Phenolic resin composite material and application thereof in etching die
By using modified fillers in composite treatment, the toughness of phenolic resin is enhanced, solving the problem of brittle fracture of phenolic resin in etching molds. This enables the widespread application of phenolic resin composite materials in etching molds while achieving both cost-effectiveness and efficiency.
Patent Information
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2025-12-09
- Publication Date
- 2026-03-27
AI Technical Summary
Phenolic resins are prone to brittle fracture and have poor toughness in etching molds due to their relatively rigid molecular structure, poor molecular chain segment mobility, and high brittleness.
By combining modified fillers, nano-silica with modifiers such as γ-aminopropyltriethoxysilane, dimethylolpropionic acid and isocyanate-propyltrimethoxysilane can enhance the toughness of phenolic resin and improve its brittle fracture problem under external force.
The improved toughness of phenolic resin composites allows them to better replace metal plates for etching, reducing production costs and increasing production efficiency.
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Abstract
Description
Technical Field
[0001] This invention belongs to the field of phenolic resin technology, specifically relating to a phenolic resin composite material and its application in etching molds. Background Technology
[0002] In the field of etching molds, traditional processes mostly use metal plates as the main etching carrier. However, with the increasing process requirements and considerations of cost and efficiency, there has been a growing trend in recent years to replace metal plates with resin plates. Resin plates have advantages such as light weight, good machinability, low cost, and environmental friendliness. They can significantly reduce the wear and energy consumption of processing equipment while ensuring accuracy.
[0003] Among numerous resin systems, phenolic resin is considered an ideal material for preparing resin plates for etching molds due to its excellent heat resistance and dimensional stability. It is a polymer formed by the condensation reaction of phenolic compounds and aldehyde compounds (industrially, phenol and formaldehyde). Its high cross-linking density between molecular chains allows it to maintain good performance under harsh environments. However, phenolic resin also has significant drawbacks that limit its application in etching molds. This is mainly because the molecular structure of phenolic resin is relatively rigid, and the molecular chain segments have poor mobility. When subjected to external impacts, it cannot effectively absorb energy and is prone to brittle fracture, i.e., poor toughness. Summary of the Invention
[0004] The purpose of this invention is to provide a phenolic resin composite material and its application in etching molds, so as to solve the problems existing in the background art.
[0005] To achieve the above objectives, the present invention provides the following solution: A method for preparing a phenolic resin composite material, the method comprising the following steps: Phenol and formaldehyde aqueous solution are added to deionized water, heated under nitrogen protection and reflux, kept at the temperature, stirred and mixed for the first time, ammonia water is added to adjust the pH, stirred under ultrasound, dehydrated for the first time, modified filler is added, stirred and mixed for the second time, and dehydrated for the second time, thus completing the preparation.
[0006] In one embodiment, the mass ratio of the phenol, the formaldehyde aqueous solution, the deionized water, and the modified filler is 50:120-125:40:3-3.5.
[0007] In one embodiment, the temperature increase refers to raising the temperature to 75-80°C.
[0008] In one embodiment, the first stirring and mixing refers to stirring for 30-60 minutes; the second stirring and mixing refers to stirring for 45-60 minutes.
[0009] In one embodiment, the ultrasonic stirring reaction refers to stirring under ultrasonic power of 300W for 4-5.5 hours.
[0010] In one embodiment, the first dehydration refers to dehydration at 40-45°C under a vacuum of -0.09MPa for 20-25 minutes; the second dehydration refers to dehydration at 90-110°C under a vacuum of -0.09MPa until constant weight.
[0011] In one embodiment, the modified filler is prepared by the following steps: Step (1): Disperse and mix nano-silica and ethanol aqueous solution under ultrasound, add γ-aminopropyltriethoxysilane, heat and react under reflux, filter, take the filter residue, wash with ethanol, dry, and obtain the first component; Step (2): Disperse and mix the first component and dimethylformamide under ultrasound, add dimethylolpropionic acid and p-toluenesulfonic acid, heat and react under nitrogen protection and reflux, filter, take the filter residue, wash with methanol, dry, and obtain the second component; Step (3): Disperse and mix the second component and tetrahydrofuran under ultrasound, add the modifier, heat under nitrogen protection and reflux, filter, take the filter residue, wash with acetone, and dry to complete the preparation.
