TW201940575A - 密著包裝用組成物、密著包裝用封合劑及密著包裝用包裝體 - Google Patents
密著包裝用組成物、密著包裝用封合劑及密著包裝用包裝體 Download PDFInfo
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- TW201940575A TW201940575A TW108109591A TW108109591A TW201940575A TW 201940575 A TW201940575 A TW 201940575A TW 108109591 A TW108109591 A TW 108109591A TW 108109591 A TW108109591 A TW 108109591A TW 201940575 A TW201940575 A TW 201940575A
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Classifications
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Abstract
本發明所提供的密著包裝用組成物，係含有熔體流動速率(JIS K7210-1999、190℃、荷重2160g)為6g/10min以上的乙烯‧不飽和羧酸共聚合體之離子聚合物(A)、及熔體流動速率(JIS K7210-1999、190℃、荷重2160g)為6g/10min以下的聚烯烴(B)之密著包裝用組成物，相對於密著包裝用組成物中的樹脂成分100質量%，聚烯烴(B)的含有量係20質量%以上且50質量%以下。
Description
本發明係關於密著包裝用組成物、密著包裝用封合劑、及密著包裝用包裝體。
所謂「密著包裝」係指將已搭載內容物(被包裝物)的底材托盤放入真空腔中，將真空腔內形成真空，經加熱的蓋材薄膜被加熱，且利用釋放上側腔的壓差使蓋材薄膜與內容物進行密接及假接著，而將內容物施行真空包裝。
習知供例如切片火腿、培根、水產加工品等施行密著包裝用的薄膜，一般係使用具有聚氯乙烯(PVC)/聚偏二氯乙烯(PVDC)/乙烯-醋酸乙烯酯共聚合體(EVA)之積層構造的薄膜。
然而，當收容含有銳利骨頭等水產加工品時、或在低溫下保存時，有薄膜對於開孔(產生針孔)的抵抗力(以下亦稱「突刺強度」)劣化之情況。又，底材(例如托盤)係聚丙烯(PP)樹脂的情況，有薄膜與托盤間之接著性差的問題。又，從環境問題而言亦要求包材的脫氯化。
柔軟且對內容物之密接性優異的食品包裝用多層膜，係揭示有至少含有：尼龍層(A)、阻氣層(B)、接著層(C)、離子聚合物層(D)、及醋酸乙烯酯含有率10%以上之乙烯-醋酸乙烯酯共聚合體層(E)的軟質多層膜，且層構成係(A)-(B)-(C)-(D)-(E)、(A)-(C)-(B)-(C)-(D)-(E)、(B)-(A)-(C)-(D)-(E)、(B)-(C)-(A)-(C)-(D)-(E)、或(A)-(B)-(A)-(C)-(D)-(E)的軟質多層膜(例如參照日本專利第3085626號公報)。
再者，作為突刺強度與內容物密接性優異的密著包裝蓋材用共擠出多層膜，揭示有一種密著包裝蓋材用共擠出多層膜，係外層配置離子聚合物樹脂(IO)層、中間層配置乙烯-醋酸乙烯酯共聚合體皂化物(EVOH)層、最內層配置醋酸乙烯酯含有率8莫耳%以上且20莫耳%以下的乙烯-醋酸乙烯酯共聚合體樹脂(EVA)或熱熔膠樹脂(HM)層，且離子聚合物樹脂(IO)層厚相對於薄膜總厚的比係40%以上且70%以下，乙烯-醋酸乙烯酯共聚合體皂化物(EVOH)層厚比係10%以下(例如參照日本專利第5034237號公報)。
如日本專利第3085626號公報、專利第5034237號公報所示，自習知起為能獲得具有各種機能的密著包裝用薄膜而進行各種嘗試。
本發明課題係於提供：可獲得相較於習知密著包裝用薄膜之下，能維持良好易剝離性、且抑制拉絲現象發生之密著包裝用薄膜的密著包裝用組成物，以及使用其之密著包裝用封合劑及密著包裝 用包裝體。
本發明係包含有以下態樣。
一種密著包裝用組成物，係含有熔體流動速率(JIS K7210-1999、190℃、荷重2160g)為6g/10min以上的乙烯‧不飽和羧酸共聚合體之離子聚合物(A)、及熔體流動速率(JIS K7210-1999、190℃、荷重2160g)為6g/10min以下的聚烯烴(B)之密著包裝用組成物，相對於上述密著包裝用組成物中的樹脂成分100質量%，上述聚烯烴(B)的含有量係20質量%以上且50質量%以下。
