200837100 九、發明說明： 【明屬々頁】 發明領域 本發明係關於一種將紙品起皺之方法，其中紙匹係使 用一種包含聚胺基醯胺表氯代醇樹脂及聚醯胺摻合物之黏 著劑組成物黏著於一起皺缸筒。 t先前技術3 發明背景 面紙之期望性質包括柔軟度、蓬鬆度、拉伸性及吸收 10度可利用蒸氣加熱之洋基造紙機(Yankee)乾燥器缸筒及刮 刀而達成。濕纖維料片於加壓輥軋面大量脫水，於該處片 材轉運至洋基造紙機表面上。此時紙匹有35_4〇%稠度。紙 張進一步於熱洋基缸筒上乾燥至90-97%稠度，以刮刀移 除。刮刀的機械動作結果導致纖維-纖維鍵結的崩解，於料 15片内部之微小折疊結構的形成。此種過程稱作為起皺。 為了發展出皺褶，紙匹必須黏著於洋基乾燥器表面 上。黏著係經由噴霧黏著劑於乾燥器上來提供。最常見之 洋基黏著劑為合成聚合物，諸如聚胺基醯胺-表氯代醇樹 脂、聚胺-表氣代醇樹脂、聚乙烯醇、聚乙酸乙烯酯、聚丙 20烯醯胺及聚醚類。使用多種低分子量化合物、油類及界面 活性劑來改性洋基塗覆性質。 包含高分子量及低分子量聚胺基醯胺表_代醇樹脂、 分別為PAE-I及PAE-II之混合物之起皺黏著劑係說明於美 國專利案6,277,242。 、 5 200837100 面紙業界對於製造極為柔軟的面紙(優質等級)極為感 興趣，該種面紙要求於極低片材水含量（小於3%)起敵。習 知起皺黏著劑於全面性乾燥時傾向於變硬而對要求低水分 起皺之全面性乾燥較為無法再度濕潤。硬質塗層結果導致 刮刀的抖動且喪失料性，可能導_刀磨耗及起敵不 均。如此大為要求有一種起敵黏著劑，其於低水分起敵條 件下仍然可維持柔軟且可再度濕潤。 、傳統熱固黏著劑極為類似持久性濕強度樹脂，形成極 10 為脆[生塗層’於南水分(大於6%)起㈣件下效果良好。若 =有車乂低又度之熱固黏著劑遠更為通用且可於更寬廣之 料片水分含量範·7%起敵。當於較低水含量起敵時了非 …、叫^通仏為容易管理，提供較佳之片材控制。改性 劑诸如多疋醇，如甘油可進一步用來調整黏著程度，改良 塗層之柔軟^: 15劑仍缺變太: 。但即使添加改性劑，習知黏著 持，要有/其用途仍然係限於水分含量大於3%。如此 持-而要有改良之起皺黏著劑組成物。 【發％内容】 發明概要 於一個會# / 20 分為基準K ^中，本發明係關於—種以聚合物活性成 醯胺表南代醇=9至_約99:1之比例包含一種或多種聚胺基 协 3、9及一種或多種聚醯胺之組成物。 法，包含— r也例中，本發明為一種起敵一紙匹之方 以聚合物活性^中之起皺缸筒，施用—黏著劑組成物， 物質為基準，該黏著劑組成物係以約1:99至 6 200837100 、、’勺99·1之重塁比包含一種或多種聚胺基醢胺表鹵代醇樹脂 及一種或多種聚醯胺；b)將紙匹朝向起皺缸筒施壓來執行 紙匹之黏著於起皺缸筒；以及c)使用刮刀從起皺缸筒上鬆 脫紙匹。 5 【實方式】 較佳實施例之詳細說明 本發明之組成物有用之聚醯胺可於適合用於形成長鏈 聚醯胺之條件下，例如於高於約13〇它之溫度下進行數小 時，伴以水副產物或醇副產物，而由一種或多種有機二綾 10酸衍生物與一種或多種多伸烷基多胺之縮聚合反應製造。 所得聚醯胺典型具有藉凝膠滲透層析術/多角光散射 (GPC/MALLS)測得之重量平均分子量約為500道爾頓至約 500,000道爾頓，以及對50%溶液於25°C而言，具有聚合物 布汝克斐(Brookfield)黏度高於約1〇〇 cps。可於聚合結束時 15加水來製造水性聚合物溶液。 通常，足量有機酸衍生物與大致上全部第一胺基反 應，但不足以與多伸烷基多胺之第二胺基反應至任何顯著 程度。於一實施例中，有機二羧酸衍生物與多伸烷基多胺 係以莫耳比約〇·8:1至約1·4:1反應。於另一個實施例中，有 20機二羧酸衍生物與多伸烷基多胺係以莫耳比約〇·9:1至約 1.0:0.9 反應。 「有機二羧酸衍生物」包括脂肪族二羧酸及芳香族二 羧酸及其相對應之酸氯化物、酸酐類及酯類及其混合物。 酯類較佳為C^C3脂肪族酯類。有機二羧酸衍生物係選擇讓 7 200837100 所得聚醯胺為水溶性或水可分散性。 代表性有機二羧酸衍生物及其衍生物包括順丁烯二 酸、丁二酸、戊二酸、己二酸、庚二酸、辛二酸、壬二酸、 癸二酸、鄰苯二甲酸、間苯二曱酸、對苯二曱酸、禁二羧 5 酸、順丁烯二酸二甲酉旨、丙二酸二甲醋、丙二酸二乙酿、 丁二酸二甲酯、丁二酸二異丙酯、戊二酸二甲酯、戊二酸 二乙酯、己二酸二甲酯、己二酸甲酯乙酯、癸二酸二甲酯、 鄰苯二甲酸二甲酯、間苯二甲酸二甲酯、對苯二甲酸二甲 酯、萘二羧酸二甲酯、二鹼基酯類(DBE)、聚（乙二醇）貳（羧 10 基甲基)醚、丁二醯氯、戊二醯氯、己二醯氯、辛二醯氣、 癸二酸鹽、鄰苯二甲醯氯、間苯二甲醯氯、對苯二甲醯氯、 萘二羧酸鹽、順丁烯二酐、丁二酐、戊二酐、鄰苯二甲酐、 1，8-萘二酐等。 「多伸烷基多胺類」一詞表示有兩個第一胺基(-NH2) 15 以及至少一個第二胺基之有機化合物，此處胺基氮原子係 藉伸烷基共同聯結，但限制條件為兩個氮原子不可附接於 同一個碳原子。代表性多伸烧基多胺包括二伸乙基三胺 (DETA)、三伸乙基四胺（TETA)、四伸乙基五胺（ΤΕΡΑ)、二 伸苯基三胺等。 20 本發明之組成物有用之聚胺基醯胺表氯代醇樹脂為水 溶性陽離子性熱固樹脂，其典型製法係經由含第二胺基之 一種或多種多伸烧基多胺與一種或多種二羧酸衍生物反應 來形成多胺基醯胺，以及然後讓該多胺基醯胺與表氯代醇 反應來形成聚胺基醯胺表氣代醇樹脂。 8 200837100 聚胺基醯胺之製備係如 製備之說明 刖文對組成物之聚醯胺成分之 於-實施例中，有機二緩酸衍生物盘多伸烧 基多胺係以莫耳比紙i至約M:1反應。於另_個實施例 中’有機二魏衍生物與多伸燒基多胺細莫耳比約〇_9:1 至約1.0:0.9反應。 聚胺基酿胺隨後與表氯代醇已經控制之條件下反應而 形成聚胺基醯胺-表氯代S|(PAE)樹脂。較佳聚胺基酿胺係 以水稀釋至約10重量百分比至約50重量百分比之濃度，溶 液冷部至約25。(：。然後足夠與聚胺基醯胺中期望量之第二 10胺基反應之表氣代醇數ϊ徐緩添加入溶液。然後混合物於 約40C至約100°C溫度加熱至達到期望之黏度，典型約為2 小時至約8小時。適當聚胺基醯胺-表氯代醇樹脂之製備係 說明於專利案6,277,242，該案以引用方式併入此處。 於一實施例中，基於聚胺基醯胺之第二級胺基，聚胺 15基醯胺係與約〇·〇1莫耳當量至約1.8莫耳當量表鹵代醇反 應0 於一實施例中，聚胺基醯胺表鹵代醇樹月旨具有重量平 均分子量約10,000至約5,000,000道爾頓；聚醯胺具有重量 平均分子量約500至約500,000道爾頓。 20 於一實施例中，表i代醇為表氯代醇。 於一實施例中，本發明之組成物以基於聚合物活性物 質約10:90至約95··5之比例，包含一種或多種聚胺基醯胺表 鹵代醇樹脂及一種或多種聚醯胺。於另一個實施例中，本 發明之組成物以基於聚合物活性物質約40:60至約80:2〇之 9 200837100 比例，包含一種或多種聚胺基醯胺表1¾代醇樹脂及一種或 多種聚醯胺。 於一實施例中，聚胺基醯胺表鹵代醇樹脂具有重量平 均分子量約50,000至約2,000,000道爾頓；聚醯胺具有重量 5 平均分子量約500至約500,000道爾頓。 於一實施例中，聚胺基醯胺表鹵代醇樹脂之製備方式 係經由以聚胺基醯胺之第二級胺基為基準，聚胺基醯胺與 約0.05莫耳當量至約0.8莫耳當量表氯代醇反應而製備。於 另一實施例中，聚胺基醯胺表i代醇樹脂之製備方式係經 10 由以聚胺基醯胺之第二級胺基為基準，聚胺基醯胺與約0.1 莫耳當量至約0.3莫耳當量表氯代醇反應而製備。 於一實施例中，聚胺基醯胺為二伸乙基三胺與選自於 己二酸、戊二酸、DBE-2二元酸酯、戊二酸二甲酯及己二 酸二甲酯或其混合物之二羧酸衍生物之反應產物。 15 於一實施例中，聚胺基醯胺為二伸乙基三胺與選自於 DBE-2二元酸S旨、己二酸、戊二酸、戊二酸二甲醋及己二 酸二甲醋或其混合物之一種或多種二羧酸衍生物之反應產 物。 於一實施例中，聚胺基醯胺表鹵代醇樹脂具有重量平 20 均分子量約50,000至約2,000,000道爾頓；聚醯胺具有重量 平均分子量約1，〇〇〇至約50,000道爾頓。 於一實施例中，聚胺基醯胺表鹵代醇樹脂具有重量平 均分子量約1〇〇,〇〇〇至約1，〇〇〇,〇〇〇道爾頓；聚醯胺具有重量 平均分子量約3,000至約20,000道爾頓。 10 ^〇837i〇〇 於〜實施例中，聚胺基醯胺表卣 二伸己基三胺及表氯代醇之三聚物脂為戊二酸、 與二伸己基三胺之絲物。 及聚_為己二酸 5 10 面。：= 广可呈稀水溶液而施用至起皺缸筒表 基溶液包含物1至約5崎量比聚胺 量2表鹵代_脂/聚醯胺組成物及物99至約50%重 分熟諳起皺黏著狀祕界人切了解此種較高百 7於混合物之理由，部分係基於只沈積極為薄層黏著 I筒上，於-實施财，沈積極薄層黏著劑於起敵 缸筒上最容易使用噴霧吊桿而達成。 水溶液之ΡΗ須經輕㈣—步讓組成物敎化。於一 實施例中’ ΡΗ係調整至約2-7。於另一個實施例中幽調 整至約4-6,之調整可使用有機酸或無機酸達成。代表性 酸類包括甲酸、乙酸、硫酸、鹽酸、碟酸等。於一實施例 15中，PH係使用硫酸或磷酸或其混合物調整。 於一實施例中，本發明之黏著組成物進一步包含一種 或多種多元醇，一種或多種磷酸鹽或其混合物。 如用於本文，「多元醇」一詞係指由伸烷基所組成以及 至多約6個羥基，其中伸烷基視需要可由一個或多個〇基或 2〇 NH基中斷所組成之單純水溶性多元醇。