Resin composition and use thereof

Abstract

The application discloses a resin composition and application thereof, and the resin composition comprises, in terms of solid weight, 10-70 parts of a benzoxazine resin containing unsaturated bonds, and 20-100 parts of a maleimide resin; wherein the benzoxazine resin containing unsaturated bonds is a mixture of a benzoxazine resin containing double bonds and a benzoxazine resin containing triple bonds. Compared with the prior art, the resin composition and application thereof can not only control the reactivity between the maleimide resin and the benzoxazine resin, improve the crosslinking network density, but also is beneficial to controlling the production speed of prepreg, and the prepreg has good apparent quality, and meanwhile has excellent high heat resistance, high modulus, low water absorption, low thermal expansion coefficient and low curing shrinkage.

Description

Technical Field

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

[0002] With the development of communication technology, electronic products are becoming smaller and smaller, more and more diverse in function, and more and more dense in circuit design. As a result, the number of chips and modules that need to be carried on printed circuit boards (PCBs) is also increasing, which in turn requires copper-clad laminates to have higher modulus, higher heat resistance and lower coefficient of thermal expansion.

[0003] As electronic products become smaller and circuit designs become denser, more and more design companies are adopting HDI (High-Intensity Displacement) technology for printed circuit board design. This technology places higher demands on the substrate material in terms of dimensional stability, resistance to repeated thermal shocks, and resistance to long-term thermal and oxygen aging, far exceeding the performance of traditional resin composition formulations.

[0004] Therefore, developing a resin composition that combines low coefficient of thermal expansion, high heat resistance, high modulus, low water absorption, and low curing shrinkage is an urgent problem to be solved in current circuit board applications. Summary of the Invention

[0005] In order to obtain a resin composition that has low coefficient of thermal expansion, high heat resistance, high modulus, low water absorption and low curing shrinkage, this application provides a resin composition and prepreg, laminate, insulating board, insulating film, circuit board and electronic device made from the resin composition.

[0006] To achieve the above-mentioned objective, one embodiment of the present invention provides a resin composition, comprising, by weight of solids:

[0007] Benzoxazine resin containing unsaturated bonds: 10-70 parts;

[0008] Maleimide resin: 20-100 parts;

[0009] The benzoxazine resin containing unsaturated bonds is a mixture of benzoxazine resin containing double bonds and benzoxazine resin containing triple bonds.

[0010] By combining maleimide resin with benzoxazine resin containing double bonds or benzoxazine resin containing triple bonds, the reactivity between maleimide resin and benzoxazine resin can be controlled, and the crosslinking network density can be increased. This also helps to control the production speed of the prepreg, giving the prepreg better appearance quality, while also possessing excellent high heat resistance, high modulus, low water absorption, low coefficient of thermal expansion, and low curing shrinkage.

[0011] To achieve the above-mentioned objective, one embodiment of the present invention also provides a resin composition comprising a prepolymer, said prepolymer being prepared by the following method:

[0012] Step (1) involves reacting maleimide resin with benzoxazine resin containing double bonds to obtain an intermediate product;

[0013] Step (2): Add a benzoxazine resin containing a triple bond to the intermediate product and react to obtain the prepolymer.

[0014] By prepolymerizing maleimide resin with benzoxazine resin containing double bonds and benzoxazine resin containing triple bonds, the rheological properties of the resin composition during lamination can be improved, and the adhesive can be well wetted into the glass fiber cloth, thereby improving the lamination processability. On the other hand, the reactivity between maleimide resin and benzoxazine resin can be controlled, the crosslinking network density can be increased, and the prepreg can have a better appearance quality, while also possessing excellent high heat resistance, high modulus, low water absorption, low coefficient of thermal expansion and low curing shrinkage.

[0015] As a further improvement of one embodiment of the present invention, the reaction conditions in the preparation method of the prepolymer are: reaction temperature of 60-170°C and reaction time of 10-120 min.

[0016] As a further improvement of one embodiment of the present invention, the reaction temperature of step (1) is 80-130°C, and the reaction temperature of step (2) is 60-100°C.

[0017] As a further improvement of one embodiment of the present invention, the resin composition further includes maleimide resin and benzoxazine resin containing unsaturated bonds, wherein the benzoxazine resin containing unsaturated bonds is a mixture of benzoxazine resin containing double bonds and benzoxazine resin containing triple bonds.

[0018] As a further improvement of one embodiment of the present invention, the resin composition further includes a benzoxazine resin without unsaturated bonds.

[0019] As a further improvement of one embodiment of the present invention, the unsaturated benzoxazine resin is one or a mixture of at least two of the following: bisphenol A type benzoxazine resin, dicyclopentadiene type benzoxazine resin, bisphenol F type benzoxazine resin, phenolphthalein type benzoxazine resin, MDA type benzoxazine resin, ODA type benzoxazine resin, or benzoxazine resin with unsaturated bond end capping.

