200401786 ⑴ 玖、發明說明 【發明所屬之技術領域】 本發明係提供胺樹脂交聯粒子與其製造方法。 【先前技術】 胺樹脂交聯粒子以其優越之物性，以往即用於去光 劑、光擴散劑、硏磨劑 '各種薄膜用塗覆劑、或聚烯烴或 聚氯乙烯、各種橡膠、各種塗料、調色劑等之充塡劑，此 外亦用於流變控制劑或著色劑等用途。目前亦正開發有關 其之各種製造方法。 例如於日本特開昭4 9 - 0 5 7 0 9 1號公報中揭示藉由胺系 化合物與甲醛反應生成作爲樹脂前驅體之初期縮合物，將 其染色後’經乳化及硬化而製造著色之胺樹脂交聯粒子， 而藉由測定丙酮|混合度準確判斷胺系化合物與甲醛之反應 終點’若於反應終了時添加染料進行染色，則可獲得賦予 耐溶劑性、耐熱性之著色胺樹脂交聯粒子，將所得粒子由 前述乳化時之水系介質分離乾燥，將乾燥物鬆碎以鬆脫其 凝集而成爲平均粒徑0.1至2 0 μηι粒子。 曰本特公平07 - 0 1 7 72 3號公報中揭示於胺系化合物與 甲醛反應生成作爲樹脂前驅體之初期縮合物時，係使用介 面活性劑及烷基苯磺酸，並於所得之生成系中添加硬化劑 使前述樹脂前驅體硬化，於前述生成系之水系介質中粒子 化而析出’獲得平均粒徑〇 . 1至2 0 μ m之胺樹脂交聯粒 t ’析出之粒子自前述水系介質分離，乾燥，使用球磨機 -4- (2) (2)200401786 以極輕之力將乾燥物鬆碎。 曰本特開昭50- 04 5 8 5 2號公報中揭示將苯并胍胺與三 聚氰胺組成之混合物及甲醛於保護膠體之存在下攪拌之， 於反應系內添加硬化觸媒使反應物硬化，獲得微細硬化粒 子，所得之粒子自反應系之水系介質中分離，乾燥，對乾 燥物輕微施力以鬆脫其凝集。 於日本特開平〇4-2 1 1 4 5 0號公報中揭示藉由胺系化合 物與甲醛反應生成作爲樹脂前驅體之初期縮合物，於其中 添加無機顏料後，經乳化及硬化而獲得著色之胺樹脂交聯 粒子’將所得粒子分離，乾燥後，使用球磨機、錘磨機、 噴射磨等粉碎機，施予能鬆脫其凝集狀態之力，亦即藉由 鬆碎使粒徑成爲5 μηι以下。其實施例記載著色胺樹脂交 聯粒子係以乳鉢將其乾燥物粉碎。 胺樹脂交聯粒子近年來隨著 ΟΑ技術領域之蓬勃發 展，而作爲LCD用之光擴散片用之光擴散劑的胺樹脂交 聯粒子之使用廣受注目。又，最近使用著色胺樹脂交聯粒 子將氯乙烯片等著色之技術亦廣泛實施。 但是，已知以胺樹脂交聯粒子作爲光擴散劑與黏合劑 樹脂共同塗佈於PET薄膜等薄片上，作爲LCD用光擴散 片時，引發產生斑點之問題。又，使用以往之著色胺樹脂 交聯粒子將氯乙烯片等著色時，亦知有發生退色之問題。 由於使用胺樹脂交聯粒子而發生斑點或退色等導致所 謂製品品質不良，於上述光擴散片或氯乙烯片以外之用 途，若使用以往之胺樹脂交聯粒子時亦有發生上述情況之 200401786 (3) 可能性。 【發明內容】 〔發明欲解決的問題〕 因此，本發明欲解決的問題即係提供不會產生上述斑 點或退色等品質不良等問題的胺樹脂交聯粒子及其製造方 法。 〔解決問題之手段〕 本發明人爲解決上述問題對胺樹脂交聯粒子深入進行 檢討。結果發現上述光擴散片中之所謂光擴散劑或氯乙烯 片之著色材料等，在慮及要求從來未有之高水準製品品質 之用途時，其平均粒徑必須滿足特定之範圍。此外亦確知 抑制特定粒徑以上之粗大粒子混合存在係屬必要。亦即， 就光擴散效果與著色效果方面，使平均粒徑落於〇. 1至2 〇 μηι之特定範圍內係屬必要，另一方面，若不能抑制4〇 μηι以上粗大粒子之個數基準於0.05%以下之特定水準量 下，則有可能引起前述產生斑點或退色之現象。爲圖解決 前述問題，抑制粗大粒子之混入特別重要。亦即，考慮以 肉眼進行識別評估時，係以所謂4 0 μ m爲特定粒徑，若該 粒徑以上之粒子大量混合存在則產生之退光或退色現象爲 肉眼可檢測而成爲缺陷。此種情況下，若特定粒徑以上之 粗大粒子存在之個數基準能滿足〇·〇5%以下之從來未有之 新穎粒徑控制基準，則可確實且有效的解決上述問題。 -6- (4) (4)200401786 本發明人等亦進一步獲得以下知識。亦即，發現於必 須要求高水準透明性等之薄膜或薄片等製品中，胺樹脂交 聯粒子之平均粒徑若小於上述範圍內，亦即有必要選自 〇 ]至5 μηι，此種情況下，於要求確保均一透明性等之情 況’粒徑爲8 μηι以上之粒子之比例以個數基準爲〇 〇5 % 以下係屬必要。 因此’本發明之胺樹脂交聯粒子係由胺系化合物與甲 醛反應而得之胺樹脂交聯粒子，其特徵爲平均粒徑〇」至 2 0 μπι，且粒徑40 μηι以上之粗大粒子之比例爲個數基準 〇 · 〇 5 %以下。 因此，上述本發明之胺樹脂交聯粒子中，使其平均粒 徑爲0 · 1至5 μ m時，以粒徑8 μ m以上之胺樹脂交聯粒子 之比例爲個數基準〇 . 〇 5 %以下爲佳。 本發明人等檢視持有上述特定平均粒徑，且同時所含 特定粒徑以上之粒子不超過特定比例之胺樹脂交聯粒子之 製造方法，結果發現將上述習知製造方法中所得之胺樹脂 交聯粒子之粉碎物實施分級極爲重要。亦即，發現與習知 方法同樣，自硬化反應後之水系介質分離胺樹脂交聯粒子 並乾燥後，使用球磨機、錘磨機、噴射磨等粉碎機，施予 可鬆解其凝集狀態之力，亦即使其鬆碎，但是該粉碎物非 維持原態，而係充分將其分級，此點極爲重要。 上述習知技術之胺樹脂交聯粒子之製造方法係於任一 方法中，雖於硬化反應後進行分離、乾燥及粉碎（鬆 碎），但並未進行粉碎物之分級。 (5) 200401786 因此，有關上述本發明中爲獲得胺樹脂交聯粒子之第 1種製造方法，其特徵係將由胺系化合物與甲醛反應所得 之胺樹脂前驅體於水系介質中乳化及硬化而獲得交聯粒子 後，將前述胺樹脂交聯粒子自前述乳化時之水系介質分 離、乾燥，將所得乾燥物粉 於上述第1種製造方法 所得之乳濁液中添加觸媒而 前述乳化開始5小時以內進 用之乳化劑以使用可構成保 繼之，有關上述本發明 2種製造方法，其特徵係將 之胺樹脂前驅體於水系介質 合液中添加觸媒使前述胺樹 子化而析出後，將前述胺樹 系介質分離、乾燥，將所得 物分級。 於上述第2種製造方法 性者爲佳，因此上述胺樹脂 上者爲佳。 因此，於本發明之第1 2種製造方法中，其前述粉 進行氣流粉碎或氣流分級及 含量爲6g/m3以下之氣體以 下，上述氣體以使用於上纽 碎，並將所得之粉碎物分級。 中，其硬化係藉由於上述乳化 進行，且上述觸媒之添加係自 行爲佳。因此，前述乳化所使 護膠體之乳化劑爲佳。 中爲獲得胺樹脂交聯粒子之第 由胺系化合物與甲醛反應所得 中與介面活性劑混合，於該混 脂前軀體自前述水系介質中粒 脂交聯粒子自前述乳化時之水 乾燥物粉碎，並將所得之粉碎 中，上述胺樹脂前驅體以水溶 前驅體之水混合度以1 0 0 %以 種製造方法中，或本發明之第 碎以後之至少一種處理中，於 粒子氣流移送時，係使用水夕） 形成氣流爲佳。因此於該情況 〔粉碎後之所有處理中更佳0 (6) (6)200401786 又，上述氣體以氧氣濃度爲l 〇%以下者更佳。另一方面於 上述粉碎後之處理領域中，爲避免因大氣所含水分而產生 粒子凝集，亦藉田控管上述大氣使其水分含量成爲6g/m3 以下爲佳。前述粉碎與分級以使用兼具粉碎與分級兩功能 之裝置進行，或前述分級亦可使用氣流分級進行。 【貫施方式】 下文詳細說明本發明之胺樹脂交聯粒子及其製造方 法’但以下說明並非用以限定本發明之範圍，只要無損於 本發明宗旨之範圍內可於以下例示之外適當加以變更而實 施。 <胺樹脂交聯粒子> 本發明之胺樹脂交聯粒子之特徵爲平均粒徑0 . 1至2 0 μη] ’且粒徑40 μΐΏ以上之粗大粒子之比例爲個數基準 〇 . 〇 5 %以下。 上述本發明之胺樹脂交聯粒子，係以後述之本發明胺 樹脂交聯粒子之第i或第2種製造方法即可獲得。 本發明之胺樹脂交聯粒子中，上述平均粒徑以〇 ·]至 1 5 μηι爲佳。若上述平均粒徑爲〇 ·丨至2 〇 μ ηι範圍以外， 則例如作爲使用本發明之胺樹脂交聯粒子與黏合劑樹脂之 光擴散片時之光擴散性能差。又，於本發明中，上述平均 粒徑係使用庫耳特多尺寸計（Coulter multisizer) -II型 (庫耳特公司製）測定者。 • 9 - (7) 200401786 本發明之胺樹脂交聯粒子中上述粒徑爲4 〇 粗大粒子個數基準之比例以0.0 3 %以下爲佳，1 更佳，0 · 01 %以下又更佳。又，上述之個數基準 粒子個數之比例者、對全部測定之粒子個數之鞋 數之比例者。具體言之，係使用粒度分布測定裝 多尺寸計-Π型（庫耳特公司製），測定 3 〇 〇 〇 〇 各粒子徑’其中粒徑爲規定以上之粒子數對全 3 0 0 0 0個之比例。 粒徑40 μηι以上之粗大粒子之比例爲個數 0 · 0 5 °/〇之粒子，係以往周知之胺樹脂交聯粒子中 粒子’例如爲作成LCD用之光擴散片，於PET 片上與黏合劑樹脂共同塗佈時，容易因粗大粒子 點。又，使用著色胺樹脂交聯粒子時，例如將養 透明基材著色時，亦發生因粗大粒子引起之退色 因此，由本發明之胺樹脂交聯粒子所形成 劑，更具體言之LCD用光擴散片之光擴散劑， 佳之實施型態。或者，由本發明之胺樹脂交聯粒 之薄膜塗覆劑亦成爲較佳之實施型態。此外，由 胺樹脂交聯粒子所形成之著色劑亦成爲較佳之實 本發明之胺樹脂交聯粒子係以平均粒徑 μηι，且粒徑8 μιη以上之粒子比例爲個數基準（ 爲佳。 本發明人發現，以本發明之胺樹脂交聯粒 粒徑爲〇. 1至5 μηι者爲對象時，當然要滿足前 μηο以上之 0.0 2 %以下 :係指表示 i大粒子個 ^置庫耳特 個粒子之 部粒子數 :基準超過 所見到之 薄膜等薄 •而產生斑 β乙烯片等 問題。 之光擴散 係成爲較 .子所形成 本發明之 施型態。 0.1 至 5 )· 0 5 %以下 子其平均 述粒徑爲 -10- (8) (8)200401786 4 0 μηι以上之粗大粒子之個數基準之比例爲〇 . 〇 5 %以下之 條件，以及若同時滿足以粒徑8 μηι作爲基準，大於該粒 徑之粒子之個數基準之比例爲0.05%以下之條件，則例如 使用作爲光擴散片之光擴散劑或氯乙烯片等之著色劑時， 可如前述般成爲具有透明性與均一性優越之品質及外觀。 又，對應於近年之LCD薄型化要求，可製作塗佈厚度甚 薄之光擴散片。 於本發明之上述較佳實施型態中，粒徑爲8 μηι以上 粒子之個數基準之比例爲〇 . 〇 5 %以下，而以0 · 0 3 %以下爲 佳，0.02 %以下更佳，〇·〇1 %以下特佳。粒徑爲8 μηι以上 粒子之比例爲個數基準超過〇 · 〇 5 %時，則恐不能獲得上述 透明性與均一性均優越之品質及外觀。 於本發明中’藉由採用規定之下述胺樹脂交聯粒子之 製造條件、粉碎條件、分級條件、粒子輸送條件之本發明 胺樹脂交聯粒子之製造方法，可容易且確實的獲得平均粒 徑與其分布爲上述特定範圍之胺樹脂交聯粒子，又該胺樹 脂交聯粒子即使於保存或貯藏中其狀態亦不易改變，具體 而言粗大粒子之量不易改變，亦爲保存安定性或貯藏安定 性優越之物。 月女樹脂父聯粒子之乾燥粉體之保存安定性或貯藏安定 性具體言之，係以平均粒徑之變化量爲分子，剛製造後之 '丨'均粒徑爲分母所得之比例表示時，以10%以下爲佳， 5 %以下更佳。又，以粒徑4 0 μ m以上之粗大粒子之量爲 为于’剛製造後該粗大粒子之量爲分母所得之比例表示 - 11 - (9) 200401786 時’以10%以下爲佳，5%以下更佳。 下文中，可容易且確實的獲得具有特定平均粒徑，且 不包含特定粒徑以上之粗大粒子（或粒子）個數基準超過 特疋比例之上述本發明之胺樹脂交聯粒子，茲詳細說明本 發明之胺樹脂父聯粒子之製造方法。又，於本說明書中， 亦將胺樹曰父聯粒子製造過程之液體狀態稱爲「乳濁液」 與「懸濁液」2種液體狀態表示，而「乳濁液」係指液體 中液體粒子以膠體粒子或更大之粗大粒子分散成爲乳狀 者，「懸濁液」係指液體中固體粒子以膠體粒子或以顯微 鏡可見程度之粒子而分散者。 (胺樹脂交聯粒子之製造方法） 以下詳細說明有關本發明胺樹脂交聯粒子之製造方 法’以其即可容易的獲得本發明之上述胺樹脂交聯粒子。 有關本發明胺樹脂交聯粒子之製造方法，其最大特徵 係將胺樹脂交聯粒子之乾燥物粉碎所得之粉碎物加以分 級。 -第]種製造方法- 本發明該胺樹脂交聯粒子之第1種製造方法（下文亦 簡稱爲「第1種製造方法」），其特徵係如上述般將由胺 系化合物與甲醛反應所得之胺樹脂前驅體於水系介質中乳 化及硬化而獲得胺樹脂交聯粒子後，將前述胺樹脂交聯粒 子自則述乳化時之水系介質分離、乾燥，將所得乾燥物粉 ;'rr -12· 4 S b (10) 200401786 碎，並將所得之粉碎物分級。 下文除說明實施第1種製造方法之胺樹月旨 一般製造方法外，同時亦說明第]種製造方法 第1種製造方法，一般而言，該胺樹脂交 造方法係包括：由胺系化合物與甲醛反應而獲 驅體之樹脂化步驟、將該樹脂化步驟所得之胺 乳化而獲得胺樹脂前驅體乳濁液之乳化步驟、 驟所得之乳濁液中添加觸媒使乳化之胺樹脂前 化反應而獲得胺樹脂交聯粒子之硬化步驟。 於樹脂化步驟中，藉由胺系化合物與甲醛 作爲初期縮合反應物之胺樹脂前驅體。胺系化 之反應一般係使用水作爲溶劑。反應形態係爲 與甲醛於水系介質中反應而成爲獲得含作爲初 物之胺樹脂前驅體的水溶液（反應液）形態， 形態之具體方法可例舉使甲醛成爲水溶液（ 態’於其中添加胺化合物而進行反應之方法， 或多聚甲醛添加至水中，於該可產生甲醛之水 胺化合物而進行反應之方法等爲宜，其中，以 因甲醛水溶液之調整槽並非必要，入手容易等 而言更佳。 又，一般而言上述反應之樹脂化步驟，以 攪拌裝置等進行攪拌爲佳。樹脂化步驟中可作 之胺系化合物並無特別限定，可例舉如苯并刖 胺基-6-苯基-sym -三畊）、環己烷甲胍胺、環 交聯粒子之 之特徵。 聯粒子之製 得胺樹脂前 樹脂前驅體 於該乳化步 驅體進行硬 反應而獲得 合物與甲醛 胺系化合物 期縮合反應 實施該反應 福馬啉）狀 或將三噁烷 溶液中添加 前者之方法 以及經濟面 使用週知之 爲原料使用 i 胺（2,4-二 己烯甲胍胺 -13- (11) (11)200401786 及三聚氰胺等。其中，一般而言，以具有三畊環之胺系化 合物更佳，此外，苯并胍胺由於具有苯環與2個反應基而 於初期縮合狀態下之染色性優越，交聯後可撓性（硬 度）、耐污染性、耐熱性、耐溶劑性、耐藥性均優越而特 佳。此等胺系化合物可單獨使用亦可2種以上倂用。 所使用之胺系化合物全體中，以上所例示之胺系化合 物（苯并胍胺、環己烷甲胍胺、環己烯甲胍胺及三聚氰 胺）之合計量以 4 0重量％以上爲佳，6 0重量％以上更 佳，8 0重量。/。以上又更佳，1 〇 〇重量％以上最佳。藉由使 以上例示之胺系化合物合計量爲4 0重量％以上則具有可 獲得所謂耐熱性、耐溶劑性優越之胺樹脂交聯粒子的效 果。 於樹脂化步驟中進行反應之胺系化合物與甲醛之莫耳 比（胺系化合物（莫耳）/甲醛（莫耳））以1/3 · 5至 1/1 .5爲佳，1/3.5至1/1 .8更佳，1/3.2至1/2最佳。若上 述莫耳比小於1 /3 . 5，則甲醛之未反應物可能太多，而若 超過1 /1 . 5，則胺系化合物之未反應物可能太多。 又’使用水作爲溶劑時，對水而言胺系化合物與甲酸 之添加量，亦即裝塡時點之胺系化合物與甲醛之濃度，只 要對反應無妨者以較高濃度爲佳。更具體而言，以可將含 反應物胺樹脂前驅體的反應液之9 5至9 8 t溫度範圍內之 黏度調節並控制於2x10·?.至5.5x l(T2pa · s ( 20至 5〕c P )之範圍內爲佳，更好於下述之乳化步驟中使乳濁液 中之fee樹脂則驅體濃度成爲3 0至6 0重量％範圍內，只要 -14- (12) (12)200401786 是可將反應液添加至乳化劑之水溶液中，或者將乳化劑或 乳化劑之水溶液添加至反應液中之濃度即可。 因此，於樹脂化步驟中獲得含胺樹脂前驅體之反應液 時，該反應液於95至98 °C溫度範圍內之黏度以2x1 0·2至 5·5χ l(T2Pa· s(20 至 55cP)爲佳，以 2.5xl0·2 至 5·5χ l(T2Pa· s (25 至 55cP)更佳，3.0χ](Γ2 至 5.5x l(T2Pa· s (30至55cP)又更佳。 上述黏度之測定方法，係以使用黏度測定機而可即時 (r e a r t i in e )掌控反應進行狀態，且可正確辨別其反應終 點之方法爲最佳。該黏度測定機可使用振動式黏度計 (MIVI ITS曰本公司製，製品名：MIVI 6001)。該黏度 測定機設有經常振動之振動部，將該振動部浸漬於反應液 中’該反應液之黏性增加則振動部之負荷增加，將該負荷 即時換算成黏度表示之。 使胺系化合物與甲醛於水中（水系介質中）反應，可 獲得所謂初期縮合反應物之胺樹脂前驅體。反應溫度係以 可即使把握反應之進行狀態，且可正確辨別其反應終點， 而於95至98 °C溫度範圍內爲宜。因此，胺系化合物與甲 醛之反應，可於反應液之黏度成爲2χ](Γ2至5.5x l(T2Pa • s範圍內之時間點，將該反應液進行冷卻等操作而終止 反應。據此可獲得含胺樹脂前驅體的反應液。又，反應時 間並無特殊限定。 有關樹脂化步驟中所得之胺樹脂前驅體，源自構成該 胺樹脂前驅體之胺系化合物之構造單元與源自甲醛之構造 (13) 200401786 單兀之莫耳比（源自胺系化合物之構造單元（莫 自甲醛之構造單元（莫耳））以]/3 · 5至1 /} 5 1/3·5至1/1.8更佳，1/3.2至1/2又更佳。藉由七 落於上述範圍內，可獲得粒度分佈窄之粒子。 又，通常反應終了時間點之反應液之黏度， 系化合物與甲醛（反應開始時）之水溶液之黏度净 提高，因此裝入原料之濃度等幾乎無影響。胺樹月旨 通常可溶於丙酮、二噁烷、甲醇、乙醇、異丙醇、 乙酸乙醋、乙酸丁醋、甲基溶纖素、乙基溶纖素、 基酮、甲苯、二甲苯等有機溶劑，而水實質上不溶 第1種製造方法，係於獲得該含胺樹脂前驅體 液之樹脂化步驟中降低反應液之黏度，而可使最終 胺樹脂交聯粒子粒徑變小。然而，若反應液之黏 2xl(T2Pa· s或大於 5.5x l(T2Pa· s時，不能獲得 子大約一致（粒度分佈窄）之胺樹脂交聯粒子。亦 反應液之黏度小於2 X ] 0 ·2 P a · s ( 2 0 c P )，則下述 驟所得之乳濁液缺乏安定性，因此於硬化步驟中將 前驅體硬化時，所得之胺樹脂交聯粒子肥大化，且 可能產生凝集而不能控制胺樹脂交聯粒子之粒徑， 獲得粒度分佈廣範圍之胺樹脂交聯粒子。又，乳濁 安定性時每次製造（每批）時，胺樹脂交聯粒子 (平均粒徑）會改變，而製品可能產生不一致之現 一方面，反應液之黏度大於5.5x l(T2Pa· s(55cf 下述乳化步驟所使用之高速攪拌機等負荷過大，由 耳）/源 爲佳， ί莫耳比 •裝入胺 I較顯著 nu驅體 丁醇、 甲基乙 於水。 