如<1>所記載的密著包裝用組成物，其中，上述乙烯‧不飽和羧酸共聚合體的不飽和羧酸含有量係10質量%以上且20質量%以下。
如<1>或ㄑ2>所記載的密著包裝用組成物，其中，上述聚烯烴(B)係含有從由丙烯所衍生構成單元、及由1-丁烯所衍生構成單元所構成群組中選擇之至少1種。
如<1>~<3>中任一項所記載的密著包裝用組成物，其中，上述離子聚合物(A)係含有從乙烯‧不飽和羧酸共聚合體的鋅離子聚合物、及乙烯‧不飽和羧酸共聚合體的鈉離子聚合物所構成群組中選擇之至少1種。
如<1>~<4>中任一項所記載的密著包裝用組成物，其中，相對於上述密著包裝用組成物中的樹脂成分100質量%，上述離子聚合物(A)的含有量係40質量%以上且80質量%以下。
如<1>~<5>中任一項所記載的密著包裝用組成物，其中，更進一步含有賦黏樹脂(C)，且相對於上述密著包裝用組成物中的樹脂成分100質量%，上述賦黏樹脂(C)的含有量係5質量%以上且25質量%以下。
一種密著包裝用封合劑，係含有<1>~<6>中任一項所記載的密著包裝用組成物。
一種密著包裝用包裝體，係具備有第1薄膜與第2薄膜，藉由使上述第1薄膜與上述第2薄膜互相密接，而將內容物施行密著包裝用的密著包裝用包裝體，其中，上述第1薄膜與上述第2薄膜中至少其中一者係具有<7>所記載的密著包裝用封合劑。
如<8>所記載的密著包裝用包裝體，其中，上述密著包裝用封合劑係配置於上述第1薄膜與上述第2薄膜至少其中一者中之接觸到上述內容物之面的至少其中一部分。
如<8>或<9>所記載的密著包裝用包裝體，其中，上述第1薄膜係具有至少1層為含離子聚合物(D)之層；上述第2薄膜係具 有上述密著包裝用封合劑。
如<10>所記載的密著包裝用包裝體，其中，上述離子聚合物(D)係含有鋅離子聚合物；含有上述離子聚合物(D)的層係配置於上述第1薄膜中之接觸到上述內容物之面的至少其中一部分。
根據本發明可提供：能獲得相較於習知密著包裝用封合劑下，維持良好易剝離性、且抑制拉絲現象發生之密著包裝用封合劑的密著包裝用組成物，以及使用其之密著包裝用封合劑及密著包裝用包裝體。
以下，針對本發明一例的實施形態進行說明。本發明並不僅侷限於以下實施形態，在本發明目的範圍內均可追加適當變更而實施。
另外，本說明書中，數值範圍的「~」係意指包含「~」前後數值。本說明書階段式記載的數值範圍中，依某數值範圍記載的上限值或下限值亦可取代為其他階段式記載數值範圍的上限值或下限值。又，本說明書所記載的數值範圍，依某數值範圍記載的上限值或下限值亦可取代為實施例所示的值。
本說明書中，組成物中的各成分量，係在組成物中相當於各成分的物質複數存在時，在無特別聲明之下係指組成物中所存在之該複數物質的總量。
本說明書中，所謂「(甲基)丙烯酸」係表示丙烯酸或甲基丙烯酸之至少一者。
本說明書的密著包裝用組成物，係含有：熔體流動速率(JIS K7210-1999、190℃、荷重2160g)為6g/10min以上的乙烯‧不飽和羧酸共聚合體之離子聚合物(A)、以及熔體流動速率(JIS K7210-1999、190℃、荷重2160g)為6g/10min以下的聚烯烴(B)。
密著包裝用組成物係藉由具備上述構成，可獲得相較於習知密著包裝用封合劑之下，能維持良好易剝離性、且抑制拉絲現象發生的密著包裝用封合劑。
以下，針對本說明書的密著包裝用組成物中所含各成分進行詳細說明。
另外，在無特別記載之下，熔體流動速率(MFR)係根據JIS K7210-1999，依190℃、2160g荷重所測定的值〔g/10分〕。
本說明書中，所謂「乙烯‧不飽和羧酸共聚合體之離子聚合物(A)」，係指乙烯‧不飽和羧酸系共聚合體(即，基質聚合物)所具有 的酸性基之至少其中一部分被金屬離子所中和的化合物。
形成離子聚合物的乙烯‧不飽和羧酸系共聚合體(即，基質聚合物)，係至少使乙烯、與不飽和羧酸進行共聚合而獲得的共聚合體，具有由乙烯所衍生構成單元、與由不飽和羧酸所衍生構成單元。
乙烯‧不飽和羧酸系共聚合體係可為嵌段共聚合體、無規共聚合體、接枝共聚合體中之任一者。
從可工業性取得的觀點而言，乙烯‧不飽和羧酸系共聚合體較佳係無規共聚合體。
由不飽和羧酸所衍生構成單元係可舉例如由：丙烯酸、甲基丙烯酸、反丁烯二酸、順丁烯二酸等所衍生的構成單元。
該等之中，作為由不飽和羧酸所衍生構成單元較佳係由丙烯酸所衍生構成單元或由甲基丙烯酸所衍生構成單元，更佳係由甲基丙烯酸所衍生構成單元。
