Bio-based modified epoxy resin composition and application thereof

Abstract

The invention provides a bio-based modified epoxy resin composition and application thereof. The bio-based modified epoxy resin composition comprises the following components: bio-based modified epoxy resin, a bio-based curing agent and filler, the bio-based modified epoxy resin is prepared from bisphenol A epoxy resin, 2, 5-furandicarboxylic acid, maleic anhydride rosin and acrylic acid rosin. Bio-based modified epoxy resin is synthesized by taking bisphenol A epoxy resin, 2, 5-furandicarboxylic acid, maleic anhydride rosin and acrylic acid rosin as raw materials, and a copper-clad plate prepared from the bio-based modified epoxy resin can achieve the performance of a copper-clad plate prepared from the bisphenol A epoxy resin; the heat resistance and cohesiveness of a copper-clad plate prepared from the bio-based modified epoxy resin provided by the invention can meet the use requirements, and the copper-clad plate also has better flame retardance.

Description

Technical Field

[0001] The present invention belongs to the technical field of copper clad laminates, and relates to a bio-based modified epoxy resin composition and an application thereof, and specifically relates to a bio-based modified epoxy resin composition and a prepreg and a metal foil-clad laminate containing the same. Background Art

[0002] Copper clad laminates are widely used as key components in electronic products and are commonly known as the "land of the electronics industry." Conventional copper clad laminates are composed of epoxy resin, fillers and reinforcing materials. The raw materials of the epoxy resin used come from petroleum, which is a resource that cannot be regenerated in the short term, posing a huge challenge to my country's petroleum consumption.

[0003] Epoxy resin is one of the main raw materials for copper clad laminates. The development of bio-based epoxy resins and bio-based low-carbon copper clad laminates that do not rely on petroleum as raw materials is a future development trend. The main raw materials of existing common bio-based epoxy resins come from vegetable oils. Vegetable oils have good flexibility, but the heat resistance and adhesion of the corresponding copper clad laminates are significantly reduced, and cannot achieve the performance of existing bisphenol A epoxy resins and their copper clad laminates.

[0004] CN117363289A discloses a bio-based modified epoxy resin insulating adhesive and a preparation method thereof, wherein bisphenol F epoxy resin is modified using linolenic acid to improve the electrical insulation, dielectric and mechanical properties of the insulating adhesive layer. However, the heat shock resistance of the copper-clad laminate prepared using the bio-based modified epoxy resin insulating adhesive of this invention needs to be further improved.

[0005] CN118373966A discloses a tung oil-modified epoxy resin, its preparation method and application. The modified epoxy resin is obtained by alkylating tung oil with bisphenol or polyphenol and then reacting with epichlorohydrin. The modified epoxy resin mainly solves the problems of high brittleness and poor impact strength of epoxy resin. However, the thermal stress of the copper clad laminate prepared from the tung oil-modified epoxy resin of the invention is insufficient.

[0006] CN114133703A discloses a method for preparing a halogen-free, low-dielectric, and high-frequency compatible FR-4 copper-clad laminate, which uses a bio-based dimer acid glycidyl ester-modified multifunctional alicyclic epoxy resin as the main resin. Its main purpose is to reduce the dielectric loss of the resin system. However, in order to ensure that the Tg of the resin system is not reduced, the invention introduces BT resin, which will significantly increase the cost.

[0007] CN115806475A discloses a low-flammability bio-based epoxy resin based on guaiacol and a preparation method thereof. The epoxy resin is synthesized using guaiacol, a degradation product of lignin, with the aim of addressing the problems of bisphenol A epoxy resin, such as high physiological toxicity, non-renewability, and poor flame retardancy. However, its flame retardancy still needs to be further improved.

