Modified epoxy resin, epoxy base laminate and manufacturing method thereof

Abstract

The present invention provides a modified epoxy resin, an epoxy base laminate and a manufacturing method thereof. The modified epoxy resin includes an interpenetrating network of a cyanate ester polymer and an epoxy resin, and the modified epoxy resin further includes boron nitride nanosheets modified by end-hydroxyl hyperbranched polyphenylene ether dispersed in the interpenetrating network. The above-mentioned modified epoxy resin of the present application is an interpenetrating network of a cyanate ester polymer and an epoxy resin, which is formed by modifying the epoxy resin with the above-mentioned modified boron nitride nanosheets and cyanate monomers in a certain ratio, and the boron nitride has a relatively high thermal conductivity. The present application uses the amino groups and hydroxyl groups existing at the lattice defects of boron nitride to modify it with end-hydroxyl hyperbranched polyphenylene ether, so that the modified epoxy resin can be improved in both thermal conductivity and heat resistance, improving the problem of poor temperature resistance of traditional epoxy copper clad laminate materials, thus meeting the application in the 5G field while reducing the cost of products.

Description

Technical Field

[0001] The present invention relates to the technical field of epoxy resin modification, and in particular, to a modified epoxy resin, an epoxy base laminate and a manufacturing method thereof. Background Art

[0002] With the continuous development of printed circuit boards (PCBs) towards high density and multi - layer, the space for mounting and installing components on PCBs has been significantly reduced, and the power requirements of power components for the whole electronic products are getting higher and higher. Inevitably, more heat is generated in a small space with high power, resulting in a decline in the electrical performance of components or even damage.

[0003] Epoxy copper clad laminates are the most widely used in the market at present, but they are restricted due to their poor heat resistance and low heat transfer efficiency. With the advent of 5G, the development of new copper clad laminates (such as PTFE, hydrocarbon copper clad laminates, etc.) gradually replaces traditional epoxy copper clad laminates, but it has become a big problem because of their high price. Summary of the Invention

[0004] The main object of the present invention is to provide a modified epoxy resin, an epoxy base laminate and a manufacturing method thereof, so as to solve the problem in the prior art that the epoxy base laminate cannot have both heat resistance and low cost.

[0005] To achieve the above object, according to one aspect of the present invention, a modified epoxy resin is provided. The modified epoxy resin includes an interpenetrating network of cyanate ester polymer and epoxy resin, and the modified epoxy resin further includes boron nitride nanosheets modified with hydroxyl - terminated hyperbranched poly(phenylene ether) dispersed in the interpenetrating network.

[0006] Further, the raw materials of the modified epoxy resin include boron nitride nanosheets, cyanate ester monomers and epoxy resin, and the weight ratio of the boron nitride nanosheets modified with hydroxyl - terminated hyperbranched poly(phenylene ether), cyanate ester monomers and epoxy resin is 1:(0.5 - 1):(5 - 20).

[0007] According to another aspect of the present invention, a manufacturing method of an epoxy base laminate is also provided, including the following steps: forming an epoxy base laminate by using the raw materials of the above - mentioned modified epoxy resin.

[0008] Further, the boron nitride nanosheets modified with hydroxyl - terminated hyperbranched poly(phenylene ether) in the raw materials of the epoxy resin are prepared by the following method: mixing a first solution in which boron nitride nanosheets are dispersed with hydroxyl - terminated hyperbranched poly(phenylene ether) so that the hydroxyl - terminated hyperbranched poly(phenylene ether) is modified onto the surface of the boron nitride nanosheets to obtain a first mixed solution; separating the solid and liquid of the first mixed solution to obtain the boron nitride nanosheets modified with hydroxyl - terminated hyperbranched poly(phenylene ether).

[0009] Further, before the step of dispersing the hydroxyl-terminated hyperbranched polyphenylene ether in the first mixed solution, the step of preparing the hydroxyl-terminated hyperbranched polyphenylene ether-modified boron nitride nanosheets further includes: centrifuging the first mixed solution to separate the unexfoliated boron nitride nanosheets in the first mixed solution. Preferably, the centrifuging rate is 5000-8000 rpm.

