Resin composition and product thereof

Abstract

The present invention provides a resin composition comprising: a component (A): 100 parts by weight of a polyphenyl ether resin containing an unsaturated carbon-carbon double bond; component (B): 1-20 parts by weight of first polyolefin modified by unhydrogenated maleic anhydride; and component (C): 5 to 100 parts by weight of a benzocyclobutene-modified second polyolefin. In addition, the invention also provides a product prepared from the resin composition, the product comprises a prepreg, a resin film, a laminated board or a printed circuit board, and the product is improved in one or more aspects of BC tension stability, solder ball thrust, a gap between a glass cloth and a resin interface and floating tin and board explosion rate.

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, or copper clad laminates) and printed circuit boards, and articles made therefrom. Background Technology

[0002] With the rapid development of electronic technology, the information processing of electronic products such as mobile communication, AI servers, and cloud storage is constantly moving towards higher frequency and higher speed signal transmission. In order to meet the needs of high-frequency and high-speed information transmission, dielectric materials with excellent dielectric properties have become the key to the production of copper foil substrates.

[0003] Hydrocarbon resins, such as polybutadiene and butadiene-styrene copolymers, have become mainstream materials in the industry due to their excellent dielectric properties. However, products made from these hydrocarbon resins suffer from defects such as poor BC tensile strength stability, low solder ball thrust, gaps at the interface between the glass cloth and the resin, and a high rate of solder drift and board breakage. This invention aims to provide a new resin composition to address one or more of the aforementioned defects. Summary of the Invention

[0004] In view of the problems encountered in the prior art, especially the inability of existing materials to meet one or more of the above-mentioned characteristic requirements, the main objective of the present invention is to provide a resin composition that can solve the above-mentioned problems, as well as prepreg, resin film, laminate or printed circuit board articles made from said resin composition.

[0005] In one aspect, the present invention provides a resin composition comprising:

[0006] Composition (A): 100 parts by weight of polyphenylene ether resin containing unsaturated carbon-carbon double bonds;

[0007] Component (B): 1-20 parts by weight of unhydrogenated maleic anhydride-modified primary polyolefin; and

[0008] Composition (C): 5-100 parts by weight of benzocyclobutene-modified second polyolefin.

[0009] In one aspect, the present invention also provides an article made from the above-described resin composition, the article comprising a prepreg, a resin film, a laminate, or a printed circuit board.

[0010] The resin composition or its product provided by the present invention improves one or more aspects of BC tensile stability, solder ball thrust, glass cloth-resin interface gap, and tin floating and bursting rate. Detailed Implementation

[0011] The following detailed description of the features and advantages of the present invention in the embodiments is sufficient to enable any person skilled in the art to understand the technical content of the present invention and implement it accordingly. Furthermore, based on the content disclosed in this specification and the claims, any person skilled in the art can easily understand the related objects and advantages of the present invention. The following embodiments further illustrate the viewpoints of the present invention in detail, but are not intended to limit the scope of the present invention in any way.

[0012] The terms used in the following description are generally used in the relevant art and should not be construed as limiting the invention, but rather as examples of terms used to describe embodiments. If any term used in the following description conflicts with its definition in the relevant art, the following definition shall prevail.

[0013] Unless otherwise specified, when describing the components or technical features of the present invention in a singular form, it may also include a plural form.

[0014] Throughout this document, the terms "including," "containing," "having," "containing," or any other similar words are open-ended conjunctions. Unless otherwise specified, these terms may also include other parts. Throughout this document, the terms "composed of," "consisting of," "remaining as," or any other similar words are closed-ended conjunctions.

[0015] The phrase "a composition comprising A, B, and C, wherein A comprises a1, a2, or a3" used throughout the document is equivalent to "a composition comprising A, B, and C, wherein A comprises a1, a2, a3, or a combination thereof," meaning "a composition comprising A, B, and C, wherein A comprises a1, a2, a3, a combination of a1 and a2, a combination of a1 and a3, a combination of a2 and a3, or a combination of a1, a2, and a3." The phrase "or a combination thereof" used throughout the document is equivalent to "or any combination thereof."

[0016] For ease of explanation, the numerical ranges described throughout should be understood to include all possible subranges and all individual values ​​(including decimals and integers) within the range. For example, "2.0 to 7.0", "between 2.0 and 7.0", "between 2.0 and 7.0", "between 2.0 and 7.0", or any other similar terms should be understood to include all subranges such as 2.0 to 7.0, 3.0 to 6.0, 4.0 to 5.0, 2.0 to 6.0, etc., including endpoint values.

[0017] The numerical values ​​described throughout include all numerical ranges that are the same as this value after rounding to the number of significant digits. For example, the value 20.0 includes the range from 19.50 to 20.49.

[0018] It should be understood that the invention can be described individually and / or in combination using each member of the Markush group.

[0019] Unless otherwise stated, the monomers described in this invention refer to molecules that can be covalently linked with the same or other molecules to form polymers.

[0020] Unless otherwise stated, the polymers described in this invention refer to products formed by the polymerization reaction of monomers. Polymers may include, but are not limited to, homopolymers (also known as self-polymers), copolymers, prepolymers, etc. Prepolymers are low molecular weight polymers with a degree of polymerization between that of the monomer and the final polymer. Polymers certainly include oligomers, but are not limited to them. Oligomers, also known as low-molecular-weight polymers, are polymers composed of 2 to 20 repeating units, typically 2 to 5 repeating units. For example, diene polymers should be understood to include diene homopolymers, diene copolymers, diene prepolymers, and diene oligomers, etc.

[0021] Unless otherwise stated, the copolymers described in this invention refer to products formed by the polymerization of two or more different monomers, including random copolymers, alternating copolymers, graft copolymers, or block copolymers, but the invention is not limited thereto. For example, a styrene-butadiene copolymer is a product formed by the polymerization of only styrene and butadiene monomers. For example, styrene-butadiene copolymers include styrene-butadiene random copolymers, styrene-butadiene alternating copolymers, styrene-butadiene graft copolymers, or styrene-butadiene block copolymers, but the invention is not limited thereto. Styrene-butadiene block copolymers include, for example, styrene-butadiene diblock copolymers and styrene-butadiene-styrene triblock copolymers, but the invention is not limited thereto. Similarly, hydrogenated styrene-butadiene copolymers include hydrogenated styrene-butadiene random copolymers, hydrogenated styrene-butadiene alternating copolymers, hydrogenated styrene-butadiene graft copolymers, or hydrogenated styrene-butadiene block copolymers. Hydrogenated styrene-butadiene block copolymers include, for example, hydrogenated styrene-butadiene diblock copolymers and hydrogenated styrene-butadiene-styrene triblock copolymers, but the present invention is not limited thereto.

[0022] It should be understood that a resin composition containing three compounds A, B, and C and one additive (a total of four components) is different from a resin composition containing a prepolymer formed from three compounds A, B, and C and one additive (a total of two components). These two types of resin compositions differ significantly in their preparation methods, physicochemical properties, and the characteristics of their finished products. The former involves directly mixing A, B, C, and the additive, while the latter requires first prepolymerizing A, B, and C under appropriate conditions to generate a prepolymer before mixing it with the additive. Since the function of the prepolymer in the resin composition differs from the function of A, B, and C, whether present individually or together, these two resin compositions should be considered different chemical substances with different chemical properties. For example, when the resin composition is heated to a semi-cured state, in the latter case, the prepolymer undergoes a partial crosslinking reaction with the crosslinking agent, rather than A, B, and C reacting individually with the crosslinking agent; therefore, the characteristics of the finished product are completely different.

[0023] Unless otherwise stated, the term "resin" as used in this invention should be understood to include monomers, polymers thereof, combinations of monomers, combinations of polymers thereof, or combinations of monomers and their polymers, but the invention is not limited thereto. For example, the term "maleimide resin" as used throughout should be understood to include maleimide monomers, maleimide polymers, combinations of maleimide monomers, combinations of maleimide polymers, or combinations of maleimide monomers and maleimide polymers.

[0024] Unless otherwise stated, the modified products of this invention include products of each resin after reactive functional group modification, products of each resin after prepolymerization with other resins, products of each resin after copolymerization with other resins, and products of each resin after crosslinking with other resins.

[0025] Unless otherwise stated, the unsaturated bonds referred to in this invention are reactive unsaturated bonds, such as unsaturated double bonds that can undergo cross-linking reactions with other functional groups or unsaturated carbon-carbon double bonds that can cross-link with other functional groups, but this invention is not limited thereto.

