CN111548478A - Preparation method of epoxy resin for aluminum plate copper coating - Google Patents
Preparation method of epoxy resin for aluminum plate copper coating Download PDFInfo
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- CN111548478A CN111548478A CN202010427729.2A CN202010427729A CN111548478A CN 111548478 A CN111548478 A CN 111548478A CN 202010427729 A CN202010427729 A CN 202010427729A CN 111548478 A CN111548478 A CN 111548478A
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/14—Polycondensates modified by chemical after-treatment
- C08G59/1433—Polycondensates modified by chemical after-treatment with organic low-molecular-weight compounds
- C08G59/1488—Polycondensates modified by chemical after-treatment with organic low-molecular-weight compounds containing phosphorus
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- 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
- B32B15/01—Layered products comprising a layer of metal all layers being exclusively metallic
- B32B15/012—Layered products comprising a layer of metal all layers being exclusively metallic one layer being formed of an iron alloy or steel, another layer being formed of aluminium or an aluminium alloy
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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
- B32B15/00—Layered products comprising a layer of metal
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- B32B15/00—Layered products comprising a layer of metal
- B32B15/20—Layered products comprising a layer of metal comprising aluminium or copper
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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
- 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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- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- 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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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B37/00—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding
- B32B37/10—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the pressing technique, e.g. using action of vacuum or fluid pressure
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- B32B37/00—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding
- B32B37/12—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by using adhesives
- B32B37/1284—Application of adhesive
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- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
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Abstract
The invention provides a preparation method of epoxy resin for copper cladding of an aluminum plate, which comprises the following steps: s1, adding a proper amount of deionized water into melamine, stirring until the melamine is completely dissolved in the deionized water, adding phytic acid, stirring at 90 ℃ for 1-3 hours to obtain a finishing liquid, wherein the mass ratio of the melamine to the phytic acid is 1: (0.5 to 1.5); s2, weighing bisphenol A epoxy resin, dissolving the bisphenol A epoxy resin in absolute ethyl alcohol, heating to 60-90 ℃ after the bisphenol A epoxy resin is completely dissolved, dropwise adding finishing liquid into a mixed liquid of the bisphenol A epoxy resin and the absolute ethyl alcohol, stirring at constant temperature, and reacting for 2-4 hours to obtain the modified epoxy resin, wherein the mass ratio of the finishing liquid to the bisphenol A epoxy resin is (30-90): 100, and the softening point of the bisphenol A epoxy resin is lower than 35 ℃. The N and P flame-retardant elements are introduced into the bisphenol A epoxy resin, so that the grafting of the flame retardant on the epoxy resin is realized, the dispersion problem of the flame retardant in the epoxy resin is solved, the bonding performance of the modified epoxy resin is ensured, and meanwhile, the thermal stability and the flame retardant performance of the modified epoxy resin are improved by utilizing the synergistic effect of the N/P flame-retardant elements and the stable net structure.
Description
Technical Field
The invention relates to the technical field of aluminum substrates, in particular to a preparation method of epoxy resin for copper cladding of an aluminum plate.