代表性多元醇包括 甘油、乙二醇、L4-丁二醇、二乙醇胺、三乙醇胺、山梨糖 醇一乙一醇、二乙一醇、丙二醇、二丙二醇、多乙二醇 等0 於一實施例中，多元醇係選自於甘油、乙二醇、山梨 11 200837100 糖醇、二乙二醇、丙二醇、多乙二醇及二乙醇胺。 於一實施例中，多元醇為甘油。 代表性鱗酸鹽包括正磷:酸、焦填酸、偏鱗酸、三聚鱗 酸、亞磷酸及次亞磷酸之鈉鹽、鉀鹽及銨鹽。磷酸鹽也包 5括經由以磷酸調整起皺組成物之pH而於原位所形成之磷酸 鹽。於一實施例中，磷酸鹽係選自於磷酸一銨、磷酸二銨、 經由以磷酸調整起皺組成物之pH而於原位所形成之磷酸鹽 及其混合物。 以乾聚合物為基準，相對於聚胺基醯胺表氣代醇樹脂/ 10 聚醯胺組成物，多元醇及/或磷酸鹽之用量典型係於約0.5% 重量比至約50%重量比之範圍。於一實施例中，期望使用 約0.5%重量比至約20%重量比多元醇及/或磷酸鹽。須了解 並非全部多元醇皆可獲得類似的結果。於某些情況下，依 據採用之溫度，所使用之特定聚胺基醯胺表氯代醇樹脂/聚 15 醯胺組成物及其它變數而定，需要常規實驗來判定欲使用 之最佳多元醇或磷酸鹽，以及判定結合特定聚胺基醯胺表 氯代醇樹脂/聚醯胺組成物之特定用量。 於一實施例中，連同該聚合物黏著劑，也呈經稀釋、 經乳化或分散成水溶液形式之離型助劑施用至洋基乾燥 20器。離型助劑與黏著劑材料於洋基乾燥器表面上交互作用 來防止塗層的過量堆積，來管理片材的黏著性，以及減少 刮刀的磨耗。代表性離型助劑包括由環烷烴油、鏈烷烴油、 植物油、礦油或合成油與乳化界面活性劑所组成之離型 油。為了形成穩定之水性分散液，離型助劑典型係與一種 12 200837100 或多種界面活性劑諸如脂肪酸、料化醇、絲化脂肪酸 等-起調配。離型助劑可於黏著劑組成物之前或之後施用 於起皺缸筒上型助射與轉劑_起娜來施用於 起皺缸筒上。 5 树明之黏著劑組成物也可組合技藝界使狀功能性 添加劑來改良面紙或紙巾的柔軟度。代表性之功能添加劑 包括含約12至約22個碳原子之脂肪鍵之有機第四級鹽，包 括二烧基味唾琳鐵第四鹽、二烧基二醯胺基胺第四鹽、— 烧基三曱基銨第四鹽、二烧基二甲基錄第四鹽、三院基一 1〇甲基銨第四鹽、乙氧化第四鹽、二烧基醋第四鹽及三院基 酯第四鹽等。額外適當功能添加劑包括聚矽氧烷類、第四 聚矽氧類、有機反應性聚矽氧烷類、胺基官能基聚二曱基 矽氧烷類等。於/實施例中，功能性添加劑係選自於二烷 基咪唑鑕第四鹽及第四聚矽氧。 15 於一實施例中，功能性添加劑可與本發明之黏著劑組 成物一起調配來施用至起皺缸筒。 前文說明之喷霧用途進一步可利用多種手段來改良， 例如經由使用設計供雙重覆蓋或三重覆蓋之喷桿，經由振 搖喷桿，以及經由從喷桿出口再循環經稀釋之起皺助劑組 20成物來改良混合且減少分離的可能。聚胺基醯胺表氯代醇 樹脂/聚醢胺組成物之目標用途也可使用PCT 2004031475 所述方法及裝置而達成。 另外，聚胺基醯胺表氣代醇樹脂/聚醯胺組成物、功能 性添加劑及/或離蜇助劑可經由使用空氣（或氣體）霧化施用 13 200837100 至起皺缸筒上，而非呈水溶液施用。 經由參考下列實例將可更加了解前文說明，實例僅供 舉例說明之用而非意圖囿限本發明之範圍。 實例1 5 己^一酸一伸乙基二胺聚合物之製備 於1〇〇〇毫升反應瓶内進給204 3克二伸乙基三胺。反應 器以氮氣掃除，將50克水，4·〇克硫酸及295.2克己二酸進給 至反應器内，同時混合物加熱至165。〇。透過冷凝器收集 水。反應混合物於165°C維持5小時。視需要可施加真空來 10提高聚合物分子量。然後以攪拌緩慢添加水(423.5克）至反 應器内，獲得50%聚胺基醯胺聚合物溶液。 實例2 己二酸-二伸乙基三胺_表氣代醇樹脂之製備 於500毫升反應器内進給114克聚醯胺(5〇%溶液，如實 15例1製備）及283克水。溶液以氮氣掃除。混合物加熱至 50°C，添加3.0克表氯代醇至反應器内。溫度維持於刈它， 每30分鐘監測產物黏度1次。當產物黏度達到3〇卬<25它， 2號心軸於30 rpm)時，藉加入16.3克15°/〇碳酸中止反應。以 硫酸將終pH調整至3.5。 2〇 實例3 水性聚胺基醯胺表氯代醇樹脂/聚醯胺組成物之製備 於1500毫升燒㈣進給人㈣2製備之聚絲醯胺表 氯代醇樹脂/聚醯胺組成物(349.75克），實例丨製備之聚胺基 醯胺（147.97克）及甘油（27.98克）。混合物混合至均質，以85% 200837100 填酸調整pH至4.〇。 實例4 撕離力黏著 由本發明之調配物所提供之黏著性係利用撕離黏著測 5試來測定。本測試測定由經加熱之金屬板撕離棉條所需之 力。首先，含15%活性物質之黏著劑組成物利用40號塗覆 桿施用至金屬板上。金屬板加熱至lOOt：，此時利用1.9 kg 圓柱形輥輪將濕（用於濕沾黏）或乾（用於乾沾黏）棉條按壓 入薄膜内。於施用棉條後，金屬板置於l〇5°C烤爐15分鐘來 1〇 乾燥棉條。然後金屬板夾緊於拉力測試裝置。棉布的一端 夾在測試器之氣動夾内，棉布的另一端由金屬板以180度角 且以恆定速度撕離。於撕離期間，金屬板控制於1〇〇。〇溫 度。代表性聚胺基醯胺表氣代醇樹脂/聚醯胺組成物與代表 性如美國專利案6,277,242所示組成物之撕離力黏著性之比 15 較顯示於表1。表1中，PAE係指聚胺基醯胺表氯代醇樹脂 及PA係指聚醯胺。 表1 撕離力黏著性資料 摻合物中PAE-Ι之分量 (占總聚合物活性物質 之 wt%) PAE-I+PA (本發明） -—--—— PAE-I+PAE-II (美國專 利6,277,242之代表） 12.5 - 182 ^^ 18.8 - 409 25.0 658 504 ^' 31.3 784 386 37.5 877 355 ^^~ 43.8 563 -------— 50.0 368 - — 如表1所示，本發明之組成物亦即PAE樹脂與聚醯胺之 15 200837100 摻合物（PAE-I+PA)，顯示比美國專利6,277,242之組成物此 處使用兩種PAE樹脂(PAE-I+PAE-II)，前者顯示較高之撕離 黏著性。 實例5 5 玻璃轉換溫度(Tg) ΤΑ 2920差動掃描量熱計DSC(TA儀器公司，德拉威州 新堡）用來測定代表性聚合物組成物之玻璃轉換溫度。聚合 物試樣係經由於105°C鑄塑薄膜製備。DSC儀器係使用銦標 準品校準。DSC分析之試樣大小約為10_15毫克。試樣係以 10 10它/分鐘之加熱速率加熱。使用半高法而由第二次掃描判 定聚合物之玻璃轉換溫度。 實例6 切變儲存模量(G，） 切變儲存模量係使用流量計AR2〇〇0(TA儀器公司，德 15 20 拉威州新堡）測定。試樣係經由從5%(w/w)聚合物溶液鑄塑 薄膜而製備。試樣於95t：烤爐内乾燥隔夜。所得薄膜以壓 模(直徑8毫米)衝孔來製造出試樣圓鍵。圓鍵於11〇。〇直空烤 爐内乾燥2小時，於使用前儲存於乾燥器。用於分析^何 為8毫米不鏽鋼平行板。切變儲存模量係於11〇。〇，^沿及 〇篇應變而於減模败。代表性㈣劑組成物之撕離力 資料、玻璃轉換溫度資料及切_存模量資料顯示於表2。 表2 ^j7(克/吋） 乾沾黏 ~0~~ Tg (°C) G，於 110°c& 1 Hz (kPa) 63 710 試樣 %聚合物 活性物質 %甘油（以產 物為基準） PH PAE-I+PA(本 15.0 0 7 877 16 200837100 發明） ---—·__ 以甘油改性 之 PAE-I+PA 15.0 3 7 1053 188 33 32 PAE-I 15.0 0 7 117 0 91 一 3700 以甘油改性 之 PAE-I 15.0 3 7 102 113 30 ----— 230 PAE-III 14.9 0 7 480 0 76 1300 以甘油改性 之 PAE-III 14.9 3 7 57 62 26 46 ^^-1 :具有戈，之莫耳比約為015之聚胺基醯胺表氯代醇樹脂 PAE-III :具有表虱代醇/胺之莫耳比約為〇1〇之聚胺基醯胺表氯代醇樹脂 5 10 15 本發明之代表性組成物之性質及撕離力黏著性資料與 市售PAE黏著劑，亦即PAE-I及PAE-III作比較。本發明之黏 著劑提供比較習知起皺黏著劑中所使用之PAE樹脂顯著更 高之撕離力。本發明之黏著劑之玻璃轉換溫度(T g)也比習知 樹脂之玻璃轉換溫度顯著更低。與黏著劑薄膜之柔軟度有 雄、切關聯之切變儲存模量G’資料，證實於極為乾燥之條件 下，本發明之黏著劑比較習知PAE樹脂遠更柔軟。 添加甘油可進一步改良黏著性，大為降低Tg&G，，於相等 甘/由含3； (3 /)，以產物為基準）時，本發明之黏著劑提供遠 較高之黏著性及顯著較低之G’。 可未脖離如申請專利範圍界定之本發明之構想及範 圍，而對本文說明之本發明之組成物、方法之操作及方法 之配置做出改變。 