Low-dielectric-loss hydrocarbon resin glue solution for copper-clad plate and preparation method of low-dielectric-loss hydrocarbon resin glue solution

Abstract

The invention discloses a low-dielectric-loss hydrocarbon resin glue solution for a copper-clad plate and a preparation method of the low-dielectric-loss hydrocarbon resin glue solution, and relates to the technical field of copper-clad plates. 1, 2-polybutadiene and a hydrogenated styrene-butadiene block copolymer are compounded to guarantee low dielectric loss; hydrocarbon resin is introduced into a cyanate ester-bismaleimide-benzoxazine resin system to prepare a composite resin system, bisphenol A cyanate ester is pre-polymerized under catalysis of zinc acetylacetonate, a triazine ring structure is formed through trimerization, the glass transition temperature is increased, the dielectric constant is reduced, phenolphthalein polyarylether sulfone improves toughness and impact strength, and the dielectric constant is reduced. Bismaleimide is added to improve the adhesive force and thermal stability, and benzoxazine is subjected to ring-opening polymerization to provide phenolic hydroxyl groups and secondary amine which participate in crosslinking to form a low-dielectric thermosetting network. The modified ammonium polyphosphate and the silica powder form a heat insulation layer, phosphorus-silicon synergistic flame retardance is formed, and UL-94V-0-level flame retardance is achieved. The copper-clad plate provided by the invention is especially suitable for the high-end fields of 5G high-frequency copper-clad plates, aerospace thermal protection coatings and the like.

Description

Technical Field

[0001] This invention relates to the field of copper clad laminate technology, specifically to a low dielectric loss hydrocarbon resin adhesive for copper clad laminates and its preparation method. Background Technology

[0002] With the rapid development of 5G communication, high-frequency high-speed circuits, and the Internet of Things, higher requirements are being placed on copper-clad laminate (CCL) materials, especially in terms of signal transmission speed and quality. Traditional CCL matrix resins (such as epoxy resin and polytetrafluoroethylene) are insufficient to meet the demands of high-frequency signal transmission due to their high dielectric constant and dielectric loss. Hydrocarbon resins, containing only carbon and hydrogen elements in their molecular chains and with low polarity of the CH bonds, possess excellent dielectric properties and have become one of the ideal matrix materials for high-frequency CCLs. However, hydrocarbon resins themselves have drawbacks such as poor heat resistance, low glass transition temperature, insufficient rigidity, and a large coefficient of thermal expansion, limiting their widespread application in high-frequency, high-speed CCLs.

[0003] In recent years, researchers have modified hydrocarbon resins using various methods to improve their overall performance. For example, by introducing cross-linking reactions of unsaturated double bonds to form a highly cross-linked interpenetrating polymer network structure, the resin is transformed from a thermoplastic to a thermosetting resin, thereby improving its mechanical strength and heat resistance. Furthermore, preparing a prepreg by combining hydrocarbon resins with low-dielectric ceramic powder and then impregnating it with glass fiber cloth can effectively improve its dielectric and mechanical properties. Simultaneously, by adding functional fillers, wetting and dispersing agents, flame retardants, antioxidants, and cross-linking agents, the performance of hydrocarbon resins can be further optimized, making them suitable for higher-frequency applications.

[0004] Currently, the application of hydrocarbon resins in high-frequency copper-clad laminates has made some progress, but it still faces some challenges, such as weak adhesion, poor filler compatibility, and low thermal conductivity. To solve these problems, this invention provides a low-dielectric-loss hydrocarbon resin adhesive for copper-clad laminates and its preparation method. Through reasonable modification and composite technology, its comprehensive performance can be further improved to meet the needs of future electronic devices for high-frequency and high-speed materials. Summary of the Invention

[0005] The purpose of this invention is to provide a low dielectric loss hydrocarbon resin adhesive for copper clad laminates and its preparation method, so as to solve the problems raised in the prior art.

