TW201546201A - 用於容器塗層之丙烯酸水性分散體 - Google Patents
用於容器塗層之丙烯酸水性分散體 Download PDFInfo
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Classifications
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
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Abstract
本發明揭示可在用於塗佈食品及飲料容器之塗層組合物中使用之丙烯酸水性分散體。該水性分散體係以下各項之反應產物:(a)疏水性乙烯基加成聚合物,其含有側鏈或末端乙烯系不飽和基團,(b)乙烯基單體混合物,其包含含有羧酸基團之乙烯基單體;該反應產物含有活性氫基團且係用鹼至少部分地中和並分散於水性介質中;該水性分散體實質上不含雙酚A及其衍生物。
Description
本發明係關於包括疏水性部分及親水性部分之接枝丙烯酸聚合物之水性分散體以及此類分散體在容器塗層中之用途。
各種塗層已用於塗佈食品及飲料容器之表面。舉例而言,有時使用卷材塗佈或片材塗佈操作塗佈金屬罐,亦即,用適合組合物塗佈適合基板(例如,鋼或鋁)之平面或卷材或片材並進行固化。經塗佈基板然後形成為罐主體或罐端部。另一選擇係,可例如藉由噴塗、浸塗及滾動塗佈將塗層組合物施加至經成形罐且然後進行固化。用於食品及飲料容器之塗層應較佳地能夠高速施加至基板並在固化時提供必要性質以在需要之最終用途中執行。舉例而言,塗層對食品接觸而言應係安全的並具有對基板之優異附著力。
用於食品及飲料容器之塗層組合物中之諸多者基於係雙酚A之聚縮水甘油醚之環氧樹脂。雙酚A在包裝塗層中作為雙酚A本身(BPA)或其衍生物(諸如,雙酚A之二縮水甘油醚(BADGE)、環氧酚醛清漆樹脂及用雙酚A及雙酚F製備之多元醇)係成問題的。儘管迄今為止可得之科學證據之權衡指示可自現有塗層釋放之小微量之BPA或BADGE不對人類造成健康風險,但此等化合物仍然被某些人認為對人體健康有害。因此,強烈希望消除來自用於食品及飲料容器之塗層之此等化合
物。因此,需要一種不含有可抽提量之BPA、BADGE或BPA之其他衍生物且具有優異性質(諸如,對基板之優異黏著力)之用於食品或飲料容器之包裝塗層組合物。
本發明提供一種物品,其包括食品或飲料罐之主體部分或端部部分以及安置在其上之塗層組合物,其中該塗層組合物包括水性分散體,該水性分散體包括以下各項之反應產物:(a)疏水性乙烯基加成聚合物,含有側鏈乙烯系不飽和基團,(b)乙烯基單體混合物,其包含含有羧酸基團之乙烯基單體;該反應產物含有活性氫基團且係用鹼至少部分地中和並分散於水性介質中;該水性分散體實質上不含雙酚A及其衍生物。
本發明進一步提供一種方法,其包括:(a)提供包括上述水性分散體之塗層組合物,(b)在將金屬基板形成為食品或飲料罐或其部分之前或之後將該塗層組合物施加至該金屬基板。
除非另有明確說明,否則本文中所用之所有數字(諸如,表達值、範圍、數量或百分比之數字)可以如同以詞「約」開始一樣來理解,即使該術語並未明確出現。此外,應注意複數術語及/或片語涵蓋其單數等效物,且反之亦然。舉例而言,「一個」聚合物、「一個」交聯劑及任何其他組分係指此等組分中之一或多者。
當涉及值之任一數值範圍時,此等範圍被理解為包含所述範圍最小值與最大值之間的任何及所有數及/或分數。
本文中所用之術語「聚合物」廣義上係指寡聚物以及均聚物與
共聚物兩者。術語「樹脂」可與「聚合物」互換使用。
除非另有清楚指出,否則術語「丙烯酸」與「丙烯酸酯」可互換使用(除非這樣做將更改所意欲之含義)且包含丙烯酸、酐,以及其衍生物,諸如其C1-C5烷基酯、較低烷基取代丙烯酸,例如C1-C2取代丙烯酸,諸如甲基丙烯酸、乙基丙烯酸等,以及其C1-C4烷基酯。術語「(甲基)丙烯酸」或「(甲基)丙烯酸酯」意欲涵蓋所指示材料(例如,(甲基)丙烯酸酯單體)之丙烯酸/丙烯酸酯以及甲基丙烯酸/甲基丙烯酸酯形式兩者。術語「(甲基)丙烯酸聚合物」係指自一或多個(甲基)丙烯酸單體製備之聚合物。
術語「酸」包含酸性鹽。