【圖式簡單說明】 (無） 【主要元件符號說明】 (無） 17200837100 IX. INSTRUCTIONS: [Ming 々 】] Field of the Invention The present invention relates to a method for creping paper products, wherein the paper is blended with a polyamine amide containing epichlorohydrin resin and polyamine. The adhesive composition of the object adheres to the crumpled cylinder. Prior Art 3 Background of the Invention The desired properties of facial tissue, including softness, bulkiness, stretchability, and absorption of 10 degrees, can be achieved using a steam heated Yankee dryer cylinder and doctor blade. The wet fibrous web is dewatered in a large amount on the pressurized rolling surface where the sheet is transferred to the surface of the Yankee paper machine. At this point the paper has a consistency of 35_4%. The paper was further dried to a temperature of 90-97% on a hot ocean cylinder and removed by a doctor blade. The mechanical action of the doctor blade results in the disintegration of the fiber-fiber bond and the formation of a tiny folded structure inside the 15 pieces. This process is called wrinkling. In order to develop wrinkles, the paper must adhere to the surface of the Yankee dryer. The adhesive is provided on the dryer via a spray adhesive. The most common ocean based adhesives are synthetic polymers such as polyamine amide-epichlorohydrin resins, polyamine-epoxy alcohol resins, polyvinyl alcohol, polyvinyl acetate, polypropylene 20 olefin amines and polyethers. class. A variety of low molecular weight compounds, oils, and surfactants are used to modify the Yankee coating properties. A creping adhesive comprising a high molecular weight and low molecular weight polyamine amide-based alcohol resin, a mixture of PAE-I and PAE-II, respectively, is described in U.S. Patent No. 6,277,242. , 5 200837100 The facial tissue industry is extremely interested in making extremely soft facial tissue (quality grade), which requires an extremely low sheet water content (less than 3%) to compete. Conventional creping adhesives tend to harden during general drying and are less wettable for general drying requiring low moisture wrinkling. Hard coating results in squeegee shake and loss of material properties, which can lead to knife wear and inconsistency. This is so great that there is a hostile adhesive that remains soft and rewet under low moisture conditions. The traditional thermosetting adhesive is very similar to the permanent wet strength resin, and the formation of the pole 10 is brittle [raw coating] works well under the south moisture (greater than 6%). If there is a low-temperature and low-temperature thermosetting adhesive, it is far more versatile and can be used against a wider material moisture content of 7%. When the enemy is at a lower water level, it is not easy to manage. It is easy to manage and provides better sheet control. Modifiers such as polyterpene alcohols, such as glycerin, can be further used to adjust the degree of adhesion and improve the softness of the coating: 15 agents are still missing too: However, even if a modifier is added, it is conventionally adhered to, and its use/use is still limited to a moisture content of more than 3%. This is the case - and there is a modified creping adhesive composition. [% of the content] Summary of the invention in a meeting # / 20 divided into the benchmark K ^, the present invention relates to a kind of polymer active into the guanamine table of the southern alcohol = 9 to _ about 99: 1 ratio of one or A plurality of compositions of polyamines 3, 9 and one or more polyamines. In the present invention, the present invention is a creping cylinder of a polymer active material, an application-adhesive composition, and a substance based on a substance, and the adhesive composition is Approx. 1:99 to 6 200837100, 'Spray 99·1 weight ratio includes one or more polyamine amide amine halohydrin resins and one or more polyamines; b) papers toward the creping cylinder Apply pressure to perform the adhesion of the paper to the creping cylinder; and c) use a spatula to release the paper from the creping cylinder. 