ACTIVE ESTER, THERMOSETTING RESIN COMPOSITION, PREPREG AND LAMINATED BOARD CONTAINING SAME

Abstract

The present invention provides an active ester, a thermosetting resin composition, a prepreg and a laminated board containing same. The active ester is a PPO main chain-containing double-ended polyfunctional active ester, and the thermosetting resin composition comprises epoxy resin and the PPO main chain-containing double-ended polyfunctional active ester. The prepreg, laminated board and copper-clad plate prepared from the thermosetting resin composition containing the PPO main chain-containing double-ended polyfunctional active ester have excellent dielectric properties, damp-heat resistance, heat resistance, extremely low water absorption and high bending strength.

Claims

1.-10. (canceled)

11. A PPO main chain-containing double-ended polyfunctional active ester resin, having a structure of formula (1): ##STR00003## wherein, R.sub.1 is ##STR00004## substituted or unsubstituted C1-C3 linear or branched alkyl, allyl or isopropenyl; R.sub.3 is H, allyl or isopropenyl; R.sub.4, R.sub.5, R.sub.6, R.sub.7 are independently selected from the group consisting of H, substituted or unsubstituted C1-C3 linear or branched alkyl, allyl, isopropenyl and OR.sub.8; R.sub.8 is substituted or unsubstituted C1-C3 linear or branched alkyl or substituted or unsubstituted phenyl; n1 and n2 are positive integers greater than 0 and satisfy 4n1+n225; n3 and n4 are identical or different, and are independently 1, 2 or 3.

12. The active ester resin of claim 11, characterized in that 6n1+n220.

13. The active ester resin of claim 11, characterized in that 8n1+n215.

14. The active ester resin of claim 11, characterized in that n3 and n4 are identical or different, and are independently 2 or 3.

15. The active ester resin of claim 11, characterized in that n3 and n4 are identical and are independently 2 or 3.

16. A thermosetting resin composition comprising an epoxy resin and the PPO main chain-containing double-ended polyfunctional active ester resin of claim 11.

17. The thermosetting resin composition of claim 16, characterized in that the PPO main chain-containing double-ended polyfunctional active ester resin accounts for 10-80% of the total weight of the thermosetting resin composition.

18. The thermosetting resin composition of claim 16, characterized in that the epoxy resin accounts for 20-50% of the total weight of the thermosetting resin composition.

19. The thermosetting resin composition of claim 16, characterized in that the thermosetting resin composition further comprises any one selected from the group consisting of cyanate ester resin, bismaleimide-triazine resin, 1,2-polybutadiene resin and styrene-butadiene resin, or a mixture of at least two of them, in an amount of 5-40% of the total weight of the thermosetting resin composition.

20. The thermosetting resin composition of claim 16, characterized in that the thermosetting resin composition further comprises an organic additive flame retardant which is a phosphorus-based flame retardant and/or a halogen-based flame retardant.

21. The thermosetting resin composition of claim 16, characterized in that the thermosetting resin composition further comprises a filler and/or a curing accelerator.

22. A prepreg comprising a reinforcing material and the thermosetting resin composition of claim 16 which is attached thereon after impregnation and drying.

23. A laminate comprising at least one sheet of the prepreg of claim 22.

24. A metal clad laminate comprising at least one sheet of the prepreg of claim 22 and a metal foil pressing on one side or both sides of superimposed prepregs.

25. A printed wiring board comprising at least one sheet of the prepreg of claim 22.

Description

EMBODIMENTS

[0037] The followings are specific embodiments of the present invention, and it should be noted that it will be apparent to those skilled in the art that a number of improvements and modifications may be made without departing from the principles of the embodiments of the present invention, and these improvements and modifications are also deemed to be in the protection scope of the present invention.

[0038] Hereinafter, the embodiments of the present invention will be described in further detail with reference to the following multiple examples. The examples of the present invention are not limited to the following specific examples. It is possible to change the implementation without departing from the scope of the claims.

EXAMPLES

(1) Redistribution of PPO

[0039] 4000 g of toluene was heated to 100 C. with stirring in a three-necked flask equipped with a stirrer, a condensing reflux tube and a thermometer, and then 2000 g of PPO resin having a number average molecular weight of 20,000 was added. When the mixture became homogeneous, 600 g of diallyl bisphenol A (DABPA) was added, and the mixture was stirred for 30 min. Then 150 g of benzoyl peroxide (BPO) dissolved in toluene was added and the temperature was maintained at 92 C. for 360 min. The product was then cooled to room temperature and then 4000 ml of methanol was added and the mixture was stirred vigorously, filtered and dried to give 2400 g of a small molecular bifunctional PPO resin (A1).

