1284141 玖、發明說明： 【發明所屬之技術領域】 本發明是有關於一種聚異氰酸鹽/壓克力混成樹脂之 製造方法，特別是指一種以含磺酸鹽官能基之水性聚異氰 5 酸鹽溶液為介質而使壓克力單體於該溶液中進行聚人反 應後得到該混成樹脂之製造方法。 【先前技術】 為符合未來環保之要求，例如IS(M4〇〇〇認證之條件要 求，與溶劑價格不斷上漲之壓力，近來很多研究者致力於 10 發明各種不需使用揮發性有機化合物(VOC)為溶劑之水性 聚異氰酸鹽樹脂(polyurethane，簡稱PU)的合成方法。除了 上述壤保之顧慮，在水為介質之情形下合成該類可分散於 水溶液之聚異氣酸鹽樹脂亦可省去傳統油性樹脂之製法中 於聚合反應後所必須的分離及中和步驟，因此可簡化製程。 15 另外’為降低生產成本而進一步使用成本較低之壓克 力樹脂與水性聚異氰酸鹽樹脂來合成水性聚異氰酸鹽/壓 克力樹脂。而一般用於製作該類樹脂之方法包含··兩者直 接攪拌混合(blending)，或透過聚異氰酸鹽樹脂與壓克力以 交聯方法製得，該方法是透過聚異氰酸鹽樹脂與壓克力分 20 別具有之特殊官能基進行縮和去水之交聯機制 (crosslinking mechanism)反應進行，該類交聯機制之製法 詳述於例如 Progress in Organic Coatings，29，175(1996)之 期刊報導，另外，美國第4927876、5173526、5331039、 5075370號發明專利案，及澳洲第41135/89號、加拿大 1284141 第2092157號專利案，及歐洲發明專利專利案Ep 〇562 282 A1等也詳細地揭露各種經交聯機制合成水性聚異氰 酸鹽/壓克力混成樹脂之製法。其中，該類交聯機制製法中使用 之聚異氰酸鹽樹脂種類多為含羧酸鹽官能基之聚異氰酸鹽樹 脂，原因在於之前合成聚異氰酸鹽樹脂之製程多以羧酸類分 子’例如二甲基丙酸(dimethylpropanic acid，簡稱DMPA)作為 反應物，但以上述交聯方法製造時反應較不完全，且無法同時 兼具聚異氰酸鹽樹脂與壓克力樹脂的優點，另外製程抑制不 易，故存在有一些需改善之問題。 ίο 15 目前一般市售之水性聚異氰酸鹽/壓克力現成樹於 大多以直接攪拌混合的方式獲得，但以此方式入成之％ 液的均勻性較差’如圖一之示意圖所示，該乳液之安a 性不佳，放置一段時間後容易造成因壓克力聚合物比重 較輕而浮在上層之分層現象，因此保存期限較短。 除了上述兩種製法，另外有部分產品是以含綾酸鹽 官能基之水性聚異氰酸鹽樹脂為介質，後加入壓克力= 體以網狀滲透法（interpenerating network，以下巧稱ipN) 聚合成聚異氰酸鹽/壓克力混成樹脂，其中兩者不形成任 何化學鍵，只以物理糾結纏繞方式存在，如圖二 如此藉由水性聚異氰酸鹽樹脂與壓克力古 v问刀于之互 相纏繞所得之乳液，可改善上述直接攪拌所得乳液會分層 之缺點，但此類含羧酸鹽官能基之聚異氰酸鹽/壓克力二 成樹脂乳液的固形分（solid content，簡寫為〇/、π»- 〜·/〇)不咼、 易黃變，且應用於塗佈在一些織物，如棉布、尼隆布广护 ^ 4 20 1284141 所具有之透濕度較差、觸感較硬，且豐厚感不佳。當固形 份太低時會造成黏度偏低，而無法增黏至適當的黏度並使 塗佈罝之控制不易，且所製得之乳液固形份偏低時也會提 高運送之成本。 【發明内容】 因此，本發明之目的，即在提供一種色相佳、不黃 變、高固形份之水性聚異氰酸鹽/壓克力混成樹脂的製 造方法。其中，所用之水性聚異氰酸鹽樹脂為含磺酸鹽 官能基之水性聚異氰酸鹽樹脂，因而可改善了上述含羧 酸鹽官能基之聚異氰酸鹽/壓克力混成樹脂之缺點。 於是，本發明之水性聚異氰酸鹽/壓克力混成樹脂之 製造方法包含一合成含磺酸鹽官能基之水性聚異氰酸鹽 樹脂的前段製程，及一經由IPN機制在該水性聚異氰酸鹽 樹脂溶液中合成水性聚異氰酸鹽/壓克力混成樹脂之後段 製程。如下所述： (一）前段製程 目如已知合成含績酸鹽官能基之水性聚異氰酸鹽 樹脂的技術已發展地非常成熟，且詳細地敘述在多篇專 利中’例如美國第4870129、4851459、4540633號發明 專利案中，及歐洲專利合作協定（PCT/EP92)第00560號 專利案、丹麥第4024567、4109477號專利申請案中， 故在此不贅述。 上述前段製程方法之其中一具體例如下：將二異 氰酸鹽與多元醇（P〇ly〇l)以1 ^〜丨_2:1之莫耳比混合。 1284141 該二異氰酸鹽之具體例可選自雙環己基甲烷二異氰酸 鹽（4,4’-diisocyanate dicyclohexymethane，簡稱 MDI)、 甲苯二異氰酸鹽（toluene diisocyanate，簡稱 TDI)、 2,2,4-三曱基 -1，6-己烷二異氰酸鹽 5 (2,2,4-trimethyl，l，6-hexane diisocyanate ，簡稱 TMDI)、六亞甲基二異氰酸鹽（hexamethylene diisocyanate，簡稱HDI)、異佛爾酮二異氰酸鹽 (isophorone diisocyanate，簡稱 IPDI)等。多元醇之具 體例可選自聚丙稀二醇（polypropylene glycol，簡稱 10 PPG)、聚亞丁基醚二醇（polytetramethylene ether glycol，簡稱 PTMG)、聚乙二醇（polyethylene glycol， 簡稱PEG)，及AA/BG/EG型聚酯多元醇（2720 polyester polyol)。之中並加入觸媒，例如二月桂酸二丁錫 (dibutyltin dilaurate，簡稱 T-12)，於 80〜90°C 之油浴 15 中反應約5小時後形成一具有異氰酸鹽親水端的預聚 合物（prepolymer)，上述之反應時間以NCO的量到達 理論值NCO%約3.19為準，其中NCO/OH之比例會影 響產品之物性，而該NCO之理論值的計算方式為習 知，在很多有關水性聚異氰酸鹽樹脂之專利中皆可 20 見，故在此不贅述。當該預聚合物形成後，立即冷卻 至50〜60°C後加入丙S同，使該預聚合物分散於丙酉同 中，接著加入含有磺酸鹽官能基之鏈延長劑，再加入 去離子水，分散成水中油狀（0/W)狀態，最後經濃縮去 除丙酮即可得到固形份約30〜40%之水性聚異氰酸鹽 1284141 樹脂分散液（A)。 (二）後段製程，為經由IPN機制在該水性聚異氰酸鹽樹 脂溶液中合成水性聚異氰酸鹽/壓克力混成樹脂製程，包 含： 5 第一步驟：在上述（A)中同時加入氧化起始劑與 還原劑，之後慢慢滴入壓克力單體，以進行壓克力之 聚合反應而得未聚合完全之水性聚異氰酸鹽/壓克力 混成樹脂。該氧化起始劑之具體例如第三丁基過氧化 氫（tert_butyl hydroperoxide，簡稱 TBHP)、過氧化氫 10 (hydrogen peroxide)、過硫酸納（sodium persulfate)、 過硫酸卸（potassium persulfate)、過硫酸銨 (ammonium persulfate)等，而該還原劑之具體例如甲 酸次硫酸納（sodium formaldehyde sulfoxylate，簡稱 SFS)、氯化鐵錯和物（ferric chloride complex)、亞鐵 15 鹽（ferrous salt)、亞硫酸氫鈉（sodium dithionite)、硫 酸氫納（sodium hydrogen sulfite)、硫酸鈉（sodium sulfite)、硫代硫酸納（sodium thiosulfate)等。以上之 氧化劑與還原劑皆可以一種或一種以上混合之方式 使用。而該壓克力單體為含雙鍵之單體，其化學結構 20 式如下： R3 〇 η2〇 ……-c-c—〇r4 其中，R3=H、CH3、C2H5 ; R4=H、CcCs 烷基。 1284141 第二步驟：在上述未聚合完全之混成樹脂中加入油 性起始劑，再加入上述之還原劑以終止反應，即可得到 水性聚異氰酸鹽樹脂/壓克力之混成樹脂。該油性起始 劑，之具體例如α，α，_偶氮雙-異丁猜 (a,a，-azobis-iso-butyronitrile)等。 上述本發明製造方法中所使用之水性聚異氰酸鹽樹脂 與壓克力單體的重量份比率較佳為不小於2，更佳為不小於 2且小於6’若該比值小於2則所製得之乳液會分層且有顆 粒存在，若是該比值大於6則成本偏高。 且本發明之後段製程的溫度需控制在約4〇〜55〇c間，在 此溫度範圍内不會影響水性聚異氰酸鹽樹脂之穩定度，同時 可加速壓克力之聚合反應。 