A high-heat-resistant low-dielectric multi-aromatic ring phosphorus-containing phenolic curing agent, a preparation method thereof, a composition for copper-clad plates and applications thereof

Abstract

The application discloses a high-heat-resistance low-dielectric multi-aromatic-ring phosphorus-containing phenolic curing agent and a preparation method thereof, a composition for copper-clad plate and application thereof, and belongs to the technical field of electronic resin synthesis. The high-heat-resistance low-dielectric multi-aromatic-ring phosphorus-containing phenolic curing agent comprises a naphthalene ring structure, a bisphenol structure, a benzene ring structure with a bulky side group and a phosphorus structure. Through the organic combination of the naphthalene ring structure, the bisphenol structure and the benzene ring structure with the bulky side group, the rigidity and flexibility of the phosphorus-containing phenolic curing agent can be balanced, the resin residual carbon can be improved, and the condensate phase flame retardation can be promoted. The high-heat-resistance low-dielectric multi-aromatic-ring phosphorus-containing phenolic curing agent is used in the preparation of the composition for copper-clad plate, and the composition for copper-clad plate is used in the preparation of the copper-clad plate. The obtained copper-clad plate has excellent comprehensive performance, i.e., a dielectric constant is less than or equal to 3.86, a dielectric loss is less than or equal to 0.0078, a glass transition temperature is greater than or equal to 185 DEG C, the plate has good toughness, and the flame retardation performance reaches the UL94V-0 level.

Description

TECHNICAL FIELD

[0001] The application belongs to the technical field of electronic resin synthesis, and specifically relates to a high-heat-resistance low-dielectric multi-aromatic-ring phosphorus-containing phenolic curing agent, a preparation method thereof, a copper-clad plate composition and application thereof. BACKGROUND

[0002] In recent years, with the miniaturization, high performance and multifunctionalization of electronic products, the number of electronic components is increased, the volume is reduced, the weight is reduced and the integration is continuously improved, which puts forward higher requirements on the substrate material used for the printed circuit board carrying electronic components to adapt to the development trend of high frequency and high speed of electronic signal processing and signal transmission, and high precision and high integration of electronic components. The requirements for the substrate material are high heat resistance, excellent dielectric properties, low water absorption, good processability and the like.

[0003] In the existing printed circuit board substrate, epoxy resin is widely used due to its good processability and comprehensive performance, but epoxy resin is flammable and cannot meet the development needs of halogen-free flame-retardant copper-clad plates. In the prior art, phosphorus-containing phenolic curing agent is one of the important ways to realize the halogen-free flame-retardant performance of copper-clad plates. Patent CN 117820579 A discloses a phosphorus-containing phenolic resin curing agent for copper-clad plates, which can make the copper-clad plate reach UL94 V0 flame-retardant grade at a lower phosphorus content of 8.0-8.5%, and the glass transition temperature of the copper-clad plate is about 161 DEG C. However, with the development of copper-clad plates towards high frequency and high speed, high integration, the heat resistance is not enough to support the use in higher heat resistance application scenarios, and the catalyst is not treated in the reaction process, the purity of the phosphorus-containing phenolic curing agent is low, which has an adverse effect on the dielectric properties of the copper-clad plate, and it is difficult to meet the use requirements of high-performance copper-clad plates. SUMMARY

[0004] The purpose of the present application is to overcome the deficiencies in the prior art, and to provide a high-heat-resistance low-dielectric multi-aromatic-ring phosphorus-containing phenolic curing agent, a preparation method thereof, a copper-clad plate composition and application thereof, so that the prepared copper-clad plate has good dielectric properties, heat resistance, flame retardant properties and toughness.

[0005] The purpose of the present application is achieved by the following technical solutions:

[0006] A high-heat-resistance low-dielectric multi-aromatic-ring phosphorus-containing phenolic curing agent, which comprises a naphthalene ring structure, a bisphenol structure, a benzene ring structure with a bulky side chain and a phosphorus structure.

