Resin composition and product thereof

Abstract

The invention discloses a resin composition and a product thereof. The resin composition comprises a polymer, and the polymer has a first structural unit as shown in a formula (1) and a second structural unit as shown in a formula (2). The resin composition can be prepared into a prepreg, a resin film, a laminated board or a printed circuit board, and at least one of the characteristics of dielectric constant, dielectric loss, tensile force to copper foil, high-temperature warping amount and the like is improved. # imgabs0 #

Description

Technical Field

[0001] The present invention relates to a resin composition, in particular to a resin composition which can be used for preparing a prepreg, a resin film, a laminate or a printed circuit board. 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 dielectric properties of circuit boards, the prior art focuses on adjusting the types or proportions of the raw resin composition. For example, hydrocarbons have been used in existing resin materials to improve dielectric properties. However, the properties of laminates and other products made of such resin materials still cannot meet the requirements. Summary of the invention

[0004] In view of the problems encountered in the prior art, especially the inability of existing materials to meet one or more of the above-mentioned property requirements, the main purpose of the present invention is to provide a resin composition that can overcome at least one of the above-mentioned technical problems and a product made using the resin composition.

[0005] In order to achieve the above object, the present invention discloses a resin composition, comprising a polymer (hereinafter referred to as "the polymer of the present invention"), which has a first structural unit represented by formula (1) and a second structural unit represented by formula (2):

[0006]

[0007] wherein Ar are the same or different and each independently represents a divalent organic group; R1 are the same or different and each independently represents a methyl group or a trifluoromethyl group; m1 are the same or different and each independently represents an integer from 6 to 8; m2 are the same or different and each independently represents an integer from 5 to 8; and n / m is between 1 and 3, such that the weight average molecular weight of the polymer is between 30,000 and 70,000.

[0008] For example, in one embodiment, the resin composition further includes an inorganic filler, a flame retardant, a hardening accelerator, an inhibitor, a solvent, a silane coupling agent, a colorant, a toughening agent or a combination thereof.

[0009] For example, in one embodiment, the resin composition further includes a multifunctional aromatic vinyl compound.

[0010] For example, in one embodiment, the resin composition includes 100 parts by weight of the polymer and 5 to 30 parts by weight of the multifunctional aromatic vinyl compound.

[0011] For example, in one embodiment, the polyfunctional aromatic vinyl compound includes a compound having a structure represented by formula (7), a compound having a structure represented by formula (8), or a combination thereof:

[0012]

[0013] 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.

[0014] For example, in one embodiment, the aforementioned article has one, more or all of the following characteristics:

[0015] The dielectric constant measured at a frequency of 10 GHz according to the method described in JIS C2565 is less than or equal to 2.77;

[0016] The dielectric loss measured at a frequency of 10 GHz according to the method described in JIS C2565 is less than or equal to 0.00168;

[0017] The copper foil tensile force measured as described in IPC-TM-650 2.4.8 is greater than or equal to 3.31 lb / in; and

[0018] The warpage measured after heat treatment at 200° C. for 30 minutes is less than or equal to 1.93 mm. BRIEF DESCRIPTION OF THE DRAWINGS

[0019] Figure 1 This is the GPC chart of the product obtained in Production Example 1 (polymer P1). DETAILED DESCRIPTION

[0020] 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 terms used in the text have the common meanings understood by those skilled in the art for the present invention. In the event of a conflict, the definitions in this specification shall prevail.

[0021] As used herein, the terms "include", "comprising", "having", "containing" or any other similar terms are open-ended transitional phrases, which are intended to cover non-exclusive inclusions. For example, a composition or article containing multiple elements is not limited to those 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 otherwise expressly stated, 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, as used herein, the interpretation of the terms "include", "comprising", "having", and "containing" should be considered to have specifically disclosed and simultaneously cover transitional terms such as "consisting of" and "consisting essentially of".

