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, 20-100 parts of a modified maleimide prepolymer, 10-80 parts of an epoxy resin, 5-60 parts of an active ester and 5-50 parts of an elastomer; the reactants of the modified maleimide prepolymer comprise an amine compound, an allyl compound and a maleimide resin; and the mass percentage of components with a number average molecular weight less than 1000 in the modified maleimide prepolymer is 10-40%. The application modifies the maleimide resin by using the amine compound and the allyl compound together, and is matched with the active ester compound and the epoxy resin, and the content of the low-molecular-weight components in the modified maleimide prepolymer is controlled, so that the compatibility among the maleimide resin, the active ester and the epoxy resin is improved, the heat resistance of the resin cured product is improved, the dielectric property and the water absorption of the resin cured product are reduced.

Description

Technical Field

[0001] The present application belongs to the technical field of electronic materials, and relates to a resin composition and the application of the resin composition in prepregs, laminates, insulating boards, insulating films, circuit substrates and electronic devices. Background Art

[0002] With the development and scale-up of 5G, PCB substrate materials need to have a lower dielectric constant and dielectric loss tangent to reduce signal delay, distortion and loss during high-speed transmission, as well as interference between signals.

[0003] Maleimide resins have excellent heat resistance, high modulus, and low CTE, and are therefore widely used in high-performance printed circuit boards. Active ester resins, as curing agents, do not produce secondary hydroxyl groups during the curing process with epoxy resins. Furthermore, due to their low polarity, the cured product has a low dielectric constant and dielectric loss tangent.

[0004] However, active esters and maleimide resins have poor compatibility, making co-curing difficult. When the two are blended, one of the components may precipitate and agglomerate or form a turbid resin solution, and a homogeneous resin solution cannot be formed. Moreover, after curing, the glass transition temperature of the mixture containing the two will show two peaks or multiple peaks, resulting in poor heat resistance of the final circuit substrate. Summary of the Invention

[0005] The present application provides a resin composition and a prepreg, a laminate, an insulating board, an insulating film, a circuit substrate and an electronic device made using the resin composition.

[0006] To achieve the above application objectives, one embodiment of the present application provides a resin composition, calculated on a solid weight basis, comprising:

[0007] 20-100 parts of modified maleimide prepolymer;

[0008] 10-80 parts of epoxy resin;

[0009] 5-60 parts of active ester;

[0010] 5-50 parts of elastomer;

[0011] The reactants of the modified maleimide prepolymer include an amine compound, an allyl compound and a maleimide resin; and in the modified bismaleimide prepolymer, the mass proportion of the component with a number average molecular weight less than 1000 is 10% to 40%.

[0012] By modifying the maleimide resin with an amine compound and an allyl compound, and adding an active ester compound and an epoxy resin, and controlling the content of the low molecular weight component in the modified maleimide prepolymer, not only the compatibility among the maleimide resin, the active ester and the epoxy resin is improved, but also the heat resistance of the resin cured product is improved, and the dielectric properties and water absorption rate are reduced.

[0013] In the modified bismaleimide prepolymer, when the mass proportion of the component with a number average molecular weight of less than 1000 is greater than 40%, phase separation will occur, that is, the bismaleimide resin will separate from the epoxy resin and other resins, resulting in low cross-linking density and easy precipitation, thereby leading to problems such as poor heat resistance and moisture-heat resistance of the resin composition; when the mass proportion of the component with a number average molecular weight of less than 1000 is less than 10%, there is a phenomenon of poor wettability between the resin and the glass fiber cloth, which leads to a decrease in the adhesion between the substrate and the copper foil, and the heat resistance of the electric furnace base plate will also be reduced.

[0014] Preferably, in the modified bismaleimide prepolymer, the mass proportion of the component with a number average molecular weight <1000 is 10%, 15%, 20%, 25%, 30%, 35% or 40%.

[0015] Preferably, in the modified bismaleimide prepolymer, the component with a number average molecular weight less than 1000 is at least one of an amine-modified maleimide resin, an allyl-modified maleimide resin, and an allyl-amine-modified maleimide resin.

[0016] Preferably, the reactants of the modified maleimide prepolymer include, by solid weight, 1 to 50 parts of the amine compound; 5 to 60 parts of the allyl compound; and 100 parts of the maleimide resin.

[0017] More preferably, the reactants of the modified maleimide prepolymer include, by solid weight, 30 to 50 parts of the amine compound; 5 to 30 parts of the allyl compound; and 100 parts of the maleimide resin.

[0018] Preferably, the preparation method of the modified maleimide prepolymer includes: dissolving and dispersing the amine compound, the allyl compound and the maleimide resin in an organic solvent, heating to 60°C to 150°C under nitrogen protection and keeping stirring, and reacting for 0.5 to 5 hours to obtain the modified bismaleimide prepolymer.

[0019] As a further improvement of one embodiment of the present application, the reactants of the modified maleimide prepolymer further include 0.5 to 10 parts by weight of an aminophenol compound, based on solid weight. This can control the overall reaction rate of the prepolymerization reaction, improve processability, and enhance the overall properties of the cured product.

