An FR4 copper clad laminate and its preparation method

Abstract

This invention relates to the field of copper clad laminate (CCL) technology, and particularly to an FR4 CCL adhesive, an FR4 CCL, and a method for preparing the same. The FR4 CCL adhesive provided by this invention comprises a resin, a curing agent, a catalyst, a filler, and a solvent; wherein the resin comprises arylacetylene resin. The CCL prepared using the FR4 CCL adhesive of this invention exhibits a dielectric constant <3.1, dielectric loss (10G) <0.003, Tg >210℃, T288 >120 minutes, flame retardancy reaching FV-0 level, peel strength >0.90 N / mm, and excellent overall performance.

Description

Technical Field

[0001] This invention relates to the field of copper clad laminate technology, and in particular to an FR4 copper clad laminate adhesive, an FR4 copper clad laminate, and a method for preparing the same. Background Technology

[0002] As electronic components evolve towards miniaturization, lightweight design, high performance, and multifunctionality, high-frequency and high-speed signal transmission becomes increasingly necessary. This necessitates electronic materials with low dielectric constants and dielectric losses, but existing materials cannot meet these requirements. Therefore, developing copper-clad laminates with low dielectric constants and low dielectric losses is of paramount importance. Summary of the Invention

[0003] In order to solve the above-mentioned technical problems in the prior art, the present invention provides an FR4 copper clad laminate adhesive, an FR4 copper clad laminate and a method for preparing the same.

[0004] The technical solution of the present invention to solve the above-mentioned technical problems is as follows:

[0005] A first aspect of the present invention is to provide an FR4 copper clad laminate adhesive, comprising a resin, a curing agent, a catalyst, a filler, and a solvent; wherein the resin comprises an arylacetylene resin.

[0006] The FR4 copper clad laminate adhesive provided by this invention uses aryl acetylene resin as the main resin and is used in combination with other components to reduce the dielectric constant and dielectric loss of the resulting copper clad laminate.

[0007] Based on the above technical solution, the present invention can also be improved in the following ways:

[0008] Furthermore, the resin also includes polyimide resin, furan resin, and dicyclopentadiene epoxy resin.

[0009] The beneficial effects of adopting the above-mentioned further technical solution are as follows: by adding polyimide resin, furan resin, and dicyclopentadiene epoxy resin to increase the resin ratio, the dielectric constant and dielectric loss of the copper clad laminate are further reduced, and the thermosetting properties are increased.

[0010] Furthermore, by weight, it comprises the following components: 35-45 parts of aryl acetylene resin, 13-25 parts of polyimide resin, 10-15 parts of furan resin, 15-27 parts of dicyclopentadiene epoxy resin, 0.2-0.5 parts of curing agent, 40-74 parts of solvent, 0.17-0.28 parts of catalyst, and 19-28 parts of filler.

[0011] The beneficial effect of adopting the above-mentioned further technical solution is that by adjusting and coordinating the proportions of each component, the dielectric constant and dielectric loss of the copper-clad laminate can be further reduced.

[0012] Furthermore, the curing agent is triethanolamine, the catalyst is imidazole, the filler includes alumina and silica powder, and the solvent includes sulfolane and toluene.

[0013] The beneficial effect of adopting the above-mentioned further technical solution is that by adding toluene, sulfolane solvent, triethanolamine curing agent, imidazole, alumina, and silica powder, the emulsified resin is completely dissolved to obtain the adhesive solution.

[0014] Furthermore, by weight, the FR4 copper clad laminate adhesive comprises 15-26 parts of toluene and 15-26 parts of sulfolane.

[0015] A second aspect of the present invention is to provide a method for preparing FR4 copper-clad laminate using the above-mentioned FR4 copper-clad laminate adhesive, comprising the following steps:

[0016] (1) Preparation of adhesive solution: Weigh each component according to the weight parts, dissolve, mix evenly, and emulsify to obtain adhesive solution;

[0017] (2) The adhesive obtained in step (1) is used to impregnate the glass fiber cloth and then dried to obtain a semi-cured sheet;

[0018] (3) Cover the copper foil with the semi-cured sheet obtained in step (2) and press it together to obtain the FR4 copper-clad laminate.

