CN102731966A - Thermosetting epoxy resin composition and prepreg and copper clad laminate made using it - Google Patents

Abstract

The invention provides a thermosetting epoxy resin composition, which comprises the following components in parts by weight: 100 parts by weight of epoxy resin; 2-10 parts by weight of a tetraphenylethane compound; 5-30 parts of linear phenolic resin; dicyandiamide, 0.5-2.2 parts by weight; 0.05 to 1.0 weight portion of curing accelerator; the thermosetting epoxy resin composition has good cohesiveness and can effectively absorb ultraviolet light; after being cured, the material has good heat resistance, toughness and machinability, high glass transition temperature and low hygroscopicity. The prepreg and the copper-clad plate manufactured by using the thermosetting epoxy resin composition have high heat resistance and low linear expansion coefficient, and are suitable for lead-free welding; the solder resist ink also has good cohesiveness, toughness and machining performance, high glass transition temperature, low hygroscopicity and ultraviolet light barrier property, and can meet the requirement of double-sided exposure of solder resist ink in PCB processing.

Description

Thermosetting epoxy resin composition and prepreg and copper clad laminate made using it

technical field

The invention relates to the field of copper-clad laminates, in particular to a thermosetting epoxy resin composition and a prepreg and a copper-clad laminate made of the composition.

Background technique

At present, electronic products are constantly trending towards miniaturization and multi-functionalization, and electronic products that process data and information are also advancing in the direction of high-speed transmission and large capacity. In order to achieve the goal of high-performance electronic products, electronic components The development of high integration is more rapid, and high-density assembly technologies such as surface mount technology (Surface Mounted Technology, SMT), chip scale package (Chip Scale Package, CSP), and system level package (System In a Package, SIP) have been fully developed. In this case, the problem of high concentration of heat sources of electronic components becomes more prominent. For this reason, this kind of electronic complete machine products requires printed circuit boards (PCBs) to have high heat resistance, high heat dissipation and high reliability under humidity and heat suitable for high-density assembly conditions.

In order to meet the needs of high-density assembly, PCBs as electronic components are also gradually moving towards higher density. PCBs are characterized by miniaturization of through holes, finer wires, thinner dielectric layers and high multi-layers. Its structure has also changed from conventional structure to Buried blind vias, high density interconnect (High Density Inverter, HDI)/build up multilayer (Build up Multilayer, BUM), embedded components and other three-dimensional structures are developing. With the development of thick and high multi-layer boards, the aspect ratio of plated through holes is increasing. In order to avoid the phenomenon of desoldering of the land and the cracking of the coating in the through holes, and improve the reliability of the PCB through holes, the heat resistance and expansion coefficient of the board are proposed. higher requirement.

With the official implementation of the EU directives WEEE (Waste Electrical and Electronic Equipment) and RoHS (Restriction of Hazardous Substances), the global electronics industry has entered the era of lead-free. In printed circuits, in the past, lead-tin alloys (such as Sn63Pb37) were used as PCB soldering materials. Lead-tin alloys have a low eutectic point of 183°C and excellent mechanical properties. However, after removing the presence of lead, the lowest eutectic point of the currently available lead-free solders (such as Sn-Ag-Cu series) reaches 217°C, which is more than 30°C higher than that of lead-tin alloys, and high-temperature soldering requires For a longer period of time, rapid cooling is required after welding, which poses severe challenges to the heat resistance and reliability of the plate.

In the PCB substrate material with glass fiber cloth as the reinforcement material, the FR-4 board of the usual epoxy system is cured by dicyandiamide (DICY), and the board has good processability, so it is widely used in PCB , but this kind of board has high hygroscopicity and low thermal decomposition temperature, which makes it difficult to meet the needs of lead-free soldering.

In addition, with the development of PCB in the direction of high density, the processing method of ultraviolet (UV) light double-sided exposure is adopted when making the solder mask layer. Ordinary FR-4 cannot absorb ultraviolet light, so that when the PCB is exposed, the ultraviolet light will pass through. Through the resin layer, the solder resist ink on the other side that should not be exposed is exposed, resulting in insufficient development and affecting the quality of the circuit.