[0020] Preferably, the aminophenol compound is a p-aminophenol compound, a m-aminophenol compound or an o-aminophenol compound.

[0021] As an optional scheme, the amine compound is selected from at least one of unsubstituted phenylenediamine, methylphenylenediamine, dimethylphenylenediamine, trimethylphenylenediamine, tetramethylphenylenediamine, xylene diamine, diaminopyridine, diaminodiphenylmethane, substituted diaminodiphenylmethane, bis[4-(4-aminophenoxy)phenyl]propane, bis[4-(4-aminophenoxy)phenyl]hexafluoropropane, diaminobenzophenone, diaminodiphenyl ether, diaminodiphenyl sulfone, diaminobiphenyl, diaminodiphenyl sulfide, diaminobinaphthyl, diaminodiphenylfluorene, diaminoanthraquinone, and amino-terminated silicone oil.

[0022] Preferably, the amine compound is selected from at least one of diaminodiphenyl ether, diaminodiphenyl sulfone, diaminodiphenylmethane, and amino-terminated silicone oil.

[0023] As an optional solution, the allyl compound is selected from at least one of diallyl bisphenol A, diallyl bisphenol F, diallyl bisphenol S, allyl phenol oxide resin, allyl phenol formaldehyde resin, and diallyl diphenyl ether.

[0024] Preferably, the allyl compound is diallyl bisphenol A.

[0025] As an optional solution, the maleimide resin is selected from at least one of the following structures:

[0026]

[0027] Me is methyl, Et is ethyl;

[0028] Me is a methyl group;

[0029] R1 is methylene or ethyl, R2 is hydrogen, methyl or ethyl, and n is an integer from 1 to 10;

[0030]

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

[0032] n is an integer from 1 to 10;

[0033] R is hydrogen, methyl or ethyl, and n is an integer from 1 to 10;

[0034] R is a methyl group, and n is an integer of 1 to 20.

[0035] Preferably, the active ester contains an unsaturated double bond. When the active ester contains an unsaturated double bond, a more homogeneous resin glue can be obtained, further improving the overall performance of the resin cured product.

[0036] As an optional solution, the active ester is at least one of the following structures:

[0037]

[0038] Wherein, Ar is an aromatic group; Ar1 ​​is an aromatic group and contains an unsaturated double bond substituent.

[0039] Preferably, the Ar group is a residue of a bisphenol structure, and Ar1 is a phenyl group or a naphthyl group containing an unsaturated double bond.

[0040] More preferably, the Ar group is a residue of bisphenol A, bisphenol F, bisphenol S, bisphenol E, dicyclopentadiene bisphenol, biphenyl bisphenol, or naphthyl bisphenol.

[0041] Preferably, the bisphenol structure contains allyl or vinyl groups.

[0042] When the active ester is an active ester compound containing a double bond, it has better compatibility with the modified bismaleimide resin containing a double bond.

[0043] As an optional scheme, the epoxy resin is selected from at least one of bisphenol A epoxy resin, bisphenol F epoxy resin, bisphenol S epoxy resin, bisphenol E epoxy resin, phosphorus-containing epoxy resin, o-cresol epoxy resin, bisphenol A novolac epoxy resin, phenol novolac epoxy resin, cresol novolac epoxy resin, triphenylmethane epoxy resin, tetraphenylethane epoxy resin, biphenyl epoxy resin, naphthalene ring epoxy resin, dicyclopentadiene epoxy resin, isocyanate epoxy resin, aralkyl linear novolac epoxy resin, alicyclic epoxy resin, glycidyl amine epoxy resin, glycidyl ether epoxy resin, and glycidyl ester epoxy resin.

[0044] Preferably, the elastomer is at least one of styrene elastomer, acrylic elastomer, methacrylate elastomer, silicone elastomer, nitrile elastomer, and core-shell rubber elastomer.

[0045] Preferably, the styrene-based elastomer is a hydrogenated or partially hydrogenated styrene-butadiene copolymer.

[0046] As an optional solution, the styrene-based elastomer is at least one of a hydrogenated or partially hydrogenated styrene-butadiene diblock copolymer and a hydrogenated or partially hydrogenated styrene-butadiene triblock copolymer.

[0047] As an optional solution, the acrylic elastomer and the methacrylate elastomer each independently contain at least one of the following structures:

[0048] Wherein, R1 is a C1-C5 alkyl group, and x is an integer from 1 to 100;

[0049] Wherein, R2 is a C1-C5 alkyl group, and y is an integer from 1 to 100;

[0050] Wherein, R3 is hydrogen or methyl, and o is an integer from 1 to 100.

[0051] More preferably, R1 is methyl, and R2 is methyl, ethyl or butyl.

[0052] As an optional solution, the silicone elastomer comprises at least one of the following structures:

[0053]

[0054]

[0055] Wherein, R is a C1-C12 hydrocarbon group or a C1-C12 alkoxy group; X is a mercapto group, an epoxy group, a hydroxyl group, a methoxy group or an amino group.

