Anti-UV epoxy resin material for copper-clad plate and preparation method of anti-UV epoxy resin material

Abstract

The invention discloses an anti-UV epoxy resin material for a copper-clad plate and a preparation method of the anti-UV epoxy resin material, and relates to the technical field of copper-clad plate materials. The prepared anti-UV epoxy resin material for the copper-clad plate is prepared by adding polyester benzotriazole and a polyacrylate derivative into bisphenol A epoxy resin, the polyester benzotriazole is prepared by reacting benzotriazole with phenylacetyl chloride polyester, and the phenylacetyl chloride polyester is prepared by reacting terephthalic acid, N-acetyl-4-(2-aminoethyl) phenylacetic acid and ethylene glycol, and then adding the polyacrylate derivative into the bisphenol A epoxy resin to obtain the anti-UV epoxy resin material for the copper-clad plate. The material is prepared by acylating chlorination, so that the material can still maintain stability under long-term ultraviolet exposure; the polyacrylate derivative is prepared by polymerizing hydroxyethyl acrylate with a phosphorus source, a nitrogen source and a silicon source, the phosphorus source is pentaerythritol diphosphate diphosphoryl chloride, the silicon source is prepared by reacting epoxy methyl diphenyl silane with melamine, the nitrogen source is diurea dihydric alcohol, and then the polyacrylate derivative is combined with the modified epoxy resin, so that the modified epoxy resin is obtained. Therefore, the material keeps good dielectric property and mechanical property.

Description

Technical Field

[0001] This invention relates to the field of copper clad laminate materials technology, specifically to a UV-resistant epoxy resin material for copper clad laminates and its preparation method. Background Technology

[0002] Copper-clad laminate, or copper clad laminate for short, is mainly used in the manufacture of printed circuit boards, electronic communications, and instruments, and is a fundamental material in the electronics industry. Currently, the matrix resin of copper clad laminate is mainly bisphenol-type epoxy resin, but its heat resistance is poor, and its dielectric constant and dielectric loss are high, which cannot meet the requirements of high-performance copper clad laminates used under high-frequency conditions.

[0003] Epoxy resin is a thermosetting resin with excellent adhesion, mechanical strength, and electrical insulation properties. However, due to its high cross-linking structure, pure epoxy resin suffers from drawbacks such as brittleness, fatigue, insufficient heat resistance, and poor impact toughness, making it difficult to meet the performance requirements for direct use as a base material for copper-clad laminates in printed circuit boards. Furthermore, the UV resistance of epoxy resin is insufficient for current environmental conditions. Given the limitations in the mechanical properties and UV resistance stability of the resin, this invention researches and prepares a UV-resistant epoxy resin material for copper-clad laminates that combines UV resistance with stability and mechanical properties to address this issue. Summary of the Invention

[0004] The technical problem to be solved by the present invention is to provide a UV-resistant epoxy resin material for copper clad laminates and a method for preparing the same.

[0005] The present invention proposes a technical solution to solve the above-mentioned technical problems: a UV-resistant epoxy resin material for copper clad laminates, which is prepared by adding polyester benzotriazole and polyacrylate derivative to bisphenol A epoxy resin; wherein the polyacrylate derivative is prepared by polymerization of hydroxyethyl acrylate with phosphorus source, nitrogen source and silicon source.

[0006] Preferably, the polyester benzotriazole is prepared by reacting 2-(2'-hydroxy-5'-methylphenyl)benzotriazole with phenylacetyl chloride polyester; the phenylacetyl chloride polyester is prepared by reacting terephthalic acid, N-acetyl-4-(2-aminoethyl)phenylacetic acid and ethylene glycol, followed by acyl chloride.

[0007] Preferably, the phosphorus source is pentaerythritol diphosphate diphosphonate chloride; and the nitrogen source is diurea diol.

[0008] Preferably, the silicon source is prepared by reacting epoxymethyldiphenylsilane with melamine.

[0009] Preferably, the method for preparing the UV-resistant epoxy resin material for the copper-clad laminate includes the following specific steps:

[0010] S1. Mix 2-(2'-hydroxy-5'-methylphenyl)benzotriazole and pyridine at a mass ratio of 1:5-6, stir well, place in an ice bath, keep warm, and add a 30-40% (w / w) dichloromethane solution of phenylacetyl chloride polyester dropwise at a rate of 1-4 ml / min. After the addition is complete, raise the temperature to 40-50°C and continue the reaction for 2-3 h. Quench with ice water, extract with dichloromethane, wash successively with 1-3% (w / w) hydrochloric acid, saturated sodium carbonate solution and saturated brine, dry with anhydrous sodium sulfate, and rotary evaporate to obtain polyester benzotriazole;

[0011] S2. Melamine and N,N-dimethylformamide are mixed at a mass ratio of 1:10-12, heated to 90-100℃, stirred and dissolved, then cooled to 80-82℃. 0.4-0.6 times the mass of melamine catalyst triethylamine and 12-15 times the mass of melamine epoxymethyldiphenylsilane are added, and the reaction is carried out for 4-6 hours. The mixture is cooled to room temperature and precipitated with petroleum ether. After filtration, it is washed 3-5 times with deionized water and methanol, and then dried under vacuum at 60-80℃ to obtain the silicon source.

