Resin composition and application thereof

Abstract

The invention discloses a resin composition and application thereof. The resin composition comprises the following components in parts by solid weight: 50-100 parts by weight of a first component; 5-60 parts by weight of a second component; 5-50 parts by weight of a third component; 0-50 parts by weight of epoxy resin; wherein the first component is a maleimide resin or a maleimide prepolymer, the second component is a cross-linking agent, the third component is an elastomer, and at least two of the first component, the second component and the third component comprise at least one of limiting groups. Compared with the prior art, the resin composition and the application thereof have the advantages that by adopting the components containing the styrene structural units, the compatibility among the components in the resin composition can be improved, the dielectric property of the resin composition can be reduced, the toughness can be improved, the warping of a plate can be improved, and excellent heat resistance and proper modulus can be kept; the comprehensive performance is excellent.

Description

Technical Field

[0001] The present application belongs to the technical field of electronic materials, and relates to a resin composition and the application of the resin composition in a prepreg, a copper-clad laminate, an insulating plate, an insulating film, a circuit substrate and an electronic device. Background Art

[0002] In recent years, with the rapid development of mobile Internet technology, high-density interconnection technology (HDI) electronic products have put forward higher requirements on the substrate of their printed circuit boards. In addition to requiring them to have high heat resistance, high modulus and excellent flame retardancy, they are also required to have lower water absorption, lower dielectric constant, lower dielectric loss value and lower thermal expansion coefficient.

[0003] Maleimide resin is one of the commonly used high-performance resin materials in the field of copper clad laminates. It is widely used for its excellent heat resistance, high modulus, low CTE, electrical insulation, good mechanical properties and dimensional stability. However, maleimide resin also has disadvantages such as high brittleness, high dielectric constant and dielectric loss, and poor processing performance, which limits its large-scale application. Summary of the invention

[0004] In order to solve the above technical problems, the present application provides a resin composition and a prepreg, a copper-clad laminate, an insulating plate, an insulating film, a circuit substrate and an electronic device made using the resin composition.

[0005] To achieve one of the above-mentioned application purposes, an embodiment of the present application provides a resin composition, which comprises, by solid weight:

[0006] 50 to 100 parts by weight of the first component;

[0007] 5 to 60 parts by weight of the second component;

[0008] 5 to 50 parts by weight of the third component;

[0009] Epoxy resin 0-50 parts by weight;

[0010] Wherein, the first component is a maleimide resin or a maleimide prepolymer, the second component is a crosslinking agent, the third component is an elastomer, and at least two of the first component, the second component, and the third component contain at least one of the following groups:

[0011]

[0012] Wherein, X1 is a C1-C5 alkyl group.

[0013] In this way, by adopting a component containing a styrene structural unit, the compatibility between the components in the resin composition can be improved, the dielectric properties of the resin composition can be reduced, the toughness can be improved, the warping of the sheet can be improved, and excellent heat resistance and appropriate modulus can be maintained, thereby having excellent comprehensive performance.

[0014] As a further improvement of one embodiment of the present application, the first component, the second component, and the third component each contain at least one of the following groups:

[0015]

[0016] Wherein, X1 is a C1-C5 alkyl group.

[0017] When the maleimide resin or maleimide prepolymer, the crosslinking agent and the elastomer all contain styrene units, the resin composition can obtain a very homogeneous mixed glue solution, which can improve the production processability and obtain a lower CTE value.

[0018] As a further improvement of one embodiment of the present application, the elastomer is a styrene elastomer.

[0019] As a further improvement of one embodiment of the present application, the elastomer is a hydrogenated or partially hydrogenated styrene elastomer.

[0020] As a further improvement of one embodiment of the present application, the elastomer is at least one of styrene-butadiene copolymer, styrene-butadiene-styrene copolymer, styrene-pentadiene copolymer, and styrene-pentadiene-styrene copolymer.

[0021] As a further improvement of one embodiment of the present application, the elastomer contains epoxy groups, anhydride groups or hydroxyl groups.

[0022] As a further improvement of one embodiment of the present application, the maleimide resin is at least one of the following structures:

[0023] R is selected from hydrogen or C1-C5 alkyl, R'

[0024] is selected from hydrogen or C1-C5 alkyl, and n is an integer from 1 to 20;

[0025] R is selected from hydrogen or C1-C5 alkyl, R' is selected from hydrogen or C1-C5 alkyl, and n is an integer from 1 to 20;

[0026]

[0027]

[0028] R1 is methylene, ethylene or R2 is hydrogen, methyl or ethyl;

[0029]

[0030] n is an integer from 1 to 10;

[0031] n is an integer from 1 to 10;

[0032] R is hydrogen, methyl or ethyl, and n is an integer of 1-10.

[0033] As a further improvement of an embodiment of the present application, the maleimide resin is at least one of structural formula (1) and structural formula (2).

[0034] As a further improvement of one embodiment of the present application, the maleimide prepolymer is selected from at least one of a prepolymer of a diallyl compound and a maleimide compound, a prepolymer of a diamine compound and a maleimide compound, a prepolymer of a polyfunctional amine and a maleimide compound, and a prepolymer of an acidic phenol compound and a maleimide compound.

