TW202208560A - 膨脹型塗料 - Google Patents
膨脹型塗料 Download PDFInfo
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- TW202208560A TW202208560A TW110115826A TW110115826A TW202208560A TW 202208560 A TW202208560 A TW 202208560A TW 110115826 A TW110115826 A TW 110115826A TW 110115826 A TW110115826 A TW 110115826A TW 202208560 A TW202208560 A TW 202208560A
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- coating composition
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- 238000000576 coating method Methods 0.000 title claims description 32
- 239000000203 mixture Substances 0.000 claims abstract description 135
- 239000008199 coating composition Substances 0.000 claims abstract description 82
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 75
- 239000000758 substrate Substances 0.000 claims abstract description 56
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 43
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 41
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 34
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- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 claims abstract description 14
- 238000000034 method Methods 0.000 claims abstract description 12
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- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 claims description 31
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 claims description 29
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- OTRAYOBSWCVTIN-UHFFFAOYSA-N OB(O)O.OB(O)O.OB(O)O.OB(O)O.OB(O)O.N.N.N.N.N.N.N.N.N.N.N.N.N.N.N Chemical compound OB(O)O.OB(O)O.OB(O)O.OB(O)O.OB(O)O.N.N.N.N.N.N.N.N.N.N.N.N.N.N.N OTRAYOBSWCVTIN-UHFFFAOYSA-N 0.000 claims description 2
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- GUSFEBGYPWJUSS-UHFFFAOYSA-N pentaazanium;[oxido(phosphonatooxy)phosphoryl] phosphate Chemical compound [NH4+].[NH4+].[NH4+].[NH4+].[NH4+].[O-]P([O-])(=O)OP([O-])(=O)OP([O-])([O-])=O GUSFEBGYPWJUSS-UHFFFAOYSA-N 0.000 description 13
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- BIKXLKXABVUSMH-UHFFFAOYSA-N trizinc;diborate Chemical compound [Zn+2].[Zn+2].[Zn+2].[O-]B([O-])[O-].[O-]B([O-])[O-] BIKXLKXABVUSMH-UHFFFAOYSA-N 0.000 description 10
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Abstract
揭示包含以總固體重量計呈5-20 wt%之量的TiO2
、呈20-55 wt%之量的磷酸源、及硼酸源、鋁源及/或二氧化矽源的膨脹型塗料組合物,同樣揭示使用此類組合物之方法及塗佈有此類組合物之基板。
Description
本發明係有關一種膨脹型塗料組合物,關於一種用該組合物塗佈基板之方法,關於一種用該組合物塗佈之基板,關於一種包含該基板之物件,包括電池。
已針對多種結構性應用使用膨脹型塗料來防止纖維素與烴燃燒。此類塗料藉由在暴露於酷熱時形成含碳炭而提供保護。當在火中形成的炭膨脹至最佳厚度且黏附至基板時及/或當該炭以一定厚度形成使得直接火焰吹打將不會逐漸損害炭完整性(諸如藉由在炭上留下裂紋)時,該炭提供最佳保護。眾多基板可受益於塗佈有此等塗料,包括(例如)用於商業及運輸基礎建設(如旅館、機場、音樂廳或離岸地點、化工廠、鑽油平台及其類似者)中之結構建築組件,其將在著火的情況下暴露於極端熱。電池,諸如鋰離子電池,亦可暴露於此類酷熱;許多電池且尤其鋰離子電池易發生熱失控,在此期間熱量及氣體自電池快速排出且產生火災。習知單一包裝防火塗料對於風化而言並不耐久,而雙包裝防火塗料太黏稠而不能以低厚度施加;因此需要經改良之耐火塗料,包括用於電池之彼等塗料。
本發明係有關一種塗料組合物,其包含:a)成膜組分;b)磷酸源;c)硼酸源;鋁源;及/或二氧化矽源;d) TiO2
;及e)氣體源;其中該TiO2
以5至20 wt%,諸如9至15 wt%之量存在,該磷酸源以20至55 wt%,諸如25至40 wt%或40至55 wt%之量存在,且其中若組分c包含硼酸源,則其以5至20 wt%,諸如9至15 wt%之量存在,若組分c包含鋁源,則其以0.1至10 wt%,諸如0.2至8 wt%之量存在,且若組分c包含二氧化矽源,則其以0.1至5 wt%,諸如0.4至1 wt%之量存在,其中wt%以該組合物之總固體重量計。組合物可形成為自支撐膜或薄片。如隨附申請專利範圍中所闡述之利用根據本發明之塗料組合物塗佈基板之方法或如本文所描述自其形成之膜或薄片及由此塗佈之基板以及包含此類經塗佈基板/膜或薄片之物件,包括至少部分地塗佈有本發明組合物之電池組件及電池以及包含本發明之自支撐膜或薄片之電池亦在本發明之範疇內。
將在下文更詳細地論述本發明。
本發明係有關一種塗料組合物,其包含:a)成膜組分;b)磷酸源;c)硼酸源;鋁源;及/或二氧化矽源;d) TiO2
;及e)氣體源;其中TiO2
以5至20 wt%,諸如9至15 wt%之量存在,磷酸源以20至55 wt%,諸如25至40 wt%或40至55 wt%之量存在,且其中若組分c包含硼酸源,則其以5至20 wt%,諸如9至15 wt%之量存在,若組分c包含鋁源,則其以0.1至10 wt%,諸如0.2至8 wt%之量存在,且若組分c包含二氧化矽源,則其以0.1至5 wt%,諸如0.4至1 wt%之量存在,其中wt%以該組合物之總固體重量計。應瞭解,組合物當未固化時之總固體重量將與固化時之總固體重量相同。
本發明塗料組合物可用於形成膨脹型塗料。亦即,當暴露於熱量(諸如在燃燒期間經歷之高溫)時,塗料經歷膨脹及炭化。本發明人已發現,在以上給定之範圍內,與TiO2
及磷酸源結合使用硼酸源、鋁源及/或二氧化矽源出人意料地產生具有所需炭形成以及與基板之所需黏附力的膨脹型塗料。「所需炭形成」意謂炭不可容易地破裂或藉由直接火焰吹打而移除,且膨脹係數可為5至25,諸如7至20,該膨脹係數為炭厚度與塗膜厚度之間的比率。「所需黏附力」意謂炭將在直接火焰吹打期間實質上保持完好,且在防火測試期間或之後不發生炭自基板之明顯脫離。因此,根據本發明之塗料組合物提供優於習知膨脹型塗料組合物之優點。
塗料組合物包含成膜組分。「成膜」意謂組合物在乾燥及/或固化後立即可在表面上形成連續膜。成膜組分可包括例如成膜樹脂及其對應之交聯劑。根據本發明,可使用任何成膜樹脂。此類樹脂可與自身反應,亦即,經歷自交聯反應,或可與交聯劑反應以形成膜。此類反應可在環境溫度或高溫下發生。「交聯劑」及其類似術語固化劑及硬化劑可在本文中互換使用。
可在成膜組分中使用任何適合之樹脂或樹脂組合,包括(但不限於)環氧樹脂、丙烯酸樹脂、聚矽氧烷樹脂、聚胺酯樹脂、聚脲樹脂、聚乙烯樹脂、酚系樹脂、脲醛樹脂、聚醯亞胺樹脂、三聚氰胺樹脂、聚酯樹脂及氰酸酯樹脂。在此等樹脂中,環氧樹脂、丙烯酸樹脂及/或聚胺酯樹脂為尤其合適的。
根據本發明使用之成膜樹脂含有一或多個彼此反應或與交聯劑上之官能基反應的官能基。適合官能基之實例包括例如酮、醯肼、碳化二亞胺、唑啉、環氧基、胺、乙烯基、醯胺、胺基甲酸酯、脲、硫醇、羧酸、(甲基)丙烯醯基、異氰酸酯、烷氧基矽烷基、酸酐、羥基及烷氧基、官能基及其組合。
能夠彼此反應之適合官能基包括例如N-羥甲基醯胺基;具有矽鍵結之可水解或可縮合基團,例如氯、羥基、烷氧基、乙醯氧基及/或酮肟基團的矽烷基;例如能夠進行氧化乾燥之烯系不飽和脂肪酸基團;甲亞胺基;氮雜環丁烷基;及能夠進行熱可逆Diels-Alder反應之基團,例如呋喃/順丁烯二醯亞胺。若樹脂含有能夠彼此反應的官能基,則視為自交聯且提供本發明膨脹型組合物不必存在固化劑。