[0012] S3. Under a nitrogen atmosphere, mix pentaerythritol diphosphate bisphosphonate (phosphoric acid), silicon source, tetrahydrofuran, and triethylamine in a molar ratio of 1:1–1.2:8–10:1, heat to 60–80°C, and react for 8–12 hours. Then add 1.1–1.3 times the molar amount of pentaerythritol diphosphate bisphosphonate (phosphoric acid) as a nitrogen source (diurea diol), heat to 150–155°C, and react for 40–60 minutes. Precipitate with deionized water and filter. Then add hydroxyethyl acrylate, p-toluenesulfonic acid (catalyst), and polymerization inhibitor. The molar ratio of hydroquinone and toluene, pentaerythritol diphosphate diphosphoryl chloride, hydroxyethyl acrylate, p-toluenesulfonic acid catalyst, and hydroquinone and toluene polymerization inhibitor is 1:2-2.2:0.02-0.04:0.001:20. The temperature is lowered to 85-95℃, and the reaction is carried out for 6-8 hours. Then, 1.4-1.6 times the mass of hydroxyethyl acrylate deionized water and 0.02-0.04 times the mass of hydroxyethyl acrylate initiator ammonium persulfate are added, and the reaction is continued for 4-6 hours to obtain polyacrylate derivatives.

[0013] S4. Bisphenol A epoxy resin and polyester benzotriazole are mixed at a mass ratio of 100:11-13, heated to 80-90℃, and stirred at 400-800 rpm for 1-2 hours. The mixture is then cooled to 50-60℃, and 0.01-0.03 times the mass of polyester benzotriazole is added as a curing agent triethylenetetramine and 0.1-0.4 times the mass of polyester benzotriazole as a polyacrylate derivative. After stirring evenly, the mixture is heated to 80-82℃ and cured for 1-2 hours. The temperature is then raised to 120-122℃ and cured for 1-2 hours. The temperature is then raised to 150-152℃ and cured for 1-2 hours. The mixture is then cooled to room temperature to obtain a UV-resistant epoxy resin material for copper-clad laminates.

[0014] Preferably, in step S1 above, the preparation method of phenylacetyl chloride polyester is as follows: terephthalic acid, N-acetyl-4-(2-aminoethyl)phenylacetic acid, ethylene glycol, and tetrabutyl titanate are mixed in a mass ratio of 100:2.5-7.5:48-50:0.05, heated to 250-252°C, and reacted at a pressure of 0.3-0.5 MPa for 3-4 hours. The temperature is then raised to 260-270°C, a vacuum is applied to 5-10 kPa, and the reaction continues for 1-2 hours. Finally, the temperature is raised to 2... The reaction was continued at 75–285℃ for 2–3 hours. After water cooling and slicing, dichloromethane (0.6–0.8 times the mass of terephthalic acid) and N,N-dimethylformamide (0.02–0.06 times the mass of terephthalic acid) were added. The mixture was placed in an ice bath and stirred until homogeneous. Then, thionyl chloride (0.7–0.9 times the mass of terephthalic acid) was added dropwise at a rate of 1–3 ml / min. The temperature was raised to 40–50℃ and the reaction was continued for 16–24 hours. The mixture was then distilled under reduced pressure to obtain phenylacetyl chloride polyester.

[0015] Preferably, the preparation method of N-acetyl-4-(2-aminoethyl)phenylacetic acid is as follows: 4-(2-aminoethyl)phenylacetic acid and acetic anhydride are mixed in an equimolar ratio and placed in pyridine with a mass of 20 to 40 times that of acetic anhydride. The mixture is heated to 60 to 70°C and reacted for 4 to 5 hours. Hydrochloric acid with a mass fraction of 1 to 3% equal to that of pyridine is added. The mixture is extracted with dichloromethane, washed 3 to 5 times successively with saturated sodium bicarbonate and saturated brine, dried with anhydrous sodium sulfate, and finally dried under vacuum at 40 to 50°C to obtain N-acetyl-4-(2-aminoethyl)phenylacetic acid.

[0016] Preferably, in step S2 above, the preparation method of epoxymethyldiphenylsilane is as follows: 1,2-epoxy-4-vinylcyclohexane, Karstedt catalyst and toluene are mixed at a mass ratio of 13-16:0.1:40-60, stirred evenly, heated to 80-82°C, and 50-60% toluene solution of methyldiphenylsilane is added dropwise at a rate of 1-3 ml / min at a mass ratio of 3.4-3.8 times that of 1,2-epoxy-4-vinylcyclohexane. The mixture is kept at 84-88°C and reacted for 6-8 hours. The mixture is then rotary evaporated to obtain epoxymethyldiphenylsilane.

[0017] Preferably, in step S3 above, the preparation method of diurea diol is as follows: 1,3-bis(1-isocyano-2-propyl)benzene and N,N-dimethylformamide are mixed at a mass ratio of 1 to 1.2:5, placed in an ice bath, stirred evenly, and then 0.93 to 0.95 times the mass of diethylene glycolamine of 1,3-bis(1-isocyano-2-propyl)benzene are added. The mixture is heated to 4 to 6°C and reacted for 18 to 24 hours. The mixture is precipitated with ethyl acetate, filtered, washed 3 to 5 times with ethyl acetate, and dried under vacuum to obtain diurea diol.

[0018] Compared with the prior art, the beneficial effects achieved by the present invention are:

[0019] The UV-resistant epoxy resin material for copper-clad laminates prepared in this invention is obtained by adding polyester benzotriazole and polyacrylate derivatives to bisphenol A epoxy resin.

