TWI708681B - 拋棄式發熱包外袋用多層膜及拋棄式發熱包 - Google Patents
拋棄式發熱包外袋用多層膜及拋棄式發熱包 Download PDFInfo
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- TWI708681B TWI708681B TW105119838A TW105119838A TWI708681B TW I708681 B TWI708681 B TW I708681B TW 105119838 A TW105119838 A TW 105119838A TW 105119838 A TW105119838 A TW 105119838A TW I708681 B TWI708681 B TW I708681B
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- layer
- outer bag
- disposable heating
- heating pack
- film
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Abstract
本發明提供一種阻止氧氣、水蒸氣等之透過之阻氣性優異,並且可防止由保存期間中所產生之氫氣引起之膨脹,且密封強度、耐衝擊性、耐候性優異的拋棄式發熱包外袋用多層膜及拋棄式發熱包。
於由包含第1阻隔層10及第2阻隔層20之多層膜所形成之拋棄式發熱包外袋中,第1阻隔層10及第2阻隔層20包含在耐熱性樹脂基材11或耐熱性樹脂基材21之至少一個面(圖1中上側)塗佈聚偏二氯乙烯而成之聚偏二氯乙烯層12或聚偏二氯乙烯層22。
Description
本發明係關於一種拋棄式發熱包外袋用多層膜及拋棄式發熱包。
拋棄式發熱包係利用由鐵粉之氧化作用所產生之發熱的發熱包,通常,將內袋收納於包含斷絕未使用時與空氣之接觸之非透氣性膜的外袋而將其密封包裝,該內袋係將含有作為發熱體之鐵粉、作為氧化觸媒之鹽、用以吸收氧氣之活性碳、使鐵發生氧化之水、用以保水之保水劑等之發熱性組合物收納於不織布或紙等之透氣性袋內而成。
拋棄式發熱包外袋之阻止空氣尤其是氧氣、水蒸氣等之透過之阻氣性必須優異。於拋棄式發熱包外袋對氧氣及水蒸氣之阻氣性較差之情形時,於長時間之保存中,拋棄式發熱包外袋內部之氣體或水蒸氣向外部逃逸而變為減壓(vacuum)狀態,外袋產生凹陷而於外觀上欠佳。又,於如此變為減壓(vacuum)狀態者在長時間之保存後用作拋棄式發熱包之情形時,多數情況下其發熱之持續時間會變短。作為構成拋棄式發熱包外袋之非透氣性膜,一般使用密封劑層之上設置有阻氣層且最外層設置有耐熱性樹脂層之多層膜。藉由重疊2片該等非透氣性多層膜,並使位於內側之密封劑層之周緣部相互地進行熱密封而形成為袋狀,從而製造拋棄式發熱包外袋。
作為構成此種拋棄式發熱包外袋之非透氣性膜,例如,使用如
下非透氣性之多層膜,其於聚烯烴系樹脂膜等基材膜之一個面設置有聚偏二氯乙烯之塗佈膜,進而,設置有乙烯-乙酸乙烯酯共聚物等熱密封性樹脂層。然而,該非透氣性之多層膜存在因長期保存而發熱持續性能降低等問題,為了解決該問題,揭示了如下非透氣性之多層膜,其設置有被氧化鋁層被覆之聚對苯二甲酸乙二酯膜、作為接著層之聚乙烯膜、及作為熱密封性樹脂層之乙烯-乙酸乙烯酯共聚物(專利文獻1)。
然而,已知若於未使用之狀態下長時間保存拋棄式發熱包,則會產生微量之氫氣。拋棄式發熱包外袋因氫氣而發生膨脹,於外觀上欠佳。又,若膨脹達到極限,則外袋會發生破損,收納於內袋之發熱性組合物發生氧化而發熱,因此,作為拋棄式發熱包之功能受損。因此,要求於長時間之保存中拋棄式發熱包外袋不發生膨脹之程度之氫氣透過性。然而,如上所述,對於拋棄式發熱包外袋,亦要求其阻止氧氣、水蒸氣等之透過之阻氣性優異。因此,若提高形成拋棄式發熱包外袋之非透氣性膜之上述阻氣性,則氫氣透過性會降低,於長時間之保存中發生膨脹。因此,作為滿足對氧氣及水蒸氣之阻氣性與氫氣透過性此種相反之條件者,申請人提出了如下多層膜,其包含對基材蒸鍍金屬或金屬氧化物而成之蒸鍍層、及於基材塗佈聚偏二氯乙烯而成之聚偏二氯乙烯層,將該多層膜用於外袋之拋棄式發熱包已由申請人推向市場。
關於包含上述蒸鍍層及聚偏二氯乙烯層之多層膜,其阻止氧氣、水蒸氣等之透過之阻氣性優異,並且可防止由保存中所產生之氫氣引起之膨脹。如此,將包含蒸鍍層及聚偏二氯乙烯層之多層膜用作拋棄式發熱包用外袋並無較大之問題,但申請人反覆研究,結果發現了以下之更應該加以改善之方面。
(1)作為製品流通時之耐久性
由於存在外袋自外部受到強烈之衝擊之情況,故而對於包含非透氣性膜之外袋,要求各層間之密封強度、耐衝擊性,以便即便受到衝擊,外袋亦不會開封、破裂。
(2)陳列於店面時之耐候性
由於存在外袋暴露於日光等紫外線之情況,故而對於包含非透氣性膜之外袋,要求即便暴露於日光等紫外線之後亦不會引起變色等外觀之變化之耐候性。
如上所述,可明確,上述包含蒸鍍層及聚偏二氯乙烯層之多層膜雖阻氣性優異,並且可防止由氫氣引起之膨脹,但於密封強度、耐衝擊性、耐候性之方面有改善之餘地。
如上所述,揭示了各種拋棄式發熱包外袋用多層膜,但期望作為製品可持續長時間地確保最適合之氣體透過性及阻氣性,且密封強度、耐衝擊性、耐候性優異之拋棄式發熱包外袋用多層膜及拋棄式發熱包。
[專利文獻1]日本專利特開平11-239584號公報
因此,本發明之目的在於提供一種拋棄式發熱包外袋用多層膜及拋棄式發熱包,其等選擇性地阻止氧氣、水蒸氣等之透過之阻氣性優異,並且可防止由保存中所產生之氫氣引起之膨脹,且密封強度、耐衝擊性、耐候性優異,尤其是可承受暴露於日光等紫外線之狀態下之長期保存(陳列)。
本發明者等人為了解決上述問題而努力研究,結果得到如下見
解,即,包含2層以上之包括基材、及於上述基材之至少一個面塗佈聚偏二氯乙烯而成之聚偏二氯乙烯層之阻隔層的多層膜可實現作為拋棄式發熱包外袋之最適合之氧氣透過性、水蒸氣透過性、氫氣透過性、密封強度、耐衝擊性、耐候性,從而完成了本發明。本發明之具體之態樣如下所述。
[1]一種拋棄式發熱包外袋用多層膜,其特徵在於包含2層以上之阻隔層,上述阻隔層包含基材、及於上述基材之至少一個面塗佈聚偏二氯乙烯而成之聚偏二氯乙烯層。
[2]如[1]所記載之拋棄式發熱包外袋用多層膜,其特徵在於不包含蒸鍍金屬或金屬氧化物而成之蒸鍍層。
[3]如[1]或[2]所記載之拋棄式發熱包外袋用多層膜,其特徵在於:上述基材係選自雙軸延伸聚丙烯、雙軸延伸聚對苯二甲酸乙二酯及雙軸延伸聚醯胺樹脂。
[4]如[1]至[3]中任一項所記載之拋棄式發熱包外袋用多層膜,其特徵在於進而包含含有熱熔合性樹脂基材之密封劑層。
