Phosphorus-containing copolymer having vinyl group, resin composition and product thereof

Abstract

Disclosed are a phosphorus-containing copolymer having a vinyl group, a resin composition including the phosphorus-containing copolymer, and an article of the resin composition. The phosphorus-containing copolymer with vinyl comprises a structural unit as shown in a formula (1-1) and a structural unit as shown in a formula (1-2). The resin composition includes 100 parts by weight of a vinyl-containing polyphenylene ether resin and 55 to 80 parts by weight of a phosphorus-containing copolymer having a vinyl group. The resin composition can be made into a prepreg, a resin film, a laminated board or a printed circuit board, and at least one of the characteristics of dielectric constant, dielectric loss, tensile force to copper foil, flame resistance, glass transition temperature, PCT water absorption and the like is improved. # imgabs0 #

Description

Technical Field

[0001] The present invention relates to the technical field of polymer materials, and in particular to a phosphorus-containing copolymer having a vinyl group, a resin composition comprising the phosphorus-containing copolymer, and a product of the resin composition. Background Art

[0002] In recent years, as electronic signal transmission methods develop towards 5G, and electronic equipment, communication devices, personal computers, etc. become more functional and miniaturized, the circuit boards used are also developing towards multi-layering, high-density wiring, and high-speed signal transmission, which puts higher requirements on the comprehensive performance of circuit substrates such as copper foil substrates.

[0003] In order to improve the comprehensive performance of the circuit substrate, the prior art focuses on adjusting the component types, amounts or ratios of the raw resin composition. However, the properties of laminates and other articles made of known resin materials still cannot fully meet the requirements. Summary of the invention

[0004] In view of the problems encountered in the prior art, in particular, the inability of existing materials to meet one or more property requirements, the main purpose of the present invention is to provide a novel resin material that can overcome at least one of the above technical problems.

[0005] In order to achieve the above object, the present invention discloses a phosphorus-containing copolymer having a vinyl group, which comprises a structural unit represented by formula (1-1) and a structural unit represented by formula (1-2),

[0006]

[0007] in:

[0008] m and n each independently represent the number of repetitions of the unit in the brackets, such that the weight average molecular weight of the phosphorus-containing copolymer having vinyl groups is between 1,000 and 50,000;

[0009] R 1 and R 3 are each independently a hydrogen atom or a C1 to C3 alkyl group; and

[0010] R 2 A monovalent functional group selected from any one of formula (1-3) to formula (1-8), wherein r and q are each independently an integer from 0 to 3;

[0011]

[0012] And the phosphorus content of the phosphorus-containing copolymer having vinyl groups is greater than or equal to 7%.

[0013] In addition, the present invention also provides a resin composition, which includes 100 parts by weight of a vinyl-containing polyphenylene ether resin and 55 to 80 parts by weight of a phosphorus-containing copolymer having a vinyl group.

[0014] For example, in one embodiment, the resin composition further includes a multifunctional aromatic vinyl-containing compound.

[0015] For example, in one embodiment, the resin composition further includes 5 to 25 parts by weight of a multifunctional aromatic vinyl-containing compound.

[0016] For example, in one embodiment, the polyfunctional aromatic vinyl-containing compound has a structure shown in the following formula (2):

[0017] Where w is between 1 and 20.

[0018] For example, in one embodiment, the phosphorus-containing copolymer having a vinyl group is used as the first copolymer, and the resin composition further includes a second copolymer, wherein the second copolymer includes a structural unit represented by formula (3-1) and a structural unit represented by formula (3-2),

[0019]

[0020] wherein x and y each independently represent the number of repetitions of the unit in the brackets, such that the weight average molecular weight of the second copolymer is between 1,000 and 30,000; and

[0021] The second copolymer has a phosphorus content greater than or equal to 7%.

[0022] For example, in one embodiment, the resin composition further includes 5 to 10 parts by weight of a second copolymer.

[0023] For example, in one embodiment, the resin composition further includes an inorganic filler, a hardening accelerator, a flame retardant, an inhibitor, a solvent, a silane coupling agent, a colorant, a toughening agent or a combination thereof.

[0024] In order to achieve the above object, the present invention also discloses a product made of the above resin composition, which includes a prepreg, a resin film, a laminate or a printed circuit board.

[0025] For example, in one embodiment, the aforementioned product has one, multiple or all of the following characteristics:

[0026] The dielectric constant measured at a frequency of 10 GHz according to the method of JIS C2565 is less than or equal to 3.33;

[0027] The dielectric loss measured at a frequency of 10 GHz according to the method of JIS C2565 is less than or equal to 0.0026;

[0028] The copper foil tensile force measured by the method of IPC-TM-650 2.4.8 is greater than or equal to 3.21 lb / in;

[0029] The flame retardancy measured according to the UL94 standard is V-0.

[0030] A glass transition temperature greater than or equal to 190°C as measured in accordance with IPC-TM-650 2.4.24.4; and

[0031] The water absorption rate measured after 5 hours of moisture absorption in the pressure cooking test according to the method of IPC-TM-650 2.6.16.1 is less than or equal to 0.28%. DETAILED DESCRIPTION

[0032] In order to enable those skilled in the art to understand the characteristics and effects of the present invention, the following is a general description and definition of the terms and expressions mentioned in the specification and claims. Unless otherwise specified, all technical and scientific words used in the text have the common meanings understood by those skilled in the art for the present invention. In case of conflict, the definitions in this specification shall prevail.

[0033] The theories or mechanisms described and disclosed herein, whether correct or incorrect, should not limit the scope of the present invention in any way, that is, the present invention can be implemented without being limited by any specific theory or mechanism.

[0034] The use of "one", "a", "an" or similar expressions to describe the components and technical features of the present invention is merely for the convenience of expression and to provide a general meaning to the scope of the present invention. Therefore, such description should be understood to include one or at least one, and the singular also includes the plural, unless it is obvious that it refers to another meaning.

[0035] As used herein, the terms "comprises," "includes," "has," "contains," or any other similar terms are open-ended transitional phrases, which are intended to cover non-exclusive inclusions. For example, a composition or article comprising a plurality of elements encompasses any one or any one of the listed elements, and is not limited to the elements listed herein, but may also include other elements that are not explicitly listed but are generally inherent to the composition or article. In addition, unless expressly 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), and both A and B are true (or exist). In addition, in this article, the terms "comprising", "including", "having", and "containing" should be interpreted as being specifically disclosed and simultaneously covering closed conjunctions such as "consisting of", "consisting of", "the remainder of", and conjunctions such as "consisting essentially of", "mainly consisting of", "mainly consisting of", "basically containing", "essentially consisting of", "essentially consisting of", and "essentially containing".

[0036] As used herein, “or a combination thereof” means “or any combination thereof”, covering any combination of more than two of the listed elements; “any one”, “any one”, “any one” means “any one”, “any one”, “any one”. For example, “a composition or its product includes A, B, C or a combination thereof”, when interpreted, covers the following situations: A is true (or exists) and B and C are false (or do not exist), B is true (or exists) and A and C are false (or do not exist), C is true (or exists) and A and B are false (or do not exist), A and B are true (or exist) and C is false (or do not exist), A and C are true (or exist) and B is false (or do not exist), B and C are true (or exist) and A is false (or do not exist), A, B and C are all true (or exist), and other elements not explicitly listed but that are typically inherent to the composition or its product.

[0037] In this article, the terms "and", "with", "and", "as well as" or other similar terms are used to connect parallel sentence components, and there is no distinction between the previous and subsequent components. The meaning of the parallel sentence components does not change after the positions of the parallel sentence components are exchanged in grammatical sense.

[0038] In this article, all features or conditions such as numerical values, quantities, contents and concentrations defined in the form of numerical ranges or percentage ranges are only for simplicity and convenience. Accordingly, the description of numerical ranges or percentage ranges should be deemed to have covered and specifically disclosed all possible sub-ranges and individual values ​​within the range (including integers and fractions), especially integer values. For example, the range description of "1.0 to 8.0", "between 1.0 and 8.0" or "between 1.0 to 8.0" should be deemed to have 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 deemed to cover endpoint values, especially sub-ranges defined by integer values, and should be deemed to have specifically disclosed individual values ​​such as 1.0, 2.0, 3.0, 4.0, 5.0, 6.0, 7.0, 8.0, etc. Unless otherwise indicated, the above explanation method applies to all contents of the entire text of the present invention, regardless of whether the scope is broad or not.

[0039] If the 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 consisting of any pair of the upper limit or preferred value (or a better value) of the range and the lower limit or preferred value (or a better value) of the range have been specifically disclosed herein, regardless of whether these ranges are disclosed separately. In addition, if a numerical range is mentioned herein, unless otherwise specified, the range should include its endpoints and all integers and fractions within the range.

[0040] In this document, numerical values ​​should be understood to have the accuracy of the number of significant digits of the numerical value, provided that the purpose of the invention can be achieved. For example, the number 40.0 should be understood to cover the range of 39.50 to 40.49.

[0041] In this article, for the use of Markush groups or optional terms to describe the features or examples of the present invention, those skilled in the art should understand that all subgroups or any individual elements in the Markush group or optional list 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 use of Markush groups or optional terms to describe the features or examples of the present invention, those skilled in the art should understand that any combination of subgroups or individual members of all elements in the Markush group or optional list 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.

