Resin composition and use of resin composition

By preparing a specific resin composition, the problems of warping and thermal expansion of copper clad laminate in semiconductor packaging substrate applications are solved, low thermal expansion rate and excellent compatibility are achieved, and moisture resistance and copper foil peel strength are improved. .

WO2025026031A1PCT designated stage expired Publication Date: 2025-02-06SHENGYI TECH (CHANGSHU) CO LTD +1
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Patent Information

Application Number
PCT/CN2024/104981
Authority / Receiving Office
WO · WO
Patent Type
Applications
Current Assignee / Owner
Priority Date
2023-07-31
Filing Date
2024-07-11
Publication Date
2025-02-06

AI Technical Summary

Technical Problem

The existing copper clad laminate is prone to warping problems in semiconductor packaging substrate applications, and has a high thermal expansion coefficient, making it difficult to meet the requirements of high-density wiring and heat resistance.

Method used

By preparing a resin composition, including maleimide resin, epoxy resin, phenolic resin, elastomer, nitrogen compounds and fillers, the proportion and type of each component are adjusted to optimize the compatibility of the resin composition and thermal expansion characteristics.

Benefits of technology

The low thermal expansion rate and excellent compatibility of the resin composition are achieved, the peel strength and moisture-heat resistance of the copper foil are improved, and the warping and thermal expansion problems of the copper clad laminate are solved.

✦ Generated by Eureka AI based on patent content.

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    Figure PCTCN2024104981-FTAPPB-I100003
Patent Text Reader

Abstract

The present application provides a resin composition and a use of the resin composition. The resin composition comprises: 10-80 parts by weight of a maleimide resin, 10-70 parts by weight of an epoxy resin, 5-50 parts by weight of a phenolic resin, an elastomer, 0.1-5 parts by weight of a nitrogen compound, and a filler; when 35<weight Wt of the elastomer≤45, the content ptl of the filler is 45-50%; when 25≤Wt≤35, ptl is 55-65%; the epoxy resin comprises at least one naphthalene ring, and / or the phenolic resin comprises at least one naphthalene ring.
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Description

Resin composition and application of the resin composition

[0001] This application is based on the Chinese patent application with application number 202310953168.3 and application date of July 31, 2023, and claims the priority of the Chinese patent application. The entire content of the above patent application is hereby introduced into this application as a reference. Technical Field

[0002] 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

[0003] In recent years, electronic devices have continued to evolve toward more functionally integrated, miniaturized, and even micro-miniaturized designs. This has led to increasingly dense wiring density within printed circuit boards (PCBs), placing increasing demands on the comprehensive performance of copper-clad laminates, particularly in terms of heat resistance and reliability. However, due to their thermal expansion, copper-clad laminates are prone to warping during packaging when used as semiconductor packaging substrates.

[0004] 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, making it difficult to achieve the required comprehensive performance.

[0005] Summary of the Invention

[0006] 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.

[0007] To achieve the above application objectives, one embodiment of the present application provides a resin composition, which comprises, by weight:

[0008] Maleimide resin, its weight W m 10 to 80 parts by weight;

[0009] Epoxy resin, its weight W h 10 to 70 parts by weight;

[0010] Phenolic resin, its weight W f 5 to 50 parts by weight;

[0011] The elastic body, whose weight is W t ;

[0012] Nitrogen compounds, whose weight W d 0.1 to 5 parts by weight;

[0013] Filler, whose 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%;

[0014] The epoxy resin contains at least one naphthalene ring, and / or the phenolic resin contains at least one naphthalene ring.

[0015] 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 content of the elastomer in the resin composition, the resin composition can have excellent compatibility, not only having a lower CTE value, but also helping to improve the peel strength of the copper foil.

[0016] Preferably, relative to 100 parts by weight of the total of maleimide resin, epoxy resin, phenolic resin and elastomer, when 35 <W t When ≤40, p tl 45-50%; when 30≤W t When ≤35, p tl It is 55-65%.

[0017] Preferably, relative to 100 parts by weight of the total of 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 55-65%.

