Resin composition and product thereof

Abstract

Disclosed is a resin composition comprising 100 parts by weight of a vinyl-containing resin and 35-65 parts by weight of a phosphorus-containing compound having a structure represented by formula (1). The resin composition can be made into various products, including resin films, prepregs, laminates or printed circuit boards, and has improved one or more of dielectric loss, tensile force to copper foil, flame resistance, X-axis thermal expansion coefficient, and other characteristics.

Description

TECHNICAL FIELD

[0001] The present invention relates to a resin composition, and in particular, to a resin composition that can be used to manufacture prepreg, resin film, laminate or printed circuit board. BACKGROUND

[0002] In recent years, with the development of electronic signal transmission towards 5G, and the high functionality and miniaturization of electronic devices, communication devices, personal computers, etc., the circuit boards used in these applications are also developing towards multi-layer, high-density wiring and high-speed signal transmission, and higher requirements are placed on the comprehensive performance of circuit substrates such as copper foil substrates.

[0003] Accordingly, there is a need to propose a novel material that can meet the current characteristics requirements of circuit boards. SUMMARY

[0004] In view of the problems encountered in the prior art, in particular the fact that the existing materials cannot meet one or more characteristic requirements, the main purpose of the present invention is to provide a resin composition and an article made of the resin composition, so that at least one or more characteristics such as dielectric loss, copper foil tensile force, flame resistance and X-axis thermal expansion coefficient are improved.

[0005] In order to achieve the above-mentioned purpose, the present invention discloses a resin composition comprising 100 parts by weight of a vinyl-containing resin and 35 to 65 parts by weight of a phosphorus-containing compound, wherein the phosphorus-containing compound has a structure represented by formula (1):

[0006]

[0007] In formula (1), R1 to R6 are each independently hydrogen or C1 to C3 alkyl, Q1 is each independently a -(C=O)- group or a *-CH2-C6H4- group, wherein * represents a bond to an oxygen atom, and G is each independently a monovalent phosphorus-containing group represented by formula (2) or formula (3);

[0008]

[0009] In formula (2), n1 and n2 are each independently an integer of 0 to 3, and R7 and R8 are each independently C1 to C3 alkyl.

[0010] For example, in an embodiment, the vinyl-containing resin comprises a vinyl-containing polyphenylene ether resin, a maleimide resin, di(vinylphenyl)ethane, a compound having a structure represented by formula (4), a styrene-butadiene copolymer, an ethylene propylene diene rubber, a diene-containing fluorene compound, a di-vinylbenzene-terminated hydrogenated polybutadiene resin, or a combination thereof,

[0011] wherein m is 1 to 20.

[0012] For example, in an embodiment, the resin composition further includes a 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide substituted with a vinylbenzyl group. For example, in an embodiment, the content of the 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide substituted with a vinylbenzyl group is 10 to 15 parts by weight, compared to 100 parts by weight of the vinyl group-containing resin.

[0013] For example, in an embodiment, the resin composition further includes an inorganic filler, a curing accelerator, a flame retardant, a polymerization inhibitor, a solvent, a silane coupling agent, a surfactant, a dyeing agent, a toughening agent, or a combination thereof.

[0014] Further, the present application also provides an article (or can be referred to as an object) made of the aforementioned resin composition, which includes a prepreg, a resin film, a laminate, or a printed circuit board.

[0015] For example, in an embodiment, the aforementioned article has one, more, or all of the following properties:

[0016] a dielectric loss of less than or equal to 0.0036, measured at a frequency of 10 GHz according to the method described in JIS C2565;

[0017] a copper foil pull strength of greater than or equal to 3.23 lb / in, measured according to the method described in IPC-TM-650 2.4.8;

[0018] a flame resistance of V-0 rating, measured according to the method described in UL94 specification; and

[0019] an X-axis coefficient of thermal expansion of less than or equal to 14.1 ppm / °C, measured according to the method described in IPC-TM-650 2.4.24.5. DETAILED DESCRIPTION

[0020] To enable persons skilled in the art to understand the features and effects of the present application, the following is a general description and definition of the terms and phrases mentioned in the specification and claims. Unless otherwise specified, all technical and scientific words used in the text have their usual meanings understood by those skilled in the art of the present application, and in the event of a conflict, the definitions in the specification shall prevail.

[0021] Theories or mechanisms described and disclosed herein, whether correct or not, should not be considered limiting on the scope of the present application, that is, the present application can be implemented without regard to any particular theory or mechanism.

[0022] As used herein, the singular forms "a", "an" and "the" include plural referents unless the context clearly dictates otherwise. The terms "comprises", "comprising", "includes", "including" and "have" or "having", as used herein, are specifically intended to be open-ended transitional phrases, and do not preclude the presence of other elements or materials. For example, a composition containing elements A, B and C can be specifically stated as including elements A, B, and C, and can also include other elements, whether or not listed. In addition, the use of "or" means "and / or" unless clearly indicated otherwise. For example, a condition A or B is satisfied by any one of the following: A is true (or present) and B is false (or not present), A is false (or not present) and B is true (or present), and both A and B are true (or present). Also, the interpretation "includes", "including", "has" or "having" should be considered as specifically disclosed and also covering the closed or semi-closed phrases "consisting of and "consisting essentially of.

[0023] As used herein, the singular forms "a", "an" and "the" include plural referents unless the context clearly dictates otherwise. The terms "comprises", "comprising", "includes", "including" and "have" or "having", as used herein, are specifically intended to be open-ended transitional phrases, and do not preclude the presence of other elements or materials. For example, a composition containing elements A, B and C can be specifically stated as including elements A, B, and C, and can also include other elements, whether or not listed. In addition, the use of "or" means "and / or" unless clearly indicated otherwise. For example, a condition A or B is satisfied by any one of the following: A is true (or present) and B is false (or not present), A is false (or not present) and B is true (or present), and both A and B are true (or present). Also, the interpretation "includes", "including", "has" or "having" should be considered as specifically disclosed and also covering the closed or semi-closed phrases "consisting of and "consisting essentially of.