[0056] Preferably, R is methyl or phenyl.

[0057] Preferably, X is a mercapto group or an epoxy group.

[0058] As a further improvement of one embodiment of the present application, the resin composition further includes 30 to 200 parts of an inorganic filler, calculated on a solid weight basis.

[0059] As an optional solution, the inorganic filler is selected from at least one of non-metallic oxides, metal nitrides, non-metallic nitrides, inorganic hydrates, inorganic salts, metal hydrates or inorganic phosphorus.

[0060] Preferably, the inorganic filler is selected from at least one of fused silica, crystalline silica, spherical silica, hollow silica, aluminum hydroxide, aluminum oxide, talc, aluminum nitride, boron nitride, silicon carbide, barium sulfate, barium titanate, strontium titanate, calcium carbonate, calcium silicate, mica, and glass fiber powder.

[0061] More preferably, the inorganic filler is at least one of fused silica, crystalline silica, spherical silica, and hollow silica; more preferably, it is surface-treated spherical silica.

[0062] As a further improvement of one embodiment of the present application, the inorganic filler is surface-treated with a silane coupling agent, and the silane coupling agent is an epoxy-containing silane coupling agent, an amino-containing silane coupling agent, a vinyl-containing silane coupling agent, an acrylate-containing silane coupling agent, or an allyl-containing silane coupling agent.

[0063] Preferably, the median particle size of the inorganic filler is 1 to 15 microns, more preferably 1 to 10 microns.

[0064] As a further improvement of one embodiment of the present application, the resin composition further comprises 0.01 to 8 parts of a catalyst based on solid weight.

[0065] As an optional solution, the catalyst is selected from at least one of imidazole catalysts, pyridine catalysts, organophosphorus catalysts, and metal salt catalysts.

[0066] As an optional solution, the imidazole catalyst is selected from at least one of 4-dimethylaminopyridine, 2-methylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, modified imidazole, and zinc octoate.

[0067] As a further improvement of one embodiment of the present application, the resin composition further comprises 5 to 60 parts by solid weight of a flame retardant.

[0068] As an optional solution, the flame retardant is at least one of a brominated flame retardant, a phosphorus flame retardant, a nitrogen flame retardant, an organosilicon flame retardant, and an organometallic flame retardant.

[0069] As an optional solution, the brominated flame retardant is selected from decabromodiphenyl ether, decabromodiphenyl ethane, brominated styrene or tetrabromophthalamide.

[0070] As an optional solution, the phosphorus flame retardant is selected from inorganic phosphorus, condensed phosphate compounds, phosphoric acid compounds, hypophosphorous acid compounds, phosphorus oxide compounds, 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, 10-(2,5-dihydroxyphenyl)-9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, 10-phenyl-9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, tris(2,6-dimethylphenyl)phosphine, (m is an integer from 1 to 5), Phosphazene or modified phosphazene;

[0071] Among them, the DOPO group is

[0072] Preferably, the phosphorus-based flame retardant is selected from condensed phosphate compounds, hypophosphorous acid compounds, and bis-DOPO compounds.

[0073] The present application also provides applications of the resin composition in prepregs, laminates, insulating boards, insulating films, circuit substrates, and electronic devices.

[0074] Due to the application of the above technical solution, this application has the following advantages compared with the prior art:

[0075] By modifying the maleimide resin with an amine compound and an allyl compound, and adding an active ester compound and an epoxy resin, and controlling the content of the low molecular weight component in the modified maleimide prepolymer, not only the compatibility among the maleimide resin, the active ester and the epoxy resin is improved, but also the heat resistance of the resin cured product is improved, and the dielectric properties and water absorption rate are reduced. DETAILED DESCRIPTION

[0076] The technical solution of the present application will be further introduced below in conjunction with specific implementation methods. The following embodiments are merely descriptive and not restrictive, and should not be used to limit the scope of protection of the present application.

[0077] One embodiment of the present application provides a resin composition and use of the resin composition in a prepreg, a laminate, an insulating board, an insulating film, a circuit substrate, and an electronic device.

[0078] This embodiment provides a resin composition, calculated on a solid weight basis, comprising:

[0079] 20-100 parts of modified maleimide prepolymer;

[0080] 10-80 parts of epoxy resin;

[0081] 5-60 parts of active ester;

[0082] 5-50 parts of elastomer;

[0083] The reactants of the modified maleimide prepolymer include an amine compound, an allyl compound and a maleimide resin; and in the modified bismaleimide prepolymer, the mass proportion of the component with a number average molecular weight less than 1000 is 10% to 40%.

[0084] Preferably, in the modified bismaleimide prepolymer, the mass proportion of the component with a number average molecular weight <1000 is 10%, 15%, 20%, 25%, 30%, 35% or 40%.

[0085] Preferably, in the modified bismaleimide prepolymer, the component with a number average molecular weight less than 1000 is at least one of an amine-modified maleimide resin, an allyl-modified maleimide resin, and an allyl-amine-modified maleimide resin.

