TW202428699A - 可固化組成物 - Google Patents
可固化組成物 Download PDFInfo
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- TW202428699A TW202428699A TW112143909A TW112143909A TW202428699A TW 202428699 A TW202428699 A TW 202428699A TW 112143909 A TW112143909 A TW 112143909A TW 112143909 A TW112143909 A TW 112143909A TW 202428699 A TW202428699 A TW 202428699A
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- poly
- styrene
- copolymer
- flame retardant
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- 239000000203 mixture Substances 0.000 title claims abstract description 166
- -1 poly(arylene ether Chemical compound 0.000 claims abstract description 92
- 239000003063 flame retardant Substances 0.000 claims abstract description 48
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 claims abstract description 42
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims abstract description 36
- 239000003999 initiator Substances 0.000 claims abstract description 31
- 229920001577 copolymer Polymers 0.000 claims abstract description 22
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims abstract description 18
- 229910052698 phosphorus Inorganic materials 0.000 claims abstract description 18
- 239000011574 phosphorus Substances 0.000 claims abstract description 18
- 229920000642 polymer Polymers 0.000 claims description 44
- 239000000945 filler Substances 0.000 claims description 41
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- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 34
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- 239000007787 solid Substances 0.000 claims description 24
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- 238000000034 method Methods 0.000 claims description 17
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- KOMNUTZXSVSERR-UHFFFAOYSA-N 1,3,5-tris(prop-2-enyl)-1,3,5-triazinane-2,4,6-trione Chemical compound C=CCN1C(=O)N(CC=C)C(=O)N(CC=C)C1=O KOMNUTZXSVSERR-UHFFFAOYSA-N 0.000 claims description 14
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- JICKLZPELARGSA-UHFFFAOYSA-N 2,4,6-triphenoxy-2,4,6-tris(2-prop-2-enylphenoxy)-1,3,5-triaza-2lambda5,4lambda5,6lambda5-triphosphacyclohexa-1,3,5-triene Chemical compound C=CCC1=CC=CC=C1OP1(OC2=CC=CC=C2)=NP(OC2=CC=CC=C2)(OC2=CC=CC=C2CC=C)=NP(OC2=CC=CC=C2)(OC2=CC=CC=C2CC=C)=N1 JICKLZPELARGSA-UHFFFAOYSA-N 0.000 claims description 5
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- XDLMVUHYZWKMMD-UHFFFAOYSA-N 3-trimethoxysilylpropyl 2-methylprop-2-enoate Chemical compound CO[Si](OC)(OC)CCCOC(=O)C(C)=C XDLMVUHYZWKMMD-UHFFFAOYSA-N 0.000 claims description 5
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- HGTUJZTUQFXBIH-UHFFFAOYSA-N (2,3-dimethyl-3-phenylbutan-2-yl)benzene Chemical compound C=1C=CC=CC=1C(C)(C)C(C)(C)C1=CC=CC=C1 HGTUJZTUQFXBIH-UHFFFAOYSA-N 0.000 claims description 4
- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical compound C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 claims description 4
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- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims description 4
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- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 claims description 3
- 229910052582 BN Inorganic materials 0.000 claims description 3
- PZNSFCLAULLKQX-UHFFFAOYSA-N Boron nitride Chemical compound N#B PZNSFCLAULLKQX-UHFFFAOYSA-N 0.000 claims description 3
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 claims description 3
- JRPBQTZRNDNNOP-UHFFFAOYSA-N barium titanate Chemical compound [Ba+2].[Ba+2].[O-][Ti]([O-])([O-])[O-] JRPBQTZRNDNNOP-UHFFFAOYSA-N 0.000 claims description 3
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical group C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 claims description 3
- WPKWPKDNOPEODE-UHFFFAOYSA-N bis(2,4,4-trimethylpentan-2-yl)diazene Chemical compound CC(C)(C)CC(C)(C)N=NC(C)(C)CC(C)(C)C WPKWPKDNOPEODE-UHFFFAOYSA-N 0.000 claims description 3
- 229910052736 halogen Inorganic materials 0.000 claims description 3
- 150000002367 halogens Chemical class 0.000 claims description 3
- PHKMWRPYLCNVJC-UHFFFAOYSA-N n'-benzyl-n-[3-[dimethoxy(prop-2-enoxy)silyl]propyl]ethane-1,2-diamine Chemical compound C=CCO[Si](OC)(OC)CCCNCCNCC1=CC=CC=C1 PHKMWRPYLCNVJC-UHFFFAOYSA-N 0.000 claims description 3
- 229910000077 silane Inorganic materials 0.000 claims description 3
- ZNOCGWVLWPVKAO-UHFFFAOYSA-N trimethoxy(phenyl)silane Chemical compound CO[Si](OC)(OC)C1=CC=CC=C1 ZNOCGWVLWPVKAO-UHFFFAOYSA-N 0.000 claims description 3
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- WQJUBZMZVKITBU-UHFFFAOYSA-N (3,4-dimethyl-4-phenylhexan-3-yl)benzene Chemical compound C=1C=CC=CC=1C(C)(CC)C(C)(CC)C1=CC=CC=C1 WQJUBZMZVKITBU-UHFFFAOYSA-N 0.000 claims description 2
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- 229910052454 barium strontium titanate Inorganic materials 0.000 claims description 2
