TW202006078A - 水性乙烯-乙烯醇共聚物分散體及塗佈有該分散體之氧氣阻擋多層膜 - Google Patents
水性乙烯-乙烯醇共聚物分散體及塗佈有該分散體之氧氣阻擋多層膜 Download PDFInfo
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Abstract
本發明提供一種乙烯-乙烯醇共聚物之水性分散體,其適用作實現可撓性或剛性基板之薄塗層的漆,其特徵在於優異的氧氣及二氧化碳阻擋效能,尤其在高濕度條件下之阻擋效能。
Description
本發明係關於一種乙烯-乙烯醇(Ethylene-Vinyl Alcohol;常縮寫為EVOH)共聚物之水性分散體,其適用作塗佈可撓性或剛性基板之漆以便達成優異的氧氣阻擋特性,其中特別提及滿足食物封裝領域之要求。
乙烯乙烯醇(EVOH)為乙烯及乙烯醇之形式共聚物,其通常藉由使乙烯及乙酸乙烯酯聚合及之後使所獲得之乙烯-乙酸乙烯酯(ethylene-vinyl acetate;EVA)水解來加以製備。EVOH共聚物通常由其以mol%為單位量測之乙烯含量界定,因此,高乙烯EVOH及低乙烯EVOH可為可商購的。
關於本發明之應用領域,熟知的是當進入包裝中之氧氣與食品反應性組分反應或促進好氧細菌生長時,可能發生高品質食品損失、存放期縮短及腐敗事件。因此,近期食品封裝領域中之研究的一個重要部分已集中於製備具有低透氧性(亦即,高阻擋)之聚合物材料。如上文所預期,藉由限制氧氣自環境穿透至氧敏感性食品或醫藥產品中,產品之品質可得到保持,存放期可增加,且其結果為廢料減少及成本節約。
除高阻擋要求之外,用於塑料包裝之材料亦應具有各種其他特徵,諸如機械強度、耐熱性、耐化學性、透明度及可撓性。
合成聚合材料廣泛用於製造多種用於食品封裝之物品,但存在習知地用於提供具有氧氣阻擋特性之塗層或層的具體聚合物,諸如乙烯-乙烯醇共聚物(EVOH)、聚醯胺(polyamide;PA)、聚乙烯醇共聚物(polyvinyl alcohol copolymer;PVOH)及聚氯乙烯(polyvinyl chloride;PVC)。
EVOH之特徵在於在乾燥條件下,即在0%相對濕度(relative humidity,RH)下的更好之氧氣阻擋效能,且關於其作為阻擋材料之用途的大部分相關問題均與其水分敏感性有關。實際上,EVOH之親水性質導致其在直接暴露於高濕度條件(典型地高於60% RH)時吸收大量水,此歸因於水分使聚合性組成物溶脹且使聚合性組成物之結晶相部分熔融的作用,且其結果為最終透氧性增加。因此,在EVOH在食品包裝中作為阻擋層之效能與包裝所暴露於之加工及儲存條件之間存在待考慮之嚴密聯繫,尤其當涉及高水分及/或高溫之惡劣條件時存在待考慮之嚴密聯繫。
EP 2164898描述一種阻擋膜,其包含按摻合物重量計介於65重量%至95重量%之間之量的第一聚合性組分及介於5重量%至35重量%之間之量的第二阻擋組分的摻合物,該第一聚合性組分具有21至30 mol%之乙烯-乙烯醇共聚物含量,該第二阻擋組分具有41-50 mol%之乙烯-乙烯醇共聚物範圍。
重要的是應注意,在上文歐洲先前技術文件中,最終阻擋膜經由擠出技術,例如管狀流延共擠出、管狀或平板流延擠出、吹塑氣泡擠出(用於單層膜)或共擠出(用於多層膜)來獲得。不論如何,擠出製程需要待使用之材料的一些特徵,例如適合於製程溫度之熔融溫度、在高溫加工條件及標準大氣壓下之熱力學穩定性(氧化/降解風險)、在壓縮及剪應力下之機械穩定性以及因高溫加工而對添加劑或填充劑選擇進行之限制,該等特徵可能限制該等材料尤其在生物相容性封裝之領域中的適用性。