Background
The aluminum substrate is a metal-based copper-clad plate with good heat dissipation function, and a single-sided board generally comprises a three-layer structure, namely a circuit layer (copper foil), an insulating layer and a metal base layer. The high-end application is also designed to be a double-sided board, and the structure of the double-sided board is a circuit layer, an insulating layer, an aluminum base, an insulating layer and a circuit layer. The aluminum-based composite board is rarely used as a composite board and can be formed by laminating a common composite board, an insulating layer and an aluminum base. The insulating layer of the aluminum substrate generally requires a certain flame retardant effect, the commonly used epoxy resin flame retardant method mainly comprises additive flame retardant and reactive flame retardant, the additive flame retardant is cheap and easy to operate, but the problem of dispersion of the flame retardant in the epoxy resin needs to be solved, otherwise, the adhesive force of the insulating layer to the aluminum plate and the copper foil is easily influenced; the reactive flame retardant has good flame retardant effect, and especially, the flame retardant effect and the thermal stability of the material can be further improved by simultaneously adding multiple flame retardant elements through the synergistic effect of the flame retardant elements and the flame retardant elements. At present, Wei Shajie and the like synthesize phosphorus-silicon hybrid by taking methyl triethoxysilane, epoxy propyl trimethoxysilane, ethyl orthosilicate and phosphoric acid as raw materials, and then the phosphorus-silicon hybrid reacts with 4, 4' -diaminodiphenylmethane and epoxy resin through curing reaction to synthesize epoxy resin condensate containing phosphorus and silicon. Epoxy resin containing a cyclotriphosphazene structure and a curing agent are representatives of a phosphorus-nitrogen synergistic flame-retardant epoxy resin system. The synthesis of epoxy resin containing cyclotriphosphazene structure usually uses hexachlorocyclotriphosphazene or hexa (4-hydroxymethylphenoxy) cyclotriphosphazene as raw material. The Xiaohoji and the like use hexachlorocyclotriphosphazene and 2, 3-epoxy-1-propanol as raw materials, an epoxy resin containing a cyclotriphosphazene structure, namely hexaglycidylcyclotriphosphazene, is obtained through nucleophilic substitution reaction, maleic anhydride and 4, 4-diamino-diphenyl-methane are selected as curing agents, and heat resistance and ablation resistance of different curing systems are researched through thermogravimetric analysis and line ablation rate. In order to further improve the heat resistance and ablation resistance of the cyclotriphosphazene epoxy resin, the cyclotriphosphazene and the epoxy chloropropane are used as raw materials for Xiao-Miao and the like to synthesize a novel high-temperature-resistant and flame-retardant aryloxy cyclotriphosphazene epoxy resin hexa (4-glycidylphenoxy) cyclotriphosphazene (HCPEP), maleic anhydride is selected as a curing agent, and cyclotriphosphazene-based organic filler, namely hexa (4-aldehyde phenoxy) cyclotriphosphazene, is added to prepare the epoxy resin composite material. Although the reaction type flame-retardant epoxy resin has a good flame-retardant effect, the bonding property is insufficient, the reaction type flame-retardant epoxy resin cannot be used for an aluminum plate copper-cladding process, and a compound with a cyclotriphosphazene structure has strong corrosivity and potential safety hazard in use. The existing commonly used flame retardant system in the field of electronic and electric appliances is a tetrabromobisphenol A reaction type flame retardant system, but a large amount of toxic smoke is generated during combustion, related regulations (RoHS) of European Union forbid the use of bromine compounds, and simultaneously, European chemical administration (ECHA) also lists part of bromine-containing flame retardants as highly concerned Substances (SVHC), so that the halogen-free flame retardant technology is more in line with the requirement of environmental development. Therefore, an epoxy resin with good flame retardant effect and good adhesion is needed.
Disclosure of Invention
The invention aims to overcome the defects of the traditional technology and provide the epoxy resin with good flame retardant effect and good adhesion, which is suitable for the aluminum plate copper-coating process.
The purpose of the invention is realized by the following technical contents: a preparation method of epoxy resin for copper cladding of an aluminum plate comprises the following steps:
s1, adding a proper amount of deionized water into melamine, stirring until the melamine is completely dissolved in the deionized water, adding phytic acid, stirring at 90 ℃ for 1-3 hours to obtain a finishing liquid, wherein the mass ratio of the melamine to the phytic acid is 1: (0.5 to 1.5);
s2, weighing bisphenol A epoxy resin, dissolving the bisphenol A epoxy resin in absolute ethyl alcohol, heating to 60-90 ℃ after the bisphenol A epoxy resin is completely dissolved, dropwise adding finishing liquid into a mixed liquid of the bisphenol A epoxy resin and the absolute ethyl alcohol, stirring at constant temperature, and reacting for 2-4 hours to obtain the modified epoxy resin, wherein the mass ratio of the finishing liquid to the bisphenol A epoxy resin is (30-90): 100, and the softening point of the bisphenol A epoxy resin is lower than 35 ℃.
Step S1 synthesis principle:
step S2 grafting principle:
R1is a phosphate group that reacts with melamine.
