CN113667276A - Halogen-free high-Tg copper-clad substrate and preparation method thereof - Google Patents
Halogen-free high-Tg copper-clad substrate and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a halogen-free high-Tg copper-clad substrate, and particularly relates to the technical field of copper-clad plates, wherein the copper-clad plate comprises a cured sheet layer and a copper foil layer, the cured sheet layer is formed by stacking a plurality of prepregs, the prepregs are composed of electronic-grade glass cloth and glue solution, and the glue solution comprises the following raw materials: modified phosphorus-containing epoxy resin, phenolic benzylidene epoxy resin, polyether-ether-ketone resin, a curing agent, a curing catalyst, inorganic filler, a processing aid and a solvent. According to the invention, the phenolic benzylidene epoxy resin, the polyether-ether-ketone resin and the modified epoxy resin containing phosphorus are blended to make the copper-clad substrate have better toughness and corrosion resistance, the carbon fiber and the glass fiber have better modification effect on the epoxy resin containing phosphorus by utilizing the bonding property of the triglycidyl isocyanurate, and the triglycidyl isocyanurate has better heat resistance and weather resistance, so that the modified epoxy resin containing phosphorus has better heat resistance, and the glass transition temperature of the plate is raised.
Description
Technical Field
The invention relates to the technical field of copper-clad plates, in particular to a halogen-free high-Tg copper-clad substrate and a preparation method thereof.
Background
With the rapid development of science and technology and the formation of large-scale industrial integration, irreparable damage is caused to the living environment of human beings, so that the environmental protection is urgent. In recent years, electronic technology is rapidly developed, electronic products have increasingly serious influence on the environment, particularly electronic garbage products, most of the electronic products adopt halogen flame retardants at present, and after the halogen flame retardants are combusted, the electronic products not only have large smoke generation amount and bad smell, but also can generate hydrogen halide gas with strong corrosiveness. In addition, it is reported in literature that halogen-containing flame retardants generate carcinogenic substances such as dioxin and dibenzofuran during pyrolysis and combustion. Therefore, the development of halogen-free flame retardant substrate materials is imperative and has become the industrial focus in the industry. On the other hand, the safety of human life is more and more receiving social attention. In order to improve the safety and reliability of electronic products, especially for 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.
With the rapid development of electronic technology, higher and more severe requirements are put forward on resin copper clad laminates, such as high Tg, high Td, low CTE, high heat resistance, high reliability and the like. In the production process of the copper-clad plate, the performance indexes can be achieved or improved by reasonably adding the filler, and some special requirements of customers are met. The existing copper-clad plate has poor temperature resistance effect in the use process and cannot meet the use requirements of people.
Disclosure of Invention
The invention aims to provide a halogen-free high-Tg copper-clad substrate and a preparation method thereof, so as to solve the problems in the background technology.
In order to achieve the purpose, the invention provides the following technical scheme: the utility model provides a there is not steamed high Tg copper-clad base plate, includes solidification lamella and copper foil layer, the solidification lamella is piled up through a plurality of prepregs and forms, the prepreg adopts electronic grade glass cloth and glue solution to constitute, the glue solution includes the raw materials of following parts by weight: 120-160 parts of modified phosphorus-containing epoxy resin, 55-70 parts of phenolic benzylidene epoxy resin, 40-60 parts of polyether ether ketone resin, 6-18 parts of curing agent, 0.5-10 parts of curing catalyst, 40-60 parts of inorganic filler, 5-15 parts of processing aid and 150 parts of solvent.
In a preferred embodiment, the glue solution comprises the following raw materials in parts by weight: 150 parts of modified phosphorus-containing epoxy resin 130-containing material, 60-65 parts of phenolic benzylidene epoxy resin, 45-55 parts of polyether ether ketone resin, 10-14 parts of curing agent, 4-6 parts of curing catalyst, 45-55 parts of inorganic filler, 8-12 parts of processing aid and 130 parts of solvent 120-containing material.