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Abstract
本揭露內容係關於一種可固化組成物,其包括至少一種聚(伸芳基醚)共聚物、至少一種含磷阻燃劑及至少一種自由基引發劑。本揭露內容亦關於使用該組成物來形成膜、層壓板、預浸體及/或電路板。
Description
相關申請案
本申請案主張2022年11月16日申請之美國臨時申請案第63/425,787號之權益,該申請案其以引用的方式併入本文中。
發明領域
本揭露內容係關於可固化組成物,以及相關方法、膜、層壓板、預浸體及電路板。
發明背景
為滿足高速計算及通信系統之逐漸增加的需求,需要進一步減少印刷電路板(PCB)層壓板之損耗因數(Df)及插入損耗。另外,由於與PCB材料之製造及處置相關之環境問題,現在許多消費型電子裝置應用均需要使用無鹵素樹脂組成物。
當前低損耗樹脂系統通常使用習知聚(伸苯基醚) (PPE)及以烴樹脂為主之調配物,已發現該等材料可提供低Df及插入損耗,但無法滿足目前所需的低Df標準。另外,儘管以烴樹脂為主之調配物可展示極低損耗,但其具有較差UL94可燃性效能。為了克服此問題,通常需要極高的阻燃劑位準,其導致較差黏附特性(例如低銅剝離及內層黏合強度(ILBS))、較差熱特性(例如低熱膨脹係數(CTE))及較差防潮性以及增加的Df。
發明概要
本揭露內容係基於以下出人意料的發現:相較於習知可固化組成物(例如含有PPE之可固化組成物),某些包括含氮聚(伸芳基醚)聚合物及含磷阻燃劑之可固化組成物可展現出優良電氣特性(例如低Dk及Df)、改良之阻燃性(例如達成UL94 V-0可燃性效能)、改良之機械特性(例如層間黏合強度)及改良之黏附特性(例如剝離強度)。
在一個態樣中,本揭露內容之特徵在於可固化組成物(例如無鹵素可固化組成物),其包括(1)至少一種聚(伸芳基醚)聚合物,其包括含有嘧啶、吡𠯤或嗒𠯤基團之單體單元;(2)至少一種含磷阻燃劑;及(3)至少一種自由基引發劑。
在另一態樣中,本揭露內容之特徵在於由本文所描述之可固化組成物製備之膜(例如,獨立膜或支撐膜)。
在另一態樣中,本揭露內容之特徵在於預浸體產品,其包括用本文所描述之可固化組成物浸漬之編織或非編織基體(例如編織或非編織織品)。
在另一態樣中,本揭露內容之特徵在於一種層壓板,其包括由本文所描述之預浸體產品製備的至少一個層。
在另一態樣中,本揭露內容之特徵在於一種用於電子產品中之電路板(例如,印刷電路板),該電路板包括本文中所描述之層壓板。
在再一態樣中,本揭露內容之特徵在於一種方法,其包括用本文所描述之可固化組成物浸漬編織或非編織基體及固化該組成物以形成預浸體產品。
所揭示之組成物及方法之一或多個實施例的細節闡述於以下描述中。所揭示之組成物及方法之其他特徵、目標及優點將自實施方式及申請專利範圍顯而易見。
較佳實施例之詳細說明
一般而言,本揭露內容係關於可固化組成物,其包括至少一種(例如二種或三種或更多種)聚(伸芳基醚)聚合物、至少一種含磷阻燃劑及至少一種(例如二種或三種或更多種)自由基引發劑。在一些實施例中,本文所描述之可固化組成物可基本上不含鹵素(例如F、Cl、Br或I)。在一些實施例中,本文所描述之聚合物可為均聚物或共聚物(例如無規共聚物、接枝共聚物、交替共聚物或嵌段共聚物)。
在一些實施例中,本文中所描述之聚(伸芳基醚)聚合物為可固化或可交聯的(例如在引發劑或熱存在下)。在一些實施例中,聚(伸芳基醚)聚合物可包括至少二個碳-碳雙鍵,其可在聚合物鏈末端(亦即在端基中)或在聚合物鏈中間(例如在側鏈中)。如本文所用,「碳-碳雙鍵」係指非芳族碳-碳雙鍵,諸如烯系基團或乙烯基。舉例而言,聚(伸芳基醚)聚合物可由含有順丁烯二醯亞胺、苯乙烯、烯丙基、烯丙基醚、丙烯酸酯、甲基丙烯酸酯或苯并㗁𠯤基團(其包括碳-碳雙鍵)之官能基封端。
在一些實施例中,本文所描述之聚(伸芳基醚)聚合物不包括碳-碳雙鍵,但包括可在加熱下產生自由基之官能基,其可交聯。此類官能基之實例為經取代或未經取代之苯基。
在一些實施例中,本文所描述之聚(伸芳基醚)聚合物可在其聚合物結構中包括氮原子。不希望受理論所束縛,咸信聚(伸芳基醚)聚合物中之氮及阻燃劑中之磷可產生協同作用,導致增加的炭形成及阻燃性。因此,使用含氮聚(伸芳基醚)聚合物可降低可固化組成物中阻燃劑之量,其繼而產生極佳特性,諸如改良之銅剝離、ILBS、CTE、防潮性及Df。
在一些實施例中,本文所描述之聚(伸芳基醚)聚合物可包括至少一個(例如,二個或三個或更多個)第一單體單元及任擇地至少一個(例如,二個或三個或更多個)不同於第一單體單元之第二單體單元。本文中提及之片語「單體單元」係指由單體形成且可與此項技術中已知之「單體重複單元」互換使用的基團。在一些實施例中,共聚物僅包括第一單體單元及任擇的第二單體單元且不包括任何其他單體單元。
在一些實施例中,本文所描述之聚(伸芳基醚)聚合物可包括含有嗒𠯤、嘧啶或吡𠯤基之單體單元。此類聚合物之實例可包括具有下文式(1)至式(3)中之一者中所示之化學結構的單體單元:
(1)、
(2)及
(3),
其中n為0、1或2;各R獨立地為具有1至20個碳原子之單價烴基(例如C
1-C
20烷基或C
6-C
20芳基)、CN、NO
2或N(R'R''),其中R'及R''中之各者為C
1-C
20烷基或芳基;且X為含有芳族基團(例如伸苯基)之二價有機基團。在一些實施例中,式(1)至式(3)中之X可具有下文式(4)中所示之化學結構:
(4),
其中m為0、1、2、3、4或5;Ar
1及Ar
2中之各者獨立地為任擇地經一或多個(例如1、2、3或4個) C
1-C
20烷基取代之芳族基團(例如伸苯基);且L為單鍵、-O-、-S-、-N(R
a)-、-C(O)-、-SO
2-、-P(O)-或具有1至20個碳原子之二價烴基(C
1-C
20烷基或
,其任擇地經一或多個(例如1、2、3、4、或5) C
1-C
10烷基取代)。
在一些實施例中,本文所描述之聚(伸芳基醚)聚合物可包括具有以下式(5)至式(9)中之一者中所示之化學結構的單體單元:
(5)、
(6)、
(7)、
(8)及
(9),
其中R
1為H、C
1-C
10烷基或芳基;R
2、R
3及R
6中之各者獨立地為C
1-C
10烷基;R
4、R
5、R
7及R
8中之各者為H或C
1-C
10烷基;p為0至4之整數;q為0至4之整數;且r為0至4之整數。
本文所描述之聚(伸芳基醚)聚合物之實例可包括具有以下化學結構中之一者的單體單元:
、
、
、
、
、
及
,
其中p、q、r、R
2、R
3及R
6如上文所定義。此類聚合物之特定實例具有以下化學結構:
,
其中n為1至100之整數。本文中所描述之聚(伸芳基醚)聚合物之市售實例包括可購自Japanese Synthetic Rubber公司之官能化聚(嘧啶芳基醚)共聚物JSR HC-G0021及HC-G0030。
在一些實施例中,聚(伸芳基醚)聚合物以本文所描述之可固化組成物之總重量或本文所描述之可固化組成物之固體含量之至少約1 wt% (例如至少約2 wt%、至少約4 wt%、至少約5 wt%、至少約6 wt%、至少約8 wt%、至少約10 wt%、至少約12 wt%、至少約14 wt%、至少約15 wt%、至少約16 wt%、至少約18 wt%、至少約20 wt%、至少約25 wt%、至少約30 wt%、至少約35 wt%或至少約40 wt%)至至多約50 wt% (例如至多約45 wt%、至多約40 wt%、至多約35 wt%、至多約30 wt%、至多約25 wt%、至多約20 wt%、至多約15 wt%或至多約10 wt%)的一量存在。不希望受理論所束縛,咸信含有本文所描述之聚(伸芳基醚)聚合物之可固化組成物可具有優良電氣特性(例如低Dk或Df)及耐燃性。
在一些實施例中,本文所描述之可固化組成物可包括至少一種(例如二種或三種或更多種)阻燃劑。在一些實施例中,阻燃劑可包括能夠與本文所描述之聚(伸芳基醚)聚合物反應的一或多個官能基(例如乙烯基、烯丙基、苯乙烯基、順丁烯二醯亞胺、甲順丁烯二醯胺或(甲基)丙烯酸酯基)。在一些實施例中,阻燃劑可對本文所描述之聚(伸芳基醚)聚合物無反應。在一些實施例中,本文所描述之阻燃劑不含鹵素(例如F、Cl、Br或I)。在一些實施例中,阻燃劑在本文所描述之固化組成物中可為可溶性的(例如具有至少約10 mg/mL的溶解度)。在一些實施例中,阻燃劑在本文所描述之固化組成物中可為不溶性的(例如具有至多約1 mg/mL的溶解度)。
在一些實施例中,阻燃劑可在其化學結構中包括磷原子。含磷阻燃劑之實例包括磷酸酯阻燃劑、亞膦酸酯阻燃劑及磷氮烯阻燃劑。適合之含磷阻燃劑之具體實例包括二乙基亞磷酸鋁(例如購自Clariant Specialty Chemicals公司的OP-935)、對二甲苯-雙-二苯基膦氧化物(例如購自Chin Yee Chemical Industries有限公司的PQ-60)、(2,5-二烯丙基氧基苯基)二苯基膦氧化物、六苯氧基環三磷氮烯(例如購自Otsuka Chemical有限公司的SPB-100)、參(2-烯丙基苯氧基)三苯氧基環三磷氮烯(例如購自Otsuka化學有限公司的SPV-100)、間苯二酚雙(二-2,6-二甲基苯基磷酸酯)(例如購自Daihachi Chemical Industry有限公司的PX-200)、氰基苯氧基(苯氧基)環磷氮烯、甲苯基氧基(苯氧基)環磷氮烯、螺環磷氮烯及含乙烯基之磷氮烯。不希望受理論所束縛,咸信阻燃劑中之磷與聚(伸芳基醚)聚合物中之氮可產生協同作用,產生增加的炭形成及阻燃性,其可減少所需阻燃劑之量且改良可固化組成物之特性(例如銅剝離、ILBS、CTE、防潮性及Df)。在一些實施例中,阻燃劑本身可在其化學結構中包括氮原子以促進此類協同效應。
在一些實施例中,本文所描述之阻燃劑可具有相對較低損耗因數(Df)。舉例而言,阻燃劑之Df可在至多約0.0025 (例如至多約0.0024、至多約0.0022、至多約0.002、至多約0.0018、至多約0.0016、至多約0.0015、至多約0.0014、至多約0.0012、至多約0.001或至多約0.0008)至至少約0.0005 (例如至少約0.0006、至少約0.0008或至少約0.001)範圍內。
在一些實施例中,阻燃劑以本文所描述之可固化組成物之總重量或本文所描述之可固化組成物之固體含量之至少約1 wt% (例如至少約2 wt%、至少約4 wt%、至少約5 wt%、至少約6 wt%、至少約8 wt%、至少約10 wt%、至少約12 wt%、至少約14 wt%、至少約15 wt%、至少約16 wt%、至少約18 wt%、至少約20 wt%、至少約25 wt%、至少約30 wt%或至少約35 wt%)至至多約45 wt% (例如至多約43 wt%、至多約41 wt%、至多約39 wt%、至多約37 wt%、至多約35 wt%、至多約30 wt%、至多約25 wt%、至多約20 wt%、至多約15 wt%或至多約10 wt%)的一量存在。
