RESIN COMPOSITION AND RESIN FILM, PREPREG, LAMINATED BOARD, COPPER-CLAD BOARD AND PRINTED CIRCUIT BOARD COMPRISING SAME

Abstract

A resin composition, and a resin film, a prepreg, a laminated board, a copper-clad board, and a printed circuit board which comprise same. The resin composition comprises a combination of thermosetting polyphenylene ether resin, vinyl organic silicon resin, and a fully hydrogenated elastomeric polymer; and based on 100 parts by weight of the sum of the addition amounts of the thermosetting polyphenylene ether resin, the vinyl organic silicon resin, and the fully hydrogenated elastomeric polymer, the addition amount of the fully hydrogenated elastomer polymer is 20-50 parts by weight. The copper-clad board prepared from the resin composition has the characteristics of low dielectric constant, low dielectric loss, excellent thermal-oxidative aging resistance, high glass transition temperature, high heat resistance, high peel strength, low water absorption rate, and the like, and can be applied to scenes such as automobile radars in worse use environments.

Claims

1. A resin composition, comprising: a thermosetting polyphenylene ether resin, a vinyl organic silicone resin and a fully hydrogenated elastomeric polymer; based on that a total addition amount of the thermosetting polyphenylene ether resin, the vinyl organic silicone resin and the fully hydrogenated elastomeric polymer is 100 parts by weight, an addition amount of the fully hydrogenated elastomeric polymer is 20-50 parts by weight.

2. The resin composition according to claim 1, wherein the thermosetting polyphenylene ether resin is a vinyl group-modified thermosetting polyphenylene ether resin.

3. The resin composition according to claim 1, wherein, based on that a total addition amount of the thermosetting polyphenylene ether resin and the vinyl organic silicone resin is 100 parts by weight, an addition amount of the vinyl organic silicone resin is 20-60 parts by weight.

4. The resin composition according to claim 1, wherein the fully hydrogenated elastomeric polymer comprises a fully hydrogenated block elastomeric polymery.

5. The resin composition according to claim 1, wherein the resin composition further comprises an initiator, and preferably a free radical initiator.

6. A resin film, which is prepared by coating the resin composition according to claim 1 on a release material, subjecting the same to drying and/or semi-curing process, and then removing the release material.

7. A prepreg, comprising a reinforcing material and the resin composition according to claim 1 which is adhered to the reinforcing material after impregnating and drying.

8. A laminate, comprising at least one prepreg according to claim 7.

9. (canceled)

10. A printed circuit board, comprising the laminate according to claim 8.

11. The resin composition according to claims 1, wherein the vinyl organic silicone resin comprises any one or a combination of at least two of a ring-structure vinyl organic silicone resin, a line-structure vinyl organic silicone resin or a 3D network-structure vinyl organic silicone resin.

12. The resin composition according to claims 2, wherein the vinyl group-modified thermosetting polyphenylene ether resin is a methacrylate-modified thermosetting polyphenylene ether resin; a number average molecular mass of the methacrylate-modified thermosetting polyphenylene ether resin is 500-10000 g/mol.

13. The resin composition according to claims 5, based on that a total addition amount of the thermosetting polyphenylene ether resin and the vinyl organic silicone resin is 100 parts by weight, an addition amount of the initiator is 1-3 parts by weight.

14. The resin composition according to any one of claims 1, wherein the fully hydrogenated elastomeric polymer comprises any one or a combination of at least two of a fully hydrogenated styrene-butadiene diblock copolymer, a fully hydrogenated styrene-butadiene-styrene triblock copolymer, a fully hydrogenated styrene-isoprene diblock copolymer or a fully hydrogenated styrene-isoprene-styrene triblock copolymer.

15. The resin composition according to any one of claims 1, wherein the fully hydrogenated elastomeric polymer is a maleic anhydride-modified fully hydrogenated elastomeric polymer, and the maleic anhydride-modified fully hydrogenated elastomeric polymer is selected from any one or a combination of at least two of a maleic anhydride-modified fully hydrogenated styrene-butadiene diblock copolymer, a maleic anhydride-modified fully hydrogenated styrene-butadiene-styrene triblock copolymer, a maleic anhydride-modified fully hydrogenated styrene-isoprene diblock copolymer or a maleic anhydride-modified fully hydrogenated styrene-isoprene-styrene triblock copolymer.

16. The resin composition according to any one of claims 15, wherein in the maleic anhydride-modified fully hydrogenated elastomeric polymer, a content of the maleic anhydride group is less than or equal to 5%.

17. The resin composition according to any one of claims 1, wherein the resin composition further comprises a flame retardant.