In a preferred embodiment, the glue solution comprises the following raw materials in parts by weight: 140 parts of modified phosphorus-containing epoxy resin, 63 parts of phenolic benzylidene epoxy resin, 50 parts of polyether-ether-ketone resin, 12 parts of curing agent, 5 parts of curing catalyst, 50 parts of inorganic filler, 10 parts of processing aid and 125 parts of solvent.
In a preferred embodiment, the phosphorus content of the modified phosphorus-containing epoxy resin is 1-3%, the epoxy equivalent of the modified phosphorus-containing epoxy resin is 180-230 g/eq, and the epoxy equivalent of the phenolic benzylidene epoxy resin is 210-200 g/eq.
In a preferred embodiment, the curing agent is a mixture of dicyandiamide and phthalic anhydride, and the weight ratio of dicyandiamide to phthalic anhydride is 1: (6-8), wherein the curing catalyst is a mixture of dimethyl imidazole and phthalic anhydride, and the weight ratio of the dimethyl imidazole to the phthalic anhydride is 1: (5-10), wherein the inorganic filler is a mixture of modified barium sulfate, aluminum hydroxide and boron nitride, and the weight ratio of the modified barium sulfate to the aluminum hydroxide to the boron nitride is 1: (1-3): (0.5-1.5), and the particle size of the inorganic filler is 0.1-20 um.
In a preferred embodiment, the processing aid comprises a silane coupling agent, a plasticizer and an antioxidant, and the weight ratio of the silane coupling agent to the plasticizer to the antioxidant is 1: (0.6-0.8): (0.5-0.8), and the solvent is one or a mixture of more than two of acetone, DMF or butanone.
A preparation method of a halogen-free high-Tg copper-clad substrate comprises the following specific preparation steps:
the method comprises the following steps: weighing phosphorus-containing epoxy resin, placing the phosphorus-containing epoxy resin in a reaction container, heating to 180 ℃ and 200 ℃, then adding triglycidyl isocyanurate, continuously stirring uniformly, completely mixing and melting the triglycidyl isocyanurate and the phosphorus-containing epoxy resin under the heating condition, then placing the mixture in an extruder for granulation, extrusion and ball milling to obtain micro powder, and placing the micro powder, carbon fibers and glass fibers in a cross-linking granulator for granulation to obtain modified phosphorus-containing epoxy resin;
step two: preparing a glue solution, namely weighing the modified phosphorus-containing epoxy resin, the phenolic benzylidene epoxy resin, the polyether-ether-ketone resin, the curing agent, the curing catalyst, the inorganic filler, the processing aid and the solvent which are obtained in the step one according to the weight parts, and uniformly mixing the weighed modified phosphorus-containing epoxy resin, the phenolic benzylidene epoxy resin, the polyether-ether-ketone resin, the curing agent, the curing catalyst, the inorganic filler, the processing aid and the solvent under the ultrasonic assistance to obtain the glue solution;
step three: preparing a prepreg, namely uniformly coating the glue solution obtained in the step two on electronic-grade glass cloth, and drying in an oven after coating to obtain the prepreg;
step four: selecting a proper amount of prepregs to be stacked together according to actual needs, then respectively covering a layer of copper foil on the surface of each of the prepregs at the top end and the surface of each of the prepregs at the bottom end, and then obtaining the halogen-free high-Tg copper-clad substrate by a hot-pressing technology.
In a preferred embodiment, the amount of the triglycidyl isocyanurate added in the first step is 1-5% of the weight of the phosphorus-containing epoxy resin, and the temperature for granulating in the crosslinking granulator in the first step is 360-380 ℃.
In a preferred embodiment, the power during the ultrasonic assistance in the second step is 800-.
In a preferred embodiment, the pressure during the hot pressing in the fourth step is 1.5-3MPa, the temperature during the hot pressing is 180-.
