1242496 A7 B7 五、發明說明（1) 發明背景 本發明有關一種包裝袋，更特別的是其有關一種適於 製造食品（諸如火腿與香腸）時包裝用之食品包裝袋。 一般而言，將火腿與香腸原料裝在可收縮薄膜組成之 包裝袋中，然後於一個承盤中熱處理該原料。此等銷售之 前，將一印刷標簽貼在該裝有食品之包裝袋表面◦因爲存 在該裝有食品之包裝袋表面上標簽粘合表面的水對於印刷 標簽貼於裝有食品之包裝袋表面的粘合強度有不良影響， 所以當該裝有食品之包裝袋自承盤取出時必須迅速去除水 ，使粘貼標簽之前不必乾燥該包裝袋表面。除了包裝食品 之外’各種其他產物亦需要表面具有良好排水或去除水性 質，而且即使以水淸洗之後其標簽粘合強度仍然良好之包 裝袋。此外，於運送時該包裝袋必須具有良好抗針孔性。 根據本發明人硏究結果，已發現層壓（A )包括含有 特定量聚萘酸伸乙酯形成單位之聚酯樹脂與含有特定量聚 對苯二甲酸伸乙酯形成單位之聚酯樹脂的摻合樹脂層，或 是含有特定量聚對苯二甲酸伸丁酯形成單位之樹脂層作爲 最外層，（B ) —阻隔氣體樹脂層與（C ) 一熱密封樹脂 層作爲最內層，以此順序層壓，並熱密封該製得層壓薄膜 ，如此製得之包裝袋顯示良好之標簽粘合強度與抗針孔性 。以上述發現爲基礎完成本發明。 發明摘要 本發明目的係提出一種可顯示良好標簽粘合強度與抗 (請先閱讀背面之注意事項再填寫本頁) ;#--------訂·—— 線· 經濟部智慧財產局員工消費合作社印製 適 度 尺 張 紙 本 格 規 4 )A S) N 一(C 準 標 家 釐 公 97 1242496 A7 _ B7__ 五、發明說明（2 ) 針孔性之包裝袋。 (請先閱讀背面之注意事項再填寫本頁) 爲達成此目的，本發明第一方面係提出一種熱密封未 經拉伸層壓薄膜製得之包裝袋，該層壓薄膜包括至少（A )一摻合樹脂層，其包括含有不少於7 0莫耳％聚萘酸伸 乙酯形成單位之聚酯樹脂與含有不少於7 0莫耳％聚對苯 一甲酸伸乙酯形成單位之聚酯樹脂，或是一種含有不少於 7 0莫耳％聚對苯二甲酸伸丁酯形成單位之聚酯樹脂；（ B ) —阻隔氣體樹脂層；與（C ) 一熱密封樹脂層， 以此順序層壓樹脂層（A ) 、 （ B )與（C.)，如此 使樹脂層（A )作爲最外層，而樹脂層（C )作爲最內層 〇 經濟部智慧財產局員工消費合作社印製 本發明第二方面係提出一種熱密封未經拉伸層壓薄膜 製得之包裝袋，該層壓薄膜包括至少（A ) —摻合樹脂層 ，其包括含有不少於7 0莫耳％聚萘酸伸乙酯形成單位之 聚酯樹脂與含有不少於7 0莫耳％聚對苯二甲酸伸乙酯形 成單位之聚酯樹脂，或是一種含有不少於7 0莫耳％聚對 苯二甲酸伸丁酯形成單位之聚酯樹脂；（D ) —粘合樹脂 層；（B ) —阻隔氣體樹脂層；（D ) —粘合樹脂層；與 (C ) 一熱密封樹脂層，1242496 A7 B7 V. Description of the invention (1) Background of the invention The present invention relates to a packaging bag, and more particularly to a food packaging bag suitable for packaging foods such as ham and sausages. Generally, the raw materials of ham and sausage are packed in a shrinkable film packaging bag, and the raw materials are heat-treated in a tray. Prior to these sales, a printed label was affixed to the surface of the food bag.Because of the water on the surface of the label with the food on the surface of the food bag, the printed label was affixed to the surface of the food bag. Adhesive strength has a bad effect, so when the packaging bag containing food is taken out of the tray, water must be removed quickly, so that the surface of the packaging bag does not have to be dried before the label is attached. In addition to packaged foods, various other products also require packaging bags that have good surface drainage or water-removal properties, and have good label adhesion even after being washed with water. In addition, the packaging bag must have good pinhole resistance during shipping. According to the results of the present inventors' investigation, it has been found that the laminate (A) includes a polyester resin containing a specific amount of polyethylene naphthalate forming units and a polyester resin containing a specific amount of polyethylene terephthalate forming units. Blended resin layer, or a resin layer containing a specific amount of polybutylene terephthalate forming unit as the outermost layer, (B)-a gas barrier resin layer and (C) a heat-sealing resin layer as the innermost layer, with The laminated film was laminated in this order, and the obtained laminated film was heat-sealed. The packaging bag thus obtained showed good label adhesive strength and pinhole resistance. The present invention has been completed based on the above findings. Summary of the Invention The purpose of the present invention is to propose a label that can show good adhesive strength and resistance (please read the precautions on the back before filling out this page); # -------- Order · —— Line · Intellectual Property of the Ministry of Economic Affairs Bureau of Consumer Cooperatives printed moderate ruled paper rules 4) AS) N one (C quasi standard Jia 97 97 42 42496 A7 _ B7__ V. Description of the invention (2) Pinhole packaging. (Please read the back of the first Note: Please fill in this page again.) In order to achieve this, the first aspect of the present invention is to propose a packaging bag made of a heat-sealed unstretched laminated film including at least (A) a blended resin layer, It includes a polyester resin containing not less than 70 mole% of polyethylene terephthalate forming units and a polyester resin containing not less than 70 mole% of polyethylene terephthalate forming units, or A polyester resin containing not less than 70 mol% polybutylene terephthalate forming units; (B)-a gas barrier resin layer; and (C) a heat-sealing resin layer, and the resin is laminated in this order Layers (A), (B), and (C.), so that the resin layer (A) serves as the most The resin layer (C) is