Resin composition and application of the resin composition

Abstract

The present invention discloses a resin composition and an application of the resin composition. The resin composition comprises, by weight, 10 to 80 parts by weight of a maleimide resin, 10 to 70 parts by weight of an epoxy resin, 5 to 50 parts by weight of a phenolic resin, an elastomer, 0.1 to 5 parts by weight of a nitrogen compound and a filler. The content of the filler is tl To meet 35 <W t When ≤45, p tl 45-50%; when 25≤W t When ≤35, p tl The epoxy resin contains at least one naphthalene ring, and / or the phenolic resin contains at least one naphthalene ring. Compared with the prior art, the present invention can make the resin composition have excellent compatibility, not only has a lower CTE value, but also is conducive to improving the peel strength of the copper foil.

Description

Technical Field

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

[0002] In recent years, electronic devices have been developing towards functional aggregation, miniaturization and even micro-miniaturization, and the wiring density in printed circuit boards has become increasingly dense, which has put higher and higher requirements on the comprehensive performance of copper-clad laminates, especially heat resistance and reliability. However, due to the characteristics of thermal expansion, copper-clad laminates are prone to warping when used in semiconductor packaging substrates.

[0003] In order to reduce the thermal expansion coefficient of the laminate, the industry usually uses low-modulus thermoplastic elastomers in copper-clad laminates to improve the flexibility of the cured product. However, the compatibility of thermoplastic resins in thermosetting resin compositions is poor, and the heat resistance of thermoplastic resins is not high enough. Therefore, the amount added to the resin composition is limited, and it is difficult to achieve the required comprehensive performance. Summary of the invention

[0004] In order to prepare a resin composition with excellent moisture and heat resistance and compatibility and a low thermal expansion coefficient, 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 prepared using the resin composition.

[0005] To achieve the above-mentioned object of the invention, one embodiment of the present invention provides a resin composition, which comprises, by weight:

[0006] Maleimide resin, its weight W m 10 to 80 parts by weight;

[0007] Epoxy resin, weight W h 10 to 70 parts by weight;

[0008] Phenolic resin, its weight W f 5 to 50 parts by weight;

[0009] The elastic body, whose weight is W t ;

[0010] Nitrogen compounds, whose weight W d 0.1 to 5 parts by weight;

[0011] Filler, its weight is W tl , its content p tl for Relative to 100 parts by weight of the total of maleimide resin, epoxy resin, phenolic resin and elastomer, when 35 <Wt When ≤45, p tl 45-50%; when 25≤W t When ≤35, p tl 55-65%;

[0012] The epoxy resin contains at least one naphthalene ring, and / or the phenolic resin contains at least one naphthalene ring.

[0013] By setting the type and content of each component in the resin composition and further limiting the content of the filler according to the different contents of the elastomer in the resin composition, the resin composition can have excellent compatibility, not only has a lower CTE value, but also is beneficial to improving the peel strength of the copper foil.

[0014] Preferably, relative to 100 parts by weight of the total of the maleimide resin, the epoxy resin, the phenolic resin and the elastomer, when 35 <W t When ≤40, p tl 45-50%; when 30≤W t When ≤35, p tl It is 55 to 65%.

[0015] Preferably, relative to 100 parts by weight of the total of the maleimide resin, epoxy resin, phenolic resin and elastomer, when 40 <W t When ≤45, p tl 45-50%; when 25≤W t <30, p tl It is 55 to 65%.

[0016] Preferably, relative to 100 parts by weight of the total of the maleimide resin, the epoxy resin, the phenolic resin and the elastomer, when 35 <W t When ≤45, p tl 45-47%; when 25≤W t When ≤35, p tl It is 60-65%.

[0017] Preferably, relative to 100 parts by weight of the total of the maleimide resin, the epoxy resin, the phenolic resin and the elastomer, when 35 <W t When ≤45, p tl 47-50%; when 25≤W t When ≤35, p tl It is 55 to 60%.

[0018] As a further improvement of one embodiment of the present invention, the maleimide resin is at least one of the following structures:

[0019] Structural formula (1);

[0020]

[0021] Wherein, R1 is methylene, ethylene or R2 is hydrogen, methyl or ethyl;

[0022]

[0023] Structural formula (6), wherein n is an integer from 1 to 10;

[0024] Structural formula (7), wherein n is an integer from 1 to 10;

[0025] Wherein, n is an integer from 1 to 10;

[0026] Structural formula (9), wherein n is an integer from 1 to 10;

[0027] Structural formula (10), wherein R is hydrogen, methyl or ethyl, and n is an integer from 1 to 10.

[0028] As a further improvement of one embodiment of the present invention, the epoxy resin includes a naphthalene-type epoxy resin, and the structure of the naphthalene-type epoxy resin is one or a mixture of at least two of the following structures:

[0029]

[0030]

[0031] Here, n is an integer from 1 to 10.

