Naphthalene-type epoxy resin, resin composition and use thereof

Abstract

The application discloses a naphthalene type epoxy resin, a resin composition and application thereof, and the naphthalene type epoxy resin comprises a compound as shown in a structural formula (1). By increasing styrene type substituents in the naphthalene type epoxy resin and matching the rigid naphthalene structure, rigid units and flexible units are cross-linked with each other, the structure of the whole cross-linking network is more compact, the decrease of heat resistance can be inhibited, the toughness can be increased, and then the cured product with high heat resistance, low dielectric constant, low dielectric loss, low CTE, high moisture resistance and high modulus can be obtained.

Description

Technical Field

[0001] This invention belongs to the field of electronic materials technology, and relates to a naphthalene-type epoxy resin, as well as a resin composition and the application of the resin composition in prepregs, laminates, insulating boards, insulating films, circuit boards and electronic devices. Background Technology

[0002] Epoxy resins possess excellent heat resistance, moisture resistance, and superior mechanical and electrical properties, making them widely used in industry. High-end applications, particularly in the electrical and electronic fields, demand even higher levels of heat resistance, moisture resistance, dielectric properties, and mechanical characteristics from epoxy resins.

[0003] Naphthalene-type epoxy resins contain at least one naphthalene ring in their molecular structure. They are characterized by heat resistance, high strength, and moisture resistance, with these properties remaining largely unchanged at higher temperatures. However, naphthalene-type epoxy resins have poor dielectric properties and toughness, making it difficult to meet the dielectric requirements for high-frequency and high-speed applications.

[0004] Therefore, developing a naphthalene-type epoxy resin that maintains good heat resistance while also possessing low dielectric constant, low dielectric loss, low CTE, and low moisture resistance is an urgent problem to be solved in current circuit board applications. Summary of the Invention

[0005] To address the issue that existing epoxy resins cannot simultaneously meet the requirements of high heat resistance, low water absorption, low thermal expansion, excellent dielectric properties, and high modulus, this invention provides a naphthalene-type epoxy resin, a resin composition, and prepregs, laminates, insulating boards, insulating films, circuit boards, and electronic devices made from the resin composition.

[0006] To achieve one of the above-mentioned objectives, one embodiment of the present invention provides a naphthalene-type epoxy resin comprising the following compounds:

[0007]

[0008] Wherein, R is hydrogen or any alkyl group from C1 to C10, R1 is hydrogen or any alkyl group from C1 to C5, and n is an integer from 1 to 10.

[0009] As a further improvement of one embodiment of the present invention, the naphthalene-type epoxy resin further includes the following compounds:

[0010]

[0011] Wherein, R2 is hydrogen or any alkyl group from C1 to C5, and n is an integer from 1 to 10.

[0012] As a further improvement of one embodiment of the present invention, in the structural formula (2), R2 is hydrogen or methyl.

[0013] As a further improvement of one embodiment of the present invention, in the naphthalene-type epoxy resin, the weight ratio of the compound represented by structural formula (1) to that represented by structural formula (2) is 50:50 to 95:5.

[0014] As a further improvement of one embodiment of the present invention, the epoxy equivalent of the naphthalene-type epoxy resin is 150-300 g / eq.

[0015] As a further improvement of one embodiment of the present invention, R1 in the structural formula (1) is hydrogen, methyl, ethyl or tert-butyl.

[0016] As a further improvement to one embodiment of the present invention, the method for preparing the naphthalene-type epoxy resin includes:

[0017] S1. Add 80-300 parts by weight of phenol and 0.5-6 parts by weight of acidic catalyst to a reaction flask, stir slowly under nitrogen protection, and after 0.5-3 hours, add 50-230 parts by weight of aromatic monoethylene compound dropwise, and then maintain the reaction temperature at 90-130℃ for 30-180 minutes to obtain a styrene-substituted phenol compound.

[0018] S2. Naphthol and formaldehyde are reacted in a 1:1 molar ratio to generate naphthol methanol, which is then reacted with the styrene-substituted phenol compound obtained in S1 under the action of an acidic catalyst. The molar ratio of naphthol methanol to the styrene-substituted phenol compound is 1:2. The reaction temperature is 50-150℃ and the reaction time is 1-15h to generate naphthol resin as shown in structural formula (3).

[0019] S3. The naphthol resin obtained in S2 is subjected to an epoxidation reaction with epichlorohydrin at a reaction temperature of 50-120°C and a reaction time of 0.5-3.5 h to obtain a naphthalene-type epoxy resin as shown in structural formula (1).

[0020]

[0021] Wherein, R is hydrogen or any alkyl group from C1 to C10, R1 is hydrogen or any alkyl group from C1 to C5, and n is an integer from 1 to 10.

[0022] As a further improvement of one embodiment of the present invention, in S3, a naphthalene-type phenolic resin as shown in structural formula (4) is added and undergoes an epoxidation reaction with epichlorohydrin to obtain a naphthalene-type epoxy resin mixture of the compound shown in structural formula (1) and the compound shown in structural formula (2).

[0023]

[0024] Wherein, R2 is hydrogen or any alkyl group from C1 to C5, and n is an integer from 1 to 10.

[0025] As a further improvement of one embodiment of the present invention, in S1, the aromatic monoethylene compound is styrene, 4-methylstyrene, 4-tert-butylstyrene, 4-ethylstyrene, 3-methylstyrene, 3-tert-butylstyrene, 3-ethylstyrene, 2-methylstyrene, 2-tert-butylstyrene or 2-ethylstyrene.

