High-activity double-bond naphthalene ring-containing halogen-free flame-retardant epoxy resin solution, resin composition for copper-clad plate and preparation method of resin composition

Abstract

The invention discloses a high-activity double-bond naphthalene ring type halogen-free flame-retardant epoxy resin solution and a preparation method thereof. The high-activity double-bond naphthalene ring type halogen-free flame-retardant epoxy resin solution is characterized in that high-activity double-bond naphthalene ring type halogen-free flame-retardant epoxy resin in the solution has a chemical structure fragment shown in (I); the preparation method comprises the following steps: generating naphthalene ring type halogen-free flame-retardant epoxy resin from 1, 4-naphthoquinone, novolac epoxy resin, DOPO and cyclohexanone under the action of an ethyl triphenyl phosphine acetate catalyst, then adding acrylic acid, reacting under the action of a catalyst trimethyl benzyl ammonium chloride and the like, and then adding butanone, thereby obtaining the high-activity double-bond naphthalene ring type halogen-free flame-retardant epoxy resin solution. Furthermore, the invention also discloses a resin composition for a copper-clad plate, which is prepared by mixing a high-activity double-bond naphthalene ring type halogen-free flame-retardant epoxy resin solution, hydrocarbon resin, special bismaleimide resin, spherical silica powder, an initiator and toluene. The antenna is good in performance, and can meet the requirements of high-frequency and high-speed 5G transmitting base stations, artificial intelligence carrier plates and the like. (I)

Description

TECHNICAL FIELD

[0001] The present application belongs to the technical field of synthesis modification and application of resin for copper-clad plate, and relates to a halogen-free flame-retardant epoxy resin solution containing a naphthalene ring type with high active double bonds, a resin composition for copper-clad plate and a preparation method thereof. The halogen-free flame-retardant epoxy resin solution containing a naphthalene ring type with high active double bonds and the resin composition for copper-clad plate are suitable for the preparation of copper-clad plates, and the printed circuit boards manufactured by the copper-clad plates can be widely used in various electronic products such as transmission base stations, artificial intelligence boards, computers, new energy vehicles and mobile communications. BACKGROUND

[0002] Copper-clad plate is a basic material for electronic industry, mainly used for processing and manufacturing printed circuit boards (PCB), and widely used in various electronic products such as transmission base stations, artificial intelligence boards, computers, new energy vehicles and mobile communications. In particular, it is applied to copper-clad plates required for high frequency and high speed such as 5G transmission base stations and artificial intelligence boards.

[0003] In the prior art, the resin for copper-clad plate tends to use low-dielectric and low-dielectric-loss hydrocarbon resin. However, the existing hydrocarbon resin has poor flame retardancy, and the chain segment is flexible, which has poor adhesion to the base material (peeling strength <1 N / mm). The copper-clad plate prepared therefrom has insufficient flame retardancy, and also has the disadvantages of poor heat resistance, low glass transition temperature, insufficient rigidity and large thermal expansion coefficient. It cannot meet the requirements of the copper-clad plate on the comprehensive performance of the resin, and greatly limits its application in copper-clad plates.

[0004] In the prior art, the resin for copper-clad plate is generally used in combination with polyphenyl ether and hydrocarbon resin to improve the comprehensive performance of the plate. However, the overall flame retardancy, adhesion to the base material and heat resistance (Tg glass transition temperature) are slightly insufficient. For example, CN120484481A discloses a resin composition and an article, which uses polyphenyl ether and hydrocarbon resin in combination to modify the performance of the copper-clad plate. CN120535952A discloses a low-dielectric resin glue solution for high-frequency and high-speed copper-clad plate, a preparation method and application thereof, which uses polyphenyl ether and hydrocarbon resin in combination, and also uses polyimide resin to improve the heat resistance. Through retrieval, no related literature has been found in the prior art that uses a halogen-free flame-retardant epoxy resin containing a naphthalene ring type with high active double bonds to improve the comprehensive performance of the copper-clad plate resin. SUMMARY

[0005] The present application aims to overcome the deficiencies in the prior art, and provides a high-activity double-bond naphthalene ring type halogen-free flame-retardant epoxy resin solution, a resin composition for copper-clad plate, and a preparation method thereof. The present application provides a novel double-bond naphthalene ring type halogen-free flame-retardant epoxy resin and a resin composition for copper-clad plate to improve the comprehensive performance of hydrocarbon resin, and is applied to the high-frequency and high-speed copper-clad plate industry. By using the present application, the technical problems of poor heat resistance (Tg<170℃), poor adhesion to glass fiber substrate (peeling strength<1N / mm), and poor flame retardancy of the hydrocarbon resin copper-clad plate in the prior art can be solved.