因此,為了在封裝解決方案中達成上文相關特徵,最相關的步驟之一由適合於製造例如漆塗層的含有EVOH之水基調配物的製備表示。
在此領域中,術語漆通常表示用於產生封裝塗層之液體調配物,其需要適合之耐物理及耐化學特性,以便保護所封裝之產品不發生任何變質且達成用於製造製程之技術效果,諸如基板濕潤、可撓性、黏著性促進及潤滑性。
就此而言,JP 2001172443揭示一種水性組成物,其包含乙烯含量為16至70 mol%(具有高乙烯含量)之乙烯-乙烯醇共聚物及乙烯含量為2至15 mol%(具有低乙烯含量)之乙烯-乙烯醇共聚物。第一乙烯-乙烯醇共聚物以細粒形式分散於水中,,且隨後分散於第二乙烯-乙烯醇共聚物之水性分散體中。在JP 2001172443中,具有高乙烯含量之EVOH視為高濕度條件下之最佳執行系統,因此,自使用具有高乙烯含量之EVOH作為主要成分開始,其次添加具有低乙烯含量之EVOH,以便改良組成物之可加工性(亦即,溶劑相容性)具體言之,JP 2001172443報導,低乙烯EVOH之量為按100重量份之第一EVOH計介於0.05重量份與100重量份之間,因此,其揭示高乙烯EVOH之量始終大於或等於低乙烯EVOH之量的組成物。
EP 1816159揭示一種基於乙烯-乙烯醇之共聚物的水性分散體,其特徵在於氣體阻擋效能、長期儲存穩定性及良好成膜特性。具體言之,EP 1816159使用乙烯含量為15-65 mol%且皂化度不低於80 mol%之EVOH共聚物;鹼中和的基於乙烯/α,β-不飽和羧酸之共聚物;及皂化度為75-100 mol%、聚合度為100-3500且含量為每100重量份EVOH共聚物0.5-100重量份的聚乙烯醇。直接所得之層壓物展示,當塗層厚度為15 μm時,在20℃及85%相對濕度之條件下量測的透氧性不高於0.286 fm/Pa•s,較佳不高於0.229 fm/Pa•s。
本發明之一個目標為提供一種基於乙烯-乙烯醇之共聚物的水性分散體,其在成膜特性方面表現優異,且在保持與厚度亦減小至低於10 μm之膜相關之優勢的同時,以具有高氣體阻擋效能為特徵。
具體言之,本發明係關於一種水性分散體,其包含呈膠囊形式的乙烯含量介於24 mol%與38 mol%之間(具有高乙烯含量)之第一乙烯-乙烯醇共聚物分散於乙烯含量低於15 mol%(具有低乙烯含量)之第二乙烯-乙烯醇共聚物中,其特徵在於該第一乙烯-乙烯醇共聚物與該第二乙烯-乙烯醇共聚物之間的重量比介於0.40與0.70之間。
考慮到上文所引用之先前技術文獻,儘管本發明亦揭示分別以低及高乙烯含量為特徵的兩種類型之EVOH的用途,但顯而易見的是,在本發明中實現之最終組成物為完全不同且新穎的。
若與先前技術相比,則本發明所主張之組成物的特徵在於高乙烯EVOH相對於低乙烯EVOH之量較低,詳言之,其重量比介於0.40與0.70之間,此係因為高乙烯EVOH相對於低乙烯EVOH之量較高造成在低於60% RH之中等相對濕度下的氧氣阻擋效能降低。此外,所主張的乙烯含量低於15 mol%之低乙烯EVOH的相對量之允許獲得水溶性系統,而所主張的具有較高乙烯含量(亦即,乙烯含量在24-38 mol%範圍內)之EVOH的相對量允許增加在高濕度條件存在下之穩定性。