[0012] Further, in step (1), the mass ratio of the nano-silica, the aqueous ethanol solution and the γ-aminopropyltriethoxysilane is 1.5-2:145-185:0.7-1.
[0013] Furthermore, in step (1), the mass fraction of the ethanol aqueous solution is 90-95%.
[0014] Further, in step (1), the ultrasonic dispersion and mixing refers to ultrasonic stirring with a power of 300-500W for 10-40 minutes for dispersion and mixing.
[0015] Furthermore, in step (1), the heating reaction refers to heating to 60-70℃ and then stirring at a constant temperature for 7-9 hours.
[0016] Further, in step (1), the drying refers to vacuum drying at 75-80°C to constant weight.
[0017] Further, in step (2), the mass ratio of the first component, the dimethylformamide, the dimethylolpropionic acid and the p-toluenesulfonic acid is 2.5-2.8:150-200:8:0.1.
[0018] Further, in step (2), the ultrasonic dispersion and mixing refers to ultrasonic stirring with a power of 300-500W for 10-20 minutes for dispersion and mixing.
[0019] Furthermore, in step (2), the heating reaction refers to heating to 80-90℃ and then stirring at a constant temperature for 6-8 hours.
[0020] Furthermore, in step (2), the drying refers to vacuum drying at 40-85°C to constant weight.
[0021] Further, in step (3), the mass ratio of the second component, the tetrahydrofuran and the modifier is 1:120-130:0.06-0.1; the modifier includes 3-isocyanate-propyltrimethoxysilane and m-toluene isocyanate; the molar ratio of 3-isocyanate-propyltrimethoxysilane and m-toluene isocyanate is 1:0.4-0.6.
[0022] Further, in step (3), the ultrasonic dispersion and mixing refers to ultrasonic stirring with a power of 300-500W for 10-15 minutes for dispersion and mixing.
[0023] Furthermore, in step (3), the heating reaction refers to heating to 40-50℃ and then stirring at a constant temperature for 2-4 hours.
[0024] Furthermore, in step (3), the drying refers to vacuum drying at 45-50°C to constant weight.
[0025] A phenolic resin composite material prepared by the above-described preparation method.
[0026] Application of a phenolic resin composite material prepared by the above preparation method in etching molds.
[0027] The beneficial effects of this invention are as follows: This invention mainly focuses on the technical improvement of inorganic particles. By using composite modified fillers, the prepared phenolic resin composite material has good toughness and is not prone to brittle fracture under external force, which expands its application in etching molds. When used as a resin plate, it can better replace metal plates for etching. In addition, the process of preparing phenolic resin composite material in this invention is simple, basically retains the inherent synthesis method, and the curing characteristics are not changed, thus balancing cost and production efficiency. Detailed Implementation
[0028] The present invention will be further described below with reference to specific embodiments. It should be understood that the specific embodiments of the present invention are only used to illustrate the spirit and principles of the present invention, and are not intended to limit the scope of the present invention. Furthermore, it should be understood that after reading the contents of the present invention, those skilled in the art can make various modifications, substitutions, deletions, corrections, or adjustments to the technical solutions of the present invention, and these equivalent technical solutions also fall within the scope defined by the claims of the present invention.
[0029] Example 1 A method for preparing a phenolic resin composite material, the method comprising the following steps: Phenol and formaldehyde aqueous solution (37% by mass) were added to deionized water, heated under nitrogen protection and reflux, kept at the temperature, stirred and mixed for the first time, ammonia water (25% by mass) was added to adjust the pH to 10, stirred under ultrasonication, dehydrated for the first time, modified filler was added, stirred and mixed for the second time, and dehydrated for the second time, thus completing the preparation.
[0030] The mass ratio of the phenol, the formaldehyde aqueous solution, the deionized water, and the modified filler is 50:120:40:3; the heating refers to heating to 75℃ (heating rate 5℃ / min); the first stirring and mixing refers to stirring for 30 min; the second stirring and mixing refers to stirring for 45 min; the ultrasonic stirring reaction refers to stirring under ultrasonic power of 300W for 4 h; the first dehydration refers to dehydration at 40℃ under vacuum of -0.09MPa for 20 min; the second dehydration refers to dehydration to constant weight at 90℃ under vacuum of -0.09MPa.
