Glue solution for copper-clad plate and preparation method of glue solution

Abstract

The invention discloses a glue solution for a copper-clad plate and a preparation method of the glue solution, and relates to the technical field of copper-clad plates. According to the prepared glue solution for the copper-clad plate, the composite epoxy resin, the curing agent, the accelerant, the solvent, the flexibilizer and the inorganic filler, the composite epoxy resin comprises bisphenol A epoxy resin, epoxy phenyl polysiloxane, itaconic acid polyaryletherketone and hydroxyl-terminated fluorine-containing vinyl polysiloxane, so that the interface bonding force with the copper plate is enhanced; the dielectric constant and the dielectric loss are effectively reduced, the peel strength and the toughness of the material are also remarkably improved, and the toughening agent is modified polyether sulfone microspheres; the modified polyethersulfone microspheres are prepared by coating polyethersulfone microspheres with hexamethylenediamine tetrapropionamide diamine, the hexamethylenediamine tetrapropionamide diamine is prepared by carrying out acylation condensation reaction on hexamethylenediamine tetramethyl propionate and ethylenediamine, and the polyethersulfone microspheres are prepared by carrying out electrostatic spinning on a spinning solution of polyethersulfone and vinylpyridine, so that the peel strength of the glue solution is remarkably improved.

Description

Technical Field

[0001] The invention relates to the technical field of copper clad laminates, in particular to an adhesive for copper clad laminates and a preparation method thereof. Background Art

[0002] Copper-clad laminates are the primary material for printed circuit board (PCB) manufacturing and are therefore essential foundational electronic materials for any electronic product or component. With the rapid development of the PCB manufacturing industry, market demand for high-performance copper-clad laminates is increasing. In today's era of comprehensive development and increasing maturity in the green and environmentally friendly era, in addition to the product's heat resistance, TG value, CTE value, and other properties, material toughness, processability, and adhesion have also become key areas of focus. The balanced development of copper-clad laminate substrate properties has become a key trend in the development of new copper-clad laminate materials.

[0003] Chinese patent CN111718678B discloses a glue for copper clad laminates and a method for preparing copper clad laminates. By rationally selecting epoxy resin for combination, introducing a new halogen-free flame retardant, and co-curing with PN and amine curing agents, the flame retardant ability of the copper clad laminates can be made to meet the UL94V-0 requirement. At the same time, the copper clad laminates have excellent thermal reliability, low water absorption, and low dielectric constant and dielectric loss, with excellent comprehensive performance. However, the glue for copper clad laminates with higher strength has not been achieved. Therefore, the present invention studies and prepares a glue for copper clad laminates that has low dielectric constant and dielectric loss while also having excellent high strength. Summary of the Invention

[0004] The technical problem to be solved by the present invention is to provide an adhesive for copper clad laminates and a preparation method thereof.

[0005] The present invention proposes a technical solution to solve the above technical problems: a glue for copper clad laminates, comprising the following components in parts by weight: 300 to 400 parts of a composite epoxy resin, 10 to 20 parts of a curing agent, 1 to 2 parts of an accelerator, 8 to 16 parts of a toughening agent, 80 to 120 parts of a solvent and 80 to 160 parts of an inorganic filler; the composite epoxy resin comprises bisphenol A epoxy resin, epoxyphenyl polysiloxane, itaconic acid polyaryletherketone and terminal hydroxyl fluorinated vinyl polysiloxane.

[0006] Preferably, the epoxyphenyl polysiloxane is 1,5-bis(glycidoxypropyl)-3-phenyl-1,1,3,5,5-pentamethyltrisiloxane; the itaconic acid polyaryletherketone is prepared by reacting itaconic acid glycidyl ester with carboxyl hyperbranched polyaryletherketone; and the terminal hydroxyl fluorine-containing vinyl polysiloxane is prepared by polymerizing octamethylcyclotetrasiloxane with trifluoropropyltrimethylcyclotrisiloxane and introducing tetramethyltetravinylcyclotetrasiloxane.

[0007] Preferably, the toughening agent is modified polyethersulfone microspheres; the modified polyethersulfone microspheres are made by coating polyethersulfone microspheres with hexamethylenediaminetetrapropionamide diamine; the hexamethylenediaminetetrapropionamide diamine is made by acylation condensation reaction of hexamethylenediaminetetrapropionic acid methyl ester and ethylenediamine; the polyethersulfone microspheres are made by electrospinning a spinning solution of polyethersulfone and vinylpyridine.

[0008] Preferably, the curing agent is one or a mixture of ethylenediamine, dicyandiamide, and diaminodiphenylamine; the accelerator is one or a mixture of 2-methylimidazole, 4-methylimidazole, and benzyldimethylamine; the solvent is one or a mixture of acetone, butanone, cyclohexanone, dimethylformamide, and hexanediol butyl ether; and the inorganic filler is one or a mixture of talc, kaolin, magnesium hydroxide, silicon dioxide, calcium carbonate, and calcium silicate.

