THERMOSETTING RESIN COMPOSITION

Abstract

Provided in the present invention is a thermosetting resin composition, comprising phosphorus-containing active ester and epoxy resin, the phosphorus-containing active ester being copolymerised using bis-aromatic formyl chloride hydrocarbyl phosphine oxide and one of bis-hydroxyl aromatic hydrocarbyl phosphine oxide, bis-hydroxyl aromatic oxyhydrocarbyl phosphine oxide, or hydroxylated DOPO, and then obtained from aromatic formyl chloride end capping; the thermosetting resin composition provided in the present invention has the advantages of good thermal stability, humidity resistance and heat resistance, a low dielectric constant and dielectric loss tangent, a low rate of water absorption, and halogen-free flame-retardant properties, and has excellent machinability; also provided in the present invention are applications of the thermosetting resin composition for resin sheet material, resin composite metal foil, prepreg, laminated plate, metal foil-clad laminated plate, and printed circuit boards.

Claims

1-8. (canceled)

9. A thermosetting resin composition, comprising: I) a curing agent comprising at least one phosphorus-containing active ester, wherein the phosphorus-containing active ester is present in an amount of 10% to 60% by weight of the total weight of an epoxy resin and the curing agent in the thermosetting resin composition, the phosphorus-containing active ester is obtained by copolymerizing a diarylformylchlorohydrocarbylphosphine oxide with at least one of a dihydroxyarylhydrocarbylphosphine oxide, a dihydroxyaryloxyhydrocarbylphosphine oxide and a hydroxylated DOPO, and then terminating by an aromatic formyl chloride, wherein the diarylformylchlorohydrocarbylphosphine oxide has a structural formula of Formula (I), ##STR00044## the dihydroxyarylhydrocarbylphosphine oxide has a structural formula of Formula (II), ##STR00045## the dihydroxyaryloxyhydrocarbylphosphine oxide has a structural formula of Formula (III), ##STR00046## the hydroxylated DOPO has a structural formula of Formula (IV), ##STR00047## the aromatic formyl chloride has a structural formula of Formula (V), ##STR00048## wherein R.sub.1 and R.sub.2 are identical or different from each other, and each independently anyone selected from the group consisting of phenyl, naphthyl, and linear or branched alkyl having 1 to 4 carbon atoms; wherein Ar.sub.1 and Ar.sub.2 are identical or different from each other, and each independently anyone selected from the group consisting of ##STR00049## ##STR00050## wherein Ar.sub.3 is anyone selected from the group consisting of ##STR00051## wherein Ar.sub.4 is anyone selected from the group consisting of ##STR00052## wherein n.sub.3 is an integer of 0-5; wherein n.sub.4 is an integer of 0-7; wherein R.sub.3 is anyone selected from the group consisting of linear or branched alkyl groups having 1 to 4 carbon atoms; II) an epoxy resin present in an amount of 30% to 60% by weight of the total weight of the epoxy resin and the curing agent in the thermosetting resin composition.

10. The thermosetting resin composition claimed in claim 9, wherein the phosphorus-containing active ester is obtained by copolymerizing a diarylformylchlorohydrocarbylphosphine oxide with a dihydroxyarylhydrocarbylphosphine oxide and then terminating by an aromatic formyl chloride, wherein the phosphorus-containing active ester has a structural formula of formula (VI), ##STR00053## wherein n is an integer of 1-20; wherein R.sub.1 and R.sub.2 are identical or different from each other, and each independently anyone selected from the group consisting of phenyl, naphthyl, and linear or branched alkyl having 1 to 4 carbon atoms; wherein Ar.sub.1 and Ar.sub.2 are identical or different from each other, and each independently anyone selected from the group consisting of ##STR00054## ##STR00055## wherein Ar.sub.4 is anyone selected from the group consisting of ##STR00056## wherein n.sub.3 is an integer of 0-5; wherein n.sub.4 is an integer of 0-7; wherein R.sub.3 is anyone selected from the group consisting of linear or branched alkyl groups having 1 to 4 carbon atoms.

