TW202112544A - 熱收縮性多層膜及熱收縮性標籤 - Google Patents
熱收縮性多層膜及熱收縮性標籤 Download PDFInfo
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- TW202112544A TW202112544A TW109122376A TW109122376A TW202112544A TW 202112544 A TW202112544 A TW 202112544A TW 109122376 A TW109122376 A TW 109122376A TW 109122376 A TW109122376 A TW 109122376A TW 202112544 A TW202112544 A TW 202112544A
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Abstract
本發明提供一種熱收縮性多層膜,該熱收縮性多層膜無論層間強度如何,均能夠製作具有高密封強度之熱收縮性標籤,且透明性亦優異。又,本發明亦提供一種使用該熱收縮性多層膜而成之熱收縮性標籤。
本發明係一種熱收縮性多層膜,其特徵在於:其係含有聚酯系樹脂之正面背面層與含有聚苯乙烯系樹脂之中間層介隔接著層被積層而成者,上述接著層含有玻璃轉移溫度為77℃以下之聚酯系樹脂。
Description
本發明係關於一種熱收縮性多層膜,該熱收縮性多層膜無論層間強度如何,均能夠製作具有高密封強度之熱收縮性標籤,並且透明性亦優異。又,本發明係關於一種使用該熱收縮性多層膜而成之熱收縮性標籤。
近年來,於寶特瓶、金屬罐等容器上多裝配有熱收縮性標籤,該熱收縮性標籤係於由熱收縮性樹脂所構成之基礎膜上實施印刷等而成。
聚苯乙烯系樹脂膜由於其低溫收縮性優異而經常用於熱收縮性標籤。然而,聚苯乙烯系樹脂膜存在耐熱性及耐溶劑性不足之問題。對此,雖然人們嘗試使用耐熱性及耐溶劑性優異之聚酯系樹脂膜,但是由於聚酯系樹脂膜低溫收縮性較差,會急劇收縮,因此裝配於容器時容易產生皺褶。又,雖然為了回收容器而往往於熱收縮性標籤上設置有齒孔,以便能夠從使用後之容器上容易地撕掉熱收縮性標籤,但是聚酯系樹脂膜之齒孔處之斷開性較差。
為了解決上述問題,例如正研究一種多層膜,其具有含有聚酯系樹脂之正面背面層、及含有聚苯乙烯系樹脂之中間層,但是防止多層膜中各層間之剝離為重要課題。
為了防止各層間之剝離而於正面背面層與中間層之間設置接著層,於專利文獻1中,記載有一種熱收縮性多層膜,其使用有「硬質聚酯系樹脂」及「軟質聚酯系樹脂、軟質苯乙烯系樹脂、硬質苯乙烯系樹脂或該等之混合物」作為接著層之接著性樹脂。
先前技術文獻
專利文獻
專利文獻1:日本特開2010-241055號公報
[發明所欲解決之課題]
將熱收縮性多層膜之一端部與另一端部重疊而製成筒狀,如圖1所示般利用溶劑密封使重疊部分熔接而製成熱收縮性標籤使用。熱收縮性標籤通過加熱爐而熱收縮,藉此緊密裝配於寶特瓶等容器。
熱收縮時由收縮所產生之應力作用於溶劑密封部,若層間強度較弱則無法獲得充分之密封強度,因此存在如圖2所示般溶劑密封部處產生層間剝離,溶劑密封部之剝落因收縮而擴大,導致外觀不良之問題,於專利文獻1中所記載之膜存在即便可提高層間強度,抑制溶劑密封部之剝落之效果亦不足之問題。
本發明之目的在於提供一種熱收縮性多層膜,該熱收縮性多層膜無論層間強度如何,均能夠製作具有高密封強度之熱收縮性標籤,且透明性亦優異。又,本發明之目的在於提供一種使用該熱收縮性多層膜而成之熱收縮性標籤。
[解決課題之技術手段]
本發明係一種熱收縮性多層膜,其特徵在於:其係含有聚酯系樹脂之正面背面層與含有聚苯乙烯系樹脂之中間層介隔接著層被積層而成者,上述接著層含有玻璃轉移溫度為77℃以下之聚酯系樹脂。
以下對本發明加以詳細敍述。
本發明人等發現,將含有聚酯系樹脂之正面背面層與含有聚苯乙烯系樹脂之中間層介隔含有具有特定物性之聚酯系樹脂之接著層進行積層,藉此可獲得無論層間強度如何,均具有高密封強度之熱收縮性標籤。又,發現可獲得透明性不會降低且外觀優異之熱收縮性標籤,從而完成本發明。
本發明之熱收縮性多層膜具有正面背面層及中間層。
再者,本說明書中,正面背面層係指正面層與背面層此二者。因此,本發明之熱收縮性多層膜具有中間層夾於正面層與背面層之間之構造。
(正面背面層)
上述正面背面層含有聚酯系樹脂。
作為上述聚酯系樹脂,例如可列舉藉由使二羧酸成分與二醇成分縮聚而獲得者。
作為上述二羧酸,例如可列舉:對苯二甲酸、鄰苯二甲酸、間苯二甲酸、琥珀酸、己二酸、癸二酸、壬二酸、辛基琥珀酸、環己烷二羧酸、萘二甲酸、富馬酸、馬來酸、伊康酸、十亞甲基羧酸、該等之酸酐及低級烷基酯等。
作為上述二羧酸,較佳為對苯二甲酸、間苯二甲酸。
上述二羧酸成分100莫耳%中,源自對苯二甲酸之成分之含量的較佳之下限為50莫耳%,更佳之下限為60莫耳%,進而較佳之下限為65莫耳%,且較佳之上限為100莫耳%。
又,上述二羧酸成分100莫耳%中,源自間苯二甲酸之成分之含量的較佳之下限為0莫耳%,且較佳之上限為40莫耳%,更佳之上限為35莫耳%,進而較佳之上限為33莫耳%。
作為上述二醇,例如可列舉:乙二醇、1,3-丙二醇、1,4-丁二醇、二乙二醇、1,5-戊二醇、1,6-己二醇、二丙二醇、三乙二醇、四乙二醇、1,2-丙二醇、1,3-丁二醇、2,3-丁二醇、新戊二醇(2,2-二甲基丙烷-1,3-二醇)、1,2-己二醇、2,5-己二醇、2-甲基-2,4-戊二醇、3-甲基-1,3-戊二醇、2-乙基-1,3-己二醇、聚四亞甲基醚二醇等脂肪族二醇類;2,2-雙(4-羥基環己基)丙烷、2,2-雙(4-羥基環己基)丙烷之環氧烷(alkylene oxide)加成物、1,4-環己二醇、1,4-環己烷二甲醇等脂環式二醇類等。
作為上述二醇,較佳為乙二醇、1,4-丁二醇、二乙二醇、1,4-環己烷二甲醇。
上述二醇成分100莫耳%中,源自乙二醇之成分之含量的較佳之下限為40莫耳%,更佳之下限為50莫耳%,進而較佳之下限為60莫耳%,且較佳之上限為100莫耳%。
