Resin composition and product thereof

Abstract

The invention discloses a resin composition and a product thereof. The resin composition comprises (A) 100 parts by weight of a copolymer having a structural unit formed by a monomer represented by a formula (1) and a structural unit formed by a monomer represented by a formula (2), and the content of the structural unit formed by the monomer represented by the formula (2) in the copolymer being 55 wt% to 90 wt%; and (B) 1-15 parts by weight of a compound represented by formula (3). The resin composition can be prepared into a prepreg, a resin film, a laminated board or a printed circuit board, and at least one of characteristics such as glass transition temperature, storage modulus attenuation rate, reflow soldering warpage, Z-axis thermal expansion rate, dielectric loss and substrate appearance is improved. # imgabs0 #

Description

Technical Field

[0001] The present invention mainly relates to a resin composition and articles made therefrom, particularly to a resin composition applicable to prepregs, resin films, laminates (such as copper foil substrates), and printed circuit boards, and articles made therefrom. Background Art

[0002] As an essential electronic component, printed circuit boards (PCBs) are applied in various fields including mobile phones, computers, communication base stations, data centers, automobiles, industrial control, aerospace, etc. The technical level and reliability of PCBs have a direct impact on the performance and stability of electronic devices. As the substrate material of PCBs, copper clad laminates (CCLs) mainly play roles in interconnection conduction, insulation, and support, and have a great influence on aspects such as signal transmission speed, energy loss, and characteristic impedance in circuits. The performance, quality, processability, reliability, stability, etc. of PCBs largely depend on the performance and quality of CCLs.

[0003] The advanced PCB packaging technology currently faces problems in aspects such as process capabilities, signal integrity, heat dissipation, and stress, which pose higher requirements for the performance of CCLs, including higher glass transition temperatures, better substrate appearances, as well as lower Z-axis thermal expansion rates, reflow warpage, storage modulus decay rates, and dielectric losses. However, the existing CCLs and the resin compositions used in their preparation still mainly focus on the conventional characteristics of CCLs and cannot fully meet the requirements of advanced PCB packaging technology. 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 technical problems, the main object of the present invention is to provide a resin composition that can overcome at least one of the above technical problems and articles made using this resin composition.

[0005] To achieve the above object, the present invention discloses a resin composition, comprising: (A) 100 parts by weight of a copolymer having structural units formed from monomers represented by formula (1) and structural units formed from monomers represented by formula (2), and the content of the structural units formed from monomers represented by formula (2) in the copolymer is 55 wt% to 90 wt%; and (B) 1 part by weight to 15 parts by weight of a compound represented by formula (3);

[0006]

[0007] In formula (1), each of R1 to R5 is independently selected from a hydrogen atom, a C1-C3 alkyl group, a C2-C3 alkenyl group, a phenyl group, a phenyl group substituted by a C1-C3 alkyl group, a phenyl group substituted by a C2-C3 alkenyl group, and a C2-C3 alkenylphenyl C1-C3 alkylene group;

[0008] In formula (2), each of R6 to R9 is independently selected from a hydrogen atom, a C1-C3 alkyl group, and a C2-C3 alkenyl group, and at least one of R6 to R9 is a C2-C3 alkenyl group;

[0009] In formula (3), each of X', Y', and Z' independently represents a hydrogen atom, a C1-C4 alkyl group, a phenyl group, or a group containing an unsaturated carbon-carbon double bond.

[0010] For example, in one embodiment, the monomer represented by formula (1) includes the monomer represented by formula (1-1), the monomer represented by formula (1-2), the monomer represented by formula (1-3), the monomer represented by formula (1-4), or a combination thereof, and the monomer represented by formula (2) includes the monomer represented by formula (2-1).

[0011]

[0012] For example, in one embodiment, the copolymer includes any one or a combination of the copolymers represented by the following formulas (4) to (19):

[0013]

[0014]

[0015] wherein, m, n, x, y, z are each independently a positive integer, and 2 ≤ m ≤ 44, 12 ≤ n ≤ 70, 2 ≤ x + z ≤ 44, 12 ≤ y ≤ 70.

[0016] For example, in one embodiment, the copolymer includes a block copolymer, a random copolymer, or a combination thereof.

[0017] For example, in one embodiment, the compound represented by formula (3) has at least one group containing an unsaturated carbon-carbon double bond.

[0018] For example, in one embodiment, in formula (3), at least one of X', Y', and Z' represents vinyl, vinylbenzyl, vinylphenyl, allyl, or (meth)acryloyloxy.

[0019] For example, in one embodiment, the compound represented by formula (3) includes any one or a combination of the compounds from formula (3-1) to formula (3-6):

[0020]

[0021]

[0022] For example, in one embodiment, the resin composition further includes a crosslinking agent containing unsaturated carbon-carbon double bonds, and the crosslinking agent containing unsaturated carbon-carbon double bonds is any one or a combination of bis(vinylphenyl)ethane, divinylbenzene, divinylnaphthalene, divinylbiphenyl, triallyl isocyanurate, triallyl cyanurate, vinylbenzocyclobutene, bis(vinylbenzyl)ether, trivinylcyclohexane, diallylbisphenol A, acrylate with bifunction or more, butadiene, decadiene, octadiene.

[0023] For example, in one embodiment, the resin composition further includes any one or a combination of a polyolefin different from the copolymer, a polyphenylene ether resin containing unsaturated carbon-carbon double bonds, a benzoxazine resin, an epoxy resin, a polyester resin, a phenolic resin, an amine curing agent, a polyamide, a polyimide, styrene maleic anhydride, a maleimide resin, and a cyanate ester.

[0024] For example, in one embodiment, the resin composition further includes any one or a combination of an inorganic filler, a flame retardant, a curing accelerator different from the compound represented by formula (3), a polymerization inhibitor, a solvent, a silane coupling agent, a dye, and a toughening agent.

[0025] To achieve the above object, the present invention also discloses an article made of the aforementioned resin composition, which includes a prepreg, a resin film, a laminate, or a printed circuit board.

[0026] For example, in one embodiment, the aforementioned article has at least one, a plurality, or all of the following characteristics:

[0027] Its glass transition temperature measured by the method of IPC-TM-650 2.4.24.4 is greater than or equal to 290 °C;

[0028] Its storage modulus decay rate measured by the method of IPC-TM-650 2.4.24.4 is less than or equal to 16%;

[0029] Its reflow warpage measured by the method of JESD22-B112A is less than or equal to 14 μm;

[0030] Its Z-axis thermal expansion rate measured by the method of IPC-TM-650 2.4.24.5 is less than or equal to 1.2%;

[0031] There are no dendritic streaks in the appearance of the substrate observed visually; and

[0032] Its dielectric loss, measured according to the method of JIS C2565 at a frequency of 10 GHz, is less than or equal to 0.00086. Detailed implementation manners

[0033] To enable those skilled in the art to understand the features and effects of the present invention, the following provides a general description and definition of the terms and phrases mentioned in the specification and claims. Unless otherwise specified, all technical and scientific terms used herein have the ordinary meaning understood by those skilled in the art with respect to the present invention. In case of conflict, the definition in this specification shall prevail.

[0034] The theories or mechanisms described and disclosed herein, whether correct or incorrect, shall not limit the scope of the present invention in any way, that is, the content of the present invention can be implemented without being limited by any specific theory or mechanism.

[0035] As used herein, the terms "a", "an", "one", or similar expressions are used to describe the components and technical features of the present invention. Such descriptions are merely for convenience of expression and to give a general meaning to the scope of the present invention. Therefore, such descriptions should be understood to include one or at least one, and the singular also includes the plural, unless clearly indicated otherwise.

[0036] In this article, the terms "comprising", "including", "having", "containing", or any other similar terms are all open-ended transitional phrases, which are intended to cover non-exclusive inclusions. For example, a composition or article thereof comprising a plurality of elements covers any one or any kind of the listed elements, and is not limited to only the elements listed herein, but may also include other elements that are not explicitly listed but are usually inherent in the composition or article. In addition, unless otherwise clearly stated to the contrary, the term "or" refers to an inclusive "or", rather than an exclusive "or". For example, any of the following situations satisfies the condition "A or B": A is true (or exists) and B is false (or does not exist), A is false (or does not exist) and B is true (or exists), A and B are both true (or exist). Furthermore, in this article, the interpretations of the terms "comprising", "including", "having", "containing" should be regarded as having specifically disclosed and simultaneously covered closed transitional phrases such as "consisting of", "composed of", "the balance being", etc., as well as connecting words such as "substantially consisting of", "mainly consisting of", "mainly composed of", "basically containing", "basically consisting of", "basically composed of", "essentially containing".

[0037] In this text, "or combinations thereof" means "any combination thereof", covering combinations of two or more of the listed elements; "any", "any kind", "any one" means "any one", "any kind", "any one". For example, when it is stated that "a composition or its product comprises A, B, C or combinations thereof", in interpretation, it covers the following situations: A is true (or present) and B and C are false (or absent), B is true (or present) and A and C are false (or absent), C is true (or present) and A and B are false (or absent), A and B are true (or present) and C is false (or absent), A and C are true (or present) and B is false (or absent), B and C are true (or present) and A is false (or absent), A, B and C are all true (or present), and other elements that are not explicitly listed but are normally inherent in the composition or its product.

[0038] In this text, the terms "and", "with", "and", "as well as" or other similar terms are used to connect parallel sentence components, and there is no primary or secondary distinction between the front and back components. The parallel sentence components do not change in meaning in terms of grammar when their positions are interchanged.

[0039] In this text, all features or conditions defined in the form of numerical ranges or percentage ranges, such as numerical values, quantities, contents and concentrations, are only for the sake of brevity and convenience. Accordingly, the description of a numerical range or percentage range should be regarded as having covered and specifically disclosed all possible sub-ranges and individual numerical values within the range (including integers and fractions), especially integer numerical values. For example, a range description of "1.0 to 8.0", "between 1.0 and 8.0" or "between 1.0 to 8.0" should be regarded as having specifically disclosed all sub-ranges such as 1.0 to 8.0, 1.0 to 7.0, 2.0 to 8.0, 2.0 to 6.0, 3.0 to 6.0, 4.0 to 8.0, 3.0 to 8.0, etc., and should be regarded as covering the endpoint values, especially sub-ranges defined by integer numerical values, and should be regarded as having specifically disclosed individual numerical values such as 1.0, 2.0, 3.0, 4.0, 5.0, 6.0, 7.0, 8.0, etc. within the range. Unless otherwise specified, the foregoing interpretation method applies to all contents of the present invention, regardless of the scope being broad or narrow.

[0040] If a quantity, concentration or other numerical value or parameter is expressed as a range, a preferred range (or a better range) or a series of upper and lower limits, it should be understood that all ranges constituted by any pair of the upper limit or preferred value (or better value) and the lower limit or preferred value (or better value) of the range have been specifically disclosed herein, regardless of whether these ranges are separately disclosed or not. In addition, when a numerical range is mentioned in this text, unless otherwise stated, the range should include its endpoints and all integers and fractions within the range.

[0041] In this text, on the premise that the purpose of the invention can be achieved, a numerical value should be understood to have the precision of the significant digits of that numerical value. For example, the number 40.0 should be understood to cover the range from 39.50 to 40.49.

[0042] In this text, for the case of using a Markush group or alternative terms to describe the features or examples of the present invention, those skilled in the art should understand that a subgroup or any individual element within the Markush group or list of alternatives can also be used to describe the present invention. For example, if X is described as "selected from the group consisting of X1, X2, and X3", it also means 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, for the case of using a Markush group or alternative terms to describe the features or examples of the present invention, those skilled in the art should understand that any combination of a subgroup or individual members within the Markush group or list of alternatives can also be used to describe the present invention. Accordingly, for example, if X is described as "selected from the group consisting of X1, X2, and X3", and Y is described as "selected from the group consisting of Y1, Y2, and Y3", it means that the claim that X is X1 and / or X2 and / or X3 and Y is Y1 and / or Y2 and / or Y3 has been fully described.

