Impact-resistant epoxy resin composition as well as preparation method and application thereof

Abstract

The invention belongs to the technical field of high polymer materials, and particularly relates to an impact-resistant epoxy resin composition as well as a preparation method and application thereof. The impact-resistant epoxy resin composition comprises the following components in parts by weight: 30-50 parts of epoxy resin, 5-10 parts of bismaleimide resin, 3-8 parts of cashew nut shell oil resin, 10-20 parts of a toughening agent, 2-5 parts of a curing agent, 0.1-2 parts of a catalyst and 20-30 parts of a diluent, the toughening agent comprises phenolic hydroxyl polyether sulfone and a nano material containing an isocyanate group; the nano material is dendritic mesoporous silicon dioxide nano particles. The epoxy resin composition provided by the invention can replace traditional resin to be applied to a high-frequency HDI copper-clad plate, and the copper-clad plate prepared from the epoxy resin composition has excellent impact resistance, heat resistance, flame retardance, peel strength and dielectric property.

Description

Technical Field

[0001] The invention belongs to the technical field of polymer materials, and particularly relates to an impact-resistant epoxy resin composition, a preparation method and an application thereof. Background Art

[0002] The current development trend of electronic products is toward lighter, shorter, smaller, higher-performance, and higher-reliability products, placing increasing demands on the performance of copper-clad laminates (CCLs). Epoxy resins, with their advantages of high reactivity, mechanical strength, chemical resistance, and electrical insulation, are widely used in the production of CCLs. However, due to their molecular configuration and the presence of a large number of polar groups after curing, epoxy resins suffer from poor impact resistance, a relatively high dielectric constant, and insufficient heat and flame resistance, limiting their application in high-frequency and HDI (high-density interconnect) CCLs.

[0003] Therefore, it is of great significance to provide an impact-resistant epoxy resin composition that also has good heat resistance and low dielectric constant.

[0004] In the prior art, Chinese patent publication number CN117343481A discloses a modified halogen-free toughening resin, its preparation method, and a method for preparing a copper-clad laminate. This technical solution sequentially adds polyester polyol and polyphosphoric acid, heats them up, reacts them, and undergoes hydrolysis, water washing, and dehydration to produce a polyester phosphate ester. An epoxy resin is then added and prepolymerized with the polyester phosphate ester to produce the desired modified flame-retardant toughening resin mixture (resin 2). In the method for preparing the copper-clad laminate, a modified halogen-free toughening resin adhesive is prepared from resin 2, a cyanate resin, a polyphenylene ether resin, a linear phenolic resin, a curing agent, a catalyst, a filler, and a solvent by controlling the order of addition, material ratio, and reaction control. A prepreg is then prepared, and the copper-clad laminate is pressed to obtain the finished modified halogen-free toughened copper-clad laminate. The modified halogen-free toughened copper-clad laminate produced by this technical solution has high flexibility, impact strength, and glass transition temperature, excellent heat resistance, and outstanding flame retardancy. However, this technical solution has a low glass transition temperature, poor heat resistance, and does not pay attention to the dielectric constant. Summary of the Invention

[0005] The present invention aims to solve at least one of the above-mentioned technical problems existing in the prior art. To this end, the present invention provides an impact-resistant epoxy resin composition. The epoxy resin composition is compounded with an epoxy resin, a bismaleimide resin, and a cashew nut shell oil resin, and a phenolic hydroxyl polyether sulfone and an isocyanate group-containing nanomaterial as a toughening agent. The resulting epoxy resin composition is used to prepare a copper-clad laminate having excellent impact resistance, heat resistance, flame retardancy, peel strength, and dielectric properties.

[0006] A second aspect of the present invention provides a method for preparing an impact-resistant epoxy resin composition.

[0007] A third aspect of the present invention provides an impact-resistant epoxy resin composition for use in preparing copper-clad laminates.

[0008] To achieve the above object, the technical solution adopted by the present invention is as follows:

[0009] The first aspect of the present invention provides an impact-resistant epoxy resin composition, comprising the following components in parts by weight: 30-50 parts of epoxy resin, 5-10 parts of bismaleimide resin, 3-8 parts of cashew nut shell oil resin, 10-20 parts of toughening agent, 2-5 parts of curing agent, 0.1-2 parts of catalyst, and 20-30 parts of diluent;

[0010] The toughening agent comprises phenolic hydroxyl polyether sulfone and a nano material containing an isocyanate group; the nano material is dendritic mesoporous silica nano particles.

[0011] Specifically, the epoxy resin is any value of 30 parts, 32 parts, 35 parts, 38 parts, 40 parts, 42 parts, 45 parts, 48 parts or 50 parts, or a range value consisting of any two points.