5 [Solution] DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS The polyamines useful in the compositions of the present invention can be used under conditions suitable for forming long chain polyamines, for example, at temperatures above about 13 Torr. Hours, accompanied by water by-products or alcohol by-products, are produced by polycondensation of one or more organic diindole 10 acid derivatives with one or more polyalkylene polyamines. The resulting polyamine typically has a weight average molecular weight of from about 500 Daltons to about 500,000 Daltons as measured by gel permeation chromatography/polygonal light scattering (GPC/MALLS), and a 50% solution at 25 °C. In all, it has a polymer Brookfield viscosity of greater than about 1 〇〇 cps. An aqueous polymer solution can be produced by adding water at the end of the polymerization. Generally, a sufficient amount of the organic acid derivative reacts with substantially all of the first amine group, but is insufficient to react with the second amine group of the polyalkylene polyamine to any significant extent. In one embodiment, the organodicarboxylic acid derivative is reacted with a polyalkylene polyamine at a molar ratio of from 8:1 to about 1.4:1. In another embodiment, the 20-membered dicarboxylic acid derivative and the polyalkylene polyamine are reacted at a molar ratio of from about 9:1 to about 1.0:0.9. The "organic dicarboxylic acid derivative" includes aliphatic dicarboxylic acids and aromatic dicarboxylic acids and their corresponding acid chlorides, acid anhydrides and esters, and mixtures thereof. The esters are preferably C^C3 aliphatic esters. The organic dicarboxylic acid derivative is selected such that the polyamine obtained in 7200837100 is water-soluble or water-dispersible. Representative organic dicarboxylic acid derivatives and derivatives thereof include maleic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, ortho-benzene Formic acid, isophthalic acid, terephthalic acid, banned dicarboxylate 5, maleic acid dimethyl hydrazine, malonic acid dimethyl vinegar, malonic acid diethylene glycol, dimethyl succinate , diisopropyl succinate, dimethyl glutarate, diethyl glutarate, dimethyl adipate, methyl adipate ethyl ester, dimethyl sebacate, phthalic acid Methyl ester, dimethyl isophthalate, dimethyl terephthalate, dimethyl naphthalene dicarboxylate, dibasic ester (DBE), poly(ethylene glycol) hydrazine (carboxyl 10-methyl) Ether, butyl dichloride, pentane chloride, hexamethylene chloride, octanedioxane, sebacate, phthalic acid, m-xylylene chloride, terephthalic acid chloride, naphthalene Carboxylate, maleic anhydride, succinic anhydride, glutaric anhydride, phthalic anhydride, 1,8-naphthalene dianhydride, and the like. The term "polyalkylene polyamines" means an organic compound having two first amine groups (-NH2) 15 and at least one second amine group, wherein the amine nitrogen atom is bonded by a derivatized alkyl group, but The restriction is that two nitrogen atoms cannot be attached to the same carbon atom. Representative polyalkylene polyamines include diethylidene triamine (DETA), triethylidenetetramine (TETA), tetraethylidene pentaamine, bistriphenyltriamine, and the like. 20 The useful composition of the present invention is a polyamine guanamine chlorohydrin resin which is a water-soluble cationic thermosetting resin, which is typically produced by one or more polyalkylene polyamines having a second amine group and one or A plurality of dicarboxylic acid derivatives are reacted to form a polyamine decylamine, and then the polyamine guanamine is reacted with an epichlorohydrin to form a polyamine guanamine oxime resin. 8 200837100 Preparation of polyamine decylamine, as described in the description of the preparation of the polyamine component of the composition - in the examples, the organic bis-acid acid derivative disc polyalkylene polyamine is Moerby paper i to about M: 1 reaction. In another embodiment, the 'organic diwei derivative is reacted with a polyalkylene polyamine fine molar ratio from about 99:1 to about 1.0:0.9. The polyamine-based amine then reacts with the epichlorohydrin under controlled conditions to form a polyamine guanamine-epichloro S | (PAE) resin. Preferably, the polyamine amine is diluted with water to a concentration of from about 10 weight percent to about 50 weight percent, with the solution