[5]如[1]至[4]中任一項所記載之拋棄式發熱包外袋用多層膜,其特徵在於:於上述2層以上之阻隔層之間進而包含接著劑層。
[6]如[1]至[5]中任一項所記載之拋棄式發熱包外袋用多層膜,其特徵在於進而包含追加之樹脂層。
[7]如[1]至[6]中任一項所記載之拋棄式發熱包外袋用多層膜,其特徵在於:於20℃、90%RH下所測定之氧氣透過度為1.5~4.5cc/(m2‧day‧atm),於40℃、90%RH下所測定之水蒸氣透過度為0.05~3.5g/(m2‧day)。
[8]一種拋棄式發熱包,其係將收納有發熱性組合物之內袋密封包裝於將如[1]至[7]中任一項所記載之拋棄式發熱包外袋用多層膜進行熱熔合而形成之外袋而成。
本發明之拋棄式發熱包外袋用多層膜具有阻止氧氣及水蒸氣之透過並且容許氫氣之透過之作為拋棄式發熱包外袋之最適合之阻氣性,且密封強度、耐衝擊性、耐候性優異。
本發明之拋棄式發熱包可防止由保存中所產生之氫氣引起之膨脹、以及由氧氣及水蒸氣之透過引起之發熱性組合物之劣化,能無損作為拋棄式發熱包之功能而長時間保存。又,本發明之拋棄式發熱包因密封強度、耐衝擊性及耐候性優異,故流通時之耐久性優異,進而,即便於陳列於店面時暴露於日光等紫外線之情形時,亦不易引起變色等外觀之變化。
10‧‧‧第1阻隔層
11‧‧‧耐熱性樹脂基材
12‧‧‧聚偏二氯乙烯層
20‧‧‧第2阻隔層
21‧‧‧耐熱性樹脂基材
22‧‧‧聚偏二氯乙烯層
30‧‧‧密封劑層
40‧‧‧接著劑層
50‧‧‧印刷油墨層
60‧‧‧追加之樹脂層
圖1係表示本發明之拋棄式發熱包外袋用多層膜之一態樣中之積層構成的說明圖。
圖2係表示本發明之拋棄式發熱包外袋用多層膜之另一態樣中之積層構成的說明圖。
圖3係表示本發明之拋棄式發熱包外袋用多層膜之進而另一態樣中之積層構成的說明圖。
以下,一面參照圖式,一面對本發明之拋棄式發熱包外袋用多層膜及拋棄式發熱包進行說明。
本發明之拋棄式發熱包外袋用多層膜之特徵在於包含2層以上之阻隔層,上述阻隔層包含基材、及於上述基材之至少一個面塗佈聚偏二氯乙烯而成之聚偏二氯乙烯層。於2層以上之阻隔層中,各阻隔層之基材可相同,亦可不同。
阻隔層之層數只要為2層以上,則並無特別限定,較理想為壁薄且發揮耐衝擊性及耐候性,較佳為2~5層,更佳為2~3層,最佳為2
層。
於圖1~3中表示本發明之拋棄式發熱包外袋用多層膜之實施態樣。拋棄式發熱包外袋用多層膜包含第1阻隔層10、第2阻隔層20及密封劑層30。於拋棄式發熱包外袋中,密封劑層30成為外袋之內側表面。
於圖1中,第1阻隔層10包含在耐熱性樹脂基材11之至少一個面(圖1中之上側)塗佈聚偏二氯乙烯而成之聚偏二氯乙烯層12。第2阻隔層20包含在耐熱性樹脂基材21之至少一個面(圖1中之下側)塗佈聚偏二氯乙烯而成之聚偏二氯乙烯層22。於圖1所示之態樣中,於第1阻隔層10之下積層有接著劑層40及密封劑層30,於第1阻隔層10之上積層有接著劑層40及印刷油墨層50。接著劑層40係用於將第1阻隔層10接著於密封劑層30、第2阻隔層20或其他層(例如,圖1中之印刷油墨層50)。印刷油墨層50可為了印刷製品說明等而視需要設置。
圖2所示之態樣除了圖1之構成以外,亦於第1阻隔層10與第2阻隔層20之間,包含追加之接著劑層40及追加之樹脂層60。設置於中間之追加之樹脂層60提高多層膜之強度。又,藉由設置追加之樹脂層60而增加多層膜整體之厚度,藉此可進而降低氣體透過性及水蒸氣透過性。
圖3所示之態樣係以如下方式積層而成,即,於密封劑層30之上積層接著劑層40,繼而,以成為耐熱性樹脂基材11及聚偏二氯乙烯層12之順序之方式積層第1阻隔層10,進而,積層接著劑層40,此外,以成為耐熱性樹脂基材21及聚偏二氯乙烯層22之順序之方式積層第2阻隔層20,然後依序介置接著劑層40及印刷油墨層50,以成為最外層之方式積層追加之樹脂層60。
包含圖1~3所示之本發明之拋棄式發熱包外袋用多層膜的拋棄式發熱包外袋藉由具備於耐熱性樹脂基材11之至少一個面塗佈聚偏二
氯乙烯而成之聚偏二氯乙烯層12作為第1阻隔層10、及於耐熱性樹脂基材21之至少一個面塗佈聚偏二氯乙烯而成之聚偏二氯乙烯層22作為第2阻隔層20,一定程度上阻斷氧氣自外袋外部向外袋內部侵入,又,容許氫氣自外袋內部向外袋外部透過。藉此,至使用時前有效地防止收納於拋棄式發熱包內袋之發熱性組合物中之鐵粉等金屬之氧化,又,有效地防止由保存中所產生之氫氣引起之外袋之膨脹。進而,藉由具備第1阻隔層10及第2阻隔層20,防止水蒸氣之透過之水蒸氣阻隔性提高。藉此,防止水分自外袋外部向外袋內部侵入,又,防止作為構成成分包含於拋棄式發熱包之發熱性組合物且發揮促進鐵粉等金屬之氧化之作用的水以水蒸氣之形式自外袋內部被釋出至外袋外部。此外,藉由具備第1阻隔層10及第2阻隔層20,密封強度、耐衝擊性優異。藉此,即便外袋受到強烈之衝擊,亦可防止外袋開封、破裂。又,藉由具備第1阻隔層10及第2阻隔層20,耐候性優異。藉此,即便外袋暴露於日光等紫外線,亦防止變色等外觀之變化。
其次,對本發明之拋棄式發熱包外袋用多層膜之構成成分及其製造方法進行說明。
第1阻隔層10包含在耐熱性樹脂基材11塗佈聚偏二氯乙烯而成之聚偏二氯乙烯層12。又,第2阻隔層20包含在耐熱性樹脂基材21塗佈聚偏二氯乙烯而成之聚偏二氯乙烯層22。
作為耐熱性樹脂基材11及耐熱性樹脂基材21,例如,可使用聚乙烯系樹脂或聚丙烯系樹脂等聚烯烴系樹脂、環狀聚烯烴系樹脂、聚苯乙烯系樹脂、丙烯腈-苯乙烯共聚物(AS(Acrylonitrile-Styrene)樹脂)、丙烯腈-丁二烯-苯乙烯共聚物(ABS(Acrylonitrile-Butadiene-Styrene)樹脂)、聚(甲基)丙烯酸系樹脂、聚碳酸酯系樹脂、聚對苯二甲酸乙二酯、聚萘二甲酸乙二酯等聚酯系樹脂、各種尼龍等聚醯胺系樹脂、聚胺基甲酸酯系樹脂、縮醛系樹脂、纖維素系樹脂、其他等各種樹脂之
膜。其中,較佳為聚酯系樹脂、聚烯烴系樹脂、或聚醯胺系樹脂之膜,尤其較佳為雙軸延伸聚丙烯、雙軸延伸聚對苯二甲酸乙二酯或雙軸延伸聚醯胺樹脂。使用上述各種樹脂之1種或其以上,使用擠出法、流延成形法、T模法、切削法、吹脹法、其他製膜化法,藉由對單獨或2種以上之各種樹脂進行多層共擠出製膜之方法,進而,藉由混合2種以上之樹脂之後進行製膜之方法等,製造各種樹脂之膜,進而,例如可利用拉幅機方式、或管式方式等向單軸或雙軸方向延伸而形成各種樹脂膜。
作為耐熱性樹脂基材11及耐熱性樹脂基材21之厚度,較佳為3~500μm,更佳為5~300μm,進而較佳為10~100μm,最佳為15~50μm。
用於耐熱性樹脂基材11及耐熱性樹脂基材21之各種樹脂膜之種類、及/或厚度可相同,亦可不同,兩者均可。
