TW591093B - Polyiscyanate curing agent for laminate adhesive, laminate adhesive comprising the same and its use - Google Patents
Polyiscyanate curing agent for laminate adhesive, laminate adhesive comprising the same and its use Download PDFInfo
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591093 經濟部中央標隼局員工消費合作社印製 A7 ____B7___五、發明説明（1 ) 發明背景 發明領域 本發明係有關於疊層黏著劑用之含親水極性基之多異 氰酸酯，含彼之疊層黏著劑以及該疊層黏著劑於膜疊層中 之應用。· 相關先前技藝 近來，基於包裝強度、商品保護性、包裝工作性、包 I 裝宣傳功效、降>4包裝成本（以低價供應大量之膜）等因 素，一種以複雜撓性包裝作爲包裝方法已顯著地發展。 在此類複雜撓性包裝中作爲疊層黏著劑者，現在的主 流是一種兩劑式固化型聚胺基甲酸酯黏著劑，其由具有含 活性氫基團（如羥基等）之樹脂（主成份）與多異氰酸酯 (固化劑）所組成，因其優異結合性、耐久性與耐熱性， 故可用在各種不同之膜中。 例如，J P - A - 5 — 1 1 2 7 6 6揭不一種含聚胺 基甲酸酯樹脂與多異氰酸酯固化劑之黏著劑，其中聚胺基 甲酸酯樹脂具有親水極性基。再者，J P — A — 7 -4 8 4 2 9揭示一種多異氰酸酯固化劑，其具有親水極性 基。 但是，在J P — A - 5-1 1 2766之多異氰酸酯 固化劑系統中，當使用非聚胺基甲酸酯樹脂之其他樹脂作 爲主成份時_，將使其對金屬箔、.金屬化膜或聚烯烴_膜之黏 性不足。此外，雖然J P — A - 4 8 4 2 9提及水性黏著 本紙張尺度適用中國國家淼準（CNS ) A4規格（210><297公釐） (請先閲讀背面之注意事項 π本頁) -裝· 、1Τ 線 591093 A7 _______ B7五、發明説明（2 ) 劑，但此水性黏著劑需要將水吹走，所以要花費較多能量 經濟部中央標準局員工消費合作社印製 發明簡述 本發明之目的在於提出一種疊層黏著劑之多異氰酸酯 固化劑，其使黏著劑具有優異耐熱性、耐久性及對金屬膜 與聚烯烴膜之黏性。 本發明另一目的爲提出具有優異耐熱性、耐久.性及對 金屬膜與聚烯烴膜黏性之疊層黏著劑，其包括上述固化劑 〇 本發明再一目的爲提出該黏著劑在膜疊層之應用。 本發明其他目的與優點以下述說明揭示。 本發明提出下列： (1 ) 一種疊層黏著劑用之多異氰酸酯固化劑，包括含親 水極性基之多異氰酸酯， (2 ) —種疊層黏著劑，包括上述（1 )之多異氰酸酯固 化劑以及含活性氫化合物， (3 )含上述（1 )之多異氰酸酯固化劑的黏著劑及含活 性氫化合物在膜疊層之應用。 發明詳述 本發明疊層黏著劑用之多異氰酸酯固化劑包括含親水 極性基之多_異氰酸酯。 _ 含親水極性基之多異氰酸酯可由有機多異氰酸酯與具 (請先閲讀背面之注意事項再一^馬本頁)591093 Printed by A7 ____B7___ of the Consumer Cooperatives of the Central Bureau of Standards of the Ministry of Economic Affairs 5. Description of the Invention (1) Background of the Invention Field of the Invention The present invention relates to polyisocyanates containing hydrophilic polar groups for laminating adhesives, and laminations containing each other. Adhesive and use of the laminated adhesive in film lamination. · Related previous techniques Recently, based on factors such as packaging strength, product protection, packaging workability, packaging promotion effectiveness, > 4 packaging costs (supplied large quantities of films at low prices), and other factors, a complex flexible packaging is used as the packaging The method has developed significantly. As a laminated adhesive in such complex flexible packaging, the mainstream now is a two-part curing polyurethane adhesive, which is composed of a resin with active hydrogen groups (such as hydroxyl groups) ( The main component) and polyisocyanate (curing agent) are used in various films because of their excellent binding, durability and heat resistance. For example, J P-A-5-1 1 2 7 6 6 reveals an adhesive containing a polyurethane resin and a polyisocyanate curing agent, in which the polyurethane resin has a hydrophilic polar group. Furthermore, J P — A — 7 -4 8 4 2 9 discloses a polyisocyanate curing agent having a hydrophilic polar group. However, in the polyisocyanate curing agent system of JP — A-5-1 1 2766, when other resins other than polyurethane resin are used as the main component, it will cause it to be applied to metal foil and metallized film. Or the viscosity of polyolefin film is insufficient. In addition, although JP — A-4 8 4 2 9 mentions water-based adhesives, the paper size is applicable to the Chinese National Miao Zhun (CNS) A4 specification (210 > < 297 mm) (please read the precautions on the back page first) -Installation · 1T line 591093 A7 _______ B7 V. Invention description (2), but this water-based adhesive requires water to be blown away, so it will take more energy to print a brief description of the invention by the Consumers' Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs The object of the invention is to provide a polyisocyanate curing agent for laminated adhesives, which makes the adhesives have excellent heat resistance, durability, and tackiness to metal films and polyolefin films. Another object of the present invention is to provide a laminated adhesive having excellent heat resistance, durability, and adhesion to a metal film and a polyolefin film, which includes the above curing agent. Another object of the present invention is to provide the adhesive on a film stack. Application of layers. Other objects and advantages of the present invention are disclosed in the following description. The present invention proposes the following: (1) a polyisocyanate curing agent for a laminating adhesive, including a polyisocyanate containing a hydrophilic polar group, (2) a laminating adhesive, including the polyisocyanate curing agent of the above (1), and Active hydrogen-containing compound, (3) the adhesive containing the polyisocyanate curing agent of the above (1) and the application of the active hydrogen-containing compound in film lamination. DETAILED DESCRIPTION OF THE INVENTION The polyisocyanate curing agent for the laminated adhesive of the present invention includes a poly-isocyanate containing a hydrophilic polar group. _ Polyisocyanates containing hydrophilic polar groups can be prepared from organic polyisocyanates and materials (please read the precautions on the back first and then ^ this page)
、ar 線 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） -5. 591093 A7 B7 五、發明説明（3 ) 有至少一個含活性氫基團之含親水極性基化合物反應而輕 易製成。 有機多異氰酸酯包括已知有機多異氰酸酯及其改質產 物。 經濟部中央標準局員工消費合作社印製 其特定例包括，例如，芳族二異氰酸酯，如，2 ’ 4 一甲苯二異氰酸酯，2，6 —甲苯二異氰酸酯，二甲苯一 1 ，4 一二異氰酸酯，二甲苯一1，3 —二異氰酸酯，二 甲苯一1 ，2 —二異氰酸酯，4，4，一二苯甲烷·二異氰 酸酯，2，4’ 一二苯甲烷二異氰酸酯，4，4’ 一二苯醚 二異氰酸酯，2 -硝基一二苯基一 4，4，一二異氰酸酯 ，2，2，一二苯丙烷一 4，4，一二異氰酸酯，3，3’ 一二甲二苯甲烷一 4，4’ 一二異氰酸酯，4，4’ 一二苯 丙烷二異氰酸酯，間苯二異氰酸酯，對苯二異氰酸酯’萘 一 1 ，4 一二異氰酸酯，萘—1，5 —二異氰酸酯，3， 3，一二甲氧二苯基一 4，4’ 一二異氰酸酯，四甲基二甲 苯基二異氰酸酯等；脂族二異氰酸酯，如，丁二異氰酸酯 ，己二異氰酸酯，3 —甲基一 1 ，5 —戊烷二異氰酸酯， 離胺酸二異氰酸酯等：環狀二異氰酸酯，如，異佛爾酮二 異氰酸酯，氫化甲苯二異氰酸酯，氫化二甲苯二異氰酸酯 ，氫化二苯甲烷二異氰酸酯等；其加成物；衍生自上述二 異氰酸酯之含縮二脲鍵多異氰酸酯、含碳二醯亞胺鍵·多異 氰酸酯、含脲亞胺鍵多異氰酸酯、含脲二酮鍵多異氰酸醋 與含異氰脲_酸酯鍵多異氰酸酯；及其聚合物。上述钶生自 二異氰酸酯之二異氰酸酯與多異氰酸酯可單獨或混合使用 -6 - 本紙張尺度適用中國國家標準（CNS >A4規格（210x297公釐） 591093 A7 B7 經濟部中央標準局員工消費合作社印製 五、發明説明（4 ) 〇 其中較佳者爲衍生自己二異氰酸酯之含異氰脲酸酯鍵 多異氰酸酯以及衍生自己二異氰酸酯之具有異氰脲酸酯鍵 與脲二酮鍵之多異氰酸酯，因其具有優異耐久性，耐熱性 等。 具有含活性氫基團之含親水極性基化合物中的親水極 性基有非離子極性基，陰極子極性基，陽離子極性基與兩 性極性基。本發明中，親水極性基可單獨或合倂使用。考 慮所得疊層黏著劑用之多異氰酸酯固化劑的安定性時，以 /非離子極性基作爲親水極性基爲佳。 具有含活性氫基團之含非離子極性基化合物有聚氧烷 醚單元醇，聚氧烷醚多元醇，聚氧烷脂肪酸酯單元醇等， 其中環氧乙院單兀至少佔5 〇mo 1 e%，重覆單元較好 爲3至90，更好爲5至50。本發明中，較好使用聚氧 烷醚單元醇與聚氧烷醚多元醇，最好是聚氧烷醚單元醇。 製備上述聚氧烷醚單元醇之起始劑有甲醇，乙醇，正 丙醇，異丙醇，正丁醇，異丁醇，第三丁醇，環己醇，酚 等。製備上述聚氧烷醚多元醇之起始劑有乙二醇，丙二醇 ’苯胺，三甲醇丙烷，甘油等。其中不超過5個碳原子之 化合物爲佳，如，甲醇，乙醇，乙二醇，丙二醇等，因其 對金屬的黏性·會變好，更好爲不超過5個碳原子之單元醇 ，如，甲醇，乙醇等。 再者 '製備上述聚氧烷脂肪酸酯單元醇之脂肪酸有乙 酸，丙酸，正丁酸，異丁酸，正戊酸，異戊酸，己二酸， (請先閲讀背面之注意事項 π本頁) 裝 訂 線 本紙乐尺度適用中國國家標準（CNS ) Α4規格（210X297公釐） 591093 A7 B7 五、發明説明（5 ) 葡糖酸，乳酸，甲氧乙酸等。其中不超過5個碳原子之脂 肪酸爲佳，如，乙酸，丙酸，正丁酸，異丁酸，正戊酸’ 異戊酸等，因其對金屬的黏性會變好。 具有含活性氫基團之含陰離子極性基化合物的適宜例 子爲由具有·至少一個含活性氫基團之有機酸與中和劑所組 成。上述有機酸可爲具有下述基團之化合物：羧酸基’磺 酸基，磷酸基，膦酸基，次膦酸基，硫代磺酸基等’這些 基團可被獨立引入或是如螫合物中之結合狀態。 經濟部中央標隼局員工消費合作社印製 具有至少^個含活性氫基團之有機酸的特定例包括羥 脂族酸，如，α -羥丙酸，羥丁二酸，二羥丁二酸，£一 羥丙烷一 1，2，3 -三羧酸，羥乙酸，α -羥丁酸，羥 硬脂酸，蓖蔴油酸，蓖蔴油硬脂酸，柳酸，扁桃酸等’以 及下列不飽和脂肪酸之羥化產物：油酸，亞油酸等；二胺 類胺基酸，如，穀醯胺，天冬醯胺，賴胺酸，二胺基丙酸 ，鳥胺酸，二胺基苯甲酸等；單胺類胺基酸，如，甘胺酸 ，丙胺酸，榖胺酸，牛磺酸，胺基己酸，胺基苯甲酸’胺 基異酞酸等；胺基磺酸，如，胺基磺酸，二胺基苯磺酸等 ;含羧基多元醇，如，2，2 —二甲醇丙酸，2，2 —二 甲醇丁酸等；螯合化合物，如，亞胺二乙酸與縮水甘油之 加成物；.5 -鈉磺醯基異酞酸或5 -鉀磺醯基異酞酸得到 之聚酯多元醇；以水或含羧基之醇作爲起始劑得到的聚己 內酯；具有含活性氫基團之聚酯或是具有含活性氫基團之 聚碳酸酯與_含羧基醇之酯交換牽物。 _ 再者，亦可使用由長鏈多元醇與上述低分子量多兀醇 -8 - 本紙張尺度適用中國國家標準（CNS ) Α4規格（210Χ297公釐） 591093 經濟部中央標準局員工消費合作社印製 A7 B7五、發明説明（6 ) 或低分子量多元胺與多元羧酸酐反應所得含羧基半酯混合 物與含羧基半醯胺混合物。特別是，當將多元醇加至如苯 均四酐或其他類似酸酐時，會形成二個羧基，所以可將一 個陰離子極性基引入該聚酯多元醇之分子鏈中。其他陰離 子極性基有磷酸等等。上述長鏈多元醇特別包括上述聚醋 多元醇，聚醚多元醇，聚碳酸酯多元醇，聚烯烴多元醇等 〇 可提及之中和劑有氨；有機胺，如，乙胺，三甲胺， 三乙胺，三異丙胺，三丁胺，三乙醇胺，N —甲基二乙醇 胺，N —苯基二乙醇胺，單乙醇胺，二甲基乙醇胺，二乙 基乙醇胺，嗎啉，N —甲基嗎啉，2 —胺基一 2 —乙基一 1 -丙醇等；鹼金屬，如，鋰，鉀、鈉等；無機鹼，如， 氫氧化鈉與氫氧化鉀；等。爲了提高乾燥後耐候性與耐水 性，較好爲氨，三甲胺與三乙胺，因其受熱易解離且揮發 性高。 該有機酸與中和劑可單獨使用或是二個以上混合使用 〇 具有含活性氫基團之含陽離子極性基化合物的例子爲 由下列組成者：具有至少一個含活性氫之基團的三級胺與 中和劑（無機或有機酸）或是四級試劑。 具有至少一個含活性氫基團之四級胺可提及之例子有 N，N —二甲基乙醇胺，n，N —二乙基乙醇胺，N，N 一二丙基乙.醇胺，N，N —二苯基乙醇胺，N —甲基一 N —乙基乙醇胺，N —甲基一 N—苯基乙醇胺，N，N —二 本紙張尺度適用中國國家標準（CNS ) μ規格（210X297公釐） Γ〇Τ (請先閱讀背面之注意事項f •裝-- F本頁) 線 591093 / 經濟部中央標準局員工消費合作社印製 A7 _ B7五、發明説明（7 ) 甲基丙醇胺，N —甲基一 N —乙基丙醇胺，N —甲基二乙 醇胺，N —乙基二乙醇胺，N —甲基二丙醇胺，N —苯基 二乙醇胺，N —苯基二丙醇胺，N -羥乙基一 N -羥丙基 甲胺，N，Ν’ —二羥乙基六氫吡畊，三乙醇胺，三異丙 醇胺，Ν —-甲基一二（3 —胺丙基）胺，Ν —甲基一二（ 2 -胺丙基）胺等。此外，亦可使用氧化烯與氨，一級胺 (如甲胺）或二級胺（如二甲胺）之加成產物。 無機與有機酸可提及之例子有氫氯酸、乙酸、.乳酸、 氰乙酸、磷酸、硫酸等。四級試劑可提及之例子有硫酸二 甲酯；苯甲基氯；溴乙醯胺；氯乙醯胺；烷基鹵，如，乙 基溴，丙基溴，丁基溴等等。 其他含陽離子極性基之化合物有一級胺鹽，二級胺鹽 ，三級胺鹽，嘧啶鎗鹽等。 具有含活性氫基團之含兩性極性基之化合物可提及的 例子係如下製成之化合物：由含四級胺基多元醇與萘迫磺 內酯（Siiltone ，此化合物具有如磺醯甜菜鹼等兩性極性 基）反應而得。 在含陰離子或陽離子極性基之化合物的例子中，中和 劑與四級試劑之添加與反應可在有機多異氰酸酯與具有含 活性氫基團之有機酸及/或四級胺反應之後，或者是具有 含活性氫基團之有機酸及/或四級胺可與中和劑或四·級試 劑反應，然後再與有機多異氰酸酯反應，含磺酸基之化合 物較好在與_有機多異氰酸酯反應前便中和。 _ 本發明疊層黏著劑用多異氰酸酯固化劑中引入之親水 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） · 1〇 _ (請先閲讀背面之注意事項、 Ar line The size of this paper applies Chinese National Standard (CNS) A4 specification (210X297 mm) -5.591093 A7 B7 V. Description of the invention (3) There is at least one active polar group containing hydrophilic polar group compounds to react easily. production. Organic polyisocyanates include known organic polyisocyanates and their modified products. Specific examples printed by the Consumer Cooperatives of the Central Bureau of Standards of the Ministry of Economic Affairs include, for example, aromatic diisocyanates such as 2 '4-toluene diisocyanate, 2,6-toluene diisocyanate, xylene-1, 4-diisocyanate, Xylene-1,3-diisocyanate, Xylene-1,2-diisocyanate, 4,4,1-diphenylmethane · diisocyanate, 2,4'-diphenylmethane diisocyanate, 4,4'-diphenylbenzene Ether diisocyanate, 2-nitro-diphenyl-1,4,4-diisocyanate, 2,2, diphenylpropane-4,4,1-diisocyanate, 3,3'-dimethyldiphenylmethane-4 , 4'-diisocyanate, 4,4'-diphenylpropane diisocyanate, m-phenylene diisocyanate, p-phenylenediisocyanate 'naphthalene-1,4-diisocyanate, naphthalene-1,5-diisocyanate, 3, 3, Dimethoxydiphenyl-4,4'-diisocyanate, tetramethylxylyl diisocyanate, etc .; aliphatic diisocyanates, such as butyl diisocyanate, hexamethylene diisocyanate, 3-methyl-1, 5 — Pentane diisocyanate Diisocyanate, etc .: cyclic diisocyanates, such as isophorone diisocyanate, hydrogenated toluene diisocyanate, hydrogenated xylene diisocyanate, hydrogenated diphenylmethane diisocyanate, etc .; adducts thereof; derived from the above-mentioned diisocyanate containing Diurea bond polyisocyanate, carbon-containing diamido bond · polyisocyanate, urea-imine bond-containing polyisocyanate, uretdione bond-containing polyisocyanate, and isocyanurate-ester bond-containing polyisocyanate; and polymerization thereof Thing. The above-mentioned diisocyanate and polyisocyanate, which are derived from diisocyanates, can be used alone or in mixture. -6-This paper size applies to Chinese national standards (CNS > A4 size (210x297 mm) 591093 A7 B7 Printed by the Consumers' Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs Preparation of the invention 5. Description of the invention (4) 〇 Among them, the polyisocyanate containing an isocyanurate bond derived from a diisocyanate and a polyisocyanate having an isocyanurate bond and a uretdione bond derived from a diisocyanate, Because of its excellent durability, heat resistance, etc. The hydrophilic polar group in the hydrophilic polar group-containing compound having an active hydrogen group includes a nonionic polar group, a cathodic polar group, a cationic polar group, and an amphoteric polar group. In the present invention The hydrophilic polar group can be used alone or in combination. When considering the stability of the polyisocyanate curing agent for the obtained laminated adhesive, it is better to use a / nonionic polar group as the hydrophilic polar group. The ionic polar group compounds include polyoxyalkyl ether unit alcohol, polyoxyalkyl ether polyol, polyoxyalkyl fatty acid ester unit alcohol, etc., among which The oxygen content of the oxygen compound is at least 50 mol 1 e%, and the repeating unit is preferably from 3 to 90, more preferably from 5 to 50. In the present invention, a polyoxyalkylene ether unit alcohol and a polyoxyalkylene ether are preferably used. The alcohol is preferably a polyoxyalkylene ether unit alcohol. The starting agents for preparing the above polyoxyalkylene ether unit alcohol are methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, and third butanol, Cyclohexanol, phenol, etc. The starting agents for preparing the above polyoxyalkylene polyols are ethylene glycol, propylene glycol 'aniline, trimethylolpropane, glycerol, etc. Among them, compounds having no more than 5 carbon atoms are preferred, such as methanol , Ethanol, ethylene glycol, propylene glycol, etc., because of its viscosity to the metal will be better, more preferably a unit alcohol of not more than 5 carbon atoms, such as methanol, ethanol, etc. Furthermore, 'the above-mentioned polyoxane The fatty acids of the fatty acid ester unit alcohol are acetic acid, propionic acid, n-butyric acid, isobutyric acid, n-valeric acid, isovaleric acid, and adipic acid. (Please read the precautions on the back page on this page first.) Applicable to China National Standard (CNS) A4 specification (210X297 mm) 591093 A7 B7 V. Description of invention (5) Portugal Acids, lactic acid, methoxyacetic acid, etc. Among them, fatty acids with no more than 5 carbon atoms are preferred, such as acetic acid, propionic acid, n-butyric acid, isobutyric acid, n-valeric acid 'isovaleric acid, etc. The viscosity becomes better. A suitable example of the anionic polar group-containing compound having an active hydrogen group is composed of an organic acid having at least one active hydrogen group and a neutralizing agent. The organic acid may have the following Compounds of groups: carboxylic acid group 'sulfonic acid group, phosphoric acid group, phosphonic acid group, phosphinic acid group, thiosulfonic acid group, etc.' These groups can be introduced independently or in a combined state such as in adducts. Specific examples of organic acids with at least ^ active hydrogen-containing organic acids printed by the Consumer Cooperative of the Central Bureau of Standards of the Ministry of Economic Affairs include hydroxyaliphatic acids such as alpha-hydroxypropionic acid, hydroxysuccinic acid, and dihydroxysuccinic acid , Hydroxypropane-1,2,3-tricarboxylic acid, glycolic acid, α-hydroxybutyric acid, hydroxystearic acid, ricinoleic acid, ricinoleic stearic acid, salicylic acid, mandelic acid, etc. 'and the following are not Hydroxylated products of saturated fatty acids: oleic acid, linoleic acid, etc .; diamine amino acids, such as Amine, asparagine, lysine, diaminopropionic acid, ornithine, diaminobenzoic acid, etc .; monoamine amino acids, such as, glycine, alanine, lysine, taurine Acid, aminohexanoic acid, aminobenzoic acid 'aminoisophthalic acid, etc .; aminosulfonic acid, such as aminosulfonic acid, diaminobenzenesulfonic acid, etc .; carboxyl-containing polyols, such as 2, 2 — Dimethanol propionic acid, 2,2-dimethanol butyric acid, etc .; chelating compounds, such as the adduct of imine diacetic acid and glycidol; .5-sodium sulfoisophthalic acid or 5-potassium sulfofluorenyl Polyester polyols obtained from isophthalic acid; polycaprolactones obtained using water or a carboxyl-containing alcohol as a starter; polyesters with active hydrogen groups or polycarbonates with active hydrogen groups and _ Carboxylic alcohol-containing transesterification products. _ Furthermore, it is also possible to use long-chain polyols and the above-mentioned low-molecular-weight polyols -8-This paper size applies to China National Standard (CNS) A4 specifications (210 × 297 mm) 591093 Employee Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs A7 B7 V. Description of the invention (6) or a mixture of a carboxyl-containing half ester and a carboxyl-containing hemiamine obtained by reacting a low molecular weight polyamine with a polycarboxylic anhydride. In particular, when a polyol is added to, for example, pyromellitic anhydride or other similar anhydrides, two carboxyl groups are formed, so an anionic polar group can be introduced into the molecular chain of the polyester polyol. Other anion polar groups include phosphoric acid and the like. The above long-chain polyols include the above-mentioned polyester polyols, polyether polyols, polycarbonate polyols, polyolefin polyols, and the like. As neutralizers, there can be mentioned ammonia; organic amines such as ethylamine, and trimethylamine. , Triethylamine, triisopropylamine, tributylamine, triethanolamine, N-methyldiethanolamine, N-phenyldiethanolamine, monoethanolamine, dimethylethanolamine, diethylethanolamine, morpholine, N-methyl Morpholine, 2-amino-2-ethyl-1-propanol, etc .; alkali metals, such as lithium, potassium, sodium, etc .; inorganic bases, such as sodium hydroxide and potassium hydroxide; etc. In order to improve the weather resistance and water resistance after drying, ammonia, trimethylamine, and triethylamine are preferred because they are easily dissociated by heat and have high volatility. The organic acid and the neutralizing agent may be used alone or in combination of two or more. Examples of the cationic polar group-containing compound having an active hydrogen group are those consisting of: a third stage having at least one active hydrogen-containing group Amines and neutralizers (inorganic or organic acids) or quaternary reagents. Examples which may be mentioned of quaternary amines having at least one active hydrogen group include N, N-dimethylethanolamine, n, N-diethylethanolamine, N, N-dipropylethyl. Alcoholamine, N, N-diphenylethanolamine, N-methyl-N-ethylethanolamine, N-methyl-N-phenylethanolamine, N, N-two paper sizes are applicable to Chinese National Standards (CNS) μ specifications (210X297 mm) ) Γ〇Τ (Please read the precautions on the back f • Installation-F page) Line 591093 / Printed by A7 _ B7 of the Consumer Cooperatives of the Central Bureau of Standards of the Ministry of Economic Affairs 5. Description of the invention (7) Methylpropanolamine, N-methyl-N-ethylpropanolamine, N-methyldiethanolamine, N-ethyldiethanolamine, N-methyldipropanolamine, N-phenyldiethanolamine, N-phenyldipropanol Amine, N-hydroxyethyl-N-hydroxypropylmethylamine, N, N'-dihydroxyethylhexahydropyramine, triethanolamine, triisopropanolamine, N-methyl-bis (3-amine Propyl) amine, N-methyldi (2-aminopropyl) amine, and the like. In addition, addition products of alkylene oxide and ammonia, primary amines (such as methylamine) or secondary amines (such as dimethylamine) can also be used. Examples of inorganic and organic acids include hydrochloric acid, acetic acid, lactic acid, cyanoacetic acid, phosphoric acid, sulfuric acid, and the like. Examples of quaternary reagents that may be mentioned are dimethyl sulfate; benzyl chloride; bromoacetamide; chloroacetamide; alkyl halides such as ethyl bromide, propyl bromide, butyl bromide and the like. Other compounds containing cationic polar groups include primary amine salts, secondary amine salts, tertiary amine salts, pyrimidine gun salts, and the like. Examples of compounds containing an amphoteric polar group containing an active hydrogen group are compounds prepared as follows: a compound containing a quaternary amine group-containing polyol and naphthyl sultone (Siiltone, this compound has, for example, sulfobetaine And other amphoteric polar groups). In the case of compounds containing anionic or cationic polar groups, the addition and reaction of the neutralizing agent and the quaternary reagent may be after the reaction of the organic polyisocyanate with the organic acid and / or quaternary amine having an active hydrogen group, or Organic acids and / or quaternary amines containing active hydrogen groups can be reacted with neutralizing agents or quaternary reagents and then reacted with organic polyisocyanates. Compounds containing sulfonic acid groups are preferably reacted with _organic polyisocyanates Neutralize before. _ The hydrophilicity introduced in the polyisocyanate curing agent for laminated adhesives of the present invention. The paper size is applicable to the Chinese National Standard (CNS) A4 specification (210X297 mm) · 1 _ (Please read the precautions on the back first