在一些實施例中,本文所描述之可固化組成物可包括至少一種(例如二種或三種或更多種)自由基引發劑。在一些實施例中,自由基引發劑可包括過氧化物(例如二-(三級丁基過氧基異丙基)苯、雙(1-甲基-1-苯乙基)過氧化物、2,5-二甲基-2,5-二(三級丁基過氧基)己炔-3、2,5-二甲基-2,5-二(三級丁基過氧基)己烷或過氧化二異丙苯)、芳族烴(例如雙(4-乙烯基苯基)乙烷、3,4-二甲基-3,4-二苯基己烷或2,3-二甲基-2,3-二苯基丁烷)或偶氮化合物(例如2,2'-偶氮雙(2,4,4-三甲基戊烷))。不希望受理論所束縛,咸信當組成物用於形成預浸體產品或層壓板時,自由基引發劑可促進可固化組成物之固化(例如藉由引發本文所描述之聚(伸芳基醚)聚合物之交聯反應)。
在一些實施例中,本文所描述之自由基引發劑為非過氧化物自由基引發劑。在不希望受理論束縛的情況下,咸信過氧化物引發劑之分解產物(及過氧化物引發劑本身)為極性的且可導致固化組成物中之Df增加。另一方面,不希望受理論束縛,咸信非過氧化物引發劑(例如烴,諸如2,3-二甲基-2,3-二苯基丁烷)不含有極性原子,且因此可降低固化組成物之Df。
在一些實施例中,本文所描述之可固化組成物可包括過氧化物自由基引發劑及非過氧化物自由基引發劑二者。在不希望受理論束縛的情況下,咸信非過氧化物引發劑可具有相對較高的活化能且因此在固化本文中所描述之組成物時可能並不有效。因此,不希望受理論束縛,咸信在一些實施例中,使用過氧化物引發劑及非過氧化物引發劑之組合可產生具有最佳固化速率及Df之可固化組成物。
在一些實施例中,本文所描述之可固化組成物不包括自由基引發劑。在一些實施例中,組成物可藉由加熱固化。
在一些實施例中,自由基引發劑以本文所描述之可固化組成物之總重量或本文所描述之可固化組成物之固體含量之至少約0.1 wt% (例如至少約0.2 wt%、至少約0.4 wt%、至少約0.5 wt%、至少約0.6 wt%、至少約0.8 wt%、至少約1 wt%、至少約1.5 wt%、至少約2 wt%、至少約2.5 wt%或至少約3 wt%)至至多約10 wt% (例如至多約9 wt%、至多約8 wt%、至多約7 wt%、至多約6 wt%、至多約5 wt%、至多約4 wt%、至多約3 wt%、至多約2.5 wt%、至多約2 wt%、至多約1.5 wt%、至多約1 wt%、至多約0.8 wt%、至多約0.6 wt%或至多約0.5 wt%)的一量存在。
在一些實施例中,本文所描述之可固化組成物可任擇地包括至少一種(例如二種或三種或更多種)不同於本文所描述之聚(伸芳基醚)聚合物的彈性體。在一些實施例中,彈性體可包括乙烯單體單元、丙烯單體單元、丁烯單體單元、異丁烯單體單元、丁二烯單體單元、異戊二烯單體單元、環己烯單體單元、苯乙烯單體單元或其組合。適合之彈性體之實例可包括聚(苯乙烯-乙烯-丁烯-苯乙烯) (SEBS)共聚物、聚(甲基苯乙烯-乙烯-丁烯-甲基苯乙烯)共聚物、與順丁烯二酸酐接枝之聚(苯乙烯-乙烯-丁烯-苯乙烯)共聚物、聚(苯乙烯-共-二乙烯基苯-共-乙基苯乙烯)共聚物、聚(甲基苯乙烯-共-4-(二甲基乙烯基矽烷基甲基)苯乙烯)共聚物、聚丁二烯、聚(丁二烯-共-苯乙烯)共聚物、聚二乙烯基苯共聚物、聚(苯乙烯-乙烯-丙烯-苯乙烯) (SEPS)共聚物、聚(苯乙烯-丁二烯-苯乙烯) (SBS)共聚物、聚(苯乙烯-異戊二烯-苯乙烯) (SIS)共聚物或聚(乙烯-丙烯-二烯) (EPD)共聚物。
在一些實施例中,彈性體以本文所描述之可固化組成物之總重量或本文所描述之可固化組成物之固體含量之至少約1 wt% (例如至少約2 wt%、至少約4 wt%、至少約5 wt%、至少約6 wt%、至少約8 wt%、至少約10 wt%、至少約15 wt%、至少約20 wt%、至少約25 wt%、至少約30 wt%或至少約35 wt%)至至多約40 wt% (例如至多約35 wt%、至多約30 wt%、至多約25 wt%、至多約20 wt%、至多約15 wt%、至多約10 wt%、至多約8 wt%、至多約6 wt%、至多約5 wt%或至多約4 wt%)的一量存在。較佳地,彈性體為本文所描述之可固化組成物之固體含量的約1 wt%至約10 wt%。在不希望受理論束縛的情況下,咸信彈性體可改良本文所描述之可固化組成物之熱特性(例如更高的玻璃轉化溫度及/或更低的熱膨脹係數)、機械特性(例如銅剝離強度及/或內層黏合強度)或電氣特性(例如Dk及/或Df)。
在一些實施例中,本文所描述之可固化組成物可包括至少一種(例如二種或三種或更多種)填充劑(例如無機填充劑)。適合填充劑之實例包括二氧化矽、氧化鋁、石英、氧化鈦、氮化硼、鈦酸鋇、鈦酸鍶鋇及聚合物顆粒。在一些實施例中,聚合物顆粒可包括含氟聚合物(例如聚四氟乙烯)。在一些實施例中,本文所描述之至少一種填充劑可包括一或多種(例如二種或三種)非中空固體填充劑及/或一或多種(例如二種或三種)中空填充劑。
在一些實施例中,填充劑可包括中空二氧化矽顆粒(例如中空二氧化矽珠粒)。不希望受理論束縛,咸信使用中空顆粒作為填充劑可改良本文所描述之可固化組成物的電氣特性(例如降低Dk及/或Df)。
在一些實施例中,本文所描述之填充劑(例如中空二氧化矽顆粒)可具有相對較高純度。舉例而言,填充劑(例如,中空二氧化矽顆粒)可包括至少約95 wt% (例如,至少約96 wt%、至少約97 wt%、至少約98 wt%、至少約99 wt%或至少約99.5 wt%)二氧化矽。不希望受理論所束縛,咸信使用高純度中空填充劑可降低由此類填充劑製成之預浸體產品或層壓板之Df,且可減少可能導致可靠性問題的金屬污染。
在一些實施例中,本文所描述之填充劑(例如中空二氧化矽顆粒)可具有相對較小的密度。舉例而言,填充劑(例如中空二氧化矽顆粒)之密度可為至多約1.5 g/cm
3(例如至多約1.4 g/cm
3、至多約1.2 g/cm
3、至多約1 g/cm
3、至多約0.8 g/cm
3、至多約0.6 g/cm
3、至多約0.5 g/cm
3或至多約0.4 g/cm
3)。在不希望受理論束縛的情況下,咸信低密度填充劑可具有相對較高孔隙度且因此使用低密度填充劑可降低由此填充劑製成之預浸體產品或層壓板的Df及/或Dk。
在一些實施例中,本文所描述之填充劑可具有相對較低介電常數(Dk)及/或相對較低損耗因數(Df)。舉例而言,本文所描述之填充劑在10 GHz下之Dk可在至多約3.1 (例如至多約3、至多約2.9、至多約2.8、至多約2.7、至多約2.6、至多約2.5、至多約2.4、至多約2.2或至多約2)至至少約1 (例如至少約1.5)範圍內。在一些實施例中,本文所描述之填充劑的損耗因數(Df)可在至多約0.002 (例如至多約0.0018、至多約0.0016、至多約0.0015、至多約0.0014、至多約0.0012、至多約0.001或至多約0.0008)至至少約0.0005 (例如至少約0.0006、至少約0.0008或至少約0.001)範圍內。
在一些實施例中,本文中提及之填充劑可具有相對較小粒度。舉例而言,填充劑可具有至多約10 μm (例如至多約8 μm、至多約6 μm、至多約5 μm、至多約4 μm或至多約2 μm)及/或至少約0.7 μm (例如至少約0.8 μm、至少約1 μm、至少約1.5 μm或至少約2 μm)之粒度D50值。不希望受理論所束縛,咸信使用具有相對較小尺寸之填充劑可減少在PCB製程期間由此類填充劑製成之預浸體產品或層壓板中之缺陷。
在一些實施例中,至少一種填充劑以本文所描述之可固化組成物之總重量或本文所描述之可固化組成物之固體含量之至少約10 wt% (例如至少約15 wt%、至少約20 wt%、至少約25 wt%、至少約30 wt%、至少約35 wt%、至少約40 wt%、至少約45 wt%、至少約50 wt%、至少約55 wt%或至少約60 wt%)至至多約65 wt% (例如至多約60 wt%、至多約55 wt%、至多約50 wt%、至多約45 wt%、至多約40 wt%、至多約35 wt%、至多約30 wt%、至多約25 wt%或至多約20 wt%)的一量存在。
在一些實施例中,本文所描述之至少一種填充劑可包括含有中空二氧化矽顆粒之第一填充劑及不同於中空二氧化矽顆粒之第二填充劑,諸如含有氮化硼、鈦酸鋇、鈦酸鍶鋇、氧化鈦、玻璃(例如中空玻璃)、含氟聚合物(例如聚四氟乙烯)或聚矽氧的填充劑。
在一些實施例中,本文所描述之可固化組成物可任擇地進一步包括至少一種(例如二種或三種或更多種)偶合劑。在一些實施例中,偶合劑可包括矽烷、鈦酸鹽或鋯酸鹽。適合之偶合劑之實例包括甲基丙烯醯氧基丙基-三甲氧基矽烷、乙烯基三甲氧基矽烷、水解乙烯基苯甲基胺基乙基胺基-丙基三甲氧基矽烷、苯基三甲氧基矽烷、對苯乙烯基三甲氧基矽烷、3-異氰酸丙基三乙氧基矽烷、3-甲基丙烯醯氧基丙基三甲氧基矽烷、四(2,2-二烯丙基氧基甲基-1-丁基)雙(二-十三烷基亞磷酸酯)鈦酸酯或四(2,2-二烯丙基氧基甲基-1-丁基)雙(二-十三烷基亞磷酸酯)鋯酸酯。不希望受理論所束縛,咸信偶合劑可改良可固化組成物中之無機填充劑之可分散性,改良可固化組成物中之填充劑與聚合物之間的黏附力以及預浸體產品中之玻璃布與可固化組成物中之聚合物之間的黏附力,改良可固化組成物之防潮性及耐溶劑性,且減少可固化組成物中之空隙的數目。
在一些實施例中,偶合劑可在填充劑包括於本文所描述之可固化組成物中之前塗覆於填充劑之表面上(例如作為表面處理劑)。在一些實施例中,偶合劑可包括於本文所描述之可固化組成物中作為獨立於填充劑之組分。
在一些實施例中,偶合劑以本文所描述之可固化組成物之總重量或本文所描述之可固化組成物之固體含量之至少約0.1 wt% (例如至少約0.2 wt%、至少約0.3 wt%、至少約0.4 wt%、至少約0.5 wt%、至少約0.6 wt%、至少約0.7 wt%、至少約0.8 wt%或至少約0.9 wt%)至至多約5 wt% (例如至多約0.9 wt%、至多約0.8 wt%、至多約0.7 wt%、至多約0.6 wt%、至多約0.5 wt%、至多約0.4 wt%、至多約0.3 wt%或至多約0.2 wt%)的一量存在。
在一些實施例中,本文所描述之可固化組成物可任擇地進一步包括至少一種(例如二種或三種或更多種)交聯劑。在一些實施例中,交聯劑可包括三聚異氰酸三烯丙酯(TAIC)、三聚氰酸三烯丙酯、雙(乙烯基苯基)醚、溴苯乙烯(例如二溴苯乙烯)、聚丁二烯、聚(丁二烯-共-苯乙烯)共聚物、二乙烯基苯、二(甲基)丙烯酸酯、順丁烯二醯亞胺化合物(例如雙順丁烯二醯亞胺)、二環戊二烯、三環戊二烯、烯丙基苯并㗁𠯤、烯丙基磷氮烯、烯丙基環磷氮烯(例如參(2-烯丙基苯氧基)三苯氧基環三磷氮烯)、2,4-二苯基-4-甲基-1-戊烯、反式二苯乙烯、5-乙烯基-2-降冰片烯、三環戊二烯、二甲橋-1H-苯并[f]茚、1,1-二苯乙烯、4-二苯甲基苯乙烯、二異丙烯基苯、二烯丙基間苯二甲酸酯、α-甲基苯乙烯、雙(乙烯基苯基)乙烷化合物(例如1,2-雙(4-乙烯基苯基)乙烷、1,2-雙(3-乙烯基苯基-4-乙烯基苯基)乙烷、1,2-雙(3-乙烯基苯基)乙烷)、矽烷(例如乙烯基矽烷或烯丙基矽烷)、矽氧烷(例如乙烯基矽氧烷或烯丙基矽氧烷)或倍半氧矽烷(例如乙烯基倍半氧矽烷或烯丙基倍半氧矽烷)。不希望受理論所束縛,咸信當組成物用於形成預浸體產品或層壓板時,交聯劑可促進可固化組成物之固化。
在一些實施例中,本文所描述之交聯劑以本文所描述之可固化組成物之總重量或本文所描述之可固化組成物之固體含量之至少約1 wt% (例如至少約2 wt%、至少約3 wt%、至少約4 wt%、至少約5 wt%、至少約6 wt%、至少約8 wt%、至少約10 wt%、至少約12 wt%、至少約14 wt%、至少約15 wt%、至少約16 wt%、至少約18 wt%或至少約20 wt%)至至多約30 wt% (例如至多約25 wt%、至多約20 wt%、至多約15 wt%、至多約10 wt%、至多約8 wt%、至多約6 wt%、至多約5 wt%或至多約4 wt%)的一量存在。在一些實施例中,本文所描述之可固化組成物可不含交聯劑。
