Copper-clad plate glue solution, high-frequency high-speed copper-clad plate and preparation method of copper-clad plate glue solution

Abstract

The invention belongs to the technical field of copper-clad plates, and particularly relates to a copper-clad plate glue solution, a high-frequency high-speed copper-clad plate and a preparation method thereof. According to the invention, furan resin is used as matrix resin, o-cresol formaldehyde epoxy, styrene-butadiene resin and butadiene-acrylonitrile copolymer are added to improve the resin proportion, increase thermoset and reduce dielectric loss. Adding toluene, a xylene solvent, a triethanolamine curing agent, imidazole, aluminum hydroxide, aluminum oxide and silica powder, and completely dissolving and emulsifying to obtain a glue solution; completely infiltrating Low DK glass fiber cloth with the obtained glue solution, and carrying out certain process treatment to form PP; the copper foil is covered with PP, and the dielectric constant of the laminated copper-clad plate is 1t through a certain laminating process; 3.0, a dielectric loss (10G) lt; 0.002, Tgt, 0.002, Tgt; the temperature is 200 DEG C, and T288gt; after 120 minutes, the flame retardance reaches FV-0 level, and the peel strength is gt; and 0.7 N / mm.

Description

Technical Field

[0001] The invention belongs to the technical field of copper clad laminates, and in particular relates to a copper clad laminate adhesive, a high-frequency and high-speed copper clad laminate and a preparation method thereof. Background Art

[0002] With technological advancements, high-frequency communications have significantly developed, driving wireless communications towards higher frequencies, shifting from the MHz to the GHz band, and ushering in information transmission into the high-frequency realm. The high-frequency and high-speed nature of electronic information products places higher demands on the high-frequency characteristics of copper-clad laminates. The dielectric constant (dk) must be small and stable, and generally, the lower the better. The signal transmission rate is inversely proportional to the square root of the material's dielectric constant, and a high dielectric constant can easily cause signal transmission delays. Dielectric loss (df) must be low, as it primarily affects signal transmission quality. Lower dielectric loss results in lower signal loss.

[0003] The high frequency and high speed of electronic products have placed higher demands on the high frequency characteristics of printed circuit boards, and high-frequency copper clad laminates are more in demand in the market. Traditional copper clad laminates can no longer meet the current market demand, and the development of high-frequency and high-speed copper clad laminates is imperative. Summary of the Invention

[0004] In response to the deficiencies in the above-mentioned prior art, the present invention provides a copper clad laminate adhesive, a high-frequency and high-speed copper clad laminate and a preparation method thereof. The adhesive adopts component materials different from those of the existing high-frequency and high-speed copper clad laminates, uses furan resin as the main resin, and adds o-cresol epoxy, styrene-butadiene resin, and butadiene-acrylonitrile copolymer to increase the resin ratio, thereby increasing thermosetting properties and reducing dielectric loss.

[0005] One of the purposes of the present invention is to provide a copper clad laminate adhesive, comprising a resin, a curing agent, a catalyst, a filler and a solvent, wherein the resin is mainly furan resin and also comprises o-cresol epoxy, styrene-butadiene resin and butadiene-acrylonitrile copolymer.

[0006] The beneficial effect of adopting the above scheme is that the present invention is different from the components of the high-frequency and high-speed copper clad laminates already available on the market in terms of the components of the copper clad laminate glue. Furan resin is used as the main resin, and o-cresol epoxy, styrene-butadiene resin, and butadiene-acrylonitrile copolymer are added to increase the resin ratio, thereby increasing thermosetting properties and reducing dielectric loss.

[0007] Furthermore, the curing agent is triethanolamine curing agent, and the catalyst is imidazole.

[0008] Furthermore, the filler includes aluminum hydroxide, aluminum oxide and silicon powder, and the solvent includes xylene and toluene.

[0009] Furthermore, in terms of weight, the glue components include 47 to 65 parts of furan resin, 8 to 14 parts of o-cresol epoxy, 21 to 26 parts of styrene-butadiene resin, 10 to 29 parts of butadiene-acrylonitrile copolymer, 0.3 to 0.6 parts of triethanolamine curing agent, 0.11 to 0.2 parts of imidazole, 18 to 22 parts of aluminum hydroxide, 18 to 22 parts of aluminum oxide, 8 to 12 parts of silicon micropowder, 33 to 50 parts of toluene, and 33 to 50 parts of xylene.