In order to improve the heat resistance of the board and meet the requirements of lead-free soldering, CN1966572A discloses an epoxy resin composition using phenolic formaldehyde as a curing agent. The composition has a relatively high thermal decomposition temperature, but it has high brittleness and high toughness. Undesirable phenomena have a negative impact on PCB machining; and in Japanese Patent Application Hei 5-51436, it discloses an epoxy resin composition, which is mainly composed of epoxy resin, dicyandiamide, and molecules containing more than two phenolic hydroxyl groups. The compound is composed of an aromatic amine with two or more amino groups in its molecule and a curing accelerator. It is stated that the composition has better adhesion. Compared with the dicyandiamide curing system, it reduces the water absorption and improves the heat resistance. High curing temperature is required; in addition, although aromatic amine is a high-temperature curing agent, it will react slowly at room temperature, so that the storage period of the adhesive sheet is greatly shortened. In addition, the system does not have the function of blocking ultraviolet light. The system uses dimethylformamide (DMF) as a solvent, and the glue has a short shelf life.

Contents of the invention

The object of the present invention is to provide a thermosetting epoxy resin composition, which has good adhesion and can effectively absorb ultraviolet light; after curing, it has good heat resistance, toughness and machinability, and has a high glass transition temperature and low hygroscopicity.

Another object of the present invention is to provide a prepreg and copper-clad laminate made of the above-mentioned thermosetting epoxy resin composition, which has high heat resistance and low thermal expansion coefficient and is suitable for lead-free soldering; it also has good adhesion Junction, toughness and machinability, high glass transition temperature, low moisture absorption and UV blocking.

To achieve the above object, the present invention provides a thermosetting epoxy resin composition, comprising components and parts by weight as follows: epoxy resin, 100 parts by weight; tetraphenol ethane compound, 2-10 parts by weight; novolak resin , 5-30 parts by weight; dicyandiamide, 0.5-2.2 parts by weight; curing accelerator, 0.05-1.0 parts by weight.

The general structural formula of the tetraphenol group ethane compound is as follows:

(Formula I)

In formula I, R is a hydrogen atom or a hydrocarbon group with 1-4 carbon atoms.

Described epoxy resin is the mixture of difunctional epoxy resin, multifunctional epoxy resin, or bifunctional epoxy resin and multifunctional epoxy resin; Described bifunctional epoxy resin is containing bisphenol A type, bisphenol F Type, or bisphenol S-type epoxy resin; the multifunctional epoxy resin is an epoxy resin with two or more epoxy groups in its molecule and an aromatic ring structure.

The epoxy equivalent of the bifunctional epoxy resin is 300-520g/eq, which is specifically bisphenol A type epoxy resin, brominated bisphenol A type epoxy resin, difunctional isocyanate and bromine-containing or non-bromine Condensate of bisphenol A epoxy resin, and 9,10-dihydro-9-oxo-10-phosphaphenanthrene hydroquinone or 9,10-dihydro-9-oxo-10-phosphaphenanthrene At least one of the condensation products of quinone and bisphenol A epoxy resin; the multifunctional epoxy resin is specifically phenol novolac epoxy resin, o-cresol novolac epoxy resin, bisphenol A novolac epoxy resin Resin, novolac epoxy resin produced by the reaction of p-phenol benzaldehyde with phenol, o-cresol or bisphenol A under the acidic catalyst and then reacted with epichlorohydrin, dicyclopentadiene or biphenyl Epoxy resin, the condensate of 9,10-dihydro-9-oxo-10-phosphaphenanthrene-10-oxide and novolac epoxy resin, and the condensate of tetraphenol ethane and epichlorohydrin at least one.

The novolac resin is a compound containing more than two phenolic hydroxyl groups in the molecule, which is specifically phenol-type Novlak, o-cresol-type Novlak, bisphenol A-type Novlak, p-hydroxybenzaldehyde and phenol, o-cresol At least one of the phenolic resin produced by the reaction of cresol or bisphenol A under the acidic catalyst, and the phosphorus-containing phenolic resin.

Between the phenolic hydroxyl equivalent number H1 in the tetraphenol ethane compound, the phenolic hydroxyl equivalent number H2 in the novolac resin, the amine equivalent number H3 in dicyandiamide, and the epoxy group equivalent number E in the epoxy resin The proportional relationship (H1+H2+2×H3)/E=0.9-1.1.