上述二醇成分100莫耳%中,源自二乙二醇之成分之含量的較佳之下限為0莫耳%,且較佳之上限為40莫耳%,更佳之上限為30莫耳%,進而較佳之上限為25莫耳%。
上述二醇成分100莫耳%中,源自1,4-環己烷二甲醇之成分之含量的較佳之下限為0莫耳%,且較佳之上限為70莫耳%,更佳之上限為60莫耳%,進而較佳之上限為50莫耳%。
作為上述聚酯系樹脂,其中,較佳為含有源自對苯二甲酸之成分作為二羧酸成分,且含有源自乙二醇及/或1,4-環己烷二甲醇之成分作為二醇成分者。藉由使用此種芳香族聚酯系無規共聚樹脂,可對熱收縮性多層膜賦予優異之收縮性。
構成上述正面背面層之聚酯系樹脂之玻璃轉移溫度的較佳之下限為55℃,更佳之下限為60℃,進而較佳之下限為65℃,且較佳之上限為95℃,更佳之上限為90℃,進而較佳之上限為85℃。
若上述玻璃轉移溫度為55℃以上,則可防止熱收縮性多層膜之收縮開始溫度變得過低、或自然收縮率變大、或變得容易產生黏連(blocking)。若上述玻璃轉移溫度為95℃以下,則可防止熱收縮性多層膜之低溫收縮性及收縮完成性降低、或低溫收縮性之降低隨著時間推移而變大、或延伸時容易產生樹脂白化。
再者,上述玻璃轉移溫度可利用依據ISO 3146之方法測定。
構成上述正面背面層之聚酯系樹脂之拉伸彈性模數的較佳之下限為超過1000 MPa,較佳之上限為4000 MPa。若上述拉伸彈性模數超過1000 MPa,則可防止熱收縮性膜之收縮開始溫度變得過低、或自然收縮率變大。若上述拉伸彈性模數為4000 MPa以下,則可防止熱收縮性多層膜之低溫收縮性及收縮完成性降低、或低溫收縮性之降低隨著時間推移而變大。上述拉伸彈性模數之更佳之下限為1500 MPa,更佳之上限為3700 MPa。
再者,上述拉伸彈性模數可利用依據ASTM-D882(TestA)之方法測定。
作為構成上述正面背面層之聚酯系樹脂之市售品,例如可列舉:「Easter」、「EmbraceLv」(Eastman Chemical公司製造)、「Bellpet」(Bell Polyester Products公司製造)、「Novaduran」(Mitsubishi Engineering-Plastics公司製造)等。
作為上述正面背面層中所包含之聚酯系樹脂,可單獨使用具有上述組成之聚酯系樹脂,亦可將具有上述組成之2種以上之聚酯系樹脂併用。
上述正面背面層可視需要含有:抗氧化劑、熱穩定劑、紫外線吸收劑、光穩定劑、潤滑劑、抗靜電劑、抗黏連劑、難燃劑、抗菌劑、螢光增白劑、著色劑等添加劑。
(中間層)
上述中間層含有聚苯乙烯系樹脂。
作為上述聚苯乙烯系樹脂,例如可列舉:芳香族乙烯基烴-共軛二烯共聚物、芳香族乙烯基烴-共軛二烯共聚物與芳香族乙烯基烴-脂肪族不飽和羧酸酯共聚物之混合樹脂、橡膠改質耐衝擊性聚苯乙烯等。藉由使用上述聚苯乙烯系樹脂,本發明之熱收縮性多層膜可從低溫便開始收縮,並且具有高收縮性。
本說明書中,芳香族乙烯基烴-共軛二烯共聚物係指含有源自芳香族乙烯基烴之成分及源自共軛二烯之成分之共聚物。
上述芳香族乙烯基烴並無特別限定,例如可列舉:苯乙烯、鄰甲基苯乙烯、對甲基苯乙烯等。該等可單獨使用,亦可將2種以上併用。
上述共軛二烯並無特別限定,例如可列舉:1,3-丁二烯,2-甲基-1,3-丁二烯,2,3-二甲基-1,3-丁二烯、1,3-戊二烯、1,3-己二烯等。該等可單獨使用,亦可將2種以上併用。
上述芳香族乙烯基烴-共軛二烯共聚物尤其就熱收縮性優異之方面而言,較佳為含有苯乙烯-丁二烯共聚物(SBS樹脂)。又,為了製作魚眼更少之熱收縮性多層膜,上述芳香族乙烯基烴-共軛二烯共聚物較佳為含有使用有2-甲基-1,3-丁二烯(異戊二烯)作為上述共軛二烯之苯乙烯-異戊二烯共聚物(SIS樹脂)、苯乙烯-異戊二烯-丁二烯共聚物(SIBS樹脂)等。
再者,上述芳香族乙烯基烴-共軛二烯共聚物可單獨含有SBS樹脂、SIS樹脂及SIBS樹脂中之任一者,亦可組合含有複數種。又,於使用SBS樹脂、SIS樹脂及SIBS樹脂中之複數種之情形時,可將各樹脂進行乾摻,亦可使用複合樹脂(compound resin),該複合樹脂係利用擠出機以特定組成將各樹脂充分捏合並造粒而成。
苯乙烯於上述聚苯乙烯系樹脂100重量%中所占之含量的較佳之下限為65重量%,更佳之下限為70重量%,進而較佳之下限為76重量%,且較佳之上限為90重量%,更佳之上限為85重量%,進而較佳之上限為83重量%。
若上述苯乙烯含量為65重量%以上,則成形加工時不易產生凝膠等異物,而可充分提高熱收縮性膜之機械強度。又,若上述苯乙烯含量為65重量%以上,則可獲得良好之密封強度。
若上述苯乙烯含量為90重量%以下,則可防止對熱收縮性膜施加張力或實施印刷等加工時之斷裂。
又,共軛二烯於上述聚苯乙烯系樹脂100重量%中所占之含量的較佳之下限為10重量%,更佳之下限為15重量%,進而較佳之下限為17重量%,且較佳之上限為35重量%,更佳之上限為30重量%,進而較佳之上限為24重量%。
若上述共軛二烯含量為10重量%以上,則可防止對熱收縮性膜施加張力或實施印刷等加工時之斷裂。
若上述共軛二烯含量為35重量%以下,則成形加工時不易產生凝膠等異物,而可充分提高熱收縮性膜之機械強度。又,若上述共軛二烯含量為35重量%以下,則可獲得良好之密封強度。
上述聚苯乙烯系樹脂之菲卡軟化溫度的較佳之下限為60℃,更佳之下限為65℃,進而較佳之下限為67℃,且較佳之上限為85℃,更佳之上限為80℃,進而較佳之上限為77℃。
若上述菲卡軟化溫度為60℃以上,則熱收縮性多層膜之低溫收縮性不會變得過高,而可防止裝配於容器時產生皺褶。若上述菲卡軟化溫度為85℃以下,則使熱收縮性多層膜之低溫收縮性變得良好,而可防止裝配於容器時產生未收縮部分。再者,上述菲卡軟化溫度可利用依據ISO 306:1994之方法測定。