[0006] To solve the above technical problems, the technical solution of the present application mainly comprises: using a high-activity double-bond naphthalene ring type halogen-free flame-retardant epoxy resin solution and a resin composition for copper-clad plate. The high-activity double-bond naphthalene ring type halogen-free flame-retardant epoxy resin solution is prepared by adding 1,4 naphthalenequinone, phenolic epoxy resin, DOPO (which is an abbreviation of 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide), and cyclohexanone to a reactor under the action of an ethyltriphenylphosphonium acetate catalyst to generate a naphthalene ring type halogen-free flame-retardant epoxy resin, and then adding acrylic acid and a trimethylbenzylammonium chloride catalyst to generate a high-activity double-bond naphthalene ring type halogen-free flame-retardant epoxy resin solution. The resin composition for copper-clad plate is composed of the high-activity double-bond naphthalene ring type halogen-free flame-retardant epoxy resin solution, hydrocarbon resin, special bismaleimide resin, spherical silicon powder, initiator, and toluene.

[0007] The content of the present application is a high-activity double-bond naphthalene ring type halogen-free flame-retardant epoxy resin solution, which is characterized in that the high-activity double-bond naphthalene ring type halogen-free flame-retardant epoxy resin in the solution has a chemical structure fragment as shown in (I): (I) In formula (I), R is an epoxy group or a double-bond-containing group, and n: 2-8.

[0008] In the content of the present application, the preparation method of the high-activity double-bond naphthalene ring type halogen-free flame-retardant epoxy resin solution is characterized by comprising the following steps: a. 80-100 parts by mass of 1,4 naphthalenequinone, 100-120 parts by mass of cyclohexanone, and 120-140 parts by mass of DOPO (which is an abbreviation of 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide) are added to a reactor, and stirring is performed to heat to 80℃, so that the 1,4 naphthalenequinone and DOPO are dissolved (completely); b. The temperature is controlled at 78-82℃, 88-92℃, and 98-102℃, and stirring is performed for 1 hour, 1 hour, and 2 hours, respectively; c. Add 500-600 parts by mass of phenolic epoxy resin, 0.1-0.4 parts by mass of ethyl triphenyl phosphonium acetate catalyst, control the temperature at 140-150°C for 1-2 hours, increase the temperature, control the temperature at 160-175°C for 2-4 hours; d. Then, decrease the temperature to 78-82°C, add 0.1-0.4 parts by mass of hydroquinone polymerization inhibitor into the reactor, mix 140-150 parts by mass of acrylic acid and 0.5-1.0 parts by mass of trimethylbenzyl ammonium chloride uniformly, and then place them into a constant pressure dropping funnel, and drop them into the reactor at a temperature of 78-82°C for 0.5 hours; e. Control the temperature at 78-82°C for 2 hours, and then control the temperature at 88-92°C for 2-4 hours, and test the acid value, wherein the acid value meets 40-50 mgKOH / 1g resin; f. When the acid value meets the requirement, decrease the temperature, add 380-420 parts by mass of butanone solvent, and stir uniformly to obtain the high active double bond naphthalene ring type halogen-free flame-retardant epoxy resin solution.

[0009] In the preparation method of the high active double bond naphthalene ring type halogen-free flame-retardant epoxy resin solution, the solid content of the prepared high active double bond naphthalene ring type halogen-free flame-retardant epoxy resin solution is 59.0-61.0%, the viscosity is 10000-16000mpas, the phosphorus content is 1.8-2.0%, and the double bond equivalent is 400-450g / mol.

