Thermosetting resin composition and use thereof

Abstract

The present invention relates to a thermosetting resin composition, which comprises: (A) cyanate ester compound and/or cyanate ester prepolymer; and (B) polyphosphonate ester and/or phosphonate-carbonate copolymer. The thermosetting resin composition provided by the present invention has low dielectric constant and dielectric loss tangent. The prepreg and copper clad laminate made from the above-mentioned thermosetting resin composition have excellent dielectric properties and wet-heat resistance, UL94 V-0 flame resistance, and good processability.

Claims

1. A thermosetting resin composition, wherein the resin composition comprises: (A) 50-90 weight parts of novolac type cyanate ester compound; ##STR00015## wherein, R.sub.4, R.sub.12, and R.sub.13 are each independently selected from the group consisting of hydrogen atom, substituted or unsubstituted C1-C4 straight chain alkyl and substituted or unsubstituted C1-C4 branched alkyl; K is any integer from 1 to 7, (B) 10-50 weight parts of phosphonate-carbonate copolymer ##STR00016## m.sub.1 is any integer from 1 to 100; n.sub.4 is any integer from 1 to 75; and (C) 15-30 weight parts of naphthol type novolac epoxy resin (I) or biphenyl type novolac epoxy resin (II); ##STR00017## wherein a.sub.1, is any integer from 1 to 10, and R.sub.7 is selected from the group consisting of hydrogen atom, substituted or unsubstituted C1-C5 straight chain alkyl and substituted or unsubstituted C1-C5 branched alkyl; ##STR00018## n is any integer from 1 to 10.

2. The thermosetting resin composition according to claim 1, wherein the thermosetting resin composition further comprises (D) filler; the filler is selected from organic fillers and/or inorganic fillers; the inorganic filler is one or more selected from the group consisting of nonmetal oxide, metal nitride, non-metal nitride, inorganic hydrate, inorganic salt, metal hydrate and inorganic phosphorus; the organic filler is any one or a mixture of at least two selected from the group of polytetrafluoroethylene powder, polyphenylene sulfide, organophosphorus compounds and polyether sulfone powder; the median particle diameter of the filler is 0.01-50m; based on the total weight of the component(A), component(B) and component(C) of 100parts, the addition amount of the component (D) is 51000 parts by weight.

3. The thermosetting resin composition according to claim 1, wherein the thermosetting resin composition further comprises component (E) catalyst; the catalyst is one or more selected from the group consisting of organic metal compounds, imidazole compounds and derivatives thereof, and tertiary amine; the metal is one or more selected from the group consisting of zinc, copper, iron, tin, cobalt and aluminum; based on the total weight of the component (A), component (B) and component (C) of 100 parts, the addition amount of component (E) catalyst is 0.01-1.0 parts by weight.

4. The thermosetting resin composition according to claim 1, wherein the thermosetting resin composition further comprises: (D) filler of 5-1000 parts by weight based on the total weight of the component (A), component (B) and component (C) of 100 parts; and (E) catalyst of 0.01-1.0 parts by weight based on the total weight of the component (A), component (B) and component (C) of 100 parts.

5. A prepreg, wherein the prepreg comprises the enhancement material and the thermosetting resin composition according to claim 1 which adheres to the enhancement material by impregnation and drying.

6. A laminate, wherein the laminate comprises at least one prepreg according to claim 5.

7. A high-frequency circuit board, wherein the high-frequency circuit board comprises at least one prepreg according to claim 5 and the copper foils covered on both sides of stacked prepregs.

Description

DETAILED DESCRIPTION

(1) To better illustrate the present invention and understand technical solution of the present invention, the typical but non-limiting embodiments of the present invention are as follows:

(2) Addressing the prepared copper clad laminate mentioned above, dielectric constant, dielectric loss factor, glass transition temperature and wet-heat resistance are all measured, and further described referring to the following embodiments.