塗佈於耐熱性樹脂基材11及耐熱性樹脂基材21之聚偏二氯乙烯樹脂較佳為偏二氯乙烯之均聚物或共聚物。該等聚合物之中,偏二氯乙烯含量較佳為處於50~98莫耳%之範圍,更佳為處於75~96莫耳%之範圍之偏二氯乙烯共聚物由於製膜性、阻氣性之平衡優異,故而較佳。作為可與偏二氯乙烯發生共聚之單體之具體例,例如,可於氯乙烯、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2-羥基乙酯等丙烯酸酯,甲基丙烯酸甲酯、甲基丙烯酸縮水甘油酯等甲基丙烯酸酯,丙烯腈、甲基丙烯腈,及丙烯酸、甲基丙烯酸、亞甲基丁二酸、順丁烯二酸等不飽和羧酸等之中選擇一種或兩種以上而使用。其中,就製膜性之方面而言,較佳為使用氯乙烯、丙烯酸酯。又,聚偏二氯乙烯樹脂亦可適當組合2種以上而使用。進而,亦可於聚偏二氯乙烯樹脂適當添加熱穩定劑或光穩定劑、潤滑劑等添加劑而使用。聚偏二氯乙烯樹脂通常係以乳液或溶液之形式使用。
作為此種聚偏二氯乙烯層12及聚偏二氯乙烯層22之形成方法,例如,可藉由將視需要溶解或分散於溶劑而製成塗佈液之聚偏二氯乙烯樹脂塗佈於耐熱性樹脂基材11及耐熱性樹脂基材21之表面的方法等形成。
聚偏二氯乙烯層12及聚偏二氯乙烯層22之厚度並無特別限定,只要根據所需之氧氣阻隔性等適當設定即可,較佳為0.5~30μm,更佳為0.8~10μm,最佳為1~2μm。
聚偏二氯乙烯層12及聚偏二氯乙烯層22之形成方法、及/或厚度可相同,亦可不同,兩者均可。
拋棄式發熱包外袋用多層膜之自耐熱性樹脂基材11觀察之聚偏二氯乙烯層12之位置、及自耐熱性樹脂基材21觀察之聚偏二氯乙烯層22之位置並無特別限定,自耐熱性樹脂基材11或耐熱性樹脂基材21觀察,可為密封劑層30(外袋之內側表面)側或與密封劑層30(外袋之內側表面)相反之側之任一者。又,如圖1及2般,於第2阻隔層20成為外袋之外側表面之情形時,就防止聚偏二氯乙烯層因與外部之接觸而受到損傷,導致阻氣性降低之觀點而言,聚偏二氯乙烯層22之位置自耐熱性樹脂基材21觀察,較佳為密封劑層30(外袋之內側表面)側。
第1阻隔層單獨、及/或第2阻隔層單獨之氧氣透過度(20℃、90%RH)較佳為1.5~20cc/(m2‧day‧atm),更佳為2.0~15cc/(m2‧day‧atm),最佳為2.0~10cc/(m2‧day‧atm)。又,第1阻隔層單獨、及/或第2阻隔層單獨之水蒸氣透過度(40℃、90%RH)較佳為1.0~20g/(m2‧day),更佳為2.5~15g/(m2‧day)。
具有上述第1阻隔層10及第2阻隔層20之本發明之拋棄式發熱包外袋用多層膜之氧氣透過度(20℃、90%RH)較佳為1.5~4.5cc/(m2‧day‧atm),更佳為2.0~4.0cc/(m2‧day‧atm),最佳為2.0~3.5cc/(m2‧day‧atm),水蒸氣透過度(40℃、90%RH)較佳為0.05~3.5
g/(m2‧day),更佳為0.05~3.0g/(m2‧day),最佳為0.05~2.5g/(m2‧day)。藉由將具有上述第1阻隔層10及第2阻隔層20之本發明之拋棄式發熱包外袋用多層膜之氧氣透過度及水蒸氣透過度設為上述數值範圍內,阻止氧氣、水蒸氣等之透過之阻氣性優異,並且可發揮能防止由保存中所產生之氫氣引起之膨脹之效果。
密封劑層30較佳為包含熱熔合性樹脂。作為熱熔合性樹脂,例如,可使用低密度聚乙烯、中密度聚乙烯、高密度聚乙烯、直鏈狀(線性)低密度聚乙烯、聚丙烯、乙烯-乙酸乙烯酯共聚物、離子聚合物樹脂、乙烯-丙烯酸乙酯共聚物、乙烯-丙烯酸共聚物、乙烯-甲基丙烯酸共聚物、乙烯-丙烯共聚物、甲基戊烯聚合物、利用丙烯酸、甲基丙烯酸、順丁烯二酸酐、反丁烯二酸、其他等不飽和羧酸對聚乙烯、聚苯乙烯、聚丙烯等聚烯烴系樹脂進行改性而成之酸改性聚烯烴系樹脂、其他等樹脂之1種或2種以上。使用上述各種樹脂之1種或其以上,使用擠出法、流延成形法、T模法、切削法、吹脹法、其他製膜化法,藉由對單獨或2種以上之各種樹脂進行多層共擠出製膜之方法,進而,藉由混合2種以上之樹脂之後進行製膜之方法等,製造各種樹脂之膜,進而,例如可利用拉幅機方式、或管式方式等向單軸或雙軸方向延伸而形成各種樹脂膜。其中,較佳為未延伸聚丙烯、雙軸延伸聚丙烯、未延伸聚乙烯、低密度聚乙烯、中密度聚乙烯、高密度聚乙烯或直鏈狀(線性)低密度聚乙烯,尤其就熱熔合性之觀點而言,更佳為未延伸聚丙烯、雙軸延伸聚丙烯或直鏈狀(線性)低密度聚乙烯。
又,作為密封劑層30之厚度,較佳為5~300μm,更佳為10~100μm,最佳為15~50μm。
拋棄式發熱包外袋用多層膜中之密封劑層30之位置並無特別限定,只要設置於外袋之內側表面則足夠,但亦可設置於外袋之外側表
面。
本發明之拋棄式發熱包外袋用多層膜可於任意之位置設置接著劑層40作為構成成分,較佳為於上述第1阻隔層10與第2阻隔層20之間設置接著劑層40,使第1阻隔層10與第2阻隔層20接著而積層。作為構成接著劑層之接著劑,可無限制地使用通常用於拋棄式發熱包外袋用多層膜之接著劑,例如,可使用醚系接著劑、聚乙酸乙烯酯系接著劑、包含丙烯酸之乙酯、丁酯、2-乙基己酯等之均聚物、或該等與甲基丙烯酸甲酯、丙烯腈、苯乙烯等之共聚物等的聚丙烯酸酯系接著劑、氰基丙烯酸酯系接著劑、包含乙烯與乙酸乙烯酯、丙烯酸乙酯、丙烯酸、甲基丙烯酸等單體之共聚物等之乙烯共聚物系接著劑、纖維素系接著劑、聚酯系接著劑、聚醯胺系接著劑、聚醯亞胺系接著劑、包含脲樹脂或三聚氰胺樹脂等之胺基樹脂系接著劑、酚樹脂系接著劑、環氧系接著劑、聚胺基甲酸酯系接著劑、反應型(甲基)丙烯酸系接著劑、包含氯丁二烯橡膠、腈橡膠、苯乙烯-丁二烯橡膠等之橡膠系接著劑、矽酮系接著劑、包含鹼金屬矽酸鹽、低熔點玻璃等之無機系接著劑、其他接著劑。接著劑之組成系可為水性型、溶液型、乳液型、分散型等任一組合物形態。又,接著劑之性狀可為膜/片狀、粉末狀、固體狀等任一形態。進而,關於接著機構,可為化學反應型、溶劑揮發型、熱熔融型、熱壓型等任一形態。關於接著劑之使用態樣,亦可無限制地使用通常所使用之態樣,例如,可於第1阻隔層10或第2阻隔層20之至少一者藉由輥塗法、凹版輥式塗佈法、接觸塗佈法、其他塗佈法、或印刷法等塗佈接著劑,繼而,使溶劑等乾燥而形成接著劑層。作為接著劑之含量,較佳為0.1~10g/m2(乾燥狀態),更佳為0.5~8g/m2(乾燥狀態),最佳為1.5~4g/m2(乾燥狀態)。
本發明之拋棄式發熱包外袋用多層膜可於任意之位置設置印刷油墨層50作為構成成分。作為印刷油墨層50,可將通常之油墨媒劑之
