Resin composition and application thereof

Abstract

The present invention provides a resin composition and its application. The resin composition comprises, based on solid weight, 20 to 100 parts by weight of a maleimide resin and / or a maleimide prepolymer, 10 to 70 parts by weight of an epoxy resin, 5 to 50 parts by weight of a phenolic resin, 10 to 200 parts by weight of an inorganic filler, and 5 to 70 parts by weight of an elastomer, wherein the elastomer is a mixture of a reactive elastomer and a non-reactive elastomer, and the epoxy resin contains at least one naphthyl group and / or the phenolic resin contains at least one naphthyl group. In this manner, the reactive elastomer and the non-reactive elastomer are mixed, while the epoxy resin and the phenolic resin contain at least one naphthyl group. While maintaining excellent heat resistance, high modulus, and low CTE, the resin composition also exhibits high toughness, a low coefficient of thermal expansion to reduce warpage defects, high compatibility, high adhesion, and low water absorption. It also has excellent processability and is suitable for use in IC packaging and high-speed and high-frequency fields, possessing broad application prospects.

Description

Technical Field

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

[0002] In recent years, electronic devices have been moving towards miniaturization and higher performance. This has led to a continuous increase in wiring density and integration within printed circuit boards (PCBs), placing higher demands on the heat resistance and reliability of copper-clad laminates. In particular, during semiconductor packaging, a significant difference in the coefficient of thermal expansion between the semiconductor component and the substrate can easily lead to stress and substrate warping, resulting in serious problems such as poor connection between the semiconductor component and the substrate. Therefore, substrate materials require a lower coefficient of thermal expansion.

[0003] In the prior art, a high content of inorganic fillers is generally added to meet the requirement of a lower thermal expansion coefficient. However, a high content of inorganic fillers increases the viscosity of the resin glue, seriously affecting the product preparation process and the drilling processability of the PCB. Therefore, it is difficult to obtain a final cured product that simultaneously meets low thermal expansion and excellent processability through this method.

[0004] Maleimide resin has excellent heat resistance, high modulus, and low CTE, and is therefore widely used in high-performance circuit substrates. However, maleimide resin has the disadvantages of high curing temperature, high water absorption, and high brittleness.

[0005] Regarding the material system of maleimide resin, currently, one solution is to modify the maleimide resin using diamine or allyl compounds, and another solution is to add liquid crystal polymers. Although these solutions can improve toughness, they will lead to a decrease in heat resistance. Another solution is to add block copolymers. This solution can also improve toughness, but on the one hand, it has poor compatibility with thermosetting resins, and on the other hand, it will lead to a decrease in the adhesion between the resin composition and the copper foil, which will affect production and processability.

[0006] Epoxy resins have long held a dominant position in circuit substrates due to their excellent processing, mechanical, electrical, and physical properties, as well as their relatively low cost. However, epoxy resins' heat resistance, thermal expansion, and dielectric properties make them difficult to meet the requirements of high-performance substrates such as packaging substrates.

[0007] In summary, it is difficult for existing technical solutions 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 of the Invention

[0008] In view of the problems existing in the prior art, the object of the present invention is to provide a resin composition, as well as a prepreg, a laminate, an insulating board, an insulating film, a circuit substrate and an electrical device using the resin composition.

[0009] To achieve the above-mentioned purpose, one embodiment of the present invention provides a resin composition. Specifically, the following technical solution is adopted:

[0010] The invention comprises, based on solid weight, 20 to 100 parts by weight of a maleimide resin and / or a maleimide prepolymer, 10 to 70 parts by weight of an epoxy resin, 5 to 50 parts by weight of a phenolic resin, 10 to 200 parts by weight of an inorganic filler and 5 to 70 parts by weight of an elastomer, wherein the elastomer is a mixture of a reactive elastomer and a non-reactive elastomer, the epoxy resin contains at least one naphthyl group and / or the phenolic resin contains at least one naphthyl group.

[0011] As an optional solution, the epoxy resin is at least one of structural formulas (1) to (10):

[0012] Structural formula (1);

[0013] Structural formula (2); Structural formula (3); Structural formula (4);

[0014] Structural formula (5);

[0015] Structural formula (6);

[0016] Structural formula (7);

[0017] Structural formula (8);

[0018] Structural formula (9);

[0019] Structural formula (10);

[0020] In the structural formulae (1) to (10), n is an integer of 1 to 10.

[0021] As an alternative, the epoxy resin contains naphthyl ether groups.

[0022] For example, the epoxy resin is selected from any one or more of the following brands: DIC HP-4032SS, HP-4770, EXA-4750, HP-4700, HP-4710, HP-6000, HP-9500, HP-9540, HP-9900 or EXA-7311.

