i332〇18 九、發明說明： 【發明所屬之技術領域^ 發明領域 本發明係有關於-種具有連續氣孔之聚胺甲酸醋多孔 5質體。 【先前技術】 背景技術 以往，具有微細連續氣孔之聚胺曱酸酯多孔質體，可 藉例如：以作為一次交聯劑之水溶性聚異氰酸酯與作為二 ι〇次交聯劑之聚胺化合物，使胺基甲酸酯乳膠進行反應來製 造(參考專利文獻1)。 【專利文獻1】日本公開公報第2003-48940號 但，由於相對於胺基甲酸酯聚合物的乳膠，只要可以 僅使用聚胺化合物作為交聯劑來製造聚胺曱酸酯多孔質 15體，即可減少所使用之成分數量，故從製造成本的觀點來 看，是非常有用的。 【發明内容】 發明欲解決之課題 本發明之目的，係提供一種僅使用聚胺化合物作為交 20 聯劑’形成具有微細連續氣孔之聚胺甲酸酯多孔質體。 用以解決課題之手段 為達成上述目的，本發明之聚胺曱酸酯係自使胺基曱 酸酯預聚物水分散體與聚胺化合物進行交聯反應獲得之膠 化物中去除水分而獲得，又，前述胺基甲酸酯預聚物水分 5 散體係由多轉、鏈增長劑 進行聚合而麟末端具4_鏈增長劑及異氰酸賴 發明效果 3基者。 本發明之聚胺甲酸g旨客 9夕孔質體， 長劑，並僅以聚胺化合物作為交聯劑 ，並可抑制製 細連續氣孔等各種用途 【實施方式】 由於含有親水性鏈增 ，故可適用於形成微 造成本。 用以實施發明之最佳形態 本發明之聚胺甲酸酯多孔 基甲_合物之胺基曱竣,聚合物 物進行交聯反應而獲得者。 /、♦胺化& ψ ,,仫扣蚀夕-inr ^明中之胺基甲酸酯預 '鏈増長劑、親水性鏈增長劑及異氰 酸醋進行聚合喊得4^有錢劍旨騎。 、鼠 (多元醇 通常使用於製造聚胺甲酸醋:並 子中含有2個以上的絲即可，並無特別限定， 如：聚醚多元醇、聚6旨多元醇、聚碳酸能多元醇、聚内醋 多兀醇、聚稀烴多元醇、丙_多謂、_油系多元醇、 卵好元料，亦可單獨歧合2触上前衫元醇來使 用。從抑制所獲得之聚胺甲酸醋多孔質體劣化的觀點來 看’其中，以使用聚碳酸酿多元醇為佳。又，前述所謂的 劣化，包含光劣化、水劣化等。 聚醚多元醇’係將氧烷化物(氧化乙烯、氧化内烯、氧 化丁烯等）及/或雜環醚（四氫呋喃等）進行聚合或共聚合所 獲得者，具體而言’可舉例如：聚乙二醇、聚丙二醇、聚 1332018 二羥曱基丙酸、2,2-二羥甲基丁酸、2,2-二羥曱基正丁酸、 2,2-二羥曱基戊酸、1,4-丁二醇-2-磺酸等，亦可單獨或混合 2種以上前述親水性鏈增長劑來使用。 親水性鏈增長劑的摻合量，會因所使用之多元醇及後 5 述異氰酸酯的種類而不同，但從可提昇所獲得之聚胺甲酸 酯聚合物的水分散性與後述膠化特性，以及可獲得具有微 細連續氣孔之聚胺曱酸酯多孔質體的觀點來看，前述親水 性鏈增長劑的摻合量，係在構成聚胺曱酸醋的全部反應成 分中，以含有〇.1~4重量％為佳，且以1~4重量％較佳，並以 10 1〜3重量％特佳。即，若親水性鏈增長劑的摻合量小於0.1 重量％，則會有使所獲得之聚胺曱酸酯的水分散性極度降 低之虞。另一方面，若親水性鏈增長劑的摻合量超過4重量 %，則會有破壞所獲得之聚胺甲酸酯水分散體的膠化特性 之虞。 15 異氰酸酯，通常使用於製造聚胺甲酸酯，並且只要在 末端具有2個以上異氰酸酯基者即可，並無特別限定，且可 舉例如：2,4-甲苯二異氰酸酯、2,6-三烯烴二異氰酸酯、4,4-二曱苯二異氰酸酯、3,3’-二氣-4,4’-二甲苯二異氰酸酯、 2,2’-二甲苯二異氰酸酯、2,4’-二曱苯二異氰酸酯、苯二甲 20 基二異氰酸酯、苯撐二異氰酸酯、1，5-萘二異氰酸酯、氫化 二曱苯二異氰酸酯、氫化苯二甲基二異氰酸酯等芳香族聚 異氰酸酯及其氫化物；1,4-環己烷二異氰酸酯、異佛爾酮二 異氰酸酯、冰片烷二異氰酸酯等脂環族聚異氰酸酯；四曱 撐二異氰酸酯、1，6-六甲撐二異氰酸酯等脂肪族聚異氰酸酯 9 等’亦可單獨或混合2種以上前述異氰酸酯來使用。 異氰酸酯的摻合量，並無特別限定，只要所獲得之胺 基甲酸醋預聚物的末端具有異鼠酸醋基即可，亦可使前述 異氰酸酯與前述多元醇、鏈增長劑及親水性鏈增長劑分別 5 所具有之活性氫基定量地反應來進行摻合。 胺基甲酸酯預聚物’可以習知方法製造，並無特別限 定，又可舉例如：在分子内不含活性氫基之有機溶劑存在 下或不存在下，將多元醇、鏈增長劑、親水性鏈增長劑與 異氰酸酯，藉一步發泡法或多段發泡法，且宜在2〇。(^〜150 10 C、並最好是在60~120 C下’反應2~1〇小時之方法等。在 此，各成分的添加順序並無特別限定。另外，反應終點最 好是以黏度監控。 為了降低製造胺基甲酸酯預聚物時的黏度而使用上述 有機溶劑’並可舉例如：丙酮、甲乙明、甲基0比洛烧酮、 15 甲苯、四氫吱喃、二氧化物、N，N，-二甲基曱醯胺等。 從控制所獲得之聚胺基甲酸酯多孔質體的外觀密度的 觀點來看’本發明中的胺基甲酸酯預聚物水分散體係使上 述胺基甲酸酯預聚物分散於水中，並相對於水之胺基甲酸 酯預聚物的摻合比例，以5〜60重量％為佳，且以1〇~50重量 20 %較佳’並以15~40重量％特佳。 胺基甲酸酯預聚物水分散體的製造方法，並無特別限 定，並可舉例如：利用混練機、乳化機、均質機等分散裝 置’混合、分散胺基甲酸酯預聚物與水之方法等。 在此’從提昇胺基甲酸酯預聚物的水分散性的觀點來 10 看’在以陰離子性鏈増長劑作為親水性鏈増長劑時，亦可 預先中和構雜基旨㈣物域水性鏈增長劑的陰離 子吐的陰離子親水基。如此之中和劑，可舉例如：三甲基 基胺一 η丙基胺、三-η-丁基胺等低級烧基胺； 及氨等無機中和劑。又，從可藉後述之去除水分程序而輕 易去除的觀點來看，其中又以使料點低於水之三甲基 胺、三乙基胺為佳。 土 又’前述中和劑的摻合量，並無特別限定，但通常以 摻合與親水性鏈增長劑的陰離子性親水基大略相等量為 佳。 此外’從提昇胺基甲酸δ旨預聚物水分散性的觀點來 看’也可適當地使用界面活性劑^又，可使用的界面活性 劑’可舉例如：高級醇氧化乙稀添加物（月桂醇聚氧化乙婦 驗、聚氧化乙針六細、聚氧化乙烯硬㈣趟、聚氧化 乙,油烯醚等)、高級醇氧化丙烯添加物、高級醇(氧化乙烯 氧化丙烯)添加物、燒基苯盼氧化乙烯添力。物(壬基苯紛聚 氧化乙_、辛基苯盼聚氧化乙_等）、芳基苯紛氧化乙 烯添加物、脂肪酸氧化乙烯添加物、脂肪酸聚乙二醇醋、 月曰肪k醢胺氧化乙稀添加物、長鏈烧基胺氧化乙稀添加 物、多元醇脂肪_氧化乙烯添加物、油脂氧化乙稀添加 物甘油知肪酸酯、聚甘油酯、季戊四醇脂肪酸酯、山梨 糖醇脂肪酸醋（山梨糖醇醋）'山梨糖醇8旨氧化乙稀添加物、 策糖脂肪酸自旨、？元醇㈣基⑽、_麵的脂肪酸酿胺 等非離子界缝性劑；院細硫酸㈣、㈣笨續酸鹽、 1332018 本發明之聚胺甲酸酯多孔質體可以習知方法製造，並 無特別限定，其方法可舉例如：均一混合上述所得之胺基 甲酸酯水分散體與聚胺化合物，再將所獲得之混合物流入 成形模塑内’並在室溫下靜置10小時以上後的狀態下，進 5行交聯反應，再從所獲得之膠化物去除水分之方法等。 