Phenolic resin glue solution for copper-clad plate and application of phenolic resin glue solution

Abstract

The invention provides a phenolic resin glue solution for a copper-clad plate. The phenolic resin glue solution is prepared from the following components in parts by weight: 32-35 parts of melamine modified phenolic resin, 20-24 parts of tung oil modified phenolic resin, 7-10 parts of a curing agent, 0.2-0.5 part of an accelerant, 4-5 parts of an auxiliary agent, 18-22 parts of filler, 8-12 parts of a flexibilizer and 70-76 parts of a solvent. The invention also provides application of the phenolic resin glue solution for the copper-clad plate. The phenolic resin glue solution for the copper-clad plate, provided by the invention, has relatively good flame retardance and toughness.

Description

Technical Field

[0001] The present invention relates to a resin adhesive, and particularly to a phenolic resin adhesive for copper clad laminates and its applications. Background Art

[0002] Copper clad laminates, also known as copper clad laminate sheets, are products made by impregnating electronic-grade fiberglass cloth with resin adhesive and then covering one or both sides with copper foil through hot pressing. They are the basic materials of the electronics industry, mainly used for manufacturing printed circuit boards, and are widely applied in electronic product fields such as televisions, radios, computers, laptops, and mobile communications. Phenolic resins are inexpensive and have good performance, being widely used in fields such as automotive, electronics, transportation, and aerospace, and can also be used as the resin adhesive for copper clad laminates.

[0003] Currently, the commonly used phenolic resin for copper clad laminates is linear phenolic resin. Linear phenolic resin has good heat resistance, water resistance, corrosion resistance, mechanical properties, etc. However, copper clad laminates have relatively high requirements for flame retardancy. Ordinary phenolic resins generally have mediocre flame retardancy and cannot meet the flame retardancy requirements of copper clad laminates. Moreover, phenolic resins are brittle and have poor toughness, which limits their further application in copper clad laminates. Summary of the Invention

[0004] The technical problem to be solved by the present invention is to provide a phenolic resin adhesive for copper clad laminates, which has better flame retardancy and toughness.

[0005] To solve the above technical problem, the technical solution of the present invention is as follows:

[0006] A phenolic resin adhesive for copper clad laminates is made from the following components in parts by weight: 32 - 35 parts of melamine-modified phenolic resin, 20 - 24 parts of tung oil-modified phenolic resin, 7 - 10 parts of curing agent, 0.2 - 0.5 part of accelerator, 4 - 5 parts of auxiliary agent, 18 - 22 parts of filler, 8 - 12 parts of toughening agent, and 70 - 76 parts of solvent.

[0007] Further, the curing agent in the present invention is triethanolamine.

[0008] Further, the accelerator in the present invention is 2-methylimidazole.

[0009] Further, the auxiliary agent in the present invention is 3-chloro-4-(difluoromethoxy)phenyl isocyanate.

[0010] Further, the filler in the present invention is alumina with an average particle size of 2.6 μm.

[0011] Further, the toughening agent in the present invention is made by the following steps:

[0012] Mix zinc nitrate, 3-bromo-2,6-dimethylbenzoic acid, N,N-dimethylacetamide, and benzoic acid, and stir for 40 - 60 minutes to obtain a mixed solution. Place the mixed solution in an oven, heat it to 110 °C and keep it warm for 48 hours. After cooling to room temperature, obtain the reactant. Filter the reactant to obtain the filter residue. Wash the filter residue with N,N-dimethylacetamide three times and then dry it for 10 - 12 hours to obtain the auxiliary agent.

[0013] Further, in the preparation steps of the toughening agent of the present invention, the ratio of zinc nitrate, 3-bromo-2,6-dimethylbenzoic acid, N,N-dimethylacetamide, and benzoic acid is 1 mmol: 0.5 mmol: 120 mL: 0.6 g. The stirring speed during stirring is 200 revolutions per minute, the heating rate of the oven is 10 °C per hour, and the drying temperature is 75 °C.