[0032] As an optional solution, the naphthalene-based epoxy resin is selected from HP-4032SS, HP-4770, EXA-4750, HP-4700, HP-4710, HP-6000, HP-9500, HP-9540, HP-9900 or EXA-7311 manufactured by DIC.

[0033] As a further improvement of one embodiment of the present invention, the epoxy resin also includes any one or more of bisphenol A epoxy resin, bisphenol F epoxy resin, phosphorus-containing epoxy resin, o-cresol epoxy resin, bisphenol A novolac epoxy resin, phenol novolac epoxy resin, trifunctional phenol-type epoxy resin, tetraphenylethane epoxy resin, biphenyl-type epoxy resin, dicyclopentadiene-type epoxy resin, isocyanate-type epoxy resin, aralkyl linear novolac epoxy resin, alicyclic epoxy resin, glycidylamine-type epoxy resin, and glycidylester-type epoxy resin.

[0034] As a further improvement of one embodiment of the present invention, the phenolic resin includes a naphthalene-type phenolic resin, and the naphthalene-type phenolic resin contains at least one of the following structures:

[0035]

[0036]

[0037] Here, n is an integer from 1 to 10.

[0038] As an optional solution, the phenolic resin is selected from EXB-9500 manufactured by DIC or SN495 manufactured by Nippon Steel Chemical.

[0039] As a further improvement of one embodiment of the present invention, the phenolic resin further includes bisphenol A phenolic resin, biphenyl phenolic resin, triazine-containing phenolic resin, bisphenol F phenolic resin or dicyclopentadiene phenolic resin.

[0040] As a further improvement of one embodiment of the present invention, the nitrogen compound contains at least one of epoxy group, mercapto group, amino group, hydroxyl group, acrylate group, methacrylate group, vinyl group, and allyl group.

[0041] As a further improvement of an embodiment of the present invention, the nitrogen compound is at least one of a modified triazine compound and a nitrogen-containing silane compound.

[0042] Preferably, the structural formula of the modified triazine compound is:

[0043]

[0044] Wherein, R1, R2, and R3 are the same or different and are independently selected from hydrogen, hydroxyl, amino, thiol, a group represented by structural formula (25), a group represented by structural formula (26), a group represented by structural formula (27) or a group represented by structural formula (28). Specifically, they are as follows:

[0045] Among them, R4 is C1-C6 alkylene, and R5 is C1-C5 alkyl.

[0046] -R6-OH, structural formula (26), wherein R6 is a C1-C5 alkylene group.

[0047] Among them, R7 is C1-C6 alkylene, and R8 is C1-C5 alkyl.

[0048] Among them, R9 and R 10 are the same or different, each independently selected from C1-C6 alkylene, R 11 It is a C1-C5 alkyl group.

[0049] More preferably, R1, R2, and R3 are each independently selected from an amino group or a thiol group.

[0050] Preferably, the structural formula of the nitrogen-containing silane compound is:

[0051] Among them, R 12 is C1-C6 alkylene, R 13 It is a C1-C5 alkyl group.

[0052] Further preferably, the nitrogen compound is a mixture of a modified triazine compound and a nitrogen-containing silane compound, and the weight ratio of the modified triazine compound to the nitrogen-containing silane compound is 1:(0.01-2).

[0053] As an optional solution, the elastomer is at least one of styrene elastomer, silicone elastomer, methacrylate elastomer, acrylate elastomer, nitrile elastomer, and core-shell rubber elastomer.

[0054] As an optional solution, the styrene-based elastomer is at least one of a diblock copolymer or a triblock copolymer of hydrogenated styrene and butadiene, and a diblock copolymer or a triblock copolymer of hydrogenated styrene and pentadiene.

[0055] As an optional scheme, the styrene elastomer is selected from SEPTONTM 2000 series (including 2002, 2004, 2005, 2006, 2063, 2104), SEPTONTM 4000 series (including 4033, 4044, 4055, 4077), SEPTONTM 8000 series (including 8004, 8006, 8007L, 8851), SEPTONTM V series (including 9461, 9475), SEPTONTM Q1250, HYBRAR 7000 series (including 7125, 7311) made by KURARE of Japan; or, the styrene elastomer is selected from H1041, H1043, H1051, H1052, H1053, H1221 made by Asahi Chemical of Japan.

[0056] As an optional solution, the silicone elastomer comprises at least one of the following structures:

[0057]

[0058] 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.

[0059] Preferably, R is methyl or phenyl.

[0060] Preferably, X is a mercapto group, an epoxy group or an amino group.

[0061] As an optional scheme, the silicone elastomer is selected from SQ-20P or KHE-8000H manufactured by Nippon Kayaku, SQ502-8 manufactured by Arakawa Chemical, AY42-119 manufactured by DuPont Toray, X-40-2670, R-170S, X-40-2705, X-40-2701, KMP-600, KMP-605, X-52-7030 manufactured by Shin-Etsu Chemical Co., Ltd., EP-2600, EP-2601, EP-2720, TMS-2670, EXL-2315, EXL-2655 manufactured by DOW.