[0024] As used herein, the singular forms "a", "an" and "the" include plural referents unless the context clearly dictates otherwise. The terms "comprises", "comprising", "includes", "including" and "have" or "having", as used herein, are specifically intended to be open-ended transitional phrases, and do not preclude the presence of other elements or materials. For example, a composition containing elements A, B and C can be specifically stated as including elements A, B, and C, and can also include other elements, whether or not listed. In addition, the use of "or" means "and / or" unless clearly indicated otherwise. For example, a condition A or B is satisfied by any one of the following: A is true (or present) and B is false (or not present), A is false (or not present) and B is true (or present), and both A and B are true (or present). Also, the interpretation "includes", "including", "has" or "having" should be considered as specifically disclosed and also covering the closed or semi-closed phrases "consisting of and "consisting essentially of.

[0025] As used herein, the singular forms "a", "an" and "the" include plural referents unless the context clearly dictates otherwise. The terms "comprises", "comprising", "includes", "including" and "have" or "having", as used herein, are specifically intended to be open-ended transitional phrases, and do not preclude the presence of other elements or materials. For example, a composition containing elements A, B and C can be specifically stated as including elements A, B, and C, and can also include other elements, whether or not listed. In addition, the use of "or" means "and / or" unless clearly indicated otherwise. For example, a condition A or B is satisfied by any one of the following: A is true (or present) and B is false (or not present), A is false (or not present) and B is true (or present), and both A and B are true (or present). Also, the interpretation "includes", "including", "has" or "having" should be considered as specifically disclosed and also covering the closed or semi-closed phrases "consisting of and "consisting essentially of.

[0026] In this document, all features or conditions of a numerical range or a percentage range are presented only for simplicity and convenience. Accordingly, the description of a numerical range or a percentage range should be considered to have encompassed and specifically disclosed all possible sub-ranges and individual numerical values within the range, particularly the integer numerical values. For example, the description of a range of "1 to 8" should be considered to have specifically disclosed all sub-ranges such as 1 to 7, 2 to 8, 2 to 6, 3 to 6, 4 to 8, 3 to 8, etc., particularly the sub-ranges defined by all integer numerical values, and to have specifically disclosed individual numerical values within the range such as 1, 2, 3, 4, 5, 6, 7, 8, etc. Similarly, the description of a range of "between 1 and 8" should be considered to have specifically disclosed all ranges such as 1 to 8, 1 to 7, 2 to 8, 2 to 6, 3 to 6, 4 to 8, 3 to 8, etc., including the end points. The foregoing interpretation method applies to all aspects of the present application, regardless of the breadth of the range, unless otherwise indicated.

[0027] If an amount or other numerical or percentage value is expressed in a range, preferably a range, or a series of upper and lower limits, it should be understood that all ranges formed by any pair of an upper limit or a preferred value of the range and a lower limit or a preferred value of the range have been specifically disclosed herein, whether or not the ranges are separately disclosed. In addition, if a range of values is referred to herein, the range is inclusive of its endpoints and all integers and fractions within the range, unless otherwise indicated.

[0028] In this document, numerical values should be construed either to have the accuracy indicated, or to the accuracy appropriate to the number of significant figures used following the rules of significant figure arithmetic, to the extent that such rules are agreed upon in the art, to the extent that such rules are not so agreed upon, then to the accuracy within one unit in the last expressed digit of the numerical value. For example, the number 40.0 should be understood to encompass a range from 39.50 to 40.49.

[0029] In this document, for situations in which Markush groups or option language is used to describe a feature or example of the application, one of ordinary skill in the art will understand that the subgroups of all members of the Markush group or option list or any subset thereof can be used to describe the application. For example, if X is described as "selected from the group consisting of X1, X2, and X3," it is intended that X be understood as having been specifically disclosed as X1, and as X1 and / or X2 and / or X3. Furthermore, for situations in which Markush groups or option language is used to describe a feature or example of the application, one of ordinary skill in the art will understand that the subgroups of all members of the Markush group or option list or any combination of individual members can be used to describe the application. Accordingly, for example, if X is described as "selected from the group consisting of X1, X2, and X3," and Y is described as "selected from the group consisting of Y1, Y2, and Y3," it is intended that X be understood as having been specifically disclosed as X1 or X2 or X3 and Y as Y1 or Y2 or Y3.

[0030] Unless otherwise specified, in the present application, a compound refers to a chemical substance formed by two or more elements connected by chemical bonds, and includes small molecule compounds and high molecular compounds, and is not limited thereto. In the present application, a compound is not limited to a single chemical substance, but can be interpreted as a same kind of chemical substances having the same component or having the same property. In addition, in the present application, a mixture refers to a combination of two or more compounds.

[0031] Unless otherwise specified, in the present application, a polymer refers to a product formed by polymerization of monomers, and often includes many high molecular aggregates, each of which is formed by repeating connection of many simple structural units by covalent bonds, and the monomer is a compound for synthesizing a polymer. The polymer can include a homopolymer, a copolymer, a prepolymer, and the like, and is not limited thereto. The homopolymer refers to a polymer formed by polymerization of one monomer. The copolymer refers to a polymer formed by polymerization of two or more monomers. The copolymer includes a random copolymer (structure is, for example, -AABABBBAAABBA-), an alternating copolymer (structure is, for example, -ABABABAB-), a graft copolymer (structure is, for example, -AA(A-BBBB)AA(A-BBBB)AAA-), and a block copolymer (structure is, for example, -AAAAA-BBBBBB-AAAAA-), and the like. The polymer certainly includes an oligomer, and is not limited thereto. The oligomer, also called an oligomer, is a polymer composed of 2 to 20 repeating units, and is usually a polymer composed of 2 to 5 repeating units.

[0032] Unless otherwise specified, in the present application, "resin" is a conventional designation of a synthetic polymer, and in the interpretation, can include a monomer, a polymer thereof, a combination of monomers, a combination of polymers thereof, or a combination of a monomer and a polymer thereof, and the like, and is not limited thereto.

