CN115651366B - Alumina-containing resin glue solution for copper-clad plate and preparation method thereof - Google Patents
Alumina-containing resin glue solution for copper-clad plate and preparation method thereof Download PDFInfo
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Abstract
The invention relates to the field of copper-clad plates, in particular to an alumina-containing resin glue solution for a copper-clad plate and a preparation method thereof. According to the invention, the composite aerogel of three flame retardant materials, namely chitosan, melamine formaldehyde resin and methyltrimethoxysilane, is prepared by a sol-gel method and supercritical carbon dioxide drying method, and is blended with epoxy resin and aluminum oxide to obtain the resin glue solution for the high-flame-retardant copper-clad plate. The chitosan can form a three-dimensional crosslinked network, and after being blended with the epoxy resin glue solution, the toughness can be improved, and the hard and brittle texture of the resin after being cured is prevented. When encountering open fire, the melamine formaldehyde resin is decomposed to generate nontoxic and harmless nitrogen and isolate oxygen, and the epoxy resin is blocked from further combustion. In addition, the methyltrimethoxysilane is an environment-friendly silicon flame retardant, and can endow aerogel with certain hydrophobic property after being chemically crosslinked with chitosan, so that the surface of the copper-clad plate is kept dry, and a circuit is protected.
Description
Technical Field
The invention relates to the technical field of copper-clad plates, in particular to an alumina-containing resin glue solution for a copper-clad plate and a preparation method thereof.
Background
The third industrial revolution has promoted the vigorous development of the PC Internet industry, and simultaneously promotes the fusion of mobile communication and Internet technology, so that the human society is led to enter an informatization era. In recent years, the development of the fifth generation mobile communication technology (called 5G for short) is in progress, and the 5G has the characteristics of high speed, low time delay and large connection, and is the basis for realizing man-machine object interconnection. At present, china occupies the head of a chelate in the technical field of new generation broadband mobile communication, so that 5G also becomes a key novel infrastructure for supporting digital, networked and intelligent transformation of economy and society in China, and has huge potential in aspects of investment stabilization, consumption promotion, upgrading promotion, new kinetic energy development of cultivation economy and the like.
Copper-clad plates are core materials for manufacturing printed circuit boards and are known as the foundation of the electronic information industry. With the development of 5G technology, the requirements on the comprehensive performance of the copper-clad plate are higher and higher. The epoxy resin is a high molecular polymer, can show a plurality of excellent performances after being cured, such as high metal adhesive force, high chemical corrosion resistance, high mechanical strength and the like, and has wide application in copper-clad plates. As the common epoxy resin belongs to inflammables, potential safety hazards exist in application, the traditional copper-clad plate adopts brominated epoxy resin to improve flame retardant property, however, the bromine-containing flame retardant can be decomposed to generate smoke and corrosive gas in the using and recycling processes, and atmospheric pollution is caused. Although aluminum oxide can greatly help the performance improvement of epoxy resin as an inorganic filler, the aluminum oxide has overlarge hardness, precipitation phenomenon easily occurs in the epoxy resin, and the performance of the epoxy resin after curing can be even affected by excessive usage. Therefore, it is very necessary to develop a novel resin glue solution containing aluminum oxide for copper-clad plates, which meets the alternating requirements of communication technology and simultaneously ensures the environmental protection.
Disclosure of Invention
The invention aims to provide a resin glue solution for a copper-clad plate and a preparation method thereof, which are used for solving the problems in the background technology.
