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    Thermosetting Resin Composition

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    cu») United States ‘US 202000628894 | 2) Patent Application Publication co) Pub. No.: US 2020/0062889 A1 LUO et al. (54) THERMOSETTING RESIN COMPOSITION (OL) Applicant: Shengyi Technology Cou Ltd. Guangdong (CN) Inventors: Cheng LUO, Guangdong (CN): Guofang TANG, Geangsdang (CN) Siangling ZHANG, Guangdong (CN) (21) Appl. Nos 16,466,002 (2) PCT Filed: Feb. 21, 2017 (85) PCTNo: — PETICN20177074297 $371 (eX), (2) Date: Jun, 3, 2019 G0) Foreign Application Priority Data Dee. 7, 2016 (CN) 2016111151288 Publication Classification (1) Inch. Ca8G 59/40 CosL 63/00 (2006.01) (2008.01) (43) Pub. Date Feb. 27, 2020 (62) US.CL CBC 2. C08G 80/4071 2013.01); COSL 2201/22 (2013.01); CoSz, 2201/02 (2013.01), CUBE. {63/00 (2013.01) on ABSTRACT Provided in the present invention is thermosetting resin ‘composition, comprising phosphorus-contaning active ester and epoxy resin, the phosphorus-containing active ester being copolymerised using bis-aromatic formyl chloride bydrocarby] phosphine oxide and one of bis-hydroxyl aro- ‘atic hydrocarby! phosphine oxide, bis-hydroxyl aromatic coxyhydracarbyl phosphine oxide, or hydroxylated DOPO, ‘and then obtained from aromatic formyl chloride end cap. Ping; the thermosetting resin composition provided ia the present invention has the advantages of good thermal sta- bility, humidity resistance and heat resistance, low dielee- trie constant and dielectric loss tangent, low rate of water absorption, and halogen-fee fame-retardaut properties, and hhas excellent machinabilty, also provided in the present invention are applications of the thermosetting resin com- positon for resin shect material, resin composite metal foi, prepreg, laminated plate, metal fol-clod laminated plate fd printed circuit Boards US 2020/0062889 AI ‘THERMOSETTING RESIN COMPOSITION ‘TECHNICAL FIELD. 10001} ‘The present invention relates to the technical field ‘of polymer materials, in particular to a thermosetting resin ‘composition, aswell as a prepreg and. printed eireuit board sing the same, BACKGROUND ART 10002} Conventional printed circuit laminates usually achieve flame retardaney by using brominated flame neta ‘dant, especially etrabrono-bisphenol A epoxy resin Which has good fame retardancy, bu will produce hydrogen bro- mide ges during combustion, Furthermore, carcinogens sich ‘8 dioxins and dibenvofirans have been detected in recent {years in combustion products of electrical and electronic ‘equipment wastes containing halogens such as bromine and ‘chlorine. Thus the application of brominated epoxy resins is Jimited. Two BU environmental directives of Waste Electr ‘al and Electronic Equipment Directive andthe Restriction ‘ofthe Use of Certain Hazardous Substances in Electrical and Electronic Equipment have been offically implemented oa Jul. 1, 2006. The development of halogen-free flame retar- ‘dant copper-lad laminates has become a hot spot in the industry. and various CCL. manufacturers have launched their on halogen-fiee flame retardant copperclad lami- 10003] The intoduetion ofa phosphorus-contaning com- pound into the resin matrix of eopper-clad laminates has come the main technieal route for the halogen-free Mame retardancy of copper-clad laminates. At present, phospho- rus-based Name retardants Widely used i the Held of copper clad laminates are mainly classified into wo types, ie. reactive type and additive type. The reactive type mainly involves DOPO-based compounds primarily comprising pPhosphonts-contsising epoxy’ resins and phosphorus-coo- taining phenolic resins and having @ phosphorus eontent of 2-10%%. However, it has been found in pratieal applications that DOPO-based compounds have a lage water absorption rate, poor dielectric properties, and worse heat and humidity resistance. The additive type miinly relates 1 phosphazeae ‘and phosphonate compounds. The additive flame retardant has low fame retardancy efficiency, and cannot achieve the flame retardant requirement unless adding more. Mean- ‘while it is easy t0 migrate tothe surface ofthe sheet during the processing of laminates due to it lower melting