Resin composition and its product

Abstract

The present invention discloses a resin composition, which comprises: (A) 100 parts by weight of a thermosetting resin, which comprises a vinyl-containing polyphenylene ether resin, a maleimide resin or a combination thereof; (B) 15 parts by weight to 50 parts by weight of a sintered body formed from aluminum nitride and boron nitride; and (C) 180 parts by weight to 280 parts by weight of titanium dioxide. In addition, the present invention also discloses an article made from the aforementioned resin composition, which comprises a prepreg, a resin film, a laminate or a printed circuit board.

Description

Technical Field

[0001] The present invention relates to a resin composition and its products, and particularly to a resin composition that can be used to prepare prepregs, resin films, laminates, or printed circuit boards. Background Art

[0002] In recent years, with the high integration of semiconductors and communications in fields such as 5G and AI, the property requirements for high-capacitance substrate materials have become increasingly high, and traditional high dielectric properties can no longer meet the current requirements for circuit boards in semiconductors.

[0003] Traditional high-capacitance antenna substrate materials are added with titanium dioxide, strontium titanate, or barium titanate. Although they can meet the requirements of high-capacitance materials, their heat dissipation is too low. Therefore, a large amount of alumina or boron nitride is generally added to improve the thermal conductivity, but relatively, the copper foil adhesion of the substrate decreases; also, with the high-speed and high-frequency signal transmission of electronic products, it is an urgent issue to have both low dielectric loss, good insulation properties such as high breakdown voltage, and relatively high dielectric constant and better thermal conductivity. Therefore, how to develop a material suitable for the above high-performance substrates is the current active effort direction in the industry. Summary of the Invention

[0004] In view of the problems encountered in the prior art, especially the fact that existing resin materials cannot meet one or more of the above property requirements, the main object of the present invention is to provide a resin composition, thereby achieving at least one good property such as high tensile strength against copper foil, high breakdown voltage, and low dielectric loss.

[0005] To achieve the above object, the present invention discloses a resin composition, which includes:

[0006] (A) 100 parts by weight of a thermosetting resin, which includes vinyl-containing polyphenylene ether resin, maleimide resin, or a combination thereof;

[0007] (B) 15 to 50 parts by weight of a sintered body formed by aluminum nitride and boron nitride (referred to as ABN); and

[0008] (C) 180 to 280 parts by weight of titanium dioxide.

[0009] For example, in one embodiment, compared with 100 parts by weight of the thermosetting resin, the aforementioned resin composition further includes 5 to 20 parts by weight of alumina.

[0010] For example, in one embodiment, the aforementioned resin composition further includes a flame retardant, a crosslinking agent, a curing accelerator, a polymerization inhibitor, a solvent, a silane coupling agent, a dye, a toughening agent, a core-shell rubber, or a combination thereof.

[0011] Another main object of the present invention is to provide an article made of the aforementioned resin composition, which includes a prepreg, a resin film, a laminate or a printed circuit board.

[0012] For example, in one embodiment, the aforementioned article has one, more than one or all of the following characteristics:

[0013] The tensile force on the copper foil measured by the method described in IPC-TM-650 2.4.8 is greater than or equal to 4.03 lb / in;

[0014] The breakdown voltage measured by the method described in IPC-TM-650 2.5.6.3 is greater than or equal to 35.5 kV;

[0015] The dielectric loss measured by the method described in JIS C2565 at a frequency of 10 GHz is less than or equal to 0.0049;

[0016] The dielectric constant measured by the method described in JIS C2565 at a frequency of 10 GHz is greater than or equal to 6.9; and

[0017] The thermal conductivity coefficient measured by the method described in ASTM-D5470 is greater than or equal to 0.61 W / (m·K). Detailed Description of the Invention

[0018] To enable those skilled in the art to understand the features and effects of the present invention, the following provides a general description and definition of the terms and expressions mentioned in the specification and claims. Unless otherwise specified, all technical and scientific terms used herein have the ordinary meaning that those skilled in the art understand for the present invention. In case of conflict, the definition in this specification shall prevail.

[0019] The theories or mechanisms described and disclosed herein, whether correct or incorrect, shall not limit the scope of the present invention in any way, that is, the content of the present invention can be implemented without being limited by any specific theory or mechanism.

[0020] In this article, the expressions "a", "an", "one kind" or similar are used to describe the components and technical features of the present invention. Such descriptions are merely for convenience of expression and give a general meaning to the scope of the present invention. Therefore, such descriptions should be understood to include one or at least one, and the singular also includes the plural, unless clearly referring to another meaning.

[0021] In this article, "or its combination" means "or any one of its combinations", and "any one", "any kind", "any one" means "any one", "any kind", "any one".

[0022] In this document, terms such as "comprising", "including", "having", "containing", or any other similar terms are open-ended transitional phrases that are intended to cover non-exclusive inclusions. For example, a composition or article containing plural elements is not limited to only those elements listed herein, but may also include other elements not explicitly listed but that are ordinarily inherent in the composition or article. In addition, unless expressly stated to the contrary, the term "or" means an inclusive "or" rather than an exclusive "or". For example, any of the following situations satisfies the condition "A or B": A is true (or exists) and B is false (or does not exist), A is false (or does not exist) and B is true (or exists), A and B are both true (or exist). Further, in this document, the terms "comprising", "including", "having", "containing" should be construed as having specifically disclosed and simultaneously covered closed transitional phrases such as "consisting of", "composed of", "the balance being", as well as transitional phrases such as "substantially consisting of", "mainly composed of", "mainly consisting of", "essentially containing", "essentially composed of", "essentially consisting of", "inherently containing".

[0023] In this document, all characteristics or conditions defined in the form of numerical ranges or percentage ranges, such as numerical values, quantities, contents, and concentrations, are for the sake of brevity and convenience only. Accordingly, the description of a numerical range or percentage range should be regarded as having covered and specifically disclosed all possible sub-ranges and individual numerical values within the range (including integers and fractions), especially integer values. For example, the range description of "1.0 to 8.0" or "between 1.0 and 8.0" should be regarded as having specifically disclosed all sub-ranges such as 1.0 to 8.0, 1.0 to 7.0, 2.0 to 8.0, 2.0 to 6.0, 3.0 to 6.0, 4.0 to 8.0, 3.0 to 8.0, etc., and should be regarded as covering the endpoint values, especially the sub-ranges defined by integer values, and should be regarded as having specifically disclosed individual numerical values within the range such as 1.0, 2.0, 3.0, 4.0, 5.0, 6.0, 7.0, 8.0, etc. Unless otherwise specified, the foregoing method of interpretation applies to all contents of this invention, regardless of the breadth of the range.

