Low dielectric resin composition with phosphorus-containing flame retardant and preparation method and application thereof

Abstract

The invention belongs to the technical field of low dielectric resin compositions, and discloses a low dielectric resin composition with phosphorus-containing flame retardant and a prepreg, resin film, laminate and printed circuit board prepared therefrom. The composition comprises the following components: (A) phosphorus-containing flame retardant; (B) vinyl compound. The phosphorus-containing flame retardant has a structure as shown in formula (I). ##STR00001## In the present invention, diphenylphosphine oxide is derivatized, and prepared a phosphorus-containing flame retardant, which has no reactive functional groups, has better dielectric properties, and has high melting point, and upon combining with a vinyl compound, a resin composition is obtained, and a laminate having low thermal expansion ratio, high heat resistance, high glass transition temperature, and low dielectric constant and dissipation factor, can be made from the resin composition, and can effectively achieve the flame resistance effect of UL94 V-0 without using halogen-containing flame retardant, and can be used in the preparation of prepregs, resin films, resin coated coppers, flexible resin coated coppers, laminates and printed circuit boards.

Claims

1. A low dielectric resin composition with phosphorus-containing flame retardant, comprising the following components: (A) 25 to 90 parts by weight of a phosphorus-containing flame retardant; and (B) 100 parts by weight of a vinyl compound; wherein, the phosphorus-containing flame retardant has a structure as shown in formula (I): ##STR00010## wherein, A is a covalent bond, C6C12 arylene, C3C12 cycloalkylene, C6C12 cycloalkenylene, methylene or C2C12 alkylene; R.sub.1 and R.sub.2 are the same or different, and are each a H, alkoxy, aryloxy, alkyl, aryl or silyl, respectively; R.sub.3 and R.sub.4 are the same or different, and are each a H, hydroxyl, and C1C6 alkyl, respectively, or one and only one of R.sub.3 and R.sub.4 forms a carbonyl with a C; each of n is a positive integer of 16 independently, wherein the vinyl compound is a vinyl polyphenylene ether resin having a structure as shown below in formula (XVI) ##STR00011## wherein, (OXO) refers to ##STR00012## (YO) refers to ##STR00013## R.sub.5 and R.sub.6 are each a hydrogen atom, R.sub.7, R.sub.8, R.sub.9, R.sub.10 and R.sub.11 are the same or different, and are each a hydrogen atom, halogen atom, alkyl, or halogen-substituted alkyl respectively; R.sub.12, R.sub.13, R.sub.18 and R.sub.19 are the same or different, and are each a halogen atom, C1-C6 alkyl or phenyl respectively; R.sub.14, R.sub.15, R.sub.16 and R.sub.17 are the same or different, and are each a hydrogen atom, halogen atom, C1-C6 alkyl or phenyl respectively; R.sub.20, R.sub.21, R.sub.22, R.sub.23, R.sub.24, R.sub.25, R.sub.26 and R.sub.27 are the same or different, and are each a halogen atom, C1-C6 alkyl, phenyl or hydrogen atom; A is a C1-C20 linear, branched, or cyclic alkylene; R.sub.28 and R.sub.29 are the same or different, and are each a halogen atom, C1-C6 alkyl or phenyl respectively; R.sub.30 and R.sub.31 are the same or different, and are each a hydrogen atom, halogen atom, C1C6 alkyl or phenyl respectively; Z represents an organic group having at least one carbon atom; and a and b are each a natural number of 130, respectively.

2. The low dielectric resin composition with phosphorus-containing flame retardant of claim 1, wherein the phosphorus-containing flame retardant has at least one of the structures as shown in the following formulae (II)(XV): ##STR00014## ##STR00015## ##STR00016## wherein, TMS represents trimethylsilyl.

3. The low dielectric resin composition with phosphorus-containing flame retardant of claim 1, further comprising at least one of vinylbenzyl compound resin, polyolefin compound, and maleimide resin.

4. The low dielectric resin composition with phosphorus-containing flame retardant of claim 3, wherein the vinylbenzyl compound resin is vinylbenzyl etherified-dicyclopentadiene-phenol resin.