1種或2種以上作為主成分,並視需要任意地添加塑化劑、穩定劑、抗氧化劑、光穩定劑、紫外線吸收劑、硬化劑、交聯劑、潤滑劑、抗靜電劑、填充劑、其他等添加劑之1種或2種以上,進而,添加染料、顏料等著色劑,並利用溶劑、稀釋劑等充分地進行混練而製備油墨組合物,繼而,使用該油墨組合物,例如藉由凹版印刷、膠版印刷、凸版印刷、網版印刷、轉印印刷、軟版印刷、其他等印刷方式,印刷所需之文字、圖形、記號、花樣等而形成。
作為油墨媒劑,可無限制地使用通常用於拋棄式發熱包外袋之油墨媒劑,例如,可列舉:亞麻仁油、桐油、大豆油、烴油、松香、松香酯、松香改性樹脂、蟲膠、醇酸樹脂、酚系樹脂、順丁烯二酸樹脂、天然樹脂、烴樹脂、聚氯乙烯系樹脂、聚乙酸乙烯酯系樹脂、聚苯乙烯系樹脂、聚乙烯醇縮丁醛樹脂、丙烯酸或甲基丙烯酸系樹脂、聚醯胺系樹脂、聚酯系樹脂、聚胺基甲酸酯系樹脂、環氧系樹脂、脲樹脂、三聚氰胺樹脂、胺基醇酸系樹脂、硝化纖維素、乙基纖維素、氯化橡膠、環化橡膠及其他之1種或2種以上。
作為印刷油墨層50之含量,較佳為0.1~10g/m2(乾燥狀態),更佳為0.5~8g/m2(乾燥狀態),最佳為1~5g/m2(乾燥狀態)。
本發明之拋棄式發熱包外袋用多層膜亦可進而包含追加之樹脂層60。追加之樹脂層60只要不阻礙本發明之拋棄式發熱包外袋用多層膜之氣體透過性及水蒸氣透過性,則可為包含任意之樹脂之層,並且可根據樹脂之特性而設置於所需之任意之位置。例如,於將可用作密封劑層30之上述熱熔合性樹脂用於追加之樹脂層60之情形時,可設置於較密封劑層30更靠外側而用作形成外袋時之熱密封部分。又,於將可用作第1阻隔層10及第2阻隔層20之基材之上述耐熱性樹脂用於追加之樹脂層60之情形時,可設置於第1阻隔層10與第2阻隔層20之間而提高多層膜之強度,或者亦可設置於與密封劑層30相反之側且較第2阻
隔層20更靠外側,即成為拋棄式發熱包外袋之外表面之位置,而使之發揮作為保護膜之功能。
追加之樹脂層60之厚度並無特別限定,較佳為3~500μm,更佳為5~300μm,進而較佳為5~100μm,最佳為5~50μm。
本發明之拋棄式發熱包外袋用多層膜可實現較佳為1.5~4.5cc/(m2‧day‧atm)、更佳為2.0~4.0cc/(m2‧day‧atm)、最佳為2.0~3.5cc/(m2‧day‧atm)之氧氣透過度(20℃、90%RH)及較佳為0.05~3.5g/(m2‧day)、更佳為0.05~3.0g/(m2‧day)、最佳為0.05~2.5g/(m2‧day)之水蒸氣透過度(40℃、90%RH)。藉由將本發明之拋棄式發熱包外袋用多層膜之氧氣透過度及水蒸氣透過度設為上述數值範圍內,阻止氧氣、水蒸氣等之透過之阻氣性優異,並且可發揮能防止由保存中所產生之氫氣引起之膨脹之效果。為了拋棄式發熱包之穩定之長期保存,需要氧氣透過度及水蒸氣透過度之兩者共同為上述範圍內,若任一者變為範圍外,則變得無法獲得所需之效果。
本發明之拋棄式發熱包外袋用多層膜可實現較佳為15.0N/15mm以上、更佳為20.0N/15mm以上、最佳為25.0N/15mm以上之密封強度。藉由將本發明之拋棄式發熱包外袋用多層膜之密封強度設為上述數值範圍,可發揮即便外袋自外部受到強烈之衝擊,外袋亦不易開封、破裂之效果。
於本發明之拋棄式發熱包外袋用多層膜中,較佳為不包含蒸鍍金屬或金屬氧化物而成之蒸鍍層。若本發明之拋棄式發熱包外袋用多層膜具有蒸鍍金屬或金屬氧化物而成之蒸鍍層,則存在蒸鍍層產生變質、變色等變化,拋棄式發熱包外袋用多層膜之外觀變差或無法發揮蒸鍍層原本之阻氣性等之情況。此種現象之原因並不明確,但認為可由聚偏二氯乙烯層12及/或聚偏二氯乙烯層22產生之氯化氫等氣體可能對蒸鍍層造成了某些影響。
其次,對本發明之拋棄式發熱包外袋用多層膜及拋棄式發熱包外袋之製造方法進行說明。
本發明之拋棄式發熱包外袋用多層膜可於積層成為第1阻隔層10之聚偏二氯乙烯樹脂塗層耐熱性樹脂、成為第2阻隔層20之聚偏二氯乙烯樹脂塗層耐熱性樹脂、密封劑層30、成為接著劑層40之接著劑、以及視需要之印刷油墨層50及追加之樹脂層60之狀態下,使用輥等進行壓接而製造。
繼而,將2片拋棄式發熱包外袋用多層膜以密封劑層30之面對向之方式重疊,並對密封劑層30之周緣部進行熱密封,藉此形成為袋狀,從而可製造拋棄式發熱包外袋。關於熱密封之態樣,可無限制地使用通常所使用之態樣,例如,可為側面密封型、兩面密封型、三面密封型、四面密封型、信封黏貼密封型、對接密封型(枕狀密封型)、帶褶密封型、平底密封型、方底密封型、直立密封型、其他熱密封形態。關於熱密封之方法,亦可無限制地使用通常所使用之方法,例如,可為桿密封、旋轉輥密封、帶密封、脈衝密封、高頻密封、超音波密封等。
本發明之拋棄式發熱包係將收納有發熱性組合物之內袋密封包裝於由上述拋棄式發熱包外袋用多層膜所形成之拋棄式發熱包外袋而成。
發熱性組合物可為通常之拋棄式發熱包所使用之發熱性組合物,並無特別限定。例如,可為含有鐵粉等金屬粉、食鹽等反應助劑、活性碳、保水劑、水及其他之發熱性組合物。具體而言,例如,可含有還原鐵粉、鑄鐵粉等鐵粉、鋁粉等金屬粉100重量份、氯化鈉等反應助劑3~10重量份、活性碳及保水劑20~40重量份、水30~90重量份、及其他等。再者,於上述發熱性組合物中,例如,可添加氫氧化鈉、氫氧化鉀、碳酸氫鈉、磷酸三鈉等鹼金屬氫氧化物及弱鹼性
之鹼金屬鹽等作為氫氣產生抑制劑,關於其使用量,可相對於金屬粉微量添加而使用。
又,收納發熱性組合物之內袋只要有金屬可於氧氣之存在下發熱之程度之透氣性即可,例如,可使用一個面利用透氣性包裝用材料而另一個面利用非透氣性包裝用材料製作之袋體、或兩個面均利用透氣性包裝用材料製作之袋體等。作為透氣性包裝用材料,例如,可使用織布或不織布、將塑膠膜或片等穿孔而成之多孔質片、該等片之複合片、其他等。又,作為非透氣性包裝用材料,例如,可使用聚乙烯系樹脂、聚丙烯系樹脂、乙烯-丙烯共聚物、乙烯-乙酸乙烯酯共聚物、離子聚合物樹脂、乙烯-丙烯酸乙酯共聚物、乙烯-丙烯酸或甲基丙烯酸共聚物、甲基戊烯聚合物、聚丁烯系樹脂、聚乙酸乙烯酯系樹脂、聚(甲基)丙烯酸系樹脂、聚丙烯腈系樹脂、聚苯乙烯系樹脂、丙烯腈-苯乙烯共聚物(AS系樹脂)、丙烯腈-丁二烯-苯乙烯共聚物(ABS系樹脂)、聚酯系樹脂、聚醯胺系樹脂、聚碳酸酯系樹脂、聚乙烯醇系樹脂、乙烯-乙酸乙烯酯共聚物之皂化物、氟系樹脂、二烯系樹脂、聚縮醛系樹脂、聚胺基甲酸酯系樹脂、硝化纖維素、其他等公知之樹脂之膜或片。關於內袋之製造方法,可無限制地使用通常公知之方法,例如,可較佳地使用關於外袋之製造於上文所述之各種熱密封法。
以下,列舉實施例及比較例進而具體地對本發明進行說明。
(實施例1)[圖1所示之拋棄式發熱包外裝用多層膜之製造]
以如下方式製造圖1所示之包含第1及第2阻隔層10、20之拋棄式發熱包外裝用多層膜,該第1及第2阻隔層10、20包含耐熱性樹脂基材11、21(雙軸延伸聚丙烯膜11、21)、及於上述耐熱性樹脂基材11、21之至少一個面塗佈聚偏二氯乙烯而成之聚偏二氯乙烯層12、22。