更具體言之,本發明所主張的高乙烯含量與低乙烯含量聚合物之間的比率相對於先前技術反轉,且考慮到在高濕度條件下使用本發明氣體阻擋層之目的,吾等之發明報導更好之透氧性效能,具體言之,其特徵在於,相對於JP 2001172443的介於10 [cc 天-1
m-2
]至15 [cc 天-1
m-2
]之間的透氧性值,在20℃及80% RH下,本發明透氧性量測值(OTR)低於10 [cc 天-1
m-2
]。
此外,本發明人發現,為了經由使EVOH之結晶形式穩定化而改良其阻擋特性,已採用一些膠囊製備途徑,諸如噴霧乾燥、乳化、奈米沉澱及超臨界流體技術。詳言之,已採用噴霧乾燥加工以產生高乙烯EVOH膠囊。所獲得的最終水性分散體之膠囊在濕環境中保持其結晶度,其特徵在於體積平均直徑介於0.1 μm與10.0 μm之間的粒度分佈及直徑大於1.0 μm之粒子存在內腔。該體積平均直徑(Volume Mean Diameter;VMD)可定義為體積加權之樣品平均粒度,其藉由乾燥分散體雷射繞射來量測且藉由使用夫朗和斐理論(Fraunhofer theory)來計算。
在一些具體實例中,水性分散體可視情況以低於10重量%之量包含醇,例如乙醇或異丙醇,以便改良塗層之均質性。
此外,為了改良最終阻擋層之效能的目的,本發明分散體可進一步包含以介於0.1重量%與7重量%之間的量添加活性或惰性填充劑。特定言之,使用活性填充劑(如沸石,例如Linde A型(Linde Type A;LTA)沸石)可改良聚合物在水分溶解度方面之效能,以誘導在低濕度條件(低於60% RH)及高濕度條件(80% RH)下較高之阻擋效能。另一方面,添加惰性填充劑(如石墨烯、氧化石墨烯或磷酸鋯)可藉由降低氧氣在聚合物網中擴散之係數來改良在乾燥條件(亦即,0%相對濕度)下之氧氣阻擋效能。
塗層之機械穩定性及黏著性可藉由以相對於EVOH量較佳介於25重量%與100重量%之間的濃度使用一些分散劑(如四乙氧基矽烷(tetraethoxysilane;TEOS))來加以改良,或可以相對於EVOH量較佳低於7重量%之濃度添加填充劑(諸如纖維素)。此外,可較佳地以按EVOH重量計介於0.5%與5%之間的量添加例如幾丁聚醣(chitosan)之添加劑,以便改良塗層之再循環相容性。
作為藉由本發明達成之第二態樣,可獲得厚度減小的經塗佈之阻擋層壓物以便保持重要特性,如透明度、混濁度水準、與塑膠基板之黏著性、可加工性、較高再循環相容性、機械穩定性及成本降低,同時保持高阻擋效能。
實際上,如在EP 1816159中所報導,已知為了達到高阻擋效能,尤其在高濕度條件下達到高阻擋效能,需要最終膜之厚度較高,通常高於10 μm。
然而,在本揭示案中,本發明人已能夠經漆塗佈之阻擋層壓物,其包含至少一個基板及至少一個塗層,其特徵在於該塗層包含乙烯含量介於24 mol%與38 mol%之間的第一乙烯-乙烯醇共聚物的膠囊及乙烯含量低於10 mol%之第二乙烯-乙烯醇共聚物,該第一及第二共聚物之相應重量比介於0.40與0.70之間,其中該塗層之厚度介於0.1 μm與10.0 μm之間。
為了製備以低厚度值為特徵的經漆塗佈之阻擋層壓物,可藉由使用螺旋桿流延來獲得分散體,蒸發溶劑,且在介於80℃與150℃之間,較佳介於130℃與150℃之間的溫度下對所獲得之塗層進行烘烤製程。替代性製備製程可為刮塗、旋塗、浸漬塗佈、凹版塗佈、3輥塗佈、槽模塗佈、針頭分配、噴射分配。所獲得的經薄塗佈之層提供優異之OTR值,同時維持封裝應用中所需要之典型特性(如透射率及混濁度值)的優異效能,