18. The resin composition according to any one of claims 17, based on that a total addition amount of the thermosetting polyphenylene ether resin, the vinyl organic silicone resin, the fully hydrogenated elastomeric polymer and the flame retardant is 100 parts by weight, an addition amount of the flame retardant is 10-30 parts by weight.

19. The resin composition according to any one of claims 1, wherein the resin composition further comprises a powder filler.

20. The resin composition according to any one of claims 19, based on that a total addition amount of the thermosetting polyphenylene ether resin, the vinyl organic silicone resin, the fully hydrogenated elastomeric polymer, the flame retardant and the powder filler is 100 parts by weight, an addition amount of the powder filler is 10-70 parts by weight.

Description

DETAILED DESCRIPTION

[0052] Technical solutions of the present application are further described below with reference to specific embodiments. Those skilled in the art should understand that the embodiments described herein are merely used for a better understanding of the present application and should not be construed as specific limitations on the present application.

[0053] Raw materials used for preparing high-speed electronic circuit base materials in the embodiments of the present application are shown in the following table:

TABLE-US-00001 Manufacturer Product Name or Grade Material Description Sabic SA9000 (with a number average molecular mass of 1900) Methyl methacrylate-modified thermosetting polyphenylene ether resin Wuhan University Silicone WD-V4 Ring-structure vinyl organic silicone resin Runhe Chemical RH-Vi306 Line-structure vinyl organic silicone resin Hangzhou Silicon-based Materials V08 3D network-structure vinyl organic silicone resin Kraton D1118 Unhydrogenated SBS resin Kraton G1726 Fully hydrogenated SBS resin Kraton KIC1-023 Maleic anhydride-modified fully hydrogenated SBS resin (containing 2.0% of maleic anhydride) Kraton KIC1-025 Maleic anhydride-modified fully hydrogenated SBS resin (containing 1.0% of maleic anhydride) Self-prepared SBS-A Maleic anhydride-modified fully hydrogenated SBS resin (containing 4.8% of maleic anhydride) Self-prepared SBS-B Maleic anhydride-modified fully hydrogenated SBS resin (containing 6.0% of maleic anhydride) AkzoNobel PERKADOX BC-FF Dicumyl peroxide AkzoNobel TRIGONOX B Di-tert-butyl peroxide Jiangsu Lianrui DQ 2028L Fused silica powder Albemarle America BT-93W Bromine-containing flame retardant Albemarle America XP-7866 Phosphorus-containing flame retardant Shanghai Honghe Low Dk1035 fiberglass cloth Fiberglass cloth

[0054] In the above table, the preparation of the maleic anhydride-modified fully hydrogenated SBS-A resin (containing 4.8% of maleic anhydride) includes that:

[0055] 5.04 g of maleic anhydride was added to 100 g of SBS block copolymer G1726 resin particles, and the resin was subjected to extrusion modification under 0.5 g of initiator BPO, so as to obtain the maleic anhydride-modified fully hydrogenated SBS-A resin, in which the content of maleic anhydride was 4.8%.

[0056] In the above table, the preparation of the maleic anhydride-modified fully hydrogenated SBS-B resin (containing 6.0% of maleic anhydride) includes that:

[0057] 6.38 g of maleic anhydride was added to 100 g of SBS block copolymer G1726 resin particles, and the resin was subjected to extrusion modification under 0.5 g of initiator BPO, so as to obtain the maleic anhydride-modified fully hydrogenated SBS-B resin, in which the content of maleic anhydride was 6.0%.

Examples 1-10

[0058] Resin compositions are prepared according to the components shown in Table 2, and copper clad laminate samples are prepared according to the following preparation method of the copper clad laminate: [0059] (1) Various components of the resin composition were mixed uniformly in toluene with a prescribed amount, and dispersed uniformly at room temperature, so as to obtain a resin liquid; and [0060] (2) The reinforcing material (Low Dk1035 fiberglass cloth) was impregnated by the resin liquid obtained in step (1), subjected to rollers for controlling the suitable mass per unit area, and dried in an oven to remove the toluene solvent, so as to obtain a 1035 prepreg. Two 1035 prepregs were stacked, provided with copper foils of HOZ thickness on the upper and lower sides, and subjected to vacuum lamination and curing for 120 min in a press at a curing pressure of 25 Kg/cm.sup.2 and a curing temperature of 200° C., so as to obtain the copper clad laminate.

