Resin composition and use thereof

Abstract

The present application relates to resin composition and application thereof. The resin composition comprises, by weight of solid: 100 parts of a first component and 50-300 parts of a second component; the first component comprises 5-70 wt% of bismaleimide resin and / or its derivative, 5-80 wt% of epoxy resin, 0.5-60 wt% of curing agent and 0.5-5 wt% of accelerator; the second component comprises silicon nitride and aluminum oxide, but does not comprise boron nitride, and the mass ratio of silicon nitride to aluminum oxide is 1 / 5-2 / 3. In the present application, silicon nitride and aluminum oxide are compatible with each other to form a heat conduction network, and heat is transferred through the heat conduction network, thereby significantly improving the thermal conductivity coefficient of the resin composition, and further improving the heat conductivity and heat resistance of the resin composition. At the same time, the second component does not contain boron nitride, which can reduce the anisotropy of the resin composition, thereby improving the heat conductivity, flowability, adhesion to copper foil of the resin composition, and reducing the cost and improving the cost performance.

Description

TECHNICAL FIELD

[0001] The present application belongs to the technical field of electronic materials, and particularly relates to a resin composition, a prepreg, a laminated board, an insulating board, an insulating film, a circuit substrate and an electronic device. BACKGROUND

[0002] With the rapid development of large-scale, super-large-scale integrated circuits and electronic equipment assembly automation technology, electronic devices are rapidly developing towards high density and integration; the power of electronic devices becomes higher and higher, and the heat generation becomes larger and larger. Literature shows that for electronic components, the reliability of products decreases by 10% for every 2℃ increase in temperature; when the temperature increases by 50℃, the service life of components is only 1 / 6 of the original. Therefore, in order to ensure the normal operation of components, heat dissipation has become a problem that needs to be solved urgently, and higher requirements for the heat dissipation of PCB substrates have also been put forward.

[0003] In a related technology, a high-thermal-conductivity and high-heat-dissipation flexible copper-clad plate is disclosed, wherein the thermal conductive insulating layer contains nitrile rubber modified epoxy resin, boron nitride, silicon nitride and aluminum oxide; in another related technology, a high-thermal-conductivity prepreg material is disclosed, wherein boron nitride and aluminum oxide combined fillers are used in the epoxy phenolic curing system. It can be seen that in the related technology, boron nitride is a common component with good thermal conductivity; however, boron nitride fillers are expensive and are prone to orientation anisotropy, resulting in reduced heat shock resistance, flowability and other properties, in addition, boron nitride also reduces the adhesion between the PCB substrate and the metal foil, i.e. reduces the peel strength between the substrate and the metal foil.

[0004] Therefore, it has positive practical significance to develop a resin composition with high cost performance, high thermal conductivity, good resin flowability and high adhesion to metal foil. SUMMARY

[0005] In order to obtain a resin composition with high cost performance, high thermal conductivity, good resin flowability and high adhesion to metal foil, the present application provides a resin composition, a prepreg, a laminated board, an insulating board, an insulating film, a circuit substrate and an electronic device.

[0006] In a first aspect, the present application provides a resin composition, which adopts the following technical solution:

[0007] The resin composition comprises, by solid weight: 100 parts of a first component and 50-300 parts of a second component; the first component comprises 5-70 wt% of bismaleimide resin and / or its derivative, 5-80 wt% of epoxy resin, 0.5-60 wt% of curing agent and 0.5-5 wt% of accelerator; the second component comprises silicon nitride and aluminum oxide, and does not comprise boron nitride, and the mass ratio of the silicon nitride and the aluminum oxide is 1 / 5-2 / 3.

[0008] By the above technical solution, the silicon nitride and the aluminum oxide are compatible with each other to form a heat conduction network, and heat is transferred through the heat conduction network, thereby improving the heat conductivity of the resin composition, and the resin composition has high heat conductivity and high heat resistance. At the same time, the resin composition does not contain boron nitride, thereby reducing the generation of anisotropy, and further improving the heat conductivity, flowability, and adhesion (peeling strength) to the copper foil of the resin composition, and reducing the cost.

[0009] As an optional solution, the surface oxygen content of the silicon nitride is less than 2wt%.

[0010] As an optional solution, the average particle size of the silicon nitride is 0.1-8μm, and the specific surface area is 1-10m 2 / g.

[0011] As an optional solution, the particles of the aluminum oxide are spherical.

