Resin composition

Abstract

The present invention relates to resin composite materials, and more particularly, to low-dielectric resin composition and prepreg, resin film, resin coated copper, laminate and printed circuit board formed therefrom. The low-dielectric resin composition includes a phosphorus-containing flame retardant as shown in formula (I) and a resin with an active unsaturated bond. The low-dielectric resin composition may further be manufactured as a prepreg, a resin film, a resin coated copper, a laminate, or a printed circuit board, having a high glass transition temperature, low dielectric property, halogen-free flame retardancy and low percent of thermal expansion of laminate.

Claims

1. A low-dielectric resin composition, comprising: (a) 18 to 80 parts by weight of a phosphorus-containing flame retardant, being expressed by formula (I) below: ##STR00010## wherein A is a phenylene or a biphenylene; and (b) 100 parts by weight of a vinyl polyphenylene ether resin, wherein a laminate made from the low-dielectric resin composition has a percent of thermal expansion as measured by reference to IPC-TM-650 2.4.24.5 of less than or equal to 2.75%, a T288 thermal resistance as measured by reference to IPC-TM-650 2.4.24.1 of greater than or equal to 65 minutes and a peel strength as measured by reference to IPC-TM-650 2.4.8 of greater than or equal to 4.00 lb/in.

2. The low-dielectric resin composition according to claim 1, wherein the phosphorus-containing flame retardant is expressed by formula (Ia) or formula (Ib): ##STR00011##

3. The low-dielectric resin composition according to claim 1, wherein the vinyl polyphenylene ether resin is a polyphenylene ether resin with a capping group having an unsaturated double bond.

4. The low-dielectric resin composition according to claim 1, wherein the vinyl polyphenylene ether resin is selected from the following: vinylbenzyl-terminated polyphenylene ether resin, methacrylate-terminated polyphenylene ether resin and a combination thereof.

5. The low-dielectric resin composition according to claim 4, wherein the vinylbenzyl-terminated polyphenylene ether resin and the methacrylate-terminated polyphenylene ether resin are expressed by formula (II) and formula (III) below respectively: ##STR00012## wherein (OXO) is ##STR00013## (YO) is ##STR00014## wherein R.sub.1 and R.sub.2 are a hydrogen atom, and R.sub.3, R.sub.4, R.sub.5, R.sub.6 and R.sub.7 are the same as or different from each other, each independently representing a hydrogen atom or an alkyl group; R.sub.8, R.sub.9, R.sub.10, R.sub.13, R.sub.14 and R.sub.15 are the same as or different from each other, each independently representing a C.sub.1 to C.sub.6 alkyl group or a phenyl group, and R.sub.11 and R.sub.12 are the same as or different from each other, each independently representing a hydrogen atom, a C.sub.1 to C.sub.6 alkyl group or a phenyl group; R.sub.16, R.sub.17, R.sub.22 and R.sub.23 are the same as or different from each other, each independently representing a C.sub.1 to C.sub.6 alkyl group or a phenyl group, and R.sub.18, R.sub.19, R.sub.20 and R.sub.21 are the same as or different from each other, each independently representing a C.sub.1 to C.sub.6 alkyl group or a phenyl group; A is a C.sub.1 to C.sub.20 linear hydrocarbon, a C.sub.1 to C.sub.20 branched hydrocarbon or a C.sub.1 to C.sub.20 cyclic hydrocarbon; R.sub.24 and R.sub.25 are the same as or different from each other, each independently representing a C.sub.1 to C.sup.6 alkyl group or a phenyl group, and R.sub.26 and R.sub.27 are the same as or different from each other, each independently representing a hydrogen atom, a C.sub.1 to C.sub.6 alkyl group or a phenyl group; Z is an organic group having at least one carbon atom; a and b are a natural number ranges from 1 to 30 respectively; c and d are 1; G is a C(CH.sub.3).sub.2, CH.sub.2 or a covalent bond; and m and n are a natural number ranges from 1 to 15 respectively.

6. The low-dielectric resin composition according to claim 5, wherein A is a C.sub.1 to C.sub.6 linear hydrocarbon, a C.sub.1 to C.sub.6 branched hydrocarbon or a C.sub.1 to C.sub.6 cyclic hydrocarbon.