[0020] As a further improvement of one embodiment of the present invention, in the benzoxazine resin containing unsaturated bonds, the content of benzoxazine resin containing triple bonds is 1-70 wt%, and the content of benzoxazine resin containing double bonds is 30-99 wt%.

[0021] More preferably, the content of benzoxazine resin containing unsaturated bonds and benzoxazine resin containing triple bonds is 1%, 3%, 5%, 10%, 15%, 20%, 25%, 30%, 35%, 40%, 45%, 50%, 55%, 60%, 65%, or 70%.

[0022] As a further improvement of one embodiment of the present invention, the benzoxazine resin containing triple bonds has carbon-carbon triple bonds at its end.

[0023] As an alternative, the triple-bonded benzoxazine resin is one or a mixture of at least two of the following structures:

[0024]

[0025]

[0026] As a further improvement of one embodiment of the present invention, the benzoxazine resin containing double bonds contains carbon-carbon double bonds at least in the side chain.

[0027] As an alternative, the double-bonded benzoxazine resin is one or a mixture of at least two of the following structures:

[0028]

[0029] Where R is -CH2-, -O-, -CH2-CH2- or no connecting bond; R0, R1 and R2 may be the same or different, each independently selected from hydrogen, alkyl or olefin groups, and at least one of R0, R1 and R2 contains an unsaturated group; R4 is -CH2-, -S-、 -O-, -CH2-CH2-, or no connecting key.

[0030] As an alternative, the alkyl group is methyl, ethyl, or tert-butyl.

[0031] As an alternative, the carbon-carbon double bond is vinyl, allyl, propenyl, methacrylate, acrylate, styrene, styrene-allyl, or styrene-propenyl.

[0032] As an alternative, the maleimide resin is one or a mixture of at least two of the following structures:

[0033] Wherein, R2 is hydrogen, methyl, or ethyl, and R1 is methylene, ethylene, or... n is 0 or an integer from 1 to 10;

[0034] Where n is an integer from 1 to 10;

[0035] Where n is an integer from 1 to 10;

[0036] Where n is an integer from 1 to 10;

[0037] Where n is an integer from 1 to 10;

[0038] Where n is an integer from 1 to 10;

[0039] Where n is an integer from 1 to 10, and m is an integer from 1 to 10;

[0040] The structural formula (23) is given, where n is an integer from 1 to 10 and m is an integer from 1 to 10.

[0041] Where n is an integer from 1 to 10;

[0042]

[0043] More preferably, the maleimide resin is a maleimide resin containing aliphatic long-chain groups, which is beneficial to reduce the dielectric constant and dielectric loss value of the prepreg when using the resin composition to prepare the prepreg.

[0044] As an alternative, the maleimide resin containing aliphatic long-chain groups is selected from BMI-3000, BMI-3000J, BMI-2500, BMI-1500, BMI-689, BMI-1400, BMI-1700, BMI-5000 or BMI-6100 from Molecular Design, and SLK-3000, SLK-2600, SLK-2500, SLK-1500 or SLK-6895 from Shin-Etsu Chemical.

[0045] As a further improvement of one embodiment of the present invention, the resin composition further includes a thermoplastic elastomer.

[0046] As an alternative, the thermoplastic elastomer is at least one of styrene-based thermoplastic elastomers, polybutadiene-based thermoplastic elastomers, silicone-based thermoplastic elastomers, methacrylate-based thermoplastic elastomers, or butyl methacrylate-based thermoplastic elastomers.

[0047] As an optional option, the styrene-based thermoplastic elastomer is selected from H1041, H1043, H1051, H1052, H1053, H1221, P1500, P2000, M1911 or M1913 from Asahi Kasei Corporation of Japan; 8004, 8006, 8076, 8104, V9827, 2002, 2005, 2006, 2007, 2104, 7125, 4033, 4044, 4055, 4077 or 4099 from Kuraray Corporation of the United States; and D1116A, D1118E, D1152E, D1170B, D1157A, D1171P, D1184A, A1535 or A1536 from Kraton Pharmaceuticals of the United States.

[0048] As an alternative, the organosilicon thermoplastic elastomer is selected from Shin-Etsu Chemical's X-40-2670, R-170S, X-40-2705, X-40-2701, KMP-600, KMP-605 or X-52-7030, or DOW's AY-42-119, EP-2600, EP-2601, EP-2720, TMS-2670, EXL-2315 or EXL-2655.

[0049] As an alternative, the methacrylate thermoplastic elastomer is selected from Akema's M51, M52, M22 or D51N, Kuraray's LA-2330, Nagase's SG-P3 series or SG-80 series.

