CN109517197B - Forming process of high-frequency high-speed nitrile-based resin copper-clad plate - Google Patents
Forming process of high-frequency high-speed nitrile-based resin copper-clad plate Download PDFInfo
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Abstract
The invention discloses a molding process of a high-frequency high-speed nitrile-based resin copper-clad plate, which mainly comprises the synthesis of nitrile-based resin and the molding process of the nitrile-based resin copper-clad plate, wherein solutes in the preparation of the nitrile-based resin are aromatic dihydric phenol, aromatic amine and paraformaldehyde, solvents are N, N-dimethylformamide and toluene, and the molar ratio of the solutes to the solvents is 1: (0.3-0.6), according to the reaction structural formula and a certain proportion, the nitrile resin monomer with a controllable structure can be obtained. And then, by optimizing reaction steps and reaction parameters and combining a copper-clad lamination process, the high-frequency high-speed nitrile resin copper-clad plate can be directly obtained, and has the characteristics of high heat resistance, high TG and excellent halogen-free flame retardance. Compared with the traditional copper-clad plate forming process, the method does not need glue mixing and particle modification and dispersion, and has simple steps and higher efficiency.
Description
Technical Field
The invention relates to the technical field of preparation and manufacturing of polymer-based composite materials, in particular to a molding process of a high-frequency high-speed nitrile-based resin copper-clad plate.
Background
With the rapid advance of information and electronic industries represented by intelligent electronic products, digital circuits gradually enter the stages of high speed information processing and high frequency signal transmission, and the entire electronic system is developed toward the direction of being light, thin, small, multifunctional, high-density, high-reliability and low-cost.
The forming process of the substrate material influences the electronic transmission performance, reliability and cost of the high-frequency high-speed copper-clad plate to a great extent. The traditional preparation process of the copper-clad plate comprises the processes of filler modification of a resin matrix, filler dispersion, resin pretreatment, gluing, resin curing and forming and the like, wherein the filler modification and dispersion steps are complicated, the efficiency is low, and the increase of the defective product amount of the copper-clad plate is easy to cause.
Therefore, the problem that needs to be solved by the technical personnel in the field is how to provide a forming process of nitrile resin for a high-frequency and high-speed copper-clad plate, which has simple and convenient operation process, high efficiency and excellent comprehensive performance.
Disclosure of Invention
In view of the above, the invention provides a high-frequency high-speed nitrile resin copper-clad plate forming process with good comprehensive performance, simplifies the current complicated forming steps, and improves the preparation efficiency of the copper-clad plate.
In order to achieve the purpose, the invention adopts the following technical scheme:
a molding process of a high-frequency high-speed nitrile resin copper-clad plate comprises the following steps:
(1) adding a polymerization reaction promoter and a solvent into the nitrile-based resin, and stirring and reacting at constant temperature of 125-;
(2) putting base cloth into a glue tank to dip the glue solution prepared in the step (1) to obtain dipped base cloth;
(3) baking the dipped base cloth obtained in the step (2) to remove the solvent to obtain a semi-cured rubber sheet;
(4) measuring the gelation time of the prepreg obtained in the step (3), coating copper after lamination, and performing compression molding in a vacuum press;
(5) and naturally cooling to room temperature to obtain the nitrile resin copper-clad plate.
In the technical scheme, the nitrile resin with a simple synthesis method and a controllable molecular structure is used as a resin matrix for the copper-clad plate, a proper temperature range is set, the pre-polymerization reaction of the nitrile resin is realized under the action of a polymerization accelerator, a nitrile resin prepolymer with a certain molecular weight and good film forming property is obtained, and the copper-clad plate material with high polymer structural strength, good temperature resistance and outstanding dielectric property is obtained under the synergistic action of temperature and pressure by utilizing the interfacial bonding action of a reactive group in a molecular structure and a copper foil and the ring-forming polymerization reaction of a nitrile functional group.
Preferably, the polymerization accelerator in step (1) includes one or a mixture of two of epoxy resin, cyanate resin and benzoxazine resin, and the amount of the polymerization accelerator is 8-25% of the total amount of the nitrile resin.
The beneficial effects of the preferred technical scheme are as follows: the accelerator selected by the system has self-polymerization reaction, when the dosage of the polymerization accelerator is lower than the range, the accelerating effect is weaker, and the nitrile resin base material capable of meeting the requirements of high-frequency and high-speed copper-clad plates can not be obtained under the condition; when the amount of the accelerator is more than this range, on the one hand, the accelerator itself undergoes self-polymerization, resulting in phase separation of the system; on the other hand, the accelerant with higher content can reduce the heat resistance and the mechanical strength of the main material nitrile-based resin to a certain extent, and cannot meet the application requirement of the target high-frequency high-speed copper-clad plate.
Preferably, the solvent in the step (1) is one or a mixture of two of N, N-dimethylformamide and acetone.