樹脂亦可含有能夠彼此反應(自交聯)之官能基及可與固化劑之官能基反應之官能基的組合。在此類情況下,可存在固化劑;在固化時,將出現兩種交聯機制-交聯劑上之官能基與樹脂之間的反應及樹脂自身之自交聯反應。
適用於本發明之環氧樹脂包含至少一種聚環氧化物。聚環氧化物通常具有至少兩個1,2-環氧基。聚環氧化物之環氧當量可在80至6000,諸如100至700範圍內。環氧化合物可為飽和或不飽和、環狀、脂族、脂環族、芳族或雜環。其可包含取代基,諸如鹵素、羥基及醚基。
適合的聚環氧化物之實例為具有一個或通常兩個1,2-環氧當量者;亦即,平均每分子具有兩個環氧基之聚環氧化物。最常用的聚環氧化物例如為諸如2,2-雙(4-羥苯基)丙烷(雙酚A)、間苯二酚、對苯二酚、苯二甲醇、間苯三酚、雙酚F及兒茶酚之多酚之聚縮水甘油醚;或諸如脂環族多元醇,諸如1,2-環己烷二醇、1,4-環己烷二醇、2,2-雙(4-羥基環己基)丙烷、1,1-雙(4-羥基環己基)乙烷、2-甲基-1,1-雙(4-羥基環己基)丙烷、2,2-雙(4-羥基-3-三級丁基環己基)丙烷、1,3-雙(羥基甲基)環己烷及1,2-雙(羥基甲基)環己烷之多元醇之聚縮水甘油醚。脂族多元醇之實例尤其包含三羥甲基戊烷二醇、乙二醇、二乙二醇、三乙二醇、1,2-丙二醇、1,4-丁二醇、1,5-戊二醇、1,2,6-己三醇、環己烷二甲醇、丙三醇、三羥甲基丙烷、氫化雙酚A、氫化雙酚F或聚醚二醇,例如聚(氧基四亞甲基)二醇、聚(氧基伸乙基)二醇、聚(氧基伸丙基)二醇及新戊烷二醇。
適合的環氧樹脂之另一群組包括多羧酸之聚縮水甘油醚,其藉由使環氧化合物(諸如表氯醇)與脂族或芳族多羧酸(諸如乙二酸、丁二酸、戊二酸、對苯二甲酸、2, 6-萘二甲酸或二聚亞麻油酸)反應而形成。此類樹脂可購自Hexion Inc.其EPIKOTE及EPON線。
可根據本發明使用之其他合適的環氧樹脂包含環氧化烯烴不飽和脂環族材料,諸如環氧脂環族醚及酯、含有氧基伸烷基之環氧樹脂、環氧酚醛清漆樹脂,其係藉由使表鹵醇與醛及單羥基或多羥基苯酚(諸如環氧苯酚酚醛清漆樹脂或環氧甲酚酚醛清漆樹脂)之縮合產物反應來製備。
此外,根據本發明使用可撓性聚環氧化物樹脂作為本發明之膨脹型組合物之多環氧官能化合物可為有利的。此等樹脂一般基本上為線性材料,但容許少量分支。適合材料之實例為環氧化大豆油、基於二聚體酸之材料,諸如EMPOL 1010樹脂,其可購自BASF SE,Ludwigshafen,Germany,及橡膠改質之聚環氧化物樹脂,諸如由雙酚A之聚縮水甘油醚及酸官能性聚丁二烯製備之產物。
根據本發明使用之可撓性聚環氧化物之其他適合實例包括由可撓性酸官能性聚酯及聚環氧化物製備之環氧官能性加合物。酸官能性聚酯之酸值可為至少10 mg KOH/g,諸如140至350 mg KOH/或180至260 mg KOH/g,如藉由ASTM 974-87所測定。
線性聚酯可比用於本文之分支鏈聚酯更適合。酸官能性聚酯可藉由有機多羧酸或其酸酐與有機多元醇之聚酯化製備。多羧酸及多元醇可為脂族或芳族二元酸及二醇。
可用於製備聚酯之二醇包括伸烷基二醇,諸如乙二醇、二乙二醇、新戊二醇,及其他二醇,諸如氫化雙酚A、環己烷二醇、環己烷二甲醇、己內酯二醇(例如ε-己內酯與乙二醇之反應產物),羥基-烷基化雙酚,聚醚二醇,例如聚(氧基四亞甲基)二醇、聚(氧基伸乙基)二醇、聚(氧基伸丙基)二醇及其類似物。亦可使用較高官能度之多元醇,但二醇可為較適合的。實例包括三羥甲基丙烷、三羥甲基乙烷、季戊四醇、丙三醇、異山梨醇、四甲基環丁烷二醇及其類似物,以及較高分子量多元醇,諸如藉由使較低分子量多元醇進行氧基烷基化反應產生之多元醇。
聚酯之酸組分可包含每分子具有2至36個碳原子之單體二羧酸或酸酐。適合之酸包括例如鄰苯二甲酸、間苯二甲酸、對苯二甲酸、四氫鄰苯二甲酸、六氫鄰苯二甲酸、己二酸、壬二酸、癸二酸、順丁烯二酸、戊二酸、氯橋酸、四氯鄰苯二甲酸、四溴鄰苯二甲酸、癸二酸、十二烷二酸、松香酸、二酚酸、五倍子酸及不同類型之其他二羧酸,例如不飽和C18
脂肪酸之Diels-Alder加合物。
聚酯可包括少量一元酸,諸如苯甲酸、硬脂酸、乙酸、羥硬脂酸及油酸。此外,可使用高級多羧酸,諸如偏苯三甲酸。當酸在上文提及時,應理解,形成酸酐之彼等酸的酸酐可用於替代酸。此外,可使用酸之低級烷基酯,諸如戊二酸二甲酯及對苯二甲酸二甲酯。
根據本發明,用於製備環氧官能加合物之聚酯可由多羧酸組分及多元醇組分製備,該多羧酸組分包含多羧酸或具有7至16個碳原子之酸的混合物,該多元醇組分包含二乙二醇之一部分。
可用於製備可撓性酸官能性聚酯及聚環氧化物之環氧官能性加合物之聚環氧化物可選自如上文針對根據本發明之聚環氧化物官能性組分所定義之彼等。
其他適合的聚環氧官能化合物為環氧官能丙烯酸樹脂。此類樹脂可藉由(甲基)丙烯酸單體視情況與乙烯基單體或包含至少一個碳-碳雙鍵之其他單體組合的自由基加成聚合來製備,其中單體組合物包含至少一種具有至少一個碳-碳雙鍵之環氧官能化合物。
適合之環氧官能性烯系不飽和單體包括例如(甲基)丙烯酸縮水甘油酯、烯丙基縮水甘油醚、乙烯基縮水甘油醚、乙烯基環氧環己烷、氧化檸檬烯、丙烯酸2-乙基縮水甘油酯、甲基丙烯酸2-乙基縮水甘油酯、丙烯酸2-(正丙基)縮水甘油酯、甲基丙烯酸2-(正丙基)縮水甘油酯、丙烯酸2-(正丁基)縮水甘油酯、甲基丙烯酸2-(正丁基)縮水甘油酯、甲基丙烯酸縮水甘油基甲酯、丙烯酸縮水甘油酯、丙烯酸(3',4'-環氧基庚基)-2-乙酯、甲基丙烯酸(3',4'-環氧基庚基)-2-乙酯、丙烯酸(6',7'-環氧基庚基)酯、甲基丙烯酸(6',7'-環氧基庚基)酯、烯丙基-3,4-環氧基庚基醚、6,7-環氧基庚基烯丙基醚、乙烯基-3,4-環氧基庚基醚、3,4-環氧基庚基乙烯基醚、6,7-環氧基庚基乙烯基醚、鄰乙烯基苯甲基縮水甘油基醚、間乙烯基苯甲基縮水甘油基醚、對乙烯基苯甲基縮水甘油基醚、3-乙烯基環氧環己烷、甲基丙烯酸α-甲基縮水甘油酯、(甲基)丙烯酸3,4-環氧環己基甲酯及其組合。
適用於製備環氧官能性丙烯酸樹脂之額外單體包括例如烯系不飽和腈化合物;乙烯基芳族單體;烯系不飽和酸之烷基酯;烯系不飽和酸之羥烷基酯;烯系不飽和酸之醯胺;烯系不飽和酸;烯系不飽和磺酸單體及/或烯系不飽和含磷之酸單體;羧酸乙烯酯;共軛二烯;具有至少兩個烯系不飽和基團之單體;及其組合。
可用於製備環氧官能性丙烯酸樹脂之烯系不飽和腈單體的實例包括以線性或分支鏈排列含有2至4個碳原子的可聚合不飽和脂族腈單體,其可經乙醯基或額外腈基取代。此類腈單體包括丙烯腈、甲基丙烯腈、α-氰基乙基丙烯腈、反丁烯二腈及其組合,其中丙烯腈尤其適用。
代表性適合的乙烯基芳族單體包括例如苯乙烯、α-甲基苯乙烯、對甲基苯乙烯、三級丁基苯乙烯及乙烯基甲苯。
可用於製備環氧官能性丙烯酸樹脂之(甲基)丙烯酸之酯包括丙烯酸或(甲基)丙烯酸之正烷基酯、異烷基酯或三級烷基酯,其中烷基具有1至20個碳原子;甲基丙烯酸與新酸之縮水甘油酯之反應產物,諸如柯赫酸、新癸酸或特戊酸及(甲基)丙烯酸羥烷酯及(甲基)丙烯酸烷氧基烷酯單體。
(甲基)丙烯酸之適合烷基酯可包括例如(甲基)丙烯酸C1
-C20
烷基酯,諸如(甲基)丙烯酸C1
-C10
烷基酯。此類丙烯酸酯單體之實例包括丙烯酸正丁酯、丙烯酸二級丁酯、丙烯酸甲酯、丙烯酸乙酯、丙烯酸己酯、丙烯酸三級丁酯、丙烯酸2-乙基-己酯、丙烯酸異辛酯、丙烯酸4-甲基-2-戊酯、丙烯酸2-甲基丁酯、甲基丙烯酸甲酯、甲基丙烯酸丁酯、甲基丙烯酸正丁酯、甲基丙烯酸異丁酯、甲基丙烯酸乙酯、甲基丙烯酸異丙酯、甲基丙烯酸己酯、甲基丙烯酸環己酯及甲基丙烯酸十六烷基酯。(甲基)丙烯酸之酯,諸如(甲基)丙烯酸甲酯、(甲基)丙烯酸乙酯、(甲基)丙烯酸丙酯、(甲基)丙烯酸丁酯、(甲基)丙烯酸2-乙基己酯及其組合,尤其適合。
可用於製備環氧官能性丙烯酸樹脂的(甲基)丙烯酸羥烷酯單體包括例如基於環氧乙烷、環氧丙烷以及高級環氧烷或其混合物的丙烯酸羥烷酯及甲基丙烯酸羥烷酯單體。實例為丙烯酸羥乙酯、丙烯酸羥丙酯、甲基丙烯酸羥乙酯、甲基丙烯酸羥丙酯及丙烯酸羥丁酯。尤其適合的為(甲基)丙烯酸2-羥基乙酯。
可用於製備環氧官能性丙烯酸樹脂之烯系不飽和酸的醯胺包括例如丙烯醯胺、甲基丙烯醯胺及二丙酮丙烯醯胺。
可用於製備環氧官能性丙烯酸樹脂之乙烯酯單體包括乙酸乙烯酯、丙烯酸乙烯酯、丁酸乙烯酯、苯甲酸乙烯酯、己酸乙烯基-2-乙酯、硬脂酸乙烯酯及柯赫酸之乙烯酯。
適用於製備環氧官能性丙烯酸樹脂之烯系不飽和羧酸單體包括例如單羧酸及二羧酸單體及二羧酸之單酯。特別適合的為含有3至5個碳原子之烯系不飽和脂族單羧酸或二羧酸或酸酐。單羧酸單體之實例包括丙烯酸、甲基丙烯酸、巴豆酸(crotonic acid),且二羧酸單體之實例包括反丁烯二酸、衣康酸(itaconic acid)、順丁烯二酸及順丁烯二酸酐。其他適合之烯系不飽和酸的實例包括乙烯基乙酸、乙烯基乳酸、乙烯基磺酸、2-甲基-2-丙烯-1-磺酸、苯乙烯磺酸、丙烯醯胺基甲基丙烷磺酸及其鹽。適合烯系不飽和羧酸單體包括(甲基)丙烯酸、巴豆酸、伊康酸、順丁烯二酸、反丁烯二酸及其組合。
適用於製備環氧官能性丙烯酸樹脂的共軛二烯單體包括諸如以下之共軛二烯單體:1,3-丁二烯、異戊二烯、2,3-二甲基-1,3-丁二烯、2,3-二甲基-1,3-丁二烯、2-氯-1,3-丁二烯、1,3-戊二烯、1,3-己二烯、2,4-己二烯、1,3-辛二烯、2-甲基-1,3-戊二烯、2,3-二甲基-1,3-戊二烯、3,4-二甲基-1,3-己二烯、2,3-二乙基-1,3-丁二烯、4,5-二乙基-1,3-辛二烯、3-丁基-1,3-辛二烯、3,7-二甲基-1,3,6-辛三烯、2-甲基-6-亞甲基-1,7-辛二烯、7-甲基-3-亞甲基-1,6-辛二烯、1,3,7-辛三烯、2-乙基-1,3-丁二烯、2-戊基-1,3-丁二烯、3,7-二甲基-1,3,7-辛三烯、3,7-二甲基-1,3,6-辛三烯、3,7,11-三甲基-1,3,6,10-十二烷四烯、7,11-二甲基-3-亞甲基-1,6,10-十二烷三烯、2,6-二甲基-2,4,6-辛三烯、2-苯基-1,3-丁二烯及2-甲基-3-異丙基-1,3-丁二烯及1,3-環己二烯及其組合。
亦可在成膜組分(諸如上文所揭示之彼等組分中之任一者)中使用兩種或多於兩種(諸如三種或多於三種或四種或多於四種)不同聚環氧基官能化合物之組合。