The invention has the technical effects and advantages that:
1. the halogen-free high-Tg copper-clad substrate prepared by the raw material formula is prepared by taking modified phosphorus-containing epoxy resin, phenolic benzylidene epoxy resin and polyether-ether-ketone resin as raw materials to prepare a glue solution, wherein the phosphorus-containing epoxy resin is modified by utilizing triglycidyl isocyanurate, carbon fibers and glass fibers, the carbon fibers and the glass fibers have better modification effect on the phosphorus-containing epoxy resin by utilizing the bonding property of the triglycidyl isocyanurate, and the triglycidyl isocyanurate has better heat resistance and weather resistance, so that the modified phosphorus-containing epoxy resin has better heat resistance, the glass transition temperature of a plate is increased, and the phenolic benzylidene epoxy resin, the polyether-ether-ketone resin and the modified epoxy resin are blended to ensure that the copper-clad substrate has better toughness and corrosion resistance;
2. according to the invention, the copper-clad plate has higher temperature resistance by adding the inorganic filler which comprises the modified barium sulfate, the aluminum hydroxide and the boron nitride, the glass transition temperature of the copper-clad plate is increased, and the thermal shock resistance effect and the peel strength of the copper-clad plate are obviously improved.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the 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:
the invention provides a halogen-free high-Tg copper-clad substrate which comprises a cured sheet layer and a copper foil layer, wherein the cured sheet layer is formed by stacking a plurality of prepregs, the prepregs are composed of electronic-grade glass cloth and glue solution, and the glue solution comprises the following raw materials in parts by weight: 120 parts of modified phosphorus-containing epoxy resin, 55 parts of phenolic benzylidene epoxy resin, 40 parts of polyether ether ketone resin, 6 parts of curing agent, 1 part of curing catalyst, 40 parts of inorganic filler, 5 parts of processing aid and 100 parts of solvent.
In a preferred embodiment, the phosphorus content of the modified phosphorus-containing epoxy resin is 2%, the epoxy equivalent of the modified phosphorus-containing epoxy resin is 200g/eq, and the epoxy equivalent of the phenolic benzylidene epoxy resin is 220 g/eq.
In a preferred embodiment, the curing agent is a mixture of dicyandiamide and phthalic anhydride, and the weight ratio of dicyandiamide to phthalic anhydride is 1: 7, the curing catalyst is a mixture of dimethyl imidazole and phthalic anhydride, and the weight ratio of the dimethyl imidazole to the phthalic anhydride is 1: 8, the inorganic filler is a mixture of modified barium sulfate, aluminum hydroxide and boron nitride, and the weight ratio of the modified barium sulfate to the aluminum hydroxide to the boron nitride is 1: 2: 1, the particle size of the inorganic filler is 0.1-20 um.
In a preferred embodiment, the processing aid comprises a silane coupling agent, a plasticizer and an antioxidant, and the weight ratio of the silane coupling agent to the plasticizer to the antioxidant is 1: 0.7: 0.6, the solvent is one or the mixture of more than two of acetone, DMF or butanone.
A preparation method of a halogen-free high-Tg copper-clad substrate comprises the following specific preparation steps:
the method comprises the following steps: weighing phosphorus-containing epoxy resin, placing the phosphorus-containing epoxy resin in a reaction container, heating to 190 ℃, adding triglycidyl isocyanurate, continuously stirring uniformly, completely mixing and melting the triglycidyl isocyanurate and the phosphorus-containing epoxy resin under the heating condition, placing the mixture in an extruder for granulation, extrusion and ball milling to obtain micro powder, and placing the micro powder, carbon fibers and glass fibers in a cross-linking granulator for granulation to obtain modified phosphorus-containing epoxy resin;
step two: preparing a glue solution, namely weighing the modified phosphorus-containing epoxy resin, the phenolic benzylidene epoxy resin, the polyether-ether-ketone resin, the curing agent, the curing catalyst, the inorganic filler, the processing aid and the solvent which are obtained in the step one according to the weight parts, and uniformly mixing the weighed modified phosphorus-containing epoxy resin, the phenolic benzylidene epoxy resin, the polyether-ether-ketone resin, the curing agent, the curing catalyst, the inorganic filler, the processing aid and the solvent under the ultrasonic assistance to obtain the glue solution;
step three: preparing a prepreg, namely uniformly coating the glue solution obtained in the step two on electronic-grade glass cloth, and drying in an oven after coating to obtain the prepreg;
step four: selecting a proper amount of prepregs to be stacked together according to actual needs, then respectively covering a layer of copper foil on the surface of each of the prepregs at the top end and the surface of each of the prepregs at the bottom end, and then obtaining the halogen-free high-Tg copper-clad substrate by a hot-pressing technology.