The beneficial effects of the preferred technical scheme are as follows: the high solubility of the two solvents to the nitrile resin is utilized, so that a resin system shows good impregnation property and uniformity; the low boiling points of the solvent and the mixed solvent are utilized to facilitate the removal of the solvent in the follow-up prepreg. In addition, the solvent system selected by the invention can adjust the molecular chain aggregation form of the nitrile resin prepolymer in the volatilization process, and adjust the dielectric property of the nitrile resin matrix to a certain degree.
Preferably, when the glue solution in the step (2) is impregnated, the mass fraction of the content of the impregnated glue solution is controlled to be 38-45% of the total mass of the impregnated base fabric.
Preferably, the baking temperature in the step (3) is set at 175-.
The beneficial effects of the preferred technical scheme are as follows: when the baking temperature is lower than the temperature, the solvent can be insufficiently removed, the glue flow is serious in the process of pressing and forming the copper-clad plate, and the defect of poor glue of the copper-clad plate is caused; when the temperature is higher than the temperature range, the polymerization reaction of the nitrile-based resin is too fast, so that the molecular weight is increased, and the resin matrix can not keep good fluidity in the compression molding process of the copper-clad plate, so that the defect of excessive gelation of the copper-clad plate is caused.
Preferably, the molding temperature in the step (4) is 180-.
The beneficial effects of the preferred technical scheme are as follows: when the molding temperature is lower than the temperature range, the nitrile resin cannot be completely cured under the set molding conditions, and the low curing degree can cause the danger of board explosion of the copper-clad plate in the subsequent use; when the forming temperature is higher than the forming temperature, the nitrile-based resin is polymerized too fast, the molecular weight distribution of the polymer is wide due to the implosion reaction, and the polymer system has the defect of high brittleness.
Preferably, the base fabric in the step (2) is a glass fiber fabric or a non-woven fabric, and the copper foil in the step (4) is an electrolytic copper foil or a rolled copper foil.
Preferably, the nitrile-based resin in step (1) includes a solute and a solvent, the solute is an aromatic dihydric phenol, an aromatic amine and paraformaldehyde, the solvent is N, N-dimethylformamide and toluene, and the molar ratio of the solute to the solvent is 1: (0.3-0.6), the specific preparation method comprises the following steps:
(1) drying aromatic dihydric phenol, aromatic amine and paraformaldehyde in a drying oven at 80 ℃ for 2 h;
(2) sequentially adding aromatic dihydric phenol, aromatic amine and paraformaldehyde into a three-necked bottle filled with N, N-dimethylformamide and toluene, stirring at room temperature at the rotating speed of 120 r/min for 10min, heating to 90-120 ℃ at the speed of 5 ℃/min, and stirring at the rotating speed of 120 r/min for reaction for 3-8 h;
(3) after the reaction is finished, raising the temperature to 140 ℃ and keeping constant-temperature stirring to continue the reaction for 2-5h to obtain viscous dark fluid;
(4) and (4) naturally cooling the deep color fluid in the step (3) to room temperature to obtain the nitrile-based resin for manufacturing the copper-clad plate.
The beneficial effects of the preferred technical scheme are as follows: the preparation of the nitrile resin involves a Mannich-like cyclization reaction, and an imine structure is formed by controlling the reaction of aromatic amine and paraformaldehyde, and then the imine structure and phenolic hydroxyl are added to form a ring so as to form a target product; the existence of moisture in the raw materials in the step (1) can hinder the reaction from occurring and proceeding, and the drying treatment can enable the synthesis reaction to easily occur, thereby realizing the structure control of the product; the slow temperature rise in the step (2) can promote the paraformaldehyde to fully react with the aromatic amine, and the addition reaction of the imine structure and the paraformaldehyde can be continuously carried out only at 90 ℃ and above, so that the setting of the temperature range can promote the effective operation of the synthesis reaction; if the temperature is lower than 90 ℃, an imine structure formed by the reaction of paraformaldehyde and aromatic amine cannot be added with phenolic hydroxyl to form a ring, so that rearrangement deformation occurs, and a target product cannot be obtained; when the temperature is higher than 120 ℃, the target product can generate a new phenolic hydroxyl group through a ring-opening reaction, and the generated phenolic hydroxyl group can seriously influence the synthesis reaction, so that the structure of the product is uncontrollable.
Preferably, in the step (2), n (aromatic dihydric phenol): n (aromatic amine): (paraformaldehyde) 1: (2-3:): (3.8-4.2), N (N, N-dimethylformamide): n (toluene) ═ 1: (0.4-0.7).