另外，亦可在不損害本發明目_範_，在本發明 之聚胺甲酸醋多孔質中含有著色劑、抗菌劑、抗氧化劑、 紫外線吸收劑、光安定劑、消泡劑、增黏劑、15{1調整劑等 添加劑，亦可單獨或混合2種以上前述添加劑來使用。 10 X ’從抑制所獲得之聚胺基甲酸酿多孔質體劣化的觀 點來看’在含有陰離子性鏈增長劑為構成成分以作為親水 性鏈增長劑之胺基甲酸醋預聚物水分散體中添加中和劑 時，亦可添加與陰離子性鏈增長劑的陰離子性親水基反應 所獲得之化合物，再使胺基甲酸醋預聚物進行交聯。如此 15之化合物，轉例如：碳化二亞胺系化合物、十坐琳系化 合物、環氧樹脂系化合物、三聚氰胺系化合物等。又，在 添加有上述化合物的情形下，由於形成陰離子性親水基與 鹽的中和劑會從陰離子性鏈增長劑解離，故可有效率地進 行後述水洗程序。 2〇 纟上述聚胺曱酸@|多孔f體的製造中，由於胺基曱酸 酿預聚物水分散體中的胺基甲酸賴預聚物末端異氛酸酿會 先與存在周園的水反應，因而通常會在將胺基甲酸醋預聚 物刀散於水中後，再於48小時内與聚胺化合物進行反應為 佳。 14 以下，顯示實施例具體6元明本發明，但本發明並不限 定於下述實施例。 (實施例1〜7及比較例1 ~3) 以第1表所示的摻合比例，在3 口圓底燒瓶中加入聚碳 5酸酯二醇〔旭化成株式會社製、商品名：Τ-4671 '數平均 分子量·· 1000〕作為多元醇、乙二醇作為鏈增長劑；2,2_ 二羥曱基丙酸作為親水性鏈增長劑、及U6_六曱撐二異氰酸 酯作為異氰酸酯，並以90 C攪拌3小時，以獲得胺基甲酸醋 預聚物。 10 將上述所獲得之胺基曱酸酯預聚物升溫至80°C，再加 入三乙胺作為中和劑、授拌2分鐘。接著，加入聚氧化乙稀 烷醚型非離子界面活性劑〔旭電化工業製、商品名：（了尹 力卜々TN-100)、HLB : 13.8、濁點：7宂〕並攪拌2分鐘。 接著，將添加有中和劑及界面活性劑之胺基曱酸酯預 15聚物加入蒸餾水中，並以乳化機攪拌5分鐘，以獲得胺基甲 酸酯預聚物水分散體。 在上述獲得之胺基曱酸酯預聚物水分散體，_邊攪拌 並添加含有乙二胺作為聚胺化合物之水溶液，再於室溫 下，以攪拌機攪拌10秒加以混合後，再使該混合物流入具 20有耐水性之成形模型内，在室溫下靜置12小時使其反應。 然後’將所獲得之反應物進行水洗，再以8〇。〇進行乾燥， 以獲得反應生成物。且，各成分的摻合比例係顯示於第丨表。 【第1表】 16 1332018 ms tbte例 277.8 I 3 \〇 8 1797 \η »〇 1047.8 100.0 1 Η 425 2993 s 212 154.9 § KM3.9 100.0 459 3242 s a 1363 o vo 10433 100.0 〇〇 4.66 攸例 l> 300.8 § § 168.7 § 10635 100.0 ci Ό 311.4 3 s 157.1 o 10527 [100.0 C4 325.0 oo a 145.8 〇\ *-H 10683 1100.0 J 〇〇 249 寸 328.0 147.1 § 1075.1 100.0 I 2 m | 338.6 oo s 142.4 卜 对* § 10827 100.0 2 r—4 336.1 00 \6 1413 00 <5 1076.0 ιω,ο 2 S3 3352 S § 141.0 Ώ 938.0 100.0 1 | 2>2^i甲絲酸 I 1,6·六甲律4娜| 三乙胺 寻斯界面活性劑 蒸傲欠 上述胺基甲战fiS預聚物水分散想(重f份） 腦己二水容ίϊϊ(重*份） •θ- Ιι 11 胺基甲 義預 1 成分名 基甲跑指 預聚物 (重*份） ' 17 1332018 依據下述方法，測定外觀密度、拉伸強度及伸長，以 作為反應生成物的物性。 [A.外觀密度] 從上述反應生成物切出尺寸為長50mmx寬50mmx厚 5 度3mm的試驗片，並測定前述試驗片的重量，再依據式：〔外 觀密度(kg/m3)〕=〔試驗片重量(g)〕+〔試驗片體積(mm3)〕 X 1〇6,求出外觀密度(根據JISK 6400)。 [B.拉伸強度] 從上述反應生成物切出尺寸為長60mmx寬1 Ommx厚 10 度2mm的試驗片，並利用自動記錄機〔株式會島津製作所 製、型號：ASG-D〕測定。使試驗片的縱向為拉伸方向來 進行測定，並利用試驗片破壞時的伸長，再依據式：〔拉伸 強度(MPa)〕=(〔斷裂強度(N)〕+〔試驗片截面積(mm2)〕， 求出拉伸強度(根據JISK6301)。 15 [C.伸長] 從上述反應生成物切出尺寸為長6〇mmx寬i〇mmx厚 度2mm的試驗片，並利用自動記錄機〔株式會島津製作所 製、型號：ASG-D〕測定。使試驗片的縱向為拉伸方向， 且以刻度20mm進行測定，並利用試驗片破壞時的伸長，再 20依據式：〔伸長(％)〕=(〔切斷時的刻度長度(mm)〕-〔刻度 距離(111111)〕）+〔刻度距離(111111)〕><1〇〇，求出拉伸強度(根 據JISK 6301) 〇 實施例1〜7及比較例1〜3所獲得之反應生成物的各種物 性係顯示於第2表。 18 1332018 【第2表】 【硌CSJ2 1 ί—^ I s： Γ^Ι s R cn ·*♦ R 1 i I 卜 o CO g i8 & rl *η § i g 寸 s g 窆 2 fN 8 CO 1 1 S | 1 I I I | 19 實施例1~7所獲得之反應生成物，顯示出特別是在作為 °及水性滚輪、OA機器用滾輪、吸水性構件、雕刻構件時的 有用物性。 又，將實施例1〜7及比較例1~3獲得之反應生成物，利 5 用數位顯微鏡〔株式會社Keyence製、型號：VH-6300〕，以 6〇〇倍的倍率觀察。將實施例1的觀察照片顯示於第1圖，並 將比較例1的觀察照片顯示於第2圖，以作為具體例。 如第1圖所示，在實施例1獲得之反應生成物係具有微 細之連續氣孔，且實施例2~7獲得之反應生成物也觀察到與 10 實施例1同樣具有微細連續氣孔。另一方面，如第2圖所示， 比較例1所獲得之反應生成物不具有多孔質構造，且呈薄膜 狀態’而比較例2〜3所獲得之反應生成物也觀察到與比較例 1同樣呈薄膜狀態。 【圖式簡單說明】 15 第1圖係實施例1所獲得之反應生成物的顯微鏡照片 (倍率：600倍）。 第2圖係比較例1所獲得之反應生成物的顯微鏡照片 (倍率：600倍）。 