Copolymers, methods of making the same, resin compositions, and articles thereof

Abstract

Disclosed is a phenylvinylsilane-divinylbenzene-styrene terpolymer, which is copolymerized from 50 to 70 parts by weight of phenylvinylsilane, 10 to 20 parts by weight of divinylbenzene, and 20 to 30 parts by weight of styrene, and the total weight of the phenylvinylsilane, divinylbenzene, and styrene is 100 parts by weight, wherein the phenylvinylsilane has a structure represented by formula (I) or formula (II). In addition, a resin composition containing the phenylvinylsilane-divinylbenzene-styrene terpolymer and a vinyl group-containing polyphenylene ether resin is also disclosed. The aforementioned resin composition can be formed into a prepreg, a resin film, a laminate, a printed circuit board, or the like.

Description

Technical Field

[0001] This invention relates to a copolymer, particularly a copolymer comprising structural units formed of phenylvinylsilane, divinylbenzene and styrene, which can be used to prepare products such as prepregs, resin films, laminates or printed circuit boards. Background Technology

[0002] In recent years, electronic technology has been developing towards higher integration, lower power consumption, and higher performance, thus placing higher demands on high-performance electronic materials.

[0003] With the arrival of the 5G era, companies not only need to continuously improve the overall performance of electronic materials, but also need to balance the relationship between the performance and cost of electronic materials in order to meet the challenges brought about by continuous technological progress.

[0004] In the manufacturing of copper clad laminate (CCL) materials, the raw material phenylvinylsilane is prone to volatilization when heated to high temperatures, resulting in not only a waste of expensive raw materials but also altering the properties of the CCL material and failing to meet performance requirements. Therefore, to reduce its volatility, lower the cost of CCL materials, and improve their overall performance—such as improving one or more properties like glass transition temperature, copper foil tensile strength, dielectric loss, or adhesive flow within the board—the inventors have conducted relevant research. Summary of the Invention

[0005] 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 copolymer that overcomes at least one of the above-mentioned technical problems, which is a phenylvinylsilane-divinylbenzene-styrene trimer, and to provide a method for manufacturing the phenylvinylsilane-divinylbenzene-styrene trimer. Furthermore, the present invention also provides a resin composition that overcomes at least one of the above-mentioned technical problems, and articles made using this resin composition. Specifically, the copolymer, resin composition, or articles thereof provided by the present invention can improve one or more aspects such as glass transition temperature, copper foil tensile strength, dielectric loss, in-plate resin flow, edge streaks, or PCT heat resistance after moisture absorption.

[0006] To achieve the aforementioned objective, in one aspect, the present invention discloses a phenylvinylsilane-divinylbenzene-styrene trimer, wherein the phenylvinylsilane-divinylbenzene-styrene trimer is copolymerized from 50 to 70 parts by weight of phenylvinylsilane, 10 to 20 parts by weight of divinylbenzene, and 20 to 30 parts by weight of styrene, and the total weight of phenylvinylsilane, divinylbenzene, and styrene is 100 parts by weight, wherein the phenylvinylsilane has the structure shown in formula (I) or formula (II):

[0007] .

[0008] For example, in one embodiment, the volatile content of the phenylvinylsilane-divinylbenzene-styrene trimer is between 40% and 60%.

[0009] For example, in one embodiment, the content of structural units formed by phenylvinylsilane in the phenylvinylsilane-divinylbenzene-styrene trimer is 30 mol% to 50 mol%.

[0010] For example, in one embodiment, the phenylvinylsilane-divinylbenzene-styrene trimer comprises the structural unit shown in formula (a) and the structural unit shown in formula (b), and further comprises any one or more of the structural units shown in formulas (c), (d), (e), and (f):

[0011] Equation (a) Equation (b)

[0012] Equation (c) Equation (d)

[0013] Equation (e) Equation (f)

[0014] Where m is an integer from 2 to 45, n is an integer from 5 to 86, J1 and J2 are each an integer from 3 to 81, and k1 and k2 are each an integer from 3 to 65.

[0015] For example, in one embodiment, the weight-average molecular weight of the phenylvinylsilane-divinylbenzene-styrene trimer is between 3,000 and 30,000.

[0016] On the other hand, the present invention provides a method for manufacturing the aforementioned phenylvinylsilane-divinylbenzene-styrene trimer, characterized in that it includes mixing 50 to 70 parts by weight of phenylvinylsilane, 10 to 20 parts by weight of divinylbenzene, and 20 to 30 parts by weight of styrene at 70 °C. o C to 130 o The reaction is carried out at C for 3 to 14 hours.

[0017] In another aspect, the present invention provides a resin composition comprising 30 to 50 parts by weight of the aforementioned phenylvinylsilane-divinylbenzene-styrene trimer and 100 parts by weight of a vinyl-containing polyphenylene ether resin.

[0018] For example, in one embodiment, the resin composition further comprises maleimide resin, maleimide triazine resin, unsaturated polyolefin resin, hydrogenated unsaturated polyolefin resin, small molecule vinyl-containing resin, styrene-maleic anhydride resin, epoxy resin, phenolic resin, benzoxazine resin, cyanate ester resin, polyester resin, polyamide resin, polyimide resin, or combinations thereof. The term "further comprises" means "also comprises".

[0019] For example, in one embodiment, the small molecule vinyl resin includes styrene, divinylbenzene, di(vinylbenzyl) ether, 1,2,4-trivinylcyclohexane, di(vinylphenyl)ethane, di(vinylphenyl)hexane, divinylphenyldimethyl ether, divinylphenyldimethylbenzene, triallyl isocyanurate, triallyl cyanurate, prepolymers of any of the foregoing components, or combinations thereof.

[0020] For example, in one embodiment, the vinyl-containing polyphenylene ether resin includes terminal vinyl benzyl polyphenylene ether resin, terminal methacrylate polyphenylene ether resin, or a combination thereof.

[0021] For example, in one embodiment, the terminal vinyl benzyl polyphenylene ether resin and the terminal methacrylate polyphenylene ether resin respectively comprise the structures shown in formula (III) and formula (IV):

[0022] Equation (III)

[0023] Formula (IV)

[0024] Among them, R1 to R 14 Each is independently H or -CH3, and W1 and W2 are independently C1 to C3 divalent aliphatic groups;

[0025] b1 is an integer from 0 to 8;

[0026] Q1 includes any one or a combination of the structures shown in equations (B-1) to (B-3):

[0027] Equation (B-1)

[0028] Equation (B-2)

[0029] Equation (B-3)

[0030] Y1 and Y2 each independently include the structure shown in equation (B-4):

[0031] Equation (B-4)

[0032] Among them, R 15 To R 30 Each is independently H or -CH3; m1 and n1 are each independently an integer from 1 to 30; and A1 is selected from covalent bonds, -CH2-, -CH(CH3)-, -C(CH3)2-, -O-, -S-, -SO2- and carbonyl groups.

[0033] For example, in one embodiment, the resin composition further includes an amine curing agent, a flame retardant, an inorganic filler, a curing accelerator, a polymerization inhibitor, a colorant, a solvent, a toughening agent, a silane coupling agent, or a combination thereof.

[0034] In another aspect, the present invention provides an article made from the resin composition, comprising a prepreg, a resin film, a laminate, or a printed circuit board.

[0035] For example, in one embodiment, the aforementioned article has one, more, or all of the following characteristics:

[0036] The glass transition temperature, measured using dynamic mechanical analysis according to the method described in IPC-TM-650 2.4.24.4, is greater than or equal to 220°C. o C;

[0037] The copper foil tensile strength measured according to the method described in IPC-TM-650 2.4.8 is greater than or equal to 3.50 lb / in;

[0038] The dielectric loss measured at a frequency of 10 GHz according to the method described in JIS C2565 is less than or equal to 0.00350; and

[0039] The amount of adhesive flowing into the board after the product is pressed is greater than or equal to 15.0 mm. Attached Figure Description

[0040] Figure 1 The NMR spectra of copolymer 2, polyphenyltrivinylsilane and polystyrene are shown in the figure.

[0041] Figure 2 This is the gel permeation chromatography (GPC) spectrum of copolymer 2.

[0042] Figure 3 This is a schematic diagram of a dendritic distribution on a copper-free substrate.

[0043] Figure 4 This is a schematic diagram showing a copper-free substrate without dendritic distribution. Detailed Implementation

[0044] To enable those skilled in the art to understand the features and effects of this invention, 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 regarding this invention, and in case of conflict, the definitions in this specification shall prevail.

[0045] In this document, the terms “comprising,” “including,” “having,” “containing,” or any similar terms are open-ended transitional phrases intended to encompass non-exclusive inclusions. For example, a composition or article containing a plurality of elements is not limited to those listed herein, but may also include other elements not explicitly listed but typically inherent to the composition or article. Furthermore, unless explicitly stated otherwise, the term “or” is inclusive, not exclusive. For example, the condition “P or Q” is satisfied in any of the following cases: P is true (or exists) and Q is false (or does not exist); P is false (or does not exist) and Q is true (or exists); both P and Q are true (or exist). Moreover, in this document, the terms “comprising,” “including,” “having,” and “containing” are interpreted as specifically revealing and simultaneously encompassing closed conjunctions such as “composed of” and conjunctions such as “substantially composed of.”

[0046] In this document, all features or conditions defined in the form of numerical ranges or percentage ranges are for the sake of brevity and convenience only. Accordingly, descriptions of numerical ranges or percentage ranges should be considered as encompassing and specifically revealing all possible subranges and individual values ​​within those ranges, particularly integer values. For example, a range description of "1 to 8" should be considered as specifically revealing all subranges such as 1 to 7, 2 to 8, 2 to 6, 3 to 6, 4 to 8, 3 to 8, etc., particularly subranges defined by all integer values, and should be considered as specifically revealing individual values ​​within those ranges such as 1, 2, 3, 4, 5, 6, 7, 8, etc. Similarly, a range description of "between 1 and 8" should be considered as specifically revealing all ranges such as 1 to 8, 1 to 7, 2 to 8, 2 to 6, 3 to 6, 4 to 8, 3 to 8, etc., including endpoint values. Unless otherwise specified, the foregoing interpretation applies to all content throughout this invention, regardless of its scope.