The beneficial effects of the preferred technical scheme are as follows: specifically, in the synthesis reaction, an imine structure is formed by utilizing the collision of paraformaldehyde and aromatic amine, and then the imine structure is added with phenolic hydroxyl, when the content of the solvent is too high, the probability of the reaction of the phenolic hydroxyl and the paraformaldehyde is equal to the reaction rate of the aromatic amine and the paraformaldehyde, so that the formation of a phenolic structure is caused, and the purity of the product is low; when the content of the solvent is too low, the solute cannot be completely dissolved, the material ratio of the reaction is influenced, and when the content of the solvent is too low, the problems of uncontrollable structures of the reaction and the product can occur;
within the disclosed molar ratio of aromatic dihydric phenol, aromatic amine and paraformaldehyde, and the molar ratio of N, N-dimethylformamide and toluene, the reaction can be carried out normally and the product structure can be controlled. However, when the molar ratio is less than the defined range, a large amount of the dihydric phenol remains in the system, resulting in a significant increase in dielectric constant and loss of the polymer formed from the product; when the molar ratio is higher than the defined range, an excess of paraformaldehyde reacts preferentially to the dihydric phenol to form a phenolic structure, which is not favorable for the structural control of the product.
Preferably, the aromatic dihydric phenol is one or more of bisphenol A, bisphenol S, phenolphthalein and 2, 6-bis (4-hydroxyphenoxy) benzonitrile; the concrete structure is as follows:
the aromatic amine is selected from any two or more than two of 4- (3-aminophenoxy) phthalonitrile, 4- (4-aminophenoxy) phthalonitrile, 4- (3-aminophenoxy) benzonitrile, 4- (4-aminophenoxy) benzonitrile, 2, 6-bis (4-aminophenoxy) benzonitrile and aniline, and the specific structure is as follows:
the beneficial effects of the preferred technical scheme are as follows: the performance of the synthetic product of the aromatic dihydric phenol and the aromatic amine provided by the invention is optimal, dihydric phenol and aromatic amine with other structures can also perform similar reaction to obtain a product with a controllable structure, but the performance of the product cannot meet the application requirement of a high-frequency high-speed copper-clad plate.
According to the technical scheme, compared with the prior art, the forming process of the high-frequency high-speed copper-clad plate with the nitrile resin is disclosed, the high-frequency high-speed copper-clad plate can be directly obtained through simple resin synthesis, prepolymer preparation and gluing processes and a copper-clad laminating process, compared with the traditional copper-clad plate forming process, glue mixing and particle modification and dispersion are not needed, the steps are simple, the efficiency is high, and the prepared copper-clad plate with the nitrile resin has more excellent performance.
Detailed Description
The technical solutions in the embodiments of the present invention are clearly and completely described below, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1
Synthesis of nitrile-based resin
(1) Firstly, bisphenol S, 4- (3-aminophenoxy) phthalonitrile and paraformaldehyde are dried for 2 hours in a drying oven at the temperature of 80 ℃;
(2) adding 28g of bisphenol S, 42 g of 4- (3-aminophenoxy) phthalonitrile, 3.5 g of aniline and 12 g of paraformaldehyde into a three-necked bottle filled with 23.2 g of DMF and 11.6 g of toluene in sequence, stirring at room temperature for 10 minutes at 120 revolutions per minute, heating to 100 ℃ at the heating rate of 5 ℃/min, keeping the stirring speed at 120 revolutions per minute, keeping the temperature until the reaction is finished, and keeping the constant temperature for 6 hours;
(3) after the reaction is finished, raising the temperature to 130 ℃, keeping stirring and constant temperature, continuing the reaction for 2.5 hours, and evaporating 10 g of toluene solvent;
(4) and obtaining viscous brown liquid after the reaction is finished, and obtaining the nitrile-based resin which can be used for manufacturing the copper-clad plate.
(II) preparation process of high-frequency high-speed copper-clad plate
(1) Adding epoxy resin accounting for 8% of the mass of the nitrile-based resin and 15ml DMF into the prepared nitrile-based resin, and stirring and reacting at constant temperature of 125 ℃ for 2 hours to obtain an impregnation glue solution;
(2) taking glass fiber cloth with a proper size, impregnating nitrile-based resin glue solution in a glue tank, and controlling the content of the impregnated glue to be 40% of the whole mass of the impregnated glass fiber cloth;
(3) the dipped glass fiber cloth passes through a baking channel with the length of 4m, the temperature is set at 175-195 ℃, the baking time is set to 10min, and the solvent is removed to obtain a prepreg;
(4) measuring the gelation time of the prepreg, coating copper after lamination, and performing compression molding in a vacuum press, wherein the molding temperature is set to be 200 ℃, the compression pressure is set to be 20MPa, and the compression molding time is 120 min;
(5) and naturally cooling to room temperature to obtain the nitrile resin copper-clad plate.
The obtained copper-clad plate based on the nitrile resin has the advantages of black interior, smooth surface, no defects such as bubbles and the like. The test results were as follows: glass transition temperature 220 ℃ (DSC test), 265 ℃ (DMA test); thermal decomposition temperature 420 ℃ (TGA test); the bending strength is 580MPa, and the bending modulus is 26 GPa; the dielectric constant is 4.5(3GHz), and the dielectric loss is 0.007(3 GHz); can well meet the application requirements of the nitrile resin for the high-frequency and high-speed copper-clad plate.
