Copper-clad plate glue solution, preparation method thereof and copper-clad plate

Abstract

The invention belongs to the technical field of copper-clad plates, and particularly relates to a copper-clad plate glue solution, a preparation method thereof and a copper-clad plate, the copper-clad plate glue solution comprises the following components by weight: 53-71 parts of BPA formaldehyde resin; 10 to 22 parts of PPO resin; 22 to 26 parts of TAIC resin; 14 to 28 parts of furan resin; 0.3 to 0.6 part of a curing agent; 0.21 to 0.46 part of a catalyst; 59 to 77 parts of filler; 30 to 70 parts of a solvent A; and 28-40 parts of a solvent B. The dielectric constant of the copper-clad plate prepared from the copper-clad plate glue solution is 1t; 3.0, a dielectric loss (10G) lt; 0.002, Tgt, 0.002, Tgt; the temperature is 210 DEG C, and T288gt; after 120 minutes, the flame retardance reaches FV-0 level, and the peel strength is gt; the dielectric constant is lower, the loss is low, the high frequency is compatible, and other indexes are not reduced.

Description

TECHNICAL FIELD

[0001] The present application belongs to the technical field of copper-clad plate, and particularly relates to a copper-clad plate glue solution, a preparation method thereof and a copper-clad plate. BACKGROUND

[0002] With the progress of science and technology, the development of high-frequency communication makes wireless communication develop towards high frequency, and the use frequency shifts from the MHz frequency band to the GHz frequency band, and information transmission enters the high-frequency field. The high-frequency and high-speed of electronic information products also have higher requirements for the high-frequency characteristics of copper-clad plates. The dielectric constant (Dk) is required to be small and stable, and generally the smaller the better, because the signal transmission rate is inversely proportional to the square root of the dielectric constant of the material, and high dielectric constant is easy to cause signal transmission delay; the dielectric loss (Df) must be small, because the dielectric loss mainly affects the quality of signal transmission, and the smaller the dielectric loss, the smaller the signal loss. The traditional copper-clad plate has been unable to meet the current market demand, and it is imperative to develop high-frequency and high-speed copper-clad plates. SUMMARY

[0003] In view of the above deficiencies of the prior art, the present application aims to provide a copper-clad plate glue solution, a preparation method thereof and a copper-clad plate

[0004] To achieve the above purpose, the technical scheme adopted is:

[0005] The first object of the present application is to provide a copper-clad plate glue solution, which comprises the following components in parts by weight:

[0006] BPA formaldehyde resin (bisphenol A formaldehyde resin): 53-71 parts; PPO resin (polyphenyl ether resin): 10-22 parts; TAIC resin (triallyl isocyanurate): 22-26 parts; furan resin: 14-28 parts; curing agent: 0.3-0.6 parts; catalyst: 0.21-0.46 parts; filler: 59-77 parts; solvent A: 30-70 parts; solvent B: 28-40 parts.

[0007] The present application has the following technical effects by adopting the above technical scheme:

[0008] The components of the present copper-clad plate glue solution take BPA formaldehyde resin as the main resin, and PPO resin, TAIC resin and furan resin are added to increase the resin ratio, increase the thermal stability and reduce the dielectric loss.

[0009] Further, the curing agent is DDS (4,4-diamino diphenyl sulfone), and the catalyst is dimethyl tetraethyl imidazole.

[0010] Further, the filler is one or more of aluminum hydroxide or silicon powder, the solvent A is xylene and / or toluene, and the solvent B is xylene and / or toluene.