[0062] As an optional solution, the methacrylate elastomer and the acrylate elastomer each independently contain at least one of the following structures:

[0063] Wherein, R1 is a C1-C5 alkyl group, and x is an integer from 1 to 100;

[0064] Wherein, R2 is a C1-C5 alkyl group, and y is an integer from 1 to 100;

[0065] Wherein, R3 is hydrogen or methyl, and o is an integer from 1 to 100.

[0066] More preferably, R1 is methyl, and R2 is methyl, ethyl or butyl.

[0067] As an optional scheme, the methacrylate elastomer is selected from M51, M52, M22 or D51N manufactured by Arkema, LA2250, LA2140, LA-2330, LA4285 manufactured by Kuraray Co., Ltd., SG-P3, SG-80H, PMS-22-1, PMS-22-4, PMS-19-5, PMS-22-5 manufactured by Nagase, Japan.

[0068] As an optional scheme, the acrylic elastomer is selected from M51, M52, M22 or D51N manufactured by Arkema, LA2250, LA2140, LA-2330, LA4285 manufactured by Kuraray Co., Ltd., SG-P3, SG-80H, PMS-22-1, PMS-22-4, PMS-19-5, PMS-22-5 manufactured by Nagase, Japan.

[0069] As a further improvement of one embodiment of the present invention, the nitrile elastomer contains carboxyl groups, hydroxyl groups, epoxy groups or amino groups.

[0070] More preferably, the nitrile elastomer contains a carboxyl group.

[0071] As a further improvement of one embodiment of the present invention, the core portion of the core-shell rubber elastomer is silicone-acrylic rubber or acrylic rubber, and the shell portion contains reactive groups.

[0072] Preferably, the shell portion of the core-shell rubber-based elastomer contains epoxy groups, hydroxyl groups, carboxyl groups or amino groups.

[0073] As an optional solution, the filler is at least one of an inorganic filler, an organic filler, and a composite filler.

[0074] Further preferably, the filler is selected from at least one of spherical 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.

[0075] More preferably, the filler is spherical silica that has been surface treated with an aniline silane coupling agent.

[0076] As a further improvement of one embodiment of the present invention, the structural formula of the phenylaminosilane coupling agent is:

[0077]

[0078] Wherein, R is a C1-C6 straight chain alkylene group, and X is a methoxy group or an ethoxy group.

[0079] As a further improvement of one embodiment of the present invention, the resin composition further includes a dispersant, and the dispersant is 0.001 to 5 parts by weight relative to 100 parts by weight of the maleimide resin, epoxy resin, phenolic resin and elastomer in total.

[0080] As an optional solution, the dispersant is selected from BYK-161 and / or BYK-111 manufactured by BYK.

[0081] As a further improvement of one embodiment of the present invention, the resin composition further comprises a coupling agent, and the coupling agent is 0.001 to 10 parts by weight relative to 100 parts by weight of the maleimide resin, the epoxy resin, the phenolic resin and the elastomer in total.

[0082] As an optional solution, the coupling agent is selected from KBM-402, KBM-403, KBM-502, KBE-503, KBM-603, KBM-903, KBM-573, KBM-602, KBM-1003 manufactured by Xinyue Chemical.

[0083] As a further improvement of one embodiment of the present invention, the resin composition further includes a catalyst.

[0084] As a further improvement of one embodiment of the present invention, the catalyst is 0.01 to 5 parts by weight relative to 100 parts by weight of the maleimide resin, epoxy resin, phenolic resin and elastomer in total.

[0085] As an optional solution, the catalyst is at least one of an imidazole catalyst, a pyridine catalyst, and an organic metal salt catalyst.

[0086] As an optional solution, the catalyst is at least one of 4-dimethylaminopyridine, 2-methylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, modified imidazole and zinc octanoate.

[0087] The present invention also provides the use of the resin composition in prepregs, laminates, insulating boards, insulating films, circuit substrates and electronic devices, which are specifically described as follows:

[0088] The present invention also provides a prepreg, comprising a reinforcing material and the above-mentioned resin composition; the resin composition is wrapped on the reinforcing material.

[0089] The preparation method of the semi-cured sheet is as follows: the resin composition is dissolved in a solvent to prepare a glue solution, and then the glue solution is applied to the reinforcing material by an impregnation method, and the impregnated reinforcing material is taken out and baked at a temperature of 100 to 180° C. for 1 to 15 minutes; after drying, the semi-cured sheet can be obtained.