[0024] If a quantity, concentration, or other numerical value or parameter is expressed as a range, a preferred range, a more preferred range, or a series of upper and lower limits, it should be understood that all ranges formed by any pair of the upper limit or preferred value or more preferred value of the range and the lower limit or preferred value or more preferred value of the range have been specifically disclosed herein, regardless of whether these ranges are separately disclosed. In addition, when a numerical range is mentioned in this document, unless otherwise stated, the range should include its endpoints and all integers and fractions within the range.

[0025] In this text, on the premise that the invention object can be achieved, the numerical value should be understood as having the precision of the significant digits of that numerical value. For example, the number 40.0 should be understood as covering the range from 39.50 to 40.49.

[0026] In this text, for the case of using a Markush group or alternative terms to describe the features or examples of the present invention, those skilled in the art should understand that all sub-groups or any individual members within the Markush group or the list of alternatives can also be used to describe the present invention. For example, if X is described as "selected from the group consisting of X 1 , X 2 and X 3 ", it also means that the claim that X is X 1 and the claim that X is X 1 and / or X 2 and / or X 3 have been fully described. Furthermore, for those using a Markush group or alternative terms to describe the features or examples of the present invention, those skilled in the art should understand that any combination of all sub-groups or individual members within the Markush group or the list of alternatives can also be used to describe the present invention. Accordingly, for example, if X is described as "selected from the group consisting of X 1 , X 2 and X 3 ", and Y is described as "selected from the group consisting of Y 1 , Y 2 and Y 3 ", it means that the claim that X is X 1 or X 2 or X 3 while Y is Y 1 or Y 2 or Y 3 has been fully described.

[0027] Unless otherwise specified, in the present invention, a compound refers to a chemical substance formed by the bonding of two or more elements through chemical bonds, including small molecule compounds and high molecular compounds, and is not limited thereto. In this text, a compound is not only limited to a single chemical substance in interpretation, but can also be interpreted as a group of chemical substances with the same composition or the same properties.

[0028] Unless otherwise specified, in the present invention, a polymer refers to a product formed by monomers through a polymerization reaction, which often includes many aggregates of macromolecules. Each macromolecule is composed of many simple structural units repeatedly connected by covalent bonds, and a monomer is a compound for synthesizing a polymer. Polymers can include homopolymers (also known as self-polymers), copolymers, prepolymers, etc., and are not limited thereto. A prepolymer refers to a chemical substance produced by a polymerization reaction of two or more compounds with a conversion rate between 10% and 90%. Polymers of course include oligomers, and are not limited thereto. An oligomer, also known as a low polymer, is a polymer composed of 2 to 20 repeating units, usually a polymer composed of 2 to 5 repeating units. For example, when interpreting a diene polymer, it includes diene homopolymers, diene copolymers, diene prepolymers, and of course also diene oligomers, etc.

[0029] Unless otherwise specified, "resin" is generally a customary name for a synthetic polymer. However, in the present invention, when interpreting "resin", it can include forms such as monomers, their polymers, combinations of monomers, combinations of their polymers, or combinations of monomers and their polymers, etc., and is not limited thereto. For example, in the present invention, when interpreting "maleimide resin", it includes maleimide monomers, maleimide polymers, combinations of maleimide monomers, combinations of maleimide polymers, or combinations of maleimide monomers and maleimide polymers.

[0030] For example, in the present invention, when interpreting "vinyl-containing", it includes vinyl, vinylene, allyl, (meth)acrylate group or a combination thereof.

[0031] Unless otherwise specified, in the present invention, modifiers (also known as modified substances) include: products after modification of the reactive functional groups of each resin, products after prepolymerization reaction of each resin with other resins, products after crosslinking of each resin with other resins, products after homopolymerization of each resin, products after copolymerization of each resin with other resins, etc. For example, but not limited to, modification can be replacing the original hydroxyl group with a vinyl group through a chemical reaction, or reacting the original terminal vinyl group with p-aminophenol to obtain a terminal hydroxyl group.

[0032] Unless otherwise specified, in the present invention, for specific examples of acrylate compounds written in the form of "(meth)", it should be understood to include both cases with and without a methyl group. For example, cyclohexanedimethanol di(meth)acrylate should be interpreted to include cyclohexanedimethanol diacrylate and cyclohexanedimethanol dimethacrylate.

[0033] It should be understood that the features disclosed in each embodiment herein can be arbitrarily combined to form the technical solutions of this application, as long as there is no contradiction in the combination of these features.

[0034] Unless otherwise specified, in this text, parts by weight represent parts of weight, which can be any weight unit, such as but not limited to weight units like kilograms, grams, pounds, etc. For example, 100 parts by weight of maleimide resin can represent 100 kilograms of maleimide resin or 100 pounds of maleimide resin.

[0035] In this text, D50 refers to the particle size corresponding to the cumulative volume distribution of the inorganic filler (also known as filler, such as but not limited to titanium dioxide) reaching 50%.

[0036] The following specific embodiments are essentially illustrative only and are not intended to limit the present invention and its uses. In addition, this text is not limited by any theory described in the foregoing prior art or the summary of the invention or the following specific embodiments or examples. The methods, reagents, and conditions used in the examples are conventional methods, reagents, and conditions in the art unless otherwise specified.

[0037] Generally speaking, the present invention mainly discloses a resin composition, which includes:

[0038] (A) 100 parts by weight of a thermosetting resin, which includes a vinyl-containing polyphenylene ether resin, a maleimide resin, or a combination thereof;

[0039] (B) 15 parts by weight to 50 parts by weight of a sintered body formed by aluminum nitride and boron nitride; and

[0040] (C) 180 parts by weight to 280 parts by weight of titanium dioxide.