[0035] As a further improvement of one embodiment of the present application, the cross-linking agent is at least one of triallyl isocyanate monomer, triallyl isocyanate monomer prepolymer, butadiene, styrene, styrene-anhydride copolymer, pentadiene, methacrylate, dicyclopentadienyl methacrylate, norbornene, and cyclopentadiene.

[0036] As a further improvement of one embodiment of the present application, the crosslinking agent is a styrene-anhydride copolymer, wherein the molar ratio of styrene to anhydride is 1:1, 2:1, 3:1, 4:1, 6:1 or 8:1.

[0037] As a further improvement of one embodiment of the present application, the structural formula of the cross-linking agent is:

[0038] Among them, m / n=1~8.

[0039] When the cross-linking agent is a styrene-anhydride copolymer, the epoxy group will react with the anhydride group and retain the styrene group. The cross-linking agent maintains very excellent resin compatibility with the maleimide resin or maleimide prepolymer containing styrene structural units and the styrene-containing elastomer, which can not only inhibit the decrease in heat resistance, but also improve the production processability to obtain a cured product with high heat resistance, low dielectric properties, low CTE and appropriate modulus value.

[0040] As a further improvement of one embodiment of the present application, the epoxy resin is at least one of dicyclopentadiene epoxy resin, phosphorus-containing epoxy resin, isocyanate-modified epoxy resin, bisphenol A epoxy resin, phenol-type novolac epoxy resin, o-cresol-type epoxy resin, epoxidized polybutadiene resin, naphthalene ring-containing epoxy resin, biphenyl epoxy resin, bisphenol F epoxy resin, trifunctional epoxy resin, hydrogenated bisphenol A epoxy resin, and hydrogenated bisphenol F epoxy resin.

[0041] As a further improvement of an embodiment of the present application, the solid weight of the epoxy resin is 5 to 40 parts by weight.

[0042] As a further improvement of an embodiment of the present application, the epoxy resin is at least one of the following structural formulas:

[0043]

[0044]

[0045]

[0046] In the above structural formula, n is an integer of 1-10.

[0047] When the epoxy resin adopts a naphthalene-type structure, a better balance can be achieved among the dielectric properties, CTE, heat resistance and modulus of the resin composition, and the resin composition has excellent dielectric properties, CTE, heat resistance and modulus.

[0048] As a further improvement of an embodiment of the present application, the resin composition further comprises 1 to 50 parts by weight of an epoxy resin curing agent, calculated on a solid weight basis.

[0049] As a further improvement of one embodiment of the present application, the epoxy resin curing agent is selected from at least one of an amine curing agent, an active ester curing agent, and a phenol curing agent.

[0050] As a further improvement of one embodiment of the present application, the amine curing agent is selected from at least one of diaminodiphenylmethane, bis[4-(4-aminophenoxy)phenyl]propane, bis[4-(4-aminophenoxy)phenyl]hexafluoropropane, diaminobenzophenone, diaminodiphenyl ether, diaminodiphenyl sulfone, diaminobiphenyl, diaminodiphenyl sulfide, diaminobinaphthyl, diaminodiphenylfluorene, diaminoanthraquinone, and dicyandiamide.

[0051] As a further improvement of one embodiment of the present application, the active ester curing agent is a dicyclopentadienyl active ester or a naphthyl active ester.

[0052] As a further improvement of an embodiment of the present application, the phenolic curing agent is a phenolic resin or a benzoxazine resin.

[0053] As a further improvement of an embodiment of the present application, the resin composition further comprises 5 to 40 parts by weight of a cyanate ester resin, calculated on a solid weight basis.

[0054] As a further improvement of one embodiment of the present application, the cyanate resin is selected from at least one of bisphenol A type cyanate resin, bisphenol F type cyanate resin, bisphenol S type cyanate resin, bisphenol E type cyanate resin, bisphenol M type cyanate resin, double bond-containing cyanate resin, phosphorus-containing cyanate resin, phenolic cyanate resin, biphenyl type cyanate resin, naphthalene ring type cyanate resin, and dicyclopentadiene type cyanate resin.

[0055] As a further improvement of an embodiment of the present application, the cyanate ester resin is a monomer, a prepolymer, a polymer or a mixture of the above three.

[0056] As a further improvement of an embodiment of the present application, the resin composition further comprises 10 to 200 parts by weight of an inorganic filler, calculated on a solid weight basis.

[0057] As a further improvement of one embodiment of the present application, the inorganic filler is selected from at least one of fused silica, crystalline silica, spherical silica, hollow silica, aluminum hydroxide, aluminum oxide, talc, aluminum nitride, boron nitride, silicon carbide, barium sulfate, barium titanate, strontium titanate, calcium carbonate, calcium silicate, mica, and glass fiber powder.

[0058] As a further improvement of an embodiment of the present application, the inorganic filler is spherical silica.