[0090] As an optional solution, the solvent is selected from at least one of acetone, butanone, methyl isobutyl ketone, N,N-dimethylformamide, N,N-dimethylacetamide, ethylene glycol methyl ether, propylene glycol methyl ether, benzene, toluene, xylene, and cyclohexane.

[0091] As an optional solution, the reinforcing material is selected from at least one of natural fibers, organic synthetic fibers, organic fabrics, and inorganic fabrics.

[0092] 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.

[0093] When the reinforcing material is glass fiber cloth, the glass fiber cloth is chemically treated with a coupling agent in advance to improve the interface bonding between the resin composition and the glass fiber cloth. The coupling agent here is preferably an epoxy silane coupling agent or an amino silane coupling agent to provide good water resistance and heat resistance.

[0094] The present invention also provides a laminate, comprising a piece of the aforementioned prepreg and a metal foil arranged on at least one side of the surface of the prepreg; or comprising a composite sheet formed by overlapping multiple pieces of the aforementioned prepreg and a metal foil arranged on at least one side of the surface of the composite sheet.

[0095] The preparation method of the laminate is: a metal foil is coated on one side or both sides of a prepreg, or at least two prepregs are stacked to form a combined sheet, a metal foil is coated on one side or both sides of the combined sheet, and a metal foil laminate is obtained by hot pressing. 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.

[0096] Preferably, the metal foil is selected from copper foil or aluminum foil. The thickness of the metal foil is 5 μm, 8 μm, 12 μm, 18 μm, 35 μm or 70 μm.

[0097] The present invention also provides an insulating plate, comprising the above resin composition.

[0098] The present invention also provides an insulating film, comprising a carrier film and the aforementioned resin composition coated thereon. The insulating film is prepared by the following method: the aforementioned resin composition is dissolved in a solvent to prepare a glue solution, and then the glue solution is coated on the carrier film, and the carrier film coated with the glue solution is heated and dried to obtain the insulating film.

[0099] As an optional solution, the solvent is selected from at least one of acetone, butanone, methyl isobutyl ketone, N,N-dimethylformamide, N,N-dimethylacetamide, ethylene glycol methyl ether, propylene glycol methyl ether, benzene, toluene, xylene, and cyclohexane.

[0100] As an optional solution, the carrier film is selected from at least one of PET film, PP film, PE film and PVC film.

[0101] The present invention also provides a circuit substrate, comprising at least one of the aforementioned prepreg, laminate, insulating plate, and insulating film. By adopting this technical solution, the heat resistance of the circuit substrate is greatly improved.

[0102] The present invention also provides an electronic device, comprising the above-mentioned circuit substrate. Since the heat resistance of the circuit substrate is greatly improved, the safety of the electronic device is significantly improved.

[0103] The beneficial technical effect of the present application is to provide a resin composition and the application of the resin composition in a prepreg, a laminate, an insulating board, an insulating film, a circuit substrate and an electronic device.

[0104] Due to the application of the above technical solution, the present invention has the following advantages compared with the prior art:

[0105] By setting the type and content of each component in the resin composition and further limiting the content of the filler according to the different contents of the elastomer in the resin composition, the resin composition can have excellent compatibility, not only has a lower CTE value, but also is beneficial to improving the peel strength of the copper foil. DETAILED DESCRIPTION

[0106] The technical solution of the present invention is further introduced below in conjunction with specific implementation methods. The following embodiments are only descriptive and not restrictive, and the protection scope of the present application cannot be limited thereto.

[0107] One embodiment of the present invention 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.

[0108] The present invention provides a resin composition, comprising, by weight:

[0109] Maleimide resin, its weight Wm 10 to 80 parts by weight;

[0110] Epoxy resin, weight W h 10 to 70 parts by weight;

[0111] Phenolic resin, its weight W f 5 to 50 parts by weight;

[0112] The elastic body, whose weight is W t ;

[0113] Nitrogen compounds, whose weight W d 0.1 to 5 parts by weight;

[0114] Filler, its weight is W tl , its content p tl for

[0115] Wherein, the epoxy resin contains at least one naphthalene ring, and / or the phenolic resin contains at least one naphthalene ring.

[0116] Relative to 100 parts by weight of the total of maleimide resin, epoxy resin, phenolic resin and elastomer, when 35 <W t When ≤45, p tl is 45-50%. In some embodiments, p tl Preferably, it is 45-47%. In other embodiments, p tl Preferably 47-50%; when 25≤W t When ≤35, p tl is 55-65%. In some embodiments, p tl Preferably, it is 60-65%. In other embodiments, p tl It is preferably 55 to 60%.

[0117] In some preferred embodiments, when 25≤W t <30, p tl 55~65%; when 30≤W t When ≤35, p tl Preferably 55-65%; when 35 <W t When ≤40, p tl Preferably 45 to 50%; when 40 <W t When ≤45, p tl It is 45 to 50%.

