Resin composition and use thereof

Abstract

The present application provides a resin composition and its application. The resin composition comprises 20-100 parts by weight of maleimide resin and / or maleimide prepolymer, 5-50 parts by weight of epoxy resin, 1-50 parts by weight of cyanate compound and 1-70 parts by weight of elastomer which is a mixture of reactive elastomer and non-reactive elastomer. Thus, the present application maintains excellent heat resistance, high modulus and low CTE, improves the brittleness of maleimide resin, increases the toughness, reduces the thermal expansion coefficient to reduce the warping defect, and makes the resin composition have high compatibility, high adhesion, low water absorption, unexpected comprehensive performance improvement and production process performance, and can be applied to IC packaging and high-speed high-frequency field, and has wide 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 application of the resin composition, and particularly relates to a prepreg, a laminated board, an insulating board, an insulating film, a circuit substrate and an electrical device using the resin composition. 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] 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.

[0004] For the material system of maleimide resin, one solution is to modify maleimide resin with diamine or allyl compound, and another solution is to add liquid crystal polymer. These solutions can improve toughness, but cause the heat resistance to decrease. Another solution is to add block copolymer, which can also improve toughness, but on the one hand, the compatibility with thermosetting resin is poor, and on the other hand, the adhesion between the resin composition and copper foil is reduced, thereby affecting the processing property.

[0005] In summary, the prior art solutions are difficult to ensure excellent heat resistance, high modulus and low CTE while taking into account excellent toughness, compatibility, adhesion and water absorption, thereby having better processability and performance. SUMMARY

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

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

[0008] The resin composition comprises 20-100 parts by weight of maleimide resin and / or maleimide prepolymer, 5-50 parts by weight of epoxy resin, 1-50 parts by weight of cyanate ester compound and 1-70 parts by weight of elastomer, which is a mixture of reactive elastomer and non-reactive elastomer, in terms of solid weight.

[0009] As an alternative, the reactive elastomer and the non-reactive elastomer are different types of compounds.

[0010] As an alternative, the reactive elastomer contains at least one of the following: hydroxyl, epoxy, amino, cyano, unsaturated double bond, mercapto, and acid anhydride.

[0011] Preferably, the reactive elastomer containing acrylate groups is a reactive elastomer containing methacrylate groups.

[0012] 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.

[0013] 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.

[0014] As an alternative, the non-reactive elastomer is at least one of styrene-based, silicone-based, and acrylate-based elastomers.

[0015] 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 TM4000 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 H1041, H1043, H1051, H1052, H1053, H1221; etc.

[0016] For example, the non-reactive silicone-based elastomer is selected from any one or more of the following brand 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.

[0017] Preferably, the non-reactive acrylate-based elastomer is a non-reactive methacrylate-based elastomer.

[0018] For example, the non-reactive acrylate-based elastomer is selected from any one or more of the following brand materials: Arkema M51, M52, M22, or D51N; Kuraray LA2250, LA2140, LA-2330, LA4285; etc.

[0019] As an option, the content ratio of the reactive elastomer and the non-reactive elastomer is 1 : (0.1-20) by weight of solid.

[0020] As an option, the content of the reactive elastomer is less than the content of the non-reactive elastomer by weight of solid.

[0021] 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 solid.

[0022] Preferably, the elastomer is a mixture of a partially hydrogenated styrene-based elastomer (which is a reactive elastomer) and a non-reactive elastomer of the methacrylate type, or a mixture of an epoxy-modified polybutadiene-based copolymer (which is a reactive elastomer) and a non-reactive elastomer of the methacrylate type, or a mixture of a partially hydrogenated styrene-based copolymer (which is a reactive elastomer) and a non-reactive elastomer of the silicone type.

[0023] As an option, the epoxy resin contains at least one naphthyl group and / or the cyanate compound contains at least one naphthyl group.

[0024] As an option, the epoxy resin includes a compound of structural formula (1) or / and a compound of structural formula (2):

[0025] Structural formula (1); wherein n is an integer from 1 to 10;

[0026] Structural formula (2). Of course, in addition thereto, the epoxy resin can also be selected from one or several of a bisphenol A epoxy resin, a bisphenol F epoxy resin, a tetraphenyl ethane epoxy resin, a triphenyl methane epoxy resin, a biphenyl type epoxy resin, a naphthalene ring type epoxy resin other than structural formula (1) and structural formula (2), a dicyclopentadiene type epoxy resin, an isocyanate type epoxy resin, an aralkyl linear phenol aldehyde epoxy resin, a bisphenol A phenol aldehyde type epoxy resin, a polyphenyl ether modified epoxy resin, an alicyclic type epoxy resin, a glycidyl amine type epoxy resin, a glycidyl ester type epoxy resin, a phosphorus-containing epoxy resin, a nitrogen-containing epoxy resin, a multi-functional epoxy resin.