11. The thermosetting resin composition claimed in claim 9, wherein the phosphorus-containing active ester is obtained by copolymerizing a diarylformylchlorohydrocarbylphosphine oxide with a dihydroxyaryloxyhydrocarbylphosphine oxide and then terminating by an aromatic formyl chloride, wherein the phosphorus-containing active ester has a structural formula of formula (VII), ##STR00057## wherein n is an integer of 1-20; wherein R.sub.1 and R.sub.2 are identical or different from each other, and each independently anyone selected from the group consisting of phenyl, naphthyl, and linear or branched alkyl having 1 to 4 carbon atoms; wherein Ar.sub.1 and Ar.sub.2 are identical or different from each other, and each independently anyone selected from the group consisting of ##STR00058## ##STR00059## wherein Ar.sub.4 is anyone selected from the group consisting of ##STR00060## wherein n.sub.3 is an integer of 0-5; wherein n.sub.4 is an integer of 0-7; wherein R.sub.3 is anyone selected from the group consisting of linear or branched alkyl groups having 1 to 4 carbon atoms.

12. The thermosetting resin composition claimed in claim 9, wherein the phosphorus-containing active ester is obtained by copolymerizing a diarylformylchlorohydrocarbylphosphine oxide with a hydroxylated DOPO and then terminating by an aromatic formyl chloride, wherein the phosphorus-containing active ester has a structural formula of formula (VIII), ##STR00061## wherein n is an integer of 1-20; wherein R.sub.1 is anyone selected from the group consisting of phenyl, naphthyl, and linear or branched alkyl having 1 to 4 carbon atoms; wherein Ar.sub.1 is anyone selected from the group consisting of ##STR00062## ##STR00063## wherein Ar.sub.2 is anyone selected from the group consisting of ##STR00064## wherein Ar.sub.4 is anyone selected from the group consisting of ##STR00065## wherein n.sub.3 is an integer of 0-5; wherein n.sub.4 is an integer of 0-7; wherein R.sub.3 is anyone selected from the group consisting of linear or branched alkyl groups having 1 to 4 carbon atoms.

13. The thermosetting resin composition claimed in claim 9, wherein the phosphorus-containing active ester is obtained by copolymerizing a diarylformylchlorohydrocarbylphosphine oxide with a dihydroxyaryloxyhydrocarbylphosphine oxide and a hydroxylated DOPO and then terminating by an aromatic formyl chloride, wherein the phosphorus-containing active ester has a structural formula of formula (IX) or (X), ##STR00066## wherein each of n.sub.1 and n.sub.2 is an integer of 0-20, and 1n.sub.1+n.sub.220; wherein each of a and b is 0 or 1, and a+b=1; wherein b must be 0 when n.sub.1 is 0; wherein a must be 0 when n.sub.2 is 0; wherein R.sub.1 and R.sub.2 are identical or different from each other, and each independently anyone selected from the group consisting of phenyl, naphthyl, and linear or branched alkyl having 1 to 4 carbon atoms; wherein Ar.sub.1 and Ar.sub.2 are identical or different from each other, and each independently anyone selected from the group consisting of ##STR00067## ##STR00068## wherein Ar.sub.3 is anyone selected from the group consisting of ##STR00069## wherein Ar.sub.4 is anyone selected from the group consisting of ##STR00070## wherein n.sub.3 is an integer of 0-5; wherein n.sub.4 is an integer of 0-7; wherein R.sub.3 is anyone selected from the group consisting of linear or branched alkyl groups having 1 to 4 carbon atoms.

14. The thermosetting resin composition claimed in claim 9, wherein the curing agent further comprises a cyanate resin and/or a bismaleimide-triazine resin; the cyanate resin and/or the bismaleimide-triazine resin are/is present in an amount of 0%-50% by weight of the total weight of the epoxy resin and the curing agent in the thermosetting resin composition.