於第2阻隔層20即具有聚偏二氯乙烯層22之雙軸延伸聚丙烯膜21(雙軸延伸聚丙烯膜21之厚度:30μm,聚偏二氯乙烯層22之厚度:1μm,氧氣透過度:9.7cc/(m2‧day‧atm),水蒸氣透過度:4.4g/(m2‧day))之聚偏二氯乙烯層22側,使用通常之凹版油墨組合物,藉由凹版印刷方式,印刷文字、圖形、記號、圖樣等而形成印刷油墨層50。其次,於上述所形成之印刷油墨層50之上,塗佈醚系接著劑並使之乾燥而形成接著劑層40。於該接著劑層40之上,以聚偏二氯乙烯層12與接著劑層40接觸之方式載置第1阻隔層10即具有聚偏二氯乙烯層12之雙軸延伸聚丙烯膜11(雙軸延伸聚丙烯膜11之厚度:30μm,聚偏二氯乙烯層12之厚度:1μm,氧氣透過度:9.7cc/(m2‧day‧atm),水蒸氣透過度:4.4g/(m2‧day)),使之積層一體化。然後,於該雙軸延伸聚丙烯膜11之上,塗佈醚系接著劑並使之燥而形成接著劑層40。於該接著劑層40之上,載置未延伸聚丙烯膜30(厚度:25μm,氧氣透過度:2400cc/(m2‧day‧atm),水蒸氣透過度:14.4g/(m2‧day)),使之積層一體化,從而製造自下層側觀察,包含未延伸聚丙烯膜30/接著劑層40/雙軸延伸聚丙烯膜11/聚偏二氯乙烯層12/接著劑層40/印刷油墨層50/聚偏二氯乙烯層22/雙軸延伸聚丙烯膜21之拋棄式發熱包外袋用多層膜。
(實施例2)[圖1所示之拋棄式發熱包外裝用多層膜之製造]
使用具有聚偏二氯乙烯層12之雙軸延伸聚對苯二甲酸乙二酯膜11(雙軸延伸聚對苯二甲酸乙二酯膜11之厚度:12μm,聚偏二氯乙烯層12之厚度:1μm,氧氣透過度:8.1cc/(m2‧day‧atm),水蒸氣透過度:10g/(m2‧day))代替具有聚偏二氯乙烯層12之雙軸延伸聚丙烯膜11(雙軸延伸聚丙烯膜11之厚度:30μm,聚偏二氯乙烯層12之厚度:1μm,氧氣透過度:9.7cc/(m2‧day‧atm),水蒸氣透過度:4.4g/(m2‧day))作為第1阻隔層10,除此以外,與實施例1同樣地製造自
下層側觀察,包含未延伸聚丙烯膜30/接著劑層40/雙軸延伸聚對苯二甲酸乙二酯膜11/聚偏二氯乙烯層12/接著劑層40/印刷油墨層50/聚偏二氯乙烯層22/雙軸延伸聚丙烯膜21之拋棄式發熱包外袋用多層膜。
(實施例3)[圖1所示之拋棄式發熱包外裝用多層膜之製造]
使用具有聚偏二氯乙烯層12之雙軸延伸聚醯胺膜11(雙軸延伸聚醯胺膜11之厚度:25μm,聚偏二氯乙烯層12之厚度:1μm,氧氣透過度:6.7cc/(m2‧day‧atm),水蒸氣透過度:9.7g/(m2‧day))代替具有聚偏二氯乙烯層12之雙軸延伸聚丙烯膜11(雙軸延伸聚丙烯膜11之厚度:30μm,聚偏二氯乙烯層12之厚度:1μm,氧氣透過度:9.7cc/(m2‧day‧atm),水蒸氣透過度:4.4g/(m2‧day))作為第1阻隔層10,除此以外,與實施例1同樣地製造自下層側觀察,包含未延伸聚丙烯膜30/接著劑層40/雙軸延伸聚醯胺膜11/聚偏二氯乙烯層12/接著劑層40/印刷油墨層50/聚偏二氯乙烯層22/雙軸延伸聚丙烯膜21之拋棄式發熱包外袋用多層膜。
(實施例4)[圖1所示之拋棄式發熱包外裝用多層膜之製造]
使用具有聚偏二氯乙烯層12、22之雙軸延伸聚對苯二甲酸乙二酯膜11、21(雙軸延伸聚對苯二甲酸乙二酯膜11、21之厚度:12μm,聚偏二氯乙烯層12、22之厚度:1μm,氧氣透過度:8.1cc/(m2‧day‧atm),水蒸氣透過度:10g/(m2‧day))代替具有聚偏二氯乙烯層12、22之雙軸延伸聚丙烯膜11、21(雙軸延伸聚丙烯膜11、21之厚度:30μm,聚偏二氯乙烯層12、22之厚度:1μm,氧氣透過度:9.7cc/(m2‧day‧atm),水蒸氣透過度:4.4g/(m2‧day))作為第1及第2阻隔層10、20,除此以外,與實施例1同樣地製造自下層側觀察,包含未延伸聚丙烯膜30/接著劑層40/雙軸延伸聚對苯二甲酸乙二酯膜11/聚偏二氯乙烯層12/接著劑層40/印刷油墨層50/聚偏二氯乙烯層22/雙軸延伸聚對苯二甲酸乙二酯膜21之拋棄式發熱包外袋用多層膜。
(實施例5)[圖1所示之拋棄式發熱包外裝用多層膜之製造]
使用具有聚偏二氯乙烯層12、22之雙軸延伸聚醚胺膜11、21(雙軸延伸聚醯胺膜11、21之厚度:25μm,聚偏二氯乙烯層12、22之厚度:1μm,氧氣透過度:6.7cc/(m2‧day‧atm),水蒸氣透過度:9.7g/(m2‧day))代替具有聚偏二氯乙烯層12、22之雙軸延伸聚丙烯膜11、21(雙軸延伸聚丙烯膜11、21之厚度:30μm,聚偏二氯乙烯層12、22之厚度:1μm,氧氣透過度:9.7cc/(m2‧day‧atm),水蒸氣透過度:4.4g/(m2‧day))作為第1及第2阻隔層10、20,除此以外,與實施例1同樣地製造自下層側觀察,包含未延伸聚丙烯膜30/接著劑層40/雙軸延伸聚醯胺膜11/聚偏二氯乙烯層12/接著劑層40/印刷油墨層50/聚偏二氯乙烯層22/雙軸延伸聚醯胺膜21之拋棄式發熱包外袋用多層膜。
(實施例6)[圖1所示之拋棄式發熱包外裝用多層膜之製造]
使用具有聚偏二氯乙烯層22之雙軸延伸聚醯胺膜21(雙軸延伸聚醯胺膜21之厚度:25μm,聚偏二氯乙烯層22之厚度:1μm,氧氣透過度:6.7cc/(m2‧day‧atm),水蒸氣透過度:9.7g/(m2‧day))代替具有聚偏二氯乙烯層22之雙軸延伸聚丙烯膜21(雙軸延伸聚丙烯膜21之厚度:30μm,聚偏二氯乙烯層22之厚度:1μm,氧氣透過度:9.7cc/(m2‧day‧atm),水蒸氣透過度:4.4g/(m2‧day))作為第2阻隔層20,並且使用具有聚偏二氯乙烯層12之雙軸延伸聚對苯二甲酸乙二酯膜11(雙軸延伸聚對苯二甲酸乙二酯膜11之厚度:12μm,聚偏二氯乙烯層12之厚度:1μm,氧氣透過度:8.1cc/(m2‧day‧atm),水蒸氣透過度:10g/(m2‧day))代替具有聚偏二氯乙烯層12之雙軸延伸聚丙烯膜11(雙軸延伸聚丙烯膜11之厚度:30μm,聚偏二氯乙烯層12之厚度:1μm,氧氣透過度:9.7cc/(m2‧day‧atm),水蒸氣透過度:4.4g/(m2‧day)))作為第1阻隔層10,除此以外,與實施例1同樣地製造自
下層側觀察,包含未延伸聚丙烯膜30/接著劑層40/雙軸延伸聚對苯二甲酸乙二酯膜11/聚偏二氯乙烯層12/接著劑層40/印刷油墨層50/聚偏二氯乙烯層22/雙軸延伸聚醯胺膜21之拋棄式發熱包外袋用多層膜。
(實施例7)[圖3所示之拋棄式發熱包外裝用多層膜之製造]