[0027] Further, the cyanate compound is a compound containing at least one cyanate group, which can be a monomer, a polymer, a prepolymer or a combination thereof.

[0028] Preferably, the cyanate compound is a prepolymer, or a combination of a prepolymer and a monomer, or a combination of a prepolymer and a polymer.

[0029] As an option, the cyanate compound is selected from at least one of a bisphenol A type cyanate, a bisphenol F type cyanate, a bisphenol E type cyanate, a bisphenol M type cyanate, a DCPD type cyanate, a naphthalene type cyanate, a biphenyl cyanate.

[0030] As an option, the cyanate compound includes a compound of structural formula (3):

[0031] Structural formula (3); wherein R is hydrogen or methyl, and n is an integer from 1 to 10.

[0032] Further, the resin composition includes 30 to 250 parts by weight of an inorganic filler, based on 100 parts by weight of the epoxy resin, the maleimide resin and / or the maleimide prepolymer, and the cyanate compound in total.

[0033] As an option, 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.

[0034] Preferably, the inorganic filler includes silica.

[0035] As an option, 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.

[0036] Further, the resin composition includes 0.001 to 5 parts by weight of a dispersant and 0.001 to 10 parts by weight of a coupling agent, based on 100 parts by weight in total.

[0037] As an option, the dispersant is selected from BYK-161 or / and BYK-111 manufactured by BYK, 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. manufactured by SHIN-ETSU CHEMICAL.

[0038] As an option, the maleimide resin contains a structural formula (4):

[0039] The structural formula (4), wherein R is hydrogen or C1 to C5 alkyl.

[0040] Preferably, the maleimide resin and / or the maleimide prepolymer is selected from any one of 4,4'-diphenylmethane bismaleimide, polyphenylmethane maleimide, m-phenylene bismaleimide, bisphenol A diphenyl ether bismaleimide, 3,3'-dimethyl-5,5'-diethyl-4,4'-diphenylmethane bismaleimide, 4-methyl-1,3-phenylene bismaleimide, 1,6-bismaleimide-(2,2,4-trimethyl)hexane, 2,3-dimethylbenzene maleimide, 2,6-dimethylbenzene maleimide, N-phenyl maleimide, maleimide containing an aliphatic long chain structure, allyl compound-modified maleimide prepolymer, amine-modified maleimide prepolymer, acidic phenol compound-modified maleimide prepolymer, cyanate-modified maleimide prepolymer, or a combination of at least two thereof.

[0041] As a preferred solution, the maleimide resin and / or maleimide prepolymer is selected from any one of allyl compound-modified maleimide prepolymer, amine-modified maleimide prepolymer, acidic phenol compound-modified maleimide prepolymer, cyanate ester-modified maleimide prepolymer or a combination of at least two of them.

[0042] 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 Yamaichi Kagaku Seiyaku Co., Ltd.; BMI, BMI-70, BMI-80 manufactured by KI Kagaku Co., Ltd.; MIR-3000, MIR-5000 manufactured by Nippon Kayaku Co., Ltd.; X9-450, X9-470 manufactured by DIC Co., Ltd.; D936, D937, D939, D950 manufactured by Sichuan Dongcai Co., Ltd.; and the like.

[0043] Further, the resin composition further comprises 1 to 60 parts by weight of a flame retardant, based on 100 parts by weight of the total of the epoxy resin, the maleimide resin and / or maleimide prepolymer, and the cyanate ester compound.

[0044] As an optional solution, the flame retardant is selected from at least one of bromine-based flame retardant, phosphorus-based flame retardant, nitrogen-based flame retardant, organic silicon-based flame retardant, organic metal-based flame retardant, and inorganic-based flame retardant.

[0045] As an optional solution, the bromine-based flame retardant is selected from decabromobiphenyl ether, decabromobiphenyl ethane, brominated styrene, or tetrabromophthalic acid diamide.