15. The thermosetting resin composition claimed in claim 9, wherein the curing agent further comprises a SMA resin; the SMA resin is present in an amount of 0%-40% by weight of the total weight of the epoxy resin and the curing agent in the thermosetting resin composition.

16. The thermosetting resin composition claimed in claim 9, wherein the curing agent further comprises a phenolic resin; the phenolic resin is present in an amount of 0%-20% by weight of the total weight of the epoxy resin and the curing agent in the thermosetting resin composition.

17. The thermosetting resin composition claimed in claim 9, wherein the curing agent further comprises an organic halogen-free flame retardant; the organic halogen-free flame retardant is present in an amount of 0-15 parts by weight, based on 100 parts by weight of the total weight of the epoxy resin and the curing agent in the thermosetting resin composition.

18. The thermosetting resin composition claimed in claim 9, wherein the thermosetting resin composition further comprises a filler and/or an accelerator.

19. The method for using the thermosetting resin composition claimed in claim 1 in resin sheet materials, resin composite metal foils, prepregs, laminates, metal foil-clad laminates and printed circuit boards.

Description

EMBODIMENTS

[0056] The technical solution of the present invention will be further described below by the specific embodiments.

[0057] The followings are the specific embodiments of the examples of the present invention. It should be noted that those skilled in the art can make some improvements and refinements without departing from the principles of the examples of the present invention. These improvements and refinements are also considered to be the protection scope of the examples of the present invention.

[0058] The embodiments of the present invention are further described below in various examples. The examples of the present invention are not limited to the specific examples below. Modifications can be made appropriately without departing from the scope of the claims.

[0059] 1. Synthesis of P-AE1

[0060] 270 g of bis(3-formylchlorophenyl)methylphosphine oxide, 168 g of ODOPB, 147 g of bis(3-hydroxyphenoxy)methylphosphine oxide and 1500 g of pyridine were stirred in a four-necked flask equipped with a stirrer, a reflux condensation tube and a thermometer, while nitrogen gas was introduced. The mixture was then warmed to 30 C. and reacted at such temperature for 4 h. 21 g of benzoyl chloride was further added to the reaction system, and the reaction was also carried out at such temperature for 2 h. The product was cooled to room temperature, and then a 5% sodium carbonate solution was added. The mixture was stirred vigorously, filtered, washed with water and dried to obtain a product numbered as P-AE1.

##STR00028##

[0061] wherein n.sub.1=10, and n.sub.2=10.

[0062] 2. Synthesis of P-AE2

[0063] 270 g of bis(4-formylchlorophenyl)methylphosphine oxide, 76.8 g of ODOPB, 269 g of bis(4-hydroxyphenoxy)methylphosphine oxide and 1500 g of pyridine were stirred in a four-necked flask equipped with a stirrer, a reflux condensation tube and a thermometer, while nitrogen gas was introduced. The mixture was then warmed to 30 C. and reacted at such temperature for 4 h. 56 g of benzoyl chloride was further added to the reaction system, and the reaction was also carried out at such temperature for 2 h. The product was cooled to room temperature, and then a 5% sodium carbonate solution was added. The mixture was stirred vigorously, filtered, washed with water and dried to obtain a product numbered as P-AE2.

##STR00029##

[0064] wherein n.sub.1=8, and n.sub.2=2.

[0065] 3. Synthesis of P-AE3

[0066] 332 g of bis(4-formylchlorophenyl)methylphosphine oxide, 259 g of ODOPB, 239.4 g of bis(4-hydroxyphenoxy)methylphosphine oxide and 1500 g of pyridine were stirred in a four-necked flask equipped with a stirrer, a reflux condensation tube and a thermometer, while nitrogen gas was introduced. The mixture was then warmed to 30 C. and reacted at such temperature for 4 h. 152 g of naphthoyl chloride was further added to the reaction system, and the reaction was also carried out at such temperature for 2 h. The product was cooled to room temperature, and then a 5% sodium carbonate solution was added. The mixture was stirred vigorously, filtered, washed with water and dried to obtain a product numbered as P-AE3.