[0031] The modified filler is prepared by the following steps: Step (1): Disperse and mix nano-silica (Shanghai Yuanye Biotechnology Co., Ltd., V32257) and ethanol aqueous solution under ultrasonication, add γ-aminopropyltriethoxysilane, heat under reflux, filter, take the filter residue, wash with ethanol, dry, and obtain the first component; Step (2): Disperse and mix the first component and dimethylformamide under ultrasound, add dimethylolpropionic acid and p-toluenesulfonic acid, heat and react under nitrogen protection and reflux, filter, take the filter residue, wash with methanol, dry, and obtain the second component; Step (3): Disperse and mix the second component and tetrahydrofuran under ultrasound, add the modifier, heat under nitrogen protection and reflux, filter, take the filter residue, wash with acetone, and dry to complete the preparation.
[0032] In step (1), the mass ratio of the nano-silica, the aqueous ethanol solution, and the γ-aminopropyltriethoxysilane is 1.5:145:0.7; the mass fraction of the aqueous ethanol solution is 90%; the ultrasonic dispersion and mixing refers to dispersion and mixing under ultrasonic stirring at a power of 300W for 10 minutes; the heating reaction refers to heating to 60℃ (heating rate 5℃ / min) and then stirring at a constant temperature for 7 hours; the drying refers to vacuum drying at 75℃ to constant weight.
[0033] In step (2), the mass ratio of the first component, the dimethylformamide, the dimethylolpropionic acid and the p-toluenesulfonic acid is 2.5:150:8:0.1; the ultrasonic dispersion and mixing refers to dispersion and mixing under ultrasonic stirring at a power of 300W for 10 minutes; the heating reaction refers to heating to 80℃ (heating rate 5℃ / min) and then stirring at a constant temperature for 6 hours; the drying refers to vacuum drying at 40℃ to constant weight.
[0034] In step (3), the mass ratio of the second component, the tetrahydrofuran, and the modifier is 1:120:0.06; the modifier includes 3-isocyanate-propyltrimethoxysilane and m-toluene isocyanate; the molar ratio of 3-isocyanate-propyltrimethoxysilane and m-toluene isocyanate is 1:0.4; the ultrasonic dispersion and mixing refers to ultrasonic stirring at a power of 300W for 10 minutes; the heating reaction refers to heating to 40℃ (heating rate 5℃ / min) and then stirring at a constant temperature for 2 hours; the drying refers to vacuum drying at 45℃ to constant weight.
[0035] A phenolic resin composite material prepared by the above-described preparation method.
[0036] Application of a phenolic resin composite material prepared by the above preparation method in etching molds.
[0037] Example 2 A method for preparing a phenolic resin composite material, the method comprising the following steps: Phenol and formaldehyde aqueous solution (37% by mass) were added to deionized water, heated under nitrogen protection and reflux, kept at the temperature, stirred and mixed for the first time, ammonia water (25% by mass) was added to adjust the pH to 10, stirred under ultrasonication, dehydrated for the first time, modified filler was added, stirred and mixed for the second time, and dehydrated for the second time, thus completing the preparation.
[0038] The mass ratio of the phenol, the formaldehyde aqueous solution, the deionized water, and the modified filler is 50:125:40:3.5; the heating refers to heating to 80℃ (heating rate 5℃ / min); the first stirring and mixing refers to stirring for 60 min; the second stirring and mixing refers to stirring for 60 min; the ultrasonic stirring reaction refers to stirring under ultrasonic power of 300W for 5.5 h; the first dehydration refers to dehydration at 45℃ under vacuum of -0.09MPa for 25 min; the second dehydration refers to dehydration to constant weight at 110℃ under vacuum of -0.09MPa.
[0039] The modified filler is prepared by the following steps: Step (1): Disperse and mix nano-silica (Shanghai Yuanye Biotechnology Co., Ltd., V32257) and ethanol aqueous solution under ultrasonication, add γ-aminopropyltriethoxysilane, heat under reflux, filter, take the filter residue, wash with ethanol, dry, and obtain the first component; Step (2): Disperse and mix the first component and dimethylformamide under ultrasound, add dimethylolpropionic acid and p-toluenesulfonic acid, heat and react under nitrogen protection and reflux, filter, take the filter residue, wash with methanol, dry, and obtain the second component; Step (3): Disperse and mix the second component and tetrahydrofuran under ultrasound, add the modifier, heat under nitrogen protection and reflux, filter, take the filter residue, wash with acetone, and dry to complete the preparation.