【主要元件符號說明】 無 20I332〇18 IX. Description of the Invention: [Technical Field of the Invention] Field of the Invention The present invention relates to a polyurethane porous plastid having continuous pores. [Prior Art] Conventionally, a porous polyurethane porous body having fine continuous pores can be, for example, a water-soluble polyisocyanate as a primary crosslinking agent and a polyamine compound as a secondary crosslinking agent. The urethane latex is reacted and produced (refer to Patent Document 1). [Patent Document 1] Japanese Laid-Open Patent Publication No. 2003-48940, however, it is possible to produce a polyamine phthalate porous body 15 using only a polyamine compound as a crosslinking agent with respect to a latex of a urethane polymer. It is very useful to reduce the amount of components used, from the viewpoint of manufacturing cost. Disclosure of the Invention Problems to be Solved by the Invention An object of the present invention is to provide a porous polyurethane body having fine continuous pores by using only a polyamine compound as a crosslinking agent. Means for Solving the Problem In order to achieve the above object, the polyamine phthalate ester of the present invention is obtained by removing moisture from a colloid obtained by crosslinking an aqueous dispersion of an amino phthalate prepolymer with a polyamine compound. Further, the urethane prepolymer moisture dispersion system is polymerized by a multi-rotation, chain extender, and the 4-terminal chain extender and the isocyanate-based effect 3 base. The polyglycolic acid of the present invention is a chelating agent, a long-acting agent, and only a polyamine compound as a crosslinking agent, and can suppress various uses such as fine continuous pores. [Embodiment] Since a hydrophilic chain is contained, Therefore, it can be applied to form a micro-cause. BEST MODE FOR CARRYING OUT THE INVENTION The amine oxime of the polyurethane urethane complex of the present invention is obtained by subjecting a polymer to a crosslinking reaction. /, ♦ Amination & ψ , , 仫 蚀 - in in in in in in in in in in in in in in in in in in in in in in in in in in in in in in in in in in in in in in in in in in Purpose ride. Or a rat (polyol is usually used for producing a polyurethane acetal: two or more kinds of filaments are contained in the merging, and are not particularly limited, and are, for example, polyether polyol, poly 6 polyol, polycarbonic polyol, Poly-intracoholic polydecyl alcohol, poly-sparing polyol, C-poly, _oil-based polyol, egg-good material, can also be used separately to contact the former shirt alcohol to use. From the viewpoint of deterioration of the porous urethane plastid, it is preferable to use a polycarbonic acid-based polyol. Further, the above-mentioned deterioration includes photodegradation, water degradation, etc. The polyether polyol is an oxyalkylate ( In particular, those obtained by polymerization or copolymerization of ethylene oxide, oxidized internal olefin, butylene oxide, etc., and/or a heterocyclic ether (tetrahydrofuran, etc.) may, for example, be polyethylene