訂 線 591093 A7 _____ 五、發明説明（8 ) 、 — - — 極性基的數量如下： 當非離子極性基引入時，多異氰酸酯固化劑中環氧乙 烷單元之含量較好爲0·1至4〇wt%，最好爲0·5 至3 〇w t %，相較於固含量而言。 當陰離子或陽離子極性基引入時，極性基之含量較好 爲0 · 1至3 · Ommo Ι/g，最好爲0 · 15至 2 · 9 m m ο 1 / g 〇 當親水極性基的量低於上述下限，其對金屬之黏性不 足。若其量高於上述上限，黏著劑之耐久性，特別是耐水 性，會變得不足。 經濟部中央標準局員工消費合作社印製 本發明疊層黏著劑用固化劑可爲與作爲額外反應物之 具有含活性氫基團之含疏水基化合物的反應產物。此具有 含活性氫基團之含疏水基化合物包括低分子量單元醇’如 ，甲醇、乙醇、正丙醇、異丙醇、正丁醇、異丁醇、第三 丁醇、戊醇、己醇、庚醇、辛醇、2 —乙基己醇、苯甲醇 、環己醇、伸烷基二醇單烷醚等；低分子量一級單胺，如 ，乙胺，丁胺，苯胺等；低分子量二級單胺’如二乙胺， 二丁胺，甲苯胺；具有含活性氫基團之聚酯；具有含活性 氫基團之聚醚，其中環氧乙烷單元的比例低於5 0 mmo 1 % ;具有含活性氫基團之聚碳酸酯；具有含活性 氫基團之聚烯烴；具有至少6個碳原子之羥基高級脂肪酸 以及其酯；等等。 有機多異氰酸酯與具有含活性氫基團之化合物劈好於 1 0至1 20°C反應，更好爲30至1 00°C。再者，與 -11 - 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） 591093 經濟部中央標準局員工消費合作社印製 A7 B7五、發明説明（9 ) 任意之具有含活性氫基團之含疏水基化合物的反應可在引 入親水極性基之同時進行或不同時候進行。此時’若需要 ，可加入胺基甲酸酯化觸媒’如’二月桂酸二丁基錫或三 伸乙基二胺。 所得疊層黏著劑用多異_酯固化劑之異氰酸酯基含 暈較好爲5至5 〇w t % ’更好爲1 0至4 t)w t%。 本發明疊層黏著劑用多異氰酸酯固化劑之平均N C〇 官能度較好爲2 · 0至5 · 0 ’最好爲2 · 0至4· 0° 當平均N C〇官能度小於2 · 0，則交聯密度會變小而使 結合強度不足。然而若平均N C〇官能度超過5 · 0，則 交聯密度會變成不必要的大，使得結合層之撓性不足。 倂用於本發明疊層黏著劑用多異氰酸酯固化劑中之作 爲主成份之含活性氫化合物在分子中含至少一個含活性氫 之基團，且較好爲數均分子量500至100000，特 別是1 0 0 0至8 0 0 0 0，之含活性氫高分子量化合物 。其例子有聚胺基甲酸酯樹脂；聚酯樹脂；聚醯胺樹脂； 丙烯酸系樹脂；香豆滿酮；蜜胺樹脂；尿素樹脂；松香樹 脂；環氧樹脂；酚樹脂；聚乙酸乙烯酯；纖維素型樹脂， 如，纖維素等；天然樹脂，如，澱粉、皮膠等；聚乙烯醇 ;及其衍生物等等，各個分子中具有至少一個含活性氫基 團。 · 該聚胺基甲酸酯樹脂除了具有胺基甲酸酯鍵之聚胺基 甲酸酯樹脂_外，還包括具有胺基甲酸酯鍵與尿素鍵_之聚胺 基甲酸酯樹脂，等等。 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） -12 - /1 (請先閱讀背面之注事項本頁) -裝· 訂 線 591093 A7 B7 五、發明説明（1〇 ) 聚胺基甲酸酯樹脂分子中包含至少一個，較好至少二 個，含活性氫基團，如，羥基等。此胺基甲酸酯樹脂與疊 層黏著劑用含親水極性基多異氰酸酯固化劑倂用而作爲兩 劑型固化類疊層黏著劑。 此聚胺基甲酸酯樹脂由已知反應從具有含活性氫基團 之化合物與有機多異氰酸酯而得。 具有含活性氫基團之化合物稱爲長鏈多元醇及/或鏈 擴充劑。本發明聚胺基甲酸酯樹脂中，較好含5 0.至9 0 wt%長鍵多兀醇。 長鏈多元醇可提及的有聚酯多元醇，聚碳酸酯多元醇 ，聚醚多元醇，聚烯烴多元醇，蔬菜油型多元醇，彼等之 共多元醇等等。這些長鏈多元醇可單獨使用或二者以上混 用。長鏈多元醇較好之數均分子量爲5 0 0至1 0 0 0 0 。鑑於黏性、耐久性等，本發明中以聚酯多元醇較佳。 上述聚酯多元醇可爲至少一個選自下列群體（A )與 至少一個選自下列群體（B )之脫水縮合反應所得聚酯多 元醇與聚酯醯胺多元醇，群體（A):多元羧酸，如，丁 二酸，己二酸，癸二酸，壬二酸，對駄酸，異駄酸，原駄 酸，六氫對酞酸，六氫異酞酸，六氫原酞酸，萘二羧酸， 苯偏三酸等；彼等之酯：彼等之酸酐；等等；群體（B ) ••低分子量多元醇，如，乙二醇，1，2 —丙二醇，1 ， 3 -丙二醇，1，3 -丁二醇，1，4 一丁二醇，1，5 一戊二醇，JL ，6 —己二醇，3 —甲基一 1 ，5 —戊二醇 ，新戊二醇，1，8 —辛二醇，1，9 一壬二醇，二乙二 (請先閲讀背面之注意事項 本頁) 經濟部中央標準局員工消費合作社印製 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） · 13 · 591093 經濟部中央標準局員工消費合作社印製 A7 B7五、發明説明（11 ) 醇，二丙二醇，1，4 一環己二甲醇，雙酚A之氧化乙烯 或氧化丙烯加成物，甘油，三甲醇丙烷，季戊四醇等；低 分子量多元胺，如，己二胺，二甲苯胺，異佛爾酮二胺等 ;低分子量胺醇，如，單乙醇胺，二乙醇胺等。本發明中 ，「低分子·量多元醇」’ 「低分子量多元胺」與「低分子 量胺醇」的「低分子量」指數均分子量爲低於5 0 0。 再者，亦可提及的有環酯（內酯）單體，例如，ε -己內酯，r—戊內酯或其他，以上述低分子量多元醇作爲 起始劑進行開環聚合所得內酯型聚酯多元醇。 聚碳酸酯多元醇可提及的有，由上述低分子量多元醇 與碳酸乙二酯、碳酸二甲酯、碳酸二乙酯、碳酸二苯酯等 進行去醇反應或去酚反應等等得到者。 聚醚多元醇可提及的有聚乙二醇，聚丙二醇，聚四伸 甲醚二醇等，其係由氧化乙烯、氧化丙烯與四氫呋喃等行 開環聚合而得：由前述共聚合之聚醚多元醇；使用上述聚 酯多元醇或聚碳酸酯多元醇作爲起始劑得到之聚酯醚多元 醇；等等。 聚烯烴多元醇可提及的例子有含羥基聚丁二烯；含羥 基聚丁二烯之氫化產物；含羥基聚異戊二烯；含羥基聚異 戊二烯之氫化產物；含羥基氯化聚丙烯；含羥基氯化聚乙 烯；等等。 蔬菜油型多元醇可提及的有蓖蔴油型多元醇，絲纖維 朊等。 _ . 長鏈多元醇除了二聚酸型多元醇與氫化二聚酸型多元 本紙張尺度適用中國國家標準（CNS) A4規格（210X297公釐1 -14- (請先閲讀背面之注意事項 Γ本頁) •裝- 訂 線 591093 A7 B7 五、發明説明（12 ) 醇外，適用者尙有聚酯樹脂；聚醯胺樹脂；丙烯酸系樹脂 :香豆滿酮；蜜胺樹脂；尿素樹脂；松香樹脂；環氧樹脂 :酚樹脂；纖維素型樹脂，如，纖維素等；天然樹脂，如 ’澱粉、皮膠等；聚乙烯醇；及其衍生物等等，只要其中 具有至少二個含活性氫基團。其數均分子量較好爲5 〇 〇 至 1 0 0 0 0。 鏈增長劑爲分子中具有至少兩個含活性氫基團之化合 物，例子有上述低分子量多元醇，低分子量多元胺，低分 子量胺醇等。其可單獨使用或二者以上倂用。 有機多異氰酸酯之例子有用於製備上述疊層黏著劑用 固化劑製備時所用有機二異氰酸酯，其改質產物等。 經濟部中央標準局員工消費合作社印製 在合成上述聚胺基甲酸酯樹脂時，有機多異氰酸酯與 具有含活性氫基團之化合物的異氰酸酯基/含活性氫基團 的比値（莫耳比）較好爲0 · 6/1至1/0 · 6。在合 成聚胺基甲酸酯樹脂時，定出不發生膠化之條件是很重要 的，其可藉由依據有機多異氰酸酯之平均N C 0官能度適 當地選擇具有含活性氫基團之化合物的含活性氫基團之平 均官能度來達成，並摻合所需起始物以符合上述條件。摻 合比係依據膠化理論（h P. Flory，Khun等人依其而理論 算出摻合比）；但是實際上，可藉由令具有含活性氫基團 之化合物與有機多異氰酸酯在考慮二者所含反應基之·反應 性比所得摻合比下反應，便不會有膠化而製成聚胺基甲酸 酯樹脂。_ _ _ 合成之聚胺基甲酸酯樹脂包含含活性氫基團或異氰酸 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） -15- 591093 A7 B7 經濟部中央標準局員工消費合作社印製 五、發明説明（13) 酯基，且數均分子量較好爲800至100000，更好 爲1000至80000。當數均分子量太大時，樹脂黏 度會太高而使加工性變差。若數均分子量太小時，結合力 會變得不足。 可用習知方法製備聚胺基甲酸酯樹脂，即，溶液反應 法：將起始物溶在有機溶劑中，然後令整個溶液進行反應 ;無溶劑反應法：無溶劑下令起始物充分混合，然後進行 反應；以及其他方法。 此外，聚胺基甲酸酯樹脂可用其他已知方法合成，例 如，單次法（one-shot method )，其中具有含活性氫基 團之化合物與有機多異氰酸酯一次地進行反應；預聚物法 ，其中先令具有含活性氫基團之化合物與過量有機二異氰 酸酯先反應成異氰酸酯基終止之預聚物，然後令此預聚物 與具有含活性氫基團之化合物反應；以及其他類似方法。 在單次法中，異氰酸酯基/含活性氫基團的比例較好 爲0 · 5至2 · 0，更好爲〇 · 8至1 · 5。當此比例低 於0 · 5，聚胺基甲酸酯樹脂的分子量變得太小，使耐久 性不足。當此比例超過2 · 0，會使異氰酸酯未參與反應 的量太大。 在預聚物法中，預聚物合成時異氰酸酯基/含活性氫 基團的比例較好爲1 · 1至5 . 0，更好爲1 · 5至 4 · 0。當此比例低於1 · 1，預聚物的分子量變得太大 ，;為以進行後續反應。當此比例超過5 · 0，黏性會變差 ./ * - (請先閲讀背面之注意事項 π本頁) 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） -16 - 591093 A7 B7 經濟部中央標準局員工消費合作社印製 五、發明説明（Μ) 在合成完以異氰酸酯基終止之預聚物後，接著要反應 之具有含活性氫基團化合物之例子有上述多元醇，多元胺 ，胺醇等。再者，若需要，部份可使用終端保護劑（end-blocking agent )，如，單胺，如乙胺、二乙胺、苯胺等； 單元醇，如甲醇、乙醇等。 在合成異氰酸酯基終止之預聚物與聚胺基甲酸酯樹脂 時，可使用產製聚胺基甲酸酯時常用之添加劑，如，觸媒 、安定劑等。觸媒的例子有三乙胺、己二胺等；金屬鹽， 如乙酸鉀、硬脂酸鋅等；有機金屬化合物，如月桂酸二丁 錫，二丁錫氧化物等。安定劑的例子有抗U V線安定劑， 如，取代苯並三唑等；抗熱氧化安定劑，如，酚衍生物等 :等等。胺基甲酸酯化之反應溫度較好爲1 0至1 2 0°C ，更好爲30至100 °C。 本發明疊層黏著劑用固化劑與疊層黏著劑可含一般黏 著劑中所用黏著劑與佐劑。添加劑與佐劑包括，例如，顏 料，染料，偶合劑，抗結塊劑，分散安定劑，黏度改良劑 ，均化劑，抗膠化劑，光安定劑，抗氧化劑，紫外光吸收 劑，耐熱改良劑，塑化劑，抗靜電劑，強化劑，觸媒，流 變劑，殺微生物劑，殺真菌劑，潤滑劑，無機與有機塡料 等。至於混煉方法則爲已知，如，攪拌、分散等。 再者，於本發明中可使用有機溶劑來調節黏度並·改善 濕潤性。有機溶劑的例子有芳族溶劑，如，甲苯、二甲苯 ，Swasol (_ COSMO OIL C〇·，LTD之芳族烴溶劑的商品名 )，Solvesso ( EXXON CHEMICAL CORP.之芳族烴溶劑 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） -17 - (請先閲讀背面之注意事項 再 本頁) •裝· J—訂 線 591093 A7 _B7 _ 五、發明説明（15) 的商品名）等；酮溶劑，如，乙酮，甲乙酮，甲異丁酮， 環己酮等；醇溶劑，如甲醇，乙醇，異丙醇等；酯溶劑， 如乙酸乙酯，乙酸丁酯，乙酸異丁酯等；二醇醚酯溶劑， 如，乙二醇乙醚乙酸酯，丙二醇甲醚乙酸酯，乙酸3 —甲 基一 3 —甲氧丁酯，3 —乙氧基丙酸乙酯等；醚溶劑，如 Η氫呋喃，二噁烷等。這些溶劑可單獨使用或兩種以上倂 用。 作爲主成份之含活性氫化合物與多異氰酸酯固化劑之 摻合比（以固含量計）爲每1 0 0重量份該含活性氫化合 物中有1至2 0 0重量份該多異氰酸酯固化劑，較好爲5 至1 8 0重量份。當多異氰酸酯固化劑之用量太低，交聯 樹脂之耐用性不足，但若用量太高，交聯樹脂之撓性不足 〇 經濟部中央標隼局員工消費合作社印製 在本發明之疊層黏著劑中，聚胺基甲酸酯樹脂可再摻 合其他樹脂，摻合比爲每1 0 0重量份聚胺基甲酸酯樹脂 中有不超過1000重量份之其他樹脂。該其他樹脂的例 子有聚醯胺樹脂，聚酯樹脂，丙烯酸系樹脂，環氧樹脂， 聚氯乙烯樹脂，乙烯-乙酸乙烯酯樹脂，腈樹脂，纖維素 樹脂（如，硝基纖維素等），石油樹脂等。 本發明疊層黏著劑對各種基板有優異黏著性，且耐久 性佳，所以可以用在各種領域中，例如，膜疊層、夾·板、 家具、汽車、鐵路、電器用品、非織物、鞋、袋等之黏著 劑，特別是_膜疊層應用。再者，對金屬或聚烯烴之勢性亦 佳，所以可作爲金屬箔、金屬化膜、聚烯烴膜等之疊層黏 •18- 本紙張尺度適用中國國家標準（CNS ) Α4規格（210Χ297公釐） 591093 經濟部中央標準局員工消費合作社印製 A7 B7五、發明説明（16 ) 著劑。 疊層之膜包括高分子膜，如，定向聚丙烯膜，未定向 聚丙烯膜，聚對酞酸乙二醇酯膜，聚對酞酸丁二醇酯膜， 聚萘酸乙二醇酯膜，聚萘酸丁二醇酯膜，耐侖膜，低密度 聚乙烯膜，·中密度聚乙烯膜，高密度聚乙烯膜，乙烯-乙 酸乙烯酯共聚物膜，乙烯一乙烯醇共聚物膜，聚氯乙烯膜 ，聚乙烯醇膜，聚苯乙烯膜，聚碳酸酯膜，聚偏氯乙烯膜 ，賽璐玢等；金屬箔，如，鋁箔、銅箔等；以蒸氣澱積塗 覆這些金屬之高分子膜；塗覆聚合物之紙與上述膜；等等 〇 高分子膜可經表面處理，如電暈放電處理等，而改善 其黏性。此外於聚合物塗覆膜的例子中，需要考慮塗覆所 用聚合物的種類，數量與表面特性。 本發明疊層黏著劑可用疊層法有濕式疊層、乾式疊層 、熱熔疊層、擠製疊層、無溶劑疊層等等。 疊層黏著劑的塗覆量較好爲0 · 5至1 0 g/m2，更 好爲1至8g/m2 (樹脂含量）。當用量在上述範圍外， 結合強度會不足。 當膜塗上黏著劑後，若需要，可令其靜置一段時間後 才疊層。所以若需要可加壓並加熱以加速固化反應。此時 ’較佳壓力爲單位面積或單位長度爲0 · 〇 1至2MP a ，較佳溫度爲4 0至1 5 0 °C。 藉由此_方法不僅可將兩張膜疊層，亦可將3張以上之 膜疊層。 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） ·巧- (請先閲讀背面之注意事項再ΙΡτ本頁) .裝· -Ί訂 線 591093 A7 B7____ 五、發明説明（17) 較佳具體例說明 下述實例用於詳細說明本發明。但本發明不應只限於 這些實例。在合成例、實例與比較例中，「份」與「％」 除非另有說明，係以重量計。 〔多異氰酸酯固化劑之合成〕 合成例1 於配有攪拌裝置，溫度計，回流冷凝管及氮氣引入管 之反應器中，置入8 6份C 一 HX (衍生自己二異氰酸酯 之含異氰脲酸酯鍵的多異氰酸酯）與1 4份單元醇〔單元 醇（1 )〕，所得混合物於7 0 °C反應3小時，得到多異 氰酸酯固化劑（固化劑A )。固化劑A之異氰酸酯基含量 爲 1 6 . 8 %。 合成侃2 經濟部中央標準局員工消費合作杜印製 於與合成例1相同的反應器中，置入9 8份14只一 20 0 (二苯基甲烷二異氰酸酯與多伸甲基一多伸苯基多 異氰酸酯之混合物）與2份單元醇〔單元醇（2)〕，所 得混合物於7 0 °C反應3小時，得到多異氰酸酯固化劑（ 固化劑B)。固化劑B之異氰酸酯基含量爲30.3%。591093 A7 _____ V. Description of the invention (8), the number of polar groups is as follows: When non-ionic polar groups are introduced, the content of ethylene oxide units in the polyisocyanate curing agent is preferably from 0.1 to 4 〇wt%, preferably 0.5 to 30wt%, compared to the solid content. When an anionic or cationic polar group is introduced, the content of the polar group is preferably 0 · 1 to 3 · Ommo Ι / g, and most preferably 0 · 15 to 2 · 9 mm ο 1 / g 〇 When the amount of the hydrophilic polar group is low At the above lower limit, its viscosity to metal is insufficient. If the amount is higher than the above upper limit, the durability of the adhesive, particularly water resistance, becomes insufficient. Printed by the Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs The curing agent for laminated adhesives of the present invention can be a reaction product with a hydrophobic group-containing compound having an active hydrogen group as an additional reactant. The hydrophobic group-containing compound having an active hydrogen-containing group includes a low molecular weight unit alcohol such as methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, third butanol, pentanol, hexanol , Heptanol, octanol, 2-ethylhexanol, benzyl alcohol, cyclohexanol, alkylene glycol monoalkyl ether, etc .; low molecular weight primary monoamines, such as ethylamine, butylamine, aniline, etc .; low molecular weight Secondary monoamines such as diethylamine, dibutylamine, toluidine; polyesters with active hydrogen groups; polyethers with active hydrogen groups, where the proportion of ethylene oxide units is less than 50 mmo 1%; polycarbonates with active hydrogen groups; polyolefins with active hydrogen groups; hydroxy higher fatty acids with at least 6 carbon atoms and their esters; etc. The organic polyisocyanate reacts with a compound having an active hydrogen group better than 10 to 120 ° C, and more preferably 30 to 100 ° C. Furthermore, and -11-This paper size applies Chinese National Standard (CNS) A4 specification (210X297 mm) 591093 Printed by A7 B7, Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs 5. Description of the invention (9) Any one containing active hydrogen The reaction of the group-containing hydrophobic group-containing compound may be performed at the same time or at different times while introducing a hydrophilic polar group. At this time, if necessary, a urethane-forming catalyst such as' dibutyltin dilaurate or triethylenediamine can be added. The isocyanate group halo of the obtained polyisoester curing agent for laminated adhesives is preferably 5 to 50 wt% ', more preferably 10 to 4 wt%. The average NC0 functionality of the polyisocyanate curing agent for laminated adhesives of the present invention is preferably 2 · 0 to 5 · 0 'and most preferably 2 · 0 to 4 · 0 °. When the average NC0 functionality is less than 2 · 0, Then, the cross-linking density becomes small and the bonding strength becomes insufficient. However, if the average N Co functionality exceeds 5 · 0, the crosslinking density becomes unnecessarily large, making the bonding layer insufficient in flexibility.