[0022] In this article, all features or conditions 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, especially integer values. For example, the range description of "1 to 8" should be deemed 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., especially the sub-ranges defined by all integer values, and should be deemed to have specifically disclosed individual values ​​such as 1, 2, 3, 4, 5, 6, 7, 8, etc. in the range. Similarly, the range description of "between 1 and 8" should be deemed 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., and include endpoint values. Unless otherwise specified, the above-mentioned interpretation method is applicable to all contents of the full text of the present invention, regardless of whether the scope is wide or not.

[0023] If the quantity or other numerical value or parameter is expressed as a range, a preferred (or preferred) range or a series of upper and lower limits, it should be understood that all ranges consisting of any upper limit or preferred value of the range and the lower limit or preferred value of the range have been specifically disclosed herein, regardless of whether such 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.

[0024] In this document, numerical values ​​should be understood to have the accuracy of the 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 from 39.50 to 40.49.

[0025] 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 members 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 those who use 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 all subgroups or individual members 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 or X2 or X3 and Y is Y1 or Y2 or Y3 has been fully described.

[0026] If not otherwise specified, in the present invention, "resin" may generally be a customary name for a synthetic polymer, but in the present invention, "resin" may include monomers, polymers thereof, combinations of monomers, combinations of polymers thereof, or combinations of monomers and polymers thereof, and is not limited thereto. A combination of monomers is a group formed by a plurality of monomers. For example, in the present invention, "maleimide resin" may include maleimide monomers, maleimide polymers, combinations of maleimide monomers, combinations of maleimide polymers, or combinations of maleimide monomers and maleimide polymers. Resins may include compounds and mixtures.

[0027] 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, and is 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 substance with the same composition or the same properties. In addition, in the present invention, a mixture refers to a combination of two or more compounds.

[0028] Herein, parts by weight represent parts by weight, which may be any weight unit, such as but not limited to grams, kilograms, pounds, etc. For example, 100 parts by weight of a polymer may represent 100 grams of a polymer, 100 kilograms of a polymer, or 100 pounds of a polymer, but is not limited thereto.

[0029] The following detailed description is merely illustrative in nature and is not intended to limit the present invention and its use. In addition, this document is not limited by any theory described in the above prior art or invention summary or the following detailed description or examples.

[0030] As mentioned above, the main purpose of the present invention is to provide a resin composition, comprising a polymer having a first structural unit represented by formula (1) and a second structural unit represented by formula (2):

[0031]

[0032] wherein Ar are the same or different and each independently represents a divalent organic group; R1 are the same or different and each independently represents a methyl group or a trifluoromethyl group; m1 are the same or different and each independently represents an integer from 6 to 8; m2 are the same or different and each independently represents an integer from 5 to 8; and n / m is between 1 and 3, such that the weight average molecular weight of the polymer is between 30,000 and 70,000.

[0033] For example, in the polymer of the present invention, Ar can be any of the following divalent organic groups, but is not limited thereto:

[0034]

[0035] Wherein z1 represents the unit repeat number, and it can be 1 to 10;

[0036]

[0037] Where z2 represents the unit repetition number, and 1≤z2≤5;

[0038] Where z3 represents the unit repetition number, and 1≤z3≤10;

[0039] Wherein z4 represents the unit repeat number, and it may be 1.3;

[0040]

[0041] , where z5 and z6 represent the unit repeat numbers, and z5 and z6 are both 3 (average value); and

[0042]

[0043] Wherein z7 represents the unit repetition number, and 1≤z7≤10.

[0044] For example, in one embodiment, in formula (1), n ​​may be between 5 and 45; in formula (2), m may be between 3 and 32, but is not limited thereto.

[0045] For example, in one embodiment, the polymer of the present invention refers to a product obtained by polymerizing a maleimide resin, a first diamine compound containing two hydroxyl groups, a second diamine compound having a carbon number of 15 to 45, and a vinyl halide, and has a first structural unit represented by formula (1) and a second structural unit represented by formula (2).

[0046] For example, in one embodiment, the polymer of the present invention may further be polymerized using a third diamine compound containing silicon and oxygen.

