TW202248277A - 結晶性聚酯樹脂及聚酯樹脂水分散體、以及使用其之黏接用或塗佈用之組成物 - Google Patents
結晶性聚酯樹脂及聚酯樹脂水分散體、以及使用其之黏接用或塗佈用之組成物 Download PDFInfo
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- polyester resin
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Classifications
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Abstract
本發明之目的係提供保存穩定性、高黏接性、耐黏連性、耐水性優異的黏接劑組成物、塗佈組成物。一種結晶性聚酯樹脂,係以多元羧酸成分與多元醇成分作為共聚成分,多元羧酸成分含有30~70莫耳%之對苯二甲酸、10~60莫耳%之1,4-環己烷二甲酸、5~30莫耳%之碳數10以下之脂肪族二羧酸,且具有磺酸鹽基之芳香族二羧酸成分之含量未達3莫耳%,多元醇成分含有50~100莫耳%之1,4-丁二醇,該結晶性聚酯樹脂之酸價為100~600eq/t,玻璃轉移溫度為-30~30℃,熔點為70~160℃,數量平均分子量為5000~40000。
Description
本發明關於結晶性聚酯樹脂及聚酯樹脂水分散體、黏接用或塗佈用之組成物。更詳細而言,係關於以聚酯樹脂水分散體作為主成分,尤其保存穩定性、黏接性、耐黏連性、耐水性優異的黏接劑、塗佈劑。
聚酯樹脂廣泛被用來作為塗料、塗佈劑及黏接劑等所使用之樹脂組成物的原料。聚酯樹脂一般係由多元羧酸與多元醇構成。多元羧酸與多元醇的選擇與組合、分子量的高低可自由地控制,獲得之聚酯樹脂使用在以塗料用途、黏接劑用途為首的各種用途。
在聚酯樹脂之分子設計中,共聚成分的選擇係重要。多元羧酸成分、多元醇成分大致分類的話,有芳香族、脂肪族、脂環族等。藉由該等成分的選擇,可決定展現聚酯樹脂之柔軟性的玻璃轉移溫度。就使用形態而言,一般係以有機溶劑溶解品、水性分散品的形式塗布於基材來使用,尤其近年因環境問題而需要水性分散體。
又,近年來,就蔬菜、水果等生鮮食品的包裝材而言,透明性、再利用性優異的聚酯容器被廣泛使用。藉由進行完全密封,可延長生鮮食品的賞味期限,作為食品之流通革命之候選之一而備受關注。與此相伴,對於包裝材之蓋材要求衛生性、直到取出內容物為止之確實的黏接性、薄膜捲繞時的耐黏連性、不會因內容物之水分而起霧的耐水性、防霧性。
例如,專利文獻1中提出一種水分散體,摻合有玻璃轉移溫度為50℃以上之聚酯樹脂(A)、玻璃轉移溫度為30℃以下之聚酯樹脂(B)。又,專利文獻2中提出一種結晶性共聚聚酯樹脂,4~10之直鏈狀脂肪族二醇成分為75莫耳%以上,且熔點為90℃以上且130℃以下,以2莫耳%以上且5莫耳%以下之範圍含有具有磺酸金屬鹽之芳香族二羧酸作為多元羧酸成分,且酸價未達4KOHmg/g。
[先前技術文獻]
[專利文獻]
[專利文獻1]日本專利5241232號公報
[專利文獻2]WO2015/045633號公報
[發明所欲解決之課題]
但是,專利文獻1中,聚酯樹脂(B)係非晶性,實施例記載之剝離強度係無實用性之強度,在兼顧耐黏連性與熱密封性方面存在問題。又,專利文獻2中,雖係結晶性聚酯樹脂,但含有具有磺酸金屬鹽之芳香族二羧酸,在衛生性、耐水性方面存在問題。
本發明係為了解決上述課題而進行努力研究,結果發現不使用磺酸金屬鹽之結晶性聚酯的高黏接性、耐黏連性、耐水性優異,而完成了本發明。
亦即,本發明旨在提供保存穩定性、高黏接性、耐黏連性、耐水性優異的黏接劑組成物、塗佈組成物。
[解決課題之手段]
一種結晶性聚酯樹脂,係以多元羧酸成分與多元醇成分作為共聚成分,多元羧酸成分含有30~70莫耳%之對苯二甲酸、10~60莫耳%之1,4-環己烷二甲酸、5~30莫耳%之碳數10以下之脂肪族二羧酸,且具有磺酸鹽基之芳香族二羧酸成分之含量未達3莫耳%,多元醇成分含有50~100莫耳%之1,4-丁二醇,該結晶性聚酯樹脂之酸價為100~600eq/t,玻璃轉移溫度為-30~30℃,熔點為70~160℃,數量平均分子量為5000~40000。
一種聚酯樹脂水分散體,含有前述結晶性聚酯樹脂。聚酯樹脂水分散體中,有機溶劑含量宜為1質量%以下。另外,令結晶性聚酯樹脂為100質量份時,宜含有0.1~10質量份之平均粒徑為1μm~30μm之無機粒子,無機粒子之細孔容積未達2.0mL/g較佳。
又,令結晶性聚酯樹脂為100質量份時,宜含有0.1~10質量份之選自由陰離子性界面活性劑及非離子性界面活性劑構成之群組中之1種以上之界面活性劑,非離子性界面活性劑之HLB值為6~14且具有聚氧伸烷基骨架較佳。
一種聚酯樹脂水分散體,含有前述結晶性聚酯樹脂。一種黏接劑組成物或塗佈組成物,含有前述聚酯樹脂水分散體。一種疊層薄膜,其特徵為係將前述黏接劑組成物或塗佈組成物與熱塑性樹脂薄膜予以疊層而成。前述熱塑性樹脂薄膜宜為聚酯系樹脂薄膜,前述黏接劑組成物層或塗佈組成物的厚度宜為0.5~10μm之範圍。
一種包裝材,具有前述疊層薄膜作為構成要素。一種食品包裝容器用蓋材,具有前述包裝材作為構成要素。一種食品包裝容器,係前述蓋材與聚酯系樹脂之疊層體。
[發明之效果]
本發明之結晶性聚酯樹脂即使不使用磺酸金屬鹽,仍可製作保存穩定性、黏接性、耐黏連性及耐水性優異的水分散體。尤其使用了前述結晶性聚酯樹脂水分散體的黏接劑組成物,作為包裝容器之蓋材進行熱密封時,與基材之黏接性優異。另外,係使用FDA認可之原料,故安全性優異,可理想地用作生鮮食品等之包裝材。
以下,針對本發明之實施形態進行詳細地說明。
<結晶性聚酯樹脂>
本發明之結晶性聚酯樹脂,係由可藉由多元羧酸與多元醇之縮聚物而獲得的化學結構構成,多元羧酸與多元醇分別由1種或2種以上之經選擇之成分構成。
作為構成本發明之結晶性聚酯樹脂的多元羧酸,宜為芳香族二羧酸、脂環族二羧酸及/或脂肪族二羧酸。
令多元羧酸成分之合計量為100莫耳%時,對苯二甲酸之共聚量需為30~70莫耳%,宜為35~65莫耳%,更佳為40~60莫耳%。藉由共聚量為30莫耳%以上,獲得之聚酯樹脂成為結晶性,耐黏連性良好。又,藉由為70莫耳%以下,熔點不會變得過高,能以熱密封時之熱量來進行熔融,黏接性會變得良好。