[0014] Further, the solvent of the present invention is ethylene glycol monomethyl ether.

[0015] Another technical problem to be solved by the present invention is to provide the application of the phenolic resin adhesive solution for copper clad laminates in copper clad laminates.

[0016] To solve the above technical problems, the technical solution is:

[0017] An application of a phenolic resin adhesive solution for copper clad laminates, comprising the following steps:

[0018] S1. Weigh each component of the phenolic resin adhesive solution for copper clad laminates by weight. Mix melamine-modified phenolic resin, tung oil-modified phenolic resin, curing agent, accelerator, and solvent, and stir at a stirring speed of 500 - 600 revolutions per minute for 1 - 2 hours. Then add other components and stir at a stirring speed of 800 - 1000 revolutions per minute for 2 - 3 hours to obtain the phenolic resin adhesive solution for copper clad laminates;

[0019] S2. Immerse bleached wood pulp paper into the phenolic resin adhesive solution for copper clad laminates obtained in step S1, and bake it at 150 - 170 °C for 1 minute to obtain a prepreg;

[0020] S3. Stack 6 prepregs obtained in step S2 together to obtain a laminated sheet. Cover each of the upper and lower surfaces of the laminated sheet with a copper foil, and place it in a hot press to hot press at 150 - 160 °C and a pressure of 30 - 40 MPa for 80 - 120 minutes to obtain a copper clad laminate.

[0021] Compared with the prior art, the present invention has the following beneficial effects:

[0022] 1) The toughness of the tung oil modified phenolic resin used in the present invention is stronger than that of ordinary phenolic resins. However, it can only play a toughening effect. With the addition of tung oil, the flame retardancy of the resin glue system becomes worse. Therefore, the present invention also uses a melamine modified phenolic resin with strong flame retardancy, and a phenolic resin glue for copper clad laminates with good toughness and flame retardancy is prepared by compounding with the tung oil modified phenolic resin.

[0023] 2) The toughening agent used in the present invention is made from zinc nitrate, 3-bromo-2,6-dimethylbenzoic acid, etc. by a solvothermal method. It has a three-dimensional network structure and can further improve the toughness of the phenolic resin glue for copper clad laminates and the copper clad laminates.

[0024] 3) The auxiliary agent used in the present invention is 3-chloro-4-difluoromethoxyphenyl isocyanate. It can promote the cross-linking reaction of the resin glue system, effectively improve the adhesiveness of the phenolic resin glue for copper clad laminates and the peel strength of the copper clad laminates, and can further improve the flame retardancy of the phenolic resin glue for copper clad laminates and the copper clad laminates. Detailed Embodiments

[0025] The present invention will be described in detail below with reference to specific embodiments. Here, the illustrative embodiments of the present invention and their descriptions are used to explain the present invention, but not to limit the present invention.

[0026] Example 1

[0027] The phenolic resin glue for copper clad laminates is made from the following components in parts by weight: 34 parts of melamine modified phenolic resin, 23 parts of tung oil modified phenolic resin, 9 parts of triethanolamine, 0.4 part of 2-methylimidazole, 4.8 parts of 3-chloro-4-difluoromethoxyphenyl isocyanate, 21 parts of alumina with an average particle size of 2.6 μm, 10 parts of toughening agent, and 75 parts of ethylene glycol monomethyl ether.

[0028] Among them, the toughening agent is made by the following steps:

[0029] Mix zinc nitrate, 3-bromo-2,6-dimethylbenzoic acid, N,N-dimethylacetamide, and benzoic acid in a ratio of 1 mmol:0.5 mmol:120 mL:0.6 g, stir at a stirring speed of 200 revolutions per minute for 50 minutes to obtain a mixed solution. Place the mixed solution in an oven, heat it to 110 °C at a heating rate of 10 °C per hour, keep it warm for 48 hours, cool it to room temperature to obtain a reaction product. Filter the reaction product to obtain a filter residue. Wash the filter residue with N,N-dimethylacetamide 3 times and then dry it at 75 °C for 11 hours to obtain the auxiliary agent.