The curing accelerator is one or more mixtures of imidazoles, organic phosphines, and tertiary amines; the imidazoles are 2-methylimidazole, 2-methyl-4-ethylimidazole, 2- At least one of undecylimidazole, 2-phenylimidazole, and 1-cyanoethyl-2-ethyl-4-methylimidazole, the tertiary amine is benzyldimethylamine, and the organic phosphine It is tributylphosphine, triphenyl, or a mixture of tributylphosphine and triphenyl.

The thermosetting epoxy resin composition also includes a solvent, which is ethylene glycol methyl ether or propylene glycol methyl ether; the weight part of the solvent is 10-30 of the weight part of dicyandiamide in the thermosetting epoxy resin composition times. The amount of the solvent is based on adding the thermosetting epoxy resin composition so that the solid content of the glue is controlled at 50-70%.

The thermosetting epoxy resin composition also includes inorganic fillers, which may or may not be added into the thermosetting epoxy resin composition. The inorganic filler is aluminum hydroxide, magnesium hydroxide, silicon dioxide, glass powder, kaolin, talcum powder, mica powder, boehmite, aluminum oxide, zinc oxide, magnesium oxide, boron nitride, aluminum nitride, or carbonic acid Calcium, preferably aluminum hydroxide, silicon dioxide, glass powder, kaolin, or talcum powder; its average particle diameter is 0.3-20 μm; its weight part, according to the organic solid content of the components in the thermosetting epoxy resin composition Calculated in 100 parts by weight, it is 5-300 parts by weight, preferably 10-60 parts by weight.

The thermosetting epoxy resin composition also includes a non-reactive flame retardant, which may or may not be added to the thermosetting epoxy resin composition. The non-reactive flame retardant is decabromodiphenylethane, ethyl-bis(tetrabromophthalimide), triazine bromide, phosphazene, aluminum metaphosphate, or melamine cyanurate. Based on 100 parts by weight of the organic solids of the components in the thermosetting epoxy resin composition, the weight part of the non-reactive flame retardant is 5-40 parts by weight, preferably 15-30 parts by weight.

The invention provides a prepreg made by using the thermosetting epoxy resin composition. The prepreg includes a base material and an epoxy resin composition attached to the base material after being impregnated and dried.

The base material is non-woven or woven glass fiber cloth.

The present invention provides a copper-clad laminate made of the prepreg. The copper-clad laminate comprises several laminated prepregs and copper foil pressed on one or both sides of the laminated prepregs. Each prepreg includes a base material and an epoxy resin composition adhered to the base material after being impregnated and dried.

Beneficial effects of the present invention: ①The thermosetting epoxy resin composition of the present invention has good adhesion and can effectively absorb ultraviolet light; after curing, it has good heat resistance, toughness and machinability, and has high glass Transition temperature and low hygroscopicity; ②The prepreg and copper-clad laminate made of the above-mentioned thermosetting epoxy resin composition in the present invention have high heat resistance and low thermal expansion coefficient, and are suitable for lead-free soldering; also have good adhesion Junction, toughness and machinability, high glass transition temperature, low moisture absorption and UV blocking properties, can meet the needs of double-sided exposure of solder resist ink in PCB processing.

In order to further understand the features and technical content of the present invention, please refer to the following detailed description of the present invention.

Detailed ways

In order to further illustrate the technical means adopted by the present invention and its effects, the following is a detailed description in conjunction with preferred embodiments of the present invention.

The invention provides a thermosetting epoxy resin composition, comprising the following components and parts by weight: epoxy resin, 100 parts by weight; tetraphenol ethane compound, 2-10 parts by weight; novolak resin, 5-30 parts by weight parts; dicyandiamide, 0.5-2.2 parts by weight; curing accelerator, 0.05-1.0 parts by weight.

The general structural formula of the tetraphenol group ethane compound is as follows:

(Formula I)

In formula I, R is a hydrogen atom or a hydrocarbon group with 1-4 carbon atoms.

Described epoxy resin is the mixture of difunctional epoxy resin, multifunctional epoxy resin, or bifunctional epoxy resin and multifunctional epoxy resin; Described bifunctional epoxy resin is containing bisphenol A type, bisphenol F Type, or bisphenol S-type epoxy resin, using bifunctional epoxy resin with excellent mechanical properties, electrical properties and thermal properties, through a large number of ether bonds in the resin to provide good toughness of the board, a large number of hydroxyl groups to Improve the bonding performance of the board; the multifunctional epoxy resin is an epoxy resin containing more than two epoxy groups and an aromatic ring structure in the molecule, and the resin system is partially introduced or fully adopts the multifunctional epoxy resin, which can Increase the cross-linking density of resin curing, thereby increasing the glass transition temperature of the sheet.