[0033] Unless otherwise specified, in the present application, a modified product (also called a modified substance) includes a product after modification of a reaction functional group of each resin, a product after prepolymerization of each resin with other resins, a product after crosslinking of each resin with other resins, a product after homopolymerization of each resin, a product after copolymerization of each resin with other resins, and the like.

[0034] In the present application, "vinyl group-containing" refers to a compound having a carbon-carbon double bond (C=C) or a derivative functional group thereof in the structure. Therefore, examples of the vinyl group-containing can include, but are not limited to, a functional group having a vinyl group, a styryl group, an allyl group, a vinylbenzyl group, a methacrylate group, and the like in the structure. Unless otherwise specified, the position of the aforementioned functional group is not particularly limited, and for example, can be located at the end of a long chain structure. Therefore, for example, the vinyl group-containing resin can represent a resin having a functional group such as a vinyl group, a styryl group, an allyl group, a vinylbenzyl group, or a methacrylate group, and is not limited thereto.

[0035] In the present disclosure, parts by weight represent parts of weight, which can be any unit of weight, such as but not limited to, grams, kilograms, pounds, and the like. For example, 100 parts by weight of a vinyl-containing resin means that it can be 100 grams of a vinyl-containing resin, 100 kilograms of a vinyl-containing resin, or 100 pounds of a vinyl-containing resin, and the like. In the present disclosure, if the amount of different ingredients is presented in a proportional relationship, the actual amount thereof can be any amount that conforms to the proportional relationship.

[0036] The following detailed description is merely illustrative in nature and is not intended to limit the application or the use of embodiments of the application. Furthermore, there is no intention to be bound by any theory of operation described in the preceding background or the following detailed description or summary or the following examples.

[0037] As described above, the main object of the present application is to provide a resin composition including 100 parts by weight of a vinyl-containing resin and 35 to 65 parts by weight of a phosphorus-containing compound, wherein the phosphorus-containing compound has a structure represented by Formula (1):

[0038]

[0039] In Formula (1), R1to R6are each independently hydrogen or a C1to C3alkyl group (such as but not limited to, a methyl group, an ethyl group, a n-propyl group, or an i-propyl group), Q1is each independently a -(C=O)- group (i.e., a carbonyl group) or a *-CH2-C6H4- group, wherein * represents a bond to an oxygen atom, and G is each independently a monovalent phosphorus-containing group represented by Formula (2) or Formula (3).

[0040]

[0041] In Formula (2), n1and n2are each independently an integer of 0 to 3, and R7and R8are each independently a C1to C3alkyl group (such as but not limited to, a methyl group, an ethyl group, a n-propyl group, or an i-propyl group).

[0042] For example, in one embodiment, the phosphorus-containing compound includes a compound represented by Formula (1-1), a compound represented by Formula (1-2), a compound represented by Formula (1-3), a compound represented by Formula (1-4), or a combination thereof.

[0043]

[0044]

[0045] In the resin composition of the present application, the content of the phosphorus-containing compound is 35 to 65 parts by weight, such as but not limited to, 35 parts by weight, 40 parts by weight, 45 parts by weight, 50 parts by weight, 55 parts by weight, 60 parts by weight, or 65 parts by weight, relative to 100 parts by weight of the vinyl-containing resin.

[0046] For example, in an embodiment, the vinyl-containing resin comprises a vinyl- containing polyphenylene ether resin, a maleimide resin, di(vinylphenyl)ethane, the aforementioned compound having the structure shown in Formula (4), a styrene- butadiene copolymer, an ethylene propylene diene rubber, a diene-containing fluorene compound, a divinylbenzene-terminated hydrogenated polybutadiene resin, or a combination thereof.

[0047] The aforementioned vinyl-containing polyphenylene ether resin can include, but is not limited to, a polyphenylene ether resin containing a vinyl group, an allyl group, a vinylbenzyl group, or a methacrylate ester. For example, in an embodiment, the aforementioned vinyl- containing polyphenylene ether resin comprises a vinylbenzyl biphenyl polyphenylene ether resin, a methacrylate polyphenylene ether resin (i.e., a methacryloyl polyphenylene ether resin), an allyl polyphenylene ether resin, a vinylbenzyl-modified bisphenol A polyphenylene ether resin, a vinyl-extended polyphenylene ether resin, or a combination thereof. For example, the aforementioned vinyl-containing polyphenylene ether resin can be a terminal vinylbenzyl polyphenylene ether resin having a number average molecular weight of about 1200 (e.g., OPE-2st 1200, available from Mitsubishi Gas Chemical Company), a terminal vinylbenzyl polyphenylene ether resin having a number average molecular weight of about 2200 (e.g., OPE-2st 2200, available from Mitsubishi Gas Chemical Company), a methacrylate-containing polyphenylene ether resin having a number average molecular weight of about 1900 to 2300 (e.g., SA9000, available from Sabic), a vinylbenzyl-modified bisphenol A polyphenylene ether resin having a number average molecular weight of about 2400 to 2800, a vinyl-extended polyphenylene ether resin having a number average molecular weight of about 2200 to 3000, or a combination thereof. Among others, the aforementioned vinyl-extended polyphenylene ether resin can include the various types of polyphenylene ether resins disclosed in U.S. Patent Application Publication No. 2016 / 0185904 Al, which is incorporated herein by reference in its entirety.

[0048] The aforementioned maleimide resin can include 4,4'-diphenylmethane bismaleimide, polyphenylmethane maleimide (or oligomer of phenylmethane maleimide), bisphenol A diphenyl ether bismaleimide, 3,3'-dimethyl-5,5'-diethyl-4,4'-diphenylmethane bismaleimide, 3,3'-dimethyl-5,5'-dipropyl-4,4'-diphenyl methane bismaleimide, m-phenylene bismaleimide, 4-methyl-1,3-phenylene bismaleimide, 1,6-bismaleimide-(2,2,4-trimethyl)hexane, N-2,3-xylylmaleimide, N-2,6-xylylmaleimide, N-phenylmaleimide, vinyl benzyl maleimide (VBM), a maleimide containing a biphenyl structure, a maleimide resin containing an aliphatic long chain structure, a prepolymer of a diallyl compound and a maleimide resin, a prepolymer of a polyfunctional amine and a maleimide resin (the polyfunctional amine includes two or more amine functional groups), a prepolymer of an acidic phenol compound and a maleimide resin, or a combination thereof. Modifications of these components are also included in the interpretation.

