CN116278238B - High-temperature-resistant epoxy resin-based copper-clad plate and preparation method thereof - Google Patents

High-temperature-resistant epoxy resin-based copper-clad plate and preparation method thereof Download PDF

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CN116278238B
CN116278238B CN202211499902.5A CN202211499902A CN116278238B CN 116278238 B CN116278238 B CN 116278238B CN 202211499902 A CN202211499902 A CN 202211499902A CN 116278238 B CN116278238 B CN 116278238B
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epoxy resin
temperature
clad plate
based copper
resistant epoxy
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CN116278238A (en
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吴海兵
王小龙
陈应峰
谢谏诤
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Jiangsu Yaohong Electronics Co ltd
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Jiangsu Yaohong Electronics Co ltd
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B5/00—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts
    • B32B5/02—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by structural features of a fibrous or filamentary layer
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B15/00—Layered products comprising a layer of metal
    • B32B15/14—Layered products comprising a layer of metal next to a fibrous or filamentary layer
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B15/00—Layered products comprising a layer of metal
    • B32B15/20—Layered products comprising a layer of metal comprising aluminium or copper
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
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    • B32B33/00—Layered products characterised by particular properties or particular surface features, e.g. particular surface coatings; Layered products designed for particular purposes not covered by another single class
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    • B32B37/00—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding
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    • B32B37/00—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding
    • B32B37/06—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the heating method
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    • B32B38/164—Drying
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    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/24—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs
    • C08J5/241—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs using inorganic fibres
    • C08J5/244—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs using inorganic fibres using glass fibres
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    • C08J5/249—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs characterised by the additives used in the prepolymer mixture
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K1/00—Printed circuits
    • H05K1/02—Details
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    • H05K1/0313—Organic insulating material
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    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K3/00—Apparatus or processes for manufacturing printed circuits
    • H05K3/0011—Working of insulating substrates or insulating layers
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    • B32B37/00—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding
    • B32B37/14—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the properties of the layers
    • B32B37/24—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the properties of the layers with at least one layer not being coherent before laminating, e.g. made up from granular material sprinkled onto a substrate
    • B32B2037/243—Coating
    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • B32B2255/00—Coating on the layer surface
    • B32B2255/02—Coating on the layer surface on fibrous or filamentary layer
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    • B32B2255/26—Polymeric coating
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    • B32B2307/30—Properties of the layers or laminate having particular thermal properties
    • B32B2307/306—Resistant to heat
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    • B32B2307/3065—Flame resistant or retardant, fire resistant or retardant
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    • B32B2307/7145—Rot proof, resistant to bacteria, mildew, mould, fungi
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    • C08J2363/00—Characterised by the use of epoxy resins; Derivatives of epoxy resins
    • C08J2363/02—Polyglycidyl ethers of bis-phenols
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Abstract

The invention relates to the technical field of copper-clad plates, in particular to a high-temperature-resistant epoxy resin-based copper-clad plate and a preparation method thereof. The invention reacts mercaptopropyl trimethoxy silane with water to generate nano silicon dioxide with mercapto, and then nano silver is loaded on the surface of the nano silicon dioxide through the reaction of mercapto and anions. The melamine formaldehyde resin can decompose and release nitrogen and isolate oxygen when encountering open flame combustion, thereby realizing the flame retardant effect. The melamine formaldehyde resin is used as a wall material, the silica loaded with nano silver is used as a core material to prepare microcapsule and epoxy resin blend, so that the phenomenon of phase separation of inorganic filler and epoxy resin blend can be effectively avoided, the heat resistance is improved, and meanwhile, a certain rigidity is given to the material; silver has a certain antibacterial effect, and the antibacterial effect is better when the silver is combined with silicon dioxide.

Description

High-temperature-resistant epoxy resin-based copper-clad plate and preparation method thereof
Technical Field
The invention relates to the technical field of copper-clad plates, in particular to a high-temperature-resistant epoxy resin-based copper-clad plate and a preparation method thereof.
Background
The third industrial revolution has led to the rapid development of the electronic information and communication technology industry and the copper-clad plate industry. The copper-clad plate is a plate-shaped material which is prepared by loading copper foil on the surface of electronic glass fiber cloth or other reinforcing materials through resin and carrying out a hot pressing process, is mainly used as a base material of a printed circuit board and plays a key role in the performance and quality of the printed circuit board. The manufacturing technology of the copper-clad plate relates to interdigitation, interpenetration and mutual promotion of multiple subjects, and is accompanied with synchronous development of the whole technical field of electronic communication.