[0040] In step (1), the mass ratio of the nano-silica, the aqueous ethanol solution, and the γ-aminopropyltriethoxysilane is 2:185:1; the mass fraction of the aqueous ethanol solution is 95%; the ultrasonic dispersion and mixing refers to dispersion and mixing under ultrasonic stirring at a power of 500W for 40 minutes; the heating reaction refers to heating to 70℃ (heating rate 5℃ / min) and then stirring at a constant temperature for 9 hours; the drying refers to vacuum drying at 80℃ to constant weight.
[0041] In step (2), the mass ratio of the first component, the dimethylformamide, the dimethylolpropionic acid and the p-toluenesulfonic acid is 2.8:200:8:0.1; the ultrasonic dispersion and mixing refers to dispersion and mixing under ultrasonic stirring at a power of 500W for 20 minutes; the heating reaction refers to heating to 90℃ (heating rate 5℃ / min) and then stirring at a constant temperature for 8 hours; the drying refers to vacuum drying at 85℃ to constant weight.
[0042] In step (3), the mass ratio of the second component, the tetrahydrofuran, and the modifier is 1:130:0.1; the modifier includes 3-isocyanate-propyltrimethoxysilane and m-toluene isocyanate; the molar ratio of 3-isocyanate-propyltrimethoxysilane and m-toluene isocyanate is 1:0.6; the ultrasonic dispersion and mixing refers to ultrasonic stirring at a power of 500W for 15 minutes; the heating reaction refers to heating to 50℃ (heating rate 5℃ / min) and then stirring at a constant temperature for 4 hours; the drying refers to vacuum drying at 50℃ to constant weight.
[0043] A phenolic resin composite material prepared by the above-described preparation method.
[0044] Application of a phenolic resin composite material prepared by the above preparation method in etching molds.
[0045] Example 3 A method for preparing a phenolic resin composite material, the method comprising the following steps: Phenol and formaldehyde aqueous solution (37% by mass) were added to deionized water, heated under nitrogen protection and reflux, kept at the temperature, stirred and mixed for the first time, ammonia water (25% by mass) was added to adjust the pH to 10, stirred under ultrasonication, dehydrated for the first time, modified filler was added, stirred and mixed for the second time, and dehydrated for the second time, thus completing the preparation.
[0046] The mass ratio of the phenol, the formaldehyde aqueous solution, the deionized water, and the modified filler is 50:122:40:3.2; the heating refers to heating to 78℃ (heating rate 5℃ / min); the first stirring and mixing refers to stirring for 45 min; the second stirring and mixing refers to stirring for 50 min; the ultrasonic stirring reaction refers to stirring under ultrasonic power of 300W for 5 h; the first dehydration refers to dehydration at 42℃ under vacuum of -0.09MPa for 24 min; the second dehydration refers to dehydration to constant weight at 100℃ under vacuum of -0.09MPa.
[0047] The modified filler is prepared by the following steps: Step (1): Disperse and mix nano-silica (Shanghai Yuanye Biotechnology Co., Ltd., V32257) and ethanol aqueous solution under ultrasonication, add γ-aminopropyltriethoxysilane, heat under reflux, filter, take the filter residue, wash with ethanol, dry, and obtain the first component; Step (2): Disperse and mix the first component and dimethylformamide under ultrasound, add dimethylolpropionic acid and p-toluenesulfonic acid, heat and react under nitrogen protection and reflux, filter, take the filter residue, wash with methanol, dry, and obtain the second component; Step (3): Disperse and mix the second component and tetrahydrofuran under ultrasound, add the modifier, heat under nitrogen protection and reflux, filter, take the filter residue, wash with acetone, and dry to complete the preparation.
[0048] In step (1), the mass ratio of the nano-silica, the aqueous ethanol solution, and the γ-aminopropyltriethoxysilane is 1.8:170:0.85; the mass fraction of the aqueous ethanol solution is 92%; the ultrasonic dispersion and mixing refers to dispersion and mixing under ultrasonic stirring at a power of 400W for 30 minutes; the heating reaction refers to heating to 65℃ (heating rate 5℃ / min) and then stirring at a constant temperature for 8 hours; the drying refers to vacuum drying at 78℃ to constant weight.