術語「食品」包含食品及飲料兩者。
術語「疏水性乙烯基加成聚合物」意指不可與胺自分散於水中之聚合物。
本文中所用之分子量係藉由凝膠滲透層析法使用聚苯乙烯標準而判定。除非另有指出,否則分子量係以數均為基礎。
疏水性乙烯基加成聚合物係自包含提供側鏈或末端乙烯系不飽和基團之乙烯基單體之乙烯基單體混合物製備。此類單體之實例係含有不同反應性(例如,(甲基)丙烯酸酯官能度及(甲基)烯丙基官能度)之兩個或兩個以上乙烯系不飽和基團之單體。此類單體之實例係(甲基)丙烯酸(甲基)烯丙基酯,諸如丙烯酸烯丙基酯及甲基丙烯酸烯丙基酯。含有(甲基)丙烯酸酯不飽和及較小反應性乙烯系不飽和之其他單體之實例係大分子單體,諸如(甲基)丙烯酸羥烷基酯(諸如,(甲基)丙烯酸羥乙基酯)與α、β-乙烯系不飽和二羧酸(諸如,馬來酸或酐及衣康酸)之縮合物。
提供側鏈或末端乙烯系不飽和之乙烯基單體以基於(a)中之乙烯基單體之總重量之5重量%至40重量%(諸如,10重量%至30重量%)之
量存在於(a)中之乙烯基單體混合物中。
(a)之乙烯基單體混合物中之其他乙烯基單體可係乙烯基芳香族單體(諸如,苯乙烯及乙烯基甲苯)、在羥烷基基團中含有自2至4個碳原子之(甲基)丙烯酸羥烷基酯(諸如,(甲基)丙烯酸羥乙基酯及(甲基)丙烯酸羥丁基酯)。(甲基)丙烯酸羥烷基酯通常以基於在(a)之製備中使用之乙烯基單體之總重量之20重量%至60重量%(諸如30重量%至50重量%)之量存在於(a)中。
疏水性乙烯基加成聚合物(a)通常具有自3000至50000(諸如,10000至40000)之數均分子量,以及5000至20000(諸如7000至15000)之側鏈或末端乙烯系不飽和基團當量。
疏水性乙烯基加成聚合物以基於在(a)及(b)製備中使用之單體之總重量之30重量%至80重量%(諸如,50重量%至70重量%)之量存在於水性分散體。
疏水性乙烯基加成聚合物(a)係使用在有機溶劑中執行之已知自由基聚合方法而製備。適合溶劑之實例係醇類,諸如正丁醇、異丙醇及二醇單烷基醚,諸如2-丁氧基乙醇,包含其混合物。自由基引發劑之實例包含過氧化物、過酸酯及偶氮二甲腈(azobiscarbonitrile)。具體實例係三級丁基過氧化物、過辛酸三級丁酯(t-butyl peroctoate)及2,2'-偶氮二(2-甲基異丁腈)。通常,將單體混合物及引發劑在80℃至150℃之聚合溫度下經約0.5小時至3小時添加至反應器皿。
如上所述,包含含有羧酸基團之乙烯基單體之乙烯基單體的混合物與疏水性乙烯基加成聚合物反應。含有羧酸基團之單體之實例係(甲基)丙烯酸、衣康酸及丁烯酸。此等單體通常以基於存在於乙烯基單體混合物(b)中之乙烯基單體之總重量之20重量%至60重量%的量使用。其他單體通常包含於(b)之乙烯基單體混合物中。實例包含乙烯基芳香族單體(諸如,苯乙烯及乙烯基甲苯),以及在烷基基團中含有
自1至12個碳原子之(甲基)丙烯酸之烷基酯。具體實例包含(甲基)丙烯酸甲基酯、(甲基)丙烯酸乙基酯、(甲基)丙烯酸丁基酯及(甲基)丙烯酸月桂基酯。
通常藉由將如上所述具有自由基引發劑之乙烯基單體(b)之混合物添加至溶解或分散於有機溶劑中之疏水性乙烯基加成聚合物(諸如,如上所述者)來得到(a)與(b)之反應產物。反應之時間及溫度一般而言係如上所述的。
(a)與(b)之相對量通常在50%至80%之(a)與20%至50%之(b)之範圍內,該等百分比係以基於(a)與(b)之總重量計。
反應產物通常具有5,000至70,000(諸如,15,000至50,000)之數均分子量,以及40至200(諸如,60至120)之酸值。通常,該反應產物含有諸如羥基之活性氫,且具有80至200(諸如,100至150)之羥基值。羥基值及酸值係基於反應產物之樹脂固體。
反應產物通常藉由以下步驟分散於水性介質中:將該反應產物添加至含有諸如氫氧化鈉之鹼基或諸如二甲基乙醇胺之三級胺之水以至少部分地中和羧酸基團。分散體之pH通常自8至10。分散體具有基於分散體之總重量之自10重量%至50重量%之樹脂固體含量。
本發明之水性聚合物分散體係穩定液體系統。其形成膜,且因而可用作用於塗佈諸如食品罐之容器之經著色及未經著色塗層組合物之黏合劑。
