THERMOSETTING RESIN COMPOSITION AND APPLICATION THEREOF

Abstract

The present invention relates to a thermosetting resin composition and application thereof, said thermosetting resin composition comprising: A: a styrene-butadiene-styrene triblock copolymer having a star-shaped structure; B: a linear olefin resin containing 1,2-ethylene, and a modifier thereof, C: at least one resin or small molecule compound substituted with an acrylic group; taking the total mass of component A, component B, and component C as 100%, the added amount of said component A is 3%-85%, the added amount of said component B is 10%-95%, and the added amount of said component C is 1%-70%. The resin composition provided by the present invention does not undergo phase separation under initiator conditions, and has high heat resistance and a relatively low dielectric constant and dielectric loss tangent value, and is capable of providing the desired dielectric properties and thermal reliability of a copper-clad plate.

Claims

1-10. (canceled)

11. A thermosetting resin composition, comprising: A: a star-structured styrene-butadiene-styrene triblock copolymer; B: a linear 1,2-position vinyl-containing olefin resin and a modified substance thereof; C: a resin or a small-molecule compound substituted with at least one acrylic group; based on a total mass of component A, component B and component C being 100%, an addition amount of the component A is 3%-85%, an addition amount of the component B is 10%-95%, and an addition amount of the component C is 1%-70%.

12. The thermosetting resin composition according to claim 11, wherein the star-structured styrene-butadiene-styrene triblock copolymer has the following structure:
Y(X).sub.m the Y is C6-C10 aryl, C1-C6 chain alkyl or C3-C6 cycloalkyl; the X is a styrene-butadiene-styrene triblock copolymer chain; the m is an integer from 3 to 5.

13. The thermosetting resin composition according to claim 11, wherein the linear 1,2-position vinyl-containing olefin resin and the modified substance thereof comprise any one or a combination of at least two of polybutadiene, a butadiene-styrene copolymer, epoxidized polybutadiene, hydroxyl-modified polybutadiene, maleic anhydride-modified polybutadiene, a maleic anhydride-modified butadiene-styrene copolymer, or olefin-modified polyphenylene ether resin.

14. The thermosetting resin composition according to claim 11, wherein the acrylic group has the following structure: ##STR00009## the R.sub.1 is selected from a hydrogen atom or methyl; wherein the wavy line mark represents a linking bond.

15. The thermosetting resin composition according to claim 11, wherein the thermosetting resin composition further comprises component D: an auxiliary crosslinker substituted with vinyl or allyl, and a polymer thereof, which has the following structure: ##STR00010## the n3 is 2 or 3; the R.sub.3 is selected from a hydrogen atom or methyl; the A has a structure selected from any one of the following: ##STR00011## wherein a sum of n4 and n5 is an integer from 10 to 20; the R.sub.4 has a structure selected from any one of the following: ##STR00012## wherein the wavy line mark represents a linking bond.

16. A prepreg, comprising a reinforcing material, and the thermosetting resin composition according to claim 11 which is adhered to the reinforcing material after impregnating and drying.

17. A laminate, comprising at least one prepreg according to claim 16.

18. The thermosetting resin composition according to claim 11, wherein the linear 1,2-position vinyl-containing olefin resin and the modified substance thereof have a number average molecular mass of 800-10000.

19. The thermosetting resin composition according to claim 11, wherein in the resin or the small-molecule compound substituted with at least one acrylic group, the resin comprises any one of ##STR00013## polybutadiene or a butadiene-styrene copolymer; wherein a sum of n1 and n2 is an integer from 10 to 20; the R.sub.2 has a structure selected from any one of the following: ##STR00014## wherein the wavy line mark represents a linking bond.

20. The thermosetting resin composition according to claim 11, wherein in the resin or the small-molecule compound substituted with at least one acrylic group, the small-molecule compound comprises any one of ##STR00015## 6-C18 linear alkane, ##STR00016## wherein the wavy line mark represents a substitution site of the acrylic group on the small-molecule compound.

21. The thermosetting resin composition according to claim 15, wherein based on a total mass of component A, component B, component C and component D being 100%, an addition amount of the component D is 1%-70%.

22. The thermosetting resin composition according to claim 15, wherein the thermosetting resin composition further comprises component E: an auxiliary crosslinker substituted with at least one maleimide group; based on a total mass of component A, component B, component C, optional component D and component E being 100%, an addition amount of the component E is 1%-50%.