[0086] Preferably, the reactants of the modified maleimide prepolymer include, by solid weight, 1 to 50 parts of the amine compound; 5 to 60 parts of the allyl compound; and 100 parts of the maleimide resin.

[0087] More preferably, the reactants of the modified maleimide prepolymer include, by solid weight, 30 to 50 parts of the amine compound; 5 to 30 parts of the allyl compound; and 100 parts of the maleimide resin.

[0088] Preferably, the preparation method of the modified maleimide prepolymer includes: dissolving and dispersing the amine compound, the allyl compound and the maleimide resin in an organic solvent, heating to 60°C to 150°C under nitrogen protection and keeping stirring, and reacting for 0.5 to 5 hours to obtain the modified bismaleimide prepolymer.

[0089] Preferably, in the preparation method of the modified maleimide prepolymer, the temperature is heated to 100° C. to 130° C. under nitrogen protection; and the reaction time is 1 h, 2 h, 3 h, 4 h or 5 h.

[0090] Optionally, the organic solvent is selected from at least one of acetone, butanone, methyl isobutyl ketone, ethylene glycol methyl ether, propylene glycol methyl ether, benzene, toluene, xylene, and cyclohexane.

[0091] Furthermore, the reactants of the modified maleimide prepolymer further include 0.5 to 10 parts of an aminophenol compound based on solid weight.

[0092] Preferably, the aminophenol compound is a p-aminophenol compound, a m-aminophenol compound or an o-aminophenol compound.

[0093] More preferably, the aminophenol compound is a p-aminophenol compound.

[0094] Optionally, the amine compound is selected from at least one of unsubstituted phenylenediamine, methylphenylenediamine, dimethylphenylenediamine, trimethylphenylenediamine, tetramethylphenylenediamine, xylene diamine, diaminopyridine, diaminodiphenylmethane, substituted diaminodiphenylmethane, bis[4-(4-aminophenoxy)phenyl]propane, bis[4-(4-aminophenoxy)phenyl]hexafluoropropane, diaminobenzophenone, diaminodiphenyl ether, diaminodiphenyl sulfone, diaminobiphenyl, diaminodiphenyl sulfide, diaminobinaphthyl, diaminodiphenylfluorene, diaminoanthraquinone, and amino-terminated silicone oil.

[0095] Preferably, the amine compound is selected from at least one of diaminodiphenyl ether, diaminodiphenyl sulfone, diaminodiphenylmethane, and amino-terminated silicone oil.

[0096] Optionally, the allyl compound is selected from at least one of diallyl bisphenol A, diallyl bisphenol F, diallyl bisphenol S, allyl phenol oxide resin, allyl phenol formaldehyde resin, and diallyl diphenyl ether.

[0097] Preferably, the allyl compound is diallyl bisphenol A.

[0098] Optionally, the maleimide resin is selected from at least one of the following structures:

[0099]

[0100] Me is methyl, Et is ethyl;

[0101] Me is a methyl group;

[0102] R1 is methylene or ethyl, R2 is hydrogen, methyl or ethyl, and n is an integer from 1 to 10;

[0103]

[0104] n is an integer from 1 to 10;

[0105] n is an integer from 1 to 10;

[0106] R is hydrogen, methyl or ethyl, and n is an integer from 1 to 10;

[0107] R is a methyl group, and n is an integer of 1 to 20.

[0108] The maleimide resin can be specifically selected from BMI-1000, BMI-2300, BMI-5100 or BMI-TMH manufactured by Yamato Chemical; BMI, BMI-70 or BMI-80 manufactured by KI Chemical; X9-470, X9-450 or X-9500 manufactured by DIC; MIR-3000 or MIR-5000 manufactured by Nippon Kayaku.

[0109] Preferably, the active ester contains an unsaturated double bond.

[0110] Optionally, the active ester is at least one of the following structures:

[0111]

[0112] Wherein, Ar is an aryl group, Ar1 is an aryl group and contains an unsaturated double bond substituent.

[0113] Preferably, the Ar group is a residue of a bisphenol structure, and Ar1 is a phenyl group or a naphthyl group containing an unsaturated double bond.

[0114] More preferably, the Ar group is a residue of bisphenol A, bisphenol F, bisphenol S, bisphenol E, dicyclopentadiene bisphenol, biphenyl bisphenol, or naphthyl bisphenol.

[0115] Preferably, the bisphenol structure contains allyl or vinyl groups.

[0116] Optionally, the epoxy resin is selected from at least one of bisphenol A epoxy resin, bisphenol F epoxy resin, bisphenol S epoxy resin, bisphenol E epoxy resin, phosphorus-containing epoxy resin, o-cresol epoxy resin, bisphenol A novolac epoxy resin, phenol novolac epoxy resin, cresol novolac epoxy resin, triphenylmethane epoxy resin, tetraphenylethane epoxy resin, biphenyl epoxy resin, naphthalene ring epoxy resin, dicyclopentadiene epoxy resin, isocyanate epoxy resin, aralkyl linear novolac epoxy resin, alicyclic epoxy resin, glycidyl amine epoxy resin, glycidyl ether epoxy resin, and glycidyl ester epoxy resin.