[0026] As a further improvement of one embodiment of the present invention, in S1, the aromatic monoethylene compound is styrene, 4-methylstyrene, or 4-tert-butylstyrene.

[0027] As a further improvement of one embodiment of the present invention, the acidic catalyst is benzenesulfonic acid or activated clay.

[0028] To achieve one of the above-mentioned objectives, one embodiment of the present invention also provides a resin composition comprising the naphthalene-type epoxy resin as described above.

[0029] As a further improvement of one embodiment of the present invention, the resin composition further includes at least one of amine curing agents, reactive ester curing agents, acid anhydride curing agents, and phenolic curing agents.

[0030] As an alternative, the amine curing agent is dicyandiamide, an aromatic diamine compound, or an aliphatic diamine compound.

[0031] As an alternative, the aromatic diamine compound is selected from at least one of unsubstituted phenylenediamine, methylphenylenediamine, dimethylphenylenediamine, trimethylphenylenediamine, tetramethylphenylenediamine, xylenediamine, diaminopyridine, diaminodiphenylmethane, substituted diaminodiphenylmethane, bis(4-(4-aminophenoxy)phenyl)propane, bis(4-(4-aminophenoxy)phenyl)hexafluoropropane, diaminobenzophenone, diaminodiphenyl ether, diaminodiphenyl sulfone, diaminobiphenyl, diaminodiphenyl sulfone, diaminonaphthalene, diaminodiphenylfluorene, and diaminoanthraquinone.

[0032] As an alternative, the aliphatic diamine compound is a hydrocarbon long-chain diamine compound whose molecular structure contains any one of C2-C36.

[0033] As an alternative, the active ester curing agent is a dicyclopentadienyl active ester or a naphthyl active ester.

[0034] As a preferred embodiment, the structure of the active ester curing agent is as follows:

[0035]

[0036] Where X is phenyl, substituted phenyl, naphthyl or substituted naphthyl, n has an average value of 0.25 to 2.5, and k is 0 or 1.

[0037] As a further improvement of one embodiment of the present invention, the substituent is amino, allyl, propenyl, methacrylate, acrylate, vinyl, or any alkyl group from C1 to C5.

[0038] As a preferred embodiment, the structural formula of the anhydride curing agent is:

[0039]

[0040] Where m / n = 1 to 8.

[0041] As a preferred embodiment, the anhydride curing agent is a styrene-maleic anhydride copolymer.

[0042] As an alternative, the phenolic curing agent is a phenolic resin or a benzoxazine resin.

[0043] As a further improvement of one embodiment of the present invention, the phenolic resin includes a naphthoid phenolic resin, which contains at least one of the following structures:

[0044]

[0045] Where n is an integer from 1 to 10.

[0046] As a further improvement to one embodiment of the present invention, the resin composition, by solid weight, comprises:

[0047] The naphthalene-type epoxy resin, 100 parts by weight

[0048] Dicyandiamide, 1-30 parts by weight;

[0049] Alternatively, the resin composition, by solid weight, comprises:

[0050] The naphthalene-type epoxy resin, 100 parts by weight

[0051] Active ester curing agent, 5-60 parts by weight;

[0052] Alternatively, the resin composition, by solid weight, comprises:

[0053] The naphthalene-type epoxy resin, 100 parts by weight

[0054] Styrene-maleic anhydride copolymer, 10-50 parts by weight;

[0055] Alternatively, the resin composition, by solid weight, comprises:

[0056] The naphthalene-type epoxy resin, 100 parts by weight

[0057] Phenolic resin, 10-60 parts by weight;

[0058] Alternatively, the resin composition, by solid weight, comprises:

[0059] The naphthalene-type epoxy resin, 100 parts by weight

[0060] Benzoxazine resin, 5-50 parts by weight.

[0061] As a further improvement to one embodiment of the present invention, the resin composition, by solid weight, further comprises:

[0062] Catalyst, 0.01–10 parts by weight,

[0063] Inorganic filler, 20-200 parts by weight.

[0064] As an alternative, the catalyst is at least one of imidazole catalysts, pyridine catalysts, organophosphorus catalysts, and organometallic salt catalysts.

[0065] As an alternative, the imidazole catalyst is at least one selected from 4-dimethylaminopyridine, 2-methylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, modified imidazole, and zinc octanoate.

[0066] As a preferred embodiment, the organophosphorus catalyst is triphenylphosphine.

[0067] As an alternative, the inorganic filler is selected from at least one of silicon dioxide, aluminum hydroxide, alumina, talc, aluminum nitride, boron nitride, silicon carbide, barium sulfate, barium titanate, strontium titanate, calcium carbonate, calcium silicate, mica, and glass fiber powder.

[0068] As a preferred option, the inorganic filler is spherical silica.

[0069] As a further improvement of one embodiment of the present invention, the inorganic filler is surface-treated with a silane coupling agent, wherein the silane coupling agent is at least one of aminosilane coupling agent, epoxysilane coupling agent, vinylsilane coupling agent, methacrylate silane coupling agent or acrylate silane coupling agent.

[0070] As a preferred embodiment, the inorganic filler is spherical silica surface-treated with an aminosilane coupling agent.