令多元羧酸成分之合計量為100莫耳%時,1,4-環己烷二甲酸之共聚量需為10~60莫耳%,宜為15~55莫耳%,更佳為20~50莫耳%。藉由共聚量為10莫耳%以上,獲得之聚酯樹脂之玻璃轉移溫度不會變得高,黏接性會變得良好。又,藉由為60莫耳%以下,聚酯樹脂之結晶性提高,耐黏連性會變得良好。
令多元羧酸成分之合計量為100莫耳%時,對苯二甲酸與1,4-環己烷二甲酸之合計共聚量,宜為40莫耳%以上,更佳為50莫耳%以上,尤佳為60莫耳%以上,又更佳為70莫耳%以上,特佳為80莫耳%以上。又,宜為95莫耳%以下,更佳為93莫耳%以下,尤佳為90莫耳%以下。藉由為前述範圍內,黏接性及耐黏連性會變得良好。
令多元羧酸成分之合計量為100莫耳%時,脂肪族二羧酸之共聚量宜為5~30莫耳%,為10~25莫耳%更佳,為15~22莫耳%尤佳。藉由脂肪族二羧酸之共聚量為5~30莫耳%,結晶性聚酯樹脂之結晶化速度得到改善,容易展現耐黏連性。又,脂肪族二羧酸之碳數宜為10以下,為8以下更佳。又,宜為2以上,為4以上更佳。藉由使碳數為10以下之脂肪族二羧酸進行共聚合,聚酯樹脂之結晶性得到改善,耐水解性會變得良好。作為碳數10以下之脂肪族二羧酸,可列舉己二酸、癸二酸、琥珀酸、富馬酸、馬來酸、伊康酸等。係FDA(Food and Drug Administration)規格175.300(b)(3)(vii)(2020年4月1日改訂版)中記載、經認可之原料,可理想地使用於食品包裝用材料,考量對於基材之黏接性、耐水性、價格等觀點,為己二酸特佳。
作為對苯二甲酸、1,4-環己烷二甲酸、碳數10以下之脂肪族二羧酸以外之多元羧酸成分,宜使用間苯二甲酸、鄰苯二甲酸、2,6-萘二甲酸、2,6-萘二甲酸二甲酯、偏苯三甲酸、二聚酸,該等可單獨使用,或可倂用2種以上。又,1,4-環己烷二甲酸宜使用順式體或順式/反式之混合物,也可為僅係反式體之1,4-環己烷二甲酸。該等化合物係FDA(Food and Drug Administration)規格175.300(b)(3)(vii)(2020年4月1日改訂版)中記載、經認可之原料,可理想地使用於食品包裝用材料。該等中,考量對於基材之黏接性、耐水性、價格等觀點,宜組合間苯二甲酸。該等多元羧酸成分之共聚量,令多元羧酸成分之合計量為100莫耳%時,宜為40莫耳%以下,為35莫耳%以下更佳,為30莫耳%以下尤佳。藉由為40莫耳%以下,結晶性聚酯樹脂之耐水解性得到改善,耐水性會變得良好。另一方面,下限並無特別限定,使該等多元羧酸進行共聚合時,宜為5莫耳%以上,更佳為10莫耳%以上。
令多元醇成分之合計量為100莫耳%時,1,4-丁二醇之共聚量需為50~100莫耳%,宜為60~100莫耳%,為70~100莫耳%更佳,為80~100莫耳%尤佳,為90~100莫耳%又更佳,為95莫耳%以上特佳,為100莫耳%亦無妨。藉由為50莫耳%以上,獲得之聚酯樹脂成為結晶性,耐黏連性會變得良好。
作為1,4-丁二醇以外之多元醇成分,宜使用FDA規格175.300(b)(3)(vii)(2020年4月1日改訂版)中記載之化合物。具體而言,可列舉:乙二醇、二乙二醇、三乙二醇、丙二醇、2,2-二甲基-1,3-丙二醇、甘油、甘露醇、新戊四醇、三羥甲基乙烷、三羥甲基丙烷。該等多元醇成分之共聚量,令多元醇成分之合計量為100莫耳%時,需為50莫耳%以下,宜為40莫耳%以下,為30莫耳%以下更佳,為20莫耳%以下尤佳,為10莫耳%以下又更佳,為5莫耳%以下特佳,為0莫耳%亦無妨。藉由為50莫耳%以下,獲得之聚酯樹脂會成為結晶性,耐黏連性會變得良好。
本發明之結晶性聚酯樹脂中,使少量的3官能以上之多元羧酸成分、多元醇成分共聚合而導入分支結構亦佳。藉此,可形成更強韌之黏接劑組成物之層(以下,亦稱為黏接劑層。)或塗佈組成物之層(以下,亦稱為塗佈層),並可發揮耐水性的改善效果。具體而言,可列舉偏苯三甲酸酐、乙二醇雙脫水偏苯三甲酸酯、三羥甲基丙烷、甘油、新戊四醇等。該等3官能以上之多元羧酸成分、多元醇成分之共聚量,令全部多元羧酸成分與全部多元醇成分之合計量為200莫耳%時,宜為0.5莫耳%以上,更佳為1莫耳%以上。又,宜為5莫耳%以下,更佳為4莫耳%以下,尤佳為3莫耳%以下。
令多元羧酸成分之合計量為100莫耳%時,具有磺酸鹽基之芳香族二羧酸成分之含量需未達3莫耳%。更佳為0.5莫耳%以下,尤佳為0.1莫耳%以下,特佳為0莫耳%。具有磺酸鹽基之芳香族二羧酸成分係FDA認可外的酸成分,故藉由減少具有磺酸鹽基之芳香族二羧酸成分量,可將本發明之結晶性聚酯樹脂使用於食品接觸用途。作為具有磺酸鹽基之芳香族二羧酸成分,例如可列舉5-磺酸基間苯二甲酸、4-磺酸基萘-2,7-二甲酸、5-[4-磺酸基苯氧基]間苯二甲酸及它們的鹼金屬鹽。鹼金屬鹽可列舉鋰、鈉、鉀等。具體例可列舉5-磺酸基間苯二甲酸鈉、5-磺酸基間苯二甲酸鉀、4-磺酸基萘-2,7-二甲酸鈉、5-[4-磺酸基苯氧基]間苯二甲酸鈉等。
令多元醇成分之合計量為100莫耳%時,具有磺酸鹽基之多元醇成分之含量宜未達3莫耳%。更佳為0.5莫耳%以下,尤佳為0.1莫耳%以下,特佳為0莫耳%。具有磺酸鹽基之多元醇成分係FDA認可外的醇成分,故藉由減少具有磺酸鹽基之多元醇成分量,可將本發明之結晶性聚酯樹脂使用於食品接觸用途。作為具有磺酸鹽基之多元醇成分,例如可列舉2-磺酸基-1,4-丁二醇之鈉鹽、2,5-二甲基-3-磺酸基-2,5-己二醇之鈉鹽等。
又,為了賦予酸價,亦可於聚酯樹脂聚合後將偏苯三甲酸酐、均苯四甲酸酐、乙二醇雙脫水偏苯三甲酸酯等酸酐等進行後添加(後加成)。進行後添加(後加成)時,有時會有多元羧酸成分與多元醇成分之合計量超過200莫耳%的情況。此時,係將除了後添加(後加成)酸酐等之成分以外的組成之合計量計算為200莫耳%。