根據本發明使用之適合的聚環氧官能化合物可包括例如雙酚A之二縮水甘油醚、雙酚F之二縮水甘油醚、間苯二酚二縮水甘油醚、環氧苯酚酚醛清漆樹脂、環氧甲酚酚醛清漆樹脂、環氧官能(聚)矽氧烷、環氧官能聚硫化物、酸化官能聚酯及聚環氧化物之環氧官能加合物,例如上文所述之彼等者。用於本發明之丙烯酸樹脂可包括例如丙烯酸或甲基丙烯酸之一或多種烷基酯視情況連同一或多種其他可聚合烯系不飽和單體之共聚物。適用的丙烯酸或甲基丙烯酸之烷基酯包括例如在烷基中含有1至30個且諸如4至18個碳原子之脂族烷基酯。非限制性實例包括例如甲基丙烯酸甲酯、甲基丙烯酸乙酯、甲基丙烯酸丁酯、丙烯酸乙酯、丙烯酸丁酯及丙烯酸2-乙基己酯。適合的其他可共聚烯系不飽和單體包括例如乙烯基芳族化合物,諸如苯乙烯及乙烯基甲苯;腈,諸如丙烯腈及4-甲基丙烯腈;鹵化乙烯及鹵化亞乙烯,諸如氯乙烯及偏二氟乙烯;及乙烯酯,諸如乙酸乙烯酯。
丙烯酸共聚物可包括羥基官能基,其通常藉由在用於產生共聚物之反應物中包括一或多種羥基官能性單體而併入至聚合物中。適用的羥基官能性單體包括典型地在羥烷基中具有2至4個碳原子之丙烯酸羥烷酯及甲基丙烯酸羥烷酯,諸如丙烯酸羥乙酯、丙烯酸羥丙酯、丙烯酸4-羥丁酯;己內酯及丙烯酸羥烷酯之羥基官能加合物;及對應甲基丙烯酸酯;以及下文所描述之β-羥基酯官能性單體。丙烯酸聚合物亦可用N-(烷氧基甲基)丙烯醯胺及N-(烷氧基甲基)甲基丙烯醯胺製備。
β-羥基酯官能性單體可由具有5至20個碳原子之烯系不飽和環氧基官能性單體及羧酸或由不可與烯系不飽和酸官能性單體聚合之含有至少5個碳原子之烯系不飽和酸官能性單體及環氧化合物製備。
用於本發明中之成膜樹脂之聚合物亦可為聚胺酯。在可使用之聚胺酯中為藉由使聚酯多元醇或丙烯酸多元醇(諸如上文所提及之彼等)與聚異氰酸酯反應以使得OH/NCO當量比大於1:1來製備之聚合性多元醇,以使得游離羥基存在於產物中。
根據本發明,成膜組分可包括環氧樹脂及丙烯酸樹脂或環氧樹脂及聚胺酯樹脂之組合,例如揭示於US 5,108,832或US 5,070,119中。
若成膜組分包含環氧樹脂及多元胺及/或聚硫醇官能化合物作為固化劑,如下文將論述,則成膜組分可進一步包含(i)(甲基)丙烯酸之β-羥基酯;(ii)不同於化合物(i)之(甲基)丙烯酸酯官能化合物;或其組合。
(甲基)丙烯酸之β-羥基酯可包含由聚環氧化物與(甲基)丙烯酸之反應產生的(甲基)丙烯酸酯基團之複數種β-羥基酯。聚環氧化物可以1: 0.1至1: 1.2,適當地1: 0.5至1: 1.2,更適當地1: 1至1: 1.05之環氧-羧酸當量比與(甲基)丙烯酸反應。(甲基)丙烯酸之尤其適合的β-羥基酯為EPIKOTE 828(雙酚A與表氯醇之反應產物)與可作為EBECRYL 3720購自Allnex之丙烯酸的反應產物。
可用於聚環氧化物與(甲基)丙烯酸之反應產物之聚環氧化物可為如上文所揭示之彼等聚環氧化物。
另外,或作為(甲基)丙烯酸(i)之β-羥基酯之替代方案,不同於化合物(i)之(甲基)丙烯酸酯官能化合物(ii)可存在於成膜組分中。藉此可調節本發明之膨脹型組合物之黏度。因此,咸信,視情況選用之組分(ii)在本發明之膨脹型組合物中充當反應性稀釋劑。本發明之膨脹型組合物之視情況選用之(甲基)丙烯酸酯官能組分(ii)可包括例如1,4-丁二醇、新戊二醇、乙二醇、1,2-丙二醇、1,3-丙二醇、2,2,4-三甲基-1,3-戊二醇、1,6-己二醇、1,4-環己烷二甲醇、對二甲苯二醇、1,4-環己烷二醇、三羥甲基乙烷、三羥甲基丙烷、新戊四醇、聚醚二醇(例如聚(氧基四亞甲基)二醇、聚(氧基伸乙基)二醇、聚(氧基伸丙基)二醇及其組合)之聚(甲基)丙烯酸酯。
如上文所指出,成膜組分亦可包含交聯劑。可根據本發明使用任何適合交聯劑,且熟習此項技術者將選擇其與成膜樹脂之官能基反應。適合交聯劑包括例如多元胺,例如聚醚胺、聚醯胺、聚環氧化物、胺基塑膠樹脂、酚系樹脂、聚異氰酸酯、聚硫醇及多元醇等。
固化劑亦可為潛伏或封端固化劑,其中可與成膜樹脂之官能基反應的實際官能基在諸如高溫之固化條件下在解封反應中產生或恢復。該類型之適合固化劑為例如封端聚異氰酸酯。因此,如本文所使用之術語聚異氰酸酯涵蓋封端及游離聚異氰酸酯。潛伏或封端固化劑尤其適合於提供單組分組合物以在施加及固化之前確保足夠的儲存穩定性及適用期。
多元胺固化劑可包括例如脂族多元胺、芳族多元胺、多元胺醯胺、聚醚胺(例如購自Huntsman Cooperation, The Woodlands, Texas之彼等)、聚矽氧烷胺、聚硫胺或其組合。實例包括二伸乙基三胺、3,3-胺基-雙丙胺、三伸乙基四胺、四伸乙基五胺、間二甲苯二胺、異佛爾酮二胺、1,3-雙(胺基乙基)環己烷、雙(4-胺基環己基)甲烷、N-胺基乙基哌、4,4'-二胺基二苯基甲烷、4,4'-二胺基-3,3'-二乙基二苯基甲烷及二胺基二苯碸且可使用多元胺與脂族脂肪酸之反應產物,諸如由BASF以商標VERSAMID出售之一系列材料,後者為特別適合的。
此外,亦可使用任何以上多元胺之加合物。多元胺之加合物係藉由多元胺與適合之反應性化合物(諸如環氧樹脂)反應而形成。此反應將減少固化劑中游離胺之含量,使得其在低溫及/或高濕環境下更有用。
作為固化劑,亦可使用各種聚醚胺,諸如購自Huntsman Corp的各種Jeffamines,包括但不限於Jeffamine D-230、Jeffamine D-400、Jeffamine 600、Jeffamine 1000、Jeffamine 2005及Jeffamine 2070等。
作為固化劑,亦可使用各種聚醯胺。一般而言,聚醯胺含有二聚體脂肪酸及聚伸乙基胺之反應產物及少量單體脂肪酸。二聚體脂肪酸係藉由單體脂肪酸之低聚合製備。聚伸乙基胺可為任何高級聚伸乙基胺,諸如二伸乙基三胺、三伸乙基四胺、四伸乙基五胺等,其中最常用的係二伸乙基三胺。當聚醯胺用作固化劑時,其可賦予塗料一或多個所需特性,諸如耐腐蝕性、耐水性及/或良好可撓性。
適用作固化劑之聚硫醇化合物可包括聚硫化物硫醇、聚醚硫醇、聚酯硫醇、基於新戊四醇之硫醇;或其組合。尤其適合之聚硫醇化合物為可購自Akzo Nobel Functional Chemicals GmbH&CoKG ,Greiz,Germany之Thioplast G4。
如上文所提及,若成膜樹脂包含環氧樹脂,則可將多元胺、聚硫醇化合物或其組合用作交聯劑。
在本發明之塗料組合物中,若使用環氧樹脂,則成膜樹脂中之組合官能基(諸如環氧基)與固化劑中之官能基之當量比可為2: 1至1: 2,諸如1.05: 1.0至1: 2,或1: 1.4至1: 2。
塗料組合物可包含任何適合量之成膜組分。舉例而言,塗料組合物可含有20重量%或更多的成膜組分,諸如30重量%或更多或40重量%或更多。塗料組合物可例如含有60重量%或更少之成膜組分,諸如50重量%或更少、或40重量%或更少。塗料組合物可例如包含量在上述值中之任一者之間的範圍內的成膜組分,諸如20 wt%至60 wt%、20 wt%至40 wt%或30 wt%至50 wt%。除非另外規定,否則如本文所報告之wt%係以組合物之總固體重量計。
本發明之塗料組合物進一步包含磷酸源。如本文所用之磷酸源意謂包含磷酸或其縮合或脫水產物(包括氧化物)或鹽、酯、醯胺或前述任一者之其他衍生物的任何含磷材料。磷酸源可包含多種材料,諸如磷酸、磷酸一銨及磷酸二銨、磷酸三苯酯、磷酸參-(2-氯乙基)酯、磷酸三(2-氯異丙基)酯、含磷之醯胺,諸如磷醯胺及焦磷酸三聚氰胺。適當地,磷源為由式(NH4
)n+2
Pn
O3n+1
表示之多磷酸銨,其中n為至少2之整數,適當地n為至少50之整數。本發明之膨脹型組合物可含有量為20 wt%或更大,諸如25 wt%或更大,或30 wt%或更大,35 wt%或更大,或40 wt%或更大的磷酸源。塗料組合物可包含量為55 wt%或更少,諸如50 wt%或更少,或45 wt%或更少,或40 wt%或更少,或35 wt%或更少的磷酸源。塗料組合物可包含量在任何上述值之間的範圍內的磷酸源,諸如20至55 wt%、例如25至40 wt%或40至55 wt%。本文所報告之wt%各自係以組合物之總固體重量計。咸信磷在膨脹型組合物中充當炭促進劑。
本發明之塗料組合物進一步包含硼酸源、鋁源及/或二氧化矽源中之至少一者。本發明之塗料組合物可因此例如含有硼酸源、鋁源或二氧化矽源中之一者。舉例而言,塗料組合物可包含硼酸源作為組分c。可替代地,塗料組合物可包含鋁源或二氧化矽源作為組分c。另一方面,塗料組合物亦可包含硼酸源、鋁源及/或二氧化矽源中之兩者或多於兩者之組合。舉例而言,根據本發明之塗料組合物可包含鋁源及二氧化矽源。如本文所用之硼酸源意謂任何含有硼酸或其縮合或脫水產物(包括氧化物)或前述中之任一者之鹽或酯的含硼材料。適合的硼酸源包括例如五硼酸銨、硼酸、金屬硼酸鹽(諸如硼酸鋅)、氧化硼、硼酸鹽(諸如硼酸鈉、硼酸鉀及硼酸銨)、硼酸酯(諸如硼酸丁酯或硼酸苯酯)及其組合。如本文所用,鋁源意謂任何含鋁材料。典型地,鋁源可為鋁化合物,詳言之,無機鋁化合物。適合之鋁源包括例如氫氧化鋁、氧化鋁(礬土)、氯化鋁、鋁鹽及其組合。舉例而言,鋁源可包含氫氧化鋁及/或氧化鋁。如本文所用之二氧化矽源意謂任何含有聚矽氧烷、矽烷、矽酸、其縮合或脫水產物(包括氧化物)或前述任一者之鹽或酯的含矽材料。適合之二氧化矽源包括例如煙霧狀二氧化矽或石英,諸如粒度低於150 μm之彼等二氧化矽,或含有二氧化矽,諸如膨潤土或高嶺土之物質。
若使用,則本發明之膨脹型組合物可含有量為5 wt%或更大,諸如6 wt%或更大,諸如7 wt%或更大,諸如8 wt%或更大,諸如9 wt%或更大,諸如10 wt%或更大之硼酸源。塗料組合物可包含量為20 wt%或更少,諸如19 wt%或更少,或18 wt%或更少,或15 wt%或更少之硼酸源。塗料組合物可包含量在任何上述值之間的範圍內的硼酸源,諸如5 wt%至20 wt%、或6 wt%至15 wt%、或9 wt%至15 wt%。若使用,則本發明之膨脹型組合物可含有量為0.1 wt%或更大,諸如0.2 wt%或更大、或0.3 wt%或更大、或0.5 wt%或更大、或1 wt%或更大、或3 wt%或更大、或5 wt%或更大的鋁源。塗料組合物可包含量為10 wt%或更少,諸如9 wt%或更少,或8 wt%或更少,或5 wt%或更少,或3 wt%或更少,或1 wt%或更少,或0.7 wt%或更少的鋁源。組合物可包含量在任何上述值之間的範圍內的鋁源,諸如0.1至10 wt%、諸如0.2至8 wt%或0.3 wt%至1 wt%。若使用,則本發明之膨脹組合物可含有量為0.1 wt%或更大、諸如0.2 wt%或更大、或0.3 wt%或更大、或0.4 wt%或更大、或0.5 wt%或更大的二氧化矽源。塗料組合物可包含量為5 wt%或更少,諸如3 wt%或更少,或2 wt%或更少,或1 wt%或更少,或0.8 wt%或更少的二氧化矽源。組合物可包含量在任何上述值之間的範圍內的二氧化矽源,諸如0.1至5 wt%,諸如0.4至1 wt%。上文所報告之wt%各自以組合物之總固體重量計。