[0006] To achieve the above objectives, the present invention provides the following technical solution: A method for preparing a low dielectric loss hydrocarbon resin adhesive for copper clad laminates includes the following preparation steps: S1: Mix methyl ethyl ketone and toluene, add molecular sieve and silica powder, stir for 4-8 hours, filter, add 1,2-polybutadiene and hydrogenated styrene-butadiene block copolymer to obtain a mixture; S2: Add bisphenol A cyanate and zinc acetylacetonate to the reactor, heat to 80-90℃, keep warm for 10-30 min, add phenolphthalein polyarylether sulfone, heat to 120-130℃, keep warm for 20-40 min, cool to 60-70℃, add N,N'-(4,4'-methylenediphenyl)bismaleimide, benzoxazine resin, and the mixture, heat to 70-90℃ under nitrogen protection and stir for 20-40 min to obtain the mixed resin solution; S3: Add flame retardant, antioxidant and crosslinking agent to the mixed resin liquid, ultrasonically disperse for 10-30 min, ultrasonically degas for 8-15 min, cool to 50-60℃ and stir for 5-10 min to obtain low dielectric loss hydrocarbon resin liquid for copper clad laminate.

[0007] In a more optimized manner, by weight, the raw material composition of the mixture in step S1 is: 20-40 parts methyl ethyl ketone, 15-25 parts toluene, 0.6-2.0 parts molecular sieve, 10-15 parts silica powder, 40-60 parts 1,2-polybutadiene, and 20-40 parts hydrogenated styrene-butadiene block copolymer. By weight, in step S2, the raw material composition of the mixed resin liquid is: 60-80 parts of mixed liquid, 40-60 parts of bisphenol A cyanate ester, 3-6 parts of phenolphthalein polyarylether sulfone, 0.1-0.5 parts of zinc acetylacetonate, 20-30 parts of N,N'-(4,4'-methylenediphenyl)bismaleimide, and 15-25 parts of benzoxazine resin; By weight, in step S3, the raw material composition of the low dielectric loss hydrocarbon resin adhesive for copper clad laminate is: 60-80 parts mixed resin liquid, 8-14 parts flame retardant, 1-2 parts antioxidant, and 1.0-2.0 parts crosslinking agent.

[0008] More preferably, the silicon micropowder is hollow silicon micropowder; the hollow silicon micropowder has an average particle size of 0.5-5 μm, a pore wall thickness of 0.1-0.7 μm, and a true density of 1.0-1.3 g / cm³. 3 ; More preferably, the flame retardant includes organic flame retardants and inorganic flame retardants; the inorganic flame retardant is one or more of phosphorus-based flame retardants, nitrogen-based flame retardants, aluminum-based flame retardants, boron-based flame retardants, and zinc stannate flame retardants; the organic flame retardant is one or more of bromine-based flame retardants and organosilicon flame retardants. More preferably, the flame retardant is modified ammonium polyphosphate, and the preparation process of the modified ammonium polyphosphate is as follows: ethanol and deionized water are added to a reaction vessel, heated to 75-90℃ and stirred for 20-40 minutes, then molten diaminodiphenylmethane and ammonium polyphosphate are added, the temperature is raised to 50-60℃ and stirred for 3-5 hours, cooled, filtered, washed with deionized water, dried and sieved to obtain modified ammonium polyphosphate; More preferably, the antioxidant is one or a combination of several of the following: pentaerythritol tetrakis[β-propionate], tris(2,4-di-tert-butylphenyl) phosphite, 2,4-di(n-octylthionyl)-6-methylphenol, and 2,6-di-tert-butyl-p-cresol; the crosslinking agent is one or a combination of several of the following: dicumyl peroxide, benzoyl peroxide, bismaleimide, di-tert-butyldicumyl peroxide, and azobisisobutyronitrile. More optimally, the antioxidant is a compound of pentaerythritol tetrakis[β-propionic acid] and tris(2,4-di-tert-butylphenyl) phosphite in a mass ratio of 3:1; it synergistically resists oxidation and prevents thermal aging. In a more optimized manner, the application of the hydrocarbon resin adhesive is as follows: the hydrocarbon resin adhesive is coated on glass fiber cloth and baked at 100-120°C for 15-30 minutes to obtain a prepreg; the prepreg and copper foil covering both sides of it are stacked together, heated and pressurized, and cooled to room temperature to obtain a copper-clad laminate. The heating and pressurizing process conditions are: temperature 170-230℃, pressure 2-5MPa, and time 120-240min.

