A resin composition and its products

Abstract

This application discloses a resin composition comprising 100 parts by weight of a polyphenylene ether resin containing unsaturated carbon-carbon double bonds and 20 to 150 parts by weight of a homopolymer of formula (1). This resin composition can be made into various products, such as prepregs, resin films, laminates, or printed circuit boards. These products possess excellent heat resistance, moisture absorption and heat resistance, and good rigidity of multilayer boards, and also exhibit characteristics such as high glass transition temperature, low dielectric loss, and low Z-axis thermal expansion coefficient.

Description

Technical Field

[0001] This application relates to a resin composition and articles thereof, and particularly to a resin composition that can be used to prepare articles such as prepregs, resin films, laminates and printed circuit boards. Background Technology

[0002] With the advent of the 5G era, printed circuit boards (PCBs) for mobile communications and automotive electronics are undergoing a new round of technological upgrades. This requires that the basic insulating materials in PCBs not only possess low dielectric properties but also high heat resistance and high dimensional stability to adapt to the processing characteristics of multiple laminations and assemblies during PCB manufacturing. In existing technologies, to achieve good dielectric properties, polyphenylene ether or polyolefin is typically selected as the main material, with triallyl isocyanurate (TAIC) as a crosslinking agent. The resulting substrate exhibits good dielectric properties, but these materials cannot simultaneously meet the increasingly demanding requirements for high heat resistance, high dimensional stability, and low dielectric properties. Therefore, there is an urgent need in this field to develop novel resin materials that combine high heat resistance, high dimensional stability, and low dielectric properties. Summary of the Invention

[0003] To address the aforementioned problems, this application provides a resin composition, comprising, in 100 parts by weight, a polyphenylene ether resin containing unsaturated carbon-carbon double bonds, the resin composition comprising:

[0004] (A) 100 parts by weight of polyphenylene ether resin containing unsaturated carbon-carbon double bonds;

[0005] (B) 20 to 150 parts by weight of homopolymer of formula (1),

[0006]

[0007] Where R is a functional group containing unsaturated carbon-carbon double bonds.

[0008] The term "homopolymer of formula (1)" or "homopolymer of monomer of formula (1)" is used.

[0009] Preferably, the resin composition comprises 30 to 150 parts by weight of the homopolymer of formula (1) based on 100 parts by weight of the polyphenylene ether resin containing unsaturated carbon-carbon double bonds.

[0010] Furthermore, the number average molecular weight of the homopolymer of formula (1) in the resin composition is between 800 and 50,000.

[0011] Furthermore, the number-average molecular weight of the homopolymer of formula (1) is preferably between 1,000 and 20,000.

[0012] Optionally, the type of homopolymer of formula (1) is not particularly limited, including but not limited to homopolymers of formula (2), homopolymers of formula (3), homopolymers of formula (4), or combinations thereof.

[0013]

[0014] Among them, R1, R2, R3, R4, R5, R6, R7, and R8 are each independently a hydrogen atom, a methyl group, or an ethyl group; Q1 is a hydrogen atom, a C1-C10 straight-chain hydrocarbon group, a C1-C10 branched hydrocarbon group, or a C3-C10 cyclic hydrocarbon group; Q2 is a C1-C10 straight-chain hydrocarbon group, a C1-C10 branched hydrocarbon group, or a C3-C10 cyclic hydrocarbon group.

[0015] Optionally, the type of polyphenylene ether resin containing unsaturated carbon-carbon double bonds described in component (A) is not limited, and may include one or more of various polyphenylene ether resins containing unsaturated carbon-carbon double bonds known in the art, such as, but not limited to, vinyl benzyl polyphenylene ether resin, (meth)acryloyl polyphenylene ether resin, vinyl polyphenylene ether resin or combinations thereof.

[0016] Further, the resin composition may, as needed, further comprise 50 to 100 parts by weight of a polyolefin. The type of polyolefin is not limited and may include one or more of a variety of olefin polymers known in the art, such as, but 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, styrene-maleic anhydride copolymer, hydrogenated polybutadiene, hydrogenated styrene-butadiene-divinylbenzene terpolymer, hydrogenated styrene-butadiene-maleic anhydride terpolymer, hydrogenated styrene-butadiene copolymer, hydrogenated styrene-isoprene copolymer, or combinations thereof.

[0017] Furthermore, in addition to the polyphenylene ether resin containing unsaturated carbon-carbon double bonds in component (A), the homopolymer of formula (1) in component (B), and the polyolefin, the resin composition of this application may further include, as needed, a crosslinking agent containing unsaturated carbon-carbon double bonds. The crosslinking agent containing unsaturated carbon-carbon double bonds is, for example, but not limited to, 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 combinations thereof.

[0018] Furthermore, the resin composition may, as needed, further include maleimide resin, benzoxazine resin, epoxy resin, silicone resin, cyanate ester resin, reactive ester, phenolic resin, amine curing agent, polyamide, polyimide, or a combination thereof.

[0019] Furthermore, the resin composition may, as needed, further include flame retardants, curing accelerators, polymerization inhibitors, inorganic fillers, solvents, silane coupling agents, surfactants, dyes, toughening agents, or combinations thereof.

[0020] The resin composition of this application can be made into various articles, including but not limited to prepregs, resin films, laminates or printed circuit boards.

[0021] In a preferred embodiment, the article made from the resin composition of this application has one, more, or all of the following characteristics:

[0022] In one embodiment, the glass transition temperature of the article, measured using a dynamic mechanical analyzer according to the method of IPC-TM-6502.4.24.4, is greater than or equal to 241°C.

[0023] In one embodiment, the ratio of the loss modulus to the storage modulus of the article, measured with reference to the method of IPC-TM-650 2.4.24.4, is less than or equal to 0.075.

[0024] In one embodiment, the heat resistance test of the multilayer board was performed on the product according to the method of IPC-TM-650 2.4.13.1, and no board cracking was observed.

[0025] In one embodiment, the moisture absorption and heat resistance of the product were tested according to the methods of IPC-TM-650 2.6.16.1 and IPC-TM-650 2.4.23, and no plate bursting was observed.

[0026] In one embodiment, the Z-axis thermal expansion coefficient, measured with reference to the method of IPC-TM-650 2.4.24.5, is less than or equal to 0.85%.

[0027] In one implementation, the dielectric loss Df measured at a frequency of 10 GHz is less than or equal to 0.0021, according to the method of JIS C2565. Attached Figure Description

[0028] Figure 1 This is the GPC spectrum of vinylbenzocyclobutene homopolymer (PVBCB). Detailed Implementation

[0029] 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.

[0030] 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.

[0031] 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.

[0032] 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".