printed as the innermost layer. The printing is performed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs. The second aspect of the present invention is to propose a packaging bag made of a heat-sealed unstretched laminated film Including at least (A)-a blended resin layer comprising a polyester resin containing not less than 70 mole% poly (naphthalate) forming units and a polyester resin containing not less than 70 mole% of poly (terephthalate) Polyester resin in ethyl ester-forming units, or a polyester resin containing not less than 70 mol% polybutylene terephthalate-forming units; (D)-adhesive resin layer; (B)-barrier Gas resin layer; (D)-adhesive resin layer; and (C) a heat-sealing resin layer,
以此順序層壓樹脂層（A ) 、（ D ) 、( B ) 、( D )與（C )，如此使樹脂層（A )作爲最外層，而樹脂層 (C )作爲最內層。 本發明第三方面係提出包括第一方面與第二方面所定 義包裝袋之食品包裝袋。 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） -5 - 1242496 A7 B7 五、發明說明（3 ) 發明詳述 下文詳細描述本發明。 (請先閱讀背面之注意事項再填寫本頁) 本發明包裝袋係熱密封未經拉伸層壓薄膜製得。該未 經拉伸層壓薄膜具有多層結構，其包括至少（A ) —摻合 樹脂層，其包括含有不少於7 0莫耳％聚萘酸伸乙酯形成 單位之聚酯樹脂與含有不少於7 0莫耳％聚對苯二甲酸伸 乙酯形成單位之聚酯樹脂，或是一種含有不少於7 〇莫耳 %聚對苯二甲酸伸丁酯形成單位之聚酯樹脂；（B ) —阻 隔氣體樹脂層；與（C ) 一熱密封樹脂層，其中以此順序 層壓樹脂層（A ) 、（ B )與（C )。此外，本發明較佳 具體實例中可於相鄰樹脂層之間插入粘合樹脂層。 構成樹脂層（A )之各別聚酯樹脂不僅包括均聚物， 其亦包括共聚物。 至於由均聚物組成之聚酯樹脂-即聚萘酸伸乙酯（ 經濟部智慧財產局員工消費合作社印製 P E N )樹脂、聚對苯二甲酸伸乙酯（p E T )樹脂或聚 對苯二甲酸伸丁酯（P B T )樹脂，其實例爲任何原本已 用以製造薄膜之習知樹脂。 至於由共聚物組成之聚酯樹脂而言，每種聚酯樹脂中 之P E N形成單位、P E T形成單位或P B T形成單位以 85至99莫耳％爲佳。 上述共聚物之組份如下。換言之，該共聚物之二羧酸 組份實例爲異苯二甲酸、苯二.甲酸、2 ，6 —萘二羧酸、 己二酸、癸二酸、含氧羧酸（諸如鄰-含氧苯酸）等。該 -6 - 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） 1242496 經濟部智慧財產局員工消費合作社印製 A7 B7 五、發明說明（4) 共聚物之乙二醇組份實例爲乙二醇、二甘醇、丙二醇、丁 二醇、1 ，4 —環己烷二甲醇、新戊二醇、聚氧化乙烯乙 二醇、聚氧化丙烯乙二醇、聚丁撐氧乙二醇（ polytetramethylene oxide glycol )等。可倂用任二或多種此 等二羧酸組份與乙二醇組份。 在聚酯樹脂（A )包括摻合樹脂之實例中，通常選用之 P E N樹脂對P E T樹脂重量比率在1:0.5至1:2範圍內。 至於該由共聚物組成之聚酯樹脂，以包含不少於7 0 莫耳％聚對苯二甲酸伸丁酯形成單位之聚酯樹脂爲佳。此 情況中，可使用數量平均分子量3 0 0至6 ，0 0 0爲佳 (500至2 ，000更佳）之聚四氧化甲烯乙二醇作爲 該聚酯樹脂之共聚組份。使用符合上述需求之共聚P B T 樹脂可製得顯示良好撓曲性且不損及耐熱性之薄膜，而且 因其熱拉伸溫度低之故，其具有比共聚P B T樹脂高之抗 針孔性。此種共聚樹脂之熔點係2 0 0至2 2 3 °C爲佳， 但是均聚P B T樹脂之熔點爲2 2 5 °C。 構成樹脂層（A )之聚酯樹脂可另外包含一種有機或 無機顆粒組成之抗結塊劑，以加強所形成包裝袋堆放貯存 時之抗結塊性質。 該有機顆粒組成之抗結塊劑實例係由聚苯乙烯、聚乙 烯、聚醯胺類、聚酯類、聚丙烯酸酯類、聚甲基丙烯酸酯 類、環氧樹脂、聚醋酸乙烯酯、聚氯乙烯等之均聚物或共 聚物組成的顆粒。該有機顆粒可另外包含一種交聯劑。由 該無機顆粒組成之抗結塊劑實例爲滑石、高嶺土、氧化矽 玉紙張尺度適用中國國家標準（CNS)A4規格(210 X 297公釐） ~ !·!!·--------^---------ί (請先閱讀背面之注意事項再填寫本頁) 1242496 A7 B7 經濟部智慧財產局員工消費合作社印製 五、發明說明（5 ) 、碳酸鈣、玻璃粉末等。 該抗結塊劑之平均顆粒大小通常約1至約1 〇 μ m。以 該樹脂爲基準，該抗結塊劑之用量通常爲1 〇 〇至 1〇，OOOppm， 1 ，〇00 至 5 ，〇0〇ppm 爲 佳。本發明中，使用由有機顆粒組成之抗結塊劑爲佳。其 中使用由聚丙烯酸酯類或聚甲基丙烯酸酯類組成有機顆粒 更佳。 該阻隔氣體樹脂層（B )係由選自包括聚醯胺類（ P A )、乙烯一醋酸乙烯基酯共聚物（（E V〇Η )之皂 化產物、聚對苯二甲酸伸乙酯（Ρ Ε Τ )、聚萘酸伸乙酯 (Ρ Ε Ν )與聚碳酸酯（P C )之任一種樹脂組成。此等 樹脂中，以聚醯胺類（P A )或乙烯一醋酸乙烯基酯共聚 物（（Ε V〇Η )之皂化產物爲佳，以聚醯胺類（p a ) 更佳。 本發明中’可使用聚縮個別原料一即聚縮（1 )具有 不少於3圓環之內醯胺，（2 )可聚合ω -胺基酸或（3 )二胺與二羧酸所製得之聚醯胺類。 該具有不少於3員環之內醯胺特定實例爲ε -己內醯胺 、庚醯己內醯胺、α —吡略烷酮、α〜六氫吡啶酮等。該可 聚合ω -胺基酸之特定實例可包括6 一胺基己酸、7 一胺 基庚酸、1 1 一胺基十一酸、9 一胺基壬酸等。 該二胺類之特定實例可包括六伸甲基二胺、九伸甲基 二胺、十一伸甲基二胺、十二伸甲基二胺、偏苯二甲基（ metaxylylene )二胺等。該二羧酸之等定實例包括對苯二甲 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） -8 - (請先閱讀背面之注意事項再填寫本頁) --------訂---------線· 1242496 A7 B7 經濟部智慧財產局員工消費合作社印製 五、發明說明（6 ) 酸、異苯二甲酸、己二酸、癸二酸、十二院二元酸、戊一 酸等。 本發明所使用之聚醯胺類特定實例可包括耐綸4、6 、7、8、11、12、6·6、6·10、6·1!、 6 · 1 2、6Τ、6/6 · 6、6/6Τ 與 6 1/6丁 等 〇 至於該熱密封樹脂層（C )，通常可使用高密度聚乙 烯（H D Ρ Ε )、中密度聚乙烯（M D Ρ Ε )、低密度聚 乙烯（L D Ρ Ε )、聚丙烯（Ρ Ρ )、乙烯醋酸乙烯基酯 共聚物（Ε V A )、乙烯一甲基丙烯酸共聚物（Ε Μ A ) 、乙烯一丙烯酸乙酯共聚物（Ε E A )、乙烯一甲基丙烯 酸甲酯共聚物（Ε Μ Μ A )、乙烯—丙烯酸（acrylatic acid )共聚物（E A A )、乙烯一甲基丙烯酸乙酯共聚物 (Ε M A A )、粘合性聚乙烯、離子鍵共聚物樹脂、 Ε V A之皂化產物、直鏈低密度聚乙烯（L 一 L D Ρ E ) 或其共聚物。此等化合物中，使用直鏈低密度聚乙烯（L 一 L D Ρ E )爲佳。 該直鏈低密度聚乙烯（L 一 L D Ρ E )係乙烯與具有* 3至1 3個碳原t且乙稀含量爲8 6至9 9 · 5莫耳 一烯烴的共聚物。該L 一 L D Ρ Ε係一種與習用高壓製造 L D Ρ Ε不同之低中密度聚乙烯。該高壓製造l D Ρ Ε與 L 一 L D Ρ Ε之差異係該高壓製造L D Ρ Ε具有多分枝分 子結構，而該L 一 L D Ρ Ε具有直鏈分子結構。製造該L 一 L D Ρ E時，可使用丁烯—1 、戊烯一 1 、己烯〜Ί 、 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） -9 (請先閱讀背面之注意事項再填寫本頁) I ϋ I I ϋ 1 -I ϋ 線· A7 1242496 ____B7_ 五、發明說明（7 ) 辛烯一 1、4 一甲基戊烯一 1等作爲與乙烯共聚之α —烯烴 。乙烯與此等α 一烯烴之共聚作用可使用所謂塞格勒一那塔 觸媒以低中壓力方法進行。上述直鏈低密度聚乙烯（1^-L D Ρ Ε )之市售產物特定實例可包括unIPOL (Union Carbide Corp.)、DOWLEX (Dow Chemical)、SQULERE (du Pont，Canada)、 MARLEX (Philips Corp.)、 NEOZEX 與 ULTZEX (Mitsui Petrochemical Co., Ltd.) 、 NISSEKI LINILEX (Nippon Petrochemical Co.，Ltd.)、 STAMILEX (DSM)等。 該粘合樹脂層通常由經改良聚烯烴樹脂（A P〇）組 成。此種A P 0 s係共聚及/或接枝聚合一種主要由乙烯 組份及/或丙烯組份組成聚烯烴樹脂與α -、β -不飽和羧 酸或其衍生物製得。 該聚烯烴樹脂之實例爲聚乙烯、聚丙烯、乙烯-丙烯 共聚物、乙烯- 丁烯- 1共聚物、乙烯-醋酸乙酯共聚物 、乙烯-丙烯酸鈉共聚物等。 