cold to about 25. (:. Then the amount of epigas alcohol sufficient to react with the desired amount of the second 10 amine group in the polyamine decylamine is slowly added to the solution. The mixture is then heated at a temperature of from about 40 C to about 100 ° C to achieve the desired viscosity. Typically, from about 2 hours to about 8 hours. The preparation of a suitable polyamine guanamine-epichlorohydrin resin is described in U.S. Patent No. 6,277,242, the disclosure of which is incorporated herein by reference. The second amine group of the amine decylamine, the polyamine 15 amide amine is reacted with about 1.8·〇1 molar equivalent to about 1.8 moles of the epihalohydrin. In one embodiment, the polyamine amide The epihalohydrin tree has a weight average molecular weight of from about 10,000 to about 5,000,000 Daltons; the polyamidoamine has a weight average molecular weight of from about 500 to about 500,000 Daltons. 20 In one embodiment, the epichlorohydrin is epichlorohydrin. Alcohol. In one embodiment, the composition of the present invention comprises one or more polyamine guanamine epihalohydrin resins and one or more in a ratio of from about 10:90 to about 95·5 based on the polymer active material. a variety of polyamines. In another embodiment, the compositions of the invention are based on polymerization The active material comprises from about 40:60 to about 80:2 99 200837100 in proportion, comprising one or more polyamine amides, a phenolic resin, and one or more polyamines. In one embodiment, the polyamine hydrazine The amine epihalohydrin resin has a weight average molecular weight of from about 50,000 to about 2,000,000 Daltons; the polyamine has a weight average molecular weight of from about 500 to about 500,000 Daltons. In one embodiment, the polyamine amide is halogenated. The alcohol resin is prepared by reacting polyamine decylamine with from about 0.05 mole equivalents to about 0.8 moles of epichlorohydrin based on the second amine group of the polyamine decylamine. In an embodiment, the polyamine decylamine i-alcohol resin is prepared by 10 based on a second amine group of polyamine decylamine, and the polyamine decylamine is from about 0.1 mole equivalent to about 0.3. Prepared by reacting a molar equivalent of a chlorohydrin. In one embodiment, the polyamine decylamine is a di-ethyltriamine and is selected from the group consisting of adipic acid, glutaric acid, DBE-2 dibasic acid ester, and pentane. a reaction product of a dicarboxylic acid dimethyl ester and a dicarboxylic acid adipate or a mixture thereof, a dicarboxylic acid derivative. 15 In an embodiment The polyamine decylamine is di-ethyltriamine and is selected from the group consisting of DBE-2 dibasic acid, adipic acid, glutaric acid, glutaric acid dimethyl vinegar and adipic acid dimethyl vinegar or a reaction product of one or more dicarboxylic acid derivatives of the mixture. In one embodiment, the polyamine decylamine epihalohydrin resin has a weight of 20 averaging molecular weight of from about 50,000 to about 2,000,000 Daltons; The average molecular weight is from about 1, 〇〇〇 to about 50,000 daltons. In one embodiment, the polyamine decylamine epihalohydrin resin has a weight average molecular weight of about 1 Torr, 〇〇〇 to about 1, 〇〇〇 , 〇〇〇 Dalton; polyamine has a weight average molecular weight of from about 3,000 to about 20,000 Daltons. 10 ^ 〇 837 〇〇 〜 实施 实施 实施 实施 实施 实施 实施 实施 实施 实施 聚 聚 聚 聚 聚 聚 聚 聚 聚 聚 聚 聚 聚 聚 聚 聚 聚 聚 聚 聚 聚 聚 聚 聚 聚 聚 聚 聚 聚 聚 聚 聚 聚 聚 聚 聚And poly_ is adipic acid 5 10 face. := Can be applied as a dilute aqueous solution to the creping cylinder base solution containing 1 to about 5 sacrificial ratio of polyamine 2 epihalo-lipid/polyamide composition and 99 to about 50% by weight The familiar clams and sticky secrets understand the reason for this higher ratio of 7 in the mixture, based in part on the deposition of only a very thin layer of adhesive I, on the implementation of the deposit, the deposition of a very thin layer of adhesive in the enemy cylinder It is the