CN110343365B - High CTI epoxy resin for copper-clad plate and preparation method thereof - Google Patents
High CTI epoxy resin for copper-clad plate and preparation method thereof Download PDFInfo
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Abstract
The invention relates to the field of epoxy resin, and particularly relates to high CTI epoxy resin for a copper-clad plate and a preparation method thereof. The feed is prepared from the following raw materials: bisphenol A liquid epoxy resin, tetrabromobisphenol A, tetrafunctional phenolic resin, phosphorus-containing epoxy resin, bisphenol A phenolic epoxy resin, an epoxy toughening agent, a catalyst and a solvent. The epoxy resin obtained by the invention has excellent flame retardance and high tracking resistance index, and also has the advantages of short reaction period, excellent mechanical property, excellent thermal stability and the like.
Description
Technical Field
The invention relates to the field of epoxy resin, and particularly relates to high CTI epoxy resin for a copper-clad plate and a preparation method thereof.
Background
The Comparative Tracking Index (CTI) is an index of a carbonized conductive path formed on the surface of a reactive insulating material in the presence of a potential difference, so that the insulating property is lost. The higher the CTI, the better the insulation. The CTI value of a common FR-4 sheet material is about 200V, and a high CTI sheet material generally requires more than 600V. The safety of human life is more and more concerned by society. In order to improve the safety and reliability of electronic products, especially the safety and reliability of insulating materials (such as motors, electrical appliances, etc.) used under humid environmental conditions, it is an important development direction in recent years to develop high-insulation products to ensure the safety and reliability of electronic products.
The CTI value tested by the high polymer material copper-clad plate refers to the highest voltage at which the surface of the material can withstand 50 drops of electrolyte (0.1% ammonium chloride aqueous solution) without forming a leakage trace, the insulation safety performance of the material is measured to a certain extent, the higher the value, the better the insulation performance of the material is represented, and therefore, the high CTI product becomes the research and development trend of the electronic industry.
The alkali-free glass fiber cloth used as a reinforcing material in the base material of the copper-clad plate has good insulating property and stable performance. In the molecular structure of the epoxy resin for binding, plasticizing and filling, the aliphatic chain and the aromatic ring have small influence on the conductivity of the base material, and bromine with flame retardant effect is polar and is easy to hydrolyze to free conductive ions. Therefore, the key point for improving the CTI value of the substrate is to reduce the content of bromine in the base material.
The invention patent application CN 109679288A discloses a halogen-free high CTI resin composition for a copper-clad plate, which comprises the following main components in parts by weight (PHR) of organic solids: (a) a mixture of phosphorus-containing epoxy resin and other epoxy resin 60-80 PHR; (b) 20-40PHR of curing agent; (c) 0.01-1PHR of curing accelerator; (d) 30-70PHR of inorganic filler; (e) 3-10PHR of phosphorus-containing flame retardant; (f) silane coupling agent 0.01-1 PHR; (g) and (4) proper amount of solvent. The copper-clad laminate prepared from the halogen-free composition has excellent tracking index (CTI is more than or equal to 600V), has the advantages of high glass transition temperature, high heat resistance and flame retardance reaching UL-94V0 level, and can be widely applied to environment-friendly halogen-free electronic materials with high CTI requirements for white appliances, inverters, outdoor charging piles and the like.
The invention patent CN 102093670A discloses a halogen-free flame-retardant epoxy resin composition and a copper-clad plate manufactured by using the same, wherein the halogen-free flame-retardant epoxy resin composition comprises: bisphenol A epoxy resin, carboxyl-terminated butadiene-acrylonitrile rubber, phosphorus-containing resin, a nitrogen flame retardant, an amine curing agent, a curing accelerator, a filler and an organic solvent. The copper-clad plate manufactured by using the halogen-free flame-retardant epoxy resin composition comprises the following components: the laminated board comprises a plurality of bonding sheets which are bonded with each other, and the halogen-free flame-retardant epoxy resin composition layer is formed by coating the halogen-free flame-retardant epoxy resin composition. The halogen-free flame-retardant epoxy resin composition has the characteristic of high tracking mark, and the copper-clad plate manufactured by using the composition has excellent comprehensive properties such as high CTI (comparative tracking index) and flame retardancy, has good processing performance, avoids the defects of dry flowers, exposed cloth marks and the like, and is suitable for manufacturing single-sided and double-sided printed circuit boards with CTI of more than or equal to 400V.
