200300164 A7 B7 五、發明説明（1 ) 一、 發明之技術領域 (請先閲讀背面之注意事項再填寫本頁) 本發明爲提供聚氯丁二烯乳膠爲主，聚異酸酯化物爲 硬化劑所成的二液型水系粘著劑，爲改善混合聚異氰酸酯 後的粘著劑之適用期的方法。 二、 先行技術 向來多數使用溶劑型粘著劑的領域，由作業員的安全 衛生或作業環境面極需改變爲水系粘著劑。但是，水系粘 著劑在粘著強度或作業性尙有很多不及溶劑型粘著劑的地 方。爲改良這些點，提案倂用異氰酸酸酯的二液型水系粘 著劑，目前使用二液型粘著劑因配合處方不斷發生適用期 短的實用上的問題。 三、 發明內容 經濟部智慧財產局員工消費合作社印製 本發明係有鑑於現狀，提供控制聚氯丁二烯系二液型 水系粘著劑之適用期的方法爲目的。本發明者等，爲達成 上述目的經深入硏究結果，有關以聚氯丁二烯乳膠爲主， 聚異酸酯化物爲硬化劑所成的二液型水系粘著劑，添加特 定的界面活性劑，發現該水系粘著劑的適用期可延長至實 用的水準，完成本發明。 即，本發明有關以聚氯丁二烯乳膠爲主，聚異酸酯化 物爲硬化劑所成的二液型水系粘著劑，以添加烷基二苯基 醚二磺酸鹽及/或聚環氧乙烷烷基醚硫酸鹽爲其特徵的延 長適用期的方法。 本紙張尺度適用中國國家標準（CNS ) A4規格（210 X 297公釐） -5- 200300164 A7 B7 五、發明説明（2 ) (請先閲讀背面之注意事項再填寫本頁) 以下詳細說明本發明的內容。本發明所謂的聚氯丁二 烯係2-氯-1,3-丁二烯（以下略爲氯丁烯）的單獨聚合物，或 氯丁烯及可與氯丁烯共聚合的單體的共聚合物，此處所謂 共聚合物係含聚氯丁二烯存在下，其他單體以接枝聚合方 式的接枝共聚合物。 可與上述氯丁烯共聚合的理想單體，可列舉如2,3-二 氯1,3-丁二烯’ 1-氯-1,3 -丁二烯，丁二烯，異戊二烯，苯 乙儲，丙儲酸腈，丙烧酸及其酯類，甲基儲酸及其酯類等 ，依必要可使使用二種以上。 取得氯丁烯的聚合方法無特別限制，一般以乳液聚合 的方法可簡易取得。又，只要是由乳液聚合所得的聚氯丁 二烯乳膠即可原樣使用於本發明。 本發明乳液聚合以外所得的聚氯丁二烯，所得聚氯丁 二烯以溶劑溶解後，該溶液於乳化液中分散，其次將有機 溶劑除去的方法取得者，因步驟增加不經濟。 經濟部智慧財產局員工消費合作社印製 聚氯丁二烯乳膠的乳液聚合所使用的乳化劑及/或分 散劑無特別的限制，可使用通常氯丁烯乳膠所使用的各種 陰離子型及或非離子型乳化劑。 陰離子型及非離子型的乳化劑有羰酸型、磺酸型、硫 酸酯型等，可舉例如玫瑰酸的鹼金屬鹽、碳數爲8〜20 的烷基磺酸酯、烷基芳基硫酸酯、萘磺酸鈉鹽與甲醛的縮 合物等，非離子型的具體例可列舉如聚乙烯醇或其共聚合 物（例如與丙烯酸胺的共聚合物）聚乙烯醚或其共聚合物（ 例如與馬來酸的共聚合物）、聚乙烯吡咯烷酮或其共聚合 本紙張尺度適用中·國國家榇準（CNS ) A4規格（210 X 297公釐） -6 - 200300164 A7 B7 五、發明説明（3 ) (請先閲讀背面之注意事項再填寫本頁) •物（例如與醋酸乙烯的共聚合物），或此等（共）聚合物經化 學修飾者，或纖維素系衍生物（羥乙基纖維素）等。其中以 上述玫瑰酸鹽最適合本發明。 有關本發明的聚氯丁二烯系乳膠中的乳化劑及/或分 散劑的添加量，以初期投入的氯丁烯單體1 00質量份（氯 丁烯單獨聚合物時），或初期投入的氯丁烯單體及共聚合 單體的合計爲100質量份（氯丁烯共聚合物時）時以0.5〜 20質量份爲理想。低於〇.5質量份時，乳化力不充分， 超過20質量份時有耐水粘著力下降的缺點。 得到本發明聚氯丁二烯系乳膠的聚合溫度無特別的限 制，聚合反應的圓滑聚合溫度以〇〜50 °C爲理想，聚合 的引發劑’以過硫酸鉀等的過硫酸鹽、第三丁基氫過氧化 物等的有機過氧化物等爲合適，但不限定於。 經濟部智慧財產局員工消費合作社印製 得到聚丁烯聚合用的連鎖移動劑的種類無特的限制。 可使用通常氯丁烯的乳液聚合所使用者。例如可使用n_ 十二烷基毓醇或叔-十二烷基酼醇等的長鏈院毓醇類、二 異丙基黃原酸二硫化物類、碘仿等的公知的連鎖移動劑。 聚氯丁二烯聚合停止劑（聚合抑制劑）無特別的限制，例如 可使用2,6 -第二級-丁基-4 -甲基酣、吩噻嗪、經基胺等。 聚氯丁二烯最終聚合率無特別限制，可任意的調節。 未反應的單體以脫單體操作除去，其方法無特別限制。 本發明的聚氯丁二烯系乳膠以濃縮，或加水稀釋等將 固形物濃度控制於必要的濃度。濃縮方法有減壓濃縮等， 但無特別限定。 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公慶） -7- 200300164 A7 B7 五、發明説明（4 ) 有關本發明的聚氯丁二烯系乳膠的性狀無特別的限制 ，聚合溫度、聚合引發劑、連鎖移動劑、聚合抑制劑、、 最終聚合率、脫單體、濃縮條件等適切的選擇，控制，可 調整固形物濃度、甲苯可溶部份的分子量、甲苯不溶部份 (膠化含量）等。 由初期粘著力及常態粘著力的平衡點來說，聚氯丁二 烯系乳膠中的氯丁烯（共）聚合物的膠化含量，以調整於3 〜60質量％爲合適。 本發明所用的烷基二苯基醚二磺酸鹽如下述化學式1 所示。式中，R以碳數6〜20的烷基爲理想，B以鉀、鈉 等的鹼金屬離子、鏡離子等爲理想。其理想的例可列舉如 十二烷基二苯基醚磺酸的二鈉或二鉀、十八烷基二苯基醚 磺酸的二鈉或二鉀等，但不限定於此。 (請先閱讀背面之注意事項再填寫本頁)200300164 A7 B7 V. Description of the invention (1) 1. Technical field of the invention (please read the precautions on the back before filling this page) The present invention is mainly to provide polychloroprene latex, and polyisoesterate is the hardener The formed two-liquid water-based adhesive is a method for improving the pot life of the adhesive after mixing polyisocyanate. 2. Advance Technology In most fields where solvent-based adhesives are used, the safety and health of the operator or the operating environment must be changed to water-based adhesives. However, water-based adhesives are inferior to solvent-based adhesives in terms of adhesive strength or workability. In order to improve these points, a two-liquid type water-based adhesive using isocyanate has been proposed. At present, the use of two-liquid type adhesives often causes practical problems of short pot life due to the formulation. III. Summary of the Invention Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs The present invention aims to provide a method for controlling the application period of polychloroprene-based two-liquid water-based adhesives in view of the current situation. In order to achieve the above-mentioned object, the present inventors have thoroughly studied the results, and related to a two-liquid type water-based adhesive mainly composed of polychloroprene latex and polyisoesterate as a hardener, and added specific interface activity It was