In a preferred embodiment, the amount of triglycidyl isocyanurate added in step one is 3% by weight of the phosphorus-containing epoxy resin, and the temperature of the cross-linking granulator during granulation in step one is 370 ℃.
In a preferred embodiment, the power of the ultrasonic assistance in the second step is 900W, the temperature inside the oven during the drying in the third step is 170 ℃, and the drying time is 10 min.
In a preferred embodiment, the pressure during the hot pressing in the fourth step is 2.5MPa, the temperature during the hot pressing is 210 ℃, and the time of the hot pressing is 50 min.
Example 2:
the invention provides a halogen-free high-Tg copper-clad substrate, which comprises the following raw materials in parts by weight: 140 parts of modified phosphorus-containing epoxy resin, 63 parts of phenolic benzylidene epoxy resin, 50 parts of polyether-ether-ketone resin, 12 parts of curing agent, 5 parts of curing catalyst, 50 parts of inorganic filler, 10 parts of processing aid and 125 parts of solvent.
Example 3:
different from the embodiments 1 and 2, the invention provides a halogen-free high-Tg copper-clad substrate, and the glue solution comprises the following raw materials in parts by weight: 160 parts of modified phosphorus-containing epoxy resin, 70 parts of phenolic benzylidene epoxy resin, 60 parts of polyether-ether-ketone resin, 18 parts of curing agent, 10 parts of curing catalyst, 60 parts of inorganic filler, 15 parts of processing aid and 150 parts of solvent.
Example 4:
the invention provides a halogen-free high-Tg copper-clad substrate which comprises a cured sheet layer and a copper foil layer, wherein the cured sheet layer is formed by stacking a plurality of prepregs, the prepregs are composed of electronic-grade glass cloth and glue solution, and the glue solution comprises the following raw materials in parts by weight: 120 parts of phosphorus-containing epoxy resin, 55 parts of phenolic benzylidene epoxy resin, 40 parts of polyether-ether-ketone resin, 6 parts of curing agent, 1 part of curing catalyst, 40 parts of inorganic filler, 5 parts of processing aid and 100 parts of solvent.
In a preferred embodiment, the phosphorus-containing epoxy resin has a phosphorus content of 2%, an epoxy equivalent of 200g/eq, and an epoxy equivalent of 220 g/eq.
In a preferred embodiment, the curing agent is a mixture of dicyandiamide and phthalic anhydride, and the weight ratio of dicyandiamide to phthalic anhydride is 1: 7, the curing catalyst is a mixture of dimethyl imidazole and phthalic anhydride, and the weight ratio of the dimethyl imidazole to the phthalic anhydride is 1: 8, the inorganic filler is a mixture of modified barium sulfate, aluminum hydroxide and boron nitride, and the weight ratio of the modified barium sulfate to the aluminum hydroxide to the boron nitride is 1: 2: 1, the particle size of the inorganic filler is 0.1-20 um.
In a preferred embodiment, the processing aid comprises a silane coupling agent, a plasticizer and an antioxidant, and the weight ratio of the silane coupling agent to the plasticizer to the antioxidant is 1: 0.7: 0.6, the solvent is one or the mixture of more than two of acetone, DMF or butanone.
A preparation method of a halogen-free high-Tg copper-clad substrate comprises the following specific preparation steps:
the method comprises the following steps: preparing glue solution, namely weighing phosphorus-containing epoxy resin, phenolic benzylidene epoxy resin, polyether ether ketone resin, a curing agent, a curing catalyst, inorganic filler, a processing aid and a solvent according to the parts by weight, and uniformly mixing the weighed phosphorus-containing epoxy resin, phenolic benzylidene epoxy resin, polyether ether ketone resin, curing agent, curing catalyst, inorganic filler, processing aid and solvent under the ultrasonic assistance action to obtain the glue solution;
step two: preparing a prepreg, namely uniformly coating the glue solution obtained in the step one on electronic-grade glass cloth, and drying in an oven after coating to obtain the prepreg;
step three: selecting a proper amount of prepregs to be stacked together according to actual needs, then respectively covering a layer of copper foil on the surface of each of the prepregs at the top end and the surface of each of the prepregs at the bottom end, and then obtaining the halogen-free high-Tg copper-clad substrate by a hot-pressing technology.