[0020] Benzotriazole polyester is prepared by reacting benzotriazole with phenylacetyl chloride polyester. Benzoacetyl chloride polyester is prepared by reacting terephthalic acid, N-acetyl-4-(2-aminoethyl)phenylacetic acid and ethylene glycol, followed by acyl chlorination. Introducing benzotriazole with flexible segments onto epoxy resin not only gives the material UV resistance, but also effectively disperses UV-induced stress and reduces the generation of microcracks, allowing the material to maintain stability under long-term UV exposure.

[0021] Polyacrylate derivatives are obtained by polymerizing hydroxyethyl acrylate with phosphorus, nitrogen, and silicon sources. The phosphorus source is pentaerythritol diphosphate diphosphoryl chloride, the silicon source is obtained by reacting epoxymethyldiphenylsilane with melamine, and the nitrogen source is diurea diol. After the pentaerythritol diphosphate diphosphoryl chloride reacts with the amino group on the silicon source, it reacts with the hydroxyl groups on the diurea diol and hydroxyethyl acrylate to form polymerizable acrylate monomers containing phosphorus, nitrogen, and silicon. The resulting polyacrylate derivatives not only have excellent flame retardant properties but also excellent UV resistance. When combined with modified epoxy resin, the material maintains good dielectric and mechanical properties. Detailed Implementation

[0022] The present invention will be specifically described below through embodiments. It should be noted that the following embodiments are only used to further illustrate the present invention and should not be construed as limiting the scope of protection of the present invention. Those skilled in the art can make some non-essential improvements and adjustments to the present invention based on the above description. Unless otherwise defined, all technical and scientific terms used herein have the same meaning as those skilled in the art.

[0023] Copper-clad laminates were laminated with UV-resistant epoxy resin copper foil, cured by hot pressing at 180°C and 30MPa for 90 minutes, cooled, and then cut to obtain copper-clad laminate substrate material with a thickness of 1.5mm, and its performance was tested.

[0024] To more clearly illustrate the method provided by the present invention, the following embodiments are provided for detailed explanation. The test methods for various indicators of the UV-resistant epoxy resin material for copper-clad laminates prepared in the embodiments and comparative examples are as follows:

[0025] UV blocking rate: The UV blocking rate of the copper clad laminate substrate material was tested according to IEC 1189-2C11.

[0026] Mechanical properties: The copper clad laminate substrate material was subjected to bending strength testing in accordance with GB / T4722.

[0027] UV aging test: The copper clad laminate substrate material was treated according to GB / T14522 and subjected to bending strength test again.

[0028] Flame retardancy: The oxygen index of the copper clad laminate substrate material was determined according to GB / T2406.

[0029] Dielectric properties: The dielectric strength of the copper clad laminate substrate material was tested in accordance with GB / T 1408.

[0030] Example 1

[0031] The method for preparing the UV-resistant epoxy resin material for the copper-clad laminate in this embodiment is as follows:

[0032] S1. 4-(2-aminoethyl)phenylacetic acid and acetic anhydride were mixed in an equimolar ratio and placed in pyridine at 20 times the mass of acetic anhydride. The mixture was heated to 60℃ and reacted for 4 hours. An equal volume of 1% hydrochloric acid was added, and the mixture was extracted with dichloromethane. The mixture was washed three times successively with saturated sodium bicarbonate and saturated brine, dried over anhydrous sodium sulfate, and finally dried under vacuum at 40℃ to obtain N-acetyl-4-(2-aminoethyl)phenylacetic acid. Terephthalic acid, N-acetyl-4-(2-aminoethyl)phenylacetic acid, ethylene glycol, and tetrabutyl titanate were mixed in a mass ratio of 100:2.5:48:0.05, heated to 250℃, and reacted at 0.3 MPa for 3 hours. The mixture was then heated to 260℃, evacuated to 5 kPa, and reacted for another hour. The mixture was then heated to 275℃ and reacted for another 2 hours. The mixture was water-cooled, sliced, and then terephthalic acid was added. 0.6 times the mass of dichloromethane and 0.02 times the mass of terephthalic acid catalyst N,N-dimethylformamide were placed in an ice bath and stirred until homogeneous. Then, 0.7 times the mass of terephthalic acid thionyl chloride was added dropwise at a rate of 1 ml / min. The temperature was raised to 40 °C and the reaction was carried out for 16 h. The mixture was then distilled under reduced pressure to obtain phenylacetyl chloride polyester. 2-(2'-hydroxy-5'-methylphenyl)benzotriazole and pyridine were mixed at a mass ratio of 1:5 and stirred until homogeneous. The mixture was placed in an ice bath and kept warm. A 30% mass fraction of phenylacetyl chloride polyester dichloromethane solution was added dropwise at a rate of 1 ml / min. After the addition was completed, the temperature was raised to 40 °C and the reaction was continued for 2 h. The reaction was quenched with ice water and then extracted with dichloromethane. The mixture was washed successively with 1% mass fraction hydrochloric acid, saturated sodium carbonate solution and saturated brine. The mixture was dried over anhydrous sodium sulfate and rotary evaporated to obtain polyester benzotriazole.