上述聚苯乙烯系樹脂之於200℃之MFR(melt flow rate,熔體流動速率)的較佳之下限為2 g/10分鐘,較佳之上限為15 g/10分鐘。若於200℃之MFR未達2 g/10分鐘,則膜之製造變得困難。若於200℃之MFR超過15 g/10分鐘,則膜之機械強度變低,會變得經不住實際使用。於200℃之MFR之更佳之下限為4 g/10分鐘,更佳之上限為12 g/10分鐘。再者,MFR可利用依據ISO 1133之方法測定。
作為構成上述中間層之聚苯乙烯系樹脂之市售品,例如可列舉:「Clearen」(電氣化學工業公司製造)、「Asaflex」(旭化成化學公司製造)、「Styrolux」(巴斯夫公司製造)、「PSJ-POLYSTYRENE」(PS Japan公司製造)等。
上述中間層可視需要含有:抗氧化劑、熱穩定劑、紫外線吸收劑、光穩定劑、潤滑劑、抗靜電劑、難燃劑、抗菌劑、螢光增白劑、著色劑等添加劑。
(接著層)
本發明之熱收縮性多層膜係上述正面背面層與上述中間層介隔含有玻璃轉移溫度為77℃以下之聚酯系樹脂之接著層被積層而成者。
藉由使用此種接著層,可製作無論層間強度如何均具有高密封強度且透明性亦優異之熱收縮性標籤。
作為構成上述接著層之聚酯系樹脂,可使用與上述正面背面層所使用之聚酯系樹脂相同者,亦可使用其他聚酯系樹脂。
構成上述接著層之聚酯系樹脂之上述二羧酸成分100莫耳%中,源自對苯二甲酸之成分之含量的較佳之下限為60莫耳%,更佳之下限為65莫耳%,進而較佳之下限為67莫耳%,且較佳之上限為100莫耳%。
又,上述二羧酸成分100莫耳%中,源自間苯二甲酸之成分之含量的較佳之下限為0莫耳%,且較佳之上限為40莫耳%,更佳之上限為35莫耳%,進而較佳之上限為33莫耳%。
上述二醇成分100莫耳%中,源自乙二醇之成分之含量的較佳之下限為50莫耳%,更佳之下限為60莫耳%,進而較佳之下限為63莫耳%,且較佳之上限為100莫耳%。
上述二醇成分100莫耳%中,源自二乙二醇之成分之含量的較佳之下限為0莫耳%,且較佳之上限為30莫耳%,更佳之上限為25莫耳%,進而較佳之上限為22莫耳%。
上述二醇成分100莫耳%中,源自1,4-環己烷二甲醇之成分之含量的較佳之下限為0莫耳%,且較佳之上限為25莫耳%,更佳之上限為22莫耳%,進而較佳之上限為20莫耳%。
構成上述接著層之聚酯系樹脂之玻璃轉移溫度為77℃以下。
若上述玻璃轉移溫度為77℃以下,則可獲得良好之密封強度。
上述玻璃轉移溫度之較佳之下限為60℃,更佳之下限為62℃,進而較佳之下限為65℃,且較佳之上限為76℃,更佳之上限為75℃,進而較佳之上限為73℃。
又,構成上述接著層之聚酯系樹脂之玻璃轉移溫度與構成上述正面背面層之聚酯系樹脂之玻璃轉移溫度的差較佳為10℃以下。
若上述玻璃轉移溫度之差為10℃以下,則可獲得良好之密封強度。
再者,上述玻璃轉移溫度可利用依據ISO 3146之方法測定。
上述接著層中上述聚酯系樹脂之含量之較佳之下限為4.7重量%,較佳之上限為96重量%。
若上述聚酯系樹脂之含量為上述範圍,則可獲得良好之密封強度。
上述聚酯系樹脂之含量之更佳之下限為47.5重量%,進而較佳之下限為48重量%,進而更佳之下限為49重量%,且更佳之上限為95重量%,進而較佳之上限為94重量%,進而更佳之上限為93重量%。
作為構成上述接著層之聚苯乙烯系樹脂,可使用與上述中間層所使用之聚苯乙烯系樹脂相同者,亦可使用其他聚苯乙烯系樹脂。於使用其他聚苯乙烯系樹脂之情形時,較佳為較中間層所使用之聚苯乙烯系樹脂更軟質者。
作為構成上述接著層之聚苯乙烯系樹脂,尤其就接著性優異之方面而言,較佳為含有芳香族乙烯基烴-共軛二烯共聚物,尤佳為含有苯乙烯-丁二烯共聚物(SBS樹脂)。於使用苯乙烯-丁二烯共聚物之情形時,就接著性優異之觀點而言,較佳為與中間層所使用之苯乙烯-丁二烯共聚物相比丁二烯之含量較多。又,為了製作接著性更優異之熱收縮性多層膜,較佳為含有使用有2-甲基-1,3-丁二烯(異戊二烯)作為上述芳香族乙烯基烴-共軛二烯共聚物之共軛二烯的苯乙烯-異戊二烯共聚物(SIS樹脂)、苯乙烯-異戊二烯-丁二烯共聚物(SIBS樹脂)等。亦可於不成為聚苯乙烯系樹脂之主成分之範圍內進而含有對芳香族乙烯基烴-共軛二烯共聚物進行氫化而成之苯乙烯-丁二烯-丁烯共聚物(SBBS樹脂)或苯乙烯-乙烯-丁烯共聚物(SEBS樹脂)等氫化苯乙烯系樹脂。若氫化苯乙烯系樹脂成為聚苯乙烯系樹脂中之主成分,則透明性變得容易降低。
再者,上述聚苯乙烯系樹脂可單獨含有SBS樹脂、SIS樹脂及SIBS樹脂中之任一者,亦可組合含有複數種。又,於使用SBS樹脂、SIS樹脂、SIBS樹脂、SBBS樹脂或SEBS樹脂中之複數種之情形時,可將各樹脂進行乾摻,亦可使用複合樹脂,該複合樹脂係利用擠出機以特定組成將各樹脂充分捏合並造粒而成。
苯乙烯於上述聚苯乙烯系樹脂100重量%中所占之含量之較佳之下限為50重量%,更佳之下限為60重量%,進而較佳之下限為73重量%,進而更佳之下限為75重量%,特佳之下限為76重量%,且較佳之上限為98重量%,更佳之上限為95重量%,進而較佳之上限為93重量%,進而更佳之上限為92重量%,特佳之上限為90重量%。
若上述苯乙烯含量為50重量%以上,則可防止成形加工時產生凝膠等異物。若上述苯乙烯含量為98重量%以下,則可充分提高層間強度。
丁二烯於上述聚苯乙烯系樹脂100重量%中所占之含量之較佳之下限為2重量%,更佳之下限為5重量%,進而較佳之下限為7重量%,進而更佳之下限為8重量%,特佳之下限為10重量%,且較佳之上限為50重量%,更佳之上限為40重量%,進而較佳之上限為27重量%,進而更佳之上限為25重量%,特佳之上限為24重量%。
若上述丁二烯含量為2重量%以上,則可充分提高層間強度。若上述丁二烯含量為50重量%以下,則可防止成形加工時產生凝膠等異物。
構成上述接著層之聚苯乙烯系樹脂之菲卡軟化溫度的較佳之下限為30℃,更佳之下限為40℃,進而較佳之下限為42℃,特佳之下限為45℃,且較佳之上限為85℃,更佳之上限為80℃,進而較佳之上限為77℃,特佳之上限為75℃。
