Glue for copper-clad laminate and preparation method thereof, copper-clad laminate and preparation method thereof

Abstract

The present invention provides a copper clad laminate adhesive and a preparation method thereof, a copper clad laminate and a preparation method thereof, and belongs to the technical field of copper clad laminates. The copper clad laminate adhesive comprises the following components, in parts by weight: a main resin: 100 parts, a curing agent: 2 to 50 parts, an accelerator: 0 to 2 parts, a filler: 0 to 40 parts, a solvent: 50 to 130 parts, 4-aminobenzoic acid phenol ester phthalonitrile: 5 to 15 parts, and core-shell particles: 5 to 15 parts. The copper clad laminate adhesive, through the combined use of 4-aminobenzoic acid phenol ester phthalonitrile and a core-shell particle toughening agent, can significantly enhance the key mechanical properties of the copper clad laminate, such as the interface shear strength between the glass fiber and the resin, and the peel strength between the resin and the copper foil.

Description

Technical Field

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

[0002] Copper-clad laminates (CCLs) are widely used due to their excellent heat resistance and flame retardancy. However, in actual use, their peel strength often needs to be improved to meet the more demanding requirements of electronic device assembly and other applications. Currently, the production process of traditional CCLs often suffers from low peel strength between the laminate and the copper foil due to factors such as the characteristics of the raw materials and the setting of process parameters. This, to a certain extent, limits their application in applications with high reliability requirements.

[0003] CN108263068A discloses a method for preparing copper-clad laminates using a polyphenylene ether resin composition. This method combines the excellent properties of low-molecular-weight polyphenylene ether, cyanate esters, active esters, low-dielectric epoxy resins, and multifunctional epoxy resins. By adjusting the respective ratios, the resulting copper-clad laminates exhibit excellent dielectric and heat resistance properties, as well as good processability. However, their peel strength is only around 1.3 N / mm, which needs to be further improved. Summary of the Invention

[0004] In order to solve the problem of low peel strength of existing copper clad laminates, the present invention provides an adhesive for copper clad laminates and a preparation method thereof, a copper clad laminate and a preparation method thereof. The adhesive for copper clad laminates can significantly enhance key mechanical properties of the copper clad laminates, such as the interface shear strength between the glass fiber and the resin, and the peel strength between the resin and the copper foil, by composite use of 4-aminobenzoic acid phenol ester phthalonitrile and a core-shell particle toughening agent.

[0005] The technical solutions of the present invention are as follows:

[0006] The present invention provides an adhesive for copper clad laminates, comprising the following components in parts by weight:

[0007] Main resin: 100 parts,

[0008] Curing agent: 2 to 50 parts,

[0009] Accelerator: 0-2 parts,

[0010] Filler: 0-40 parts,

[0011] 4-aminobenzoic acid phenol ester phthalonitrile: 5-15 parts,

[0012] Core-shell particles: 5 to 15 parts.

[0013] In a specific embodiment, the 4-aminobenzoic acid phenol ester phthalonitrile includes at least one of 4-aminobenzoic acid phenol ester phthalonitrile, 4-aminobenzoic acid diphenol ester phthalonitrile and 4-aminobenzoic acid bisphenol A type phthalonitrile.

[0014] The structural formulas of 4-aminobenzoic acid phenol ester phthalonitrile, 4-aminobenzoic acid diphenol ester phthalonitrile and 4-aminobenzoic acid bisphenol A type phthalonitrile are shown in formula (I) to formula (III):

[0015]

[0016] wherein R1 is any one of -H, -CH3, and -OCH3, R2 is any one of -H, -CH3, and -OCH3, and X is any one of -CH2-, -S-, -SO2-, -C(CH3)2-, and -C(CF3)2-. R1 and R2 are specifically in the ortho or meta position.

[0017] These compounds can be used alone or in combination, depending on the specific application scenarios, such as differences in temperature resistance requirements and dielectric loss.

[0018] In a specific embodiment, the core-shell particles include at least one of a structure with methyl methacrylate-acrylonitrile copolymer as the shell and butadiene-styrene copolymer as the core, a structure with polybutyl acrylate copolymer as the core and acrylonitrile-styrene copolymer as the shell, a structure with polymethyl methacrylate as the shell and polybutyl acrylate as the core, a structure with polymethyl methacrylate as the shell and butadiene rubber as the core, and a structure with polymethyl methacrylate as the shell and silica as the core.