[0042] Unless otherwise specified, in the present invention, a compound refers to a chemical substance formed by two or more elements connected by chemical bonds, including small molecule compounds and polymer compounds, but not limited thereto. The compound herein is not limited to a single chemical substance when interpreted, but can also be interpreted as the same type of chemical substances with the same composition or the same properties.

[0043] If not otherwise specified, in the present invention, polymer refers to the product formed by monomer polymerization, often including many polymer aggregates, each polymer is composed of many simple structural units repeatedly connected by covalent bonds, and the monomer is a compound that synthesizes the polymer. The polymer may include homopolymers, copolymers, prepolymers, etc., and is not limited thereto. Homopolymer refers to a polymer polymerized from one monomer. Copolymer refers to a polymer polymerized from two or more monomers. Copolymers include random copolymers (structures such as -AABABBBAAABBA-), alternating copolymers (structures such as -ABABABAB-), graft copolymers (structures such as -AA(A-BBBB)AA(A-BBBB)AAA-) and block copolymers (structures such as -AAAAA-BBBBBB-AAAAA-), etc. Prepolymer refers to a polymer with a lower molecular weight between the monomer and the final polymer, and the prepolymer contains reactive functional groups that can be further polymerized to obtain a fully cross-linked or hardened product with a higher molecular weight. If not otherwise specified, in the present invention, polymers certainly include oligomers, and are not limited thereto. Oligomers, also known as low polymers, are polymers composed of 2 to 20 repeating units, usually 2 to 5 repeating units.

[0044] If not otherwise specified, the "resin" in the present invention is a customary name for a synthetic polymer, which may include monomers, polymers thereof, combinations of monomers, combinations of polymers thereof, or combinations of monomers and polymers thereof, etc., and is not limited thereto.

[0045] If not specifically stated, herein, “having a vinyl group” or “containing a vinyl group” is interpreted to include containing a vinyl group, a vinylbenzyl group, a vinylene group, an allyl group or a (meth)acrylate group, but is not limited thereto.

[0046] Unless otherwise specified, the alkyl, alkenyl, and monomer described in the present invention include their various isomers when interpreted. For example, propyl should be interpreted as including n-propyl and isopropyl.

[0047] Unless otherwise specified, in the present invention, parts by weight represent relative parts by weight in the composition, which may be any weight unit, such as but not limited to kilograms, kilograms, grams, pounds, etc. For example, 100 parts by weight of the vinyl-containing polyphenylene ether resin may represent 100 kilograms of the vinyl-containing polyphenylene ether resin or 100 pounds of the vinyl-containing polyphenylene ether resin.

[0048] It should be understood that the features disclosed in the various embodiments herein may be arbitrarily combined to form the technical solution of the present invention, as long as there is no contradiction in the combination of these features.

[0049] The following specific embodiments are merely illustrative in nature and are not intended to limit the present invention and its use. In addition, this article is not limited by any theory described in the above prior art or summary of the invention or the following specific embodiments or examples. The methods, reagents and conditions used in the examples are conventional methods, reagents and conditions in the art unless otherwise stated.

[0050] As mentioned above, the main purpose of the present invention is to provide a phosphorus-containing copolymer having a vinyl group, which comprises a structural unit represented by formula (1-1) and a structural unit represented by formula (1-2).

[0051]

[0052] In formula (1-1) and formula (1-2), m and n each independently represent the number of repetitions of the unit in the brackets (both m and n are not 0), so that the weight average molecular weight of the phosphorus-containing copolymer having vinyl groups is between 1,000 and 50,000. In other words, the values ​​of m and n are not particularly limited, as long as the weight average molecular weight of the phosphorus-containing copolymer having vinyl groups is between 1,000 and 50,000. For example, m can be any value between 2 and 120, such as 2, 5, 10, 20, 30, 40, 50, 60, 70, 80, 90, 100, 110 or 120, and n can be any value between 3 and 500, such as 3, 5, 10, 50, 100, 150, 200, 250, 300, 350, 400, 450, 490 or 500. For example, the weight average molecular weight of the phosphorus-containing copolymer having a vinyl group may be about 1,000, 3,000, 5,000, 7,000, 9,000, 10,000, 15,000, 20,000, 25,000, 30,000, 35,000, 40,000, 45,000, or 50,000.

[0053] In formula (1-1) and formula (1-2), R 1 and R 3 R is independently a hydrogen atom or a C1 to C3 alkyl group (eg, methyl, ethyl, n-propyl or isopropyl). 2 A monovalent functional group selected from any one of formula (1-3) to formula (1-8), wherein r and q are each independently an integer from 0 to 3 (e.g., 0, 1, 2 or 3):

[0054]

[0055] The phosphorus content of the vinyl group-containing copolymer of the present invention is greater than or equal to 7%, such as greater than or equal to 7%, greater than or equal to 7.5%, greater than or equal to 8%, greater than or equal to 8.5%, greater than or equal to 9%, greater than or equal to 9.5%, or greater than or equal to 9.9%. For example, the phosphorus content of the vinyl group-containing copolymer is between 7% and 10%.

[0056] The phosphorus-containing copolymer having vinyl groups may be a random copolymer, an alternating copolymer, a graft copolymer or a block copolymer. In other words, the structural unit represented by formula (1-1) and the structural unit represented by formula (1-2) may be connected in any manner to form the phosphorus-containing copolymer having vinyl groups of the present invention.

[0057] The phosphorus-containing copolymer having vinyl groups can provide a flame retardant effect due to the presence of phosphorus atoms (such as DPPO groups or DOPO groups) in the structure. In addition, the phosphorus-containing copolymer having vinyl groups can react with other components in the resin composition, such as a cross-linking reaction, due to the presence of reactive vinyl groups in the structure.

[0058] For example, in one embodiment, the products made of the phosphorus-containing copolymer with vinyl groups of the present invention can be improved in one or more properties such as dielectric loss and solvent compatibility. For example, the products made of the phosphorus-containing copolymer with vinyl groups of the present invention, such as copper-free substrates, preferably have a dielectric loss of less than or equal to 0.0025, such as less than or equal to 0.0025, less than or equal to 0.0024, less than or equal to 0.0023 or less than or equal to 0.0022, such as a dielectric loss between 0.0022 and 0.0025. The aforementioned dielectric loss is measured at a frequency of 10 GHz with reference to the method described in JIS C2565. For example, the phosphorus-containing copolymer with vinyl groups of the present invention and a solvent (such as butanone, toluene or a combination thereof) are placed in a transparent glass bottle and stirred evenly. After being left standing at room temperature (about 25° C.) for 24 hours, no precipitation is observed by visual observation, indicating that the phosphorus-containing copolymer with vinyl groups of the present invention has good solvent compatibility.

[0059] The phosphorus-containing copolymer having vinyl groups of the present invention can be prepared in various ways. For example, in one embodiment, an aldehyde (e.g., formaldehyde) and a triphenylphosphine dipole (as a Wittig reagent, such as 4-vinylbenzyl (triphenyl) phosphonium chloride) can be subjected to a Wittig reaction in an alkaline environment (e.g., potassium hydroxide) to generate an olefin (e.g., divinylbenzene) and triphenylphosphine oxide. The aforementioned olefin can be reacted with a phosphorus-containing compound (e.g., p-vinylbenzyl-DPPO) to obtain the phosphorus-containing copolymer having vinyl groups of the present invention.

[0060] On the other hand, the present invention also provides a resin composition, which includes 100 parts by weight of a vinyl-containing polyphenylene ether resin and 55 to 80 parts by weight of the aforementioned phosphorus-containing copolymer having a vinyl group. In other words, compared to 100 parts by weight of the vinyl-containing polyphenylene ether resin, the resin composition of the present invention may include 55, 60, 65, 70, 75 or 80 parts by weight of the phosphorus-containing copolymer having a vinyl group.

[0061] For example, in one embodiment, in the resin composition of the present invention, the content of phosphorus atoms is preferably greater than or equal to 2%, more preferably greater than or equal to 2.4%, such as between 2% and 4%, such as between 2.4% and 3.5%, and is not limited thereto.

[0062] For example, in one embodiment, the vinyl-containing polyphenylene ether resin may include various polyphenylene ether resins whose terminals are modified by vinyl or allyl groups. In addition, the vinyl-containing polyphenylene ether resin may also be a polyphenylene ether resin whose terminals are modified by (meth)acrylate.