point (generally losser than 150° C.), thus affecting the peror- rmanoes of the sheet, 10004] In addition, in order to meet the processability of the PCB and the performance requirements of the terminal ‘electronic produc, its necessary for coppersclad substrate materials to have good dielectric properties, heat resistance sand mechanical properties, and albo to have good processing ‘characteristics, high peel strength and excellent heat and humidity resistance, [0005] -Dicarboxyphenyl hydrocarbyl phosphine oxide is 3 reactive phosphorus-containing curing ageat, and dihy- droxyphenyl hydrocarbyl phosphine oxide and hydroxy” ‘containing phosphaphentanthrene can be cured with epoxy resins, bt the reactive groups thereof which are carboxy groups or hydroxyl groups will produce more secondary hydroxy! groups with lage polanty after the reaction with ‘epoxy resin, resulting in poor dielecsic properties of the Feb. 27, 2020 ceured product. Moreover, carboxyl groups and hydroxyl sroups are highly reactive, esulting in extremely difficalt processing control thereof, CNIOS3846744. discloses ‘composition composed of polyphosphonate orland a phos shonate-carbonate copolymer having hydroxyl groups and ‘an epoxy, wherein the ative group is a phenolic hydroxy] rou, which also tas the problem of poor dielectric prop- fertics, CNIO3694642A discloses using epoxy resins, «yanate compounds ovfand eyanate prepolymer, polyphios- Phonate or/and phosphonate-carbonate copolymers for the preparation of halogen-free UL4 V0 flame retardant bay fing good dielectric properties and good heat and humidity resistance, However, it has «lower pecl strength, interlayer ‘adhesion and flexural strength, DISCLOSURE OF THE INVENTION [0006] ‘The inventors found by research thatthe phospho- ris-contaiing active ester with a special strcture as the ‘curing agent of epoxy resins does not generate secondary hydroxyl groups with a large polarity when reacting with the ‘pony resins, so a to make the system have poo dielectric properties. Meanwhile, i isa phosphorus-contaning active ‘ester curing agent, and has a halogen-free flame retardant effect when used a a curing agent, Moreover, it hes a high flame retardant efficiency, and can make the sheots reach ‘UL94'V-0 halogen-free fame retardant effect when added in 4 small amount or without adding other lame retardants 0007] On such a basis, one of the objects of the present invention iso provide a thermoseting resin composition, as ‘well as a prepreg and a laminate for printed circuit boards Using the same. The laminate for printed cieuit boards prodiced sing the resin composition has high glass tran ‘ion temperate, excellent dielectric properties, high heat resistance, excellent peel strength and good processability. and can achieve halogencfree fame retardancy and reach UL94 V0, [0008] The present inventors conducted intensive studies in order to achieve the above object, and found, asa result that @ composition obtained by appropriately mixing an epoxy resin, a phosphorus-containing active ester having a special strcture, and optionally other curing agents can achieve the above object [0009] That is to say, the present invention discloses the {allowing technical solution, i. a thermosetting resin com- position comprising an epoxy resin and a curing agent, ‘whorein the curing agent comprises at lest one phosphorus conaining active ester having a special siracture [0010] The thermosetting resin composition of the present invention uses & phosphorus-containing active ester having fa special siruetire as a curing agent for an epoxy resi, The active estor group asa reactive group has a high content, and «an be eured with an epoxy resin (0 obtain 2 ‘having a high crosslinking density, s0 as to ob ‘having high heat resistance and high Te. The phosphonis- containing active ester having a special strictare contsins ‘aromatic groups in a high content, which has a positive effect on the glass transition temperature and flame retar- ancy, The active ester unit in the molecule does not ‘generite secondary hydroxyl groups having a large polarity After reacting wih the epoxy resin, which can eliminate the tisadvantage of poor dislectrie properies brought by sec- ondary