[0019] This type of core-shell structure enables the core-shell particles to exert a unique synergistic effect in the glue system, effectively dispersing stress and improving the peel strength of the material through the action between different phase interfaces.

[0020] In one embodiment, the main resin includes at least one of bisphenol A epoxy resin, brominated bisphenol A epoxy resin, bisphenol F epoxy resin, novolac epoxy resin, and brominated phenol epoxy resin;

[0021] The curing agent includes at least one of dicyandiamide, dimethyl diphenyl sulfone, boron trifluoride monoethylamine, linear phenolic resin, and nitrogen-containing phenolic resin;

[0022] The accelerator includes at least one of 2-methylimidazole, 2-phenylimidazole, 2-phenyl, 4-methylimidazole, benzyldimethylamine, and 2-methyl-4-ethylimidazole;

[0023] The filler includes at least one of silicon dioxide, hollow ceramic microspheres, aluminum hydroxide, magnesium hydroxide, aluminum oxide, and talc.

[0024] Different fillers can be selected in a targeted manner according to the specific performance requirements of the required product. For example, silicon dioxide can improve the insulation and heat resistance of the copper clad laminate; hollow ceramic microspheres can reduce the dielectric constant; aluminum hydroxide and magnesium hydroxide have flame retardant effects, etc. By rationally matching fillers, the comprehensive performance of the copper clad laminate can be optimized.

[0025] In a specific embodiment, the invention further comprises: a solvent: 60 to 120 parts.

[0026] In a specific embodiment, the solvent includes at least one of dimethylformamide, acetone, butanone, toluene, xylene, propylene glycol methyl ether, ethylene glycol methyl ether, and cyclohexanone.

[0027] Different solvents can be selected based on the performance requirements of the desired product, such as matching the solubility properties of the curing agent.

[0028] The present invention also provides a method for preparing a copper clad laminate adhesive, comprising the following steps:

[0029] First, a solvent with a mass of 5 to 10 times that of the curing agent is used to dissolve the curing agent; then, 4-aminobenzoic acid phenol ester phthalonitrile and core-shell particles are added to the remaining solvent and stirred at 45 to 60° C. to mix evenly; then, the mixture is mixed with the main resin and stirred at high speed for 20 to 60 minutes until uniform; the dissolved curing agent is continued to be added and stirred to mix evenly; then, the filler is added and stirred at high speed emulsification for 30 to 60 minutes until uniform; finally, the accelerator is added and stirred at high speed emulsification for 20 to 60 minutes until uniform; after maintaining high speed shear emulsification stirring for 5 to 10 hours, the preparation is completed.

[0030] The high-speed stirring speed is 1500-3000RPM, the high-speed shear emulsification stirring speed is 1500-3000RPM, and the speed in the specific embodiments can be 2000RPM.

[0031] The present invention also provides a method for preparing a copper clad laminate, comprising the following steps:

[0032] The above-mentioned glue liquid is applied on the glass fiber cloth to form a glue layer of uniform thickness, and then dried to evaporate the solvent in the glue liquid to form a prepreg. The prepreg is then compounded with copper foil and pressed to prepare a copper clad laminate.

[0033] In one embodiment, the gluing is performed at a temperature of 180 to 210°C and a speed of 10 to 30 m / min; the pressing is performed at a pressure of 25 to 35 kg / cm 2 , press at a temperature of 170-190°C for 60-120 minutes.

[0034] The present invention also provides a copper clad plate, which is prepared by the above-mentioned preparation method.

[0035] Compared with the prior art, the present invention has the following beneficial effects:

[0036] (1) Optimization of interface properties: The synergistic effect of 4-aminobenzoic acid phenol ester phthalonitrile and core-shell particle toughening agent greatly improves the interfacial compatibility and bonding strength between glass fiber and resin. The presence of amino groups on 4-aminobenzoic acid phenol ester phthalonitrile can improve the wettability of epoxy resin on glass fiber cloth. The surface of glass fiber cloth usually has a certain polarity, and the polarity of amino groups enables it to produce a strong interaction with the surface of glass fiber cloth, promoting epoxy resin to better wet the glass fiber cloth, allowing epoxy resin to fully penetrate into the pores and fibers of the glass fiber cloth, increasing the contact area, and thus improving the interfacial bonding strength. At the same time, amino groups can also be adsorbed on the surface of glass fiber cloth to form an interfacial transition layer, which enhances the bonding between glass fiber cloth and epoxy resin.

