An impact-resistant epoxy resin composition, and a method of making and using the same

Abstract

The application belongs to the technical field of polymer materials, and particularly relates to an impact-resistant epoxy resin composition, 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 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 nano material containing isocyanate groups. The nano material is dendritic mesoporous silica nanoparticles. The epoxy resin composition provided by the application can be used in high frequency and HDI copper-clad plates to replace traditional resins, and the prepared copper-clad plate has excellent impact resistance, heat resistance, flame resistance, peeling strength and dielectric properties.

Description

TECHNICAL FIELD

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

[0002] The development trend of electronic products is lighter, shorter, smaller, high performance and high reliability, so the performance requirements of copper-clad plate are also getting higher and higher. Epoxy resin has the advantages of high reactivity, high mechanical strength, chemical resistance and electrical insulation performance, and is widely used in the production of copper-clad plate. However, due to its own molecular configuration and the presence of a large number of polar groups after curing, the epoxy resin has the disadvantages of poor impact resistance, large dielectric constant, insufficient heat resistance and flame retardance, which limits its application in high-frequency and HDI (high-density interconnection) copper-clad plate.

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

[0004] A Chinese patent with publication number CN117343481A discloses a modified halogen-free toughening resin, a preparation method thereof and a preparation method of a copper-clad plate. In the technical solution, polyester polyol and polyphosphoric acid are sequentially added and reacted by increasing the temperature, and then the polyester phosphoric acid ester is prepared by hydrolysis, water washing and water removal. Then, the epoxy resin is added and pre-polymerized with the polyester phosphoric acid ester to obtain the required modified flame-retardant toughening resin mixture (resin 2). In the preparation method of the copper-clad plate, the modified halogen-free toughening resin glue is prepared by controlling the adding order, material ratio, reaction control and other configurations of the resin 2, cyanate ester resin, polyphenyl ether resin, linear phenolic resin, curing agent, catalyst, filler and solvent, and then the semi-cured sheet is prepared and the copper-clad plate is pressed to obtain the modified halogen-free toughening copper-clad plate product. The modified halogen-free toughening copper-clad plate has high flexibility, impact strength and glass transition temperature, excellent heat resistance, outstanding flame retardant effect and other characteristics. However, the glass transition temperature is low, the heat resistance is poor, and the dielectric constant is not concerned. SUMMARY

[0005] The present application aims to solve at least one of the above technical problems in the prior art. To this end, the purpose of the present application is to provide an impact-resistant epoxy resin composition, which uses epoxy resin, bismaleimide resin, cashew nut shell oil resin, phenolic hydroxyl polyether sulfone and nano material containing isocyanate group as toughening agent, and the obtained copper-clad plate has excellent impact resistance, heat resistance, flame retardance, peel strength and dielectric properties.

[0006] The second aspect of the present application provides a preparation method of an impact-resistant epoxy resin composition.

[0007] The third aspect of the present application provides a use of the impact-resistant epoxy resin composition in the preparation of copper-clad plates.

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

[0009] The first aspect of the present application provides an impact-resistant epoxy resin composition, which comprises the following components 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 nano material containing isocyanate groups; the nano material is dendritic mesoporous silica nanoparticles.

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

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

[0013] Specifically, the cashew nut shell oil resin is 3 parts, 4 parts, 5 parts, 6 parts, 7 parts or 8 parts, any one value or a range value composed of any two point values.

[0014] Specifically, the toughening agent is 10 parts, 12 parts, 14 parts, 15 parts, 16 parts, 18 parts or 20 parts, any one value or a range value composed of any two point values.

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

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

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

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

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

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

[0021] In some preferred embodiments, the total chlorine content of the trifunctional bisphenol A type epoxy resin is < 600 ppm.

[0022] < 600 ppm.

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

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

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

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

[0027] In some preferred embodiments, the cashew nut shell liquid resin has a viscosity < 60000 cps (25°C).

[0028] In a preferred embodiment, the cashew nut shell liquid resin has a viscosity of 40000-51000 cps (25°C), and is sourced from Kadlec, with the trade name NX-4778.

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

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

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

[0032] In a preferred embodiment, the aromatic polymeric polyamine type bismaleimide resin is sourced from Jinan Shengquan Group Co., Ltd., with the trade name 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 polyether sulfone and 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 value or a range value consisting of any two point values in 1:5, 1:6, 1:1:8, 1:9:1:10, 2:5, 2:6, 2:7, 2:8 or 2:9.