(3) Embodiment 1

(4) A container is taken, added with bisphenol A type cyanate ester resin BA230S (LONZA Company, Cyano equivalent is 139 g/eq) of 80 parts by weight, then added with phosphonate-carbonate copolymer FRX CO 95 (FRX Polymers Company, phosphorous content is 10.8%) of 20 parts by weight and stirred uniformly. Then it is added with catalyst Zinc caprylate of 0.08 parts by weight and solvent butanone and stirred uniformly to obtain a glue solution. Glass fiber cloth (model number: 2116, thickness: 0.08 mm) is impregnated into the glue solution mentioned above, controlled to an appropriate thickness, and then dried to remove the solvent to obtain the prepreg. Several pieces of prepared prepregs are stacked, one piece of copper foils is cladded on both sides of the stacked prepregs, and they are cured in a hot press machine to obtain a copperclad laminate. The cured temperature is 150-250 C., cured press is 25-60 kg/cm.sup.2 and cured time is 90-120 min.

(5) Embodiment 2

(6) A container is taken, added with bisphenol A type cyanate ester resin BA230S (LONZA Company, Cyano equivalent is 139 g/eq) of 55 parts by weight, then added with phosphonate-carbonates copolymer FRX CO 95 (FRX Polymers Company, phosphorous content is 10.6%) of 45 parts by weight and stirred uniformly. Then it is added with catalyst Zinc caprylate of 0.035 parts by weight and solvent butanone and stirred uniformly to obtain a glue solution. Glass fiber cloth (model number: 2116, thickness: 0.08 mm) is impregnated into the glue solution mentioned above, controlled to an appropriate thickness, and then dried to remove the solvent to obtain the prepreg. Several pieces of prepared prepregs are stacked, one piece of copper foils is cladded on both sides of the stacked prepregs, and they are cured in a hot press machine to obtain a copperclad laminate. The cured temperature is 150-250 C., cured press is 25-60 kg/cm.sup.2 and cured time is 90-120 min.

(7) Embodiment 3

(8) A container is taken, added with novolac type cyanate ester resin PT-30 (LONZA Company, Cyano equivalent is 139 g/eq) of 90 parts by weight, then added with polyphosphonate ester HM1100 (FRX Polymers Company, Phosphorus content is 10.8%) of 10 parts by weight and stirred uniformly. Then it is added with catalyst Zinc caprylate of 0.035 parts by weight and solvent butanone and stirred uniformly to obtain a glue solution. Glass fiber cloth (model number: 2116, thickness: 0.08 mm) is impregnated into the glue solution mentioned above, controlled to an appropriate thickness, and then dried to remove the solvent to obtain the prepreg. Several pieces of prepared prepregs are stacked, one piece of copper foils is cladded on both sides of the stacked prepregs, and they are cured in a hot press machine to obtain a copperclad laminate. The cured temperature is 150-250 C., cured press is 25-60 kg/cm.sup.2 and cured time is 90-120 min.

(9) Embodiment 4

(10) A container is taken, added with novolac type cyanate ester resin PT-30 (LONZA Company) of 55 parts by weight and dicyclopentadiene type novolac epoxy resin HP-7200H (Japan DIC Company, EEW is 278 g/eq) of 30 parts by weight, then added with phosphonate-carbonates copolymer FRX CO3000 (FRX Polymers Company, Phosphorus content is 10.6%) of 15 parts by weight and stirred uniformly. Then it is added with catalyst Zinc caprylate of 0.035 parts by weight and solvent butanone and stirred uniformly to obtain a glue solution. Glass fiber cloth (model number: 2116, thickness: 0.08 mm) is impregnated into the glue solution mentioned above, controlled to an appropriate thickness, and then dried to remove the solvent to obtain the prepreg. Several pieces of prepared prepregs are stacked, one piece of copper foils is cladded on both sides of the stacked prepregs, and they are cured in a hot press machine to obtain a copperclad laminate. The cured temperature is 150-250 C., cured press is 25-60 kg/cm.sup.2 and cured time is 90-120 min.