[0047] If a quantity or other numerical value or parameter is expressed as a range, preferred range, or a series of upper and lower limits, it should be understood that this document has specifically disclosed all ranges consisting of any upper or preferred value of that range and the lower or preferred value of that range, whether such ranges are disclosed separately or not. Furthermore, when a range of numerical values ​​is mentioned herein, unless otherwise stated, the range shall include its endpoints and all integers and fractions within the range.

[0048] In this document, numerical values ​​are to be understood as having a precision with significant digits, provided that the purpose of the invention is achieved. For example, the number 40.0 should be understood to cover a range from 39.50 to 40.49.

[0049] In this document, when Markush groups or alternative terms are used to describe features or examples of the invention, those skilled in the art should understand that subgroups of all members within a Markush group or option list, or any individual member, can also be used to describe the invention. For example, if X is described as "selected from the group consisting of X1, X2, and X3," it also indicates that the claim that X is X1 and the claim that X is X1 and / or X2 and / or X3 have been fully described. Furthermore, when Markush groups or alternative terms are used to describe features or examples of the invention, those skilled in the art should understand that any combination of subgroups of all members within a Markush group or option list, or any individual member, can also be used to describe the invention. Accordingly, for example, if X is described as "selected from the group consisting of X1, X2, and X3," and Y is described as "selected from the group consisting of Y1, Y2, and Y3," it indicates that the claim that X is X1 or X2 or X3 and Y is Y1 or Y2 or Y3 has been fully described. In this article, "or a combination thereof" means "or any combination thereof".

[0050] Unless otherwise specified, "resin" can generally be a common name for a synthetic polymer. However, in this invention, "resin" can be interpreted as monomers, polymers thereof, combinations of monomers, combinations of polymers thereof, or combinations of monomers and their polymers, etc., and is not limited thereto. For example, "maleimide resin" in this invention can be interpreted as maleimide monomers (maleimide small molecule compounds), maleimide polymers, combinations of maleimide monomers, combinations of maleimide polymers, or combinations of maleimide monomers and maleimide polymers.

[0051] Unless otherwise specified, in this invention, a compound refers to a chemical substance formed by two or more elements linked by chemical bonds, including, but not limited to, small molecule compounds and polymeric compounds. In this invention, a compound is not limited to a single chemical substance, but can also be interpreted as a class of chemical substances having the same component or the same properties. Furthermore, in this invention, a mixture refers to a combination of two or more compounds, and mixtures may also contain copolymers or other auxiliaries, etc., and are not limited thereto.

[0052] Unless otherwise specified, in this invention, a polymer refers to the product formed by the polymerization reaction of monomers, often comprising an aggregate of many high molecules, each of which is composed of many simple structural units linked by repeated covalent bonds. The monomer is the compound that synthesizes the polymer. Polymers may include homopolymers (also known as self-polymers), copolymers, prepolymers, etc., but are not limited to these.

[0053] Homopolymers refer to chemical substances formed by the polymerization, addition polymerization, or condensation polymerization of a single compound. Copolymers refer to chemical substances formed by the polymerization, addition polymerization, or condensation polymerization of two or more compounds, including 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. Unless otherwise specified, copolymers in this invention refer to polymers obtained by copolymerizing monomers of phenylvinylsilane, divinylbenzene, and styrene. In this invention, copolymers only need to contain phenylvinylsilane, divinylbenzene, and styrene segments; whether the polymer backbone and side chain units are modified or altered is not particularly limited. In other words, the interpretation of the phenylvinylsilane-divinylbenzene-styrene trimer of this invention should simultaneously cover both unmodified and modified cases.

[0054] Unless otherwise specified, in this invention, a prepolymer refers to a polymer with a lower molecular weight, which is between that of a monomer and the final polymer, and the prepolymer contains reactive functional groups that can undergo further polymerization to obtain a fully cross-linked or hardened product with a higher molecular weight.

[0055] 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, but are usually composed of 2 to 5 repeating units.

[0056] Unless otherwise specified, in this invention, modified products (also referred to as modified materials) 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 homopolymerization of each resin, products after copolymerization of each resin with other resins, etc. For example, but not limited to, modification may involve replacing the original hydroxyl groups with vinyl groups through a chemical reaction, or obtaining terminal hydroxyl groups by chemically reacting the original terminal vinyl groups with p-aminophenol.

[0057] Unless otherwise specified, the alkyl, alkenyl, and hydrocarbon groups mentioned in this invention are interpreted to include their various isomers. For example, propyl should be interpreted to include n-propyl and isopropyl.

[0058] Unless otherwise specified, "vinyl-containing" in this invention refers to a compound structure containing an vinyl carbon-carbon double bond (C=C) or a derivative functional group thereof. Therefore, examples of vinyl-containing compounds include, but are not limited to, compounds containing vinyl, allyl, vinyl benzyl, or methacrylate functional groups. Unless otherwise specified, the position of the aforementioned functional groups is not particularly limited; for example, they may be located at the end of a long chain structure. Therefore, for example, vinyl-containing polyphenylene ether resin represents, but is not limited to, polyphenylene ether resins containing vinyl, allyl, vinyl benzyl, or methacrylate functional groups.

[0059] Unless otherwise specified, the unsaturated bond referred to in this invention 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.

[0060] In this document, parts by weight represent the number of parts of weight, which can be any unit of weight, such as, but not limited to, kilograms, grams, pounds, etc. For example, 100 parts by weight of vinyl polyphenylene ether resin can mean 100 kilograms of vinyl polyphenylene ether resin or 100 pounds of vinyl polyphenylene ether resin.

[0061] The following detailed embodiments are merely illustrative in nature and are not intended to limit the invention or its uses. Furthermore, this document is not limited to the foregoing prior art or the invention itself, or to any theory described in the following detailed embodiments or examples. Unless otherwise stated, the methods, reagents, and conditions used in the examples are conventional methods, reagents, and conditions in the art.

[0062] As previously stated, the main objective of this invention is to provide a phenylvinylsilane-divinylbenzene-styrene trimer (which may be simply referred to as a "polymer"), wherein the phenylvinylsilane-divinylbenzene-styrene trimer is copolymerized from 50 to 70 parts by weight of phenylvinylsilane, 10 to 20 parts by weight of divinylbenzene, and 20 to 30 parts by weight of styrene, and the total weight of phenylvinylsilane, divinylbenzene, and styrene is 100 parts by weight, wherein the phenylvinylsilane has the structure shown in formula (I) or formula (II) as follows:

[0063] .

[0064] In one embodiment, for example, the divinylbenzene includes o-divinylbenzene, m-divinylbenzene, p-divinylbenzene, or combinations thereof.

[0065] In one embodiment, for example, based on a total weight of 100 parts by weight of phenylvinylsilane, divinylbenzene, and styrene, wherein phenylvinylsilane comprises 50 to 70 parts by weight, such as, but not limited to, 50, 60, or 70 parts by weight; divinylbenzene comprises 10 to 20 parts by weight, such as, but not limited to, 10, 15, or 20 parts by weight; and styrene comprises 20 to 30 parts by weight, such as, but not limited to, 20, 25, or 30 parts by weight. In one embodiment, for example, the weight parts of phenylvinylsilane, divinylbenzene, and styrene are 50, 20, and 30 parts by weight, respectively. In one embodiment, for example, the weight parts of phenylvinylsilane, divinylbenzene, and styrene are 60, 10, and 30 parts by weight, respectively. In one embodiment, for example, the weight parts of phenylvinylsilane, divinylbenzene, and styrene are 60, 15, and 25 parts by weight, respectively. In one embodiment, for example, the parts by weight of phenylvinylsilane, divinylbenzene, and styrene are 70 parts by weight, 10 parts by weight, and 20 parts by weight, respectively.

[0066] The copolymer described in this invention is obtained by copolymerizing phenylvinylsilane, divinylbenzene and styrene, and this invention has several advantages over phenylvinylsilane.

[0067] For example, in one embodiment, the phenylvinylsilane-divinylbenzene-styrene trimer of the present invention has the following advantages:

[0068] 1. Using the volatility test method, weigh 2 grams of resin (phenylvinylsilane, divinylbenzene, or styrene) or copolymer into a tray, and heat it at 170°C. oBake in oven C for 1 hour, cool, and weigh (m). The volatile content can be calculated as [(2-m) / 2]*100%. Surprisingly, compared to the raw materials phenylvinylsilane, divinylbenzene, and styrene, the volatility of the phenylvinylsilane-divinylbenzene-styrene trimer of this invention is significantly reduced, for example, its volatile content is between 40% and 60%, such as 40%, 45%, 50%, 55%, or 60%, and is not limited thereto. The relevant volatile content data are as follows:

[0069]

[0070] 2. Compared to the expensive phenylvinylsilane, the cost of phenylvinylsilane-divinylbenzene-styrene trimer is reduced by more than 30%.

[0071] 3. Compared to phenylvinylsilane, the addition of phenylvinylsilane-divinylbenzene-styrene trimer to resin compositions can simultaneously improve the glass transition temperature and copper foil tensile strength of the products.

[0072] In one embodiment, for example, the content of structural units formed by phenyl vinylsilane in the phenyl vinylsilane-divinylbenzene-styrene trimer of the present invention is 30 mol% to 50 mol%.

[0073] In one embodiment, for example, the phenylvinylsilane-divinylbenzene-styrene trimer of the present invention comprises the structural unit shown in formula (a) (from divinylbenzene) and the structural unit shown in formula (b) (from styrene), and further comprises any one or more of the structural units shown in formulas (c), (d), (e) and (f) (from phenylvinylsilane):

[0074] Equation (a) Equation (b)

[0075] Equation (c) Equation (d)

[0076] Equation (e) Equation (f)

[0077] Where m is an integer from 2 to 45, n is an integer from 5 to 86, J1 and J2 are each an integer from 3 to 81, and k1 and k2 are each an integer from 3 to 65.