[0041] Unless otherwise specified, the vinyl-containing polyphenylene ether resin mentioned in each embodiment of the present invention may include various polyphenylene ether resins modified at the ends via vinyl, allyl, or (meth)acrylate groups, such as but not limited to vinylbenzyl biphenyl polyphenylene ether resin, methacrylate-containing polyphenylene ether resin, vinylbenzyl bisphenol A polyphenylene ether resin, vinyl-extended polyphenylene ether resin, or a combination thereof.

[0042] For example, in one embodiment, the vinyl-containing polyphenylene ether resin may include various types of vinyl-containing polyphenylene ether resins known in the art. The vinyl-containing polyphenylene ether resin suitable for the present invention is not particularly limited and may be any one or more commercially available products, self-made products, or combinations thereof. In certain embodiments, any one or more of the following vinyl-containing polyphenylene ether resins may be used: vinylbenzyl biphenyl polyphenylene ether resin (such as OPE-2st, available from Mitsubishi Gas Chemical Company), methacrylate-containing polyphenylene ether resin (such as SA9000, available from Sabic), vinylbenzyl bisphenol A polyphenylene ether resin, vinyl-extended polyphenylene ether resin, or combinations thereof. The vinyl-extended polyphenylene ether resin may include various polyphenylene ether resins in the US patent application with publication number 2016 / 0185904A1, the entire content of which is incorporated herein by reference.

[0043] For example, in one embodiment, the maleimide resin of the present invention includes monomers, polymers or combinations thereof having one or more maleimide functional groups in the molecule. Unless otherwise specified, the maleimide resin used in the present invention is not particularly limited and can be any one or more maleimide resins suitable for the production of prepregs (or prepregs), resin films, laminates or printed circuit boards. In some embodiments, any one or more of the following maleimide resins can be used: 4,4'-diphenylmethanebismaleimide, oligomer of phenylmethane maleimide (or polyphenylmethane maleimide), bisphenol A diphenyl ether bismaleimide, 3,3'-dimethyl-5,5'-diethyl-4,4'-diphenylmethanebismaleimide (or bis-(3-ethyl-5-methyl-4-maleimidephenyl)methane), 3,3'-dimethyl-5,5'-dipropyl-4,4'-diphenylmethane bismaleimide, biphenyl maleimide, m-phenylenebismaleimide, 4-methyl-1,3-phenylenebismaleimide, 1,6-bismaleimide-(2,2,4-trimethyl)hexane, N-2,3-xylylmaleimide, N-2,6-xylylmaleimide.6-xylylmaleimide, N-phenylmaleimide, diethyl bismaleimidotoluene, vinyl benzylmaleimide (VBM), vinyl cyclopentadiene-modified maleimide, maleimide resin containing an aliphatic long-chain structure, prepolymer of diallyl compound and maleimide resin (such as prepolymer of 4,4'-diphenylmethane bismaleimide and diallyl bisphenol A), prepolymer of diamine and maleimide resin, prepolymer of polyfunctional amine and maleimide resin, prepolymer of acidic phenolic compound and maleimide resin, or a combination thereof. Unless otherwise specified, the aforementioned maleimide resin also includes modified products of these components in interpretation.,

[0044] For example, the maleimide resin may be a maleimide resin produced by Daiwakasei Industry Co., Ltd. under the trade names BMI-1000, BMI-1000H, BMI-1100, BMI-1100H, BMI-2000, BMI-2300, BMI-3000, BMI-3000H, BMI-4000, BMI-5000, BMI-5100, BMI-TMH, BMI-7000, and BMI-7000H, or a maleimide resin produced by K.I. Chemical Co., Ltd. under the trade names BMI-70, BMI-80, etc., or a maleimide resin produced by Nippon Kayaku Co., Ltd. under the trade name MIR-3000, or a maleimide resin produced by Evonik Chemical Co., Ltd. under the trade name DE-TDAB, or a maleimide resin produced by HOS-Technik under the trade name Homide801, or a modified maleimide resin produced by Shin-Etsu under the trade name 5G 001s.

[0045] For example, the maleimide resin containing an aliphatic long-chain structure may be a maleimide resin produced by Designer Molecular Co., Ltd. under the trade names BMI-689, BMI-1400, BMI-1500, BMI-1700, BMI-2500, BMI-3000, BMI-5000, and BMI-6000. For example, the maleimide resin containing an aliphatic long-chain structure may have at least one maleimide functional group connected to a substituted or unsubstituted long-chain aliphatic group. Among them, the long-chain aliphatic group may be an aliphatic group with carbon number C 5 to C 50 For example, the aliphatic group with carbon number C 10 to C 50 、C 20 to C 50 、C30 to C 50 、C 20 to C 40 or C 30 to C 40 , but not limited thereto. For example, examples of commercially available maleimide resins containing aliphatic long-chain structures are as follows:

[0046] BMI-689:

[0047] BMI-1400:

[0048] BMI-1500:

[0049] BMI-1700:

[0050] BMI-2500:

[0051] BMI-3000, BMI-5000, BMI-6000:

[0052]

[0053] The sintered body formed by aluminum nitride and boron nitride can be prepared under conditions and by methods known in the art. For example, in one embodiment, the sintered body formed by aluminum nitride and boron nitride is formed by mixing aluminum nitride and boron nitride in a weight ratio of 4:1 to 16:1, mixing sintering aids such as calcium carbonate, sodium carbonate, boric acid, etc., and shaping by known methods such as a metal mold and cold isostatic pressing (CIP), and then sintering for 1 to 30 hours in a non-oxidizing gas environment such as nitrogen or argon at a temperature of 1,500 °C to 2,200 °C to produce a sintered body formed by aluminum nitride and boron nitride. Preferably, the sintered body is formed by aluminum nitride and boron nitride in a weight ratio of 6:1 to 14:1.

[0054] Unless otherwise specified, the particle size distribution (D50) of the sintered body formed by aluminum nitride and boron nitride can be ≤30 μm, preferably 5 μm ≤ D50 ≤ 25 μm, but not limited thereto.

[0055] Unless otherwise specified, the titanium dioxide contained in the resin composition of the present invention is not particularly limited, and can be various titanium dioxides suitable for the manufacture of prepregs, resin films, laminates or printed circuit boards.