本說明書中，乙烯‧不飽和羧酸共聚合體的離子聚合物(A)之不飽和羧酸含有量，係相對於乙烯‧不飽和羧酸系共聚合體的總構成單元為10質量%以上且20質量%以下，從抑制拉絲現象發生的觀點而言，更佳係10質量%以上且18質量%以下、特佳係10質量%以上且17質量%以下。
另外，所謂「乙烯‧不飽和羧酸共聚合體的不飽和羧酸含有量」， 係指由不飽和羧酸所衍生構成單元，相對於乙烯‧不飽和羧酸系共聚合體的總構成單元的含有量。
由乙烯所衍生構成單元的含有率，係相對於乙烯‧不飽和羧酸系共聚合體的總構成單元，較佳係80質量%以上且90質量%以下、更佳係82質量%以上且90質量%以下、特佳係83質量%以上且90質量%以下。
乙烯‧不飽和羧酸系共聚合體係除了由乙烯所衍生構成單元、與由不飽和羧酸所衍生構成單元之外，亦可含有由乙烯與不飽和羧酸以外之單體所衍生的構成單元(以下亦稱「其他構成單元」)。
其他構成單元係可舉例如由：不飽和羧酸酯；乙烯以外的不飽和烴(例如：丙烯、丁烯、1,3-丁二烯、戊烯、1,3-戊二烯、1-己烯等)；乙烯酯(例如：醋酸乙烯酯、丙酸乙烯酯等)；乙烯基硫酸、乙烯基硝酸等酸化物；鹵化合物(例如：氯乙烯、氟乙烯等)；含乙烯基之一級及二級胺化合物；一氧化碳、二氧化硫等所衍生的構成單元。
該等之中，其他構成單元較佳係由不飽和羧酸酯所衍生的構成單元。
作為不飽和羧酸酯係在能與乙烯及不飽和羧酸進行共聚合之前提下，其餘並無特別的限制，可舉例如：不飽和羧酸烷基酯。
不飽和羧酸烷基酯係可舉例如：丙烯酸甲酯、丙烯酸乙酯、丙烯酸異丙酯、丙烯酸異丁酯、丙烯酸正丁酯、丙烯酸異辛酯等丙烯 酸烷基酯；甲基丙烯酸甲酯、甲基丙烯酸乙酯、甲基丙烯酸異丁酯、甲基丙烯酸正丁酯、甲基丙烯酸異辛酯等甲基丙烯酸烷基酯；順丁烯二酸二甲酯、順丁烯二酸二乙酯等順丁烯二酸烷基酯等烷基酯中之烷基碳數為1~12的不飽和羧酸烷基酯。
該等之中，不飽和羧酸烷基酯特佳係例如：丙烯酸甲酯、丙烯酸乙酯、丙烯酸異丙酯、丙烯酸異丁酯、丙烯酸正丁酯、甲基丙烯酸甲酯、甲基丙烯酸乙酯、甲基丙烯酸異丁酯、甲基丙烯酸正丁酯、甲基丙烯酸異辛酯等丙烯酸或甲基丙烯酸的烷基酯，更佳係丙烯酸或甲基丙烯酸的低級烷基酯(例如：烷基碳數2~5的烷基酯)。
當乙烯‧不飽和羧酸系共聚合體係含有由不飽和羧酸酯所衍生構成單元時，乙烯‧不飽和羧酸系共聚合體的較佳具體例係可舉例如：乙烯‧(甲基)丙烯酸‧(甲基)丙烯酸烷基酯共聚合體(例如：乙烯‧(甲基)丙烯酸‧丙烯酸甲酯共聚合體、乙烯‧(甲基)丙烯酸‧丙烯酸乙酯共聚合體、乙烯‧(甲基)丙烯酸‧丙烯酸丁酯共聚合體等)。
其他構成單元的含有量，從確保柔軟性的觀點而言，相對於乙烯‧不飽和羧酸系共聚合體的總構成單元，較佳係0.1質量%~10質量%、更佳係1質量%~5質量%。
作為用於乙烯‧不飽和羧酸系共聚合體所具有酸性基之中和時的金屬離子並無特別的限制。
金屬離子係可舉例如：鋰、鈉、鉀、銣、銫等鹼金屬離子；鎂、鈣等鹼土族金屬離子；鋅等過渡金屬離子；鋁等各種金屬離子等等。
從可輕易取得工業化製品的觀點而言，金屬離子較佳係從鋅離子、鎂離子及鈉離子所構成群組中選擇至少1種，更佳係從鋅離子及鈉離子所構成群組中選擇至少1種，特佳係鋅離子。
金屬離子係可單獨使用1種、或併用2種以上。
乙烯‧不飽和羧酸共聚合體的離子聚合物(A)之中和度，較佳係90莫耳%以下、更佳係5莫耳%~80莫耳%、特佳係10莫耳%~70莫耳%。
若中和度為90莫耳%以下，可適度抑制離子凝聚、且能更加抑制流動性降低、更適當地維持成形加工性。
若中和度為5莫耳%以上，可更有效地發揮離子聚合物樹脂的性能。
另外，本說明書中所謂「中和度」係表示相對於乙烯‧不飽和羧酸系共聚合體(即，基質聚合物)所具有酸性基(特別係羧基)的莫耳數，金屬離子之摻合比率(莫耳%)。
乙烯‧不飽和羧酸共聚合體的離子聚合物(A)可使用已上市的市售物。市售物係可舉例如：三井‧杜邦高分子化學股份有限公司製、HIMILAN(註冊商標)系列等。
乙烯‧不飽和羧酸共聚合體的離子聚合物(A)之熔體流動速率(MFR)，從抑制拉絲現象發生的觀點而言係6g/10min以上、較佳係 8g/10min以上、更佳係10g/10min以上、特佳係12g/10min以上。
熔體流動速率(MFR)的上限並無特別的限制，從加工性的觀點而言，較佳係400g/10min以下、更佳係30g/10min以下、特佳係25g/10min以下、最佳係20g/10min以下。