The above is a common improvement scheme adopted in the existing industry in China, but the blending of the bromine-free epoxy resin in the glue solution system can improve the CTI value, but the flame retardant performance is obviously reduced along with the increase of the bromine-free epoxy blending amount, and the flame retardant performance exceeding a certain amount (the content of the bromine-free resin on the surface adhesive tape is more than 50 percent) can not reach the V0 grade requirement.
The invention patent application CN 105482753a discloses a high CTI resin composition, which comprises brominated epoxy resin in parts by weight of solids: 80-125 parts of dicyandiamide: 2.0-3.0 parts of curing accelerator: 0.05-0.15 parts of filler composition: 70-100 parts. After the resin composition is combined by using the fillers in a specific proportion, the CTI value of a DICY curing brominated epoxy system is improved from originally less than 200V to 600V; after the high CTI filler combination is used in a DICY curing brominated epoxy system, the thermal conductivity of the plate is obviously improved, and the thermal conductivity is improved to 0.8-1.0W/m.k from 0.3-0.4W/m.k; after the high CTI filler combination is used in a DICY curing brominated epoxy system, the production cost of the high CTI filler combination plate is not obviously changed compared with the production cost of the high CTI filler combination plate without the high CTI filler combination plate. Although the CTI index is improved, the flame retardance is greatly reduced.
At present, no epoxy resin for the copper-clad plate with excellent flame retardance and high tracking resistance index exists, and the epoxy resin has the advantages of short reaction period, excellent mechanical property, excellent thermal stability and the like.
Disclosure of Invention
The invention provides a high CTI epoxy resin for a copper-clad plate, aiming at solving the problems that although the CTI index is improved in the prior art, the flame retardance is greatly reduced, and the problems of poor mechanical property, poor thermal stability and the like of the epoxy resin in the prior art.
The high CTI epoxy resin for the copper-clad plate comprises the following raw materials: bisphenol A liquid epoxy resin, tetrabromobisphenol A, tetrafunctional phenolic resin, phosphorus-containing epoxy resin, bisphenol A phenolic epoxy resin, an epoxy toughening agent, a catalyst and a solvent.
Further, the tetrafunctional phenolic resin is 1,1,2, 2-tetrakis (4-hydroxyphenyl) ethane.
Further, the phosphorus-containing epoxy resin is one of DOPO type epoxy resins.
Further, the epoxy toughening agent is one of carboxyl-terminated butyronitrile, polyether, phenol oxide and polyimide.
Still further, the epoxy toughener is a phenolic oxygen.
Further, the catalyst is one or more of triphenyl phosphine, ethyl triphenyl phosphonium bromide, tetrabutyl ammonium bromide and tetramethylammonium chloride.
Still further, the catalyst is ethyl triphenyl phosphonium bromide.
Further, the solvent is one of acetone, butanone, toluene and cyclohexanone.
Still further, the solvent is acetone.
Further, the feed is prepared from the following raw materials in parts by weight: 460 parts of bisphenol A type liquid epoxy resin 420-220 parts, 200-220 parts of tetrabromobisphenol A, 10-15 parts of tetrafunctional phenolic resin, 30-50 parts of phosphorus-containing epoxy resin, 50-70 parts of bisphenol A type phenolic epoxy resin, 50-70 parts of epoxy toughening agent, 0.01-0.2% of tetrabromobisphenol A as catalyst and 200 parts of solvent 190-200.
Further, bisphenol a type liquid epoxy resin: tetrabromobisphenol A: tetra-functional phenolic resin 1.5-1.7: 1: 0.05-0.07.