[0033] S2. 1,2-Epoxy-4-vinylcyclohexane, Karstedt catalyst, and toluene were mixed at a mass ratio of 16:0.1:40. After stirring until homogeneous, the mixture was heated to 80°C. A 50% toluene solution of methyldiphenylsilane, with a mass fraction of 3.4 times that of 1,2-epoxy-4-vinylcyclohexane, was added dropwise at a rate of 1 ml / min. The mixture was kept at 84°C and reacted for 6 h. The mixture was then rotary evaporated to obtain epoxymethyldiphenylsilane. Melamine and N,N-dimethylformamide were mixed at a mass ratio of 1:10. The mixture was heated to 90°C and stirred until dissolved. After cooling to 80°C, a catalyst of triethylamine with a mass fraction of 0.4 times that of melamine and an epoxymethyldiphenylsilane with a mass fraction of 12 times that of melamine were added. The mixture was reacted for 4 h. After cooling to room temperature, the mixture was precipitated with petroleum ether. The precipitate was filtered and washed three times with deionized water and methanol. The precipitate was then dried under vacuum at 60°C to obtain a silicon source.

[0034] S3. 1,3-bis(1-isocyano-2-propyl)benzene and N,N-dimethylformamide were mixed at a mass ratio of 1:5, placed in an ice bath, and stirred until homogeneous. Then, 0.93 times the mass of diethylene glycolamine of 1,3-bis(1-isocyano-2-propyl)benzene was added, the mixture was heated to 4°C, and reacted for 18 h. The mixture was precipitated with ethyl acetate, filtered, washed three times with ethyl acetate, and dried under vacuum to obtain diurea diol. Under a nitrogen atmosphere, pentaerythritol diphosphate diphosphoryl chloride, a silicon source, tetrahydrofuran, and triethylamine were mixed in a molar ratio of 1:1:8:1, heated to 60°C, and reacted for 8 h. Then, pentaerythritol diphosphate diphosphoryl chloride was added. A nitrogen source, bisurea diol, with a molar amount of 1.1 times that of chlorine, was heated to 150°C and reacted for 40 min. The mixture was then precipitated with deionized water and filtered. Hydroxyethyl acrylate, p-toluenesulfonic acid catalyst, hydroquinone inhibitor, and toluene were added. The molar ratio of pentaerythritol diphosphate diphosphoryl chloride, hydroxyethyl acrylate, p-toluenesulfonic acid catalyst, hydroquinone inhibitor, and toluene was 1:2:0.02:0.001:20. The mixture was then cooled to 85°C and reacted for 6 h. Finally, deionized water with a molar amount of 1.4 times that of hydroxyethyl acrylate and ammonium persulfate initiator with a molar amount of 0.02 times that of hydroxyethyl acrylate were added, and the reaction was continued for 4 h to obtain a polyacrylate derivative.

[0035] S4. Bisphenol A epoxy resin and polyester benzotriazole are mixed at a mass ratio of 100:11, heated to 80°C, stirred at 400 rpm for 1 hour, cooled to 50°C, and added triethylenetetramine (0.01 times the mass of polyester benzotriazole) as a curing agent and polyacrylate derivative (0.1 times the mass of polyester benzotriazole). After stirring evenly, the mixture is heated to 80°C and cured for 1 hour, then heated to 120°C and cured for 1 hour, then heated to 150°C and cured for 1 hour. The mixture is then cooled to room temperature to obtain a UV-resistant epoxy resin material for copper-clad laminates.

[0036] Example 2

[0037] The method for preparing the UV-resistant epoxy resin material for the copper-clad laminate in this embodiment is as follows:

[0038] S1. 4-(2-aminoethyl)phenylacetic acid and acetic anhydride were mixed in an equimolar ratio and placed in pyridine at 30 times the mass of acetic anhydride. The mixture was heated to 65℃ and reacted for 4.5 h. An equal volume of 2% hydrochloric acid (by mass fraction) was added to the mixture. The mixture was extracted with dichloromethane, washed four times successively with saturated sodium bicarbonate and saturated brine, dried over anhydrous sodium sulfate, and finally dried under vacuum at 45℃ to obtain N-acetyl-4-(2-aminoethyl)phenylacetic acid. Terephthalic acid, N-acetyl-4-(2-aminoethyl)phenylacetic acid, ethylene glycol, and tetrabutyl titanate were mixed in a mass ratio of 100:5:49:0.05. The mixture was heated to 251℃ and 0.4 MPa and reacted for 3.5 h. The temperature was then raised to 265℃, and a vacuum of 8 kPa was applied. The reaction continued for 1.5 h. The temperature was raised to 280℃ and the reaction continued for 2.5 h. The mixture was water-cooled, sliced, and then terephthalic acid was added. Dichloromethane (0.7 times the mass of terephthalic acid) and N,N-dimethylformamide (0.04 times the mass of terephthalic acid) were placed in an ice bath and stirred until homogeneous. Then, thionyl chloride (0.8 times the mass of terephthalic acid) was added dropwise at a rate of 2 ml / min. The temperature was raised to 45 °C, and the reaction was carried out for 20 h. The mixture was then distilled under reduced pressure to obtain phenylacetyl chloride polyester. 2-(2'-hydroxy-5'-methylphenyl)benzotriazole and pyridine were mixed at a mass ratio of 1:5.5, stirred until homogeneous, and placed in an ice bath. The mixture was kept at this temperature, and a 35% (w / w) solution of phenylacetyl chloride polyester in dichloromethane was added dropwise at a rate of 3 ml / min. After the addition was completed, the temperature was raised to 45 °C, and the reaction was continued for 2.5 h. The reaction was quenched with ice water, extracted with dichloromethane, washed successively with 2% (w / w) hydrochloric acid, saturated sodium carbonate solution, and saturated brine, dried over anhydrous sodium sulfate, and rotary evaporated to obtain polyester benzotriazole.