The epoxy equivalent of the bifunctional epoxy resin is 300-520g/eq. When the epoxy equivalent is lower than 300g/eq, the brittleness of the cured product will increase. When the epoxy equivalent is greater than 520g/eq, the cured product will vitrify The transition temperature will decrease, and the bifunctional epoxy resin can be used alone or in combination of two or more; the bifunctional epoxy resin is specifically bisphenol A epoxy resin, brominated bisphenol A epoxy resin, bifunctional Condensates of isocyanate and brominated or non-brominated bisphenol A epoxy resin, and 9,10-dihydro-9-oxo-10-phosphaphenanthrene hydroquinone or 9,10-dihydro- At least one of the condensation products of 9-oxo-10-phosphaphenanthraxone and bisphenol A epoxy resin; the multifunctional epoxy resin is specifically phenol novolac epoxy resin, orthocresol novolac ring Oxygen resin, bisphenol A novolac epoxy resin, novolac epoxy resin generated by the reaction of p-phenol benzaldehyde with phenol, o-cresol or bisphenol A under the acidic catalyst and then reacted with epichlorohydrin , dicyclopentadiene type or biphenyl type epoxy resin, condensate of 9,10-dihydro-9-oxo-10-phosphaphenanthrene-10-oxide and novolac epoxy resin, and tetraphenol ethane At least one of the condensates with epichlorohydrin, the introduction of the multifunctional epoxy will increase the crosslink density of the resin composition and improve the heat resistance. The multifunctional epoxy resin can be used alone or in two Use a mix of the above.

The use of the tetraphenol-based ethane compound improves the heat resistance of the board, reduces the hygroscopicity of the board, can further increase the crosslinking density of the resin, raise the glass transition temperature of the board, and increase the ability to absorb ultraviolet light, thereby having UV light blocking effect.

The novolac resin is a compound containing more than two phenolic hydroxyl groups in the molecule, which is specifically phenol-type Novlak, o-cresol-type Novlak, bisphenol A-type Novlak, p-hydroxybenzaldehyde and phenol, o-cresol At least one of the phenolic resin produced by the reaction of cresol or bisphenol A under the acidic catalyst, and the phosphorus-containing phenolic resin.

Between the phenolic hydroxyl equivalent number H1 in the tetraphenol ethane compound, the phenolic hydroxyl equivalent number H2 in the novolac resin, the amine equivalent number H3 in dicyandiamide, and the epoxy group equivalent number E in the epoxy resin The proportional relationship of (H1+H2+2×H3)/E=0.9-1.1, at this time, the cured product has better moisture resistance and glass transition temperature.

The curing accelerator is one or more mixtures of imidazoles, organic phosphines, and tertiary amines; the imidazoles are 2-methylimidazole, 2-methyl-4-ethylimidazole, 2- At least one of undecylimidazole, 2-phenylimidazole, and 1-cyanoethyl-2-ethyl-4-methylimidazole, the tertiary amine is benzyldimethylamine, and the organic phosphine It is tributylphosphine, triphenyl, or a mixture of tributylphosphine and triphenyl.

The thermosetting epoxy resin composition also includes a solvent; the solvent is mainly used for dissolving dicyandiamide and phenolic resin, and an organic solvent with a boiling point below 160° C. that does not contain nitrogen can be used, and the use of a nitrogen-containing organic solvent will promote environmental The curing of epoxy resin glue affects storage performance; the solvent is acetone, butanone, cyclohexanone, methyl alcohol, ethylene glycol methyl ether, ethylene glycol ethyl ether or propylene glycol methyl ether, preferably ethylene glycol methyl ether or propylene glycol Methyl ether; the amount of solvent is based on adding the thermosetting epoxy resin composition so that the solid content of the glue is controlled at 50-70%, wherein the total weight of the solvent ethylene glycol methyl ether or propylene glycol methyl ether , which is 10-30 times of the weight part of dicyandiamide in the thermosetting epoxy resin composition.