與該聚烯烴樹脂共聚之α -、β -不飽和羧酸或其衍生 物實例爲丙烯酸、甲基丙烯酸、甲基丙烯酸甲酯、丙烯酸 鈉、丙烯酸鋅、醋酸乙烯基酯、甲基丙烯酸縮水甘油酯等 。此等α -、β 一不飽和羧酸或其衍生物可存在該聚烯烴樹 脂之分子鏈中，其數量不多於4 0莫耳％。 與該聚烯烴樹脂接枝之α -、β -不飽和羧酸或其衍生 物實例爲丙烯酸、甲基丙烯酸、ethacylie酸、順式丁烯二 酸、延胡索酸、此等酸類之酐類、此等酸類之酯類等。用 (請先閱讀背面之注音？事項再填寫本頁) ------—訂--------1▲ 經濟部智慧財產局員工消費合作社印製 -^1 1 ^1 ϋ ϋ I - 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） 10 1242496 A7 _ B7 五、發明說明（8 ) 於改良該聚烯烴樹脂之此等化合物中，以順式丁烯二酸酉干 尤佳。此等接枝化合物之用量爲〇 · 〇 1至2 5重量％， 以〇 · 0 5至1 · 5重量％爲佳’其係鮮該聚烯烴樹脂重 量爲基準。 該接枝聚合作用可以習用方法進行，即通常於1 5 〇 至3 0 〇 °C樹脂溫度下熔融混合該聚烯烴樹脂與α 一、p 一 不飽和羧酸或其衍生物。該接枝聚合作用中，爲有效進行 該反應’於該反應混合物中添加有機過氧化物爲佳，諸如α ，α’ -雙一第三丁基過氧一鄰二異丙基苯，其用量爲 〇 . 0 0 1至0 · 0 5重量％，此係以該聚烯烴樹脂與α 一 、β -不飽和羧酸或其衍生物總重爲基準。 該未經拉伸層壓薄膜中，以聚萘酸伸乙酯樹脂與聚對 苯二甲酸伸乙酯樹脂之摻合物所組成或是聚對苯二甲酸伸 丁酯組成之樹脂層（A )作爲包裝袋最外層，以熱密封樹 脂所組成之樹脂層（C )作爲該包裝袋之最內層，以阻隔 氣體樹脂所組成之樹脂層（B )作爲介於樹脂層（a )與 (C )間之中間層。樹脂層（A )之厚度通常爲5至 1〇Ο μ m ’以1 0至7 Ο μ m爲佳。樹脂層（β )之厚度 通常爲5至5〇μ m，以1〇至3〇μ m爲佳。樹脂層（C )之厚度通常爲20至1 ΟΟμπι，以3〇至70μηι爲佳 。本發明較佳具體實例中介於相鄰樹脂層間之粘合層厚度 通常爲2至3 0 μ m，以5至1 5 μ m爲佳。 例如先以下流水冷模製方法使用一共擠製圓模形成一 管狀主體，然後熱止封該管狀主體一端製造本發明之包裝 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐)「11: (請先閱讀背面之注意事項再填寫本頁) - 經濟部智慧財產局員工消費合作社印製 — — — — — — — 11111111 — — — — — — l·! I — — — — — — — — — 1242496 A7 B7 經濟部智慧財產局員工消費合作社印製 五、發明說明（9 ) 袋。該層壓薄膜可由T模方法製得。通常以橫摺方法進行 熱密封作用。本技藝中已習知該共擠製模製法與橫摺法， 下文中簡述其適用製程。 在共擒製模製法中’通常將一個具有內部塡料環之水 容器置於該圓形模下方。另外，將一導板與捲取滾筒安置 於該水容器之下。經由該圓形模共擠製多種原料樹脂，但 是實質上避免拉伸該樹脂。該共擠製樹脂通過用以冷卻之 塡料環後，所形成之管形層壓薄膜通過該導板，並送至該 捲取滾筒，如此折疊，取得雙層薄膜形式之薄膜。因此， 製得之層壓薄膜實質上未經拉伸。此外，在較佳具體實例 中’該層壓薄膜顯示之縱向（M D )與橫向（T D )任一 方向熱收縮百分比（J I S Κ 6 7 3 4 )不大於5 % 〇 該橫摺方法係用以折疊並密封該薄膜管狀主體末端部 分之方法。在習用橫摺方法中，該管狀薄膜開口末端形成 長方形，自靠近每個壁中線將一組相對的壁向內折。折疊 另一組壁’並以排列方式交疊在該折疊之相對壁上，於其 間形成橫摺。該製得之折疊管狀薄膜係使用一熱密封棒沿 著其橫摺末端部分熱密封。 本:發明之包裝袋適於用在食品包裝袋，例如用以製造 火腿與香腸之包裝袋、裝塡礦泉水之飮料包裝袋等。尤其 是該包裝袋最外層係由特定聚酯樹脂組成之故，即使甫自 承盤取出’該包裝袋仍可顯示優良之標簽粘合強度。本發 曰月@ €之技術優點係該最外層由具有高排水性或去除水 本紙張尺度適时關家鮮（CN^；格⑽x 297公餐）~—-— (請先閱讀背面之注意事項再填寫本頁)The resin layers (A), (D), (B), (D), and (C) are laminated in this order, so that the resin layer (A) is the outermost layer and the resin layer (C) is the innermost layer. A third aspect of the present invention is a food packaging bag including the packaging bag defined in the first aspect and the second aspect. This paper size applies to China National Standard (CNS) A4 specifications (210 X 297 mm) -5-1242496 A7 B7 V. Description of the invention (3) Detailed description of the invention The invention is described in detail below. (Please read the precautions on the back before filling this page) The packaging bag of the present invention is made of heat-sealed unstretched laminated film. The unstretched laminated film has a multilayer structure including at least (A) -blended resin layer, which includes a polyester resin containing not less than 70 mol% polyethylene naphthalate forming units and a resin containing Polyester resin with less than 70 mole% poly (ethylene terephthalate) forming units, or a polyester resin containing not less than 70 mole% of polybutylene terephthalate forming units; ( B) — a gas barrier resin layer; and (C) a heat-sealing resin layer, in which the resin layers (A), (B), and (C) are laminated in this order. In addition, in a preferred embodiment of the present invention, an adhesive resin layer may be interposed between adjacent resin layers. The respective polyester resins constituting the resin layer (A) include not only homopolymers but also copolymers. As for the polyester resin composed of homopolymer, namely polyethylene naphthalate (PEN printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs) resin, polyethylene terephthalate (p ET) resin or polyparaphenylene Butyl dicarboxylate (PBT) resin is exemplified by any conventional resin that has been used to make films. As for the polyester resin composed of a copolymer, the P E N forming unit, the P E T forming unit, or the P B T forming unit in each polyester resin is preferably 85 to 99 mol%. The composition of the above copolymer is as follows. In other words, examples of the dicarboxylic acid component of the copolymer are isophthalic acid, benzene dicarboxylic acid, 2,6-naphthalenedicarboxylic acid, adipic acid, sebacic acid, and oxygen-containing carboxylic acids such as o-oxygen Benzoic acid) and so on. The -6-This paper size is in accordance with Chinese National Standard (CNS) A4 (210 X 297 mm) 1242496 Printed by the Consumers ’Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs A7 B7 V. Description