[0047] Examples of the above-mentioned silicon-oxygen-containing third diamine compounds include, but are not limited to, silicon-oxygen-containing third diamine compounds produced by Shin-Etsu Chemical Co., Ltd. with trade names such as PAM-E, KF-8010, X-22-161A, X-22-161B, KF-8012, KF-8008, X-22-1660B-3 and X-22-9409, or silicon-oxygen-containing third diamine compounds produced by Wacker Co., Ltd. with trade names such as NH-02-D, NH-15-D, NH-30-D, NH-130-D and NH-200-D.

[0048] For example, in one embodiment, one of the technical features of the polymer of the present invention is that it still retains vinyl functional groups after polymerization, and the vinyl functional groups can further undergo cross-linking reactions.

[0049] In addition to the aforementioned polymer of the present invention, the resin composition of the present invention may further include a maleimide resin, a vinyl-containing polyphenylene ether resin, a polyolefin resin or a combination thereof as required.

[0050] The maleimide resin may 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, m-phenylene bismaleimide, 4-methyl-1,3-phenylene bismaleimide, and bisphenol A diphenyl ether bismaleimide. bismaleimide), 1,6-bismaleimide-(2,2,4-trimethyl)hexane, maleimide resins with aromatic propylene groups, and maleimide resins containing aliphatic long chain structures.

[0051] For example, examples of maleimide resins 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 KI Chemical Co., Ltd. under the trade names of BMI-70, BMI-80, or maleimide resins produced by Nippon Kayaku Co., Ltd. under the trade names of MIR-5000. For example, maleimide resins containing aliphatic long chain structures (e.g., containing C5 to C 50 Examples of maleimide resins having aliphatic long chain structures include, but are not limited to, maleimide resins produced by designer molecules under the trade names of BMI-689, BMI-1400, BMI-1500, BMI-1700, BMI-2500, BMI-3000, BMI-5000 and BMI-6000.

[0052] 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 methacrylate group. For example, in one embodiment, the vinyl-containing polyphenylene ether resin includes a vinyl benzyl biphenyl polyphenylene ether resin, a methacrylate polyphenylene ether resin (i.e., a methacryloyl 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-2st 1200, 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.

[0053] The above-mentioned polyolefin resin may include, but is not limited to, polybutadiene, polyisoprene, styrene-butadiene copolymer, styrene-isoprene copolymer, styrene-butadiene-divinylbenzene terpolymer, maleic anhydride added polybutadiene-styrene copolymer, vinyl-polybutadiene-urea oligomer, maleic anhydride added polybutadiene, polymethylstyrene, hydrogenated polybutadiene, hydrogenated styrene-butadiene-divinylbenzene terpolymer, hydrogenated maleic anhydride added polybutadiene-styrene copolymer, hydrogenated styrene-butadiene copolymer, hydrogenated styrene-isoprene copolymer or a combination thereof.

[0054] In addition to the aforementioned polymer, the resin composition of the present invention may further include inorganic fillers, flame retardants, hardening accelerators, 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 0.5 to 300 parts by weight, such as 5, 10, 20, 30, 40, 50, 60, 70, 80, 90, 100, 150, 200, 250 or 300 parts by weight, such as 30 to 150 parts by weight, and for example 200 to 300 parts by weight, relative to 100 parts by weight of the polymer of the present invention.

[0055] 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 polymer of the present invention, the amount of the inorganic filler used in the present invention is not particularly limited, for example, it can be 50 parts by weight to 200 parts by weight, preferably 100 parts by weight to 150 parts by weight.

[0056] For example, the flame retardant may be any one or more flame retardants suitable for use in the manufacture 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), 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, 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.

[0057] 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 A novolac), DOPO-BPFN (DOPO-bisphenol F novolac) or DOPO-BPSN (DOPO-bisphenol S novolac).

[0058] 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, and the hardening initiator includes but is not limited to: diisopropylbenzene peroxide, tert-butyl peroxybenzoate, dibenzoyl peroxide (BPO), 2,5-dimethyl-2,5-di(tert-butylperoxy)-3-hexyne (25B) and bis(tert-butylperoxyisopropyl)benzene or a combination thereof. For example, compared to 100 parts by weight of the polymer of the present invention, the content of the hardening accelerator used in the present invention can be 0.01 to 5 parts by weight, preferably 0.5 to 2 parts by weight.