glycol, polypropylene glycol, or poly 1332018. Hydroxymercaptopropionic acid, 2,2-dimethylolbutanoic acid, 2,2-dihydroxyindolyl butyric acid, 2,2-dihydroxyinvaleric acid, 1,4-butanediol-2- A sulfonic acid or the like may be used alone or in combination of two or more kinds of the aforementioned hydrophilic chain extenders. The amount of the hydrophilic chain extender may be used. The type of the polyol and the latter isocyanate are different, but the water dispersibility of the obtained polyurethane polymer and the gelation property described later can be improved, and the polyamine phthalate porous having fine continuous pores can be obtained. From the viewpoint of the plastid, the amount of the hydrophilic chain extender blended is preferably from 1 to 4% by weight, and from 1 to 4% by weight of the total reaction component constituting the polyamine phthalic acid vinegar. % is preferable, and is particularly preferably 10 1 to 3 % by weight. That is, if the blending amount of the hydrophilic chain extender is less than 0.1% by weight, the water dispersibility of the obtained polyamine phthalate is extremely lowered. On the other hand, if the blending amount of the hydrophilic chain extender exceeds 4% by weight, there is a possibility that the gelation property of the obtained polyurethane aqueous dispersion is deteriorated. 15 Isocyanate is usually used for The polyurethane is not particularly limited as long as it has two or more isocyanate groups at the terminal, and examples thereof include 2,4-toluene diisocyanate and 2,6-triene diisocyanate. 4-diphenylene diisocyanate, 3,3'-digas-4,4'-xylene Isocyanate, 2,2'-xylene diisocyanate, 2,4'-diphenylene diisocyanate, phthalic acid diisocyanate, phenylene diisocyanate, 1,5-naphthalene diisocyanate, hydrogenated diphenylene diisocyanate An aromatic polyisocyanate such as hydrogenated dimethyl diisocyanate or a hydrogenated product thereof; an alicyclic polyisocyanate such as 1,4-cyclohexane diisocyanate, isophorone diisocyanate or borneol diisocyanate; The aliphatic polyisocyanate 9 such as isocyanate or 1,6-hexamethylene diisocyanate may be used alone or in combination of two or more kinds of the above isocyanates. The blending amount of the isocyanate is not particularly limited as long as the obtained amino carboxylic acid vinegar is obtained. The terminal of the prepolymer may have an isocitrate group, and the isocyanate may be quantitatively reacted with the active hydrogen group of each of the polyol, the chain extender and the hydrophilic chain extender to be blended. The urethane prepolymer can be produced by a conventional method, and is not particularly limited, and examples thereof include a polyol and a chain extender in the presence or absence of an organic solvent having no active hydrogen group in the molecule. , a hydrophilic chain extender and an isocyanate, by a one-step foaming method