構成本發明中之結晶性聚酯樹脂的多元羧酸成分及多元醇成分,可使用衍生自生物質資源的原料。生物質資源包含利用植物的光合作用將太陽的光能轉化為澱粉、纖維素等形式所儲存者、食用植物體生長的動物身體、加工植物體、動物體而得的製品等。其中,更佳的生物質資源為植物資源,例如可列舉:木材、稻草、稻殼、米糠、陳米、玉米、甘蔗、木薯、西谷米、豆渣、玉米芯、樹薯渣、甘蔗渣、植物油渣、塊莖塊根、蕎麥、大豆、油脂、廢紙、造紙殘渣、水產品殘渣、家畜排泄物、污水污泥、食品廢棄物等。尤佳為玉米、甘蔗、木薯、西谷米。
製造本發明之結晶性聚酯樹脂時,例如可使用鈦酸四正丁酯、鈦酸四異丙酯、乙醯丙酮氧鈦(titanium oxideacetylacetonate)等鈦化合物、三氧化銻、三丁氧基銻等銻化合物、氧化鍺、四正丁氧基鍺等鍺化合物,其他可使用鎂、鐵、鋅、錳、鈷、鋁等之乙酸鹽等作為聚合觸媒。該等觸媒可使用1種,或倂用2種以上。
製造本發明之結晶性聚酯樹脂的聚合縮合反應之方法並無特別限定,例如有如下方法等:1)將多元羧酸與多元醇於任意觸媒存在下進行加熱,經過脫水酯化步驟並實施脫多元醇-縮聚反應;2)將多元羧酸之醇酯體與多元醇於任意觸媒存在下進行加熱,經過酯交換反應並實施脫多元醇-縮聚反應。前述1)、2)之方法中,亦可將酸成分之一部分或全部置換為酸酐。
本發明之結晶性聚酯樹脂之玻璃轉移溫度(Tg)為-30~30℃,宜為-25~25℃,更佳為-20~20℃。藉由為前述下限值以上,將疊層薄膜捲繞成輥狀時,可抑制黏連的發生。藉由為前述上限值以下,於室溫剝離時,亦具有樹脂之柔軟性,黏接性會變得良好。
本發明中所稱結晶性,係指利用差示掃描型熱量計(DSC),以20℃/分鐘從-100℃升溫至250℃,在該升溫過程中展示明確的熔解峰部者。
本發明之結晶性聚酯樹脂之熔點(Tm)為70~160℃,宜為75~155℃,更佳為80~150℃。藉由熔點為前述下限值以上,結晶性會變得良好,可展現優異的耐黏連性。又,藉由熔點為前述上限值以下,即使於低溫下樹脂仍會充分熔融,且即使於低溫進行熱密封,亦不會發生密封不良。另外,即使進行塗布之基材使用聚酯薄膜等塑膠薄膜,亦不會發生該基材變形等的問題。
結晶性聚酯樹脂之還原黏度(ηsp/c),宜為0.2~1.2dl/g。更佳為0.4~1.1dl/g,尤佳為0.6~1.0dl/g。藉由為前述下限值以上,樹脂凝聚力會變得良好,可展現優異的黏接性。又,藉由為前述上限值以下,可製作水分散體。還原黏度可藉由變化該結晶性聚酯樹脂之聚合時間、溫度、聚合時之減壓程度(減壓聚合時)來任意調整。
結晶性聚酯樹脂之酸價為100~600eq/t,宜為150~550eq/t,更佳為200~500eq/t。藉由為前述上限值以下,不會成為低分子量,故樹脂凝聚力會變得良好,可展現優異的黏接性。又,藉由為前述下限值以上,可製作水分散體。
結晶性聚酯樹脂之數量平均分子量(Mn)宜為5000~40000。更佳為6000~35000,尤佳為8000~30000。藉由為前述下限值以上,樹脂凝聚力會變得良好,可展現優異的黏接性。又,藉由為前述上限值以下,可製作水分散體。數量平均分子量可藉由變化該結晶性聚酯樹脂之聚合時間、溫度、聚合時之減壓程度(減壓聚合時)來任意調整。此外,數量平均分子量係利用凝膠滲透層析法(以下稱為GPC、標準物質:聚苯乙烯樹脂、移動相:四氫呋喃)測得之值。
<聚酯樹脂水分散體>
本發明之聚酯樹脂水分散體係含有前述結晶性聚酯樹脂及水,並視需要含有有機溶劑之水分散體。令聚酯樹脂水分散體為100質量%時,有機溶劑宜為50質量%以下,為30質量%以下更佳,為15質量%以下尤佳,為1質量%以下特佳。亦可不含有機溶劑,但在工業上含有約0.1質量%亦無妨。藉由聚酯樹脂水分散體之有機溶劑為50質量%以下,水分散體之保存穩定性得到改善。此外,製造本發明之聚酯樹脂水分散體的方法並無特別限定。
本發明之聚酯樹脂水分散體中使用的有機溶劑之沸點,宜為100℃以上,為105℃以上更佳,為110℃以上尤佳,為115℃以上特佳,為120℃以上最佳。藉由沸點為100℃以上,可使結晶性聚酯樹脂熔融,並可輕易地水分散化。又,宜為180℃以下,為175℃以下更佳,為170℃以下尤佳,為165℃以下特佳,為160℃以下最佳。藉由沸點為180℃以下,幾乎沒有乾燥時之殘留溶劑,不會有捲繞時之黏連發生等的問題。
本發明之聚酯樹脂水分散體中使用的有機溶劑,並無特別限定,可列舉:異丙醇、異丁醇、異胺基醇等醇、乙二醇單甲醚、乙二醇單乙醚、乙二醇單異丙醚、乙二醇單丁醚(以下,亦稱為「正丁基賽珞蘇」或「n-BuCS」。)、乙二醇單第三丁醚(以下,亦稱為「第三丁基賽珞蘇」或「t-BuCS」。)、丙二醇單丁醚、甲乙酮等。該等有機溶劑可單獨使用或將2種以上倂用。其中,為正丁基賽珞蘇、第三丁基賽珞蘇特佳。
相對於前述結晶性聚酯樹脂100質量份,有機溶劑宜為200質量份以下,為150質量份以下更佳,為100質量份以下尤佳,為50質量份以下特佳。藉由為前述上限值以下,乾燥時之殘留溶劑減少,不會有捲繞時之黏連發生等的問題。又,保存穩定性亦變得良好。下限並無特別限定,工業上為1質量份以上則無問題,為10質量份以上亦無妨。
相對於前述結晶性聚酯樹脂100質量份,水宜為150質量份以上,為170質量份以上更佳,為200質量份以上尤佳。藉由為前述下限值以上,結晶性聚酯樹脂會分散於水中,可獲得本發明之聚酯樹脂水分散體。又,宜為500質量份以下,為450質量份以下更佳,為400質量份以下尤佳。藉由為前述上限值以下,生產效率改善,在工業上係有利。
本發明之聚酯樹脂水分散體中含有的結晶性聚酯樹脂相之粒徑,宜為20nm以上,為30nm以上更佳,為40nm以上尤佳,為50nm以上特佳。藉由為前述下限值以上,製膜性改善,可抑制分散粒子間之融合、凝聚,並可抑制增黏、分散不良發生的情況。又,宜為250nm以下,為200nm以下更佳,為150nm以下尤佳。藉由為前述上限值以下,可維持優異的分散穩定性、製膜性,獲得之皮膜的外觀與性能會變得良好。此處,粒徑係指結晶性聚酯樹脂之粒徑,更含有其他聚酯樹脂等含有2種以上之聚酯樹脂時,係指2種以上之聚酯樹脂之平均粒徑。
<無機粒子>