[0059] 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, it is preferably an alkyl group with a carbon number of 4 or less such as methyl or ethyl. 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 atoms or atomic groups in the inhibitor being replaced by other atoms or atomic groups. For example, the hydrogen atoms in the inhibitor are replaced by atomic groups such as amino, hydroxyl, ketocarbonyl, etc.

[0060] For example, the solvent applicable to 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 the like solvents or mixed solvents thereof. The amount of the aforementioned solvent is not particularly limited, and the amount of the solvent added can be adjusted according to the required viscosity of the resin composition.

[0061] 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.

[0062] For example, the coloring agent may include but is not limited to dye or pigment.

[0063] 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 may include but is not limited to carboxyl-terminated butadieneacrylonitrile rubber (CTBN), core-shell rubber, and other compounds or combinations thereof.

[0064] In addition, in one embodiment, in addition to the polymer of the present invention, the resin composition of the present invention may also include a polyfunctional aromatic vinyl compound as needed. For example, in one embodiment, the resin composition of the present invention includes 100 parts by weight of the polymer and 5 to 30 parts by weight of the polyfunctional aromatic vinyl compound.

[0065] The aforementioned multifunctional aromatic vinyl compound refers to a compound containing two or more aromatic vinyl groups in its structure, and its structure is not particularly limited. For example, in one embodiment, the multifunctional aromatic vinyl compound includes a compound having a structure shown in formula (7), a compound having a structure shown in formula (8), or a combination thereof:

[0066]

[0067] 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.

[0068] For example, the resin composition of each embodiment of the present invention can be made into a semi-cured sheet, which includes a reinforcing material and a layered object disposed on the reinforcing material. The layered object is obtained by heating the aforementioned resin composition at a high temperature to form a semi-cured state (B-stage). The baking temperature for making the semi-cured sheet is between 90°C and 140°C, preferably between 100°C and 120°C. The reinforcing material can be any one of a fiber material, 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 can be a commercially available glass fiber cloth that can be used for various printed circuit boards, such as E-type glass cloth, D-type glass cloth, S-type glass cloth, T-type glass cloth, L-type glass cloth or Q-type glass cloth, wherein the types of fibers include yarn and roving, etc., and the form may include open fiber or unopen fiber. The aforementioned non-woven fabric preferably includes a liquid crystal resin non-woven fabric, such as a polyester non-woven fabric, a polyurethane non-woven fabric, etc., and is not limited thereto. The aforementioned fabric may also include a liquid crystal resin fabric, such as a polyester fabric or a polyurethane 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.

[0069] For example, the resin composition of each embodiment of the present invention can be made into a resin film, which is obtained by semi-curing the aforementioned resin composition after baking and heating. The resin composition can be selectively coated on a polyethylene terephthalate film (PET film), a polyimide film (PI film), a copper foil or a copper foil with adhesive, and then semi-cured after baking and heating, so that the resin composition forms a resin film.

[0070] For example, the resin composition of each embodiment of the present invention can be made into a laminate, which includes two metal foils and an insulating layer disposed between the metal foils. The insulating layer can be obtained by curing (C-stage) the 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 80 to 150 minutes, preferably 90 to 120 minutes. The insulating layer can be formed by curing (C-stage) the semi-cured sheet or resin film. The metal foil may include copper, aluminum, nickel, platinum, silver, gold or an alloy thereof, for example, the metal foil may be copper foil. In one embodiment, the laminate is a copper clad laminate (CCL).

[0071] 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.

[0072] In one embodiment, the resin composition provided by the present invention can improve at least one of the following properties: dielectric constant, dielectric loss, tensile force on copper foil, and high-temperature warpage.