[0059] As a further improvement of one embodiment of the present application, the inorganic filler is surface treated with a silane coupling agent, and the silane coupling agent is at least one of an aminosilane coupling agent, an epoxysilane coupling agent or a double bond-containing silane coupling agent.

[0060] As a further improvement of an embodiment of the present application, the resin composition further comprises 5 to 60 parts by weight of a flame retardant, calculated on a solid weight basis.

[0061] As a further improvement of an embodiment of the present application, the flame retardant is at least one of a bromine-based flame retardant, a phosphorus-based flame retardant, a nitrogen-based flame retardant, an organosilicon flame retardant, and an organic metal salt flame retardant.

[0062] As an optional solution, the brominated flame retardant is selected from decabromodiphenyl ether, decabromodiphenyl ethane, brominated styrene or tetrabromophthalamide.

[0063] As an optional solution, the phosphorus flame retardant is selected from inorganic phosphorus, condensed phosphate compounds, phosphoric acid compounds, hypophosphorous acid compounds, phosphorus oxide compounds, 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, 10-(2,5-dihydroxyphenyl)-9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, 10-phenyl-9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, tris(2,6-dimethylphenyl)phosphine, (m is an integer from 1 to 5), Phosphazene or modified phosphazene.

[0064] Among them, DOPO group is

[0065] As an optional solution, the flame retardant is a condensed phosphate ester, a hypophosphite or a bis-DOPO compound.

[0066] As a further improvement of an embodiment of the present application, the resin composition further comprises 0.01 to 5 parts by weight of a catalyst, calculated on a solid weight basis.

[0067] As an optional solution, the catalyst is at least one of an imidazole catalyst, an organic phosphorus catalyst, a pyridine catalyst, and an organic metal salt catalyst.

[0068] As an optional solution, the catalyst is at least one of 4-dimethylaminopyridine, 2-methylimidazole, 2-ethyl-4-methylimidazole, triphenylphosphine, 2-phenylimidazole and zinc octanoate.

[0069] The present application also provides the use of the above resin composition in prepregs, copper-clad laminates, insulating plates, insulating films, circuit substrates and electronic devices, which are specifically described as follows:

[0070] The present application also provides a prepreg, comprising a reinforcing material and the aforementioned resin composition; the resin composition is wrapped on the reinforcing material.

[0071] The preparation method of the semi-cured sheet is as follows: the resin composition is dissolved in a solvent to prepare a glue solution, and then the glue solution is applied to the reinforcing material by an impregnation method, and the impregnated reinforcing material is taken out and baked at a temperature of 100 to 180° C. for 1 to 15 minutes; after drying, the semi-cured sheet can be obtained.

[0072] As an optional solution, the solvent is selected from at least one of acetone, butanone, methyl isobutyl ketone, N,N-dimethylformamide, N,N-dimethylacetamide, ethylene glycol methyl ether, propylene glycol methyl ether, benzene, toluene, xylene, and cyclohexane.

[0073] As an optional solution, the reinforcing material is selected from at least one of natural fibers, organic synthetic fibers, organic fabrics, and inorganic fabrics.

[0074] Preferably, the reinforcing material is glass fiber cloth. The glass fiber cloth is preferably open fiber cloth or flat cloth. More preferably, the glass fiber cloth is E glass fiber cloth, S glass fiber cloth, T glass fiber cloth or Q glass fiber cloth.

[0075] In addition, when the reinforcing material is glass fiber cloth, the glass fiber cloth is chemically treated with a coupling agent in advance to improve the interface bonding between the resin composition and the glass fiber cloth. The coupling agent here is preferably an epoxy silane coupling agent or an amino silane coupling agent to provide good water resistance and heat resistance.

[0076] The present application also provides a copper clad laminate, comprising a piece of the aforementioned prepreg and a metal foil arranged on at least one side of the surface of the prepreg; or comprising a composite sheet formed by overlapping multiple pieces of the aforementioned prepreg and a metal foil arranged on at least one side of the surface of the composite sheet.

[0077] The preparation method of the copper clad laminate is as follows: a metal foil is coated on one side or both sides of a prepreg, or at least two prepregs are stacked to form a composite sheet, a metal foil is coated on one side or both sides of the composite sheet, and the copper clad laminate is obtained by hot pressing. The hot pressing conditions are as follows: a pressure of 0.2 to 2 MPa, a temperature of 150 to 250° C., and a pressing time of 2 to 4 hours.

[0078] Preferably, the metal foil is selected from copper foil or aluminum foil. The thickness of the metal foil is 5 μm, 8 μm, 12 μm, 18 μm, 35 μm or 70 μm.

[0079] The present application also provides an insulating board, comprising at least one of the aforementioned prepreg sheets.

[0080] The present application also provides an insulating film, comprising a carrier film and the above-mentioned resin composition coated thereon.

[0081] The insulating film is prepared by the following method: the resin composition is dissolved in a solvent to prepare a glue solution, the glue solution is then coated on a carrier film, and the carrier film coated with the glue solution is heated and dried to obtain the insulating film.