Comparative Examples 1-8

[0061] Resin compositions are prepared according to the components shown in Table 3, and copper clad laminate samples are prepared according to the following preparation method of the copper clad laminate: [0062] (1) Various components of the resin composition were mixed uniformly in toluene with a prescribed amount, and dispersed uniformly at room temperature, so as to obtain a resin liquid; and [0063] (2) The reinforcing material (Low Dk1035 fiberglass cloth) was impregnated by the resin liquid obtained in step (1), subjected to rollers for controlling the suitable mass per unit area, and dried in an oven to remove the toluene solvent, so as to obtain a 1035 prepreg. Two 1035 prepregs were stacked, provided with copper foils of HOZ thickness on the upper and lower sides, and subjected to vacuum lamination and curing for 120 min in a press at a curing pressure of 25 Kg/cm.sup.2 and a curing temperature of 200° C., so as to obtain the copper clad laminate.

Performance Test

[0064] The following performance tests are carried out for the copper clad laminates obtained in the above examples and comparative examples: [0065] (1) Dielectric constant and dielectric loss test: the SPDR (split post dielectric resonator) method was used for the test, and the test condition was A state and the frequency was 10 GHz. [0066] (2) Glass transition temperature (Tg) test: the test was performed according to the DMA method specified in IPC-TM-650 2.4.24. [0067] (3) T300 (with copper): with reference to IPC-TM-650 2.4.24.1, the board with copper foil was used for the test at a temperature of 300° C. [0068] (4) Copper foil peel strength (PS) test: IPC-TM-650 2.4.8; copper foil peel resistance tester. [0069] (5) Water absorption rate test: the test was performed according to IPC-TM-650 2.6.2.1 method. [0070] (6) Aging resistance test: the board was baked in an oven at 125° C. for 30 days, and Dk / Df were measured before and after baking the board.

[0071] The results of the above performance test are shown in Tables 2 and 3.

TABLE-US-00002 Raw Materials and Performances Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 Example 7 Example 8 Example 9 SA9000 75 75 75 75 75 75 80 70 50 WD-V4 25 0 0 0 0 0 0 0 0 RH-Vi306 0 25 0 0 0 0 0 0 0 V08 0 0 25 25 25 25 20 30 50 D1118 0 0 0 0 0 0 0 0 0 G1726 40 0 0 0 0 0 0 0 0 KIC1-023 0 40 0 0 70 100 30 60 90 KIC1-025 0 0 40 0 0 0 0 0 0 SBS-A 0 0 0 40 0 0 0 0 0 SBS-B 0 0 0 0 0 0 0 0 0 PERKADOX BC-FF 0 0 0 0 0 0 0 0 0 TRIGONOX B 2.0 2.0 2.0 2.0 2.0 2.0 1.0 2.0 3.0 BT-93W 0 0 0 0 0 0 20 40 60 XP-7866 0 0 0 0 0 0 0 0 0 DQ 2028L 0 0 0 0 0 0 60 160 250 Dielectric constant (10 GHz) 2.5 2.4 2.5 2.6 2.4 2.3 2.8 3.0 3.5 Dielectric loss (10 GHz) 0.0020 0.0022 0.0021 0.0023 0.0019 0.0018 0.0021 0.0020 0.0022 Tg (°C) 200 180 205 203 199 191 201 203 198 T300 (min) > 60 min > 60 min > 60 min > 60 min > 60 min > 60 min > 60 min > 60 min > 60 min PS (N/mm) 0.8 0.8 0.8 0.8 0.8 0.8 0.9 1.0 1.0 Water absorption rate (%) 0.09 0.09 0.09 0.09 0.09 0.09 0.09 0.09 0.09 Thermal aging resistance 125° C./30 days increment of Dk 0.03 0.03 0.04 0.02 0.03 0.03 0.03 0.03 0.02 Thermal aging resistance 125° C./30 days increment of Df 0.0006 0.0005 0.0004 0.0003 0.0004 0.0003 0.0005 0.0004 0.0005