[0073] For example, the resin composition provided by the present invention or the product made therefrom may satisfy one, more or all of the following characteristics:

[0074] The dielectric constant measured at a frequency of 10 GHz according to the method described in JIS C2565 is less than or equal to 2.77, for example, between 2.52 and 2.77, or between 2.52 and 2.54; the dielectric loss measured at a frequency of 10 GHz according to the method described in JIS C2565 is less than or equal to 0.00168, for example, between 0.00108 and 0.00168, or between 0.00108 and 0.00142;

[0075] The copper foil tensile force measured by the method described in IPC-TM-650 2.4.8 is greater than or equal to 3.31 lb / in, such as between 3.31 lb / in and 3.48 lb / in; and

[0076] The warpage measured after heat treatment at 200° C. for 30 minutes is less than or equal to 1.93 mm, for example, between 1.53 mm and 1.93 mm, or between 1.53 mm and 1.56 mm.

[0077] Various polymers were prepared according to the amounts of the main reactants (monomers) in Tables 1 to 2 and the textual descriptions of Preparation Examples 1 to 13. In addition, various raw materials from the following sources were used to prepare the resin compositions of the Examples of the present invention and the Comparative Examples of the present invention according to the amounts in Tables 3 to 5, and further prepared into various test samples.

[0078] The chemical raw materials used in the polymer production examples, resin composition examples and resin composition comparative examples are as follows:

[0079] Polymers P1 to P13: as described in Production Examples 1 to 13.

[0080] BMI-TMH: 1,6-bismaleimide-(2,2,4-trimethyl)hexane, purchased from Yamato Chemical Industry Co., Ltd. MIR-5000: maleimide resin having the structure shown in formula (3), wherein 1≤k≤5, purchased from Nippon Kayaku Co., Ltd.

[0081]

[0082] BMI-2300: polyphenylmethane maleimide, purchased from Yamato Chemical Industry Co., Ltd.

[0083] BAP: 2,2-bis(3-amino-4-hydroxyphenyl)propane

[0084] (2,2-bis(3-amino-4-hydroxyphenyl)propane), commercially available.

[0085] 6FAP: 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane

[0086] (2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane), commercially available. BAS: bis(3-amino-4-hydroxyphenyl)sulfone, commercially available.

[0087] Primer 1075-1: a diamine compound having a structure represented by formula (4-1), purchased from East Hope Chemical.

[0088]

[0089] Primer 1075-2: a diamine compound having a structure represented by formula (4-2), purchased from East Hope Chemical.

[0090]

[0091] Primer 1075-3: a diamine compound having a structure represented by formula (4-3), purchased from East Hope Chemical.

[0092]

[0093] TFMB: 2,2'-bis(trifluoromethyl)-4,4'-biphenylenediamine

[0094] (2,2'-bis(trifluoromethyl)benzidine), commercially available.

[0095] VBC: 4-vinylbenzyl chloride, commercially available.

[0096] The compound represented by the formula (5): as described in Preparation Example 14.

[0097] Where x represents the number of unit repeats, and its weight average molecular weight is about 56,000.

[0098] The compound represented by the formula (6): as described in Preparation Example 15.

[0099] Where y represents the number of unit repeats, and its weight average molecular weight is about 56,000.

[0100] CW-PVE: The structure is shown in formula (7), purchased from Heying.

[0101]

[0102] CW-PPVE: The structure is shown in formula (8), purchased from Heying.

[0103]

[0104] SC-2050: spherical silica, purchased from Admatechs.

[0105] 25B: 2,5-dimethyl-2,5-di(tert-butylperoxy)-3-hexyne

[0106] di(tert-butylperoxy)-3-hexyne) was purchased from Nippon Oil & Fats Co.

[0107] Anisole: Commercially available.

[0108] Various polymers were prepared according to the following textual description, wherein the monomers used in the polymerization reaction and their amounts can be found in Table 1 and Table 2.

[0109] Production Example 1

[0110] 2 mol of BMI-TMH, 0.6 mol of BAP, 0.4 mol of Primer 1075-1 and 100 ml of solvent (such as anisole) were added to a three-necked flask and stirred continuously to obtain a mixed solution. The mixed solution was heated from room temperature to 120°C and stirred continuously for 6 hours, then heated to 155°C, and 1 mol of VBC was added to react for 4 hours. Finally, 0.1 wt% to 1 wt% of 1,4-benzenediol based on the total amount of the above raw materials (excluding the solvent) was added to terminate the reaction to obtain the polymer P1 of the present invention, whose weight average molecular weight was about 56,000. The polymer P1 was analyzed by gel permeation chromatography, and the results are as follows: Figure 1 shown.