本發明之組合物進一步包含二氧化鈦(TiO2
)。根據本發明之組合物可包含量為5 wt%或更大,諸如6 wt%或更大、或7 wt%或更大、或8 wt%或更大、或9 wt%或更大、或10 wt%或更大的TiO2
。塗料組合物可包含量為20 wt%或更少,諸如19 wt%或更少,或18 wt%或更少,或17 wt%或更少,或15 wt%或更少,或13 wt%或更少,或10 wt%或更少的TiO2
。組合物可包含量在任何上述值之間的範圍內之TiO2
,諸如5至20 wt%、諸如5至10 wt%、或10 wt%至18 wt%。上文所報告之wt%各自以組合物之總固體重量計。
如上文所指出,本發明人已發現,在上文給定之範圍內,與TiO2
及磷酸源結合使用硼酸源、鋁源及/或二氧化矽源產生具有所需炭形成以及對基板之所需黏附力的膨脹型塗料。因此,本發明組合物提供優於類似組合物之優點,在該等類似組合物中所述元素中之一或多者缺失及/或在所述範圍外使用。
本發明塗料組合物進一步包含氣體源。「氣體源」係指當熱分解時提供膨脹氣體之化合物。膨脹氣體用以引起膨脹型組合物在暴露於高溫或火焰時發泡及膨脹。由於此膨脹,形成之炭為用以隔絕及保護底層基板之厚的多單元材料。任何適合之膨脹氣體源可用於本發明之膨脹組合物中,諸如含氮材料。適合的含氮材料之實例包括三聚氰胺、磷酸之鹽、胍、羥甲基化三聚氰胺、六甲氧基甲基三聚氰胺、脲、二甲脲、焦磷酸三聚氰胺、二氰二胺、磷酸甲脒脲及甘胺酸。亦可使用其他習知膨脹氣體源,諸如釋放二氧化碳之彼等材料。實例為鹼土金屬,諸如碳酸鈣或碳酸鎂。亦可使用釋放水蒸氣之化合物,因為其在加熱時分解,例如氫氧化鈣、二氫氧化鎂或三氫氧化鋁,可膨脹石墨亦可。此類化合物之其他實例亦為硼酸源,諸如硼酸及硼酸衍生物,諸如硼酸酯及金屬硼酸鹽。氣體源(諸如三聚氰胺)可以1 wt%或更大(諸如2 wt%或更大,或3 wt%或更大)的量用於本發明之膨脹型組合物中。根據本發明之組合物可包含量為例如10 wt%或更少、或8 wt%或更少、或7 wt%或更少、或5 wt%或更少的氣體源。組合物可包含量在任何上述值之間的範圍內的氣體源,諸如1至10 wt%,諸如3至7 wt%。所報告之wt%各自以組合物之總固體重量計。
本發明之塗料可含有一或多種適用於膨脹型塗料之額外添加劑。此類添加劑之實例包括鋅源、酸源、金屬氧化物(例如,預水解之正矽酸四乙酯、異丙醇鈦)、碳源、無機填料、玻璃纖維及/或礦物纖維(例如,來自PPG,Coatforce之CHOPVANTAGE或來自Lapinus之Roxul纖維)、流變添加劑、有機溶劑、顏料、泡沫穩定劑及其組合。
視情況存在之鋅源可包含多種材料。咸信鋅材料可有助於在炭中形成小孔結構。炭之小孔可提供基板之較佳隔絕,且能夠較好地保持炭完整性且黏附至基板。因此,使炭破裂及炭與基板之脫離降至最少,且向底層基板給予較大保護措施。為鋅源之適合材料之實例包括氧化鋅;鋅鹽,諸如硼酸鋅及磷酸鋅、碳酸鋅;亦可使用鋅金屬。
酸源可選自磷酸銨、多磷酸銨、二磷酸二銨、五硼酸二銨、磷酸產生材料、硼酸、金屬或有機硼酸鹽及其組合。
應理解,本發明組合物之許多組分可在組合物中提供一種以上功能。舉例而言,磷、鋅、硼及膨脹氣體可各自由單獨源材料提供,或替代地,單一材料可為此等組分中之超過一者的源。舉例而言,焦磷酸三聚氰胺可提供磷及膨脹氣體兩者之源,硼酸鋅可提供鋅源及硼酸源;磷酸鋅可提供鋅源及磷酸源,及其類似物。
視情況選用之增強填料可選自大量習知利用之材料,包括纖維加強物及片狀加強物,其可比其他填料更適合。纖維加強物之實例包括玻璃纖維、陶瓷纖維(例如氧化鋁/氧化矽)、石墨纖維、礦物纖維及玄武岩纖維。片狀加強物包括錘式研磨玻璃薄片、雲母及矽灰石。其他適合之填料包括金屬氧化物、黏土、滑石、二氧化矽、矽藻土、LAPINUS纖維及各種顏料。認為增強填料幫助在炭形成之前及期間控制防火組合物膨脹,使得所得炭較硬且均一。當存在時,以膨脹型組合物之總固體重量計,增強填料(諸如玻璃纖維及/或礦物纖維)通常以5.0 wt%或更低,諸如4 wt%或更低,諸如3 wt%或更低的量存在於組合物中。根據本發明之組合物可例如以0.1 wt%或更大,諸如0.2 wt%或更大、0.5 wt%或更大或1 wt%或更大之量包含增強填料。組合物可包含量在上述任何值之間的範圍內的增強填料,諸如0.1 wt%至5.0 wt%或1 wt%至4 wt%。所報告之wt%各自以組合物之總固體重量計。
本發明之膨脹型組合物亦可含有各種習知添加劑,諸如流變添加劑、有機溶劑、泡沫穩定劑、顏料、火焰擴散控制劑及其類似物。此等成分為視情況選用的且可以不同量添加。典型地,若使用額外添加劑,則其以1 wt%或更多,諸如2 wt%或更多,或5 wt%或更多,或10 wt%或更多之總量存在。若使用,則額外添加劑可以例如20 wt%或更少,諸如15 wt%或更少,或12 wt%或更少之量存在於根據本發明之組合物中。組合物可包含量在任何上述值之間的範圍內的視情況選用之額外添加劑,諸如1至20 wt%,諸如2至20 wt%或5-15 wt%。所報告之wt%各自以組合物之總固體重量計。
膨脹型組合物可為單組分(「1K」),或多組分組合物,諸如雙組分(「2K」)或更多組分。1K組合物將理解為係指其中全部塗料組分在製造之後、儲存期間等保存於相同容器中之組合物。1K組合物可施加於基板且藉由任何習知手段(諸如藉由加熱、強制空氣及其類似手段)固化。本發明組合物亦可為多組分的,其將理解為此類組合物,其中將各種組分分開保存直至施加前。本發明組合物可為熱塑性或熱固性的。舉例而言,本發明組合物可封裝為2K系統,其中成膜樹脂在第一封裝(A)及與其對應之固化劑在第二封裝(B)中,藉以用於塗料組合物之全部其他組分以任何組合用於封裝(A)或封裝(B)中或兩者中,或一些或全部可用於一或多種其他封裝(C)中。個別封裝在膨脹型組合物使用之前混合。
本發明之可固化膨脹型組合物可呈厚材料(諸如膠泥)形式。組合物尤其適合無溶劑且噴塗。必要時,薄化可藉由多種習知溶劑實現,諸如二甲苯、二氯甲烷或1,1,1-三氯乙烷。
可塗覆本發明之可固化膨脹型塗料組合物以提供所需的各種乾膜厚度。適合之乾膜厚度可在10至20,000微米,諸如50至5000微米,諸如100至2000微米範圍內。所要乾膜厚度(「DFT」)可取決於應用而變化。為了用於建築結構組件,範圍介於200微米至20,000微米(諸如300微米至1000微米或3000微米至15000微米)之DFT可為合適的。對用於鋰電池之用途,範圍介於200至5000微米(諸如200至1000或1000至5000)之DFT可為合適的。
或者,本發明之膨脹型組合物可形成為自支撐膜或薄片。可隨後固化自支撐膜或薄片以形成交聯膨脹型自支撐膜或薄片。一般而言,本發明之可固化膨脹型組合物可藉由熟習此項技術者熟知之任何技術,例如鑄塑法、藉由用塗料浸漬網及其類似方法形成為膜或薄片。在將交聯膨脹型自支撐膜或薄片施加至基板之前,膜或薄片可經固化以形成交聯膨脹型自支撐膜或薄片。亦在本發明之範圍內的為在形成步驟之後,將未固化膜或薄片施加至基板且隨後固化以獲得根據本發明之交聯膨脹層。膜或薄片可經由黏著劑施加至基板。
本發明組合物及自支撐薄片或膜可施加至此項技術中已知之任何基板,例如汽車基板、船舶基板、工業基板、重型設備、封裝基板、板材、地板及傢俱、服裝、包括外殼及電路板且包括消費型電子裝置之電子裝置(諸如電腦、筆記型電腦、智慧型電話、平板電腦、電視、遊戲設備、電腦設備、電腦配件、MP3播放器及其類似物之外殼)、玻璃及透明物體、包括高爾夫球之體育設備及其類似者。此等基板可例如為金屬的或非金屬的。金屬基板包括錫、鋼、鍍錫鋼、鉻鈍化鋼、鍍鋅鋼、鋁及鋁箔。如本文所用之金屬薄片係指平滑金屬薄片及捲曲金屬薄片,其經捲曲、未經捲曲以用於塗佈且隨後再捲曲以用於運輸至製造商。非金屬基板包括聚合、塑膠、聚酯、聚烯烴、聚醯胺、纖維素、聚苯乙烯、聚丙烯酸、聚(萘二甲酸伸乙酯)、聚丙烯、聚乙烯、耐綸、EVOH、聚乳酸、其他「綠色」聚合基板、聚(對苯二甲酸伸乙酯) (「PET」)、聚碳酸酯、聚碳酸酯丙烯醯丁二烯苯乙烯(「PC/ABS」)、SMC、碳纖維、聚醯胺、木材、膠合板、木材複合物、粒子板、中等密度纖維板、水泥、石材、玻璃、紙、紙板、紡織品、皮革(合成與天然)及其類似物。基板可為結構之部分或車輛之部分。如本文中所使用之「結構」係指建築物、橋、運輸基礎設施、鑽油平台、油平台、水塔、電源線塔、支撐結構、風力渦輪機、牆壁、橋墩、碼頭、堤、壩、運輸容器、拖車及暴露於腐蝕性環境之任何金屬結構的任何部分。如本文中所使用之「車輛」在其最廣泛意義上係指所有類型之車輛,諸如但不限於汽車、卡車、公共汽車、牽引車、收穫器、重型設備、箱車、高爾夫球車、摩托車、自行車、軌道車、地鐵車、飛機、直升機、所有大小之船及其類似物。
基板可為已經以某種方式處理以便賦予視覺效應及/或色效應之基板。舉例而言,在塗覆塗料組合物之前,基板可經鹼清潔、脫氧、機械清潔、超音波清潔、溶劑刮擦、粗糙化、電漿清潔或蝕刻、暴露於化學氣相沈積、經助黏劑處理、鍍敷、陽極化、退火、包層或其任何組合。可在塗覆塗料組合物之前使用前述方法中之任一者處理基板,諸如藉由在塗覆塗料組合物之前將基板浸漬於清潔機及/或脫氧浴中。亦可在塗覆塗料組合物之前對基板進行鍍覆。如本文中所使用,「電鍍」係指在基板表面上方沈積金屬。基體亦可經3D印刷。
如上文所論述,基板可包含電池或電池組件。電池可為(例如)電動車電池,且電池組件可為電動車電池組件。「電池組件」可為電池中所發現之任何組件,諸如鋰離子電池。電池組件可包含電極、電池單元、電池殼、電池模組、電池組、電池盒、電池單元殼、電池組殼、電池蓋及托盤、熱管理系統、電池外殼、模組外殼、模組裝架、電池側板、電池單元罩殼、冷卻模組、冷卻管、冷卻片、冷卻板、母線、電池框架、電氣連接、金屬線、或銅或鋁導體或電纜。