[0118] The maleimide resin may be at least one of the following structures:

[0119]

[0120]

[0121] Wherein, R1 is methylene, ethylene or R2 is hydrogen, methyl or ethyl;

[0122]

[0123] Wherein, n is an integer from 1 to 10;

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

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

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

[0127] Structural formula (10), Wherein, R is hydrogen, methyl or ethyl, and n is an integer of 1 to 10.

[0128] The epoxy resin preferably includes a naphthalene-type epoxy resin, and the structure of the naphthalene-type epoxy resin is one or a mixture of at least two of the following structures:

[0129]

[0130]

[0131] Here, n is an integer from 1 to 10.

[0132] The naphthalene type epoxy resin may be selected from HP-4032SS, HP-4770, EXA-4750, HP-4700, HP-4710, HP-6000, HP-9500, HP-9540, HP-9900 or EXA-7311 manufactured by DIC.

[0133] Furthermore, the epoxy resin also includes any one or more of bisphenol A epoxy resin, bisphenol F epoxy resin, phosphorus-containing epoxy resin, o-cresol epoxy resin, bisphenol A novolac epoxy resin, phenol novolac epoxy resin, trifunctional phenol-type epoxy resin, tetraphenylethane epoxy resin, biphenyl-type epoxy resin, dicyclopentadiene-type epoxy resin, isocyanate-type epoxy resin, aralkyl linear novolac epoxy resin, alicyclic epoxy resin, glycidylamine-type epoxy resin, and glycidylester-type epoxy resin.

[0134] The phenolic resin preferably comprises a naphthalene-type phenolic resin, wherein the naphthalene-type phenolic resin contains at least one of the following structures:

[0135]

[0136]

[0137] Here, n is an integer from 1 to 10.

[0138] The phenolic resin may be selected from EXB-9500 manufactured by DIC or SN495 manufactured by Nippon Steel Chemical.

[0139] Preferably, the phenolic resin further includes bisphenol A phenolic resin, biphenyl phenolic resin, triazine-containing phenolic resin, bisphenol F phenolic resin or dicyclopentadiene phenolic resin.

[0140] The nitrogen-based compound preferably contains at least one of an epoxy group, a mercapto group, an amino group, a hydroxyl group, an acrylate group, a methacrylate group, a vinyl group, and an allyl group.

[0141] The nitrogen compound is preferably at least one of a modified triazine compound and a nitrogen-containing silane compound.

[0142] Preferably, the structural formula of the modified triazine compound is:

[0143]

[0144] Wherein, R1, R2, and R3 are the same or different and are independently selected from hydrogen, hydroxyl, amino, thiol, a group represented by structural formula (25), a group represented by structural formula (26), a group represented by structural formula (27) or structural formula (28), preferably an amino or thiol. Specifically,

[0145] Among them, R4 is C1-C6 alkylene, and R5 is C1-C5 alkyl.

[0146] -R6-OH, structural formula (26), wherein R6 is a C1-C5 alkylene group.

[0147] Structural formula (27), wherein R7 is a C1-C6 alkylene group and R8 is a C1-C5 alkyl group.

[0148] Among them, R9 and R 10 are the same or different, each independently selected from C1-C6 alkylene, R 11 It is a C1-C5 alkyl group.

[0149] The structural formula of the nitrogen-containing silane compound is preferably:

[0150] Among them, R 12 is C1-C6 alkylene, R 13 It is a C1-C5 alkyl group.

[0151] The nitrogen compound is preferably a mixture of a modified triazine compound and a nitrogen-containing silane compound, and the weight ratio of the modified triazine compound to the nitrogen-containing silane compound is 1:(0.01-2).

[0152] The elastomer may be selected from at least one of styrene-based elastomers, silicone-based elastomers, methacrylate-based elastomers, acrylate-based elastomers, nitrile-based elastomers, and core-shell rubber-based elastomers.

[0153] The styrene-based elastomer is preferably at least one of a diblock copolymer or a triblock copolymer of hydrogenated styrene and butadiene, and a diblock copolymer or a triblock copolymer of hydrogenated styrene and pentadiene.

[0154] Specifically, the styrene elastomer is preferably selected from SEPTONTM 2000 series (including 2002, 2004, 2005, 2006, 2063, 2104), SEPTONTM 4000 series (including 4033, 4044, 4055, 4077), HYBRAR7000 series (including 7125, 7311), SEPTONTM 8000 series (including 8004, 8006, 8007L, 8851), SEPTONTM V series (including 9461, 9475), SEPTONTM Q1250 manufactured by KURARE of Japan; or, the styrene elastomer is selected from H1041, H1043, H1051, H1052, H1053, H1221 manufactured by Asahi Chemical of Japan.

[0155] The silicone elastomer preferably comprises at least one of the following structures:

[0156]

[0157]

[0158] Wherein, R is a C1-C12 hydrocarbon group or a C1-C12 alkoxy group, preferably a methyl group or a phenyl group; X is a mercapto group, an epoxy group, a hydroxyl group, a methoxy group or an amino group, preferably a mercapto group, an epoxy group or an amino group.