[0063] For example, in one embodiment, the vinyl-containing polyphenylene ether resin refers to a polyphenylene ether resin containing a vinyl group, and examples thereof may include but are not limited to polyphenylene ether resins containing a vinyl group, an allyl group, a vinyl benzyl group, or a (meth)acrylate group. For example, in one embodiment, the vinyl-containing polyphenylene ether resin includes a vinyl benzyl biphenyl polyphenylene ether resin, a (meth)acrylate polyphenylene ether resin (i.e., a (meth)acryloyl polyphenylene ether resin), an allyl polyphenylene ether resin, a vinyl benzyl-modified bisphenol A polyphenylene ether resin, a vinyl chain-extended polyphenylene ether resin, or a combination thereof. For example, the vinyl-containing polyphenylene ether resin may be a vinyl benzyl biphenyl polyphenylene ether resin having a number average molecular weight of about 1200 (e.g., OPE-2st1200, available from Mitsubishi Gas Chemical Co., Ltd.), a vinyl benzyl biphenyl polyphenylene ether resin having a number average molecular weight of about 2200 (e.g., OPE-2st 2200, available from Mitsubishi Gas Chemical Co., Ltd.), a methacrylate polyphenylene ether resin having a number average molecular weight of about 1900 to 2300 (e.g., SA9000, available from Sabic Corporation), a vinyl benzyl-modified bisphenol A polyphenylene ether resin having a number average molecular weight of about 2400 to 2800, a vinyl chain-extended polyphenylene ether resin having a number average molecular weight of about 2200 to 3000, or a combination thereof. The vinyl chain-extended polyphenylene ether resin may include various types of polyphenylene ether resins disclosed in U.S. Patent Application Publication No. 2016 / 0185904A1, which is incorporated herein by reference in its entirety.

[0064] In addition to the aforementioned components, the resin composition of the present invention may further include other components as necessary.

[0065] For example, in one embodiment, the resin composition of the present invention further comprises a polyfunctional aromatic vinyl-containing compound. The amount of the polyfunctional aromatic vinyl-containing compound is not particularly limited and can be adjusted as needed. For example, in one embodiment, compared to 100 parts by weight of the vinyl-containing polyphenylene ether resin, the resin composition of the present invention further comprises 5 to 25 parts by weight of the polyfunctional aromatic vinyl-containing compound, such as 5, 10, 15, 20 or 25 parts by weight of the polyfunctional aromatic vinyl-containing compound.

[0066] The type of the polyfunctional aromatic vinyl-containing compound is not particularly limited. For example, in one embodiment, the polyfunctional aromatic vinyl-containing compound has a structure shown in the following formula (2):

[0067]

[0068] wherein w represents the number of repetitions of the structural unit in brackets, and w is between 1 and 20, for example 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19 or 20.

[0069] For example, in one embodiment, the resin composition of the present invention further includes other copolymers different from the phosphorus-containing copolymer having vinyl groups. For example, in one embodiment, if the phosphorus-containing copolymer having vinyl groups is used as the first copolymer, the resin composition of the present invention may further include a second copolymer, and the second copolymer includes a structural unit represented by formula (3-1) and a structural unit represented by formula (3-2):

[0070]

[0071] In formula (3-1) and formula (3-2), x and y each independently represent the number of repetitions of the unit in the brackets, so that the weight average molecular weight of the second copolymer is between 1,000 and 30,000. For example, x can be any value between 2 and 70, such as 2, 5, 10, 20, 30, 40, 50, 60 or 70, and y can be any value between 2 and 150, such as 2, 5, 10, 50, 100 or 150. For example, the weight average molecular weight of the second copolymer can be about 1,000, 3,000, 5,000, 7,000, 9,000, 10,000, 15,000, 20,000, 25,000 or 30,000.

[0072] For example, in one embodiment, the phosphorus content of the second copolymer is greater than or equal to 7%, such as greater than or equal to 7%, greater than or equal to 7.5%, greater than or equal to 8%, greater than or equal to 8.5%, greater than or equal to 9%, greater than or equal to 9.5%, or greater than or equal to 9.9%. For example, the phosphorus content of the second copolymer is between 7% and 10%.

[0073] The second copolymer may be a random copolymer, an alternating copolymer, a graft copolymer or a block copolymer. In other words, the structural unit represented by formula (3-1) and the structural unit represented by formula (3-2) may be connected in any manner to form the second copolymer.

[0074] The amount of the second copolymer is not particularly limited and can be adjusted as needed. For example, in one embodiment, the resin composition of the present invention further includes 5 to 10 parts by weight of the second copolymer relative to 100 parts by weight of the vinyl-containing polyphenylene ether resin.

[0075] In addition to the aforementioned components, the resin composition of the present invention may further include inorganic fillers, hardening accelerators, flame retardants, polymerization inhibitors, solvents, silane coupling agents, coloring agents, toughening agents or combinations thereof as needed. If not otherwise specified, the content of any of the aforementioned components may be 0.1 to 300 parts by weight, such as 0.01, 0.1, 0.5, 1, 5, 10, 20, 30, 40, 50, 60, 70, 80, 90, 100, 150, 200, 250 or 300 parts by weight, such as 1 to 100 parts by weight, 30 to 150 parts by weight or 200 to 300 parts by weight, and is not limited thereto.

[0076] For example, the inorganic filler may be any one or more inorganic fillers suitable for the production of prepregs, resin films, laminates or printed circuit boards, and specific examples include but are not limited to: silicon dioxide (molten, non-molten, porous or hollow), aluminum oxide, aluminum hydroxide, magnesium oxide, 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, zirconium oxide, mica, boehmite (AlOOH), calcined talc, talc, silicon nitride or calcined kaolin. In addition, the inorganic filler may be spherical, fibrous, plate-like, granular, flaky or needle-like, and may be selectively pretreated with a silane coupling agent. For example, compared to 100 parts by weight of the vinyl-containing polyphenylene ether resin, the amount of the inorganic filler used in the present invention is not particularly limited, for example, it can be 80 parts by weight to 180 parts by weight, preferably 100 parts by weight to 150 parts by weight. For example, in one embodiment, the resin composition of the present invention includes 100 parts by weight of the vinyl-containing polyphenylene ether resin, 55 to 80 parts by weight of the phosphorus-containing copolymer having vinyl groups, and 5 to 40 parts by weight of boron nitride, and the thermal conductivity and dielectric loss of the product thereof can be improved.

[0077] For example, the hardening accelerator (including the hardening initiator) may include a catalyst such as a Lewis base or a Lewis acid. The Lewis base may include one or more of imidazole, boron trifluoride amine complex, ethyltriphenyl phosphonium chloride, 2-methylimidazole (2MI), 2-phenyl-1H-imidazole (2PZ), 2-ethyl-4-methylimidazole (2E4MI), triphenylphosphine (TPP) and 4-dimethylaminopyridine (DMAP). The Lewis acid may include a metal salt compound such as a metal salt compound of manganese, iron, cobalt, nickel, copper, zinc, etc., such as a metal catalyst such as zinc octoate and cobalt octoate. The hardening accelerator also includes a hardening initiator, such as a peroxide that can generate free radicals. The hardening initiator includes but is not limited to: diisopropylbenzene peroxide, tert-butyl perbenzoate, dibenzoyl peroxide (BPO), 2,5-dimethyl-2,5-di(tert-butylperoxy)-3-hexyne (25B) and bis(tert-butylperoxyisopropyl)benzene or a combination thereof.

[0078] For example, the flame retardant may be any one or more flame retardants suitable for the production of prepregs, resin films, laminates or printed circuit boards, such as but not limited to phosphorus-containing flame retardants, preferably including: ammonium polyphosphate, hydroquinone bis-(diphenylphosphate), bisphenol A bis-(diphenylphosphate), tri(2-carboxyethyl)phosphine (TCEP), tri(chloroisopropyl) phosphate, trimethyl phosphate (TMP), dimethyl methyl phosphonate (DMMP), resorcinol bis(dixylenyl phosphate) Phosphate), RDXP, such as PX-200, PX-201, PX-202 and other commercial products), phosphazene (phosphazene, such as SPB-100, SPH-100, SPV-100 and other commercial products), melamine polyphosphate, DOPO (9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide) and its derivatives or resins, DPPO (diphenylphosphine oxide) and its derivatives or resins, melamine cyanurate, tri-hydroxy ethyl isocyanurate, aluminum phosphinate (such as OP-930, OP-935 and other products) or a combination thereof.

[0079] For example, the flame retardant may be a DPPO compound (such as a bis-DPPO compound, such as commercially available products such as PQ-60), a DOPO compound (such as a bis-DOPO compound), a DOPO resin (such as DOPO-HQ, DOPO-NQ, DOPO-PN, DOPO-BPN), a DOPO-bonded epoxy resin, etc., wherein DOPO-PN is a DOPO phenol novolac compound, and DOPO-BPN may be a bisphenol novolac compound such as DOPO-BPAN (DOPO-bisphenol Anovolac), DOPO-BPFN (DOPO-bisphenol F novolac) or DOPO-BPSN (DOPO-bisphenol S novolac). The content of the flame retardant may be adjusted as required, and the resin composition may not contain the flame retardant, in which case the content of the flame retardant is 0 parts by weight, which means that the resin composition does not intentionally add the flame retardant.

