TW201720899A - 水性聚合物乳液及由其形成之水性黏著劑組合物 - Google Patents
水性聚合物乳液及由其形成之水性黏著劑組合物 Download PDFInfo
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Abstract
本發明提供一種水性聚合物乳液,其包括:i)按聚合物之總乾重計,20乾重%至80乾重%之乙酸乙烯酯作為聚合單元;ii)按聚合物之總乾重計,20乾重%至80乾重%之α,β-烯系不飽和羧酸酯單體作為聚合單元;iii)按聚合物之總乾重計,0.1乾重%至5乾重%之穩定劑單體作為聚合單元;iv)按聚合物之總乾重計,0.05乾重%至1乾重%之界面活性劑,其中所述水性聚合物乳液之黏度小於100cps。本發明亦提供一種包括所述水性聚合物乳液之水性黏著劑組合物。
Description
本發明係關於水性聚合物乳液。本發明亦係關於含有此類水性聚合物乳液之水性黏著劑組合物,其用於層壓物、紡織物及不織布纖維。
水性乙酸乙烯酯聚合物乳液在黏著劑工業中廣泛用作黏合劑,此係因為其與丙烯酸乳液相比相對便宜。乙酸乙烯酯具有高水溶性,高單體-聚合物膨脹比率及高鏈轉移常數。然而,在黏著劑中使用乙酸乙烯酯單體可能損害聚合物乳液之乳液儲存穩定性。通常,此問題可藉由以下來解決:藉由增加所添加界面活性劑之量,或藉由向乙酸乙烯酯聚合物乳液中添加諸如聚乙烯醇(「PVOH」)及羥乙基(「HEC」)之保護性膠體以提供所需穩定性。然而,添加高含量之界面活性劑不經濟,且可能對乳液水敏感性具有負面作用,其可能引起在黏著劑中發泡以及使黏著效能(諸如黏結強度)劣化。添加保護性膠體亦可能導致高乳液黏度。
因此,期望提供具有低黏度及可接受之乳液儲存穩定性的水性乙酸乙烯酯聚合物乳液,及具有可接受之黏著
效能(諸如黏結強度及熱密封強度)的含有此類水性乙酸乙烯酯聚合物乳液之水性黏著劑組合物。
本發明提供一種具有低黏度及可接受之乳液儲存穩定性的新穎水性乙酸乙烯酯聚合物乳液,及一種具有可接受之黏著效能(諸如黏結強度及熱密封強度)的含有此類水性乙酸乙烯酯聚合物乳液之水性黏著劑組合物。
在本發明之第一態樣中,提供一種水性聚合物乳液,其包括:i)按聚合物之總乾重計,20乾重%至80乾重%之乙酸乙烯酯作為聚合單元;ii)按聚合物之總乾重計,20乾重%至80乾重%之α,β-烯系不飽和羧酸酯單體作為聚合單元;iii)按聚合物之總乾重計,0.1乾重%至5乾重%之穩定劑單體作為聚合單元;iv)按聚合物之總乾重計,0.05乾重%至1乾重%之界面活性劑,其中所述水性聚合物乳液之黏度小於100cps。
在本發明之第二態樣中,提供一種水性黏著劑組合物,其包括所述水性聚合物乳液。
一種水性聚合物乳液,其包括按聚合物之總乾重計,20乾重%至80乾重%、較佳30乾重%至55乾重%、且更佳35乾重%至50乾重%之乙酸乙烯酯作為聚合單元。
所述水性聚合物乳液進一步包括按聚合物之總
乾重計,20乾重%至80乾重%、較佳45乾重%至70乾重%、且更佳50乾重%至65乾重%之α,β-烯系不飽和羧酸酯單體作為聚合單元。
α,β-烯系不飽和羧酸酯單體之適合實例包含(甲基)丙烯酸酯單體,亦即甲基丙烯酸酯或丙烯酸酯單體,諸如丙烯酸甲酯、丙烯酸乙酯、丙烯酸丁酯、丙烯酸2-乙基己酯、丙烯酸癸酯、丙烯酸月桂酯、甲基丙烯酸甲酯、甲基丙烯酸丁酯、甲基丙烯酸異癸酯、甲基丙烯酸月桂酯、丙烯酸2-羥基丁酯、甲基丙烯酸2-羥乙酯及甲基丙烯酸2-羥基丙酯;衣康酸酯(itaconic ester)單體,諸如衣康酸二甲酯、衣康酸二丁酯;及順丁烯二酸酯,順丁烯二酸二辛酯;較佳地,α,β-烯系不飽和羧酸酯單體為丙烯酸乙酯、甲基丙烯酸甲酯、丙烯酸丁酯、丙烯酸2-乙基己酯及其任何組合。更佳地,α,β-烯系不飽和羧酸酯單體為丙烯酸丁酯、丙烯酸2-乙基己酯及其任何組合。
