Resin composition and use thereof

Abstract

The present application provides a resin composition and its application. The resin composition comprises, by weight: 20-100 parts of a maleimide resin; 1-80 parts of an allyl-modified imide resin; 5-70 parts of a mixture of a reactive elastomer and a non-reactive elastomer; and 30-200 parts of an inorganic filler. By adding 5-70 parts of the reactive elastomer and the non-reactive elastomer, and simultaneously adding the allyl-modified imide resin, the resin composition has excellent heat resistance, high modulus, low CTE, high toughness, reduced thermal expansion coefficient to reduce warping defects, high compatibility, high adhesion, low water absorption, ensures comprehensive performance, and can also improve the production process, and has a broad application prospect.

Description

TECHNICAL FIELD

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

[0002] In the process of semiconductor packaging, if the thermal expansion coefficients of the semiconductor element and the substrate are too different, stress is easily generated to cause the substrate to warp, thereby causing serious problems such as poor connection between the semiconductor element and the substrate. Therefore, the substrate material needs to have a lower thermal expansion coefficient.

[0003] In the prior art, a high content of inorganic filler is generally added to meet the requirement of low thermal expansion coefficient, but the high content of inorganic filler increases the viscosity of the resin glue solution, seriously affects the product preparation process, and affects the drilling processability of the PCB, so it is difficult to obtain a final cured product that meets both low thermal expansion and excellent processability by this method.

[0004] Maleimide resin has excellent heat resistance, high modulus and low CTE, and is widely used in high-performance circuit substrates. However, maleimide resin has the disadvantages of high curing temperature, high water absorption and high brittleness. The existing solutions to overcome the disadvantages of maleimide resin will cause new defects to some extent, such as decreased heat resistance, poor compatibility, reduced adhesion, etc.

[0005] In summary, there is no existing technology that can guarantee excellent heat resistance, high modulus, low CTE, and excellent toughness, compatibility, adhesion and water absorption at the same time. SUMMARY

[0006] In view of the problems in the prior art, the purpose of the present application is to provide a resin composition and the application of the resin composition in a prepreg, a laminated board, an insulating board, an insulating film, a circuit substrate and an electrical device.

[0007] To achieve the above-mentioned purpose of the application, an embodiment of the present application provides a resin composition. The following technical solutions are specifically adopted:

[0008] The resin composition comprises, by weight based on the solid content:

[0009] Maleimide resin and / or maleimide prepolymer, 20-100 parts by weight;

[0010] Allyl-modified imide resin, 1-80 parts by weight;

[0011] A mixture of reactive elastomer and non-reactive elastomer, 5-70 parts by weight; and

[0012] Inorganic filler, 30-200 parts by weight.

[0013] Thus, in the system of maleimide resin, 5-70 parts by weight of reactive elastomer and non-reactive elastomer are added, and allyl-modified imide resin is added at the same time, so that the resin composition has excellent heat resistance, high modulus, low CTE, high toughness, reduced thermal expansion coefficient to reduce warpage defects, high compatibility, high adhesion, low water absorption, ensures the comprehensive performance, and can also improve the production process, and has wide application prospect.

[0014] As an alternative, the allyl-modified imide resin comprises a structural formula (1):

[0015] Structural formula (1);

[0016] In which, R group is

[0017] For example, the allyl-modified imide resin is selected from BANI-M, BANI-H or BANI-X of Maruyama Chemical.

[0018] As an alternative, the reactive elastomer and the non-reactive elastomer are at least one of styrene, silicone, and acrylate.

[0019] As a preferred alternative, the non-reactive elastomer is a non-reactive elastomer of styrene, the reactive elastomer is a reactive elastomer of acrylate; or the non-reactive elastomer is a non-reactive elastomer of styrene, the reactive elastomer is a reactive elastomer of silicone; or the non-reactive elastomer is a non-reactive elastomer of silicone, the reactive elastomer is a reactive elastomer of acrylate; or the non-reactive elastomer is a non-reactive elastomer of acrylate, the reactive elastomer is a reactive elastomer of silicone. Thus, when the reactive elastomer and the non-reactive elastomer are combined as described above, excellent compatibility and low CTE are exhibited in the resin composition, and the overall cured product has very excellent comprehensive performance, such as very little decrease in heat resistance, maintaining low water absorption and high peel strength.

[0020] As an alternative, the reactive elastomer contains at least one of hydroxyl, epoxy, amino, cyano, unsaturated double bond, mercapto, and anhydride group.

[0021] As an optional option, the reactive elastomer is selected from at least one of the following: partially hydrogenated polybutadiene, partially hydrogenated styrene-butadiene copolymer, partially hydrogenated styrene-butadiene-styrene copolymer, partially hydrogenated styrene-pentadiene copolymer, anhydride-modified styrene-butadiene copolymer, epoxy-modified polybutadiene resin, epoxy-modified acrylate copolymer, epoxy-modified methacrylate copolymer, cyanoacrylate copolymer, cyanomethacrylate copolymer, epoxy-containing silicone rubber, and epoxy-containing silicone resin.

[0022] For example, the reactive elastomer is selected from any one or more of the following grades of materials: Asahi Kasei Corporation P1083, P1500 P5051, P2000 M1943 M1913 M1911; KURARE Hybrar TM 5125, HYBRAR TM 5127, SEPTON TM HG252; Nagase-manufactured SG-P3, SG-80H, PMS-22-1, PMS-22-4, PMS-19-5, PMS-22-5; Nippon Kayaku-manufactured SQ-20P, KHE-8000H; Arakawa Chemical-manufactured SQ502-8; DuPont Toray-manufactured AY42-119; etc.

[0023] As an alternative, the non-reactive elastomer is at least one of styrene-based, silicone-based, and acrylate-based elastomers.