[0035] In some preferred embodiments, the average particle size of the phenolic hydroxyl polyether sulfone is ≤40 μm, the molecular weight is ≥50000 g / mol, and the hydroxyl content is >50 Micro-equiv / g.

[0036] In some preferred embodiments, the average particle size of the phenolic hydroxyl polyether sulfone is ≤40 μm, the molecular weight is ≥50000 g / mol, and the hydroxyl content is >50 Micro-equiv / g.

[0037] In a preferred embodiment, the average particle size of the phenolic hydroxyl polyether sulfone is 35 μm, the molecular weight is 55000 g / mol, the hydroxyl content is >50 Micro-equiv / g, and it is sourced from Shanghai Zhongsi Industrial Co., Ltd. and the brand is 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 preparation method of 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, performing grafting reaction, and after the reaction is completed, performing washing and drying to obtain the isocyanate group-containing nanomaterial.

[0040] In some preferred embodiments, the grafting reaction is performed 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 application are in the form of powder or water dispersion.

[0044] In a preferred embodiment, the dendritic mesoporous silica nanoparticles are in a water dispersion form, which are available from Nanjing Dongna Biotech Co., Ltd. with the product code of DMSNs, the concentration of 5 mg / L and the 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 octoate.

[0047] In some preferred embodiments, the temperature of the grafting reaction is 72-78℃ and the time is 4-5h.

[0048] Specifically, the temperature of the grafting reaction is any one value or a range value consisting of any two point values selected from 72℃, 73℃, 74℃, 75℃, 76℃, 77℃ and 78℃.

[0049] Specifically, the time of the grafting reaction is any one value or a range value consisting of any two point values selected from 4h, 4.5h and 5h.

[0050] In some preferred embodiments, the curing agent is selected from at least one of dicyandiamide, diamine-based diphenyl methane and diamine-based diphenyl sulfone.

[0051] In some preferred embodiments, the catalyst is selected from at least one of imidazole, 2-methyl imidazole, 2-ethyl imidazole and 2-phenyl imidazole.

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

[0053] The second aspect of the present application provides a preparation method of the impact-resistant epoxy resin composition, which comprises the following steps: firstly, uniformly stirring the epoxy resin, the bismaleimide resin, the cashew nut shell oil resin and the diluent, then uniformly stirring the toughening agent, and finally uniformly stirring the curing agent and the catalyst to obtain the impact-resistant epoxy resin composition.

[0054] The third aspect of the present application provides an application of the impact-resistant epoxy resin composition in the preparation of the copper-clad plate.

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

[0056] 1. The epoxy resin composition provided by the present application uses epoxy resin, bismaleimide resin and cashew shell oil resin in combination, wherein the rigid aromatic ring structure of the bismaleimide resin provides heat resistance and flame retardancy, but the toughness of the epoxy resin and the bismaleimide resin is poor after curing, and the long-chain aliphatic hydrocarbon structure contained in the cashew shell oil resin endows the system with flexibility, improves the toughness of the epoxy resin, and further improves the heat resistance and impact resistance of the copper-clad plate, and also has high peel strength.

[0057] 2. The present application introduces isocyanate groups on the surface of dendritic mesoporous silica nanoparticles through grafting reaction of 1,5-naphthalene diisocyanate with the hydroxyl groups on the surface of the dendritic mesoporous silica nanoparticles; the dendritic mesoporous silica nanoparticles containing isocyanate groups are compounded with phenolic hydroxyl polyether sulfone as a toughening agent; wherein 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, optimizing the crosslinking density, and the high specific surface area of the dendritic mesoporous silica nanoparticles increases the contact area with the resin matrix, further effectively dispersing impact stress; the specific 1,5-naphthalene diisocyanate is used to modify the dendritic mesoporous silica nanoparticles, further improving 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 and the phenolic hydroxyl polyether sulfone jointly act on the epoxy resin, bismaleimide resin and cashew shell oil resin in the system, and the prepared epoxy resin composition makes the copper-clad plate have excellent impact resistance, heat resistance, and also has high peel strength and dielectric properties. BRIEF DESCRIPTION OF DRAWINGS

[0058] Figure 1 The transmission electron microscope picture of the dendritic mesoporous silica nanoparticles used in Examples 1-4, Comparative Examples 1-4 and Comparative Example 6 of the present application.