[0046] As an optional solution, the phosphorus-based flame retardant is provided as inorganic phosphorus, inorganic phosphorus compound, or organic phosphorus compound. The inorganic phosphorus compound is any one of phosphoric acid compound, hypophosphorous acid compound, or phosphorus oxide compound, and the organic phosphorus compound is 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)phosphane, or phosphazene, wherein m is an integer of 1 to 5.

[0047] As an optional solution, the nitrogen-based flame retardant is selected from triazine compound, cyanuric acid compound, isocyanic acid compound, phenothiazine, and the like.

[0048] As an option, the organosilicon flame retardant can be organosilicon oil, organosilicon rubber, organosilicon resin, etc.

[0049] As an option, the organometallic flame retardant can be ferrocene, acetylacetone metal complex, organometallic carbonyl compound, etc.

[0050] As an option, the inorganic flame retardant can be aluminum hydroxide, magnesium hydroxide, aluminum oxide, barium oxide, etc.

[0051] Further, the resin composition further comprises 0.01-5 parts by weight of a catalyst, which is at least one of imidazole catalyst, pyridine catalyst, and organometallic salt catalyst.

[0052] As an option, the catalyst is at least one of 4-dimethylaminopyridine, 2-methylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, modified imidazole, and zinc octoate.

[0053] To achieve the above-mentioned object, one embodiment of the present application provides an application of a resin composition. The technical scheme is specifically as follows:

[0054] The resin composition is the resin composition described above, which comprises 20-100 parts by weight of maleimide resin and / or maleimide prepolymer, 5-50 parts by weight of epoxy resin, 1-50 parts by weight of cyanate compound, and 1-70 parts by weight of elastomer, which is a mixture of reactive elastomer and non-reactive elastomer, in terms of solid weight.

[0055] The application is the application of the resin composition in prepreg, laminated board, insulating board, insulating film, circuit board, and electrical device.

[0056] As an option, the resin composition is applied to prepreg, which comprises the resin composition and reinforcing material, and the resin composition is attached to the surface of the reinforcing material.

[0057] As an option, the preparation method of the prepreg is that the resin composition is dissolved with solvent to form glue solution, the reinforcing material is immersed in the glue solution, and then the immersed reinforcing material is baked at 100-180℃ for 1-15 min, and the prepreg is obtained after drying.

[0058] As an option, the at least one 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.

[0059] 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 selected from glass fiber cloth, preferably using an open fiber cloth or flat cloth; and the glass fiber cloth is preferably E glass fiber cloth, S glass fiber cloth, T glass fiber cloth, or Q glass fiber cloth.

[0060] 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.

[0061] Further, the resin composition is applied to a laminate, which is a metal-clad laminate.

[0062] As an option, the laminate includes a sheet of the prepreg and a metal foil attached to at least one side surface of the prepreg.

[0063] Specifically, the method for preparing the laminate is to cover a metal foil on one side or both sides of a sheet of the prepreg, and to hot-press form a metal-clad laminate under the conditions of 0.2-2 MPa and 150-250°C for 2-4 hours.

[0064] As an option, the laminate includes a combined sheet formed by folding two or more sheets of the prepreg on each other, and a metal foil attached to at least one side surface of the combined sheet.

[0065] Specifically, the method for preparing the laminate is to fold two or more sheets of the prepreg on each other to form a combined sheet, to cover a metal foil on one side or both sides of the combined sheet, and to hot-press form a metal-clad laminate under the conditions of 0.2-2 MPa and 150-250°C for 2-4 hours.

[0066] As an option, the metal foil can be a copper foil, an aluminum foil, or other metal materials, and the thickness thereof can be preferably, for example, 5 μm, 8 μm, 12 μm, 18 μm, 35 μm, or 70 μm.

[0067] Further, the resin composition is applied to an insulating board.

[0068] Further, the resin composition is applied to an insulating film, which includes an insulating resin layer formed of the resin composition.

[0069] Further, the resin composition is applied to a circuit substrate, which includes any one of the prepreg, the laminate, the insulating board, and the insulating film.

[0070] Further, the resin composition is applied to any one of the prepreg, the laminate, the insulating board, the insulating film, and the circuit substrate.