[0033] 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 regarded as having been specifically disclosed and simultaneously covering closed conjunctions such as “composed of,” “consisting of,” and “remaining as,” as well as open conjunctions such as “essentially composed of,” “mainly composed of,” “mainly composed of,” “basically containing,” “basically composed of,” “basically composed of,” and “essentially containing.”

[0034] 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 those ranges, particularly integer values. For example, range descriptions such as "1.0 to 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, particularly subranges defined by integer values, and should be considered as specifically disclosing individual numerical values ​​within those 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 content throughout this application, regardless of its scope.

[0035] 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 disclosed separately. Furthermore, when a range of numerical values ​​is mentioned herein, unless otherwise stated, the range should include its endpoints and all integers and fractions within the range.

[0036] 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.

[0037] 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 element 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 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 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," it indicates that 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.

[0038] 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.

[0039] 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.

[0040] 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.

[0041] 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.

[0042] 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.

[0043] 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.

[0044] Unless otherwise specified, the alkyl and alkenyl groups mentioned in this application are interpreted to include their various isomers. For example, propyl should be interpreted to include both n-propyl and isopropyl.

[0045] 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 polyolefin means that it can be 100 kilograms of polyolefin or 100 pounds of polyolefin.

[0046] 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.

[0047] 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.

[0048] For example, this application discloses a resin composition comprising, in 100 parts by weight, a polyphenylene ether resin containing unsaturated carbon-carbon double bonds, the resin composition comprising:

[0049] (A) 100 parts by weight of polyphenylene ether resin containing unsaturated carbon-carbon double bonds;

[0050] (B) 20 to 150 parts by weight of homopolymer of formula (1),

[0051]

[0052] Where R is a functional group containing unsaturated carbon-carbon double bonds.

[0053] Unless otherwise specified, the amount of each component added in the resin composition described in this application is calculated based on a total addition of 100 parts by weight of the polyphenylene ether resin containing unsaturated carbon-carbon double bonds in component (A). The amount of the homopolymer of formula (1) in component (B) can be 20 to 150 parts by weight, 30 to 120 parts by weight, or 100 to 150 parts by weight, preferably 30 to 150 parts by weight. When the amount of the homopolymer of formula (1) in component (B) in the resin composition exceeds 150 parts by weight, the copper foil peel strength of the product made using the resin composition will decrease significantly, affecting the application of the product. When the amount of the homopolymer of formula (1) in component (B) in the resin composition is less than 20 parts by weight, the glass transition temperature of the product made using the resin composition will decrease significantly, failing to meet the application requirements.

[0054] In some embodiments, the number-average molecular weight Mn of the homopolymer of formula (1) can be 800 to 50,000, 800 to 1,000, or 20,000 to 50,000, preferably 1,000 to 20,000. The range of the number of repeating units (n) of the monomer in formula (1) in the homopolymer can be calculated from the value of the number-average molecular weight Mn. Preferably, n is an integer from 3 to 400.

[0055] In some implementations, R in equation (1) can be a functional group containing the following structural formula:

[0056]

[0057] In some embodiments, the homopolymer of formula (1) includes homopolymers of formula (2), homopolymers of formula (3), homopolymers of formula (4), or combinations thereof.

[0058]

[0059] Wherein, R1, R2, R3, R4, R5, R6, R7, and R8 are each independently a hydrogen atom, a methyl group, or an ethyl group; Q1 is a hydrogen atom, a C1-C10 straight-chain hydrocarbon group, a C1-C10 branched hydrocarbon group, or a C3-C10 cyclic hydrocarbon group; Q2 is a C1-C10 straight-chain hydrocarbon group, a C1-C10 branched hydrocarbon group, or a C3-C10 cyclic hydrocarbon group; preferably, Q1 is a hydrogen atom, a C1-C3 hydrocarbon group, or a C3 cyclic hydrocarbon group, and Q2 is a C1-C3 hydrocarbon group or a C3 cyclic hydrocarbon group.

[0060] In some embodiments, R in formula (1) can be vinyl, (meth)acryloyl, allyl, or vinylbenzyl.

[0061] The polyphenylene ether resin containing unsaturated carbon-carbon double bonds applicable to this application is not particularly limited, and may be any one or more polyphenylene ether resins containing unsaturated carbon-carbon double bonds 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. Examples include, but are not limited to, vinyl benzyl polyphenylene ether resin, (meth)acryloyl polyphenylene ether resin, vinyl polyphenylene ether resin, or combinations thereof.

[0062] The polyphenylene ether resins containing unsaturated carbon-carbon double bonds used in this application all possess unsaturated carbon-carbon double bonds and a phenylene ether backbone. The unsaturated carbon-carbon double bonds are reactive functional groups, capable of self-polymerization upon heating, or undergoing free radical polymerization with other unsaturated components in the resin composition, ultimately resulting in cross-linking and curing. The cured product exhibits high heat resistance and low dielectric properties. Preferably, the polyphenylene ether resins containing unsaturated carbon-carbon double bonds include those with 2,6-dimethyl substitution on the phenylene ether backbone. The methyl group, after substitution, forms a steric hindrance, making it difficult for the oxygen atoms on the ether to form hydrogen bonds or van der Waals forces, thus reducing hygroscopicity and resulting in even lower dielectric properties.

[0063] Typically, the polyphenylene ether containing unsaturated carbon-carbon double bonds suitable for this application may have the structure shown in formula (5):

[0064]

[0065] Wherein, a and b are each independent positive integers from 1 to 30; preferably, a and b are each independent positive integers from 1 to 10; more preferably, a and b are each independent positive integers from 1 to 5.

[0066] -(OMO)- has the structure shown in equation (6) or equation (7):

[0067]

[0068] L has the structure shown in equation (8):

[0069]

[0070] Among them, R9, R 10 R 15 and R 16 Whether the atoms are the same or different, each is independently a halogen atom, a C1-C6 alkyl group, or a phenyl group; R 11 R 12 R 13 and R 14 Whether the R9 and R1 are the same or different, each is independently a hydrogen atom, a halogen atom, a C1-C6 alkyl group, or a phenyl group; in some embodiments, R9, R1, R2, R3, R4, R5, R6, R7, R8, R9 ... 10 R 11 R 14 R 15and R 16 Each is a methyl group independently;

[0071] R 17 R 18 R 19 R 20 R 21 R 22 R 23 and R 24 Whether the atoms are the same or different, each is independently a halogen atom, a C1-C6 alkyl group, a phenyl group, or a hydrogen atom; in some embodiments, R 17 R 18 R 23 and R 24 Each is a methyl group independently;

[0072] A is a C1-C20 straight-chain hydrocarbon group, a C1-C20 branched hydrocarbon group (such as a branched alkyl group), or a C3-C20 cyclic hydrocarbon group (such as a cycloalkyl group), preferably -CH2- or -C(CH3)2-;