活性 The active hydrogen-containing compound used as the main component in the polyisocyanate curing agent for laminated adhesives of the present invention contains at least one active hydrogen-containing group in the molecule, and preferably has a number average molecular weight of 500 to 100,000, especially 1 0 0 0 to 8 0 0 0, high molecular weight compounds containing active hydrogen. Examples are polyurethane resins; polyester resins; polyamide resins; acrylic resins; coumarone; melamine resins; urea resins; rosin resins; epoxy resins; phenol resins; polyvinyl acetate Cellulose-based resins, such as cellulose, natural resins, such as starch, leather glue, etc .; polyvinyl alcohol; and its derivatives, etc., each molecule has at least one active hydrogen-containing group. · In addition to the polyurethane resin having a urethane bond, the polyurethane resin also includes a polyurethane resin having a urethane bond and a urea bond, and many more. This paper size is applicable to Chinese National Standard (CNS) A4 specification (210X297mm) -12-/ 1 (Please read the note on the back page first)-Binding line 591093 A7 B7 V. Description of the invention (1〇) Poly The urethane resin contains at least one, preferably at least two, molecules containing an active hydrogen group, such as a hydroxyl group and the like. This urethane resin and a laminating adhesive are used as a two-component curing type laminating adhesive for a hydrophilic polar group-containing polyisocyanate curing agent. This polyurethane resin is obtained by a known reaction from a compound having an active hydrogen group and an organic polyisocyanate. Compounds having active hydrogen-containing groups are called long-chain polyols and / or chain extenders. The polyurethane resin of the present invention preferably contains 50.90 to 90% by weight of long-bonded polyol. As long-chain polyols, polyester polyols, polycarbonate polyols, polyether polyols, polyolefin polyols, vegetable oil polyols, their copolyols and the like can be mentioned. These long-chain polyols may be used alone or in combination of two or more. The long-chain polyhydric alcohol preferably has a number average molecular weight of 500 to 100 000. In view of viscosity, durability, etc., a polyester polyol is preferred in the present invention. The above-mentioned polyester polyol may be a polyester polyol and a polyesteramine polyol obtained by dehydration condensation reaction of at least one group (A) selected from the following group (B), group (A): polycarboxylic acid Acids, such as, succinic acid, adipic acid, sebacic acid, azelaic acid, p-ortho-, iso-ortho-, ortho-ortho-, hexahydroterephthalic acid, hexahydroisophthalic acid, hexahydroorthophthalic acid Naphthalenedicarboxylic acid, trimellitic acid, etc .; their esters: their anhydrides; etc .; group (B) •• low molecular weight polyols, such as ethylene glycol, 1, 2-propanediol, 1, 3 -Propylene glycol, 1,3-butanediol, 1,4-monobutylene glycol, 1,5-pentanediol, JL, 6-hexanediol, 3-methyl-1, 5-pentanediol, neopentyl Diol, 1,8 —octanediol, 1,9 monononane, diethylene glycol (please read the note on the back page first) Printed on the paper standard applicable to Chinese standards (CNS) A4 specification (210X297 mm) · 13 · 591093 Printed by the Consumers' Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs A7 B7 V. Description of the invention (11) Alcohol, dipropylene glycol 1,4 monocyclohexanedimethanol, ethylene oxide or propylene oxide adducts of bisphenol A, glycerol, trimethylolpropane, pentaerythritol, etc .; low molecular weight polyamines, such as hexamethylenediamine, xylylamine, isophorone Diamine, etc .; low molecular weight amine alcohols, such as, monoethanolamine, diethanolamine, etc. In the present invention, the "low-molecular-weight polyol", "low-molecular-weight polyol" and "low-molecular-weight amine alcohol" have a "low molecular weight" index average molecular weight of less than 500. Furthermore, cyclic ester (lactone) monomers, such as ε-caprolactone, r-valerolactone or others, can also be mentioned by using the above-mentioned low-molecular-weight polyhydric alcohol as the initiator to perform ring-opening polymerization. Ester type polyester polyol. As the polycarbonate polyol, mention may be made of the above-mentioned low molecular weight polyol and ethylene carbonate, dimethyl carbonate, diethyl carbonate, diphenyl carbonate and the like in a dealcoholization reaction or a dephenolization reaction. . Polyether polyols that can be mentioned include polyethylene glycol, polypropylene glycol, polytetramethylene ether glycol, etc., which are obtained by ring-opening polymerization of ethylene oxide, propylene oxide, and tetrahydrofuran, etc .: from the aforementioned copolymerized polymer Ether polyols; polyester ether polyols obtained using the above polyester polyols or polycarbonate polyols as starters; and the like. Examples of polyolefin polyols that can be mentioned are hydroxy-containing polybutadiene; hydroxy-containing polybutadiene; hydrogenated products; hydroxy-containing polyisoprene; hydroxy-containing polyisoprene; hydroxychlorinated Polypropylene; hydroxychlorinated polyethylene; etc. As the vegetable oil type polyol, castor oil type polyol, silk fiber tincture and the like can be mentioned. _. Except for dimer acid polyols and hydrogenated dimer acid polyols for long chain polyols, the paper size is applicable to Chinese National Standard (CNS) A4 specifications (210X297 mm 1 -14- (Please read the precautions on the back first) Page) • Packing-Thread 591093 A7 B7 V. Description of the Invention (12) In addition to alcohol, those who apply are polyester resins; polyamide resins; acrylic resins: coumarone; melamine resins; urea resins; rosin Resins; epoxy resins: phenol resins; cellulose resins, such as cellulose; natural resins, such as' starch, leather glue, etc .; polyvinyl alcohol; and its derivatives, etc., as long as there are at least two of them containing active Hydrogen group. The number-average molecular weight is preferably from 500 to 1000. The chain extender is a compound having at least two active hydrogen groups in the molecule, examples of which are the above-mentioned low-molecular-weight polyols and low-molecular-weight polyhydric alcohols. Amine, low molecular weight amine alcohol, etc. It can be used alone or in combination of two or more. Examples of the organic polyisocyanate include the organic diisocyanate used in the preparation of the above-mentioned curing agent for laminated adhesives, its modified products, etc. Economy Printed by the Consumer Standards Cooperative of the Central Bureau of Standards. When synthesizing the above-mentioned polyurethane resins, the ratio of organic polyisocyanates to isocyanate groups / active hydrogen groups containing compounds containing active hydrogen groups is larger (molar ratio). It is preferably 0. 6/1 to 1/0. 6. When synthesizing the polyurethane resin, it is important to determine the conditions under which gelation does not occur, which can be determined by the average NC 0 of the organic polyisocyanate. The functionality is appropriately selected to achieve the average functionality of the active hydrogen group-containing compound having the active hydrogen group-containing compound, and the required starting materials are blended to meet the above conditions. The blending ratio is based on the gelation theory (h P Flory, Khun, et al. Theoretically calculated the blending ratio); but in fact, it can be obtained by considering the ratio of the reactivity between the reactive hydrogen group-containing compound and the organic polyisocyanate The reaction at the blending ratio will not cause gelation to make a polyurethane resin. _ _ _ The synthetic polyurethane resin contains active hydrogen groups or isocyanate. This paper is suitable for China. National Standard (CNS) A4 Specification (210X 297 mm) -15- 591093 A7 B7 Printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs 5. Description of the invention (13) Ester group, and the number average molecular weight is preferably 800 to 100,000, more preferably 1,000 to 80,000. When the average molecular weight is too large, the viscosity of the resin will be too high and the processability will be deteriorated. If the number average molecular weight is too small, the binding force will be insufficient. Polyurethane resins can be prepared by conventional methods, that is, the solution reaction method : Dissolve the starting material in an organic solvent, and then make the entire solution react; Solventless reaction method: Make the starting material thoroughly mixed without solvent, and then perform the reaction; and other methods. In addition, polyurethane resin can be used Synthesis by other known