TWI828349B - 用於可周溫交聯固化之乙烯基分枝酯類與乙烯基矽烷共聚物組合物之無黃化催化劑及其用途 - Google Patents
用於可周溫交聯固化之乙烯基分枝酯類與乙烯基矽烷共聚物組合物之無黃化催化劑及其用途 Download PDFInfo
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- C09D143/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing boron, silicon, phosphorus, selenium, tellurium, or a metal; Coating compositions based on derivatives of such polymers
- C09D143/04—Homopolymers or copolymers of monomers containing silicon
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- C08F218/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an acyloxy radical of a saturated carboxylic acid, of carbonic acid or of a haloformic acid
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- C08F218/04—Vinyl esters
- C08F218/10—Vinyl esters of monocarboxylic acids containing three or more carbon atoms
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- C08F230/085—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal containing a metal containing silicon the monomer being a polymerisable silane, e.g. (meth)acryloyloxy trialkoxy silanes or vinyl trialkoxysilanes
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Abstract
本發明係關於用於可低溫(＜80℃)濕氣固化之雙封裝著色塗料中以替代錫鹽的催化劑之組合物。基於低毒性羥胺之該等催化劑單獨或與有機酸組合提供淺色及高效塗料。
Description
本發明係關於用於可低溫(<80℃)濕氣固化之單封裝著色塗料中以替代錫鹽的催化劑之組合物。基於低毒性羥胺之該等催化劑單獨或與有機酸組合提供淺色及高效塗料。
在塗料調配物中使用矽烷為所熟知的，且丙烯酸-矽烷塗料組合物尤其具有可接受的固化速率，且產物薄膜在固化後具有良好的物理及化學特性。當前用於此等塗料之催化劑為錫基鹽；然而，此等錫組合物之一個重要缺點為其高毒性。數十年來，行業一直致力於找到解決此主要缺點的方案。
US 3,094,497係關於胺羧酸鹽作為催化劑用於矽烷縮合之用途。實例1提供由一級胺、二級胺及三級胺與羧酸及多磷酸鹽組合製成之催化劑的清單。但其未提及羥胺。
US 3,208,961揭示諸如一氧化鉛及碳酸鉛之鉛化合物與羧酸銨鹽之「原位」組合。
US10640641描述無錫可固化組合物，其具有(A)一或多種具有含反應性矽基團之有機聚合物，其中至少一種聚合物具有(..)飽和烴聚合物及(甲基)丙烯酸酯聚合物；(B)0.001至20重量份(...)由一或多種金屬脒錯合物及一或多種胺羧酸鹽組成之矽烷醇縮合催化劑。
JP-A-5-117519或EP 0 538 881揭示藉由同時使用羧酸及胺而突然改良固化效能，但此等組合物缺乏足夠黏附性。另外，此類催化劑之儲存穩定性亦不理想且在儲存此類組合物期間可能出現過早膠凝。揭示一系列適合羧酸及胺。其中惟有的羥胺異丙醇胺及單乙醇胺。該文獻未提及實際使用羥胺之實例，亦無任何證據表明作者發現羥胺比其他胺具有優良特性。亦沒有論述胺對顏色之影響及一些胺在該方面可能具有的更佳效能。
此清楚地表明，塗料行業仍在尋找出於環境及毒性態樣考慮，應當替代當前錫有機鹽的替代性催化劑。
在對尤其丙烯酸-矽烷塗料組合物之固化進行研究後，吾人發現單獨使用位阻一級羥胺或與有機酸組合使用會為行業提供錫催化劑之替代品。
本發明係關於單獨或與有機酸組合之依結構1中所定義之位阻一級羥胺之催化劑的用途。
本發明之胺為如下一級胺，其中在四級碳原子上至少一個取代基為
羥基官能基。
R1=CH3、CH2CH3、CH(CH3)2、CH2CH(CH3)2、烷基、環烷基、芳基，R2=烷基、環烷基、芳基、羥烷基、CH2OH、CH2CH2OH，R1及R2可鍵聯成環狀結構，例如形成環己烷環。
此系列之實例為：2-胺基-2-甲基丙-1-醇(AMP)
或2-胺基-2-乙基-1,3-丙二醇(AEP)
及參(羥甲基)胺基甲烷，本發明之另一實施例為結構1之羥胺與有機酸之組合。較佳有機酸為烷基羧酸：R3 COOH，其中R3為CH3、CH2CH3、烷基、分枝鏈烷基、環烷基。
酸之實例包括：乙酸、丙酸、己酸、2-乙基己酸、新癸酸(來自Hexion Inc.之Versatic 10)。
本發明之另一實施例為一種單組分溶劑基可固化塗料組合物，其包含有機聚合物與如上之位阻一級羥胺單獨或與有機酸之組合，其中該有機聚合物具有含矽基團，該含矽基團可藉由形成矽氧烷鍵而交聯。該有機聚合物較佳含有具有C2至C13碳原子之羧酸之乙烯基酯類。該單組分溶劑基可固化塗料組合物較佳含有經胺基取代之矽烷化合物及/或經環氧基取代之矽烷化合物。
結構1之羥胺較佳以基於固體樹脂之0.2至5重量百分比之濃度使用。最佳含量在基於固體樹脂之0.5至3.5Wt%之間。
羥胺與有機酸之組合以基於固體樹脂之0.3與5重量%之間的濃度使用。酸與胺之間的比率在0.1/1至5/1之間，且較佳在2/1至1.2/1之間。胺與酸之組合展示出協同效應，其產生依下文實例中所給出之改良薄膜特性。