[0073] R 25 R 26 R 27 and R 28 Whether they are the same or different, each is independently a hydrogen atom, a halogen atom, a C1-C6 alkyl group or a phenyl group, preferably each is independently a hydrogen atom or -CH3;

[0074] Z has the structure shown in equation (9), equation (10), or equation (11):

[0075]

[0076] Among them, R 34 R 35 For hydrogen atoms; R 29 R 30 R 31 R 32 and R 33 Whether identical or different, each is independently a hydrogen atom, a halogen atom, an alkyl group, or a halogen-substituted alkyl group. Preferably, the alkyl group is a C1-C6 alkyl group, and the halogen-substituted alkyl group is preferably a C1-C6 alkyl group substituted with halogen. Q3 and Q4 are each independently an organic group having at least one carbon atom, and the organic group optionally includes one or more of a hydrogen atom, an oxygen atom, a nitrogen atom, a sulfur atom, and a halogen atom. In some embodiments, Q3 and Q4 are methylene (-CH2-). In some embodiments, R... 29 To R 33 Each is an independent hydrogen atom or a C1 to C6 alkyl group.

[0077] In some embodiments, the polyphenylene ether resin containing unsaturated carbon-carbon double bonds includes, but is not limited to, vinyl benzyl polyphenylene ether resins with a number average molecular weight of about 1200 (e.g., OPE-2st 1200, available from Mitsubishi Gas Chemical Company), vinyl benzyl polyphenylene ether resins with a number average molecular weight of about 2200 (e.g., OPE-2st 2200, available from Mitsubishi Gas Chemical Company), vinyl benzyl polyphenylene ether resins with a number average molecular weight of about 2400 to 2800 (e.g., vinyl benzyl bisphenol A polyphenylene ether resin), (meth)acryloyl polyphenylene ether resins with a number average molecular weight of about 1900 to 2300 (e.g., SA9000, available from Sabic Company), vinyl polyphenylene ether resins with a number average molecular weight of about 2200 to 3000, or combinations thereof. The vinyl polyphenylene ether resin may include various polyphenylene ether resins disclosed in U.S. Patent Application US20160185904A1, all of which are incorporated herein by reference. Among them, ethylene benzyl polyphenylene ether resin includes, but is not limited to, ethylene benzyl biphenyl polyphenylene ether resin, ethylene benzyl bisphenol A polyphenylene ether resin, or combinations thereof.

[0078] Furthermore, in addition to the aforementioned components, the resin composition of this application may further include polyolefins as needed. Based on 100 parts by weight of polyphenylene ether resin containing unsaturated carbon-carbon double bonds, the polyolefin may be 50 to 100 parts by weight, 50 to 80 parts by weight, or 80 to 100 parts by weight.

[0079] 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.

[0080] The polyolefins described in this application 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. Typically, the number average molecular weight is between 1000 and 150000. Due to the large molecular weight of polyolefins and the regular, repeating carbon-carbon bonds in the main chain, the molecules have low polarity, which can reduce the dielectric properties of the cured product.

[0081] In some embodiments, 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, styrene-maleic anhydride copolymer, 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.

[0082] In some embodiments, the polyolefin is preferably a butadiene-based or isoprene-based diene polymer, a hydrogenated butadiene-based or isoprene-based 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.

[0083] In some embodiments, this application uses polybutadiene (B3000) manufactured by Nippon Soda and styrene-butadiene random copolymer (Ricon 100) manufactured by Cray Valley.

[0084] In addition to the polyphenylene ether resin containing unsaturated carbon-carbon double bonds in component (A), the homopolymer of formula (1) in component (B), and the polyolefin, the resin composition of this application may further include, as needed, a crosslinking agent containing unsaturated carbon-carbon double bonds. Such crosslinking agents include, but are not limited to, 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.

[0085] Unless otherwise specified, the total amount of polyphenylene ether resin containing unsaturated carbon-carbon double bonds is 100 parts by weight, and the amount of crosslinking agent containing unsaturated carbon-carbon double bonds added can be from 1 part by weight to 50 parts by weight, preferably from 5 parts by weight to 30 parts by weight, and the ratio between them can be adjusted as needed.

[0086] In addition to the polyphenylene ether resin containing unsaturated carbon-carbon double bonds in component (A), the homopolymer of formula (1) in component (B), and the polyolefin, the resin composition may, as needed, further include maleimide resin, benzoxazine resin, epoxy resin, silicone resin, cyanate ester resin, reactive ester, phenolic resin, amine curing agent, polyamide, polyimide, or combinations thereof. Modifications of these components are also included in the interpretation.

[0087] Unless otherwise specified, the total mass of polyphenylene ether resin containing unsaturated carbon-carbon double bonds is 100 parts by weight. The amount of any one of the following components can be added from 1 part by weight to 100 parts by weight: maleimide resin, benzoxazine resin, epoxy resin, silicone resin, cyanate ester resin, reactive ester, phenolic resin, amine curing agent, polyamide and polyimide. The ratio between them can be adjusted as needed.

[0088] The maleimide resin applicable to 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, maleimide resins including the following may be used: 4,4′-diphenylmethane bismaleimide, polyphenylmethane maleimide (or oligomer of phenylmethane maleimide), bisphenol Adiphenyl 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), 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.

[0089] For example, maleimide resins can be those produced by Daiwakasei Industry Co., Ltd. under trade names such as BMI-1000, BMI-1000H, BMI-1100, BMI-1100H, BMI-2000, BMI-2300, BMI-3000, BMI-3000H, BMI-4000, BMI-5000, BMI-5100, BMI-TMH, BMI-7000, and BMI-7000H, or those produced by KI Chemical Co., Ltd. under trade names such as BMI-70 and BMI-80.

[0090] For example, maleimide resins containing aliphatic long-chain structures can be maleimide resins produced by the designer's subsidiary under trade names such as BMI-689, BMI-1400, BMI-1500, BMI-1700, BMI-2500, BMI-3000, BMI-5000 and BMI-6000.

[0091] The examples of benzoxazine resins applicable to 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 be, but is not limited to, trade names LZ-8270, LZ-8280, LZ-8290, or LPY 11051 manufactured by Huntsman, PF-3500 manufactured by Changchun Resin, or HFB-2006M manufactured by Showa Polymer Co., Ltd.