[0078] The molecular weight of the phenylvinylsilane-divinylbenzene-styrene trimer described in this invention is not particularly limited. In one embodiment, for example, the weight-average molecular weight of the phenylvinylsilane-divinylbenzene-styrene trimer can be between 3,000 and 30,000, such as, but not limited to, 3,000, 10,000, 15,000, 20,000, 25,000, or 30,000, and for example, its weight-average molecular weight is 21,228.

[0079] Another major objective of this invention is to provide a method for manufacturing the aforementioned phenylvinylsilane-divinylbenzene-styrene trimer, comprising mixing 50 to 70 parts by weight of phenylvinylsilane, 10 to 20 parts by weight of divinylbenzene, and 20 to 30 parts by weight of styrene at 70 °C. o C to 130 o The reaction is carried out at C for 3 to 14 hours.

[0080] For example, in one embodiment, the heating time can be between 3 and 14 hours, such as between 4 and 13 hours, or between 5 and 12 hours, or between 6 and 11 hours, or between 7 and 10 hours, or between 8 and 9 hours. The reaction temperature can be between 70°C and 80°C. o C to 130 o Between C, for example, between 80 o C to 120 o Between C, or between 90 o C to 110 o Between C, or between 100 o C to 120 o Between C.

[0081] For example, in one embodiment, a catalyst, a free radical initiator, or a combination thereof may be used as needed during the reaction, such as, but not limited to, α,α'-bis(tert-butylperoxide-m-isopropyl)benzene, 2,3-dimethyl-2,3-diphenylbutane, 2,5-dimethyl-2,5-di(tert-butylperoxide)-3-hexyne, benzoyl peroxide, 3,3',5,5'-tetramethyl-1,4-diphenoxyquinone, chloroquinone, 2,4,6-tritert-butylphenol, tert-butyl peroxide monocarbonate, azobisisobutylonitrile, or a combination thereof. Additionally, in one embodiment, a metal carboxylate may be used as needed during the reaction. The amount of the catalyst, free radical initiator or combination thereof may be between 0.5% and 1.0% of the total amount (e.g., parts by weight) of phenylvinylsilane, divinylbenzene and styrene, for example between 0.6% and 0.9%, or between 0.7% and 0.8%.

[0082] For example, in one embodiment, the copolymer of the present invention (i.e., phenylvinylsilane-divinylbenzene-styrene trimer) is prepared as follows:

[0083] Preparation Example 1

[0084] Under nitrogen protection, 50 parts by weight of phenyltrivinylsilane, 20 parts by weight of divinylbenzene, 30 parts by weight of styrene, and 0.6 parts by weight of 2,5-dimethyl-2,5-di(tert-butylperoxy)-3-hexyne (hereinafter referred to as 25B) were added to a three-necked flask, and the mixture was heated to 90°C. o C to 110 o C. Stir the reaction for 5 to 8 hours. After the reaction is complete, cool to room temperature to obtain product 1. Then, add product 1 dropwise to methanol to precipitate and filter to obtain white solid 1. Place white solid 1 in a vacuum drying oven at 50°C. o C to 70 o After being placed at C for 6 to 12 hours, the resulting white solid 2 (i.e., product 2) is copolymer 1, which contains 32 mol% of structural units formed by phenyltrivinylsilane. It is the phenylvinylsilane-divinylbenzene-styrene trimer of the present invention.

[0085] Preparation Example 2

[0086] In a three-necked flask, 60 parts by weight of phenyltrivinylsilane, 10 parts by weight of divinylbenzene, 30 parts by weight of styrene, and 0.6 parts by weight of 25B were added. The other steps were the same as in Preparation Example 1 to obtain copolymer 2, which has a content of 36 mol% of structural units formed by phenyltrivinylsilane. It is the phenyltrivinylsilane-divinylbenzene-styrene trimer of the present invention.

[0087] Preparation Example 3

[0088] In a three-necked flask, 60 parts by weight of phenyltrivinylsilane, 15 parts by weight of divinylbenzene, 25 parts by weight of styrene, and 0.6 parts by weight of 25B were added. The other steps were the same as in Preparation Example 1, and copolymer 3 was obtained. The content of structural units formed by phenyltrivinylsilane was 38 mol%, which is the phenyltrivinylsilane-divinylbenzene-styrene trimer of the present invention.

[0089] Preparation Example 4

[0090] 70 parts by weight of phenyltrivinylsilane, 10 parts by weight of divinylbenzene, 20 parts by weight of styrene and 0.6 parts by weight of 25B were added to a three-necked flask. Other steps were the same as in Preparation Example 1 to obtain copolymer 4, which has a content of 44 mol% of structural units formed by phenyltrivinylsilane. It is the phenyltrivinylsilane-divinylbenzene-styrene trimer of the present invention.

[0091] Preparation Example 5

[0092] In a three-necked flask, 60 parts by weight of diphenyldivinylsilane, 10 parts by weight of divinylbenzene, 30 parts by weight of styrene, and 0.6 parts by weight of 25B were added. The other steps were the same as in Preparation Example 1, and copolymer 5 was obtained. The content of structural units formed by diphenyldivinylsilane was 36 mol%, which is the phenyldivinylsilane-divinylbenzene-styrene trimer of the present invention.

[0093] Figure 1 The NMR spectra of copolymer 2, polyphenyltrivinylsilane, and polystyrene (standard material: TSM tetramethylsilane) are shown below. The top spectrum is the NMR spectrum of copolymer 2, the middle spectrum is the NMR spectrum of polyphenyltrivinylsilane, and the bottom spectrum is the NMR spectrum of polystyrene. Because divinylbenzene or styrene readily undergoes self-polymerization at high temperatures, and phenyltrivinylsilane may self-polymerize at high temperatures with an initiator, the NMR spectrum of its self-polymerized product is used to rule out the possibility of self-polymerization of the raw materials in this case.

[0094] In the lower 1H NMR spectrum of polystyrene, a CH peak connected to the benzene ring on the polystyrene main chain is observed at approximately 2.4 ppm. In the middle 1H NMR spectrum of polyphenyltrivinylsilane, a C=C double bond peak appears at 5.5–6.5 ppm. Since divinylbenzene has a network cross-linked structure and is insoluble in deuterated chloroform (CDCl3), its 1H NMR spectrum could not be measured. However, the position of the CH peak connected to the benzene ring on the main chain in divinylbenzene is not significantly different from that in polystyrene. Comparison revealed that the 1H NMR spectrum of copolymer 2 showed a C=C double bond peak at 5.5–6.5 ppm, and characteristic peaks of polystyrene (divinylbenzene) appeared in both the 1.0–2.0 ppm CH saturated bond region and the benzene ring region. This indicates that the raw materials phenyltrivinylsilane, divinylbenzene, and styrene underwent copolymerization to form copolymer 2, which is the phenylvinylsilane-divinylbenzene-styrene trimer of this invention.

[0095] Figure 2 The image shows the gel permeation chromatography (GPC) spectrum of copolymer 2. Testing confirmed that the weight-average molecular weight of copolymer 2 is 21228, demonstrating that the weight-average molecular weight of copolymer 2 is significantly larger than that of its raw material monomers (i.e., phenylvinylsilane, divinylbenzene, and styrene). Therefore, copolymer 2 has indeed undergone a copolymerization reaction.

[0096] Comparative Preparation Example 1

[0097] Add 35 parts by weight of phenyltrivinylsilane, 25 parts by weight of divinylbenzene, 40 parts by weight of styrene and 0.6 parts by weight of 25B to a three-necked flask, and follow the same steps as in Preparation Example 1 to obtain Comparative copolymer 1.

[0098] Comparative Preparation Example 2

[0099] Add 80 parts by weight of phenyltrivinylsilane, 5 parts by weight of divinylbenzene, 15 parts by weight of styrene and 0.6 parts by weight of 25B to a three-necked flask, and follow the same steps as in Preparation Example 1 to obtain Comparative copolymer 2.

[0100] Comparative preparation example 3

[0101] Add 35 parts by weight of diphenyldivinylsilane, 25 parts by weight of divinylbenzene, 40 parts by weight of styrene and 0.6 parts by weight of 25B to a three-necked flask, and follow the same steps as in Preparation Example 1 to obtain Comparative copolymer 3.

[0102] Comparative preparation example 4

[0103] Add 60 parts by weight of phenyltrivinylsilane, 40 parts by weight of divinylbenzene and 0.6 parts by weight of 25B to a three-necked flask, and follow the same steps as in Preparation Example 1 to obtain Comparative copolymer 4.

[0104] Comparative preparation example 5

[0105] 60 parts by weight of diphenyldivinylsilane, 40 parts by weight of divinylbenzene and 0.6 parts by weight of 25B were added to a three-necked flask, and the other steps were the same as in Preparation Example 1, to obtain Comparative copolymer 5.

[0106] Comparative preparation example 6

[0107] Add 60 parts by weight of phenyltrivinylsilane, 40 parts by weight of styrene and 0.6 parts by weight of 25B to a three-necked flask, and follow the same steps as in Preparation Example 1 to obtain Comparative copolymer 6.

[0108] Comparative preparation example 7

[0109] Add 60 parts by weight of diphenyldivinylsilane, 40 parts by weight of styrene and 0.6 parts by weight of 25B to a three-necked flask, and follow the same steps as in Preparation Example 1 to obtain Comparative copolymer 7.

[0110] Comparative Preparation Example 8

[0111] In a three-necked flask, 60 parts by weight of allyltrimethylsilane, 10 parts by weight of divinylbenzene, 30 parts by weight of styrene and 0.6 parts by weight of 25B were added, and the other steps were the same as in Preparation Example 1, to obtain Comparative copolymer 8.

[0112] Comparative preparation example 9

[0113] In a three-necked flask, 60 parts by weight of diphenyldivinylsilane, 40 parts by weight of styrene-butadiene copolymer (Ricon 100, purchased from Cray Valley) and 0.6 parts by weight of 25B were added, and the other steps were the same as in Preparation Example 1, to obtain Comparative copolymer 9.

[0114] Comparative Preparation Example 10

[0115] Add 60 parts by weight of divinylbenzene, 40 parts by weight of styrene and 0.6 parts by weight of 25B to a three-necked flask, and follow the same steps as in Preparation Example 1 to obtain Comparative copolymer 10.