[0010] A second object of the present invention is to provide a high-frequency and high-speed copper clad laminate, comprising the high-frequency and high-speed copper clad laminate glue.

[0011] A third object of the present invention is to provide a method for preparing a high-frequency and high-speed copper-clad laminate, using the high-frequency and high-speed copper-clad laminate adhesive, comprising the following steps:

[0012] (1) By weight, 47 to 65 parts of furan resin, 8 to 14 parts of o-cresol epoxy, 21 to 26 parts of styrene-butadiene resin, 10 to 29 parts of butadiene-acrylonitrile copolymer, 0.3 to 0.6 parts of triethanolamine curing agent, 24 to 37 parts of toluene solvent, and 24 to 37 parts of xylene solvent are added to a container and stirred to fully dissolve;

[0013] (2) adding 0.11 to 0.2 parts by weight of imidazole to the mixed solution of step (1) and stirring to fully dissolve it;

[0014] (3) adding 18 to 22 parts of aluminum hydroxide, 18 to 22 parts of aluminum oxide, and 8 to 12 parts of silicon powder to the mixed solution obtained in step (2) and stirring the mixture to fully emulsify;

[0015] (4) adding 9 to 13 parts by weight of xylene solvent and 9 to 13 parts by weight of toluene solvent to the mixed solution obtained in step (3) to adjust the viscosity and stir uniformly to obtain a glue solution;

[0016] (5) The adhesive obtained in step (4) is completely and evenly impregnated into the low DK glass fiber cloth to obtain PP;

[0017] (6) Pressing the PP-coated copper foil obtained in step (5) to obtain a high-frequency and high-speed copper-clad laminate.

[0018] Furthermore, in step (4), the gelling time of the glue solution is 110 to 145 seconds, and the glue solution is uniform and stable.

[0019] Furthermore, the step (5) includes the following specific steps: completely and evenly soaking the glue obtained in step (4) into the LowDK glass fiber cloth, and baking it in an oven at 165° C. for 3 to 5 minutes to obtain PP.

[0020] Furthermore, the PP has a uniform appearance and a rubber content of 65-77%.

[0021] Furthermore, the step (6) includes the following specific steps: stacking the PP obtained in step (5), covering both sides with copper foil, hot pressing for 3 hours and keeping warm for 1 hour in a vacuum press, with a pressure of 5 to 17 MPa and a temperature of 160 to 210° C., to obtain the high-frequency and high-speed copper clad laminate.

[0022] Compared with the prior art, the present invention has the following beneficial effects:

[0023] (1) The present invention uses furan resin as the main resin, and adds o-cresol epoxy, styrene-butadiene resin, and butadiene-acrylonitrile copolymer to increase the resin ratio, thereby increasing thermosetting properties and reducing dielectric loss.

[0024] (2) The present invention differs from the existing high-frequency and high-speed copper clad laminates on the market in terms of the composition of the copper clad laminate glue. The present invention adopts a new type of resin, a new type of curing agent, a catalyst, a solvent, and a filler for mixing, which provides another possibility for the preparation of high-frequency and high-speed copper clad laminates.

[0025] (3) The copper clad laminate provided by the present invention has a dielectric constant of <3.0, a dielectric loss (10G) <0.002, a Tg>200°C, a T288>120 minutes, a flame retardancy reaching FV-0 level, and a peel strength>0.7N / mm. DETAILED DESCRIPTION

[0026] The present invention is described below with reference to examples, which are only used to explain the present invention and are not used to limit the scope of the present invention.

[0027] Example 1

[0028] A method for preparing a high-frequency and high-speed copper-clad laminate comprises the following steps:

[0029] (1) At room temperature, 47 parts of furan resin, 10 parts of o-cresol epoxy, 21 parts of styrene-butadiene resin, 17 parts of butadiene-acrylonitrile copolymer, 0.5 parts of triethanolamine curing agent, 29 parts of toluene solvent, and 29 parts of xylene solvent were added to a container and stirred to fully dissolve;

[0030] (2) At room temperature, 0.11 parts by weight of imidazole was added to the mixed solution of step (1) and stirred to fully dissolve it;

[0031] (3) Add 19 parts of aluminum hydroxide, 19 parts of aluminum oxide, and 8 parts of silicon powder to the mixed solution of step (2) and stir evenly to fully emulsify;

[0032] (4) Add 9 parts by weight of xylene solvent and 9 parts by weight of toluene solvent to the mixed solution of step (3) to adjust the viscosity and stir evenly to obtain a glue solution; the glue solution gelation time is 128 seconds, and the glue solution is uniform and stable;

[0033] (5) The glue obtained in step (4) was evenly distributed on the low DK glass fiber cloth, and baked in an oven at 165° C. for 4 minutes to obtain PP; the PP had a uniform appearance and a glue content of 67%.