[0012] As an optional solution, the silicon nitride and the aluminum oxide are both surface treated by a silane coupling agent.

[0013] Further preferably, the silane coupling agent is a mixture of one or more of an amino silane coupling agent, a carbon-carbon double bond containing silane coupling agent, and an epoxy silane coupling agent; and more preferably, the silane coupling agent is preferably an amino silane coupling agent, and the molecular structure thereof is as shown below:

[0014] The brand is preferably KBM-573 manufactured by Shin-Etsu Chemical or Z-6883 manufactured by Dow Corning.

[0015] As an optional solution, the second component is preferably 80-200 parts by mass, and the mass ratio of the silicon nitride to the aluminum oxide is 1 / 3-1 / 2.

[0016] As an optional solution, the structural formula of the bismaleimide resin is selected from one or more of the following:

[0017]

[0018]

[0019]

[0020] wherein: R is hydrogen, methyl or ethyl, R2 is hydrogen, methyl or ethyl, and R1 is methylene, ethylene or n is an integer of 1-10.

[0021] ​As an option, the derivative of the bismaleimide resin is a modified product obtained by modifying the above-mentioned bismaleimide resin with an allyl compound, a diamine compound, a polyphenylene ether compound, or a siloxane compound. Among them, modification with an allyl compound or a diamine compound is preferred.

[0022] As an option, the content of the bismaleimide resin or the derivative of the bismaleimide resin in the resin composition is preferably 5 to 60 wt%.

[0023] As an option, the epoxy resin is one or a mixture of two or more of bisphenol A epoxy resin, bisphenol F epoxy resin, phosphorus-containing epoxy resin, o-cresol novolac epoxy resin, bisphenol A novolac epoxy resin, phenol novolac epoxy resin, trifunctional phenol-type epoxy resin, tetraphenyl ethane epoxy resin, biphenyl-type epoxy resin, naphthalene ring-type epoxy resin, dicyclopentadiene-type epoxy resin, aralkyl novolac epoxy resin, glycidyl amine-type epoxy resin, glycidyl ester-type epoxy resin.

[0024] Further preferably, the epoxy resin is a biphenyl-type epoxy resin

[0025] As an option, the curing agent is one or a mixture of two or more selected from the group consisting of phenol resin, dicyandiamide, diamino diphenyl sulfone, diamino diphenyl ether, styrene-maleic anhydride copolymer, benzoxazine compound, active ester, polyphenylene ether, and anhydride. Among them, the phenol resin can be a phenol novolac resin, a biphenyl-type phenol resin.

[0026] Further preferably, the curing agent is a phenol resin, an active ester, or a diamino diphenyl sulfone.

[0027] As an option, the accelerator is at least one of 2-methylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 2-undecylimidazole, 1-benzyl-2-methylimidazole, 2-heptadecylimidazole, 2-isopropylimidazole, 2-phenyl-4-methylimidazole, 2-dodecylimidazole, 1-cyanoethyl-2-methylimidazole, or a modified imidazole represented by the following structure.

[0028] wherein R3, R4, R5, and R6 are the same or different, and each is a methyl group, an ethyl group, or a tert-butyl group, A is a methylene group, an ethylene group, -S- or P200F50 manufactured by JER can be used.

[0029] wherein R3, R4, R5, and R6 are the same or different, and each is a methyl group, an ethyl group, or a tert-butyl group, A is a methylene group, an ethylene group, -S-, or aromatic hydrocarbon group, G8009L, the first industrial product, can be used.

[0030] As an option, the resin composition further comprises a silane coupling agent, and the silane coupling agent is 0.001-10 parts by weight with respect to 100 parts by weight of the resin composition. The silane coupling agent is an epoxy silane coupling agent.

[0031] As an option, the resin composition further comprises a dispersant, and the dispersant is 0.001-10 parts by weight with respect to 100 parts by weight of the resin composition. The dispersant is a mixture of one or more of phosphoric acid ester, modified polyurethane.

[0032] Further preferably, the weight ratio of the silane coupling agent and the dispersant is (2:1)-(10:1).

[0033] As an option, the resin composition further comprises a flame retardant, and the flame retardant is 1-50 parts by weight with respect to 100 parts by weight of the resin composition. The flame retardant is selected from a mixture of one or more of a bromine-based flame retardant, a phosphorus-based flame retardant, a nitrogen-based flame retardant, an organic silicon flame retardant, an organic metal salt flame retardant.