[0049] In step (2), the mass ratio of the first component, the dimethylformamide, the dimethylolpropionic acid and the p-toluenesulfonic acid is 2.6:180:8:0.1; the ultrasonic dispersion and mixing refers to dispersion and mixing under ultrasonic stirring at a power of 400W for 15 minutes; the heating reaction refers to heating to 85℃ (heating rate 5℃ / min) and then stirring at a constant temperature for 7 hours; the drying refers to vacuum drying at 70℃ to constant weight.
[0050] In step (3), the mass ratio of the second component, the tetrahydrofuran, and the modifier is 1:125:0.08; the modifier includes 3-isocyanate-propyltrimethoxysilane and m-toluene isocyanate; the molar ratio of 3-isocyanate-propyltrimethoxysilane and m-toluene isocyanate is 1:0.5; the ultrasonic dispersion and mixing refers to ultrasonic stirring at a power of 400W for 12 minutes; the heating reaction refers to heating to 45℃ (heating rate 5℃ / min) and then stirring at a constant temperature for 3 hours; the drying refers to vacuum drying at 48℃ to constant weight.
[0051] A phenolic resin composite material prepared by the above-described preparation method.
[0052] Application of a phenolic resin composite material prepared by the above preparation method in etching molds.
[0053] The technical solution of the present invention will be further explained as follows: Phenolic resins suffer from poor toughness and are prone to brittle fracture, which hinders their practical application. In view of this, the present invention improves the technology based on the toughening technology of inorganic particles. Nano-silica is a commonly used filler in industry, with advantages such as low cost and wide availability. When added to phenolic resin, it can achieve toughening through mechanisms such as dissipating impact energy and providing skeletal support. However, nano-silica is often limited by agglomeration and interfacial bonding problems, and usually cannot be used directly, requiring modification treatment.
[0054] Therefore, this invention utilizes a conventional silane coupling agent, γ-aminopropyltriethoxysilane, for amino modification. Since amino / hydroxyl groups readily undergo amidation / esterification with carboxyl groups, this invention adds dimethylolpropionic acid to the above-mentioned structure to generate a hyperbranched polymer with hydroxyl groups at the ends. Finally, appropriate amounts of 3-isocyanate-propyltrimethoxysilane and m-toluene isocyanate are further added. Through the reaction of hydroxyl groups with isocyanate groups, the silanoxy groups and benzene rings are modified. The above operations not only improve the toughening effect but also reduce particle aggregation and strengthen interfacial bonding. Specifically, the molecular chains of the hyperbranched polymer contain a large number of alkanes, have high degree of free rotation and good flexibility, and can synergistically achieve toughening with nano-silica. After hydrolysis, the modified silanoxy groups readily react with the hydroxyl groups of phenolic resin, promoting interfacial bonding and reducing aggregation. The modified benzene rings can form non-covalent bonds with phenolic resin through complementary electron clouds, further improving interfacial bonding.
[0055] It is important to emphasize that the amount of modified siloxy groups and benzene rings should not be excessive. Too much siloxy groups and benzene rings will have a negative effect on toughness. This is because, due to steric hindrance, too many siloxy groups and benzene rings will hinder the cross-linking of the phenolic resin during curing, resulting in a decrease in cross-linking density.
[0056] Comparative Example 1 Comparative Example 1 and Example 3 differ in that 3-isocyanate-propyltrimethoxysilane is replaced with the same amount of m-toluene isocyanate.
[0057] Comparative Example 2 Comparative Example 2 and Example 3 differ in that m-toluene isocyanate is replaced with the same amount of 3-isocyanate-propyltrimethoxysilane.
[0058] Comparative Example 3 Comparative Example 3 differs from Example 3 in that the modified filler was replaced with the same mass of the second component (the preparation method is the same as in Example 3).
[0059] Comparative Example 4 Comparative Example 4 is different from Example 3 in that the modified filler is replaced with the same mass of the first component (the preparation method is the same as in Example 3).
[0060] Comparative Example 5 Compared with Example 3, Comparative Example 5 differs in that the mass ratio of the second component, the tetrahydrofuran, and the modifier is changed from 1:125:0.08 to 1:125:0.3.
[0061] Comparative Example 6 Comparative Example 6 is compared with Example 3, except that the modified filler was replaced with the same mass of deionized water.