[0037] (2) At the same time, the special core-shell structure of the core-shell particles enables them to act as a "bridge" at the interface, further promoting the interaction between the glass fiber and the resin, and effectively reducing interface defects and stress concentration points. This optimization of interface performance significantly improves the interface shear strength, allowing the glass fiber and the resin to work better together when the copper clad laminate is subjected to external forces, making it less likely for interface debonding to occur, thereby greatly improving the overall mechanical properties and reliability of the copper clad laminate.

[0038] (3) Improved peel strength: 4-aminobenzoic acid phenol ester phthalonitrile contains amino and cyano groups. Among them, the amino group reacts with the epoxy group of the epoxy resin to form a covalent bond, which increases the cross-linking density between the molecular chains, improves the cohesive strength of the epoxy resin, and can better resist the separation at the interface under the action of external forces, thereby improving the peel strength. The cyano group is a strong polar group that increases the rigidity of the molecular chain, improves the strength and hardness of the epoxy resin, and the intermolecular force between the cyano groups (such as dipole-dipole interaction) enhances the cohesive strength, which is conducive to improving the peel strength. The core-shell particle toughening agent effectively disperses the stress generated during the peeling process through its dispersion and stress transfer effect in the resin matrix, avoiding local peeling caused by stress concentration. The synergistic effect of the two significantly enhances the bonding force between the resin and the copper foil, greatly improves the stability of the copper clad laminate during the assembly and use of electronic products, reduces the risk of delamination caused by insufficient peel strength, and extends the service life of electronic products. DETAILED DESCRIPTION

[0039] The present invention will be further described below with reference to specific examples, but the embodiments of the present invention are not limited thereto.

[0040] Example 1

[0041] Glue formula

[0042] 100g of main resin (brominated bisphenol A epoxy resin), 3g of curing agent (dicyandiamide), 0.2g of accelerator (benzyldimethylamine), 8g of 4-aminobenzoic acid phenol ester phthalonitrile, 5g of core-shell particle toughening agent (methyl methacrylate-acrylonitrile copolymer as the shell and butadiene-styrene copolymer as the core), and solvent (50g of dimethylformamide and 20g of acetone). The structural formula of 4-aminobenzoic acid phenol ester phthalonitrile in this embodiment is shown in Formula (IV):

[0043]

[0044] R1 is -CH3.

[0045] Preparation method:

[0046] Glue preparation

[0047] Dissolve the curing agent (dicyandiamide) in a solvent (dimethylformamide) at a concentration five times the curing agent's mass. Add the main resin (brominated bisphenol A epoxy resin) to the reactor. Then, in a separate container, add 4-aminobenzoic acid phenol ester phthalonitrile and a core-shell particle toughener (methyl methacrylate-acrylonitrile copolymer as the shell, butadiene-styrene copolymer as the core) to the remaining dimethylformamide and acetone solvent mixture at 60°C. Stir at high speed for 30 minutes to mix thoroughly. This mixture forms mixed solution ①. Add mixed solution ① to the main resin reactor and stir at high speed for 20 minutes until uniform. Continue adding the dissolved curing agent (dicyandiamide) and stirring at high speed for 20 minutes until uniform. Add the accelerator (benzyldimethylamine) and stir at high speed for 60 minutes until uniform. Maintain high-speed shear emulsification stirring for 6 hours to complete the preparation.

[0048] Gluing and lamination

[0049] The prepared glue solution was applied to the glass fiber cloth through a glue applicator in an oven at 190° C. at a speed of 20 m / min, with an RC of 54%, to prepare a prepreg.

[0050] After 6 sheets of prepreg were laminated with copper foil, they were placed in a laminator under a pressure of 30 kg / cm 2 , and pressed at a temperature of 170°C for 90 minutes to prepare a copper clad laminate.