[0009] Compared with the prior art, the beneficial effects of the present invention are: The purpose of this invention is to provide a low dielectric loss hydrocarbon resin adhesive for copper clad laminates and its preparation method. By optimizing the resin system, modifying the filler and crosslinking reaction, its comprehensive performance is improved, making it suitable for higher frequency applications.

[0010] Hollow silica powder can reduce the viscosity of resin adhesive and improve impregnation uniformity; the mixed solvent of methyl ethyl ketone and toluene can effectively dissolve 1,2-polybutadiene and hydrogenated styrene-butadiene block copolymer, and the compounding of 1,2-polybutadiene and hydrogenated styrene-butadiene block copolymer ensures low dielectric loss; molecular sieves are used to efficiently adsorb trace amounts of moisture in the solvent to prevent subsequent curing problems, and nitrogen protection prevents polymer oxidation; the crosslinking agent dicumyl peroxide decomposes to generate free radicals, which initiate the polymerization of 1,2-polybutadiene double bonds to form a three-dimensional network and enhance interfacial strength. Hydrocarbon resins suffer from poor dielectric loss and resistance to heat and oxygen aging. This invention introduces hydrocarbon resins into a cyanate ester-bismaleimide-benzoxazine resin system to prepare a cyanate ester-bismaleimide-benzoxazine-hydrocarbon composite resin system. Bisphenol A cyanate is prepolymerized under zinc acetylacetonate catalysis, forming a triazine ring structure through trimerization, which increases the glass transition temperature and reduces the dielectric constant. Phenolphthalein-type polyarylene sulfone forms hydrogen bonds with cyanate ester, improving toughness and impact strength. The addition of bismaleimide improves adhesion and thermal stability. The ring-opening polymerization of benzoxazine provides phenolic hydroxyl groups and secondary amines, improving processing fluidity and participating in crosslinking, synergistically reducing the dielectric constant. In addition, the residual double bonds of bismaleimide co-crosslink with 1,2-polybutadiene, avoiding oxidation under nitrogen protection, forming a low-dielectric flexible-rigid interpenetrating network. The combination of multiple functional materials achieves a synergistic effect of low dielectric loss, high heat resistance, good flame retardancy, and high toughness.

[0011] Ammonium polyphosphate is an environmentally friendly intumescent flame retardant, a highly efficient organic-inorganic composite flame retardant. It is heat-resistant and has excellent flame retardancy, decomposing at high temperatures to release ammonia and phosphoric acid, thus inhibiting combustion. No harmful gases are generated during combustion. Phosphorus-based flame retardants are low in toxicity and highly efficient, suitable for halogen-free requirements, and can be applied to electronic materials. Modified ammonium polyphosphate forms dense covalent bonds, improving flame retardant efficiency, catalyzing resin dehydration to char, and forming a heat-insulating layer with silicon micropowder, achieving a phosphorus-silicon synergistic flame retardancy rating of UL-94V-0. Ammonium polyphosphate undergoes phosphorus hydrolysis to generate phosphate esters, which can undergo transesterification with the phenolic hydroxyl groups in hydrocarbon resins. The phosphate esters promote char formation and enhance flame retardancy. The remaining amino groups in the modified ammonium polyphosphate react with the mixed resin liquid, enhancing interfacial adhesion. Furthermore, the amino groups in the modified ammonium polyphosphate can form a covalent cross-linked network with the hydroxyl groups in the resin, improving bond strength.

[0012] This low dielectric loss hydrocarbon resin adhesive for copper clad laminates has excellent low dielectric loss, thermal stability and durability, good flame retardancy, and broad application prospects, especially in high-end fields such as 5G communication, high frequency circuit boards, and aerospace. Detailed Implementation

[0013] The technical solutions in the embodiments of the present invention will be clearly and completely described below. Obviously, the described embodiments are only some embodiments of the present invention, and not all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those skilled in the art without creative effort are within the scope of protection of the present invention.