5. The low dielectric resin composition with phosphorus-containing flame retardant of claim 3, wherein the polyolefin compound is at least one of styrene-butadiene-divinylbenzene copolymer, hydrogenated styrene-butadiene-divinylbenzene copolymer, styrene-butadiene-maleic anhydride copolymer, polybutadiene-urethane-methyl methacrylate copolymer, styrene-butadiene copolymer, polybutadiene homopolymer, styrene-isoprene-styrene copolymer, maleinized styrene-butadiene copolymer, methyl styrene copolymer, petroleum resin, and cyclic olefin copolymer; the maleimide resin is at least one of 4,4-bismaleimido diphenylmethane, phenylmethane maleimide oligomer, N,N-metaphenylene bismaleimide, bisphenol A biphenyl ether bismaleimide, 3,3-dimethyl-5,5-diethyl-4,4-diphenylmethane bismaleimide, N,N-(4-methyl-1,3-phenylene)bismaleimide, 1,6-bismaleimido-(2,2,4-trimethyl)hexane, 2,3-dimethylphenyl maleimide, 2,6-dimethylphenyl maleimide, N-phenyl maleimide, and the prepolymer of the abovementioned compound.

6. The low dielectric resin composition with phosphorus-containing flame retardant of claim 1, wherein the phosphorus content in the resin composition with phosphorus-containing flame retardant is 23.5 wt %.

7. The low dielectric resin composition with phosphorus-containing flame retardant of claim 1, wherein the melting point of the phosphorus-containing flame retardant is higher than 300 C.

8. The low dielectric resin composition with phosphorus-containing flame retardant of claim 1, further comprising at least one of the following additives: curing accelerator, solvent, crosslinking agent, silane coupling agent, and inorganic filler.

Description

DESCRIPTION OF DRAWINGS

(1) FIG. 1 is a TGA (Thermogravimetric Analysis) diagram of the phosphorus-containing flame retardant prepared in the example 1.

(2) FIG. 2 is a DSC melting point diagram of the phosphorus-containing flame retardant prepared in example 1.

(3) FIG. 3 is a FTIR spectrogram of DPPO.

(4) FIG. 4 is a FTIR spectrogram of the phosphorus-containing flame retardant prepared in example 1.

DESCRIPTION OF EMBODIMENTS

(5) Hereinafter the present invention is further described in detail in combination with the examples and the accompanying drawings, but the embodiments of the present invention are not limited thereto.

(6) The chemical names used in the following examples are as follows:

(7) DPPO: diphenylphosphine oxide, purchased from Eumate International Corp.

(8) SA-9000: methylacrylate-terminated bisphenol A polyphenylene ether resin, purchased from Sabic Company.

(9) OPE-2st: vinylbenzyl ether-terminated diphenyl polyphenylene ether resin, purchased from Mitsubishi Gas Chemical Company.

(10) Ricon184Ma6: styrene-butadiene-maleic anhydride copolymer, purchased from Cray Valley Company.

(11) Ricon257: styrene-butadiene-divinylbenzene copolymer, purchased from Cray Valley Company.

(12) Homide108: phenylmethane maleimide, purchased from Hos-Technik Company.

(13) SPB-100: phosphazene compound, purchased from Otsuka Chemical Co., Ltd.

(14) PX-200: resorcinol bis[di(2,6-dimethylphenyl)phosphate], purchased from Daihachi Chemical Industry Co., Ltd.

(15) XZ92741: DOPO-bisphenol A phenolic novolac resin, purchased from Dow chemical.

(16) DCP: dicumyl peroxide, purchased from Eumate International Corp.

(17) R-45vt: polybutadiene-urethane-methyl methacrylate, purchased from Cray Valley Company.

(18) SQ-5500: spherical silicon dioxide treated with alkyl siloxane compound, purchased from Admatechs Company.

(19) DP-85T: vinylbenzyl etherified-dicyclopentadiene-phenol resin, purchased from Chin Yee Chemical Industries Ltd.

(20) PPE/VBE 7205L: modified vinyl polyphenylene ether, purchased from Chin Yee Chemical Industries Ltd.