[0012] Specifically, the bismaleimide resin is any value among 5 parts, 6 parts, 7 parts, 8 parts, 9 parts or 10 parts, or a range value consisting of any two values.

[0013] Specifically, the cashew nut shell oil resin is any value among 3 parts, 4 parts, 5 parts, 6 parts, 7 parts or 8 parts, or a range value consisting of any two points.

[0014] Specifically, the toughening agent is any value among 10 parts, 12 parts, 14 parts, 15 parts, 16 parts, 18 parts or 20 parts, or a range value consisting of any two points.

[0015] Specifically, the curing agent is any value among 2 parts, 3 parts, 4 parts or 5 parts, or a range value consisting of any two values.

[0016] Specifically, the catalyst is any value among 0.1 parts, 0.5 parts, 0.8 parts, 1 part, 1.5 parts, 1.8 parts or 2 parts, or a range value consisting of any two values.

[0017] Specifically, the diluent is any one of 20 parts, 12 parts, 24 parts, 26 parts, 28 parts or 30 parts, or a range consisting of any two of the values.

[0018] In some preferred embodiments, the epoxy resin includes trifunctional bisphenol A epoxy resin and DOPO modified epoxy resin.

[0019] In some preferred embodiments, the mass ratio of the trifunctional bisphenol A epoxy resin to the DOPO-modified epoxy resin is 1-2:1-2.

[0020] Specifically, the mass ratio of the trifunctional bisphenol A epoxy resin to the DOPO-modified epoxy resin is any value of 1:1, 1:2 or 2:1, or a range consisting of any two values.

[0021] In some preferred embodiments, the total chlorine content of the trifunctional bisphenol A epoxy resin is

[0022] <600ppm.

[0023] In a preferred embodiment, the trifunctional bisphenol A epoxy resin is sourced from Shanghai Zhongsi Industrial Co., Ltd., with a brand name of EP-4100HF, an epoxy equivalent of 182 g / eq, and a total chlorine content of <600 ppm.

[0024] In some preferred embodiments, the DOPO-modified epoxy resin is a DOPO-modified novolac epoxy resin.

[0025] In some preferred embodiments, the phosphorus content of the DOPO-modified novolac epoxy resin is 2-3%.

[0026] In a preferred embodiment, the DOPO-modified phenolic epoxy resin is from Tongyu New Materials (Guangdong) Co., Ltd., brand: TER628K70, with a phosphorus content of 2.4%.

[0027] In some preferred embodiments, the viscosity of the cashew nut shell oil resin is ≤60,000 cps (25° C.).

[0028] In a preferred embodiment, the cashew nut shell oil resin has a viscosity of 40,000-51,000 cps (25° C.) and is sourced from Cardolite with a brand name of NX-4778.

[0029] In some preferred embodiments, the bismaleimide resin is selected from at least one of a diphenylmethane bismaleimide resin and an aromatic polymer polyamine bismaleimide resin.

[0030] In a preferred embodiment, the bismaleimide resin is an aromatic polymer polyamine type bismaleimide resin.

[0031] In some preferred embodiments, the weight average molecular weight of the aromatic polymeric polyamine bismaleimide resin is 800-1200.

[0032] In a preferred embodiment, the aromatic polymer polyamine bismaleimide resin is from Jinan Shengquan Group Co., Ltd., with a brand name of PFB502, a solid content of 70±2%, and a weight-average molecular weight of 900±100.

[0033] In some preferred embodiments, the mass ratio of the phenolic hydroxyl polyethersulfone to the isocyanate group-containing nanomaterial is 1-2:5-10.

[0034] Specifically, the mass ratio of the phenolic hydroxyl polyether sulfone and the isocyanate group-containing nanomaterial is any one of 1:5, 1:6, 1:1:8, 1:9:1:10, 2:5, 2:6, 2:7, 2:8 or 2:9, or a range consisting of any two of the values.

[0035] In some preferred embodiments, the average particle size of the phenolic hydroxy polyether sulfone is ≤40 μm, and the molecular weight is

[0036] ≥50000g / mol, hydroxyl content>50Micro-equiv / g.

[0037] In a preferred embodiment, the phenolic hydroxyl polyethersulfone has an average particle size of 35 μm, a molecular weight of 55,000 g / mol, a hydroxyl content of >50 Micro-equiv / g, and is sourced from Shanghai Zhongsi Industrial Co., Ltd. with a brand name of E2020P SRMicro.

[0038] In some preferred embodiments, the isocyanate group-containing nanomaterial is obtained by grafting dendritic mesoporous silica nanoparticles and 1,5-naphthalene diisocyanate under the action of a catalyst.