[0092] The epoxy resins applicable to this application may be various epoxy resins known in the art, including but not limited to, bisphenol A epoxy resin, bisphenol F epoxy resin, bisphenol S epoxy resin, bisphenol AD ​​epoxy resin, phenolic (novolac) epoxy resin, trifunctional epoxy resin, tetrafunctional epoxy resin, multifunctional 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. The phenolic epoxy resin may be phenol novolac epoxy resin, bisphenol Anovolac epoxy resin, bisphenol F novolac epoxy resin, biphenylnovolac epoxy resin, phenol benzaldehyde epoxy resin, phenolaralkyl novolac epoxy resin, or o-cresol novolac epoxy resin; the phosphorus-containing epoxy resin may be DOPO (9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide) epoxy resin, DOPO-HQ epoxy resin, or a combination thereof.The aforementioned DOPO epoxy resin may include DOPO-containing phenol novolac epoxy resin, DOPO-containing cresol novolac epoxy resin, DOPO-containing bisphenol-A novolac epoxy resin, 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.

[0093] The silicone resins applicable to this application may be various silicone resins known in the art, including but not limited to polyalkyl silicone resins, polyaryl silicone resins, polyalkylaryl silicone resins, modified silicone resins, or combinations 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 Corning 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.

[0094] There are no particular limitations on the cyanate resins applicable to this application; any cyanate resin having an Ar-OC≡N structure is acceptable, wherein Ar can be a substituted or unsubstituted aromatic group. Specific examples 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. 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 may be, for example, cyanate ester resins produced by Lonza under trade names such as primaset PT-15, PT-30S, PT-60S, BA-200, BA-230S, BA-3000S, BTP-2500, BTP-6020S, DT-4000, DT-7000, ULL-950S, HTL-300, CE-320, LVT-50, LeCy, etc.

[0095] The active esters applicable to this application may be various active polyester resins 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 sold by Dai Nippon Ink Chemical under the trade names HPC-8000 and HPC-8150.

[0096] The phenolic resins applicable to this application include, but are not limited to, monofunctional, difunctional, or polyfunctional phenolic resins, including all phenolic resins known for use in the manufacture of prepregs, such as phenolic resins, phenoloxy resins, phenolic resins, etc. Phenolic resins include phenolic resins, o-methylphenolic resins, and bisphenol A resins.

[0097] The amine curing agents applicable to this application may include, but are not limited to, diaminodiphenyl sulfone, diaminodiphenylmethane, diaminodiphenyl ether, diaminodiphenyl sulfide, dicyandiamide, or combinations thereof.

[0098] The polyamides applicable to this application may be various polyamide resins known in the art, including but not limited to various commercially available polyamide resin products.

[0099] The polyimide applicable to this application may be any type of polyimide resin known in the art, including but not limited to various commercially available polyimide resin products.

[0100] Furthermore, in addition to the aforementioned components, the resin composition of this application may selectively further include flame retardants, inorganic fillers, curing accelerators, polymerization inhibitors, solvents, silane coupling agents, surfactants, dyes, toughening agents, or combinations thereof, as needed.

[0101] Unless otherwise specified, the amount of flame retardant used in this application may be adjusted as needed, with the total mass of polyphenylene ether resin containing unsaturated carbon-carbon double bonds being 100 parts by weight, and the amount of flame retardant being, for example, but not limited to, 1 to 100 parts by weight.

[0102] The flame retardant applicable to 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, brominated or phosphorus-containing flame retardants. Brominated flame retardants preferably include decabromodiphenyl ethane, and phosphorus-containing flame retardants preferably include: ammonium polyphosphate, hydroquinone bis-(diphenyl phosphate), bisphenol A bis-(diphenyl phosphate), tri(2-carboxyethyl)phosphine (TCEP), trichloroisopropyl phosphate, trimethyl phosphate (TMP), dimethyl methyl phosphonate (DMMP), and resorcinol bis-(dixylenyl)phosphate. phosphate), RDXP (such as commercially available products such as PX-200, PX-201, PX-202, etc.), phosphazene compounds (such as commercially available products such as SPB-100, SPH-100, SPV-100, etc.), melamine polyphosphate, DOPO and its derivatives (such as bisDOPO compounds) or resins, DPPO (diphenylphosphine oxide) and its derivatives (such as bisDPPO compounds) or resins, melamine cyanurate and tri-hydroxy ethyl isocyanurate, aluminum phosphonate (such as products such as OP-930, OP-935, etc.) or combinations thereof.

[0103] For example, flame retardants can be DPPO compounds (such as bisDPPO compounds), DOPO compounds (such as bisDOPO compounds), DOPO resins (such as DOPO-HQ, DOPO-NQ, DOPO-PN, DOPO-BPN), DOPO-bonded epoxy resins, etc., where DOPO-PN is DOPO phenolic resin, and DOPO-BPN can be bisphenolic resins such as DOPO-BPAN (DOPO-bisphenol A novolac), DOPO-BPFN (DOPO-bisphenol F novolac), or DOPO-BPSN (DOPO-bisphenol S novolac).

[0104] Unless otherwise specified, the amount of inorganic filler used in this application may be adjusted as needed. The total mass of polyphenylene ether resin containing unsaturated carbon-carbon double bonds is 100 parts by weight. The amount of inorganic filler is, for example, but not limited to, 1 to 300 parts by weight, preferably 50 to 200 parts by weight, and more preferably 120 to 180 parts by weight.

[0105] The inorganic filler used in this application 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: 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, the inorganic filler 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.

[0106] Unless otherwise specified, the total mass of the polyphenylene ether resin containing unsaturated carbon-carbon double bonds is 100 parts by weight. The amounts of curing accelerator, polymerization inhibitor, silane coupling agent, surfactant, and dye used in this application can be adjusted as needed. The amount of any one of the above components is, for example, but not limited to, 1 to 20 parts by weight. Preferably, the amount of curing accelerator can be 0.5 to 5.0 parts by weight, more preferably 0.8 to 1.0 parts by weight.

[0107] Curing accelerators suitable for 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, cobalt octanoate, etc. Curing accelerators also include curing initiators, such as peroxides that can generate free radicals, including but not limited to dibenzoyl peroxide. 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)dicarbonate peroxide or combinations thereof.

[0108] The polymerization inhibitors applicable to 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 applicable to 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 applicable to 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 applicable to this application include, but are not limited to, 1,1-diphenyl-2-trinitrophenylhydrazine (DPPH), triphenylmethyl, or combinations thereof.

[0109] 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. 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.

[0110] The silane coupling agents applicable to this application may include silane compounds (such as, but not limited to, siloxane compounds), which can be further classified according to the type of functional group as amino silane compounds, epoxy silane compounds, vinyl silane compounds, ester silane compounds, hydroxy silane compounds, isocyanate silane compounds, methacryloyloxy silane compounds, and acryloyloxy silane compounds.

[0111] The main function of adding surfactants to the resin composition in this application is to enable inorganic fillers to be uniformly dispersed in the resin composition.