[0009] Preferably, the method for preparing the adhesive for copper clad laminate comprises the following specific steps:

[0010] S1. Under a nitrogen atmosphere, carboxyl hyperbranched poly(aryletherketone) and N-methylpyrrolidone were mixed in a mass ratio of 1:15-20, heated to 80-90°C, stirred and dissolved, and then 0.02-0.04 times the mass of the carboxyl hyperbranched poly(aryletherketone) as catalyst tetrabutylammonium bromide and 2.4-2.6 times the mass of the carboxyl hyperbranched poly(aryletherketone) as catalyst glycidyl itaconic acid ester were added. The mixture was heated to 80-90°C, reacted for 4-5 hours, cooled and precipitated with ice methanol, filtered, washed with methanol and acetone 3-5 times in sequence, and dried in vacuo at 60-70°C to obtain itaconic acid poly(aryletherketone);

[0011] S2. Bisphenol A epoxy resin, epoxyphenyl polysiloxane, itaconic acid polyaryletherketone and terminal hydroxyl fluorine-containing vinyl polysiloxane were mixed in a mass ratio of 50:4 to 8:3:2 to 4, heated to 80 to 90 ° C, and stirred at 400 to 600 rpm for 6 to 8 hours to obtain a composite epoxy resin;

[0012] S3. Hexamethylenediaminetetrapropionate methyl ester and methanol were mixed in a mass ratio of 1.05 to 1.15:2, and ethylenediamine in an amount of 0.55 to 0.57 times the mass of hexamethylenediaminetetrapropionate methyl ester was added at a rate of 1 to 3 ml / min. The mixture was heated to 40 to 42 ° C. The reaction was allowed to proceed for 24 h. After rotary evaporation, ether was precipitated 3 to 5 times and vacuum distilled to obtain hexamethylenediaminetetrapropionamide diamine.

[0013] S4. Under a nitrogen atmosphere, polyethersulfone microspheres, hexamethylenediaminetetrapropionamide diamine, and N,N-dimethylacetamide were mixed in a mass ratio of 1:5 to 6:5, stirred uniformly, heated to 80-90°C, reacted for 12-18 hours, cooled to room temperature, precipitated with methanol, washed 3-5 times with methanol and then with acetone, and dried in vacuo at 60-80°C to produce modified polyethersulfone microspheres, which serve as a toughening agent.

[0014] S5. Add solvent, curing agent and composite epoxy resin to the glue tank, stir evenly, add accelerator, toughening agent and inorganic filler, raise the temperature to 40-60°C, stir at 800-1000 rpm and mature for 6-10 hours to prepare the glue for copper clad laminate.

[0015] Preferably, in the above step S1, the preparation method of glycidyl itaconate is: mixing itaconic acid, triphenylphosphine, p-hydroxyanisole and glycidyl methacrylate in a mass ratio of 3.6-3.8:0.18-0.2:0.1:8-10, heating to 108-110°C, reacting for 6-8 hours, cooling to room temperature and filtering, distilling under reduced pressure, washing with deionized water 3-5 times, and drying over anhydrous sodium sulfate to obtain glycidyl itaconate.

[0016] Preferably, in step S1 above, the preparation method of the carboxyl hyperbranched polyaryletherketone is as follows: under a nitrogen atmosphere, phloroglucinol, difluorobenzophenone, phenolphthalein, dimethyl sulfoxide and toluene are mixed in a mass ratio of 3-3.5:4:3-3.4:18:15, heated to 138-142° C., reacted for 2-3 hours, heated to 174-176° C., reacted for 2-3 hours, cooled to 145-148° C., added N,N-dimethylformamide (10-30 times the mass of phloroglucinol), stirred evenly, cooled to 80-90° C., reacted for 30-50 minutes, allowed to stand and separate, and precipitated with an ethanol mixture, wherein the ethanol mixture contains ethanol, deionized water and 37% hydrochloric acid in a mass ratio of 1:1:0.1-0.4, is transferred to deionized water and washed 3-5 times, and finally dried to obtain the carboxyl hyperbranched polyaryletherketone.

[0017] Preferably, in the above step S2, the preparation method of the terminal hydroxyl fluorine-containing vinyl polysiloxane is as follows: under a nitrogen atmosphere, octamethylcyclotetrasiloxane, trifluoropropyltrimethylcyclosiloxane and tetramethyltetravinylcyclotetrasiloxane are mixed in a mass ratio of 23:49-50:27-28, heated to 90-92°C, reacted for 30-50 minutes, and then heated to 110-112°C. A 25% aqueous solution of tetramethylammonium hydroxide in an amount of 0.04-0.08 times the mass of octamethylcyclotetrasiloxane and a capping agent of 0.02-0.04 times the mass of octamethylcyclotetrasiloxane are added, the reaction is continued for 3-4 hours, the temperature is raised to 148-152°C, the reaction is carried out for 2-4 hours, and the reduced pressure distillation is carried out to obtain the terminal hydroxyl fluorine-containing vinyl polysiloxane.

[0018] Preferably, in the above step S3, the preparation method of hexamethylenediaminetetrapropionate methyl ester is: mixing hexamethylenediamine and methanol in a mass ratio of 10 to 12:50, heating to 40 to 45° C., adding sodium methoxide as a catalyst in an amount of 0.01 to 0.03 times the mass of hexamethylenediamine, and adding methyl acrylate in an amount of 6 to 8 times the mass of hexamethylenediamine dropwise at a rate of 1 to 3 ml / min, and then adding phenothiazine as a polymerization inhibitor in an amount of 0.01 to 0.03 times the mass of hexamethylenediamine, reacting for 24 hours, and separating and purifying by column chromatography using methanol and dichloromethane in a volume ratio of 1:20 as eluents to obtain hexamethylenediaminetetrapropionate methyl ester.

[0019] Preferably, in the above step S4, the preparation method of polyethersulfone microspheres is: polyethersulfone powder, 4-vinylpyridine and N,N-dimethylformamide are mixed in a mass ratio of 3 to 6:4:40, heated to 60 to 80°C, ultrasonically dispersed at 60 to 80kHz, and allowed to stand for degassing. During electrospinning, at 15 to 25kV, a push speed of 1.5 to 2.5mL / h, a receiving distance of 8 to 10cm, and a coagulation temperature of 28 to 30°C, filtered and washed with deionized water 3 to 5 times, and dried to obtain polyethersulfone microspheres.