23. The thermosetting resin composition according to claim 22, wherein the thermosetting resin composition further comprises component F: a filler; the filler comprises an inorganic filler and/or an organic filler.

24. The thermosetting resin composition according to claim 23, wherein the filler has a median particle size of 0.01-50 ?m.

25. The thermosetting resin composition according to claim 23, wherein based on a total mass of component A, component B, component C, optional component D, and optional component E being 100%, an addition amount of the component F is 1%-400%, preferably 20%-300%, and more preferably 30%-300%.

26. The thermosetting resin composition according to claim 23, wherein the thermosetting resin composition further comprises component G: a radical initiator; the radical initiator comprises any one or a combination of at least two of organic peroxide, a carbon radical initiator or an azo radical initiator; based on a total mass of component A, component B, component C, optional component D, and optional component E being 100%, an addition amount of the component G is 0.01%-6%, preferably 0.1%-2%, and more preferably 0.5%-4%.

27. The thermosetting resin composition according to claim 26, wherein the thermosetting resin composition further comprises component H: a flame retardant; the flame retardant comprises a non-halogenated flame retardant and/or a halogenated flame retardant.

28. The thermosetting resin composition according to claim 27, wherein based on a total mass of component A, component B, component C, optional component D, and optional component E being 100%, an addition amount of the component H is 1%-50%.

29. The thermosetting resin composition according to claim 23, wherein the thermosetting resin composition further comprises component I: a coupling agent; based on a total mass of component F being 100%, an addition amount of the component I is 0.25%-4%.

30. The thermosetting resin composition according to claim 29, wherein the coupling agent comprises any one or a combination of at least two of vinyl siloxane, methacrylic siloxane or aniline siloxane.

Description

DETAILED DESCRIPTION

[0084] The technical solutions of the present application will be further described below through embodiments. It should be apparent to those skilled in the art that the embodiments are only used for a better understanding of the present application and should not be regard as a specific limitation of the present application.

[0085] Table 1 shows the materials and their grade information involved in the examples and comparative examples below.

TABLE-US-00001 TABLE 1 Component Manufacturer Grade A: a star-structured styrene- Lee Chang Yung, Taiwan 3401 butadiene-styrene triblock Lee Chang Yung, Taiwan 3411 copolymer Lee Chang Yung, Taiwan 3414 Kraton, Shanghai DX0222 A: a linear styrene-butadiene- Kraton, Shanghai DX408 styrene triblock copolymer (SBS) B: a linear olefin resin and a Nippon Soda, Japan B1000 modified substance thereof Nippon Soda, Japan B2000 Nippon Soda, Japan B3000 Cray Valley, USA R100 Cray Valley, USA R181 C: a resin or a small-molecule Sabic, Saudi SA9000 compound substituted with at Sartomer, USA CD535 least one acrylic group Cray Valley, USA R3500 Sartomer, USA SR368NS Sartomer, USA SR295NS D: an auxiliary crosslinker Mitsubishi Gas, Japan OPE-1200 substituted with vinyl or allyl, Fangruida, Hunan TAIC-A and a polymer thereof Fangruida, Hunan TMAIC Evonik, Germany TVCH Nippon Steel, Japan ODV Wujin Linchuan Chemical, BVPE Jiangsu E: an auxiliary crosslinker Honghu, Hubei BDM substituted with at least one Feixiang, Jiangsu BMI-E maleimide group F: a filler Novoray, Jiangsu DQ1028L G: a radical initiator Nouryon, USA BIPB Nouryon, USA DYBP H: a flame retardant Albemarle, USA XP7866 Albemarle, USA 8010 I: a coupling agent Dow OFS-6030 Shin-Etsu, Japan KBM-573 Shin-Etsu, Japan KBM-1003

Examples 1-17 and Comparative Examples 1-3

[0086] Thermosetting resin compositions were prepared according to the components shown in Tables 2 to 4 (raw materials were added by parts by weight), and samples of copper clad laminates were prepared according to the following preparation method.

[0087] (1) The prescribed amounts of each component were dissolved, mixed and added into a reaction kettle, and diluted with toluene to an appropriate viscosity, stirred and mixed well to obtain a resin liquid.

[0088] (2) The 106 fiberglass cloth was impregnated with the above resin solution, and then dried to remove the solvent to obtain prepregs. The obtained prepregs were laminated with each other and then with two 35 RTF copper foils on two sides, respectively, and then cured in a hot press to prepare a copper clad laminate, in which the curing was carried out at 200? C. and a 30 kg/cm.sup.2 for 200 min.