Further, the bisphenol a type liquid epoxy resin: tetrabromobisphenol A: tetra-functional phenolic resin ═ 1.6: 1: 0.06.
the invention also provides a preparation method of the epoxy resin, which comprises the following steps:
(1) adding bisphenol A type liquid epoxy resin, heating and stirring under the protection of nitrogen, and then adding tetrabromobisphenol A and tetrafunctional phenolic resin to react to obtain a mixed solution A;
(2) adding a catalyst into the mixed solution A for reaction to obtain intermediate resin;
(3) adding bisphenol A type liquid epoxy resin into the intermediate resin again, and stirring for reaction to obtain brominated epoxy resin;
(4) stopping introducing nitrogen, adding a solvent to dissolve brominated epoxy resin, stirring until the brominated epoxy resin is completely dissolved, then adding phosphorus-containing epoxy resin, bisphenol A type novolac epoxy resin and an epoxy toughening agent to react, and filtering to obtain the epoxy resin.
Further, the step (1) is heated to 80-90 ℃ under the protection of nitrogen.
Further, the stirring speed in the step (1) is 50-1000r/min, and the stirring time is 5-30 min.
Further, after the tetrabromobisphenol A and the tetrafunctional phenolic resin are added in the step (1), the mixing temperature is raised to 110-120 ℃ within 30-60min, and the temperature is kept at 110-120 ℃ for 5-30 min.
Further, a catalyst is added in the step (2) for reaction, and the reaction condition is that the temperature is raised to 165-175 ℃ for reaction for 0.5-4 h.
Further, the reaction conditions after the bisphenol A type liquid epoxy resin is added in the step (3) are as follows: the reaction temperature is 145-155 ℃, the reaction time is 15-30min, and the stirring speed is 50-1000 r/min.
Further, in the step (1), 330 parts by weight of bisphenol A type liquid epoxy resin is added; in the step (3), 130 parts by weight of bisphenol A type liquid epoxy resin is added.
And (3) further, adding phosphorus-containing epoxy resin, bisphenol A type novolac epoxy resin and an epoxy toughening agent in the step (4) for reaction, and stopping the reaction when the solid content reaches 74-76%.
Further, the method comprises the following steps:
(1) adding 330 parts of bisphenol A liquid epoxy resin 310-4 parts into a reaction kettle, heating to 80-90 ℃ under the protection of nitrogen, starting stirring, adding 220 parts of tetrabromobisphenol A200-15 parts of tetrafunctional phenolic resin; wherein the bisphenol A type liquid epoxy resin, the tetrabromobisphenol A and the tetrafunctional phenolic resin are mixed according to the mass ratio of 1.5-1.7: 1: adding the mixture into a reaction kettle in a ratio of 0.05-0.07; after the feeding is finished, the temperature is raised to 110-120 ℃ within 30-60min to obtain a mixed solution A;
(2) adding a catalyst into the mixed solution A; wherein the dosage of the catalyst is 0.05 percent of the addition of tetrabromobisphenol A, the catalyst is one or a mixture of more of triphenyl phosphine, ethyl triphenyl phosphonium bromide, tetrabutyl ammonium bromide and tetramethylammonium chloride, and the preferable catalyst is ethyl triphenyl phosphonium bromide; heating and controlling the temperature at 165-175 ℃, and reacting for 2-4h to obtain intermediate resin;
(3) adding 130 parts of bisphenol A liquid epoxy resin 110-plus into the intermediate resin again, controlling the temperature at 155-plus 145 ℃, and reacting for 15-30min under stirring to obtain brominated epoxy resin;
(4) stopping introducing nitrogen, adding 190 and 200 parts of solvent to dissolve brominated epoxy resin, and stirring; wherein the solvent is one of acetone, butanone, toluene and cyclohexanone, and the preferable solvent is acetone; after the dissolution is finished, adding 30-50 parts of phosphorus-containing epoxy resin, 50-70 parts of bisphenol A type novolac epoxy resin and 50-70 parts of epoxy toughening agent, sampling to measure the solid content, and filtering and discharging when the solid content reaches 74-76% to obtain the high CTI epoxy resin for the copper-clad plate; the epoxy toughening agent is one of carboxyl-terminated butyronitrile, polyether, phenoxy and polyimide, and the preferred epoxy toughening agent is phenoxy.