(11) Embodiment 5

(12) A container is taken, added with novolac type cyanate ester resin PT-30 (LONZA Company) of 55 parts by weight and alkylbenzene type novolac epoxy resin NC-2000L (Nippon Kayaku Co., Ltd., EEW is 238 g/eq) of 30 parts by weight, then added with polyphosphonate ester FRX OL5000 (FRX Polymers Company, Phosphorus content is 10.8%) of 15 parts by weight and stirred uniformly. Then it is added with catalyst Zinc caprylate of 0.035 parts by weight and solvent butanone and stirred uniformly to obtain a glue solution. Glass fiber cloth (model number: 2116, thickness: 0.08 mm) is impregnated into the glue solution mentioned above, controlled to an appropriate thickness, and then dried to remove the solvent to obtain the prepreg. Several pieces of prepared prepregs are stacked, one piece of copper foils is cladded on both sides of the stacked prepregs, and they are cured in a hot press machine to obtain a copperclad laminate. The cured temperature is 150-250 C., cured press is 25-60 kg/cm.sup.2 and cured time is 90-120 min.

(13) Embodiment 6

(14) A container is taken, added with novolac type cyanate ester resin PT-30 (LONZA Company) of 60 parts by weight and naphthol type novolac epoxy resin NC-7000L (Nippon Kayaku Co., Ltd., EEW is 232 g/eq) of 30 parts by weight, then added with phosphonate-carbonates copolymer FRX CO6000 (FRX Polymers Company, Phosphorus content is 10.6%) of 10 parts by weight and stirred uniformly. Then it is added with catalyst Zinc caprylate of 0.035 parts by weight and solvent butanone and stirred uniformly to obtain a glue solution. Glass fiber cloth (model number: 2116, thickness: 0.08 mm) is impregnated into the glue solution mentioned above, controlled to an appropriate thickness, and then dried to remove the solvent to obtain the prepreg. Several pieces of prepared prepregs are stacked, one piece of copper foils is cladded on both sides of the stacked prepregs, and they are cured in a hot press machine to obtain a copperclad laminate. The cured temperature is 150-250 C., cured press is 25-60 kg/cm.sup.2 and cured time is 90-120 min.

(15) Embodiment 7

(16) A container is taken, added with bisphenol A type cyanate ester resin BA230S (LONZA Company, Cyano equivalent is 139 g/eq) of 60 parts by weight and bisphenol type novolac epoxy resin N690 (Japan DIC Company, EEW is 205 g/eq) of 15 parts by weight, then added with phosphonate-carbonates copolymer FRX CO6000 (FRX Polymers Company, Phosphorus content is 10.6%) of 25 parts by weight and stirred uniformly. Then it is added with catalyst Zinc caprylate of 0.035 parts by weight and solvent butanone and stirred uniformly to obtain a glue solution. Glass fiber cloth (model number: 2116, thickness: 0.08 mm) is impregnated into the glue solution mentioned above, controlled to an appropriate thickness, and then dried to remove the solvent to obtain the prepreg. Several pieces of prepared prepregs are stacked, one piece of copper foils is cladded on both sides of the stacked prepregs, and they are cured in a hot press machine to obtain a copperclad laminate. The cured temperature is 150-250 C., cured press is 25-60 kg/cm.sup.2 and cured time is 90-120 min.

(17) Embodiment 8

(18) A container is taken, added with novolac type cyanate ester resin PT-30 (LONZA Company) of 60 parts by weight, bisphenol novolac type epoxy resin N690 (Japan DIC Company, EEW is 205 g/eq) of 15 parts by weight, then added with phosphonate-carbonate copolymer FRX CO6000 (FRX Polymers Company, Phosphorus content is 10.6%) of 25 parts by weight and stirred uniformly. Then it is added with catalyst Zinc caprylate of 0.035 parts by weight and solvent butanone and stirred uniformly to obtain a glue solution. Glass fiber cloth (model number: 2116, thickness: 0.08 mm) is impregnated into the glue solution mentioned above, controlled to an appropriate thickness, and then dried to remove the solvent to obtain the prepreg. Several pieces of prepared prepregs are stacked, one piece of copper foils is cladded on both sides of the stacked prepregs, and they are cured in a hot press machine to obtain a copperclad laminate. The cured temperature is 150-250 C., cured press is 25-60 kg/cm.sup.2 and cured time is 90-120 min.