TABLE-US-00003 Raw Materials and Performances Example 10 Compara tive Example 1 Compara tive Example 2 Compara tive Example 3 Compara tive Example 4 Compara tive Example 5 Compara tive Example 6 Compara tive Example 7 Compara tive Example 8 SA9000 75 75 75 75 75 75 75 75 75 WD-V4 0 25 0 0 0 0 0 0 0 RH-Vi306 0 0 25 0 0 0 0 0 0 V08 25 0 0 25 25 25 25 25 25 D1118 0 0 0 0 40 0 0 0 0 G1726 0 0 0 0 0 10 20 122 150 KIC1-023 0 0 0 0 0 0 0 0 0 KIC1-025 0 0 0 0 0 0 0 0 0 SBS-A 0 0 0 0 0 0 0 0 0 SBS-B 40 0 0 0 0 0 0 0 0 PERKADOX BC-FF 0 0 0 0 0 0 0 0 0 TRIGONOX B 2.0 2.0 2.0 2.0 2.0 2.0 2.0 2.0 2.0 BT-93W 0 0 0 0 0 0 0 0 0 XP-7866 0 0 0 0 0 0 0 0 0 DQ 2028L 0 0 0 0 0 0 0 0 0 Dielectric constant (10 GHz) 2.9 2.9 2.8 3.0 2.5 2.8 2.9 2.2 2.1 Dielectric loss (10 GHz) 0.0024 0.0028 0.0029 0.0028 0.0020 0.0027 0.0028 0.0017 0.0016 Tg (°C) 208 207 183 210 201 189 180 150 143 T300 (min) > 60 min > 60 min > 60 min > 60 min > 60 min > 60 min > 60 min > 60 min > 60 min PS (N/mm) 0.8 0.8 0.8 0.8 0.8 0.8 0.8 0.8 0.8 Water absorption rate (%) 0.12 0.09 0.09 0.09 0.09 0.09 0.09 0.09 0.09 Thermal aging resistance 125° C./30 days increment of Dk 0.02 0.05 0.05 0.04 0.03 0.03 0.02 0.03 0.02 Thermal aging resistance 125° C./30 days increment of Df 0.0002 0.0015 0.0016 0.0015 0.003 0.0015 0.0014 0.0003 0.0002

[0072] It can be seen from Tables 2 and 3 that the copper clad laminates, prepared by the resin composition provided in the present application which includes the thermosetting polyphenylene ether resin, the vinyl organic silicone resin and the fully hydrogenated elastomeric polymer, have excellent thermal-oxidative aging stability of dielectric constant and dielectric loss in addition to low dielectric constant and low dielectric loss, and also have high glass transition temperature, high heat resistance, high peel strength, low water absorption rate and other comprehensive performances.

[0073] By comparing Comparative Examples 1-3 with Examples 1-3, it can be seen that, for the resin system that includes the modified polyphenylene ether and vinyl organic silicone resin but includes no fully hydrogenated elastomeric resin (Comparative Examples 1-3), the dielectric loss of the base material is relatively high and reaches up to 0.0028-0.0029, and the thermal-oxidative aging performance of dielectric loss for the base material is poor, in which the dielectric loss increases by 0.0015-0.0016 after 30 days of thermal-oxidative aging at 125° C., which cannot meet the market demand.

[0074] By comparing Comparative Example 4 with Example 3, it can be seen that, when the unhydrogenated elastomeric polymer (Comparative Example 4) is used, the thermal-oxidative aging performance of dielectric loss for the base material is poor, in which the dielectric loss of the base material increases by 0.003 after 30 days of thermal-oxidative aging at 125° C., which cannot meet the market demand.

[0075] By comparing Comparative Examples 5-6 with Examples 2, 5 and 6, it can be seen that, when the addition amount of the fully hydrogenated elastomeric polymer is less than 20 parts by weight (based on that a total addition amount of the thermosetting polyphenylene ether resin, the vinyl organic silicone resin and the fully hydrogenated elastomeric polymer is 100 parts by weight) in Comparative Examples 5-6, the dielectric loss of the base material is relatively high and reaches up to 0.0027-0.0028, and the thermal-oxidative aging performance of dielectric loss for the base material is poor, in which the dielectric loss increases by 0.0014-0.0015 after 30 days of thermal-oxidative aging at 125° C., which cannot meet the market demand.

[0076] By comparing Comparative Examples 7-8 with Examples 2, 5 and 6, it can be seen that, when the addition amount of the fully hydrogenated elastomeric polymer is more than 50 parts by weight (based on that a total addition amount of the thermosetting polyphenylene ether resin, the vinyl organic silicone resin and the fully hydrogenated elastomeric polymer is 100 parts by weight) in Comparative Examples 7-8, the glass transition temperature of the base material is relatively low and reaches as low as 143-150° C., causing hidden dangers to dimensional stability and heat resistant reliability, which cannot meet the market demand.

[0077] By comparing Example 10 with Example 4, it can be seen that, when the content of maleic anhydride is 6.0% in the maleic anhydride-modified fully hydrogenated elastomeric resin (Example 10), the dielectric loss of the base material is relatively high, and the Df value is 0.0024, which proves that the dielectric loss of the base material can be further reduced in the present application while the excellent thermal-oxidative aging performance is guaranteed by preferably selecting a content of maleic anhydride to be less than or equal to 5%, so as to improve the comprehensive performance of the board.

[0078] The applicant has stated that although the detailed method of the present application is described through the above embodiments, the present application is not limited to the above detailed method, which means that the implementation of the present application does not necessarily depend on the above detailed method. It should be apparent to those skilled in the art that any improvements made to the present application, equivalent substitutions of various raw materials of the product, the addition of adjuvant ingredients, the selection of specific manners, etc., all fall within the protection scope and the disclosure scope of the present application.