水性聚合物乳液進一步包括按聚合物之總乾重計,0.1乾重%至5乾重%、較佳0.1乾重%至2.5乾重%、且更佳0.1乾重%至1.5乾重%之穩定劑單體作為聚合單元。
穩定劑單體之適合實例包含苯乙烯磺酸鈉、乙烯基磺酸鈉、2-丙烯醯胺基-2-甲基丙磺酸、丙烯醯胺、丙烯酸、甲基丙烯酸、衣康酸及其任何組合。
水性聚合物乳液可進一步包括除乙酸乙烯酯以外之乙烯酯單體。乙烯酯單體之適合實例包含丙酸乙烯酯、新壬酸乙烯酯、新癸酸乙烯酯、2-乙基己酸乙烯酯、特戊酸乙烯酯、柯赫酸乙烯酯及其任何組合。
水性聚合物乳液之玻璃轉移溫度(「Tg」)為8℃至-43℃,較佳-14℃至-32℃,且更佳-23℃至-30℃。本文中之Tg使用福克斯等式(Fox Equation)來計算(T.G.Fox,《美國物理學會公報(Bull.Am.Physics Soc.)》,第1卷,第3期,第123頁(1956))。
水性聚合物乳液之固體含量為30%至60%。其較佳為35%至50%,且更佳為41%至45%。
如藉由博勒飛公司(Brookfield)LVT圓盤刻度黏度計(在60rpm下,2號軸)所量測,水性聚合物乳液之黏度小於100cps,較佳小於50cps,且更佳小於30cps。
水性聚合物乳液之粒度為150nm至500nm,且較佳250nm至350nm。
較佳地,按聚合物之總重量計,水性聚合物乳液之粗粒度小於0.2重量%,較佳小於0.02重量%,且更佳小於0.01重量%。藉由經由325目過濾器過濾200g水性聚合物乳液,且隨後乾燥及稱重經乾燥之粗粒來測定粗粒度。
本文所用之聚合方法可使用已知用於製備水性乳液聚合物之方法來進行。
水性聚合物乳液進一步包括按聚合物之總乾重計,0.05乾重%至1乾重%、較佳0.05乾重%至0.5乾重%、且更佳0.05乾重%至0.3乾重%之界面活性劑作為乳化劑。
界面活性劑較佳為陰離子型界面活性劑與非離子型界面活性劑之組合,其中離子型界面活性劑與非離子型界面活性劑之莫耳比為0.5至20、較佳1至10、且更佳2至5。
陰離子型界面活性劑之適合實例包含硫酸鹽、磺酸鹽、磷酸鹽、羧酸鹽及其任何組合。較佳地,陰離子型界面活性劑為磺酸鹽,諸如十二烷基苯磺酸鈉、十二烷基磺酸鈉、十二烷基二苯醚二磺酸鈉、正癸基二苯醚二磺酸鈉、十二烷基苯磺酸異丙胺及己基二苯醚二磺酸鈉。更佳地,陰離子型界面活性劑為十二烷基苯磺酸鈉。
非離子型界面活性劑之適合實例包含聚氧乙烯化之烷基酚、聚氧乙烯化之醇、環氧乙烷-環氧丙烷嵌段共聚物、聚氧乙烯化之脂肪酸酯。較佳地,非離子型界面活性劑為具有如RO-(CH2CH2O)nH之通用分子的聚氧乙烯化之醇,其中R為烷基。更佳地,烷基R為C12-C18,且氧亞乙基-(CH2CH2O)-大於20。可商購之非離子型界面活性劑包含來自陶氏化學公司(The Dow Chemical Company)之TERGITOLTM 15-S-40。
較佳地,本發明之水性聚合物乳液不包含保護性膠體。保護性膠體可為(1)天然或經改質之天然產物,諸如瓊脂膠、阿拉伯膠、黃蓍膠、水溶性澱粉、果膠、明膠及海藻酸鹽,及經改質之纖維素,諸如羥乙基纖維素及羧甲基纖維素;或(2)合成產物,諸如水解程度為70至100mol%之聚乙烯醇。
藉由黏著劑領域中熟知之技術製備包括所述水性聚合物乳液之水性黏著劑組合物。視情況,此類黏著劑組合物可包括其他水、乳膠黏合劑、交聯劑及添加劑,諸如流變改質劑、殺生物劑、潤濕及消泡劑。較佳地,水性黏著劑組合物不包含在製備水性黏著劑組合物期間進一步添加任何