[0023] As an optional solution, the epoxy resin may also contain one or more of bisphenol A epoxy resin, bisphenol F epoxy resin, phosphorus-containing epoxy resin, o-cresol epoxy resin, bisphenol A novolac epoxy resin, phenol novolac epoxy resin, trifunctional phenol-type epoxy resin, tetraphenylethane epoxy resin, biphenyl-type epoxy resin, dicyclopentadiene-type epoxy resin, isocyanate-type epoxy resin, aralkyl linear novolac epoxy resin, alicyclic epoxy resin, glycidylamine-type epoxy resin, and glycidylester-type epoxy resin.

[0024] As an optional solution, the maleimide resin and / or maleimide prepolymer contains structural formula (17):

[0025] Structural formula (17); wherein, R is hydrogen or C1-C5 alkyl.

[0026] Preferably, the maleimide resin and / or maleimide prepolymer is selected from 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-dimethylphenylmaleimide, 2,6-dimethylphenylmaleimide, N-phenylmaleimide, maleimide containing aliphatic long chain structure, allyl compound modified maleimide prepolymer, amine modified maleimide prepolymer, acidic phenol compound modified maleimide prepolymer, cyanate modified maleimide prepolymer, any one or a combination of at least two thereof.

[0027] For example, the maleimide resin and / or maleimide prepolymer is selected from any one or more of the following brands: 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 Yamato Chemical Industry Co., Ltd.; BMI, BMI-70, BMI-80 manufactured by KI Chemical Industry Co., Ltd. of Japan; MIR-3000, MIR-5000 manufactured by Nippon Kayaku Co., Ltd.; X9-450, X9-470 manufactured by DIC Corporation of Japan; D936, D937, D939, D950 manufactured by Sichuan Dongcai Materials Co., Ltd.; and the like.

[0028] As an optional solution, the phenolic resin is at least one of structural formulas (11) to (13):

[0029] Structural formula (11);

[0030] Structural formula (12);

[0031] Structural formula (13);

[0032] In the structural formulae (11) to (13), n is an integer of 1 to 10.

[0033] For example, the phenolic resin is EXB-9500 manufactured by DIC or SN495 manufactured by Nippon Steel Chemical.

[0034] As an optional solution, the phenolic resin further contains bisphenol A phenolic resin, biphenyl phenolic resin, triazine-containing phenolic resin, bisphenol F phenolic resin or dicyclopentadiene phenolic resin.

[0035] As an optional solution, 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.

[0036] As an optional scheme, the reactive elastomer is selected from 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, cyanoacrylate copolymer, cyanomethacrylate copolymer, epoxy-containing silicone rubber, and epoxy-containing silicone resin.

[0037] For example, the reactive elastomer is selected from any one or more of the following brands: P1083, P1500, P5051, P2000, M1943, M1913, M1911; KURARE 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 manufactured by Nagase, Japan; SQ-20P, KHE-8000H manufactured by Nippon Kayaku; SQ502-8 manufactured by Arakawa Chemical; AY42-119 manufactured by DuPont Toray; etc.

[0038] As an optional solution, the non-reactive elastomer is at least one of styrene, silicone, and acrylate.

[0039] For example, the non-reactive styrene elastomer is selected from any one or more of the following brands: 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 H1041, H1043, H1051, H1052, H1053, H1221; etc.

[0040] For example, the silicone-based non-reactive elastomer is selected from any one or more of the following brands: X-40-2670, R-170S, X-40-2705, X-40-2701, KMP-600, KMP-605, X-52-7030 manufactured by Shin-Etsu Chemical; EP-2600, EP-2601, EP-2720, TMS-2670, EXL-2315, EXL-2655, etc. manufactured by DOW.

[0041] For example, the acrylic non-reactive elastomer is selected from any one or more of the following brands: M51, M52, M22 or D51N manufactured by Arkema; LA2250, LA2140, LA-2330, LA4285 manufactured by Kuraray Co., Ltd.; and the like.

[0042] As an optional solution, based on solid weight, the content ratio of the reactive elastomer to the non-reactive elastomer is 1:(0.1-20).

[0043] As an option, the reactive elastomer is present in an amount less than the non-reactive elastomer on a solids weight basis.

[0044] 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 based on solid weight.

[0045] As an alternative, the non-reactive elastomer has structural formula (14) and / or structural formula (15):

[0046] Structural formula (14); R1 is a C1-C5 alkyl group, and x is an integer from 1 to 100;

[0047] Structural formula (15); R2 is a C1-C5 alkyl group, and y is an integer from 1 to 100.