methods, for example, one-shot method in which a compound having an active hydrogen group is reacted with an organic polyisocyanate at one time; a prepolymer method in which a shilling has an active hydrogen group The compound is reacted with excess organic diisocyanate to form an isocyanate terminated prepolymer, and then the prepolymer is reacted with a compound having an active hydrogen group; and other similar method. In the one-shot method, the ratio of the isocyanate group / active hydrogen-containing group is preferably from 0.5 to 2.0, and more preferably from 0.8 to 1.5. When this ratio is lower than 0.5, the molecular weight of the polyurethane resin becomes too small, resulting in insufficient durability. When this ratio exceeds 2.0, the amount of isocyanate not participating in the reaction will be too large. In the prepolymer method, the ratio of the isocyanate group / active hydrogen group-containing group in the prepolymer synthesis is preferably 1.1 to 5.0, and more preferably 1.5 to 4.0. When this ratio is lower than 1.1, the molecular weight of the prepolymer becomes too large for the subsequent reaction. When this ratio exceeds 5 · 0, the viscosity will become worse. / *-(Please read the note on the back page π) This paper size applies the Chinese National Standard (CNS) A4 specification (210X297 mm) -16-591093 A7 B7 Printed by the Consumer Cooperative of the Central Bureau of Standards of the Ministry of Economic Affairs. 5. Description of the Invention (M) After synthesizing a prepolymer terminated with an isocyanate group, examples of compounds having an active hydrogen group to be reacted are the above-mentioned polyols. Polyamines, amine alcohols, etc. Furthermore, if necessary, some end-blocking agents can be used, such as monoamines such as ethylamine, diethylamine, and aniline; unit alcohols such as methanol and ethanol. In synthesizing isocyanate terminated prepolymers and polyurethane resins, additives commonly used in the production of polyurethanes, such as catalysts and stabilizers, can be used. Examples of the catalyst are triethylamine, hexamethylenediamine, etc .; metal salts, such as potassium acetate, zinc stearate, etc .; organometallic compounds, such as dibutyltin laurate, dibutyltin oxide, and the like. Examples of stabilizers are anti-U V-line stabilizers, such as substituted benzotriazole, etc .; anti-oxidative stabilizers, such as, phenol derivatives, etc .: and the like. The carbamate reaction temperature is preferably 10 to 120 ° C, more preferably 30 to 100 ° C. The curing agent for laminated adhesives and laminated adhesives of the present invention may contain an adhesive and an adjuvant used in general adhesives. Additives and adjuvants include, for example, pigments, dyes, coupling agents, anti-caking agents, dispersion stabilizers, viscosity improvers, leveling agents, anti-gelling agents, light stabilizers, antioxidants, ultraviolet light absorbers, heat resistance Improvers, plasticizers, antistatic agents, strengthening agents, catalysts, rheological agents, microbicides, fungicides, lubricants, inorganic and organic additives, etc. As for the kneading method, it is known, such as stirring, dispersing and the like. Furthermore, in the present invention, an organic solvent can be used to adjust the viscosity and improve the wettability. Examples of organic solvents are aromatic solvents such as toluene, xylene, Swasol (trade name of aromatic hydrocarbon solvents of COSMO OIL CO., LTD), Solvesso (aromatic hydrocarbon solvents of EXXON CHEMICAL CORP.) Paper size Applicable to China National Standard (CNS) A4 specification (210X297 mm) -17-(Please read the precautions on the back before this page) • Installation · J—Booking line 591093 A7 _B7 _ V. Trade name of the invention description (15) ), Etc .; ketone solvents, such as ethyl ketone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, etc .; alcohol solvents, such as methanol, ethanol, isopropanol, etc .; ester solvents, such as ethyl acetate, butyl acetate, isopropyl acetate Butyl ester, etc .; Glycol ether ester solvents, such as ethylene glycol ether acetate, propylene glycol methyl ether acetate, 3-methyl-3-methoxybutyl acetate, ethyl 3-ethoxypropionate, etc. ; Ether solvents, such as trihydrofuran, dioxane, etc .; These solvents can be used alone or in combination of two or more. The blending ratio (based on solid content) of the active hydrogen-containing compound and the polyisocyanate curing agent as the main component is 1 to 200 parts by weight of the polyisocyanate curing agent per 100 parts by weight of the active hydrogen-containing compound, It is preferably 5 to 180 parts by weight. When the amount of the polyisocyanate curing agent is too low, the durability of the crosslinked resin is insufficient, but if the amount is too high, the flexibility of the crosslinked resin is insufficient. The employee's cooperative of the Central Bureau of Standards of the Ministry of Economic Affairs prints the laminated adhesive of the present invention. In the agent, the polyurethane resin may be further blended with other resins, and the blending ratio is not more than 1,000 parts by weight of the other resins per 100 parts by weight of the polyurethane resin. Examples of this other resin are polyamide resin, polyester resin, acrylic resin, epoxy resin, polyvinyl chloride resin, ethylene-vinyl acetate resin, nitrile resin, cellulose resin (e.g., nitrocellulose, etc.) , Petroleum resin, etc. The laminated adhesive of the present invention has excellent adhesion to various substrates and has good durability, so it can be used in various fields, such as film laminates, plywood, boards, furniture, automobiles, railways, electrical appliances, non-wovens, shoes , Bags, etc., especially _ film laminated applications. In addition, it has good potential for metals or polyolefins, so it can be used as a laminated adhesive for metal foils, metallized films, polyolefin films, etc. 18- This paper size applies to China National Standard (CNS) A4 specifications (210 × 297) (%) 591093 A7 B7 printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs 5. Description of Invention (16). Laminated films include polymer films such as oriented polypropylene film, unoriented polypropylene film, polyethylene terephthalate film, polybutylene terephthalate film, polyethylene naphthalate film Polybutylene naphthalate film, nylon film, low density polyethylene film, · medium density polyethylene film, high density polyethylene film, ethylene-vinyl acetate copolymer film, ethylene-vinyl alcohol copolymer film, Polyvinyl chloride film, polyvinyl alcohol film, polystyrene film, polycarbonate film, polyvinylidene chloride film, celluloid, etc .; metal foils, such as aluminum foil, copper foil, etc .; these metals are coated by vapor deposition Polymer film; polymer coated paper and the above film; etc. 0 polymer film can be surface treated, such as corona discharge treatment, to improve its viscosity. In addition, in the case of the polymer coating film, it is necessary to consider the kind, quantity, and surface characteristics of the polymer used for coating. The laminating adhesive of the present invention can be laminated by a wet lamination method, a dry lamination method, a hot melt lamination method, an extruded lamination method, a solventless lamination method, or the like. The coating amount of the laminated adhesive is preferably from 0.5 to 10 g / m2, more preferably from 1 to 8 g / m2 (resin content). When the amount is outside the above range, the bonding strength may be insufficient. When the film is coated with an adhesive, it can be allowed to stand for a period of time before laminating, if necessary. So if necessary, pressurize and heat to accelerate the curing reaction. At this time, 'preferable pressure is unit area or unit length of 0 · 〇 1 to 2 MP a, and preferred temperature is 40 to 150 ° C. By this method, not only two films can be laminated, but also three or more films can be laminated. This paper size is applicable to Chinese National Standard (CNS) A4 specification (210X297 mm). • Qiao-(Please read the precautions on the back before ipτ page). Installation ·-Binding line 591093 A7 B7____ 5. Description of the invention (17) The following specific examples are used to illustrate the present invention in detail. However, the present invention should not be limited to these examples. In the synthesis examples, examples, and comparative examples, "parts" and "%" are by weight unless otherwise specified. [Synthesis of polyisocyanate curing agent] Synthesis Example 1 In a reactor equipped with a stirring device, a thermometer, a reflux condenser and a nitrogen introduction tube, 86 parts of C-HX (isocyanuric acid containing diisocyanate derived from its own diisocyanate) was placed. An ester-bonded polyisocyanate) and 14 parts of a unit alcohol [unit alcohol (1)], and the resulting mixture was reacted at 70 ° C for 3 hours to obtain a polyisocyanate curing agent (curing agent A). The isocyanate group content of the curing agent A was 16.8%. Synthetic Kan 2 Consumption cooperation between employees of the Central Bureau of Standards, Ministry of Economic Affairs, was printed in the same reactor as in Synthesis Example 1, and put 98 parts 14 14-20 0 (diphenylmethane diisocyanate and polymethylated polyisocyanate) A mixture of phenyl polyisocyanate) and 2 parts of a unit alcohol [unit alcohol (2)], and the resulting mixture was reacted at 70 ° C for 3 hours to obtain a polyisocyanate curing agent (curing agent B). The isocyanate group content of the curing agent B was 30.3%.