若上述菲卡軟化溫度為30℃以上,則可防止熱收縮性多層膜於裝配於容器時因加熱而於各層間產生層間剝離。若上述菲卡軟化溫度為85℃以下,則可進一步提高熱收縮性多層膜之接著強度。
再者,上述菲卡軟化溫度可利用依據ISO 306之方法測定。
構成上述接著層之聚苯乙烯系樹脂於200℃之MFR(melt flow rate)之較佳之下限為2 g/10分鐘,較佳之上限為15 g/10分鐘。若於200℃之MFR未達2 g/10分鐘,則樹脂於連續生產步驟中滯留於擠出機內,變得容易產生凝膠等異物。若於200℃之MFR超過15 g/10分鐘,則於製膜步驟中未充分施加壓力,厚度變動容易變大。於200℃之MFR之更佳之下限為4 g/10分鐘,更佳之上限為12 g/10分鐘。再者,MFR可利用依據ISO 1133之方法測定。
上述接著層中上述聚苯乙烯系樹脂之含量之較佳之下限為2重量%,較佳之上限為95重量%。
若上述聚苯乙烯系樹脂之含量為上述範圍,則可獲得良好之密封強度。
上述聚苯乙烯系樹脂之含量之更佳之下限為2.5重量%,進而較佳之下限為3重量%,進而更佳之下限為4重量%,且更佳之上限為47.5重量%,進而較佳之上限為47重量%,進而更佳之上限為46重量%。
用於上述接著層之聚酯系彈性體係由作為硬鏈段之聚酯及作為富有橡膠彈性之軟鏈段之聚醚或聚酯所構成者。
作為上述硬鏈段之聚酯例如可列舉芳香族聚酯等。
作為上述軟鏈段之聚酯例如可列舉脂肪族聚酯等。
又,作為上述軟鏈段之聚醚例如可列舉聚伸烷基醚二醇等脂肪族聚醚等。
其中,較佳為由作為硬鏈段之芳香族聚酯及作為軟鏈段之脂肪族聚醚所構成之嵌段共聚物、或由作為硬鏈段之芳香族聚酯及作為軟鏈段之脂肪族聚酯所構成之嵌段共聚物,更佳為由作為硬鏈段之芳香族聚酯及作為軟鏈段之聚伸烷基醚二醇所構成之嵌段共聚物。
作為上述聚酯系彈性體,於使用由芳香族聚酯及聚伸烷基醚二醇所構成之嵌段共聚物之情形時,由聚伸烷基醚二醇所構成之鏈段之比率的較佳之下限為5重量%,較佳之上限為90重量%。若未達5重量%,則與中間層之接著性降低,若超過90重量%,則對正面背面層之接著性降低。更佳之下限為30重量%,更佳之上限為80重量%,進而較佳之下限為55重量%。
作為上述聚伸烷基醚二醇,例如可列舉:聚乙二醇、聚(伸丙基醚)二醇、聚(四亞甲基醚)二醇、聚(六亞甲基醚)二醇等。
上述聚伸烷基醚二醇之數量平均分子量的較佳之下限為400,較佳之上限為6000。更佳之下限為600,更佳之上限為4000,進而較佳之下限為1000,進而較佳之上限為3000。藉由使用具有上述範圍內之數量平均分子量之聚伸烷基醚二醇,可獲得良好之層間強度而較佳。再者,本說明書中,數量平均分子量係指利用凝膠滲透層析法(GPC)測得者。
作為製作上述聚酯系彈性體之方法並無特別限定,例如可藉由以下方法製作:以(i)碳數2~12之脂肪族及/或脂環式二醇、(ii)芳香族二羧酸及/或脂環式二羧酸或該等之酯、及(iii)數量平均分子量為400~6000之聚伸烷基醚二醇為原料,藉由酯化反應或酯交換反應獲得低聚物後,進而使低聚物縮聚。
作為上述碳數2~12之脂肪族及/或脂環式二醇,例如可使用作為聚酯之原料、尤其是作為聚酯系熱塑性彈性體之原料而常用者。具體而言,例如可列舉:乙二醇、丙二醇、三亞甲基二醇、1,4-丁二醇、1,4-環己二醇、1,4-環己烷二甲醇等。該等中,較佳為乙二醇、1,4-丁二醇,更佳為1,4-丁二醇。該等可單獨使用,亦可將2種以上併用。
作為上述芳香族二羧酸及/或脂環式二羧酸,例如可使用作為聚酯之原料、尤其是作為聚酯系熱塑性彈性體之原料而常用者。具體而言,例如可列舉:對苯二甲酸、間苯二甲酸、鄰苯二甲酸、2,6-萘二甲酸、環己烷二羧酸等。該等中,較佳為對苯二甲酸、2,6-萘二甲酸,更佳為對苯二甲酸。該等可單獨使用,亦可將2種以上併用。
作為上述聚酯系彈性體中之市售者,例如可列舉:商品名「Primalloy」(三菱化學公司製造)、商品名「Pelprene」(東洋紡織公司製造)、商品名「Hytrel」(東麗杜邦公司製造)等。
上述聚酯系彈性體之熔點較佳為120~200℃。若未達120℃,則存在耐熱性降低,作為熱收縮性標籤而被覆於容器時容易從溶劑密封部分產生剝離之情形,若超過200℃,則存在無法獲得充分之接著強度之情形。更佳之下限為130℃,更佳之上限為190℃。
再者,上述熔點可利用依據ISO 3146之方法,使用示差掃描熱量計(島津製作所公司製造,DSC-60)測定。
上述聚酯系彈性體之熔點取決於作為硬鏈段之聚酯及作為軟鏈段之聚醚或聚酯之共聚合比率或結構。通常聚酯系彈性體之熔點容易依賴於作為軟鏈段之聚醚或聚酯之共聚合量,若聚醚或聚酯之共聚合量較多,則熔點變低,若聚醚或聚酯之共聚合量較少,則熔點變高。
又,可藉由變更共聚合成分來調整作為構成聚酯系彈性體之硬鏈段之聚酯的熔點,從而調整聚酯系彈性體整體之熔點。
又,若作為軟鏈段之聚醚或聚酯之分子量變小,則因所獲得之聚酯系彈性體之嵌段性降低而熔點變得容易降低。
上述聚酯系彈性體之硬度計硬度之較佳之下限為10,較佳之上限為80。藉由將硬度計硬度設為10以上,上述接著層之機械強度提高。藉由將硬度計硬度設為80以下,上述接著層之柔軟性及耐衝擊性提高。硬度計硬度之更佳之下限為15,更佳之上限為70,進而較佳之下限為20,進而較佳之上限為60。
再者,上述硬度計硬度可藉由使用D型硬度計,利用依據ISO 18517之方法測定。
上述聚酯系彈性體之比重之較佳之下限為0.95,較佳之上限為1.20。藉由將比重設為0.95以上,可賦予耐熱性,並且可抑制作為熱收縮性標籤被覆容器時從溶劑密封部分剝離。又,藉由將比重設為1.20以下,可提高正面背面層與中間層之接著強度。
上述比重之更佳之下限為0.98,更佳之上限為1.18。
再者,上述比重可利用依據ASTM D 792之方法,使用水中置換法測定。
構成上述接著層之聚酯系彈性體之拉伸彈性模數的較佳之下限為1 MPa,較佳之上限為1000 MPa。若上述拉伸彈性模數未達1 MPa,則上述接著層之機械強度變得容易降低。若上述拉伸彈性模數超過1000 MPa,則正面背面層與中間層之接著強度變得容易降低。上述拉伸彈性模數之更佳之下限為5 MPa,更佳之上限為900 MPa。再者,上述拉伸彈性模數可利用依據ASTM-882(TestA)之方法測定。