In order to solve the technical problems, the invention provides the following technical scheme: a resin glue solution for copper-clad plates and a preparation method thereof comprise the following steps:
step 1: dissolving melamine and anhydrous sodium carbonate in deionized water, heating to 50-60 ℃ in a water bath, stirring for 20-30 min, adding formaldehyde solution with the mass concentration of 37% after substances in the system are uniformly mixed, continuously stirring to be transparent, and carrying out prepolymerization at normal temperature for 3-5 h in a sealing manner to obtain a mixed solution A;
step 2: preparing an acetic acid solution with the mass concentration of 1%, adding chitosan, stirring for 2-3 hours at normal temperature, adding a formaldehyde solution with the mass concentration of 40%, continuously stirring for 5-10 minutes, sealing, standing and prepolymerizing for 1-2 hours to obtain a mixed solution B;
step 3: mixing the mixed solution A and the mixed solution B, regulating the pH value to 4.5-5 by acetic acid, adding methyltrimethoxysilane to obtain a mixed solution C, and stirring and uniformly mixing to obtain wet gel;
step 4: performing solvent exchange after the wet gel is aged, and drying by adopting supercritical carbon dioxide to obtain composite aerogel;
step 5: heating bisphenol A epoxy resin at 50-75 ℃, adding a curing agent, acetone, an accelerator, composite aerogel and alumina, and uniformly mixing to obtain the alumina-containing resin glue solution for the copper-clad plate.
In step 1, the water bath heating temperature is 50-60 ℃.
In the step 1, the mixed solution A comprises, by weight, 10-15 parts of melamine, 0.3-0.5 part of anhydrous sodium carbonate, 100 parts of deionized water and 16-20 parts of formaldehyde solution.
Further, in the step 2, the mass concentration of the acetic acid solution is 1%.
In step 2, the content of each component in the mixed solution B is 10-12 parts by weight of acetic acid solution, 0.1-0.2 part by weight of chitosan and 0.1-0.13 part by weight of formaldehyde solution.
Further, in the step 3, the amount of each component is 10-15 parts by weight of mixed solution A; 1-2 parts of mixed solution B;4.5 to 5 parts of methyltrimethoxysilane.
Further, in the step 4, the aging temperature of the wet gel is 40-45 ℃; the aging time is 36-48 h.
In step 4, the specific method of solvent exchange is that absolute ethanol is used for exchange for 60-72 h, and then acetone is used for exchange for 60-72 h.
In step 5, the bisphenol A epoxy resin is heated to a temperature of 50 to 75 ℃.
Further, in step 5, the content of each component in the resin glue solution containing alumina for copper-clad plate is 120-150 parts by weight of bisphenol A epoxy resin, 20-35 parts by weight of curing agent, 8-12 parts by weight of acetone, 3-7 parts by weight of accelerator, 20-30 parts by weight of composite aerogel and 10-20 parts by weight of alumina.
Further, in step 5, the curing agent is any one of ethylenediamine, hexamethylenediamine, diethylenetriamine, maleic anhydride and phthalic anhydride; the accelerator is any one of imidazole curing accelerator, organic phosphine curing accelerator or tertiary amine curing accelerator.
Compared with the prior art, the invention has the following beneficial effects: the invention prepares the resin glue solution containing the aluminum oxide for the copper-clad plate, and prepares the chitosan/melamine formaldehyde resin/methyltrimethoxysilane flame-retardant aerogel through a sol-gel method and supercritical carbon dioxide drying. The chitosan is a rich and renewable natural polymer, has good biocompatibility and degradability, can form a three-dimensional crosslinked network, and can improve the toughness of the cured material after being blended with epoxy resin glue solution. The linear chain of the chitosan macromolecules contains a large number of hydroxyl groups and amino groups, the chitosan fiber macromolecules have orderly structure arrangement and high crystallinity, so that the chitosan has good thermal stability, the limiting oxygen index of the chitosan is 38%, and the chitosan has good flame retardance; the melamine formaldehyde resin and the methyltrimethoxysilane are flame-retardant materials, and the chitosan/melamine formaldehyde resin/methyltrimethoxysilane flame-retardant aerogel, the epoxy resin, the aluminum oxide and the like are blended, so that the copper-clad plate with high flame retardance is obtained, and when open flame is encountered, the melamine formaldehyde resin is decomposed to generate nontoxic and harmless nitrogen, so that oxygen is isolated, and the epoxy resin is blocked from further combustion. In addition, the melamine formaldehyde resin can improve the mechanical strength of the chitosan aerogel; the methyltrimethoxysilane is an environment-friendly silicon flame retardant, and can endow aerogel with certain hydrophobic property after being chemically crosslinked with chitosan, thereby being beneficial to the surface drying of the copper-clad plate and protecting a circuit.