Phosphoric acid groups on phytic acid and amino groups of melamine react to generate an intermediate with a net structure, and the phosphoric acid groups are ensured to be remained by the phytic acid by controlling the mass ratio of the phytic acid to the melamine. The bisphenol A epoxy resin has epoxy groups with high activity at two ends, and can react with phosphate groups which are not reacted with amino groups on the intermediate generated in the step S1 under the heating condition, so that N and P flame-retardant elements are introduced into the bisphenol A epoxy resin, the grafting of the flame retardant on the epoxy resin is realized, the dispersion problem of the flame retardant in the epoxy resin is solved, the bonding performance of the modified epoxy resin is ensured, and meanwhile, the thermal stability and the flame retardant performance of the modified epoxy resin are improved by utilizing the synergistic effect of the N/P flame-retardant elements and the stable net structure.
In one embodiment of the present invention, the bisphenol A epoxy resin in step S2 is an E-44 epoxy resin.
The E-44 epoxy resin has good adhesive property and good electrical insulation property.
In one embodiment of the present invention, the mass ratio of the bisphenol a epoxy resin to the absolute ethyl alcohol in step S2 is 5: 2. The mass ratio of the bisphenol A epoxy resin to the absolute ethyl alcohol is 5:2, so that the bisphenol A epoxy resin is fully dispersed, and the subsequent grafting reaction with the finishing liquid is more sufficient.
In one embodiment of the present invention, phytic acid is slowly added dropwise to melamine in step S1. In order to avoid the violent heat release caused by too fast dropping of the phytic acid, the phytic acid is slowly dropped by a separating funnel.
In one embodiment of the invention, the mass ratio of the finishing liquid to the bisphenol A epoxy resin in the step S2 is (30-60): 100. The addition amount of the finishing liquid is too large, so that the viscosity of the obtained modified epoxy resin is too large, and the subsequent treatment and application are not facilitated.
Due to the adoption of the technical scheme, compared with the prior art, the invention has the advantages that:
phosphoric acid groups on phytic acid and amino groups of melamine react to generate an intermediate with a net structure, and the phosphoric acid groups are ensured to be remained by the phytic acid by controlling the mass ratio of the phytic acid to the melamine. The bisphenol A epoxy resin has epoxy groups with high activity at two ends, and can react with phosphate groups which are not reacted with amino groups on the intermediate generated in the step S1 under the heating condition, so that N and P flame-retardant elements are introduced into the bisphenol A epoxy resin, the grafting of the flame retardant on the epoxy resin is realized, the dispersion problem of the flame retardant in the epoxy resin is solved, the bonding performance of the modified epoxy resin is ensured, and meanwhile, the thermal stability and the flame retardant performance of the modified epoxy resin are improved by utilizing the synergistic effect of the N/P flame-retardant elements and the stable net structure.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1
A preparation method of epoxy resin for copper cladding of an aluminum plate comprises the following steps:
s1, adding a proper amount of deionized water into melamine, stirring until the melamine is completely dissolved in the deionized water, slowly dropwise adding phytic acid into the mixed solution of the melamine and absolute ethyl alcohol, stirring at 90 ℃ for 1h to obtain a finishing liquid, wherein the mass ratio of the melamine to the phytic acid is 1: 0.5;
s2, weighing E-44 epoxy resin, dissolving the E-44 epoxy resin in absolute ethyl alcohol, wherein the mass ratio of the E-44 epoxy resin to the absolute ethyl alcohol is 5:2, heating to 60 ℃ after the E-44 epoxy resin is completely dissolved, dropwise adding finishing liquid into the mixed liquid of the E-44 epoxy resin and the absolute ethyl alcohol, stirring at constant temperature for 2 hours, and reacting to obtain the modified epoxy resin, wherein the mass ratio of the finishing liquid to the E-44 epoxy resin is 30: 100.
The modified epoxy resin is used for the aluminum plate copper-clad process.
After the modified epoxy resin is cured, the linear ablation rate is tested according to GJB 323A-96.
And (4) preparing heat-conducting insulating glue.
Adding the modified epoxy resin into a three-necked bottle, heating to (35 +/-5) DEG C, adding acetone and dimethylformamide, and mixing for 30 min; adding dicyandiamide and 2-methylimidazole, and mixing for 30 min; adding silicon powder, and stirring at a high speed of 3000 +/-350 r/min for 60 min for later use, wherein the mass ratio of the modified epoxy resin to the acetone to the dimethylformamide to the dicyandiamide to the 2-methylimidazole to the silicon powder is 100:70:10:2.5:1.3:300 respectively.