[0059] Figure 2 The transmission electron microscope picture of the mesoporous silica nanoparticles used in Comparative Example 5 of the present application. DETAILED DESCRIPTION

[0060] In order to have a clearer understanding of the technical features, objectives and effects of the present application, the specific implementation schemes will be described in detail.

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

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

[0063] Example 1

[0064] The present example discloses an impact-resistant epoxy resin composition, which is composed of the following components by weight: epoxy resin 30 parts, bismaleimide resin 5 parts, cashew nut shell oil resin 3 parts, toughening agent 10 parts, curing agent 2 parts, catalyst 0.5 parts, diluent 20 parts.

[0065] The epoxy resin is composed of trifunctional bisphenol A type epoxy resin and DOPO modified epoxy resin with a mass ratio of 1:1.

[0066] The trifunctional bisphenol A type epoxy resin is from Shanghai Zhongsi Industry Co., Ltd., with a brand name of 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 DOPO modified phenolic epoxy resin; the DOPO modified phenolic epoxy resin is from Tongyu New Materials (Guangdong) Co., Ltd., with a brand name of TER628K70, and a phosphorus content of 2.4%.

[0068] The bismaleimide resin is aromatic polymeric amine type bismaleimide resin; the aromatic polymeric amine type 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.

[0069] The cashew nut shell oil resin has a viscosity of 40000-51000 cps (25°C) and is from Cadere, with a brand name of NX-4778.

[0070] The toughening agent is composed of phenolic hydroxyl polyether sulfone and isocyanate group-containing nanomaterials with a mass ratio of 1:6.

[0071] The phenolic hydroxyl polyether sulfone has an average particle size of 35 μm, a molecular weight of 55000 g / mol, and a hydroxyl content of >50 Micro-equiv / g, and is from Shanghai Zhongsi Industry Co., Ltd., with a brand name of E2020P SR Micro.

[0072] The preparation method of the isocyanate group-containing nanomaterial is as follows: dendritic mesoporous silica nanoparticles are placed in ethyl acetate (CAS No. 141-78-6), 1,5-naphthalene diisocyanate and dibutyltin dilaurate (CAS No. 77-58-7) are added, a grafting reaction is carried out at 75℃ for 4h under a nitrogen protective atmosphere, and after the reaction is completed, washing and drying are carried out to obtain the isocyanate group-containing nanomaterial.

[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 a water-dispersed form, are sourced from Nanjing Dongna Biological Technology Co., Ltd., have a product code of DMSNs, a concentration of 5mg / L and a particle size of 200nm, and a transmission electron microscope picture thereof is as shown in Figure 1 .

[0075] The 1,5-naphthalene diisocyanate is sourced from Guangzhou Haoyi New Material 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: first, the epoxy resin, bismaleimide resin, cashew nut shell oil resin and diluent are stirred uniformly, then the toughening agent is added and stirred uniformly, and finally the curing agent and catalyst are added and stirred uniformly to obtain the impact-resistant epoxy resin composition.

[0080] Example 2

[0081] The impact-resistant epoxy resin composition disclosed in the example is prepared from the following components in parts by weight: epoxy resin 38 parts, bismaleimide resin 7 parts, cashew nut shell oil resin 5 parts, toughening agent 16 parts, curing agent 3.5 parts, catalyst 1 part and diluent 28 parts.

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

[0083] The trifunctional bisphenol A type epoxy resin is sourced from Shanghai Zhongsiji Industrial Co., Ltd. and has a product code of EP-4100HF, an epoxy equivalent weight of 182g / eq and a total chlorine content of <600ppm.

[0084] The DOPO modified epoxy resin is a DOPO modified phenolic epoxy resin; the DOPO modified phenolic epoxy resin is from Tongyu New Material (Guangdong) Co., Ltd., and the model number is TER628K70, and the phosphorus content is 2.4%.

[0085] The bismaleimide resin is an aromatic polymeric polyamine type bismaleimide resin; the aromatic polymeric polyamine type bismaleimide resin is from Jinan Shengquan Group Co., Ltd., and the model number is PFB502, and the solid content is 70±2%, and the weight average molecular weight is 900±100.

