1302560 經濟部智慧財產局員工消費合作社印製 A7 B7 五、發明説明（彳） 一、 發明之技術領域 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 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。 ϋϋ ·1ϋ ·ϋϋ ^mn i^m *——^1 t i^m I— n mt— teemetmi f_li V ^ mu —mi imMMMB (請先閱讀背面之注意事項再填寫本頁) 本^紙張尺度適用中國國家標準（CNS ) M規格（210X 297公釐）~_ 5 1302560 A7 B7 五、發明説明（2 ) 以下詳細說明本發明的內容。本發明所謂的聚氯丁二 儲係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-l，3-丁二烯，丁二烯，異戊二烯，苯 &烯’丙烯酸腈，丙烯酸及其酯類，甲基烯酸及其酯類等 ’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。 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.國國家標準（CNS ) A4規格（210X297公釐） (請先閲讀背面之注意事項再填寫本頁) 裝------訂-----^ 經濟部智慧財產局8工消費合作社印製 13025601302560 Ministry of Economic Affairs Intellectual Property Office Staff Consumer Cooperatives Printed A7 B7 V. INSTRUCTIONS (彳) 1. Field of the Invention The present invention provides a polychloroprene latex mainly composed of a polychloroprene latex and a hardener. The two-component aqueous adhesive is a method for improving the pot life of the adhesive after mixing the polyisocyanate. Second, the first technology In the field of the majority of the use of solvent-based adhesives, the operator's safety and health or the working environment needs to be changed to a water-based adhesive. However, the water-based adhesive has a lot of adhesive strength or workability, which is inferior to the solvent-based adhesive. In order to improve these points, it is proposed to use a two-component water-based adhesive of isocyanate. At present, the use of a two-component adhesive has a practical problem of short application period due to the formulation. DISCLOSURE OF THE INVENTION The present invention has been made in view of the circumstances, and provides a method for controlling the pot life of a polychloroprene two-liquid type aqueous adhesive. The present inventors have intensively studied the results of the above-mentioned objects, and added a specific interfacial activity to a two-liquid type aqueous adhesive mainly composed of a polychloroprene latex and a polyisophthalate compound as a curing agent. The agent has been found to have a pot life of the water-based adhesive which can be extended to a practical level to complete the present invention. That is, the present invention relates to a two-liquid type aqueous adhesive mainly composed of a polychloroprene latex and a polyisophthalate compound as a hardener, to add an alkyl diphenyl ether disulfonate and/or a poly Ethylene oxide alkyl ether sulfate is a method characterized by extended pot life. Ϋϋ ·1ϋ ·ϋϋ ^mn i^m *——^1 ti^m I- n mt- teemetmi f_li V ^ mu —mi imMMMB (please read the notes on the back and fill out this page) National Standard (CNS) M Specification (210X 297 mm)~_ 5 1302560 A7 B7 V. Description of Invention (2) The contents of the present invention will be described in detail below. The so-called polychloroprene reservoir is a separate polymer of 2-chloro-1,3-butadiene (hereinafter abbreviated as chlorobutene), or a chlorobutene and a monomer copolymerizable with chlorobutene. Copolymer, here the so-called copolymer is a graft copolymerized copolymer of other monomers in the presence of polychloroprene. Preferred monomers which can be copolymerized with the above chlorobutene include, for example, 2,3-dichloro1,3-butadiene, 1-chloro-1,3-butadiene, butadiene, isoprene. , Benzene & ene acrylonitrile, acrylic acid and esters thereof, methenoic acid and esters thereof, etc. may be used in combination of two or more. The polymerization method for obtaining chlorobutene is not particularly limited, and it is generally easily obtained by emulsion polymerization. Further, the polychloroprene latex obtained by emulsion polymerization can be used as it is in the present invention. In the polychloroprene obtained by the emulsion polymerization of the present invention, the obtained polychloroprene is dissolved in a solvent, and the solution is dispersed in an emulsion. Secondly, the method of removing the organic solvent is obtained, and the step is uneconomical. The emulsifier and/or the dispersing agent used in the emulsion polymerization of the polychloroprene latex are not particularly limited, and various anionic or nonionic emulsifiers which are usually used for the chlorobutylene latex can be used. Examples of the