The preparation process of the copper-clad plate relates to the welding technology. The traditional welding technology uses cheap tin-lead alloy as welding flux, and lead is a toxic heavy metal element which pollutes the ecological environment and further endangers the human health although the quality of the welded product is reliable. Lead-free welding technology is becoming the mainstream from the concepts of safety and environmental protection. Compared with the traditional welding technology, the temperature of lead-free welding is higher, which puts higher demands on the heat resistance and the thermal stability of the printed circuit board.
The epoxy resin is a high molecular polymer, can show a plurality of excellent performances after being cured, such as high metal adhesion, high chemical corrosion resistance and the like, and has wide application in copper-clad plates. However, the epoxy resin has a poor temperature resistance, which greatly limits the application range. The conventional modification method mainly makes up for short plates with insufficient temperature resistance of the epoxy resin by adding high-temperature-resistant inorganic filler, and the epoxy resin is separated from the inorganic filler, so that the mechanical property and the glass transition temperature of the epoxy resin are reduced, and the cured epoxy resin is embrittled to influence the use quality. Therefore, development of a high-temperature-resistant epoxy resin-based copper-clad plate is very necessary.
Disclosure of Invention
The invention aims to provide a high-temperature-resistant epoxy resin-based copper-clad plate and a preparation method thereof, so as to solve the problems in the background technology.
In order to solve the technical problems, the invention provides the following technical scheme: a high-temperature-resistant epoxy resin-based copper-clad plate and a preparation method thereof comprise the following steps:
step 1:
s1: weighing mercaptopropyl trimethoxy silane, adding the mercaptopropyl trimethoxy silane into deionized water, and continuously stirring until the droplets of mercaptopropyl trimethoxy silane completely disappear; adding ammonia water to regulate the pH value, and continuously stirring for 24-36 hours at room temperature to obtain suspension; centrifuging the suspension, filtering out filtrate, washing filter residues with deionized water and ethanol to obtain silica microspheres with mercapto groups on the surfaces;
s2: dispersing the prepared silicon dioxide microspheres into silver nitrate solution at the temperature of 25-30 ℃, continuously stirring and reacting for 5min, centrifuging, washing with water to obtain silicon dioxide microspheres loaded with nano silver, and dispersing in ethanol solution for later use;
step 2: mixing melamine, formaldehyde and deionized water, mechanically stirring to completely dissolve the melamine, adding a sodium carbonate solution to adjust the pH value of the system to 8-9, and then heating and stirring to react for 3-5 hours to obtain a colorless transparent prepolymer;
step 3: mixing the silica microsphere loaded with nano silver in the step 1 and the prepolymer in the step 2, adding a surfactant, stirring and emulsifying at 65-75 ℃, regulating the pH value to 3-4 by dilute sulfuric acid, reacting for 24-30 h, and washing, filtering and drying to obtain microcapsules;
step 4: heating bisphenol A epoxy resin at 50-75 ℃, adding a curing agent, acetone and microcapsules, and uniformly mixing to obtain resin glue solution; and (3) coating the resin glue solution on glass fiber cloth, drying in a baking oven at 75 ℃ for 10-15 min, coating the copper foil on the resin glue solution, placing the copper foil in a hot press for 2-4 h, taking out and curing for 1-2 h, and thus obtaining the high-temperature-resistant epoxy resin-based copper-clad plate.
Further, in S1, 0.5 to 0.6 part of mercaptopropyl trimethoxy silane and 25 to 30 parts of deionized water by weight.
In S1, ammonia is used for adjusting the pH value to 9.0-10.5.
Further, in S2, 0.4 to 0.6 part by weight of silicon dioxide microspheres, 1.5 to 2 parts by weight of silver nitrate and 8 to 10 parts by weight of deionized water.
Further, in the step 2, 1 to 3 parts of melamine, 2.5 to 7.5 parts of formaldehyde and 4.25 to 13 parts of deionized water by weight are adopted.
In step 2, the temperature of the heating and stirring reaction is 65-80 ℃.
Further, in the step 3, 40 to 45 percent of silica microspheres loaded with nano silver, 50 to 55 percent of prepolymer and 5 percent of surfactant by weight.
In the step 3, the pH value is adjusted to 3-4 by dilute sulfuric acid.
Further, in step 3, the surfactant is any one of sodium dodecyl benzene sulfonate, tween 80, sodium dodecyl sulfate, lithium dodecyl sulfate and alpha-sodium alkenyl sulfonate.
Further, in the step 4, 150 to 180 parts of bisphenol A epoxy resin, 30 to 40 parts of curing agent, 20 to 30 parts of acetone and 10 to 20 parts of microcapsule by weight.