In a preferred embodiment, the power of the ultrasonic assistance in the first step is 900W, and the temperature inside the oven is 170 ℃ during the drying in the second step, and the drying time is 10 min.
In a preferred embodiment, the pressure during the hot pressing in the third step is 2.5MPa, the temperature during the hot pressing is 210 ℃, and the time of the hot pressing is 50 min.
Example 5:
the invention provides a halogen-free high-Tg copper-clad substrate which comprises a cured sheet layer and a copper foil layer, wherein the cured sheet layer is formed by stacking a plurality of prepregs, the prepregs are composed of electronic-grade glass cloth and glue solution, and the glue solution comprises the following raw materials in parts by weight: 120 parts of modified phosphorus-containing epoxy resin, 55 parts of phenolic benzylidene epoxy resin, 40 parts of polyether ether ketone resin, 6 parts of curing agent, 1 part of curing catalyst, 5 parts of processing aid and 100 parts of solvent.
In a preferred embodiment, the phosphorus content of the modified phosphorus-containing epoxy resin is 2%, the epoxy equivalent of the modified phosphorus-containing epoxy resin is 200g/eq, and the epoxy equivalent of the phenolic benzylidene epoxy resin is 220 g/eq.
In a preferred embodiment, the curing agent is a mixture of dicyandiamide and phthalic anhydride, and the weight ratio of dicyandiamide to phthalic anhydride is 1: 7, the curing catalyst is a mixture of dimethyl imidazole and phthalic anhydride, and the weight ratio of the dimethyl imidazole to the phthalic anhydride is 1: 8.
in a preferred embodiment, the processing aid comprises a silane coupling agent, a plasticizer and an antioxidant, and the weight ratio of the silane coupling agent to the plasticizer to the antioxidant is 1: 0.7: 0.6, the solvent is one or the mixture of more than two of acetone, DMF or butanone.
A preparation method of a halogen-free high-Tg copper-clad substrate comprises the following specific preparation steps:
the method comprises the following steps: weighing phosphorus-containing epoxy resin, placing the phosphorus-containing epoxy resin in a reaction container, heating to 190 ℃, adding triglycidyl isocyanurate, continuously stirring uniformly, completely mixing and melting the triglycidyl isocyanurate and the phosphorus-containing epoxy resin under the heating condition, placing the mixture in an extruder for granulation, extrusion and ball milling to obtain micro powder, and placing the micro powder, carbon fibers and glass fibers in a cross-linking granulator for granulation to obtain modified phosphorus-containing epoxy resin;
step two: preparing a glue solution, namely weighing the modified phosphorus-containing epoxy resin, the phenolic benzylidene epoxy resin, the polyether-ether-ketone resin, the curing agent, the curing catalyst, the processing aid and the solvent which are obtained in the step one according to the weight parts, and uniformly mixing the weighed modified phosphorus-containing epoxy resin, the phenolic benzylidene epoxy resin, the polyether-ether-ketone resin, the curing agent, the curing catalyst, the processing aid and the solvent under the ultrasonic assistance action to obtain the glue solution;
step three: preparing a prepreg, namely uniformly coating the glue solution obtained in the step two on electronic-grade glass cloth, and drying in an oven after coating to obtain the prepreg;
step four: selecting a proper amount of prepregs to be stacked together according to actual needs, then respectively covering a layer of copper foil on the surface of each of the prepregs at the top end and the surface of each of the prepregs at the bottom end, and then obtaining the halogen-free high-Tg copper-clad substrate by a hot-pressing technology.