(19) Embodiment 9

(20) A container is taken, added with bisphenol A type cyanate ester resin BA230S (LONZA Company, Cyano equivalent is 139 g/eq) of 60 parts by weight and bisphenol novolac type epoxy resin N690 (Japan DIC Company, EEW is 205 g/eq) of 15 parts by weight, then added with polyphosphonate ester FRX 100 (FRX Polymers Company, Phosphorus content is 10.8%) of 30 parts by weight and stirred uniformly. Then it is added with catalyst Zinc caprylate of 0.035 parts by weight and solvent butanone and stirred uniformly to obtain a glue solution. Glass fiber cloth (model number: 2116, thickness: 0.08 mm) is impregnated into the glue solution mentioned above, controlled to an appropriate thickness, and then dried to remove the solvent to obtain the prepreg. Several pieces of prepared prepregs are stacked, one piece of copper foils is cladded on both sides of the stacked prepregs, and they are cured in a hot press machine to obtain a copperclad laminate. The cured temperature is 150-250 C., cured press is 25-60 kg/cm.sup.2 and cured time is 90-120 min.

(21) Embodiment 10

(22) A container is taken, added with novolac type cyanate ester resin PT-30 (LONZA Company) of 60 parts by weight and dicyclopentadiene type epoxy resin HP-7200H (Japan DIC Company, EEW is 278 g/eq) of 6 parts by weight, then added with phosphonate-carbonate copolymer FRX CO6000 (FRX Polymers Company, Phosphorus content is 10.6%) of 40 parts by weight and stirred uniformly. Then it is added with catalyst Zinc caprylate of 0.035 parts by weight and solvent butanone and stirred uniformly to obtain a glue solution. Glass fiber cloth (model number: 2116, thickness: 0.08 mm) is impregnated into the glue solution mentioned above, controlled to an appropriate thickness, and then dried to remove the solvent to obtain the prepreg. Several pieces of prepared prepregs are stacked, one piece of copper foils is cladded on both sides of the stacked prepregs, and they are cured in a hot press machine to obtain a copperclad laminate. The cured temperature is 150-250 C., cured press is 25-60 kg/cm.sup.2 and cured time is 90-120 min.

(23) Embodiment 11

(24) A container is taken, added with novolac type cyanate ester resin PT-30 (LONZA Company) of 70 parts by weight and dicyclopentadiene type epoxy resin HP-7200H (Japan DIC Company, EEW is 278 g/eq) of 35 parts by weight, then added with phosphonate-carbonate copolymer FRX CO6000 (FRX Polymers Company, Phosphorus content is 10.6%) of 30 parts by weight and stirred uniformly. Then it is added with catalyst Zinc caprylate of 0.035 parts by weight and solvent butanone and stirred uniformly to obtain a glue solution. Glass fiber cloth (model number: 2116, thickness: 0.08 mm) is impregnated into the glue solution mentioned above, controlled to an appropriate thickness, and then dried to remove the solvent to obtain the prepreg. Several pieces of prepared prepregs are stacked, one piece of copper foils is cladded on both sides of the stacked prepregs, and they are cured in a hot press machine to obtain a copperclad laminate. The cured temperature is 150-250 C., cured press is 25-60 kg/cm.sup.2 and cured time is 90-120 min.

