THERMOSET RESIN COMPOSITION, AND PREPREG AND LAMINATED BOARD MADE OF SAME

Abstract

The present invention relates to a thermoset resin composition and prepreg made of the same and laminated board. The thermoset resin composition comprises the following constituents in parts by weight: 50-150 parts of cyanate; 30-120 parts of epoxy resin; 20-70 parts of allyl benzene maleic anhydride; 20-100 parts of polyphenyl ether; 30-100 parts of halogen-free flame retardant; 0.05 to 5 parts of curing accelerator; 50-200 parts of filler. The prepreg and the laminated board made of the thermoset resin composition have comprehensive performance such as low dielectric constant, low dielectric loss, superior flame retardancy, thermal resistance and wet resistance etc., and is suitable for use in a halogen-free high-frequency multilayer circuit board.

Claims

1-10. (canceled)

11. A thermosetting resin composition comprising the following components in parts by weight: 50-150 parts of a cyanate; 30-120 parts of an epoxy resin; 20-70 parts of an allyl benzene-maleic anhydride having the following chemical structural formula: ##STR00004## wherein x is 1-4, 6 and 8; n is 1-12; x and n are both integers; 20-100 parts of a polyphenyl ether; 30-100 parts of a halogen-free flame retardant; 0.05-5 parts of a curing accelerator; and 50-200 parts of a filler.

12. The thermosetting resin composition of claim 11, wherein the cyanate is selected from the group consisting of: ##STR00005## wherein, X.sub.1 and X.sub.2 are each independently selected from at least one of R, Ar, SO.sub.2 or O; R is selected from the group consisting of C(CH.sub.3).sub.2, CH(CH.sub.3), CH.sub.2 and substituted or unsubstituted dicyclopentadienyl; Ar is selected from the group consisting of substituted or unsubstituted benzene, biphenyl, naphthalene, phenolic aldehyde, bisphenol A, bisphenol A phenolic aldehyde, bisphenol F and bisphenol F phenolic aldehyde; n is an integer of greater than or equal to 1; and Y is an aliphatic functional group or aromatic functional group.

13. The thermosetting resin composition of claim 11, wherein the epoxy resin is selected from the group consisting of bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol AD type epoxy resin, bisphenol Z type epoxy resin, bisphenol M type epoxy resin, bisphenol AP type epoxy resin, bisphenol TMC type epoxy resin, biphenyl epoxy resin, alkyl novolac epoxy resin, dicyclopentadiene epoxy resin, bisphenol A type novolac epoxy resin, o-cresol type novolac epoxy resin, phenol type novolac epoxy resin, trifunctional epoxy resin, tetrafunctional epoxy resin, isocyanate modified epoxy resin and naphthalene type epoxy resin, and a mixture of at least two of the foregoing.

14. The thermosetting resin composition of claim 11, wherein the polyphenyl ether has a number-average molecular weight of 1000-4000.

15. The thermosetting resin composition of claim 11, wherein the halogen-free flame retardant is selected from the group consisting of phosphazene, ammonium polyphosphate, tri-(2-carboxyethyl)phosphine, tri-(isopropylchloro)phosphate, trimethyl phosphate, dimethyl-methyl phosphate, resorcinol bis-xylyl phosphate, phosphorus-nitrogen compounds, melamine polyphosphate, melamine cyanurate, tri-hydroxyethyl isocyanurate, 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide and DOPO-containing novolac resin, and a mixture of at least two of the foregoing.

16. The thermosetting resin composition of claim 11, wherein the curing accelerator is selected from the group consisting of imidazole, metal salts, tertiary amines or piperidine compounds, and a mixture of at least two of the foregoing.

17. The thermosetting resin composition of claim 11, wherein the curing accelerator is selected from the group consisting of 2-methylimidazole, undecyl imidazole, 2-ethyl-4-methylimidazole, 2-phenyl-imidazole, 1-cyanoethyl substituted imidazole, benzyldimethylamine, cobalt acetylacetonate, copper acetylacetonate and zinc isooctanoate, and a mixture of at least two of the foregoing.

18. The thermosetting resin composition of claim 11, wherein the filler is an inorganic or organic filler.

19. The thermosetting resin composition of claim 11, wherein the filler is an inorganic filler selected from the group consisting of aluminum hydroxide, alumina, magnesium hydroxide, magnesium oxide, aluminum oxide, silicon dioxide, calcium carbonate, aluminum nitride, boron nitride, silicon carbide, titanium dioxide, zinc oxide, zirconium oxide, mica, boehmite, calcined talc, talc powder, silicon nitride and calcined kaolin, and a mixture of at least two of the foregoing.

