TW434144B - Biaxially oriented film to be laminated on a metal - Google Patents
Biaxially oriented film to be laminated on a metal Download PDFInfo
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- TW434144B TW434144B TW85108782A TW85108782A TW434144B TW 434144 B TW434144 B TW 434144B TW 85108782 A TW85108782 A TW 85108782A TW 85108782 A TW85108782 A TW 85108782A TW 434144 B TW434144 B TW 434144B
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434 彳 44 A7 B7 經濟部中央標準局貝工消费合作社印裝 五、發明説明 ( 〆 ) 1 1 本 發 明 是 開 於 * 種 積 層 在 金 靨 上 之 雙 軸 拉 伸 薄 m 明 1 1 確 的 説 f 本 發 明 是 酯 於 一 種 積 層 在 金 羼 上 之 雙 轅 拉 伸 薄 1 | 膜 t 而 此 種 薄 睽 在 積 層 於 金 屬 板 上 之 後 再 進 行 製 罐 加 X 請 1 1 1 ( 例 如 拉 伸 ) 製 成 金 靥 罐 之 場 合 » 具 備 掻 佳 的 成 形 加 I 先 閲 1 :| 性 1 因 為 其 不 僅 與 金 腸 板 之 粘 著 性 極 佳 1 氣 味 保 持 性 ( 讀 背 1 I 保 番 性 ) 及 低 溫 耐 衝 擊 性 也 都 極 為 優 異 並 且 還 具 備 良 之 注 1 i 意 I 好 的 成 瞑 性 ( 例 如 擠 ‘成 形 加 工 性 及 可 位 伸 性 ) » 因 此 事 項 1 1 適 用 於 飲 料 雄 或 食 品 罐 等 金 屬 罐 〇 1 金 鼷 繙 之 内 表 面 和 外 表 面 通 常 都 會 被 覆 塗 雇 以 防 止 腐 寫 本 頁 i. 1 蝕 〇 為 簡 化 製 程 » 並 改 良 術 生 條 件 及 防 止 污 染 等 > 最 近 1 1 已 開 發 出 一 種 不 使 用 有 機 溶 劑 而 使 金 属 罐 具 備 防 绣 性 之 1 I 方 法 〇 而 最 廣 泛 使 用 的 方 法 是 将 熱 塑 性 樹 脂 薄 膜 塗 覆 在 1 1 鍍 錫 銷 板 無 鎢 銷 板 或 鋁 板 等 金 靥 板 表 面 之 後 • 再 利 用 訂 I 拉 伸 成 形 方 法 製 成 金 屬 罐 0 躭 熱 塑 性 樹 脂 薄 膜 而 曰 * 通 1 1 1 常 是 使 用 聚 酯 薄 膜 Q 1 i 曰 本 專 利 特 開 昭 56 -J 0 4 5 1 號 公 報 及 B 本 專 利 恃 閉 平 1 - 1 I 132546號 公 報 掲 示 — 種 經 由 一 低 熔 黏 聚 酯 之 粘 著 層 積 層 1 A 在 金 颶 板 上 之 雙 軸 拉 伸 聚 對 苯 二 甲 酸 乙 二 酯 薄 瞑 如 此 1 得 到 的 積 層 金 屬 板 則 做 為 製 罐 材 料 使 用 〇 雖 然 雙 軸 拉 伸 i 1 聚 對 苯 二 甲 酸 乙 二 酯 薄 膜 具 備 m 佳 的 耐 熱 性 和 保 番 性 % 1 1 但 其 成 形 加 工 性 卻 顯 得 不 足 » 因 此 在 製 罐 加 X 的 過 程 中 f * 薄 膜 很 容 易 因 殺 青 形 成 撤 開 裂 或 破 裂 t 而 造 成 比 較 大 I Λ* 的 變 形 〇 1 1 在 B 本 專 利 特 開 平 1- 192545號 -3 - 公 報 及 曰 本 専 利 特 開 平 羼1 I 1 1 1 1 張 紙 本 举 標 家 圃 國 中 用 適 Μ 公 97 2 434 彳 4 4 A7 經濟部中央標準局貝工消费合作社印製 _._B7_五、發明説明(> ) 2-57339號公報中掲示一種將非晶性或結晶性極低之芳 族聚醱材料積層在金屬板上,所得到的積層金屬板則做 為製罐材料使用。 雖然該非晶性或結晶性極低之芳族聚酯薄膜具備棰佳 的成形加工性,但保香性卻很差,而且在後處理過程中 ,例如製罐之後的印刷或高溫殺菌處理,或長期儲存的 過程中很容易變脆,因泚當其承受外力衝擊時,很容易 變質並産生裂痕。 歐洲專利EP-A-0653455 A1中掲示一種積層在金屬上 之多層膜,其第一層(A1)是熔點高於20ITC之聚酯樹脂 ,第二層(A2)是聚硝酸酯或由熔黏高於20(TC之聚酯樹 脂與聚硪酸酯組成之樹脂组成物,而樹脂組成物中聚磺 酸酯樹脂之含量相對於聚酯樹脂與聚磺酸酯樹脂之總重 量基底,至少在1重量%以上;當此種多層膜積層在金 屬板上之後,進行衝擊並通電(酎衝擊試驗),顯示其 電流值不到fl.laA;總厚度則在5-100//11之範圍内。 然而,歐洲專利EP-A-0653455 A1中並沒有提到第二 層之樹脂組成物中是否同時使用兩種不同的聚酯。 本發明的目的之一是提供一種新頴的積層在金屬板上 之多層膜。 本發明另一目的是提供一種積層在金屬板上之多層膜 ,此種没有被著色且不含任何氣泡之多層膜具備極佳的 成形加工性,因此在擠製成形的過程中不曾發生”熔融 攝盪(neltswing)"現象,而在拉伸過程中也不會破裂。 * —. n I ' n ϋ 東 (诗先閲讀背面之注意事項孑k寫本頁) 本紙張尺度適用中國國家標率(CNS )八4規格(210X297公釐) A7 434 14 4 B7 ____ 五、發明説明(々) 本發明另一目的是提供一種積層在金屬板上之多層膜 ,其不僅具備極佳的低溫耐衝擊性及與金臑板之粘著性 ,氣味保持性或保香性(以下均簡稱保香性)也棰為優 異,並且還具備良好的成膜性(例如擠製成形加工性及 可拉伸性)〇 本發明其他目的和優點經由以下敘述將可以更為明顯 根據本發明,上述積層在金靥上之雙軸拉伸薄膜之目 的和優點均可以蒱得,此積層膜之組成如下: (A) 由以對苯二甲酸乙二酯為主重複單位組成之聚酯 層形成第一層, (B) 由聚酯與聚磺酸酯組成之樹脂組成物形成第二層 ,所諝樹脂组成物實質上含有如下化學式⑴所示之重複 單位: (請先閲讀背面之注意事項-Γΐκ-寫本頁) 尺 張 -纸 |本434 彳 44 A7 B7 Printed by the Shellfish Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs 5. Description of the invention (〆) 1 1 This invention is based on a biaxially stretched thin layer of gold laminated on a gold frame. f The present invention is a double-layer stretch film 1 | film t laminated on a metal frame, and this thin layer is laminated on a metal plate before canning and adding X. Please make 1 1 1 (such as stretching) In the case of gold tin cans »It has excellent molding and I. Read 1: | Sex 1 because it not only has excellent adhesion to the gold intestine plate 1 odor retention (read back 1 I retention) and low temperature resistance The impact properties are also extremely excellent and also have a good note. 1 i. I. Good forming properties (such as extrusion processability and stretchability) »Therefore, item 1 1 is suitable for metal cans such as beverage males and food cans. 01 The inner and outer surfaces of the maggot I ’m writing to prevent corrosion on this page. I. 1 Etching. To simplify the process »and improve the operating conditions and prevent pollution, etc. > Recently 1 1 Has developed a metal can with anti-embroidery resistance without using organic solvents. 1 I Method 0 The most widely used method is to coat a thermoplastic resin film on the surface of a gold-plated plate such as a tin-plated pin plate without a tungsten pin plate or an aluminum plate. Resin film * 1 1 1 is often used polyester film Q 1 i Japanese Patent Laid-Open No. Sho 56 -J 0 4 5 1 and B Japanese Patent No. 1- 1 I 132546 shows- The laminated metal sheet obtained by laminating a low-melt polyester adhesive layer 1 A biaxially stretched polyethylene terephthalate on a gold hurdle sheet 1 is used as a can material. Biaxially stretched i 1 poly Ethylene terephthalate film has good heat resistance and heat retention% 1 1 but its forming processability is not enough »Therefore, during the process of adding X to the can, f * film is easily broken due to cyanide formation or cracking. Deformation caused by breaking t causes a relatively large I Λ * 〇 1 1 Used in B Japanese Patent Laid-Open No. 1-192545-3-Gazette and Japanese Bento Lit Kaiping 1 I 1 1 1 1 Applicable to the public 97 2 434 彳 4 4 A7 Printed by the Shellfish Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs _._ B7_ V. Description of the Invention (>) No. 2-57339 shows a method to reduce the amorphousness or crystallinity to extremely low The aromatic polyfluorene material is laminated on a metal plate, and the obtained laminated metal plate is used as a can-making material. Although the amorphous or extremely low-crystalline aromatic polyester film has excellent formability, it has poor fragrance retention, and is used in post-processing processes, such as printing after canning or high-temperature sterilization, or It is easy to become brittle during long-term storage, because when it is subjected to external force, it is easy to deteriorate and crack. European patent EP-A-0653455 A1 shows a multilayer film laminated on a metal. The first layer (A1) is a polyester resin with a melting point higher than 20ITC, and the second layer (A2) is a polynitrate or melt-bonded. A resin composition of more than 20 ° C of a polyester resin and a polyacrylate, and the content of the polysulfonate resin in the resin composition is relative to the total weight of the polyester resin and the polysulfonate resin. 1% by weight or more; when this multilayer film is laminated on a metal plate, it is impacted and energized (酎 impact test), showing that its current value is less than fl.laA; the total thickness is in the range of 5-100 // 11 However, the European patent EP-A-0653455 A1 does not mention whether two different polyesters are used in the resin composition of the second layer at the same time. One of the objects of the present invention is to provide a new layer of laminated metal sheet The other object of the present invention is to provide a multilayer film laminated on a metal plate. This multilayer film, which is not colored and does not contain any bubbles, has excellent forming processability, and therefore is extruded. "Neltswing" never happened " phenomenon, and it will not break during the stretching process. * —. n I 'n ϋ East (Notes on the back of the poem before reading 孑 k write this page) This paper scale applies to China National Standards (CNS) 4 specifications (210X297 mm) A7 434 14 4 B7 ____ 5. Description of the invention (々) Another object of the present invention is to provide a multilayer film laminated on a metal plate, which not only has excellent low temperature impact resistance and gold resistance. The fascia is also excellent in adhesiveness, odor retention, or aroma retention (hereinafter referred to as aroma retention), and also has good film-forming properties (such as extrusion molding processability and stretchability). Other objects and advantages of the invention will become more apparent through the following description. According to the present invention, the objects and advantages of the above-mentioned laminated biaxially stretched film on the gold foil can be obtained. The composition of the laminated film is as follows: (A) The polyester layer composed of ethylene terephthalate as the main repeating unit forms the first layer, (B) the resin layer composed of polyester and polysulfonate forms the second layer, and the resin composition substantially contains The repeating unit shown in the following chemical formula ⑴: ( Please read the notes on the back-Γΐκ-Write this page) Ruler-Paper |
合 結5-5-以含 含司之 、也結 基 2 鐽^Ξ 其 之 子R1子 原 ,原 硪出碩 烷,戎環 之 子^ ^ 00 ^ ^ 硪 璟0 在 環 齒 含 從 0 且 而 立 0 自 各 η 出0 中 群 之 子 原 素 齒 及 或 準 標 家 圉 i國 i中 -用 適 選 中 群 之 基 有 再 外 另 基 燏 值和 基 ο 苯表 、代 基僳 烷, 之立、 子獨 原自 硪各 0 η -5和Consolidate 5-5- to contain the base, also the base 2 鐽 ^ Ξ Its son R1 child original, the original 硪 out of a large alkane, the son of the Rong ring ^ ^ 00 ^ ^ 硪 璟 0 in the ring teeth containing 0 and stand 0 Out of each η, the primary element of the group and the quasi-standard home group-the basis of the selected group is the external base value and the base ο benzene table, substituted oxane, Ziduyuan has its own 0 η -5 and
一釐 公 7 29 X 經濟部中央樣準局負工消費合作社印製 434 彳 4 4 A7 B7五、發明説明(4 ) 聚碩酸酯和聚酯之含量相對於其總重量基底,分別為20 -50重置ί和50-80重量X;聚凿實質上是包括以對苯二甲 酸乙二酯為主重複單位組成且末端羧基濃度在5當fi/ l〇e克(eq./106 g)以上之第一種聚酯及以對苯二甲酸 丁二酯為主重複單位組成且末端羧基湊度在20酋量/10 克以下之第二種聚酯;第一種聚酯和第二種聚酯之含董 相對於其總重量基底,,都在10-30重童X之間;而其中 (C)第一層和第二層之平面拉伸偽數都在0.05-0.10之 範圍内β 如上所述,本發明雙軸拉伸薄瞑包含兩層。其中第一 層是由以對苯二甲酸乙二酯為主重複單位组成之聚酯所 形成。聚酯中對苯二甲酸乙二酯之含量相對於缠重複單 位基底,至少在5G莫耳5£以上,而以8G莫耳5;以上為較佳 ,又以85莫耳3t以上為更佳,90莫耳X以上又更佳。在本 發明中,相對於總重複單位基底,含8 0 - 1 0 0莫耳X對苯 二甲酸乙二酯之聚酯很輕易就可以製得,而且很方便使 用。 能夠與此類聚酯共聚合的二羧酸例子包括芳族二羧酸 ,例如異苯二甲酸、苯二甲酸和2,6-或2,7-萘二甲酸; 脂族二羧酸,例如己二酸、王二酸、癸二酸和癸二甲酸 :脂環二羧酸,例如1,4 -琛己烷二甲酸。能夠與此類聚 酯共聚合的二元醇成分之例子包括脂族二醇,例如二甘 醇、丁二醇和己二醇;以及脂環二醇,例如1,4-琛己二 甲醇β其軍獨或混合使用均可。 (請先閲讀背面之注意事項尸.V寫本頁) 本紙張尺度適用中國國家榡準(CNS ) Α4規格(210Χ29?公釐) 經濟部中央揉準局負工消费合作社印製 434144 A7 _.._B7 .五、發明説明(r ) 這些聚酯之熔黏都在20(TC以上,而以210·〇以上為較 佳。如果使用了低熔黏聚酯,則所裂得的薄膜之耐熱性 及耐衝擊性會比較差。 上述聚酯之本質粘度(在35«C之鄰氣苯酚中拥定)以 0.5-0.9為較佳,而以0_6-〇_8為特佳。 逭些聚酯可利用傳统之熔融聚合法製備。製備聚_時 所使用的觭媒比較好的邊鍺(Ge}化合物觸媒或敎(Ti)化 合物_媒。從降低寡聚物含量的觀點來看,較佳的聚合 法為固相聚合法。尤其當聚碩酸酷經混合及熔化之後, 在銻(Sb>化合物觸媒存在的情況下對聚酯進行聚合反慝 將幫肋去羧反應而産生會形成氣泡之二氣化硪β因此銻 觸媒並不適合。 構成本發明雙輪拉伸薄膜之第二層傺由聚硪酸酯輿聚 酯組成。 聚《酸_實質上包含以上化學式(1)所示之重複單位 。在以上化學式(1)中,R1和R2所代表的含1-5傭碩原 子之烷基可為直鍵或支鏈烷基,例如乙基、正丙基、異 丙基、正丁基、異丁基、戊基等。 (請先閲讀背面之注$項漭扠寫本頁) 己 環 和 基 戊 環 括 包 子 例 的 基 烷 琛 之 子 原 碩 環0 6 I 5 含 基 和 1 氣 含 、 的氟 表從 代你 所子 4 原 i素 鹵 0 述 所 上 如 子 例 之 基 烷 子 原 硪0 出0 中 群 等 溴 中 其 是 的 佳 較 中 位 單 複 •Γ: 3 之 示 所 0) 式 學 化 述 上 和 單 複 重 酯 酸 碩 A 酚 雙 之 ο 於 等 η 和 η 且 f 基 甲 為 本紙張尺度適用中國闺家橾準(CNS ) Λ4*ΜΜ 210X297公釐) 434144 經濟部中央標準局貝工消费合作社印裝 A7 B7五、發明説明(έ ) 位。 適用於本發明之聚硪酸酯,其中的重後單位可能舆上 述化學式(1)所示者相同,也可能是至少兩種如化學式 (1)所示不同類型之重複單位。 聚碩酸酯通常是在已知酸受體或分子量調節劑存在的 情況下利用相開二元酚舆溶於溶劑中(例如二氯甲烷) 之硪酸酯先質(例如光< 氣)之反應製得(界面聚合法) ,或利用相關二元酚與硪酸酯先質(例如硪酸二苯酯) 之酯交換反應製得(熔融聚合法)β 本發明所使用之聚硪酸酯可利用以下方法製得: 0)在界面聚合法中,以過量二元酚與硝酸酯先質反醞 之方法; ¢)在界面聚合法中,進行封端反應之方法; ⑶在界面聚合法中,調整二元·與碩酸酯先質比例之 方法; ⑷在熔融聚合法中,多元羥化合物是在聚合反醢完成 之後才加入之方法;以及 © —種方法,其中是以末端羥基含量在20莫耳/ 10 e 克以下之聚碳酸酯與適量二元酚進行熔融混合,必要時 還加入觸媒以使得聚碩酸酯與二元酚互相反應而提高末 端羥基之含量》 聚碩酸酯之拈度平均分子量以1〇〇G〇-4GO()()為較佳, 而以1 0 0 0 G - 3 5 0 G 0為更佳。 構成第二層之聚酯實質上包括以對苯二甲酸乙二酯為 -8 - (請先閱讀背面之注意事項ν4'寫本頁) 本紙張尺度適用中國國家標牟(CNS ) Α4規格(2ΙΟΧ297公釐) 經濟部中央樣準局負工消費合作社印裝 434 Μ 4 Α7 Β7五、發明説明(7 ) 主重複單位組成且末端羧基嬝度在5當量/10e克以上 之第一種聚酯,以及以對苯二甲酸丁二酯為主重複單位 紐成且末端羧基濃度在20當量/10e克以下之第二種聚 酯。 第一種聚酯之末端羧基濃度必須在5當最/10®克以 上。此末端羧基濃度如果在5當量/1G6克以下,則聚 硪酸酯在聚簾中之分散>性就比較差,如此薄膜将很難拉 伸,較壞的情況甚至無法拉伸。 末端羧基濃度以7當量/1G6克以上為較佳,而以12 當量/1G6克以上為更佳,又以15當量/106克為特佳 β末端羧基濃度最好是在20當量/10e克以下β 就以對苯二甲酸乙二酯為主重複單位组成之第一種聚 酯而言,上述用於第一種聚酯之例子均睦用,在此不多 赘述。 在第一種聚酯中,對苯二甲酸乙二_之含量相對於總 重複單位基底,以80-100奠耳X為較佳 在第二種聚酯中,對笨二甲酸丁二酯之含量相對於總 重複單位基底,至少在50重量X以上。此含量以至少80 契耳X為較佳,而以至少8 5莫耳X為更桂,至少8 5莫耳X 又更佳,待佳的是至少95奠耳 做為與第二種聚酯共聚合之第三層成分之二羧酸例子 包括:芳香族二羧酸,例如異苯二甲酸、苯二甲酸、2, 6-或2,7-萊二甲酸;脂族二羧酸,例如己二酸、壬二酸 、癸二酸和癸二甲酸;脂琛二羧酸,例如1,4-環己烷二 -9- (請先閲讀背面之注意事項/^寫本頁) 本纸張尺度適用中國國家搮準(CNS ) Α4規格(210><297公釐) 經濟部中央揉準局負工消费合作社印策 1 1 4 4434 1 4 4ti a7 _B7_____五、發明説明(f ) 甲酸·做為與第二種聚酯共聚合之另一種第三層成分之 二元醇例子包括:脂族二酵,例如二甘酵、丁二醇和己 二醇;以及脂琛二醇,例如丨,4 -琛己二甲酵。其單獨或 混合使用均可。 第二種聚_之末端羧基濃度必須在20當量/1Ge克以 下,而以17當量/10β克以下為較佳,又以5-17當量/ 106克為更佳,特佳的ν是5-15當量/1〇β克。 以對笨二甲酸丁二_為主重複單位組成之第二種聚鲔 的作用是要增強聚碩酸酯在聚酯相中之分散性,以抑制 擠製成形過程中"熔融攞盪Uelt swing)"之現象及在拉 伸過程中之破裂現象,而得以改良成膜性《此聚酯之末 端羧基濃度如高於20當量/ lfls克*則将不再具有改良 聚硪酸_之分散性及成膜性之效果》 第二種聚酯之熔黏最好在20(TC以上.而以210·Ό為更 佳。此熔點如果太低,則所製成的薄膜之耐熱性和耐衝 擊性都會不足β 第二種聚_之本質拈度(在35°C鄺氡苯酚中測定)以 0.6-1.6為較佳,而以0.7-1. 5為特佳。 如同上述以對苯二甲酸乙二酯為主重複單位組成之聚 酯一樣,使用鍺化合物觸媒或鈦化合物觸媒並利用固相 聚合法製備第二種聚酯是比較好的。鍺化合物之較佳例 子包括:⑴非晶氣化緒,⑵撖晶氣化緒,©在齡金屬、 齡土金屬或其混合物存在的情況下溶在二元醇中之氣化 緒溶液,⑷氣化緒之水溶液。鈦化合物之較佳例子包括 -I 0 - (請先聞讀背面之注意事項寫本頁) 本紙張尺度適用中國國家梯準(CNS ) A4規格(210X297公嫠) 434 1 4 4 ^ A7 B7 經濟部中央揉準局貝工消费合作社印掣 五、發明説明(9 ) 四丁氣钛及乙酸鈦等。 構成第二層的聚硪酸酯和聚酯之含量相對於其跑重量 基底,分別為20-50重董X和50-80重量X。如果聚®酸酿 之比率高於50重量X,朗在濟製成形的過程中"箱融摄强 之現象及在拉伸過程中之破裂現象都會頻頻發生,使得 成膜性也變差β如果聚硪酸酯之比率低於20重量X,則 低溫耐衡擊性將無法獲^得改良。 聚_中第一種聚酯和第二種聚酯之含量相對於第一種 聚酯與第二種聚酯之结重量基底,都在10-90重ft X之範圃内《 如果第二種聚酯之比率高於90重量X,或第一種聚酯 之tb率低於1〇重量X,則所製得的薄膜會被箸色,而且 也會因為其與聚砍酸酯之去羧反_而形成二氧化硪,導 致其中含有氣泡,這樣將很難形成薄膜。反之,如果第 二種聚酯之比率高於90重童X,則將無法改良聚磺酸酯 在聚酯相中之分散性,因此在擠製成形過程中"熔融振 通"之現象及在拉伸過程中之破裂現象也無法獾得抑制 之效果。 第一種聚酯對第二種聚酯之摻合比(重量X)以20-85/ 80-15為較佳,而以4 0 -8 0/6 0- 2 0為更佳。 在第二層中所含之聚碩酸酯具有末端羥基〇此末端羥 基之作用是要使第二層(Β)要舆金羼板黏合在一起•在 第二層中聚碩酸酯和聚酯之末端羥基缌濃度以至少25當 量/i〇e克為較佳•而以至少3 0當董/1〇β克為更佳, -11- .---------— 装------、1Τ------^ (請先閲讀背面之注意事項:¼寫本頁) 本紙張尺度逋用中®國家梂準(CNS ) A4规格< 2I0X297公釐) 經濟部中夬橾率局員工消费合作社印製 A? 4 1 4 4Λ3 A7 B7 " . I I 五、發明说明(l° ) 又以40-200當量/10β克為最佳· 如上所述,第二層是由聚胡酸®與聚酿之組成物所形 成。組成物中最好含有磷化合物。磷化合物可抑制聚硪 酸酯與聚酯之反應,因此得以防止製成之薄膜由於去羧 反鼴産生二氧化硪所導致的著色現象。然而’如果碟含 暈太离,則第二聚®所具有的改良聚硪酸醏分散性之效 果將逋到破壊,因此其^成膜性也變差了 磷化合物之含 量以2 G - 1 0 0 ρ ρ 為較佳,而以4 0 _ 1 〇 〇 Ρ Ρ »為更佳,又以4 0 -50ΡΡ*為最佳。 磷化合物不管是無機或有機皆可,例如亞转酸、磷酸 、焦磷酸、匍磷酸、及其鹽類、二烷基和三烷基瞵、二 芳基和三芳基瞵、箪烷基和二烷基次除酸、單芳基和二 芳基麟酸、亞磷酸酯、磷酸酯、聚磷酸等,其中以亞磷 酸、磷酸、亞磷酸®和磷酸酯為較佳》醋類的例子包括 低級烷基(如甲基和乙基)歯、苯酯、二元醇(如乙二 醇)之_類、等等β 磷化合物可在製造聚酯和/或聚碩酸酯之過程中加入 ,也可在熔融擠製的過程中加入。 第二層中含聚硝酸酯與聚酵之組成物具有海/島狀結 晶,其中聚硪酸酯是以島狀型態(分散柙)分散在海狀 聚酯中(連鑲相)。聚硪酸酯島狀物看起來是一園粒子 β如果對箸雙_拉伸薄膜之设長及横長方向切割•得到 切面上粒子之平均長徑在〇.1-20# 之間β具儎此種平 均長徑之粒子如分散成獨立相(島狀)•則在擠製成形 -1 2- (請先閱讀背面之注意事項萝%寫本頁) 本纸張尺度適用中國固家標率(CNS ) Α4規格(210Χ297公嫠) 434144- 經濟部中失梂準局員工消费合作社印製 A7 B7五、發明説明(") 的過程中”熔融振盥"之現象及在拉伸過程中之破裂現象 均可獲得抑制,因此得到的是耐衝擊性®佳之雙轎拉伸 薄膜》 上述切面上聚硪酸酯鳥狀物之大小最好在0.1-10;« 之間,而以〇 1-5 # B為更佳。 在本發明雙軸拉伸薄膜中,構成其第一層的聚酯以及 構成第二層之聚碩酸酴與聚酯之組成物中,必要時可以 分散或摻入一些添加劑,例如抗氣化_、熱安定_、紫 外光吸收劑、可塑劑、無機粒子、有機粒子、抗靜霣劑 等β 本發明雙軸拉伸薄膜之中心線平均表面粗楢度Ua)以 至少5-150πβ為較佳,而以l〇-6fln·為更佳e Ra如果能在 上述範圍内,就能夠輕易製得薄睽》 為諝整雙軸拉伸薄膜之表面粗糙度(Ra)能在上述5-150η·範圍内•可将趙滑爾加人第一層之聚酯中,和/ 或加入第二層之聚碩酸醱與聚酯之組成物中,或對聚磺 酸酯相及聚醣相進行適度的相分離》 加入的潤滑劑,不管是無機或有機均可.而以無機濶 滑劑為較佳〇 無機潤滑劑的例子包括:矽石、鋁氣、二氣化鈦、硪 酸鈣、碕酸餌等。有機涠滑劑的例子包括:交職聚苯乙 烯粒子、交聯矽樹脂粒子等。潤滑劑之平均粒徑在2.5 以下是比較好的,而以〇 · 01-2 _ 0私置為較佳。當潤滑 劑之平均粒徑大於2.5# «時,針孔會在成形階段已經變 -1 3- I------------參------ir------東 {請先閲讀背面之注意事項罗寫本頁) 本紙張尺度適用中国國家標準(CNS ) A4现格(2I0X297公釐) 434 M4 A7 ______B7五、發明説明(> > 形的部位之較粗粒子(例如10jK飄以上j處開始形成, 靦重時甚至導致破裂。 從抗針孔性的觀黠來看,待性的箱滑涮是平均粒悝在 2.5// b以下,且平均粒徑比(長徑/短徑)為j 〇-1 2 之單分散性潤滑劑,例如球狀矽石、球狀二氣化鈦球 狀結' 球狀交K矽鋦樹脂粒子等。 