15 上述本發明的製造方法中同時添加氧化起始劑與還屑 劑之目的是使兩者進行氧化還原反應以產生自由基，之後奴 自由基聚合反應而得壓克力之聚合物，而加人油性起始劑之 目的在於使聚異氰酸鹽樹脂中心點之壓克力單體聚合完 =如此所得之混成樹脂不含壓克力味，依照本發明方法製 &日守，壓克力單體之聚合度可高於99 5%。 本發明之製造方法所得的水性聚異氰酸鹽/壓克 =:脂可使水性聚異氮酸鹽樹脂與壓克力均句的分 :‘繞，因此安定性佳、不會分層，且色相佳、不會黃 20 1284141 處理、傢倶塗料、軟木塗料、裝飾漆、塑膠和金屬塗佈等。 其中塗佈在織物上時，可使織物兼具水性聚異氰酸鹽樹脂與 壓克力樹脂之透濕防水、柔軟、具豐厚感等特性。因此依本 發明之製造方法所得之水性聚異氰酸鹽/壓克力混成樹脂比 5 傳統之油性聚異氰酸鹽樹脂樹脂、含羧酸基之聚異氰酸鹽/ 壓克力混成樹脂更具產品優勢。 【實施方式】 <實施例1> (一） 前段製程：取3重量份之AA/BG/EG型聚酯多元醇、6 10 重量份之聚亞丁基醚二醇、1重量份之聚丙烯二醇混合後 升溫至90QC，於真空下除水直到無氣泡產生為止。在 80〜90°C反應溫度下加入2.5重量份之雙環己基甲烷二異 氰酸鹽，反應30分鐘後滴入5滴25%之二月桂酸二丁錫， 再反應至NCO%達理論值（約3.19%)後將溫度降至50°C， 15 然後加入10重量份之丙酮攪拌均勻以降低黏度。接著加入 0.04重量份之聯氨、0.05重量份之1，2-乙二胺，及0.7重 量份之二胺磺酸鹽類分子[N-(2-aminoethyl)-2-aminoethane sulfonic acid sodium salt，C4H12N2〇3S · Na]進行反應約 1 小 時，至反應完畢後慢慢加入22.5重量份的純水，熟成約1 20 小時之後再將丙酮抽出即可得含磺酸鹽官能基之水性聚異 氰酸鹽樹脂溶液(A)，其固形份約37.6%。 (二） 後段製程··第一步驟：取1〇〇重量份之（A)液，在 45-50°C溫度下慢慢滴入含0.12重量份之第三丁基過氧 化氫、0.07重量份之曱醛次硫酸鈉、含有0.02重量份 10 1284141 之氯化鐵錯和物之水溶液，其中水之重量份為6 8，、、 • 2同 完後添加18.8重量份之丙烯酸-2-乙基己g旨（簡稱 2-EHA)，添加速度需控制於三小時内以防顆粒產生。第 二步驟：接續第一步驟再加入溶於〇·7重量份之丙酉同中 5 的〇.07重量份α，α，-偶氮雙-異丁腈作為油性起始劑，同 時也加入溶於0.7重量份水溶液中的0·07重量份曱醛次 硫酸鈉，滴完後繼續反應2小時，即可得含磺酸鹽官能 基之水性聚異氰酸鹽/壓克力混成樹脂。 將剛合成之混成樹脂以1〇5〇C溫度烘烤下測得其固形份 10 (S_C·%)、黏度（viSC0Sity，25°C )，及酸度（PH)值詳載於附表一， 另外，表一中同時列出該混成樹脂於75cc之烘箱内放置7天 烘烤後之物性值，以及放置二個月後之乳液安定性與色相。 <實施例2> 同<實施例1>之操作條件及使用量，不同之處在於所 15 使用之壓克力單體為丁基丙烯酸酯（butyl acrylate)。所得混 成樹脂之物性、安定性與色相亦詳載於附表一中。 <實施例3> 同< 實施例1>之操作條件及使用量，不同之處在於所使 用之壓克力單體為甲基丙烯酸曱酯（methyl methacrylate)。 20 所得混成樹脂之物性、安定性與色相亦詳載於附表一中， 而有關物性測試之方法亦列於表一之附註中。 <實施例4〉 同<實施例1>之操作條件，不同之處在於所使用之水性 pU與壓克力單體的比例為4 : 1，所得混成樹脂之物性、安 1284141 定性與色相亦詳載於附表一中。 【比較例】 前段製程： 在80CC之溫度下將100重量份之聚丁烯己二酸酯 5 (polybutylene-adipate，簡稱 PBA-2000)除水後，加入 9 重量 份之 1，6-亞己基二異氰酸酯（l，6-hexamethylene diisocyanate，簡稱HDI)、6重量份之異佛爾嗣二異氰酸酉旨 (Iisophorone diisocyanate，簡稱 IPD)、10 重量份之二曱基丙 酸（dimethylpropanic acid，簡稱 DMPA)、10 重量份之 1-曱基 10 -2-吼硌烧酉同（l-methyl-2-pyrrolidone，簡稱 NMP)—起反應， 四小時後NCO%為2.65%約達理論值（2.7%)，即可開始降溫 至40〜50°C，再加入110重量份之丙酮攪拌5分鐘後，加入 三乙基胺（triethylamine，簡稱TEA) 11 · 1重量份中和，之後加 入純水289重量份使其轉相，再加入鏈延長劑乙二胺 15 (ethylene diamine，簡稱 EDA)0.7 重量份及聯氨（hydrazine) 0.7重量份後熟成約1小時之後再將丙酮抽出，即可得樹脂 分散液（A)，測得其固形分為32.2% 。 後段製程： 步驟1 :取100重量份之（A)液，在40〜50°C溫度下慢慢 20 滴入含0.1重量份之第三丁基過氧化氫、0.06重量份之曱醛 次硫酸鈉、含有0.017重量份之氣化鐵錯和物之水溶液，其 中水之重量份為5.88，滴完後添加16.1重量份之丙烯酸·2-乙基酸酯（簡稱2-ΕΗΑ )，添加速度需控制於3小時内以防 顆粒產生。 12 1284141 步驟2 ·接著再加入溶於〇·6重量份之丙酮中的〇〇6重量份 之α，α’-偶氮雙-異丁腈作為油性起始劑，同時也加入溶於〇·6 重量份水溶液中0·06重量份曱醛次硫酸鈉，滴完後繼續反應 2小時，即可得紱酸鹽官能基之水性聚異氰酸鹽/壓克力混成 5 樹脂。 【織物塗佈之應用與評價】 除了上述樹脂乳液之物性比較，為進一步比較用途之一 的織物塗佈效果。本發明巾分別將上述實施例與比較例之混 成樹脂以料加；η塗佈於全棉布，及糊狀塗佈於尼龍布來比 10較它們的透濕度、豐厚感、觸感等特性，並詳載於附表一中。 以下分別簡介該二種塗佈之配方與流程： 泡珠塗佈於全棉布：取5〇g之混成樹脂與2g之白色膏 (R_3〇)、3.5g之溶於6g熱水的起泡劑（RF)、2g之（X-042)、 lg之架橋劑（M-3)、ig之穩泡劑（STA)、25g之滑劑（silica 15 S〇1)、4滴之增稠劑（HM-4〇0)混合。再將上述配方塗佈在全 棉布上並於100〇C下烘烤2分鐘後予以壓平，之後再於 下烘烤2分鐘。 糊狀塗佈於尼隆布：將一尼隆基布撥水含浸於撥水劑 (FC3552)之水溶液中，其中撥水劑與水之重量比為0.3:100, 20 之後於100。(：下忸、座？八#7々 ^ ^ 、 /、烤2刀鐘可付一撥水布，後將已調配好之 k佈液進行第一次塗佈於該撥水布上，後於1 下烘烤2 :知’再進仃第二次塗佈，之後再於，c下烘烤2分鐘， 取後在15G C下進行2分鐘之架橋反應即可完成糊狀塗佈。 由附表中可知，依照本發明之製造方法所得之 <實施 13 1284141 例1〜3〉中含磺酸鹽官能基之水性聚異氰酸鹽/壓克力混成樹 脂的固形份、黏度、酸度值在放置7天後幾乎沒有改變，表 示該樹脂乳液之安定性良好。同樣地，其在放置二個月後仍 然維持其不分層之良好安定性，及白色透明之色相。然而， 5該 < 比較例 >之含羧酸鹽官能基聚異氰酸鹽/壓克力混成樹脂 之固形份比〈實施例1〜3>來得低，且在放置二個月後會產生 黃變的現象。 歸納上述，依照本發明之製造方法所得之含磺酸鹽官能 基水性聚異氰酸鹽/壓克力混成樹脂，不僅不會產生如傳統油 10性樹脂含有有機溶劑之環保問題，且兼用水性聚異氰酸鹽樹 脂與壓克力兩種化合物可降低成本。另外，合成過程中是經 由IPN機制進行壓克力之聚合反應，故水性聚異氰酸鹽樹脂 與壓克力間疋以物理性纏繞方式糾結在一起，不會產生如傳 統直接攪拌後乳液會分層之缺點。且依照本發明之製造方 15法，使用含有磺酸鹽官能基的水性聚異氰酸鹽樹脂作為介 質，可改善部分市面上以含羧酸鹽官能基之聚異氰酸鹽樹脂 為主成分之水性聚異氰酸鹽/壓克力混成樹脂會黃變之缺 點。同時應用於塗佈在一些織物上時所具有之透濕度、豐厚 感、觸感皆比含羧酸鹽官能基之水性聚異氰酸鹽/壓克力混成 2〇 樹脂較佳。 惟以上所述者，僅為本發明之較佳實施例而已，當不能以 此限定本發明實施之範圍，即大凡依本發明申請專利二圍:發 明說明書内容所作之簡單的等效變化與修飾，皆應仍屬本發^ 專利涵蓋之範圍内。 