構成上述接著層之聚酯系彈性體之玻璃轉移溫度的較佳之下限為-70℃,更佳之下限為-35℃,進而較佳之下限為-30℃,且較佳之上限為55℃,更佳之上限為53℃,進而較佳之上限為50℃。
若上述玻璃轉移溫度為-70℃以上,則不易產生樹脂黏連,而可使操作性良好。若上述玻璃轉移溫度為55℃以下,則可使正面背面層與中間層之接著強度良好。
再者,上述聚酯系彈性體之玻璃轉移溫度可根據tanδ峰計算,該tanδ峰係利用依據ISO 6721-4之方法獲得。
上述聚酯系彈性體亦可為改質物。作為改質物,可例示對上述聚酯系彈性體接枝例如α,β-乙烯性不飽和羧酸改質而成之聚酯系彈性體。
作為上述α,β-乙烯性不飽和羧酸,例如可列舉:丙烯酸、馬來酸、富馬酸、四氫富馬酸、伊康酸、檸康酸、巴豆酸、異巴豆酸等不飽和羧酸;2-辛烯-1-基琥珀酸酐、2-十二烯-1-基琥珀酸酐、2-十八烯-1-基琥珀酸酐、馬來酸酐、2,3-二甲基馬來酸酐、溴馬來酸酐、二氯馬來酸酐、檸康酸酐、伊康酸酐、1-丁烯-3,4-二羧酸酐、1-環戊烯-1,2-二羧酸酐、1,2,3,6-四氫鄰苯二甲酸酐、3,4,5,6-四氫鄰苯二甲酸酐、外-3,6-環氧-1,2,3,6-四氫鄰苯二甲酸酐、5-降莰烯-2,3-二羧酸酐、甲基-5-降莰烯-2,3-二羧酸酐、內-雙環[2.2.2]辛-5-烯-2,3-二羧酸酐、雙環[2.2.2]辛-7-烯-2,3,5,6-四羧酸酐等不飽和羧酸酐。該等中,就反應性較高之方面而言,較佳為酸酐。
上述接著層中之上述聚酯系彈性體之含量的較佳之下限為0.3重量%,較佳之上限為80重量%。
若上述聚酯系彈性體之含量為上述範圍,則可獲得良好之密封強度。
上述聚酯系彈性體之含量的更佳之下限為0.5重量%,進而較佳之下限為0.7重量%,進而更佳之下限為0.8重量%,且更佳之上限為28重量%,進而較佳之上限為27重量%,進而更佳之上限為26重量%。
上述接著層可視需要含有抗氧化劑、熱穩定劑、紫外線吸收劑、光穩定劑、潤滑劑、抗靜電劑、難燃劑、抗菌劑、螢光增白劑、著色劑等添加劑。
(膜)
本發明之熱收縮性多層膜整體之厚度的較佳之下限為10 μm,較佳之上限為100 μm,更佳之下限為15 μm,更佳之上限為80 μm,進而較佳之下限為20 μm,進而較佳之上限為70 μm。若熱收縮性多層膜整體之厚度為上述範圍內,則可獲得優異之熱收縮性、印刷或中封(center seal)等優異之薄片材加工(converting)性、優異之裝配性。
又,本發明之熱收縮性多層膜中,上述正面背面層之厚度相對於熱收縮性多層膜整體之厚度的較佳之下限為5%,較佳之上限為25%,上述中間層之厚度相對於熱收縮性多層膜整體之厚度的較佳之下限為50%,較佳之上限為90%。若上述正面背面層及上述中間層之厚度為上述範圍內,則可獲得高層間強度、高透明性等。
本發明之熱收縮性多層膜中,上述接著層之厚度的較佳之下限為0.3 μm,較佳之上限為3.0 μm。若上述接著層之厚度未達0.3 μm,則存在上述接著層無法獲得充分之接著性之情況。若上述接著層之厚度超過3.0 μm,則存在熱收縮性多層膜之熱收縮特性、光學特性變差之情況。上述接著層之厚度之更佳之下限為0.5 μm,更佳之上限為2.0 μm。
再者,可藉由扣除上述接著層之厚度而調整上述正面背面層及上述中間層之厚度,而調整熱收縮性多層膜整體之厚度。
又,例如,本發明之熱收縮性多層膜為正面層(A)/接著層(E)/中間層(B)/接著層(E)/背面層(C)之5層構造,於熱收縮性多層膜整體之厚度為40 μm之情形時,上述正面層(A)及上述背面層(C)之厚度分別較佳為2.0~10.0 μm,更佳為3.0~8.0 μm。又,上述接著層(E)之厚度較佳為0.3~3.0 μm,更佳為0.5~2.0 μm。又,上述中間層(B)之厚度較佳為19.0~35.4 μm,更佳為20.0~33.0 μm。
進而本發明之熱收縮性多層膜亦可為如正面層(A)/接著層(E)/中間層(B)/接著層(E)/中間層(B)/接著層(E)/中間層(B)/接著層(E)/背面層(C)般於正面層(A)、背面層(C)之間重複接著層(E)/中間層(C)/接著層(E)單元而構成。於熱收縮性多層膜整體之厚度為40 μm之情形時,上述正面層(A)及上述背面層(C)之厚度分別較佳為2.0~10.0 μm,更佳為3.0~8.0。又,上述接著層(E)之合計厚度較佳為1.0~10.0 μm,更佳為1.5~8.0 μm。又,上述中間層(B)之合計厚度較佳為18.0~34.0 μm,更佳為19.0~31.0 μm。
作為於正面層(A)、背面層(C)之間重複上述接著層(E)/中間層(C)/接著層(E)單元而構成之方法,可利用進料模組(feed block)使從複數個擠出機所擠出之樹脂合流,亦可暫時先使接著層(E)/中間層(C)/接著層(E)單元合流後,再使用多層化器(multiplier)構成重複單元。
若於正面層(A)、背面層(C)之間重複上述接著層(E)/中間層(C)/接著層(E)單元而構成,則於對標籤施加衝擊時應力被分散而可抑制剝離。
本發明之熱收縮性多層膜中,主收縮方向上之收縮率於70℃、10秒時較佳為5~50%,更佳為8~47%,進而較佳為10~45%,特佳為15~45%,於80℃、10秒時較佳為35~70%,更佳為38~69%,進而較佳為41~68%,特佳為43~67%,於沸水、10秒時較佳為65~85%,更佳為68~83%,進而較佳為70~82%。藉由設為此種收縮率,可利用熱風通道、蒸氣通道賦予優異之收縮完成性。
本發明之熱收縮性多層膜之與主收縮方向(TD方向)正交之方向(MD方向)之常溫下的層間強度之較佳之下限為0.05 N/10 mm,更佳之下限為0.1 N/10 mm,且較佳之上限為15 N/10 mm,更佳之上限為10 N/10 mm。