[0026] The unsaturated carbon-carbon double bonds described in this invention include vinyl, vinylbenzyl, (meth)acryloyl, allyl, or combinations thereof, but this invention is not limited thereto. Vinyl should be understood to include vinyl and vinylidene (also known as vinylidene), and (meth)acryloyl should be understood to include acryloyl and methacryloyl. Therefore, unless otherwise stated, the polyphenylene ether resin containing unsaturated carbon-carbon double bonds described in this invention includes polyphenylene ether resins having any one of the functional groups selected from vinyl, vinylbenzyl, (meth)acryloyl, and allyl, but this invention is not limited thereto.

[0027] Unless otherwise stated, any compound described in this invention includes its various isomers. For example, propyl is understood to include isopropyl and n-propyl.

[0028] Unless otherwise stated, parts by weight as used in this invention refer to parts by weight, which can be any unit of weight, such as kilograms, grams, pounds, etc., but the invention is not limited thereto. For example, 100 parts by weight of polyphenylene ether resin containing unsaturated carbon-carbon double bonds can represent 100 kilograms of polyphenylene ether resin containing unsaturated carbon-carbon double bonds or 100 pounds of polyphenylene ether resin containing unsaturated carbon-carbon double bonds. If the resin solution includes both solvent and resin, then the parts by weight of the (solid or liquid) resin generally refers to the weight unit of the (solid or liquid) resin and does not include the weight unit of the solvent in the solution, while the parts by weight of the solvent refers to the weight unit of the solvent. It should be understood that features of various embodiments of the invention may be combined with each other, either partially or entirely.

[0029] It should be understood that the following embodiments are illustrative in all respects and do not limit the invention, and are intended to illustrate the scope of the technical concept of the invention. Therefore, the scope of the invention is not limited to the embodiments shown.

[0030] As described above, this invention mainly discloses a resin composition comprising the following components:

[0031] Composition (A): 100 parts by weight of polyphenylene ether resin containing unsaturated carbon-carbon double bonds.

[0032] Component (B): 1-20 parts by weight of unhydrogenated maleic anhydride-modified primary polyolefin,

[0033] Composition (C): 5-100 parts by weight of benzocyclobutene-modified second polyolefin.

[0034] In one embodiment, for example, the unhydrogenated maleic anhydride-modified first polyolefin includes maleic anhydride addition polybutadiene, maleic anhydride addition polyisoprene, maleic anhydride addition styrene-butadiene copolymer, maleic anhydride addition styrene-isoprene copolymer, or combinations thereof. These components should be understood to include modified or derivative versions of these components. The unhydrogenated maleic anhydride-modified first polyolefin has unsaturated carbon-carbon double bonds.

[0035] In one embodiment, for example, the benzocyclobutene-modified second polyolefin includes any one or a combination of benzocyclobutene-modified polyolefins containing heteroatoms and benzocyclobutene-modified polyolefins without heteroatoms.

[0036] In one embodiment, for example, the heteroatom-containing polyolefin includes any one or a combination of maleic anhydride addition polybutadiene, maleic anhydride addition polyisoprene, maleic anhydride addition styrene-butadiene copolymer, maleic anhydride addition styrene-isoprene copolymer, vinyl-polybutadiene-urea polymer, silane-modified styrene-butadiene copolymer, terminal acryloyl polybutadiene, and epoxy-containing polybutadiene. These components should be understood to include modified or derivative versions of these components.

[0037] In one embodiment, for example, the heteroatom-free polyolefin includes any one or a combination of polybutadiene, polyisoprene, styrene-butadiene copolymer, styrene-isoprene copolymer, styrene-butadiene-divinylbenzene polymer, styrene-ethylene-divinylbenzene polymer, and styrene-ethylvinylbenzene-divinylbenzene polymer. These components should be understood to include modified or derivative versions of these components.

[0038] In one embodiment, for example, the mass ratio of the benzocyclobutene-modified polyolefin without heteroatoms to the benzocyclobutene-modified polyolefin containing heteroatoms is preferably 2:3 to 24:1.

[0039] Unless otherwise specified, the amount of each component added in the resin composition of the present invention is calculated based on a total amount of 100 parts by weight of polyphenylene ether resin containing unsaturated carbon-carbon double bonds. For example, relative to 100 parts by weight of polyphenylene ether resin containing unsaturated carbon-carbon double bonds, the amount of unhydrogenated maleic anhydride modified first polyolefin is 1 to 20 parts by weight, including, for example, 1 part by weight, 5 parts by weight, 8 parts by weight, 10 parts by weight, 12 parts by weight, 15 parts by weight, and 20 parts by weight. Relative to 100 parts by weight of polyphenylene ether resin containing unsaturated carbon-carbon double bonds, the amount of benzocyclobutene modified second polyolefin is 5 to 100 parts by weight, including, for example, 5 parts by weight, 20 parts by weight, 40 parts by weight, 50 parts by weight, 60 parts by weight, 80 parts by weight, and 100 parts by weight. However, the present invention is not limited thereto.

[0040] The polyphenylene ether resin containing unsaturated carbon-carbon double bonds of the present invention can be any one or more polyphenylene ether resins containing unsaturated carbon-carbon double bonds that can be used to prepare prepregs, resin films, laminates or printed circuit boards, and can be any one or more commercially available products, homemade products or combinations thereof, such as any one or a combination of vinyl benzyl polyphenylene ether resin, (meth)acryloyl polyphenylene ether resin, vinyl polyphenylene ether resin, allyl polyphenylene ether resin, or allyl polyphenylene ether resin, but the present invention is not limited thereto.

[0041] The polyphenylene ether resins containing unsaturated carbon-carbon double bonds of the present invention 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 components in the resin composition containing unsaturated bonds, 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.

[0042] In one embodiment, for example, the polyphenylene ether resin containing unsaturated carbon-carbon double bonds includes 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, but the invention is not limited thereto. 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. For example, in one embodiment, the vinyl benzyl polyphenylene ether resin includes vinyl benzyl biphenyl polyphenylene ether resin, vinyl benzyl bisphenol A polyphenylene ether resin, or a combination thereof, but the present invention is not limited thereto.

[0043] In one embodiment, for example, the resin composition of the present invention may also contain, as needed, any one or a combination thereof of polyolefins, crosslinking agents containing unsaturated carbon-carbon double bonds, silicone resins, benzoxazine resins, epoxy resins, polyester resins, phenolic resins, amine curing agents, polyamides, polyimides, styrene-maleic anhydride, maleimide resins, cyanate ester resins, and maleimide-triazine resins.

[0044] Unless otherwise stated, in the resin composition of the present invention, the amounts of polyolefins, crosslinking agents containing unsaturated carbon-carbon double bonds, silicone resins, benzoxazine resins, epoxy resins, polyester resins, phenolic resins, polyamides, polyimides, styrene-maleic anhydride, maleimide resins, cyanate ester resins, and maleimide-triazine resins, which are different from components (B) and (C), can be adjusted as needed. For example, each component can be independently 1 to 100 parts by weight, such as 1 part by weight, 5 parts by weight, 10 parts by weight, 15 parts by weight, 20 parts by weight, 25 parts by weight, 50 parts by weight, or 100 parts by weight, but the present invention is not limited thereto. For example, the amount of amine curing agent can be adjusted as needed relative to 100 parts by weight of polyphenylene ether resin containing unsaturated carbon-carbon double bonds, for example, the amount of amine curing agent can be 1 to 30 parts by weight, but the present invention is not limited thereto.

[0045] The polyolefins of the present invention, different from components (B) and (C), can be any one or more polyolefins different from components (B) and (C) applicable to the preparation of prepregs, resin films, laminates, or printed circuit boards, and can be any one or more commercially available products, homemade products, or combinations thereof. The polyolefins of the resin compositions of the present invention, different from components (B) and (C), include polybutadiene, polyisoprene, styrene-butadiene copolymer, styrene-isoprene copolymer, styrene-butadiene-divinylbenzene polymer, vinyl-polybutadiene-urea polymer, polymethylstyrene, hydrogenated polybutadiene, hydrogenated polyisoprene, hydrogenated styrene-butadiene-divinylbenzene polymer, hydrogenated maleic anhydride addition polybutadiene, hydrogenated maleic anhydride addition styrene-butadiene polymer, hydrogenated styrene-butadiene copolymer, hydrogenated styrene-isoprene copolymer, styrene-ethylene-divinylbenzene polymer, styrene-ethylvinylbenzene-divinylbenzene polymer, or combinations thereof, but the present invention is not limited thereto.