[0010] In the preparation method of the high active double bond naphthalene ring type halogen-free flame-retardant epoxy resin solution, the product production providing enterprise and model (brand) of the phenolic epoxy resin can be EMTE638 of Shandong Aimonter New Material Co., Ltd.

[0011] The product production providing enterprise and model (brand) of the ethyl triphenyl phosphonium acetate can be: reagent of Chengdu Kolon Chemicals Co., Ltd.

[0012] The test method of the acid value is: according to the national standard GB / T 7304-2014.

[0013] The definition of "solid content" described herein is: The percentage of the mass of non-volatiles in the total mass of 1g sample after 1 hour of baking in an oven at 160°C.

[0014] Another aspect of the present invention is a resin composition for copper-clad laminates, characterized in that the resin composition for copper-clad laminates comprises 50-60 parts by weight of a halogen-free flame-retardant epoxy resin solution containing highly active double-bonded naphthalene rings, 90-110 parts by weight of a hydrocarbon resin, 50-60 parts by weight of a special bismaleimide resin, 80-120 parts by weight of spherical silica powder, 0.1-0.4 parts by weight of an initiator, and 60-80 parts by weight of toluene.

[0015] In another aspect of this invention: the highly reactive double-bonded naphthalene ring-type halogen-free flame-retardant epoxy resin solution has the chemical structural segment shown in (Ⅰ): (I) In equation (I): R is Epoxy groups or Contains double bond groups, n: 2-8; The special bismaleimide resin is a compound having the following chemical structural formula: ; The hydrocarbon resin is either polystyrene-butadiene resin or polystyrene resin. The initiator is either dicumyl peroxide or benzoyl peroxide.

[0016] In another aspect of this invention: The manufacturer and model of the special bismaleimide resin is: DFE268 of Sichuan Dongcai Technology Group Co., Ltd. The manufacturer and model of the polystyrene-butadiene resin is: DFE403 of Sichuan Dongcai Technology Group Co., Ltd. The name and model of the polystyrene resin manufacturer are: DFE405 of Sichuan Dongcai Technology Group Co., Ltd. The manufacturer and model of the spherical silica powder is: NOVOPOWDER DQ, produced by Jiangsu Lianrui New Materials Co., Ltd.

[0017] In another aspect of the present invention, the preparation method of the halogen-free flame-retardant epoxy resin solution containing highly active double-bonded naphthalene rings includes the following steps: a. Add 80-100 parts by weight of 1,4-naphthoquinone, 100-120 parts by weight of cyclohexanone, and 120-140 parts by weight of DOPO (an abbreviation for 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide) to the reactor, stir and heat to 80°C to dissolve (completely) 1,4-naphthoquinone and DOPO. b. Stir the reaction at temperatures of 78–82℃, 88–92℃, and 98–102℃ for 1 hour, 1 hour, and 2 hours respectively; c. Add 500-600 parts by weight of phenolic epoxy resin and 0.1-0.4 parts by weight of ethyltriphenylphosphine acetate catalyst, and react at 140-150℃ for 1-2 hours. Then raise the temperature and react at 160-175℃ for 2-4 hours. d. Then cool down to 78-82℃, add 0.1-0.4 parts by weight of hydroquinone polymerization inhibitor into the reactor, mix 140-150 parts by weight of acrylic acid and 0.5-1.0 parts by weight of trimethylbenzylammonium chloride evenly and place it into a constant pressure dropping funnel, and drip it into the reactor at a temperature of 78-82℃ over 0.5 hours; e. Control the temperature at 78-82℃ for 2 hours, then control the temperature at 88-92℃ for 2-4 hours, and test the acid value. The acid value should meet the requirement of 40-50 mg KOH / 1g resin. f. When the acid value reaches the required level, cool down and add 380-420 parts by weight of butanone solvent, stir evenly, and a halogen-free flame-retardant epoxy resin solution containing highly active double-bonded naphthalene rings is obtained.

[0018] The method for preparing the halogen-free flame-retardant epoxy resin solution containing highly active double-bonded naphthalene rings is characterized in that: the prepared halogen-free flame-retardant epoxy resin solution containing highly active double-bonded naphthalene rings has a solid content of 59.0-61.0%, a viscosity of 10000-16000 mPa·s, a phosphorus content of 1.8-2.0%, and a double bond equivalent of 400-450 g / mol.