[0043] Unless otherwise specified, in the present invention, a compound refers to a chemical substance formed by the connection of two or more elements through chemical bonds, including small molecule compounds and high molecular compounds, and is not limited thereto. In this text, a compound is not limited to a single chemical substance when being interpreted, but can also be interpreted as a group of chemical substances having the same composition or the same properties.

[0044] Unless otherwise specified, in the present invention, a polymer refers to a product formed by monomers through a polymerization reaction, which often includes aggregates of many macromolecules. Each macromolecule is formed by repeating covalent bonds of many simple structural units, and a monomer is a compound that synthesizes a polymer. Polymers can include homopolymers, copolymers, prepolymers, etc., and are not limited thereto. A homopolymer refers to a polymer formed by polymerization of one type of monomer. A copolymer refers to a polymer formed by polymerization of two or more types of monomers. Copolymers include random copolymers (with a structure such as -AABABBBAAABBA-), alternating copolymers (with a structure such as -ABABABAB-), graft copolymers (with a structure such as -AA(A-BBBB)AA(A-BBBB)AAA-), and block copolymers (with a structure such as -AAAAA-BBBBBB-AAAAA-), etc. For example, the styrene-butadiene copolymer in the present invention may include styrene-butadiene random copolymer, styrene-butadiene alternating copolymer, styrene-butadiene graft copolymer, or styrene-butadiene block copolymer when interpreted. A prepolymer refers to a polymer with a relatively low molecular weight between that of a monomer and the final polymer, and the prepolymer contains reactive functional groups that can further undergo a polymerization reaction to obtain a higher molecular weight product with complete cross-linking or hardening. Polymers of course include oligomers, and are not limited thereto. An oligomer, also known as a low polymer, is a polymer composed of 2 to 20 repeating units, usually a polymer composed of 2 to 5 repeating units.

[0045] For those skilled in the art, a resin composition containing three compounds A, B, and C and an additive (a total of four components), and a resin composition containing a prepolymer formed from three compounds A, B, and C and an additive (a total of two components) are different resin compositions. The two are completely different in many aspects such as the preparation method, their own physical and chemical properties, and the properties of their products. For example, the former is to mix A, B, C, and the additive to form a resin composition, while the latter requires first subjecting the mixture including A, B, and C to a prepolymerization reaction under appropriate conditions to form a prepolymer, and then mixing the prepolymer with the additive to obtain a resin composition. For example, for those skilled in the art, the above two resin compositions have completely different compositions, and since the functions exerted by the prepolymer formed from the three compounds A, B, and C in the resin composition are completely different from the functions exerted by A, B, and C individually or jointly in the resin composition, the two resin compositions should be regarded as completely different chemical substances and have completely different chemical statuses. For example, for those skilled in the art, since the above two resin compositions are completely different chemical substances, their products will not have the same properties. For example, for a resin composition including a prepolymer formed from three compounds A, B, and C and a crosslinking agent, since A, B, and C have partially reacted or transformed during the prepolymerization reaction to form a prepolymer, when the resin composition is heated at a high temperature to form a semi-cured state later, a partial crosslinking reaction occurs between the prepolymer and the crosslinking agent, rather than a partial crosslinking reaction between A, B, and C individually and the crosslinking agent. Therefore, the products formed from the two resin compositions will also be completely different and have completely different properties.

[0046] Unless otherwise specified, the "resin" in the present invention is a conventional name for a synthetic polymer. When interpreting, it may include forms such as monomers, their polymers, combinations of monomers, combinations of their polymers, or combinations of monomers and their polymers, etc., and is not limited thereto.

[0047] Unless otherwise specified, in the present invention, the modified products include products obtained by modifying the reactive functional groups of each resin, products obtained by prepolymerization reaction of each resin with other resins, products obtained by crosslinking of each resin with other resins, products obtained by copolymerization of each resin with other resins, and so on.

[0048] Unless otherwise specified, the unsaturated bonds described in the present invention refer to reactive unsaturated bonds, such as but not limited to unsaturated double bonds that can undergo crosslinking reactions with other functional groups, such as but not limited to unsaturated carbon-carbon double bonds that can undergo crosslinking reactions with other functional groups.

[0049] The unsaturated carbon-carbon double bonds in the present invention preferably include, but are not limited to, vinyl, vinylbenzyl, vinylphenyl, (meth)acryloyloxy, allyl or combinations thereof. When interpreting vinyl, it should include vinyl and vinylene. When interpreting (meth)acryloyloxy, it should include acryloyloxy and methacryloyloxy.

[0050] Unless otherwise specified, the alkyl groups, alkenyl groups, and monomers described in the present invention, when interpreted, include their various isomers. For example, propyl should be interpreted as including n-propyl and isopropyl.

[0051] Unless otherwise specified, in the present invention, parts by weight represent relative weight parts in the composition, which can be any weight unit, such as, but not limited to, weight units such as kilograms, kilograms, grams, pounds, etc. For example, 100 parts by weight of a copolymer means it can be 100 kilograms of the copolymer or 100 pounds of the copolymer.

[0052] Unless otherwise specified, in the present invention, wt% represents weight (or mass) percentage.

[0053] It should be understood that the features disclosed in each embodiment herein can be arbitrarily combined to form the technical solutions of the present invention, as long as there is no contradiction in the combination of these features.

[0054] The present invention will be described below in specific embodiments and examples. It should be understood that these specific embodiments and examples are merely exemplary and are not intended to limit the scope and use of the present invention. The methods, reagents, and conditions used in the examples are conventional methods, reagents, and conditions in the art unless otherwise specified.

[0055] As mentioned above, the present invention mainly discloses a resin composition, which comprises the following components:

[0056] (A) 100 parts by weight of a copolymer, the copolymer having a structural unit formed by the monomer represented by formula (1) and a structural unit formed by the monomer represented by formula (2), and the content of the structural unit formed by the monomer represented by formula (2) in the copolymer is 55 wt% to 90 wt%; and

[0057] (B) 1 part by weight to 15 parts by weight of the compound represented by formula (3);

[0058]

[0059] Among them, in formula (1), each of R1 to R5 is independently selected from a hydrogen atom, a C1-C3 alkyl group (such as a methyl group, an ethyl group or a propyl group), a C2-C3 alkenyl group (such as a vinyl group or an allyl group), a phenyl group, a phenyl group substituted by a C1-C3 alkyl group (such as an ethylphenyl group), a phenyl group substituted by a C2-C3 alkenyl group (such as a vinylphenyl group), and a C2-C3 alkenylphenyl C1-C3 alkylene group (such as a vinylphenylethylene group);

[0060] In formula (2), each of R6 to R9 is independently selected from a hydrogen atom, a C1-C3 alkyl group (such as a methyl group, an ethyl group or a propyl group), and a C2-C3 alkenyl group (such as a vinyl group or an allyl group), and at least one of R6 to R9 is a C2-C3 alkenyl group (such as a vinyl group or an allyl group);

[0061] In formula (3), each of X', Y' and Z' independently represents a hydrogen atom, a C1-C4 alkyl group (such as a methyl group, an ethyl group, a propyl group or a butyl group), a phenyl group or a group containing an unsaturated carbon-carbon double bond (such as a vinyl group, a vinylbenzyl group, a (meth)acryloyloxy group, an allyl group, a vinylphenyl group or a combination thereof).

[0062] In the present invention, the copolymer may be a copolymer having a structural unit formed from the monomer represented by formula (1) and a structural unit formed from the monomer represented by formula (2), or a mixture of two or more copolymers having different structures of a structural unit formed from the monomer represented by formula (1) and a structural unit formed from the monomer represented by formula (2).

[0063] For example, in one embodiment, the copolymer has a structural unit formed from the monomer represented by formula (1) and a structural unit formed from the monomer represented by formula (2), and the content of the structural unit formed from the monomer represented by formula (2) in the copolymer is 55 wt% to 90 wt%.

[0064] For example, in one embodiment, the monomer represented by formula (1) includes any one or a combination of the monomers represented by formula (1-1), formula (1-2), formula (1-3) and formula (1-4), and the monomer represented by formula (2) includes the monomer represented by formula (2-1).

[0065]

[0066] For example, in one embodiment, the copolymer is preferably a random copolymer or a block copolymer, more preferably a block copolymer.

[0067] For example, in one embodiment, the number average molecular weight (Mn) of the copolymer is: 1000 ≤ Mn ≤ 30000. Preferably, the number average molecular weight (Mn) of the copolymer is: 1500 ≤ Mn ≤ 20000.

[0068] For example, in one embodiment, the copolymer comprises any one or a combination of the copolymers represented by the following formulas (4) to (19):

[0069]

[0070]

[0071] In formulas (4) to (19), m, n, x, y, and z are each independently a positive integer and satisfy the following relationships: 2 ≤ m ≤ 44, 12 ≤ n ≤ 70, 2 ≤ x + z ≤ 44, 12 ≤ y ≤ 70. For example but not limited to, m = 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, 30, 31, 32, 33, 34, 35, 36, 37, 38, 39, 40, 41, 42, 43, or 44; n = 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, 30, 31, 32, 33, 34, 35, 36, 37, 38, 39, 40, 41, 42, 43, 44, 45, 46, 47, 48, 49, 50, 51, 52, 53, 54, 55, 56, 57, 58, 59, 60, 61, 62, 63, 64, 65, 66, 67, 68, 69, or 70; x + z = 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, 30, 31, 32, 33, 34, 35, 36, 37, 38, 39, 40, 41, 42, 43, or 44; y = 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, 30, 31, 32, 33, 34, 35, 36, 37, 38, 39, 40, 41, 42, 43, 44, 45, 46, 47, 48, 49, 50, 51, 52, 53, 54, 55, 56, 57, 58, 59, 60, 61, 62, 63, 64, 65, 66, 67, 68, 69, or 70. And in formulas (4) to (19), the content of the structural unit formed by the monomer represented by formula (2) is 55 wt% to 90 wt%.

[0072] In the above formulas (4) to (19), formulas (4) to (11) represent triblock copolymers, and each structural unit is bonded in sequence. For example, formula (4) represents that a structural unit (represented by a) formed by x monomers of formula (1), a structural unit (represented by b) formed by y monomers of formula (2) and a structural unit (represented by a) formed by z monomers of formula (1) are bonded in sequence. For example, when x is 2, y is 12, and z is 3 in formula (4), the connection between each structural unit is as follows -aa-bbbbbbbbbbbb-aaa-. Formulas (12) to (19) represent random copolymers, and each structural unit is bonded in a random manner. This structural formula is used only for the convenience of expression. For example, formula (12) represents that a structural unit (represented by a) formed by m monomers of formula (1) and a structural unit (represented by b) formed by n monomers of formula (2) are bonded in a random manner. For example, when m is 9 and n is 12 in formula (12), the connection between the structural units is irregular, such as but not limited to the following structure -aababbbaaabbbbabbaabb-.

[0073] For example, in one embodiment, the copolymer includes any one or a combination of block copolymers shown in formula (4) to (11), random copolymers shown in formula (12) to (19). Preferably, the copolymer includes any one or a combination of block copolymers shown in formula (4) to (11). For example, in one embodiment, the product prepared using the copolymers shown in formula (4) to (19) and the compound shown in formula (3) has both a higher glass transition temperature and excellent substrate appearance, lower Z-axis thermal expansion coefficient, reflow soldering warpage, storage modulus attenuation rate, and dielectric loss. Further, in one embodiment, when the copolymer is preferably a block copolymer shown in formula (4) to (11), the above-mentioned properties are significantly improved, especially with a lower storage modulus attenuation rate, Z-axis thermal expansion coefficient and reflow soldering warpage.