[0039] In some preferred embodiments, the method for preparing the isocyanate group-containing nanomaterial comprises the following steps: placing dendritic mesoporous silica nanoparticles in a solvent, adding 1,5-naphthalene diisocyanate and a catalyst, carrying out a grafting reaction, and washing and drying after the reaction to obtain the isocyanate group-containing nanomaterial.

[0040] In some preferred embodiments, the grafting reaction is carried out under nitrogen protection.

[0041] In some preferred embodiments, the mass ratio of the dendritic mesoporous silica nanoparticles, the solvent, 1,5-naphthalene diisocyanate and the catalyst is 0.1-0.2:20-30:2-4:0.015-0.03.

[0042] In some preferred embodiments, the particle size of the dendritic mesoporous silica nanoparticles is 100-200 nm.

[0043] The dendritic mesoporous silica nanoparticles in the present invention are in powder form or water-dispersed form.

[0044] In a preferred embodiment, the dendritic mesoporous silica nanoparticles are in a water-dispersed form and are sourced from Nanjing Donna Biotechnology Co., Ltd. with a product number of DMSNs, a concentration of 5 mg / L, and a particle size of 200 nm.

[0045] In some preferred embodiments, the solvent is selected from at least one of ethanol, ethyl acetate, chloroform and dichloromethane.

[0046] In some preferred embodiments, the catalyst is selected from at least one of dibutyltin dilaurate and stannous isooctanoate.

[0047] In some preferred embodiments, the grafting reaction temperature is 72-78° C., and the time is 4-5 hours.

[0048] Specifically, the temperature of the grafting reaction is any one of 72° C., 73° C., 74° C., 75° C., 76° C., 77° C. or 78° C., or a range consisting of any two of the values.

[0049] Specifically, the grafting reaction time is any one of 4 hours, 4.5 hours or 5 hours, or a range consisting of any two of the values.

[0050] In some preferred embodiments, the curing agent is selected from at least one of dicyandiamide, diaminodiphenylmethane and diaminodiphenylsulfone.

[0051] In some preferred embodiments, the catalyst is selected from at least one of imidazole, 2-methylimidazole, 2-ethylimidazole and 2-phenylimidazole.

[0052] In some preferred embodiments, the diluent is selected from at least one of acetone, butanone, toluene, xylene, methanol and isopropanol.

[0053] The second aspect of the present invention provides a method for preparing an impact-resistant epoxy resin composition, comprising the following steps: first, mixing epoxy resin, bismaleimide resin, cashew nut shell oil resin and diluent, then adding a toughening agent and mixing, and finally adding a curing agent and a catalyst and mixing.

[0054] A third aspect of the present invention provides an impact-resistant epoxy resin composition for use in preparing copper-clad laminates.

[0055] Compared with the prior art, the present invention has the following beneficial effects:

[0056] 1. The epoxy resin composition provided by the present invention adopts epoxy resin, bismaleimide resin and cashew nut shell oil resin for compound use, wherein the rigid aromatic ring structure of bismaleimide resin provides heat resistance and flame retardancy, but the epoxy resin and bismaleimide resin have poor toughness after curing, while the long-chain aliphatic hydrocarbon structure contained in cashew nut shell oil resin gives the system flexibility, improves the toughness of epoxy resin, thereby improving the heat resistance of copper clad laminate while improving its impact resistance, and also has high peel strength.

[0057] 2. The present invention introduces isocyanate groups on the surface of dendritic mesoporous silica nanoparticles through the grafting reaction of 1,5-naphthalene diisocyanate and the hydroxyl groups on the surface of dendritic mesoporous silica nanoparticles; the dendritic mesoporous silica nanoparticles containing isocyanate groups are compounded with phenolic hydroxyl polyether sulfone as a toughening agent: the isocyanate groups on the surface of the dendritic mesoporous silica nanoparticles containing isocyanate groups can react with the epoxy resin and phenolic hydroxyl polyether sulfone in the system to optimize the crosslinking density, while the high specific surface area of the dendritic mesoporous silica nanoparticles increases the contact surface with the resin matrix, further The method effectively disperses the impact stress in one step; the dendritic mesoporous silica nanoparticles are modified with a specific 1,5-naphthalene diisocyanate to further improve the heat resistance; the phenolic hydroxyl polyether sulfone forms an energy dissipation network in the matrix through the flexibility of its polymer chain, inhibiting crack propagation; the dendritic mesoporous silica nanoparticles containing isocyanate groups work together with the phenolic hydroxyl polyether sulfone, and the epoxy resin, bismaleimide resin and cashew nut shell oil resin in the system to prepare an epoxy resin composition that makes the copper clad laminate have excellent impact resistance and heat resistance while also having high peel strength and dielectric properties. BRIEF DESCRIPTION OF THE DRAWINGS

[0058] Figure 1 These are transmission electron microscope images of the dendritic mesoporous silica nanoparticles used in Examples 1-4, Comparative Examples 1-4, and Comparative Example 6 of the present invention.