[0018] Preferably, 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 45-47%; when 25≤W t When ≤35, p tl It is 60-65%.

[0019] Preferably, relative to 100 parts by weight of the total of maleimide resin, epoxy resin, phenolic resin and elastomer, when 35 <W t When ≤45, ptl 47-50%; when 25≤W t When ≤35, p tl It is 55-60%.

[0020] As a further improvement of one embodiment of the present application, the maleimide resin is at least one of the following structures:

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

[0022] Wherein, n is an integer from 1 to 10;

[0023] Wherein, n is an integer from 1 to 10; Wherein, n is an integer from 1 to 10;

[0024] Wherein, n is an integer from 1 to 10;

[0025] Wherein, R is hydrogen, methyl or ethyl, and n is an integer of 1 to 10.

[0026] As a further improvement of one embodiment of the present application, 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:

[0027] Here, n is an integer from 1 to 10.

[0028] As a further improvement of one embodiment of the present application, 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.

[0029] As a further improvement of one embodiment of the present application, the phenolic resin includes a naphthalene-type phenolic resin, and the naphthalene-type phenolic resin contains at least one of the following structures:

[0030] Here, n is an integer from 1 to 10.

[0031] As a further improvement of one embodiment of the present application, the phenolic resin further includes bisphenol A phenolic resin, biphenyl phenolic resin, triazine-containing phenolic resin, bisphenol F phenolic resin or dicyclopentadiene phenolic resin.

[0032] As a further improvement of one embodiment of the present application, the nitrogen compound contains at least one of epoxy, thiol, amino, hydroxyl, acrylate, methacrylate, vinyl, and allyl groups.

[0033] As a further improvement of an embodiment of the present application, the nitrogen compound is at least one of a modified triazine compound and a nitrogen-containing silane compound.

[0034] Preferably, the structural formula of the modified triazine compound is:

[0035] 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:

[0036] Wherein, R4 is C1-C6 alkylene, and R5 is C1-C5 alkyl.

[0037] Wherein, R6 is a C1-C5 alkylene group.

[0038] Wherein, R7 is C1-C6 alkylene, and R8 is C1-C5 alkyl.

[0039] Among them, R9 and R 10 The same or different, each independently selected from C1-C6 alkylene, R 11 It is a C1-C5 alkyl group.

[0040] More preferably, R1, R2, and R3 are each independently selected from an amino group or a thiol group.

[0041] Preferably, the structural formula of the nitrogen-containing silane compound is:

[0042] Among them, R 12 is C1-C6 alkylene, R 13 It is a C1-C5 alkyl group.

[0043] More 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).

[0044] 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.

[0045] As an optional solution, the styrene-based elastomer is at least one of a diblock copolymer or triblock copolymer of hydrogenated styrene and butadiene, and a diblock copolymer or triblock copolymer of hydrogenated styrene and pentadiene.

[0046] As an optional solution, the silicone elastomer comprises at least one of the following structures:

[0047] 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.

[0048] Preferably, R is methyl or phenyl.

[0049] Preferably, X is a mercapto group, an epoxy group or an amino group.

[0050] As an optional solution, the methacrylate elastomer and the acrylate elastomer each independently contain at least one of the following structures:

[0051] Wherein, R1 is a C1-C5 alkyl group, and x is an integer from 1 to 100;

[0052] Wherein, R2 is a C1-C5 alkyl group, and y is an integer from 1 to 100;

[0053] Wherein, R3 is hydrogen or methyl, and o is an integer from 1 to 100.

[0054] More preferably, R1 is methyl, and R2 is methyl, ethyl or butyl.

[0055] As a further improvement of one embodiment of the present application, the nitrile elastomer contains carboxyl groups, hydroxyl groups, epoxy groups or amino groups.

[0056] More preferably, the nitrile elastomer contains a carboxyl group.

[0057] As a further improvement of one embodiment of the present application, the core portion of the core-shell rubber elastomer is silicone-acrylic rubber or acrylic rubber, and the shell portion contains reactive groups.

[0058] Preferably, the shell portion of the core-shell rubber-based elastomer contains epoxy groups, hydroxyl groups, carboxyl groups or amino groups.