[0019] Furthermore, step (1) includes the following steps:

[0020] S1. Weigh out the aryl acetylene resin, polyimide resin, furan resin, dicyclopentadiene epoxy resin, curing agent and solvent from Part 1 according to the weight proportions, and mix and stir until completely dissolved.

[0021] S2. Weigh the catalyst according to the weight proportions and add it to the mixed solution of S1, and stir until completely dissolved;

[0022] S3. Weigh the filler according to the weight proportions and add it to the mixed solution of S2, stir and emulsify;

[0023] S4. Weigh out the second part of the solvent according to the weight ratio and add it to the mixed solution in S3. Stir well to obtain the adhesive solution.

[0024] Furthermore, the first portion of solvent comprises 30 to 52 parts by weight, and the second portion of solvent comprises 10 to 22 parts by weight.

[0025] Furthermore, based on parts by weight, the first portion of solvent comprises 15-26 parts of toluene solvent and 15-26 parts of sulfolane solvent, and the second portion of solvent comprises 5-11 parts of sulfolane solvent and 5-11 parts of toluene solvent.

[0026] The beneficial effect of adopting the above-mentioned further technical solution is that the solvent is added in two parts. The first part of the solvent is used to fully dissolve each component, and the second part of the solvent is used to adjust the viscosity of the mixture and make the mixture fully mixed, thereby obtaining a uniform and stable adhesive solution.

[0027] Furthermore, in step (1), the gelation time of the adhesive is 280~320 seconds; in step (2), the drying process is to dry in an oven at 180~190℃ for 3~5 minutes, and the adhesive content of the semi-cured sheet is 47~56%.

[0028] The beneficial effect of adopting the above-mentioned further technical solution is that the adhesive is evenly distributed on the glass fiber cloth and dried, resulting in a uniform appearance of the semi-cured sheet.

[0029] Further, in step (3), several semi-cured sheets are stacked in sequence, copper foil is covered on both sides, and then the pressure is controlled at 5~17 MPa and the temperature at 160~210℃ in a vacuum press for 2~4 hours and heat preservation for 1~3 hours to obtain FR4 copper clad laminate.

[0030] The beneficial effect of adopting the above-mentioned further technical solution is that: after the above-mentioned lamination process, a copper-clad laminate is produced, and the copper-clad laminate has excellent comprehensive performance.

[0031] Another aspect of the present invention is to provide an FR4 copper clad laminate, which is prepared by the above-described method for preparing FR4 copper clad laminate.

[0032] Compared with the prior art, the present invention has the following technical effects:

[0033] (1) In this invention, aryl acetylene resin is used as the main resin, and polyimide resin, furan resin and dicyclopentadiene epoxy resin are added to increase the resin ratio. While increasing the thermosetting properties, the dielectric constant and dielectric loss are reduced.

[0034] (2) The components of the resin liquid of the present invention are combined, and copper-clad laminate is prepared by using aryl acetylene resin, combined with curing agent, catalyst, solvent and filler in proportion, and the performance of the copper-clad laminate is improved.

[0035] (3) The copper clad laminate provided by the present invention has a dielectric constant of <3.1, dielectric loss (10G) <0.003, Tg>210℃, T288>120 minutes, flame retardancy reaches FV-0 level, peel strength>0.90N / mm, and excellent comprehensive performance. Detailed Implementation

[0036] The following specific embodiments illustrate the implementation of the present invention. Those skilled in the art can easily understand other advantages and effects of the present invention from the content disclosed in this specification. Although the description of the present invention is presented in conjunction with preferred embodiments, this does not mean that the features of the invention are limited to these embodiments. On the contrary, the purpose of describing the invention in conjunction with embodiments is to cover other options or modifications that may be derived based on the claims of the present invention. To provide a deep understanding of the invention, many specific details will be included in the following description. The invention may also be implemented without using these details. Furthermore, to avoid confusion or obscuring the focus of the invention, some specific details will be omitted in the description. It should be noted that, unless otherwise specified, the embodiments and features in the embodiments of the present invention can be combined with each other.

[0037] Example 1

[0038] The method for preparing low-dielectric-low-loss FR4 copper-clad laminate includes the following steps:

[0039] (1) At room temperature, by weight, add 35 parts of aryl acetylene resin, 13 parts of polyimide resin, 10 parts of furan resin, 15 parts of dicyclopentadiene epoxy resin, 0.2 parts of triethanolamine curing agent, 15 parts of toluene solvent, and 15 parts of sulfolane solvent into a container and stir until fully dissolved.