In step 4, the curing agent is any one of ethylenediamine, hexamethylenediamine, diethylenetriamine, maleic anhydride, tetraethylenepentamine and phthalic anhydride.
Compared with the prior art, the invention has the following beneficial effects: the invention dissolves sulfhydryl propyl trimethoxy silane in water to react to generate sulfhydryl-bearing nano silicon dioxide, and nano silver is loaded on the surface of the nano silicon dioxide through the reaction of sulfhydryl and silver ions; preparing microcapsules by taking melamine-formaldehyde resin obtained by reacting melamine with formaldehyde as a wall material and taking nano-silver-loaded nano-silica microspheres as core materials; and blending the microcapsule with epoxy resin, curing agent and the like, and attaching the microcapsule with copper foil to prepare the epoxy resin-based copper-clad plate. The nano silicon dioxide loaded with nano silver has good heat resistance and can endow the material with certain rigidity; silver has a certain antibacterial effect, and the antibacterial effect is better when the silver is combined with silicon dioxide. The melamine formaldehyde resin can decompose and release nitrogen when encountering open flame combustion, and isolate oxygen, thereby realizing the flame retardant effect. Because melamine formaldehyde and epoxy resin are thermosetting materials, the toughness can be improved after blending. In addition, the inorganic filler and the epoxy resin are blended to generate phase separation, so that the mechanical property and the glass transition temperature of the epoxy resin are reduced, the cured epoxy resin becomes brittle, and the use quality is affected; the problem can be solved by using melamine formaldehyde resin to wrap and prepare the microcapsule, and the high-temperature-resistant epoxy resin-based copper-clad plate is obtained.
Detailed Description
The following description of the technical solutions in the embodiments of the present invention will be clear and complete, and it is obvious that the described embodiments are only some embodiments of the present invention, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
The main materials and sources thereof in the following examples are as follows: mercaptopropyl trimethoxysilane is available from the pharmaceutical chemical company, inc., wohana white, CAS number: 4420-74-0; melamine is from zhihong chemical industry, CAS no: 108-78-1; anhydrous sodium carbonate from nine chemicals, CAS no: 497-19-8; formaldehyde was from jia hong fine chemicals limited, CAS No.: 50-00-0; bisphenol A epoxy resin E51 comes from forest chemical industry, and has an average molecular weight of 4500-5000; ammonia comes from the civil engineering, CAS number: 1336-21-6; silver nitrate is from Allatin, CAS number 7761-88-8; ethanol was from aladine, CAS No.: 64-17-5; sodium lauryl sulfate was from stonerformance chemistry, CAS No.: 151-21-3; tetraethylenepentamine is from north China chemical industry, CAS no: 112-57-2, acetone from aladine, CAS No.: 67-64-1; sulfuric acid from aladine, CAS no: 7664-93-9.
Example 1:
step 1:
s1: weighing 0.05kg of mercaptopropyl trimethoxysilane, adding the mercaptopropyl trimethoxysilane into 2.5kg of deionized water, and continuously stirring until the droplets of mercaptopropyl trimethoxysilane completely disappear; adding ammonia water to adjust the pH value to 9, and continuously stirring for 24 hours at room temperature to obtain suspension; centrifuging the suspension, filtering out filtrate, washing filter residues with deionized water and ethanol to obtain silica microspheres with mercapto groups on the surfaces;
s2: mixing 0.4kg of silicon dioxide microspheres, 1.5kg of silver nitrate and 8kg of deionized water at 25 ℃, continuously stirring and reacting for 5min, centrifuging, washing to obtain nano-silver loaded silicon dioxide microspheres, and dispersing in ethanol solution for later use;
step 2: mixing 1kg of melamine, 2.5kg of formaldehyde and 4.25kg of deionized water, mechanically stirring to completely dissolve the melamine, adding a sodium carbonate solution to adjust the pH value of the system to 8, heating to 65 ℃, and stirring to react for 3 hours to obtain a colorless transparent prepolymer;
step 3: mixing the silica microspheres loaded with nano silver in the step 1 and the prepolymer in the step 2, adding sodium dodecyl sulfate, stirring and emulsifying at 65 ℃, regulating the pH value to 3 by dilute sulfuric acid, reacting for 24 hours, and washing, filtering and drying to obtain microcapsules; the content of each component is 40% of silicon dioxide microsphere loaded with nano silver, 55% of prepolymer and 5% of sodium dodecyl benzene sulfonate by weight.