[0024] For example, the styrene-based non-reactive elastomer is selected from any one or more of the following grades: SEPTON, manufactured by KURARE, Japan. TM 2000 series (2002, 2004, 2005, 2006, 2063, 2104), SEPTON TM 4000 series (4033, 4044, 4055, 4077), HYBRAR TM 7000 series (7125, 7311), SEPTON TM 8000 series (8004, 8006, 8007L, 8851), SEPTON TM V series (9461, 9475), SEPTON TM Q1250; Asahi Kasei's H1041, H1043, H1051, H1052, H1053, H1221; etc.

[0025] For example, the non-reactive silicone-based elastomer is selected from any one or more of the following brand materials: Shin-Etsu Chemical's X-40-2670, R-170S, X-40-2705, X-40-2701, KMP-600, KMP-605, X-52-7030; DOW's EP-2600, EP-2601, EP-2720, TMS-2670, EXL-2315, EXL-2655, etc.

[0026] Preferably, the non-reactive acrylate-based elastomer is a non-reactive methacrylate-based elastomer.

[0027] For example, the non-reactive acrylate-based elastomer is selected from any one or more of the following brand materials: Arkema's M51, M52, M22, or D51N; Kuraray's LA2250, LA2140, LA-2330, LA4285; etc.

[0028] As an option, the content ratio of the reactive elastomer to the non-reactive elastomer is 1 : (0.1-20) by weight of solid.

[0029] As an option, the content of the reactive elastomer is less than the content of the non-reactive elastomer by weight of solid.

[0030] Preferably, the content ratio of the reactive elastomer to the non-reactive elastomer is 1 :2, 1 :3, 1 :4, 1 :5, 1 :6, 1 :7, 1 :8, 1 :9, 1 :10, 1 :11, 1 :12, 1 :13, 1 :14, 1 :15, 1 :16, 1 :17, 1 :18, 1 :19, or 1 :20 by weight of solid.

[0031] As an option, the reactive elastomer and the non-reactive elastomer are different kinds of compounds. Specifically, the reactive elastomer and the non-reactive elastomer do not contain the same repeating structural unit, for example, when the reactive elastomer contains a butadiene-based repeating structural unit, the non-reactive elastomer does not contain a butadiene-based repeating structural unit.

[0032] As an option, the resin composition further includes an epoxy resin or / and a cyanate ester resin.

[0033] As an option, the epoxy resin can also be selected from one or more of bisphenol A epoxy resin, bisphenol F epoxy resin, bisphenol S epoxy resin, bisphenol E epoxy resin, phosphorus-containing epoxy resin, o-cresol novolac 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 epoxy resin, dicyclopentadiene epoxy resin, isocyanate epoxy resin, aralkyl novolac epoxy resin, alicyclic epoxy resin, glycidyl amine epoxy resin, glycidyl ether epoxy resin, glycidyl ester epoxy resin.

[0034] Preferably, the epoxy resin includes a compound of structural formula (1) or / and a compound of structural formula (2):

[0035] Structural formula (1); wherein n is an integer from 1 to 10;

[0036] Structural formula (2).

[0037] As an option, the resin composition includes 1 to 30 parts by weight of the epoxy resin based on 100 parts by weight of the maleimide resin and / or maleimide prepolymer and allyl-modified imide resin in total.

[0038] As an option, the cyanate ester resin is a compound containing at least one cyanate group, which can be a monomer, a polymer, a prepolymer, or a combination thereof. Preferably, the cyanate ester resin is a prepolymer, or a combination of a prepolymer and a monomer, or a combination of a prepolymer and a polymer.

[0039] As an option, the cyanate ester resin is selected from at least one of bisphenol A cyanate ester, bisphenol F cyanate ester, bisphenol E cyanate ester, bisphenol M cyanate ester, DCPD cyanate ester, naphthalene cyanate ester, phenol novolac cyanate ester, and biphenyl cyanate ester.

[0040] As an option, the resin composition includes 1 to 35 parts by weight of the cyanate ester resin based on 100 parts by weight of the maleimide resin and / or maleimide prepolymer and allyl-modified imide resin in total.

[0041] As an option, the cyanate ester resin includes a compound of structural formula (3):

[0042] Structural formula (3); wherein R is hydrogen or methyl, and n is an integer from 1 to 10.

[0043] Further, the maleimide resin and / or maleimide prepolymer comprises a compound of structural formula (9)

[0044] at least one of structural formula (18):

[0045] structural formula (9);

[0046] structural formula (10);

[0047] structural formula (11);

[0048] structural formula (12), wherein R2 is hydrogen, methyl or ethyl, R1 is methylene, ethylene or

[0049] structural formula (13);

[0050] structural formula (14), wherein n is an integer from 1 to 10;

[0051] structural formula (15), wherein n is an integer from 1 to 10;

[0052] structural formula (16), wherein n is an integer from 1 to 10;

[0053] structural formula (17), wherein n is an integer from 1 to 10;

[0054] structural formula (18), wherein R is hydrogen, methyl or ethyl, n is an integer from 1 to 10.

[0055] For example, the maleimide resin is selected from any one or more of the following trade name materials: BMI-1000, BMI-1000H, BMI-1100, BMI-1100H, BMI-2000, BMI-2300, BMI-3000, BMI-3000H, BMI-4000H, BMI-5000, BMI-5100, BMI-7000, BMI-7000H, manufactured by Taimei Chemicals Co., Ltd.; BMI, BMI-70, BMI-80, manufactured by KI Chemicals Co., Ltd., Japan; MIR-3000, MIR-5000, manufactured by Japan Chemicals Co., Ltd.; X9-450, X9-470, manufactured by DIC Co., Ltd., Japan; D936, D937, D939, D950, manufactured by Sichuan Dongcai Co., Ltd.; and the like.

