TWI714641B - 聚酯系標籤及包裝容器 - Google Patents
聚酯系標籤及包裝容器 Download PDFInfo
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- TWI714641B TWI714641B TW105131663A TW105131663A TWI714641B TW I714641 B TWI714641 B TW I714641B TW 105131663 A TW105131663 A TW 105131663A TW 105131663 A TW105131663 A TW 105131663A TW I714641 B TWI714641 B TW I714641B
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Abstract
本發明的目的在於提供一種標籤,即使厚度薄,在運送時的耐龜裂性亦良好。本發明的聚酯系標籤之特徵為滿足以下(1)至(6)的條件:(1)前述標籤的基材膜的厚度為8μm以上30μm以下;(2)構成前述標籤之聚酯的極限黏度為0.58dl/g以上;(3)前述標籤的主收縮方向以及相對於主收縮方向呈正交之方向的拉伸破斷伸長度皆為5%以上;(4)針對構成前述標籤之基材膜以偏光ATR法來求得1340cm-1下的吸光度以及1410cm-1下的吸光度的情況下,前述標籤的主收縮方向的吸光度比(1340cm-1/1410cm-1)與相對於主收縮方向呈正交之方向的吸光度比(1340cm-1/1410cm-1)之差為0.2以上;(5)針對構成前述標籤之基材膜以溫度調變示差掃描熱析儀測定可逆熱容量曲線時的Tg前後的比熱容量差△Cp為0.2J/(g.℃)以上;(6)前述標籤的鉛直方向的長度的最大值與最小值的差為3mm以下。
Description
本發明係關於一種熱收縮性聚酯系膜經熱收縮後的聚酯系標籤以及由此標籤所被覆之包裝容器。
近年來,在作為玻璃瓶或塑料瓶等的保護及兼作為商品的標示之標籤包裝、帽蓋封條(cap seal)、集積包裝等用途中,傾向於使用耐熱性高、易焚化、耐溶劑性優異之聚酯系的熱收縮性膜,逐漸作為收縮標籤而被廣泛地利用,隨著PET(polyethylene terephthalate;聚對苯二甲酸乙二酯)瓶容器飲料等的增加,熱收縮性膜使用量亦在增加。
先前作為PET瓶被覆用熱收縮性標籤而言,係使用厚度為40μm至60μm之熱收縮性膜(例如專利文獻1)。然而,在經過利用內容物之後,用於包裝用之熱收縮性膜即成為單純的垃圾。於此,受到所謂儘可能減少垃圾之環境意識的提高,膜製造商亦進行將熱收縮性聚酯系膜的厚度變薄之研究。
然而,當熱收縮性標籤的厚度變薄的情況下,由於熱
收縮後的標籤(以下所稱之標籤係指熱收縮後的標籤)的厚度當然變薄,故可能在貨車運輸時經標籤被覆之製品彼此之間碰撞而產生標籤的開裂或撕裂(即所謂的龜裂)。一般的熱收縮性膜於主收縮方向的拉伸破斷強度雖高,但由於相對於收縮方向呈正交之方向的拉伸破斷強度低,故在厚度經薄化之標籤中,容易由於運送時的搖晃或振動及製品彼此之間的接觸而導致龜裂產生。
另一方面,在專利文獻2所記載的發明中,推測是將熱收縮性聚酯膜的長度方向與寬度方向的兩方向的拉伸破斷強度提高,即使是厚度薄之標籤亦具有強度,而於運送中的龜裂等的發生頻率低。然而,與一般的熱收縮性膜的製造方法作比較,專利文獻2的製造方法非常複雜,而需要增大製造設備,有著初始投資費用高等問題。
專利文獻1:日本特開2003-12831號公報。
專利文獻2:日本特許第5240387號公報。
有鑑於前述情況,本發明的課題係提供一種標籤,即使使用厚度薄而強度相對較低的膜,龜裂的發生頻率仍較
少。
可解決前述問題之本發明之聚酯系標籤,其特徵在於滿足以下(1)至(6)的條件。
(1)標籤的基材膜的厚度為8μm以上30μm以下。
(2)構成標籤之聚酯的極限黏度為0.58dl/g以上。
(3)標籤的主收縮方向以及相對於主收縮方向呈正交之方向的拉伸破斷伸長度皆為5%以上。
(4)針對構成標籤之基材膜以偏光ATR(attenuated total reflection;衰減全反射)法來求得1340cm-1下的吸光度以及1410cm-1下的吸光度的情況下,標籤的主收縮方向的吸光度比(1340cm-1/1410cm-1)與相對於主收縮方向呈正交之方向的吸光度比(1340cm-1/1410cm-1)之差為0.2以上。
(5)針對構成標籤之基材膜以溫度調變示差掃描熱析儀測定可逆熱容量曲線時的Tg前後的比熱容量差△Cp為0.2J/(g.℃)以上。