Example 1: Preparation of Phosphorus-Containing Flame Retardant of Formula (III)

(21) 206 g of DPPO (Diphenylphosphine Oxide), 90 g of dichloro-p-xylene, and 1200 g of 1,2-dichlorobenzene were stirred and mixed, then heated and reacted for 12 to 24 hours at 160 C. under nitrogen atmosphere, cooled down to the ambient temperature and filtrated, dried in vacuum, thus obtaining Compound A as shown in formula (III), as a white powder, with a phosphorus content in the compound A of about 12%.

(22) Analysis: the Td value measured from the TGA test was: 379 C. (at 5% decomposition, the results shown in FIG. 1); the melting point measured from the DSC test was 334 C. (the results shown in FIG. 2), whereas in the prior art, the melting point of the phosphazene compound (SPB-100) was 110 C., the melting point of the condensed phosphate (PX-200) was 105 C., and the phosphorus-containing phenolic novolac resin, such as DOPO-bisphenol A phenolic novolac resin, was a liquid resin at the ambient temperature. Therefore, the phosphorus-containing flame retardant prepared in the present invention had a higher melting point.

(23) The DPPO and Compound A were carried out an infrared scanning, and the peak analysis were shown in tables 12 and FIGS. 34, and as shown in the figures, the PH functional group of the DPPO had a peak at 2300 cm.sup.12354 cm.sup.1 on FTIR, which was disappeared in the infrared spectra of the synthesized Compound A, which demonstrated that the object product, Compound A having a structure as shown in formula (III), was prepared successfully.

(24) ##STR00009##

(25) TABLE-US-00001 TABLE 1 The peak analysis of the infrared spectrum of the DPPO No. Position Intensity No. Position Intensity 1 3835.72 45.8092 2 3799.08 45.9235 3 3747.01 45.5569 4 3646.73 43.2362 5 3438.46 33.4289 6 3056.62 41.4701 7 2337.3 43.0893 8 1826.26 48.9266 9 1648.84 44.5571 10 1590.99 45.4855 11 1540.85 49.9950 12 1484.92 48.6728 13 1438.64 34.1160 14 1398.14 51.8242 15 1313.29 51.6502 16 1182.15 28.7802 17 1126.22 31.0794 18 1070.3 49.3251 19 1025.94 52.9918 20 948.806 35.1476 21 921.807 44.3150 22 856.239 57.5654 23 746.317 38.9094 24 721.247 45.3299 25 696.177 30.0476 26 551.542 50.2220 27 524.543 40.5313 28 493.688 46.5779 29 404.978 72.7421

(26) TABLE-US-00002 TABLE 2 The peak analysis of the infrared spectrum of Compound A No. Position Intensity No. Position Intensity 1 3442.31 46.5563 2 3073.98 48.3190 3 3056.62 46.5098 4 3010.34 49.4743 5 2935.13 45.9393 6 2888.84 49.9798 7 2354.66 57.9169 8 1965.11 60.7359 9 1920.75 61.5511 10 1897.61 61.3681 11 1824.33 62.7822 12 1776.12 63.8974 13 1670.05 63.3185 14 1590.99 62.1484 15 1509.99 55.2477 16 1484.92 58.2636 17 1436.71 39.4720 18 1403.92 59.0824 19 1336.43 62.2717 20 1317.14 63.9278 21 1236.15 50.0672 22 1195.65 37.3148 23 1182.15 27.7416 24 1132.01 50.5852 25 1118.51 40.1215 26 1068.37 53.9037 27 1029.8 60.6920 28 997.017 61.8595 29 977.733 67.5493 30 921.807 66.9168 31 858.168 35.9386 32 823.455 65.5616 33 786.815 49.2939 34 746.317 41.7239 35 730.889 38.3904 36 713.533 39.0719 37 692.32 31.8651 38 615.181 70.4798 39 559.255 26.8222 40 512.972 27.9870 41 495.616 42.9809 42 447.404 62.9133 43 428.12 72.8920 44 412.692 61.9466

Example 2: Preparation of the Low Dielectric Resin Composition with Phosphorus-Containing Flame Retardant

(27) The relevant components were mixed thoroughly according to the formulations as shown in tables 38, thus obtaining a resin composition of the resin varnish, wherein E represented the low dielectric resin composition with phosphorus-containing flame retardant of the present invention, and C represented the comparative example.