[0039] S2. 1,2-Epoxy-4-vinylcyclohexane, Karstedt catalyst, and toluene were mixed at a mass ratio of 14:0.1:50. After stirring until homogeneous, the mixture was heated to 81°C. A 55% toluene solution of methyldiphenylsilane, with a mass fraction of 3.6 times that of 1,2-epoxy-4-vinylcyclohexane, was added dropwise at a rate of 2 ml / min. The mixture was kept at 86°C and reacted for 7 h. The mixture was then rotary evaporated to obtain epoxymethyldiphenylsilane. Melamine and N,N-dimethylformamide were mixed at a mass ratio of 1:11. The mixture was heated to 95°C and stirred until dissolved. After cooling to 81°C, a catalyst of triethylamine with a mass fraction of 0.5 times that of melamine and an epoxymethyldiphenylsilane with a mass fraction of 13.5 times that of melamine were added. The mixture was reacted for 5 h. After cooling to room temperature, the mixture was precipitated with petroleum ether. The precipitate was filtered and washed four times with deionized water and methanol. The precipitate was then dried under vacuum at 70°C to obtain a silicon source.

[0040] S3. 1,3-bis(1-isocyano-2-propyl)benzene and N,N-dimethylformamide were mixed at a mass ratio of 1.1:5, placed in an ice bath, and stirred until homogeneous. Then, 0.94 times the mass of diethylene glycolamine (1,3-bis(1-isocyano-2-propyl)benzene) was added, the mixture was heated to 5°C, and reacted for 21 h. The mixture was precipitated with ethyl acetate, filtered, washed four times with ethyl acetate, and dried under vacuum to obtain diurea diol. Under a nitrogen atmosphere, pentaerythritol diphosphate diphosphoryl chloride, a silicon source, tetrahydrofuran, and triethylamine were mixed in a molar ratio of 1:1.1:9:1, heated to 70°C, and reacted for 10 h. Then, pentaerythritol diphosphate diphosphoryl chloride was added. A nitrogen source, bisurea diol, with a molar amount of phosphoryl chloride of 1.2 times, was heated to 153°C and reacted for 50 min. The mixture was then precipitated with deionized water and filtered. Hydroxyethyl acrylate, p-toluenesulfonic acid catalyst, hydroquinone inhibitor, and toluene were then added. The molar ratio of pentaerythritol diphosphate bisphosphonate, hydroxyethyl acrylate, p-toluenesulfonic acid catalyst, hydroquinone inhibitor, and toluene was 1:2.1:0.03:0.001:20. The mixture was then cooled to 90°C and reacted for 7 h. Finally, deionized water with a molar amount of 1.5 times the mass of hydroxyethyl acrylate and ammonium persulfate initiator with a molar amount of 0.03 times the mass of hydroxyethyl acrylate were added, and the reaction was continued for 5 h to obtain a polyacrylate derivative.

[0041] S4. Bisphenol A epoxy resin and polyester benzotriazole are mixed at a mass ratio of 100:12, heated to 85°C, stirred at 600 rpm for 1.5 h, cooled to 55°C, and added triethylenetetramine (0.02 times the mass of polyester benzotriazole) as a curing agent and polyacrylate derivative (0.3 times the mass of polyester benzotriazole). After stirring evenly, the mixture is heated to 81°C and cured for 1.5 h, then heated to 121°C and cured for 1.5 h, then heated to 151°C and cured for 1.5 h. The mixture is then cooled to room temperature to obtain a UV-resistant epoxy resin material for copper-clad laminates.

[0042] Example 3

[0043] The method for preparing the UV-resistant epoxy resin material for the copper-clad laminate in this embodiment is as follows:

[0044] S1. 4-(2-aminoethyl)phenylacetic acid and acetic anhydride were mixed in an equimolar ratio and placed in pyridine at 40 times the mass of acetic anhydride. The mixture was heated to 70℃ and reacted for 5 h. An equal volume of 3% hydrochloric acid (by mass fraction) was added to the mixture. The mixture was extracted with dichloromethane, washed five times successively with saturated sodium bicarbonate and saturated brine, dried over anhydrous sodium sulfate, and finally dried under vacuum at 50℃ to obtain N-acetyl-4-(2-aminoethyl)phenylacetic acid. Terephthalic acid, N-acetyl-4-(2-aminoethyl)phenylacetic acid, ethylene glycol, and tetrabutyl titanate were mixed in a mass ratio of 100:7.5:50:0.05, heated to 252℃ and 0.5 MPa, and reacted for 4 h. The mixture was then heated to 270℃, evacuated to 10 kPa, and reacted for another 2 h. The mixture was then heated to 285℃ and reacted for another 3 h. The mixture was water-cooled, sliced, and then terephthalic acid was added. Dichloromethane (0.8 times the mass of terephthalic acid) and N,N-dimethylformamide (0.06 times the mass of terephthalic acid) were placed in an ice bath and stirred until homogeneous. Then, thionyl chloride (0.9 times the mass of terephthalic acid) was added dropwise at a rate of 3 ml / min. The temperature was raised to 50 °C, and the reaction was carried out for 24 h. The mixture was then distilled under reduced pressure to obtain phenylacetyl chloride polyester. 2-(2'-hydroxy-5'-methylphenyl)benzotriazole and pyridine were mixed at a mass ratio of 1:6, stirred until homogeneous, and placed in an ice bath. The mixture was kept at this temperature, and a 40% (w / w) solution of phenylacetyl chloride polyester in dichloromethane was added dropwise at a rate of 4 ml / min. After the addition was completed, the temperature was raised to 50 °C, and the reaction was continued for 3 h. The mixture was quenched with ice water, extracted with dichloromethane, washed successively with 3% (w / w) hydrochloric acid, saturated sodium carbonate solution, and saturated brine, dried over anhydrous sodium sulfate, and rotary evaporated to obtain polyester benzotriazole.