found that the useful life of the water-based adhesive can be extended to a practical level, and the present invention has been completed. That is, the present invention relates to a two-liquid water-based adhesive made mainly of polychloroprene latex and a polyisoesterate as a hardener, in which an alkyldiphenyl ether disulfonate and / or a polymer are added. Ethylene oxide alkyl ether sulfate is a method for extending the pot life. This paper size applies Chinese National Standard (CNS) A4 specification (210 X 297 mm) -5- 200300164 A7 B7 V. Description of the invention (2) (Please read the precautions on the back before filling this page) The following describes the invention in detail Content. The so-called polychloroprene-based 2-chloro-1,3-butadiene (hereinafter referred to as chloroprene) alone polymer, or chloroprene and a monomer copolymerizable with chloroprene Copolymer. Here, the so-called copolymer is a graft copolymer in which other monomers are graft-polymerized in the presence of polychloroprene. Ideal monomers that can be copolymerized with the above chloroprene, such as 2,3-dichloro1,3-butadiene '1-chloro-1,3-butadiene, butadiene, isoprene , Benzene ethyl acid storage, propion acid nitrile, propionic acid and its esters, methyl storage acid and its esters, etc., if necessary, two or more kinds can be used. The polymerization method for obtaining chloroprene is not particularly limited. Generally, it can be easily obtained by emulsion polymerization. Any polychloroprene latex obtained by emulsion polymerization can be used in the present invention as it is. The polychloroprene obtained in the present invention other than the emulsion polymerization, the obtained polychloroprene is dissolved in a solvent, the solution is dispersed in an emulsion, and the method of removing the organic solvent next is uneconomical due to the increase in steps. The emulsifiers and / or dispersants used in the emulsion polymerization of polychloroprene latex printed by employees' consumer cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs are not particularly limited. Various anionic and non-ionic types commonly used in chloroprene latex can be used. Ionic emulsifier. Anionic and non-ionic emulsifiers include carbonyl acid type, sulfonic acid type, and sulfate type. Examples include alkali metal salts of rose acid, alkyl sulfonates having 8 to 20 carbon atoms, and alkyl aryl groups. Sulfuric acid esters, condensates of sodium salt of naphthalenesulfonic acid and formaldehyde, and specific examples of nonionics include polyvinyl alcohol or a copolymer thereof (for example, a copolymer with acrylic acid amine), polyvinyl ether, or a copolymer thereof. (Such as copolymers with maleic acid), polyvinylpyrrolidone or its copolymers This paper is applicable to China · National Standards (CNS) A4 (210 X 297 mm) -6-200300164 A7 B7 V. Invention Note (3) (Please read the notes on the back before filling out this page) • Substances (such as copolymers with vinyl acetate), or those (co) polymers that have been chemically modified, or cellulose derivatives ( Hydroxyethyl cellulose) and so on. Among them, the above-mentioned rosates are most suitable for the present invention. The amount of the emulsifier and / or dispersant in the polychloroprene-based latex of the present invention is 100 parts by mass of the chloroprene monomer initially charged (in the case of a chloroprene single polymer), or the initial amount of When the total of the chloroprene monomer and the comonomer is 100 parts by mass (in the case of the chloroprene copolymer), 0.5 to 20 parts by mass is preferable. If it is less than 0.5 parts by mass, the emulsifying power is insufficient, and when it exceeds 20 parts by mass, there is a disadvantage that the water-resistant adhesive force is reduced. The polymerization temperature for obtaining the polychloroprene-based latex of the present invention is not particularly limited. The smooth polymerization temperature of the polymerization reaction is preferably 0 to 50 ° C. The polymerization initiator is a persulfate such as potassium persulfate, a third Organic peroxides and the like such as butyl hydroperoxide are suitable, but are not limited thereto. Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs. There are no specific restrictions on the types of chain mobile agents used for polybutene polymerization. Users of emulsion polymerization of chloroprene in general can be used. For example, well-known chain transfer agents such as n-dodecyl alcohol or tert-dodecyl alcohol such as long chain alcohols, diisopropylxanthic acid disulfides, iodoform and the like can be used. The polychloroprene polymerization stopper (polymerization inhibitor) is not particularly limited, and for example, 2,6-secondary-butyl-4-methylfluorene, phenothiazine, meridylamine, and the like can be used. The final polymerization rate of polychloroprene is not particularly limited and can be arbitrarily adjusted. The unreacted monomer is removed by a monomer removal operation, and the method is not particularly limited. The polychloroprene-based latex of the present invention controls the solid content to a necessary concentration by concentrating or diluting with water. The concentration method includes, but is not particularly limited to, concentrated under reduced pressure. This paper size is applicable to Chinese National Standard (CNS) A4 specification (210X297 public holiday) -7- 200300164 A7 B7 V. Description of the invention (4) There is no special restriction on the properties of the polychloroprene-based latex of the present invention, and the polymerization temperature , Polymerization initiator, chain transfer agent, polymerization inhibitor, final polymerization rate, demonomerization, concentration conditions and other appropriate choices, control, can adjust the solids concentration, the molecular weight of the toluene soluble part, the toluene insoluble part ( Gelation content) and so on. From the balance of the initial adhesion and normal adhesion, the gel content of the chloroprene (co) polymer in the polychloroprene-based latex is suitably adjusted to 3 to 60% by mass. The alkyl diphenyl ether disulfonate used in the present invention is represented by the following Chemical Formula 1. In the formula, R is preferably an alkyl group having 6 to 20 carbon atoms, and B is preferably an alkali metal ion such as potassium, sodium, or a mirror ion. Preferred examples thereof include, but are not limited to, disodium or dipotassium of dodecyl diphenyl ether sulfonic acid, and disodium or dipotassium of octadecyl diphenyl ether sulfonic acid. (Please read the notes on the back before filling this page)
經濟部智慧財產局員工消費合作社印製 本發明使用的聚環氧烷撐烷基醚硫酸鹽如下述化學式 2所示。式中，R1以碳數6〜20的烷基爲理想，特別以 1 〇〜1 6爲更理想。R2以碳數2〜6的烷撐基爲理想，特 別以2〜4爲更理想。B爲鈉、鉀等的鹼金屬離子、銨離 子等。理想的例可列示如聚環氧乙烷十二烷基醚硫酸的鈉 鹽或鉀鹽，聚環氧乙烷十八烷基醚硫酸的鈉鹽或鉀鹽等， 本紙張尺度適用中國國家標準（CNS ) A4規格（21〇X297公釐） -8- 200300164 A7 ______ B7 五、發明説明（5 ) 但不限定於此。 (請先閲讀背面之注意事項再填寫本頁) R1' (0'R2〇 n-S〇4 · B 化學式 2 院基二苯基醚二磺酸鹽及或聚環氧乙基硫酸鹽的添加 里無特別的限定，以1⑼質量份添加5質量份以下爲理想 。大於5質量份的添加量可能對粘著特性有不良影響。 其中亦以1 00質量份聚氯丁二烯添加0.0 1〜2質量理想。 院基一苯基醚二磺酸鹽及或聚環氧乙烷烷基硫酸鹽的 添加方法無特別限制，直接原樣或水溶液的添加方法爲簡 便。院基二苯基醚二磺酸鹽及或聚環氧乙烷烷基硫酸鹽的 添加時期’在添加聚異氰酸酯之前即無特別限定，一定要 在添加聚異氰酸酯前均勻的分散。又，適用期的延長效果 係由添加本發明所示的持有特定的構造的界面活性劑而開 始發現，並非任何界面活性劑均可發現。 經濟部智慧財產局員工消費合作社印製 本發明有關的聚異氰酸酯化合物，係爲分子中含2個 以上的異氰酸酯基化合物。