[0074] The copolymer having the structural unit formed by the monomer represented by formula (1) and the structural unit formed by the monomer represented by formula (2) of the present invention can be prepared by various methods known to those skilled in the art. For example, the copolymer can be prepared by the following method:

[0075] 1. A copolymer having a structural unit formed from a monomer represented by formula (1) and a structural unit formed from a monomer represented by formula (2) is a block copolymer.

[0076] Under the conditions of 0 °C to 40 °C and in an inert atmosphere, a solvent and an anionic initiator are added to a reaction vessel and rapidly stirred. First, a grams of the first monomer represented by formula (1) is added, and after reacting for 4 to 18 hours, b grams of the monomer represented by formula (2) is added, and after continuing to react for 4 to 18 hours, finally c grams of the second monomer represented by formula (1) is added, and the reaction is continued for 4 to 18 hours to obtain the block copolymer. Among them, the first monomer represented by formula (1) and the second monomer represented by formula (1) may be the same or different, and a, b, and c satisfy the following relationship: (b / (a + b + c)) × 100% = 55% to 90%.

[0077] The solvent in the above steps may be, for example but not limited to, a polar solvent (such as tetrahydrofuran) or a non-polar solvent (such as cyclohexane), and preferably tetrahydrofuran.

[0078] The anionic initiator in the above steps may be, for example but not limited to, n-butyllithium or tert-butyllithium, and preferably n-butyllithium.

[0079] The inert atmosphere in the above steps may be, for example but not limited to, an argon atmosphere or a nitrogen atmosphere, and preferably an argon atmosphere.

[0080] 2. A copolymer having a structural unit formed from the monomer represented by formula (1) and a structural unit formed from the monomer represented by formula (2) is a random copolymer.

[0081] Under the conditions of 20 °C to 70 °C, a solvent and a mixture of the monomer represented by formula (1) and the monomer represented by formula (2) (where the mass content of the monomer represented by formula (2) in the mixture is 55 wt% to 90 wt%, and the total molar amount of the mixture is d moles) are added to a reaction vessel, stirred evenly, and a cationic initiator (molar amount is e moles) is continuously added, and the reaction is carried out for 4 to 72 hours to obtain a random copolymer in which the content of the structural unit formed from the monomer represented by formula (2) is 55 wt% to 90 wt%. d and e satisfy the following relationship: (e / d) × 100% = 0.5% to 25%.

[0082] The solvent in the above steps may be, for example but not limited to, n-propyl acetate, n-butyl acetate or tetrahydrofuran, and preferably n-propyl acetate.

[0083] The cationic initiator in the above steps may be, for example but not limited to, boron trifluoride diethyl ether, boron trifluoride methyl ether or aluminum trichloride, and preferably boron trifluoride diethyl ether.

[0084] Compared with 100 parts by weight of the aforementioned copolymer, the resin composition of the present invention contains 1 to 15 parts by weight of the compound represented by formula (3).

[0085] For example, in one embodiment, the compound represented by the formula (3) has at least one group containing an unsaturated carbon-carbon double bond.

[0086] For example, in one embodiment, in the formula (3), at least one of X', Y' and Z' represents vinyl, styryl, allyl or (meth)acryloyloxy.

[0087] For example, in one embodiment, the compound represented by the formula (3) includes any one or a combination of the compounds represented by the formula (3-1) to the compounds represented by the formula (3-6):

[0088]

[0089]

[0090] For example, in one embodiment, the resin composition of the present invention further includes a crosslinking agent containing an unsaturated carbon-carbon double bond. For example, relative to 100 parts by weight of the copolymer, the resin composition of the present invention may contain 1 to 50 parts by weight of a crosslinking agent containing an unsaturated carbon-carbon double bond, preferably 5 to 35 parts by weight of a crosslinking agent containing an unsaturated carbon-carbon double bond.

[0091] The crosslinking agent containing an unsaturated carbon-carbon double bond applicable to the present invention refers to a small molecule compound with two or more functional groups containing an unsaturated carbon-carbon double bond and a molecular weight less than or equal to 1000, and its molecular weight is preferably between 100 and 900, more preferably between 100 and 800. For example, the crosslinking agent containing an unsaturated carbon-carbon double bond is bis(vinylphenyl)ethane (BVPE), divinylbenzene (DVB), divinylnaphthalene, divinylbiphenyl, triallyl isocyanurate (TAIC), triallyl cyanurate (TAC), vinylbenzocyclobutene (VBCB), bis(vinylbenzyl)ether (BVBE), trivinylcyclohexane (TVCH), diallylbisphenol A (DABPA), acrylate with two or more functional groups, butadiene, decadiene, octadiene or any combination thereof.

[0092] The acrylate with two or more functional groups includes various bifunctional acrylates, trifunctional acrylates or acrylates with four or more functional groups known in the art, and can be purchased from Shin-Nakamura Chemical Co., Ltd., Kyoeisha Chemical Co., Ltd., Nippon Kayaku Co., Ltd. or Sartomer Company. Specific examples include, but are not limited to, diallyl isophthalate (DAIP), dioxane diol diacrylate, tricyclodecane dimethanol diacrylate, tricyclodecane dimethanol dimethacrylate or any combination thereof.

[0093] For example, in one embodiment, the resin composition of the present invention may further optionally include a polyolefin different from the copolymer, a polyphenylene ether resin containing an unsaturated carbon-carbon double bond, a benzoxazine resin, an epoxy resin, a polyester resin, a phenolic resin, an amine curing agent, a polyamide, a polyimide, styrene maleic anhydride, a maleimide resin, a cyanate ester, or any combination thereof.

[0094] For example, in one embodiment, the resin composition of the present invention further includes a polyolefin different from the copolymer. For example, with respect to 100 parts by weight of the copolymer, the resin composition of the present invention may contain 1 part by weight to 500 parts by weight of a polyolefin different from the copolymer, preferably 5 parts by weight to 100 parts by weight of a polyolefin different from the copolymer.

[0095] For example, in one embodiment, the polyolefin different from the copolymer applicable to the present invention is not particularly limited, and may be any one or more polyolefins different from the copolymer applicable to the preparation of prepregs, resin films, laminates or printed circuit boards, and may be any one or more commercially available products, self-made products or combinations thereof. For example, the polyolefins different from the copolymer applicable to the present invention include, but are not limited to, diene polymers, monoene polymers, hydrogenated diene polymers or combinations thereof. The diene polymer refers to a polymer of a hydrocarbon compound containing two unsaturated carbon-carbon double bonds in the molecule, and the monoene polymer refers to a polymer of a hydrocarbon compound containing one unsaturated carbon-carbon double bond in the molecule. The polyolefins different from the copolymer applicable to the present invention include, for example, but are not limited to, polybutadiene, polyisoprene, styrene-butadiene copolymer, styrene-isoprene copolymer, styrene-butadiene-divinylbenzene polymer, maleic anhydride-added polybutadiene-styrene copolymer, vinyl-polybutadiene-urethane polymer, maleic anhydride-added polybutadiene, polymethylstyrene, hydrogenated polybutadiene, hydrogenated polyisoprene, hydrogenated styrene-butadiene-divinylbenzene polymer, hydrogenated maleic anhydride-added styrene-butadiene copolymer, hydrogenated styrene-butadiene copolymer, hydrogenated styrene-isoprene copolymer, epoxy group-containing polybutadiene, and multi-functional vinyl aromatic copolymers, or any combination thereof.

[0096] For example, unless otherwise specified, the multi-functional vinyl aromatic copolymers used in the present invention may include various multi-functional vinyl aromatic copolymers disclosed in US Patent Application US20070129502A1, which are incorporated herein by reference in their entirety.

[0097] For example, in one embodiment, the resin composition of the present invention further includes a polyphenylene ether resin containing an unsaturated carbon-carbon double bond. For example, with respect to 100 parts by weight of the copolymer, the resin composition of the present invention may contain 1 to 500 parts by weight of the polyphenylene ether resin containing an unsaturated carbon-carbon double bond, preferably 5 to 100 parts by weight of the polyphenylene ether resin containing an unsaturated carbon-carbon double bond.

[0098] For example, in one embodiment, the polyphenylene ether resin containing an unsaturated carbon-carbon double bond applicable to the present invention is not particularly limited, and may be any one or more polyphenylene ether resins containing an unsaturated carbon-carbon double bond applicable to the preparation of prepregs, resin films, laminates or printed circuit boards, and may be any one or more commercially available products, self-made products or combinations thereof. For example, it includes but is not limited to any one or a combination of vinylbenzyl polyphenylene ether resin, (meth)acryloyloxy polyphenylene ether resin and vinyl polyphenylene ether resin.

[0099] The polyphenylene ether resin containing an unsaturated carbon-carbon double bond of the present invention has an unsaturated carbon-carbon double bond and a phenyl ether backbone, wherein the unsaturated carbon-carbon double bond is a reactive functional group, which can self-polymerize after heating, and can also undergo a free radical polymerization reaction with other components containing unsaturated bonds in the resin composition and finally crosslink and cure. Preferably, the polyphenylene ether resin containing an unsaturated carbon-carbon double bond includes a polyphenylene ether resin containing an unsaturated carbon-carbon double bond with 2,6-dimethyl substitution on the phenyl ether backbone. After substitution, the methyl groups form steric hindrance, making it difficult for the oxygen atom on the ether to generate hydrogen bonds or van der Waals forces and absorb moisture.

[0100] For example, in one embodiment, the polyphenylene ether resin containing an unsaturated carbon-carbon double bond includes but is not limited to a vinylbenzyl polyphenylene ether resin with a number average molecular weight of about 1200 (such as OPE-2st 1200, available from Mitsubishi Gas Chemical Company), a vinylbenzyl polyphenylene ether resin with a number average molecular weight of about 2200 (such as OPE-2st 2200, available from Mitsubishi Gas Chemical Company), a vinylbenzyl polyphenylene ether resin with a number average molecular weight of about 2400 to 2800 (such as vinylbenzyl bisphenol A polyphenylene ether resin), a (meth)acryloyloxy polyphenylene ether resin with a number average molecular weight of about 1900 to 2300 (such as SA9000, available from Sabic Company), a vinyl polyphenylene ether resin with a number average molecular weight of about 2200 to 3000 or a combination thereof. Among them, the vinyl polyphenylene ether resin may include various polyphenylene ether resins disclosed in US Patent Application US20160185904A1, which are all incorporated herein by reference. For example, in one embodiment, the vinylbenzyl polyphenylene ether resin includes but is not limited to a vinylbenzyl biphenyl polyphenylene ether resin, a vinylbenzyl bisphenol A polyphenylene ether resin or a combination thereof.

[0101] Unless otherwise specified, in the resin composition of the present invention, the amounts of benzoxazine resin, epoxy resin, polyester resin, phenol resin, polyamide, polyimide, styrene maleic anhydride, maleimide resin, and cyanate ester are not particularly limited with respect to 100 parts by weight of the copolymer. For example, they can be from 1 part by weight to 100 parts by weight, such as but not limited to 1 part 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. The amount of amine curing agent is also not particularly limited with respect to 100 parts by weight of the copolymer. For example, it can be from 1 to 15 parts by weight, such as but not limited to 1 part by weight, 4 parts by weight, 7.5 parts by weight, 12 parts by weight, or 15 parts by weight.