[0071] In summary, compared with the prior art, the resin composition of the embodiment of the present application has the advantages that: in the system of maleimide resin, epoxy resin, and cyanate ester compound, the reactive elastomer and the non-reactive elastomer are added and mixed, which maintains excellent heat resistance, high modulus, and low CTE, improves the brittleness of the maleimide resin, i.e., improves the toughness, reduces the thermal expansion coefficient to reduce the warping defect, and further has high compatibility, high adhesion, and low water absorption, achieves unexpected comprehensive performance improvement and production process performance, can be applied to IC packaging and high-speed high-frequency fields, and has wide application prospects. DETAILED DESCRIPTION

[0072] The following describes the specific embodiments of the present application. It should be noted that those skilled 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 protection scope of the embodiments of the present application.

[0073] The present application provides a resin composition with improved performance in these aspects, and further provides a prepreg, a laminate, an insulating board, an insulating film, a circuit substrate, and an electrical device using the resin composition.

[0074] Specifically, the embodiment of the present application provides a resin composition. The resin composition includes 20-100 parts by weight of maleimide resin and / or maleimide prepolymer, 5-50 parts by weight of epoxy resin, 1-50 parts by weight of cyanate ester compound, and 1-70 parts by weight of elastomer, which is a mixture of reactive elastomer and non-reactive elastomer, in terms of solid weight.

[0075] Thus, in the maleimide resin and / or maleimide prepolymer system, the reactive elastomer and the non-reactive elastomer are added and mixed, which maintains excellent heat resistance, high modulus, and low CTE, improves brittleness, i.e., increases toughness, and reduces thermal expansion coefficient to reduce warpage defects, and further provides the resin composition with high compatibility, high adhesion, and low water absorption, without generating new defects of poor compatibility and adhesion as in the background art, and achieves unexpected comprehensive performance improvement and production process performance, and can be applied to IC packaging and high-speed high-frequency fields, and has a broad application prospect.

[0076] 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, the reactive elastomer contains a butadiene-based repeating structural unit, and the non-reactive elastomer does not contain a butadiene-based repeating structural unit.

[0077] As an option, 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.

[0078] As an option, 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.

[0079] 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 TMHG252; 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.

[0080] As an alternative, the non-reactive elastomer is at least one of styrene-based, silicone-based, and acrylate-based elastomers.

[0081] 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.

[0082] 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.

[0083] Preferably, the acrylate-based non-reactive elastomer is a methacrylate-based non-reactive elastomer.

[0084] 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.

[0085] As an alternative, the content ratio of the reactive elastomer to the non-reactive elastomer is 1:(0.1 to 20) by solid weight.

[0086] As an option, the content of the reactive elastomer is less than the content of the non-reactive elastomer, by weight of solids.

[0087] 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 solids.

[0088] Thus, when too much reactive elastomer is added in the resin composition, the compatibility between different resins is good at room temperature, but the toughening groups with large molecular weight are difficult to be uniformly distributed in the whole cured product under high temperature conditions, affecting 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, affecting 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 according to the present application, the compatibility, CTE, water absorption and heat resistance can be considered.

[0089] Preferably, the elastomer is a mixture of a partially hydrogenated styrene-based elastomer (which is a reactive elastomer) and a non-reactive elastomer of methacrylate, or a mixture of an epoxy-modified polybutadiene-based copolymer (which is a reactive elastomer) and a non-reactive elastomer of methacrylate, or a mixture of a partially hydrogenated styrene-based copolymer (which is a reactive elastomer) and a non-reactive elastomer of silicone.

[0090] As an option, the epoxy resin contains at least one naphthyl group and / or the cyanate compound contains at least one naphthyl group.

[0091] As an option, the epoxy resin comprises a compound of structural formula (1) or / and a compound of structural formula (2):

[0092] Structural formula (1); wherein n is an integer of 1-10;

[0093] Formula (2). Of course, in addition to these, the epoxy resin can also be selected from one or more of a bisphenol A epoxy resin, a bisphenol F epoxy resin, a tetraphenylethane epoxy resin, a triphenylmethane epoxy resin, a biphenyl type epoxy resin, a naphthalene ring type epoxy resin other than Formula (1) and Formula (2), a dicyclopentadiene type epoxy resin, an isocyanate type epoxy resin, an aralkyl novolac epoxy resin, a bisphenol A novolac type epoxy resin, a polyphenylene ether modified epoxy resin, an alicyclic type epoxy resin, a glycidyl amine type epoxy resin, a glycidyl ester type epoxy resin, a phosphorus-containing epoxy resin, a nitrogen-containing epoxy resin, a multifunctional epoxy resin.