可舉例如甲苯撐二異氰酸酯 (TDI)、二甲苯撐二異氰酸酯（xdi)、ι，3-雙（異氰酸甲酯） 環己烷、六甲撐二異氰酸酯（HDI)、原菠烷二異氰酸酯 (NBDI)、四甲基二甲苯撐二異氰酸酯、異富爾酮二異氰酸 酯（IPDI)、4,4’-二苯基甲烷二異氰酸酯（MDI)、三甲基六 甲撐二異氰酸酯（TMDI)、對-苯撐二異氰酸酯（PPDI)、三 甲基甘氨酸二異氰酸酯（LDI)、萘撐二異氰酸酯（NDI)、環 己基二異氰酸酯（CHDI)、三苯基甲烷-4,4’，4M-三異氰酸酯 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） -9- 200300164 A7 B7 五、發明説明（6 ) 、硫代磷-三-(對-異氰酸苯基酯）等。 (請先閲讀背面之注意事項再填寫本頁) 又，此聚異氰酸酯化合物的異氰酸酯基以嵌段劑掩蔽 的所謂嵌段異氰酸酯，或聚異氰酸酯化合物所衍生的聚氨 基甲酸預聚物，含有2個以上異氰酸酯基者亦含於本發明 所言的聚異氰酸酯化合物。 水系粘著劑，由分散性觀點，一般可使用聚異氰酸酯 化合物賦予非離子型親水基成爲可水分散構造的無皂型水 分散性聚異氰酸酯爲理想。 本發明的聚氯丁二烯系二液型粘著劑，除必須成分以 外，可任意的添加粘著賦與劑、增粘劑、金屬氧化物、塡 充劑、造膜助劑、紫外線吸收劑、氧化防止劑、可塑劑、 加硫劑、加硫促進劑、消泡劑等，添加此等添加劑，可平 衡實用時之初期粘著力、耐水粘著力、粘著保持時間等的 特性。 經濟部智慧財產局員工消費合作社印製 水系粘著劑配合粘著賦與劑時，其種類無特別限定。 具體可列舉如玫瑰酸樹脂、聚合玫瑰酸樹脂、α -蒎烯樹 月旨、/3 -蒎烯樹脂、萜烯酚樹脂、C5餾分系石油樹脂、C9 餾分系石油樹脂、C5/C9餾分石油樹脂、DCPD系石油樹脂 、烷基酚樹脂、二甲苯樹脂、黃豆酮-茚樹脂等，爲得到 充分的初期粘著力，以軟化溫度在50〜160°C的樹脂爲理 想。 粘著賦與劑的添加方法並無特別限制，爲樹脂能均勻 的分散，以已成爲水性乳液後再添加爲理想。 粘著賦與劑的水性乳液之製造方法，係以甲苯等的有 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） -10- 經濟部智慧財產局員工消費合作社印製 200300164 Α7 ___________ Β7 五、發明説明（7 ) 機溶劑溶解後，再使用乳化劑於水中乳化/分散後，有機 溶劑於減壓下加熱脫除的方法，及粉碎成微粒子後乳化/ 分散的方法等，以前者可製作更微細粒子爲理想。 本發明的聚氯丁二烯系乳膠組成物，由配合增粘劑可 調節任意的粘度。具體的增粘劑可列舉如聚乙烯醇（PVA) 、聚丙烯酸鈉、水溶性聚氨基甲酸乙酯、結合型聚氨基甲 酸乙酯系乳液、鹼膨潤型丙烯酸系乳液、羧基甲基纖維素 (CMC)、甲基纖維素（MC)、羥基乙基纖維素（HEC)、羥基 丙基纖維素（HPC)、合成蒙脫石等。 增粘劑的配合量，以100質量份聚氯丁二烯系乳膠固 體成分，添加0.01〜10質量份（換算成固體成分），理想 以0·01〜2質量份爲合適。 適用本發明的聚氯丁二儲系二液型水系粘著劑的適用 期延長方法的用途，無特別限制，可適用於全數要求高粘 著強度的用途。具體的如鞋產業、家具、木工用途、簡易 潛水服、屋頂建材、汽車用、建築用等種種用途。 四、發明的實施方式 以下以實施例及比較例更詳細說明本發明的效果，本 發明不限於實施例。又，以下說明如無特別預告，「份」 及「％」以質量爲準。 [合成例1] 使用內容積爲3公升的反應器，於氮氣流下投入 本紙張尺度適用中國國家標準（CNS ) Α4規格（210 X 297公釐） (請先閱讀背面之注意事領再填寫本頁) -裝- 訂 -11 - 200300164 A7 B7 五、發明説明（8 ) 請 先 閱 讀 背 面 之 注 意 事 1 00份水、5份不均化玫瑰酸、〇. 6份氫氧化鈉、〇. 7份氫 氧化鉀、0 · 3份甲醛萘磺酸縮合物的鈉鹽、〇. 3份亞硫酸 氫鈉，溶解後在攪拌下加入1 〇〇份氯丁烯單體及〇.丨4份 η-十二烷基毓醇。使用過硫酸鉀作爲引發劑，於氮氣環境 下於10°C聚合，聚合率達90%時加入吩噻嗪的懸濁液停 止聚合。減壓下除去未反應的單體，得到聚氯丁二烯乳膠 。更於減壓下蒸發水分進行濃縮，調整固體成分爲50質 量％ 〇 [實施例1] 使用合成例1所得的聚氯丁二烯乳膠，對聚氯丁二烯 乳膠、粘著賦與樹脂乳液、氧化鋅乳液、十二烷基二苯基 醚磺酸二鈉等以表1所示比例配合攪拌。更添加增粘劑，· 調整粘度至1 0 0 0〜1 5 0 0 m P a · S的範圍，作爲水系粘著劑 的主劑。 此主劑添加如表1所示的聚異氰酸酯化合物，攪拌後 成爲二液型水系粘著劑。 經濟部智慧財產局員工消費合作社印製 又，此處所示配合比例全數以聚氯丁二烯乳膠中的聚 氯丁二烯1 00份，所對應的各配合藥品換算爲固體成分的 份數。 實施例1經調整的粘著劑，其適用期及粘著試驗依以 下所述實施。 又，粘著試驗所使用的試料如以下方式調製。 上述所得的粘著劑，以毛刷依300 g/cm2(固體成分換 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） -12- 200300164 A7 B7 五、發明説明（9 ) (請先閲讀背面之注意事項再填寫本頁) 算）塗覆於帆布（#9)上。放置20分鐘後，將所得的帆布切 割，以2片帆布的粘著劑面相對貼合，以手輥輪壓合。調 治5天後供粘著試驗。 [適用期試驗] 添加聚異氰酸酯後立即作外觀觀察（有無凝固物）、實 施粘度測定。評價依三階段判定，與添加前僅少許的變化 狀態判爲正常（〇），粘度僅少許上昇尙在可使用判爲可使 用範圍內（△)，發生凝固，或粘度大幅增加判爲使用困難 的狀態（X)。 [常態粘著力評價試驗] 經5天調治的試料，使用拉力試驗機於室溫下，以 200 mm /分鐘的延伸速度測定T型剝離強度。 [耐熱粘著力評價試驗] 經濟部智慧財產局員工消費合作社印製 經5天調治的試料，使用拉力試驗機於80°C溫度下 ，以200 mm /分鐘的延伸速度測定τ型剝離強度。 [常態粘著力評價試驗] 經5天調治的試料，使用拉力試驗機於室溫下，以 200 mm /分鐘的延伸速度測定τ型剝離強度。 [耐水粘著力評價試驗] 本紙張尺度適用中國國家標準（CNS )八4規格（21〇><297公釐） -13- 200300164 A7 B7 五、發明説明（10) 經5天調治的試料’於室溫以純水浸漬2天。2天後 取出試料將水分輕拭抹乾’立即使用拉力試驗機於室溫下 ，以200 mm /分鐘的延伸速度測定T型剝離強度。 [實施例2及比較例1〜5] 除使用表1所記載的粘著劑配方以外，與實施例1同 樣，所得的試料的粘著試驗結果彙集如表1所示。 (請先閱讀背面之注意事填寫本頁) 經濟部智慧財產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） -14- 200300164 A7 B7 五、發明説明（11) 表 經濟部智慧財產局員工消費合作社印製 實方f g例 比較例 1 2 1 2 3 4 5 粘著劑處方[份] CR乳膠 100 100 100 100 100 100 100 樹脂乳液（1) 50 50 50 50 50 50 50 氧化鋅乳液(2) 1 1 1 1 1 1 1 PELEX SSH(3) 0.4 - - - - - - EMUL D-3-D(4) - 0.4 - - - - - EMUL 10(5) - - - 0,4 - - - NEOPELEX - - - - 0.4 - - NO.25(6) PELEX CS(7) - - - - - 0.4 - EMULGEN E-220(8) - - - - - - 0.4 增粘劑A20L(9) 適量 適量 適量 適量 適量 適量 適量 TAKENET WD- 4 4 4 4 4 4 4 730(10) 適用期試驗（11) 1小時後 〇 〇 〇 Δ 〇 〇 0 3小時後 〇 〇 Δ X 〇 〇 〇 6小時後 〇 〇 X X X Δ X 24小時後 Δ Δ X X X X X 粘著力[N/mm] 常態粘著力 5.0 4.5 4.2 4.3 4.6 4.4 4.3 耐熱粘著力 2.2 2.1 2.2 2.2 2.1 1.9 1.9 耐水粘著力 3.0 2.8 2.7 2.7 2.6 2.9 1.9 (請先閲讀背面之注意事項再填寫本I) 0, 本紙張尺度適用中國國家標隼（CNS ) A4規格（210X297公釐） -15- 200300164 A7 B7 五、發明説明（12) (1) TAMANOL E-100 (固體成分53%) /日本荒川化學工業 株式會社製 (請先閲讀背面之注意事項再填寫本頁) (2) AZ-SW (固體成分53%) /日本大崎工業株式會社製 (3) 烷基二苯基醚磺酸二鈉/日本花王株式會社製 (4) 聚環氧乙院院基（CIO - C16)釀硫酸納/日本花王株式 會社製 (5) 月桂基硫酸鈉/日本花王株式會社製 (6) 十二烷基苯磺酸鈉 /日本花王株式會社製 (7) 二辛基磺化琥珀酸鈉 /日本花王株式會社製 (8) 聚環氧乙烷十六烷基醚 /日本花王株式會社製 (9) ARON A-20L /日本東亞合成株式會社製 (10) 水分散型聚異氰酸酯/日本三井武田化學株式會社 製 (11) 適用期試驗評價 〇：僅少許變化、△:粘度增加可使用、X :不能使用 產業上之可利用性 經濟部智慧財產局員工消費合作社印製 有關本發明的聚氯丁二烯爲主劑，以聚異氰酸酯化合 物爲硬化劑所成的二液型粘著劑，由添加烷基二苯基醚二 磺酸鹽及/或聚環氧乙烷醚硫酸鹽，不會對粘著物性有不 良影響，可延長聚氯丁二烯系二液型粘著劑的適用期。 