[0102] For example, in one embodiment, the benzoxazine resin may be various benzoxazine resins known in the art. Specific examples include but are not limited to 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 or a combination thereof. Suitable commercially available products include, for example, 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) sold by Huntsman, or KZH-5031 (vinyl modified benzoxazine resin), KZH-5032 (phenyl modified benzoxazine resin) sold by Kolon Industries of Korea. Among them, the diamine type benzoxazine resin may be diaminodiphenylmethane benzoxazine resin, diaminodiphenyl ether type benzoxazine resin, diaminodiphenyl sulfone benzoxazine resin, diaminodiphenyl sulfide benzoxazine resin or a combination thereof, and is not limited thereto.

[0103] For example, in one embodiment, the epoxy resin may be various epoxy resins known in the art. From the perspective of improving the heat resistance of the resin composition, the epoxy resin includes, but is not limited to, for example, bisphenol A epoxy resin, bisphenol F epoxy resin, bisphenol S epoxy resin, bisphenol AD epoxy resin, novolac epoxy resin, trifunctional epoxy resin, tetrafunctional epoxy resin, multifunctional novolac epoxy resin, dicyclopentadiene (DCPD) epoxy resin, phosphorus-containing epoxy resin, p-xylene epoxy resin, naphthalene-type epoxy resin (such as naphthol-type epoxy resin), benzofuran-type epoxy resin, isocyanate-modified epoxy resin, or any combination thereof. In the present invention, for example, the novolac epoxy resin may be phenol novolac 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. In the present 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-HQ-containing phenol novolac epoxy resin, DOPO-HQ-containing o-cresol novolac epoxy resin, and DOPO-HQ-containing bisphenol-A novolac epoxy resin, and is not limited thereto.

[0104] For example, in one embodiment, the polyester resin may be various polyester resins known in the art. Specific examples include, but are not limited to, polyester resins containing dicyclopentadiene structures and polyester resins containing naphthalene ring structures or combinations thereof. Specific examples include, but are not limited to, those sold by Dainippon Ink and Chemicals under the trade names HPC-8000 or HPC-8150.

[0105] For example, in one embodiment, the phenolic resin may be various phenolic resins known in the art. Specific examples include, but are not limited to, phenolic resins or phenoxy resins, where the phenolic resins include at least one or a combination of phenol novolac resins, o-cresol novolac resins, bisphenol-A novolac resins, naphthol novolac resins, biphenol novolac resins, and dicyclopentadiene novolac resins, and are not limited thereto.

[0106] For example, in one embodiment, the amine curing agent may be various amine curing agents known in the art. Specific examples include, but are not limited to, at least one or a combination of diaminodiphenyl sulfone, diaminodiphenyl methane, diaminodiphenyl ether, diaminodiphenyl sulfide, and dicyandiamide.

[0107] For example, in one embodiment, the polyamide may be various polyamides known in the art. Specific examples include, but are not limited to, various commercially available polyamide resin products.

[0108] For example, in one embodiment, the polyimide may be various polyimides known in the art. Specific examples include, but are not limited to, various commercially available polyimide resin products.

[0109] For example, in one embodiment, the styrene maleic anhydride can be various types 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, but are not limited to, styrene maleic anhydride copolymers with trade names SMA-1000, SMA-2000, SMA-3000, EF-30, EF-40, EF-60, and EF-80 sold by Cray Valley, or styrene maleic anhydride copolymers with trade names C400, C500, C700, and C900 sold by Polyscope.

[0110] For example, in one embodiment, the maleimide resin may be various maleimide resins known in the art. Specific examples include, but are not limited to: 4,4'-diphenylmethane bismaleimide, polyphenylmethanemaleimide, bisphenol A diphenyl etherbismaleimide, 3,3'-dimethyl-5,5'-diethyl-4,4'-diphenylmethane bismaleimide, 3,3'-dimethyl-5,5'-dipropyl-4,4'-diphenylmethane bismaleimide, m-phenylene bismaleimide, 4-methyl-1,3-phenylene bismaleimide, 1,6-bismaleimide-(2,2,4-trimethyl)hexane, N-2,3-xylylmaleimide, N-2,6-xylylmaleimide, N-phenylmaleimide, vinylbenzyl maleimide (VBM), maleimide containing a biphenyl structure, maleimide resin containing an aliphatic structure with 10 to 50 carbon atoms, maleimide containing an indane structure, maleimide containing an isopropyl group and a meta-arylene structure, or any combination thereof. Modifications of these components are also included in the interpretation, such as, but not limited to, maleimide resin modified with diallyl compounds, maleimide resin modified with diamines, maleimide resin modified with polyfunctional amines, maleimide resin modified with acidic phenolic compounds, maleimide resin modified with cyanate esters, or combinations thereof.

[0111] For example, maleimide resins such as, but not limited to, 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 maleimide resins produced by K.I Chemical Co., Ltd. under the trade names BMI-70, BMI-80, etc., or maleimide resins produced by Nippon Kayaku Co., Ltd. under the trade names MIR-3000 or MIR-5000, etc.

[0112] For example, maleimide resins having an aliphatic structure with 10 to 50 carbon atoms, or so-called imide-extended maleimide resins, may include various types of imide-extended maleimide resins disclosed in Taiwan Patent Application Publication No. TW200508284A, which are hereby incorporated by reference in their entirety. Maleimide resins having an aliphatic structure with 10 to 50 carbon atoms suitable for the present invention include, for example, but are not limited to, maleimide resins produced by Designer Molecular Co., Ltd. under the trade names BMI-689, BMI-1400, BMI-1500, BMI-1700, BMI-2500, BMI-3000, BMI-5000, and BMI-6000.

[0113] In the present invention, for example, in one embodiment, the cyanate ester-modified maleimide resin (or so-called maleimide triazine resin) can be various types of maleimide triazine resins known in the art. Specific examples include, but are not limited to: maleimide triazine resins obtained by polymerizing maleimide resins with bisphenol A type cyanate ester resins, maleimide triazine resins obtained by polymerizing maleimide resins with bisphenol F type cyanate ester resins, maleimide triazine resins obtained by polymerizing maleimide resins with phenol novolac type cyanate ester resins, and maleimide triazine resins obtained by polymerizing maleimide resins with cyanate ester resins containing a dicyclopentadiene structure. In one embodiment, the maleimide triazine resin can be obtained by polymerizing the aforementioned maleimide resin and the aforementioned cyanate ester resin in any molar ratio. For example, the molar ratio of the maleimide resin to the cyanate ester resin can be 1:1 to 1:10, such as, but not limited to, 1:1, 1:2, 1:4, 1:6, 1:8, or 1:10.

[0114] In the present invention, for example, in one embodiment, the cyanate ester can be various cyanate ester resins known in the art, such as compounds having an Ar-O-C≡N structure, where Ar can be a substituted or unsubstituted aromatic group. From the perspective of improving the heat resistance of the resin composition, specific examples include, but are not limited to, 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. Among them, the phenolic cyanate ester resin can be a bisphenol A phenolic cyanate ester resin, a bisphenol F phenolic cyanate ester resin, or a combination thereof. For example, the cyanate ester resin can be cyanate ester resins with 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, LeCy, etc., produced by Lonza.

[0115] For example, in one embodiment, the resin composition further includes any one or a combination of an inorganic filler, a flame retardant, a curing accelerator different from the compound represented by formula (3), a polymerization inhibitor, a solvent, a silane coupling agent, a dye, and a toughening agent.

[0116] In the present invention, for example, in one embodiment, the inorganic filler can be any one or more inorganic fillers suitable for preparing prepregs, resin films, laminates, or printed circuit boards. Specific examples include, but are not limited to: silica (molten, non-molten, porous, or hollow type), alumina, aluminum hydroxide, magnesia, magnesium hydroxide, calcium carbonate, aluminum nitride, boron nitride, aluminum silicon 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, zirconia, mica, boehmite (AlOOH), calcined talc, talc, silicon nitride, zirconium tungstate, spodumene, calcined kaolin, or combinations thereof. In addition, the inorganic filler can be spherical (including solid spherical or hollow spherical), fibrous, plate-like, granular, flaky, or whisker-like, and can be selectively pretreated with a silane coupling agent. For example, in one embodiment, with respect to 100 parts by weight of the copolymer, the resin composition of the present invention can further include 10 parts by weight to 300 parts by weight of an inorganic filler, preferably 50 parts by weight to 300 parts by weight of an inorganic filler, more preferably 80 parts by weight to 200 parts by weight of an inorganic filler, but not limited thereto.

[0117] In the present invention, for example, in one embodiment, the flame retardant can be any one or more flame retardants suitable for preparing prepregs, resin films, laminates or printed circuit boards, including but not limited to phosphorus-containing flame retardants or bromine-containing flame retardants. The bromine-containing flame retardant preferably includes decabromodiphenylethane, and the phosphorus-containing flame retardant preferably includes hydroquinone bis-(diphenyl phosphate), bisphenol A bis-(diphenylphosphate), tri(2-carboxyethyl)phosphine (TCEP), tris(2-chloroisopropyl) phosphate, trimethyl phosphate (TMP), dimethyl methyl phosphonate (DMMP), resorcinol bis(dixylenyl phosphate) (RDXP, such as commercially available products PX-200, PX-201, PX-202, etc.), ammonium polyphosphate, melamine polyphosphate, diphenylphosphine oxide (DPPO) and its derivatives (such as bis-DPPO compounds) or resins, melamine cyanurate and tri-hydroxy ethyl isocyanurate, aluminum hypophosphite salts (such as products OP-930, OP-935, etc.) or combinations thereof.

[0118] For example, in one embodiment, the flame retardant can be a flame retardant sold by Katayama Chemical Industry Co., Ltd., including but not limited to 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. The flame retardant of the present invention can include one or more of the above.

[0119] For example, unless otherwise specified, the resin composition of the present invention may further include 1 to 100 parts by weight of a flame retardant, preferably 1 to 50 parts by weight of a flame retardant, based on 100 parts by weight of the copolymer, but is not limited thereto.

[0120] In the present invention, for example, in one embodiment, a curing accelerator different from the compound represented by formula (3) may include a catalyst such as a Lewis base or a Lewis acid. Among them, 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 (2E4MZ), triphenylphosphine (TPP), and 4-dimethylaminopyridine (DMAP). The Lewis acid may include metal salt compounds such as metal salt compounds of manganese, iron, cobalt, nickel, copper, zinc, etc., such as zinc octoate, cobalt octoate and other metal catalysts. The curing accelerator also includes a curing initiator, such as a peroxide that can generate free radicals. The curing initiator includes but is not limited to: dicumyl peroxide (DCP), tert-butyl peroxybenzoate, dibenzoyl peroxide (BPO), 2,5-dimethyl-2,5-bis(tert-butylperoxy)-3-hexyne (25B), and bis(tert-butylperoxyisopropyl)benzene or a combination thereof. For example, in one embodiment, the resin composition of the present invention may further include 0.001 to 5 parts by weight of a curing accelerator different from the compound represented by formula (3), preferably 0.01 to 3.5 parts by weight of a curing accelerator different from the compound represented by formula (3), more preferably 0.1 to 2.0 parts by weight of a curing accelerator different from the compound represented by formula (3), based on 100 parts by weight of the copolymer, but is not limited thereto.