[0019] The method for preparing the halogen-free flame-retardant epoxy resin solution containing highly active double-bonded naphthalene rings is characterized in that: the product manufacturer and model (brand) of the phenolic epoxy resin can be EMTE638 from Shandong Aimont New Material Co., Ltd.

[0020] Compared with the prior art, the present invention has the following features and beneficial effects: (1) This invention uses a combination of highly active double-bonded naphthalene ring type halogen-free flame-retardant epoxy resin and hydrocarbon resin. Due to the phosphorus element in the highly active double-bonded naphthalene ring type halogen-free flame-retardant epoxy resin, the copper-clad laminate achieves V0 flame retardancy. The introduction of naphthalene ring can improve heat resistance (Tg increases). Due to the introduction of a small amount of hydroxyl groups, the adhesion between the resin and the glass fiber substrate is greatly improved (peel strength > 1 N / mm). (2) By using the present invention, the introduction of special bismaleimide resin can also greatly improve the heat resistance of copper clad laminate, so that Tg > 210℃. (3) The resin cured product prepared by using the high-activity double-bonded naphthalene ring type halogen-free flame-retardant epoxy resin (solution) of the present invention has a Tg ≥ 210℃ (high heat resistance), peel strength ≥ 1 N / mm (high adhesion), and flame retardancy reaches V0 (high flame retardancy). At the same time, it has the low dielectric (< 2.8) and low dielectric loss (< 0.001) of hydrocarbon resin, which can meet the needs of high-frequency and high-speed 5G base stations, artificial intelligence carrier boards, etc. The high-activity double-bonded naphthalene ring type halogen-free flame-retardant epoxy resin (solution) and copper-clad laminate resin composition provided by the present invention can meet the needs of high-frequency and high-speed 5G base stations, artificial intelligence carrier boards, etc., and meet the performance requirements of high-end copper-clad laminate resin. (4) The preparation process of the product of the present invention is simple, easy to operate, and highly practical. Detailed Implementation

[0021] The embodiments given below are intended to further illustrate the present invention, but should not be construed as limiting the scope of protection of the present invention. Any non-essential improvements and adjustments made to the present invention by those skilled in the art based on the above description of the present invention still fall within the scope of protection of the present invention.

[0022] Examples 1-1 to 1-8: The preparation method of a halogen-free flame-retardant epoxy resin solution containing highly reactive double-bonded naphthalene rings includes the following steps: a. Add 80-100 parts by weight of 1,4-naphthoquinone, 100-120 parts by weight of cyclohexanone, and 120-140 parts by weight of DOPO (an abbreviation for 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide) to the reactor, stir and heat to 80°C to completely dissolve 1,4-naphthoquinone and DOPO; b. Stir the reaction at temperatures of 78–82℃ (i.e., 80±2℃), 88–92℃ (i.e., 90±2℃), and 98–102℃ (i.e., 100±2℃) for 1 hour, 1 hour, and 2 hours respectively. c. Add 500-600 parts by weight of phenolic epoxy resin and 0.1-0.4 parts by weight of ethyltriphenylphosphine acetate catalyst, and react at 140-150℃ for 1-2 hours. Then raise the temperature and react at 160-175℃ for 2-4 hours. d. Then cool down to 78-82℃ (i.e. 80±2℃), add 0.1-0.4 parts by weight of hydroquinone polymerization inhibitor into the reactor, mix 140-150 parts by weight of acrylic acid and 0.5-1.0 parts by weight of trimethylbenzylammonium chloride evenly and place it into a constant pressure dropping funnel, and drip it into the reactor at a temperature of 78-82℃ over 0.5 hours; e. Control the temperature at 78~82℃ (i.e. 80±2℃) for 2 hours, then control the temperature at 88~92℃ (i.e. 90±2℃) for 2~4 hours, and test the acid value. The acid value should meet the requirement of 40~50mgKOH / 1g resin. f. When the acid value reaches the required level, cool down and add 380-420 parts by weight of butanone solvent, stir evenly, and a halogen-free flame-retardant epoxy resin solution containing highly active double-bonded naphthalene rings is obtained.