[0049] For example, examples of the maleimide resin include, but are not limited to, maleimide resins produced by Daiwakasei Industry Co., Ltd. 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 maleimide resins produced by K.I Chemical Co., Ltd. under the trade names of BMI-70, BMI-80, or maleimide resins produced by Japan Chemicals Co., Ltd. under the trade names of MIR-3000 or MIR-5000, and the like. For example, examples of the maleimide resin containing an aliphatic long chain structure (e.g., containing C5 to C 50 Examples of the maleimide resin containing an aliphatic long chain structure (e.g., containing C5 to C

[0050] For example, in an embodiment, the aforementioned di(vinylphenyl)ethane includes, but is not limited to, 1,2-bis(4-vinylphenyl)ethane, 1,2-(3-vinylphenyl-4-vinylphenyl)ethane, 1,2-bis(3-vinylphenyl)ethane, or a combination thereof.

[0051] For example, in an embodiment, the styrene-diene copolymer in the present application includes, but is not limited to, a styrene-diene random copolymer, a styrene-diene alternating copolymer, a styrene-diene graft copolymer, a styrene-diene block copolymer, or a combination thereof.

[0052] For example, in an embodiment, the ethylene propylenediene rubber (EPDM) in the present application refers to a rubber obtained by copolymerization of ethylene, propylene, and a diene monomer.

[0053] In addition to the aforementioned components, the resin composition of the present application can further include, as necessary, a 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (DOPO) substituted with a vinylbenzyl group. The amount of the aforementioned 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide substituted with a vinylbenzyl group is not particularly limited, and can be, for example, 10 to 15 parts by weight, relative to 100 parts by weight of the vinyl group-containing resin.

[0054] In one embodiment, the resin composition of the present application can further include, as necessary, an inorganic filler, a curing accelerator, a flame retardant, a polymerization inhibitor, a solvent, a silane coupling agent, a surfactant, a dyeing agent, a toughening agent, or a combination thereof. If not otherwise specified, the content of any of the aforementioned components can be 0.001 to 300 parts by weight, for example, 0.001, 0.01, 0.1, 1, 5, 10, 20, 30, 40, 50, 60, 70, 80, 90, 100, 150, 200, 250, or 300 parts by weight, for example, 30 to 150 parts by weight, and for example, 200 to 300 parts by weight, relative to 100 parts by weight of the vinyl group-containing resin.

[0055] The aforementioned inorganic filler can be any one or more inorganic fillers suitable for use in the manufacture of a resin film, a prepreg, a laminate, or a printed circuit board, and specific examples include, but are not limited to, silica (fused, unfused, porous, or hollow), alumina, aluminum hydroxide, magnesium oxide, magnesium hydroxide, calcium carbonate, aluminum nitride, boron nitride, aluminum silicon carbide, silicon carbide, titanium dioxide, zinc oxide, zirconium oxide, mica, boehmite (AlOOH), calcined talc, talc, silicon nitride, calcined kaolin, hollow porous particles, or a combination thereof. In addition, the inorganic filler can be in a spherical, fibrous, platy, particulate, flaky, acicular, or a combination thereof, and can optionally be pretreated with a silane coupling agent. In some embodiments, the present application uses silica (SC2050) sold by Admatechs. For example, the inorganic filler used in the present application can be in an amount of 1 to 300 parts by weight, relative to 100 parts by weight of the vinyl group-containing resin.

[0056] The aforementioned curing accelerator (including a curing initiator) can include a catalyst such as a Lewis base or a Lewis acid. Among them, the Lewis base can 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 can include a metal salt compound such as a manganese, iron, cobalt, nickel, copper, zinc, or the like, and a metal catalyst such as zinc octoate, cobalt octoate, or the like.

[0057] The curing accelerator can also include a curing initiator, such as a free radical generating peroxide, including but not limited to, dibenzoyl peroxide, dicumyl peroxide, 2,5-dimethyl-2,5-di(tert-butylperoxy)hexane, 2,5-dimethyl-2,5-di(tert-butylperoxy)-3-hexyne, di-tert-butyl peroxide, di(tert-butylperoxyisopropyl)benzene, di(tert-butylperoxy)phthalate, di(tert-butylperoxy)isophthalate, tert-butyl peroxybenzoate, 2,2-bis(tert-butylperoxy)butane, 2,2-bis(tert-butylperoxy)octane, 2,5-dimethyl-2,5-di(benzoylperoxy)hexane, lauryl peroxide, tert-hexyl peroxypivalate, di-butylperoxyisopropylbenzene, bis(4-tert-butylcyclohexyl)peroxydicarbonate, or combinations thereof. For example, the curing accelerator used in the present application can be used in an amount of 0.01 to 5 parts by weight, preferably 0.1 to 0.5 parts by weight, based on 100 parts by weight of the vinyl-containing resin.

[0058] For example, the above flame retardant can be any one or more of different phosphorus compound-containing flame retardants suitable for manufacturing prepreg, resin film, laminate, or printed circuit board, such as, but not limited to, phosphorus-containing flame retardants, preferably can include: ammonium polyphosphate, hydroquinone bis-(diphenyl phosphate), bisphenol A bis-(diphenylphosphate), tri(2-carboxyethyl)phosphine (TCEP), tris(chloroisopropyl)phosphate, trimethyl phosphate (TMP), dimethylmethyl phosphonate (DMMP), resorcinol bis(dixylenylphosphate) (RDXP, such as commercially available products of PX-200, PX-201, PX-202, etc.), phosphazene (such as commercially available products of SPB-100, SPH-100, SPV-100, etc.), 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 ethylisocyanurate, aluminum hypophosphite salt (such as products of OP-930, OP-935, etc.), or a combination thereof.