(6)前述標籤的鉛直方向的長度的最大值與最小值的差為3mm以下。
較佳為相對於主收縮方向呈正交之方向的拉伸破斷強度為5MPa以上60MPa以下。
構成標籤之聚酯較佳為於構成該聚酯之單位100莫耳%中具有源自丙二醇的單位5莫耳%以上15莫耳%以下。
本發明還包含一種包裝容器,該包裝容器的外周的至
少一部分具有前述標籤。
本發明的標籤可對應薄化的要求且抑制運送時的龜裂的發生。
本發明的標籤係熱收縮後的標籤,係藉由將熱收縮性聚酯系膜的兩端部重疊後以有機溶劑黏合所形成之管狀的熱收縮性聚酯系標籤被覆於PET瓶且熱收縮而得。在此,所謂端部係指寬度方向(沿長度方向的方向)的端部。
前述熱收縮性聚酯系膜係不僅包含僅由1層之聚酯所構成之膜,亦包含如以聚酯/聚酯以外的樹脂/聚酯之積層構成(亦可為5層以上)的膜,即其外側之層皆成為聚酯之積層膜。
用於熱收縮性聚酯系膜之聚酯較佳係以對苯二甲酸乙二酯單元作為主要構成成分。這是因為其具有優異的強度及耐熱性。於聚酯的構成單元100莫耳%中,對苯二甲酸乙二酯單元較佳為50莫耳%以上,更佳為60莫耳%以上,又更佳為70莫耳%以上。
作為構成前述聚酯之其它的二羧酸成分,可列舉例如:間苯二甲酸、鄰苯二甲酸、2,6-萘二羧酸等的芳香族二羧酸;己二酸、壬二酸、癸二酸、癸烷二羧酸等的脂肪族二羧酸;以及1,4-環己烷二羧酸等的脂環式二羧酸等。
此外,較佳為使聚酯中不含有三價以上的多元羧酸(例如偏苯三酸、均苯四酸及其酸酐等)。使用含有這些多元羧酸的聚酯所得到之熱收縮性聚酯系膜係難以達到必要的高收縮率。
作為構成聚酯之二醇成分而言,除了乙二醇以外,可列舉例如:1,3-丙二醇、2,2-二乙基-1,3-丙二醇、2-n-丁基-2-乙基-1,3-丙二醇、2,2-異丙基1,3-丙二醇、2,2-二-n-丁基-1,3-丙二醇、1,4-丁二醇、己二醇、新戊二醇等的脂肪族二醇;1,4-環己烷二甲醇等的脂環式二醇;以及雙酚A等的芳香族系二醇等。
其中較佳為使用1,4-環己烷二甲醇等的脂環式二醇、或是具有碳數為3個至6個之二醇(例如1,3-丙二醇、1,4-丁二醇、新戊二醇、己二醇等)。特別是當使用1,3-丙二醇的情況下,容易得到滿足本發明的必要條件即前述(1)至(6)的條件之聚酯。
在本發明中,由於如下的理由而較佳使用1,3-丙二醇。一般而言,若欲提高熱收縮性聚酯系膜的長度方向的熱收縮率的拉伸破斷強度而進行縱向拉伸的情況下,通常會導致長度方向的熱收縮率提高以及緊經(tight end)等問題。此所稱「緊經」係指被覆於瓶而經熱收縮之標籤的邊緣彎曲(例如上端緣向下彎曲或是下端緣向上彎曲)而變成為不良的外觀。亦即所謂在瓶的鉛直方向(高度方向)的標籤的長度變短的現象。然後,在前述專利文獻2中,為了抑制這種問題,需要在縱向拉伸後施加中間熱處理;或是於縱向拉伸後、中間熱處理時及最終熱處理時等進行對長度方向之鬆弛處理,為此使得製造方法變得複雜。
然而,經發明人銳意研究發現,若合併使用1,3-丙二醇作為二醇成分,則即使未於縱向拉伸後的中間熱處理或對長度方向施加鬆弛處理,仍可將長度方向的熱收縮率維持為低。其理由雖不明確,但認為是由於1,3-丙二醇的直鏈結構在拉伸聚酯時,可抑制分子配向中晶體結構的生成。
構成標籤之聚酯較佳為於構成該聚酯之單位100莫耳%中具有源自丙二醇的單位5莫耳%以上15莫耳%以下。若小於5莫耳%的情況下,長度方向的熱收縮率會變高,可能導致被覆於瓶而經熱收縮時發生緊經等問題,故而不佳。較佳為6莫耳%以上,更佳為8莫耳%以上,尤佳為10莫耳%以上。丙二醇衍生的單元的上限沒有特別的限
定,由於若增加丙二醇衍生的單元其原料成本會變高,因此較佳為15莫耳%左右。
此外,聚酯係較佳於全聚酯樹脂中之多元醇成分100莫耳%中或是多元羧酸成分100莫耳%中的可成為非晶質成分之1種以上的單體成分的合計為17莫耳%以上,更佳為18莫耳%以上,更佳為19莫耳%以上,尤佳為20莫耳%以上。此外可成為非晶質成分之單體成分的合計的上限並沒有特別限定,較佳為30莫耳%。藉由將非晶質成分量設定為前述範圍,可獲得玻璃轉移溫度(Tg)調整為60℃至80℃之聚酯。
作為可成為非晶質成分之單體而言,可列舉例如:新戊二醇、1,4-環己烷二甲醇、間苯二甲酸、1,4-環己烷二羧酸、2,6-萘二羧酸、2,2-二乙基-1,3-丙二醇、2-n-丁基-2-乙基-1,3-丙二醇、2,2-異丙基1,3-丙二醇、2,2-二-n-丁基-1,3-丙二醇、己二醇。在這些中較佳為使用新戊二醇、1,4-環己烷二甲醇或是間苯二甲酸。