薄膜之表面粗梅度泰根據JIS B (1601-1982方法測得 之中心線平均表面粗櫨度,其值表示如(Ra:n·),公式 如下,其中L像在中心線方向薄膜表面粗糙度曲線擷取 的長度拥定值•此擷取部份之中心線代表X 舆此部 份垂直放大的方向代表Ϊ值,表面粗糙度曲線以Y = f(x) 表示》One centimeter 7 29 X Printed by the Central Procurement Bureau of the Ministry of Economic Affairs and Consumer Cooperatives 434 彳 4 4 A7 B7 V. Description of the invention (4) The content of the polyester and polyester relative to their total weight base is 20, respectively -50 reset and 50-80 weight X; polychisel essentially consists of ethylene terephthalate as the main repeating unit and the terminal carboxyl group concentration is 5 when fi / l0e grams (eq./106 g ) The first polyester above and the second polyester composed mainly of butyl terephthalate and repeating units, and the terminal carboxyl group content is less than 20 μg / 10 g; the first polyester and the second Relative to the total weight of the base, the content of this polyester is between 10-30 weights X; and (C) the plane tensile pseudo numbers of the first and second layers are in the range of 0.05-0.10. Inner β As described above, the biaxially stretched sheet of the present invention includes two layers. The first layer is formed of a polyester composed of ethylene terephthalate as the main repeating unit. The content of ethylene terephthalate in polyester relative to the substrate of the repeating unit is at least 5 G Mol 5 £, and 8 G Mol 5; the above is better, and 85 Mo 3 3t is more preferred , 90 Moore X and better. In the present invention, a polyester containing 80 to 100 moles of ethylene terephthalate can be easily produced with respect to the total repeating unit substrate, and is convenient to use. Examples of dicarboxylic acids that can be copolymerized with such polyesters include aromatic dicarboxylic acids such as isophthalic acid, phthalic acid and 2,6- or 2,7-naphthalenedicarboxylic acid; aliphatic dicarboxylic acids such as Adipic acid, adipic acid, sebacic acid, and sebacic acid: alicyclic dicarboxylic acids, such as 1,4-hexanehexanedicarboxylic acid. Examples of glycol components that can be copolymerized with such polyesters include aliphatic diols, such as diethylene glycol, butanediol, and hexanediol; and alicyclic diols, such as 1,4-hexanehexanedimethanol β which Military independence or mixed use. (Please read the note on the back. V write this page) This paper size is applicable to China National Standard (CNS) Α4 size (210 × 29? Mm) Printed by the Central Consumers ’Bureau of the Ministry of Economic Affairs and Consumer Cooperatives 434144 A7 _. ._B7. V. Description of the invention (r) The melt adhesion of these polyesters is above 20 (TC, and more preferably 210 · 0 or more. If low-melt polyester is used, the heat resistance of the resulting film is The impact resistance and impact resistance will be relatively poor. The intrinsic viscosity of the above polyester (retained in the gaseous phenol of 35 «C) is preferably 0.5-0.9, and particularly preferably 0_6-〇_8. Ester can be prepared by the traditional melt polymerization method. The side-germanium (Ge) compound catalyst or the gadolinium (Ti) compound catalyst used in the preparation of poly_ is better. From the viewpoint of reducing the content of oligomers, The preferred polymerization method is a solid-phase polymerization method. Especially after the polymer acid is mixed and melted, the polymerization reaction of the polyester in the presence of an antimony (Sb> compound catalyst) will help the ribs to decarboxylate. The second gaseous 硪 β which is formed by the formation of air bubbles is therefore not suitable for the antimony catalyst. The second layer of fluorene is composed of polyester and polyester. The polyacid contains essentially the repeating unit shown in the above chemical formula (1). In the above chemical formula (1), R1 and R2 represent 1-5 The alkyl group of the main atom can be a straight or branched chain alkyl group, such as ethyl, n-propyl, isopropyl, n-butyl, isobutyl, pentyl, etc. (Please read the note on the back first. Fork to write on this page) Hexane and pentyl rings include the examples of the children of the alkanes, the original master ring 0 6 I 5 containing radicals and 1 gas containing, the fluorine table from the substitution of your son 4 original halogen halogen 0 as described above For example, the basic alkyl group of the original group is 0, 0 is the middle group and the bromine is better than the median single complex. Γ: 3 is shown. Of ο equal to η and η and f base paper is based on the Chinese paper standard (CNS) Λ4 * MM 210X297 mm) 434144 Printed by the Bayer Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs A7 B7 V. Description of the invention ( The polyacrylates suitable for use in the present invention may have a heavy unit that is based on the above formula (1). The same, or it may be at least two different types of repeating units as shown in chemical formula (1). Polyesters usually use phase-opened dihydric phenol to dissolve in the presence of known acid acceptors or molecular weight regulators. Prepared by the reaction of a precursor of an acetic acid ester in a solvent (such as dichloromethane) (such as light < (Melt polymerization method) β produced by transesterification reaction of ester) β The polyphosphonate used in the present invention can be prepared by the following methods: 0) In the interfacial polymerization method, excess dihydric phenol and nitrate precursors are reacted. Method; ¢) the method of carrying out the end-capping reaction in the interfacial polymerization method; ⑶ the method of adjusting the ratio of the binary and the precursors in the interfacial polymerization method; ⑷ in the melt polymerization method, the polyhydric hydroxy compound is A method for adding after the polymerization reaction is completed; and a method in which a polycarbonate having a terminal hydroxyl content of less than 20 mols per 10 e g is melt-mixed with an appropriate amount of a dihydric phenol, and a contact is added if necessary Mediator Phenols react with each other to increase the content of terminal hydroxyl groups. "The average molecular weight of polyether ester is preferably 100 Go-4 GO () (), and more preferably 100 G-3 50 G 0. good. The polyester constituting the second layer essentially includes ethylene terephthalate as -8-(Please read the note on the back first ν4 'to write this page) This paper size applies to China National Standards (CNS) Α4 specifications ( 2 ΙΟχ297 mm) Printed by the Central Procurement Bureau of the Ministry of Economic Affairs, Consumer Work Cooperative, 434 M 4 Α7 Β7 V. Description of the invention (7) The first polyester consisting of a main repeating unit and a terminal carboxyl group degree of 5 equivalent / 10e or more And a second polyester with butylene terephthalate as the main repeating unit and a terminal carboxyl group concentration of 20 equivalents / 10e or less. The first polyester must have a terminal carboxyl group concentration of 5 to 10/10 g. If the concentration of the terminal carboxyl group is less than 5 equivalents / 1G6 g, the dispersion > properties of the polyacrylate in the poly curtain will be poor, so that the film will be difficult to stretch, and even in a worse case, it cannot be stretched. The terminal carboxyl group concentration is preferably 7 equivalents / 1G6 g or more, and more preferably 12 equivalents / 1G6 g or more, and 15 equivalents / 106 g is particularly preferable. The β terminal carboxyl group concentration is preferably 20 equivalents / 10e g or less β As far as the first polyester composed of ethylene terephthalate as the main repeating unit is concerned, the above-mentioned examples for the first polyester are all compatible, so I will not repeat them here. In the first polyester, the content of ethylene terephthalate relative to the total repeating unit substrate is preferably 80-100 Molar X. In the second polyester, the content of The content is at least 50 weight X or more relative to the total repeating unit base. This content is preferably at least 80 deciles X, more preferably at least 85 moles X, and at least 85 moles X is even better. At least 95 moles is preferred as the second polyester Examples of the dicarboxylic acids of the copolymerized third layer include: aromatic dicarboxylic acids such as isophthalic acid, phthalic acid, 2, 6- or 2,7-dicarboxylic acid; aliphatic dicarboxylic acids such as Adipic acid, azelaic acid, sebacic acid, and sebacic acid; fatty acids such as 1,4-cyclohexanedi-9- (please read the notes on the back first / write this page) Zhang scale is applicable to China National Standard for Standards (CNS) Α4 (210 > < 297 mm) Printed by the Central Labor Bureau of the Ministry of Economic Affairs and Consumer Cooperatives 1 1 4 4434 1 4 4ti a7 _B7_____ 5. Description of the invention (f) Formic acid · Examples of glycols which are another third layer component copolymerized with the second polyester include: aliphatic secondary enzymes such as diglycol, butanediol, and hexanediol; and aliphatic diols such as丨, 4-Chen Dimethonate. They can be used alone or in combination. The concentration of the terminal carboxyl group of the second poly_ must be less than 20 equivalents / 1Ge g, preferably less than 17 equivalents / 10βg, and more preferably 5-17 equivalents / 106 g. The particularly preferred ν is 5- 15 equivalents / 10 gram. The second type of polyfluorene composed of butadiene dibenzoate as the main repeating unit is to enhance the dispersion of the polyester in the polyester phase in order to suppress the melt-fluid Uelt during extrusion. swing) " phenomenon and the rupture phenomenon during the stretching process, which can improve the film-forming property "If the terminal carboxyl group concentration of this polyester is higher than 20 equivalents / lfls gram *, it will no longer have improved polyacid The effect of dispersibility and film-forming properties "The melt adhesion of the second polyester is preferably 20 ° C or more. 210 · Ό is more preferred. If this melting point is too low, the heat resistance of the resulting film and Impact resistance will be less than β. The intrinsic degree of the second poly (determined in phenol at 35 ° C) is preferably from 0.6 to 1.6, and particularly from 0.7 to 1.5. As mentioned above with p-benzene Ethylene diformate is the same as polyester with main repeating unit. It is better to use the germanium compound catalyst or titanium compound catalyst and use solid phase polymerization to prepare the second polyester. The preferred examples of germanium compounds include: ⑴Amorphous gasification thread, ⑵ 撖 Crystal gasification thread, © in age metals, age earth metals or mixtures thereof Under normal circumstances, it is dissolved in glycol, and it is dissolved in diol. The preferred examples of titanium compounds include -I 0-(Please read the notes on the back to write this page) This paper is applicable to China National Ladder Standard (CNS) A4 specification (210X297 cm) 434 1 4 4 ^ A7 B7 Printed by the Central Government Bureau of the Ministry of Economic Affairs, Shellfish Consumer Cooperative, V. Description of the invention (9) Tetrabutyl titanium, titanium acetate, etc. The content of the polyester and polyester in the second layer is 20-50 wt% X and 50-80 wt X, respectively. During the forming process, the phenomenon of “box melting and strong shooting” and the rupture phenomenon in the stretching process will frequently occur, making the film formation worse. Β If the ratio of polyacrylate is less than 20 weight X, the low temperature resistance The balance will not be improved. The content of the first polyester and the second polyester in the polymer is 10-90 weight relative to the weight of the first polyester and the second polyester. In the range of ft X, "If the ratio of the second polyester is higher than 90 weight X, or the tb ratio of the first polyester is less than 10 weight X , The resulting film will be blackened, and it will also form hafnium dioxide due to the decarboxylation of polycarboxylate, resulting in the inclusion of air bubbles, which will make it difficult to form a thin film. Conversely, if the second If the ratio of this kind of polyester is higher than 90%, the dispersion of polysulfonate in the polyester phase cannot be improved. Therefore, the phenomenon of "melt vibration" during extrusion and the stretching process The cracking phenomenon cannot be suppressed. The blending ratio (weight X) of the first polyester to the second polyester is preferably 20-85 / 80-15, and 4 0 -8 0 / 6 0- 2 0 is better. The polyester contained in the second layer has terminal hydroxyl groups. The purpose of this terminal hydroxyl group is to make the second layer (B) adhere to the gold plate. The terminal hydroxyl hydrazone concentration of the ester is preferably at least 25 equivalents / ioe gram • and more preferably at least 30 equivalents / 10 gram, -11- .----------- ------ 、 1Τ ------ ^ (Please read the note on the back first: write this page) This paper is in use ® National Standard (CNS) A4 Specification & 2I0X297 mm) Printed by the Consumer Cooperatives of the China Economic and Trade Bureau of the Ministry of Economic Affairs A? 4 1 4 4Λ3 A7 B7 ". II V. Description of the invention (l °) 40-200 equivalent / 10βg is the best. The second layer is formed by the composition of Polyuronic Acid® and Poly Brew. The composition preferably contains a phosphorus compound. Phosphorus compounds can inhibit the reaction between polyesters and polyesters, thus preventing the coloration of the resulting films due to decarboxylation and osmium dioxide. However, if the dish contains too much halo, the effect of the improved polydispersity of the second poly® will be reduced, so its film-forming properties are also deteriorated. The content of the phosphorus compound is 2 G-1 0 0 ρ ρ is preferred, and 40 _ 1 〇〇ΡΡ »is more preferred, and 40-50 PP * is most preferred. Phosphorous compounds can be either inorganic or organic, such as hypophosphoric acid, phosphoric acid, pyrophosphoric acid, phosphonium phosphate, and salts thereof, dialkyl and trialkylphosphonium, diaryl and triarylphosphonium, phosphonium alkyl, and diphosphonium Alkyl hypo-acid, monoaryl and diaryllinamic acid, phosphites, phosphates, polyphosphoric acid, etc. Among them, phosphorous acid, phosphoric acid, phosphorous acid® and phosphate are preferred. Examples of vinegars include lower grades Alkyl (such as methyl and ethyl) fluorene, phenyl esters, glycols (such as ethylene glycol), etc. Beta phosphorus compounds can be added during the manufacture of polyesters and / or polyesters, It can also be added during melt extrusion. The composition containing polynitrate and polymerase in the second layer has sea / island crystals, in which the polyacrylate is dispersed in an island-like form (dispersed 柙) in a sea-like polyester (continuous mosaic phase). Polyurethane islands appear to be one-round particles. If you cut the length and width of the double-stretched film, the average length of the particles on the cut surface is between 0.1-20 #. If such particles with an average major diameter are dispersed into independent phases (islands), then they are extruded into a shape. 1 2- (Please read the precautions on the back first. Write this page) This paper is applicable to the Chinese standard (CNS) A4 specification (210 × 297 gong) 434144- The printing of A7 B7 by the Consumer Cooperatives of the Ministry of Economic Affairs, Bureau of Labor and Social Security, China 5. The phenomenon of "melt vibration" in the process of " ", and the stretching process The cracking phenomenon can be suppressed, so the impact resistance ® excellent double sedan stretch film is obtained. The size of the polyacrylic bird on the above cut surface is preferably between 0.1-10; «, and 〇 1-5 #B is more preferred. In the biaxially stretched film of the present invention, the polyester constituting the first layer thereof and the composition of polyethylene terephthalate and polyester constituting the second layer may be dispersed or dispersed as necessary. Incorporates additives such as anti-gasification_, thermal stability_, UV absorber, plasticizer, Particles, organic particles, antistatic agents, etc. β The centerline average surface roughness Ua) of the biaxially stretched film of the present invention is preferably at least 5-150πβ, and more preferably 10-6fln. E Ra if If it is within the above range, it is easy to make a thin film. "For finishing the surface roughness (Ra) of the biaxially stretched film can be within the above 5-150η · range. • You can add Zhao Huaerga to the first layer. Polyester, and / or added to the second layer of polysulfonic acid and polyester composition, or moderate phase separation of polysulfonate phase and polysaccharide phase "added lubricant, whether inorganic or Both organic and inorganic lubricants are preferred. Examples of inorganic lubricants include: silica, aluminum gas, titanium dioxide, calcium acetate, calcium acid bait, etc. Examples of organic lubricants include: Polystyrene particles, cross-linked silicone resin particles, etc. The average particle size of the lubricant is better than 2.5, and 0 · 01-2 _ 0 is better. When the average particle size of the lubricant is greater than 2.5 # «When the pinhole has changed during the forming phase -1 3- I ------------ Refer to ---- ir ------ East {Please read the back Attention Xiang Luo wrote this page) This paper size is in accordance with Chinese National Standard (CNS). A4 is now standard (2I0X297mm) 434 M4 A7 ______B7 V. Description of the invention (> > From the point of view of anti-pinhole resistance, the average grain size is less than 2.5 // b, and the average grain size ratio (longer diameter / shorter diameter) ) Is a monodisperse lubricant of j 〇-12, for example, spherical silica, spherical digassed titanium spherical knots, spherical interstitial silica resin particles, and the like. The surface roughness of the film is measured according to JIS B (1601-1982). The average surface roughness of the centerline is expressed as (Ra: n ·). The formula is as follows, where L image is rough in the centerline direction. The length of the degree curve captures a fixed value. • The center line of the extracted part represents X and the direction of vertical magnification of this part represents the threshold value. The surface roughness curve is represented by Y = f (x).