[0059] For example, the above-mentioned flame retardant can be a DPPO compound (e.g., a bis-DPPO compound such as commercially available products such as PQ-60), a DOPO compound (e.g., a bis-DOPO compound), a DOPO resin (e.g., DOPO-HQ, DOPO-NQ, DOPO-PN, DOPO-BPN), a DOPO-bonded epoxy resin, and the like, wherein DOPO-PN is a DOPO phenol novolac compound, DOPO-BPN can be a bisphenol novolac compound such as DOPO-bisphenol A novolac (DOPO-BPAN), DOPO-bisphenol F novolac (DOPO-BPFN), or DOPO-bisphenol S novolac (DOPO-BPSN), and the like.

[0060] In one embodiment, for example, the polymerization inhibitor described herein is not particularly limited and can be, for example, any of the various types of polymerization inhibitors known in the art, including but not limited to various commercially available polymerization inhibitor products. For example, the above-mentioned polymerization inhibitor can include, but is not limited to, 1,1-diphenyl-2-trinitrophenylhydrazine, methacrylonitrile, a dithioester, a nitroxide stable free radical, a triphenylmethyl free radical, a metal ion free radical, a sulfur free radical, hydroquinone, p-methoxyphenol, p-benzoquinone, phenothiazine, β-phenylnaphthylamine, p-tert-butylcatechol, methylene blue, 4,4'-butylidenebis(6-tert-butyl-3-methylphenol), 2,2'-methylenebis(4-ethyl-6-tert-butylphenol), or a combination thereof. For example, the above-mentioned nitroxide stable free radical can include, but is not limited to, a 2,2,6,6-substituted-1-piperidinyloxy free radical or a 2,2,5,5-substituted-1-pyrrolidinyloxy free radical, and the like, from cyclic hydroxylamine. As the substituent, an alkyl group having a carbon number of 4 or less, such as a methyl group or an ethyl group, is preferred. As a specific nitroxide free radical compound, 2,2,6,6-tetramethyl-1-piperidinyloxy free radical, 2,2,6,6-tetraethyl-1-piperidinyloxy free radical, 2,2,6,6-tetramethyl-4-oxo-1-piperidinyloxy free radical, 2,2,5,5-tetramethyl-1-pyrrolidinyloxy free radical, 1,1,3,3-tetramethyl-2-isoindolinyl free radical, N,N-di-tert-butylamineoxy free radical, and the like, can be exemplified. Instead of the nitroxide free radical, a stable free radical such as a galvinoxyl free radical can also be used. The polymerization inhibitor suitable for the resin composition of the present application can also be a product derived from substitution of a hydrogen atom or a group in the polymerization inhibitor with another atom or group. For example, a product derived from substitution of a hydrogen atom in the polymerization inhibitor with an amino group, a hydroxyl group, a ketone carbonyl group, and the like.

[0061] The main role of adding the solvent is to change the solid content of the resin composition and adjust the viscosity of the resin composition. For example, the solvent can include, but is not limited to, methanol, ethanol, ethylene glycol monomethyl ether, acetone, butanone (also known as methyl ethyl ketone), methyl isobutyl ketone, cyclohexanone, toluene, xylene, methoxyethyl acetate, ethoxyethyl acetate, propoxyethyl acetate, ethyl acetate, dimethylformamide, dimethylacetamide, propylene glycol methyl ether, and the like, or a mixture thereof. The amount of the aforementioned solvent is not particularly limited, and the amount of the solvent added can be adjusted according to the desired viscosity of the resin composition.

[0062] The aforementioned silane coupling agent can include various silane compounds (such as, but not limited to, siloxane compounds) and combinations thereof, which can be classified into aminosilane, epoxide silane, vinyl silane, acrylate silane, methacrylate silane, hydroxyl silane, isocyanate silane, methacryloyloxy silane, and acryloyloxy silane, according to the type of functional group.

[0063] The main role of adding the surfactant in the present application is to uniformly disperse the inorganic filler in the resin composition.

[0064] The dyeing agent suitable for the present application can include, but is not limited to, a dye or a pigment.

[0065] The main role of adding the toughening agent is to improve the toughness of the resin composition. The toughening agent can include, but is not limited to, a rubber resin, a carboxyl-terminated butadiene acrylonitrile rubber (CTBN), a core-shell rubber, or a combination thereof.

[0066] In addition to the aforementioned resin composition, the present application also provides an article made of the aforementioned resin composition, such as a component suitable for various electronic products, including but not limited to a prepreg, a resin film, a laminate, or a printed circuit board.

[0067] For example, the resin composition of the present application can be prepared as a prepreg, which includes a reinforcing material and a layer disposed on the reinforcing material. The layer is prepared by heating the aforementioned resin composition at a high temperature to form a semi-cured state (B-stage). The baking temperature for preparing the prepreg is between 80°C and 160°C, preferably between 100°C and 140°C. The reinforcing material can be any one of a fiber material, a woven fabric, a non-woven fabric, and the woven fabric preferably includes a glass fiber fabric. The type of glass fiber fabric is not particularly limited and can be any of various glass fiber fabrics that can be used for printed circuit boards, such as an E-type glass fabric, a D-type glass fabric, an S-type glass fabric, a T-type glass fabric, an L-type glass fabric, a Q-type glass fabric, or a QL-type glass fabric (a mixed structure glass fabric made of Q glass and L glass). The type of glass fiber includes yarn and roving, and the form includes opened or unopened, and the end face shape includes a round or flat shape. 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 the like, 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, and the like, 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 optionally pre-treated with a silane coupling agent. The prepreg is subsequently heated to cure (C-stage) to form an insulating layer.

[0068] For example, the resin composition of the present application can be prepared as a resin film, which is obtained by heating the aforementioned resin composition to semi-cure by baking. The resin composition can be optionally coated on a support material, which includes but is not limited to a liquid crystal resin film, a polytetrafluoroethylene film, a polyethylene terephthalate film (PET film), a polyimide film (PI film), a metal foil, or a resin-coated copper (RCC), and is then heated to form a semi-cured state by baking to form a resin film of the resin composition.