[0082] As an optional solution, the solvent is selected from at least one of acetone, butanone, methyl isobutyl ketone, N,N-dimethylformamide, N,N-dimethylacetamide, ethylene glycol methyl ether, propylene glycol methyl ether, benzene, toluene, xylene, and cyclohexane.

[0083] As an optional solution, the carrier film is selected from at least one of PET film, PP film, PE film and PVC film.

[0084] The present application also provides a circuit substrate, comprising at least one of the aforementioned prepreg, copper-clad laminate, insulating plate, and insulating film.

[0085] The present application also provides an electronic device, comprising the aforementioned circuit substrate.

[0086] The present application provides a resin composition and application of the resin composition in a prepreg, a copper-clad laminate, an insulating plate, an insulating film, a circuit substrate and an electronic device.

[0087] Due to the application of the above technical solution, the present application has the following advantages compared with the prior art:

[0088] By using components containing styrene structural units, the compatibility between the components in the resin composition can be improved, the dielectric properties of the resin composition can be reduced, the toughness can be improved, the warping of the sheet can be improved, and excellent heat resistance and appropriate modulus can be maintained, thereby having excellent comprehensive performance. DETAILED DESCRIPTION

[0089] The technical solution of the present application is further introduced below in conjunction with specific implementation methods. The following embodiments are merely descriptive and not restrictive, and the protection scope of the present application cannot be limited by them.

[0090] One embodiment of the present application provides a resin composition and the use of the resin composition in a prepreg, a copper-clad laminate, an insulating board, an insulating film, a circuit substrate and an electronic device.

[0091] The resin composition, measured by solid weight, comprises:

[0092] 50 to 100 parts by weight of the first component;

[0093] 5 to 60 parts by weight of the second component;

[0094] 5 to 50 parts by weight of the third component;

[0095] Epoxy resin 0-50 parts by weight;

[0096] Wherein, the first component is a maleimide resin or a maleimide prepolymer, the second component is a crosslinking agent, the third component is an elastomer, and at least two of the first component, the second component, and the third component contain at least one of the following groups:

[0097]

[0098] Wherein, X1 is a C1-C5 alkyl group.

[0099] That is to say, two of the first component, the second component, and the third component contain at least one of the above-mentioned groups, and the at least one above-mentioned group contained in one of the two may be the same as or different from the at least one above-mentioned group contained in the other one; or, all three contain at least one of the above-mentioned groups, and the at least one above-mentioned group contained in any one of the three may be the same as or different from the at least one above-mentioned group contained in the other two.

[0100] Preferably, the first component, the second component, and the third component each contain at least one of the following groups:

[0101]

[0102] Wherein, X1 is a C1-C5 alkyl group.

[0103] That is to say, the first component, the second component, and the third component all contain at least one of the above-mentioned groups, and the at least one above-mentioned group contained in any one of the three may be the same as the at least one above-mentioned group contained in the other two, or the three may be different from each other.

[0104] When the maleimide resin or maleimide prepolymer, the crosslinking agent and the elastomer all contain styrene units, the resin composition can obtain a very homogeneous mixed glue solution, which can improve the production processability and obtain a lower CTE value.

[0105] Preferably, the elastomer is a styrene elastomer.

[0106] Preferably, the elastomer is a hydrogenated or partially hydrogenated styrene elastomer.

[0107] Preferably, the elastomer is at least one of styrene-butadiene copolymer, styrene-butadiene-styrene copolymer, styrene-pentadiene copolymer and styrene-pentadiene-styrene copolymer.

[0108] Preferably, the elastomer contains epoxy groups, anhydride groups or hydroxyl groups.

[0109] The elastomer can be selected from SEPTONTM 2000 series (2002, 2004, 2005, 2006, 2063, 2104), SEPTONTM 4000 series (4033, 4044, 4055, 4077), HYBRAR TM7000 series (7125, 7311), SEPTONTM 8000 series (8004, 8006, 8007L, 8851), SEPTONTM V series (9461, 9475), SEPTONTMQ1250; the elastomer can also be H1041, H1043, H1051, H1052, H1053, H1221, M1913 manufactured by Asahi Kasei.

[0110] Preferably, the maleimide resin is at least one of the following structures:

[0111] R is selected from hydrogen or C1-C5 alkyl, R' is selected from hydrogen or C1-C5 alkyl, and n is an integer from 1 to 20;

[0112] R is selected from hydrogen or C1-C5 alkyl, R' is selected from hydrogen or C1-C5 alkyl, and n is an integer from 1 to 20;

[0113]

[0114] R1 is methylene, ethylene or R2 is hydrogen, methyl or ethyl;

[0115]

[0116] n is an integer from 1 to 10;

[0117] n is an integer from 1 to 10;

[0118] R is hydrogen, methyl or ethyl, and n is an integer of 1-10.

[0119] More preferably, the maleimide resin is at least one of structural formula (1) and structural formula (2).

[0120] Preferably, the maleimide prepolymer is at least one selected from prepolymers of diallyl compounds and maleimide compounds, prepolymers of diamine compounds and maleimide compounds, prepolymers of polyfunctional amines and maleimide compounds, and prepolymers of acidic phenol compounds and maleimide compounds.