[0112] The dyeing agents applicable to this application may include, but are not limited to, dyes or pigments.

[0113] The main function of adding toughening agents in this application is to improve the toughness of the resin composition. Toughening agents may include, but are not limited to, carboxyl-terminated butadiene acrylonitrile rubber (CTBN), core-shell rubber, and other rubbers. Unless otherwise specified, the amount of toughening agent used in this application can be adjusted as needed. For example, but not limited to, 5 to 50 parts by weight of the total mass of the polyphenylene ether resin containing unsaturated carbon-carbon double bonds.

[0114] 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.

[0115] For example, the resin composition described in this application can be made into a prepreg.

[0116] 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 preferably includes fiberglass cloth. There are no particular limitations on the type of fiberglass cloth; it can be commercially available fiberglass cloth suitable for various printed circuit boards, such as E-type fiberglass cloth, D-type fiberglass cloth, S-type fiberglass cloth, T-type fiberglass cloth, L-type fiberglass cloth, or Q-type fiberglass 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 polyester nonwoven fabric, polyurethane nonwoven fabric, etc., but is not limited thereto. The aforementioned woven fabric may also include liquid crystal resin woven fabric, such as polyester woven fabric or polyurethane woven fabric, etc., but is not limited thereto. This reinforcing material increases the mechanical strength of the prepreg. In a preferred embodiment, the reinforcing material may also be selectively pretreated with a silane coupling agent. The prepreg subsequently undergoes heating and curing (C-stage) to form an insulating layer.

[0117] In one embodiment, the resin compositions are mixed uniformly 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 composition to adhere to the fiberglass cloth. Finally, the cloth is heated and baked at an appropriate temperature until it reaches a semi-cured state to obtain a semi-cured sheet.

[0118] 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. As another example, 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.

[0119] 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.

[0120] In one embodiment, the aforementioned multilayer board can be further processed into a printed circuit board.

[0121] 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 the prepreg is cured using a vacuum lamination apparatus at a temperature of 190 to 220°C for 90 to 180 minutes. 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.

[0122] 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:

[0123] In one embodiment, the glass transition temperature of the article, as measured by a dynamic mechanical analyzer with reference to the method of IPC-TM-6502.4.24.4, is greater than or equal to 241°C, for example, between 241°C and 280°C.

[0124] In one embodiment, the ratio of the loss modulus to the storage modulus of the article, measured with reference to the method of IPC-TM-6502.4.24.4, is less than or equal to 0.075, for example, between 0.045 and 0.075.

[0125] In one embodiment, the heat resistance of the multilayer board was tested according to the method of IPC-TM-6502.4.13.1, and no board cracking was observed.

[0126] In one embodiment, the moisture absorption and heat resistance of the product were tested according to the methods of IPC-TM-6502.6.16.1 and IPC-TM-6502.4.23, and no plate bursting was observed.

[0127] In one embodiment, the Z-axis thermal expansion coefficient, measured with reference to the method of IPC-TM-6502.4.24.5, is less than or equal to 0.85%, for example, between 0.38% and 0.85%.

[0128] In one implementation, referring to the method of JIS C2565, the dielectric loss Df measured at a frequency of 10 GHz is less than or equal to 0.0021, for example, between 0.0016 and 0.0021.

[0129] This application prepares the resin compositions of the embodiments of this application according to the dosage in Table 1, and prepares the resin compositions of the comparative examples of this application according to the dosage in Table 2, and further prepares them into various test samples or articles.

[0130] The chemical reagents used in the following examples and comparative examples are as follows:

[0131] 1. Polybutadiene, trade name B3000, purchased from Japan Soda.

[0132] 2. Styrene-butadiene random copolymer: trade name Ricon100, purchased from CrayValley.

[0133] 3. Vinylbenzocyclobutene homopolymer (PVBCB), self-made, with molecular weights of approximately 800, 1000, 4000, 20000 and 50000 respectively.

[0134] 4. Acryloylbenzocyclobutene homopolymer (PABCB), self-made, with a molecular weight of approximately 1000.

[0135] 5. Ethylene benzylbenzocyclobutene homopolymer (PVBBCB), self-made, with a molecular weight of approximately 1000.

[0136] 6. Vinylbenzocyclobutene (VBCB), purchased from Mianyang Dagaote.

[0137] 7. Acryloylbenzocyclobutene (ABCB), self-made.

[0138] 8. Ethylene benzylbenzocyclobutene (VBBCB), self-made.

[0139] 9. Benzocyclobutene (BCB), purchased from Mianyang Dagaote.

[0140] 10. Methacrylamide polyphenylene ether resin, trade name: SA9000, purchased from Sabic.

[0141] 11. Ethylene benzyl polyphenylene ether resin, trade name: OPE-2st 1200, purchased from Mitsubishi Gas Chemical Company.

[0142] 12. Ethylene benzyl polyphenylene ether resin, trade name: OPE-2st 2200, purchased from Mitsubishi Gas Chemical Company.

[0143] 13. Triallyl isocyanurate, trade name TAIC, purchased from Chin Yu Enterprise Co., Ltd.

[0144] 14. Inorganic filler, spherical silica, trade name SC2500-SVJ, purchased from Admatechs.

[0145] 15. Hardening accelerator, 2,5-dimethyl-2,5-di(tert-butylperoxy)-3-hexyne, trade name 25B, purchased from Nippon Oils & Fats Co., Ltd.

[0146] 16. Solvent, toluene, purchased from Sinopec.

[0147] In Tables 1 and 2, “appropriate amount” for solvent means the amount of solvent required to achieve the desired solid content in the resin composition. For example, the solid content of the adhesive in Tables 1 and 2 is 62 wt%.

[0148] The homemade chemical reagents used in the examples and comparative examples were prepared as follows:

[0149] Manufacturing Example 1

[0150] Preparation of Acryloylbenzocyclobutene (ABCB)

[0151] Benzocyclobutene, acryloyl chloride (molar ratio of benzocyclobutene to acryloyl chloride is 1:0.9), and an appropriate amount of dichloromethane were dissolved and stirred evenly, and then added to a reaction flask along with a highly active catalyst (e.g., but not limited to anhydrous aluminum trichloride). The temperature was raised to 40°C and refluxed for 4 hours. The catalyst was first removed by filtration, and then dichloromethane and acryloyl chloride were removed by rotary evaporation. After washing with n-hexane several times, the product acryloylbenzocyclobutene ABCB was obtained by placing it in a forced-air oven at 30°C for 12 hours.