[0014] Example 1: A method for preparing a low dielectric loss hydrocarbon resin adhesive for copper clad laminates, comprising the following preparation steps: S1: Mix methyl ethyl ketone and toluene, add molecular sieve and hollow silica powder, stir for 5 hours, filter, add 1,2-polybutadiene and hydrogenated styrene-butadiene block copolymer to obtain a mixture; S2: Add bisphenol A cyanate and zinc acetylacetonate to the reactor, heat to 90°C, keep warm for 15 min, add phenolphthalein polyarylether sulfone, heat to 125°C, keep warm for 30 min, cool to 65°C, add N,N'-(4,4'-methylenediphenyl)bismaleimide, benzoxazine resin, and the mixture, heat to 85°C under nitrogen protection and stir for 30 min to obtain the mixed resin solution; S3: Add flame retardant, antioxidant and dicumyl peroxide to the mixed resin solution, ultrasonically disperse for 20 min, ultrasonically degas for 10 min, cool to 60℃ and stir for 7 min to obtain low dielectric loss hydrocarbon resin solution for copper clad laminate. In step S1, by weight, the raw material composition of the mixture is: 30 parts methyl ethyl ketone, 20 parts toluene, 1.5 parts molecular sieve, 12 parts hollow silica powder, 55 parts 1,2-polybutadiene, and 35 parts hydrogenated styrene-butadiene block copolymer. By weight, in step S2, the raw material composition of the mixed resin liquid is: 70 parts of mixed liquid, 60 parts of bisphenol A cyanate ester, 4 parts of phenolphthalein polyarylether sulfone, 0.4 parts of zinc acetylacetonate, 25 parts of N,N'-(4,4'-methylenediphenyl)bismaleimide, and 15 parts of benzoxazine resin. By weight, in step S3, the raw material composition of the low dielectric loss hydrocarbon resin adhesive for copper clad laminate is: 65 parts mixed resin liquid, 14 parts flame retardant, 2 parts antioxidant, and 1.8 parts dicumyl peroxide. The hollow silicon micropowder has a particle size of 3 μm, a pore wall thickness of 0.5 μm, and a true density of 1.1 g / cm³. 3 ; The flame retardant is modified ammonium polyphosphate. The preparation process of the modified ammonium polyphosphate is as follows: ethanol and deionized water are added to a reaction vessel, heated to 85°C and stirred for 30 minutes, then molten diaminodiphenylmethane and ammonium polyphosphate are added, the temperature is raised to 60°C and stirred for 4 hours, cooled, filtered, washed three times with deionized water, dried and sieved to obtain modified ammonium polyphosphate. The modified ammonium polyphosphate has the following raw material composition by weight: 200 parts ethanol, 10 parts deionized water, 10 parts diaminodiphenylmethane, and 20 parts ammonium polyphosphate. The antioxidant is a compound of pentaerythritol tetrakis[β-propionic acid] and tris(2,4-di-tert-butylphenyl) phosphite in a mass ratio of 3:1.