因此,本發明進一步有關於至少部分用本發明之塗料組合物塗佈之物件。本發明之塗料組合物可施加至呈任何形式之物件,諸如塗料組合物或交聯膨脹型自支撐膜或薄片。當提及膜或薄片時,「施加至」及其任何變體意謂膜/薄片可諸如藉助於黏著層貼附至物件,或定位於物件內或置放於物件內,諸如鄰近於物件之固定或可移動部件。該物件可為結構。該物件可為車輛。該物件可為電池組件或電池,諸如鋰離子電池。舉例而言,本發明之塗料組合物或交聯自支撐膜或薄片可施加至電池,尤其鋰離子電池之任何結構元件以獲得根據本發明之電池。該電池可包含界定外殼之外壁元件及視情況選用之內壁元件,其中該交聯膨脹型塗料或交聯膨脹型自支撐膜或薄片至少部分地施加至該等外壁元件中之任一者的外側及/或內側及/或該等內壁元件中之任一者(若存在)的任何側面。外壁及/或內壁元件可包含例如複合物、鋼、鋁及/或聚碳酸酯。本發明塗料組合物可特別適合於在電池上使用,因為其形成具有相對較小膨脹之強炭,使其適合於電池模組與殼體之間的有限間隙空間。
電池,尤其鋰離子電池,可為包含複數個個別電池單元之電池組,其中本發明塗料或交聯膨脹型自支撐膜或薄片經定位以使個別電池單元中之至少一些在膨脹狀態及視情況炭化狀態下(諸如在兩個電池單元之間)彼此熱絕緣。另外,可固化膨脹型塗料組合物或交聯膨脹型自支撐膜或薄片可施加至如上文所論述之電池組的外殼壁及內部分隔壁或鄰近於該等外殼壁及內部分隔壁置放。
可能需要在電池內及/或周圍使用一或多種額外阻燃材料及/或緩解火災的構件。舉例而言,熱絕緣材料或高強度材料或其類似者可包裹電池單元或以其他方式定位於電池單元之間,或包裹電池外殼之周邊或內部。此類材料之實例包括玻璃纖維、礦物棉、二氧化矽/二氧化矽纖維、氧化鋁、Kevlar、Nomex、矽酸鈣或矽酸鈣纖維;此等材料可例如呈薄片或其他自支撐形式。亦可使用發泡體,諸如具有阻燃劑之聚胺酯/聚脲發泡體。亦可採用物理障壁,諸如插入於電池單元、雲母板、氣凝膠覆層及/或含礦物/玻璃/碳纖維之覆層之間的冷卻片。
為了為包含電池之物件及其使用者提供防火保護,亦在本發明之範圍內的為將可固化膨脹型塗料組合物或交聯膨脹型自支撐膜或薄片在電池與物件之間鄰近於電池施加至物件之一部分以使物件與電池隔絕。在此類情況下,可採用習知電池或根據本發明之電池。物件可為(例如)行動電話、平板電腦或膝上型電腦。
替代地,物件可為車輛,諸如混合車或電動車、公共汽車或卡車。在此類車輛中,電池(尤其鋰離子電池)歸因於其重量作為扁平電池組定位於車輛本體(例如,車體)之地板部分下方係常見的。在此類情況下,本發明之塗料或交聯膨脹型自支撐膜或薄片可在電池與車輛本體之間鄰近於電池施加至車輛的地板部分。藉此,在電池或電池起火之熱失控的事件下,車體,尤其是客艙係藉由本發明之塗層/膜保護,使得火焰將不會擴散至客艙中且客艙之加熱將會被限制較長時間段,使得乘客在此類事故的情況下將具有足夠的時間來安全地逃出該車輛。
本發明之組合物可藉由此項技術中之任何標準手段施加,諸如電塗、噴霧、靜電噴霧、浸漬滾塗、刷塗及其類似方式,包括機器人施加。
除非另外明確地規定,否則如本文所使用,諸如彼等表示值、範圍、量或百分比之數值的所有數值均可讀取為如同前面加上詞語「約」,即使該術語並未明確地出現。此外,本文所列舉之任何數值範圍意欲包括其中包含之所有子範圍。單數涵蓋複數,且反之亦然。舉例而言,儘管在本文中提及「成膜組分」、「成膜樹脂」、「磷酸源」、「硼酸源」、「二氧化矽源」、「鋁源」、「氣體源」及其類似者,但可使用此等中之每一者中之一或多者及任何其他組分。又,如本文中所使用,術語「聚合物」意欲指預聚物、寡聚物及均聚物與共聚物兩者;前綴「聚」係指兩種或兩種以上。當給出範圍時,彼等範圍之任何端點及/或彼等範圍內之數值可與本發明之範疇組合。「包括」、「諸如」、「例如」及其類似術語意謂「包括/諸如/例如但不限於」。除非另外明確指明,否則術語「丙烯酸」及「丙烯酸酯」可互換使用(除非互換使用將改變預期意義)且包括丙烯酸、酸酐及其衍生物、經低級烷基取代之丙烯酸(例如,經C1
-C2
取代之丙烯酸,諸如甲基丙烯酸、乙基丙烯酸等)及其C1
-C6
烷基酯及羥烷基酯。
鑒於前文,本發明因此尤其係關於(但不限於)以下態樣:
在第一態樣中,揭示一種塗料組合物,該塗料組合物包含:
a)成膜組分;
b)磷酸源;
c)硼酸源、鋁源及/或二氧化矽源中之至少一者;
d) TiO2
;及
e)氣體源;
其中該TiO2
以5至20 wt%之量存在,該磷酸源以20至55 wt%之量存在,且其中若組分c包含硼酸源,則其以5至20 wt%之量存在,若組分c包含鋁源,則其以0.1至10 wt%之量存在,且若組分c包含二氧化矽源,則其以0.1至5 wt%之量存在,其中wt%以該組合物之總固體重量計。
第二態樣係關於根據前述第一態樣之塗料組合物,其中TiO2
以按組合物之總固體重量計9至15 wt%之量存在。
第三態樣係關於如前述第一態樣或第二態樣中任一項之塗料組合物,其中該磷酸源以25至40 wt%之量存在。
第四態樣係關於如前述第一態樣或第二態樣中任一項之塗料組合物,其中該磷酸源以按組合物之總固體重量計40至55 wt%之量存在。
第五態樣係關於如前述第一態樣至第四態樣中任一項之塗料組合物,其中組分c包含硼酸源,其中該硼酸源較佳以按該組合物之總固體重量計9至15 wt%之量存在。
第六態樣係關於如前述第一態樣至第五態樣中任一項之塗料組合物,其中組分c包含鋁源,其中該鋁源較佳以按組合物之總固體重量計0.2至8 wt%之量存在。
第七態樣係關於如前述第一態樣至第六態樣中任一項之塗料組合物,其中組分c包含二氧化矽源,其中該二氧化矽源較佳以按該組合物之總固體重量計0.4至1 wt%之量存在。
第八態樣係關於如前述第一態樣至第七態樣中任一項之塗料組合物,其中該成膜組分以按組合物之總固體重量計20-60 wt%之量存在。
第九態樣係關於如前述第一態樣至第八態樣中任一項之塗料組合物,其中該氣體源以1-10 wt%之量存在,其中wt%係以該組合物之總固體重量計。
第十態樣係關於如前述第一態樣至第九態樣中任一項之塗料組合物,其中塗料組合物進一步包含按組合物之總固體重量計至多4 wt%之量的纖維,諸如玻璃纖維及/或礦物纖維。
第十一態樣係關於如前述第一態樣至第十態樣中任一項之塗料組合物,其中該塗料組合物進一步包含總量為2-20 wt%之一或多種添加劑,其中wt%係以該組合物之總固體重量計。
第十二態樣係關於如前述第一態樣至第十一態樣中任一項之塗料組合物,其中該成膜組分包含成膜樹脂及視情況選用之其對應之交聯劑,諸如環氧樹脂及胺交聯劑。
第十三態樣係關於如前述第一態樣至第十二態樣中任一項之塗料組合物,其中該磷酸源包含磷酸銨、磷酸三苯酯及/或磷酸參(2-氯異丙基)酯,較佳包含多磷酸銨。
第十四態樣係關於如前述第一態樣至第十三態樣中任一項之塗料組合物,其中該硼酸源(若使用)包含金屬硼酸鹽五硼酸銨及/或硼酸。
第十五態樣係關於如前述第一態樣至第十四態樣中任一項之塗料組合物,其中該鋁源(若使用)包含氫氧化鋁及/或氧化鋁。
第十六態樣係關於如前述第一態樣至第十五態樣中任一項之塗料組合物,其中該二氧化矽源(若使用)包含煙霧狀二氧化矽。
第十七態樣係關於如前述第一態樣至第十六態樣中任一項之塗料組合物,其中該氣體源包含三聚氰胺、脲及/或可膨脹石墨。
第十八態樣係關於一種自支撐膜或薄片,其由根據前述第一態樣至第十七態樣中任一項之塗料組合物形成。
此外,在第十九態樣中,揭示一種用於塗佈基板之方法,該方法包含向基板之至少一部分施用根據前述第一態樣至第十七態樣中任一項之塗料組合物或根據前述第十八態樣之膜或薄片。
第二十態樣係關於根據前述第十九態樣之方法,其中基板包含金屬,諸如鋁或鋼,或塑膠,諸如聚碳酸酯。
在第二十一態樣中,揭示根據如前述第十九態樣或第二十態樣中任一項之方法塗佈之基板。
此外,第二十二態樣係關於包含根據前述第二十一態樣之基板的物件。
第二十三態樣係關於如前述第二十二態樣之物件,其中該物件包含車輛或結構。
第二十四態樣係關於如前述第二十二態樣之物件,其中該物件包含鋰離子電池。
第二十五態樣係關於如前述第二十四態樣之物件,其中電池包含界定外殼之外壁元件及視情況選用之內壁元件,其中塗料組合物或膜或薄片至少部分施用至外壁元件中之任一者之外側及/或內側及/或施用至內壁元件中之任一者(若存在)之任何側面。
第二十六態樣係關於如前述第二十五態樣之物件,其中外壁及/或內壁元件中之任一者包含複合物、鋼、鋁及/或聚碳酸酯。
第二十七態樣係關於如前述第二十四態樣至第二十六態樣中任一項之物件,其中該電池係包含複數個個別電池單元之電池組,其中該塗料組合物或膜或薄片經定位以使個別電池單元中之至少兩者在膨脹狀態及視情況炭化狀態下彼此熱絕緣;且其中該電池視情況包含一或多種額外阻燃材料及/或緩解火災的構件。
在第二十八態樣中,揭示一種電池組件,其中該電池組件至少部分塗佈有如前述第一至第十七態樣中任一項之塗料組合物或根據前述第十八態樣之膜或薄片已施加至該電池組件。
第二十九態樣係關於如前述第二十八態樣之電池組件,其中電池組件包含電動車電池組件。
另一態樣係關於根據前述第二十八態樣或第二十九態樣中任一項的電池組件,其中,電池組件包含電池單元、電池殼、電池模組電池組、電池盒、電池單元殼、電池組殼、電池蓋及托盤、熱管理系統、電池外殼、模組外殼、模組裝架、電池側板、電池單元罩殼、冷卻模組、冷卻管、冷卻片、冷卻板、母線、電池框架、電氣連接、金屬線、銅或鋁導體或電纜,或其任何組合。
實例
以下實例意欲說明本發明且不應解釋為以任何方式限制本發明。
實例
使用下文展示之成分製備多種塗料調配物(調配物1至13)。各塗料調配物之主劑藉由在分散機下以高旋轉速度分散所有組分直至調配物中之粒子尺寸低於100微米來製備。各塗料調配物之硬化劑藉由在分散機下以高旋轉速度分散所有組分直至調配物中之粒子尺寸低於100微米來製備。分散速度及分散板尺寸分別為2000 rpm及80 mm,容器直徑為180 mm。緊接著在施加之前,主劑及硬化劑以下表中所展示之相對量混合。藉由混合器或刮勺混合主劑及硬化劑,直至混合物之顏色變得均勻且無團塊。將塗料調配物各自以無空氣噴霧施加來施加於150×75×1.2 mm鋁板上,且針對1200±50℃炬火持續10分鐘來測試由此形成之塗層,其中氣體壓力為2巴及燃燒器直徑為30 mm。監控鋁板之背面處的溫度。評估塗層之膨脹係數,其被定義為經膨脹塗層與原始塗層之厚度之間的比率,所形成之炭及其與基板之黏附力。結果概述於下表1中。調配物 1: (APP: 硼酸鹽 : TiO2