[0121] The maleimide compound can be selected from BMI-1000, BMI-1000H, BMI-1100, BMI-1100H, BMI-2000, BMI-2300, BMI-3000, BMI-3000H, BMI-4000H, BMI-5000, BMI-5100, BMI-7000, BMI-7000H manufactured by Yamato Chemical Industry Co., Ltd., or BMI, BMI-70, BMI-80 manufactured by KI Chemical Industry Co., Ltd., or MIR-3000, MIR-5000 manufactured by Nippon Kayaku Co., Ltd., or X9-450, X9-470 manufactured by DIC Corporation of Japan, or D936, D937, D939, D950 manufactured by Sichuan Dongcai Co., Ltd.

[0122] The maleimide compound is preferably BMI-2300 manufactured by Yamato Chemical Industry Co., Ltd., BMI-70 and BMI-80 manufactured by KI Chemical Industry Co., Ltd., or MIR-3000 manufactured by Nippon Kayaku Co., Ltd.

[0123] Preferably, the crosslinking agent is at least one of triallyl isocyanate monomer, triallyl isocyanate monomer prepolymer, butadiene, styrene, styrene-anhydride copolymer, pentadiene, methacrylate, dicyclopentadienyl methacrylate, norbornene, and cyclopentadiene.

[0124] Preferably, the crosslinking agent is a styrene-anhydride copolymer, wherein the molar ratio of styrene to anhydride is 1:1, 2:1, 3:1, 4:1, 6:1 or 8:1.

[0125] Preferably, the cross-linking agent has the structural formula:

[0126] Among them, m / n=1~8.

[0127] When the cross-linking agent is a styrene-anhydride copolymer, the epoxy group will react with the anhydride group and retain the styrene group. The cross-linking agent maintains very excellent resin compatibility with the maleimide resin or maleimide prepolymer containing styrene structural units and the styrene-containing elastomer, which can not only inhibit the decrease in heat resistance, but also improve the production processability to obtain a cured product with high heat resistance, low dielectric properties, low CTE and appropriate modulus value.

[0128] Preferably, the epoxy resin is at least one of dicyclopentadiene epoxy resin, phosphorus-containing epoxy resin, isocyanate-modified epoxy resin, bisphenol A epoxy resin, phenol novolac epoxy resin, o-cresol novolac epoxy resin, epoxidized polybutadiene resin, naphthalene ring-containing epoxy resin, biphenyl epoxy resin, bisphenol F epoxy resin, trifunctional epoxy resin, hydrogenated bisphenol A epoxy resin, and hydrogenated bisphenol F epoxy resin.

[0129] Preferably, the solid weight of the epoxy resin is 5 to 40 parts by weight.

[0130] Preferably, the epoxy resin is at least one of the following structural formulas:

[0131]

[0132]

[0133] In the above structural formula, n is an integer of 1-10.

[0134] When the epoxy resin adopts a naphthalene-type structure, a better balance can be achieved among the dielectric properties, CTE, heat resistance and modulus of the resin composition, and the resin composition has excellent dielectric properties, CTE, heat resistance and modulus.

[0135] The naphthalene ring-containing epoxy resin can be HP-6000 manufactured by DIC or NC-7000 manufactured by Nippon Kayaku.

[0136] Furthermore, the resin composition further comprises 1 to 50 parts by weight of an epoxy resin curing agent based on solid weight.

[0137] Preferably, the epoxy resin curing agent is selected from at least one of an amine curing agent, an active ester curing agent, and a phenol curing agent.

[0138] Preferably, the amine curing agent is selected from at least one of diaminodiphenylmethane, bis[4-(4-aminophenoxy)phenyl]propane, bis[4-(4-aminophenoxy)phenyl]hexafluoropropane, diaminobenzophenone, diaminodiphenyl ether, diaminodiphenyl sulfone, diaminobiphenyl, diaminodiphenyl sulfide, diaminobinaphthyl, diaminodiphenylfluorene, diaminoanthraquinone and dicyandiamide.

[0139] Preferably, the active ester curing agent is a dicyclopentadienyl active ester or a naphthyl active ester.

[0140] Preferably, the phenolic curing agent is a phenolic resin or a benzoxazine resin.

[0141] Furthermore, the resin composition further comprises 5 to 40 parts by weight of cyanate ester resin based on solid weight.

[0142] As an optional scheme, the cyanate ester resin is selected from at least one of bisphenol A type cyanate ester resin, bisphenol F type cyanate ester resin, bisphenol S type cyanate ester resin, bisphenol E type cyanate ester resin, bisphenol M type cyanate ester resin, double bond-containing cyanate ester resin, phosphorus-containing cyanate ester resin, phenolic cyanate ester resin, biphenyl type cyanate ester resin, naphthalene ring type cyanate ester resin, and dicyclopentadiene type cyanate ester resin.

[0143] Preferably, the cyanate ester resin is a monomer, a prepolymer, a polymer or a mixture thereof.

[0144] Furthermore, the resin composition further comprises 10 to 200 parts by weight of an inorganic filler based on solid weight.