[0071] As a further improvement of one embodiment of the present invention, the average particle size D50 of the inorganic filler is 1 to 10 μm, preferably 2 to 5 μm.

[0072] As a further improvement of one embodiment of the present invention, the resin composition further includes 5 to 60 parts by weight of flame retardant, based on solid weight.

[0073] As an alternative, the flame retardant is selected from at least one of bromine-based flame retardants, phosphorus-based flame retardants, nitrogen-based flame retardants, organosilicon flame retardants, and organometallic salt flame retardants.

[0074] As an alternative, the brominated flame retardant is selected from decabromodiphenyl ether, decabromodiphenyl ethane, styrene bromide, or tetrabromophthalamide.

[0075] As an optional embodiment, the phosphorus-based flame retardant is selected from inorganic phosphorus, condensed phosphate compounds, phosphoric acid compounds, hypophosphoric acid compounds, phosphorus oxide compounds, 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (DOPO), 10-(2,5-dihydroxyphenyl)-9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (DOPO-HQ), 10-phenyl-9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, tris(2,6-dimethylphenyl)phosphine, etc. (m is an integer from 1 to 5)

[0076] Phosphazene or modified phosphazene.

[0077] As an alternative, the flame retardant is a condensed phosphate compound, hypophosphite, or a bisDOPO compound.

[0078] The present invention also provides the application of the above-mentioned resin composition in prepregs, laminates, insulating boards, insulating films, circuit boards, and electronic devices, as detailed below:

[0079] The present invention also provides a semi-cured sheet comprising a reinforcing material and the aforementioned resin composition; the resin composition is coated on the reinforcing material.

[0080] The method for preparing the prepreg is as follows: the aforementioned resin composition is dissolved in a solvent to form an adhesive solution, and then the adhesive solution is coated onto the reinforcing material by impregnation. The impregnated reinforcing material is then taken out and baked at a temperature of 100-180°C for 1-15 minutes. After drying, the prepreg is obtained.

[0081] As an alternative, 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.

[0082] As an alternative, the reinforcing material is selected from at least one of natural fibers, organic synthetic fibers, organic fabrics, and inorganic fabrics.

[0083] 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, or Q-glass fiber cloth.

[0084] Furthermore, when the reinforcing material is glass fiber cloth, the glass fiber cloth is pre-treated with a coupling agent to improve the interfacial bonding between the resin composition and the glass fiber cloth. Preferably, the coupling agent used here is an epoxy silane coupling agent or an amino silane coupling agent to provide good water resistance and heat resistance.

[0085] The present invention also provides a laminate comprising a prepreg sheet and a metal foil disposed on at least one surface of the prepreg sheet; or comprising a composite sheet formed by stacking multiple prepreg sheets together and a metal foil disposed on at least one surface of the composite sheet.

[0086] By adopting this technical solution, the laminate has the characteristics of low thermal expansion coefficient, high glass transition temperature, low dielectric constant, and low dielectric loss value.

[0087] The method for preparing the laminate is as follows: A metal foil is coated onto one or both surfaces of a prepreg, or at least two prepregs are stacked to form a composite sheet, and a metal foil is coated onto one or both surfaces of the composite sheet. The laminate is then hot-pressed to obtain a metal foil laminate. The hot-pressing conditions are: pressure 0.2–2 MPa, temperature 150–250°C, and pressing time 2–4 hours.

[0088] Preferably, the metal foil is selected from copper foil or aluminum foil. The thickness of the metal foil is 5μm, 8μm, 12μm, 18μm, 35μm or 70μm.

[0089] The present invention also provides an insulating board comprising the aforementioned resin composition. By employing this technical solution, the thermal conductivity and heat resistance of the insulating board are significantly improved.

[0090] The present invention also provides an insulating film, comprising a carrier film and the aforementioned resin composition coated thereon. By employing this technical solution, the thermal index of the insulating film is significantly improved.

[0091] The insulating film is prepared by the following method: the aforementioned resin composition is dissolved in a solvent to form an adhesive solution, which is then coated onto a carrier film. After the carrier film coated with the adhesive solution is heated and dried, the insulating film is obtained.

[0092] As an alternative, 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.

[0093] As an alternative, the carrier film is selected from at least one of PET film, PP film, PE film, and PVC film.

[0094] The present invention also provides a circuit board comprising at least one of the aforementioned prepreg, laminate, insulating board, and insulating film. By employing this technical solution, the heat resistance of the circuit board is greatly improved.

[0095] The present invention also provides an electronic device including the aforementioned circuit board. Because the heat resistance of the circuit board is greatly improved, the safety of the electronic device is significantly enhanced.

[0096] The present invention also provides the application of the above-described resin composition in prepregs, laminates, insulating boards, insulating films, circuit boards, and electronic devices.

[0097] Due to the application of the above technical solution, the present invention has the following beneficial effects compared with the prior art:

[0098] (1) By adding styrene substituents to naphthalene-type epoxy resin and combining it with rigid naphthalene structure, the rigid and flexible units are cross-connected, making the overall cross-linked network structure more compact. This not only inhibits the decrease in heat resistance but also increases toughness, thereby obtaining a cured product with high heat resistance, low dielectric constant, low dielectric loss, low CTE, high resistance to humid heat and high modulus.