[0034] (6) Stack 5 sheets of PP prepared in step (5) as required, cover both sides with 18-micron copper foil, and hot-press for 3 hours at a pressure of 5-17 MPa and a temperature of 160-210° C. in a vacuum press, and keep warm for 1 hour to obtain a high-frequency and high-speed copper-clad laminate.

[0035] Example 2

[0036] A method for preparing a high-frequency and high-speed copper-clad laminate comprises the following steps:

[0037] (1) At room temperature, 55 parts of furan resin, 13 parts of o-cresol epoxy, 24 parts of styrene-butadiene resin, 23 parts of butadiene-acrylonitrile copolymer, 0.5 parts of triethanolamine curing agent, 33 parts of toluene solvent, and 33 parts of xylene solvent were added to a container and stirred to fully dissolve;

[0038] (2) adding 0.15 parts by weight of imidazole to the mixed solution of step (1) at room temperature and stirring to fully dissolve it;

[0039] (3) Add 20 parts of aluminum hydroxide, 20 parts of aluminum oxide, and 10 parts of silicon powder to the mixed solution of step (2) and stir evenly to fully emulsify;

[0040] (4) Adding 11 parts by weight of xylene solvent and 11 parts by weight of toluene solvent to the mixed solution of step (3) to adjust the viscosity and stir evenly to obtain a glue solution; the gelling time of the glue solution is 117 seconds, and the glue solution is uniform and stable;

[0041] (5) The glue obtained in step (4) is evenly distributed on the low DK glass fiber cloth, and baked in an oven at 165° C. for 3 minutes to obtain PP; the PP has a uniform appearance and a glue content of 70%.

[0042] (6) Stack 5 sheets of PP prepared in step (5) as required, cover both sides with 18-micron copper foil, and hot-press for 3 hours at a pressure of 5-17 MPa and a temperature of 160-210° C. in a vacuum press, and keep warm for 1 hour to obtain a high-frequency and high-speed copper-clad laminate.

[0043] Example 3

[0044] A method for preparing a high-frequency and high-speed copper-clad laminate comprises the following steps:

[0045] (1) At room temperature, 63 parts of furan resin, 13 parts of o-cresol epoxy, 26 parts of styrene-butadiene resin, 28 parts of butadiene-acrylonitrile copolymer, 0.6 parts of triethanolamine curing agent, 35 parts of toluene solvent, and 35 parts of xylene solvent were added to a container and stirred to fully dissolve;

[0046] (2) At room temperature, 0.19 parts by weight of imidazole was added to the mixed solution of step (1) and stirred to fully dissolve it;

[0047] (3) Add 21 parts of aluminum hydroxide, 21 parts of aluminum oxide, and 11 parts of silicon powder to the mixed solution of step (2) and stir evenly to fully emulsify;

[0048] (4) Adding 12 parts by weight of xylene solvent and 12 parts by weight of toluene solvent to the mixed solution of step (3) to adjust the viscosity and stir evenly to obtain a glue solution; the gelling time of the glue solution is 134 seconds, and the glue solution is uniform and stable;

[0049] (5) The glue obtained in step (4) is evenly distributed on a low DK glass fiber cloth and baked in an oven at 165° C. for 5 minutes to obtain PP; the PP has a uniform appearance and a glue content of 73%.

[0050] (6) Stack 5 sheets of PP prepared in step (5) as required, cover both sides with 18-micron copper foil, and hot-press for 3 hours at a pressure of 5-17 MPa and a temperature of 160-210° C. in a vacuum press, and keep warm for 1 hour to obtain a high-frequency and high-speed copper-clad laminate.