hydroxyl groups having a large polarity, so as 10 ‘make excellent dielectric properties. The ester bond formed by the reaction of the phosphorus-containing active ester US 2020/0062889 AI having a special structure with the epoxy’ has a low water absomption rate, hereby improving the disadvantages of poor heat and humidity resistance of the phosphorus-con- taining compounds, In addition, the phosphorus-containing ‘etive ester having u special structure contains phosphors jn the main sirctoral monomers therof, and have a high ‘overall phosphorus content, which can achieve a halogen- fe flame retardant effect. Moreover, it has a high flame retardant eficioney, and can reach UL94 V-0 fame retardant ‘effect when added ina small amount or without adding other ‘lame retardants. [0011] The present invention discloses utilizing a phos- Phorus-contsining ative ester having a highly symmetrical special structure, which can significantly improve the glass transition temperamee and heat resistance of a prepreg and laminate for printed circuit boards made from the resin ‘composition, and make them have excellent dielectric prop ‘erties, low water absorption, good heat and humidity resis: tance and good processability, and can achieve halogen-free flame retardancy and reach ULO4 V-0, The components are described in detail below. 10012] According to the present invention, the phospho- rus-containing active ester is obtained by copolymerizing & ». said aromatic formyl chloride has a structural formula of oma (V), ‘wherein R, and Rare identical or fferent from each other, and each independently anyone selected from the group consisting of phenyl, naphih!, and linear or branched alky having 1 to 4 carbon atoms, wherein the linear or branched alkyl having 1 to 4 carbon uioms is anyone selected rom the sacup consisting of methyl, ethyl, propyl, butyl, isopropyl, Ssobutyl, and tet-butyl; ‘wherein Ar, and Ar, are identical o¢ diferent from each other, and ach independently anyone selected from the rovp consisting of | US 2020/0062889 AI -continved OO <> 3 <)- ore nd ‘eH Feb. 27, 2020 continued iG OS. ‘wherein Ary is anyone selected from the group consisting of Oy ‘wherein Ar is anyone selected from the group consisting of ae wherein a, isan integer of 0-5, eg. 0, 1, 23,4 oF S: ‘wherein ng is an integer of 07, eg. 0, 1,2,3,4, 5.60075 ‘wherein Ris anyone selected from the group consisting of linear or branched alkyl groups having 1 to 4 carbo atoms, eg, anyone selected from the group consisting of meth, cetiyl, propyl, buts, isopropyl, isobutyl, and tert-butyl. [0013] Preferably, the phosphorus-containing active ester is obtained by catbylphosphine oxide with a phosphine oxide and then termi ehlorie, wherein the phosphorus sontaining ative ester has 4 strctural Formula of formula (VD), US 2020/0062889 AI Feb. 27, 2020 : oma 0) i A000 nf — te & & specifically, the strwctral Formula ean be the fllowing stot, coo. coe 4 coo. coe Preferably, the phosphiorus-containing tive ester is phosphine oxide and then terminating by an aromatic formyl ‘obtained by copolymerizing a diaryliomaylehlorohydocar- chloride, wherein the phosphorus-coataining ative ester has bylphosphine oxide with a dihydroxyaryloxyhydrocasbyl- a sinictural formila of forma (VID), wtofet Foal (V1 specifically, the structural formula ean be the following structure, ~ Oo US 2020/0062889 AI Feb. 27, 2020 continued of j od Preferably, the phosphorws-containing octive ester is ‘obtained by copolymerizing a diaryormylehlorohydrocar- bylphosphine oxide with a hydroxylated DOPO and thea terminating by an aromatic formyl chloride, wherein the phosphionis-contsining active ester has a structural formula ‘of formula (VI), enla(V) taf anol bet specifically, the structural formula ean be the following US 2020/0062889 AI continued 9 8 QP OO Preferably, the phosphorus-containing active ester is ‘obtained by copolymerizing a diaryformylehlotohydrocar- bylphosphine oxide with a dihydroxyaryloxyhydrocaehyl- phosphine oxide and a hydroxylated DOPO and then temic nating by an aromatic formyl chloride, wherein the phosphonis-contsining active ester as a structural formula ‘of formula (IX) oF (X). O- Feb. 27, 2020 20 ogg Feb. 27, 2020 US 2020/0062889 