界面活性劑。
將水性黏著劑組合物施用於普通基板(諸如雙軸定向之聚丙烯膜、聚酯膜或耐綸膜)之表面上,且經乾燥以形成乾燥層。當剩餘水小於所施用之黏著劑組合物的10%時,所施用之黏著劑組合物視為乾燥的。
在所施用黏著劑組合物之乾燥層上覆蓋真空金屬化之流延聚丙烯膜、流延聚丙烯膜或聚乙烯膜,以使得形成雙軸定向的聚丙烯膜/黏著劑/真空金屬化之流延聚丙烯膜複合物(複合膜,且亦稱為層壓物)。層壓物較佳經受機械力以將膜按壓得甚至更緊密。此類機械力較佳藉由使層壓物在輥之間通過來施加。較佳地,輥經加熱。
在本發明中,除非另外指示,否則各較佳技術解決方案及更佳技術解決方案中之技術特徵可彼此組合以形成新技術解決方案。為簡潔起見,說明書略去對此等組合之描述。然而,藉由組合此等技術特徵而獲得之所有技術解決方案應視為在字面上以明確方式描述於本發明說明書中。
I. 原材料:
II. 測試方法
1. 乳液儲存穩定性(穩定性)
記錄新鮮聚合物乳液樣品之pH值、固體含量、黏度及粗粒度。隨後,將新鮮聚合物乳液樣品中之每一者傾入至250ml玻璃瓶中,不在乳液表面頂部留下自由空間。接著用圍繞蓋子的其他膠帶恰當地密封瓶子。將經密封之瓶子置於50℃烘箱中,且老化一段時間,接著取出且在室溫中冷卻。再次量測經老化之聚合物乳液樣品的pH值、固體含量(頂部及底部)及黏度,且進一步觀測其膠凝、出現粗粒或分離。亦記錄在烘箱中老化之時間。
2. 黏結強度
將由黏著劑組合物製備之層壓物切成15mm寬之條帶,以便使用可購自英斯特朗公司(Instron Corporation)之5940系列單管柱台面系統在250mm/min十字頭速度下進
行T剝離測試。在測試期間,由手指略微牽拉各條帶之尾部以確保尾部與剝離方向保持90度。各樣品測試三個條帶且計算平均值。結果以N/15mm為單位。值愈高,則黏結強度愈佳。
3. 熱密封強度
將由黏著劑組合物製備之層壓物在可購自Brugger Company之HSG-C熱密封機中在140℃密封溫度及300N壓力下熱密封1秒,接著冷卻且切成15mm寬之條帶,以便使用可購自英斯特朗公司之5940系列單管柱台面系統在250mm/min十字頭速度下進行熱密封強度測試。各樣品測試三個條帶且計算平均值。結果以N/15mm為單位。值愈高,則熱密封強度愈佳。
III. 實例
1. 製備水性聚合物乳液
本發明實例1:
單體乳液製備:在聚合之前,藉由向攪拌溶液中緩慢添加435.0g去離子水、9.6g DS-4、11.5g V3525、854.5g BA、36.0g AA及548.0g VA來製備乳化之單體混合物。
聚合:將含有0.9g碳酸氫鈉及730.0g去離子水之溶液置放於配備有熱電偶、冷凝器及攪拌器之5頸5公升圓底燒瓶中,且在氮氣下將其加熱至74℃。向燒瓶中裝入含0.01g FeSO4、0.01g EDTA四鈉鹽、3.2g APS及28.7g執行種子(perform seed)之51.0g去離子水。當溫度處於74℃下時,在210分鐘內饋入單體混合物以及3.2g APS溶解於148.0g去離子水中及0.7g IAA溶解於148.0g去離子水中之共饋
料溶液。將聚合反應溫度維持在73℃-75℃下。在添加完成後,使反應混合物冷卻至70℃,隨後在45分鐘內,在攪拌下逐步添加3.0g t-BHP(70%活性物含量)於28.2g去離子水中及2.3g SBS溶解於28.2g去離子水中之溶液。在饋料完成後,使反應物冷卻至室溫。接著在30分鐘內逐滴添加含6.8g Na2CO3之78.2g去離子水以將pH值調節至6.0-8.0。接著,在30分鐘內,在攪拌下添加0.11g KATHONTM LX殺生物劑。添加恰當量之去離子水以將最終固體調節至42%-45%。