用於容器塗層之塗層組合物通常藉助於與形成膜之聚合物之官能基團反應之固化劑而配製。
通常,固化劑係酚醛塑膠或酚-甲醛樹脂以及胺基塑膠或三嗪-甲醛樹脂。酚-甲醛樹脂較佳地具有可溶性酚醛樹脂類型。適合酚類之實例係酚自身、丁基酚、二甲酚及甲酚。經常使用通常用丁醇醚化之甲酚-甲醛樹脂。對於酚醛樹脂製備中之化學,參考「The Chemistry
and Application of Phenolic Resins or Phenolplasts」,第V卷,第I部分,Dr.Oldring編輯;John Wiley & Sons/Cita Technology Limited,London,1997。市售之酚醛樹脂之實例係PHENODUR® PR285及BR612以及在商標BAKELITE®下售賣之彼等樹脂(通常係BAKELITE 6581LB)。
胺基塑膠樹脂之實例係彼等藉由將諸如三聚氰胺或苯井胍胺之三嗪與甲醛反應而形成者。較佳地,此等縮合物通常用甲醇、乙醇及丁醇(包含其等之混合物)醚化。對於胺基塑膠樹脂之化學製備及使用,參見「The Chemistry and Applications of Amino Crosslinking Agents or Aminoplast」,第V卷,第II部分,第21頁及其後,Dr.Oldring編輯;John Wiley & Sons/Cita Technology Limited,London,1998。此等樹脂在商標MAPRENAL®下(諸如,MAPRENAL MF980)以及在商標CYMEL®下(諸如,CYMEL 303及CYMEL 1128)市售,可自Cytec Industries獲得。
通常,形成膜之聚合物係以30重量%至95重量%(諸如70重量%至90重量%)之量使用,且交聯劑以5重量%至70重量%(諸如10重量%至30重量%)之量存在,該等重量百分比係基於塗層組合物中之總樹脂固體重量。
塗層組合物可含有諸如聚酯多元醇、聚醚多元醇及聚胺基甲酸酯多元醇之佐劑樹脂,以最大化所得之塗層之某些性質。當存在時,佐劑樹脂係以基於塗層組合物之樹脂固體重量之高達50重量%(通常2重量%至50重量%)之量使用。
通常存在於塗層組合物中之另一選用成分係觸媒以增加塗層組合物之固化或交聯之速率。一般而言,可使用酸觸媒且其通常以約0.05重量%至5重量%之量存在。適合觸媒之實例係十二烷基苯磺酸、甲磺酸、對甲苯磺酸、二壬基萘二磺酸及苯膦酸。已發現本發明之塗
層組合物中之酸觸媒的量由於存在磷酸與環己烷二甲醇之聚縮水甘油醚之反應產物而不如正常情況下期望的大。此反應產物係酸性的且已發現貢獻於塗層組合物之固化。
亦可使用藉由將潤滑力施加至在形成容器中使用之經塗佈金屬基板之片材促進金屬容器之製造之潤滑劑。潤滑劑之實例包含巴西棕櫚蠟及聚乙烯類型之潤滑劑。若使用,則潤滑劑較佳地以基於塗層組合物中之樹脂固體之重量的至少0.1重量%存在於塗層組合物中。
另一有用的選用成分係顏料,諸如二氧化鈦。若使用,則顏料以基於塗層組合物中之固體總重量之不大於70重量%(較佳地不大於40重量%)之量存在於塗層組合物中。
表面活性劑可包含於塗層組合物中以輔助流動及基板之潤濕。
適合表面活性劑之實例包含(但不限於)壬基酚聚醚及鹽。若使用,則表面活性劑以基於塗層組合物中之樹脂固體之重量的至少0.01%且不大於10%之量存在。
在本發明之實務中使用之組合物係實質上不含、可基本上不含以及可完全不含雙酚A及其衍生物或殘餘物,包含雙酚A(「BPA」)及雙酚A二縮水甘油醚(「BADGE」)。該等組合物有時被稱為「非故意BPA」,此乃因BPA(包括其衍生物或殘餘物)並非故意添加,但可因不可避免之環境污染而以痕量存在。該等組合物亦可實質上不含及可基本上不含以及可完全不含雙酚F及其衍生物或殘餘物,包含雙酚F及雙酚F二縮水甘油醚(「BPFG」)。在此內容脈絡下,所用術語「實質上不含」意指該等組合物含有小於1000百萬分率(ppm)上文所提及化合物、其衍生物或殘餘物中之任一者,「基本上不含」意指其小於100ppm,且「完全不含」意指其小於20十億分率(ppb)。
本發明之塗層組合物可施加至所有種類之容器且尤其良好地適用於在食品及飲料罐(例如,兩片式罐、三片式罐等)上使用。除食品