為了提供對本發明，包括其代表性優點之較佳理解，提供以下實例。
為使熟習此項技術者可更全面地理解本文中所呈現之本發明，闡述以下程序及實例。除非另外指明，否則本申請案中應用以下量測單位及定義：所有份數及百分比均以重量計；溫度均為攝氏度(℃)。
實驗
對於以下實例，根據以下程序得到資料。
固體：固體為存在於塗料調配物中之非揮發性物質的重量百分比。其係藉由在110℃下通風烘箱中持續1小時之重量損失來量測。
黏度：黏度為聚合物製備物之流動抗性。黏度係藉由布絡克菲爾德
黏度計(Brookfield viscosimeter)測定。
分子量：分子量係以重量及數量平均Mw形式給出，藉由凝膠滲透層析儀測定，其使用聚苯乙烯作為參考物，四氫呋喃作為溶離溶劑，及折射率作為偵測項，依DIN標準55672中所描述
適用期：適用期係在此期間聚合物組合物可用於特定應用之時間的估算。適用期通常藉由調配系統在進行施加後在封閉罐中使其初始黏度增加一倍所花費的時間來測定。
存放期：存放期為所調配之黏合劑可在典型儲存條件下儲存而不喪失其效能之時間的估算。存放期通常藉由量測黏度變化來測定。
耐溶劑性：ASTM D4752涉及用浸有甲基乙基酮MEK之粗棉布摩擦烘烤薄膜之表面，直至薄膜出現失效或破裂。摩擦被視為雙重摩擦(向前摩擦一次及向後摩擦一次構成雙重摩擦)。
硬度：柯尼希(Koenig)擺錘硬度測試係基於擺錘擺動之幅度在支撐於更軟表面上時下降更快的原理。存在若干硬度測試，其將振盪運動之阻尼與表面硬度聯繫起來。
顏色：對樹脂進行視覺上的比較，水白色樹脂得分為0，而顏色最深的樹脂得分為5。
執行以下實例且提供以說明本發明，且不應解釋為限制本發明之範疇。
向配備有攪拌器及冷凝器之反應器中饋入表1之成分
將乙酸丁酯倒入反應器中且加熱至115℃。達到該溫度後，添加Luperox 531M80且開始在4小時內饋入單體混合物及Luperox。隨後，在將反應器溫度保持在115℃的同時在一小時內投與促進劑混合物。最後，將反應器冷卻至低於60℃。
用乙酸丁酯稀釋實例1之樹脂以獲得100cP之黏度且與如表2中所呈現之催化劑的一部分混合。
藉由刮塗機以大約100微米之濕厚度將經調配之透明塗料塗覆於鋼板
上，且使其在大約23℃及50%相對濕度下乾燥及固化至少一週(168小時)。塗料之固化及硬化之演變藉由柯尼希硬度量測。且視覺評估液體樣品之黃化。將樣品自0(無黃化)至4(強黃化)分級。
表2之結論；根據非錫催化劑，僅AMP及DBU展示出高反應性。另外，AMP在低濃度下產生較淺顏色。二丁胺產生非常良好之反應性但毒性極高。亦應瞭解，不同於所使用之其他胺，1%含量之AMP及AEP不會導致樹脂黃化。
AMP及AEP將高反應性、低黃化及無錫之益處結合。
向配備有攪拌器及冷凝器之反應器中饋入表3之成分
將乙酸丁酯倒入反應器中且加熱至105℃。達到該溫度後，添加Luperox 531M80且開始在4小時內饋入單體混合物及Luperox。隨後，在將反應器溫度保持在105℃的同時在一小時內投與促進劑混合物。將反應器冷卻至低於60℃，將2phm乙烯基三甲氧基矽烷添加至樹脂中，且最後添加30phm乙酸正丁酯以將黏度降低至約100cP。
實例3塗料之製備：使用240g實例2之樹脂、6.49g分散劑Disperplast P、2.3g調平劑BYK 358N、2.3g消泡劑BYK 077、4.66g流掛控制劑Solthix 250及129.7
g疏水性二氧化鈦Ti-Pure R350進行研磨來製備1K濕氣固化塗料。對於調漿，使用58.4g丙酸乙氧基乙酯及59.9g甲基戊基酮。較佳為低含水量品質成分以避免罐中塗料過早固化。最後，添加3%固體聚合物Coatosil MP200作為助黏劑。
評估用於透明塗料之催化劑：將一系列催化劑與實例2之樹脂混合。藉由刮塗機以大約100微米之濕厚度將經如此調配之透明塗料塗覆於鋼板上，且使其在大約23℃及50%相對濕度下乾燥及固化至少一週(168小時)。塗料之固化及硬化之演變藉由柯尼希硬度及耐溶劑性量測。
根據此表之結論：所用羧酸(Versatic 10)與羥胺(AMP)之間存在協同效應。
Claims (6)
- 一種單組分溶劑基可固化塗料組合物，其包含：(A)具有含矽基團之有機聚合物，該含矽基團可藉由形成矽氧烷鍵而交聯，其中該有機聚合物含有具有C2至C13碳原子之羧酸之乙烯基酯類；(B)如下之位阻一級羥胺：
- 如請求項1之組合物，其中該結構1之位阻一級羥胺以基於固體樹脂之0.2至5Wt%之間的濃度使用。
- 如請求項1之組合物，其中該位阻一級羥胺與有機酸之組合以基於固體樹脂之0.3與5重量%之間的濃度使用，酸/胺之重量比為0.1/1至5/1之間。
- 如請求項1之組合物，其中結構1之該位阻一級羥胺為羥胺，其為2-胺基-2-甲基丙-1-醇或2-胺基-2-乙基-1,3-丙二醇。
- 如請求項1之組合物，其中該有機酸係選自乙酸、丙酸、己酸、新癸酸及其組合。
- 如請求項1至5中任一項之組合物，其含有經胺基取代之矽烷化合物及/或經環氧基取代之矽烷化合物。
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| EP21075012.1A EP4159803A1 (en) | 2021-10-04 | 2021-10-04 | Non yellowing catalyst used for ambient cure of compositions comprising copolymers of vinyl branched ester and vinyl silane and use thereof |
| EP21075012.1 | 2021-10-04 |
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| TW202323458A TW202323458A (zh) | 2023-06-16 |
| TWI828349B true TWI828349B (zh) | 2024-01-01 |
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| Country | Link |