[0010] Further, the step of forming the epoxy base laminate using the raw materials of the epoxy resin includes: mixing the molten cyanate ester monomer with the hydroxyl-terminated hyperbranched polyphenylene ether-modified boron nitride nanosheets to obtain a second mixed solution; mixing the second mixed solution with the epoxy resin and heating for a polymerization reaction to form a third mixed solution containing a prepolymer. Preferably, the heating temperature is 80-120 °C; using the third mixed solution and a reinforcing material to form a prepreg, stacking the prepregs in multiple layers and performing a hot pressing polymerization reaction to form an interpenetrating network of the cyanate ester polymer and the epoxy resin. Preferably, the hot pressing temperature is 150-180 °C and the time is 2-4 h.

[0011] Further, the viscosity of the third mixed solution is 1500-3000 cp.

[0012] Further, impregnating the glass fiber cloth with the third mixed solution to form a prepreg.

[0013] Further, the areal density of the prepreg is 150-180 g / m 2 .

[0014] According to another aspect of the present invention, an epoxy base laminate is provided, and the epoxy base laminate is made by the above manufacturing method.

[0015] Applying the technical solution of the present invention, a modified epoxy resin is provided. The modified epoxy resin is an interpenetrating network of a cyanate ester polymer and an epoxy resin, and its raw materials include hydroxyl-terminated hyperbranched polyphenylene ether-modified boron nitride nanosheets, a cyanate ester monomer, and an epoxy resin. The hydroxyl-terminated hyperbranched polyphenylene ether-modified boron nitride nanosheets are dispersed in the interpenetrating network. The above modified epoxy resin of the present application is an interpenetrating network of a cyanate ester polymer and an epoxy resin, which is formed by modifying the epoxy resin with the above-mentioned modified boron nitride nanosheets and the cyanate ester monomer in a certain ratio. Moreover, the thermal conductivity of boron nitride is relatively high. The present application uses the amino and hydroxyl groups existing at the lattice defects of boron nitride to modify it with hydroxyl-terminated hyperbranched polyphenylene ether, so that the modified epoxy resin can be improved in terms of thermal conductivity and heat resistance, and the problem of poor temperature resistance of traditional epoxy copper clad laminate materials is improved, so as to meet the application in the 5G field while reducing the cost of the product. Specific Embodiments

[0016] It should be noted that, without conflict, the embodiments and features in the embodiments of the present invention may be combined with each other. The present invention will be described in detail below with reference to the embodiments.

[0017] In order to enable those skilled in the art to better understand the solution of the present invention, the technical solutions in the embodiments of the present invention will be clearly and completely described below in conjunction with the embodiments of the present invention. Obviously, the described embodiments are only a part of the embodiments of the present invention, rather than all the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those of ordinary skill in the art without creative work shall fall within the protection scope of the present invention.

[0018] It should be noted that the terms "first", "second", etc. in the description and claims of the present invention are used to distinguish similar objects, and do not necessarily need to describe a specific order or sequence. It should be understood that such data can be interchanged under appropriate circumstances for the embodiments of the present invention described herein. In addition, the terms "comprising" and "having" and any variations thereof are intended to cover non-exclusive inclusion. For example, a process, method, system, product or device comprising a series of steps or units does not necessarily have to be limited to those steps or units clearly listed, but may include other steps or units not clearly listed or inherent to these processes, methods, products or devices.

[0019] As introduced in the background art, epoxy copper clad laminates are the most widely used in the current market, but they are limited due to their poor heat resistance and low heat transfer efficiency. With the advent of 5G, the development of new copper clad laminates (such as PTFE, hydrocarbon copper clad laminates, etc.) gradually replaces traditional epoxy copper clad laminates, but it has become a great problem due to their high price.

[0020] In order to solve the above technical problems, the present application proposes a modified epoxy resin, which includes an interpenetrating network of cyanate ester polymer and epoxy resin, and boron nitride nanosheets modified with terminal hydroxyl hyperbranched polyphenylene ether are dispersed in the interpenetrating network.

[0021] The above modified epoxy resin in the present application is an interpenetrating network of cyanate ester polymer and epoxy resin, which is formed by modifying epoxy resin with the above-mentioned modified boron nitride nanosheets and cyanate ester monomers in a certain ratio. Moreover, the thermal conductivity of boron nitride is relatively high. The present application uses terminal hydroxyl hyperbranched polyphenylene ether to modify boron nitride at the lattice defects where amino groups and hydroxyl groups exist, so that the modified epoxy resin can be improved in both thermal conductivity and heat resistance, and the problem of poor temperature resistance of traditional epoxy copper clad laminate materials is improved. Thus, while meeting the application in the 5G field, the cost of the product is reduced.