[0051] Example 2

[0052] Glue formula

[0053] 100g of main resin (brominated bisphenol A epoxy resin), 2.7g of curing agent (dicyandiamide), 0.2g of accelerator (benzyldimethylamine), 0.05g of accelerator (2-methylimidazole), 10g of 4-aminobenzoic acid diphenyl ester phthalonitrile, 5g of core-shell particle toughening agent (with polymethyl methacrylate as shell and polybutyl acrylate as core), and solvent (50g of dimethylformamide and 20g of butanone). The structural formula of 4-aminobenzoic acid diphenyl ester phthalonitrile in this embodiment is shown in Formula (V):

[0054]

[0055] R2 is -CH3.

[0056] Preparation method:

[0057] Glue preparation

[0058] Dissolve the curing agent (dicyandiamide) in a solvent (dimethylformamide) at a concentration five times the curing agent's mass. Add the main resin (brominated bisphenol A epoxy resin) to the reactor. Then, in a separate container, add 4-aminobenzoic acid diphenyl ester phthalonitrile and a core-shell particle toughener (polymethyl methacrylate shell, polybutyl acrylate core) to the remaining dimethylformamide and butanone solvent mixture at 60°C. Stir at high speed for 30 minutes to mix thoroughly. This portion becomes mixed solution ①. Add mixed solution ① to the main resin reactor and stir at high speed for 20 minutes until uniform. Continue adding the dissolved curing agent (dicyandiamide) and stirring at high speed for 20 minutes until uniform. Add the accelerator (benzyldimethylamine) and accelerator (2-methylimidazole) and stir at high speed for 60 minutes until uniform. Maintain high-speed shear emulsification stirring for 6 hours to complete the preparation.

[0059] Gluing and lamination

[0060] The prepared glue solution was applied to the glass fiber cloth through a glue applicator in an oven at 190° C. at a speed of 20 m / min, with an RC of 54%, to prepare a prepreg.

[0061] After 6 sheets of prepreg were laminated with copper foil, they were placed in a laminator under a pressure of 30 kg / cm 2 , and pressed at a temperature of 170°C for 90 minutes to prepare a copper clad laminate.

[0062] Example 3

[0063] Glue formula

[0064] 100g of main resin (brominated bisphenol A epoxy resin), 24g of curing agent (linear phenolic resin), 0.08g of accelerator (2-methyl-4-ethylimidazole), fillers (10g of aluminum hydroxide, 15g of silicon dioxide), 5g of 4-aminobenzoic acid bisphenol A phthalonitrile, 15g of core-shell particle toughening agent (polymethyl methacrylate as the shell and silicon dioxide as the core), and solvents (50g of dimethylformamide and 20g of acetone). The structural formula of 4-aminobenzoic acid bisphenol A phthalonitrile is shown in formula (III), where X is -C(CH3)2-.

[0065] Preparation method:

[0066] Glue preparation

[0067] Dissolve the curing agent (linear phenolic resin) in a solvent (dimethylformamide) at a concentration five times the curing agent's mass. Add the main resin (brominated bisphenol A epoxy resin) to the reactor. Then, in a separate container, add 4-aminobenzoic acid bisphenol A phthalonitrile and a core-shell particle toughener (polymethyl methacrylate shell, silica core) to the remaining dimethylformamide and acetone solvent mixture at 50°C. Stir at high speed for 30 minutes to mix thoroughly. This mixture forms mixed solution ①. Add mixed solution ① to the main resin reactor and stir at high speed for 20 minutes until uniform. Continue adding the dissolved curing agent (linear phenolic resin) and stirring at high speed for 20 minutes until uniform. Add fillers (aluminum hydroxide and silica) and stir at high speed for 30 minutes until uniform. Finally, add the accelerator (2-methyl-4-ethylimidazole) and stir at high speed for 60 minutes until uniform. After aging with high-speed stirring for 6 hours, the preparation is complete.

[0068] Gluing and lamination

[0069] The prepared glue solution was applied to the glass fiber cloth through a glue applicator in an oven at 190° C. at a speed of 20 m / min, with an RC of 54%, to prepare a prepreg.

[0070] After 6 sheets of prepreg were laminated with copper foil, they were placed in a laminator under a pressure of 30 kg / cm 2 , and pressed at a temperature of 190°C for 90 minutes to prepare a copper clad laminate.

[0071] Comparative Example 1

[0072] Glue formula

[0073] Main resin (brominated bisphenol A type epoxy resin) 100g, curing agent (dicyandiamide) 3g, accelerator (benzyldimethylamine) 0.2g, solvent (dimethylformamide 50g, acetone 20g).

