High-toughness anti-aging phenolic resin-based copper-clad plate and preparation method thereof

Abstract

The invention relates to the technical field of phenolic resin copper-clad plates, in particular to a high-toughness anti-aging phenolic resin-based copper-clad plate and a preparation method thereof. Comprising the following steps: 1, mixing modified phenolic resin, bisphenol A epoxy resin, a modified organic silicon elastomer, a curing agent and a modified compatibilizer in a solvent to obtain a phenolic resin glue solution; 2, glass fiber cloth is soaked in the phenolic resin glue solution for 10 min to 20 min, curing is conducted for 25 min to 35 min at the temperature of 130 DEG C to 150 DEG C, and then lamination forming is conducted; therefore, the high-toughness anti-aging phenolic resin-based copper-clad plate is obtained.

Description

Technical Field

[0001] The invention relates to the technical field of phenolic resin copper clad laminates, in particular to a high-toughness, aging-resistant phenolic resin-based copper clad laminate and a preparation method thereof. Background Art

[0002] With the rapid development of the electronics industry, the requirements for copper-clad laminates (CCLs) are increasing. As a key component of printed circuit boards (PCBs), CCLs must not only provide excellent electrical conductivity and mechanical support, but also possess excellent heat resistance, aging resistance, flame retardancy, and high toughness. Phenolic resin, due to its excellent insulation properties, mechanical strength, and chemical resistance, is an ideal substrate for CCL production.

[0003] In the prior art, phenolic resins have a relatively rigid molecular structure, a high crosslink density, and a lack of sufficient flexible segments, resulting in low toughness. This makes it difficult for phenolic resin-based copper-clad laminates to disperse and absorb energy through the deformation and movement of their molecular chains when subjected to external impact. When the impact force reaches a certain level, the internal stress of the material cannot be effectively released, which can easily lead to the formation of local stress concentration points, which in turn trigger the initiation and propagation of cracks.

[0004] In addition, due to the unstable groups in the phenolic resin structure, the phenolic resin-based copper clad laminate will be easily affected by environmental factors during long-term use, resulting in poor toughness, causing the resin to degrade or age, thereby affecting its performance.

[0005] In summary, it is of great significance to prepare a high-toughness and aging-resistant phenolic resin-based copper clad laminate. Summary of the Invention

[0006] The object of the present invention is to provide a high-toughness, aging-resistant phenolic resin-based copper clad laminate and a preparation method thereof, so as to solve the problems raised in the above background technology.

[0007] In order to solve the above technical problems, the present invention provides the following technical solutions:

[0008] A method for preparing a high-toughness, aging-resistant phenolic resin-based copper-clad laminate comprises the following steps:

[0009] Step 1: Mixing a modified phenolic resin, a bisphenol A epoxy resin, a modified silicone elastomer, a curing agent, and a modified compatibilizer in a solvent to obtain a phenolic resin glue solution;

[0010] Step 2: Soak the glass fiber cloth in the phenolic resin glue for 10 to 20 minutes, then cure it at 130 to 150° C. for 25 to 35 minutes, and then laminate it to obtain a phenolic resin-based copper clad laminate.

[0011] More optimally, the raw materials of the phenolic resin glue include the following components, calculated by mass: 20 to 30 parts of modified phenolic resin, 25 to 35 parts of bisphenol A epoxy resin, 10 to 20 parts of modified silicone elastomer, 5 to 10 parts of curing agent, 3 to 5 parts of modified compatibilizer, and 60 to 100 parts of solvent.

[0012] Furthermore, the solvent includes one or more of acetone and butanone.

[0013] More optimally, the preparation method of the modified phenolic resin is:

[0014] S1-1: Add linear phenolic resin and potassium hydroxide to n-butanol, stir at 75-85°C for 1-2 hours, then add chloroethyl acrylate and react at 60-80°C for 4-6 hours, cool, and filter to obtain modified phenolic resin A;

[0015] S1-2: Under ultraviolet light, a photoinitiator, modified phenolic resin A, 1,3,5-tris(3-mercaptobutyryloxyethyl)-1,3,5-triazine-2,4,6(1H,3H,5H)-trione, and maleimide are added to tetrahydrofuran and reacted at 20-40° C. for 30-60 min to obtain modified phenolic resin B;

[0016] S1-3: Octamethylcyclotetrasiloxane, tetramethylammonium hydroxide, and deionized water are mixed and reacted at a temperature of 80-100° C. for 3-5 hours, followed by adding dibutyltin dilaurate, toluene, and (3-aminopropyl)trimethoxysilane and reacting at 100-120° C. for 4-6 hours, followed by distillation and purification to obtain an amino-terminated silicone oligomer; the amino-terminated silicone oligomer and modified phenolic resin B are added to a 50wt%-60wt% pyridine aqueous solution, and refluxed at 90-100° C. for 5-7 hours to obtain a modified phenolic resin.