[0051] Comparative Example 1

[0052] A method for preparing a copper clad laminate comprises the following steps:

[0053] (1) Weigh the following components of the adhesive solution by weight: 47 parts of furan resin, 21 parts of styrene-butadiene resin, 17 parts of butadiene-acrylonitrile copolymer, 0.5 parts of triethanolamine curing agent, 29 parts of toluene solvent, and 29 parts of xylene solvent, add them into a container and stir until they are fully dissolved; 0.11 parts of imidazole, 19 parts of aluminum hydroxide, 19 parts of aluminum oxide, and 8 parts of silicon micropowder are added to the mixture and stirred evenly to fully emulsify;

[0054] (2) The glue obtained in step (1) was completely and evenly impregnated into ordinary glass fiber cloth, and then baked in an oven at 165°C for 4 minutes to obtain a PP glue content of 67%;

[0055] (3) Stack 5 sheets of PP prepared in step (2) as required, cover both sides with 18-micron copper foil, and hot-press in a vacuum press at a pressure of 5-17 MPa and a temperature of 160-210° C. for 1.5 h, and keep warm for 1 h to obtain a copper-clad laminate.

[0056] Comparative Example 2

[0057] A method for preparing a copper clad laminate comprises the following steps:

[0058] (1) At room temperature, 47 parts by weight of bisphenol A epoxy resin, 10 parts by weight of o-cresol epoxy, 21 parts by weight of styrene-butadiene resin, 17 parts by weight of butadiene-acrylonitrile copolymer, 0.5 parts by weight of triethanolamine curing agent, 29 parts by weight of toluene solvent, and 29 parts by weight of xylene solvent were added to a container and stirred to fully dissolve;

[0059] (2) At room temperature, 0.11 parts by weight of imidazole was added to the mixed solution of step (1) and stirred to fully dissolve it;

[0060] (3) Add 19 parts of aluminum hydroxide, 19 parts of aluminum oxide, and 8 parts of silicon powder to the mixed solution of step (2) and stir evenly to fully emulsify;

[0061] (4) Add 9 parts by weight of xylene solvent and 9 parts by weight of toluene solvent to the mixed solution of step (3) to adjust the viscosity and stir evenly to obtain a glue solution; the glue solution gelation time is 128 seconds, and the glue solution is uniform and stable;

[0062] (5) The glue obtained in step (4) was evenly distributed on the low DK glass fiber cloth, and baked in an oven at 165° C. for 4 minutes to obtain PP; the PP had a uniform appearance and a glue content of 67%.

[0063] (6) Stack 5 sheets of PP prepared in step (5) as required, cover both sides with 18-micron copper foil, and hot-press for 3 hours at a pressure of 5-17 MPa and a temperature of 160-210° C. in a vacuum press, and keep warm for 1 hour to obtain a high-frequency and high-speed copper-clad laminate.

[0064] Test method description:

[0065] (1) Dielectric constant: GB / T 4722-2017-8.5;

[0066] (2) Dielectric loss (10G): GB / T 4722-2017-8.5;

[0067] (3)Tg(DSC): GB / T 4722-2017-6.7.1;

[0068] (4)T288: GB / T 4722-2017-6.11;

[0069] (5) Peel strength (N / mm): GB / T 4722-2017-7.2.1;

[0070] (6) Flame retardancy: GB / T 4722-2017-6.4.1;

[0071] The test data of each embodiment and comparative example are shown in Table 1.

[0072] Table 1. Test data of various embodiments and comparative examples

[0073] Test items Example 1 Example 2 Example 3 Comparative Example 1 Comparative Example 2 Dielectric constant 2.82 2.85 2.88 4.27 3.98 Dielectric loss (10G) 0.0012 0.0017 0.0012 0.0064 0.0040 Tg(DSC) / ℃ 210 209 215 163 178 T288 / min >120 >120 >120 57 80 Peel strength N / mm 0.71 0.71 0.73 0.46 0.53 flame retardancy FV-0 FV-0 FV-0 FV-0 FV-0

[0074] By comparing the test experimental data in Table 1, it can be seen that the dielectric constant of the copper clad laminate of the embodiment is <3.0, the dielectric loss (10G) is <0.002, Tg>200°C, T288>120 minutes, the flame retardancy reaches FV-0 level, and the peel strength is >0.7N / mm.