of the invention (4) Ethylene glycol group of copolymer Examples are ethylene glycol, diethylene glycol, propylene glycol, butylene glycol, 1,4-cyclohexanedimethanol, neopentyl glycol, polyethylene oxide ethylene glycol, polypropylene oxide ethylene glycol, polybutylene oxide Ethylene glycol (polytetramethylene oxide glycol), etc. Any two or more of these dicarboxylic acid components and ethylene glycol components may be used. In the case where the polyester resin (A) includes a blended resin, the weight ratio of P E N resin to P E T resin is usually selected in the range of 1: 0.5 to 1: 2. As for the polyester resin composed of a copolymer, a polyester resin containing not less than 70 mol% polybutylene terephthalate forming units is preferred. In this case, polytetramethylene glycol having a number-average molecular weight of 300 to 6,000, and more preferably 500 to 2,000, may be used as a copolymerization component of the polyester resin. The copolymerized P B T resin that meets the above requirements can be used to produce films that exhibit good flexibility without compromising heat resistance, and because of its low heat stretching temperature, it has higher pinhole resistance than the copolymerized P B T resin. The melting point of this copolymer resin is preferably from 200 to 2 3 ° C, but the melting point of the homopolymerized P B T resin is 2 2 5 ° C. The polyester resin constituting the resin layer (A) may further include an anti-caking agent composed of organic or inorganic particles to enhance the anti-caking properties of the formed packaging bags when stacked and stored. Examples of the anti-caking agent composed of the organic particles are made of polystyrene, polyethylene, polyamides, polyesters, polyacrylates, polymethacrylates, epoxy resins, polyvinyl acetate, polymer Particles composed of homopolymers or copolymers such as vinyl chloride. The organic particles may further include a crosslinking agent. Examples of the anti-caking agent composed of the inorganic particles are talc, kaolin, and silicon oxide paper. Applicable to China National Standard (CNS) A4 (210 X 297 mm). -^ --------- ί (Please read the precautions on the back before filling out this page) 1242496 A7 B7 Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 5. Description of the invention (5), calcium carbonate, glass Powder etc. The average particle size of the anticaking agent is usually about 1 to about 10 μm. Based on the resin, the amount of the anti-caking agent is usually 1,000 to 10,000 ppm, and preferably 1,000 to 5,000 ppm. In the present invention, an anti-caking agent composed of organic particles is preferably used. Among them, it is more preferable to use organic particles composed of polyacrylates or polymethacrylates. The gas barrier resin layer (B) is selected from the group consisting of saponification products including polyamines (PA), ethylene-vinyl acetate copolymer ((EV〇EV)), polyethylene terephthalate (PE) T), any of polyethylene naphthalate (PEN) and polycarbonate (PC) resins. Among these resins, polyamines (PA) or ethylene vinyl acetate copolymer ( The saponified product of (E V〇Η) is more preferred, and polyamidoamines (pa) are more preferred. In the present invention, it is possible to use polycondensation of individual raw materials-that is, polycondensation (1) has not less than 3 rings 醯Amines, (2) polymerizable omega-amino acids or (3) diamines and polycarboxylic acids made from polyamidoamines. The specific example of the phosphonium amine having not less than 3 members is ε-caprolactone Amidoamine, heptamine caprolactam, α-pyrrolidone, α ~ hexahydropyridone, etc. Specific examples of the polymerizable omega-amino acid may include 6-aminocaproic acid, 7-aminoheptanoic acid Acid, 1 1 monoaminoundecanoic acid, 9 monoaminononanoic acid, etc. Specific examples of the diamines may include hexamethylenediamine, nonamethyldiamine, undecymethyldiamine, Twelve extensions Diamine, metaxylylene diamine, etc. Equal examples of this dicarboxylic acid include terephthalate. This paper is sized to the Chinese National Standard (CNS) A4 (210 X 297 mm) -8- (Please read the precautions on the back before filling this page) -------- Order --------- line · 1242496 A7 B7 Printed by the Employees' Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs (6) Acid, isophthalic