##STR00030##

[0067] wherein n.sub.1=3, and n.sub.2=3.

[0068] 4. Synthesis of P-AE4

[0069] 627 g of bis(4-(4-benzoylchloro)phenylsulfonyl)phenylphosphine oxide, 673 g of 10-(2,7-dihydroxynaphthyl)-10-hydro-9-oxa-10-phosphaphenanthrene-10-oxide and 1500 g of pyridine were stirred in a four-necked flask equipped with a stirrer, a reflux condensation tube and a thermometer, while nitrogen gas was introduced. The mixture was then warmed to 30 C. and reacted at such temperature for 4 h. 352 g of naphthoyl chloride was further added to the reaction system, and the reaction was also carried out at such temperature for 2 h. The product was cooled to room temperature, and then a 5% sodium carbonate solution was added. The mixture was stirred vigorously, filtered, washed with water and dried to obtain a product numbered as P-AE4.

##STR00031##

[0070] wherein n=3.

[0071] 5. Synthesis of P-AE5

[0072] 403 g of bis(4-benzoylchloro)phenylphosphine oxide, 558 g of bis(4-hydroxyphenyl)phenylphosphine oxide and 1500 g of pyridine were stirred in a four-necked flask equipped with a stirrer, a reflux condensation tube and a thermometer, while nitrogen gas was introduced. The mixture was then warmed to 30 C. and reacted at such temperature for 4 h. 238 g of benzoyl chloride was further added to the reaction system, and the reaction was also carried out at such temperature for 2 h. The product was cooled to room temperature, and then a 5% sodium carbonate solution was added. The mixture was stirred vigorously, filtered, washed with water and dried to obtain a product numbered as P-AE5.

##STR00032##

[0073] wherein n=3.

[0074] 6. Synthesis of P-AE6

[0075] 627 g of bis(4-(4-benzoylchloro)phenylsulfonyl)phenylphosphine oxide, 988 g of bis(4-hydroxybiphenylyloxy)phenylphosphine oxide and 1500 g of pyridine were stirred in a four-necked flask equipped with a stirrer, a reflux condensation tube and a thermometer, while nitrogen gas was introduced. The mixture was then warmed to 30 C. and reacted at such temperature for 4 h. 390 g of benzoyl chloride was further added to the reaction system, and the reaction was also carried out at such temperature for 2 h. The product was cooled to room temperature, and then a 5% sodium carbonate solution was added. The mixture was stirred vigorously, filtered, washed with water and dried to obtain a product numbered as P-AE6.

##STR00033##

[0076] wherein n=1.

[0077] The above phosphorus-containing active ester P-AE, a halogen-free epoxy resin and a curing accelerator, a halogen-free flame retardant and a filler were uniformly mixed in a certain ratio in a solvent, and the solid content of the glue was controlled to be 65%. A 2116 fiberglass cloth was impregnated with the above glue to control the appropriate thickness thereof, then was baked in an oven at 115-175 C. for 2-15 minutes to produce a prepreg. Then several prepregs were stacked together, and 18 m RTF copper foil was stacked on both sides thereof, to produce a copper-clad laminate at a curing temperature of 170-250 C., a curing pressure of 25-60 kg/cm.sup.2 and a curing time of 60-300 min.

[0078] The materials and brand informations thereof in Examples 1-21 and Comparative Examples 1-12 are as follows:

[0079] (A)

[0080] P-AE1: Self-Made Phosphorus-Containing Active Ester

##STR00034##

[0081] wherein n.sub.1=10, and n.sub.2=10.