[0145] As an optional solution, the inorganic filler is selected from at least one of fused silica, crystalline silica, spherical silica, hollow silica, aluminum hydroxide, aluminum oxide, talc, aluminum nitride, boron nitride, silicon carbide, barium sulfate, barium titanate, strontium titanate, calcium carbonate, calcium silicate, mica, and glass fiber powder.

[0146] Preferably, the inorganic filler is spherical silica.

[0147] More preferably, the inorganic filler is surface treated with a silane coupling agent, and the silane coupling agent is at least one of an aminosilane coupling agent, an epoxysilane coupling agent or a double-bond-containing silane coupling agent.

[0148] Furthermore, the resin composition further comprises 5 to 60 parts by weight of a flame retardant based on solid weight.

[0149] As an optional solution, the flame retardant is at least one of a bromine flame retardant, a phosphorus flame retardant, a nitrogen flame retardant, an organosilicon flame retardant, and an organic metal salt flame retardant.

[0150] As an optional solution, the brominated flame retardant is selected from decabromodiphenyl ether, decabromodiphenyl ethane, brominated styrene or tetrabromophthalamide.

[0151] As an optional solution, the phosphorus flame retardant is selected from inorganic phosphorus, condensed phosphate compounds, phosphoric acid compounds, hypophosphorous acid compounds, phosphorus oxide compounds, 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, 10-(2,5-dihydroxyphenyl)-9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, 10-phenyl-9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, tris(2,6-dimethylphenyl)phosphine, (m is an integer from 1 to 5), Phosphazene or modified phosphazene.

[0152] As an optional solution, the flame retardant is a condensed phosphate ester, a hypophosphite or a bis-DOPO compound.

[0153] Furthermore, the resin composition further comprises 0.01 to 5 parts by weight of a catalyst based on solid weight.

[0154] As an optional solution, the catalyst is at least one of an imidazole catalyst, an organic phosphorus catalyst, a pyridine catalyst, and an organic metal salt catalyst.

[0155] As an optional solution, the catalyst is at least one of 4-dimethylaminopyridine, 2-methylimidazole, 2-ethyl-4-methylimidazole, triphenylphosphine, 2-phenylimidazole and zinc octanoate.

[0156] The present application also provides the use of the above resin composition in prepregs, copper-clad laminates, insulating plates, insulating films, circuit substrates and electronic devices, which are specifically described as follows:

[0157] The present application also provides a prepreg, comprising a reinforcing material and the aforementioned resin composition; the resin composition is wrapped on the reinforcing material.

[0158] The preparation method of the semi-cured sheet is as follows: the resin composition is dissolved in a solvent to prepare a glue solution, and then the glue solution is applied to the reinforcing material by an impregnation method, and the impregnated reinforcing material is taken out and baked at a temperature of 100 to 180° C. for 1 to 15 minutes; after drying, the semi-cured sheet can be obtained.

[0159] As an optional solution, the solvent is selected from at least one of acetone, butanone, methyl isobutyl ketone, N,N-dimethylformamide, N,N-dimethylacetamide, ethylene glycol methyl ether, propylene glycol methyl ether, benzene, toluene, xylene, and cyclohexane.

[0160] As an optional solution, the reinforcing material is selected from at least one of natural fibers, organic synthetic fibers, organic fabrics, and inorganic fabrics.

[0161] Preferably, the reinforcing material is glass fiber cloth. The glass fiber cloth is preferably open fiber cloth or flat cloth. More preferably, the glass fiber cloth is E glass fiber cloth, S glass fiber cloth, T glass fiber cloth or Q glass fiber cloth.

[0162] In addition, when the reinforcing material is glass fiber cloth, the glass fiber cloth is chemically treated with a coupling agent in advance to improve the interface bonding between the resin composition and the glass fiber cloth. The coupling agent here is preferably an epoxy silane coupling agent or an amino silane coupling agent to provide good water resistance and heat resistance.

[0163] The present application also provides a copper clad laminate, comprising a piece of the aforementioned prepreg and a metal foil arranged on at least one side of the surface of the prepreg; or comprising a composite sheet formed by overlapping multiple pieces of the aforementioned prepreg and a metal foil arranged on at least one side of the surface of the composite sheet.

[0164] The preparation method of the copper clad laminate is as follows: a metal foil is coated on one side or both sides of a prepreg, or at least two prepregs are stacked to form a composite sheet, a metal foil is coated on one side or both sides of the composite sheet, and the copper clad laminate is obtained by hot pressing. The hot pressing conditions are as follows: a pressure of 0.2 to 2 MPa, a temperature of 150 to 250° C., and a pressing time of 2 to 4 hours.

[0165] Preferably, the metal foil is selected from copper foil or aluminum foil. The thickness of the metal foil is 5 μm, 8 μm, 12 μm, 18 μm, 35 μm or 70 μm.

[0166] The present application also provides an insulating board, comprising at least one of the aforementioned prepreg sheets.

[0167] The present application also provides an insulating film, comprising a carrier film and the above-mentioned resin composition coated thereon.

