PHOSPHORUS-CONTAINING OLEFIN POLYMER, METHOD FOR PREPARING THE SAME, AND COMPOSITION AND ARTICLE COMPRISING THE SAME
20170342185 · 2017-11-30
Inventors
Cpc classification
H05K2201/0158
ELECTRICITY
International classification
H05K3/02
ELECTRICITY
Abstract
The present invention provides a novel phosphorus-containing olefin polymer that comprises cycloolefin as a first component and a vinyl phosphorus-containing compound as a second component. The present invention further provides a method for producing such phosphorus-containing olefin polymer and a composition and an article comprising the same.
Claims
1. A phosphorus-containing olefin polymer, comprising: (1) a first component; and (2) a second component, wherein the first component is cycloolefin, and the second component is a vinyl phosphorus-containing compound.
2. The phosphorus-containing olefin polymer of claim 1, wherein the vinyl phosphorus-containing compound is selected from the group consisting of a vinyl DOPO compound, a vinyl DPPO compound, a vinyl phosphazene compound, vinyl phosphate, an acrylate DOPO compound and a combination thereof.
3. The phosphorus-containing olefin polymer of claim 2, wherein the vinyl DOPO compound comprises one of the following structural formulae: ##STR00015## wherein n is an integer of from 1 to 4, and ##STR00016## wherein Y is —CH.sub.2— or —CH.sub.2—O—CH.sub.2—; n is a natural number of from 1 to 4; c is a natural number of from 1 to 4; and d is 0 or a natural number of from 1 to 6; wherein the vinyl DPPO compound comprises the following structural formula: ##STR00017## wherein the vinyl phosphazene compound comprises one of the following structural formulae: ##STR00018## wherein n is an integer of from 1 to 6, and ##STR00019## wherein m is an integer of from 1 to 6; wherein the vinyl phosphate comprises one of the following structural formulae: ##STR00020## wherein the acrylate DOPO compound comprises the following structural formula: ##STR00021##
4. The phosphorus-containing olefin polymer of claim 1, wherein the cycloolefin is selected from the group consisting of dicyclopentadiene represented by formula (10), norbornene represented by formula (11) and a combination thereof, ##STR00022## wherein m is a natural number of from 1 to 10.
5. The phosphorus-containing olefin polymer of claim 1, wherein the phosphorus- containing olefin polymer further comprises a third component.
6. The phosphorus-containing olefin polymer of claim 5, wherein the third component is selected from the group consisting of divinylbenzene, bis(vinylbenzene)ether, bis(4-vinylphenyl)methane, bis(4-vinylphenyl)ethane, styrene, ethylene, butadiene and diethyl diallylmalonate.
7. A method for manufacturing a phosphorus-containing olefin polymer, comprising: polymerizing a first monomer and a second monomer in the presence of a catalyst to form a phosphorus-containing olefin polymer, wherein the first monomer is cycloolefin, and the second monomer is a vinyl phosphorus-containing compound.
8. The method for manufacturing a phosphorus-containing olefin polymer of claim 7, wherein the catalyst is selected from the group consisting of peroxide, a ruthenium catalyst and a metallocene catalyst.
9. The method for manufacturing a phosphorus-containing olefin polymer of claim 8, wherein the ruthenium catalyst is a Grubbs catalyst.
10. A composition, comprising the phosphorus-containing olefin polymer of claim 1.
11. An article manufactured from the composition of claim 10, wherein the article is a resin film, resin coated copper, a prepreg, a laminate or a printed circuit board.
Description
BRIEF DESCRIPTION OF THE DRAWINGS
[0045]
[0046]
DETAILED DESCRIPTION OF THE INVENTION
Preparation Example 1
[0047] To a glass reaction bottle, 20 g toluene, 60 g ally phosphazene compound (SPV-100 available from Otsuka Chemical Co., Ltd.), 40 g dicyclopentadiene monomer (Dicyclopentadiene available from Sigma-Aldrich) and 0.01 g Grubbs catalyst II (Grubbs Catalyst 2nd Generation available from Sigma-Aldrich) were added to obtain a solution. The solution was heated to 80° C. and stirred for 12 hours. Then, the solution was cooled to room temperature to obtain a dark brown liquid solution, i.e., phosphorus-containing olefin polymer product A of the present invention (product A). The theoretical value of phosphorus atomic content of the phosphorus-containing olefin polymer is 7.2%.