[0023] In the preparation method of the halogen-free flame-retardant epoxy resin solution containing highly active double-bonded naphthalene rings, the obtained halogen-free flame-retardant epoxy resin solution has a solid content of 59.0-61.0%, a viscosity of 10000-16000 mPa·s, a phosphorus content of 1.8-2.0%, and a double bond equivalent of 400-450 g / mol.

[0024] In the preparation method of the halogen-free flame-retardant epoxy resin solution containing highly active double-bonded naphthalene rings, the product manufacturer and model (brand) of the phenolic epoxy resin is EMTE638 from Shandong Aimont New Material Co., Ltd.; the 1,4-naphthoquinone is produced and supplied by Kawasaki Chemical Industry Co., Ltd.; and the DOPO is 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide produced and supplied by Shouguang Weidong Chemical Co., Ltd.

[0025] Examples 1-1 to 1-8 use different amounts of raw materials and process parameters, and the test data of the prepared halogen-free flame-retardant epoxy resin solutions containing highly active double-bonded naphthalene rings are shown in Table 1 below.

[0026] Table 1: Formulation amounts (raw material amounts in kg) and process parameters for preparing highly reactive double-bonded naphthalene ring-type halogen-free flame-retardant epoxy resin solutions, and test data of the obtained solutions:

[0027] Note: In Table 1: Temperature A (°C) is the specific temperature at which the temperature is controlled in step c, which is 140–150°C; Temperature B (°C) is the specific temperature at which the temperature is controlled in step c, which is 160–175°C; Reaction time M (h) is the specific time for the reaction at 140–150°C for 1–2 hours in step c; Reaction time N (h) is the specific time for the reaction at 160–175°C for 2–4 hours in step c; and Reaction time W (h) is the specific reaction time for the reaction at 88–92°C for 2–4 hours in step e.

[0028] Examples 2-1 to 2-8: A resin composition for copper-clad laminates, comprising 50-60 parts by weight of a highly active double-bonded naphthalene ring-type halogen-free flame-retardant epoxy resin solution, 90-110 parts by weight of a hydrocarbon resin, 50-60 parts by weight of a special bismaleimide resin, 80-120 parts by weight of spherical silica powder, 0.1-0.4 parts by weight of an initiator, and 60-80 parts by weight of toluene, wherein the resin composition for copper-clad laminates is prepared by mixing and stirring the above components evenly; wherein the highly active double-bonded naphthalene ring-type halogen-free flame-retardant epoxy resin solution is the highly active double-bonded naphthalene ring-type halogen-free flame-retardant epoxy resin solution prepared in Examples 1-1 to 1-8 above.

[0029] The manufacturer and model of the special bismaleimide resin is: DFE268 of Sichuan Dongcai Technology Group Co., Ltd. The hydrocarbon resin is either polystyrene-butadiene resin or polystyrene resin; The manufacturer and model of the polystyrene-butadiene resin is: DFE403 of Sichuan Dongcai Technology Group Co., Ltd. The name and model of the polystyrene resin manufacturer are: DFE405 of Sichuan Dongcai Technology Group Co., Ltd. The manufacturer and model of the spherical silica powder is: NOVOPOWDER DQ, Jiangsu Lianrui New Material Co., Ltd. The initiator is either dicumyl peroxide or benzoyl peroxide.

[0030] Examples 2-1 to 2-8 used different formulations and dosages of the above components, cured them to make test strips, and then tested their performance, as shown in Table 2 below.

[0031] Table 2: Formulation and dosage data of resin compositions for copper clad laminates in Examples 2-1 to 2-8, and performance data after curing (unit: parts by mass, specific unit: kg):

[0032] Note: "1-1" in Table 2 refers to the highly active double-bonded naphthalene ring type halogen-free flame-retardant epoxy resin solution prepared in "Example 1-1".