[0048] Preferably, the elastomer is a mixture of a partially hydrogenated styrene elastomer (which is a reactive elastomer) and a non-reactive elastomer of the methacrylate type, or a mixture of an epoxy-modified polybutadiene copolymer (which is a reactive elastomer) and a non-reactive elastomer of the methacrylate type, or a mixture of a partially hydrogenated styrene copolymer (which is a reactive elastomer) and a non-reactive elastomer of the silicone type.

[0049] As an optional solution, the inorganic filler is spherical silica surface-treated with an aminosilane coupling agent, and the aminosilane coupling agent has the structural formula (16):

[0050] Structural formula (16);

[0051] Wherein, R is a C1-C6 straight-chain alkylene group, and X is a methoxy group or an ethoxy group.

[0052] As an optional solution, the inorganic filler may also include at least one of 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.

[0053] As an optional solution, the inorganic filler is surface-treated with a silane coupling agent, and the silane coupling agent is at least one of an aminosilane coupling agent, a carbon-carbon double bond-containing silane coupling agent, or an epoxy silane coupling agent.

[0054] Furthermore, the resin composition comprises 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.

[0055] As an optional solution, the dispersant is selected from BYK-161 and / or 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 Xinyue Chemical.

[0056] Furthermore, based on 100 parts by weight of the epoxy resin, maleimide resin and / or maleimide prepolymer, and phenolic resin in total, the resin composition further comprises 1 to 60 parts by weight of a flame retardant.

[0057] As an optional solution, the flame retardant is selected from at least one of brominated flame retardants, phosphorus flame retardants, nitrogen flame retardants, organosilicon flame retardants, organometallic flame retardants, and inorganic flame retardants.

[0058] As an optional solution, the brominated flame retardant is selected from decabromodiphenyl ether, decabromodiphenyl ethane, brominated styrene or tetrabromophthalamide.

[0059] As an optional solution, the phosphorus-based flame retardant is set to inorganic phosphorus, an inorganic phosphorus compound or an organic phosphorus-containing compound. Wherein, the inorganic phosphorus compound is any one of a phosphoric acid compound, a hypophosphorous acid compound, and a phosphorus oxide compound, and the organic phosphorus-containing compound is a condensed phosphate 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 phosphazene, wherein m is an integer of 1-5.

[0060] As an optional solution, the nitrogen-based flame retardant is selected from triazine compounds, cyanuric acid compounds, isocyanic acid compounds, phenothiazine, etc.

[0061] As an optional solution, the organic silicon flame retardant can be organic silicon oil, organic silicon rubber, organic silicon resin, etc.

[0062] As an optional solution, the organic metal flame retardant can be ferrocene, acetylacetone metal complex, organic metal carbonyl compound, etc.

[0063] As an optional solution, the inorganic flame retardant can be aluminum hydroxide, magnesium hydroxide, aluminum oxide, barium oxide, etc.

[0064] Furthermore, the resin composition further comprises 0.01 to 5 parts by weight of a catalyst, wherein the catalyst is at least one of an imidazole catalyst, a pyridine catalyst, and an organic metal salt catalyst.

[0065] As an optional solution, the catalyst is at least one of 4-dimethylaminopyridine, 2-methylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, modified imidazole, and zinc octoate.

[0066] To achieve the above-mentioned purpose, one embodiment of the present invention provides an application of a resin composition. Specifically, the following technical solution is adopted:

[0067] The resin composition adopts the resin composition described above, and the resin composition comprises, based on solid weight, 20 to 100 parts by weight of a maleimide resin and / or a maleimide prepolymer, 10 to 70 parts by weight of an epoxy resin, 5 to 50 parts by weight of a phenolic resin, 10 to 200 parts by weight of an inorganic filler, and 5 to 70 parts by weight of an elastomer, wherein the elastomer is a mixture of a reactive elastomer and a non-reactive elastomer, the epoxy resin contains at least one naphthyl group and / or the phenolic resin contains at least one naphthyl group;

[0068] The application is the application of the resin composition in prepregs, laminates, insulating boards, insulating films, circuit substrates and electrical devices.

[0069] As an optional solution, the resin composition is applied to a prepreg, the prepreg comprises the resin composition and a reinforcing material, and the resin composition is attached to the surface of the reinforcing material.

[0070] As an optional solution, the preparation method of the semi-cured sheet is: dissolving the resin composition with a solvent to prepare a glue solution, impregnating the reinforcing material in the glue solution, and then baking the impregnated reinforcing material at 100-180°C for 1-15 minutes, and the semi-cured sheet can be obtained after drying.

[0071] As an optional solution, the solvent is at least one 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.

[0072] As an alternative, 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 glass fiber cloth, preferably open fiber cloth or flat cloth; and preferably, the glass fiber cloth is E glass fiber cloth, S glass fiber cloth, T glass fiber cloth, or Q glass fiber cloth.