本說明書的密著包裝用組成物，係含有熔體流動速率(JIS K7210-1999、190℃、荷重2160g)為6g/10min以下的聚烯烴(B)。
本發明的聚烯烴(B)之熔體流動速率(MFR)係6g/10min以下。聚烯烴(B)的熔體流動速率(MFR)較佳係5g/10min以下、更佳係4g/10min以下。
藉由聚烯烴(B)的熔體流動速率(MFR)為6g/10min以下，可獲得良好的易剝離性。熔體流動速率(MFR)的下限並無特別的限定，從加工性的觀點而言，較佳係1g/10min以上、更佳係2g/10min以上。
聚烯烴(B)係從剝離性的觀點而言，較佳係含有從由丙烯所衍生構成單元及由1-丁烯所衍生構成單元所構成群組中選擇至少1種、更佳係由丙烯所衍生構成單元。聚烯烴(B)較佳係以從由丙烯所衍生構成單元及由1-丁烯所衍生構成單元所構成群組中選擇至少1種為主成分含有。聚烯烴(B)係可舉例如：丙烯同元聚合物、以丙烯為主成分之丙烯與其他α-烯烴(例如乙烯、1-丁烯、1-戊烯、4-甲基-1-戊烯等)的共聚合體、1-丁烯同元聚合物、1-丁烯與其他α-烯烴的共聚合體等。
此處所謂「主成分」係指構成單元的含有量相對於聚烯烴(B)總構成單元為50質量%以上。所謂「聚烯烴(B)係以從由丙烯所衍生構成單元及由1-丁烯所衍生構成單元所構成群組中選擇至少1種為主成分含有」，係指當聚烯烴(B)係含有由丙烯所衍生構成單元與由1-丁烯所衍生構成單元時，由丙烯所衍生構成單元與由1-丁烯所衍生構成單元的總含有量為50質量%以上。
更具體而言，聚烯烴(B)的代表例係可例示如：聚丙烯、丙烯‧乙烯無規共聚合體、丙烯‧乙烯‧1-丁烯無規共聚合體、聚1-丁烯、1-丁烯‧丙烯無規共聚合體等。
本說明書的密著包裝用組成物，從維持良好易剝離性、抑制拉絲現象發生的觀點而言，將密著包裝用組成物中的樹脂成分設為100質量%時，乙烯‧不飽和羧酸共聚合體的離子聚合物(A)含有量較佳係40質量%以上且80質量%以下、更佳係50質量%以上且75質量%以下、特佳係50質量%以上且70質量%以下。
再者，從同樣的觀點而言，將密著包裝用組成物中的樹脂成分設為100質量%時，聚烯烴(B)的含有量係20質量%以上且50質量%以下、更佳係20質量%以上且45質量%以下、更佳係25質量%以上且45質量%以下。
本說明書中所謂「樹脂成分」係指密著包裝用組成物中所含的離子聚合物(A)、聚烯烴(B)及賦黏樹脂(C)。
再者，本說明書的密著包裝用組成物亦可更進一步含有賦黏樹 脂(C)。
賦黏樹脂(C)之例係可舉例如：脂肪族系烴樹脂、脂環族系烴樹脂、芳香族系烴樹脂、苯乙烯系樹脂、萜烯樹脂、松脂類等。
脂肪族系烴樹脂例係可舉例如以：1-丁烯、異丁烯、丁二烯、1,3-戊二烯、異戊二烯、間戊二烯等C4~C5單或二烯烴為主成分的聚合體等。
脂環族系烴樹脂之例係可舉例如：由廢料C4~C5餾分中的二烯成分進行環化二聚化後再經聚合的樹脂；由環戊二烯等環狀單體進行聚合的樹脂；由芳香族系烴樹脂進行核內氫化的樹脂等。芳香族系烴樹脂之例係可舉例如：乙烯基甲苯、茚、α-甲基苯乙烯等以C9~C10之乙烯基芳香族烴為主成分的樹脂等等。
此處所謂「主成分」係指該構成單元的含有量相對於烴樹脂總構成單元為50質量%以上。
苯乙烯系烴樹脂之例係可舉例如：苯乙烯、乙烯基甲苯、α-甲基苯乙烯、異丙烯基甲苯等聚合體等。
萜烯系樹脂之例係可舉例如：α-蒎烯聚合體、β-蒎烯聚合體、二戊烯聚合體、萜烯-酚共聚合體、α-蒎烯-酚共聚合體、氫化萜烯樹脂等。
松脂類之例係可舉例如：松脂、聚合松脂、氫化松脂、松脂酯、松脂酚樹脂及其酯等。
該等之中，更佳係使用氫化芳香族烴樹脂、氫化萜烯樹脂等氫化型樹脂。
賦黏樹脂(C)的含有量係從維持良好易剝離性的觀點而言，將密著包裝用組成物的樹脂成分設為100質量%時，較佳係0質量%以上且25質量%以下、更佳係1質量%以上且25質量%以下、又更佳係5質量%以上且25質量%以下、特佳係5質量%以上且20質量%以下、最佳係5質量%以上且18質量%以下。
本說明書的密著包裝用組成物中係除了上述成分之外，亦可摻合任意添加劑。此種添加劑係可舉例如：抗氧化劑、熱安定劑、光安定劑、抗靜電劑、滑劑、著色劑等。尤其從提升組成物加工性的觀點而言，較佳係摻合滑劑。此種滑劑係可舉例如：脂肪酸醯胺、高分子量聚乙二醇、氫化篦麻油、二氧化矽等。
此種滑劑相對於上述密著包裝用組成物合計量100質量份，當有機化合物滑劑的情況係摻合100ppm~10000ppm左右，又當如二氧化矽般之無機化合物滑劑時係摻合0.1質量%~3質量%左右較為有效。