在一些實施例中,本文所描述之可固化組成物可任擇地進一步包括至少一種(例如二種或三種或更多種)有機溶劑。在一些實施例中,有機溶劑包括2-庚酮、甲基乙基酮、甲基異丁基酮、甲基正戊基酮、甲基異戊基酮、環戊酮、環己酮、苯、苯甲醚、甲苯、1,3,5-三甲基苯、二甲苯、丙二醇單甲醚、丙二醇單甲醚乙酸酯或其組合。
在一些實施例中,有機溶劑以本文所描述之可固化組成物之總重量之至少約1 wt% (例如至少約5 wt%、至少約10 wt%、至少約15 wt%、至少約20 wt%、至少約25 wt%、至少約30 wt%、至少約35 wt%或至少約40 wt%)至至多約50 wt% (例如至多約45 wt%、至多約40 wt%、至多約35 wt%、至多約30 wt%、至多約25 wt%、至多約20 wt%、至多約15 wt%或至多約10 wt%)的一量存在。不希望受理論所束縛,咸信若有機溶劑小於約1 wt%之可固化組成物,則可固化組成物之黏度可能過高,可能使得可固化組成物不易於加工。另外,不希望受理論所束縛,咸信若有機溶劑大於可固化組成物之約50 wt%,則可固化組成物之黏度可能過低,從而由於不能潤濕而無法使塗佈組成物保持在基體表面上,此可降低塗佈均一性及塗佈效率。
在一些實施例中,當組成物澆鑄成膜時,本文所描述之可固化組成物在10 GHz下的介電常數(Dk)為至多約3.1 (例如至多約3、至多約2.9、至多約2.8、至多約2.7、至多約2.6、至多約2.5、至多約2.4、至多約2.2或至多約2)至至少約1.5。在一些實施例中,當組成物澆鑄成膜時,本文所描述之可固化組成物的損耗因數(Df)為至多約0.002 (例如至多約0.0018、至多約0.0016、至多約0.0015、至多約0.0014、至多約0.0012、至多約0.001或至多約0.0008)至至少約0.0005 (例如至少約0.0006、至少約0.0008或至少約0.001)。
本文所描述之可固化組成物可藉由此項技術中熟知之方法製備。舉例而言,可固化組成物可藉由將組分混合在一起來製備。
在一些實施例中,本揭露內容之特徵在於由本文所描述之可固化組成物製備之膜(例如,獨立膜或支撐膜)。舉例而言,可藉由在基體上塗佈可固化組成物以形成由基體支撐之膜來製備支撐膜。作為另一實例,可藉由將可固化組成物塗佈在基體上以形成層(例如聚合層)且自基體移除(例如剝離)層以形成獨立膜來製備獨立膜。在一些實施例中,膜(例如獨立膜或支撐膜)部分固化。在一些實施例中,膜(例如獨立膜或支撐膜)未固化。
在一些實施例中,本文所描述之膜在10 GHz下的介電常數(Dk)可為至多約3.1 (例如至多約3、至多約2.9、至多約2.8、至多約2.7、至多約2.6、至多約2.5、至多約2.4、至多約2.2或至多約2)至至少約1.5。在一些實施例中,本文所描述之膜的損耗因數(Df)可為至多約0.002 (例如至多約0.0018、至多約0.0016、至多約0.0015、至多約0.0014、至多約0.0012、至多約0.001或至多約0.0008)至至少約0.0005 (例如至少約0.0006、至少約0.0008或至少約0.001)。
在一些實施例中,本文所描述之可固化組成物可塗覆於金屬基體(例如銅箔)之表面以形成樹脂塗佈之金屬基體(例如樹脂塗佈之銅箔)。在此類經樹脂塗佈之金屬基體中,可固化組成物可經固化(例如部分或完全)或未經固化。經樹脂塗佈之金屬基體可用作用於構建印刷電路板(PCB)或佈線板中之多層電路的介電材料。
在一些實施例中,本揭露內容之特徵在於由本文所描述之可固化組成物製備之預浸體產品。在一些實施例中,預浸體產品包括用本文所描述之可固化組成物浸漬之基底材料(例如,編織或非編織基體(諸如織品或纖維材料))。基底材料亦稱為支撐或增強材料。本文所描述之預浸體產品可用於電子工業中,例如以產生印刷佈線板或電路板。
在一些實施例中,本揭露內容之特徵在於一種由本文所描述之不具有基底材料(例如,編織或非編織基體(諸如織品或纖維材料))之可固化組成物製備的未增強膜(例如,獨立膜或支撐膜)。舉例而言,可藉由在基體上塗佈可固化組成物以形成由基體支撐之膜來製備支撐膜。作為另一實例,可藉由將可固化組成物塗佈在基體上以形成層(例如聚合層)且自基體移除(例如剝離)層以形成獨立膜來製備獨立膜。在一些實施例中,膜(例如獨立膜或支撐膜)部分固化。在一些實施例中,膜(例如獨立膜或支撐膜)未固化。本文所描述之未增強膜可在電子工業中用作堆疊膜,例如以生產IC封裝及印刷佈線板或電路板。
一般而言,本文中所描述之預浸體產品可藉由用本文中所描述之可固化組成物浸漬基底材料(通常以玻璃纖維為主,呈編織或非編織基體或呈單向定向平行長絲之交叉層壓板形式),接著將可固化組成物完全或部分地固化(例如在約150℃至約250℃範圍內之溫度下)來製造。浸漬有部分固化組成物之基底材料通常被稱作「預浸體」。如本文中所提及,術語「預浸體」及「預浸體產品」係可互換地使用的。為了由預浸體製造印刷佈線板,預浸體之一或多個層與例如一或多個銅層層壓在一起。
在一些實施例中,用於本文所描述之預浸體中之基底材料(例如,含有編織或非編織基體)可包括無機纖維基底材料,諸如玻璃及石棉。出於阻燃性之觀點,玻璃纖維基底材料較佳。玻璃纖維基底材料之實例包括(但不限於)使用E玻璃、NE玻璃(來自Nittobo, Japan)、C玻璃、D玻璃、S玻璃、T玻璃、石英玻璃、L玻璃、L2玻璃或NER玻璃之編織品;玻璃非編織品,其中用有機黏合劑將短纖維黏成薄片狀材料;及將玻璃纖維及其他纖維類型混合且製成織品的彼等者。
在一些實施例中,預浸體可藉由將本文所描述之可固化組成物浸漬至基底材料(例如編織或非編織基體)中,接著乾燥來產生。在一些實施例中,本文所描述之預浸體可具有如本文所定義之至少約50 wt% (例如至少約52 wt%、至少約54 wt%、至少約55 wt%、至少約56 wt%、至少約58 wt%、至少約60 wt%、至少約62 wt%、至少約64 wt%或至少約65 wt%)至至多約80 wt% (例如至多約78 wt%、至多約76 wt%、至多約75 wt%、至多約74 wt%、至多約72 wt%、至多約70 wt%、至多約68 wt%、至多約66 wt%或至多約65 wt%)之樹脂含量。
在一些實施例中,金屬基體可塗覆至由此形成的預浸體之一個或二個表面以形成層壓板。在一些實施例中,以上形成之預浸體可任擇地視需要與一或多層預浸體層壓以製造複合結構,且金屬箔(例如銅或鋁箔)可塗覆於複合結構之一個或二個表面以獲得層壓板(或覆金屬層壓板)。由此形成之層壓板可任擇地經受進一步處理,諸如加壓及熱壓,其可至少部分(或完全)固化預浸體層。層壓板(例如覆銅箔層壓板)可進一步用額外預浸體層分層且固化,以製得多層印刷電路板。
在一些實施例中,本揭露內容之特徵在於一種層壓板,其包括由本文所描述之預浸體產品製備之至少一個(例如二個或三個或更多個)層。在一些實施例中,層壓板可包括(1)銅基體(例如銅箔)及(2)層壓於銅基體上之至少一個預浸體層。在一些實施例中,預浸體層之一個或二個表面可與銅基體層壓。在一些實施例中,本揭露內容之特徵在於多層層壓板,其中本文所描述之多個覆銅箔層壓板堆疊於彼此頂部上,任擇地在二個覆銅箔層壓板之間具有一或多個預浸體層。由此形成之多層層壓板可經壓製及固化以形成多層印刷電路板。
在一些實施例中,將未增強膜(例如獨立膜或支撐膜)用作堆疊材料以達成更薄厚度之IC封裝及印刷電路板。
在一些實施例中,未增強膜(例如獨立膜或支撐膜)之厚度為至多約150 µm (例如至多約100 µm、至多約90 µm、至多約80 µm、至多約70 µm、至多約60 µm或至多約40 µm)至至少約10 µm。
在一些實施例中,預浸體層(亦即,由本文中所描述之預浸體產品製備之層)或層壓板在10 GHz下的介電常數(Dk)為至多約3.1 (例如至多約3、至多約2.9、至多約2.8、至多約2.7、至多約2.6或至多約2.5)至至少約2.2。
在一些實施例中,預浸體層(亦即,由本文中所描述之預浸體產品製備之層)或層壓板之損耗因數(Df)為至多約0.002 (例如至多約0.0019、至多約0.0018、至多約0.0017、至多約0.0016、至多約0.0015、至多約0.0014、至多約0.0013、至多約0.0012、至多約0.0011或至多約0.001)至至少約0.0005 (例如至少約0.0006、至少約0.0008或至少約0.001)。在不希望受理論束縛的情況下,咸信具有相對低Dk及/或Df之預浸體層或層壓板可減少層壓板或多層電路板結構之總介電損耗及較低信號損耗。
在一些實施例中,固化未增強膜之損耗因數(Df)為至多約0.003 (例如至多約0.0026、至多約0.0024、至多約0.0022、至多約0.0020、至多約0.0018、至多約0.0016、至多約0.0014、至多約0.0012、至多約0.0011或至多約0.001)至至少約0.0005 (例如至少約0.0006、至少約0.0008或至少約0.001)。在不希望受理論束縛的情況下,咸信具有相對低Dk及/或Df之預浸體層或層壓板可減少層壓板或多層電路板結構之總介電損耗及較低信號損耗。
在一些實施例中,本揭露內容之特徵在於一種自本文中所描述之層壓板獲得之印刷電路板或佈線板。舉例而言,可藉由對覆銅箔層壓板的銅箔執行電路處理來獲得印刷電路板或佈線板。電路處理可藉由例如在銅箔的表面上形成光阻圖案、藉由蝕刻移除箔片的不必要部分、移除光阻圖案、藉由鑽孔形成所需通孔、再次形成光阻圖案、電鍍以連接通孔且最後移除光阻圖案來進行。在與上文所描述相同的條件下,在以上述方式獲得的印刷佈線板的表面上額外層壓上述覆銅箔層壓板,隨後以與上述相同的方式進行電路處理,可獲得多層印刷電路板或佈線板。在此狀況下,未必總必需要形成通孔,且可其位置形成通路孔,或可形成二者。舉例而言,在印刷電路板(PCB)中,電路板之不同層上的對應位置中之二個焊盤可藉由穿過板之通路孔電性連接,其中通路孔可藉由電鍍使其導電。接著將此等層壓板層壓所需次數以形成印刷電路板或佈線板。
以上方式製造之印刷電路板或佈線板可與銅基體以內層電路板形式層壓於一個或二個表面上。此層壓模製通常在加熱及加壓下進行。多層印刷電路板可接著藉由以與上文所描述相同的方式對所得覆金屬箔層壓板執行電路處理來獲得。
實例
本揭露內容將參照以下實例較詳細地說明,該等實例係出於說明之目的且不應解釋為限制本揭露內容之範疇。
材料