And (5) preparing a prepreg.
And (3) drying the heat-conducting insulating adhesive with the thickness of 0.1mm on a copper foil for 4-8 min at 160 ℃ in hot air on gluing equipment to prepare a prepreg, and placing the prepreg in a dryer for later use.
And (3) preparing the aluminum-based copper-clad plate.
And laminating the semi-solidified and aluminum plates one by one, and pressing in a hot press. The pressing process conditions are as follows: maintaining the pressure at 130 ℃ and 3MPa for 30min, then heating to 185 ℃ and pressing at 20 MPa for 5 h, cooling to room temperature along with a press, and taking out.
The test is carried out according to the 7.2 peeling strength test method in GB/T4722 & 2017 and the test is carried out according to the 6.5 thermal stress test method in GB/T4722 & 2017.
Example 2
A preparation method of epoxy resin for copper cladding of an aluminum plate comprises the following steps:
s1, adding a proper amount of deionized water into melamine, stirring until the melamine is completely dissolved in the deionized water, slowly dropwise adding phytic acid into the mixed solution of the melamine and absolute ethyl alcohol, stirring at 90 ℃ for 3 hours to obtain a finishing liquid, wherein the mass ratio of the melamine to the phytic acid is 1: 1.5;
s2, weighing E-44 epoxy resin, dissolving the E-44 epoxy resin in absolute ethyl alcohol, wherein the mass ratio of the E-44 epoxy resin to the absolute ethyl alcohol is 5:2, heating to 90 ℃ after the E-44 epoxy resin is completely dissolved, dropwise adding finishing liquid into the mixed liquid of the E-44 epoxy resin and the absolute ethyl alcohol, stirring at constant temperature for 4 hours, and reacting to obtain the modified epoxy resin, wherein the mass ratio of the finishing liquid to the E-44 epoxy resin is 60: 100.
The modified epoxy resin is used for the aluminum plate copper-clad process.
After the modified epoxy resin is cured, the linear ablation rate is tested according to GJB 323A-96.
And (4) preparing heat-conducting insulating glue.
Adding the modified epoxy resin into a three-necked bottle, heating to (35 +/-5) DEG C, adding acetone and dimethylformamide, and mixing for 30 min; adding dicyandiamide and 2-methylimidazole, and mixing for 30 min; adding silicon powder, and stirring at a high speed of 3000 +/-350 r/min for 60 min for later use, wherein the mass ratio of the modified epoxy resin to the acetone to the dimethylformamide to the dicyandiamide to the 2-methylimidazole to the silicon powder is 100:70:10:2.5:1.3:300 respectively.
And (5) preparing a prepreg.
And (3) drying the heat-conducting insulating adhesive with the thickness of 0.1mm on a copper foil for 4-8 min at 160 ℃ in hot air on gluing equipment to prepare a prepreg, and placing the prepreg in a dryer for later use.
And (3) preparing the aluminum-based copper-clad plate.
And laminating the semi-solidified and aluminum plates one by one, and pressing in a hot press. The pressing process conditions are as follows: maintaining the pressure at 130 ℃ and 3MPa for 30min, then heating to 185 ℃ and pressing at 20 MPa for 5 h, cooling to room temperature along with a press, and taking out.
The test is carried out according to the 7.2 peeling strength test method in GB/T4722 & 2017 and the test is carried out according to the 6.5 thermal stress test method in GB/T4722 & 2017.
Example 3
A preparation method of epoxy resin for copper cladding of an aluminum plate comprises the following steps:
s1, adding a proper amount of deionized water into melamine, stirring until the melamine is completely dissolved in the deionized water, slowly dropwise adding phytic acid into the mixed solution of the melamine and absolute ethyl alcohol, stirring at 90 ℃ for 3 hours to obtain a finishing liquid, wherein the mass ratio of the melamine to the phytic acid is 1: 1.5;
s2, weighing E-35 epoxy resin, dissolving the E-35 epoxy resin in absolute ethyl alcohol, wherein the mass ratio of the E-35 epoxy resin to the absolute ethyl alcohol is 5:2, heating to 90 ℃ after the E-35 epoxy resin is completely dissolved, dropwise adding finishing liquid into the mixed liquid of the E-35 epoxy resin and the absolute ethyl alcohol, stirring at constant temperature for reaction for 4 hours, and obtaining modified epoxy resin, wherein the mass ratio of the finishing liquid to the E-35 epoxy resin is 60: 100.