[0034] The bromine-based flame retardant is selected from a mixture of one or more of decabromodiphenyl ether, decabromodiphenyl ethane, brominated styrene, tetrabromophthalic amide.

[0035] The phosphorus-based flame retardant is selected from a mixture of one or more of inorganic phosphorus, a phosphoric acid ester compound, a phosphoric acid compound, a hypophosphorous acid compound, a phosphorus oxide compound, 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),

[0036] (m is an integer of 1-5), 10-phenyl-9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, tris(2,6-dimethylphenyl) phosphorus, phosphazene, a mixture of one or more of modified phosphazene (such as brand SPB-100), modified phosphazene (such as brand BP-PZ, PP-PZ, SPCN-100, SPV-100 and SPB-100L), DOPO, DOPO-HQ,

[0037] The nitrogen-based flame retardant is selected from a mixture of one or more of triazine compounds, cyanuric acid compounds, isocyanic acid compounds, phenothiazine.

[0038] The organic silicon flame retardant is selected from a mixture of one or more of organic silicon oil, organic silicon rubber, organic silicon resin.

[0039] The organometallic flame retardant is selected from one or more of a mixture of ferrocene, acetylacetone metal complex, organometallic carbonyl compound.

[0040] Further preferably, the flame retardant is a high melting point phosphorus-containing flame retardant, such as

[0041] As an alternative, the resin composition further comprises a dye, the dye being 0.001-10 parts by weight with respect to 100 parts by weight of the resin composition. The dye is selected from one or a mixture of both of a fluorescent dye, a black dye.

[0042] Further preferably, the fluorescent dye can be selected from a pyrazoline compound, and the black dye can be selected from liquid or powder carbon black, pyridine complex, azo complex, aniline black, black talc powder, cobalt chromium chromium metal oxide, azine or phthalocyanine.

[0043] In a second aspect, the present application provides a prepreg, which employs the following technical solution:

[0044] The prepreg comprises a reinforcing material and the resin composition of the first aspect; the resin composition is wrapped on the reinforcing material.

[0045] By employing the above technical solution, the thermal conductivity and heat resistance of the prepreg are significantly improved.

[0046] The prepreg is prepared by the following method: the resin composition is dissolved with a solvent to prepare a glue solution, and then the glue solution is coated on the reinforcing material by the method of immersion, and the immersed reinforcing material is baked at 100-180°C for 1-15 min; after drying, the prepreg is obtained.

[0047] As an alternative, the organic solvent is one or a mixture of more than one of acetone, butanone, methyl isobutyl ketone, propylene glycol methyl ether, benzene, toluene, xylene, cyclohexane, N, N-dimethylformamide, N, N-dimethylacetamide, ethylene glycol methyl ether.

[0048] As an alternative, the reinforcing material is one or a mixture of more than one of organic fabric, inorganic fabric, natural fiber, organic synthetic fiber.

[0049] Further preferably, the reinforcing material employs glass fiber cloth, and the glass fiber cloth specifically is open fiber cloth or flat cloth.

[0050] In addition, in order to improve the bonding between the interface of the resin composition and the glass fiber cloth, the glass fiber cloth is preferably chemically treated. The chemical treatment method is preferably coupling agent treatment; the coupling agent used is preferably epoxy silane or amino silane, so as to provide good water resistance and heat resistance.

[0051] In a second aspect, the present application provides a prepreg, wherein a resin composition is dissolved by a solvent to form a glue solution, a reinforcing material is immersed in the glue solution, and the prepreg is obtained by drying the reinforcing material after being immersed; and the prepreg has a thermal conductivity of 0.95 W / mK to 1.10 W / mK.

[0052] In a third aspect, the present application provides a laminate, which comprises a metal foil and the prepreg of the second aspect; and the metal foil is arranged on at least one side surface of the prepreg or a combination of a plurality of prepregs.

[0053] The laminate comprises a metal foil and the prepreg of the second aspect; and the metal foil is arranged on at least one side surface of the prepreg or a combination of a plurality of prepregs.

[0054] By using the above technical solution, the thermal index (heat resistance, thermal conductivity, etc.) of the laminate is significantly improved.

[0055] The method for manufacturing the laminate comprises the following steps: the metal foil is attached to one side or both sides of a prepreg or a combination of a plurality of prepregs, and then the laminate is obtained by pressing at a pressure of 0.2-2 MPa and a temperature of 150-250℃ for 2-4 hours.