[0045] S2. 1,2-Epoxy-4-vinylcyclohexane, Karstedt catalyst, and toluene were mixed at a mass ratio of 16:0.1:60. After stirring until homogeneous, the mixture was heated to 82°C. A 60% toluene solution of methyldiphenylsilane, with a mass fraction of 3.8 times that of 1,2-epoxy-4-vinylcyclohexane, was added dropwise at a rate of 3 ml / min. The mixture was kept at 88°C and reacted for 8 h. The mixture was then rotary evaporated to obtain epoxymethyldiphenylsilane. Melamine and N,N-dimethylformamide were mixed at a mass ratio of 1:12. The mixture was heated to 100°C and stirred until dissolved. After cooling to 82°C, a catalyst of triethylamine with a mass fraction of 0.6 times that of melamine and an epoxymethyldiphenylsilane with a mass fraction of 15 times that of melamine were added. The mixture was reacted for 6 h. After cooling to room temperature, the mixture was precipitated with petroleum ether. The precipitate was filtered and washed five times with deionized water and methanol. The precipitate was then dried under vacuum at 80°C to obtain a silicon source.

[0046] S3. 1,3-bis(1-isocyano-2-propyl)benzene and N,N-dimethylformamide were mixed at a mass ratio of 1.2:5, placed in an ice bath, and stirred until homogeneous. Then, 0.95 times the mass of diethylene glycolamine (1,3-bis(1-isocyano-2-propyl)benzene) was added, the mixture was heated to 6°C, and reacted for 24 h. The mixture was precipitated with ethyl acetate, filtered, washed five times with ethyl acetate, and dried under vacuum to obtain diurea diol. Under a nitrogen atmosphere, pentaerythritol diphosphate diphosphoryl chloride, a silicon source, tetrahydrofuran, and triethylamine were mixed in a molar ratio of 1:1.2:10:1, heated to 80°C, and reacted for 12 h. Then, pentaerythritol diphosphate diphosphoryl chloride was added. A nitrogen source, bisurea diol, with a molar amount of phosphoryl chloride of 1.3 times, was heated to 155°C and reacted for 60 min. The mixture was precipitated with deionized water and filtered. Then, hydroxyethyl acrylate, p-toluenesulfonic acid catalyst, hydroquinone and toluene were added. The molar ratio of pentaerythritol diphosphate bisphosphonate, hydroxyethyl acrylate, p-toluenesulfonic acid catalyst, hydroquinone and toluene was 1:2.2:0.04:0.001:20. The mixture was cooled to 95°C and reacted for 8 h. Then, deionized water with a molar amount of 1.6 times the mass of hydroxyethyl acrylate and ammonium persulfate initiator with a molar amount of 0.04 times the mass of hydroxyethyl acrylate were added, and the reaction was continued for 6 h to obtain a polyacrylate derivative.

[0047] S4. Bisphenol A epoxy resin and polyester benzotriazole are mixed at a mass ratio of 100:13, heated to 90°C, stirred at 800 rpm for 2 hours, cooled to 60°C, and then added triethylenetetramine (0.03 times the mass of polyester benzotriazole) as a curing agent and polyacrylate derivative (0.4 times the mass of polyester benzotriazole). After stirring evenly, the mixture is heated to 82°C and cured for 2 hours, then heated to 122°C and cured for 2 hours, then heated to 152°C and cured for 2 hours. The mixture is then cooled to room temperature to obtain a UV-resistant epoxy resin material for copper-clad laminates.

[0048] Comparative Example 1

[0049] The preparation method of Comparative Example 1 is the same as that of Example 2. The difference between the UV-resistant epoxy resin material used in this copper-clad laminate and that in Example 2 is that the polyester benzotriazole is prepared by reacting benzotriazole with N-acetyl-4-(2-aminoethyl)phenylacetic acid chlorinated with acetyl chloride.

[0050] Comparative Example 2

[0051] The preparation method of Comparative Example 2 is the same as that of Example 2. The difference between the UV-resistant epoxy resin material used for this copper-clad laminate and that of Example 2 is that it is prepared by adding 2-(2'-hydroxy-5'-methylphenyl)benzotriazole and polyacrylate derivatives to bisphenol A epoxy resin.

[0052] Comparative Example 3

[0053] The preparation method of Comparative Example 3 is the same as that of Example 2. The difference between the UV-resistant epoxy resin material used in this copper-clad laminate and that in Example 2 is that the polyacrylate derivative is obtained by polymerization of hydroxyethyl acrylate with phosphorus and silicon sources.