In a preferred embodiment, the amount of triglycidyl isocyanurate added in step one is 3% by weight of the phosphorus-containing epoxy resin, and the temperature of the cross-linking granulator during granulation in step one is 370 ℃.
In a preferred embodiment, the power of the ultrasonic assistance in the second step is 900W, the temperature inside the oven during the drying in the third step is 170 ℃, and the drying time is 10 min.
In a preferred embodiment, the pressure during the hot pressing in the fourth step is 2.5MPa, the temperature during the hot pressing is 210 ℃, and the time of the hot pressing is 50 min.
The copper-clad substrates prepared in the above examples 1 to 5 were respectively used as an experimental group 1, an experimental group 2, an experimental group 3, an experimental group 4, and an experimental group 5, and commercially available copper-clad substrates were used as a control group, and the selected copper-clad substrates were subjected to the detection of glass transition temperature, flame retardancy (UL94), heat distortion temperature, and peel strength. The test results are shown in table one:
watch 1
As shown in the table I, compared with the traditional copper-clad plate, the copper-clad plate produced by the invention has better glass transition temperature, high temperature resistance effect and flame resistance, and higher peel strength, compared with the example 1, the example 4 adopts the common phosphorus-containing epoxy resin, the glass transition temperature and the high temperature resistance effect are reduced compared with the example 1, the example 5 does not add the inorganic filler, the glass transition temperature and the high temperature resistance effect are reduced, and the peel strength is poorer compared with the example 1, the invention takes the modified phosphorus-containing epoxy resin, the phenolic benzylidene epoxy resin and the polyether ether ketone resin as the raw materials to prepare the glue solution, the phosphorus-containing epoxy resin utilizes triglycidyl isocyanurate, carbon fiber and glass fiber to modify, the carbon fiber and the glass fiber can have better modification effect on the phosphorus-containing epoxy resin by utilizing the bonding property of the triglycidyl isocyanurate, the triglycidyl isocyanurate has good heat resistance and weather resistance, so that the modified phosphorus-containing epoxy resin has good heat resistance, the glass transition temperature of the plate is raised, and the copper-clad substrate has good toughness and corrosion resistance by blending the phenolic benzylidene epoxy resin, the polyether-ether-ketone resin and the modified epoxy resin; by adding the inorganic filler which comprises modified barium sulfate, aluminum hydroxide and boron nitride, the copper-clad plate has higher temperature resistance, the glass transition temperature of the copper-clad substrate is increased, and the thermal shock resistance effect and the peel strength of the copper-clad plate are obviously improved.
And finally: the above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents, improvements and the like that are within the spirit and principle of the present invention are intended to be included in the scope of the present invention.
Claims (10)
1. The utility model provides a there is not steamed high Tg copper-clad base plate, includes solidification lamella and copper foil layer, the solidification lamella forms through a plurality of prepregs are piled up, the prepreg adopts electronic grade glass cloth and glue solution to constitute its characterized in that: the glue solution comprises the following raw materials in parts by weight: 120-160 parts of modified phosphorus-containing epoxy resin, 55-70 parts of phenolic benzylidene epoxy resin, 40-60 parts of polyether ether ketone resin, 6-18 parts of curing agent, 0.5-10 parts of curing catalyst, 40-60 parts of inorganic filler, 5-15 parts of processing aid and 150 parts of solvent.
2. The halogen-free high-Tg copper-clad substrate of claim 1, wherein: the glue solution comprises the following raw materials in parts by weight: 150 parts of modified phosphorus-containing epoxy resin 130-containing material, 60-65 parts of phenolic benzylidene epoxy resin, 45-55 parts of polyether ether ketone resin, 10-14 parts of curing agent, 4-6 parts of curing catalyst, 45-55 parts of inorganic filler, 8-12 parts of processing aid and 130 parts of solvent 120-containing material.
3. The halogen-free high-Tg copper-clad substrate of claim 1, wherein: the glue solution comprises the following raw materials in parts by weight: 140 parts of modified phosphorus-containing epoxy resin, 63 parts of phenolic benzylidene epoxy resin, 50 parts of polyether-ether-ketone resin, 12 parts of curing agent, 5 parts of curing catalyst, 50 parts of inorganic filler, 10 parts of processing aid and 125 parts of solvent.