[0008] Therefore, in the art, it is desired to develop a bio-based modified epoxy resin composition, the copper clad laminate prepared from which not only has heat resistance and bonding properties comparable to those of copper clad laminates prepared using bisphenol A epoxy resin, but also has higher thermal stress and better flame retardancy. Summary of the Invention

[0009] In response to the shortcomings of the prior art, the present invention aims to provide a bio-based modified epoxy resin composition and its application. This invention primarily addresses the prior art issue that copper-clad laminates (CCLs) made using bio-based modified epoxy resins synthesized from vegetable oils cannot achieve the same performance as CCLs made using bisphenol A epoxy resins, primarily resulting in significantly reduced heat resistance and adhesion. Furthermore, the present invention utilizes bio-based raw materials to replace a portion of the bisphenol A epoxy resin, making it more environmentally friendly.

[0010] To achieve this object, the present invention adopts the following technical solutions:

[0011] In a first aspect, the present invention provides a bio-based modified epoxy resin composition, wherein the bio-based modified epoxy resin composition comprises the following components: a bio-based modified epoxy resin, a bio-based curing agent, and a filler;

[0012] The raw materials for preparing the bio-based modified epoxy resin include bisphenol A epoxy resin, 2,5-furandicarboxylic acid, maleic anhydride rosin and acrylic rosin.

[0013] The present invention synthesizes a bio-based modified epoxy resin by using bisphenol A epoxy resin, 2,5-furandicarboxylic acid, maleic anhydride rosin, and acrylic rosin as raw materials. The copper-clad laminate prepared with the bio-based modified epoxy resin can achieve the performance of a copper-clad laminate prepared with bisphenol A epoxy resin. The heat resistance and adhesion of the copper-clad laminate prepared with the bio-based modified epoxy resin provided by the present invention can meet the use requirements, and the laminate also has high thermal stress and good flame retardancy.

[0014] The present invention abandons vegetable oil monomers containing long carbon chain structural units that lead to reduced heat resistance and adhesion, and selects cyclic bio-based monomers containing rigidity in the molecular structure to react with bisphenol A epoxy resin to obtain a bio-based modified epoxy resin with better heat resistance and adhesion.

[0015] Preferably, the bisphenol A epoxy resin includes E51 epoxy resin.

[0016] Preferably, the raw materials for preparing the bio-based modified epoxy resin include the following components in parts by weight: 100 parts of bisphenol A epoxy resin, 5 to 15 parts of 2,5-furandicarboxylic acid (for example, 5 parts, 6 parts, 7 parts, 8 parts, 9 parts, 10 parts, 11 parts, 12 parts, 13 parts, 14 parts or 15 parts, and specific values ​​between the above points. Due to space limitations and for the sake of simplicity, the present invention no longer exhaustively lists the specific values ​​included in the range), 5 to 15 parts of maleic anhydride rosin (for example, 5 parts, 6 parts, 7 parts, 8 parts, 9 parts, 10 parts, 11 parts, 12 parts, 13 parts, 14 parts or 15 parts, and specific point values ​​between the above point values. Due to space limitations and for the sake of simplicity, the present invention no longer exhaustively lists the specific point values ​​included in the said range), 15 to 25 parts of acrylic rosin (for example, it can be 15 parts, 16 parts, 17 parts, 18 parts, 19 parts, 20 parts, 21 parts, 22 parts, 23 parts, 24 parts or 25 parts, and specific point values ​​between the above point values. Due to space limitations and for the sake of simplicity, the present invention no longer exhaustively lists the specific point values ​​included in the said range).

[0017] Preferably, the epoxy equivalent of the bio-based modified epoxy resin is 300 to 600 g / eq, for example, it can be 300 g / eq, 320 g / eq, 340 g / eq, 350 g / eq, 360 g / eq, 380 g / eq, 400 g / eq, 420 g / eq, 440 g / eq, 450 g / eq, 460 g / eq, 480 g / eq, 500 g / eq, 520 g / eq, 540 g / eq, 550 g / eq, 560 g / eq, 580 g / eq or 600 g / eq, as well as specific values ​​between the above points. Due to space limitations and for the sake of simplicity, the present invention no longer exhaustively lists the specific points included in the range.