[0054] Comparative Example 4

[0055] The preparation method of Comparative Example 4 is the same as that of Example 2. The difference between the UV-resistant epoxy resin material used in this copper-clad laminate and that in Example 2 is that the polyacrylate derivative is obtained by polymerization of hydroxyethyl acrylate with phosphorus and nitrogen sources.

[0056] Comparative Example 5

[0057] The preparation method of Comparative Example 5 is the same as that of Example 2. The difference between the UV-resistant epoxy resin material used in this copper-clad laminate and that in Example 2 is that the polyacrylate derivative is obtained by polymerization of hydroxyethyl acrylate with nitrogen and silicon sources.

[0058] Comparative Example 6

[0059] The preparation method of Comparative Example 6 is the same as that of Example 2. The difference between the UV-resistant epoxy resin material used in this copper-clad laminate and that in Example 2 is that polyester benzotriazole and polyacrylate are added to the bisphenol A epoxy resin, and the polyacrylate is obtained by homopolymerization of hydroxyethyl acrylate.

[0060] Example of effect

[0061] Table 1 below shows the performance test results of the UV-resistant epoxy resin materials for copper-clad laminates prepared in the examples and comparative examples;

[0062] Table 1

[0063]

[0064] As can be seen from the performance data comparison in Table 1, the UV-resistant epoxy resin material for copper-clad laminates prepared by this invention is not only lightweight, but also has excellent UV resistance, stability, mechanical properties and dielectric properties.

[0065] A comparison of the experimental data from Examples 1, 2, and 3 and Comparative Examples 1 and 2 reveals that introducing benzotriazole with flexible segments into epoxy resin not only gives the material UV resistance, but also effectively disperses the stress induced by ultraviolet radiation, reduces the generation of microcracks, and enables the material to maintain stability under long-term ultraviolet exposure.

[0066] A comparison of the experimental data from Examples 1, 2, and 3 and Comparative Examples 3, 4, 5, and 6 reveals that pentaerythritol diphosphate diphosphonate chloride reacts with the amino groups on the silicon source, and then reacts with the hydroxyl groups on the diurea diol and hydroxyethyl acrylate to form polymerizable acrylate monomers containing phosphorus, nitrogen, and silicon. The resulting polyacrylate derivatives not only possess excellent flame retardant properties but also outstanding UV resistance. Furthermore, when combined with modified epoxy resin, the material maintains good dielectric and mechanical properties.

[0067] Obviously, the above embodiments are merely examples to clearly illustrate the embodiments of the present invention, and are not intended to limit the embodiments of the present invention. Those skilled in the art will recognize that other variations or modifications can be made based on the above description. It is neither necessary nor possible to exhaustively list all embodiments here. However, these obvious variations or modifications derived from the spirit of the present invention are still within the protection scope of the present invention.

Claims

1. A UV-resistant epoxy resin material for copper-clad laminates, characterized in that, It is prepared by adding polyester benzotriazole and polyacrylate derivative to bisphenol A epoxy resin; the polyacrylate derivative is prepared by polymerization of hydroxyethyl acrylate with phosphorus source, nitrogen source and silicon source.

2. The UV-resistant epoxy resin material for copper-clad laminates according to claim 1, characterized in that, The polyester benzotriazole is prepared by reacting 2-(2'-hydroxy-5'-methylphenyl)benzotriazole with phenylacetyl chloride polyester; the phenylacetyl chloride polyester is prepared by reacting terephthalic acid, N-acetyl-4-(2-aminoethyl)phenylacetic acid and ethylene glycol, followed by acyl chloride.

3. The UV-resistant epoxy resin material for copper-clad laminates according to claim 1, characterized in that, The phosphorus source is pentaerythritol diphosphate diphosphonate chloride; the nitrogen source is diurea diol.

4. The UV-resistant epoxy resin material for copper-clad laminates according to claim 1, characterized in that, The silicon source is prepared by reacting epoxymethyldiphenylsilane with melamine.

5. The method for preparing a UV-resistant epoxy resin material for copper-clad laminates according to claim 1, characterized in that, The specific steps include the following: S1. Mix 2-(2'-hydroxy-5'-methylphenyl)benzotriazole and pyridine at a mass ratio of 1:5-6, stir well, place in an ice bath, keep warm, and add a 30-40% (w / w) dichloromethane solution of phenylacetyl chloride polyester dropwise at a rate of 1-4 ml / min. After the addition is complete, raise the temperature to 40-50°C and continue the reaction for 2-3 h. Quench with ice water, extract with dichloromethane, wash successively with 1-3% (w / w) hydrochloric acid, saturated sodium carbonate solution and saturated brine, dry with anhydrous sodium sulfate, and rotary evaporate to obtain polyester benzotriazole; S2. Melamine and N,N-dimethylformamide are mixed at a mass ratio of 1:10-12, heated to 90-100℃, stirred and dissolved, then cooled to 80-82℃. 0.4-0.6 times the mass of melamine catalyst triethylamine and 12-15 times the mass of melamine epoxymethyldiphenylsilane are added, and the reaction is carried out for 4-6 hours. The mixture is cooled to room temperature and precipitated with petroleum ether. After filtration, it is washed 3-5 times with deionized water and methanol, and then dried under vacuum at 60-80℃ to obtain the silicon source. S3. Under a nitrogen atmosphere, mix pentaerythritol diphosphate bisphosphonate (phosphoric acid), silicon source, tetrahydrofuran, and triethylamine in a molar ratio of 1:1–1.2:8–10:1, heat to 60–80°C, and react for 8–12 hours. Then add 1.1–1.3 times the molar amount of pentaerythritol diphosphate bisphosphonate (phosphoric acid) as a nitrogen source (diurea diol), heat to 150–155°C, and react for 40–60 minutes. Precipitate with deionized water and filter. Then add hydroxyethyl acrylate, p-toluenesulfonic acid (catalyst), and polymerization inhibitor. The molar ratio of hydroquinone and toluene, pentaerythritol diphosphate diphosphoryl chloride, hydroxyethyl acrylate, p-toluenesulfonic acid catalyst, and hydroquinone and toluene polymerization inhibitor is 1:2-2.2:0.02-0.04:0.001:

20. The temperature is lowered to 85-95℃, and the reaction is carried out for 6-8 hours. Then, 1.4-1.6 times the mass of hydroxyethyl acrylate deionized water and 0.02-0.04 times the mass of hydroxyethyl acrylate initiator ammonium persulfate are added, and the reaction is continued for 4-6 hours to obtain polyacrylate derivatives. S4. Bisphenol A epoxy resin and polyester benzotriazole are mixed at a mass ratio of 100:11-13, heated to 80-90℃, and stirred at 400-800 rpm for 1-2 hours. The mixture is then cooled to 50-60℃, and 0.01-0.03 times the mass of polyester benzotriazole is added as a curing agent triethylenetetramine and 0.1-0.4 times the mass of polyester benzotriazole as a polyacrylate derivative. After stirring evenly, the mixture is heated to 80-82℃ and cured for 1-2 hours. The temperature is then raised to 120-122℃ and cured for 1-2 hours. The temperature is then raised to 150-152℃ and cured for 1-2 hours. The mixture is then cooled to room temperature to obtain a UV-resistant epoxy resin material for copper-clad laminates.

6. The method for preparing a UV-resistant epoxy resin material for copper-clad laminates according to claim 5, characterized in that, In step S1 above, the preparation method of phenylacetyl chloride polyester is as follows: terephthalic acid, N-acetyl-4-(2-aminoethyl)phenylacetic acid, ethylene glycol, and tetrabutyl titanate are mixed in a mass ratio of 100:2.5–7.5:48–50:0.05, heated to 250–252°C, and reacted at a pressure of 0.3–0.5 MPa for 3–4 hours. The temperature is then raised to 260–270°C, a vacuum is applied to 5–10 kPa, and the reaction continues for 1–2 hours. Finally, the temperature is raised to 275°C. The mixture was heated to 285℃ and reacted for 2–3 hours. After water cooling and slicing, 0.6–0.8 times the mass of terephthalic acid in dichloromethane and 0.02–0.06 times the mass of terephthalic acid in N,N-dimethylformamide catalyst were added. The mixture was placed in an ice bath and stirred until homogeneous. Then, 0.7–0.9 times the mass of terephthalic acid in thionyl chloride was added dropwise at a rate of 1–3 ml / min. The temperature was raised to 40–50℃ and the reaction was carried out for 16–24 hours. The mixture was then distilled under reduced pressure to obtain phenylacetyl chloride polyester.

7. The method for preparing a UV-resistant epoxy resin material for copper-clad laminates according to claim 6, characterized in that, The preparation method of N-acetyl-4-(2-aminoethyl)phenylacetic acid is as follows: 4-(2-aminoethyl)phenylacetic acid and acetic anhydride are mixed in an equimolar ratio and placed in pyridine with a mass of 20 to 40 times that of acetic anhydride. The mixture is heated to 60 to 70°C and reacted for 4 to 5 hours. Hydrochloric acid with a mass fraction of 1 to 3% equal to that of pyridine is added. The mixture is extracted with dichloromethane, washed 3 to 5 times successively with saturated sodium bicarbonate and saturated brine, dried with anhydrous sodium sulfate, and finally dried under vacuum at 40 to 50°C to obtain N-acetyl-4-(2-aminoethyl)phenylacetic acid.

8. The method for preparing a UV-resistant epoxy resin material for copper-clad laminates according to claim 5, characterized in that, In step S2 above, the preparation method of epoxymethyldiphenylsilane is as follows: 1,2-epoxy-4-vinylcyclohexane, Karstedt catalyst and toluene are mixed at a mass ratio of 13-16:0.1:40-60. After stirring evenly, the mixture is heated to 80-82°C. A toluene solution of 50-60% methyldiphenylsilane, with a mass fraction of 3.4-3.8 times that of 1,2-epoxy-4-vinylcyclohexane, is added dropwise at a rate of 1-3 ml / min. The mixture is kept at 84-88°C and reacted for 6-8 hours. The mixture is then rotary evaporated to obtain epoxymethyldiphenylsilane.

9. The method for preparing a UV-resistant epoxy resin material for copper-clad laminates according to claim 5, characterized in that, In step S3 above, the preparation method of diurea diol is as follows: 1,3-bis(1-isocyano-2-propyl)benzene and N,N-dimethylformamide are mixed at a mass ratio of 1 to 1.2:5, placed in an ice bath, stirred evenly, and then 0.93 to 0.95 times the mass of diethylene glycolamine of 1,3-bis(1-isocyano-2-propyl)benzene are added. The mixture is heated to 4 to 6°C and reacted for 18 to 24 hours. The mixture is precipitated with ethyl acetate, filtered, washed 3 to 5 times with ethyl acetate, and dried under vacuum to obtain diurea diol.

Images