[0046] The crosslinking agent containing unsaturated carbon-carbon double bonds in the resin composition of the present invention is any one or a combination of divinylbenzene (DVB), divinylnaphthalene, divinylbiphenyl, triallyl isocyanurate (TAIC), triallyl cyanurate (TAC), vinylbenzocyclobutene (VBCB), bis(vinylbenzyl)ether (BVBE), trivinylcyclohexane (TVCH), diallyl bisphenol A (DABPA), butadiene, decadiene, and octadiene.

[0047] In this invention, for example, the silicone resin may be any type of silicone resin known in the art, including polyalkyl silicone resin, polyaryl silicone resin, polyalkylaryl silicone resin, modified silicone resin, or combinations thereof. Modified silicone resins include amino-modified silicone resin, epoxy-modified silicone resin, methacrylamide-modified silicone resin, hydroxyl-modified silicone resin, carboxyl-modified silicone resin, or combinations thereof, but this invention is not limited thereto. Preferably, the amino-modified silicone resins of the present invention include, for example, amino-modified silicone resins manufactured by Shin-Etsu Chemical Industry Co., Ltd. under the 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 manufactured by Toray-Dow Corning Co., Ltd. under the trade names BY-16-853U, BY-16-853, BY-16-853B, etc.; amino-modified silicone resins manufactured by Momentive Performance Materials JAPAN Co., Ltd. under the trade names XF42-C5742, XF42-C6252, XF42-C5379, etc.; or combinations thereof. The epoxy-modified silicone resins of the present invention include, for example, the X-22-163 series manufactured by Shin-Etsu Chemical Industry Co., Ltd. The methacrylamide-modified silicone resin of the present invention is, for example, the X-22-164 series manufactured by Shin-Etsu Chemical Industry Co., Ltd.

[0048] In this invention, for example, the benzoxazine resin may be any type of benzoxazine resin known in the art, including bisphenol A type benzoxazine resin, bisphenol F type benzoxazine resin, phenolphthalein type benzoxazine resin, dicyclopentadiene type benzoxazine resin, phosphorus-containing benzoxazine resin, diamine type benzoxazine resin, and phenyl, vinyl, or allyl modified benzoxazine resin, but this invention is not limited thereto. Applicable commercially available products include, for example, Huntsman's trade names LZ-8270 (phenolphthalein type benzoxazine resin), LZ-8298 (phenolphthalein type benzoxazine resin), LZ-8280 (bisphenol F type benzoxazine resin), LZ-8290 (bisphenol A type benzoxazine resin), or Kolon Industries' trade names KZH-5031 (vinyl modified benzoxazine resin) and KZH-5032 (phenyl modified benzoxazine resin). The diamine-type benzoxazine resin may be a diaminodiphenylmethane benzoxazine resin, a diaminodiphenyl ether benzoxazine resin, a diaminodiphenyl sulfone benzoxazine resin, a diaminodiphenyl sulfide benzoxazine resin, or a combination thereof, but the present invention is not limited thereto.

[0049] In this invention, for example, the epoxy resin can be any type of epoxy resin known in the art. From the perspective of improving the heat resistance of the resin composition, the epoxy resin includes any one or a combination of bisphenol A epoxy resin, bisphenol F epoxy resin, bisphenol S epoxy resin, bisphenol AD ​​epoxy resin, phenolic (novolac) epoxy resin, trifunctional epoxy resin, tetrafunctional epoxy resin, multifunctional phenolic epoxy resin, dicyclopentadiene (DCPD) epoxy resin, phosphorus-containing epoxy resin, p-xylene epoxy resin, naphthalene-type epoxy resin (e.g., naphthol-type epoxy resin), benzofuran-type epoxy resin, and isocyanate-modified epoxy resin, but the invention is not limited thereto. In this invention, for example, 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. In this invention, for example, the phosphorus-containing epoxy resin may be DOPO (9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide) epoxy resin, DOPO-HQ epoxy resin, or a combination thereof.The aforementioned DOPO epoxy resin may be selected from one or more of DOPO-containing phenol novolac epoxy resin, DOPO-containing o-cresol novolac epoxy resin, and DOPO-containing bisphenol-A novolac epoxy resin; the aforementioned DOPO-HQ epoxy resin may be selected from one or more of DOPO-containing phenol novolac epoxy resin, DOPO-HQ-containing o-cresol novolac epoxy resin, and DOPO-HQ-containing bisphenol-A novolac epoxy resin, but the present invention is not limited thereto.

[0050] In this invention, for example, the polyester resin may be any type of polyester resin known in the art, including polyester resins containing a dicyclopentadiene structure, polyester resins containing a biphenyl structure, and polyester resins containing a naphthalene ring structure, but this invention is not limited thereto. The polyester resin includes trade names HPC-8000, HPC-8800, or HPC-8150 sold by Dai Nippon Ink Chemical, but this invention is not limited thereto.

[0051] In this invention, for example, the phenolic resin can be any type of phenolic resin known in the art, including phenolic resin or phenoxy resin, wherein the phenolic resin includes phenolic resin, o-methylphenolic resin, bisphenol A phenolic resin, naphthol phenolic resin, biphenyl phenolic resin and dicyclopentadienol resin, but this invention is not limited thereto.

[0052] In this invention, for example, the amine curing agent may be any type of amine curing agent known in the art, including at least one or a combination of diaminodiphenyl sulfone, diaminodiphenylmethane, diaminodiphenyl ether, diaminodiphenyl sulfide and dicyandiamide, but the invention is not limited thereto.

[0053] In this invention, for example, the polyamide can be any type of polyamide known in the art, including various commercially available polyamide resin products, but the invention is not limited thereto.

[0054] In this invention, for example, the polyimide can be any type of polyimide known in the art, including various commercially available polyimide resin products, but the invention is not limited thereto.

[0055] In this invention, for example, styrene-maleic anhydride can be any type of styrene-maleic anhydride known in the art, wherein the ratio of styrene (St) to maleic anhydride (MA) can be 1 / 1, 2 / 1, 3 / 1, 4 / 1, 6 / 1, 8 / 1, or 12 / 1. Specific examples include styrene-maleic anhydride copolymers such as SMA-1000, SMA-2000, SMA-3000, EF-30, EF-40, EF-60, and EF-80 sold by Cray Valley, or styrene-maleic anhydride copolymers such as C400, C500, C700, and C900 sold by Polyscope, but this invention is not limited thereto.

[0056] In this invention, for example, the maleimide resin can be any type of maleimide resin known in the art, including: 4,4'-diphenylmethane bismaleimide, polyphenylmethane maleimide (or oligomer of phenylmethane maleimide), bisphenol A diphenylether bismaleimide, and 3,3'-dimethyl-5,5'-diethyl-4,4'-diphenylmethane bismaleimide. bismaleimide), 3,3'-dimethyl-5,5'-dipropyl-4,4'-diphenylmethane bismaleimide, m-phenylene bismaleimide, 4-methyl-1,3-phenylene bismaleimide bismaleimide), 1,6-bismaleimide-(2,2,4-trimethyl)hexane, n-2,3-dimethylphenylmaleimide, n-2,6-dimethylphenylmaleimide, N-phenylmaleimide, vinylbenzylmaleimide Maleimide (VBM), maleimides containing a biphenyl structure, maleimides containing isopropyl and meta-aryl structures, maleimides containing an indane structure, maleimide resins containing an aliphatic structure with 10 to 50 carbon atoms, 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, but the invention is not limited thereto. These components should be understood to include modified products containing these components.

[0057] For example, maleimide resins include those produced by Daiwakasei Industry Co., Ltd. under the 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, or those produced by KI Chemical Co., Ltd. under the trade names BMI-70, BMI-80, etc., or those produced by Nippon Kayaku Co., Ltd. under the trade names MIR-3000 or MIR-5000, etc., or maleimide resins containing indane structures produced by DIC, but the present invention is not limited thereto.

[0058] For example, aliphatic maleimide resins containing 10 to 50 carbon atoms, 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, but the present invention is not limited thereto. The aliphatic maleimide resins containing 10 to 50 carbon atoms of the present invention may include 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, but the present invention is not limited thereto.

[0059] In this invention, for example, the cyanate ester can be any type of cyanate ester resin known in the art, such as compounds having an Ar-OC≡N structure, wherein Ar can be a substituted or unsubstituted aromatic group. From the perspective of improving the heat resistance of the resin composition, cyanate esters include phenolic cyanate ester resins, bisphenol A cyanate ester resins, bisphenol F cyanate ester resins, cyanate ester resins containing a dicyclopentadiene structure, cyanate ester resins containing a naphthalene ring structure, phenolphthalein cyanate ester resins, adamantane cyanate ester resins, fluorene cyanate ester resins, or combinations thereof, but this invention is not limited thereto. The phenolic cyanate ester resin can be bisphenol A phenolic cyanate ester resin, bisphenol F phenolic cyanate ester resin, or combinations thereof. For example, cyanate ester resins can be those 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, ULL950S, HTL-300, CE-320, LVT-50, and LeCy.