[0059] As an optional solution, the filler is at least one of an inorganic filler, an organic filler, and a composite filler.

[0060] 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.

[0061] More preferably, the filler is spherical silica that has been surface-treated with an phenylaminosilane coupling agent.

[0062] As a further improvement of one embodiment of the present application, the structural formula of the phenylaminosilane coupling agent is:

[0063] Wherein, R is a C1-C6 straight-chain alkylene group, and X is a methoxy group or an ethoxy group.

[0064] As a further improvement of one embodiment of the present application, 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.

[0065] As a further improvement of one embodiment of the present application, the resin composition further includes 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, epoxy resin, phenolic resin and elastomer in total.

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

[0067] As a further improvement of one embodiment of the present application, the catalyst is 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.

[0068] As an optional solution, the catalyst is at least one of an imidazole catalyst, a pyridine catalyst, and an organic metal salt catalyst.

[0069] 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 octoate.

[0070] The present application also provides applications of the resin composition in prepregs, laminates, insulating boards, insulating films, circuit substrates, and electronic devices, as specifically described below:

[0071] 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.

[0072] 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.

[0073] The present application also provides an insulating board comprising the aforementioned resin composition.

[0074] The present application also provides an insulating film, comprising a carrier film and the aforementioned resin composition coated thereon.

[0075] The present application 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.

[0076] The present application also provides an electronic device comprising the aforementioned circuit substrate. Since the heat resistance of the circuit substrate is greatly improved, the safety of the electronic device is significantly improved.

[0077] The beneficial technical effect of the present application is to provide a resin composition and the application of the resin composition in prepregs, laminates, insulating boards, insulating films, circuit substrates and electronic devices.

[0078] Due to the application of the above technical solution, this application has the following advantages compared with the prior art:

[0079] 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 content of the elastomer in the resin composition, the resin composition can have excellent compatibility, not only having a lower CTE value, but also helping to improve the peel strength of the copper foil. DETAILED DESCRIPTION

[0080] 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.

[0081] 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.

[0082] The present application provides a resin composition, comprising, by weight:

[0083] Maleimide resin, its weight W m 10 to 80 parts by weight;

[0084] Epoxy resin, its weight W h 10 to 70 parts by weight;

[0085] Phenolic resin, its weight W f 5 to 50 parts by weight;

[0086] The elastic body, whose weight is W t ;

[0087] Nitrogen compounds, whose weight W d 0.1 to 5 parts by weight;

[0088] Filler, whose weight is W tl , its content p tl for

[0089] Wherein, the epoxy resin contains at least one naphthalene ring, and / or the phenolic resin contains at least one naphthalene ring.

[0090] 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%.

[0091] In some preferred embodiments, when 25≤W t <30, p tl 55~65%; when 30≤W t When ≤35, p tl Preferably 55 to 65%; when 35 <W t When ≤40, p tl Preferably 45 to 50%; when 40 <W t When ≤45, p tl It is 45-50%.

[0092] The maleimide resin can be at least one of the following structures:

[0093] Wherein, R1 is methylene, ethylene or R2 is hydrogen, methyl or ethyl;

[0094] Wherein, n is an integer from 1 to 10;

[0095] Wherein, n is an integer from 1 to 10; Wherein, n is an integer from 1 to 10;

[0096] Wherein, n is an integer from 1 to 10;

[0097] Wherein, R is hydrogen, methyl or ethyl, and n is an integer of 1 to 10.

[0098] The epoxy resin preferably includes a naphthalene-type epoxy resin, the structure of which is one or a mixture of at least two of the following structures:

[0099] Here, n is an integer from 1 to 10.

[0100] The naphthalene-type epoxy resin can 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.

[0101] 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.

[0102] The phenolic resin preferably comprises a naphthalene-type phenolic resin containing at least one of the following structures:

[0103] Here, n is an integer from 1 to 10.

[0104] The phenolic resin may be selected from EXB-9500 manufactured by DIC or SN495 manufactured by Nippon Steel Chemical.

[0105] 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.

[0106] The nitrogen 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.