The modified epoxy resin is used for the aluminum plate copper-clad process.
After the modified epoxy resin is cured, the linear ablation rate is tested according to GJB 323A-96.
And (4) preparing heat-conducting insulating glue.
Adding the modified epoxy resin into a three-necked bottle, heating to (35 +/-5) DEG C, adding acetone and dimethylformamide, and mixing for 30 min; adding dicyandiamide and 2-methylimidazole, and mixing for 30 min; adding silicon powder, and stirring at a high speed of 3000 +/-350 r/min for 60 min for later use, wherein the mass ratio of the modified epoxy resin to the acetone to the dimethylformamide to the dicyandiamide to the 2-methylimidazole to the silicon powder is 100:70:10:2.5:1.3:300 respectively.
And (5) preparing a prepreg.
And (3) drying the heat-conducting insulating adhesive with the thickness of 0.1mm on a copper foil for 4-8 min at 160 ℃ in hot air on gluing equipment to prepare a prepreg, and placing the prepreg in a dryer for later use.
And (3) preparing the aluminum-based copper-clad plate.
And laminating the semi-solidified and aluminum plates one by one, and pressing in a hot press. The pressing process conditions are as follows: maintaining the pressure at 130 ℃ and 3MPa for 30min, then heating to 185 ℃ and pressing at 20 MPa for 5 h, cooling to room temperature along with a press, and taking out.
The test is carried out according to the 7.2 peeling strength test method in GB/T4722 & 2017 and the test is carried out according to the 6.5 thermal stress test method in GB/T4722 & 2017.
Example 4
A preparation method of epoxy resin for copper cladding of an aluminum plate comprises the following steps:
s1, adding a proper amount of deionized water into melamine, stirring until the melamine is completely dissolved in the deionized water, slowly dropwise adding phytic acid into the mixed solution of the melamine and absolute ethyl alcohol, stirring at 90 ℃ for 3 hours to obtain a finishing liquid, wherein the mass ratio of the melamine to the phytic acid is 1: 1.5;
s2, weighing E-42 epoxy resin, dissolving the E-42 epoxy resin in absolute ethyl alcohol, wherein the mass ratio of the E-42 epoxy resin to the absolute ethyl alcohol is 5:2, heating to 90 ℃ after the E-42 epoxy resin is completely dissolved, dropwise adding finishing liquid into the mixed liquid of the E-42 epoxy resin and the absolute ethyl alcohol, stirring at constant temperature for reaction for 4 hours, and obtaining modified epoxy resin, wherein the mass ratio of the finishing liquid to the E-42 epoxy resin is 60: 100.
The modified epoxy resin is used for the aluminum plate copper-clad process.
After the modified epoxy resin is cured, the linear ablation rate is tested according to GJB 323A-96.
And (4) preparing heat-conducting insulating glue.
Adding the modified epoxy resin into a three-necked bottle, heating to (35 +/-5) DEG C, adding acetone and dimethylformamide, and mixing for 30 min; adding dicyandiamide and 2-methylimidazole, and mixing for 30 min; adding silicon powder, and stirring at a high speed of 3000 +/-420 r/min for 60 min for later use, wherein the mass ratio of the modified epoxy resin to the acetone to the dimethylformamide to the dicyandiamide to the 2-methylimidazole to the silicon powder is 100:70:10:2.5:1.3:300 respectively.
And (5) preparing a prepreg.
And (3) drying the heat-conducting insulating adhesive with the thickness of 0.1mm on a copper foil for 4-8 min at 160 ℃ in hot air on gluing equipment to prepare a prepreg, and placing the prepreg in a dryer for later use.
And (3) preparing the aluminum-based copper-clad plate.
And laminating the semi-solidified and aluminum plates one by one, and pressing in a hot press. The pressing process conditions are as follows: maintaining the pressure at 130 ℃ and 3MPa for 30min, then heating to 185 ℃ and pressing at 20 MPa for 5 h, cooling to room temperature along with a press, and taking out.