[0040] (2) At room temperature, add 0.17 parts by weight of imidazole to the mixture in step (1) and stir until it is fully dissolved;

[0041] (3) By weight, add 8 parts of alumina and 11 parts of silica powder to the mixture in step (2) and stir until fully emulsified;

[0042] (4) By weight, add 5 parts of sulfolane solvent and 5 parts of toluene solvent to the mixture in step (3) and stir evenly to obtain the adhesive solution; the gelation time of the adhesive solution is 320s, and the adhesive solution is uniform and stable.

[0043] (5) The adhesive solution obtained in step (4) is evenly distributed on Low DK fiberglass cloth (low dielectric fiberglass cloth) and baked in an oven at 185°C for 5 minutes to obtain a semi-cured sheet; the semi-cured sheet has a uniform appearance and an adhesive content of 47%;

[0044] (6) Stack 6 semi-cured sheets obtained in step (5) according to requirements, cover both sides with 18-micron copper foil, and hot press in a vacuum press with a pressure of 5 MPa and a temperature of 160℃ for 3 hours and heat preservation for 2 hours to obtain copper-clad laminate.

[0045] Example 2

[0046] The method for preparing low-dielectric-low-loss FR4 copper-clad laminate includes the following steps:

[0047] (1) At room temperature, by weight, 39 parts of aryl acetylene resin, 17 parts of polyimide resin, 13 parts of furan resin, 20 parts of dicyclopentadiene epoxy resin, 0.3 parts of triethanolamine curing agent, 17 parts of toluene solvent, and 17 parts of sulfolane solvent are added to a container and stirred until fully dissolved.

[0048] (2) At room temperature, add 0.22 parts by weight of imidazole to the mixture in step (1) and stir until it is fully dissolved;

[0049] (3) By weight, add 10 parts alumina and 14 parts silica powder to the mixture in step (2) and stir until fully emulsified;

[0050] (4) By weight, add 7 parts of sulfolane solvent and 7 parts of toluene solvent to the mixture in step (3) and stir evenly to obtain the adhesive solution; the gelation time of the adhesive solution is 293s, and the adhesive solution is uniform and stable.

[0051] (5) The adhesive solution obtained in step (4) is evenly distributed on Low DK fiberglass cloth and baked in an oven at 185°C for 3.5 minutes to obtain a semi-cured sheet; the semi-cured sheet has a uniform appearance and an adhesive content of 53%;

[0052] (6) Stack 6 semi-cured sheets obtained in step (5) according to requirements, cover both sides with 18-micron copper foil, and hot press in a vacuum press with a pressure of 12 MPa and a temperature of 180℃ for 3 hours and heat preservation for 2 hours to obtain copper-clad laminate.

[0053] Example 3

[0054] The method for preparing low-dielectric-low-loss FR4 copper-clad laminate includes the following steps:

[0055] (1) At room temperature, by weight, add 44 parts of aryl acetylene resin, 25 parts of polyimide resin, 15 parts of furan resin, 25 parts of dicyclopentadiene epoxy resin, 0.4 parts of triethanolamine curing agent, 25 parts of toluene solvent, and 25 parts of sulfolane solvent into a container and stir until fully dissolved.

[0056] (2) At room temperature, add 0.25 parts by weight of imidazole to the mixture in step (1) and stir until it is fully dissolved;

[0057] (3) By weight, add 12 parts alumina and 16 parts silica powder to the mixture in step (2) and stir evenly to fully emulsify;

[0058] (4) By weight, add 11 parts of sulfolane solvent and 11 parts of toluene solvent to the mixture in step (3) and stir evenly to obtain the adhesive solution; the gelation time of the adhesive solution is 280s, and the adhesive solution is uniform and stable.

[0059] (5) Distribute the adhesive obtained in step (4) evenly on Low DK fiberglass cloth and bake it in an oven at 185°C for 3 minutes to obtain a semi-cured sheet; the semi-cured sheet has a uniform appearance and an adhesive content of 55%.

[0060] (6) Stack 6 semi-cured sheets obtained in step (5) according to requirements, cover both sides with 18-micron copper foil, and hot press in a vacuum press with a pressure of 17 MPa and a temperature of 210℃ for 3 hours and heat preservation for 2 hours to obtain copper-clad laminate.