[0017] More optimally, in the raw materials of the modified phenolic resin, the mass ratio of amino-terminated silicone oligomer to modified phenolic resin B is 2-3:5-8;

[0018] In the raw materials of the modified phenolic resin B, the mass ratio of the modified phenolic resin A, 1,3,5-tris(3-mercaptobutyryloxyethyl)-1,3,5-triazine-2,4,6(1H,3H,5H)-trione, and maleimide is 5-6:7-8:1-2.

[0019] More optimally, the raw materials of the modified phenolic resin A include the following components, calculated by mass: 3 to 6 parts of linear phenolic resin, 0.02 to 0.05 parts of potassium hydroxide, 30 to 40 parts of n-butanol, and 1 to 2 parts of chloroethyl acrylate;

[0020] The raw materials of the amino-terminated silicone oligomer include the following components, calculated by mass: 3 to 4 parts of octamethylcyclotetrasiloxane, 0.1 to 0.2 parts of tetramethylammonium hydroxide, 5 to 10 parts of deionized water, 0.1 to 0.2 parts of dibutyltin dilaurate, 40 to 50 parts of toluene, and 4 to 5 parts of (3-aminopropyl)trimethoxysilane.

[0021] More optimally, the preparation process of the modified silicone elastomer is:

[0022] S2-1: Trifluoropropylmethylcyclotrisiloxane and octamethylcyclotetrasiloxane are melted at 110-130°C and 8-12 mmHg under reduced pressure, followed by addition of potassium hydroxide, reduced pressure at 130-150°C, followed by ring-opening polymerization at 150-170°C for 8-12 hours, and cooled to obtain a modified silicone elastomer.

[0023] More optimally, in the raw materials of the modified silicone elastomer, the mass ratio of trifluoropropylmethylcyclotrisiloxane to octamethylcyclotetrasiloxane is 1.5 to 2:1.

[0024] More optimally, the preparation process of the modified compatibilizer is:

[0025] S3-1: Octamethylcyclotetrasiloxane, vinyltrimethoxysilane and 3-glycidyloxypropyltrimethoxysilane are added to toluene in a mass ratio of 1:1 to 1.2:1 to 1.5, potassium hydroxide is added, and ring-opening polymerization is carried out at 150 to 170°C for 6 to 10 hours. The modified compatibilizer is obtained by distillation under reduced pressure.

[0026] More optimally, the curing agent includes one or more of an isocyanate curing agent and an acid anhydride curing agent.

[0027] More optimally, a method for preparing a high-toughness, aging-resistant phenolic resin-based copper clad laminate obtains a high-toughness, aging-resistant phenolic resin-based copper clad laminate.

[0028] Among them, a modified phenolic resin A containing vinyl, 1,3,5-tris(3-mercaptobutyryloxyethyl)-1,3,5-triazine-2,4,6(1H,3H,5H)-trione, and maleimide were synthesized through a thiol click reaction to synthesize a modified phenolic resin B, which has good flexibility. The introduction of triazine and acylide groups enhances aging resistance. Subsequently, a hydroxyl-terminated polydimethylsiloxane oligomer was obtained through ring-opening polymerization of octamethylcyclotetrasiloxane and initiation with deionized water. This was then hydrolyzed and condensed with (3-aminopropyl)trimethoxysilane to form an amino-terminated silicone oligomer, and a modified phenolic resin was obtained through an aminothiol reaction. The modified compatibilizer, through ring-opening polymerization and condensation, contains vinyl, epoxy, and silicone blocks, which can enhance the compatibility and dispersibility of epoxy resins, modified phenolic resins, and modified silicone elastomers.

[0029] The proposed solution uses amino-terminated silicone oligomers as internal toughening agents to modify phenolic resins, while modified silicone elastomers serve as external toughening agents, enhancing the toughness of the material at both micro and macro levels. Modified compatibilizers also form an "island structure" to further enhance toughness and aging resistance.