The test is carried out according to the 7.2 peeling strength test method in GB/T4722 & 2017 and the test is carried out according to the 6.5 thermal stress test method in GB/T4722 & 2017.
Example 5
A preparation method of epoxy resin for copper cladding of an aluminum plate comprises the following steps:
s1, adding a proper amount of deionized water into melamine, stirring until the melamine is completely dissolved in the deionized water, slowly dropwise adding phytic acid into the mixed solution of the melamine and absolute ethyl alcohol, stirring at 90 ℃ for 3 hours to obtain a finishing liquid, wherein the mass ratio of the melamine to the phytic acid is 1: 1.5;
s2, weighing E-51 epoxy resin, dissolving the E-51 epoxy resin in absolute ethyl alcohol, wherein the mass ratio of the E-51 epoxy resin to the absolute ethyl alcohol is 5:2, heating to 90 ℃ after the E-51 epoxy resin is completely dissolved, dropwise adding finishing liquid into the mixed liquid of the E-51 epoxy resin and the absolute ethyl alcohol, stirring at constant temperature for 4 hours, and obtaining modified epoxy resin, wherein the mass ratio of the finishing liquid to the E-51 epoxy resin is 60: 100.
The modified epoxy resin is used for the aluminum plate copper-clad process.
After the modified epoxy resin is cured, the linear ablation rate is tested according to GJB 323A-96.
And (4) preparing heat-conducting insulating glue.
Adding the modified epoxy resin into a three-necked bottle, heating to (35 +/-5) DEG C, adding acetone and dimethylformamide, and mixing for 30 min; adding dicyandiamide and 2-methylimidazole, and mixing for 30 min; adding silicon powder, and stirring at a high speed of 3000 +/-510 r/min for 60 min for later use, wherein the mass ratio of the modified epoxy resin to the acetone to the dimethylformamide to the dicyandiamide to the 2-methylimidazole to the silicon powder is 100:70:10:2.5:1.3:300 respectively.
And (5) preparing a prepreg.
And (3) drying the heat-conducting insulating adhesive with the thickness of 0.1mm on a copper foil for 4-8 min at 160 ℃ in hot air on gluing equipment to prepare a prepreg, and placing the prepreg in a dryer for later use.
And (3) preparing the aluminum-based copper-clad plate.
And laminating the semi-solidified and aluminum plates one by one, and pressing in a hot press. The pressing process conditions are as follows: maintaining the pressure at 130 ℃ and 3MPa for 30min, then heating to 185 ℃ and pressing at 20 MPa for 5 h, cooling to room temperature along with a press, and taking out.
The test is carried out according to the 7.2 peeling strength test method in GB/T4722 & 2017 and the test is carried out according to the 6.5 thermal stress test method in GB/T4722 & 2017.
Example 6
A preparation method of epoxy resin for copper cladding of an aluminum plate comprises the following steps:
s1, adding a proper amount of deionized water into melamine, stirring until the melamine is completely dissolved in the deionized water, slowly dropwise adding phytic acid into the mixed solution of the melamine and absolute ethyl alcohol, stirring at 90 ℃ for 3 hours to obtain a finishing liquid, wherein the mass ratio of the melamine to the phytic acid is 1: 1.5;
s2, weighing E-44 epoxy resin, dissolving the E-44 epoxy resin in absolute ethyl alcohol, wherein the mass ratio of the E-44 epoxy resin to the absolute ethyl alcohol is 5:2, heating to 90 ℃ after the E-44 epoxy resin is completely dissolved, dropwise adding finishing liquid into the mixed liquid of the E-44 epoxy resin and the absolute ethyl alcohol, stirring at constant temperature for 4 hours, and reacting to obtain the modified epoxy resin, wherein the mass ratio of the finishing liquid to the E-44 epoxy resin is 90: 100.
The modified epoxy resin is used for the aluminum plate copper-clad process.
After the modified epoxy resin is cured, the linear ablation rate is tested according to GJB 323A-96.
And (4) preparing heat-conducting insulating glue.