主要元件對照表 雷射光束 本紙張尺度適用中國國家標準（CNS ) A4規格（210 X 297公釐） -16- 200300164 A7Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs, the polyalkylene oxide alkyl ether sulfate used in the present invention is shown in Chemical Formula 2 below. In the formula, R1 is preferably an alkyl group having 6 to 20 carbon atoms, and particularly preferably 10 to 16 carbon atoms. R2 is preferably an alkylene group having 2 to 6 carbon atoms, and particularly preferably 2 to 4 carbon atoms. B is an alkali metal ion such as sodium and potassium, an ammonium ion, and the like. Ideal examples can be listed as sodium or potassium salt of polyethylene oxide dodecyl ether sulfate, sodium or potassium salt of polyethylene oxide octadecyl ether sulfate, etc. This paper is applicable to China Standard (CNS) A4 specification (21 × 297 mm) -8-200300164 A7 ______ B7 5. Description of the invention (5) But not limited to this. (Please read the precautions on the back before filling out this page) R1 '(0'R2〇nS〇4 · B Chemical Formula 2 Addition of nominal diphenyl ether disulfonate and / or polyoxyethyl sulfate It is particularly limited that it is desirable to add 1 mass part or less to 5 mass parts. An addition amount greater than 5 mass parts may adversely affect the adhesion characteristics. Among them, 100 mass parts of polychloroprene is added to 0.0 1 to 2 masses. The method for adding the academic monophenyl ether disulfonate and / or polyethylene oxide alkyl sulfate is not particularly limited, and the method for directly adding the same or an aqueous solution is simple. The academic diphenyl ether disulfonate The addition period of the polyethylene oxide alkyl sulfate is not particularly limited before adding the polyisocyanate, and it must be uniformly dispersed before adding the polyisocyanate. The extension effect of the pot life is shown by adding the present invention I started to discover a surfactant with a specific structure, and not all surfactants can be found. The Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs printed the polyisocyanate compound of the present invention, which contains 2 molecules in the molecule. Isocyanate-based compounds, for example, tolyl diisocyanate (TDI), xylene diisocyanate (xdi), ι, 3-bis (isocyanate) cyclohexane, hexamethylene diisocyanate (HDI), Ortho-Spinane Diisocyanate (NBDI), Tetramethylxylene Diisocyanate, Isophorone Diisocyanate (IPDI), 4,4'-Diphenylmethane Diisocyanate (MDI), Trimethylhexamethylene diisocyanate (TMDI), p-phenylene diisocyanate (PPDI), trimethylglycine diisocyanate (LDI), naphthalene diisocyanate (NDI), cyclohexyl diisocyanate (CHDI), triphenylmethane-4,4 ', 4M-triisocyanate This paper size applies to Chinese National Standard (CNS) A4 specification (210X297 mm) -9-200300164 A7 B7 V. Description of the invention (6), Phosphoro-tri- (p-isocyanate phenyl ester) ) Etc. (Please read the precautions on the back before filling out this page) Also, the so-called block isocyanate of which the isocyanate group of this polyisocyanate compound is masked with a blocking agent, or a polyurethane prepolymer derived from a polyisocyanate compound, Contains 2 or more isocyanates The ester group is also included in the polyisocyanate compound referred to in the present invention. From the viewpoint of dispersibility, a water-based adhesive can generally use a polyisocyanate compound to impart a nonionic hydrophilic group to a soap-free water-dispersible structure with a water-dispersible structure. Polyisocyanate is preferred. The polychloroprene-based two-liquid type adhesive of the present invention can optionally add an adhesion promoter, a tackifier, a metal oxide, a filler, and a film in addition to the essential components. Additives, UV absorbers, oxidation inhibitors, plasticizers, vulcanization agents, vulcanization accelerators, defoamers, etc. Adding these additives can balance initial adhesion, water resistance, and adhesion retention time in practical use And other characteristics. Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs. When water-based adhesives are used in combination with adhesives, their types are not particularly limited. Specific examples include rose acid resin, polymerized rose acid resin, α-pinene resin, / 3-pinene resin, terpene phenol resin, C5 distillate petroleum resin, C9 distillate petroleum resin, C5 / C9 distillate petroleum For resins, DCPD-based petroleum resins, alkylphenol resins, xylene resins, daidzein-indene resins, etc., in order to obtain sufficient initial adhesion, resins having a softening temperature of 50 to 160 ° C are preferred. The method for adding the tackifier is not particularly limited. The resin can be uniformly dispersed, and it is preferable to add it after it has become an aqueous emulsion. The manufacturing method of the water-based emulsion of the adhesive agent is based on toluene and other paper standards that are applicable to the Chinese National Standard (CNS) A4 (210X297 mm) -10- printed by the Intellectual Property Bureau of the Ministry of Economic Affairs and Consumer Cooperatives 200300164 Α7 ___________ Β7 V. Description of the invention (7) After dissolving the organic solvent, emulsifying / dispersing in water with an emulsifier, removing the organic solvent by heating under reduced pressure, and emulsifying / dispersing after crushing into fine particles, etc., previously It is desirable to make finer particles. The polychloroprene-based latex composition of the present invention can be adjusted to an arbitrary viscosity by blending a thickener. Specific tackifiers include, for example, polyvinyl alcohol (PVA), sodium polyacrylate, water-soluble polyurethane, bonded polyurethane emulsion, alkali-swelling acrylic emulsion, and carboxymethyl cellulose ( CMC), methyl cellulose (MC), hydroxyethyl cellulose (HEC), hydroxypropyl cellulose (HPC), synthetic montmorillonite, and the like. The blending amount of the tackifier is based on 100 parts by mass of the polychloroprene-based latex solid component, and 0.01 to 10 parts by mass (equivalent to the solid content) is added, and preferably 0.01 to 2 parts by mass is suitable. The application of the method for extending the pot life of the polychloroprene storage-type two-liquid water-based adhesive of the present invention is not particularly limited, and it can be applied to all applications requiring high adhesive strength. Specific uses such as the shoe industry, furniture, carpentry, simple wetsuits, roof building materials, automotive, construction and other uses. 4. Embodiments of the Invention The effects of the present invention will be described in more detail with examples and comparative examples below. The present invention is not limited to the examples. In the following description, unless there is any special notice, "parts" and "%" are based on quality. [Synthesis example 1] Using a reactor with a volume of 3 liters, and putting it under a nitrogen stream, the paper size is applicable to the Chinese National Standard (CNS) A4 specification (210 X 297 mm) (Please read the precautions on the back before filling in this Page)-Packing-Book-11-200300164 A7 B7 V. Description of the invention (8) Please read the note on the back first: 100 parts of water, 5 parts of heterogeneous rose acid, 0.6 parts of sodium