The performance of the high CTI epoxy resin for the copper-clad plate is closely related to the selected main resin, the invention adopts tetrafunctional epoxy resin as the main resin, and bisphenol A type liquid epoxy resin, tetrabromobisphenol A and tetrafunctional phenolic resin are mixed according to a proper mass ratio, particularly 1.6: 1: 0.06, high conversion rate of resin synthesis, short reaction period and improved production benefit. The tetrafunctional epoxy resin has high epoxy functionality, can provide a plurality of crosslinking points, is easy to form a highly crosslinked three-dimensional structure, and a cured product of the tetrafunctional epoxy resin has excellent mechanical strength, electrical insulation performance, water resistance, chemical resistance, higher glass transition temperature and thermal stability, and simultaneously has a UV shielding function.
In order to enable the flame retardance of a curing system to meet the international standard UL94V-0 grade used by electric products, the phosphorus-containing epoxy resin is introduced into the epoxy resin, so that bromine and phosphorus are synergistically flame-retardant, the flame resistance of the epoxy resin is enhanced, and the epoxy resin is more effective and environment-friendly than the conventional flame-retardant modification by only using a halogen-containing compound.
Because of the special three-dimensional net-shaped internal structure of the pure epoxy resin after curing, the crack propagation of the pure epoxy resin is represented by brittle propagation, the crosslinking density is high, the internal stress is large, and the obtained product has insufficient toughness, large brittleness and poor impact resistance. The invention solves the problems by selecting proper raw material combination.
The epoxy value of the high CTI epoxy resin for the copper-clad plate prepared by the invention is 2.4-2.6mmol/g, the bromine content is 15.0-17.0%, the viscosity (25 ℃) is 500-1000 mPas, and the hydrolytic chlorine is less than or equal to 300 ppm.
Compared with the prior art, the invention has the beneficial effects that:
(1) the invention adopts the tetrafunctional epoxy resin as the main resin, and the tetrafunctional epoxy resin is dissolved in an acetone solution after chemical modification and physical blending treatment, so that a condensate of the tetrafunctional epoxy resin has excellent mechanical strength, electrical insulation property, water resistance, chemical resistance, higher glass transition temperature and thermal stability, and simultaneously has the UV shielding function.
(2) Compared with the traditional method of singly using halogen-containing compounds to carry out flame retardant modification, the method is more effective and environment-friendly.
(3) Because of the special three-dimensional net-shaped internal structure of the pure epoxy resin after curing, the crack propagation of the pure epoxy resin is represented by brittle propagation, the crosslinking density is high, the internal stress is large, and the obtained product has insufficient toughness, large brittleness and poor impact resistance. The invention solves the above problems by adding appropriate raw material components.
(4) The high CTI epoxy resin for the copper-clad plate has the advantages of high CTI, excellent flame retardance, UV shielding function and the like. The copper foil substrate prepared by the invention can meet the requirements of CTI (CTI is more than or equal to 600) and flame retardance up to UL-94V0 level.
Detailed Description
The invention will be further described with reference to specific embodiments, the advantages and features of which will become apparent from the description, but which are given by way of illustration only and are not intended to limit the scope of the invention in any way. It will be understood by those skilled in the art that various changes in form and details may be made therein without departing from the spirit and scope of the invention, and that such changes and modifications may be made without departing from the spirit and scope of the invention.