[0060] In this invention, for example, the maleimide triazine resin can be any type of maleimide triazine resin known in the art, including: maleimide triazine resin obtained by polymerizing maleimide resin with bisphenol A type cyanate resin, maleimide triazine resin obtained by polymerizing maleimide resin with bisphenol F type cyanate resin, maleimide triazine resin obtained by polymerizing maleimide resin with phenolic phenolic cyanate resin, and maleimide triazine resin obtained by polymerizing maleimide resin with cyanate resin containing a dicyclopentadiene structure, but this invention is not limited thereto. In one embodiment, the maleimide triazine resin can be obtained by polymerizing the aforementioned maleimide resin and the aforementioned cyanate resin in any molar ratio; for example, the molar ratio of maleimide resin to cyanate resin can be 1:1 to 10, such as 1:1, 1:2, 1:4, 1:6, 1:8, 1:10, but this invention is not limited thereto.

[0061] In one embodiment, for example, the resin composition further includes a curing accelerator, a polymerization inhibitor, a flame retardant, an inorganic filler, a surface treatment agent, a dye, a toughening agent, a solvent, or a combination thereof.

[0062] In this invention, for example, the curing accelerator (including the curing initiator) may include a Lewis base or Lewis acid catalyst. The Lewis base may include one or more of the following: imidazole, boron trifluoride amine complex, ethyltriphenyl phosphonium chloride, 2-methylimidazole (2MI), 2-phenyl-1H-imidazole (2PZ), 2-ethyl-4-methylimidazole (2E4MZ), triphenylphosphine (TPP), and 4-dimethylaminopyridine (DMAP). The Lewis acid may include metal salt compounds, such as manganese, iron, cobalt, nickel, copper, zinc, etc., and metal catalysts such as zinc octanoate and cobalt octanoate. Curing accelerators also include curing initiators, such as peroxides that can generate free radicals. Curing initiators include diisopropylbenzene peroxide (DCP), tert-butyl peroxybenzoate, dibenzoyl peroxide (BPO), 2,5-dimethyl-2,5-di(tert-butylperoxy)-3-hexyne (25B), and bis(tert-butylperoxyisopropyl)benzene or combinations thereof, but the invention is not limited thereto. For example, in one embodiment, the resin composition of the present invention may further contain 0.01 to 5.0 parts by weight of curing accelerator, preferably 0.01 to 4.0 parts by weight, and more preferably 0.1 to 3.0 parts by weight of curing accelerator, compared to 100 parts by weight of polyphenylene ether resin containing unsaturated carbon-carbon double bonds, but the invention is not limited thereto.

[0063] In this invention, for example, the polymerization inhibitor may include 1,1-diphenyl-2-trinitrophenylhydrazine, methacrylonitrile, nitroxide-stabilized free radicals, triphenylmethyl free radicals, metal ion free radicals, sulfur free radicals (e.g., dithioesters), hydroquinone, p-methoxyphenol, p-benzoquinone, phenthiazide, β-phenylnaphthylamine, p-tert-butylcatechol, methylene blue, 4,4'-butylenebis(6-tert-butyl-3-methylphenol), and 2,2'-methylenebis(4-ethyl-6-tert-butylphenol) or combinations thereof, but the invention is not limited thereto. For example, the aforementioned nitroxide-stabilized free radicals may include 2,2,6,6-substituted-1-piperidinoxy free radicals or 2,2,5,5-substituted-1-pyrrolidineoxy free radicals derived from cyclic hydroxylamines. As substituents, preferably alkyl groups with four or fewer carbon atoms, such as methyl or ethyl, but the invention is not limited thereto. Nitrogen oxide free radical compounds include 2,2,6,6-tetramethyl-1-piperidineoxy radical, 2,2,6,6-tetraethyl-1-piperidineoxy radical, 2,2,6,6-tetramethyl-4-oxo-1-piperidineoxy radical, 2,2,5,5-tetramethyl-1-pyrrolidineoxy radical, 1,1,3,3-tetramethyl-2-isodihydroindoleoxy radical, N,N-di-tert-butylamineoxy radical, etc., but the present invention is not limited thereto. Stable free radicals such as galvinoxyl radicals can also be used instead of nitrogen oxide free radicals. The polymerization inhibitor of the resin composition of the present invention can also be a product derived from the substitution of hydrogen atoms or atomic groups in the polymerization inhibitor by other atoms or atomic groups. For example, products derived from the substitution of hydrogen atoms in the polymerization inhibitor by atomic groups such as amino, hydroxyl, and ketone carbonyl groups. For example, in one embodiment, based on 100 parts by weight of polyphenylene ether resin containing unsaturated carbon-carbon double bonds, the resin composition of the present invention may further include 0.001 parts by weight to 20 parts by weight of a polymerization inhibitor, preferably 0.01 parts by weight to 10 parts by weight of a polymerization inhibitor, but the present invention is not limited thereto.

[0064] In this invention, for example, the flame retardant can be any one or more flame retardants applicable to the preparation of prepregs, resin films, laminates, or printed circuit boards, including phosphorus-containing flame retardants or bromine-containing flame retardants. Bromine-containing flame retardants preferably include decabromodiphenyl ethane, but the invention is not limited thereto. Preferred phosphorus-containing flame retardants include: 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), RDXP (such as commercially available products like PX-200, PX-201, PX-202), ammonium polyphosphate, and melamine polyphosphate. Polyphosphate, phosphazene compounds (such as commercially available products like SPB-100, SPH-100, SPV-100), 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (DOPO) compounds and their derivatives or resins (e.g., bisDOPO compounds), diphenylphosphine oxide (DPPO) compounds and their derivatives or resins (e.g., bisDPPO compounds), melamine cyanurate and tri-hydroxyethyl isocyanurate, aluminum phosphonates (e.g., OP-930, OP-935), or combinations thereof.

[0065] In this invention, for example, the flame retardant may be a flame retardant sold by Katayama Chemical Industry Co., Ltd., including V1, V2, V3, V4, V5, V7, S-2, S-4, E-4c, E-7c, E-8g, E-9g, E-10g, E-100, B-3, W-1o, W-2h, W-2o, W-3o, W-4o, OX-1, OX-2, OX-4, OX-6, OX-6+, OX-7, OX-7+, OX-13, BPE-1, BPE-3, HyP-2, API-9, CMPO, ME-20, C-1R, C-1S, C-3R, C-3S, or C-11R, but this invention is not limited thereto. The flame retardant of this invention may include one or more of the above.

[0066] For example, in one embodiment, the resin composition of the present invention may further include 1 to 100 parts by weight of a flame retardant, preferably 5 to 50 parts by weight, relative to 100 parts by weight of the polyphenylene ether resin containing unsaturated carbon-carbon double bonds.

[0067] In this invention, for example, the inorganic filler may be any one or more inorganic fillers applicable to the preparation of prepregs, resin films, laminates, or printed circuit boards, including: silica (molten, non-molten, porous, or hollow), alumina, aluminum hydroxide, magnesium oxide, magnesium hydroxide, calcium carbonate, aluminum nitride, boron nitride, silicon aluminum carbide, silicon carbide, titanium dioxide, barium titanate, lead titanate, strontium titanate, calcium titanate, magnesium titanate, barium zirconate, lead zirconate, magnesium zirconate, lead zirconate titanate, zinc molybdate, calcium molybdate, magnesium molybdate, ammonium molybdate, zinc molybdate-modified talc, zinc oxide, zirconium oxide, mica, boehmite (AlOOH), calcined talc, talc, silicon nitride, zirconium tungstate, litharge, calcined kaolin, or combinations thereof, but this invention is not limited thereto. Furthermore, the inorganic filler can be spherical (including solid or hollow spheres), fibrous, plate-like, granular, flake-like, or needle-like, and can be selectively pretreated with a silane coupling agent. In addition, the inorganic filler can be prepared by various methods, such as melt processing, deflagration, and chemical synthesis. Furthermore, the particle size of the inorganic filler is not particularly limited, but the median particle size D50 can be 1 to 45 micrometers, preferably 1 to 15 micrometers, and more preferably 1 to 10 micrometers. For example, in one embodiment, relative to 100 parts by weight of the polyphenylene ether resin containing unsaturated carbon-carbon double bonds, the resin composition of the present invention may further comprise 10 to 300 parts by weight of the inorganic filler, preferably 50 to 300 parts by weight, and more preferably 75 to 300 parts by weight, but the present invention is not limited thereto.