[0050] As a further improvement of one embodiment of the present invention, the resin composition further includes a flame retardant.

[0051] As an alternative, the flame retardant is at least one of the following: brominated flame retardants, phosphorus-based flame retardants, nitrogen-based flame retardants, organosilicon flame retardants, organometallic flame retardants, and inorganic flame retardants.

[0052] As an alternative, the brominated flame retardant is selected from decabromodiphenyl ether, decabromodiphenyl ethane, styrene bromide, or tetrabromophthalamide.

[0053] 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) Phosphazene or modified phosphazene.

[0054] More preferably, the modified phosphorus is phosphorus containing unsaturated double bonds.

[0055] As an alternative, the nitrogen-based flame retardant is selected from triazine compounds, cyanuric acid compounds, isocyanate compounds, and phenothiazine compounds.

[0056] As an optional option, the silicone flame retardant is selected from silicone oil, silicone rubber, and silicone resin.

[0057] As an alternative, the organometallic flame retardant is selected from ferrocene, acetylacetone metal complexes, and organometallic carbonyl compounds.

[0058] As an alternative, the inorganic flame retardant is selected from aluminum hydroxide, magnesium hydroxide, aluminum oxide, and barium oxide.

[0059] As a further improvement of one embodiment of the present invention, the resin composition further includes a catalyst.

[0060] As an alternative, the catalyst is at least one of imidazole catalysts, pyridine catalysts, and organometallic salt catalysts.

[0061] As an alternative, the catalyst is at least one selected from 4-dimethylaminopyridine, 2-methylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, modified imidazole, and zinc octanoate.

[0062] As an alternative, the modified imidazole is one or a mixture of at least two of the following structures:

[0063]

[0064] Among them, R3, R4, R5 and R6 may be the same or different, and each is independently selected from methyl, ethyl or tert-butyl; A is methylene, ethylene, ... -S-、 Or aromatic hydrocarbon group; B is methylene, ethylene, -S- or

[0065] Specifically, the modified imidazole of structural formula (26) can be the modified imidazole of Daiichi Kogyo Co., Ltd. with the brand name G8009L; the modified imidazole of structural formula (27) can be the modified imidazole of JER Corporation with the brand name P200F50.

[0066] As a further improvement of one embodiment of the present invention, the resin composition further includes filler.

[0067] As an alternative, the packing material is at least one of inorganic packing material, organic packing material, and composite packing material.

[0068] More preferably, the filler is selected from spherical silica, alumina, or aluminum hydroxide, and more preferably from spherical silica.

[0069] As a further improvement of one embodiment of the present invention, the filler is surface-treated with a silane coupling agent, wherein the silane coupling agent is at least one of an aminosilane coupling agent, a carbon-carbon double bond silane coupling agent, or an epoxysilane coupling agent.

[0070] As an alternative, the silane coupling agent is selected from the following structures:

[0071]

[0072] 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:

[0073] 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.

[0074] 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.

[0075] 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.

[0076] As an alternative, the reinforcing material is selected from at least one of natural fibers, organic synthetic fibers, organic fabrics, and inorganic fabrics.

[0077] 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.

[0078] Furthermore, when the reinforcing material is glass fiber cloth, a coupling agent is used to chemically treat the glass fiber cloth to improve the interfacial bonding between the resin composition and the glass fiber cloth. The coupling agent used here is preferably an epoxy silane coupling agent or an amino silane coupling agent to provide good water resistance and heat resistance.

[0079] 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.

[0080] 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.

[0081] 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.

[0082] 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.

[0083] 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.

[0084] 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.

[0085] 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.

[0086] 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.

[0087] As an alternative, the carrier film is selected from at least one of PET film, PP film, PE film, and PVC film.

[0088] 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.

[0089] 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.

[0090] The beneficial technical effects of this application are: to provide a resin composition and the application of the resin composition in prepreg, laminate, insulating board, insulating film, circuit board and electronic device.

[0091] Due to the application of the above technical solution, the present invention has the following advantages compared with the prior art:

[0092] (1) By combining maleimide resin with benzoxazine resin containing double bonds and benzoxazine resin containing triple bonds, it is possible not only to control the reactivity between maleimide resin and benzoxazine resin and improve the crosslinking network density, but also to control the production speed of the prepreg, so that the prepreg has a better appearance quality, and at the same time has excellent high heat resistance, high modulus, low water absorption, low coefficient of thermal expansion and low curing shrinkage.

[0093] (2) By prepolymerizing maleimide resin with benzoxazine resin containing double bonds and benzoxazine resin containing triple bonds, the rheological properties of the resin composition during lamination can be improved, and the adhesive can be well wetted into the glass fiber cloth, thereby improving the lamination processability. Detailed Implementation

[0094] 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.