anionic and nonionic emulsifiers include a carboxylic acid type, a sulfonic acid type, a sulfate type, and the like, and examples thereof include an alkali metal salt of rosin acid, an alkyl sulfonate having a carbon number of 8 to 20, and an alkylaryl group. Sulfate, a condensate of sodium naphthalenesulfonate and formaldehyde, and the like, and specific examples of the nonionic type include polyvinyl alcohol or a copolymer thereof (for example, a copolymer with an acrylamide), a polyvinyl ether or a copolymer thereof. (for example, copolymer with maleic acid), polyvinylpyrrolidone or its copolymerization paper size applicable to national standard (CNS) A4 specification (210X297 mm) (please read the notes on the back and fill out this page) ) ------ set-----^ Ministry of Economic Affairs Intellectual Property Bureau 8 workers consumer cooperatives printed 1302560
經濟部智慧財產局員工消費合作社印製 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10()質量份（氯 丁燒單獨聚合物時），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）時以〇.5〜 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〇〜5 〇 °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。 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 _ 十二烷基锍醇或叔-十二烷基巯醇等的長鏈烷锍醇類、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 -第三級-丁基-4 -甲基酣、吩噻嗪、羥基胺等。 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。 本紙張尺度通用中.國國家標隼（CNS ) A4規格（210Χ 297公釐） «威------1T-----^ (請先閱讀背面之注意事項再填寫本頁) 1302560 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、銨離子等爲理想。其理想的例可列舉如 十二烷基二苯基醚磺酸的二鈉或二_、十八烷基二苯基醚 磺酸的二鈉或二鉀等，但不限定於此。Ministry of Economic Affairs, Intellectual Property Office, employee consumption cooperative printing (for example, copolymer with vinyl acetate), or chemically modified (co)polymer, or cellulose derivative (hydroxyethyl cellulose). Among them, the above rose salt is most suitable for the present invention. The amount of the emulsifier and/or the dispersing agent to be added to the polychloroprene latex of the present invention is 10 parts by mass of the chlorobutene monomer initially charged (in the case of chloroprene alone polymer), or an initial stage. When the total amount of the chloroprene monomer and the copolymerized monomer to be charged is 100 parts by mass (when the chlorobutene copolymer is used), it is preferably from 5 to 20 parts by mass. When the amount is less than 5 parts by mass, the emulsifying power is insufficient, and when it exceeds 20 parts by mass, the water-resistant adhesive strength is lowered. The polymerization temperature of the polychloroprene latex of the present invention is not particularly limited. The smooth polymerization temperature of the polymerization reaction is preferably 〇~5 〇°c, and the polymerization initiator is a persulfate such as potassium persulfate. An organic peroxide or the like such as tributyl hydroperoxide is suitable, but is not limited thereto. There is no particular limitation on the type of the chain transfer agent used for the polymerization of polybutene. A user of emulsion polymerization of usually chlorobutene can be used. For example, a well-known chain shifting agent such as long-chain alkyl sterol such as n-dodecyl decyl alcohol or tert-dodecyl decyl alcohol, diisopropyl xanthogen disulfide, iodoform or the like can be used. . The polychloroprene polymerization stopper (polymerization inhibitor) is not particularly limited, and for example, 2,6-tertiary-butyl-4-methyloxime, phenothiazine, hydroxylamine or the like can be used. The final polymerization rate of the polychloroprene is not particularly limited and can be arbitrarily adjusted. The unreacted monomer is removed by a demonomerization operation, and the method is not particularly limited. The polychloroprene latex of the present invention is controlled to a necessary concentration by concentration or dilution with water. The concentration method is concentrated under reduced pressure or the like, but is not particularly limited. This paper scale is used in the national standard (CNS) A4 specification (210Χ 297 mm) «威------1T-----^ (please read the notes on the back and fill out this page) 1302560 A7 B7 V. DESCRIPTION OF THE INVENTION (4) The properties of the polychloroprene latex of the present invention are not particularly limited, and polymerization temperature, polymerization initiator, chain shifting agent, polymerization inhibitor, final polymerization ratio, and demonomerization Suitable conditions such as concentration conditions, control, adjustment of solid concentration, molecular weight of toluene soluble fraction, toluene insoluble fraction (gelatinization content), and the like. The gelation content of the chloroprene (co)polymer in the polychloroprene latex is preferably adjusted to 3 to 60% by mass from the balance between the initial adhesion and the normal adhesion. 