[0080] For example, the above-mentioned inhibitor may include, but is not limited to, 1,1-diphenyl-2-trinitrophenylhydrazine, methacrylonitrile, 2,2,6,6-tetramethyl-1-oxy-piperidine, dithioester, nitrogen oxide stable free radical, triphenylmethyl free radical, metal ion free radical, sulfur free radical, hydroquinone, p-methoxyphenol, p-benzoquinone, phenothiazine, β-phenylnaphthylamine, p-tert-butylcatechol, methylene blue, 4,4'-butylenebis(6-tert-butyl-3-methylphenol) and 2,2'-methylenebis(4-ethyl-6-tert-butylphenol) or a combination thereof. For example, the above-mentioned nitrogen oxide stable free radical may include, but is not limited to, nitrogen oxide free radicals from cyclic hydroxylamines such as 2,2,6,6-substituted-1-piperidinyloxy free radical or 2,2,5,5-substituted-1-pyrrolidinyloxy free radical. As a substituent, an alkyl group with a carbon number of 4 or less, such as methyl or ethyl, is preferred. Specific nitrogen oxide free radical compounds are not limited, and examples include but are not limited to 2,2,6,6-tetramethyl-1-piperidinyloxy free radicals, 2,2,6,6-tetraethyl-1-piperidinyloxy free radicals, 2,2,6,6-tetramethyl-4-oxo-1-piperidinyloxy free radicals, 2,2,5,5-tetramethyl-1-pyrrolidinyloxy free radicals, 1,1,3,3-tetramethyl-2-isoindolinyloxy free radicals, N,N-di-tert-butylamineoxy free radicals, etc. Stable free radicals such as galvinoxyl free radicals can also be used to replace nitrogen oxide free radicals. The inhibitor suitable for the resin composition of the present invention can also be a product derived from the hydrogen atom or atomic group in the inhibitor being replaced by other atoms or atomic groups. For example, the hydrogen atom in the inhibitor is replaced by an atomic group such as an amino group, a hydroxyl group, a ketocarbonyl group, etc.

[0081] For example, the solvent suitable for the resin composition of the present invention is not particularly limited, and can be any solvent suitable for dissolving the resin composition of the present invention, including but not limited to: methanol, ethanol, ethylene glycol monomethyl ether, anisole, acetone, butanone (also known as methyl ethyl ketone), methyl isobutyl ketone, cyclohexanone, toluene, xylene, methoxyethyl acetate, ethoxyethyl acetate, propoxyethyl acetate, ethyl acetate, dimethylformamide, dimethylacetamide, propylene glycol methyl ether and other solvents or mixed solvents thereof. The amount of the aforementioned solvent is not particularly limited, and the amount of solvent added can be adjusted according to the viscosity required for the resin composition. For example, in one embodiment, the amount of solvent added is adjusted to a total solid content of 50wt% to 85wt% for addition, but is not limited thereto.

[0082] For example, the silane coupling agent may include a silane compound (such as but not limited to a siloxane compound), which may be further divided into an amino silane compound, an epoxy silane compound, a vinyl silane compound, an acrylate silane compound, a methacrylate silane compound, a hydroxy silane compound, an isocyanate silane compound, a methacryloxy silane compound, and an acryloxy silane compound according to the type of functional group.

[0083] If not specifically stated, the coloring agent applicable to the present invention may include but is not limited to dyes or pigments.

[0084] In the present invention, the main function of adding a toughening agent is to improve the toughness of the resin composition. For example, the toughening agent suitable for the present invention may include but is not limited to carboxyl-terminated butadieneacrylonitrile rubber (CTBN), core-shell rubber, ethylene-propylene rubber and other compounds or their combinations.

[0085] For example, in one embodiment, the resin composition of the present invention may further include maleimide resin, polyolefin, small molecule vinyl compound or a combination thereof.

[0086] For example, in one embodiment, the maleimide resin includes monomers or combinations thereof having one or more maleimide functional groups in the molecule. Unless otherwise specified, the maleimide resin used in the present invention is not particularly limited and may be any one or more maleimide resins suitable for making prepregs (or prepregs), resin films, laminates or printed circuit boards.In certain embodiments, the maleimide resin includes 4,4'-diphenylmethane bismaleimide resin, oligomer of phenylmethane maleimide (or polyphenylmethane maleimide), bisphenol A diphenyl ether bismaleimide resin, 3,3'-dimethyl-5,5'-diethyl-4,4'-diphenylmethane bismaleimide, bismaleimide) (also known as bis(3-ethyl-5-methyl-4-maleimidephenyl)methane), 3,3'-dimethyl-5,5'-dipropyl-4,4'-diphenylmethane bismaleimide, biphenylmaleimide, m-phenylene bismaleimide, 4-methyl-1,3-phenylene bismaleimide, bismaleimide), 1,6-bismaleimide-(2,2,4-trimethyl)hexane, 2,3-dimethylbenzenemaleimide (N-2,3-xylylmaleimide), 2,6-dimethylbenzenemaleimide (N-2,6-xylylmaleimide), N-phenylmaleimide, diethylbismaleimidotoluene, vinyl benzyl maleimide (VBM), maleimide resin containing aliphatic long chain structure or a combination thereof. If not otherwise specified, the aforementioned maleimide resin also includes modified products of these components when interpreted.

[0087] For example, the maleimide resin may be a maleimide resin produced by Daiwakasei Industry under the trade names of 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 a maleimide resin produced by KI Chemical under the trade names of BMI-70, BMI-80, or a maleimide resin produced by Nippon Kayaku under the trade names of MIR-3000, MIR-5000, or a maleimide resin produced by Evonik Chemical under the trade name of DE-TDAB.

[0088] For example, the maleimide resin containing an aliphatic long chain structure may be a maleimide resin produced by a designer molecular company under the trade names of BMI-689, BMI-1400, BMI-1500, BMI-1700, BMI-2500, BMI-3000, BMI-5000 and BMI-6000.

[0089] For example, in one embodiment, the aforementioned polyolefin includes polybutadiene, polyisoprene, styrene-butadiene copolymer, styrene-isoprene copolymer, styrene-butadiene-divinylbenzene terpolymer, maleic anhydride added styrene-butadiene copolymer, vinyl-polybutadiene-urea oligomer, maleic anhydride added butadiene copolymer, polymethylstyrene, hydrogenated polybutadiene, hydrogenated styrene-butadiene-divinylbenzene terpolymer, maleic anhydride added hydrogenated styrene-butadiene copolymer, hydrogenated styrene-butadiene copolymer, hydrogenated styrene-isoprene copolymer, olefin-based rubber (polyoctene rubber, ethylene propylene rubber (EPM), ethylene propylene diene rubber (EPDM)), etc.) or a combination thereof.

[0090] For example, in one embodiment, the aforementioned small molecule vinyl compound refers to a vinyl compound with a molecular weight less than or equal to 1000, preferably a molecular weight between 100 and 900, and more preferably a molecular weight between 100 and 800. In one embodiment, the small molecule vinyl compound includes but is not limited to divinylbenzene, bis(vinylbenzyl)ether (BVBE), bis(vinylphenyl)ethane (BVPE), triallyl isocyanurate (TAIC), triallyl cyanurate (TAC), 1,2,4-trivinylcyclohexane (TVCH) or any one or a combination thereof.

[0091] The resin compositions of the aforementioned embodiments can be made into various products, such as components suitable for various electronic products, including but not limited to prepregs, resin films, laminates or printed circuit boards.

[0092] For example, the resin composition of the present invention can be made into a prepreg (or prepreg).

[0093] For example, the prepreg of the present invention has a reinforcing material and a layered object disposed on the reinforcing material, and the layered object is formed by heating the aforementioned resin composition to a semi-cured state (B-stage) at a high temperature. The baking temperature for making the prepreg is, for example, between 100°C and 140°C. The reinforcing material may be a fiber material or a non-fiber material, and the reinforcing material may be in the form of any one of a woven fabric and a non-woven fabric, and the woven fabric preferably includes a glass fiber cloth. The type of glass fiber cloth is not particularly limited, and may be a commercially available glass fiber cloth that can be used for various printed circuit boards, such as an E-type glass fiber cloth, a D-type glass fiber cloth, an S-type glass fiber cloth, a T-type glass fiber cloth, an L-type glass fiber cloth, or a Q-type glass fiber cloth, wherein the types of fibers include yarns and rovings, and the forms may include open fibers or unopen fibers. 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, and is not limited thereto. The aforementioned woven fabric may also include a liquid crystal resin woven fabric, such as a polyester woven fabric or a polyurethane woven fabric, and is not limited thereto. The reinforcing material can increase the mechanical strength of the prepreg. In a preferred embodiment, the reinforcing material can also be selectively pretreated with a silane coupling agent. The prepreg is subsequently heated and cured (C-stage) to form an insulating layer.

[0094] For example, the resin compositions may be uniformly mixed to form a varnish, which is placed in an impregnation tank, and the glass fiber cloth is then immersed in the impregnation tank to allow the resin composition to adhere to the glass fiber cloth, which is then heated and baked at an appropriate temperature to a semi-cured state to obtain a semi-cured sheet.

[0095] For example, the resin composition of the present invention can be made into a resin film.

[0096] For example, in one embodiment, the resin film of the present invention is formed by baking and heating the resin composition to a semi-cured state (B-stage). For example, the resin composition can be selectively coated on a liquid crystal resin film, a polyethylene terephthalate film (PET film) or a polyimide film. For another example, the resin compositions of the various embodiments of the present invention can be coated on a copper foil respectively, so that the resin composition is evenly attached, and then heated and baked at a temperature of 100°C to 140°C for 3 to 10 minutes to form a resin film in a semi-cured state, thereby obtaining a copper foil-clad resin film.

[0097] For example, the resin composition of the present invention can be made into a laminate.