此外,漆塗層之組成物的特徵亦在於作為CO2
阻擋層之相關效能,以使得其及相應層壓物適合於在受控大氣壓下進行食品封裝應用。
在一些具體實例中,層壓結構之基板可選自由以下組成之非限制性群:聚對苯二甲酸伸乙酯(Polyethylene Terephthalate;PET)、聚醯胺(PA)、聚呋喃酸伸乙酯(Polyethylene Furanoate;PEF)、聚乙烯(Polyethylene;PE)、聚丙烯(Polypropylene;PP)、聚己二酸對苯二甲酸伸丁酯(Polybutylene Adipate Terephthalate;PBAT)、聚丁二酸伸丁酯(Polybutylene Succinate;PBS)、聚乳酸(Polylactic Acid;PLA)、聚羥基烷酸酯(Polyhydroxyalkanoates;PHA)、澱粉摻合物、木質素纖維素摻合物及賽璐玢(cellophane),其厚度介於8 μm與150 μm之間。
在其他可能具體實例中,該經漆塗佈之層壓物可在於多層系統,該多層系統進一步包含黏著劑層,如聚胺基甲酸酯層壓黏著劑,其可經定位以與經塗佈之層、與基板或與其兩者接觸。
在下文中,將參照以下實施例更詳細地解釋本發明。
根據本發明,在樣品A-H中,高乙烯EVOH膠囊已藉由以下來加以製備:將乙烯-乙烯醇共聚物添加至保持在攪拌下之水醇溶液(100 rpm及80℃下)中。在聚合物溶解後,已將所得調配物噴霧乾燥,且必要時已進一步對其進行噴射研磨處理,以便獲得體積平均直徑為5 μm(±20%)且D90低於10 μm(其中D90定義為累積粒度分佈之90%所處的粒子尺寸)的單分散膠囊。隨後將此調配物添加至乙烯含量低於15 mol%之低乙烯EVOH共聚物的水性調配物中,以便得到具有目標氣體阻擋特性之最終水性分散體。最後,為了製備經漆塗佈之阻擋層壓物,已使用螺旋桿來使分散體流延,已蒸發溶劑,且在80℃與150℃之間的溫度下對所獲得之塗層進行烘烤製程。
已使用上文所描述之方法但使用處於本發明所主張之範圍外的EVOH共聚物之間相對比率來製備比較性樣品1、2及3。
已根據EP 1816159製備比較性樣品4。具體言之,已藉由在80℃下在攪拌下將丙烯酸及NaOH溶解於H2
O中來製備第一溶液(A)。對於第二溶液(B),已在80℃下在攪拌下將27 mol%之量的EVOH溶解於2-丙醇及H2
O中。之後,已將第一溶液(A)注射至第二溶液(B)中,且將所得溶液在5℃下冷卻12小時,且隨後與基於低乙烯EVOH(15 mol%)之溶液混合且之後流延。
表1:樣品及比較性樣品之清單
樣品組成物A至H係根據本發明,且與以兩種EVOH組分之間比率不同為特徵的比較性樣品1、2及3的值相比以及與根據EP 1816159製備之比較性樣品4相比,樣品組成物A至H的單位厚度之相對OTR值(OTR/μm)好得多。
對於所有上文樣品及比較性樣品所獲得之結果(概述於表1中)指出,處於本發明所主張之範圍外(低於0.4或高於0.7)的高乙烯含量與低乙烯含量EVOH之間重量比產生不適合於厚度減小(亦即,低於10.0 μm)且在高濕度條件中具有高氣體阻擋層要求之膜的透氧性值。
CO2
透過速率藉由以下來加以量測:將樣品的兩個表面暴露於50% RH(50% RH/50% RH)下,且隨後將阻擋層壓物的經漆塗佈之表面上的相對濕度增加至80% RH之值(80% RH/50% RH)。