= 15.2 : 31.2: 0) - 比較實例 調配物 1- 主劑 ( 主劑 : 硬化劑 = 4:1)
1
Hexion2
Gabriel performance products3
Nippon electric glass4
Elementis Specialties5
Clariant AG6
R J Marshall Co調配物 1- 硬化劑 ( 主劑 : 硬化劑 = 4:1)
7
Huntsman8
Huntsman9
BASF10
Allnex調配物 2: (APP: 硼酸鹽 : TiO2
= 15.2 : 29.4: 2.7) - 比較實例 調配物 2- 主劑 ( 主劑 : 硬化劑 = 3:1)
11
The Chemours Company LLC調配物 2- 硬化劑 ( 主劑 : 硬化劑 = 3:1)
調配物 3: (APP: 硼酸鹽 : TiO2
= 15.2 : 27.5: 4.6) - 比較實例 調配物 3- 主劑 ( 主劑 : 硬化劑 = 3:1)
調配物 3- 硬化劑 ( 主劑 : 硬化劑 = 3:1)
調配物 4: (APP: 硼酸鹽 : TiO2
= 15.7: 18.5: 5.9) - 比較實例 調配物 4- 主劑 ( 主劑 : 硬化劑 = 7:3)
調配物 4- 硬化劑 ( 主劑 : 硬化劑 = 7:3)
調配物 5: (APP: 硼酸鹽 : TiO2
= 29.3 : 19.6: 5.9) 調配物 5- 主劑 ( 主劑 : 硬化劑 = 4:1)
調配物 5- 硬化劑 ( 主劑 : 硬化劑 = 4:1)
調配物 6: (APP: 硼酸鹽 : TiO2
= 35.3 : 10.3: 9.2) 調配物 6- 主劑 ( 主劑 : 硬化劑 = 4:1)
調配物 6- 硬化劑 ( 主劑 : 硬化劑 = 4:1)
調配物 7: (APP: 硼酸鹽 : TiO2
= 40.7: 14.5: 13.3) 調配物 7- 主劑 ( 主劑 : 硬化劑 = 2:1)
調配物 7- 硬化劑 ( 主劑 : 硬化劑 = 2:1)
調配物 8: (APP: 硼酸鹽 : TiO2
= 52.1: 0: 7.2) - 比較實例 調配物 8- 主劑 ( 主劑 : 硬化劑 = 4:1)
調配物 8- 硬化劑 ( 主劑 : 硬化劑 = 4:1)
調配物 9: (APP: Al(OH)3
: TiO2
= 51.9: 0.2: 7.2) 調配物 9- 主劑 ( 主劑 : 硬化劑 = 4:1)
11
Bisley & Company Pty Ltd調配物 9- 硬化劑 ( 主劑 : 硬化劑 = 4:1)
調配物 10: (APP: Al(OH)3
: TiO2
= 42.6: 9.5: 7.2) 調配物 10- 主劑 ( 主劑 : 硬化劑 = 4:1)
調配物 10- 硬化劑 ( 主劑 : 硬化劑 = 4:1)
調配物 11: (APP: Al2
O3
: TiO2
= 51.9: 0.2: 7.2) 調配物 11- 主劑 ( 主劑 : 硬化劑 = 4:1)
12
Bisley & Company Pty Ltd調配物 11- 硬化劑 ( 主劑 : 硬化劑 = 4:1)
調配物 12: (APP: SiO2
: TiO2
= 51.6: 0.5: 7.2) 調配物 12- 主劑 ( 主劑 : 硬化劑 = 4:1)
13
Brenntag調配物 12- 硬化劑 ( 主劑 : 硬化劑 = 4:1)
調配物 13: (APP: SiO2
: Al2
O3
: TiO2
= 51.1: 0.5: 0.5: 7.2) 調配物 13- 主劑 ( 主劑 : 硬化劑 = 4:1)
調配物 13- 硬化劑 ( 主劑 : 硬化劑 = 4:1)
表1
組分 | 商標名 | 集合中的重量% |
雙酚F二縮水甘油醚 | EPIKOTE 8621 | 21.1 |
腰果殼液體 | ROYOXY RAD-913 | 3.2 |
玻璃纖維 | CHOPVANTAGE 31563 | 4.1 |
蓖麻油衍生物 | THIXATROL ST4 | 0.2 |
多磷酸銨 | EXOLIT AP 4225 | 15.2 |
硼酸鋅 | C-TEC CT-ZB 4006 | 31.2 |
組分 | 商標名 | 集合中的重量% |
(參-2,4,6-二甲基胺基甲苯酚) | Accelerator 960-17 | 1.7 |
聚醯胺胺 | Aradur 1408 | 18.7 |
蓖麻油衍生物 | THIXATROL ST | 0.1 |
鎂鋁海泡石 | ATTAGEL 509 | 1.9 |
三聚氰胺 | 再結晶三聚氰胺10 | 2.6 |
組分 | 商標名 | 集合中的重量% |
雙酚F二縮水甘油醚 | EPIKOTE 862 | 21.1 |
腰果殼液體 | ROYOXY RAD-913 | 3.2 |
玻璃纖維 | CHOPVANTAGE 3156 | 3.2 |
蓖麻油衍生物 | THIXATROL ST | 0.2 |
多磷酸銨 | EXOLIT AP 422 | 15.2 |
硼酸鋅 | C-TEC CT ZB 400 | 29.4 |
二氧化鈦 | TI-PURE R-70611 | 2.7 |
組分 | 商標名 | 集合中的重量% |
(參-2,4,6-二甲基胺基甲苯酚) | Accelerator 960-1 | 1.7 |
聚醯胺胺 | Aradur 140 | 18.7 |
蓖麻油衍生物 | THIXATROL ST | 0.1 |
鎂鋁海泡石 | ATTAGEL 50 | 1.9 |
三聚氰胺 | 再結晶三聚氰胺 | 2.6 |
組分 | 商標名 | 集合中的重量% |
雙酚F二縮水甘油醚 | EPIKOTE 862 | 21.1 |
腰果殼液體 | ROYOXY RAD-913 | 3.2 |
玻璃纖維 | CHOPVANTAGE 3156 | 3.1 |
蓖麻油衍生物 | THIXATROL ST | 0.2 |
多磷酸銨 | EXOLIT AP-422 | 15.2 |
硼酸鋅 | C-TEC CT ZB 400 | 27.5 |
二氧化鈦 | TI-PURE R-706 | 4.6 |
組分 | 商標名 | 集合中的重量% |
(參-2,4,6-二甲基胺基甲苯酚) | Accelerator 960-1 | 1.7 |
聚醯胺胺 | Aradur 140 | 18.7 |
蓖麻油衍生物 | THIXATROL ST | 0.1 |
鎂鋁海泡石 | ATTAGEL 50 | 1.9 |
三聚氰胺 | 再結晶三聚氰胺 | 2.5 |
組分 | 商標名 | 集合中的重量% |
雙酚F二縮水甘油醚 | EPIKOTE 862 | 25.2 |
腰果殼液體 | ROYOXY RAD-913 | 3.5 |
玻璃纖維 | CHOPVANTAGE 3156 | 1.4 |
蓖麻油衍生物 | THIXATROL ST | 0.2 |
多磷酸銨 | EXOLIT AP 422 | 15.7 |
硼酸鋅 | C-TEC CT ZB 400 | 18.5 |
二氧化鈦 | TI-PURE R-706 | 5.9 |
組分 | 商標名 | 集合中的重量% |
(參-2,4,6-二甲基胺基甲苯酚) | Accelerator 960-1 | 1.9 |
聚醯胺胺 | Aradur 140 | 23.0 |
蓖麻油衍生物 | THIXATROL ST | 0.1 |
鎂鋁海泡石 | ATTAGEL 50 | 1.9 |
三聚氰胺 | Recrystalllized melamine | 2.7 |
組分 | 商標名 | 集合中的重量% |
雙酚F二縮水甘油醚 | EPIKOTE 862 | 18.5 |
腰果殼液體 | ROYOXY RAD-913 | 3.2 |
玻璃纖維 | CHOPVANTAGE 3156 | 1.4 |
蓖麻油衍生物 | THIXATROL ST | 0.2 |
多磷酸銨 | EXOLIT AP 422- | 29.3 |
硼酸鋅 | C-TEC CT ZB 400 | 19.6 |
二氧化鈦 | TI-PURE R-706 | 5.9 |
組分 | 商標名 | 集合中的重量% |
(參-2,4,6-二甲基胺基甲苯酚) | Accelerator 960-1 | 1.1 |
聚醯胺胺 | Aradur 140 | 16.3 |
蓖麻油衍生物 | THIXATROL ST | 0.1 |
鎂鋁海泡石 | ATTAGEL 50 | 1.9 |
三聚氰胺 | 再結晶三聚氰胺 | 2.5 |
組分 | 商標名 | 集合中的重量% |
雙酚F二縮水甘油醚 | EPIKOTE 862 | 18.6 |
腰果殼液體 | ROYOXY RAD-913 | 3.2 |
玻璃纖維 | CHOPVANTAGE 3156 | 1.4 |
蓖麻油衍生物 | THIXATROL ST | 0.2 |
多磷酸銨 | EXOLIT AP 422 | 35.3 |
硼酸鋅 | C-TEC CT ZB 400 | 10.3 |
二氧化鈦 | TI-PURE R-706 | 9.2 |
組分 | 商標名 | 集合中的重量% |
(參-2,4,6-二甲基胺基甲苯酚) | Accelerator 960-1 | 1.0 |
聚醯胺胺 | Aradur 140 | 18.2 |
蓖麻油衍生物 | THIXATROL ST | 0.1 |
三聚氰胺 | 再結晶三聚氰胺 | 2.5 |
組分 | 商標名 | 集合中的重量% |
雙酚F二縮水甘油醚 | EPIKOTE 862 | 11.4 |
腰果殼液體 | ROYOXY RAD-913 | 3.2 |
玻璃纖維 | CHOPVANTAGE 3156 | 1.4 |
蓖麻油衍生物 | THIXATROL ST | 0.2 |
多磷酸銨 | EXOLIT AP 422 | 20.7 |
硼酸鋅 | C-TEC CT ZB 400 | 14.5 |
二氧化鈦 | TI-PURE R-706 | 13.3 |
組分 | 商標名 | 集合中的重量% |
(參-2,4,6-二甲基胺基甲苯酚) | Accelerator 960-1 | 1.1 |
聚醯胺胺 | Aradur 140 | 10.2 |
多磷酸銨 | EXOLIT AP 422 | 20.0 |