[0098] For example, in one embodiment, the laminated board of the present invention includes at least two metal foils and an insulating layer disposed between the metal foils. The insulating layer can be obtained by curing (C-stage) the aforementioned resin composition under high temperature and high pressure conditions, wherein the suitable curing temperature can be between 180°C and 240°C, preferably between 200°C and 220°C, and the curing time is 60 to 150 minutes, preferably 90 to 120 minutes. The insulating layer can be formed by curing (C-stage) the aforementioned semi-cured sheet or resin film. The metal foil can include copper, aluminum, nickel, platinum, silver, gold or their alloys, for example, the metal foil can be copper foil. In one embodiment, the laminated board is a copper clad laminate (CCL).

[0099] In addition, the aforementioned laminate can be further processed through a circuit manufacturing process to form a circuit board, such as a printed circuit board.

[0100] In one embodiment, the resin composition provided by the present invention or the product made therefrom can improve at least one of the properties including dielectric constant, dielectric loss, tensile strength on copper foil, flame resistance, glass transition temperature and PCT water absorption.

[0101] For example, in one embodiment, the resin composition provided by the present invention or the product made therefrom has one, more or all of the following characteristics:

[0102] The dielectric constant measured at a frequency of 10 GHz according to the method of JIS C2565 is less than or equal to 3.33, for example, between 3.01 and 3.33;

[0103] The dielectric loss measured at a frequency of 10 GHz according to the method of JIS C2565 is less than or equal to 0.0026, for example, between 0.0013 and 0.0026;

[0104] The copper foil tensile force measured according to IPC-TM-650 2.4.8 is greater than or equal to 3.21 lb / in, such as between 3.21 lb / in and 3.46 lb / in;

[0105] The flame retardancy measured according to the UL94 standard is V-0.

[0106] A glass transition temperature measured in accordance with IPC-TM-650 2.4.24.4 is greater than or equal to 190°C, such as between 190°C and 219°C; and

[0107] The water absorption rate measured after 5 hours of moisture absorption in a pressure cooking test according to the method of IPC-TM-650 2.6.16.1 is less than or equal to 0.28%, for example, between 0.16% and 0.28%.

[0108] Various copolymers were prepared according to the textual description of Synthesis Examples 1 to 15. In addition, various raw materials from the following sources were used to prepare the resin compositions of the embodiments of the present invention and the comparative examples of the present invention according to the amounts in Tables 1 to 5, and further prepared into various test samples.

[0109] The chemical raw materials used in the synthesis examples of copolymers, examples of resin compositions and comparative examples of resin compositions are as follows:

[0110] CP1 to CP15: phosphorus-containing copolymers having vinyl groups, as the first copolymer, as described in Synthesis Examples 1 to 15.

[0111] SA9000: polyphenylene ether resin containing methacrylate, purchased from Sabic.

[0112] DPPE-VBT50: vinyl-containing polyphenylene ether resin, purchased from First Industrial Pharmaceutical.

[0113] MIR-5000: biphenyl aralkyl type maleimide resin, purchased from Nippon Kayaku Co., Ltd.

[0114] BMI-3000: Maleimide resin with aliphatic long chain structure, purchased from Designer Molecular Company.

[0115] Ricon 100: Styrene-butadiene copolymer, available from Cray Valley.

[0116] Ricon 257: Styrene-butadiene-divinylbenzene terpolymer, available from Cray Valley.

[0117] BVPE: 1,2-bis(p-vinylphenyl)ethane, commercially available.

[0118] ESTENAMER 8012: trans-polyoctenamer rubber, available from Akrochem.

[0119] p-vinylbenzyl-DPPO: The structure is as follows, purchased from Shandong Xingshun New Materials Co., Ltd.

[0120]

[0121] p-vinylbenzyl-DOPO: The structure is as follows, purchased from Chengqi Co., Ltd.

[0122]

[0123] Vinyl-DOPO: The structure is as follows, purchased from Shandong Xingshun New Materials Co., Ltd.

[0124]

[0125] Divinylbenzene (DVB): commercially available.

[0126] The polyfunctional aromatic vinyl-containing compound has the structure shown in formula (2), as described in Synthesis Example 16.

[0127] The second copolymer: includes the structural unit represented by formula (3-1) and the structural unit represented by formula (3-2), as described in Synthesis Example 17.

[0128] SC2050: silicon dioxide, purchased from Admatechs.

[0129] Azo compound: 2,2'-azobis(2,4,4-trimethylpentane) purchased from FUJIFILM Wako Pure Chemical.

[0130] Anisole: Commercially available.

[0131] Synthesis example 1

[0132] Add p-vinylbenzyl-DPPO, 4-vinylbenzyl (triphenyl) phosphonium chloride (purchased from Shandong Xingshun New Materials Co., Ltd.), 0.5wt% of the total weight of the above raw materials, 2,2'-azobis (2,4,4-trimethylpentane) and solvent (such as dimethylacetamide, DMAc) into a three-necked flask, the solid content is about 30wt%, wherein the molar ratio of p-vinylbenzyl-DPPO to 4-vinylbenzyl (triphenyl) phosphonium chloride is 2.1:2.0. Continue stirring to obtain a mixed solution, raise the temperature of the mixed solution from room temperature to 120°C and continue stirring for 16 hours, and after purification, add 9wt% of formaldehyde, 2wt% of potassium hydroxide and an appropriate amount of tetrahydrofuran (THF) relative to the above purified product, react for 4 hours, and purify at a weight ratio of 7 / 3 for methanol / water to obtain a copolymer CP1, which is a phosphorus-containing copolymer with vinyl groups of the present invention. Copolymer CP1 includes the structural unit represented by formula (1-1) and the structural unit represented by formula (1-2), wherein R 1 is a hydrogen atom, R 2 The structure is shown in formula (1-3) and r and q are both 0, R 3 The phosphorus content of the copolymer CP1 was 7.0%, and the weight average molecular weight of the copolymer CP1 measured by GPC was about 18,900.

[0133] In this article, unless otherwise specified, the weight average molecular weight (Mw) is calculated by comparing the results of gel permeation chromatography (GPC) with standard polystyrene. The measuring device used for gel permeation chromatography is HLC-8020 chromatograph sold by TOSOH, and the columns sold by TOSOH are TSK guard column HXL-H, TSK gel GMHXL (×2) and TSK gel G2000HXL, respectively. The solvent used is tetrahydrofuran, and the measuring temperature is 40°C.

[0134] Synthesis example 2

[0135] Add p-vinylbenzyl-DOPO, divinylbenzene, 0.5 wt% of the total weight of the above raw materials, azobisisobutyronitrile (AIBN) and a solvent (such as DMAc) into a three-necked flask, the solid content is about 30 wt%, and the molar ratio of p-vinylbenzyl-DOPO to divinylbenzene is 1.2:1.0. Continue stirring to obtain a mixed solution, heat the mixed solution from room temperature to 70°C and continue stirring for 13 hours, then heat it to 110°C and continue stirring for 13 hours, and purify it to obtain copolymer CP2, which is a phosphorus-containing copolymer with vinyl groups of the present invention. Copolymer CP2 includes the structural unit shown in formula (1-1) and the structural unit shown in formula (1-2), wherein R 1 is a hydrogen atom, R 2 The structure is shown in formula (1-4), R 3 The phosphorus content of the copolymer CP2 was 7.0%, and the weight average molecular weight of the copolymer CP2 measured by GPC was about 19,100.

[0136] Synthesis example 3

[0137] Add diphenyl (vinyl) phosphine oxide (CAS No: 2096-78-8, commercially available), 4-vinylbenzyl (triphenyl) phosphonium chloride, 0.5 wt% of the total weight of the above raw materials, 2,2'-azobis (2,4,4-trimethylpentane) and solvent (such as DMAc) into a three-necked flask, the solid content is about 30 wt%, wherein the molar ratio of diphenyl (vinyl) phosphine oxide to 4-vinylbenzyl (triphenyl) phosphonium chloride is 1.5:1.0. Continue stirring to obtain a mixed solution, heat the mixed solution from room temperature to 120 ° C and continue stirring for 16 hours, after purification, add 9 wt% of formaldehyde, 2 wt% of potassium hydroxide and an appropriate amount of THF relative to the above purified product, react for 4 hours, and purify at a methanol / water weight ratio of 7 / 3 to obtain a copolymer CP3, which is a phosphorus-containing copolymer with vinyl groups of the present invention. The copolymer CP3 comprises the structural unit represented by formula (1-1) and the structural unit represented by formula (1-2), wherein R 1 is a hydrogen atom, R 2 The structure is shown in formula (1-7) and r and q are both 0, R 3 The phosphorus content of the copolymer CP3 was 9.9%, and the weight average molecular weight of the copolymer CP3 measured by GPC was about 18,900.