The thermosetting epoxy resin composition also includes inorganic fillers, which may or may not be added into the thermosetting epoxy resin composition. The inorganic filler is aluminum hydroxide, magnesium hydroxide, silicon dioxide, glass powder, kaolin, talcum powder, mica powder, boehmite, aluminum oxide, zinc oxide, magnesium oxide, boron nitride, aluminum nitride, or carbonic acid Calcium, preferably aluminum hydroxide, silicon dioxide, glass powder, kaolin, or talcum powder; its average particle size is 0.3-20 μm, and when the average particle size exceeds 20 μm, it will cause blockage in the filter screen for gluing and filtering foreign matter. In addition, the filler is easy to settle in the glue of the epoxy resin composition; the amount of the inorganic filler can be adjusted according to the purpose of use, and its parts by weight are calculated according to 100 parts by weight of the organic solids of the components in the thermosetting epoxy resin composition , is 5-300 parts by weight, preferably 10-60 parts by weight. The inorganic filler is used to reduce the water absorption and thermal expansion coefficient of the composition.

The thermosetting epoxy resin composition also includes a non-reactive flame retardant, which may or may not be added to the thermosetting epoxy resin composition. The non-reactive flame retardant is used to improve the flame retardancy of the epoxy resin composition, and it is decabromodiphenylethane, ethyl-bis(tetrabromophthalimide), triazine bromide, Phosphazene, aluminum metaphosphate, or melamine cyanurate. Based on 100 parts by weight of the organic solids of the components in the thermosetting epoxy resin composition, the weight part of the non-reactive flame retardant is 5-40 parts by weight, preferably 15-30 parts by weight.

Mix the epoxy resin, tetraphenol ethane compound, phenolic resin, dicyandiamide, and curing accelerator described in the present invention with an organic solvent, and use stirring and dispersing equipment to uniformly mix them, thereby making a printed circuit Thermosetting epoxy resin composition for panels.

The present invention also provides a prepreg made of the thermosetting epoxy resin composition, the prepreg comprising a base material and an epoxy resin composition attached to the base material after being impregnated and dried.

The base material is non-woven or woven glass fiber cloth.

The base material is impregnated with the above-prepared thermosetting epoxy resin composition for printed circuit boards, and dried in a gluing machine (120-180° C.) to prepare a semi-cured prepreg for printed circuit boards.

The present invention further provides a copper-clad laminate made of the above-mentioned prepreg, the copper-clad laminate comprises several laminated prepregs, and copper foil laminated on one or both sides of the laminated prepregs , each prepreg includes a base material and an epoxy resin composition adhered to the base material after being impregnated and dried.

The above-mentioned prepregs are laminated according to the required number of sheets, and copper foil is laminated on one or both sides of the laminate, and then placed on a laminator at 120-200°C, heated and pressed, and finally cured and formed to form a Copper clad laminates for printed circuit board processing. The copper foil can also be replaced by aluminum foil, silver foil or stainless steel foil.

The present invention is illustrated and described in detail through the following examples. The composition formulas of the examples and comparative examples of the thermosetting epoxy resin composition are shown in Table 1 and Table 2. See Table 3 and Table 4 for the physical property data of the glass transition temperature, peel strength, solder dip resistance time, water absorption rate and ultraviolet light transmittance of the copper-clad laminates produced in the examples and comparative examples.

The specific components of the thermosetting epoxy resin composition are as follows:

(A) epoxy resin:

A1: brominated bisphenol A type epoxy resin (DER530A80, epoxy equivalent is 430g/eq, produced by American DOW Chemical Company);

A2: phosphorus-containing epoxy resin (DER92530, the epoxy equivalent is 325g/eq, produced by DOW Chemical Company of the United States);

A3: o-cresol type Novrak epoxy resin (EPON164, epoxy equivalent 210g/eq, produced by American Momentive Chemical Company).

(B) tetraphenol ethane compound:

B1: Multifunctional phenolic compound (KPE-F3110, produced by Korea Kolon Chemical Company);

B2: multifunctional phenolic compound (SD-357B, produced by Momentive Chemical Company, USA).

(C) Novolac resin

C1: phenol-formaldehyde Nofrak resin (KPH-F2003, produced by Korea Kolon Chemical Company);

C2: bisphenol A type Novella resin (EXP0382, produced by Shandong Shengquan Chemical Company).

(D) Dicyandiamide (produced in Ningxia Darong).

(E) Curing accelerator: (2-E-4MI, produced by Shikoku Chemicals, Japan).