[0056] Unless otherwise specified, the particle size distribution (D50) of the aforementioned titanium dioxide can be 0.5 μm ≤ D50 ≤ 5 μm, but not limited thereto.

[0057] In addition to the aforementioned thermosetting resin, the sintered body formed from aluminum nitride and boron nitride, and titanium dioxide, the resin composition of the present invention may also include other components as needed.

[0058] For example, in one embodiment, the resin composition of the present invention may also selectively further include alumina as needed. For example, but not limited to, compared with 100 parts by weight of the thermosetting resin, the resin composition of the present invention includes 5 to 20 parts by weight of alumina.

[0059] Unless otherwise specified, the particle size distribution (D50) of the aforementioned alumina may be 0.5 μm ≤ D50 ≤ 10 μm, but is not limited thereto.

[0060] For example, in one embodiment, the resin composition of the present invention may also selectively further include a flame retardant, a crosslinking agent, a hardening accelerator, a polymerization inhibitor, a solvent, a silane coupling agent, a coloring agent, a toughening agent, a core-shell rubber, or a combination thereof. For example, in one embodiment, compared with 100 parts by weight of the thermosetting resin, the content of any one of the aforementioned components may be 0.01 to 300 parts by weight, such as, but not limited to, 0.01 to 3 parts by weight, 30 to 80 parts by weight, or 50 to 300 parts by weight.

[0061] Unless otherwise specified, the flame retardant applicable to the present invention can be any one or more flame retardants applicable to the production of prepregs, resin films, laminates or printed circuit boards, such as, but not limited to, phosphorus-containing flame retardants, preferably including: ammonium polyphosphate, hydroquinone bis-(diphenyl phosphate), bisphenol A bis-(diphenylphosphate), tri(2-carboxyethyl)phosphine (TCEP), tris(chloroisopropyl) phosphate, trimethyl phosphate (TMP), dimethyl methylphosphonate (DMMP), resorcinol bis(dixylenylphosphate) (RDXP, such as commercially available products like PX-200, PX-201, PX-202, etc.), phosphazene (such as commercially available products like SPB-100, SPH-100, SPV-100, etc.), melamine polyphosphate, 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (DOPO) and its derivatives (such as bis-DOPO compounds) or resins, diphenylphosphine oxide (DPPO) and its derivatives (such as bis-DPPO compounds) or resins, melamine cyanurate, tri-hydroxyethylisocyanurate, aluminum hypophosphite salts (such as products like OP-930, OP-935, etc.) or combinations thereof. Unless otherwise specified, the dosage of the above flame retardants is not particularly limited.

[0062] For example, the flame retardant may be a DPPO compound (such as a bis-DPPO compound), 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., where DOPO-PN is a DOPO phenol novolac resin, and DOPO-BPN may be a bisphenol novolac resin such as DOPO-BPAN (DOPO-bisphenol A novolac), DOPO-BPFN (DOPO-bisphenol F novolac), or DOPO-BPSN (DOPO-bisphenol S novolac). Without special specification, the dosage of the above flame retardant is not particularly limited.

[0063] For example, in one embodiment, the crosslinking agent applicable to the present invention may be various crosslinking agents known in the art for resin compositions, including but not limited to triallyl isocyanurate, polyolefins, or combinations thereof. For example, compared with 100 parts by weight of the thermosetting resin, in the resin composition of the present invention, the dosage of the above crosslinking agent is not particularly limited, and preferably may be 50 parts by weight to 70 parts by weight.

[0064] Without special specification, the dosage of the curing accelerator used in the present invention can be adjusted as needed. For example, compared with 100 parts by weight of the thermosetting resin, in the resin composition of the present invention, the dosage of the above curing accelerator is not particularly limited. For example, it may be 0.1 part by weight to 15 parts by weight, such as 0.1 part by weight to 0.5 part by weight, or for another example, 1 part by weight to 10 parts by weight.

[0065] For example, the above-mentioned curing accelerators (including curing initiators) may include catalysts such as Lewis bases or Lewis acids. Among them, the Lewis bases may include imidazole, boron trifluoride amine complex, ethyltriphenyl phosphonium chloride, 2-methylimidazole (2MI), 2-phenyl-1H-imidazole (2PZ), 2-ethyl-4-methylimidazole (2E4MI), triphenylphosphine (TPP), 4-dimethylaminopyridine (DMAP), or combinations thereof. The Lewis acids may include metal salt compounds, such as metal salt compounds of manganese, iron, cobalt, nickel, copper, zinc, etc., such as zinc octoate, cobalt octoate and other metal catalysts. The curing accelerator also includes a curing initiator, for example, a peroxide that can generate free radicals. The curing initiator includes but is not limited to: diisopropylbenzene peroxide, tert-butyl peroxybenzoate, dibenzoyl peroxide (BPO), 2,5-dimethyl-2,5-bis(tert-butylperoxy)-3-hexyne (25B), bis(tert-butylperoxyisopropyl)benzene, or combinations thereof.

[0066] The polymerization inhibitor applicable to the present invention has the function of inhibiting the polymerization reaction. Without specific indication, its specific examples are not particularly limited and may include various molecular-type polymerization inhibitors, stable free radical-type polymerization inhibitors known in the art, or combinations thereof. For example, the molecular-type polymerization inhibitors applicable to the present invention include but are not limited to phenolic compounds, quinone compounds, aromatic amine compounds, aromatic nitro compounds, sulfur-containing compounds, variable-valence metal chlorides, or combinations thereof. More specifically, the molecular-type polymerization inhibitors applicable to the present invention include but are not limited to phenol, hydroquinone, 4-tert-butylcatechol, benzoquinone, chloroquinone, 1,4-naphthoquinone, trimethylquinone, aniline, nitrobenzene, Na 2 S, FeCl 3 , CuCl 2 , or combinations thereof. For example, the stable free radical-type polymerization inhibitors applicable to the present invention include but are not limited to 1,1-diphenyl-2-trinitrophenylhydrazine (DPPH), triphenylmethyl radical, or combinations thereof.