Example 2
Synthesis of nitrile-based resin
(1) Firstly, bisphenol A, 4- (3-aminophenoxy) phthalonitrile and paraformaldehyde are dried in a drying oven at 80 ℃ for 2 hours;
(2) sequentially adding 22.8 g of bisphenol A, 42 g of 4- (3-aminophenoxy) phthalonitrile, 3.5 g of aniline and 12 g of paraformaldehyde into a three-necked bottle filled with 23.2 g of DMF and 11.6 g of toluene, stirring at room temperature for 10 minutes at 120 revolutions per minute, heating to 110 ℃ at the heating rate of 5 ℃/min, keeping the stirring speed at 120 revolutions per minute, keeping the temperature until the reaction is finished, and keeping the constant temperature for 5 hours;
(3) after the reaction is finished, heating to 135 ℃, keeping stirring and constant temperature, continuing the reaction for 2.5 hours, and evaporating 10 g of toluene solvent;
(4) and obtaining viscous brown liquid after the reaction is finished, and obtaining the nitrile-based resin which can be used for manufacturing the copper-clad plate.
(II) preparation process of high-frequency high-speed copper-clad plate
(1) Adding epoxy resin and 15ml DMF accounting for 15 percent of the mass of the nitrile resin into the prepared nitrile resin, and stirring and reacting for 1.5 hours at a constant temperature of 130 ℃ to obtain an impregnation glue solution;
(2) taking glass fiber cloth with a proper size, impregnating nitrile-based resin glue solution in a glue tank, and controlling the content of the impregnated glue to be 38% of the whole mass of the impregnated glass fiber cloth;
(3) the dipped film passes through a baking channel with the length of 4m, the temperature is set at 175-195 ℃, the baking time is set to 10min, and the solvent is removed to obtain a prepreg;
(4) measuring the gelation time of the prepreg, coating copper after lamination, and performing compression molding in a vacuum press, wherein the molding temperature is set to be 180 ℃, the compression pressure is set to be 20MPa, and the compression molding time is 140 min;
(5) and naturally cooling to room temperature to obtain the nitrile resin copper-clad plate.
The obtained copper-clad plate based on the nitrile resin has the advantages of black interior, smooth surface, no defects such as bubbles and the like. The test results were as follows: glass transition temperature of 200 ℃ (DSC test), 255 ℃ (DMA test); thermal decomposition temperature 405 ℃ (TGA test); the bending strength is 560MPa, and the bending modulus is 25 GPa; the dielectric constant is 4.6(3GHz), the dielectric loss is 0.007(3 GHz); can well meet the application requirements of the nitrile resin for the high-frequency and high-speed copper-clad plate.
Example 3
Synthesis of nitrile-based resin
(1) Firstly, phenolphthalein, 4- (4-aminophenoxy) phthalonitrile and paraformaldehyde are dried in a drying oven at 80 ℃ for 2 hours;
(2) adding 31.8 g of phenolphthalein, 40 g of 4- (4-aminophenoxy) phthalonitrile, 4.65 g of benzene and 12 g of paraformaldehyde into a three-necked bottle filled with 30.3 g of DMF and 15.1 g of toluene in sequence, stirring for 10 minutes at room temperature at 120 revolutions/min, then heating to 110 ℃ at the heating rate of 5 ℃/min, keeping the stirring speed at 120 revolutions/min, keeping the temperature until the reaction is finished, and keeping the constant temperature for 4 hours;
(3) after the reaction is finished, raising the temperature to 130 ℃, keeping stirring and constant temperature, continuing the reaction for 3 hours, and evaporating 14 g of toluene solvent;
(4) and obtaining viscous tan liquid after the reaction is finished, and obtaining the nitrile-based resin for manufacturing the copper-clad plate.
(II) preparation process of high-frequency high-speed copper-clad plate
(1) Adding cyanate ester resin and 15ml DMF accounting for 10% of the mass of the nitrile resin into the prepared nitrile resin, and stirring and reacting at the constant temperature of 135 ℃ for 2 hours to obtain an impregnation glue solution;
(2) taking glass fiber cloth with a proper size, impregnating nitrile-based resin glue solution in a glue tank, and controlling the content of the impregnated glue to be 40% of the whole mass of the impregnated glass fiber cloth;
(3) the dipped film passes through a baking channel with the length of 4m, the temperature is set at 175-195 ℃, the baking time is set to 12min, and the solvent is removed to obtain a prepreg;
(4) measuring the gelation time of the prepreg, coating copper after lamination, and performing compression molding in a vacuum press, wherein the molding temperature is set to be 200 ℃, the compression pressure is set to be 18MPa, and the compression molding time is 120 min;
(5) and naturally cooling to room temperature to obtain the nitrile resin copper-clad plate.
The obtained copper-clad plate based on the nitrile resin has the advantages of black interior, smooth surface, no defects such as bubbles and the like. The test results were as follows: glass transition temperature 218 ℃ (DSC test), 267 ℃ (DMA test); thermal decomposition temperature 420 ℃ (TGA test); the bending strength is 545MPa, and the bending modulus is 24 GPa; the dielectric constant is 4.5(3GHz), the dielectric loss is 0.008(3 GHz); can well meet the application requirements of the nitrile resin for the high-frequency and high-speed copper-clad plate.