[0117] Preferably, the elastomer is at least one of styrene elastomer, acrylic elastomer, methacrylate elastomer, silicone elastomer, nitrile elastomer, and core-shell rubber elastomer.

[0118] Preferably, the styrene-based elastomer is a hydrogenated or partially hydrogenated styrene-butadiene copolymer.

[0119] Specifically, the styrene-based elastomer is at least one of a hydrogenated or partially hydrogenated styrene-butadiene diblock copolymer and a hydrogenated or partially hydrogenated styrene-butadiene triblock copolymer.

[0120] The styrene elastomer can be specifically selected from SEPTON™ 2000 series (including 2002, 2004, 2005, 2006, 2063, 2104), SEPTON™ 4000 series (including 4033, 4044, 4055, 4077), HYBRAR TM 7000 series (including 7125, 7311), SEPTON™ 8000 series (including 8004, 8006, 8007L, 8851), SEPTON™ V series (including 9461, 9475), SEPTON™ Q1250; or, the styrene elastomer is selected from H1041, H1043, H1051, H1052, H1053, H1221 manufactured by Asahi Chemical Industry Co., Ltd.

[0121] As an optional solution, the acrylic elastomer and the methacrylate elastomer each independently contain at least one of the following structures:

[0122] Wherein, R1 is a C1-C5 alkyl group, and x is an integer from 1 to 100;

[0123] Wherein, R2 is a C1-C5 alkyl group, and y is an integer from 1 to 100;

[0124] Wherein, R3 is hydrogen or methyl, and o is an integer from 1 to 100.

[0125] More preferably, R1 is methyl, and R2 is methyl, ethyl or butyl.

[0126] The acrylic elastomer can be specifically selected from M51, M52, M22 or D51N manufactured by Arkema, LA2250, LA2140, LA-2330 or LA4285 manufactured by Kuraray Co., Ltd., SG-P3, SG-80H, PMS-22-1, PMS-22-4, PMS-19-5 or PMS-22-5 manufactured by Nagase, Japan.

[0127] The methacrylate elastomer can be specifically selected from M51, M52, M22 or D51N manufactured by Arkema, LA2250, LA2140, LA-2330 or LA4285 manufactured by Kuraray Co., Ltd., SG-P3, SG-80H, PMS-22-1, PMS-22-4, PMS-19-5 or PMS-22-5 manufactured by Nagase, Japan.

[0128] As an optional solution, the silicone elastomer comprises at least one of the following structures:

[0129]

[0130] Wherein, R is a C1-C12 hydrocarbon group or a C1-C12 alkoxy group; X is a mercapto group, an epoxy group, a hydroxyl group, a methoxy group or an amino group.

[0131] Preferably, R is methyl or phenyl.

[0132] Preferably, X is a mercapto group or an epoxy group.

[0133] The silicone elastomer can be specifically selected from SQ-20P or KHE-8000H produced by Nippon Kayaku, SQ502-8 produced by Arakawa Chemical, AY42-119 produced by DuPont Toray, X-40-2670, R-170S, X-40-2705, X-40-2701, KMP-600, KMP-605 or X-52-7030 produced by Shin-Etsu Chemical Co., Ltd., EP-2600, EP-2601, EP-2720, TMS-2670, EXL-2315 or EXL-2655 produced by DOW.

[0134] Furthermore, the resin composition further comprises 30 to 200 parts of inorganic filler based on solid weight.

[0135] Optionally, the inorganic filler is selected from at least one of non-metallic oxides, metal nitrides, non-metallic nitrides, inorganic hydrates, inorganic salts, metal hydrates or inorganic phosphorus.

[0136] Preferably, the inorganic filler is selected from at least one of fused silica, crystalline silica, spherical silica, hollow silica, aluminum hydroxide, aluminum oxide, talc, aluminum nitride, boron nitride, silicon carbide, barium sulfate, barium titanate, strontium titanate, calcium carbonate, calcium silicate, mica, and glass fiber powder.

[0137] More preferably, the inorganic filler is at least one of fused silica, crystalline silica, spherical silica, and hollow silica; more preferably, it is surface-treated spherical silica.

[0138] Furthermore, the inorganic filler is surface treated with a silane coupling agent, and the silane coupling agent is an epoxy-containing silane coupling agent, an amino-containing silane coupling agent, a vinyl-containing silane coupling agent, an acrylate-containing silane coupling agent, or an allyl-containing silane coupling agent.

[0139] Preferably, the median particle size of the inorganic filler is 1 to 15 microns, more preferably 1 to 10 microns.

[0140] Specifically, the median particle size of the inorganic filler is preferably 1 micron, 2 microns, 5 microns, 8 microns, 10 microns, 11 microns, 12 microns, 13 microns, or 14 microns.

[0141] Furthermore, the resin composition further comprises 0.01 to 8 parts of a catalyst based on solid weight.

[0142] Optionally, the catalyst is selected from at least one of imidazole catalysts, pyridine catalysts, organophosphorus catalysts, and metal salt catalysts.