經濟部中央標奉局員工消费合作社印製 中 靥。的保的致 包 值 一成觸之佳不 *0) 定 第構接層掻分掉: 拥 成磨相二備成變備 次。形積互第具味味製 五值酯者板,卻氣香法 為均聚兩属觸餍有的方 Ka平以,金接 1 的中下 ,的换層與接第中物以 Μ 到構二是直之物含用 25得結第層物層含内利 0.次層成二含二内得可4-為四積形第内第罐免膜-1 度餘之 _ 之之護Β也薄 長其瞑聚膜雄保金,伸 準取薄和層.屬以使上拉 擦後伸酯積金用以面軸 ,之拉酸,與但得表雙 中值軸碩構則,此膜之 明大雙聚结層差因薄構 發最明以種一較,到结 本掉發後此第tb性附餍 在除本然於而性香圾雙 剔 ,由,香保被 1-111— —1 裝— —訂— I — I i^ {請先聞讀背面之注項f%寫本頁) 本纸張尺度適用中國國家橾率(CNS ) A4洗格(210X297公釐) 434 1 44 經濟部中央標準局貝工消费合作社印裂 A7 ____B7____五、發明説明(Η ) 括分別将構成不同層的聚酯以及聚磺酸酯與聚酯之組成 物熔融、共擠製、積層並熔合在一起、雙軸拉伸及熱固 化等步驟之方法,⑵包括分別將聚硪酸酯以及聚磺酸® 與聚酯之組成物熔融及擠製形成傾別的薄膜、拉伸、積 層並將薄睽熔合在一起等步驟之方法。 雙軸拉伸之方法包括顆序雙軸拉伸方法、同時雙軸拉 伸方法、充氣方法(inflation Bethod)等* 如此製得的本發明薄膜之结厚度介於5-100#·之間, 而以10-75# 為較佳β第一層(A)對第二層(B>之厚度比 (A/B)以1/99-5G/50為較佳,而以5/95-40/60為更佳, 又以1 G / 9 0 - 3 0 / 7 0為待佳 本發明雙軸拉伸薄膜之第一層(Α)和第二層(Β>之平面 拉伸傺數必須在G . 0 5 - 0 . 1 0之間。 f = l(nx +ny )/2 卜 ηζ 其中nx,ny和分別代表縱向,播向和厚度方向 之折射率》 上述方程式中之折射例是依下述方法_定《· 在阿貝(Abbe)折射計的目鏡侧裝置一福振Μ分析儀, 然後使用箪色光(NaD射線)測定所諝各方向薄膜之折射 率。使用的固定液為二碘甲烷,测定溫度為25刃。 平面拉伸镍數如果太小,則當深拉成形之拉伸比太 高時,將會有裂痕問題發生,平面拉伸你數如太大,則 在深拉成形的過程中將很容易發生破裂現象。 本發明雙_拉伸薄膜之15 0eC熱收綰率以不到整籲薄 暌设之10X為較佳〇 -15- 1^1 i^i ^nk .^——F ^^^1 f-. In 1^1 ml ^eJ (請先閲讀背面之注意事項再4寫本頁) 本紙張尺度適用中國國家標率(CNS ) A4規格(210X297公嫠) 434144 * A7 B7 經濟部中央揉率局貝工消費合作社印家 五、發明説明(<4 ) 熱收缩率砍以下方法測定:於室溫下在薄暌樣品上禳 註兩黏(間隔ID»),然後在有15ITC熱空氣循環的烘 箱中置放30分鐘,随即冷卻到室溫,澜量標註點加熱前 後的間隔,此加熱前後間隔的差除以加熱前間隔邸代表 熱收縮率。 如果薄膜之熱收縮率(150°C)太大,則當薄瞑積層到 金屬板上時,尺寸維小>程度就會比較大,而導致在薄膜 上面形成«缩之類的缺陷很容易發生β 位在本發明雙軸拉伸薄膜之損失揮性模數α")最离溫 度處的尖峰溫度以1D0-16(TC為較佳。 損失彈性模數你使用動態黏彈性測定裝置在10Hz頻率 及土 2 5 X 1 0 - 4動態位移條件下测得β 位在損失彈性模數(ΕΗ)最高溫度處的尖峰溫度可以根 據聚硝酸酯和聚_之組成,及熔融混合程度做適度的諏 整。最高尖峰溫度如高於160 eC,則薄膜將變得很難拉 伸,如此將使連鑲膜成形性變差。此最高尖峰溫度如低 於lfl〇"C,則經製罐之後的薄膜之附衝擊性将受得很差。 此外,本發明雙軸拉伸薄_在縱向10(TC之裂斷伸長 率(em )以及在横向10ITC之裂街伸長率(Ετ )最好能祺 足以下方程式: (EM + ET) / 2 > 150,及 -50 ^ Em - Ετ £ 250 使用裝有加熱探針之抗拉試Jg機對10 mir寬矩形樣品進 行抗拉試驗,試驗溫度為l〇D°C,夾頭間距IDcb,加壓 -1 6- ----ΙΓ,------装-- (請先閲讀背面之注意事項異毛寫本頁)Printed by the Consumer Cooperative of the Central Standard Bureau of the Ministry of Economic Affairs. The guaranteed package value is as good as one touch. * 0) The structure of the connection layer is divided: the second is the second, the second is the second. The shape and mutual taste of the five-value ester plate, but the aroma method is to homogenize the two genus of contact with some square Ka Ping Yi, the gold connection of the middle and lower, and the first layer of the middle to the M to The second structure is a straight object containing 25. The first layer contains the internal benefit of 0. The second layer is composed of two containing two internal adducts. It is also thin and long, and the poly film male security deposit is stretched to obtain the thin layer. It is used to make the ester gold deposits used to pull the shaft and pull the acid, and it has the double-median axis. The difference between this film's bright and large agglomeration layer is the most obvious because of the thin structure. After the hair loss of the result, the tb sexual attachment will be double-sexed in addition to the original. 1-111— —1 Pack — — Order — I — I i ^ {Please read and read the note f% on the back to write this page) This paper size is applicable to China National Standard (CNS) A4 Washing (210X297mm) ) 434 1 44 A7 ____B7____ Printed by the Shellfish Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs 5. Description of the Invention (Η) Includes melting and co-extrusion of the polyester and the composition of polysulfonate and polyester respectively , Laminated and fused together, biaxially stretched and The method of curing and other steps includes the steps of melting and extruding the composition of polyacetate and polysulfonic acid® and polyester to form a separate film, stretching, laminating, and fusing the thin sheets together. . Biaxial stretching methods include particle sequence biaxial stretching method, simultaneous biaxial stretching method, inflation bethod, etc. * The thickness of the film of the present invention thus prepared is between 5-100 # ·, 10-75 # is preferred. The thickness ratio (A / B) of the first layer (A) to the second layer (B / gt) is preferably 1 / 99-5G / 50, and 5 / 95-40. / 60 is more preferable, and 1 G / 9 0-3 0/7 0 is still to be selected. The biaxially stretched film of the present invention has the first layer (Α) and the second layer (B >) of which the plane stretching ratio must be Between G. 0 5-0. 1 0. f = l (nx + ny) / 2 b ηζ where nx, ny and the refractive indices in the longitudinal, propagation, and thickness directions, respectively, are examples of refraction in the above equation: According to the following method, set up a Fukun M analyzer on the eyepiece side of the Abbe refractometer, and then use the color light (NaD rays) to measure the refractive index of the film in each direction. The fixing solution used is Diiodomethane, the measurement temperature is 25 edges. If the number of plane stretch nickel is too small, when the stretch ratio of deep drawing is too high, cracks will occur. If the number of plane stretch is too large, then Deep drawn The cracking phenomenon will easily occur in the process. The thermal recovery rate of 15 0eC of the double-stretched film of the present invention is preferably less than 10X, which is a thin film. 0-15- 1 ^ 1 i ^ i ^ nk. ^ ——F ^^^ 1 f-. In 1 ^ 1 ml ^ eJ (Please read the precautions on the back before writing this page) This paper size is applicable to China National Standard (CNS) A4 size (210X297mm) 434144 * A7 B7 Yin Jia, Central Kneading Bureau, Ministry of Economic Affairs, Shellfish Consumer Cooperative, V. Explanation of the invention (< 4) The heat shrinkage rate is determined by the following method: two thin sticks are injected on the thin sample at room temperature (interval ID ») Then place it in an oven with 15ITC hot air circulation for 30 minutes, then cool to room temperature, mark the interval before and after heating, and divide the difference between the interval before and after heating by the interval before heating to represent the thermal shrinkage. If the film If the thermal shrinkage rate (150 ° C) is too large, when the thin layer is laminated on the metal plate, the dimension dimension will be small> and the defects such as «shrinkage» will easily occur on the film β. The peak temperature of the loss modulus α ") located in the biaxially stretched film of the present invention is 1D0-16 (TC The loss modulus of elasticity. You use a dynamic viscoelasticity measuring device to measure the peak temperature of β at the highest temperature of the loss modulus of elasticity (ΕΗ) at a frequency of 10 Hz and a dynamic displacement of 2 5 X 1 0-4. The composition of polynitrate and poly_ and the degree of melt mixing are moderately tempered. If the highest peak temperature is higher than 160 eC, the film will become difficult to stretch, which will worsen the moldability of the continuous film. If the highest peak temperature is lower than lf10 " C, the impact resistance of the film after canning will be poor. In addition, the biaxially stretched thin film of the present invention is best to have the following elongation at 10 (TC elongation at break (em) in TC) and the elongation at break (Eτ) in transverse direction of 10 ITC: (EM + ET) / 2 > 150, and -50 ^ Em-Ετ £ 250 The tensile test was performed on a 10 mir wide rectangular sample using a tensile test Jg machine equipped with a heated probe, the test temperature was 10 ° C, the chuck spacing IDcb, Pressurizing-1 6- ---- ΙΓ, ------ install-(Please read the precautions on the back first and write this page)
,tT 本紙張尺度適用中國國家揉準(CNS > A4規格(210X297公釐} 434144 經濟部+央揉準局貝工消费合作社印製 A7 _B7五、發明説明(β ) 速率為1〇 c*/*in,當樣品斷裂時之伸長率(3t)即代表其 100 W裂斷伸長率》设向代表與横向垂直的薄膜擠製方 向。 100°C裂斷伸長率可根據聚碘酸®和聚酯之組成、熔 融混合程度及薄膜拉伸條件做若干調整。如果(εμ+ετ) /2之值在150以下,薄膜將很難拉伸,且遽鑛膜成形性 會顯箸降低。如果)/2小於-50,則薄膜會變得 很如此很容易在输送階段破裂β此值如高於250, 薄膜之各向異性會逹到棰端值,則薄膜在積層膜之後的 低溫耐衝擊性會顯箸降低。 本發明雙軸拉伸薄膜中以熔融及淬火製成的薄膜在DSC 之低溫結晶‘化之尖峰溫度(Tec丨)與對上述樣品再進行熔 融及淬火三次循環(绝共四次循環)的薄膜在DSC之低 溫结晶化尖峄溫度(Tcc4)之溫度差(Tcc4-Tccl)最好是 在1G- 6 0°C之間。 T c c 1和T c c 4測定方法如下β 取20b g樣品,以每分鐘2QeC之升溫速率從室粗加熱到 90-C ,保持在90*C下3分鐘,然後將樣品匣取出在一置 放在冰上之鋁箔上面進行淬火及熱固化。所得樣品在DSC 中以每分艟20°C之升溫速率加熱,讀出此樣品低溫結晶 化尖峰溫度(T c c 1)。 同樣地,取2卩《g樣品,以毎分鐘20*C之升溫速率從室 溫加熱到290 °C,保持在290 °C下3分鐘,然後將樣品匣 取出在一置放在冰上之鋁箔上面進行淬火及熱固化。此 -1 7 - ----------^裝------訂------▲ (請先聞讀背面之注意事項/4-、寫本頁) 本紙張尺度適用中國國家橾準(CNS ) A4現格(2丨0X297公嫠) 經濟部中央標準局員工消费合作社印装 4 3 4 1 4 4 A7 B7五、發明説明(4 ) 程序反覆進行四次之後所得樣品在DSC中以毎分鐘2(TC 之升®速率加熱,讀出此樣品低瞄結晶化尖峰溫度 (Tcc4 ) β 低溫結晶化之尖峰溫度Tccl和Tcc4可根據聚磺酸_和 聚酯之組成、熔融混合程度及磷化合物之添加量做若干 調整β當此尖峰溫度差(Tcc4-Tccl)小於10°〇時,薄膜 將很難泣伸,而連鑕膜> 成形性也快速下降β若此尖峰溫 度差大於60°C,則經製罐之後的耐衝擊性將變差,這都 不是我們所希望的。 要製備本發明雙軸拉伸薄膜,先對一未拉伸薄膜進行 拉伸,然後熱固化,選擇的拉伸比和熱固化條件如下: 縱向拉伸比為2.5-3.6倍,横向拉伸比為2.7-3.6倍,熱 固化溫度為15G-220 °C ( 160-200 eC較佳)。 如上所述,本發明雙軸拉伸薄膜是由第一層和第二層 組成,但3外還可包含一與第二層鄰接之第三層。 第三層係以對苯二甲酸乙二酯為主重複單位之聚酯所 形成。此類聚酯的例子與第一餍相同。因此,對第一層 聚酯之描述對第三層也同樣有效。 就具有第三層之本發明雙軸拉伸薄膜而言,必須了解 到第三層之平面拉伸俗數及Ra與具有上逑兩層結構之本 發明雙軸拉伸薄膜之第二層相同。 第三層之厚度在〇.5-lfl# 之間是比較好的。 就本發明雙軸拉伸薄膜所要積層之金靥板(待別是用 於製罐者)而言,鍍錫辆板、無錫銷板、鋁板及其他鋼 -1 8 - ----„------------1T------β (請先聞讀背面之注意事項V"寫本頁) 本紙張尺度適用中國圉家揉牟(CNS ) Α4現格U10X297公釐) 434 14 4 A7 B7 經濟部中央標準局貝工消费合作社印衷 五、發明説明 ( ) 1 板 都 適 甩 0 將 薄 膜 積 層 膜 在 金 屬 板 上 之 方 法 如 下 : 1 1 0) 將 金 颶 板 加 熱 到 比 薄 膜 之 软 化 點 還 高 之 溫 度 使 薄 1 I 膜 與 其 積 層 之 後 9 予 以 冷 部 * 使 兩 者 粘 合 在 一 起 〇 請 1 ! (?) 薄 膜 預 先 用 底 塗 層 塗 佈 形 成 黏 箸 靥 9 然 後 將 此 黏 箸 先 聞 1 | 層 積 層 在 與 其 鄰 接 之 金 羼 板 上 面 〇 任 何 已 知 之 黏 箸 劑 皆 背 ft 1 I 適 用 » 例 如 環 氧 基 黏 著 劑 、 璟 氣 / 酯 -基黏著劑, 醇酸 之 注 1 I 意 I 樹 脂 基 黏 著 劑 等 〇 孝 項 1 1 要 將 本 發 明 m 軸 拉 伸 薄 膜 積 層 在 金 屬 板 上 面 比 較 好 T % 1 的 方 法 是 由 聚 m 酸 酯 與 聚 酯 之 組 成 物 所 形 成 之 第 二 層 或 寫 本 頁 裝 1 由 聚 酯 所 形 成 之 第 三 層 與 金 屬 板 接 m > 而 由 聚 酯 所 形 成 1 | 之 第 一 層 則 與 金 屬 罐 之 内 含 物 接 觸 9 以 改 良 m 衝 擊 性 、 1 | 舆 金 屬 板 之 鈷 箸 性 及 保 香 性 〇 例 如 將 本 發 明 含 第 —* 層 和 1 1 第 二 層 之 雙 軸 拉 伸 薄 膜 積 層 在 金 属 罐 之 内 倒 且 第 二 層 訂 | 必 須 與 金 屬 罐 直 接 接 觴 〇 1 I 以 下 將 對 本 發 明 做 更 進 一 步 的 說 明 〇 然 而 這 些 例 子 1 對 本 發 明 並 無 限 制 〇 聚 酯 和 聚 磺 酸 酯 待 性 值 之 m 定 及 薄 1 ! 膜 之 評 估 標 準 如 下 * Λ ⑴ 聚 酯 之 本 質 粘 度 [V ] 1 1 在 3 5°C 之 鄰 氯 苯 酚 中 m 定 〇 1 I 聚 酯 之 熔 點 π B ) 及 玻 璃 轉 移 溫 度 Π g ) 1 1 以 示 差 掃 描 卡 計 (DSC )測定。 1 © 聚 酯 之 末 端 羧 基 濃 度 1 I 用 四 溴 苯 酚 藍 做 為 指 示 劑 9 以 氫 氣 化 銪 苯 甲 醇 溶 液 在 1 1 苯 酚 舆 四 氣 乙 烷 之 混 合 溶 劑 (2 :ί 1)中進行滴定測得。 1 I -1 9- 1 1 1 1 本紙張尺度適用中國國家榡準(CNS ) A4規格(2丨OX297公釐) 434144 A7 B7 經濟部中央標準局貝工消費合作社印装 五、發明説明 ( ) ! (4) 聚 硪 酸 酯 之 粘 度 平 均 分 子 (M V) 1 根 據 以 下 Sc hn el 1公式以在二氣甲烷溶液中拥得之本 1 I 質 粘 度 U V ])計 算 得 到 0 1 1 請 1 1 IV ] 先 閲 1 1 Log Mv = 一 -log — 讀 t I C .83 1.23 X 10 -4 背 面 1 I (5) 聚 碩 酸 酯 之 末 端 羥 基 濃 度 音 1 1 利 用 bb 色 法 (D i e Μ r ο ίο 1 . C he 1 . 88(1965) PP • 2 15) 1 1 1 根 據 介 於 T i C1 4 與 末 端 羥 基 之 間 的 交 互反應 m 得 〇 i m 薄 模 之 擠 製 成 形 加 X 性 % 本 頁 裝 1 觀 察 熔 融 聚 合 物 之 擠 製 狀 態 * 然 後 根據以 下 檩 準 評 估。 1 | © 在 擠 製 成 形 過 程 中 没 有 發 生 ”熔融揠皤" 現 象 % 擠 製 1 成 形 極 為 穩 定 〇 1 1 〇 : 在 擠 製 成 形 遇 程 中 幾 乎 沒 有 發 生 "熔融搌盪" 現 象 » 訂 | 擠 製 成 形 可 算 穩 定 1 1 A ; 在 擠 製 成 形 過 程 中 偶 而 會 發 生 "熔融擺盪H 現 象 t 擠 1 1 製 成 形 不 穩 定 〇 1 1 X 在 擠 製 成 形 過 程 中 頻 頻 發 生 ”熔融擬遢" 現 象 * 擠 m A 成 形 實 質 上 兀 全 不 可 能 〇 1 (7) 薄 瞑 之 可 拉 伸 性 ! 1 觀 察 薄 膜 之 拉 伸 狀 態 9 然 後 根 據 以 下標準 評 估 〇 I ® : 在 拉 伸 過 程 中 没 有 發 生 破 裂 現 象 ,拉伸 m 為 穩 定 ! Ο * 在 拉 伸 遇 程 中 幾 乎 没 有 發 生 破 裂 現象, 拉 伸 可 算 穩 1 1 定 0 I 1 △ * 4 在 拉 伸 過 程 中 偶 而 會 發 生 破 裂 現 象,拉 伸 不 穩 定 〇 1 1 -2 0 - 1 1 i 1 本紙張尺度逍用中國囷家標準(CNS ) A4規格(2丨OX 297公釐) 434144 Α7 Β7 經濟部中央橾準局貝工消费合作社印装 五、發明説明(π ) X :在拉伸過程中頻頻發生破裂現象,拉伸實質上完全 不可能。 ⑻薄膜之處理性質(捲嬈性) 在5Q0iB寬,2Q00II長的薄膜上形成剝離層及保持層之 後,將薄膜捲好β詳細檢査捲筒外觀,計算上面具有如 画1所示長徑1毫米以上塊狀突起之數目,然後根據以 下標準評估。 λ ❾:長徑1 m以上塊狀突起之數目為 Ο :長徑1 «1以上塊狀突起之數目在1-5之間。 X :長徑1 m以上塊狀突起之數目在6掴以上。 (9)表面粗梃度(R a ) 用針觸型(needle contact type}表面粗糖度計 (SURFCORDER SE-30C, Kosaka Laboratories Ltd.^ 製)_定,條件為針半徑2yU*,接觸壓〇.〇3g,截斷值 ΰ · 2 5 咖 β 脚連績膜成形性 進行48小時的連绩膜成形,然後根據以下標準評估。 ® :在48小時的連鑛膜成形期間,薄膜破裂發生次數在 一次以下β 〇 :在4δ小時的連鑛暌成形期間,薄膜破裂發生2-3次。 Λ :在48小時的連鑛膜成形期間,薄膜破裂發生4-5次。 X :在48小時的連鑛膜成形期間,薄嫫破裂發生6次以 上《 (Η)聚硪酸酯之平均長徑 -2 1- (請先閲讀背面之注意事項r^.寫本頁) 裝· 訂 本紙張尺度適用中國國家樣準<CNS)A4規格(210X297公釐) 經濟部中央榇率局負工消费合作社印«. 434144, A7 B7______五、發明説明(/ ) 薄膜樣品用超薄切Η機切片(包括舆薄膜厚度平行及 垂直之方向)製成薄膜切Μ。使用8«1〇4在此切片樣品 的聚碩酸酯部份染色,然後用穿透式電子顯微鏡顯撖照 相(加速電壓為100 KV),從顯撖相片(放大倍率: 5000-10000倍)中量得至少20镝聚碩酸酯之長徑,計算 其平均值β (12>損失彈性模數(Ε 4之最高尖峰溫度 損失彈性模數<Ε")葆使用動態黏揮性拥定裝置在10ΗΖ 頻率及±25X10 - 4動態位移條件下拥得β位在此損失 彈性模數最高溫度處之尖峰溫度即代表損失彈性模數 (£")之最高尖峰溫度》 (1 3 ) 1 0 tr C裂斷伸長率 使用裝有加熱探針之抗拉試驗機(Tensilon Universal Tensile Tester of Toyo Baldwin Co.,Ltd.製),在 10 *«寬之矩形樣品上進行抗拉試驗,潮定溫度為l〇(TC, 夾頭間距為lOcia,壓縮速率為lOce/nin。當樣品破裂時 之伸長率(X)即代表其100*0裂斷伸長率。 < 1 4 )低溫結晶化尖峰溫度(T c c 1和T c c 4 > 使用DSC,取20· g樣品,以20Ό之升溫速率從室溫加 熱到2 9 (TC ,保持在2 9 (TC 3分鐘,然後淬火。取此樣品 之低溫結晶化尖峰溫度代表Tccle 冏樣地,薄膜經上述包含加熱、維持在高溫及淬火的 四次循瓖之後,再以20°C之升溫速率將浑火樣品加热, 濟(得之低租結晶化尖峰溫度卽代表Tcc4e -22- ----------謂裝------訂------β (請先閲讀背面之注意事項...心寫本頁) 本紙張尺度逍用中國®家橾準(CNS ) Α4現格(210Χ297公釐) 經濟部中央梂率局貝工消费合作社印製 '4 3 4 1 4 4 j A7 _B7_五、發明説明(W ) (1 S )剝離強度 將兩锸相同類型的薄暌置放在兩片210#·厚的供板中 間,此銷板已先用鉻酸電解處理過,要評估剝離強度的 那一層是放在外側(與金屬板接觴),辆板《上之後用 熱壓器以20 kg/cn2之壓力在285 °C下加熱30秒鐘。所 得積層板切成l〇m寬,50 SB長之樣品試件。在此樣品末 端部扮預先塗以201·昏的脱模劑,以謓積層板可以Ml利 分開,兩片積層板從塗有2 0»«寛的脱模劑部份以相反方 向分開形成T字型,分開部份的兩端都用抗拉試驗機固 定,測定其在2〇β·/«ΰη加壓速率下之剝離弘度(依JIS Κ6854方法)。 U6)低溫耐衝擊性 如效所述相同方法製備以單一薄膜和箪一銷板構成之 積雇板。此積層板製成之後在5QT:水中存放5天,然後 根據JIS K54QD方法對此積層板進行耐衝擊變形試驗。 也就是説,以曲率半徑5 Β»之衝模固定在沒有稹層之 薄膜上面,然後以3G0g靜重從2flc«高度掉落到此衝棋上 面。同時有5腳厚之橡腠板置放在積靥板下面。 經此耐衝擊變形試驗之後,將一電棰囿定在此沒有積 層之薄膜上面,同時另有一電極固定在浸有IX鹽水溶液 之棉布上面,此棉布置放在積層板的另一艟薄膜表面( 即接受掉落靜重的位置> ^施加6V電壓測定電流值•電 流值(A)越小表示其低溫晒衡擊性越好^ (17)保香性 -23- I----------^------1T------2 (請先閲讀背面之注意事項·Γ_本頁) 本纸張尺度適用中國®家揉率(CNS ) Α4规格(210X297公釐) 經濟部中央棣率局貝工消费合作社印裝 4 3 4 Μ 4 , Α7 ________Β7 ___五'發明説明(》) 將積層板切成150 Μ直徑之圖盤,使用拉伸模及衡床 進行四陏段的深拉成形製成直徑5 5»«之側邊無鏠容器( 以下簡稱金鼷罐)。 此内側具有積屬膜之金颳罐裝湛2 0 ΡΡ» d-串之水溶 液之後靜置5天。然後剝開薄膜,將剝開的薄膜切成15 caX15cia試件,隨即以80°C之溫度加熱30分鐘·然後用 氣相層析術測定毎克勝膜所吸附的d-寧之數量。圾附量 越小表示保香性越好。保香性根據以下標準轷估9 〇 :吸附董等於或小於聚對苯二甲酸乙二 △:吸附量稍大於聚對苯二甲酸乙二酯β X:圾附量大於聚對苯二甲酸乙二酯β 實施例1 - 8和比較例1 - 4 〔用於聚酯腠層(第一層(Α))之聚合物之製備〕 利用固相聚合法以聚對苯二甲酸乙二酯與12其耳X異 苯二甲酸共聚合,異笨二甲酸之本質拈度為0.64,楱在 二氧化鍺觸媒存在的情況下製得,其中含Β.3重逢Ϊ平均 粒徑比為1 . 1且平均粒徑為0 · 3 ;u 之二氣化鈦β此聚酯 之熔黠為22 9Τ:,玻瑰轉移溫度為73*0 β 〔聚硪酸酯之製備〕 將216份重碩酸二苯酯,228份重雙酚Α以及0.05份重 雙酚A之二銷鹽裝人一反醮器中,該反應器裝有攪拌器 及具有氮氣入口之真空蒸皤系统,此反應条統在室溫下 先經真空除氣之後,再引入氮氣取代,引入氮氣的步费 反覆進行三次。然後在常壓及19Q°C下加熱30分鏡進行 -2 4- (請先閲讀背面之注意事項寫本頁) 本紙張尺度適用中國國家橾隼(CNS ) Α4規格(210Χ297公釐) ^3414 4 經濟部中央標準局貝工消费合作社印^ A7 B7 五、發明説明(>〇 反磨,在60分艟之内使磨>力慢慢降到5D**Hg<>然後在大 约60分鏡之内將反應溫度加熱到290 ·(:,在此加熱同畤 真空是從50 ilHg變化到1 eBHg以下。在此反ϋ過程 中,苯酚會因為反應而蒸皤出來。在此相同條件下進行 反醮40分鐘之後,得到末端羥基鼉度為73當量/ 10 e克 •且粘度平均分子量(Μ v )為2 6 , 0 0 0之聚硪酸\ [用於聚硝酸酯/聚酴組成物膜層(第二層(Β))之聚合 物以及積靥膜之製備] 依表1所示比例混合聚對苯二甲酸乙二酯舆聚對苯二甲 酸丁二酯製備上述聚碩酸酯與聚酯之混合物,然後加入 β 〇ΡΡ·(以磷濃度表示)磷酸做為磷化合物。所得混合 物連同第一層<Α)用雙層鏟模共擠製製成雙層未拉伸薄 膜。在此擠製程序中,經乾燥之後,第一磨(Α)之聚酯 聚合物是在約280 eC之聚合溫度下使用擠製機進行熔賺 擠製,而第二層(Β)也在约29(TC之聚合溫度下熔融擠製 。經此雙靥模製得之積層膜冷卻之後捲嬈在鑄棍上面即 獲得未拉伸薄膜。