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: 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; acetic acid was from mikrin, CAS no: 64-19-7; chitosan was from ravigneaux biotechnology, CAS no: 9012-76-4, and the average molecular weight is 1200-1500; methyltrimethoxysilane is from the cori new material, CAS no: 1185-55-3; acetone was from mikrin, CAS no: 67-64-1; bisphenol A epoxy resin (E-03 type) was obtained from Henan Kao commercial Co., ltd., CAS number: 25085-99-8; ethylenediamine is from south Beijing reagent, CAS number: 107-15-3;2MZ-a from japan four kingdom formation; alumina was from new wear resistant materials limited, CAS No.: 1344-28-1.
Example 1:
step 1: dissolving 1kg of melamine and 0.03kg of anhydrous sodium carbonate in 10kg of deionized water, heating to 50 ℃ in a water bath, stirring for 20min, adding 1.6kg of 37% formaldehyde solution by mass concentration after substances in the system are uniformly mixed, continuously stirring to be transparent, and sealing and placing in a room temperature for prepolymerization for 3h to obtain a mixed solution A;
step 2: adding 0.01kg of chitosan into 1kg of acetic acid solution with the mass concentration of 1%, stirring for 2 hours at normal temperature, adding 0.01kg of formaldehyde solution with the mass concentration of 40%, continuously stirring for 5 minutes, sealing, standing and prepolymerizing for 1 hour to obtain a mixed solution B;
step 3: mixing 1kg of mixed solution A and 0.1kg of mixed solution B, regulating the pH value to 4.5 by acetic acid, adding 0.45kg of methyltrimethoxysilane to obtain mixed solution C, and stirring and uniformly mixing to obtain wet gel;
step 4: aging wet gel at 40deg.C for 36 hr, then performing solvent exchange, firstly exchanging with anhydrous ethanol for 60 hr, and then exchanging with acetone for 60 hr; drying by supercritical carbon dioxide to obtain composite aerogel;
step 5: heating 12kg of bisphenol A epoxy resin at 50-75 ℃, adding 2kg of ethylenediamine, 0.8kg of acetone, 0.3kg of 2MZ-A, 2kg of composite aerogel and 1kg of alumina, and uniformly mixing to obtain the alumina-containing resin glue solution for the copper-clad plate.
Example 2:
step 1: dissolving 1.2kg of melamine and 0.35kg of anhydrous sodium carbonate in 10kg of deionized water, heating to 55 ℃ in a water bath, stirring for 25min, adding 1.8kg of 37% formaldehyde solution by mass concentration after substances in the system are uniformly mixed, continuously stirring until the mixture is transparent, and sealing and pre-polymerizing for 4h at normal temperature to obtain a mixed solution A;
step 2: adding 0.012kg of chitosan into 1.1kg of acetic acid solution with the mass concentration of 1%, stirring for 2.5h at normal temperature, adding 0.011kg of formaldehyde solution with the mass concentration of 40%, continuously stirring for 10min, sealing, standing and prepolymerizing for 1.5h to obtain a mixed solution B;
step 3: mixing 1.2kg of mixed solution A and 0.15 kg of mixed solution B, regulating the pH value to 5 by acetic acid, adding 0.48 methyltrimethoxysilane to obtain mixed solution C, and stirring and uniformly mixing to obtain wet gel;
step 4: aging wet gel at 45deg.C for 42 hr, then performing solvent exchange, firstly exchanging with anhydrous ethanol for 65 hr, and then exchanging with acetone for 65 hr; drying by supercritical carbon dioxide to obtain composite aerogel;
step 5: 13kg of bisphenol A epoxy resin is heated at 60 ℃, 3kg of ethylenediamine, 0.8kg of acetone, 0.5kg of 2MZ-A, 2.6kg of composite aerogel and 1.2 alumina are added and mixed uniformly, and the resin glue solution containing alumina for the copper-clad plate can be obtained.