[0073] Preferably, the glass fiber cloth is chemically treated with a coupling agent such as epoxy silane or amino silane to provide good water resistance and heat resistance and improve the interface bonding between the resin composition and the glass fiber cloth.

[0074] Furthermore, the resin composition is applied to a laminate, and the laminate is a metal foil-clad laminate.

[0075] As an optional solution, the laminate includes a sheet of the prepreg and a metal foil attached to at least one side surface of the prepreg.

[0076] Specifically, the laminate is prepared by covering one or both sides of a prepreg with metal foil, pressing at 0.2-2 MPa and 150-250° C. for 2-4 hours to obtain a metal foil laminate.

[0077] As an optional solution, the laminate includes a composite sheet formed by overlapping two or more prepregs and a metal foil attached to at least one surface of the composite sheet.

[0078] Specifically, the preparation method of the laminate is: stacking two or more semi-cured sheets to form a composite sheet, covering one or both sides of the composite sheet with metal foil, pressing at 0.2-2 MPa and 150-250°C for 2-4 hours to obtain a metal foil laminate by hot pressing.

[0079] As an optional solution, the metal foil may be copper foil, aluminum foil or other metal materials, and its thickness may preferably be 5 μm, 8 μm, 12 μm, 18 μm, 35 μm or 70 μm.

[0080] Furthermore, the resin composition is applied to an insulation board.

[0081] Furthermore, the resin composition is applied to an insulating film, which includes an insulating resin layer composed of the resin composition.

[0082] Furthermore, the resin composition is applied to a circuit substrate, and the circuit substrate includes any one of the prepreg, the laminate, the insulating plate, and the insulating film.

[0083] Furthermore, the resin composition is applied to an electrical device, and the electrical device includes any one of the prepreg, the laminate, the insulating plate, the insulating film, and the circuit substrate.

[0084] In summary, compared with the prior art, the beneficial effect of one embodiment of the present invention is that: a reactive elastomer and a non-reactive elastomer are added to the system of maleimide resin, epoxy resin, and phenolic resin, and the epoxy resin and the phenolic resin contain at least one naphthyl group. While maintaining excellent heat resistance, high modulus, and low CTE, the resin composition also has high toughness, low thermal expansion coefficient to reduce warping defects, high compatibility, high adhesion, low water absorption, and excellent processability. It can be applied to IC packaging and high-speed and high-frequency fields, and has broad application prospects. DETAILED DESCRIPTION

[0085] The following is a specific implementation of the embodiment of the present invention. It should be noted that for ordinary technicians in this field, several improvements and modifications can be made without departing from the principles of the embodiment of the present invention. These improvements and modifications are also considered to be within the scope of protection of the embodiment of the present invention.

[0086] The present invention provides a resin composition, and based on the resin composition, further provides a prepreg, a laminate, an insulating plate, an insulating film, a circuit substrate and an electrical device using the resin composition.

[0087] Specifically, one embodiment of the present invention provides a resin composition. The resin composition comprises, based on solid weight, 20 to 100 parts by weight of a maleimide resin and / or a maleimide prepolymer, 10 to 70 parts by weight of an epoxy resin, 5 to 50 parts by weight of a phenolic resin, 10 to 200 parts by weight of an inorganic filler, and 5 to 70 parts by weight of an elastomer, wherein the elastomer is a mixture of a reactive elastomer and a non-reactive elastomer, the epoxy resin contains at least one naphthyl group, and / or the phenolic resin contains at least one naphthyl group.

[0088] In this way, reactive elastomers and non-reactive elastomers are added to the system of maleimide resin, epoxy resin, and phenolic resin, and the epoxy resin and phenolic resin contain at least one naphthyl group. While maintaining excellent heat resistance, high modulus, and low CTE, the resin composition also has high toughness, low thermal expansion coefficient to reduce warping defects, high compatibility, high adhesion, low water absorption, and excellent processability. It can be used in IC packaging and high-speed and high-frequency fields, and has broad application prospects.

[0089] As an optional solution, the epoxy resin is at least one of structural formulas (1) to (10):

[0090] Structural formula (1); Structural formula (2); Structural formula (3); Structural formula (4);

[0091] Structural formula (5);

[0092] Structural formula (6);

[0093] Structural formula (7);

[0094] Structural formula (8);

[0095] Structural formula (9);

[0096] Structural formula (10);

[0097] In the structural formulae (1) to (10), n is an integer of 1 to 10.

[0098] As an alternative, the epoxy resin contains naphthyl ether groups.

[0099] For example, the epoxy resin is selected from any one or more of the following brands: DIC HP-4032SS, HP-4770, EXA-4750, HP-4700, HP-4710, HP-6000, HP-9500, HP-9540, HP-9900 or EXA-7311.