以如下方式製造圖3所示之包含第1及第2阻隔層10、20之拋棄式發熱包外裝用多層膜,該第1及第2阻隔層10、20包含耐熱性樹脂基材11、21(雙軸延伸聚丙烯膜11、雙軸延伸聚對苯二甲酸乙二酯膜21)、及於上述耐熱性樹脂基材11、21之至少一個面塗佈聚偏二氯乙烯而成之聚偏二氯乙烯層12、22。
於第1阻隔層10即具有聚偏二氯乙烯層12之雙軸延伸聚丙烯膜11(雙軸延伸聚丙烯膜11之厚度:30μm,聚偏二氯乙烯層12之厚度:1μm,氧氣透過度:9.7cc/(m2‧day‧atm),水蒸氣透過度:4.4g/(m2‧day))之聚偏二氯乙烯層12側,塗佈醚系接著劑並使之乾燥而形成接著劑層40。於該接著劑層40之上,以雙軸延伸聚對苯二甲酸乙二酯膜21與接著劑層40接觸之方式載置第2阻隔層20即具有聚偏二氯乙烯層22之雙軸延伸聚對苯二甲酸乙二酯膜21(雙軸延伸聚對苯二甲酸乙二酯膜21之厚度:12μm,聚偏二氯乙烯層22之厚度:1μm,氧氣透過度:8.1cc/(m2‧day‧atm),水蒸氣透過度:10g/(m2‧day)),使之積層一體化。又,於第1阻隔層10之雙軸延伸聚丙烯膜11側,塗佈醚系接著劑並使之乾燥而形成接著劑層40。於該接著劑層40之上,載置未延伸聚丙烯膜30(厚度:20μm,氧氣透過度:1500cc/(m2‧day‧atm),水蒸氣透過度:8g/(m2‧day)),使之積層一體化。進而,於第2阻隔層20之聚偏二氯乙烯層22之上塗佈醚系接著劑並使之乾燥而形成接著劑層40。另一方面,於追加之樹脂層60即雙軸延伸聚丙烯膜(厚度:20μm,氧氣透過度:1500cc/(m2‧day‧atm),水蒸氣透過度:8g/(m2‧day))之上,使用通常之凹版油墨組合
物,藉由凹版印刷方式,印刷文字、圖形、記號、圖樣等而形成印刷油墨層50。然後,使與第2阻隔層20之聚偏二氯乙烯層22相鄰之接著劑層40與上述所形成之印刷油墨層50積層一體化,從而製造自下層側觀察,包含未延伸聚丙烯膜30/接著劑層40/雙軸延伸聚丙烯膜11/聚偏二氯乙烯層12/接著劑層40/雙軸延伸聚對苯二甲酸乙二酯膜21/聚偏二氯乙烯層22/接著劑層40/印刷油墨層50/雙軸延伸聚丙烯膜60之拋棄式發熱包外袋用多層膜。
(實施例8~13)[圖3所示之拋棄式發熱包外裝用多層膜之製造]
使用下述表1所示之膜代替具有聚偏二氯乙烯層22之雙軸延伸聚對苯二甲酸乙二酯膜21(雙軸延伸聚對苯二甲酸乙二酯膜21之厚度:12μm,聚偏二氯乙烯層22之厚度:1μm,氧氣透過度:8.1cc/(m2‧day‧atm),水蒸氣透過度:10g/(m2‧day)作為第2阻隔層20,並且使用下述表1所示之膜代替雙軸延伸聚丙烯膜(厚度:20μm,氧氣透過度:1500cc/(m2‧day‧atm),水蒸氣透過度:8g/(m2‧day))作為追加之樹脂層60,除此以外,與實施例7同樣地分別製造拋棄式發熱包外袋用多層膜。
KPET#12:具有聚偏二氯乙烯層之雙軸延伸聚對苯二甲酸乙二酯膜(雙軸延伸聚對苯二甲酸乙二酯膜之厚度:12μm,聚偏二氯乙烯層之厚度:1μm,氧氣透過度:8.1cc/(m2‧day‧atm),水蒸氣透過
度:10g/(m2‧day))
KOPP#20:具有聚偏二氯乙烯層之雙軸延伸聚丙烯膜(雙軸延伸聚丙烯膜之厚度:20μm,聚偏二氯乙烯層之厚度:1μm,氧氣透過度:8.1cc/(m2‧day‧atm),水蒸氣透過度:5g/(m2‧day))
KONY#15:具有聚偏二氯乙烯層之雙軸延伸聚醯胺膜(雙軸延伸聚醯胺膜之厚度:15μm,聚偏二氯乙烯層之厚度:1μm,氧氣透過度:8.1cc/(m2‧day‧atm),水蒸氣透過度:10g/(m2‧day))
PET#12:雙軸延伸聚對苯二甲酸乙二酯膜(厚度:12μm,氧氣透過度:80cc/(m2‧day‧atm),水蒸氣透過度:50g/(m2‧day))
ONY#15:雙軸延伸聚醯胺膜(厚度:15μm,氧氣透過度:30cc/(m2‧day‧atm),水蒸氣透過度:250g/(m2‧day))
(比較例1)
於具有聚偏二氯乙烯層之雙軸延伸聚丙烯膜(雙軸延伸聚丙烯膜之厚度:30μm,聚偏二氯乙烯層之厚度:1μm,氧氣透過度:9.7cc/(m2‧day‧atm),水蒸氣透過度:4.4g/(m2‧day))之聚偏二氯乙烯層側,與實施例1同樣地形成印刷油墨層及接著劑層。於該接著劑層之上,載置直鏈狀低密度聚乙烯膜(厚度:30μm,氧氣透過度:5000cc/(m2‧day‧atm),水蒸氣透過度:16.6g/(m2‧day))之後,於該直鏈狀低密度聚乙烯膜之上,與上述同樣地設置接著劑層,進而於其上載置乙烯-乙酸乙烯酯共聚物膜(厚度:30μm,氧氣透過度:10000cc/(m2‧day‧atm),水蒸氣透過度:75g/(m2‧day)),使之積層一體化,從而製造自下層側觀察,包含乙烯-乙酸乙烯酯共聚物膜/接著劑層/直鏈狀低密度聚乙烯膜/接著劑層/印刷油墨層/聚偏二氯乙烯層/雙軸延伸聚丙烯膜之拋棄式發熱包外袋用多層膜。
(比較例2)
使用於其一個面具有2層聚偏二氯乙烯層之雙軸延伸聚丙烯膜(雙
軸延伸聚丙烯膜之厚度:30μm,2層聚偏二氯乙烯層之總厚度:2μm,氧氣透過度:5.5cc/(m2‧day‧atm),水蒸氣透過度:4.4g/(m2‧day))代替具有聚偏二氯乙烯層之雙軸延伸聚丙烯膜(雙軸延伸聚丙烯膜之厚度:30μm,聚偏二氯乙烯層之厚度:1μm,氧氣透過度:9.7cc/(m2‧day‧atm),水蒸氣透過度:4.4g/(m2‧day)),除此以外,與比較例1同樣地製造自下層側觀察,包含乙烯-乙酸乙烯酯共聚物膜/接著劑層/直鏈狀低密度聚乙烯膜/接著劑層/印刷油墨層/聚偏二氯乙烯層/聚偏二氯乙烯層/雙軸延伸聚丙烯膜之拋棄式發熱包外袋用多層膜。再者,2層聚偏二氯乙烯層係藉由於作為基材之雙軸延伸聚丙烯膜塗佈第1層聚偏二氯乙烯並使之乾燥之後,進而於其上塗佈第2層聚偏二氯乙烯並使之乾燥而製造。
(比較例3)
使用具有壁厚之聚偏二氯乙烯層之雙軸延伸聚丙烯膜(雙軸延伸聚丙烯膜之厚度:30μm,聚偏二氯乙烯層之厚度:2μm,氧氣透過度:5.5cc/(m2‧day‧atm),水蒸氣透過度:4.5g/(m2‧day))代替具有聚偏二氯乙烯層之雙軸延伸聚丙烯膜(雙軸延伸聚丙烯膜之厚度:30μm,聚偏二氯乙烯層之厚度:1μm,氧氣透過度:9.7cc/(m2‧day‧atm),水蒸氣透過度:4.4g/(m2‧day)),除此以外,與比較例1同樣地製造自下層側觀察,包含乙烯-乙酸乙烯酯共聚物膜/接著劑層/直鏈狀低密度聚乙烯膜/接著劑層/印刷油墨層/壁厚之聚偏二氯乙烯層/雙軸延伸聚丙烯膜之拋棄式發熱包外袋用多層膜。
(比較例4)