[0075] Compared with Comparative Examples 1-2, Examples 1-3 have significantly improved dielectric constants, dielectric loss, Tg, and other indicators. Other basic indicators of Examples 1-3 are also better than those of Comparative Examples 1-2. Therefore, the present invention provides a new high-frequency and high-speed copper-clad laminate and a preparation method thereof. Compared with existing copper-clad laminates, the new copper-clad laminate has a lower dielectric constant, low loss, and high-frequency compatibility, while maintaining other indicators.

[0076] The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention. Any modifications, equivalent substitutions, improvements, etc. made within the spirit and principles of the present invention should be included in the scope of protection of the present invention.

Claims

1. A copper clad laminate adhesive, characterized in that: The invention comprises resin, curing agent, catalyst, filler and solvent. The resin takes furan resin as main resin and also comprises o-cresol epoxy, styrene-butadiene resin and butadiene-acrylonitrile copolymer.

2. The copper clad laminate adhesive according to claim 1, characterized in that The curing agent is triethanolamine curing agent, and the catalyst is imidazole.

3. The copper clad laminate adhesive according to claim 1, characterized in that The filler includes aluminum hydroxide, aluminum oxide and silicon powder, and the solvent includes xylene and toluene.

4. The copper clad laminate adhesive according to claim 1, characterized in that In terms of weight, the glue components include 47 to 65 parts of furan resin, 8 to 14 parts of o-cresol epoxy, 21 to 26 parts of styrene-butadiene resin, 10 to 29 parts of butadiene-acrylonitrile copolymer, 0.3 to 0.6 parts of triethanolamine curing agent, 0.11 to 0.2 parts of imidazole, 18 to 22 parts of aluminum hydroxide, 18 to 22 parts of aluminum oxide, 8 to 12 parts of silicon micropowder, 33 to 50 parts of toluene, and 33 to 50 parts of xylene.

5. A high-frequency and high-speed copper-clad laminate, characterized in that: The invention comprises the high-frequency and high-speed copper clad laminate adhesive according to any one of claims 1 to 4.

6. A method for preparing a high-frequency and high-speed copper-clad laminate, characterized in that: Using the high-frequency and high-speed copper clad laminate adhesive according to any one of claims 1 to 4 comprises the following steps: (1) By weight, 47 to 65 parts of furan resin, 8 to 14 parts of o-cresol epoxy, 21 to 26 parts of styrene-butadiene resin, 10 to 29 parts of butadiene-acrylonitrile copolymer, 0.3 to 0.6 parts of triethanolamine curing agent, 24 to 37 parts of toluene solvent, and 24 to 37 parts of xylene solvent are added to a container and stirred to fully dissolve; (2) adding 0.11 to 0.2 parts by weight of imidazole to the mixed solution of step (1) and stirring to fully dissolve it; (3) adding 18 to 22 parts of aluminum hydroxide, 18 to 22 parts of aluminum oxide, and 8 to 12 parts of silicon powder to the mixed solution obtained in step (2) and stirring the mixture to fully emulsify; (4) adding 9 to 13 parts by weight of xylene solvent and 9 to 13 parts by weight of toluene solvent to the mixed solution obtained in step (3) to adjust the viscosity and stir uniformly to obtain a glue solution; (5) The adhesive obtained in step (4) is completely and evenly impregnated into the low DK glass fiber cloth to obtain PP; (6) Pressing the PP-coated copper foil obtained in step (5) to obtain a high-frequency and high-speed copper-clad laminate.

7. The preparation method according to claim 6, characterized in that In step (4), the gelling time of the glue solution is 110 to 145 seconds, and the glue solution is uniform and stable.

8. The preparation method according to claim 6, characterized in that The step (5) comprises the following specific steps: completely and evenly soaking the Low DK glass fiber cloth with the glue obtained in the step (4), and baking it in an oven at 165° C. for 3 to 5 minutes to obtain PP.

9. The preparation method according to claim 6, characterized in that The PP has a uniform appearance and a rubber content of 65-77%.

10. The preparation method according to claim 6, characterized in that The step (6) comprises the following specific steps: stacking the PP obtained in step (5), covering both sides with copper foil, hot pressing for 3 hours and keeping warm for 1 hour in a vacuum press, at a pressure of 5 to 17 MPa and a temperature of 160 to 210° C., to obtain the high-frequency and high-speed copper-clad laminate.