接箸在130 Ό之溫度下對此未拉伸薄 膜横向拉伸到3.0倍,然後也在130 4C之溫度下绺向拉伸 到3.0倍,最後在18fl °C之溫度熱固化即製得雙軸拉伸稹 雇膜》 -25- 本紙張尺度適用中國困家橾牟(CMS ) Α4規格(210Χ2ίΐ7公釐) (請先閲讀背面之注意事項/枷寫本頁) 裝_ *1T* 434144, tT This paper size is applicable to the Chinese national standard (CNS > A4 size (210X297 mm) 434144 Printed by the Ministry of Economic Affairs + Central Standards Bureau Beige Consumer Cooperative A7 _B7 V. Description of the invention (β) rate is 10c * / * in, when the sample breaks, the elongation (3t) represents its 100 W breaking elongation. "Set to represent the film extrusion direction perpendicular to the transverse direction. The breaking elongation at 100 ° C can be determined according to polyiodic acid and Make some adjustments to the composition of polyester, the degree of melt mixing, and the stretching conditions of the film. If the value of (εμ + ετ) / 2 is less than 150, the film will be difficult to stretch, and the shape of the arsenic film will be significantly reduced. ) / 2 is less than -50, the film will become so easy to rupture during the conveying phase. If this value is higher than 250, the anisotropy of the film will reach the end value, and the film will have low temperature impact resistance after lamination. The properties of the biaxially stretched film of the present invention are melted and quenched. The peak temperature (Tec 丨) of the low temperature crystallization of DSC and the melting and quenching of the above-mentioned samples are repeated three times. Four cycles) of thin film crystallization at DSC The temperature difference (Tcc4-Tccl) of Tcc4) is preferably between 1G and 60 ° C. The measurement methods of Tcc1 and Tcc4 are as follows: β Take a 20b g sample and heat it from the chamber at a heating rate of 2QeC per minute. To 90-C, keep at 90 * C for 3 minutes, then take out the sample box on an aluminum foil placed on ice for quenching and heat curing. The obtained sample is heated at a temperature of 20 ° C per minute in DSC. Heat and read the sample's low-temperature crystallization spike temperature (T cc 1). Similarly, take 2 卩 g sample and heat from room temperature to 290 ° C at a heating rate of 20 * C for 毎 minutes and keep at 290 ° C Leave it for 3 minutes, then take out the sample box on an aluminum foil placed on ice for quenching and heat curing. This-1 7----------- ^ install ------ order- ----- ▲ (Please read the precautions on the back / 4-, write this page) This paper size is applicable to China National Standards (CNS) A4 now (2 丨 0X297 public) Employees of the Central Standards Bureau of the Ministry of Economic Affairs Printed by a consumer cooperative 4 3 4 1 4 4 A7 B7 V. Description of the invention (4) After the procedure is repeated four times, the sample obtained is heated in DSC at a rate of 毎 minutes 2 (liters of TC®), and the sample is read at a low end. Peak temperature (Tcc4) β The peak temperature Tccl and Tcc4 for low temperature crystallization can be adjusted according to the composition of polysulfonic acid and polyester, the degree of melt mixing and the amount of phosphorus compounds added. Β When this peak temperature difference (Tcc4-Tccl When the temperature is less than 10 ° 〇, the film will be difficult to stretch, and the flail film > formability will decrease rapidly. If the peak temperature difference is greater than 60 ° C, the impact resistance after canning will be deteriorated. None is what we want. To prepare the biaxially stretched film of the present invention, an unstretched film is first stretched and then thermally cured. The selected stretching ratio and thermal curing conditions are as follows: the longitudinal stretching ratio is 2.5-3.6 times and the transverse stretching ratio It is 2.7-3.6 times, and the heat curing temperature is 15G-220 ° C (160-200 eC is preferred). As described above, the biaxially stretched film of the present invention is composed of a first layer and a second layer, but the third layer may further include a third layer adjacent to the second layer. The third layer is formed of polyester with ethylene terephthalate as the main repeating unit. Examples of such polyesters are the same as the first fluorene. Therefore, the description of the first layer of polyester is also valid for the third layer. As far as the biaxially stretched film of the present invention having the third layer is concerned, it is necessary to understand that the plane stretch number and Ra of the third layer are the same as the second layer of the biaxially stretched film of the present invention having a two-layer structure of the upper layer. . The thickness of the third layer is preferably between 0.5-lfl #. As far as the gold slabs to be laminated of the biaxially stretched film according to the present invention (to be other than those used for can-making) are concerned, tin-plated vehicle boards, tin-free pin plates, aluminum plates, and other steels are used. ----------- 1T ------ β (Please read the precautions on the back V " write this page) This paper size is applicable to Chinese family members (CNS) Α4 is now U10X297 (Mm) 434 14 4 A7 B7 Impressions of the Bayer Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs 5. Description of the invention () 1 The plates are suitable for throwing 0 The method of laminating thin films on metal plates is as follows: 1 1 0) The board is heated to a temperature higher than the softening point of the film, so that the thin 1 I film is laminated with the 9 cold section * to bond the two together. Please 1! (?) The film is coated with an undercoat layer in advance to form an adhesive layer.靥 9 Then read this adhesive 1 | Laminated on top of the gold plate adjacent to it 〇 Any known adhesive is back ft 1 I Applicable »For example epoxy based adhesive, radon / -Based adhesive, alkyd Note 1 I means I resin based adhesive, etc. Item 1 1 It is better to laminate the m-axis stretched film of the present invention on a metal plate. The second layer or writing sheet made of polyester composition 1 The third layer made of polyester is connected to the metal plate m > and the first layer made of polyester 1 | is connected to the metal can The inclusions 9 are contacted to improve the m impact properties, the cobalt properties of the metal sheet, and the fragrance retention properties. For example, the biaxially stretched film of the present invention containing the first-* layer and the second layer of 1 1 is laminated on the metal. Inside the tank and the second layer is ordered | Must be directly connected to the metal tank 〇1 I The following will further explain the present invention 〇 However, these examples 1 are not limited to the invention 〇 Polyester and polysulfonate properties M fixed and thin 1! The evaluation criteria are as follows: Λ 本质 Intrinsic viscosity of the polyester [V] 1 1 M is determined in o-chlorophenol at 35 ° C 〇1 I Melting point of the polyester π B) and glass transition temperature Π g) 1 1 Scanning card meter (DSC) measurement. 1 © Polyester terminal carboxyl group concentration 1 I Tetrabromophenol blue is used as an indicator. 9 Hydrogenated benzyl alcohol solution is titrated in 1 1 phenol and tetrakisethane mixed solvent (2: ί 1). . 1 I -1 9- 1 1 1 1 This paper size is applicable to China National Standards (CNS) A4 (2 丨 OX297 mm) 434144 A7 B7 Printed by the Bayer Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs 5. Description of the invention () (4) Viscosity average molecule (MV) 1 of polyacetate 1 Calculated according to the following formula Sc hn el 1 and obtained in the digas methane solution 1 I mass viscosity UV]) Calculated 0 1 1 Please 1 1 IV ] Read 1 1 Log Mv = 1-log — read t IC .83 1.23 X 10 -4 on the back 1 I (5) terminal hydroxyl concentration tone of poly (ester) 1 1 using the bb color method (D ie Μ r ο ίο 1. C he 1. 88 (1965) PP • 2 15) 1 1 1 Based on the interaction reaction between T i C1 4 and the terminal hydroxyl group m to obtain 〇im. 1 Observe the extruded state of the molten polymer * and then evaluate according to the following criteria. 1 | © "Melting" does not occur during extrusion molding% Extrusion 1 Forming is extremely stable 〇1 1 〇: "Melting undulation" phenomenon rarely occurs during extrusion molding | Extrusion can be regarded as stable 1 1 A; occasionally during the extrusion process " melting swing H phenomenon t extrusion 1 1 instability of the formation 〇1 1 X frequently occurs during extrusion "; Phenomenon * Extrusion of m A is virtually impossible. 0 (7) The stretchability of thin film! 1 Observe the stretched state of the film 9 and then evaluate it according to the following criteria. Ⅰ: It does not occur during the stretching process. Breaking phenomenon, the stretching m is stable! 〇 * There is almost no breaking phenomenon during the stretching process, and the stretching can be regarded as stable 1 1 set 0 I 1 △ * 4 During the stretching process However, the cracking phenomenon will occur and the stretching will be unstable. 0 1 1 -2 0-1 1 i 1 The size of this paper is in accordance with Chinese Standard (CNS) A4 (2 丨 OX 297 mm) 434144 Α7 Β7 Central Ministry of Economic Affairs Printed by the Zhuhai Bureau Shellfish Cooperative Cooperative V. Description of the Invention (π) X: Frequent breakage occurs during stretching, and stretching is virtually impossible. ⑻The processing properties of the film (rolling property) After forming a release layer and a retaining layer on a 5Q0iB wide and 2Q00II long film, roll the film. Check the appearance of the roll in detail. The number of the above lumps was then evaluated according to the following criteria. λ ❾: The number of block protrusions with a length of 1 m or more is 0: The number of block protrusions with a length of 1 «1 or more is between 1-5. X: The number of block-like protrusions with a length of 1 m or more is 6 mm or more. (9) Surface roughness (R a) is determined using a needle contact type surface roughness meter (SURFCORDER SE-30C, manufactured by Kosaka Laboratories Ltd.), provided that the needle radius is 2 μU * and the contact pressure. 〇3g, cut-off value ΰ · 2 5 β β-continuous film formability 48-hour continuous film formation, and then evaluated according to the following criteria: ®: During the 48-hour continuous mineral film formation, the number of film cracking occurred in The following β once: 2-3 times during the formation of continuous mineral ore during 4δ hours, thin film rupture occurred 2-3 times. Λ: 4-5 times during the formation of continuous mineral ore film formation. X: continuous 48 hours During the formation of the mineral film, the cracking of the thin cymbal occurred more than 6 times. ((Η) The average major diameter of the polyacrylate-2 1- (Please read the precautions on the back side r ^. Write this page). China National Standards < CNS) A4 size (210X297 mm) Printed by the Consumers ’Cooperative of the Central Government Bureau of the Ministry of Economic Affairs«. 434144, A7 B7 ______ V. Description of the invention (/) Ultra-thin cutting machine for film samples (/) Including the thickness of the film (parallel and vertical directions) to make a film cut. Use 8 «1〇4 to stain the polysterate portion of this section sample, and then use a transmission electron microscope to take a photograph (acceleration voltage of 100 KV), and take a photo from the photograph (magnification: 5000-10000 times) Obtain at least 20 长 long diameter of polyetherate, and calculate its average value β (12> loss elastic modulus (maximum peak temperature loss elastic modulus of Ε 4 < Ε ") 葆 using dynamic viscous viscous Under the conditions of 10 位 Z frequency and ± 25X10-4 dynamic displacement, the peak temperature of the β position at the highest temperature of the loss elastic modulus is the highest peak temperature of the loss elastic modulus (£ ") "(1 3) 1 0 tr C Elongation at break Using a tensile tester (manufactured by Tensilon Universal Tensile Tester of Toyo Baldwin Co., Ltd.) equipped with a heated probe, a tensile test was performed on a 10 * «wide rectangular sample. The temperature is 10 (TC, the chuck distance is 10 cia, and the compression rate is 10 ce / nin. When the sample is broken, the elongation (X) represents its 100 * 0 elongation at break. ≪ 1 4) Low temperature crystallization spike Temperature (T cc 1 and T cc 4 > Using DSC, take a 20 · g sample at 20Ό The temperature rate was heated from room temperature to 29 ° C, held at 29 ° C for 3 minutes, and then quenched. The low-temperature crystallization spike temperature of this sample represents the Tccle sample. The film was heated, maintained at high temperature, and quenched as described above. After four cycles of heating, the muddy fire sample was heated at a heating rate of 20 ° C. (The low-temperature crystallization peak temperature obtained by T represents Tcc4e -22- ---------- predicated- ----- Order ------ β (Please read the precautions on the back ... write this page first) This paper size is easy to use China® furniture standard (CNS) Α4 is now (210 × 297 mm) "4 3 4 1 4 4 j A7 _B7_" printed by the Central Government Bureau of the Ministry of Economic Affairs, Shellfish Consumer Cooperative, V. Description of the invention (W) (1 S) Peel strength Place two thin sheets of the same type on two pieces of 210 # · In the middle of the thick supply plate, this pin plate has been electrolytically treated with chromic acid. The layer to evaluate the peel strength is placed on the outside (connected with the metal plate). The pressure of kg / cn2 was heated at 285 ° C for 30 seconds. The obtained laminated board was cut into a sample specimen of 10m width and 50 SB length. The end of this sample was pre-coated with 201 · faint peel. It can be separated by using a concrete laminate. The two laminates are separated from each other in the opposite direction from the mold release agent coated with 20 »« 寛 to form a T-shape. Both ends of the separated part are tested by a tensile tester. Fix and measure the peeling degree at 20β · / «ΰη pressure rate (according to JIS K6854 method). U6) Low-temperature impact resistance The same method as described above was used to prepare a composite sheet composed of a single film and a single pin plate. After the laminated board was made, it was stored in 5QT: water for 5 days, and then the laminated board was subjected to an impact deformation resistance test according to the JIS K54QD method. In other words, a die with a radius of curvature of 5 B »is fixed on the film without a cymbal layer, and then it is dropped from the height of 2flc« to the punch with a static weight of 3G0g. At the same time, a 5-foot-thick oak cymbal board was placed under the cymbal board. After this impact deformation test, an electrode was fixed on the film without lamination, and another electrode was fixed on the cotton cloth impregnated with IX saline solution. The cotton was placed on the surface of the other film of the laminate. (That is, the position where the static weight is accepted) ^ Measure the current value by applying a voltage of 6V • The smaller the current value (A), the better the low temperature balance resistance ^ (17) fragrance retention -23- I ---- ------ ^ ------ 1T ------ 2 (Please read the notes on the back first. Γ_This page) This paper size is applicable to China® home kneading rate (CNS) Α4 specification (210X297 mm) Printed by the Central Government Bureau of the Ministry of Economic Affairs, Shellfish Consumer Cooperative, 4 3 4 Μ 4, Α7 ________B7 ___ Five 'Invention Description (") Cut the laminated board into a 150 MW diameter dial, and use a drawing die And deep-drawing with four scales and a weighing bed to form a sideless container with a diameter of 5 5 »« (hereinafter referred to as a golden canister). The inner side is a gold scraper can with a built-up film. 2 0 PP »d- The aqueous solution of the string was left to stand for 5 days. Then the film was peeled off, and the peeled film was cut into 15 caX15cia test pieces, and then heated at 80 ° C for 30 minutes. Then the gas phase layer was used. The amount of d-Ning adsorbed by 毎 克 胜 膜 was determined by surgery. The smaller the amount of rubbish attached, the better the fragrance retention. The fragrance retention is estimated according to the following criteria: 〇: The adsorption Dong is equal to or less than polyethylene terephthalate. △: The amount of adsorption is slightly larger than polyethylene terephthalate β X: The amount of refuse attached is larger than polyethylene terephthalate β Examples 1 to 8 and Comparative Examples 1 to 4 Preparation of a layer of polymer (A))] Copolymerization of polyethylene terephthalate with 12 isophthalic acid X isophthalic acid by solid-phase polymerization method, the intrinsic degree of isobenzoic acid is 0.64, 楱It is prepared in the presence of germanium dioxide catalyst, which contains B.3 reunion. The average particle size ratio is 1.1 and the average particle size is 0.3. U bis gasification titanium β melting point of this polyester It is 22 9T :, the glass transition temperature is 73 * 0 β [preparation of polyacetate] 216 parts by weight of diphenyl ether, 