[0095] One embodiment of the present invention provides a resin composition and its application in prepregs, laminates, insulating boards, insulating films, circuit boards, and electronic devices.

[0096] First Implementation Method

[0097] This embodiment provides a resin composition comprising, by solid weight:

[0098] Benzoxazine resin containing unsaturated bonds: 10-70 parts;

[0099] Maleimide resin: 20-100 parts;

[0100] The benzoxazine resin containing unsaturated bonds is a mixture of benzoxazine resin containing double bonds and benzoxazine resin containing triple bonds.

[0101] Furthermore, the resin composition further includes 5 to 45 parts by weight of a benzoxazine resin without unsaturated bonds.

[0102] Preferably, the resin composition, by solid weight, comprises:

[0103] Benzoxazine resin containing double bonds: 10-40 parts;

[0104] Benzoxazine resin containing triple bonds: 3-20 parts;

[0105] Benzoxazine resin without unsaturated bonds: 5-10 parts;

[0106] Maleimide resin: 40-70 parts.

[0107] Furthermore, the unsaturated benzoxazine resin is one or a mixture of at least two of the following: bisphenol A type benzoxazine resin, dicyclopentadiene type benzoxazine resin, bisphenol F type benzoxazine resin, phenolphthalein type benzoxazine resin, MDA type benzoxazine resin, ODA type benzoxazine resin, or benzoxazine resin with unsaturated bond end capping.

[0108] Preferably, in the benzoxazine resin containing unsaturated bonds, the content of benzoxazine resin containing triple bonds is 1-70 wt%, and the content of benzoxazine resin containing double bonds is 30-99 wt%.

[0109] More preferably, the content of benzoxazine resin containing unsaturated bonds and benzoxazine resin containing triple bonds is 1%, 3%, 5%, 10%, 15%, 20%, 25%, 30%, 35%, 40%, 45%, 50%, 55%, 60%, 65%, or 70%.

[0110] Furthermore, the benzoxazine resin containing triple bonds has carbon-carbon triple bonds at its ends.

[0111] Optionally, the triple-bonded benzoxazine resin is one or a mixture of at least two of the following structures:

[0112]

[0113]

[0114] Furthermore, the benzoxazine resin containing double bonds contains carbon-carbon double bonds at least in the side chain.

[0115] Optionally, the double-bonded benzoxazine resin is one or a mixture of at least two of the following structures:

[0116]

[0117]

[0118] Where R is -CH2-, , -O-, -CH2-CH2- or no connecting bond; R0, R1 and R2 may be the same or different, each independently selected from hydrogen, alkyl or olefin groups, and at least one of R0, R1 and R2 contains an unsaturated group; R4 is -CH2-, -S-、 -O-, -CH2-CH2-, or no connecting key.

[0119] Optionally, the alkyl group is methyl, ethyl, or tert-butyl.

[0120] Optionally, the carbon-carbon double bond is vinyl, allyl, propenyl, methacrylate, acrylate, styrene, styrene-allyl, or styrene-propenyl.

[0121] Optionally, the maleimide resin is one or a mixture of at least two of the following structures:

[0122]

[0123] Wherein, R2 is hydrogen, methyl, or ethyl, and R1 is methylene, ethylene, or... n is 0 or an integer from 1 to 10;

[0124] Where n is an integer from 1 to 10;

[0125] Where n is an integer from 1 to 10;

[0126] Where n is an integer from 1 to 10;

[0127] Where n is an integer from 1 to 10;

[0128] Where n is an integer from 1 to 10;

[0129] Where n is an integer from 1 to 10, and m is an integer from 1 to 10;

[0130] Where n is an integer from 1 to 10, and m is an integer from 1 to 10;

[0131] Where n is an integer from 1 to 10;

[0132]

[0133] More preferably, the maleimide resin is a maleimide resin containing aliphatic long-chain groups.

[0134] Optionally, the maleimide resin containing aliphatic long-chain groups is selected from BMI-3000, BMI-3000J, BMI-2500, BMI-1500, BMI-689, BMI-1400, BMI-1700, BMI-5000 or BMI-6100 from Molecular Design, and SLK-3000, SLK-2600, SLK-2500, SLK-1500 or SLK-6895 from Shin-Etsu Chemical.

[0135] Furthermore, the resin composition also includes a thermoplastic elastomer.

[0136] Preferably, in this embodiment, the thermoplastic elastomer is 1 to 60 parts by weight relative to 100 parts by weight of the total resin. Here, "resin" refers to a benzoxazine resin containing unsaturated bonds, a maleimide resin, or a benzoxazine resin without unsaturated bonds. If the resin composition includes a benzoxazine resin containing unsaturated bonds and a maleimide resin, then 100 parts by weight of the total resin refers to 100 parts by weight of the benzoxazine resin containing unsaturated bonds and the maleimide resin. If the resin composition includes a benzoxazine resin containing unsaturated bonds, a maleimide resin, and a benzoxazine resin without unsaturated bonds, then 100 parts by weight of the total resin refers to 100 parts by weight of the benzoxazine resin containing unsaturated bonds, the maleimide resin, and the benzoxazine resin without unsaturated bonds. This principle applies throughout.