[0067] The main function of adding a solvent in the present invention is to dissolve each component in the resin composition, change the solid content of the resin composition, and adjust the viscosity of the resin composition. For example, the solvent may include, but is not limited to, solvents such as methanol, ethanol, ethylene glycol monomethyl ether, acetone, methyl ethyl ketone (also known as butanone), methyl isobutyl ketone, cyclohexanone, toluene, xylene, methoxyethyl acetate, ethoxyethyl acetate, propoxyethyl acetate, ethyl acetate, propylene glycol methyl ether, dimethylformamide, dimethylacetamide, and N-methylpyrrolidone, or a mixed solvent thereof. The amount of the foregoing solvent is not particularly limited, and the addition amount of the solvent can be adjusted according to the viscosity required by the resin composition.

[0068] Unless otherwise specified, the silane coupling agent applicable to the present invention may include silane compounds (silane, such as, but not limited to, siloxane compounds), and can be further divided into amino silane compounds, epoxide silane compounds, vinyl silane compounds, ester group silane compounds, hydroxyl silane compounds, isocyanate group silane compounds, methacryloxy silane compounds, and acryloxy silane compounds according to the type of functional group. The amount of the foregoing silane coupling agent is not particularly limited, and the addition amount of the silane coupling agent can be adjusted according to the dispersibility of the inorganic filler in the resin composition.

[0069] Unless otherwise specified, the colorant applicable to the present invention may include, but is not limited to, dyes or pigments.

[0070] The main function of adding a toughening agent in the present invention is to improve the toughness of the resin composition. Unless otherwise specified, the toughening agent applicable to the present invention may include, but is not limited to, rubbers such as carboxyl-terminated butadieneacrylonitrile rubber (CTBN).

[0071] The resin compositions of the various embodiments of the present invention can be made into various products (also known as articles) by various processing methods, including but not limited to prepregs, resin films, laminates, or printed circuit boards.

[0072] For example, the resin composition described in the present invention can be made into a prepreg.

[0073] For example, in one embodiment, the prepreg of the present invention has a reinforcing material and a layer disposed on the reinforcing material, and the layer is formed by heating the aforementioned resin composition to a semi-cured state (B-stage) at a high temperature. The baking temperature for producing the prepreg is, for example, between 130°C and 170°C. The reinforcing material can be a fiber material or a non-fiber material, and the form of the reinforcing material can be any one of woven fabrics and non-woven fabrics, and the woven fabric preferably includes a glass fiber cloth. The type of the glass fiber cloth is not particularly limited and can be a commercially available glass fiber cloth that can be used for various printed circuit boards, such as E-type glass fiber cloth, D-type glass fiber cloth, S-type glass fiber cloth, T-type glass fiber cloth, L-type glass fiber cloth, or Q-type glass fiber cloth, wherein the types of fibers include yarns and rovings, etc., and the forms can include fibrillated or non-fibrillated. The aforementioned non-woven fabric preferably includes a liquid crystal resin non-woven fabric, such as a polyester non-woven fabric, a polyurethane non-woven fabric, etc., and is not limited thereto. The aforementioned woven fabric can also include a liquid crystal resin woven fabric, such as a polyester woven fabric or a polyurethane woven fabric, etc., and is not limited thereto. 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. After the prepreg is subsequently heated for curing (C-stage), an insulating layer is formed.

[0074] For example, in one embodiment, the resin compositions can be uniformly mixed respectively to form a varnish, the varnish is placed in an impregnation tank, and then the glass fiber cloth is immersed in the impregnation tank so that the resin composition adheres to the glass fiber cloth, and then it is heated and baked at an appropriate temperature to the semi-cured state to obtain the prepreg.

[0075] For example, the resin composition of the present invention can be made into a resin film.

[0076] For example, in one embodiment, the resin film of the present invention is formed by heating the resin composition to the semi-cured state by baking. For example, the resin composition can be selectively coated on a liquid crystal resin film, a polyethylene terephthalate film (PET film), or a polyimide film, and then heated and baked at an appropriate heating temperature to the semi-cured state to form a resin film. Another example is that the resin compositions of the embodiments of the present invention can be respectively coated on a copper foil to make the resin composition uniformly adhere, and then heated and baked at an appropriate temperature to the semi-cured state to obtain a resin film.

[0077] For example, the resin composition of the present invention can be made into a laminate.

[0078] For example, in one embodiment, the laminate according to the present invention comprises at least two metal foils and at least one insulating layer, the insulating layer is disposed between the two metal foils, and the insulating layer can be cured from the aforementioned resin composition under high temperature and high pressure (C-stage). The applicable curing temperature is, for example, between 190°C and 210°C, preferably between 195°C and 205°C, the curing time is 90 to 120 minutes, preferably 100 to 110 minutes, and the applicable pressure is 30 kg / cm 2 to 40 kg / cm 2 between, preferably 35 kg / cm 2 . The aforementioned insulating layer can be obtained by curing the aforementioned prepreg or resin film. The material of the aforementioned metal foil can be copper, aluminum, nickel, platinum, silver, gold or their alloys, such as copper foil. In a preferred embodiment, the laminate is a copper foil substrate (also known as a copper clad laminate).

[0079] For example, in one embodiment, the aforementioned laminate can be further processed into a printed circuit board via circuit processing.

[0080] For example, in one embodiment, one of the manufacturing methods of the printed circuit board according to the present invention can be to use a double-sided copper foil substrate with a thickness of 28 mils and 0.5 ounce HVLP (hyper very low profile) copper foil (such as product EM-891, available from Taiguang Electronic Materials Co., Ltd.). After drilling, electroplating is performed to form electrical conduction between the upper copper foil and the lower copper foil. Then, the upper copper foil and the lower copper foil are etched to form an inner layer circuit. Next, the inner layer circuit is subjected to brownification and roughening treatment to form an uneven structure on the surface to increase roughness. Then, the copper foil, the aforementioned prepreg, the aforementioned inner layer circuit, the aforementioned prepreg, and the copper foil are stacked in sequence, and then a vacuum laminating device is used to heat at a temperature of 190°C to 210°C for 90 to 120 minutes to cure the insulating layer material of the prepreg. Then, various circuit board manufacturing processes known in the art, such as blackening treatment, drilling, and copper plating, are performed on the copper foil on the outermost surface, and a printed circuit board can be obtained.