[0030] The application of the phenolic resin glue for copper clad laminates in manufacturing copper clad laminates includes the following steps:

[0031] S1. Weigh each component of the phenolic resin adhesive for copper clad laminate by weight parts. Mix melamine-modified phenolic resin, tung oil-modified phenolic resin, triethanolamine, 2-methylimidazole, and ethylene glycol monomethyl ether, and stir at a stirring speed of 500 revolutions per minute for 2 hours. Then add other components and stir at a stirring speed of 900 revolutions per minute for 2.5 hours to obtain the phenolic resin adhesive for copper clad laminate.

[0032] S2. Immerse the bleached wood pulp paper into the phenolic resin adhesive for copper clad laminate obtained in step S1, and bake at 160 °C for 1 minute to obtain a prepreg.

[0033] S3. Stack 6 prepregs obtained in step S2 together to obtain a laminated sheet, cover a copper foil on each of the upper and lower surfaces of the laminated sheet, and place it in a hot press to hot press at 155 °C and a pressure of 35 MPa for 100 minutes to obtain a copper clad laminate.

[0034] Example 2

[0035] The phenolic resin adhesive for copper clad laminate is made of the following components by weight parts: 32 parts of melamine-modified phenolic resin, 20 parts of tung oil-modified phenolic resin, 7 parts of triethanolamine, 0.2 part of 2-methylimidazole, 4 parts of 3-chloro-4-difluoromethoxyphenyl isocyanate, 18 parts of alumina with an average particle size of 2.6 μm, 8 parts of toughening agent, and 70 parts of ethylene glycol monomethyl ether.

[0036] Among them, the toughening agent is made by the following steps:

[0037] Mix zinc nitrate, 3-bromo-2,6-dimethylbenzoic acid, N,N-dimethylacetamide, and benzoic acid in a ratio of 1 mmol:0.5 mmol:120 mL:0.6 g, and stir at a stirring speed of 200 revolutions per minute for 40 minutes to obtain a mixed solution. Place the mixed solution in an oven, heat it to 110 °C at a heating rate of 10 °C per hour, and keep it warm for 48 hours. After cooling to room temperature, obtain a reaction product. Filter the reaction product to obtain a filter residue. Wash the filter residue with N,N-dimethylacetamide 3 times and dry it at 75 °C for 10 hours to obtain an auxiliary agent.

[0038] The application of the phenolic resin adhesive for copper clad laminate in manufacturing a copper clad laminate includes the following steps:

[0039] S1. Weigh each component of the phenolic resin adhesive for copper clad laminate by weight parts. Mix melamine-modified phenolic resin, tung oil-modified phenolic resin, triethanolamine, 2-methylimidazole, and ethylene glycol monomethyl ether, and stir at a stirring speed of 600 revolutions per minute for 1 hour. Then add other components and stir at a stirring speed of 1000 revolutions per minute for 2 hours to obtain the phenolic resin adhesive for copper clad laminate.

[0040] S2. Immerse the bleached wood pulp paper into the phenolic resin adhesive for copper clad laminate obtained in step S1, and bake at 170 °C for 1 minute to obtain a prepreg.

[0041] S3. Stack the six prepregs obtained in step S2 together to obtain a laminated sheet, cover each of the upper and lower surfaces of the laminated sheet with a copper foil, and place it in a hot press for hot pressing at 160 °C and a pressure of 30 MPa for 80 minutes to obtain a copper clad laminate.