[0138] Synthesis example 4

[0139] Add bis(3,5-dimethylphenyl)vinylbenzyl phosphine oxide (purchased from Chengqi Co., Ltd.), 4-vinylbenzyl (triphenyl) phosphine chloride, 0.5wt% of the total weight of the above raw materials 2,2'-azobis(2,4,4-trimethylpentane) and solvent (such as DMAc) into a three-necked flask, the solid content is about 30wt%, wherein the molar ratio of bis(3,5-dimethylphenyl)vinylbenzyl phosphine oxide to 4-vinylbenzyl (triphenyl) phosphine chloride is 9.0:1.0. Continue stirring to obtain a mixed solution, raise the temperature of the mixed solution from room temperature to 120°C and continue stirring for 16 hours, and after purification, add 9wt% of formaldehyde, 2wt% of potassium hydroxide and an appropriate amount of THF relative to the above purified product, react for 4 hours, and purify at a methanol / water weight ratio of 7 / 3 to obtain a copolymer CP4, which is a phosphorus-containing copolymer with vinyl groups of the present invention. Copolymer CP4 includes the structural unit represented by formula (1-1) and the structural unit represented by formula (1-2), wherein R 1 is a hydrogen atom, R 2 The structure is shown in formula (1-3) and r and q are both 2, R 3 The phosphorus content of the copolymer CP4 was 7.1%, and the weight average molecular weight of the copolymer CP4 measured by GPC was about 1,500.

[0140] Synthesis example 5

[0141] Basically the same as Synthesis Example 1, except that the mixed solution was heated from room temperature to 140°C and stirred for 26 hours to obtain copolymer CP5, which has the same structural unit as copolymer CP1 and is a phosphorus-containing copolymer with vinyl groups of the present invention. The phosphorus content of copolymer CP5 is 7.0%, and the weight average molecular weight of copolymer CP5 measured by GPC is about 49,900.

[0142] Synthesis example 6

[0143] A compound having a structure shown in formula (4) (purchased from Hexin Chemical), 4-vinylbenzyl (triphenyl) phosphonium chloride, 0.5 wt% of the total weight of the above raw materials, and a solvent (such as DMAc) are added to a three-necked flask, and the solid content is about 30 wt%, wherein the molar ratio of the compound having a structure shown in formula (4) to 4-vinylbenzyl (triphenyl) phosphonium chloride is 5.0:1.0. Stirring is continued to obtain a mixed solution, and the mixed solution is heated from room temperature to 120°C and stirred for 16 hours. After purification, 9 wt% of formaldehyde, 2 wt% of potassium hydroxide and an appropriate amount of THF relative to the above purified product are added, and the reaction is carried out for 4 hours. Purification is carried out at a methanol / water weight ratio of 7 / 3 to obtain a copolymer CP6, which is a phosphorus-containing copolymer having a vinyl group of the present invention. Copolymer CP6 includes a structural unit shown in formula (1-1) and a structural unit shown in formula (1-2), wherein R 1 is methyl, R 2 The structure is shown in formula (1-5) and r and q are both 0, R 3 The phosphorus content of the copolymer CP6 was 9.5%, and the weight average molecular weight of the copolymer CP6 measured by GPC was about 18,900.

[0144]

[0145] Synthesis Example 7

[0146] A compound having a structure shown in formula (5) (purchased from Hexin Chemical), divinylbenzene, 0.5 wt% of the total weight of the above raw materials, and a solvent (such as DMAc) are added to a three-necked flask, and the solid content is about 30 wt%, wherein the molar ratio of the compound having a structure shown in formula (5) to divinylbenzene is 1.0:1.0. Stirring is continued to obtain a mixed solution, and the mixed solution is heated from room temperature to 70°C and stirred for 13 hours, and then heated to 110°C and stirred for 13 hours. After purification, copolymer CP7 is obtained, which is a phosphorus-containing copolymer having vinyl groups according to the present invention. Copolymer CP7 includes a structural unit shown in formula (1-1) and a structural unit shown in formula (1-2), wherein R 1 is methyl, R 2 The structure is shown in formula (1-6), R 3 The phosphorus content of the copolymer CP7 was 7.0%, and the weight average molecular weight of the copolymer CP7 measured by GPC was about 18,800.

[0147]

[0148] Synthesis example 8

[0149] Basically the same as Synthesis Example 1, except that the molar ratio of p-vinylbenzyl-DPPO to 4-vinylbenzyl (triphenyl) phosphonium chloride is changed from 2.1:2.0 to 1.3:3.0, to obtain copolymer CP8. Copolymer CP8 has the same structural unit as copolymer CP1. The phosphorus content of copolymer CP8 is 5.0%, and the weight average molecular weight of copolymer CP8 is about 18,900 as determined by GPC.

[0150] Synthesis example 9

[0151] Basically the same as Synthesis Example 2, except that the molar ratio of p-vinylbenzyl-DOPO to divinylbenzene is changed from 1.2:1.0 to 1.0:2.0, to obtain copolymer CP9. Copolymer CP9 has the same structural unit as copolymer CP2. The phosphorus content of copolymer CP9 is 5.2%, and the weight average molecular weight of copolymer CP9 measured by GPC is about 19,000.

[0152] Synthesis example 10

[0153] 4.5 g of p-vinylbenzyl-DPPO, 0.0225 g of AIBN and a solvent (e.g., DMAc) were added to a three-necked flask, with a solid content of about 30 wt %. After continuous stirring until uniform, the temperature was raised from room temperature to 120° C. and the stirring was continued for 16 hours. After purification, a homopolymer CP10 was obtained, which includes the structural unit shown in formula (1-1), wherein R 1 is a hydrogen atom, R 2 The structure is represented by formula (1-3), and r and q are both 0. The phosphorus content of the homopolymer CP10 is 9.7%, and the weight average molecular weight of the homopolymer CP10 measured by GPC is about 18,700.

[0154] Synthesis Example 11

[0155] 10 g of divinylbenzene, 0.05 g of boron trifluoride and a solvent (such as toluene) were added to a three-necked flask, with a solid content of about 30 wt %. After continuous stirring until uniform, the temperature was raised from room temperature to 90° C. and the stirring was continued for 8 hours. After purification, a homopolymer CP11 was obtained, which includes a structural unit shown in formula (1-2), wherein R 3 The phosphorus content of the homopolymer CP11 was 0%, and the weight average molecular weight of the homopolymer CP11 measured by GPC was about 18,600.

[0156] Synthesis example 12

[0157] Add p-vinylbenzyl-DPPO, styrene, 0.5 wt% of the total weight of the above raw materials, and a solvent (such as DMAc) into a three-necked flask, with a solid content of about 30 wt%, wherein the molar ratio of p-vinylbenzyl-DPPO to styrene is 0.9:1.1. Continue stirring to obtain a mixed solution, raise the temperature of the mixed solution from room temperature to 120°C and continue stirring for 16 hours, and after purification, obtain a copolymer CP12, which includes a structural unit represented by formula (1-1) and a structural unit represented by formula (1-9), wherein R 1 is a hydrogen atom, R 2 The structure is shown in formula (1-3), and r and q are both 0. The phosphorus content of the copolymer CP12 is 7.0%, and the weight average molecular weight of the copolymer CP12 measured by GPC is about 18,800.

[0158]

[0159] Synthesis example 13

[0160] The method is basically the same as Synthesis Example 1, except that the mixed solution is heated from room temperature to 140° C. and stirred for 36 hours to obtain copolymer CP13, whose structural unit is the same as copolymer CP1. The phosphorus content of copolymer CP13 is 7.0%, and the weight average molecular weight of copolymer CP13 is about 80,000 as determined by GPC.

[0161] Synthesis example 14

[0162] Basically the same as Synthesis Example 1, except that the mixed solution was stirred for 1 hour to obtain copolymer CP14, whose structural unit is the same as copolymer CP1. The phosphorus content of copolymer CP14 is 7.0%, and the weight average molecular weight of copolymer CP14 is about 500 as determined by GPC.

[0163] Synthesis Example 15

[0164] Add vinyl-DOPO, divinylbenzene, 0.5 wt% of AIBN and solvent (such as DMAc) to a three-necked flask, with a solid content of about 30 wt%, wherein the molar ratio of vinyl-DOPO to divinylbenzene is 1.0:1.0. Continue stirring to obtain a mixed solution, heat the mixed solution from room temperature to 70°C and continue stirring for 13 hours, then heat it to 110°C and continue stirring for 13 hours, and purify to obtain copolymer CP15, which is a phosphorus-containing copolymer with vinyl according to the present invention. Copolymer CP15 includes the structural unit shown in formula (1-1) and the structural unit shown in formula (1-2), wherein R 1 is a hydrogen atom, R 2 The structure is shown in formula (1-8), R 3The phosphorus content of the copolymer CP15 was 8.3%, and the weight average molecular weight of the copolymer CP15 measured by GPC was about 19,000.

[0165] Synthesis example 16

[0166] 296 parts by weight of 2-bromoethylbenzene (manufactured by Tokyo Chemical Industry Co., Ltd.), 70 parts by weight of α,α'-dichloro-p-xylene (manufactured by Tokyo Chemical Industry Co., Ltd.) and 18.4 parts by weight of methanesulfonic acid (manufactured by Tokyo Chemical Industry Co., Ltd.) were reacted at 130°C for 8 hours, cooled to room temperature, neutralized with sodium hydroxide aqueous solution, and extracted with 1,200 parts by weight of toluene. The organic layer was washed with water. The solvent and excess 2-bromoethylbenzene were distilled off under heating and reduced pressure to obtain an intermediate product. Among them, the molar ratio of 2-bromoethylbenzene to α,α'-dichloro-p-xylene can be 4:1; methanesulfonic acid is used as an acidic catalyst, and can be replaced by other acidic catalysts such as hydrochloric acid and phosphoric acid; the reaction conditions can be 40°C to 180°C for 0.5 to 20 hours.