AI US 2020/0062889 AI Feb. 27, 2020 specifically, the structural formula can be the following US 2020/0062889 AI Feb. 27, 2020 10 The phosphorus-containing active ester ofthe present inven continued tion ean also be obtained by copolymerizing a diaryform- ROOF yitloroyccarylpboephine oxide with diycroxyary- ° Ioxyhydocerbylphosphine oxide and i : Aitydroxyarhydrocarhpiphospne oxide and then temi- i nating by an aromatic formyl chloride, wherein the phos- 7 phorus-containing active ester has a structural formula of formula (XD, ey men we 40- oe ‘wherein isan integer of 1-20, eg. 1,2,3, 4,5, 6, 7,8 9, continued Worth 12 1314 eof, 18 19 ora ern och ty and nis niger oF 040,645 81,4 8567, 0 . 3, tie ia, tet 15 fos 1%, 1819 00 0, and a0, om 80, ands Lo Te nd ora, isl, anny 195 are esc independently anyone selected from the group consisting of CH. 4(O- Feb. 27, 2020 continued a a is anyone selected from the group consisting of hydrogen ftom and substituted or unsubsitited linear or branched alkyl groups having a carbon number of 1-5, e. anyone Selected from the group consisting of methyl, ey, propyl butyl, pentyl, isopropyl, isobutyl, ter-buryl, and isopentyl: wherein n; is an integer of 110, eg. 1, 2.3.4, 5,6.7,8,9 or 1 [0019] Preferably, said glycidyl amines are anyone sclectod from the group consisting of tiglycidyl-p-ansino- eo, ali! winene ene, may ino-limethylenebenzene, teraglyeidyl-44'liaminod shonin, tnahciyi+fsiamndpton se ‘etraglyciyl-4,9-liamioodiphenyl ether, ttraglyeidyl-1 aminomethyleyelohexane, and @ mixture of af least 60 selected therefrom, [0020] The halogen-free thermosetting resin composition of the present invention comprises the halogen-free epoxy resin having the specific molecular structure described fahove, which has high Tusctionality aad good dielectic properties. The eured product thereof has @ high Ty and @ Tow water absorption rate [021] According to the present invention, the curing ‘agent may furher comprise a cyanate resin andlor a bisma- leimide-tiazine resin, wherein the eyanate resin has the following structure, ra ‘wherein R,, is anyone selected from the group consisting of cH, US 2020/0062889 AI -comtinsed Te is i ee ~ ot bi : ‘and a mixture of atleast wo selected therefrom: Ry, Ry, Ry Ry, Ryor Ry,» Rys and Ry, are each independently anyone selected from the group consisting of hydrogen atom and substituted or unsubstituted inear or branched alkyl groups having a carbon number of 1-4, eg. anyone selected from the group consisting of methyl, ethyl, propyl butyl, isopro- pyl, isobutyl, and tert-butyl 10022] Preferably, said eyanate resin is anyone select from the group consisting of 2,2-bis(4-) ie bod = ture was then warmed to 30° C. and reacted at such ‘temperature for 4h 352 z of maphhoyl chloride was furher added to the reaction system, and the reaction was also carried out at such temperature for 2h, The product was cooled to room temperature, and then a $% sodium carbon- ate solution was added. The mixture was stirred vigorously, filtered, washed with water and dried to obtain a product nbered a8 P-AES US 2020/0062889 AI Feb. 27, 2020 7 10070] wherein n-3. [0071] 5. Synthesis of PALS 10072] 403g of bis(4-benzoylchloro)phenylpbosphine ‘oxide, 558 of bis(4-tytdroxypheny)pheny}phiosphine ‘oxide and 1500 g of pyridine Were sted in a foursnecked flask equipped with a timer reflux condensation tube and 4 thermometer, while nitrogen gas was introduced, The mixture was then warmed to 30° C. and reacted at such temperature for 4 h. 238 g of benzoyl chloride was further added to the reaction system, and the reaction was also ‘carried out at such temperature for 2 h. The product was ‘cooled to room temperature, and then 2 59% sodium carbon- ‘ate solution was added. The mixture was sired vigorously, fikered, washed with water and dried to obtain a product numbered as P-ABS, ed 10073] 10073) 10075] 627 g of bis(4-(4-beazoylclorojphenylsulfonyl) Pheaylphosphine oxide, JSS of bis(4-hydroxybiphenyly= loxy}phenyphosphine oxide and 1500 p of pyridine were stir in a fouenecked flask equipped with a stirrer efhix ‘condensation tobe snd themometer, while nitrogen 0s 2 was introduced. The mixture was then warmed to 30° C. and reacted a such