200842155 九、發明說明 【發明所屬之技術領域】 本發明係關於多孔體及其製造方法。 【先前技術】 作爲製造多孔體的方法有例如：將樹脂與二氧化碳或 氨氣等揮發型發泡劑混練，藉由揮發氣體使混練物發泡的 方法；與將分解型發泡劑與樹脂混練，藉由分解型發泡劑 之分解所產生的氣體使混練物發泡的方法。作爲分解型發 泡劑有偶氮二甲醯胺、二亞硝基四亞甲四胺及肼撐二甲醯 胺。 利用此等之發泡的方法之情況，可形成獨立氣泡型態 的發泡體。其中曾被提出的方法爲：藉由對發泡體施加機 械性變形破壞獨立氣泡以得到形成有連續氣泡的多孔體（ 參照專利文獻1 )。然而，此方法中，要破壞全部獨立氣 泡甚難，故欲得到連續氣泡的比例高的多孔體有困難。 因此，習知的方法爲：使熱塑性樹脂與較其熔點高的 水溶性粉末進行熔融混練以得到成形物，然後，自成形物 萃取水溶性粉末以得到多孔體的方法（以下亦稱爲「萃取 法」）（參照專利文獻2 )。 另一方面，作爲附加有各種機能的樹脂發泡體或樹脂 多孔體，曾被提出者爲例如：塡充有多孔質粒子之複合發 泡體（專利文獻3 )、含有無機吸濕劑之樹脂多孔體（專 利文獻4 )。 -5- 200842155 專利文獻1 :日本專利特公昭62- 1 9294號公報 專利文獻2 :日本專利特開2 0 0 2 - 3 2 2 3 1 0號公報 專利文獻3 :日本專利特開2002- 1 829號公報 專利文獻4:日本專利特開2002-191929號公報 【發明內容】 (發明所欲解決之課題） 然而，於上述的萃取法中，若使用多量水溶性粉末， 於用以得到成形物之成形步驟中混練物的流動性會降低， 會有成形性變差、或外觀變差之傾向。因此，藉由提高水 溶性粉末之塡充率（混合比例）欲得到氣孔率充分高的多 孔體事實上有困難。 又，由於係藉由自實質上未形成氣泡的實心成形品進 行萃取而形成氣泡，故須自平滑的表面朝向內部一邊漸進 地將露出的密實表面溶解一邊萃取出粉末。因而，萃取時 間長，也是問題。 本發明爲鑑於此等情形而提出者，其第一目的爲提供 氣孔率高的多孔體及其製造方法。再者，本發明之第二目 的爲提供於短時間得到多孔體之製造方法。本發明之第三 目的爲提供嶄新的機能性多孔體及其製造方法。 (解決課題之手段） 本發明之多孔體之製造方法，具備：將含有高分子物 質、氣孔形成劑及分解型發泡劑之組成物的成形物，加熱 -6 - 200842155 至使該高分子物質熔融之溫度，藉由分解型發泡劑的分解 而使該成形物發泡之步驟；及藉由使氣孔形成劑溶解於溶 劑中而從發泡之成形物中萃取該氣孔形成劑，於成形物內 形成連續氣泡之步驟。 依據上述本發明之製造方法，藉由組合發泡及萃取， 依序進行此等，可於短時間得到具有高氣孔率的多孔體。 上述氣孔形成劑以含有具有比該高分子物質的熔點 Ma高的熔點Mb之第1成分爲佳。藉此，將含有高分子物 質及氣孔形成劑的組成物，於含有未熔融的氣孔形成劑之 狀態下使高分子物質熔融而進行混練，可容易地得到含有 粉末狀或粒子狀的氣孔形成劑之成形用混練物。其結果可 使其更有效率地形成連續氣泡。 氣孔形成劑之第1成分以具有100〜3 5 0°C的熔點Mb 之多元醇爲佳。多元醇以季戊四醇爲佳。 於氣孔形成劑含有上述第1成分的情況，上述組成物 以含有高分子物質1 00重量份、氣孔形成劑的第1成分 50〜400重量份、及分解型發泡劑1〜50重量份爲佳。 氣孔形成劑以再含有具有比該高分子物質的熔點Ma 低的熔點Me之第2成分爲佳。此第2成分以聚環氧乙烷 爲佳。 於氣孔形成劑含有上述第1及第2成分的情況，上述 組成物以含有高分子物質1 0 〇重量份、氣孔形成劑的第1 成分40〜45 0重量份、氣孔形成劑的第2成分20〜450重量 份、及分解型發泡劑1〜5 0重量份爲佳。 200842155 本發明之製造方法，以再具備：以Ma以上，且低於 M b及分分解型發泡劑的分解溫度M d中較低的溫度之溫度 ’熔融混練該組成物之步驟；及使經熔融混練的該組成物 成形後得到該組成物之步驟爲佳。此情況下，以使該組成 物利用擠壓成形法、壓延成形法、加壓成形法或射出成形 法成形後得到該成形物爲佳。 高分子物質以熱塑性樹脂或熱塑性彈性體爲佳。高分 子物質亦可爲烯烴系樹脂或聚酯系樹脂。高分子物質亦可 爲乙烯-乙酸乙烯酯共聚物。 上述溶劑以水或水性溶劑爲佳。 上述組成物亦可再含有機能性塡充材。藉此，可對多 孔體賦予利用連續氣泡之各種機能。 上述機能性塡充材以機能性高分子粒子爲佳。此機能 性高分子粒子以分子鑄型爲佳。此機能性高分子粒子以離 子交換樹脂爲佳。 構成機能性高分子粒子之高分子化合物與構成多孔體 之高分子物質的溶解度參數的差以1以內爲佳。 機能性高分子粒子以於表面上具有官能基爲佳。此官 能基以具有與該高分子物質的反應性爲佳。 本發明之多孔體含有形成連續氣泡之高分子物質，且 具有50〜90容積％的氣孔率。 本發明之多孔體亦可再含上述有機能性塡充材。此情 況下，機能性塡充材以露出於該連續氣泡的壁面爲佳。上 述多孔體由於氣孔率高，故若使機能性塡充材露出於連續 -8 - 200842155 氣泡的壁面時，可特別有效地發揮機能性塡充材的f幾能。 機能性高分子粒子以藉由其表面的官能基與_胃# + 物質的反應而與該高分子物質鍵結爲佳。 本發明之多孔體，可含有形成連續氣泡之高分子物M 、與爲分子鑄型之機能性筒分子粒子。又，本發明之多孔 體亦可含有形成連續氣泡之高分子物質與離子交換樹脂之 機能性高分子粒子。 本發明之過濾材具備上述本發明之多孔體。本發明之 離子交換體母材具備上述本發明之多孔體。 (發明之效果） 依據本發明之製造方法，可於短時間得到氣孔率高的 多孔體。又，依據本發明之製造方法，由於在發泡後除去 氣孔形成劑，故可形成連續氣泡，可於短的萃取時間容易 地製造透水性良好的多孔體。於製造方法高氣孔率的多孔 體之情況亦可降低氣孔形成劑的使用量，氣孔形成劑亦可 容易地除去。因此’生產效率佳，且可得到更牢固之多孔 體。 本發明之多孔體由於氣孔率高故有良好的通氣性，尤 其適合於過濾用過濾材料、離子交換構造材、平板型管柱 等。 又’依據本發明之製造方法，可容易地得到於使用機 能性塡充材時’可於維持良好的透水性等之下，一邊賦予 利用連續氣泡之各種機能的多孔體。 200842155 【實施方式】 以下就本發明之較佳實施形態做說明。惟本發明並非 限定於下述之實施形態° 本實施形態之多孔體之製造方法具備·將含有局分子 物質、氣孔形成劑及分解型發泡劑之組成物熔融混練的步 驟；使熔融混練之組成物（混練物）成形得到成形物的步 驟；將成形物加熱至使高分子物質熔融之溫度，藉由分解 型發泡劑的分解而使成形物發泡之步驟；及藉由使氣孔形 成劑溶解於溶劑中而從發泡之該成形物中萃取該氣孔形成 劑，於該成形物內形成連續氣泡之萃取步驟。 作爲上述高分子物質較佳者可使用熱塑性樹脂、熱塑 性彈性體或此等之混合物。高分子物質之熔點 Ma以 100〜3 00 °c爲佳。 熱塑性樹脂以適於擠壓成形、壓延成形、或射出成形 者爲佳。因此，熱塑性樹脂以熔點爲100〜3 00 °c者爲佳。 作爲較佳的熱塑性樹脂之具體例可舉出：聚乙烯、聚丙烯 、乙烯-乙酸乙烯酯共聚物及乙烯-乙酸乙烯酯共聚物皂化 物之類的烯烴系樹脂、聚對苯二甲酸乙二酯及聚對苯二甲 酸丁二酯之類的聚酯系樹脂、乙烯-甲基丙烯酸共聚物、 聚苯乙烯、AS樹脂、ABS樹脂、聚醯胺6、聚醯胺6 · 6 、聚碳酸酯、聚縮醛、及聚乙烯醇。此等熱塑性樹脂可1 種單獨使用’或組合2種以上使用。此等之中尤以烯烴系 樹脂及聚酯系樹脂爲佳。 -10- 200842155 熱塑性彈性體爲賦予橡膠狀彈性之軟性區段（ segment )及用以形成三維網目的節結之由硬性區段所構 成的高分子材料，於常溫下呈現橡膠彈性’於高溫下爲可 塑性。因此，熱塑性彈性體可藉由擠壓成形、壓延成形、 或射出成形而容易地成形。 作爲熱塑性彈性體的具體例可舉出：硬性區段爲聚苯 乙烯軟性區段爲聚丁二烯、聚異戊二烯、或此等之加氫物 的聚苯乙烯系彈性體，硬性區段爲聚乙烯或聚丙烯軟性區 段爲丁基橡膠或EPDM (乙烯-丙烯-二烯共聚物）的聚烯 烴系彈性體，硬性區段爲聚醯胺軟性區段爲聚酯或聚醚的 聚醯胺系彈性體、硬性區段爲聚酯軟性區段爲聚醚的聚酯 系彈性體，及硬性區段爲具有胺基甲酸酯鍵結之胺基甲酸 酯系嵌段軟性區段爲聚酯或聚醚的聚胺基甲酸酯系彈性體 。此等可1種單獨使用，或組合2種以上作爲高分子物質 使用。 作爲氣孔形成劑可用可溶於萃取溶劑於藉由溶劑萃取 時可形成氣泡的特性之材料。因此，具有於使高分子物質 與氣孔形成劑一起進行熔融混練時，可得到粉末狀或粒子 狀的氣孔形成劑分散於高分子物質中所成之混練物的特性 的粉末狀或粒子狀之材料爲可較佳地適用作爲氣孔形成劑 〇 氣孔形成劑含有比高分子物質的熔點Ma高的熔點Mb 的有機化合物之第1成分（以下有時亦稱爲「第一氣孔形 成劑」）°第一氣孔形成劑於含有高分子物質的組成物之 -11 - 200842155 成形溫度中可維持固體狀態。因此，藉由用第一氣孔形成 劑，於萃取後可容易地有效率地形成連續氣泡。 多孔體之製造方法，亦可包含：將多孔體用組成物之 成形物（係於熔點Ma之高分子物質外再含有具有較Ma 高的熔點Mb的第一氣孔形成劑及具有較Ma高的熱分解 溫度Md的分解型發泡劑所成者）加熱至Md以上使其發 泡的步驟；與於不會溶解高分子物質而可溶解第一氣孔形 成劑的溶劑中進行第一氣孔形成劑之萃取的步驟。 第一氣孔形成劑之熔點Mb以40〜35 (TC爲佳。熔點 Mb的下限以100°C爲佳，以1501：爲更佳。熔點Mb的上 限以30(TC爲更佳。例如，高分子物質的熔點Ma爲100°C 〜3 0 0 °C的情況，第一氣孔形成劑的熔點Mb以在Ma以上 且超過100°C並爲3 5 0°C以下爲佳，以150°C〜3 00°C爲更佳 〇 作爲第一氣孔形成劑，以使用碳數2〜5的程度之多元 醇及尿素爲佳。作爲多元醇的具體例，可舉出季戊四醇、 L-赤蘚醇、D_赤蘚醇、中（meso)-赤蘚醇及四甲基乙二 醇。此等材料中尤以季戊四醇爲佳。由於季戊四醇爲親水 性，故作爲萃取步驟中所用的溶劑可選擇水或水性溶劑。 又，季戊四醇之熔點依其純度而變化，通常熔點於1 80 °C 〜2 6 0 °C之熔點，故容易與各種高分子物質組合使用。而且 ，季戊四醇由於自熔融狀態至固化的速度快，故成形物的 冷卻時間可縮短，有益於提高生產性。 第一氣孔形成劑可1種單獨使用，亦可組合2種以上 -12- 200842155 使用。於組合2種以上的情況，藉由組合粒徑不同的材料 、於成形溫度下之剛性不同的材料，可更容易地改變氣孔 之形成狀態。 氣孔形成劑以再含有具有比該高分子物質的熔點Ma 低的熔點Me之第2成分（以下有時亦稱爲「第二氣孔形 成劑」）爲佳。第二氣孔形成劑的熔點Me以50〜200 °C爲 佳。作爲第二氣孔形成劑可舉出例如聚環氧乙烷及聚乙二 醇。其中，基於熔融黏度等之考量尤以聚環氧乙烷（以分 子量100萬〜800萬尤佳）爲佳。 第一氣孔形成劑及視需要而使用之第二氣孔形成劑於 用以得到成形用之混練物的熔融混練中，須均一地分散於 高分子物質中是重要的。因此，可適當地使用分散劑。作 爲此分散劑可舉出例如：硬脂酸之類的高級脂肪酸、硬脂 醇之類的高級脂肪醇、石蠟、及硬脂醯胺、棕櫚醯胺、亞 甲雙硬脂醯胺、以及乙烯雙硬脂醯胺之類的高級脂肪酸醯 胺。 分解型發泡劑爲藉由加熱至既定的分解溫度Md以上 時分解而產生氣體而使成形物發泡的成分。作爲分解型發 泡劑的具體例可舉出：偶氮二甲醯胺（ADCA，分解溫度 195〜2 10°C )、偶氮雙異丁腈（AIBN，分解溫度98〜l〇2°C )、偶氮二羧酸鋇（分解溫度240〜25 0 °C )、二亞硝基五 亞甲四胺（DPT，分解溫度 200〜205 °C) 、p，p，-氧雙苯磺 醯基醯肼（OBSH，分解溫度157〜162°C )、及對苯磺醯基 醯肼（TSH，分解溫度103〜111°C)。 -13- 200842155 於選定分解型發泡劑之時，須考慮上述之含 物質及氣孔形成劑的混練物之成形溫度與分解型 分解溫度的關係。分解型發泡劑之分解溫度下之 熔融黏度若太高，因發泡劑之分解所產生的氣體 到混練物的機械強度壓抑，致使混練物難以發泡 若混練物的熔融黏度若太低，則產生的氣體會容 練物而飛散，故亦難以發泡。由此觀點考量，例 子物質爲烯烴系樹脂的情況，作爲分解型發泡劑 氮二甲醯胺（ADCA )及二亞硝基五亞甲四胺（ 特佳。 又，爲得到更良好的發泡狀態，組成物中亦 聯劑及/或交聯助劑。作爲交聯劑可使用例如： 基過氧化物、2,5-二甲基-2，5-二（第三丁基過氧 及2,5-二甲基-2，5-二（第三丁基過氧）己炔-3等 氧化物。上述交聯助劑亦可組合2種以上使用。 量，相對於高分子物質100重量份，以0〜5重量 以2重量份以下爲更佳。爲使交聯劑的效果更容 交聯劑的量以0.2重量份以上爲佳，以0.4重量 更佳。交聯劑若過少，發泡狀態之增進效果有減 ，若過多，發泡度之提高有變得困難之傾向。 作爲交聯助劑可舉出例如：三羥甲丙烷三甲 酯、三羥甲丙烷三丙烯酸酯、二甲基丙烯酸乙二 異三聚氰酸三烯丙酯。交聯助劑亦可組合二種以 交聯助劑的量，相對於高分子物質1 〇〇重量份， 有高分子 發泡劑之 混練物的 壓力會受 。反之， 易突破混 如於高分 ，尤以偶 DPT )爲 可含有交 雙異苯丙 )己烷、 之有機過 交聯劑的 份爲佳， 易發揮， 份以上爲 小之傾向 基丙烯酸 醇酯、及 上使用。 以0〜2重 -14- 200842155 量份爲佳，以1 · 5重量份以下爲更佳。交聯助劑的量即使 超過2重量份，發泡性的改善效果無法明顯地再提高。爲 使交聯助劑的效果容易發揮，以〇 · 1重量份以上爲佳。 用以得到成形物之上述組成物，亦可再含有機能性塡 充材。機能性塡充材爲對多孔體賦予特定的機能的有機或 無機塡充材。作爲機能性塡充材可用可賦予多孔體例如， 硏磨機能、熱傳導機能、熱傳導防止機能、導電性機能、 光線吸收機能、分子篩機能、離子交換機能或分子鑄型機 能的材料。 作爲無機的機能性塡充材有：二氧化砂、氧化錦及氧 化硒等之硏磨劑，碳酸鈣及氧化矽等之熱傳導或防止熱傳 導之物質，金、銀、銅等之熱傳導性或導電性的金屬粒子 、二氧化鈦等之顏料粒子。 作爲有機機能性塡充材有以高分子化合物形成的機能 性高分子粒子。機能性高分子粒子可爲離子交換樹脂粒子 、分子鑄型、硏磨劑、或有機顏料。又，機能性高分子粒 子亦可爲聚苯乙烯多孔體粒子。聚苯乙烯多孔體粒子爲例 如作爲凝膠色層分析的管柱塡充材所使用的粒子，亦可含 有用二乙烯苯形成的交聯構造。機能性高分子粒子亦可爲 聚乙烯粉等之改質用局分子微粒子。 機能性塡充材，可爲無機與有機的複合材料。作爲用 於機能性塡充材的複合材料之例爲在聚苯乙烯粒子上鍍金 的粒子。 於機能性塡充材有熔點或分解點時，此等溫度，以較 -15- 200842155 前述之Ma、Mb及Me之中的最低溫度高爲佳，以較Ma、 Mb及Me之中的最高溫度高爲更佳。機能性塡充材之熔點 或分解點以較前述之多孔體製造步驟中機能性塡充材所負 荷的溫度高爲佳。 爲使機能性高分子粒子均一地分散於用以形成多孔體 的高分子物質中，構成機能性高分子粒子之高分子化合物 與構成多孔體之高分子物質之間，溶解度參數的差以1以 內爲佳，以〇 · 5以內爲更佳。 溶解度參數（solubility parameter; SP値）爲於聚合 物手冊（Polymer Handbook) IV-341 頁數〜IV-3 6 8 頁（與 H. -G. ELIAS 協同下，J. BRANDRUP/E. H. IMMERGUT 編；INTERSCIENCE PUBLISHERS 發行）中所示之「 SOLUBILITY PARAMETER VALUE」（H. Burrell 著）所 說明之値。又，於「溶劑手冊」（淺原照三、戶倉仁一郎 、大河原信、熊野谿從、妹尾學編著，講談社科學1976 年第1版發行，1 993年第13刷發行）第91〜93頁中亦有 就同樣的溶解度參數做說明。溶解度參數可用small的方 法或藉由實驗求出。 small的方法中，於SP値爲6，分子中或反復單位之 原子及基的全部F値之總和爲Σ F (此處，F値爲molar-attraction constant (分 子引力 常數） ，單位爲（cal · cm3 )1/2/mol，25°C))，分子量（或反復單位之分子量）爲 Μ，分子之密度爲P時，SP値（5可由下式求出。 -16- 200842155 [數學式1] 又，主要取代基之F値如下述： 甲基（H3C-) : 214 甲撐（methylene)基（-CH2-; 2 級碳）：133 亞甲（methylene)基（H2C=(雙鍵））：190 甲炔基（methyne )基（HC ; 3級碳）：28 次甲基（methyne)基（-HC=(雙鍵））：111 四級碳：9 3 酯基（-COO·) ： 3 1 0 二級羥基（-〇 Η ) : 3 0 0 苯基：735 伸苯(phenylene)基：658 依據上式，乙烯-乙酸乙烯酯共聚物（乙烯： 烯=9 : 1 (莫耳比）、密度0.93 )的5爲8.5 (反 C22H4202的分子量：3 3 8.5 6 )，苯乙烯-二乙烯苯共 苯乙烯：二乙烯苯=1 : 1 (莫耳比）、密度 0·90 ) 7.2 (反復單位C18H19的分子量：234.3 2 )，聚（ 丙烯酸乙二醇酯）聚合物（密度1 . 1 )的6爲7 · 7 ( 位C1GH1404的分子量：198.21 )，聚（二甲基丙烯 酯）（密度1.1 )的5爲8.3 (反復單位CmH1605 S : 228.24 )。 於機能性高分子粒子爲分子鑄型的情況，可使 型載持於形成多孔體之高分子物質上。如此之多孔 乙酸乙 復單位 聚物（ 的δ爲 二甲基 反復單 酸甘油 的分子 分子鑄 體，於 -17- 200842155 用分子鑄型的微量有機化合物之捕捉及捕捉後的微量有機 化合物之回收時，操作方便。由於在多孔體內形成連續氣 泡，故只要對載持有分子鑄型的多孔體進行透水即可採取 水中所含有的微量特定有機化合物。因而，亦可用多孔體 作爲過濾材的一種。爲用於此目的，多孔體以具有高透水 性者爲佳。 作爲用作爲分子鑄型使用之機能性高分子粒子可舉出 習知之作爲分子嵌入聚合物（imprint polymer)的高分子 粒子。嵌入聚合物在特定的條件下可選擇性地吸附標的物 質，並於特定的條件下釋出所吸附的標的物質。 此等嵌入聚合物，爲藉由使由標的物質或其類似化合 物所構成的鑄型分子與機能性單體進行氫鍵結般的非共價 鍵結的相互作用而自行會合後，在交聯劑存在下進行聚合 ，然後將鑄型分子除去的方法所得到之聚合物。於利用塊 狀聚合的情況，對得到之聚合物適當地粉碎而可使用。於 利用懸浮聚合的情況，可得到粒子狀的嵌入聚合物，此情 況，並非一定得粉碎。爲得到粒子狀的嵌入聚合物，較佳 者爲種子聚合的方法，尤其是周知的二段膨潤聚合法或多 段膨潤聚合法。 作爲上述標的物質並無特別限制，以較低分子量者爲 佳。由於 PCB (過氯聯苯（perchlorobiphenyl))、雙酉分 A、溴化雙酚A、及戴奧辛等爲環境荷爾蒙，故受到矚目 〇 於雙酚A爲標的物質的情況，不僅其本身，亦可使用 -18- 200842155 對第二丁基苯酌作爲鑄型分子。又，於溴化雙酚A爲標的 物質的情況’不僅其本身，亦可使用2,6-雙-(三氟甲基 )-本甲酸作爲纟尋型分子使用。 ί乍胃用以得到嵌入聚合物所使用之機能性單體，可用 具有聚合性（尤其是自由基聚合性）之化合物。機能性單 體具有於聚合端基（site )以外之與標的物質互相作用的 端基（鹼性基、酸性基等官能基）。作爲機能性單體之具 體例可舉出：乙烯基吡啶、乙烯基咪唑、丙烯酸、甲基丙 烯酸、順式丁烯二酸、順式丁烯二酸酐、衣康酸、丙烯酸 2-經乙酯、甲基丙烯酸2_羥乙酯、丙烯醯胺、甲基丙烯醯 胺' 丙嫌腈、甲基丙烯腈、甲基丙烯酸縮水甘油酯及乙酸 乙烯。 作爲用以得到嵌入聚合物所用的交聯劑，以具有2個 以上雙鍵的自由基聚合性化合物爲佳。作爲具體例有··乙 二醇二甲基丙烯酸酯、乙二醇二丙烯酸酯、甘油二甲基丙 烯酸酯、甘油二丙烯酸酯、四亞甲二醇二甲基丙烯酸酯、 季戊四醇四甲基丙烯酸酯及二乙烯苯。與具有2個以上雙 鍵的自由基聚合性化合物一起，可適當地倂用具有丨個自 由基聚合性化合物（以下稱爲「1官能單體」）。作爲此 1官能單體有：甲基丙烯酸甲酯、甲基丙烯酸乙酯、甲基 丙烯酸丁酯、甲基丙烯酸辛酯、及甲基丙烯酸2 -乙己酯等 之甲基丙烯酸烷酯、丙烯酸甲酯、丙烯酸乙酯、丙烯酸丁 酯、丙烯酸辛酯、及丙烯酸2 -乙己酯等之丙烯酸烷酯、以 及苯乙烯。 -19- 200842155 上述二段膨潤聚合法或多段膨潤聚合法包含 二甲酸二丁酯等膨潤助劑使聚苯乙烯等之可膨潤 粒子膨潤；使膨潤之粒子和鑄型分子、機能性單 劑（視需要可倂用1官能單體）及聚合起始劑一 溶劑中，使粒子再膨潤後進行昇溫，使機能性粒 劑一起聚合。聚合起始劑以預先溶解於膨潤助劑 中爲佳。 上述膨潤助劑之較佳者爲周知的以苯二甲酸 聚合物的可塑劑。作爲膨潤助劑亦可使用1官能 聯劑、非水溶性有機溶劑。 作爲上述之溶劑以水或水性溶劑爲佳。作爲 有水與水溶性有機溶劑之混合溶劑。作爲水溶性 ，可舉出例如：甲醇、乙醇及異丙醇等醇、丙酮 及環己酮等之酮、以及二異丙醚及二丁醚等之醚 使粒子與其他成分妥適地懸浮，以在溶劑中添加 等高分子分散劑及陰離子界面活性劑等界面活性 又，藉由使上述聚合物粒子與交聯劑等和苯、甲 苯、環己烷及己烷等非水溶性有機溶劑倂用，可 性的粒子狀嵌入聚合物。嵌入聚合物若爲多孔性 出較多的標的物質之吸附端基，故爲較佳。作爲 劑與界面活性劑可使用後述者。 作爲多段膨潤聚合法，可使聚合物粒子依序 潤助劑膨潤、以非水溶性有機溶劑膨潤、及以交 ，然後再進行聚合。此情況，可於聚合前的任意 :藉由苯 的聚合物 體、交聯 起懸浮於 子與交聯 或交聯劑 爲代表之 單體、交 水性溶劑 有機溶劑 、甲乙酮 。又，爲 聚乙烯醇 劑爲佳。 苯、二甲 得到多孔 ，則可露 聚合起始 進行以膨 聯劑膨潤 時間點使 -20- 200842155 粒子懸浮於溶劑（水或水性溶劑）中。 如上述般之利用於分子鑄型的製造之任一聚合法中， 於聚合的最後階段或其終了後，再添加有1個官能基的單 體使其聚合，可對分子鑄型進行表面改質。作爲此種有1 個官能基的單體，可使用與上述機能性單體同樣者。藉此 ’可得到在表面有官能基之嵌入聚合物粒子。使用此官能 基可使得吸附或鍵結至嵌入聚合物的載持體更爲容易。例 如’作爲有1個官能基的單體係使用有羧基的1官能單體 所得到之嵌入聚合物，將其與作爲用以形成多孔體的高分 子物質之乙烯-乙酸乙烯酯共聚物組合的情況，藉由嵌入 聚合物的羧基與乙烯-乙酸乙烯酯共聚物的乙醯基之酯交 換反應，可使嵌入聚合物鍵結於多孔體。藉此，可使嵌入 聚合物載持於多孔體。 分子鑄型、離子交換樹脂等機能性塡充材（機能性高 分子粒子），爲使其充分發揮其機能，以露出於多孔體之 連續氣泡的壁面爲佳。因此，構成機能性塡充材的高分子 化合物與構成多孔體的高分子物質之溶解度參數的差以i 以內爲佳，以0.5以內爲更佳。藉此，可使機能性塡充材 均一地分散而可確保機能性塡充材容易地露出於多孔體表 面。或者，亦可使溶解度參數的差作成此等範圍外（亦即 ，使溶解度參數的差大於0.5或1)而使機能性高分子粒 子與高分子物質難以相混。此情況，在多孔體壁面藉由吸 附或化學鍵結等之相互作用而阻止相連結，於使用較少量 的機能性高分子粒子下可發揮較大的效果。因此，以對機 -21 - 200842155 能性高分子粒子表面’以可和構成多孔體的高分子物質相 互作用之官能基進行表面改質爲佳。基於此觀點等，機能 性高分子粒子以在其表面具有和構成多孔體的高分子物質 有反應性的官能基爲佳。作爲此官能基例如有竣基。 於作爲機能性塡充材係用機能性高分子粒子之分子鑄 型的情況，可用發泡劑及氣孔形成劑之任一者，亦可用兩 者。於未用發泡劑時，亦可用交聯劑及交聯助劑。 機能性高分子粒子的大小可爲任意，其最大粒徑以 0.1〜1 000 // m爲佳。又，機能性塡充材的量以相對於高分 子物質100重量份爲0.1〜300重量份爲佳，以0.5〜200重 量份爲更佳。 用以得到多孔體的組成物之較佳調配比如下述。於下 述之各調配比中尤以括弧內之數値範圍爲更佳。又，於下 述之任一組成中亦可追加用以改善混練作業性的分散劑乃 不言而喻者。 高分子物質 100重量份 第一氣孔形成劑 50〜400重量份（100〜350重量份） 分解型發泡劑 1〜50重量份（3〜20重量份） 分散劑 〇〜3重量份（0.1〜1重量份） 交聯劑 〇〜5重量份（0.2〜2重量份） 交聯助劑 〇〜2重量份（0〜1.5重量份） 又，於用第二氣孔形成劑的情況，以下述之調配比爲 佳。 高分子物質 1〇〇重量份 -22- 200842155 第一氣孔形成劑 40〜450重量份（80〜3 00重量份） 第二氣孔形成劑 20〜45 0重量份（40〜3 00重量份） 分解型發泡劑 1〜50重量份（3〜20重量份） 分散劑 〇〜3重量份（0.1〜1重量份） 交聯劑 〇〜5重量份（0.2〜2重量份） 交聯助劑 〇〜2重量份（0〜1.5重量份） 於用機能性塡充材的情況，以下述之調配比爲佳。 高分子物質 1〇〇重量份 第一氣孔形成劑 50〜400重量份 分解型發泡劑 1〜50重量份（100〜3 5 0重量份） 機能性塡充材 〇·1〜300重量份（0.5〜200重量份） 又，此情況，亦可用下述之調配比。 高分子物質 1〇〇重量份 第一氣孔形成劑 50〜400重量份（100〜3 5 0重量份） 分解型發泡劑 1〜50重量份（3〜20重量份） 分散劑 〇〜3重量份（0.1〜1重量份） 交聯劑 〇〜5重量份（0.2〜2重量份） 交聯助劑 〇〜2重量份（0〜1.5重量份） 機能性塡充材〇·1〜3 00重量份（0.5〜200重量份） 再者，於用第二氣孔形成劑的情況，以下述之調配比 爲佳。 高分子物質 100重量份 氣孔形成劑之第1成分 40〜4 5 0重量份（80〜3 00重 量份） -23- 200842155 氣孔形成劑之第2成分 20〜450重量份（40〜300重 量份） 分解型發泡劑 1〜50重量份（3〜20重量份） 機能性塡充材 〇·1〜300重量份（0.5〜200重量份） 又，此情況，亦可用下述之調配比。 高分子物質 1〇〇重量份 第一氣孔形成劑 40〜450重量份（80〜3 00重量份） 第二氣孔形成劑 20〜45 0重量份（40〜3 00重量份） 分解型發泡劑 1〜50重量份（3〜20重量份） 分散劑 〇〜3重量份（0· 1〜1重量份） 交聯劑 〇〜5重量份（0.2〜2重量份） 交聯助劑 〇〜2重量份（0〜1 .5重量份） 機能性塡充材 〇· 1〜3 00重量份（0.5〜200重量份） 氣孔形成劑若過少，會有氣孔率降低之傾向。氣孔形 成劑若過多，氣孔率會變得過大，致機械強度與成形性有 降低之傾向。又，第二氣孔形成劑由於在熔融混練時負擔 作爲熔融之改質劑的作用，故第一氣孔形成劑可含有較第 二氣孔形成劑爲多。發泡劑若過少，則實質上無法發泡， 而過多則會造成外觀不良等。 於組成物及使用其所得到之成形物中，第一氣孔形成 劑及第二氣孔形成劑的合計量，相對於成形物全體，以 4 0〜90容積％爲佳，以50〜85容積％爲更佳。此合計量若未 滿4 0容積％，則萃取時間有增長的傾向，若超過8 5容積 %，則得到之多孔體的機械強度與成形性有降低之傾向。 -24- 200842155 組成物亦可含有界面活性劑。藉此，於用水或水性溶 劑萃取氣孔形成劑時可更有效率地萃取。作爲界面活性劑 可爲陰離子界面活性劑、陽離子界面活性劑及非離子界面 活性劑之任一者。作爲陰離子界面活性劑可使用例如：十 一丨兀本細酸鈉之類的焼基苯磺酸鹽、於院基直接附加 SOJa基之院基磺酸鹽、於萘附加s〇3Na基之四氫萘 磺酸鹽、及油酸鈉等之高級脂肪酸鹽。作爲陽離子界面活 性劑有：三烷基苄基銨鹽、及四烷基銨鹽等。作爲非離子 界面活性劑有：聚環氧乙烷烷基醚、聚環氧乙烷烷基苯基 醚、聚環氧乙烷烷基胺、聚環氧乙烷烷基胺脂肪酸酯、烷 基二乙醇胺、羥烷基單乙醇胺、及烷基二乙醇醯胺等 等。界面活性劑的量，相對於高分子物質1 〇〇重量份，以 0〜5重量份爲佳’以〇·5〜3重量份爲更佳。 用以得到多孔體之組成物，於上述成分之外，爲了提 高熔融混練之效率等目的，在不脫離本發明之精神的範圍 內可視需要添加氧化防止劑、金屬劣化防止劑、紫外線吸 收劑、防黏著劑、及顏料等。 於混練步驟中，係一邊使高分子物質熔融之下對含有 高分子物質、氣孔形成劑及分解型發泡劑之組成物進行熔 融混練。熔融混練可用通常對熱塑性樹脂、熱塑性彈性體 之熔融混練所用的方法進行。具體而言，可用混練輥、韓 歇爾混合機、單軸擠壓機或雙軸擠壓機進行熔融混練。混 練後的混練物，必要時可剪切成顆粒狀。 於用第一氣孔形成劑的情況，較佳者爲，在高分子物 -25- 200842155 質的熔點Ma以上，且低於第一氣孔形成劑的熔點Mb及 分解型發泡劑的分解溫度Md中較低的溫度之溫度下，對 組成物進行熔融混練。藉此，可容易地得到粉末狀或粒子 狀之第一氣孔形成劑均一地分散之混練物。 於成形步驟中，對藉由熔融混練得到之混練物進行賦 形成爲成形物。換言之，係將混練物成形得到成形物。成 形步驟係與混練步驟同時或於其後進行。混練物可成形爲 片狀、薄膜狀、矩形狀、圓筒狀、圓柱狀、及角柱狀等任 意之形狀。成形方法可依所要的成形物之形狀而決定。片 狀之成形物可藉由加壓成形法、壓延成形法、或擠壓成形 法得到。圓筒形、圓柱形、及角柱形之成形物可藉由擠壓 成形法得到。其他任意三維形狀之成形物可藉由射出成形 法得到。三維形狀之成形物可先使混練物成形爲片狀後， 藉由真空成形法、壓空成形法等賦形爲三維形狀而得到。 發泡步驟中，對由混練物得到之成形物（實心成形物 )加熱使其發泡。發泡步驟係藉由使成形物昇溫至混練於 成形物中之分解型發泡劑的分解溫度而進行。昇溫，例如 可於高溫槽中進行。昇溫時，成形物會軟化致會黏著到底 材之情形。尤其於片狀成形物的情況特別容易黏著到底材 。因此，較佳者爲，使成形物載置於氟樹脂片等之具有脫 模性的片材上使其發泡。又，於三維形狀的成形物之情況 ，以使成形物載置於不會變形的適當之治具上爲佳。 於萃取步驟中，用可溶劑氣孔形成劑之溶劑自經發泡 的成形物萃取出氣孔形成劑。上述溶劑只要是實質上不會 -26- 200842155 溶解高分子物質而會溶解氣孔形成劑之單獨溶劑或混合溶 劑皆可，並無特別限制，可依高分子物質及氣孔形成劑的 種類而適當地選擇。惟基於對環境的影響等之考量以水或 水性溶劑（水性媒體）爲佳。 作爲水性溶劑，可使用水與水溶性有機溶劑之混合溶 劑。作爲水溶性有機溶劑可舉出例如：甲醇、乙醇及異丙 醇等之醇、丙酮、甲乙酮及環己酮等之酮、以及二異丙醚 及二丁醚等之醚。水溶性有機溶劑的比例以在溶劑全體中 爲5 0質量％以下爲佳。 萃取可藉由使發泡步驟後之成形物浸漬於容納於槽中 之液溫爲常溫〜6 0 °C的水或水溶性溶劑中的方法進行。此 時，使溶劑例如用螺桿等攪拌，於高分子物質爲彈性體材 料般有伸縮性的材料之情況，可使成形物反復通過2輥等 進行擠壓加工，可縮短萃取時間。 萃取時間依成形物的厚度、發泡倍率等而改變，通常 係選擇於10〜2 00小時之間。萃取後，使附著於成形物之 溶劑乾燥，可得到形成有連續氣泡的多孔體。 本實施形態之方法中’藉由適當地調整高分子物質、 氣孔形成劑、及分解型發泡劑等之種類及其量、與製造條 件，可得到各種孔徑、各種氣孔率的多孔體。尤其，依據 本實施形態可於短時間容易地得到具有高氣孔率的多孔體 〇 於發泡步驟中，成形物會發泡。藉由發泡，可得到比 發泡前膨脹的成形物。例如’於將高分子物質爲4 0容積％ -27- 200842155 、氣孔形成劑的合計量爲60容積％的組成物成形得到體積 爲3 mL的成形物之情況，若不經過發泡步驟，僅藉由萃取 而形成多孔體，則會萃取出6 0容積％ ( 1 · 8 mL )的氣孔形 成劑，得到藉由其餘之40容積％ ( 1 .2mL )的高分子物質 所形成之表觀體積爲3 mL的多孔體（氣孔率60容積 。相對於此，於使與上述同樣的組成的3 mL之組成物藉由 發泡步驟膨脹爲表觀體積4mL之情況，可得到於萃取後藉 由1.2mL的高分子物質形成的表觀體積爲4mL之多孔體 (氣孔率70容積％ )。亦即，藉由經過發泡步驟，使用與 未經發泡步驟的情況中用以得到表觀體積爲3 mL的多孔體 之組成物爲同樣量的高分子物質，可得到表觀體積爲4mL 的多孔體。 由上述事實可得知：本發明中，（一）藉由加入發泡 步驟，可得到以往的方法（未含發泡步驟）中依成形性的 觀點於成形上有困難之高氣孔率的多孔體。（二）若減少 萃取量，可更廉價地製造與以往的方法同樣氣孔率的多孔 體。（三）於萃取實心的成形物時，係自平滑的表面漸進 地往內部邊溶解下邊萃取，故萃取時間長；相對於此’於 將發泡體萃取出的情況，由於係使氣泡往內部氣泡傳達而 邊溶解下邊萃取，故萃取時間較短’是其優點。 依據本實施形態的方法，可容易地製作5 〇〜90容積％ 的氣孔率之多孔體，而且，甚至亦可得到80〜90容積°/。之 以往所無的高氣孔率之多孔體。又，藉由萃取形成之氣泡 爲連續氣泡，故可得到高氣孔率且形成連續氣泡的多孔體 -28- 200842155 。由於形成連續氣泡，故可得到透水性優異的多孔體。 藉由本實施形態之方法得到的多孔體爲連續氣泡型者 。此多孔體，由於透氣性及透水性優異，故可較佳地適用 於各種過濾材、離子交換體母材等。又，由於含水性亦優 異，此多孔體亦可用於化妝用粉撲材、印泥材、插花等之 水分補給材等。再者，此多孔體亦可較佳地適用於隔音材 、包溫材、衝擊緩衝材、防震材及緩衝材等。 圓柱狀之多孔體可應用於例如作爲有離子交換能之平 板型管柱。依據本發明可於短時間製作高開孔率之平板型 管柱。又，例如將圓柱狀多孔體的一端出入花盆的土中， 另一端插入放至於花盆側的水層中之水中，水可藉由毛細 管現象移動經多孔體而可供給至花盆。亦即，可使用多孔 體於供水用途。 圓柱狀的多孔體，可藉由具備下述步驟的方法製作， 其爲例如：將上述組成物之圓柱狀的成形物配置於具有較 該成形物之直徑大的內徑的管狀容器內的步驟、藉由對管 狀容器內的成形物加熱使其發泡的步驟、自發泡之成形物 萃取氣孔形成劑的步驟。亦可藉由具有··在上述發泡步驟 後將發泡成形物自管狀容器取出的步驟、自發泡成形物萃 取氣孔形成劑的步驟、將萃取後之發泡成形物收容於管狀 容器內的步驟之方法來得到圓柱狀多孔體。作爲管狀容器 可用例如，玻璃管、塑膠管、鋼管等。 [實施例] -29- 200842155 (實施例1 ) 將作爲高分子物質之乙烯-乙酸乙烯酯共聚物（三井-杜邦聚合化學（股）製，商品名：艾巴弗列克斯P 1 007， 熔點94°C ) 100重量份、作爲第一氣孔形成劑之季戊四醇 (廣榮化學工業（股）製，商品名：片塔利特，熔點2 5 4 °C ) 225重量份、作爲第二氣孔形成劑之聚環氧乙烷（住 友精化（股）製，商品名：PEO-18Z，熔點65°C ) 225重 量份、作爲發泡劑之偶氮二甲醯胺（大塚化學（股）製， 商品名：優尼佛姆AZ，分解溫度199 °C ) 9重量份、以及 界面活性劑（花王（股）製，商品名：艾雷克特羅斯特利 巴-TS-5 ) 1重量份及交聯劑（日本油脂（股）製，商品名 :巴枯密爾）0.8重量份用輥進行混練（混練溫度：1 5 (TC )。將混練物用加壓成形機（衝壓力5 0噸）於1 5 (TC加熱 5分鐘後，將其冷卻，得到250mmx250mmx厚度3mm的片 狀成形物。然後，將該成形物置放於高溫槽中之氟樹脂片 上，藉由在2 3 0 °C加熱5分鐘使成形物發泡。 使發泡過之成形物浸漬於水槽中4 0 °C的水中，於表1 之實施例1的萃取時間欄位所示之萃取時間之間，邊以攪 拌機攪拌水下邊萃取出氣孔形成劑。萃取後，使成形物於 40 °C乾燥爐中乾燥24小時，得到形成有連續氣泡的多孔 體0 (實施例2 ) 除了將發泡劑的量改爲4 · 5重量份之外，係以與實施 -30- 200842155 例1同樣的方法得到形成有連續氣泡的多孔體。 (實施例3 ) 除了將第一氣孔形成劑的量改爲1 00重量份、將第二 氣孔形成劑的量改爲1 〇 〇重量份之外，係以與實施例1同 樣的方法得到形成有連續氣泡的多孔體。 (實施例4 ) 除了將發泡劑的量改爲4 · 5重量份之外，係以與實施 例3同樣的方法得到形成有連續氣泡的多孔體。 (實施例5 ) 除了將成形物的厚度改爲1 〇mm之外，係以與實施例 1同樣的方法得到形成有連續氣泡的多孔體。 (實施例6 ) 除了將發泡劑的量改爲4.5重量份之外，係以與實施 例5同樣的方法得到形成有連續氣泡的多孔體。 (比較例1 ) 將作爲高分子物質之乙烯-乙酸乙烯酯共聚物（三井-杜邦聚合化學（股）製，商品名：艾巴弗列克斯P 1 〇 〇 7 ) 1 00重量份、作爲第一氣孔形成劑之季戊四醇（廣榮化學 工業（股）製，商品名：片塔利特）2 2 5重量份、作爲第 -31 - 200842155 二氣孔形成劑之聚環氧乙烷（住友精化（股）製，商品名 :PEO-18Z ) 225重量份、以及界面活性劑（花王（股） 製’商品名：艾雷克特羅斯特利巴_TS-5 ) i重量份及交聯 劑（日本油脂（股）製，商品名：巴枯密爾）〇. 8重量份 用輥進行混練（混練溫度：1 5 〇。(：）。將混練物用加壓成 形機（衝壓力5 0噸）於1 5 〇 〇C加熱5分鐘後，將其冷卻， 得到250mmx250mmx厚度3mm的成形物。 然後’使發泡過之成形物浸漬於水槽中40 °C的水中， 於表1所示之萃取時間之間，邊以攪拌機攪拌水下邊萃取 出氣孔形成劑。萃取後，使成形物於4CTC乾燥爐中乾燥 2 4小時，得到多孔體。 (比較例2 ) 除了將第一氣孔形成劑的量改爲1 〇 〇重量份、將第二 氣孔形成劑的量改爲1 〇 〇重量份之外，係以與比較例1同 樣的方法得到多孔體。 (比較例3 ) 除了將成形物的厚度改爲1 〇mm之外，係以與比較例 1同樣的方法得到多孔體。 實施例及比較例中得到的多孔體之氣孔率及透水性之 測定結果示於表1。氣孔率及透水性之測定係對萃取前及 # Φ既定時間後的成形物以下述步驟進行。 -32- 200842155 (1 )氣孔率（容積％ ) 用東京科學（股）製空氣比較式比重計1 0 0 〇型，測 定在真空中的多孔體之容積VI，VI及由多孔體之長、寬 、高尺寸所算出的容積V，藉由下式求出氣孔率。 多孔體之氣孔率=(1-(乂1/¥))\1〇〇[容積％] (2 )透水性 圖1爲透水性測定裝置之示意圖。使多孔體1夾在東 洋濾紙（股）製過濾用過濾材固定器（filter holder)( 內徑35mm) 2與有同樣內徑35mm的容器3之間，用夾鉗 4夾住。使容器3的連接口 5連接到減壓泵，將容器內的 空氣依箭頭A的方向吸引，使容器內減壓至lOcmHg。於 維持減壓之下供給5 OmL的純水至過濾用濾材固定器2， 使該純水通過多孔體1往容器3內移動。測定自開始供給 純水至於濾材固定器2內的純水不見爲止的時間（秒）， 以其作爲透水性的指標。 -33- 200842155 [表i] 發泡步驟 厚度 (mm) 萃取前 萃取] 後 氣孔率 mm%] 萃取時間 [小時] 5 10 20 40 90 實施例1 有 3 29 氣孔率[容積％] 62 83 88 88 89 透水性[秒] - • • 4 3 實施例2 有 3 20 氣孔率[容積％] 58 80 85 85 85 透水性[秒] • 5 5 實施例3 有 3 38 氣孔率[容積％] 63 75 80 81 82 實施例4 有 3 30 氣孔率[容積％] 57 67 73 78 79 實施例5 有 10 23 氣孔率[容積％] 32 41 57 82 87 實施例6 有 10 10 氣孔率[容積％] 20 30 47 73 83 比較例1 ^Γι I Γ. 1111: J \ \\ 3 5 氣孔率[容積％] 25 43 70 76 80 透水性[秒] 議 麵 220 70 比較例2 Μ j\ \\ 3 4 氣孔率[容積％] 18 30 45 60 66 比較例3 Μ j\ \\ 10 5 氣孔率[容積％] 12 19 33 50 73 圖2爲表示實施例1、實施例2及比較例1的氣孔率 與萃取時間之關係的曲線圖。由此等結果可知：於經過發 泡步驟製作之實施例1及實施例2的多孔體，於萃取時間 爲約1 5小時的階段，可萃取達到氣孔率至飽和程度，且 其氣孔率達到8 5容積％以上。另一方面，於未經發泡步驟 得到之比較例1的多孔體，至萃取終了約須60〜80小時。 再者，比較例1之氣孔率爲約80容積％的程度，與實施例 1、2之8 5容積％比較爲較低之水平。 又，經發泡步驟所製作之實施例1、2的多孔體之透 水時間短，此等多孔體顯示出非常良好的透水性。另一方 面，未經過發泡步驟所製作之比較例1的多孔體之透水時 間長，其透水性與實施例1、2比較爲較差。 -34- 200842155 圖3爲爲表示實施例3、實施例4及比較例2的氣孔 率與萃取時間之關係的曲線圖。由此等結果可知··於經過 發泡步驟製作之實施例3及實施例4的多孔體，於萃取時 間爲約2 0小時的階段’可萃取達到氣孔率至飽和程度， 且其氣孔率達到80容積％以上。另一方面，於未經發泡步 驟得到之比較例2的多孔體，即使萃取達9 0小時，氣孔 率也僅達到6 5容積％的程度。 圖4爲表示實施例5、實施例6及比較例3的萃取時 間與多孔體的氣孔率之關係的曲線圖。由此等結果可知： 於經過發泡步驟製作之實施例5及實施例6的多孔體，於 萃取時間爲約40小時的階段，可萃取達到氣孔率至飽和 程度，且其氣孔率達到8 0容積％左右。另一方面，於未經 發泡步驟得到之比較例3的多孔體，至萃取終了須9〇小 時以上。 以下述之做法製作參考例1〜4的機能性高分子粒子， 其係作爲以雙酚A作爲標的物質之分子鑄型。 參考例1 :機能性高分子粒子（用高分子化合物之分 子鑄型）之製造（聚合方法：使用聚苯乙烯粒子之種子聚 合） 於平均粒徑1 // m之聚苯乙烯粒子6.9g、膨潤助劑（ 苯二甲酸二丁酯）4.5g、界面活性劑十二烷硫酸鈉〇.7g及 水4 0 g的混合物中，添加二甲基丙烯酸乙二醇酯/4 _乙烯基 吡啶/對第二丁基苯酚/ (莫耳比4 0 / 8 /1 )的混合物6 3.9 g、 -35- 200842155 聚合起始劑（2,2’-偶氣雙-2,4 - 一·甲基戊膳）3.2g、聚乙嫌 醇2 5 · 9 g、十二烷硫酸鈉2 · 2 g、甲苯4 7 · 0 g、水3 2 0 g之經 均一分散者，在25 °C下攪拌3 60分鐘，使聚苯乙烯粒子膨 潤，然後，昇溫至50°C進行240分鐘聚合。經過240分鐘 後，添加用以對粒子用甲基丙烯酸基進行表面改質之甲基 丙烯酸2.4g，繼續進行聚合600分鐘。其後，將聚合物以 過濾分離，將反應物以水、甲醇、四氫呋喃洗淨，除去對 第三丁基苯酚。得到的機能性高分子粒子（分子鑄型）之 平均粒徑爲5 // m。又，此分子鑄型的溶解度係以前式計 算的結果，爲9.9。 參考例2 :機能性高分子粒子（苯乙烯-二乙烯苯共聚 合物粒子）之製造 除了用苯乙烯/二乙烯苯/(莫耳比1 /1 )的混合物 48.6g取代二甲基丙烯酸乙二醇酯/4-乙烯基吡啶/對第三丁 基苯酚的混合物63.9g之外，係以與參考例1同樣地進行 聚合。於聚合經過240分鐘後未進行甲基丙烯酸之添加。 此外，係以與參考例丨同樣的做法製造苯乙烯/二乙烯苯 共聚物粒子。得到之共聚物粒子之平均粒徑爲4.5 // m。又 ’共聚物粒子（分子鑄型）的溶解度參數藉由前式計算之 結果爲7.2。 參考例3 :機能性高分子粒子（二甲基丙烯酸乙二醇 酯）之製造 -36- 200842155 除了用二甲基丙烯酸乙二醇酯55.lg取代二甲基丙烯 酸乙二醇酯/4-乙烯基吡啶/對第三丁基苯酚的混合物63.9g 之外，係以與參考例1同樣地進行聚合。於聚合經過240 分鐘後未進行甲基丙烯酸之添加。此外，係以與參考例1 同樣的做法製造二甲基丙烯酸乙二醇酯聚合物粒子。得到 之聚合物粒子之平均粒徑爲5/zm。又，聚合物粒子（分 子鑄型）的溶解度參數藉由前式計算之結果爲7.7。 參考例4 :機能性高分子粒子（二甲基丙烯酸甘油酯 聚合物粒子）之製造 除了用二甲基丙烯酸甘油酯5 5 · 6 g取代二甲基丙烯酸 乙二醇酯/4-乙烯基吡啶/對第三丁基苯酚的混合物63.9 g 之外，係以與參考例1同樣地進行聚合。於聚合經過2 4 0 分鐘後未進行甲基丙烯酸之添加。此外，係以與參考例1 同樣的做法製造二甲基丙烯酸甘油酯聚合物粒子（分子鑄 型）。得到之聚合物粒子之平均粒徑爲4.5 // m。又，聚合 物粒子的溶解度參數藉由前式計算之結果爲8.3。 (實施例7 ) 將作爲高分子物質之乙烯-乙酸乙烯酯共聚物（三井-杜邦聚合化學（股）製，商品名：艾巴弗列克斯P 1 〇〇7， 密度：〇.9 3g/ml，溶解度參數：8.5 ) 100重量份、作爲第 一氣孔形成劑之季戊四醇（廣榮化學工業（股）製，商品 名：片塔利特）225重量份、作爲第二氣孔形成劑之聚環 -37- 200842155 氧乙烷（住友精化（股）製，商品名：PEO-18Z ) 225重 量份、作爲發泡劑之偶氮二甲醯胺（大塚化學（股）製’ 商品名：優尼佛姆AZ ) 4.5重量份、以及界面活性劑（花 王（股）製，商品名：艾雷克特羅斯特利巴-TS-5 ) 1重量 份及交聯劑（日本油脂（股）製，商品名：巴枯密爾） 〇. 8重量份、及上述參考例1中得到之分子鑄型5重量份 用輥進行混練（混練溫度：1 5 〇 °C )。將混練物用加壓成 形機（衝壓力5 0噸）於1 5 0它加熱5分鐘後，將其冷卻， 得到250mmx250mmx厚度3mm的片狀成形物。然後，將 該成形物置放於高溫槽中之氟樹脂片上，藉由在2 3 0 °C加 熱5分鐘使成形物發泡。 使該成形物浸漬於水槽中40 °C的水中，於90小時之 間，邊以攪拌機攪拌水下邊萃取出氣孔形成劑。萃取後， 使成形物於40 °C乾燥爐中乾燥24小時，得到形成有連續 氣泡的多孔體。 (實施例8 ) 除了分子鑄型的量改爲2重量份之外，係以與實施例 7同樣的方法得到多孔體。 (實施例9 ) 除了分子鑄型的量改爲1重量份之外，係以與實施例 7同樣的方法得到多孔體。 -38- 200842155 (實施例1 〇) 除了分子鑄型的量改爲〇重量份之外，係以與實施例 7同樣的方法得到多孔體。 使用實施例7〜1 0的多孔體，以下述步驟作成雙酚a 的吸附等溫線。吸附等溫線係用弗洛因德立希之吸附等溫 式（JIS Z 8 8 3 0 )作成。 準備妥在水中溶解〇.〇 13 g/L的濃度之雙酚A所成的 水溶液，用其作爲吸附試料。對分別得自實施例7〜1 〇之 各多孔體（吸附材），於2重量％到0 · 〇 〇 4重量％的範圍中 以8〜9點不同濃度加入吸附試料lOOmL，施予5分鐘超音 波振動後，進行20小時攪拌。其後，測定雙酚A的多孔 體所吸附的量。吸附量係由吸附試料中的雙酚A之殘餘_ 度求出。殘餘濃度係藉由下述液體層析進行分析，依據g 另外調整之標準樣品的面積比而求出。由得到之吸附羹g 弗洛因德立希之吸附等溫式（JIS Z 8 8 3 0 )求出。其結$ 如表1所示。 (液體層析條件） 管柱：Shimpak VP-ODS (島津製作所（股）， 4.6mm (內徑）xl50mm) 流速：0.8mL/分鐘200842155 IX. Description of the Invention [Technical Field of the Invention] The present invention relates to a porous body and a method for producing the same. [Prior Art] As a method for producing a porous body, for example, a method in which a resin is kneaded with a volatile foaming agent such as carbon dioxide or ammonia gas, and a kneaded material is foamed by a volatile gas; and a decomposable foaming agent is kneaded with a resin. A method of foaming a kneaded material by a gas generated by decomposition of a decomposing foaming agent. As the decomposable foaming agent, there are azo dimethyl hydrazine, dinitroso tetramethylenetetramine, and dimethyl hydrazine. In the case of such a foaming method, a foam of a closed cell type can be formed. Among them, a method has been proposed in which a closed cell is broken by mechanical deformation of a foam to obtain a porous body in which continuous cells are formed (refer to Patent Document 1). However, in this method, it is difficult to destroy all of the independent bubbles, and it is difficult to obtain a porous body having a high proportion of continuous bubbles. Therefore, a conventional method is a method in which a thermoplastic resin is melt-kneaded with a water-soluble powder having a higher melting point to obtain a molded product, and then a water-soluble powder is extracted from the molded product to obtain a porous body (hereinafter also referred to as "extraction". Method) (refer to Patent Document 2). On the other hand, as a resin foam or a resin porous body to which various functions have been added, for example, a composite foam filled with porous particles (Patent Document 3) and a resin containing an inorganic moisture absorbent have been proposed. Porous body (Patent Document 4). -5-200842155 Patent Document 1: Japanese Patent Publication No. Sho 62-119294 Patent Document 2: Japanese Patent Laid-Open No. 2 0 0 2 - 3 2 2 3 1 0 Patent Document 3: Japanese Patent Laid-Open 2002- 1 In the above extraction method, if a large amount of water-soluble powder is used, it is used to obtain a molded product. In the molding step, the fluidity of the kneaded material is lowered, and the formability is deteriorated or the appearance tends to be deteriorated. Therefore, it is actually difficult to obtain a porous body having a sufficiently high porosity by increasing the charge ratio (mixing ratio) of the water-soluble powder. Further, since the bubbles are formed by extraction from a solid molded article in which bubbles are not substantially formed, it is necessary to gradually extract the powder from the smooth surface toward the inside while gradually extracting the exposed dense surface. Therefore, the extraction time is long and is also a problem. The present invention has been made in view of such circumstances, and a first object thereof is to provide a porous body having a high porosity and a method for producing the same. Further, a second object of the present invention is to provide a method for producing a porous body in a short period of time. A third object of the present invention is to provide a novel functional porous body and a method of producing the same. (Means for Solving the Problem) The method for producing a porous body according to the present invention includes: heating a molded article containing a polymer material, a pore forming agent, and a composition of a decomposable foaming agent, to -6 - 200842155 to the polymer substance a melting temperature, a step of foaming the molded product by decomposition of the decomposable foaming agent; and extracting the pore forming agent from the foamed molded article by dissolving the pore forming agent in a solvent to form The step of forming continuous bubbles in the object. According to the production method of the present invention described above, by combining foaming and extraction, the porous body having a high porosity can be obtained in a short time. The pore-forming agent is preferably a first component containing a melting point Mb higher than the melting point Ma of the polymer material. In this way, the polymer material and the pore-forming agent are melted and melted in a state in which the polymer material and the pore-forming agent are contained, and the pore-forming agent containing powder or particles can be easily obtained. The kneading material for forming. As a result, it is possible to form continuous bubbles more efficiently. The first component of the pore-forming agent is preferably a polyol having a melting point Mb of 100 to 350 °C. The polyol is preferably pentaerythritol. In the case where the pore-forming agent contains the first component, the composition is composed of 100 parts by weight of the polymer material, 50 to 400 parts by weight of the first component of the pore-forming agent, and 1 to 50 parts by weight of the decomposable foaming agent. good. The pore-forming agent preferably contains a second component having a melting point Me lower than the melting point Ma of the polymer material. This second component is preferably polyethylene oxide. In the case where the pore-forming agent contains the first and second components, the composition contains 10 parts by weight of the polymer material, 40 parts by weight of the first component of the pore-forming agent, and 40 parts by weight of the pore-forming agent, and the second component of the pore-forming agent. 20 to 450 parts by weight and 1 to 50 parts by weight of the decomposable foaming agent are preferred. 200842155 The manufacturing method of the present invention further comprises the steps of: melt-kneading the composition at a temperature lower than a temperature lower than the decomposition temperature M d of the M b and the decomposition-type foaming agent; and The step of obtaining the composition by melt-kneading the composition is preferred. In this case, the molded article is preferably obtained by molding the composition by an extrusion molding method, a calender molding method, a pressure molding method or an injection molding method. The polymer material is preferably a thermoplastic resin or a thermoplastic elastomer. The polymer material may be an olefin resin or a polyester resin. The high molecular substance may also be an ethylene-vinyl acetate copolymer. The above solvent is preferably water or an aqueous solvent. The above composition may further contain a functional enamel. Thereby, various functions of the continuous bubble can be imparted to the porous body. The functional enthalpy is preferably a functional polymer particle. This functional polymer particle is preferably a molecular mold. This functional polymer particle is preferably an ion exchange resin. The difference between the solubility parameter of the polymer compound constituting the functional polymer particles and the polymer material constituting the porous body is preferably within 1 or less. The functional polymer particles preferably have a functional group on the surface. The functional group preferably has reactivity with the polymer material. The porous body of the present invention contains a polymer material which forms continuous bubbles, and has a porosity of 50 to 90% by volume. The porous body of the present invention may further contain the above organic energy entangled material. In this case, the functional sputum is preferably exposed to the wall surface of the continuous bubble. Since the porous body has a high porosity, when the functional enthalpy is exposed to the wall surface of the continuous -8 - 200842155 bubble, the functional energy of the functional enthalpy can be utilized particularly effectively. The functional polymer particles are preferably bonded to the polymer substance by a reaction of a functional group on the surface thereof with a substance of the stomach #+. The porous body of the present invention may contain a polymer M which forms a continuous bubble and a functional molecule molecular particle which is a molecular mold. Further, the porous body of the present invention may contain functional polymer particles which form a polymer material of continuous bubbles and an ion exchange resin. The filter material of the present invention comprises the above porous body of the present invention. The ion exchanger base material of the present invention comprises the above porous body of the present invention. (Effect of the Invention) According to the production method of the present invention, a porous body having a high porosity can be obtained in a short time. Further, according to the production method of the present invention, since the pore-forming agent is removed after the foaming, continuous bubbles can be formed, and the porous body having good water permeability can be easily produced in a short extraction time. In the case of producing a porous body having a high porosity, the amount of the pore former can be reduced, and the pore former can be easily removed. Therefore, the production efficiency is good, and a stronger porous body can be obtained. The porous body of the present invention has a good air permeability because of its high porosity, and is particularly suitable for a filter material for filtration, an ion exchange structure material, a flat type column, and the like. Further, according to the production method of the present invention, it is possible to easily obtain a porous body which can provide various functions of continuous bubbles while maintaining a good water permeability or the like when the functional sputum is used. [Embodiment] Hereinafter, preferred embodiments of the present invention will be described. However, the present invention is not limited to the embodiment described below. The method for producing a porous body according to the present embodiment includes a step of melting and kneading a composition containing a local molecular substance, a pore forming agent, and a decomposable foaming agent, and melting and kneading. a step of molding a composition (kneaded product) to obtain a molded product; heating the molded product to a temperature at which the polymer material is melted, a step of foaming the molded product by decomposition of the decomposition type foaming agent; and forming pores by venting The agent is dissolved in a solvent to extract the pore former from the foamed molded article, and an extraction step of forming continuous bubbles in the formed product. As the above polymer material, a thermoplastic resin, a thermoplastic elastomer or a mixture of these may be preferably used. The melting point of the polymer substance is preferably from 100 to 30,000 °C. The thermoplastic resin is preferably one suitable for extrusion molding, calender molding, or injection molding. Therefore, the thermoplastic resin preferably has a melting point of 100 to 300 ° C. Specific examples of preferred thermoplastic resins include olefin-based resins such as polyethylene, polypropylene, ethylene-vinyl acetate copolymer, and ethylene-vinyl acetate copolymer saponified product, and polyethylene terephthalate. Polyester