[0068] In this invention, for example, the surface treatment agent may include silane compounds (e.g., siloxane compounds), which can be further classified according to the type of functional group as amino silane compounds, epoxy silane compounds, vinyl silane compounds, hydroxy silane compounds, isocyanate silane compounds, methacryloxy silane compounds, and acryloyloxy silane compounds. The main function of adding the surface treatment agent in this invention is to enable the inorganic filler to be uniformly dispersed in the resin composition, but this invention is not limited thereto. For example, in one embodiment, relative to 100 parts by weight of polyphenylene ether resin containing unsaturated carbon-carbon double bonds, the resin composition of this invention may further include 0.001 parts by weight to 20 parts by weight of the surface treatment agent, preferably 0.01 parts by weight to 10 parts by weight of the surface treatment agent, but this invention is not limited thereto.

[0069] In this invention, for example, the dyeing agent may include dye or pigment. For example, in one embodiment, based on 100 parts by weight of a polyphenylene ether resin containing unsaturated carbon-carbon double bonds, the resin composition of this invention may further include 0.001 parts by weight to 10 parts by weight of the dyeing agent, preferably 0.01 parts by weight to 5 parts by weight of the dyeing agent, but the invention is not limited thereto.

[0070] The main function of adding toughening agents in this invention is to improve the toughness of the resin composition. In this invention, for example, the toughening agent may include carboxyl-terminated butadiene acrylonitrile rubber (CTBN), core-shell rubber, ethylene propylene rubber, or combinations thereof, but this invention is not limited thereto. For example, in one embodiment, based on 100 parts by weight of polyphenylene ether resin containing unsaturated carbon-carbon double bonds, the resin composition of this invention may further include 1 to 20 parts by weight of toughening agent, preferably 3 to 10 parts by weight of toughening agent, but this invention is not limited thereto.

[0071] In this invention, for example, the solvent can be any solvent suitable for dissolving the resin composition of this invention, including: methanol, ethanol, ethylene glycol monomethyl ether, acetone, butanone (also known as methyl ethyl ketone), methyl isobutyl ketone, cyclohexanone, N-methylpyrrolidone, toluene, xylene, methoxyethyl acetate, ethoxyethyl acetate, propoxyethyl acetate, ethyl acetate, dimethylformamide, dimethylacetamide, propylene glycol methyl ether acetate, etc., or mixtures thereof, but this invention is not limited thereto. The amount of solvent added is intended to completely dissolve the resin and adjust to a specific total solids content of the resin composition. For example, in one embodiment, the amount of solvent added is adjusted to a total solids content of 50% to 85% (by weight) of the resin composition, but this invention is not limited thereto.

[0072] In addition to the aforementioned resin composition, the present invention also provides an article made from the above-mentioned resin composition, such as a component in various electronic products, including: a prepreg, a resin film, a laminate, or a printed circuit board, but the present invention is not limited thereto.

[0073] For example, the resin composition of the present invention can be made into a prepreg, which includes a reinforcing material and a layer disposed on the reinforcing material. The layer is obtained by heating the aforementioned resin composition at a high temperature to form a semi-cured state (B-stage). The baking temperature for making the prepreg is between 100°C and 180°C, preferably between 120°C and 160°C. The reinforcing material can be any of a fiber material, woven fabric, or nonwoven fabric, and the woven fabric preferably includes glass fiber cloth. There is no particular limitation on the type of glass fiber cloth, and it can be various glass fiber cloths that can be used for printed circuit boards, such as E-type glass fiber cloth, D-type glass fiber cloth, S-type glass fiber cloth, T-type glass fiber cloth, L-type glass fiber cloth, Q-type glass fiber cloth, or QL-type glass fiber cloth (a glass fiber cloth with a mixed structure made of Q glass and L glass); the type of glass fiber includes yarn and roving, etc., and the form includes open fiber or closed fiber, and the end face shape includes round or flat shape. The aforementioned nonwoven fabric preferably includes liquid crystal resin nonwoven fabric, such as polyester nonwoven fabric, polyurethane nonwoven fabric, etc., but the present invention is not limited to this. The aforementioned fabric may also include liquid crystal resin fabric, such as polyester fabric or polyurethane fabric, but the present invention is not limited thereto. This reinforcing material can increase the mechanical strength of the prepreg. In one 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.

[0074] For example, the resin composition of the present invention can be made into a resin film, which is obtained by baking and heating the aforementioned resin composition to form a semi-cured state. The resin composition can be selectively coated onto a support material, including a liquid crystal resin film, a polytetrafluoroethylene film, a polyethylene terephthalate film (PET film), a polyimide film (PI film), a metal foil, or a resin-coated copper foil (RCC), and then baked and heated to form a semi-cured state, thereby forming a resin film from the resin composition. However, the present invention is not limited thereto.

[0075] For example, the resin composition of the present invention can be used to form various laminates comprising at least two metal foils and at least one insulating layer disposed between the two metal foils. The insulating layer can be formed by curing the aforementioned resin composition under high temperature and high pressure (C-stage). Applicable curing temperatures are, for example, between 190°C and 220°C, preferably between 200°C and 210°C, with a curing time of 90 to 180 minutes, preferably 120 to 150 minutes. Applicable pressing pressures are, for example, between 300 psi and 550 psi, preferably between 400 psi and 550 psi. The aforementioned insulating layer can be obtained by curing the aforementioned prepreg or resin film. The aforementioned metal foils can be made of copper, aluminum, nickel, platinum, silver, gold, or alloys thereof, such as copper foil. In a preferred embodiment, the laminate is a copper foil substrate.

[0076] In one embodiment, the aforementioned multilayer board can be further processed into a printed circuit board. One method of manufacturing the printed circuit board of the present invention involves using a double-sided copper-clad laminate (e.g., product EM-827, available from Taiguang Electronic Materials (Kunshan) Co., Ltd.) 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 and increase roughness. Then, the copper foil, the aforementioned prepreg, the aforementioned inner layer circuit board, the aforementioned prepreg, and the copper foil are stacked sequentially, and then heated in a vacuum lamination apparatus at a temperature of 190°C–220°C for 90–180 minutes to cure the insulating layer material of the prepreg. Next, various circuit board processes known in the art, such as blackening, drilling, and copper plating, are performed on the outermost copper foil to obtain a printed circuit board.

[0077] For example, in one embodiment, the article made from the resin composition of the foregoing embodiments contains reinforcing or supporting materials and a semi-cured or cured product obtained by heating and chemically crosslinking the resin composition.

[0078] For example, in one embodiment, the resin composition disclosed in this invention and various articles prepared therefrom preferably have one or more of the following characteristics:

[0079] The BC tension difference measured and calculated according to the method described in IPC-TM-650 2.4.8 is less than or equal to 0.3 lb / in, for example, between 0.05 lb / in and 0.3 lb / in;

[0080] The solder bleed rate measured according to the method of IPC-TM-650 2.4.13.1 was 0%.

[0081] The solder ball thrust is tested using a solder ball thruster and is greater than or equal to 805 gf, for example, between 805 and 1329 gf.

[0082] Scanning electron microscopy (SEM) was used to observe that the interface between the substrate glass cloth and the resin was seamless.

[0083] The resin compositions of the embodiments and comparative examples of the present invention were prepared using various raw materials from the following sources in accordance with the amounts specified in Tables 1 to 5, and were further prepared into various test samples.

[0084] The chemical raw materials used in the embodiments and comparative examples of this invention are as follows:

[0085] SA9000: (Meth)acryloyl polyphenylene ether resin, purchased from Sabic.

[0086] OPE-2st 1200: Ethylene benzyl-terminated polyphenylene ether resin, purchased from Mitsubishi Gas Chemical.

[0087] OPE-2st 2200: Ethylene benzyl-terminated polyphenylene ether resin, purchased from Mitsubishi Gas Chemical.

[0088] Ricon 131MA5: Unhydrogenated maleic anhydride addition polybutadiene, purchased from Cray Valley.

[0089] Ricon 130MA8: Unhydrogenated maleic anhydride addition polybutadiene, purchased from Cray Valley.

[0090] Ricon 130MA13: Unhydrogenated maleic anhydride addition polybutadiene, purchased from Cray Valley.