temperature for 4h, 390 g of benzoyl chloride wos further added to the reaiion system, and the waetion was also caried out at such temperature for h, The product was cooled to room temperature, and then a 59% Sodium carbonate solution was added. The mixture was Stimed vigorously, filterd, washed with water and dried to jobiain a product numbered as P-AEO. Feb. 27, 2020 US 2020/0062889 AI 18 +O OX) US 2020/0062889 AI 10076) wherein n=1 10077] The above phosphonis-containing active ester P-AE, a halogen-fre epoxy resin and a curing accelerator, ‘a halogea-free flame retardant and a filler were uniforaly mixed ina certain rato in a solvent, andthe solid content of the glue was controlled to be 65%, A 2116 fiberglass cloth ‘was impregnated with the above ge to contro the appro> Pate thickness thereof, then was baked in an oven at 115-175® C. for 2-15 minutes to proxioce « prepreg. Then several prepregs were stacked together, and 18 ym RIF C\-1e Feb. 27, 2020 ‘copper Foil was stacked on both sides thereof, to produce @ ‘opper-clad laminate at curing temperature of 170-250? C. 4 curing pressure of 25-60 kyem™ and a curing time of {60-300 min, [0078] The materials and brand informations thereof in Examples 1-21 aad Comparative Examples 1-12 are as follows: [o079] (ay [0080] P-AEI: Self-Mode Phosphonis-Contsining Active Ester [0081] wherein n,=10, and ny [0082] P-AE2: Self-Made Phosphorus-Containing Active ster [oosa} [oos4} wherein n,-8, and n: P-AE3: Self-Made Phosphorus-Containing Active Eser US 2020/0062889 AI Feb. 27, 2020 20 sontincd on 7 ye iL i i ot VIL Sco. =. [0085] wherein 9-3, and 3, fonts] Pale SdeAe Phosphons-Contining Active Ester (0087) wherein n-3. [0088] _P-AFS: Self Made Phosphorus-Containing Active Ester coo! [0089] wherein n-3. [0090] | P-AP6: SelfMade Phosphorus-Containing Active Baer Feb. 27, 2020 US 2020/0062889 AI ai OX) US 2020/0062889 AI Feb. 27, 2020 2 0091) wherein 0092} BHPPO: oxide [0096] (B) Cyanate [097] CY.40; Wugiao resin factory, DCPD-ype eyiante [098] Pres: LONCZ, 0099} CEOIPS: Jiangsu Tiangi bisphenol A-type eyanate [0100] CEOIMO: Jiangsu Tiangi, bisphenol Aype eyanate resin [0101] (C) Epoxy Resin [0102] _HP-7200HHF: DIC, DCPDaype epoxy resin hav- ing an epoxy equivalent of 288 [0103] HP-7200H-75M: DIC, DCPDAype epoxy resin having an epoxy equivalent of 280 [0104] HP-6000- DIC, Epoxy resin having an epoxy ‘equivalent of 250 [0105] 11P.9900- DIC, Naphholaype epoxy resin having fan epoxy equivalent of 274 [0106] NC-300011: Nippon Kayak, Biphenyl epoxy resin having an epoxy equivalent of 294 [0107] | SKE-1: Shankote, special epoxy resin having an ; epoxy equivalent of 120 I [0108] "SKE-3: Shankote, special epoxy resin having an ee eee ‘COOH epoxy equivalent of 120 [0109] (D) Phenolic Resin [110] DOW92741: Phosphorus-containing novolac resi, Dow Chemical [0111] SEB-0904PM60; Phosphorus-containing novela resin, SHIN-A [0112] SHIN-1655TM6S: Phosphorss-containing. novolac resin, SHIN-A [0113] 2812: linear novolac resin, MOMENTIVE (Kore) [o1t4] (P) Phosphorus-Containing Flame Retardant {009s} ODOPB: 1042,5.cihydroxyphenyl)-IO-hydeo-9- [0118] SPB-100: Otsuka Chemical, phosphazene Mame ‘oxa-10-phosphaphenanthrene-IO-oxide retardant having a phosphorus [0116] conteat of 13.4% [on7] (SMa. [118] EF40: SMA, Sadoms [0119] BE60: SMA, Sadoma [0120] E80: SMA, Sadoma [121] FF1000: SMA, Sadoma [0122] (G) Accelerator [0123] 24M7: 2-cthy!-4-methylimidazole, Shikoku [124] DMAP: 4-timedhylaminopyridine, Guangrong Chemical [0125] BICATZ: zine isooctanoate, The Shepherd Chemi- to ‘om «al Company (0126) (1) Filler [0127] Molten silica (having an average particle size of 0.1-10 yun and a purity of 99% or more) [0128] Tables 1-4 involve the formulation compositions ‘and the physical property data of Examples 1-21, and Tables ‘546 involve the formulation compositions and the physical [0095] | FRX-3001 property data of Comparative Examples 1-12. 