[0022] The raw materials of the above-mentioned modified epoxy resin include boron nitride nanosheets modified with hydroxyl-terminated hyperbranched polyphenylene ether, cyanate ester monomers, and epoxy resin. In order to further improve the thermal conductivity and heat resistance of the interpenetrating network system, the weight ratio of the boron nitride nanosheets modified with hydroxyl-terminated hyperbranched polyphenylene ether, cyanate ester monomers, and epoxy resin is 1:(0.5 - 1):(5 - 20).

[0023] According to another aspect of the present invention, there is also provided a method for manufacturing an epoxy-based laminate, including the following steps: forming an epoxy-based laminate by using the raw materials of the above-mentioned modified epoxy resin.

[0024] In the method for manufacturing the above-mentioned epoxy-based laminate of the present invention, boron nitride (BN) with a relatively high thermal conductivity is used. The amino and hydroxyl groups existing at the lattice defects of BN are used to modify the boron nitride nanosheets with hydroxyl-terminated hyperbranched polyphenylene ether, and the epoxy resin is modified by the above-mentioned boron nitride nanosheets and cyanate ester in a certain ratio. The formed interpenetrating network system has improved thermal conductivity and heat resistance, and solves the problem of poor temperature resistance of traditional epoxy copper clad laminate materials, thereby meeting the application in the 5G field while reducing the cost of the product.

[0025] Exemplary embodiments of the method for manufacturing an epoxy-based laminate provided according to the present invention will be described in more detail below. However, these exemplary embodiments can be implemented in many different forms and should not be construed as being limited only to the embodiments described herein. It should be understood that these embodiments are provided to make the disclosure of the present application thorough and complete, and to fully convey the concept of these exemplary embodiments to those of ordinary skill in the art.

[0026] First, the preparation of boron nitride nanosheets modified with hydroxyl-terminated hyperbranched polyphenylene ether is carried out. By using the amino and hydroxyl groups at the surface defects of the boron nitride nanosheets, the hydroxyl-terminated hyperbranched polyphenylene ether is used to modify them, and the modified boron nitride nanosheets have a catalytic effect on cyanate ester.

[0027] In a preferred embodiment, the above-mentioned boron nitride nanosheets modified with hydroxyl-terminated hyperbranched polyphenylene ether are prepared by the following method: mixing a first solution in which boron nitride nanosheets are dispersed with hydroxyl-terminated hyperbranched polyphenylene ether to modify the hydroxyl-terminated hyperbranched polyphenylene ether onto the surface of the boron nitride nanosheets to obtain a first mixed solution; separating the solid and liquid of the first mixed solution to obtain the boron nitride nanosheets modified with hydroxyl-terminated hyperbranched polyphenylene ether.

[0028] In the above-mentioned preferred embodiment, the solvent for dispersing the boron nitride nanosheets can be an N-methylpyrrolidone solution (NMP solution). In order to improve the dispersibility of the boron nitride nanosheets in the solvent, the boron nitride nanosheets can be ultrasonically treated in the solvent.

[0029] Before the step of dispersing the above-mentioned hydroxyl-terminated hyperbranched polyphenylene ether in the first mixed solution, the step of preparing the boron nitride nanosheets modified with hydroxyl-terminated hyperbranched polyphenylene ether may further include: centrifuging the first mixed solution to separate the unexfoliated boron nitride nanosheets in the first mixed solution. Preferably, the rate of the above-mentioned centrifuging is 5000-8000 rpm. By the above-mentioned centrifuging to remove the unexfoliated boron nitride nanosheets in the first mixed solution, a first mixed solution with uniformly dispersed boron nitride nanosheets is obtained.

[0030] Then, the cyanate ester is melted to form a liquid, and the above-mentioned boron nitride nanosheets modified with hydroxyl-terminated hyperbranched polyphenylene ether are mixed with the molten cyanate ester liquid to obtain a second mixed solution. Preferably, the temperature at which the cyanate ester monomer is melted can be 100 °C.