Step 4: heating 15kg bisphenol A epoxy resin at 50 ℃, adding 3kg tetraethylenepentamine, 2kg acetone and 1kg microcapsule, and uniformly mixing to obtain resin glue solution; and (3) coating the resin glue solution on glass fiber cloth, drying in a 75 ℃ oven for 10min, coating the copper foil on the resin glue solution, placing in a hot press for 2h, taking out and curing for 1h, and thus obtaining the high-temperature-resistant epoxy resin-based copper-clad plate.
Example 2:
step 1:
s1: weighing 0.052kg of mercaptopropyl trimethoxysilane, adding the mercaptopropyl trimethoxysilane into 2.8kg of deionized water, and continuously stirring until the droplets of mercaptopropyl trimethoxysilane completely disappear; adding ammonia water to adjust the pH value to 9.5, and continuously stirring at room temperature for 28 hours to obtain suspension; centrifuging the suspension, filtering out filtrate, washing filter residues with deionized water and ethanol to obtain silica microspheres with mercapto groups on the surfaces;
s2: mixing 0.45kg of silicon dioxide microspheres, 1.8kg of silver nitrate and 9kg of deionized water at 30 ℃, continuously stirring and reacting for 5min, centrifuging, washing with water to obtain nano-silver loaded silicon dioxide microspheres, and dispersing in ethanol solution for later use;
step 2: mixing 1.25kg of melamine, 3.2kg of formaldehyde and 6.5kg of deionized water, mechanically stirring to completely dissolve the melamine, adding a sodium carbonate solution to adjust the pH value of the system to 8.5, heating to 70 ℃, and stirring for reacting for 4 hours to obtain a colorless transparent prepolymer;
step 3: mixing the silica microspheres loaded with nano silver in the step 1 and the prepolymer in the step 2, adding sodium dodecyl sulfate, stirring and emulsifying at 70 ℃, regulating the pH value to 3.5 by dilute sulfuric acid, reacting for 25 hours, and washing, filtering and drying to obtain microcapsules; the content of each component is 42% of silicon dioxide microsphere loaded with nano silver, 53% of prepolymer and 5% of sodium dodecyl benzene sulfonate by weight.
Step 4: heating 16kg bisphenol A epoxy resin at 65 ℃, adding 3.2kg tetraethylenepentamine, 2.2kg acetone and 1.6kg microcapsule, and uniformly mixing to obtain resin glue solution; and (3) coating the resin glue solution on glass fiber cloth, drying in a baking oven at 75 ℃ for 12min, coating the copper foil on the resin glue solution, placing the copper foil in a hot press for 2.5h, taking out and curing for 1.5h, and thus obtaining the high-temperature-resistant epoxy resin-based copper-clad plate.
Example 3:
step 1:
s1: weighing 0.056kg of mercaptopropyl trimethoxysilane, adding the mercaptopropyl trimethoxysilane into 2.85kg of deionized water, and continuously stirring until the droplets of mercaptopropyl trimethoxysilane completely disappear; adding ammonia water to adjust the pH value to 10, and continuously stirring for 27h at room temperature to obtain suspension; centrifuging the suspension, filtering out filtrate, washing filter residues with deionized water and ethanol to obtain silica microspheres with mercapto groups on the surfaces;
s2: mixing 0.45kg of silicon dioxide microspheres, 1.8kg of silver nitrate and 9kg of deionized water at 28 ℃, continuously stirring and reacting for 5min, centrifuging, washing to obtain nano-silver loaded silicon dioxide microspheres, and dispersing in ethanol solution for later use;
step 2: mixing 2.5kg of melamine, 5.5kg of formaldehyde and 9kg of deionized water, mechanically stirring to completely dissolve the melamine, adding a sodium carbonate solution to adjust the pH value of the system to 9, heating to 75 ℃, and stirring to react for 1.5h to obtain a colorless transparent prepolymer;
step 3: mixing the silica microspheres loaded with nano silver in the step 1 and the prepolymer in the step 2, adding sodium dodecyl sulfate, stirring and emulsifying at 75 ℃, regulating the pH value to 3.5 by dilute sulfuric acid, reacting for 30 hours, and washing, filtering and drying to obtain microcapsules; the components comprise 44% of silica microsphere loaded with nano silver, 51% of prepolymer and 5% of sodium dodecyl benzene sulfonate by weight.
Step 4: heating 17kg of bisphenol A epoxy resin at 65 ℃, adding 3.4kg of tetraethylenepentamine, 2.5kg of acetone and 1.3kg of microcapsules, and uniformly mixing to obtain resin glue solution; and (3) coating the resin glue solution on glass fiber cloth, drying in a baking oven at 75 ℃ for 15min, coating the copper foil on the resin glue solution, placing the copper foil in a hot press for 4h, taking out and curing for 2h, and thus obtaining the high-temperature-resistant epoxy resin-based copper-clad plate.