[0116] Comparative Preparation Example 11

[0117] Five parts by weight of divinylbenzene, 15 parts by weight of styrene, and 0.12 parts by weight of 25B were added to a three-necked flask, and the other steps were the same as in Preparation Example 1, to obtain comparative copolymer 11.

[0118] Comparative preparation example 12

[0119] Add 60 parts by weight of phenyltrivinylsilane, 40 parts by weight of methacrylate and 0.6 parts by weight of 25B to a three-necked flask, and follow the same steps as in Preparation Example 1 to obtain comparative copolymer 12.

[0120] Another major object of the present invention is to provide a resin composition comprising the aforementioned phenylvinylsilane-divinylbenzene-styrene trimer and a vinyl polyphenylene ether resin, for example comprising 30 to 50 parts by weight of the aforementioned phenylvinylsilane-divinylbenzene-styrene trimer and 100 parts by weight of the vinyl polyphenylene ether resin.

[0121] Unless otherwise specified, the resin compositions of the present invention may also include, as needed, maleimide resin, maleimide triazine resin, unsaturated polyolefin resin, hydrogenated unsaturated polyolefin resin, small molecule vinyl-containing resin, styrene-maleic anhydride resin, epoxy resin, phenolic resin, benzoxazine resin, cyanate ester resin, polyester resin, polyamide resin, polyimide resin, or combinations thereof.

[0122] For example, in one embodiment, the small molecule vinyl-containing resin refers to a vinyl compound with a molecular weight less than or equal to 1000, preferably with a molecular weight between 100 and 900, and more preferably with a molecular weight between 100 and 800. For example, the small molecule vinyl-containing resin includes, but is not limited to, styrene, divinylbenzene, bis(vinylbenzyl) ether, 1,2,4-trivinylcyclohexane (TVCH), bis(vinylphenyl)ethane (BVPE), divinylphenyl hexane, divinylphenyl dimethylene ether, divinylphenyl dimethylenebenzene, triallyl isocyanurate (TAIC), and / or triallyl cyanurate (TAC). In one embodiment, the small molecule vinyl-containing resin comprises a prepolymer of any of the foregoing components. In one embodiment, the vinyl-containing resin comprises any of the foregoing components, a prepolymer of any of the foregoing components, or a combination thereof.

[0123] For example, in one embodiment, the vinyl-containing polyphenylene ether resin used in this invention refers to a polyphenylene ether compound or mixture having an vinyl carbon-carbon double bond (C=C) or its derivative functional groups. Examples of the aforementioned vinyl carbon-carbon double bond (C=C) or its derivative functional groups may include, but are not limited to, functional groups containing vinyl, vinylidene, allyl, vinylbenzyl, methacrylate, etc., in the structure. Unless otherwise specified, the position of the aforementioned functional groups is not particularly limited, for example, they may be located at the end of a long chain structure. In other words, in this invention, vinyl-containing polyphenylene ether resin represents a polyphenylene ether resin containing reactive vinyl or its derivative functional groups, examples of which may include, but are not limited to, polyphenylene ether resins containing vinyl, vinylidene, allyl, vinylbenzyl, or methacrylate.

[0124] For example, in one embodiment, the vinyl-containing polyphenylene ether resin used in this invention includes terminal vinyl benzyl polyphenylene ether resin, terminal methacrylate polyphenylene ether resin (i.e., terminal methacryloyl polyphenylene ether resin), terminal allyl polyphenylene ether resin, or a combination thereof.

[0125] For example, the terminal vinyl benzyl polyphenylene ether resin and the terminal methacrylate polyphenylene ether resin respectively comprise the structures shown in formula (III) and formula (IV):

[0126] Equation (III)

[0127] Formula (IV)

[0128] Among them, R1 to R 14 Each is independently H or -CH3, and W1 and W2 are independently C1 to C3 divalent aliphatic groups;

[0129] b1 is an integer from 0 to 8;

[0130] Q1 includes any one or a combination of the structures shown in equations (B-1) to (B-3):

[0131] Equation (B-1)

[0132] Equation (B-2)

[0133] Equation (B-3)

[0134] Y1 and Y2 each independently include the structure shown in equation (B-4):

[0135] Equation (B-4)

[0136] Among them, R 15 To R 30 Each is independently H or -CH3; m1 and n1 are each independently an integer from 1 to 30; and A1 is selected from covalent bonds, -CH2-, -CH(CH3)-, -C(CH3)2-, -O-, -S-, -SO2- and carbonyl groups.

[0137] For example, the vinyl-containing polyphenylene ether resin may be SA9000 sold by Sabic Corporation, vinyl benzyl polyphenylene ether resin with a number average molecular weight of approximately 1200 (e.g., OPE-2st 1200, available from Mitsubishi Gas Chemical Company), vinyl benzyl polyphenylene ether resin with a number average molecular weight of approximately 2200 (e.g., OPE-2st 2200, available from Mitsubishi Gas Chemical Company), vinyl benzyl modified bisphenol A polyphenylene ether resin with a number average molecular weight of approximately 2400 to 2800, vinyl chain-extended polyphenylene ether resin with a number average molecular weight of approximately 2200 to 3000, or combinations thereof. The vinyl chain-extended polyphenylene ether resin may include various polyphenylene ether resins disclosed in U.S. Patent Application Publication No. 2016 / 0185904 A1, the entire contents of which are incorporated herein by reference.

[0138] For example, in one embodiment, the maleimide resin used in this invention refers to a compound or mixture having one or more maleimide functional groups in its molecule. Unless otherwise specified, the maleimide resin used in this invention is not particularly limited and may be any one or more maleimide resins suitable for manufacturing prepregs, resin films, laminates, or printed circuit boards. Specific examples include, but are not limited to, 4,4'-diphenylmethane bismaleimide, benzene maleimide oligomers, m-phenylene bismaleimide, bisphenol A diphenyl ether bismaleimide, 3,3'-dimethyl-5,5'-diethyl-4,4'-diphenylmethane bismaleimide, 4-methyl-1,3-phenylene bismaleimide, 1,6-bismaleimide-(2,2,4-trimethyl)hexane, 2,3-dimethylbenzenemaleimide, 2,6-dimethylbenzenemaleimide, N-phenylmaleimide, maleimide resins containing aliphatic long-chain structures, or combinations thereof. Furthermore, unless otherwise specified, the maleimide resin described in this invention also includes prepolymers of the aforementioned resins, such as prepolymers of diallyl compounds and maleimide resins, prepolymers of diamines and maleimide resins, prepolymers of polyfunctional amines and maleimide resins, or prepolymers of acidic phenolic compounds and maleimide resins, and is not limited thereto.

[0139] For example, maleimide resins can be those produced by Daiwakasei Corporation under trade names such as BMI-1000, BMI-1000H, BMI-1100, BMI-1100H, BMI-2000, BMI-2300, BMI-3000, BMI-3000H, BMI-4000H, BMI-5000, BMI-5100, BMI-7000, and BMI-7000H; or those produced by KI Chemical Corporation under trade names such as BMI-70 and BMI-80; or those produced by Sichuan Dongcai Technology Co., Ltd. under trade names such as D928, D930, D932, D934, D936, D937, and D938.

[0140] For example, maleimide resins containing aliphatic long-chain structures can be maleimide resins manufactured 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. For example, maleimide resins containing aliphatic long-chain structures can have at least one maleimide functional group linked to a substituted or unsubstituted long-chain aliphatic group. The long-chain aliphatic group can have a carbon number from C5 to C6. 50 Aliphatic groups, such as those with a carbon number of C 10 To C 50 C20 To C 50 C 30 To C 50 C 20 To C 40 Or C 30 To C 40 However, this is not a limitation. For example, commercially available maleimide resins containing aliphatic long-chain structures are as follows:

[0141] BMI-689:

[0142] BMI-1400:

[0143] BMI-1500:

[0144] BMI-1700:

[0145] BMI-2500:

[0146] BMI-3000, BMI-5000, BMI-6000:

[0147]

[0148] For example, in one embodiment, the ratio of styrene (S) to maleic anhydride (MA) in the styrene-maleic anhydride resin used in this invention can be 1:1, 2:1, 3:1, 4:1, 6:1, or 8:1, such as, but not limited to, styrene-maleic anhydride copolymers sold by Cray Valley under the trade names SMA-1000, SMA-2000, SMA-3000, EF-30, EF-40, EF-60, and EF-80, or styrene-maleic anhydride copolymers sold by Polyscope under the trade names C400, C500, C700, and C900. Furthermore, the styrene-maleic anhydride resin can also be an esterified styrene-maleic anhydride copolymer, such as esterified styrene-maleic anhydride copolymers purchased from Cray Valley under the trade names SMA1440, SMA17352, SMA2625, SMA3840, and SMA31890. Unless otherwise specified, the above-mentioned styrene-maleic anhydride resin may be added independently or in combination to the resin composition of the present invention.

[0149] For example, in one embodiment, the unsaturated polyolefin resin of the present invention may be any one or more polyolefin resins containing unsaturated carbon-carbon double bonds suitable for manufacturing prepregs, resin films, laminates, or printed circuit boards. Specific examples include, but are not limited to, at least one or a combination of styrene-butadiene-divinylbenzene terpolymers, styrene-butadiene-maleic anhydride terpolymers, styrene-butadiene-styrene terpolymers, vinyl-polybutadiene-urethane oligomers, styrene-butadiene copolymers, styrene-isoprene copolymers, polybutadiene, methylstyrene homopolymers, petroleum resins, and cyclic olefin copolymers.

[0150] For example, in one embodiment, the hydrogenated unsaturated polyolefin resin of the present invention is obtained by hydrogenating an unsaturated polyolefin resin, and can be any one or more hydrogenated unsaturated polyolefin resins without unsaturated carbon-carbon double bonds suitable for manufacturing prepregs, resin films, laminates, or printed circuit boards. Specific examples include, but are not limited to, at least one or a combination of hydrogenated styrene-butadiene copolymer and hydrogenated styrene-isoprene copolymer.