Example 3:
step 1: dissolving 1.3kg of melamine and 0.03kg of anhydrous sodium carbonate in 10kg of deionized water, heating to 60 ℃ in a water bath, stirring for 30min, adding 1.7kg of 37% formaldehyde solution by mass concentration after substances in the system are uniformly mixed, continuously stirring until the mixture is transparent, and sealing and pre-polymerizing for 5h at normal temperature to obtain a mixed solution A;
step 2: adding 0.018 part of chitosan into 1.15kg of acetic acid solution with the mass concentration of 1%, stirring for 3 hours at normal temperature, adding 0.013 part of formaldehyde solution with the mass concentration of 40%, continuously stirring for 10 minutes, sealing, standing and prepolymerizing for 2 hours to obtain a mixed solution B;
step 3: mixing 1.3kg of mixed solution A and 0.18kg of mixed solution B, regulating the pH value to 5 by acetic acid, adding 0.47kg of methyltrimethoxysilane to obtain mixed solution C, and stirring and uniformly mixing to obtain wet gel;
step 4: aging wet gel at 45deg.C for 48 hr, then performing solvent exchange, firstly exchanging with anhydrous ethanol for 72 hr, and then exchanging with acetone for 72 hr; drying by supercritical carbon dioxide to obtain composite aerogel;
step 5: 15 parts of bisphenol A epoxy resin is heated at 75 ℃, 3.5kg of ethylenediamine, 1.2kg of acetone, 0.7kg of 2MZ-A, 2.8kg of composite aerogel and 2kg of alumina are added and uniformly mixed, and then the resin glue solution containing alumina for the copper-clad plate can be obtained.
Example 4:
step 1: dissolving 1.4kg of melamine and 0.038kg of anhydrous sodium carbonate in 10kg of deionized water, heating to 60 ℃ in a water bath, stirring for 30min, adding 1.9kg of 37% formaldehyde solution by mass concentration after substances in the system are uniformly mixed, continuously stirring until the mixture is transparent, and sealing and pre-polymerizing for 5h at normal temperature to obtain a mixed solution A;
step 2: adding 0.019 parts of chitosan into 1.12kg of acetic acid solution with the mass concentration of 1%, stirring for 3 hours at normal temperature, adding 0.013 parts of formaldehyde solution with the mass concentration of 40%, continuously stirring for 10 minutes, sealing, standing and prepolymerizing for 2 hours to obtain a mixed solution B;
step 3: mixing 1.45kg of mixed solution A and 0.18kg of mixed solution B, regulating the pH value to 5 by acetic acid, adding 0.5kg of methyltrimethoxysilane to obtain mixed solution C, and stirring uniformly to obtain wet gel;
step 4: aging wet gel at 45deg.C for 48 hr, then performing solvent exchange, firstly exchanging with anhydrous ethanol for 72 hr, and then exchanging with acetone for 72 hr; drying by supercritical carbon dioxide to obtain composite aerogel;
step 5: 15 parts of bisphenol A epoxy resin is heated at 75 ℃, 3.7kg of ethylenediamine, 1.2kg of acetone, 0.8kg of 2MZ-A, 2.4kg of composite aerogel and 1.9kg of alumina are added and uniformly mixed, and then the alumina-containing resin glue solution for the copper-clad plate can be obtained.