[0107] The nitrogen compound is preferably at least one of a modified triazine compound and a nitrogen-containing silane compound.

[0108] Preferably, the structural formula of the modified triazine compound is:

[0109] wherein R1, R2, and R3 are the same or different and are independently selected from hydrogen, hydroxyl, amino, thiol, a group represented by formula (25), a group represented by formula (26), a group represented by formula (27) or a group represented by formula (28), and are preferably amino or thiol. Specifically,

[0110] Wherein, R4 is C1-C6 alkylene, and R5 is C1-C5 alkyl.

[0111] Wherein, R6 is a C1-C5 alkylene group.

[0112] Wherein, R7 is C1-C6 alkylene, and R8 is C1-C5 alkyl.

[0113] Among them, R9 and R 10 The same or different, each independently selected from C1-C6 alkylene, R 11 It is a C1-C5 alkyl group.

[0114] The structural formula of the nitrogen-containing silane compound is preferably:

[0115] Among them, R 12 is C1-C6 alkylene, R 13 It is a C1-C5 alkyl group.

[0116] 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).

[0117] The elastomer may be selected from at least one of styrene-based elastomers, silicone-based elastomers, methacrylate-based elastomers, acrylic-based elastomers, nitrile-based elastomers, and core-shell rubber-based elastomers.

[0118] The styrene-based elastomer is preferably at least one of a diblock copolymer or triblock copolymer of hydrogenated styrene and butadiene, and a diblock copolymer or triblock copolymer of hydrogenated styrene and pentadiene.

[0119] Specifically, the styrene elastomer is preferably 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.

[0120] The silicone elastomer preferably comprises at least one of the following structures:

[0121] 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.

[0122] Silicone elastomers 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.

[0123] The methacrylate elastomer and the acrylate elastomer each independently preferably contain at least one of the following structures:

[0124] Wherein, R1 is a C1-C5 alkyl group, and x is an integer from 1 to 100;

[0125] Wherein, R2 is a C1-C5 alkyl group, and y is an integer from 1 to 100;

[0126] Wherein, R3 is hydrogen or methyl, and o is an integer from 1 to 100.

[0127] More preferably, R1 is methyl, and R2 is methyl, ethyl or butyl.

[0128] Methacrylate elastomers and acrylic elastomers can be selected from M51, M52, M22 or D51N manufactured by Arkema, LA2250, LA2140, LA-2330, LA4285 manufactured by Kuraray Co., Ltd., and SG-P3, SG-80H, PMS-22-1, PMS-22-4, PMS-19-5, PMS-22-5 manufactured by Nagase, Japan.

[0129] 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.

[0130] The core portion of the core-shell rubber-based elastomer is silicone-acrylic rubber or acrylic rubber, and the shell portion contains reactive groups, preferably epoxy groups, hydroxyl groups, carboxyl groups, or amino groups.

[0131] The filler is selected from at least one of inorganic fillers, organic fillers, and composite fillers, and is preferably 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.

[0132] The filler is more preferably spherical silica that has been surface-treated with an aminosilane coupling agent. The structural formula of the aminosilane coupling agent is:

[0133] Wherein, R is a C1-C6 straight-chain alkylene group, and X is a methoxy group or an ethoxy group.

[0134] Furthermore, the resin composition further comprises a dispersant, and the dispersant is present 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.

[0135] The dispersant may be selected from BYK-161 and / or BYK-111 manufactured by BYK.

[0136] Furthermore, the resin composition further comprises a dispersant and a coupling agent. The coupling agent is present in an amount of 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.

[0137] 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.

[0138] Furthermore, the resin composition further comprises a catalyst, preferably 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.

[0139] 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 octoate.

[0140] The present application also provides a prepreg, comprising a reinforcing material and the aforementioned resin composition, wherein the resin composition is wrapped on the reinforcing material.

[0141] 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.

[0142] The solvent can 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.

[0143] 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.

[0144] Furthermore, when glass fiber cloth is used as the reinforcing material, 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.

[0145] The present application also provides a laminate 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.