[0015] Example 2: A method for preparing a low dielectric loss hydrocarbon resin adhesive for copper clad laminates, comprising the following preparation steps: S1: Mix methyl ethyl ketone and toluene, add molecular sieve and hollow silica powder, stir for 7 hours, filter, add 1,2-polybutadiene and hydrogenated styrene-butadiene block copolymer to obtain a mixture; S2: Add bisphenol A cyanate and zinc acetylacetonate to the reactor, heat to 82°C, hold for 22 min, add phenolphthalein polyarylether sulfone, heat to 125°C, hold for 40 min, cool to 60°C, add N,N'-(4,4'-methylenediphenyl)bismaleimide, benzoxazine resin, and the mixture, heat to 77°C under nitrogen protection and stir for 35 min to obtain the mixed resin solution; S3: Add flame retardant, antioxidant and dicumyl peroxide to the mixed resin solution, ultrasonically disperse for 30 min, ultrasonically degas for 15 min, cool to 55℃ and stir for 10 min to obtain low dielectric loss hydrocarbon resin solution for copper clad laminate. By weight, in step S1, the raw material composition of the mixture is: 40 parts methyl ethyl ketone, 25 parts toluene, 1.2 parts molecular sieve, 13 parts hollow silica powder, 45 parts 1,2-polybutadiene, and 25 parts hydrogenated styrene-butadiene block copolymer. By weight, in step S2, the raw material composition of the mixed resin liquid is: 75 parts of mixed liquid, 45 parts of bisphenol A cyanate ester, 6 parts of phenolphthalein polyarylether sulfone, 0.3 parts of zinc acetylacetonate, 25 parts of N,N'-(4,4'-methylenediphenyl)bismaleimide, and 20 parts of benzoxazine resin. By weight, in step S3, the raw material composition of the low dielectric loss hydrocarbon resin adhesive for copper clad laminate is: 70 parts mixed resin liquid, 11 parts flame retardant, 2 parts antioxidant, and 1.5 parts dicumyl peroxide. The hollow silicon micropowder has a particle size of 3 μm, a pore wall thickness of 0.5 μm, and a true density of 1.1 g / cm³. 3 ; The flame retardant is modified ammonium polyphosphate. The preparation process of the modified ammonium polyphosphate is as follows: ethanol and deionized water are added to a reaction vessel, heated to 85°C and stirred for 30 minutes, then molten diaminodiphenylmethane and ammonium polyphosphate are added, the temperature is raised to 60°C and stirred for 4 hours, cooled, filtered, washed three times with deionized water, dried and sieved to obtain modified ammonium polyphosphate. The modified ammonium polyphosphate has the following raw material composition by weight: 200 parts ethanol, 10 parts deionized water, 10 parts diaminodiphenylmethane, and 20 parts ammonium polyphosphate. The antioxidant is a compound of pentaerythritol tetrakis[β-propionic acid] and tris(2,4-di-tert-butylphenyl) phosphite in a mass ratio of 3:1.

[0016] Example 3: A method for preparing a low dielectric loss hydrocarbon resin adhesive for copper clad laminates, comprising the following preparation steps: S1: Mix methyl ethyl ketone and toluene, add molecular sieve and hollow silica powder, stir for 4 hours, filter, add 1,2-polybutadiene and hydrogenated styrene-butadiene block copolymer to obtain a mixture; S2: Add bisphenol A cyanate and zinc acetylacetonate to the reactor, heat to 90°C, keep warm for 15 min, add phenolphthalein polyarylether sulfone, heat to 130°C, keep warm for 24 min, cool to 70°C, add N,N'-(4,4'-methylenediphenyl)bismaleimide, benzoxazine resin, and the mixture, heat to 80°C under nitrogen protection and stir for 25 min to obtain the mixed resin solution; S3: Add flame retardant, antioxidant and dicumyl peroxide to the mixed resin solution, ultrasonically disperse for 15 min, ultrasonically degas for 15 min, cool to 60℃ and stir for 8 min to obtain low dielectric loss hydrocarbon resin solution for copper clad laminate. By weight, in step S1, the raw material composition of the mixture is: 40 parts methyl ethyl ketone, 25 parts toluene, 1.0 part molecular sieve, 15 parts hollow silica powder, 45 parts 1,2-polybutadiene, and 40 parts hydrogenated styrene-butadiene block copolymer. By weight, in step S2, the raw material composition of the mixed resin liquid is: 80 parts of mixed liquid, 50 parts of bisphenol A cyanate ester, 6 parts of phenolphthalein polyarylether sulfone, 0.5 parts of zinc acetylacetonate, 20 parts of N,N'-(4,4'-methylenediphenyl)bismaleimide, and 25 parts of benzoxazine resin. By weight, in step S3, the raw material composition of the low dielectric loss hydrocarbon resin adhesive for copper clad laminate is: 80 parts mixed resin liquid, 8 parts flame retardant, 2 parts antioxidant, and 2.0 parts dicumyl peroxide. The hollow silicon micropowder has a particle size of 3 μm, a pore wall thickness of 0.5 μm, and a true density of 1.1 g / cm³. 3 ; The flame retardant is modified ammonium polyphosphate. The preparation process of the modified ammonium polyphosphate is as follows: ethanol and deionized water are added to a reaction vessel, heated to 85°C and stirred for 30 minutes, then molten diaminodiphenylmethane and ammonium polyphosphate are added, the temperature is raised to 60°C and stirred for 4 hours, cooled, filtered, washed three times with deionized water, dried and sieved to obtain modified ammonium polyphosphate. The modified ammonium polyphosphate has the following raw material composition by weight: 200 parts ethanol, 10 parts deionized water, 10 parts diaminodiphenylmethane, and 20 parts ammonium polyphosphate. The antioxidant is a compound of pentaerythritol tetrakis[β-propionic acid] and tris(2,4-di-tert-butylphenyl) phosphite in a mass ratio of 3:1.