[0082] P-AE2: Self-Made Phosphorus-Containing Active Ester

##STR00035##

[0083] wherein n.sub.1=8, and n.sub.2=2.

[0084] P-AE3: Self-Made Phosphorus-Containing Active Ester

##STR00036##

[0085] wherein n.sub.1=3, and n.sub.2=3.

[0086] P-AE4: Self-Made Phosphorus-Containing Active Ester

##STR00037##

[0087] wherein n=3.

[0088] P-AE5: Self-Made Phosphorus-Containing Active Ester

##STR00038##

[0089] wherein n=3.

[0090] P-AE6: Self-Made Phosphorus-Containing Active Ester

##STR00039##

[0091] wherein n=1.

[0092] BHPPO: Bis(4-hydroxyphenoxy)phenylphosphine oxide

##STR00040##

[0093] BCPPO: Bis(4-carboxyphenyl)phenylphosphine oxide

##STR00041##

[0094] ODOPB: 10-(2,5-dihydroxyphenyl)-10-hydro-9-oxa-10-phosphaphenanthrene-10-oxide

##STR00042##

[0095] FRX-3001:

##STR00043##

[0096] (B) Cyanate

[0097] CY-40: Wuqiao resin factory, DCPD-type cyanate resin

[0098] PT60S: LONCZ, Novolac type cyanate resin

[0099] CE01PS: Jiangsu Tianqi, bisphenol A-type cyanate resin

[0100] CE01MO: Jiangsu Tianqi, bisphenol A-type cyanate resin

[0101] (C) Epoxy Resin

[0102] HP-7200HHH: DIC, DCPD-type epoxy resin having an epoxy equivalent of 288

[0103] HP-7200H-75M: DIC, DCPD-type epoxy resin having an epoxy equivalent of 280

[0104] HP-6000: DIC, Epoxy resin having an epoxy equivalent of 250

[0105] HP-9900: DIC, Naphthol-type epoxy resin having an epoxy equivalent of 274

[0106] NC-3000H: Nippon Kayaku, Biphenyl epoxy resin having an epoxy equivalent of 294

[0107] SKE-1: Shankote, special epoxy resin having an epoxy equivalent of 120

[0108] SKE-3: Shankote, special epoxy resin having an epoxy equivalent of 120

[0109] (D) Phenolic Resin

[0110] DOW92741: Phosphorus-containing novolac resin, Dow Chemical

[0111] SEB-0904PM60: Phosphorus-containing novolac resin, SHIN-A

[0112] SHN-1655TM65: Phosphorus-containing novolac resin, SHIN-A

[0113] 2812: linear novolac resin, MOMENTIVE (Korea)

[0114] (E) Phosphorus-Containing Flame Retardant

[0115] SPB-100: Otsuka Chemical, phosphazene flame retardant having a phosphorus

[0116] content of 13.4%

[0117] (F) SMA

[0118] EF40: SMA, Sadoma

[0119] EF60: SMA, Sadoma

[0120] EF80: SMA, Sadoma

[0121] EF1000: SMA, Sadoma

[0122] (G) Accelerator

[0123] 2E4MZ: 2-ethyl-4-methylimidazole, Shikoku

[0124] DMAP: 4-dimethylaminopyridine, Guangrong Chemical

[0125] BICAT Z: zinc isooctanoate, The Shepherd Chemical Company

[0126] (H) Filler

[0127] Molten silica (having an average particle size of 0.1-10 m and a purity of 99% or more)

[0128] Tables 1-4 involve the formulation compositions and the physical property data of Examples 1-21, and Tables 5-6 involve the formulation compositions and the physical property data of Comparative Examples 1-12.