[0007] As some embodiments of the present application, the high-heat-resistance low-dielectric multi-aromatic-ring phosphorus-containing phenolic curing agent comprises the following structural units (I), (II) and (III):

[0008]

[0009] In formula (I), R1 is any one of ether bond, cyclohexyl, fluorenyl, phenyl, and biphenyl;

[0010] R2 and R4 are selected from R3 and R5 are selected from methylene, In formula (II), R6 is selected from R7 and R8 are selected from methylene, and R7 and R8 are not simultaneously

[0011]

[0012] In formula (III), R9 and R 10 are selected from methylene, and R9 and R 10 are not simultaneously

[0013] R 11 is an alkyl or aralkyl group with a carbon number of 4-8, including but not limited to t-butyl, p-t-octyl, cycloalkyl, phenyl, and o-methylphenyl.

[0014] In addition, to achieve the above object, the application also provides a preparation method of a high-heat-resistant low-dielectric multi-aromatic ring phosphorus-containing phenolic curing agent, comprising the following steps:

[0015] S1. Reacting α-naphthol, a monophenol compound with a bulky side group, a bisphenol compound, and an aldehyde compound under the action of an alkaline catalyst to obtain a hydroxymethyl compound;

[0016] S2. After the hydroxymethyl compound is sequentially subjected to a neutralization reaction, an etherification reaction, and a purification step, it is subjected to a dealcoholization reaction with a phosphorus-containing compound, and then the obtained product is diluted with a first solvent to a resin solution of 60%-65%, which is the high-heat-resistant low-dielectric multi-aromatic ring phosphorus-containing phenolic curing agent.

[0017] In the above neutralization reaction, an acidic compound is used to neutralize the alkaline catalyst, and the generated salt is removed by washing, so as to achieve the purpose of purification and further improve the purity of the high-heat-resistant low-dielectric multi-aromatic ring phosphorus-containing phenolic curing agent.

[0018] The acidic compound includes but is not limited to hydrochloric acid, sulfuric acid, phosphoric acid, formic acid, oxalic acid, glacial acetic acid, methylsulfonic acid, and p-toluene sulfonic acid.

[0019] As some embodiments of the present application, the bisphenol compound has a chemical structure general formula shown in formula (IV):

[0020]

[0021]

[0022] In formula (IV), R 12 selected from ether bond, cyclohexyl, fluorenyl, phenyl, biphenyl;

[0023] The monophenol with bulky side group has a general chemical structure shown in formula (V):

[0024]

[0025] In formula (V), R 13 is an alkyl or aralkyl group with carbon number of 4-8, including but not limited to tert-butyl, p-t-octyl, cycloalkyl, phenyl, o-methylphenyl.

[0026] As some embodiments of the present application, the aldehyde compound is formaldehyde aqueous solution or paraformaldehyde.

[0027] As some embodiments of the present application, the basic catalyst is a compound that can generate phenolate from phenolic hydroxyl group, including but not limited to sodium carbonate, potassium carbonate, sodium hydroxide, potassium hydroxide, trimethylamine, triethylamine.

[0028] As some embodiments of the present application, the phosphorus-containing compound is selected from 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (DOPO) and diphenyl phosphine oxide (DPO).

[0029] As some embodiments of the present application, the first solvent is selected from any one or two of ethanol, isopropanol, n-butanol, propylene glycol monomethyl ether, ethylene glycol monomethyl ether, acetone, butanone, methyl isobutyl ketone.

[0030] As some embodiments of the present application, the molar ratio of naphthol, monophenol with bulky side group and bisphenol compound is (0.3-1):(0.1-0.5):1, and the molar amount of aldehyde compound is 2.0-2.9 times of the molar amount of phenolic hydroxyl group.

[0031] As some embodiments of the present application, the hydroxymethylation reaction is carried out at 50-80℃, and in order to increase the solubility of materials and the reaction effect, an appropriate amount of alcohol solvent can be added to the reaction materials, such as ethanol, n-propanol, n-butanol, n-pentanol, propylene glycol monomethyl ether, ethylene glycol monomethyl ether, propylene glycol, ethylene glycol.

[0032] As some embodiments of the present application, in step S2, the etherification reaction is a reaction of the hydroxymethyl compound after neutralization reaction with primary alcohol at 70-110℃, and the temperature of the dealcoholization reaction is 160-185℃.

[0033] In addition, in order to achieve the above-mentioned purpose, the present application also provides a resin composition for copper-clad plate, which comprises the following components by weight:

[0034] 100 parts of a multifunctional epoxy resin, 16-45 parts of an active ester curing agent, 93-162 parts of a high-heat-resistant low-dielectric multi-aromatic ring phosphorus-containing phenolic curing agent, 0.63-7.0 parts of an accelerator, and 85-133 parts of a filler.