10093] BCPPO: _Bis(4-carboxyphenyl)phen oxide Hy ¢ cy Ho oto. ont cay o cy US 2020/0062889 AI Paes He raic9M ps0 Nes BMAP Space econ ‘aiDMAY* ¢ bau cter Wer sean Space econ Tebwarc Dutt ci) Sar oo Sea ce TebMAyc Feb. 27, 2020 23 TABLE 1 2 Bungie s Bumped Gaale S Eunple 6 ” ee fe o 3 0 % oo 'oas—on 8s wo oes sass TABLE 2 Tample? Bani Bampled Example 10 _Fanple th ob 000 TABLE 3 ‘ample 12 Empl 13 Hanple Beane 18 Faample 16 US 2020/0062889 AI Feb. 27, 2020 24 ‘TABLI S-continued ‘ample 12 Bumple 18 angle 4 Bangle 18 ample 16 att Gti) a eee a a Dato Gi) ‘anom ——000% ——naors—omss ona Wer sbiopion% — 002008 reven ox x¢ > Peni oo 2 0 0 Flame menianey 0 | vo TABLE 4 ‘anple 17 _Eumple 18 angle 19 Eeanple 20 Faanple 2 owsrs s SuN-STMGS Bea an ot a a Spiel scon 28 = s = s TeDMay & bus 0 bo ws Dito Gi) Me 3 3 a AIO Gi) toe Ooors dons Oss at Wier abmmionss am Ok fs lane tanancy vo va va TABLE S ‘comp. Cony. Comp. Camp. Camp, Cn. ‘ahs L_Euample2_Bsanple 3 Egle 4 Baan S$ Bhanple 6 Sitios mn a Bruns ‘ing cne antag, 095 Sarsemiooss OR atnay es" rehog’n Ten is) Tenthgns” 22 ancien 4S US 2020/0062889 AI Feb. 27, 2020 25 TABLE 6 Example 7 Gump Eunpe 9 famnc 10 Bewmple 12 Fabs 70 y Barro. sw x Foc Era SN I6SSTM6S proms 30 ot o # » “ rao dean Spheres slcon 300" aap suo ee Pe 354% “oases Sony Saem Sa Fiance can ah m Do Gti) 014 “Reutiogin Goi 01 oon TasKmin 8 $ 5 ji 10129] Additional descriptions of the PCT6 i perfor- tive Example 3 with Example 13, it ean be seen that the mance icon: "y” ropresents tht delamination and papeora ‘ecumed, “0” represents hat delamination and popearn did [0130] The above characteristics are tested a follows [0131] (1) Glass wanton temperature (Tz) Determined ‘seconting to the DMC method specified ia IPC-IM-650 2a24 [0132] 2) Dielectric constant and diletie loss fro, “Tested according to the SPDR mthod, [0183] "G) Evaluation of eat and unity resistance (PCT): The copper filo the surface of the copperclad Jaminate was etched and the substrate was evausted. The substrate was placed in pressure cooker and treated st 120° and 105 KPa for 6, and then immersed ia in froace ‘1 288 C. When there was delamination and popeoen the ‘corresponding time was recorded. When the substrate had ‘ot hon bubbled or delaminated i the tn face for moe than min, the valuation could bo ended 0134)" (4) T288 tested with a TMA instrament according tothe T300 test method specified in IPC-TM-650 2.4.24 {0135} (6) Water Absorption: tested according 0 the test method speifod in IPC-IM650 2.6.2.1 10136] (6) Flame retardaney: tested sosording to the UL standard method. {0137} From the comparison ofthe data ia Tables 1 followings ean be note. 10138] "By comparing Comparative Pxample 1 with Example 6, itcan be seen thatthe coppet-clad laminate prepared by using ODOBDP aod te alogenfre epoxy resi In Comparative Example 1 has worse dielecrie properties, poor heat esstnce and heat and unity resistance high ‘water absorption rte snd low Tg. By comparing Compara. five Fxample 2 with Example 9, 1 canbe seen that ODOBP and cyanate resin were tod togsther in. Comparative Example 2 to cure the halogen-free epoxy resin, and the catalytic activity of ODOPR to eyanate resin was to high resulig in file to fora a sheet By comparing Comparac the copper-clad laminate prepared hy curing the halogen-free {epoxy resin with ODOBP and SMA resin in Comparative Jectrc properties, poor heat resi sorption rate. By comparing Comparative Example 4 with Example 20, it can be seen that the copperclad laminate prepared by curing the halogen-free epoxy resin with ODOBP and phenolic resin in Comparative Example 4 has worse dielectric properties, poor heat resistance and heat and ‘humidity resistance, high Water absorption rate and low Te. [By comparing Comparative Example 5 with Pxampes 6,3 canbe seen that FRX3001 is used to eure the halogen-free fpoxy resin in Example 5: due to poor reetivity and low (OFF content of FRX3001, the copperclad laminates cannot bbe made. By comparing Comparative Example 6 wih Example 9, it can be seen that the copper-clad laminate prepared by curing the halogen-free epoxy resin. with FFRX3001 an! cyanate resin in Comparative Example 6 has worse dielectric properties, low Tg, poor heat resistance and heat and humidity resistance, high water absorption and poor flame retardancy. [0139] Further, it can be seen by comparing Comparative Example 7 with Example 6 that the copperclad laminate prepared in Comparative Example 7 from phosphors-con- ‘aining active ester ina content higher than that in Fxample 6 has high water