本發明之聚酯樹脂水分散體藉由添加無機粒子,可進一步改善耐黏連性、乾燥後之順滑性。所添加之無機粒子之利用雷射法測得之平均粒徑宜為1μm以上,為2μm以上特佳。藉由為前述下限值以上,乾燥後之塗膜之表層會形成適度的凹凸,可改善順滑性、耐黏連性。又,宜為30μm以下,為20μm以下更佳。藉由為前述上限值以下,乾燥後之塗膜之凹凸受到抑制,粒子彼此的物理衝擊所致之滑落、密接性變得良好。令前述結晶性聚酯為100質量份時,無機粒子的添加量宜為0.1質量份以上,更佳為0.2質量份以上。藉由含量為前述下限值以上,可展現耐黏連性的效果。又,宜為10質量份以下,更佳為8質量份以下,尤佳為7質量份以下。藉由為前述上限值以下,可維持黏接性。再者,前述無機粒子之細孔容積宜未達2.0mL/g,未達1.6mL/g更佳,未達1.0mL/g尤佳。藉由為前述上限值以下,可抑制黏接性的降低。細孔容積可使用氮氣吸附測定裝置進行測定。
本發明之聚酯樹脂水分散體所使用的無機粒子,只要是具有前述粒徑之無機粒子,則無特別限定,例如可列舉含有鎂、鈣、鋇、鋅、鋯、鉬、矽、銻、或鈦等金屬之氧化物、氫氧化物、硫酸鹽、碳酸鹽、或矽酸鹽等的無機粒子。該等無機粒子之中,為矽膠、膠態二氧化矽、沉降二氧化矽特佳。
<界面活性劑>
藉由在本發明之聚酯樹脂水分散體中添加界面活性劑,可賦予防霧性、抗靜電性。界面活性劑宜為陰離子性界面活性劑或非離子性界面活性劑。藉由使用陰離子性界面活性劑或非離子性界面活性劑,可賦予防霧性而不會損及黏接性。陰離子性界面活性劑與非離子性界面活性劑亦可組合使用。
作為陰離子性界面活性劑,可列舉:高級醇之硫酸酯鹽、高級烷基磺酸鹽、高級羧酸鹽、烷基苯磺酸鹽、聚氧乙烯烷基硫酸鹽、聚氧乙烯烷基苯醚硫酸鹽、乙烯基磺酸基琥珀酸鹽。該等可單獨使用或將2種以上組合使用。
作為非離子性界面活性劑,可列舉:聚氧乙烯烷基醚、聚氧乙烯烷基苯基醚、聚乙二醇脂肪酸酯、環氧乙烷環氧丙烷嵌段共聚物、聚氧乙烯脂肪醯胺、環氧乙烷-環氧丙烷共聚物等具有聚氧乙烯結構之化合物、山梨醇酐衍生物。該等可單獨使用或將2種以上組合使用。
令結晶性聚酯樹脂為100質量份時,界面活性劑的添加量宜為0.1質量份以上,更佳為0.3質量份以上,尤佳為0.7質量份以上。藉由為上述下限值以上,防霧性良好。又,宜為10質量份以下,為9質量份以下更佳,為8質量份以下尤佳,為7質量份以下特佳。藉由為前述上限值以下,可維持黏接性。
前述非離子性界面活性劑中,非離子性界面活性劑之HLB值宜為6以上,更佳為6.5以上,尤佳為7以上。藉由使用前述下限值以上者,防霧性良好。又,宜為14以下,為13.5以下更佳,為13以下尤佳。藉由使用前述上限值以下者,可維持黏接性。再者,宜使用具有聚氧伸烷基骨架之非離子性界面活性劑。藉由使用具有該骨架之非離子性界面活性劑,可抑制界面活性劑之過度滲出、轉印所致之黏接性降低、防霧性降低。
本發明之聚酯樹脂水分散體,除黏接劑之外,還可理想地用來作為塗佈劑、熱密封劑之原料,尤其適合於黏接劑用途。
<黏接用或塗佈用之組成物>
本發明之黏接用或塗佈用之組成物,係含有前述聚酯樹脂水分散體作為必要成分之組成物。
本發明之黏接用或塗佈用之組成物,在不損及本發明之性能的範圍內,可摻合其他聚酯樹脂或其水分散體、各種添加劑而使用。添加劑並無特別限定,可列舉用以形成表面凹凸的前述無機粒子、有機粒子、蠟類等。
作為有機粒子,例如可列舉:聚甲基丙烯酸甲酯樹脂、聚苯乙烯樹脂、尼龍樹脂、三聚氰胺樹脂、苯并胍胺樹脂、酚醛樹脂、脲樹脂、矽樹脂、甲基丙烯酸酯樹脂、或丙烯酸酯樹脂等聚合物粒子、或纖維素粉末、硝化纖維素粉末、木粉、廢紙粉、稻殼粉、澱粉等。聚合物粒子可利用乳化聚合、懸浮聚合、分散聚合、無皂聚合、微懸浮聚合等聚合法來獲得。前述有機粒子可在不損及本發明之效果的範圍內使用。粒子的形狀可為粉末狀、粒狀、顆粒狀、平板狀、針狀等任意形狀,並無限定。
蠟類之具體例可列舉:液體石蠟、天然石蠟、微晶石蠟(micro wax)、合成石蠟、聚乙烯蠟等烴系蠟類;硬脂酸等脂肪酸系蠟類;硬脂醯胺、棕櫚醯胺、亞甲基雙硬脂醯胺、伸乙基雙硬脂醯胺、油醯胺、乙磺醯胺(esylic acid amide)等脂肪酸系醯胺蠟;脂肪酸之低級醇酯、脂肪酸之多元醇酯、脂肪酸聚二元醇酯等酯系蠟;十六烷醇、硬酯醇等醇系蠟;烯烴系蠟、蓖麻蠟(castor wax)、棕櫚蠟(carnauba wax)等天然物蠟;由碳數12~30之脂肪酸衍生而得之金屬皂類等。前述蠟類可在不損及本發明之效果的範圍內使用。
<疊層薄膜>
本發明之疊層薄膜,係於基材薄膜之至少單面疊層了由本發明之黏接用或塗佈用之組成物構成之黏接劑層或塗佈層而得的薄膜。疊層薄膜係藉由於基材薄膜塗布前述組成物後,進行乾燥處理而獲得。
就基材薄膜而言,只要是可由本發明之黏接用或塗佈用之組成物形成黏接劑層或塗佈層者,則無特別限定,宜為熱塑性樹脂薄膜,例如可列舉:聚酯系樹脂薄膜、聚丙烯系樹脂薄膜、聚醯胺系樹脂薄膜、聚乙烯醇系樹脂薄膜、聚偏二氯乙烯系樹脂薄膜。其中,考量適合作為食品包裝容器之蓋材的方面,為聚酯系樹脂薄膜更佳。
基材薄膜之厚度宜為5μm以上,更佳為10μm以上。藉由為前述下限值以上,基材薄膜之耐久性會變得良好。又,宜為50μm以下,更佳為30μm以下。藉由為前述上限值以下,實用上可使用作為食品包裝容器之蓋材。
黏接劑層之厚度宜為0.5μm以上,更佳為1μm以上。藉由為前述下限值以上,黏接性會變得良好。又,宜為10μm以下,更佳為5μm以下。藉由為前述上限值以下,黏接性、熱密封性會變得良好。
本發明之疊層薄膜的黏接性、防霧性優異,故適合作為包裝材之構成要素。其中,作為生鮮食品等之食品包裝容器之蓋材係理想。作為食品包裝容器之蓋材使用時,藉由將疊層薄膜之黏接劑層面與食品包裝容器進行疊層,可將內容物予以密封。食品包裝容器並無特別限定,宜為聚酯系樹脂。
[實施例]
以下,舉實施例更詳細地說明本發明。惟,本發明不限定於實施例。在實施例中及比較例中,簡稱為「份」者係表示「質量份」。
<物性評價方法>
(結晶性聚酯樹脂之組成的測定)
使用400MHz之
1H-核磁共振光譜裝置(
1H-NMR),進行構成結晶性聚酯樹脂之多元羧酸成分、多元醇成分之莫耳比定量。溶劑係使用氘代氯仿。
(結晶熔點(Tm)及玻璃轉移溫度(Tg)的測定)
使用Seiko Instruments(股)製差示掃描熱量分析計(DSC)DSC-220,將樣品(結晶性聚酯樹脂)5mg密封在鋁塞蓋型容器中,以20℃/分鐘之升溫速度從-100℃升溫至250℃並進行測定,求出熔解熱之最大峰部溫度作為結晶熔點。又,玻璃轉移溫度係使用前述測定裝置,以同樣條件求出玻璃轉移溫度以下之基線之延長線與從峰部之上升部分到峰部頂點之間顯示最大傾斜度之切線的交點之溫度。