acid, adipic acid, sebacic acid, dodecanedioic acid, glutaric acid, etc. Specific examples of polyamides used in the present invention may include nylon 4, 6, 7 , 8,11,12,6 · 6,6 · 10,6 · 1 !, 6 · 1 2, 6T, 6/6 · 6, 6 / 6T and 6 1/6 D, etc. As for the heat-sealing resin layer (C), usually high density polyethylene (HD PP), medium density polyethylene (MD PP), low density polyethylene (LD PP), polypropylene (PP), ethylene vinyl acetate copolymer (E VA), ethylene-methacrylic acid copolymer (E Μ A), ethylene-ethyl acrylate copolymer (E EA), ethylene-methyl methacrylate copolymer (E Μ Μ A), ethylene-propylene Acrylatic acid copolymer (EAA), ethylene monoethyl methacrylate copolymer (E MAA), adhesive polyethylene, ionomer copolymer resin, saponified product of EVA, linear low density polyethylene ( L-LD PE) or a copolymer thereof. Among these compounds, linear low-density polyethylene (L-LD PE) is preferably used. The linear low-density polyethylene (L-LD PE) is a kind of ethylene and A copolymer having * 3 to 13 carbon atoms t and an ethylene content of 8 6 to 9 9 · 5 mole monoolefin. The L-L DPP is a kind of low-medium density polyethylene which is different from the conventional high-pressure manufacturing L DPP. The difference between the high-pressure manufacturing LDPE and L-LPDEP is that the high-pressure manufacturing LDPE has a multi-branched molecular structure, and the L-LPDEP has a linear molecular structure. When manufacturing this L-LD PE, you can use butene-1, pentene-1, hexene ~ Ί, this paper size is applicable to China National Standard (CNS) A4 (210 X 297 mm) -9 (please first Read the notes on the back and fill in this page) I ϋ II ϋ 1 -I ϋ Line · A7 1242496 ____B7_ V. Description of the invention (7) Octene-1, 4-methylpentene-1, etc. -Olefins. The copolymerization of ethylene with these α-olefins can be performed in a low-medium pressure method using a so-called Segler-Natta catalyst. Specific examples of the commercially available products of the above-mentioned linear low-density polyethylene (1 ^ -LD PE) may include unIPOL (Union Carbide Corp.), DOWLEX (Dow Chemical), SQULERE (du Pont, Canada), MARLEX (Philips Corp. ), NEOZEX and ULTZEX (Mitsui Petrochemical Co., Ltd.), NISSEKI LINILEX (Nippon Petrochemical Co., Ltd.), STAMILEX (DSM), etc. This adhesive resin layer is usually composed of a modified polyolefin resin (A PO). This A P 0 s system is copolymerized and / or graft polymerized by a polyolefin resin mainly composed of an ethylene component and / or a propylene component and α-, β-unsaturated carboxylic acid or a derivative thereof. Examples of the polyolefin resin are polyethylene, polypropylene, ethylene-propylene copolymer, ethylene-butene-1 copolymer, ethylene-ethyl acetate copolymer, ethylene-sodium acrylate copolymer, and the like. Examples of α-, β-unsaturated carboxylic acids or derivatives thereof copolymerized with the polyolefin resin are acrylic acid, methacrylic acid, methyl methacrylate, sodium acrylate, zinc acrylate, vinyl acetate, glycidyl methacrylate Esters, etc. These α-, β-unsaturated carboxylic acids or their derivatives may be present in the molecular chain of the polyolefin resin in an amount of not more than 40 mole%. Examples of α-, β-unsaturated carboxylic acids or derivatives thereof grafted with the polyolefin resin are acrylic acid, methacrylic acid, ethacylie acid, maleic acid, fumaric acid, anhydrides of these acids, and the like Acids and esters. Use (Please read the phonetic on the back? Matters before filling out this page) -------- Order -------- 1 ▲ Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs-^ 1 1 ^ 1 ϋ ϋ I-This paper size is in accordance with Chinese National Standard (CNS) A4 (210 X 297 mm) 10 1242496 A7 _ B7 V. Description of the invention (8) Among these compounds that improve the polyolefin resin, cis-butyl Dried arsenate is particularly preferred. These grafting compounds are used in an amount of 0. 0 to 25.5% by weight, preferably 0. 