又,本發明之熱收縮性多層膜之主收縮方向(TD方向)之層間強度的較佳之下限為0.05 N/10 mm,更佳之下限為0.1 N/10 mm,且較佳之上限為15 N/10 mm,更佳之上限為10 N/10 mm。
本發明之熱收縮性多層膜之密封強度的較佳之下限為2.35 N/10 mm,更佳之下限為2.4 N/10 mm,且較佳之上限為15 N/10 mm,更佳之上限為10 N/10 mm。
製造本發明之熱收縮性多層膜之方法並無特別限定,較佳為藉由共擠壓法使各層同時成形之方法。於上述共擠壓法係藉由T型模頭來進行共擠壓之情形時,積層之方法可為進料模組方式、多歧管(multi-manifold)方式、或將該等併用之方法中之任一者。
作為製造本發明之熱收縮性多層膜之方法,具體而言,例如可列舉以下方法:將構成上述正面背面層、上述中間層及上述接著層之原料分別投入擠出機,藉由多層模頭擠出為片狀,利用抽取輥進行冷卻固化後,進行單軸或雙軸延伸。
作為上述延伸之方法,例如可使用輥延伸法、拉幅機延伸法或該等之組合。延伸溫度根據構成膜之樹脂之軟化溫度、對熱收縮性多層膜所要求之收縮特性等而變更,較佳之下限為65℃,較佳之上限為120℃,更佳之下限為70℃,更佳之上限為115℃。主收縮方向之延伸倍率根據構成膜之樹脂、延伸手段、延伸溫度等而變更,較佳為3倍以上,更佳為4倍以上,且較佳為7倍以下,更佳為6.5倍以下。藉由設為此種延伸溫度及延伸倍率,可達成優異之厚度精度,又,亦可防止撕齒孔時產生層間剝離而僅內面側之正面背面層殘留於容器上。
本發明之熱收縮性多層膜之用途並無特別限定,本發明之熱收縮性多層膜無論層間強度如何,均可製作具有高密封強度之熱收縮性標籤,並且透明性亦優異,因此可適宜地用作例如裝配於寶特瓶、金屬罐等容器之熱收縮性標籤之基礎膜。使用本發明之熱收縮性多層膜而成之熱收縮性標籤亦為本發明之一。
[發明之效果]
根據本發明,可提供一種熱收縮性多層膜,該熱收縮性多層膜無論層間強度如何,均能夠製作具有高密封強度之熱收縮性標籤,且透明性亦優異。又,可提供一種使用該熱收縮性多層膜而成之熱收縮性標籤。
以下揭示實施例對本發明之態樣進一步詳細地加以說明,但本發明並不僅限定於該等實施例。
實施例及比較例中,使用以下原料。
(聚酯系樹脂)
・PET-1:芳香族聚酯共聚物(玻璃轉移溫度69℃),其含有作為二羧酸成分之源自對苯二甲酸之成分100莫耳%、及作為二醇成分之源自乙二醇之成分65莫耳%、源自二乙二醇之成分20莫耳%、源自1,4-環己烷二甲醇之成分15莫耳%
・PET-2:芳香族聚酯共聚物(玻璃轉移溫度70℃),其含有作為二羧酸成分之源自對苯二甲酸之成分70莫耳%、源自間苯二甲酸之成分30莫耳%、及作為二醇成分之源自乙二醇之成分100莫耳%
・PET-3:芳香族聚酯共聚物(玻璃轉移溫度72℃),其含有作為二羧酸成分之源自對苯二甲酸之成分100莫耳%、及作為二醇成分之源自乙二醇之成分70莫耳%、源自二乙二醇之成分10莫耳%、源自1,4-環己烷二甲醇之成分20莫耳%
・PET-4:芳香族聚酯共聚物(玻璃轉移溫度82℃),其含有作為二羧酸成分之源自對苯二甲酸之成分100莫耳%、及作為二醇成分之源自乙二醇之成分70莫耳%、源自1,4-環己烷二甲醇之成分30莫耳%
(聚苯乙烯系樹脂)
・PS-1:苯乙烯-丁二烯嵌段共聚物(苯乙烯成分76重量%、丁二烯成分24重量%、菲卡軟化溫度70℃、MFR 8 g/10分鐘)
・PS-2:苯乙烯-丁二烯嵌段共聚物(苯乙烯成分78重量%、丁二烯成分22重量%、菲卡軟化溫度72℃、MFR 7 g/10分鐘)
(聚酯系彈性體)
・TPE-1:由作為硬鏈段之聚酯、及作為軟鏈段之聚醚所構成之未改質聚酯-聚醚嵌段共聚物(東麗杜邦公司製造,Hytrel 2521,硬度計硬度55,玻璃轉移溫度45℃)
(實施例1)
作為構成正面背面層之樹脂,使用聚酯系樹脂(PET-1)100重量%。
作為構成中間層之樹脂,使用聚苯乙烯系樹脂(PS-2)100重量%。
作為構成接著層之樹脂,使用聚酯系樹脂(PET-1)75重量%、聚苯乙烯系樹脂(PS-1)20重量%、及聚酯系彈性體(TPE-1)5重量%。
將該等投入至料筒溫度(barrel temperature)為160~250℃之擠出機中,從250℃之多層模頭擠出為5層構造之片狀,利用30℃之抽取輥進行冷卻固化。繼而,於預熱區105℃、延伸區90℃、熱固定區85℃之拉幅延伸機內以延伸倍率6倍進行延伸後,利用捲取機進行捲取,藉此獲得與主收縮方向正交之方向為MD、主收縮方向為TD之熱收縮性多層膜。
所獲得之熱收縮性多層膜之總厚度為40 μm,為正面背面層(5.5 μm)/接著層(0.9 μm)/中間層(27.2 μm)/接著層(0.9 μm)/正面背面層(5.5 μm)之5層構造。
(實施例2)
作為構成接著層之樹脂,使用聚酯系樹脂(PET-2)75重量%、聚苯乙烯系樹脂(PS-1)20重量%、及聚酯系彈性體(TPE-1)5重量%。
除此以外,與實施例1同樣地獲得5層構造之熱收縮性多層膜。
(實施例3)
作為構成接著層之樹脂,使用聚酯系樹脂(PET-3)75重量%、聚苯乙烯系樹脂(PS-1)20重量%、及聚酯系彈性體(TPE-1)5重量%。
除此以外,與實施例1同樣地獲得5層構造之熱收縮性多層膜。
(實施例4)
作為構成接著層之樹脂,使用聚酯系樹脂(PET-1)50重量%、聚苯乙烯系樹脂(PS-1)45重量%、及聚酯系彈性體(TPE-1)5重量%。
除此以外,與實施例1同樣地獲得5層構造之熱收縮性多層膜。
(實施例5)
作為構成接著層之樹脂,使用聚酯系樹脂(PET-1)90重量%、聚苯乙烯系樹脂(PS-1)5重量%、及聚酯系彈性體(TPE-1)5重量%。
除此以外,與實施例1同樣地獲得5層構造之熱收縮性多層膜。
(實施例6)
作為構成接著層之樹脂,使用聚酯系樹脂(PET-1)85重量%、聚苯乙烯系樹脂(PS-1)10重量%、及聚酯系彈性體(TPE-1)5重量%。
除此以外,與實施例1同樣地獲得5層構造之熱收縮性多層膜。
(實施例7)