[0091] Ricon 131MA10: Unhydrogenated maleic anhydride addition polybutadiene, purchased from Cray Valley.

[0092] Ricon 156MA17: Unhydrogenated maleic anhydride addition polybutadiene, purchased from Cray Valley.

[0093] Ricon 184MA6: Unhydrogenated maleic anhydride addition styrene-butadiene copolymer, purchased from Cray Valley.

[0094] P1: Self-made, detailed below.

[0095] P2: Self-made, detailed below.

[0096] P3: Homemade, detailed below.

[0097] P4: Homemade, detailed below.

[0098] P5: Homemade, detailed below.

[0099] P6: Homemade, detailed below.

[0100] P7: Homemade, detailed below.

[0101] P8: Homemade, detailed below.

[0102] P9: Homemade, detailed below.

[0103] P10: Homemade, detailed below.

[0104] BVPE: Bis(vinylphenyl)ethane, purchased from Linchuan Chemical.

[0105] TAIC: Triallyl isocyanurate, purchased from Sartomer.

[0106] Ricon 100: Styrene-butadiene copolymer, purchased from Cray Valley.

[0107] B1000: Polybutadiene, purchased from Japan Soda.

[0108] B3000: Polybutadiene, purchased from Japan Soda.

[0109] SBS-A: Styrene-butadiene block copolymer, purchased from Japan Soda.

[0110] EA-3000: Terminally acryloyl polybutadiene, purchased from Nippon Soda.

[0111] X-12-1281A-ES: Silane-modified styrene-butadiene copolymer, purchased from Shin-Yue Chemical.

[0112] JP-100: Epoxy-containing polybutadiene, purchased from Japan Soda.

[0113] FG1901: Hydrogenated maleic anhydride-modified styrene-butadiene copolymer, purchased from KRATON.

[0114] 25B: 2,5-Dimethyl-2,5-bis(tert-butylperoxy)-3-hexyne, purchased from Nippon Oils & Fats Co., Ltd.

[0115] Spherical silica: The median particle size D50 is about 2.5±2 micrometers. It is chemically synthesized spherical silica produced by microemulsion and surface treated with silane coupling agent. It is commercially available.

[0116] Solvent: Toluene and methyl ethyl ketone in a weight ratio of 2:1. Both toluene and methyl ethyl ketone are commercially available. The solvent content is expressed as "appropriate amount," meaning that the solvent content is adjusted to make the overall solid content of the resin composition 60% to 68% (solid content, S / C = 60% to 68%).

[0117] Preparation Example 1: P1

[0118] Add 200 g of B1000, 183 g of 4-bromobenzocyclobutene, 4.5 g of palladium acetate, 30.4 g of tris(o-methylphenyl)phosphine, 202 g of triethylamine, and 2000 mL of anhydrous acetonitrile / tetrahydrofuran (DMF) mixed solvent to the reaction vessel. Vacuum and nitrogen gas are purged and repeated three times. The reaction is then heated under nitrogen protection and refluxed for 36 hours. The conversion rate of 4-bromobenzocyclobutene is tested by gas chromatography. Heating is stopped when the expected conversion rate (>50%) is reached. The reaction is cooled to room temperature and petroleum ether is added and stirred. The salt and palladium catalyst generated in the reaction are removed by filtration. The filtrate is subjected to column chromatography and rotary evaporation to obtain a pale yellow viscous liquid P1.

[0119] Preparation Example 2: P2

[0120] Add 200 g of B3000, 183 g of 4-bromobenzocyclobutene, 4.5 g of palladium acetate, 30.4 g of tris(o-methylphenyl)phosphine, 202 g of triethylamine, and 3000 mL of anhydrous acetonitrile / DMF mixed solvent to the reaction vessel. Vacuum and nitrogen gas are purged and repeated three times. The reaction is then heated under nitrogen protection and refluxed for 48 hours. The conversion rate of 4-bromobenzocyclobutene is tested by gas chromatography. Heating is stopped when the expected conversion rate (>50%) is reached. The reaction is cooled to room temperature and petroleum ether is added and stirred. The salt and palladium catalyst generated in the reaction are removed by filtration. The filtrate is subjected to column chromatography and rotary evaporation to obtain a pale yellow viscous liquid P2.

[0121] Preparation Example 3: P3

[0122] Add 450 g of Ricon 100, 183 g of 4-bromobenzocyclobutene, 6.75 g of palladium acetate, 36.48 g of tris(o-methylphenyl)phosphine, 202 g of triethylamine, and 3500 mL of anhydrous acetonitrile / DMF mixed solvent to the reaction vessel. Vacuum and nitrogen gas are purged and repeated three times. The reaction is then heated under nitrogen protection and refluxed for 72 hours. The conversion rate of 4-bromobenzocyclobutene is tested by gas chromatography. Heating is stopped when the expected conversion rate (>50%) is reached. The reaction is cooled to room temperature and petroleum ether is added and stirred. The salt and palladium catalyst generated in the reaction are removed by filtration. The filtrate is subjected to column chromatography and rotary evaporation to obtain a pale yellow viscous liquid P3.

[0123] Preparation Example 4: P4

[0124] Add 260 g of SBS-A, 128.1 g of 4-bromobenzocyclobutene, 4.5 g of palladium acetate, 30.4 g of tris(o-methylphenyl)phosphine, 101 g of triethylamine, and 3000 mL of anhydrous acetonitrile / cyclohexane / DMF mixed solvent to the reaction vessel. After evacuating and purging with nitrogen three times, heat under nitrogen protection and reflux for 72 hours. The conversion rate of 4-bromobenzocyclobutene is tested by gas chromatography. Heating is stopped when the expected conversion rate (>50%) is reached. After cooling the reaction to room temperature, petroleum ether is added and stirred. The salt and palladium catalyst generated in the reaction are removed by filtration. The filtrate is subjected to column chromatography and rotary evaporation to obtain a pale yellow solid P4.

[0125] Preparation Example 5: P5

[0126] Add 470 g of Ricon 131MA5, 183 g of 4-bromobenzocyclobutene, 6.75 g of palladium acetate, 36.48 g of tris(o-methylphenyl)phosphine, 202 g of ethylamine, and 3500 mL of anhydrous acetonitrile / DMF mixed solvent to the reactor. Vacuum and nitrogen gas are purged and repeated three times. The reactor is then heated under nitrogen protection and refluxed for 50 hours. The conversion rate of 4-bromobenzocyclobutene is tested by gas chromatography. Heating is stopped when the expected conversion rate (>50%) is reached. The reaction is cooled to room temperature and petroleum ether is added and stirred. The salt and palladium catalyst generated in the reaction are removed by filtration. The filtrate is subjected to column chromatography and rotary evaporation to obtain a yellow viscous liquid P5.

[0127] Preparation Example 6: P6

[0128] Add 250 g of Ricon 156MA17, 183 g of 4-bromobenzocyclobutene, 6.75 g of palladium acetate, 36.48 g of tris(o-methylphenyl)phosphine, 202 g of triethylamine, and 3500 mL of anhydrous acetonitrile / DMF mixed solvent to the reactor. Vacuum and nitrogen gas are purged and repeated three times. The reactor is then heated under nitrogen protection and refluxed for 60 hours. The conversion rate of 4-bromobenzocyclobutene is tested by gas chromatography. Heating is stopped when the expected conversion rate (>50%) is reached. The reaction is cooled to room temperature and petroleum ether is added and stirred. The salt and palladium catalyst generated in the reaction are removed by filtration. The filtrate is subjected to column chromatography and rotary evaporation to obtain a yellow viscous liquid P6.

[0129] Preparation Example 7: P7

[0130] Add 455 g of Ricon 184MA6, 128.1 g of 4-bromobenzocyclobutene, 4.5 g of palladium acetate, 30.4 g of tris(o-methylphenyl)phosphine, 101 g of triethylamine, and 3000 mL of anhydrous acetonitrile / DMF mixed solvent to the reactor. Vacuum and nitrogen gas are purged and repeated three times. The reactor is then heated under nitrogen protection and refluxed for 72 hours. The conversion rate of 4-bromobenzocyclobutene is tested by gas chromatography. Heating is stopped when the expected conversion rate (>50%) is reached. The reaction is cooled to room temperature and petroleum ether is added and stirred. The salt and palladium catalyst generated in the reaction are removed by filtration. The filtrate is subjected to column chromatography and rotary evaporation to obtain a yellow viscous liquid P7.