absorption rate, heat resistance and heat and humidity resistance. By comparing Comparative Example 8 ‘with Example 6, it ean be seen that, when the phosphors ‘containing ative ester is used in Comparative Example 8 ‘content higher than that in Example 6, laminates eannot be ‘made due wo insulicient curing stent. [0140] By comparing Comparative Example 9 with Example 6, it can be seen that the eopper-clad laminate prepared from BHPPO and the halogen-fre epary’ resin in Comparative Fxample 9 has worse dielectric properties, poor heat resistance and heat and humidity resistance, high "Water absorption rate and low Tg. By comparing Compara- US 2020/0062889 AI 26 tive Example 10 with Example 6, it can be seen that the ‘copper-clad laminate prepared ftom BCPPO and the halo- en-ffee epoxy resin in Comparative Example 10 has worse diclecric properties, poor heat resistance and beat and humidity resistance and high water absorplion rate [0141] In Comparative Examples 11 and 12, organic ear boxwlic acid and phenol are used together as an epoxy curing agent. Due to higher rate diference ofthe reaction between, ‘carboxylic acid and epoxy and between phenol and epoxy. ‘carboxylic aeid rapidly participates in the curing eaetion as, ‘8 resull, while phenol hardly participates inthe reucton in the system or in a low amount, It acts as plasticizer in the ‘curing system, resulting in an extremely low Ty afer curing and a low T288. Moreover, due to the presence of phenolic hydroxy! group with 2 high polarity, there are shortcomings such as poor dielectric properties and high water absorption rate, [0142] From the above results, it ean be seen that, by replacing ODOBP and FRX as well as BPO and BCPPO with the phosphorus-containing active ester of the present invention, the prepregs and laminates for printed circuit boards made from the stive ester and components such as ‘shalogen-ve epoxy resin have a glass transition tempera ture of up to 245° C., excelent dioleteie properties, water absomption controled inthe range of 0.06-0.14%, high heat resistance, excellent heat and humidity resistance and good processability, excellent Mame retardant elicieney. and cua achieve ULI4 V20 when P content is 1.5%. [0143] As described above, as compared with general Taminates, the prepregs and laminates for printed circuit boards made from the halogen-ffee thermosetting re ‘composition provides! by the present invention have high pass transition temperature, exeellet dielectric properties, Jow water absorption, high heat resistance, excellent heat 1nd humidity resistance and good processability, and can achieve halogen-fee fame retardancy and reach UL V0. [0148] The above-described examples ate merely pre- erred examples of the present inveation, Those ordinarily skilled in the art can make various other comesponding ‘changes and modifications in aecordance withthe technical solutions and technical concept of the present invention, and all such changes and modifications shall fall within the cope of the claims of the present invention, 148. (canceled) 9, A thermosetting resin composition, comprising: 1) a curing agent comprising at least one phosphors containing active ester wherein the phosphorus-con- taining active ester is present in an amount of 10% to {60% by weight ofthe total weight of an epoxy resin and the curing agent in the thermosetting resin composition, the phosphorus-containing active ester is obtained by ‘copolymerizng a diarylformylehorohydrocarbylphos- ‘ine oxide with at least one of a dihydroxyaxylbydro- carbylphosphine oxide, a dihydroxyaryloxyhydrocarb- ylphosphine oxide and a hydroxylated DOPO, and then terminating by an aromatic formyl chloride, wherein Feb. 27, 2020 the diarylformylehlorohydrocarbylphosphine oxide has a Stevctnral formula of Foal (), esr) the dihydroxyarylhydrmearbylphosphine oxide has a Siavclimal formula of Foam (1), on the dihydroxyaryloxyhydrocarbylphosphine oxide has a Sinicinmal formula of Formula (IID, Fowl HOA, —-0 F008 the hydrowylated DOPO has a strctural formula of Por: mula (IV), Foal V) Il HO An—o8 ‘the aromatic formyl chloride has @ structural formula of Formula (V), wherein R, and R, are identical or different from each ‘other, and each