作為構成接著層之樹脂,使用聚酯系樹脂(PET-1)79重量%、聚苯乙烯系樹脂(PS-1)20重量%、及聚酯系彈性體(TPE-1)1重量%。
除此以外,與實施例1同樣地獲得5層構造之熱收縮性多層膜。
(實施例8)
作為構成接著層之樹脂,使用聚酯系樹脂(PET-1)77重量%、聚苯乙烯系樹脂(PS-1)20重量%、及聚酯系彈性體(TPE-1)3重量%。
除此以外,與實施例1同樣地獲得5層構造之熱收縮性多層膜。
(實施例9)
作為構成接著層之樹脂,使用聚酯系樹脂(PET-1)55重量%、聚苯乙烯系樹脂(PS-1)20重量%、及聚酯系彈性體(TPE-1)25重量%。
除此以外,與實施例1同樣地獲得5層構造之熱收縮性多層膜。
(比較例1)
作為構成接著層之樹脂,使用聚酯系樹脂(PET-4)75重量%、聚苯乙烯系樹脂(PS-1)20重量%、及聚酯系彈性體(TPE-1)5重量%。
除此以外,與實施例1同樣地獲得5層構造之熱收縮性多層膜。
(評價)
對實施例及比較例所獲得之熱收縮性多層膜進行以下評價。將熱收縮性多層膜之構成及評價結果示於表1。
(1)層間剝離強度
將熱收縮性多層膜切成長100 mm×寬10 mm之尺寸,如圖1所示將膜端部之一部分進行層間剝離後,以拉伸速度200 mm/min,如圖2所示般將其沿180度方向剝離,使用剝離強度試驗機(HEIDON TYPE17,新東科學公司製造)測定此時之強度。再者,關於層間剝離強度,各實施例及比較例使用4個試片,測定TD方向、MD方向之層間剝離強度,並計算其等之平均值。
(2)密封強度
使用1,3-二氧雜環戊烷(1,3-dioxolane)100重量份與環己烷30重量份之混合溶劑將熱收縮性多層膜之兩端接著,將於寬10 mm之範圍內接著而成之密封部切成長100 mm×寬10 mm之尺寸,將密封部之一部分剝離後,以拉伸速度200 mm/min將其沿180°方向剝離,使用剝離強度試驗機(HEIDON TYPE17,新東科學公司製造)測定此時之強度。再者,關於密封強度,各實施例及比較例使用4個試片,測定TD方向之密封強度,計算其等之平均值,並按照以下基準進行了評價。
〇:密封強度為2.4 N/10 mm以上
×:密封強度未達2.4 N/10 mm
又,按照以下基準對其與層間剝離強度之關係進行了評價。
〇:TD方向、MD方向中任一方向之層間剝離強度為0.5 N/10 mm以下,密封強度為2.4 N/10 mm以上
△:TD方向、MD方向之層間剝離強度均超過0.5 N/10 mm,密封強度為2.4 N/10 mm以上
×:密封強度未達2.4 N/10 mm
(3)霧度
使用NDH 5000(日本電色工業公司製造)利用依據JIS K 7136之方法來測定所獲得之熱收縮性多層膜之霧度,按照以下基準進行了評價。
〇:霧度未達6%
×:霧度為6%以上
[表1]
[產業上之可利用性]
實施例1 | 實施例2 | 實施例3 | 實施例4 | 實施例5 | 實施例6 | 實施例7 | 實施例8 | 實施例9 | 比較例1 | ||||
構成樹脂 (重量%) | 正面背面層 | 聚酯系樹脂 | PET-1 | 100 | 100 | 100 | 100 | 100 | 100 | 100 | 100 | 100 | 100 |
中間層 | 聚苯乙烯系樹脂 | PS-2 | 100 | 100 | 100 | 100 | 100 | 100 | 100 | 100 | 100 | 100 | |
接著層 | 聚苯乙烯系樹脂 | PS-1 | 20 | 20 | 20 | 45 | 5 | 10 | 20 | 20 | 20 | 20 | |
聚酯系彈性體 | TPE-1 | 5 | 5 | 5 | 5 | 5 | 5 | 1 | 3 | 25 | 5 | ||
聚酯系樹脂 | PET-1 | 75 | - | - | 50 | 90 | 85 | 79 | 77 | 55 | - | ||
PET-2 | - | 75 | - | - | - | - | - | - | - | - | |||
PET-3 | - | - | 75 | - | - | - | - | - | - | - | |||
PET-4 | - | - | - | - | - | - | - | - | - | 75 | |||
二羧酸 (莫耳%) | 對苯二甲酸 | 100 | 70 | 100 | 100 | 100 | 100 | 100 | 100 | 100 | 100 | ||
間苯二甲酸 | - | 30 | - | - | - | - | - | - | - | - | |||
二醇 (莫耳%) | 乙二醇 | 65 | 100 | 70 | 65 | 65 | 65 | 65 | 65 | 65 | 70 | ||
二乙二醇 | 20 | - | 10 | 20 | 20 | 20 | 20 | 20 | 20 | - | |||
1,4-環己烷二甲醇 | 15 | - | 20 | 15 | 15 | 15 | 15 | 15 | 15 | 30 | |||
玻璃轉移溫度(℃) | 69 | 70 | 72 | 69 | 69 | 69 | 69 | 69 | 69 | 82 | |||
評價 | 層間剝離強度(N/10 mm) | MD | 0.9 | 0.9 | 0.4 | 0.8 | 0.3 | 0.8 | 0.4 | 0.8 | 1.0 | 0.4 | |
TD | 0.9 | 0.9 | 0.4 | 0.8 | 0.4 | 0.8 | 0.8 | 0.8 | 1.0 | 0.3 | |||
密封強度 (N/10 mm) | N/10 mm | 3.5 | 4.0 | 3.6 | 4.1 | 2.5 | 4.1 | 2.4 | 3.2 | 4.5 | 2.3 | ||
評價 | 〇 | 〇 | 〇 | 〇 | 〇 | 〇 | 〇 | 〇 | 〇 | × | |||
與層間剝離強度之關係 | △ | △ | 〇 | △ | △ | △ | 〇 | △ | △ | × | |||