使用滑劑時，將本說明書的密著包裝用組成物擠出塗佈加工於基材時，具有防止薄膜彼此間發生相黏、或對金屬輥黏附之情形，且能提高回捲等後續步驟之操作性等優點。
本說明書的密著包裝用組成物，若考慮到成形性與密封特性，則熔體流動速率較佳係1g/10min~400g/10min、更佳係1g/10min~150g/10min。
本揭示的密著包裝用封合劑係含有上述密著包裝用組成物。
封合劑中，密著包裝用組成物係可使用單層，但亦可在基材上將封合劑作為熱封層進行積層後使用。此種基材係延伸或無延伸薄膜，例如：聚對苯二甲酸乙二酯等聚酯；聚醯胺、聚丙烯、聚乙烯、乙烯‧醋酸乙烯酯共聚合體、乙烯‧不飽和羧酸酯共聚合體、乙烯‧不飽和羧酸共聚合體或其離子聚合物、乙烯‧乙烯醇共聚合體等薄膜；紙、鋁箔；經蒸鍍鋁、二氧化矽、氧化鋁、氧化鎂等的薄膜；經塗佈聚偏二氯乙烯、聚乙烯醇等阻氣材的薄膜等。該等基材係可為單層、亦可為2層以上的積層品。
本說明書中作為將密著包裝用組成物積層於基材的方法，係可舉例如：將密著包裝用組成物直接擠出層合於基材上的方法；使利用吹脹或T型模頭澆鑄成形而呈薄膜狀的密著包裝用組成物，積層於基材上的所謂熱壓合法、乾式疊層法、夾心層壓法、共擠出吹脹法、共擠出T型模頭法等一般方法，任一方法均可適用。
本說明書中，密著包裝用封合劑的厚度較佳係1μm~200μm、更佳係2μm~100μm、特佳係5μm~50μm。
再者，將密著包裝用封合劑使用為剝離薄膜時，基材厚度係從剝離時的操作性觀點而言，較佳係30μm~500μm左右。將密著包裝 用封合劑使用為底材時，基材的厚度並無特別的限制。
本揭示的密著包裝用包裝體係具備有第1薄膜與第2薄膜，藉由使上述第1薄膜與上述第2薄膜互相密接，而將內容物予以密著包裝的密著包裝用包裝體；其中，上述第1薄膜與上述第2薄膜之至少其中一者係具有上述密著包裝用封合劑。
再者，密著包裝用封合劑最好配置於第1薄膜及第2薄膜中之接觸於內容物之一面的至少其中一部分。根據另一實施形態，密著包裝用封合劑最好配置於第1薄膜與第2薄膜至少其中一者中之接觸到內容物之一面的至少其中一部分。
根據另一實施形態，密著包裝用封合劑最好配置於第1薄膜與第2薄膜至少其中一者中之第1薄膜與第2薄膜所相對向側之一面的至少其中一部分。
此處所謂「內容物」係包括有各種飲食品、醫藥品等各種物品，在能施行密著包裝之前提下，其餘並無特別的限定。
本說明書的密著包裝用包裝體係至少具備有第1薄膜與第2薄膜。
再者，亦可為第1薄膜與第2薄膜雙方均具備有含本說明書密著包裝用組成物之密著包裝用封合劑的態樣，亦可僅第1薄膜具備上述密著包裝用封合劑的態樣，亦可僅第2薄膜具備有上述密著包裝用封合劑的態樣。
此處，第1薄膜與第2薄膜係可為單層、亦可為2層以上的積層體。又，第1薄膜與第2薄膜係分別可為相同的層構成，又亦可為不同的層構成，並無特別的限定。
根據一實施形態，從深抽拉性的觀點而言，最好第1薄膜與第2薄膜中之至少其中一者含有離子聚合物(D)。可為第1薄膜係具有至少1層之含離子聚合物(D)的層，第2薄膜係具有密著包裝用封合劑的態樣；亦可第1薄膜係具有密著包裝用封合劑，第2薄膜係具有至少1層之含離子聚合物(D)的層的態樣。
再者，亦可第1薄膜係具有：至少1層之含離子聚合物(D)之層與密著包裝用封合劑的態樣，亦可第2薄膜為具有：至少1層之含離子聚合物(D)之層與密著包裝用封合劑的態樣。
另外，第1薄膜與第2薄膜的具體層構成、第1薄膜與第2薄膜的組合，係可配合密著包裝用包裝體的用途、目的，再行適當組合。
此處，含離子聚合物(D)之層的離子聚合物(D)，係在利用金屬離子之凝聚力的合成樹脂之前提下，其餘並無特別的限定。
金屬離子係可舉例如：鋰、鈉、鉀、銣、銫等鹼金屬離子；鎂、鈣等鹼土族金屬離子；鋅等過渡金屬離子；鋁等各種金屬離子等等，更佳係從鋅離子與鈉離子所構成群組中選擇至少一種，特佳係鋅離子。
再者，形成離子聚合物(D)的基質聚合物並無特別的限定，較佳係乙烯‧不飽和羧酸系共聚合體，可例示如上述離子聚合物(A)。
若第1薄膜與第2薄膜中至少其中一者係設有含離子聚合物(D)之層的情況，離子聚合物(D)較佳係鋅離子聚合物。此時，含鋅離子聚合物之層最好配置於接觸到內容物之一面的少其中一部分。
此處所謂「鋅離子聚合物」，較佳係使用乙烯‧不飽和羧酸系共聚合體作為基質聚合物。
雖不僅侷限於以下態樣，以下以將第1薄膜應用於蓋材側，將第2薄膜應用於托盤(底材)側的情況為例，說明本說明書的密著包裝用包裝體。