[0030] Among them, due to the high brittleness of phenolic resin, the resulting phenolic resin-based copper-clad laminates have poor toughness. To improve the toughness of phenolic resin-based copper-clad laminates, amino-terminated silicone oligomers are introduced as internal toughening agents to modify the phenolic resin, grafting silicone blocks onto the phenolic resin molecular chain. Ether bonds, maleimides, and other substances are introduced to further enhance the internal toughness of the phenolic resin, thereby improving the product's flexibility at the microscopic level. Subsequently, during the preparation of the overall adhesive solution, fluorine-containing silicone elastomers are introduced as external toughening agents in the form of independent dispersed phases within the phenolic resin. When the product is subjected to external forces, these elastomer particles can absorb and disperse energy, preventing crack propagation and further improving flexibility. The two work synergistically to improve toughness. In addition, the similar silicone structure facilitates the subsequent formation of a stable "island structure" under the action of the modified compatibilizer.

[0031] With the help of a modified compatibilizer, the fluorosilicone elastomer acts as the "island" and the modified phenolic resin as the "sea," further improving dispersibility and preventing the "island" from agglomerating, forming an "island structure." The modified compatibilizer reduces the interfacial tension between the two phases, enhancing interfacial bonding and effectively improving the dispersibility of the fluorosilicone elastomer in the modified phenolic resin, preventing the agglomeration of the "island" phase. This uniform and stable "island structure" not only optimizes the material's microstructure but also further enhances its toughness, enabling the product to more effectively transmit and disperse stress when subjected to force.

[0032] Among them, since traditional phenolic resin-based copper clad laminates are prone to aging during long-term use, in order to solve this problem, the solution introduces elements such as silicon and fluorine, triazine, long chain groups, etc. to synergistically improve the heat resistance and humidity resistance, further improve the product's aging resistance, and thus extend the product's service life.

[0033] Compared with the prior art, the present invention has the following beneficial effects:

[0034] The proposed solution uses amino-terminated silicone oligomers as internal toughening agents to modify phenolic resins, while modified silicone elastomers serve as external toughening agents, enhancing the toughness of the material at both micro and macro levels. Modified compatibilizers also form an "island structure" to further enhance toughness and aging resistance. DETAILED DESCRIPTION

[0035] The following is a clear and complete description of the technical solutions in the embodiments of the present invention. Obviously, the embodiments described are only some embodiments of the present invention, not all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without making any creative efforts are within the scope of protection of the present invention.

[0036] It should be noted that the following parts are by mass, and all raw materials involved in the present invention are purchased from manufacturers without any special restrictions, and illustratively include: in the following embodiments, the product number of the linear phenolic resin is WA95196-500g; the product number of the bisphenol A epoxy resin is 15507; and the CAS number of the photoinitiator is 606-28-0.

[0037] Example 1: A method for preparing a high-toughness, aging-resistant phenolic resin-based copper-clad laminate, comprising the following steps:

[0038] Step 1: S1: Add 4.5 parts of linear phenolic resin and 0.03 parts of potassium hydroxide to 35 parts of n-butanol, stir at 80°C for 1.5 hours, then add 1.5 parts of chloroethyl acrylate and react at 70°C for 5 hours, cool and filter to obtain modified phenolic resin A; S2: Under ultraviolet light, add modified phenolic resin A, 1,3,5-tris(3-mercaptobutyryloxyethyl)-1,3,5-triazine-2,4,6(1H,3H,5H)-trione and maleimide to tetrahydrofuran in a mass ratio of 5.5:8:1.2, add a photoinitiator and react at 30°C for 45 minutes to obtain modified phenolic resin B;

[0039] S3: 3.5 parts of octamethylcyclotetrasiloxane, 0.15 parts of tetramethylammonium hydroxide, and 8 parts of deionized water were mixed and reacted at 90° C. for 4 hours, followed by adding 0.15 parts of dibutyltin dilaurate, 45 parts of toluene, and 4.5 parts of (3-aminopropyl)trimethoxysilane and reacting at 110° C. for 5 hours, and purified by distillation to obtain an amino-terminated silicone oligomer; the amino-terminated silicone oligomer and modified phenolic resin B were added to a 55 wt % pyridine aqueous solution in a mass ratio of 2.5:7, and refluxed at 95° C. for 6 hours to obtain a modified phenolic resin;