[0017] Comparative Example 1: Using Example 1 as the control group, in step S2, bisphenol A cyanate was not added to the mixed resin solution, and other processes were normal.

[0018] Comparative Example 2: Using Example 1 as the control group, ammonium polyphosphate was used to replace the modified ammonium polyphosphate, while other processes were normal.

[0019] Sources of raw materials used (for illustrative purposes only): The raw materials used in this technical solution are all products currently available on the market: Molecular sieve (12173-28-3, 98%): a product sold by Linyi Azeroth Biotechnology Co., Ltd. under the product name 3A Molecular Siev; 1,2-Polybutadiene (SCPP-80176, 9003-17-2, 99%): Hubei Baidu Chemical Co., Ltd.; Hydrogenated styrene-butadiene block copolymer: a product sold by Taiwan Li Changrong Chemical Co., Ltd. under the product name Globalprene®. Products sold by 9552: Bisphenol A cyanate (1156-51-0, 99%): Sold by Xinyi Yongcheng Chemical Co., Ltd. under product number 001; Zinc acetylacetonate (14024-63-6, 99%): Sold by Hubei Xinkang Pharmaceutical Chemical Co., Ltd.; N,N'-(4,4'-methylenediphenyl)bismaleimide (13676-54-5, 99%): Sold by Wuhan Xinxin Jiali Biotechnology Co., Ltd.; Benzooxazine resin: Sold by Huaibei Lvzhouxin Materials Co., Ltd. under product number LZ-99; Phenolphthalein-type polyarylether sulfone: Sold by Solvay, USA under product number 3100P. Products; Ammonium polyphosphate (68333-79-9, 99%): Hubei Xinhongli Chemical Co., Ltd.; Diaminodiphenylmethane (101-77-9, 99%): Shanghai Tongyuan Chemical Co., Ltd.; Pentaerythritol tetrakis[β-propionate] (6683-19-8, 99%): Hubei Yongkuo Technology Co., Ltd.; Tris(2,4-di-tert-butylphenyl) phosphite (31570-04-4, 99%): Hubei Wande Chemical Co., Ltd.; Dicumyl peroxide (80-43-3, 99%): Shanghai Yuejiang Titanium Dioxide Chemical Products Co., Ltd.; Butanone, toluene, ethanol, analytical grade, commercially available.

[0020] Performance testing: The hydrocarbon resin solutions prepared in the examples and comparative examples were tested. The prepared hydrocarbon resin solution is heated and cured in a mold to obtain a sample.

[0021] (1) Dielectric property test: The resin sample was made into a disc with a diameter of 50 mm and a thickness of 1 mm. Gold electrodes were sputtered on the surface. The dielectric constant (Dk) and dielectric loss (Df) were measured by coaxial waveguide method under the conditions of 10 GHz frequency, 25 ℃ temperature and 50% RH humidity. The average value of three measurements was taken. The system error was calibrated with a standard polytetrafluoroethylene sample before the test.