[0081] In one embodiment, the resin composition provided by the present invention can improve at least one of the properties of the product such as the tensile strength of the copper foil, breakdown voltage, dielectric loss, dielectric constant, and thermal conductivity coefficient.

[0082] For example, the product made of the resin composition provided by the present invention can satisfy one, more, or all of the following properties:

[0083] Measured by the method described in IPC-TM-650 2.4.8, the tensile strength of the copper foil is greater than or equal to 4.03 lb / in, for example, greater than or equal to 4.11 lb / in, or for example, between 4.03 lb / in and 4.33 lb / in;

[0084] Measured by the method described in IPC-TM-650 2.5.6.3, the breakdown voltage is greater than or equal to 35.5 kV, for example, greater than or equal to 41.0 kV, or for example, between 35.5 kV and 43.0 kV;

[0085] Measured by the method described in JIS C2565 at a frequency of 10 GHz, the dielectric loss is less than or equal to 0.0049, for example, less than or equal to 0.0043, or for example, between 0.0039 and 0.0049;

[0086] Measured by the method described in JIS C2565 at a frequency of 10 GHz, the dielectric constant is greater than or equal to 6.9, for example, greater than or equal to 7.1, or for example, between 6.9 and 7.9; and

[0087] Measured by the method described in ASTM-D5470, the thermal conductivity is greater than or equal to 0.61 W / (m·K), for example, greater than or equal to 0.66 W / (m·K), or for example, between 0.61 W / (m·K) and 0.74 W / (m·K).

[0088] Using various raw materials from the following sources, the resin compositions of the examples and comparative examples of the present invention were respectively formulated according to the dosages in Tables 1 to 4, and further made into various test samples.

[0089] The chemical raw materials used in the examples and comparative examples of the present invention are as follows:

[0090] SA9000: Polyphenylene ether resin containing methacrylate, purchased from Sabic.

[0091] OPE-2st(1200): Polyphenylene ether resin containing vinylbenzyl biphenyl, purchased from Mitsubishi Gas Chemical.

[0092] OPE-2st(2200): Polyphenylene ether resin containing vinylbenzyl biphenyl, purchased from Mitsubishi Gas Chemical.

[0093] DE-TDAB: Diethyl bismaleimidotoluene, purchased from Evonik.

[0094] BMI-1000: 4,4'-Diphenylmethane bismaleimide, purchased from Daiwa Kasei Co., Ltd.

[0095] MIR-3000: Biphenyl maleimide, purchased from Nippon Kayaku Co., Ltd.

[0096] BMI-70: Bis(3-ethyl-5-methyl-4-maleimidophenyl)methane, purchased from K.I Chemical.

[0097] BMI-2300: Polystyrene methane maleimide, purchased from Daiwa Kasei Co., Ltd.

[0098] BMI-1500: Maleimide resin containing aliphatic long-chain structure, purchased from Designer Molecules, Inc.

[0099] BMI-1700: Maleimide resin containing aliphatic long-chain structure, purchased from Designer Molecules, Inc.

[0100] BMI-3000: Maleimide resin containing aliphatic long-chain structure, purchased from Designer Molecules, Inc.

[0101] BMI-80: Bisphenol A diphenyl ether bismaleimide, purchased from K.I Chemical.

[0102] Homide801: Prepolymer of 4,4’-diphenylmethanebismaleimide and diallylbisphenol A, purchased from HOS-Technik.

[0103] 5G 001s: Vinyl cyclopentadiene modified maleimide, purchased from Shin-Etsu.

[0104] TAIC: Triallyl isocyanurate, commercially available.

[0105] Ricon 100: Butadiene-styrene copolymer, purchased from Cray Valley.

[0106] ABN-020: Sintered body formed by aluminum nitride and boron nitride (weight ratio of aluminum nitride to boron nitride is 6:1 to 14:1), the particle size distribution (D50) of the sintered body is 5μm ≤ D50 ≤ 25μm, purchased from Hongjun Yingcai.

[0107] AlN: Aluminum nitride, trade name AlN-010S, purchased from Hongjun Yingcai.

[0108] BN: Boron nitride, trade name CFP007ST, purchased from 3M.

[0109] TiO 2 : Titanium dioxide, trade name HT0210, purchased from Suiye.

[0110] SrTiO 3 : Strontium titanate, purchased from Xinchang Ceramics.

[0111] BaTiO 3 : Barium titanate, purchased from Xinchang Ceramics.

[0112] Al 2 O 3 : Aluminum oxide, purchased from Hongjun Yingcai.

[0113] 25B: 2,5 - dimethyl - 2,5 - di(tert - butylperoxy)-3 - hexyne, (2,5 - dimethyl - 2,5 - di(tert - butylperoxy)-3 - hexyne), purchased from NOF Corporation.

[0114] Mixed solvent: A mixed solvent of methyl ethyl ketone (MEK) and toluene, where the weight ratio of methyl ethyl ketone to toluene is 1:1, prepared by oneself.

[0115] The compositions (all in parts by weight) of the resin compositions in the examples and comparative examples and the results of property tests are shown in the following table:

[0116] [Table 1] Compositions (unit: parts by weight) of the resin compositions in the examples and results of property tests

[0117]

[0118]

[0119] [Table 2] Compositions (unit: parts by weight) of the resin compositions in the examples and results of property tests

[0120]

[0121]

[0122] [Table 3] Compositions (unit: parts by weight) of the resin compositions in the comparative examples and results of property tests

[0123]

[0124]

[0125] [Table 4] Compositions (unit: parts by weight) of the resin compositions in the comparative examples and results of property tests

[0126]

[0127]

[0128]

[0129] The above-mentioned characteristics are prepared by the following method for the object to be measured (sample), and then the characteristics are analyzed according to specific conditions.

[0130] 1. Prepreg: The resin compositions of the above-mentioned examples (listed in Tables 1 to 2) and the resin compositions of the above-mentioned comparative examples (listed in Tables 3 to 4) are respectively selected. Each chemical reagent in the resin composition is uniformly mixed to form a varnish, wherein all the solid chemical reagents that can be dissolved in the varnish have been dissolved. The varnish is placed in an impregnation tank, and then a glass fiber cloth (for example, an E-glass fiber fabric with a specification of 1080, purchased from Asahi Corporation) is immersed in the above-mentioned impregnation tank so that the resin composition adheres to the glass fiber cloth, and it is heated to a semi-cured state (B-Stage) at 130°C to 170°C to obtain a prepreg. The resin content of the prepreg made of 1080 glass fiber cloth is about 70%.