(25) Embodiment 12

(26) A container is taken, added with novolac type cyanate ester resin PT-30 (LONZA Company) of 60 parts by weight and alkylbenzene type novolac epoxy resin NC-2000L (Nippon Kayaku Co., Ltd., EEW is 238 g/eq) of 12 parts by weight, then added with phosphonate-carbonate copolymer FRX CO6000 (FRX Polymers Company, Phosphorus content is 10.6%) of 40 parts by weight and stirred uniformly. Then it is added with silicon dioxide of 15.6 parts by weight and solvent butanone, and stirred uniformly to obtain a glue solution. Glass fiber cloth (model number: 2116, thickness: 0.08 mm) is impregnated into the glue solution mentioned above, controlled to an appropriate thickness, and then dried to remove the solvent to obtain the prepreg. Several pieces of prepared prepregs are stacked, one piece of copper foils is cladded on both sides of the stacked prepregs, and they are cured in a hot press machine to obtain a copperclad laminate. The cured temperature is 150-250 C., cured press is 25-60 kg/cm.sup.2 and cured time is 90-120 min.

(27) Embodiment 13

(28) A container is taken, added with novolac type cyanate ester resin PT-30 (LONZA Company) of 70 parts by weight and naphthol type novolac epoxy resin NC-7000L (Nippon Kayaku Co., Ltd., EEW is 232 g/eq) of 30 parts by weight, then added with phosphonate-carbonate copolymer FRX CO6000 (FRX Polymers Company, Phosphorus content is 10.6%) of 30 parts by weight and stirred uniformly. Then it is added with silicon dioxide subject to surface treatment with vinyl trimethoxy silane of 150 parts by weight and solvent butanone, and stirred uniformly to obtain a glue solution. Glass fiber cloth (model number: 2116, thickness: 0.08 mm) is impregnated into the glue solution mentioned above, controlled to an appropriate thickness, and then dried to remove the solvent to obtain the prepreg. Several pieces of prepared prepregs are stacked, one piece of copper foils is cladded on both sides of the stacked prepregs, and they are cured in a hot press machine to obtain a copperclad laminate. The cured temperature is 150-250 C., cured press is 25-60 kg/cm.sup.2 and cured time is 90-120 min.

(29) Embodiment 14

(30) A container is taken, added with novolac type cyanate ester resin PT-30 (LONZA Company) of 70 parts by weight and biphenyl type novolac epoxy resin NC-3000H (Nippon Kayaku Co., Ltd., EEW is 288 g/eq) of 30 parts by weight, then added with phosphonate-carbonate copolymer FRX CO6000 (FRX Polymers Company, Phosphorus content is 10.6%) of 30 parts by weight and stirred uniformly. Then it is added with silicon dioxide SC2050 (Admatechs, D50: 0.5 m) of 100 parts by weight and solvent butanone, and stirred uniformly to obtain a glue solution. Glass fiber cloth (model number: 2116, thickness: 0.08 mm) is impregnated into the glue solution mentioned above, controlled to an appropriate thickness, and then dried to remove the solvent to obtain the prepreg. Several pieces of prepared prepregs are stacked, one piece of copper foils is cladded on both sides of the stacked prepregs, and they are cured in a hot press machine to obtain a copperclad laminate. The cured temperature is 150-250 C., cured press is 25-60 kg/cm.sup.2 and cured time is 90-120 min.

COMPARATIVE EXAMPLE 1

(31) A container is taken, added with novolac type cyanate ester resin PT-30 (LONZA Company) of 60 parts by weight and bisphenol novolac type epoxy resin N690 (Japan DIC Company, EEW is 205 g/eq) of 15 parts by weight, then added with flame retardant phosphonate ester PX-200 (Daihachi Chemical Industry, Phosphorus content is 9%) of 25 parts by weight and stirred uniformly. Then it is added with catalyst Zinc caprylate of 0.035 parts by weight and solvent butanone, and stirred uniformly to obtain a glue solution. Glass fiber cloth (model number: 2116, thickness: 0.08 mm) is impregnated into the glue solution mentioned above, controlled to an appropriate thickness, and then dried to remove the solvent to obtain the prepreg. Several pieces of prepared prepregs are stacked, one piece of copper foils is cladded on both sides of the stacked prepregs, and they are cured in a hot press machine to obtain a copperclad laminate. The cured temperature is 150-250 C., cured press is 25-60 kg/cm.sup.2 and cured time is 90-120 min.