相關蓋材與托盤的層構成係可使用習知公知的層構成。
此處，當由含離子聚合物(D)之層(IO)、EVOH層(B)、乙烯-醋酸乙烯酯共聚合體樹脂層(EVA)、熱熔膠樹脂層(HM)、含聚乙烯之層(PE)、含聚丙烯之層(PP)、含尼龍之層(Ny)、二醇改質聚對苯二甲酸乙二酯樹脂層(PET-G)、發泡基材、以及本說明書的密著包裝用封合劑(EZP)表示時，可形成例如以下的層構成。
上述離子聚合物(D)係可為與本說明書密著包裝用封合劑(EZP)所含的離子聚合物(A)相同，亦可為不同。
另外，雖省略相關接著劑層的表述，但視需要亦可適當使用於各層間。
(1-1)IO/B/EVA(內容物側)
(1-2)PE/IO/B/EVA/IO(內容物側)
(1-3)IO/B/HM(內容物側)
(1-4)IO/B/IO/EVA(內容物側)
(1-5)IO/EVA/IO/EZP(內容物側)
(1-6)Ny/IO/B/EVA/IO(內容物側)
(1-7)PE/IO/Ny/B/EVA/IO(內容物側)
(1-8)Ny/IO/Ny/B/Ny/EVA/IO(內容物側)
(1-9)PET-G/B/IO/EZP(內容物側)
(2-1)發泡基材/PP/B/EZP(內容物側)
(2-2)PP/B/PP/IO(內容物側)
(2-3)PP/B/PP/EZP(內容物側)
例如若蓋材係上述(1-1)的情況，蓋材的積層構成係可例示依序積層著：含離子聚合物(D)之層(IO)、EVOH層(B)、乙烯-醋酸乙烯酯共聚合體樹脂層(EVA)，且該等層中，乙烯-醋酸乙烯酯共聚合體樹脂層(EVA)位於最靠近內容物側。此時，乙烯-醋酸乙烯酯共聚合體樹脂層(EVA)係可直接接觸於內容物，亦可在上述乙烯-醋酸乙烯酯共聚合體樹脂層(EVA)、與上述內容物之間隔著其他層。
上述蓋材與托盤(底材)中，較佳組合係[(1-1)或(1-2)或(1-6)或(1-7)]、與[(2-1)或(2-3)]、(1-5)與[((2-1)或(2-2)]，更佳組合係[(1-1)或(1-2)]與[(2-1)或(2-3)]，特佳組合係(1-2)與(2-1)。
上述(1-2)與(2-1)的組合，換言之，蓋材係具有至少1層之至少含有離子聚合物(D)的層，另一方面，托盤(底材)係設有本揭示密著包裝用封合劑(EZP)的實施形態。
該實施形態可適用於將食品、藥劑等施行密著包裝的用途。
上述實施形態中，當蓋材接觸到食品(內容物)之一面的至少其中一部分係含有鋅離子聚合物的層，且托盤(底材)接觸到食品(內容物)之一面的至少其中一部分係含有鋅離子聚合物的本揭示之密著包裝用封合劑時，因為具有延長食品(內容物)保存期限的效果，故可謂最佳實施形態。
以下，針對本發明利用實施例進行更具體說明，惟本發明在不逾越主旨前提下，並不僅侷限於以下實施例。
再者，熔體流動速率(MFR)係根據JIS K7210-1999測定。
將以下樹脂依照表1所示摻合比例，依裝填量成為10kg的方式進行混合。丟入擠出機(65mm 、L/D=28、前端杜爾麥基式螺紋螺桿)中，依加工溫度160℃施行熔融混練而製作樹脂組成物，獲得本發明的樹脂組成物(實施例)、與比較用樹脂組成物(比較例)。
‧離子聚合物1：乙烯‧甲基丙烯酸共聚合體之Zn中和物[乙烯單元含有量85質量%、甲基丙烯酸單元含有量15質量%、Zn中和度21%、MFR(190℃、2160g荷重)16g/10分]
‧離子聚合物2：乙烯‧甲基丙烯酸共聚合體之Zn中和物[乙烯單元含有量89質量%、甲基丙烯酸單元含有量11質量%、Na中和度37%、MFR(190℃、2160g荷重)11g/10分]
‧離子聚合物3：乙烯‧甲基丙烯酸共聚合體之Zn中和物[乙烯單元含有量85質量%、甲基丙烯酸單元含有量15質量%、Zn中和度23%、MFR(190℃、2160g荷重)5g/10分]
‧離子聚合物4：乙烯‧甲基丙烯酸共聚合體之Zn中和物[乙烯單元含有量88質量%、甲基丙烯酸單元含有量12質量%、Zn中和度36%、MFR(190℃、2160g荷重)1.5g/10分]
‧離子聚合物5：乙烯‧甲基丙烯酸共聚合體之Na中和物[乙烯單元含有量85質量%、甲基丙烯酸單元含有量15質量%、Na中和度30%、MFR(190℃、2160g荷重)2.8g/10分]
‧PP-1：聚丙烯[無規式、MFR(190℃、2160g荷重)3.1g/10分、MFR(230℃、2160g荷重)6g/10分、Prime Polymer公司製F317DV]