[0100] As an optional solution, the epoxy resin may also contain one or more of bisphenol A epoxy resin, bisphenol F epoxy resin, phosphorus-containing epoxy resin, o-cresol epoxy resin, bisphenol A novolac epoxy resin, phenol novolac epoxy resin, trifunctional phenol-type epoxy resin, tetraphenylethane epoxy resin, biphenyl-type epoxy resin, dicyclopentadiene-type epoxy resin, isocyanate-type epoxy resin, aralkyl linear novolac epoxy resin, alicyclic epoxy resin, glycidylamine-type epoxy resin, and glycidylester-type epoxy resin.

[0101] As an optional solution, the maleimide resin and / or maleimide prepolymer contains structural formula (17):

[0102] Structural formula (17); wherein, R is hydrogen or C1-C5 alkyl.

[0103] Preferably, the maleimide resin and / or maleimide prepolymer is selected from 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-dimethylphenylmaleimide, 2,6-dimethylphenylmaleimide, N-phenylmaleimide, maleimide containing aliphatic long chain structure, allyl compound modified maleimide prepolymer, amine modified maleimide prepolymer, acidic phenol compound modified maleimide prepolymer, cyanate modified maleimide prepolymer, any one or a combination of at least two thereof.

[0104] For example, the maleimide resin and / or maleimide prepolymer is selected from any one or more of the following brands: 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 Yamato Chemical Industry Co., Ltd.; BMI, BMI-70, BMI-80 manufactured by KI Chemical Industry Co., Ltd. of Japan; MIR-3000, MIR-5000 manufactured by Nippon Kayaku Co., Ltd.; X9-450, X9-470 manufactured by DIC Corporation of Japan; D936, D937, D939, D950 manufactured by Sichuan Dongcai Materials Co., Ltd.; and the like.

[0105] As an optional solution, the phenolic resin is at least one of structural formulas (11) to (13):

[0106] Structural formula (11);

[0107] Structural formula (12);

[0108] Structural formula (13);

[0109] In the structural formulae (11) to (13), n is an integer of 1 to 10.

[0110] For example, the phenolic resin is EXB-9500 manufactured by DIC or SN495 manufactured by Nippon Steel Chemical.

[0111] As an optional solution, the phenolic resin further contains bisphenol A phenolic resin, biphenyl phenolic resin, triazine-containing phenolic resin, bisphenol F phenolic resin or dicyclopentadiene phenolic resin.

[0112] As an optional solution, 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.

[0113] As an optional scheme, the reactive elastomer is selected from 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, cyanoacrylate copolymer, cyanomethacrylate copolymer, epoxy-containing silicone rubber, and epoxy-containing silicone resin.

[0114] For example, the reactive elastomer is selected from any one or more of the following brands: P1083, P1500, P5051, P2000, M1943, M1913, M1911; KURARE 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 manufactured by Nagase, Japan; SQ-20P, KHE-8000H manufactured by Nippon Kayaku; SQ502-8 manufactured by Arakawa Chemical; AY42-119 manufactured by DuPont Toray; etc.

[0115] As an optional solution, the non-reactive elastomer is at least one of styrene, silicone, and acrylate.

[0116] For example, the non-reactive styrene elastomer is selected from any one or more of the following brands: SEPTON manufactured by KURARE, Japan TM 2000 series (2002, 2004, 2005, 2006, 2063, 2104), SEPTON TM 4000 series (4033, 4044, 4055, 4077), HYBRAR TM7000 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.

[0117] For example, the silicone-based non-reactive elastomer is selected from any one or more of the following brands: X-40-2670, R-170S, X-40-2705, X-40-2701, KMP-600, KMP-605, X-52-7030 manufactured by Shin-Etsu Chemical; EP-2600, EP-2601, EP-2720, TMS-2670, EXL-2315, EXL-2655, etc. manufactured by DOW.

[0118] For example, the acrylic non-reactive elastomer is selected from any one or more of the following brands: M51, M52, M22 or D51N manufactured by Arkema; LA2250, LA2140, LA-2330, LA4285 manufactured by Kuraray Co., Ltd.; and the like.

[0119] As an optional solution, based on solid weight, the content ratio of the reactive elastomer to the non-reactive elastomer is 1:(0.1-20).

[0120] As an option, the reactive elastomer is present in an amount less than the non-reactive elastomer on a solids weight basis.

[0121] 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 based on solid weight.

[0122] When too much reactive elastomer is added to a resin composition, compatibility between different resins is good at room temperature. However, at high temperatures, the larger molecular weight toughening groups are difficult to evenly distribute throughout the entire cured product, affecting CTE, water absorption, and heat resistance. When too little reactive elastomer is added to a resin composition, compatibility between different resins is poor at room temperature, affecting large-scale production processability and making it difficult to obtain a resin composition with stable overall performance. However, the ratio of the reactive elastomer to the non-reactive elastomer according to the present invention can achieve a balance between compatibility, CTE, water absorption, and heat resistance.