[0011] The second object of the present application is to provide a preparation method of copper-clad plate glue solution, comprising the following steps:

[0012] S1: at room temperature, BPA formaldehyde resin, PPO resin, TAIC resin, furan resin, curing agent and solvent are added into a container for stirring to make them fully dissolved, obtaining a dissolved solution;

[0013] S2: at room temperature, a catalyst is added into the dissolved solution in S1 for stirring to make it fully dissolved, obtaining a mixed solution;

[0014] S3: a filler is added into the mixed solution in S2 and stirred uniformly to fully emulsify, obtaining an emulsion;

[0015] S4: a solvent is added into the emulsion in S3 to adjust the viscosity, and stirred uniformly to gel, obtaining a uniform and stable copper-clad plate glue solution.

[0016] Further, the gelation time of the glue solution in S4 is 250-270s.

[0017] Further, the A solvent in S1 is 16-40 parts of toluene solvent and 15-27 parts of xylene solvent; and the B solvent in S4 is 10-17 parts of xylene solvent and 10-17 parts of toluene solvent.

[0018] The third object of the present application is to provide a high-frequency and high-speed copper-clad plate prepared by the above copper-clad plate glue solution.

[0019] Further, the preparation method of the copper-clad plate comprises the following steps:

[0020] The above copper-clad plate glue solution is completely and uniformly infiltrated into the glass fiber cloth, which is baked in a 185℃ oven for 2-4min to obtain a prepreg;

[0021] A plurality of the above prepregs with smooth surface and uniform coating are stacked, and copper foils are attached to the top and bottom, which are placed in a vacuum hot press with a pressure of 5-17MPa and a temperature of 160-210℃, and hot-pressed for 3h and kept for 1h to obtain a high-frequency and high-speed copper-clad plate.

[0022] Further, the glue content of the prepreg is 60-75wt%.

[0023] Further, the glass fiber cloth is a Low DK glass fiber cloth.

[0024] Compared with the prior art, the present application has the following advantages:

[0025] (1) The present invention adopts BPA formaldehyde resin, PPO resin, TAIC resin, furan resin, curing agent DDS, catalyst combined with solvent and filler to provide another possibility for the preparation of high-frequency and high-speed copper clad laminates;

[0026] (2) The present invention uses BPA formaldehyde resin as the main resin, and adds PPO resin, TAIC resin, and furan resin to increase the resin ratio. PPO resin has good thermal stability, Tg ≥ 200°C, and low thermal expansion, meeting the requirements of mechanical and electrical properties of copper clad laminates. TAIC resin has good dimensional stability and good heat and water resistance, which is beneficial for improving the heat resistance and flame retardancy of the board. Furan resin increases thermosetting properties while reducing dielectric loss.

[0027] (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>210°C, a T288>120 minutes, a flame retardancy reaching FV-0 level, and a peel strength>1.0N / mm. DETAILED DESCRIPTION

[0028] 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.

[0029] Example 1

[0030] A method for preparing a high-frequency and high-speed copper-clad laminate comprises the following steps:

[0031] 1. Preparation of copper clad laminate glue:

[0032] S1: At room temperature, 54 parts by weight of BPA formaldehyde resin, 12 parts by weight of PPO resin, 23 parts by weight of TAIC resin, 17 parts by weight of furan resin, 0.35 parts by weight of DDS, 21 parts by weight of toluene solvent, and 17 parts by weight of xylene solvent were added to a container and stirred until fully dissolved to obtain a solution;

[0033] S2: At room temperature, add 0.23 parts by weight of dimethyltetraethylimidazole to the solution in S1 and stir until it is fully dissolved;

[0034] S3: Add 19 parts of aluminum hydroxide and 41 parts of silicon powder by weight to the mixed solution in S2 and stir evenly to fully emulsify to obtain an emulsion;

[0035] S4: 17 parts by weight of xylene solvent and 17 parts by weight of toluene solvent were added to the emulsion in S3 to adjust the viscosity, and the mixture was stirred evenly. The gelling time of the adhesive was 253 seconds, and a uniform and stable copper clad laminate adhesive was obtained.

[0036] 2. Preparation of prepreg:

[0037] The glue solution obtained in S4 is evenly distributed on Low DK glass fiber cloth, and is baked in a 185°C oven for 3 minutes to obtain a PP sheet; the PP sheet has a uniform appearance and a glue content of 62%.