[0089] Performance Test

[0090] (1) Glass transition temperature (T.sub.g): tested by the DMA test, with reference to the DMA test method specified in IPC-TM-650 2.4.24.

[0091] (2) Dielectric constant (Dk) and dielectric loss factor (Df): tested with reference to the SPDR method.

[0092] (3) Evaluation of moisture and heat resistance (PCT): the copper foil on the surface of the copper clad laminate was etched and made into three 100 mm?100 mm substrates. Evaluation of the substrate: the substrate was placed in a pressure cooker and treated at 120? C. and 105 KPa for 6 hours, and then impregnated in a tin furnace at 288? C., and the time was recorded when the substrate delaminated and burst; when the substrate had held on for more than 5 min in the tin furnace without blistering or delamination, the evaluation could be terminated. In the evaluation, O means that there is no bursting or delamination within 5 min, X means that there is bursting and delamination within 5 min, and more X means more terrible heat-mositure resistance; the test results of three substrates were recorded. Exemplarily, record 000 if all three substrates have no delamination and bursting, and record OOX if two of them have no delamination and bursting but one has delamination and bursting.

[0093] (4) T330: a sample was prepared and tested by the TMA instrument with reference to the T300 method specified in IPC-TM-650 2.4.24.1, and the temperature was heated to 330? C. to investigate the time of delamination and bursting; when the time was more than 60 min, the evaluation could be terminated.

[0094] (5) Heat resistance: the sheet was prepared into 300 mm?300 mm copper clad samples, placed in an oven with a stable temperature of 288? C. and baked for 3 h, and then cooled to 30? C. within 1 h; then, observe whether the copper foil surface of the sheets blistered, and mark X for blistering, and mark O for no blistering.

[0095] (6) Phase separation: the sheet resin was inspected by SEM for phase separation, and mark 000 if the resin phase separation size was less than 1 ?m; mark OOX if the resin phase separation size was 1-3 ?m; mark OXX if the resin phase separation size was less than 3-5 ?m; mark XXX if the resin phase separation size was more than 5 ?m.

[0096] (7) Coefficient of thermal expansion (CTE): tested by the TMA instrument with reference to the CTE test standard specified in IPC-TM-650 2.4.24.1.

[0097] Results of the above tests are shown in Table 2-4.

TABLE-US-00002 TABLE 2 Example Example Example Example Example Example Example 1 2 3 4 5 6 7 A 3401 10 10 3414 20 20 3411 40 85 DX0222 3 DX408 B B1000 20 40 10 19 60 B2000 60 B3000 27 R100 R181 C SA9000 70 70 CD535 20 10 R3500 20 1 SR368NS 5 SR295NS D OPE-1200 70 TAIC-A 10 TMAIC TVCH ODV BVPE E BDM BMI-E F DQ1028L 30 50 100 200 300 50 90 G BIPB 1.5 1.5 2.5 3 1.2 DYBP 1.6 0.9 H XP7866 40 40 30 50 8010 50 30 40 I OFS-6030 0.5 4 1 KBM-573 3 KBM-1003 0.9 Performance Tg(DMA)/? C. 218 >250 >250 220 237 210 >250 Dk(10 G) 3 3 3.2 3.3 3.5 3.2 3.2 Df(10 G) 0.0023 0.0023 0.0023 0.0018 0.0022 0.0023 0.0019 T330(with >60 >60 >60 >60 >60 >60 >60 copper)/min 288? C./3 h ? ? ? ? ? ? ? PCT/6 h ??? ??? ??? ??? ??? ??? ??? Phase ??? ??? ??? ??? ??? ??? ??? separation CTE 2.50% 2.00% 1.70% 1.70% 1.30% 2.50% 1.70%