[0056] Further, the resin composition further comprises 0.1 to 30 parts by weight of a molybdenum compound.

[0057] As an alternative, the molybdenum compound is molybdenum disulfide, molybdenum dioxide, molybdenum trioxide, barium molybdate, potassium molybdate, phosphomolybdic acid, sodium phosphomolybdate, silicomolybdate, molybdenum boride, molybdenum nitride, molybdenum carbide, zinc molybdate or a hydrate thereof, amine molybdate or a hydrate thereof, calcium molybdate or a hydrate thereof, sodium molybdate or a hydrate thereof, nickel molybdate or a hydrate thereof, ketone molybdate or a hydrate thereof, iron molybdate or a hydrate thereof, or an organomolybdenum compound.

[0058] Preferably, the molybdenum compound is zinc molybdate. In particular, the molybdenum compound is selected from at least one of anhydrous zinc molybdate, hydrous zinc molybdate (Zn3Mo2O8(OH)2), amine molybdate, amine molybdate hydrate ((NH4)Zn2Mo9(H2O)), molybdenum dialkyldithiocarbamate, molybdenum dialkyldithiophosphate, talc coated with zinc molybdate, montmorillonite coated with zinc molybdate, and silica coated with zinc molybdate.

[0059] More preferably, the molybdenum compound is talc coated with zinc molybdate or talc coated with calcium molybdate.

[0060] For example, the molybdenum compound is selected from Huber's KG-911C, KG-911A, or 1100.

[0061] As an alternative, the inorganic 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.

[0062] Preferably, the inorganic filler comprises silica.

[0063] As an alternative, the inorganic filler is surface treated with a silane coupling agent, which is at least one of an amino silane coupling agent, a carbon-carbon double bond containing silane coupling agent, or an epoxy silane coupling agent.

[0064] Further, the resin composition comprises 0.001 to 5 parts by weight of a dispersing agent and 0.001 to 10 parts by weight of a coupling agent, per 100 parts by weight of the resin composition.

[0065] As an alternative, the dispersing agent is selected from BYK-161 or / and BYK-111 by BYK-Chemie, and the coupling agent is selected from KBM-402, KBM-403, KBM-502, KBE-503, KBM-603, KBM-903, KBM-573, KBM-602, KBM-1003, etc. by Shin-Etsu Chemical.

[0066] Further, the resin composition further includes 1 to 60 parts by weight of a flame retardant, based on 100 parts by weight of the allyl-modified imide resin, the maleimide resin, and / or the maleimide prepolymer in total.

[0067] As an option, the flame retardant is selected from at least one of a bromine-based flame retardant, a phosphorus-based flame retardant, a nitrogen-based flame retardant, an organic silicon flame retardant, an organic metal flame retardant, and an inorganic flame retardant.

[0068] As an option, the bromine-based flame retardant is selected from decabromodiphenyl ether, decabromodiphenyl ethane, brominated styrene, or tetrabromophthalic diamide.

[0069] As an option, the phosphorus-based flame retardant is provided as an inorganic phosphorus, an inorganic phosphorus compound, or an organic phosphorus compound. The inorganic phosphorus compound is any one of a phosphoric acid compound, a hypophosphorous acid compound, or a phosphorus oxide compound, and the organic phosphorus compound is a condensed phosphoric acid ester compound, 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, or a phosphazene, in which m is an integer of 1 to 5.

[0070] As an option, the nitrogen-based flame retardant is selected from a triazine compound, a cyanuric acid compound, an isocyanic acid compound, a phenothiazine, or the like.

[0071] As an option, the organic silicon flame retardant can be an organic silicon oil, an organic silicon rubber, an organic silicon resin, or the like.

[0072] As an option, the organic metal flame retardant can be ferrocene, an acetylacetone metal complex, an organic metal carbonyl compound, or the like.

[0073] As an option, the inorganic flame retardant can be aluminum hydroxide, magnesium hydroxide, aluminum oxide, barium oxide, or the like.

[0074] Further, the resin composition further includes 0.01 to 5 parts by weight of a catalyst, which is at least one of an imidazole-based catalyst, a pyridine-based catalyst, and an organic metal salt-based catalyst.

[0075] As an option, the catalyst is at least one of 4-dimethylaminopyridine, 2-methylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, a modified imidazole, and zinc octoate.

[0076] To achieve the above object, one embodiment of the present application provides an application of a resin composition. The technical scheme is specifically as follows.

[0077] The resin composition comprises, by weight based on the solid weight, 20-100 parts of a maleimide resin and / or a maleimide prepolymer; 1-80 parts of an allyl-modified imide resin; 5-70 parts of a mixture of a reactive elastomer and a non-reactive elastomer; and 30-200 parts of an inorganic filler.

[0078] The application is the application of the resin composition in prepreg, laminated board, insulating board, insulating film, circuit board and electrical device.

[0079] As an option, the resin composition is applied to a prepreg, wherein the prepreg comprises the resin composition and a reinforcing material, and the resin composition is attached to the surface of the reinforcing material.

[0080] As an option, the preparation method of the prepreg is as follows: the resin composition is dissolved in a solvent to form a glue solution, the reinforcing material is immersed in the glue solution, and then the immersed reinforcing material is baked at 100-180°C for 1-15 min, and the dried prepreg is obtained.

[0081] As an option, the at least one solvent is selected from acetone, butanone, toluene, methyl isobutyl ketone, N, N-dimethylformamide, N, N-dimethylacetamide, ethylene glycol methyl ether, propylene glycol methyl ether, benzene, toluene, xylene and cyclohexane.

[0082] As an option, the reinforcing material is selected from at least one of natural fiber, organic synthetic fiber, organic fabric and inorganic fabric. More preferably, the reinforcing material is a glass fiber cloth, and the glass fiber cloth preferably uses an open fiber cloth or a flat cloth; and the glass fiber cloth is preferably an E glass fiber cloth, an S glass fiber cloth, a T glass fiber cloth or a Q glass fiber cloth.