[0099] (2) By using the aforementioned naphthalene-type epoxy resin, the resin composition can have high heat resistance, low dielectric constant, low dielectric loss, low CTE, high resistance to damp heat and high modulus, thus making it suitable for the field of high frequency and high speed substrate materials. Detailed Implementation

[0100] The technical solution of the present invention will be further described below with reference to specific embodiments. The following embodiments are only descriptive and not limiting, and cannot be used to limit the scope of protection of this application.

[0101] This invention provides a naphthalene-type epoxy resin, a resin composition, and prepregs, laminates, insulating boards, insulating films, circuit boards, and electronic devices made using the resin composition, that is, the application of the resin composition in prepregs, laminates, insulating boards, insulating films, circuit boards, and electronic devices.

[0102] First, one embodiment of the present invention provides a naphthalene-type epoxy resin, comprising the following compounds:

[0103]

[0104] Wherein, R is hydrogen or any alkyl group from C1 to C10, R1 is hydrogen or any alkyl group from C1 to C5, and n is an integer from 1 to 10.

[0105] By adding styrene-based substituents to naphthalene-type epoxy resins and combining them with a rigid naphthalene structure, the rigid and flexible units are cross-connected, resulting in a denser overall cross-linked network. This not only inhibits the decline in heat resistance but also increases toughness, thereby obtaining a cured product that combines high heat resistance, low dielectric constant, low dielectric loss, low CTE, high resistance to humid heat, and high modulus.

[0106] Furthermore, the naphthalene-type epoxy resin also includes the following compounds:

[0107]

[0108] Wherein, R2 is hydrogen or any alkyl group from C1 to C5, and n is an integer from 1 to 10.

[0109] By adding the compound shown in structural formula (2) to the naphthalene-type epoxy resin, the decrease in heat resistance can be further suppressed while maintaining good compatibility, and excellent dielectric properties and coefficient of thermal expansion can be obtained, while also having good processability and adhesive flowability.

[0110] Preferably, in the structural formula (2), R2 is hydrogen or methyl.

[0111] More preferably, in the naphthalene-type epoxy resin, the weight ratio of the compound represented by the structural formula (1) to that represented by the structural formula (2) is 50:50 to 95:5.

[0112] Preferably, the epoxy equivalent of the naphthalene-type epoxy resin is 150-300 g / eq.

[0113] Preferably, R1 in the structural formula (1) is hydrogen, methyl, ethyl or tert-butyl.

[0114] Furthermore, the preparation method of the naphthalene-type epoxy resin includes:

[0115] S1. Add 80-300 parts by weight of phenol and 0.5-6 parts by weight of acidic catalyst to a reaction flask, stir slowly under nitrogen protection, and after 0.5-3 hours, add 50-230 parts by weight of aromatic monoethylene compound dropwise, and then maintain the reaction temperature at 90-130℃ for 30-180 minutes to obtain a styrene-substituted phenol compound.

[0116] S2. Naphthol and formaldehyde are reacted in a 1:1 molar ratio to generate naphthol methanol, which is then reacted with the styrene-substituted phenol compound obtained in S1 under the action of an acidic catalyst. The molar ratio of naphthol methanol to the styrene-substituted phenol compound is 1:2. The reaction temperature is 50-150℃ and the reaction time is 1-15h to generate naphthol resin as shown in structural formula (3).

[0117] S3. The naphthol resin obtained in S2 is subjected to an epoxidation reaction with epichlorohydrin at a reaction temperature of 50-120°C and a reaction time of 0.5-3.5 h to obtain a naphthalene-type epoxy resin as shown in structural formula (1).

[0118]

[0119] Wherein, R is hydrogen or any alkyl group from C1 to C10, R1 is hydrogen or any alkyl group from C1 to C5, and n is an integer from 1 to 10.

[0120] Further, in this embodiment, in S3, a naphthalene-type phenolic resin as shown in structural formula (4) is added and undergoes an epoxidation reaction with epichlorohydrin to obtain a naphthalene-type epoxy resin mixture of the compound shown in structural formula (1) and the compound shown in structural formula (2).

[0121]

[0122] Wherein, R2 is hydrogen or any alkyl group from C1 to C5, and n is an integer from 1 to 10.

[0123] Of course, in other embodiments, a naphthalene-type epoxy resin mixture of the compound shown in structural formula (1) and the compound shown in structural formula (2) can also be obtained by directly adding the compound shown in structural formula (1) to the compound shown in structural formula (2).

[0124] Preferably, in S1, the aromatic monoethylene compound is styrene, 4-methylstyrene, 4-tert-butylstyrene, 4-ethylstyrene, 3-methylstyrene, 3-tert-butylstyrene, 3-ethylstyrene, 2-methylstyrene, 2-tert-butylstyrene or 2-ethylstyrene; more preferably, it is styrene, 4-methylstyrene or 4-tert-butylstyrene.

[0125] The acidic catalyst is preferably benzenesulfonic acid or activated clay.

[0126] One embodiment of the present invention also provides a resin composition comprising the naphthalene-type epoxy resin as described above. By employing the aforementioned naphthalene-type epoxy resin, the resin composition can possess high heat resistance, low dielectric constant, low dielectric loss, low CTE, high resistance to damp heat, and high modulus, thereby making it suitable for the field of high-frequency and high-speed substrate materials.

[0127] Furthermore, the resin composition further includes at least one of amine curing agents, reactive ester curing agents, acid anhydride curing agents, and phenolic curing agents.