霧度(%) | 4.2 | 4.8 | 4.9 | 5.5 | 4.2 | 4.6 | 4.5 | 4.1 | 5.6 | 5.5 | |||
〇 | 〇 | 〇 | 〇 | 〇 | 〇 | 〇 | 〇 | 〇 | 〇 |
根據本發明,可提供一種熱收縮性多層膜,該熱收縮性多層膜無論層間強度如何,均能夠製作具有高密封強度之熱收縮性標籤,且透明性亦優異。又,亦可提供一種使用該熱收縮性多層膜而成之熱收縮性標籤。
1:正面背面層
2:中間層
3:接著層
[圖1]係表示熱收縮性標籤之溶劑密封部之示意圖。
[圖2]係表示溶劑密封部之剝離狀態之示意圖。
[圖3]係表示層間強度評價中膜之剝離方法之示意圖。
[圖4]係表示層間強度評價中膜之剝離方法之示意圖。
Claims (6)
- 一種熱收縮性多層膜,其係含有聚酯系樹脂之正面背面層與含有聚苯乙烯系樹脂之中間層介隔接著層被積層而成者,其特徵在於: 上述接著層含有玻璃轉移溫度為77℃以下之聚酯系樹脂。
- 如請求項1之熱收縮性多層膜,其中,接著層含有2~95重量%之聚苯乙烯系樹脂、4.7~96重量%之聚酯系樹脂、及0.3~80重量%之聚酯系彈性體。
- 如請求項1或2之熱收縮性多層膜,其中,構成接著層之聚酯系樹脂含有二羧酸成分及二醇成分,上述二羧酸成分100莫耳%中,含有60~100莫耳%之源自對苯二甲酸之成分、0~40莫耳%之源自間苯二甲酸之成分,上述二醇成分100莫耳%中,含有50~100莫耳%之源自乙二醇之成分、0~25莫耳%之源自二乙二醇之成分、0~25莫耳%之源自1,4-環己烷二甲醇之成分。
- 2或3之熱收縮性多層膜,其中,構成接著層之聚苯乙烯系樹脂為芳香族乙烯基烴-共軛二烯共聚物。
- 2、3或4之熱收縮性多層膜,其中,構成接著層之聚酯系彈性體由作為硬鏈段之聚酯及作為軟鏈段之聚醚構成。
- 一種熱收縮性標籤,其包含請求項1、2、3、4或5之熱收縮性多層膜。
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JP (1) | JPWO2021039072A1 (zh) |
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TW200631777A (en) * | 2004-11-10 | 2006-09-16 | Mitsubishi Plastics Inc | Heat shrinkable laminated film, and mold article, heat shrinkable label and container using the same |
PL1839849T3 (pl) * | 2005-01-11 | 2013-05-31 | Mitsubishi Chem Corp | Termokurczliwa folia warstwowa, formowany wyrób zawierający folię i termokurczliwa etykieta i pojemnik |
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CA2656809C (en) | 2006-07-12 | 2015-12-08 | Gunze Limited | Heat shrinkable multilayer film and heat shrinkable label |
JP5235494B2 (ja) * | 2007-05-15 | 2013-07-10 | 三菱樹脂株式会社 | 積層フィルム、並びに該フィルムを用いた成形品、熱収縮性ラベル及び該ラベルを装着した容器 |
JP5466016B2 (ja) * | 2007-11-14 | 2014-04-09 | 三菱樹脂株式会社 | 積層体、並びに該積層体を用いた熱収縮性フィルム、熱収縮性ラベル、及び該ラベルを装着した容器 |
JP5235760B2 (ja) | 2009-04-08 | 2013-07-10 | 三菱樹脂株式会社 | 熱収縮性積層フィルム、該フィルムを用いた成形品、熱収縮性ラベル及び容器 |
JP5294974B2 (ja) * | 2009-05-14 | 2013-09-18 | 三菱樹脂株式会社 | 熱収縮性積層フィルム、該フィルムを用いた成形品、熱収縮性ラベル及び容器 |
JP5700920B2 (ja) * | 2009-09-09 | 2015-04-15 | 三菱樹脂株式会社 | 熱収縮性積層フィルム、該フィルムを用いた成形品、熱収縮性ラベル及び容器 |
WO2014148554A1 (ja) * | 2013-03-19 | 2014-09-25 | 株式会社フジシールインターナショナル | シュリンクラベルおよびその製造方法 |
JP6122799B2 (ja) * | 2014-03-03 | 2017-04-26 | グンゼ株式会社 | 熱収縮性多層フィルム及び熱収縮性ラベル |
WO2015182451A1 (ja) * | 2014-05-27 | 2015-12-03 | グンゼ株式会社 | 熱収縮性多層フィルム、熱収縮性多層フィルムの製造方法、及び、熱収縮性ラベル |
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EP4023440A1 (en) | 2022-07-06 |
MX2022002168A (es) | 2022-03-22 |
KR20220054281A (ko) | 2022-05-02 |
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WO2021039072A1 (ja) | 2021-03-04 |
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