easiest to use with a spray boom. The aqueous solution must be deuterated by light (four)-steps. In one embodiment, the tether is adjusted to about 2-7. In another embodiment, the adjustment is to about 4-6, and the adjustment can be achieved using an organic or inorganic acid. Representative acids include formic acid, acetic acid, sulfuric acid, hydrochloric acid, dish acid, and the like. In an embodiment 15, the pH is adjusted using sulfuric acid or phosphoric acid or a mixture thereof. In one embodiment, the adhesive composition of the present invention further comprises one or more polyols, one or more phosphates or mixtures thereof. As used herein, the term "polyol" refers to a simple water-soluble composition consisting of an alkylene group and up to about 6 hydroxyl groups, wherein the alkylene group may be interrupted by one or more sulfhydryl groups or 2 〇NH groups. Polyol. Representative polyols include glycerin, ethylene glycol, L4-butanediol, diethanolamine, triethanolamine, sorbitol monoethyl alcohol, diethyl alcohol, propylene glycol, dipropylene glycol, polyethylene glycol, etc. In one embodiment The polyol is selected from the group consisting of glycerin, ethylene glycol, and sorbitol 11 200837100 sugar alcohol, diethylene glycol, propylene glycol, polyethylene glycol, and diethanolamine. In one embodiment, the polyol is glycerin. Representative sulphates include orthophosphorus: acid, pyroic acid, meta- squaric acid, trimeric squaric acid, sodium and hypophosphite salts, potassium salts and ammonium salts. The phosphate also includes a phosphate formed in situ by adjusting the pH of the creping composition with phosphoric acid. In one embodiment, the phosphate is selected from the group consisting of monoammonium phosphate, diammonium phosphate, phosphate formed in situ via pH adjusting the creping composition with phosphoric acid, and mixtures thereof. The polyol and/or phosphate is typically present in an amount of from about 0.5% by weight to about 50% by weight, based on the dry polymer, relative to the polyamine decylamine epoxide resin/10 polyamine composition. The scope. In one embodiment, it is desirable to use from about 0.5% by weight to about 20% by weight of polyol and/or phosphate. It is important to understand that not all polyols can achieve similar results. In some cases, depending on the temperature employed, the particular polyamine guanamine chlorohydrin resin/poly 15 guanamine composition and other variables used, routine experimentation is required to determine the optimum polyol to use. Or phosphate, and to determine the specific amount of the combination of the specific polyamine guanamine chlorohydrin resin / polyamide composition. In one embodiment, together with the polymeric binder, a release aid that is also diluted, emulsified or dispersed into an aqueous solution is applied to the Yankee Dryer. The release aid and the adhesive material interact on the surface of the Yankee dryer to prevent excessive build-up of the coating to manage the adhesion of the sheet and to reduce the wear of the blade. Representative release auxiliaries include release oils composed of naphthenic oils, paraffinic oils, vegetable oils, mineral oils or synthetic oils and emulsifying surfactants. In order to form a stable aqueous dispersion, the release aid is typically formulated with a 12 200837100 or a plurality of surfactants such as fatty acids, catalyzed alcohols, silk fatty acids, and the like. The release aid can be applied to the creping cylinder prior to or after application of the adhesive composition to the creping cylinder. 