[0048] Product A was analyzed in Fourier transform infrared spectroscopy (FTIR) and the results are shown in
Preparation Example 2
[0049] To a glass reaction bottle, 20 g toluene, 60 g allyl phosphazene compound (SPV-100available from Otsuka Chemical Co., Ltd.), 40 g 5-viny -2-norbornene (5-vinyl-2-norbornene available from Sigma-Aldrich) monomer and 0.01 g Grubbs catalyst II (Grubbs Catalyst 2nd Generation available from Sigma-Aldrich) were added to obtain a solution. The solution was heated to 80° C. and stirred for 12 hours. Then, the solution was cooled to room temperature to obtain a dark brown liquid solution, i.e., phosphorus-containing olefinpolymer product B of the present invention (product B).
Preparation Example 3
[0050] To a glass reaction bottle, 20 g toluene, 60 g DOPO-HQ terminal vinylated compound (i.e. vinylbenzyl-etherified-DOPO, synthesized by Elite Material Co., Ltd. and disclosed in U.S. Patent Application No.: U.S. Ser. No. 14/520,779, U.S. Patent Publication No.: 2015-0166788), 40 g dicyclopentadiene monomer (Dicyclopentadiene available from Sigma-Aldrich) and 0.01 g Grubbs catalyst II (Grubbs Catalyst 2nd Generation available from Sigma-Aldrich) were added to obtain a solution. The solution was heated to 80° C. and stirred for 12 hours. Then, the solution was cooled to room temperature to obtain a light brown liquid solution, i.e., phosphorus-containing olefin polymer product C of the present invention (product C).
Preparation Example 4
[0051] To a glass reaction bottle, 20 g toluene, 60 g DOPO-HQ terminal vinylated compound (synthesized by Elite Material Co., Ltd. and disclosed in U.S. Patent Application No.: U.S. Ser. No. 4/520,779, U.S. Patent Publication No.: 2015-0166788), 40 g 5-vinyl-2-norbornene (available from Sigma-Aldrich) monomer and 0.01 g Grubbs catalyst II (Grubbs Catalyst 2nd Generation available from Sigma-Aldrich) were added to obtain a solution. The solution was heated to 80° C. and stirred for 12 hours. Then, the solution was cooled to room temperature to obtain light brown liquid solution, i.e., phosphorus-containing olefin polymer product D of the present invention (product D).
[0052] Preparation Example 5
[0053] The phosphorus-containing olefin polymer of this example was prepared based on the method described in Preparation Example 1 except that in this example, cyclopentadiene monomer (Dicyclopentadiene available from Sigma-Aldrich) was replaced with commercial cycloolefin (Topas COC 5013 available from TOPAS Advanced Polymers Inc.) to obtain a dark brown liquid solution, i.e., phosphorus-containing olefin polymer product E of the present invention (product E).
Preparation Example 6
[0054] The phosphorus-containing olefin polymer of this example was prepared based on the method described in Preparation Example 1, except that in this example, 40 g allyl phosphazene compound (SPV-100 available from Otsuka Chemical Co., Ltd.) and 60 g dicyclopentadiene monomer (Dicyclopentadiene available from Sigma-Aldrich) were used to obtain a dark brown liquid solution, i.e., phosphorus-containing olefin polymer product F of the present invention (product F).
Preparation Example 7
[0055] To a glass reaction bottle, 20 g toluene, 40 g dicyclopentadiene monomer (Dicyclopentadiene available from Sigma-Aldrich) and 0.01 g Grubbscatalyst II (Grubbs Catalyst 2nd Generation available from Sigma-Aldrich) were added to obtain a solution. The solution was heated to 80° C. and stirred for 12 hours. Then, the solution was cooled to room temperature to obtain light brown liquid solution i.e., phosphorus-containing olefin polymer product G of the present invention (product G).
[0056] Preparation Example 8
[0057] The phosphorus-containing olefin polymer of this example was prepared based on the method described in Preparation Example 7, except that in this example, 40 g dicyclopentadiene monomer (Dicyclopentadiene) was replaced with 40 g 5-vinyl-2-norbornene (available from Sigma-Aldrich) monomer to obtain a light brown liquid solution, i.e., phosphorus-containing olefin polymer product H of the present invention (product H).
Preparation Example 9
[0058] The phosphorus-containing olefin polymer of this example was prepared based on the method described in Preparation Example 1, except that in this example, 60 g allyl phosphazene compound(SPV-100) was replaced with 60 g triallyl isocyanurate (TAIC available from Kingyorker Enterprise Co. Ltd.) to obtain a light brown liquid solution, i.e., phosphorus-containing olefin polymer product I of the present invention (product I).