[0121] In the present invention, for example, in one embodiment, the polymerization inhibitor may include but is not limited to 1,1-diphenyl-2-trinitrophenylhydrazine, methacrylonitrile, nitroxide stable free radicals, triphenylmethyl free radicals, metal ion free radicals, sulfur free radicals (such as including but not limited to dithioesters), hydroquinone, p-methoxyphenol, p-benzoquinone, phenothiazine, β-phenylnaphthylamine, p-tert-butylcatechol, methylene blue, 4,4'-butylidenebis(6-tert-butyl-3-methylphenol), and 2,2'-methylenebis(4-ethyl-6-tert-butylphenol) or a combination thereof. For example, the above nitroxide stable free radicals may include but are not limited to nitroxyl radicals derived from cyclic hydroxylamines such as 2,2,6,6-tetramethyl-1-oxyl-piperidine, 2,2,6,6-substituted-1-piperidineoxyl radicals, or 2,2,5,5-substituted-1-pyrrolidinyloxyl radicals. As substituents, alkyl groups having four or less carbon atoms such as methyl or ethyl are preferred. There is no limitation on the specific nitroxyl radical compound, and examples include but are not limited to 2,2,6,6-tetramethyl-1-piperidineoxyl radical, 2,2,6,6-tetraethyl-1-piperidineoxyl radical, 2,2,6,6-tetramethyl-4-oxo-1-piperidineoxyl radical, 2,2,5,5-tetramethyl-1-pyrrolidinyloxyl radical, 1,1,3,3-tetramethyl-2-isobenzofuranoneoxyl radical, N,N-di-tert-butylamineoxyl radical, etc. Stable free radicals such as galvinoxyl free radicals can also be used instead of nitroxyl free radicals. The polymerization inhibitor suitable for the resin composition of the present invention may also be a product derived by substituting a hydrogen atom or atomic group in the polymerization inhibitor with other atoms or atomic groups. For example, a product derived by substituting a hydrogen atom in the polymerization inhibitor with atomic groups such as amino, hydroxyl, or ketone carbonyl. For example, in one embodiment, the resin composition of the present invention may further include 0.001 to 20 parts by weight, preferably 0.001 to 10 parts by weight, of a polymerization inhibitor relative to 100 parts by weight of the copolymer, but is not limited thereto.

[0122] In the present invention, for example, in one embodiment, the solvent may be any solvent suitable for dissolving the resin composition of the present invention, including but not limited to: 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 and other solvents or a mixed solvent thereof. The amount of the solvent added is for the purpose of completely dissolving the resin and adjusting to a specific total solid content of the resin composition. For example, in one embodiment, the amount of the solvent added is adjusted so that the total solid content of the resin composition is 50 wt% to 85 wt%, but is not limited thereto.

[0123] In the present invention, for example, in one embodiment, the silane coupling agent may include silane compounds (silane, such as but not limited to siloxane compounds), and can be further classified into amino silane compounds, epoxide silane compounds, vinyl silane compounds, hydroxyl silane compounds, isocyanate group silane compounds, methacryloxy silane compounds, and acryloxy silane compounds according to the types of functional groups. For example, in one embodiment, with respect to 100 parts by weight of the copolymer, the resin composition of the present invention may further include 0.001 to 20 parts by weight of the silane coupling agent, preferably 0.01 to 10 parts by weight of the silane coupling agent, but not limited thereto.

[0124] In the present invention, for example, in one embodiment, the colorant may include but not limited to dyes or pigments. For example, in one embodiment, with respect to 100 parts by weight of the copolymer, the resin composition of the present invention may further include 0.001 to 10 parts by weight of the colorant, preferably 0.01 to 5 parts by weight of the colorant, but not limited thereto.

[0125] In the present invention, the main function of adding the toughening agent is to improve the toughness of the resin composition. For example, the toughening agent applicable to the present invention may include but not limited to compounds such as carboxyl-terminated butadieneacrylonitrile rubber (CTBN), core-shell rubber, ethylene-propylene rubber, or combinations thereof. For example, in one embodiment, with respect to 100 parts by weight of the copolymer, the resin composition of the present invention may further include 1 to 20 parts by weight of the toughening agent, preferably 3 to 10 parts by weight of the toughening agent, but not limited thereto.

[0126] The resin compositions of the foregoing embodiments can be made into various products, such as components applicable to various electronic products, including but not limited to prepregs, resin films, laminates, or printed circuit boards.

[0127] For example, the resin composition of the present invention can be made into a prepreg, which includes a reinforcing material and a layer formed on the reinforcing material. The layer is obtained by forming the resin composition into a semi-cured state (B-stage) through high-temperature heating. The baking temperature for making the prepreg is between 120°C and 180°C, preferably between 120°C and 160°C. The reinforcing material can be any one of fiber materials, woven fabrics, and non-woven fabrics, and the woven fabric preferably includes a glass fiber cloth. The type of the glass fiber cloth is not particularly limited and can be various glass fiber cloths that can be used for printed circuit boards, such as E-type glass cloth, D-type glass cloth, S-type glass cloth, T-type glass cloth, L-type glass cloth, Q-type glass cloth, or QL-type glass cloth (a glass cloth with a mixed structure made of Q glass and L glass); the types of glass fibers include yarns and rovings, etc., the forms include fibrillated or non-fibrillated, and the end face shapes include circular or flat shapes. The aforementioned non-woven fabric preferably includes a liquid crystal resin non-woven fabric, such as a polyester non-woven fabric, a polyurethane non-woven fabric, etc., and is not limited thereto. The aforementioned woven fabric can also include a liquid crystal resin woven fabric, such as a polyester woven fabric or a polyurethane woven fabric, etc., and 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. After the prepreg is subsequently heated for curing (C-stage), an insulating layer is formed.

[0128] For example, the resin composition of the present invention can be made into a resin film, which is obtained by semi-curing the resin composition through baking and heating. The resin composition can be selectively coated on a liquid crystal resin film, a polytetrafluoroethylene film, a polyethylene terephthalate film (PET film), a polyimide film (PI film), a copper foil, or a copper foil with adhesive, and then formed into a semi-cured state through baking and heating, so that the resin composition forms a resin film.

[0129] For example, the resin composition described in the present invention can be made into various laminates, which include at least two metal foils and at least one insulating layer. The insulating layer is disposed between the two metal foils, and the insulating layer can be cured from the aforementioned resin composition under high temperature and high pressure (C-stage). The applicable curing temperature is, for example, between 190°C and 220°C, preferably between 200°C and 210°C, the curing time is 90 to 180 minutes, preferably 120 to 150 minutes, and the applicable lamination pressure is, for example, between 300 psi and 550 psi, preferably between 400 psi and 500 psi. The aforementioned insulating layer can be obtained by curing the aforementioned prepreg or resin film. The material of the aforementioned metal foil can be copper, aluminum, nickel, platinum, silver, gold, or their alloys, such as copper foil. In a preferred embodiment, the laminate is a copper foil substrate.

[0130] In one embodiment, the foregoing laminated board can be further processed through circuitry to form a printed circuit board. One way to fabricate the printed circuit board of the present invention can be to use a double-sided copper clad laminate with a thickness of 28 mils and 1 ounce of HTE (High Temperature Elongation) copper foil (such as product EM-827, available from Taiguang Electronic Materials). After drilling, electroplating is performed to form electrical conduction between the upper copper foil and the lower copper foil. Then, the upper copper foil and the lower copper foil are etched to form the inner layer circuit. Next, the inner layer circuit is subjected to brownification and roughening treatment to form an uneven structure on the surface to increase the roughness. Then, the copper foil, the foregoing prepreg, the foregoing inner layer circuit board, the foregoing prepreg, and the copper foil are stacked in sequence, and then heated for 90 to 180 minutes in an environment with a temperature of 190°C to 220°C using a vacuum lamination device to cure the insulating layer material of the prepreg. Next, various circuit board processings known in the art, such as blackening treatment, drilling, and copper plating, are performed on the copper foil on the outermost surface to obtain a printed circuit board.

[0131] For example, in one embodiment, various articles prepared from the resin composition disclosed in the present invention preferably have one, multiple, or all of the following characteristics:

[0132] The glass transition temperature measured according to the method of IPC-TM-650 2.4.24.4 is greater than or equal to 290°C, for example, between 290°C and 358°C;

[0133] The storage modulus attenuation rate measured according to the method of IPC-TM-650 2.4.24.4 is less than or equal to 16%, for example, between 6% and 16%;

[0134] The reflow warpage measured according to the method of JESD22-B112A is less than or equal to 14 μm, for example, between 5 μm and 14 μm;

[0135] The Z-axis thermal expansion rate measured according to the method of IPC-TM-650 2.4.24.5 is less than or equal to 1.2%, for example, between 0.6% and 1.2%;

[0136] The dielectric loss measured according to the method of JIS C2565 at a frequency of 10 GHz is less than or equal to 0.00086, for example, between 0.00070 and 0.00086; and

[0137] There are no dendritic streaks observed visually on the substrate appearance.

[0138] Various raw materials from the following sources were used to prepare the resin compositions of the examples and comparative examples of the present invention according to the dosages shown in Tables 1 to 5, and various test samples were further prepared therefrom.

[0139] The chemical raw materials used in the examples and comparative examples of the present invention are as follows:

[0140] Copolymers A1 to A11 and B1 to B4: Refer to Synthesis Examples 1 to 12. Among them, copolymers A1 to A11 are the copolymers of the present invention (having a structural unit formed by the monomer represented by formula (1) and a structural unit formed by the monomer represented by formula (2), and the content of the structural unit formed by the monomer represented by formula (2) in the copolymer is 55 wt% to 90 wt%); in copolymers B1 and B2, the content of the structural unit formed by the monomer represented by formula (2) in the copolymer is not within the range of 55 wt% to 90 wt%; copolymer B3 is a homopolymer of the monomer represented by formula (2), and is placed in the column of copolymers for convenient side-by-side comparison; copolymer B4 does not have a structural unit formed by the monomer represented by formula (2).

[0141] Compound of formula (3-1): 2,3-dimethyl-2,3-diphenylbutane, purchased from Wuxi Zhufeng Chemical Industry.

[0142] Compound of formula (3-2): 1,1,2,2-tetraphenylethane, purchased from Wuxi Zhufeng Chemical Industry.

[0143] Compound of formula (3-3): 2,3-dimethyl-2,3-diisopropylphenylbutane, purchased from Wuxi Zhufeng Chemical Industry.

[0144] Compound of formula (3-4): Self-synthesized, details are as follows.

[0145] Compound of formula (3-5): Self-synthesized, details are as follows.

[0146] Compound of formula (3-6): Self-synthesized, details are as follows.

[0147] DCP: Dicumyl peroxide, purchased from NOF Corporation.

[0148] 25B: 2,5-dimethyl-2,5-di(tert-butylperoxy)-3-hexyne, purchased from NOF Corporation.

[0149] 2E4MZ: 2-ethyl-4-methylimidazole, purchased from Chin Yu Enterprise Co., Ltd.

[0150] B-3000: Polybutadiene, purchased from Nippon Soda.

[0151] Ricon 100: Styrene-butadiene copolymer, purchased from Cray Valley.

[0152] SBS-A: Styrene-butadiene-styrene triblock copolymer, purchased from Nippon Soda Co., Ltd.

[0153] H-1051: Hydrogenated polybutadiene-styrene copolymer, purchased from Asahi Kasei Corporation.

[0154] BVPE: Bis(vinylphenyl)ethane, purchased from Linchuan Chemical Industry.

[0155] SC-2500SVJ: Spherical silica, purchased from Admatechs.

[0156] Toluene: Purchased from Sinopec. The content of toluene is expressed as "appropriate amount", representing that the content of toluene is adjusted so that the total solid content of the resin composition is 60% to 68% (solid content, S / C = 60% - 68%).