Example 4:
step 1:
s1: weighing 0.054kg of mercaptopropyl trimethoxysilane, adding the mercaptopropyl trimethoxysilane into 2.8kg of deionized water, and continuously stirring until the droplets of mercaptopropyl trimethoxysilane completely disappear; adding ammonia water to adjust the pH value to 9.5, and continuously stirring for 27h at room temperature to obtain suspension; centrifuging the suspension, filtering out filtrate, washing filter residues with deionized water and ethanol to obtain silica microspheres with mercapto groups on the surfaces;
s2: mixing 0.5kg of silicon dioxide microspheres, 1.65kg of silver nitrate and 8.5kg of deionized water at 30 ℃, continuously stirring and reacting for 5min, centrifuging, washing with water to obtain silicon dioxide microspheres loaded with nano silver, and dispersing in ethanol solution for later use;
step 2: mixing 2.3kg of melamine, 5.6kg of formaldehyde and 12kg of deionized water, mechanically stirring to completely dissolve the melamine, adding a sodium carbonate solution to adjust the pH value of the system to 8.5, heating to 80 ℃, and stirring to react for 1.5h to obtain a colorless transparent prepolymer;
step 3: mixing the silica microspheres loaded with nano silver in the step 1 and the prepolymer in the step 2, adding sodium dodecyl sulfate, stirring and emulsifying at 70 ℃, regulating the pH value to 3.5 by dilute sulfuric acid, reacting for 27h, and washing, filtering and drying to obtain microcapsules; the components comprise 43% of silicon dioxide microsphere loaded with nano silver, 52% of prepolymer and 5% of sodium dodecyl benzene sulfonate by weight.
Step 4: heating 17kg of bisphenol A epoxy resin at 65 ℃, adding 3.4kg of tetraethylenepentamine, 2.5kg of acetone and 1kg of microcapsules, and uniformly mixing to obtain resin glue solution; and (3) coating the resin glue solution on glass fiber cloth, drying in a 75 ℃ oven for 10min, coating the copper foil on the resin glue solution, placing in a hot press for 3h, taking out and curing for 2h, and thus obtaining the high-temperature-resistant epoxy resin-based copper-clad plate.
Example 5:
step 1:
s1: weighing 0.058kg of mercaptopropyl trimethoxysilane, adding the mercaptopropyl trimethoxysilane into 2.85kg of deionized water, and continuously stirring until the droplets of mercaptopropyl trimethoxysilane completely disappear; adding ammonia water to adjust the pH value to 9-10.5, and continuously stirring at room temperature for 36h to obtain suspension; centrifuging the suspension, filtering out filtrate, washing filter residues with deionized water and ethanol to obtain silica microspheres with mercapto groups on the surfaces;
s2: mixing 0.6kg of silicon dioxide microspheres, 1.7kg of silver nitrate and 9.5kg of deionized water at 30 ℃, continuously stirring and reacting for 5min, centrifuging, washing with water to obtain silicon dioxide microspheres loaded with nano silver, and dispersing in ethanol solution for later use;
step 2: mixing 1kg of melamine, 3kg of formaldehyde and 8.5kg of deionized water, mechanically stirring to completely dissolve the melamine, adding a sodium carbonate solution to adjust the pH value of the system to 9, heating to 70 ℃, and stirring to react for 1.5h to obtain a colorless transparent prepolymer;
step 3: mixing the silica microspheres loaded with nano silver in the step 1 and the prepolymer in the step 2, adding sodium dodecyl sulfate, stirring and emulsifying at 70 ℃, regulating the pH value to 3.5 by dilute sulfuric acid, reacting for 26 hours, and washing, filtering and drying to obtain microcapsules; the content of each component is 45% of silicon dioxide microsphere loaded with nano silver, 50% of prepolymer and 5% of sodium dodecyl benzene sulfonate by weight.
Step 4: heating 16.5kg bisphenol A epoxy resin at 50 ℃, adding 3kg tetraethylenepentamine, 2kg acetone and 1kg microcapsule, and uniformly mixing to obtain resin glue solution; and (3) coating the resin glue solution on glass fiber cloth, drying in a baking oven at 75 ℃ for 15min, coating the copper foil on the resin glue solution, placing in a hot press for 3h, taking out and curing for 1.2h, and thus obtaining the high-temperature-resistant epoxy resin-based copper-clad plate.