20. The thermosetting resin composition of claim 11, wherein the filler is an organic filler selected from the group consisting of polytetrafluoroethylene powder, polyphenylene sulfide and polyethersulfone powder, and a mixture of at least two of the foregoing.

21. The thermosetting resin composition of claim 11, wherein the filler has a particle size of 0.01-50 m.

22. A prepreg prepared from the thermosetting resin composition of claim 11, wherein the prepreg comprises a matrix material, and the thermosetting resin composition is attached thereon after impregnation and drying.

23. The prepreg of claim 22, wherein the matrix material is a non-woven or woven glass fiber cloth.

24. A laminate comprising the prepreg of claim 22.

25. A printed circuit board comprising the laminate of claim 24.

Description

EXAMPLES: PROCESS FOR PREPARING COPPER CLAD LAMINATES

[0048] A cyanate, an epoxy resin, allyl benzene-maleic anhydride, a polyphenylene ether, a halogen-free flame retardant, a curing accelerator, a filler and a solvent were put into a container and stirred to make the mixture uniformly into a glue. The solid content of the solution was adjusted to 60%-70% with the solvent to obtain a glue solution, i.e. a thermosetting resin composition glue solution. A 2116 electronic grade glass cloth was impregnated with the glue, baked into a prepreg by an oven. 6 pieces of 2116 prepregs were covered with electrolytic copper foils having a thickness of 35 m on both sides, vacuum-laminated in a hot press, cured at 190 C. for 120 min to obtain copper clad laminates.

[0049] The components and contents thereof (based on parts by weight) in Examples 1-6 and Comparison Examples 1-5 are shown in Table 1. The component codes and the corresponding component names are shown as follows. [0050] (A) Cyanate: HF-10 (Product name from Shanghai Hui Feng trading) [0051] (B) Epoxy resin [0052] (B-1) Biphenyl epoxy resin: NC-3000-H (Product name from Nippon Kayaku); [0053] (B-2) Dicyclopentadiene epoxy resin: HP-7200H (Product name from Dainippon Ink and Chemicals) [0054] (C-1) Allyl benzene-maleic anhydride synthesized in the preparation example; [0055] (C-2) Styrene-maleic anhydride oligomer: SMA-EF40 (Product name from Sartomer); [0056] (D-1) Polyphenyl ether having a low molecular weight: MX90 (Product name from SABIC Innovative Plastics) having a number-average molecular weight of 1000-4000; [0057] (D-2) Polyphenyl ether having a high molecular weight: Sabic640-111 (Product name from SABIC Innovative Plastics) having a number-average molecular weight of 15000-20000; [0058] (E) Halogen-free flame retardant; [0059] (E-1) PX-200 (Product name from Daihachi Chemical Industry Co.); [0060] (E-2) SPB-100 (Product name from Otsuka Chemical Co.); [0061] (G) Curing accelerator; [0062] (H) Filler: molten silica.

[0063] The processes for preparing CCLs in Examples 1-6 and Comparison Examples 1-5 are the same as those in the examples.

[0064] The glass transition temperature (Tg), peeling strength (PS), dielectric constant (Dk) and dielectric loss angle tangent (Tg), flame retardancy, dip soldering resistance and water absorption after PCT 2h of the copper clad laminates prepared in Examples 1-6 and Comparison Examples 1-5 were tested by the following methods, and the test results are shown in Table 2.

[0065] The performance parameters are tested by the following methods. [0066] A Glass transition temperature (Tg): tested according to the DSC method as stipulated under IPC-TM-650 2.4.25 in accordance with DSC; [0067] B Peeling strength (PS): testing the peeling strength of the metal cover layer under the testing conditions of after thermal stress in the method of IPC-TM-650 2.4.8; [0068] C Dielectric constant (Dk) and dielectric loss angle tangent (DO: testing dielectric constant (Dk) and dielectric loss angle tangent (DO under 1 GHz by the resonance method using a stripe line according to IPC-TM-650 2.5.5.5; [0069] D Flame retardancy: tested according to the UL-94 standard; [0070] E Dip soldering resistance and water absorption after PCT 2h:

[0071] The copper clad laminate was immersed in a copper etching solution to remove the surface copper foils, and to evaluate the substrate. The substrate was placed in a pressure cooker and treated at 121 C. and 2 atm for 2 hours. After the water absorption was measured, the substrate was immersed in a tin furnace having a temperature of 288 C. The corresponding time was recorded when the substrate is bubbled or split. The evaluation was finished when the substrate had no foaming or stratification in the tin furnace for more than 5 min.