7. The low-dielectric resin composition according to claim 5, wherein A is CH.sub.2 or C(CH.sub.3).sub.2.

8. The low-dielectric resin composition according to claim 5, wherein Z is a C.sub.1 to C.sub.6 alkyl group.

9. The low-dielectric resin composition according to claim 5, wherein Z is an organic group having at least one carbon atom, and the organic group further comprises an oxygen atom or a nitrogen atom.

10. The low-dielectric resin composition according to claim 5, wherein Z is a methylene (CH.sub.2).

11. The low-dielectric resin composition according to claim 5, wherein a and b are the same as or different from each other, and a and b are a natural number ranges from 1 to 10 respectively.

12. The low-dielectric resin composition according to claim 1, wherein when an amount of the vinyl polyphenylene ether resin of the low-dielectric resin composition is 100 parts by weight, an amount of the phosphorus-containing flame retardant ranges from 20 to 80 parts by weight.

13. The low-dielectric resin composition according to claim 1, wherein the low-dielectric resin composition further comprises a polyolefin in an amount ranges from 10 to 70 parts by weight and maleimide in an amount of 5 to 50 parts by weight.

14. The low-dielectric resin composition according to claim 1, wherein the low-dielectric resin composition further comprises: epoxy resin, phenol resin, benzoxazine resin, styrene-maleic anhydride resin, polyester, an amine curing agent, polyamide, polyimide, a curing accelerator, a solvent, a silane coupling agent, and an inorganic filler or a combination thereof.

15. The low-dielectric resin composition according to claim 14, wherein the phenol resin is selected from the following: hydroxy polyphenylene ether resin, phenoxy resin, and phenolic resin and a combination thereof.

16. A prepreg made from the low-dielectric resin composition according to claim 1.

17. A resin film made from the low-dielectric resin composition according to claim 1.

18. A resin coated copper, made from the low-dielectric resin composition according to claim 1.

19. A laminate, made from a prepreg, a rein film, or a resin coated copper which is made from the low-dielectric resin composition according to claim 1.

20. A printed circuit board, made from the laminate according to claim 19.

21. The low-dielectric resin composition according to claim 1, wherein the low-dielectric resin composition further comprises a monomer comprising an unsaturated reactive functional group, and the monomer comprising the unsaturated reactive functional group is styrene, divinylbenzene, trivinylcyclohexane or a combination thereof.

22. The low-dielectric resin composition according to claim 1, wherein the low-dielectric resin composition further comprises: polyolefin, cyanate ester resin, maleimide, triallyl isocyanurate, triallyl cyanurate and a combination thereof.

23. A low-dielectric resin composition, comprising: (a) 18 to 80 parts by weight of a phosphorus-containing flame retardant, being expressed by formula (I) below: ##STR00015## wherein A is a phenylene or a biphenylene; and (b) 100 parts by weight of a vinyl polyphenylene ether resin, wherein a laminate made from the low-dielectric resin composition has a percent of thermal expansion as measured by reference to IPC-TM-650 2.4.24.5 of less than or equal to 3.00%, a T288 thermal resistance as measured by reference to IPC-TM-650 2.4.24.1 of greater than or equal to 65 minutes, a flame retardancy as measured in accordance with the UL94 rating to evaluate flame retardancy level represented by V-1 or V-0 and a peel strength as measured by reference to IPC-TM-650 2.4.8 of greater than or equal to 4.00 lb/in.

Description

BRIEF DESCRIPTION OF THE DRAWINGS

(1) FIG. 1 shows a DSC analysis diagram of the melting point of the compound A.

(2) FIG. 2 shows a FTIR spectrum of the compound A.

DETAILED DESCRIPTION

(3) The following applications are the further explanations of the present invention. However, the applications of the present invention are not limited by the embodiments listed below. All various modifications or adjustment accorded with the principles or the spirits of the present invention are regarded as the concepts of the present invention.

(4) In the condition without particularly interpretation, the materials and experimental methods of the present invention are the regular materials and methods.

(5) The chemicals for use in the embodiments are as follows:

(6) SPB-100: phosphazene, available from Otsuka Chemical.

(7) PX-200: resorcinol bis[di(2,6-dimethylphenyl)phosphate], available from Daihachi Chemical.

(8) XZ92741: DOPO-bisphenol A novolac resin, available from Dow chemical.

(9) OPE-2st: Vinylbenzyl-terminated polyphenylene ether resin, available from Mitsubishi Gas Chemical.