Example 6:
step 1:
s1: weighing 0.056kg of mercaptopropyl trimethoxysilane, adding the mercaptopropyl trimethoxysilane into 2.75kg of deionized water, and continuously stirring until the droplets of mercaptopropyl trimethoxysilane completely disappear; adding ammonia water to adjust the pH value to 10, and continuously stirring at room temperature for 28 hours to obtain suspension; centrifuging the suspension, filtering out filtrate, washing filter residues with deionized water and ethanol to obtain silica microspheres with mercapto groups on the surfaces;
s2: mixing 0.5kg of silicon dioxide microspheres, 1.8kg of silver nitrate and 9kg of deionized water at 27 ℃, continuously stirring and reacting for 5min, centrifuging, washing with water to obtain silicon dioxide microspheres loaded with nano silver, and dispersing in ethanol solution for later use;
step 2: mixing 3kg of melamine, 7.5kg of formaldehyde and 13kg of deionized water, mechanically stirring to completely dissolve the melamine, adding a sodium carbonate solution to adjust the pH value of the system to 9, heating to 80 ℃, and stirring to react for 1.5h to obtain a colorless transparent prepolymer;
step 3: mixing the silica microspheres loaded with nano silver in the step 1 and the prepolymer in the step 2, adding sodium dodecyl sulfate, stirring and emulsifying at 75 ℃, regulating the pH value to 3.5 by dilute sulfuric acid, reacting for 24-30 h, and washing, filtering and drying to obtain microcapsules; the content of each component is 45% of silicon dioxide microsphere loaded with nano silver, 50% of prepolymer and 5% of sodium dodecyl benzene sulfonate by weight.
Step 4: heating 16.5kg bisphenol A epoxy resin at 60 ℃, adding 3.7kg tetraethylenepentamine, 2.3kg acetone and 1.3kg microcapsule, and uniformly mixing to obtain resin glue solution; and (3) coating the resin glue solution on glass fiber cloth, drying in a baking oven at 75 ℃ for 10min, coating the copper foil on the resin glue solution, placing the copper foil in a hot press for 2-4 h, taking out and curing for 1-2 h, and thus obtaining the high-temperature-resistant epoxy resin-based copper-clad plate.
Comparative example 1:
and preparing the epoxy resin copper-clad plate without adding microcapsules.
Heating 15kg of bisphenol A epoxy resin at 50 ℃, adding 3kg of tetraethylenepentamine and 2kg of acetone, and uniformly mixing to obtain resin glue solution; and (3) coating the resin glue solution on glass fiber cloth, drying in a 75 ℃ oven for 10min, coating the copper foil on the resin glue solution, placing in a hot press for 2h, taking out and curing for 1h, and thus obtaining the high-temperature-resistant epoxy resin-based copper-clad plate.
Comparative example 2:
and (3) preparing the epoxy resin-based copper-clad plate by adding only nano silicon dioxide.
Step 1: weighing 0.052kg of mercaptopropyl trimethoxysilane, adding the mercaptopropyl trimethoxysilane into 2.8kg of deionized water, and continuously stirring until the droplets of mercaptopropyl trimethoxysilane completely disappear; adding ammonia water to adjust the pH value to 9.5, and continuously stirring at room temperature for 28 hours to obtain suspension; centrifuging the suspension, filtering out filtrate, washing filter residues with deionized water and ethanol to obtain silica microspheres;
step 2: heating 16kg bisphenol A epoxy resin at 65 ℃, adding 3.2kg tetraethylenepentamine, 2.2kg acetone and 1.6kg microcapsule, and uniformly mixing to obtain resin glue solution; and (3) coating the resin glue solution on glass fiber cloth, drying in a baking oven at 75 ℃ for 12min, coating the copper foil on the resin glue solution, placing the copper foil in a hot press for 2.5h, taking out and curing for 1.5h, and thus obtaining the high-temperature-resistant epoxy resin-based copper-clad plate.
Comparative example 3:
and (3) preparing the epoxy resin-based copper-clad plate by only adding melamine formaldehyde resin.
Step 1: mixing 2.5kg of melamine, 5.5kg of formaldehyde and 9kg of deionized water, mechanically stirring to completely dissolve the melamine, adding a sodium carbonate solution to adjust the pH value of the system to 9, heating to 75 ℃, and stirring to react for 1.5h to obtain a colorless transparent prepolymer; regulating the pH value to 3.5 by dilute sulfuric acid, reacting for 30 hours, and washing, filtering and drying to obtain melamine formaldehyde resin;
step 2: heating 17kg of bisphenol A epoxy resin at 65 ℃, adding 3.4kg of tetraethylenepentamine, 2.5kg of acetone and 1.3kg of melamine formaldehyde resin, and uniformly mixing to obtain resin glue solution; and (3) coating the resin glue solution on glass fiber cloth, drying in a baking oven at 75 ℃ for 15min, coating the copper foil on the resin glue solution, placing the copper foil in a hot press for 4h, taking out and curing for 2h, and thus obtaining the high-temperature-resistant epoxy resin-based copper-clad plate.