Adding the modified epoxy resin into a three-necked bottle, heating to (35 +/-5) DEG C, adding acetone and dimethylformamide, and mixing for 30 min; adding dicyandiamide and 2-methylimidazole, and mixing for 30 min; adding silicon powder, and stirring at a high speed of 3000 +/-350 r/min for 60 min for later use, wherein the mass ratio of the modified epoxy resin to the acetone to the dimethylformamide to the dicyandiamide to the 2-methylimidazole to the silicon powder is 100:70:10:2.5:1.3:300 respectively.
And (5) preparing a prepreg.
And (3) drying the heat-conducting insulating adhesive with the thickness of 0.1mm on a copper foil for 4-8 min at 160 ℃ in hot air on gluing equipment to prepare a prepreg, and placing the prepreg in a dryer for later use.
And (3) preparing the aluminum-based copper-clad plate.
And laminating the semi-solidified and aluminum plates one by one, and pressing in a hot press. The pressing process conditions are as follows: maintaining the pressure at 130 ℃ and 3MPa for 30min, then heating to 185 ℃ and pressing at 20 MPa for 5 h, cooling to room temperature along with a press, and taking out.
The test is carried out according to the 7.2 peeling strength test method in GB/T4722 & 2017 and the test is carried out according to the 6.5 thermal stress test method in GB/T4722 & 2017.
Comparative example 1
300ml of tetrahydrofuran and 149.28g of sodium hydride (50%) are added into a 1L three-mouth reaction bottle, then 50ml of tetrahydrofuran solution dissolved with 157.78g of methoxy ethanol is added into the reaction bottle dropwise under stirring at the temperature of 20-30 ℃, and after the addition, the reaction is carried out for 30min at the temperature of 30 ℃. Then the temperature is reduced to 5 ℃, 100ml of tetrahydrofuran solution dissolved with 100g of hexachlorocyclotriphosphazene is dripped into the reaction bottle, and the reaction is carried out for 30h at the temperature of 50 ℃ after the dripping is finished. The reaction solution was filtered, and tetrahydrofuran was distilled off under reduced pressure from the filtrate to give a pale yellow turbid viscous liquid, 150ml of methylene chloride was then added to the liquid, the liquid was washed with distilled water until the aqueous phase became neutral, the organic phase was separated, and methylene chloride in the organic phase was distilled off under reduced pressure to give hexa (4-methoxyethoxy) cyclotriphosphazene as a yellow viscous transparent liquid.
The hexa (4-methoxyethoxy) cyclotriphosphazene is used for the aluminum plate copper cladding process.
And (4-methoxyethoxy) cyclotriphosphazene is taken and solidified, and the linear ablation rate is tested according to GJB 323A-96.
And (4) preparing heat-conducting insulating glue.
Adding hexa (4-methoxyethoxy) cyclotriphosphazene into a three-necked bottle, heating to (35 +/-5) ℃, adding acetone and dimethylformamide, and mixing for 30 min; adding dicyandiamide and 2-methylimidazole, and mixing for 30 min; adding silicon powder, and stirring at a high speed for 60 min at a rotating speed of (3000 +/-350) r/min for later use, wherein the mass ratio of the hexa (4-methoxyethoxy) cyclotriphosphazene to the acetone to the dimethylformamide to the dicyandiamide to the 2-methylimidazole to the silicon powder is 100:70:10:2.5:1.3:300 respectively.
The test is carried out according to the 7.2 peeling strength test method in GB/T4722 & 2017 and the test is carried out according to the 6.5 thermal stress test method in GB/T4722 & 2017.
Comparative example 2
A preparation method of epoxy resin for copper cladding of an aluminum plate comprises the following steps:
s1, adding a proper amount of deionized water into melamine, stirring until the melamine is completely dissolved in the deionized water, slowly dropwise adding phytic acid into the mixed solution of the melamine and absolute ethyl alcohol, stirring at 90 ℃ for 3 hours to obtain a finishing liquid, wherein the mass ratio of the melamine to the phytic acid is 1: 1.5;
and S2, stirring and mixing the finishing liquid and the E-44 epoxy resin uniformly at normal temperature, wherein the mass ratio of the finishing liquid to the E-44 epoxy resin is 60:100, and obtaining the epoxy resin added with the flame retardant.
The epoxy resin added with the flame retardant is used for the aluminum plate copper-cladding process.
And (3) curing the epoxy resin added with the flame retardant, and testing the linear ablation rate according to GJB 323A-96.