[0157] Synthesis Example 1: Preparation of St-VBCB-St Block Copolymer

[0158] At 40 °C, 1 liter of dehydrated tetrahydrofuran (THF) was added to a Schlenk reaction flask. It was evacuated under liquid nitrogen environment and purged with nitrogen. The above operations were repeated three times. Then 1.64 grams of n-butyllithium was added and stirred rapidly. First, styrene (hereinafter referred to as St) was added. After reacting for 10 hours, 4-vinylbenzocyclobutene (hereinafter referred to as VBCB) was added. After continuing to react for 10 hours, St was added (the mass ratio of the three was 22.5:55:22.5, totaling 50 ml). After continuing to react for 10 hours, a compound shown in formula (4) with a VBCB content of 55 wt% was obtained, with Mn of about 2002 - 2340, labeled as A1.

[0159] At 30 °C, 1 liter of dehydrated cyclohexane was added to a Schlenk reaction flask. It was evacuated under liquid nitrogen environment and purged with nitrogen. The above operations were repeated three times. Then 0.87 grams of n-butyllithium was added and stirred rapidly. First, St was added. After reacting for 18 hours, VBCB was added. After continuing to react for 18 hours, St was added (the mass ratio of the three was 12.5:75:12.5, totaling 50 ml). After continuing to react for 18 hours, a compound shown in formula (4) with a VBCB content of 75 wt% was obtained, with Mn of about 3692 - 4030, labeled as A2.

[0160] Under the ice-water condition at 0 °C, 1 L of water-free THF was added to a Schlenk reaction flask. It was evacuated under a liquid nitrogen environment and then filled with nitrogen, and the above operations were repeated three times. 0.42 g of tert-butyllithium was added and stirred rapidly. First, St was added. After reacting for 6 hours, VBCB was added. After reacting for another 6 hours, St (the mass ratio of the three is 5:90:5, totaling 50 mL) was added. After reacting for another 6 hours, a compound shown in formula (4) with a VBCB content of 90 wt% was obtained, with Mn of about 8242 - 8580, labeled as A3.

[0161] Synthesis Example 2: Preparation of Ethylstyrene-VBCB-Ethylstyrene Block Copolymer

[0162] Under the condition of 25 °C, 1 L of water-free THF was added to a Schlenk reaction flask. It was evacuated under a liquid nitrogen environment and then filled with nitrogen, and the above operations were repeated three times. 0.27 g of n-butyllithium was added and stirred rapidly. First, m-ethylstyrene was added. After reacting for 12 hours, VBCB was added. After reacting for another 12 hours, m-ethylstyrene (the mass ratio of the three is 12.5:75:12.5, totaling 50 mL) was added. After reacting for another 12 hours, a compound shown in formula (6) with a VBCB content of 75 wt% was obtained, with Mn of about 13702 - 14092, labeled as A4.

[0163] Synthesis Example 3: Preparation of DVB-VBCB-DVB Block Copolymer

[0164] Under the condition of 25 °C, 1 L of water-free THF was added to a Schlenk reaction flask. It was evacuated under a liquid nitrogen environment and then filled with nitrogen, and the above operations were repeated three times. 0.054 g of n-butyllithium was added and stirred rapidly. First, o-divinylbenzene (o-DVB) was added. After reacting for 4 hours, VBCB was added. After reacting for another 4 hours, o-DVB (the mass ratio of the three is 12.5:75:12.5, totaling 10 mL) was added. After reacting for another 4 hours, a compound shown in formula (10) with a VBCB content of 75 wt% was obtained, with Mn of about 13650 - 14040, labeled as A5.

[0165] Synthesis Example 4: Preparation of BVPE-VBCB-BVPE Block Copolymer

[0166] Under the condition of 25 °C, 1 L of dehydrated THF was added to a Schlenk reaction flask, evacuated under liquid nitrogen environment, purged with nitrogen, and the above operations were repeated three times. Then, 0.052 g of n-butyllithium was added and stirred rapidly. First, p-bis(vinylphenyl)ethane (BVPE) was added. After reacting for 4 h, VBCB was added. After reacting for another 4 h, BVPE (the mass ratio of the three was 5:90:5, totaling 10 mL) was added. After reacting for another 4 h, a compound shown in formula (11) with a VBCB content of 90 wt% was obtained, with Mn of about 13286 - 13884, labeled as A6.

[0167] Synthesis Example 5: Preparation of St-VBCB Random Copolymer

[0168] 21 g of n-propyl acetate and 50 g of a mixture of VBCB and St (where the mass fraction of VBCB was 90%) were added to a reaction flask, stirred evenly, and then 2.8 g of boron trifluoride diethyl ether was added. The temperature was raised to 40 °C and reacted for 72 h to obtain a compound shown in formula (12) with a VBCB content of 90 wt%, with Mn of about 7800 - 9812, labeled as A7.

[0169] 50 g of n-butyl acetate and 50 g of a mixture of VBCB and St (where the mass fraction of VBCB was 55%) were added to a reaction flask, stirred evenly, and then 9.8 g of boron trifluoride methyl ether was added. The reaction was carried out at 20 °C for 36 h to obtain a compound shown in formula (12) with a VBCB content of 55 wt%, with Mn of about 1864 - 3012, labeled as A8.

[0170] Synthesis Example 6: Preparation of Ethylstyrene-VBCB Random Copolymer

[0171] 70 g of tetrahydrofuran and 50 g of a mixture of VBCB and p-ethylstyrene (where the mass fraction of VBCB was 75%) were added to a reaction flask, stirred evenly, and then 9.2 g of aluminum trichloride was added. The temperature was raised to 70 °C and reacted for 4 h to obtain a compound shown in formula (13) with a VBCB content of 75 wt%, with Mn of about 1987 - 4653, labeled as A9.

[0172] Synthesis Example 7: Preparation of DVB-VBCB Random Copolymer

[0173] 23 g of n-propyl acetate and 10 g of a mixture of VBCB and m-divinylbenzene (m-DVB) (where the mass fraction of VBCB was 75%) were added to a reaction flask, stirred evenly, and then 0.44 g of boron trifluoride diethyl ether was added. The temperature was raised to 40 °C and reacted for 4 h to obtain a compound shown in formula (17) with a VBCB content of 75 wt%, with Mn of about 8045 - 9638, labeled as A10.

[0174] Synthesis Example 8: Preparation of BVPE-VBCB Random Copolymer

[0175] Add 20 g of n-propyl acetate and 10 g of a mixture of VBCB and BVPE (where the mass ratio of VBCB is 90%) to a reaction flask, stir evenly, then add 0.42 g of boron trifluoride diethyl ether, raise the temperature to 40 °C and react for 4 hours to obtain a compound of formula (19) with a VBCB content of 90 wt%, Mn is about 9134 - 11065, labeled as A11.

[0176] Synthesis Example 9: Preparation of St-VBCB Random Copolymer (VBCB content is 50 wt%)

[0177] Add 50 g of n-propyl acetate and 50 g of a mixture of VBCB and St (where the mass ratio of VBCB is 50%) to a reaction flask, stir evenly, then add 1.09 g of boron trifluoride diethyl ether, raise the temperature to 40 °C and react for 72 hours to obtain a St-VBCB random copolymer (VBCB content is 50 wt%), labeled as B1.

[0178] Synthesis Example 10: Preparation of St-VBCB Random Copolymer (VBCB content is 30 wt%)

[0179] Add 50 g of n-propyl acetate and 50 g of a mixture of VBCB and St (where the mass ratio of VBCB is 30%) to a reaction flask, stir evenly, then add 1.09 g of boron trifluoride diethyl ether, raise the temperature to 40 °C and react for 72 hours to obtain a St-VBCB random copolymer (VBCB content is 30 wt%), labeled as B2.

[0180] Synthesis Example 11: Preparation of VBCB Homopolymer (VBCB content is 100 wt%)

[0181] Add 50 g of n-propyl acetate and 50 g of VBCB to a reaction flask, stir evenly, then add 1.09 g of boron trifluoride diethyl ether, raise the temperature to 40 °C and react for 48 hours to obtain a VBCB homopolymer (VBCB content is 100 wt%), labeled as B3.

[0182] Synthesis Example 12: Preparation of BCB-Modified DVB-St Copolymer (structural formula is as follows)

[0183]

[0184] After evacuating the reactor and purging it with nitrogen three times repeatedly, 2.5 moles of 4-bromobenzocyclobutene, 7.5 moles of divinylbenzene, 0.0075 moles of palladium acetate, 0.03 moles of tris(o-tolyl)phosphine, 2.63 moles of triethylamine and 2 liters of dry acetonitrile were added. After replacing the system with nitrogen once again, the temperature was raised to 58 °C in a water bath. After 48 hours, the reaction was terminated. After cooling to room temperature, a large amount of salt precipitated out. Then, filtration was carried out to remove the solid and palladium black. The filtrate was concentrated by rotary evaporation to remove the solvent, and then filtered through silica gel. The filtrate obtained from this filtration was distilled under reduced pressure at 80 °C to 90 °C to remove the unreacted raw materials, obtaining a pale yellow liquid. Then, it was purified by distillation under reduced pressure at 90 °C and 150 °C in sequence to obtain the divinylbenzene monomer with benzocyclobutene monosubstitution.

[0185] 0.025 moles of the divinylbenzene monomer with benzocyclobutene monosubstitution and 0.025 moles of styrene monomer were added to a single-necked flask. After covering with a rubber stopper and evacuating and purging with nitrogen three times repeatedly, 22 mL of toluene was added by injection. The reaction was stirred at 100 °C for 10 hours, cooled to room temperature, and precipitated with methanol three times to obtain a white powder, which was the BCB-modified DVB-St copolymer, labeled as B4.

[0186] Synthesis Example 13: Self-made compound of formula (3-4)

[0187] 1 mole of 1,1'-bis(4-bromophenyl)ethane, 1.2 moles of a tetrahydrofuran solution of vinylmagnesium bromide, and 0.05 moles of palladium dichloride were successively added to a three-necked flask under nitrogen protection and refluxed for 24 hours. Then, the reaction was quenched by adding a saturated ammonium chloride aqueous solution, and extracted with dichloromethane solution. After combining the organic phases, the solvent was evaporated to obtain a crude product, which was separated by column chromatography to obtain 0.9 moles of 1,1'-bis(4-vinylphenyl)ethane.

[0188] 0.8 moles of 1,1'-bis(4-vinylphenyl)ethane, 1.6 moles of N-bromosuccinimide, 0.05 moles of dibenzoyl peroxide and an appropriate amount of carbon tetrachloride were successively added to a three-necked flask, and refluxed for 12 hours. The reaction solution was washed three times with a sodium thiosulfate solution, and the solvent was evaporated to obtain a dry powder solid, which was recrystallized from acetone to obtain 1,1'-bis(4-vinylphenyl)-1-bromoethane.

[0189] 0.5 moles of 1,1'-bis(4-vinylphenyl)-1-bromoethane and 1 mole of silver-activated zinc powder were successively added to a reaction flask, and reacted for 2 hours. After cooling to room temperature, the reaction was quenched with saturated ammonium chloride, filtered to remove the unreacted zinc powder, and separated by column chromatography to obtain 2,3-tetrakis(4-vinylphenyl)butane, labeled as the compound of formula (3-4), and the structural formula is as follows.

[0190]

[0191] Synthesis Example 14: Self-made compound of formula (3-5)

[0192] Add 0.01 mol of 4-isopropylbenzaldehyde, 0.02 mol of N-bromosuccinimide, 0.05 mol of dibenzoyl peroxide and 10 mL of carbon tetrachloride into a reaction flask, reflux for 12 hours. After concentrating the product, purify it by chromatography column to obtain 2-bromo-2-(4-formylphenyl)propane.