在以下實例中,BVPE係雙(4-乙烯基苯基)乙烷,來自Regina Electronic materials有限公司。Araldite MT 35610係雙酚A苯并㗁𠯤,購自Huntsman公司。BMI-TMH係1,6-雙順丁烯二醯亞胺(2,2,4-三甲基)己烷,購自Daiwakasei Industries公司。P-d苯并㗁𠯤及LDAIC購自Shikoku Kasei公司。NE-X-9470S購自DIC公司。LME 11613購自Huntsman公司。共聚物A係指美國專利第11,130,861號之實例1中所描述之共聚物A。SBS-A係一種苯乙烯-丁二烯共聚物,購自Nisso America公司。SEBS-A係一種由順丁烯二酸酐改質之SEBS彈性體。MSEBMS係一種聚(甲基苯乙烯-乙烯-丁烯-甲基苯乙烯)共聚物。M1913係一種SEBS彈性體,其含有約30 wt%苯乙烯單體單元或30 wt%聚苯乙烯且藉由順丁烯二酸酐改質,購自Asahi Kasei公司。Kraton 1536、Kraton 1648及Kraton D1623係SEBS彈性體,購自Kraton公司。Vector 4411係一種SIS彈性體,購自Dexco Polymers公司。Septon 2104係一種SEPS彈性體,其含有約65 wt%苯乙烯單體單元或65 wt%聚苯乙烯,購自Kuraray有限公司。Tuftec™ MP10係經胺改質之SEBS,購自Asahi Kasei公司。Ricon-100係一種丁二烯苯乙烯共聚物,購自Cray Valley公司。HC-G0021及HC-G0030係苯乙烯封端之含N聚(伸芳基醚)聚合物,購自Japanese Synthetic Rubber公司。EQ2410-SMC及EQ1010-SMC分別係平均直徑為2微米及0.6微米之實心球形二氧化矽顆粒,購自Zhejiang Third Age Material Technology有限公司(中國)。SC2500-SVJ為具有表面改質之實心二氧化矽且可購自Admatechs有限公司。SS-15V係一種球形二氧化矽,購自Sibelco公司。HS-200-TM (三甲基矽烷基結合的)、HS-200-MT (甲基丙烯醯基矽烷基結合的)、HS-200-VN (乙烯基矽烷基結合的)及HS-200 (未經處理)購自AGC Si-Tech有限公司。
BES5-1150P為購自Regina Electronics公司的含磷阻燃劑(亦即,對二甲苯-雙-二苯基膦氧化物),且經研磨以將粒度減小至小於10微米。PQ-60係一種含磷阻燃劑(亦即,對二甲苯-雙-二苯基膦氧化物),購自Chin Yee Chemical Industries有限公司。OP945係一種有機亞膦酸酯,購自Clariant's Plastics & Coatings有限公司。BP-PZ係一種磷氮烯阻燃劑,購自Otsuka Chemical有限公司。Altexia係6H-二苯并[c,e][1,2]氧雜磷-6,6'-(1,4-乙二基)雙-6,6'-二氧化物,購自Albemarle公司。PX-200係間苯二酚雙(二-2,6-二甲基苯基磷酸酯),購自Daihachi Chemical Industry有限公司。SPB-100係六苯氧基環三磷氮烯,購自Otsuka Chemical有限公司。SPV-100係參(2-烯丙基苯氧基)三苯氧基環三磷氮烯,購自Otsuka Chemical有限公司。Saytex-8010係一種含溴阻燃劑(亦即,1,1'(乙烷-1,2-二基)雙[五溴-苯]),購自Albemarle公司。FP-72TP係環磷氮烯衍生物阻燃劑,購自Fushimi Pharmaceutical有限公司。CCDFB及CC-P3係非過氧化物引發劑(亦即,分別為2,3-二甲基-2,3-二苯基丁烷及聚-1,4-二異丙基苯)購自United Initiators公司。過丁基D係一種過氧化物引發劑(亦即,二-三級丁基過氧化物),購自NOF公司。VR-110係一種偶氮基引發劑(亦即,2,2'-偶氮雙(2,4,4-三甲基戊烷)),購自Fujifilm公司。DiDOPO係6,6'-(1-苯乙烷-1,2-二基)雙(6H-二苯并[c,e][1,2]氧雜磷6-氧化物),購自Life Chemical公司(中國)。VulCup R係α,α-雙(三級丁基過氧基)二異丙基苯,來自Arkema公司。DYBP係2,5-二甲基-2,5-二(三級丁基過氧基)己炔-3,購自United Initiator公司。DCP係過氧化二異丙苯,購自Arkema股份公司。OFS-6030係甲基丙烯醯氧基丙基三甲氧基矽烷,購自Dow公司。OFS-6224係水解乙烯基苯甲基胺基乙基胺基丙基三甲氧基矽烷,購自Dow Chemical公司。OFS-6124係苯基三甲氧基矽烷,購自Dow Chemical公司。SIB 1817.0係1,2-雙(三乙氧基矽烷基)乙烷,購自Gelest公司。
通用程序1 製備預浸體及層壓板
藉由將可溶性樹脂組分溶解於甲苯中來製備可固化組成物。添加不溶性二氧化矽及阻燃劑組分且使用轉子-定子混合器將其分散於樹脂清漆中。將可固化組成物倒入接地金屬盤中且藉由將玻璃布(1078NE玻璃或2116NE玻璃)拉過間隙寬度為11-12密耳的金屬棒間隙,來浸漬有可固化組成物。在室溫下用氣流將樣品乾燥10分鐘,且隨後加熱至130℃持續4分鐘以形成乾燥預浸體。將經乾燥預浸體切割成12×12吋的片塊,且用1盎司HS2-M2-VSP銅箔(Mitsui Mining & Smelting)層壓二個預浸體層的二側,以形成層壓板。層壓板如下進行固化。在將層壓板固定至壓製機中之後,對二層預浸體施加200 psi、250 psi、300 psi、350 psi或450 psi之壓力,其隨後使用下文所描述之循環A至K中的一種進行固化:
循環A:層壓板以6℉/分鐘之加熱速率自室溫加熱至420℉,在420℉下保持2小時,且以10℉/分鐘之冷卻速率冷卻至室溫。層壓壓力為350 psi。
循環B:層壓板以6℉/分鐘之加熱速率自室溫加熱至310℉,在310℉下保持30分鐘,以6℉/分鐘之加熱速率自310℉加熱至420℉,在420℉下保持80分鐘,且以10℉/分鐘之冷卻速率冷卻至室溫。層壓壓力為350 psi。
循環C:層壓板以6℉/分鐘之加熱速率自室溫加熱至420℉,在420℉下保持3小時,且以10℉/分鐘之冷卻速率冷卻至室溫。層壓壓力為350 psi。
除層壓壓力為200 psi以外,循環D與循環C類似。
除層壓壓力為250 psi以外,循環E與循環C類似。
除層壓壓力為300 psi以外,循環F與循環C類似。
除層壓板在450℉下保持180分鐘以外,循環G與循環C類似。
循環H:層壓板以6℉/分鐘之加熱速率自室溫加熱至350℉,在350℉下保持30分鐘,以6℉/分鐘之加熱速率自350℉加熱至420℉,在420℉下保持60分鐘,且以10℉/分鐘之冷卻速率冷卻至室溫。層壓壓力為450 psi。
除層壓板在420℉下保持150分鐘以外,循環I與循環H類似。
除層壓板壓力為250 psi以外,循環J與循環H類似。
除層壓板在420℉下保持120分鐘以外,循環K與循環H類似。
製備用於量測樹脂流動之未增強膜
藉由將可溶性樹脂組分溶解於甲苯中來製備可固化組成物。添加不溶性二氧化矽及阻燃劑組分且使用轉子-定子混合器將其分散於樹脂清漆中。隨後使用線繞包裹的鐵Mayer濕膜塗覆棒將樹脂組成物塗佈至聚合物離型塗佈紙上,使其厚度一致。紙載體上之樹脂組成物隨後在150℃下加熱十分鐘或直至所有甲苯均蒸發。隨後將固結樹脂組成物自離型塗佈紙分離以得到未增強膜。
製備用於Dk /Df 及CTE 量測之未增強層壓板
隨後使用以下循環L將上述未增強膜層壓於二片0.5盎司HS1 VSP銅箔之間以得到雙側覆銅箔層壓板。對樣品的一部分進行蝕刻以移除銅,用於量測介電特性,而其他部分保留銅,用於量測銅剝離強度。
循環L:層壓板以6℉/分鐘之加熱速率自室溫加熱至450℉,在450℉下保持2小時,且以10℉/分鐘之冷卻速率冷卻至室溫。層壓壓力為約50 psi。
製備用於可燃性測試之未增強樣品
用塗覆器將樹脂組成物塗佈於PET膜上,且在80℃下乾燥10分鐘,使得乾燥之後的樹脂組成物層之厚度為40 μm。使用分批式真空壓力層壓機MVLP-300,將樹脂薄片層壓至厚度為0.2 mm且無銅箔的FR-4基體的二側。藉由將壓力降低至13帕或更小之壓力持續30秒來進行層壓。隨後將層壓板在1.0 MPa壓力下,在110℃下壓製30秒。在自支撐物剝離PET膜之後,以相同方式將40 μm厚的樹脂薄片層壓於二側上直至厚度達到160 μm。將PET膜剝離且將層壓之樣品在氮氣氛圍下,在230℃下固化2小時。將固化之樣品切割成寬度為12.7 mm且長度為12.7 mm之片塊。如上文所描述製備一組五個樣品。
通用程序 2 特性量測樹脂含量(RC)
量測玻璃布之重量,隨後使其塗佈有可固化組成物。在塗佈及乾燥之後,量測由此形成之預浸體的總重量。基於以下等式計算RC:
RC = (總預浸體重量-玻璃布重量)/(總預浸體重量)×100%
Cu剝離強度測試
使用IPC-TM-650測試方法手冊2.4.8.剝離強度,基於每單位面積1盎司Cu重量來量測由2116NE玻璃製備之層壓板的Cu剝離強度。聯合SSTM-1模型(United SSTM-1 Model)
Dk及Df測試
Df及Dk值藉由使用分後介電諧振器(SPC)方法進行分析。在10 GHz下的Df及Dk值藉由來自Agilent Technologies的網路分析器N5230A來量測。「AB」係指在將樣品保持在120℃下2小時之後的量測。「RT」係指在將樣品保持在45至55%濕度下16小時之後的量測。除CE-6 (其資料自由2116NE玻璃製備之層壓板獲得)及FE-25至FE-35以外,下文所提及之Dk及Df結果獲自由1078NE玻璃製備之層壓板。
樹脂流動
使用IPC-TM-650測試方法手冊2.3.17來量測未增強膜之樹脂流動。
CTE量測
25℃至260℃之CTE (z軸)值由來自TA Instruments的TMA 450使用0.25吋×0.25吋之未增強層壓板量測。
可燃性
基於UL94,使用具有2116NE玻璃布的12層層壓板或使用具有FR-4基體的未增強層壓板(如通常程序1所撰寫)進行可燃性評估。
實例1:可固化組成物及比較可固化組成物之製備及表徵
根據通用程序1製備調配物實例1至24 (FE-1至FE-24)。此等組成物之組分及由此等組成物形成之層壓板的特性概述於以下表1及表2中。表1中所示之百分比係指組分在組成物之總固體含量中所占的重量百分比。層壓板由1078NE或2116NE玻璃布預浸體薄片及1盎司HS2-M2-VSP銅箔(Mitsui Mining & Smelting)製成。使用循環A固化FE-1至FE-11 (FE-9除外)。使用循環D固化FE-9。使用循環B固化FE-12。使用循環C固化FE-13、FE-14、FE-16及FE-19至FE-20。使用循環E固化FE-15、FE-17、FE-18及FE-21。使用循環F固化FE-22及FE-24。使用循環G固化FE-23。
表1
表2
聚 ( 伸芳基醚 ) | 阻燃劑 | 彈性體 | 填充劑 | 交聯劑 | 引發劑 | 總計 | |
FE-1 | HC-G0021 34.26% | PQ60 17.68% | 無 | EQ2410-SMC 45% | BVPE 2.17% | CCDFB 0.89% | 100% |
FE-2 | HC-G0021 34.26% | PQ60 17.68% | 無 | EQ2410-SMC 41.95% | BVPE 4.34% | CCDFB 1.77% | 100% |
FE-3 | HC-G0021 30.48% | PQ60 17.97% | SEBS-A 0.54% Septon 2104 2.16% | EQ2410-SMC 45.74% | BVPE 2.21% | CCDFB 0.9% | 100% |
FE-4 | HC-G0021 30.48% | BES5-1150P 16.31% | SEBS-A 0.54% Septon 2104 2.16% | EQ2410-SMC 45.74% | BVPE 3.32% | CCDFB 1.45% | 100% |