本發明實例2-8:
藉由使用為本發明實例1所概述之程序來製備聚合物乳液。單體乳液之重量詳述於表1中。
比較實例1:
單體乳液製備:在聚合之前,藉由向攪拌溶液中緩慢添加435.0g去離子水、9.6g DS-4、0.9g 15-S-40、11.5
g V3535、883.1g BA、14.4g AA及540.8g VA來製備乳化之混合物。
聚合:將含有0.9g碳酸氫鈉及587.3g去離子水之溶液置放於配備有熱電偶、冷凝器及攪拌器之5頸5公升圓底燒瓶中,且在氮氣下將其加熱至74℃。裝入分散於143.6g熱水中之7.18g HEC。向鍋中裝入含0.01g FeSO4、0.01g EDTA四鈉鹽、3.2g APS及28.7g執行種子之51.0g去離子水。當溫度處於74℃下時,在210分鐘內饋入單體乳液以及3.2g APS溶解於148.0g去離子水中及0.7g IAA溶解於148.0g去離子水中之共饋料溶液。將聚合反應溫度維持在73℃-75℃下。在添加完成後,使反應混合物冷卻至70℃,隨後在45分鐘內,在攪拌下逐步添加3.0g t-BHP(70%活性物含量)於28.2g去離子水中及2.3g SBS溶解於28.2g去離子水中之溶液。在饋料完成後,使反應物冷卻至室溫。在30分鐘內逐滴添加6.8g Na2CO3於78.2g水中之溶液以將pH值調節至6.0~8.0。接著在攪拌30分鐘下添加0.11g KATHONTM LX殺生物劑。添加恰當量之去離子水以將最終固體調節至42%-45%。
比較實例2:
單體乳液製備:在聚合之前,藉由向攪拌溶液中緩慢添加435.0g去離子水、9.6g DS-4、0.9g 15-S-40、11.5g V3535、883.1g BA、14.4g AA及540.8g VA來製備乳化之單體混合物。
聚合:將含有0.9g碳酸氫鈉及605.0g去離子水之溶液置放於配備有熱電偶、冷凝器及攪拌器之5頸5公升圓底燒瓶中,且在氮氣下將其加熱至74℃。裝入分散於125.0g
熱水中之14.6g PVOH。向鍋中裝入含0.01g FeSO4、0.01g EDTA四鈉鹽、3.2g APS及28.7g執行種子之51.0g去離子水。當溫度處於74℃下時,在210分鐘內饋入單體乳液以及3.2g APS溶解於148.0g去離子水中及0.7g IAA溶解於148.0g去離子水中之共饋料溶液。將聚合反應溫度維持在73℃-75℃下。在添加完成後,使反應混合物冷卻至70℃,隨後在45分鐘內,在攪拌下逐步添加3.0g t-BHP(70%活性物含量)於28.2g去離子水中及2.3g SBS溶解於28.2g去離子水中之溶液。在饋料完成後,使反應物冷卻至室溫。在30分鐘內逐滴添加6.8g Na2CO3於78.2g水中之溶液以將pH值調節至6.0~8.0。接著在攪拌30分鐘下添加0.11g KATHONTM LX殺生物劑。添加恰當量之去離子水以將最終固體調節至42%-45%。
比較實例3:
單體乳液製備:在聚合之前,藉由向攪拌溶液中緩慢添加435.0g去離子水、51.2g DS-4、15.8g 15-S-40、11.5g V3535、789.8g BA、14.4g AA及634.5g VA來製備乳化之單體混合物。