Example 4
Synthesis of nitrile-based resin
(1) Firstly, drying 2, 6-bis (4-hydroxyphenoxy) benzonitrile, 4- (4-aminophenoxy) phthalonitrile and paraformaldehyde in a drying oven at 80 ℃ for 2 hours;
(2) adding 31.9 g of 2, 6-bis (4-hydroxyphenoxy) benzonitrile, 35.2 g of 4- (4-aminophenoxy) phthalonitrile, 5g of aniline and 12 g of paraformaldehyde into a three-necked flask filled with 30.3 g of DMF and 15.1 g of toluene in sequence, stirring at room temperature for 10 minutes at 120 revolutions per minute, heating to 115 ℃ at the heating rate of 5 ℃/min, keeping the stirring speed at 120 revolutions per minute, keeping the temperature until the reaction is finished, and keeping the constant temperature for 6 hours;
(3) after the reaction is finished, raising the temperature to 135 ℃, keeping stirring and constant temperature, continuing the reaction for 5 hours, and evaporating 14 g of toluene solvent;
(4) and obtaining viscous tan liquid after the reaction is finished, and obtaining the nitrile-based resin for manufacturing the copper-clad plate.
(II) preparation process of high-frequency high-speed copper-clad plate
(1) Adding cyanate ester resin and 15ml DMF accounting for 15% of the mass of the nitrile resin into the prepared nitrile resin, and stirring and reacting at the constant temperature of 135 ℃ for 2 hours to obtain an impregnation glue solution;
(2) taking glass fiber cloth with a proper size, impregnating nitrile-based resin glue solution in a glue tank, and controlling the content of the impregnated glue to be 40% of the whole mass of the impregnated glass fiber cloth;
(3) the dipped film passes through a baking channel with the length of 4m, the temperature is set at 175-;
(4) measuring the gelation time of the prepreg, coating copper after lamination, and performing compression molding in a vacuum press, wherein the molding temperature is set to be 200 ℃, the compression pressure is set to be 15MPa, and the compression molding time is 120 min;
(5) and naturally cooling to room temperature to obtain the nitrile resin copper-clad plate.
The obtained copper-clad plate based on the nitrile resin has the advantages of black interior, smooth surface, no defects such as bubbles and the like. The test results were as follows: glass transition temperature 198 ℃ (DSC test), 246 ℃ (DMA test); thermal decomposition temperature 406 ℃ (TGA test); the bending strength is 545MPa, and the bending modulus is 24 GPa; the dielectric constant is 4.5(3GHz), the dielectric loss is 0.008(3 GHz); can well meet the application requirements of the nitrile resin for the high-frequency and high-speed copper-clad plate.
Example 5
Synthesis of nitrile-based resin
(1) Firstly, drying 2, 6-bis (4-hydroxyphenoxy) benzonitrile, 4- (4-aminophenoxy) benzonitrile and paraformaldehyde in a drying oven at 80 ℃ for 2 hours;
(2) adding 31.9 g of 2, 6-bis (4-hydroxyphenoxy) benzonitrile, 42 g of 4- (4-aminophenoxy) benzonitrile, 8g of aniline and 12 g of paraformaldehyde into a three-necked flask filled with 30.3 g of DMF and 15.1 g of toluene in sequence, stirring at room temperature for 10 minutes at 120 revolutions per minute, heating to 110 ℃ at a heating rate of 5 ℃/min, keeping the stirring speed at 120 revolutions per minute, keeping the temperature until the reaction is finished, and keeping the constant temperature for 6 hours;
(3) after the reaction is finished, raising the temperature to 135 ℃, keeping stirring and constant temperature, continuing the reaction for 4 hours, and evaporating 14 g of toluene solvent;
(4) and obtaining viscous tan liquid after the reaction is finished, and obtaining the nitrile-based resin which can be used for manufacturing the copper-clad plate.
(II) preparation process of high-frequency high-speed copper-clad plate
(1) Adding cyanate ester resin accounting for 10% of the mass of the nitrile resin, benzoxazine resin accounting for 10% of the mass of the nitrile resin and 20mLDMF into the prepared nitrile resin, and stirring and reacting at a constant temperature of 135 ℃ for 2 hours to obtain an impregnation glue solution;
(2) taking a non-woven fabric with a proper size, impregnating a nitrile-based resin glue solution in a glue tank, and controlling the content of the impregnated glue to be 40% of the whole mass of the impregnated non-woven fabric;
(3) the dipped film passes through a baking channel with the length of 4m, the temperature is set at 175-195 ℃, the baking time is set to 10min, and the solvent is removed to obtain a prepreg;
(4) measuring the gelation time of the prepreg, coating copper after lamination, and performing compression molding in a vacuum press, wherein the molding temperature is set to be 190 ℃, the compression pressure is set to be 20MPa, and the compression molding time is 150 min;
(5) and naturally cooling to room temperature to obtain the copper-clad plate based on the nitrile-based resin.