另外,較佳為使聚酯中不含有碳數8個以上的二醇(例如辛二醇等)、或是3價以上的多元醇(例如三羥甲基丙烷、三羥甲基乙烷、甘油、雙甘油等)。使用含有這些二醇或多元醇的聚酯所得到的熱收縮性聚酯系標籤則難以達成必要的高收縮率。此外,較佳為使聚酯中儘可能不含有二乙二
醇、三乙二醇、聚乙二醇。
形成用於本發明的標籤之熱收縮性聚酯系膜之樹脂之中,根據需要可添加各種的添加劑,例如蠟類、抗氧化劑、抗靜電劑、結晶成核劑、黏度降低劑、熱穩定劑、著色用顏料、抗著色劑、紫外線吸收劑等。
在形成前述熱收縮性聚酯系膜之樹脂中,較佳為添加作為潤滑劑之微粒以改善膜的操作性。作為微粒可任意選擇,例如作為無機系微粒可列舉:二氧化矽、氧化鋁、二氧化鈦、碳酸鈣、高嶺土、硫酸鋇等;例如作為有機系微粒可列舉:丙烯酸系樹脂粒子、三聚氰胺樹脂粒子、矽氧烷樹脂粒子、交聯聚苯乙烯粒子等。微粒的平均粒徑可於0.05μm至3.0μm的範圍內(在以庫侖特計數器測定的情況)根據需要而適當地選擇。
作為在形成熱收縮性聚酯系膜之樹脂中調配前述微粒的方法而言,例如雖然可於製造聚酯系樹脂之任意的階段中進行添加,但較佳為於酯化的階段,或是於酯交換反應結束後、縮合聚合反應開始前的階段中作為分散在乙二醇等之漿料添加而進行縮合聚合反應。此外,較佳為藉由使用附通氣孔之混練擠出機將分散於乙二醇或水等之微粒的漿料與聚酯系樹脂原料進行摻合之方法、或是使用混練擠出機將經乾燥之微粒與聚酯系樹脂原料進行摻合之方法
等。
為了改善膜表面的黏合性,可對前述熱收縮性聚酯系膜施加電暈處理、塗膜處理或火焰處理等。
另外,前述熱收縮性聚酯系膜亦包含至少含有1層聚酯系樹脂層之積層型的聚酯膜。當聚酯系樹脂層積層有2層以上時,其聚酯系樹脂層可為相同組成的聚酯亦可為不同組成的聚酯。
此外,就可作為聚酯以外之其它層而積層之層而言,只要是熱塑性樹脂層即可,並沒有特別的限定,由價格或熱收縮特性來看,較佳為聚苯乙烯系樹脂層。其它的層可為1層或亦可為2層以上。
作為聚苯乙烯系樹脂,原可使用苯乙烯、α-甲基苯乙烯或p-甲基苯乙烯等苯乙烯衍生物所構成之均聚物、共聚物,亦可使用可與苯乙烯或苯乙烯衍生物進行共聚合之單體,例如:丙烯酸、甲基丙烯酸、該些的金屬鹽類(例如鈉、鉀、鋰、鎂、鈣、鋅、鐵等金屬鹽類)、丙烯酸酯、甲基丙烯酸酯等脂肪族不飽和羧酸或與其衍生物之共聚物、或丁二烯等的嵌段共聚物。其中較佳為聚苯乙烯、苯乙烯-丁基丙烯酸酯共聚物、苯乙烯-丁二烯嵌段共聚物等。另外,聚苯乙烯系樹脂中,亦可為了降低熱收縮起始溫度或提高耐
衝擊性之目的而調配塑化劑、相溶劑等。
聚苯乙烯系樹脂中,較佳為添加熱塑性樹脂及/或橡膠成分。作為熱塑性樹脂,可列舉如:具有無規結構之聚苯乙烯、AS(acrylonitrile-styrene;丙烯腈-苯乙烯共聚物)樹脂、ABS(acrylonitrile-butadiene-styrene;丙烯腈-丁二烯-苯乙烯共聚物)樹脂等的苯乙烯樹脂;聚對苯二甲酸乙二酯、聚萘二甲酸乙二酯、聚對苯二甲酸丁二酯等的聚酯系樹脂;尼龍6、尼龍66、尼龍12、尼龍4、聚六亞甲己二醯胺等的聚醯胺系樹脂;聚乙烯、聚丙烯、聚丁烯等的聚烯烴樹脂等。
另一方面,作為橡膠成分,較佳為作為其構成成分而含有苯乙烯系化合物之橡膠狀共聚物,例如可由苯乙烯及橡膠成分中各選出一種以上經共聚合而成之隨機、嵌段或是接枝共聚物。作為這樣的橡膠狀共聚物,例如可列舉:苯乙烯-丁二烯共聚物橡膠、苯乙烯-異戊二烯嵌段共聚物、將該些的丁二烯部分的一部分或是全部氫化的橡膠、丙烯酸甲酯-丁二烯-苯乙烯共聚物橡膠、丙烯腈-丁二烯-苯乙烯共聚物橡膠、丙烯腈-丙烯酸烷基酯-丁二烯-苯乙烯共聚物橡膠、甲基丙烯酸甲酯-丙烯酸烷基酯-丁二烯-苯乙烯共聚物橡膠等。作為構成成分而含有前述苯乙烯系化合物之橡膠狀共聚物,由於具有苯乙烯單元,故對於具有間規結構之聚苯乙烯系樹脂的分散性良好,對於聚苯乙烯系
樹脂的可塑性改良效果大。此外,作為相溶性調整劑而言,可適宜地使用作為構成成分而含有前述苯乙烯系化合物之橡膠狀共聚物。
另一方面,作為橡膠成分而言,可使用其它如天然橡膠、聚丁二烯、聚異戊二烯、聚異丁烯、氯丁橡膠、乙烯-丙烯共聚物橡膠、胺甲酸乙酯橡膠、矽氧烷橡膠、丙烯酸橡膠、聚醚-酯橡膠、聚酯-酯橡膠等。
此外,聚苯乙烯系樹脂的重量平均分子量較佳為10,000以上,更佳為50,000以上。重量平均分子量小於10,000者由於膜的強度保持性或耐熱性容易下降而不佳。重量平均分子量的上限沒有特別限定,但若超過150萬則可能產生伴隨拉伸張力的增大而發生破斷等,因此不佳。
聚苯乙烯系樹脂係在市面上已有各種製造商販賣之各種等級,故亦可使用市售品。