[0083] Preferably, the glass fiber cloth is chemically treated by a coupling agent such as an epoxy silane or an amino silane to provide good water resistance and heat resistance, and to improve the interfacial bonding between the resin composition and the glass fiber cloth.

[0084] Further, the resin composition is applied to a laminated board, and the laminated board is a metal-clad laminated board.

[0085] As an option, the laminated board comprises a piece of the prepreg and a metal foil attached to at least one side surface of the prepreg.

[0086] Specifically, the preparation method of the laminated plate is: covering the metal foil on one side or both sides of the semi-cured sheet, and hot pressing at 0.2-2 MPa and 150-250 DEG C for 2-4 hours to obtain the metal foil laminated plate.

[0087] As an alternative, the laminated plate comprises a combined sheet formed by folding two or more semi-cured sheets together and a metal foil attached to at least one side of the combined sheet.

[0088] Specifically, the preparation method of the laminated plate is: covering the metal foil on one side or both sides of the semi-cured sheet, and hot pressing at 0.2-2 MPa and 150-250 DEG C for 2-4 hours to obtain the metal foil laminated plate.

[0089] As an alternative, the metal foil can be copper foil, aluminum foil or other metal materials, and the thickness can be preferably 5 μm, 8 μm, 12 μm, 18 μm, 35 μm or 70 μm.

[0090] Further, the resin composition is applied to an insulating plate.

[0091] Further, the resin composition is applied to an insulating film, which comprises an insulating resin layer formed by the resin composition.

[0092] Further, the resin composition is applied to a circuit substrate, which comprises any one of the semi-cured sheet, the laminated plate, the insulating plate and the insulating film.

[0093] Further, the resin composition is applied to an electrical device, which comprises any one of the semi-cured sheet, the laminated plate, the insulating plate, the insulating film and the circuit substrate.

[0094] In summary, compared with the prior art, the embodiment of the present application has the following advantages: in the system of maleimide resin, 5-70 parts by weight of reactive elastomer and non-reactive elastomer are added, and allyl-modified imide resin is added at the same time, so that the resin composition has excellent heat resistance, high modulus, low CTE, high toughness, reduced thermal expansion coefficient to reduce warpage defects, high compatibility, high adhesion, low water absorption, and ensures the comprehensive performance, and the production process can also be improved, which has a wide application prospect. DETAILED DESCRIPTION

[0095] The following describes specific embodiments of the present application. It should be noted that those of ordinary skill in the art can make several improvements and refinements without departing from the principles of the embodiments of the present application, and these improvements and refinements are also considered within the scope of protection of the embodiments of the present application.

[0096] The present application provides a resin composition, and based on the resin composition, further provides a prepreg, a laminate, an insulating board, an insulating film, a circuit substrate, and an electrical device using the resin composition, in order to address the current situation that there is no technology that can ensure excellent heat resistance, high modulus, low CTE, excellent toughness, compatibility, adhesion, and water absorption.

[0097] Specifically, an embodiment of the present application provides a resin composition.

[0098] The resin composition comprises, by weight based on the solid weight:

[0099] a maleimide resin, 20 to 100 parts by weight;

[0100] an allyl-modified imide resin, 1 to 80 parts by weight;

[0101] a mixture of a reactive elastomer and a non-reactive elastomer, 5 to 70 parts by weight; and

[0102] an inorganic filler, 30 to 200 parts by weight.

[0103] In this way, in the system of the maleimide resin, 5 to 70 parts by weight of the reactive elastomer and the non-reactive elastomer are added, and the allyl-modified imide resin is added at the same time, so that the resin composition has excellent heat resistance, high modulus, low CTE, high toughness, low thermal expansion coefficient to reduce warpage defects, high compatibility, high adhesion, low water absorption, ensures comprehensive performance, and can also improve the production process, and has a wide application prospect.

[0104] As an optional solution, the allyl-modified imide resin comprises a structural formula (1):

[0105] the structural formula (1);

[0106] wherein, R is

[0107] For example, the allyl-modified imide resin is selected from BANI-M, BANI-H, or BANI-X of Maruzen Chemical Co., Ltd.

[0108] As an optional solution, the reactive elastomer and the non-reactive elastomer are at least one of styrene-based, silicone-based, and acrylate-based.

[0109] As a preferred embodiment, the non-reactive elastomer is a styrene-based non-reactive elastomer, and the reactive elastomer is an acrylate-based reactive elastomer; or, the non-reactive elastomer is a styrene-based non-reactive elastomer, and the reactive elastomer is a silicone-based reactive elastomer; or, the non-reactive elastomer is a silicone-based non-reactive elastomer, and the reactive elastomer is an acrylate-based reactive elastomer; or, the non-reactive elastomer is an acrylate-based non-reactive elastomer, and the reactive elastomer is a silicone-based reactive elastomer. In this way, when the reactive elastomer and the non-reactive elastomer are used in the above combinations, excellent compatibility and low CTE are exhibited in the resin composition, and the overall cured product has very excellent comprehensive performance, such as very little decrease in heat resistance, maintaining a low water absorption rate, and high peel strength.

[0110] As an optional embodiment, the reactive elastomer contains at least one of a hydroxyl group, an epoxy group, an amino group, a cyano group, an unsaturated double bond, a mercapto group, and an anhydride group.

[0111] As an optional embodiment, the reactive elastomer is at least one of partially hydrogenated polybutadiene, partially hydrogenated styrene-butadiene copolymer, partially hydrogenated styrene-butadiene-styrene copolymer, partially hydrogenated styrene-pentadiene copolymer, anhydride-modified styrene-butadiene copolymer, epoxy-modified polybutadiene resin, epoxy-modified acrylate copolymer, epoxy-modified methacrylate copolymer, cyano-containing acrylate copolymer, cyano-containing methacrylate copolymer, epoxy-containing silicone rubber, and epoxy-containing silicone resin.