14 Ϊ284141 【囷式簡單說明】 氰酸鹽樹脂與壓克力以直 間之分佈狀態。 闺—：說明傳統上將水性聚異 接授摔方式混合時，該兩種聚合物 圖二：說明使用本發明之方法合成水性聚異氰酸鹽/壓克 力混成樹脂時，該兩種聚合物間糾結纏繞之狀態。 表一：本發明之實施例和比較例之混成樹脂的物性與加 工後性質之比較。 15 1284141 【圖式之主要元件代表符號說明】 無 161284141 发明, the invention description: [Technical field of the invention] The present invention relates to a method for producing a polyisocyanate/acrylic hybrid resin, in particular to an aqueous polyisocyanate containing a sulfonate functional group. 5 The acid salt solution is a medium, and an acrylic resin is subjected to a polymerization reaction in the solution to obtain a method for producing the mixed resin. [Prior Art] In order to meet the requirements of future environmental protection, such as IS (M4〇〇〇 certification conditions, and the pressure of rising solvent prices, many researchers have recently committed to 10 inventions that do not require the use of volatile organic compounds (VOC). A method for synthesizing an aqueous polyisocyanate resin (PU) which is a solvent. In addition to the above-mentioned concerns of loam, it is also possible to synthesize such a polyisocyanate resin which can be dispersed in an aqueous solution in the case where water is a medium. The separation and neutralization steps necessary for the polymerization reaction in the conventional oil-based resin process are omitted, so that the process can be simplified. 15 In addition, the lower cost acrylic resin and aqueous polyisocyanate are further used to reduce the production cost. Salt resin to synthesize aqueous polyisocyanate/acrylic resin. The method generally used to make this kind of resin includes: · directly blending or blending with polyisocyanate resin and acrylic It is obtained by a cross-linking method, which is a cross-linking mechanism for shrinking and dehydrating through a polyisocyanate resin and a special functional group having an acrylic component. Anism) reaction, the method of which is described in detail in, for example, the Journal of Progress in Organic Coatings, 29, 175 (1996), in addition, the invention patents of the United States 4927876, 5173526, 5331039, 5075370, and Australia A method for synthesizing an aqueous polyisocyanate/acrylic hybrid resin by a cross-linking mechanism is also disclosed in detail in Patent No. 41,135/89, Canadian Patent No. 1,284,414, No. 2,092, 157, and European Patent No. 562 282 A1. Among them, the polyisocyanate resin used in the process of the cross-linking mechanism is mostly a polyisocyanate resin containing a carboxylate functional group, because the process for synthesizing the polyisocyanate resin is mostly a carboxylic acid. A molecule such as dimethylpropanic acid (DMPA) is used as a reactant, but the reaction is less complete when the above crosslinking method is used, and the advantages of the polyisocyanate resin and the acrylic resin cannot be simultaneously achieved. In addition, the process inhibition is not easy, so there are some problems that need to be improved. ίο 15 Currently, the commercially available water-based polyisocyanate/acrylic ready-made trees are mostly mixed directly. The method is obtained in combination, but the uniformity of the liquid obtained in this way is poor. As shown in the schematic diagram of Fig. 1, the emulsion has poor safety, and it is easy to cause the specific gravity of the acrylic polymer after being placed for a period of time. Light and floating in the upper layer, so the shelf life is shorter. In addition to the above two methods, some products are based on an aqueous polyisocyanate resin containing a phthalate functional