[0059] Figure 2 This is a transmission electron microscope image of the mesoporous silica nanoparticles used in Comparative Example 5 of the present invention. DETAILED DESCRIPTION

[0060] In order to have a clearer understanding of the technical features, purposes and effects of the present invention, a specific implementation scheme is now described in detail.

[0061] The present invention is further described below with reference to the following examples, but the present invention is not limited to the following examples. The implementation conditions used in the examples can be further adjusted according to the specific requirements of different applications. The implementation conditions not specified are conventional conditions in the industry. The technical features involved in the various embodiments of the present invention may be combined with each other as long as they do not conflict with each other.

[0062] In the following examples and comparative examples, unless otherwise specified, all raw materials used were commercially available or prepared by conventional methods in the art.

[0063] Example 1

[0064] This embodiment discloses an impact-resistant epoxy resin composition, which comprises the following components in parts by weight: 30 parts of epoxy resin, 5 parts of bismaleimide resin, 3 parts of cashew nut shell oil resin, 10 parts of toughening agent, 2 parts of curing agent, 0.5 parts of catalyst, and 20 parts of diluent.

[0065] The epoxy resin consists of trifunctional bisphenol A epoxy resin and DOPO modified epoxy resin in a mass ratio of 1:1.

[0066] The trifunctional bisphenol A epoxy resin is from Shanghai Zhongsi Industrial Co., Ltd., with the brand name EP-4100HF, an epoxy equivalent weight of 182 g / eq, and a total chlorine content of <600 ppm.

[0067] The DOPO-modified epoxy resin is a DOPO-modified novolac epoxy resin; the DOPO-modified novolac epoxy resin is from Tongyu New Materials (Guangdong) Co., Ltd., with the brand name TER628K70 and a phosphorus content of 2.4%.

[0068] The bismaleimide resin is an aromatic polymer polyamine type bismaleimide resin; the aromatic polymer polyamine type bismaleimide resin is sourced from Jinan Shengquan Group Co., Ltd., with a brand name of PFB502, a solid content of 70±2%, and a weight average molecular weight of 900±100.

[0069] The cashew nut shell oil resin has a viscosity of 40,000-51,000 cps (25° C.) and is sourced from Cardolite with the brand name NX-4778.

[0070] The toughening agent consists of phenolic hydroxyl polyether sulfone and nanomaterial containing isocyanate group in a mass ratio of 1:6.

[0071] The phenolic hydroxy polyether sulfone has an average particle size of 35 μm, a molecular weight of 55,000 g / mol, a hydroxyl content of >50 Micro-equiv / g, and is sourced from Shanghai Zhongsi Industrial Co., Ltd. with the brand name E2020P SR Micro.

[0072] The preparation method of the nanomaterial containing isocyanate groups comprises the following steps: placing dendritic mesoporous silica nanoparticles in ethyl acetate (CAS number: 141-78-6), adding 1,5-naphthalene diisocyanate and dibutyltin dilaurate (CAS number: 77-58-7), carrying out a grafting reaction at 75° C. for 4 hours under a nitrogen protective atmosphere, and washing and drying after the reaction to obtain the nanomaterial containing isocyanate groups.

[0073] The mass ratio of the dendritic mesoporous silica nanoparticles, ethyl acetate, 1,5-naphthalene diisocyanate and dibutyltin dilaurate is 0.1:25:3:0.02.

[0074] The dendritic mesoporous silica nanoparticles are in water-dispersible form and are sourced from Nanjing Dongna Biotechnology Co., Ltd. The product number is DMSNs, with a concentration of 5 mg / L and a particle size of 200 nm. The transmission electron microscope image is shown below. Figure 1 shown.

[0075] The 1,5-naphthalene diisocyanate is sourced from Guangzhou Haoyi New Materials Technology Co., Ltd., and has an NCO content of 40%.

[0076] The curing agent is dicyandiamide (CAS No.: 461-58-5).

[0077] The catalyst is 2-methylimidazole (CAS No.: 693-98-1).

[0078] The diluent is acetone (CAS No.: 67-64-1).

[0079] The preparation method of the impact-resistant epoxy resin composition is as follows: firstly, epoxy resin, bismaleimide resin, cashew nut shell oil resin and diluent are uniformly stirred, then toughening agent is added and uniformly stirred, and finally curing agent and catalyst are added and uniformly stirred to obtain the composition.

[0080] Example 2

[0081] This embodiment discloses an impact-resistant epoxy resin composition, which comprises the following components in parts by weight: 38 parts of epoxy resin, 7 parts of bismaleimide resin, 5 parts of cashew nut shell oil resin, 16 parts of toughening agent, 3.5 parts of curing agent, 1 part of catalyst, and 28 parts of diluent.