及飲料容器之外,該等塗層組合物亦可施加至用於噴霧劑應用(諸如,除臭劑及噴發膠)之容器。
兩片式罐係藉由接合罐主體(通常係經拉製金屬主體)與罐端部(通常係經拉製金屬端部)而製造。本發明之塗層適合在食品或飲料接觸情景中使用且可在此等罐之內側或外側上使用。其適用於噴塗施加、液體塗層、沖洗塗層、片材塗層、上覆式清漆塗層及側縫塗層。
噴塗塗佈包含將塗層組合物引入至預成形包裝容器之內側或外側中。適用於噴塗塗佈之典型預成形包裝容器包含食品罐、啤酒及飲料容器,以及諸如類似者。經噴塗預成形容器然後經受加熱以移除殘留溶劑並使塗層硬化。
卷材塗層闡述為由金屬(例如,鋼或鋁)組成之連續卷材之通常藉由滾動塗料施加之塗層。一旦經塗佈,塗層卷材便經受熱、紫外線及/或電磁固化短循環,以用於硬化(例如,乾燥及固化)塗層。卷材塗層提供可製作成經成形物品(諸如,兩片式拉製食品罐、三片式食品罐、食品罐端部、拉製及拉伸罐、飲料罐端部,以及諸如類似者)之經塗佈金屬(例如,鋼及/或鋁)基板。
沖洗塗層商業上闡述為具有保護劑塗料薄層之兩片式拉製及拉伸(「D&I」)罐之外部之塗層。此等D&I罐之外部係藉由使預成形兩片式D&I罐在塗層組合物之簾幕下通過而「經沖洗塗佈」。反轉罐,亦即,罐之敞開端部當通過簾幕時處於「向下」位置中。塗層組合物之此簾幕呈「瀑布狀」外觀。一旦此等罐在塗層組合物之此簾幕下通過,液體塗層材料有效地塗佈每一罐之外部。透過使用「空氣刀」移除多餘塗層。一旦所要量之塗料施加至每一罐之外部,每一罐通過熱、紫外線及/或電磁固化烘箱以硬化(例如,乾燥及固化)塗層。經塗佈罐在固化烘箱之界限內之滯留時間通常自1分鐘至5分鐘。此烘箱內之固化溫度將通常介於自150℃至220℃之範圍內。
片材塗層闡述為已預切割成正方形或矩形「片材」之多種材料(例如,鋼或鋁)之單獨片的塗層。此等片材之典型尺寸係大約一平方米。一旦經塗佈,便固化每一片材。一旦經硬化(例如,乾燥及固化),便聚集經塗佈基板之片材並準備用於後續製作。片材塗層提供可成功地製作成經成形物品(諸如,兩片式拉製食品罐、三片式食品罐、食品罐端部、拉製及拉伸罐、飲料罐端部,以及諸如類似者)之經塗佈金屬(例如,鋼或鋁)基板。
側縫塗佈闡述為液體塗料在經成形三片式食品罐之焊接區域上方之噴塗施加。當三片式食品罐處於製備中時,經塗佈基板之矩形片形成為圓柱體。圓柱體之成形由於矩形之每一側經由熱焊接之焊接而呈現為永久性的。一旦經焊接,每一罐通常需要液體塗料層,其保護經曝露「焊接部」免於對所含納之食品之後續腐蝕或其他效應。發揮此作用之液體塗層被稱為「側縫條紋」。典型側縫條紋係經噴塗施加且除小熱、紫外線及/或電磁烘箱之外亦經由來自焊接操作之殘餘熱而快速固化。
提供以下實例以輔助理解本發明,且該等實例不應被視為限制本發明之範疇。除非另有指出,否則所有份數及百分比均以重量計。
以下實例顯示水性分散體之製備,該水性分散體係自以下各項之反應產物製備:(a)具有側接乙烯系不飽和基團之疏水性乙烯基加成聚合物;(b)包含甲基丙烯酸之乙烯基單體混合物。該反應產物用胺部分地中和並分散於水中。
用43.67份數之正丁醇、143.29份數之2-丁氧基乙醇以及100.0份數之異丙醇裝載三公升圓底四頸燒瓶,該燒瓶配備有攪拌器、氮入口管、溫度計及回流冷凝器。逐漸地加熱燒瓶以在約98℃下回流。在聚
合期間維持該回流。在單獨器皿中,製備含有251.57份數之苯乙烯、201.59份數之甲基丙烯酸羥乙基酯、6.90份數之甲基丙烯酸烯丙基酯以及16.67份數之過辛酸三級丁酯之單體/引發劑混合物。在98℃下,將單體/引發劑混合物以穩定速率經2.5小時添加至反應器。當單體/引發劑混合物添加完成時,用添加至燒瓶之11.67份數之2-丁氧基乙醇沖洗單體/引發劑混合物器皿。將批料在98℃下保持30分鐘。在該固持之後,安裝迪安斯塔克裝置以及回流冷凝器。將批料溫度升高至128℃,且洗提出約91.88份數之異丙醇並將其聚集於迪安斯塔克裝置中。在洗提期間,在單獨器皿中,製備包括112.38份數之甲基丙烯酸、112.38份數之甲基丙烯酸正丁基酯、25.01份數之苯乙烯、6.13份數之過乙酸三級丁酯(50%水性溶液)、139.05份數之正丁醇及74.90份數之2-丁氧基乙醇之單體/引發劑/溶劑混合物。