[0128] Preferably, the amine curing agent is dicyandiamide, an aromatic diamine compound, or an aliphatic diamine compound.

[0129] Optionally, the aromatic diamine compound is selected from at least one of unsubstituted phenylenediamine, methylphenylenediamine, dimethylphenylenediamine, trimethylphenylenediamine, tetramethylphenylenediamine, xylenediamine, diaminopyridine, diaminodiphenylmethane, substituted diaminodiphenylmethane, bis(4-(4-aminophenoxy)phenyl)propane, bis(4-(4-aminophenoxy)phenyl)hexafluoropropane, diaminobenzophenone, diaminodiphenyl ether, diaminodiphenyl sulfone, diaminobiphenyl, diaminodiphenyl sulfone, diaminonaphthalene, diaminodiphenylfluorene, and diaminoanthraquinone.

[0130] Optionally, the aliphatic diamine compound is a hydrocarbon long-chain diamine compound containing any one of C2-C36 in its molecular structure.

[0131] Optionally, the active ester curing agent is a dicyclopentadienyl active ester or a naphthyl active ester.

[0132] Preferably, the structure of the active ester curing agent is as follows:

[0133]

[0134] Where X is phenyl, substituted phenyl, naphthyl or substituted naphthyl, n has an average value of 0.25 to 2.5, and k is 0 or 1.

[0135] Preferably, the substituent is an amino, allyl, propenyl, methacrylate, acrylate, vinyl, or any alkyl group selected from C1-C5.

[0136] Specifically, the active ester curing agent is selected from DIC-manufactured HPC-8000, HPC-8000H, HPC-8000L, HPC-8150, HPC-8100, HPC-8100L, EXB-8500, HPC-8200, EXB-9451, EXB-9460, EXB-9460S or EXB-9411, etc.

[0137] Preferably, the structural formula of the anhydride curing agent is:

[0138]

[0139] Wherein, m / n = 1 to 8. Preferably, m / n is 1, 2, 3, 4, 5, 6, 7 or 8.

[0140] Preferably, the anhydride curing agent is a styrene-maleic anhydride copolymer.

[0141] Preferably, the phenolic curing agent is a phenolic resin or a benzoxazine resin.

[0142] Furthermore, the phenolic resin includes a naphthalene-type phenolic resin, which contains at least one of the following structures:

[0143]

[0144]

[0145] Where n is an integer from 1 to 10.

[0146] As a preferred embodiment, the resin composition, by solid weight, comprises:

[0147] The naphthalene-type epoxy resin, 100 parts by weight

[0148] Dicyandiamide, 1 to 30 parts by weight.

[0149] As another preferred embodiment, the resin composition, by solid weight, comprises:

[0150] The naphthalene-type epoxy resin, 100 parts by weight

[0151] Active ester curing agent, 5-60 parts by weight.

[0152] As another preferred embodiment, the resin composition, by solid weight, comprises:

[0153] The naphthalene-type epoxy resin, 100 parts by weight

[0154] Styrene-maleic anhydride copolymer, 10-50 parts by weight.

[0155] As another preferred embodiment, the resin composition, by solid weight, comprises:

[0156] The naphthalene-type epoxy resin, 100 parts by weight

[0157] Phenolic resin, 10-60 parts by weight.

[0158] As another preferred embodiment, the resin composition, by solid weight, comprises:

[0159] The naphthalene-type epoxy resin, 100 parts by weight

[0160] Benzoxazine resin, 5-50 parts by weight.

[0161] Furthermore, the resin composition, by solid weight, further comprises:

[0162] Catalyst, 0.01–10 parts by weight,

[0163] Inorganic filler, 20-200 parts by weight.

[0164] Preferably, the catalyst is at least one of imidazole catalysts, pyridine catalysts, organophosphorus catalysts, and organometallic salt catalysts.

[0165] Preferably, the imidazole catalyst is at least one selected from 4-dimethylaminopyridine, 2-methylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, modified imidazole, and zinc octanoate.

[0166] The organophosphorus catalyst is preferably triphenylphosphine.

[0167] Optionally, the inorganic filler is selected from at least one of silicon dioxide, aluminum hydroxide, alumina, talc, aluminum nitride, boron nitride, silicon carbide, barium sulfate, barium titanate, strontium titanate, calcium carbonate, calcium silicate, mica, and glass fiber powder.

[0168] The inorganic filler is preferably spherical silica.

[0169] Preferably, the inorganic filler is surface-treated with a silane coupling agent, wherein the silane coupling agent is at least one of aminosilane coupling agent, epoxysilane coupling agent, vinylsilane coupling agent, methacrylate silane coupling agent, or acrylate silane coupling agent.

[0170] The inorganic filler is preferably spherical silica surface-treated with an aminosilane coupling agent.

[0171] The average particle size D50 of the inorganic filler is 1-10 μm, preferably 2-5 μm.

[0172] Furthermore, the resin composition, by solid weight, also includes 5 to 60 parts by weight of a flame retardant.

[0173] Optionally, the flame retardant is selected from at least one of bromine-based flame retardants, phosphorus-based flame retardants, nitrogen-based flame retardants, organosilicon flame retardants, and organometallic salt flame retardants.

[0174] The brominated flame retardant is preferably selected from decabromodiphenyl ether, decabromodiphenyl ethane, styrene bromide, or tetrabromophthalamide.