[0131] 2. Copper-clad laminate 1 (or copper foil laminate 1, formed by laminating two prepregs): Prepare two reverse treated copper foils with a thickness of 18 μm and two prepregs made of E-glass fiber cloth with a specification of 1080 impregnated with each sample to be measured (each group of examples or each group of comparative examples). The resin content of each prepreg is about 70%. Stack them in the order of copper foil, two prepregs, and copper foil, and laminate them under vacuum conditions, a lamination pressure of 30 kg / cm 2 to 40 kg / cm 2 and at 190°C to 210°C for 90 minutes to 120 minutes to form copper-clad laminate 1. Among them, the two mutually laminated prepregs are cured to form an insulating layer between the two copper foils, and the resin content of the insulating layer is about 70%.

[0132] 3. Copper-clad laminate 2 (or copper foil laminate 2, formed by laminating six prepregs): Prepare two reverse treated copper foils with a thickness of 18 μm and six prepregs made of E-glass fiber cloth with a specification of 1080 impregnated with each sample to be measured (each group of examples or each group of comparative examples). The resin content of each prepreg is about 70%. Stack them in the order of copper foil, six prepregs, and copper foil, and laminate them under vacuum conditions, a lamination pressure of 30 kg / cm 2 to 40 kg / cm 2 and at 190°C to 210°C for 90 minutes to 120 minutes to form copper-clad laminate 2. Among them, the six mutually laminated prepregs are cured to form an insulating layer between the two copper foils, and the resin content of the insulating layer is about 70%.

[0133] 4. Copper-clad substrate 3 (also known as copper foil substrate 3, formed by laminating eight prepregs): Prepare two RTF copper foils (reverse treated copper foil) with a thickness of 18 microns and eight prepregs made of E-glass fiber cloth with a specification of 1080 impregnated with each sample to be tested (each set of examples or each set of comparative examples). The resin content of each prepreg is approximately 70%. Stack them in the order of copper foil, eight prepregs, and copper foil, and laminate them under vacuum conditions at a lamination pressure of 30 kg / cm 2 to 40 kg / cm 2 and a temperature of 190°C to 210°C for 90 minutes to 120 minutes to form copper-clad substrate 3. Among them, the eight mutually stacked prepregs are cured to form an insulating layer between the two copper foils, and the resin content of the insulating layer is approximately 70%.

[0134] 5. Copper-free substrate 1 (formed by laminating two prepregs): Etch the copper foils on both sides of the above copper-clad substrate 1 to obtain copper-free substrate 1, which is formed by laminating two prepregs and has a resin content of approximately 70%.

[0135] 6. Copper-free substrate 2 (formed by laminating eight prepregs): Etch the copper foils on both sides of the above copper-clad substrate 3 to obtain copper-free substrate 2, which is formed by laminating eight prepregs and has a resin content of approximately 70%.

[0136] For the aforementioned samples to be tested, the descriptions of each test method and its characteristic analysis items are as follows:

[0137] Copper foil tensile strength (0.5 ounce) (Hoz peeling strength, Hoz P / S)

[0138] Select the above copper-clad substrate 2 (formed by laminating six prepregs) and cut it into rectangular samples with a width of 24 mm and a length greater than 60 mm. Etch the surface copper foil, leaving only a strip of copper foil with a width of 3.18 mm and a length greater than 60 mm. Use a universal tensile strength testing machine to measure at room temperature (about 25°C) according to the method described in IPC-TM-650 2.4.8 to measure the force required to pull the 0.5-ounce copper foil away from the surface of the substrate insulating layer, with the unit of lb / in. In this field, the higher the copper foil tensile strength, the better. For copper foil substrates with a measured value of dielectric loss between 0.0040 and 0.0080 at a frequency of 10 GHz, a difference in copper foil tensile strength greater than or equal to 0.5 lb / in represents a significant difference in copper foil tensile strength between different substrates.

[0139] Breakdown voltage (BDV)

[0140] Select the above copper-free substrate 2 (formed by laminating eight prepregs) as the sample to be tested (with dimensions of 75 mm in length, 50 mm in width, and 1.6 mm in height), and measure each sample to be tested according to the method described in IPC-TM-650 2.5.6.3. Immerse the above sample in insulating oil (transformer oil, purchased from Great Wall Lubricants), and increase the voltage of the above sample from 0 V at a rate of 500 V per second on the test device. When the leakage current of the sample shows greater than 5 mA, record the current voltage value, which is the breakdown voltage. The unit of the breakdown voltage is volt (abbreviated as V). In this field, a difference in BDV values less than 1 kV indicates that there is no significant difference in the breakdown voltages of the substrates (no significant difference means there is no significant technical difficulty), and a difference in BDV values greater than or equal to 1 kV indicates that there is a significant difference in the breakdown voltages of different substrates (there is a significant technical difficulty).

[0141] Dissipation factor (Df)

[0142] In the measurement of the dissipation factor, select the above copper-free substrate 1 (formed by laminating two prepregs, with a resin content of approximately 70%) as the sample to be tested. Use a microwave dielectric analyzer (purchased from AET Corporation, Japan), and refer to the method described in JIS C2565 to measure each sample to be tested at room temperature (about 25°C) and at a frequency of 10 GHz to obtain the dissipation factor. The lower the dissipation factor, the better the dielectric properties of the sample to be tested. At a measurement frequency of 10 GHz and when the Df value is in the range of 0.0040 to 0.0080, a difference in Df values less than 0.0005 indicates that there is no significant difference in the dissipation factors of the substrates (no significant difference means there is no significant technical difficulty), and a difference in Df values greater than or equal to 0.0005 indicates that there is a significant difference in the dissipation factors of different substrates (there is a significant technical difficulty).