[0168] The insulating film is prepared by the following method: the resin composition is dissolved in a solvent to prepare a glue solution, the glue solution is then coated on a carrier film, and the carrier film coated with the glue solution is heated and dried to obtain the insulating film.

[0169] As an optional solution, the solvent is selected from at least one of acetone, butanone, methyl isobutyl ketone, N,N-dimethylformamide, N,N-dimethylacetamide, ethylene glycol methyl ether, propylene glycol methyl ether, benzene, toluene, xylene, and cyclohexane.

[0170] As an optional solution, the carrier film is selected from at least one of PET film, PP film, PE film and PVC film.

[0171] The present application also provides a circuit substrate, comprising at least one of the aforementioned prepreg, copper-clad laminate, insulating plate, and insulating film.

[0172] The present application also provides an electronic device, comprising the aforementioned circuit substrate.

[0173] The present application provides a resin composition and application of the resin composition in a prepreg, a copper-clad laminate, an insulating plate, an insulating film, a circuit substrate and an electronic device.

[0174] The technical solution of the present application is further described below in conjunction with some specific preparation examples, embodiments and comparative examples. Of course, these embodiments are only a part of the many variations of the embodiments of the present application, but not all.

[0175] Preparation Example 1

[0176] Step (1), add 242.4 g of 2-ethylaniline, 242 g of xylene and 80 g of activated clay to a reaction bottle, stir evenly, and heat to 125° C. to react for 30 min; then add 272 g of DVB810 (wherein the molar ratio of divinylbenzene to ethylstyrene is 81:19) dropwise over 2 h, and continue to react for 1 h; then heat to 185° C. to react for 4 h to obtain an intermediate amine compound;

[0177] Step (2), take 117.7g of maleic acid and 700g of toluene, stir evenly at room temperature, continue to add 214g of intermediate amine compound and 175g of DMF solvent, and then react for 2h, then add 37.1g of p-toluenesulfonic acid hydrate, heat to 120°C, and then perform dehydration, neutralization and reduced pressure distillation to obtain concentrated maleimide compound, i.e. maleimide resin A.

[0178] Preparation Example 2

[0179] Maleimide prepolymer B was obtained by reacting 100 g of a maleimide resin (BMI-2300 manufactured by Yamato Chemical Industry Co., Ltd.) with 60 g of diallyl bisphenol A at 110° C. for 90 minutes.

[0180] Examples and Comparative Examples

[0181] The chemical components and contents of the resin compositions of Examples 1 to 5 and Comparative Examples 1 to 4 are shown in Table 1.

[0182] Table 1

[0183]

[0184] Among them, maleimide resin A is prepared in Preparation Example 1, maleimide prepolymer B is prepared in Preparation Example 2, maleimide resin C is BMI-2300 manufactured by Yamato Chemical Industry Co., Ltd., crosslinking agent A is TAIC, crosslinking agent B is EF40 manufactured by Sartomer of the United States, elastomer A is V9475 manufactured by KURARE, elastomer B is M1913 manufactured by Asahi Chemical Industry Co., Ltd., elastomer C is methacrylate manufactured by KURARE, cyanate resin is bisphenol A type cyanate resin manufactured by Tianqi, epoxy resin is HP6000 manufactured by DIC, catalyst is 2-ethyl-4-methylimidazole manufactured by Shikoku Chemical Industry Co., Ltd., inorganic filler is spherical silica manufactured by Lianrui, D 50 =3μm.

[0185] The above examples and comparative examples also prepare prepregs, including E glass fiber cloth as a reinforcing material and a resin composition coated on the glass fiber cloth by an impregnation method, wherein the glass fiber cloth is a fiber-spreading cloth pre-treated with an epoxy silane coupling agent.

[0186] Specifically, the components of the resin compositions of Examples 1 to 5 and Comparative Examples 1 to 4 were dissolved in butanone, stirred and mixed, and then diluted into a glue solution with a solid content of 65 wt %; the E glass fiber cloth used as a reinforcing material was pretreated with an epoxy silane coupling agent, immersed in the above-mentioned glue solution, taken out after infiltration, placed in a blast drying oven at 160° C., and baked for 3 to 6 minutes to obtain a prepreg.

[0187] The above examples and comparative examples also prepared copper clad laminates by the following method:

[0188] Take the above-mentioned semi-cured sheet, cut it to 300×300mm, and stack it into a composite sheet with a certain stacking structure. Then, place a low-profile electrolytic copper foil with a thickness of 12μm on both sides of the composite sheet, place it in a vacuum hot press, and hot press it for 1.5h at a pressure of 1.5MPa and a temperature of 220℃ to obtain a copper clad laminate.

[0189] The above examples and comparative examples also prepare insulating boards comprising at least one of the above-mentioned prepregs.

[0190] The above examples and comparative examples also prepare insulating films, including a carrier film and the above resin composition coated thereon.

[0191] The above embodiments and comparative examples also prepare circuit substrates, including one of the above prepregs, by using conventional preparation methods in the prior art, which will not be described in detail herein.