Example 1
(1) Preparation of resin:
adding 320 parts of bisphenol A liquid epoxy resin into a reaction kettle, heating to 80 ℃ under the protection of nitrogen, starting stirring, stirring for 15min under the condition that the stirring speed is 500r/min, adding 200 parts of tetrabromobisphenol A, 12 parts of 1,1,2, 2-tetra (4-hydroxyphenyl) ethane, adding bisphenol A liquid epoxy resin, tetrabromobisphenol A and tetrafunctional phenolic resin according to the mass ratio of 1.65: 1: adding the mixture into a reaction kettle according to the proportion of 0.06, heating to 115 ℃ within 40min after the addition is finished, adding 0.1 part of ethyl triphenyl phosphonium bromide, heating and controlling the temperature to 165 ℃, and reacting for 3h to obtain intermediate resin; adding 110 parts of bisphenol A liquid epoxy resin into the reaction kettle again, controlling the temperature at 148 ℃, and stirring and reacting for 15min under the condition that the stirring speed is 600r/min to obtain brominated epoxy resin; and stopping introducing nitrogen, adding 190 parts of acetone to dissolve brominated epoxy resin, stirring until the brominated epoxy resin is completely dissolved, adding 40 parts of phosphorus-containing epoxy resin, 55 parts of bisphenol A type novolac epoxy resin and 60 parts of phenol oxygen, sampling to measure that the solid content is 75.8%, filtering and discharging to obtain the high CTI epoxy resin for the copper-clad plate. The epoxy value was 2.5mmol/g, bromine content was 15.2%, viscosity (25 ℃ C.) was 750mPa.s, and hydrolysis chlorine was 50 ppm.
(2) The application of the resin in the preparation of the copper-clad plate substrate comprises the following steps:
adding 2.63 parts by weight of dicyandiamide curing agent, 0.1 part by weight of curing accelerator 2-methylimidazole, 21 parts by weight of solvent Dimethylformamide (DMF) and 42 parts by weight of inorganic filler aluminum hydroxide into 131.9 parts by weight of resin, uniformly mixing to prepare a resin adhesive solution with a solid content of 60-70%, soaking glass fiber cloth into the epoxy resin adhesive solution, baking the resin adhesive solution in an oven at 170 ℃ to prepare a semi-cured PP sheet, and pressing and molding the PP sheet by using a hot press under the hot pressing condition of 175 ℃ 35Kg/cm320 min. The substrate has a CTI (50D) of more than 600 as measured by GB/T4207-2003 and a flame resistance (UL94) of V-0 as measured by UL94 vertical burning.
Example 2
(1) Preparation of resin:
adding 310 parts of bisphenol A type liquid epoxy resin into a reaction kettle, heating to 90 ℃ under the protection of nitrogen, starting stirring, stirring for 30min under the condition that the stirring speed is 50r/min, adding 200 parts of tetrabromobisphenol A, 10 parts of 1,1,2, 2-tetra (4-hydroxyphenyl) ethane, adding bisphenol A type liquid epoxy resin, tetrabromobisphenol A and tetrafunctional phenolic resin according to the mass ratio of 1.55: 1: adding the mixture into a reaction kettle according to the proportion of 0.05, heating to 110 ℃ within 30min after the addition is finished, adding 0.4 part of mixture of tetrabutylammonium bromide and tetramethylammonium chloride, heating and controlling the temperature to be 175 ℃, and reacting for 0.5h to obtain intermediate resin; adding 130 parts of bisphenol A liquid epoxy resin into the reaction kettle again, controlling the temperature at 145 ℃, and stirring and reacting for 30min under the condition that the stirring speed is 50r/min to obtain brominated epoxy resin; stopping introducing nitrogen, adding 200 parts of cyclohexanone to dissolve brominated epoxy resin, stirring until the brominated epoxy resin is completely dissolved, adding 30 parts of phosphorus-containing epoxy resin, 50 parts of bisphenol A type novolac epoxy resin and 50 parts of polyether, sampling to measure that the solid content is 74.6%, filtering and discharging to obtain the high CTI epoxy resin for the copper-clad plate. The epoxy value was 2.46mmol/g, the bromine content was 15.9%, the viscosity (25 ℃ C.) was 852 mPas, and the hydrolysis chlorine was 70 ppm.