independently anyone selected from the ‘goup consisting of phenyl, naphthyl, and linear or branched alk! having 1 10 4 earbon atoms; swherwin Ary and Ar, are identical or different from cach ‘other, and each independently anyone selected from the ‘roup consisting of a WOK US 2020/0062889 AI Feb. 27, 2020 28 continued Oe wherein ny is an integer of 0-7, By ‘wherein Ris anyone selected from the group consisting cry of linear or branched alkyl groups having 1 to 4 carbon atoms; on > a p— yan epoxy resin present in an amount of 30% to 0% by 7 ‘weight of the total weight of the epoxy resin and the es curing agent in the thermosetting resin composition, % 10, The thermoseting resin composition claimed in claim 9, wherein the phosphorus-containing active ester is ‘obtained by copolymerizing a diaryormslehlorohydrvcar- bylphosphine oxide with a dihydnoxyarylhydrocarbylphos- phine oxide and then terminating by an aromatic formyl ‘chloride, wherein the phosphorus-contaning active ester has a structural formula of formula (VD), on wherein n isa integer of 1-205 continued herein Ry and Ry are identieal or different from each ie ‘other, and wach independently anyone selected from the ‘ group consisting of phenyl, naphthyl, and Tinear or branched alkyl having 1 10 4 carbon atoms: ‘wherein Ary and Ar. are identical or different from each ‘other, and each indepenstently anyone selected from the troup consisting of oro tt nea: ° 5

    +H 9 US 2020/0062889 AI Feb. 27, 2020 29 -continved continued ( ) ( ) ) C ) ‘wherein Ar, is anyone selected from the group consisting BK om ud ‘ens ‘wherein n, isan integer of 05; ‘wherein n, is an integer of 07, ‘wherwin R, is anyone selected ffom the grup consisting ‘of finea or branches alkyl groups having 1 to 4 carbon 11. The thermosetting resin composition claimed in ela 9, wherein the phosphoriscontsining active ester is obtained by copolsmerizing a diary formylehlorobydrocar- bylphosphine oxide with a dihydroxyaryloxyhydrocarby!- phosphine oxide and then terminating by an aromati formyl chloride, wherein the phosphorus-contining active ester has 4 structural Formula of formula (VI), FoomlaV) wherein is an integer of 1-204 wherein Ry and R, are identieal or differen from each ‘other, and each independently anyone selected from the ‘goup consisting of phenyl, naphthyl, and linear or branched alkyl having 1 10 4 carbon atoms: wherein Ary and Ary are identical or dilfeent from each ‘other, and each independently ‘anyone selected from the ‘Broup consisting of US 2020/0062889 AI 31 12, The thermoserting resin composition claimed in claim 9, wherein the phosphorus-containing active ester is ‘obtained by copolymerizing a diarylformylchlorohydrocar- bylphosphine oxide with a hydroxylated DOPO and thea terminating by an aromatic forms] chloride, wherein the phosphoris-containing active ester has a stractural formula ‘of formula (VII), ‘wherein n isan intoger of 1-20 ‘wherein Ris anyone selected from the group consisting of phenyl aaphthy, and linear or Branca alkyl hav- ing 1 to 4 carbon atoms; wherein Ar i anyone selected from the group consisting of wo te - <><) <> OS <)+ oy LO- 3-7-8 & Feb. 27, 2020 -continsed OX g yr HG ms ad ‘eH, US 2020/0062889 AI -continved OK) wherein Ax is anyone selected from the group consisting Bone ig : : 4 Feb. 27, 2020 continued ‘wherein Ar is anyone selected from the group consisting wherein a, isan integer of 05; ‘wherein n, is an integer of 0-7, ‘wherein Ry is anyone selected irom the group consisting ‘of linear of branched alkyl groups having 1 to 4 carbon 13, The thermoseting resin composition clsimed in elaimn 9, wherein the phosphoruscontaining active ester is ‘obtained by copolymerizing a diarylformylehlorohydrocar- bylphosphine oxide with a dihydeoxyaryloxyhydrocarby phosphine oxide and a hydroxylated DOPO and then tr hating by an aromatic formyl chloride, wherein the Phosphoris-containing active ester has a stetural formula of formula (IX) or (X), Fon 8) a e & L, ae t { [i o-m-09fi-o- ty oid US 2020/0062889 AI Feb. 27, 2020 33 wherein each of 1, and ny is an integer of 0-20, and continued pare) cin ich an and ash rela 8 nt be Oe 0, 0; acs tt be O whe 9 0 <)p-

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