於雙軸延伸聚丙烯膜(厚度:20μm,氧氣透過度:1500cc/(m2‧day‧atm),水蒸氣透過度:8g/(m2‧day))之一個面,與實施例1同樣地形成印刷油墨層及接著劑層。於該接著劑層之上,以接著劑層與鋁之蒸鍍層接觸之方式載置具有鋁之蒸鍍層之雙軸延伸聚對苯二甲酸乙
二酯膜(厚度:12μm,蒸鍍層之厚度:約600埃以下,氧氣透過度:1.5cc/(m2‧day‧atm),水蒸氣透過度1.7g/(m2‧day)),使之積層一體化。進而,於具有鋁之蒸鍍層之雙軸延伸聚對苯二甲酸乙二酯膜之與鋁之蒸鍍層相反之側形成接著劑層之後,於其上載置直鏈狀低密度聚乙烯膜(厚度:30μm,氧氣透過度:5000cc/(m2‧day‧atm),水蒸氣透過度:16.6g/(m2‧day)),使之積層一體化,從而製造自下層側觀察,包含直鏈狀低密度聚乙烯膜/接著劑層/雙軸延伸聚對苯二甲酸乙二酯膜/鋁之蒸鍍層/接著劑層/印刷油墨層/雙軸延伸聚丙烯膜之拋棄式發熱包外袋用多層膜。
(參考例)
於具有聚偏二氯乙烯層之雙軸延伸聚丙烯膜(雙軸延伸聚丙烯膜之厚度:20μm,聚偏二氯乙烯層之厚度:1μm,氧氣透過度:8.1cc/(m2‧day‧atm),水蒸氣透過度:5g/(m2‧day))之聚偏二氯乙烯層側,使用通常之凹版油墨組合物,藉由凹版印刷方式,印刷文字、圖形、記號、圖樣等而形成印刷油墨層。其次,於上述所形成之印刷油墨層之上,塗佈醚系接著劑並使之乾燥而形成接著劑層。於該接著劑層之上,以鋁蒸鍍層與接著劑層接觸之方式載置具有鋁之蒸鍍層之未延伸聚丙烯膜(厚度:25μm,蒸鍍層之厚度:約600埃以下,氧氣透過度:10cc/(m2‧day‧atm),水蒸氣透過度:0.5g/(m2‧day)),使之積層一體化,從而製造自下層側觀察,包含未延伸聚丙烯膜/鋁之蒸鍍層/接著劑層/印刷油墨層/聚偏二氯乙烯層/雙軸延伸聚丙烯膜之拋棄式發熱包外袋用多層膜。
(評價)
使用實施例1~6、比較例1~4、及參考例中所製造之拋棄式發熱包外袋用多層膜,如下所述,進行(1)氧氣透過度、(2)水蒸氣透過度、(3)加速試驗後之外觀之評價、(4)加速試驗後之發熱性能(持續時
間)之評價、(5)密封強度、(6)耐衝擊性之評價、(7)耐候性之評價。
(1)氧氣透過度之測定
於以下之溫度及濕度之條件下,使用以下之測定機械,於以下之測定條件下測定氧氣透過度(cc/(m2‧day‧atm))。
溫度:20℃,濕度:90%RH,測定機械:膜康(mocon)公司製造之OX-TRAN 2/20,測定方法:每隔30分鐘、連續測定20次
(2)水蒸氣透過度之測定
於以下之溫度及濕度之條件,使用以下之測定機械,於以下之測定條件下測定水蒸氣透過度(g/(m2‧day))。
溫度:40℃,濕度:90%RH,測定機械:膜康(mocon)公司製造之OX-TRAN 2/20,測定方法:每隔30分鐘、連續測定20次
(3)加速試驗後之外觀之評價
分別準備2片實施例1~6、比較例1~4、及參考例之拋棄式發熱包外袋用多層膜,使密封劑層之熱熔合性基材(實施例1~6、參考例:未延伸聚丙烯膜,比較例1~3:乙烯-乙酸乙烯酯共聚物膜,比較例4:直鏈狀低密度聚乙烯膜)之面對向而重疊之後,對其外周緣部進行三面熱密封而製造形成密封部,並且於上方具有開口部之三面熱密封型之拋棄式發熱包外袋。
製備包含鐵粉22g、活性碳6g、保水劑6g、水10g之發熱性組合物,繼而,將該發熱性組合物填充包裝於一個面由包含聚乙烯膜之透氣性多孔質內袋構成,另一個面包含聚乙烯膜之非透氣性內袋,從而製造包含單個包裝體之黏貼型之拋棄式發熱包。
其次,自上述所製造之拋棄式發熱包外袋之開口部,填充上述所製造之包含單個包裝體之拋棄式發熱包,其後,對該開口部進行熱
密封而形成上方密封部,從而製造拋棄式發熱包製品。
重疊5片以此方式而獲得之拋棄式發熱包製品,並將其載置於台之上,測定重疊5片之狀態下之高度(mm)(以下,設為「高度H1(mm)」)。其次,於重疊5片拋棄式發熱包製品之狀態下,於50℃之溫度保存3個月,於3個月期間中,每隔1週測定重疊5片之狀態下之高度(mm)。並且,將經過3個月後之高度設為「高度H2(mm)」。但是,於在保存期間中,拋棄式發熱包製品之外袋發生膨脹而破損之情形時,將破損前最大之高度設為「高度H2(mm)」。然後,算出H2-H1(mm)之值,對照以下之表2之基準,作為加速試驗後之外觀之評價。
(4)加速試驗後之發熱性能(持續時間)之評價
與上述「(3)加速試驗後之外觀之評價」同樣地製造拋棄式發熱包製品。
對於以此方式而獲得之10個拋棄式發熱包製品,將拋棄式發熱包外袋開封並將拋棄式發熱包取出,基於JIS S4100對作為拋棄式發熱包之發熱性能進行試驗。將其持續時間之平均值作為「發熱性能(持續時間)/初期」(以下,設為「持續時間T1」)。
另一方面,對於以如上所述之方式而獲得之10個拋棄式發熱包製品,於50℃之溫度保存3個月之後,將拋棄式發熱包外袋開封並將拋棄式發熱包取出,基於JIS S4100對作為拋棄式發熱包之發熱性能
進行試驗。將其持續時間之平均值作為「發熱性能(持續時間)/加速試驗後」(以下,設為「持續時間T2」)。
然後,算出T2/T1×100(%)之值,對照以下之表3之基準,作為加速試驗後之發熱性能(持續時間)之評價。
(5)密封強度
分別準備2片實施例1~6、比較例1~4、及參考例之拋棄式發熱包外袋用多層膜,使密封劑層之熱熔合性基材(實施例1~6、參考例:未延伸聚丙烯膜,比較例1~3:乙烯-乙酸乙烯酯共聚物膜,比較例4:直鏈狀低密度聚乙烯膜)之面對向而重疊後,於溫度160℃、壓力0.25MPa、時間0.5秒之條件下,遍及重疊之拋棄式發熱包外袋用多層膜之一端側之全長而形成密封寬度10mm之熱密封部。自該具有熱密封部之2片拋棄式發熱包外袋用多層膜之積層體,各自切下3片寬度15mm×長度50mm之短條狀之試樣(包含寬度15mm×長度10mm之熱密封部),並使用拉伸試驗機(TCE公司製造,製品名AUTOCOM),以拉伸速度300mm/min、夾具間隔10mm測定剝離強度(N/15mm),並算出平均值。
密封強度之數值若為13.0N/15mm以上之數值範圍,則對用作拋棄式發熱包用外袋而言並無較大之問題,若為15.0N/15mm以上之數值範圍,則即便外袋自外部受到強烈之衝擊,外袋亦不易開封、破裂。
(6)耐衝擊性之評價
(6-1)運輸試驗
與上述「(3)加速試驗後之外觀之評價」同樣地製造拋棄式發熱包製品。