hydroxide, 0.7 Parts of potassium hydroxide, 0.3 parts of sodium salt of formaldehyde naphthalenesulfonic acid condensate, 0.3 parts of sodium bisulfite, and after dissolving, 100 parts of chloroprene monomer and 0.4 parts of η were added under stirring. -Dodecyl alcohol. Using potassium persulfate as an initiator, polymerization was carried out at 10 ° C under a nitrogen atmosphere. When the polymerization rate reached 90%, a suspension of phenothiazine was added to stop the polymerization. Unreacted monomer was removed under reduced pressure to obtain a polychloroprene latex. The water was evaporated and concentrated under reduced pressure, and the solid content was adjusted to 50% by mass. [Example 1] Using the polychloroprene latex obtained in Synthesis Example 1, a polychloroprene latex and a tackifier resin were added. , Zinc oxide emulsion, disodium dodecyl diphenyl ether sulfonate and the like are mixed and stirred in the ratio shown in Table 1. Add a tackifier, and adjust the viscosity to the range of 100 to 150 m P a · S as the main agent of the water-based adhesive. A polyisocyanate compound shown in Table 1 was added to this base agent, and after stirring, it became a two-liquid water-based adhesive. Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs. The proportions shown here are based on 100 parts of polychloroprene in polychloroprene latex, and the corresponding medicines are converted to solid parts. . In Example 1, the adjusted adhesive, its pot life and adhesion test were carried out as described below. The samples used for the adhesion test were prepared as follows. The adhesive obtained above is 300 g / cm2 with a brush (the solid content is changed to the paper size and the Chinese National Standard (CNS) A4 specification (210X297 mm) is applied) -12- 200300164 A7 B7 V. Description of the invention (9) ( Please read the notes on the back before filling in this page) Calculate) Apply on canvas (# 9). After standing for 20 minutes, the obtained canvas was cut, and the two canvases were adhered to each other with their adhesive surfaces facing each other, and pressed with a hand roller. Adhesion test was provided after 5 days of conditioning. [Period test] After adding the polyisocyanate, observe the appearance immediately (with or without coagulation) and measure the viscosity. The evaluation was judged in three stages. Only a small change from before addition was regarded as normal (0), and the viscosity only increased slightly. Within the usable range, it was judged to be usable (△), and solidification occurred, or the viscosity increased significantly. Status (X). [Normal Adhesion Evaluation Test] The T-peel strength was measured using a tensile tester at room temperature at a stretch rate of 200 mm / min using a test specimen prepared for 5 days. [Heat resistance evaluation test] Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs. A 5-day-conditioned sample was tested at 80 ° C using a tensile tester at a tensile speed of 200 mm / min to measure the τ-type peel strength. [Normal Adhesion Evaluation Test] The test piece prepared after 5 days was measured at room temperature using a tensile tester at a stretching speed of 200 mm / min to measure the τ-type peel strength. [Water-resistant adhesion evaluation test] This paper size is in accordance with Chinese National Standard (CNS) 8-4 specification (21〇 < 297 mm) -13- 200300164 A7 B7 V. Description of the invention (10) Samples adjusted after 5 days 'Immerse in pure water at room temperature for 2 days. After 2 days, the sample was taken out, and the water was wiped and dried. Immediately using a tensile tester at room temperature, the T-peel strength was measured at an extension speed of 200 mm / min. [Example 2 and