228 parts by weight of bisphenol A and 0.05 parts by weight of bisphenol A are sold In the reactor, the reactor is equipped with a stirrer and a vacuum steaming system with a nitrogen inlet. The reaction strip is first degassed under vacuum at room temperature and then replaced with nitrogen. The nitrogen gas step is repeated three times. Then, the 30 minute mirror is heated at normal pressure and 19Q ° C for -2 4- (Please read the precautions on the back first to write this page) The paper size is applicable to the Chinese national standard (CNS) Α4 specifications (210 × 297 mm) ^ 3414 4 Printed by the Shellfish Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs ^ A7 B7 V. Description of the invention (> 〇 Anti-grinding, make the mill > force slowly drop to 5D within 60 minutes ** Hg < > The reaction temperature was then heated to 290 in about 60 minutes. (: Here, the heating vacuum was changed from 50 ilHg to less than 1 eBHg. During this reaction, phenol is distilled off due to the reaction. After carrying out incubation under the same conditions for 40 minutes, a polyphosphonic acid having a terminal hydroxyl group degree of 73 equivalents / 10 g and a viscosity average molecular weight (Mv) of 2 6, 0 0 0 was obtained. Polyester / Polyfluorene Composition Film (Polymer (Second Layer (B)) Polymer and Preparation of Film)] Blend polyethylene terephthalate and polybutylene terephthalate in the proportions shown in Table 1. A mixture of the above-mentioned polybasic acid ester and polyester was prepared, and then β-OPP (indicated by phosphorus concentration) phosphoric acid was added as a phosphorus compound. The resulting mixture, together with the first layer < A), was co-extruded with a double-layer spade die to form a double-layer unstretched film. In this extrusion process, after drying, the polyester polymer of the first mill (A) is melt extruded using an extruder at a polymerization temperature of about 280 eC, and the second layer (B) is also Melt extrusion at a polymerization temperature of about 29 ° C. The laminated film prepared by this double-roller mold is cooled and rolled on a cast stick to obtain an unstretched film. Then, it is unstretched at a temperature of 130 ° C. The film is stretched to 3.0 times in the transverse direction, and then stretched to 3.0 times in the direction of 130 4C. Finally, it is thermally cured at 18fl ° C to obtain a biaxially stretched film. -25- This paper size Applicable to China's impoverished family (CMS) Α4 specification (210 × 2ίΐ7 mm) (Please read the precautions on the back / write this page first) Pack_ * 1T * 434144
7 7 A B 五、發明説明(μ ) 表1 聚碳酸酯 (重量%) 聚酯 (重量%) 聚對苯二甲酸乙烯酯 (雷量%) 聚對苯二甲酸丁稀醋 (重量%) 比較例1 18 82 60 40 實施例1 22 78 60 40 實施例2 40 60 60 40 比較例2 62 > 38 60 40 比較例3 40 60 8 92 實施例3 40 60 12 88 實施例4 40 60 20 80 實施例5 40 60 40 60 實施例6 40 60 80 20 實施例7 40 60 85 15 實施例8 40 60 88 12 比較例4 40 60 92 8 f K------- 裝-------ST--1----^ (請先閲讀背面之注意事項 Ί填寫本頁) 如此製得之雙軸拉伸薄膜,其第一層(A)之平面拉伸 换數為0.06,第二層(B)之平面拉伸係數為〇_〇5,第一 _ (A)之厚度為6# 1,第二層(B)之厚度為24// *。此薄 膜之l5GeC熱收縮率為5-75;。 經濟部中央標準局員工消费合作社印製 上述聚對苯二甲酸乙二酯和聚對苯二甲酸丁二酯均利 用固相聚合法製備β前者若使用二氣化鍺梅媒時,本質 粘度為0.64,熔點為255 °C,玻璃轉移溫度為T8eC,而 -2 6 - 本紙張尺度逍用中國國家標牟(CNS ) A4規格(210X297公釐) 4341447 7 AB V. Description of the invention (μ) Table 1 Polycarbonate (wt.%) Polyester (wt.%) Polyethylene terephthalate (% by weight) Polybutylene terephthalate (wt.%) Comparison Example 1 18 82 60 40 Example 1 22 78 60 40 Example 2 40 60 60 40 Comparative Example 2 62 > 38 60 40 Comparative Example 3 40 60 8 92 Example 3 40 60 12 88 Example 4 40 60 20 80 Example 5 40 60 40 60 Example 6 40 60 80 20 Example 7 40 60 85 15 Example 8 40 60 88 12 Comparative Example 4 40 60 92 8 f K --------------------- --ST--1 ---- ^ (Please read the precautions on the back first and fill in this page) The biaxially stretched film thus prepared has a first layer (A) with a plane stretching factor of 0.06, The plane elongation coefficient of the second layer (B) is 0-5, the thickness of the first layer (A) is 6 # 1, and the thickness of the second layer (B) is 24 // *. The thermal shrinkage of l5GeC of this film is 5-75; The above-mentioned polyethylene terephthalate and polybutylene terephthalate were printed by the Consumer Cooperative of the Central Bureau of Standards of the Ministry of Economic Affairs, both of which were prepared by solid-phase polymerization. When the former is used, the intrinsic viscosity is 0.64, melting point is 255 ° C, glass transition temperature is T8eC, and -2 6-This paper size uses China National Standards (CNS) A4 specifications (210X297 mm) 434144
A B 經濟部中央揉隼局具工消费合作社印製 五、發明説明(<) 末端羧基濃度為15當量/1(]6克,若使用鈦酸四丁酯® 媒時,本質粘度為1.1,熔點為223 °C,玻璃鹌移溫度為 32eC,而末端羧基濃度為1〇當童/1〇6克。 評估結果示K表2中。從表中可看出本發明雙軸拉伸 薄膜具備極佳的擠裂成形加工性、可拉伸性、舆金屬板 之黏著性、低溫耐衝擊性及保香性。 表2 擠製成形加工性 可拉伸性 剝離強度 (kg/cm) 低溫耐衝擊性 (mA) 保香性 比較例1 〇 〇 6 0.5 〇 實施例1 ◎ ◎ 6 0.2 〇 實施例2 ◎ ◎ 3 0.1 〇 比較例2 X X 比較例3 Δ Δ 3 0.5 〇 實施例3 0 〇 2.5 0.1 〇 實施例4 〇 〇 2.5 0.1 〇 實施例5 ◎ ◎ 3 0.1 〇 實施例6 ◎ ◎ 3 0.1 〇 實施例7 〇 〇 3 0.1 〇 實施例8 〇 〇 3 0.1 〇 比較例4 X X _ -27- 本纸張尺度適用中國圉家揉準(CNS)八4说格(210XW公釐) •-Il·--------,裝------訂------A (請先閱讀背面之注意事項罗%·寫本頁) 434144 經濟部中夬樣率局負工消费合作社印装 A7 _B7___五、發明説明( 比較例5 在實施例2中,只使用第二雇(B)(厚度3Q#b> ,而 不使用第一層(A)積雇.發現其保香性降到X之水準β 賁施例9-16和比較例6-7 将216份重碩酸二苯酯,2 2 8份重雙酚Α以及〇·〇5份重 雙酚Α之二納鹽裝入一反窸器中,該反暱器裝有攪拌器 及具有氪氣入口之真空^蒸脯糸統,此反應糸統在室溫下 先經其空除氣之後,再引入氤氣取代,引入氪氣的步驟 反覆進行三次。然後在常壓及190T!下加熱3D分鐘進行 反應,在60分鐘之内使壓力慢慢降到50 *BHge然後在 大約60分鐘之内将反應溫度加熱到29Q-C,在此加熱同 時,真空是從5t) BnHg變化到1 *BHg以下。在此反應過 程中,苯酚會因為反應而蒸脯出來。在此相同條件下進 行反應40分鐘之後,得到末端羥基«度為48當量/I0e 克,且拈度平均分子量U v )為2 8,0 0 0之聚硪酸酯。如此 製得之聚硪酸酯舆做為磷化合物之4 5 PPB (以镑磨度表 示)ADK STAB 2 112 (Asahi Denka Eogyo Co . , Ltd·公 司製)混合,然後熔融擠製》 〔積層膜之製備〕 利用固相聚合法製備聚對苯二甲酸乙二酯(其本質粘度 為0.64,偽在二氧化鍺觸媒存在的情況下製得.其中含 0.2重量X平均粒徑比為1.1且平均粒徑為0.3> *之二氣 化鈦)。此一聚對苯二甲酸乙二酯之熔點為2 5 5 °C •玻 璃轉移溫度為78 *C (用於第一層(A)之聚合物)。 -2 8 - — —ί 1— ^裝 IΪΤ_^ (請先閲讀背面之注意事項rih-寫本頁) 本纸張尺度適用中國國家標準(CNS ) A4規格(210X297公釐) 經濟部中央標準局負工消費合作社印裝 434144 ^ A7 B7 五、發明説明(”) 如表3所示將40重量%以上製得之聚硪酸酯,60重量 %由聚對苯二甲酸乙二酯基聚_<70重童!Π舆聚對苯二 甲酸丁二酯基聚酯(3〇重量X)組成之聚酯乾混》 此聚對苯二甲酸乙二酯基聚酷和聚對苯二甲酸丁二酯 基聚酯皆利用固相聚合法製備》前者是使用二氣化鍺觸 媒,後者則使用鈦酸四丁酯觸媒"如表3所示改變預聚 合物之本質粘度、固相> 聚合反應中之固相聚合時間及末 端羧基濃度。 表3 PET基聚酯 mm 本質粘度 熔點 CC) 玻璃雛歷 CC) 末端钱基濃度 (當量/106克) 比較例6 PET 0.75 255 78 4 實施例9 PET 0.75 255 78 12 實施例10 PET 0.75 255 78 20 實施例11 PET 0.75 255 78 30 實施例12 PET 0.75 255 78 30 實施例13 PET 0.75 255 78 30 比較例7 PET 0.75 255 78 30 實施例14 PETI12 0.75 229 74 25 實施例15 PETI12 0.75 229 74 12 實施例16 PETI12 0.75 229 74 30 -2 9- 本纸張尺度適用中國闺家標準(CNS ) Α4現格(2丨0X297公釐) 1.1-Γ------..袭------ΐτ------J- (請先閲讀背面之注意事項荨填寫本頁) 434 14 4 ^ A7 B7Printed by the Central Government Bureau of the Ministry of Economic Affairs and the Industrial Cooperative Cooperative. V. Description of the invention (<) The terminal carboxyl group concentration is 15 equivalents / 1 () 6 grams. When using tetrabutyl titanate® medium, the intrinsic viscosity is 1.1, The melting point is 223 ° C, the glass transition temperature is 32eC, and the terminal carboxyl group concentration is 10 tango / 106 g. The evaluation results are shown in Table 2. K can be seen from the table that the biaxially stretched film of the present invention has Excellent extrusion processability, stretchability, metal sheet adhesion, low temperature impact resistance and fragrance retention. Table 2 Extrusion processability stretchability peel strength (kg / cm) low temperature resistance Impact (mA) Fragrance retention Comparative Example 1 〇06 0.5 〇 Example 1 ◎ ◎ 6 0.2 〇 Example 2 ◎ ◎ 3 0.1 〇 Comparative Example 2 XX Comparative Example 3 Δ Δ 3 0.5 〇 Example 3 0 〇2.5 0.1 〇 Example 4 〇 2.5 2.5 〇 Example 5 ◎ ◎ 3 0.1 〇 Example 6 ◎ ◎ 3 0.1 〇 Example 7 〇 03 0.1 〇 Example 8 〇 03 0.1 〇 Comparative Example 4 XX -27 The size of this paper is applicable to the standard of China National Family Standard (CNS) 8-4 (210XW mm) • -Il · --------, installed ------ order- ----- A (Please read the precautions on the back of this page, and write this page) 434144 Printed by the Ministry of Economic Affairs, Consumers Cooperative, A7 _B7___ 5. Explanation of the invention (Comparative Example 5 in Example 2 In the use, only the second employment (B) (thickness 3Q # b>) was used, and the first layer (A) was not used. It was found that its fragrance retention decreased to the level of X β 贲 Examples 9-16 and Comparative Example 6 -7 Put 216 parts of diphenyl heavy acid, 2.8 parts by weight of bisphenol A, and 0.05 parts by weight of bisphenol A sodium salt into a reactor, which is equipped with a stirrer And a vacuum steamed preserved meat system with a radon inlet, this reaction system is first degassed at room temperature, then replaced by radon gas, the step of introducing radon gas is repeated three times. Then at normal pressure and 190T The reaction is heated for 3D minutes, and the pressure is gradually reduced to 50 * BHge within 60 minutes, and then the reaction temperature is heated to 29Q-C within about 60 minutes. At the same time, the vacuum is changed from 5t) BnHg Below 1 * BHg. During this reaction, phenol will be steamed out due to the reaction. After carrying out the reaction under the same conditions for 40 minutes, the terminal hydroxyl group is 48 Polyester with equivalent weight / I0e grams and a degree average molecular weight U v) of 28,000. The thus-obtained polyacrylate is 4 5 PPB (expressed in pounds) as a phosphorus compound. ADK STAB 2 112 (manufactured by Asahi Denka Eogyo Co., Ltd.) is mixed and then melt-extruded. [Preparation of laminated film] Polyethylene terephthalate (its intrinsic viscosity is 0.64, Pseudo-prepared in the presence of germanium dioxide catalyst. It contains 0.2% by weight x average particle size ratio of 1.1 and average particle size of 0.3 > The melting point of this polyethylene terephthalate is 2 5 5 ° C • The glass transition temperature is 78 * C (for the polymer of the first layer (A)). -2 8-— — 1 — ^ 装 IΪΤ_ ^ (Please read the precautions on the back rih-write this page first) This paper size applies to China National Standard (CNS) A4 (210X297 mm) Central Bureau of Standards, Ministry of Economic Affairs Printed by a consumer co-operative cooperative 434144 ^ A7 B7 V. Description of the invention (") As shown in Table 3, 40% by weight or more of the polyacrylate was prepared, and 60% by weight of polyethylene terephthalate-based poly- < 70 Chongtong! Π Polyester terephthalate-based polyester (30 weight X) dry blend of polyester >> This polyethylene terephthalate-based polycool and polyterephthalate The succinate-based polyesters are all prepared by solid-phase polymerization. The former uses a digassed germanium catalyst, and the latter uses a tetrabutyl titanate catalyst. As shown in Table 3, the intrinsic viscosity of the prepolymer is changed. Phase > Solid-phase polymerization time and terminal carboxyl group concentration in the polymerization reaction. Table 3 PET-based polyester mm intrinsic viscosity melting point CC) glass calendar CC) terminal pen group concentration (equivalent / 106 g) Comparative Example 6 PET 0.75 255 78 4 Example 9 PET 0.75 255 78 12 Example 10 PET 0.75 255 78 20 Example 11 PET 0.75 255 78 30 Example 12 PET 0.75 255 78 30 Example 13 PET 0.75 255 78 30 Comparative Example 7 PET 0.75 255 78 30 Example 14 PETI12 0.75 229 74 25 Example 15 PETI12 0.75 229 74 12 Example 16 PETI12 0.75 229 74 30 -2 9 -This paper size is applicable to the Chinese Girl Standard (CNS) Α4 (2 丨 0X297mm) 1.1-Γ ------ .. Attack ------ 袭 τ ------ J- (Please read the precautions on the back first to fill in this page) 434 14 4 ^ A7 B7
五、發明説明() PET:聚對苯二甲酸乙二酯 PETI12:與12莫耳X異苯二甲酸共聚合之PET 表3(續) PBT基聚酯 本質粘度 熔點 CC) 玻璃轉移酿 (°C) 末端羧基濃度 (當量/1〇6克) 比較例6 PBTI5 0.9 218 28 8 實施例9 PBTI5 0.9 2 18 28 8 實施例10 PBTI5 0.9 218 28 8 實施例11 PBTI5 0.9 218 28 8 實施例12 PBTI5 0.9 218 28 12 實施例Π ΡΒΤΪ5 0.9 218 28 18 比較例7 PBTI5 0.9 218 28 22 實施例14 PBT 0.9 223 32 10 實施例15 PBT 0.9 223 32 18 實施例16 PBTI5 0.9 218 28 8 {請先閱讀背面之注意Ϋ項V--填寫本頁) .裝- 訂 經濟部中央搮準局貝工消費合作杜印袈 PET:聚對苯二甲酸丁二酯 PETI5:與5莫耳5ί異苯二甲酸共聚合之PBT 上述聚對苯二甲酸乙二酯和聚磺酸酯-聚酷摻合聚合 物皆依一般常用的方法乾燥,然後分別饋入各自的擠製 機中形成雙層共擠製積層膜,摻合聚合物從共擠製狹縫 熔融擠製出來,聚對苯二甲酸乙二酯之聚合溫度為280 -3 0 - 本紙張尺度適用中國國家標準(CNS ) Α4规格(2tOx297公釐) 434144 A7 B7 五、發明説明(β ) °C,而摻合聚合物之聚合溫度為2 8 0- 2 90°Ce共擠製膜 經冷卻之後捲鏡在一铸棍上面製成未拉伸薄膜。 接箸在135 °C之溫度下對此未拉伸薄睽横向拉伸到3.0 倍,然後也在135 °C之溫度下縱向拉伸到3.0倍,最後在 180 "C之溫度熱固化邸製得雙轴拉伸薄膜 在如此製得之雙軸拉伸薄膜中,聚對苯二甲酸乙二酯 層之厚度為5#·,平面^拉伸係數為0.0 7,摻合聚合物層 之厚度為20#*,平面拉伸偽數為0.06。薄膜之150"C熱 收缩率為5-73:。 評估結果示於表4中。當聚對苯二甲馥乙二酯基聚酯 之末端羧基濃度在5當量/ lfl6克以上,且聚對苯二甲 酸丁二酯基聚酯之末端羧基濃度在20當量/ l〇e克以下 ,所得薄膜具備掻佳的舆金靥板之黏箸性,而薄膜之成 膜性(擠製成形加工性和可拉伸性)也能夠令人保意。 l·----=-----j 裝------訂------i (請先閱讀背面之注意事項vv寫本頁) 經濟部中央橾準局員工消費合作社印裝 -3 1- 本紙張尺度適用中國國家橾準(CNS > A4規格(210X297公釐) 434144 A7 B7 經濟部中央梯準局員工消費合作社印製 五、發明説明(丨 表4 擠製成形加工性 可拉伸性 剝離強度 (kg/cm) 讎耐衝擊性 (mA) 保香性 比較例6 Δ X 實施例9 ◎ 〇 2.5 0.1 〇 實施例10 ◎ ◎ 2.5 0.1 〇 實施例11 ◎ ◎ 2.5 0.1 〇 實施例12 ◎ ◎ 3.0 0.1 〇 實施例1 3 〇 〇 3.5 0.1 〇 比較例7 X X 實施例14 ◎ ◎ 2.0 0.1 〇 實施例15 〇 〇 2.0 0.1 〇 實施例16 ◎ ◎ 2.5 0.1 〇 實施例17-20 以40重量5;實施例1-8中使用之聚硪酸》與60重童Ϊ實 施例11中使用的由聚對苯二甲酸乙二酯和聚對苯二甲酸 丁二酯與5莫耳X異苯二甲酸共聚合組成之聚酯乾混, 做為磷化合物之 ADK STAB 2112 (Asahi Denka Kogyo Co., Ltd.公司製)之添加量(以磷鼷度表示)示於表5 中,依實施例11柑同條件製得積層膜。 結果示於表5中。我們發現當磷化合物之添加董在20 -10 0 PP*之間時,可得到待別好的結果。 -32- 張尺度通用中國国家搮隼(CNS > Α4说格(210X297公釐) ---.l·---------裝------訂------i (請先Μ讀背面之注意事項Η%寫本頁) 434 1 44 Α7 Β7 經濟部中央標準局貝工消费合作社印装 五、發明説明(〜) 卖5 實施例17 磷化雜添加量 (PPm) 擠製成形加工性 可拉伸性 剝離強度 (kg/cm) 麟耐衝擊性 (mA) 保香性 22 〇 〇 2.5 0.1 〇 實施例18 40 ◎ ◎ 2.5 0.1 〇 實施例19 50 ◎ ◎ 2.5 0.1 〇 實施例20 95 ◎ 3.0 0.1 〇 實施例21-27和比較例8-11 〔用於聚酯膜層(第一層(A))之聚合物之製備〕 利用固相聚合法以聚對苯二甲酸乙二酯與12奠耳X異 苯二甲酸共聚合,異苯二甲酸之本質粘度為0.64,傜在 二氣化鍺觴媒存在的情況下製得,其中含3重量X平均 粒徑比為1.1且平均粒徑為G.3jub之二氣化鈦·此聚酯 之熔酤為229 °C,玻璃轉移溫度為73 °Ce 使用的聚硝酸酯與實施例1-8相同。 〔用於聚碩酸酯-聚酯組成物膜層(第二靥(B))之聚合 物之製備,以及稹雇膜之製備〕 依表6所示比例混合聚對苯二甲酸乙二»舆聚對苯二 甲酸丁二酯製備上述聚硪酸酯與聚酯混合物,然後加入 4 〇ΡΡ·(以磷獏度表示〉磷酸做為磷化合物。所得混合 物連同第一層(Α)用雙層薄模共擠製製成雙雇未拉伸薄 膜。在此擠製程序中,第一雇(Α)之聚酯聚合物經乾燥 之後在約28JTC之聚合溫度下使用擠製機進行熔敲擠製 -33- ‘紙張尺度適用中國固家揉準(CNS ) Α4規格(210Χ297公釐) 裝------訂------J- (請先閲讀背面之注意事項/¾寫本Κ ) 434144 經濟部中央標準局員工消費合作社印装 PET:聚對苯二甲酸乙二酯 PBT :聚對苯二甲酸丁二酯 -34- A7 B7 五、發明説明(Ρ ) ,而第二層(B)也在約29G°C之聚合溫度下熔融擠製。經 此雙靥模製得之積層膜聚合物冷卻之後捲繞在鑲棍上面 即獲得未拉伸薄膜》接箸在130"C之溫度下對此未拉伸 薄膜横向拉伸到3.0倍,然後在14 ETC之溫度下縱向拉伸 到3.4倍,最後在180°C之溫度熱固化即製得雙軸拉伸積 联。 