I 合成例3 於與合成例1相同的反應器中，筐入8 6份c 一 Η X ，：L〇份單元醇〔單元醇（3)〕，與4份另種單元醇〔 -20- 本紙張尺度適用中國國家標準（CNS ) Α4規格（210 X 297公釐） 591093 A7 ____B7_ 五、發明説明（18) 單元醇（4 )〕’所得混合物於7 0 °C反應3小時，得到 多異氰酸酯固化劑（固化劑C )。固化劑c之異氰酸酯基 含量爲ί 7 · 7 %。 合成例4 · 於與合成例1相同的反應器中，置入9 8份I P D I 與6份三辛基膦並加熱至5 0 °C。.然後加入2份多元醇〔 多元醇（1 )〕與所得混合物於7 0 °C反應3小時.，得到 多異氰酸酯固化劑（固化劑D )。固化劑D之異氰酸酯基 含量爲3 7 · '0 %。 合成例5 經濟部中央標率局員工消費合作社印製 於與合成例1相同的反應器中，置入3 0 〇 〇份 HD I與6份三辛基膦（生成脲二酮與生成異氰脲酸酯之 觸媒）並於6 5至7 0 °C加熱攪拌，然後於相同溫度反應 6小時。接著加入3 · 5份磷酸以中斷反應，得到異氰酸 酯基含量爲3 0 · 3%之淺黃色反應混合物。以薄膜蒸餾 於1 20°C，0 · 0 ITo 1： r除去反應混合物中未反應 的HD I ，得到衍生自HD I之含脲二酮鍵的多異氰酸酯 ，其異氰酸酯基含量爲18·7%。經FT—IR與C1: - NMR確認產物中存在有異氰酸酯鍵，脲二酮鍵與異氰 脲酸酯鍵。此外，將產物加熱至1 8 0°C使脲二酮鍵解離 ’測量原有異氰酸酯基與脲二酮鍵解離之異氰酸酯P的總 量爲3 0 · 8 %。所以脲二酮鍵解離之異氰酸酯基的量爲 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） -21 - 591093 A7 B7 五、發明説明（19) 12 . 1%。再者，異氰脲酸酯鍵的量爲19 . 2%。 接著，於與合成例1相同的反應器中，置入8 6份衍 生自H DI之含脲二酮鍵的多異氰酸酯與1 4份單元醇（ 1 )，所得混合物於7 0 t反應3小時，得到多異氰酸酯 固化劑（固-化劑E )。固化劑E之異氰酸酯基含量爲 14.7%。 合成例1至5所用材料與所得異氰酸酯固化劑的異氰 酸酯基含量示於表1。 .. 經濟部中央標準局員工消費合作社印製 -22· 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） 591093 A7 B7 五、發明説明（20) 产 表 1 經濟部中央標準局員工消費合作社印製 合成例 1 2 3 4 5 有機多異氰酸酯（份） C-HX MR-200 IPDI HDI-衍生，含鍵之多異氰 酸酯 、 86 98 86 98 86 具有含活性氫基團之含 親水基化合物 （份） 單元醇（1) 單元醇（2) 單元醇（3) 多元醇（1) 14 2 10 2 14 具有含活性氫基團之含 疏水基化合物 （份） 單元醇（4) 4 固化劑 A B C D E 異氰酸酯基含量（％) 16.8 30.3 17.7 37.0 14.7 合成例1至5與表1中， (請先閱讀背面之注意事項v 裝-- 攀巧本頁) ··I訂 線 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） -23- 591093 經濟部中央標準局員工消費合作社印製 A7 B7五、發明説明（21 ) C - Η X ： Coronate HX(NIPPON POLYURETHANE INDUST RY CO·，LTD·製造，異氰酸酯基含量爲2 1 · 3 %) MR-200 : Millionate MR-200 ( NIPPON POLYURETHANE INDUSTRY CO., LTD.製造，異氰酸酯基含量爲31.0%) I P D I 異佛爾酮二異氰酸酯 H D I :己二異氰酸酯 單元醇（1):將ΕΟ/ΡΟ=1·〇〇/〇(莫耳比）加 至M e Ο Η，作爲起始劑，所形成之單元醇（數均.分子量 :4 0 0 ) 單元醇（2):將Ε0/Ρ0=80/20 (莫耳比）加 至E t ΟΗ，作爲起始劑，所形成之單元醇（數均分子量 ••7 0 0 ) 單元醇（3):將E〇/P〇 = 90/10 (莫耳比）加 至Me OH，作爲起始劑，所形成之單元醇（數均分子量 ：1 0 0 0 ) 單元醇（4 ):順蓖麻酸甲酯 多元醇（1) ··將EO/P〇 = 90/10 (莫耳比）加 至EG，作爲起始劑，所形成之二元醇（數均分子量：1 0 0 0 ) 上述單元醇（1)至（4)與多元醇（1)中， E：〇··氧化乙烯 P〇：氧化丙烯 M e〇Η : _甲醇 _ _ E t〇Η :乙醇 (請先閲讀背面之注意事項再邊馬本頁) -裝· 訂 本紙張尺度適用中國國家標準（CNS ) Α4規格（210Χ297公釐） -24- 591093 A7 B7 五、發明説明（22) E G :乙二醇 〔聚胺基甲酸酯樹脂之合成〕 合成例6 於配有攪拌裝置，溫度計，氮氣引入管及回流冷凝管 之反應器中，置入1 8 6份多元醇（多元醇A)與3 5 0 份乙酸乙酯，所得混合物於3 0 °C ·進行溶解。接著加入 8 3份I P D I與〇 · 〇 3份D B T D L，所得混合物於 7 0 °C反應3小時，然後冷卻至3 0 °C。將事先製好的胺 溶液（350 份MEK，29 份 I PDA 與 2 份MEA) V 加入反應混合物中進行反應，得到固含量爲3 0 %之聚胺 基甲酸酯樹脂（PU — 1)。 請 先 閱 讀 背 面 ί 事 項 本 頁 裝 訂 經濟部中央標準局員工消費合作社印製 合成例7 於與合成例6相同的反應器中，置入2 4 6份多元醇 (多元醇Β) ，13份NPG與200份乙酸乙酯，所得 混合物於3 0 °C進行溶解。接著加入4 1份T D I與 0 · 0 3份D B T D L，所得混合物於8 0 °C反應4小時 。隨著胺基甲酸酯化反應的進行，黏度會升高，所以分數 次加入1 5 0份乙酸乙酯。當I R分析中的異氰酸酯基峰 線消失，再以3 5 0份乙酸乙酯稀釋反應產物，得到·固含 量爲30%之聚胺基甲酸酯樹脂（PU — 2)。 合成例8 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） -25- 線 591093 A7 ____Β7_ 五、發明説明（23 ) 於與合成例1相同的反應器中，置入1 7 9份多元醇 B，89份另種多元醇（多元醇C)，與200份乙酸乙 酯，所得混合物於3 0 °C進行溶解。接著加入3 2份 Η 6 X D I與〇 · 〇 3份D B T D L，所得混合物於8 0 °C 反應。隨著胺基甲酸酯化反應的進行，黏度會升高，所以 分數次加入1 5 0份乙酸乙酯。當I R分析中的異氰酸酯 基峰線消失，再以3 5 0份乙酸乙.酯稀釋反應產物，得到 固含量爲3 0%之聚胺基甲酸酯樹脂（PU — 3 )..。 合成例9 於與合成例1相同的反應器中，置入7 7 8份多元醇 (多元醇D)並加熱至5 0°C。接著加入2 2 2份MD I ，所得混合物於8 0 °C反應。當I R分析中的異氰酸酯基 峰線消失，終止反應，得到固含量爲1 〇 〇 %之聚胺基甲 酸酯樹脂（PU - 4)。 , 合成例6至9所用材料與所得聚胺基甲酸酯樹脂的固 含量示於表2。 ---------裝— (請先閲讀背面之注意事項\^|^本頁) 訂 線 經濟部中央標隼局員工消費合作社印製 -26- 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公羡） 591093I Synthesis Example 3 In the same reactor as in Synthesis Example 1, 86 parts of c 1 Η X were put in a basket: L0 parts of a unit alcohol [unit alcohol (3)], and 4 parts of another unit alcohol [-20- The size of this paper applies Chinese National Standard (CNS) A4 specification (210 X 297 mm) 591093 A7 ____B7_ V. Description of the invention (18) Unit alcohol (4)] 'The resulting mixture is reacted at 70 ° C for 3 hours to obtain polyisocyanate Curing agent (curing agent C). The isocyanate group content of the curing agent c was 7%. Synthesis Example 4 · In the same reactor as in Synthesis Example 1, 98 parts of I P D I and 6 parts of trioctylphosphine were placed and heated to 50 ° C. Then, 2 parts of a polyol [polyol (1)] was added and reacted with the obtained mixture at 70 ° C for 3 hours to obtain a polyisocyanate curing agent (curing agent D). The isocyanate group content of the curing agent D was 37. 0%. Synthesis Example 5 Printed in the same reactor as Synthesis Example 1 by the Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs, 3,000 parts of HD I and 6 parts of trioctylphosphine (uretdione formation and isocyanide formation) Catalyst of urate) and heating and stirring at 65 to 70 ° C, and then reacting at the same temperature for 6 hours. Then, 3.5 parts of phosphoric acid was added to stop the reaction, and a pale yellow reaction mixture having an isocyanate group content of 30. 3% was obtained. Thin film distillation at 120 ° C, 0 · 0 ITo 1: r removes unreacted HD I in the reaction mixture to obtain a polyisocyanate containing uretdione bond derived from HD I, whose isocyanate group content is 18.7% . FT-IR and C1: -NMR confirmed the existence of isocyanate bond, uretdione bond and isocyanurate bond in the product. In addition, the product was heated to 180 ° C to dissociate the uretdione bond ', and the total amount of isocyanate P measured by dissociation of the original isocyanate group and the uretdione bond was 30 · 8%. Therefore, the amount of isocyanate groups dissociated from the uretdione bond is the Chinese paper standard (CNS) A4 (210X297 mm) for this paper size. -21-591093 A7 B7 V. Description of the invention (19) 12.1%. Furthermore, the amount of the isocyanurate bond was 19.2%. Next, in the same reactor as in Synthesis Example 1, 86 parts of the uretdione bond-containing polyisocyanate derived from HDI and 14 parts of the unit alcohol (1) were placed, and the resulting mixture was reacted at 70 t for 3 hours. To obtain a polyisocyanate curing agent (curing agent E). The isocyanate group content of the curing agent E was 14.7%. Table 1 shows the isocyanate group content of the materials used in Synthesis Examples 1 to 5 and the obtained isocyanate curing agent. .. Printed by the Consumer Cooperatives of the Central Bureau of Standards of the Ministry of Economic Affairs -22 · This paper size applies to the Chinese National Standard (CNS) A4 (210X297 mm) 591093 A7 B7 V. Description of the invention (20) Production table 1 Central Bureau of Standards of the Ministry of Economic Affairs Printed and Synthesized Example by Employee Consumer Cooperative 1 2 3 4 5 Organic polyisocyanate (parts) C-HX MR-200 IPDI HDI-derived, bond-containing polyisocyanate, 86 98 86 98 86 Hydrophilic group containing active hydrogen group Compound (parts) Monoalcohol (1) Monoalcohol (2) Monoalcohol (3) Polyol (1) 14 2 10 2 14 Hydrophobic group-containing compound (parts) with active hydrogen group Monoalcohol (4) 4 Cured ABCDE Isocyanate group content (%) 16.8 30.3 17.7 37.0 14.7 Synthetic Examples 1 to 5 and Table 1, (Please read the precautions on the back first v Equipment-Pan Qiao page) ·· I Dimensions This paper size is applicable to China National Standard (CNS) A4 Specification (210X297 mm) -23- 591093 Printed by the Consumers' Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs A7 B7 V. Invention Description (21) C-Η X: Coronate HX (NIPPON POLYURETHANE INDUST RY CO ·, LTD · Production Isocyanate group content: 21 · 3%) MR-200: Millionate MR-200 (manufactured by NIPPON POLYURETHANE INDUSTRY CO., LTD., Isocyanate group content: 31.0%) IPDI isophorone diisocyanate HDI: hexamethylene diisocyanate unit alcohol (1): E0 / P0 = 1 · 〇〇 / 〇 (Molar ratio) is added to Me e 0 Η, as a starter, the unit alcohol (number average. Molecular weight: 4 0 0) unit alcohol ( 2): E0 / P0 = 80/20 (Molar ratio) is added to E t 〇Η, as a starter, the unit alcohol (number average molecular weight •• 7 0 0) unit alcohol (3): E 〇 / P〇 = 90/10 (Molar ratio) added to Me OH, as a starting agent, the unit alcohol (number average molecular weight: 1 0 0 0) unit alcohol (4): methyl ricinoleate Polyol (1) ···························································· 1) to (4) and the polyol (1), E: 〇 ·· ethylene oxide P〇: propylene oxide M e〇Η: _ methanol _ _ E t〇Η: ethanol (Please read the precautions on the back before Margin page)-bound · bound paper size Using China National Standard (CNS) A4 specification (210 × 297 mm) -24-591093 A7 B7 V. Description of the invention (22) EG: ethylene glycol [synthesis of polyurethane resin] Synthesis example 6 In a reactor of a device, a thermometer, a nitrogen introduction tube and a reflux condenser, 186 parts of a polyol (polyol A) and 350 parts of ethyl acetate were placed, and the resulting mixture was dissolved at 30 ° C. Next, 83 parts of IP D I and 0.3 parts of D B T D L were added, and the resulting mixture was reacted at 70 ° C for 3 hours, and then cooled to 30 ° C. An amine solution (350 parts of MEK, 29 parts of I PDA and 2 parts of MEA) V prepared in advance was added to the reaction mixture for reaction to obtain a polyurethane resin (PU-1) having a solid content of 30%. Please read on the back