group, followed by the addition of acrylic = The body is polymerized into a polyisocyanate/acrylic hybrid resin by an interpenerating network (hereinafter referred to as ipN), in which the two do not form any chemical bonds, only exist in physical entanglement and winding, as shown in Figure 2. The emulsion obtained by interweaving the aqueous polyisocyanate resin and the acrylic granules can improve the delamination of the above-mentioned direct agitation emulsion, but such a carboxylate-containing functional group is different. The solid content of the cyanate/acrylic resin emulsion (solid content, abbreviated as 〇/, π»-~·/〇) is not sticky, easy to yellow, and is applied to some fabrics, such as cotton, Nilongbu Guangfu ^ 4 20 1284 141 has a poor moisture permeability, a hard touch, and a poor sense of richness. When the solid content is too low, the viscosity is low, the viscosity is not increased to an appropriate viscosity, and the control of the coating is not easy, and the low solid content of the emulsion obtained also increases the cost of transportation. SUMMARY OF THE INVENTION Accordingly, it is an object of the present invention to provide a process for producing an aqueous polyisocyanate/acrylic hybrid resin which is excellent in hue, non-yellowing, and high in solids. Wherein, the aqueous polyisocyanate resin used is an aqueous polyisocyanate resin containing a sulfonate functional group, thereby improving the above-mentioned polyisocyanate/acrylic mixed resin containing a carboxylate functional group. The shortcomings. Thus, the method for producing an aqueous polyisocyanate/acrylic hybrid resin of the present invention comprises a sizing process for synthesizing an aqueous polyisocyanate resin containing a sulfonate functional group, and an aqueous polymerization via an IPN mechanism. The subsequent step of synthesizing the aqueous polyisocyanate/acrylic hybrid resin in the isocyanate resin solution. As described below: (1) Front-end process The technique of synthesizing an aqueous polyisocyanate resin containing a functional acid-functional group has been developed to be very mature, and is described in detail in several patents', for example, US Pat. No. 4,870,129. In the invention patents of No. 4,851,459 and 4,056,063, and the European Patent Cooperation Agreement (PCT/EP92) No. 00560, and the Danish Patent Nos. 4,024,567 and 4,109,477, each of which is hereby incorporated herein by reference. One of the above-mentioned first-stage process methods is specifically as follows: a diisocyanate is mixed with a polyol (P〇ly〇l) at a molar ratio of 1 ^ to 丨 2:1. 1284141 The specific example of the diisocyanate may be selected from the group consisting of 4,4'-diisocyanate dicyclohexymethane (MDI), toluene diisocyanate (TDI), 2, 2,4-trimethyl-1,6-hexane diisocyanate 5 (2,2,4-trimethyl,1,6-hexane diisocyanate, TMDI for short), hexamethylene diisocyanate ( Hexamethylene diisocyanate (HDI), isophorone diisocyanate (IPDI), and the like. Specific examples of the polyhydric alcohol may be selected from the group consisting of polypropylene glycol (abbreviated as 10 PPG), polytetramethylene ether glycol (PTMG), polyethylene glycol (PEG), and AA. /BG/EG type polyester polyol (2720 polyester polyol). And adding a catalyst, such as dibutyltin dilaurate (T-12), reacted in an oil bath 15 at 80-90 ° C for about 5 hours to form a pre-isocyanate hydrophilic end Prepolymer, the above reaction time is based on the amount of NCO reaching the theoretical value NCO% of about 3.19, wherein the ratio of NCO / OH will affect the physical properties of the product, and the theoretical value of the NCO is calculated in the conventional Many patents relating to aqueous polyisocyanate resins can be found in the patent, and therefore will not be described here. After the prepolymer is formed, it is immediately cooled to 50 to 60 ° C, and then added with the same S, the prepolymer is dispersed in the same, then a chain extender containing a sulfonate functional group is added, and then added. The ionized water is dispersed in an oily (0/W) state in water, and finally, acetone is concentrated to obtain an aqueous polyisocyanate 1284141 resin dispersion (A) having a solid content of about 30 to 40%. (2) The latter stage process for synthesizing an aqueous polyisocyanate/acrylic hybrid resin in the aqueous polyisocyanate resin solution via an IPN mechanism, comprising: 5 First step: simultaneously in the above (A) An oxidation initiator and a reducing agent are added, and then an acrylic monomer is slowly dropped to carry out an acrylic polymerization reaction to obtain an unpolymerized aqueous polyisocyanate/acrylic mixed resin. Specific examples of the oxidation initiator are, for example, tert-butyl hydroperoxide (TBHP), hydrogen peroxide, sodium persulfate, potassium persulfate, persulfate. Ammonium persulfate, etc., and specific examples of the reducing agent such as sodium formaldehyde sulfoxylate (SFS), ferric chloride complex, ferrous salt, sulfurous acid Sodium dithionite, sodium hydrogen sulfite, sodium sulfite, sodium thiosulfate, and the like. The above oxidizing agent and reducing agent may be used in one form or a mixture of more than one. The acrylic monomer is a monomer containing a double bond, and its chemical structure is 20 as follows: R3 〇η2〇...-cc-〇r4 wherein R3=H, CH3, C2H5; R4=H, CcCs alkyl . 1284141 Second step: an aqueous starting agent is added to the above-mentioned unpolymerized mixed resin, and the above reducing agent is added to terminate the reaction, whereby an aqueous polyisocyanate resin/acrylic mixed resin can be obtained. The oily initiator is specifically, for example, α,α, _azobis-iso-butyronitrile or the like. The ratio by weight of the aqueous polyisocyanate resin to the acrylic monomer used in the above production method of the present invention is preferably not less than 2, more preferably not less than 2 and less than 6', if the ratio is less than 2 The resulting emulsion will be layered and have particles present, and if the ratio is greater than 6, the cost will be high. Moreover, the temperature of the subsequent process of the present invention is controlled to be between about 4 Torr and 55 〇c, and the stability of the aqueous polyisocyanate resin is not affected in this temperature range, and the polymerization reaction of the acryl is accelerated. 15 In the above manufacturing method of the present invention, the purpose of simultaneously adding an oxidizing initiator and a swarfing agent is to carry out a redox reaction to generate a radical, and then a radical polymerization of the radical to obtain an acrylic polymer. The purpose of the human oily starter is to polymerize the acrylic monomer at the center of the polyisocyanate resin. The mixed resin thus obtained does not contain the acrylic taste, and is prepared according to the method of the present invention. The degree of polymerization of the monomer can be higher than 99 5%. The aqueous polyisocyanate / gram = grease obtained by the production method of the invention can make the aqueous polyisocyanate resin