[0056] The number of prepregs can be determined according to the required thickness of the laminate. The metal foil can be a copper foil, an aluminum foil or other conventional metal foils; and the thickness of the metal foil is not particularly limited, for example, 5 μm, 8 μm, 12 μm, 18 μm, 35 μm or 70 μm.

[0057] In a fourth aspect, the present application provides an insulating plate, which comprises the prepreg of the second aspect.

[0058] The insulating plate comprises the prepreg of the second aspect.

[0059] By using the above technical solution, the thermal conductivity and heat resistance of the insulating plate are significantly improved.

[0060] In a fifth aspect, the present application provides an insulating film, which comprises a base film and the resin composition of the first aspect; and the resin composition is coated on the base film.

[0061] The insulating film comprises a base film and the resin composition of the first aspect; and the resin composition is coated on the base film.

[0062] By using the above technical solution, the thermal index of the insulating film is significantly improved.

[0063] The prepreg is manufactured by the following method: the resin composition is dissolved by a solvent to form a glue solution, and then the glue solution is coated on a carrier film; and the insulating film is obtained by drying the carrier film after being coated with the glue solution.

[0064] As an option, the organic solvent is a mixture of one or more 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.

[0065] As an option, the carrier film is a mixture of one or more of a PE film, a PVC film, a PET film, and a PP film.

[0066] In a sixth aspect, the present application provides a circuit substrate, which adopts the following technical solution:

[0067] The circuit substrate comprises at least one of the prepreg of the second aspect, the laminated board of the third aspect, the insulating board of the fourth aspect, and the insulating film of the fifth aspect.

[0068] By adopting the above technical solution, the heat resistance of the circuit substrate is greatly improved.

[0069] In a seventh aspect, the present application provides an electronic device, which adopts the following technical solution:

[0070] The electronic device comprises the circuit substrate of the sixth aspect.

[0071] By adopting the above technical solution, since the heat resistance of the circuit substrate is greatly improved, the safety of the electronic device is significantly improved.

[0072] The present application has the beneficial technical effects that a resin composition, a prepreg, a laminated board, an insulating board, an insulating film, a circuit substrate, and an electronic device are provided. The silicon nitride and the aluminum oxide in the second component of the present application are compatible with each other to form a heat conduction network, and heat is transferred through the heat conduction network, thereby significantly improving the heat conduction coefficient of the resin composition of the present application, and further improving the heat conduction and heat resistance of the resin composition. At the same time, the second component does not contain boron nitride, which can reduce the anisotropy of the resin composition, thereby improving the heat conduction, flowability, and adhesion to the copper foil of the resin composition, and reducing the cost and improving the cost performance. BRIEF DESCRIPTION OF DRAWINGS

[0073] Figure 1 The rheological curve comparison chart of Example 1 and Comparative Example 1. DETAILED DESCRIPTION

[0074] The present application will now be further described in detail by examples, which are only descriptive and not limiting, and cannot limit the protection scope of the present application.

[0075] The present application discloses a resin composition comprising, by weight of solids: a first component 100 parts and a second component 50-300 parts; the first component comprising 5-70 wt% of a bismaleimide resin and / or its derivative, 5-80 wt% of an epoxy resin, 0.5-60 wt% of a curing agent and 0.5-5 wt% of an accelerator; the second component comprising silicon nitride and aluminum oxide, and not comprising boron nitride, the mass ratio of the silicon nitride and aluminum oxide being 1 / 5-2 / 3. In some embodiments, the content of the bismaleimide resin or the derivative of the bismaleimide resin in the resin composition is preferably 5-60 wt%; the second component is preferably 80-200 mass parts, and the mass ratio of the silicon nitride and aluminum oxide is 1 / 3-1 / 2.

[0076] wherein the silicon nitride has a surface oxygen content of less than 2 wt%, an average particle size of 0.1-8 μm, and a specific surface area of 1-10 m 2 / g. The aluminum oxide particles are spherical.

[0077] In order to improve the compatibility of the silicon nitride, aluminum oxide and resin, in some embodiments, the silicon nitride and aluminum oxide are both surface treated with a silane coupling agent. The silane coupling agent is a mixture of one or more of an amino silane coupling agent, a carbon-carbon double bond-containing silane coupling agent and an epoxy silane coupling agent. Preferably, the silane coupling agent is an amino silane coupling agent, and its molecular structure is as shown below:

[0078] The trade name is preferably KBM-573 manufactured by Shin-Etsu Chemical or Z-6883 manufactured by Dow Corning.