(還原黏度(單位:dl/g)的測定)
將結晶性聚酯樹脂之試樣0.1g溶解於苯酚/四氯乙烷(質量比6/4)之混合溶劑25cc中,於測定溫度30℃使用烏氏黏度管進行測定。
(數量平均分子量的測定)
數量平均分子量係利用凝膠滲透層析法(標準物質:聚苯乙烯樹脂、移動相:四氫呋喃)進行測定。
將以四氫呋喃對試樣進行溶解及/或稀釋,使樹脂濃度成為約0.5質量%,並利用孔徑0.5μm之聚四氟化乙烯製膜過濾器進行過濾而得者作為測定用試樣,利用以四氫呋喃作為移動相,並以差示折射計作為檢測器的凝膠滲透層析法測定分子量。流速設定為1mL/分鐘,管柱溫度設定為40℃。管柱係使用昭和電工製KF-802、804L、806L。
(酸價的測定)
將結晶性聚酯樹脂之試樣0.2g溶解於40ml之氯仿中,利用0.01N之氫氧化鉀乙醇溶液進行滴定,求出聚酯樹脂每10
6g之當量(eq/t)。指示劑係使用酚酞。
(1)保存穩定性
將聚酯樹脂水分散體於25℃下保存(靜置)6個月,確認外觀、形狀(黏度)變化。
<評價基準>
○:外觀、形狀(黏度)沒有變化。
△:觀察到白濁、沉降物,但形狀(黏度)沒有變化。
×:發生黏度上升、分離、或分散不良。
(評價用疊層薄膜的製作)
將實施例、比較例中獲得之黏接劑組成物塗布於厚度25μm之聚酯薄膜(東洋紡(股)公司製、E5107)之電暈處理面,使乾燥後之厚度成為2.5g/m
2。然後,於160℃乾燥30秒,得到評價用疊層薄膜。
(2)剝離強度(黏接性)
將評價用疊層薄膜之黏接劑層面,以溫度160℃、壓力2.8kgf/cm
2、1秒之條件熱密封於厚度350μm之未延伸非晶PET片材。之後,切出25mm寬之試驗片,於25℃、以拉伸速度100mm/min進行180°剝離試驗,測定剝離強度。
<評價基準>
○:800gf/25mm以上
△:500gf/25mm以上且未達800gf/25mm
×:未達500gf/25mm
(3)耐黏連性(實施例1~8、比較例1~8)
將評價用疊層薄膜之黏接劑層面重疊於聚酯薄膜(東洋紡(股)公司製、E5107)之電暈未處理面,製作試驗樣品。之後,於40℃、0.9kgf/cm
2之壓力下保存1天,並依下列判定基準確認耐黏連性。
<評價基準>
○:試驗樣品完全沒有黏性。
△:試驗樣品有些微黏性,但係使用上無問題的範圍。
×:試驗樣品有黏性,係使用上有問題的範圍。
(4)高壓力下耐黏連性(實施例9~15)
將評價用疊層薄膜之黏接劑層面重疊於聚酯薄膜(東洋紡(股)公司製、E5107)之電暈未處理面,製作試驗樣品。之後,於25℃、30MPa之壓力下保存1天,並依下列判定基準確認耐黏連性。
<評價基準>
○:試驗樣品完全沒有黏性。
△:試驗樣品有些微黏性,但係使用上無問題的範圍。
×:試驗樣品有黏性,係使用上有問題的範圍。
(5)耐水性
將於剝離強度之評價項目製作之試驗片在25℃之水中浸漬1天。之後,針對試驗片依據剝離強度之測定方法進行測定,將其作為耐水性的評價。
<評價基準>
○:800gf/25mm以上
△:500gf/25mm以上且未達800gf/25mm
×:未達500gf/25mm
(6)剝離強度穩定性
將於剝離強度之評價項目製作之試驗片於25℃靜置4週。之後,針對試驗片依據剝離強度之測定方法進行測定,依下式算出剝離強度保持率。將其作為剝離強度穩定性的評價。
強度保持率(%)=(靜置後之剝離強度)÷(靜置前之剝離強度)×100
<評價基準>
○:95%以上
△:90%以上且未達95%
×:未達90%
(7)初始防霧性
在容量100cm
3之容器中裝入55℃之熱水50ml,將評價用疊層薄膜之黏接劑層面對準容器之口部,以膠帶固定並蓋上蓋子。之後,在5℃之恆溫槽中靜置30分鐘,以目視依下列判定基準確認防霧效果。
<評價基準>
○:於薄膜表面形成連續的水膜,可見性良好。
△:有部分水滴附著於薄膜表面,但可見性良好。
×:有水滴附著於薄膜表面,或可見性惡化。
(8)經時之防霧性
將評價用疊層薄膜之黏接劑層面重疊於聚酯薄膜(東洋紡(股)公司製、E5107)之電暈未處理面,製作試驗樣品。之後,於25℃、30MPa之壓力下保存1天。之後,將評價用疊層薄膜與聚酯薄膜剝離。於容量100cm
3之容器中裝入55℃之熱水50ml,將剝下之評價用疊層薄膜之黏接劑層面對準容器之口部,以膠帶固定並蓋上蓋子。之後,在5℃之恆溫槽中靜置30分鐘,以目視依下列判定基準確認防霧效果。
<評價基準>
○:於薄膜表面形成連續的水膜,可見性良好。
△:有部分水滴附著於薄膜表面,但可見性良好。
×:有水滴附著於薄膜表面,或可見性惡化。
此外,初始防霧性評價為×時,沒有評價經時之防霧性。
(9)轉移性
將評價用疊層薄膜之黏接劑層面重疊於聚酯薄膜(東洋紡(股)公司製、E5107)之電暈未處理面,製作試驗樣品。之後,於25℃、30MPa之壓力下保存1天。之後,將評價用疊層薄膜與聚酯薄膜剝離。於容量100cm
3之容器中裝入55℃之熱水50ml,將剝下之聚酯薄膜之電暈未處理面(與評價用疊層薄膜之黏接劑層面接觸之面)對準容器之口部,以膠帶固定並蓋上蓋子。之後,在5℃之恆溫槽中靜置30分鐘,以目視依下列判定基準確認防霧效果。
<評價基準>
〇:水滴附著於薄膜表面,未確認到因界面活性劑所獲致之防霧性。
△:有部分水滴附著於薄膜表面,確認到部分因界面活性劑所獲致之防霧性。
×:於薄膜表面形成連續的水膜,確認到因界面活性劑所獲致之防霧性。
此外,初始防霧性評價或經時之防霧性評價為×時,沒有評價轉移性。
-結晶性聚酯樹脂之實施例-
<結晶性聚酯樹脂(A-1)之合成>
於配備有攪拌機、溫度計、加熱器、冷卻裝置、餾出用冷卻器之反應槽內,加入對苯二甲酸375質量份、1,4-環己烷二甲酸148質量份、己二酸198質量份、偏苯三甲酸酐9質量份、1,4-丁二醇813質量份及鈦酸四丁酯0.5質量份,升溫至220℃,同時歷時4小時進行酯化反應。酯化反應結束後,邊將系內升溫至250℃邊歷時60分鐘減壓至10torr,進一步減壓至1torr以下之真空下,於250℃進行縮聚反應直至預定黏度。之後,使氮氣流入系內並冷卻至220℃,添加偏苯三甲酸酐27質量份,使其反應30分鐘。反應結束後,取出結晶性聚酯樹脂並冷卻,藉此得到結晶性聚酯樹脂(A-1)。