[0035] As some embodiments of the present application, the multifunctional epoxy resin is a resin compound containing three or more epoxy groups, including but not limited to any one or more of a phenol-type novolac epoxy resin, a dicyclopentadiene phenol-type epoxy resin, a bisphenol A-type novolac epoxy resin, a biphenyl phenol-type epoxy resin, an o-cresol novolac epoxy resin, an aralkyl phenol epoxy resin, a phenol benzaldehyde epoxy resin, and a tetraphenyl ethane epoxy resin.

[0036] The active ester curing agent is a compound having an active ester group.

[0037] As some embodiments of the present application, the accelerator includes but is not limited to 4-dimethylaminopyridine, 2-methylimidazole, 1-benzyl-2-methylimidazole, 2-ethyl-4-methylimidazole, 2-ethylimidazole, 2-ethyl-4-methylimidazole, and other imidazoles; 2-(dimethylaminomethyl)phenol and other tertiary amines; triphenylphosphine and other phosphines.

[0038] As some embodiments of the present application, the filler includes but is not limited to silicon dioxide, montmorillonite, magnesium oxide, aluminum oxide, mica powder, barium sulfate, kaolin, silicon nitride, boron nitride, zirconium oxide, aluminum nitride, graphite, titanium dioxide, talc, and iron oxide.

[0039] As some embodiments of the present application, the resin composition for copper-clad plates further includes a second solvent, which includes but is not limited to acetone, butanone, cyclohexanone, methyl isobutyl ketone, toluene, propylene glycol monomethyl ether, and propylene glycol methyl ether acetate, and can be selected from one or two of them.

[0040] As some embodiments of the present application, the high-heat-resistant low-dielectric multi-aromatic ring phosphorus-containing phenolic curing agent has a phosphorus content of 8.0-9.2%, and the amount of the phosphorus-containing compound is determined according to the phosphorus content.

[0041] In addition, to achieve the above-mentioned purpose, the present application also provides the use of the resin composition for copper-clad plates in the preparation of high-heat-resistant low-dielectric epoxy resin-based copper-clad plates, and the preparation method of the high-heat-resistant low-dielectric epoxy resin-based copper-clad plates is as follows:

[0042] S1. The resin composition for copper-clad plates is configured into a resin glue solution, and then a glass fiber cloth is arranged in the resin glue solution for impregnation, taken out, hung at room temperature to remove most of the solvent, and placed in an oven at a temperature of 130-170°C for baking for 1-10 min to prepare a high-heat-resistant low-dielectric epoxy resin-based semi-cured sheet;

[0043] S2. The several layers of prepreg are laminated and copper foils are attached on both sides, and then placed in a vacuum hot press, with the temperature raised from room temperature to 170℃ at a rate of 3℃ / min, the pressure raised from 0.5MPa to 4MPa at a rate of 0.1MPa / 1min, vacuumed to within 50torr, and kept under pressure for 1-2h, then the temperature is raised to 180-210℃ and kept under pressure for 4-8h, the pressure is released and the product is naturally cooled, thus the high heat resistance and low dielectric constant epoxy resin-based copper clad plate is obtained.

[0044] Compared with the prior art, the present application has the following advantages:

[0045] (1) The high heat resistance and low dielectric constant multi-aromatic ring phosphorus-containing phenolic curing agent skeleton structure of the present application contains bulky side benzene ring structure, naphthalene ring structure and bisphenol structure. The bulky side benzene ring structure can increase the free volume of the molecular structure, reduce the polarizability, and reduce the dielectric constant and dielectric loss of the phosphorus-containing phenolic curing agent. The naphthalene ring structure has high rigidity, which can provide good heat resistance and mechanical properties. The bisphenol compound can provide sufficient crosslinking structure, which also helps to provide good heat resistance and mechanical properties. The biphenyl, phenyl and cyclohexane groups on the bisphenol compound can also improve the dielectric properties. Through the organic combination of the three structure units, the rigidity of the phosphorus-containing phenolic curing agent can be balanced, and cracks or cracks in the cured product can be avoided due to excessive rigidity during the curing process. At the same time, the naphthalene ring and bisphenol fluorene structures can improve the resin carbon residue and promote the condensate phase flame retardation.