聚合:將含有0.9g碳酸氫鈉及730.0g去離子水之溶液置放於配備有熱電偶、冷凝器及攪拌器之5頸5公升圓底燒瓶中,且在氮氣下將其加熱至74℃。向鍋中裝入含0.01g FeSO4、0.01g EDTA四鈉鹽、3.2g APS及28.7g執行種子之51.0g去離子水。當溫度處於74℃下時,在210分鐘內饋入單體乳液以及3.2g APS溶解於148.0g去離子水中及0.7g IAA溶解於148.0g去離子水中之共饋料溶液。將聚合反應溫度維持在73℃-75℃下。在添加完成後,使反應混合物冷卻至
70℃,隨後在45分鐘內,在攪拌下逐步添加3.0g t-BHP(70%活性物含量)於28.2g去離子水中及2.3g SBS溶解於28.2g去離子水中之溶液。在饋料完成後,使反應物冷卻至室溫。在30分鐘內逐滴添加6.8g Na2CO3於78.2g水中之溶液以將pH值調節至6.0~8.0。接著在攪拌30分鐘下添加0.11g KATHONTM LX殺生物劑。添加恰當量之去離子水以將最終固體調節至42%-45%。
本發明實例1至8及比較實例1至3中之界面活性劑、保護性膠體、穩定劑單體、乙酸乙烯酯及α,β-烯系不飽和羧酸酯單體的重量百分比詳述於表2中。
2. 製備水性黏著劑組合物
以上水性聚合物乳液不經進一步調配即用作水性黏著劑組合物。
3. 製備層壓物
BOPP及VMCPP膜不經任何預處理即使用。將黏著劑塗佈在BOPP上,乾燥,且與VMCPP膜組合,獲得黏著劑塗層重量以乾重計為1.8g/m2之BOPP/黏著劑/VMCPP膜複合物。隨後,使經組合之BOPP/黏著劑/VMCPP膜複合物在50℃固化1天。
IV. 施用效能測試結果
如表3所說明,本發明實例1至8之所有水性聚合物乳液滿足效能要求,且展現良好乳液儲存穩定性(大於1個月)及低黏度(小於100cps)。分別使用HEC或PVOH作為保護性膠體的比較實例1及比較實例2之水性聚合物乳液兩者展現高黏度(大於300cps)及不良乳液儲存穩定性(粗粒度大於1%)。儘管比較實例4(RovaceTM黏合劑662)展現良好乳液儲存穩定性,但黏度(大於300cps)高於所期望的小於100cps之效能要求,此係歸因於高界面活性劑含量及所添加之保護性膠體。
如表4所說明,由包括本發明實例3至5之水性聚合物乳液的水性黏著劑組合物製備之層壓物展現良好黏結強度(大於1.0N/15nm)及熱密封強度(大於10N/15nm)黏著劑效能。尤其,本發明實例5展示與用作效能目標基準
之比較實例5(由苯乙烯-丙烯酸乳液製備之RobondTM黏合劑L-70D)相當的經優化效能。儘管比較實例3之水性聚合物乳液展現良好穩定性及低黏度,但由包括比較實例3之水性聚合物乳液的水性黏著劑組合物製備之層壓物的黏結強度(小於0.5N/nm)由於高界面活性劑含量而比本發明實例3至5低得多。
Claims (12)
- 一種水性聚合物乳液,其包括:i)按所述聚合物之總乾重計,20乾重%至80乾重%之乙酸乙烯酯作為聚合單元;ii)按所述聚合物之總乾重計,20乾重%至80乾重%之α,β-烯系不飽和羧酸酯單體作為聚合單元;iii)按所述聚合物之總乾重計,0.1乾重%至5乾重%之穩定劑單體作為聚合單元;iv)按所述聚合物之總乾重計,0.05乾重%至1乾重%之界面活性劑,其中所述水性聚合物乳液之黏度小於100cps。
- 如申請專利範圍第1項之水性聚合物乳液,其中所述水性聚合物乳液之所述黏度小於50cps。
- 如申請專利範圍第1項之水性聚合物乳液,其中所述水性聚合物乳液之所述黏度小於30cps。
- 如申請專利範圍第1項之水性聚合物乳液,其中所述水性聚合物乳液包括按所述聚合物之總乾重計,0.05乾重%至0.5乾重%之界面活性劑。
- 如申請專利範圍第1項之水性聚合物乳液,其中所述界面活性劑為陰離子型界面活性劑與非離子型界面活性劑之組合,其中離子型界面活性劑與非離子型界面活性劑之莫耳比為0.5至20。