TABLE-US-00003 TABLE 3 Example Example Example Example Example Example Example 8 9 10 11 12 13 14 A 3401 20 3414 3411 40 DX0222 20 20 20 30 20 DX408 B B1000 40 50 50 30 65 B2000 B3000 R100 20 R181 20 C SA9000 20 20 CD535 R3500 5 5 SR368NS 1 SR295NS 10 5 D OPE-1200 TAIC-A TMAIC 15 TVCH 10 ODV 29 20 BVPE 40 E BDM 10 BMI-E 45 20 F DQ1028L 70 80 100 60 400 100 50 G BIPB 1.6 1.6 7 1 1 DYBP 0.2 1 1 H XP7866 40 30 8010 30 20 20 20 I OFS-6030 KBM-573 KBM-1003 0.7 0.8 1 0.6 Performance Tg(DMA)/? C. >250 >250 >250 >250 >250 >250 >250 Dk(10 G) 3.1 3.3 3 30 3.4 3.3 3.1 Df(10 G) 0.0022 0.0020 0.0021 0.0022 0.0018 0.0028 0.0023 T330(with >60 >60 >60 >60 >60 >60 >60 copper)/min 288? C./3 h ? ? ? ? ? ? ? PCT/6 h ??? ??? ??? ??? ??? ??? ??? Phase ??? ??? ??? ??? ??? ??? ??? separation CTE 2.00% 1.20% 1.10% 1.20% 0.80% 0.80% 1.20%

TABLE-US-00004 TABLE 4 Example Example Example Comparative Comparative Comparative 15 16 17 Example 1 Example 2 Example 3 A 3401 10 10 1 3414 3411 DX0222 25 15 DX408 10 B B1000 15 5 29 20 B2000 B3000 25 15 R100 R181 C SA9000 25 15 85 70 70 CD535 R3500 1 SR368NS SR295NS D OPE-1200 74 TAIC-A TMAIC TVCH ODV BVPE 20 E BDM BMI-E 5 55 F DQ1028L 50 50 50 30 30 30 G BIPB 1 DYBP 1 1 1.6 1.6 1.6 H XP7866 30 8010 30 30 50 50 50 I OFS-6030 KBM-573 KBM-1003 Performance Tg(DMA)/?C. >250 201 >250 210 213 180 Dk(10 G) 3.1 3 3.2 3.4 3.2 3 Df(10 G) 0.0023 0.0024 0.0028 0.0027 0.0023 0.0023 T330(with >60 >60 >60 >60 40 20 copper)/min 288? C./3 h ? X X X X X PCT/6 h ??? ?XX XXX ??? ?XX ??X Phase ??? ?XX XXX ??? XXX XXX separation CTE 1.50% 2.80% 1.00% 4.00% 2.40% 5.00%

[0098] As can be seen from Tables 2-4, the resin composition provided by the present application has effectively relieved phase separation phenomenon, and the prepared copper clad laminate has high heat resistance, low dielectric constant, low dielectric loss tangent value, and high reliability. The glass transition temperature can reach more than or equal to 210? C., Dk is less than or equal to 3.5, Df is less than or equal to 0.0030, the time of delamination and bursting is more than 60 min in the T330 (with copper) test, no bursting or delamination appears in the pressure cooker test within 5 min, the phase separation size of the resin composition is less than 1 ?m, and the coefficient of thermal expansion is less than or equal to 2.5%.

[0099] From the comparison between Example 1 and Comparative Example 3, it can be seen that the problem of phase separation is effectively relieved in the present application by adding the star-structured SBS (Example 1), compared with adding the linear SBS (Comparative Example 3), and the heat resistance and CTE are guaranteed.

[0100] As can be seen from the comparison between Example 1 and Comparative Examples 1-2, the above beneficial effects can be achieved only when the star-structured styrene-butadiene-styrene triblock copolymer, the linear 1,2-position vinyl-containing olefin resin and the modified substance thereof, and the resin or the small-molecule compound substituted with at least one acrylic group are added in the proportion prescribed by the present application. If the addition amount of the resin or the small-molecule compound substituted with at least one acrylic group is too high and the addition amount of the linear 1,2-position vinyl-containing olefin resin is too low (Comparative Example 1), the crosslinking density will be too low, resulting in insufficient heat resistance, poor dielectric properties and poor CTE; if the addition amount of the star-structured styrene-butadiene-styrene triblock copolymer is too low (Comparative Example 2), the resin will have phase separation, resulting in poor heat resistance and poor heat-mositure resistance.

[0101] Although the detailed method of the present application is illustrated through the embodiments in the present application, the present application is not limited to the detailed method, which means that the present application is not necessarily rely on the detailed method to be implemented. It should be apparent to those skilled in the art that any improvement to the present application, equivalent substitution of each raw material of the product of the present application and the addition of auxiliary ingredients, the choice of specific methods, etc., all fall within the protection scope and disclosure scope of the present application.