[0151] For example, in one embodiment, the epoxy resin used in this invention may be any type of epoxy resin known in the art, including but not limited to, bisphenol A epoxy resin, bisphenol F epoxy resin, bisphenol S epoxy resin, bisphenol AD ​​epoxy resin, phenolic (novolac) epoxy resin, trifunctional epoxy resin, tetrafunctional epoxy resin, multifunctional 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. The phenolic epoxy resin may be phenolnovolac epoxy resin, bisphenol A novolac epoxy resin, bisphenol F novolac epoxy resin, biphenyl novolac epoxy resin, phenolbenzaldehyde epoxy resin, phenol aralkyl 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 be selected from one or more of the following: DOPO-containing phenolic novolac epoxy resin, DOPO-containing 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 the following: DOPO-containing phenolic novolac epoxy resin, DOPO-containing cresol novolac epoxy resin, and DOPO-containing bisphenol-A novolac epoxy resin.

[0152] For example, in one embodiment, the phenolic resin described in this invention may be a monofunctional, difunctional, or multifunctional phenolic resin. There is no particular limitation on the type of phenolic resin mentioned above; all phenolic resins currently used in the industry are within the scope of phenolic resins to which this invention applies. Preferably, the phenolic resin is selected from phenoxy resins, phenolic resins, or combinations thereof.

[0153] For example, in one embodiment, the benzoxazine resin of the present invention may be a bisphenol A type benzoxazine resin, a bisphenol F type benzoxazine resin, a phenolphthalein type benzoxazine resin, a dicyclopentadiene benzoxazine resin, or a phosphorus-containing benzoxazine resin, such as Huntsman's trade name LZ-8270 (phenolphthalein type benzoxazine resin), LZ-8280 (bisphenol F type benzoxazine resin), LZ-8290 (bisphenol A type benzoxazine resin) or Showa Polymer Co., Ltd.'s trade name HFB-2006M.

[0154] For example, in one embodiment, the cyanate resin of the present invention may be any type of cyanate resin known in the art, including but not limited to cyanate resins having an Ar-OC≡N structure (where Ar is an aromatic group, such as benzene, naphthalene or anthracene), phenolic cyanate resin, bisphenol A cyanate resin, bisphenol A cyanate resin, bisphenol F cyanate resin, bisphenol F cyanate resin, cyanate resin containing a dicyclopentadiene structure, cyanate resin containing a naphthalene ring structure, phenolphthalein cyanate resin or combinations thereof. Examples of cyanate ester resins include, but are not limited to, cyanate ester resins manufactured 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.

[0155] For example, in one embodiment, the polyester resin of the present invention is formed by esterification of an aromatic compound having a dicarboxylic acid group and an aromatic compound having a dihydroxyl group, such as, but not limited to, HPC-8000, HPC-8150 or HPC-8200 available from Dai Nippon Ink Chemical.

[0156] For example, in one embodiment, the polyamide resin of the present invention may be any type of polyamide resin known in the art, including but not limited to various commercially available polyamide resin products.

[0157] For example, in one embodiment, the polyimide resin described in this invention may be any type of polyimide resin known in the art, including but not limited to various commercially available polyimide resin products.

[0158] For example, in one embodiment, the maleimide triazine resin described in this invention is not particularly limited and may be any one or more maleimide triazine resins suitable for manufacturing prepregs, resin films, laminates, or printed circuit boards. For example, the maleimide triazine resin may be obtained by polymerizing the cyanate resin with the maleimide resin. The maleimide triazine resin may be, for example, but not limited to, obtained by polymerizing bisphenol A cyanate resin with maleimide resin, bisphenol F cyanate resin with maleimide resin, phenolic phenolic cyanate resin with maleimide resin, or a dicyclopentadiene-containing cyanate resin with maleimide resin. For example, the maleimide triazine resin may be obtained by polymerizing cyanate resin with maleimide resin in any molar ratio. For example, the cyanate resin may be 1 to 10 moles relative to 1 mole of maleimide resin. For example, but not limited to, the cyanate resin is 1, 2, 4 or 6 moles relative to 1 mole of maleimide resin.

[0159] Unless otherwise specified, there are no particular restrictions on the ratio of phenylvinylsilane-divinylbenzene-styrene trimer and vinyl polyphenylene ether resin.

[0160] For example, in one embodiment, the resin composition comprises 100 parts by weight of a vinyl polyphenylene ether resin and 30 to 50 parts by weight of a phenyl vinylsilane-divinylbenzene-styrene trimer.

[0161] In one embodiment, in addition to the above-mentioned phenylvinylsilane-divinylbenzene-styrene trimer and any one or more vinyl polyphenylene ether resins, the resin composition disclosed in this invention may further include, as needed, amine curing agents, flame retardants, inorganic fillers, curing accelerators, polymerization inhibitors, colorants, solvents, toughening agents, silane coupling agents, or combinations thereof.

[0162] For example, in one embodiment, the resin composition, in addition to the above-mentioned vinyl polyphenylene ether resin and phenyl vinylsilane-divinylbenzene-styrene trimer, further includes amine curing agents, flame retardants, inorganic fillers, curing accelerators, polymerization inhibitors, colorants, solvents, toughening agents, silane coupling agents, or combinations thereof.

[0163] For example, in one embodiment, the amine curing agent of the present invention may be dicyandiamide, diaminodiphenyl sulfone, diaminodiphenylmethane, diaminodiphenyl ether, diaminodiphenyl sulfide or a combination thereof, but is not limited thereto.

[0164] For example, in one embodiment, the flame retardant of the present invention can be any one or more flame retardants suitable for the manufacture of prepregs, resin films, laminates, or printed circuit boards. Specific examples include, but are not limited to, phosphorus-containing flame retardants, such as at least one, two, or a combination of two or more from the following group: ammonium polyphosphate, hydroquinone bis-(diphenylphosphate), bisphenol A bis-(diphenylphosphate), tri(2-carboxyethyl) phosphine (TCEP), trichloroisopropyl phosphate, trimethyl phosphate (TMP), dimethyl methyl phosphonate (DMMP), resorcinol bis(dixylenyl phosphate) (RDXP). Commercially available products such as PX-200, PX-201, and PX-202, phosphazene compounds such as SPB-100, SPH-100, and SPV-100, melamine polyphosphate, DOPO and its derivatives or resins, diphenylphosphine oxide (DPPO) and its derivatives or resins, melamine cyanurate, tri-hydroxyethyl isocyanurate, aluminum phosphonates (such as OP-930 and OP-935), or combinations thereof.

[0165] For example, the flame retardant used in this invention may be a DPPO compound (such as a bisDPPO compound), a DOPO compound (such as a bisDOPO compound), a DOPO resin (such as DOPO-HQ, DOPO-NQ, DOPO-PN, DOPO-BPN), or a DOPO-bonded epoxy resin, etc., wherein DOPO-PN is a DOPO phenolic compound, and DOPO-BPN may be a bisphenolic compound such as DOPO-BPAN (DOPO-bisphenol Anovolac), DOPO-BPFN (DOPO-bisphenol F novolac), or DOPO-BPSN (DOPO-bisphenol Snovolac).

[0166] For example, in one embodiment, the inorganic filler of the present invention can be any one or more inorganic fillers suitable for the manufacture of resin films, prepregs, 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, zinc oxide, zirconium oxide, mica, boehmite (AlOOH), calcined talc, talc, silicon nitride, or calcined kaolin. Furthermore, the aforementioned inorganic filler can be spherical, fibrous, plate-like, granular, flake-like, or needle-like, and can be selectively pretreated with a silane coupling agent.

[0167] In one embodiment, for example, the curing accelerator (including curing initiator) of the present invention may include a Lewis base or Lewis acid catalyst. The Lewis base may include one or more of imidazole, boron trifluoride amine complex, ethyltriphenyl phosphonium chloride, 2-methylimidazole (2MI), 2-phenyl-1H-imidazole (2PZ), 2-ethyl-4-methylimidazole (2E4MI), triphenylphosphine (TPP), and 4-dimethylaminopyridine (DMAP). The Lewis acid may include 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 (i.e., initiators), such as peroxides that can generate free radicals. Curing initiators include, but are not limited to: dicumyl peroxide, tert-butyl peroxybenzoate, dibenzoyl peroxide (BPO), 2,5-dimethyl-2,5-di(tert-butylperoxy)-3-hexyne (25B), bis(tert-butylperoxyisopropyl)benzene, or combinations thereof.

[0168] In one embodiment, for example, the polymerization inhibitor described in this invention is not particularly limited, and may be any type of polymerization inhibitor known in the art, including but not limited to various commercially available polymerization inhibitor products. For example, the above-mentioned polymerization inhibitor may include, but is not limited to, 1,1-diphenyl-2-trinitrophenylhydrazine, methacrylonitrile, disulfide, nitrogen oxide stabilized free radical, triphenylmethyl free radical, metal ion free radical, sulfur free radical, hydroquinone, p-methoxyphenol, p-benzoquinone, phenathiazide, β-phenylnaphthylamine, p-tert-butylcatechol, methylene blue, 4,4'-butylenebis(6-tert-butyl-3-methylphenol), 2,2'-methylenebis(4-ethyl-6-tert-butylphenol), or combinations thereof.

[0169] For example, the aforementioned stable nitroxide radicals may include, but are not limited to, nitroxide radicals derived from cyclic hydroxylamines, such as 2,2,6,6-substituted-1-piperidinoxy radicals or 2,2,5,5-substituted-1-pyrrolidineoxy radicals. As substituents, alkyl groups with 4 or fewer carbon atoms, such as methyl or ethyl, are preferred. Specific examples of nitroxide radical compounds include 2,2,6,6-tetramethyl-1-piperidinoxy radicals, 2,2,6,6-tetraethyl-1-piperidinoxy radicals, 2,2,6,6-tetramethyl-4-oxo-1-piperidinoxy radicals, 2,2,5,5-tetramethyl-1-pyrrolidineoxy radicals, 1,1,3,3-tetramethyl-2-isodihydroindole oxygen radicals, and N,N-di-tert-butylamine oxygen radicals. Stable radicals such as galvinoxyl radicals may also be used instead of nitroxide radicals.