[0137] More preferably, the thermoplastic elastomer is 5 to 30 parts by weight relative to 100 parts by weight of the total resin.

[0138] Optionally, the thermoplastic elastomer is at least one of styrene-based thermoplastic elastomers, polybutadiene-based thermoplastic elastomers, silicone-based thermoplastic elastomers, methacrylate-based thermoplastic elastomers, or butyl methacrylate-based thermoplastic elastomers.

[0139] Optionally, the styrene-based thermoplastic elastomer is selected from H1041, H1043, H1051, H1052, H1053, H1221, P1500, P2000, M1911 or M1913 of Asahi Kasei Corporation of Japan, 8004, 8006, 8076, 8104, V9827, 2002, 2005, 2006, 2007, 2104, 7125, 4033, 4044, 4055, 4077 or 4099 of Kuraray Corporation of the United States, and D1116A, D1118E, D1152E, D1170B, D1157A, D1171P, D1184A, A1535 or A1536 of Kraton Corporation of the United States.

[0140] Optionally, the organosilicon thermoplastic elastomer is selected from Shin-Etsu Chemical's X-40-2670, R-170S, X-40-2705, X-40-2701, KMP-600, KMP-605 or X-52-7030, or DOW's AY-42-119, EP-2600, EP-2601, EP-2720, TMS-2670, EXL-2315 or EXL-2655.

[0141] Optionally, the methacrylate thermoplastic elastomer is selected from Akema's M51, M52, M22 or D51N, Kuraray's LA-2330, and Nagase's SG-P3 series or SG-80 series.

[0142] Furthermore, the resin composition also includes a flame retardant.

[0143] Preferably, in this embodiment, the flame retardant is 1 to 50 parts by weight relative to 100 parts by weight of the total resin.

[0144] Optionally, the flame retardant is at least one of the following: brominated flame retardants, phosphorus-based flame retardants, nitrogen-based flame retardants, organosilicon flame retardants, organometallic flame retardants, and inorganic flame retardants.

[0145] Optionally, the brominated flame retardant is selected from decabromodiphenyl ether, decabromodiphenyl ethane, styrene bromide, or tetrabromophthalamide.

[0146] Optionally, 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) Phosphazene or modified phosphazene.

[0147] More preferably, the modified phosphorus is phosphorus containing unsaturated double bonds.

[0148] Optionally, the nitrogen-based flame retardant is selected from triazine compounds, cyanuric acid compounds, isocyanate compounds, and phenothiazine compounds.

[0149] Optionally, the organosilicon flame retardant is selected from organosilicon oil, organosilicon rubber, and organosilicon resin.

[0150] Optionally, the organometallic flame retardant is selected from ferrocene, acetylacetone metal complexes, and organometallic carbonyl compounds.

[0151] As an alternative, the inorganic flame retardant is selected from aluminum hydroxide, magnesium hydroxide, aluminum oxide, and barium oxide.

[0152] Furthermore, the resin composition also includes a catalyst.

[0153] Preferably, in this embodiment, the catalyst is 0.001 to 5 parts by weight relative to 100 parts by weight of the total resin.

[0154] Optionally, the catalyst is at least one of imidazole catalysts, pyridine catalysts, and organometallic salt catalysts.

[0155] Optionally, the catalyst is at least one selected from 4-dimethylaminopyridine, 2-methylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, modified imidazole, and zinc octanoate.

[0156] Optionally, the modified imidazole is one or a mixture of at least two of the following structures:

[0157]

[0158] Among them, R3, R4, R5 and R6 may be the same or different, and each is independently selected from methyl, ethyl or tert-butyl; A is methylene, ethylene, ... -S-、 Or aromatic hydrocarbon group; B is methylene, ethylene, -S- or

[0159] Specifically, the modified imidazole of structural formula (26) can be the modified imidazole of Daiichi Kogyo Co., Ltd. with the brand name G8009L; the modified imidazole of structural formula (27) can be the modified imidazole of JER Corporation with the brand name P200F50.

[0160] Furthermore, the resin composition also includes fillers.

[0161] Preferably, in this embodiment, the filler is 20 to 200 parts by weight relative to 100 parts by weight of the total resin.

[0162] Optionally, the packing material is at least one of inorganic packing material, organic packing material, and composite packing material.

[0163] More preferably, the filler is selected from spherical silica, alumina, or aluminum hydroxide, and more preferably from spherical silica.