再來對本發明的標籤的特性進行說明。本發明的標籤是熱收縮性聚酯系膜經熱收縮後之物。當使其熱收縮時,一般以於瓶安裝熱收縮性標籤(熱收縮前的標籤)之狀態下使其熱收縮。本發明的標籤係標籤的基材膜的厚度為8μm以上30μm以下。由於本發明的目的在於薄化標籤,故厚度必須在此範圍內。標籤的基材膜的厚度更佳為9μm以上28μm以下,又更佳為10μm以上26μm以下,尤佳為20μm
以下。
構成本發明的標籤的聚酯的極限黏度為0.58dl/g以上。若標籤的極限黏度為0.58dl/g以上,則標籤的拉伸破斷伸長度亦可提高,而龜裂的發生頻率降低。更佳為0.60dl/g以上,又更佳為0.61dl/g以上。極限黏度雖為高較佳,但若太高則對生產膜時擠出原料之機械等的負擔會變高,因此上限為0.9dl/g。
本發明的標籤於主收縮方向以及相對於主收縮方向呈正交之方向的拉伸破斷伸長度皆為5%以上。若標籤的拉伸破斷伸長度高,則龜裂的發生頻率降低。標籤的主收縮方向的拉伸破斷伸長度更佳為15%以上,又更佳為25%以上。拉伸破斷伸長度雖為高較佳,但考慮到製造熱收縮性標籤時會變得容易受到溶劑攻擊或是熱收縮性標籤長期儲存時特性會變得容易變化,其上限為50%。另外,本發明的標籤雖然是熱收縮後的標籤,但仍具有熱收縮的餘力,例如將被覆於瓶之標籤剝離而浸漬於80℃左右的熱水,則會熱收縮。因此,可知此時收縮之方向為主收縮方向。出於同樣的理由,相對於標籤的主收縮方向呈正交之方向的拉伸破斷伸長度更佳為6%以上,又更佳為7%以上。此外,由於與前述同樣的原因,其上限大約為20%。
本發明的標籤係針對構成標籤之基材膜以偏光ATR
法來求得1340cm-1下的吸光度以及1410cm-1下的吸光度的情況下,標籤的主收縮方向的吸光度比(1340cm-1/1410cm-1)與相對於主收縮方向呈正交之方向的吸光度比(1340cm-1/1410cm-1)之差為0.2以上。當此差小於0.2的情況下,為抑制緊經等外觀不良,不得不實施如專利文獻2中記載的複雜的生產方法。前述的差更佳為0.22以上,又更佳為0.24以上。前述吸光度比係表示分子配向的反式構象(trans conformation)的比率。反式構象被認為是表示分子鏈的交纏狀態,若反式構象的比率較高,則分子鏈的交纏的狀態亦高。因此,主收縮方向的吸光度比與相對於主收縮方向呈正交之方向的吸光度比的差小即意味著長度方向的收縮率接近於寬度方向的收縮率。另外,由於所謂偏光ATR法係對試樣表面(數μm左右)的分子配向進行分析的手段,因此於積層型的聚酯膜中,最外層的聚酯層中之吸光度比成為前述的數值。另外,吸光度比的測量方法如後所述。此外,所謂構成標籤之基材膜係指將印刷層及熱收縮性膜以外的其它的層除外之意。
本發明的標籤係對於構成標籤之基材膜以溫度調變示差掃描熱析儀測定可逆熱容量曲線時的Tg前後的比熱容量差△Cp(相當於可動非晶量(movable amorphous content))必需為0.2J/(g.℃)以上。若對於標籤試樣以溫度調變示差掃描熱析儀測定可逆熱容量曲線,則在相當於Tg之溫度下基線會偏移。偏移前後的值的差稱為比熱容量差△Cp,
此相當於可動非晶量。所謂可動非晶係指Tg附近分子鏈開始移動之非晶,可與剛性非晶作區別,該剛性非晶若在未變得較Tg高的溫度則分子鏈不會成為可移動的狀態。發明人發現此可動非晶的量會影響熱收縮率。然後,為了獲得高熱收縮率且於長度方向不易收縮之膜,重要的是不使可動非晶變成剛性非晶、或是使剛性非晶的大部分變成可動非晶。若△Cp小於0.2J/(g.℃),則由於可動非晶量少,故容易受到作成熱收縮性標籤時的溶劑攻擊所導致的不良影響;此外被認為作成熱收縮性標籤後的長期儲存所致使的標籤的劣化大。若劣化大,則熱收縮後的標籤變脆,容易產生龜裂。△Cp更佳為0.23J/(g.℃)以上,又更佳為0.26J/(g.℃)以上。另外,由前述觀點來看,其上限並沒有特別的限定,若考慮到構成熱收縮性標籤之基材膜的自然收縮率的增加,上限大約為0.6J/(g.℃)左右。
在本發明的標籤中,標籤的鉛直方向(高度方向)的長度的最大值與最小值的差為3mm以下。所謂標籤的長度係指當被覆於瓶之狀態的標籤之鉛直方向的長度。若造成緊經,則標籤的鉛直方向的長度的最大值與最小值的差可能超過3mm,意謂造成外觀不良。因此,在本發明中鉛直方向的長度的最大值與最小值的差設為3mm以下。標籤的鉛直方向的長度的最大值與最小值的差較佳為2mm以下,更佳為1mm以下。
在本發明的標籤中,較佳為相對於主收縮方向呈正交之方向的拉伸破斷強度為5MPa以上60MPa以下。若小於5MPa,則標籤的強度不足而容易發生龜裂。較佳為7MPa以上,更佳為9MPa以上。拉伸破斷強度雖為高較佳,但由於有不得不實施如專利文獻2中記載的複雜的生產方法之虞,因此上限為60MPa。