[0086] The cashew nut shell liquid resin has a viscosity of 40000-51000 cps (25℃), and is from Cadere, and the model number is NX-4778.

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

[0088] The phenolic hydroxyl polyether sulfone has an average particle size of 35 μm, a molecular weight of 55000 g / mol, and a hydroxyl content of >50 Micro-equiv / g, and is from Shanghai Zhongsi Industry Co., Ltd., and the model number is E2020P SR Micro.

[0089] The preparation method of the isocyanate group-containing nanomaterial is as follows: dendritic mesoporous silica nanoparticles are placed in ethyl acetate (CAS number: 141-78-6), 1,5-naphthalene diisocyanate and dibutyltin dilaurate (CAS number: 77-58-7) are added, a grafting reaction is carried out under a nitrogen protection atmosphere at 75℃ for 4h, and after the reaction is completed, washing and drying are carried out to obtain the isocyanate group-containing nanomaterial.

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

[0091] The dendritic mesoporous silica nanoparticles are in a water dispersion form, are from Nanjing Dongna Biological Technology Co., Ltd., and the article number is DMSNs, the concentration is 5 mg / L, and the particle size is 200 nm, and the transmission electron microscope picture is as shown in Figure 1 .

[0092] The 1,5-naphthalene diisocyanate is from Guangzhou Haoyi New Material Technology Co., Ltd., and the NCO content is 40%.

[0093] The curing agent is dicyandiamide (CAS number: 461-58-5).

[0094] The catalyst is 2-methylimidazole (CAS number: 693-98-1).

[0095] The diluent is acetone (CAS number: 67-64-1).

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

[0097] Example 3

[0098] The impact-resistant epoxy resin composition disclosed in the embodiment comprises the following components 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 is composed of a trifunctional bisphenol A type epoxy resin and a DOPO modified epoxy resin in a mass ratio of 1:1.

[0100] The trifunctional bisphenol A type epoxy resin is sourced from Shanghai Zhongsi Industry Co., Ltd., with a brand name of EP-4100HF and 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 phenolic epoxy resin, which is sourced from Tongyu New Material (Guangdong) Co., Ltd., with a brand name of TER628K70 and a phosphorus content of 2.4%.

[0102] The bismaleimide resin is an aromatic polymeric amine type bismaleimide resin, which 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 Kardie, with a brand name of NX-4778.

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

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

[0106] The preparation method of the isocyanate group-containing nanomaterial is as follows: dendritic mesoporous silica nanoparticles are placed in ethyl acetate (CAS No. 141-78-6), 1,5-naphthalene diisocyanate and dibutyltin dilaurate (CAS No. 77-58-7) are added, a grafting reaction is carried out at 75℃ for 4h under a nitrogen protective atmosphere, and after the reaction is completed, washing and drying are carried out to obtain the isocyanate group-containing nanomaterial.

[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 a water-dispersed form, are sourced from Nanjing Dongna Biological Technology Co., Ltd., have a product code of DMSNs, a concentration of 5mg / L and a particle size of 200nm, and a transmission electron microscope picture thereof is as shown in Figure 1

[0109] The 1,5-naphthalene diisocyanate is sourced from Guangzhou Haoyi New Material 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: the epoxy resin, bismaleimide resin, cashew nut shell oil resin and diluent are stirred uniformly, the toughening agent is then added and stirred uniformly, and finally the curing agent and catalyst are added and stirred uniformly to obtain the impact-resistant epoxy resin composition.

[0114] Example 4

[0115] The impact-resistant epoxy resin composition disclosed in the example is prepared from the following components in parts by weight: epoxy resin 50 parts, bismaleimide resin 10 parts, cashew nut shell oil resin 8 parts, toughening agent 20 parts, curing agent 5 parts, catalyst 1.5 parts and diluent 30 parts.

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

[0117] The trifunctional bisphenol A type epoxy resin is sourced from Shanghai Zhongsiji Industrial Co., Ltd. and has a product code of EP-4100HF, an epoxy equivalent weight of 182g / eq and a total chlorine content of <600ppm.

[0118] ​The DOPO modified epoxy resin is a DOPO modified phenolic epoxy resin; the DOPO modified phenolic epoxy resin is from Tongyu New Material (Guangdong) Co., Ltd., and the model number is TER628K70, and the phosphorus content is 2.4%.