[0170] The polymerization inhibitors suitable for the resin compositions of the present invention can also be products derived from the substitution of hydrogen atoms or groups of atoms in the polymerization inhibitor by other atoms or groups of atoms. For example, products derived from the substitution of hydrogen atoms in the polymerization inhibitor by groups such as amino, hydroxyl, or ketone carbonyl.

[0171] In one embodiment, for example, the dyeing agent suitable for the present invention may include, but is not limited to, dyes or pigments.

[0172] In one embodiment, for example, the main function of adding a solvent is to change the solid content of the resin composition and adjust its viscosity. For example, the solvent may include, but is not limited to, methanol, ethanol, ethylene glycol monomethyl ether, acetone, butanone (also known as methyl ethyl ketone), methyl isobutyl ketone, cyclohexanone, toluene, xylene, methoxyethyl acetate, ethoxyethyl acetate, propoxyethyl acetate, ethyl acetate, dimethylformamide, dimethylacetamide, propylene glycol methyl ether, and other solvents or mixtures thereof.

[0173] In one embodiment, for example, the main function of adding a toughening agent is to improve the toughness of the resin composition. The toughening agent may include, but is not limited to, compounds such as carboxyl-terminated butadiene acrylonitrile rubber (CTBN), core-shell rubber, or combinations thereof.

[0174] In one embodiment, for example, the silane coupling agent used in this invention may include silane compounds (such as, but not limited to, siloxane compounds), which may be further classified according to the type of functional group as amino silane compounds, epoxy silane compounds, vinyl silane compounds, acrylate silane compounds, methacrylate silane compounds, hydroxy silane compounds, isocyanate silane compounds, methacryloxy silane compounds, and acryloyloxy silane compounds.

[0175] The resin compositions of the foregoing embodiments can be made into various articles, such as components for various electronic products, including but not limited to prepregs, resin films, laminates or printed circuit boards.

[0176] For example, the resin compositions of various embodiments of the present invention can be made into prepregs, which include 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 can be 100°C. o C to 200 o Between C and . The reinforcing material can be any of fiber materials, woven fabrics, or nonwoven fabrics, 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, D-type, S-type, T-type, L-type, 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 can also include liquid crystal resin woven fabric, such as polyester woven fabric or polyurethane woven fabric, etc., but is not limited thereto. This reinforcing material can increase the mechanical strength of the prepreg. In a preferred embodiment, the reinforcing material can also be selectively pretreated with a silane coupling agent. The prepreg forms an insulating layer after subsequent heating and curing (C-stage).

[0177] For example, the resin compositions of various embodiments of the present invention can be made into resin films, which are obtained by baking and heating the aforementioned resin compositions to achieve semi-curing. The resin composition can be selectively coated onto polyethylene terephthalate film (PET film), polyimide film (PI film), copper foil, or adhesive-backed copper foil, and then baked and heated to form a semi-cured state, thereby forming a resin film.

[0178] For example, the resin compositions of various embodiments of the present invention can be made into a laminate comprising two metal foils and an insulating layer disposed between the metal foils. The insulating layer can be obtained by curing the aforementioned resin composition under high temperature and high pressure conditions (C-stage), wherein a suitable curing temperature can be between 180°C and 190°C. o C to 300 o Between C, preferably 200 o C to 280 o The curing time is between 90 and 180 minutes, preferably between 120 and 150 minutes. The insulating layer can be formed by curing (C-stage) the aforementioned prepreg or resin film. The metal foil may include copper, aluminum, nickel, platinum, silver, gold, or alloys thereof; for example, the metal foil may be copper foil.

[0179] Preferably, the aforementioned laminate is a copper clad laminate (CCL).

[0180] Furthermore, the aforementioned multilayer board can be further processed through circuit manufacturing processes to form a circuit board, such as a printed circuit board.

[0181] Preferably, the resin composition or product thereof provided by the present invention can improve one or more aspects such as glass transition temperature, copper foil tensile strength, dielectric loss, amount of resin flowing into the board, edge stripes, or heat resistance after moisture absorption.

[0182] For example, the resin composition or articles thereof provided by the present invention may satisfy one, more or all of the following characteristics:

[0183] The glass transition temperature, measured using dynamic mechanical analysis according to the method described in IPC-TM-650 2.4.24.4, is greater than or equal to 220°C. o C, for example, between 220 o C and 233 o Between C;

[0184] The copper foil tensile strength measured according to the method described in IPC-TM-650 2.4.8 is greater than or equal to 3.50 lb / in, for example, between 3.50 lb / in and 3.80 lb / in;

[0185] The dielectric loss measured at a frequency of 10 GHz according to the method described in JIS C2565 is less than or equal to 0.00350, for example, between 0.00315 and 0.00350;

[0186] The amount of adhesive flowing into the board after lamination is greater than or equal to 15.0 mm, for example, between 15.0 mm and 26.0 mm;

[0187] The product (e.g., without a copper substrate) has no edge striations visible to the naked eye; and

[0188] The product underwent a pressure cooking test according to the method described in IPC-TM-650 2.6.16.1, followed by a heat resistance test according to the method described in IPC-TM-650 2.4.23, and no plate bursting occurred.

[0189] The resin compositions of the embodiments and comparative examples of the present invention were prepared according to the amounts specified in Tables 1 to 5 using various raw materials from the following sources, and further processed into various test samples or articles. The composition and test results of the resin compositions of the embodiments and comparative examples are shown in Tables 1 to 5 (all units are parts by weight).

[0190] Copolymer 1 to Copolymer 5: from Preparation Examples 1 to 5.

[0191] Comparative copolymers 1 to 12: derived from comparative preparation examples 1 to 12.

[0192] Phenylacetylsilane: as shown in formula (I), purchased from Suzhou Sisso.

[0193] Diphenyldivinylsilane: as shown in formula (II), purchased from Suzhou Sisso.

[0194] Divinylbenzene: Purchased from Nippon Steel Chemical Co., Ltd., Japan.

[0195] Styrene: Commercially available, source is not limited.

[0196] Allyltrimethylsilane: Commercially available, source is not limited.

[0197] Ricon 100: Styrene-butadiene copolymer, purchased from Cray Valley.

[0198] Methacrylates: Commercially available, source is not limited.

[0199] SA9000: Terminal dimethacrylate polyphenylene ether resin, purchased from Sabic.

[0200] OPE-2st 2200: Terminal divinyl benzyl polyphenylene ether resin, purchased from Sabic.

[0201] ODV1: A multifunctional vinyl aromatic copolymer with a Mw of 28,600, containing ethyl vinylbenzene, divinylbenzene and styrene structural units, purchased from Nippon Steel Chemical Co., Ltd., Japan.

[0202] ODV2: A multifunctional vinyl aromatic copolymer with a Mw of 89,000, comprising ethyl vinylbenzene, divinylbenzene, styrene, and methacrylate structural units, purchased from Nippon Steel Chemical Co., Ltd., Japan.

[0203] SC-2500SMJ: Spherical silica treated with acrylate-based silane coupling agent, purchased from Admatechs.

[0204] 25B: 2,5-Dimethyl-2,5-Di(tert-butylperoxy)-3-hexyne, purchased from Nippon Oil Co., Ltd.

[0205] MEK: Butyl ketone, commercially available, source is not limited.

[0206] Toluene: Purchased from Qiangdi.

[0207] In the table, "Z" represents the total amount of all components in the resin composition of each example or comparative example excluding (i.e., not containing) inorganic fillers and solvents. For example, "Z*1.0" means that the amount of inorganic filler added is 1.0 times the aforementioned Z. For example, "Z*0.6" in Example E1 means that the amount of inorganic filler added is 90.3 parts by weight (150.5 parts by weight multiplied by 0.6).

[0208] In the table, "appropriate amount" for solvent addition means the amount of solvent used to achieve the ideal solid content of the overall resin composition. For resin compositions using both methyl ethyl ketone (MEK) and toluene as solvents, "appropriate amount" means the total amount of these two solvents is sufficient to achieve the ideal solid content of the overall resin composition, for example, but not limited to, a solid content of 70% by weight.

[0209] The composition and test results of the resin compositions in the examples and comparative examples are shown in Tables 1 to 5 (all units are parts by weight):

[0210] [Table 1] Composition (parts by weight) and property test results of the resin compositions in the examples

[0211]

[0212] [Table 2] Composition (parts by weight) and property test results of the resin compositions in the examples

[0213]

[0214] [Table 3] Composition (parts by weight) and property test results of comparative example resin compositions

[0215]

[0216] [Table 4] Composition (parts by weight) and property test results of comparative example resin compositions

[0217]

[0218] [Table 5] Composition (parts by weight) and property test results of comparative example resin compositions

[0219]

[0220] The various resin compositions shown in Tables 1 to 5 were prepared as follows: varnish and various test samples were prepared according to the following methods, and the characteristics were measured according to specific test conditions to obtain test results.

[0221] Varnish (or adhesive)

[0222] Each embodiment (represented by E, such as E1 to E12) or comparative example (represented by C, such as C1 to C21) is added to a mixing tank according to the amounts in Tables 1 to 5 and stirred. The resulting resin composition is called resin varnish.

[0223] Taking Example E1 as an example, 100 parts by weight of vinyl polyphenylene ether resin (SA9000) and 50 parts by weight of copolymer 1 were added to a stirrer containing an appropriate amount of toluene and an appropriate amount of methyl ethyl ketone (the solvent "appropriate amount" in Tables 1 to 5 represents the amount of solvent used to obtain the ideal solid content of the resin composition, for example, the solid content of the varnish is 70% by weight). The mixture was stirred until all solid components were dissolved into a homogeneous liquid phase. Then, "Z*0.6" parts by weight of spherical silica SC-2500SMJ (i.e., 90.3 parts by weight) were added and stirred until completely dispersed. Then, 0.5 parts by weight of curing accelerator (25B, which is first dissolved in an appropriate amount of solvent) were added and stirred for 1 hour to obtain the varnish of resin composition E1.