[0020] Compared with the prior art, the present invention has the following beneficial effects:

[0021] The adhesive for copper clad laminate prepared by the present invention comprises composite epoxy resin, curing agent, accelerator, solvent, toughening agent and inorganic filler;

[0022] The composite epoxy resin includes bisphenol A epoxy resin, epoxyphenyl polysiloxane, itaconic acid polyaryletherketone and terminal hydroxyl fluorinated vinyl polysiloxane. The epoxyphenyl polysiloxane is 1,5-bis(glycidoxypropyl)-3-phenyl-1,1,3,5,5-pentamethyltrisiloxane. The itaconic acid polyaryletherketone is prepared by the reaction of itaconic acid glycidyl ester and carboxyl hyperbranched polyaryletherketone. The terminal hydroxyl fluorinated vinyl polysiloxane is prepared by the polymerization of octamethylcyclotetrasiloxane and trifluoropropyltrimethylcyclotrisiloxane and the introduction of tetramethyltetravinylcyclotetrasiloxane. The itaconic acid polyaryletherketone with a hyperbranched structure is introduced into the cross-linked structure of the composite resin, combined with the low surface energy of the fluorosilicone material, to enhance the polar bonding ability, thereby enhancing the interfacial bonding force with the copper plate. Then, by participating in the formation of the cross-linked network of the composite epoxy resin curing, it not only effectively reduces the dielectric constant and dielectric loss, but also significantly improves the peel strength and toughness of the material.

[0023] The toughening agent is modified polyethersulfone microspheres; the modified polyethersulfone microspheres are made by coating polyethersulfone microspheres with hexamethylenediaminetetrapropionamide diamine, which is made by the acylation condensation reaction of hexamethylenediaminetetrapropionate methyl ester and ethylenediamine. The polyethersulfone microspheres are made by electrospinning the spinning solution of polyethersulfone and vinylpyridine. The long-chain amide structure formed on the surface of the polyethersulfone microspheres can effectively disperse stress and form an island structure or an interpenetrating network with the composite epoxy resin. A denser cross-linked network can be formed during the curing process, significantly improving the peel strength of the adhesive. DETAILED DESCRIPTION

[0024] The present invention is described in detail below through examples. It should be noted that the following examples are intended only to further illustrate the present invention and are not to be construed as limiting the scope of protection of the present invention. Those skilled in the art may make non-essential improvements and adjustments to the present invention based on the above disclosure. Unless otherwise defined, all professional and scientific terms used herein have the same meanings as those familiar to those skilled in the art.

[0025] The copper clad laminates prepared in the examples and comparative examples were made into prepregs using a vertical glue machine. The glue content and fluidity were controlled to be 40%. Six prepregs and copper foil were stacked and placed in a laminator under a pressure of 30 kg / cm 2 , the temperature is 180℃, and the pressing is carried out for 60 minutes to obtain a copper clad laminate.

[0026] In order to more clearly illustrate the method provided by the present invention, the following examples are used to describe in detail the various index testing methods of the adhesive for copper clad laminate prepared in the examples and comparative examples as follows:

[0027] Dielectric properties: The dielectric constant and dielectric loss of the copper clad laminates prepared in the examples and comparative examples were tested with reference to GB / T4722.

[0028] Flexibility: The copper clad laminates prepared in the examples and comparative examples were bent 5000 times with the adhesive to observe whether there were any cracks.

[0029] Peel strength: The adhesives for copper clad laminates prepared in the examples and comparative examples were subjected to a peel strength test according to GB / T4722.

[0030] Example 1

[0031] In the adhesive for copper clad laminates in this embodiment, the weight proportions of the components are: 300 parts of composite epoxy resin, 10 parts of curing agent ethylenediamine, 1 part of accelerator 2-methylimidazole, 8 parts of toughening agent, 80 parts of solvent acetone and 80 parts of inorganic filler talc.

[0032] The preparation method of the adhesive for copper clad laminate in this embodiment is as follows:

[0033] S1. Itaconic acid, triphenylphosphine, p-hydroxyanisole and glycidyl methacrylate were mixed in a mass ratio of 3.6:0.18:0.1:8, heated to 108 ° C, reacted for 6 hours, cooled to room temperature, filtered, distilled under reduced pressure, washed three times with deionized water, and dried over anhydrous sodium sulfate to obtain glycidyl itaconic acid; under a nitrogen atmosphere, phloroglucinol, difluorobenzophenone, phenolphthalein, dimethyl sulfoxide and toluene were mixed in a mass ratio of 3:4:3:18:15, heated to 138 ° C, reacted for 2 hours, heated to 174 ° C, reacted for 2 hours, cooled to 145 ° C, added N, N-dimethylformamide 10 times the mass of phloroglucinol, stirred evenly, cooled to 80 ° C, reacted for 30 minutes, and allowed to stand for separation. layer, precipitated with an ethanol mixture, the ethanol mixture containing ethanol, deionized water and 37% hydrochloric acid in a mass ratio of 1:1:0.1, transferred to deionized water and boiled and washed three times, and finally dried to obtain a carboxyl hyperbranched polyaryletherketone; under a nitrogen atmosphere, the carboxyl hyperbranched polyaryletherketone and N-methylpyrrolidone were mixed in a mass ratio of 1:15, heated to 80°C, stirred and dissolved, and then 0.02 times the mass of the carboxyl hyperbranched polyaryletherketone as catalyst tetrabutylammonium bromide and 2.4 times the mass of the carboxyl hyperbranched polyaryletherketone as catalyst glycidyl ester were added, heated to 80°C, reacted for 4h, cooled and precipitated with ice methanol, filtered and washed three times with methanol and acetone in sequence, and dried in vacuo at 60°C to obtain itaconic acid polyaryletherketone;