The obtained copper-clad plate based on the nitrile resin has the advantages of black interior, smooth surface, no defects such as bubbles and the like. The test results were as follows: glass transition temperature 210 ℃ (DSC test), 266 ℃ (DMA test); a thermal decomposition temperature of 432 ℃ (TGA test); the bending strength is 550MPa, and the bending modulus is 28 GPa; the dielectric constant is 4.4(3GHz), and the dielectric loss is 0.007(3 GHz); can well meet the application requirements of the nitrile resin for the high-frequency and high-speed copper-clad plate.
Example 6
Synthesis of nitrile-based resin
(1) Firstly, phenolphthalein, 4- (4-aminophenoxy) phthalonitrile and paraformaldehyde are dried in a drying oven at 80 ℃ for 2 hours;
(2) adding 31.8 g of phenolphthalein, 40 g of 4- (4-aminophenoxy) phthalonitrile, 4.65 g of benzene and 12 g of paraformaldehyde into a three-necked bottle filled with 30.3 g of DMF and 15.1 g of toluene in sequence, stirring for 10 minutes at room temperature at 120 revolutions/min, then heating to 110 ℃ at the heating rate of 5 ℃/min, keeping the stirring speed at 120 revolutions/min, keeping the temperature until the reaction is finished, and keeping the constant temperature for 4 hours;
(3) after the reaction is finished, raising the temperature to 130 ℃, keeping stirring and constant temperature, continuing the reaction for 3 hours, and evaporating 14 g of toluene solvent;
(4) and obtaining viscous tan liquid after the reaction is finished, and obtaining the nitrile-based resin for manufacturing the copper-clad plate.
(II) preparation process of high-frequency high-speed copper-clad plate
(1) Adding cyanate ester resin accounting for 10% of the mass of the nitrile resin and benzoxazine resin accounting for 15% of the mass of the nitrile resin into the prepared nitrile resin, and 20mLDMF, stirring and reacting at a constant temperature of 135 ℃ for 2 hours to obtain an impregnation glue solution;
(2) taking glass fiber cloth with a proper size, impregnating nitrile-based resin glue solution in a glue tank, and controlling the content of the impregnated glue to be 45% of the whole mass of the impregnated glass fiber cloth;
(3) the dipped film passes through a baking channel with the length of 4m, the temperature is set at 175-195 ℃, the baking time is set to 10min, and the solvent is removed to obtain a prepreg;
(4) measuring the gelation time of the prepreg, coating copper after lamination, and performing compression molding in a vacuum press, wherein the molding temperature is set to be 190 ℃, the compression pressure is set to be 20MPa, and the compression molding time is 150 min;
(5) and naturally cooling to room temperature to obtain the nitrile resin copper-clad plate.
The obtained copper-clad plate based on the nitrile resin has the advantages of black interior, smooth surface, no defects such as bubbles and the like. The test results were as follows: glass transition temperature 240 ℃ (DSC test), 270 ℃ (DMA test); the thermal decomposition temperature was 438 ℃ (TGA test); the bending strength is 568MPa, and the bending modulus is 27 GPa; the dielectric constant is 4.5(3GHz), and the dielectric loss is 0.007(3 GHz); can well meet the application requirements of the nitrile resin for the high-frequency and high-speed copper-clad plate.
Comparative example 1
The comparative example provides a molding process of nitrile resin for a high-frequency and high-speed copper-clad plate, the specific steps are basically the same as those of the embodiment 1, and the difference is that: in the step (1) of the molding process (II) of the comparative example, 5 mass percent of epoxy resin and 15ml DMF are added into the prepared nitrile-based resin, and the mixture is stirred and reacted for 2 hours at a constant temperature of 125 ℃ to obtain an impregnation glue solution;
the obtained copper-clad plate based on the nitrile resin has the advantages of black interior, smooth surface, no defects such as bubbles and the like. The test results were as follows: glass transition temperature 212 ℃ (DSC test), 258 ℃ (DMA test); thermal decomposition temperature 390 ℃ (TGA test); the bending strength is 524MPa, and the bending modulus is 22 GPa; a dielectric constant of 4.7(3GHz) and a dielectric loss of 0.009(3 GHz);
although the nitrile resin can meet the application requirements of the nitrile resin for the high-frequency and high-speed copper-clad plate, the comprehensive performance is lower than that of the implementation case.
Comparative example 2
The comparative example provides a molding process of nitrile resin for a high-frequency and high-speed copper-clad plate, the specific steps are basically the same as those of the embodiment 2, and the difference is that: in the step (1) of the molding process (II) of the comparative example, epoxy resin and 15ml DMF with the mass fraction of 30 percent are added into the prepared nitrile-based resin, and the mixture is stirred and reacted for 1.5 hours at the constant temperature of 130 ℃ to obtain impregnation glue solution;
the obtained copper-clad plate based on the nitrile resin has the advantages of black interior, smooth surface, no defects such as bubbles and the like. The test results were as follows: glass transition temperature 195 ℃ (DSC test), 235 ℃ (DMA test); thermal decomposition temperature of 388 ℃ (TGA test); the bending strength is 546MPa, and the bending modulus is 21.8 GPa; a dielectric constant of 4.8(3GHz) and a dielectric loss of 0.009(3 GHz);
although the nitrile resin can meet the application requirements of the nitrile resin for the high-frequency and high-speed copper-clad plate, the comprehensive performance is lower than that of the implementation case.