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 or sodium, or an ammonium ion. Preferable examples thereof include, but are not limited to, disodium lauryl diphenyl ether sulfonate or disodium or dipotassium di- or octadecyl diphenyl ether sulfonic acid.
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 10〜16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（210X297公釐） (請先閱讀背面之注意事項再填寫本頁) 士^- - i 二 -- I - - ----- \» - - - I -I —1- I ^ 經濟部智慧財產局員工消費合作社印製 1302560 A7 B7 五、發明説明（5 ) 但不限定於此。 (請先閱讀背面之注意事項再填寫本頁)The polyalkylene oxide alkyl ether sulfate used in the present invention is represented by the following Chemical Formula 2. In the formula, R1 is preferably an alkyl group having 6 to 20 carbon atoms, 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 or potassium, or an ammonium ion. Desirable examples include sodium or potassium salt of polyethylene oxide lauryl ether sulfate, sodium or potassium salt of polyethylene oxide stearyl ether sulfate, etc. National Standard (CNS) A4 Specification (210X297 mm) (Please read the note on the back and fill out this page) 士^- - i 二-- I - - ----- \» - - - I -I —1- I ^ Ministry of Economic Affairs Intellectual Property Bureau Staff Consumer Cooperative Printed 1302560 A7 B7 V. Invention Description (5) But it is not limited to this. (Please read the notes on the back and fill out this page)
Rl- (0-R2-) n-S〇4 · B 化學式 2 烷基二苯基醚二磺酸鹽及或聚環氧乙基硫酸鹽的添加 量無特別的限定，以100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100質量份聚氯丁二烯添加0.01〜2質量理想。 烷基二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。烷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)、1,3-雙（異氰酸甲酉旨） 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，V，4”-三異氰酸酯 本紙張尺度通用中.國國家標隼（CNS ) A4規格（210X 297公釐) ~ 1302560 A7 B7 五、發明説明（6 ) 、硫代磷-三-(對-異氰酸苯基酯）等。 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。 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隼（CNS )八4規格（210X297公釐） (請先閲讀背面之注意事項再填寫本頁) -裝 經濟部智慧財產局員工消費合作社印製 1302560 A7 _______B7 五、發明説明（7 ) (請先閲讀背面之注意事¾再填寫本頁) 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1 00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烯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。 經濟部智慧財產局員工消費合作社印製 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 ) A4規格（21〇X：297公釐） 1302560 經濟部智慧財產局員工消費合作社印製 A7 B7 五、發明説明（8 ) 100份水、5份不均化玫瑰酸、0.6份氫氧化鈉、0.7份氫 氧化鉀、0·3份甲醛萘磺酸縮合物的鈉鹽、0.3份亞硫酸 氫鈉，溶解後在攪拌下加入1 00份氯丁烯單體及0.1 4份 η-十二烷基巯醇。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1000〜1 500 mPa W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。 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100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（210X 297公釐） -------、裝------訂-----^ (請先閲讀背面之注意事碩苒填寫本頁) 1302560 A7 ____B7 五、發明説明（9 ) 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（Ο)，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T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T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 ) Ai見格（210X297公釐） "" (請先閲讀背面之注意事項再填寫本頁) -裝 訂 經濟部智慧財產局員工消費合作社印製 1302560 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τ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頊再填寫本頁) .m I ϋϋ ϋϋ ml (ϋ TJ nn —ϋ m 0¾ i 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（210 X 297公釐） 1302560 A7 B7 五、發明説明（11) 經濟部智慧財產局員工消費合作社印製 表1 實施例 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i式驗（11) 1小時後 〇 〇 〇 △ 〇 〇 〇 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 L9 (請先閲讀背面之注意事項再填寫本頁) -—ι_ϋ dm ·ϋ>ϋ immetm Mm tMmMMMt - mi ·1.1· ml mi 本紙張尺度適用中.國國家標準（CNS ) A4規格（210X297公釐） 1302560 經濟部智慧財產局員工消費合作社印製 A7 B7 五、發明説明（12) U) TAMANOL E-100 (固體成分53%) /日本荒川化學工業 株式會社製 (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) 聚環氧乙烷烷基（CIO - C1 6)醚硫酸鈉/日本花王株$ 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 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。 