Comparative Examples 1 to 5] Table 1 shows the results of the adhesion test of the obtained samples in the same manner as in Example 1 except that the adhesive formulations described in Table 1 were used. (Please read the notes on the back first and fill out this page) The paper size printed by the Employees' Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs applies the Chinese National Standard (CNS) A4 specification (210X297 mm) -14- 200300164 A7 B7 V. Description of the invention ( 11) Table fg Example printed by the Consumers' Cooperative of the Intellectual Property Bureau of the Ministry of Economy Comparative Example 1 2 1 2 3 4 5 Adhesive prescription [parts] CR latex 100 100 100 100 100 100 100 Resin emulsion (1) 50 50 50 50 50 50 50 Zinc oxide emulsion (2) 1 1 1 1 1 1 1 PELEX SSH (3) 0.4------EMUL D-3-D (4)-0.4-----EMUL 10 (5) ---0,4---NEOPELEX----0.4--NO.25 (6) PELEX CS (7)-----0.4-EMULGEN E-220 (8)------0.4 increase Adhesive A20L (9) Right amount Right amount Right amount Right amount Right amount TAKENET WD- 4 4 4 4 4 4 4 730 (10) Pot life test (11) After 1 hour 〇〇 △ 〇〇 3 After 〇〇Δ X 〇〇〇〇 After 6 hours XXX Δ X After 24 hours Δ Δ XXXXX Adhesive force [N / mm] Normal adhesive force 5.0 4.5 4.2 4.3 4.6 4.4 4.3 Heat resistance Adhesive force 2.2 2.1 2.2 2.2 2.1 1.9 1.9 Water-resistant adhesive force 3.0 2.8 2.7 2.7 2.6 2.9 1.9 (Please read the notes on the back before filling in this I) 0, This paper size applies to China National Standard (CNS) A4 specification (210X297) -15- 200300164 A7 B7 V. Description of the invention (12) (1) TAMANOL E-100 (53% solid content) / Japan Arakawa Chemical Industry Co., Ltd. (Please read the precautions on the back before filling this page) ( 2) AZ-SW (53% solid content) / made by Japan's Osaki Industry Co., Ltd. (3) disodium alkyl diphenyl ether sulfonate / made by Japan's Kao Corporation (4) polyethylene oxide courtyard base (CIO- C16) Sodium sulfate / manufactured by Kao Corporation (5) sodium lauryl sulfate / manufactured by Kao Corporation (6) sodium dodecylbenzenesulfonate / manufactured by Kao Corporation (7) dioctylsulfonated amber Sodium / Kao Corporation (8) Polyethylene Oxide Cetyl Ether / Kao Corporation (9) ARON A-20L / Japan Toa Synthetic Corporation (10) Water-dispersible Polyisocyanate / Made by Mitsui Takeda Chemical Co., Ltd. (11) Potential test evaluation 〇: Only slight change △: Viscosity increase can be used, X: Can not be used Industrially, the Intellectual Property Bureau of the Ministry of Economic Affairs, Employees Cooperative Cooperative printed the polychloroprene as the main agent of the present invention, and the polyisocyanate compound was used as the hardener. Two-liquid type adhesive, by adding alkyl diphenyl ether disulfonate and / or polyethylene oxide ether sulfate, will not adversely affect the physical properties of the adhesive, and can prolong the polychloroprene type The pot life of liquid adhesive. Comparison Table of Main Components Laser Beam This paper size is applicable to Chinese National Standard (CNS) A4 specification (210 X 297 mm) -16- 200300164 A7
7 B 五、發明説明（13) 2 透光性基體 3 1 第1介電質層 4 相變化型記錄層 32 第2介電質層 5 反射層 20 支撐基體 6 保護層 --------批衣-- (請先閲讀背面之注意事項再填寫本頁) 訂 經濟部智慧財產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（210X 297公釐） -17-7 B V. Description of the invention (13) 2 Translucent substrate 3 1 First dielectric layer 4 Phase-change recording layer 32 Second dielectric layer 5 Reflective layer 20 Supporting substrate 6 Protective layer ------ -Approval of clothing-(Please read the precautions on the back before filling this page) Order the paper printed by the Employees' Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs to apply the Chinese National Standard (CNS) A4 size (210X 297 mm) -17 -