[0040] Step 2: Trifluoropropylmethylcyclotrisiloxane and octamethylcyclotetrasiloxane were melted at a mass ratio of 1.8:1 at 120° C. and 10 mmHg under reduced pressure, followed by the addition of potassium hydroxide, followed by reduced pressure at 140° C., followed by ring-opening polymerization at 160° C. for 10 hours, and cooling to obtain a modified silicone elastomer;

[0041] Step 3: S3-1: Octamethylcyclotetrasiloxane, vinyltrimethoxysilane, and 3-glycidyloxypropyltrimethoxysilane were added to toluene in a mass ratio of 1:1.1:1.3, potassium hydroxide was added, and ring-opening polymerization was carried out at 160° C. for 8 hours, followed by distillation under reduced pressure to obtain a modified compatibilizer;

[0042] Step 4: Mix 25 parts of modified phenolic resin, 30 parts of bisphenol A epoxy resin, 15 parts of modified silicone elastomer, 8 parts of toluene diisocyanate, and 4 parts of modified compatibilizer in 80 parts of acetone to obtain phenolic resin glue; take 5 pieces of glass fiber cloth and soak them in the phenolic resin glue for 15 minutes, and then cure them at 140°C for 30 minutes to obtain a semi-cured sheet; cover both sides of the semi-cured sheet stack with copper foil with a thickness of 18 μm, and perform hot pressing at a pressure of 15 MPa and a temperature of 220°C for 4 hours to obtain a phenolic resin-based copper clad laminate.

[0043] Example 2: A method for preparing a high-toughness, aging-resistant phenolic resin-based copper-clad laminate, comprising the following steps:

[0044] Step 1: S1: Add 4.5 parts of linear phenolic resin and 0.03 parts of potassium hydroxide to 35 parts of n-butanol, stir at 80°C for 1.5 hours, then add 1.5 parts of chloroethyl acrylate and react at 70°C for 5 hours, cool and filter to obtain modified phenolic resin A; S2: Under ultraviolet light, add modified phenolic resin A, 1,3,5-tris(3-mercaptobutyryloxyethyl)-1,3,5-triazine-2,4,6(1H,3H,5H)-trione and maleimide to tetrahydrofuran in a mass ratio of 5.5:8:1.2, add a photoinitiator and react at 30°C for 45 minutes to obtain modified phenolic resin B;

[0045] S3: 3.5 parts of octamethylcyclotetrasiloxane, 0.15 parts of tetramethylammonium hydroxide, and 8 parts of deionized water were mixed and reacted at 90° C. for 4 hours, followed by adding 0.15 parts of dibutyltin dilaurate, 45 parts of toluene, and 4.5 parts of (3-aminopropyl)trimethoxysilane and reacting at 110° C. for 5 hours, and purified by distillation to obtain an amino-terminated silicone oligomer; the amino-terminated silicone oligomer and modified phenolic resin B were added to a 55 wt % pyridine aqueous solution in a mass ratio of 2.5:7, and refluxed at 95° C. for 6 hours to obtain a modified phenolic resin;

[0046] Step 2: Trifluoropropylmethylcyclotrisiloxane and octamethylcyclotetrasiloxane were melted at a mass ratio of 1.8:1 at 120° C. and 10 mmHg under reduced pressure, followed by the addition of potassium hydroxide, followed by reduced pressure at 140° C., followed by ring-opening polymerization at 160° C. for 10 hours, and cooling to obtain a modified silicone elastomer;

[0047] Step 3: S3-1: Octamethylcyclotetrasiloxane, vinyltrimethoxysilane, and 3-glycidyloxypropyltrimethoxysilane were added to toluene in a mass ratio of 1:1.1:1.3, potassium hydroxide was added, and ring-opening polymerization was carried out at 160° C. for 8 hours, followed by distillation under reduced pressure to obtain a modified compatibilizer;

[0048] Step 4: Mix 20 parts of modified phenolic resin, 25 parts of bisphenol A epoxy resin, 10 parts of modified silicone elastomer, 5 parts of toluene diisocyanate, and 3 parts of modified compatibilizer in 60 parts of acetone to obtain phenolic resin glue; take 5 pieces of glass fiber cloth and soak them in the phenolic resin glue for 15 minutes, and then cure them at 140°C for 30 minutes to obtain a semi-cured sheet; cover both sides of the semi-cured sheet stack with copper foil with a thickness of 18 μm, and perform hot pressing at a pressure of 15 MPa and a temperature of 220°C for 4 hours to obtain a phenolic resin-based copper clad laminate.