‧PP-2：聚丙烯[均質式、MFR(190℃、2160g荷重)3.2g/10分、MFR(230℃、2160g荷重)7g/10分、Prime Polymer公司製F107BV]
‧PP-3：聚丙烯[無規式、MFR(190℃、2160g荷重)6.5g/10分、MFR(230℃、2160g荷重)25g/10分、Prime Polymer公司製F329RA]
‧PB-1：聚丁烯-1[均質式、MFR(190℃、2160g荷重)3.7g/10 分、三井化學公司製BL4000]
‧賦黏樹脂：荒川化學工業(股)公司製"ARKON AM-1"(環球法軟化點115℃之脂環族烴樹脂)
其次，依如下示，使用上述所獲得樹脂組成物製作積層體，並評價。
其中，比較例2、3所示樹脂組成物的造粒性差，無法製作積層體。
另外，表1中「-」係表示未含該成分。
使用所獲得樹脂組成物製作積層體。詳言之，使用40mm 之3種3層澆鑄成形機，依加工溫度200℃施行共擠出的樹脂係選擇乙烯‧甲基丙烯酸共聚合體(酸含量9質量%、MFR8g/10分)，利用230℃、加工速度25m/分的擠出層合法，在預先作成的PET(12μm)/PE(15μm)基材上，積層40μm的乙烯‧甲基丙烯酸共聚合體、厚20μm之上述所獲得樹脂組成物，而製得PET(12μm)/PE(15μm)/乙烯‧甲基丙烯酸共聚合體(40μm)/樹脂組成物(封合劑層)(20μm)的積層體。
所獲得積層體在厚0.1mm的Zn離子聚合物之薄膜(基材)上， 依積層體之封合劑層側相對向於Zn離子聚合物薄膜的方式，於按押力0.2MPa、加熱溫度160℃、加熱時間1.0秒條件下施行熱封，然後在室溫下放置24小時。然後，將從積層體朝MD方向與TD方向切取出的寬15mm之試驗片雙面，朝相反方向(180℃剝離方向)拉伸，求取最大應力。將該最大應力(N/15mm)設為樹脂組成物之對Zn離子聚合物的MD方向及TD方向剝離強度(N/15mm)。測定結果如表1所示。
其中，超過1.0N/15mm且在10N/15mm以下，係較佳剝離強度。
再者，Zn離子聚合物薄膜係使用乙烯‧甲基丙烯酸共聚合體的Zn中和物[乙烯單元含有量85質量%、甲基丙烯酸單元含有量15質量%、Zn中和度59%、MFR(190℃、2160g荷重)0.9g/10分]，利用40mm 單層澆鑄成形機，於230℃進行製作。
於上述剝離強度的評價中，目視觀察剝離部。剝離部分有形成細絲狀樹脂的情況。此情形通稱為「拉絲現象」。此現象不僅影響外觀，當取出屬於食品之內容物時，有絲片不幸附著於食品等異物混入的觀感，故屬於不佳特性。目視記錄有無拉絲現象。測定結果如表1所示。
將實施例1所獲得積層體，在厚0.1mm的Na離子聚合物薄膜(基材)上，依積層體之封合劑層側相對向於Na離子聚合物薄膜的方式，於按押力0.2MPa、加熱溫度140℃、加熱時間1.0秒條件下 施行熱封，在室溫下放置24小時。然後，將從積層體切取出的寬15mm試驗片雙面朝相反方向(180℃剝離方向)拉伸，求取最大應力。將該最大應力(N/15mm)設為樹脂組成物對Na離子聚合物之剝離強度(N/15mm)。除了改變熱封溫度之外，其餘均依照與上述條件同樣地施行測定，亦求取熱封溫度160℃下，樹脂組成物對Na離子聚合物之剝離強度。又，依照與上述同樣地觀察有無拉絲現象。
測定結果如表2所示
此處，超過1.0N/15mm、且在10N/15mm以下，係屬較佳剝離強度。
再者，Na離子聚合物薄膜係使用乙烯‧甲基丙烯酸共聚合體的Na中和物[乙烯單元含有量85質量%、甲基丙烯酸單元含有量15質量%、Na中和度54%、MFR(190℃、2160g荷重)0.9g/10分]，利用40mm 單層澆鑄成形機，於230℃下進行製作。
將實施例1所獲得積層體，在厚0.1mm的EVA(乙烯‧醋酸乙烯酯共聚合體)薄膜(基材)上，依積層體之封合劑層側相對向於EVA薄膜的方式，於按押力0.2MPa、加熱溫度140℃、加熱時間1.0秒條件下施行熱封，在室溫下放置24小時。然後，將從積層體切取出的寬15mm試驗片雙面朝相反方向(180℃剝離方向)拉伸，求取最大應力。將該最大應力(N/15mm)設為樹脂組成物對EVA之剝離強度(N/15mm)。除了改變熱封溫度之外，其餘均依照與上述條件同樣地施行測定，亦求取熱封溫度160℃下，樹脂組成物對EVA之剝離強度。又，依照與上述同樣地觀察有無拉絲現象。
測定結果如表2所示
此處，超過1.0N/15mm、且在10N/15mm以下，係屬較佳剝離強度。