[0074] Preparation method:

[0075] Glue preparation

[0076] Dissolve the curing agent (dicyandiamide) in a solvent (dimethylformamide) 5 times the mass of the curing agent. Add the main resin (brominated bisphenol A epoxy resin) to the reactor; add the remaining solvent (dimethylformamide and acetone) and stir at high speed for 10 minutes until uniform. Add the dissolved curing agent (dicyandiamide) and stir at high speed for 20 minutes until uniform. Add the accelerator (benzyldimethylamine) and stir at high speed for 60 minutes until uniform. After maintaining high-speed shear emulsification stirring for 6 hours, the preparation is complete.

[0077] Gluing and lamination

[0078] The prepared glue solution was applied to the glass fiber cloth through a glue applicator in an oven at 190° C. at a speed of 20 m / min, with an RC of 54%, to prepare a prepreg.

[0079] After 6 sheets of prepreg were laminated with copper foil, they were placed in a laminator under a pressure of 30 kg / cm 2 , and pressed at a temperature of 170°C for 90 minutes to prepare a copper clad laminate.

[0080] Comparative Example 2

[0081] Glue formula

[0082] Main resin (brominated bisphenol A type epoxy resin) 100g, curing agent (dicyandiamide) 2.7g, accelerator (benzyldimethylamine) 0.2g, accelerator (2-methylimidazole) 0.05g, core-shell particle toughening agent (structure with polymethyl methacrylate as shell and polybutyl acrylate as core) 5g, solvent (dimethylformamide 50g, butanone 20g).

[0083] Preparation method:

[0084] Glue preparation

[0085] Dissolve the curing agent (dicyandiamide) in a solvent (dimethylformamide) at a concentration five times the curing agent's mass. Add the main resin (brominated bisphenol A epoxy resin) to the reactor. Then, in a separate container, add the core-shell particle toughening agent (a structure with polymethyl methacrylate as the shell and polybutyl acrylate as the core) to the remaining dimethylformamide and butanone solvent mixture at 60°C. Stir at high speed for 30 minutes to mix thoroughly. This portion becomes mixed solution ①. Add mixed solution ① to the main resin reactor and stir at high speed for 20 minutes until uniform. Continue adding the dissolved curing agent (dicyandiamide) and stirring at high speed for 20 minutes until uniform. Add the accelerator (benzyldimethylamine) and accelerator (2-methylimidazole) and stir at high speed for 60 minutes until uniform. Maintain high-speed shear emulsification stirring for 6 hours to complete the preparation.

[0086] Gluing and lamination

[0087] The prepared glue solution was applied to the glass fiber cloth through a glue applicator in an oven at 190° C. at a speed of 20 m / min, with an RC of 54%, to prepare a prepreg.

[0088] After 6 sheets of prepreg were laminated with copper foil, they were placed in a laminator under a pressure of 30 kg / cm 2 , and pressed at a temperature of 170°C for 90 minutes to prepare a copper clad laminate.

[0089] Comparative Example 3

[0090] Glue formula

[0091] Main resin (brominated bisphenol A type epoxy resin) 100g, curing agent (dicyandiamide) 2.7g, accelerator (benzyldimethylamine) 0.2g, accelerator (2-methylimidazole) 0.05g, 4-aminobenzoic acid diphenyl ester phthalonitrile (structural formula is the same as Example 2) 10g, solvent (dimethylformamide 50g, butanone 20g).

[0092] Preparation method:

[0093] Glue preparation

[0094] Dissolve the curing agent (dicyandiamide) in a solvent (dimethylformamide) at a concentration five times the curing agent's mass. Add the main resin (brominated bisphenol A epoxy resin) to the reactor. Then, in a separate container, add 4-aminobenzoic acid diphenyl ester phthalonitrile to the remaining dimethylformamide and butanone solvent mixture at 60°C. Stir at high speed for 30 minutes to mix thoroughly. This portion becomes mixed solution ①. Add mixed solution ① to the main resin reactor and stir at high speed for 20 minutes until uniform. Continue adding the dissolved curing agent (dicyandiamide) and stirring at high speed for 20 minutes until uniform. Add the accelerator (benzyldimethylamine) and accelerator (2-methylimidazole) and stir at high speed for 60 minutes until uniform. Maintain high-speed shear emulsification stirring for 6 hours to complete the preparation.