之反應 所得之 度小於 最終粒 即，若 乳化步 胺樹脂 粒子間 而可能 液缺乏 之粒徑 象。另 >)時則 於其剪 (14) (14)200401786 切力降低，而可能無法充分攪拌（使乳濁）反應液°因 此，不能控制最終所得之胺樹脂交聯粒子之粒徑’且可能 獲得粒度分佈範圍廣之胺樹脂交聯粒子。據此’於樹脂化 步驟中將反應液黏度調整於上述黏度範圍，即成爲可獲得 本發明胺樹脂交聯粒子之較佳實施形態。 乳化步驟係將樹脂化步驟所得之胺樹脂前驅體乳化而 獲得胺樹脂前驅體之乳濁液。進行乳化時，例如以使用可 構成保護膠體之乳化劑爲佳，可構成保護膠體之水溶性聚 合物所成之乳化劑更佳。 上述乳化劑可使用聚乙烯醇、羧甲基纖維素、褐藻酸 鈉、聚丙烯酸、水溶性聚丙烯酸鹽、聚乙烯吡咯烷酮等。 此等乳化劑可使用全量均溶解於水中之水溶液狀態，或其 一部分爲水溶液狀態，餘者使用原來狀態（例如粉狀、顆 粒狀、液狀等）。以上例示之乳化劑中，考慮乳濁液之安 定性、與觸媒之相互作用等時，以使用聚乙烯醇更佳，聚 乙烯醇可使用完全皂化物，亦可使用部分皂化物。又，聚 乙烯醇之聚合度並無特別限定。對前述樹脂化步驟所得之 胺樹脂前驅體而言乳化劑之使用量多時，所生成粒子之粒 徑有變小之傾向。乳化劑之使用量對前述樹脂化步驟所得 之肢樹目曰則驅體1 0 0重量份以1至3 0重量份爲佳，1至5 重量份更佳。其使用量若在上述範圍之外，則乳濁液可能 缺乏安定性。： 乳化步驟例如係於乳化劑之水溶液中，添加上述樹脂 化步驟所得之胺樹脂前驅體濃度（固形物濃度）爲3 0至 -17 - (15) (15)200401786 6 0重量％範圍內之反應液後，於5 0至]〇 〇。(：溫度範圍內 使乳濁化爲佳，以6 0至1 〇 〇 °C更佳，7 0至9 5 °C又更佳。 乳化劑水溶液之濃度並無特殊限定，只要可將胺樹脂前驅 體之濃度調節至上述範圍內之濃度即可。上述胺樹脂前驅 體之濃度若小於3 0重量％，則胺樹脂交聯粒子之生產性 可能降低，若超過60重量％則所得胺樹脂交聯粒子可能 肥大化且粒子間可能凝集，由於不能控制胺樹脂交聯粒子 之粒徑，而可能獲得粒度分佈範圍廣之胺樹脂交聯粒子。 乳化步驟中之攪拌方法爲使用可更強力攪拌的裝置 (具高剪切力之裝置）之方法，具體言之，例如以使用高 速攪拌機或混合機、TK混合機（特殊機化工業（股） 製）、高速分散機、耶芭拉硏磨機（Ebalamizer ) ((股）荏原製作所製）、高壓均質機（（股）泉食品機 械（I z u m i f ο 〇 d m a c h i n a 1· y )製）、靜力混合機（（股） 諾理塔巾G米得製）等之方法爲佳。 於乳化步驟中，係以促進樹脂化步驟所得之胺樹脂前 驅體乳化至成爲規定粒徑爲佳，該規定粒徑可視最終所期 望胺樹脂交聯粒子之粒徑而適當設定。具體言之，藉由適 當考慮容器或攪拌翼之種類、攪拌速度、攪拌時間、乳化 溫度等而進行乳化，使經乳化之胺樹脂前驅體之平均粒徑 成爲〇 · 1至2 0 μ m爲佳，0 · 5至2 0 μ m更佳，1至1 5 μ m 又更佳。藉由進行乳化使胺樹脂前驅體成爲上述粒徑範 圍，即可獲得最終爲下述之期望粒徑範圍之胺樹脂交聯粒 子。 -18- (16) (16)200401786 於第1種製造方法中’爲了可更確實防止最終所得之 胺樹脂交聯粒子牢固凝集，視需要可於上述乳化步驟後所 得之乳濁液中添加無機粒子。無機粒子較佳者可具體例舉 氧化矽微粒子、氧化鍩微粒子、鋁粉、氧化鋁溶_、雪梨 溶膠（Seleaesol )等較佳，其中就取得容易度而言，以氧 化矽微粒子更佳。無機粒子之比表面積以10至400 m 2/g 爲佳，20至3 5 0m2/g更佳，30至3 0 0 m2/g又更佳。無機 粒子之粒徑以 0.2 μηι以下更佳，〇. 1 μηι以下又更佳， 0·〇5 μιτι以下最佳。比表面積或粒徑若爲上述範圍內，因 可防止最終所得之胺樹脂交聯粒子牢固凝集，而能發揮更 進一步之優越效果。 於乳濁液中添加無機粒子之方法並無特別限定，具體 言之，例如直接將無機粒子以原狀（粒子狀）添加之方 法、以無機粒子分散於水中之分散液狀態添加之方法等。 對乳濁液而言無機粒子之添加量，對乳濁液中所含胺樹脂 前驅體1〇〇重量份以1至30重量份爲佳，2至28重量份 更佳’ 3至2 5重量份又更佳。若小於1重量份則不能充 分防止最終所得之胺樹脂交聯粒子牢固凝集，若超過3 〇 重量份則可能產生只有無機粒子之凝集物。又，添加無機 粒子時之攪样方法，就使無機粒子牢固於胺樹脂交聯粒子 方面而言’以使用前述之強力攪拌裝置（具高剪切力之裝 置）的方法較佳1v 於硬化步·驟中’將觸媒（詳言之爲硬化觸媒）添加至 上述乳化步驟所得之乳濁液中，進行經乳化之胺樹脂前驅 -19- (17) (17)200401786 體之硬化反應（使胺樹脂前驅體以乳濁狀態進行硬化）而 獲得胺樹脂交聯粒子（詳言之爲胺樹脂交聯粒子之懸濁 液）。 上述觸媒（硬化觸媒）以酸觸媒爲佳。酸觸媒可使用 例如鹽酸、硫酸、磷酸等無機酸；此等無機酸之銨鹽；磺 醯胺酸；苯磺酸、對甲苯磺酸、十二烷基苯磺酸等磺酸 類；苯二甲酸、苯甲酸、乙酸、丙酸、水楊酸等有機酸。 以上例示之酸觸媒中，就硬化速度方面而言以無機酸爲 佳，此外，就對裝置之腐蝕性、無機酸使用時之安全性等 而言，以硫酸爲更佳。又，使用硫酸爲上述觸媒時，例如 與使用十二烷基苯磺酸者相較時，其最終所得之胺樹脂交 聯粒子不會變色而耐溶劑性高等而較佳。此等可僅使用一 種，亦可2種以上倂用。上述觸媒之使用量，對上述乳化 步驟所得乳濁液中胺樹脂前驅體1 〇〇重量份，以〇. 1至5 重量份爲佳，0.3至4·5重量份更佳，0.5至4.0重量份又 更佳。觸媒之使用量若超過5重量份，則乳濁狀態破壞， 粒子間可能產生凝集，若小於〇 · 1重量份則反應所需時間 長，而硬化可能不足。又’同樣的，上述觸媒之使用量對 作爲原料化合物使用之胺系化合物1莫耳以0.0 02莫耳爲 佳，0.005莫耳更佳，〇.〇1至0.1莫耳又更佳。觸媒之使 用量對胺系化合物1莫其若小於0·002莫耳，則反應所需 時間長，而硬化可能不足° 硬化步驟中之硬化反應，較好於1 5 (常溫）至80 t，更好於20至70°C ’最好於30至60°C下至少維持1 60 (18) 200401786 小時後，於常壓或加壓下較好於60至1 50°C ’更好於 至]3 0 °C，最好於6 0至]0 0 °C之溫度範圍內進行。硬化 應之反應溫度若低於60 °C則不能充分硬化’所得胺樹 交聯粒子之耐溶劑性或耐熱性可能降低，若超過1 5 0 °c 必須使用堅牢之加壓反應器而不經濟。 硬化反應之終點可依據取樣或目視判斷。又’硬化 應之反應時間並無特別限定。 硬化步驟中之攪拌方法較好以一般週知之攪拌裝置 於攪拌下進行爲佳。 硬化步驟中，以使乳濁狀態之胺樹脂前驅體硬化所 胺樹脂交聯粒子之平均粒徑成爲0.1至20 μηι爲佳，（ 至2 Ο μ m更佳，1至1 5 μ m又更佳。 第1種製造方法中，可包含將染料溶解於水所得之 ί谷液添加至胺樹脂前驅體之乳濁液或胺樹脂交聯粒子之 濁液的著色步驟。 胺樹脂前驅體或胺樹脂交聯粒子與染料之親合性 越。於所得胺樹脂前驅體之乳濁液或胺樹脂交聯粒子之 濁液的著色步驟所添加之染料，只要可溶於水之染料， 即水溶性染料即可，並無特別限定。水溶性染料具體而 可爲例如若丹明Β、若丹明6 G C Ρ (以上，住友化學工 股份有限公司製）、甲基紫FN、維多利亞藍FN等鹼 染料；喹啉黃-S S -5 G、喹啉黃-S S - G C (以上，中央合成 學股份有限公司製）、酸性品紅〇、甲基紫FB、維多 亞藍FB等酸性染料等，並無特別限定。此等染料可單 反 脂 則 反 等 得 ).5 水 懸 優 懸 亦 言 業 性 化 利 獨 -21 - (19) (19)200401786 使用，亦可2種以上倂用。 水溶液中染料之濃度並無特別限定，但以〇 .；[〜5重 量％範圍內更佳，1〜3重量％範圍內又更佳。若染料濃度 低於G . 1重量％則因所添加之水溶液量增多，而降低胺樹 脂粒子之生產性。另一方面，若染料濃度超過5重量％則 乳濁液之安定性降低，因而所得胺樹脂交聯粒子肥大化而 粒子間亦可能產生凝集。又，調製將染料溶於水所成之水 溶液之調製方法，以及將水溶液添加並於乳濁液中混合之 方法並無特別限定。 第1種製造方法中，視需要亦可於上述樹脂化步驟所 得之反應液中，另添加染料作爲前段著色步驟。該染料只 要可分散於水之染料，亦即油溶性染料亦可，並無特別限 定。油溶性染料具體而言可爲例如油性橘B、油性藍BA (以上’中央合成化學股份有限公司製）、偶氮可溶性 黃-4GF、偶氮可溶性快速藍-GLA、油性橘TR-71等溶劑 可溶染料；快速黃-Y L、快速藍F G、散利通粉紅F F 3 B、 散利通粉紅3 B等分散染料；等，並無特別限定。此等染 料可單獨使用，亦可2種以上倂用。藉由進行將油溶性染 料分散於水而得之分散液加至樹脂化步騾所得反應液之前 段著色步驟與前述著色步驟，可更充分且均勻的著色，亦 即可獲得各個粒子之色調更爲整齊之胺樹脂粒子。 將油溶性染料分散於水而得之分散液中染料之含量並 無特別限定，但以1〜5 0重量％範圍內更佳，2 0〜4 0重量 %範圍內又更佳。若染料含量小於1重量％則因所添加分 4b b •22 - (20) (20)200401786 散液量增多，因而有降低胺樹脂交聯粒子生產性之情形。 另一方面，若染料含量超過5 0重量％則分散液之流動性 降低’因而添加時作業性不佳且添加操作繁雜。又，由於 油溶性染料對水缺乏沾濕性，因此將該染料分散於水時， 可視需要使用分散助劑。將染料分散於水而調製分散液之 方法以及將分散液添加至反應液中並混合之方法並無特別 限定。 上述反應液（溶液）於添加由染料分散於水而得之分 散液後，例如以使用碳酸鈉、氫氧化鈉、氫氧化鉀、氨水 等鹼劑調節至pH爲6至1 2之範圍內，更好爲7至9之 範圍內。據此，可充分控制硬化步驟中胺樹脂前驅體之縮 合•硬化。鹼劑之使用量等並無特別限定。鹼劑雖以水溶 液狀態添加至反應液並混合之方法爲宜，但該方法並無特 別限定。 第1種製造方法中，可包含將含上述硬化步驟所得胺 樹脂交聯粒子之懸濁液加以中和之中和步驟。中和步驟係 於上述硬化步驟中使用硫酸等酸觸媒作爲硬化觸媒之情況 下進行爲佳。藉由中和步驟可去除上述酸觸媒（具體言之 即將酸觸媒中和），例如，於下述加熱步驟等將胺樹脂交 聯粒子加熱時，可抑制胺樹脂交聯粒子之變色（例如變 黃）。以對經著色之胺樹脂交聯粒子亦有防止變黃之效 果，而可獲得耐熱性優越Z鮮明著色粒子之中和步驟爲較 佳之實施形態。 所謂中和步驟之「中和」係將含胺樹脂交聯粒子之懸200401786 ⑴ 玖, description of the invention [Technical field to which the invention belongs] The present invention provides amine resin crosslinked particles and a method for producing the same. [Prior art] Amine resin cross-linked particles have been used as coating agents for various films, such as delustering agents, light diffusing agents, and honing agents, or polyolefin or polyvinyl chloride, various rubbers, various Fillers for paints, toners, etc. are also used for rheology control agents and colorants. Various manufacturing methods are also being developed. For example, Japanese Patent Application Laid-Open No. 4 9-0 5 7 0 9 1 discloses that an initial condensate formed as a resin precursor is formed by the reaction of an amine compound with formaldehyde, and is dyed and then 'emulsified and hardened to produce a colored product. Amine resin crosslinked particles, and by measuring the acetone | mixing degree, the end point of the reaction between amine compounds and formaldehyde can be accurately determined. If dyeing is added at the end of the reaction to dye, amine resin cross-linking imparting solvent resistance and heat resistance can be obtained. The particles are separated and dried from the aqueous medium at the time of the emulsification, and the dried material is pulverized to loosen its aggregation to become particles having an average particle diameter of 0.1 to 20 μm. Japanese Patent Publication No. 07-0 1 7 72 3 discloses that when an amine compound reacts with formaldehyde to form an initial condensation product as a resin precursor, a surfactant and an alkylbenzenesulfonic acid are used. A hardener is added to the system to harden the resin precursor, and the particles are precipitated in the aqueous medium of the formation system to precipitate 'to obtain an average particle diameter of 0.1 to 20 μm of the amine resin cross-linked particles t'. The aqueous medium was separated and dried, and the dried matter was pulverized using a ball mill -4- (2) (2) 200401786 with extremely light force. Japanese Patent Publication No. 50-04 5 8 5 2 discloses that a mixture of benzoguanamine and melamine and formaldehyde are stirred in the presence of a protective colloid, and a hardening catalyst is added to the reaction system to harden the reactants. Fine hardened particles are obtained, and the obtained particles are separated from the reaction-based aqueous medium, dried, and the dried matter is lightly applied to loosen its agglutination. Japanese Unexamined Patent Publication No. 04-2 1 1450 discloses that an initial condensate formed as a resin precursor is formed by reacting an amine compound with formaldehyde, and an inorganic pigment is added to the resin to emulsify and harden to obtain a colored product. The amine resin cross-linked particles are separated, and after drying, a force such as a ball mill, a hammer mill, and a jet mill is applied to release the aggregated state, that is, the particle size is reduced to 5 μηι by loosening. the following. In the examples, it is described that the colored amine resin crosslinked particles are ground in a mortar and the dried product is pulverized. Amine resin crosslinked particles have been actively developed in recent years in the technical field of OA, and the use of amine resin crosslinked particles as a light diffusing agent for a light diffusing sheet for LCDs has attracted wide attention. Recently, a technique for coloring vinyl chloride sheets and the like using colored amine resin crosslinked particles has also been widely implemented. However, it is known that the use of amine resin crosslinked particles as a light diffusing agent together with a binder resin on a sheet such as a PET film, and the use as a light diffusing sheet for LCDs causes a problem of spotting. In addition, when coloring vinyl chloride sheets and the like using conventionally colored amine resin crosslinked particles, it is also known that there is a problem of discoloration. Due to the use of amine resin crosslinked particles, the so-called product quality is caused by specks or discoloration. For applications other than the above light diffusion sheet or vinyl chloride sheet, the above situation also occurs when using conventional amine resin crosslinked particles. 