Preparation Example 10
[0059] The phosphorus-containing olefin polymer of this example was prepared based on the method described in Preparation Example 1, except that in this example, 60 g allyl phosphazene compound (SPV-100) was not used. A light brown liquid solution was thus obtained to be polydicyclopentadiene.
[0060] Polydicyclopentadiene was analyzed by Fourier transform infrared spectroscopy (FTIR) and was compared with the spectrogram of product A. The results are shown in
Example and Comparative Example
[0061] As shown in the following Table 1 to Table 6, the components and addition amounts of the resin compositions and the properties of laminates are listed.
[0062] Material Source [0063] SFV-100: Allyl phosphazene flame retardant (i.e., formula (5), wherein n=3˜6) available from Otsuka Chemical Co., Ltd. [0064] DCPD monomer: Dicyclopentadiene monomer available from Sigma-Aldrich. [0065] Grubbs catalyst II (Grubbs Catalyst 2nd Generation, (1,3-bis-(2,4,6-trimethylphenyl)-2-imidazolidinylidene)dichloro(o-isopropoxyphenylmethylene)ruthenium)): available from Sigma-Aldrich. [0066] 5-vinyl-2-norbornene monomer: available from Sigma-Aldrich. [0067] DOPO-HQ terminal vinylated compound: synthesized by Elite Material Co., Ltd. (disclosed in U.S. Patent Application No.: U.S. Ser. No. 14/520,779, U.S. Patent Publication No.: 2015-0166788) [0068] Topas COC 5013: Commercial cycloolefin polymer free of reaction functional groups and available from Topas Inc. [0069] TAIC: Triallyl isocyanurate available from Kingyorker Enterprise Co., Ltd. [0070] 25B: Peroxide available from Nippon Oil & Fats Co., Ltd. [0071] SC-2050 SVJ: Spherical silica available from Admatechs. [0072] OPE-2st 2200: Vinyl polyphenylene oxide, available from MITSUBISHI GAS CHEMICAL COMPANY, INC. [0073] BMI-80: Maleimide available from KI Chemical. [0074] Ricon-257: styrene-butadiene-divinylbenzene terpolymer available from Cray Valley. [0075] Toluene: available from Chambeco. [0076] MEK: Methyl ethyl ketone available from Chambeco.
[0077] Method for Preparing Test Samples of Examples and Comparative Examples:
[0078] Each of the resin compositions in different groups of Examples and Comparative Examples was added to a stirring tank for stirring until complete dissolution and uniform mixing. The resin composition solution was placed in a impregnation tank, and then a fiber glass cloth (2116 E-fiber glass cloth) was impregnated in the above impregnation tank, such that the resin composition attached to and impregnated in fiber glass cloth. The fiber glass cloth was baked at a temperature of from 120 to 170° C. to become semi-cured (B-Staged), and thus a prepreg was obtained.
[0079] 1. Copper Clad Laminate (Four-Ply):
[0080] Two HTE (High Temperature Elongation) copper foils (0.5 ounces for each) (a thickness of 18 micrometers) and four prepregs made from each of the test samples were provided. In each prepreg, the resin content was about 55%. One copper foil, four prepregs and one copper foil were stacked sequentially, and then were laminated in a vacuum condition at 195° C. for 2 hours to form a copper clad laminate for each group, wherein the four laminated prepregs were cured to form an insulating layer between two copper foils and the resin content in the insulating layer was about 55%.
[0081] 2. Copper-Free Laminate (Four-Ply):
[0082] The above copper clad laminates (four-ply) were etched to remove the copper foils on two sides, so as to obtain a copper-free laminate (four-ply). The copper-free laminate (four-ply) was formed by laminating four prepregs (C-staged), and the resin content of the copper-free laminate (four-ply) was about 55%.
[0083] 3. Copper-Free Laminate (Two-Ply):
[0084] Two HTE (High Temperature Elongation) copper foils (0.5 ounces for each) (a thickness of 18 micrometers) and two prepregs made from each of the test samples were provided. In each prepreg, the resin content was about 55%. One copper foil, two prepregs and one copper foil were stacked sequentially, and then were laminated in a vacuum condition at 195° C. for 2 hours to form a copper clad laminate for each group, wherein the two laminated prepregs were cured to form an insulating layer between two copper foils and the resin content in the insulating layer was about 55%.