Comparative example 4:
directly blending melamine formaldehyde resin and nano silicon dioxide to prepare the epoxy resin-based copper-clad plate.
Step 1: weighing 0.054kg of mercaptopropyl trimethoxysilane, adding the mercaptopropyl trimethoxysilane into 2.8kg of deionized water, and continuously stirring until the droplets of mercaptopropyl trimethoxysilane completely disappear; adding ammonia water to adjust the pH value to 9.5, and continuously stirring for 27h at room temperature to obtain suspension; centrifuging the suspension, filtering out filtrate, washing filter residues with deionized water and ethanol to obtain silica microspheres with mercapto groups on the surfaces;
step 2: mixing 2.3kg of melamine, 5.6kg of formaldehyde and 12kg of deionized water, mechanically stirring to completely dissolve the melamine, adding a sodium carbonate solution to adjust the pH value of the system to 8.5, heating to 80 ℃, and stirring to react for 1.5h to obtain a colorless transparent prepolymer; adjusting the pH value to 3.5 by dilute sulfuric acid, reacting for 27h, and washing, filtering and drying to obtain melamine formaldehyde resin;
step 4: heating 17kg of bisphenol A epoxy resin at 65 ℃, adding 3.4kg of tetraethylenepentamine, 2.5kg of acetone and 1kg of microcapsules, and uniformly mixing to obtain resin glue solution; and (3) coating the resin glue solution on glass fiber cloth, drying in a 75 ℃ oven for 10min, coating the copper foil on the resin glue solution, placing in a hot press for 3h, taking out and curing for 2h, and thus obtaining the high-temperature-resistant epoxy resin-based copper-clad plate.
Experiment: the following tests were carried out for examples 1 to 6 and comparative examples 1 to 4, respectively:
flame retardancy: testing according to the method specified in UL 94;
thermal stability: heating to 500 ℃ under nitrogen atmosphere at a heating rate of 5 ℃/min, and recording the temperature at which heat loss occurs;
peel strength: according to the method of IPC-TM-650-2.4.8B;
elongation at break: testing by an HY-5080 universal tensile testing machine;
antibacterial properties: the cured epoxy resin with the diameter of 5cm is placed in a culture dish of candida albicans, and the bacterial colony number is measured for 48 hours, so that the antibacterial rate is obtained.
The experimental results are shown in the following table:
conclusion: the epoxy resin-based copper-clad plate prepared by the method has excellent high temperature resistance and good flame retardant effect; the toughness is high, and the elongation at break and the peel strength are relatively high; the product has a certain antibacterial effect due to the metal silver and the silicon dioxide. With the reference of example 1, the data of comparative example 1 show that the performances of the epoxy resin-based copper-clad plate are poor under the condition of no microcapsule addition; with the example 2 as a reference, the data of the comparative example 2 show that the toughness of the product is poor and the peel strength and the breaking elongation are reduced after the silicon dioxide is directly doped; taking example 3 as a reference, the data of comparative example 3 show that the product prepared by adding melamine formaldehyde resin only has slightly reduced thermal stability despite good flame retardant properties; the data of comparative example 4, which has been presented with reference to example 4, shows that the flame retardancy and thermal stability are not reduced but the toughness of the product is deteriorated after the melamine formaldehyde resin is directly blended with silica. Therefore, the epoxy resin-based copper-clad plate prepared by the invention can be used under high temperature conditions, and has good toughness and antibacterial property.
Finally, it should be noted that: the foregoing description is only a preferred embodiment of the present invention, and the present invention is not limited thereto, but it is to be understood that modifications and equivalents of some of the technical features described in the foregoing embodiments may be made by those skilled in the art, although the present invention has been described in detail with reference to the foregoing embodiments. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention should be included in the protection scope of the present invention.