[0123] As an alternative, the reactive elastomer and the non-reactive elastomer are different compounds. Specifically, the reactive elastomer and the non-reactive elastomer do not contain the same repeating structural units. For example, when the reactive elastomer contains butadiene repeating structural units, the non-reactive elastomer does not contain butadiene repeating structural units.

[0124] Preferably, the elastomer is a mixture of a partially hydrogenated styrene elastomer (which is a reactive elastomer) and a non-reactive elastomer of the methacrylate type, or a mixture of an epoxy-modified polybutadiene copolymer (which is a reactive elastomer) and a non-reactive elastomer of the methacrylate type, or a mixture of a partially hydrogenated styrene copolymer (which is a reactive elastomer) and a non-reactive elastomer of the silicone type.

[0125] As an alternative, the non-reactive elastomer has structural formula (14) and / or structural formula (15):

[0126] Structural formula (14); R1 is a C1-C5 alkyl group, and x is an integer from 1 to 100;

[0127] Structural formula (15); R2 is a C1-C5 alkyl group, and y is an integer from 1 to 100.

[0128] As an optional solution, the inorganic filler is spherical silica surface-treated with an aminosilane coupling agent, and the aminosilane coupling agent has the structural formula (16):

[0129] Structural formula (16);

[0130] Wherein, R is a C1-C6 straight-chain alkylene group, and X is a methoxy group or an ethoxy group.

[0131] As an optional solution, the inorganic filler may also include at least one of aluminum hydroxide, aluminum oxide, talc, aluminum nitride, boron nitride, silicon carbide, barium sulfate, barium titanate, strontium titanate, calcium carbonate, calcium silicate, mica, and glass fiber powder.

[0132] As an optional solution, the inorganic filler is surface-treated with a silane coupling agent, and the silane coupling agent is at least one of an aminosilane coupling agent, a carbon-carbon double bond-containing silane coupling agent, or an epoxy silane coupling agent.

[0133] Furthermore, the resin composition comprises 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.

[0134] As an optional solution, the dispersant is selected from BYK-161 and / or 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 Xinyue Chemical.

[0135] Furthermore, based on 100 parts by weight of the epoxy resin, maleimide resin and / or maleimide prepolymer, and phenolic resin in total, the resin composition further comprises 1 to 60 parts by weight of a flame retardant.

[0136] As an optional solution, the flame retardant is selected from at least one of a brominated flame retardant, a phosphorus flame retardant, a nitrogen flame retardant, an organosilicon flame retardant, an organometallic flame retardant, and an inorganic flame retardant. Of course, the type of flame retardant is not limited thereto. It is understood that the added flame retardant can be selected based on the specific application of the laminate. For example, for applications requiring halogen, non-halogen flame retardants such as phosphorus flame retardants (e.g., preferably phosphazenes or flame retardants containing bis-DOPO) or nitrogen flame retardants are preferred.

[0137] As an optional solution, the brominated flame retardant is selected from decabromodiphenyl ether, decabromodiphenyl ethane, brominated styrene or tetrabromophthalamide.

[0138] As an optional solution, the phosphorus-based flame retardant is set to inorganic phosphorus, an inorganic phosphorus compound or an organic phosphorus-containing compound. Wherein, the inorganic phosphorus compound is any one of a phosphoric acid compound, a hypophosphorous acid compound, and a phosphorus oxide compound, and the organic phosphorus-containing compound is a condensed phosphate 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 phosphazene, wherein m is an integer of 1-5.

[0139] As an optional solution, the nitrogen-based flame retardant is selected from triazine compounds, cyanuric acid compounds, isocyanic acid compounds, phenothiazine, etc.

[0140] As an optional solution, the organic silicon flame retardant can be organic silicon oil, organic silicon rubber, organic silicon resin, etc.

[0141] As an optional solution, the organic metal flame retardant can be ferrocene, acetylacetone metal complex, organic metal carbonyl compound, etc.

[0142] As an optional solution, the inorganic flame retardant can be aluminum hydroxide, magnesium hydroxide, aluminum oxide, barium oxide, etc.

[0143] Furthermore, the resin composition further comprises 0.01 to 5 parts by weight of a catalyst, wherein the catalyst is at least one of an imidazole catalyst, a pyridine catalyst, and an organic metal salt catalyst.

[0144] As an optional solution, the catalyst is at least one of 4-dimethylaminopyridine, 2-methylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, modified imidazole, and zinc octoate.