[0033] The sample preparation process of Examples 2-1 to 2-8 is as follows: After all component materials are mixed, they are stirred at 50±2℃ for 1 hour. After being mixed evenly, they are impregnated with electronic fiberglass cloth, the solvent is dried, and then pressed into plates. The pressing process is: 150℃ / 1h + 180℃ / 2h + 210℃ / 3h. Then the temperature is lowered, the plate is taken out, and the sample is made. The peel strength, Tg, flame retardancy, dielectric constant, and dielectric loss are tested.

[0034] In the above embodiments: unless otherwise specified, the percentage examples used are mass (weight) percentage examples or percentage examples known to those skilled in the art; unless otherwise specified, the proportions used are mass (weight) proportions; the weight parts can all be grams or kilograms.

[0035] In the above embodiments, the process parameters (temperature, time, etc.) and the values ​​of each component dosage in each step are ranges, and any point can be applied.

[0036] The technical contents of this invention and the above embodiments that are not specifically described are the same as those of the prior art, and the raw materials are all commercially available products.

[0037] The foregoing describes the basic principles and main features of the present invention, as well as its advantages. Those skilled in the art should understand that the present invention is not limited to the above embodiments. The embodiments and descriptions in the specification are merely illustrative of the principles of the present invention. Various changes and modifications can be made to the present invention without departing from its spirit and scope, and all such changes and modifications fall within the scope of the present invention as claimed. The present invention is not limited to the above embodiments; all aspects described in the present invention can be implemented and have the aforementioned good effects.

Claims

1. A halogen-free flame-retardant epoxy resin solution containing a naphthalene ring type having a high activity double bond, characterized by: The halogen-free flame-retardant epoxy resin with naphthalene ring containing high active double bond in the solution has the chemical structure fragment shown as (I): （Ⅰ） In formula (I): R is an epoxy group or a double bond-containing group, n: 2-8.

2. The method of claim 1, wherein the preparation of the high active double bond-containing naphthalene ring type halogen-free flame retardant epoxy resin solution is characterized by: The method comprises the following steps: a. 80-100 parts by mass of 1,4-naphthoquinone, 100-120 parts by mass of cyclohexanone, and 120-140 parts by mass of DOPO are added into a reactor, and stirring is performed to heat the mixture to 80°C, so that the 1,4-naphthoquinone and the DOPO are dissolved; b. The temperature is controlled at 78-82°C, 88-92°C, and 98-102°C, and stirring is performed for 1 hour, 1 hour, and 2 hours, respectively; c. 500-600 parts by mass of a phenolic epoxy resin and 0.1-0.4 parts by mass of an ethyl triphenyl phosphonium acetate catalyst are further added, the temperature is controlled at 140-150°C, and reaction is performed for 1-2 hours, the temperature is increased, the temperature is controlled at 160-175°C, and reaction is performed for 2-4 hours; d. Then, the temperature is decreased to 78-82°C, 0.1-0.4 parts by mass of hydroquinone is added into the reactor, 140-150 parts by mass of acrylic acid and 0.5-1.0 parts by mass of trimethylbenzyl ammonium chloride are uniformly mixed, and the mixture is placed into a constant-pressure dropping funnel and dropped into the reactor at a temperature of 78-82°C for 0.5 hours; e. The temperature is controlled at 78-82°C, reaction is performed for 2 hours, the temperature is controlled at 88-92°C, reaction is performed for 2-4 hours, and the acid value is tested, and the acid value meets the requirement of 40-50 mgKOH / 1g of resin; f. When the acid value meets the requirement, the temperature is decreased, 380-420 parts by mass of butanone is added, and stirring is performed to obtain the halogen-free flame-retardant epoxy resin with naphthalene ring containing high active double bond.

3. The method for preparing the halogen-free flame-retardant epoxy resin solution containing highly active double-bonded naphthalene rings according to claim 2, characterized in that: The halogen-free flame-retardant epoxy resin with naphthalene ring containing high active double bond in the solution has the chemical structure fragment shown as (I):

4. The method for preparing a halogen-free flame-retardant epoxy resin solution containing a highly active double-bonded naphthalene ring as described in claim 2 or 3, characterized in that: The product production enterprise and the model of the phenolic epoxy resin are EMTE638 of Shandong Aimonter New Material Co., Ltd.