05 to 1.5% by weight ', based on the weight of the polyolefin resin. The graft polymerization can be performed by a conventional method, that is, the polyolefin resin is usually melt-mixed with α-, p-unsaturated carboxylic acid or a derivative thereof at a resin temperature of 150 to 300 ° C. In the graft polymerization, it is better to add an organic peroxide to the reaction mixture, such as α, α′-bis-third-butylperoxy-o-diisopropylbenzene, in order to effectively perform the reaction, and the amount thereof It is from 0.001 to 0.05% by weight based on the total weight of the polyolefin resin and α-, β-unsaturated carboxylic acid or its derivative. In this unstretched laminated film, a resin layer composed of a blend of polyethylene naphthalate resin and polyethylene terephthalate resin or polybutylene terephthalate (A ) As the outermost layer of the packaging bag, the resin layer (C) composed of the heat-sealing resin is used as the innermost layer of the packaging bag, and the resin layer (B) composed of the gas barrier resin is used as the intervening resin layer (a) and ( C) the middle layer. The thickness of the resin layer (A) is usually 5 to 100 μm, and preferably 10 to 70 μm. The thickness of the resin layer (β) is usually 5 to 50 µm, and preferably 10 to 30 µm. The thickness of the resin layer (C) is usually 20 to 100 μm, and preferably 30 to 70 μm. In the preferred embodiment of the present invention, the thickness of the adhesive layer between the adjacent resin layers is usually 2 to 30 μm, and preferably 5 to 15 μm. For example, the following flowing water cooling molding method first uses a co-extruded round die to form a tubular body, and then heat-seals one end of the tubular body to manufacture the packaging of the present invention. The paper size is applicable to China National Standard (CNS) A4 (210 X 297 mm) ) "11: (Please read the precautions on the back before filling out this page)-Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs — — — — — — — 11111111 — — — — — — l ·! I — — — — — — — — — 1242496 A7 B7 Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs. 5. Description of the invention. (9) Bag. The laminated film can be made by T-die method. It is usually heat-sealed by horizontal folding method. This technique The co-extrusion molding method and the horizontal folding method are already known in China, and the applicable processes are briefly described below. In the co-clamp molding method, a water container with an inner material loop is usually placed under the circular mold. In addition, a guide plate and a winding drum are placed under the water container. A plurality of raw resins are co-extruded through the circular die, but the resin is substantially prevented from being stretched. The co-extruded resin is used to After the material loop is removed, the formed tubular laminated film passes through the guide plate and is sent to the take-up roller, which is then folded to obtain a film in the form of a double-layer film. Therefore, the obtained laminated film is substantially In addition, in a preferred embodiment, the percentage of heat shrinkage (JIS κ 6 7 3 4) in the longitudinal direction (MD) and the transverse direction (TD) of the laminated film is not more than 5%. The method is a method for folding and sealing the end portion of the tubular body of the film. In the conventional transverse folding method, the opening end of the tubular film is formed into a rectangle, and a group of opposite walls is folded inward from near the centerline of each wall. Folding another A set of walls' are arranged in an overlapping manner on the opposite wall of the fold to form a horizontal fold therebetween. The obtained folded tubular film is heat-sealed along its horizontal fold end portion using a heat-sealing rod. This invention The packaging bag is suitable for use in food packaging bags, such as packaging bags for making ham and sausage, packaging bags containing mineral water, etc. In particular, the outermost layer of the packaging bag is composed of a specific polyester resin. Fu Zi The packaging bag can still show the excellent label adhesive strength when taken out of the tray. The technical advantage of this month @ € is that the outermost layer is made of paper with high drainage or water-removable paper (CN ^;格 ⑽x 297 公 餐） ~ —-— (Please read the notes on the back before filling this page)