or a multi-stage foaming method, and preferably at 2 Torr. (^~150 10 C, and preferably at 60 to 120 C, the reaction is carried out for 2 to 1 hour, etc. Here, the order of addition of each component is not particularly limited. Further, the reaction end point is preferably viscosity. Monitoring. In order to reduce the viscosity when manufacturing the urethane prepolymer, the above organic solvent is used. For example, acetone, methyl bromide, methyl carbitol, 15 toluene, tetrahydrofuran, and dioxide are used. , N, N, dimethyl decylamine, etc. From the viewpoint of controlling the apparent density of the porous polyurethane porous body obtained, the urethane prepolymer water in the present invention The dispersion system disperses the above urethane prepolymer in water and is preferably 5 to 60% by weight, and 1 to 50% by weight, based on the blending ratio of the urethane prepolymer of water. 20% is preferable and is preferably 15 to 40% by weight. The method for producing the aqueous dispersion of the urethane prepolymer is not particularly limited, and examples thereof include a kneading machine, an emulsifying machine, a homogenizer, and the like. Dispersing device 'mixing, dispersing urethane prepolymer with water, etc. Here's pre-polymerization from elevated urethane From the viewpoint of water dispersibility of the substance, when the anionic chain length agent is used as the hydrophilic chain length agent, the anionic hydrophilic group of the anion spit of the (4) aqueous chain extender of the domain may be neutralized in advance. The neutralizing agent may, for example, be a lower alkylamine such as trimethylamine-n-propylamine or tri-n-butylamine; or an inorganic neutralizing agent such as ammonia. Further, it may be removed from the latter. In view of the easy removal by the moisture program, it is preferable that the material is lower than the trimethylamine or triethylamine in water. The amount of the aforementioned neutralizing agent is not particularly limited, but Usually, it is preferably equal to the anionic hydrophilic group of the hydrophilic chain extender. It is also preferable to use a surfactant from the viewpoint of improving the water dispersibility of the prepolymer of the urethane. Further, as the surfactant which can be used, for example, a higher alcohol oxyethylene oxide addition (lauric alcohol polyoxyethylene oxide test, polyoxyethylene hexafluoride, polyethylene oxide hard (tetra) ruthenium, polyoxyethylene ethoxylate, oleyl ether) Etc.), higher alcohol propylene oxide additive, higher alcohol (oxidized B) Addition of propylene oxide), benzoyl benzoate, ethylene oxide, etc. (mercaptobenzene condensed ethylene oxide _, octyl benzene, polyethylene oxide _, etc.), aryl benzene ethylene oxide additive, fatty acid ethylene oxide addition , fatty acid polyethylene glycol vinegar, ruthenium amide, ethylene oxide addition, long-chain alkylamine oxide ethylene addition, polyol fat _ ethylene oxide additive, fat oxidized ethylene addition, glycerin Acid ester, polyglycerol ester, pentaerythritol fatty acid ester, sorbitol fatty acid vinegar (sorbitol vinegar) 'sorbitol 8 ethoxylate added, sugar fatty acid self-purpose, ?