在洗提出異丙醇之後,移除迪安斯塔克裝置並將設置改變回筆直回流冷凝器。然後將單體/引發劑/溶劑混合物以穩定速率經2小時添加至反應器,同時將溫度維持在約128℃下。當單體/引發劑/溶劑混合物添加完成時,用其後添加至反應器之7.89份數之2-丁氧基乙醇沖洗單體/引發劑/溶劑混合物器皿。將批料在128℃下保持1小時。然後冷卻批料。當批料達到100℃時,經5分鐘裝載59.76份數之二甲基乙醇胺。然後經20分鐘裝載1001.15份數之DI水。此批料產出具有33.33% NV、0.119±0.026μm之粒子大小、15380厘泊之黏度以及15093之數均分子量之聚合物分散體。
以下實例類似於實例1,但用甲基丙烯酸羥丙基酯置換甲基丙烯酸羥乙基酯。
用43.67份數之正丁醇、143.29份數之2-丁氧基乙醇以及100.0份數之異丙醇裝載三公升圓底四頸燒瓶,該燒瓶配備有攪拌器、氮入口
管、溫度計及回流冷凝器。逐漸地加熱燒瓶以在約98℃下回流。在聚合期間維持該回流。在單獨器皿中,製備含有251.57份數之苯乙烯、201.59份數之甲基丙烯酸羥丙基酯、6.90份數之甲基丙烯酸烯丙基酯以及16.67份數之過辛酸三級丁酯之單體/引發劑混合物。在98℃下,將單體/引發劑混合物以穩定速率經2.5小時添加至反應器。當單體/引發劑混合物添加完成時,用添加至燒瓶之11.67份數之2-丁氧基乙醇沖洗單體/引發劑混合物器皿。將批料在98℃下保持30分鐘。在該固持之後,安裝迪安斯塔克裝置以及回流冷凝器。將批料溫度升高至128℃,且洗提出約83.75份數之異丙醇並將其聚集於迪安斯塔克裝置中。在洗提期間,在單獨器皿中,製備包括112.38份數之甲基丙烯酸、112.38份數之甲基丙烯酸正丁基酯、25.01份數之苯乙烯、6.13份數之過乙酸三級丁酯(50%水性溶液)、139.05份數之正丁醇以及74.90份數之2-丁氧基乙醇之單體/引發劑/溶劑混合物。在洗提出異丙醇之後,移除迪安斯塔克裝置並將設置改變回筆直回流冷凝器。然後將單體/引發劑/溶劑混合物以穩定速率經2小時添加至反應器,同時將溫度維持在約128℃下。當單體/引發劑/溶劑混合物添加完成時,用其後添加至反應器之7.89份數之2-丁氧基乙醇沖洗單體/引發劑/溶劑混合物器皿。將批料在128℃下保持1小時。然後冷卻批料。當批料達到100℃時,經5分鐘裝載59.76份數之二甲基乙醇胺然後經20分鐘裝載1001.15份數之DI水。此批料產出具有31.26% NV、0.117±0.025μm之粒子大小、6250厘泊之黏度以及14199之數均分子量之聚合物分散體。
以下實例類似於實例1,但在兩個聚合階段中使用同一溫度。
用43.67份數之正丁醇、143.29份數之2-丁氧基乙醇以及100.0份數之異丙醇裝載三公升圓底四頸燒瓶,該燒瓶配備有攪拌器、氮入口
管、溫度計及回流冷凝器。逐漸地加熱燒瓶以在約98℃下回流。在聚合期間維持該回流。在單獨器皿中,製備含有251.57份數之苯乙烯、201.59份數之甲基丙烯酸羥乙基酯、6.90份數之甲基丙烯酸烯丙基酯以及16.67份數之過辛酸三級丁酯之單體/引發劑混合物。在98℃下,將單體/引發劑混合物以穩定速率經2.5小時添加至反應器。當單體/引發劑混合物添加完成時,用添加至燒瓶之11.67份數之2-丁氧基乙醇沖洗單體/引發劑混合物器皿。將批料在98℃下保持30分鐘。在固持期間,在單獨器皿中,製備包括112.38份數之甲基丙烯酸、112.38份數之甲基丙烯酸正丁基酯、25.01份數之苯乙烯、6.13份數之過乙酸三級丁基(50%水性溶液)、139.05份數之正丁醇以及74.90份數之2-丁氧基乙醇之單體/引發劑/溶劑混合物。在固持之後,無需洗提異丙醇以升高溫度,然後將單體/引發劑/溶劑混合物以穩定速率經2小時添加至反應器,同時將溫度維持在約98℃下。當單體/引發劑/溶劑混合物添加完成時,用其後添加至反應器之7.89份數之2-丁氧基乙醇沖洗單體/引發劑/溶劑混合物器皿。將批料在98℃下保持1小時。然後冷卻批料且經5分鐘裝載59.76份數之二甲基乙醇胺。然後經20分鐘裝載1001.15份數之DI水。此批料產出具有31.43% NV、0.164±0.038μm之粒子大小、10280厘泊之黏度以及16719之數均分子量之聚合物分散體。