200401786 ( 3) Possibility. [Summary of the Invention] [Problems to be Solved by the Invention] Therefore, the problem to be solved by the present invention is to provide amine resin crosslinked particles which do not cause problems such as the above-mentioned spots and discoloration, and a method for producing the same. [Means for Solving the Problems] The present inventors conducted in-depth examinations on the amine resin crosslinked particles in order to solve the above problems. As a result, it was found that the so-called light diffusing agent or the coloring material of the vinyl chloride film in the light diffusing sheet mentioned above must have a specific range in consideration of the average particle diameter when taking into consideration applications that have never before attained a high level of product quality. It is also known that it is necessary to suppress the presence of coarse particles having a specific particle size or larger. That is, in terms of the light diffusion effect and the coloring effect, it is necessary to make the average particle diameter fall within a specific range of 0.1 to 20 μm. On the other hand, if the number of coarse particles above 40 μm cannot be suppressed, At a certain level below 0.05%, it may cause the aforementioned phenomenon of spots or discoloration. In order to solve the aforementioned problems, it is particularly important to suppress the incorporation of coarse particles. In other words, when the recognition and evaluation with the naked eye is considered, the so-called 40 μm is used as a specific particle size. If a large amount of particles having a particle size larger than the particle size are mixed in a large amount, the phenomenon of decolorization or discoloration is detectable by the naked eye and becomes a defect. In this case, if the number of coarse particles with a particle size larger than a specific particle size can meet a novel particle size control standard that has never been below 0.05%, the above problems can be reliably and effectively solved. -6- (4) (4) 200401786 The inventors have further obtained the following knowledge. That is, it has been found that in products such as films or sheets that require high levels of transparency, if the average particle diameter of the amine resin crosslinked particles is smaller than the above range, that is, it must be selected from 0] to 5 μηι. In the case where uniform transparency is required, the ratio of particles with a particle size of 8 μm or more is required to be 0.05% or less on a number basis. Therefore, the amine resin crosslinked particles of the present invention are amine resin crosslinked particles obtained by reacting an amine compound with formaldehyde, and are characterized by coarse particles having an average particle size of 0 ″ to 20 μπι and a particle diameter of 40 μηι or more. The proportion is based on the number basis of 0.05% or less. Therefore, in the above-mentioned amine resin crosslinked particles of the present invention, when the average particle diameter is 0.1 to 5 μm, the ratio of the amine resin crosslinked particles having a particle diameter of 8 μm or more is used as the number basis. 〇 It is preferably less than 5%. The present inventors reviewed a method for producing amine resin crosslinked particles having the above-mentioned specific average particle diameter, and at the same time containing particles having a specific particle size of not more than a specific ratio, and found that the amine resin obtained in the above-mentioned conventional manufacturing method was obtained. It is extremely important to classify the ground particles of the crosslinked particles. That is, it was found that the amine resin cross-linked particles were separated from the aqueous medium after the hardening reaction and dried in the same manner as in the conventional method, and then a force such as a ball mill, a hammer mill, and a jet mill was used to release the aggregation state. Even if it is loose, it is extremely important that the pulverized material does not maintain its original state, but is fully classified. The method for producing the amine resin crosslinked particles of the above-mentioned conventional technique is any method. Although the separation, drying, and pulverization (looseness) are performed after the hardening reaction, the pulverized material is not classified. (5) 200401786 Therefore, the first manufacturing method for obtaining amine resin crosslinked particles in the present invention is characterized by emulsifying and hardening an amine resin precursor obtained by reacting an amine compound with formaldehyde in an aqueous medium. After the particles are crosslinked, the amine resin crosslinked particles are separated from the aqueous medium during the emulsification, and dried. The obtained dried powder is added to a catalyst in the emulsion obtained by the first manufacturing method, and the emulsification is started for 5 hours. The use of an emulsifier for internal use can constitute a continuation of the above-mentioned two production methods of the present invention, which are characterized in that the amine resin precursor is added to a water-based medium mixture to add a catalyst to precipitate the amine tree and precipitate, The aforementioned amine dendrimer-based medium was separated and dried, and the resultant was classified. The second manufacturing method is preferred, and the above amine resin is preferred. Therefore, in the twelfth manufacturing method of the present invention, the aforementioned powder is subjected to airflow pulverization or airflow classification and a gas content of 6 g / m3 or less, and the above-mentioned gas is used for smashing and the obtained pulverized product is classified. . In this case, the hardening is carried out due to the emulsification described above, and the addition of the catalyst is excellent in self-behavior. Therefore, the emulsifier of the protective colloid by the aforementioned emulsification is preferable. In order to obtain amine resin crosslinked particles, the first is obtained by reacting an amine compound with formaldehyde and mixed with a surfactant, and the fat-mixed precursor is pulverized from the water-dried product during the emulsification in the fat-mixed precursor from the aforementioned aqueous medium. And in the obtained pulverization, the above-mentioned amine resin precursor is water-soluble precursor with a water mixing degree of 100% in a variety of manufacturing methods, or in at least one treatment after the first crushing of the present invention, during the particle airflow transfer It is better to use water to form air flow. Therefore, in this case, [all treatments after pulverization are more preferable. 