FE-5 | HC-G0021 30.27% | BES5-1150P 16.89% | Septon 2104 3.30% | EQ2410-SMC 45.42% | BVPE 2.68% | CCDFB 1.44% | 100% |
FE-6 | HC-G0021 30.48% | BES5-1150P 16.31% | Kraton 1536 0.54% Septon 2104 2.16% | EQ2410-SMC 45.74% | BVPE 3.32% | CCDFB 1.45% | 100% |
FE-7 | HC-G0021 30.48% | BES5-1150P 17.97% | 共聚物A 1.11% SEBS-A 0.54% Septon 2104 2.16% | EQ2410-SMC 45.74% | BVPE 1.11% | CCDFB 0.9% | 100% |
FE-8 | HC-G0030 31.87% | BES5-1150P 19.69% | SEBS-A 0.43% M1913 0.43% Septon 2104 3.44% | EQ1010-SMC 40.60% | BVPE 2.36% | CCDFB 1.18% | 100% |
FE-9 | HC-G0030 26.89% HC-G0024 2.99% | BES5-1150P 15.86% PX-200 1.98% | SEBS-A 0.69% SBS-A 1.95% Septon 2104 1.96% | EQ2410-SMC 46.8% | None | CCDFB 0.88% | 100% |
FE-10 | HC-G0030 29.84% | BES5-1150P 17.59% | SBS-A 2.11% Septon 2104 2.11% | EQ2410-SMC 44.78% | BVPE 2.60% | CCDFB 0.88% VR-110 0.09% | 100% |
FE-11 | HC-G0030 32.30% | PQ-60 17.97% | MSEBMS 3.17% | EQ2410-SMC 28.97% EQ1010-SMC 14.48% | BVPE 2.21% | CCDFB 0.90% | 100% |
FE-12 | HC-G0030 31.62% | BES5-1150P 17.59% | MSEBMS 3.10% Septon 2104 0.57% | EQ2410-SMC 28.35% EQ1010-SMC 14.18% | BVPE 3.25% | CCDFB 1.32% Perbutyl D 0.02% | 100% |
FE-13 | HC-G0030 17.13% SA9000 17.13% | BES5-1150P 17.68% | 無 | EQ2410-SMC 45.00% | BVPE 2.17% | CCDFB 0.89% | 100% |
FE-14 | HC-G0030 30.48% | OP945 17.97% | SEBS-A 0.54% Septon 2104 2.16% | EQ2410-SMC 45.74% | BVPE 2.21% | CCDFB 0.90% | 100% |
FE-15 | HC-G0030 21.40% HC-G0024 8.71% | BES5-1150P 17.62% | SBS-A 1.71% MP-10 2.60% | EQ2410-SMC 46.78% | LME 11613 0.45% | CCDFB 0.73% | 100% |
FE-16 | HC-G0030 30.48% | Altexia 17.97% | SEBS-A 0.54% Septon 2104 2.16% | EQ2410-SMC 45.74% | BVPE 2.21% | CCDFB 0.90% | 100% |
FE-17 | HC-G0030 30.48% | PX-200 17.97% | SEBS-A 0.54% Septon 2104 2.16% | EQ2410-SMC 45.74% | BVPE 2.21% | CCDFB 0.90% | 100% |
FE-18 | HC-G0030 30.48% | DiDOPO 17.97% | SEBS-A 0.54% Septon 2104 2.16% | EQ2410-SMC 45.74% | BVPE 2.21% | CCDFB 0.90% | 100% |
FE-19 | HC-G0030 30.48% | BES5-1150P 16.31% | SBS-A 0.54% Septon 2104 2.16% | EQ2410-SMC 45.74% | BVPE 3.32% | CCDFB 1.45% | 100% |
FE-20 | HC-G0030 30.48% | FP-72TP 17.97% | SEBS-A 0.54% Septon 2104 2.16% | EQ2410-SMC 45.74% | BVPE 2.21% | CCDFB 0.90% | 100% |
FE-21 | HC-G0030 25.4% HC-G0024 4.48% | BES5-1150P 17.62% | SBS-A 1.73% MP-10 2.65% | EQ2410-SMC 46.8% | LME 11613 0.43% | CCDFB 0.89% | 100% |
FE-22 | HC-G0030 24.8% HC-G0024 5.08% | BES5-1150P 17.62% | SBS-A 1.73% MP-10 2.25% Septon 2104 0.40% | EQ2410-SMC 46.8% | LME 11613 0.43% | CCDFB 0.89% | 100% |
FE-23 | HC-G0030 23.11% HC-G0024 4.98% | BES5-1150P 17.28% | SBS-A 0.57% MP-10 2.56% | EQ2410-SMC 47.83% | BVPE 2.12% TAIC 1.2% | CC-P3 0.35% | 100% |
FE-24 | HC-G0030 25.94% HC-G0024 5.31% | BES5-1150P 18.43% | SBS-A 1.47% MP-10 2.77% | EQ2410-SMC 43.08 % HS-200-VN 1.84% | BVPE 0.79% | CC-P3 0.37% | 100% |
銅剝離 (WG/XG ;磅 / 吋 ) | Dk [AB] | Dk [IPC] | Df [AB] | Df [IPC] | RC (%) | UL94 V-0 | |
FE-1 | 4.2 / 4.2 | 3.22 | 3.20 | 0.0013 | 0.0014 | 70.6 | 通過 |
FE-2 | 3.7 / 3.7 | 3.25 | 3.27 | 0.0012 | 0.0012 | 71.6 | 通過 |
FE-3 | 3.5 / 3.0 | 3.4 | 3.4 | 0.0013 | 0.0014 | 73.8 | 通過 |
FE-4 | 3.7 / 3.9 | 3.36 | 3.36 | 0.0012 | 0.0014 | 72.7 | 通過 |
FE-5 | 3.2 / 3.3 | 3.23 | 3.23 | 0.0013 | 0.0014 | 70.0 | 通過 |
FE-6 | 3.4 / 3.9 | 3.32 | 3.36 | 0.0012 | 0. 0014 | 76.0 | 通過 |
FE-7 | 3.0 / 3.0 | 3.21 | 3.21 | 0.0013 | 0.0014 | 73.4 | 通過 |
FE-8 | 2.3 / 2.5 | 3.10 | 3.10 | 0.0012 | 0.0015 | 67.5 | 通過 |
FE-9 | 3.2 / 3.2 | 3.22 | 3.22 | 0.0011 | 0.0012 | 74.2 | 通過 |
FE-10 | 3.1 /3.1 | 3.28 | 3.28 | 0.0013 | 0.0013 | 70.8 | 通過 |
FE-11 | 3.3 / 3.2 | 3.32 | 3.36 | 0.0013 | 0.0013 | 73.7 | 通過 |
FE-12 | 3.5 / 3.3 | 3.23 | 3.25 | 0.0014 | 0.0015 | 69.9 | 通過 |
FE-13 | N/A / 2.6 | 3.19 | 3.21 | 0.0014 | 0.0015 | 72.8 | 通過 |
FE-14 | 1.6 / 1.8 | 3.20 | 3.20 | 0.0018 | 0.0018 | 69.3 | 通過 |
FE-15 | 4.1 / 4.1 | 3.28 | 3.29 | 0.0011 | 0.0012 | 76.1 | 通過 |
FE-16 | N/A | 3.33 | 3.33 | 0.0013 | 0.0014 | 70.1 | 通過 |
FE-17 | 3.5 / 3.6 | 3.64 | 3.64 | 0.0016 | 0.0016 | 55.2 | 通過 |
FE-18 | 3.5 / 2.9 | 3.38 | 3.42 | 0.0017 | 0.0025 | 68.9 | 通過 |
FE-19 | 2.8 / 3.6 | 3.29 | 3.29 | 0.0013 | 0.0014 | 68.4 | 通過 |
FE-20 | 2.5 / 2.6 | 3.33 | 3.32 | 0.0013 | 0.0013 | 69.6 | 通過 |
FE-21 | 4.1 / 3.9 | 3.20 | 3.22 | 0.0012 | 0.0013 | 73.1 | 通過 |
FE-22 | 4.1 / 3.6 | 3.28 | 3.28 | 0.0012 | 0.0013 | 73.8 | 通過 |
FE-23 | 4.3 / 4.2 | 3.37 | 3.37 | 0.0012 | 0.0014 | 72.1 | 通過 |
FE-24 | 3.7 / 3.4 | 3.18 | 3.19 | 0.0013 | 0.0013 | 71.3 | 通過 |
如表2中所示,FE-1至FE-24 (全部包括含N聚(伸芳基醚)及含磷阻燃劑)出人意料地展現優異的電氣特性(例如相對較低的Df)及機械特性(例如相對較高的Cu剝離強度,亦即高於3.0磅/吋)。
此外,如表2中所示,本發明實例展現優良的阻燃性且通常符合UL94 V-0可燃性標準。
比較調配物實例1至10 (CE-1至CE-10)根據通用程序1製備。此等組成物之組分及由此等組成物形成之層壓板的特性概述於以下表3及表4中。表3中所示之百分比係指組分在組成物之總固體含量中所占的重量百分比。層壓板由1078NE或2116NE玻璃布及1盎司HS1-M2-VSP銅箔(Mitsui Mining & Smelting)製成。使用循環H固化CE-1及CE-2。使用循環I固化CE-3至CE-5。使用循環J固化CE-6至CE-9。使用循環K固化CE-10。
表3
表4