本發明中所使用的熱收縮性聚酯系膜,係可將前述聚酯原料藉由擠出機而熔融擠出形成未拉伸膜,將該未拉伸膜藉由以下所示之預定的方法作拉伸且進行熱處理而獲得。進行積層的情況下,可使用複數的擠出機、供料頭(feed block)或是多歧管(multi-manifold)即可。另外,聚酯係可藉由將前述適合的二羧酸成分與二醇成分以習知的方法進行縮合聚合而獲得。此外,通常將片(chip)狀的聚酯混合2種以上以作為膜的原料而使用。
具體而言,作為膜以及標籤的製造方法,係將原料片使用料斗乾燥機、槳式乾燥機或是真空乾燥機等進行乾燥,以200℃至280℃的溫度擠出成膜狀。或者是將未乾燥的聚酯原料於通氣式擠出機內一面去除水分一面相同地擠出成膜狀。擠出時亦可採用T模法或管式法等現有的任何方法。另外,擠出時的溫度設為不超過280℃。若熔融溫度過高,則作成標籤時的極限黏度降低而容易產生龜裂,因此不佳。擠出後,將熔融樹脂快速冷卻而獲得未拉伸膜。
另外,此「未拉伸膜」中亦含有為輸送膜而作用有必要的張力之膜。另外,作為快速冷卻的方法,可合適地採用藉由將熔融樹脂由噴嘴鑄塑至旋轉滾筒上而快速冷卻進行固化,而獲得實質上未配向的樹脂片材之方法。
對此未拉伸膜進行拉伸處理。拉伸處理係可於藉由前述鑄塑輥等冷卻後而連續進行,亦可在冷卻後暫時捲繞成卷之後再進行。
主收縮方向為膜橫向(寬度)方向一事由於在生產效率上係實用的,故以下係例示將主收縮方向設為橫向方向的情況的拉伸法。另外,在將主收縮方向設為膜縱向(長度)方向的情況下,亦可將下述方法中的拉伸方向變更90°等而依據通常的操作進行拉伸。
首先,將前述所獲得之未拉伸膜,根據需要以輥於70℃至100℃加熱、較佳於80℃至90℃加熱後,在1.1倍至1.8倍的範圍內,利用輥的速度差進行縱向拉伸。所得之縱向拉伸後的膜根據需要以80℃至120℃作預熱、較佳以90℃至110℃作預熱後,於橫向方向(相對於擠出方向呈正交之方向)以拉幅機等拉伸3.0倍以上、較佳為3.5倍以上7倍以下。拉伸溫度為65℃以上100℃以下、較佳為70℃以上95℃以下。
此外,橫向拉伸後,以較拉伸溫度高1℃至30℃的溫度下進行熱處理較佳。熱處理係為了緩和拉伸後的膜的緊張狀態而進行,且以熱處理時的溫度進行熱收縮率的調整或減少自然收縮率係有效的。然而,作為熱處理的缺點而言,若拉伸後的膜於熱處理區進行加熱則會發生曲折現象(Bowing Phenomenon)而有著寬度方向的物性變差的問題(參考文獻:成型加工,4(5),312(1992))。藉此,可獲得成為本發明的標籤之熱收縮性聚酯系膜。
前述熱收縮性聚酯系膜可以習知的方法而作成熱收縮性標籤。具體而言,於裁切為期望寬度之熱收縮性聚酯系膜上施加合適的印刷,藉由溶劑黏合等將膜的左右端部重疊而接合,以製造管膜。將此管膜裁切至適當的長度,作成管狀標籤。作為黏合用的有機溶劑,較佳為1,3-二氧戊烷或是四氫呋喃等環醚類。其它可使用苯、甲苯、二甲苯、三甲苯等芳香族烴,二氯甲烷、三氯甲烷等鹵代烴,苯酚等酚類,或是該些的混合物。
對於前述標籤藉由習知的方法形成穿孔後,被覆於PET瓶,將該PET瓶載於帶式輸送機等,使其通過吹附蒸汽型的收縮隧道(蒸汽隧道)或是吹附熱風型的收縮隧道(熱風隧道)的內部。通過這些隧道時標籤進行熱收縮,藉此熱收縮後的標籤被安裝於PET瓶等的瓶裝容器上。本發明的標籤即此熱收縮後的標籤。
作為包裝對象物,可列舉如從飲料用的PET瓶到各種的瓶、罐、點心或便當等的塑料容器及紙製的箱等。一般來說,使熱收縮性標籤進行熱收縮而被覆於這些包裝對象物的情況下,使該標籤大約熱收縮5%至70%的程度而緊貼於包裝體。被覆於包裝對象物上的標籤,可施加印刷、亦可不加印刷。另外,本發明還包含一種包裝容器,該容器的外周的至少一部分具有本發明的標籤。
本申請係基於2015年9月30日所申請之日本國特許出願第2015-195298號為基礎而主張優先權的權益。在此援引2015年9月30日提出申請之日本特許出願第2015-195298號的說明書的全部內容作為本案之參考。
以下藉由實施例對於本發明作詳細的說明,但下述實施例並非限制本發明,在不脫離本發明的精神的範圍內實施變更的情況亦包含於本發明的範圍。另外,實施例以及比較例所得之膜以及標籤的物性的測定方法如下所述。
[熱收縮率(熱水熱收縮率)]
將熱收縮性聚酯系膜沿著長度方向以及與其鉛直方向(寬度方向)裁切為10cm×10cm的正方形,於90℃±0.5℃的熱水中以無負荷狀態浸漬10秒使其熱收縮後,立即於25
℃±0.5℃的水中浸漬10秒後,從水中拉出,測定試樣的縱向及橫向的長度,依據下式求得其值。
熱收縮率(%)={(收縮前的長度-收縮後的長度)/收縮前的長度}
在本實施例中,膜的收縮率最大的方向(主收縮方向)為寬度方向。