0 (6) (6) 200401786] It is more preferable that the above-mentioned gas has an oxygen concentration of 10% or less. On the other hand, in the above-mentioned pulverized processing field, in order to avoid particle agglomeration due to moisture in the atmosphere, it is better to control the atmosphere to control the above-mentioned atmosphere to make the moisture content below 6 g / m3. The aforementioned pulverization and classification may be performed using a device having both pulverization and classification functions, or the aforementioned classification may also be performed using air flow classification. [Implementation Mode] The following describes the amine resin crosslinked particles of the present invention and a method for producing the same in detail. However, the following description is not intended to limit the scope of the present invention, as long as it does not impair the scope of the present invention, it can be appropriately applied in addition to the following examples. Change and implement. < Amine resin crosslinked particles > The amine resin crosslinked particles of the present invention are characterized by an average particle diameter of 0.1 to 20 μη] 'and a ratio of coarse particles having a particle diameter of 40 μΐΏ or more is a number basis. 〇 5% or less. The above-mentioned amine resin crosslinked particles of the present invention can be obtained by the i-th or second production method of the amine resin crosslinked particles of the present invention described later. In the amine resin crosslinked particles of the present invention, the above average particle diameter is preferably from 0 to 15 μm. If the average particle diameter is outside the range of from 0.1 to 20 μηι, for example, the light diffusion performance when the light diffusion sheet using the amine resin crosslinked particles and the binder resin of the present invention is poor is used. In the present invention, the average particle diameter is measured using a Coulter multisizer-II type (manufactured by Coulter Corporation). • 9-(7) 200401786 In the amine resin crosslinked particles of the present invention, the ratio of the above-mentioned particle size to 4 〇 The number of coarse particles is preferably 0.03% or less, more preferably 1, and less than 0.01%. In addition, the above-mentioned number is based on the ratio of the number of particles and the ratio of the number of shoes to the total number of particles measured. Specifically, a particle size distribution measurement multi-meter-type (made by Coulter Co., Ltd.) was used to measure each particle diameter of 3,000, in which the number of particles having a particle diameter of a predetermined value or more was used for all 3 0 0 0 0 Ratio. The proportion of coarse particles with a particle size of 40 μηι or more is the number of particles of 0 · 0 5 ° / 〇, which are particles in the conventionally known amine resin crosslinked particles. For example, it is a light diffusion sheet for LCD, which is bonded to a PET sheet. When the resin resin is applied together, it is easy to cause dots due to coarse particles. In addition, when colored amine resin crosslinked particles are used, for example, when the transparent substrate is colored, discoloration due to coarse particles also occurs. Therefore, the agent for forming the amine resin crosslinked particles of the present invention, more specifically, light diffusion for LCD A sheet of light diffusing agent, a good implementation form. Alternatively, the film coating agent of the amine resin crosslinked particles of the present invention also becomes a preferred embodiment. In addition, the coloring agent formed by the amine resin crosslinked particles has also become a better practice. The amine resin crosslinked particles of the present invention are preferably based on the number of particles having an average particle size of μηι and a particle size of 8 μm or larger. The inventors have found that when the particle size of the amine resin crosslinked particles of the present invention is 0.1 to 5 μηι, of course, it is necessary to satisfy the above μηο above 0.0 2% or less: it means that i large particles are stored. The number of particles in the part of the ear particles: the standard exceeds the thinness of the thin film and the like, which causes problems such as the spot β vinyl sheet. The light diffusion system is relatively small. The application form of the present invention is formed. 0.1 to 5) · 0 5% or less, whose average particle size is -10- (8) (8) 200401786 4 0 μηι or more, the ratio of the number of coarse particles based on the ratio of 0.05% or less, and if the particle size is also satisfied at the same time If 8 μηι is used as a reference, and the ratio of the number of particles larger than the particle size is 0.05% or less, for example, when a light-diffusing agent such as a light-diffusing sheet or a coloring agent such as a vinyl chloride sheet is used, it can become as described above. Excellent transparency and uniformity Quality and appearance. In addition, in response to the thinning requirements of LCDs in recent years, light diffusion sheets with very thin coating thicknesses can be produced. In the above-mentioned preferred embodiment of the present invention, the ratio of the number of particles with a particle diameter of 8 μηι or more is based on 0.05% or less, and preferably 0.03% or less, and more preferably 0.02% or less. 0.001% is particularly preferred. When the ratio of the particles having a particle diameter of 8 μm or more is greater than 0.5%, the quality and appearance of superior transparency and uniformity may not be obtained. In the present invention, 'the average particle size can be easily and reliably obtained by the method for producing the amine resin crosslinked particle of the present invention using the prescribed production conditions, pulverization conditions, classification conditions, and particle transport conditions of the following amine resin crosslinked particles. The amine resin crosslinked particles whose diameter and distribution are in the above specific range, and the state of the amine resin crosslinked particles are not easy to change even during storage or storage. Specifically, the amount of coarse particles is not easy to change, and it is also for stability or storage. Good stability. Preservation stability or storage stability of the dry powder of the moon-daughter resin paternal particles. Specifically, it is expressed by the ratio of the average particle diameter change as the numerator, and the '丨' average particle diameter immediately after manufacture is the ratio obtained by the denominator. It is preferably less than 10%, and more preferably less than 5%. In addition, the amount of coarse particles with a particle diameter of 40 μm or more is expressed as a ratio obtained by 'the amount of coarse particles immediately after manufacturing is a denominator-11-(9) at 200401786', preferably 10% or less, 5 % Is better. Hereinafter, the above-mentioned amine resin crosslinked particles of the present invention having a specific average particle diameter and not including the number of coarse particles (or particles) above the specific particle diameter exceeding the specific ratio can be easily and surely described in detail. The method for producing amine resin parent particle of the present invention. In addition, in this specification, the liquid state of the amine tree parent particle manufacturing process is also referred to as "emulsion" and "suspension", and "emulsion" refers to the liquid in the liquid. Particles are dispersed as colloidal particles or larger coarse particles to become milky. "Suspension" refers to those in which solid particles in a liquid are dispersed as colloidal particles or particles visible to a microscope. (Method for producing amine resin crosslinked particles) The method for producing the amine resin crosslinked particles of the present invention 'will be described in detail below, so that the amine resin crosslinked particles of the present invention can be easily obtained. The