreg sheets laminated together) was selected as the test sample (100 mm long, 100 mm wide, and 3 mm high). Each test sample was measured according to the method described in ASTM D3638. A voltage of 100V was applied to the sample on the test apparatus, and then one drop of 0.1 wt% ammonium chloride aqueous solution was added every 30 seconds. This titration was continued until tracking occurred. If no tracking occurred after more than 50 drops, the voltage was increased by 5V to 105V, and the voltage value that the sample could withstand was recorded. Each voltage increase of 5V was used for testing, with the voltage range from 100V to 400V. The unit for the relative tracking index is volt (V).

[0199] 2. Breakdown Voltage (BDV)

[0200] The copper-free substrate (composed of eight prepreg sheets laminated together) was selected as the test sample (75 mm long, 50 mm wide, and 1.6 mm high). The test samples were measured according to the method described in IPC-TM-650 2.5.6.3. The samples were immersed in insulating oil (e.g., transformer oil, purchased from Great Wall Lubricating Oil), and the voltage was increased from 0V to 500V per second on the test apparatus. When the leakage current of the sample exceeded 5 mA, the voltage value was recorded; this is the breakdown voltage. The unit of breakdown voltage is kilovolt (kV).

[0201] 3. Dielectric loss (Df)

[0202] The copper-free substrates (2-ply, formed by laminating two prepreg sheets) were selected as the test samples. A microwave dielectric analyzer (purchased from AET Corporation, Japan) was used, and the dielectric loss of each sample was measured at room temperature (approximately 25°C) and a frequency of 10 GHz, following the method described in JIS C2565. Lower dielectric loss indicates better dielectric performance. A difference in dielectric loss greater than or equal to 0.001 indicates a significant difference (presenting significant technical difficulty).

[0203] 4. Copper foil peeling strength (P / S)

[0204] The copper-containing substrate (composed of eight prepreg sheets laminated together) was selected as the test sample. The copper foil tensile strength was measured using a universal tensile testing machine, referring to the method in IPC-TM-650 2.4.8. A higher copper foil tensile strength indicates a stronger bond between the copper foil and the insulating layer. The unit for copper foil tensile strength is pounds per inch (lb / in).

[0205] The following phenomena can be observed from Tables 1 to 3.

[0206] Examples E1 and E8 to E10, using the polyphenylene ether resin with the structure shown in Formula (1) of this application, compared with Comparative Examples C1 and C2 using other polyphenylene ether resins, show excellent relative tracking index and breakdown voltage, while maintaining better dielectric loss and copper foil pull strength. Example E2, using the polyphenylene ether resin with the structure shown in Formula (1) of this application, compared with Comparative Example C5 using a double-terminated amino polyphenylene ether resin (with the structure shown in Formula (16)), shows excellent relative tracking index and breakdown voltage, while maintaining better dielectric loss and copper foil pull strength.

[0207] By comparing Examples E1 and E2 to E7 of this application, it can be found that using the polyphenylene ether resin with the structure shown in Formula (1) combined with one or more of maleimide resin, a crosslinking agent containing unsaturated carbon-carbon double bonds, and polyolefin can further improve the relative tracking index and breakdown voltage, while maintaining better dielectric loss and copper foil tensile strength. By comparing Examples E1 and E8 of this application, it can be found that the smaller the number-average molecular weight of the polyphenylene ether resin with the structure shown in Formula (1), the higher the copper foil tensile strength.

[0208] Comparing Comparative Examples C1 and C2, and observing Comparative Examples C3 and C4, it can be found that even with different combinations of fillers, satisfactory results could not be achieved in terms of characteristics such as relative tracking index and breakdown voltage. Similarly, comparing Comparative Example C5, and observing Comparative Example C6, it can be found that even with more different types of fillers, satisfactory results could not be achieved in terms of characteristics such as relative tracking index and breakdown voltage.

[0209] Furthermore, comparing Example E2 and Comparative Example C7, it can be found that if the polyphenylene ether resin having the structure shown in Formula (1) is not used, but instead the raw materials required for manufacturing the polyphenylene ether resin having the structure shown in Formula (1) of the present invention, such as diamino-terminated polyphenylene ether resin (having the structure shown in Formula (16)), terephthalaldehyde, p-aminophenol and 4-chloro-methylstyrene, are used in the resin composition to prepare the article, the resulting article cannot achieve satisfactory results in terms of characteristics such as relative tracking index, breakdown voltage, dielectric loss and copper foil tensile strength.

[0210] The above embodiments are merely illustrative in nature and are not intended to limit the embodiments of this application or the application or use of such embodiments. In this application, terms such as "example" mean "as an example, illustration, or description." Any exemplary embodiment herein is not necessarily to be interpreted as preferred or more advantageous than other embodiments, unless otherwise indicated.