蓖麻油衍生物 | THIXATROL ST | 0.1 |
三聚氰胺 | 再結晶三聚氰胺 | 3.9 |
組分 | 商標名 | 集合中的重量% |
雙酚F二縮水甘油醚 | EPIKOTE 862 | 14.2 |
腰果殼液體 | ROYOXY RAD-913 | 2.7 |
玻璃纖維 | CHOPVANTAGE 3156 | 1.7 |
蓖麻油衍生物 | THIXATROL ST | 0.2 |
多磷酸銨 | EXOLIT AP 422 | 52.1 |
二氧化鈦 | TI-PURE R-706 | 7.2 |
組分 | 商標名 | 集合中的重量% |
(參-2,4,6-二甲基胺基甲苯酚) | Accelerator 960-1 | 1.1 |
聚醯胺胺 | Aradur 140 | 12.2 |
蓖麻油衍生物 | THIXATROL ST | 0.1 |
三聚氰胺 | 再結晶三聚氰胺 | 8.5 |
組分 | 商標名 | 集合中的重量% |
雙酚F二縮水甘油醚 | EPIKOTE 862 | 14.2 |
腰果殼液體 | ROYOXY RAD-913 | 2.7 |
玻璃纖維 | CHOPVANTAGE 3156 | 1.7 |
氫氧化鋁 | ALUMINUM HYDROXIDE11 | 0.2 |
蓖麻油衍生物 | THIXATROL ST | 0.2 |
多磷酸銨 | EXOLIT AP 422 | 51.9 |
二氧化鈦 | TI-PURE R-706 | 7.2 |
組分 | 商標名 | 集合中的重量% |
(參-2,4,6-二甲基胺基甲苯酚) | Accelerator 960-1 | 1.1 |
聚醯胺胺 | Aradur 140 | 12.2 |
蓖麻油衍生物 | THIXATROL ST | 0.1 |
三聚氰胺 | 再結晶三聚氰胺 | 8.5 |
組分 | 商標名 | 集合中的重量% |
雙酚F二縮水甘油醚 | EPIKOTE 862 | 14.2 |
腰果殼液體 | ROYOXY RAD-913 | 2.7 |
玻璃纖維 | CHOPVANTAGE 3156 | 1.7 |
氫氧化鋁 | ALUMINUM HYDROXIDE | 9.5 |
蓖麻油衍生物 | THIXATROL ST | 0.2 |
多磷酸銨 | EXOLIT AP 422 | 42.6 |
二氧化鈦 | TI-PURE R-706 | 7.2 |
組分 | 商標名 | 集合中的重量% |
(參-2,4,6-二甲基胺基甲苯酚) | Accelerator 960-1 | 1.1 |
聚醯胺胺 | Aradur 140 | 12.2 |
蓖麻油衍生物 | THIXATROL ST | 0.1 |
三聚氰胺 | 再結晶三聚氰胺 | 8.5 |
組分 | 商標名 | 集合中的重量% |
雙酚F二縮水甘油醚 | EPIKOTE 862 | 14.2 |
腰果殼液體 | ROYOXY RAD-913 | 2.7 |
玻璃纖維 | CHOPVANTAGE 3156 | 1.7 |
氧化鋁 | CALCINED ALUMINA12 | 0.2 |
蓖麻油衍生物 | THIXATROL ST | 0.2 |
多磷酸銨 | EXOLIT AP 422 | 51.9 |
二氧化鈦 | TI-PURE R-706 | 7.2 |
組分 | 商標名 | 集合中的重量% |
(參-2,4,6-二甲基胺基甲苯酚) | Accelerator 960-1 | 1.1 |
聚醯胺胺 | Aradur 140 | 12.2 |
蓖麻油衍生物 | THIXATROL ST | 0.1 |
三聚氰胺 | 再結晶三聚氰胺 | 8.5 |
組分 | 商標名 | 集合中的重量% |
雙酚F二縮水甘油醚 | EPIKOTE 862 | 14.2 |
腰果殼液體 | ROYOXY RAD-913 | 2.7 |
玻璃纖維 | CHOPVANTAGE 3156 | 1.7 |
二氧化矽 | FUMED SILICA13 | 0.5 |
蓖麻油衍生物 | THIXATROL ST | 0.2 |
多磷酸銨 | EXOLIT AP 422 | 51.6 |
二氧化鈦 | TI-PURE R-706 | 7.2 |
組分 | 商標名 | 集合中的重量% |
(參-2,4,6-二甲基胺基甲苯酚) | Accelerator 960-1 | 1.1 |
聚醯胺胺 | Aradur 140 | 12.2 |
蓖麻油衍生物 | THIXATROL ST | 0.1 |
三聚氰胺 | 再結晶三聚氰胺 | 8.5 |
組分 | 商標名 | 集合中的重量% |
雙酚F二縮水甘油醚 | EPIKOTE 862 | 14.2 |
腰果殼液體 | ROYOXY RAD-913 | 2.7 |
玻璃纖維 | CHOPVANTAGE 3156 | 1.7 |
二氧化矽 | FUMED SILICA | 0.5 |
氧化鋁 | CALCINED ALUMINA | 0.5 |
蓖麻油衍生物 | THIXATROL ST | 0.2 |
多磷酸銨 | EXOLIT AP 422 | 51.1 |
二氧化鈦 | TI-PURE R-706 | 7.2 |
組分 | 商標名 | 集合中的重量% |
(參-2,4,6-二甲基胺基甲苯酚) | Accelerator 960-1 | 1.1 |
聚醯胺胺 | Aradur 140 | 12.2 |
蓖麻油衍生物 | THIXATROL ST | 0.1 |
三聚氰胺 | 再結晶三聚氰胺 | 8.5 |
調配物 | APP (wt%) | Al(OH)3 (wt%) | Al2 O3 (wt%) | SiO2 (wt%) | TiO2 (wt%) | 硼酸鹽 (wt%) | 厚度(μm) | 膨脹係數 | 10分鐘後之溫度(℃) | 炭之圖片 |
1 | 15.2 | 0 | 0 | 0 | 0 | 31.2 | 500 | 2~3 | 510 | 圖1 |
2 | 15.2 | 0 | 0 | 0 | 2.7 | 29.4 | 500 | 2~3 | 430 | 圖2 |
3 | 15.2 | 0 | 0 | 0 | 4.6 | 27.5 | 500 | 2~3 | 460 | 圖3 |
4 | 15.7 | 0 | 0 | 0 | 5.9 | 18.5 | 500 | 3~4 | 470 | 圖4 |
5 | 29.3 | 0 | 0 | 0 | 5.9 | 19.6 | 500 | 5 | 400 | 圖5 |
6 | 35.3 | 0 | 0 | 0 | 9.2 | 10.3 | 500 | 8 | 350 | 圖6(a) 圖6(b) |
7 | 40.7 | 0 | 0 | 0 | 13.3 | 14.5 | 500 | 10 | 320 | 圖7 |
8 | 52.1 | 0 | 0 | 0 | 7.2 | 0 | 500 | 30 | 440 | 圖8 |
9 | 51.9 | 0.2 | 0 | 0 | 7.2 | 0 | 500 | 10 | 320 | 圖9 |
10 | 42.6 | 9.5 | 0 | 0 | 7.2 | 0 | 500 | 8 | 350 | 圖10 |
11 | 51.9 | 0 | 0.2 | 0 | 7.2 | 0 | 500 | 15 | 330 | 圖11 |
12 | 51.6 | 0 | 0 | 0.5 | 7.2 | 0 | 500 | 20 | 340 | 圖12 |
13 | 51.1 | 0 | 0.5 | 0.5 | 7.2 | 0 | 500 | 20 | 330 | 圖13 |
如自以上結果可見,具有硼酸鹽但無TiO2
且APP小於20 wt%之調配物1產生不可接受之炭,其未充分膨脹且在膨脹之後不黏附於基板。對於調配物2、3及4可見類似結果,該等調配物中使用小於5 wt% TiO2
及/或小於20 wt% APP;炭未能具有充分膨脹,且在暴露基板上未發現炭殘留,表明炭之較差基板黏附力。具有TiO2
但無硼酸鹽之調配物8亦產生不可接受的結果,在於其膨脹過於廣泛,導致低炭密度,且因此藉由火炬火焰吹打移除炭層。調配物5、6及7,其中TiO2
及硼酸鹽之量各自在以總固體重量計5-20 wt%範圍內,且APP在以總固體重量計20-55 wt%範圍內,即使在15 mm火炬直徑下2巴火焰吹打壓力下仍產生可接受的炭及可接受的黏附力。「良好黏附力」之明顯實例可在調配物6之第二圖片中,其中展示了炭之橫截面;炭為緻密的且未見與基板明顯脫離。具有所列舉量之TiO2
、APP、鋁源及/或二氧化矽源的調配物9至13亦產生可接受之炭及黏附力結果。
儘管上文已出於說明之目的描述本發明之特定實例,但對熟習此項技術者將顯而易見,在不脫離所附申請專利範圍中所定義之本發明的情況下,可對本發明細節進行大量變化。
表1包括用調配物1-13之實驗或比較膨脹型塗料組合物塗佈之基板經受1200±50℃炬火10分鐘之後經塗佈基板的相片。調配物6亦包括在經歷炬火之後經塗佈面板之側視圖。
Claims (19)
- 本發明係有關一種塗料組合物,其包含: a)成膜組分; b)磷酸源; c)硼酸源;鋁源;及/或二氧化矽源; d) TiO2 ;及 e)氣體源; 其中該TiO2 以5至20 wt%,諸如9至15 wt%之量存在,該磷酸源以20至55 wt%,諸如25至40 wt%或40至55 wt%之量存在,且其中若組分c包含硼酸源,則其以5至20 wt%,諸如9至15 wt%之量存在,若組分c包含鋁源,則其以0.1至10 wt%,諸如0.2至8 wt%之量存在,且若組分c包含二氧化矽源,則其以0.1至5 wt%,諸如0.4至1 wt%之量存在,其中wt%以該組合物之總固體重量計。
- 如請求項1之塗料組合物,其中該成膜組分以20-60 wt%之量存在及/或該氣體源以1-10 wt%之量存在,其中wt%以該組合物之總固體重量計。
- 如前述請求項中任一項之塗料組合物,其進一步包含至多4 wt%之量的纖維,諸如玻璃纖維及/或礦物纖維,其中wt%以該組合物之總固體重量計。
- 如前述請求項中任一項之塗料組合物,其進一步包含總量為2-20 wt%之一或多種添加劑,其中wt%以該組合物之總固體重量計。