Example 5:
step 1: dissolving 1.35kg of melamine and 0.049kg of anhydrous sodium carbonate in 9kg of deionized water, heating to 60 ℃ in a water bath, stirring for 30min, adding 2kg of 37% formaldehyde solution by mass concentration after substances in the system are uniformly mixed, continuously stirring to be transparent, and sealing and placing in a room temperature for prepolymerization for 5h to obtain a mixed solution A;
step 2: adding 0.016kg of chitosan into 1.03kg of acetic acid solution with the mass concentration of 1%, stirring for 2.5 hours at normal temperature, adding 0.012kg of formaldehyde solution with the mass concentration of 40%, continuously stirring for 10 minutes, sealing, standing and prepolymerizing for 2 hours to obtain a mixed solution B;
step 3: mixing 1.85kg of mixed solution A and 0.14kg of mixed solution B, regulating the pH value to 5 by acetic acid, adding 0.5kg of methyltrimethoxysilane to obtain mixed solution C, and stirring uniformly to obtain wet gel;
step 4: aging wet gel at 45deg.C for 56 hr, then performing solvent exchange, firstly exchanging with anhydrous ethanol for 68 hr, and then exchanging with acetone for 68 hr; drying by supercritical carbon dioxide to obtain composite aerogel;
step 5: 13kg of bisphenol A epoxy resin is heated at 50 ℃, 3.4kg of 2MZ-A, 1kg of acetone, 0.48kg of ethylenediamine, 2.5kg of composite aerogel and 1.6kg of alumina are added and uniformly mixed, and then the resin glue solution containing alumina for the copper-clad plate can be obtained.
Example 6:
step 1: dissolving 1.42kg of melamine and 0.045kg of anhydrous sodium carbonate in 9.6kg of deionized water, heating to 60 ℃ in a water bath, stirring for 30min, adding 2kg of 37% formaldehyde solution by mass concentration after substances in the system are uniformly mixed, continuously stirring until the mixture is transparent, and sealing and pre-polymerizing for 5h at normal temperature to obtain a mixed solution A;
step 2: adding 0.015kg of chitosan into 1.19kg of acetic acid solution with the mass concentration of 1%, stirring for 3 hours at normal temperature, adding 0.012kg of formaldehyde solution with the mass concentration of 40%, continuously stirring for 10 minutes, sealing, standing and prepolymerizing for 2 hours to obtain a mixed solution B;
step 3: mixing 1.5kg of mixed solution A and 0.2kg of mixed solution B, regulating the pH value to 4.5 by acetic acid, adding 0.5kg of methyltrimethoxysilane to obtain mixed solution C, and stirring uniformly to obtain wet gel;
step 4: aging wet gel at 45deg.C for 48 hr, then performing solvent exchange, firstly exchanging with absolute ethanol for 70 hr, and then exchanging with acetone for 70 hr; drying by supercritical carbon dioxide to obtain composite aerogel;
step 5: 13.5kg of bisphenol A epoxy resin is heated at 50 ℃, 3kg of 2MZ-A, 1kg of acetone, 0.5kg of ethylenediamine, 3kg of composite aerogel and 1.4kg of alumina are added and mixed uniformly, and then the alumina-containing resin glue solution for the copper-clad plate can be obtained.
Comparative example 1:
no composite aerogel was added.
Heating 14kg bisphenol A epoxy resin at 50 ℃, adding 3.5kg 2MZ-A, 1kg acetone, 0.5kg ethylenediamine and 1.4kg alumina, and uniformly mixing to obtain the alumina-containing resin glue solution for the copper-clad plate.
Comparative example 2:
aerogel was prepared without chitosan.
Step 1: dissolving 1.2kg of melamine and 0.35kg of anhydrous sodium carbonate in 10kg of deionized water, heating to 55 ℃ in a water bath, stirring for 25min, adding 1.8kg of 37% formaldehyde solution by mass concentration after substances in the system are uniformly mixed, continuously stirring until the mixture is transparent, and sealing and pre-polymerizing for 4h at normal temperature to obtain a mixed solution A;
step 2: regulating the pH value to 5 by acetic acid, adding 0.48kg of methyltrimethoxysilane into 1.2kg of mixed solution A, and stirring and uniformly mixing to obtain wet gel;
step 3: aging wet gel at 45deg.C for 42 hr, then performing solvent exchange, firstly exchanging with anhydrous ethanol for 65 hr, and then exchanging with acetone for 65 hr; drying by supercritical carbon dioxide to obtain composite aerogel;
step 4: 13kg of bisphenol A epoxy resin is heated at 60 ℃, 3kg of ethylenediamine, 0.8kg of acetone, 0.5kg of 2MZ-A, 2.6kg of composite aerogel and 1.2 alumina are added and mixed uniformly, and the resin glue solution containing alumina for the copper-clad plate can be obtained.