[0049] Example 3: A method for preparing a high-toughness, aging-resistant phenolic resin-based copper-clad laminate, comprising the following steps:

[0050] Step 1: S1: Add 4.5 parts of linear phenolic resin and 0.03 parts of potassium hydroxide to 35 parts of n-butanol, stir at 80°C for 1.5 hours, then add 1.5 parts of chloroethyl acrylate and react at 70°C for 5 hours, cool and filter to obtain modified phenolic resin A; S2: Under ultraviolet light, add modified phenolic resin A, 1,3,5-tris(3-mercaptobutyryloxyethyl)-1,3,5-triazine-2,4,6(1H,3H,5H)-trione and maleimide to tetrahydrofuran in a mass ratio of 5.5:8:1.2, add a photoinitiator and react at 30°C for 45 minutes to obtain modified phenolic resin B;

[0051] S3: 3.5 parts of octamethylcyclotetrasiloxane, 0.15 parts of tetramethylammonium hydroxide, and 8 parts of deionized water were mixed and reacted at 90° C. for 4 hours, followed by adding 0.15 parts of dibutyltin dilaurate, 45 parts of toluene, and 4.5 parts of (3-aminopropyl)trimethoxysilane and reacting at 110° C. for 5 hours, and purified by distillation to obtain an amino-terminated silicone oligomer; the amino-terminated silicone oligomer and modified phenolic resin B were added to a 55 wt % pyridine aqueous solution in a mass ratio of 2.5:7, and refluxed at 95° C. for 6 hours to obtain a modified phenolic resin;

[0052] Step 2: Trifluoropropylmethylcyclotrisiloxane and octamethylcyclotetrasiloxane were melted at a mass ratio of 1.8:1 at 120° C. and 10 mmHg under reduced pressure, followed by the addition of potassium hydroxide, followed by reduced pressure at 140° C., followed by ring-opening polymerization at 160° C. for 10 hours, and cooling to obtain a modified silicone elastomer;

[0053] Step 3: S3-1: Octamethylcyclotetrasiloxane, vinyltrimethoxysilane, and 3-glycidyloxypropyltrimethoxysilane were added to toluene in a mass ratio of 1:1.1:1.3, potassium hydroxide was added, and ring-opening polymerization was carried out at 160° C. for 8 hours, followed by distillation under reduced pressure to obtain a modified compatibilizer;

[0054] Step 4: Mix 30 parts of modified phenolic resin, 35 parts of bisphenol A epoxy resin, 20 parts of modified silicone elastomer, 10 parts of toluene diisocyanate, and 5 parts of modified compatibilizer in 100 parts of acetone to obtain phenolic resin glue; take 5 pieces of glass fiber cloth and soak them in the phenolic resin glue for 15 minutes, and then cure them at 140°C for 30 minutes to obtain a semi-cured sheet; cover both sides of the semi-cured sheet stack with copper foil with a thickness of 18 μm, and perform hot pressing at a pressure of 15 MPa and a temperature of 220°C for 4 hours to obtain a phenolic resin-based copper clad laminate.

[0055] Comparative Example 1: Based on Example 1, the internal toughening agent (amino-terminated silicone oligomer) was not added, and the other processes remained unchanged, and were replaced by:

[0056] Step 1: S1: Add 4.5 parts of linear phenolic resin and 0.03 parts of potassium hydroxide to 35 parts of n-butanol, stir at 80°C for 1.5 hours, then add 1.5 parts of chloroethyl acrylate and react at 70°C for 5 hours, cool and filter to obtain modified phenolic resin A; S2: Under ultraviolet light, add modified phenolic resin A, 1,3,5-tris(3-mercaptobutyryloxyethyl)-1,3,5-triazine-2,4,6(1H,3H,5H)-trione and maleimide to tetrahydrofuran in a mass ratio of 5.5:8:1.2, add a photoinitiator and react at 30°C for 45 minutes to obtain a modified phenolic resin.