[0034] S2. Under a nitrogen atmosphere, octamethylcyclotetrasiloxane, trifluoropropyltrimethylcyclosiloxane and tetramethyltetravinylcyclotetrasiloxane were mixed in a mass ratio of 23:49:27, heated to 90°C, reacted for 30 minutes, and then heated to 110°C. A 25% aqueous solution of tetramethylammonium hydroxide was added at a catalyst mass fraction of 0.04 times the mass of octamethylcyclotetrasiloxane and a capping agent of 0.02 times the mass of octamethylcyclotetrasiloxane in deionized water. The reaction was continued for 3 hours, heated to 148°C, reacted for 2 hours, and distilled under reduced pressure to obtain a terminal hydroxyl-containing fluorinated vinyl polysiloxane; bisphenol A epoxy resin, epoxyphenyl polysiloxane, itaconic acid polyaryletherketone and terminal hydroxyl-containing fluorinated vinyl polysiloxane were mixed in a mass ratio of 50:4:3:2, heated to 80°C, and stirred at 400 rpm for 6 hours to obtain a composite epoxy resin;

[0035] S3. Hexamethylenediamine and methanol were mixed in a mass ratio of 10:50, heated to 40°C, sodium methoxide as a catalyst in an amount of 0.01 times the mass of hexamethylenediamine was added, and methyl acrylate in an amount of 6 times the mass of hexamethylenediamine was added dropwise at a rate of 1 ml / min, and then phenothiazine as a polymerization inhibitor in an amount of 0.01 times the mass of hexamethylenediamine was added. The mixture was reacted for 24 hours, and methanol and dichloromethane in a volume ratio of 1:20 were used as eluents. The mixture was separated and purified by column chromatography to obtain hexamethylenediaminetetrapropionate methyl ester; hexamethylenediaminetetrapropionate methyl ester and methanol were mixed in a mass ratio of 1.05:2, ethylenediamine in an amount of 0.55 times the mass of hexamethylenediaminetetrapropionate methyl ester was added at a rate of 1 ml / min, the mixture was heated to 40°C, the mixture was reacted for 24 hours, ether was precipitated three times after rotary evaporation, and vacuum distillation was performed to obtain hexamethylenediaminetetrapropionamide diamine;

[0036] S4. Polyethersulfone powder, 4-vinylpyridine and N,N-dimethylformamide were mixed in a mass ratio of 3:4:40, heated to 60°C, ultrasonically dispersed on ice at 60kHz, and allowed to stand for degassing. During electrospinning, the mixture was subjected to 15kV, a push injection rate of 1.5mL / h, a receiving distance of 8cm, and a coagulation temperature of 28°C. The mixture was filtered and washed three times in deionized water, and then dried to obtain polyethersulfone microspheres. Under a nitrogen atmosphere, polyethersulfone microspheres, hexamethylenediaminetetrapropionamide diamine and N,N-dimethylacetamide were mixed in a mass ratio of 1:5:5, stirred evenly, heated to 80°C, reacted for 12h, cooled to room temperature, precipitated with methanol, washed four times with methanol and acetone, and dried in vacuo at 70°C to obtain modified polyethersulfone microspheres, which are toughening agents.

[0037] S5. Add solvent, curing agent and composite epoxy resin to the glue tank, stir evenly, add accelerator, toughening agent and inorganic filler, heat to 40 ° C, stir at 800 rpm and mature for 6 hours to prepare a copper clad laminate glue

[0038] Example 2

[0039] In the adhesive for copper clad laminates in this embodiment, the weight proportions of the components are: 350 parts of composite epoxy resin, 15 parts of curing agent dicyandiamide, 1.5 parts of accelerator 4-methylimidazole, 12 parts of toughening agent, 100 parts of solvent hexanediol butyl ether and 120 parts of inorganic filler magnesium hydroxide.

[0040] The preparation method of the adhesive for copper clad laminate in this embodiment is as follows:

[0041] S1. Itaconic acid, triphenylphosphine, p-hydroxyanisole and glycidyl methacrylate were mixed in a mass ratio of 3.7:0.19:0.1:9, heated to 109 ° C, reacted for 7 hours, cooled to room temperature, filtered, distilled under reduced pressure, washed with deionized water 4 times, and dried over anhydrous sodium sulfate to obtain glycidyl itaconic acid; under a nitrogen atmosphere, phloroglucinol, difluorobenzophenone, phenolphthalein, dimethyl sulfoxide and toluene were mixed in a mass ratio of 3.3:4:3.2:18:15, heated to 139 ° C, reacted for 2.5 hours, heated to 175 ° C, reacted for 2.5 hours, cooled to 147 ° C, added N, N-dimethylformamide 20 times the mass of phloroglucinol, stirred evenly, and cooled to 85 ° C, reacted for 40 minutes, The mixture was allowed to stand for stratification and precipitated with an ethanol mixture, wherein the ethanol mixture contained ethanol, deionized water and 37% hydrochloric acid in a mass ratio of 1:1:0.3, and the mixture was transferred to deionized water and boiled and washed 4 times, and finally dried to obtain a carboxyl hyperbranched polyaryletherketone; under a nitrogen atmosphere, the carboxyl hyperbranched polyaryletherketone was mixed with N-methylpyrrolidone in a mass ratio of 1:18, the mixture was heated to 85°C, stirred and dissolved, and 0.03 times the mass of the carboxyl hyperbranched polyaryletherketone as catalyst tetrabutylammonium bromide and 2.5 times the mass of the carboxyl hyperbranched polyaryletherketone as catalyst glycidyl ester were added, the mixture was heated to 85°C, reacted for 4.5h, cooled and precipitated with ice methanol, filtered and washed 4 times with methanol and acetone in sequence, and dried in vacuo at 65°C to obtain itaconic acid polyaryletherketone;