以下實例類似於實例1,但在聚合之兩個階段中使用甲基丙烯酸羥乙基酯。
用43.67份數之正丁醇、143.29份數之2-丁氧基乙醇以及100.0份數之異丙醇裝載三公升圓底四頸燒瓶,該燒瓶配備有攪拌器、氮入口管、溫度計及回流冷凝器。逐漸地加熱燒瓶以在約98℃下回流。在聚合期間維持該回流。在單獨器皿中,製備含有251.57份數之苯乙烯、201.59份數之甲基丙烯酸羥乙基酯、6.90份數之甲基丙烯酸烯丙基酯
以及16.67份數之過辛酸三級丁酯之單體/引發劑混合物。在98℃下,將單體/引發劑混合物經2.5小時裝載至反應器中。當單體/引發劑混合物添加完成時,用添加至燒瓶之11.67份數之2-丁氧基乙醇沖洗單體/引發劑混合物器皿。將批料在98℃下保持30分鐘。在該固持之後,安裝迪安斯塔克裝置以及回流冷凝器。將批料溫度升高至128℃,且洗提出約79.17份數之異丙醇並將其聚集於迪安斯塔克裝置中。在洗提期間,在單獨器皿中,製備包括112.38份數之甲基丙烯酸、91.93份數之甲基丙烯酸正丁基酯、20.46份數之苯乙烯、25.00份數之甲基丙烯酸羥乙基酯、6.13份數之過乙酸三級丁基(50%水性溶液)、139.05份數之正丁醇以及74.90份數之2-丁氧基乙醇之單體/引發劑/溶劑混合物。在洗提出異丙醇之後,移除迪安斯塔克裝置並將設置改變回筆直回流冷凝器。然後將單體/引發劑/溶劑混合物以穩定速率經2小時添加至反應器,同時將溫度維持在約128℃下。當單體/引發劑/溶劑混合物添加完成時,用其後添加至反應器之7.89份數之2-丁氧基乙醇沖洗單體/引發劑/溶劑混合物器皿。將批料在128℃下保持1小時。然後冷卻批料。當批料達到100℃時,經5分鐘裝載59.76份數之二甲基乙醇胺。然後經20分鐘裝載1001.15份數之DI水。此批料產出具有31.94% NV、0.117±0.043μm之粒子大小、20240厘泊之黏度以及16588之數均分子量之聚合物分散體。
以下實例類似於實例1,但在聚合之第一階段中不使用甲基丙烯酸烯丙基酯。
用66.49份數之正丁醇及218.19份數之2-丁氧基乙醇裝載三公升圓底四頸燒瓶,該燒瓶配備有攪拌器、氮入口管、溫度計及回流冷凝器。將燒瓶逐漸加熱至約110℃。在單獨器皿中,製備含有313.71份數之苯乙烯、251.38份數之甲基丙烯酸羥乙基酯以及28.38份數之過辛
酸三級丁酯之單體/引發劑混合物。在110℃下,將單體/引發劑混合物經2.5小時添加至反應器。當單體/引發劑混合物添加完成時,用添加至燒瓶之11.67份數之2-丁氧基乙醇沖洗單體/引發劑混合物器皿。將批料在110℃下保持30分鐘。在該固持之後,將批料溫度升高至128℃。在溫度升高期間,在單獨器皿中,製備包括60.83份數之甲基丙烯酸、60.83份數之甲基丙烯酸正丁基酯、13.54份數之苯乙烯、6.64份數之過乙酸三級丁基(50%水性溶液)、116.23份數之正丁醇以及8.18份數之DI水之單體/引發劑/溶劑混合物。在128℃下,然後將單體/引發劑/溶劑混合物在穩定狀態下經4小時裝載至反應器中,同時將溫度維持在約128℃下。當單體/引發劑混合物添加完成時,用其後添加至反應器之7.89份數之2-丁氧基乙醇沖洗單體/引發劑/溶劑混合物器皿。將批料在128℃下保持1小時。然後冷卻批料。當批料達到100℃時,經5分鐘裝載32.35份數之二甲基乙醇胺。然後經20分鐘裝載1001.15份數之DI水。此批料產出具有16.39±5.666μm之粒子大小、50厘泊之黏度以及8264之數均分子量之聚合物懸浮液。分離分散體相單獨達過夜。
以下實例類似於實例1,然而,將以一個階段中而非兩個階段來進行聚合。
用43.67份數之正丁醇、143.29份數之2-丁氧基乙醇以及8.12份數之異丙醇裝載三公升圓底四頸燒瓶,該燒瓶配備有攪拌器、氮入口管、溫度計及回流冷凝器。將燒瓶逐漸加熱至約128℃。在單獨器皿中,製備含有276.58份數之苯乙烯、201.59份數之甲基丙烯酸羥乙基酯、6.90份數之甲基丙烯酸烯丙基酯、112.38份數之甲基丙烯酸、112.38份數之甲基丙烯酸正丁基酯、16.67份數之過辛酸三級丁酯、6.13份數之過乙酸三級丁基(50%水性溶液)、139.05份數之正丁醇以及