[0112] For example, the reactive elastomer is selected from any one or more of the following brands of materials: Asahi Kasei P1083, P1500, P5051, P2000, M1943, M1913, M1911; HYBRAR TM 5125, HYBRAR TM 5127, SEPTON TM HG252; SG-P3, SG-80H, PMS-22-1, PMS-22-4, PMS-19-5, PMS-22-5 by Nippon Seki, SQ-20P, KHE-8000H by Nippon Kayaku, SQ502-8 by Arakawa Chemical, AY42-119 by Du Pont-Dow Corning, and the like.

[0113] As an alternative, the non-reactive elastomer is at least one of styrene-based, silicone-based, and acrylate-based elastomers.

[0114] For example, the styrene-based non-reactive elastomer is selected from any one or more of the following grades: SEPTON, manufactured by KURARE, Japan. TM 2000 series (2002, 2004, 2005, 2006, 2063, 2104), SEPTON TM 4000 series (4033, 4044, 4055, 4077), HYBRAR TM 7000 series (7125, 7311), SEPTON TM 8000 series (8004, 8006, 8007L, 8851), SEPTON TM V series (9461, 9475), SEPTON TM Q1250; Asahi Kasei's H1041, H1043, H1051, H1052, H1053, H1221; etc.

[0115] For example, the non-reactive silicone elastomer is selected from any one or more of the following grades of materials: Shin-Etsu Chemical X-40-2670, R-170S, X-40-2705, X-40-2701, KMP-600, KMP-605, X-52-7030; DOW EP-2600, EP-2601, EP-2720, TMS-2670, EXL-2315, EXL-2655, etc.

[0116] Preferably, the acrylate-based non-reactive elastomer is a methacrylate-based non-reactive elastomer.

[0117] For example, the acrylate-based non-reactive elastomer is selected from any one or more of the following grades of materials: Arkema M51, M52, M22 or D51N; Kuraray Co., Ltd. LA2250, LA2140, LA-2330, LA4285; etc.

[0118] As an alternative, the content ratio of the reactive elastomer to the non-reactive elastomer is 1:(0.1 to 20) by solid weight.

[0119] As an alternative, the content of the reactive elastomer is less than the content of the non-reactive elastomer by solid weight.

[0120] Preferably, the content ratio of the reactive elastomer and the non-reactive elastomer is 1:2, 1:3, 1:4, 1:5, 1:6, 1:7, 1:8, 1:9, 1:10, 1:11, 1:12, 1:13, 1:14, 1:15, 1:16, 1:17, 1:18, 1:19 or 1:20 by weight of the solid.

[0121] When too much reactive elastomer is added in the resin composition, the compatibility between different resins is good at room temperature, but it is difficult for the toughness group with large molecular weight to be uniformly distributed in the whole cured product under high temperature conditions, which affects the CTE, water absorption and heat resistance; when too little reactive elastomer is added in the resin composition, the compatibility between different resins is poor, which affects the processability in mass production, and it is difficult to obtain a resin composition with stable comprehensive performance. However, based on the content ratio of the reactive elastomer and the non-reactive elastomer in the present application, the compatibility, CTE, water absorption and heat resistance can be considered.

[0122] As an optional solution, the reactive elastomer and the non-reactive elastomer are different kinds of compounds. Specifically, the reactive elastomer and the non-reactive elastomer do not contain the same repeating structural unit, for example, the reactive elastomer contains butadiene repeating structural unit, and the non-reactive elastomer does not contain butadiene repeating structural unit.

[0123] As an optional solution, the resin composition further comprises an epoxy resin or / and a cyanate ester resin.

[0124] As an optional solution, the epoxy resin can be selected from one or more of bisphenol A epoxy resin, bisphenol F epoxy resin, bisphenol S type epoxy resin, bisphenol E type epoxy resin, phosphorus-containing epoxy resin, o-cresol formaldehyde epoxy resin, bisphenol A formaldehyde epoxy resin, phenol formaldehyde epoxy resin, cresol formaldehyde epoxy resin, triphenylmethane epoxy resin, tetraphenyl ethane epoxy resin, biphenyl type epoxy resin, naphthalene ring type epoxy resin, dicyclopentadiene type epoxy resin, isocyanate type epoxy resin, aralkyl linear phenol formaldehyde epoxy resin, alicyclic epoxy resin, glycidyl amine type epoxy resin, glycidyl ether type epoxy resin, glycidyl ester type epoxy resin.

[0125] Preferably, the epoxy resin comprises a compound of structural formula (1) or / and a compound of structural formula (2):

[0126] Structural formula (1); wherein n is an integer of 1-10;

[0127] Structural formula (2).

[0128] As an option, the resin composition includes 1 to 30 parts by weight of an epoxy resin, based on 100 parts by weight of the maleimide resin and / or maleimide prepolymer and allyl-modified imide resin in total.

[0129] As an option, the cyanate ester resin is at least one selected from the group consisting of bisphenol A type cyanate ester, bisphenol F type cyanate ester, bisphenol E type cyanate ester, bisphenol M type cyanate ester, DCPD type cyanate ester, naphthalene type cyanate ester, phenol-aldehyde type cyanate ester, and biphenyl cyanate ester.

[0130] As an option, the cyanate ester resin is at least one selected from the group consisting of bisphenol A type cyanate ester, bisphenol F type cyanate ester, bisphenol E type cyanate ester, bisphenol M type cyanate ester, DCPD type cyanate ester, naphthalene type cyanate ester, phenol-aldehyde type cyanate ester, and biphenyl cyanate ester.