[0143] Optionally, the imidazole catalyst is selected from at least one of 4-dimethylaminopyridine, 2-methylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, modified imidazole, and zinc octoate.

[0144] Furthermore, the resin composition further comprises 5 to 60 parts by weight of a flame retardant.

[0145] Optionally, the flame retardant is at least one of a brominated flame retardant, a phosphorus flame retardant, a nitrogen flame retardant, an organosilicon flame retardant, and an organometallic flame retardant.

[0146] Optionally, the brominated flame retardant is selected from decabromodiphenyl ether, decabromodiphenyl ethane, brominated styrene or tetrabromophthalamide.

[0147] Optionally, the phosphorus flame retardant is selected from inorganic phosphorus, condensed phosphate compounds, phosphoric acid compounds, hypophosphorous acid compounds, phosphorus oxide compounds, 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, 10-(2,5-dihydroxyphenyl)-9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, 10-phenyl-9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, tris(2,6-dimethylphenyl)phosphine, (m is an integer from 1 to 5), Phosphazene or modified phosphazene;

[0148] Among them, the DOPO group is

[0149] Preferably, the phosphorus-based flame retardant is selected from condensed phosphate compounds, hypophosphorous acid compounds, and bis-DOPO compounds.

[0150] The present application also provides a prepreg, comprising a reinforcing material and the aforementioned resin composition; the resin composition is wrapped around the reinforcing material.

[0151] The preparation method of the semi-cured sheet is as follows: the resin composition is dissolved in a solvent to prepare a glue solution, the glue solution is then applied to the reinforcing material by an impregnation method, the impregnated reinforcing material is taken out and baked at a temperature of 100 to 180° C. for 1 to 15 minutes; and the semi-cured sheet is obtained after drying.

[0152] 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.

[0153] Optionally, the reinforcing material is selected from at least one of natural fibers, organic synthetic fibers, organic fabrics, and inorganic fabrics.

[0154] 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.

[0155] In addition, when the reinforcing material is glass fiber cloth, the glass fiber cloth is chemically treated with a coupling agent to improve the interfacial bonding between the resin composition and the glass fiber cloth. The coupling agent is preferably an epoxy silane coupling agent or an amino silane coupling agent to provide good water resistance and heat resistance.

[0156] The present application also provides a laminate comprising a piece of the aforementioned prepreg and a metal foil disposed on at least one surface of the prepreg; or comprising a composite sheet formed by overlapping a plurality of the aforementioned prepregs and a metal foil disposed on at least one surface of the composite sheet.

[0157] The laminate is prepared by coating one or both sides of a prepreg with metal foil, or by stacking at least two prepregs to form a composite sheet, coating one or both sides of the composite sheet with metal foil, and then hot pressing to form the metal foil laminate. The hot pressing conditions are: a pressure of 0.2 to 2 MPa, a temperature of 150 to 250°C, and a pressing time of 2 to 4 hours.

[0158] Preferably, the metal foil is selected from copper foil or aluminum foil, and has a thickness of 5 μm, 8 μm, 12 μm, 18 μm, 35 μm or 70 μm.

[0159] The present application also provides an insulating board comprising the aforementioned resin composition.

[0160] The present application also provides an insulating film, comprising a carrier film and the aforementioned resin composition coated thereon.

[0161] The insulating film is prepared by the following method: the resin composition is dissolved in a solvent to prepare a glue solution, the glue solution is then coated on a carrier film, and the carrier film coated with the glue solution is heated and dried to obtain the insulating film.

[0162] 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.

[0163] Optionally, the carrier film is selected from at least one of PET film, PP film, PE film and PVC film.

[0164] The present application also provides a circuit substrate, comprising at least one of the aforementioned prepreg, laminate, insulating plate, and insulating film.

[0165] The present application also provides an electronic device including the aforementioned circuit board.

[0166] The technical solutions of the present application will be further described below in combination with some specific preparation examples, examples and comparative examples. Of course, these examples are only a part of the numerous changed examples contained in the embodiments of the present application, but not all.

[0167] Preparation Example 1

[0168] A modified maleimide prepolymer A was prepared in this preparation example, and the specific steps are as follows:

[0169] In a reaction vessel equipped with a thermometer, a stirring device, a reflux condenser tube, and a volume of 1 L, 50.0 g of amino-terminated silicone oil (Shin-Etsu Chemical, X-22-161B), 110.0 g of diallyl bisphenol A, 200.0 g of maleimide resin (structural formula (1)), 180 g of N,N-dimethylformamide, and 180 g of propylene glycol monomethyl ether were added, and reacted at 120°C for 4 h to obtain a solution of modified maleimide prepolymer A. Using gel permeation chromatography (GPC), according to the calibration curve of standard polystyrene, it was measured that the mass fraction of components with a number average molecular weight <1000 was 15%.