TABLE-US-00001 TABLE 1 Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 P-AE1 40 P-AE2 40 P-AE3 45 P-AE4 50 10 P-AE5 10 P-AE6 30 60 HP-7200H-75M 45 HP-7200HHH 40 HP-9900 20 NC-3000H 60 35 50 50 SKE-3 15 DMAP 0.01 0.05 0.1 0.2 0.2 0.5 Spherical silicon 0 25 25 25 25 300 P % 4.28% 4.31% 4.99% 4.17% 3.18% 3.07% Tg(DMA)/ C. 180 195 185 190 187 185 Dk(10 GHz) 3.8 3.8 3.8 3.8 3.8 3.8 Df(10 GHz) 0.008 0.0085 0.0083 0.0075 0.0075 0.0075 Water absorption/% 0.12 0.12 0.14 0.12 0.12 0.09 PCT/6 h T288/min >60 >60 >60 >60 >60 >60 Flame retardancy V-0 V-0 V-0 V-0 V-0 V-0

TABLE-US-00002 TABLE 2 Example 7 Example 8 Example 9 Example 10 Example 11 P-AE1 10 30 20 20 40 CE01MO 50 CEO1PS 40 CY-40 30 PT-60S 20 10 HP-7200HHH 10 HP-6000 50 HP-9900 60 NC-3000H 50 SKE-1 30 SKE-3 30 SPB-100 3.6 DMAP 0.01 0.08 0.1 1 0.3 Spherical silicon 100 25 25 25 5 P % 1.50% 3.21% 2.14% 2.14% 4.28% Tg(DMA)/ C. 245 235 205 205 198 Dk(10 GHz) 4 3.8 3.8 3.9 3.8 Df(10 GHz) 0.0072 0.072 0.07 0.008 0.0075 Water absorption/% 0.1 0.07 0.07 0.07 0.08 PCT/6 h T288/min >60 >60 >60 >60 >60 Flame retardancy V-0 V-0 V-0 V-0 V-0

TABLE-US-00003 TABLE 3 Example 12 Example 13 Example 14 Example 15 Example 16 P-AE1 20 P-AE2 20 20 P-AE3 20 P-AE4 50 EF1000 20 25 10 EF40 30 40 EF60 15 EF80 10 HP-6000 50 HP-9900 60 40 SKE-1 30 SKE-3 30 2E4MZ 0.1 0.1 0.1 0.1 DMAP 1 Spherical silicon 25 25 25 25 25 P % 2.14% 2.15% 2.22% 2.39% 4.17% Tg(DMA)/ C. 195 180 190 195 198 Dk(10 GHz) 3.8 3.8 3.8 3.8 3.8 Df(10 GHz) 0.0088 0.008 0.0075 0.0065 0.0072 Water absorption/% 0.09 0.09 0.09 0.06 0.07 PCT/6 h T288/min >60 >60 >60 >60 >60 Flame retardancy V-0 V-0 V-0 V-0 V-0

TABLE-US-00004 TABLE 4 Example 17 Example 18 Example 19 Example 20 Example 21 P-AE1 20 P-AE2 30 P-AE3 25 P-AE4 35 P-AE6 50 DOW92741 5 SEB-0904PM60 5 SHN-1655TM65 5 2812 15 15 20 15 5 HP-7200H-M75 45 HP-7200HHH 45 HP-6000 50 HP-9900 55 NC-3000H 60 2E4MZ 0.1 0.1 0.1 0.1 0.1 Spherical silicon 25 25 25 25 25 P % 2.59% 3.27% 3.23% 3.27% 2.56% Tg(DMA)/ C. 180 185 180 190 195 Dk(10 GHz) 3.8 3.8 3.8 3.8 3.8 Df(10 GHz) 0.008 0.0075 0.0075 0.0085 0.007 Water absorption/% 0.08 0.08 0.08 0.08 0.085 PCT/6 h T288/min >60 >60 >60 >60 >60 Flame retardancy V-0 V-0 V-0 V-0 V-0