(2) The application of the resin in the preparation of the copper-clad plate substrate comprises the following steps:
adding 2.58 parts by weight of curing agent dicyandiamide, 0.1 part by weight of curing accelerator 2-methylimidazole, 19.8 parts by weight of solvent Dimethylformamide (DMF) and 45 parts by weight of inorganic filler aluminum hydroxide into 133 parts by weight of resin 1, uniformly mixing to prepare a resin adhesive solution with a solid content of 60-70%, soaking glass fiber cloth into the epoxy resin adhesive solution, baking in an oven at 170 ℃ to prepare a semi-cured PP sheet, and pressing and molding by using a hot press, wherein the hot pressing condition is 175 ℃ 35Kg/cm320 min. The substrate has a CTI (50D) of greater than 600 and a flame resistance (UL94) of V-0.
Example 3
(1) Preparation of resin:
330 parts of bisphenol A liquid epoxy resin is put into a reaction kettle, the mixture is heated to 85 ℃ under the protection of nitrogen, stirring is started, stirring is carried out for 5min under the condition that the stirring speed is 1000r/min, 220 parts of tetrabromobisphenol A, 15 parts of 1,1,2, 2-tetra (4-hydroxyphenyl) ethane, bisphenol A liquid epoxy resin, tetrabromobisphenol A and tetrafunctional phenolic resin are put into the reaction kettle in a mass ratio of 1.5: 1: adding the mixture into a reaction kettle according to the proportion of 0.07, heating to 120 ℃ within 60min after the addition is finished, adding 0.022 part of triphenyl phosphorus, heating and controlling the temperature to 170 ℃, and reacting for 2 hours to obtain intermediate resin; adding 120 parts of bisphenol A liquid epoxy resin into the reaction kettle again, controlling the temperature at 150 ℃, and stirring and reacting for 8min under the condition that the stirring speed is 650r/min to obtain brominated epoxy resin; stopping introducing nitrogen, adding 195 parts of toluene to dissolve brominated epoxy resin, stirring until the brominated epoxy resin is completely dissolved, adding 35 parts of phosphorus-containing epoxy resin, 55 parts of bisphenol A type novolac epoxy resin and 60 parts of carboxyl-terminated butyronitrile, sampling to measure that the solid content is 76%, filtering and discharging to obtain the high CTI epoxy resin for the copper-clad plate. The epoxy value was 2.47mmol/g, the bromine content was 15.5%, the viscosity (25 ℃ C.) was 821 mPas, and the hydrolysis chlorine content was 66 ppm.
(2) The application of the resin in the preparation of the copper-clad plate substrate comprises the following steps: adding 2.59 parts by weight of curing agent dicyandiamide, 0.1 part by weight of curing accelerator 2-methylimidazole, 18.7 parts by weight of solvent Dimethylformamide (DMF) and 43 parts by weight of inorganic filler aluminum hydroxide into 134.2 parts by weight of resin 1, uniformly mixing to prepare a resin adhesive solution with a solid content of 60-70%, soaking glass fiber cloth into the epoxy resin adhesive solution, baking in an oven at 170 ℃ to prepare a semi-cured PP sheet, and performing press-molding by using a hot press, wherein the hot press condition is 175 ℃ C. 35Kg/cm320 min. The substrate has a CTI (50D) of greater than 600 and a flame resistance (UL94) of V-0.
Comparative example 1
Compared with example 1, the mass ratio of the bisphenol A type liquid epoxy resin, the tetrabromobisphenol A and the tetrafunctional phenolic resin is different.