[0131] As an option, the resin composition includes 1 to 35 parts by weight of a cyanate ester resin, based on 100 parts by weight of the maleimide resin and / or maleimide prepolymer and allyl-modified imide resin in total.

[0132] As an option, the cyanate ester resin includes a compound of structural formula (3):

[0133] Structural formula (3); wherein R is hydrogen or methyl, and n is an integer of 1 to 10.

[0134] Further, the maleimide resin and / or maleimide prepolymer includes at least one of structural formula (9)

[0135] to structural formula (18):

[0136] Structural formula (9);

[0137] Structural formula (10);

[0138] Structural formula (11);

[0139] Structural formula (12); wherein R2 is hydrogen, methyl, or ethyl, and R1 is methylene, ethylene, or

[0140] Structural formula (13);

[0141] Structural formula (14); wherein n is an integer of 1 to 10;

[0142] Structural Formula (15) wherein n is an integer from 1 to 10;

[0143] Structural Formula (16) wherein n is an integer from 1 to 10;

[0144] Structural Formula (17) wherein n is an integer from 1 to 10;

[0145] Structural Formula (18) wherein R is hydrogen, methyl or ethyl, and n is an integer from 1 to 10.

[0146] For example, the maleimide resin is selected from any one or more of the following trade name materials: BMI-1000, BMI-1000H, BMI-1100, BMI-1100H, BMI-2000, BMI-2300, BMI-3000, BMI-3000H, BMI-4000H, BMI-5000, BMI-5100, BMI-7000, BMI-7000H, manufactured by Yamazaki Chemical Co., Ltd.; BMI, BMI-70, BMI-80, manufactured by KI Chemical Co., Ltd., Japan; MIR-3000, MIR-5000, manufactured by Nippon Kayaku Co., Ltd.; X9-450, X9-470, manufactured by DIC Corp., Japan; D936, D937, D939, D950, manufactured by Sichuan Dongcai Co., Ltd.; and the like.

[0147] Further, the resin composition further comprises 0.1 to 30 parts by weight of a molybdenum compound.

[0148] As an option, the molybdenum compound is molybdenum disulfide, molybdenum dioxide, molybdenum trioxide, barium molybdate, potassium molybdate, phosphomolybdic acid, sodium phosphomolybdate, silicomolybdate, boron molybdate, molybdenum nitride, molybdenum carbide, zinc molybdate or a hydrate thereof, amine molybdate or a hydrate thereof, calcium molybdate or a hydrate thereof, sodium molybdate or a hydrate thereof, nickel molybdate or a hydrate thereof, ketone molybdate or a hydrate thereof, iron molybdate or a hydrate thereof, or an organic molybdenum compound.

[0149] Preferably, the molybdenum compound is zinc molybdate. In particular, the molybdenum compound is selected from at least one of anhydrous zinc molybdate, hydrous zinc molybdate (Zn3Mo2O8(OH)2), amine molybdate, amine molybdate hydrate ((NH4)Zn2Mo9·(H2O)), molybdenum dialkyldithiocarbamate, molybdenum dialkyldithiophosphate sulfidoxylate, talc coated with zinc molybdate, montmorillonite coated with zinc molybdate, and silica coated with zinc molybdate.

[0150] More preferably, the molybdenum compound is talc coated with zinc molybdate or talc coated with calcium molybdate.

[0151] For example, the molybdenum compound is selected from Huber's KG-911C, KG-911A or 1100.

[0152] As an alternative, the inorganic 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, glass fiber powder.

[0153] Preferably, the inorganic filler comprises silica.

[0154] As an alternative, the inorganic filler is surface treated with a silane coupling agent, which is at least one of an amino silane coupling agent, a carbon-carbon double bond containing silane coupling agent or an epoxy silane coupling agent.

[0155] Further, the resin composition comprises 0.001 to 5 parts by weight of a dispersing agent and 0.001 to 10 parts by weight of a coupling agent per 100 parts by weight.

[0156] As an alternative, the dispersing agent is selected from BYK-161 or / and BYK-111 by BYK-Chemie and the coupling agent is selected from KBM-402, KBM-403, KBM-502, KBM-503, KBM-603, KBM-903, KBM-573, KBM-602, KBM-1003, etc. by Shin-Etsu Chemical.

[0157] Further, the resin composition comprises 1 to 60 parts by weight of a flame retardant per 100 parts by weight of the sum of the allyl-modified imide resin, the maleimide resin and / or the maleimide prepolymer.

[0158] As an alternative, the flame retardant is selected from at least one of a bromine-based flame retardant, a phosphorus-based flame retardant, a nitrogen-based flame retardant, an organic silicon-based flame retardant, an organic metal-based flame retardant, an inorganic-based flame retardant. Of course, the kind of the flame retardant is not limited thereto, and it is understood that the added flame retardant can be selected according to the specific application field of the laminate, for example, an application field having a requirement for halogen, preferably a non-halogen flame retardant, such as a phosphorus-based flame retardant (for example, preferably a phosphazene or a flame retardant containing double DOPO) or a nitrogen-based flame retardant.

[0159] As an alternative, the bromine-based flame retardant is selected from decabromodiphenyl ether, decabromodiphenyl ethane, brominated styrene or tetrabromophthalic diamide.

[0160] As an optional embodiment, the phosphorus-based flame retardant is configured as inorganic phosphorus, inorganic phosphorus compound, or organic phosphorus-containing compound. Specifically, the inorganic phosphorus compound is any one of a phosphoric acid compound, a hypophosphoric acid compound, or a phosphorus oxide compound; the organic phosphorus-containing compound is a condensed phosphate ester compound, 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, etc. Or phosphazene, where m is an integer from 1 to 5.