[0038] 3. Preparation of copper-clad plate:

[0039] The PP sheet prepared in step 2 is stacked according to requirements, and 18-micron copper foil is covered on the upper and lower surfaces. The high-frequency high-speed copper-clad plate is obtained by hot pressing in a vacuum press at a pressure of 5-17 MPa and a temperature of 160-210°C for 3 hours and heat preservation for 1 hour.

[0040] Example 2:

[0041] A method for preparing a high-frequency high-speed copper-clad plate, comprising the following steps:

[0042] 1. Preparation of copper-clad plate glue solution:

[0043] S1: At room temperature, 60 parts of BPA formaldehyde resin, 18 parts of PPO resin, 23 parts of TAIC resin, 20 parts of furan resin, 0.5 parts of DDS, and 16 parts of toluene solvent, 15 parts of dimethylbenzene solvent are added to a container and stirred to dissolve completely, to obtain a dissolved solution;

[0044] S2: At room temperature, 0.35 parts of dimethyltetraethyl imidazole is added to the dissolved solution in S1 and stirred to dissolve completely;

[0045] S3: 23 parts of aluminum hydroxide and 47 parts of silicon powder are added to the mixed solution in S2 and stirred uniformly to emulsify completely, to obtain an emulsion;

[0046] S4: 20 parts of dimethylbenzene solvent and 20 parts of toluene solvent are added to the emulsion in S3 to adjust the viscosity, and stirred uniformly, the glue solution has a gelation time of 263 seconds, and a uniform and stable copper-clad plate glue solution is obtained.

[0047] 2. Preparation of prepreg:

[0048] The glue solution obtained in S4 is evenly distributed on Low DK glass fiber cloth, and is baked in a 185°C oven for 2 minutes to obtain a PP sheet; the PP sheet has a uniform appearance and a glue content of 66%.

[0049] 3. Preparation of copper-clad plate:

[0050] The PP sheet prepared in step 2 is stacked according to requirements, and 18-micron copper foil is covered on the upper and lower surfaces. The high-frequency high-speed copper-clad plate is obtained by hot pressing in a vacuum press at a pressure of 5-17 MPa and a temperature of 160-210°C for 3 hours and heat preservation for 1 hour.

[0051] Example 3

[0052] A preparation method of a high-frequency high-speed copper-clad plate, comprising the following steps:

[0053] 1. Preparation of a copper-clad plate glue solution:

[0054] S1: At room temperature, 70 parts of BPA formaldehyde resin, 20 parts of PPO resin, 26 parts of TAIC resin, 26 parts of furan resin, 0.53 parts of DDS, and 30 parts of toluene solvent, 22 parts of dimethylbenzene solvent were added to a container and stirred to make them fully dissolved, obtaining a dissolved solution;

[0055] S2: At room temperature, 0.45 parts of dimethyltetraethyl imidazole was added to the dissolved solution in S1 and stirred to make it fully dissolved;

[0056] S3: 19 parts of aluminum hydroxide and 40 parts of silicon powder were added to the mixed solution in S2 and stirred uniformly to make it fully emulsified, obtaining an emulsion;

[0057] S4: 15 parts of dimethylbenzene solvent and 15 parts of toluene solvent were added to the emulsion in S3 to adjust the viscosity, and stirred uniformly, the glue solution gelation time was 267s, obtaining a uniform and stable copper-clad plate glue solution.

[0058] 2. Preparation of a prepreg:

[0059] The glue solution obtained in S4 was uniformly distributed on a Low DK glass fiber cloth, and was baked in a 185℃ oven for 3.5min to obtain a PP sheet; the PP sheet had a uniform appearance and a glue content of 74%.