[0145] Furthermore, one embodiment of the present invention provides an application of a resin composition, which specifically adopts the following technical solution:

[0146] The resin composition adopts the resin composition described above, and the resin composition comprises, based on solid weight, 20 to 100 parts by weight of a maleimide resin and / or a maleimide prepolymer, 10 to 70 parts by weight of an epoxy resin, 5 to 50 parts by weight of a phenolic resin, 10 to 200 parts by weight of an inorganic filler, and 5 to 70 parts by weight of an elastomer, wherein the elastomer is a mixture of a reactive elastomer and a non-reactive elastomer, the epoxy resin contains at least one naphthyl group and / or the phenolic resin contains at least one naphthyl group;

[0147] The application is the application of the resin composition in prepregs, laminates, insulating boards, insulating films, circuit substrates and electrical devices.

[0148] As an optional solution, the resin composition is applied to a prepreg, the prepreg comprises the resin composition and a reinforcing material, and the resin composition is attached to the surface of the reinforcing material.

[0149] As an optional solution, the preparation method of the semi-cured sheet is: dissolving the resin composition with a solvent to prepare a glue solution, impregnating the reinforcing material in the glue solution, and then baking the impregnated reinforcing material at 100-180°C for 1-15 minutes, and the semi-cured sheet can be obtained after drying.

[0150] As an optional solution, the solvent is at least one 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.

[0151] As an alternative, 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 glass fiber cloth, preferably open fiber cloth or flat cloth; and preferably, the glass fiber cloth is E glass fiber cloth, S glass fiber cloth, T glass fiber cloth, or Q glass fiber cloth.

[0152] Preferably, the glass fiber cloth is chemically treated with a coupling agent such as epoxy silane or amino silane to provide good water resistance and heat resistance and improve the interface bonding between the resin composition and the glass fiber cloth.

[0153] Furthermore, the resin composition is applied to a laminate, and the laminate is a metal foil-clad laminate.

[0154] As an optional solution, the laminate includes a sheet of the prepreg and a metal foil attached to at least one side surface of the prepreg.

[0155] Specifically, the laminate is prepared by covering one or both sides of a prepreg with metal foil, pressing at 0.2-2 MPa and 150-250° C. for 2-4 hours to obtain a metal foil laminate.

[0156] As an optional solution, the laminate includes a composite sheet formed by overlapping two or more prepregs and a metal foil attached to at least one surface of the composite sheet.

[0157] Specifically, the preparation method of the laminate is: stacking two or more semi-cured sheets to form a composite sheet, covering one or both sides of the composite sheet with metal foil, pressing at 0.2-2 MPa and 150-250°C for 2-4 hours to obtain a metal foil laminate by hot pressing.

[0158] As an optional solution, the metal foil may be copper foil, aluminum foil or other metal materials, and its thickness may preferably be 5 μm, 8 μm, 12 μm, 18 μm, 35 μm or 70 μm.

[0159] Furthermore, the resin composition is applied to an insulation board.

[0160] Furthermore, the resin composition is applied to an insulating film, which includes an insulating resin layer composed of the resin composition.

[0161] Preferably, the insulating film further comprises a carrier film, and the insulating resin layer is attached to the surface of the carrier film through a coating process.

[0162] Preferably, the carrier film is selected from polyethylene terephthalate film, release film, copper foil or aluminum foil, preferably polyethylene terephthalate film.

[0163] Preferably, the insulating film further comprises 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 limiting.

[0164] The preparation method of the insulating film includes: adding the resin composition into a solvent to dissolve it to prepare a glue solution of the resin composition; coating the glue solution of the resin composition on the carrier film; and then heating and drying the carrier film, so that the glue solution of the resin composition forms the insulating resin layer, thereby obtaining the insulating film.

[0165] 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.

[0166] 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, it is not limited thereto.

[0167] Furthermore, the resin composition is applied to a circuit substrate, and the circuit substrate includes any one of the prepreg, the laminate, the insulating plate, and the insulating film.

[0168] Furthermore, the resin composition is applied to an electrical device, and the electrical device includes any one of the prepreg, the laminate, the insulating plate, the insulating film, and the circuit substrate.

[0169] Compared with the existing technology, the present invention has the following beneficial effects: a reactive elastomer and a non-reactive elastomer are added to the system of maleimide resin, epoxy resin and phenolic resin, and the epoxy resin and the phenolic resin contain at least one naphthyl group. While maintaining excellent heat resistance, high modulus and low CTE, the resin composition also has high toughness, low thermal expansion coefficient to reduce warping defects, high compatibility, high adhesion, low water absorption, excellent processability, can be applied to IC packaging and high-speed and high-frequency fields, and has broad application prospects.

[0170] The present invention will be described in detail below with reference to specific embodiments and comparative examples.