resin such as ester and polybutylene terephthalate, ethylene-methacrylic acid copolymer, polystyrene, AS resin, ABS resin, polyamine 6, polyamine 6 · 6 , polycarbonate Esters, polyacetals, and polyvinyl alcohols. These thermoplastic resins may be used singly or in combination of two or more. Among these, an olefin resin and a polyester resin are preferable. -10- 200842155 Thermoplastic elastomer is a soft segment that imparts rubbery elasticity and a polymer material composed of a hard segment for forming a three-dimensional mesh knot. It exhibits rubber elasticity at normal temperature. For plasticity. Therefore, the thermoplastic elastomer can be easily formed by extrusion molding, calender molding, or injection molding. Specific examples of the thermoplastic elastomer include a polystyrene elastomer in which the rigid segment is a polystyrene soft segment, a polybutadiene, a polyisoprene, or a hydrogenated product thereof, and the hard segment is polyethylene or poly. The soft section of propylene is a polyolefin elastomer of butyl rubber or EPDM (ethylene-propylene-diene copolymer), and the rigid section is a polyamine-based elastomer in which the polybenzazole soft section is polyester or polyether, and the hard section is agglomerated. a polyester-based elastomer in which the ester soft segment is a polyether, and a hard segment in which the urethane-based block soft segment having a urethane bond is a polyester or a polyether-based polyurethane-based elastomer body. These may be used alone or in combination of two or more kinds as a polymer material. As the pore-forming agent, a material which is soluble in an extraction solvent and which is capable of forming a bubble upon extraction by a solvent can be used. Therefore, when the polymer material is melt-kneaded together with the pore-forming agent, a powdery or particulate material which can obtain the characteristics of the kneaded product in which the pore-forming agent in a powder form or a particle form is dispersed in the polymer material can be obtained. The first component (hereinafter sometimes referred to as "first pore-forming agent") of the organic compound having a melting point Mb higher than the melting point Ma of the polymer substance as the pore-forming agent 〇 pore-forming agent can be preferably applied. A pore former can maintain a solid state at a molding temperature of -11 - 200842155 of a composition containing a polymer substance. Therefore, by using the first pore-forming agent, continuous bubbles can be easily and efficiently formed after the extraction. The method for producing a porous body may include: forming a molded article of a porous body composition (containing a first pore-forming agent having a melting point Mb higher than Ma) and having a height higher than Ma, in addition to the polymer material having a melting point Ma a step of heating to a temperature above Md to cause foaming, and a first pore forming agent in a solvent capable of dissolving the first pore-forming agent without dissolving the polymer substance The step of extraction. The melting point Mb of the first pore-forming agent is preferably 40 to 35 (TC is preferred. The lower limit of the melting point Mb is preferably 100 ° C, more preferably 1501: the upper limit of the melting point Mb is 30 (TC is more preferable. For example, high When the melting point Ma of the molecular substance is from 100 ° C to 300 ° C, the melting point Mb of the first pore-forming agent is preferably not less than Ma and more than 100 ° C and not more than 350 ° C, preferably 150 ° C. ～300°C is more preferable as the first pore-forming agent, and it is preferable to use a polyol having a carbon number of 2 to 5 and urea. Specific examples of the polyhydric alcohol include pentaerythritol and L-erythritol. , D_erythritol, meso-erythritol and tetramethyl glycol. Especially among these materials, pentaerythritol is preferred. Since pentaerythritol is hydrophilic, water can be selected as the solvent used in the extraction step. Or the aqueous solvent. Further, the melting point of pentaerythritol varies depending on the purity thereof, and usually has a melting point of 180 ° C to 260 ° C, so it is easy to use in combination with various polymer materials. Moreover, pentaerythritol is self-melting to solidification. The speed is fast, so the cooling time of the formed product can be shortened, which is beneficial to improve productivity. The pore-forming agent may be used singly or in combination of two or more kinds of -12-200842155. In the case of combining two or more types, it is possible to combine materials having different particle diameters and materials having different rigidity at the molding temperature. The formation state of the pores is easily changed. The pore-forming agent preferably contains a second component (hereinafter sometimes referred to as a "second pore-forming agent") having a melting point Me lower than the melting point Ma of the polymer material. The melting point Me of the two-pore former is preferably from 50 to 200 ° C. Examples of the second pore-forming agent include polyethylene oxide and polyethylene glycol. Among them, polyepoxy is particularly considered based on melt viscosity and the like. Ethane (equivalent to a molecular weight of 1,000,000 to 8,000,000) is preferred. The first pore-forming agent and, if necessary, the second pore-forming agent are uniformly dispersed in the melt-kneading for obtaining the kneaded material for forming. The polymer material is important. Therefore, a dispersing agent can be suitably used. Examples of the dispersing agent include higher fatty acids such as stearic acid, higher fatty alcohols such as stearyl alcohol, paraffin, and hard. Lipidamine, brown a higher fatty acid guanamine such as decylamine, methylenebisstearylamine, or ethylene bis-lipidamine. The decomposition type foaming agent is formed by decomposing by heating to a predetermined decomposition temperature Md or more to form a gas. As a specific example of the decomposition type foaming agent, azomethicin (ADCA, decomposition temperature: 195 to 2 10 ° C), azobisisobutyronitrile (AIBN, decomposition temperature 98) ~l〇2°C), arsenazodicarboxylate (decomposition temperature 240~25 0 °C), dinitrosopentamethylenetetramine (DPT, decomposition temperature 200~205 °C), p,p, - oxybisbenzenesulfonyl hydrazine (OBSH, decomposition temperature 157 to 162 ° C), and p-benzenesulfonyl hydrazine (TSH, decomposition temperature 103 to 111 ° C). -13- 200842155 When selecting a decomposable foaming agent, the relationship between the forming temperature of the above-mentioned mixture of the substance and the pore former and the decomposition type decomposition temperature should be considered. If the melt viscosity at the decomposition temperature of the decomposing foaming agent is too high, the mechanical strength of the gas generated by the decomposition of the foaming agent to the kneaded material is suppressed, so that the kneaded material is difficult to foam. If the melt viscosity of the kneaded material is too low, Then, the generated gas will be scattered by the contents and it is difficult to foam. From this point of view, the example material is an olefin-based resin, and it is a decomposable foaming agent, nitrogen dimethyl hydrazine (ADCA) and dinitrosopentamethylenetetramine (excellent. Further, in order to obtain a better hair In the bubble state, the composition is also a crosslinking agent and/or a crosslinking assistant. As the crosslinking agent, for example, a base peroxide, 2,5-dimethyl-2,5-di (t-butylperoxy) can be used. And an oxide such as 2,5-dimethyl-2,5-di(t-butylperoxy)hexyne-3. The crosslinking assistant may be used in combination of two or more kinds. 100 parts by weight, more preferably 0 to 5 parts by weight and 2 parts by weight or less. To make the effect of the crosslinking agent more suitable for the amount of the crosslinking agent is 0. 2 parts by weight or more is preferred, with 0. 4 weight is better. If the amount of the crosslinking agent is too small, the effect of improving the foaming state is reduced, and if it is too large, the improvement in the degree of foaming tends to be difficult. Examples of the crosslinking assistant include trimethylolpropane trimethyl ester, trimethylolpropane triacrylate, and triallyl ethylene dimethacrylate. The crosslinking assistant may also be combined with two kinds of crosslinking assistants, and the pressure of the kneaded material having the polymer foaming agent may be affected by 1 part by weight of the polymer material. On the other hand, it is easy to break through the high-scoring, especially the DPT), which is an organic cross-linking agent which can contain bis-isophenylpropanyl hexane, and is easy to exert. Ester, and used on. It is preferably 0 to 2 weights -14 to 200842155, more preferably 1 to 5 parts by weight. When the amount of the crosslinking assistant is more than 2 parts by weight, the effect of improving the foaming property cannot be remarkably improved. In order to facilitate the effect of the crosslinking assistant, it is preferably 1 part by weight or more. The above composition for obtaining a molded article may further contain a functional filler. The functional sputum filling material is an organic or inorganic cerium filling material which imparts a specific function to the porous body. As the functional enthalpy, a material which can impart a function to a porous body such as a honing function, a heat conduction function, a heat conduction prevention function, a conductivity function, a light absorbing function, a molecular sieve function, an ion exchange function or a molecular mold function can be given. As inorganic functional sputum fillers: cerium oxide, oxidized bromine and oxidized selenium honing agent, calcium carbonate and cerium oxide, etc., heat conduction or heat conduction prevention materials, thermal conductivity or conductivity of gold, silver, copper, etc. Pigment particles such as metallic particles or titanium dioxide. As the organic functional enthalpy, there are functional polymer particles formed of a polymer compound. The functional polymer particles may be ion exchange resin particles, molecular molds, honing agents, or organic pigments. Further, the functional polymer particles may be polystyrene porous particles. The polystyrene porous particles are, for example, particles used as a column and column filler for gel color layer analysis, and may also have a crosslinked structure formed of divinylbenzene. The functional polymer particles may be modified molecular particles such as polyethylene powder. Functional enamel, which can be a composite of inorganic and organic materials. An example of a composite material for functional enamel filler is a gold-plated particle on polystyrene particles. When the functional enthalpy has a melting point or a decomposition point, the temperature is preferably higher than the lowest temperature among Ma, Mb and Me as described in -15-200842155, which is the highest among Ma, Mb and Me. The temperature is higher and better. The melting point or decomposition point of the functional enthalpy is preferably higher than the temperature at which the functional enthalpy is charged in the porous body manufacturing step described above. In order to uniformly disperse the functional polymer particles in the polymer material for forming the porous body, the difference between the solubility parameters of the polymer compound constituting the functional polymer particles and the polymer material constituting the porous body is within 1 It is better to use 〇·5 or less. Solubility parameter (SP値) is the Polymer Handbook IV-341 Pages ~ IV-3 6 8 pages (with H. -G. ELIAS, J. BRANDRUP/E. H. "SOLUBILITY PARAMETER VALUE" (H., published in IMMERGUT; INTERSCIENCE PUBLISHERS) Burrell's note. In addition, in the "Solvent Handbook" (Asakura No. 3, Hiroshi Ichiro, Okawa Kasumi, Kumano Sori, and Sister Tail, Talk about Social Science, 1st Edition, 1976, 13th, 993, pp. 91-93) The same solubility parameters are also explained. The solubility parameter can be determined by the method of small or by experiment. In the small method, the sum of all the F 原子 of the atom in the molecule or the repeating unit is Σ F (where F 値 is the molar-attraction constant), and the unit is (cal). · cm3 ) 1/2 / mol, 25 ° C)), the molecular weight (or the molecular weight of the repeating unit) is Μ, and when the density of the molecule is P, SP 値 (5 can be obtained by the following formula. -16- 200842155 [Mathematical formula 1] Further, the main substituent F is as follows: methyl (H3C-): 214 methylene group (-CH2-; grade 2 carbon): 133 methylene group (H2C=(double bond) )): 190 methyne (HC; grade 3 carbon): 28 methyne (-HC = (double bond)): 111 quaternary carbon: 9 3 ester group (-COO· ) : 3 1 0 Secondary hydroxyl group (-〇Η ) : 3 0 0 Phenyl group: 735 Phenylene group: 658 According to the above formula, ethylene-vinyl acetate copolymer (ethylene: ene = 9: 1 (Mo Ear ratio), density 0. 93) of 5 is 8. 5 (molecular weight of anti-C22H4202: 3 3 8. 5 6 ), styrene-divinylbenzene styrene: divinylbenzene = 1: 1 (mole ratio), density 0·90) 7. 2 (molecular weight of repeating unit C18H19: 234. 3 2 ), poly(ethylene glycol acrylate) polymer (density 1). 1) of 6 is 7 · 7 (molecular weight of C1GH1404: 198. 21), poly(dimethyl methacrylate) (density 1. 1) of 5 is 8. 