[0042] S2. Under a nitrogen atmosphere, octamethylcyclotetrasiloxane, trifluoropropyltrimethylcyclosiloxane and tetramethyltetravinylcyclotetrasiloxane were mixed in a mass ratio of 23:49.5:27, heated to 91 ° C, reacted for 40 minutes, and then heated to 111 ° C. 0.06 times the mass of octamethylcyclotetrasiloxane was added. A 25% tetramethylammonium hydroxide aqueous solution of the catalyst mass fraction and 0.03 times the mass of the octamethylcyclotetrasiloxane were added as a capping agent, deionized water, and the reaction was continued for 3.5 hours. The temperature was raised to 150 ° C. The reaction was continued for 3 hours, and the mixture was distilled under reduced pressure to obtain a terminal hydroxyl-containing fluorine-containing vinyl polysiloxane; bisphenol A epoxy resin, epoxyphenyl polysiloxane, itaconic acid polyaryletherketone and terminal hydroxyl-containing fluorine-containing vinyl polysiloxane were mixed in a mass ratio of 50:6:3:3, heated to 85 ° C, and stirred at 500 rpm for 7 hours to obtain a composite epoxy resin;

[0043] S3. Hexamethylenediamine and methanol were mixed in a mass ratio of 11:50, heated to 43°C, sodium methoxide as a catalyst in an amount of 0.02 times the mass of hexamethylenediamine was added, and methyl acrylate in an amount of 7 times the mass of hexamethylenediamine was added dropwise at a rate of 2 ml / min, followed by addition of phenothiazine as a polymerization inhibitor in an amount of 0.02 times the mass of hexamethylenediamine. The mixture was reacted for 24 hours, and methanol and dichloromethane in a volume ratio of 1:20 were used as eluents. The mixture was separated and purified by column chromatography to obtain hexamethylenediaminetetrapropionate methyl ester; hexamethylenediaminetetrapropionate methyl ester and methanol were mixed in a mass ratio of 1.1:2, ethylenediamine in an amount of 0.56 times the mass of hexamethylenediaminetetrapropionate methyl ester was added at a rate of 2 ml / min, the mixture was heated to 41°C, the mixture was reacted for 24 hours, ether was precipitated four times after rotary evaporation, and vacuum distillation was performed to obtain hexamethylenediaminetetrapropionamide diamine;

[0044] S4. Polyethersulfone powder, 4-vinylpyridine and N,N-dimethylformamide were mixed in a mass ratio of 4.5:4:40, heated to 70°C, ultrasonically dispersed on ice at 70kHz, and allowed to stand for degassing. During electrospinning, the mixture was subjected to 20 kV, a push injection rate of 2 mL / h, a receiving distance of 9 cm, and a coagulation temperature of 29°C. The mixture was filtered and washed four times in deionized water, and dried to obtain polyethersulfone microspheres. Under a nitrogen atmosphere, polyethersulfone microspheres, hexamethylenediaminetetrapropionamide diamine and N,N-dimethylacetamide were mixed in a mass ratio of 1:5.5:5, stirred evenly, heated to 85°C, reacted for 16 hours, cooled to room temperature, precipitated with methanol, washed four times with methanol and acetone, and dried in vacuo at 70°C to obtain modified polyethersulfone microspheres, which are toughening agents.

[0045] S5. Add solvent, curing agent and composite epoxy resin to the glue tank, stir evenly, add accelerator, toughening agent and inorganic filler, raise the temperature to 50°C, stir at 900 rpm and mature for 8 hours to prepare the glue for copper clad laminate.

[0046] Example 3

[0047] In the adhesive for copper clad laminates in this embodiment, the weight proportions of the components are: 400 parts of composite epoxy resin, 20 parts of curing agent diaminodiphenylamine, 2 parts of accelerator 2-methylimidazole, 16 parts of toughening agent, 120 parts of solvent dimethylformamide and 160 parts of inorganic filler calcium carbonate.

[0048] The preparation method of the adhesive for copper clad laminate in this embodiment is as follows:

[0049] S1. Itaconic acid, triphenylphosphine, p-hydroxyanisole and glycidyl methacrylate were mixed in a mass ratio of 3.8:0.2:0.1:10, heated to 110 ° C, reacted for 8 hours, cooled to room temperature, filtered, distilled under reduced pressure, washed with deionized water 5 times, and dried over anhydrous sodium sulfate to obtain glycidyl itaconic acid; under a nitrogen atmosphere, phloroglucinol, difluorobenzophenone, phenolphthalein, dimethyl sulfoxide and toluene were mixed in a mass ratio of 3.5:4:3.4:18:15, heated to 142 ° C, reacted for 3 hours, heated to 176 ° C, reacted for 3 hours, cooled to 148 ° C, added N, N-dimethylformamide 30 times the mass of phloroglucinol, stirred evenly, cooled to 90 ° C, reacted for 50 minutes, and then stirred. The layers were separated and precipitated with an ethanol mixture, wherein the ethanol mixture contained ethanol, deionized water and 37% hydrochloric acid in a mass ratio of 1:1:0.4, and the mixture was transferred to deionized water and boiled and washed 5 times, and finally dried to obtain a carboxyl hyperbranched polyaryletherketone; under a nitrogen atmosphere, the carboxyl hyperbranched polyaryletherketone was mixed with N-methylpyrrolidone in a mass ratio of 1:20, the temperature was raised to 90°C, and after stirring and dissolving, 0.04 times the mass of the carboxyl hyperbranched polyaryletherketone of catalyst tetrabutylammonium bromide and 2.6 times the mass of the carboxyl hyperbranched polyaryletherketone of itaconic acid glycidyl ester were added, the temperature was raised to 90°C, the reaction was carried out for 5 hours, the temperature was lowered and the mixture was precipitated with ice methanol, the mixture was filtered and washed 5 times with methanol and acetone in sequence, and the mixture was vacuum dried at 70°C to obtain itaconic acid polyaryletherketone;