[0131] Preparation Example 8: P8

[0132] Add 200 g of EA-3000, 183 g of 4-bromobenzocyclobutene, 4.5 g of palladium acetate, 30.4 g of tris(o-methylphenyl)phosphine, 202 g of triethylamine, and 3000 mL of anhydrous acetonitrile / DMF mixed solvent to the reactor. Vacuum and nitrogen gas are purged and repeated three times. The reactor is then heated under nitrogen protection and refluxed for 48 hours. The conversion rate of 4-bromobenzocyclobutene is tested by gas chromatography. Heating is stopped when the expected conversion rate (>50%) is reached. The reaction is cooled to room temperature and petroleum ether is added and stirred. The salt and palladium catalyst generated in the reaction are removed by filtration. The filtrate is subjected to column chromatography and rotary evaporation to obtain a yellow viscous liquid P8.

[0133] Preparation Example 9: P9

[0134] Add 455 g of X-12-1281A-ES, 128.1 g of 4-bromobenzocyclobutene, 4.5 g of palladium acetate, 30.4 g of tris(o-methylphenyl)phosphine, 101 g of triethylamine, and 3000 mL of anhydrous acetonitrile / cyclohexane / DMF mixed solvent to the reaction vessel. After evacuating and purging with nitrogen three times, heat under nitrogen protection and reflux for 72 hours. The conversion rate of 4-bromobenzocyclobutene is tested by gas chromatography. Heating is stopped when the expected conversion rate (>50%) is reached. After cooling the reaction to room temperature, petroleum ether is added and stirred. The salt and palladium catalyst generated in the reaction are removed by filtration. The filtrate is subjected to column chromatography and rotary evaporation to obtain a pale yellow solid P9.

[0135] Preparation Example 10: P10

[0136] Add 260 g of JP-100, 183 g of 4-bromobenzocyclobutene, 4.5 g of palladium acetate, 30.4 g of tris(o-methylphenyl)phosphine, 202 g of triethylamine, and 2000 mL of anhydrous acetonitrile / DMF mixed solvent to the reactor. Vacuum and nitrogen gas are purged and repeated three times. The reactor is then heated under nitrogen protection and refluxed for 40 hours. The conversion rate of 4-bromobenzocyclobutene is tested by gas chromatography. Heating is stopped when the expected conversion rate (>50%) is reached. The reaction is cooled to room temperature and petroleum ether is added and stirred. The salt and palladium catalyst generated in the reaction are removed by filtration. The filtrate is subjected to column chromatography and rotary evaporation to obtain a pale yellow viscous liquid P10.

[0137] The composition (all units are parts by weight) and sample characteristic test results of the resin compositions of the embodiments and comparative examples of the present invention are shown in Tables 1 to 5:

[0138] Table 1. Composition and property test results of the resin compositions in Examples E1 to E6

[0139]

[0140] Table 2. Composition and property test results of the resin compositions in Examples E7 to E12

[0141]

[0142] Table 3. Composition and property test results of the resin compositions in Examples E13 to E18

[0143]

[0144] Table 4. Composition and property test results of the resin compositions of comparative examples C1 to C6.

[0145]

[0146] Table 5. Composition and property test results of the resin compositions of comparative examples C7 to C9.

[0147]

[0148] Manufacturing of prepreg (PP, also known as bonding sheet)

[0149] The resin compositions used in the examples or comparative examples were uniformly mixed to form a varnish. This varnish was then injected into an impregnation tank, and glass fiber cloth (e.g., L-glass fiber fabric of specification 2116 or 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 then heated at 130°C to 160°C to a semi-cured state (B-Stage) to obtain a prepreg. The prepreg made using 1078 L-glass fiber cloth had a resin content of approximately 67%; the prepreg made using 2116 L-glass fiber cloth had a resin content of approximately 55%.

[0150] The characteristic testing methods and characteristic analysis items of the embodiments and comparative examples of the present invention are as follows:

[0151] 1. BC tensile strength difference (BC tensile strength is the peeling strength of bonding sheet and core)

[0152] (1) Preparation of a copper-free inner layer substrate (core)

[0153] Two 18-micron thick ultra-low surface roughness (HVLP) copper foils and eight prepregs made of resin composition and L-glass fiber cloth of 2116 from the examples or comparative examples are prepared. The HVLP copper foils, eight prepregs and one HVLP copper foil are stacked in sequence and pressed under vacuum conditions, pressure of 500 psi and 200°C for 2 hours to form a copper-containing inner layer substrate I. The copper-containing inner layer substrate I is etched to remove the copper foils on both sides to obtain a copper-free inner layer substrate I.

[0154] (2) Evaluation of substrate preparation

[0155] Two high-temperature high-elongation (HTE) copper foils with a thickness of 18 micrometers, two prepregs made of the resin composition in the examples or comparative examples and L-glass fiber cloth of 2116, and one copper-free inner layer substrate I are prepared. The HTE copper foil, one prepreg, one copper-free inner layer substrate I, one prepreg, and one HTE copper foil are stacked in the following order, and the substrate I is pressed under vacuum conditions, pressure of 500 psi, and temperature of 200°C for 2 hours to form evaluation substrate I.

[0156] (3) Determination of the difference in BC tension

[0157] Three 0.5-inch x 5-inch strips were cut from the edge and center regions of the aforementioned evaluation substrate I. A universal tensile testing machine was used, and measurements were performed according to the method described in IPC-TM-650 2.4.8. No copper foil etching was required during the process, and the test location was the interface between the prepreg and the copper-free inner layer substrate I. The interfacial tensile force between the prepreg and the copper-free inner layer substrate I on both sides of each strip was measured, in lb / in. The average interfacial tensile force between the prepreg and the copper-free inner layer substrate I on both sides of the three strips cut from the center region was recorded as F1, and the average interfacial tensile force between the prepreg and the copper-free inner layer substrate I on both sides of the three strips cut from the edge region was recorded as F2. The difference in BC tensile force between the center and edge regions was calculated as F1 - F2. A smaller difference in BC tensile force between the center and edge regions indicates better BC tensile force stability.

[0158] 2. Thrust of the tin ball

[0159] (1) Preparation of copper-containing inner layer substrate

[0160] That is, the aforementioned copper-containing inner layer substrate I.

[0161] (2) Evaluation of substrate preparation

[0162] Both sides of the copper-containing inner layer substrate I were browned. Then, a prepreg made of resin composition and L-glass fiber cloth of 1078 was laminated on both sides of the browned inner layer substrate. Then, a 35-micron HTE copper foil was laminated on the surface of each of the two prepregs. The substrate was then pressed under vacuum conditions, pressure of 500 psi, and temperature of 200°C for 2 hours to form a four-layer board. Then, the outer layer circuit was fabricated and solder mask was formed on the four-layer board to form evaluation substrate II. The diameter of the pads on evaluation substrate II is 0.5 mm.

[0163] (3) Measurement of the thrust of the solder ball

[0164] On the pads of the aforementioned evaluation substrate II, a solder ball is implanted on both the front and back sides. A solder ball pushing machine is used to test the pushing force of the solder balls on both sides, with the unit being gf. The pusher width is set to 0.05 inches. The average value of the pushing force of the solder balls on both sides is taken as the pushing force of each evaluation substrate II. The higher the value of the pushing force, the better. A higher pushing force indicates a stronger bonding force between the substrate and the solder ball, and thus better solderability.

[0165] 3. Bonding Gap at the Interface between Fiberglass and Resin

[0166] Take the aforementioned copper-free inner layer substrate I and prepare a cross section. Observe the interface between the glass fiber cloth and the resin in each cross section under a scanning electron microscope (SEM) to see if there are gaps. If there are no gaps, it is marked as OK; if there are gaps, it is marked as NG. No gaps are preferred.

[0167] 4. Solder floating delamination rate

[0168] (1) Preparation of copper-free inner layer substrate II

[0169] Two 18-micron thick ultra-low surface roughness (HVLP) copper foils and a prepreg made of the resin composition in the example or comparative example and two 2116 L-glass fiber cloths are prepared. The HVLP copper foil, two prepregs and one HVLP copper foil are stacked in sequence and pressed under vacuum conditions, pressure of 500 psi and 200°C for 2 hours to form a copper-containing inner layer substrate II. The copper-containing inner layer substrate is etched to remove the copper foil on both sides to obtain a copper-free inner layer substrate II.

[0170] (2) Evaluation of substrate preparation

[0171] Prepare 8 prepregs made of 1078 L-glass fiber cloth and 3 copper-free inner layer substrates II as described above. Stack them alternately in the order of 1 copper-free inner layer substrate II and 2 prepregs. Then, stack 18-micron thick HVLP copper foil on the outermost front and back sides respectively. Press them together under vacuum conditions, pressure of 500 psi, and 200°C for 2 hours to form an eight-layer board. Then, drill holes and electroplate the eight-layer board to form evaluation substrate III.