[0152] Manufacturing Example 2

[0153] Preparation of ethylene benzylbenzocyclobutene (VBBCB)

[0154] Benzocyclobutene, chloromethylstyrene (molar ratio of benzocyclobutene to chloromethylstyrene is 1:0.8), and an appropriate amount of dichloromethane were dissolved and stirred evenly, and then added to a reaction flask along with a highly active catalyst (e.g., but not limited to anhydrous aluminum trichloride). The temperature was raised to 40°C and refluxed for 6 hours. The catalyst was first removed by filtration, and then the dichloromethane was removed by rotary evaporation. After washing with n-hexane several times, the product was placed in a forced-air oven at 30°C for 12 hours to obtain ethylene benzylbenzocyclobutene (VBBCB).

[0155] Manufacturing Example 3

[0156] Preparation of vinylbenzocyclobutene homopolymer (PVBCB)

[0157] First, 0.5 moles of vinylbenzocyclobutene monomer and 0.01 moles of 2,2,6,6-tetramethylpiperidine-nitrogen oxide (2,2,6,6-tetramethylpiperidine-nitrogen oxide) were added to the Schlenck reaction flask. (The main function of 2,2,6,6-tetramethylpiperidine-nitrogen oxide is to control the polymerization rate and prevent the polymerization reaction from being too fast, so as to obtain a product with the ideal molecular weight. After treatment with methanol solution, the crude product does not contain 2,2,6,6-tetramethylpiperidine-nitrogen oxide, that is, 2,2,6,6-tetramethylpiperidine-nitrogen oxide will not appear in the product structural formula.) Then, the reaction flask was placed in a liquid nitrogen environment for 2 minutes to freeze, followed by evacuation for 5 minutes, and then argon was introduced. The above process is repeated three times to purge the oxygen from the bottle; then the reaction bottle is placed in an oil bath at 130°C and the reaction time is controlled to be 24 hours to obtain the crude polymer of vinylbenzocyclobutene (this reaction is a living free radical polymerization, and different reaction times can yield polymer products with different molecular weights); while stirring, the crude product is added dropwise to the methanol solution, and after the addition is complete, stirring is continued for 0.5 hours, filtered, and vacuum dried to obtain the final product vinylbenzocyclobutene homopolymer (PVBCB), as shown in the following formula (12), where R1, R2, and Q1 are all hydrogen atoms. By GPC testing, the number average molecular weight Mn of the product is calculated to be approximately 4000:

[0158]

[0159] The GPC spectrum of PVBCB (Mn≈4000) is as follows: Figure 1 As shown.

[0160] Using the above method, under the same conditions, the reaction time was controlled to be 6 hours, 9 hours, 72 hours and 100 hours respectively, and PVBCBs with Mn≈800, Mn≈1000, Mn≈20000 and Mn≈50000 as shown in equation (12) can be obtained in turn.

[0161] Manufacturing Example 4

[0162] Preparation of acryloylbenzocyclobutene homopolymer (PABCB)

[0163] By replacing the vinylbenzocyclobutene monomer in Manufacturing Example 3 with an acryloylbenzocyclobutene monomer, and using the same method under the same conditions, the reaction time was controlled to be 9 hours to prepare the acryloylbenzocyclobutene homopolymer PABCB (Mn≈1000) as shown in Equation (13), where R3, R4, and R5 are all hydrogen atoms:

[0164]

[0165] Manufacturing Example 5

[0166] Preparation of ethylene benzyl benzocyclobutene homopolymer (PVBBCB)

[0167] By replacing the vinylbenzocyclobutene monomer in Manufacturing Example 3 with ethylenebenzylbenzocyclobutene monomer, and using the same method under the same conditions, the reaction time was controlled to be 9 hours to prepare the ethylenebenzylbenzocyclobutene homopolymer PVBBCB (Mn≈1000) as shown in Equation (14), where R6, R7, and R8 are all hydrogen atoms, and Q2 is a methylene group:

[0168]

[0169] The characteristic tests of Examples E1 to E13 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 3 and 4.

[0170] 1. Precursor Sheet: The resin compositions of the above embodiments (listed in Table 1) and the resin compositions of the above comparative examples (listed in Table 2) were selected respectively. The resin compositions were uniformly mixed to form a varnish with a solid content of 62 wt%. The varnish was placed in an impregnation tank, and then glass fiber cloth (for example, L-glass fiber fabric of specification 2116 or L-glass fiber fabric of specification 1078, both purchased from Asahi Corporation) was immersed in the impregnation tank to allow the resin composition to adhere to the glass fiber cloth. The mixture was heated at 130°C to 170°C to form a semi-cured state (B-Stage) to obtain a precursor sheet.

[0171] 2. Copper Foil Substrate (6-ply, formed by laminating six prepreg sheets): Two 18-micron thick ultra-low surface roughness (HVLP) copper foils and six 2116 L-glass fiber cloths were prepared, impregnated with prepreg sheets prepared from each test sample (each set of examples or comparative examples). Each prepreg sheet had a resin content of approximately 55%. The prepreg sheets were stacked in the following order: one HVLP copper foil, six prepreg sheets, and one HVLP copper foil. They were then laminated under vacuum conditions, a pressure of 420 psi, and 200°C for 2 hours to form a copper foil substrate. The six stacked prepreg sheets cured to form an insulating layer between the two copper foils, with a resin content of approximately 55%.

[0172] 3. Copper-free substrate (6-ply, made of six prepreg sheets laminated together): The copper foil substrate mentioned above is etched to remove two copper foils to obtain a copper-free substrate (6-ply). The copper-free substrate is made of six prepreg sheets laminated together, and the resin content of the copper-free substrate is about 55%.

[0173] 4. Copper-free substrate (2-ply, formed by laminating two prepreg sheets): Prepare two 18-micron thick ultra-low surface roughness (HVLP) copper foils and two 1078 L-glass fiber cloths impregnated with prepreg sheets prepared from each test sample (each set of examples or comparative examples). Lay the copper foil, two prepreg sheets, and copper foil in that order, and press them together under vacuum conditions, a pressure of 420 psi, and 200°C for 2 hours to form a copper foil-containing substrate (2-ply, formed by laminating two prepreg sheets). Next, etch the copper foil substrate to remove the copper foil from both sides to obtain a copper-free substrate (2-ply). This copper-free substrate is formed by laminating two prepreg sheets, and the resin content of the copper-free substrate (2-ply) is approximately 70%.

[0174] For the aforementioned test substance, the characteristics were analyzed in the following manner.

[0175] 1. Glass transition temperature (Tg)

[0176] For the measurement of glass transition temperature, the copper-free substrate (6-ply) mentioned above was selected as the test sample. A dynamic mechanical analyzer (DMA) was used, and the glass transition temperature of each test sample was measured according to the method described in IPC-TM-6502.4.24.4, "Glass Transition and Modulus of Materials Used in High Density Interconnection (HDI) and Microvias-DMA Method," with units expressed in °C. The measurement temperature range was 50–400 °C, with a temperature rise rate of 2 °C / min; higher glass transition temperatures were preferred.