74.90份數之2-丁氧基乙醇之單體/引發劑/溶劑混合物。在128℃下,將單體/引發劑/溶劑混合物在穩定狀態下經4.5小時添加至反應器。當單體/引發劑混合物添加完成時,用添加至反應器之19.56份數之2-丁氧基乙醇沖洗單體/引發劑/溶劑混合物器皿。將批料在128℃下保持1小時。After the hold,the批料was then cooled。當批料達到100℃時,經5分鐘裝載59.76份數之二甲基乙醇胺。然後經20分鐘裝載1001.15份數之DI水。此批料產出具有32.20% NV、10360厘泊之黏度以及11048之數均分子量之聚合物溶液。
用實例1至3之水性樹脂分散體配製穩定塗層組合物,如在下文之表1、表3及表5中概述。自比較實例6配製塗層組合物,如針對實例1至3大體上闡述。然而,在製備之後短時間內分離組合物相。將塗層組合物噴塗至2片式錫板罐中並在250℉(121℃)下烘烤2分鐘15秒且然後在425℉(218℃)下烘烤2分鐘30秒。用雞肉與米湯以及酸化番茄醬熱裝填該等罐,並在250℉(121℃)下殺菌60分鐘。然後將經裝填罐儲存於120℉(49℃)下之熱室中。週期性地評定腐蝕、黏附及染色,並在下文之表2、表4及表6中概述試驗結果。結果係基於三重量測。
在表2、表4及表6中,黏附係指主體部分黏附,而彎曲邊緣黏附係指底部邊緣區域上之黏附。劃格法黏附測試方法用於評估主體部分及彎曲邊緣黏附兩者。0至10之評定量表用於黏附評估,其中「10」之評定指示無附損失且「0」之評定指示完全黏附損失。對於染色及腐蝕評估,網格系統用於可視化地判定失敗之方格數,且然後計算0至10之數值評定量表。對於染色,「10」之評定指示在方格之任一者中無染色,且「0」之評定指示整個網格系統上方之膜之顏色之完全改變。對於腐蝕,「10」之評定指示在方格之任一者中不發生可見腐蝕,「0」之評定指示整個網格系統上方之100%覆蓋率之腐蝕。在表
2中報告之塗層膜顯示對雞肉與米湯之良好包裝效能。除在底部區域之外,觀察到優異總體抗腐蝕性、抗染色性以及黏附性。可在罐之頂部上看見輕微黏附失敗及一定腐蝕,然而在頂部空間區域中看見優異性質。塗層膜顯示對酸化番茄醬之優異包裝效能。抗腐蝕性、黏附性及抗染色性係突出的。
1來自Air Products之非離子表面活性劑。
用實例2之樹脂分散體配製之塗層組合物在下文之表3中報告。腐蝕、黏附及染色結果在下文之表4中報告。經塗佈膜顯示對雞肉與
米湯之良好包裝效能。該塗層具有與實例1中類似之效能。在底部上看見稍微較佳腐蝕。對於酸化番茄醬,塗層膜在底部上具有稍微較差腐蝕,但總體而言效能係突出的。
用實例3之樹脂分散體配製之塗層組合物在下文之表5中報告。
腐蝕、黏附及染色結果在下文之表6中報告。對於雞肉與米湯,塗層膜在底部上具有較差腐蝕及染色。其他區域(例如,頂部空間、沿口)具有與實例1及實例2中相等之效能。然而,對於酸化番茄醬,塗層膜具有最佳包裝效能。未看見腐蝕、染色或黏附失敗。
儘管上文已出於說明目的闡述本發明之特定實施例,但對彼等熟習此項技術者顯然將可對本發明細節作出多種改變,而不背離如隨附申請專利範圍中所界定之本發明。
儘管已以「包括」之措詞闡述本發明之各項實施例,但基本上由...組成或由...組成之實施例亦在本發明之範疇內。
Claims (24)
- 一種物品,其包括食品或飲料罐之主體部分或端部部分以及安置在其上之塗層組合物,其中該塗層組合物包括水性分散體,該水性分散體包括以下各項之反應產物:(a)疏水性乙烯基加成聚合物,其含有側鏈或末端乙烯系不飽和基團,(b)乙烯基單體混合物,其包含含有羧酸基團之乙烯基單體;該反應產物含有活性氫基團且係用鹼至少部分地中和並分散於水性介質中;該水性分散體實質上不含雙酚A及其衍生物。
- 如請求項1之物品,其中(a)與(b)之該反應產物係在非水性介質中進行。
- 如請求項1之物品,其中該疏水性乙烯基加成聚合物不可與胺自分散於水中。
- 如請求項1之物品,其中(a)含有活性氫基團。
- 如請求項1之物品,其中該反應產物具有40至200之酸值。