-ol (4) base (10), _ surface A non-ionic intercalating agent such as a fatty acid-derived amine; a fine sulfuric acid (4), (4) a suspending acid salt, 1332018. The porous polyurethane porous body of the present invention can be produced by a known method, and is not particularly limited, and the method can be exemplified. For example, if the aqueous urethane dispersion obtained above is uniformly mixed with the polyamine compound, and the obtained mixture is poured into the molding, and left at room temperature for 10 hours or more, 5 rows are obtained. Cross-linking reaction, and then obtained from A method of removal of moisture. In addition, the polyurethane, the antibacterial agent, the antioxidant, the ultraviolet absorber, the light stabilizer, the antifoaming agent, and the tackifier may be contained in the porous polyurethane of the present invention without impairing the scope of the present invention. An additive such as 15{1 adjuster may be used alone or in combination of two or more of the above additives. 10 X 'from the viewpoint of suppressing the deterioration of the polyaminocarboxylic acid-grown porous body obtained by the inhibition of the aqueous dispersion of the amino carboxylic acid acetal prepolymer having the anionic chain extender as a constituent component as a hydrophilic chain extender When a neutralizing agent is added, a compound obtained by reacting an anionic hydrophilic group with an anionic chain extender may be added, and the amino carboxylic acid vinegar prepolymer may be crosslinked. The compound of the above 15 is, for example, a carbodiimide compound, a decidene compound, an epoxy resin compound or a melamine compound. Further, in the case where the above compound is added, since the neutralizing agent which forms the anionic hydrophilic group and the salt dissociates from the anionic chain extender, the water washing procedure described later can be efficiently performed. 2〇纟In the manufacture of the above polyamine niobic acid@|porous f body, the amino acid lysate prepolymer end oleic acid in the aqueous dispersion of the amino phthalic acid emulsifiable prepolymer will firstly exist with the presence of Zhouyuan The water reacts, and it is usually preferred to carry out the reaction with the polyamine compound within 48 hours after dispersing the urethane methacrylate prepolymer knife in water. 