[0175] The phosphorus-based flame retardant is preferably derived from inorganic phosphorus, condensed phosphate compounds, phosphoric acid compounds, hypophosphites, phosphorus oxide compounds, 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (DOPO), 10-(2,5-dihydroxyphenyl)-9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (DOPO-HQ), 10-phenyl-9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, tris(2,6-dimethylphenyl)phosphine, etc.

[0176] (m is an integer from 1 to 5) Phosphazene or modified phosphazene.

[0177] The phosphorus-based flame retardant is more preferably a condensed phosphate compound, hypophosphite, or a bisDOPO compound.

[0178] This application also provides a semi-cured sheet comprising a reinforcing material and the aforementioned resin composition; the resin composition is coated on the reinforcing material.

[0179] The method for preparing the prepreg is as follows: the aforementioned resin composition is dissolved in a solvent to form an adhesive solution, and then the adhesive solution is coated onto the reinforcing material by impregnation. The impregnated reinforcing material is then taken out and baked at a temperature of 100-180°C for 1-15 minutes. After drying, the prepreg is obtained.

[0180] Optionally, 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.

[0181] Optionally, the reinforcing material is selected from at least one of natural fibers, organic synthetic fibers, organic fabrics, and inorganic fabrics.

[0182] 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, or Q-glass fiber cloth.

[0183] Furthermore, when the reinforcing material is glass fiber cloth, the glass fiber cloth is chemically treated with a coupling agent. The coupling agent is preferably an epoxy silane coupling agent or an amino silane coupling agent.

[0184] The present invention also provides a laminate comprising a prepreg sheet and a metal foil disposed on at least one surface of the prepreg sheet; or comprising a composite sheet formed by stacking multiple prepreg sheets together and a metal foil disposed on at least one surface of the composite sheet.

[0185] By adopting this technical solution, the laminate has the characteristics of low thermal expansion coefficient, high glass transition temperature, low dielectric constant, and low dielectric loss value.

[0186] The method for preparing the laminate is as follows: A metal foil is coated onto one or both surfaces of a prepreg, or at least two prepregs are stacked to form a composite sheet, and a metal foil is coated onto one or both surfaces of the composite sheet. The laminate is then hot-pressed to obtain a metal foil laminate. The hot-pressing conditions are: pressure 0.2–2 MPa, temperature 150–250°C, and pressing time 2–4 hours.

[0187] Preferably, the metal foil is selected from copper foil or aluminum foil. The thickness of the metal foil is 5μm, 8μm, 12μm, 18μm, 35μm or 70μm.

[0188] The present invention also provides an insulating board comprising the aforementioned resin composition.

[0189] The present invention also provides an insulating film comprising a carrier film and the aforementioned resin composition coated thereon.

[0190] The insulating film is prepared by the following method: the aforementioned resin composition is dissolved in a solvent to form an adhesive solution, which is then coated onto a carrier film. After the carrier film coated with the adhesive solution is heated and dried, the insulating film is obtained.

[0191] Optionally, 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.

[0192] Optionally, the carrier film is selected from at least one of PET film, PP film, PE film, and PVC film.

[0193] The present invention also provides a circuit board comprising at least one of the aforementioned prepreg, laminate, insulating board, and insulating film.

[0194] The present invention also provides an electronic device, including the aforementioned circuit board.

[0195] The technical solutions of this application will be further described below with reference to some specific synthetic examples, embodiments, and comparative examples. Of course, these embodiments are only a part of the many variations contained in the implementation of this invention, and not all of them.

[0196] Synthesis example 1

[0197] This synthetic example discloses a method for preparing a naphthalene-type epoxy resin, comprising the following steps:

[0198] S1. Add 1 mol of phenol and 1 g of benzenesulfonic acid catalyst to a reaction flask, stir slowly under nitrogen protection, heat to 105℃, add 1 mol of styrene dropwise over 1.5 h, and then maintain for 90 min to allow the reaction to be complete, to obtain a styrene-substituted phenol compound.

[0199] S2. Take 1 mol of naphthol compound and 260 g of butanone solvent, stir to dissolve evenly, then add 1 mol of formaldehyde, react at 40℃ for 2 h, and neutralize with hydrochloric acid after the reaction to obtain naphthol methanol;

[0200] Take 1 mol of the styrene-substituted phenol compound obtained from S1 and 2 mol of naphthol methanol, and carry out a condensation reaction under the catalysis of 1.0 g benzenesulfonic acid. After reacting at 40°C for 2 h, the temperature is raised to 70°C and the reaction continues for 8 h. After the reaction is completed, the naphthalene-type phenolic resin is generated by water washing and heating under reduced pressure. In the structural formula (3), R is methyl and R1 is hydrogen.

[0201] S3. The naphthalene-type phenolic resin obtained in S2 is subjected to an epoxidation reaction with epichlorohydrin at a reaction temperature of 90°C and a reaction time of 2 hours to obtain naphthalene-type epoxy resin A as shown in structural formula (1), where R in structural formula (1) is methyl and R1 is hydrogen.

[0202] Synthesis example 2

[0203] This synthetic example discloses a method for preparing a naphthalene-type epoxy resin, comprising the following steps:

[0204] S1. Add 1 mol of phenol and 1 g of benzenesulfonic acid catalyst to a reaction flask, stir slowly under nitrogen protection, heat to 105℃, add 1 mol of 4-methylstyrene dropwise over 1.5 h, and then maintain for 90 min to allow the reaction to be complete, to obtain a phenol compound containing styrene-substituted groups.