聚 ( 伸芳基醚 ) | 阻燃劑 | 彈性體 | 填充劑 | 交聯劑 | 引發劑 | 總計 | |
CE-1 | SA9000 26.01% | OP945 19.53% PQ-60 10.07% SPV-100 3.00% | MSEBMS 6.57% | EQ2410-SMC 20% OFS-6224 0.56% OFS-6124 0.28% SIB1817.0 0.10% | TAIC 13.73% | VulCup R 0.15% | 100% |
CE-2 | SA9000 18.10% | OP935 20.95% BES5-1150P 7.59% SPV-100 3.22% | MSEBMS 5.98% | EQ2410-SMC 25.02% OFS-6224 0.54% OFS-6124 0.27% SIB1817.0 0.08% | TAIC 18.10% | VulCup R 0.15% | 100% |
CE-3 | SA9000 17.08% | OP935 20.96% BES5-1150P 7.59% SPV-100 3.22% | MSEBMS 5.98% | EQ2410-SMC 25.00% OFS-6224 0.54% OFS-6124 0.27% SIB1817.0 0.08% | TAIC 17.08% | VulCup R 0.05% CCDFB 2.15% | 100% |
CE-4 | SA9000 17.08% | OP935 22.50% BES5-1150P 7.59% FP-700 3.22% | MSEBMS 5.98% | EQ2410-SMC 23.46% OFS-6224 0.54% OFS-6124 0.27% SIB1817.0 0.08% | TAIC 17.08% | VulCup R 0.05% CCDFB 2.15% | 100% |
CE-5 | SA9000 17.08% | OP935 24.18% BES5-1150P 7.59% FP-700 3.22% | MSEBMS 5.98% | EQ2410-SMC 21.78% OFS-6224 0.54% OFS-6124 0.27% SIB1817.0 0.08% | TAIC 17.08% | VulCup R 0.05% CCDFB 2.15% | 100% |
CE-6 | SA9000 26.93% | PQ-60 28.52% | 無 | SC2500-SVJ 26.04% OFS-6030 0.20% | TAIC 17.95% | DYBP 0.21% DCP 0.15% | 100% |
CE-7 | SA9000 21.38% | OP935 22.44% | Ricon 100 4.88% | SC2500-SVJ 28.72% OFS-6030 0.56% OFS-6124 0.28% SIB1817.0 0.10% | TAIC 21.38% | VulCup R 0.26% | 100% |
CE-8 | SA9000 21.38% | Altexia 22.44% | Ricon 100 4.88% | SC2500-SVJ 28.72% OFS-6030 0.56% OFS-6124 0.28% SIB1817.0 0.10% | TAIC 21.38% | VulCup R 0.26% | 100% |
CE-9 | SA9000 21.38% | Saytex 8010 22.44% | Ricon 100 4.88% | SC2500-SVJ 28.72% OFS-6030 0.56% OFS-6124 0.28% SIB1817.0 0.10% | TAIC 21.38% | VulCup R 0.26% | 100% |
CE-10 | SA9000 24.01% | OP935 19.53% FP-72TP 7.07% SPV-100 3.00% | MSEBMS 6.57% | EQ2410-SMC 24.10% OFS-6224 0.56% OFS-6124 0.28% SIB1817.0 0.10% | TAIC 12.73% | VulCup R 0.05% CCDFB 2.00% | 100% |
銅剝離 (WG/XG ;磅 / 吋 ) | Dk [AB] | Dk [IPC] | Df [AB] | Df [IPC] | RC (%) | UL94 V-0 | |
CE-1 | 2.9 / 2.9 | 3.04 | 3.04 | 0.0020 | 0.0024 | 73.2 | 失敗 |
CE-2 | 3.3 / 2.8 | 3.45 | 3.41 | 0.0022 | 0.0026 | 75.5 | 通過 |
CE-3 | N/A | 3.11 | 3.14 | 0.0020 | 0.0023 | 70.6 | 失敗 |
CE-4 | 1.8 / 2.2 | 3.03 | 3.06 | 0.0021 | 0.0025 | 79.3 | 通過 |
CE-5 | 2.3 / 2.1 | 3.11 | 3.12 | 0.0021 | 0.0023 | 77.1 | 失敗 |
CE-6 | N/A / 2.3 | 3.32 | 3.41 | 0.0018 | 0.0020 | 60 | 通過 |
CE-7 | 3.4 / 4.1 | 3.14 | 3.14 | 0.0029 | 0.0030 | 72 | 通過 |
CE-8 | 4.3 / 4.6 | 3.14 | 3.17 | 0.0024 | 0.0026 | 72 | 通過 |
CE-9 | 5.8 / 5.9 | 3.22 | 3.24 | 0.0021 | 0.0026 | 76 | 通過 |
CE-10 | 3.5 / 3.5 | 3.18 | 3.18 | 0.0022 | 0.0024 | 72 | 通過 |
如表4中所示,CE-1至CE-10 (其中之各者不包括本文所描述之聚(伸芳基醚))展現相對不良的電氣特性(例如相對較高的Df)。不希望受理論所束縛,咸信,由於CE-1至CE-10中之PPE聚合物與包括聚(伸芳基醚)之本揭露內容之可固化組成物相比具有相對較高的最小熔融黏度,此等組成物與包括聚(伸芳基醚)之本揭露內容之可固化組成物相比需要包括更低的二氧化矽填充劑位準,其將產生較高Df。且若此等組成物包括較高位準之二氧化矽或阻燃劑,則由於高黏度及流動較差會導致樹脂組成物之間的黏附性變差,因此機械特性(如ILBS)亦會變差。
另外,CE-6展現相對較差黏附特性(例如銅剝離強度值低於3磅/吋)。在不希望受理論束縛的情況下,咸信高阻燃劑位準使得銅剝離強度降低。
根據通用程序1中未增強膜之製備及未增強層壓板之製備的部分來製備調配物實例25至35 (FE-25至FE-35)。此等組成物之組分及由此等組成物形成之層壓板的特性概述於以下表5及表6中。
表5
表6
聚 ( 伸芳基醚 ) | 阻燃劑 | 彈性體 | 填充劑 | 交聯劑 | 引發劑 | 總計 | |
FE-25 | HC-G0030 14.03% | SPV-100 22.48% BES5-1150P 18.98% | Kraton D1623 7.17% | HS-200-TM 19.56% OFS-6030 0.43% | 雙酚A苯并㗁𠯤 11.08% BVPE 4.93% | CCDFB 1.34% | 100% |
FE-26 | HC-G0030 14.03% | SPV-100 22.48% BES5-1150P 18.98% | Kraton D1623 7.17% | HS-200-TM 19.56% OFS-6030 0.43% | 雙酚A苯并㗁𠯤 11.08% LDAIC 4.93% | CCDFB 1.34% | 100% |
FE-27 | HC-G0030 14.03% | SPV-100 22.48% BES5-1150P 18.98% | Kraton D1623 7.17% Vector 4411 2.69% | HS-200-TM 19.56% OFS-6030 0.43% | 雙酚A苯并㗁𠯤 11.08% LDAIC 2.24% | CCDFB 1.34% | 100% |
FE-28 | HC-G0030 14.40% | SPV-100 23.07% BES5-1150P 17.92% | Kraton D1623 7.35% Vector 4411 5.06% | HS-200-MT 19.01% OFS-6030 0.44% | 雙酚A苯并㗁𠯤 11.38% | CCDFB 1.38% | 100% |
FE-29 | HC-G0030 14.40% | SPV-100 23.07% BES5-1150P 17.92% | Kraton D1623 7.35% Vector 4411 5.06% | HS-200-MT 19.01% OFS-6030 0.44% | P-d苯并㗁𠯤 11.38% | CCDFB 1.38% | 100% |
FE-30 | HC-G0030 14.40% | SPV-100 23.07% BES5-1150P 17.92% | Vector 4411 12.41% | HS-200-MT 19.01% OFS-6030 0.44% | 雙酚A苯并㗁𠯤 5.86% LME 11613 5.52% | CCDFB 1.38% | 100% |
FE-31 | HC-G0030 14.40% | SPV-100 23.07% BES5-1150P 17.92% | Vector 4411 12.41% | HS-200-MT 19.01% OFS-6030 0.44% | BMI-TMH 8.97% LDAIC 2.41% | CCDFB 1.38% | 100% |
FE-32 | HC-G0030 19.66% | SPV-100 22.89% BES5-1150P 17.77% | Kraton D1623 7.30% Vector 4411 5.02% | HS-200-TM 19.66% OFS-6030 0.44% | 雙酚A苯并㗁𠯤 5.81% | CCDFB 1.37% | 100% |
FE-33 | HC-G0030 17.36% | SPV-100 22.89% BES5-1150P 17.77% | Kraton D1623 7.30% Vector 4411 5.02% | HS-200-TM 19.66% OFS-6030 0.44% | 雙酚A苯并㗁𠯤 5.81% BMI-TMH 2.40% | CCDFB 1.37% | 100% |
FE-34 | HC-G0030 14.28% | SPV-100 22.89% BES5-1150P 17.77% | Kraton D1623 7.30% Vector 4411 2.50% | HS-200-TM 19.66% OFS-6030 0.44% | 雙酚A苯并㗁𠯤 11.29% NEX9470S 2.50% | CCDFB 1.37% | 100% |
FE-35 | HC-G0030 17.36% | SPV-100 25.28% BES5-1150P 17.77% | Kraton D1623 7.30% Vector 4411 5.02% | HS-200-TM 19.66% OFS-6030 0.44% | 雙酚A苯并㗁𠯤 5.81% | CCDFB 1.37% | 100% |