[0046] (2) The resin composition for copper clad plate of the present application contains high heat resistance and low dielectric constant multi-aromatic ring phosphorus-containing phenolic curing agent. The resin composition for copper clad plate has the performance characteristics of the high heat resistance and low dielectric constant multi-aromatic ring phosphorus-containing phenolic curing agent. The resin composition for copper clad plate of the present application also contains a multi-functional epoxy resin, which has excellent comprehensive performance. The resin composition for copper clad plate of the present application also contains an active ester curing agent, which does not produce polar hydroxyl groups during the curing process, further realizing the low dielectric properties of the resin composition.

[0047] (3) The copper clad plate prepared from the resin composition for copper clad plate of the present application has the performance characteristics of the resin composition for copper clad plate of the present application. The obtained copper clad plate has excellent comprehensive performance: the dielectric constant is ≤3.86 and the dielectric loss is ≤0.0078 at 10GHz; the glass transition temperature is ≥185℃, the plate has good toughness, and the flame retardation performance reaches UL94 V-0 level.

[0048] (4) The preparation process of the present application is easy to operate. The high heat resistance and low dielectric constant multi-aromatic ring phosphorus-containing phenolic curing agent and the resin composition for copper clad plate prepared by the present application are suitable for high-performance printed circuit board field and have strong practicality. DETAILED DESCRIPTION

[0049] Preparation of the first part of high heat resistance low dielectric multi-aromatic ring phosphorus-containing phenolic curing agent (Example 1-1~1-3)

[0050] Example 1-1

[0051] In a four-necked flask equipped with a mechanical stirrer, a thermometer, nitrogen, and a reflux condenser, 200 parts by mass of water, 390 parts by mass of ethanol, 42.4 parts by mass of sodium hydroxide, 172.8 parts by mass of paraformaldehyde, 50.4 parts by mass of α-naphthol, 61.8 parts by mass of p-octylphenol, and 268 parts by mass of bisphenol Z were sequentially added, and the mixture was stirred and heated to 70°C for 6 hours. After the reaction, the mixture was neutralized by adding hydrochloric acid, and 1135 parts by mass of ethanol was added and reacted at 72°C for 5 hours. Then, the mixture was washed with water at 65~75°C, and the water phase was removed from the upper layer. The washing operation was repeated three times. The resin layer was dissolved in ethanol, and 836.4 parts by mass of DOPO was added. The mixture was slowly heated to 170°C and stirred for 5 hours. Then, 800 parts by mass of propylene glycol methyl ether was added to obtain the high heat resistance low dielectric multi-aromatic ring phosphorus-containing phenolic curing agent of Example 1-1, which had a phosphorus content of 8.8% and a solid content of 63.1%.

[0052] Example 1-2

[0053] In a four-necked flask equipped with a mechanical stirrer, a thermometer, nitrogen, and a reflux condenser, 220 parts by mass of water, 425 parts by mass of ethanol, 56 parts by mass of sodium hydroxide, 191.7 parts by mass of paraformaldehyde, 72 parts by mass of α-naphthol, 51 parts by mass of 4-phenylphenol, and 268 parts by mass of bisphenol Z were sequentially added, and the mixture was stirred and heated to 65°C for 7 hours. After the reaction, the mixture was neutralized by adding hydrochloric acid, and 2031 parts by mass of n-butanol was added and reacted at 100°C for 4 hours by using a water separator. Then, the mixture was washed with water at 70~80°C, and the water phase was removed from the lower layer. The washing operation was repeated three times. The resin layer was dissolved in ethanol, and 849.6 parts by mass of DOPO was added. The mixture was slowly heated to 170°C and stirred for 5 hours. Then, 847 parts by mass of ethylene glycol methyl ether was added to obtain the high heat resistance low dielectric multi-aromatic ring phosphorus-containing phenolic curing agent of Example 1-1, which had a phosphorus content of 8.6% and a solid content of 62.7%.