(10) SA-9000: Methacrylate-terminated polyphenylene ether resin, available from Sabic.

(11) MIR-3000-70MT: biphenyl maleimide, available from Nippon Kayaku.

(12) 25B: 2,5-dimethyl-2,5-di(tert-butylperoxy)-3-hexyne, available from Nippon Oils & Fats.

(13) SC-2050 SV: spherical silicon dioxide, available from Admatech.

(14) H-1051: hydrogenated styrene butadiene copolymer, available from Asahi Kasei.

(15) Ricon100: butadiene-styrene copolymer, available from Cray valley.

(16) Ricon184MA6: styrene-butadiene-maleic anhydride copolymer, available from Cray valley.

(17) DVB: divinylbenzene, available from Sigma Aldrich.

(18) TAC: triallyl cyanurate, available from Sigma Aldrich.

(19) Compound A: phosphorus-containing flame retardant with high melting point.

Embodiment 1: A Method of Making Compound A

(20) 2 moles (approximately 432 g) of DOPO (9,10-Dihydro-9-Oxa-10-Phosphaphenantrene-10-Oxide), 1 mole (approximately 128 g) of 1,4-bis(chloromethyl)benzene and 2400 g of dichlorobenzene solvent are placed in a blender and are heated to 150 C. and stirred for dissolving the solids, so as to form a evenly mixed solution, and the solution is continuously heated and stirred for 24 hours.

(21) Then, cool the solution to room temperature before washing with hexane and filtering the solution, so as to obtain a white crystal product. Bake the white crystal product for 6 hours under 120 C. to obtain a white powder product, and grind the white powder product to particles whose particle size D50 is 6 m (representing an amount of the particles whose particle sizes smaller than 6 m is 50 volume % of the total amount of the particles), so as to obtain compound A.

(22) The compound A is analyzed by the reflection-type fourier transform infrared spectroscopy (reflection-type FTIR), and the result is shown in FIG. 2. The FTIR spectrum reveals absorption peaks indicative of a P-Ph at 1594 cm.sup.1, a PO at 1205 cm.sup.1 and a PO-Ph at 908 cm.sup.1.

(23) According to the analysis result of the FTIR, the obtained product has a phosphorus-containing flame retardant expressed by formula (Ia).

(24) The melting point of the compound A measured by DSC is approximately 278 C. Thus, the compound A is the flame retardant with high melting point.

Embodiment 2: Various Low-Dielectric Resins Composition

(25) The main components of the low-dielectric resin composition are the phosphorus-containing flame retardant and resin components.

(26) Various kinds of the low-dielectric resin compositions are shown in Tables 1, 3, 5.

(27) According to the low-dielectric resin compositions shown in the tables, mix each components evenly, so as to obtain a resin varnish of the resin composition, wherein E1 to E12 represent the examples of low-dielectric resin compositions with the phosphorus-containing flame retardant of the present invention, and C1 to C16 represent the comparative examples.

Embodiment 3: Preparation of Resin Film

(28) Coat the resin varnish of each of the resin compositions prepared according to the aforementioned E1 to E12 and C1 to C16 on a PET film (or a PI film) respectively, make the resin composition (approximately 30 m of thickness) adhere to the film evenly, and undergo a heat baking process to become semi-cured, so as to obtain a resin film, wherein the condition of the heat baking process includes the baking time of 4 minutes under 160 C.

Embodiment 4: Preparation of Resin Coated Copper

(29) Coat the resin varnish of each of the resin compositions prepared according to the aforementioned E1 to E12 and C1 to C16 on a copper foil respectively, make the resin composition (approximately 30 m of thickness) adhere to the foil evenly, and undergo a heat baking process to become semi-cured, so as to obtain a resin coated copper, wherein the condition of the heat baking process includes the baking time of 4 minutes under 160 C.

Embodiment 5: Preparation of Composite Material with Low Dielectric Constant

(30) Coat the resin varnish of each of the resin compositions prepared according to the aforementioned E1 to E12 and C1 to C16 on a PI film of the resin side of the resin coated copper respectively to obtain the structure of the copper foil, the PI film and the resin composition layer by layer, make the resin composition (approximately 30 m of thickness) adhere to the film evenly, and undergo a heat baking process to become semi-cured, so as to obtain a flexible resin coated copper, wherein the condition of the heat baking process includes the baking time of 4 minutes under 160 C., and the PI film may be at least one of TPI (thermoplastic polyimide) and PI (polyimide).