[0085] Subsequently, the above copper clad laminate (two-ply) was etched to remove the copper foils on two sides, so as to obtain a copper-free laminate (two-ply). The copper-free laminate (two-ply) was formed by laminating two prepregs (C-staged). The resin content of the copper-free laminate (two-ply) was about 55%.
[0086] Laminate Property Analysis Item and a Test Method Thereof:
1. Determination of Laminate Appearance
[0087] The surface of the copper-free laminate (four-ply) was visually determined to be flat and smooth or weave exposed. The size of the copper-free laminate is 9×12 inch.sup.2. If the surface of the copper-free laminate has at least one more than 1×1 cm.sup.2 weave exposure, such laminate is determined as a dry plate. If the surface of the laminate is flat and smooth, no dry plate occurs. Weave exposure is determined based on the common knowledge of a person skilled in the art. If a dry plate phenomenon occurs on a laminate, such laminate cannot be used in the subsequent multilayer sheets or circuit boards.
2. Glass Transition Temperature
[0088] In a glass transition temperature test, the above copper-free laminate (four-ply) was used as a sample. The glass transition temperature of the sample was measure by using Dynamic Mechanical Analyzer (DMA) and referring to the method described in IPC-TM-650 2.4.24.4 Glass Transition and Modulus of Materials Used in High Density Interconnection (HDI) and Microvias-DMA Method.
3. Percent of Thermal Expansion
[0089] In the measurement of the percent of thermal expansion, a copper-free laminate (four-ply) was used as a sample. The measurement was performed by using a thermal mechanical analyzer (TMA), heating in a heating rate of 10° C./min from 50° C. to 260° C. and referring to the method described in IPC-TM-650 2.4.24.5 to determine the dimensional change of each sample (unit: %). The lower a percent of thermal expansion is, the better the laminate is.
4. T288 Thermal Resistance
[0090] In a T288 thermal resistance test, the above copper clad laminate with 6.5 mm×6.5 mm was used as a sample. At a constant temperature of 288° C., a thermal mechanical analyzer (TMA) was used and based on the method described in IPC-TM-650 2.4.24.1, the time that no delamination occurred after the copper clad laminate was heated was measured. A longer time means that the thermal resistance of the copper clad laminate made from the resin composition is better.
5. Solder Dipping (SID)
[0091] In a solder dipping test, the above copper clad laminate (four-ply) was used as a sample. The method described in IPC-TM-650 2.4.23 Soldering Resistance of Laminate Materials to measure each sample was referred to. Each sample was dipped in a solder pot with a constant temperature of 288° C. for 10 seconds, and then was taken out at room temperature for 10 seconds. The above steps were repeated and the repeat number was recorded until the laminate was delaminated. In general, the more the repeat number for each sample in solder dipping without delamination is, the better the thermal resistance of an article (such as copper clad laminate) made from the resin composition is.
6. Dielectric Constant and Dissipation Factor:
[0092] In the measurements of a dielectric constant and a dissipation factor, the above copper-free laminate (two-ply) was used as a sample. A microwave dielectrometer (available from Japan AET Company) was used and based on the method described in. TIS C2565, each sample was measured at room temperature (about 25° C.) and a frequency of 10 GHz. The lower a dielectric constant and a dissipation factor are, the better the dielectric properties of a sample are. The Dk value difference smaller than or equivalent to 0.05 means that laminates do not have a significant difference in dielectric constant while the Dk value difference greater than 0.05 means that different laminates have a significant difference in dielectric constant. The Df value difference smaller than or equivalent to 0.0005 means that laminates do not have a significant difference in dissipation factor while the Df value difference greater than 0.0005 means that different laminates has a significant difference in dissipation factor.
7. Dissipation Factor Post-Moisture Absorption
[0093] In the measure of a dissipation factor post-moisture absorption, the above copper-free laminate (two-ply) was used as a sample. The sample was placed in 121° C. saturated water vapor (pressure cooking test, PCT test) for 5-hour moisture absorption, and then a dissipation factor test was performed. The method for testing the dissipation factor is the same as that in the above item 6.
8. High Temperature Dissipation Factor
[0094] In a high temperature dissipation factor test, the above copper-free laminate (two-ply) was used as a sample. The test method is the same as that in the above item 6, except that the measurement at room temperature (about 25° C.) was conducted at 120° C.