Comparative example 3:
aerogels were prepared without the addition of methyltrimethoxysilane.
Step 1: dissolving 1.3kg of melamine and 0.03kg of anhydrous sodium carbonate in 10kg of deionized water, heating to 60 ℃ in a water bath, stirring for 30min, adding 1.7kg of 37% formaldehyde solution by mass concentration after substances in the system are uniformly mixed, continuously stirring until the mixture is transparent, and sealing and pre-polymerizing for 5h at normal temperature to obtain a mixed solution A;
step 2: adding 0.018 part of chitosan into 1.15kg of acetic acid solution with the mass concentration of 1%, stirring for 3 hours at normal temperature, adding 0.013 part of formaldehyde solution with the mass concentration of 40%, continuously stirring for 10 minutes, sealing, standing and prepolymerizing for 2 hours to obtain a mixed solution B;
step 3: mixing 1.3kg of mixed solution A and 0.18kg of mixed solution B, and stirring uniformly to obtain wet gel;
step 4: aging wet gel at 45deg.C for 48 hr, then performing solvent exchange, firstly exchanging with anhydrous ethanol for 72 hr, and then exchanging with acetone for 72 hr; drying by supercritical carbon dioxide to obtain composite aerogel;
step 5: 15 parts of bisphenol A epoxy resin is heated at 75 ℃, 3.5kg of ethylenediamine, 1.2kg of acetone, 0.7kg of 2MZ-A, 3kg of composite aerogel and 2kg of alumina are added and mixed uniformly, and then the resin glue solution containing alumina for the copper-clad plate can be obtained.
Comparative example 4:
aerogel was prepared without adding melamine formaldehyde resin.
Step 1: adding 0.019kg of chitosan into 1.12kg of acetic acid solution with the mass concentration of 1%, and stirring for 3 hours at normal temperature to obtain a mixed solution A; regulating the pH value of the mixed solution A to 5 by using acetic acid, adding 0.5kg of methyltrimethoxysilane, and stirring and uniformly mixing to obtain wet gel;
step 2: aging wet gel at 45deg.C for 48 hr, then performing solvent exchange, firstly exchanging with anhydrous ethanol for 72 hr, and then exchanging with acetone for 72 hr; drying by supercritical carbon dioxide to obtain composite aerogel;
step 3: heating 15kg bisphenol A epoxy resin at 75 ℃, adding 3.7kg ethylenediamine, 1.2kg acetone, 0.8kg 2MZ-A, 2.8kg composite aerogel and 1.9kg alumina, and uniformly mixing to obtain the alumina-containing resin glue solution for the copper-clad plate.
Experiment:
coating the resin glue solution containing aluminum oxide prepared in examples 1-6 and comparative examples 1-4 on glass fiber cloth, drying in an oven at 75 ℃ for 10-15 min, coating copper foil on the resin glue solution, placing in a hot press for 120-240 min, taking out and curing for 1-2 h, and obtaining the flame-retardant copper-clad plate.
Flame retardancy: testing according to the method specified in UL 94;
weight loss on heat: heating to 600 ℃ under nitrogen atmosphere at a heating rate of 5 ℃/min, and recording the temperature when the mass loss of the sample is 5%;
tensile strength: the tensile property is tested according to GB/T528-2009 by adopting an HY-5080 universal tensile testing machine.
Water absorption rate: the copper-clad plate with the size of 50 multiplied by 50mm is firstly dried for 30min at 110 ℃, is weighed after being cooled to room temperature, is marked as w1, is then put into a 2atm pressure cooker to be steamed for 2 hours, is taken out to wipe off water on the plate surface, is weighed as w2, and calculates the water absorption rate as (w 2-w 1)/w 1.