Dk [AB] | Df [AB] | 樹脂流動 (%) | CTE (ppm/℃ ) | UL94 V-0 | |
FE-25 | 2.21 | 0.0024 | 92 | 41 | 通過 |
FE-26 | 2.14 | 0.0023 | 90 | 33 | 通過 |
FE-27 | 2.16 | 0.0025 | 79 | 41 | 通過 |
FE-28 | 2.13 | 0.0026 | 81 | 31 | 通過 |
FE-29 | 2.16 | 0.0026 | 89 | 26 | 通過 |
FE-30 | 2.20 | 0.0021 | N/A | 39 | 通過 |
FE-31 | 2.24 | 0.0019 | 68 | N/A | 通過 |
FE-32 | 2.20 | 0.0019 | 88 | 48 | 通過 |
FE-33 | 2.20 | 0.0019 | 77 | 62 | 通過 |
FE-34 | 2.21 | 0.0022 | 83 | 43 | 通過 |
FE-35 | 2.19 | 0.0020 | 91 | 41 | 通過 |
如表6中所示,FE-25至FE-35 (全部包括含N聚(伸芳基醚)及含磷阻燃劑)出人意料地展現出極低Dk、高樹脂流動、低CTE及良好阻燃性。
其他實施例在以下申請專利範圍之範疇內。
(無)
Claims (50)
- 一種可固化組成物,其包含: 至少一種包含一單體單元之聚(伸芳基醚)聚合物,該單體單元包含嘧啶、吡𠯤或嗒𠯤基團; 至少一種含磷阻燃劑;及 至少一種自由基引發劑。
- 如請求項1之組成物,其中該至少一種聚(伸芳基醚)聚合物由一官能基封端,該官能基包含順丁烯二醯亞胺、苯乙烯、烯丙基、烯丙基醚、丙烯酸酯、甲基丙烯酸酯、三聚異氰酸酯或苯并㗁𠯤基團。
- 如請求項1之組成物,其中該至少一種聚(伸芳基醚)聚合物包含式(5)至式(9)中之一者的單體單元: (5)、 (6)、 (7)、 (8)及 (9), 其中R 1為H、C 1-C 10烷基或芳基;R 2、R 3及R 6中之各者獨立地為C 1-C 10烷基;R 4、R 5、R 7及R 8中之各者為H或C 1-C 10烷基;p為0至4之整數;q為0至4之整數;且r為0至4之整數。
- 如請求項1之組成物,其中該至少一種聚(伸芳基醚)聚合物以該組成物之固體含量之約1 wt%至約50 wt%的量存在。
- 如請求項1之組成物,其中該至少一種含磷阻燃劑包含二乙基亞磷酸鋁、對二甲苯-雙-二苯基膦氧化物、(2,5-二烯丙基氧基苯基)二苯基膦氧化物、六苯氧基環三磷氮烯、參(2-烯丙基苯氧基)三苯氧基環三磷氮烯、間苯二酚雙(二-2,6-二甲基苯基磷酸酯)、氰基苯氧基(苯氧基)環磷氮烯、甲苯基氧基(苯氧基)環磷氮烯、螺環三磷氮烯或含乙烯基之磷氮烯。
- 如請求項1之組成物,其中該阻燃劑以該組成物之固體含量之約1 wt%至約50 wt%的量存在。
- 如請求項1之組成物,其中該阻燃劑以該組成物之固體含量之約1 wt%至約40 wt%的量存在。
- 如請求項1之組成物,其進一步包含至少一種填充劑。
- 如請求項8之組成物,其中該至少一種填充劑包含二氧化矽、氧化鋁、石英、二氧化鈦、氮化硼、鈦酸鋇、鈦酸鍶鋇或聚合物顆粒。
- 如請求項8之組成物,其中該至少一種填充劑包含中空顆粒。
- 如請求項10之組成物,其中該等中空顆粒包含中空二氧化矽顆粒或中空聚合物顆粒。
- 如請求項10之組成物,其中該等顆粒具有約0.7 µm至約10 µm之平均直徑。
- 如請求項8之組成物,其中該至少一種填充劑以該組成物之固體含量之約10 wt%至約65 wt%的量存在。
- 如請求項1之組成物,其中該至少一種自由基引發劑包含過氧化物、烴或偶氮化合物。
- 如請求項14之組成物,其中該至少一種自由基引發劑包含雙(4-乙烯基苯基)乙烷、2,2'-偶氮雙(2,4,4-三甲基戊烷)、二-(三級丁基過氧基異丙基)苯、雙(1-甲基-1-苯乙基)過氧化物、2,5-二甲基-2,5-二(三級丁基過氧基)己炔-3、2,5-二甲基-2,5-二(三級丁基過氧基)己烷、過氧化二異丙苯、3,4-二甲基-3,4-二苯基己烷或2,3-二甲基-2,3-二苯基丁烷。
- 如請求項1之組成物,其中該至少一種自由基引發劑以該組成物之固體含量之約0.1 wt%至約10 wt%的量存在。
- 如請求項1之組成物,其進一步包含至少一種彈性體。
- 如請求項17之組成物,其中該至少一種彈性體包含聚(苯乙烯-乙烯-丁烯-苯乙烯)共聚物、聚(甲基苯乙烯-乙烯-丁烯-甲基苯乙烯)共聚物、與順丁烯二酸酐接枝之聚(苯乙烯-乙烯-丁烯-苯乙烯)共聚物、聚(苯乙烯-共-二乙烯基苯-共-乙基苯乙烯)共聚物、聚(甲基苯乙烯-共-4-(二甲基乙烯基矽烷基甲基)苯乙烯)共聚物、聚丁二烯、聚(丁二烯-共-苯乙烯)共聚物、聚二乙烯基苯共聚物、聚(苯乙烯-乙烯-丙烯-苯乙烯)共聚物、聚(苯乙烯-丁二烯-苯乙烯)共聚物、聚(苯乙烯-異戊二烯-苯乙烯)共聚物或聚(乙烯-丙烯-二烯)共聚物。
- 如請求項17之組成物,其中該彈性體以該組成物之固體含量之約1 wt%至約40 wt%的量存在。
- 如請求項1之組成物,其進一步包含至少一種有機溶劑。
- 如請求項20之組成物,其中該至少一種有機溶劑包含甲基乙基酮、甲基異丁基酮、環戊酮、環己酮、甲苯或二甲苯。
- 如請求項20之組成物,其中該至少一種有機溶劑以該組成物之總重量之約1 wt%至約50 wt%的量存在。
- 如請求項1之組成物,其進一步包含至少一種交聯劑。
- 如請求項23之組成物,其中該至少一種交聯劑包含雙(4-乙烯基苯基)乙烷、三聚氰酸三烯丙酯、三聚異氰酸三烯丙酯、三聚異氰酸三甲基烯丙酯、聚丁二烯、聚(丁二烯-共-苯乙烯)共聚物、二乙烯基苯、(甲基)丙烯酸酯化合物、雙酚A二烯丙基醚、苊烯、氰酸酯、苯并㗁𠯤或雙順丁烯二醯亞胺。
- 如請求項23之組成物,其中該至少一種交聯劑以該組成物之固體含量之約1 wt%至約30 wt%的量存在。
- 如請求項1之組成物,其進一步包含至少一種偶合劑。
- 如請求項26之組成物,其中該至少一種偶合劑包含矽烷、鈦酸鹽或鋯酸鹽。
- 如請求項27之組成物,其中該至少一種偶合劑包含甲基丙烯醯氧基丙基三甲氧基矽烷、乙烯基三甲氧基矽烷、水解乙烯基苯甲基胺基乙基胺基丙基三甲氧基矽烷、苯基三甲氧基矽烷、對苯乙烯基三甲氧基矽烷、3-異氰酸丙基三乙氧基矽烷、3-甲基丙烯醯氧基丙基三甲氧基矽烷、四(2,2-二烯丙基氧基甲基-1-丁基)雙(二-十三烷基亞磷酸酯)鈦酸酯或四(2,2-二烯丙基氧基甲基-1-丁基)雙(二-十三烷基亞磷酸酯)鋯酸酯。
- 如請求項26之組成物,其中該至少一種偶合劑以該組成物之固體含量之約0.1 wt%至約5 wt%的量存在。
- 如請求項1之組成物,其中該組成物基本上不含鹵素。
- 一種膜,其係由如請求項1之組成物製備。
- 如請求項31之膜,其中該膜具有至多約3.1之介電常數。
- 如請求項31之膜,其中該膜具有至多約0.002之損耗因數。
- 一種預浸體產品,其包含用如請求項1之組成物浸漬的編織或非編織基體。
- 如請求項34之預浸體產品,其中該基體包含玻璃布。
- 一種層壓板,其包含至少一個由如請求項34之預浸體產品製備之層。
- 如請求項36之層壓板,其進一步包含該至少一個層之一表面上的至少一個金屬箔。
- 如請求項37之層壓板,其中該金屬箔係銅箔。
- 一種用於一電子產品中之電路板,其包含如請求項36之層壓板。
- 一種方法,其包含: 用如請求項1之組成物浸漬編織或非編織基體;及 固化該組成物以形成預浸體產品。
- 如請求項40之方法,其中固化該組成物係在約150℃至約250℃範圍內之溫度下進行。
- 如請求項40之方法,其進一步包含將該預浸體產品塗覆至一金屬箔以形成一層壓板。
- 如請求項42之方法,其進一步包含將該層壓板轉換成一印刷電路板。
- 如請求項1之組成物,其中存在液態含磷阻燃劑。
- 如請求項44之組成物,其中該液態含磷阻燃劑係可交聯的。
- 如請求項44之組成物,其中該液態含磷阻燃劑以該組成物之固體含量之約1 wt%至約30 wt%的量存在。
- 如請求項44之組成物,其中該可交聯液態含磷阻燃劑為參(2-烯丙基苯氧基)三苯氧基環三磷氮烯。
- 如請求項47之組成物,其中該阻燃劑之總量為該組成物之固體含量的約1 wt%至約50 wt%。
- 如請求項44之組成物,其中該至少一種填充劑包含中空二氧化矽顆粒。
- 如請求項49之組成物,其中該等中空二氧化矽顆粒以該組成物之固體含量之約10 wt%至約35 wt%的量存在。
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US202263425787P | 2022-11-16 | 2022-11-16 | |
US63/425,787 | 2022-11-16 |
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US (1) | US20240174803A1 (zh) |
JP (1) | JP2024072808A (zh) |
KR (1) | KR20240075715A (zh) |
CN (1) | CN118047913A (zh) |
TW (1) | TW202428699A (zh) |
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JP2002026493A (ja) * | 2000-07-06 | 2002-01-25 | Nippon Zeon Co Ltd | ソルダーマスク用硬化性組成物及び多層回路基板 |
CN112979707B (zh) * | 2021-03-03 | 2022-09-02 | 威海金威化学工业有限责任公司 | 一种三(2-烯丙基)苯氧基三苯氧基环三磷腈的制备方法 |
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- 2023-11-14 JP JP2023193712A patent/JP2024072808A/ja active Pending
- 2023-11-14 TW TW112143909A patent/TW202428699A/zh unknown
- 2023-11-14 US US18/509,002 patent/US20240174803A1/en active Pending
- 2023-11-14 KR KR1020230157275A patent/KR20240075715A/ko unknown
- 2023-11-14 CN CN202311510090.4A patent/CN118047913A/zh active Pending
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JP2024072808A (ja) | 2024-05-28 |
KR20240075715A (ko) | 2024-05-29 |
US20240174803A1 (en) | 2024-05-30 |
CN118047913A (zh) | 2024-05-17 |
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