[0050] S2. Under a nitrogen atmosphere, octamethylcyclotetrasiloxane, trifluoropropyltrimethylcyclosiloxane and tetramethyltetravinylcyclotetrasiloxane were mixed in a mass ratio of 23:50:28, heated to 92°C, reacted for 50 minutes, and then heated to 112°C. A 25% aqueous solution of tetramethylammonium hydroxide was added at a catalyst mass fraction of 0.08 times the mass of octamethylcyclotetrasiloxane and a capping agent of 0.04 times the mass of octamethylcyclotetrasiloxane in deionized water. The reaction was continued for 4 hours, heated to 152°C, reacted for 4 hours, and distilled under reduced pressure to obtain a terminal hydroxyl-containing fluorinated vinyl polysiloxane; bisphenol A epoxy resin, epoxyphenyl polysiloxane, itaconic acid polyaryletherketone and terminal hydroxyl-containing fluorinated vinyl polysiloxane were mixed in a mass ratio of 50:8:3:4, heated to 90°C, and stirred at 600 rpm for 8 hours to obtain a composite epoxy resin;

[0051] S3. Hexamethylenediamine and methanol were mixed in a mass ratio of 12:50, heated to 45°C, sodium methoxide as a catalyst in an amount of 0.03 times the mass of hexamethylenediamine was added, and methyl acrylate in an amount of 8 times the mass of hexamethylenediamine was added dropwise at a rate of 3 ml / min, and then phenothiazine as a polymerization inhibitor in an amount of 0.03 times the mass of hexamethylenediamine was added. The mixture was reacted for 24 hours, and methanol and dichloromethane in a volume ratio of 1:20 were used as eluents. The mixture was separated and purified by column chromatography to obtain hexamethylenediaminetetrapropionate methyl ester; hexamethylenediaminetetrapropionate methyl ester and methanol were mixed in a mass ratio of 1.15:2, ethylenediamine in an amount of 0.57 times the mass of hexamethylenediaminetetrapropionate methyl ester was added at a rate of 3 ml / min, the mixture was heated to 42°C, the mixture was reacted for 24 hours, ether was precipitated 5 times after rotary evaporation, and vacuum distillation was performed to obtain hexamethylenediaminetetrapropionamide diamine;

[0052] S4. Polyethersulfone powder, 4-vinylpyridine and N,N-dimethylformamide were mixed in a mass ratio of 6:4:40, heated to 80°C, ultrasonically dispersed on ice at 80kHz, and allowed to stand for degassing. During electrospinning, the mixture was subjected to 25kV, a push injection rate of 2.5mL / h, a receiving distance of 10cm, and a coagulation temperature of 30°C. The mixture was filtered and washed 5 times in deionized water, and dried to obtain polyethersulfone microspheres. Under a nitrogen atmosphere, polyethersulfone microspheres, hexamethylenediaminetetrapropionamide diamine and N,N-dimethylacetamide were mixed in a mass ratio of 1:6:5, stirred evenly, heated to 90°C, reacted for 18h, cooled to room temperature, precipitated with methanol, washed 5 times with methanol and acetone, and dried in vacuo at 80°C to obtain modified polyethersulfone microspheres, which are toughening agents.

[0053] S5. Add solvent, curing agent and composite epoxy resin to the glue tank, stir evenly, add accelerator, toughening agent and inorganic filler, raise the temperature to 60°C, stir at 1000 rpm and mature for 10 hours to prepare the glue for copper clad laminate.

[0054] Comparative Example 1

[0055] The preparation method of Comparative Example 1 is the same as that of Example 2. The difference between the adhesive for copper clad laminate and Example 2 is that the composite epoxy resin only includes bisphenol A epoxy resin, epoxyphenyl polysiloxane and terminal hydroxyl fluorine-containing vinyl polysiloxane.

[0056] Comparative Example 2

[0057] The preparation method of Comparative Example 2 is the same as that of Example 2. The difference between the adhesive for copper clad laminate and Example 2 is that the composite epoxy resin only includes bisphenol A epoxy resin, epoxyphenyl polysiloxane and itaconic acid polyaryletherketone.

[0058] Comparative Example 3

[0059] The preparation method of Comparative Example 3 is the same as that of Example 2. The difference between the adhesive for copper clad laminate and Example 2 is that the composite epoxy resin includes bisphenol A epoxy resin, itaconic acid polyaryletherketone and terminal hydroxyl fluorine-containing vinyl polysiloxane.

[0060] Comparative Example 4

[0061] The preparation method of Comparative Example 4 is the same as that of Example 2. The difference between the adhesive for copper clad laminate and Example 2 is that the toughening agent is only polyethersulfone microspheres.

[0062] Comparative Example 5

[0063] The preparation method of Comparative Example 5 is the same as that of Example 2. The difference between the adhesive for copper clad laminate and Example 2 is that the modified polyethersulfone microspheres are prepared by coating polyethersulfone microspheres with ethylenediamine.