[0193] Add 0.01 mol of 2-bromo-2-(4-formylphenyl)propane and 0.02 mol of silver-activated zinc powder into a reaction flask, react for 2 hours, filter to remove the unreacted zinc powder, and purify by chromatography column to obtain 2,3-dimethyl-2,3-bis(4-formylphenyl)butane.

[0194] Add anhydrous calcium chloride into tetrahydrofuran, let it stand overnight to remove water. Add 0.01 mol of 2,3-dimethyl-2,3-bis(4-formylphenyl)butane, 0.015 mol of methyltriphenylphosphonium bromide and 15 mL of tetrahydrofuran into a four-necked flask. Slowly add 0.015 mol of potassium tert-butoxide under ice-water bath condition, react at room temperature for 2 hours. Add saturated aqueous solution of ammonium chloride to inactivate the phosphonium ylide, filter to remove the excess salt. Add 0.03 mol of calcium bromide into the obtained filtrate, stir for 18 hours, filter. The obtained crude product is purified by chromatography column to obtain 2,3-dimethyl-2,3-bis(4-vinylphenyl)butane, marked as the compound of formula (3-5), and the structural formula is as follows.

[0195]

[0196] Synthesis Example 15: Self-made compound of formula (3-6)

[0197] Add the tetrahydrofuran solution of 0.6 mol of acetophenone into a three-necked flask under nitrogen protection, dropwise add 1.8 mol of titanium tetrachloride under ice bath, stir at room temperature for 10 minutes after dropping, and reflux for 12 hours. After monitoring the reaction by TLC and cooling to room temperature, add potassium carbonate solution to precipitate, filter to obtain the filter cake, then extract with dichloromethane, and finally evaporate the solvent to obtain 0.25 mol of 1,2-dimethylstilbene.

[0198] Add the dichloromethane solution of 0.24 mol of benzoic peroxide into the dichloromethane solution of 0.2 mol of 1,2-dimethylstilbene in a three-necked flask under ice bath, react at room temperature for 24 hours after dropping, and the reaction is completed by TLC detection. Extract the organic phase with sodium thiosulfate solution and sodium bicarbonate solution in turn, evaporate the solvent to obtain a dry powder solid, and recrystallize with acetone to obtain 0.16 mol of 1,2-dimethylstilbene epoxide.

[0199] Add a tetrahydrofuran solution of 0.15 mol of 1,2-dimethylstilbene epoxide to a three-necked flask, add 0.6 mol of 10% sulfuric acid solution at room temperature, and after refluxing for 8 hours, the reaction is completed. Pour the reaction solution into 5 L of cold water to precipitate a solid, filter to obtain a filter cake, and recrystallize with ethanol to obtain 0.14 mol of 1,2-dimethyl diphenylbutanediol.

[0200] Add 0.1 mol of 1,2-dimethyl diphenylbutanediol, 0.15 mol of methacryloyl chloride, and toluene to a three-necked flask equipped with a water separator in sequence. Slowly add 0.01 mol of concentrated sulfuric acid. After refluxing for 24 hours, neutralize the reaction solution with 10% sodium hydroxide solution, extract with ethyl acetate, wash with saturated brine, evaporate the solvent to obtain a dry powder solid, and recrystallize with isopropanol / n-hexane to obtain 0.08 mol of 2,3-diphenylbutane-2,3-diyl bis(2-methylacrylate), labeled as the compound of formula (3-6), and the structural formula is as follows.

[0201]

[0202] The compositions and characteristic test results of the resin compositions of the examples and comparative examples of the present invention are shown in Tables 1 to 5: [Table 1] Compositions (unit: parts by weight) and characteristic test results of the resin compositions of the examples

[0203]

[0204] [Table 2] Compositions (unit: parts by weight) and characteristic test results of the resin compositions of the examples

[0205]

[0206] [Table 3] Compositions (unit: parts by weight) and characteristic test results of the resin compositions of the examples

[0207]

[0208] [Table 4] Compositions (unit: parts by weight) and characteristic test results of the resin compositions of the comparative examples

[0209]

[0210] [Table 5] Compositions (unit: parts by weight) and characteristic test results of the resin compositions of the comparative examples

[0211]

[0212] In this application, for the characteristic tests of the examples and comparative examples, the test articles (samples) are prepared with reference to the following method, and then carried out according to the specific test conditions.

[0213] 1. B-stage prepreg A: The resin compositions in the examples or comparative examples were respectively selected, uniformly mixed to form a varnish, placed in an impregnation tank, and then a glass fiber cloth (e.g., L-glass fiber fabric with a specification of 2116) was immersed in the impregnation tank to attach the resin composition to the glass fiber cloth, and heated to the B-stage at 150°C to 170°C to obtain a B-stage prepreg with a resin content of 53%.

[0214] 2. B-stage prepreg B: The resin compositions in the examples or comparative examples were respectively selected, uniformly mixed to form a varnish, placed in an impregnation tank, and then a quartz glass fiber cloth (e.g., with a specification of 1080) was immersed in the impregnation tank to attach the resin composition to the glass fiber cloth, and heated to the B-stage at 150°C to 170°C to obtain a B-stage prepreg with a resin content of 70%.

[0215] 3. Copper-clad laminate (8-ply, laminated from 8 B-stage prepregs): Prepare 2 pieces of ultra-low surface roughness (HVLP) copper foils with a thickness of 18 μm and 8 B-stage prepregs A made by impregnating 2116 L-glass fiber cloths with each sample to be tested (each group of examples or each group of comparative examples). The resin content of each B-stage prepreg is approximately 53%. Stack them in the order of 1 piece of HVLP copper foil, 8 B-stage prepregs, and 1 piece of HVLP copper foil, and laminate at 200°C under a pressure of 500 psi for 2 hours under vacuum conditions to form a copper-clad laminate. Among them, the 8 mutually stacked B-stage prepregs are cured to form an insulating layer between the two copper foils, and the resin content of the insulating layer is approximately 53%.

[0216] 4. Copper-free laminate (8-ply, laminated from 8 B-stage prepregs): The two copper foils of the above copper-clad laminate (8-ply) were removed by etching to obtain a copper-free laminate (8-ply). The copper-free laminate is laminated from 8 B-stage prepregs, and the resin content of the copper-free laminate is approximately 53%.

[0217] 5. Copper-free substrate (2-ply, laminated from two prepregs): Prepare two ultra-low surface roughness (HVLP) copper foils with a thickness of 18 μm and two prepregs B impregnated with each sample to be tested (each set of examples or each set of comparative examples) made from 1080 quartz glass fiber cloth. Stack them in the order of copper foil, two prepregs, and copper foil, and laminate them under vacuum conditions at a pressure of 500 psi and 200 °C for 2 hours to form a copper-containing substrate (2-ply, laminated from two prepregs). Then, etch away the copper foils on both sides of the above copper-containing substrate (2-ply) to obtain a copper-free substrate (2-ply), which is laminated from two prepregs, and the resin content of the copper-free substrate (2-ply) is about 70%.

[0218] 6. Ten-layer board: Prepare a copper-containing substrate of EM-LX (available from Taiguang Electronic Materials Co., Ltd., with a thickness of 3 mils, using 1078E-glass fiber cloth and 18-μm-thick HTE copper foil). Make circuits on the surface copper foil of the copper-containing substrate (such as the well-known exposure, lithography, and etching processes, which will not be elaborated here) to obtain a core board. After obtaining the core board, prepare prepreg C (made from the resin compositions of each set of examples and comparative examples respectively, using 1027L-glass fiber cloth). Stack one prepreg C on each side of the core board, and stack another 18-μm-thick HTE copper foil on the other side of prepreg C relative to the core board, and laminate and cure it under vacuum conditions at a high temperature (200 °C) and high pressure (360 psi) for 2 hours to complete the first lamination. Then, perform a drilling process to make alignment holes, and then perform an in-hole metallization process and a circuit process to complete the first build-up step, thereby forming a four-layer board. Repeat the above build-up steps to form a six-layer board (second build-up, second lamination), an eight-layer board (third build-up, third lamination), until a ten-layer board (fourth build-up, fourth lamination) is formed.

[0219] For the aforementioned samples to be tested, the description of each test method and its characteristic analysis items is as follows:

[0220] 1. Glass transition temperature (Tg)

[0221] Select the aforementioned copper-free substrate (8-ply) as the sample to be tested, and use a dynamic mechanical analyzer (DMA) to measure the glass transition temperature of each sample to be tested according to the method described in IPC-TM-650 2.4.24.4 (2012), with the unit of °C. The measurement temperature range is 50 °C to 400 °C, and the temperature rise rate is 2 °C / minute.

[0222] 2. Storage modulus decay rate

[0223] Select the aforementioned copper-free substrate (8-ply) to fabricate the sample to be tested. Referring to the method of IPC-TM-650 2.4.24.4, use a dynamic mechanical analyzer (DMA) to measure the storage modulus of the sample. The measurement temperature range is 50°C to 400°C, and the temperature rise rate is 2°C per minute. Record the storage modulus of the sample at 50°C, denoted as E’ 50 , with the unit of MPa; and record the storage modulus of the sample at 250°C, denoted as E’ 250 , with the unit of MPa. Calculate the storage modulus decay rate according to the following formula: ((E’ 50 - E’ 250 ) / E’ 50 ) * 100%. When the relative difference in the storage modulus decay rate is greater than or equal to 1%, it indicates a significant difference (significant technical difficulty) between different samples.

[0224] 3. Reflow warpage

[0225] Select the aforementioned ten-layer board and cut a sample with length and width dimensions of 150 mm × 78 mm. Use the TherMoire instrument sold by Akrometrix company and refer to the test method of JESD22-B112A to perform reflow soldering on the ten-layer board. During the process, first raise the temperature from 30°C to 260°C, and then measure the maximum and minimum warpage values of the ten-layer board at 260°C and 30°C. The difference between the two is the reflow warpage (i.e., the maximum warpage minus the minimum warpage), with the unit of μm. When the difference in reflow warpage is greater than or equal to 1 μm, it indicates a significant difference (significant technical difficulty) between different samples.

[0226] 4. Percent of thermal expansion, z-axis, Z-PTE

[0227] Select the aforementioned copper-free substrate (8-ply) to fabricate the samples to be tested, and perform thermal mechanical analysis (TMA) according to the method of IPC-TM-650 2.4.24.5. Heat from 50 °C to 260 °C at a heating rate of 10 °C per minute, and measure the Z-axis thermal expansion rate (unit: %) of each sample to be tested in the temperature range of 50 °C to 260 °C. When the measured value of the Z-axis thermal expansion rate is less than or equal to 1%, a difference in the measured value of the Z-axis thermal expansion rate greater than or equal to 0.1% represents a significant difference (significant technical difficulty) between different samples. For example, the difference in the measured values between Example E1 and Comparative Example C1 of this application is 1.2% - 0.9% = 0.3%, indicating a significant difference between E1 and C1; on the other hand, the improvement in the Z-axis thermal expansion rate of Example E1 compared to Comparative Example C1 is 0.3% / 1.2% * 100 = 25%, that is, the Z-axis thermal expansion rate of Example E1 is reduced by 25% compared to Comparative Example C1.

[0228] 5. Dielectric Dissipation Factor (Df)

[0229] Select the aforementioned copper-free substrate (2-ply) as the samples to be tested, and use a microwave dielectric analyzer (purchased from AET Corporation, Japan). Refer to the method described in JIS C2565 (1992) to measure each sample at room temperature (about 25 °C) and at a frequency of 10 GHz. In the range where the measured frequency is 10 GHz and the Df value is less than 0.001, a difference in the Df value greater than or equal to 0.00002 represents a significant difference (significant technical difficulty) between the dielectric losses of different substrates.