| Examples | Flame retardancy | 5% thermal weight loss/. Degree.C | Tensile Strength/MPa | Water absorption/% |
| Example 1 | V-0 | 379 | 88.1 | 0.27 |
| Example 2 | V-0 | 372 | 89.9 | 0.29 |
| Example 3 | V-0 | 375 | 89.6 | 0.31 |
| Example 4 | V-0 | 380 | 88.7 | 0.25 |
| Example 5 | V-0 | 377 | 89.5 | 0.27 |
| Example 6 | V-0 | 381 | 90.3 | 0.30 |
| Comparative example 1 | V-1 | 326 | 80.2 | 0.71 |
| Comparative example 2 | / | / | 81.7 | / |
| Comparative example 3 | / | / | / | 0.68 |
| Comparative example 4 | / | 349 | / | / |
Conclusion: comparing the data of examples 1-6 with the data of comparative example 1, the aerogel prepared by the invention can improve the flame retardant property, the thermal stability and the toughness of the resin glue solution containing aluminum oxide. With the example 2 as a reference, the data of the comparative example 2 show that the addition of chitosan can improve the toughness of the epoxy resin and the tensile strength of the cured epoxy resin; with the example 3 as a reference, the data of the comparative example 3 show that the methyltrimethoxysilane can reduce the water absorption of the epoxy resin and keep the surface of the copper-clad plate dry, so that the circuit can be protected; with reference to example 4, the data of comparative example 4 shows that melamine formaldehyde resin can not only enhance the flame retardancy of epoxy resin, but also enhance the thermal stability of epoxy resin.
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 (3)
1. A preparation method of an alumina-containing resin glue solution for a copper-clad plate is characterized by comprising the following steps: the method comprises the following steps:
step 1: dissolving melamine and anhydrous sodium carbonate in deionized water, heating in a water bath, stirring, adding formaldehyde solution after substances in a system are uniformly mixed, continuously stirring until the mixture is transparent, and carrying out sealed prepolymerization for 3-5 hours to obtain a mixed solution A; the water bath heating temperature is 50-60 ℃; in the mixed solution A, the content of each component is 10 to 15 parts by weight of melamine, 0.3 to 0.5 part by weight of anhydrous sodium carbonate, 100 parts by weight of deionized water and 16 to 20 parts by weight of formaldehyde solution;
step 2: preparing an acetic acid solution, adding chitosan, stirring, adding formaldehyde solution, continuously stirring for 5-10 min, sealing, standing and prepolymerizing for 1-2 h to obtain a mixed solution B; in the mixed solution B, the contents of the components are 10-12 parts by weight of acetic acid solution, 0.1-0.2 part by weight of chitosan and 0.1-0.13 part by weight of formaldehyde solution;
step 3: mixing the mixed solution A and the mixed solution B, regulating the pH value to 4.5-5 by acetic acid, adding methyltrimethoxysilane to obtain a mixed solution C, and stirring and uniformly mixing to obtain wet gel; the weight of each component is 10-15 parts of mixed solution A, 1-2 parts of mixed solution B and 4.5-5 parts of methyltrimethoxysilane;
step 4: performing solvent exchange after the wet gel is aged, and drying by adopting supercritical carbon dioxide to obtain composite aerogel; the aging temperature of the wet gel is 40-45 ℃; aging time is 36-48 h; the solvent exchange method is that absolute ethyl alcohol is used for exchange for 60-72 hours, and then acetone is used for exchange for 60-72 hours;
step 5: heating bisphenol A epoxy resin at 50-75 ℃, adding a curing agent, acetone, an accelerator, composite aerogel and alumina, and uniformly mixing to obtain an alumina-containing resin glue solution for a copper-clad plate; 120-150 parts of bisphenol A epoxy resin, 20-35 parts of curing agent, 8-12 parts of acetone, 3-7 parts of accelerator, 20-30 parts of composite aerogel and 10-20 parts of alumina.
2. The preparation method of the alumina-containing resin glue solution for the copper-clad plate according to claim 1, which is characterized by comprising the following steps: in the step 5, the curing agent is any one of ethylenediamine, hexamethylenediamine, diethylenetriamine, maleic anhydride and phthalic anhydride; the accelerator is any one of imidazole curing accelerator, organic phosphine curing accelerator or tertiary amine curing accelerator.
3. The resin glue solution containing aluminum oxide for copper-clad plate according to claim 1 or 2.
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