[0079] The structural formula of the bismaleimide resin is selected from a mixture of one or more of:

[0080]

[0081]

[0082]

[0083] wherein: R is hydrogen, methyl or ethyl, R2 is hydrogen, methyl or ethyl, and R1 is methylene, ethylene or n is an integer of 1-10.

[0084] ​The derivative of the bismaleimide resin is a modified product obtained by modifying the above-mentioned bismaleimide resin with an allyl compound, a diamine compound, a polyphenylene ether compound, or a siloxane compound. Among them, modification with an allyl compound or a diamine compound is preferred; more preferably, an allyl compound is mixed with the bismaleimide at a mass ratio of 5-80: 100 and reacted at 80-160°C for 10-120 min, and then cooled to room temperature to obtain an allyl-modified bismaleimide prepolymer.

[0085] The epoxy resin is a mixture of one or more of a mixture of bisphenol A epoxy resin, bisphenol F epoxy resin, phosphorus-containing epoxy resin, o-cresol novolac epoxy resin, bisphenol A novolac epoxy resin, phenol novolac epoxy resin, trifunctional phenol-type epoxy resin, tetraphenyl ethane epoxy resin, biphenyl-type epoxy resin, naphthalene ring-type epoxy resin, dicyclopentadiene-type epoxy resin, aralkyl novolac epoxy resin, glycidyl amine-type epoxy resin, glycidyl ester-type epoxy resin. In some embodiments, the epoxy resin is preferably a biphenyl-type epoxy resin.

[0086] The curing agent is a mixture of one or more selected from the group consisting of phenol formaldehyde resin, dicyandiamide, diaminodiphenyl sulfone, diaminodiphenyl ether, styrene-maleic anhydride copolymer, benzoxazine compound, active ester, polyphenylene ether, acid anhydride. Among them: the phenol formaldehyde resin can be phenol formaldehyde NOVOLAC resin, biphenyl-type phenol formaldehyde resin. In some embodiments, the curing agent is preferably phenol formaldehyde resin, active ester or diaminodiphenyl sulfone.

[0087] The accelerator is imidazole.

[0088] The resin composition can further comprise a silane coupling agent, the silane coupling agent being 0.001-10 parts by weight based on 100 parts by weight of the resin composition. In some embodiments, the silane coupling agent is preferably an epoxy silane coupling agent.

[0089] The resin composition can further comprise a dispersant, the dispersant being 0.001-10 parts by weight based on 100 parts by weight of the resin composition. In some embodiments, the dispersant is preferably a mixture of one or both of phosphate esters, modified polyurethanes.

[0090] In addition, in some embodiments, the weight ratio of the silane coupling agent and the dispersant is preferably (2:1)-(10:1).

[0091] The resin composition can further comprise a flame retardant in an amount of 1 to 50 parts by weight based on 100 parts by weight of the resin composition. The flame retardant is selected from the group consisting of one or more of a bromine-based flame retardant, a phosphorus-based flame retardant, a nitrogen-based flame retardant, a silicone-based flame retardant, an organic metal salt-based flame retardant. In some embodiments, the bromine-based flame retardant is preferably one or more of decabromodiphenyl ether, decabromodiphenyl ethane, brominated styrene, tetrabromophthalic diamide; the phosphorus-based flame retardant is preferably one or more of inorganic phosphorus, phosphate ester compound, phosphoric acid compound, hypophosphorous acid compound, phosphorus oxide compound, 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), (m is an integer of 1 to 5), 10-phenyl-9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, tris(2,6-dimethylphenyl) phosphorus, phosphazene, modified phosphazene, or a mixture of one or more thereof; wherein the phosphorus-based flame retardant is more preferably phosphazene (such as trade name SPB-100), modified phosphazene (such as trade names BP-PZ, PP-PZ, SPCN-100, SPV-100, and SPB-100L), DOPO, DOPO-HQ, the nitrogen-based flame retardant is preferably one or more of triazine compound, cyanuric acid compound, isocyanic acid compound, phenothiazine; the silicone-based flame retardant is preferably one or more of silicone oil, silicone rubber, silicone resin; the organic metal salt-based flame retardant is preferably one or more of ferrocene, acetylacetone metal complex, organic metal carbonyl compound.

[0092] It is to be noted that the type of flame retardant is not limited to the above; it is to be understood that the added flame retardant can be selected according to the specific application field of the laminate, for example, in the application field requiring halogen, a non-halogen flame retardant is preferred.