Embodiment 6: Preparation of Prepreg

(31) After respectively mixing the resin compositions of the aforementioned examples and the comparative examples in a blender evenly, they are placed in an impregnation tank respectively. Then, a glass fiber fabric (2116 E-glass fiber fabric, available from Nan Ya Plastics Industry) is respectively immersed into the impregnation tank to allow the resin composition to adhere to the glass fiber fabric before undergoing a heat baking process to become semi-cured, thereby forming a prepreg.

Embodiment 7: Preparation of Copper-Clad Laminate

(32) Four pieces of the prepregs respectively prepared above according to the aforementioned embodiments and two pieces of copper foils with a thickness of 18 m are supplied. The copper foil, four pieces of the prepregs and copper foil are stacked in sequence before being laminated against each other under vacuum at 210 C. for two hours to form a copper-clad laminate, wherein, the stacked four pieces of prepregs are cured to form the insulating layer between the two copper foils.

Embodiment 8: Analysis of Properties

(33) The resin compositions having the phosphaphenanthrene-based compounds in E1 to E12 and the resin compositions in C1 to C16 are selected in this test example. Each resin composition is evenly mixed in a blender before being put into an impregnation tank respectively. Then, a glass fiber fabric (2116 E-glass fiber fabric, available from Nan Ya Plastics Industry) is immersed into the impregnation tank to allow the resin composition to adhere to the glass fiber fabric before undergoing a heat baking process under 120 C.-160 C. to become semi-cured, thereby forming a prepreg.

(34) Preparation of the Test Samples for Property Analysis:

(35) 1. Copper-Clad Laminate (Four Plies):

(36) Two pieces of copper foils with a thickness of 18 m, and four pieces of the prepregs manufactured according to the selected test sample are supplied, wherein each prepreg has a thickness of 0.127 mm. The content of the resin of each prepreg is about 55%. The copper foil, four pieces of the prepregs and copper foil are stacked in sequence before being laminated against each other under vacuum at 210 C. for two hours to form a copper-clad laminate. Wherein, the stacked four pieces of prepregs are cured to form the insulating layer between the two copper foils, and the content of the resin of the insulating layer is about 55%.

(37) 2. Copper-Free Laminate (Four Plies):

(38) The aforementioned copper-clad laminate is etched to remove the two copper foils to obtain the copper-free laminate (four plies). Wherein the insulating layer of the copper-free laminate (four plies) is formed with four laminated prepregs, and the content of the resin of the copper-free laminate (four plies) is about 55%.

(39) 3. Copper-Free Laminate (Double Plies):

(40) Two pieces of copper foils with a thickness of 18 m and two pieces of the prepregs manufactured according to the selected test samples mentioned above are supplied, wherein each of the prepregs has a thickness of 0.127 mm. The content of the resin of each prepreg is about 55%. The copper foil, two pieces of the prepreg and copper foil are stacked in sequence before being laminated against each other under vacuum at 210 C. for two hours to form a double plies copper-clad laminate.

(41) Next, the double plies copper-clad laminate undergoes etching to remove the two copper foils so as to obtain the copper-free laminate (double plies). Wherein the insulating layer is formed with two laminated prepregs, and the content of the resin of the copper-free laminate (double plies) is about 55%.

(42) The property analysis of this test example includes the following items.

(43) 1. Glass Transition Temperature (Tg):

(44) To measure the glass transition temperature, the copper-free laminate (four plies) is selected as the test sample. The glass transition temperature of each test sample is measured by a dynamic mechanical analysis (DMA) according to IPC-TM-650 2.4.24.4 test method.

(45) 2. Percent of Thermal Expansion (Dimension Change, CTE Z-Axis):

(46) To measure the percent of thermal expansion, the copper-free laminate (four plies) is selected as the test sample. When heating the temperature from 50 C. to 260 C., the percent of thermal expansion of each test samples is measured by a thermal mechanical analyzer (TMA) according to IPC-TM-650 2.4.24.5 test method in this temperature range, wherein the unit is percentage (%). Lower the percent of dimension change is preferred, which means the resin composition has better properties when it is applied to the printed circuit board.