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| EP (1) | EP4159803A1 (zh) |
| KR (1) | KR20240065298A (zh) |
| CN (1) | CN118076676A (zh) |
| CA (1) | CA3232761A1 (zh) |
| TW (1) | TWI828349B (zh) |
| WO (1) | WO2023059477A1 (zh) |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20090076217A1 (en) * | 2007-09-17 | 2009-03-19 | Gommans Louie H | One component polysiloxane coating compositions and related coated substrates |
| WO2021018410A1 (en) * | 2019-07-30 | 2021-02-04 | Hexion Research Belgium Sa | One pack ambient cure crosslinkable copolymers of vinyl branched ester and vinyl silane compositions and use thereof |
Family Cites Families (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3094497A (en) | 1960-07-28 | 1963-06-18 | Dow Corning | Condensation catalysts |
| US3208961A (en) | 1963-05-13 | 1965-09-28 | Dow Coruing Corp | In situ catalyst forming compositions and process |
| JP3122775B2 (ja) | 1991-10-24 | 2001-01-09 | 鐘淵化学工業株式会社 | 硬化性組成物 |
| EP2424914B1 (en) * | 2009-04-29 | 2014-08-13 | Coatings Foreign IP Co. LLC | Water-based two-component coating compositions |
| DE112016000869T5 (de) | 2015-02-23 | 2018-01-18 | King Industries, Inc. | Härtbare Beschichtungszusammensetzungen von Silan-funktionellen Polymeren |
| DK3363827T3 (da) * | 2017-02-21 | 2019-12-02 | Hexion Res Belgium Sa | Omgivelsestemperatur hærdende tværbindende copolymere af forgrenet vinylester og vinylsilanfremstiling og anvendelse deraf |
-
2021
- 2021-10-04 EP EP21075012.1A patent/EP4159803A1/en not_active Withdrawn
-
2022
- 2022-09-27 KR KR1020247013485A patent/KR20240065298A/ko unknown
- 2022-09-27 WO PCT/US2022/044864 patent/WO2023059477A1/en active Application Filing
- 2022-09-27 CN CN202280066839.8A patent/CN118076676A/zh active Pending
- 2022-09-27 CA CA3232761A patent/CA3232761A1/en active Pending
- 2022-10-04 TW TW111137653A patent/TWI828349B/zh active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20090076217A1 (en) * | 2007-09-17 | 2009-03-19 | Gommans Louie H | One component polysiloxane coating compositions and related coated substrates |
| WO2021018410A1 (en) * | 2019-07-30 | 2021-02-04 | Hexion Research Belgium Sa | One pack ambient cure crosslinkable copolymers of vinyl branched ester and vinyl silane compositions and use thereof |
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| Publication number | Publication date |
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| KR20240065298A (ko) | 2024-05-14 |
| CN118076676A (zh) | 2024-05-24 |
| CA3232761A1 (en) | 2023-04-13 |
| WO2023059477A1 (en) | 2023-04-13 |
| EP4159803A1 (en) | 2023-04-05 |
| TW202323458A (zh) | 2023-06-16 |
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