[0031] After obtaining the above-mentioned second mixed solution, the above-mentioned second mixed solution is used as a modifier to be mixed with epoxy resin and heated to carry out a polymerization reaction to form a third mixed solution containing a prepolymer. Preferably, the temperature of the above-mentioned heating is 80-120 °C.

[0032] Then, the above-mentioned third mixed solution containing a prepolymer is used to form a prepreg with a reinforcing material. The prepregs are stacked in multiple layers and hot-pressed to carry out a polymerization reaction to form an interpenetrating network of cyanate ester polymer and epoxy resin. Preferably, the temperature of the above-mentioned hot-pressing is 150-180 °C, and the time is 2-4 h.

[0033] In a preferred embodiment, the above-mentioned reinforcing material is a glass fiber cloth. The above-mentioned third mixed solution containing a prepolymer is impregnated into the glass fiber cloth to form a prepreg; the prepregs are stacked in multiple layers and hot-pressed to form an epoxy laminate.

[0034] More preferably, during the process of mixing the above-mentioned second mixed solution with the above-mentioned epoxy resin and heating, when the viscosity of the reaction system reaches 1500-3000 cp, the heating is stopped to obtain the above-mentioned third mixed solution. The third mixed solution satisfying the above viscosity range can be better impregnated in the fiber cloth to form a prepreg, which is beneficial to the production of epoxy laminates after the prepregs are laminated.

[0035] To improve the performance of the epoxy laminate after lamination, more preferably, the areal density of the above-mentioned prepreg is 150-180 g / m 2

[0036] To improve the performance of the epoxy laminate after lamination, more preferably, the temperature of the above-mentioned hot-pressing is 150-180 °C, and the time is 2-4 h.

[0037] According to another aspect of the present invention, an epoxy laminate is further provided, and the epoxy laminate is made by the above-mentioned manufacturing method.

[0038] The modified epoxy resin used in the above manufacturing method is an interpenetrating network system obtained by modifying epoxy resin with BN nanomaterials and cyanate ester in a certain ratio, which has improved thermal conductivity and heat resistance, and solves the problem of poor temperature resistance of traditional epoxy copper clad laminate materials. Thus, while meeting the application requirements in the 5G field, the cost of the product is reduced.

[0039] The following will further illustrate the manufacturing method of the above epoxy base laminate of the present invention in combination with examples and comparative examples.

[0040] Example 1

[0041] This example provides a manufacturing method of an epoxy base laminate, including the following steps:

[0042] Step 1: Preparation of surface-modified boron nitride nanosheets

[0043] Weigh 5 g of boron nitride powder into 100 ml of NMP solution, stir and ultrasonically treat for 8 h, centrifuge the treated mixed solution in a centrifuge at 8000 rpm, remove the unpeeled boron nitride powder in the lower layer, collect the upper-layer mixed solution, disperse hyperbranched hydroxyl-terminated polyphenylene ether into the upper-layer clear liquid, mix well, and dry by suction filtration to obtain the final powder.

[0044] Step 2: Preparation of epoxy base laminate

[0045] Weigh an appropriate amount of cyanate ester monomer (Yangzhou Tianqi New Materials, bisphenol A cyanate ester monomer, C01MO), heat and melt it at 100 °C, add the boron nitride powder modified with hydroxyl-terminated hyperbranched polyphenylene ether in Step 1 into the above molten cyanate ester, and mix and stir well;

[0046] Add the above mixed solution into an epoxy resin solution (Nantong Xingchen Synthetic Materials Co., Ltd., model WSR618 (E51), Phoenix brand, epoxy equivalent 184 - 195 g / mol, volatile matter ≤ 1.5%), stir well at 100 °C. The weight ratio of the surface-modified boron nitride powder, cyanate ester monomer, and epoxy resin is 1:1:20. Stop heating when the viscosity of the system reaches 3000 cp;

[0047] Impregnate the above mixed solution into a 2116-type glass fiber cloth to prepare a prepreg with a surface density of 160 g / m 2 ², and then stack multiple layers and hot-press at 150 °C for 2 h and at 180 °C for 2 h.

[0048] Example 2

[0049] The difference between the manufacturing method of the epoxy base laminate provided in this example and that in Example 1 lies in:

[0050] The weight ratio of the surface-modified boron nitride powder, cyanate ester monomer and epoxy resin is 1:1:18.