[0042] Example 3

[0043] The phenolic resin adhesive solution for copper clad laminates is made of the following components by weight: 33 parts of melamine-modified phenolic resin, 21 parts of tung oil-modified phenolic resin, 8 parts of triethanolamine, 0.3 part of 2-methylimidazole, 4.2 parts of 3-chloro-4-difluoromethoxyphenyl isocyanate, 19 parts of alumina with an average particle size of 2.6 μm, 9 parts of toughening agent, and 72 parts of ethylene glycol monomethyl ether.

[0044] Among them, the toughening agent is made by the following steps:

[0045] Mix zinc nitrate, 3-bromo-2,6-dimethylbenzoic acid, N,N-dimethylacetamide, and benzoic acid in a ratio of 1 mmol:0.5 mmol:120 mL:0.6 g, stir at a stirring speed of 200 revolutions per minute for 45 minutes to obtain a mixed solution, place the mixed solution in an oven, heat it to 110 °C at a heating rate of 10 °C per hour, keep it warm for 48 hours, cool it to room temperature to obtain a reaction product, filter the reaction product to obtain a filter residue, wash the filter residue with N,N-dimethylacetamide 3 times, and dry it at 75 °C for 10.5 hours to obtain an auxiliary agent.

[0046] The application of the phenolic resin adhesive solution for copper clad laminates in the manufacture of copper clad laminates includes the following steps:

[0047] S1. Weigh each component of the phenolic resin adhesive solution for copper clad laminates by weight, mix melamine-modified phenolic resin, tung oil-modified phenolic resin, triethanolamine, 2-methylimidazole, and ethylene glycol monomethyl ether, stir at a stirring speed of 500 revolutions per minute for 1.5 hours, then add other components, and stir at a stirring speed of 800 revolutions per minute for 3 hours to obtain the phenolic resin adhesive solution for copper clad laminates;

[0048] S2. Immerse the bleached wood pulp paper into the phenolic resin adhesive solution for copper clad laminates obtained in step S1, and bake it at 165 °C for 1 minute to obtain a prepreg;

[0049] S3. Stack the six prepregs obtained in step S2 together to obtain a laminated sheet, cover each of the upper and lower surfaces of the laminated sheet with a copper foil, and place it in a hot press for hot pressing at 152 °C and a pressure of 38 MPa for 90 minutes to obtain a copper clad laminate.

[0050] Example 4

[0051] The phenolic resin adhesive solution for copper clad laminates is made from the following components in parts by weight: 35 parts of melamine-modified phenolic resin, 24 parts of tung oil-modified phenolic resin, 10 parts of triethanolamine, 0.5 part of 2-methylimidazole, 5 parts of 3-chloro-4-difluoromethoxyphenyl isocyanate, 22 parts of alumina with an average particle size of 2.6 μm, 12 parts of toughening agent, and 76 parts of ethylene glycol monomethyl ether.

[0052] Among them, the toughening agent is made by the following steps:

[0053] Mix zinc nitrate, 3-bromo-2,6-dimethylbenzoic acid, N,N-dimethylacetamide, and benzoic acid in a ratio of 1 mmol:0.5 mmol:120 mL:0.6 g, stir at a stirring speed of 200 revolutions per minute for 60 minutes to obtain a mixed solution. Place the mixed solution in an oven, heat it to 110 °C at a heating rate of 10 °C per hour, keep it warm for 48 hours, cool it to room temperature to obtain a reaction product. Filter the reaction product to obtain a filter residue, wash the filter residue with N,N-dimethylacetamide 3 times, and dry it at 75 °C for 12 hours to obtain an auxiliary agent.