[0170] Preparation Example 2

[0171] A modified maleimide prepolymer B was prepared in this preparation example, and the specific steps are as follows:

[0172] In a reaction vessel equipped with a thermometer, a stirring device, a reflux condenser tube, and a volume of 1 L, 50.0 g of 3,3'-diaminodiphenylmethane, 110.0 g of diallyl bisphenol S, 200.0 g of maleimide resin (structural formula (3)), 180 g of N,N-dimethylformamide, and 180 g of propylene glycol monomethyl ether were added, and reacted at 130°C for 3 h to obtain a solution of modified maleimide resin B. Using gel permeation chromatography (GPC), according to the calibration curve of standard polystyrene, it was measured that the mass fraction of components with a number average molecular weight <1000 was 35%.

[0173] Preparation Example 3

[0174] A modified maleimide prepolymer C was prepared in this preparation example, and the specific steps are as follows:

[0175] 50.0 g of 4,4'-diaminodiphenyl ether, 110.0 g of diallyl bisphenol A, 200.0 g of maleimide resin (structural formula (7)), 180 g of N,N-dimethylformamide, and 180 g of propylene glycol monomethyl ether were added to a 1 L reaction vessel equipped with a thermometer, a stirring device, and a reflux condenser. The mixture was reacted at 120°C for 4 h to obtain a solution of modified maleimide prepolymer C. Gel permeation chromatography (GPC) was used to convert the solution to a standard polystyrene calibration curve, and the mass proportion of the component with a number average molecular weight of less than 1000 was determined to be 15%.

[0176] Preparation Example 4

[0177] This preparation example prepared a modified maleimide prepolymer D, and the specific steps are as follows:

[0178] 50.0 g of diaminodiphenylmethane, 110.0 g of diallyl bisphenol A, 200.0 g of maleimide resin (structural formula (8)), 180 g of N,N-dimethylformamide, and 180 g of propylene glycol monomethyl ether were added to a 1 L reaction vessel equipped with a thermometer, a stirring device, and a reflux condenser. The mixture was reacted at 120° C. for 4 h to obtain a solution of modified maleimide prepolymer D. Gel permeation chromatography (GPC) was used to convert the solution to a standard polystyrene calibration curve, and the mass proportion of the component with a number average molecular weight of less than 1000 was determined to be 15%.

[0179] Comparative Preparation Example 5

[0180] This preparation example prepared a modified maleimide prepolymer E, and the specific steps are as follows:

[0181] 50.0 g of amino-terminated silicone oil (X-22-161B manufactured by Shin-Etsu Chemical), 110.0 g of diallyl bisphenol A, 200.0 g of maleimide resin (structural formula (1)), 180 g of N,N-dimethylformamide, and 180 g of propylene glycol monomethyl ether were added to a 1 L reaction vessel equipped with a thermometer, a stirring device, and a reflux condenser. The mixture was reacted at 120° C. for 2 h to obtain a solution of modified maleimide prepolymer E. Gel permeation chromatography (GPC) was used to convert the mass of the component with a number average molecular weight of less than 1000 to a value of 45% based on a calibration curve of standard polystyrene.

[0182] Example

[0183] The chemical components and contents of the resin compositions of Examples 1 to 4 and Comparative Examples 1 to 4 are shown in Table 1.

[0184]

[0185]

[0186] Among them, epoxy resin A is biphenyl-type epoxy resin A produced by Shengquan, epoxy resin B is naphthalene-type HP-6000 produced by DIC, active ester A is HP-8000 produced by DIC, active ester B is prepared by the method in patent WO2018235425, active ester C is 3480P01 produced by Kyoho, elastomer A is M51 produced by Akema, elastomer B is SGP3 produced by Nagano, the catalyst is 2-methylimidazole produced by Shikoku Chemical, and the inorganic filler is spherical silica produced by Lianrui, with a median particle size of 3 microns.

[0187] This embodiment also discloses a prepreg, comprising a glass fiber cloth as a reinforcing material and a resin composition coated on the glass fiber cloth by an impregnation method. The glass fiber cloth is a spread fiber cloth and is pretreated with an epoxy silane coupling agent.

[0188] Wherein, the prepreg is prepared by the following method:

[0189] The resin compositions of Examples 1 to 4 and Comparative Examples 1 to 4 were diluted with N, N-dimethylacetamide to form a glue solution with a solid content of 60 wt%;

[0190] The E glass fiber cloth used as the reinforcement material was pretreated with an epoxy silane coupling agent, immersed in the above-mentioned glue solution, taken out after being soaked, placed in a blast drying oven at 160° C., and baked for 3 to 6 minutes to obtain a prepreg.

[0191] This embodiment also discloses a laminate, which is prepared by the following method:

[0192] The above-mentioned prepreg was cut into 300×300mm, and then a 12μm thick electrolytic copper foil was placed on both sides of the prepreg, stacked into a certain stacking structure, placed in a vacuum hot press, and hot pressed for 4 hours at a pressure of 1.5MPa and a temperature of 200℃ to obtain a 1mm thick copper-clad laminate.

[0193] This embodiment further discloses an insulating board, comprising the above-mentioned prepreg, which is prepared by a conventional preparation method in the prior art, and will not be described in detail here.