[0022] (2) Glass transition temperature test: The sample was cut into 30mm×10mm×1mm substrate strips. The temperature was first raised from 25℃ to 150℃ at a heating rate of 10℃ / min to eliminate the thermal history. After cooling to 25℃, the temperature was scanned to 300℃ at a heating rate of 10℃ / min. The glass transition temperature (Tg) at this heating rate was analyzed.

[0023] (3) Flame retardancy test: According to the UL94 vertical burning rating test, the sample is cut into standard size of 125mm×13mm×3mm, vertically fixed on the sample holder, and a methane flame (flame height 20mm) is applied to the lower end of the sample for 10 seconds. The burning time, whether the dripping material ignites the cotton wool, and the self-extinguishing time are recorded. Five samples are tested in each group, and the UL-94 V-0, V-1 or V-2 rating is evaluated according to the burning behavior.

[0024] The test results are as follows: Table 1

[0025] The analysis results are as follows: This invention proposes a method for preparing a low dielectric loss hydrocarbon resin adhesive for copper clad laminates, achieving low dielectric loss, thermal stability, and UL-94V-0 flame retardancy, which can be widely applied in the field of copper clad laminate technology.

[0026] In terms of dielectric properties, the prepared hydrocarbon resin solution exhibits excellent low dielectric characteristics. Measured using the microwave dielectric stripline resonator method, its dielectric constant (Dk) is 2.57-2.66 at 10 GHz, and its dielectric loss (Df) is less than 0.015. This indicates that the resin solution has good dielectric properties for high-frequency signal transmission, effectively reducing signal attenuation and loss, making it suitable for high-end electronic devices such as 5G communications and high-frequency circuit boards. The glass transition temperature of this hydrocarbon resin adhesive is 234-245℃, significantly higher than the conventional Tg value. It can maintain good mechanical properties and structural stability even in high-temperature environments, making it suitable for high heat density applications. Passing the UL94 vertical burning test, the hydrocarbon resin adhesive achieves a V-0 flammability rating, with a self-extinguishing time of less than 10 seconds after initial ignition and no dripping. Its excellent flame-retardant properties are mainly due to the addition of modified ammonium polyphosphate flame retardant, which releases a large amount of non-flammable gas at high temperatures, inhibiting the combustion reaction and thus improving the fire safety of the material.

[0027] Hydrocarbon resin adhesives are constructed through a four-step reaction involving cyanate trimerization, bismaleimide addition, benzoxazine ring-opening, and polybutadiene co-crosslinking, resulting in a resin system with high heat resistance, low dielectric constant, and strong toughness. Bisphenol A cyanate is prepolymerized under zinc acetylacetonate catalysis, forming a triazine ring structure through trimerization, which increases the glass transition temperature and further reduces the dielectric constant. Without the addition of bisphenol A cyanate to the mixed resin solution, dispersibility deteriorates, dielectric constant fluctuates excessively, resulting in low dielectric properties. At the same time, interfacial bonding fails, leading to poor compatibility with the resin. Replacing it with ordinary ammonium polyphosphate reduces flame retardant efficiency. Unmodified ammonium polyphosphate has weak interfacial bonding with the resin, making it easy to detach during combustion, reducing the oxygen index, increasing hygroscopicity, and catalyzing the hydrolysis of cyanate by absorbing moisture. The dielectric loss increases from 0.0020 to 0.0039, and poor water resistance weakens the interface, resulting in instability.

[0028] 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 implemented 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 exemplary and non-limiting, and the scope of the invention is defined by the appended claims rather than the foregoing description. Thus, it is intended that all variations falling within the meaning and scope of equivalents of the claims be included within the present invention.

Claims

1. A method for preparing a low dielectric loss hydrocarbon resin adhesive for copper clad laminates, characterized in that, The preparation steps include the following: S1: Mix methyl ethyl ketone and toluene, add molecular sieve and silica powder, stir for 4-8 hours, filter, add 1,2-polybutadiene and hydrogenated styrene-butadiene block copolymer to obtain a mixture; S2: Add bisphenol A cyanate and zinc acetylacetonate to the reactor, heat up and keep warm for 10-30 min, add phenolphthalein polyarylether sulfone, heat up and keep warm for 20-40 min, cool down and add bismaleimide, benzoxazine resin and mixture, heat up and stir for 20-40 min under nitrogen protection to obtain mixed resin solution. S3: Add flame retardant, antioxidant and crosslinking agent to the mixed resin liquid, ultrasonically disperse for 10-30 min, ultrasonically degas for 8-15 min, cool and stir for 5-10 min to obtain low dielectric loss hydrocarbon resin liquid for copper clad laminate.