I — — — — — — — ^-------I I崖 1242496 A7 B7 五、發明說明（i〇) (請先閱讀背面之注意事項再填寫本頁) 性質之樹脂組成◦然而，如下文對照實例所述，例如使用 與P B T樹脂相似之P E T樹脂或P E N樹脂無法達到本 發明包裝袋此種技術優點。因此，使用特定摻合樹脂或 P B T樹脂所獲得之效果是非常出乎意料的結果。 尤其是，本發明包裝袋最外層係由含有不少於7 0莫 耳％聚對苯二甲酸伸丁酯形成單位之聚酯樹脂組成時，該 層壓薄膜本身可以顯示出良好的抗捲曲性質。詳言之，最 外層係上述聚酯樹脂以外樹脂所組成之包裝袋開口末端容 易捲曲，因此其不適於裝塡原料。然而，本發明包裝袋最 外層係由含有不少於7 0莫耳％聚對苯二甲酸伸丁酯單位 之聚酯樹脂組成，其沒有習用包裝袋所遭遇的缺點。 實施例： 現在參考下列實施例詳述本發明，但本發明不受限於 此等實施例，而且在本發明範疇內可能存在各種改良。 實施例1 : 經濟部智慧財產局員工消費合作社印製 一種具有多層結構之層壓薄膜：以下流水冷式模製法 使用五層共擠製圓形模將P B T層（8 μ m ) / A P〇層（ 6 μ m ) / N Y (耐綸 6 )層（1 6 μ m ) / A P 〇層（6 μ m ) / L — L D P E層（4 4 μ m )製成管形。製造該層 壓薄膜時，將作爲抗結塊劑且平均顆粒大小爲6 μ m之聚甲 基丙烯酸甲酯（Ρ Μ Μ A )顆粒添加於原P B T樹脂中， 其添加量爲2 ，0 0 0 p p m。該擠製溫度爲2 4 〇 °〇 ’ 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐）-13- 經濟部智慧財產局員工消費合作社印製 1242496 A7 -----------B7_ 一 五、發明說明（11 ) 水冷温度爲2 8 °C ’該薄膜之捲取速度爲1 5 m /分鐘。 將該製得之管狀層壓薄膜裁切成預定長度。對該經裁切薄 Θ吴進行橫摺處理，沿著該薄膜一末端外圍熱密封，如此製 &最外層由P B T組成且最內層由l 一 l D P E組成之橫 摺包裝袋。 事先烹煮之火腿原料裝入該橫摺e d包裝袋之後，毀 該包裝袋置於一承盤中熱密封該原料，如此製得接近縱向 中央方形區域爲8 cmx 8 cm且長度爲3 5 cm之長方 形火腿。以下列方法評估該製得經包裝火腿產物之標簽粘 合強度、抗結塊性質、抗針孔性與抗捲曲性。結果示於表 (lj標簽粘合強 將一標簽粘貼在甫自承盤取出之火腿產物，並測量其 撕落強度（g / 1 5 mm)。 (2)抗針孔件： 對十個包裝袋（每個實例十個包裝袋）實例進行於一 2〇°C冷凍運送試驗（巡迴整個Shikoku區域）。測量運送 時破裂之包裝袋個數評估該包裝袋之抗針孔性。 (3 )抗結塊忡皙： 將表面經乾燥之包裝火腿產物相疊以測量其滑動性質 。使用一張力試驗機進行該測量，以克數表示測量該滑動 性質。該克數愈小，滑動性質愈高，而且抗結塊性質愈良 好。 (4 )抗捲曲件質： (請先閱讀背面之注咅3事項再填寫本頁} -------· I----I I --I I I I------i----------- 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公爱） 14 1242496 A7 ______B7___ 五、發明說明（12 ) 肉眼觀察每個橫摺包裝袋開口末端之捲曲情況。 Μ例2與3及對照實例1至3 : 進行實施例1所定義之相同程序，除了使用 表1所 示之樹脂作爲最外層之外，如此製得橫摺包裝袋，然後包 裝火腿產物。實施例3中使用熔點爲2 2 2 °C且含有 2 · 5莫耳％數量平均分子量爲1 ，〇〇〇之聚丁撐氧乙 一醇作爲共聚組份之共聚P B T樹脂。附帶也，以實施例 1相同方式混合該最外層原料與2 ，0 0 0 p p m平均顆 粒大小爲6 μ m之Ρ Μ Μ A顆粒。以實施例1相同方式評估 該製得包裝火腿產物之標簽粘合強度、抗結塊性質與抗針 孔性。結果示於表2。 表1I — — — — — — — — ^ ------- II Cliff 1242496 A7 B7 V. Description of the invention (i〇) (Please read the notes on the back before filling this page) Properties of resin composition ◦ However, as follows As described in the comparative example, for example, the use of PET resin or PEN resin similar to PBT resin cannot achieve the technical advantages of the packaging bag of the present invention. Therefore, the effect obtained by using a specific blend resin or P B T resin is a very unexpected result. In particular, when the outermost layer of the packaging bag of the present invention is composed of a polyester resin containing not less than 70 mol% polybutylene terephthalate forming units, the laminated film itself can exhibit good anti-curling properties. . In detail, the outermost layer is an open end of a packaging bag made of a resin other than the above-mentioned polyester resin, and is easily curled, so it is not suitable for containing raw materials. However, the outermost layer of the packaging bag of the present invention is composed of a polyester resin containing not less than 70 mol% polybutylene terephthalate units, which does not have the disadvantages encountered with conventional packaging bags. Examples: The present invention will now be described in detail with reference to the following examples, but the present invention is not limited to these examples, and various modifications may exist within the scope of the present invention. Example 1: The consumer cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs prints a laminated film with a multi-layer structure: the following water-cooled molding method uses a five-layer co-extruded circular die to PBT layer (8 μm) / AP0 layer (6 μm) / NY (Nylon 6) layer (16 μm) / AP 〇 layer (6 μm) / L — LDPE layer (44 μm) is made into a tube shape. When the laminated film was manufactured, polymethyl methacrylate (PMA) particles having an average particle size of 6 μm as an anti-caking agent were added to the original PBT resin, and the amount of the addition was 2.0 0 ppm. The extrusion temperature is 2 40 °° '. This paper size is in accordance with China National Standard (CNS) A4 (210 X 297 mm). 13- Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs 1242496 A7 ----- ------ B7_ One or five, description of the invention (11) Water cooling temperature is 2 8 ° C 'The winding speed of the film is 15 m / min. The obtained tubular laminated film is cut into a predetermined length. The cut thin film Θ is cross-folded and heat-sealed along the periphery of one end of the film, so that a < outer layer is composed of P B T and the inner layer is composed of 1 to 1 D P E is a horizontally folded packaging bag. After the pre-cooked ham raw materials are loaded into the horizontally folded ed packaging bag, the packaging bag is destroyed and placed in a tray to heat-seal the raw material, so that the longitudinal central square area is 8 cm x 8 cm and the