Wherein the preparation process of the resin is as follows:
adding 310 parts of bisphenol A type liquid epoxy resin into a reaction kettle, heating to 80 ℃ under the protection of nitrogen, starting stirring, stirring for 15min under the condition that the stirring speed is 500r/min, adding 250 parts of tetrabromobisphenol A, 20 parts of 1,1,2, 2-tetra (4-hydroxyphenyl) ethane, adding bisphenol A type liquid epoxy resin, tetrabromobisphenol A and tetrafunctional phenolic resin according to the mass ratio of 1.24: 1: adding the mixture into a reaction kettle according to the proportion of 0.08, heating to 115 ℃ within 40min after the addition is finished, adding 0.1 part of ethyl triphenyl phosphonium bromide, heating and controlling the temperature to 165 ℃, and reacting for 3h to obtain intermediate resin; adding 110 parts of bisphenol A liquid epoxy resin into the reaction kettle again, controlling the temperature at 148 ℃, and stirring and reacting for 15min under the condition that the stirring speed is 600r/min to obtain brominated epoxy resin; and stopping introducing nitrogen, adding 190 parts of acetone to dissolve brominated epoxy resin, stirring until the brominated epoxy resin is completely dissolved, adding 40 parts of phosphorus-containing epoxy resin, 55 parts of bisphenol A type novolac epoxy resin and 60 parts of phenol oxygen, sampling to measure that the solid content is 75.8%, filtering and discharging to obtain the high CTI epoxy resin for the copper-clad plate.
Comparative example 2
Compared with the embodiment 1, the epoxy toughening agent is different, the nano titanium dioxide is adopted as the toughening agent, and other conditions are the same.
Comparative example 3
The catalyst was different compared to example 1.
Comparative example 3 used a catalyst that was a mixture of tetrabutylammonium bromide, butyltriphenylammonium bromide, and polyethylene glycol mixed in a weight ratio of 0.2:1: 0.07. The other conditions were the same.
Effect example 1 mechanical Strength
The peel strength was determined according to IPC-TM-6502.4.8 and the results were as follows:
effect example 2 Heat stability test
The glass transition temperature was determined according to IPC-TM-6502.4.25 and the results were as follows:
the comprehensive test result shows that the method has the following advantages:
(1) the invention adopts the tetrafunctional epoxy resin as the main resin, and the tetrafunctional epoxy resin is dissolved in an acetone solution after chemical modification and physical blending treatment, so that a condensate of the tetrafunctional epoxy resin has excellent mechanical strength, electrical insulation property, water resistance, chemical resistance, higher glass transition temperature and thermal stability, and simultaneously has the UV shielding function.
(2) Compared with the traditional method of singly using halogen-containing compounds to carry out flame retardant modification, the method is more effective and environment-friendly.
(3) Because of the special three-dimensional net-shaped internal structure of the pure epoxy resin after curing, the crack propagation of the pure epoxy resin is represented by brittle propagation, the crosslinking density is high, the internal stress is large, and the obtained product has insufficient toughness, large brittleness and poor impact resistance. The invention solves the above problems by adding appropriate raw material components.
(4) The high CTI epoxy resin for the copper-clad plate has the advantages of high CTI, excellent flame retardance, UV shielding function and the like. The copper foil substrate prepared by the invention can meet the requirements of CTI (CTI is more than or equal to 600) and flame retardance up to UL-94V0 level.
The technical means disclosed by the scheme of the invention are not limited to the technical means disclosed above, and the technical means also comprises the technical scheme formed by any combination of the technical features. While the foregoing is directed to embodiments of the present invention, it will be appreciated by those skilled in the art that various changes and modifications may be made without departing from the principles of the invention, and it is intended to claim all such modifications and alterations as fall within the true scope of the invention.
Claims (9)
1. The high CTI epoxy resin for the copper-clad plate is characterized by comprising the following raw materials in parts by weight: 420-460 parts of bisphenol A liquid epoxy resin, 200-220 parts of tetrabromobisphenol A, 10-15 parts of tetrafunctional phenolic resin, 30-50 parts of phosphorus-containing epoxy resin, 50-70 parts of bisphenol A phenolic epoxy resin, 50-70 parts of epoxy toughening agent, 0.01-0.2 percent of tetrabromobisphenol A as catalyst and 200 parts of solvent 190-;
the preparation method of the high CTI epoxy resin for the copper-clad plate comprises the following steps:
(1) adding bisphenol A type liquid epoxy resin, heating and stirring under the protection of nitrogen, and then adding tetrabromobisphenol A and tetrafunctional phenolic resin to obtain a mixed solution A; wherein, bisphenol A type liquid epoxy resin: tetrabromobisphenol A: tetra-functional phenolic resin 1.5-1.7: 1: 0.05-0.07;
(2) adding a catalyst into the mixed solution A for reaction to obtain intermediate resin;
(3) adding bisphenol A type liquid epoxy resin into the intermediate resin again, and stirring for reaction to obtain brominated epoxy resin;
(4) stopping introducing nitrogen, adding a solvent to dissolve brominated epoxy resin, stirring until the brominated epoxy resin is completely dissolved, then adding phosphorus-containing epoxy resin, bisphenol A type novolac epoxy resin and an epoxy toughening agent to react, and filtering to obtain the epoxy resin;
the tetrafunctional phenolic resin is 1,1,2, 2-tetra (4-hydroxyphenyl) ethane; the epoxy toughening agent is one of carboxyl-terminated butyronitrile, polyether, phenoxy and polyimide; the catalyst is ethyl triphenyl phosphonium bromide.