[0177] 2. The ratio of loss modulus to energy storage modulus (DMA - tan δ)

[0178] In the DMA-tan δ measurement, the copper-free substrate (6-ply) mentioned above was selected as the test sample. A dynamic mechanical analyzer (DMA) was used, and the glass transition temperature, loss modulus, and storage modulus of each test sample were measured according to the method described in IPC-TM-6502.4.24.4 Glass Transition and Modulus of Materials Used in High Density Interconnection (HDI) and Microvias-DMA Method. The ratio of loss modulus to storage modulus at the glass transition temperature is the DMA-tan δ. The measurement temperature range was 50–400 °C, with a temperature rise rate of 2 °C / min. A smaller DMA-tan δ indicates better sample rigidity.

[0179] 3. Heat resistance of multi-layer boards

[0180] The core board was fabricated as follows: A prepreg (approximately 55% resin content per prepreg) was prepared by impregnating each test sample (each example or comparative example) with a 2116 L-glass fiber cloth. An ultra-low surface roughness copper foil (18 micrometers thick) was laminated onto both sides of the prepreg. The prepreg was then pressed and cured under vacuum, high temperature (200°C), and high pressure (420 psi) for 2 hours to obtain a copper-containing core board. Next, the copper foil on both sides of the copper-containing core board was etched away to obtain a copper-free core board (5 mils thick). Three copper-free core boards were prepared according to this method; then, two ultra-low surface roughness copper foils (18 micrometers thick) and eight sheets of 1078 L-glass fiber cloth were prepared, impregnated with prepregs (each prepreg containing approximately 70% resin) prepared from each test sample (each set of examples or comparative examples). The preparation process involved copper foil, two prepregs (made using 1078 L-glass fiber cloth), one copper-free core board, two prepregs (made using 1078 L-glass fiber cloth), one copper-free core board, two prepregs (made using 1078 L-glass fiber cloth), and one copper-free core board. A copper core board, two prepreg sheets (made of 1078 L-glass fiber cloth), and copper foil are stacked sequentially and pressed under vacuum conditions, pressure of 420 psi, and 200°C for 2 hours to form an eight-layer board with copper foil on the outer layer. The board is then cut into a rectangular sample (5.9 inches long and 2.2 inches wide). Through holes with a total of 500 holes and a diameter of 0.3 mm are formed on the surface of the rectangular sample using circuit board drilling technology (20*25 through hole matrix, with a vertical distance of 0.25 mm between adjacent hole walls). Copper is then electroplated on the hole walls to obtain a multilayer board heat resistance test sample.

[0181] In the heat resistance test of multilayer boards, the aforementioned multilayer board heat resistance test samples were used. Referring to the method described in IPC-TM-6502.4.13.1, the sample was placed horizontally (i.e., in contact) with the molten solder surface in a constant-temperature solder bath at 288°C. During each test, one side of the sample was placed on the solder surface for 10 seconds. After 10 seconds, the sample was removed from the solder surface and cooled at room temperature for 30 seconds. The same side of the sample was then placed on the solder surface again for 10 seconds, and then removed again and cooled at room temperature for 30 seconds. This process was repeated 10 times, with each group using 3 samples of the same specifications. The samples were then sliced ​​and examined using an optical microscope to check for any signs of delamination in the inner layers. If no delamination occurred after 10 cycles of solder bleeding for all 3 samples, the test was marked "pass," indicating no delamination. If at least one of the 3 samples delaminated after 10 cycles of solder bleeding, the test was marked "NG," indicating delamination had occurred. The aforementioned "board bursting" can be understood as interlayer delamination or blistering. Board bursting can occur between any layers of the substrate. For example, interlayer delamination between insulating layers can be called board bursting, as can blistering and separation between copper foil and insulating layers. Multilayer boards, because they contain multiple layers of copper foil and have undergone circuit board drilling, have heat resistance test results that more accurately reflect the heat resistance of the printed circuit board. The heat resistance test results of ordinary double-layer boards that have not undergone circuit board drilling cannot accurately predict the heat resistance of multilayer boards, that is, cannot predict the heat resistance of printed circuit boards.

[0182] 4. Moisture absorption and heat resistance test (pressure cooking test, PCT)

[0183] In the moisture absorption and heat resistance test, the copper-free substrate (6-ply) mentioned above was selected as the test sample. Following the method in IPC-TM-650 2.6.16.1, a pressure cooking test (PCT) was conducted for 5 hours (test temperature 121℃, relative humidity 100%). Then, following the method in IPC-TM-650 2.4.23, the sample was immersed in a tin bath at a constant temperature of 288℃. After immersion for 20 seconds, the sample was removed to observe whether any delamination or blistering occurred. Three samples of the same specifications were tested in each group. If any sample showed delamination (marked X), it indicated that the insulating layer of the substrate had partially separated or blistered. If the test result was no delamination (marked O), it indicated that no delamination or blistering occurred. OOO represents no delamination in any of the three samples, XXX represents delamination in all three samples, and OXX represents two delaminations and one non-delamination in the three samples.

[0184] 5. Z-axis thermal expansion coefficient (percent thermal expansion, z-axis, Z-PTE)

[0185] In the measurement of Z-axis thermal expansion coefficient, a copper-free substrate (6-ply) was selected as the test sample for thermomechanical analysis (TMA). The sample was heated at a rate of 10°C per minute, from 50°C to 260°C. The Z-axis thermal expansion coefficient (in %) of each test sample within the temperature range of 50°C to 260°C was measured according to the method of IPC-TM-6502.4.24.5. A lower Z-axis thermal expansion coefficient is better.

[0186] 6. Dielectric loss (dissipation factor, Df)

[0187] In the dielectric loss measurement, the copper-free substrate (2-ply) mentioned above was selected as the test sample. A microwave dielectric analyzer (purchased from AET Corporation, Japan) was used, and the method of JIS C2565 was followed to measure each test sample at a frequency of 10 GHz. The lower the dielectric loss, the better the dielectric properties of the test sample. At the measurement frequency of 10 GHz and within the range where the Df value is less than 0.0030, a difference in Df value less than 0.0001 indicates that there is no significant difference in dielectric loss between the substrates, while a difference in Df value greater than or equal to 0.0001 indicates that there is a significant difference in dielectric loss between different substrates (presenting significant technical difficulties).

[0188]

[0189]

[0190]

[0191] The following phenomena can be observed from Tables 1 to 4.