[0018] Preferably, the bio-based modified epoxy resin is prepared by the following method:

[0019] Bisphenol A epoxy resin, 2,5-furandicarboxylic acid, maleic anhydride rosin, acrylic acid rosin and solvent in a prescribed amount are mixed and reacted to obtain the bio-based modified epoxy resin.

[0020] Preferably, the solvent comprises N,N-dimethylformamide.

[0021] Preferably, based on the total weight of bisphenol A epoxy resin, 2,5-furandicarboxylic acid, maleic anhydride rosin, and acrylic rosin as 100%, the amount of the solvent is 0.05% to 0.2%, for example, it can be 0.05%, 0.06%, 0.08%, 0.1%, 0.12%, 0.14%, 0.15%, 0.16%, 0.18% or 0.2%, as well as specific values ​​between the above points. Due to space limitations and for the sake of simplicity, the present invention no longer exhaustively lists the specific points included in the range.

[0022] Preferably, the reaction temperature is 120-140°C, for example, it can be 120°C, 125°C, 130°C, 135°C or 140°C, as well as specific point values ​​between the above point values. Due to space limitations and for the sake of simplicity, the present invention no longer exhaustively lists the specific point values ​​included in the range. The reaction time is 3-5h, for example, it can be 3h, 3.5h, 4h, 4.5h or 5h, as well as specific point values ​​between the above point values. Due to space limitations and for the sake of simplicity, the present invention no longer exhaustively lists the specific point values ​​included in the range.

[0023] Preferably, the bio-based curing agent includes any one of cardanol phenolic resin, tung oil phenolic resin, and epoxy soybean oil phenolic resin, or a combination of at least two thereof.

[0024] Preferably, the filler includes any one of tetrabromobisphenol A, aluminum hydroxide, polyphosphate amine, aluminum hypophosphite, and magnesium hydroxide, or a combination of at least two thereof.

[0025] Preferably, the bio-based modified epoxy resin composition comprises the following components in parts by weight: 100 parts of a bio-based modified epoxy resin, 25 to 40 parts of a bio-based curing agent (for example, 25 parts, 26 parts, 28 parts, 30 parts, 32 parts, 34 parts, 36 parts, 38 parts or 40 parts, and specific values ​​between the above points. Due to space limitations and for the sake of simplicity, the present invention does not exhaustively list the specific values ​​included in the range), and 30 to 80 parts of a filler. (For example, it can be 30 parts, 32 parts, 34 parts, 36 parts, 38 parts, 40 parts, 42 parts, 44 parts, 46 parts, 48 ​​parts, 50 parts, 52 parts, 54 parts, 56 parts, 58 parts, 60 parts, 62 parts, 64 parts, 66 parts, 68 parts, 70 parts, 72 parts, 74 parts, 76 parts, 78 parts or 80 parts, as well as specific point values ​​between the above point values. Due to space limitations and for the sake of simplicity, the present invention no longer exhaustively lists the specific point values ​​included in the said range).

[0026] Preferably, the bio-based modified epoxy resin composition further comprises a curing accelerator.

[0027] Preferably, the curing accelerator includes any one of tertiary amines, tertiary phosphines, organic metal complexes, quaternary ammonium salts or imidazole compounds (such as 2-methylimidazole) or a combination of at least two thereof.

[0028] Preferably, the weight portion of the curing accelerator is 0.05 to 0.2 parts, for example, it can be 0.05 parts, 0.06 parts, 0.08 parts, 0.1 parts, 0.12 parts, 0.14 parts, 0.15 parts, 0.16 parts, 0.18 parts or 0.2 parts, as well as specific values ​​between the above points. Due to space limitations and for the sake of simplicity, the present invention no longer exhaustively lists the specific points included in the range.

[0029] The “parts” and “parts by weight” involved in the present invention are all calculated based on solid content and do not include solvents, dispersants, etc.