Comparative example 3
The comparative example provides a molding process of nitrile resin for a high-frequency and high-speed copper-clad plate, the specific steps are basically the same as those of embodiment 3, and the difference is that: in the step (1) of the molding process (II) of the comparative example, 10 mass percent of cyanate ester resin and 15ml DMF are added into the prepared nitrile-based resin, and the mixture is stirred and reacted for 2 hours at a constant temperature of 115 ℃ to obtain an impregnation glue solution;
the obtained copper-clad plate based on the nitrile-based resin has the defects of black interior, smooth surface, local poor glue phenomenon, no air bubbles and the like. The test results were as follows: glass transition temperature 215 ℃ (DSC test), 260 ℃ (DMA test); the thermal decomposition temperature was 408 ℃ (TGA test); the bending strength is 502MPa, and the bending modulus is 20.5 GPa; a dielectric constant of 4.7(3GHz) and a dielectric loss of 0.009(3 GHz);
although the nitrile resin can meet the application requirements of the nitrile resin for the high-frequency and high-speed copper-clad plate, the comprehensive performance is lower than that of the implementation case.
Comparative example 4
The comparative example provides a molding process of nitrile resin for a high-frequency and high-speed copper-clad plate, the specific steps are basically the same as those of embodiment 4, and the difference is that: in the step (3) of the molding process (II) of the comparative example, the dipped film passes through a baking channel with the length of 4m, the temperature is set at 175-;
the obtained copper-clad plate based on the nitrile resin has black interior, smooth surface and non-uniform pore defect inside, and may be a defect caused by residual solvent. The test results were as follows: glass transition temperature of 200 ℃ (DSC test), 248 ℃ (DMA test); thermal decomposition temperature 410 ℃ (TGA test); the bending strength is 525MPa, and the bending modulus is 21 GPa; a dielectric constant of 4.7(3GHz) and a dielectric loss of 0.009(3 GHz);
although the nitrile resin can meet the application requirements of the nitrile resin for the high-frequency and high-speed copper-clad plate, the comprehensive performance is lower than that of the implementation case.
Comparative example 5
The comparative example provides a molding process of nitrile resin for a high-frequency and high-speed copper-clad plate, the specific steps are basically the same as those of embodiment 4, and the difference is that: in the step (3) of the molding process (II) of the comparative example, the dipped film passes through a baking channel with the length of 4m, the temperature is set at 175-;
the copper-clad plate based on the nitrile-based resin has the defects of black interior, no air bubbles and the like, but the surface of the composite plate after the copper foil is removed has lines, and the prepreg is over-gelled and poor in flowability possibly due to overlong drying time. The test results were as follows: glass transition temperature 195 ℃ (DSC test), 240 ℃ (DMA test); thermal decomposition temperature 415 ℃ (TGA test); the bending strength is 515MPa, and the bending modulus is 20.5 GPa; a dielectric constant of 4.8(3GHz) and a dielectric loss of 0.009(3 GHz);
although the nitrile resin can meet the application requirements of the nitrile resin for the high-frequency and high-speed copper-clad plate, the comprehensive performance is lower than that of the implementation case.
From the above examples 1 to 6 and comparative examples 1 to 5, it can be analyzed that: compared with the comparative examples 1 to 5, the molding process parameters selected in the examples 1 to 7 of the invention can prepare the nitrile resin copper-clad plate with the optimal performance; the selected reaction process and parameter setting play an important role in the effect of the final nitrile-based resin copper-clad plate.
The embodiments in the present description are described in a progressive manner, each embodiment focuses on differences from other embodiments, and the same and similar parts among the embodiments are referred to each other. The device disclosed by the embodiment corresponds to the method disclosed by the embodiment, so that the description is simple, and the relevant points can be referred to the method part for description.
The previous description of the disclosed embodiments is provided to enable any person skilled in the art to make or use the present invention. Various modifications to these embodiments will be readily apparent to those skilled in the art, and the generic principles defined herein may be applied to other embodiments without departing from the spirit or scope of the invention. Thus, the present invention is not intended to be limited to the embodiments shown herein but is to be accorded the widest scope consistent with the principles and novel features disclosed herein.