3 (repeated unit CmH1605 S: 228. twenty four ). In the case where the functional polymer particles are molecular molds, they can be supported on the polymer material forming the porous body. Such a porous acetic acid complex unit (molecular molecular cast of δ is a repeating monoglyceride of dimethyl group, and recovery of trace organic compounds after capture and capture by a trace amount of organic compounds of a molecular mold at -17-200842155 In the case of forming a continuous bubble in the porous body, a specific amount of a specific organic compound contained in the water can be taken as long as the porous body carrying the molecular mold is permeable to water. Therefore, a porous body can also be used as a filter material. For the purpose, the porous body is preferably one having a high water permeability. The functional polymer particles used as the molecular mold are polymer particles which are conventionally used as an imprint polymer. The embedded polymer selectively adsorbs the target substance under specific conditions and releases the adsorbed target substance under specific conditions. The embedded polymer is formed by casting the target substance or the like. After the non-covalent bonding interaction between the type molecule and the functional monomer is self-joining, A polymer obtained by a method of performing polymerization in the presence of a solvent and then removing the mold molecules. In the case of using a bulk polymerization, the obtained polymer may be appropriately pulverized and used. In the case of suspension polymerization, particles may be obtained. In the case of a plug-in polymer, it is not necessarily pulverized. In order to obtain a particulate embedded polymer, a seed polymerization method is preferred, in particular a well-known two-stage swelling polymerization method or a multi-stage swelling polymerization method. The substance is not particularly limited, and it is preferably a lower molecular weight. Since PCB (perchlorobiphenyl), biguanide A, brominated bisphenol A, and dioxin are environmental hormones, they are exposed to the double When phenol A is the target substance, not only itself, but also -18-200842155 can be used as a mold molecule for the second butylbenzene. Moreover, in the case where brominated bisphenol A is the target substance, not only itself, but also 2,6-bis-(trifluoromethyl)-formic acid can be used as a sputum-seeking molecule. The sputum can be used to obtain a functional monomer for embedding a polymer, which can be polymerized ( It is a compound of a radical polymerizable compound. The functional monomer has a terminal group (a functional group such as a basic group or an acidic group) which interacts with a target substance other than a polymerization site. Specific examples thereof include vinyl pyridine, vinyl imidazole, acrylic acid, methacrylic acid, maleic acid, maleic anhydride, itaconic acid, 2-ethyl acrylate, and methacrylic acid 2_ Hydroxyethyl ester, acrylamide, methacrylamide, acrylonitrile, methacrylonitrile, glycidyl methacrylate, and vinyl acetate. As a crosslinking agent used to obtain an embedded polymer, it has two The radically polymerizable compound having the above double bond is preferred. Specific examples include ethylene glycol dimethacrylate, ethylene glycol diacrylate, glycerin dimethacrylate, glycerin diacrylate, and tetramethylene. Alcohol dimethacrylate, pentaerythritol tetramethacrylate and divinylbenzene. A radical polymerizable compound (hereinafter referred to as "monofunctional monomer") having a radical polymerizable compound having two or more double bonds can be suitably used. Examples of the monofunctional monomer include alkyl methacrylate, ethyl methacrylate, butyl methacrylate, octyl methacrylate, and 2-ethylhexyl methacrylate such as alkyl methacrylate and acrylic acid. An alkyl acrylate such as an ester, ethyl acrylate, butyl acrylate, octyl acrylate, or 2-ethylhexyl acrylate, and styrene. -19- 200842155 The above two-stage swelling polymerization method or multi-stage swelling polymerization method comprises a swelling aid such as dibutyl dicarboxylate to swell the swellable particles such as polystyrene; and the swelled particles and the mold molecules and the functional single agent ( If necessary, a monofunctional monomer and a polymerization initiator-solvent may be used to re-swell the particles and then raise the temperature to polymerize the functional granules together. The polymerization initiator is preferably dissolved in the swelling aid in advance. The above swelling aid is preferably a plasticizer known as a phthalic acid polymer. As the swelling aid, a one-functional crosslinking agent or a water-insoluble organic solvent can also be used. As the above solvent, water or an aqueous solvent is preferred. It is a mixed solvent of water and a water-soluble organic solvent. Examples of the water-soluble include alcohols such as methanol, ethanol, and isopropyl alcohol, ketones such as acetone and cyclohexanone, and ethers such as diisopropyl ether and dibutyl ether, so that the particles and other components are properly suspended. The addition of a polymer dispersant such as a polymer dispersant or an anionic surfactant to a solvent is carried out by using the polymer particles and a crosslinking agent, and a water-insoluble organic solvent such as benzene, toluene, cyclohexane or hexane. , a viscous particle-like embedded polymer. It is preferred that the intercalation polymer is a porous end of the adsorbed end group of the target substance. As the agent and the surfactant, those described later can be used. As the multistage swelling polymerization method, the polymer particles can be swelled by a sequential fluxing aid, swollen with a water-insoluble organic solvent, and then crosslinked, followed by polymerization. In this case, it may be any one before the polymerization: a monomer represented by a polymer of benzene, a monomer which is suspended by a crosslinking agent or a crosslinking agent, a crosslinking solvent, an organic solvent, and methyl ethyl ketone. Further, it is preferably a polyvinyl alcohol agent. When benzene and dimethyl are porous, the initial polymerization can be carried out by swelling with a swelling agent, and the -20-200842155 particles are suspended in a solvent (water or aqueous solvent). In any of the polymerization methods used for the production of a molecular mold as described above, a monomer having one functional group is further polymerized at the final stage of the polymerization or after the end thereof, and the molecular mold can be surface-modified. quality. As such a monomer having one functional group, the same as the above functional monomer can be used. Thereby, embedded polymer particles having functional groups on the surface can be obtained. The use of this functional group makes it easier to adsorb or bond to the carrier in which the polymer is embedded. For example, 'the embedded polymer obtained by using a monofunctional monomer having a carboxyl group as a single system having one functional group is combined with an ethylene-vinyl acetate copolymer as a polymer material for forming a porous body. In this case, the intercalation polymer can be bonded to the porous body by transesterification of the carboxyl group of the intercalating polymer with the ethylene group of the ethylene-vinyl acetate copolymer. Thereby, the embedded polymer can be carried on the porous body. Functional functional materials such as molecular molds and ion exchange resins (functional high molecular particles) are preferably exposed to the wall surface of the continuous cells of the porous body in order to fully exert their functions. Therefore, the difference between the solubility parameter of the polymer compound constituting the functional enthalpy and the polymer material constituting the porous body is preferably within i, and is 0. Less than 5 is better. Thereby, the functional enthalpy can be uniformly dispersed to ensure that the functional enamel material is easily exposed on the surface of the porous body. Alternatively, the difference in solubility parameter may be made outside of the range (i.e., the difference in solubility parameter is greater than 0. 5 or 1) makes it difficult to mix functional polymer particles with high molecular substances. In this case, the phase of the porous body wall is prevented by the interaction of adsorption or chemical bonding, and a large effect can be exerted by using a small amount of the functional polymer particles. Therefore, it is preferable to carry out surface modification by the functional group which interacts with the polymer substance which comprises a porous body with the surface of the energy-polymer particle of the -21 - 200842155. Based on this viewpoint or the like, the functional polymer particles are preferably a functional group having a reactivity with a polymer material constituting the porous body on the surface thereof. As such a functional group, for example, a mercapto group is used. In the case of a molecular mold of a functional polymer particle for functional urethane, any of a foaming agent and a pore forming agent may be used, or both. When a blowing agent is not used, a crosslinking agent and a crosslinking assistant can also be used. The size of the functional polymer particles can be any, and the maximum particle diameter is 0. 1 to 1 000 // m is preferred. Further, the amount of the functional sputum is 0% by weight relative to 100 parts by weight of the high molecular substance. 1 to 300 parts by weight is preferred, with 0. 5 to 200 parts by weight is more preferred. A preferred formulation of the composition for obtaining a porous body is as follows. In the respective blending ratios described below, the range of the number in the brackets is particularly preferable. Further, it is needless to say that a dispersant for improving kneading workability may be added to any of the following compositions. High molecular weight 100 parts by weight First pore former 50 to 400 parts by weight (100 to 350 parts by weight) Decomposable foaming agent 1 to 50 parts by weight (3 to 20 parts by weight) Dispersant 〇~3 parts by weight (0. 1 to 1 part by weight) Crosslinking agent 〇~5 parts by weight (0. 2~2 parts by weight) Crosslinking aid 〇~2 parts by weight (0~1. 5 parts by weight) Further, in the case of using the second pore-forming agent, the following blending ratio is preferred. Polymer substance 1 part by weight - 22 - 200842155 First pore former 40 to 450 parts by weight (80 to 30,000 parts by weight) Second pore former 20 to 45 parts by weight (40 to 30,000 parts by weight) Type foaming agent 1 to 50 parts by weight (3 to 20 parts by weight) Dispersing agent 〇 ~ 3 parts by weight (0. 1 to 1 part by weight) Crosslinking agent 〇~5 parts by weight (0. 2~2 parts by weight) Crosslinking aid 〇~2 parts by weight (0~1. 5 parts by weight) In the case of functional enamel filling, the following blending ratio is preferred. 1 g of the polymer material 1 part by weight of the first pore former, 50 to 400 parts by weight of the decomposable foaming agent, 1 to 50 parts by weight (100 to 350 parts by weight), functional 塡 filling material, 1 to 300 parts by weight ( 0. 5 to 200 parts by weight) Further, in this case, the following mixing ratio can also be used. 1 g of the polymer material 1 part by weight of the first pore-forming agent 50 to 400 parts by weight (100 to 350 parts by weight) 1 to 50 parts by weight of the decomposing foaming agent (3 to 20 parts by weight) Dispersant 〇 〜 3 weight Share (0. 1 to 1 part by weight) Crosslinking agent 〇~5 parts by weight (0. 2~2 parts by weight) Crosslinking aid 〇~2 parts by weight (0~1. 5 parts by weight) functional 塡 filling material 1 1~3 00 parts by weight (0. 5 to 200 parts by weight) Further, in the case of using the second pore-forming agent, the following mixing ratio is preferred. 100 parts by weight of the polymer material, the first component of the pore-forming agent 40 to 450 parts by weight (80 to 30,000 parts by weight) -23- 200842155 The second component of the pore-forming agent 20 to 450 parts by weight (40 to 300 parts by weight) 1 to 50 parts by weight of the decomposable foaming agent (3 to 20 parts by weight) Functional 塡 filling material 1 1 to 300 parts by weight (0. 5 to 200 parts by weight) Further, in this case, the following mixing ratio can also be used. Polymer substance 1 part by weight of the first pore former 40 to 450 parts by weight (80 to 30,000 parts by weight) Second pore former 20 to 45 parts by weight (40 to 30,000 parts by weight) Decomposable foaming agent 1 to 50 parts by weight (3 to 20 parts by weight) Dispersant 〇 3 parts by weight (0·1 to 1 part by weight) Crosslinking agent 〇 5 parts by weight (0. 2~2 parts by weight) Crosslinking aid 〇~2 parts by weight (0~1. 5 parts by weight) Functional 塡 filling material 〇·1~3 00 parts by weight (0. 5 to 200 parts by weight) If the amount of the pore forming agent is too small, the porosity tends to decrease. If the amount of the pore forming agent is too large, the porosity will become too large, and the mechanical strength and formability tend to be lowered. Further, since the second pore-forming agent acts as a melting modifier during melt-kneading, the first pore-forming agent may contain more than the second pore-forming agent. If the amount of the foaming agent is too small, foaming is substantially impossible, and if it is too large, the appearance is poor. In the composition and the molded article obtained by using the same, the total amount of the first pore-forming agent and the second pore-forming agent is preferably 40 to 90% by volume, and 50 to 85 % by volume based on the entire molded product. For better. When the total amount is less than 40% by volume, the extraction time tends to increase, and if it exceeds 5% by volume, the mechanical strength and formability of the obtained porous body tend to be lowered. -24- 200842155 The composition may also contain a surfactant. Thereby, the extraction can be performed more efficiently when the pore former is extracted with water or an aqueous solvent. The surfactant may be any of an anionic surfactant, a cationic surfactant, and a nonionic surfactant. As the anionic surfactant, for example, a mercaptobenzenesulfonate such as eleven sodium sulfonate may be used, and a SOJ-based sulfonate may be directly added to the hospital base, and a s〇3Na group may be added to the naphthalene. Higher fatty acid salts such as hydrogen naphthalene sulfonate and sodium oleate. Examples of the cationic surfactant include a trialkylbenzylammonium salt and a tetraalkylammonium salt. As the nonionic surfactant, there are: polyethylene oxide alkyl ether, polyethylene oxide alkylphenyl ether, polyethylene oxide alkylamine, polyethylene oxide alkylamine fatty acid ester, and alkane. Diethanolamine, hydroxyalkyl monoethanolamine, and alkyldiethanolamine and the like. The amount of the surfactant is preferably from 0 to 5 parts by weight based on 1 part by weight of the polymer material, and more preferably from 5 to 3 parts by weight. In order to obtain the composition of the porous body, in addition to the above-described components, in order to improve the efficiency of the melt-kneading, an oxidation preventive agent, a metal deterioration preventive agent, an ultraviolet absorber, or the like may be added as needed within the scope of the spirit of the present invention. Anti-adhesives, pigments, etc. In the kneading step, the composition containing the polymer substance, the pore forming agent, and the decomposable foaming agent is melted and kneaded while the polymer substance is melted. The melt kneading can be carried out by a method generally used for melt kneading of a thermoplastic resin or a thermoplastic elastomer. Specifically, the melt kneading can be carried out by a kneading roll, a Hanschel mixer, a uniaxial extruder or a twin-screw extruder. The kneaded mixture after the mixing can be cut into granules if necessary. In the case of using the first pore-forming agent, it is preferably at least the melting point Ma of the polymer-25-200842155 and lower than the melting point Mb of the first pore-forming agent and the decomposition temperature Md of the decomposition-type blowing agent. The composition is melt-kneaded at a lower temperature. Thereby, a kneaded product in which a powdery or particulate first pore-forming agent is uniformly dispersed can be easily obtained. In the forming step, the kneaded material obtained by melt kneading is formed into a molded product. In other words, the kneaded material is shaped to obtain a molded product. The forming step is performed simultaneously with or after the kneading step. The kneaded material can be formed into any shape such as a sheet shape, a film shape, a rectangular shape, a cylindrical shape, a cylindrical shape, and a prismatic shape. The forming method can be determined depending on the shape of the desired molded article. The sheet-like formed product can be obtained by a press molding method, a calender molding method, or an extrusion molding method. The cylindrical, cylindrical, and angular column shaped articles can be obtained by extrusion molding. Other shapes of any three-dimensional shape can be obtained by injection molding. The molded article having a three-dimensional shape can be obtained by forming a kneaded material into a sheet shape and then shaping it into a three-dimensional shape by a vacuum forming