[Tg前後的比熱容量差△Cp]
使用溫度調變示差掃描熱析儀(DSC、「Q100」;TA Instruments公司製),於密封式鋁鍋(hermetic aluminum pan)內精秤10.0mg±0.2mg的熱收縮性聚酯系膜或熱收縮後的標籤作為樣品,以MDSC(註冊商標)加熱模式(heat-only mode)、平均升溫速度1.0℃/min、調變周期40秒作測定,獲得可逆熱容量曲線。在所得的熱容量曲線中,利用附屬的分析軟體(TA Instruments公司製;TA Analysis)求得反曲點,依據下式求得反曲點(玻璃轉移溫度;Tg)前後的熱容量差,設為可逆熱容量差△Cp(J/(g.℃))。在此,前述的反曲點係指當可逆熱容量曲線是沒有凹凸的理想曲線的情況下,將可逆熱容量曲線微分2次時的值為0的點。
可逆熱容量差△Cp(J/(g.℃))=(較Tg更高溫側的熱容量)-(較Tg更低溫側的熱容量)
在此,畫出於熱容量曲線中之較Tg更高溫側的熱容量曲線的基線的延長線。將由Tg+5℃至Tg+15℃的範圍的
熱容量曲線的基線以及藉由最小平方法作成直線擬合者作為前述較Tg更高溫側的熱容量曲線的基線的延長線。然後,求得於反曲點(Tg)中與切線的交點,讀取此交點中Y軸(可逆熱容量)的值以作為高溫側的熱容量。接著,將由Tg-15℃至Tg-5℃的範圍的熱容量曲線的基線以及藉由最小平方法作成直線擬合者作為前述較Tg更低溫側的熱容量曲線的基線的延長線。然後,求得於反曲點(Tg)中與切線的交點,讀取此交點中Y軸(可逆熱容量)的值以作為低溫側的熱容量,並將高溫側的熱容量與低溫側的熱容量的差設為熱容量差△Cp(J/(g.℃))。
針對熱收縮性聚酯系膜或是熱收縮後的標籤,以偏光ATR法來求得1340cm-1下的吸光度以及1410cm-1下的吸光度比(1340cm-1/1410cm-1)。具體而言,利用FT-IR(Fourier transform infrared spectroscopy;傅立葉轉換紅外光譜)裝置(「FTS 60A/896」、Varian公司製),以ATR法利用測定波長領域(650cm-1至4000cm-1)、累計次數128次、施加偏光之紅外線吸收光譜的吸收帶而進行。由所得之吸光度比依據下式求得其差,作為吸光度比的差。
吸光度比的差=標籤主收縮方向的吸光度比-相對於標籤主收縮方向呈正交之方向的吸光度比
[拉伸破壞強度、伸長度]
製作測定方向為140mm,而與測定方向呈正交之方向
為20mm的長條狀的試驗片。使用萬能拉伸試驗機「DSS-100」(島津製作所製),在下列的條件下進行拉伸試驗:將試驗片的兩端以夾盤分別把持單側20mm(夾盤間距離100mm)、氛圍溫度23℃、拉伸速度200mm/min;設拉伸破壞時的強度(應力)為拉伸破壞強度(MPa)、伸長設為拉伸破斷伸長度(%)。
[極限黏度]
精秤原料片0.1g或是標籤0.1g,溶解於25ml的苯酚/四氯乙烷=3/2(質量比)的混合溶劑後,以奥士華黏度計於30℃±0.1℃作測定。極限黏度[η]係由下式(哈金斯公式)所求得。
在此,ηsp:比黏度,t0:使用奥士華黏度計之溶劑的落下時間,t:使用奥士華黏度計之片(或是標籤)溶液的落下時間,C:片(或是標籤)溶液的濃度。另外,在實際的測定中,於哈金斯公式中設k=0.375並以下述近似式計算出
極限黏度。
[熱收縮性標籤的製作方法]
在以下實施例及比較例中所製作之膜輥上以寬度約242mm作切割,並分割為預定的長度而捲繞,藉此製作小型的切割卷。利用東洋油墨公司製造的草、金、白色的墨水,於此切割卷重覆施加標籤用的印刷(3色印刷)。此外,於每個標籤中之膜的長度方向上以大約22mm的間隔形成為2條平行之經過膜全長度方向的穿孔(大約直徑1mm的孔以大約間隔4mm排列之穿孔)。藉由將熱收縮性膜的兩端部以二氧戊環黏合,以製作圓筒狀的熱收縮性標籤(以熱收縮性膜的主收縮方向作為圓周方向之標籤)。之後,於長度方向上以210mm為節距作切割而作成熱收縮性標籤,於500ml的方型PET瓶(本體部係邊長55mm的剖面正方形,頸部的最小部為邊長25mm的剖面正方形)被覆標籤,於區域溫度80℃的Fuji Astec Inc製造的蒸汽隧道(型號;SH-1500-L)內部,以2.5秒通過,藉此使標籤熱收縮而安裝於瓶。另外,在安裝時使頸部中邊長31mm的正方形部
分作為標籤的上端的方式作調整。
[標籤(熱收縮後)的老化]
將安裝完成標籤的PET瓶以每24支為單位裝一個紙箱,設想於夏天的倉庫作儲存,而於45℃的環境試驗室儲存60天。
[標籤(熱收縮後)的物性測定]