(28) TABLE-US-00003 TABLE 3 The formulation list of the low dielectric resin composition with phosphorus-containing flame retardant (unit: parts by weight) Resin composition Components E1 E2 C1 C2 C3 C4 C5 C6 Flame High melting point Compound 35 35 35 35 retardant phosphorus-containing A flame retardant Low melting point SPB-100 35 35 phosphorus-containing flame retardant Condensed phosphate PX-200 35 Hydroxyl-containing XZ92741 35 phosphorus-containing flame retardant Vinyl Vinylbenzylether OPE-2st 100 100 100 100 100 compound polyphenylene ether Methacrylate SA-9000 100 100 100 polyphenylene ether Maleimide Homide108 30 30 Peroxide Peroxide DCP 3 3 3 3 3 3 3 3 Inorganic Spherical silicon SE5500 60 60 60 60 60 60 60 60 filler dioxide Solvent Toluene 100 100 100 100 100 100 100 100 Butanone 30 30 30 30 30 30 30 30

(29) TABLE-US-00004 TABLE 4 The formulation list of the low dielectric resin composition with phosphorus-containing flame retardant (unit: parts by weight) Resin composition Components E3 E4 E5 E6 E7 E8 Flame High melting point Compound A 35 45 45 45 50 35 retardant phosphorus-containing flame retardant Low melting point SPB-100 phosphorus-containing flame retardant Condensed phosphate PX-200 Hydroxyl-containing XZ92741 phosphorus-containing flame retardant Vinyl Vinylbenzyl ether OPE-2st 100 100 100 100 100 100 compound polyphenylene ether Styrene-polybutadiene- Ricon257 30 15 15 60 divinylbenzene Styrene-polybutadiene- Ricon184MA6 15 15 5 maleic anhydride copolymer Maleimide Homide108 30 Peroxide Peroxide DCP 3 3 3 3 3 3 Inorganic Spherical silicon SE-5500 60 60 60 60 60 60 filler dioxide Solvent Toluene 100 100 100 100 100 100 Butanone 30 30 30 30 30 30

(30) TABLE-US-00005 TABLE 5 The formulation list of the low dielectric resin composition with phosphorus-containing flame retardant (unit: parts by weight) Resin composition Components E9 E10 E11 E12 E13 E14 Flame High melting point Compound A 45 45 90 25 70 70 retardant phosphorus-containing flame retardant Low melting point SPB-100 phosphorus-containing flame retardant Condensed phosphate PX-200 Hydroxyl-containing XZ92741 phosphorus-containing flame retardant Vinyl Vinylbenzyl ether OPE-2st 100 100 100 100 100 100 compound polyphenylene ether Styrene-polybutadiene- Ricon257 35 35 divinylbenzene polybutadiene-urethane- R-45vt 15 methyl methacrylate Styrene-polybutadiene- Ricon184MA6 7.5 7.5 maleic anhydride copolymer Maleimide Homide108 50 15 35 35 Peroxide Peroxide DCP 3 3 3 3 3 3 Inorganic Spherical silicon SQ-5500 60 60 60 60 60 60 filler dioxide Solvent Toluene 100 100 100 100 100 100 Butanone 30 30 30 30 30 30

(31) TABLE-US-00006 TABLE 6 The formulation list of the low dielectric resin composition with phosphorus-containing flame retardant (unit: parts by weight) Resin composition Components E15 E16 Flame retardant High melting point Compound A 70 70 phosphorus-containing flame retardant Low melting point SPB-100 phosphorus-containing flame retardant Condensed phosphate PX-200 Hydroxyl-containing XZ92741 phosphorus-containing flame retardant Vinyl Vinylbenzyl DP-85T 50 30 compound etherified-dicyclopenta- diene-phenol resin Styrene-polybutadiene- Ricon257 35 30 divinylbenzene Modified PPE/VBE 50 70 vinylpolyphenylene ether 7205L Styrene-polybutadiene- Ricon184MA6 7.5 7.5 maleic anhydride copolymer Maleimide Homide108 35 35 Peroxide Peroxide DCP 3 3 Inorganic filler Spherical silicon dioxide SQ-5500 60 60 Solvent Toluene 100 100 Butanone 30 30