biggest feature of the method for producing amine resin crosslinked particles of the present invention is that the pulverized material obtained by pulverizing the dried material of the amine resin crosslinked particles is classified. -No. 1 Production Method-The first production method of the amine resin crosslinked particles of the present invention (hereinafter also referred to as "the first production method") is characterized in that it is obtained by reacting an amine compound with formaldehyde as described above. After the amine resin precursor is emulsified and hardened in an aqueous medium to obtain amine resin crosslinked particles, the amine resin crosslinked particles are separated and dried from the aqueous medium during the emulsification, and the resulting dried powder is powder; 'rr -12 · 4 S b (10) 200401786 was crushed, and the resulting crushed product was classified. In addition to the general manufacturing method of the amine tree that implements the first manufacturing method, the following also describes the first manufacturing method and the first manufacturing method. In general, the amine resin manufacturing method includes: from amine compounds Resinization step obtained by reacting with formaldehyde to obtain a precursor, emulsification step of emulsifying the amine obtained in the resinization step to obtain an amine resin precursor emulsion, before adding a catalyst to the emulsion obtained in the step to emulsify the amine resin Curing step to obtain amine resin crosslinked particles. In the resinization step, an amine resin precursor using an amine compound and formaldehyde as an initial condensation reactant. The amination reaction generally uses water as a solvent. The reaction form is a form that reacts with formaldehyde in an aqueous medium to obtain an aqueous solution (reaction liquid) containing a precursor of an amine resin as a precursor. A specific method of the form may include making formaldehyde into an aqueous solution (a state where an amine compound is added and The method of performing the reaction, or the method of adding paraformaldehyde to water, and the method of reacting with the water amine compound that can generate formaldehyde are suitable. Among them, it is not necessary to adjust the tank due to the formaldehyde aqueous solution, and it is easier to get started. In general, the resinization step of the above reaction is preferably carried out by stirring with a stirring device or the like. The amine-based compound that can be used in the resinization step is not particularly limited, and examples thereof include benzofluorenyl-6-benzene. -Sym-three farming), cyclohexanemethanamine, and the characteristics of cyclic crosslinked particles. A method for preparing an amine resin before a crosslinked particle. A resin precursor is subjected to a hard reaction in the emulsification step to obtain a compound and a formaldehyde amine compound. The reaction is performed in the form of a fumaline) or a method of adding the former to a trioxane solution. It is also known to use i-amines (2,4-dihexenemethanamine-13- (11) (11) 200401786, melamine, etc.) as raw materials. Among them, in general, amines with three farming rings are used. The compound is better. In addition, benzoguanamine has excellent dyeability in the initial condensation state because it has a benzene ring and two reactive groups. It has flexibility (hardness), stain resistance, heat resistance, and solvent resistance after crosslinking. It is superior and extremely resistant. These amine compounds can be used alone or in combination of two or more. Among the amine compounds used, the amine compounds (benzoguanamine, cyclohexyl) exemplified above Alkylguanidine, cyclohexenemethanamine and melamine) are more preferably 40% by weight or more, more preferably 60% by weight or more, 80% by weight and more preferably 100% by weight. The above is best. By making the above example When the total amount of the amine-based compound is 40% by weight or more, it has the effect of obtaining so-called amine resin crosslinked particles having excellent heat resistance and solvent resistance. Molar ratio of the amine-based compound and formaldehyde reacted in the resinization step. (Amine compounds (Mole) / Formaldehyde (Mole)) is preferably 1/3 · 5 to 1/1 .5, more preferably 1 / 3.5 to 1/1 .8, and 1 / 3.2 to 1/2 is most If the molar ratio is less than 1/3. 5, the unreacted formaldehyde may be too much, and if it exceeds 1/1. 5, the unreacted matter of the amine compound may be too much. Also, use water as In the case of a solvent, the amount of amine compound and formic acid added to water, that is, the concentration of the amine compound and formaldehyde at the time of installation, as long as the reaction is not harmful, a higher concentration is preferred. More specifically, The viscosity of the reaction solution containing the reactant amine resin precursor in the temperature range of 9 5 to 9 8 t is adjusted and controlled within the range of 2 × 10 ··. To 5.5xl (T2pa · s (20 to 5) c P). It is better than the following emulsification step to make the fee resin in the emulsion into a range of 30 to 60% by weight, as long as -14- (12) (12) 200401786 is the concentration at which the reaction solution can be added to the aqueous solution of the emulsifier, or the emulsifier or the aqueous solution of the emulsifier can be added to the reaction solution. Therefore, the amine-containing resin precursor is obtained in the resinization step. When the reaction solution is used, the viscosity of the reaction solution in the temperature range of 95 to 98 ° C is preferably 2x1 0 · 2 to 5.5xl (T2Pa · s (20 to 55cP)), and 2.5xl0 · 2 to 5.5xl (T2Pa · s (25 to 55cP) is better, 3.0χ] (Γ2 to 5.5xl (T2Pa · s (30 to 55cP)) is even better. The above-mentioned viscosity measurement method is based on the use of a viscosity measuring machine, which can control the progress of the reaction in real time (r e a r t i in e), and can accurately identify the end point of the reaction. As the viscosity measuring machine, a vibration type viscometer (MIVI ITS, manufactured by our company, product name: MIVI 6001) can be used. The viscosity measuring machine is provided with a vibrating part that is constantly vibrating. The vibrating part is immersed in the reaction solution. The viscosity of the reaction solution increases, and the load of the vibrating part increases. By reacting an amine compound with formaldehyde in water (in an aqueous medium), an amine resin precursor of a so-called initial condensation reaction product can be obtained. The reaction temperature is such that the progress of the reaction can be grasped and the end point of the reaction can be accurately discriminated, and a temperature range of 95 to 98 ° C is preferable. Therefore, the reaction between the amine compound and formaldehyde can be terminated at a time point when the viscosity of the reaction solution becomes 2χ] (Γ2 to 5.5xl (T2Pa • s), such as cooling the reaction solution. A reaction solution containing an amine resin precursor. There is no particular limitation on the reaction time. The amine resin precursor obtained in the resinization step is derived from the structural unit of the amine compound that forms the amine resin precursor and from the formaldehyde. Structure (13) 200401786 Unite Morse ratio (construction unit derived from amine compounds (moulding unit from formaldehyde (mole)) with] / 3 · 5 to 1 /} 5 1/3 · 5 to 1 /1.8 is better, 1 / 3.2 to 1/2 is even better. By falling in the above range, particles with narrow particle size distribution can be obtained. In addition, the viscosity of the reaction liquid at the time point of the end of the reaction is usually a compound and formaldehyde (At the beginning of the reaction) The viscosity of the aqueous solution is increased, so