[0119] The bismaleimide resin is an aromatic polymeric polyamine type bismaleimide resin; the aromatic polymeric polyamine type bismaleimide resin is from Jinan Shengquan Group Co., Ltd., and the model number is PFB502, and the solid content is 70±2%, and the weight average molecular weight is 900±100.

[0120] The cashew nut shell liquid resin has a viscosity of 40000-51000 cps (25℃), and is from Cadere, and the model number is NX-4778.

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

[0122] The phenolic hydroxyl polyether sulfone has an average particle size of 35 μm, a molecular weight of 55000 g / mol, and a hydroxyl content of >50 Micro-equiv / g, and is from Shanghai Zhongsi Industry Co., Ltd., and the model number is E2020P SR Micro.

[0123] The preparation method of the isocyanate group-containing nanomaterial is as follows: dendritic mesoporous silica nanoparticles are placed in ethyl acetate (CAS number: 141-78-6), 1,5-naphthalene diisocyanate and dibutyltin dilaurate (CAS number: 77-58-7) are added, a grafting reaction is carried out under a nitrogen protection atmosphere at 75℃ for 4h, and after the reaction is completed, washing and drying are carried out to obtain the isocyanate group-containing nanomaterial.

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

[0125] The dendritic mesoporous silica nanoparticles are in a water dispersion form, are from Nanjing Dongna Biological Technology Co., Ltd., and the article number is DMSNs, the concentration is 5 mg / L, and the particle size is 200 nm, and the transmission electron microscope picture is as shown in Figure 1 .

[0126] The 1,5-naphthalene diisocyanate is from Guangzhou Haoyi New Material Technology Co., Ltd., and the NCO content is 40%.

[0127] The curing agent is dicyandiamide (CAS number: 461-58-5).

[0128] The catalyst is 2-methylimidazole (CAS number: 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: first, the epoxy resin, bismaleimide resin, cashew nut shell oil resin and diluent are stirred uniformly, then the toughening agent is added and stirred uniformly, and finally the curing agent and catalyst are added and stirred uniformly.

[0131] Comparative Example 1

[0132] This comparative example discloses an impact-resistant epoxy resin composition, which is different from Example 4 in that the cashew nut shell oil resin is replaced by tung oil modified phenolic resin, which is derived from Jining Baiyi Chemical Co., Ltd.; the rest are the same.

[0133] Comparative Example 2

[0134] This comparative example discloses an impact-resistant epoxy resin composition, which is different from Example 4 in that the toughening agent is a 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 is different from Example 4 in that the toughening agent is a nano material containing isocyanate groups; the rest are the same.

[0137] Comparative Example 4

[0138] This comparative example discloses an impact-resistant epoxy resin composition, which is different from Example 4 in that the toughening agent is composed of phenolic hydroxyl polyether sulfone and dendritic mesoporous silica nanoparticles in a mass ratio of 1:6; the rest are the same.

[0139] Comparative Example 5

[0140] This comparative example discloses an impact-resistant epoxy resin composition, which is different from Example 4 in that the dendritic mesoporous silica nanoparticles are replaced by the same mass of mesoporous silica nanoparticles; the mesoporous silica nanoparticles are derived from Nanjing Dongna Biological Technology Co., Ltd., with a product code of MSNs; the particle size is 100 nm; the transmission electron microscope image is shown in Figure 2 ; the rest are the same.

[0141] Comparative Example 6

[0142] This comparative example discloses an impact-resistant epoxy resin composition, which is different from Example 3 in that 1,5-naphthalene diisocyanate is replaced by the same mass of hexamethylene diisocyanate, which is derived from Wanhua Chemical Group Co., Ltd., with an NCO content of 49.7%; the rest are the same.