[0143] Dielectric constant (Dk)

[0144] In the measurement of the dielectric constant, the above copper-free substrate 1 (formed by laminating two prepregs, with a resin content of about 70%) was selected as the sample to be measured. A microwave dielectrometer (purchased from AET Corporation, Japan) was used to measure 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, for high-dielectric-constant materials, a difference in Dk value less than 0.5 indicates that the dielectric constants of the substrates are not significantly different (no significant difference means no significant technical difficulty), and a difference in Dk value greater than or equal to 0.5 indicates that there is a significant difference in the dielectric constants of different substrates (there is a significant technical difficulty).

[0145] Thermal conductivity (Tk)

[0146] The above copper-free substrate 2 (formed by laminating eight prepregs) was selected as the sample to be measured (with dimensions of 31 mm in length, 31 mm in width, and 0.85 mm in height), and each sample to be measured was measured according to the method described in ASTM-D5470. The above sample was heated starting from room temperature (about 25°C) on the test device. When the temperature reached 80°C at the 30th minute after heating, a thermal conductivity measuring instrument (model LW-9091ir, purchased from Ruiling Technology) was used to calculate the thermal conductivity analysis value to obtain the thermal conductivity. The unit of thermal conductivity is W / (m·K). In this field, a difference in Tk value less than 0.1 W / (m·K) indicates that the thermal conductivities of the substrates are not significantly different (no significant difference means no significant technical difficulty), and a difference in Tk value greater than or equal to 0.1 W / (m·K) indicates that there is a significant difference in the thermal conductivities of different substrates (there is a significant technical difficulty).

[0147] Based on the above test results, the following phenomena can be observed.

[0148] In Examples E1 to E16 of the resin composition using 100 parts by weight of the thermosetting resin, 15 to 50 parts by weight of the sintered body formed by aluminum nitride and boron nitride, and 180 to 280 parts by weight of titanium dioxide according to the present invention, the effects of a tensile strength on copper foil greater than or equal to 4.03 lb / in, a breakdown voltage greater than or equal to 35.5 kV, and a dielectric loss less than or equal to 0.0049 can be achieved simultaneously.

[0149] Compared with Examples E1 to E16, Comparative Examples C1, C2, and C9 that did not use the sintered body formed by aluminum nitride and boron nitride of the present invention, and Comparative Examples C3, C4, C10, and C11 that did not use titanium dioxide could not achieve the above effects simultaneously.

[0150] Compared with Examples E1 to E16, if the addition amount of the sintered body formed by aluminum nitride and boron nitride in the resin composition falls outside the range of 15 parts by weight to 50 parts by weight, such as Comparative Examples C5 to C6, at least one of the properties such as the tensile strength of the copper foil, the breakdown voltage, and the dielectric loss cannot meet the requirements.

[0151] Compared with Examples E1 to E16, if the addition amount of titanium dioxide in the resin composition falls outside the range of 180 parts by weight to 280 parts by weight, such as Comparative Examples C7 to C8, at least one of the properties such as the tensile strength of the copper foil, the breakdown voltage, and the dielectric loss also cannot meet the requirements.

[0152] Generally speaking, the resin composition of the present invention can simultaneously achieve effects such as a tensile strength of the copper foil greater than or equal to 4.03 lb / in, a breakdown voltage greater than or equal to 35.5 kV, a dielectric loss less than or equal to 0.0049, a dielectric constant greater than or equal to 6.9, and a thermal conductivity greater than or equal to 0.61 W / (m·K).

[0153] 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 text, the term "exemplary" means "as an example, a paradigm, or an illustration". Any exemplary embodiment in this text is not necessarily to be construed as being better or more advantageous than other embodiments.

[0154] In addition, although at least one exemplary embodiment or comparative example has been presented in the foregoing embodiments, it should be understood that there can still be a large number of variations in the present invention. It should also be understood that the embodiments described herein are not intended to limit the scope, use, or aspects of the claimed application target in any way. On the contrary, the foregoing embodiments will provide those skilled in the art with a simple guide to implement one or more of the embodiments. Furthermore, various changes can be made to the functions and arrangements of the components without departing from the scope defined by the claims, and the claims include known equivalents and all foreseeable equivalents at the time of filing this patent application.

Claims

1. A resin composition, characterized in that, it comprises: (A) 100 parts by weight of a thermosetting resin, which comprises a vinyl-containing polyphenylene ether resin, a maleimide resin or a combination thereof; (B) 15 to 50 parts by weight of a sintered body formed from aluminum nitride and boron nitride; and (C) 180 to 280 parts by weight of titanium dioxide.

2. The resin composition according to claim 1, characterized in that, the vinyl-containing polyphenylene ether resin comprises a vinylbenzyl biphenyl polyphenylene ether resin, a methacrylate-containing polyphenylene ether resin, a vinylbenzyl bisphenol A polyphenylene ether resin, a vinyl-extended polyphenylene ether resin or a combination thereof.

3. The resin composition according to claim 1, characterized in that, the maleimide resin comprises diethyl bis(maleimidomethyl)toluene, 4,4'-diphenylmethane bismaleimide, biphenyl maleimide, polyphenylmethane maleimide, bisphenol A diphenyl ether bismaleimide, 3,3'-dimethyl-5,5'-diethyl-4,4'-diphenylmethane bismaleimide, a maleimide resin containing an aliphatic long-chain structure, a prepolymer of 4,4'-diphenylmethane bismaleimide and diallyl bisphenol A, a vinylcyclopentadiene-modified maleimide or a combination thereof.

4. The resin composition according to claim 1, characterized in that, it further comprises 5 to 20 parts by weight of alumina.

5. The resin composition according to claim 1, characterized in that, it further comprises a flame retardant, a crosslinking agent, a curing accelerator, a polymerization inhibitor, a solvent, a silane coupling agent, a dye, a toughening agent, a core-shell rubber or a combination thereof.

6. An article made from the resin composition according to claim 1, characterized in that, it comprises a prepreg, a resin film, a laminate or a printed circuit board.

7. The article according to claim 6, characterized in that, the tensile strength against copper foil measured by the method described in IPC-TM-650 2.4.8 is greater than or equal to 4.03 lb / in.

8. The article according to claim 6, characterized in that, the breakdown voltage measured by the method described in IPC-TM-650 2.5.6.3 is greater than or equal to 35.5 kV.

9. The article according to claim 6, characterized in that, the dielectric loss measured by the method described in JIS C2565 at a frequency of 10 GHz is less than or equal to 0.0049.

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