再者，EVA薄膜係使用乙烯‧醋酸乙烯酯共聚合體[乙烯單元含有量90質量%、醋酸乙烯酯單位含有量10質量%、MFR(190℃、2160g荷重)9g/10分]，利用40mm 單層澆鑄成形機，於200℃下進行製作。
將實施例1所獲得積層體，在厚0.1mm的LDPE(低密度聚乙烯)薄膜(基材)上，依積層體之封合劑層側相對向於LDPE薄膜的方式，於按押力0.2MPa、加熱溫度140℃、加熱時間1.0秒條件下施行熱封，在室溫下放置24小時。然後，將從積層體切取出的寬15mm試驗片雙面朝相反方向(180℃剝離方向)拉伸，求取最大應力。將該最大應力(N/15mm)設為樹脂組成物對LDPE之剝離強度(N/15mm)。除了改變熱封溫度之外，其餘均依照與上述條件同樣地施行測定，亦求取熱封溫度160℃下，樹脂組成物對LDPE之剝離強度。又，依照與上述同樣地觀察有無拉絲現象。
測定結果如表2所示
此處，超過1.0N/15mm、且在10N/15mm以下，係屬較佳剝離強度。
再者，LDPE薄膜係使用高壓法低密度聚乙烯[917kg/m3、MFR(190℃、2160g荷重)7g/10分]，利用40mm 單層澆鑄成形機，於200℃下進行製作。
由表1得知，由本實施例的密著包裝用組成物所獲得之密著包裝用封合劑，係維持良好的易剝離性，且能抑制拉絲現象發生。另一方面，由比較例的密著包裝用組成物所獲得之密著包裝用封合劑，係剝離性不良，或者即使剝離性良好，但仍有發生拉絲現象，所以任一者均較遜於實施例。
再者，由表2得知，由實施例1的密著包裝用組成物所獲得之密著包裝用封合劑，對如Zn離子聚合物薄膜等各種基材均維持良好的易剝離性，且未出現拉絲現象。
另外，2018年3月20日所提出申請得日本專利申請案第2018-053520號揭示的全部內容，均參照並援引於本說明書中。
本說明書所記載的所有文獻、專利申請案、及技術規格，係藉由參照而援引各個文獻、專利申請案、及技術規格，係依照具體且各者記載情況相同程度援引於本說明書中。
Claims (11)
- 一種密著包裝用組成物，係含有下述成分者：熔體流動速率(JIS K7210-1999、190℃、荷重2160g)為6g/10min以上的乙烯‧不飽和羧酸共聚合體之離子聚合物(A)；以及熔體流動速率(JIS K7210-1999、190℃、荷重2160g)為6g/10min以下的聚烯烴(B)；相對於上述密著包裝用組成物中的樹脂成分100質量%，上述聚烯烴(B)的含有量係20質量%以上且50質量%以下。
- 如請求項1之密著包裝用組成物，其中，上述乙烯‧不飽和羧酸共聚合體的不飽和羧酸含有量係10質量%以上且20質量%以下。
- 如請求項1之密著包裝用組成物，其中，上述聚烯烴(B)係含有從由丙烯所衍生構成單元及由1-丁烯所衍生構成單元所構成群組中選擇之至少1種。
- 如請求項1之密著包裝用組成物，其中，上述離子聚合物(A)係含有從乙烯‧不飽和羧酸共聚合體的鋅離子聚合物及乙烯‧不飽和羧酸共聚合體的鈉離子聚合物所構成群組中選擇之至少1種。
- 如請求項1之密著包裝用組成物，其中，相對於上述密著包裝用組成物中的樹脂成分100質量%，上述離子聚合物(A)的含有量係40質量%以上且80質量%以下。
- 如請求項1之密著包裝用組成物，其中，更進一步含有賦黏樹脂(C)，相對於上述密著包裝用組成物中的樹脂成分100質量%，上述賦黏樹脂(C)的含有量係5質量%以上且25質量%以下。
- 一種密著包裝用封合劑，係含有請求項1至6中任一項之密著 包裝用組成物。
- 一種密著包裝用包裝體，係具備有第1薄膜與第2薄膜，藉由使上述第1薄膜與上述第2薄膜互相密接，而將內容物施行密著包裝用的密著包裝用包裝體，其中，上述第1薄膜與上述第2薄膜中至少其中一者係具有請求項7之密著包裝用封合劑。
- 如請求項8之密著包裝用包裝體，其中，上述密著包裝用封合劑係配置於上述第1薄膜與上述第2薄膜至少其中一者中之接觸到上述內容物之面的至少其中一部分。
- 如請求項8之密著包裝用包裝體，其中，上述第1薄膜係具有至少1層之含離子聚合物(D)之層；上述第2薄膜係具有上述密著包裝用封合劑。
- 如請求項10之密著包裝用包裝體，其中，上述離子聚合物(D)係含有鋅離子聚合物；含有上述離子聚合物(D)的層係配置於上述第1薄膜之接觸到上述內容物之面的至少其中一部分。
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