method or a pressure forming method. In the foaming step, the molded product (solid molded product) obtained from the kneaded material is heated to be foamed. The foaming step is carried out by raising the temperature of the molded product to the decomposition temperature of the decomposable foaming agent kneaded in the molded product. The temperature rise can be carried out, for example, in a high temperature bath. When the temperature rises, the molded product softens to cause adhesion to the substrate. Especially in the case of sheet-like shaped articles, it is particularly easy to adhere to the substrate. Therefore, it is preferred that the molded article is placed on a release sheet such as a fluororesin sheet to be foamed. Further, in the case of a molded article having a three-dimensional shape, it is preferable to mount the molded article on a suitable jig that does not deform. In the extraction step, the pore former is extracted from the foamed shaped article using a solvent of a solvent-forming pore former. The solvent is not particularly limited as long as it is a solvent or a mixed solvent in which the pore-forming agent is dissolved in a substantially undissolved polymer material, and is not particularly limited, and may be appropriately selected depending on the type of the polymer material and the pore-forming agent. select. Water or an aqueous solvent (aqueous medium) is preferred based on considerations such as the influence on the environment. As the aqueous solvent, a mixed solvent of water and a water-soluble organic solvent can be used. The water-soluble organic solvent may, for example, be an alcohol such as methanol, ethanol or isopropyl alcohol, a ketone such as acetone, methyl ethyl ketone or cyclohexanone or an ether such as diisopropyl ether or dibutyl ether. The ratio of the water-soluble organic solvent is preferably 50% by mass or less based on the entire solvent. The extraction can be carried out by immersing the molded article after the foaming step in water or a water-soluble solvent having a liquid temperature of from room temperature to 60 °C. In this case, the solvent is stirred by a screw or the like, for example, and when the polymer material is a material having elasticity as an elastomer material, the molded product can be repeatedly subjected to extrusion processing by a two-roll or the like, and the extraction time can be shortened. The extraction time varies depending on the thickness of the molded article, the expansion ratio, and the like, and is usually selected between 10 and 200 hours. After the extraction, the solvent adhering to the molded product is dried to obtain a porous body in which continuous bubbles are formed. In the method of the present embodiment, a porous body having various pore diameters and various porosity can be obtained by appropriately adjusting the types and amounts of the polymer material, the pore-forming agent, and the decomposable foaming agent, and the production conditions. In particular, according to the present embodiment, a porous body having a high porosity can be easily obtained in a short period of time. In the foaming step, the molded article is foamed. By foaming, a molded article which is expanded before foaming can be obtained. For example, in the case where a polymer having a polymer content of 40% by volume -27 to 200842155 and a total amount of the pore-forming agent of 60% by volume is molded, a molded product having a volume of 3 mL is obtained, and if the foaming step is not performed, only When the porous body is formed by extraction, 60% by volume (1·8 mL) of the pore former is extracted, and the remaining 40% by volume (1. 2 mL of the polymer material has an apparent volume of 3 mL of a porous body (porosity of 60 vol.), in contrast, a 3 mL composition having the same composition as described above is expanded by a foaming step. In the case of a volume of 4 mL, it can be obtained by extraction after 1. The apparent volume formed by 2 mL of the polymer material was 4 mL of a porous body (porosity: 70% by volume). That is, by the foaming step, the same amount of the polymer substance used to obtain the porous body having an apparent volume of 3 mL in the case of the non-foaming step is used, and an apparent volume of 4 mL can be obtained. Porous body. From the above facts, it can be seen that, in the present invention, (a) by adding a foaming step, it is possible to obtain a porous having a high porosity which is difficult to form in the conventional method (without a foaming step) from the viewpoint of formability. body. (2) When the amount of extraction is reduced, a porous body having the same porosity as that of the conventional method can be produced at a lower cost. (3) When the solid molded product is extracted, it is gradually extracted from the smooth surface to the inner side, so the extraction time is long; in contrast, in the case of extracting the foam, the bubble is made to the inside. The bubble is conveyed while the lower side is extracted, so the extraction time is shorter' is an advantage. According to the method of the present embodiment, a porous body having a porosity of 5 〇 to 90% by volume can be easily produced, and even 80 to 90 vol. A porous body having a high porosity which has not been used in the past. Further, since the bubbles formed by the extraction are continuous bubbles, a porous body having a high porosity and forming continuous bubbles can be obtained -28-200842155. Since the continuous bubbles are formed, a porous body excellent in water permeability can be obtained. The porous body obtained by the method of the present embodiment is a continuous bubble type. Since the porous body is excellent in gas permeability and water permeability, it can be preferably applied to various filter materials, ion exchanger base materials, and the like. Further, since the water content is also excellent, the porous body can also be used as a moisture replenishing material such as a cosmetic puff material, an ink pad, or a flower arrangement. Further, the porous body can be preferably applied to a sound insulating material, a packaged temperature material, an impact buffer material, a shockproof material, a cushioning material, and the like. The cylindrical porous body can be applied, for example, as a flat-plate type column having ion exchange energy. According to the present invention, a flat type column having a high opening ratio can be produced in a short time. Further, for example, one end of the cylindrical porous body is taken into the soil of the flower pot, and the other end is inserted into the water in the water layer on the side of the flower pot, and the water can be supplied to the flower pot by the movement of the porous body by the capillary phenomenon. That is, a porous body can be used for water supply purposes. The cylindrical porous body can be produced by a method comprising the step of disposing a cylindrical molded article of the above composition in a tubular container having an inner diameter larger than the diameter of the molded product. The step of foaming by heating the molded product in the tubular container or the step of extracting the pore forming agent from the molded product. The step of taking out the foamed molded article from the tubular container after the foaming step, the step of extracting the pore forming agent from the foamed molded article, and the foamed molded article after the extraction may be accommodated in the tubular container. The method of the step is to obtain a cylindrical porous body. As the tubular container, for example, a glass tube, a plastic tube, a steel tube or the like can be used. [Examples] -29- 200842155 (Example 1) An ethylene-vinyl acetate copolymer (manufactured by Mitsui-DuPont Polymer Chemicals Co., Ltd., trade name: Aba Flix P 1 007, as a polymer material, Melting point 94 ° C) 100 parts by weight of pentaerythritol as a first pore-forming agent (manufactured by Kwong Wing Chemical Industry Co., Ltd., trade name: Tablet Tallet, melting point 2 5 4 ° C) 225 parts by weight as a second pore Forming agent of polyethylene oxide (manufactured by Sumitomo Seika Co., Ltd., trade name: PEO-18Z, melting point 65 ° C) 225 parts by weight, azo dimethyl hydrazine as a blowing agent (Otsuka Chemical Co., Ltd.) System, trade name: Unifom AZ, decomposition temperature 199 °C) 9 parts by weight, and surfactant (King (stock), trade name: Aileke Trosteriba - TS-5) 1 weight And cross-linking agent (Japanese fat (stock) system, trade name: Bacumir) 0. 8 parts by weight was kneaded by a roller (kneading temperature: 15 (TC). The kneaded material was heated at 15 (15 ton) with a press molding machine (pressure: 50 tons), and then cooled to obtain 250 mm x 250 mm x thickness 3 mm. Then, the molded product was placed on a fluororesin sheet in a high temperature bath, and the molded product was foamed by heating at 203 ° C for 5 minutes. The foamed molded product was immersed in a water tank. In the water at 40 ° C, the pore former was extracted while stirring under a stirring machine in the extraction time column of Example 1 of Table 1. After the extraction, the molded product was dried at 40 ° C. The oven was dried for 24 hours to obtain a porous body 0 in which continuous bubbles were formed (Example 2). The same procedure as in Example 1 of the practice of -30-200842155 was carried out except that the amount of the foaming agent was changed to 4.6 parts by weight. A porous body in which continuous bubbles were formed was obtained. (Example 3) Except that the amount of the first pore-forming agent was changed to 100 parts by weight and the amount of the second pore-forming agent was changed to 1 part by weight, A porous body in which continuous bubbles were formed was obtained in the same manner as in Example 1. Example 4) A porous body in which continuous bubbles were formed was obtained in the same manner as in Example 3 except that the amount of the foaming agent was changed to 4.6 parts by weight. (Example 5) In addition to changing the thickness of the molded product A porous body in which continuous bubbles were formed was obtained in the same manner as in Example 1 except that the thickness was 1 mm. (Example 6) The amount of the foaming agent was changed to 4. A porous body in which continuous bubbles were formed was obtained in the same manner as in Example 5 except for 5 parts by weight. (Comparative Example 1) 100 parts by weight of an ethylene-vinyl acetate copolymer (manufactured by Mitsui-DuPont Polymer Chemical Co., Ltd., trade name: Aba Flix P 1 〇〇7) as a polymer material Pentaerythritol of the first pore-forming agent (manufactured by Kwong Wing Chemical Industry Co., Ltd., trade name: Tablet Talit) 2 2 5 parts by weight, polyethylene oxide as the first -31 - 200842155 two-porosity forming agent (Sumitomo (stock) system, trade name: PEO-18Z) 225 parts by weight, and surfactant (Kao (share) system 'commodity name: Aileke Trostriba _TS-5) i parts by weight and cross-linking Agent (Japanese fat (stock) system, trade name: Bacumir) 〇. 8 parts by weight was kneaded by a roll (kneading temperature: 15 〇. (:). The kneaded product was heated at 15 ° C for 5 minutes using a press molding machine (pressure of 50 tons), and then cooled to obtain 250 mm x 250 mm x 3 mm molded product. Then, the foamed molded product was immersed in water at 40 ° C in a water bath, and between the extraction times shown in Table 1, the pore former was extracted while stirring under a stirrer. Thereafter, the molded product was dried in a 4 CTC drying oven for 24 hours to obtain a porous body. (Comparative Example 2) The amount of the second pore-forming agent was changed except that the amount of the first pore-forming agent was changed to 1 part by weight. In the same manner as in Comparative Example 1, a porous body was obtained in the same manner as in Comparative Example 1. (Comparative Example 3) The same procedure as in Comparative Example 1 was carried out except that the thickness of the molded product was changed to 1 〇 mm. The porous body was obtained. The results of measurement of the porosity and water permeability of the porous body obtained in the examples and the comparative examples are shown in Table 1. The measurement of the porosity and the water permeability was carried out for the molded article before the extraction and after the predetermined time of #Φ. Steps are carried out. -32- 200842155 (1) Porosity Volume %) The volume VI of the porous body in a vacuum, VI, and the volume V calculated from the length, width, and height of the porous body were measured using a Tokyo Scientific Co., Ltd. air comparative type hydrometer 100 〇 type. The porosity is determined by the following formula: Porosity of porous body = (1-(乂1/¥))\1〇〇 [% by volume] (2) Water permeability Fig. 1 is a schematic diagram of a water permeability measuring device. The body 1 is sandwiched between a filter holder (inner diameter 35 mm) 2 for filtration of Toyo filter paper (sand) and a container 3 having the same inner diameter of 35 mm, and is clamped by a clamp 4. The interface 5 is connected to the decompression pump, and the air in the container is sucked in the direction of the arrow A, and the pressure in the container is reduced to 10 cmHg. Under the reduced pressure, 5 OmL of pure water is supplied to the filter medium holder 2 for filtration. The pure water moves through the porous body 1 into the container 3. The time (seconds) from the start of supply of pure water to the pure water in the filter holder 2 is measured, and it is used as an index of water permeability. -33- 200842155 [Table i ] Foaming step thickness (mm) Pre-extraction extraction] Post-porosity mm%] Extraction time [hours] 5 10 20 40 90 Example 1 3 29 Porosity [% by volume] 62 83 88 88 89 Water permeability [seconds] - • • 4 3 Example 2 There are 3 20 Porosity [% by volume] 58 80 85 85 85 Water permeability [seconds] • 5 5 Example 3 There are 3 38 Porosity [% by volume] 63 75 80 81 82 Example 4 There are 3 30 Porosity [% by volume] 57 67 73 78 79 Example 5 There are 10 23 Porosity [% by volume] 32 41 57 82 87 Example 6 10 10 Porosity [% by volume] 20 30 47 73 83 Comparative Example 1 ^Γι I Γ. 1111: J \ \\ 3 5 Porosity [% by volume] 25 43 70 76 80 Water permeability [seconds] Discussion 220 70 Comparative Example 2 Μ j\ \\ 3 4 Porosity [% by volume] 18 30 45 60 66 Comparison Example 3 Μ j\ \\ 10 5 Porosity [% by volume] 12 19 33 50 73 Fig. 2 is a graph showing the relationship between the porosity and the extraction time in Example 1, Example 2, and Comparative Example 1. From the results, it was found that the porous bodies of Example 1 and Example 2 produced by the foaming step were extractable to a porosity to saturation level at a stage of extraction time of about 15 hours, and the porosity thereof was 8 5 vol% or more. On the other hand, the porous body of Comparative Example 1 obtained in the non-foaming step was about 60 to 80 hours from the end of the extraction. Further, the porosity of Comparative Example 1 was about 80% by volume, which was lower than that of 5% by volume of Examples 1 and 2. Further, the porous bodies of Examples 1 and 2 produced by the foaming step had a short water permeation time, and these porous bodies showed very good water permeability. On the other hand, the porous body of Comparative Example 1 which was produced without the foaming step had a long water permeable period, and the water permeability thereof was inferior to those of Examples 1 and 2. -34- 200842155 Fig. 3 is a graph showing the relationship between the porosity and the extraction time in Example 3, Example 4, and Comparative Example 2. From the results, it can be seen that the porous bodies of Examples 3 and 4 which were produced by the foaming step were extracted at a stage of extraction time of about 20 hours to achieve a porosity to a degree of saturation, and the porosity thereof was achieved. 