針對實施例1~6、比較例1~4及參考例之各樣品,準備以此方式而獲得之拋棄式發熱包製品各64個,並將64個拋棄式發熱包製品按各樣品分別裝入至1個瓦楞紙箱(高度15cm×寬度36.5cm×深度25.3cm),並利用國際貨物航空郵件將該瓦楞紙箱自日本大阪運輸至中國上海,又,於中國上海接收瓦楞紙箱之後,利用同樣之運輸郵件送回日本大阪。自以此方式運輸之瓦楞紙箱取出64個拋棄式發熱包製品,對於全部拋棄式發熱包製品,目視確認外袋有無開封、破裂。又,作為AGELESS密封檢查,對於進行過目視確認後之64個拋棄式發熱包製品,於外袋之熱密封部以外之部位開洞,將滲透液(成分:脂肪酸酯,高沸點烴,紅色塗料)噴霧於外袋內,確認自熱密封部有無滲透液之漏出。然後,對照以下之表4之基準,作為運輸試驗之評價。
(6-2)掉落試驗
與上述「(3)加速試驗後之外觀之評價」同樣地製造拋棄式發熱包製品。
針對實施例1~6、比較例1~4及參考例之各樣品,準備以此方
式而獲得之拋棄式發熱包製品各64個,並將64個拋棄式發熱包製品按各樣品分別裝入至1個瓦楞紙箱(高度15cm×寬度36.5cm×深度25.3cm),使該瓦楞紙箱自1m之高度以1角3稜6面之方向自由掉落至水平放置於地面之鐵板之上各1次,總計自由掉落10次。自以此方式掉落之瓦楞紙箱取出64個拋棄式發熱包製品,對於全部拋棄式發熱包製品,目視確認外袋有無開封、破裂。又,與上述「(6-1)運輸試驗」同樣地進行AGELESS密封檢查,確認自熱密封部有無滲透液之漏出。然後,對照上述「(6-1)運輸試驗」之表4之基準,作為掉落試驗之評價。
(7)耐候性之評價
與上述「(3)加速試驗後之外觀之評價」同樣地製造拋棄式發熱包製品。
對於以此方式獲得之拋棄式發熱包製品,於放射照度0.35W/m2、波長300~800nm、黑面板溫度42℃、濕度52%RH、20小時之條件下,使用氙氣耐候試驗機(6.5kW氙氣電弧燈式促進耐候性試驗機,東洋精機製作所股份有限公司製造,Atlas Ci4000)進行光照射,進行促進耐候性試驗。
然後,觀察光照射後之拋棄式發熱包製品之外觀,對照以下之表5之基準,作為耐候性之評價。
若上述表6之外觀評價為「無變化」,則即便於長時間保存拋棄式發熱包製品之後,外觀亦無變化,可作為製品於市場販賣。另一方面,若上述表6之外觀評價為「稍有減壓傾向」、「減壓傾向」、「稍有膨脹傾向」或「膨脹傾向」,則於長時間保存拋棄式發熱包製品之後,外觀發生變化,欠佳。
根據上述表6之結果,於實施例1~4及6中,加速試驗前後之包裝製品之外觀無變化,且即便於長時間保存之後,製品之發熱功能亦無劣化。又,於實施例1~6中,拋棄式發熱包外袋之水蒸氣透過度較低,水蒸氣不易通過,因此,水分不易自外部侵入至外袋內部,又,作為拋棄式發熱包之成分所含有之水分不易逃逸至外部,於長時間保存之後,亦充分地發揮作為拋棄式發熱包之功能。進而,根據上述表7之結果,於實施例1~6中,因密封強度、耐衝擊性優異,故即便外袋自外部受到強烈之衝擊,外袋亦不會開封、破裂。此外,於實施例1~6中,因耐候性優異,故即便外袋暴露於日光等紫外線,亦不會引起變色等外觀之變化。
另一方面,於比較例1~4中,加速試驗前後之包裝製品之外觀產生變化,於長時間保存拋棄式發熱包製品之後,在外觀上變為欠佳之狀態。又,於比較例1~3中,外袋之水蒸氣透過度較高,水蒸氣易於通過,因此,水分易於自外部侵入至外袋內部,進而,作為拋棄式發熱包之發熱性組合物成分所含有之水分易於逃逸至外部,於長時間保存之後,無法作為拋棄式發熱包充分地發熱。進而,於比較例4中,認定有顯著之膨脹傾向,熱密封部分因該膨脹而破損,於製品開封前,發熱包與外部氣體接觸,發熱已經結束。
於參考例中,加速試驗前後之包裝製品之外觀無變化,且即便於長時間保存之後,作為製品之發熱功能亦無劣化。又,於參考例中,拋棄式發熱包外袋之水蒸氣透過度較低,水蒸氣不易通過,因此,水分不易自外部侵入至外袋內部,又,作為拋棄式發熱包之成分所含有之水分不易逃逸至外部,於長時間保存之後,亦充分地發揮作為拋棄式發熱包之功能。如此,作為製品並無較大之問題,但若與實施例1~6相比,則如表7之結果般,密封強度、耐衝擊性及耐候性較低。
又,填充包裝於一個面由包含聚乙烯膜之透氣性穿孔內袋構成,另一個面包含聚乙烯膜之非透氣性內袋,從而製造包含單個包裝體之非黏貼型之拋棄式發熱包,並與實施例1~6進行相同之試驗,成為與實施例1~6同樣良好之結果。
10‧‧‧第1阻隔層
11‧‧‧耐熱性樹脂基材
12‧‧‧聚偏二氯乙烯層
20‧‧‧第2阻隔層
21‧‧‧耐熱性樹脂基材
22‧‧‧聚偏二氯乙烯層
30‧‧‧密封劑層
40‧‧‧接著劑層
50‧‧‧印刷油墨層
Claims (8)
- 一種拋棄式發熱包外袋用多層膜,其特徵在於包含2層以上之阻隔層,上述阻隔層包含基材、及於上述基材之至少一個面塗佈聚偏二氯乙烯而成之聚偏二氯乙烯層。
- 如請求項1之拋棄式發熱包外袋用多層膜,其不包含蒸鍍金屬或金屬氧化物而成之蒸鍍層。
- 如請求項1或2之拋棄式發熱包外袋用多層膜,其中上述基材係選自雙軸延伸聚丙烯、雙軸延伸聚對苯二甲酸乙二酯及雙軸延伸聚醯胺樹脂。
- 如請求項1或2之拋棄式發熱包外袋用多層膜,其進而包含含有熱熔合性樹脂基材之密封劑層,上述之密封劑層係設置於上述拋棄式發熱包外袋之內側表面、外側表面或該等二者上。
- 如請求項1或2之拋棄式發熱包外袋用多層膜,其於上述2層以上之阻隔層之間進而包含接著劑層。
- 如請求項1或2之拋棄式發熱包外袋用多層膜,其進而包含追加之樹脂層。
- 如請求項1或2之拋棄式發熱包外袋用多層膜,其於20℃、90%RH下所測定之氧氣透過度為1.5~4.5cc/(m2‧day‧atm),於40℃、90%RH下所測定之水蒸氣透過度為0.05~3.5g/(m2‧day)。
- 一種拋棄式發熱包,其係將收納有發熱性組合物之內袋密封包裝於將如請求項1至7中任一項之拋棄式發熱包外袋用多層膜進行熱熔合而形成之外袋而成。
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US20200060870A1 (en) * | 2017-05-12 | 2020-02-27 | University Of Massachusetts | Apparatus and Methods for Establishing and Maintaining Bodily Temperature Levels |
TW201934830A (zh) * | 2018-02-06 | 2019-09-01 | 智能紡織科技股份有限公司 | 可加熱織物 |
JP2020103490A (ja) * | 2018-12-27 | 2020-07-09 | 桐灰化学株式会社 | 発熱具 |
JP2022158547A (ja) * | 2021-04-02 | 2022-10-17 | 小林製薬株式会社 | 化学カイロ用外袋用フィルム |
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