[0051] Example 3

[0052] The difference between the method for manufacturing the epoxy base laminate provided in this example and that in Example 1 lies in:

[0053] The weight ratio of the surface-modified boron nitride powder, cyanate ester monomer and epoxy resin is 1:1:8.

[0054] Example 4

[0055] The difference between the method for manufacturing the epoxy base laminate provided in this example and that in Example 1 lies in:

[0056] The weight ratio of the surface-modified boron nitride powder, cyanate ester monomer and epoxy resin is 1:0.5:5.

[0057] Example 5

[0058] The difference between the method for manufacturing the epoxy base laminate provided in this example and that in Example 1 lies in:

[0059] The weight ratio of the surface-modified boron nitride powder, cyanate ester monomer and epoxy resin is 1:1:3.

[0060] Example 6

[0061] The difference between the method for manufacturing the epoxy base laminate provided in this example and that in Example 1 lies in:

[0062] The weight ratio of the surface-modified boron nitride powder, cyanate ester monomer and epoxy resin is 1:2:10.

[0063] Example 7

[0064] The difference between the method for manufacturing the epoxy base laminate provided in this example and that in Example 1 lies in:

[0065] Centrifuge the treated mixed solution in a centrifuge at 5000 rpm.

[0066] Example 8

[0067] The difference between the method for manufacturing the epoxy base laminate provided in this example and that in Example 1 lies in:

[0068] Centrifuge the treated mixed solution in a centrifuge at 3000 rpm.

[0069] Example 9

[0070] The difference between the method for manufacturing the epoxy base laminate provided in this example and that in Example 1 lies in:

[0071] The boron nitride powder modified with hydroxyl-terminated hyperbranched polyphenylene ether was added to the above cyanate ester solution, and after being fully mixed and stirred evenly, the above mixed solution was added to the epoxy resin solution and stirred evenly at 80 °C.

[0072] Example 10

[0073] The difference between the method for manufacturing the epoxy base laminate provided in this example and that in Example 1 lies in:

[0074] The boron nitride powder modified with hydroxyl-terminated hyperbranched polyphenylene ether was added to the above cyanate ester solution, and after being fully mixed and stirred evenly, the above mixed solution was added to the epoxy resin solution and stirred evenly at 120 °C.

[0075] Example 11

[0076] The difference between the method for manufacturing the epoxy base laminate provided in this example and that in Example 1 lies in:

[0077] The boron nitride powder modified with hydroxyl-terminated hyperbranched polyphenylene ether was added to the above cyanate ester solution, and after being fully mixed and stirred evenly, the above mixed solution was added to the epoxy resin solution and stirred evenly at 70 °C.

[0078] Example 12

[0079] The difference between the method for manufacturing the epoxy base laminate provided in this example and that in Example 1 lies in:

[0080] The above mixed solution was added to the epoxy resin solution and stirred evenly, and the heating was stopped when the viscosity of the system reached 2000 cp.

[0081] Example 13

[0082] The difference between the method for manufacturing the epoxy base laminate provided in this example and that in Example 1 lies in:

[0083] The above mixed solution was added to the epoxy resin solution and stirred evenly, and the heating was stopped when the viscosity of the system reached 1500 cp.

[0084] Example 14

[0085] The difference between the method for manufacturing the epoxy base laminate provided in this example and that in Example 1 lies in:

[0086] The mixed solution was impregnated into the glass fiber cloth of model 2116 to prepare a prepreg with a surface density of 150 g / m 2 and then multiple layers were stacked and hot-pressed at 150 °C for 4 h.

[0087] Example 15

[0088] The difference between the method for manufacturing the epoxy base laminate provided in this embodiment and that in Embodiment 1 lies in that:

[0089] The mixed solution is impregnated into a glass fiber cloth of Model 2116 to prepare a prepreg with a surface density of 150 g / m 2 , and then multiple layers are stacked and hot-pressed at 180 °C for 2 h.

[0090] The laminates prepared in the above Embodiments 1 to 15 are subjected to thermal performance and dielectric performance tests, and the test results are shown in the following table.