there is little effect on the concentration of the raw materials. The amine tree is usually soluble in acetone, dioxane, methanol, ethanol, isopropanol, ethyl acetate, and acetic acid. Butyl vinegar, methyl cellulose, ethyl cellulose Organic solvents such as ketones, toluene, xylene, and water are substantially insoluble. The first manufacturing method is to reduce the viscosity of the reaction solution in the resinization step of obtaining the amine-containing resin precursor liquid, so that the final amine resin can be cross-linked. The particle size of the crosslinked particles becomes smaller. However, if the viscosity of the reaction solution is 2xl (T2Pa · s or more than 5.5xl (T2Pa · s), amine resin crosslinked particles with approximately uniform particles (narrow particle size distribution) cannot be obtained. If the viscosity is less than 2 X] 0 · 2 P a · s (2 0 c P), the emulsion obtained in the following step lacks stability. Therefore, when the precursor is hardened in the hardening step, the obtained amine resin crosslinked particles Hypertrophy, and aggregation may occur and the particle size of the amine resin crosslinked particles cannot be controlled to obtain amine resin crosslinked particles with a wide range of particle size distribution. In addition, the amine resin crosslinks each time it is manufactured (per batch) during opacification stability. The average particle size will change, and the product may be inconsistent. On the one hand, the viscosity of the reaction solution is greater than 5.5xl (T2Pa · s (55cf, the high-speed stirrer used in the emulsification step described below is too heavy, by ear) / Source is better, ί Ear ratio • Loaded with amine I more significantly, butanol, methyl ethyl in water. The degree of reaction is smaller than the final particle, that is, the particle size of the amine resin particles may be lacking if emulsified. Another > (14) (14) 200401786, the shear force is reduced, and the reaction solution may not be sufficiently stirred (make it opacified). Therefore, the particle size of the finally obtained amine resin crosslinked particles cannot be controlled and the particle size may be obtained. Widely distributed amine resin crosslinked particles. According to this, the viscosity of the reaction solution is adjusted to the above viscosity range in the resinization step, which becomes a preferred embodiment for obtaining the amine resin crosslinked particles of the present invention. The emulsification step is to emulsify the amine resin precursor obtained in the resinization step to obtain an emulsion of the amine resin precursor. For emulsification, for example, it is preferable to use an emulsifier that can constitute a protective colloid, and an emulsifier made of a water-soluble polymer that can constitute a protective colloid is more preferred. Examples of the emulsifier include polyvinyl alcohol, carboxymethyl cellulose, sodium alginate, polyacrylic acid, water-soluble polyacrylate, and polyvinylpyrrolidone. These emulsifiers can be used in the form of an aqueous solution in which all of them are dissolved in water, or a part of them can be in the form of an aqueous solution, and the rest can be used in the original state (for example, powder, granule, liquid, etc.). Among the emulsifiers exemplified above, when considering the stability of the emulsion and the interaction with the catalyst, polyvinyl alcohol is more preferably used. Polyvinyl alcohol may be completely saponified or partially saponified. The degree of polymerization of polyvinyl alcohol is not particularly limited. For the amine resin precursor obtained in the aforementioned resinization step, when the amount of the emulsifier used is large, the particle size of the generated particles tends to be small. The amount of the emulsifier used is preferably 1 to 30 parts by weight, and more preferably 1 to 5 parts by weight, based on 100 parts by weight of the limbs obtained in the aforementioned resination step. If the amount used is outside the above range, the emulsion may lack stability. : The emulsification step is, for example, in an aqueous solution of an emulsifier, and the amine resin precursor concentration (solid content concentration) obtained by adding the above-mentioned resinization step is within a range of 30 to -17-(15) (15) 200401786 6 0% by weight. After the reaction solution was between 50 and 100%. (: It is better to make the opacification in the temperature range, more preferably 60 to 100 ° C, and more preferably 70 to 95 ° C. The concentration of the emulsifier aqueous solution is not particularly limited as long as the amine resin can be used The concentration of the precursor may be adjusted to a concentration within the above range. If the concentration of the amine resin precursor is less than 30% by weight, the productivity of the amine resin crosslinked particles may decrease, and if it exceeds 60% by weight, the obtained amine resin crosslinks The crosslinked particles may be enlarged and the particles may agglomerate. Because the particle size of the amine resin crosslinked particles cannot be controlled, it is possible to obtain amine resin crosslinked particles with a wide particle size distribution range. The stirring method in the emulsification step is to use a stronger stirring. The method of installing the device (device with high shear force), specifically, for example, using a high-speed mixer or mixer, a TK mixer (special chemical industry (stock)), a high-speed disperser, a Yebara honing machine (Ebalamizer) ((share) Kashihara Manufacturing Co., Ltd.), high-pressure homogenizer ((share) Izumif ο 〇dmachina 1 · y)), static mixer ((share) Norritta Gmide system) In the emulsification step, it is preferable to emulsify the amine resin precursor obtained in the resinization step to a predetermined particle diameter, and the predetermined particle diameter may be appropriately determined according to the particle diameter of the final desired amine resin crosslinked particles. Specifically, the emulsification is performed by appropriately considering the type of the container or the stirring blade, the stirring speed, the stirring time, the emulsifying temperature, and the like, so that the average particle diameter of the emulsified amine resin precursor becomes 0.1 to 20 μ. m is preferable, 0.5 to 20 μm is more preferable, and 1 to 15 μm is more preferable. By emulsifying the amine resin precursor to the above-mentioned particle size range, the desired particle finally obtained as follows can be obtained Amine resin crosslinked particles with a diameter range. -18- (16) (16) 200401786 In the first production method, 'in order to more reliably prevent the finally obtained amine resin crosslinked particles from agglutinating firmly, if necessary, it can be used in the above emulsification step. Inorganic particles are added to the emulsion obtained afterwards. Preferred inorganic particles include silicon oxide microparticles, hafnium oxide microparticles, aluminum powder, alumina solution, and Seleaesol. Among them, it is easy to obtain. In other words, silica particles are better. The specific surface area of the inorganic particles is preferably 10 to 400 m 2 / g, more preferably 20 to 350 m 2 / g, and even more preferably 30 to 300 m 2 / g. The particle size is more preferably 0.2 μηι or less, 0.1 μηι or less, and most preferably 0.05 μm or less. If the specific surface area or particle diameter is within the above range, the finally obtained amine resin crosslinked particles can be prevented from being firm. Agglomeration can exert further superior effects. The method of adding inorganic particles to the emulsion is not particularly limited, and specifically, for example, a method of directly adding inorganic particles in the form of particles (particles) or dispersing inorganic particles in