[0069] For example, the resin composition of the present application can be prepared as various laminates, which include at least two metal foils and at least one insulating layer disposed between the two metal foils, and the insulating layer can be cured (C-stage) from the aforementioned resin composition at a high temperature and a high pressure, for example, a curing temperature of between 180°C and 240°C, preferably between 200°C and 220°C, a curing time of 90 to 150 minutes, preferably 90 to 120 minutes, and a pressurizing pressure of between 250 psi and 600 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 an alloy thereof, for example, a copper foil. In a preferred embodiment, the laminate is a copper foil substrate.

[0070] In one embodiment, the aforementioned laminate can be further processed via a circuit process to form a circuit board, such as a printed circuit board.

[0071] For example, in one embodiment, the aforementioned articles of manufacture comprising the resin composition of each of the embodiments described herein can comprise a reinforcing material or support material and a semi-cured or cured product obtained by chemically crosslinking the resin composition upon heating.

[0072] In one or more embodiments, the articles of manufacture prepared from the resin composition of the present application can satisfy at least one, preferably at least two, more, or all of the following properties:

[0073] a dielectric loss of less than or equal to 0.0036, such as between 0.0028 and 0.0036, measured at a frequency of 10 GHz according to the method described in JIS C2565;

[0074] a copper foil pull strength of greater than or equal to 3.23 lb / in, such as between 3.23 lb / in and 3.68 lb / in, or between 3.58 lb / in and 3.68 lb / in, measured according to the method described in IPC-TM-650 2.4.8;

[0075] a flame resistance of V-0 rating, measured according to the method described in UL94 specification; and

[0076] an X-axis coefficient of thermal expansion of less than or equal to 14.1 ppm / °C, such as between 11.0 ppm / °C and 14.1 ppm / °C, or between 11.0 ppm / °C and 11.2 ppm / °C, measured according to the method described in IPC-TM-650 2.4.24.5.

[0077] The methods for measuring the aforementioned properties are described in detail below.

[0078] The resin compositions of the embodiments of the present application and the comparative examples of the present application were prepared by blending the various raw materials from the following sources in the amounts described in Tables 1-3, and further forming test samples.

[0079] The chemical raw materials used in the synthesis examples of the present application, the embodiments of the present application, and the comparative examples of the present application are as follows:

[0080] The compound of formula (1-1) had the structure shown above and was purchased from Sigma-Aldrich.

[0081] The compound of formula (1-2) had the structure shown above and was purchased from Sigma-Aldrich.

[0082] The compound of formula (1-3) had the structure shown above and was purchased from Sigma-Aldrich.

[0083] OPE-2st 2200: End-capped vinylbenzyl polyphenylene ether resin, available from Mitsubishi Gas Chemical.

[0084] SA9000: Methyl methacrylate containing polyphenylene ether resin, available from Sabic.

[0085] MIR-5000: Biphenyl aralkyl type maleimide resin, available from Japan Elastomer.

[0086] BVPE: Bis(vinylphenyl)ethane, commercially available.

[0087] Compound of Formula (4): Structure shown above, prepared according to Synthetic Example 1.

[0088] Ricon 100: Styrene-butadiene copolymer, available from Cray Valley.

[0089] 67: Ethylene propylene diene rubber, available from Lion Elastomers.

[0090] CHR-2st: Dione containing fluorene compound, available from Shandong Xingshun New Material.

[0091] MD3501: Divinylbenzene-terminated hydrogenated polybutadiene resin, available from Kraton Corporation.

[0092] p-vinylbenzyl-DOPO (p-vinylbenzyl-9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide): Structure shown below, available from Shandong Xingshun New Material Co., Ltd.

[0093]

[0094] DiDOPO-DHBP: Prepared according to Synthetic Example 2.

[0095] OP-935: Aluminum diethylphosphinate, available from Clariant.

[0096] SPV-100: Allyl phosphazene compound, available from Daito Chemical.

[0097] SC2050: Silica, available from Admatechs Corporation.

[0098] 25B: 2,5-Dimethyl-2,5-di(tert-butylperoxy)-3-hexyne, commercially available.

[0099] MEK: Methyl ethyl ketone, commercially available.

[0100] Synthetic Example 1

[0101] After 296 parts by weight of 2-bromoethylbenzene (purchased from Tokyo Chemical Industry Co., Ltd.), 70 parts by weight of α,α'-dichlorop-xylene (purchased from Tokyo Chemical Industry Co., Ltd.), and 18.4 parts by weight of methanesulfonic acid (purchased from Tokyo Chemical Industry Co., Ltd.) were reacted at 130°C for 8 hours, they were cooled to room temperature, neutralized with an aqueous sodium hydroxide solution, and extracted with 1200 parts by weight of toluene. The organic layer was washed with water. The solvent and excess 2-bromoethylbenzene were distilled off under reduced pressure with heating to obtain an intermediate product. The molar ratio of 2-bromoethylbenzene to α,α'-dichlorop-xylene can be 4:1; methanesulfonic acid can be replaced with other acidic catalysts such as hydrochloric acid, phosphoric acid, etc.; and the reaction conditions can be 40°C to 180°C for 0.5 to 20 hours.

[0102] After 22 parts by weight of the above intermediate product, 50 parts by weight of toluene (other aromatic solvents such as xylene can also be used), 150 parts by weight of dimethyl sulfoxide (other aprotic polar solvents such as dimethyl sulfone can also be used), 15 parts by weight of water, and 5.4 parts by weight of sodium hydroxide (other basic catalysts such as potassium hydroxide, potassium carbonate can also be used) were reacted at 40°C for 5 hours, they were cooled to room temperature, and 100 parts by weight of toluene was added. The organic layer was washed with water, and the solvent was distilled off under reduced pressure with heating to obtain a compound having the structure shown in Formula (4).

[0103] Synthesis Example 2

[0104] After 2 moles of 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (DOPO) and 1 mole of 4,4'-dihydroxybenzophenone were added to a reaction device, they were reacted at 190°C for 3 hours to obtain DiDOPO-DHBP having the following structure.