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Claims (16)
- 一種水性分散體,其包含 呈膠囊形式的乙烯含量介於24 mol%與38 mol%之間之第一乙烯-乙烯醇共聚物,及 乙烯含量低於15 mol%之第二乙烯-乙烯醇共聚物, 其特徵在於該第一乙烯-乙烯醇共聚物與該第二乙烯-乙烯醇共聚物之間的重量比介於0.40與0.70之間。
- 如請求項1所述之水性分散體,其中該呈膠囊形式之第一乙烯-乙烯醇共聚物的乙烯含量介於27 mol%與32 mol%之間。
- 如請求項1或2所述之水性分散體,其中醇以介於5重量%與10重量%之間的量進行添加。
- 如請求項1或2所述之水性分散體,其中該等第一乙烯-乙烯醇共聚物膠囊之特徵在於體積平均直徑介於0.1 μm與10.0 μm之間的粒度分佈。
- 如請求項4所述之水性分散體,其中直徑大於1.0 μm之該等第一乙烯-乙烯醇共聚物膠囊之特徵在於存在內腔。
- 如請求項1或2所述之水性分散體,其中填充物以介於0.1重量%與7重量%之間的量進行添加。
- 如請求項6所述之水性分散體,其中該填充物選自由以下組成之群中:沸石、石墨烯、氧化石墨烯、纖維素及磷酸鋯。
- 如請求項1或2所述之水性分散體,其中四乙氧基矽烷(tetraethoxysilane;TEOS)以相對於EVOH介於25重量%與100重量%之間的量進行添加。
- 如請求項1或2所述之水性分散體,其中幾丁聚醣以相對於EVOH介於0.5重量%與5重量%之間的量進行添加。
- 一種經漆塗佈之阻擋層壓物,其包含至少一個基板及至少一個塗層,其特徵在於該塗層包含呈膠囊形式的乙烯含量介於24 mol%與38 mol%之間之第一乙烯-乙烯醇共聚物,及乙烯含量低於15 mol%之第二乙烯-乙烯醇共聚物,該等共聚物之相應重量比介於0.40與0.70之間。
- 如請求項10所述之經漆塗佈之阻擋層壓物,其中該基板選自由以下組成之群中:聚對苯二甲酸伸乙酯(Polyethylene Terephthalate;PET)、聚醯胺(Polyamide;PA)、聚呋喃酸伸乙酯(Polyethylene Furanoate;PEF)、聚乙烯(Polyethylene;PE)、聚丙烯(Polypropylene;PP)、聚己二酸對苯二甲酸伸丁酯(Polybutylene Adipate Terephthalate;PBAT)、聚丁二酸伸丁酯(Polybutylene Succinate;PBS)、聚乳酸(Polylactic Acid;PLA)、聚羥基烷酸酯(Polyhydroxyalkanoates;PHA)、澱粉摻合物、木質素纖維素摻合物及賽璐玢(cellophane)。
- 如請求項10或11所述之經漆塗佈之阻擋層壓物,其中該基板之厚度介於8 µm與150 µm之間。
- 如請求項10或11所述之經漆塗佈之阻擋層壓物,其中該塗層之厚度介於0.1 µm與10.0 µm之間。
- 如請求項10或11所述之經漆塗佈之阻擋層壓物,其中其進一步包含黏著劑層。
- 如請求項14所述之經漆塗佈之阻擋層壓物,其中該塗層與該黏著劑層接觸。
- 如請求項14所述之經漆塗佈之阻擋層壓物,其中該黏著劑層為聚胺基甲酸酯層壓黏著劑。
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