[0094] Further, the cyanate compound is a compound containing at least one cyanate group, which can be a monomer, a polymer, a prepolymer, or a combination thereof.

[0095] Preferably, the cyanate compound is a prepolymer, or a combination of a prepolymer and a monomer, or a combination of a prepolymer and a polymer.

[0096] As an option, the cyanate compound is selected from at least one of a bisphenol A cyanate, a bisphenol F cyanate, a bisphenol E cyanate, a bisphenol M cyanate, a DCPD cyanate, a naphthalene cyanate, a biphenyl cyanate.

[0097] As an option, the cyanate compound includes a compound of Formula (3):

[0098] Formula (3); wherein R is hydrogen or methyl, and n is an integer of 1 to 10.

[0099] Further, the resin composition further includes 30 to 250 parts by weight of an inorganic filler, based on 100 parts by weight of the epoxy resin, the maleimide resin and / or the maleimide prepolymer, and the cyanate compound in total.

[0100] As an option, the inorganic filler is selected from at least one of spherical silica, aluminum hydroxide, aluminum oxide, talc powder, aluminum nitride, boron nitride, silicon carbide, barium sulfate, barium titanate, strontium titanate, calcium carbonate, calcium silicate, mica, glass fiber powder.

[0101] Preferably, the inorganic filler includes silica.

[0102] As an option, 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.

[0103] Further, the resin composition includes 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.

[0104] As an option, the dispersing agent is selected from BYK-161 or / and BYK-111 manufactured by BYK, 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. manufactured by SHIN-ETSU CHEMICAL.

[0105] As an option, the maleimide resin contains a structural formula (4):

[0106] The structural formula (4), wherein R is hydrogen or C1 to C5 alkyl.

[0107] Preferably, the maleimide resin and / or maleimide prepolymer is selected from any one of or a combination of at least two of 4,4'-diphenylmethane bismaleimide, polybenzylmethane maleimide, m-styryl bismaleimide, bisphenol A diphenyl ether bismaleimide, 3,3'-dimethyl-5,5'-diethyl-4,4'-diphenylmethane bismaleimide, 4-methyl-1,3-styryl bismaleimide, 1,6-bismaleimide-(2,2,4-trimethyl)hexane, 2,3-dimethylbenzene maleimide, 2,6-dimethylbenzene maleimide, N-phenyl maleimide, maleimide containing an aliphatic long chain structure, allyl compound modified maleimide prepolymer, amine modified maleimide prepolymer, acidic phenol compound modified maleimide prepolymer, cyanate ester modified maleimide prepolymer.

[0108] As an option, the maleimide resin and / or maleimide prepolymer is selected from any one of or a combination of at least two of allyl compound modified maleimide prepolymer, amine modified maleimide prepolymer, acidic phenol compound modified maleimide prepolymer, cyanate ester modified maleimide prepolymer.

[0109] 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.; MIR-3000, MIR-5000 manufactured by Japan Chemicals Co., Ltd.; X9-450, X9-470 manufactured by DIC Corporation; D936, D937, D939, D950 manufactured by Sichuan Dongcai Co., Ltd.; and the like.

[0110] Further, the resin composition further includes 1 to 60 parts by weight of a flame retardant, based on 100 parts by weight of the total of the epoxy resin, the maleimide resin and / or the maleimide prepolymer, and the cyanate compound.

[0111] 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-based flame retardant, an organic metal-based flame retardant, and an inorganic-based flame retardant. Of course, the type of the flame retardant is not limited to this, 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, and 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 is preferred.

[0112] As an option, the bromine-based flame retardant is selected from decabromodiphenyl ether, decabromodiphenyl ethane, brominated styrene, or tetrabromophthalic diamide.

[0113] As an option, the phosphorus-based flame retardant is provided as an inorganic phosphorus, an inorganic phosphorus compound, or an organic phosphorus-containing 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-containing 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)phosphane, or a phosphazene, wherein m is an integer of 1 to 5.

[0114] As an option, the nitrogen-based flame retardant is selected from a triazine compound, a cyanuric acid compound, an isocyanic acid compound, a phenothiazine, and the like.

[0115] As an option, the organic silicon flame retardant can be an organic silicon oil, an organic silicon rubber, an organic silicon resin, etc.

[0116] As an option, the organic metal flame retardant can be ferrocene, an acetylacetone metal complex, an organic metal carbonyl compound, etc.