[0030] A solvent may also be added to the bio-based modified epoxy resin composition. The amount of solvent added is selected by those skilled in the art based on experience and process requirements to achieve a suitable viscosity for the bio-based modified epoxy resin composition, thereby facilitating coating of the bio-based modified epoxy resin composition. The solvent in the bio-based modified epoxy resin composition will partially or completely evaporate during subsequent drying, semi-curing, or full curing steps.

[0031] The solvent of the present invention is not particularly limited. Generally, one or a mixture of at least two of the following solvents can be used: ethers such as ethylene glycol methyl ether, diethylene glycol ethyl ether, and diethylene glycol butyl ether; ketones such as acetone, butanone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone; aromatic hydrocarbons such as toluene, xylene, and mesitylene; or ester solvents such as ethoxyethyl acetate and ethyl acetate.

[0032] The bio-based modified epoxy resin composition provided by the present invention is prepared by the following method, which comprises: mixing and uniformly dispersing the components in the bio-based modified epoxy resin composition to obtain the bio-based modified epoxy resin composition.

[0033] In a second aspect, the present invention provides a prepreg, comprising a reinforcing material and the bio-based modified epoxy resin composition according to the first aspect, which is attached to the reinforcing material after impregnation and drying.

[0034] Preferably, the reinforcing material includes any one of glass fiber cloth, non-woven fabric, organic fiber cloth, or a combination of at least two of them.

[0035] In a third aspect, the present invention provides a metal foil-clad laminate comprising one or at least two stacked prepregs as described in the second aspect, and metal foil located on one or both sides of the stacked prepregs.

[0036] Preferably, the metal foil comprises copper foil.

[0037] Preferably, the metal foil-clad laminate is prepared by the following method:

[0038] A laminated structure comprising at least one prepreg is provided, one side or both sides of the laminated structure are covered with metal foil, and hot pressing is performed to obtain the metal foil clad laminate.

[0039] Preferably, the hot pressing temperature is 130-190°C (for example, it can be 130°C, 135°C, 140°C, 145°C, 150°C, 155°C, 160°C, 165°C, 170°C, 175°C, 180°C, 185°C or 190°C, as well as specific point values ​​between the above point values. Due to space limitations and for the sake of simplicity, the present invention no longer exhaustively lists the specific point values ​​included in the range), and the hot pressing pressure is 4-8 MPa (for example, it can be 4 MPa, 4.5 MPa, 5 MPa, 5.5 MPa, 6 MPa , 6.5MPa, 7MPa, 7.5MPa, 8MPa, and specific point values ​​between the above-mentioned point values. Due to space limitations and for the sake of simplicity, the present invention no longer exhaustively lists the specific point values ​​included in the said range), the hot pressing time is 100-150min (for example, it can be 100min, 110min, 120min, 130min, 140min or 150min, and specific point values ​​between the above-mentioned point values. Due to space limitations and for the sake of simplicity, the present invention no longer exhaustively lists the specific point values ​​included in the said range).

[0040] Compared with the prior art, the present invention has at least the following beneficial effects:

[0041] The bio-based modified epoxy resin composition provided by the present invention has good heat resistance and adhesion. The copper-clad laminate prepared from the bio-based modified epoxy resin has a Tg (DSC) of ≥130°C and a peel strength (HOZ) of ≥1.05N / mm. In the prior art, the copper-clad laminate prepared using plant oil-based epoxy resin has a Tg (DSC) of approximately 100°C and a peel strength (HOZ) of approximately 0.75N / mm, which cannot meet the performance requirements of the copper-clad laminate prepared using bisphenol A epoxy resin for Tg (DSC) ≥130°C and peel strength (HOZ) ≥1.05N / mm. Moreover, the copper-clad laminate prepared using the bio-based modified epoxy resin composition provided by the present invention has a thermal stress of ≥300 seconds and meets the flame retardancy of V-0 level. DETAILED DESCRIPTION

[0042] The technical solution of the present invention is further described below by way of specific embodiments. It should be understood by those skilled in the art that the embodiments are merely to help understand the present invention and should not be regarded as specific limitations of the present invention.