Method of adding dispersion state in water. The amount of inorganic particles added to the emulsion is preferably 1 to 30 parts by weight, and more preferably 2 to 28 parts by weight based on 100 parts by weight of the amine resin precursor contained in the emulsion. Serving is even better. If it is less than 1 part by weight, the amine resin crosslinked particles finally obtained cannot be sufficiently prevented from agglutinating sufficiently, and if it exceeds 30 parts by weight, aggregates containing only inorganic particles may be generated. In addition, the method of stirring the inorganic particles when adding the inorganic particles to the amine resin cross-linked particles is to 'use a strong stirring device (a device with a high shear force) as described above, preferably 1v at the hardening step. · In the step, a catalyst (more specifically, a hardening catalyst) is added to the emulsion obtained in the above emulsification step, and the emulsified amine resin precursor -19- (17) (17) 200401786 is hardened ( The amine resin precursor is hardened in an opacified state) to obtain amine resin crosslinked particles (specifically, a suspension of amine resin crosslinked particles). The catalyst (hardening catalyst) is preferably an acid catalyst. For the acid catalyst, inorganic acids such as hydrochloric acid, sulfuric acid and phosphoric acid can be used; ammonium salts of these inorganic acids; sulfonamide; sulfonic acids such as benzenesulfonic acid, p-toluenesulfonic acid, and dodecylbenzenesulfonic acid; Organic acids such as formic acid, benzoic acid, acetic acid, propionic acid, and salicylic acid. Among the acid catalysts exemplified above, inorganic acids are preferred in terms of hardening speed, and sulfuric acid is more preferred in terms of the corrosion resistance of the device and the safety of the inorganic acids during use. When sulfuric acid is used as the catalyst, for example, when compared with those using dodecylbenzenesulfonic acid, the amine resin crosslinked particles finally obtained are not discolored and have high solvent resistance. These may be used alone or in combination of two or more. The amount of the catalyst used is preferably 1000 parts by weight of the amine resin precursor in the emulsion obtained in the emulsification step, 0.1 to 5 parts by weight, more preferably 0.3 to 4.5 parts by weight, and 0.5 to 4.0. Parts by weight are even better. If the amount of the catalyst used exceeds 5 parts by weight, the opacified state will be destroyed, and agglomeration may occur between particles. If it is less than 0.1 parts by weight, the reaction will take a long time, and hardening may be insufficient. In the same manner, the amount of the catalyst used is preferably 0.02 mol, more preferably 0.005 mol, and even more preferably 0.001 to 0.1 mol for the amine compound 1 mol used as the raw material compound. The amount of catalyst used is less than 0 · 002 mol for the amine compound 1 and the time required for the reaction is long, and the hardening may be less than ° The hardening reaction in the hardening step is preferably 15 (normal temperature) to 80 t Better than 20 to 70 ° C 'preferably maintained at 30 to 60 ° C for at least 1 60 (18) 200401786 hours, better than 60 to 150 ° C under normal pressure or pressure' better than To] 3 0 ° C, preferably within a temperature range of 60 to] 0 0 ° C. If the reaction temperature of the hardening reaction is lower than 60 ° C, it will not be fully hardened. The solvent resistance or heat resistance of the obtained amine tree crosslinked particles may be reduced. If it exceeds 150 ° c, a strong pressurized reactor must be used, which is uneconomical. . The end point of the sclerosis reaction can be determined by sampling or visual inspection. The reaction time for the 'hardening reaction' is not particularly limited. The stirring method in the hardening step is preferably carried out under stirring using a generally known stirring device. In the hardening step, the average size of the crosslinked amine resin crosslinked particles is preferably 0.1 to 20 μηι, so that the amine resin precursor hardened in the opacified state becomes 0.1 to 20 μm, more preferably 1 to 15 μm and more The first manufacturing method may include a coloring step of adding a cereal solution obtained by dissolving a dye in water to an emulsion of an amine resin precursor or a cloud solution of amine resin crosslinked particles. An amine resin precursor or amine The more affinity the resin crosslinked particles have with the dye. The dye added in the coloring step of the emulsion of the amine resin precursor obtained or the turbid liquid of the amine resin crosslinked particles is water soluble as long as it is water soluble. The dye is not particularly limited. Specific examples of the water-soluble dye include rhodamine B, rhodamine 6 GC P (above, manufactured by Sumitomo Chemical Industries, Ltd.), methyl violet FN, and Victoria blue FN. Dyes; acid dyes such as quinoline yellow-SS-5G, quinoline yellow-SS-GC (above, manufactured by Chuo Synthetics Co., Ltd.), acid fuchsin 0, methyl violet FB, and vitaro blue FB, etc., There is no particular limitation. These dyes can be obtained by reversing SLR lipids. ) .5 Suspension is excellent. It is also used for industrialization. -21-(19) (19) 200401786 It can also be used for more than 2 types. The concentration of the dye in the aqueous solution is not particularly limited, but it is more preferably within a range of 0 to 5% by weight, and even more preferably within a range of 1 to 3% by weight. If the dye concentration is lower than G. 1% by weight, the productivity of the amine resin particles is reduced due to the increase in the amount of the aqueous solution added. On the other hand, if the dye concentration exceeds 5% by weight, the stability of the emulsion is reduced, so that the obtained amine resin crosslinked particles become enlarged and aggregation between the particles may occur. The method for preparing an aqueous solution prepared by dissolving a dye in water, and the method for adding an aqueous solution and mixing it in an emulsion are not particularly limited. In the first manufacturing method, if necessary, a dye may be added to the reaction solution obtained in the resinization step as a first-stage coloring step. The dye is not particularly limited as long as it is a water-soluble dye, that is, an oil-soluble dye. Specific examples of the oil-soluble dye include oily orange B, oily blue BA (above 'Central Synthetic Chemical Co., Ltd.'), azo-soluble yellow-4GF, azo-soluble fast blue-GLA, and oil-based orange TR-71. Soluble dyes; disperse dyes such as fast yellow-YL, fast blue FG, Sanlitong Pink FF 3 B, and Sanlitong Pink 3 B; etc. are not particularly limited. These dyes can be used alone or in combination of two or more. By adding a dispersion liquid obtained by dispersing an oil-soluble dye in water to the reaction coloring step and the aforementioned coloring step of the reaction liquid obtained in the resinization step, the coloring can be more fully and uniformly, and the hue of each particle can be obtained. Neat amine resin particles. The content of the dye in the dispersion obtained by dispersing the oil-soluble dye in water is not particularly limited, but it is more preferably in the range of 1 to 50% by weight, and even more preferably in the range of 20 to 40% by weight. If the content of the dye is less than 1% by weight, the added liquid 4b b • 22-(20) (20) 200401786 increases the amount of liquid dispersion, and thus the productivity of the amine resin crosslinked particles may be reduced. On the other hand, if the content of the dye is more than 50% by weight, the fluidity of the dispersion is lowered ', so that the workability during addition is not good and the addition operation is complicated. In addition, since