<結晶性聚酯樹脂(A-2)~(A-16)之合成>
以與結晶性聚酯樹脂(A-1)之合成例同樣之步驟,合成聚酯樹脂(A-2)~(A-16)。樹脂組成及物性的測定結果示於表1。
[表1]
結晶性聚酯樹脂 | A-1 | A-2 | A-3 | A-4 | A-5 | A-6 | A-7 | A-8 | A-9 | A-10 | A-11 | A-12 | A-13 | A-14 | A-15 | A-16 | ||
組成 | 多元羧酸成分 (莫耳%) | 對苯二甲酸 | 50 | 34 | 65 | 60 | 60 | 42 | 50 | 50 | 75 | 25 | 45 | 50 | 34 | 34 | 50 | 45 |
1,4-環己 烷二甲酸 | 29 | 45 | 15 | 29 | 29 | 32 | 29 | 27 | 24 | 65 | 54 | 29 | 20 | 29 | 30 | |||
間苯二甲酸 | 20 | 20 | ||||||||||||||||
己二酸 | 20 | 20 | 19 | 10 | 5 | 20 | 20 | 9 | 20 | 46 | 46 | 20 | 20 | |||||
癸二酸 | 10 | |||||||||||||||||
5-磺酸基間苯二甲酸 | 5 | |||||||||||||||||
偏苯三 甲酸酐 | 1 | 1 | 1 | 1 | 1 | 1 | 1 | 3 | 1 | 1 | 1 | 1 | 0 | 1 | 1 | |||
偏苯三甲酸酐(酸加成) | 3 | 3 | 3 | 3 | 3 | 3 | 2 | 5 | 3 | 3 | 3 | 3 | 3 | 3 | 1 | |||
多元醇 成分 (莫耳%) | 1,4-丁二醇 | 100 | 100 | 100 | 50 | 100 | 100 | 100 | 100 | 100 | 100 | 80 | 40 | 100 | 100 | 100 | 100 | |
二乙二醇 | 50 | 20 | 60 | |||||||||||||||
物性 | ηsp/c(dl/g) | 0.60 | 0.65 | 0.62 | 0.54 | 0.70 | 0.62 | 0.58 | 0.35 | 0.60 | 0.54 | 0.57 | 0.60 | 0.40 | 0.62 | 0.50 | 0.60 | |
數量平均 分子量Mn | 15000 | 15000 | 16000 | 15500 | 18000 | 15000 | 14300 | 8500 | 16000 | 13800 | 14200 | 15500 | 12000 | 15500 | 10000 | 15000 | ||
酸價(eq/t) | 350 | 310 | 360 | 352 | 345 | 350 | 180 | 450 | 330 | 360 | 333 | 320 | 285 | 260 | 80 | 20 | ||
Tg(℃) | -12 | -14 | 1 | 1 | 2 | 12 | -10 | -15 | 27 | -10 | 4 | -25 | -24 | -30 | -16 | -13 | ||
Tm(℃) | 120 | 95 | 158 | 110 | 150 | 104 | 123 | 116 | 178 | 無峰部 | 117 | 無峰部 | 83 | 89 | 120 | 115 |
<實施例1>
-聚酯樹脂水分散體(B)之製造例-
<聚酯樹脂水分散體(B-1)之製造>
依下列步驟將結晶性聚酯樹脂(A-1)進行水分散化。於具備攪拌機、冷凝器、溫度計之反應容器中,加入結晶性聚酯樹脂(A-1)100份、乙二醇單丁醚40份、甲乙酮120份、異丙醇30份,於80℃歷時3小時使樹脂溶解。然後,投入二甲基胺基乙醇3.6份並攪拌30分鐘。然後,投入溫水260份並攪拌1小時。之後邊將內溫升溫至100℃,邊餾去甲乙酮、異丙醇,得到聚酯樹脂水分散體(B-1)。進行各種特性評價的結果示於表2。
-聚酯樹脂水分散體(C)之製造例-
<聚酯樹脂水分散體(C-1)之製造>
依下列步驟將結晶性聚酯樹脂(A-1)進行水分散化。於具備攪拌機、冷凝器、溫度計之反應容器中,加入結晶性聚酯樹脂(A-1)100份、甲乙酮120份,於75℃下邊攪拌邊將樹脂溶解。確認樹脂完全溶解後,加入異丙醇30份,進一步攪拌30分鐘。然後,投入二甲基胺基乙醇3.6份並攪拌30分鐘。然後,投入溫水300份,並攪拌1小時。之後,邊將內溫升溫至100℃,邊餾去甲乙酮、異丙醇,得到不含有機溶劑的聚酯樹脂水分散體(C-1)。進行保存穩定性評價的結果示於表2。
<實施例2~8、比較例1~8>
變更結晶性聚酯樹脂的種類,除此以外,以與聚酯樹脂水分散體(B-1)之製造例同樣之步驟,得到聚酯樹脂水分散體(B-2)~(B-16)。進行各種特性評價的結果示於表2。
[表2]
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 | 比較例1 | 比較例2 | 比較例3 | 比較例4 | 比較例5 | 比較例6 | 比較例7 | 比較例8 | ||
聚酯樹脂水分散體B | B-1 | B-2 | B-3 | B-4 | B-5 | B-6 | B-7 | B-8 | B-9 | B-10 | B-11 | B-12 | B-13 | B-14 | B-15 | B-16 | |
結晶性聚 酯樹脂 (質量份) | A-1 | A-2 | A-3 | A-4 | A-5 | A-6 | A-7 | A-8 | A-9 | A-10 | A-11 | A-12 | A-13 | A-14 | A-15 | A-16 | |
100 | 100 | 100 | 100 | 100 | 100 | 100 | 100 | 100 | 100 | 100 | 100 | 100 | 100 | 100 | 100 | ||