[0172] (3) Determination of the rate of tin-blown circuit board

[0173] The aforementioned evaluation substrate III was cut into six 2.2-inch * 5.9-inch samples. Each sample was placed in a tin bath at 288°C for 10 seconds to bleach in tin, then removed and cooled for 30 seconds. This cycle was repeated 20 times. The samples were then sliced ​​and observed under an optical microscope to check for any signs of delamination. The delamination rate was calculated as: number of delamination holes * 100% / total number of holes. A lower delamination rate was better. The term "delamination" can be understood as interlayer peeling or blistering. Delamination can occur between any layers of the substrate. For example, interlayer peeling between insulating layers can be called delamination, as can blistering separation between copper foil and insulating layers.

[0174] Based on the comprehensive reference to the characteristic test results in Tables 1 to 5, the following phenomena can be clearly observed:

[0175] From Examples E1 to E18, it can be determined that the resin composition and articles thereof of the present invention can be improved in one or more aspects, such as BC tensile stability, solder ball thrust, gap at the interface between glass cloth and resin, and solder bleed rate.

[0176] The benzocyclobutene-modified second polyolefins contained in Examples E1 to E9 are either benzocyclobutene-modified polyolefins containing heteroatoms or benzocyclobutene-modified polyolefins without heteroatoms. The benzocyclobutene-modified second polyolefins contained in Examples E10 to E18 are a combination of benzocyclobutene-modified polyolefins containing heteroatoms and benzocyclobutene-modified polyolefins without heteroatoms. Resin compositions and articles using the combination of benzocyclobutene-modified polyolefins containing heteroatoms and benzocyclobutene-modified polyolefins without heteroatoms show significant improvements in at least two properties simultaneously: BC tensile stability and solder ball thrust, compared to resin compositions and articles using either benzocyclobutene-modified polyolefins containing heteroatoms or benzocyclobutene-modified polyolefins without heteroatoms alone.

[0177] Comparing Examples E1-E18 and Comparative Examples C1-C2, it can be seen that: compared to 100 parts by weight of polyphenylene ether resin containing unsaturated carbon-carbon double bonds, if the amount of unhydrogenated maleic anhydride modified first polyolefin used is not in the range of 1-20 parts by weight, the corresponding resin composition and its products are significantly deteriorated in at least three characteristics: BC tensile stability, solder ball thrust, and solder drift and blowout rate.

[0178] Comparing Examples E1-E18 and Comparative Examples C3-C4, it can be seen that: compared to 100 parts by weight of polyphenylene ether resin containing unsaturated carbon-carbon double bonds, if the amount of benzocyclobutene-modified second polyolefin used is not in the range of 5-100 parts by weight, the corresponding resin composition and its products are significantly deteriorated in at least three characteristics: BC tensile stability, solder ball thrust, and solder drift and blowout rate.

[0179] Comparing Examples E1 to E18 with Comparative Examples C2, C3 and C5, it can be seen that if the resin composition does not simultaneously contain polyphenylene ether resin with unsaturated carbon-carbon double bonds, unhydrogenated maleic anhydride modified first polyolefin, and benzocyclobutene modified second polyolefin, the product will significantly deteriorate in at least three characteristics: BC tensile stability, solder ball thrust and solder drift / explosion rate.

[0180] Comparative Examples E1-E18 and Comparative Examples C6-C7 show that the resin composition and its products using the unhydrogenated maleic anhydride modified first polyolefin of the present invention have significantly improved at least in terms of BC tensile stability and solder ball thrust compared to the use of unmodified polyolefin (Ricon 100) or hydrogenated maleic anhydride modified polyolefin (FG1901).

[0181] Comparative Examples E1-E18 and Comparative Examples C8-C9 show that the resin composition and its products using the benzocyclobutene-modified second polyolefin of the present invention have significantly improved at least in three aspects: BC tensile stability, solder ball thrust and solder drift rate, compared with the use of unmodified polyolefin (Ricon 100 or B-1000).

[0182] The above embodiments are merely illustrative and are not intended to limit the invention or its application. In this invention, terms like "embodiment" refer to "as an example or illustration." Unless otherwise stated, any exemplary embodiment herein should not be considered superior to other embodiments. Although at least one exemplary or comparative example has been provided in the foregoing embodiments, it should be understood that various variations of the invention are possible. The scope of the invention is not limited to the illustrated embodiments. Therefore, it will be apparent to those skilled in the art that simple modifications to the exemplary embodiments of the invention fall within the scope of the technical spirit of the invention.

Claims

1. A resin composition, characterized in that, include: Composition (A): 100 parts by weight of polyphenylene ether resin containing unsaturated carbon-carbon double bonds; Component (B): 1-20 parts by weight of unhydrogenated maleic anhydride modified primary polyolefin; as well as Composition (C): 5-100 parts by weight of benzocyclobutene-modified second polyolefin.

2. The resin composition according to claim 1, characterized in that, The polyphenylene ether resin containing unsaturated carbon-carbon double bonds includes any one or a combination of vinyl benzyl polyphenylene ether resin, (meth)acryloyl polyphenylene ether resin, vinyl polyphenylene ether resin, allyl polyphenylene ether resin, and polyphenylene ether resin.

3. The resin composition according to claim 1, characterized in that, The unhydrogenated maleic anhydride-modified first polyolefin includes any one or a combination of maleic anhydride addition polybutadiene, maleic anhydride addition polyisoprene, maleic anhydride addition styrene-butadiene copolymer, and maleic anhydride addition styrene-isoprene copolymer.

4. The resin composition according to claim 1, characterized in that, The benzocyclobutene-modified second polyolefin includes any one or a combination of benzocyclobutene-modified polyolefins containing heteroatoms and benzocyclobutene-modified polyolefins without heteroatoms.

5. The resin composition according to claim 4, characterized in that, The heteroatom-containing polyolefins include any one or a combination thereof, maleic anhydride addition polybutadiene, maleic anhydride addition polyisoprene, maleic anhydride addition styrene-butadiene copolymer, maleic anhydride addition styrene-isoprene copolymer, vinyl-polybutadiene-urea polymer, silane-modified styrene-butadiene copolymer, terminal acryloyl polybutadiene, and epoxy-containing polybutadiene.

6. The resin composition according to claim 4, characterized in that, The polyolefins that do not contain heteroatoms include any one or a combination of polybutadiene, polyisoprene, styrene-butadiene copolymer, styrene-isoprene copolymer, styrene-butadiene-divinylbenzene polymer, styrene-ethylene-divinylbenzene polymer, and styrene-ethylvinylbenzene-divinylbenzene polymer.

7. The resin composition according to claim 4, characterized in that, The mass ratio of the benzocyclobutene-modified polyolefin without heteroatoms to the benzocyclobutene-modified polyolefin containing heteroatoms is 2:3 to 24:

1.

8. 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 is any one or a combination of divinylbenzene, divinylnaphthalene, divinylbiphenyl, triallyl isocyanurate, triallyl cyanurate, vinylbenzocyclobutene, di(vinylbenzyl) ether, trivinylcyclohexane, diallyl bisphenol A, butadiene, decanadiene, and octadiene.

9. The resin composition according to claim 1, characterized in that, The resin composition further includes any one or a combination thereof of polyolefins, silicone resins, benzoxazine resins, epoxy resins, polyester resins, phenolic resins, amine curing agents, polyamides, polyimides, styrene-maleic anhydride, maleimide resins, cyanate ester resins, and maleimide-triazine resins, which are different from components (B) and (C).

10. The resin composition according to claim 1, characterized in that, The resin composition further includes a curing accelerator, a polymerization inhibitor, a flame retardant, an inorganic filler, a surface treatment agent, a dye, a toughening agent, a solvent, or a combination thereof.

11. An article made from the resin composition according to claim 1, characterized in that, include: Prepreg, resin film, laminate, or printed circuit board.

12. The article of claim 11, characterized in that, The article has one, more, or all of the following characteristics: The BC tension difference measured and calculated according to the method of IPC-TM-650 2.4.8 is less than or equal to 0.3 lb / in; The solder bleed rate measured according to the method of IPC-TM-650 2.4.13.1 was 0%. The solder ball thrust was tested using a solder ball thruster and found to be greater than or equal to 805gf. Scanning electron microscopy revealed that the interface between the substrate glass cloth and the resin was seamless.

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