[0095] Gluing and lamination

[0096] The prepared glue solution was applied to the glass fiber cloth through a glue applicator in an oven at 190° C. at a speed of 20 m / min, with an RC of 54%, to prepare a prepreg.

[0097] After 6 sheets of prepreg were laminated with copper foil, they were placed in a laminator under a pressure of 30 kg / cm 2 , and pressed at a temperature of 170°C for 90 minutes to prepare a copper clad laminate.

[0098] Comparative Example 4

[0099] Glue formula

[0100] Main resin (brominated bisphenol A type epoxy resin) 100g, curing agent (dicyandiamide) 2.7g, accelerator (benzyldimethylamine) 0.2g, accelerator (2-methylimidazole) 0.05g, solvent (dimethylformamide 50g, butanone 20g).

[0101] Preparation method:

[0102] Glue preparation

[0103] Use a solvent (dimethylformamide) with a mass 5 times that of the curing agent to dissolve the curing agent (dicyandiamide). Add the main resin (brominated bisphenol A epoxy resin) to the reactor; add the remaining solvent (dimethylformamide and butanone) and stir at high speed for 10 minutes until uniform. Continue to add the dissolved curing agent (dicyandiamide) and stir at high speed for 20 minutes until uniform. Add the accelerator (benzyldimethylamine) and accelerator (2-methylimidazole) and stir at high speed for 60 minutes until uniform. After maintaining high-speed shear emulsification stirring for 6 hours, the preparation is complete.

[0104] Gluing and lamination

[0105] The prepared glue solution was applied to the glass fiber cloth through a glue applicator in an oven at 190° C. at a speed of 20 m / min, with an RC of 54%, to prepare a prepreg.

[0106] After 6 sheets of prepreg were laminated with copper foil, they were placed in a laminator under a pressure of 30 kg / cm 2 , and pressed at a temperature of 170°C for 90 minutes to prepare a copper clad laminate.

[0107] Comparative Example 5

[0108] Glue formula

[0109] Main resin (brominated bisphenol A type epoxy resin) 100g, curing agent (linear phenolic resin) 24g, accelerator (2-methyl-4-ethylimidazole) 0.08g, filler (aluminum hydroxide 10g, silica 15g), solvent (dimethylformamide 50g, acetone 20g).

[0110] Preparation method:

[0111] Glue preparation

[0112] Use a solvent (dimethylformamide) with a mass 5 times that of the curing agent to dissolve the curing agent (linear phenolic resin). Add the main resin (brominated bisphenol A epoxy resin) to the reactor; add the remaining solvent (dimethylformamide and acetone) and stir at high speed for 20 minutes until uniform. Continue to add the dissolved curing agent (linear phenolic resin) and stir at high speed for 20 minutes until uniform. Add fillers (aluminum hydroxide and silica) and stir at high speed emulsification for 30 minutes until uniform. Finally, add the accelerator (2-methyl-4-ethylimidazole) and stir at high speed emulsification for 60 minutes until uniform. After maintaining high-speed shear emulsification stirring for 6 hours, the preparation is complete.

[0113] Gluing and lamination

[0114] The prepared glue solution was applied to the glass fiber cloth through a glue applicator in an oven at 190° C. at a speed of 20 m / min, with an RC of 54%, to prepare a prepreg.

[0115] After 6 sheets of prepreg were laminated with copper foil, they were placed in a laminator under a pressure of 30 kg / cm 2 , and pressed at a temperature of 190°C for 90 minutes to prepare a copper clad laminate.

[0116] Performance comparison:

[0117]

[0118] Micro-debonding method:

[0119] Test Method: Mount a fiber specimen with a resin droplet fixed to it on a testing machine, aligning the fiber axis with the machine's loading direction. Adjust the tool or fixture to contact the resin droplet. The fixture applies shear force to the resin droplet, gradually debonding it from the fiber surface. Record data such as maximum load and displacement during the test, and observe the debonding process.

[0120] Calculate interfacial shear strength: Based on the maximum load, fiber diameter, and resin droplet length recorded during the test, calculate the interfacial shear strength using the formula τ = F / πdL, where τ is the interfacial shear strength, F is the maximum load, d is the fiber diameter, and L is the resin droplet length.