[0062] Test case The phenolic resin composite materials prepared in Example 3 and Comparative Examples 1-6 were used to prepare test specimens. The method was as follows: the specimens were placed in a flat vulcanizing machine preheated to 150°C and hot-pressed (conditions: temperature 165°C, pressure 20 MPa, holding pressure for 15 min). After removal, they were cured at 170°C for 6 h, allowed to cool naturally to room temperature, and then cut into 8mm*8mm*64mm pieces. Unnotched impact strength tests were performed according to standard GB / T 1843-2008.
[0063] The data in Table 1 below show that the phenolic resin composite material of the present invention has the highest impact strength, reaching 4.7 kJ / m. 2 This reflects better toughness and makes it less prone to brittle fracture when subjected to external forces.
[0064] Table 1. Test Results This invention mainly focuses on the technical improvement of inorganic particles. By using composite modified fillers, the prepared phenolic resin composite material has good toughness and is not prone to brittle fracture under external force, which expands its application in etching molds. When used as a resin plate, it can better replace metal plates for etching. In addition, the process of preparing phenolic resin composite material in this invention is simple, basically retains the inherent synthesis method, and the curing characteristics are not changed, thus balancing cost and production efficiency.
[0065] The above description is merely a preferred embodiment of the present invention and is not intended to limit the invention. Various modifications and variations can be made to the present invention by those skilled in the art. Any modifications, equivalent substitutions, improvements, etc., made within the spirit and principles of the present invention are included within the scope of protection of the present invention.
Claims
1. A method for preparing a phenolic resin composite material, characterized in that: The preparation method includes the following steps: Phenol and formaldehyde aqueous solution are added to deionized water, heated under nitrogen protection and reflux, kept at the temperature, stirred and mixed for the first time, ammonia water is added to adjust the pH, stirred under ultrasound, dehydrated for the first time, modified filler is added, stirred and mixed for the second time, and dehydrated for the second time, thus completing the preparation.
2. The method for preparing a phenolic resin composite material according to claim 1, characterized in that: The mass ratio of the phenol, the formaldehyde aqueous solution, the deionized water, and the modified filler is 50:120-125:40:3-3.
5.
3. The method for preparing a phenolic resin composite material according to claim 1, characterized in that: The heating refers to raising the temperature to 75-80℃; the ultrasonic stirring reaction refers to stirring the reaction under ultrasonic power of 300W for 4-5.5 hours.
4. The method for preparing a phenolic resin composite material according to claim 1, characterized in that: The modified filler is prepared by the following steps: Step (1): Disperse and mix nano-silica and ethanol aqueous solution under ultrasound, add γ-aminopropyltriethoxysilane, heat and react under reflux, filter, take the filter residue, wash with ethanol, dry, and obtain the first component; Step (2): Disperse and mix the first component and dimethylformamide under ultrasound, add dimethylolpropionic acid and p-toluenesulfonic acid, heat and react under nitrogen protection and reflux, filter, take the filter residue, wash with methanol, dry, and obtain the second component; Step (3): Disperse and mix the second component and tetrahydrofuran under ultrasound, add the modifier, heat under nitrogen protection and reflux, filter, take the filter residue, wash with acetone, and dry to complete the preparation.
5. The method for preparing a phenolic resin composite material according to claim 4, characterized in that: In step (1), the mass ratio of the nano-silica, the aqueous ethanol solution and the γ-aminopropyltriethoxysilane is 1.5-2:145-185:0.7-1.
6. The method for preparing a phenolic resin composite material according to claim 4, characterized in that: In step (2), the mass ratio of the first component, the dimethylformamide, the dimethylolpropionic acid and the p-toluenesulfonic acid is 2.5-2.8:150-200:8:0.
1.
7. The method for preparing a phenolic resin composite material according to claim 4, characterized in that: In step (2), the heating reaction refers to heating to 80-90℃ and then stirring at a constant temperature for 6-8 hours.
8. The method for preparing a phenolic resin composite material according to claim 4, characterized in that: In step (3), the mass ratio of the second component, the tetrahydrofuran and the modifier is 1:120-130:0.06-0.1; the modifier includes 3-isocyanate-propyltrimethoxysilane and m-toluene isocyanate; the molar ratio of 3-isocyanate-propyltrimethoxysilane and m-toluene isocyanate is 1:0.4-0.
6.
9. A phenolic resin composite material prepared by the preparation method according to any one of claims 1-8.
10. The application of a phenolic resin composite material prepared by the preparation method according to any one of claims 1-8 in an etching mold.