14 Hereinafter, the present invention will be specifically described with reference to the following examples, but the present invention is not limited to the following examples. (Examples 1 to 7 and Comparative Examples 1 to 3) Polycarbonate 5 ester diol (manufactured by Asahi Kasei Co., Ltd., trade name: Τ-) was added to a 3-neck round bottom flask at the blending ratio shown in Table 1 4671 'number average molecular weight · 1000】 as a polyol, ethylene glycol as a chain extender; 2,2-dihydromercaptopropionic acid as a hydrophilic chain extender, and U6_hexamethylene diisocyanate as an isocyanate, and The mixture was stirred at 90 C for 3 hours to obtain a urethane hydroxyacetate prepolymer. 10 The amino phthalate prepolymer obtained above was heated to 80 ° C, and triethylamine was added as a neutralizing agent for 2 minutes. Next, a polyethylene oxide ether type nonionic surfactant (manufactured by Asahi Kasei Co., Ltd., trade name: (Yin Li Bu TN-100), HLB: 13.8, cloud point: 7 宂) was added and stirred for 2 minutes. Next, an amino phthalate prepolymer added with a neutralizing agent and a surfactant was added to distilled water, and stirred by an emulsifier for 5 minutes to obtain an aqueous dispersion of the urethane prepolymer. The aqueous dispersion of the amino phthalate prepolymer obtained above is stirred and added with an aqueous solution containing ethylenediamine as a polyamine compound, and then stirred at room temperature for 10 seconds in a stirrer, and then mixed. The mixture was poured into a molding mold having water resistance of 20, and allowed to stand at room temperature for 12 hours to cause a reaction. The resulting reaction was then washed with water and again at 8 Torr. The crucible is dried to obtain a reaction product. Moreover, the blending ratio of each component is shown in the third table. [Table 1] 16 1332018 ms tbte Example 277.8 I 3 \〇8 1797 \η »〇1047.8 100.0 1 Η 425 2993 s 212 154.9 § KM3.9 100.0 459 3242 sa 1363 o vo 10433 100.0 〇〇4.66 Example l> 300.8 § § 168.7 § 10635 100.0 ci Ό 311.4 3 s 157.1 o 10527 [100.0 C4 325.0 oo a 145.8 〇\ *-H 10683 1100.0 J 〇〇249 inch 328.0 147.1 § 1075.1 100.0 I 2 m | 338.6 oo s 142.4 § 10827 100.0 2 r—4 336.1 00 \6 1413 00 <5 1076.0 ιω, ο 2 S3 3352 S § 141.0 Ώ 938.0 100.0 1 | 2>2^i 甲丝酸 I 1,6·六甲律4娜 | Ethylamine stalk interface active agent steaming proud of the above-mentioned amine-based warfare fiS prepolymer water dispersion thought (heavy f parts) brain two water capacity ϊϊ (heavy * parts) • θ- Ιι 11 Amino-based pre- 1 ingredient Prescription base (weight * part) ' 17 1332018 The apparent density, tensile strength and elongation were measured as the physical properties of the reaction product according to the following method. [A. Appearance Density] A test piece having a length of 50 mm x a width of 50 mm and a thickness of 5 mm 3 mm was cut out from the above reaction product, and the weight of the test piece was measured, and according to the formula: [appearance density (kg/m3)] = [ Test piece weight (g)] + [test piece volume (mm3)] X 1〇6, and the apparent density (according to JIS K 6400) was