and the acrylic acid sentence: 'wound, so the stability is good and the layer is not separated. And the color is good, not yellow 20 1284141 treatment, furniture coating, cork coating, decorative paint, plastic and metal coating. When coated on the fabric, the fabric can combine the properties of the water-based polyisocyanate resin and the acrylic resin to be moisture-permeable, waterproof, soft, and rich. Therefore, the aqueous polyisocyanate/acrylic hybrid resin obtained by the production method of the present invention is more than 5 conventional oily polyisocyanate resin, carboxylic acid group-containing polyisocyanate/acrylic mixed resin. More product advantages. [Embodiment] <Example 1> (I) First stage process: 3 parts by weight of AA/BG/EG type polyester polyol, 6 10 parts by weight of polybutylene ether glycol, and 1 part by weight of polypropylene After the diol was mixed, the temperature was raised to 90 QC, and water was removed under vacuum until no bubbles were generated. 2.5 parts by weight of dicyclohexylmethane diisocyanate was added at a reaction temperature of 80 to 90 ° C, and after 30 minutes of reaction, 5 drops of 25% dibutyltin dilaurate were added dropwise, and then reacted until NCO% reached a theoretical value ( After about 3.19%), the temperature was lowered to 50 ° C, 15 and then 10 parts by weight of acetone was added and stirred to reduce the viscosity. Next, 0.04 parts by weight of hydrazine, 0.05 parts by weight of 1,2-ethylenediamine, and 0.7 parts by weight of a diamine sulfonic acid sodium salt [N-(2-aminoethyl)-2-aminoethane sulfonic acid sodium salt, C4H12N2〇3S · Na] is reacted for about 1 hour. After the reaction is completed, 22.5 parts by weight of pure water is slowly added, and after aging for about 20 hours, the acetone is extracted to obtain an aqueous polyisocyanate containing a sulfonate functional group. The acid salt solution (A) had a solid content of about 37.6%. (2) After-stage process··First step: Take 1 part by weight of (A) solution, and slowly add 0.12 part by weight of t-butyl hydroperoxide and 0.07 weight at 45-50 °C. a portion of acetal sodium sulfoxylate, an aqueous solution containing 0.02 parts by weight of 10 1284141 of ferric chloride, wherein the weight of water is 6.8, and the same is added after 18.8 parts by weight of acrylic acid-2-B Based on the purpose of 2-EHA, the rate of addition should be controlled within three hours to prevent particle formation. The second step: followed by the first step and then adding 07.07 parts by weight of α,α,-azobis-isobutyronitrile dissolved in 〇·7 parts by weight of propylene sulfonium as the oily starter, and also added 0.17 parts by weight of sodium sulfoxylate sodium sulfate dissolved in 0.7 parts by weight of the aqueous solution, and the reaction was continued for 2 hours after the completion of the dropwise addition to obtain an aqueous polyisocyanate/acrylic mixed resin containing a sulfonate functional group. The solid mixture 10 (S_C·%), viscosity (viSC0Sity, 25°C), and acidity (PH) value of the newly synthesized mixed resin were measured at a temperature of 1〇5〇C, and the acidity (PH) value is shown in Table 1. In addition, Table 1 also lists the physical properties of the mixed resin after 7 days of baking in a 75 cc oven, and the emulsion stability and hue after two months of standing. <Example 2> The operating conditions and the amounts of use of <Example 1> differ in that the acrylic monomer used in 15 is butyl acrylate. The physical properties, stability and hue of the resulting mixed