[0054] The application of the phenolic resin adhesive solution for copper clad laminates in manufacturing copper clad laminates includes the following steps:

[0055] S1. Weigh each component of the phenolic resin adhesive solution for copper clad laminates in parts by weight. Mix melamine-modified phenolic resin, tung oil-modified phenolic resin, triethanolamine, 2-methylimidazole, and ethylene glycol monomethyl ether, stir at a stirring speed of 600 revolutions per minute for 1.5 hours, then add other components, and stir at a stirring speed of 900 revolutions per minute for 2 hours to obtain the phenolic resin adhesive solution for copper clad laminates;

[0056] S2. Immerse bleached wood pulp paper into the phenolic resin adhesive solution for copper clad laminates obtained in step S1, and bake it at 150 °C for 1 minute to obtain a semi-cured sheet;

[0057] S3. Stack 6 semi-cured sheets obtained in step S2 together to obtain a laminated sheet, cover each of the upper and lower surfaces of the laminated sheet with a copper foil, and place it in a hot press to hot press at 150 °C and a pressure of 40 MPa for 120 minutes to obtain a copper clad laminate.

[0058] Example 5

[0059] The phenolic resin adhesive solution for copper clad laminates is made from the following components in parts by weight: 33 parts of melamine-modified phenolic resin, 22 parts of tung oil-modified phenolic resin, 8 parts of triethanolamine, 0.3 part of 2-methylimidazole, 4.5 parts of 3-chloro-4-difluoromethoxyphenyl isocyanate, 20 parts of alumina with an average particle size of 2.6 μm, 11 parts of toughening agent, and 74 parts of ethylene glycol monomethyl ether.

[0060] Among them, the toughening agent is made by the following steps:

[0061] Mix zinc nitrate, 3-bromo-2,6-dimethylbenzoic acid, N,N-dimethylacetamide, and benzoic acid in a ratio of 1 mmol:0.5 mmol:120 mL:0.6 g, stir for 55 minutes at a stirring speed of 200 revolutions per minute to obtain a mixed solution. Place the mixed solution in an oven, heat it to 110 °C at a heating rate of 10 °C per hour, keep it warm for 48 hours, cool it to room temperature to obtain a reaction product, filter the reaction product to obtain a filter residue, wash the filter residue 3 times with N,N-dimethylacetamide, and dry it at 75 °C for 11.5 hours to obtain an auxiliary agent.

[0062] The application of the phenolic resin adhesive solution for copper clad laminates in the manufacture of copper clad laminates includes the following steps:

[0063] S1. Weigh each component of the phenolic resin adhesive solution for copper clad laminates by weight. Mix melamine-modified phenolic resin, tung oil-modified phenolic resin, triethanolamine, 2-methylimidazole, and ethylene glycol monomethyl ether, stir for 2 hours at a stirring speed of 500 revolutions per minute, then add other components, and stir for 2.5 hours at a stirring speed of 800 revolutions per minute to obtain the phenolic resin adhesive solution for copper clad laminates;

[0064] S2. Immerse bleached wood pulp paper into the phenolic resin adhesive solution for copper clad laminates obtained in step S1, and bake it at 155 °C for 1 minute to obtain a prepreg;

[0065] S3. Stack 6 prepregs obtained in step S2 together to obtain a laminated sheet, cover each of the upper and lower surfaces of the laminated sheet with a copper foil, and place it in a hot press to hot press at 157 °C and a pressure of 32 MPa for 110 minutes to obtain a copper clad laminate.

[0066] Comparative Example 1

[0067] The difference from Example 1 is that the melamine-modified phenolic resin in the components of the phenolic resin adhesive solution for copper clad laminates is replaced with ordinary linear phenolic resin.

[0068] Comparative Example 2

[0069] The difference from Example 1 is that the tung oil-modified phenolic resin in the components of the phenolic resin adhesive solution for copper clad laminates is replaced with ordinary linear phenolic resin.

[0070] Comparative Example 3

[0071] The difference from Example 1 is that the toughening agent is not included in the components of the phenolic resin adhesive solution for copper clad laminates, and the preparation step of the toughening agent is omitted.

[0072] Comparative Example 4

[0073] The difference from Example 1 is that 3-chloro-4-difluoromethoxyphenyl isocyanate is not included in the components of the phenolic resin adhesive solution for copper clad laminates.