[0043] Preparation Example 1

[0044] In this preparation example, a bio-based modified epoxy resin is provided, and the preparation method includes the following steps:

[0045] 100 parts of E51 epoxy resin, 10 parts of 2,5-furandicarboxylic acid (carboxyl equivalent 78 g / mol), 20 parts of acrylic rosin (carboxyl equivalent 233 g / mol, acrylic acid content 10%), 9 parts of maleic anhydride rosin (carboxyl equivalent 267 g / mol, maleic anhydride content 5%), and N,N-dimethylformamide were added to a three-necked flask, the stirrer was turned on, and the temperature was raised to 130° C., the timing was started, and the reaction was carried out for 3.5 hours. The epoxy resin equivalent was tested. When the epoxy equivalent was qualified, the heating was stopped to obtain the bio-based modified epoxy resin (denoted as A-1), whose epoxy equivalent was 476 g / eq. After cooling, the product was bottled for later use;

[0046] Wherein, based on the total weight of E51 epoxy resin, 2,5-furandicarboxylic acid, maleic anhydride rosin and acrylic rosin being 100%, the amount of N,N-dimethylformamide used is 0.1%.

[0047] Preparation Example 2-5

[0048] The only difference from Preparation Example 1 is that the amount and / or parameters of the raw materials and the reaction conditions are different, as shown in Table 1. The contents not shown in Table 1 are considered to be the same as those in Preparation Example 1.

[0049] Table 1

[0050]

[0051] Comparative Preparation Example 1

[0052] In this comparative preparation example, a 2,5-furandicarboxylic acid-modified bisphenol A bio-based epoxy resin is provided, and the preparation method includes the following steps:

[0053] 100 parts of E51 epoxy resin, 22 parts of 2,5-furandicarboxylic acid (carboxyl equivalent 78 g / mol), and N,N-dimethylformamide were added to a three-necked flask, and the stirrer was turned on. When the temperature reached 130° C., the timing was started and the reaction was allowed to proceed for 3.5 hours. The epoxy resin equivalent was tested. When the epoxy equivalent was qualified, heating was stopped to obtain the 2,5-furandicarboxylic acid modified bisphenol A bio-based epoxy resin (denoted as A-D1), whose epoxy equivalent was 473 g / eq. After cooling, the resin was bottled for later use;

[0054] Wherein, based on the total weight of E51 epoxy resin and 2,5-furandicarboxylic acid being 100%, the amount of N,N-dimethylformamide used is 0.1%.

[0055] Comparative Preparation Example 2

[0056] In this comparative preparation example, an epoxy soybean oil-modified bisphenol A bio-based epoxy resin is provided, and the preparation method includes the following steps:

[0057] 100 parts of E51 epoxy resin, 60 parts of epoxidized soybean oil maleic anhydride (carboxyl equivalent 380 g / mol, maleic anhydride content 20%), and N,N-dimethylformamide were added to a three-necked flask, and the stirrer was turned on. When the temperature reached 130° C., the timer was started and the reaction was carried out for 3.5 hours. The epoxy resin equivalent was tested. When the epoxy equivalent was qualified, the heating was stopped to obtain the epoxidized soybean oil-modified bisphenol A bio-based epoxy resin (denoted as A-D2), whose epoxy equivalent was 419 g / eq. After cooling, the resin was bottled for later use;

[0058] Wherein, based on the total weight of E51 epoxy resin and epoxidized soybean oil maleic anhydride being 100%, the amount of N,N-dimethylformamide used is 0.1%.

[0059] Comparative Preparation Example 3

[0060] In this comparative preparation example, a bio-based modified epoxy resin is provided, and the preparation method includes the following steps:

[0061] 100 parts of E51 epoxy resin, 10 parts of 2,5-furandicarboxylic acid (carboxyl equivalent 78 g / mol), 20 parts of acrylic rosin (carboxyl equivalent 233 g / mol, acrylic acid content 10%), and N,N-dimethylformamide were added to a three-necked flask, and the stirrer was turned on. When the temperature reached 130° C., the timing was started and the reaction was allowed to proceed for 3.5 hours. The epoxy resin equivalent was tested. When the epoxy equivalent was qualified, heating was stopped to obtain the bio-based modified epoxy resin (denoted as A-D3) with an epoxy equivalent of 398 g / eq. The product was cooled and bottled for later use.