[0082] The epoxy resin consists of trifunctional bisphenol A epoxy resin and DOPO modified epoxy resin in a mass ratio of 1:1.

[0083] The trifunctional bisphenol A epoxy resin is from Shanghai Zhongsi Industrial Co., Ltd., with the brand name EP-4100HF, an epoxy equivalent weight of 182 g / eq, and a total chlorine content of <600 ppm.

[0084] The DOPO-modified epoxy resin is a DOPO-modified novolac epoxy resin; the DOPO-modified novolac epoxy resin is from Tongyu New Materials (Guangdong) Co., Ltd., with the brand name TER628K70 and a phosphorus content of 2.4%.

[0085] The bismaleimide resin is an aromatic polymer polyamine type bismaleimide resin; the aromatic polymer polyamine type bismaleimide resin is sourced from Jinan Shengquan Group Co., Ltd., with a brand name of PFB502, a solid content of 70±2%, and a weight average molecular weight of 900±100.

[0086] The cashew nut shell oil resin has a viscosity of 40,000-51,000 cps (25° C.) and is sourced from Cardolite with the brand name NX-4778.

[0087] The toughening agent consists of phenolic hydroxyl polyether sulfone and nanomaterial containing isocyanate group in a mass ratio of 1:6.

[0088] The phenolic hydroxy polyether sulfone has an average particle size of 35 μm, a molecular weight of 55,000 g / mol, a hydroxyl content of >50 Micro-equiv / g, and is sourced from Shanghai Zhongsi Industrial Co., Ltd. with the brand name E2020P SR Micro.

[0089] The preparation method of the nanomaterial containing isocyanate groups comprises the following steps: placing dendritic mesoporous silica nanoparticles in ethyl acetate (CAS number: 141-78-6), adding 1,5-naphthalene diisocyanate and dibutyltin dilaurate (CAS number: 77-58-7), carrying out a grafting reaction at 75° C. for 4 hours under a nitrogen protective atmosphere, and washing and drying after the reaction to obtain the nanomaterial containing isocyanate groups.

[0090] The mass ratio of the dendritic mesoporous silica nanoparticles, ethyl acetate, 1,5-naphthalene diisocyanate and dibutyltin dilaurate is 0.1:25:3:0.02.

[0091] The dendritic mesoporous silica nanoparticles are in water-dispersible form and are sourced from Nanjing Dongna Biotechnology Co., Ltd. The product number is DMSNs, with a concentration of 5 mg / L and a particle size of 200 nm. The transmission electron microscope image is shown below. Figure 1 shown.

[0092] The 1,5-naphthalene diisocyanate is sourced from Guangzhou Haoyi New Materials Technology Co., Ltd., and has an NCO content of 40%.

[0093] The curing agent is dicyandiamide (CAS No.: 461-58-5).

[0094] The catalyst is 2-methylimidazole (CAS No.: 693-98-1).

[0095] The diluent is acetone (CAS No.: 67-64-1).

[0096] The preparation method of the impact-resistant epoxy resin composition is as follows: firstly, epoxy resin, bismaleimide resin, cashew nut shell oil resin and diluent are uniformly stirred, then toughening agent is added and uniformly stirred, and finally curing agent and catalyst are added and uniformly stirred to obtain the composition.

[0097] Example 3

[0098] This embodiment discloses an impact-resistant epoxy resin composition, which comprises the following components in parts by weight: 44 parts of epoxy resin, 8 parts of bismaleimide resin, 6 parts of cashew nut shell oil resin, 16 parts of toughening agent, 4 parts of curing agent, 1.2 parts of catalyst, and 26 parts of diluent.

[0099] The epoxy resin consists of trifunctional bisphenol A epoxy resin and DOPO modified epoxy resin in a mass ratio of 1:1.

[0100] The trifunctional bisphenol A epoxy resin is from Shanghai Zhongsi Industrial Co., Ltd., with the brand name EP-4100HF, an epoxy equivalent weight of 182 g / eq, and a total chlorine content of <600 ppm.

[0101] The DOPO-modified epoxy resin is a DOPO-modified novolac epoxy resin; the DOPO-modified novolac epoxy resin is from Tongyu New Materials (Guangdong) Co., Ltd., with the brand name TER628K70 and a phosphorus content of 2.4%.

[0102] The bismaleimide resin is an aromatic polymer polyamine type bismaleimide resin; the aromatic polymer polyamine type bismaleimide resin is sourced from Jinan Shengquan Group Co., Ltd., with a brand name of PFB502, a solid content of 70±2%, and a weight average molecular weight of 900±100.