[0074] Experimental Example 1: Flame Retardancy Test

[0075] Test reference standard / method: GB / T2406 - 1993 standard.

[0076] Test instrument: Oxygen index analyzer.

[0077] Test object / target: Limiting oxygen index of the copper - clad laminates prepared in Examples 1 - 5, Comparative Example 1, and Comparative Example 4.

[0078] The higher the limiting oxygen index, the better the flame retardancy. The test results are shown in Table 1:

[0079] Limiting oxygen index (%) Example 1 30.3 Example 2 30.8 Example 3 30.6 Example 4 29.9 Example 5 30.1 Comparative Example 1 22.4 Comparative Example 4 25.8

[0080] Table 1

[0081] As can be seen from Table 1, the limiting oxygen indices of Examples 1 - 5 of the present invention are all relatively high, indicating that the present invention has good flame retardancy. Some components of the phenolic resin adhesive used in Comparative Example 1 and 4 are different from those in Example 1. Compared with Example 1, the limiting oxygen index of Comparative Example 1 has decreased significantly, indicating that the melamine - modified phenolic resin used in the present invention can effectively improve the flame retardancy of the phenolic resin adhesive for copper - clad laminates and the copper - clad laminates; the limiting oxygen index of Comparative Example 4 has also decreased to some extent, indicating that the 3 - chloro - 4 - difluoromethoxyphenyl isocyanate used in the present invention can also improve the flame retardancy of the phenolic resin adhesive for copper - clad laminates and the copper - clad laminates.

[0082] Experimental Example 2: Toughness Test

[0083] Test reference standard / method: GB / T1043 - 2008 standard.

[0084] Test instrument: Impact testing machine.

[0085] Test object / target: Impact resistance of the copper - clad laminates prepared in Examples 1 - 5, Comparative Example 2, and Comparative Example 3.

[0086] The higher the impact resistance, the better the toughness. The test results are shown in Table 2:

[0087] <![CDATA[Impact strength (kJ·m -2 )]]> Example 1 8.28 Example 2 8.09 Example 3 8.17 Example 4 8.52 Example 5 8.41 Comparative Example 2 5.37 Comparative Example 3 5.54

[0088] Table 2

[0089] As can be seen from Table 2, the impact resistances of Examples 1 - 5 of the present invention are all relatively high, indicating that the present invention has good toughness. Some components of the phenolic resin adhesive used in Comparative Example 2 and 3 are different from those in Example 1. Compared with Example 1, the impact resistances of Comparative Example 2 and 3 have both decreased significantly, indicating that the tung - oil - modified phenolic resin and toughening agent used in the present invention can effectively improve the toughness of the phenolic resin adhesive for copper - clad laminates and the copper - clad laminates.

[0090] Experimental Example 3: Peel Strength Test

[0091] Test reference standard / method: IPC-TM-650 standard.

[0092] Test instrument: Peel strength tester, with a peel speed of 50 mm / min and a peel angle of 90°.

[0093] Test object and target: Peel strength of the copper clad laminates prepared in Examples 1-5 and Comparative Example 4.

[0094] The test results are shown in Table 3:

[0095] Peeling strength (N / mm) Example 1 1.67 Example 2 1.53 Example 3 1.55 Example 4 1.69 Example 5 1.62 Comparative Example 4 1.03

[0096] Table 3

[0097] As can be seen from Table 3, the peel strengths of Examples 1-5 of the present invention are all relatively high. Some components of the phenolic resin adhesive used in Comparative Example 4 are different from those in Example 1. Compared with Example 1, the peel strength of Comparative Example 4 has decreased significantly, indicating that the 3-chloro-4-difluoromethoxyphenyl isocyanate used in the present invention can effectively improve the adhesiveness of the phenolic resin adhesive for copper clad laminates and the peel strength of the copper clad laminates.