[0093] In addition, in some more preferred embodiments, the flame retardant is preferably a high melting point phosphorus-containing flame retardant, such as

[0094] The resin composition can further comprise a dye in an amount of 0.001 to 10 parts by weight based on 100 parts by weight of the resin composition. The dye is selected from the group consisting of one or more of a fluorescent dye, a black dye. In some embodiments, the fluorescent dye is preferably a pyrazoline compound; the black dye is preferably carbon black in liquid or powder form, pyridine complex, azo complex, aniline black, black talc powder, cobalt chromium chromium metal oxide, azine, or phthalocyanine.

[0095] The present application also discloses a prepreg comprising a reinforcing material and the resin composition described above. In some embodiments, the reinforcing material is preferably one or more of a mixture of organic fabric, inorganic fabric, natural fiber, and organic synthetic fiber.

[0096] The present application also discloses a laminate comprising a metal foil and the prepreg described above; the metal foil is disposed on at least one side surface of the prepreg or a combination of one or more prepregs.

[0097] The present application also discloses an insulating board comprising the prepreg described above.

[0098] The present application also discloses an insulating film comprising a base film and the resin composition described above; wherein: the high-frequency resin is coated on the base film. In some embodiments, the carrier film is preferably one or more of a mixture of PE film, PVC film, PET film, and PP film.

[0099] The present application also discloses a circuit substrate comprising one or more of a mixture of the prepreg, the laminate, the insulating board, and the insulating film described above.

[0100] The present application also discloses an electronic device comprising the circuit substrate described above.

[0101] Preparation Example 1

[0102] The present preparation example discloses a preparation method of an allyl-modified bismaleimide prepolymer, comprising the following steps:

[0103] P1, mix 100 g of bismaleimide (Daiwako, BMI-2300) and 50 g of bisphenol A type allyl compound uniformly.

[0104] P2, place the mixture obtained in P1 at 100°C for 70 min to obtain a transparent product.

[0105] P3, cool the transparent product obtained in P2 to room temperature to obtain an allyl-modified bismaleimide prepolymer.

[0106] Example 1

[0107] The present example discloses a resin composition prepared by mixing the following raw materials: 30 g of bismaleimide resin, 20 g of bisphenol A type epoxy resin, 30 g of biphenyl type epoxy resin, 15 g of phenol formaldehyde resin, 4.5 g of 4,4'-diamino diphenyl sulfone (DDS), 0.5 g of imidazole, 86 g of silicon nitride A, and 171 g of aluminum oxide (the mass ratio of silicon nitride A to aluminum oxide is 0.529:1).

[0108] In the formula, the bismaleimide resin is BMI-2300 from Japan Dawa; the biphenyl type epoxy resin is NC-3000 from Huaxi; the phenolic resin and 4,4'-diamino diphenyl sulfone are curing agents; and the imidazole is an accelerator.

[0109] The silicon nitride A is SN-1040 from Lianrui New Material, which has a D50 of 1.0 μm, a surface oxygen content of 1.5 wt%, and a surface treated with a silane coupling agent; and the alumina is SLA-2 from Anhui Yishitong, which has a spherical shape. 50

[0110] The embodiment also discloses a prepreg, which comprises a glass fiber cloth and a resin composition impregnated in the glass fiber cloth. The glass fiber cloth is a reinforcing material, and in this embodiment, is a fiber opening cloth, and the surface of which is treated with an epoxy silane coupling agent.

[0111] The prepreg is prepared by the following method:

[0112] S11, the resin composition is diluted in acetone to form a glue solution with a solid content of 60 wt%.

[0113] S12, the glue solution obtained in S11 is coated on the glass fiber cloth and impregnated for 5 min; and then the glass fiber cloth is placed in a 160℃ air drying oven for 5 min to obtain a prepreg.

[0114] The embodiment also discloses a laminated board prepared by the following method:

[0115] S21, the prepreg is cut to a target size (the size is determined according to actual conditions and is not particularly limited herein), and an electrolytic copper foil (18 mm thick) is attached to each side surface of the prepreg.

[0116] S22, the pressure of a vacuum hot press is adjusted to 1.5 MPa. The prepreg and copper foil combination obtained in S21 is placed in the vacuum hot press, and is hot pressed at a temperature of 150℃ for 2 h, and then is hot pressed at a temperature of 200℃ for 120 min to obtain a laminated board.