[0159] 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, X-52-7030 produced by Shin-Etsu Chemical Co., Ltd., EP-2600, EP-2601, EP-2720, TMS-2670, EXL-2315, EXL-2655 produced by DOW.

[0160] The methacrylate elastomer and the acrylate elastomer each independently preferably contain at least one of the following structures:

[0161] Wherein, R1 is a C1-C5 alkyl group, and x is an integer from 1 to 100;

[0162] Wherein, R2 is a C1-C5 alkyl group, and y is an integer from 1 to 100;

[0163] Wherein, R3 is hydrogen or methyl, and o is an integer from 1 to 100.

[0164] More preferably, R1 is methyl, and R2 is methyl, ethyl or butyl.

[0165] Methacrylate elastomers and acrylate elastomers can be selected from M51, M52, M22 or D51N manufactured by Arkema, LA2250, LA2140, LA-2330, LA4285 manufactured by Kuraray Co., Ltd., SG-P3, SG-80H, PMS-22-1, PMS-22-4, PMS-19-5, PMS-22-5 manufactured by Nagase, Japan.

[0166] The nitrile elastomer preferably contains a carboxyl group, a hydroxyl group, an epoxy group or an amino group, and more preferably contains a carboxyl group.

[0167] The core portion of the core-shell rubber-based elastomer is silicone-acrylic rubber or acrylic rubber, and the shell portion contains a reactive group, preferably an epoxy group, a hydroxyl group, a carboxyl group, or an amino group.

[0168] The filler is selected from at least one of inorganic fillers, organic fillers, and composite fillers, preferably at least one of spherical 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.

[0169] The filler is more preferably spherical silica that has been surface treated with an aminosilane coupling agent, and the structural formula of the aminosilane coupling agent is:

[0170]

[0171] Wherein, R is a C1-C6 straight chain alkylene group, and X is a methoxy group or an ethoxy group.

[0172] Furthermore, the resin composition further comprises a dispersant, and the dispersant is in an amount of 0.001 to 5 parts by weight relative to 100 parts by weight of the total of the maleimide resin, the epoxy resin, the phenolic resin and the elastomer.

[0173] The dispersant may be selected from BYK-161 and / or BYK-111 manufactured by BYK.

[0174] Furthermore, the resin composition further comprises a dispersant and a coupling agent, and the coupling agent is 0.001 to 10 parts by weight relative to 100 parts by weight of the total of the maleimide resin, the epoxy resin, the phenolic resin and the elastomer.

[0175] The coupling agent can be selected from KBM-402, KBM-403, KBM-502, KBE-503, KBM-603, KBM-903, KBM-573, KBM-602, KBM-1003 manufactured by Xinyue Chemical.

[0176] Furthermore, the resin composition further comprises a catalyst, and the catalyst is preferably present in an amount of 0.01 to 5 parts by weight relative to 100 parts by weight of the total of the maleimide resin, the epoxy resin, the phenolic resin and the elastomer.

[0177] The catalyst can be selected from at least one of imidazole catalysts, pyridine catalysts, and organic metal salt catalysts, preferably at least one of 4-dimethylaminopyridine, 2-methylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, modified imidazole, and zinc octanoate.

[0178] The present invention also provides a prepreg, comprising a reinforcing material and the above-mentioned resin composition, wherein the resin composition is wrapped on the reinforcing material.

[0179] The preparation method of the semi-cured sheet is as follows: the resin composition is dissolved in a solvent to prepare a glue solution, and then the glue solution is applied to the reinforcing material by an impregnation method, and the impregnated reinforcing material is taken out and baked at a temperature of 100 to 180° C. for 1 to 15 minutes; after drying, the semi-cured sheet can be obtained.

[0180] The solvent may be 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] The reinforcing material can be selected from at least one of natural fibers, organic synthetic fibers, organic fabrics, and inorganic fabrics, preferably glass fiber cloth, more preferably E glass fiber cloth, S glass fiber cloth, or Q glass fiber cloth. The glass fiber cloth is preferably open fiber cloth or flat cloth.

[0182] In addition, when the reinforcing material is glass fiber cloth, the glass fiber cloth is chemically treated with a coupling agent in advance, and the coupling agent is preferably an epoxy silane coupling agent or an amino silane coupling agent.

[0183] The present invention also provides a laminated board, comprising a metal foil and the above-mentioned prepreg; the metal foil is arranged on at least one side surface of the prepreg or a combination of multiple prepregs.