- 如申請專利範圍第1項之水性聚合物乳液,其中所述水性聚合物乳液不包括保護性膠體。
- 如申請專利範圍第1項之水性聚合物乳液,其中所述水性 聚合物乳液之玻璃轉移溫度為8℃至-43℃。
- 如申請專利範圍第1項之水性聚合物乳液,其中所述水性聚合物乳液之玻璃轉移溫度為-23℃至-30℃。
- 如申請專利範圍第1項之水性聚合物乳液,其中所述水性聚合物乳液之粒度為150nm至500nm。
- 如申請專利範圍第1項之水性聚合物乳液,其中所述α,β-烯系不飽和羧酸酯單體為(甲基)丙烯酸酯單體。
- 如申請專利範圍第1項之水性聚合物乳液,其中所述水性聚合物乳液進一步包括除乙酸乙烯酯以外之乙烯酯單體。
- 一種水性黏著劑組合物,其包括如申請專利範圍第1項至第11項中任一項之水性聚合物乳液。
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CN105086886B (zh) * | 2015-09-23 | 2017-05-10 | 广州宏昌胶粘带厂 | 单组分自交联型耐高温乳液压敏胶及其制备方法和应用 |
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2015
- 2015-12-08 EP EP15909989.4A patent/EP3387029B1/en active Active
- 2015-12-08 BR BR112018009945-7A patent/BR112018009945B1/pt active IP Right Grant
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- 2015-12-08 WO PCT/CN2015/096614 patent/WO2017096514A1/en active Application Filing
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US10975273B2 (en) | 2021-04-13 |
EP3387029A1 (en) | 2018-10-17 |
RU2018122476A3 (zh) | 2019-12-20 |
JP2019504132A (ja) | 2019-02-14 |
CN108290986B (zh) | 2023-11-28 |
JP6849679B2 (ja) | 2021-03-24 |
AR106828A1 (es) | 2018-02-21 |
EP3387029B1 (en) | 2021-10-20 |
RU2018122476A (ru) | 2019-12-20 |
RU2754556C2 (ru) | 2021-09-03 |
MX2018006262A (es) | 2018-11-09 |
TWI791421B (zh) | 2023-02-11 |
CN108290986A (zh) | 2018-07-17 |
WO2017096514A1 (en) | 2017-06-15 |
EP3387029A4 (en) | 2019-07-03 |
BR112018009945B1 (pt) | 2022-01-04 |
US20180298247A1 (en) | 2018-10-18 |
BR112018009945A2 (pt) | 2018-11-06 |
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