of the matter. Binding page printed by the Consumer Standards Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs. Synthesis Example 7 In the same reactor as Synthesis Example 6, put 2 4 6 parts of polyol (polyol B) and 13 parts of NPG. With 200 parts of ethyl acetate, the resulting mixture was dissolved at 30 ° C. Then 41 parts of T D I and 0.3 parts of D B T D L were added, and the resulting mixture was reacted at 80 ° C for 4 hours. As the urethane reaction proceeds, the viscosity will increase, so 150 parts of ethyl acetate are added in portions. When the isocyanate peak line disappeared in the IR analysis, the reaction product was diluted with 350 parts of ethyl acetate to obtain a polyurethane resin (PU-2) with a solid content of 30%. Synthesis Example 8 This paper size is in accordance with Chinese National Standard (CNS) A4 specification (210X297 mm) -25- line 591093 A7 ____ Β7_ V. Description of the invention (23) In the same reactor as Synthesis Example 1, put 1 7 9 Parts of polyol B, 89 parts of another polyol (polyol C), and 200 parts of ethyl acetate, and the resulting mixture was dissolved at 30 ° C. Next, 32 parts of Η 6 X D I and 0.3 parts of D B T D L were added, and the resulting mixture was reacted at 80 ° C. As the urethane reaction proceeds, the viscosity will increase, so 150 parts of ethyl acetate are added in several portions. When the isocyanate group peak line in the IR analysis disappeared, the reaction product was diluted with 350 parts of ethyl acetate to obtain a polyurethane resin (PU-3) with a solid content of 30%. Synthesis Example 9 In the same reactor as in Synthesis Example 1, 7 78 parts of a polyol (polyol D) was placed and heated to 50 ° C. Then 22 2 parts of MD I were added, and the resulting mixture was reacted at 80 ° C. When the isocyanate peak line disappeared in the IR analysis, the reaction was terminated to obtain a polyurethane resin (PU-4) having a solid content of 1000%. Table 2 shows the solid contents of the materials used in Synthesis Examples 6 to 9 and the polyurethane resins obtained. --------- Installation— (Please read the notes on the back first \ ^ | ^ this page) Printed by the Staff Consumer Cooperative of the Central Standardization Bureau of the Ministry of Economics-26- This paper size applies to Chinese national standards ( CNS) A4 specifications (210X297 public envy) 591093
A B 五、發明説明（24 ) 表2 經濟部中央標隼局員工消費合作社印製 - 合成例 6 7 8 9 長鏈多元醇 （份） 多元醇A 多元醇B 多元醇C 多元醇D 186 246 179 89 778 鏈增長劑 （份） IPDA NPG 29 13 有機多異氰酸酯（份） IPDI TDI HeXDI MDI 83 41 32 222 反應終結劑· （份） MEA 2 胺基甲酸酯 （份） DBTDL 0.0 3 0.03 0.03 溶劑 （份） 乙酸乙酯 MEK 350 350 700 700 固含量 （％) 30 30 30 100 聚胺基甲酸酯樹脂 PU-1 PU-2 PU-3 PU-4 (請先閲讀背面之注意事項再本頁) 裝. ,I 丁 --" 線 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） -27- 591093 A7 B7 經濟部中央標準局員工消費合作社印製 五、發明説明（25) 合成例6至9與表2中， 多元醇A : 3 —甲基一 1，5 —戊二醇與己二酸所形成之 聚酯二醇（數均分子量：1 000) 多元醇B ··乙二醇/新戊二醇=1/1 (莫耳比）己二酸 /異酞酸=·1/1 (莫耳比）所形成之聚酯二醇（數均分 子量：2 0 0 0 ) 多元醇C :松香衍生之二醇（ΚΕ-6 0 1 ’ Arakawa Kagaku Kogyo K. K.之商品名，數均分子量：1 〇 〇 〇 ) 多元醇D : 3 —甲基一 1 ，5 —戊二醇與己二酸所形成之 聚酯二醇（數均分子量：500) I pda :異佛爾酮二胺 N P G :新戊二醇 IPDI :異佛爾酮二異氰酸酯 TDI:2，4一甲苯二異氰酸酯 H6XD I :氫化二甲苯二異氰酸酯 MDI : 4，4’ 一二苯基甲烷二異氰酸酯 Μ E A :單乙醇胺 DBTDL :二月桂酸二丁基錫 Μ E K :甲乙酮 〔結合測試一 1〕 (黏著劑配方） 以表3_所示配方製成黏著劑A D - 1至A D — 8。表 3所示比例係以固含量計。 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） -28 - (請先閲讀背面之注意事項v .裝-- 为马本頁) 訂 線 591093AB 5. Description of the invention (24) Table 2 Printed by the Consumer Cooperative of the Central Bureau of Standards of the Ministry of Economic Affairs-Synthesis Example 6 7 8 9 Long chain polyol (parts) Polyol A Polyol B Polyol C Polyol D 186 246 179 89 778 Chain extender (part) IPDA NPG 29 13 Organic polyisocyanate (part) IPDI TDI HeXDI MDI 83 41 32 222 Reaction terminator · (part) MEA 2 Urethane (part) DBTDL 0.0 3 0.03 0.03 Solvent ( Parts) Ethyl acetate MEK 350 350 700 700 Solid content (%) 30 30 30 100 Polyurethane resin PU-1 PU-2 PU-3 PU-4 (Please read the precautions on the back before this page) Packing, I Ding-" The size of the paper used in the paper is applicable to the Chinese National Standard (CNS) A4 (210X297 mm) -27- 591093 A7 B7 Printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs 5. Description of the invention (25) In Synthesis Examples 6 to 9 and Table 2, Polyol A: Polyester diol (number average molecular weight: 1 000) formed from 3-methyl-1,5-pentanediol and adipic acid Polyol B ·· Ethylene glycol / neopentyl glycol = 1/1 (Mole ratio) adipic acid / isophthalic acid = · 1/1 (Mole ratio) Polyester diol (number average molecular weight: 2000) Polyol C: rosin-derived diol (trade name of KE-6 0 1 'Arakawa Kagaku Kogyo KK, number average molecular weight: 1,000) Alcohol D: polyester diol (number-average molecular weight: 500) formed from 3-methyl-1,5-pentanediol and adipic acid I pda: isophorone diamine NPG: neopentyl glycol IPDI: Isophorone diisocyanate TDI: 2,4-monotoluene diisocyanate H6XD I: hydrogenated xylene diisocyanate MDI: 4, 4 'monodiphenylmethane diisocyanate M EA: monoethanolamine DBTDL: dibutyltin dilaurate EK : Methyl ethyl ketone [Combination Test 1] (Adhesive Formulation) Adhesives AD-1 to AD-8 were prepared with the formula shown in Table 3_. The ratios shown in Table 3 are in terms of solids. This paper size applies to Chinese National Standard (CNS) A4 specification (210X297 mm) -28-(Please read the precautions on the back v. Installation-for the page of the horse) Thread 591093
A B7 五、發明説明（26) - i /〇 tA B7 V. Description of Invention (26)-i / 〇 t
表3 X 聚胺; .； 基甲酸酯 费脂 i 卜 八1。◦ $異嶔酸_固化劑 （ ，+'' — PU-1 PU- 2 PU- 3 ( A B C D \ E C-L C-HL C-HX AD-1 100 15 AD-2 100 15 AD-3 100 15 AD-4 100 15 AD-5 50 50 15 AD-6 100 15 AD-7 100 15 AD-8 100 15 (請先閲讀背'面乏注意事項本頁) -裝· 訂 線 經濟部中央標準局員工消費合作社印製 表3中。， C 一 L :甲苯二異氰酸酯加成物固化劑（Coronate L， NIPPON POLYURETHANE INDUSTRY CO., LTD.之商口口口名 ，固含量爲7 5 % ) C 一 H L :己二異氰酸酯加成物固化劑（Coronate HL， NIPPON POLYURETHANE INDUSTRY CO., LTD.之商口口口名 ，固含量爲7 5 % ) ' C 一 HX :衍生自HD I之含異氰酸酯鍵的多異氰酸酯固 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） • 29 - 591093 A7 B7 經濟部中央標隼局員工消費合作社印製 五、發明説明（27) 化齊！I ( Coronate HX, NIPPON POLYURETHANE INDUSTRY CO·，LTD.之商品名，固含量爲1 〇 〇%) (結合強度測量） 實例1 於乾式疊層機中安置AD-1，電暈處理PET膜（ 膜厚1 2#).，鋁箔（膜厚7//)·，電暈8處理CPP膜 (膜厚70//)。以凹版印刷滾輪將AD — 1塗覆在電暈 處理P E T膜之電暈處理表面上使AD - 1塗覆乾重爲 3 · 5g/m2。然後令膜通過8CTC的乾燥烘箱，再以 100°Cx〇 · 3MPa之滾輪將鋁箔疊層上去。接著， 以凹版印刷滾輪將AD-1塗覆在鋁箔上使AD—1塗覆 乾重爲3 · 5g/m2。然後通過80°C的乾燥烘箱，再以 10 0°Cx〇 · 3MPa之滾輪將電暈處理CPP膜疊層 上去。膜的速度爲5 〇m/分鐘。疊層所得組合體於4 0 °C固化3天得到疊層膜（疊層膜A )。 將疊層膜A裁成1 5mm寬，於2 5°C與5 0%RH 測量環境以3 0 0 m m /分鐘拉伸速度進行T 一剝離測試 〇 此外，以1 8 0 °C X 0 · 3 Μ P a X 1秒的條件將疊 層膜A的三邊熱封製成一個袋子且C P P面在裡面，然後 於袋子中裝入蕃茄醬/沙拉油/醋=1/1/1 (重量比 )的混合物_，以上述相同條件熱封使袋子密閉。袋子於 1 2 0 °C煮沸3 0分鐘後進行T 一剝離測試（試樣寬：. (請先閱讀背面之注意事項 本頁) -裝‘ 線 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） -30- 591093 經濟部中央標準局員工消費合作社印製 A7 B7 五、發明説明（28) 15mm，拉伸速度：300mm/分鐘，測量環境： 25〇C 與 50%RH)。 實例2至5與比較例1至3 重覆實例1的步驟，但將A D - 1換成A D - 2至 A D - 8任一者，製成疊層膜，然後令其進行與實例1相 同的測試。 實例1至5與比較例1至3所得測試結果如表4所示 -31 - 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） 591093Table 3 X Polyamine;.; ◦ $ Isoic acid_curing agent (, + '' — PU-1 PU- 2 PU- 3 (ABCD \ E CL C-HL C-HX AD-1 100 15 AD-2 100 15 AD-3 100 15 AD -4 100 15 AD-5 50 50 15 AD-6 100 15 AD-7 100 15 AD-8 100 15 (Please read the "Notes on the back" first page)-Assembly and Threading Staff Consumption of the Central Standards Bureau of the Ministry of Economic Affairs Cooperative printed in Table 3., C-L: Toluene diisocyanate adduct curing agent (Coronate L, NIPPON POLYURETHANE INDUSTRY CO., LTD., Trade name, solid content of 75%) C-HL: Hexamethylene diisocyanate adduct curing agent (Coronate HL, NIPPON POLYURETHANE INDUSTRY CO., LTD., Trade name, solid content 75%) '' C-HX: polyisocyanate with isocyanate bond derived from HD I The size of the solid paper is in accordance with the Chinese National Standard (CNS) A4 (210X297 mm) • 29-591093 A7 B7 Printed by the Staff Consumer Cooperative of the Central Bureau of Standards of the Ministry of Economic Affairs 5. Description of the invention (27) All in all! I (Coronate HX, Trade name of NIPPON POLYURETHANE INDUSTRY CO., LTD. (Solid content is 100%) (bonding strength measurement) Example 1 AD-1 was placed in a dry laminator, corona treated PET film (film thickness 1 2 #)., Aluminum foil (film thickness 7 //) ·, Corona 8-treated CPP film (film thickness 70 //). AD-1 was coated on the corona-treated surface of the corona-treated PET film with a gravure printing roller so that the dry weight of AD-1 was 3 · 5g / m2 The film was then passed through a 8CTC drying oven, and the aluminum foil was laminated with a roller at 100 ° C x 0.3 MPa. Then, AD-1 was coated on the aluminum foil with a gravure printing roller to make the dry weight of AD-1 coated as 3 · 5g / m2. Then pass through a drying oven at 80 ° C, and then stack the corona-treated CPP film with a roller at 100 ° Cx 0.3MPa. The speed of the film is 50m / min. The resulting combination is laminated The body was cured at 40 ° C for 3 days to obtain a laminated film (laminated film