80% by volume or more. On the other hand, in the porous body of Comparative Example 2 obtained in the non-foaming step, even when the extraction was carried out for 90 hours, the porosity was only about 65 % by volume. Fig. 4 is a graph showing the relationship between the extraction time of Examples 5, 6 and 3 and the porosity of the porous body. From the results, it was found that the porous bodies of Examples 5 and 6 which were produced by the foaming step were extractable to a porosity to saturation level at a stage of extraction time of about 40 hours, and the porosity thereof reached 80. The volume is about %. On the other hand, the porous body of Comparative Example 3 obtained in the non-foaming step was required to be at least 9 hours in the end of the extraction. The functional polymer particles of Reference Examples 1 to 4 were produced as follows, and were used as a molecular mold having bisphenol A as a target substance. Reference Example 1: Production of functional polymer particles (molecular mold of polymer compound) (polymerization method: seed polymerization using polystyrene particles) Polystyrene particles having an average particle diameter of 1 / m. 9g, swelling aid (dibutyl phthalate) 4. 5g, surfactant surfactant sodium lauryl sulfate. A mixture of 7 g and 40 g of water is added to a mixture of ethylene glycol dimethacrylate / 4 - vinylpyridine / p-tert - butylphenol / (mole ratio 4 0 / 8 / 1). 9 g, -35- 200842155 Polymerization initiator (2,2'-dioxobis-2,4-methylammonium) 3. 2g, polyethylidene alcohol 2 5 · 9 g, sodium dodecyl sulfate 2 · 2 g, toluene 4 7 · 0 g, water 3 2 0 g of uniform dispersion, stirred at 25 ° C for 3 60 minutes, The polystyrene particles were swollen and then heated to 50 ° C for 240 minutes to polymerize. After 240 minutes, a methacrylic acid for surface modification of the particles with a methacrylic acid group was added. 4g, the polymerization was continued for 600 minutes. Thereafter, the polymer was separated by filtration, and the reactant was washed with water, methanol and tetrahydrofuran to remove p-tert-butylphenol. The obtained functional polymer particles (molecular mold) had an average particle diameter of 5 // m. Further, the solubility of the molecular mold is the result of the previous calculation, which is 9. 9. Reference Example 2: Production of functional polymer particles (styrene-divinylbenzene copolymer particles) In addition to a mixture of styrene/divinylbenzene/(mol ratio 1 /1) 48. 6g of a mixture of ethylene glycol dimethacrylate/4-vinylpyridine/p-tert-butylphenol 63. Polymerization was carried out in the same manner as in Reference Example 1 except for 9 g. No addition of methacrylic acid was carried out after 240 minutes of polymerization. Further, styrene/divinylbenzene copolymer particles were produced in the same manner as in Reference Example. The average particle diameter of the obtained copolymer particles is 4. 5 // m. Further, the solubility parameter of the copolymer particles (molecular mold) was calculated by the above formula as a result of 7. 2. Reference Example 3: Production of functional polymer particles (ethylene glycol dimethacrylate) -36- 200842155 In addition to ethylene glycol dimethacrylate 55. Lg substituted ethylene glycol dimethacrylate / 4-vinyl pyridine / p-tert-butyl phenol mixture 63. Polymerization was carried out in the same manner as in Reference Example 1 except for 9 g. No addition of methacrylic acid was carried out after 240 minutes of polymerization. Further, ethylene glycol dimethacrylate polymer particles were produced in the same manner as in Reference Example 1. The obtained polymer particles had an average particle diameter of 5 / zm. Further, the solubility parameter of the polymer particles (molecular mold) is calculated by the former formula as 7. 7. Reference Example 4: Production of Functional Polymer Particles (Glycerol Dimethacrylate Polymer Particles) Instead of using ethylene glycol dimethacrylate 5 5 · 6 g in place of ethylene glycol dimethacrylate / 4-vinylpyridine / a mixture of p-tert-butylphenol 63. Polymerization was carried out in the same manner as in Reference Example 1 except for 9 g. No addition of methacrylic acid was carried out after 240 minutes of polymerization. Further, glyceryl dimethacrylate polymer particles (molecular mold) were produced in the same manner as in Reference Example 1. The average particle diameter of the obtained polymer particles is 4. 5 // m. Further, the solubility parameter of the polymer particles is calculated by the above formula as a result of 8. 3. (Example 7) An ethylene-vinyl acetate copolymer (manufactured by Mitsui & DuPont Polymer Chemicals Co., Ltd., trade name: Aba Flix P 1 〇〇7, density: 将. 9 3g/ml, solubility parameter: 8. 5) 100 parts by weight of pentaerythritol as a first pore-forming agent (manufactured by Kwong Wing Chemical Industry Co., Ltd., trade name: Tablet Talit) 225 parts by weight, polycyclo-37-200842155 as a second pore-forming agent Ethane (Sumitomo Refinery Co., Ltd., trade name: PEO-18Z) 225 parts by weight, azo dimethyl hydrazine as a foaming agent (Otsuka Chemical Co., Ltd.) Product name: Univer AZ 4. 5 parts by weight, and a surfactant (manufactured by Kao Co., Ltd., trade name: Elektrostroma-TS-5) 1 part by weight and a crosslinking agent (manufactured by Nippon Oil & Fat Co., Ltd., trade name: Ba枯密尔) 〇. 8 parts by weight and 5 parts by weight of the molecular mold obtained in the above Reference Example 1 were kneaded by a roll (kneading temperature: 15 ° C). The kneaded product was heated by a press molding machine (pressure of 50 tons) at 550 for 5 minutes, and then cooled to obtain a sheet-like formed product of 250 mm x 250 mm x 3 mm thick. Then, the molded product was placed on a fluororesin sheet in a high temperature bath, and the molded product was foamed by heating at 260 °C for 5 minutes. The molded product was immersed in water at 40 ° C in a water bath, and the pore former was extracted while stirring under a stirring machine for 90 hours. After the extraction, the molded product was dried in a drying oven at 40 °C for 24 hours to obtain a porous body in which continuous bubbles were formed. (Example 8) A porous body was obtained in the same manner as in Example 7 except that the amount of the molecular mold was changed to 2 parts by weight. (Example 9) A porous body was obtained in the same manner as in Example 7 except that the amount of the molecular mold was changed to 1 part by weight. -38-200842155 (Example 1 多孔) A porous body was obtained in the same manner as in Example 7 except that the amount of the molecular mold was changed to 〇 by weight. Using the porous bodies of Examples 7 to 10, the adsorption isotherms of bisphenol a were prepared in the following procedure. The adsorption isotherm was prepared by the adsorption isothermal equation of Freundlich (JIS Z 8 8 3 0). Ready to dissolve in the water. An aqueous solution of bisphenol A at a concentration of 13 g/L was used as an adsorption sample. Each of the porous bodies (adsorbed materials) obtained in each of Examples 7 to 1 was added to a sample of 100 mL at a concentration of 8 to 9 points in a range of 2% by weight to 0% by weight to 5% by weight, and was applied for 5 minutes. After the ultrasonic vibration, the mixture was stirred for 20 hours. Thereafter, the amount of adsorption of the porous body of bisphenol A was measured. The amount of adsorption was determined from the residual _ degree of bisphenol A in the adsorption sample. The residual concentration was analyzed by the following liquid chromatography, and was determined based on the area ratio of the standard sample adjusted by g. It was determined from the adsorption adsorption isotherm (JIS Z 8 8 3 0 ) of the obtained adsorbent 羹g Freundlich. Its knot $ is shown in Table 1. (Liquid chromatography conditions) Column: Shimpak VP-ODS (Shimadzu Corporation (shares), 4. 6mm (inside diameter) xl50mm) Flow rate: 0. 8mL/min
溫度：40°C 偵測器UV220nm 移動相：乙腈：水=6 : 4 -39- 200842155 [表2] 相對於多孔體中之高分子 物質的分子鑄型之比例 [質量％1 吸附等溫式 [mg/g] 實施例7 5 23.4C0·57 實施例8 2 16.2 C0·70 實施例9 1 4.87 C°54 實施例10 0 6.9 C°76 上述表中，「C」爲雙酚A之平衡時的殘餘濃度（g/L )。藉由上述吸附等溫式可得知相對於雙酚A之平衡時溶 液中的殘餘濃度爲基準之對吸附材1 g之雙酚A的吸附量 (mg )。 吸附率爲50% (亦即雙酚A的殘餘濃度爲0.0065g/L (C = 0· 0 06 5 ))時的吸附量可算出如表3所示。 [表3] 相對於多孔體中之高分子 物質的分子鑄型之比例 mm%] 多孔體每單位質量之雙酚 A吸附量 『mg/gl 實施例7 5 1.32 實施例8 2 0.48 實施例9 1 0.32 實施例10 0 0.15 由表3的結果可知：藉由導A分子禱型至多孔體中 可提高吸附性能。藉由使分子禱型的量作成1重量份' 2 重量份 重爨份，與未用分子鑄型之實施例1 0比較，分 -40- 200842155 別可發揮約2倍、約3倍、及約9倍的吸附性能。 對實施例7〜9的多孔體之截面以電子顯微鏡照相（ 1 000倍）進行觀察。圖5、6及7分別爲表示實施例7、8 及9中得到的多孔體之截面之電子顯微鏡照相（倍率1 〇〇〇 倍）。對任一多孔體皆就附著於細孔壁之機能性塡充材（ 分子鑄型）粒子進行觀察。依實施例7、實施例8及實施 例9的順序，可觀察到機能性塡充材（分子鑄型）粒子係 依序增加。於本實施例之情況，分子鑄型與構成多孔體的 高分子物質之溶解度參數的差爲1.4。吾人認爲，於分子 鑄型表面，藉由表面改質而存在有羧基，藉由其與構成多 孔體的高分子物質之相互作用，分子鑄型之粒子會相連而 固定於多孔體表面。 再就除了於參考例1中得到之分子鑄型的量改爲1 0 重量份或1 5重量份之外係以與實施例7同樣的方法得到 的多孔體之截面，亦藉由電子顯微鏡進行觀察，得知：依 分子鑄型的量爲1重量份、2重量份、5重量份、10重量 份及1 5重量份的順序，可觀察到在多孔體表面的分子鑄 型粒子依序增多。 圖8爲爲實施例1 0中得到之多孔體的電子顯微鏡照 相（35倍、100倍、1〇〇〇倍、2000倍）。當然未能觀察 到機能性塡充材的粒子。 (實施例1 1 ) 將作爲高分子物質之乙烯-乙酸乙烯酯共聚物（EVA， -41 - 200842155 三井-杜邦聚合化學（股）製，商品名··艾巴弗列克斯 P 1 007，密度：0.93g/ml，溶解度參數：8.5 ) 100重量份 、作爲第一氣孔形成劑之季戊四醇（廣榮化學工業（股） 製，商品名：片塔利特）22 5重量份、作爲第二氣孔形成 劑之聚環氧乙烷（住友精化（股）製，商品名：PEO-18Z )2 2 5重量份、作爲發泡劑之偶氮二甲酿胺（大塚化學（ 股）製，商品名：優尼佛姆AZ ) 4.5重量份、以及界面活 性劑（花王（股）製，商品名：艾雷克特羅斯特利巴-T S -5 ) 1重量份、交聯劑（日本油脂（股）製，商品名：巴枯 密爾）0.8重量份、及參考例4中得到之二甲基丙烯酸甘 油酯5重量份用輥進行混練（混練溫度：1 5 0 °C )。將混 練物用加壓成形機（衝壓力5 0噸）於1 5 0 °C加熱5分鐘後 ，將其冷卻，得到250mmx250mmx厚度3mm的成形物。 然後，將該成形物置放於高溫槽中之氟樹脂片上，藉由在 2 3 加熱5分鐘使成形物發泡。 然後，使該成形物浸漬於水槽中4 0 °C的水中，於表3 所不之實施例4之卒取時間欄位的萃取時間（5〜9 0小時） 之間，邊以攪拌機攪拌水下邊萃取出氣孔形成劑。萃取後 ，使成形物於4 0 °C乾燥爐中乾燥2 4小時，得到形成有連 續氣泡的多孔體。 (實施例1 2 ) 將作爲高分子物質之乙燃-乙酸乙;)：希酯共聚物（E V A， 二井-杜邦聚合化學（股）製’商品名：艾巴弗列克斯 -42- 200842155 P 1 007，密度：〇.93g/ml，溶解度參數：8·5) 100重量份 、作爲第一氣孔形成劑之季戊四醇（廣榮化學工業（股） 製，商品名：片塔利特）22 5重量份、作爲第二氣孔形成 劑之聚環氧乙烷（住友精化（股）製，商品名：PEO-18Z )225重量份、作爲發泡劑之偶氮二甲醯胺（大塚化學（ 股）製，商品名：優尼佛姆AZ ) 4 · 5重量份、以及界面活 性劑（花王（股）製，商品名：艾雷克特羅斯特利巴-TS-5 ) 1重量份、交聯劑（日本油脂（股）製，商品名：巴枯 密爾）〇. 8重量份、及上述參考例3中得到之二甲基丙烯 酸乙二醇酯5重量份用輥進行混練（混練溫度：1 50 °C ) 。將混練物用加壓成形機（衝壓力50噸）於150°C加熱5 分鐘後，將其冷卻，得到 250mmx250mmx厚度 3mm的成 形物。然後，將該成形物置放於高溫槽中之氟樹脂片上， 藉由在2 3 0 °C加熱5分鐘使成形物發泡。 然後，使該成形物浸漬於水槽中4 0 °C的水中9 0小時 ，邊以攪拌機攪拌水下邊萃取出氣孔形成劑。萃取後，使 成形物於40 °C乾燥爐中乾燥24小時，得到形成有連續氣 泡的多孔體。 (實施例1 3 ) 將作爲高分子物質之乙烯-乙酸乙烯酯共聚物（EVA， 三井-杜邦聚合化學（股）製，商品名：艾巴弗列克斯 P 1 007，密度：〇.93g/ml，溶解度參數：8.5) 100重量份 、作爲第一氣孔形成劑之季戊四醇（廣榮化學工業（股） -43- 200842155 製，商品名：片塔利特）225重量份、作爲第二氣孔形成 劑之聚環氧乙烷（住友精化（股）製），商品名·· PEO-18Z ) 22 5重量份、作爲發泡劑之偶氮二甲醯胺（大塚化 學（股）製，商品名：優尼佛姆AZ ) 4 · 5重量份、以及界 面活性劑（花王（股）製，商品名：艾雷克特羅斯特利 巴-TS-5 ) 1重量份、交聯劑（日本油脂（股）製，商品名 :巴枯密爾）〇 · 8重量份、及上述參考例2中得到之苯乙 烯-二乙烯基苯共聚物5重量份用輥進行混練（混練溫度 :1 5 0 °C )。將混練物用加壓成形機（衝壓力5 0噸）於 150°C加熱5分鐘後，將其冷卻，得到25 0mmx2 5 0mmx厚 度3 mm的成形物。然後，將該成形物置放於高溫槽中之 氟樹脂片上，藉由在2 3 0 °C加熱5分鐘使成形物發泡。 然後，使該成形物浸漬於水槽中4 0 °C的水中9 0小時 ，邊以攪拌機攪拌水下邊萃取出氣孔形成劑。萃取後，使 成形物於40 °C乾燥爐中乾燥24小時，得到形成有連續氣 泡的多孔體。 圖9、1 0及1 1爲爲實施例1 1〜1 3中得到之含入有機 能性塡充材的多孔體截面之電子顯微鏡照相。各圖中’右 下爲35倍、左下爲1〇〇倍、右上爲1〇〇〇倍、左上爲2000 倍的照相。溶解度參數與構成多孔體之高分子物質最近似 的二甲基丙烯酸甘油酯聚合物粒子，和與構成多孔體之高 分子物質之溶解度參數的差較大的二甲基丙烯酸乙二醇酯 聚合物粒子相比，可於多孔體的細孔壁面觀察到較多。 -44- 200842155 (實施例1 4 ) 將作爲高分子物質之聚乙烯樹脂（旭化成（股）製， 商品名：桑特克LD F2225 ’由溶劑溶解性以實驗求出的 溶解度參數爲8 · 1 ’熔點1 1 2 °C ) 1 〇 〇重量份、作爲第一氣 孔形成劑之季戊四醇（廣榮化學工業（股）製，商品名： 片塔利特）22 5重量份、作爲第二氣孔形成劑之聚環氧乙 烷（住友精化（股）製’商品名：Ρ Ε Ο - 1 8 Z ) 2 2 5重量份 、作爲發泡劑之偶氮二甲醯胺（大塚化學（股）製，商品 名：優尼佛姆AZ ) 4 · 5重量份、以及界面活性劑（花王（ 股）製，商品名：艾雷克特羅斯特利巴-TS-5) 1重量份、 交聯劑（日本油脂（股）製，商品名：巴枯密爾）〇. 8重 量份、及上述參考例4中得到之二甲基丙烯酸甘油酯聚合 物粒子5重量份用輥進行混練（混練溫度：1 5 0 °C )。將 混練物用加壓成形機（衝壓力5 0噸）於1 5 0 °C加熱5分鐘 後，將其冷卻，得到2 5 0 m m X 2 5 0 m m X厚度 3 m m的成形物 。然後，將該成形物置放於高溫槽中之氟樹脂片上，藉由 在23 0 t加熱5分鐘使成形物發泡。 使該成形物浸漬於水槽中4 0 °C的水中，於表4之實施 例4的萃取時間欄位所示之萃取時間（5〜90小時）之間， 邊以攪拌機攪拌水下邊萃取出氣孔形成劑。萃取後，使成 形物於4(TC乾燥爐中乾燥24小時，得到形成有連續氣泡 的多孔體。 (實施例1 5 ) -45- 200842155 將作爲高分子物質之聚乙烯樹脂（PE、旭化成（ 製，商品名：桑特克LD F2225 ) 1 00重量份、作爲第 孔形成劑之季戊四醇（廣榮化學工業（股）製，商品 片塔利特）225重量份、作爲第二氣孔形成劑之聚環 烷（住友精化（股）製，商品名：Ρ Ε Ο -1 8 Z ) 2 2 5重 、作爲發泡劑之偶氮二甲醯胺（大塚化學（股）製， 名：優尼佛姆AZ ) 4·5重量份、以及界面活性劑（花 股）製，商品名：艾雷克特羅斯特利巴-TS-5 ) 1重量 交聯劑（日本油脂（股）製，商品名：巴枯密爾）〇. 量份、及上述參考例3中得到之二甲基丙烯酸乙二醇 合物粒子5重量份用輥進行混練（混練溫度：1 5 0 °C 將混練物用加壓成形機（衝壓力50噸）於150 °C加熱 鐘後，將其冷谷卩，得到 250mmx250mmx厚度 3mm的 物。然後，將該成形物置放於高溫槽中之氟樹脂片上 由在2 3 0 °C加熱5分鐘使其發泡。 然後，使該成形物浸漬於水槽中40°C的水中90 ，邊以攪拌機攪拌水下邊萃取出氣孔形成劑。萃取後 成形物於4 0 °C乾燥爐中乾燥2 4小時，得到形成有連 泡的多孔體。 (實施例1 6 ) 將作爲高分子物質之聚乙烯樹脂（PE、旭化成（ 製，商品名：桑特克LDF2225) 100重量份、作爲第 孔形成劑之季戊四醇（廣榮化學工業（股）製’商品 股） 一氣 名： 氧乙 量份 商品 王（ 份、 8重 酯聚 )〇 5分 成形 ，藉 小時 ，使 續氣 股） 一氣 名· -46- 200842155 片塔利特）225重量份、作爲第二氣孔形成劑之聚環氧乙 烷（住友精化（股）製，商品名·· PEO-18Z ) 225重量份 、作爲發泡劑之偶氮二甲醯胺（大塚化學（股）製，商品 名：優尼佛姆AZ ) 4 · 5重量份、以及界面活性劑（花王（ 股）製，商品名：艾雷克特羅斯特利巴-TS-5 ) 1重量份、 交聯劑（日本油脂（股）製，商品名：巴枯密爾）0 · 8重 量份、及上述參考例2中得到之苯乙烯-二乙烯基苯共聚 物粒子5重量份用輥進行混練（混練溫度·· 1 5 0 °C )。將 混練物用加壓成形機（衝壓力5 0噸）於1 5 (TC加熱5分鐘 後，將其冷卻，得到2 5 0 m m X 2 5 0 m m X厚度3 m m的成形物 。然後，將該成形物置放於高溫槽中之氟樹脂片上，藉由 在23 0 °C加熱5分鐘使其發泡。 然後，使該成形物浸漬於水槽中4(TC的水中90小時 ，邊以攪拌機攪拌水下邊萃取出氣孔形成劑。萃取後，使 成形物於4 0 °C乾燥爐中乾燥2 4小時，得到形成有連續氣 泡的多孔體。 圖1 2、1 3及1 4爲爲實施例1 4〜1 6中得到之含入有機 能性塡充材的多孔體截面之電子顯微鏡照相。各圖中，右 下爲35倍、左下爲100倍、右上爲1000倍、左上爲2000 倍的照相。與實施例1 1〜1 3同樣地，溶解度參數與構成多 孔體之高分子物質最近似的二甲基丙烯酸甘油酯聚合物粒 子，和與構成多孔體之高分子物質之溶解度參數的差較大 的二甲基丙烯酸乙二醇酯聚合物粒子及苯乙烯-二乙烯基 苯共聚物粒子相比，可於多孔體的細孔壁面觀察到較多。 -47- 200842155 (比較例4 ) 將作爲高分子物質之乙烯-乙酸乙烯酯共 三井-杜邦聚合化學（股）製，商品名：] P 1 007 ) 1 00重量份、作爲第一氣孔形成劑 廣榮化學工業（股）製，商品名：片塔利特 、作爲第二氣孔形成劑之聚環氧乙烷（住友 ，商品名：PEO-18Z) 225重量份、以及界 王（股）製，商品名：艾雷克特羅斯特利巴. 份、交聯劑（日本油脂（股）製，商品名 〇·8重量份用輥進行混練（混練溫度：150°C 用加壓成形機（衝壓力5 0噸）於1 5 0 °C加熱 其冷卻，得到250mmx250mmx厚度3mm的成 然後，使該成形物浸漬於水槽中40°C的 所示之比較例2之萃取時間欄位的萃取時間 之間，邊以攪拌機攪拌水下邊萃取出氣孔形 ，使成形物於4 0 °C乾燥爐中乾燥2 4小時， 續氣泡的多孔體。 (比較例5 ) 除了用聚乙烯樹脂（PE、旭化成（股） 桑特克LD F2225 )作爲高分子物質之外，係 同樣的方法得到多孔體。 於實施例7〜1 6及比較例4、5中得到的 聚物（EVa， 文巴弗列克斯 之季戊四醇（ )225重量ί分 精化（股）製 面活性劑（花 -TS-5) 1 重纛 :巴枯密爾） )。將混練物 5分鐘後，將 形物。 水中，於表4 (5〜9 0小時） 成劑。萃取後 得到形成有連 製，商品名： 以與比較例4 多孔體之氣孔 -48- 200842155 率及透水性係以上述方法測定。將測定結果與調配比一倂 示於表4。 -49- 200842155 [表4] 高分子 物質 發泡劑 機能性塡充材 成形物厚度 [mm] 成形物之製造 多孔儀 1性能 種類 重量份 發泡步驟 萃取時間 [小時] 氣孔率 [容積％] 透水性 [秒] 實施例7 EVA 有 參考例1 5 3 有 90 81 實施例8 EVA 有 參考例1 2 3 有 90 83 實施例9 EVA 有 參考例1 1 3 有 90 84 實施例10 EVA 有 — — 3 有 90 85 實施例11 EVA 有 參考例4 5 3 有 5 55 10 77 20 80 40 81 20 90 82 10 實施例12 EVA 有 參考例3 5 3 有 90 81 實施例13 EVA 有 參考例2 5 3 有 90 81 實施例14 PE 有 參考例4 5 3 有 5 52 10 74 20 78 40 79 40 90 80 30 實施例15 PE 有 參考例3 5 3 有 90 80 實施例16 PE 有 參考例2 5 3 有 90 80 比較例4 EVA 無 3 無 5 25 10 43 20 70 40 76 220 90 80 70 比較例5 PE 無 3 無 5 21 10 39 20 67 40 73 350 90 77 140 -50- 200842155 圖1 5爲表示實施例1 1及比較例4中之氣孔率與萃取 時間之關係的曲線圖。可知：於經過發泡步驟製作之實施 例1 1的多孔體，於萃取時間爲大約1 5小時的階段，可萃 取至氣孔率達到飽和狀態，其氣孔率，無關乎塡充有5質 量份機能性塡充材，皆達到8 0容積％以上。另一方面，於 未經發泡步驟製作之比較例4的多孔體，須40〜60小時之 長時間萃取率方可達到飽和。又，比較例4之氣孔率無關 乎未塡充機能性塡充材，僅能達到80容積％的程度。 又，經發泡步驟製作之實施例1 1的多孔體，透水時 間短，其透水性非常良好。另一方面，未經發泡步驟製作 之比較例4的多孔體，透水時間長，其透水性差。 圖1 6爲表示實施例1 4及比較例5中之氣孔率與萃取 時間之關係的曲線圖。可知：於經過發泡步驟製作之實施 例1 4的多孔體，於萃取時間爲大約20小時的階段，可萃 取至氣孔率達到飽和狀態，其氣孔率，無關乎塡充有5質 量份機能性塡充材，皆達到80容積％以上。另一方面，於 未經發泡步驟製作之比較例5的多孔體，須60〜80小時之 長時間萃取率方可達到飽和。又，比較例5之氣孔率無關 乎未塡充機能性塡充材，爲77容積％的程度，較實施例 14低。 又，經發泡步驟製作之實施例1 4的多孔體’透水時 間短，其透水性非常良好。另一方面’未經發泡步驟製作 之比較例4的多孔體，透水時間長，其透水性差。 綜合上述者觀之可知：於使用發泡劑在萃取步驟前使 -51 - 200842155 成形物發泡的情況，與無發泡步驟的情況比較，氣孔率較 高。其理由吾人認爲在於藉由發泡步驟使得成形物蓬鬆而 可相應地提高氣孔率。亦即，可知藉由使用發泡劑在萃取 步驟前使成形物發泡，可用較少的材料以較短的萃取時間 得到咼氣孔率的多孔體。藉此可壓低加工費。再者，得到 之多孔體’由透水性試驗的結果可得知其爲透水性良好之 形成有連續氣泡的多孔體。 (實施例1 7 ) 將作爲筒分子物質之乙燃-乙酸乙；)：希酯共聚物（三井-杜邦聚合化學（股）製，商品名：艾巴弗列克斯P i 〇 〇 7， 密度：0.93g/ml，溶解度參數：8·5 ) 1〇〇重量份、作爲第 一氣孔形成劑之季戊四醇（廣榮化學工業（股）製，商品 名：片塔利特）22 5重量份、作爲第二氣孔形成劑之聚環 氧乙烷（住友精化（股）製，商品名：ρ Ε Ο -1 8 Ζ ) 2 2 5重 量份、作爲發泡劑之偶氮二甲醯胺（大塚化學（股）製， 商品名：優尼佛姆ΑΖ ) 4.5重量份、以及界面活性劑（花 王（股）製，商品名：艾雷克特羅斯特利巴-T S - 5 ) 1重量 份及交聯劑（雙異苯丙過氧化物）0.8重量份、及市售之 膠體型強酸性陽離子交換樹脂（交聯化聚苯乙烯磺酸鈉型 陽離子交換樹脂、粒徑範圍200〜240// m ( 85 %以上），表 觀密度：8 05 §/1^，水分：52〜55.5%)100重量份用輥進行 混練（混練溫度：1 5 0 °C )。 將得到的混練物用二軸擠壓基（螺桿徑20mm )，於 -52- 200842155 缸體溫度1 5 0 °C下進行擠壓成形，得到直徑3 mm的圓柱狀 成形物。將此圓柱狀成形物切斷成長度1 0cm，插入內徑 3.5mm、外徑4.5mm的玻璃管中。將插入玻璃管中之圓柱 狀成形物置入恆溫槽中，藉由在250°C下加熱使其發泡。 發泡後，將玻璃管破壞取出圓柱狀之發泡成形物。 然後，使該成形物浸漬於水槽中40 °C的水中，於90 小時之間，邊以攪拌機攪拌水下邊萃取出氣孔形成劑。萃 取後，使成形物於40°C乾燥爐中乾燥24小時，得到形成 有連續氣泡的多孔體。 (實施例1 8 ) 以與實施例1 7同樣的做法得到之混練物，用加壓成 形機（衝壓力5 0噸）於1 5 0 °C加熱5分鐘後，將其冷卻， 得到2 5 0 m m X 2 5 0 m m X厚度3 m m的片狀成形物。然後，將 該成形物置放於高溫槽中之氟樹脂片上，藉由在23(TC加 熱5分鐘使其發泡。 然後，使該成形物浸漬於水槽中4 0 °C的水中9 0小時 ’邊以攪拌機攪拌水下邊萃取出氣孔形成劑。萃取後，使 成形物於40 °C乾燥爐中乾燥24小時，得到形成有連續氣 泡片狀的多孔體。 測定實施例1 7、1 8中得到之多孔體的氣孔率及離子 交換容量。實施例1 8亦測定透水性。離子交換容量係以 下述步驟測定。組成物之調配比與多孔體之評價結果示於 表 5、6。 -53- 200842155 離子交換容量之測定方法 將約〇.5g之試料置入；joomL燒瓶中，用甲 水各進行1 0分鐘的超音波處理。然後，將試料 輕拭除，將試料浸漬於1.5M-鹽酸水溶液20mL 以攪拌棒輕壓表面以除去空氣，一邊施加超音波 然後，取出試料，將試料浸漬於新的1.5M-鹽 2 OmL中，再同前施加超音波3小時。其後，以 分洗淨，將水去除後使試料移入玻璃皿中，使其 一晚。將經乾燥之試料移入1 0 0 m L的三角燒瓶 1M-氯化鈉水溶液20mL，以薄膜蓋住，於邊施加 使試料浸漬於1 M-氯化鈉水溶液中6小時。然後 爲指示劑之酚酞0 . 1 m L，使用0.1 Μ -氫氧化鈉水 滴定。用 〇 · 1 Μ -鹽酸水溶液對〇 . 1 Μ -氫氧化鈉水 其校正因子（factor )値，進行測定値之修正。 出離子交換能Q。 離子交換能Q[meq./g]=xyf/m X :氫氧化鈉溶液之濃度[N] y :滴定量[mL] m :試料質量（乾燥質量）[g] f :氫氧化鈉溶液之較正因子値 醇及超純 的水氣輕 中，一邊 3小時。 酸水溶液 超純水充 真空乾燥 中，力0入 超音波下 ，加入作 溶液進行 溶液求出 用下式求 -54- 200842155 [表5] 高分子物質 第一氣孔 第二氣孔 發泡劑 界面 交聯劑 機能性塡充材 形成劑 形成劑 活性劑 種類 重量份 重量份 重量份 重量份 重量份 重量份 種類 重量份 實施例 17 ' 18 EVA 100 225 225 45 1 0.8 離子交 換樹脂 100 [表6] 成形物之發泡與萃取 多孔體性能 發泡步驟 萃取時間 [小時] 氣孔率 Γ%1 透水性 [秒] 離子交換容量 [meq./dry-g] 實施例17 有 80 78 1.44 實施例18 有 90 80 10 1.44 如上表所示般，藉由用離子交換樹脂作爲機能性塡充 材，可得到有高離子交換能之圓柱狀或片狀的多孔體。圓 柱狀的多孔體可有效地適用於作爲平板型管柱。 【圖式簡單說明】 圖1爲表示透水性測定裝置之示意圖。 圖2爲表示實施例1、實施例2及比較例1的萃取時 間與多孔體的氣孔率之關係的曲線圖。 圖3爲表示實施例3、實施例4及比較例2的萃取時 間與多孔體的氣孔率之關係的曲線圖。 圖4爲表示實施例5、實施例6及比較例3的萃取時 間與多孔體的氣孔率之關係的曲線圖。 圖5爲實施例7中得到之多孔體的電子顯微鏡照相（ -55- 200842155 倍率1 ο ο 〇倍）。 圖6爲實施例8中得到之多孔體的電子顯微鏡照相（ 倍率1 0 0 0倍）。 圖7爲實施例9中得到之多孔體的電子顯微鏡照相（ 倍率1 〇 〇 〇倍）。 圖8爲實施例1 〇中得到之多孔體的電子顯微鏡照相 (右下：35倍、左下：100倍、右上：1〇0〇倍、左上： 2〇〇〇 倍）。 ® 9爲實施例1 1中得到之多孔體的電子顯微鏡照相 (右下：35倍、左下：1〇〇倍、右上：1 000倍、左上： 200〇 倍）。 圖1 0爲實施例1 2中得到之多孔體的電子顯微鏡照相 (右下：35倍、左下：100倍、右上：1〇〇〇倍、左上： 2000 倍）。 ® 1 1爲實施例1 3中得到之多孔體的電子顯微鏡照相 (右下：35倍、左下：100倍、右上：1000倍、左上： 2000 倍）。 1 2爲實施例1 4中得到之多孔體的電子顯微鏡照相 (右下：35倍、左下：1〇〇倍、右上·· 1000倍、左上： 2〇〇〇 倍）。 1 3爲實施例1 5中得到之多孔體的電子顯微鏡照相 :35倍、左下·· 100倍、右上：1000倍、左上： 圖 (右下 2〇〇〇 倍 ® 1 4爲實施例1 6中得到之多孔體的電子顯微鏡照相 -56 - 200842155 (右下：3 5倍、左下：1 〇 0倍、右上：10 0 〇倍、左上： 2 0 00 倍）〇 圖1 5爲表示實施例1 1及比較例4中之萃取時間與多 孔體的氣孔率之關係的曲線圖。 圖1 6爲表示實施例1 4及比較例中之萃取時間與多孔 體的氣孔率之關係的曲線圖。 【主要元件符號說明】 1 :多孔體 2 :過濾用濾材固定器 3 :附減壓泵連接口容器 4 :夾鉗 5 :減壓泵連接口 -57-Temperature: 40 ° C Detector UV 220 nm Mobile phase: acetonitrile: water = 6 : 4 - 39 - 200842155 [Table 2] Relative to the molecular mold of the polymer substance in the porous body [mass % 1 adsorption isotherm [mg/g] Example 7 5 23.4C0·57 Example 8 2 16.2 C0·70 Example 9 1 4.87 C°54 Example 10 0 6.9 C°76 In the above table, "C" is the balance of bisphenol A. Residual concentration at time (g/L). According to the above adsorption isotherm, the amount (mg) of adsorption of 1 g of bisphenol A to the adsorbent based on the residual concentration in the solution at the equilibrium of bisphenol A can be known. The adsorption amount at the time of the adsorption rate of 50% (that is, the residual concentration of bisphenol A was 0.0065 g/L (C = 0·0 06 5 )) was calculated as shown in Table 3. [Table 3] The ratio of the molecular mold to the polymer material in the porous body mm%] The amount of bisphenol A adsorbed per unit mass of the porous body "mg/gl Example 7 5 1.32 Example 8 2 0.48 Example 9 1 0.32 Example 10 0 0.15 From the results of Table 3, it is understood that the adsorption performance can be improved by guiding the A molecule to the porous body. By making the molecular prayer type into 1 part by weight of '2 parts by weight by weight, compared with the example 10 of the unused molecular mold, the number -40-200842155 can be about 2 times, about 3 times, and About 9 times the adsorption performance. The cross sections of the porous bodies of Examples 7 to 9 were observed by electron microscopy (1,000 times). Figs. 5, 6 and 7 are electron micrographs (magnification: 1 倍) showing the cross sections of the porous bodies obtained in Examples 7, 8, and 9, respectively. Any of the porous bodies was observed for the functional sputum (molecular mold) particles attached to the pore walls. According to the procedures of Example 7, Example 8, and Example 9, it was observed that the functional entangled material (molecular mold) particle system was sequentially increased. In the case of this embodiment, the difference in solubility parameter between the molecular mold and the polymer material constituting the porous body was 1.4. It is believed that on the surface of the molecular mold, a carboxyl group is present by surface modification, and by interaction with a polymer substance constituting the porous body, the particles of the molecular mold are connected and fixed to the surface of the porous body. The cross section of the porous body obtained in the same manner as in Example 7 except that the amount of the molecular mold obtained in Reference Example 1 was changed to 10 parts by weight or 15 parts by weight, and was also carried out by an electron microscope. It was observed that, in the order of 1 part by weight, 2 parts by weight, 5 parts by weight, 10 parts by weight, and 15 parts by weight of the molecular mold, it was observed that the molecular mold particles on the surface of the porous body were sequentially increased. . Fig. 8 is an electron microscope photograph (35 times, 100 times, 1 inch, 2000 times) of the porous body obtained in Example 10. Of course, the particles of functional sputum were not observed. (Example 1 1 ) An ethylene-vinyl acetate copolymer (EVA, -41 - 200842155, manufactured by Mitsui & DuPont Polymer Chemicals Co., Ltd., trade name · Aba Fleix P 1 007, Density: 0.93 g/ml, solubility parameter: 8.5) 100 parts by weight of pentaerythritol as a first pore-forming agent (manufactured by Kwong Wing Chemical Industry Co., Ltd., trade name: Tablet Talit) 22 5 parts by weight, as a second a polyethylene oxide of a pore-forming agent (manufactured by Sumitomo Seika Co., Ltd., trade name: PEO-18Z), 2 2 5 parts by weight, and a azo urethane as a foaming agent (manufactured by Otsuka Chemical Co., Ltd.) Product name: Unifoam AZ) 4.5 parts by weight, and surfactant (made by Kao (stock), trade name: Elektrostroma-TS -5) 1 part by weight, crosslinker (Japanese fat 0.8 parts by weight of the product (trade name: Bacum Mill) and 5 parts by weight of the glycerol dimethacrylate obtained in Reference Example 4 were kneaded by a roll (kneading temperature: 150 ° C). The kneaded product was heated at 150 ° C for 5 minutes by a press molding machine (pressure of 50 tons), and then cooled to obtain a molded product of 250 mm x 250 mm x thickness of 3 mm. Then, the molded product was placed on a fluororesin sheet in a high temperature bath, and the molded product was foamed by heating at 2 3 for 5 minutes. Then, the formed product was immersed in water at 40 ° C in a water bath, and stirred in a mixer with the extraction time (5 to 90 hours) of the stroke time field of Example 4 in Table 3. The pore former is extracted underneath. After the extraction, the molded product was dried in a drying oven at 40 ° C for 24 hours to obtain a porous body in which continuous bubbles were formed. (Example 1 2) Ethylene-acetate as a polymer substance;): H-ester copolymer (EVA, manufactured by Mitsui-DuPont Polymer Chemicals Co., Ltd.) Trade name: Aiba Flix-42- 200842155 P 1 007, density: 〇.93 g/ml, solubility parameter: 8·5) 100 parts by weight of pentaerythritol as a first pore-forming agent (manufactured by Kwong Wing Chemical Industry Co., Ltd., trade name: Tablet Talit) 22 5 parts by weight of polyethylene oxide (manufactured by Sumitomo Seika Co., Ltd., trade name: PEO-18Z) as a second pore-forming agent, 225 parts by weight, azo dimethyl hydrazine as a foaming agent (Otsuka Chemical Co., Ltd.) (share) system, trade name: Unifrom AZ) 4 · 5 parts by weight, and surfactant (made by Kao (stock), trade name: Elektrostroma-TS-5) 1 part by weight And a crosslinking agent (manufactured by Nippon Oil & Fats Co., Ltd., trade name: Bacum Mill) 8. 8 parts by weight, and 5 parts by weight of ethylene glycol dimethacrylate obtained in the above Reference Example 3, kneaded by a roller ( Mixing temperature: 1 50 °C). The kneaded product was heated at 150 ° C for 5 minutes by a press molding machine (pressure: 50 tons), and then cooled to obtain a molded product of 250 mm x 250 mm x thickness of 3 mm. Then, the molded product was placed on a fluororesin sheet in a high temperature bath, and the molded product was foamed by heating at 230 ° C for 5 minutes. Then, the molded product was immersed in water at 40 ° C for 90 hours in a water bath, and the pore former was extracted while stirring under a stirrer. After the extraction, the molded product was dried in a drying oven at 40 °C for 24 hours to obtain a porous body in which continuous bubbles were formed. (Example 1 3) Ethylene-vinyl acetate copolymer (EVA, manufactured by Mitsui-DuPont Polymer Chemicals Co., Ltd., trade name: Aibaflex P 1 007, density: 〇.93 g) /ml, solubility parameter: 8.5) 100 parts by weight of pentaerythritol as a first pore-forming agent (manufactured by Kwong Wing Chemical Industry Co., Ltd. -43-200842155, trade name: Tablet Talit) 225 parts by weight as a second pore Forming agent of polyethylene oxide (manufactured by Sumitomo Seika Co., Ltd., trade name · PEO-18Z) 22 5 parts by weight, azo dimethyl hydrazine as a foaming agent (manufactured by Otsuka Chemical Co., Ltd.) Product name: Unifrom AZ) 4 · 5 parts by weight, and surfactant (made by Kao (trade), trade name: Elektrostroma-TS-5) 1 part by weight, crosslinker ( Japanese fats and oils (stock), trade name: Bacum Mill) 8·8 parts by weight, and 5 parts by weight of the styrene-divinylbenzene copolymer obtained in the above Reference Example 2 were kneaded by a roll (kneading temperature: 1) 5 0 °C). The kneaded product was heated at 150 ° C for 5 minutes by a press molding machine (pressure of 50 tons), and then cooled to obtain a molded product of 25 0 mm x 2 50 mm x 3 mm thick. Then, the molded product was placed on a fluororesin sheet in a high temperature bath, and the molded product was foamed by heating at 260 °C for 5 minutes. Then, the molded product was immersed in water at 40 ° C for 90 hours in a water bath, and the pore former was extracted while stirring under a stirrer. After the extraction, the molded product was dried in a drying oven at 40 °C for 24 hours to obtain a porous body in which continuous bubbles were formed. Fig. 9, 10 and 11 are electron micrographs of the cross section of the porous body containing the organic chelating material obtained in Examples 1 1 to 13. In each figure, 'the lower right is 35 times, the lower left is 1〇〇 times, the upper right is 1〇〇〇 times, and the upper left is 2000 times. The dimethacrylate polymer particle having the solubility parameter closest to the polymer material constituting the porous body and the ethylene glycol dimethacrylate polymer having a large difference from the solubility parameter of the polymer material constituting the porous body Compared with the particles, much more can be observed on the pore walls of the porous body. -44- 200842155 (Example 1 4) The solubility parameter of the polyethylene resin (product of Asahi Kasei Co., Ltd., trade name: Santek LD F2225) obtained from the solvent solubility was experimentally determined to be 8 · 1 'Melting point 1 1 2 ° C ) 1 〇〇 by weight of pentaerythritol as a first pore-forming agent (manufactured by Kwong Wing Chemical Industry Co., Ltd., trade name: Talite) 22 parts by weight as a second pore formation Polyethylene oxide (Sumitomo Refinery Co., Ltd.' trade name: Ρ Ε Ο - 1 8 Z ) 2 2 5 parts by weight, azo dimethyl hydrazine as a blowing agent (Otsuka Chemical Co., Ltd.) System, trade name: Univers AZ) 4 · 5 parts by weight, and surfactant (King (stock), trade name: Aileke Trosteriba - TS-5) 1 part by weight, cross-linking (manufactured by Nippon Oil & Fats Co., Ltd., trade name: Bacum Mill) 8. 8 parts by weight, and 5 parts by weight of the glyceryl dimethacrylate polymer particles obtained in the above Reference Example 4, kneaded by a roller (kneading temperature) :1 5 0 °C ). The kneaded product was heated at 150 ° C for 5 minutes by a press molding machine (pressure of 50 tons), and then cooled to obtain a molded product having a thickness of 2 m 0 m 2 X 2 5 m m X 3 m m . Then, the molded product was placed on a fluororesin sheet in a high temperature bath, and the molded product was foamed by heating at 230 Torr for 5 minutes. The molded product was immersed in water at 40 ° C in a water bath, and extracted between the extraction time (5 to 90 hours) shown in the extraction time column of Example 4 of Table 4, while stirring under water with a stirrer. Forming agent. After the extraction, the molded product was dried in a 4 (TC drying oven for 24 hours to obtain a porous body in which continuous bubbles were formed. (Example 15) -45 - 200842155 A polyethylene resin (PE, Asahi Kasei (a polymer material)) Manufactured, trade name: Santek LD F2225) 00 parts by weight of pentaerythritol (manufactured by Kwong Wing Chemical Industry Co., Ltd., commercial product Talit) as a second pore forming agent, 225 parts by weight, as a second pore forming agent Polycycloalkane (Sumitomo Refinery Co., Ltd., trade name: Ρ Ε Ο -1 8 Z ) 2 2 5 weight, azo dimethyl hydrazine as a foaming agent (Dayu Chemical Co., Ltd., name: excellent Nifum AZ) 4·5 parts by weight, and surfactant (flower stock), trade name: Aileke Trostriba-TS-5) 1 weight cross-linking agent (made by Nippon Oil & Fats Co., Ltd.) Product name: Bacum Mill) 量. The parts and the 5 parts by weight of the ethylene glycol dimethacrylate particles obtained in the above Reference Example 3 were kneaded by a roller (kneading temperature: 150 ° C. After heating the clock at 150 °C with a press molding machine (pressure of 50 tons), it was cooled to a cold valley to obtain a thickness of 250 mm x 250 mm x. Then, the molded product was placed on a fluororesin sheet in a high temperature bath and foamed by heating at 260 ° C for 5 minutes. Then, the molded product was immersed in water at 40 ° C in a water tank 90 The pore former was extracted while stirring under a stirrer. After the extraction, the formed product was dried in a drying oven at 40 ° C for 24 hours to obtain a porous body in which bubbles were formed. (Example 16) Polyethylene resin (PE, Asahi Kasei (product name: Santek LDF2225) 100 parts by weight, pentaerythritol as a pore former (Golden Chemical Industry Co., Ltd. 