[0194] This embodiment further discloses a circuit substrate, including the above-mentioned prepreg, which is prepared by a conventional preparation method in the prior art, and will not be described in detail here.

[0195] The copper clad laminates obtained in Examples 1-4 and Comparative Examples 1-4 were subjected to performance testing, and the test results are shown in Table 2. The performance testing method includes:

[0196] (1) Glass transition temperature (Tg): DMA (thermomechanical analysis) method was used to test in accordance with the method specified in IPC-TM-6502.4.25, with a heating rate of 10°C / min.

[0197] (2) Peel strength: Test the peel strength of the copper foil layer according to the "after thermal stress" experimental conditions in IPC-TM-650 2.4.8 method.

[0198] (3) Tin immersion heat resistance: A 50×50 mm double-sided copper-clad laminate was immersed in 288°C solder and the time for the sample to delaminate and form bubbles was recorded.

[0199] (4) Resistance to moist heat and tin immersion (PCT, 6H): PCT (Pressure Cooking Test) 2atm, cook at 121℃ for 6h, then immerse in solder at 288℃ for more than 30min, and record the time for the sample to delaminate and bubble.

[0200] (5) Water absorption after PCT 6H: After PCT cooking, the water absorption was calculated according to IPC-TM-6502.6.2.1. Specifically, three samples with a length × width of 10 cm × 10 cm and a thickness of 0.4 mm, with the electrolytic copper foil removed from both sides, were dried at 100°C for 2 hours and weighed. The weight was recorded as W1. The samples were then treated in a pressure cooker at 121°C and 2 atmospheres for 2 hours. The samples were weighed and recorded as W2. The water absorption was determined as (W2 - W1) / W1 × 100%.

[0201] (6) X / Y-axis thermal expansion coefficient (CTE): The TMA method was used to measure the CTE in accordance with IPC-TM-650, with a heating rate of 10°C / min and a test temperature range of 30 to 100°C.

[0202] Table 2

[0203]

[0204] Referring to Table 1, compared with the comparative example, the resin composition of the embodiment of the present application not only has excellent compatibility, but also the copper clad laminate prepared therefrom has high heat resistance, low CTE and low water absorption.

[0205] It should be understood that although this specification is described in terms of implementation methods, not every implementation method contains only one independent technical solution. This narrative method of the specification is only for the sake of clarity. Those skilled in the art should regard the specification as a whole. The technical solutions in each implementation method can also be appropriately combined to form other implementation methods that can be understood by those skilled in the art.

[0206] The detailed descriptions listed above are merely specific descriptions of feasible implementation methods of the present application. They are not intended to limit the scope of protection of the present application. Any equivalent implementation methods or changes that do not deviate from the technical spirit of the present application should be included in the scope of protection of the present application.

Claims

1. A resin composition, characterized in that By solid weight, comprising: 20-100 parts of modified maleimide prepolymer; 10-80 parts of epoxy resin; 5-60 parts of active ester; 5-50 parts of elastomer; The reactants of the modified maleimide prepolymer include, by solid weight, 1 to 50 parts of an amine compound, 5 to 60 parts of an allyl compound, and 100 parts of a maleimide resin; and in the modified bismaleimide prepolymer, the mass proportion of the component with a number average molecular weight less than 1000 is 10% to 40%; The amine compound is selected from at least one of unsubstituted phenylenediamine, methylphenylenediamine, dimethylphenylenediamine, trimethylphenylenediamine, tetramethylphenylenediamine, xylene diamine, diaminopyridine, diaminodiphenylmethane, substituted diaminodiphenylmethane, bis[4-(4-aminophenoxy)phenyl]propane, bis[4-(4-aminophenoxy)phenyl]hexafluoropropane, diaminobenzophenone, diaminodiphenyl ether, diaminodiphenyl sulfone, diaminobiphenyl, diaminodiphenyl sulfide, diaminobinaphthyl, diaminodiphenylfluorene, diaminoanthraquinone, and amino-terminated silicone oil; The allyl compound is selected from at least one of diallyl bisphenol A, diallyl bisphenol F, diallyl bisphenol S, allyl phenol oxide resin, allyl phenol formaldehyde resin and diallyl diphenyl ether.

2. The resin composition according to claim 1, wherein The reactants of the modified maleimide prepolymer further include 0.5 to 10 parts of an aminophenol compound based on solid weight.

3. The resin composition according to claim 1, wherein The active ester contains an unsaturated double bond.

4. The resin composition according to claim 1, wherein The elastomer is at least one of styrene elastomer, acrylic elastomer, methacrylate elastomer, silicone elastomer, nitrile elastomer, and core-shell rubber elastomer.

5. The resin composition according to claim 4, characterized in that The styrene-based elastomer is a hydrogenated or partially hydrogenated styrene-butadiene copolymer.

6. The resin composition according to claim 1, characterized in that The invention further comprises 30 to 200 parts of inorganic fillers based on solid weight.

7. Use of the resin composition according to any one of claims 1 to 6 in prepregs, laminates, insulating boards, insulating films, circuit boards and electronic devices.

Images