9. Flame Retardant Test
[0095] In a flame retardant test, a copper-free laminate (four-ply) with 125 mm×13 mm was used as a sample. Based on the method of UL94, measurement was performed and the results of flame retardant analyses can be expressed as V-0, V-1, and V-2, wherein the flame retardant of V-0 is better than the flame retardant of V-1 and the flame retardant of V-1 is better than the flame retardant of V-2. If a sample is burned up, the flame retardant is the worst.
TABLE-US-00001 TABLE 1 Resin Name of raw composition Component material E1 E2 E3 E4 E5 C1 C2 C3 C4 Polymer Product A prepared in Preparation Example 1 Product A 100 Product B prepared in Preparation Example 2 Product B 100 Product C prepared in Preparation Example 3 Product C 100 Product D prepared in Preparation Example 4 Product D 100 Product E prepared in Preparation Example 5 Product E 100 Product F prepared in Preparation Example 6 Product F 100 Product G prepared in Preparation Example 7 Product G 100 40 40 Product H prepared in Preparation Example 8 Product H Product I prepared in Preparation Example 9 Product I Monomer DCPD monomer 5-vinyl-2-norbornene monomer cycloolefin polymer Topas COC TAIC 5013 Flame retardant allyl phosphazene SPV-100 20 60 DOPO-HQ terminal vinylated compound 60 Catalyst ruthenium catalyst Grubbs 2nd 0.01 0.01 peroxide 25B 1 1 1 1 1 1 1 1 1 Inorganic filler spherical silica SC-2050 SVJ 30 30 30 30 30 30 30 30 30 Solvent toluene 100 100 100 100 100 100 100 100 100
TABLE-US-00002 TABLE 2 Property Test Item of laminate (Method) Unit E1 E2 E3 E4 E5 C1 C2 C3 C4 appearance dry plate no unit No No No No No YES No No No (visually determined) Glass transition Tg (DMA) ° C. 140 153 147 177 151 107 170 115 112 temperature Percent of Dimensional % 3.09 3.01 2.99 2.94 3.03 3.43 3.42 3.54 3.34 thermal change expansion (TMA) T288 thermal T288 (TMA) minute 61 62 60 62 60 10 15 10 10 resistance Solder dipping S/D cycle >20 >20 >20 >20 >20 5 >20 15 15 Dielectric Dk@10 GHz no unit 3.58 3.52 3.65 3.61 3.57 3.65 3.45 3.56 3.86 constant @25° C. Dissipation factor Df@10 GHz no unit 0.0053 0.0048 0.0056 0.0053 0.0055 0.0064 0.0045 0.0048 0.0068 @25° C. Dissipation factor Df@10 GHz no unit 0.0055 0.0051 0.0059 0.0055 0.0057 0.0070 0.0048 0.0051 0.0071 post-moisture @25° C. absorption after 5-hour PCT High temperature Df@10 GHz no unit 0.0054 0.0050 0.0058 0.0054 0.0056 0.0067 0.0048 0.0052 0.0072 dissipation factor & @120° C. Flame retardance UL94 no unit V-0 V-0 V-0 V-0 V-0 V-0 Burned V-0 V-0 test out
TABLE-US-00003 TABLE 3 Resin Name of raw composition Component material C5 C6 C7 C8 C9 C10 C11 C12 C13 Polymer Product A prepared in Preparation Product A Example 1 Product B prepared in Preparation Product B Example 2 Product C prepared in Preparation Product C Example 3 Product D prepared in Preparation Product D Example 4 Product E prepared in Preparation Product E Example 5 Product F prepared in Preparation Product F Example 6 Product G prepared in Preparation Product G Example 7 Product H prepared in Preparation Product H 100 40 40 Example 8 Product I prepared in Preparation Product I 100 40 40 Example 9 Monomer DCPD monomer 40 5-vinyl-2-norbornene monomer 40 cycloolefin polymer Topas COC 40 TAIC 5013 Flame allyl phosphazene SPV-100 60 60 60 60 60 retardant DOPO-HQ terminal vinylated 60 60 compound Catalyst ruthenium catalyst Grubbs 2nd 0.01 0.01 0.01 0.01 0.01 0.01 0.01 0.01 0.01 peroxide 25B 1 1 1 1 1 1 1 1 1 Inorganic spherical silica SC-2050 30 30 30 30 30 30 30 30 30 filler SVJ Solvent toluene 100 100 100 100 100 100 100 100 100