本紙張尺度適用中國國家標準（CNS ) A4規格（210X 297公釐） 裝 訂 ^ (請先閱讀背面之注意事項再填寫本頁)Rl-(0-R2-) nS〇4 · B The amount of the alkyl diphenyl ether disulfonate and the polyepoxyethyl sulfate added is not particularly limited, and 5 parts by mass is added in 100 parts by mass. The following are ideal. The addition amount of more than 5 parts by mass may have an adverse effect on the adhesion characteristics. It is also preferably added in an amount of 0.01 to 2 by mass of 100 parts by mass of polychloroprene. The method of adding the alkyl diphenyl ether disulfonate or the polyethylene oxide alkyl sulfate is not particularly limited, and the method of directly adding the aqueous solution or the aqueous solution is simple. The addition timing of the alkyl diphenyl ether disulfonate or the polyethylene oxide alkyl sulfate is not particularly limited until the polyisocyanate is added, and it is necessary to uniformly disperse the polyisocyanate before adding it. Further, the effect of prolonging the pot life was discovered by adding a surfactant having a specific structure as shown in the present invention, and not any surfactant was found. Printed by the Ministry of Economic Affairs, the Intellectual Property Office, and the Consumer Cooperatives. The polyisocyanate compound according to the present invention contains two or more isocyanate-based compounds in the molecule. For example, tolylene diisocyanate (TDI), xylene diisocyanate (XDI), 1,3-bis (isocyanate) cyclohexane, hexamethylene diisocyanate (HDI), raw spinane diisocyanate (NBDI), tetramethylxylene diisocyanate, isofulone diisocyanate (IPDI), 4,4'-diphenylmethane diisocyanate (MDI), trimethylhexamethylene diisocyanate (TMDI), pair -phenyl diisocyanate (PPDI), trimethylglycine diisocyanate (LDI), naphthalene diisocyanate (NDI), cyclohexyl diisocyanate (CHDI), triphenylmethane-4,V,4"-triisocyanate Paper size general national standard (CNS) A4 specification (210X 297 mm) ~ 1302560 A7 B7 V. Description of invention (6), thiophosphorus-tris-(p-phenyl isocyanate). Further, a so-called blocked isocyanate in which the isocyanate group of the polyisocyanate compound is masked by a block agent, or a polyurethane prepolymer derived from a polyisocyanate compound, which contains two or more isocyanate groups, is also included in the present invention. Isocyanate compound. Water-based adhesive, From the viewpoint of dispersibility, it is generally preferred to use a polyisocyanate compound to impart a non-ionic hydrophilic group to a soap-free water-dispersible polyisocyanate having a water-dispersible structure. The polychloroprene-based two-liquid type adhesive of the present invention is preferably In addition to the essential components, an adhesion agent, a tackifier, a metal oxide, a chelating agent, a film forming aid, a UV absorber, an oxidation inhibitor, a plasticizer, a sulfurizing agent, and a vulcanization accelerator may be added arbitrarily. When the additives are added, the additives such as the initial adhesion, the water-resistant adhesion, and the adhesion holding time can be balanced in practical use. When the water-based adhesive is used in combination with the adhesion-imparting agent, the type thereof is not particularly limited. Specific examples thereof include rose acid resin, polymerized rose acid resin, α-pinene tree, /3-terpene resin, terpene phenol resin, C5 fraction petroleum resin, C9 fraction petroleum resin, and C5/C9 fraction petroleum. Resin, DCPD-based petroleum resin, alkylphenol resin, xylene resin, soybean acid-ruthenium resin, etc., in order to obtain sufficient initial adhesion, it is preferable to use a resin having a softening temperature of 50 to 160 ° C. The method of adding the agent is not particularly limited, and the resin can be uniformly dispersed, and it is preferably added after the aqueous emulsion is added. The method for producing the aqueous emulsion of the adhesion-imparting agent is applied to the paper scale of toluene or the like. China National Standard (CNS) Eight 4 Specifications (210X297 mm) (Please read the note on the back and fill out this page) - Installed by the Ministry of Economic Affairs, Intellectual Property Bureau, Staff Consumer Cooperative, Printed 1302560 