determined. [B. Tensile strength] A test piece having a length of 60 mm x a width of 1 Omm x a thickness of 10 degrees 2 mm was cut out from the reaction product, and was measured by an automatic recorder (manufactured by Shimadzu Corporation, model: ASG-D). The longitudinal direction of the test piece is measured in the direction of stretching, and the elongation at the time of failure of the test piece is used, and according to the formula: [tensile strength (MPa)] = ([rupture strength (N)] + [cross-sectional area of the test piece ( Mm2)], the tensile strength (according to JIS K6301) was determined. 15 [C. Elongation] A test piece having a size of 6 mm mm×width i〇mmx and a thickness of 2 mm was cut out from the above reaction product, and an automatic recording machine was used. It is measured by the model manufactured by Shimadzu Corporation, model: ASG-D. The longitudinal direction of the test piece is the direction of stretching, and the measurement is performed at a scale of 20 mm, and the elongation at the time of failure of the test piece is used. Then, according to the formula: [elongation (%)] = ([scale length (mm) at the time of cutting] - [scale distance (111111)]) + [scale distance (111111)] ><1〇〇, tensile strength (according to JIS K 6301) The various physical properties of the reaction products obtained in Examples 1 to 7 and Comparative Examples 1 to 3 are shown in Table 2. 18 1332018 [Table 2] [硌CSJ2 1 ί—^ I s: Γ^Ι s R cn · *♦ R 1 i I 卜 o CO g i8 & rl *η § ig sg 窆2 fN 8 CO 1 1 S | 1 III | 19 Examples 1~7 The reaction product obtained shows the useful properties especially when used as a water roller, an OA machine roller, a water absorbing member, and an engraving member. Further, the reactions obtained in Examples 1 to 7 and Comparative Examples 1 to 3 were obtained. The product was observed with a digital microscope (manufactured by Keyence Co., Ltd., model: VH-6300) at a magnification of 6 〇〇. The observation photograph of Example 1 is shown in Fig. 1, and the observation of Comparative Example 1 was observed. The photograph is shown in Fig. 2 as a specific example. As shown in Fig. 1, the reaction product obtained in Example 1 has fine continuous pores, and the reaction products obtained in Examples 2 to 7 were also observed. 10 Example 1 has fine continuous pores. On the other hand, as shown in Fig. 2, the reaction product obtained in Comparative Example 1 does not have a porous structure and is in a film state, and Comparative Examples 2 to 3 are obtained. The reaction product was observed to have a film state as in Comparative Example 1. [Simplified description of the drawing] 15 Fig. 1 is a micrograph of a reaction product obtained in Example 1 (magnification: 600 times). Fig. 2 is a comparison The reaction obtained in Example 1 Micrograph of the product (magnification: 600 times) [Main component symbol description] None 20