- 如前述請求項中任一項之塗料組合物,其中該成膜組分包含環氧樹脂及胺交聯劑,該磷酸源包含磷酸銨、磷酸三苯酯及/或磷酸三(2-氯異丙基)酯,該硼酸源若使用則包含金屬硼酸鹽、五硼酸銨及/或硼酸,且該氣體源包含三聚氰胺、脲及/或可膨脹石墨,該鋁源若使用則包含氫氧化鋁及/或氧化鋁,且該二氧化矽源若使用則包含煙霧狀二氧化矽。
- 一種自支撐膜或薄片,其由如前述請求項中任一項之塗料組合物形成。
- 一種用於塗佈基板之方法,其包含將如請求項1至5中任一項之塗料組合物或如請求項6之膜或薄片施加至該基板之至少一部分。
- 如請求項7之方法,其中該基板包含金屬,諸如鋁或鋼,或塑膠,諸如聚碳酸酯。
- 一種基板,其根據如請求項7或8中任一項之方法塗佈。
- 一種物件,其包含如請求項9之基板。
- 如請求項10之物件,其中該物件包含鋰離子電池。
- 如請求項11之物件,其中該電池包含界定外殼之外壁元件及視情況選用之內壁元件,其中該塗料組合物或膜或薄片至少部分地施加至該等外壁元件中之任一者的外側及/或內側及/或在該等內壁元件存在時施加至該等內壁元件中之任一者的任何側面。
- 如請求項12之物件,其中該等外壁及/或內壁元件中之任一者包含複合物、鋼、鋁及/或聚碳酸酯。
- 如請求項11至13中任一項之物件,其中該電池為包含複數個個別電池單元之電池組,其中該塗料組合物或膜或薄片經定位以使該等個別電池單元中之至少兩者在膨脹狀態及視情況炭化狀態下彼此熱絕緣;且其中該電池視情況包含一或多種額外阻燃材料及/或緩解火災的構件。
- 如請求項10之物件,其中該物件包含車輛。
- 如請求項10之物件,其中該物件包含結構。
- 如請求項10之物件,其中該物件為電池組件,該電池組件至少部分地塗佈有如請求項1至5中任一項之塗料組合物或如請求項6之膜或薄片已施加至該電池組件。
- 如請求項17之電池組件,其中該電池組件包含電動車電池組件。
- 如請求項17或18之電池組件,其中該電池組件包含電池單元、電池殼、電池模組電池組、電池盒、電池單元殼、電池組殼、電池蓋及托盤、熱管理系統、電池外殼、模組外殼、模組裝架、電池側板、電池單元罩殼、冷卻模組、冷卻管、冷卻片、冷卻板、母線、電池框架、電氣連接、金屬線、銅或鋁導體或電纜,或其任何組合。
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US202063018812P | 2020-05-01 | 2020-05-01 | |
US63/018,812 | 2020-05-01 | ||
US202163161214P | 2021-03-15 | 2021-03-15 | |
US63/161,214 | 2021-03-15 |
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TW110115826A TW202208560A (zh) | 2020-05-01 | 2021-04-30 | 膨脹型塗料 |
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EP (1) | EP4143265A1 (zh) |
JP (1) | JP2023524073A (zh) |
KR (1) | KR20230004639A (zh) |
CN (2) | CN115485340B (zh) |
CA (1) | CA3175422A1 (zh) |
MX (1) | MX2022013721A (zh) |
TW (1) | TW202208560A (zh) |
WO (1) | WO2021222685A1 (zh) |
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WO2024020483A1 (en) * | 2022-07-22 | 2024-01-25 | Ppg Industries Ohio, Inc. | Fire retardant coatings |
KR20240058526A (ko) * | 2022-10-26 | 2024-05-03 | 주식회사 케이씨씨 | 도료 조성물 |
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Publication number | Priority date | Publication date | Assignee | Title |
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US4879320A (en) * | 1989-03-15 | 1989-11-07 | Hastings Otis | Intumescent fire-retardant coating material |
GB2246136A (en) * | 1990-07-18 | 1992-01-22 | Prometheus Developments Ltd | Intumescent coating compositions |
US5070119A (en) | 1990-09-28 | 1991-12-03 | Ppg Industries, Inc. | Flexible intumescent coating composition |
US5108832A (en) | 1990-09-28 | 1992-04-28 | Ppg Industries, Inc. | Flexible intumescent coating composition |
GB9215184D0 (en) | 1992-07-17 | 1992-09-02 | Alcan Int Ltd | Intumescent systems |
EP1404766A1 (en) * | 2001-06-01 | 2004-04-07 | W. & J. Leigh & Co. | Coating compositions |
US20040002559A1 (en) * | 2002-04-10 | 2004-01-01 | Malisa Troutman | Flame retardant coatings |
GB0428005D0 (en) * | 2004-12-21 | 2005-01-26 | W & J Leigh & Co | Intumescent coating compositions |
CN101857756B (zh) * | 2010-07-08 | 2012-07-25 | 内蒙古兴泰建筑有限责任公司 | 一种钢结构防火涂料 |
CN102108236A (zh) * | 2010-12-30 | 2011-06-29 | 北京虹霞正升涂料有限责任公司 | 一种用于超薄型钢结构的防火防腐涂料 |
WO2013179218A1 (en) * | 2012-05-28 | 2013-12-05 | L-M-J Nation Security Llc | Fire resistant paint for application to an outdoor or indoor surface, articles of manufacture, an apparatus for manufacture and a process for manufacture thereof |
EP3055365B1 (en) * | 2013-10-11 | 2018-06-27 | Huntsman International LLC | Polyisocyanate-based intumescent coating |
CN105694620B (zh) * | 2016-04-03 | 2018-05-11 | 北京化工大学 | 一种高固含量水性超薄膨胀型防火涂料及其制备方法 |
SG11202101846UA (en) * | 2018-08-28 | 2021-03-30 | Ppg Ind Ohio Inc | Battery comprising an intumescent layer |
GB201816974D0 (en) * | 2018-10-18 | 2018-12-05 | Advanced Insulation Ltd | A mixture curable to provide an intumescent coating material |
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2021
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- 2021-04-30 KR KR1020227039940A patent/KR20230004639A/ko unknown
- 2021-04-30 CN CN202180032080.7A patent/CN115485340B/zh active Active
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- 2021-04-30 WO PCT/US2021/030061 patent/WO2021222685A1/en unknown
- 2021-04-30 MX MX2022013721A patent/MX2022013721A/es unknown
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MX2022013721A (es) | 2022-12-13 |
EP4143265A1 (en) | 2023-03-08 |
JP2023524073A (ja) | 2023-06-08 |
KR20230004639A (ko) | 2023-01-06 |
US20230183496A1 (en) | 2023-06-15 |
CN117487389A (zh) | 2024-02-02 |
CN115485340B (zh) | 2023-12-08 |
CA3175422A1 (en) | 2021-11-04 |
CN115485340A (zh) | 2022-12-16 |
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