表6 聚碳酸酯 ί重畺0Λ) 聚酯 (簠量%、 PET (重量%) PBT (重量%) 聚碳酸酯分散粒子之長徑 (μηι) 比較例8 18 82 40 60 0.9 實施例21 22 78 40 60 0.7 實施例22 40 60 40 60 1.7 比較例9 62 38 40 60 無法拉伸 比較例10 40 60 8 92 0.3 實施例23 40 60 12 88 0.8 實施例24 40 60 20 80 1.0 實施例25 40 60 60 40 3.1 實施例26 40 60 80 20 4.3 實施例27 40 60 88 12 15.0 比較例Π 40 60 92 8 無法拉伸 夂紙張尺度適用中國國家標準(CNS ) A4規格(210X297公釐) I----P------^本------1T------2 (請先聞讀背面之注意事項H^寫本頁) 434144 A7 __B7_ 五、發明説明(W )V. Description of the invention () PET: polyethylene terephthalate PETI12: PET copolymerized with 12 mol X isophthalic acid Table 3 (continued) PBT-based polyester intrinsic viscosity melting point CC) glass transfer brewing (° C) Terminal carboxyl group concentration (equivalents / 106 g) Comparative Example 6 PBTI5 0.9 218 28 8 Example 9 PBTI5 0.9 2 18 28 8 Example 10 PBTI5 0.9 218 28 8 Example 11 PBTI5 0.9 218 28 8 Example 12 PBTI5 0.9 218 28 12 Example Π ΒΒΤΪ5 0.9 218 28 18 Comparative Example 7 PBTI5 0.9 218 28 22 Example 14 PBT 0.9 223 32 10 Example 15 PBT 0.9 223 32 18 Example 16 PBTI5 0.9 218 28 8 {Please read the back page first Attention item V--Fill in this page). Packing-Order the Ministry of Economic Affairs, Central Bureau of Standards, Shellfish Consumer Cooperation, Du Yin 袈 PET: Polybutylene terephthalate PETI5: Copolymerized with 5 mol 5 liters of isophthalic acid PBT The above polyethylene terephthalate and polysulfonate-polycopolymer blends are all dried according to commonly used methods, and then fed to their respective extrusion machines to form double-layer co-extruded laminated films. Blended polymer melt extruded from co-extrusion slit, polyethylene terephthalate Polymerization temperature is 280 -3 0-This paper size applies Chinese National Standard (CNS) A4 specification (2tOx297 mm) 434144 A7 B7 5. Description of the invention (β) ° C, and the polymerization temperature of the blended polymer is 2 8 0 -2 90 ° Ce co-extruded film is cooled and rolled into an unstretched film on a casting rod after cooling. The unstretched thin film was then stretched to 3.0 times in the transverse direction at a temperature of 135 ° C, and then 3.0 times in the longitudinal direction at a temperature of 135 ° C, and finally heat cured at a temperature of 180 " C. Preparation of biaxially stretched film In the biaxially stretched film thus prepared, the thickness of the polyethylene terephthalate layer was 5 # ·, and the plane ^ stretch coefficient was 0.0 7, and the polymer layer was blended with The thickness is 20 # *, and the plane drawing pseudo-number is 0.06. The film's 150 " C thermal shrinkage is 5-73 :. The evaluation results are shown in Table 4. When the terminal carboxyl group concentration of the poly (terephthalene) ethylene-based polyester is more than 5 equivalents / lfl6 g, and the terminal carboxyl group concentration of the polybutylene terephthalate-based polyester is less than 20 equivalents / 10e g The obtained film has excellent adhesion to the gold plate, and the film-forming properties (extrusion processability and stretchability) of the film can also be assured. l · ---- = ----- j outfit ------ order ------ i (please read the precautions on the back vv first to write this page) The Central Consumers' Bureau of the Ministry of Economic Affairs, the Consumer Cooperatives Imprint-3 1- This paper size applies to China National Standards (CNS > A4 size (210X297 mm) 434144 A7 B7 Printed by the Consumer Cooperatives of the Central Ladder Standard Bureau of the Ministry of Economic Affairs 5. Description of the invention (Table 4 Extrusion) Processability Stretchability Peel Strength (kg / cm) 冲击 Impact Resistance (mA) Fragrance Retaining Comparative Example 6 Δ X Example 9 ◎ 〇 2.5 0.1 〇 Example 10 ◎ ◎ 2.5 0.1 〇 Example 11 ◎ ◎ 2.5 0.1 ○ Example 12 ◎ 3.0 3.0 〇 Example 1 3 〇 3.5 3.5 〇 Comparative Example 7 XX Example 14 ◎ ◎ 2.0 0.1 〇 Example 15 〇 2.0 2.0 〇 Example 16 ◎ ◎ 2.5 0.1 〇 Example 17 -20 at 40 weight 5; Polyacrylic acid used in Example 1-8 "and 60 weights of Tongren, which are composed of polyethylene terephthalate and polybutylene terephthalate and 5 used in Example 11. Polyester dry blend blended with Mohr X isophthalic acid as ADK STAB 2112 (Asahi Denka Kogyo Co., Ltd. The addition amount (expressed as phosphate) is shown in Table 5. The laminated film was prepared under the same conditions as in Example 11. The results are shown in Table 5. We found that when the phosphorus compound was added at 20-10 0 PP. * In between, you can get good results. -32- Zhang scale general Chinese national 搮 隼 (CNS > Α4 grid (210X297 mm) ---. L · --------- Install ------ order ------ i (please read the precautions on the back Η% write this page) 434 1 44 Α7 Β7 Printed by the Shellfish Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs (~) Sell 5 Example 17 Phosphate addition amount (PPm) Extrusion molding processability Stretchability Peel strength (kg / cm) Lin Impact resistance (mA) Fragrance retention 22 〇2.5 0.1 〇 Example 18 40 ◎ ◎ 2.5 0.1 〇Example 19 50 ◎ ◎ 2.5 0.1 〇Example 20 95 ◎ 3.0 0.1 〇 Examples 21-27 and Comparative Examples 8-11 [for polyester film layer (first layer (A)) Preparation of polymers] Copolymerization of polyethylene terephthalate and 12 mol X isophthalic acid by solid-phase polymerization. The intrinsic viscosity of isophthalic acid is 0.64. Existence It was prepared as follows, which contained 3 weight X average particle size ratio of 1.1 and average particle size of G.3jub. Titanium vaporized · The melting point of this polyester was 229 ° C, and the glass transition temperature was 73 ° C. The nitrate was the same as in Examples 1-8. [Preparation of Polymer for Polyester-Polyester Composition Film Layer (Secondary (B)), and Preparation of Polyester Film] Blend polyethylene terephthalate in the proportion shown in Table 6 » Polybutylene terephthalate was used to prepare the above-mentioned polyphosphonate and polyester mixture, and then 4PP · (expressed as phosphoric acid degree> phosphoric acid as a phosphorus compound was added. The resulting mixture together with the first layer (A) was doubled. Co-extrusion of a thin layer die to make a double-stretched unstretched film. In this extrusion process, the polyester polymer of the first (A) is dried and melt-knocked using an extruder at a polymerization temperature of about 28 JTC. Extrusion -33- 'The paper size is applicable to China Gujia Standard (CNS) Α4 size (210 × 297 mm) Packing --- ----------- J- (Please read the precautions on the back / ¾ K) 434144 Printed PET: Polyethylene terephthalate PBT: Polybutylene terephthalate-34- A7 B7 Printed in the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs The layer (B) is also melt-extruded at a polymerization temperature of about 29G ° C. The laminated film polymer obtained by this double-mould molding is cooled and wound on the inlay stick That is to obtain an unstretched film, then this unstretched film was stretched to 3.0 times in the transverse direction at a temperature of 130 " C, and then stretched to 3.4 times in the longitudinal direction at a temperature of 14 ETC, and finally at a temperature of 180 ° C. Biaxially stretched product is obtained by heat curing. Table 6 Polycarbonate (Weight, 0Λ) Polyester (% by weight, PET (% by weight), PBT (% by weight)) Long diameter (μηι) of polycarbonate dispersed particles Comparative Example 8 18 82 40 60 0.9 Example 21 22 78 40 60 0.7 Example 22 40 60 40 60 1.7 Comparative Example 9 62 38 40 60 Unstretchable Comparative Example 10 40 60 8 92 0.3 Example 23 40 60 12 88 0.8 Example 24 40 60 20 80 1.0 Example 25 40 60 60 40 3.1 Example 26 40 60 80 20 4.3 Example 27 40 60 88 12 15.0 Comparative Example Π 40 60 92 8 Cannot be stretched 夂 Paper dimensions are applicable to Chinese national standards ( CNS) A4 specification (210X297mm) I ---- P ------ ^ copy ------ 1T ------ 2 (please read the precautions on the back first H ^ write copy (Page) 434144 A7 __B7_ V. Description of the invention (W)
如此製得之雙軸拉伸薄膜,其第一層<A)之平面拉伸 偽數為0.06,第二層(B)之平面拉伸偽數為0.05,第一 層(A)之厚度為6#·,第二層(B)之厚度為24#·β此薄 暌之150°C熱收縮率為5-7U 上述聚對苯二甲酸乙二酯和聚對苯二甲酸丁二酯均利 用固相聚合法製備。前者若使用二氧化緒《媒時,本質 粘度為0.64,熔點為2&5eC,玻璃轉移溫度為78°C,而 末端羧基濃度為15當量/ l〇e克,若使用鈦酸四丁酯觸 媒時,本質粘度為1.1,熔點為223 °C,玻璃轉移溫度為 32°C,而末端羧基濃度為10當量/106克。 評估結果示於表7中。從表中可看出本發明雙軸拉伸 薄膜具備棰佳的擠製成形加工性、可拉伸性、與金屬板 之黏箸性、低溫耐衝擊性及保番性。 - ,裝 訂J (請先閱讀背面之注意事項V4寫本頁) 經濟部中央標率局貝工消费合作社印衷 -3 5- 本紙張尺度適用中國國家橾準(CNS ) A4規格(2丨Ο X 297公釐) 434144 A7 B7 五、發明説明(料) 表7 擠製成形加工性 可拉伸性 剝離強度 (kg/cm) 低溫耐衝擊性 (mA) 保香性 比較例8 〇 〇 6 0.8 〇 實施例21 ◎ ◎ 6 0.2 〇 實施例22 ◎ ◎ 3 0.1 〇 比較例9 X X 比較例I 〇 Δ Δ 3 0.5 〇 實施例23 〇 〇 2.5 0.1 〇 實施例24 〇 〇 2.5 0.1 〇 實施例25 ◎ ◎ 3 0.1 〇 實施例26 ◎ ◎ 3 0.1 〇 實施例27 〇 〇 3 0.1 〇 比較例11 X X 實施例28-3 4和比較例12_13 依實施例9-16和比較例6-T相同方法製備雙軸拉伸薄 膜,但其中PET基聚酯和PBT基聚酯之末端羧基濃度分別 如表8所示改變。結果示於表8和表9中。 ----η------Ί 裝------訂------i (請先閲讀背面之注意事項/¾寫本頁) 經濟部中央標準局負工消费合作社印装 -36- 本紙張尺度適用中國國家榡準(CNS ) A4規格(210X297公釐) 4 34 4 4The biaxially stretched film thus prepared has a plane stretch pseudo-number of the first layer < A) of 0.06, a plane stretch pseudo-number of the second layer (B) of 0.05, and a thickness of the first layer (A). The thickness is 6 # ·, the thickness of the second layer (B) is 24 # · β, the thermal shrinkage of the thin film at 150 ° C is 5-7U, and the above polyethylene terephthalate and polybutylene terephthalate All were prepared by solid-phase polymerization. For the former, if the medium is used, the intrinsic viscosity is 0.64, the melting point is 2 & 5eC, the glass transition temperature is 78 ° C, and the terminal carboxyl group concentration is 15 equivalents / 10e g. In the medium, the intrinsic viscosity is 1.1, the melting point is 223 ° C, the glass transition temperature is 32 ° C, and the terminal carboxyl group concentration is 10 equivalents / 106 g. The evaluation results are shown in Table 7. It can be seen from the table that the biaxially stretched film of the present invention has excellent extrusion processability, stretchability, adhesion to metal plates, low temperature impact resistance, and heat retention. -, Binding J (Please read the note on the back V4 first to write this page) The Central Standards Bureau of the Ministry of Economic Affairs, Peigong Consumer Cooperative Co., Ltd.-3 5- This paper size is applicable to China National Standard (CNS) A4 specification (2 丨 〇 X 297 mm) 434144 A7 B7 V. Description of the invention (material) Table 7 Extrusion molding processability Tensile peeling strength (kg / cm) Low temperature impact resistance (mA) Comparative example of fragrance retention 8 〇〇0.8 0.8 〇Example 21 ◎ ◎ 6 0.2 〇Example 22 ◎ ◎ 3 0.1 〇Comparative Example 9 XX Comparative Example I 〇Δ Δ 3 0.5 〇Example 23 〇2.5 2.5 〇Example 24 〇2.5 0.1 〇Example 25 ◎ ◎ 3 0.1 〇 Example 26 ◎ ◎ 3 0.1 〇 Example 27 〇 03 0.1 〇 Comparative Example 11 XX Example 28-3 4 and Comparative Example 12_13 According to the same method of Example 9-16 and Comparative Example 6-T The film was stretched axially, but the terminal carboxyl group concentrations of the PET-based polyester and the PBT-based polyester therein were changed as shown in Table 8. The results are shown in Tables 8 and 9. ---- η ------ Ί 装 ------ 订 ------ i (Please read the precautions on the back / write this page) The Central Standards Bureau of the Ministry of Economic Affairs, Consumer Cooperatives Printing -36- This paper size is applicable to China National Standard (CNS) A4 (210X297 mm) 4 34 4 4
A 五、發明説明(V) 表8 PET PBT 聚碳酸酯分散粒子之長徑 末端羧基濃度 (當量A 06克) 末端羧基濃度 (當量/106克) (μπι) 比較例12 4 6 無法拉伸 實施例28 15 ' 6 6.7 實施例29 25 6 4.3 實施例30 35 6 2.8 實施例3 1 35 10 3.7 比較例13 35 25 無法拉伸 實施例32 30 8 3.0 實施例33 15 16 4.1 實施例34 35 6 3.5 I---η-----'袭—— (請先閱讀背面之注意事項-if填寫本頁)A V. Description of the invention (V) Table 8 Concentration of long-term terminal carboxyl group (equivalent A 06 g) of PET PBT polycarbonate dispersed particles Terminal carboxyl group concentration (equivalent / 106 g) (μπι) Comparative Example 12 4 6 Unstretchable implementation Example 28 15 '6 6.7 Example 29 25 6 4.3 Example 30 35 6 2.8 Example 3 1 35 10 3.7 Comparative Example 13 35 25 Unstretchable Example 32 30 8 3.0 Example 33 15 16 4.1 Example 34 35 6 3.5 I --- η ----- 'attack—— (Please read the precautions on the back-if you fill out this page)
'IT 經濟部中央橾準局貝工消費合作社印製 -37- 本紙張尺度14用中國國家梯準(CNS ) A4規格(210X297公釐) 434144 A7 B7 五、發明説明(斗) 表9 擠製成彤加工性 可拉伸性 剝離強度 (kg/cm) 低溫耐衝擊性 (mA) 縣性 比較例12 Δ X 實施例28 ◎ 〇 3.0 0.1 〇 實施例29 ◎ .◎ 2.5 0.1 〇 實施例30 ◎ ◎ 2.5 0.1 〇 實施例3 1 ◎ ◎ 2.5 0.1 〇 比較例13 X X 實施例32 ◎ ◎ 2.5 0.1 〇 實施例33 〇 〇 2.5 0.1 〇 實施例34 ◎ ◎ 2.5 0.1 〇 (請先閱讀背面之注意事項%4寫本頁) 裝. 經濟部中夬標隼局貝工消费合作社印製 實施例35-43和比較例14-U 用於聚酯膜層(第一 1(A))之聚合物及用於聚碳酸 酯-聚醋組成物膜層(第二靥(B))之聚合物與實施例卜8 和比較例1 - 4相同。 〔用於聚酯膜層(第三層(Ο)之聚合物之製備〕 利用固相聚合法以聚對苯二甲酸乙二酯舆15莫耳X異 苯二甲酸共聚合,異苯二甲酸之本質粘度為0.60,傜在 二氧化緒觸媒存在的情況下製得。此聚酯之熔點為218 .°C,玻璃轉移溫度為72°0。 〔積層膜之製備〕 -3 8 ^ Λ 本紙張尺度適用中國囷家標準(CNS ) A4規格(2】0Χ297公釐) 1 λ /1 1 4 4^ Α7 Β7 經濟部中央梯準局員工消费合作社印裝 五、發明説明(β ) 用於第一層(A>之聚酯,用於第二層(B>之聚碩酸酯-聚酯组成物,以及用於第三層(C)之聚酯如上所述用三 層楔依以上顒序共擠製製得三層未拉伸積層膜。 第一層(A)與第三層(C)之聚酯聚合物經乾燥之後,在 約28 (TC之聚合溫度下使用擠製機進行熔融擠製,而第 二層(B)也在約29G"C之聚合溫度下熔融擠製。經此三雇 模製得之稹層膜冷卻之< 後捲繞在鑄棍上面即播得未拉伸 薄膜。接著在130 °C之溫度下對此未拉伸薄膜横向拉伸 到3.0倍,然後在135 °C之溫度下縱向拉伸到3.G倍,最 後在180°C之溫度熱固化即製得雙軸拉伸積雇膜。 如此製得之雙軸拉伸薄膜,其第一層(A)之平面拉伸 像數為0.06,第二層(B>之平面拉伸係數為0.05,第三 層(C)之平面拉伸係數為Q.06,第一層(A)之厚度為3# η ,第二層(Β)之厚度為24/iB,第三層(C)之厚度為 。此薄膜之150DC熱牧缩率為5-7Χ。 評估結果示於表10中。本發明三層雙軸拉伸薄膜具備 搔佳的擠裂成形加工性、可拉伸性、低溫对衡擊性及保 香性,而與金屬板之黏著性也獲得極大的改良。 表10同時也示出在第二層(B)之組成物中使用的聚酯 和聚硪酸酯之熔點。 -39- 本紙張尺度適用中國國家標準(CNS) A4規格(210X297公釐) ί 1 ^—^1 - - ll· j. ^^^1 ^lfl ^^^1 一eJ (請先閲讀背面之注意事項#仏寫本頁) 434144, A7 B7 五、發明説明(4) 表10 組成物之熔點 (°C ) 擠觀形加工性 可拉伸性 剝離強度 (kg/cm) 雜耐衝擊性 (mA) 保香性 比較例14 *251/220 〇 〇 7 0.5 〇 實施例35 250/220 ◎ ◎ 7 0.2 〇 實施例36 251/221 ◎ ◎ 7 0.1 〇 實施例37 251/- ◎ ◎ 7 0.1 〇 比較例15 25 1/- X X 比較例16 -/224 Δ Δ 7 0.5 〇 實施例38 -/224 〇 〇 7 0.1 〇 實施例39 -/223 〇 〇 7 0.1 〇 實施例40 251/221 ◎ ◎ 7 0.1 〇 實施例41 252/- ◎ ◎ 7 0.1 〇 實施例42 252/- 〇 〇 7 0.1 〇 實施例43 253/- 〇 〇 7 0.1 〇 比較例Π 253/- X X *聚對苯二甲酸乙二酯之熔點/聚對苯二甲酸丁二酯之 fit· m itt rtt it rn n I tit j 1 \ J. HJ^i flf .¾. .1 ^ (請先聞讀背面之注意事項V%寫本頁) 經濟部中夬橾隼局貝工消费合作社印製 熔點 實施例4 4 - 5 1和比較例1 8 - 1 9 用於第一層(A)之聚合物及用於第二層(B)之聚碩酸酯 -聚酯組成物膜層之聚合物舆實施例9-16和比較例6-7相 同。 [用於聚酯膜靥(第三層(C>)之聚合物之製備〕 -4 0 - 本紙張尺度逍用中國困家標牟(CNS ) A4规格(210X297公釐) 434144 A 7 B7 五、發明説明(衫) 利用固相聚合法以聚對笨二甲酸乙二酷與7莫耳X異 苯二甲酸共聚合,異苯二甲酸之本質粘度為0·β0,镍在 二氣化緒梅媒存在的情況下製得β此聚酯之熔點為2 38 eC,玻璃轉移S度為76°Ce 〔積層糢之製備〕 上述聚對苯二甲酸乙二酯、聚硪酸酯-聚a組成物及 聚對苯二甲酸乙二酷之,共聚物皆依一般常用的方法乾燥 ,然後分別饋入各自的擠》機中形成三層共擠製積層膜 。聚對苯二甲酸乙二酯、聚磺酸酯-聚酯組成物及聚對 苯二甲酸乙二酯之共聚物從共擠製狹缝熔融擠製出來, 其聚合溫度分別為2 8 (TC、2 8 0 - 2 9 Q-C、及大約2 8 (TC。 共擠製膜經冷卻之後捲繞在一鑲棍上面製成依上述順序 積層之未拉伸積層薄膜。 捺著在135 90之溫度下對此未拉伸薄膜横向拉伸到3.fl 倍,然後也在135 eC之溫度下縱向拉伸到3.0倍,最後在 180°C之溫度熱固化卽製得雙軸拉伸積層膜》 如此製得之雙軸拉伸薄膜,其第一層(A)(聚對苯二 甲酸乙二酯層)之平面拉伸傲數為〇·Μ,第二層(B)( 聚硪酸酯-聚酯層)之平面拉伸係數為〇.06,第一層 (n m i tn 1^1 ^^^1 I. 1^1 i I i in^'J (請先閲讀背面之注意事項再填寫本頁) 經濟部中夹樣準局負工消费合作社印*. Αί 5 1 為為 度度 厚厚 之之 >薄 (C此 層 。三 } 第物 *聚 ί 共 之 酯二 乙 酸 (B二 層苯 二對 第聚 ο 2 為 度 厚 為 率 縮 收 熱 ρ 表 於 示 果 结 15估 之評 膜 % 7 酯 聚 基 酷二 乙 酸 甲二 苯 對 聚 當 〇 中 \-4 畺 當 5 在 度 濃 基. 羧 端 末 之 甲二 苯 對 聚 且 上 以 克 本纸浪尺度適用中國國家搮準(CNS ) A4规格(2!0X297公釐) 434144 A7 B7 五、發明説明(〇 ) 酸丁二酯基聚酯之末端羧基濃度在2 0當量/106克以下 時,所得薄膜即具備榴佳的輿金羼抿之黏着性,而成膜 性(濟製成形加工性和可拉伸性)也能夠令人谋意。 :---,h------.裝------訂 I.------义 (請先閲讀背面之注f項/¾寫本頁) 經濟部中央樣準局貝工消费合作社印製 賁施例5 2 - 5 5 以40重量Ϊ!實施例35-43中使用之聚硝酸酯與60重量% 實施例46中使用的由聚對苯二甲酸乙二酯和聚對苯二甲 酸丁二酯舆5莫耳X異苯二甲酸共聚合組成之聚酯乾混 ,做為碟化合物之 ADK STAB 2 112. {Asahi Denka Kogyo Co., Ltd.公司製)之添加量(以磷濃度表示)示於表 -4 2 -'Printed by the Central Consumers' Bureau of the Ministry of Economic Affairs, Shellfish Consumer Cooperatives-37- This paper size 14 uses the Chinese National Standard (CNS) A4 specification (210X297 mm) 434144 A7 B7 V. Description of the invention (bucket) Table 9 Extrusion Chengtong processability, stretchability, peeling strength (kg / cm), low temperature impact resistance (mA), county-level comparative example 12 ΔX Example 28 ◎ 3.0 3.0 0.1 Example 29 ◎. ◎ 2.5 0.1 〇 Example 30 ◎ ◎ 2.5 0.1 〇 Example 3 1 ◎ ◎ 2.5 0.1 〇 Comparative Example 13 XX Example 32 ◎ ◎ 2.5 0.1 〇 Example 33 〇 2.5 2.5 〇 Example 34 ◎ ◎ 2.5 0.1 〇 (Please read the notes on the back first% (4 write this page). Packaging. The Ministry of Economic Affairs of the Ministry of Economic Affairs, Bureau of Shellfish Consumer Cooperatives printed Examples 35-43 and Comparative Example 14-U. Polymers and Applications for Polyester Film (First 1 (A)) The polymer applied to the polycarbonate-polyacetate composition film layer (second step (B)) is the same as that in Example 8 and Comparative Examples 1-4. [Preparation of polymer for polyester film layer (third layer (0)] Copolymerization of 15 mol X isophthalic acid with polyethylene terephthalate and isophthalic acid by solid phase polymerization method, isophthalic acid The intrinsic viscosity is 0.60, which is prepared in the presence of a dioxin catalyst. The melting point of this polyester is 218 ° C and the glass transition temperature is 72 ° 0. [Preparation of laminated film] -3 8 ^ Λ This paper size is in accordance with the Chinese Standard (CNS) A4 specification (2) 0 × 297 mm. 1 λ / 1 1 4 4 ^ Α7 Β7 Printed by the Consumer Cooperative of the Central Ladder Bureau of the Ministry of Economic Affairs. 