針對老化後的接觸PET瓶本體部之標籤測定各種物性。此外,針對實施例5中標籤外側的聚酯層的物性作測定。另外,印刷部係藉由以甲基乙基酮浸潤於布且以此布擦拭而去除。
[標籤(熱收縮後)的失真]
以是否有標籤的失真(亦即緊經)作為收縮後的完成度進行評價。具體而言,測定標籤的鉛直方向的長度,若最大值與最小值的差為3mm以下則評為○,若超過3mm則評為X。
[有無發生龜裂]
將上述裝有老化後的PET瓶之紙箱3箱載於卡車的載台上,以合計48小時以上的方式使卡車行進。從紙箱中取出PET瓶,以目視調查標籤是否有龜裂。在72支的PET瓶中,即便有1支含有龜裂的情況亦評為X,完全沒有龜
裂的情況則評價為○。
[聚酯原料的調製]
[合成例1(聚酯的合成)]
在酯化反應罐中,添加57036質量份的對苯二甲酸(TPA)、33244質量份的乙二醇(EG)、15733質量份的新戊二醇(NPG)、作為縮合聚合催化劑的23.2質量份的三氧化銻、5.0質量份的醋酸鈉(鹼金屬化合物)以及46.1質量份的三甲基磷酸酯(磷化合物),壓力調至0.25MPa,於220℃至240℃攪拌120分鐘藉此進行酯化反應。將反應罐復壓成常壓,加入3.0質量份的乙酸鈷.四水鹽類以及124.1質量份的乙酸鎂.四水鹽類,以240℃攪拌10分鐘後,以75分鐘減壓至1.33hPa,並升溫至280℃。以280℃持續攪拌至熔融黏度成為4500泊(poise)為止(約70分鐘)後,以股束狀於水中排出。將排出物以股束切割器進行切割,藉此獲得片B。片B的極限黏度為0.75dl/g。
[合成例2]
藉由與合成例1相同的方法獲得表1所示之組成的片A、片C。表中DEG為二乙二醇的縮寫,PD為1,3-丙二醇的縮寫。另外,在片A中以相對於聚酯之2,000ppm的比率添加作為潤滑劑的SiO2(FUJI SILYSIA CHEMICAL LTD.製SYLYSIA266)。片A的極限黏度為0.75dl/g,片C為0.92dl/g。
此外,表2係表示實施例5所使用之市售的聚苯乙烯系樹脂。另外,「CLEAREN」為電氣化學工業公司的註冊商標,而「Tufprene」為旭化成化學公司的註冊商標。
[實施例1]
<熱收縮性膜的製造方法>
對於前述片A、片B及片C分別進行預乾燥,如表3所示,以20質量%的片A、70質量%的片B及10質量%的片C作混合而裝入擠出機中。將此混合樹脂熔融於260℃中而由T模中擠出,與表面溫度已冷卻至30℃之旋轉的金屬輥接觸而快速冷卻,藉此獲得厚度為121μm的未拉伸膜。此時的未拉伸膜的抽取速度(金屬輥的旋轉速度)約為20m/min。此外,未拉伸膜的Tg為73℃。
將前述未拉伸膜導至縱向拉伸機。在縱向拉伸機的預熱輥上將膜表面溫度預熱至85℃為止,利用輥的速度差而縱向拉伸至1.5倍。縱向拉伸以表面溫度30℃的輥作冷卻。
將所得到的縱向拉伸後的膜導至拉幅機(橫向拉伸機)。預熱步驟的溫度設為100℃、拉伸步驟的溫度設為75℃,於寬度方向拉伸4.5倍。將橫向拉伸後的膜於88℃下以8秒鐘、緊張狀態下進行熱處理。之後冷卻,將兩邊緣部切斷去除而捲繞成寬度800mm之輥狀,藉此將厚度為18μm的拉伸膜經過預定的長度而連續地製造。所得之膜以及由所得之膜所製作經熱收縮而老化後的標籤的物性藉由前述方法進行評價。評價結果如表4所示。分別以表4A表示膜的特性結果,以表4B表示老化後標籤特性的結果
(以下相同)。可知未發生龜裂而為良好的標籤。
[實施例2]
除了將熔融溫度提高至280℃以外,以與實施例1相同的方式,製造厚度為18μm的膜。評價結果如表4所示。相較於膜時雖由於老化而極限黏度略有下降,但不發生龜裂而為良好的標籤。
[實施例3]
除了將片A、片B及片C變更為質量比30:60:10以外,以與實施例1相同的方式,製造厚度為18μm的膜。評價結果如表4所示。相較於膜時雖由於老化而Tg前後的比熱容量差△Cp有下降,但不發生龜裂而為良好的標籤。
[實施例4]
除了將未拉伸膜的厚度設為60μm以外,以與實施例1相同的方式,製造厚度為9μm的膜。評價結果如表4所示。不發生龜裂而為良好的標籤。
[實施例5]
利用共擠出法,將芯層形成用樹脂、表層形成用樹脂以及黏合劑層形成用樹脂由各別的擠出機(第一擠出機至第三擠出機)熔融擠出而積層於模具(T模)內,藉由氣刀法纏繞於已冷卻至30℃之旋轉的金屬輥而快速冷卻,藉此獲
得厚度為121μm且三種五層構成的未拉伸膜,即芯層的正面和背面兩側積層有中間層(黏合劑層),並於這些中間層的外側各自積層有表層之構成。未拉伸膜的各層的形成方法(至熔融擠出為止的步驟)如下。另外,在以下的說明中,從聚苯乙烯系樹脂積層片的表側依序為第一層、第二層、第三層、第四層、第五層(亦即第五層的表面為金屬輥接觸面)。此時的未拉伸膜的抽取速度(金屬輥的旋轉速度)約為20m/min。