[0054] Example 1-3

[0055] In a four-port reaction flask equipped with a mechanical stirrer, thermometer, nitrogen, reflux condenser, 150 parts by mass of water, 473 parts by mass of n-butanol, 39.2 parts by mass of sodium hydroxide, 175.8 parts by mass of paraformaldehyde, 108 parts by mass of α-naphthol, 34 parts by mass of 4-phenylphenol, and 262.8 parts by mass of bisphenol fluorene were sequentially added, and the mixture was stirred uniformly and then raised to 60°C for 8 hours of reaction. After the reaction was completed, the reaction mixture was neutralized by adding an appropriate amount of hydrochloric acid, 1756 parts by mass of n-butanol was added, and the mixture was refluxed at 105°C for 3 hours using a water separator. Then, an appropriate amount of water was added to wash the resin at 70-80°C, and the water phase was removed from the lower layer. The washing operation was repeated three times. The upper resin layer was taken, 773.2 parts by mass of DOPO was added, and the temperature was slowly raised to 175°C for 6 hours of stirring. Then, 700 parts by mass of ethylene glycol methyl ether and 10 parts by mass of butanone were added to obtain the high-heat-resistant low-dielectric multiring phosphorus-containing phenolic aldehyde curing agent of Example 1-1, which had a phosphorus content of 8.3% and a solid content of 62.5%.

[0056] Preparation of the second part of the high-heat-resistant low-dielectric epoxy resin-based copper-clad plate (Examples 2-4)

[0057] The steps for preparing the resin composition for copper-clad plate and the high-heat-resistant low-dielectric epoxy resin-based copper-clad plate are as follows:

[0058] S1: 100 parts by mass of multifunctional epoxy resin, 16-45 parts by mass of active ester curing agent, 93-162 parts by mass of high-heat-resistant low-dielectric multiring phosphorus-containing phenolic aldehyde curing agent, 0.63-7.0 parts by mass of accelerator, 85-133 parts by mass of filler, and an appropriate amount of second solvent were uniformly mixed to prepare a resin glue solution. The total mass of the multifunctional epoxy resin, high-heat-resistant low-dielectric multiring phosphorus-containing phenolic aldehyde curing agent, accelerator, and filler accounted for 64%-66% of the mass of the resin composition for copper-clad plate. A glass fiber cloth was immersed in the resin glue solution, taken out, hung at room temperature to remove most of the solvent, and then placed in an oven at a temperature of 130-170°C for 1-10 minutes of baking to prepare a high-heat-resistant low-dielectric epoxy resin-based prepreg;

[0059] S2: A plurality of prepregs were laminated, and copper foils were attached to both sides. The laminated structure was placed in a vacuum hot press, and the temperature was raised from room temperature to 170°C at a rate of 3°C / min. The pressure was raised from 0.5 MPa to 4 MPa at a rate of 0.1 MPa / 1 min, the vacuum was drawn to within 50 torr, and the pressure was maintained for 1-2 hours. Then, the temperature was raised to 180-210°C, and the pressure was maintained for 4-8 hours. The pressure was released, and the structure was naturally cooled to obtain a high-heat-resistant low-dielectric epoxy resin-based copper-clad plate.

[0060] Table 1 shows the component allocation and performance parameters in Examples 2-4. The component amounts in Table 1 are in parts by mass.

[0061] A1: high heat resistance and low dielectric phosphorus-containing phenolic curing agent with multi-aromatic rings prepared in Example 1-1;

[0062] A2: high heat resistance and low dielectric phosphorus-containing phenolic curing agent with multi-aromatic rings prepared in Example 1-2;

[0063] A3: high heat resistance and low dielectric phosphorus-containing phenolic curing agent with multi-aromatic rings prepared in Example 1-3;

[0064] B1: DCPD epoxy resin 7200H;

[0065] B2: biphenyl epoxy resin DC3000H;

[0066] C: active ester curing agent DFE617;

[0067] D: 2-ethyl-4-methylimidazole;

[0068] E: silicon dioxide;

[0069] F: butanone.