[0117] The embodiment also discloses an insulating board comprising a piece of the prepreg prepared by a conventional preparation method, which is not described herein.

[0118] The embodiment also discloses an insulating film comprising a base film and a resin layer coated on the base film. The resin layer is composed of the resin composition, and the thickness of the resin layer is 0.1 mm; and the base film is a PET film.

[0119] The insulating film is prepared by the following method:

[0120] ​S31, the resin composition is diluted in cyclohexane to form a glue solution; the solid content of the glue solution is controlled to be 50wt%.

[0121] S32, the glue solution obtained in S31 is applied on a PET base film; then the base film is placed in a 120°C air drying oven for 2 minutes to obtain an insulation film, and the thickness of the resin composition film is controlled to be 0.1mm.

[0122] The present embodiment also discloses a circuit substrate comprising a piece of the above-mentioned prepreg, which is prepared by using a conventional preparation method known in the art, and thus will not be described herein.

[0123] The present embodiment also discloses an electronic device comprising the above-mentioned circuit substrate. After using the substrate, the thermal index of the electronic device is greatly improved.

[0124] Example 2

[0125] The present embodiment is basically the same as Example 1, except that the mass ratio of silicon nitride to aluminum oxide in the raw materials of the resin composition is changed to 0.338:1; see Table 1 for details.

[0126] Table 1: Composition ratio of Examples 1-3 and Comparative Examples 1-4

[0127]

[0128]

[0129] Note: the unit of the amount of each component added is g.

[0130] Example 3

[0131] The present embodiment is basically the same as Example 1, except that the allyl-modified bismaleimide prepolymer obtained in Preparation Example 1 is used to replace the bismaleimide resin in an equal amount in the raw materials of the resin composition, and the mass ratio of silicon nitride to aluminum oxide is changed to 0.637:1; see Table 1 for details.

[0132] Example 4

[0133] The present embodiment is basically the same as Example 1, except that the silicon nitride B (manufactured by Linkwin) with a surface oxygen content of 2.9wt% is used in the raw materials of the resin composition; see Table 1 for details.

[0134] Comparative Example 1

[0135] The main difference between the present comparative example and Example 1 is that boron nitride is added in the raw materials of the resin composition; see Table 1 for details.

[0136] Comparative Example 2

[0137] The main difference between this comparative example and Example 3 is that the mass ratio of silicon nitride to alumina in the raw material of the resin composition is changed to 0.184:1; see Table 1.

[0138] Comparative Example 3

[0139] The main difference between this comparative example and Example 1 is that the mass ratio of silicon nitride to alumina in the raw material of the resin composition is changed to 0.784:1; see Table 1.

[0140] Sample testing

[0141] The prepregs obtained in Examples 1-3 and Comparative Examples 1-4 were tested for performance, and the results are shown in Table 2.

[0142] (1) Thermal conductivity: measured according to ASTM D5470 method.

[0143] (2) Glass transition temperature (Tg): measured according to differential scanning calorimetry method, with a heating rate of 10°C / min.

[0144] (3) Peel strength (PS): the peel strength of the metal cover layer was tested according to the "after thermal stress" test conditions in IPC-TM-650 method using the laminated board a.

[0145] (4) Flowability: four prepregs were stacked together, with a piece of centrifugal film placed on top and bottom, and a small press was placed at a temperature of 171°C and a pressure of 10 kg / cm 2 for 10 min. The weight before pressing M1 and the weight after pressing M2 were measured, and the flowability = (M1-M2)*100 / M1.

[0146] (5) Substrate appearance: the prepreg was made into a circuit substrate, the copper foil on the top and bottom of the circuit substrate was etched, and the substrate appearance was observed.

[0147] Table 2 Performance testing of samples obtained in Examples 1-3 and Comparative Examples 1-4

[0148]

[0149] As can be seen from Table 2, when the resin composition does not contain boron nitride, the flowability and peel strength of the obtained prepreg are significantly increased, and the dry flower phenomenon of the substrate is improved; at the same time, when the resin composition does not contain boron nitride, the cost is greatly reduced, and the cost performance is improved.

[0150] In addition, as can be seen from the rheological curve comparison chart of Example 1 and Comparative Example 1, the rheological window of Example 1 is wider, and the minimum melt viscosity is lower, indicating that the resin flowability is better during high-temperature lamination, which is beneficial to process control.