[0105]

[0106] The compositions (in parts by weight) and property tests of the resin compositions of the examples and comparative examples are shown below.[Table 1] Compositions (in parts by weight) and property tests of the resin compositions of the examples

[0107]

[0108]

[0109] [Table 2] Compositions (in parts by weight) and property tests of the resin compositions of the examples

[0110]

[0111]

[0112] [Table 3] Composition (unit: parts by weight) and properties of comparative resin compositions

[0113]

[0114]

[0115] The aforementioned properties were measured for the test substance (sample) prepared according to the following method, and the properties were analyzed according to the specific conditions.

[0116] 1. prepreg 1 (PP 1)

[0117] Each of the resin compositions (unit: parts by weight) of the examples and comparative examples was used to prepare a varnish by adding and mixing each component of the resin composition in a stirring tank. The varnish was placed in an impregnation tank, and a glass fiber fabric (for example, L-glass fiber fabric of 1078 size, purchased from Asahi) was immersed in the impregnation tank, so that the resin composition was attached to the glass fiber fabric. Then, the glass fiber fabric was heated at 100 to 140°C to be in a B-stage state, and prepreg 1 was obtained, which had a resin content of about 70%.

[0118] 2. prepreg 2 (PP 2)

[0119] Each of the resin compositions (unit: parts by weight) of the examples and comparative examples was used to prepare a varnish by adding and mixing each component of the resin composition in a stirring tank. The varnish was placed in an impregnation tank, and a glass fiber fabric (for example, L-glass fiber fabric of 2116 size, purchased from Asahi) was immersed in the impregnation tank, so that the resin composition was attached to the glass fiber fabric. Then, the glass fiber fabric was heated at 100 to 140°C to be in a B-stage state, and prepreg 2 was obtained, which had a resin content of about 70%.

[0120] 3. copper-containing substrate 1 (obtained by laminating two prepregs 1)

[0121] Two 1 oz. thick HVLP (hyper very low profile) copper foils and two 1078 L-glass fiber cloth were prepared for each of the prepreg 1 (70% resin content) to be tested (each group of examples or each group of comparative examples). The copper foils, two prepregs 1 and copper foils were stacked in the order of copper foil, two prepregs 1 and copper foil, and were pressed under vacuum at 250 psi to 600 psi and 200 °C to 220 °C for 90 minutes to 120 minutes to form a copper-containing substrate 1. The two prepregs 1 were cured to form an insulating layer between the two copper foils, and the insulating layer had a resin content of about 70%.

[0122] 4. Copper-free substrate 1 (two prepregs 1 pressed together)

[0123] The copper-containing substrate 1 pressed together from the two prepregs 1 was etched to remove the copper foils on both sides to obtain a copper-free substrate 1 (two prepregs 1 pressed together).

[0124] 5. Copper-containing substrate 2 (two prepregs 2 pressed together)

[0125] The copper-containing substrate 2 pressed together from the two prepregs 2 was etched to remove the copper foils on both sides to obtain a copper-free substrate 2 (two prepregs 2 pressed together).

[0126] 6. Copper-free substrate 2 (two prepregs 2 pressed together)

[0127] The copper-containing substrate 2 pressed together from the two prepregs 2 was etched to remove the copper foils on both sides to obtain a copper-free substrate 2 (two prepregs 2 pressed together).

[0128] 7. Copper-containing substrate 3 (six prepregs 1 pressed together)

[0129] The copper-containing substrate 3 pressed together from the six prepregs 1 was etched to remove the copper foils on both sides to obtain a copper-free substrate 3 (eight prepregs 1 pressed together).

[0130] 8. Copper-containing substrate 4 (eight prepregs 1 pressed together)

[0131] The copper-containing substrate 4 pressed together from the eight prepregs 1 was etched to remove the copper foils on both sides to obtain a copper-free substrate 3 (eight prepregs 1 pressed together).

[0132] 9. Copper-free substrate 3 (eight prepregs 1 pressed together)

[0133] The copper-containing substrate 4 pressed together from the eight prepregs 1 was etched to remove the copper foils on both sides to obtain a copper-free substrate 3 (eight prepregs 1 pressed together).

[0134] For the aforementioned samples to be tested, the test methods and their characteristic analysis items are described as follows:

[0135] Dissipation factor (Df)

[0136] In the measurement of dielectric loss, the above-mentioned copper-free substrate 1 (two prepregs 1 are laminated to form, and the resin content is about 70%) is selected as the sample to be measured. A microwave dielectrometer (purchased from AET Company, Japan) is used to measure the dielectric loss of each sample to be measured at room temperature (about 25°C) and at a frequency of 10 GHz according to the method described in JIS C2565. At a measurement frequency of 10 GHz, and when the Df value is less than or equal to 0.0100, the difference in Df value is less than 0.0010, which means that there is no significant difference in the dielectric loss of the substrate (there is no significant technical difficulty), and when the difference in Df value is greater than or equal to 0.0010, it means that there is a significant difference between the dielectric losses of different substrates (there is a significant technical difficulty).

[0137] One-ounce (1 oz) peeling strength (1 oz P / S)

[0138] A copper-containing substrate 3 (six prepregs 1 are laminated to form) is prepared, cut into an oblong sample with a width of 24 mm and a length of 80 mm, and the surface copper foil is etched, leaving only a long strip of copper foil with a width of 3.18 mm and a length of more than 60 mm. The one-ounce (1 oz) peeling strength (1 oz P / S) of the sample is measured in lb / in at room temperature (about 25°C) by using a universal tensile strength testing machine according to the method described in IPC-TM-650 2.4.8. In the field, the higher the copper foil peeling strength, the better.

[0139] Flame resistance

[0140] A copper-free substrate 3 (formed by laminating eight prepregs 1) is prepared as the sample to be measured. The measurement is carried out according to the UL94 specification method, and the flame resistance analysis result is represented by V-0, V-1, V-2, etc., wherein the flame resistance of V-0 is better than that of V-1, the flame resistance of V-1 is better than that of V-2, and the sample is burned out, which is the worst.