(32) TABLE-US-00007 TABLE 7 The formulation list of the low dielectric resin composition with phosphorus-containing flame retardant (unit: parts by weight) Resin composition Components C7 C8 C9 C10 C11 Flame High melting point Compound A 100 20 retardant phosphorus-containing flame retardant Low melting point SPB-100 70 phosphorus-containing flame retardant Condensed phosphate PX-200 70 Hydroxyl-containing XZ92741 70 phosphorus-containing flame retardant Vinyl Vinylbenzyl ether OPE-2st 100 100 100 100 100 compound polyphenylene ether Styrene-polybutadiene- Ricon257 35 35 35 35 divinylbenzene Styrene-polybutadiene- Ricon184MA6 7.5 7.5 7.5 7.5 maleic anhydride copolymer Maleimide Homide108 35 35 35 35 Peroxide Peroxide DCP 3 3 3 3 3 Inorganic Spherical silicon SQ5500 60 60 60 60 60 filler dioxide Solvent Toluene 100 100 100 100 100 Butanone 30 30 30 30 30

(33) TABLE-US-00008 TABLE 8 The formulation list of the low dielectric resin composition with phosphorus-containing flame retardant (unit: parts by weight) Resin composition Components C12 C13 C14 C15 C16 C17 Flame High melting point Compound A 70 70 70 70 70 70 retardant phosphorus-containing flame retardant Low melting point SPB-100 phosphorus-containing flame retardant Condensed phosphate PX-200 Hydroxyl-containing XZ92741 phosphorus-containing flame retardant Vinyl Vinylbenzyl ether OPE-2st 100 100 100 100 100 100 compound polyphenylene ether Styrene-polybutadiene- Ricon257 70 5 35 35 35 35 divinylbenzene Styrene-polybutadiene- Ricon184MA6 7.5 7.5 20 1 7.5 7.5 maleic anhydride copolymer Maleimide Homide108 35 35 35 35 60 10 Peroxide Peroxide DCP 3 3 3 3 3 3 Inorganic Spherical silicon SQ5500 60 60 60 60 60 60 filler dioxide Solvent Toluene 100 100 100 100 100 100 Butanone 30 30 30 30 30 30

(34) The resin composition components in the abovementioned E1E16 and C1C17 were mixed to homogenous in a stirring tank respectively, then placed into an impregnation tank, and subsequently a glass fiber cloth (2116 glass fiber cloth, purchased from Nan Ya Plastics Corporation) was passed through the abovementioned impregnation tank, to make the resin composition adhered onto the glass fiber cloth, then heated and baked into a semi-cured state, thus obtaining a prepreg.

(35) Four sheets of the prepregs taken from each type of the prepregs prepared above respectively, and two sheets of 18 m coppers were superimposed in the order of copper foil, four sheets of the prepregs, and copper foil, then laminated in vacuum at 210 C. for 2 hours, thus forming a copper clad laminate, wherein the four sheets of the prepregs were cured and formed an insulating layer between the two sheets of coppers.

(36) The physical properties of the abovementioned copper clad laminates and the copper-free laminates after etching off the copper foil were determined respectively, including the copper-free laminates obtained by laminating four sheets of the prepregs, with a resin content of about 55%, except that the dielectric constants and dissipation factors were determined on the copper-free laminates made from two sheets of prepregs, the other physical properties of the copper-free laminates were all determined on the laminates made from four sheets of the prepregs, and the physical properties to be determined comprised glass transition temperature (Tg, measured on a DMA (Dynamic Mechanical Analysis) instrument, IPC-TM-650 2.4.24.4), heat resistance (T288, measured by TMA (Thermo Mechanical Analyzer), wherein the copper clad laminate was measured for the time that the plate did not burst during heating at 288 C., IPC-TM-650 2.4.24.1), thermal expansion ratio (CTE z-axis, dimension change: 50260 C., measured on a TMA Thermo Mechanical Analyzer instrument, IPC-TM-650 2.4.24.5, %, the lower dimension changes representing the better results), copper clad laminate solder dip test (solder dipping, S/D, 288 C., 10 sec, measured the number of heat cycles), dielectric constant (Dk, measured on an AET microwave dielectric analyzer, JIS C2565, the lower Dk values representing the better dielectric properties), dissipation factor (Df, measured on an AET microwave dielectric analyzer, JIS C2565, the lower Df values representing the better dielectric properties), and flame resistance (flaming test, UL94, with the grade rank V-0 being better than V-1).