[0117] As an option, the inorganic flame retardant can be aluminum hydroxide, magnesium hydroxide, aluminum oxide, barium oxide, etc.

[0118] Further, the flame retardant is preferably a phosphorus-based flame retardant.

[0119] Further, the resin composition further comprises 0.01-5 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.

[0120] 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.

[0121] Further, an embodiment of the present application provides an application of the resin composition. Specifically, the following technical solution is adopted:

[0122] The resin composition is the resin composition described above, which comprises 20-100 parts by weight of a maleimide resin and / or a maleimide prepolymer, 5-50 parts by weight of an epoxy resin, 1-50 parts by weight of a cyanate compound, and 1-70 parts by weight of an elastomer, which is a mixture of a reactive elastomer and a non-reactive elastomer, in terms of solid weight;

[0123] The application is the application of the resin composition in prepreg, laminated board, insulating board, insulating film, circuit substrate, and electrical device.

[0124] 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.

[0125] As an option, the preparation method of the prepreg is as follows: the resin composition is dissolved with 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℃ for 1-15 min, and the prepreg is obtained after drying.

[0126] As an option, the at least one selected from the group consisting of 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.

[0127] As an option, the reinforcing material is at least one selected from the group consisting 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.

[0128] 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.

[0129] Further, the resin composition is applied to a laminate, which is a metal-clad laminate.

[0130] As an option, the laminate includes a piece of the prepreg and a metal foil attached to at least one side surface of the prepreg.

[0131] Specifically, the method for preparing the laminate is to cover a metal foil on one side or both sides of a piece of the prepreg, and to hot-press form a metal-clad laminate under the conditions of 0.2-2 MPa and 150-250°C for 2-4 hours.

[0132] As an option, the laminate includes 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.

[0133] Specifically, the method for preparing the laminate is to fold two or more pieces of the prepreg to form a combined piece, to cover a metal foil on one side or both sides of the combined piece, and to hot-press form a metal-clad laminate under the conditions of 0.2-2 MPa and 150-250°C for 2-4 hours.

[0134] As an option, the metal foil can be a copper foil, an aluminum foil, or other metal materials, and the thickness thereof can be preferably, for example, 5 μm, 8 μm, 12 μm, 18 μm, 35 μm, or 70 μm.

[0135] Further, the resin composition is applied to an insulating board.

[0136] Further, the resin composition is applied to an insulating film, which includes an insulating resin layer formed of the resin composition.

[0137] Preferably, the insulating film further comprises a carrier film, and the insulating resin layer is attached to the surface of the carrier film by a coating process.

[0138] Preferably, the carrier film is selected from polyethylene terephthalate film, release film, copper foil or aluminum foil, preferably polyethylene terephthalate film.

[0139] Preferably, the insulating film further comprises a protective film layer, which is attached to the side of the insulating resin layer 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, of course, not limited thereto.

[0140] The preparation method of the insulating film comprises: 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.

[0141] 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.

[0142] 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, of course, not limited thereto.

[0143] Further, the resin composition is applied to any one of the semi-cured sheet, the laminated board, the insulating board, and the insulating film.

[0144] Further, the resin composition is applied to any one of the semi-cured sheet, the laminated board, the insulating board, and the insulating film.

[0145] Compared with the prior art, the present application has the following beneficial effects: in the maleimide resin system, reactive elastomers and non-reactive elastomers are added, and the two kinds of elastomers are mixed and used, which not only maintains excellent heat resistance, high modulus and low CTE, but also improves the problem of large brittleness of the maleimide resin, i.e. improves the toughness, and reduces the thermal expansion coefficient to reduce the warping defect, and also can make the resin composition have high compatibility, high adhesion, low water absorption, achieve unexpected comprehensive performance improvement and production process performance, can be applied to IC packaging and high-speed high-frequency field, and has wide application prospect.

[0146] The present application will be described in detail below with specific examples and comparative examples.

[0147] Specifically, each of the examples and comparative examples provides a resin composition, the components of the resin composition and the weight parts (based on solid weight) of each component are shown in Table 1, and the specific grade materials of each component in Table 1 are shown in Table 2.