5 Shuming's adhesive composition can also be combined with technical functional additives to improve the softness of facial tissue or paper towels. Representative functional additives include organic fourth-grade salts having a fat linkage of from about 12 to about 22 carbon atoms, including a dialkyl-based salined iron fourth salt, a dialkyldiamine-amine amine fourth salt, Pyridyl triammonium ammonium fourth salt, dialkyl dimethyl record fourth salt, three-yard base-one hydrazine methyl ammonium fourth salt, ethoxylated fourth salt, dialkyl vinegar fourth salt and three hospitals The fourth salt of the ester or the like. Additional suitable functional additives include polyoxyalkylenes, fourth polyoxins, organic reactive polyoxyalkylenes, amine functional polydidecyloxanes, and the like. In the embodiment, the functional additive is selected from the group consisting of a dialkyl imidazolium fourth salt and a fourth polyfluorene oxide. In one embodiment, a functional additive can be formulated with the adhesive composition of the present invention for application to a creping cylinder. The spray application described above can be further modified by a variety of means, for example by using a spray bar designed for double or triple coverage, by vibrating the spray bar, and by recycling the diluted crepe assistant set from the spray bar outlet. 20% to improve mixing and reduce the possibility of separation. The intended use of the polyamine guanamine chlorohydrin resin/polyamine composition can also be achieved using the methods and apparatus described in PCT 2004031475. In addition, the polyamine decylamine epoxide resin/polyamine composition, the functional additive and/or the hydrazine auxiliaries can be applied by atomization using air (or gas) 13 200837100 to the creping cylinder, and Not applied in aqueous solution. The foregoing description may be better understood by reference to the following examples, which are not intended to be Example 1 Preparation of a hexanoic acid-extended ethyldiamine polymer 204 3 g of di-ethyltriamine was fed in a 1 ml flask. The reactor was purged with nitrogen, and 50 g of water, 4·g of sulfuric acid and 295.2 g of adipic acid were fed into the reactor while the mixture was heated to 165. Hey. Water is collected through the condenser. The reaction mixture was maintained at 165 ° C for 5 hours. A vacuum may be applied as needed to increase the molecular weight of the polymer. Water (423.5 g) was then slowly added with stirring to the reactor to obtain a 50% polyamine amide polymer solution. Example 2 Preparation of adipic acid-diethylethylamine _epoxide alcohol resin 114 g of polyamidamine (5 〇% solution, as prepared in Example 15) and 283 g of water were fed in a 500 ml reactor. The solution was purged with nitrogen. The mixture was heated to 50 ° C and 3.0 g of epichlorohydrin was added to the reactor. The temperature was maintained at 刈 and the product viscosity was monitored once every 30 minutes. When the product viscosity reached 3 〇卬 < 25, and the spindle No. 2 was at 30 rpm, the reaction was stopped by adding 16.3 g of 15 ° / hydrazine carbonate. The final pH was adjusted to 3.5 with sulfuric acid. 2〇Example 3 Preparation of aqueous polyamine decylamine epichlorohydrin resin/polyamine composition in 1500 ml of fired (iv) feeder (4) 2 prepared polysilamide chlorohydrin resin/polyamine composition ( 349.75 g), an example of the preparation of polyamine amide (147.97 g) and glycerol (27.98 g). The mixture was mixed until homogeneous, and the pH was adjusted to 4. 以 with 85% of 200837100. Example 4 Peeling Adhesion Adhesion provided by the formulation of the present invention was determined using a tear-off adhesion test. This test measures the force required to tear a sliver from a heated metal sheet. First, an adhesive composition containing 15% of an active material was applied to a metal plate using a No. 40 coating rod. The metal plate was heated to 100 t: at this time a wet (for wet) or dry (for dry) sliver was pressed into the film using a 1.9 kg cylindrical roller. After applying the sliver, the metal plate was placed in an oven at 10 ° C for 15 minutes to dry the sliver. The metal plate is then clamped to the tensile test device. One end of the cotton cloth was clamped in the pneumatic clamp of the tester, and the other end of the cotton cloth was peeled off by a metal plate at a constant angle of 180 degrees. During the tearing off, the metal plate is controlled at 1 inch. 