[0062] Wherein, based on the total weight of E51 epoxy resin, 2,5-furandicarboxylic acid and acrylic rosin being 100%, the amount of N,N-dimethylformamide used is 0.1%.

[0063] Comparative Preparation Example 4

[0064] In this comparative preparation example, a bio-based modified epoxy resin is provided, and the preparation method includes the following steps:

[0065] 100 parts of E51 epoxy resin, 10 parts of 2,5-furandicarboxylic acid (carboxyl equivalent 78 g / mol), 9 parts of maleic anhydride rosin (carboxyl equivalent 267 g / mol, maleic anhydride content 5%), and N,N-dimethylformamide were added to a three-necked flask, and the stirrer was turned on. When the temperature reached 130° C., the timer was started and the reaction was allowed to proceed for 3.5 hours. The epoxy resin equivalent was tested. When the epoxy equivalent was qualified, the heating was stopped to obtain the bio-based modified epoxy resin (denoted as A-D4) with an epoxy equivalent of 315 g / eq. The product was cooled and bottled for later use.

[0066] Wherein, based on the total weight of E51 epoxy resin, 2,5-furandicarboxylic acid and maleic anhydride rosin being 100%, the amount of N,N-dimethylformamide used is 0.1%.

[0067] The raw materials used in the following examples and comparative examples are as follows:

[0068] (A) Bio-based modified epoxy resin

[0069] A-1 to A-5 provided by Preparation Examples 1-5, respectively;

[0070] A-D1 to A-D4 provided by Comparative Preparation Examples 1-4, respectively;

[0071] (B) Bio-based curing agent

[0072] Cardanol phenolic resin: cardanol modified phenol formaldehyde phenolic resin, brand PF9300;

[0073] (C) Filler: aluminum hydroxide;

[0074] (D) Curing accelerator

[0075] Imidazole compounds: 2-methylimidazole;

[0076] (E) Bisphenol A epoxy resin: E20 bisphenol A epoxy resin.

[0077] Example 1

[0078] A bio-based modified epoxy resin composition. The specific components and usage (parts by weight) of the bio-based modified epoxy resin composition are shown in Table 2.

[0079] A copper-clad laminate, the preparation method of which is as follows:

[0080] According to the formula in Table 2, the bio-based modified epoxy resin, bio-based curing agent, and curing accelerator were added to a container and stirred to mix evenly. Then, the filler was added and stirred evenly using a high-speed disperser. Finally, butanone was added to adjust the solid content of the solution to 70% to prepare a glue solution.

[0081] Glass fiber cloth was impregnated with the prepared adhesive solution and dried in an oven to obtain a fabric prepreg. Eight of the above fabric prepregs were stacked, and copper foil was placed on both sides of the outer sides of the fabric prepregs. The prepregs were then hot-pressed at a temperature of 180°C, a pressure of 6 MPa, and a time of 120 min to produce a copper-clad laminate with a thickness of 1.5 mm.

[0082] The performance of the copper clad laminate is tested as follows:

[0083] (1) Thermal stress: Measured according to the thermal stress test method specified in GT / T 4722-2017;

[0084] (2) Glass transition temperature: measured according to the glass transition temperature test method specified in GT / T 4722-2017;

[0085] (3) Peel strength: Determined according to the peel strength test method specified in IPC-TM-650 2.4.8;

[0086] (4) Flame retardancy: tested in accordance with the UL94 "50W (20mm) vertical burning test: V-0, V-1 and V-2" test method.

[0087] The test results are shown in Table 4.