[0057] Comparative Example 2: Based on Example 1, no modified compatibilizer was added, and the other processes remained unchanged, specifically:

[0058] Step 1: S1: Add 4.5 parts of linear phenolic resin and 0.03 parts of potassium hydroxide to 35 parts of n-butanol, stir at 80°C for 1.5 hours, then add 1.5 parts of chloroethyl acrylate and react at 70°C for 5 hours, cool and filter to obtain modified phenolic resin A; S2: Under ultraviolet light, add modified phenolic resin A, 1,3,5-tris(3-mercaptobutyryloxyethyl)-1,3,5-triazine-2,4,6(1H,3H,5H)-trione and maleimide to tetrahydrofuran in a mass ratio of 5.5:8:1.2, add a photoinitiator and react at 30°C for 45 minutes to obtain modified phenolic resin B;

[0059] S3: 3.5 parts of octamethylcyclotetrasiloxane, 0.15 parts of tetramethylammonium hydroxide, and 8 parts of deionized water were mixed and reacted at 90° C. for 4 hours, followed by adding 0.15 parts of dibutyltin dilaurate, 45 parts of toluene, and 4.5 parts of (3-aminopropyl)trimethoxysilane and reacting at 110° C. for 5 hours, and purified by distillation to obtain an amino-terminated silicone oligomer; the amino-terminated silicone oligomer and modified phenolic resin B were added to a 55 wt % pyridine aqueous solution in a mass ratio of 2.5:7, and refluxed at 95° C. for 6 hours to obtain a modified phenolic resin;

[0060] Step 2: Trifluoropropylmethylcyclotrisiloxane and octamethylcyclotetrasiloxane were melted at a mass ratio of 1.8:1 at 120° C. and 10 mmHg under reduced pressure, followed by the addition of potassium hydroxide, followed by reduced pressure at 140° C., followed by ring-opening polymerization at 160° C. for 10 hours, and cooling to obtain a modified silicone elastomer;

[0061] Step 3: Mix 25 parts of modified phenolic resin, 30 parts of bisphenol A epoxy resin, 15 parts of modified silicone elastomer, and 8 parts of toluene diisocyanate in 80 parts of acetone to obtain a phenolic resin glue; take 5 pieces of glass fiber cloth and soak them in the phenolic resin glue for 15 minutes, and then cure them at 140°C for 30 minutes to obtain a semi-cured sheet; cover both sides of the semi-cured sheet stack with copper foil with a thickness of 18 μm, and perform hot pressing at a pressure of 15 MPa and a temperature of 220°C for 4 hours to obtain a phenolic resin-based copper clad laminate.

[0062] Comparative Example 3: Based on Example 1, no external toughening agent (modified silicone elastomer) was added, and the rest of the process remained unchanged, specifically:

[0063] Step 1: S1: Add 4.5 parts of linear phenolic resin and 0.03 parts of potassium hydroxide to 35 parts of n-butanol, stir at 80°C for 1.5 hours, then add 1.5 parts of chloroethyl acrylate and react at 70°C for 5 hours, cool and filter to obtain modified phenolic resin A; S2: Under ultraviolet light, add modified phenolic resin A, 1,3,5-tris(3-mercaptobutyryloxyethyl)-1,3,5-triazine-2,4,6(1H,3H,5H)-trione and maleimide to tetrahydrofuran in a mass ratio of 5.5:8:1.2, add a photoinitiator and react at 30°C for 45 minutes to obtain modified phenolic resin B;

[0064] S3: 3.5 parts of octamethylcyclotetrasiloxane, 0.15 parts of tetramethylammonium hydroxide, and 8 parts of deionized water were mixed and reacted at 90° C. for 4 hours, followed by adding 0.15 parts of dibutyltin dilaurate, 45 parts of toluene, and 4.5 parts of (3-aminopropyl)trimethoxysilane and reacting at 110° C. for 5 hours, and purified by distillation to obtain an amino-terminated silicone oligomer; the amino-terminated silicone oligomer and modified phenolic resin B were added to a 55 wt % pyridine aqueous solution in a mass ratio of 2.5:7, and refluxed at 95° C. for 6 hours to obtain a modified phenolic resin;

[0065] Step 2: S3-1: Octamethylcyclotetrasiloxane, vinyltrimethoxysilane, and 3-glycidyloxypropyltrimethoxysilane were added to toluene in a mass ratio of 1:1.1:1.3, potassium hydroxide was added, and ring-opening polymerization was carried out at 160° C. for 8 hours, followed by distillation under reduced pressure to obtain a modified compatibilizer;

[0066] Step 3: Mix 25 parts of modified phenolic resin, 30 parts of bisphenol A epoxy resin, 8 parts of toluene diisocyanate, and 4 parts of modified compatibilizer in 80 parts of acetone to obtain phenolic resin glue; take 5 pieces of glass fiber cloth and soak them in the phenolic resin glue for 15 minutes, and then cure them at 140°C for 30 minutes to obtain a semi-cured sheet; cover both sides of the semi-cured sheet stack with copper foil with a thickness of 18 μm, and perform hot pressing at a pressure of 15 MPa and a temperature of 220°C for 4 hours to obtain a phenolic resin-based copper clad laminate.