'commodity stocks) One gas name: Oxygen B Commodity king (part, 8 heavy ester poly) 〇 5 minutes forming, borrowing hours, make the gas-filled stock) one gas name · -46- 200842155 tablets Talit) 225 parts by weight, as the second pore forming agent of the polyethylene oxide Alkane (Sumitomo Refinery Co., Ltd., trade name · PEO-18Z) 225 parts by weight, azo dimethyl hydrazine as a foaming agent (manufactured by Otsuka Chemical Co., Ltd., trade name: Univer AZ) 4 · 5 parts by weight, and surfactant (Kao) , trade name: Ayrek Trosteriba-TS-5) 1 part by weight, cross-linking agent (made by Nippon Oil & Fats Co., Ltd., trade name: Bacumir) 0 · 8 parts by weight, and the above reference examples 5 parts by weight of the styrene-divinylbenzene copolymer particles obtained in 2 were kneaded by a roll (kneading temperature · 150 ° C). The kneaded material was subjected to a press molding machine (pressure of 50 tons) at 1 5 (When the TC was heated for 5 minutes, it was cooled to obtain a molded product of 2500 mm X 2 50 mm X thickness 3 mm. Then, the molded product was placed on a fluororesin sheet in a high temperature bath, and was foamed by heating at 23 ° C for 5 minutes. Then, the molded product was immersed in a water bath 4 (water of TC for 90 hours, and the pore former was extracted while stirring under a stirrer. After the extraction, the molded product was dried in a drying oven at 40 ° C for 24 hours to obtain a molded product. The porous body in which the continuous bubbles are formed. Fig. 1, 2, and 3 are the electron microscope photographs of the cross section of the porous body containing the organic energy enthalpy obtained in Examples 14 to 16. The lower right is 35 times, the lower left is 100 times, the upper right is 1000 times, and the upper left is 2000 times. Similarly to the first to third embodiments, the solubility parameter is the closest to the dimethyl group constituting the porous body. The glycerin acrylate polymer particles are comparable to the ethylene glycol dimethacrylate polymer particles and the styrene-divinylbenzene copolymer particles having a large difference in solubility parameter of the polymer material constituting the porous body. The surface of the pores of the porous body was observed to be more. -47- 200842155 (Comparative Example 4) Ethylene-vinyl acetate as a polymer material was manufactured by Mitsui-DuPont Polymerization Chemical Co., Ltd., trade name:] P 1 007 ) 100 parts by weight as the first air hole Ingredients: Guangrui Chemical Industry Co., Ltd., trade name: tatarite, polyethylene oxide as second pore forming agent (Sumitomo, trade name: PEO-18Z) 225 parts by weight, and king ), the product name: Ayrek Trosteriba. Parts, cross-linking agent (made by Nippon Oil & Fats Co., Ltd., trade name 〇·8 parts by weight by kneading with a roller (kneading temperature: 150 °C by pressure forming) The machine (pressure of 50 tons) was heated and cooled at 150 ° C to obtain a 250 mm x 250 mm x thickness of 3 mm, and then the formed product was immersed in a water bath at 40 ° C in the extraction time column of Comparative Example 2 shown. Between the extraction time, the pore shape was extracted while stirring with a stirrer, and the molded body was dried in a drying oven at 40 ° C for 24 hours to continue the porous body of the bubbles. (Comparative Example 5) In addition to polyethylene resin (PE) Asahi Kasei Co., Ltd. (Sanctuary LD F2225) A porous body was obtained by the same method as a polymer material. The polymers obtained in Examples 7 to 16 and Comparative Examples 4 and 5 (EVa, Wenbuff) Leek's pentaerythritol ( ) 225 weights aliquots (strand) surfactants Flower-TS-5) 1 Heavy 纛: Bacumir)). After mixing the mixture for 5 minutes, the form is formed. In water, it is formed in Table 4 (5~90 hours). , Trade name: The porosity and the water permeability of the porous body of Comparative Example 4 were measured by the above method. The measurement results and the compounding ratio are shown in Table 4. -49- 200842155 [Table 4] Polymer Material foaming agent Functional 塡 Filling material thickness [mm] Manufacturing of shaped product Perforator 1 Performance type Weight part foaming step Extraction time [hour] Porosity [% by volume] Water permeability [seconds] Example 7 EVA Reference Example 1 5 3 Yes 90 81 Example 8 EVA Reference Example 1 2 3 Yes 90 83 Example 9 EVA Reference Example 1 1 3 Yes 90 84 Example 10 EVA Yes — 3 There are 90 85 Example 11 EVA Yes Reference Example 4 5 3 Yes 5 55 10 77 20 80 40 81 20 90 82 10 Example 12 EVA Reference Example 3 5 3 Yes 90 81 Example 13 EVA Reference Example 2 5 3 Yes 90 81 Example 14 PE Reference Example 4 5 3 Yes 5 52 10 74 20 78 40 79 40 90 80 30 Example 15 PE Reference Example 3 5 3 Yes 90 80 Example 16 PE Reference Example 2 5 3 Yes 90 80 Comparative Example 4 EVA No 3 No 5 25 10 43 20 70 40 76 220 90 80 70 Comparative Example 5 PE No 3 No 5 21 10 39 20 67 40 73 350 90 77 140 -50- 200842155 Figure 15 is a graph showing the relationship between the porosity and the extraction time in Example 1 1 and Comparative Example 4. It can be seen that the porous body of Example 11 produced by the foaming step can be extracted until the porosity reaches a saturated state at a stage of extraction time of about 15 hours, and the porosity thereof is irrelevant to 5 parts by mass. The sputum filling materials are all above 80% by volume. On the other hand, the porous body of Comparative Example 4 which was produced without the foaming step was subjected to a long extraction time of 40 to 60 hours to reach saturation. Further, the porosity of Comparative Example 4 was only about 80% by volume, irrespective of the unfilled functional enthalpy. Further, the porous body of Example 1 produced by the foaming step had a short water permeability and a very good water permeability. On the other hand, the porous body of Comparative Example 4 which was produced without the foaming step had a long water permeable time and was inferior in water permeability. Fig. 16 is a graph showing the relationship between the porosity and the extraction time in Example 14 and Comparative Example 5. It can be seen that the porous body of Example 14 produced by the foaming step can be extracted until the porosity reaches a saturated state at a stage of extraction time of about 20 hours, and the porosity thereof is irrelevant to 5 mass parts of functionality. The enamel filling materials all reach 80% by volume or more. On the other hand, the porous body of Comparative Example 5 which was produced without the foaming step was subjected to a long extraction time of 60 to 80 hours to reach saturation. Further, the porosity of Comparative Example 5 was lower than that of Example 14 irrespective of the unfilled functional enthalpy, which was 77% by volume. Further, the porous body of Example 14 produced by the foaming step had a short water permeable time and a very good water permeability. On the other hand, the porous body of Comparative Example 4 which was produced without the foaming step had a long water permeable time and was inferior in water permeability. In view of the above, it is known that the foaming agent is used to foam the molded product of -51 - 200842155 before the extraction step, and the porosity is higher as compared with the case of the non-foaming step. The reason for this is considered to be that the porosity of the molded body is made by the foaming step, and the porosity is accordingly increased. That is, it is understood that the formed body is foamed by using a foaming agent before the extraction step, and a porous body having a helium porosity can be obtained with a shorter extraction time with less material. This can reduce the processing fee. Further, as a result of the water permeability test, the obtained porous body ' was found to be a porous body in which continuous bubbles were formed with good water permeability. (Example 1 7) Ethylene-acetic acid B as a molecular substance of a cartridge;): a homopolymer (manufactured by Mitsui-DuPont Polymer Chemicals Co., Ltd., trade name: Aba Flix P i 〇〇7, Density: 0.93 g/ml, solubility parameter: 8·5) 1 part by weight, pentaerythritol as a first pore-forming agent (manufactured by Kwong Wing Chemical Industry Co., Ltd., trade name: Tablet Talit) 22 parts by weight Polyethylene oxide as a second pore-forming agent (manufactured by Sumitomo Seika Co., Ltd., trade name: ρ Ε Ο -1 8 Ζ ) 2 2 5 parts by weight, azo dimethyl hydrazine as a foaming agent (Otsuka Chemical Co., Ltd., trade name: Univerfol) 4.5 parts by weight, and surfactant (King (stock), trade name: Elektrostroma - TS - 5) 1 weight And cross-linking agent (bisisophenylpropionate) 0.8 parts by weight, and commercially available colloidal strong acid cation exchange resin (crosslinked polystyrene sulfonate sodium type cation exchange resin, particle size range 200~240 // m (85% or more), apparent density: 8 05 §/1^, moisture: 52 to 55.5%) 100 parts by weight by roller ( Mixing temperature: 1 50 °C). The obtained kneaded product was extruded by a biaxial pressing base (screw diameter: 20 mm) at -52 to 200842155 at a cylinder temperature of 150 ° C to obtain a cylindrical molded product having a diameter of 3 mm. This cylindrical molded product was cut into a length of 10 cm, and inserted into a glass tube having an inner diameter of 3.5 mm and an outer diameter of 4.5 mm. The cylindrical shaped insert inserted into the glass tube was placed in a thermostatic chamber and foamed by heating at 250 °C. After the foaming, the glass tube was broken to take out a cylindrical foam molded product. Then, the molded product was immersed in water at 40 ° C in a water bath, and the pore former was extracted while stirring under a stirring machine for 90 hours. After the extraction, the molded product was dried in a drying oven at 40 ° C for 24 hours to obtain a porous body in which continuous bubbles were formed. (Example 1 8) The kneaded product obtained in the same manner as in Example 17 was heated at 150 ° C for 5 minutes by a press molding machine (pressure of 50 tons), and then cooled to obtain 2 5 . 0 mm X 2 5 0 mm X Sheet-shaped molded product with a thickness of 3 mm. Then, the molded product was placed on a fluororesin sheet in a high temperature bath, and foamed by heating at 23 (TC for 5 minutes. Then, the formed product was immersed in water at 40 ° C for 90 hours in a water tank). The pore former was extracted while stirring under a stirrer. After the extraction, the molded product was dried in a drying oven at 40 ° C for 24 hours to obtain a porous body in which a continuous bubble sheet was formed. The measurement examples 7 and 18 were obtained. Porosity and ion exchange capacity of the porous body. The water permeability was also measured in Example 18. The ion exchange capacity was measured by the following procedure. The formulation ratio of the composition and the evaluation results of the porous body are shown in Tables 5 and 6. 200842155 Method for measuring ion exchange capacity A sample of about 55 g was placed in a joom L flask, and each of the water was subjected to ultrasonic treatment for 10 minutes. Then, the sample was lightly wiped off, and the sample was immersed in 1.5 M-hydrochloric acid. 20 mL of an aqueous solution was lightly pressed against a surface with a stirring bar to remove air, and ultrasonic waves were applied, and then the sample was taken out, and the sample was immersed in a new 1.5 M-salt 2 mL, and ultrasonic waves were applied for 3 hours. Thereafter, the mixture was washed. Net, go water After the sample was transferred to a glass dish, it was allowed to pass overnight. The dried sample was transferred to a 10 M aqueous solution of 1 M sodium chloride in a 1000 mL round flask, covered with a film, and applied while immersing the sample in 1 M. - 6 hours in an aqueous solution of sodium chloride, then 0.1 mM of phenolphthalein as indicator, using 0.1 Μ-NaOH to titrate. 〇·1 Μ-hydrochloric acid aqueous solution to 〇. 1 Μ-sodium hydroxide water Correction factor (factor) 値, correction of measurement 。. Ion exchange energy Q. Ion exchange energy Q[meq./g]=xyf/m X : concentration of sodium hydroxide solution [N] y : titration [mL ] m : sample quality (dry quality) [g] f : the correcting factor of sodium hydroxide solution sterol and ultrapure water vapor light, one side for 3 hours. Acid aqueous solution ultra-pure water filled with vacuum drying, force 0 into the super Under the sound wave, the solution is added as a solution to obtain the solution. The following formula is used to determine -54- 200842155 [Table 5] Polymer substance First pore Second pore foaming agent Interfacial crosslinking agent Functionality 塡 Filling agent forming agent Active agent type Parts by weight parts by weight parts by weight parts by weight Example 17 ' 18 EVA 100 225 225 45 1 0.8 Ion exchange resin 100 [Table 6] Foaming and extraction of a molded product Performance of a foaming step Extraction time [hour] Porosity Γ%1 Water permeability [second] Ion exchange Capacity [meq./dry-g] Example 17 80 78 1.44 Example 18 90 80 10 1.44 As shown in the above table, high ion exchange energy can be obtained by using an ion exchange resin as a functional chelating material. A cylindrical or sheet-like porous body. The cylindrical porous body can be effectively applied as a flat type column. BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is a schematic view showing a water permeability measuring device. Fig. 2 is a graph showing the relationship between the extraction time and the porosity of the porous body in Example 1, Example 2, and Comparative Example 1. Fig. 3 is a graph showing the relationship between the extraction time and the porosity of the porous body in Example 3, Example 4, and Comparative Example 2. Fig. 4 is a graph showing the relationship between the extraction time of Examples 5, 6 and 3 and the porosity of the porous body. Fig. 5 is an electron micrograph of the porous body obtained in Example 7 (-55-200842155 magnification 1 ο ο 〇). Fig. 6 is an electron microscope photograph (magnification: 1000 times) of the porous body obtained in Example 8. Fig. 7 is an electron microscope photograph (magnification: 1 〇 〇 倍) of the porous body obtained in Example 9. Fig. 8 is an electron micrograph of the porous body obtained in Example 1 (bottom right: 35 times, lower left: 100 times, upper right: 1 〇 0 〇, upper left: 2 倍 times). ® 9 was an electron microscope photograph of the porous body obtained in Example 1 (bottom right: 35 times, lower left: 1 inch, upper right: 1 000 times, upper left: 200 times). Fig. 10 is an electron microscope photograph of the porous body obtained in Example 1 (bottom right: 35 times, lower left: 100 times, upper right: 1 inch, upper left: 2000 times). ® 1 1 is an electron microscope photograph of the porous body obtained in Example 13 (bottom right: 35 times, lower left: 100 times, upper right: 1000 times, upper left: 2000 times). 1 2 is an electron microscope photograph of the porous body obtained in Example 1 (bottom right: 35 times, lower left: 1 〇〇, upper right · 1000 times, upper left: 2 倍 times). 1 3 is an electron microscope photograph of the porous body obtained in Example 1 5: 35 times, the lower left · · 100 times, the upper right: 1000 times, the upper left: the figure (the lower right 2 times times 1 4 is the embodiment 1 6 Electron Microscope Photography of Porous Body Obtained - 56 - 200842155 (bottom right: 3 5 times, lower left: 1 〇 0 times, upper right: 10 〇 times, upper left: 2 00 times) 〇 Figure 15 is an example 1 is a graph showing the relationship between the extraction time and the porosity of the porous body in Comparative Example 4. Fig. 16 is a graph showing the relationship between the extraction time and the porosity of the porous body in Example 14 and Comparative Example. [Explanation of main component symbols] 1 : Porous body 2 : Filter media holder for filtration 3 : With decompression pump connection port container 4 : Clamp 5 : Decompression pump connection port - 57-