[0070] In Table 1, the relevant standards used for the technical indicators are as follows:

[0071] Glass transition temperature Tg: determined by dynamic mechanical analysis (DMA) according to the DMA method specified in IPC-TM-650 2.4.24.4;

[0072] Carbon residue: tested by thermogravimetric analysis (TGA) under a nitrogen atmosphere at a heating rate of 10°C / min;

[0073] Dielectric constant Dk and dielectric loss Df: tested by SPDR method according to the method specified in IEC 61189-2-721 to obtain 10GHz data;

[0074] Thermal delamination time T300: determined according to the method specified in IPC-TM-650 2.4.24.1;

[0075] Panel toughness: a falling weight impact tester is used, the impact tester has a falling weight height of 40cm and a falling weight mass of 1kg. The toughness is evaluated as follows: the clearer and thinner the cross at the impact site, the better the product toughness, indicated by ; the more blurred and larger the cross, the worse the product toughness and the greater the brittleness, indicated by ; the cross is between clear and blurred, indicating that the product toughness is general, indicated by ;

[0076] Immersion soldering time with copper foil: a panel sample with a size of 100mm x 100mm and double-sided copper foil is immersed in 288°C soldering tin, and the average value of the time when delamination and board explosion do not occur is taken;

[0077] UL 94 flame retardant performance test: according to UL94 vertical burning test method.

[0078] Comparative Example

[0079] 100 parts by mass of DCPD epoxy resin 7200H, 138 parts by mass of phosphorus-containing phenolic curing agent (DOW 92741, phosphorus content about 9.0%, solid content 57%), 34 parts by mass of active ester curing agent DFE617, 2.7 parts by mass of 2-methylimidazole, 100 parts by mass of silica, 168 parts by mass of butanone were prepared into a resin sizing solution with a mass percentage content of 65%±1%, then the glass cloth was immersed, and the glass cloth immersed with the resin sizing solution was baked at a temperature of 130℃-170℃ for 1-10 min to prepare a low-loss prepreg;

[0080] 6 pieces of low-loss prepreg were stacked and copper foil was attached on both sides, and placed in a vacuum hot press, the temperature was raised from room temperature to 175℃ at a rate of 3℃ / min, the pressure was raised from 0.5MPa to 4MPa at a rate of 0.1MPa / 1min, vacuum was drawn to within 50torr, and the pressure was kept for 1-2h, then the temperature was raised to 190℃ and kept for 5h, the pressure was released and naturally cooled, to prepare a copper-clad plate of Comparative Example 1.

[0081] Table 1:

[0082]

[0083]

[0084] As can be seen from Table 1, the copper-clad plate prepared by using the high-heat-resistant low-dielectric multi-aromatic ring phosphorus-containing phenolic curing agent and the resin composition for copper-clad plate of the present application has good dielectric properties, heat resistance, flame retardant properties and toughness. The copper-clad plate prepared by using the commercially available phosphorus-containing phenolic curing agent of Comparative Example 1 has poor heat resistance and dielectric properties.

[0085] Comparative Example 2-4, it can be seen that the high-heat-resistant low-dielectric multi-aromatic ring phosphorus-containing phenolic curing agent of the present application can achieve UL94 V-0 flame retardant grade of the plate at a lower phosphorus content (<9%), can effectively improve the glass transition temperature of the plate to above 185℃, improve the dielectric loss to ≤0.0078, and at the same time can maintain good toughness of the plate.

Claims

1. A high heat-resistant, low-dielectric polyaromatic phosphorus-containing phenolic curing agent, characterized in that, The high heat-resistant, low-dielectric polyaromatic phosphorus-containing phenolic curing agent includes a naphthalene ring structure, a bisphenol structure, a benzene ring structure with large-volume side groups, and a phosphorus structure. The high heat-resistant, low dielectric polyaromatic phosphorus-containing phenolic curing agent comprises the structural units shown in (Ⅰ), (Ⅱ), and (Ⅲ) below: In formula (Ⅰ), R1 is any one of ether, cyclohexyl, fluorenyl, phenyl, and biphenyl; R2 and R4 are selected from R3 and R5 are selected from methylene, In formula (II), R6 is selected from R7 and R8 are selected from methylene, Furthermore, R7 and R8 are not simultaneously... or ; In formula (Ⅲ), R9, R 10 Selected from methylene, And R9, R 10 Not at the same time or ; R 11 It is an alkyl or aralkyl group with 4 to 8 carbon atoms.

2. The preparation method of the high heat-resistant, low dielectric polyaromatic ring phosphorus-containing phenolic curing agent according to claim 1, R 11 Selected from tert-butyl, p-tert-octyl, cycloalkyl, phenyl, and o-methylphenyl.