[0040] Bifunctional PPO resins having different number average molecular weights can be obtained by repeating the above operations, changing the proportion of the reactants of redistributing the PPO resin and changing reaction temperature and reaction time, as shown in the following table:

TABLE-US-00001 A1 A2 A3 A4 A5 A6 PPO 2000 2000 2000 2000 2000 2000 DABPA 600 480 360 320 / / BPA / / / / 300 240 BPO 150 150 150 120 100 80 reaction 92 100 90 100 90 92 temperature/ C. reaction time/min 360 240 240 240 240 300 Mn 1304 1600 1909 2433 2658 3024

(2) Acylation Reaction

[0041] 530 g of trimesoyl chloride was charged into a 5000 ml three-necked flask equipped with a stirrer, a thermometer, a condenser (with a drying tube and a gas absorption device). Then the stirrer was started and the flask was slowly heated with oil bath. When trimesoyl chloride melted to be liquid state, 376 g of phenol was slowly added. At this time, the formed gas HCl escaped continuously and the contents seemed to have boiling phenomenon. When the reaction is not too intense, the reaction temperature was gradually increased to 120 C. and maintained for 1.5-2 h (until no HCl gas escaped). Then, 1000 g of the redistributed small molecular bifunctional PPO resin was added and the mixture was stirred and heated. After reacting for 2 h and the contents became cooler, the reaction mixture was gradually poured into 4000 ml of water with stirring, comminuted, filtered, washed with water, washed with ethanol and then dried to give 1345 g of the product, which is a PPO main chain-containing double-ended hexafunctional active ester resin B4 with an ester equivalent of 332 g/mol.

[0042] PPO main chain-containing double-ended polyfunctional active ester resins having different numbers of ester functional groups and different ester equivalents can be obtained by repeating the above operations, changing the redistributed PPO resins with different number average molecular weights and acyl chlorides and phenols, as shown in the following table:

TABLE-US-00002 B1 B2 B3 B4 B5 B6 B7 Terephthaloyl chloride/g 203 203 Trimesoyl chloride/g 530 530 1,2,4,5-benzene tetra acyl 328 328 328 chloride/g phenol/g 94 282 376 282 p-hydroxyanisole/g 124 496 372 A1/g 1000 A2/g 700 A3/g 800 800 A4/g 2000 A5/g 1200 A6/g 1400 number of ester 4 4 8 6 6 8 8 functional groups ester equivalent (g/mol) 513 605 354 332 540.5 448.5 517

Synthesis Comparative Example: Synthesis of ANCO-rPPE

[0043] 3600 g of toluene was heated to 100 C. with stirring in a three-necked flask equipped with a stirrer, a condensing reflux tube and a thermometer, and then 3600 g of PPO resin having a number average molecular weight of 20,000 was added. When the mixture became homogeneous, 540 g of bisphenol A (BPA) was added, and the mixture was stirred for 30 min. Then 720 g of 75% aqueous benzoyl peroxide (BPO) solution was added and the contents were kept at a temperature of 100 C. to react for 120 min. The product was then cooled to room temperature and then 8000 ml of methanol was added and the mixture was stirred vigorously, filtered and dried to give 4000 g of bifunctional PPO resin having a number average molecular weight of 3400.

[0044] 500 g of the above modified PPO resin was dissolved in 5000 ml of methylene chloride and 100 g of 50 wt % aqueous sodium hydroxide solution was added thereto. After 10 min, 49.9 g of tetrabutylammonium hydrogen sulfate (TBAHS) was added and the mixture was stirred at room temperature for 10 min, followed by the addition of 324.5 g of N,N-diallyl-2-chloroacetamide. After the reaction was carried out at room temperature for about 13 hours, 500 ml of deionized water was added, and the mixture was stirred for 30 min, then the aqueous layer was removed. The organic layer was washed with saturated brine, deionized water and concentrated to 1000 ml and then slowly poured into 5000 ml of methanol to precipitate. The obtained precipitate was washed twice with methanol and dried to give 500 g of ANCO-rPPE.