[0091]

[0092]

[0093] From the above description, it can be seen that the above embodiments of the present invention achieve the following technical effects:

[0094] The above-mentioned modified epoxy resin in this application is an interpenetrating network of cyanate ester polymer and epoxy resin, which is formed by modifying epoxy resin with the above-mentioned modified boron nitride nanosheets and cyanate ester monomers in a certain ratio. Moreover, the boron nitride has a relatively high thermal conductivity. In this application, the amino groups and hydroxyl groups existing at the lattice defects of boron nitride are used to modify it with hydroxyl-terminated hyperbranched polyphenylene ether, so that the modified epoxy resin can be improved in both thermal conductivity and heat resistance, and the problem of poor heat resistance of traditional epoxy copper clad laminate materials is improved, thus meeting the application in the 5G field while reducing the cost of the product.

[0095] The above are only the preferred embodiments of the present invention and are not intended to limit the present invention. For those skilled in the art, the present invention can have various changes and modifications. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention shall be included within the protection scope of the present invention.

Claims

1. A modified epoxy resin, characterized in that, The modified epoxy resin includes an interpenetrating network of a cyanate ester polymer and an epoxy resin, and the modified epoxy resin further includes boron nitride nanosheets modified with hydroxyl-terminated hyperbranched polyphenylene ether dispersed in the interpenetrating network; The raw materials of the modified epoxy resin include boron nitride nanosheets modified with hydroxyl-terminated hyperbranched polyphenylene ether, cyanate ester monomers, and epoxy resin, and the weight ratio of the boron nitride nanosheets modified with hydroxyl-terminated hyperbranched polyphenylene ether, the cyanate ester monomers, and the epoxy resin is 1:(0.5 - 1):(5 - 20).

2. A method for manufacturing an epoxy-based laminate, characterized in that, It includes the following steps: Using the raw materials of the modified epoxy resin described in Claim 1 to form the epoxy base laminate.

3. The manufacturing method according to claim 2, characterized in that, The boron nitride nanosheets modified with hydroxyl-terminated hyperbranched polyphenylene ether in the raw materials of the modified epoxy resin are prepared by the following method: Mixing a first solution in which boron nitride nanosheets are dispersed with hydroxyl-terminated hyperbranched polyphenylene ether so that the hydroxyl-terminated hyperbranched polyphenylene ether is modified onto the surface of the boron nitride nanosheets to obtain a first mixed solution; Solid-liquid separating the first mixed solution to obtain the boron nitride nanosheets modified with hydroxyl-terminated hyperbranched polyphenylene ether.

4. The manufacturing method according to claim 3, characterized in that, Before the step of dispersing the hydroxyl-terminated hyperbranched polyphenylene ether in the first mixed solution, the step of preparing the boron nitride nanosheets modified with hydroxyl-terminated hyperbranched polyphenylene ether further includes: Centrifuging the first mixed solution.

5. The manufacturing method according to claim 4, characterized in that, The rate of the centrifuging is 5000 - 8000 rpm.

6. The manufacturing method according to claim 3, characterized in that, The step of using the raw materials of the modified epoxy resin to form the epoxy base laminate includes: Mixing the molten cyanate ester monomers with the boron nitride nanosheets modified with hydroxyl-terminated hyperbranched polyphenylene ether to obtain a second mixed solution; Mixing the second mixed solution with the epoxy resin and heating for a polymerization reaction to form a third mixed solution containing a prepolymer; Using the third mixed solution and a reinforcing material to form a prepreg, stacking the prepregs in multiple layers and performing a hot pressing polymerization reaction to form an interpenetrating network of a cyanate ester polymer and the epoxy resin.

7. The manufacturing method according to claim 6, characterized in that, The temperature of the heating is 80 - 120 °C.

8. The manufacturing method according to claim 6, characterized in that, The temperature of the hot pressing is 150 - 180 °C, and the time is 2 - 4 h.

9. The manufacturing method according to claim 6, characterized in that, The viscosity of the third mixed solution is 1500 - 3000 cp.

10. The manufacturing method according to claim 6, characterized in that, Impregnating the third mixed solution into a glass fiber cloth to form the prepreg.

11. The manufacturing method according to claim 6, characterized in that, The areal density of the prepreg is 150~180 g / m 2 .

12. An epoxy-based laminate, characterized in that, The epoxy base laminate is made by the manufacturing method according to any one of Claims 2 to 11.

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