[0205] S2. Take 1 mol of naphthol compound and 260 g of butanone solvent, stir to dissolve evenly, then add 1 mol of formaldehyde, react at 40℃ for 2 h, and neutralize with hydrochloric acid after the reaction to obtain naphthol methanol;

[0206] Take 1 mol of the styrene-substituted phenol compound obtained from S1 and 2 mol of naphthol methanol, and carry out a condensation reaction under the catalysis of 1.0 g benzenesulfonic acid. After reacting at 40°C for 2 h, the temperature is raised to 70°C and the reaction continues for 8 h. After the reaction is completed, the naphthalene-type phenolic resin is generated by water washing and heating under reduced pressure, as shown in structural formula (3), and R in structural formula (1) is methyl and R1 is methyl.

[0207] S3. The naphthalene-type phenolic resin obtained in S2 is subjected to an epoxidation reaction with epichlorohydrin at a reaction temperature of 90°C and a reaction time of 2 hours to obtain naphthalene-type epoxy resin A as shown in structural formula (1), where R in structural formula (1) is hydrogen and R1 is methyl.

[0208] Synthesis example 3

[0209] This synthetic example discloses a method for preparing a naphthalene-type epoxy resin, comprising the following steps:

[0210] S1. Add 1 mol of phenol and 1 g of benzenesulfonic acid catalyst to a reaction flask, stir slowly under nitrogen protection, heat to 105℃, add 1 mol of 4-tert-butylstyrene dropwise over 1.5 h, and then maintain for 90 min to allow the reaction to be complete, to obtain a styrene-substituted phenol compound.

[0211] S2. Take 1 mol of naphthol compound and 260 g of butanone solvent, stir to dissolve evenly, then add 1 mol of formaldehyde, react at 40℃ for 2 h, and neutralize with hydrochloric acid after the reaction to obtain naphthol methanol;

[0212] Take 1 mol of the styrene-substituted phenol compound obtained from S1 and 2 mol of naphthol methanol, and carry out a condensation reaction under the catalysis of 1.0 g benzenesulfonic acid. After reacting at 40°C for 2 h, the temperature is raised to 70°C and the reaction continues for 8 h. After the reaction is completed, the naphthalene-type phenolic resin is generated by water washing and heating under reduced pressure, as shown in structural formula (3), and R in structural formula (1) is methyl and R1 is tert-butyl.

[0213] S3. The naphthalene-type phenolic resin obtained in S2 is subjected to an epoxidation reaction with epichlorohydrin at a reaction temperature of 90°C and a reaction time of 2h to obtain naphthalene-type epoxy resin A as shown in structural formula (1), where R in structural formula (1) is methyl and R1 is tert-butyl.

[0214] Examples 1-6 and Comparative Examples 1-3 each disclose a resin composition, the chemical composition and content of which are shown in Table 1, wherein the content of the chemical composition is in parts by weight based on solid weight.

[0215] Table 1

[0216]

[0217] Among them, the naphthalene-type epoxy resin D is NC-7000 manufactured by Nippon Kayaku, the naphthalene-type epoxy resin E is HP-6000 manufactured by DIC, the phenolic resin is bisphenol A type phenolic resin manufactured by Shengquan, the dicyclopentadiene type active ester is HPC-8000 manufactured by DIC, the benzoxazine resin is bisphenol A type benzoxazine resin manufactured by Dongcai, the styrene-maleic anhydride copolymer is EF40 manufactured by Sartomer of the United States, the 2-methylimidazole is manufactured by Shikoku Kasei, and the silica is spherical silica manufactured by Lianrui with a D50 of 3μm.

[0218] The above embodiments and comparative examples also disclose a prepreg, comprising a glass fiber cloth as a reinforcing material and a resin composition coated onto the glass fiber cloth by an impregnation method. The glass fiber cloth is a split-fiber cloth and is pretreated with an epoxy silane coupling agent.

[0219] The prepreg is prepared by the following method:

[0220] The components of the above resin composition were dissolved in methyl ethyl ketone, stirred and mixed, and then diluted to a solution with a solid content of 65 wt%.

[0221] The E-glass fiber cloth, which serves as the reinforcing material, is pretreated with an epoxy silane coupling agent, then impregnated in the above-mentioned adhesive solution. After impregnation, it is removed and placed in a forced-air drying oven at 160°C for 3–6 minutes to obtain a semi-cured sheet.

[0222] The above embodiments and comparative examples also disclose a laminate prepared by the following method:

[0223] The prepreg was cut to 300×300mm. Then, a low-profile electrolytic copper foil with a thickness of 12μm was placed on each side of the prepreg and stacked into a certain structure. The stack was placed in a vacuum hot press and hot-pressed for 1.5h under a pressure of 1.5MPa and a temperature of 220℃ to obtain a copper-clad laminate with a thickness of 1mm.

[0224] The above embodiments and comparative examples also disclose an insulating board, including a prepreg sheet, which is prepared using conventional preparation methods of the prior art, and will not be described in detail here.

[0225] The above embodiments and comparative examples also disclose a circuit board, including a prepreg, which is prepared using conventional preparation methods of the prior art, and will not be described in detail here.