[0192] Compared to Comparative Example C5, Examples E1 to E10 and Example E12 compared to Comparative Example C6 have added homopolymer of Formula (1), resulting in a significant increase in glass transition temperature. Unlike C5 and C6, they did not exhibit board bursting phenomenon in the heat resistance and moisture absorption heat resistance tests of multilayer boards. They also have a lower ratio of loss modulus to storage modulus, lower Z-axis thermal expansion coefficient and lower dielectric loss, which means they exhibit good rigidity, heat resistance, dimensional stability and dielectric properties.

[0193] Unlike comparative examples C1 to C4, which added monomers with the structure shown in formula (1), examples E1 to E7 added homopolymers of formula (1). Example E11 replaced the monomers of formula (1) with homopolymers of formula (1) compared to comparative example C7. Examples E1 to E7 and E11 had significantly higher glass transition temperatures. In the heat resistance and moisture absorption heat resistance tests of multilayer boards, they did not exhibit the same board explosion phenomenon as C1 to C4 and C7. They also had lower ratios of loss modulus to storage modulus, Z-axis thermal expansion coefficient and dielectric loss, and showed good rigidity, heat resistance, dimensional stability and dielectric properties.

[0194] Compared to E3, E9 to E10, where 30 to 150 parts by weight of the homopolymer of formula (1) were added, E8 added 20 parts by weight of the homopolymer of formula (1). It can be seen that as the amount of homopolymer of formula (1) added decreases, the glass transition temperature decreases to a certain extent, the ratio of loss modulus to storage modulus increases to a certain extent, and the Z-axis thermal expansion coefficient increases to a certain extent. However, no board bursting occurred in the heat resistance and moisture absorption heat resistance tests of the multilayer board, and the dielectric properties remained good.

[0195] Compared to the vinylbenzocyclobutene homopolymer (PVBCB) with a number-average molecular weight (Mn) of approximately 1000-20000 added in Examples E2-E4, the PVBCB added in Example E1 has an Mn of approximately 800, and the PVBCB added in Example E5 has an Mn of approximately 50000. The characteristic results show that E1 and E5 did not experience board breakage in the heat resistance and moisture absorption heat resistance tests of multilayer boards, but the glass transition temperature decreased to a certain extent, and the ratio of loss modulus to storage modulus and the Z-axis thermal expansion coefficient increased to a certain extent. The performance in terms of heat resistance, rigidity, and dimensional stability was relatively worse.

[0196] Example E13 further added polyolefin resin and a crosslinking agent containing unsaturated carbon-carbon double bonds (TAIC). The results show that it did not explode in the heat resistance and moisture absorption heat resistance tests of multilayer boards, maintained good dielectric properties, had a relatively high glass transition temperature, and had a relatively low ratio of loss modulus to storage modulus and Z-axis thermal expansion coefficient, which better met the requirements for improving heat resistance, rigidity and dimensional stability.

[0197] 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.

[0198] 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, Based on 100 parts by weight of a polyphenylene ether resin containing unsaturated carbon-carbon double bonds, the resin composition comprises: (A) 100 parts by weight of polyphenylene ether resin containing unsaturated carbon-carbon double bonds; (B) 20 to 150 parts by weight of homopolymer of formula (1), Where R represents a functional group containing an unsaturated carbon-carbon double bond. The number average molecular weight of the homopolymer of formula (1) is between 800 and 50,000.

2. The resin composition according to claim 1, characterized in that, The resin composition comprises 30 to 150 parts by weight of the homopolymer of formula (1).

3. The resin composition according to claim 1, characterized in that, The number average molecular weight of the homopolymer of formula (1) is between 1,000 and 20,000.

4. The resin composition according to claim 1, characterized in that, The homopolymer of formula (1) includes homopolymers of formula (2), homopolymers of formula (3), homopolymers of formula (4), or combinations thereof. Among them, R1, R2, R3, R4, R5, R6, R7, and R8 are each independently a hydrogen atom, a methyl group, or an ethyl group; Q1 is a hydrogen atom, a C1-C10 straight-chain hydrocarbon group, a C1-C10 branched hydrocarbon group, or a C3-C10 cyclic hydrocarbon group; Q2 is a C1-C10 straight-chain hydrocarbon group, a C1-C10 branched hydrocarbon group, or a C3-C10 cyclic hydrocarbon group.

5. The resin composition according to claim 1, characterized in that, The polyphenylene ether resin containing unsaturated carbon-carbon double bonds includes vinyl benzyl polyphenylene ether resin, (meth)acryloyl polyphenylene ether resin, vinyl polyphenylene ether resin, or combinations thereof.

6. The resin composition according to claim 1, characterized in that, The resin composition further includes 50 to 100 parts by weight of a polyolefin, said polyolefin including 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, styrene-maleic anhydride copolymer, hydrogenated polybutadiene, hydrogenated styrene-butadiene-divinylbenzene terpolymer, hydrogenated styrene-butadiene-maleic anhydride terpolymer, hydrogenated styrene-butadiene copolymer, hydrogenated styrene-isoprene copolymer, or combinations thereof.

7. The resin composition according to claim 1, characterized in that, The resin composition further includes a crosslinking agent containing unsaturated carbon-carbon double bonds, wherein the crosslinking agent containing unsaturated carbon-carbon double bonds includes 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.

8. The resin composition according to claim 1, characterized in that, The resin composition further includes maleimide resin, benzoxazine resin, epoxy resin, silicone resin, cyanate ester resin, reactive ester, phenolic resin, polyamide, polyimide, or a combination thereof.

9. The resin composition according to claim 1, characterized in that, The resin composition further includes flame retardants, curing accelerators, polymerization inhibitors, inorganic fillers, solvents, silane coupling agents, surfactants, dyes, toughening agents, or combinations thereof.

10. An article made from the resin composition according to any one of claims 1 to 9, characterized in that, The products include prepregs, resin films, laminates, or printed circuit boards.

11. The article of claim 10, characterized in that, The article has at least one of the following characteristics: The glass transition temperature of the article, as measured by using a dynamic mechanical analyzer and referring to the method of IPC-TM-650 2.4.24.4, is greater than or equal to 241°C. The ratio of the loss modulus to the storage modulus of the product, measured according to the method of IPC-TM-650 2.4.24.4, is less than or equal to 0.075; The product was subjected to a multilayer board heat resistance test according to the method of IPC-TM-650 2.4.13.1, and no board cracking was observed. The moisture absorption and heat resistance of the product were tested according to the methods of IPC-TM-650 2.6.16.1 and IPC-TM-650 2.4.23, and no plate bursting was observed. The Z-axis thermal expansion coefficient, measured according to the method of IPC-TM-650 2.4.24.5, is less than or equal to 0.85%. According to the method of JIS C2565, the dielectric loss Df of the article, measured at a frequency of 10 GHz, is less than or equal to 0.0021.

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