[0111] Production Example 2

[0112] The method is basically the same as Preparation Example 1, except that Primer 1075-1 is replaced with Primer 1075-2 to obtain the polymer P2 of the present invention, which has a weight average molecular weight of about 56,000.

[0113] Production Example 3

[0114] The method is basically the same as Preparation Example 1, except that Primer 1075-1 is replaced with Primer 1075-3 to obtain the polymer P3 of the present invention, which has a weight average molecular weight of about 56,000.

[0115] Production Example 4

[0116] The process is basically the same as that in Preparation Example 1, except that BAP is replaced with 6FAP to obtain the polymer P4 of the present invention, which has a weight average molecular weight of about 56,000.

[0117] Production Example 5

[0118] The method is basically the same as Preparation Example 1, except that BMI-TMH is replaced with MIR-5000 to obtain the polymer P5 of the present invention, which has a weight average molecular weight of about 56,000.

[0119] Production Example 6

[0120] The process is basically the same as that in Preparation Example 1, except that the mixed solution is heated from room temperature to 120° C. and stirred for 3 hours to obtain the polymer P6 of the present invention, whose weight average molecular weight is about 30,000.

[0121] Production Example 7

[0122] The process is basically the same as that in Preparation Example 1, except that the mixed solution is heated from room temperature to 120° C. and stirred for 8 hours to obtain the polymer P7 of the present invention, which has a weight average molecular weight of about 70,000.

[0123] Production Example 8

[0124] The method is basically the same as Preparation Example 1, except that 0.7 mol of BAP and 0.3 mol of Primer 1075-1 are added to obtain the polymer P8 of the present invention, and the weight average molecular weight thereof is about 56,000.

[0125] Production Example 9

[0126] The method is basically the same as Preparation Example 1, except that 0.8 mol of BAP and 0.2 mol of Primer 1075-1 are added to obtain the polymer P9 of the present invention, whose weight average molecular weight is about 56,000.

[0127] Production Example 10

[0128] The process is basically the same as that in Preparation Example 1, except that Primer 1075-1 is replaced with TFMB to obtain a polymer P10 having a weight average molecular weight of about 56,000.

[0129] Production Example 11

[0130] The process is basically the same as that in Preparation Example 5, except that BAP is replaced with BAS in Preparation Example 11 to obtain a polymer P11 having a weight average molecular weight of about 56,000.

[0131] Production Example 12

[0132] The process is basically the same as that of Preparation Example 1, except that VBC is not used in Preparation Example 12. The polymer P12 obtained has a weight average molecular weight of about 56,000.

[0133] Production Example 13

[0134] The method is basically the same as Preparation Example 9, except that BMI-TMH is replaced with BMI-2300 to obtain the polymer P13 of the present invention, which has a weight average molecular weight of about 56,000.

[0135] Production Example 14

[0136] 1 mol of BMI-TMH, 1 mol of BAP and 50 ml of anisole were added to a three-necked flask and stirred continuously to obtain a mixed solution. The mixed solution was heated from room temperature to 120° C. and stirred continuously for 6 hours. The temperature was then raised to 155° C. and 1 mol of VBC was added to react for 4 hours. Finally, 0.1 wt % to 1 wt % of 1,4-dihydroquinone based on the total amount of the above raw materials (excluding the solvent) was added to terminate the reaction to obtain a compound of the structure shown in formula (5) with a weight average molecular weight of about 56,000.

[0137] Production Example 15

[0138] 1 mol of BMI-TMH, 1 mol of Primer 1075-1 and 50 ml of anisole were added to a three-necked flask and stirred continuously to obtain a mixed solution. The mixed solution was heated from room temperature to 120° C. and stirred continuously for 6 hours to obtain a compound of the structure represented by formula (6) with a weight average molecular weight of about 56,000.