[0167] 22 parts by weight of the intermediate product, 50 parts by weight of toluene (other aromatic solvents such as xylene may also be used), 150 parts by weight of dimethyl sulfoxide (other aprotic polar solvents such as dimethyl sulfone may also be used), 15 parts by weight of water and 5.4 parts by weight of sodium hydroxide (other alkaline catalysts such as potassium hydroxide and potassium carbonate may also be used) are reacted at 40°C for 5 hours, cooled to room temperature, and then 100 parts by weight of toluene is added. The organic layer is washed with water, and the solvent is distilled off under heating and reduced pressure to obtain a polyfunctional aromatic vinyl-containing compound having a structure shown in formula (2).

[0168] Synthesis Example 17

[0169] Add p-vinylbenzyl-DPPO, N-(2,6-xylyl)maleimide (commercially available), 0.5wt% of the total weight of the above raw materials, and a solvent (such as DMAc) into a three-necked flask, with a solid content of about 30wt%, wherein the molar ratio of p-vinylbenzyl-DPPO to N-(2,6-xylyl)maleimide is 2.0:1.0. Continue stirring to obtain a mixed solution, heat the mixed solution from room temperature to 120°C and continue stirring for 16 hours, and purify to obtain a second copolymer, which includes the structural unit shown in formula (3-1) and the structural unit shown in formula (3-2). The phosphorus content of the second copolymer is 7.4%, and the weight average molecular weight of the second copolymer determined by GPC is about 18,000.

[0170] The resin composition compositions (all in parts by weight) and characteristic tests of the embodiments and comparative examples are shown below, wherein parts by weight refer to the parts by weight when the solid content of each component added in each set of embodiments or comparative examples is 100%. For example, embodiment E1 uses 55 parts by weight of copolymer CP1, which means that 55 parts by weight of copolymer CP1 with a solid content of 100% is used. In addition, not all of CP1 to CP15 are copolymers, for example, CP10 and CP11 are homopolymers, but for the convenience of comparison, they are collectively referred to as copolymers and are all listed under the field of the first copolymer.

[0171] [Table 1] Composition (unit: weight parts) and property tests of the resin composition of the embodiment

[0172]

[0173]

[0174] [Table 2] Composition (unit: weight parts) and characteristic tests of the resin composition of the embodiment

[0175]

[0176]

[0177] [Table 3] Composition (unit: weight parts) and characteristic tests of the resin composition of the embodiment

[0178]

[0179] [Table 4] Composition (unit: weight parts) and characteristic tests of comparative resin compositions

[0180]

[0181] [Table 5] Composition (unit: weight parts) and property tests of comparative resin compositions

[0182]

[0183]

[0184] On the other hand, for the products CP1 to CP15 obtained in Synthesis Examples 1 to 15, their dielectric loss and solvent compatibility can be measured or evaluated respectively in the following manners.

[0185] Dielectric loss: Add any one of CP1 to CP15 and solvent DMAc into a stirring tank and mix them evenly to form a varnish. Place the varnish in an impregnation tank, and then immerse a glass fiber cloth (e.g., L-glass fiber cloth with a specification of 1078, purchased from Asahi) in the impregnation tank to attach each copolymer to the glass fiber cloth, and then heat it at 100°C to 140°C to a semi-cured state (B-Stage) to obtain a prepreg, whose resin content is about 70%. Prepare two HVLP (hyper very low profile) copper foils with a thickness of 0.5 ounces and two of the above prepregs, and stack them in the order of copper foil, two prepregs, and copper foil, and press them for 90 minutes to 120 minutes under vacuum conditions, a pressing pressure of 250psi to 600psi, and a temperature of 200°C to 220°C to form a copper-containing substrate. The copper-containing substrate is etched to remove the copper foil on both sides to obtain a copper-free substrate. The copper-free substrate is selected as the test sample, and a microwave dielectrometer (purchased from Japan AET Company) is used to measure each test sample at room temperature (about 25°C) and a frequency of 10 GHz according to the method described in JIS C2565 to obtain the dielectric loss.

[0186] Solvent compatibility: Place any one of CP1 to CP15 and a mixed solvent (butyl ethyl ketone / toluene) in a transparent glass bottle at a weight ratio of 1:5 and stir evenly. Leave it at room temperature (about 25°C) for 24 hours and observe visually whether there is precipitation. If precipitation is produced, it is marked as "incompatible", indicating that the solvent compatibility is poor; conversely, if there is no precipitation, it is marked as "compatible", indicating that the solvent compatibility is good.

[0187] The test results of dielectric loss and solvent compatibility are shown in Table 6.

[0188] [Table 6] Test results of dielectric loss and solvent compatibility

[0189]

[0190] It can be observed from Table 6 that the phosphorus-containing copolymers having vinyl groups (e.g., CP1-CP7, CP15) or products made therefrom of the present invention have a dielectric loss of less than or equal to 0.0025 measured at a frequency of 10 GHz according to the method described in JIS C2565 and have good solvent compatibility. On the other hand, other polymers (e.g., CP8-CP14) cannot simultaneously satisfy the above good properties.

[0191] In addition, for the resin compositions of the aforementioned embodiments and comparative examples, various properties listed in Tables 1 to 5 can be measured. The aforementioned properties are prepared by preparing the test object (sample) in the following manner, and then the properties are analyzed according to specific conditions.

[0192] 1. Prepreg (PP)

[0193] The resin compositions of the embodiments and comparative examples (in parts by weight) were respectively used, and each component of the resin composition was added into a stirring tank and mixed evenly to form a varnish. The varnish was placed into an impregnation tank, and then a glass fiber cloth (e.g., L-glass fiber cloth with a specification of 1078, purchased from Asahi) was immersed in the impregnation tank to make the resin composition adhere to the glass fiber cloth, and then heated at 100° C. to a semi-cured state (B-Stage) to obtain a semi-cured sheet, whose resin content was about 70%.

[0194] 2. Copper-containing substrate 1 (made of two prepreg sheets pressed together)

[0195] Prepare two 0.5 ounce HVLP (hyper very low profile) copper foils and two 1078-gauge L-glass fiber cloths impregnated with the prepregs made from the samples to be tested (each set of embodiments or each set of comparative examples), and the resin content of each prepreg is about 70%. The copper foil, two prepregs, and copper foil are stacked in the order of lamination, and pressed for 90 minutes to 120 minutes under vacuum conditions, a lamination pressure of 250 psi to 600 psi, and a temperature of 200° C. to 220° C. to form a copper-containing substrate 1. The two prepregs are cured to form an insulating layer between the two copper foils, and the resin content of the insulating layer is about 70%.

[0196] 3. Copper-containing substrate 2 (made of six prepreg sheets pressed together)

[0197] The preparation method is basically the same as that of the copper-containing substrate 1, except that the insulating layer is composed of six prepreg sheets.

[0198] 4. Copper-containing substrate 3 (made of eight prepreg sheets pressed together)

[0199] The preparation method is basically the same as that of the copper-containing substrate 1, except that the insulating layer is composed of eight prepreg sheets.

[0200] 5. Copper-containing substrate 4 (made of twelve prepreg sheets pressed together)

[0201] The preparation method is basically the same as that of the copper-containing substrate 1, except that the insulating layer is composed of twelve prepreg sheets.

[0202] 6. Copper-free substrate 1 (made of two prepregs pressed together)

[0203] The copper-containing substrate 1 formed by pressing two prepregs is etched to remove the copper foils on both sides, thereby obtaining a copper-free substrate 1 (formed by pressing two prepregs).

[0204] 7. Copper-free substrate 2 (made of eight prepreg sheets pressed together)

[0205] The copper-containing substrate 3 formed by pressing eight prepregs is etched to remove the copper foil on both sides, thereby obtaining a copper-free substrate 2 (formed by pressing eight prepregs).

[0206] 8. Copper-free substrate 3 (made of twelve prepreg sheets pressed together)

[0207] The copper-containing substrate 4 formed by pressing twelve prepregs is etched to remove the copper foil on both sides, thereby obtaining a copper-free substrate 3 (formed by pressing twelve prepregs).

[0208] For the above-mentioned samples to be tested, the test methods and their characteristic analysis items are described as follows:

[0209] Dielectric constant (Dk)

[0210] In the measurement of the dielectric constant, the above-mentioned copper-free substrate 1 (made of two semi-cured sheets pressed together, with a resin content of about 70%) was selected as the sample to be tested. A microwave dielectrometer (purchased from AET Company of Japan) was used to measure each sample to be tested at room temperature (about 25°C) and at a frequency of 10 GHz, referring to the method described in JIS C2565, to obtain the dielectric constant. The lower the dielectric constant, the better the dielectric properties of the sample to be tested. At a measurement frequency of 10 GHz, for low dielectric constant materials, a difference in Dk values ​​less than 0.10 means that there is no significant difference in the dielectric constants of different substrates (there is no significant technical difficulty), and a difference in Dk values ​​greater than or equal to 0.10 means that there is a significant difference between the dielectric constants of different substrates (there is a significant technical difficulty).