[0146] The laminate can be prepared by coating one or both sides of a prepreg sheet with metal foil, or by stacking at least two prepreg sheets to form a composite sheet, coating one or both sides of the composite sheet with metal foil, and then hot-pressing the resulting metal foil laminate. The hot-pressing conditions are: a pressure of 0.2-2 MPa, a temperature of 150-250°C, and a pressing time of 2-4 hours. The metal foil can be 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.

[0147] The present application also provides an insulating board comprising the aforementioned prepreg.

[0148] The present application also provides an insulating film, comprising a base film and the aforementioned resin composition coated thereon.

[0149] 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.

[0150] 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.

[0151] The present application also provides a circuit substrate, comprising at least one of the aforementioned prepreg, laminate, insulating plate, and insulating film.

[0152] The present application also provides an electronic device comprising the aforementioned circuit substrate.

[0153] The technical solution of the present application is further described below with reference to some specific examples and comparative examples. Of course, these examples are only a part of the many variations of the embodiments of the present application, but not all of them.

[0154] Example

[0155] 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.

[0156] Among them, the maleimide resin is MIR-3000 produced by Nippon Kayaku, the epoxy resin A is HP-6000 produced by DIC, the epoxy resin B is NC-3000 produced by Nippon Kayaku, the phenolic resin A is SN495 produced by Nippon Steel Chemical, the phenolic resin B is Noflak type produced by Tosai, the elastomer A is SG-P3 produced by Nagase, Japan, the elastomer B is AY42-119 produced 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 produced by Shin-Etsu Chemical, and the nitrogen compound B is an aminosilicone-modified triazine, specifically VD-5 produced by Shikoku Chemical.

[0157] 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-spread cloth pretreated with an epoxy silane coupling agent.

[0158] Specifically, the resin compositions of 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 60 wt%; the E glass fiber cloth used as the 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.

[0159] This embodiment also discloses a laminate, which is prepared by the following method:

[0160] 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.

[0161] 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.

[0162] 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.

[0163] 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:

[0164] (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.

[0165] (2) X-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.

[0166] (3) Water absorption: 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 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, weighed, and 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 determined to be (W2-W1) / W1×100%.

[0167] (4) Moisture and heat resistance (PCT): Take three 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. After drying at 100°C for 2 h, treat them in a pressure cooker at 121°C and 2 atmospheres for 6 h. Then immerse them in a tin furnace at 288°C for 20 seconds and visually observe whether there is delamination or blistering.

[0168] (5) Peel strength (PS): The peel strength of the copper foil layer of the laminate is tested according to the "after thermal stress" experimental conditions in the IPC-TM-650 method.

[0169] Table 2

[0170] As shown in Table 2, compared with the comparative example, the copper-clad laminate prepared from the resin composition of the embodiment of the present application not only has excellent compatibility, a low CTE value, excellent moisture and heat resistance, but also significantly improved peel strength between the copper foil and the laminate. Specifically:

[0171] (1) Comparing Example 1 with Comparative Examples 1 and 3, Example 1 exhibited excellent compatibility between the resin and filler, peeling performance, and moisture and heat resistance, whereas Comparative Example 1 exhibited poor compatibility between the resin and filler and deteriorated peeling performance, and Comparative Example 3 exhibited poor moisture and heat resistance.

[0172] (2) Comparing Example 2 with Comparative Example 2, Example 2 exhibits excellent compatibility between the resin and filler, peeling performance, and moisture and heat resistance, while Comparative Example 2 exhibits a relatively high CTE.

[0173] (3) Comparison of Example 4 and Comparative Example 4 shows that when no elastomer is added and the CTE is reduced by simply increasing the filler content (filler content exceeds 65%), the CTE reduction effect is not significant, and the peeling performance is deteriorated, and separation of the resin and filler occurs;

[0174] (4) Comparison of Example 5 and Comparative Example 5 shows that when no filler is added and the CTE is reduced only by 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.

[0175] 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.

[0176] 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 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 ; 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.

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 from 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 claim 1 in prepregs, laminates, insulating boards, insulating films, circuit substrates and electronic devices.

Citation Information

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