[0060] 3. Preparation of a copper-clad plate:

[0061] The PP sheet prepared in step 2 was stacked according to requirements, and 18 microns of copper foil was covered on the upper and lower surfaces, and was hot-pressed in a vacuum press with a pressure of 5-17MPa and a temperature of 160-210℃ for 3h and 1h of holding, obtaining a high-frequency high-speed copper-clad plate.

[0062] Comparative Example 1:

[0063] A preparation method of a copper-clad plate, comprising the following steps:

[0064] 1. Preparation of a copper-clad plate glue solution:

[0065] At room temperature, 54 parts of o-cresol formaldehyde epoxy resin, 12 parts of PPO resin, 17 parts of polytetrafluoroethylene resin, 23 parts of TAIC resin, 0.35 parts of DDS curing agent, 17 parts of xylene solvent, 21 parts of toluene solvent, 0.23 parts of dimethyl tetraethyl imidazole and 60 parts of aluminum hydroxide filler are added to the container for stirring to make them fully dissolved to obtain a dissolved solution;

[0066] 2. Preparation of prepreg:

[0067] The above obtained glue solution is fully and uniformly infiltrated into ordinary glass fiber cloth, which is baked in a 185°C oven for 3 minutes to obtain a PP sheet with a glue content of 62%.

[0068] 3. Preparation of copper-clad plate:

[0069] The PP sheet prepared in step 2 is stacked according to requirements, and 18 microns of copper foil is covered on the upper and lower surfaces. In a vacuum press with a pressure of 5-17 MPa and a temperature of 160-210°C, hot pressing is performed for 3 hours and heat preservation is performed for 1 hour to obtain a high-frequency high-speed copper-clad plate.

[0070] Comparative Example 2:

[0071] A method for preparing a copper-clad plate, comprising the following steps:

[0072] 1. Preparation of copper-clad plate glue solution:

[0073] S1: At room temperature, 54 parts of bisphenol A type epoxy resin, 12 parts of PPO resin, 23 parts of TAIC resin, 17 parts of furan resin, 0.35 parts of DDS and 21 parts of toluene solvent, 17 parts of xylene solvent are added to the container for stirring to make them fully dissolved to obtain a dissolved solution;

[0074] S2: At room temperature, 0.23 parts of dimethyl tetraethyl imidazole is added to the dissolved solution in S1 for stirring to make it fully dissolved;

[0075] S3: 19 parts of aluminum hydroxide and 41 parts of silicon powder are added to the mixed solution in S2 and stirred uniformly to make it fully emulsified to obtain an emulsion;

[0076] S4: 17 parts of xylene solvent and 17 parts of toluene solvent are added to the emulsion in S3 to adjust the viscosity, and the glue solution is stirred uniformly. The glue setting time is 253 seconds, and a uniform and stable copper-clad plate glue solution is obtained.

[0077] 2. Preparation of prepreg:

[0078] The glue solution obtained in S4 is uniformly distributed on Low DK glass fiber cloth, which is baked in a 185°C oven for 3 minutes to obtain a PP sheet; the PP sheet has a uniform appearance and a glue content of 62%.

[0079] 3. Preparation of copper-clad plate:

[0080] The PP sheet prepared in step 2 is stacked according to requirements, 9 sheets are stacked, and 18 microns of copper foil is covered on the upper and lower surfaces. The copper-clad plate is obtained by hot pressing for 3 hours and heat preservation for 1 hour in a vacuum press with a pressure of 5-17 MPa and a temperature of 160-210 DEG C.

[0081] Test method description:

[0082] (1) Dielectric constant: GB / T 4722-2017-8.5;

[0083] (2) Dielectric loss (10G): GB / T 4722-2017-8.5;

[0084] (3) Tg (DSC): GB / T 4722-2017-6.7.1;

[0085] (4) T288: GB / T 4722-2017-6.11;

[0086] (5) Peel strength (N / mm): GB / T 4722-2017-7.2.1;

[0087] (6) Flame retardancy: GB / T 4722-2017-6.4.1;

[0088] The test data of each embodiment and the comparative example are shown in Table 1.