(3) A Composition of a PPO Main Chain-Containing Double-Ended Polyfunctional Active Ester Resin and an Epoxy Resin

[0045] An epoxy resin, the PPO main chain-containing double-ended polyfunctional active ester resin obtained by the above-mentioned method, and a curing accelerator were uniformly mixed in a certain proportion in a solvent, and the solid content of the glue solution was controlled to be 65%. A 2116 glass cloth was impregnated into the above-mentioned glue solution and controlled to have an appropriate thickness, and then was baked in an oven at 115-175 C. for 2-15 minutes to prepare a prepreg. Then, several sheets of prepreg were stacked together with both sides thereof being stacked with copper foils, and were cured at a curing temperature of 170-250 C. and a curing pressure of 25-60 kg/cm.sup.2 for 60-300 min to obtain a copper clad laminate, as shown in the following table.

TABLE-US-00003 Ex. Ex. Ex. Ex. Ex. Ex. Ex. Ex. Ex. 3-1 3-2 3-3 3-4 3-5 3-6 3-7 3-8 3-9 B1 65 70 B2 75 68 B3 75 B4 55 55 B5 70 B6 60 B7 ANCO-rPPE SA9000 HPC-8000-65T SA90 SA9000 HP-7200HHH 35 32 45 40 HP-7200H-75M 45 NC-7300L 30 30 SKE-3 25 25 DMAP 0.08 0.08 0.08 0.08 0.08 0.08 2E4MZ 0.1 0.1 0.1 Zinc isooctanoate Ex. Comp. Comp. Comp. Comp. Comp. 3-10 Ex. 3-1 Ex. 3-2 Ex. 3-3 Ex. 3-4 Ex. 3-5 B1 B2 85 B2 B4 B5 B6 B7 80 ANCO-rPPE 55 SA9000 55 HPC-8000-651 55 SA90 50 SA9000 HP-7200HHH 45 45 45 HP-7200H-75M 50 NC-7300L SKE-3 20 15 DMAP 0.08 0.08 0.06 0.08 0.08 2E4MZ 0.1 Zinc 1 isooctanoate

[0046] Properties of laminates are shown in the following table.

TABLE-US-00004 Ex. Ex. Ex. Ex. Ex. Ex. Ex. Ex. Ex. 3-1 3-2 3-3 3-4 3-5 3-6 3-7 3-8 3-9 Tg (DMA) 182 192 183 210 185 180 173 190 175 Td (5% loss) 381 380 382 380 384 380 373 380 372 T288 38 40 33 60 38 35 28 40 27 PCT/2 h 3/3 3/3 3/3 3/3 3/3 3/3 3/3 3/3 3/3 Water 0.07 0.06 0.10 0.05 0.07 0.08 0.09 0.06 0.09 absorption/% Dk (10 GHZ) 3.75 3.7 3.6 3.55 3.75 3.8 3.85 3.7 3.85 Df (10 GHZ) 0.005 0.004 0.0025 0.0020 0.005 0.007 0.0075 0.004 0.007 Ex. Comp. Comp. Comp. Comp. Ex. Comp. Ex. 3-10 Ex. 3-1 Ex. 3-2 Ex. 3-3 3-4 3-5 Tg (DMA) 182 165 155 140 Laminate Alkene Td (5% loss) 377 370 350 346 cannot be terminated T288 25 10 5 22 made, ester-based PCT/2 h 3/3 3/3 3/0 3/0 since polyphenylene Water 0.08 0.13 0.08 0.1 ANCO-rPPE ether absorption/% does not react does not react Dk (10 GHZ) 3.6 3.9 3.6 4.00 with EP with epoxy Df (10 GHZ) 0.002 0.011 0.002 0.0085 resin

Analysis of Properties:

[0047] As can be seen from the examples, optimally, the number of active ester functional groups was 8.

[0048] From the comparation of Comparative Example 1 and Example 6, it can be concluded that when the same epoxy resin was cured using different active ester curing agents with the same ratio, the cured system with B4 has enhanced heat resistance, since B4 contains PPO main chain which has strong rigidity.

(4) A Composition of a PPO Main Chain-Containing Double-Ended Polyfunctional Active Ester Resin, an Epoxy Resin and a Cyanate Ester

[0049] An epoxy resin, an esterified PPO resin, a cyanate ester resin and a curing accelerator were uniformly mixed in a certain proportion in a solvent, and the solid content of the glue solution was controlled to be 65%. A 2116 glass cloth was impregnated into the above-mentioned glue solution and controlled to have an appropriate thickness, and then was baked in an oven at 115-175 C. for 2-15 minutes to prepare a prepreg. Then, several sheets of prepreg were stacked together with both sides thereof being stacked with copper foils, and were cured at a curing temperature of 170-250 C. and a curing pressure of 25-60 kg/cm.sup.2 for 60-300 min to obtain a copper clad laminate, as shown in the following table.