[0192] The copper clad laminates obtained in Examples 1 to 5 and Comparative Examples 1 to 4 were subjected to performance testing, and the test results are shown in Table 2. The performance testing method includes:

[0193] (1) Glass transition temperature (Tg): The test was conducted using the DMA (thermomechanical analysis) method in accordance with IPC-TM-6502.4.25, with a heating rate of 10°C / min and a frequency of 10 Hz.

[0194] (2) CTE (X / Y axis): TMA was used, the heating rate was 5°C / min, and the test temperature range was 50-120°C;

[0195] (3) Dk and Df: The dielectric constant Dk and dielectric loss Df at 10 GHz were measured using the plate method in accordance with IPC-TM-650 2.5.5.9.

[0196] (4) Modulus: Tested using the DMA (thermomechanical analysis) method in accordance with IPC-TM-650 2.4.24.4;

[0197] (5) Substrate quality: When there are no resin agglomerates larger than 10 μm in the substrate, it is represented as 0; when there are a small amount of resin agglomerates larger than 10 μm in the substrate, it is represented as Δ; when there are a large amount of resin agglomerates larger than 10 μm in the substrate, it is represented as X.

[0198] Table 2

[0199]

[0200]

[0201] Referring to Table 2, compared with the comparative example, the resin composition of the embodiment of the present application has excellent compatibility and production processability, and the copper clad laminate further prepared therefrom not only has excellent heat resistance, low dielectric constant and dielectric loss value, but also has an appropriate modulus value.

[0202] It should be understood that although this specification is described according to implementation modes, not every implementation mode contains only one independent technical solution. This description of the specification is only for the sake of clarity. Those skilled in the art should regard the specification as a whole. The technical solutions in each implementation mode may also be appropriately combined to form other implementation modes that can be understood by those skilled in the art.

[0203] The detailed descriptions listed above are merely specific descriptions of feasible implementation methods of the present application. They are not intended to limit the scope of protection of the present application. Any equivalent implementation methods or changes that do not deviate from the technical spirit of the present application should be included in the scope of protection of the present application.

Claims

1. A resin composition, characterized in that By solid weight, including: 50 to 100 parts by weight of the first component; 5 to 60 parts by weight of the second component; 5 to 50 parts by weight of the third component; Epoxy resin 0-50 parts by weight; Wherein, the first component is a maleimide resin or a maleimide prepolymer, the second component is a crosslinking agent, the third component is an elastomer, and at least two of the first component, the second component, and the third component contain at least one of the following groups: Wherein, X1 is a C1-C5 alkyl group.

2. The resin composition according to claim 1, characterized in that The elastomer is a styrene elastomer.

3. The resin composition according to claim 1, characterized in that The elastomer is at least one of styrene-butadiene copolymer, styrene-butadiene-styrene copolymer, styrene-pentadiene copolymer and styrene-pentadiene-styrene copolymer.

4. The resin composition according to claim 1, characterized in that The maleimide resin is at least one of the following structures: Structural formula (1), R is selected from hydrogen or C1-C5 alkyl, R' is selected from hydrogen or C1-C5 alkyl, and n is an integer from 1 to 20; Structural formula (2), R is selected from hydrogen or C1-C5 alkyl, R' is selected from hydrogen or C1-C5 alkyl, and n is an integer from 1 to 20; Structural formula (6), R1 is methylene, ethylene or R2 is hydrogen, methyl or ethyl; n is an integer from 1 to 10; n is an integer from 1 to 10; R is hydrogen, methyl or ethyl, and n is an integer of 1-10.

5. The resin composition according to claim 1, characterized in that The crosslinking agent is at least one of triallyl isocyanate monomer, triallyl isocyanate monomer prepolymer, butadiene, styrene, styrene-anhydride copolymer, pentadiene, methacrylate, dicyclopentadienyl methacrylate, norbornene, and cyclopentadiene.

6. The resin composition according to claim 5, characterized in that The crosslinking agent is a styrene-anhydride copolymer, wherein the molar ratio of styrene to anhydride is 1:1, 2:1, 3:1, 4:1, 6:1 or 8:

1.

7. The resin composition according to claim 1, characterized in that The epoxy resin is at least one of the following structural formulas: In the above structural formula, n is an integer of 1-10.

8. The resin composition according to claim 1, characterized in that The invention further comprises 5 to 40 parts by weight of cyanate resin based on solid weight.

9. The resin composition according to claim 8, characterized in that The cyanate ester is selected from at least one of bisphenol A cyanate ester resin, bisphenol F cyanate ester resin, bisphenol S cyanate ester resin, bisphenol E cyanate ester resin, bisphenol M cyanate ester resin, double bond-containing cyanate ester resin, phosphorus-containing cyanate ester resin, phenolic cyanate ester resin, biphenyl cyanate ester resin, naphthalene ring cyanate ester resin and dicyclopentadiene cyanate ester resin.

10. Use of the resin composition according to any one of claims 1 to 9 in prepregs, copper-clad laminates, insulating boards, insulating films, circuit substrates and electronic devices.

Images