5. Description of Invention (β) is used for The polyester of the first layer (A >, a polyester-polyester composition for the second layer (B >), and the polyester for the third layer (C), as described above, have a three-layer wedge. Three layers of unstretched laminated film were prepared by sequential co-extrusion. After the polyester polymers of the first layer (A) and the third layer (C) were dried, the extruder was used at a polymerization temperature of about 28 (TC). Melt extrusion is performed, and the second layer (B) is also melt extruded at a polymerization temperature of about 29 G " C. The 稹 layer film obtained through the three-shot molding is cooled < The unstretched film was sown above. Then the unstretched film was stretched to 3.0 times in the transverse direction at a temperature of 130 ° C, then stretched to 3.G times in the longitudinal direction at a temperature of 135 ° C, and finally at 180 ° C. The biaxially stretched film is prepared by thermal curing at a temperature of ° C. The biaxially stretched film thus prepared has a plane stretched image number of 0.06 for the first layer (A), and a second layer (B > The plane tensile coefficient is 0.05, the plane tensile coefficient of the third layer (C) is Q.06, the thickness of the first layer (A) is 3 # η, and the thickness of the second layer (B) is 24 / iB. The thickness of the three layers (C) is. The 150DC thermal shrinkage ratio of this film is 5-7 ×. The evaluation results are shown in Table 10. The three-layer biaxially stretched film of the present invention has excellent extrusion molding processability, can be Tensile properties, low temperature impact resistance and fragrance retention, and the adhesion to metal plates have also been greatly improved. Table 10 also shows the polyesters and polymers used in the composition of the second layer (B). The melting point of gallate. -39- This paper size is in accordance with Chinese National Standard (CNS) A4 (210X297 mm) ί 1 ^ — ^ 1--ll · j. ^^^ 1 ^ lfl ^^^ 1 eJ (Please read the note on the back # (Written on this page) 434144, A7 B7 V. Description of the invention (4) Table 10 Melting point (° C) of the composition Extrusion processability Stretchability Peel strength (kg / cm) Miscellaneous impact resistance (mA) Guarantee Fragrance Comparative Example 14 * 251/220 〇07 0.5 〇 Example 35 250/220 ◎ ◎ 7 0.2 〇 Example 36 251/221 ◎ ◎ 7 0.1 〇 Example 37 251 /-◎ ◎ 7 0.1 〇 Comparative Example 15 25 1 /-XX Comparative Example 16-/ 224 Δ Δ 7 0.5 〇 Example 38-/ 224 〇07 0.1 〇 Example 39-/ 223 〇07 0.1 〇 Example 40 251/221 ◎ ◎ 7 0.1 〇 Implementation Example 41 252 /-◎ ◎ 7 0.1 〇 Example 42 252 /-〇07 0.1 〇 Example 43 253 /-〇07 0.1 〇 Comparative Example Π 253 /-XX * Melting point of polyethylene terephthalate / The fit of polybutylene terephthalate · m itt rtt it rn n I tit j 1 \ J. HJ ^ i flf .¾. .1 ^ (Please read the precautions on the back first V% write this page) Melting point printed by Zhongli Bureau Shellfish Consumer Cooperative of the Ministry of Economic Affairs Example 4 4-5 1 and Comparative Examples 1 8-1 9 Polymer used in the first layer (A) and polymer used in the second layer (B) Polyester-polyester composition The polymer film layer Yu Example 9-16 and Comparative Examples 6-7 are the same. [Preparation of polymer for polyester film 第三 (third layer (C >)]-4 0-This paper is scaled to China Standards (CNS) A4 (210X297 mm) 434144 A 7 B7 5 Description of the invention (shirt) Copolymerization of poly (ethylene terephthalate) and 7 mol X isophthalic acid by solid phase polymerization method, the intrinsic viscosity of isophthalic acid is 0 · β0, and nickel In the presence of plum media, β is obtained. The melting point of this polyester is 2 38 eC, and the glass transition S degree is 76 ° Ce. [Preparation of laminated mold] The above polyethylene terephthalate, polyacetate-polya The composition and polyethylene terephthalate are cool, and the copolymers are dried according to commonly used methods, and then fed to their respective extrusion machines to form three-layer co-extruded laminated films. Polyethylene terephthalate , Polysulfonate-polyester composition and polyethylene terephthalate copolymer are melt-extruded from co-extrusion slits, and their polymerization temperatures are 2 8 (TC, 2 8 0-2 9 QC And about 2 8 (TC.) The co-extruded film is cooled and wound on an inlaid stick to make an unstretched laminated film laminated in the above order. The unstretched film was stretched to 3.fl times in the transverse direction at a temperature of 5 90, and then 3.0 times in the longitudinal direction at a temperature of 135 eC. Finally, it was thermally cured at a temperature of 180 ° C to obtain a biaxially drawn film. Extruded layer film "The biaxially stretched film thus prepared had a first layer (A) (polyethylene terephthalate layer) having a plane stretch number of 0 · M and a second layer (B) ( Polyester-polyester layer) has a plane tensile coefficient of 0.06, and the first layer (nmi tn 1 ^ 1 ^^^ 1 I. 1 ^ 1 i I i in ^ 'J (Please read the Please fill in this page again.) Printed by the Ministry of Economic Affairs of the Ministry of Economic Affairs of the Sample Cooperative Consumer Cooperatives Co., Ltd. * Αί 5 1 is the thickness of the thick > thin (C this layer. Three) Articles * Poly Co-Ester Diacetic acid (B two-layer benzene di-para-poly ο 2 is the degree of thickness and the rate of heat shrinkage ρ is shown in the evaluation of the evaluation of the film 15% 7 esters of poly (diphenylene) benzene diacetic acid p-poly (p-phenylene) in the 0- 4 畺 当 5 at the concentration. The carboxyl-terminated methylbenzene is p-polymerized and the Chinese paper standard (CNS) A4 (2! 0X297 mm) is applied on the scale of the paper. 434144 A7 B7 V. Description of the invention ( 〇) Butyric acid When the terminal carboxyl group concentration of the ester-based polyester is less than 20 equivalents / 106 g, the obtained film has the adhesiveness of Lujiayujin, and the film forming property (formability and stretchability) is also good. Can be intriguing .: ---, h ------. Install -------- order I .------ meaning (please read the note f on the back / ¾ write this page) ) Printed by the Central Bureau of the Ministry of Economic Affairs, Shellfish Consumer Cooperative, Example 5 2-5 5 at 40% by weight! Polynitrate used in Examples 35-43 and 60% by weight of polymer pair used in Example 46 A dry blend of a polyester composed of ethylene phthalate and polybutylene terephthalate copolymerized with 5 mol X isophthalic acid as a dish compound. ADK STAB 2 112. {Asahi Denka Kogyo Co., Ltd.) is shown in Table-4 2-
表II 擠製成形加工性 可拉伸性 剝離強度 (kg/cm) 低溫耐衝擊性 (mA) 保香性 比較例18 Δ X 實施例44 ◎ 〇 6 0.1 〇 實施例45 ◎ ◎ 6 0.1 〇 實施例46 ◎ ◎ 6 0.1 〇 實施例47 ◎ ◎ 6 0.1 〇 實施例48 〇 〇 6 0.1 〇 比較例18 X X 實施例49 ◎ ◎ 6 0.1 〇 實施例50 〇 〇 5.5 0.1 〇 實施例5 1 ◎ ◎ 6 0.1 〇 本紙张尺度逋用中國固家樣牟(CNS > A4说格(210X297公釐) 434144 A7 B7_ 五、發明説明(4f ) 12中,依實施例48相同條件製得積層膜。 結果示於表12中。我們發現當磷化合物之添加量在20 -1 0 0 ΡΡβ之間時,可得到恃別好的結果。 (請先聞讀背面之注意事項-if%寫本頁) ,裝. 實施例56-62 在賁施例36中,第三層(C)聚酯中共聚合使用之異苯 二甲酸之用童如表13所示改變。各聚酯之熔黏也示於表 1 3中β ,tr Λ . 經濟部中央揉準局負工消費合作社印製 -43- 表12 磷化合物添加量 (ppm) 擠製成形加工性 可拉伸性 剝離強度 (kg/cm) 縱耐衝擊性 (mA) 保香性 實施例52 22 〇 〇 6 0.1 〇 實施例53 40 ◎ ◎ 6 0.1 〇 實施例54 50 ◎ ◎ 6 0.1 〇 實施例55 95 ◎ ◎ 6 0.1 〇 本紙張尺度適用中國國家樣準(CNS ) A4規格(210X297公釐) 434144 五、發明説明 表13 共聚合異苯二甲酸之用量(莫耳%) 熔點(°C ) 實施例56 0 (聚對苯二甲酸乙烯) 255 實施例57 2 250 實施例58 " 4 245 實施例59 10 230 實施例60 15 218 實施例61 20 205 實施例62 25 193 结果示於表14中。當異苯二甲酸之用量在3-20奠耳X 之間(實施例5 8 - 6 1)時,可得到待別好的結果β (請先閱讀背面之注意事項74寫本頁) •裝· 經濟部中央標隼局員工消費合作社印製 -44- 本紙張尺度適用中國國家標準(CNS ) Α4说格(2丨0X297公釐) Δ Δ 1— 4 3 4Table II Extrusion processability, stretchability, peeling strength (kg / cm), low temperature impact resistance (mA), aroma retention, comparative example 18 ΔX Example 44 ◎ 〇6 0.1 〇 Example 45 ◎ ◎ 6 0.1 〇 Implementation Example 46 ◎ ◎ 6 0.1 〇 Example 47 ◎ ◎ 6 0.1 〇 Example 48 〇 〇 6 0.1 〇 Comparative Example 18 XX Example 49 ◎ ◎ 6 0.1 〇 Example 50 〇 5.5 5.5 〇 Example 5 1 ◎ ◎ 6 0.1 〇 This paper size is based on Chinese solid sample (CNS > A4 grid (210X297 mm) 434144 A7 B7_ 5. In the description of the invention (4f) 12, the laminated film was prepared under the same conditions as in Example 48. The results are shown. In Table 12. We found that when the phosphorus compound is added in the amount of 20 -1 0 0 PPβ, good results can be obtained. (Please read the precautions on the back-if% write this page), install Examples 56-62 In Example 36, the copolymerization of isophthalic acid used in the third layer (C) polyester was changed as shown in Table 13. The melt adhesion of each polyester is also shown in Table 1. 3 中 β, tr Λ. Printed by the Central Consumers' Bureau of the Ministry of Economic Affairs and the Consumer Cooperatives -43- Table 12 Addition of Phosphorus Compounds ( ppm) Extrusion processability Stretchability Peel strength (kg / cm) Longitudinal impact resistance (mA) Fragrance retention Example 52 22 〇〇0.1 0.1 〇Example 53 40 ◎ ◎ 6 0.1 〇Example 54 50 ◎ ◎ 6 0.1 〇 Example 55 95 ◎ ◎ 6 0.1 〇 This paper size is applicable to China National Standard (CNS) A4 specification (210X297 mm) 434144 V. Description of the invention Table 13 Amount of copolymerized isophthalic acid (Mole %) Melting point (° C) Example 56 0 (polyethylene terephthalate) 255 Example 57 2 250 Example 58 " 4 245 Example 59 10 230 Example 60 15 218 Example 61 20 205 Example 62 The results of 25 193 are shown in Table 14. When the amount of isophthalic acid is between 3 and 20 Moore X (Examples 5 8-6 1), good results can be obtained β (Please read the (Note 74 written on this page) • Printed by the Consumer Cooperative of the Central Bureau of Standards of the Ministry of Economic Affairs -44- This paper size is applicable to the Chinese National Standard (CNS) Α4 grid (2 丨 0X297 mm) Δ Δ 1— 4 3 4
A B 五、發明説明(4〇 表14 擠製成形加工性 可拉伸性 剝離強度 (kg/cm) 低溫耐衝擊性 (mA) 保香性 實施例56 ◎ ◎ 5 O.l 〇 實施例57 ◎ ◎ 5.5 0. I 〇 實施例58 ◎ < ◎ 6 O.l 〇 實施例59 ◎ ◎ 6.5 O.l 〇 實施例60 ◎ ◎ 7 O.l 〇 實施例6 I ◎ ◎ 7.5 O.l 〇 實施例62 〇 〇 8 0」 〇 ----U------' ^-- (請先閲讀背面之注意事項弄填寫本頁) 經濟部中央標準局貝工消费合作社印裂 實施例63-68 在實施例46中,用於第三層(C)之聚對笨二甲酸乙二 酷層共聚合使用之異苯二甲酸之厚度如表15所示以確保 第二層(B)與第三層(C)之總厚度為21//祖。 所得結果示於表15中。當第三層(C)之厚度在0.5-10 之間時(實施例64-67),可得到特別好的結果。尤 其當第三層之厚度為I-5/ub時(實施例65和66),結果 更佳〇 -4 5- 本紙張尺度通用十菌國家標準(CNS ) Α4規格(2!0X297公嫠) 訂 4341 44 五 _ 經濟部中央揉準局貝工消资合作社印裝 A7 B7 發明説明(44) 表15 第三層(C)厚度 (㈣ 擠製成形加工性 可拉伸性 剝離瓣 (kg/cm) 麟耐衝擊性 (mA) 實施例63 0.1 ◎ ◎ 4.5 0.2 〇 實施例64 0.5 ◎ ◎ 5 0.1 〇 實施例65 2 ◎ 6 0.1 〇 實施例66 5 ◎ ◎ 6.5 0.1 〇 實施例67 8 ◎ ◎ 7 0.1 〇 實施例68 12 ◎ ◎ 7.5 0.3 〇 實施例6 9- 7 5和比較例20-23 除 了依表 16 所示比率之 ADK STAB 2112 (Asahi Denka Kogyo Co., Ltd.公荀製)取代6〇ΡΡ«ι磷酸,以及第二靥 (B)之组成物如表16所示改變之外.依實施例1-8和tb較 例1-4同樣方法裂備未拉伸薄膜。 -46* 本紙張尺度逍用中囷國家揉率(CNS ) A4规格(210X297公釐) n-n n I - m i -ill n \ I - In 1 (請先聞讀背面之注項声填寫本頁) 434144 A7AB 5. Description of the invention (40 Table 14 Extrusion processability Stretchability Peel strength (kg / cm) Low temperature impact resistance (mA) Fragrance retention Example 56 ◎ ◎ 5 Ol 〇 Example 57 ◎ ◎ 5.5 0.1 I 〇 Example 58 ◎ < ◎ 6 Ol 〇 Example 59 ◎ ◎ 6.5 Ol 〇 Example 60 ◎ ◎ 7 Ol 〇 Example 6 I ◎ 7.5 Ol 〇 Example 62 〇 0 0 0 〇- --U ------ '^-(Please read the precautions on the back and fill out this page first.) The Central Standards Bureau of the Ministry of Economic Affairs, Shellfish Consumer Cooperative, printed examples 63-68. In Example 46, The thickness of the isophthalic acid used in the copolymerization of the third layer (C) of polyethylene terephthalate is shown in Table 15 to ensure that the total thickness of the second layer (B) and the third layer (C) is 21 // 祖. The results obtained are shown in Table 15. When the thickness of the third layer (C) is between 0.5-10 (Examples 64-67), particularly good results can be obtained. Especially when the thickness of the third layer (C) When the thickness is I-5 / ub (Examples 65 and 66), the results are better. 0-4 5- This paper is a universal standard for ten bacteria (CNS) Α4 size (2! 0X297 cm). Printed with A7 B7 by the Central Bureau of the Ministry of Plastics and Rubber Cooperatives. Description of the invention (44) Table 15 Thickness of the third layer (C) (㈣ Extrusion processability Stretchable peeling flap (kg / cm) Lin impact resistance (mA) Example 63 0.1 ◎ ◎ 4.5 0.2 〇Example 64 0.5 ◎ ◎ 5 0.1 〇Example 65 2 ◎ 6 0.1 〇Example 66 5 ◎ ◎ 6.5 0.1 〇Example 67 8 ◎ ◎ 7 0.1 〇Example 68 12 ◎ ◎ 7.5 0.3 〇 Example 6 9- 7 5 and Comparative Examples 20-23 Except ADK STAB 2112 (manufactured by Asahi Denka Kogyo Co., Ltd.) in the ratio shown in Table 16 in place of 6〇ΡΡιι phosphoric acid And the composition of the second (B) is changed as shown in Table 16. The unstretched film was prepared in the same manner as in Examples 1-8 and tb compared with Examples 1-4. Central China National Kneading Rate (CNS) A4 (210X297 mm) nn n I-mi -ill n \ I-In 1 (Please read the note on the back to fill out this page first) 434144 A7
B 五、發明説明() 表1 6 聚碳酸酯 (重量%) 聚酯 (重量%) PET (重量 PBT (重量%) 磷基穩定劑 (ppm) 比較例20 18 82 40 60 40 實施例69 22 78 40 60 40 實施例70 40 60 40 60 40 比較例21 62 38 40 60 40 比較例22 40 60 8 92 40 實施例71 40 60 12 88 40 實施例72 40 60 20 80 40 實施例73 40 60 60 40 40 實施例74 40 60 80 20 40 實施例75 40 60 88 12 40 比較例23 40 60 92 8 40B. Description of the invention (Table 6) Polycarbonate (wt.%) Polyester (wt.%) PET (wt. PBT (wt.%) Phosphorus-based stabilizer (ppm) Comparative Example 20 18 82 40 60 40 Example 69 22 78 40 60 40 Example 70 40 60 40 60 40 Comparative Example 21 62 38 40 60 40 Comparative Example 22 40 60 8 92 40 Example 71 40 60 12 88 40 Example 72 40 60 20 80 40 Example 73 40 60 60 40 40 Example 74 40 60 80 20 40 Example 75 40 60 88 12 40 Comparative Example 23 40 60 92 8 40
經濟部中央標準局負工消費合作社印II PET:聚對苯二甲酸乙二酯 PBT.·聚對苯二甲酸丁二酯評估結果示於表17中。從表中可看出本發明雙軸拉伸積 層膜具備極佳的擠製成形加工性、可拉伸性、與金鼸板 之黏箸性、低溫酌衝擊性及保香性》 -47- 本紙張尺度逋用中國國家標準(CNS ) A4规格(2丨0X297公釐)The results of the evaluation by the Central Standards Bureau of the Ministry of Economic Affairs and Consumer Cooperatives II PET: Polyethylene terephthalate PBT. · Polybutylene terephthalate are shown in Table 17. It can be seen from the table that the biaxially stretched laminated film of the present invention has excellent extrusion processability, stretchability, adhesion to the gold plate, low-temperature impact resistance, and fragrance retention "-47- This paper uses Chinese National Standard (CNS) A4 (2 丨 0X297 mm)
Il·,—-------裝------訂------A (諳先閱讀背面之注意事項孑楱寫本頁) 434 1 4 4Il ·, ---------- install ------ order ------ A (谙 read the precautions on the back first, write this page) 434 1 4 4
A B 五、發明説明(4各) 表17 最高尖峰溫度 (ETC) 擠製成形加工性 可拉伸性 剝離強度 (kg/cm) 寵耐衝擊性 (mA) 保香性 比較例20 130 ◎ ◎ 6 0.5 〇 實施例69 142 ◎ ◎ 6 0.2 〇 實施例70 144 ◎ ◎ 3 0.1 〇 比較例21 > X X 比較例22 108 Δ △ 3 0.5 〇 實施例71 112 〇 〇 2.5 0.1 〇 實施例72 120 〇 〇 2.5 0.1 〇 實施例73 148 ◎ ◎ 3 0.1 〇 實施例74 156 ◎ ◎ 3 0.1 〇 實施例75 157 〇 〇 3 0.1 〇 比較例23 „ Π X X . 經濟部中央揉準局貝工消費合作社印製 實施例7 6 - 8 4和比較例2 4 · 2 7 用於第一層(Α)之聚合物及所用之聚磺酸酯均與實施 例1-8和比較例1-4相同。 [用於聚硪酸酯-聚醱組成物膜層(第二層(Β))之聚合物 以及積層膜之製備〕 依表18所示比例混合上述聚碩酸酯與聚酯混合物(聚 酯混合物你依表18所示比例使與12Μ耳X異苯二甲酸共 聚合後做為第一雇U)用之聚對苯二甲酸乙二酯與聚對 4 8 ——|<-----i------tr------A (請先閱讀背面之注意事項-f.4:寫本頁) 本紙張尺度適用中國國家橾準(CNS ) A4«L格(2丨OX297公釐) 434144 Α7 Β7 五、發明説明(47 ) 苯二甲酸丁二酯混合後所得之混合物),然後依表18所 示用量加入《I酸做為磷化合物。所得混合物連同第一層 (A)用雙層鑄棋共擠製裂成雙層未拉伸薄咦β在此擠製 程序中,第一層(Α)之聚酯聚合物經乾燥之後是在約28G •C之聚合溫度下使用擠製機進行熔融擠製,而第二層(Β) &在約2 3 (TC之聚合溫度下熔融擠製。經此雙層模製得 之積®膜聚合物冷卻么後捲繞在鑄輥上面邸獲得未拉伸 薄腠》未拉伸薄膜接著依表19所示拉伸比及溫度進行縱 向及横向拉伸,同樣也依表19所示溫度熱固化,如此邸 製得雙軸拉伸積層膜。 (請先閏讀背面之注意事項$寫本頁) 經濟部中央標準局—工消費合作社印製 •49- 本紙張尺度適用中國國家標牟(CNS ) Α4说格(210Χ297公羞) 434144AB 5. Description of the invention (4 each) Table 17 Maximum peak temperature (ETC) Extrusion molding processability Stretchability Peel strength (kg / cm) Impact resistance (mA) Comparative example 20 130 ◎ ◎ 6 0.5 〇Example 69 142 ◎ ◎ 6 0.2 〇Example 70 144 ◎ ◎ 3 0.1 〇Comparative Example 21 > XX Comparative Example 22 108 Δ △ 3 0.5 〇Example 71 112 〇2.5 0.1 〇Example 72 120 〇 2.5 0.1 〇Example 73 148 ◎ ◎ 3 0.1 〇Example 74 156 ◎ ◎ 3 0.1 〇Example 75 157 〇〇3 0.1 〇Comparative Example 23 „Π XX. Printed and implemented by Shellfish Consumer Cooperatives, Central Bureau of the Ministry of Economic Affairs Examples 7 6-8 4 and Comparative Example 2 4 · 2 7 The polymers used in the first layer (A) and the polysulfonic acid esters used were the same as in Examples 1-8 and Comparative Examples 1-4. Polyurethane-Polyfluorene Composition Film (Polymer (Second Layer (B)) Polymer and Preparation of Laminated Film)] Mix the above-mentioned poly-ester and polyester mixture in the proportion shown in Table 18 The ratios shown in Table 18 make poly (p-phenylene) used as the first polymer after copolymerization with 12Mear X isophthalic acid. Ethylene formate and polypara 4 8 —— | < ----- i ------ tr ------ A (Please read the precautions on the back first-f.4: Write this page ) This paper size applies to China National Standards (CNS) A4 «L (2 丨 OX297 mm) 434144 A7 B7 V. Description of the invention (47) The mixture obtained by mixing butyl phthalate), and then according to Table 18 The amount shown is added with "I acid as a phosphorus compound. The resulting mixture is co-extruded with a first layer (A) into a double-layered unstretched thin film β in a double-layer cast chess. In this extrusion process, the first layer ( The polyester polymer of A) is melt-extruded using an extruder at a polymerization temperature of about 28 G • C, and the second layer (B) & is melt-extruded at a polymerization temperature of about 2 3 (TC). After the double-layered molded polymer is cooled, it is wound on a casting roll to obtain an unstretched film. The unstretched film is then stretched in the longitudinal direction and according to the stretching ratio and temperature shown in Table 19. Horizontal stretching is also thermally cured at the temperature shown in Table 19. In this way, a biaxially stretched laminated film is prepared. (Please read the notes on the back first to write this page) Central Standards Bureau of the Ministry of Economic Affairs-Industrial Consumption • 49- cooperatives printed in this paper scale applicable Chinese national standard Mu (CNS) Α4 said grid (210Χ297 public shame) 434 144