resin are also detailed in Schedule 1. <Example 3> The operating conditions and usage amounts of <Example 1> differ in that the acrylic monomer used is methyl methacrylate. The physical properties, stability and hue of the resulting blended resin are also detailed in Schedule 1, and the methods for physical property testing are also listed in the notes to Table 1. <Example 4> The operating conditions of <Example 1> differ in that the ratio of the aqueous pU to the acrylic monomer used was 4:1, the physical properties of the obtained mixed resin, and the properties of the 2,804,141 qualitative and hue It is also detailed in Schedule 1. [Comparative Example] Pre-stage process: After removing 100 parts by weight of polybutylene-adipate (PBA-2000) at a temperature of 80 CC, 9 parts by weight of 1,6-hexylene group was added. Diisoisocyanate (1,6-hexamethylene diisocyanate, HDI for short), 6 parts by weight of Iisophorone diisocyanate (IPD), 10 parts by weight of dimethylpropanic acid (abbreviated as dimethylpropanic acid) DMPA), 10 parts by weight of 1-mercapto 10 -2-pyrrolidone (NMP) - reacted. After four hours, the NCO% was 2.65% to about the theoretical value (2.7). %), can start to cool down to 40~50 ° C, and then add 110 parts by weight of acetone for 5 minutes, then add triethylamine (TEA) 11 · 1 part by weight to neutralize, then add pure water 289 The parts are converted into phase by weight, and then 0.7 part by weight of ethylene diamine (EDA) and 0.7 parts by weight of hydrazine are added, and after aging for about 1 hour, the acetone is extracted to obtain a resin. The dispersion (A) was measured to have a solid shape of 32.2%. After-stage process: Step 1: Take 100 parts by weight of (A) solution, and slowly add 20 parts by weight of tributyl hydroperoxide and 0.06 part by weight of furfural hyposulfuric acid at a temperature of 40 to 50 °C. Sodium, an aqueous solution containing 0.017 parts by weight of a gasified iron complex, wherein the weight of water is 5.88, and after the completion of the dropwise addition, 16.1 parts by weight of acrylic acid 2-ethyl ester (abbreviated as 2-ΕΗΑ) is added, and the addition speed is required. Control within 3 hours to prevent particle generation. 12 1284141 Step 2 · Then add 6 parts by weight of α,α'-azobis-isobutyronitrile dissolved in 6 parts by weight of acetone as an oily starter, and also added to 〇· 6 parts by weight of aqueous solution of sodium aldehyde sulfoxylate in 6 parts by weight of the aqueous solution, and the reaction was continued for 2 hours after the completion of the dropwise addition to obtain an aqueous polyisocyanate/acrylic mixed 5 resin of a citrate functional group. [Application and Evaluation of Fabric Coating] In addition to the physical properties of the above resin emulsions, it is a further comparison of the fabric coating effect of one of the uses. The towel of the present invention is prepared by adding the mixed resin of the above-mentioned embodiment and the comparative example, and applying η to the cotton cloth, and applying the paste to the nylon cloth to have a characteristic of moisture permeability, richness, and touch. And it is detailed in Schedule 1. The following two formulations and processes are described separately: Foam beads coated on cotton cloth: 5 gram of mixed resin and 2 g of white paste (R_3 〇), 3.5 g of foaming agent dissolved in 6 g of hot water (RF), 2g (X-042), lg bridging agent (M-3), ig stabilizer (STA), 25g slip (silica 15 S〇1), 4 drops of thickener ( HM-4〇0) mixed. The above formulation was applied to a cotton cloth and baked at 100 ° C for 2 minutes, then flattened, and then baked for 2 minutes. Paste coating on nylon cloth: Impregnate a Nilon-based cloth in an aqueous solution of a water-repellent agent (FC3552), wherein the weight ratio of water-repellent to water is 0.3:100, 20 and then 100. (: 下忸,座?