[0103] The cashew nut shell oil resin has a viscosity of 40,000-51,000 cps (25° C.) and is sourced from Cardolite with the brand name NX-4778.

[0104] The toughening agent consists of phenolic hydroxyl polyether sulfone and nanomaterial containing isocyanate group in a mass ratio of 1:6.

[0105] The phenolic hydroxy polyether sulfone has an average particle size of 35 μm, a molecular weight of 55,000 g / mol, a hydroxyl content of >50 Micro-equiv / g, and is sourced from Shanghai Zhongsi Industrial Co., Ltd. with the brand name E2020P SR Micro.

[0106] The preparation method of the nanomaterial containing isocyanate groups comprises the following steps: placing dendritic mesoporous silica nanoparticles in ethyl acetate (CAS number: 141-78-6), adding 1,5-naphthalene diisocyanate and dibutyltin dilaurate (CAS number: 77-58-7), carrying out a grafting reaction at 75° C. for 4 hours under a nitrogen protective atmosphere, and washing and drying after the reaction to obtain the nanomaterial containing isocyanate groups.

[0107] The mass ratio of the dendritic mesoporous silica nanoparticles, ethyl acetate, 1,5-naphthalene diisocyanate and dibutyltin dilaurate is 0.1:25:3:0.02.

[0108] The dendritic mesoporous silica nanoparticles are in water-dispersible form and are sourced from Nanjing Dongna Biotechnology Co., Ltd. The product number is DMSNs, with a concentration of 5 mg / L and a particle size of 200 nm. The transmission electron microscope image is shown below. Figure 1 shown.

[0109] The 1,5-naphthalene diisocyanate is sourced from Guangzhou Haoyi New Materials Technology Co., Ltd., and has an NCO content of 40%.

[0110] The curing agent is dicyandiamide (CAS No.: 461-58-5).

[0111] The catalyst is 2-methylimidazole (CAS No.: 693-98-1).

[0112] The diluent is acetone (CAS No.: 67-64-1).

[0113] The preparation method of the impact-resistant epoxy resin composition is as follows: firstly, epoxy resin, bismaleimide resin, cashew nut shell oil resin and diluent are uniformly stirred, then toughening agent is added and uniformly stirred, and finally curing agent and catalyst are added and uniformly stirred to obtain the composition.

[0114] Example 4

[0115] This embodiment discloses an impact-resistant epoxy resin composition, which comprises the following components in parts by weight: 50 parts of epoxy resin, 10 parts of bismaleimide resin, 8 parts of cashew nut shell oil resin, 20 parts of toughening agent, 5 parts of curing agent, 1.5 parts of catalyst, and 30 parts of diluent.

[0116] The epoxy resin consists of trifunctional bisphenol A epoxy resin and DOPO modified epoxy resin in a mass ratio of 1:1.

[0117] The trifunctional bisphenol A epoxy resin is from Shanghai Zhongsi Industrial Co., Ltd., with the brand name EP-4100HF, an epoxy equivalent weight of 182 g / eq, and a total chlorine content of <600 ppm.

[0118] The DOPO-modified epoxy resin is a DOPO-modified novolac epoxy resin; the DOPO-modified novolac epoxy resin is from Tongyu New Materials (Guangdong) Co., Ltd., with the brand name TER628K70 and a phosphorus content of 2.4%.

[0119] The bismaleimide resin is an aromatic polymer polyamine type bismaleimide resin; the aromatic polymer polyamine type bismaleimide resin is sourced from Jinan Shengquan Group Co., Ltd., with a brand name of PFB502, a solid content of 70±2%, and a weight average molecular weight of 900±100.

[0120] The cashew nut shell oil resin has a viscosity of 40,000-51,000 cps (25° C.) and is sourced from Cardolite with the brand name NX-4778.

[0121] The toughening agent consists of phenolic hydroxyl polyether sulfone and nanomaterial containing isocyanate group in a mass ratio of 1:6.

[0122] The phenolic hydroxy polyether sulfone has an average particle size of 35 μm, a molecular weight of 55,000 g / mol, a hydroxyl content of >50 Micro-equiv / g, and is sourced from Shanghai Zhongsi Industrial Co., Ltd. with the brand name E2020P SR Micro.

[0123] The preparation method of the nanomaterial containing isocyanate groups comprises the following steps: placing dendritic mesoporous silica nanoparticles in ethyl acetate (CAS number: 141-78-6), adding 1,5-naphthalene diisocyanate and dibutyltin dilaurate (CAS number: 77-58-7), carrying out a grafting reaction at 75° C. for 4 hours under a nitrogen protective atmosphere, and washing and drying after the reaction to obtain the nanomaterial containing isocyanate groups.