5. A resin composition for a copper-clad plate, characterized by: The resin composition for the copper-clad plate is composed of 50-60 parts by mass of the halogen-free flame-retardant epoxy resin with naphthalene ring containing high active double bond, 90-110 parts by mass of a hydrocarbon resin, 50-60 parts by mass of a special bismaleimide resin, 80-120 parts by mass of spherical silicon powder, 0.1-0.4 parts by mass of an initiator, and 60-80 parts by mass of toluene.

6. The resin composition for a copper-clad plate according to Claim 5, characterized by: The halogen-free flame-retardant epoxy resin with naphthalene ring containing high active double bond in the solution has the chemical structure fragment shown as (I): （Ⅰ） In formula (I): R is an epoxy group or a group containing a double bond, n: 2-8; The special bismaleimide resin is a compound with the chemical structure shown as follows: ； The hydrocarbon resin is any one of a polybutadiene styrene resin and a polystyrene resin. The initiator is any one of dicumyl peroxide and benzoyl peroxide.

7. The resin composition for the copper-clad plate according to claim 5 or 6, characterized in that: The product production enterprise name and the model of the special bismaleimide resin are DFE268 of Sichuan Dongcai Science and Technology Group Co., Ltd. The product production enterprise name and the model of the polybutadiene styrene resin are DFE403 of Sichuan Dongcai Science and Technology Group Co., Ltd. The product production enterprise name and model of the polystyrene resin are DFE405 of Sichuan Dongcai Science and Technology Group Co., Ltd.; The product production enterprise name and model of the spherical silicon powder are NOVOPOWDER DQ of Jiangsu Lianrui New Material Co., Ltd.

8. The resin composition for a copper-clad plate according to claim 5 or 6, characterized by: The preparation method of the halogen-free naphthalene ring type epoxy resin solution containing high-activity double bonds comprises the following steps: a. 80-100 parts by mass of 1,4-naphthoquinone, 100-120 parts by mass of cyclohexanone, and 120-140 parts by mass of DOPO are added to a reactor, and stirring is performed to heat to 80°C, so that the 1,4-naphthoquinone and the DOPO are dissolved; b. The temperature is controlled at 78-82°C, 88-92°C, and 98-102°C, and stirring is performed for 1 hour, 1 hour, and 2 hours, respectively; c. Then, 500-600 parts by mass of a phenolic epoxy resin and 0.1-0.4 parts by mass of an ethyl triphenyl phosphonium acetate catalyst are added, the temperature is controlled at 140-150°C, and reaction is performed for 1-2 hours, the temperature is increased, the temperature is controlled at 160-175°C, and reaction is performed for 2-4 hours; d. Then, the temperature is decreased to 78-82°C, 0.1-0.4 parts by mass of hydroquinone is added to the reactor, 140-150 parts by mass of acrylic acid and 0.5-1.0 parts by mass of trimethylbenzyl ammonium chloride are uniformly mixed, and then placed in a constant-pressure dropping funnel, and dropped into the reactor at a temperature of 78-82°C for 0.5 hours; e. The temperature is controlled at 78-82°C, and reaction is performed for 2 hours, then the temperature is controlled at 88-92°C, and reaction is performed for 2-4 hours, and the acid value is tested, and the acid value meets 40-50 mgKOH / 1g resin; f. When the acid value meets the requirement, the temperature is decreased, 380-420 parts by mass of butanone solvent is added, and stirring is performed to obtain the halogen-free naphthalene ring type epoxy resin solution containing high-activity double bonds.

9. The method for preparing the halogen-free flame-retardant epoxy resin solution containing highly active double-bonded naphthalene rings according to claim 8, characterized in that: The solid content of the prepared halogen-free naphthalene ring type epoxy resin solution containing high-activity double bonds is 59.0-61.0%, the viscosity is 10,000-16,000 mPas, the phosphorus content is 1.8-2.0%, and the double bond equivalent is 400-450 g / mol.

10. The method for preparing a halogen-free flame-retardant epoxy resin solution containing a highly active double-bonded naphthalene ring as described in claim 8 or 9, characterized in that: The product production enterprise and model of the phenolic epoxy resin are EMTE638 of Shandong Aimonter New Material Co., Ltd.

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