[0211] 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 in this application. It should also be understood that the embodiments described herein are not intended to limit the scope, use, or configuration of the claimed technical solution in any way. Rather, the foregoing embodiments will provide a simple guide for those skilled in the art to implement one or more of the described embodiments and their equivalents. Moreover, the claims include known equivalents and all foreseeable equivalents at the time of filing of this patent application.

Claims

1. A resin composition, characterized in that, Includes a polyphenylene ether resin having the structure shown in formula (1) and additives; In equation (1), n ​​is an integer from 1 to 10, A1 has the structure shown in equation (2), and A2 each has the structure shown in equation (6), equation (7) or equation (8) independently; In equation (2), a and b are each independent integers from 0 to 100, and a and b are not both 0; -OXO- has the structure shown in equation (3) or equation (4); Y has the structure shown in equation (5); In formula (3), R1, R2, R7 and R8 are the same or different from each other, and each is independently a C1 to C6 alkyl group; R3, R4, R5 and R6 are the same or different from each other, and each is independently a hydrogen atom or a C1 to C6 alkyl group. In equation (4), R9, R 10 R 11 R 12 R 13 R 14 R 15 and R 16 They may be the same or different from each other, and each is independently a C1 to C6 alkyl or hydrogen atom; A is a C1 to C6 divalent hydrocarbon group; In equation (5), R 17 R 18 R 19 and R 20 They may be the same or different from each other, and each is independently a hydrogen atom or a C1 to C6 alkyl group; In equation (6), R 21 R 22 and R 23 Each is an independent hydrogen atom or a C1-C6 alkyl group; Q6 is a C1-C6 divalent alkyl group or does not exist; In equation (7), R 24 R 25 and R 26 Each is an independent hydrogen atom or a C1-C6 alkyl group; Q7 is a C1-C6 divalent alkyl group or does not exist; In equation (8), R 27 R 28 and R 29 Each atom is a hydrogen atom or a C1 to C6 alkyl group.

2. The resin composition according to claim 1, characterized in that, In formula (1), A2 independently includes vinyl, (meth)acryloyl, allyl or vinylbenzyl.

3. The resin composition according to claim 1, characterized in that, The polyphenylene ether resin having the structure shown in formula (1) includes: a polyphenylene ether resin having the structure shown in formula (9), a polyphenylene ether resin having the structure shown in formula (10), a polyphenylene ether resin having the structure shown in formula (11), a polyphenylene ether resin having the structure shown in formula (12), a polyphenylene ether resin having the structure shown in formula (13), a polyphenylene ether resin having the structure shown in formula (14), or a combination thereof:

4. The resin composition according to claim 1, characterized in that, The additives include maleimide resins, crosslinking agents containing unsaturated carbon-carbon double bonds, polyolefins, flame retardants, fillers, curing accelerators, or combinations thereof.

5. The resin composition according to claim 4, characterized in that, The crosslinking agent containing unsaturated carbon-carbon double bonds is 1,2-bis(vinylphenyl)ethane, divinylbenzyl ether, divinylbenzene, divinylnaphthalene, divinylbiphenyl, tert-butylstyrene, triallyl isocyanurate, triallyl cyanurate, 1,2,4-trivinylcyclohexane, diallyl bisphenol A, styrene, butadiene, decanadiene, octadiene, vinylcarbazole, acrylate, or a combination thereof.

6. The resin composition according to claim 1, characterized in that, The resin composition comprises 100 parts by weight of the polyphenylene ether resin having the structure shown in formula (1) and 0.1 to 350 parts by weight of the additive.

7. The resin composition according to claim 6, characterized in that, The additives include 5 to 30 parts by weight of maleimide resin, 15 to 50 parts by weight of a crosslinking agent containing unsaturated carbon-carbon double bonds, 15 to 30 parts by weight of polyolefin or a combination thereof.

8. The resin composition according to claim 1, characterized in that, The resin composition further comprises benzoxazine resin, epoxy resin, silicone resin, cyanate ester resin, reactive ester, phenolic resin, styrene-maleic anhydride, amine curing agent, polyamide, polyimide, polymerization inhibitor, silane coupling agent, surfactant, dye, toughening agent, solvent, or a combination thereof.

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

10. The article of claim 9, characterized in that, The relative tracking index of the product, measured according to the method described in ASTM D3638, is greater than or equal to 300V.

11. The article of claim 9, characterized in that, The breakdown voltage of the product measured according to the method described in IPC-TM-6502.5.6.3 is greater than or equal to 40kV.

12. The article of claim 9, characterized in that, The dielectric loss of the product, measured at a frequency of 10 GHz according to the method described in JIS C2565, is less than or equal to 0.0047.

13. The article of claim 9, 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 2.80 lb / in.

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