[0124] The mass ratio of the dendritic mesoporous silica nanoparticles, ethyl acetate, 1,5-naphthalene diisocyanate and dibutyltin dilaurate is 0.1:25:3:0.02.

[0125] The dendritic mesoporous silica nanoparticles are in water-dispersible form and are sourced from Nanjing Dongna Biotechnology Co., Ltd. The product number is DMSNs, with a concentration of 5 mg / L and a particle size of 200 nm. The transmission electron microscope image is shown below. Figure 1 shown.

[0126] The 1,5-naphthalene diisocyanate is sourced from Guangzhou Haoyi New Materials Technology Co., Ltd., and has an NCO content of 40%.

[0127] The curing agent is dicyandiamide (CAS No.: 461-58-5).

[0128] The catalyst is 2-methylimidazole (CAS No.: 693-98-1).

[0129] The diluent is acetone (CAS No.: 67-64-1).

[0130] The preparation method of the impact-resistant epoxy resin composition is as follows: firstly, epoxy resin, bismaleimide resin, cashew nut shell oil resin and diluent are uniformly stirred, then toughening agent is added and uniformly stirred, and finally curing agent and catalyst are added and uniformly stirred to obtain the composition.

[0131] Comparative Example 1

[0132] This comparative example discloses an impact-resistant epoxy resin composition, which differs from Example 4 in that the cashew nut shell oil resin is replaced with a tung oil-modified phenolic resin, which is sourced from Jining Baiyi Chemical Co., Ltd.; all other aspects are the same.

[0133] Comparative Example 2

[0134] This comparative example discloses an impact-resistant epoxy resin composition, which differs from Example 4 in that the toughening agent is phenolic hydroxyl polyether sulfone; the rest are the same.

[0135] Comparative Example 3

[0136] This comparative example discloses an impact-resistant epoxy resin composition, which differs from Example 4 in that the toughening agent is a nanomaterial containing an isocyanate group; all other aspects are the same.

[0137] Comparative Example 4

[0138] This comparative example discloses an impact-resistant epoxy resin composition, which differs from Example 4 in that the toughening agent consists of phenolic hydroxyl polyethersulfone and dendritic mesoporous silica nanoparticles in a mass ratio of 1:6; all other aspects are the same.

[0139] Comparative Example 5

[0140] This comparative example discloses an impact-resistant epoxy resin composition. The difference from Example 4 is that the dendritic mesoporous silica nanoparticles are replaced with mesoporous silica nanoparticles of equal mass; the mesoporous silica nanoparticles are from Nanjing Dongna Biotechnology Co., Ltd., with the product number MSNs; the particle size is 100 nm; the transmission electron microscope image thereof is as follows: Figure 2 shown; all others are the same.

[0141] Comparative Example 6

[0142] This comparative example discloses an impact-resistant epoxy resin composition, which differs from Example 3 in that 1,5-naphthalene diisocyanate is replaced with hexamethylene diisocyanate of equal mass, which is sourced from Wanhua Chemical Group Co., Ltd. and has an NCO content of 49.7%. All other aspects are the same.

[0143] Application Examples

[0144] Electronic grade glass fiber cloth (from Tongcheng County Tongli Glass Fiber Co., Ltd., thickness of 0.033 ± 0.012 mm, model: 106) was immersed in the epoxy resin composition of Examples 1-4 and Comparative Examples 1-6, respectively, and after immersion for 10 seconds, it was taken out and cured at 180 ° C for 3 minutes to prepare a prepreg. The prepreg was covered with 40 μm copper foil on both sides and hot pressed at a temperature of 200 ° C and a pressure of 35 kg / cm 2 After pressing for 120 minutes, the copper clad laminate samples were obtained and the following performance tests were performed on the copper clad laminate samples:

[0145] 1. Impact resistance: Use a drop hammer impact tester to test, with a drop hammer weight of 1 kg and a drop hammer height of 1 meter. Measure the drop mark area. The smaller the area, the better the impact resistance.

[0146] 2. Peel strength: Tested in accordance with GB / T 4722-2017-7.2.1;

[0147] 3. Flame retardancy: tested in accordance with GB / T 4722-2017-6.4.1;

[0148] 4. Heat resistance: GB / T 4722-2017-6.11 is used to test the thermal stratification time at 288°C;

[0149] 5. Dielectric constant: The dielectric constant at 10 Hz is tested in accordance with GB / T 4722-2017-8.5.