(47) 3. Solder Dipping (S/D):

(48) To measure the solder dipping, the aforementioned copper-clad laminate (four plies) is selected as the test sample. According to IPC-TM-650 2.4.23 test method, each test sample is immersed in the solder pot with a constant temperature of 288 C. for 10 seconds each time, then, removed from the solder pot for 10 seconds in the room temperature, and then, immersed in the solder pot for 10 seconds again. Repeat the steps above to test the total cycle of thermal resistance without delamination of each test sample. The more total cycles of the test sample indicates that the thermal resistance of the copper-clad laminate made from the resin composition is better.

(49) 4. Thermal Resistance Test (T288):

(50) In the T288, the aforementioned copper-clad laminate (four plies) is selected as the test sample. According to IPC-TM-650 2.4.24.1 test method, the duration of each test sample sustaining heat under a constant temperature of 288 C. without delamination is measured by thermal mechanical analyzer (TMA).

(51) 5. Dielectric Constant (Dk) and Dissipation Factor (Df):

(52) To measure the dielectric constant and the dissipation factor, the aforementioned copper-free laminate (double plies) is selected as the test sample, measured at 10 GHz by a microwave dielectrometer (purchased from AET) according to JIS C2565 test method. The lower dielectric constant and lower dissipation factor indicates that the dielectric properties of the test sample are better.

(53) 6. Flame Retardancy:

(54) In the flame retardancy test, the copper-free laminate (four plies) is selected as the test sample. The flame retardancy test is performed according to UL94 test method, and the analysis results are illustrated in the rankings V-0, V-1, and V-2, wherein the ranking V-0 is superior to V-1, V1 is superior to V-2 and burnout is the worst.

(55) 7. Peel Strength (P/S)

(56) To measure the peel strength, the aforementioned copper-clad laminate (four plies) is selected as the test sample. According to IPC-TM-650 2.4.8 test method, wherein the unit is lb/in.

(57) The results of property analysis of the test samples prepared from the resin compositions of E1 to E12 and C1 to C16 are enumerated in Table 2, Table 4 and Table 6.

(58) TABLE-US-00001 TABLE 1 The component examples (I) of the compositions Composition of resin Component E1 E2 E3 E4 C1 C2 C3 C4 C5 C6 C7 Flame Phosphorus- Compound A 25 25 25 25 retardant containing flame retardant with high melting point Phosphorus- SPB-100 25 60 25 containing flame retardant with low melting point Condensed PX-200 25 70 phosphate ester Phosphorus- XZ92741 25 55 containing flame retardant with hydroxyl group Resin with Vinylbenzyl OPE-2st 100 100 100 100 100 100 100 100 an active polyphenylene unsaturated ether bond Methacrylate SA-9000 100 100 100 polyphenylene ether Maleimide MIR-3000- 30 30 70MT Peroxide Peroxide 25B 1 1 1 1 1 1 1 1 1 1 1 Inorganic Spherical SC-2050 SV 70 70 70 70 70 70 70 70 70 70 70 filler silicon dioxide Solvent Toluene 100 100 100 100 100 100 100 100 100 100 100 MEK 30 30 30 30 30 30 30 30 30 30 30

(59) TABLE-US-00002 TABLE 2 The properties of laminate made from the component examples (I) of the compositions Analysis Property of item laminate (method) E1 E2 E3 E4 C1 C2 Glass Tg (DMA) C. 201 220 209 220 190 155 transition temperature Percent of Dimension % 2.15 2.12 2.36 2.31 3.04 3.35 thermal change expansion (TMA) Thermal T288 (TMA) Minute >70 >70 65 68 55 30 resistance at 288 C. Solder S/D Cycle >20 >20 >20 >20 >20 16 dipping Dielectric Dk@10 GHz Unit 3.50 3.58 3.57 3.71 3.68 3.74 constant free Dissipation Df@10 GHz Unit 0.0059 0.0062 0.0061 0.0068 0.0063 0.0075 factor free Flame UL94 Second V-0 V-0 V-0 V-0 V-1 V-0 retardancy Analysis Property of item laminate (method) C3 C4 C5 C6 C7 Glass Tg (DMA) C. 166 140 184 172 194 transition temperature Percent of Dimension % 3.24 3.86 2.72 3.23 3.03 thermal change expansion (TMA) Thermal T288 (TMA) Minute 38 15 15 8 50 resistance at 288 C. Solder S/D Cycle 18 10 8 5 >20 dipping Dielectric Dk@10 GHz Unit 3.74 3.87 3.70 3.95 3.68 constant free Dissipation Df@10 GHz Unit 0.0065 0.0079 0.0114 0.0129 0.0066 factor free Flame UL94 Second V-2 V-0 V-1 V-0 V-1 retardancy