Claims (10)

1. A preparation method of a high-temperature-resistant epoxy resin-based copper-clad plate is characterized by comprising the following steps: the method comprises the following steps:
step 1:
s1: adding mercaptopropyl trimethoxy silane into deionized water and stirring; adding ammonia water to regulate pH value to obtain suspension; centrifuging and filtering the suspension, and washing filter residues with deionized water and ethanol to obtain silica microspheres with mercapto groups on the surfaces;
s2: dispersing the prepared silica microspheres with mercapto groups on the surface into silver nitrate solution, continuing stirring reaction, centrifuging, washing with water to obtain silica microspheres loaded with nano silver, and dispersing in ethanol solution for later use;
step 2: mixing melamine, formaldehyde and deionized water, mechanically stirring to completely dissolve the melamine, adding a sodium carbonate solution to adjust the pH value of the system, and heating and stirring to react to obtain a colorless transparent prepolymer;
step 3: mixing the silica microspheres loaded with nano silver in the step 1 and the prepolymer in the step 2, adding a surfactant, heating, stirring and emulsifying, regulating the pH value with dilute sulfuric acid, and washing, filtering and drying to obtain microcapsules;
step 4: heating bisphenol A epoxy resin, adding a curing agent, acetone and microcapsules, and uniformly mixing to obtain resin glue solution; and coating the resin glue solution on glass fiber cloth, semi-curing, coating the copper foil on the resin glue solution, and hot-pressing and curing to obtain the high-temperature-resistant epoxy resin-based copper-clad plate.
2. The method for preparing the high-temperature-resistant epoxy resin-based copper-clad plate according to claim 1, which is characterized by comprising the following steps: in S1, 0.5 to 0.6 part of mercaptopropyl trimethoxy silane and 25 to 30 parts of deionized water by weight; the pH value is regulated to 9.0-10.5 by ammonia water.
3. The method for preparing the high-temperature-resistant epoxy resin-based copper-clad plate according to claim 1, which is characterized by comprising the following steps: in S2, 0.4 to 0.6 part by weight of silicon dioxide microsphere with mercapto group on the surface, 1.5 to 2 parts by weight of silver nitrate and 8 to 10 parts by weight of deionized water.
4. The method for preparing the high-temperature-resistant epoxy resin-based copper-clad plate according to claim 1, which is characterized by comprising the following steps: in the step 2, 1 to 3 parts of melamine, 2.5 to 7.5 parts of formaldehyde and 4.25 to 13 parts of deionized water by weight.
5. The method for preparing the high-temperature-resistant epoxy resin-based copper-clad plate according to claim 1, which is characterized by comprising the following steps: in the step 2, the temperature of the heating and stirring reaction is 65-80 ℃; and regulating the pH value of the system to 8-9 by using the sodium carbonate solution.
6. The method for preparing the high-temperature-resistant epoxy resin-based copper-clad plate according to claim 1, which is characterized by comprising the following steps: in the step 3, the pH value is regulated to 3 to 4 by dilute sulfuric acid; 40-45% of silica microsphere loaded with nano silver, 50-55% of prepolymer and 5% of surfactant.
7. The method for preparing the high-temperature-resistant epoxy resin-based copper-clad plate according to claim 1, which is characterized by comprising the following steps: in the step 3, the surfactant is any one of sodium dodecyl benzene sulfonate, tween 80, sodium dodecyl sulfate, lithium dodecyl sulfate and alpha-sodium alkenyl sulfonate.
8. The method for preparing the high-temperature-resistant epoxy resin-based copper-clad plate according to claim 1, which is characterized by comprising the following steps: in the step 4, 150 to 180 parts of bisphenol A epoxy resin, 30 to 40 parts of curing agent, 20 to 30 parts of acetone and 10 to 20 parts of microcapsule by weight.
9. The method for preparing the high-temperature-resistant epoxy resin-based copper-clad plate according to claim 1, which is characterized by comprising the following steps: in the step 4, the curing agent is any one of ethylenediamine, hexamethylenediamine, diethylenetriamine, maleic anhydride, tetraethylenepentamine and phthalic anhydride.
10. The high-temperature-resistant epoxy resin-based copper-clad plate prepared by the preparation method of the high-temperature-resistant epoxy resin-based copper-clad plate according to any one of claims 1 to 9.
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CN113717497A (en) * 2021-09-13 2021-11-30 贵溪奥泰铜业有限公司 Production method of high-flexibility copper-clad plate
CN113831684A (en) * 2021-09-09 2021-12-24 山东金宝电子股份有限公司 Epoxy resin glue solution, prepreg and glass fiber epoxy resin copper-clad plate containing epoxy resin glue solution and preparation method of prepreg and glass fiber epoxy resin copper-clad plate
CN113844128A (en) * 2021-09-09 2021-12-28 江苏耀鸿电子有限公司 Lead-free high-heat-resistance copper-clad plate and preparation method thereof
CN114274618A (en) * 2021-12-21 2022-04-05 江苏联鑫电子工业有限公司 Halogen-containing high-Tg high-speed copper-clad plate for communication server and preparation method thereof

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JP2000154301A (en) * 1998-11-20 2000-06-06 Toshiba Chem Corp Resin composition for glass epoxy copper-clad laminate
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