[0150] The test results are shown in the following table:

[0151]

[0152]

[0153] It can be seen from the above data that the copper clad laminate prepared by using the epoxy resin composition prepared by the present invention has excellent impact resistance and also has high peel strength, good flame retardancy, good heat resistance and good dielectric properties;

[0154] The epoxy resin composition prepared by compounding epoxy resin, bismaleimide resin and cashew nut shell oil resin in the present invention can improve the impact resistance, peel strength and heat resistance of the copper clad laminate; in Comparative Example 1, the cashew nut shell oil resin is replaced with tung oil-modified phenolic resin, resulting in a decrease in the impact resistance, peel strength and heat resistance of the copper clad laminate;

[0155] The present invention adopts phenolic hydroxyl polyether sulfone and a self-made nanomaterial containing isocyanate groups as toughening agents. The epoxy resin composition obtained by the synergistic effect of the two improves the impact resistance and heat resistance of the copper clad laminate while also improving the peel strength of the copper clad laminate. Among them, the nanomaterial containing isocyanate groups prepared by modifying dendritic mesoporous silica nanoparticles with 1,5-naphthalene diisocyanate can significantly improve the impact resistance and heat resistance of the copper clad laminate while also affecting the peel strength and dielectric properties of the copper clad laminate.

[0156] Comparative Examples 2 and 3 used only a single-component toughening agent, resulting in decreased impact resistance, peel strength, and heat resistance of the copper clad laminate.

[0157] The dendritic mesoporous silica nanoparticles in Comparative Example 4 were not modified with 1,5-naphthalene diisocyanate; in Comparative Example 5, the dendritic mesoporous silica nanoparticles were replaced with mesoporous silica nanoparticles of equal mass; and in Comparative Example 6, 1,5-naphthalene diisocyanate was replaced with hexamethylene diisocyanate of equal mass; resulting in a decrease in the impact resistance, peel strength, heat resistance and dielectric properties of the copper clad laminate.

[0158] Finally, it should be noted that the above content is only used to illustrate the technical solution of the present invention, rather than to limit the scope of protection of the present invention. Simple modifications or equivalent substitutions of the technical solution of the present invention by ordinary technicians in this field do not deviate from the essence and scope of the technical solution of the present invention.

Claims

1. An impact-resistant epoxy resin composition, characterized in that The invention comprises the following components in parts by weight: 30-50 parts of epoxy resin, 5-10 parts of bismaleimide resin, 3-8 parts of cashew nut shell oil resin, 10-20 parts of toughening agent, 2-5 parts of curing agent, 0.1-2 parts of catalyst, and 20-30 parts of diluent; The toughening agent comprises phenolic hydroxyl polyether sulfone and a nano material containing an isocyanate group; the nano material is dendritic mesoporous silica nano particles.

2. The impact-resistant epoxy resin composition according to claim 1, characterized in that The epoxy resin includes trifunctional bisphenol A epoxy resin and DOPO modified epoxy resin; The total chlorine content of the trifunctional bisphenol A epoxy resin is less than 600 ppm; The DOPO modified epoxy resin is a DOPO modified novolac epoxy resin; The phosphorus content of the DOPO-modified novolac epoxy resin is 2-3%.

3. The impact-resistant epoxy resin composition according to claim 2, characterized in that The bismaleimide resin is selected from at least one of diphenylmethane bismaleimide resin and aromatic polymer polyamine bismaleimide resin.

4. The impact-resistant epoxy resin composition according to claim 3, characterized in that The isocyanate group-containing nanomaterial is obtained by grafting dendritic mesoporous silica nanoparticles and 1,5-naphthalene diisocyanate under the action of a catalyst.

5. The impact-resistant epoxy resin composition according to any one of claims 1 to 4, characterized in that The preparation method of the nanomaterial containing isocyanate groups comprises the following steps: placing dendritic mesoporous silica nanoparticles in a solvent, adding 1,5-naphthalene diisocyanate and a catalyst, carrying out a grafting reaction, and washing and drying after the reaction to obtain the nanomaterial containing isocyanate groups.

6. The impact-resistant epoxy resin composition according to claim 5, characterized in that The mass ratio of the dendritic mesoporous silica nanoparticles, the solvent, 1,5-naphthalene diisocyanate and the catalyst is 0.1-0.2:20-30:2-4:0.015-0.

03.

7. The impact-resistant epoxy resin composition according to claim 5, characterized in that The particle size of the dendritic mesoporous silica nanoparticles is 100-200 nm.

8. The impact-resistant epoxy resin composition according to claim 5, characterized in that The grafting reaction temperature is 72-78° C. and the time is 4-5 hours.

9. The method for preparing the impact-resistant epoxy resin composition according to any one of claims 1 to 8, characterized in that: The method comprises the following steps: firstly, evenly stirring epoxy resin, bismaleimide resin, cashew nut shell oil resin and diluent, then adding toughening agent and stirring evenly, and finally adding curing agent and catalyst and stirring evenly to obtain the product.

10. Use of the impact-resistant epoxy resin composition according to any one of claims 1 to 8 in the preparation of copper-clad laminates.

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