[0067] Comparative Example 4: Based on Example 1, the amino-terminated silicone oligomer was replaced with an aminosilane coupling agent, and the rest of the process remained unchanged, and was replaced with:

[0068] Step 1: S1: Add 4.5 parts of linear phenolic resin and 0.03 parts of potassium hydroxide to 35 parts of n-butanol, stir at 80°C for 1.5 hours, then add 1.5 parts of chloroethyl acrylate and react at 70°C for 5 hours, cool and filter to obtain modified phenolic resin A; S2: Under ultraviolet light, add modified phenolic resin A, 1,3,5-tris(3-mercaptobutyryloxyethyl)-1,3,5-triazine-2,4,6(1H,3H,5H)-trione and maleimide to tetrahydrofuran in a mass ratio of 5.5:8:1.2, add a photoinitiator and react at 30°C for 45 minutes to obtain modified phenolic resin B;

[0069] S3: adding aminosilane coupling agent KH550 and modified phenolic resin B to a 55 wt % pyridine aqueous solution in a mass ratio of 1:7, and refluxing at 95° C. for 6 hours to obtain a modified phenolic resin.

[0070] Testing experiment: The high-toughness and aging-resistant phenolic resin-based copper clad laminates prepared in Examples 1 to 3 and Comparative Examples 1 to 4 were subjected to performance testing: The high-toughness and aging-resistant phenolic resin-based copper clad laminates prepared in Examples 1 to 3 and Comparative Examples 1 to 4 were tested and compared in terms of bending properties before and after aging at 300° C. for 80 hours with reference to GB / T 9341-2008 to evaluate their effects on toughness and aging resistance. The results are shown in Table 1.

[0071]

[0072]

[0073] Table 1

[0074] Results Analysis: The data in Table 1 demonstrates that the proposed solution utilizes amino-terminated silicone oligomers as internal toughening agents to modify the phenolic resin, while modified silicone elastomers serve as external toughening agents. This improves the toughness of the material at both the micro and macro levels. Furthermore, the modified compatibilizer forms an "island structure," further enhancing toughness and aging resistance.

[0075] It will be apparent to those skilled in the art that the present invention is not limited to the details of the exemplary embodiments described above and that the invention can be embodied in other specific forms without departing from the spirit or essential characteristics of the invention. Therefore, the embodiments should be considered in all respects as illustrative and non-restrictive, and the scope of the invention is defined by the appended claims rather than the foregoing description, and it is intended that all variations that come within the meaning and range of equivalents of the claims be embraced therein.

Claims

1. A method for preparing a high-toughness, aging-resistant phenolic resin-based copper-clad laminate, characterized by: The following steps are involved: Step 1: Mixing a modified phenolic resin, a bisphenol A epoxy resin, a modified silicone elastomer, a curing agent, and a modified compatibilizer in a solvent to obtain a phenolic resin glue solution; Step 2: Soak the glass fiber cloth in phenolic resin glue for 10 to 20 minutes, cure it at 130 to 150° C. for 25 to 35 minutes, and then laminate it to obtain a phenolic resin-based copper clad laminate.

2. The method for preparing a high-toughness, aging-resistant phenolic resin-based copper-clad laminate according to claim 1, wherein: The raw materials of the phenolic resin glue include the following components, calculated by mass: 20 to 30 parts of modified phenolic resin, 25 to 35 parts of bisphenol A epoxy resin, 10 to 20 parts of modified silicone elastomer, 5 to 10 parts of curing agent, 3 to 5 parts of modified compatibilizer, and 60 to 100 parts of solvent.