[0211] Dielectric loss (dissipation factor, Df)

[0212] In the measurement of dielectric loss, the above-mentioned copper-free substrate 1 (made of two semi-cured sheets pressed together, with a resin content of about 70%) was selected as the sample to be tested. A microwave dielectrometer (purchased from AET Company of Japan) was used to measure each sample to be tested at room temperature (about 25°C) and at a frequency of 10 GHz, referring to the method described in JIS C2565, to obtain the dielectric loss. At a measurement frequency of 10 GHz and a Df value ranging from 0.0010 to 0.0030, a difference in Df value of less than 0.0010 indicates that there is no significant difference in the dielectric loss of the substrate (there is no significant technical difficulty), and a difference in Df value greater than or equal to 0.0010 indicates that there is a significant difference between the dielectric losses of different substrates (there is a significant technical difficulty).

[0213] Copper foil pull (0.5 oz peeling strength, 0.5 oz P / S)

[0214] Prepare a copper-containing substrate 2 (made of six prepregs pressed together), cut into a rectangular sample with a width of 24 mm and a length of 80 mm, and etch the surface copper foil, leaving only a long strip of copper foil with a width of 3.18 mm and a length greater than 60 mm. Use a universal tensile strength tester to measure at room temperature (about 25°C) with reference to the method described in IPC-TM-650 2.4.8, and measure a 0.5 ounce (half-ounce) copper foil tensile force (0.5oz P / S) in lb / in. In this field, the higher the copper foil tensile force, the better.

[0215] Flame resistance

[0216] Prepare a copper-free substrate 2 (composed of eight prepreg sheets laminated together) as the sample to be tested. According to the UL94 standard method, the flame retardancy analysis results are expressed in V-0, V-1, and V-2 grades, where V-0 has better flame retardancy than V-1, V-1 has better flame retardancy than V-2, and the sample burnout is the worst.

[0217] Glass transition temperature (Tg)

[0218] Prepare a copper-free substrate 3 (composed of twelve prepreg sheets laminated together) as a sample to be tested for dynamic mechanical analysis (DMA), heat the sample at a heating rate of 2°C per minute, and measure the glass transition temperature (in °C) of each sample to be tested in accordance with the method described in IPC-TM-650 2.4.24.4. The higher the glass transition temperature, the better the sample characteristics.

[0219] Pressure Cooking (PCT) Water Absorption

[0220] A copper-free substrate 1 (made of two prepregs pressed together) with a length of 2 inches and a width of 2 inches was selected as the sample to be tested. Each sample to be tested was placed in an oven at 105±10°C for baking for 1 hour and then taken out. After cooling at room temperature (about 25°C) for 10 minutes, the weight of the copper-free substrate was weighed as W1. Then, according to the method described in IPC-TM-650 2.6.16.1, a pressure cooking test (PCT) was performed to absorb moisture for 5 hours (test temperature 121°C and relative humidity 100%), and the water remaining on the surface of the substrate was wiped dry. After wiping dry, the weight obtained was the weight of the copper-free substrate after water absorption, which was W2. The pressure cooking (PCT) water absorption was calculated according to the formula: water absorption rate W (%) = ((W2-W1) / W1) × 100%, and the unit of water absorption rate was %. The lower the pressure cooking water absorption rate, the better the sample characteristics.

[0221] By referring to the test results in Tables 1 to 5, the following phenomena can be clearly observed.

[0222] Compared with Examples E1 to E16 in which the resin composition contains the phosphorus-containing copolymer with vinyl group of the present invention, Comparative Examples C1 to C8 use other polymers or monomers, and at least one of their properties such as dielectric constant, dielectric loss, copper foil tensile force, flame retardancy, glass transition temperature, and PCT water absorption cannot achieve satisfactory results.

[0223] Compared with Comparative Examples C1 to C8, Examples E1 to E16 using the phosphorus-containing copolymer having a vinyl group of the present invention can simultaneously achieve a better dielectric constant (the dielectric constant measured at a frequency of 10 GHz by the method of JIS C2565 is less than or equal to 3.33), a lower dielectric loss (the dielectric loss measured at a frequency of 10 GHz by the method of JIS C2565 is less than or equal to 0.0026), a higher tensile force on copper foil (the tensile force on copper foil measured by the method of IPC-TM-650 2.4.8 is greater than or equal to 3.21 lb / in), better flame retardancy (the flame retardancy measured by the method of UL94 specification reaches V-0 grade), a more excellent glass transition temperature (the glass transition temperature measured by the method of IPC-TM-650 2.4.24.4 is greater than or equal to 190°C) and PCT water absorption (measured by the method of IPC-TM-650 2.4.24.4). The water absorption rate measured after 5 hours of pressure cooking test according to method 2.6.16.1 is less than or equal to 0.28%).

[0224] In addition, by observing the test results of Examples E10 to E15, it can be found that if the resin composition further includes a multifunctional aromatic vinyl-containing compound or the second copolymer disclosed in the present invention, further improvements can be obtained in at least one or more of the aforementioned properties, such as but not limited to the glass transition temperature.

[0225] The above embodiments are essentially only for auxiliary explanation and are not intended to limit the embodiments of the application object or the application or use of such embodiments. In this article, the term "exemplary" means "as an example, example or illustration". Any exemplary embodiment in this article is not necessarily interpreted as being more preferred or more advantageous than other embodiments.

[0226] In addition, although at least one exemplary embodiment or comparative example has been proposed in the aforementioned embodiments, it should be understood that the present invention can still have a large number of variations. It should also be understood that the embodiments described herein are not intended to limit the scope, use or configuration of the requested application subject matter in any way. On the contrary, the aforementioned embodiments will provide a simple guide for those skilled in the art to implement the one or more embodiments described. Furthermore, various changes can be made to the functions and arrangements of the components without departing from the scope defined by the claims, and the claims include known equivalents and all foreseeable equivalents at the time of filing the present patent application.

Claims

1. A phosphorus-containing copolymer having a vinyl group, characterized in that comprising a structural unit represented by formula (1-1) and a structural unit represented by formula (1-2), in: m and n each independently represent the number of repetitions of the unit in the brackets, such that the weight average molecular weight of the phosphorus-containing copolymer having vinyl groups is between 1,000 and 50,000; R1 and R3 are each independently a hydrogen atom or a C1 to C3 alkyl group; and R2 is a monovalent functional group selected from any one of formula (1-3) to formula (1-8), wherein r and q are each independently an integer from 0 to 3; And the phosphorus content of the phosphorus-containing copolymer having vinyl groups is greater than or equal to 7%.

2. A resin composition, characterized in that The resin composition comprises 100 parts by weight of a vinyl-containing polyphenylene ether resin and 55 to 80 parts by weight of the phosphorus-containing copolymer having a vinyl group as claimed in claim 1 .

3. The resin composition according to claim 2, characterized in that The resin composition further includes a polyfunctional aromatic vinyl-containing compound.

4. The resin composition according to claim 3, characterized in that The resin composition includes 5 to 25 parts by weight of the polyfunctional aromatic vinyl-containing compound.

5. The resin composition according to claim 3, characterized in that The polyfunctional aromatic vinyl-containing compound has a structure shown in the following formula (2): Where w is between 1 and 20.

6. The resin composition according to claim 2, characterized in that The phosphorus-containing copolymer having a vinyl group is used as a first copolymer, and the resin composition further includes a second copolymer, wherein the second copolymer includes a structural unit represented by formula (3-1) and a structural unit represented by formula (3-2), wherein x and y each independently represent the number of repetitions of the unit in the brackets, such that the weight average molecular weight of the second copolymer is between 1,000 and 30,000; and The second copolymer has a phosphorus content greater than or equal to 7%.

7. The resin composition according to claim 6, characterized in that The resin composition includes 5 to 10 parts by weight of the second copolymer.

8. The resin composition according to claim 2, characterized in that The resin composition further includes an inorganic filler, a hardening accelerator, a flame retardant, an inhibitor, a solvent, a silane coupling agent, a colorant, a toughening agent or a combination thereof.

9. A product made from the resin composition according to claim 2, characterized in that: The product includes a prepreg, a resin film, a laminate or a printed circuit board.

10. The article according to claim 9, characterized in that The dielectric constant of the product measured at a frequency of 10 GHz according to the method of JIS C2565 is less than or equal to 3.

33.

11. The article according to claim 9, characterized in that The dielectric loss of the product measured at a frequency of 10 GHz according to the method of JIS C2565 is less than or equal to 0.0026.

12. The article of claim 9, wherein: The copper foil tensile force of the product measured by the method of IPC-TM-6502.4.8 is greater than or equal to 3.21 lb / in.

13. The article of claim 9, wherein: The flame retardancy of the product measured according to the method of UL94 specification reaches V-0 grade.

14. The article of claim 9, wherein: The glass transition temperature of the product measured by referring to the method of IPC-TM-6502.4.24.4 is greater than or equal to 190°C.

15. The article of claim 9, wherein: The product is subjected to a pressure cooking test according to the method of IPC-TM-6502.6.16.1 and the water absorption rate measured after 5 hours of moisture absorption is less than or equal to 0.28%.

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