[0139] [Table 1] Monomers involved in different polymers and their amounts (molar number)

[0140] Polymer No. P1 P2 P3 P4 P5 P6 P7 BMI-TMH 2 2 2 2 2 2 MIR-5000 2 BMI-2300 BAP 0.6 0.6 0.6 0.6 0.6 0.6 6FAP 0.6 BAS Primer 1075-1 0.4 0.4 0.4 0.4 0.4 Primer 1075-2 0.4 Primer 1075-3 0.4 TFMB VBC 1 1 1 1 1 1 1

[0141] [Table 2] Monomers involved in different polymers and their amounts (molar number)

[0142]

[0143]

[0144] The resin composition compositions (all in parts by weight) and property tests of the embodiments and comparative examples are shown below, where 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 100 parts by weight of polymer P1, which means that 100 parts by weight of polymer P1 with a solid content of 100% is used.

[0145] [Table 3] Composition (unit: weight parts) and property tests of the resin composition of the embodiment

[0146]

[0147] [Table 4] Composition (unit: weight parts) and property tests of the resin composition of the embodiment

[0148]

[0149]

[0150] [Table 5] Composition (unit: weight parts) and property tests of comparative resin compositions

[0151]

[0152]

[0153] The above characteristics are prepared by referring to the following method to prepare the object to be tested (sample), and then the characteristics are analyzed according to specific conditions.

[0154] 1. Prepreg (PP)

[0155] The resin compositions of the embodiments and comparative examples (in parts by weight) were used respectively, 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., L2-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%.

[0156] 2. Copper-containing substrate 1 (made of two prepreg sheets pressed together)

[0157] Prepare two 0.5 ounce HVLP (hyper very low profile) copper foils and two 1078-gauge L2-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%.

[0158] 3. Copper-containing substrate 2 (made of six prepreg sheets pressed together)

[0159] 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.

[0160] 4. Copper-free substrate 1 (made of two prepregs pressed together)

[0161] 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).

[0162] 5. Copper-free substrate 2 (made of six prepreg sheets pressed together)

[0163] The copper-containing substrate 2 formed by pressing six prepregs is etched to remove the copper foil on both sides, thereby obtaining a copper-free substrate 2 (formed by pressing six prepregs).

[0164] For the above-mentioned samples to be tested, the test methods and their characteristic analysis items are described as follows:

[0165] Dielectric constant (Dk)

[0166] 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%) is selected as the sample to be tested. A microwave dielectrometer (purchased from AET Company of Japan) is 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 0.15 means that there is no significant difference in the dielectric constant of the substrate (there is no significant technical difficulty), and a difference in Dk values ​​greater than or equal to 0.15 means that there is a significant difference between the dielectric constants of different substrates (there is a significant technical difficulty).

[0167] Dielectric loss (dissipation factor, Df)

[0168] 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%) is selected as the sample to be tested. A microwave dielectrometer (purchased from AET Company of Japan) is used, and the method described in JIS C2565 is referred to, and each sample to be tested is measured at room temperature (about 25°C) and at a frequency of 10GHz to obtain the dielectric loss. The lower the dielectric loss, the better the dielectric properties of the sample to be tested. At a measurement frequency of 10GHz and a Df value ranging from 0.0010 to 0.0030, a difference in Df value of less than 0.0005 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 0.0005 indicates that there is a significant difference between the dielectric losses of different substrates (there is a significant technical difficulty).

[0169] Copper foil pull (0.5 oz peeling strength, 0.5 oz P / S)

[0170] 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 0.5 ounces (half-ounce) of copper foil tension (0.5oz P / S) in lb / in. In this field, the higher the copper foil tension, the better. Generally speaking, if the difference in copper foil tension (0.5 ounce) of a substrate with a resin content of about 70% is greater than or equal to 0.3 lb / in, it means that there is a significant difference in the copper foil tension (0.5 ounce) of different substrates (there is a significant technical difficulty).