A7 _______B7 V. Invention Description (7) (Please read the notes on the back 3⁄4 and then fill out this page.) After the solvent is dissolved, use the emulsifier to emulsify/disperse in water, remove the organic solvent under reduced pressure, and emulsifie/disperse after pulverizing into fine particles. The method, etc., the former can make more fine particles ideal. The polychloroprene latex composition of the present invention can be adjusted to have an arbitrary viscosity by blending a tackifier. Specific examples of the tackifier include 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 amount of the tackifier to be added is 0.01 to 10 parts by mass (in terms of solid content), preferably 0.01 to 2 parts by mass, based on 100 parts by mass of the polychloroprene latex solid component. The application of the method for extending the application period of the polychloroprene-based two-liquid type aqueous pressure-sensitive adhesive of the present invention is not particularly limited, and can be applied to applications requiring high adhesion strength in all. Specific applications such as footwear industry, furniture, woodworking, simple diving suits, roofing building materials, automotive, and construction. Printed by the Intellectual Property Office of the Ministry of Economic Affairs, Employees' Consumption Cooperatives IV. Embodiments of the Invention The effects of the present invention will be described in more detail below with reference to examples and comparative examples, but the present invention is not limited to the examples. In addition, the following descriptions are based on the absence of special notices. The "parts" and "%" are based on the quality. [Synthesis Example 1] Using a reactor with an internal volume of 3 liters, it was put into the paper scale under a nitrogen flow. National Standard (CNS) A4 Specification (21〇X: 297 mm) 1302560 Ministry of Economic Affairs Intellectual Property Office Staff Consumption Co-operative printing A7 B7 V. Description of invention (8) 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 naphthalenesulfonic acid condensate, 0.3 part of sodium hydrogen sulfite was dissolved, and after dissolution, 100 parts of chlorobutene monomer and 0.14 part of η-dodecyl decyl alcohol were added with stirring. Using potassium persulfate as an initiator, polymerization was carried out at 10 ° C under a nitrogen atmosphere, and the suspension of phenothiazine was stopped at a polymerization rate of 90%. The unreacted monomer was removed under reduced pressure to obtain a polychloroprene latex. The water was evaporated under reduced pressure and concentrated to adjust the solid content to 50% by mass. [Example 1] The polychloroprene latex obtained in Synthesis Example 1 was used to impart a resin emulsion to the polychloroprene latex and the adhesive. The zinc oxide emulsion, disodium dodecyl diphenyl ether sulfonate, and the like were blended and stirred in the proportions shown in Table 1. Further, a tackifier is added to adjust the viscosity to a range of 1000 to 1 500 mPa W as a main component of the water-based adhesive. This main agent was added with a polyisocyanate compound as shown in Table 1, and after stirring, it became a two-liquid type aqueous adhesive. Further, the blending ratios shown herein are 100 parts of polychloroprene in the polychloroprene latex, and the respective compounded products are converted into solid components. The adhered adhesive of Example 1 was tested for pot life and adhesion test as described below. Moreover, the sample used for the adhesion test was prepared as follows. The adhesive obtained above is based on a brush of 300 g/cm2 (the solid content is changed to the paper size. The national standard (CNS) A4 specification (210X 297 mm) -------, - ----Book-----^ (Please read the back of the note first, fill out this page) 1302560 A7 ____B7 V. Invention description (9) Calculate) coated on canvas (#9). After standing for 20 minutes, the obtained canvas was cut, and the adhesive faces of the two canvases were attached to each other, and pressed by a hand roller. The adhesion test was carried out 5 days after the treatment. [Purchase test] Immediately after the addition of the polyisocyanate, the appearance was observed (with or without coagulum), and the viscosity was measured. The evaluation was judged by three stages, and only a slight change state before the addition was judged to be normal (Ο), the viscosity was only slightly increased, and it was judged that the solidification occurred in the usable range (Δ), or the viscosity was greatly increased. State (X). [Normal adhesion evaluation test] The T-peel strength was measured at a stretching speed of 200 mm/min using a tensile tester at room temperature for 5 days. [Heat-Resistant Adhesion Evaluation Test] The T-peel strength was measured at a stretching speed of 200 mm/min using a tensile tester at a temperature of 80 ° C for 5 days. [Normal adhesion evaluation test] The T-peel strength was measured at a stretching speed of 200 mm/min using a tensile tester at room temperature for 5 days. [Water resistance evaluation test] This paper size is applicable to the national standard (CNS) Ai (210X297 mm) "" (Please read the note on the back and fill out this page) - Binding Ministry of Economics intellectual property Bureau employee consumption cooperative printed 1302560 A7 B7 V. Invention description (10) The sample treated for 5 days was immersed in pure water for 2 days at room temperature. After 2 days, the sample was taken out and the water was wiped dry, and the tensile strength of the type τ was measured immediately at room temperature using a tensile tester at an extension speed of 200 mm / minute. [Example 2 and Comparative Examples 1 to 5] The results of the adhesion test of the obtained samples were as shown in Table 1, except that the adhesive formulations described in Table 1 were used. (Please read the note on the back and fill out this page.) .m I ϋϋ ϋϋ ml (ϋ TJ nn —ϋ m 03⁄4 i Ministry of Economic Affairs Intellectual Property Office Staff Consumer Cooperative Printed Paper Size Applicable Chinese National Standard (CNS A4 size (210 X 297 mm) 1302560 A7 B7 V. Description of invention (11) Ministry of Economic Affairs Intellectual Property Office Staff Consumer Cooperatives Printed Table 1 Example 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 Tackifier A20L(9) Appropriate amount Appropriate amount Appropriate amount TAKENET WD- 4 4 4 4 4 4 4 730(10) Applicable period i test (11) After 1 hour 〇〇〇 △ 〇〇〇 3 hours later 〇〇 Δ X 〇〇〇 6 hours 〇〇 XXX Δ X 24 hours after Δ Δ XXXXX adhesion [N/mm] State adhesion 5.0 4.5 4.2 4.3 4.6 4.4 4.3 Heat resistance 2.2 2.1 2.2 2.2 2.1 1.9 1.9 Water resistance 3.0 2.8 2.7 2.7 2.6 2.9 L9 (Please read the note on the back and fill out this page) -—ι_ϋ dm ·ϋ> ϋ immetm Mm tMmMMMt - mi ·1.1· ml mi This paper scale applies to the national standard (CNS) A4 specification (210X297 mm) 1302560 Ministry of Economic Affairs Intellectual Property Bureau employee consumption cooperative printed A7 B7 V. Invention description (12) U) TAMANOL E-100 (solid content 53%) /Ara Japan Chemical Industry Co., Ltd. (2) AZ-SW (solid content 53%) /Japan Osaki Industries Co., Ltd. (3) Alkyl diphenyl ether sulfonic acid Disodium/Japan Kao Co., Ltd. (4) Polyethylene oxide alkyl (CIO-C1 6) ether sodium sulfate / Japanese Kao strain Co., Ltd. (5) Sodium lauryl sulfate / manufactured by Kasuga Co., Ltd. (6) Sodium dodecylbenzenesulfonate/manufactured by Kasuga Co., Ltd. (7) Dioctylsulfonated sodium succinate/manufactured by Kasuga Co., Ltd. (8) Polyethylene oxide cetyl ether/manufactured by Kasuga Corporation (9) ARON A-20L / manufactured by Japan East Asia Synthetic Co., Ltd. (10) Water-dispersed poly Cyanate ester / manufactured by Mitsui Takeda Chemical Co., Ltd. (11) Applicable period test evaluation 〇: only a slight change, △: viscosity increase can be used, X: industrial availability cannot be used. Polychloroprene according to the present invention As a main agent, a two-liquid type adhesive composed of a polyisocyanate compound as a hardening agent, which is added by an alkyl diphenyl ether disulfonate and/or a polyethylene oxide ether sulfate, does not adhere to The physical properties have an adverse effect, which can extend the pot life of the polychloroprene two-liquid adhesive. This paper size applies to the Chinese National Standard (CNS) A4 specification (210X 297 mm). Binding ^ (Please read the note on the back and fill out this page)