2. The method for preparing a low dielectric loss hydrocarbon resin adhesive for copper clad laminates according to claim 1, characterized in that: By weight, in step S1, the raw material composition of the mixture is: 20-40 parts methyl ethyl ketone, 15-25 parts toluene, 0.6-2.0 parts molecular sieve, 10-15 parts silica powder, 40-60 parts 1,2-polybutadiene, and 20-40 parts hydrogenated styrene-butadiene block copolymer.

3. The method for preparing a low dielectric loss hydrocarbon resin adhesive for copper clad laminates according to claim 1, characterized in that: By weight, in step S2, the raw material composition of the mixed resin liquid is: 60-80 parts of mixed liquid, 40-60 parts of bisphenol A cyanate ester, 3-6 parts of phenolphthalein polyarylether sulfone, 0.1-0.5 parts of zinc acetylacetonate, 20-30 parts of bismaleimide, and 15-25 parts of benzoxazine resin.

4. The method for preparing a low dielectric loss hydrocarbon resin adhesive for copper clad laminates according to claim 1, characterized in that: By weight, in step S3, the raw material composition of the low dielectric loss hydrocarbon resin adhesive for copper clad laminate is: 60-80 parts mixed resin liquid, 8-14 parts flame retardant, 1-2 parts antioxidant, and 1.0-2.0 parts crosslinking agent.

5. The method for preparing a low dielectric loss hydrocarbon resin adhesive for copper clad laminates according to claim 1, characterized in that: The antioxidant is one or more of pentaerythritol tetrakis[β-propionate], tris(2,4-di-tert-butylphenyl) phosphite, 2,4-di(n-octylthionyl)-6-methylphenol, and 2,6-di-tert-butyl-p-cresol; the crosslinking agent is one or more of dicumyl peroxide, benzoyl peroxide, bis-tert-butyldicumyl peroxide, and azobisisobutyronitrile.

6. The method for preparing a low dielectric loss hydrocarbon resin adhesive for copper clad laminates according to claim 1, characterized in that: The antioxidant is a compound of pentaerythritol tetrakis[β-propionic acid] and tris(2,4-di-tert-butylphenyl) phosphite in a mass ratio of 3:

1.

7. The method for preparing a low dielectric loss hydrocarbon resin adhesive for copper clad laminates according to claim 1, characterized in that: The silicon micropowder is hollow silicon micropowder; the average particle size of the hollow silicon micropowder is 0.5-5 μm, its pore wall thickness is 0.1-0.7 μm, and its true density is 1.0-1.3 g / cm³. 3 .

8. The method for preparing a low dielectric loss hydrocarbon resin adhesive for copper clad laminates according to claim 1, characterized in that: The flame retardant is one or a combination of several of the following: phosphorus-based flame retardants, nitrogen-based flame retardants, aluminum-based flame retardants, boron-based flame retardants, and zinc stannate flame retardants.

9. The method for preparing a low dielectric loss hydrocarbon resin adhesive for copper clad laminates according to claim 1, characterized in that: The flame retardant is modified ammonium polyphosphate. The preparation process of the modified ammonium polyphosphate is as follows: ethanol and deionized water are added to a reaction vessel, heated to 75-90℃ and stirred for 20-40 minutes, then molten diaminodiphenylmethane and ammonium polyphosphate are added, the temperature is raised to 50-60℃ and stirred for 3-5 hours, cooled, filtered, washed three times with deionized water, dried and sieved to obtain modified ammonium polyphosphate.

10. A low dielectric loss hydrocarbon resin adhesive for copper clad laminates, characterized in that: Prepared by the preparation method according to any one of claims 1-9.

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