[0061] Comparative Example

[0062] A method for preparing a copper-clad laminate includes the following steps:

[0063] (1) Weigh the components of the adhesive solution according to the following weight parts: 53 parts polyimide resin, 30 parts bisphenol A type epoxy resin, 0.2 parts dicyandiamide curing agent, 45 parts toluene solvent, 0.03 parts imidazole and 45 parts alumina filler, mix them thoroughly and stir evenly to obtain the adhesive solution;

[0064] (2) The adhesive solution obtained in step (1) is completely and uniformly impregnated with ordinary fiberglass cloth, and baked in an oven at 200°C for 5 minutes to obtain a semi-cured sheet with an adhesive content of 54%;

[0065] (3) Stack 6 semi-cured sheets obtained in step (2) according to the requirements, cover both sides with 18-micron copper foil, and hot press them in a vacuum press at a pressure of 5 MPa and a temperature of 150°C for 1.5 hours to obtain copper-clad laminate.

[0066] Test method description:

[0067] (1) Dielectric constant: GB / T 4722-2017-8.5;

[0068] (2) Dielectric loss (10G): GB / T 4722-2017-8.5;

[0069] (3) Tg (DSC): GB / T 4722-2017-6.7.1;

[0070] (4) T288: GB / T 4722-2017-6.11;

[0071] (5) Peel strength (N / mm): GB / T 4722-2017-7.2.1;

[0072] (6) Flame retardancy: GB / T 4722-2017-6.4.1;

[0073] The test data for each embodiment and comparative example are shown in Table 1.

[0074] Table 1. Test data for each embodiment and comparative example.

[0075]

[0076] By comparing the test data in Table 1, it can be seen that the copper clad laminate of the embodiment has a dielectric constant of <3.0, dielectric loss (10G) of <0.003, Tg of >210℃, T288 of >120 minutes, flame retardancy of FV-0 level, and peel strength of >0.90N / mm.

[0077] Compared with Comparative Example 1, Examples 1-3 show significant improvements in dielectric constant, dielectric loss, and Tg, and other basic indicators are also superior to those of Comparative Example 1. Therefore, this invention provides a novel high-frequency, high-speed copper-clad laminate and its preparation method. Compared with existing copper-clad laminates, this novel copper-clad laminate has a lower dielectric constant, low loss, and high-frequency compatibility, while maintaining other indicators and exhibiting excellent overall performance.

[0078] 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 within the protection scope of the present invention.

Claims

1. An FR4 copper-clad laminate, characterized in that, The preparation method includes the following steps, based on parts by weight: (1) Preparation of adhesive solution: S1, weigh 35-45 parts of aryl acetylene resin, 13-25 parts of polyimide resin, 10-15 parts of furan resin, 15-27 parts of dicyclopentadiene epoxy resin, 0.2-0.5 parts of curing agent, and the first part of solvent, and mix and stir until completely dissolved; S2, weigh 0.17-0.28 parts of catalyst and add them to the mixed solution of S1, and stir until completely dissolved; S3, weigh 19-28 parts of filler and add them to the mixed solution of S2, stir and emulsify; S4, weigh the second part of solvent and add it to the mixed solution of S3, stir evenly, and the adhesive solution is obtained; (2) The adhesive obtained in step (1) is used to impregnate the glass fiber cloth and then dried to obtain a semi-cured sheet; (3) Cover the prepreg obtained in step (2) with copper foil and press it together to obtain the FR4 copper-clad laminate; The first part of the solvent has a weight of 30 to 52 parts, and the second part of the solvent has a weight of 10 to 22 parts.

2. The method for preparing FR4 copper-clad laminate according to claim 1, characterized in that, The gelation time of the adhesive is 280~320 seconds; in step (2), the drying process is to dry in an oven at 180~190℃ for 3~5 minutes, and the adhesive content of the semi-cured sheet is 47~56%.

3. The method for preparing FR4 copper-clad laminate according to claim 1, characterized in that, In step (3), several prepreg sheets are stacked in sequence, copper foil is covered on both sides, and then the pressure is controlled at 5~17 MPa and the temperature at 160~210℃ in a vacuum press for 2~4 hours and heat preservation for 1~3 hours to obtain FR4 copper clad laminate.

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