TABLE-US-00001 TABLE 1 Example Example Example Example Example Example Comparison Comparison Comparison Comparison Comparison 1 2 3 4 5 6 Example 1 Example 2 Example 3 Example 4 Example 5 A 100 100 100 100 50 150 100 100 100 100 100 B-1 80 80 80 40 30 60 80 80 40 80 80 B-2 40 60 40 C-1 25 35 60 35 20 70 5 60 60 C-2 25 60 D-1 50 50 50 50 20 100 50 50 50 D-2 50 E-1 20 20 20 20 42 20 20 20 20 20 E-2 45 45 45 45 30 58 45 45 45 45 45 G q.s q.s q.s q.s q.s q.s q.s q.s q.s q.s q.s H 110 110 110 110 50 200 110 110 110 110 110

TABLE-US-00002 TABLE 2 Com- Com- Com- Com- Com- Ex- Ex- Ex- Ex- Ex- Ex- parison parison parison parison parison Test ample ample ample ample ample ample Ex- Ex- Ex- Ex- Ex- items 1 2 3 4 5 6 ample 1 ample 2 ample 3 ample 4 ample 5 Tg(DSC) 185 190 197 191 191 194 171 180 170 198 195 ( C.) Peeling 1.48 1.43 1.42 1.41 1.43 1.42 1.50 144 1.55 1.42 1.41 strength (N/mm) Dielectric 3.6 3.6 3.5 3.6 3.6 3.5 3.8 3.8 3.9 4.0 3.6 constant (1GHz) Dielectric loss 0.0046 0.0042 0.0040 0.0042 0.0042 0.0040 0.0048 0.0045 0.0058 0.0080 0.0042 (1GHz) Combustibility V-0 V-0 V-0 V-0 V-0 V-0 V-0 V-0 V-0 V-0 V-0 PCT (min) >5 >5 >5 >5 >5 >5 >5 >5 3 3 >5 PCT water 0.32 0.30 0.29 0.29 0.30 0.30 0.34 0.32 0.30 0.32 0.29 absorption Processability Better Better Better Better Better Better Better Better Better Better Worse

[0072] It can be seen according to the data in Tables 1 and 2 that, [0073] (1) As can be seen from Examples 1 to 3, the glass transition temperature of the substrate could be remarkably improved, and the dielectric properties and the PCT water absorption rate could also be improved, along with the increase of the amount of allyl benzene-maleic anhydride in Examples 1-3; by comparing Examples 1 and 3 with Comparison Examples 1-2, it could be found that the dielectric properties and the PCT water absorption of Examples 1 and 3 were significantly lower than those of Comparison Examples 1-2, which showed that the addition of allyl benzene-maleic anhydride of the present invention in Examples 1 and 3 improved the dielectric properties and PCT water absorption and increased the glass transition temperature of the substrate as compared to using styrene-maleic anhydride in Comparison Examples 1-2; [0074] (2) As can be seen from Examples 4-6 and Comparison Example 3, the components to be used were controlled within certain weight ranges, so that the substrates had excellent overall properties; by comparing Comparison Example 3 with Example 4, it could be found that, when the amount of allyl benzene-maleic anhydride was reduced to 5 parts by weight, the dielectric properties of the substrate were significantly deteriorated; the glass transition temperature was significantly reduced, and it could not pass the 2-hour PCT test; [0075] (3) As can be seen from Example 3 and Comparison Example 4, the dielectric constant, dielectric loss and PCT water absorption of Example 3 were lower than those of Comparison Example 4, and Comparison Example 4 could not pass the 2h PCT test; it was found that the dielectric properties in Example 3 was remarkably improved after adding a polyphenyl ether having a low molecular weight as compared to Comparison Example 4 in which a polyphenyl ether having a low molecular weight was not added; moreover, Example 3 could pass the 2h PCT test; by comparing Example 3 with Comparison Example 5, it can be found that, although their overall properties were equivalent, the use of a polyphenylene ether having a high molecular weight resulted in poor processability.

[0076] According to Examples 1 to 6, it was found that the laminates prepared by using the thermosetting resin composition of the present invention have a dielectric constant of 3.6 or less, a dielectric loss of 0.0040 to 0.0046, and have excellent flame retardancy, heat resistance, moisture resistance and other comprehensive performances. The flame retardancy thereof can reach the V-0 standard in the flame retardant test UL-94, and PCT water absorption is 0.29-0.32. Thus they are suitable for use in halogen-free high-frequency multilayer circuit boards.

[0077] In summary, the thermosetting resin composition of the present invention has a low dielectric constant, low dielectric loss, excellent heat resistance and cohesiveness while ensuring halogen-free flame retardancy, and is suitable for use in halogen-free high frequency multilayer circuit boards.

[0078] Certainly, the above-described examples are merely illustrative examples of the present invention and are not intended to limit the implement scope of the present invention. Therefore any equivalent changes or modifications according to the principles within the patent scope of the present invention are all included in the scope of the present patent.