7 7 A B 五、發明説明(4) 表18 聚碳酸酯 (重量°/〇 聚酯 (重量%) PET (重量 ΡΒΤ (重量%) 磷基穩定劑 (ppm) 比較例24 18 82 40 60 60 實施例76 22 78 40 60 60 實施例Τ7 40 60 40 60 50 比較例25 62 Λ. 38 40 60 40 比較例26 40 60 S 92 80 實施例78 40 60 12 88 80 實施例79 40 60 20 80 60 實施例80 40 60 60 40 40 實施例81 40 60 80 20 20 實施例82 40 60 88 12 20 比較例27 40 60 92 8 20 實施例83 40 60 40 60 50 實施例84 40 60 40 60 50 (請先閱讀背面之注意事項者填寫本頁) 經濟部中央標準局員工消費合作社印製 PET:聚對苯二甲酸乙二酯 PBT:聚對苯二甲酸丁二酯 如此製得之雙軸拉伸薄膜,其第一層(A)之平面拉伸 傷數為0.06,第二層(B) 6之平面拉伸傜數為〇.〇5,第 一層(A )之厚度為6// a ,第二層(B )之厚度為2 4 # 。此 薄膜之150eC熱收縮率為5-7X。 -50- 本纸張尺度適用中國國家揉準(CNS ) A4規格(2〗0Χ297公釐) 434144 A7 B? 五、發明説明(49 ) 表19 縱向拉伸溫度 (°C) 縱向拉伸比 橫向拉伸溫度 (°C) 橫向拉伸比 熱固化溫度 (°C) 比較例24 120 2.9 140 3.0 180 實施例76 120 2.9 140 3.0 180 實施例77 120 2.9 140 3.0 180 比較例25 120 2.9 140 3.0 180 比較例26 120 2.9 140 3.0 180 實施例78 120 2.9 140 3.0 180 實施例79 120 2.9 140 3.0 180 實施例80 120 2.9 140 3.0 180 實施例81 120 2.9 140 3.0 180 實施例82 120 2.9 140 3.0 180 比較例27 120 2.9 140 3.0 180 實施例83 120 2.5 135 3.4 180 實施例84 120 3.2 140 2.8 180 (請先閲讀背面之注意事項声4寫本頁) 經濟部中央標準局負工消費合作社印製 評估結果示於表20中^從表中可看出本發明雙軸拉伸 積層膜具備搔佳的擠製成形加工性、可拉伸性、與金羼 板之黏著性、低溫酎衝擊性及保香性。 -5 1- 本紙張尺度適用中國國家橾率(CNS ) A4規格(210X297公釐) 434144 A7 B7 五、發明説明(ί-) 表20 (Em+Et)/2 Em-Et 擠製成形加工性 連續膜性質 剝離強度 (kg/cm) 讎耐衝擊性 (mA) 保香性 比較例24 230 -20 ◎ ◎ 7.0 0.6 〇 實施例76 230 20 ◎ ◎ 6.0 0.2 〇 實施例77 210 100 ◎ 3.0 0.1 〇 比較例25 160 120 X X . 比較例26 250 140 Δ 〇 2.0 0.5 〇 實施例78 250 120 〇 ◎ 2.5 0.1 〇 實施例79 245 130 〇 ◎ 3.0 0.1 〇 實施例80 180 80 ◎ 〇 3.5 0.1 〇 實施例81 160 80 ◎ 〇 3.0 0.1 〇 寅施例82 160 60 〇 〇 3.0 0.1 〇 比較例27 155 30 X X 實施例83 170 240 〇 〇 3.0 0.2 〇 實施例84 160 -40 〇 〇 3.0 0.1 〇 -----------裝-- (請先W讀背面之注意事項孑¾寫本頁) -訂 經濟部中央榉準局貝工消费合作社印装 實施例85-92和比較例28-29 用於第一層(A)之聚硪酸酯及聚對苯二甲酸乙二酯均 與實施例1-8和比較例卜4相同。使用AM STAB PEP-8作 為聚碩酸酯之磷基穩定剤。如表21所示將40重量U此種聚磺酸酯以及60重量χ由聚-52 - 本纸張尺度適用中國國家標準(CNS ) A4規格(2丨0X297公釐) 434144 A77 7 AB V. Description of the invention (4) Table 18 Polycarbonate (wt ° / 〇 polyester (wt.%) PET (wt. PBT (wt.%) Phosphorus-based stabilizer (ppm) Comparative Example 24 18 82 40 60 60 Implementation Example 76 22 78 40 60 60 Example T7 40 60 40 60 50 Comparative Example 25 62 Λ. 38 40 60 40 Comparative Example 26 40 60 S 92 80 Example 78 40 60 12 88 80 Example 79 40 60 20 80 60 Implementation Example 80 40 60 60 40 40 Example 81 40 60 80 20 20 Example 82 40 60 88 12 20 Comparative Example 27 40 60 92 8 20 Example 83 40 60 40 60 50 Example 84 40 60 40 60 50 (Please first Those who read the notes on the back fill in this page) The biaxially stretched film made of PET: polyethylene terephthalate PBT: polybutylene terephthalate, printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs, The number of plane tensile injuries of the first layer (A) is 0.06, the number of plane tensile injuries of the second layer (B) 6 is 0.05, and the thickness of the first layer (A) is 6 / a. The thickness of the second layer (B) is 2 4 #. The 150eC thermal shrinkage of this film is 5-7X. -50- This paper size is applicable to China National Standard (CNS) A4 (2) 0 × 297 mm 434144 A7 B? V. Description of the invention (49) Table 19 Longitudinal stretching temperature (° C) Longitudinal stretching ratio Lateral stretching temperature (° C) Lateral stretching ratio heat curing temperature (° C) Comparative Example 24 120 2.9 140 3.0 180 Example 76 120 2.9 140 3.0 180 Example 77 120 2.9 140 3.0 180 Comparative Example 25 120 2.9 140 3.0 180 Comparative Example 26 120 2.9 140 3.0 180 Example 78 120 2.9 140 3.0 180 Example 79 120 2.9 140 3.0 180 Implementation Example 80 120 2.9 140 3.0 180 Example 81 120 2.9 140 3.0 180 Example 82 120 2.9 140 3.0 180 Comparative Example 27 120 2.9 140 3.0 180 Example 83 120 2.5 135 3.4 180 Example 84 120 3.2 140 2.8 180 (Please first (Please read the note on the back of this page and write this page.) The evaluation results printed by the Central Standards Bureau of the Ministry of Economic Affairs and Consumer Cooperatives are shown in Table 20. It can be seen from the table that the biaxially stretched laminated film of the present invention has excellent extrusion. Formability, stretchability, adhesion to gold-plated sheet, low-temperature impact resistance, and fragrance retention. -5 1- This paper size is applicable to China National Standard (CNS) A4 specification (210X297 mm) 434144 A7 B7 V. Description of invention (ί-) Table 20 (Em + Et) / 2 Em-Et Extrusion processability Continuous film properties Peel strength (kg / cm) 冲击 Impact resistance (mA) Fragrance retention Comparative Example 24 230 -20 ◎ 7.0 0.6 〇 Example 76 230 20 ◎ ◎ 6.0 0.2 〇 Example 77 210 100 ◎ 3.0 0.1 〇 Comparative Example 25 160 120 XX. Comparative Example 26 250 140 Δ 〇2.0 0.5 〇Example 78 250 120 〇 ◎ 2.5 0.1 〇Example 79 245 130 〇 ◎ 3.0 0.1 〇Example 80 180 80 ◎ 〇3.5 0.1 〇Example 81 160 80 ◎ 〇3.0 0.1 〇 Example 82 160 60 〇3.0 3.0 〇 Comparative Example 27 155 30 XX Example 83 170 240 〇3.0 3.0 〇 Example 84 160 -40 〇3.0 3.0 -------- ------ Equipment-(Please read the precautions on the back 孑 ¾write this page)-Order the printing of Examples 85-92 and Comparative Examples 28-29 of the Central Beef Consumer Cooperative of the Ministry of Economic Affairs Polyester and polyethylene terephthalate on the first layer (A) are the same as those of Examples 1-8 and Comparative Example 4. AM STAB PEP-8 is used as a phosphorus-based stabilized plutonium of a polybasic acid ester. As shown in Table 21, 40 weight U of this polysulfonate and 60 weight χ by poly-52-this paper size applies Chinese National Standard (CNS) A4 specifications (2 丨 0X297 mm) 434144 A7
7 B 五、發明说明(θ ) 對苯二甲酸乙二酯基聚酯(40重董與聚對苯二甲酸丁 二酯基聚酯(6U重童J!)組成之聚酯乾混在一起》 聚對苯二甲酸乙二酯基聚酯和聚對苯二甲酸丁二酯基 聚酯皆以固相聚合物方法製成。前者使用二氧化緒觸媒 ,後者則使用钛酸四丁酯觸媒,預聚合物之本質拈度, 在固相聚合反應中之固柑聚合時間,以及末端羧基濃度 均如表21所示有所改變 表21 PET基聚酯 麵 本質粘度 熔點 CC) 玻璃轉移溫度 (°C) 末端羧基濃度 (當量/1〇6克) 比較例28 PETI12 0.75 229 74 4 實施例85 PETI12 0.75 229 74 12 實施例86 PETI12 0.75 229 74 20 實施例87 PETI12 0.75 229 74 30 實施例88 PETI12 0.75 229 74 30 實施例89 PETI12 0.75 229 74 30 比較例2 9 PETI12 0.75 229 74 30 實施例90 PETI12 0.75 225 78 25 實施例91 PETI12 0.75 225 78 12 實施例92 PETI12 0.75 225 78 30 經濟部中央樣準局員工消费合作社印装 PET:聚對苯二甲酸乙二酷 PETI12:與12莫耳!Ϊ異苯二甲酸共聚合之PET -53- (請先聞讀背面之注意事項再填寫本頁) 本紙張尺度適用中國國家標準(CNS ) A4現格(2丨0X29"?公釐) 4 4 47 B V. Description of the invention (θ) Polyethylene terephthalate-based polyester (polyester composed of 40 weights of Dong and polybutylene terephthalate (6U heavy boy J!) Dry blended together " Both polyethylene terephthalate-based polyester and polybutylene terephthalate-based polyester are made by a solid-phase polymer method. The former uses a dioxin catalyst and the latter uses a tetrabutyl titanate catalyst. Medium, the pre-polymer's intrinsic degree, the solid polymerization time in the solid phase polymerization reaction, and the terminal carboxyl group concentration are changed as shown in Table 21 Table 21 PET-based polyester surface intrinsic viscosity melting point CC) glass transition temperature (° C) Concentration of terminal carboxyl groups (equivalents / 106 g) Comparative Example 28 PETI12 0.75 229 74 4 Example 85 PETI12 0.75 229 74 12 Example 86 PETI12 0.75 229 74 20 Example 87 PETI12 0.75 229 74 30 Example 88 PETI12 0.75 229 74 30 Example 89 PETI12 0.75 229 74 30 Comparative Example 2 9 PETI12 0.75 229 74 30 Example 90 PETI12 0.75 225 78 25 Example 91 PETI12 0.75 225 78 12 Example 92 PETI12 0.75 225 78 30 Central Ministry of Economy Associate Bureau Staff Consumer Cooperative Printing PET: Poly Ethyl terephthalate PETI12: with 12 moles! ΪIsophthalic acid copolymerized PET -53- (Please read the precautions on the back before filling out this page) This paper size applies Chinese National Standard (CNS) A4 (2 丨 0X29 "? Mm) 4 4 4
AA
7 B 五、發明説明() 表21(續) PBT基聚酯 mm 本質粘度 熔點 CC) 玻璃轉移雛 (°C) 末端羧基濃度 (當量/106克) 比較例2S PBTI5 0,9 218 28 8 實施例85 ΡΒΤΪ5 0.9 218 28 8 實施例86 PBTI5 0.9 218 28 8 實施例87 PBTI5 0.9 218 28 8 實施例88 PBTI5 0.9 218 28 12 實施例89 PBTI5 0.9 218 28 20 比較例29 PBTI5 0.9 218 28 22 實施例90 PBT 0.9 223 32 10 實施例9 1 PBT 0.9 223 32 18 實施例92 PBTI5 0.9 223 28 8 ----------裝-- (诗先閲讀背面之注意事項孑%寫本頁) 經濟部中央標準局貝工消費合作杜印裝 PBT:聚對苯二甲酸丁二酯 PETI5 :與5莫耳5:異苯二甲酸共聚合之PBT 依實施例1-8和比較例1-4製得雙軸拉伸薄膜。橫向拉 伸是在140°C下進行。評估結果示於表22中。 -54- 本纸張尺度適用t國國家標準(CNS ) A4規格(210X297公釐) 434144 A7 B7 五、發明説明(Η ) 經濟部中央標準局貝工消费合作社印製 表22 擠製成形加工性 可拉伸性 剝離強度 (kg/cm) 低溫耐衝擊性 (mA) 保香性 比較例28 Δ X 實施例85 ◎ 〇 2.5 0.1 〇 實施例86 ◎ ◎ 2.5 0.1 〇 實施例87 ◎ -¼ ◎ 3.0 0.1 〇 實施例88 ◎ ◎ 3.0 0.1 〇 實施例89 〇 〇 3.5 0.1 〇 比較例29 X X 實施例90 ◎ ◎ 2.0 0.2 〇 實施例9 1 / 〇 〇 2.0 0.1 〇 實施例92 ◎ ◎ 3.0 0.1 〇 實施例93-9&和比較例30-33 實施例6 9 - 7 5和比較例20-23之雙軸拉伸薄膜,其低溫 結晶化尖峰溫度(Tccl和Tcc4}、擠製成形加工性以及可 拉伸性示於表2 3中。 -----------装-- (锖先閲讀背面之注意事項%填寫本頁) 訂 -55- 本紙張尺度適用中國國家標準(CNS ) A4規格(210X 297公釐) 4 3 4 彳 4 4 A7 B7 五、發明説明(Μ )7 B V. Description of the invention () Table 21 (continued) PBT-based polyester mm intrinsic viscosity melting point CC) glass transition chick (° C) terminal carboxyl group concentration (equivalent / 106 g) Comparative Example 2S PBTI5 0,9 218 28 8 Implementation Example 85 PBS 5 0.9 218 28 8 Example 86 PBTI5 0.9 218 28 8 Example 87 PBTI5 0.9 218 28 8 Example 88 PBTI5 0.9 218 28 12 Example 89 PBTI5 0.9 218 28 20 Comparative Example 29 PBTI5 0.9 218 28 22 Example 90 PBT 0.9 223 32 10 Example 9 1 PBT 0.9 223 32 18 Example 92 PBTI5 0.9 223 28 8 ---------- install-(Notes on the back of the poem before reading 孑% write this page) Economy Ministry of Central Standards Bureau, Shellfish, Consumer Cooperation, DuPont PBT: Polybutylene terephthalate PETI5: PBT copolymerized with 5 mol 5: Isophthalic acid. Manufactured according to Examples 1-8 and Comparative Examples 1-4. A biaxially stretched film was obtained. The lateral stretching is performed at 140 ° C. The evaluation results are shown in Table 22. -54- This paper size is applicable to the national standard (CNS) A4 specification (210X297 mm) 434144 A7 B7 V. Description of the invention (Η) Printed by the Central Standards Bureau of the Ministry of Economic Affairs, Shellfish Consumer Cooperatives. 22 Forming processability Tensile peeling strength (kg / cm) Low temperature impact resistance (mA) Fragrance retention Comparative Example 28 Δ X Example 85 ◎ 〇2.5 0.1 〇Example 86 ◎ ◎ 2.5 0.1 〇Example 87 ◎ -¼ ◎ 3.0 0.1 〇Example 88 ◎ ◎ 3.0 0.1 〇Example 89 〇〇3.5 0.1 〇Comparative Example 29 XX Example 90 ◎ ◎ 2.0 0.2 〇Example 9 1 / 〇2.0 2.0 〇Example 92 ◎ ◎ 3.0 0.1 〇Example 93-9 & and Comparative Examples 30-33 Examples 6 9-7 5 and Comparative Examples 20-23 The biaxially stretched films have low-temperature crystallization peak temperatures (Tccl and Tcc4), extrusion processability, and drawability The extensibility is shown in Table 2. 3. ----------- Installation-(锖 Please read the notes on the back first% to fill out this page) Order-55- This paper size applies to China National Standard (CNS) A4 specification (210X 297 mm) 4 3 4 彳 4 4 A7 B7 V. Description of the invention (M)
表23 Tccl Tcc4 Tcc4-Tcc 1 擠製成形加工性 可拉伸性 °c °c °c 比較例30 95 132 37 ◎ ◎ 實施例93 95 134 39 ◎ ◎ 實施例94 92 137 45 ◎ ◎ 比較例3 1 91 138 47 X X 比較例3 2 60 104 44 Δ 0 實施例95 66 108 42 〇 ◎ 實施例96 75 110 35 〇 ◎ 實施例97 115 145 30 ◎ 〇 實施例98 152 170 18 ◎ 〇 實施例99 156 172 16 〇 〇 比較例3 3 157 170 13 X X 實施例100-107和bb較例34-37實施例1-8和比較例1-4之雙軸拉伸薄膜,其每一侮之 中心線表面粗糙度(Ra)示於表24*0 (請先閲讀背面之注意事項龙填寫本頁) 裝' 訂 經濟部中央標隼局貝工消费合作社印装 -56- 本紙張尺度適用中國國家標率(CNS > A4规格(210X297公釐} 434144Table 23 Tccl Tcc4 Tcc4-Tcc 1 Extrusion processability stretchability ° c ° c ° c Comparative Example 30 95 132 37 ◎ ◎ Example 93 95 134 39 ◎ ◎ Example 94 92 137 45 ◎ ◎ Comparative Example 3 1 91 138 47 XX Comparative Example 3 2 60 104 44 Δ 0 Example 95 66 108 42 〇 ◎ Example 96 75 110 35 〇 ◎ Example 97 115 145 30 ◎ 〇 Example 98 152 170 18 ◎ 〇 Example 99 156 172 16 〇Comparative Example 3 3 157 170 13 XX Examples 100-107 and bb Comparative Examples 34-37 Examples 1-8 and Comparative Examples 1-4 The biaxially stretched films, each centerline surface Roughness (Ra) is shown in Table 24 * 0 (please read the precautions on the back to fill in this page first) (CNS > A4 size (210X297 mm) 434144
A B 五、發明説明(β) 表24 Ra(nm) 比較例34 23 實施例100 25 實施例101 27 比較例35 比較例36 13 實施例102 15 實施例103 17 實施例104 20 實施例105 37 實施例106 54 實施例107 110 比較例37 • ----------装-- (請先聞讀背面之注意事項再績寫本頁) 經濟部中失標準為員工消费合作社印裝 -57- 本紙張尺度適用中國國家標率(CNS )戍4说格(2I0X297公釐)AB 5. Description of the invention (β) Table 24 Ra (nm) Comparative Example 34 23 Example 100 25 Example 101 27 Comparative Example 35 Comparative Example 36 13 Example 102 15 Example 103 17 Example 104 20 Example 105 37 Implementation Example 106 54 Example 107 110 Comparative Example 37 • ---------- Installation-(Please read the precautions on the back before writing this page) The standard of the Ministry of Economic Affairs is printed for employee consumer cooperatives -57- This paper size applies to China National Standards (CNS) 4 grid (2I0X297 mm)
Claims (1)
Applications Claiming Priority (5)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP8023862A JPH09216322A (en) | 1996-02-09 | 1996-02-09 | Biaxially oriented laminated film for laminating to metal plate |
JP8023863A JPH09216323A (en) | 1996-02-09 | 1996-02-09 | Biaxially oriented laminated film for laminating to metal plate |
JP8023861A JPH09216321A (en) | 1996-02-09 | 1996-02-09 | Biaxially oriented laminated film for laminating to metal plate |
JP8508596A JPH09272190A (en) | 1996-04-08 | 1996-04-08 | Biaxially drawn laminated film for laminating metal sheet |
JP8086499A JPH09277473A (en) | 1996-04-09 | 1996-04-09 | Biaxially oriented laminated film for laminated metal plate |
Publications (1)
Publication Number | Publication Date |
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TW434144B true TW434144B (en) | 2001-05-16 |
Family
ID=27520577
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
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TW85108782A TW434144B (en) | 1996-02-09 | 1996-07-19 | Biaxially oriented film to be laminated on a metal |
Country Status (1)
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TW (1) | TW434144B (en) |
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1996
- 1996-07-19 TW TW85108782A patent/TW434144B/en not_active IP Right Cessation
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