[0089] Table 1 Test data of each embodiment and the comparative example

[0090]

[0091] As can be seen from the test data in Table 1, the dielectric constant of the copper-clad plate of the embodiment is less than 3.0, the dielectric loss (10G) is less than 0.002, the Tg is greater than 210 DEG C, the T288 is greater than 120 minutes, the flame retardancy reaches FV-0 level, and the peel strength is greater than 1.0 N / mm.

[0092] Compared with the comparative examples 1-2, the dielectric constant, dielectric loss, Tg and other indicators of the embodiments 1-3 are obviously improved, and the other basic indicators of the embodiments 1-3 are also better than those of the comparative examples 1-2. Therefore, the copper-clad plate prepared by the copper-clad plate glue solution adopted by the present application has lower dielectric constant, low loss, compatible high frequency, and other indicators are not reduced compared with the existing copper-clad plate.

[0093] The above merely describes preferred embodiments of the present application and is not used to limit the present application, and any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present application shall be included in the protection scope of the present application.

Claims

1. A copper clad laminate adhesive, characterized in that: Calculated by weight, it includes the following components: BPA formaldehyde resin: 53-71 parts; PPO resin: 10-22 parts; TAIC resin: 22-26 parts; furan resin: 14-28 parts; curing agent: 0.3-0.6 parts; catalyst: 0.21-0.46 parts; filler: 59-77 parts; solvent A: 30-70 parts; solvent B: 28-40 parts.

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

3. The copper clad laminate adhesive according to claim 1, characterized in that The filler is one or more of aluminum hydroxide and silicon micropowder, the solvent A is xylene and / or toluene, and the solvent B is xylene and / or toluene.

4. A method for preparing the copper clad laminate adhesive according to any one of claims 1 to 3, characterized in that: The steps include: S1: At room temperature, add BPA formaldehyde resin, PPO resin, TAIC resin, furan resin, curing agent and solvent A into a container and stir to fully dissolve them to obtain a solution; S2: At room temperature, add the catalyst to the solution in S1 and stir to fully dissolve it to obtain a mixed solution; S3: adding the filler to the mixed solution in S2 and stirring evenly to fully emulsify to obtain an emulsion; S4: adding solvent B to the emulsion in S3 to adjust the viscosity, stirring evenly, and gelling to obtain a uniform and stable copper clad laminate glue.

5. The method for preparing the copper clad laminate adhesive according to claim 4, wherein: The gelling time of the glue in S4 is 250 to 270 seconds.

6. The method for preparing the copper clad laminate adhesive according to claim 4, wherein: The solvent A in the S1 is 16 to 40 parts of toluene solvent and 15 to 27 parts of xylene solvent; the solvent B in the S4 is 15 to 20 parts of xylene solvent and 15 to 20 parts of toluene solvent.

7. A copper clad laminate, characterized in that: The copper clad laminate is prepared using the adhesive solution described in any one of claims 1 to 3.

8. The copper clad laminate according to claim 7, characterized in that: The method for preparing the copper clad laminate comprises the following steps: The copper clad laminate adhesive is completely and evenly impregnated into the glass fiber cloth, and then baked in an oven at 185° C. for 2 to 4 minutes to obtain a prepreg; Take several sheets of the prepreg with smooth surface and uniform coating, stack them, attach copper foil on the top and bottom, place them in a vacuum hot press with a pressure of 5-17 MPa and a temperature of 160-210°C, hot press for 3 hours and keep warm for 1 hour to produce a high-frequency and high-speed copper clad laminate.

9. The copper clad laminate according to claim 8, characterized in that: The prepreg has a glue content of 60-75 wt%.

10. The copper clad laminate according to claim 8, characterized in that: The glass fiber cloth is Low DK glass fiber cloth.

Images