[0141] X-axis coefficient of thermal expansion (X-CTE)

[0142] A copper-free substrate 2 (made by pressing two prepregs 2) was prepared as a sample to be measured, and thermal mechanical analysis (TMA) was performed. The copper-free substrate 2 was cut into a sample having a length of 24 mm and a width of 3 mm. The sample was heated at a temperature increase rate of 10°C per minute from 35°C to 350°C, and the X-axis thermal expansion coefficient (unit: ppm / °C) of each sample to be measured in the temperature range of 40°C to 125°C (al) was measured according to the method described in IPC-TM-650 2.4.24.5. The X-axis thermal expansion coefficient referred to herein means the thermal expansion coefficient in the X-axis direction of the sample. The lower the X-axis thermal expansion coefficient, the better the dimensional expansion and contraction characteristics. When the difference in the X-axis thermal expansion coefficient between the substrates is greater than or equal to 1.0 ppm / °C, it means that there is a significant difference in the X-axis thermal expansion coefficient between the substrates (there is a significant technical difficulty).

[0143] Referring to the test results of Tables 1 to 3 collectively, the following phenomena can be clearly observed.

[0144] From Examples E1 to E13, it can be confirmed that the resin composition and the product thereof according to the present application can be improved in one or more of dielectric loss, copper foil pull, flame resistance, and X-axis thermal expansion coefficient.

[0145] Comparing Examples E1 to E13 and Comparative Examples C1 to C3, it can be found that, compared to 100 parts by weight of the vinyl-containing resin, if the resin composition does not use the phosphorus-containing compound having the structure represented by formula (1), but uses other phosphorus-containing compounds, at least one of the characteristics of the corresponding resin composition and the product thereof, such as dielectric loss, copper foil pull, and X-axis thermal expansion coefficient, is significantly deteriorated.

[0146] Comparing Examples E1 to E13 and Comparative Examples C4 to C5, it can be found that, compared to 100 parts by weight of the vinyl-containing resin, if the amount of the phosphorus-containing compound having the structure represented by formula (1) in the resin composition is not in the range of 35 parts by weight to 65 parts by weight, at least one of the characteristics of the corresponding resin composition and the product thereof, such as dielectric loss, copper foil pull, and X-axis thermal expansion coefficient, is significantly deteriorated.

[0147] In addition, comparing Examples E1 to E9 and Examples E10 to E13, it can be found that, if the resin composition contains the p-vinylbenzyl-DOPO, at least one of the characteristics of the corresponding resin composition and the product thereof, such as copper foil pull and X-axis thermal expansion coefficient, can be further improved.

[0148] The above embodiments and examples are merely illustrative in nature and are not intended to limit the embodiments of the application or the application or uses of such embodiments. In this document, the terms "example" and "exemplary" mean "serving as an example, instance, or illustration." Any implementation of the described examples are not necessarily considered to be preferred or advantageous over other implementations, unless otherwise specified.

[0149] Furthermore, although one or more exemplary embodiments or examples have been described herein, it is to be understood that the application can be embodied in various forms or modifications without departing from the spirit or essential characteristics thereof. Also, it is to be understood that the application is not limited in its application to the details set forth and that the application is capable of other embodiments or being practiced or carried out in various ways. Also, it is to be understood that the phraseology and terminology employed herein are for the purpose of description and should not be regarded as limiting. As such, the foregoing description is not intended to be exhaustive or to limit the application to the precise forms disclosed, and obviously many modifications and variations are possible in light of the above teachings. The examples and embodiments described herein are further intended to provide examples of components and / or to provide an example from which a person of ordinary skill in the art can practice the application, but are not intended to limit the application to these examples. Also, it will be understood that any numerical range recited herein includes all values from the lower and upper limits unless otherwise indicated.

Claims

1. A resin composition, characterized in that, The resin composition comprises 100 parts by weight of a vinyl-containing resin and 35 to 65 parts by weight of a phosphorus-containing compound having the structure shown in formula (1): In formula (1), R1 to R6 are each independently hydrogen or C1 to C3 alkyl groups, Q1 is each independently a -(C=O)- group or *-CH2-C6H4- group, where * represents bonded to an oxygen atom, and G is each independently a monovalent phosphorus-containing group as shown in formula (2) or formula (3). In equation (2), n1 and n2 are each independent integers from 0 to 3, and R7 and R8 are each independent alkyl groups from C1 to C3.

2. The resin composition according to claim 1, characterized in that, The vinyl-containing resins include vinyl polyphenylene ether resins, maleimide resins, di(vinylphenyl)ethane, compounds having the structure shown in formula (4), styrene-butadiene copolymers, ethylene propylene diene rubber, diene-containing fluorene compounds, divinylbenzene-terminated hydrogenated polybutadiene resins, or combinations thereof. Where m ranges from 1 to 20.

3. The resin composition according to claim 1, characterized in that, The resin composition further includes 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide substituted with vinylbenzyl.

4. The resin composition according to claim 3, characterized in that, Compared to 100 parts by weight of vinyl-containing resin, the content of 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide substituted with vinyl benzyl is 10 to 15 parts by weight.

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

6. An article made from the resin composition of claim 1, comprising a prepreg, a resin film, a laminate, or a printed circuit board.

7. The article of claim 6, wherein the dielectric loss measured at a frequency of 10 GHz by the method described in accordance with JIS C2565 is less than or equal to 0.0036.

8. The article of claim 6, wherein the tensile strength to copper foil, as measured by the method described in IPC-TM-650 2.4.8, is greater than or equal to 3.23 lb / in.

9. The article of claim 8, wherein the tensile strength to copper foil, as measured by the method described in IPC-TM-650 2.4.8, is greater than or equal to 3.58 lb / in.

10. The article of claim 6, wherein the flame retardancy measured in accordance with the method specified in UL94 reaches a V-0 rating.

11. The article of claim 6, wherein the X-axis coefficient of thermal expansion, measured with reference to the method of IPC-TM-650 2.4.24.5, is less than or equal to 14.1 ppm / ℃.

12. The article of claim 11, wherein the X-axis coefficient of thermal expansion, measured with reference to the method of IPC-TM-650 2.4.24.5, is less than or equal to 11.2 ppm / ℃.

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