And (4) preparing heat-conducting insulating glue.
Adding the epoxy resin added with the flame retardant into a three-necked bottle, heating to 35 +/-5 ℃, adding acetone and dimethylformamide, and mixing for 30 min; adding dicyandiamide and 2-methylimidazole, and mixing for 30 min; adding silicon powder, stirring at a high speed of 3000 +/-350 r/min for 60 min for later use, wherein the mass ratio of the epoxy resin, the acetone, the dimethyl formamide, the dicyandiamide, the 2-methylimidazole and the silicon powder added with the flame retardant is 100:70:10:2.5:1.3:300 respectively.
And (5) preparing a prepreg.
And (3) drying the heat-conducting insulating adhesive with the thickness of 0.1mm on a copper foil for 4-8 min at 160 ℃ in hot air on gluing equipment to prepare a prepreg, and placing the prepreg in a dryer for later use.
And (3) preparing the aluminum-based copper-clad plate.
And laminating the semi-solidified and aluminum plates one by one, and pressing in a hot press. The pressing process conditions are as follows: maintaining the pressure at 130 ℃ and 3MPa for 30min, then heating to 185 ℃ and pressing at 20 MPa for 5 h, cooling to room temperature along with a press, and taking out.
The test is carried out according to the 7.2 peeling strength test method in GB/T4722 & 2017 and the test is carried out according to the 6.5 thermal stress test method in GB/T4722 & 2017.
The test data for examples 1-6 and comparative examples 1-2 are shown in Table 1.
TABLE 1 Linear ablation Rate, Peel Strength and high temperature resistance of examples 1-6 and comparative examples 1-2
| Numbering | Line ablation rate mm/s | Peel strength N/mm | Time/s of high temperature resistance |
| Example 1 | 0.326 | 1.46 | 567 |
| Example 2 | 0.311 | 1.52 | 570 |
| Example 3 | 0.330 | 1.27 | 570 |
| Example 4 | 0.337 | 1.31 | 533 |
| Example 5 | 0.346 | 1.26 | 521 |
| Example 6 | 0.314 | 1.40 | 566 |
| Comparative example 1 | 0.292 | 1.12 | 519 |
| Comparative example 2 | 0.447 | 1.22 | 221 |
Furthermore, it should be understood that although the present description refers to embodiments, not every embodiment may contain only a single embodiment, and such description is for clarity only, and those skilled in the art should integrate the description, and the embodiments may be combined as appropriate to form other embodiments understood by those skilled in the art.
Claims (5)
1. The preparation method of the epoxy resin for aluminum plate copper cladding is characterized by comprising the following steps:
s1, adding a proper amount of deionized water into melamine, stirring until the melamine is completely dissolved in the deionized water, adding phytic acid, and stirring at 90 ℃ for 1-3 hours to obtain a finishing liquid, wherein the mass ratio of the melamine to the phytic acid is 1: (0.5 to 1.5);
s2, weighing bisphenol A epoxy resin, dissolving the bisphenol A epoxy resin in absolute ethyl alcohol, heating to 60-90 ℃ after the bisphenol A epoxy resin is completely dissolved, dropwise adding the finishing liquid into the mixed liquid of the bisphenol A epoxy resin and the absolute ethyl alcohol, stirring at constant temperature, and reacting for 2-4 hours to obtain the modified epoxy resin, wherein the mass ratio of the finishing liquid to the bisphenol A epoxy resin is (30-90): 100, and the softening point of the bisphenol A epoxy resin is lower than 35 ℃.
2. The method of claim 1, wherein the epoxy resin is prepared by the following steps: the bisphenol a epoxy resin in step S2 is an E-44 epoxy resin.
3. The method of claim 1, wherein the epoxy resin is prepared by the following steps: the mass ratio of the bisphenol a epoxy resin to the absolute ethyl alcohol in the step S2 is 5: 2.
4. The method of claim 1, wherein the epoxy resin is prepared by the following steps: the phytic acid is slowly added dropwise to the melamine in step S1.
5. The method of claim 1, wherein the epoxy resin is prepared by the following steps: in the step S2, the mass ratio of the finishing liquid to the bisphenol A epoxy resin is (30-60): 100.
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