(60) TABLE-US-00003 TABLE 3 The component examples (II) of the compositions Composition of resin Component E5 E6 E7 E8 E9 E10 E11 Flame Phosphorus- compound A 35 40 35 35 80 20 60 retardant containing flame retardant with high melting point Phosphorus- SPB-100 containing flame retardant with low melting point Condensed PX-200 phosphate ester Phosphorus- XZ92741 containing flame retardant with hydroxyl group Resin with an Vinylbenzyl OPE-2st 100 100 100 100 100 100 100 active polyphenylene unsaturated ether bond Polybutadiene- D-1118 5 5 5 styrene copolymer Polybutadiene- Ricon100 50 60 20 20 styrene copolymer Styrene- Ricon184MA6 15 5 polybutadiene- maleic anhydride copolymer Maleimide MIR-3000- 50 5 7 70MT Triallyl TAC isocyanurate Divinylbenzene DVB Peroxide Peroxide 25B 1 1 1 1 1 1 1 Inorganic Spherical SC-2050 SV 70 70 70 70 70 70 70 filler silicon dioxide Solvent Toluene 100 100 100 100 100 100 100 MEK 30 30 30 30 30 30 30 Composition of resin Component E12 C8 C9 C10 C11 C12 C13 Flame Phosphorus- compound A 60 18 90 10 retardant containing flame retardant with high melting point Phosphorus- SPB-100 60 containing flame retardant with low melting point Condensed PX-200 60 phosphate ester Phosphorus- XZ92741 60 containing flame retardant with hydroxyl group Resin with an Vinylbenzyl OPE-2st 100 100 100 100 100 100 100 active polyphenylene unsaturated ether bond Polybutadiene- D-1118 5 5 5 5 5 styrene copolymer Polybutadiene- Ricon100 15 styrene copolymer Styrene- Ricon184MA6 5 5 5 5 5 polybutadiene- maleic anhydride copolymer Maleimide MIR-3000- 7 7 7 7 7 70MT Triallyl TAC 10 isocyanurate Divinylbenzene DVB 10 Peroxide Peroxide 25B 1 1 1 1 1 1 1 Inorganic Spherical SC-2050 SV 70 70 70 70 70 70 70 filler silicon dioxide Solvent Toluene 100 100 100 100 100 100 100 MEK 30 30 30 30 30 30 30

(61) TABLE-US-00004 TABLE 4 The properties of laminate made from the component examples (II) of the compositions Property Analysis of item laminate (method) E5 E6 E7 E8 E9 E10 E11 Glass Tg (DMA) C. 198 194 234 210 184 200 210 transition temperature Percent of Dimension % 2.41 2.75 2.05 2.21 2.65 2.14 1.93 thermal change expansion (TMA) Thermal T288 Minute >70 >70 >70 >70 >70 >70 >70 resistance (TMA) at 288 C. Solder S/D Cycle >20 >20 >20 >20 >20 >20 >20 dipping Dielectric Dk@10 GHz Unit 3.41 3.43 3.60 3.50 3.70 3.50 3.50 constant free Dissipation Df@10 GHz Unit 0.0052 0.0047 0.0058 0.0056 0.0060 0.0053 0.0052 factor free Flame UL94 Second V-0 V-0 V-0 V-0 V-0 V-0 V-0 retardancy Property Analysis of item laminate (method) E12 C8 C9 C10 C11 C12 C13 Glass Tg (DMA) C. 208 199 179 190 185 180 190 transition temperature Percent of Dimension % 1.98 2.14 2.73 3.0 3.54 3.49 2.71 thermal change expansion (TMA) Thermal T288 Minute >70 >70 59 64 64 30 3 resistance (TMA) at 288 C. Solder S/D Cycle >20 >20 >20 >20 >20 >20 12 dipping Dielectric Dk@10 GHz Unit 3.50 3.50 3.80 3.60 3.70 3.70 4.10 constant free Dissipation Df@10 GHz Unit 0.0051 0.0053 0.0062 0.0056 0.0063 0.0063 0.0123 factor free Flame UL94 Second V-0 V-1 V-0 burn V-2 burn V-1 retardancy out out