TABLE-US-00005 Ex. Ex. Ex. Ex. Ex. Ex. Ex. 4-1 4-2 4-3 4-4 4-5 4-6 4-7 B1 50 B2 50 75 B3 50 B4 50 10 B5 43 B6 B7 SA9000 HPC-8000-65T HP-7200HHH 45 50 40 HP-7200H-75M 35 35 NC-7300L 37 SKE-3 20 CY-40 5 40 10 20 PT30S 15 15 5 HF-10 Silicon powder 33.4 33.4 33.4 33.4 33.4 33.4 33.4 DMAP 0.08 0.08 0.08 0.08 0.08 0.08 Zinc isooctanoate 0.003 0.024 0.006 0.012 Cobalt 0.009 0.009 0.003 acetylacetonate 2E4MZ 0.1 Ex. Ex. Comp. Comp. Comp. Comp. 4-8 4-9 Ex. 4-1 Ex. 4-2 Ex. 4-3 Ex. 4-4 B1 B2 B3 B4 8 25 B5 B6 35 80 B7 30 SA9000 HPC-8000-65T 22 HP-7200HHH 41 HP-7200H-75M NC-7300L 40 18 60 SKE-3 40 25 CY-40 PT30S 50 HF-10 25 30 2 41 18 Silicon powder 33.4 33.4 33.4 33.4 33.4 DMAP 0.08 0.08 0.06 0.008 Zinc isooctanoate 0.015 0.018 0.001 0.024 0.015 0.015 Cobalt acetylacetonate 2E4MZ 0.1 0.1

[0050] Properties of laminates are shown in the following table.

TABLE-US-00006 Ex. Ex. Ex. Ex. Ex. Ex. Ex. 4-1 4-2 4-3 4-4 4-5 4-6 4-7 Tg (DSC) 183 200 186 192 202 193 202 Td (5% loss) 395 395 395 395 395 395 395 T300/min >60 >60 >60 >60 >60 >60 >60 PCT/2 h 3/3 3/3 3/3 3/3 3/3 3/3 3/3 Water 0.07 0.1 0.07 0.07 0.07 0.07 0.07 absorption/% Dk (10 GHZ) 3.8 3.85 3.8 3.8 3.8 3.7 3.75 Df (10 GHZ) 0.008 0.006 0.007 0.0050 0.0050 0.007 0.0053 Ex. Ex. Comp. Ex. Comp. Ex. Comp. Ex. Comp. Ex. 4-8 4-9 4-1 4-2 4-3 4-4 Tg (DSC) 205 206 180 195 189 220 Td (5% loss) 395 390 375 330 388 400 T300/min >60 >60 5 43 25 >60 PCT/2 h 3/3 3/3 3/1 3/0 3/3 3/0 Water 0.07 0.10 0.07 0.3 0.15 0.20 absorption/% Dk (10 GHZ) 3.7 3.8 3.75 3.85 3.75 3.85 Df (10 GHZ) 0.0055 0.005 0.006 0.0095 0.006 0.006

[0051] The informations relating to the materials and tradenames thereof are as follows.

HPC-8000-65T: DIC, DCPD active ester, ester equivalent: 223;
HP-7200HHH: DIC, DCPD epoxy resin, epoxy equivalent: 288;
HP-7200H-75M: DIC, DCPD epoxy resin, epoxy equivalent: 280;
NC-7300L: NIPPON KAYAKU, naphthol type phenolic epoxy resin, epoxy equivalent: 214;
SKE-3: Shang kete, Special Epoxy Resin, epoxy equivalent: 120;
SA90: SABIC, small molecular difunctional polyphenylene ether, hydroxyl equivalent: 850;
SA9000: SABIC, small molecular acrylate terminated polyphenylene ether, CY-40: Wuqiao Resin Plant, DCPD cyanate ester resin;
PT30S: LONCZ, phenolic cyanate ester resin;
HF-10: Shanghai Huifeng, bisphenol A cyanate ester resin;
DMAP: 4-dimethylaminopyridine;
2E4MZ: 2-ethyl-4-methylimidazole.

[0052] The applicant states that: the present invention illustrates the detailed method of the present invention by the above examples, but the present invention is not limited to the detailed method, that is, it does not mean that the present invention must be conducted relying on the above detailed method. Those skilled in the art should understand that any modification to the present invention, any equivalent replacement of each raw material of the present invention and the addition of auxiliary ingredient, the selection of specific embodiment and the like all fall into the protection scope and the disclosure scope of the present invention.