[0164] Furthermore, the filler is surface-treated with a silane coupling agent, wherein the silane coupling agent is at least one of an aminosilane coupling agent, a carbon-carbon double bond silane coupling agent, or an epoxysilane coupling agent.

[0165] Optionally, the silane coupling agent is selected from the following structures:

[0166]

[0167] 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.

[0168] 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.

[0169] 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.

[0170] Optionally, the reinforcing material is selected from at least one of natural fibers, organic synthetic fibers, organic fabrics, and inorganic fabrics.

[0171] 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.

[0172] 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.

[0173] 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.

[0174] 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.

[0175] 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.

[0176] 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.

[0177] The present invention also provides an insulating board comprising the aforementioned resin composition.

[0178] The present invention also provides an insulating film comprising a carrier film and the aforementioned resin composition coated thereon.

[0179] 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.

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

[0182] The present invention also provides a circuit board comprising at least one of the aforementioned prepreg, laminate, insulating board, and insulating film.

[0183] The present invention also provides an electronic device, including the aforementioned circuit board.

[0184] Second Implementation Method

[0185] The difference between this second embodiment and the first embodiment is that:

[0186] This embodiment provides a resin composition comprising a prepolymer, said prepolymer being prepared by the following method:

[0187] Step (1) involves reacting maleimide resin with benzoxazine resin containing double bonds to obtain an intermediate product;

[0188] Step (2): Add a benzoxazine resin containing a triple bond to the intermediate product and react to obtain the prepolymer.

[0189] Furthermore, the reaction conditions in the preparation method of the prepolymer are: a reaction temperature of 60–170°C and a reaction time of 10–120 min.

[0190] Furthermore, the reaction temperature of step (1) is 80-130°C, and the reaction temperature of step (2) is 60-100°C.

[0191] In embodiments of this implementation that include a thermoplastic elastomer, the thermoplastic elastomer is 1 to 60 parts by weight relative to 100 parts by weight of the prepolymer.

[0192] In embodiments that include flame retardants, the flame retardant is 1 to 50 parts by weight relative to 100 parts by weight of the prepolymer.

[0193] In embodiments that include a catalyst, the catalyst is 0.001 to 5 parts by weight relative to 100 parts by weight of the prepolymer.

[0194] In embodiments that include fillers, the filler is 20 to 200 parts by weight relative to 100 parts by weight of the prepolymer.

[0195] As a further improvement to this embodiment, the resin composition further includes maleimide resin and benzoxazine resin containing unsaturated bonds, wherein the benzoxazine resin containing unsaturated bonds is a mixture of benzoxazine resin containing double bonds and benzoxazine resin containing triple bonds.

[0196] In further optimized embodiments of this invention, the resin is used in the following examples: in examples including thermoplastic elastomers, the content of the thermoplastic elastomer is 1 to 60 parts by weight relative to 100 parts by weight of the resin and the prepolymer; in examples including flame retardants, the content of the flame retardant is 1 to 50 parts by weight relative to 100 parts by weight of the resin and the prepolymer; in examples including catalysts, the content of the catalyst is 0.001 to 5 parts by weight relative to 100 parts by weight of the resin and the prepolymer; and in examples including fillers, the content of the filler is 20 to 200 parts by weight relative to 100 parts by weight of the resin and the prepolymer.

[0197] The second embodiment is identical to the first embodiment except for the differences mentioned above, and will not be repeated here.

[0198] The technical solution of this application will be further described below with reference to some specific preparation examples, embodiments, and comparative examples. Of course, these embodiments are only a part of the many variations contained in the implementation of the present invention, and not all of them.

[0199] Preparation Example 1

[0200] This preparation example discloses a method for preparing a prepolymer, including the following steps:

[0201] Step (1): Add 75g of maleimide resin (Yamato Kasei BMI-2300), 40g of benzoxazine resin (Dongcai, DFE148) with double bonds in the side chain, and 80g of acetone to the reaction flask and stir until uniform. Heat to 100°C and react for 40 minutes to obtain the intermediate product.

[0202] Step (2): Add 10g of benzoxazine resin with triple bond structure (1) to the intermediate product, control the reaction temperature to 80℃ and react for 20min to obtain prepolymer A.

[0203] Preparation Example 2

[0204] This preparation example discloses a method for preparing a prepolymer, including the following steps:

[0205] Step (1): Add 70g of maleimide resin (Yamato Kasei BMI-2300), 35g of benzoxazine resin (Tokyo Denki, DFE156) with double bonds at the end, and 70g of acetone to the reaction flask and stir until uniform. Heat to 100°C and react for 40 minutes to obtain the intermediate product.

[0206] Step (2): Add 15g of benzoxazine resin with triple bond structure (1) to the intermediate product, control the reaction temperature to 80℃ and react for 20min to obtain prepolymer B.