(62) TABLE-US-00005 TABLE 5 The component examples (III) of the compositions Composition of resin Component E1 C14 C15 C16 Flame retardant Phosphorus-containing Compound A 25 flame retardant with high melting point Phosphorus-containing Compound B 25 28 flame retardant (formula (IV)) Phosphorus-containing Compound C 25 flame retardant (formula (V)) Resin with Vinylbenzyl OPE-2st 100 100 100 100 an active polyphenylene ether unsaturated bond Peroxide Peroxide 25B 1 1 1 1 Inorganic Spherical silicon SC-2050 SV 70 70 70 70 filler dioxide Solvent Toluene 100 100 100 100 MEK 30 30 30 30

(63) TABLE-US-00006 TABLE 6 The properties of laminate made from the component examples (III) of the compositions Property of Analysis item laminate (method) E1 C14 C15 C16 Peel strength P/S (Hoz) lb/in 4.3 3.5 3.25 3.13 between the laminate and the copper foil Percent of Dimension change % 2.05 2.56 2.9 2.51 thermal (TMA) expansion Thermal T288 (TMA) Minute >70 >70 >70 65 resistance at 288 C. Solder dipping S/D Cycle >20 >20 >20 >20 Flame retardancy UL94 Second V-0 V-1 V-0 V-0

(64) Further researching the properties of the product (the laminate for example), the result demonstrates the importance of the selection of the phosphorus-containing compound and the resin.

(65) From the Table 1 and Table 2, to compare the composition comprises the resin with an active unsaturated bond with the compound A as the phosphorus-containing compound and the composition comprises the phosphorus-containing flame retardant SPB-100, PX-200 and XZ92741 individually (the comparisons of the compositions E1 to E4 and the compositions C1 to C7 which are shown in Table 1), the glass transition temperature of the product made from the composition comprising the compound A and the resin with an active unsaturated bond is higher than the other three evidently. In addition, the percent of thermal expansion of the product made from the composition comprising the compound A and the resin with an active unsaturated bond is lower than the other three evidently, and the dielectric constant and the dissipation factor of the product made from the composition comprising the compound A and the resin with an active unsaturated bond are lower than the other three evidently.

(66) The desired effect of the present invention can be obtained provided that the resin in collocation with the compound A, the phosphorus-containing flame retardant, comprises an unsaturated bond. In the resin, selecting the vinylbenzyl polyphenylene ether or the methacrylate polyphenylene ether is more profitable, and the outstanding effect is shown in the aforementioned tables.

(67) The preferred embodiment is the resin further comprises maleimide (the composition E2 and E4 shown in Table 1), such that the glass transition temperature, the low dielectric property, the thermal resistance and the percent of thermal expansion are all well improved, and more particularly, the improvement of the glass transition temperature is the most evident.

(68) The most preferred embodiment having the best overall properties is that the composition comprises the compound A as the flame retardant, and the resin with an active unsaturated bond comprises the vinylbenzyl polyphenylene ether, the polybutadiene-styrene copolymer, the styrene-polybutadiene-maleic anhydride copolymer and maleimide at the same time (the compositions E11 and E12 shown in Table 3).

(69) Unanticipatedly, as shown in Table 5 to Table 6, comparing the composition E1 (the collocation of the compound A and the vinylbenzyl polyphenylene ether) with other compositions (C14 to C16, the collocation of the compound B or the compound C and the vinylbenzyl polyphenylene ether), the laminate made from the composition E1 not only features a great dielectric property, a great flame retardancy and a great thermal resistance but also improves a peel strength between the laminate and the copper foil.

(70) The aforementioned embodiments are the adoptable applications of the present invention. However, the applications of the present invention are not limited by the aforementioned embodiments. The alterations, modifications, substitutions, combinations and simplification without departing from the spirit and principles of the present invention are all equivalent replacement of the present invention and are contained in the claimed scope of the present invention.

(71) Those skilled in the art will readily observe that numerous modifications and alterations of the device and method may be made while retaining the teachings of the invention. Accordingly, the above disclosure should be construed as limited only by the metes and bounds of the appended claims.