3. The method for preparing a high-toughness, aging-resistant phenolic resin-based copper-clad laminate according to claim 2, wherein: The preparation method of the modified phenolic resin is: S1-1: Add linear phenolic resin and potassium hydroxide to n-butanol, stir at 75-85°C for 1-2 hours, then add chloroethyl acrylate and react at 60-80°C for 4-6 hours, cool, and filter to obtain modified phenolic resin A; S1-2: Under ultraviolet light, a photoinitiator, modified phenolic resin A, 1,3,5-tris(3-mercaptobutyryloxyethyl)-1,3,5-triazine-2,4,6(1H,3H,5H)-trione, and maleimide are added to tetrahydrofuran and reacted at 20-40° C. for 30-60 min to obtain modified phenolic resin B; S1-3: Octamethylcyclotetrasiloxane, tetramethylammonium hydroxide, and deionized water are mixed and reacted at a temperature of 80-100° C. for 3-5 hours, followed by adding dibutyltin dilaurate, toluene, and (3-aminopropyl)trimethoxysilane and reacting at 100-120° C. for 4-6 hours, followed by distillation and purification to obtain an amino-terminated silicone oligomer; the amino-terminated silicone oligomer and modified phenolic resin B are added to a 50wt%-60wt% pyridine aqueous solution, and refluxed at 90-100° C. for 5-7 hours to obtain a modified phenolic resin.

4. The method for preparing a high-toughness, aging-resistant phenolic resin-based copper-clad laminate according to claim 3, wherein: In the raw materials of the modified phenolic resin, the mass ratio of amino-terminated silicone oligomer to modified phenolic resin B is 2-3:5-8; In the raw materials of the modified phenolic resin B, the mass ratio of the modified phenolic resin A, 1,3,5-tris(3-mercaptobutyryloxyethyl)-1,3,5-triazine-2,4,6(1H,3H,5H)-trione, and maleimide is 5-6:7-8:1-2.

5. The method for preparing a high-toughness, aging-resistant phenolic resin-based copper-clad laminate according to claim 4, wherein: The raw materials of the modified phenolic resin A include the following components, calculated by mass: 3 to 6 parts of linear phenolic resin, 0.02 to 0.05 parts of potassium hydroxide, 30 to 40 parts of n-butanol, and 1 to 2 parts of chloroethyl acrylate; The raw materials of the amino-terminated silicone oligomer include the following components, calculated by mass: 3 to 4 parts of octamethylcyclotetrasiloxane, 0.1 to 0.2 parts of tetramethylammonium hydroxide, 5 to 10 parts of deionized water, 0.1 to 0.2 parts of dibutyltin dilaurate, 40 to 50 parts of toluene, and 4 to 5 parts of (3-aminopropyl)trimethoxysilane.

6. The method for preparing a high-toughness, aging-resistant phenolic resin-based copper-clad laminate according to claim 2, wherein: The preparation process of the modified silicone elastomer is as follows: S2-1: Trifluoropropylmethylcyclotrisiloxane and octamethylcyclotetrasiloxane are melted at 110-130°C and 8-12 mmHg under reduced pressure, followed by addition of potassium hydroxide, reduced pressure at 130-150°C, followed by ring-opening polymerization at 150-170°C for 8-12 hours, and cooled to obtain a modified silicone elastomer.

7. The method for preparing a high-toughness, aging-resistant phenolic resin-based copper-clad laminate according to claim 6, wherein: In the raw materials of the modified silicone elastomer, the mass ratio of trifluoropropylmethylcyclotrisiloxane to octamethylcyclotetrasiloxane is 1.5-2:

1.

8. The method for preparing a high-toughness, aging-resistant phenolic resin-based copper-clad laminate according to claim 2, wherein: The preparation process of the modified compatibilizer is as follows: S3-1: Octamethylcyclotetrasiloxane, vinyltrimethoxysilane and 3-glycidyloxypropyltrimethoxysilane are added to toluene in a mass ratio of 1:1 to 1.2:1 to 1.5, potassium hydroxide is added, and ring-opening polymerization is carried out at 150 to 170°C for 6 to 10 hours. The modified compatibilizer is obtained by distillation under reduced pressure.

9. The method for preparing a high-toughness, aging-resistant phenolic resin-based copper-clad laminate according to claim 2, wherein: The curing agent includes one or more of an isocyanate curing agent and an acid anhydride curing agent.

10. A high-toughness, aging-resistant phenolic resin-based copper-clad laminate prepared according to the method for preparing a high-toughness, aging-resistant phenolic resin-based copper-clad laminate according to any one of claims 1 to 9.

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