〇 Temperature. The ratio of the representative polyamine decylamine epoxide resin/polyamine composition to the tear adhesion adhesion of the composition shown in U.S. Patent No. 6,277,242 is shown in Table 1. In Table 1, PAE means polyamine guanamine epichlorohydrin resin and PA means polyamine. Table 1 Part of PAE-Ι in the tear-off adhesive data blend (% by weight of total polymer active material) PAE-I+PA (Invention) ----- PAE-I+PAE-II (Representative of US Patent 6,277,242) 12.5 - 182 ^^ 18.8 - 409 25.0 658 504 ^' 31.3 784 386 37.5 877 355 ^^~ 43.8 563 -------— 50.0 368 - — As shown in Table 1, The composition of the invention, namely PAE resin and polyamine 15 200837100 blend (PAE-I+PA), shows a composition compared to US Patent 6,277,242. Two PAE resins (PAE-I+PAE-II) are used herein. The former shows a higher tear adhesion. Example 5 5 Glass Transition Temperature (Tg) ΤΑ The 2920 differential scanning calorimeter DSC (TA Instruments, Newcastle, Delaware) was used to determine the glass transition temperature of a representative polymer composition. The polymer samples were prepared by casting a film at 105 °C. DSC instruments are calibrated using indium standards. The sample size for DSC analysis was approximately 10-15 mg. The sample was heated at a heating rate of 10 10 /min. The glass transition temperature of the polymer was determined by a second scan using the half height method. Example 6 Shear Storage Modulus (G,) Shear storage modulus was measured using a flow meter AR2〇〇0 (TA Instruments, De 15 20 Newcastle, Latvia). The samples were prepared by casting a film from a 5% (w/w) polymer solution. The samples were dried overnight in an oven at 95t. The obtained film was punched with a stamper (diameter: 8 mm) to produce a sample round key. The round key is at 11 〇. Dry in a straight oven for 2 hours and store in a desiccator before use. For analysis ^ what is 8 mm stainless steel parallel plate. The shear storage modulus is at 11 〇. 〇, ^ along the 应变 strain and the loss of the model. The tearing force data, glass transition temperature data and cut-and-storage modulus data of representative (four) agent compositions are shown in Table 2. Table 2 ^j7 (g / 吋) dry adhesion ~0~~ Tg (°C) G, at 110 ° c & 1 Hz (kPa) 63 710 sample % polymer active material % glycerol (based on product) PH PAE-I+PA (Invention 15.0 0 7 877 16 200837100) ----·__ PAE-I+PA modified with glycerol 15.0 3 7 1053 188 33 32 PAE-I 15.0 0 7 117 0 91 a 3700 PAE-I modified with glycerol 15.0 3 7 102 113 30 ----- 230 PAE-III 14.9 0 7 480 0 76 1300 PAE-III modified with glycerol 14.9 3 7 57 62 26 46 ^^-1 : Polyamine guanamine chlorohydrin resin PAE-III having a molar ratio of about 015: polyamine amide having a molar ratio of oxime to an amine of about 1 表Alcohol Resin 5 10 15 The properties of the representative compositions of the present invention and the peeling adhesion data are compared with commercially available PAE adhesives, namely PAE-I and PAE-III. The adhesive of the present invention provides a significantly higher tear force than the PAE resin used in conventional creping adhesives. The glass transition temperature (Tg) of the adhesive of the present invention is also significantly lower than the glass transition temperature of conventional resins. The shear storage modulus G' data, which is visibly related to the softness of the adhesive film, confirms that the adhesive of the present invention is much softer than the conventional PAE resin under extremely dry conditions. The addition of glycerol can further improve the adhesion, greatly reducing the Tg & G, and the equivalent of the sugar / from the 3; (3 /), based on the product), the adhesive of the present invention provides a much higher adhesion and significant Lower G'. Variations in the configuration of the compositions, methods, and methods of the invention described herein may be made without departing from the spirit and scope of the invention. [Simple description of the diagram] (None) [Explanation of main component symbols] (None) 17