(37) Among them, the physical property testing results of the laminates prepared from the resin compositions in E1E2 and C1C6 were listed in table 9, and the physical property testing results of the laminates prepared from the resin compositions in E3E16 and C7C17 were listed tables 1012. Compared the examples with the comparative examples synthetically, it can be seen that as compared those using Compound A with those using the general phosphorus-containing additives, the results showed that the laminates had lower Dk and Df values, and lower thermal expansion ratio (the dimension change in z-axis).

(38) TABLE-US-00009 TABLE 9 The performance indexes of the laminate made from the low dielectric resin composition with phosphorus-containing flame retardant Property Test method E1 E2 C1 C2 C3 C4 C5 C6 Tg DMA instrument 195 215 185 160 178 205 188 206 (glass transition temperature, IPC-TM-650 2.4.24.4/ C.) CTE Measurements on a 2.1 1.8 3.1 3.4 2.8 2.4 3.1 2.4 (50~260 C.) TMA instrument (thermal mechanical analyzer), IPC-TM-650 2.4.24.5, % T288 At 288 C., heat 64 >70 60 30 15 63 60 68 resistance, IPC-TM-650 2.4.24.1/min S/D Solder dipping test, >20 >20 >20 15 8 >20 >20 >20 288 C., 10 sec, measured the number of heat cycles Dk 10 GHz, AET 3.5 3.5 3.6 3.6 3.7 3.5 3.5 3.5 microwave dielectric analyzer, JIS C2565 Df 10 GHz, AET, 0.0048 0.0053 0.0059 0.0055 0.0110 0.0065 0.0065 0.0066 microwave dielectric analyzer, JIS C2565 Flame Burning test UL94 V-0 V-0 V-1 V-2 V-1 V-0 V-0 V-0 resistance

(39) TABLE-US-00010 TABLE 10 The performance indexes of the laminate made from the low dielectric resin composition with phosphorus-containing flame retardant Property Test method E3 E4 E5 E6 E7 E8 E9 E10 Tg DMA instrument 195 198 193 210 188 195 230 205 (glass transition temperature, IPC-TM-650 2.4.24.4/ C.) CTE Measurements on a 2.1 2.5 2.5 1.9 2.8 2.3 1.5 2 (50~260 C.) TMA instrument (thermal mechanical analyzer), IPC-TM-650 2.4.24.5, % T288 At 288 C., heat 61 62 63 >70 55 65 >70 >70 resistance, IPC-TM-650 2.4.24.1/min S/D Solder dipping test, >20 >20 >20 >20 >20 >20 >20 >20 288 C., 10 sec, measured the number of heat cycles Dk 10 GHz, AET 3.5 3.4 3.5 3.5 3.5 3.6 3.6 3.5 microwave dielectric analyzer, JIS C2565 Df 10 GHz, AET 0.0048 0.0045 0.0045 0.0056 0.0043 0.0055 0.0059 0.0058 microwave dielectric analyzer, JIS C2565 Flame Burning test UL94 V-0 V-0 V-0 V-0 V-0 V-0 V-0 V-0 resistance