Claims (7)
1. A molding process of a high-frequency high-speed nitrile-based resin copper-clad plate is characterized by comprising the following steps:
(1) adding a polymerization reaction promoter and a solvent into the nitrile-based resin, and stirring and reacting at constant temperature of 125-;
(2) putting base cloth into a glue tank to dip the glue solution prepared in the step (1) to obtain dipped base cloth;
(3) baking the dipped base cloth obtained in the step (2) to remove the solvent to obtain a semi-cured rubber sheet;
(4) measuring the gelation time of the prepreg obtained in the step (3), coating copper after lamination, and performing compression molding in a vacuum press;
(5) naturally cooling to room temperature to obtain the nitrile resin copper-clad plate;
the polymerization reaction accelerant in the step (1) comprises one or a mixture of two of epoxy resin, cyanate resin and benzoxazine resin, and the dosage of the polymerization reaction accelerant is 8-25% of the total amount of the nitrile resin;
the nitrile resin in the step (1) comprises a solute and a solvent, wherein the solute is aromatic dihydric phenol, aromatic amine and paraformaldehyde, the solvent is N, N-dimethylformamide and toluene, and the molar ratio of the solute to the solvent is 1: (0.3-0.6), the specific preparation method comprises the following steps:
(1.1) drying the aromatic dihydric phenol, the aromatic amine and the paraformaldehyde in a drying oven at 80 ℃ for 2 hours;
(1.2) sequentially adding aromatic dihydric phenol, aromatic amine and paraformaldehyde into a three-necked bottle filled with N, N-dimethylformamide and toluene, stirring at room temperature at the rotating speed of 120 r/min for 10min, heating to 90-120 ℃ at the speed of 5 ℃/min, and stirring at the rotating speed of 120 r/min for reaction for 3-8 h;
(1.3) after the reaction is finished, raising the temperature to 120-140 ℃, keeping constant temperature and stirring for continuing the reaction for 2-5h to obtain viscous dark fluid;
(1.4) naturally cooling the dark color fluid in the step (1.3) to room temperature to obtain nitrile-based resin for manufacturing a copper-clad plate;
n (aromatic dihydric phenol) in the step (1.2): n (aromatic amine): (paraformaldehyde) = 1: (2-3): (3.8-4.2), N (N, N-dimethylformamide): n (toluene) = 1: (0.4-0.7).
2. The forming process of the high-frequency high-speed nitrile-based resin copper-clad plate according to claim 1, wherein the solvent in the step (1) is one or a mixture of N, N-dimethylformamide and acetone.
3. The forming process of the high-frequency high-speed nitrile-based resin copper-clad plate according to claim 1, wherein the mass fraction of the content of the impregnated glue solution is controlled to be 38-45% of the total mass of the impregnated base fabric when the glue solution in the step (2) is impregnated.
4. The molding process of the high-frequency high-speed copper-clad nitrile-based resin plate as claimed in claim 1, wherein the baking temperature in the step (3) is set at 175-195 ℃, and the baking time is set at 8-15 min.
5. The forming process of the high-frequency high-speed nitrile-based resin copper-clad plate as claimed in claim 1, wherein the forming temperature in the step (4) is 180-.
6. The forming process of the high-frequency high-speed nitrile-based resin copper-clad plate according to claim 1, wherein the base cloth in the step (2) is glass fiber cloth or non-woven cloth, and the copper in the step (4) is electrolytic copper foil or rolled copper foil.
7. The process for molding the high-frequency and high-speed copper-clad plate with nitrile-based resin according to claim 1, wherein the aromatic dihydric phenol is one or more selected from bisphenol A, bisphenol S, phenolphthalein, and 2, 6-bis (4-hydroxyphenoxy) benzonitrile, and the aromatic amine is selected from any two or more selected from 4- (3-aminophenoxy) phthalonitrile, 4- (4-aminophenoxy) phthalonitrile, 4- (3-aminophenoxy) benzonitrile, 4- (4-aminophenoxy) benzonitrile, 2, 6-bis (4-aminophenoxy) benzonitrile, and aniline.
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| CN115380023A (en) * | 2020-03-31 | 2022-11-22 | 日铁化学材料株式会社 | Polyhydroxy resin, epoxy resin, method for producing same, epoxy resin composition using same, and cured product |
| CN111761753A (en) * | 2020-07-08 | 2020-10-13 | 铜陵华科电子材料有限公司 | Prepreg coated glass cloth soaking device |
| CN113292455A (en) * | 2021-05-18 | 2021-08-24 | 电子科技大学 | Benzoxazine-nitrile-group-containing resin curing agent and preparation method and application thereof |
| CN114506098B (en) * | 2022-02-24 | 2023-07-21 | 四川金象赛瑞化工股份有限公司 | Resin-based fiber reinforced composite material for copper-clad plate and preparation method thereof |
| CN116333491B (en) * | 2023-05-26 | 2023-08-04 | 汕头超声覆铜板科技有限公司 | Halogen-free resin composition suitable for high-speed communication and application thereof |
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Effective date of registration: 20230116 Address after: No. 28, Guangshun Road, Haojiang District, Shantou City, Guangdong Province, 515000 Patentee after: Shantou Ultrasonic Copper Clad Plate Technology Co.,Ltd. Address before: 515000 lot E04, Shantou Free Trade Zone, Shantou City, Guangdong Province Patentee before: GUANGDONG SHANTOU ULTRASONIC ELECTRONIC CO.,LTD. COPPER CLAD FACTORY |