[0207] Comparative Preparation Example 1

[0208] This preparation example discloses a method for preparing a prepolymer, including the following steps:

[0209] Add 70g of maleimide resin (Yamato Kasei BMI-2300), 35g of benzoxazine resin (Tosai-made, DFE156) with double bonds at the end, and 70g of acetone to the reaction flask and stir until homogeneous. Heat to 100°C and react for 50 minutes to obtain prepolymer C.

[0210] Comparative Preparation Example 2

[0211] This preparation example discloses a method for preparing a prepolymer, including the following steps:

[0212] Add 70g of maleimide resin (Yamato Kasei BMI-2300), 20g of benzoxazine resin with triple bond structure (1) and 70g of acetone to a reaction flask, stir and mix evenly, heat to 80℃ and react for 40min to obtain prepolymer D.

[0213] Example 1

[0214] This embodiment discloses a resin composition, which is composed of the following raw materials: 30g of benzoxazine resin containing double bonds, 8g of benzoxazine resin containing triple bonds, 62g of maleimide resin, 15g of thermoplastic elastomer, 9g of flame retardant, 0.1g of catalyst, and 120g of filler.

[0215] Among them, the benzoxazine resin containing double bonds is DFE148 manufactured by Tosai, the benzoxazine resin containing triple bonds is structural formula (1), the maleimide resin is BMI-2300 manufactured by Yamato Chemical, the thermoplastic elastomer is H1052 manufactured by Asahi Chemical, the flame retardant is SPV-100 manufactured by Otsuka Chemical, the catalyst is 2-ethyl-4-methylimidazolium manufactured by Shikoku Chemical, and the filler is spherical silica manufactured by Kingi.

[0216] This embodiment also discloses 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.

[0217] The prepreg is prepared by the following method:

[0218] The above resin composition was diluted with N,N-dimethylacetamide to form a liquid with a solid content of 60 wt%.

[0219] 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.

[0220] This embodiment also discloses a laminate prepared by the following method:

[0221] The prepreg was cut to 300×300mm. Then, an electrolytic copper foil with a thickness of 18μm 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 4 hours under a pressure of 1.5MPa and a temperature of 200℃ to obtain a copper-clad laminate with a thickness of 1mm.

[0222] This embodiment also discloses an insulating board, including a prepreg sheet as described above, which is prepared using conventional preparation methods of the prior art, and will not be described in detail here.

[0223] This embodiment also discloses a circuit board, including the above-mentioned prepreg, which is prepared by conventional preparation methods of the prior art, and will not be described in detail here.

[0224] Example 2

[0225] This embodiment is basically the same as Embodiment 1, except that:

[0226] In the raw materials of the resin composition, the double-bonded benzoxazine resin is DFE156 manufactured by Dongcai, the triple-bonded benzoxazine resin is 10g, the maleimide resin is BMI-3000 manufactured by Molecular Design Company, and the flame retardant is 15g of decabromodiphenyl ethane.

[0227] Example 3

[0228] This embodiment is basically the same as Embodiment 1, except that:

[0229] The amount of benzoxazine resin containing double bonds in the raw materials of the resin composition is 25g, and it also includes 5g of benzoxazine resin without unsaturated bonds. The benzoxazine resin without unsaturated bonds is DFE127A manufactured by Dongcai.

[0230] Example 4

[0231] This embodiment is basically the same as Embodiment 1, except that the composition of the raw materials of the resin composition is different.

[0232] Specifically, it consists of: 100g of prepolymer A, 15g of thermoplastic elastomer, 15g of flame retardant, 0.1g of catalyst, and 120g of filler.

[0233] The thermoplastic elastomer is H1052 manufactured by Asahi Kasei, the flame retardant is decabromodiphenyl ethane, the catalyst is 2-ethyl-4-methylimidazolium manufactured by Shikoku Kasei, and the filler is spherical silica manufactured by Kingi.

[0234] Example 5

[0235] This embodiment is basically the same as embodiment 4, except that prepolymer B is used instead of prepolymer A.

[0236] Example 6

[0237] This embodiment is basically the same as Embodiment 1, except that the composition of the raw materials of the resin composition is different.

[0238] Specifically, the composition is as follows: 10g of benzoxazine resin containing double bonds, 5g of benzoxazine resin containing triple bonds, 25g of maleimide resin, 60g of prepolymer A, 15g of thermoplastic elastomer, 9g of flame retardant, 0.1g of catalyst, and 120g of filler.

[0239] The maleimide resin used is BMI-3000 manufactured by Molecular Design Company.

[0240] Comparative Example 1

[0241] The main difference between this comparative example and Example 1 is that the composition of the raw materials for the resin composition is different.