[0171] Warpage at high temperature

[0172] Prepare a copper-free substrate 2 (composed of six semi-cured sheets pressed together), cut it into a size of 10 cm in length and 10 cm in width, and measure the warping of the sample after it is placed in an environment of 200°C for 30 minutes. The measurement method is to place the aforementioned sample on a marble platform, and use a height gauge to measure the vertical distance between the corner with the largest warping and the marble plane, in mm. In the warping measurement, the number of samples is 6, and the average distance is taken. As far as this field is concerned, the smaller the high-temperature warping, the better. Generally speaking, if the difference in high-temperature warping is greater than or equal to 0.2 mm, it means that there are significant differences between different samples (there are significant technical difficulties).

[0173] By referring to the test results in Tables 3 to 5, the following phenomena can be clearly observed.

[0174] Compared with Examples E1 to E14 using the polymer of the present invention, Comparative Examples C1 to C5 using other polymers cannot achieve satisfactory results in at least one property such as dielectric constant, dielectric loss, copper foil tension, and high-temperature warpage. Compared with Comparative Examples C1 to C5, Examples E1 to E14 using the polymer of the present invention can simultaneously achieve lower dielectric constant (dielectric constant measured at a frequency of 10 GHz according to the method described in JIS C2565 is less than or equal to 2.77), lower dielectric loss (dielectric loss measured at a frequency of 10 GHz according to the method described in JIS C2565 is less than or equal to 0.00168), higher copper foil tension (copper foil tension measured according to the method described in IPC-TM-650 2.4.8 is greater than or equal to 3.31 lb / in), and lower high-temperature warpage (warpage measured at a temperature of 200°C for 30 minutes is less than or equal to 1.93 mm). In addition, if the polymer of the present invention and one or more polyfunctional aromatic vinyl compounds are used simultaneously, at least one or more of the above-mentioned properties can be further improved.

[0175] The above embodiments are essentially only for auxiliary explanation and are not intended to limit the embodiments of the application target 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 better or more advantageous than other embodiments.

[0176] 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 changes. It should also be understood that the embodiments described herein are not intended to limit the scope, use or configuration of the requested application object 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 when the present patent application is filed.

Claims

1. A resin composition, characterized in that The resin composition includes a polymer having a first structural unit represented by formula (1) and a second structural unit represented by formula (2): wherein Ar are the same or different and each independently represents a divalent organic group; R1 are the same or different and each independently represents a methyl group or a trifluoromethyl group; m1 are the same or different and each independently represents an integer from 6 to 8; m2 are the same or different and each independently represents an integer from 5 to 8; and n / m is between 1 and 3, such that the weight average molecular weight of the polymer is between 30,000 and 70,000.

2. The resin composition according to claim 1, characterized in that The resin composition further comprises an inorganic filler, a flame retardant, a hardening accelerator, an inhibitor, a solvent, a silane coupling agent, a colorant, a toughening agent or a combination thereof.

3. The resin composition according to claim 1, characterized in that The resin composition further comprises a multifunctional aromatic vinyl compound.

4. The resin composition according to claim 3, characterized in that The resin composition includes 100 parts by weight of the polymer and 5 to 30 parts by weight of the multifunctional aromatic vinyl compound.

5. The resin composition according to claim 3, characterized in that The multifunctional aromatic vinyl compound includes a compound having a structure shown in formula (7), a compound having a structure shown in formula (8), or a combination thereof:

6. A product made from the resin composition according to claim 1, characterized in that: The product includes a prepreg, a resin film, a laminate or a printed circuit board.

7. The product according to claim 6, characterized in that The dielectric constant of the product measured at a frequency of 10 GHz according to the method described in JIS C2565 is less than or equal to 2.

77.

8. The product according to claim 6, characterized in that The dielectric loss of the product measured at a frequency of 10 GHz according to the method described in JIS C2565 is less than or equal to 0.00168.

9. The product according to claim 6, characterized in that The copper foil tensile force of the product measured according to the method described in IPC-TM-6502.4.8 is greater than or equal to 3.31 lb / in.

10. The product according to claim 6, characterized in that The warpage of the product measured after heat treatment at 200° C. for 30 minutes is less than or equal to 1.93 mm.

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