TABLE-US-00005 TABLE 5 Comp. Comp. Comp. Comp. Comp. Comp. Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 P-AE6 ODOPB 60 20 20 35 FRX3001 60 20 CY-40 30 30 EF40 30 SHN-1655TM65 5 2812 15 HP-7200HHH 40 45 40 HP-6000 50 50 50 2E4MZ 0.1 0.1 DMAP 0.5 0.1 0.5 0.1 Spherical silicon 300 25 25 25 300 25 P % 5.81% 1.94% 1.94% 3.74% 6.00% 2.00% Tg (DMA)/ C. 180 ODOPB is too 180 170 FRX-3001 180 Dk (10 GHz) 4.3 high in 4.2 4.3 has low 4 Df (10 GHz) 0.014 catalytic 0.011 0.0011 activity, 0.0095 Water absorption/% 0.2 activity for 0.12 0.4 resulting in 0.1 PCT/6 h XXX cyanate esters, XXX XXX failure to XXX T288/min 15 resulting in 32 24 form sheet 45 Flame retardancy V-0 failure to form V-0 V-0 V-1 sheets

TABLE-US-00006 TABLE 6 Comp. Comp. Comp. Comp. Comp. Comp. Example Example 7 Example 8 Example 9 Example 10 Example 11 12 P-AE6 70 9 ODOPB 30 BHPPO 60 30 BCPPO 60 30 30 FRX3001 CY-40 EF40 SHN-1655TM65 2812 HP-7200HHH 30 91 40 40 40 40 HP-6000 2E4MZ DMAP 0.5 0.5 0.5 0.5 0.5 0.5 Spherical silicon 300 300 300 300 300 300 P % 3.54% 0.45% 5.44% 5.08% 5.26% 5.45% Tg(DMA)/ C. 170 Insufficient 180 185 160 170 Dk(10 GHz) 4.3 curing agent, 4.3 4.3 4.3 4.3 Df(10 GHz) 0.014 resulting in 0.014 0.012 0.014 0.012 Water 0.2 failure to 0.2 0.15 0.2 0.15 absorption/% form sheets PCT/6 h XXX XXX XXX XXX XXX T288/min 15 5 15 1.5 3 Flame V-0 V-0 V-0 V-0 V-0 retardancy

[0129] Additional descriptions of the PCT/6 h performance icons: x represents that delamination and popcorn occurred, O represents that delamination and popcorn did not occur.

[0130] The above characteristics are tested as follows.

[0131] (1) Glass transition temperature (Tg): Determined according to the DMC method specified in IPC-TM-650 2.4.24.

[0132] (2) Dielectric constant and dielectric loss factor: Tested according to the SPDR method.

[0133] (3) Evaluation of heat and humidity resistance (PCT): The copper foil on the surface of the copper-clad laminate was etched and the substrate was evaluated. The substrate was placed in a pressure cooker and treated at 120 C. and 105 KPa for 6 h, and then immersed in a tin furnace at 288 C. When there was delamination and popcorn, the corresponding time was recorded. When the substrate had not been bubbled or delaminated in the tin furnace for more than 5 min, the evaluation could be ended.

[0134] (4) T288: tested with a TMA instrument according to the T300 test method specified in IPC-TM-650 2.4.24.1.

[0135] (5) Water Absorption: tested according to the test method specified in IPC-TM-650 2.6.2.1.

[0136] (6) Flame retardancy: tested according to the UL standard method.

[0137] From the comparisons of the data in Tables 1-6, the followings can be noted.