[0184] The laminate can be prepared by the following method: a metal foil is coated on one side or both sides of a prepreg, or at least two prepregs are stacked to form a composite sheet, a metal foil is coated on one side or both sides of the composite sheet, and a metal foil laminate is obtained by hot pressing. 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. The metal foil is selected from copper foil or aluminum foil, and the thickness is 5 μm, 8 μm, 12 μm, 18 μm, 35 μm or 70 μm.

[0185] The present invention also provides an insulating plate, comprising the aforementioned prepreg.

[0186] The present invention also provides an insulating film, comprising a base film and the above-mentioned resin composition coated thereon.

[0187] The preparation method of the insulating film is as follows: the resin composition is dissolved in a solvent to prepare a glue solution, the glue solution is coated on a carrier film, and the carrier film coated with the glue solution is heated and dried to obtain the insulating film.

[0188] The solvent may be 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. The carrier film is preferably at least one of PET film, PP film, PE film, and PVC film.

[0189] The present invention also provides a circuit substrate, comprising at least one of the aforementioned prepreg, laminate, insulating plate, and insulating film.

[0190] The present invention also provides an electronic device, comprising the above-mentioned circuit substrate.

[0191] The technical solution of the present application is further described below in conjunction with some specific embodiments and comparative examples. Of course, these embodiments are only a part of the many variations of the embodiments of the present invention, but not all.

[0192] Example

[0193] The chemical components and contents of the resin compositions of Examples 1 to 6 and Comparative Examples 1 to 5 are shown in Table 1.

[0194]

[0195] Among them, the maleimide resin is MIR-3000 made by Nippon Kayaku, the epoxy resin A is HP-6000 made by DIC, the epoxy resin B is NC-3000 made by Nippon Kayaku, the phenolic resin A is SN495 made by Nippon Steel Chemical, the phenolic resin B is Noflak type made by Tozai, the elastomer A is SG-P3 made by Nagase, Japan, the elastomer B is AY42-119 made by DuPont Toray, the catalyst is 2-methylimidazole, the filler is spherical silica surface-treated with an aminosilane coupling agent, the nitrogen compound A is aminophenylsilane, specifically KBM-573 made by Shin-Etsu Chemical, and the nitrogen compound B is an aminosilicone-modified triazine, specifically VD-5 made by Shikoku Chemical.

[0196] This embodiment also discloses a prepreg, comprising glass fiber cloth as a reinforcing material and a resin composition coated on the glass fiber cloth by an impregnation method, wherein the glass fiber cloth is a fiber-spreading cloth pre-treated with an epoxy silane coupling agent.

[0197] Specifically, the resin compositions of the above-mentioned Examples 1 to 6 and Comparative Examples 1 to 5 were diluted with N, N-dimethylacetamide to form a glue solution with a solid content of 60wt%; the E glass fiber cloth used as a reinforcing material was pretreated with an epoxy silane coupling agent, immersed in the above-mentioned glue solution, taken out after infiltration, placed in a blast drying oven at 160°C, and baked for 3 to 6 minutes to obtain a semi-cured sheet.

[0198] This embodiment also discloses a laminate, which is prepared by the following method:

[0199] The above-mentioned semi-cured sheet was cut into 300×300mm, and then a 12μm thick electrolytic copper foil was placed on both sides of the semi-cured sheet, 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.

[0200] This embodiment also discloses an insulating board, including a prepreg sheet as described above, which is prepared by a conventional preparation method in the prior art, and will not be described in detail herein.

[0201] This embodiment also discloses a circuit substrate, including a prepreg sheet as described above, which is prepared by a conventional preparation method in the prior art, and will not be described in detail herein.

[0202] The copper-clad laminates obtained in Examples 1 to 6 and Comparative Examples 1 to 5 were subjected to performance testing, and the test results are shown in Table 2. The performance testing method includes:

[0203] (1) Glass transition temperature (Tg): The test was conducted using the DMA (thermomechanical analysis) method in accordance with IPC-TM-6502.4.25, with a heating rate of 10°C / min.

[0204] (2) X-axis thermal expansion coefficient (CTE): measured by TMA method in accordance with IPC-TM-650 method, with a heating rate of 10°C / min and a test temperature range of 30 to 100°C.

[0205] (3) Water absorption: The water absorption rate was measured according to the method of 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 were taken, and the electrolytic copper foil on both sides was removed. The samples were dried at 100°C for 2 h, and weighed. The weight was recorded as W1. The samples were then placed in a pressure cooker and treated at 121°C and 2 atmospheres for 6 h. The samples were weighed and the weight was recorded as W2. The water absorption rate was measured as (W2-W1) / W1×100%.

[0206] (4) Moisture and heat resistance (PCT): Take 3 samples with a length × width of 10 cm × 10 cm and a thickness of 0.8 mm, with the electrolytic copper foil removed from both sides. Dry them at 100°C for 2 h, treat them in a pressure cooker at 121°C and 2 atmospheres for 6 h, immerse them in a tin furnace at 288°C for 20 seconds, and visually observe whether there is stratification or blistering.