2. The epoxy resin of claim 1, wherein the phosphorous-containing epoxy resin is a DOPO-type epoxy resin; the solvent is one of acetone, butanone, toluene and cyclohexanone.
3. The epoxy resin of claim 1, wherein the epoxy toughener is phenol oxygen; the solvent is acetone.
4. A process for the preparation of the epoxy resin according to any one of claims 1 to 3, comprising the steps of:
(1) adding bisphenol A type liquid epoxy resin, heating and stirring under the protection of nitrogen, and then adding tetrabromobisphenol A and tetrafunctional phenolic resin to obtain a mixed solution A;
(2) adding a catalyst into the mixed solution A for reaction to obtain intermediate resin;
(3) adding bisphenol A type liquid epoxy resin into the intermediate resin again, and stirring for reaction to obtain brominated epoxy resin;
(4) stopping introducing nitrogen, adding a solvent to dissolve brominated epoxy resin, stirring until the brominated epoxy resin is completely dissolved, then adding phosphorus-containing epoxy resin, bisphenol A type novolac epoxy resin and an epoxy toughening agent to react, and filtering to obtain the epoxy resin.
5. The method for preparing epoxy resin according to claim 4, wherein the step (1) is heated to 80-90 ℃ under the protection of nitrogen; the stirring speed is 50-1000r/min, and the stirring time is 5-30 min.
6. The method for preparing epoxy resin as claimed in claim 4, wherein the temperature of the mixture is raised to 110-120 ℃ within 30-60min after the tetrabromobisphenol A and the tetrafunctional phenolic resin are added in step (1), and the temperature is maintained at 110-120 ℃ for 5-30 min.
7. The method for preparing epoxy resin as claimed in claim 4, wherein the catalyst is added in step (2) for reaction under the conditions of temperature rise to 165-175 ℃ for 0.5-4 h.
8. The method for preparing epoxy resin according to claim 4, wherein the reaction conditions after adding bisphenol A type liquid epoxy resin in step (3) are as follows: the reaction temperature is 145-155 ℃, the reaction time is 15-30min, and the stirring speed is 50-1000 r/min.
9. The preparation method of the epoxy resin according to claim 4, wherein the phosphorus-containing epoxy resin, the bisphenol A novolac epoxy resin and the epoxy toughening agent are added in the step (4) for reaction, and the reaction is terminated when the solid content reaches 74-76%.
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| CN113278260A (en) * | 2021-06-23 | 2021-08-20 | 江苏扬农锦湖化工有限公司 | Composite modified epoxy resin, preparation method thereof and application thereof in automobile copper-clad plate |
| CN113698738B (en) * | 2021-08-27 | 2022-10-21 | 江苏耀鸿电子有限公司 | Flame-retardant copper-clad plate and preparation method thereof |
| CN115489183B (en) * | 2022-07-26 | 2023-07-21 | 江苏耀鸿电子有限公司 | Phenolic resin reinforced high-toughness copper-clad plate and preparation method thereof |
| CN115612063A (en) * | 2022-09-27 | 2023-01-17 | 江苏扬农锦湖化工有限公司 | Composite epoxy resin, preparation method thereof, pouring material and application thereof |
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