水 (質量份) | 260 | 260 | 260 | 260 | 260 | 260 | 260 | 260 | 260 | 260 | 260 | 260 | 260 | 260 | 260 | 260 | |
乙二醇單 丁醚 (質量份) | 40 | 40 | 40 | 40 | 40 | 40 | 40 | 40 | 40 | 40 | 40 | 40 | 40 | 40 | 40 | 40 | |
保存穩定性 | 評價 | △ | ○ | △ | ○ | △ | ○ | △ | △ | × | ○ | ○ | ○ | × | △ | × | ○ |
白濁 | 白濁 | 白濁 | 白濁 | 白濁 | 增黏 | 分離 | 白濁 | 分散 不良 | |||||||||
剝離 強度 | 剝離強度 [gf/25mm] | 810 | 900 | 550 | 960 | 600 | 680 | 760 | 550 | 100 | 870 | 830 | 920 | 750 | 760 | 無法 評價 | 900 |
評價 | ○ | ○ | △ | ○ | △ | △ | △ | △ | × | ○ | ○ | ○ | △ | △ | 無法 評價 | ○ | |
耐黏 連性 | 評價 | ○ | △ | ○ | △ | ○ | △ | ○ | ○ | ○ | × | × | × | △ | × | 無法 評價 | ○ |
耐水性 | 剝離強度 [gf/25mm] | 700 | 650 | 520 | 840 | 580 | 600 | 700 | 510 | 100 | 520 | 810 | 380 | 410 | 390 | 無法 評價 | 200 |
評價 | △ | △ | △ | ○ | △ | △ | △ | △ | × | △ | ○ | × | × | × | 無法 評價 | × | |
C-1 | |||||||||||||||||
聚酯樹脂水分散體C | 結晶性聚 酯樹脂 (質量份) | A-1 | |||||||||||||||
100 | |||||||||||||||||
水 (質量份) | 300 | ||||||||||||||||
保存穩定性 | 評價 | ○ |
<實施例9>
在混合有水42質量份、異丙醇25質量份之混合溶劑中,邊攪拌邊緩慢添加聚酯樹脂水分散體(C-1)100質量份,將聚酯樹脂水分散體進行稀釋。然後,添加無機粒子(D-1)0.34質量份,邊攪拌邊充分地進行無機粒子之分散,得到含有無機粒子之聚酯水分散體(E-1)。進行各種特性評價的結果示於表3。
<實施例10~15>
變更無機粒子的種類及量,除此以外,以與實施例9同樣之步驟得到含有無機粒子之聚酯樹脂水分散體(E-2)~(E-6)。此外,實施例15係不含無機粒子之示例。進行各種特性評價的結果示於表3。
無機粒子係使用如下者。
D-1:SYLOBLOC ED2(GRACE公司製二氧化矽、粒徑=4.2μm、細孔容積=1.8ml/g)
D-2:SYLOID K200(GRACE公司製二氧化矽、粒徑=2.5μm、細孔容積=1.6ml/g)
D-3:SYLOBLOC 35(GRACE公司製二氧化矽、粒徑=3.9μm、細孔容積=1.0ml/g)
D-4:SYLOBLOC S200(GRACE公司製二氧化矽、粒徑=3.2μm、細孔容積=0.6ml/g)
[表3]
實施例 9 | 實施例 10 | 實施例 11 | 實施例 12 | 實施例 13 | 實施例 14 | 實施例 15 | ||
含有無機粒子之聚酯樹脂水分散體 | E-1 | E-2 | E-3 | E-4 | E-5 | E-6 | - | |
聚酯樹脂水分散體 | 分散體 | C-1 | C-1 | C-1 | C-1 | C-1 | C-1 | C-1 |
質量份 | 100 | 100 | 100 | 100 | 100 | 100 | 100 | |
水 | 質量份 | 42 | 42 | 42 | 42 | 42 | 42 | 42 |
異丙醇 | 質量份 | 25 | 25 | 25 | 25 | 25 | 25 | 25 |
無機 粒子 | 種類 | D-1 | D-1 | D-1 | D-2 | D-3 | D-4 | - |
粒徑(μm) | 4.2 | 4.2 | 4.2 | 2.5 | 3.9 | 3.2 | - | |
細孔容積 (ml/g) | 1.8 | 1.8 | 1.8 | 1.6 | 1 | 0.6 | - | |
質量份 | 0.34 | 0.88 | 1.75 | 1.75 | 1.75 | 1.75 | - | |
剝離 強度 | 剝離強度 [gf/25mm] | 1010 | 1150 | 890 | 950 | 1020 | 1040 | 930 |
評價 | ○ | ○ | ○ | ○ | ○ | ○ | ○ | |
剝離強度穩定性 | 保持率 [%] | 92% | 91% | 75% | 94% | 100% | 98% | 100% |
評價 | △ | △ | × | △ | ○ | ○ | ○ | |
高壓力下耐黏連性 | ○ | ○ | ○ | ○ | ○ | ○ | △ |
<實施例16>
於混合溶解有水42質量份、異丙醇25質量份、界面活性劑(F-1)1.3質量份之界面活性劑溶解液中,邊攪拌邊緩慢添加聚酯樹脂水分散體(C-1)100質量份。然後,添加無機粒子(D-1)0.34份,邊攪拌邊充分地進行無機粒子之分散,得到含有界面活性劑之聚酯水分散體(G-1)。進行各種特性評價的結果示於表4。
<實施例17~23>
變更界面活性劑的種類及量,除此以外,以與實施例16同樣之步驟得到含有界面活性劑之聚酯樹脂水分散體(G-2)~(G-7)。此外,實施例23係不含界面活性劑之示例。進行各種特性評價的結果示於表4。
界面活性劑係使用如下者。
F-1:EMULGEN 404(花王(股)公司製非離子性界面活性劑、聚氧乙烯油基醚、HLB值=8.8)
F-2:EMULGEN 709(花王(股)公司製非離子性界面活性劑、聚氧乙烯烷基醚、HLB值=13.3)