[0242] Specifically, the composition is: 38g of benzoxazine resin without unsaturated bonds, 62g of maleimide resin, 15g of thermoplastic elastomer, 9g of flame retardant, 0.1g of catalyst, and 120g of filler.

[0243] Among them, the benzoxazine resin without unsaturated bonds is DFE127A manufactured by Dongcai.

[0244] Comparative Example 2

[0245] This comparative example is basically the same as Example 4, except that prepolymer C is used instead of prepolymer A.

[0246] Comparative Example 3

[0247] This comparative example is basically the same as Example 4, except that prepolymer D is used instead of prepolymer A.

[0248] Comparative Example 4

[0249] The main difference between this comparative example and Example 1 is that the composition of the raw materials for the resin composition is different.

[0250] Specifically, the composition is: 40g of benzoxazine resin containing double bonds, 60g of maleimide resin, 15g of thermoplastic elastomer, 15g of flame retardant, 0.1g of catalyst, and 120g of filler.

[0251] Among them, the benzoxazine resin containing double bonds is DFE156 manufactured by Dongcai, the maleimide resin is BMI-3000 manufactured by Molecular Design Company, and the flame retardant is decabromodiphenyl ethane.

[0252] Comparative Example 5

[0253] The main difference between this comparative example and Example 1 is that the composition of the raw materials for the resin composition is different.

[0254] Specifically, the composition is: 38g of benzoxazine resin containing triple bonds, 62g of maleimide resin, 15g of thermoplastic elastomer, 9g of flame retardant, 0.1g of catalyst, and 120g of filler.

[0255] The copper-clad laminates obtained in Examples 1-6 and Comparative Examples 1-5 were subjected to performance testing, and the test results are shown in Table 1. The performance testing methods included:

[0256] (1) Glass transition temperature (Tg): The test was performed using the DMA (thermomechanical analysis) method according to the method specified in IPC-TM-6502.4.25, with a heating rate of 10℃ / min.

[0257] (2) Water absorption rate: The water absorption rate was determined according to the method of IPC-TM-6502.6.2.1. Specifically, three samples with a length × width of 10cm × 10cm and a thickness of 0.4mm were taken and the electrolytic copper foil was removed from both sides. They were dried at 100℃ for 2 hours, weighed, and the weight was recorded as W1. Then, they were treated in a pressure cooker at 121℃ and 2 atmospheres for 2 hours, weighed, and the weight was recorded as W2. The water absorption rate was determined to be (W2-W1) / W1×100%.

[0258] (3) 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 10℃ / min and the test temperature range was 30~100℃.

[0259] (4) Dk (10 GHz): Measured according to the IPC-TM-650 method.

[0260] (5) Df(10GHz): Measured according to the IPC-TM-650 method.

[0261] (6) Curing shrinkage rate: The TMA method was used to determine the shrinkage rate of the cured material before and after the temperature cycled from room temperature to 260℃ and back to room temperature.

[0262] Table 1

[0263]

[0264] Among them, in the appearance of the semi-cured sheet, no defects are indicated as О, slight resin deficiency is indicated as Δ, and large area of ​​dried flower defects are indicated as ※.

[0265] Referring to Table 1, compared to the comparative example, the copper-clad laminate prepared from the resin composition of the present invention not only has excellent appearance quality, but also high heat resistance, high modulus, low water absorption, low coefficient of thermal expansion, and low curing shrinkage.

[0266] 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.

[0267] 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 resin composition, characterized in that, By solid weight, including: Benzoxazine resin containing unsaturated bonds: 10~70 parts; Maleimide resin: 20~100 parts; The benzoxazine resin containing unsaturated bonds is a mixture of benzoxazine resin containing double bonds and benzoxazine resin containing triple bonds; The benzoxazine resin containing triple bonds is one or a mixture of at least two of the following structures: , structural formula (1); , structural formula (2); , structural formula (3); , structural formula (4); , structural formula (5); , structural formula (6); , structural formula (7); The benzoxazine resin containing double bonds is one or a mixture of at least two of the following structures: , structure (8); , structural formula (9); , structural formula (10); , structural formula (11); Where R is , , , , , , , , Or there may be no connecting bond; R0, R1, and R2 may be the same or different, each independently selected from hydrogen, alkyl, or olefinic groups, and at least one of R0, R1, and R2 contains an unsaturated group; R4 is , , , , , , , , Or there is no connection key.

2. The resin composition according to claim 1, characterized in that, It also includes benzoxazine resins without unsaturated bonds.

3. The resin composition according to claim 1, characterized in that, The benzoxazine resin containing unsaturated bonds contains 1-70 wt% benzoxazine resin containing triple bonds and 30-99 wt% benzoxazine resin containing double bonds.

4. The use of a resin composition as described in any one of claims 1 to 3 in prepreg, laminate, insulating board, insulating film, circuit board and electronic device.

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