[0151] From the results of Comparative Examples 1-3 and Comparative Examples 2-3, it can be found that when the mass ratio of silicon nitride and aluminum oxide is between 1 / 5 and 2 / 3, the obtained prepreg has both ideal thermal conductivity and peeling strength; when the mass ratio of silicon nitride and aluminum oxide is below 1 / 5 (Comparative Example 1), the obtained prepreg has good peeling strength but the thermal conductivity value is significantly reduced, only 0.70 W / mK; when the mass ratio of silicon nitride and aluminum oxide is above 2 / 3 (Comparative Example 2), the obtained prepreg has good thermal conductivity but has low peeling strength with copper foil and the substrate appears dry flower phenomenon.

[0152] From the results of Comparative Example 1 and Example 4, it can be found that when the surface oxygen content of silicon nitride is more than 2wt%, the thermal conductivity and peeling strength of the obtained prepreg are reduced, and the substrate appears dry flower. Preferably, the thermal conductivity of the prepreg is between 0.95 W / mK and 1.10 W / mK.

[0153] Based on the above ideal embodiments of the present application, through the above description, relevant personnel can make various changes and modifications without deviating from the scope of the technical idea of the present application. The technical scope of the present application is not limited to the content of the specification, and the technical scope must be determined according to the scope of the claims.

Claims

1. A resin composition characterized by: The composition comprises, by weight of the solid: 100 parts of a first component and 80-200 parts of a second component; the first component comprises 5-70 wt% of a bismaleimide resin and / or its derivative, 5-80 wt% of an epoxy resin, 0.5-60 wt% of a curing agent and 0.5-5 wt% of an accelerator; the second component only comprises silicon nitride and alumina, but does not comprise boron nitride, and the mass ratio of the silicon nitride to the alumina is 1 / 3-1 / 2; the surface oxygen content of the silicon nitride is less than 2 wt%, the average particle size is 0.1-8 μm, and the specific surface area is 1-10 m 2 / g; and the alumina particles are spherical.

2. The resin composition according to claim 1, characterized by: Silicon nitride and aluminum oxide are compatible with each other to form a heat conducting network.

3. The resin composition according to claim 1, characterized by: The structural formula of the bismaleimide resin is selected from the group consisting of: A mixture of one or more of them; wherein: R is hydrogen, methyl or ethyl, R2is hydrogen, methyl or ethyl, R1is methylene, ethylene or n is an integer from 1 to 10.

4. The resin composition according to claim 1, characterized by: The derivative of the bismaleimide resin is a modified product obtained by modifying the bismaleimide resin with an allyl compound, a diamine compound, a polyphenylene ether compound, or a siloxane compound.

5. The resin composition according to claim 1, characterized by: The epoxy resin is one or a mixture of two or more selected from the group consisting of bisphenol A epoxy resin, bisphenol F epoxy resin, phosphorus-containing epoxy resin, o-cresol novolac epoxy resin, bisphenol A novolac epoxy resin, phenol novolac epoxy resin, trifunctional phenol-type epoxy resin, tetraphenyl ethane epoxy resin, biphenyl-type epoxy resin, naphthalene ring-type epoxy resin, dicyclopentadiene-type epoxy resin, aralkyl linear phenol novolac epoxy resin, glycidyl amine-type epoxy resin, and glycidyl ester-type epoxy resin.

6. The resin composition according to claim 1, characterized by: The curing agent is one or a mixture of two or more selected from the group consisting of phenol novolac resin, dicyandiamide, diamino diphenyl sulfone, diamino diphenyl ether, styrene-maleic anhydride copolymer, benzoxazine compound, active ester, polyphenylene ether, and anhydride.

7. The resin composition according to claim 1, characterized by: The accelerator is imidazole.

8. The resin composition according to any one of claims 1 to 7, characterized by: The silane coupling agent is one or a mixture of two or more selected from the group consisting of amino silane coupling agent, carbon-carbon double bond-containing silane coupling agent, and epoxy silane coupling agent. The dispersant is one or a mixture of two or more selected from the group consisting of phosphate ester and modified polyurethane.

9. A prepreg, characterized by, The resin composition is dissolved in a solvent to form a glue solution, the reinforcing material is immersed in the glue solution, and the immersed reinforcing material is heated and dried to obtain the prepreg, and the thermal conductivity of the prepreg is 0.95-1.10 W / mK.

10. Use of the resin composition according to any one of claims 1-8 in a prepreg, a laminated board, an insulating board, an insulating film, a circuit substrate, and an electrical device.

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