[0138] By comparing Comparative Example 1 with Example 6, it can be seen that the copper-clad laminate prepared by using ODOBP and the halogen-free epoxy resin in Comparative Example 1 has worse dielectric properties, poor heat resistance and heat and humidity resistance, high water absorption rate and low Tg. By comparing Comparative Example 2 with Example 9, it can be seen that ODOBP and cyanate resin were used together in Comparative Example 2 to cure the halogen-free epoxy resin, and the catalytic activity of ODOPB to cyanate resin was too high, resulting in failure to form a sheet. By comparing Comparative Example 3 with Example 13, it can be seen that the copper-clad laminate prepared by curing the halogen-free epoxy resin with ODOBP and SMA resin in Comparative Example 3 has worse dielectric properties, poor heat resistance and heat and humidity resistance, and high water absorption rate. By comparing Comparative Example 4 with Example 20, it can be seen that the copper-clad laminate prepared by curing the halogen-free epoxy resin with ODOBP and phenolic resin in Comparative Example 4 has worse dielectric properties, poor heat resistance and heat and humidity resistance, high water absorption rate and low Tg. By comparing Comparative Example 5 with Examples 6, it can be seen that FRX3001 is used to cure the halogen-free epoxy resin in Example 5; due to poor reactivity and low OH.sup. content of FRX3001, the copper-clad laminates cannot be made. By comparing Comparative Example 6 with Example 9, it can be seen that the copper-clad laminate prepared by curing the halogen-free epoxy resin with FRX3001 and cyanate resin in Comparative Example 6 has worse dielectric properties, low Tg, poor heat resistance and heat and humidity resistance, high water absorption and poor flame retardancy.

[0139] Further, it can be seen by comparing Comparative Example 7 with Example 6 that the copper-clad laminate prepared in Comparative Example 7 from phosphorus-containing active ester in a content higher than that in Example 6 has high water absorption rate, heat resistance and heat and humidity resistance. By comparing Comparative Example 8 with Example 6, it can be seen that, when the phosphorus-containing active ester is used in Comparative Example 8 in a content higher than that in Example 6, laminates cannot be made due to insufficient curing agent.

[0140] By comparing Comparative Example 9 with Example 6, it can be seen that the copper-clad laminate prepared from BHPPO and the halogen-free epoxy resin in Comparative Example 9 has worse dielectric properties, poor heat resistance and heat and humidity resistance, high water absorption rate and low Tg. By comparing Comparative Example 10 with Example 6, it can be seen that the copper-clad laminate prepared from BCPPO and the halogen-free epoxy resin in Comparative Example 10 has worse dielectric properties, poor heat resistance and heat and humidity resistance and high water absorption rate.

[0141] In Comparative Examples 11 and 12, organic carboxylic acid and phenol are used together as an epoxy curing agent. Due to higher rate difference of the reaction between carboxylic acid and epoxy and between phenol and epoxy, carboxylic acid rapidly participates in the curing reaction as a result, while phenol hardly participates in the reaction in the system or in a low amount. It acts as a plasticizer in the curing system, resulting in an extremely low Tg after curing and a low T288. Moreover, due to the presence of phenolic hydroxyl group with a high polarity, there are shortcomings such as poor dielectric properties and high water absorption rate.

[0142] From the above results, it can be seen that, by replacing ODOBP and FRX as well as BHPPO and BCPPO with the phosphorus-containing active ester of the present invention, the prepregs and laminates for printed circuit boards made from the active ester and components such as a halogen-free epoxy resin have a glass transition temperature of up to 245 C., excellent dielectric properties, water absorption controlled in the range of 0.06-0.14%, high heat resistance, excellent heat and humidity resistance and good processability, excellent flame retardant efficiency, and can achieve UL94 V-0 when P content is 1.5%.

[0143] As described above, as compared with general laminates, the prepregs and laminates for printed circuit boards made from the halogen-free thermosetting resin composition provided by the present invention have high glass transition temperature, excellent dielectric properties, low water absorption, high heat resistance, excellent heat and humidity resistance and good processability, and can achieve halogen-free flame retardancy and reach UL94 V-0.

[0144] The above-described examples are merely preferred examples of the present invention. Those ordinarily skilled in the art can make various other corresponding changes and modifications in accordance with the technical solutions and technical concept of the present invention, and all such changes and modifications shall fall within the scope of the claims of the present invention.