3. The preparation method of a high heat-resistant, low-dielectric polyaromatic ring phosphorus-containing phenolic curing agent according to claim 1 or 2, characterized in that, Includes the following steps: S1. α-Naphthol, monophenols with large side groups, bisphenol compounds, and aldehyde compounds are reacted with an alkaline catalyst to obtain hydroxymethyl compounds; S2. The hydroxymethyl compound is subjected to neutralization reaction, etherification reaction and purification steps in sequence, and then subjected to a dealcoholization reaction with a phosphorus-containing compound. The resulting product is then diluted with the first solvent to a 60%~65% resin solution, which is the high heat-resistant, low dielectric polyaromatic ring phosphorus-containing phenolic curing agent.

4. The preparation method of a high heat-resistant, low-dielectric polyaromatic ring phosphorus-containing phenolic curing agent according to claim 3, characterized in that, The bisphenol compound has the general chemical structure shown in formula (Ⅳ): （Ⅳ） In equation (Ⅳ), R 12 Selected from ether bonds, cyclohexyl, fluorenyl, phenyl, and biphenyl; The monophenol with large-volume side groups has the general chemical structural formula shown in formula (V): （Ⅴ） In equation (V), R 13 It is an alkyl or aralkyl group having 4 to 8 carbon atoms; R 13 Selected from tert-butyl, p-tert-octyl, cycloalkyl, phenyl, and o-methylphenyl.

5. The preparation method of a high heat-resistant, low-dielectric polyaromatic ring phosphorus-containing phenolic curing agent according to claim 3, characterized in that, The molar ratio of α-naphthol, monophenols with large side groups, and bisphenol compounds is (0.3~1):(0.1~0.5):1; the molar amount of aldehyde compounds is 2.0~2.9 times the molar amount of phenolic hydroxyl groups.

6. The preparation method of a high heat-resistant, low-dielectric polyaromatic ring phosphorus-containing phenolic curing agent according to claim 3, characterized in that, In step S2, the etherification reaction is a reaction between a hydroxymethyl compound and a primary alcohol at 70-110°C after neutralization; the dealcoholization reaction is carried out at 160-185°C.

7. A resin composition for copper-clad laminates, characterized in that, Includes the following components by weight: 100 parts of multifunctional epoxy resin, 16-45 parts of reactive ester curing agent, 93-162 parts of high heat-resistant, low dielectric polyaromatic phosphorus-containing phenolic curing agent as described in claim 1 or 2, 0.63-7.0 parts of accelerator, and 85-133 parts of filler.

8. The resin composition for copper-clad laminates according to claim 7, characterized in that, The multifunctional epoxy resin is a resin compound containing three or more epoxy groups, selected from any one or more of the following: phenolic epoxy resin, dicyclopentadiene phenolic epoxy resin, bisphenol A phenolic epoxy resin, biphenyl phenolic epoxy resin, o-cresol phenolic epoxy resin, aralkyl phenolic epoxy resin, phenol benzaldehyde epoxy resin, and tetraphenol ethane epoxy resin. The active ester curing agent is a compound with active ester groups.

9. The resin composition for copper-clad laminates according to claim 7, characterized in that, High heat-resistant, low dielectric polyaromatic phenolic curing agent with phosphorus content of 8.0~9.2%.

10. The application of the resin composition for copper-clad laminates according to any one of claims 7-9 in the preparation of high heat-resistant, low-dielectric epoxy resin-based copper-clad laminates, characterized in that, The preparation method of the high heat-resistant, low-dielectric epoxy resin-based copper clad laminate is as follows: S1. Prepare a resin solution by using a resin composition for copper clad laminate, then place glass fiber in the resin solution for immersion and remove it, hang it at room temperature to remove most of the solvent, and then place it in an oven at 130℃~170℃ for 1~10min to obtain a high heat-resistant, low dielectric epoxy resin-based semi-cured sheet. S2. Several layers of semi-cured sheets are stacked together, and copper foil is attached to both sides. The sheets are placed in a vacuum hot press and heated from room temperature to 170°C at a rate of 3°C / min. The pressure is increased from 0.5MPa to 4MPa at a rate of 0.1MPa / 1min. The vacuum is then reduced to less than 50 torr and the sheets are kept pressed for 1-2 hours. The temperature is then increased to 180-210°C and the pressure is kept constant for 4-8 hours. The pressure is then released and the sheets are allowed to cool naturally to obtain the high heat-resistant, low dielectric epoxy resin-based copper-clad laminate.

Images