COMPARATIVE EXAMPLE 2

(32) A container is taken, added with bisphenol A type cyanate ester resin BA230S (LONZA Company, Cyano equivalent is 139 g/eq) of 60 parts by weight and bisphenol novolac type epoxy resin N690 (Japan DIC Company, EEW is 205 g/eq) of 15 parts by weight, then added with phosphazene flame retardant SP-100 (Otsuka Chemical, Phosphorus content is 13.4%) of 25 parts by weight and stirred uniformly. Then it is added with catalyst Zinc caprylate of 0.035 parts by weight and solvent butanone, and stirred uniformly to obtain a glue solution. Glass fiber cloth (model number: 2116, thickness: 0.08 mm) is impregnated into the glue solution mentioned above, controlled to an appropriate thickness, and then dried to remove the solvent to obtain the prepreg. Several pieces of prepared prepregs are stacked, one piece of copper foils is cladded on both sides of the stacked prepregs, and they are cured in a hot press machine to obtain a copperclad laminate. The cured temperature is 150-250 C., cured press is 25-60 kg/cm.sup.2 and cured time is 90-120 min.

COMPARATIVE EXAMPLE 3

(33) A container is taken, added with bisphenol A type cyanate ester resin BA230S (LONZA Company, Cyano equivalent is 139 g/eq) of 60 parts by weight and bisphenol novolac type epoxy resin N690 (Japan DIC Company, EEW is 205 g/eq) of 15 parts by weight, then added with flame retardant phosphate ester FP-600 (ADEKA, Phosphorus content is 8.9%) of 30 parts by weight and stirred uniformly. Then it is added with catalyst Zinc caprylate of 0.035 parts by weight and solvent butanone, and stirred uniformly to obtain a glue solution. Glass fiber cloth (model number: 2116, thickness: 0.08 mm) is impregnated into the glue solution mentioned above, controlled to an appropriate thickness, and then dried to remove the solvent to obtain the prepreg. Several pieces of prepared prepregs are stacked, one piece of copper foils is cladded on both sides of the stacked prepregs, and they are cured in a hot press machine to obtain a copperclad laminate. The cured temperature is 150-250 C., cured press is 25-60 kg/cm.sup.2 and cured time is 90-120 min.

COMPARATIVE EXAMPLE 4

(34) A container is taken, added with novolac type cyanate ester resin PT-30 (LONZA Company, Cyano equivalent is 139 g/eq) of 55 parts by weight and dicyclopentadiene type epoxy resin HP-7200H (Japan DIC Company, EEW is 278 g/eq) of 30 parts by weight, then stirred uniformly. Then it is added with catalyst Zinc caprylate of 0.035 parts by weight and solvent butanone, and stirred uniformly to obtain a glue solution. Glass fiber cloth (model number: 2116, thickness: 0.08 mm) is impregnated into the glue solution mentioned above, controlled to an appropriate thickness, and then dried to remove the solvent to obtain the prepreg. Several pieces of prepared prepregs are stacked, one piece of copper foils is cladded on both sides of the stacked prepregs, and they are cured in a hot press machine to obtain a copperclad laminate. The cured temperature is 150-250 C., cured press is 25-60 kg/cm.sup.2 and cured time is 90-120 min.

(35) TABLE-US-00001 TABLE 1 Physical Property Data of Each Embodiment and Comparative Example performance Embodiment Embodiment Embodiment Embodiment Embodiment Embodiment index 1 2 3 4 5 6 Tg(DMA)/ C. 268 260 325 280 270 265 Dk(5G) 3.8 3.85 3.8 3.7 3.8 3.9 Df(5G) 0.0055 0.006 0.0065 0.006 0.0055 0.005 Water 0.10 0.13 0.15 0.13 0.12 0.10 Absorption, % Wet-heat 3/3 3/3 3/3 3/3 3/3 2/3 Resistance Flame V-0 V-0 V-0 V-0 V-0 V-0 Resistance