[0088] Examples 2-10, Comparative Examples 1-5

[0089] A bio-based modified epoxy resin composition and a copper-clad laminate containing the same, which differ from Example 1 in that the formula of the resin composition is different, as shown in Tables 2 and 3; wherein the unit of the amount of each component is "parts by weight"; the preparation method and performance testing method of the copper-clad laminate are the same as those in Example 1.

[0090] Table 2

[0091]

[0092]

[0093] Table 3

[0094]

[0095] Table 4

[0096]

[0097]

[0098] As can be seen from Table 4, within the preferred range, the copper-clad laminates prepared from the bio-based modified epoxy resin composition provided by the embodiments of the present invention have glass transition temperatures above 130°C, peel strengths above 1.05 N / mm, thermal stresses (288°C, solder float) above 300 seconds, and flame retardancy up to V-0 level. In other words, the copper-clad laminates prepared from the bio-based modified epoxy resin composition provided by the present invention have the advantage of excellent comprehensive performance in terms of heat resistance, peel strength, and flame retardancy.

[0099] Analysis of Example 1 and Examples 9-10 shows that the peel strength or Tg of Examples 9-10 is not as good as that of Example 1, which proves that in the bio-based modified epoxy resin composition of the present invention, the performance is better when the epoxy equivalent of the bio-based modified epoxy resin is in the range of 300-600 g / eq.

[0100] Analysis of Example 1 and Examples 5-6 shows that the Tg or peel strength of Examples 5-6 is not as good as that of Examples 1-2, proving that in the bio-based modified epoxy resin composition of the present invention, the performance is better when the weight proportion of the bio-based curing agent is in the range of 25-40 parts.

[0101] Analysis of Example 1 and Examples 7-8 shows that the flame retardancy or peel strength of Examples 7-8 is not as good as that of Examples 1-2, proving that in the bio-based modified epoxy resin composition of the present invention, the performance is better when the weight proportion of filler is in the range of 30-80 parts.

[0102] Analysis of Example 1 and Comparative Example 1 shows that the Tg of Comparative Example 1 is not as good as that of Example 1, which proves that in the bio-based modified epoxy resin composition of the present invention, the 2,5-furandicarboxylic acid maleic rosin acrylic rosin modified bisphenol A bio-based epoxy resin has better performance than the 2,5-furandicarboxylic acid modified bisphenol A bio-based epoxy resin.

[0103] Analysis of Example 1 and Comparative Example 2 shows that the Tg and peel strength of Comparative Example 2 are not as good as those of Example 1, which proves that in the bio-based modified epoxy resin composition of the present invention, the bisphenol A bio-based epoxy resin modified with 2,5-furandicarboxylic acid maleic rosin acrylic rosin has better performance than the bisphenol A bio-based epoxy resin modified with epoxidized soybean oil.

[0104] Analysis of Example 1 and Comparative Example 3 shows that the Tg of Comparative Example 3 is not as good as that of Example 1, which proves that in the bio-based modified epoxy resin composition of the present invention, the 2,5-furandicarboxylic acid maleic rosin acrylic rosin modified bisphenol A bio-based epoxy resin has better performance than the 2,5-furandicarboxylic acid acrylic rosin modified bisphenol A bio-based epoxy resin.

[0105] Analysis of Example 1 and Comparative Example 4 shows that the Tg of Comparative Example 4 is not as good as that of Example 1, which proves that in the bio-based modified epoxy resin composition of the present invention, the bisphenol A bio-based epoxy resin modified with 2,5-furandicarboxylic acid maleic rosin acrylic rosin has better performance than the bisphenol A bio-based epoxy resin modified with 2,5-furandicarboxylic acid maleic anhydride rosin.

[0106] Analysis of Example 1 and Comparative Example 5 shows that the performance of Example 1 is comparable to that of Comparative Example 5, demonstrating that in the bio-based modified epoxy resin composition of the present invention, the performance of the bisphenol A bio-based epoxy resin modified with 2,5-furandicarboxylic acid maleic rosin acrylic rosin can be comparable to that of the bisphenol A epoxy resin.