[0098] The above embodiments merely illustrate the principles and effects of the present invention, rather than limiting the present invention. Any person familiar with this technology can modify or change the above embodiments without departing from the spirit and scope of the present invention. Therefore, all equivalent modifications or changes completed by those with ordinary knowledge in the technical field without departing from the spirit and technical idea disclosed by the present invention should still be covered by the claims of the present invention.

Claims

1. A phenolic resin adhesive solution for copper clad laminates, characterized in that: It is made from the following components in parts by weight: 32 - 35 parts of melamine - modified phenolic resin, 20 - 24 parts of tung oil - modified phenolic resin, 7 - 10 parts of curing agent, 0.2 - 0.5 part of accelerator, 4 - 5 parts of auxiliary agent, 18 - 22 parts of filler, 8 - 12 parts of toughening agent, and 70 - 76 parts of solvent.

2. The phenolic resin adhesive solution for copper clad laminate according to claim 1, characterized in that: The curing agent is triethanolamine.

3. The phenolic resin adhesive solution for copper clad laminate according to claim 1, wherein: The accelerator is 2 - methylimidazole.

4. A phenolic resin adhesive solution for copper clad laminates according to claim 1, wherein: The auxiliary agent is 3 - chloro - 4 - difluoromethoxyphenyl isocyanate.

5. The phenolic resin adhesive solution for copper clad laminate according to claim 1, wherein: The filler is alumina with an average particle size of 2.6 μm.

6. The phenolic resin glue solution for copper clad laminate according to claim 1, characterized in that: The toughening agent is prepared by the following steps: Mix zinc nitrate, 3 - bromo - 2,6 - dimethylbenzoic acid, N,N - dimethylacetamide, and benzoic acid, stir for 40 - 60 minutes to obtain a mixed solution. Place the mixed solution in an oven, heat it to 110 °C and keep it warm for 48 hours. After cooling to room temperature, obtain a reaction product. Filter the reaction product to obtain a filter residue. Wash the filter residue with N,N - dimethylacetamide 3 times and then dry it for 10 - 12 hours to obtain the auxiliary agent.

7. The phenolic resin adhesive solution for copper clad laminate according to claim 6, characterized in that: In the preparation steps of the toughening agent, the ratio of zinc nitrate, 3 - bromo - 2,6 - dimethylbenzoic acid, N,N - dimethylacetamide, and benzoic acid is 1 mmol:0.5 mmol:120 mL:0.6 g. The stirring speed during stirring is 200 revolutions per minute, the heating rate of the oven is 10 °C per hour, and the drying temperature is 75 °C.

8. The phenolic resin adhesive solution for copper clad laminate according to claim 1, wherein: The solvent is ethylene glycol monomethyl ether.

9. Use of a phenolic resin adhesive solution for a copper - clad laminate according to any one of claims 1 - 8 in the manufacture of a copper - clad laminate.

10. The application according to claim 9, characterized in that: It includes the following steps: S1. Weigh each component of the phenolic resin adhesive solution for a copper - clad laminate by weight. Mix the melamine - modified phenolic resin, tung oil - modified phenolic resin, curing agent, accelerator, and solvent, and stir at a stirring speed of 500 - 600 revolutions per minute for 1 - 2 hours. Then add other components and stir at a stirring speed of 800 - 1000 revolutions per minute for 2 - 3 hours to obtain the phenolic resin adhesive solution for a copper - clad laminate. S2. Immerse bleached wood pulp paper into the phenolic resin adhesive solution for a copper - clad laminate obtained in step S1, and bake it at 150 - 170 °C for 1 minute to obtain a prepreg. S3. Stack 6 prepregs obtained in step S2 together to obtain a laminated sheet. Cover each of the upper and lower surfaces of the laminated sheet with a copper foil, and place it in a hot press to hot - press at 150 - 160 °C and a pressure of 30 - 40 MPa for 80 - 120 minutes to obtain a copper - clad laminate.