[0224] In addition, according to the ingredient amounts listed in Tables 1 to 5, and referring to the method for preparing the varnish of Example E1, varnishes of other Examples E2 to E12 and Comparative Examples C1 to C21 were prepared.

[0225] Prepreg (using 2116 E-glass fiber cloth)

[0226] The resin compositions of the different examples (E1 to E12) and comparative examples (C1 to C21) listed in Tables 1 to 5 were added in batches to a mixing tank, mixed thoroughly, and stirred until completely dissolved into varnish. The resin compositions were then placed in an impregnation tank. Fiberglass cloth (e.g., E-fiberglass cloth of specification 2116) was passed through the impregnation tank to adhere the resin composition to the fiberglass cloth, and the mixture was heated to 120°C. o C to 150 o Heating at C to a semi-cured state (B-Stage) yields a semi-cured sheet (resin content approximately 52%).

[0227] Prepreg (using 1080 E-glass fiber cloth)

[0228] The resin compositions from the different examples (E1 to E12) and comparative examples (C1 to C21) listed in Tables 1 to 5 were added in batches to a mixing tank, mixed thoroughly, and stirred until completely dissolved into varnish. The resin compositions were then placed in an impregnation tank. Fiberglass cloth (e.g., E-fiberglass cloth of specification 1080) was passed through the impregnation tank to adhere the resin composition to the fiberglass cloth, and the mixture was heated to 120°C. o C to 150 o Heating at C to a semi-cured state (B-Stage) yields a semi-cured sheet (resin content approximately 71%).

[0229] Copper foil substrate (made by laminating five prepreg sheets)

[0230] Two 18-micron thick ultra-low profile copper foils (HVLP copper foil) and five prepregs (using 1080E glass fiber cloth) were prepared in batches. Each prepreg contained approximately 71% resin. The copper foil, five prepregs, and copper foil were stacked in that order and subjected to vacuum conditions at 210°C. o Each copper foil substrate is formed by pressing under pressure for 2 hours. Among them, five prepregs stacked together are cured (C-stage) to form an insulating layer between the two copper foils. The resin content of the insulating layer is about 71%.

[0231] Copper foil substrate (made by laminating eight prepreg sheets)

[0232] Two 18-micron thick ultra-low profile copper foils (HVLP copper foil) and eight prepregs (using 2116E-glass fiber cloth) were prepared in batches. Each prepreg contained approximately 52% resin. The copper foil, eight prepregs, and copper foil were stacked in that order and subjected to vacuum conditions at 210°C. o Each copper foil substrate is formed by pressing under pressure for 2 hours. Among them, eight prepregs stacked together are cured (C-stage) to form an insulating layer between the two copper foils. The resin content of the insulating layer is about 52%.

[0233] Copper-free substrate (made by laminating eight prepreg sheets)

[0234] The copper foil substrate (made of eight prepregs laminated together) is etched to remove the copper foil on both sides to obtain a copper-free substrate, which is made of eight prepregs laminated together and has a resin content of about 52%.

[0235] Copper-free substrate (made by laminating two prepreg sheets)

[0236] Two 18-micron thick ultra-low profile 2 copper foils (HVLP2 copper foil) and two prepregs (using 1080 E-glass fiber cloth) made from various resin compositions were prepared in batches. Each prepreg contained approximately 71% resin. The copper foil, two prepregs, and copper foil were stacked in that order and subjected to vacuum conditions at 210°C. o Under pressure (C-stage) for 2 hours, each copper foil substrate is formed. Then, the copper foil on both sides of the copper foil substrate is etched away to obtain a copper-free substrate. Among them, two prepreg sheets are cured (C-stage) to form an insulating layer between the two copper foils. The resin content of the insulating layer is about 71%.

[0237] The test methods and their characteristic analysis items are described below.

[0238] 1. Glass transition temperature (Tg)

[0239] In the glass transition temperature test, a copper-free substrate (composed of eight prepreg sheets laminated together) was selected as the test sample for dynamic mechanical analysis (DMA). The temperature rise rate was 2°C per minute. o The sample was heated at 35°C. o C rises to 380 oWithin the temperature range of C, the glass transition temperature of each sample was measured according to the method described in IPC-TM-650 2.4.24.4 (unit: ). o C). A higher glass transition temperature indicates better sample properties.

[0240] For example, articles made from the resin compositions disclosed in this invention have a high glass transition temperature, as measured with reference to the method described in IPC-TM-6502.4.24.4, such as a glass transition temperature Tg greater than or equal to 220°C. o C, for example, between 220 o C and 233 o Between C, for example, greater than or equal to 220 o C, 221 o C, 224 o C, 227 o C, 229 o C, 230 o C, 231 o C, 232 o C or 233 o C.

[0241] 2. Copper foil tensile strength (or peel strength, P / S)

[0242] A copper foil substrate (made by laminating eight prepreg sheets) was cut into rectangular samples with a width of 24 mm and a length greater than 60 mm. The surface copper foil was then etched, leaving only a strip of copper foil with a width of 3.18 mm and a length greater than 60 mm. A universal tensile strength tester was used at room temperature (approximately 25°C). o C) Measure the force (lb / in) required to pull the copper foil away from the substrate surface according to the method described in IPC-TM-650 2.4.8. A higher copper foil pull force is better, and a difference of 0.1 lb / in or greater is considered significant (indicating significant technical difficulty).

[0243] For example, an article made from the resin composition disclosed in this invention has a copper foil tensile strength, measured with reference to the method described in IPC-TM-650 2.4.8, that is greater than or equal to 3.50 lb / in, preferably greater than or equal to 3.50 lb / in, 3.60 lb / in, 3.65 lb / in, 3.70 lb / in, 3.75 lb / in, or 3.80 lb / in, for example, between 3.50 lb / in and 3.80 lb / in.

[0244] 3. Dielectric loss (dissipation factor, Df)

[0245] For dielectric loss measurement, the copper-free substrate (composed of two prepreg sheets laminated together) was selected as the test sample. A microwave dielectric analyzer (purchased from AET Corporation, Japan) was used to measure the dielectric loss of each sample at a frequency of 10 GHz, following the method described in JIS C2565. Lower dielectric loss indicates better dielectric properties of the test sample.

[0246] At a measurement frequency of 10 GHz, when the Df value is less than or equal to 0.005, 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 (which presents significant technical difficulties).

[0247] For example, an article made from the resin composition disclosed in this invention has a dielectric loss of less than or equal to 0.00350 when measured at a frequency of 10 GHz, as described in JIS C2565, for example, between 0.00315 and 0.00350, for example, less than or equal to 0.00315, 0.00320, 0.00325, 0.00330, 0.00340 or 0.00350.

[0248] 4. Adhesive flow rate inside the board

[0249] First, prepare a copper-containing substrate of EM-827 as a copper-containing core board (available from Zhongshan Taiguang Electronic Materials Co., Ltd., which uses 7628 E-glass fiber cloth and 1 ounce HTE copper foil). The thickness of the copper-containing core board is 28 mils. The surface copper foil of this copper-containing core board is treated with a known browning process to obtain a browned core board.

[0250] Prepare in batches a prepreg (made of 1080 E-glass fiber cloth, each prepreg has a resin content of about 71%, a thickness of about 4.5 mils, and a length and width of 17 inches and 15 inches respectively) and a brown core board with a thickness of 28 mils and a length and width of 18 inches and 16 inches respectively, wherein the prepreg has a diamond-shaped opening with a length and width of 4 inches in the center (a diamond-shaped space of 4 inches * 4 inches is punched out in the center of the prepreg using a known punching machine).

[0251] The substrate is constructed by stacking a 0.5 oz HTE copper foil (reverse-pressed, meaning the bright side of the copper foil contacts the prepreg), a prepreg, and a browned core board in sequence, followed by vacuum and high temperature (200°C). oC) Under high pressure (360 psi) and curing conditions for 2 hours, a copper-containing multilayer board is obtained. After removing the surface copper foil of this copper-containing multilayer board, an in-board resin flow sample is obtained. Take the in-board resin flow sample, and use the sides of a 4-inch * 4-inch rhombus as the baseline. Divide each side into 4 equal parts with 3 bisecting points, and measure the resin flow amount at each of the 12 points (i.e., the vertical resin flow distance at each of the 12 points). Calculate the average value of the resin flow amount at the 12 points to obtain the in-board resin flow amount (average value), in mm. Generally, the in-board resin flow amount is preferably between 15.0 mm and 26.0 mm. For example, the in-board resin flow amount of an article made from the resin composition disclosed in this invention after lamination is greater than or equal to 15.0 mm.

[0252] 5. Stripes on the edge of the board

[0253] The copper foil on both sides of the copper foil substrate (made by laminating five prepreg sheets) is etched away to obtain a copper-free substrate. The surface condition of the insulating layer on the copper-free substrate is then visually inspected. If a dendritic distribution appears along the board edge, it indicates poor compatibility or significant differences in flowability in the resin composition, resulting in unevenness. Dendritic distribution on the substrate will cause uneven characteristics (poor reliability) and a significant reduction in yield in subsequent circuit boards, such as poor dielectric properties, low heat resistance, uneven thermal expansion, or poor interlayer bonding. A schematic diagram of a copper-free substrate with a dendritic distribution is shown below. Figure 3 A schematic diagram of a copper-free substrate without dendritic distribution is shown below. Figure 4 .

[0254] 6. Heat resistance after moisture absorption (PCT)

[0255] The copper-free substrate sample (composed of eight prepreg sheets laminated together) was selected and subjected to a pressure cooking test (PCT) for 5 hours (test temperature 121°C) as described in IPC-TM-650 2.6.16.1. o After immersing at a constant temperature of 288°C (with a relative humidity of 100%), refer to the method described in IPC-TM-650 2.4.23. o The board is immersed in a solder bath (C) for 20 seconds, then removed to observe for any signs of delamination, such as interlayer peeling between insulating layers. Interlayer peeling can occur as bubbling and separation between any layers of the substrate.

[0256] For example, articles made from the resin compositions disclosed in this invention, when subjected to a heat resistance test after moisture absorption according to the methods described in IPC-TM-6502.6.16.1 and IPC-TM-650 2.4.23, do not exhibit plate bursting. A result of no plate bursting is recorded as "pass" to indicate a pass, while a result of plate bursting is recorded as "fail" to indicate a fail.