(36) TABLE-US-00002 TABLE 2 Physical Property Data of Each Embodiment and Comparative Example (continued) Embodiment Embodiment Embodiment Embodiment Embodiment performance index 7 8 9 10 11 Tg(DMA)/ C. 245 335 245 325 310 Dk(5G) 3.85 3.85 3.85 3.85 3.84 Df(5G) 0.0065 0.0075 0.0065 0.0065 0.0065 water Absorption, % 0.12 0.13 0.12 0.15 0.15 Wet-heat Resistance 3/3 3/3 3/3 3/3 3/3 Flame Resistance V-0 V-0 V-0 V-0 V-0

(37) TABLE-US-00003 TABLE 3 Physical Property Data of Each Embodiment and Comparative Example (continued) Embodiment Embodiment Embodiment performance index 12 13 14 Tg(DMA)/ C. 254 310 315 Dk(5G) 3.8 3.9 3.9 Df(5G) 0.0065 0.005 0.0045 Water Absorption, % 0.11 0.10 0.09 Wet-heat Resistance 3/3 3/3 3/3 Flame resistance V-0 V-0 V-0

(38) TABLE-US-00004 TABLE 4 Physical Property Data of Each Embodiments and Comparative Examples (continued) performance Comparative Comparative Comparative Comparative index Example 1 Example 2 Example 3 Example 4 Tg(DMA)/ C. 150 180 160 320 Dk(5G) 3.95 3.95 3.95 3.8 Df(5G) 0.009 0.006 0.009 0.009 Water 0.25 0.25 0.25 0.3 Absorption, % Wet-heat 0/3 1/3 0/3 3/3 Resistance Flame V-0 V-1 V-0 V-1 resistance

(39) The methods of performance testing above are as follows:

(40) (1) glass transition temperature (Tg): measuring with DMA assay. Take measurement with the DMA assay specified in IPC-TM-650 2.4.24;

(41) (2) dielectric constant and dielectric loss factor: take measurement with SPDR method;

(42) (3) wet-heat resistance evaluation: evaluating the substrate lamina after the copper foil on the surface of copper-clad laminate was etched; treating the substrate lamina in a pressure cooker at 120 C., 105 KPa for 4 hours; then impregnating the substrate lamina in a tin furnace at 288 C.; recording the corresponding time once the substrate lamina is delaminated; ending the evaluation if no bubble or delamination occurred after the substrate lamina was in a tin furnace for 5 min;

(43) (4) flame resistance: measuring with UL94 standard method.

(44) Physical Properties Analysis

(45) It is shown by the physical property data in table 1-4: in Comparative Examples 1-3, the prior phosphonate ester is used as flame retardant and equated to plasticizer in the system due to its low molecular weight and non-reactivity. Compared with Embodiments 1-14, the glass transition temperature is obviously reduced by phosphonate ester, thereby the wet-heat resistance is poor, water-absorption rate is high, and the requirements of heat resistance of present lead-free technology cannot be met. In Comparative Example 4, excellent heat resistance and low water-absorption can be achieved without addition of flame retardant, but flame resistance is poor, lower than V-0 level, thus it can not meet the requirement of the laminates.

(46) In summary, compared with the common copper-clad laminate, the copper-clad laminate of the present invention achieves halogen-free flame resistance, and at the same time has excellent dielectric properties, higher glass transition temperature, and good wet-heat resistance, thus it is suitable for the application field of lead-free high speed communication.

(47) The above are merely preferred embodiments of the present invention. Those skilled in the art can make numerous variations and changes according to the technical solution and spirit of the present invention, which all fall in the protection scope of the claims of the present invention.

(48) The applicant stated that the present invention employ the embodiments above to describe the detailed components the present invention, but the present invention is not limited to the detailed components above, i.e. it does not mean that the present invention must rely on the detailed components above to be implemented. Persons skilled in the art should understand, any improvement of the present invention, the equivalent replacement to the raw materials of the present invention product, addition of auxiliary ingredients, selection of specific mode, etc. all fall within the protection scope and disclosure scope of the present invention.