[0230] 6. Substrate Appearance

[0231] Take the aforementioned copper-free substrate (8-ply, laminated from 8 prepregs), and visually observe whether there are dendritic stripes (abbreviated as stripes) on the surface of the substrate at the edge of the panel. If there are no dendritic stripes at the edge of the panel (a schematic diagram of the absence of stripe phenomenon can be referred to Figure 6 in US Patent No. US11,434,367B2), it is recorded as pass; if dendritic stripes appear at the edge of the panel (a schematic diagram of the stripe phenomenon can be referred to Figure 4 in US Patent No. US 11,434,367 B2), it is recorded as NG.

[0232] Based on the comprehensive reference to the characteristic test results in Tables 1 to 5, the following phenomena can be clearly observed:

[0233] 1. Examples E1 to E19 used a copolymer having a structural unit formed from the monomer represented by formula (1) and a structural unit formed from the monomer represented by formula (2) (hereinafter simply referred to as the copolymer of the present invention). The monomer represented by formula (1) may be, for example, styrene (St), ethylstyrene, divinylbenzene (DVB), or bis(vinylphenyl)ethane (BVPE). The monomer represented by formula (2) may be, for example, 4-vinylbenzocyclobutene (VBCB). The content of the structural unit formed from the monomer represented by formula (2) in the copolymer was 55 wt% to 90 wt%. The copolymers used in Examples E1 to E12 and E18 to E19 were block copolymers, and the copolymers used in Examples E13 to E17 were random copolymers. In Comparative Examples C1 and C2, the amount of the compound represented by formula (3) was outside the scope of the present invention; in the copolymers of Comparative Examples C3 and C4, the content of the structural unit formed from the monomer represented by formula (2) in the copolymer was outside the scope of the present invention (the VBCB content in C3 was 50 wt%, and the VBCB content in C4 was 30 wt%); Comparative Example C5 used a VBCB homopolymer (VBCB content was 100 wt%); Comparative Example C6 used a BCB-modified DVB-St copolymer different from the copolymer of the present invention; Comparative Examples C7 to C10 used polyolefins different from the copolymer of the present invention; Comparative Examples C11 to C13 used curing accelerators different from the compound represented by formula (3) of the present invention.

[0234] 2. Examples E1 to E19 used 100 parts by weight of the copolymer of the present invention and added 1 to 15 parts by weight of the compound represented by formula (3). Compared with Comparative Examples C1 and C2, which used 100 parts by weight of the copolymer of the present invention and added 0 parts by weight and 20 parts by weight of the compound represented by formula (3) respectively, the following properties were significantly improved: storage modulus decay rate and reflow warpage. Among them, the storage modulus decay rate of the samples in Examples E1 to E19 was less than or equal to 16%, and the reflow warpage was less than or equal to 14 μm; in contrast, the storage modulus decay rate of Comparative Examples C1 and C2 was greater than or equal to 20%, and the reflow warpage was greater than or equal to 16 μm.

[0235] 3. Examples E1 to E19 used the copolymer of the present invention and added the compound shown in formula (3). Compared with Comparative Examples C3 and C4 that used copolymers with VBCB content outside the scope of the present invention and added the compound shown in formula (3), and Comparative Example C6 that used a BCB-modified DVB-St copolymer different from the copolymer of the present invention and added the compound shown in formula (3), the following properties were significantly improved: the decay rate of storage modulus. Among them, the decay rates of storage modulus of the samples in Examples E1 to E19 were all less than or equal to 16%, while the decay rates of storage modulus of the samples in Comparative Examples C3, C4, and C6 were all greater than or equal to 17%. In addition, Examples E1 to E19 used the copolymer of the present invention and added the compound shown in formula (3). Compared with Comparative Example C5 that used a VBCB homopolymer (VBCB content was 100 wt%) and added the compound shown in formula (3), the following properties were significantly improved: dielectric loss and substrate appearance. Among them, the dielectric losses of the samples in Examples E1 to E19 were all less than or equal to 0.00086, and there were no stripes on the substrate appearance. The dielectric loss of Comparative Example C5 was 0.00096, and there were stripe phenomena on the substrate appearance.

[0236] 4. Examples E1 to E19 used the copolymer of the present invention and added the compound shown in formula (3). Compared with Comparative Examples C7 to C10 that used polyolefins different from the copolymer of the present invention and added the compound shown in formula (3), the following properties were significantly improved: glass transition temperature, decay rate of storage modulus, warpage during reflow soldering, Z-axis thermal expansion rate, dielectric loss, and substrate appearance. Among them, the glass transition temperatures of the samples in Examples E1 to E19 were all greater than or equal to 290 °C, the decay rates of storage modulus were all less than or equal to 16%, the warpage during reflow soldering was all less than or equal to 14 μm, the Z-axis thermal expansion rates were all less than or equal to 1.2%, the dielectric losses were all less than or equal to 0.00086, and there were no stripes on the substrate appearance. In contrast, the glass transition temperatures of Comparative Examples C7 to C10 were all less than 110 °C, the decay rates of storage modulus were all greater than or equal to 81%, the warpage during reflow soldering was all greater than or equal to 30 μm, the Z-axis thermal expansion rates were all greater than or equal to 2.5%, the dielectric losses were all greater than or equal to 0.00090, and there were stripe phenomena on the substrate appearance.

[0237] 5. Examples E1 to E19 used the copolymer of the present invention and added the compound shown in formula (3). Compared with Comparative Examples C11 to C13 that used the copolymer of the present invention and added a curing accelerator different from the compound shown in formula (3) of the present invention, the following properties were significantly improved: decay rate of storage modulus and dielectric loss. Among them, the decay rates of storage modulus of the samples in Examples E1 to E19 were all less than or equal to 16%, and the dielectric losses were all less than or equal to 0.00086. In contrast, the decay rates of storage modulus of Comparative Examples C11 to C13 were all greater than or equal to 18%, and the dielectric losses were all greater than or equal to 0.00106.

[0238] 6. For Examples E1 to E12 and E18 to E19 of the present invention, the copolymer used is a block copolymer and a compound represented by formula (3) is added. Compared with Examples E13 to E17 in which the copolymer of the present invention used is a random copolymer and a compound represented by formula (3) is added, various properties are significantly improved, especially having a lower storage modulus decay rate, Z-axis thermal expansion rate, and reflow warpage.

[0239] The above embodiments are essentially only for auxiliary explanation and are not intended to limit the embodiments of the present application or the application or use of these embodiments. In the present application, terms similar to "example" represent "as an example, illustration, or explanation". Any exemplary embodiment herein is not necessarily to be construed as being preferred or more advantageous than other embodiments, unless otherwise specified.

[0240] In addition, although at least one exemplary embodiment or comparative example has been presented in the foregoing embodiments, it should be understood that there can still be numerous variations in the present application. It should also be understood that the embodiments described herein are not intended to limit the scope, use, or configuration of the claimed technical solution in any way. On the contrary, the foregoing embodiments will provide those skilled in the art with a simple guide to implement the one or more embodiments and their equivalent forms described. Furthermore, the claims include known equivalent forms and all foreseeable equivalent forms at the time of filing this patent application.

Claims

1. A resin composition, characterized in that, The resin composition includes: (A) 100 parts by weight of a copolymer having a structural unit formed from a monomer represented by formula (1) and a structural unit formed from a monomer represented by formula (2), and the content of the structural unit formed from the monomer represented by formula (2) in the copolymer is 55 wt% to 90 wt%; and (B) 1 part by weight to 15 parts by weight of a compound represented by formula (3); In formula (1), each of R1 to R5 is independently selected from a hydrogen atom, a C1 - C3 alkyl group, a C2 - C3 alkenyl group, a phenyl group, a phenyl group substituted by a C1 - C3 alkyl group, a phenyl group substituted by a C2 - C3 alkenyl group, and a C2 - C3 alkenylphenyl C1 - C3 alkylene group; In formula (2), each of R6 to R9 is independently selected from a hydrogen atom, a C1 - C3 alkyl group, and a C2 - C3 alkenyl group, and at least one of R6 to R9 is a C2 - C3 alkenyl group; In formula (3), each of X', Y', and Z' independently represents a hydrogen atom, a C1 - C4 alkyl group, a phenyl group, or a group containing an unsaturated carbon - carbon double bond.

2. The resin composition according to claim 1, characterized in that, The monomer represented by formula (1) includes the monomer represented by formula (1 - 1), the monomer represented by formula (1 - 2), the monomer represented by formula (1 - 3), the monomer represented by formula (1 - 4), or a combination thereof, and the monomer represented by formula (2) includes the monomer represented by formula (2 - 1).

3. The resin composition according to claim 1, characterized in that, The copolymer includes any one or a combination of the copolymers represented by the following formula (4) to formula (19): Wherein, m, n, x, y, and z are each independently a positive integer, and 2 ≤ m ≤ 44, 12 ≤ n ≤ 70, 2 ≤ x + z ≤ 44, 12 ≤ y ≤ 70.

4. The resin composition according to claim 1, characterized in that, The copolymer includes a block copolymer, a random copolymer, or a combination thereof.

5. The resin composition according to claim 1, characterized in that, The compound represented by formula (3) has at least one group containing an unsaturated carbon - carbon double bond.

6. The resin composition according to claim 1, characterized in that, In formula (3), at least one of X', Y', and Z' represents a vinyl group, a vinylbenzyl group, a vinylphenyl group, an allyl group, or a (meth)acryloyloxy group.

7. The resin composition according to claim 1, characterized in that, The compound represented by formula (3) includes any one or a combination of the compounds from formula (3 - 1) to formula (3 - 6):

8. The resin composition according to claim 1, characterized in that, The resin composition further includes a cross - linker containing an unsaturated carbon - carbon double bond, and the cross - linker containing an unsaturated carbon - carbon double bond is any one or a combination of bis(vinylphenyl)ethane, divinylbenzene, divinylnaphthalene, divinylbiphenyl, triallyl isocyanurate, triallyl cyanurate, vinylbenzocyclobutene, bis(vinylbenzyl)ether, trivinylcyclohexane, diallylbisphenol A, polyfunctional acrylates, butadiene, decadiene, octadiene.

9. The resin composition according to claim 1, characterized in that, The resin composition further includes any one or a combination of a polyolefin different from the copolymer, a polyphenylene ether resin containing an unsaturated carbon - carbon double bond, a benzoxazine resin, an epoxy resin, a polyester resin, a phenolic resin, an amine curing agent, a polyamide, a polyimide, styrene maleic anhydride, a maleimide resin, a cyanate ester.

10. The resin composition according to claim 1, characterized in that, The resin composition further includes any one or a combination of an inorganic filler, a flame retardant, a curing accelerator different from the compound represented by formula (3), a polymerization inhibitor, a solvent, a silane coupling agent, a dye, a toughening agent.

11. An article made of the resin composition according to any one of claims 1 to 10, characterized in that, The article includes a prepreg, a resin film, a laminate, or a printed circuit board.

12. The article according to claim 11, characterized in that, The article has one, more than one, or all of the following characteristics: Its glass transition temperature measured according to the method of IPC-TM-650 2.4.24.4 is greater than or equal to 290 °C; The decay rate of its storage modulus calculated according to the method of IPC-TM-650 2.4.24.4 is less than or equal to 16%; Its reflow warpage measured according to the method of JESD22-B112A is less than or equal to 14 μm; Its Z-axis thermal expansion rate measured according to the method of IPC-TM-650 2.4.24.5 is less than or equal to 1.2%; and Its dielectric loss measured at a frequency of 10 GHz according to the method of JIS C2565 is less than or equal to 0.00086.

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