[0171] Specifically, each embodiment and comparative example provides a resin composition, the components of the resin composition and the weight parts of each component (based on solid weight) are shown in Table 1, and the specific brand materials of each component in Table 1 are shown in Table 2.

[0172] [Table 1]

[0173]

[0174]

[0175] [Table 2]

[0176]

[0177] The resin compositions of the embodiments and comparative examples were weighed according to the components and weight parts shown in Table 1, and then dissolved in a solvent to prepare an adhesive solution with a solid content of 60%. The adhesive solution was applied to T-glass fiber cloth and soaked, then taken out and baked in a 160°C forced air drying oven for 3 to 6 minutes to prepare a prepreg.

[0178] The prepared prepreg is cut into 300mm×300mm, and then a piece of electrolytic copper foil is stacked on the upper and lower sides of the prepreg respectively to form a certain stacking structure, and then sent into a vacuum press for pressing to obtain a copper-clad laminate.

[0179] The properties of the copper-clad laminates obtained in the above embodiments and comparative examples are shown in Table 3.

[0180] [Table 3]

[0181]

[0182] Notes to Table 3:

[0183] 1) Tg: glass transition temperature, using DMA (thermomechanical analysis) at a heating rate of 10°C / min;

[0184] 2) Dk and Df: measured at 10 GHz using the flat plate method according to IPC-TM-650 2.5.5.9;

[0185] 3) CTE(XY,α1): X / Y coefficient of thermal expansion, using TMA (thermomechanical analysis), a heating rate of 10°C / min, and a test temperature range of 30-100°C;

[0186] 4) Water Absorption: Three samples, 10 cm x 10 cm, 0.40 mm thick, with the metal foil removed from both sides, were dried at 100°C for 2 hours and weighed (W1). The samples were then cooked in a pressure cooker at 121°C and 2 atm for 2 hours and weighed (W2). The water absorption was determined as (W2 - W1) / W1 × 100%.

[0187] 5) PCT 1hr: Heat resistance after wet heat treatment (immersion tinning). Three samples, 10 cm x 10 cm, 0.80 mm thick, with metal foil removed from both sides, were dried at 100°C for 2 hours. The samples were then heat-treated at 121°C and 2 atmospheres for 1 hour using a pressure cooker tester. The samples were then immersed in a tin bath at 288°C for 20 seconds and visually inspected for delamination. If any of the three samples showed no delamination, they were scored as "passed." If any delamination was present, they were scored as "failed."

[0188] 6) Peel strength: The peel strength of the metal cover layer was tested according to the "after thermal stress" experimental conditions in IPC-TM-650 2.4.8 method.

Claims

1. A resin composition, characterized in that The invention relates to a novel composition comprising, based on solid weight, 20 to 100 parts by weight of a maleimide resin and / or a maleimide prepolymer, 10 to 70 parts by weight of an epoxy resin, 5 to 50 parts by weight of a phenolic resin, 10 to 200 parts by weight of an inorganic filler, and 5 to 70 parts by weight of an elastomer, wherein the elastomer is a mixture of a reactive elastomer and a non-reactive elastomer, the epoxy resin contains at least one naphthyl group and / or the phenolic resin contains at least one naphthyl group; and the content ratio of the reactive elastomer to the non-reactive elastomer, based on solid weight, is 1:(0.1 to 20).

2. The resin composition according to claim 1, wherein The epoxy resin is at least one of the structural formulas (1) to (10): Structural formula (1); Structural formula (2); Structural formula (3); Structural formula (4); Structural formula (5); Structural formula (6); Structural formula (7); Structural formula (8); Structural formula (9); Structural formula (10); Wherein, n in structural formula (1) to structural formula (10) is an integer of 1 to 10.

3. The resin composition according to claim 1, wherein 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 acid anhydride group.

4. The resin composition according to claim 1, characterized in that The non-reactive elastomer is at least one of styrene, silicone or acrylic.

5. The resin composition according to claim 4, characterized in that The non-reactive elastomer has the structural formula (14) and / or the structural formula (15): Structural formula (14); R1 is a C1-C5 alkyl group, and x is an integer from 1 to 100; Structural formula (15); R2 is a C1~C5 alkyl group, and y is an integer from 1 to 100.

6. The resin composition according to claim 1, characterized in that The phenolic resin is at least one of the structural formulas (11) to (13): Structural formula (11); Structural formula (12); Structural formula (13); Wherein, n in structural formula (11) to structural formula (13) is an integer of 1 to 10.

7. The resin composition according to claim 1, characterized in that The inorganic filler is spherical silica surface-treated with an aminosilane coupling agent, and the aminosilane coupling agent has a structural formula (16): Structural formula (16); Wherein, R is a C1-C6 straight-chain alkylene group, and X is a methoxy group or an ethoxy group.

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

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