TABLE-US-00004 TABLE 4 Property Test Item of laminate (Method) Unit C5 C6 C7 C8 C9 C10 C11 C12 C13 appearance dry plate no unit No No No No No No No No Yes (visually determined) Glass transition Tg (DMA) ° C. 142 135 131 161 134 132 101 124 131 temperature Percent of Dimensional % 3.24 3.56 3.56 3.46 3.76 3.67 3.76 3.76 3.56 thermal change expansion (TMA) T288 thermal T288 (TMA) minute 10 15 15 15 15 13 6 16 10 resistance Solder dipping S/D cycle 15 17 18 18 13 19 12 14 11 Dielectric Dk@10 GHz no unit 3.86 3.58 3.78 3.71 3.88 3.63 3.78 3.68 3.68 constant @25° C. Dissipation factor Df@10 GHz no unit 0.0058 0.0058 0.0059 0.0061 0.0068 0.0061 0.0068 0.0065 0.0063 @25° C. Dissipation factor Df@10 GHz no unit 0.0061 0.0062 0.0064 0.0066 0.0075 0.0067 0.0071 0.0069 0.0068 post-moisture @25° C. absorption after 5-hour PCT High temperature Df@10 GHz no unit 0.0062 0.0061 0.0062 0.0065 0.0077 0.0069 0.0073 0.0071 0.0067 dissipation factor & @120° C. Flame retardance UL94 no unit Burned V-0 V-0 Burned V-0 V-0 V-0 V-0 V-0 test out out
TABLE-US-00005 TABLE 5 Name of raw Resin composition Component material E6 E7 E8 E9 E10 C14 C15 C16 C17 Polymer Product A prepared in Preparation Example 1 Product A 40 Product B prepared in Preparation Example 2 Product B 40 Product C prepared in Preparation Example 3 Product C 40 Product D prepared in Preparation Example 4 Product D 40 Product E prepared in Preparation Example 5 Product E 40 Product F prepared in Preparation Example 6 Product F 40 Product G prepared in Preparation Example 7 Product G 40 Product H prepared in Preparation Example 8 Product H 40 Product I prepared in Preparation Example 9 Product I 40 Monomer DCPD monomer 5-vinyl-2-norbornene monomer cycloolefin polymer Topas COC TAIC 5013 Polyphenylene vinyl polyphenylene oxide OPE-2st 2200 60 60 60 60 60 60 60 60 60 oxide Linear olefin styrene-butadiene-divinylbenzene terpolymer Ricon-257 15 15 15 15 15 15 15 15 15 Maleimide maleimide BMI-80 10 10 10 10 10 10 10 10 10 Flame retardant allyl phosphazene SPV-100 20 60 60 60 DOPO-HQ terminal vinylated compound Catalyst ruthenium catalyst Grubbs 2nd peroxide 25B 1 1 1 1 1 1 1 1 1 Inorganic filler spherical silica SC-2050 SVJ 30 30 30 30 30 30 30 30 30 Solvent toluene 100 100 100 100 100 100 100 100 100 MEK 30 30 30 30 30 30 30 30 30
TABLE-US-00006 TABLE 6 Property Test Item of laminate (Method) Unit E6 E7 E8 E9 E10 C14 C15 C16 C17 appearance dry plate no unit No No No No No No No No No (visually determined) Glass transition Tg (DMA) ° C. 189 192 195 191 189 159 154 195 194 temperature Percent of Dimensional % 2.88 2.78 2.83 2.91 2.99 3.17 3.23 3.31 3.14 thermal change expansion (TMA) T288 thermal T288 (TMA) minute >70 >70 >70 >70 >70 30 30 30 30 resistance Solder dipping S/D cycle >20 >20 >20 >20 >20 18 17 18 19 Dielectric Dk@10 GHz no unit 3.62 3.66 3.65 3.68 3.52 3.65 3.65 3.65 3.65 constant @25° C. Dissipation factor Df@10 GHz no unit 0.0055 0.0053 0.0057 0.0054 0.0055 0.0053 0.0056 0.0055 0.0058 @25° C. Dissipation factor Df@10 GHz no unit 0.0057 0.0055 0.0059 0.0057 0.0057 0.0055 0.0060 0.0060 0.0065 post-moisture @25° C. absorption after 5-hour PCT High temperature Df@10 GHz no unit 0.0056 0.0054 0.0058 0.0057 0.0056 0.0055 0.0060 0.0061 0.0066 dissipation factor & @120° C. Flame retardance UL94 no unit V-0 V-0 V-0 V-0 V-0 V-0 V-0 V-0 V-0