F-3:NOIGEN ES-149D(第一工業製藥(股)公司製非離子性界面活性劑、聚氧乙烯油酸酯、HLB值=11.5)
F-4:EMULGEN 210P(花王(股)公司製非離子性界面活性劑、聚氧乙烯鯨蠟醚、HLB值=10.7)
F-5:DISPONIL SDS G(BASF公司製陰離子性界面活性劑、脂肪族醇硫酸鈉)
F-6:Rheodol TW-O120V(花王(股)公司製非離子性界面活性劑、聚氧乙烯山梨醇酐單油酸酯、HLB值=15.0)
F-7:POEM M-300(RIKEN VITAMIN(股)公司製非離子性界面活性劑、甘油單月桂酸酯、HLB值=5.4)
[表4]
實施例 16 | 實施例 17 | 實施例 18 | 實施例 19 | 實施例 20 | 實施例 21 | 實施例 22 | 實施例 23 | ||
含有界面活性劑之聚酯樹脂水分散體 | G-1 | G-2 | G-3 | G-4 | G-5 | G-6 | G-7 | - | |
聚酯樹脂水分散體 | 分散體 | C-1 | C-1 | C-1 | C-1 | C-1 | C-1 | C-1 | C-1 |
質量份 | 100 | 100 | 100 | 100 | 100 | 100 | 100 | 100 | |
水 | 質量份 | 42 | 42 | 42 | 42 | 42 | 42 | 42 | 42 |
異丙醇 | 質量份 | 25 | 25 | 25 | 25 | 25 | 25 | 25 | 25 |
無機 粒子 | 種類 | D-1 | D-1 | D-1 | D-1 | D-1 | D-1 | D-1 | D-1 |
質量份 | 0.34 | 0.34 | 0.34 | 0.34 | 0.34 | 0.34 | 0.34 | 0.34 | |
界面活性劑 | 種類 | F-1 | F-2 | F-3 | F-4 | F-5 | F-6 | F-7 | - |
HLB值 | 8.8 | 13.3 | 11.5 | 10.7 | - | 15.0 | 5.4 | - | |
質量份 | 1.3 | 1.3 | 1.3 | 1.3 | 1.3 | 1.3 | 1.3 | - | |
剝離 強度 | 剝離強度 [gf/25mm] | 920 | 890 | 780 | 830 | 720 | 590 | 860 | 930 |
評價 | ○ | ○ | △ | ○ | △ | △ | ○ | ○ | |
防霧性 | 初始防霧性 | ○ | ○ | ○ | ○ | ○ | △ | △ | × |
經時之防霧性 | ○ | ○ | ○ | ○ | ○ | - | × | - | |
轉移性 | ○ | ○ | ○ | ○ | △ | - | - | - |
由表2可知,實施例1~8中,水分散性、保存穩定性、黏接性、耐黏連性及耐水性的平衡良好,係良好。反觀比較例1中,聚酯樹脂之熔點高,水分散體之保存穩定性差。另外,剝離強度低,耐水性差。比較例2及4中,聚酯樹脂之結晶性低,不具熔點,故耐黏連性差。比較例3中,未共聚合脂肪族二羧酸,故結晶性低,耐黏連性差。比較例5及6中,聚酯樹脂之脂肪族二羧酸之共聚量多,結晶性不足,故水解容易進行,水分散體之保存穩定性、耐水性、或耐黏連性差。比較例7中,聚酯樹脂之酸價低,分散不良,故未能獲得水分散體。因此,無法測定剝離強度等特性。比較例8中,使用了5-磺酸基間苯二甲酸,故雖可製作水分散體,但耐水性差。
由表3可知,相較於不含無機粒子之實施例15,含有無機粒子之實施例9~14的耐黏連性更良好。又,實施例13、14中,剝離強度穩定性更良好。
由表4可知,相較於不含界面活性劑之實施例23,含有界面活性劑之實施例16~22中可展現防霧性。再者,係非離子性界面活性劑且HLB值為特定範圍內之界面活性劑的實施例16~19中,剝離強度、初始防霧性、經時之防霧性、轉移性的平衡良好,係良好。
[產業上利用性]
本發明之黏接劑組成物或塗佈組成物、及使用該組成物之疊層薄膜,作為包裝容器之蓋材進行熱密封時,與基材之黏接性優異,兼具耐黏連性、及優異的防霧性。
Claims (14)
- 一種結晶性聚酯樹脂,係以多元羧酸成分與多元醇成分作為共聚成分,多元羧酸成分含有30~70莫耳%之對苯二甲酸、10~60莫耳%之1,4-環己烷二甲酸、5~30莫耳%之碳數10以下之脂肪族二羧酸,且具有磺酸鹽基之芳香族二羧酸成分之含量未達3莫耳%,多元醇成分含有50~100莫耳%之1,4-丁二醇,該結晶性聚酯樹脂之酸價為100~600eq/t,玻璃轉移溫度為-30~30℃,熔點為70~160℃,數量平均分子量為5000~40000。
- 一種聚酯樹脂水分散體,含有如請求項1之結晶性聚酯樹脂。
- 如請求項2之聚酯樹脂水分散體,其有機溶劑含量為1質量%以下。
- 如請求項2或3之聚酯樹脂水分散體,其中,令結晶性聚酯樹脂為100質量份時,含有0.1~10質量份之平均粒徑為1μm以上且30μm以下之無機粒子。
- 如請求項4之聚酯樹脂水分散體,其中,該無機粒子之細孔容積未達2.0mL/g。
- 如請求項2或3之聚酯樹脂水分散體,其中,令結晶性聚酯樹脂為100質量份時,含有0.1~10質量份之選自由陰離子性界面活性劑及非離子性界面活性劑構成之群組中之1種以上之界面活性劑。
- 如請求項6之聚酯樹脂水分散體,其中,該非離子性界面活性劑具有6~14之HLB值,且具有聚氧伸烷基骨架。
- 一種黏接用或塗佈用之組成物,含有如請求項2至7中任一項之聚酯樹脂水分散體。
- 一種疊層薄膜,係將塗布如請求項8之黏接用或塗佈用之組成物而得之層、及熱塑性樹脂薄膜予以疊層而成。
- 如請求項9之疊層薄膜,其中,熱塑性樹脂薄膜為聚酯系樹脂薄膜。
- 如請求項9或10之疊層薄膜,其中,塗布黏接用或塗佈用之組成物而得之層的厚度為0.5~10μm之範圍。
- 一種包裝材,具有如請求項9至11中任一項之疊層薄膜作為構成要素。
- 一種食品包裝容器用蓋材,具有如請求項12之包裝材作為構成要素。
- 一種食品包裝容器,係如請求項13之食品包裝容器用蓋材與聚酯系樹脂之疊層體。
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