[0064] Comparative Example 6

[0065] The preparation method of Comparative Example 6 is the same as that of Example 2. The difference between the adhesive for copper clad laminate and Example 2 is that the adhesive only includes composite epoxy resin, curing agent, accelerator, solvent and inorganic filler.

[0066] Effect Examples

[0067] Table 1 below shows the performance test results of the adhesives for copper clad laminates prepared in Examples and Comparative Examples.

[0068] Table 1

[0069]

[0070] From the comparison of the performance data in Table 1, it can be seen that the adhesive for copper clad laminate prepared by the present invention not only has excellent adhesion, flexibility and antibacterial properties;

[0071] From the comparison of the experimental data of Example 1, Example 2, Example 3 and Comparative Example 1, Comparative Example 2, Comparative Example 3, it can be found that by compounding bisphenol A epoxy resin, epoxyphenyl polysiloxane, itaconic acid polyaryletherketone and terminal hydroxyl fluorinated vinyl polysiloxane, itaconic acid polyaryletherketone with a hyperbranched structure is introduced into the cross-linked structure of the composite resin, combined with the low surface energy of the fluorosilicone material, the polar bonding ability is enhanced, thereby enhancing the interfacial bonding force with the copper plate, and then by participating in the formation of the composite epoxy resin cured cross-linking network, not only the dielectric constant and dielectric loss are effectively reduced, but also the peel strength and toughness of the material are significantly improved.

[0072] From the comparison of the experimental data of Example 1, Example 2, Example 3 and Comparative Example 4, Comparative Example 5, Comparative Example 6, it can be found that the long-chain amide structure formed on the surface of the polyethersulfone microspheres can effectively disperse stress and form an island structure or an interpenetrating network with the composite epoxy resin. A denser cross-linked network can be formed during the curing process, significantly improving the peel strength of the glue.

[0073] Obviously, the above embodiments are merely examples for the purpose of clearly illustrating the embodiments of the present invention and are not intended to limit the embodiments of the present invention. Those skilled in the art will readily appreciate that other variations or modifications based on the above description are possible. It is not necessary and impossible to enumerate all embodiments here. However, such obvious variations or modifications arising from the spirit of the present invention remain within the scope of protection of the present invention.

Claims

1. A glue for copper clad laminate, characterized in that: The invention comprises the following components in parts by weight: 300 to 400 parts of a composite epoxy resin, 10 to 20 parts of a curing agent, 1 to 2 parts of an accelerator, 8 to 16 parts of a toughening agent, 80 to 120 parts of a solvent and 80 to 160 parts of an inorganic filler; the composite epoxy resin comprises bisphenol A epoxy resin, epoxyphenyl polysiloxane, itaconic acid polyaryletherketone and terminal hydroxyl fluorine-containing vinyl polysiloxane.

2. The adhesive for copper clad laminate according to claim 1, characterized in that: The epoxyphenyl polysiloxane is 1,5-bis(glycidoxypropyl)-3-phenyl-1,1,3,5,5-pentamethyltrisiloxane; the itaconic acid polyaryletherketone is prepared by reacting itaconic acid glycidyl ester with carboxyl hyperbranched polyaryletherketone; and the terminal hydroxyl fluorine-containing vinyl polysiloxane is prepared by polymerizing octamethylcyclotetrasiloxane and trifluoropropyltrimethylcyclotrisiloxane and introducing tetramethyltetravinylcyclotetrasiloxane.

3. The adhesive for copper clad laminate according to claim 1, characterized in that: The toughening agent is modified polyethersulfone microspheres; the modified polyethersulfone microspheres are made by coating polyethersulfone microspheres with hexamethylenediaminetetrapropionamide diamine; the hexamethylenediaminetetrapropionamide diamine is made by the acylation condensation reaction of hexamethylenediaminetetrapropionic acid methyl ester and ethylenediamine; the polyethersulfone microspheres are made by electrostatic spinning of a spinning solution of polyethersulfone and vinylpyridine.

4. The adhesive for copper clad laminate according to claim 1, characterized in that: The curing agent is one of ethylenediamine, dicyandiamide, and diaminodiphenylamine, or a mixture of several thereof; the accelerator is one of 2-methylimidazole, 4-methylimidazole, and benzyldimethylamine; the solvent is one of acetone, butanone, cyclohexanone, dimethylformamide, and hexanediol butyl ether, or a mixture of several thereof; and the inorganic filler is one of talc, kaolin, magnesium hydroxide, silicon dioxide, calcium carbonate, and calcium silicate, or a mixture of several thereof.