length is 3 5 cm Rectangular ham. The label adhesion strength, anti-caking properties, pinhole resistance and curl resistance of the prepared packaged ham product were evaluated by the following methods. The results are shown in the table (1j label adhesive strength, a label was attached to the ham product taken from the tray, and the tear strength (g / 15 mm) was measured. (2) anti-pinhole parts: for ten packages The bag (ten bags per example) was subjected to a freezing transport test at 20 ° C (touring the entire Shikoku area). The number of bags broken during transport was measured to evaluate the pinhole resistance of the bag. (3) Anti-clumping: Laminate the dried ham products on the surface to measure the sliding properties. Use a force tester to measure the sliding properties. The sliding properties are measured in grams. The smaller the grams, the higher the sliding properties. , And the better the anti-caking properties. (4) Anti-curl quality: (Please read Note 3 on the back before filling out this page} ------- · I ---- II --III I ------ i ----------- This paper size applies to China National Standard (CNS) A4 (210 X 297 public love) 14 1242496 A7 ______B7___ V. Description of the invention (12) Visual observation Curling of the open end of each horizontally folded packaging bag. Examples M and 2 and Comparative Examples 1 to 3: The same procedure as defined in Example 1 was performed. In addition to using the resin shown in Table 1 as the outermost layer, a horizontally folded packaging bag was prepared in this manner, and then the ham product was packaged. In Example 3, a melting point of 2 2 2 ° C and a number average molecular weight of 2.5 mole% was used. Copolymer PBT resin having a butylene oxide glycol of 1,000 as a copolymerization component. Incidentally, the outermost raw material was mixed with 2,000 ppm in the same manner as in Example 1 with an average particle size of 6 μm. P MM A particles. In the same manner as in Example 1, the label adhesion strength, anti-caking properties, and pin-hole resistance of the prepared packaged ham product were evaluated. The results are shown in Table 2. Table 1
實施例與對照實例 層結構 實施例1 PBT/APO/NY/APO/L-LDPE 實施例2 PEN與PET摻合物（重量比率爲 l:l)/APO/NY/APO/L-LDPE 實施例3 PBT/APO/NY/APO/L-LDPE 對照實例1 PET/APO/NY/APO/L-LDPE 對照實例2 PEN/APO/NY/APO/L-LDPE 對照實例3 NY/APO/NY/APO/L-LDPE 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） -15- (請先閱讀背面之注意事項再填寫本頁) 經濟部智慧財產局員工消費合作社印製 ---------tr---------^-------1 ——·---------- 1242496 A7 B7 五、發明說明（13) 表2 實施例與 對照實例 標簽粘合 強度 (g /1 5 m m 寬） 抗結塊性質 (g) 抗針孔性 (個數） 抗捲曲性 質（方向） 實施例1 632 23 2 〇 Μ ^ \\\ 實施例2 571 25 1 0 捲曲 (向內捲曲） 實施例3 632 235 0 Μ j \ \\ 對照實例1 272 247 2 捲曲 (向內捲曲） 對照實例2 3 18 258 2 捲曲 (向內捲曲） 對照實例3 22 240 9 捲曲 (向內捲曲） (請先閱讀背面之注咅？事項再填寫本頁) 經濟部智慧財產局員工消費合作社印製 0 β -- I I I I I I I — — — — — — — — — — — — — — — — — — l· — — I" — — — — — — — — — — 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） -16·Examples and Comparative Examples Layer Structure Example 1 PBT / APO / NY / APO / L-LDPE Example 2 PEN and PET Blend (weight ratio of 1: 1) / APO / NY / APO / L-LDPE Example 3 PBT / APO / NY / APO / L-LDPE Comparative Example 1 PET / APO / NY / APO / L-LDPE Comparative Example 2 PEN / APO / NY / APO / L-LDPE Comparative Example 3 NY / APO / NY / APO / L-LDPE This paper size applies to Chinese National Standard (CNS) A4 (210 X 297 mm) -15- (Please read the precautions on the back before filling this page) Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs- -------- tr --------- ^ ------- 1 ---------------- 1242496 A7 B7 V. Description of the invention (13) Table 2 Examples and comparative examples Label adhesion strength (g / 1 5 mm width) Anti-caking property (g) Anti-pinhole property (number) Anti-curling property (direction) Example 1 632 23 2 〇Μ ^ \ \\ Example 2 571 25 1 0 Curled (curled inward) Example 3 632 235 0 Μ j \ \\ Comparative Example 1 272 247 2 Curled (curled inward) Comparative Example 2 3 18 258 2 Curled (curled inward) ) Comparative example 3 22 240 9 Curling (curling inward) (Please read the note on the back first? Matters (Fill in this page) Printed by the Intellectual Property Bureau of the Ministry of Economic Affairs, Consumer Cooperatives 0 β-IIIIIII — — — — — — — — — — — — — — — l · — — I " — — — — — — — — — — This paper size applies to China National Standard (CNS) A4 (210 X 297 mm) -16 ·