- 如請求項1之物品,其中(a)係由選自由以下各項組成之類別之乙烯基單體混合物製備:(i)芳香族乙烯基單體,(ii)在羥烷基基團中含有自2至4個碳原子之(甲基)丙烯酸羥烷基酯,以及(iii)含有(甲基)丙烯酸酯不飽和及較小反應性乙烯系不飽和兩者之單體。
- 如請求項6之物品,其中(ii)以基於乙烯基單體之總重量之5重量%至40重量%之量存在於該乙烯基單體混合物中。
- 如請求項6之物品,其中(iii)係選自由以下各項組成之群組:(甲基)丙烯酸(甲基)烯丙基酯以及(甲基)丙烯酸羥烷基酯與α、β-乙烯系不飽和二羧酸之縮合物。
- 如請求項1之物品,其中(a)具有3,000至50,000之數均分子量。
- 如請求項1之物品,其中(a)具有5,000至20,000之側鏈或末端乙烯系不飽和基團當量。
- 如請求項1之物品,其中(b)含有選自由以下各項組成之群組之單體:芳香族乙烯基單體以及在烷基基團中含有自1至12個碳原子之(甲基)丙烯酸烷基酯。
- 如請求項1之物品,其中該反應產物具有5,000至70,000之數均分子量。
- 如請求項1之物品,其中該活性氫係羥基,且該反應產物具有基於該反應產物之樹脂固體之80至200之羥基值。
- 如請求項1之物品,其另外含有與該活性氫基團反應之交聯劑。
- 如請求項14之物品,其中該交聯劑係選自由以下各項組成之群組:胺基塑膠及酚醛塑膠。
- 如請求項15之物品,其中該交聯劑以基於該水性分散體之樹脂固體之重量的5重量%至70重量%之量存在於該水性分散體中。
- 如請求項1之物品,其具有基於該水性分散體之總重量之10重量%至50重量%的樹脂固體含量。
- 如請求項1之物品,其中當以每平方英吋4毫克之乾燥膜厚度存在於飲料罐端部上時,該塗層組合物在曝露於含有溶於水中之1重量% NaCl之室溫電解質溶液達10秒之後使小於2毫安之電流通過。
- 一種方法,其包括:(a)提供包括水性分散體之塗層組合物,該水性分散體包括以下各項之反應產物:(i)疏水性乙烯基加成聚合物,其含有側鏈或末端乙烯系不飽和基團, (ii)乙烯基單體混合物,其包含含有羧酸基團之乙烯基單體;該反應產物含有活性氫基團且係用鹼至少部分地中和並分散於水性介質中;該水性分散體實質上不含雙酚A及其衍生物;(b)在將金屬基板形成為食品或飲料罐或其部分之前或之後將該塗層組合物施加至該金屬基板。
- 如請求項19之方法,其中將該塗層組合物施加至罐端部。
- 如請求項19之方法,其中樹脂分散體之(a)具有5,000至20,000之側鏈或末端乙烯系不飽和基團當量。
- 如請求項19之方法,其中該水性分散體之該反應產物具有5,000至70,000之數均分子量。
- 如請求項19之方法,其中該塗層組合物含有與該活性氫基團反應之交聯劑。
- 如請求項19之方法,其中該交聯劑係選自由以下各項組成之群組:胺基塑膠及酚醛塑膠。
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US10233349B2 (en) | 2019-03-19 |
RU2670753C1 (ru) | 2018-10-25 |
CA2938578A1 (en) | 2015-08-13 |
AU2015214373B2 (en) | 2017-05-25 |
EP3102620B1 (en) | 2018-07-18 |
MX2016010133A (es) | 2017-02-15 |
KR20160118301A (ko) | 2016-10-11 |
KR101967513B1 (ko) | 2019-04-09 |
CN106103513A (zh) | 2016-11-09 |
AR099239A1 (es) | 2016-07-06 |
WO2015120005A1 (en) | 2015-08-13 |
CN106103513B (zh) | 2020-04-28 |
EP3102620A1 (en) | 2016-12-14 |
ES2686713T3 (es) | 2018-10-19 |
TWI664248B (zh) | 2019-07-01 |
AU2015214373A1 (en) | 2016-08-18 |
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