[0107] The applicant states that while the above-described embodiments illustrate the bio-based modified epoxy resin composition and its applications, the present invention is not limited to these embodiments. This does not necessarily mean that the present invention must rely on these embodiments for implementation. Those skilled in the art will appreciate that any improvements to the present invention, equivalent substitutions for raw materials in the present invention, addition of auxiliary components, and selection of specific methods, etc., fall within the scope of protection and disclosure of the present invention.

Claims

1. A bio-based modified epoxy resin composition, characterized in that The bio-based modified epoxy resin composition comprises the following components: a bio-based modified epoxy resin, a bio-based curing agent and a filler; The raw materials for preparing the bio-based modified epoxy resin include bisphenol A epoxy resin, 2,5-furandicarboxylic acid, maleic anhydride rosin and acrylic rosin.

2. The bio-based modified epoxy resin composition according to claim 1, characterized in that The bisphenol A type epoxy resin includes E51 epoxy resin.

3. The bio-based modified epoxy resin composition according to claim 1 or 2, characterized in that The raw materials for preparing the bio-based modified epoxy resin include the following components in parts by weight: 100 parts of bisphenol A epoxy resin, 5-15 parts of 2,5-furandicarboxylic acid, 5-15 parts of maleic anhydride rosin, and 15-25 parts of acrylic rosin.

4. The bio-based modified epoxy resin composition according to any one of claims 1 to 3, characterized in that The epoxy equivalent of the bio-based modified epoxy resin is 300 to 600 g / eq.

5. The bio-based modified epoxy resin composition according to any one of claims 1 to 4, characterized in that: The bio-based modified epoxy resin is prepared by the following method: Mixing the formulated amount of bisphenol A epoxy resin, 2,5-furandicarboxylic acid, maleic anhydride rosin, acrylic rosin and solvent, and reacting to obtain the bio-based modified epoxy resin; Preferably, the solvent comprises N,N-dimethylformamide; Preferably, the amount of the solvent is 0.05% to 0.2%, based on the total weight of bisphenol A epoxy resin, 2,5-furandicarboxylic acid, maleic anhydride rosin, and acrylic rosin as 100%; Preferably, the reaction temperature is 120-140° C., and the reaction time is 3-5 h.

6. The bio-based modified epoxy resin composition according to any one of claims 1 to 5, characterized in that: The bio-based curing agent includes any one or a combination of at least two of cardanol phenolic resin, tung oil phenolic resin, and epoxy soybean oil phenolic resin; Preferably, the filler includes any one of tetrabromobisphenol A, aluminum hydroxide, polyphosphate amine, aluminum hypophosphite, and magnesium hydroxide, or a combination of at least two thereof.

7. The bio-based modified epoxy resin composition according to any one of claims 1 to 6, characterized in that: The bio-based modified epoxy resin composition comprises the following components in parts by weight: 100 parts of bio-based modified epoxy resin, 25-40 parts of bio-based curing agent, and 30-80 parts of filler.

8. The bio-based modified epoxy resin composition according to any one of claims 1 to 7, characterized in that: The bio-based modified epoxy resin composition also includes a curing accelerator; Preferably, the curing accelerator comprises any one or a combination of at least two of a tertiary amine, a tertiary phosphine, an organic metal complex, a quaternary ammonium salt or an imidazole compound; Preferably, the weight portion of the curing accelerator is 0.05 to 0.2 parts.

9. A prepreg, characterized in that: The prepreg comprises a reinforcing material and the bio-based modified epoxy resin composition according to any one of claims 1 to 8 attached to the reinforcing material by impregnation and drying; Preferably, the reinforcing material includes any one of glass fiber cloth, non-woven fabric, organic fiber cloth, or a combination of at least two of them.

10. A metal foil-clad laminate, characterized in that: The metal foil-clad laminate comprises one or at least two laminated prepregs according to claim 9, and metal foil located on one or both sides of the laminated prepregs; Preferably, the metal foil comprises copper foil.

Images