.第一層、第五層(表層)的形成
將前述片A與片B各自使用摻合機裝置進行預乾燥後,將其預乾燥後的25質量份的片A與65質量份的片B與10質量份的片C於摻合機進行混合後,以定量螺旋進料器連續供給至第一擠出機正上方的料斗。然後,將所供給的片A至片C的混合物在260℃下由單軸式的第一擠出機的T模熔融擠出(以可積層於中間層的外層的方式而熔融擠出,該中間層係積層於芯層的正反面的外側)。為了使由T模的擠出穩定,於擠出機與T模之間夾設有螺旋型且為並聯型的齒輪泵。
.第二層、第四層(黏合劑層)的形成
將前述片D使用摻合機裝置進行預乾燥後,將其預乾燥後的片D以定量螺旋進料器連續供給至第二擠出機正上方的料斗。然後,將所供給的片D由單軸式的第二擠出機
的T模熔融擠出(以可積層於芯層的正反面的外側的方式而熔融擠出)。另外,第二擠出機的溫度調整至200℃。此外,與藉由第一擠出機的擠出相同,為了使由T模的擠出穩定,於擠出機與T模之間夾設有螺旋型且為並聯型的齒輪泵。
.第三層(芯層)的形成
將前述片E、片F、片G各自使用摻合機裝置進行預乾燥後,以定量螺旋進料器連續將這些的片E、片F、片G各別供給至混合器內。另外,設片E的供給量為43質量%,片F的供給量為43質量%,片G的供給量為14質量%。之後,將在混合器內混合之片E、片F、片G的混合原料以定量螺旋進料器連續供給至第三擠出機正上方的料斗。然後,將所供給的片E、片F、片G(經混合後者)由單軸式的第三擠出機的T模熔融擠出。另外,第三擠出機的溫度亦調整至200℃。此外,與藉由第一擠出機的擠出或第二擠出機的擠出相同,為了使由T模的擠出穩定,於擠出機與T模之間夾設有螺旋型且為並聯型的齒輪泵。
在藉由前述各擠出機的樹脂的擠出中,未拉伸膜的形成中第一擠出機至第三擠出機的排出量係調整為使第一層/第二層/第三層/第四層/第五層的厚度成為33/3/49/3/33(總厚度121μm)的方式。評價結果如表4所示。不發生龜裂而為良好的標籤。
[比較例1]
除了將熔融溫度提高至310℃以外,以與實施例1相同的方式製造厚度為18μm的膜。評價結果如表4所示。相較於膜時由於老化使得長度方向的拉伸破斷伸長度、極限黏度及Tg前後的比熱容量差△Cp下降,而發生龜裂,為不合適的標籤。
[比較例2]
除了將片A與片B的質量比變更為30:70以外,以與實施例1相同的方式製造厚度為18μm的膜。評價結果如表4所示。膜的長度方向的收縮率高而發生緊經,為不合適的標籤。
[比較例3]
除了將片A、片B及片C的質量比變更為5:80:15以外,以與實施例2相同的方式製造厚度為18μm的膜。評價結果如表4所示。由於老化使得極限黏度及拉伸破斷伸長度下降而發生龜裂,為不合適的標籤。
[比較例4]
除了將未拉伸膜的厚度設為27μm以外,以與實施例2相同的方式,製造厚度為4μm的膜。由於老化使得極限黏度略為下降,但因標籤的厚度薄,而發生龜裂,為不合適的標籤。
[參考例1]
除了將未拉伸膜的厚度設為270μm以外,以與比較例1相同的方式,製造厚度為40μm的膜。評價結果如表4所示。由於老化使得極限黏度略為下降,但因標籤的厚度厚,並沒有發生龜裂。
本發明的標籤可對應於薄化的要求且抑制運送時的龜裂的發生,故有用於作為飲料用瓶的標籤等。
Claims (3)
- 一種聚酯系標籤,其滿足以下(1)至(7)的條件:(1)前述標籤的基材膜的厚度為8μm以上30μm以下;(2)構成前述標籤之聚酯的極限黏度為0.58dl/g以上;(3)前述標籤的主收縮方向以及相對於主收縮方向呈正交之方向的拉伸破斷伸長度皆為5%以上;(4)針對構成前述標籤之基材膜以偏光衰減全反射法來求得1340cm-1下的吸光度以及1410cm-1下的吸光度的情況下,前述標籤的主收縮方向的吸光度比(1340cm-1/1410cm-1)與相對於主收縮方向呈正交之方向的吸光度比(1340cm-1/1410cm-1)之差為0.2以上;(5)針對構成前述標籤之基材膜以溫度調變示差掃描熱析儀測定可逆熱容量曲線時的Tg前後的比熱容量差ΔCp為0.2J/(g.℃)以上;(6)前述標籤的鉛直方向的長度的最大值與最小值的差為3mm以下;(7)前述標籤相對於主收縮方向呈正交之方向的拉伸破斷強度為5MPa以上60MPa以下。
- 如請求項1所記載之聚酯系標籤,其中構成標籤之聚酯係在構成聚酯之單位100莫耳%中,具有源自丙二醇的單位為5莫耳%以上15莫耳%以下。
- 一種包裝容器,該包裝容器的外周的至少一部分具有如請求項1或2所記載之標籤。
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