[0143] Application Example

[0144] The 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 compositions of Examples 1-4 and Comparative Examples 1-6, taken out after 10 s of immersion, and cured at 180℃ for 3 min to prepare a prepreg. The prepreg was covered with a 40 μm copper foil on both sides and hot-pressed to bond, the hot-pressing temperature was 200℃, the hot-pressing pressure was 35 kg / cm 2 , and a copper-clad plate sample was obtained after 120 min of pressing. The copper-clad plate sample was subjected to the following performance tests:

[0145] 1. Impact resistance: tested by a falling weight impact tester, the weight of the falling weight was 1 kg, the falling height was 1 meter, the area of the impact mark was measured, and the smaller the area, the better the impact resistance;

[0146] 2. Peel strength: detected according to GB / T 4722-2017-7.2.1;

[0147] 3. Flame retardancy: detected according to GB / T 4722-2017-6.4.1;

[0148] 4. Heat resistance: detected according to GB / T 4722-2017-6.11, the heat delamination time under the condition of 288℃;

[0149] 5. Dielectric constant: detected according to GB / T 4722-2017-8.5, the dielectric constant under 10 Hz.

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

[0151]

[0152]

[0153] As can be seen from the above data, the copper-clad plate prepared from the epoxy resin composition prepared by the present application has excellent impact resistance, as well as high peel strength, good flame retardancy, good heat resistance and good dielectric properties;

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

[0155] The phenolic hydroxyl polyether sulfone and the self-prepared nano material containing isocyanate groups are used as toughening agents, and the epoxy resin composition obtained through the synergistic effect of the two improves the impact resistance and heat resistance of the copper-clad plate, and also improves the peel strength of the copper-clad plate; the nano material 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 plate, and also affects the peel strength and dielectric properties of the copper-clad plate.

[0156] Comparative Example 2 and Comparative Example 3 only use single-component toughening agents, resulting in a decrease in the impact resistance, peel strength and heat resistance of the copper-clad plate;

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

[0158] Finally, it should be noted that the above content is only used to illustrate the technical solutions of the present application, and is not a limitation on the protection scope of the present application. Simple modifications or equivalent replacements of the technical solutions of the present application made by those skilled in the art do not deviate from the essence and scope of the technical solutions of the present application.

Claims

1. An impact resistant epoxy resin composition characterized by comprising, The components include the following weight parts: epoxy resin 30-50 parts, bismaleimide resin 5-10 parts, cashew shell oil resin 3-8 parts, toughening agent 10-20 parts, curing agent 2-5 parts, catalyst 0.1-2 parts, diluent 20-30 parts; The toughening agent includes phenolic hydroxyl polyether sulfone and isocyanate group-containing nanomaterial; the nanomaterial is dendritic mesoporous silica nanoparticles; The mass ratio of the phenolic hydroxyl polyether sulfone and the isocyanate group-containing nanomaterial is 1:6; The isocyanate group-containing nanomaterial is obtained by grafting dendritic mesoporous silica nanoparticles and 1,5-naphthalene diisocyanate under the action of a catalyst.

2. The impact-resistant epoxy resin composition according to claim 1, characterized in that, The epoxy resin includes trifunctional bisphenol A type epoxy resin and DOPO modified epoxy resin; The total chlorine content of the trifunctional bisphenol A type epoxy resin is <600 ppm; The DOPO modified epoxy resin is DOPO modified phenolic epoxy resin; The phosphorus content of the DOPO modified phenolic 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 type bismaleimide resin and aromatic polymeric polyamine type bismaleimide resin.

4. The impact-resistant epoxy resin composition according to any one of claims 1 to 3, characterized in that, The preparation method of the isocyanate group-containing nanomaterial includes the following steps: placing dendritic mesoporous silica nanoparticles in a solvent, adding 1,5-naphthalene diisocyanate and a catalyst, performing grafting reaction, and after the reaction is completed, performing washing and drying to obtain the isocyanate group-containing nanomaterial.

5. The impact-resistant epoxy resin composition according to claim 4, 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.

6. The impact-resistant epoxy resin composition according to claim 4, characterized in that, The particle size of the dendritic mesoporous silica nanoparticles is 100-200 nm.

7. The impact-resistant epoxy resin composition according to claim 4, wherein The temperature of the grafting reaction is 72-78℃, and the time is 4-5h.

8. A process for the production of the impact-resistant epoxy resin composition according to any one of claims 1 to 7, characterized in that, The method includes the following steps: first, stirring the epoxy resin, the bismaleimide resin, the cashew shell oil resin and the diluent uniformly, then adding the toughening agent and stirring uniformly, and finally adding the curing agent and the catalyst and stirring uniformly to obtain the epoxy resin composition.

9. Use of the impact-resistant epoxy resin composition according to any one of claims 1-7 in the preparation of copper-clad plates.

Images