[0226] The copper-clad laminates obtained in Examples 1-7 and Comparative Examples 1-3 were subjected to performance testing, and the test results are shown in Table 2. The performance testing methods included:

[0227] (1) Glass transition temperature (Tg): The test was conducted using the DMA (thermomechanical analysis) method according to the method specified in IPC-TM-6502.4.25, with a heating rate of 10℃ / min and a frequency of 10Hz.

[0228] (2) Dk (10 GHz): The plate method in IPC-TM-650 2.5.5.9 was used for measurement.

[0229] (3) Df(10GHz): The plate method in IPC-TM-650 2.5.5.9 was used for measurement.

[0230] (4) Coefficient of thermal expansion (CTE) of X / Y axis: The TMA method was used to determine the CTE according to the IPC-TM-650 method. The heating rate was 5℃ / min and the test temperature range was 50~120℃.

[0231] (5) Modulus: The TMA method in IPC-TM-650 2.4.24.4 was used for determination.

[0232] Table 1

[0233]

[0234]

[0235] Referring to Table 2, compared with the comparative example, the copper-clad laminate prepared by the resin composition of the present invention has high heat resistance, low dielectric constant, low dielectric loss, low CTE, high resistance to damp heat and high modulus, and can therefore be applied to the field of high frequency and high speed substrate materials.

[0236] It should be understood that although this specification describes embodiments, not every embodiment contains only one independent technical solution. This way of describing the specification is only for clarity. Those skilled in the art should regard the specification as a whole. The technical solutions in each embodiment can also be appropriately combined to form other embodiments that can be understood by those skilled in the art.

[0237] The detailed descriptions listed above are merely specific descriptions of feasible embodiments of the present invention, and are not intended to limit the scope of protection of the present invention. All equivalent embodiments or modifications made without departing from the spirit of the present invention should be included within the scope of protection of the present invention.

Claims

1. A naphthalene-type epoxy resin, characterized in that, Including the following compounds: Wherein, R is hydrogen or any alkyl group from C1 to C10, R1 is hydrogen or any alkyl group from C1 to C5, and n is an integer from 1 to 10.

2. The naphthalene-type epoxy resin according to claim 1, characterized in that, It also includes the following compounds: Wherein, R2 is hydrogen or any alkyl group from C1 to C5, and n is an integer from 1 to 10.

3. The naphthalene-type epoxy resin according to claim 2, characterized in that, The weight ratio of the compound represented by structural formula (1) to that represented by structural formula (2) is 50:50 to 95:

5.

4. The naphthalene-type epoxy resin according to claim 1 or 2, characterized in that, The epoxy equivalent of the naphthalene-type epoxy resin is 150-300 g / eq.

5. The naphthalene-type epoxy resin according to claim 1, characterized in that, Its preparation methods include: S1. Add 80-300 parts by weight of phenol and 0.5-6 parts by weight of acidic catalyst to a reaction flask, stir slowly under nitrogen protection, and after 0.5-3 hours, add 50-230 parts by weight of aromatic monoethylene compound dropwise, and then maintain the reaction temperature at 90-130℃ for 30-180 minutes to obtain a styrene-substituted phenol compound. S2. Naphthol and formaldehyde are reacted in a 1:1 molar ratio to generate naphthol methanol, which is then reacted with the styrene-substituted phenol compound obtained in S1 under the action of an acidic catalyst. The molar ratio of naphthol methanol to the styrene-substituted phenol compound is 1:

2. The reaction temperature is 50-150℃ and the reaction time is 1-15h to generate naphthol resin as shown in structural formula (3). S3. The naphthalene-type phenolic resin obtained in S2 is subjected to an epoxidation reaction with epichlorohydrin at a reaction temperature of 50-120℃ and a reaction time of 0.5-3.5h to obtain a naphthalene-type epoxy resin as shown in structural formula (1). Wherein, R is hydrogen or any alkyl group from C1 to C10, R1 is hydrogen or any alkyl group from C1 to C5, and n is an integer from 1 to 10.

6. A resin composition, characterized in that, Includes the naphthalene-type epoxy resin as described in any one of claims 1 to 5.

7. The resin composition according to claim 6, characterized in that, It also includes at least one of amine curing agents, reactive ester curing agents, acid anhydride curing agents, and phenolic curing agents.

8. The resin composition according to claim 7, characterized in that, By solid weight, including: The naphthalene-type epoxy resin, 100 parts by weight Dicyandiamide, 1-30 parts by weight; Alternatively, the resin composition, by solid weight, comprises: The naphthalene-type epoxy resin, 100 parts by weight Active ester curing agent, 5-60 parts by weight; Alternatively, the resin composition, by solid weight, comprises: The naphthalene-type epoxy resin, 100 parts by weight Styrene-maleic anhydride copolymer, 10-50 parts by weight; Alternatively, the resin composition, by solid weight, comprises: The naphthalene-type epoxy resin, 100 parts by weight Phenolic resin, 10-60 parts by weight; Alternatively, the resin composition, by solid weight, comprises: The naphthalene-type epoxy resin, 100 parts by weight Benzoxazine resin, 5-50 parts by weight.

9. The resin composition according to any one of claims 6 to 8, characterized in that, In terms of solid weight, it also includes: Catalyst, 0.01–10 parts by weight, Inorganic filler, 20-200 parts by weight.

10. The use of a resin composition according to any one of claims 6 to 9 in prepreg, laminate, insulating board, insulating film, circuit board and electronic device.

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