5. The method for preparing a copper clad laminate adhesive according to claim 1, wherein: The specific steps include: S1. Under a nitrogen atmosphere, carboxyl hyperbranched poly(aryletherketone) and N-methylpyrrolidone were mixed in a mass ratio of 1:15-20, heated to 80-90°C, stirred and dissolved, and then 0.02-0.04 times the mass of the carboxyl hyperbranched poly(aryletherketone) as catalyst tetrabutylammonium bromide and 2.4-2.6 times the mass of the carboxyl hyperbranched poly(aryletherketone) as catalyst glycidyl itaconic acid ester were added. The mixture was heated to 80-90°C, reacted for 4-5 hours, cooled and precipitated with ice methanol, filtered, washed with methanol and acetone 3-5 times in sequence, and dried in vacuo at 60-70°C to obtain itaconic acid poly(aryletherketone); S2. Bisphenol A epoxy resin, epoxyphenyl polysiloxane, itaconic acid polyaryletherketone and terminal hydroxyl fluorine-containing vinyl polysiloxane were mixed in a mass ratio of 50:4 to 8:3:2 to 4, heated to 80 to 90 ° C, and stirred at 400 to 600 rpm for 6 to 8 hours to obtain a composite epoxy resin; S3. Hexamethylenediaminetetrapropionate methyl ester and methanol were mixed in a mass ratio of 1.05 to 1.15:2, and ethylenediamine in an amount of 0.55 to 0.57 times the mass of hexamethylenediaminetetrapropionate methyl ester was added at a rate of 1 to 3 ml / min. The mixture was heated to 40 to 42 ° C. The reaction was allowed to proceed for 24 h. After rotary evaporation, ether was precipitated 3 to 5 times and vacuum distilled to obtain hexamethylenediaminetetrapropionamide diamine. S4. Under a nitrogen atmosphere, polyethersulfone microspheres, hexamethylenediaminetetrapropionamide diamine, and N,N-dimethylacetamide were mixed in a mass ratio of 1:5 to 6:5, stirred uniformly, heated to 80-90°C, reacted for 12-18 hours, cooled to room temperature, precipitated with methanol, washed 3-5 times with methanol and then with acetone, and dried in vacuo at 60-80°C to produce modified polyethersulfone microspheres, which serve as a toughening agent. S5. Add solvent, curing agent and composite epoxy resin to the glue tank, stir evenly, add accelerator, toughening agent and inorganic filler, raise the temperature to 40-60°C, stir at 800-1000 rpm and mature for 6-10 hours to prepare the glue for copper clad laminate.

6. The method for preparing a copper clad laminate adhesive according to claim 5, wherein: In the above step S1, the preparation method of glycidyl itaconate is: mixing itaconic acid, triphenylphosphine, p-hydroxyanisole and glycidyl methacrylate in a mass ratio of 3.6-3.8:0.18-0.2:0.1:8-10, heating to 108-110°C, reacting for 6-8 hours, cooling to room temperature and filtering, distilling under reduced pressure, washing with deionized water 3-5 times, and drying over anhydrous sodium sulfate to obtain glycidyl itaconate.

7. The method for preparing a copper clad laminate adhesive according to claim 5, wherein: In step S1, the preparation method of the carboxyl hyperbranched polyaryletherketone is as follows: under a nitrogen atmosphere, phloroglucinol, difluorobenzophenone, phenolphthalein, dimethyl sulfoxide, and toluene are mixed in a mass ratio of 3-3.5:4:3-3.4:18:15, the mixture is heated to 138-142° C., reacted for 2-3 hours, then heated to 174-176° C., reacted for 2-3 hours, cooled to 145-148° C., N,N-dimethylformamide (10-30 times the mass of phloroglucinol) is added, stirred evenly, cooled to 80-90° C., reacted for 30-50 minutes, allowed to stand and separate, and precipitated with an ethanol mixture. The ethanol mixture, which contains ethanol, deionized water, and 37% hydrochloric acid in a mass ratio of 1:1:0.1-0.4, is transferred to deionized water and washed 3-5 times, and finally dried to obtain the carboxyl hyperbranched polyaryletherketone.

8. The method for preparing a copper clad laminate adhesive according to claim 5, wherein: In the above step S2, the preparation method of the terminal hydroxyl fluorine-containing vinyl polysiloxane is as follows: under a nitrogen atmosphere, octamethylcyclotetrasiloxane, trifluoropropyltrimethylcyclosiloxane and tetramethyltetravinylcyclotetrasiloxane are mixed in a mass ratio of 23:49-50:27-28, heated to 90-92°C, reacted for 30-50 minutes, and then heated to 110-112°C. A 25% tetramethylammonium hydroxide aqueous solution with a catalyst mass fraction of 0.04-0.08 times the mass of octamethylcyclotetrasiloxane and a capping agent of 0.02-0.04 times the mass of octamethylcyclotetrasiloxane are added. Deionized water is added, the reaction is continued for 3-4 hours, the temperature is raised to 148-152°C, the reaction is carried out for 2-4 hours, and reduced pressure distillation is performed to obtain the terminal hydroxyl fluorine-containing vinyl polysiloxane.

9. The method for preparing a copper clad laminate adhesive according to claim 5, wherein: In the above step S3, the preparation method of hexamethylenediaminetetrapropionate methyl ester is as follows: hexamethylenediamine and methanol are mixed in a mass ratio of 10 to 12:50, the temperature is raised to 40 to 45° C., sodium methoxide as a catalyst in an amount of 0.01 to 0.03 times the mass of hexamethylenediamine is added, and methyl acrylate in an amount of 6 to 8 times the mass of hexamethylenediamine is added dropwise at a rate of 1 to 3 ml / min, and phenothiazine as a polymerization inhibitor in an amount of 0.01 to 0.03 times the mass of hexamethylenediamine is added, the reaction is carried out for 24 hours, and methanol and dichloromethane in a volume ratio of 1:20 are used as eluents, and the mixture is separated and purified by column chromatography to obtain hexamethylenediaminetetrapropionate methyl ester.

10. The method for preparing a glue for copper clad laminate according to claim 5, characterized in that: In the above step S4, the preparation method of polyethersulfone microspheres is: polyethersulfone powder, 4-vinylpyridine and N,N-dimethylformamide are mixed in a mass ratio of 3 to 6:4:40, heated to 60 to 80°C, ultrasonically dispersed at 60 to 80kHz, and allowed to stand for degassing. During electrospinning, at 15 to 25kV, a push speed of 1.5 to 2.5mL / h, a receiving distance of 8 to 10cm, and a coagulation temperature of 28 to 30°C, the mixture is filtered and washed with deionized water 3 to 5 times, and dried to obtain polyethersulfone microspheres.

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