[0257] Based on the test results in Tables 1 to 5, the following phenomena can be observed.

[0258] By comparing Examples E1-E12 with Comparative Examples C1-C2, it can be confirmed that by using 100 parts by weight of vinyl polyphenylene ether resin and 30-50 parts by weight of phenyl vinylsilane-divinylbenzene-styrene trimer, compared to when the amount of phenyl vinylsilane-divinylbenzene-styrene trimer is outside the above range, the product obtained by the present invention can simultaneously achieve one, more, or all of the following technical effects: improved copper foil tensile strength, reduced dielectric loss, appropriate in-board adhesive flow, no board edge streaks, and passing the heat resistance test after moisture absorption.

[0259] By comparing Examples E1-E4, E7-E8 with Comparative Examples C3-C9, it can be confirmed that the copolymer obtained by reacting 50 to 70 parts by weight of phenylvinylsilane, 10 to 20 parts by weight of divinylbenzene, and 20 to 30 parts by weight of styrene, compared with the comparative copolymer obtained by copolymerizing phenylvinylsilane with divinylbenzene or styrene alone in amounts outside the above range, the product obtained by the present invention can simultaneously achieve one, more, or all of the technical effects of improving glass transition temperature, copper foil tensile strength, in-plate adhesive flow, and passing the heat resistance test after moisture absorption.

[0260] By comparing Examples E1-E4, E7-E8 with Comparative Examples C10-C13, it can be confirmed that the copolymer obtained by reacting 50 to 70 parts by weight of phenylvinylsilane, 10 to 20 parts by weight of divinylbenzene, and 20 to 30 parts by weight of styrene, compared with compounds whose monomer types or amounts are outside the above range, can simultaneously achieve one, more, or all of the following technical effects: increased glass transition temperature, increased copper foil tensile strength, reduced dielectric loss, increased adhesive flow within the board, no edge streaks, or passing the heat resistance test after moisture absorption.

[0261] By comparing Comparative Examples E1-E4, E7-E8 and Comparative Examples C14-C15, it can be confirmed that the phenylvinylsilane-divinylbenzene-styrene trimer of the present invention, compared with multifunctional vinyl aromatic copolymers, not only has lower reactivity and can provide longer operating time for subsequent processes, but its products can also simultaneously improve one, multiple or all of the following technical effects: increase glass transition temperature, increase copper foil tensile strength, increase in-plate adhesive flow, or pass the heat resistance test after moisture absorption.

[0262] By comparing Comparative Examples E1-E4, E7-E8 and Comparative Examples C16-C21, it can be confirmed that in the resin composition, the addition of 50 parts by weight of phenylvinylsilane-divinylbenzene-styrene trimer in this invention, compared to adding only 50 parts by weight of phenyltrivinylsilane, 50 parts by weight of divinylbenzene, and 50 parts by weight of styrene, or combining phenyltrivinylsilane with a multifunctional vinyl aromatic copolymer, combining phenyltrivinylsilane with a divinylbenzene-styrene copolymer, or adding 30 parts by weight of uncopolymerized phenyltrivinylsilane, 5 parts by weight of divinylbenzene, and 15 parts by weight of styrene, the copolymer obtained by this invention can simultaneously achieve one, multiple, or all of the following technical effects: increased glass transition temperature, increased copper foil tensile strength, reduced dielectric loss, improved in-plate flow, absence of edge streaks, or passing of wet heat resistance tests.

[0263] By comparing Examples E1-E12 with Comparative Examples C1-C21, it can be confirmed that the present invention, by using 100 parts by weight of a vinyl polyphenylene ether resin and 30 to 50 parts by weight of a phenyl vinylsilane-divinylbenzene-styrene trimer complex, enables the prepared substrate to simultaneously achieve a glass transition temperature greater than or equal to 220°C. o C. One, more, or all of the following technical effects: copper foil tensile strength greater than or equal to 3.50 lb / in, dielectric loss less than or equal to 0.00350, and adhesive flow within the board greater than or equal to 15.0 mm. Conversely, comparative examples C1 to C21, which do not use the technical solution of this invention, cannot simultaneously achieve the aforementioned technical effects.

[0264] The above embodiments are merely illustrative in nature and are not intended to limit the embodiments of the subject matter of the application or the application or use of such embodiments. In this document, the term "illustrative" means "as an example, illustration, or description." Any illustrative embodiment herein should not necessarily be interpreted as preferred or more advantageous than other embodiments.

[0265] 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 possible with respect to the invention. It should also be understood that the embodiments described herein are not intended to limit the scope, use, or configuration of the claimed subject matter in any way. Rather, the foregoing embodiments will provide a simple guide for those skilled in the art to implement one or more of the described embodiments. Moreover, various changes can be made to the function and arrangement of the elements without departing from the scope defined by the claims, and the claims include known equivalents and all foreseeable equivalents at the time of filing of this patent application.

Claims

1. A phenylvinylsilane-divinylbenzene-styrene trimer, characterized in that, The phenylvinylsilane-divinylbenzene-styrene trimer is copolymerized from 50 to 70 parts by weight of phenylvinylsilane, 10 to 20 parts by weight of divinylbenzene, and 20 to 30 parts by weight of styrene, wherein the total weight of phenylvinylsilane, divinylbenzene, and styrene is 100 parts by weight, and wherein the phenylvinylsilane has the structure shown in formula (I) or formula (II) below: Formula (I) Equation (II).

2. The phenylvinylsilane-divinylbenzene-styrene trimer according to claim 1, characterized in that, Its volatility ranges between 40% and 60%.

3. The phenylvinylsilane-divinylbenzene-styrene trimer according to claim 1, characterized in that, The content of structural units formed by phenylvinylsilane is 30 mol% to 50 mol%.

4. The phenylvinylsilane-divinylbenzene-styrene trimer according to claim 1, characterized in that, It includes the structural unit shown in equation (a) and the structural unit shown in equation (b), and also includes any one or more of the structural units shown in equations (c), (d), (e), and (f): Equation (a) Equation (b) Equation (c) Equation (d) Equation (e) Equation (f) Where m is an integer from 2 to 45, n is an integer from 5 to 86, J1 and J2 are each an integer from 3 to 81, and k1 and k2 are each an integer from 3 to 65.

5. The phenylvinylsilane-divinylbenzene-styrene trimer according to claim 1, characterized in that, Its weight-average molecular weight is between 3,000 and 30,000.

6. A method for manufacturing the phenylvinylsilane-divinylbenzene-styrene trimer as described in claim 1, characterized in that, This includes 50 to 70 parts by weight of phenylvinylsilane, 10 to 20 parts by weight of divinylbenzene, and 20 to 30 parts by weight of styrene in a solution of 70 parts by weight. o C to 130 o The reaction is carried out at C for 3 to 14 hours.

7. A resin composition, characterized in that, It comprises 30 to 50 parts by weight of the phenylvinylsilane-divinylbenzene-styrene trimer as described in claim 1 and 100 parts by weight of a vinyl-containing polyphenylene ether resin.

8. The resin composition according to claim 7, characterized in that, Further including maleimide resins, maleimide triazine resins, unsaturated polyolefin resins, hydrogenated unsaturated polyolefin resins, small molecule vinyl-containing resins, styrene-maleic anhydride resins, epoxy resins, phenolic resins, benzoxazine resins, cyanate ester resins, polyester resins, polyamide resins, polyimide resins, or combinations thereof.

9. The resin composition according to claim 8, characterized in that, The small molecule vinyl resin includes styrene, divinylbenzene, di(vinylbenzyl) ether, 1,2,4-trivinylcyclohexane, di(vinylphenyl)ethane, di(vinylphenyl)hexane, divinylphenyldimethyl ether, divinylphenyldimethylbenzene, triallyl isocyanurate, triallyl cyanurate, prepolymers of any of the foregoing components, or combinations thereof.

10. The resin composition according to claim 7, characterized in that, The vinyl-containing polyphenylene ether resin includes terminal vinyl benzyl polyphenylene ether resin, terminal methacrylate polyphenylene ether resin, or a combination thereof.

11. The resin composition according to claim 10, characterized in that, The terminal vinyl benzyl polyphenylene ether resin and the terminal methacrylate polyphenylene ether resin respectively comprise the structures shown in formula (III) and formula (IV): Equation (III) Formula (IV) Among them, R1 to R 14 Each is independently H or -CH3, and W1 and W2 are independently C1 to C3 divalent aliphatic groups; b1 is an integer from 0 to 8; Q1 includes any one or a combination of the structures shown in equations (B-1) to (B-3): Equation (B-1) Equation (B-2) Equation (B-3) Y1 and Y2 each independently include the structure shown in equation (B-4): Equation (B-4) Among them, R 15 To R 30 Each is independently H or -CH3; m1 and n1 are each independently an integer from 1 to 30; and A1 is selected from covalent bonds, -CH2-, -CH(CH3)-, -C(CH3)2-, -O-, -S-, -SO2- and carbonyl groups.

12. The resin composition according to claim 7, characterized in that, It also includes amine curing agents, flame retardants, inorganic fillers, curing accelerators, polymerization inhibitors, colorants, solvents, toughening agents, silane coupling agents, or combinations thereof.

13. An article made from the resin composition of claim 7, characterized in that, The products include prepregs, resin films, laminates, or printed circuit boards.

14. The article of claim 13, characterized in that, The glass transition temperature of the product, measured using dynamic mechanical analysis according to IPC-TM-650 2.4.24.4, is greater than or equal to 220°C. o C.

15. The article of claim 13, characterized in that, The copper foil tensile strength of the product, measured according to the method described in IPC-TM-650 2.4.8, is greater than or equal to 3.50 lb / in.

16. The article of claim 13, characterized in that, The dielectric loss of the product, measured at a frequency of 10 GHz according to the method described in JIS C2565, is less than or equal to 0.00350.

17. The article of claim 13, characterized in that, The amount of adhesive flowing into the board after the product is pressed is greater than or equal to 15.0 mm.

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