[0161] As an alternative, the nitrogen-based flame retardant is selected from triazine compounds, cyanuric acid compounds, isocyanate compounds, phenothiazine, etc.

[0162] As an alternative, the organosilicon flame retardant can be organosilicon oil, organosilicon rubber, organosilicon resin, etc.

[0163] As an alternative, the organometallic flame retardant may be ferrocene, acetylacetone metal complex, organometallic carbonyl compound, etc.

[0164] As an alternative, the inorganic flame retardant may be aluminum hydroxide, magnesium hydroxide, aluminum oxide, barium oxide, etc.

[0165] Furthermore, the resin composition further includes 0.01 to 5 parts by weight of a catalyst, wherein the catalyst is at least one of an imidazole catalyst, a pyridine catalyst, or an organometallic salt catalyst.

[0166] As an alternative, the catalyst is at least one of 4-dimethylaminopyridine, 2-methylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, modified imidazole, and zinc octanoate.

[0167] Furthermore, one embodiment of the present invention provides an application of the resin composition. Specifically, the following technical solution is adopted:

[0168] The resin composition is the resin composition described above, which, by solid weight, comprises 20 to 100 parts by weight of maleimide resin and / or maleimide prepolymer; 1 to 80 parts by weight of allyl modified imide resin; 5 to 70 parts by weight of a mixture of reactive and non-reactive elastomers; and 30 to 200 parts by weight of inorganic filler.

[0169] The application refers to the use of the resin composition in prepregs, laminates, insulating boards, insulating films, circuit boards, and electrical devices.

[0170] As an option, the resin composition is applied to a prepreg, which comprises the resin composition and a reinforcing material, and the resin composition is attached to the surface of the reinforcing material.

[0171] As an option, the prepreg is prepared by dissolving the resin composition in a solvent to form a glue solution, immersing the reinforcing material in the glue solution, and then baking the immersed reinforcing material at 100-180°C for 1-15 min, and drying to obtain the prepreg.

[0172] As an option, the at least one solvent is selected from acetone, butanone, toluene, methyl isobutyl ketone, N, N-dimethylformamide, N, N-dimethylacetamide, ethylene glycol methyl ether, propylene glycol methyl ether, benzene, toluene, xylene, and cyclohexane.

[0173] As an option, the reinforcing material is selected from at least one of natural fibers, organic synthetic fibers, organic fabrics, and inorganic fabrics. More preferably, the reinforcing material is a glass fiber cloth, which preferably uses an open fiber cloth or a flat cloth; and the glass fiber cloth is preferably an E glass fiber cloth, an S glass fiber cloth, a T glass fiber cloth, or a Q glass fiber cloth.

[0174] Preferably, the glass fiber cloth is chemically treated with a coupling agent such as an epoxy silane or an amino silane to provide good water resistance and heat resistance, and to improve the interfacial bonding between the resin composition and the glass fiber cloth.

[0175] Further, the resin composition is applied to a laminate, which is a metal-clad laminate.

[0176] As an option, the laminate comprises a piece of the prepreg and a metal foil attached to at least one side surface of the prepreg.

[0177] Specifically, the laminate is prepared by coating a metal foil on one side or both sides of a piece of the prepreg, and hot-pressing at 0.2-2 MPa and 150-250°C for 2-4 hours to obtain a metal-clad laminate.

[0178] As an option, the laminate comprises a combined piece formed by folding two or more pieces of the prepreg, and a metal foil attached to at least one side surface of the combined piece.

[0179] Specifically, the laminate is prepared by folding two or more pieces of the prepreg to form a combined piece, coating a metal foil on one side or both sides of the combined piece, and hot-pressing at 0.2-2 MPa and 150-250°C for 2-4 hours to obtain a metal-clad laminate.

[0180] As an option, the metal foil can be a copper foil, an aluminum foil or other metal material, and the thickness thereof can be preferably, for example, 5 μm, 8 μm, 12 μm, 18 μm, 35 μm or 70 μm.

[0181] Further, the resin composition is applied to an insulating plate.

[0182] Further, the resin composition is applied to an insulating film, which includes an insulating resin layer composed of the resin composition.

[0183] Preferably, the insulating film further includes a carrier film, and the insulating resin layer is attached to the surface of the carrier film by a coating process.

[0184] Preferably, the carrier film is selected from a polyethylene terephthalate film, a release film, a copper foil or an aluminum foil, and is preferably a polyethylene terephthalate film.

[0185] Preferably, the insulating film further includes a protective film layer, which is attached to the side of the insulating resin layer facing away from the carrier film and covers the insulating resin layer. Preferably, the protective film layer and the carrier film are made of the same material, but this is not a limitation.

[0186] The method for preparing the insulating film includes: dissolving the resin composition in a solvent to prepare a resin composition glue; coating the resin composition glue on the carrier film; and then heating and drying the carrier film, so that the resin composition glue forms the insulating resin layer, thereby obtaining the insulating film.

[0187] Preferably, the solvent is selected from one or more of acetone, butanone, toluene, methyl isobutyl ketone, N, N-dimethylformamide, N, N-dimethylacetamide, ethylene glycol methyl ether and propylene glycol methyl ether.

[0188] Preferably, in the step of heating and drying the carrier film, the heating and drying conditions are baking at 100-200°C for 1-10 minutes, but this is not a limitation.

[0189] Further, the resin composition is applied to a circuit substrate, which includes any one of the prepreg, the laminate, the insulating plate and the insulating film.

[0190] Further, the resin composition is applied to an electrical device, which includes any one of the prepreg, the laminate, the insulating plate, the insulating film and the circuit substrate.