[0207] (5) Peel strength (PS): The peel strength of the copper foil layer of the laminate was tested according to the "after thermal stress" experimental conditions in the IPC-TM-650 method.

[0208] Table 2

[0209]

[0210] Referring to Table 2, compared with the comparative example, the copper-clad laminate further prepared from the resin composition of the embodiment of the present invention not only has excellent compatibility, a low CTE value, excellent moisture and heat resistance, but also significantly improves the peel strength between the copper foil and the laminate. Specifically:

[0211] (1) Comparing Example 1 with Comparative Examples 1 and 3, Example 1 has excellent compatibility between the resin and the filler, peeling performance, and moisture and heat resistance, while Comparative Example 1 has poor compatibility between the resin and the filler and deteriorated peeling performance, and Comparative Example 3 has poor moisture and heat resistance;

[0212] (2) Comparing Example 2 with Comparative Example 2, the compatibility of the resin and filler, the peeling performance, and the moisture and heat resistance of Example 2 are all excellent, while Comparative Example 2 has the problem of high CTE;

[0213] (3) By comparing Example 4 with Comparative Example 4, it can be seen that when no elastomer is added and the CTE is reduced by only increasing the filler content (filler content exceeds 65%), the CTE reduction effect is not significant, and the peeling performance is deteriorated, and the resin and filler are separated;

[0214] (4) By comparing Example 5 with Comparative Example 5, it can be seen that when no filler is added and the CTE is reduced by only increasing the elastomer content (exceeding 45%), the CTE reduction effect is not significant, and problems such as poor moisture and heat resistance and deteriorated peeling performance of the system will occur.

[0215] It should be understood that although this specification is described according to implementation modes, not every implementation mode contains only one independent technical solution. This description of the specification is only for the sake of clarity. Those skilled in the art should regard the specification as a whole. The technical solutions in each implementation mode may also be appropriately combined to form other implementation modes that can be understood by those skilled in the art.

[0216] The detailed descriptions listed above are only specific descriptions of feasible implementation methods of the present invention. They are not intended to limit the scope of protection of the present invention. All equivalent implementation methods or changes that do not deviate from the technical spirit of the present invention should be included in the scope of protection of the present invention.

Claims

1. A resin composition, characterized in that By weight, including: Maleimide resin, its weight W m 10 to 80 parts by weight; Epoxy resin, weight W h 10 to 70 parts by weight; Phenolic resin, its weight W f 5 to 50 parts by weight; The elastic body, whose weight is W t 25 to 45 parts by weight; Nitrogen compounds, whose weight W d 0.1 to 5 parts by weight; Filler, its weight is W tl , its content p tl for Relative to 100 parts by weight of the total of maleimide resin, epoxy resin, phenolic resin and elastomer, when 35 <W t When ≤45, p tl 45-50%; when 25≤W t When ≤35, p tl 55-65%; The epoxy resin contains at least one naphthalene ring, and / or the phenolic resin contains at least one naphthalene ring; The nitrogen compound is at least one of a modified triazine compound and a nitrogen-containing silane compound.

2. The resin composition according to claim 1, characterized in that The epoxy resin includes a naphthalene-type epoxy resin, and the structure of the naphthalene-type epoxy resin is one of the following structures or a mixture of at least two of them: Here, n is an integer from 1 to 10.

3. The resin composition according to claim 1, characterized in that The phenolic resin includes a naphthalene-type phenolic resin, and the naphthalene-type phenolic resin contains at least one of the following structures: Here, n is an integer from 1 to 10.

4. The resin composition according to claim 1, characterized in that The phenolic resin also includes bisphenol A phenolic resin, biphenyl phenolic resin, triazine-containing phenolic resin, bisphenol F phenolic resin or dicyclopentadiene phenolic resin.

5. The resin composition according to claim 1, characterized in that The elastomer is at least one of styrene elastomer, silicone elastomer, methacrylate elastomer and acrylate elastomer.

6. The resin composition according to claim 5, characterized in that The methacrylate elastomer and the acrylate elastomer each independently contain at least one of the following structures: Wherein, R1 is a C1-C5 alkyl group, and x is an integer from 1 to 100; Wherein, R2 is a C1-C5 alkyl group, and y is an integer from 1 to 100; Wherein, R3 is hydrogen or methyl, and o is an integer of 1 to 100.

7. The resin composition according to claim 5, characterized in that The silicone elastomer comprises at least one of the following structures: 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.

8. The resin composition according to claim 1, characterized in that The filler is selected from at least one of spherical 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.

9. The resin composition according to claim 8, characterized in that The filler is spherical silica that has been surface treated with an aminophenylsilane coupling agent, and the structural formula of the aminophenylsilane coupling agent is: Wherein, R is a C1-C6 straight chain alkylene group, and X is a methoxy group or an ethoxy group.

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

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