[0148] [Table 1]

[0149]

[0150]

[0151] [Table 2]

[0152] Material Grade Maleimide resin 1 BMI-2300, Dainichiseika Maleimide resin 2 MIR-3000, Nippon Kayaku Epoxy resin 1 HP-6000, DIC Epoxy resin 2 NC-3000, Nippon Kayaku Cyanate resin 1 Bisphenol A type, Yangzhou Tianqi Cyanate resin 2 Naphthalene type, Yangzhou Tianqi Reactive elastomer 1 SG-P3, Nippon Zeon Reactive elastomer 2 M1913, Asahi Kasei Non-reactive elastomer 1 H1052, Asahi Kasei Non-reactive elastomer 2 LA2140, Kuraray Flame retardant Decabromobisphenol A, Albemarle Catalyst 2-Ethyl-4-methylimidazole Filler Spherical silica

[0153] The resin composition of each example and comparative example is weighed according to the components and weight parts shown in Table 1, then a glue solution is prepared by solvent dissolution 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°C air drying oven for baking for 3-6 min, to obtain a prepreg.

[0154] The prepared prepreg is cut to 300mm x 300mm, then one electrolytic copper foil is respectively stacked on the upper and lower sides of the prepreg, and the stack is sent into a vacuum press to press and obtain a copper-clad laminate.

[0155] The properties of the copper-clad laminates obtained in each of the above examples and comparative examples are shown in Table 3.

[0156] [Table 3]

[0157]

[0158] Table 3 Notes:

[0159] 1) Tg: glass transition temperature, DMA (thermal mechanical analysis) is used, the heating rate is 10°C / min;

[0160] 2) Dk and Df: flat plate method according to IPC-TM-650 2.5.5.9, measured at 10GHz;

[0161] 3) CTE (X-Y, a1): X / Y thermal expansion coefficient, TMA (thermal mechanical analysis) is used, the heating rate is 10°C / min, the test temperature range is 30-100°C;

[0162] 4) Water absorption: Take 3 samples of 10 cm x 10 cm, 0.40 mm thick, both sides of the metal foil removed, dried at 100°C for 2 hours, weighed, and recorded as Wl; then in a pressure cooker test machine, at 121°C, 2 atmospheres for 2 hours, weighed, and recorded as W2, the water absorption is (W2-Wl) / Wl x 100%;

[0163] 5) PCT 1 hr: Tin immersion resistance after moisture heat treatment, take 3 samples of 10 cm x 10 cm, 0.80 mm thick, both sides of the metal foil removed, dried at 100°C for 2 hours, then use a pressure cooker test machine, at 121°C, 2 atmospheres for 1 hour, then immersed in a tin furnace at 288°C for 20 seconds, visually observe whether there is delamination, if there is no delamination in 3, record as

pass

not pass

[0164] 6) Peel strength: According to the "after thermal stress" test conditions in IPC-TM-650 2.4.8 method, test the peel strength of the metal cover layer.

[0165] 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 description of the specification is 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.

[0166] 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, Based on solid weight, the product comprises 20-100 parts by weight of maleimide resin and / or maleimide prepolymer, 5-50 parts by weight of epoxy resin, 1-50 parts by weight of cyanate ester compound, and 1-70 parts by weight of elastomer, wherein the elastomer is a mixture of reactive and non-reactive elastomers, wherein the epoxy resin contains at least one naphthyl group and / or the cyanate ester compound contains at least one naphthyl group; based on solid weight, the ratio of the reactive elastomer to the non-reactive elastomer is 1:(0.1-20).

2. The resin composition according to claim 1, characterized in that, The reactive elastomer and the non-reactive elastomer are different types of compounds.

3. The resin composition according to claim 2, characterized in that, The reactive elastomer contains at least one of the following: hydroxyl, epoxy, amino, cyano, unsaturated double bond, mercapto, and acid anhydride.

4. The resin composition according to claim 3, characterized in that, 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.

5. The resin composition according to claim 2, characterized in that, The non-reactive elastomer is at least one of styrene, silicone, or acrylate.

6. The resin composition according to claim 1, characterized in that, The content of the reactive elastomer is less than the content of the non-reactive elastomer by solid weight.

7. The resin composition according to claim 5, characterized in that, The acrylate-based non-reactive elastomer is a methacrylate-based non-reactive elastomer.

8. The resin composition according to claim 1, characterized in that, The epoxy resin includes compounds of structural formula (1) and / or compounds of structural formula (2): The structure is (1); where n is an integer from 1 to 10; Structural formula (2).

9. The use of any one of the resin compositions of claims 1 to 8 in prepregs, laminates, insulating boards, insulating films, circuit boards, and electrical devices.

Images