八#7々^ ^, /, Bake 2 knives can pay a water cloth, then the prepared k cloth liquid is applied to the water cloth for the first time, after Bake 2 at 1 : Know 're-feed the second coat, then bake for 2 minutes at c, take the bridging reaction at 15G C for 2 minutes to complete the paste coating. As can be seen from the attached table, the solid content, viscosity, and acidity of the aqueous polyisocyanate/acrylic mixed resin containing the sulfonate functional group in the 13 1284141 Examples 1 to 3> obtained according to the production method of the present invention. The value hardly changed after 7 days of standing, indicating that the stability of the resin emulsion was good. Similarly, it maintained its good stability without delamination and a white transparent hue after being left for two months. However, 5 <Comparative Example> The solid content ratio of the carboxylate-containing polyisocyanate/acrylic hybrid resin is lower than that of Examples 1 to 3, and yellowing occurs after standing for two months. Phenomenon. Incorporating the above-mentioned sulfonate-containing functional aqueous polyisocyanate/acrylic mixture obtained according to the production method of the present invention Resin not only does not cause environmental problems such as the traditional oil 10-resin containing organic solvents, but also the water-based polyisocyanate resin and acrylic compound can reduce the cost. In addition, the synthesis process is carried out by the IPN mechanism. The polymerization of keili, so that the aqueous polyisocyanate resin and the acryl are entangled in a physical winding manner, and do not have the disadvantage that the emulsion will be layered after the conventional direct stirring, and the manufacturing according to the invention The method of Fang 15 uses an aqueous polyisocyanate resin containing a sulfonate functional group as a medium to improve the aqueous polyisocyanate which is mainly composed of a polyisocyanate resin containing a carboxylate functional group. The salt/acrylic hybrid resin will have the disadvantage of yellowing. At the same time, it can be applied to some fabrics with moisture permeability, richness and touch compared with aqueous polyisocyanates containing carboxylate functional groups. It is preferred that the acryl composite 2 〇 resin is the only preferred embodiment of the present invention, and the scope of the present invention cannot be limited thereto, that is, the patent application according to the present invention: The simple equivalent changes and modifications made in the contents of the manual shall remain within the scope of this patent. 14 Ϊ284141 [Simple description of 囷] The distribution of cyanate resin and acryl is in a straight state. : Description of the two polymers that have traditionally been mixed in a water-based polyisotropy mode. Figure 2: illustrates the use of the method of the present invention to synthesize an aqueous polyisocyanate/acrylic hybrid resin. The state of entanglement and entanglement. Table 1: Comparison of physical properties and post-process properties of the mixed resin of the examples and comparative examples of the present invention. 15 1284141 [Description of main components of the drawings] No. 16