[0121] The above disclosure is merely a preferred embodiment of the present invention, which certainly cannot be used to limit the scope of the present invention. Therefore, equivalent changes made according to the claims of the present invention still fall within the scope of the present invention.

Claims

1. A glue for copper clad laminate, characterized in that: In parts by weight, it comprises the following components: Main resin: 100 parts, Curing agent: 2~50 parts, Accelerator: 0~2 parts, Filler: 0~40 parts, 4-aminobenzoic acid phenol ester phthalonitrile: 5-15 parts, Core-shell particles: 5~15 parts, and solvent: 50~130 parts; The main resin includes at least one of bisphenol A epoxy resin, brominated bisphenol A epoxy resin, bisphenol F epoxy resin, and novolac epoxy resin; The core-shell particles include at least one of a structure with methyl methacrylate-acrylonitrile copolymer as the shell and butadiene-styrene copolymer as the core, a structure with polymethyl methacrylate as the shell and polybutyl acrylate as the core, a structure with polymethyl methacrylate as the shell and butadiene rubber as the core, and a structure with polymethyl methacrylate as the shell and silica as the core; The 4-aminobenzoic acid phenol ester phthalonitrile includes at least one of 4-aminobenzoic acid phenol ester phthalonitrile, 4-aminobenzoic acid diphenol ester phthalonitrile and 4-aminobenzoic acid bisphenol A type phthalonitrile; The structural formulas of 4-aminobenzoic acid phenol ester phthalonitrile, 4-aminobenzoic acid diphenol ester phthalonitrile and 4-aminobenzoic acid bisphenol A type phthalonitrile are as follows ( )~Formula( ) as shown: Wherein, R1 is any one of -H, -CH3, and -OCH3, R2 is any one of -H, -CH3, and -OCH3, and X is -C(CH3)2-.

2. The adhesive for copper clad laminate according to claim 1, characterized in that: The curing agent includes at least one of dicyandiamide, boron trifluoride monoethylamine, linear phenolic resin, and nitrogen-containing phenolic resin; The accelerator includes at least one of 2-methylimidazole, 2-phenylimidazole, 4-methylimidazole, benzyldimethylamine, and 2-methyl-4-ethylimidazole; The filler includes at least one of silicon dioxide, hollow ceramic microspheres, aluminum hydroxide, magnesium hydroxide, aluminum oxide, and talc.

3. The adhesive for copper clad laminate according to claim 1, characterized in that: The solvent includes at least one of dimethylformamide, acetone, butanone, toluene, xylene, propylene glycol methyl ether, ethylene glycol methyl ether, and cyclohexanone.

4. The method for preparing a glue for copper clad laminate according to any one of claims 1 to 3, characterized in that: The steps include: First, a solvent with a mass of 5 to 10 times that of the curing agent is used to dissolve the curing agent; then, 4-aminobenzoic acid phenol ester phthalonitrile and core-shell particles are added to the remaining solvent, stirred at 45 to 60° C. to mix evenly, and then mixed with the main resin, and stirred at high speed for 20 to 60 minutes until uniform; continue to add the dissolved curing agent and stir to mix evenly; then add the filler and stir at high speed emulsification for 30 to 60 minutes until uniform; finally, add the accelerator and stir at high speed emulsification for 20 to 60 minutes until uniform; after maintaining high speed emulsification stirring for 5 to 10 hours, the preparation is completed.

5. A method for preparing a copper clad laminate, characterized in that: The following steps are involved: The adhesive liquid described in any one of claims 1 to 3 is applied to the glass fiber cloth to form an adhesive layer with uniform thickness; then the adhesive liquid is dried to volatilize the solvent in the adhesive liquid to form a prepreg; and the prepreg is compounded with copper foil and pressed to prepare a copper clad laminate.

6. The method for preparing a copper clad laminate according to claim 5, wherein: Gluing is done at 180-210°C at a speed of 10-30 m / min; The pressing process is carried out at a pressure of 25 to 35 kg / cm² and a temperature of 170 to 190°C for 60 to 120 minutes.

7. A copper clad laminate, characterized in that: The invention is prepared by the preparation method according to any one of claims 5 to 6.

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