A). The laminated film A was cut to a width of 15 mm, and the measurement environment was at 25 ° C and 50% RH at 300 mm / min. T-peel test was performed at the tensile speed. In addition, the three sides of the laminated film A were heat-sealed into a bag under the condition of 180 ° CX 0 · 3 MPa x 1 second with the CPP side inside, and then Bags of ketchup / salad The mixture of oil / vinegar = 1/1/1 (weight ratio) is heat sealed under the same conditions as described above to seal the bag. The bag was boiled at 120 ° C for 30 minutes and subjected to T-peel test (sample width :. (Please read the precautions on the back page first)-Packing 'The size of the paper is applicable to China National Standard (CNS) A4 specifications (210X297 mm) -30- 591093 Printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs A7 B7 V. Description of the invention (28) 15mm, tensile speed: 300mm / min, measurement environment: 25 ° C and 50% RH). Examples 2 to 5 and Comparative Examples 1 to 3 were repeated in the same manner as in Example 1, except that AD-1 was replaced with any of AD-2 to AD-8 to make a laminated film, which was then subjected to the same procedure as in Example 1. test. The test results obtained in Examples 1 to 5 and Comparative Examples 1 to 3 are shown in Table 4. -31-This paper size applies the Chinese National Standard (CNS) A4 specification (210X297 mm) 591093
A B 五、發明説明（29 ) 表4 經濟部中央標準局員工消費合作社印裝 黏著劑 剝離強度 (gf/1 5mm) 乾餾處理後之剝 離強度（gf/15mm) PET/A1 Al/CPP PET/ΑΙ Al/CPP 實例 1 AD-1 400 1200 400 1100 PETf Alf PETf - Alf • 2 AD-2 360 970 380 1050 PETf Alf PETf Alf 3 AD-3 380 1080 400 1050 PETf Alf PETf Alf 4 AD-4 400 1100 390 1100 PETf Alf PETf Alf 5 AD-5 370 1000 350 1000 PETf Alf PETf Alf 1 /AD-6 / 400 740 280 590 ί f PETf Alf 比較例 1 1 2 1 AD-7 380 680 250 5 8 0 il PETf Alf I 3 AD-8 390 750 260 640 PETf Alf 實例1至5，比較例1至3與表4中， (請先閱讀背面之注意事項本頁) -絮· -— ί 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） -32 - 591093 A7 _____B7 _ 五、發明説明（30) PET:聚對酞酸乙二醇酯 A 1 :鋁箔 CPP:未定向聚丙烯 PETf : PET材料失敗 A 1 f :鋁材料失敗 〔結合測試一 2〕 (黏著劑配方） 以表5所示配方製成黏著劑（AD - 9至AD - 1 2 (請先閲讀背面之注意事項AB V. Description of the invention (29) Table 4 Peeling strength of printed adhesives (gf / 1 5mm) by the Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs Peeling strength after retorting (gf / 15mm) PET / A1 Al / CPP PET / ΑΙ Al / CPP Example 1 AD-1 400 1200 400 1100 PETf Alf PETf-Alf • 2 AD-2 360 970 380 1050 PETf Alf PETf Alf 3 AD-3 380 1080 400 1050 PETf Alf PETf Alf 4 AD-4 400 1100 390 1100 PETf Alf PETf Alf 5 AD-5 370 1000 350 1000 PETf Alf PETf Alf 1 / AD-6 / 400 740 280 590 ί f PETf Alf Comparative Example 1 1 2 1 AD-7 380 680 250 5 8 0 il PETf Alf I 3 AD-8 390 750 260 640 PETf Alf Examples 1 to 5, Comparative Examples 1 to 3, and Table 4, (Please read the precautions on the back page first)-·· -— ί The paper size is applicable to Chinese national standards (CNS ) A4 specification (210X297 mm) -32-591093 A7 _____B7 _ V. Description of the invention (30) PET: polyethylene terephthalate A 1: aluminum foil CPP: unoriented polypropylene PETf: PET material failure A 1 f : Aluminum material failed [Combination Test 1 2] (Adhesive formulation) Made with the formulation shown in Table 5 Adhesives (AD-9 to AD-1 2 (Please read the precautions on the back first
•本頁) 經濟部中央標準局員工消費合作社印製 (結合強度測量） 實例6 以滾輪塗覆器將AD - 9 (已加熱至6 0 °C)塗覆在 電暈處理PET膜（膜厚1 2//)之電暈處理表面上使黏 著劑塗覆量爲2 . Og/m 2。然後將此塗覆有黏著劑之 PE 丁膜以l〇〇°Cx〇 · 3MPa之疊層滾輪疊層在蒸 氣澱積有鋁之聚丙烯膜（膜厚6 0 ")的鋁箔表面上。膜 的速度爲5 Om /分鐘。疊層所得組合體於4 0°C固化3 天得到疊層膜（疊層膜I )。 將疊層膜I裁成1 5mm寬，於2 5°C與50%·ΙΙΗ 測量環境以3 0 0 m m /分鐘拉伸速度進行Τ 一剝離測試 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） · 33 · 訂 線 591093• This page) Printed by the Consumer Cooperative of the Central Bureau of Standards of the Ministry of Economic Affairs (combined with strength measurement) Example 6 AD-9 (heated to 60 ° C) was coated with a roller coater on a corona-treated PET film (film thickness Og / m 2 on the corona-treated surface of 1 2 //). Then, the adhesive-coated PE butyl film was laminated on a surface of an aluminum foil having a vapor-deposited polypropylene film (film thickness 60 ") by laminating rollers at 100 ° C x 0.3 MPa. The speed of the film was 5 Om / min. The obtained laminated body was cured at 40 ° C for 3 days to obtain a laminated film (laminated film I). The laminated film I was cut to a width of 15 mm at a temperature of 25 ° C and 50% · ΙΙΗ. The measurement environment was carried out at a tensile speed of 300 mm / min. T-peel test The paper dimensions are applicable to China National Standard (CNS) A4 specifications (210X297 mm) · 33 · 591093
A B7 五、發明説明（31) 實例7與比較例4與5 重覆實例6的步驟，但將AD-9換成AD〜i〇至 AD — 12任一者，製成疊層膜，然後令其進行與實例6 相同的測試。 實例6·與7與比較例4與5所得測試結果如袠5所示 表5 黏著 劑 主成份 固化劑 剝離 強度 (gf/1 5 mm) PES PU-4 A C-HX 實例 6 AD-9 100 70 370PETf 7 AD-10 100 70 390PETf 比較 4 AD-1 1 100 70 250 例 5 AD-12 100 70 280 經濟部中央標準局員工消費合作社印製 (請先閲讀背面之注意事項本頁) 線 實例6與7，比較例4與5與表5中， PES ··乙二醇/新戊二醇= 30/70 (莫耳比）與異 酞酸/癸二酸=6 0/40 (莫耳比）所形成之聚酯二醇 (數均分子量：1000)A B7 V. Description of the invention (31) Example 7 and Comparative Examples 4 and 5 The steps of Example 6 were repeated, but AD-9 was replaced with any of AD ~ i0 to AD-12 to make a laminated film, and then Let it be tested the same as in Example 6. Example 6 · and 7 and Comparative Examples 4 and 5 The test results are shown in 袠 5. Table 5 Adhesive main component curing agent peel strength (gf / 1 5 mm) PES PU-4 A C-HX Example 6 AD-9 100 70 370PETf 7 AD-10 100 70 390PETf Comparison 4 AD-1 1 100 70 250 Example 5 AD-12 100 70 280 Printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs (please read the precautions on the back page first) Line Example 6 And 7, Comparative Examples 4 and 5 and Table 5, PES ·· ethylene glycol / neopentyl glycol = 30/70 (molar ratio) and isophthalic acid / sebacic acid = 6 0/40 (molar ratio ) Formed polyester diol (number average molecular weight: 1000)
C_HX 衍生自HD I之含異氰酸酯鍵的多異氰酸酯固 化劑(Coronate HX，NIPPON POLYURETHANE INDUSTRY 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） -34- 591093 A7 B7 五、發明説明（32) CO·，LTD.之商品名） PET:聚對酞酸乙二醇酯 VM — C P P :蒸氣澱積有鋁之未定向聚丙烯膜 VETf : PET材料失敗 如上所述’本發明可提出疊層黏著劑用之多異氰酸酯 固化劑’其具有優異耐熱性、耐久性與對金屬膜與聚烯烴 膜有優異黏性’以及包括此多異氰酸酯固化劑之疊層黏著 劑，此外’亦可於膜疊層時使用此疊層黏著劑。 (請先閱讀背面之注意事項ν -裝-- ▼馬本頁)C_HX Polyisocyanate curing agent containing isocyanate bond derived from HD I (Coronate HX, NIPPON POLYURETHANE INDUSTRY) This paper size is applicable to China National Standard (CNS) A4 specification (210X297 mm) -34- 591093 A7 B7 V. Description of the invention (32 ) Product name of CO., LTD.) PET: polyethylene terephthalate VM — CPP: vapor-deposited non-oriented polypropylene film VETf: PET material failed as described above. 'The present invention can propose a laminate Polyisocyanate curing agent for adhesives 'It has excellent heat resistance, durability and excellent adhesion to metal films and polyolefin films' and a laminating adhesive including this polyisocyanate curing agent, in addition, it can also be used for film lamination Use this laminated adhesive. (Please read the precautions on the back ν-equipment-▼ horse page)
、1T 線 經濟部中央標準局員工消費合作杜印製 -35- 本纸張尺度適用中國國家標準（CNS ) Α4規格（210X297公釐）Line 1T Printed by the Consumer Co-operation of the Central Bureau of Standards of the Ministry of Economic Affairs -35- This paper size applies to China National Standard (CNS) Α4 specifications (210X297 mm)
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| JP25745697A JP4022912B2 (en) | 1997-09-05 | 1997-09-05 | Laminate adhesive using polyisocyanate curing agent for laminate adhesive |
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| JP5515274B2 (en) * | 2008-10-27 | 2014-06-11 | 日本ポリウレタン工業株式会社 | Curing agent for two-component polyurethane resin paint, method for producing the same, and two-component polyurethane resin paint |
| JPWO2010150673A1 (en) * | 2009-06-23 | 2012-12-10 | コニシ株式会社 | Two-component fractional application type fast-curing water-based adhesive and bonding method using the water-based adhesive |
| JP5657990B2 (en) * | 2009-10-14 | 2015-01-21 | 三井化学株式会社 | Laminating adhesive |
-
1997
- 1997-09-05 JP JP25745697A patent/JP4022912B2/en not_active Expired - Fee Related
-
1999
- 1999-02-22 TW TW88102567A patent/TW591093B/en not_active IP Right Cessation
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| TWI417425B (en) * | 2008-06-27 | 2013-12-01 | Fih Hong Kong Ltd | Method for blocking micro-holes of micro-arc oxidation film |
| TWI486418B (en) * | 2013-07-08 | 2015-06-01 | Everest Textile Co Ltd | Breathable polyurethane adhesive |
| US11795267B2 (en) | 2016-12-12 | 2023-10-24 | Dic Corporation | Aqueous urethane resin composition and synthetic leather |
Also Published As
| Publication number | Publication date |
|---|---|
| JP4022912B2 (en) | 2007-12-19 |
| JPH1180699A (en) | 1999-03-26 |
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| Date | Code | Title | Description |
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| MM4A | Annulment or lapse of patent due to non-payment of fees |