(F) solvent

F1: Ethylene glycol methyl ether;

F2: propylene glycol methyl ether;

F3: N,N-Dimethylformamide

Table 1. each embodiment and comparative example formula (by solid amount)

Example 1 Example 2 Example 3 Example 4 Comparative example 1 Comparative example 2 Comparative example 3 A1 100 100 0 90 100 0 100 A2 0 0 80 0 0 100 0 A3 0 0 20 10 0 0 0 B1 4 6 0 7 0 0 0 B2 0 0 8 0 0 0 0 C1 6 0 12 0 0 0 10 C2 0 11 0 11 0 0 0 D 1.6 0.9 1.4 1.0 3 3.4 1.6 E 0.08 0.12 0.3 0.1 0.15 0.6 0.09 F1 twenty four 0 28 5 0 0 twenty four F2 0 twenty four 0 20 0 0 0 F3 0 0 0 0 28 32 0

Table 3. Physical property data of each embodiment and comparative example

The test methods for the above characteristics are as follows:

(A) Glass transition temperature (Tg)

According to differential scanning calorimetry (DSC), the measurement is carried out in accordance with the DSC method specified in IPC-TM-6502.4.25.

(B) Peel strength (PS)

According to the "after thermal stress" experimental condition in the IPC-TM-6502.4.8 method, the peel strength of the metal cap layer is tested.

(C) Soldering resistance time

Dip a double-sided copper foil plate with a size of 100X100mm in a solder bath heated to 288°C, and calculate the time from immersion to the plate delamination explosion.

(D) Water absorption

Accurately weigh the substrate with a size of 100X100mm (denoted as weight W1), then put it into a pressure cooker, and cook under pressure at 121°C and 105KPa for 2 hours, take out and wipe off the water on the surface, and then make Weigh (denoted as weight W2), and calculate the water absorption rate of the board (W1-W2)/W1(%).

(E) UV transmittance

Using a 3kw UV lamp and a UV intensity meter (365nm band), place the substrate with the etched copper foil at a distance of 45cm from the UV lamp, and test the UV light intensity (denoted as U1) and UV light penetration through the board without the board After the UV light intensity (U2), calculate the transmittance U2/U1 (%).

In summary, the thermosetting epoxy resin composition of the present invention has good adhesion and can effectively absorb ultraviolet light; after curing, it has good heat resistance, toughness and machinability, and has a high glass transition temperature and low hygroscopicity. The prepreg and copper-clad laminate made of the above-mentioned thermosetting epoxy resin composition in the present invention have high heat resistance and low thermal expansion coefficient, so it has a long dip-soldering resistance time and is suitable for lead-free soldering; it also has good adhesion, toughness and Machinability, high glass transition temperature, low moisture absorption and UV blocking properties, can meet the needs of double-sided exposure of solder resist ink in PCB processing.

As mentioned above, for those of ordinary skill in the art, various other corresponding changes and deformations can be made according to the technical scheme and technical concept of the present invention, and all these changes and deformations should belong to the protection scope of the claims of the present invention .

Claims (13)

1. a thermosetting epoxy resin composition, is characterized in that, comprises component and weight part thereof as follows: epoxy resin, 100 weight parts; Tetraphenol group ethane compound, 2-10 weight part; Novolac resin, 5 parts by weight -30 parts by weight; dicyandiamide, 0.5-2.2 parts by weight; curing accelerator, 0.05-1.0 parts by weight. 2. thermosetting epoxy resin composition as claimed in claim 1, is characterized in that, the general structural formula of described tetraphenol group ethane compound is as follows:

(Formula I) In formula I, R is a hydrogen atom or a hydrocarbon group with 1-4 carbon atoms. 3. thermosetting epoxy resin composition as claimed in claim 1, is characterized in that, described epoxy resin is bifunctional epoxy resin, multifunctional epoxy resin or bifunctional epoxy resin and multifunctional epoxy resin The mixture; the bifunctional epoxy resin is an epoxy resin containing bisphenol A type, bisphenol F type or bisphenol S type structure; the multifunctional epoxy resin contains more than two epoxy groups in the molecule and Epoxy resins with an aromatic ring structure. 4. thermosetting epoxy resin composition as claimed in claim 3, is characterized in that, the epoxy equivalent of described bifunctional epoxy resin is 300-520g/eq, and it is specifically bisphenol A type epoxy resin, bromine Bisphenol A type epoxy resin, condensation product of difunctional isocyanate and bromine-containing or non-bromine bisphenol A type epoxy resin, and 9,10-dihydro-9-oxo-10-phosphaphenanthrene p-phenylene At least one of the condensation products of diphenol or 9,10-dihydro-9-oxo-10-phosphaphenanthaquinone and bisphenol A epoxy resin; the multifunctional epoxy resin is specifically phenolic novolac Epoxy resin, o-cresol novolac epoxy resin, bisphenol A novolac epoxy resin, p-phenol benzaldehyde and phenol, o-cresol or bisphenol A under the reaction of an acidic catalyst to generate a phenolic resin and then react with epoxy Novolak type epoxy resin, dicyclopentadiene type or biphenyl type epoxy resin, 9,10-dihydro-9-oxo-10-phosphaphenanthrene-10-oxide and novolac epoxy resin produced by the reaction of chloropropane Condensate, and at least one of the condensation products of tetraphenol ethane and epichlorohydrin. 5. thermosetting epoxy resin composition as claimed in claim 1, is characterized in that, described novolac resin is the compound that contains more than two phenolic hydroxyl groups in the molecule, and it is specifically phenolic Nofrak, o-cresol type Novlak, bisphenol A type Novlak, at least one of the phenolic resin formed by the reaction of p-hydroxybenzaldehyde and phenol, o-cresol or bisphenol A under an acidic catalyst, and phosphorus-containing phenolic resin. 6. thermosetting epoxy resin composition as claimed in claim 1, is characterized in that, in described tetraphenol group ethane compound, phenolic hydroxyl equivalent number H1, in described novolac resin, phenolic hydroxyl equivalent number H2, dicyandiamide The proportional relationship between the equivalent number of amino groups H3 in the epoxy resin and the equivalent number of epoxy groups in the epoxy resin (H1+H2+2×H3)/E=0.9-1.1. 7. thermosetting epoxy resin composition as claimed in claim 1, is characterized in that, described curing accelerator is the mixture of one or more in imidazoles, organic phosphine and tertiary amine; The imidazoles For 2-methylimidazole, 2-methyl-4-ethylimidazole, 2-undecylimidazole, 2-phenylimidazole, and 1-cyanoethyl-2-ethyl-4-methylimidazole The tertiary amine is benzyldimethylamine, and the organic phosphine is tributylphosphine, triphenyl, or a mixture of tributylphosphine and triphenyl. 8. thermosetting epoxy resin composition as claimed in claim 1, is characterized in that, also comprises solvent, and this solvent is ethylene glycol methyl ether or propylene glycol methyl ether; The weight part of solvent is described thermosetting epoxy resin combination 10-30 times the weight of dicyandiamide in the product. 9. thermosetting epoxy resin composition as claimed in claim 1, is characterized in that, also comprises inorganic filler, and this inorganic filler is aluminum hydroxide, magnesium hydroxide, silicon dioxide, glass powder, kaolin, talcum powder, mica powder, boehmite, aluminum oxide, zinc oxide, magnesium oxide, boron nitride, aluminum nitride, or calcium carbonate, the average particle diameter of which is 0.3-20 μm; the weight part of the inorganic filler is based on the thermosetting epoxy resin Based on 100 parts by weight of the organic solids of the components in the composition, it is 5-300 parts by weight, preferably 10-60 parts by weight. 10. thermosetting epoxy resin composition as claimed in claim 1, is characterized in that, also comprises non-reactive flame retardant, and this non-reactive flame retardant is decabromodiphenylethane, ethyl-bis(tetrafluoroethylene) bromophthalimide), triazine bromide, phosphazene, aluminum metaphosphate, or melamine cyanurate; calculated on 100 parts by weight of the organic solids of the components in the thermosetting epoxy resin composition , The weight portion of the non-reactive flame retardant is 5-40 weight parts, preferably 15-30 weight parts. 11. A prepreg made of the thermosetting epoxy resin composition according to claim 1, characterized in that the prepreg comprises a base material and an epoxy resin composition attached to the base material after being impregnated and dried. 12 . The prepreg made of thermosetting epoxy resin composition according to claim 11 , wherein the base material is non-woven or woven glass fiber cloth. 13 . 13. A copper-clad laminate made using the prepreg according to claim 11, wherein the copper-clad laminate comprises several stacked prepregs, and is pressed on one side of the stacked prepregs. or copper foil on both sides.