4. The halogen-free high-Tg copper-clad substrate of claim 1, wherein: the phosphorus content of the modified phosphorus-containing epoxy resin is 1-3%, the epoxy equivalent of the modified phosphorus-containing epoxy resin is 200-eq, and the epoxy equivalent of the phenolic benzylidene epoxy resin is 230-eq.
5. The halogen-free high-Tg copper-clad substrate of claim 1, wherein: the curing agent is a mixture of dicyandiamide and phthalic anhydride, and the weight ratio of dicyandiamide to phthalic anhydride is 1: (6-8), wherein the curing catalyst is a mixture of dimethyl imidazole and phthalic anhydride, and the weight ratio of the dimethyl imidazole to the phthalic anhydride is 1: (5-10), wherein the inorganic filler is a mixture of modified barium sulfate, aluminum hydroxide and boron nitride, and the weight ratio of the modified barium sulfate to the aluminum hydroxide to the boron nitride is 1: (1-3): (0.5-1.5), and the particle size of the inorganic filler is 0.1-20 um.
6. The halogen-free high-Tg copper-clad substrate of claim 1, wherein: the processing aid comprises a silane coupling agent, a plasticizer and an antioxidant, wherein the weight ratio of the silane coupling agent to the plasticizer to the antioxidant is 1: (0.6-0.8): (0.5-0.8), and the solvent is one or a mixture of more than two of acetone, DMF or butanone.
7. A preparation method of a halogen-free high-Tg copper-clad substrate is characterized by comprising the following steps: the preparation method comprises the following specific steps:
the method comprises the following steps: weighing phosphorus-containing epoxy resin, placing the phosphorus-containing epoxy resin in a reaction container, heating to 180 ℃ and 200 ℃, then adding triglycidyl isocyanurate, continuously stirring uniformly, completely mixing and melting the triglycidyl isocyanurate and the phosphorus-containing epoxy resin under the heating condition, then placing the mixture in an extruder for granulation, extrusion and ball milling to obtain micro powder, and placing the micro powder, carbon fibers and glass fibers in a cross-linking granulator for granulation to obtain modified phosphorus-containing epoxy resin;
step two: preparing a glue solution, namely weighing the modified phosphorus-containing epoxy resin, the phenolic benzylidene epoxy resin, the polyether-ether-ketone resin, the curing agent, the curing catalyst, the inorganic filler, the processing aid and the solvent which are obtained in the step one according to the weight parts, and uniformly mixing the weighed modified phosphorus-containing epoxy resin, the phenolic benzylidene epoxy resin, the polyether-ether-ketone resin, the curing agent, the curing catalyst, the inorganic filler, the processing aid and the solvent under the ultrasonic assistance to obtain the glue solution;
step three: preparing a prepreg, namely uniformly coating the glue solution obtained in the step two on electronic-grade glass cloth, and drying in an oven after coating to obtain the prepreg;
step four: selecting a proper amount of prepregs to be stacked together according to actual needs, then respectively covering a layer of copper foil on the surface of each of the prepregs at the top end and the surface of each of the prepregs at the bottom end, and then obtaining the halogen-free high-Tg copper-clad substrate by a hot-pressing technology.
8. The method for preparing the halogen-free high-Tg copper-clad substrate according to claim 7, wherein the method comprises the following steps: the addition amount of the triglycidyl isocyanurate in the step one is 1-5% of the weight of the phosphorus-containing epoxy resin, and the temperature of the cross-linking granulator in the step one is 360-380 ℃.
9. The method for preparing the halogen-free high-Tg copper-clad substrate according to claim 7, wherein the method comprises the following steps: the power during the ultrasonic assistance in the second step is 800-.
10. The method for preparing the halogen-free high-Tg copper-clad substrate according to claim 7, wherein the method comprises the following steps: the pressure during the hot pressing in the fourth step is 1.5-3MPa, the temperature during the hot pressing is 180-240 ℃, and the time of the hot pressing is 40-60 min.
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