[0191] Compared with the prior art, the present application has the following beneficial effects: in the maleimide resin system, the reactive elastomer and the non-reactive elastomer are added and mixed, which not only maintains excellent heat resistance, high modulus and low CTE, but also improves the brittleness of the maleimide resin, i.e. improves the toughness, reduces the thermal expansion coefficient to reduce the warping defect, and also makes the resin composition have high compatibility, high adhesion, low water absorption, unexpected comprehensive performance improvement and production process performance, which can be applied to IC packaging and high-speed high-frequency field, and has wide application prospect.

[0192] The content of the present application will be described in detail below with specific examples and comparative examples.

[0193] Specifically, each of the examples and comparative examples provides a resin composition, the components of the resin composition and the weight parts (calculated by solid weight) of each component are shown in Table 1, and the specific brand materials of each component in Table 1 are shown in Table 2.

[0194] [Table 1]

[0195]

[0196]

[0197] [Table 2]

[0198]

[0199]

[0200] The resin composition of each example and comparative example is weighed according to the components and weight parts shown in Table 1, and then dissolved by solvent to prepare a glue solution with a solid content of 60%, the glue solution is coated on a T glass fiber cloth and soaked, then taken out and placed in a 160℃ air drying oven for baking for 3-6min to prepare a prepreg.

[0201] The prepared prepreg is cut to 300mm×300mm, and then one electrolytic copper foil is respectively stacked on the upper and lower sides of the prepreg to form a certain stack, which is sent into a vacuum press to press and prepare a copper-clad laminate.

[0202] The properties of the copper-clad laminates obtained in each of the above examples and comparative examples are shown in Table 3.

[0203] [Table 3]

[0204]

[0205] Table 3 Note:

[0206] 1) Tg: glass transition temperature, measured by DMA (Dynamic Mechanical Analysis) at a heating rate of 10°C / min, "none" means Tg is higher than 350°C;

[0207] 2) Dk and Df: measured at 10 GHz using the plate method according to IPC-TM-650 2.5.5.9;

[0208] 3) CTE (X-Y, a1): X / Y coefficient of thermal expansion, measured by TMA (Thermal Mechanical Analysis) at a heating rate of 10°C / min, in the temperature range 30-100°C;

[0209] 4) Water absorption: 3 samples of 10 cm x 10 cm, 0.40 mm thick, with the metal foil removed from both sides, are dried at 100°C for 2 hours, weighed, and the weight recorded as W1. The samples are then treated in a Pressure Cooker test machine at 121°C and 2 atmospheres for 2 hours, weighed, and the weight recorded as W2. The water absorption is determined as (W2-W1) / W1 x 100%;

[0210] 5) PCT 1 hr: immersion tin resistance after hydrothermal treatment. 3 samples of 10 cm x 10 cm, 0.80 mm thick, with the metal foil removed from both sides, are dried at 100°C for 2 hours, then treated in a Pressure Cooker test machine at 121°C and 2 atmospheres for 1 hour. The samples are then immersed in a tin bath at 288°C for 20 seconds, and visually inspected for delamination. If none of the 3 samples delaminates, the test is recorded as "pass". If any of the 3 samples delaminates, the test is recorded as "fail".

[0211] 6) Peel strength: measured according to the "after thermal stress" test conditions of IPC-TM-650 2.4.8, for the metal cap layer.

[0212] It should be understood that although the present specification is described in terms of embodiments, not every embodiment contains only one independent technical solution, and the present specification is described in this way only for the sake of clarity, and those skilled in the art should consider the specification as a whole, and the technical solutions in each embodiment can also be appropriately combined to form other embodiments that those skilled in the art can understand.

[0213] The series of detailed descriptions listed above are only specific descriptions of the feasible embodiments of the present application, and are not intended to limit the protection scope of the present application, and any equivalent embodiments or changes made without departing from the spirit of the present application should be included in the protection scope of the present application.

Claims

1. A resin composition, characterized in that, By solid weight, including: Maleimide resin and / or maleimide prepolymer, 20 to 100 parts by weight; Allyl-modified imide resin, 1-80 parts by weight; A mixture of reactive elastomers and non-reactive elastomers, 5 to 70 parts by weight; the ratio of the reactive elastomer to the non-reactive elastomer, based on solid weight, is 1:(0.1 to 20); Molybdenum compounds, 0.1 to 30 parts by weight; and, Inorganic filler, 30~200 parts by weight; The allyl-modified imide resin comprises the structural formula (1): Structural formula (1); Where R is , , , , or .

2. The resin composition according to claim 1, characterized in that, The reactive elastomer and the non-reactive elastomer are at least one of styrene-based, organosilicon-based, and acrylate-based elastomers, respectively.

3. The resin composition according to claim 2, characterized in that, The non-reactive elastomer is a styrene-based non-reactive elastomer, and the reactive elastomer is an acrylate-based reactive elastomer; or, the non-reactive elastomer is a styrene-based non-reactive elastomer, and the reactive elastomer is an organosilicon-based reactive elastomer; or, the non-reactive elastomer is an organosilicon-based non-reactive elastomer, and the reactive elastomer is an acrylate-based reactive elastomer; or, the non-reactive elastomer is an acrylate-based non-reactive elastomer, and the reactive elastomer is an organosilicon-based reactive elastomer.

4. The resin composition according to claim 1, characterized in that, The reactive elastomer contains at least one of the following: hydroxyl, epoxy, amino, cyano, unsaturated double bond, mercapto, and acid anhydride.

5. The resin composition according to claim 1, characterized in that, The reactive elastomer and the non-reactive elastomer are different types of compounds, and the reactive elastomer and the non-reactive elastomer do not contain the same repeating structural units.

6. The resin composition according to claim 1, characterized in that, The molybdenum compound is zinc molybdate.

7. The resin composition according to claim 1, characterized in that, The resin composition further includes epoxy resin and / or cyanate ester resin.

8. The use of a resin composition according to any one of claims 1 to 7 in prepreg, laminate, insulating board, insulating film, circuit board and electrical device.

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