(40) TABLE-US-00011 TABLE 11 The performance indexes of the laminate made from the low dielectric resin composition with phosphorus-containing flame retardant Property Test method E11 E12 E13 E14 E15 E16 C7 C8 Tg DMA instrument 202 195 212 215 210 203 212 185 (glass transition temperature, IPC-TM-650 2.4.24.4/ C.) CTE Measurements on a 2.6 2.5 1.9 1.9 2.5 2.7 1.8 3 (50~260 C.) TMA instrument (thermal mechanical analyzer), IPC-TM-650 2.4.24.5% T288 At 288 C., heat 30 65 >70 >70 >70 >70 >70 64 resistance IPC-TM-650 2.4.24.1/min S/D Solder dipping test, >20 >20 >20 >20 >20 >20 >20 >20 288 C., 10 sec, measured the number of heat cycles Dk 10 GHz, AET 3.7 3.5 3.5 3.5 3.4 3.5 3.8 3.6 microwave dielectric analyzer, JIS C2565 Df 10 GHz, AET 0.0059 0.0051 0.0053 0.0053 0.0052 0.0053 0.0061 0.0051 microwave dielectric analyzer, JIS C2565 Flame Burning test UL94 V-0 V-0 V-0 V-0 V-0 V-0 V-0 Burn resistance out

(41) TABLE-US-00012 TABLE 12 The performance indexes of the laminate made from the low dielectric resin composition with phosphorus-containing flame retardant Property Test method C9 C10 C11 C12 C13 C14 C15 C16 C17 Tg DMA, 180 175 185 155 195 190 196 235 190 IPC-TM-650 2.4.24.4/ C.) CTE IPC-TM-650 3.1 3.1 2.8 3.8 2.2 2.8 2.2 1.5 2.8 (50~260 C.) 2.4.24.5% T288 At 288 C., heat 64 30 15 15 50 55 58 >70 57 resistance IPC-TM-650 2.4.24.1/min S/D Solder dipping >20 >20 15 15 >20 >20 >20 >20 >20 test, 288 C., 10 sec, measured the number of heat cycles Dk 10 GHz, AET 3.7 3.7 4.1 3.3 3.5 3.7 3.5 3.7 3.6 microwave dielectric analyzer, JIS C2565 Df 10 GHz, AET 0.0061 0.0058 0.0120 0.0048 0.0059 0.0057 0.0057 0.006 0.0058 microwave dielectric analyzer, JIS C2565 Flame Burning test UL94 V-2 Burn V-1 V-0 V-0 V-0 V-0 V-0 V-0 resistance out

(42) The result analysis:

(43) It can be seen from the data in the abovementioned tables, that as compared with those in C1C6, those in E1 and E2 in the present invention substantially had lower dimension changes, and the laminates prepared therefrom had lower thermal expansion ratios. At the same time, the low dielectric resin compositions with phosphorus-containing flame retardant of the present invention had excellent heat resistances. As compared E1 and E2 with C1C3, it can be seen that the low dielectric resin compositions with the present invention had excellent flame resistances and can effectively achieve the flame resistance effects of UL94 V-0, due to containing the specific phosphorus-containing flame retardants.

(44) As compared the data in E4E7 with those in C8C12, it can be seen that the low dielectric resin composition with phosphorus-containing flame retardant of the present invention further decreased the dissipation factors, obtained better dielectric properties, and made the systems achieved better dielectric properties (the lower dielectric properties representing the better results) due to the addition of the styrene polymer.

(45) As compared the data in E13 and E14 of the present invention with those in C7, it can be seen that the formulation combination, under which the low dielectric resin compositions with phosphorus-containing flame retardants of the present invention had the highest thermal stabilities, and lower thermal expansion ratios and better dielectric properties, was the best formulation.

(46) As described above, the low dielectric resin compositions with phosphorus-containing flame retardants of the present invention, due to containing the specific components and proportions, can achieve low thermal expansion ratios, low dielectric constants, low dissipation factors, high heat resistances and high flame resistances; and can be made into prepregs or resin films, and in turn achieved the purpose for applying in copper clad laminates and printed circuit boards; and in terms of the industrial availability, the requirements on the current market can be fully met by using the products derived from the present invention.

(47) The abovementioned examples are the preferred embodiments of the present invention, but the embodiments of the present invention are not limited thereto, any other changes, modifications, substitutions, combinations and simplifications, all of which shall be the equivalent replacements, without departing from the spirit and principle of the present invention, are all encompassed in the scope of protection of the present invention.