oil-soluble dyes lack wettability to water, when dispersing the dyes in water, a dispersing aid may be used if necessary. A method of dispersing a dye in water to prepare a dispersion liquid, and a method of adding a dispersion liquid to a reaction liquid and mixing them are not particularly limited. After the above reaction solution (solution) is added with a dispersion liquid obtained by dispersing a dye in water, for example, it is adjusted to a pH of 6 to 12 by using an alkaline agent such as sodium carbonate, sodium hydroxide, potassium hydroxide, and ammonia water. More preferably, it is in the range of 7 to 9. Accordingly, the condensation and hardening of the amine resin precursor in the hardening step can be sufficiently controlled. The amount of the alkali agent used is not particularly limited. Although the method of adding the alkaline agent to the reaction solution in the form of an aqueous solution and mixing it is preferable, the method is not particularly limited. The first production method may include a neutralization step of neutralizing the suspension containing the amine resin crosslinked particles obtained in the above-mentioned curing step. The neutralization step is preferably performed when an acid catalyst such as sulfuric acid is used as the hardening catalyst in the hardening step. The neutralization step can remove the above-mentioned acid catalyst (specifically, neutralize the acid catalyst). For example, when the amine resin crosslinked particles are heated in the following heating step or the like, the discoloration of the amine resin crosslinked particles can be suppressed ( Such as turning yellow). The colored amine resin cross-linked particles also have an effect of preventing yellowing, and can obtain an embodiment in which the neutralization step, which is superior in heat resistance and Z sharply colored particles, is obtained. The so-called "neutralization" of the neutralization step is a suspension of amine-containing resin crosslinked particles
-23- (21) (21)200401786 濁液的pH調成5以上爲佳，pH調成5至9更佳。該懸濁 液之pH若小於5，因酸觸媒殘留而於後述加熱步驟等 中，胺樹脂交聯粒子會變色。藉中和將該懸濁液的pH調 節成上述範圍內，即可獲得硬度高、耐溶劑性及耐熱性優 越且不變色之胺樹脂交聯粒子。 中和步驟所使用之中和劑例如以鹼性物質爲宜。該鹼 性物質爲例如碳酸鈉、氫氧化鈉、氫氧化鉀、氨等，其中 就處理容易方面而言以氫氧化鈉爲佳，以使用氫氧化鈉水 溶液爲宜。此等可單獨使用，亦可2種以上倂用。 第1種製造方法中，亦可包含自硬化步驟後或中和步 驟後所得胺樹脂交聯粒子之懸濁液中取出該胺樹脂交聯粒 子之分離步驟。又，第1種製造方法中，自懸濁液中分離 並取出胺樹脂交聯粒子係指將經硬化而得之胺樹脂交聯粒 子乳化時（乳化步驟時）自水系介質分離而取出者。 自懸濁液中分離並取出胺樹脂交聯粒子之方法（分離 方法）可例舉如過濾法或使用離心機等分離機等簡便方 法，並無特別限定，可使用一般週知方法。又，自懸濁液 取出之胺樹脂交聯粒子，視需要亦可用水等洗淨。 第1種製造方法中，較好進行將經分離步驟取出之胺 樹脂交聯粒子，於I 3 0至1 9 0 °c加熱之加熱步驟。藉由加 熱步驟可去除附著於胺樹脂交聯粒子之水分及殘留之游離 甲醛，且可更進一步促進胺樹脂交聯粒子之合（交 聯）。上述加熱溫度低於I 3 (TC時，不能充分促進胺樹脂 交聯粒子內之縮合（父聯），而可能無法提昇胺樹脂交聯 -24- (22) (22)200401786 粒子之硬度、耐溶劑性及耐熱性，若超過]9 0 °C則所得胺 樹脂交聯粒子有變色之可能。即使進行上述中和步驟之情 況，亦同樣受到加熱溫度在上述範圍外時之相同影響。藉 由進行中和步驟，並使胺樹脂交聯粒子之加熱溫度在上述 範圍內，可獲得硬度高、耐溶劑性及耐熱性優越且不變色 之胺樹脂交聯粒子。 加熱步驟中之加熱方法並無特別限定，可使用一般週 知之加熱方法。 加熱步驟例如可於使胺樹脂交聯粒子含水率成爲3重 量％以下之階段終止。又，加熱時間並無特別限定。 第1種製造方法中，更好將胺樹脂交聯粒子自懸濁液 分離取出，並乾燥（加熱）、粉碎而得之胺樹脂交聯粒子 粉體，進一步分級成爲平均粒徑0.1至20 μηι，且粒徑40 μηι以上之粗大粒子爲個數基準0.05%以下之胺樹脂交聯 粒子。 於胺樹脂交聯粒子之製造方法中，加熱步驟所產生之 排出氣體中含有害之甲醛爲向來存在之問題，迄今一般係 以水吸收或燃燒處理。然而，由於吸收時必須大量水，且 需要長時間吸收而不經濟。因此，該步驟產生之含甲醛排 出氣體以使用白金爲主成分之觸媒進行燃燒處理爲佳。 第1種製造方法中，經硬化反應步驟所得之胺樹脂交 聯粒子，係如前述般，將其於乳化時自水系介質分離並乾 燥，將所得之乾燥物粉碎，最後再將所得之粉碎物進行分 級。 -25- (23) (23)200401786 進行前述粉碎之粉碎步驟係指於硬化、分離、乾燥 (加熱）步驟中將凝集之胺樹脂交聯粒子鬆碎之步驟。 又，進行前述分級之分級步驟係指減少乳化步驟所生成之 微小粒子、特定粒徑以上之粗大粒子或粒子、以及於前述 粉碎步驟未能鬆碎之凝集粗大粒子或凝集粒子的步驟，可 爲僅進行分級之步驟’亦可爲同時進行分級及粉碎之步 驟。又，同時進行前述粉碎與分級時，可於粉碎後分級， 亦可同時進行粉碎與分級。 第〗種製造方法中，粉碎步驟與分級步驟可使用粉碎 機與分級機各別之裝置，亦可使用兼具粉碎與分級二機能 之裝置（粉碎分級機）。粉碎機可例舉如梵它姆磨 (B a n t a m υ mill)、帕魯貝硏磨機（P a ] b e 1 a i z e r，細川微 米（Hosokawa micron) (股）製） ，山普磨 (Samplemill，不二粉末（股）製）、噴射磨等。分級機 可例舉如微分離器（細川微米（股）製））、微米分級器 ((股）精心（Sesin )企業製）、土波分級器（TURBO CLASSIFIER，日淸工程（股）製）等。粉碎分級機可例 舉如 LABO JET (日本新馬其（Newmatch)工業（股） 製）、噴射粉碎分級機S T J -2 0 0 ((股）精心企業製）。 粉碎分級機就經濟面理由而言因係緊密裝置而爲較佳形 態。 粉碎及/或分級之條件並無特別限定，例如於上述粉 碎處理以後之至少一個處理（粉碎及/或分級之步驟以及 其間之步驟或其後步驟中之至少一個處理步驟。以下同） -26- (24) 200401786 中’爲形成氣流所使用之氣體其條件以水分含量控制在 6g/m3以下爲佳，以水分含量控制在5g/m3以下之氣體更 佳’水分含量控制在4g/m3以下之氣體又更佳，水分含量 控制在3 g/m3以下之氣體再更佳，特別是水分含量控制在 2g/m3以下之氣體，最好是水分含量控制在lg/ni3以下之 氣體。形成氣流所使用之氣體係指粉碎或分級之步驟所使 用之氣體，亦包含各步驟間粒子傳送（粒子運送）所使用 之氣體。水分含量控制如上述情況之理由，係於將前述硬 化所得之粉體粉碎及/或分級之步驟中，或於各步驟間傳 送（運送）之步驟中，形成氣流所使用之氣體若使用水分 含量多於6g/m3之氣體，例如使用一般空氣（大氣）時， 曾經粉碎及/或分級之部分粒子可能再度凝集成爲粗大粒 子。又，水分含量之下限並無特別限定，理想者爲0，但 現實上爲例如 0.05g/m3以上。使用前述粉碎分級機時， 以使用控制成爲上述水分含量之氣體特佳，可容易且確實 而有效的獲得特定粒徑以上之粒子（4 0 μηΐ以上之粗大粒 子等）之比例在特定標準以下之上述本發明之胺樹脂交聯 粒子。 粉碎及/或分級之條件爲上述中，粉碎以後之所有處 理（粉碎之步驟、分級之步驟、該等間之步驟或其等後之 步驟等所有處理步驟。以下相同）中，有關形成氣流所使 用氣體之條件以將其水分含量控制於上述範圍內爲佳。 粉碎及/或分級之條件係於上述粉碎後以使用控制爲 上述水分含量之氣體用於大氣管理爲佳。上述大氣管理可 -27- (25) (25)200401786 具體例舉如將進行前述粉碎或分級等胺樹脂交聯粒子各種 處理操作之室內藉使用上述氣體而管理水分含量等。藉由 上述大氣管理’例如’將自粉碎裝置排出之粉碎物以暴露 於周圍大氣之狀態傳送至下一分級裝置之投入口時，經由 控制各步驟間粒子傳送（運送）間氣體之水分含量，則即 使短暫經過暴露於周圍大氣之過程，亦可有效防止部分粒 子再度凝集成爲粗大粒子。 上述粉碎及/或分級後之步驟中，使用控制在上述水 分含量之氣體，或於上述粉碎後之步驟中，大氣管理係使 用控制在上述水分含量之氣體，則可容易的達到本發明規 定之上述特定粒徑以上之粗大粒子或粒子之比例在特定標 準以下。 上述分級後於密封容器內保存及貯藏時，於該密封容 器內充塡控制爲上述水分含量之氣體，則可獲得優越之保 存安定性及貯藏安定性效果。亦即，使用控制爲上述水分 含量之氣體以密封容器保存之方法爲本發明之較佳形態。 以該保存方法保存及貯藏之胺樹脂交聯粒子，可成爲不僅 在保存及貯藏之前或之後均能滿足上述特定之平均粒徑與 特定粒徑以上之粗大粒子或粒子之比例在特定標準以下之 粒度分佈特性’且如下述般具有非常顯著之保存安定性及 貯藏安定性之本發明胺樹脂交聯粒子。 有關保存安定性及貯藏安定性，係將分級後所得之樹 脂交聯粒子，使用滿足上述水分含量條件之氣體於密封容 器內保存]個月，並評估特定粒徑以上之粗大粒子或粒子 >28- (26) (26)200401786 之比例變化程度。具體言之，以「保存前特定粒徑以上之 粗大粒子或粒子之比例（％ )」爲a，以「保存後特定粒 徑以上之粗大粒子或粒子之比例（％ )」爲b時，以下式 (A ) (| a-b | / a )X10 0(% ) (A) 求得之値評估之，該値以30%以下爲佳，20%以下更 佳，】〇%以下又更佳，5%以下再更佳，特別是1%以下最 佳。又’ 1個月期間於密封容器內保存之評估値以及6個 月期間於密封容器內保存之評估値能滿足上述範圍者最 佳。 於上述粉碎及/或分級後之步驟中，有關形成粉碎及/ 或分級時之氣流所用氣體之條件，因有粉塵爆發之危險 性，以使用氧氣濃度低之惰性氣體爲佳，具體言之，氧氣 濃度以10%以下爲佳，5%以下更佳，3%以下又更佳。此 類惰性氣體可例舉如氮氣、氦氣、氬氣等稀有氣體，而就 經濟性方面以氮氣爲佳。其氧氣濃度條件可與上述水分含 量之條件合倂控制，亦可與上述水分含量之條件分開各別 控制，但以前者爲佳。 分級方式可大致區分爲乾式及濕式，濕式之情況其後 必須施予乾燥步驟，因於乾燥時粒子會凝集成爲粗大粒 子，必須再度施予乾式分級，其步驟繁雜而不佳。就可使 涉一驟簡略化言之以乾式分級爲佳。乾式分級之方式可大致 區分爲氣流分級方式、篩方式。使用篩方式時，胺樹脂交 聯粒子因粒子交聯變硬’篩孔有粒子阻塞時不易去除（勉 >29- (27) (27)200401786 強去除時則篩孔會變形），就容易連續生產方面以氣流分 級方式爲佳。 以上述氣流分級方式進行分級步驟時，胺樹脂交聯粒 子粉體之供給速度以控制在0 . 1 5至〗〇 Qkg/h爲佳，0 1至 5 〇k g/h更佳。若控制供給速度使滿足上述範圍，即可容易 的獲得前述之本發明胺樹脂交聯粒子。 同樣的，以氣流分級方式進行分級步驟時，氣流之總 風量以控制在0 : 5至3 0 m3 / m i η爲佳，0.5至2 5 m3 / m i η更 佳。若控制總風量使滿足上述範圍，即可容易的獲得前述 之本發明胺樹脂交聯粒子。 又’上述總風量係指形成氣流分級用氣流所用氣體之 總量。一般爲了形成氣流係使用風扇等將分級機內之氣體 及流入（通入）分級機內之氣體排出，此種情況總排氣量 即爲總風量。以氣流分級方式進行上述分級步驟時，最好 控制上述供給速度以及總風量使均能滿足上述條件。 以氣流分級方式進行上述分級步驟時，上述供給速度 以及總風量之比「總風量/供給速度」以控制使滿足01-5 0爲佳，0 · 1至3 0更佳，0.5至1 0又更佳。上述比小於 〇 · 1時，胺樹脂交聯粒子之收量可能降低，若超過5 0則特 定粒徑以上之粗大粒子可能增多。 如上述般，自懸濁液中分離硬化所得之胺樹脂交聯粒 子並乾燥、粉碎再分'級，可獲得特定粒徑以上之粗大粒子 (或粒子）個數基準之含有比例降低至特定標準以下之胺 樹脂交聯粒子。 -30- (28) (28)200401786 於第]種製造方法中，如上述採用氣流粉碎分級或氣 流分級方式，並使用將水分含量降低至特定標準之氣體作 爲傳送氣體（運送用空氣等），則於連續一系列步驟中亦 不會混入餘份水分等，而可安定的製造該胺樹脂交聯粒子 並密封於容器內。 於第1種製造方法中，上述硬化亦可於乳化所得之乳 濁液中添加觸媒而進彳了，且前述觸媒之添加以自上述乳化 開始後5小時內進行爲佳。 如此’錯由將乳化開始（胺樹脂前驅體與乳化劑（乳 化劑水溶液）開始混合時）至硬化開始（添加觸媒時）之 時間（下文亦稱爲乳化時間）控制爲5小時以內，即可容 易的獲得個數基準之含有比例降低至規定之標準以下之胺 樹脂交聯粒子。 上述乳化時間以4小時以內爲佳，3小時以內更佳， 2小時以內又更佳，1小時以內最佳，上述時間若超過5 小時則特定粒徑以上之粗大粒子（或粒子）之發生量會增 加而不宜。 有關自前述乳化時間開始至終止間之操作係如前述以 乳化開始爲起始而以硬化開始爲終了之外，並無特別限 制。 然而，例如①可將含胺樹脂前驅體之反應液與乳化劑 攪拌混合使胺樹脂前驅體成乳濁狀態後，停止攪拌並靜置 使冷卻至規定之溫度、②亦可於上述冷卻後進行添加規定 之無機粒子等之其他步驟、③亦可於達規定之乳濁狀態爲 31 - (29) (29)200401786 止均繼續上述攪拌混合，其後於添加觸媒之前亦可一邊繼 續攪拌（以較開始時爲和緩之攪拌爲佳）一邊冷卻，並無 特殊限定。 一般而言，例如進行如上述③之操作時，咸認若乳化 時間長則由於其充分攪拌而對乳濁狀粒子施加剪切力之時 間增長，因而粗大粒子減少，又，例如進行上述①或②之 操作時，咸認一旦成爲乳濁狀態則各個粒子係藉由靜置冷 卻而呈安定之單獨分散狀態，粗大粒子不會增加。然而令 人驚訝的是，上述①至③等任一情況下，可確認其乳化時 間若超過5小時，則粗大粒子之發生量有增加之傾向。原 因雖未確定，例如由於繼續施予一定時間以上之剪切力或 繼續維持一定時間以上之靜置狀態等，則乳化物中之粒子 表面之乳化膜破壞，而易發生凝集所致。 上述第]種製造方法，係可容易的獲得本發明胺樹脂 交聯粒子之方法，亦即，由於可容易的獲得平均粒徑〇.] 至2 0 μηι ’且粒徑4 0 以上之粗大粒子之比例爲個數基 準0 · 0 5 %以下之胺樹脂交聯粒子而爲較佳之方法。 -第2種製造方法- 本發明該胺樹脂交聯粒子之第2種製造方法（下文亦 簡稱爲「第2種製造方法」），其特徵係將由胺系化合物 與甲醛反應所得之胺樹脂廊驅體於水系介質中與介面活性 劑混合’於該混合液中添加觸媒使前述胺樹脂前軀體自前 述水系介質中粒子化析出後，將前述胺樹脂交聯粒子自前 -32- (30) (30)200401786 述乳化時之水系介質分離、乾燥，將所得乾燥物粉碎，並 將所得之粉碎物分級者。 第2種製造方法’雖亦係依據第1種方法所述之樹脂 化步驟’亦即藉由胺系化合物與甲醛反應之步驟而獲得胺 樹脂前驅體，但第2種製造方法係將該樹脂化步驟所得之 胺樹脂前驅體於水系介質中施予與介面活性劑混合之混合 步驟，以及於該混合液中施予添加觸媒使藉由胺樹脂前驅 體之硬化而粒子化及析出而獲得胺樹脂交聯粒子之硬化· 粒子化步驟之點係與第1種製造方法不同。 本發明之胺樹脂交聯粒子以平均粒徑0.1至2 0 μηι， 且粒徑4 0 μηι以上之粗大粒子之比例爲個數基準0 · 0 5 %以 下爲佳，該範圍內之粒子中，亦如前述以平均粒徑0 . 1至 5 μηι，且粒徑8 μηι以上之粒子之比例爲個數基準0.05% 以下爲佳。第1或第2種製造方法中，具有該較佳平均粒 徑等之本發明胺樹脂交聯粒子較佳爲以第2種製造方法獲 得。第2種製造方法之較佳狀態係藉由於水溶液狀態下開 始胺樹脂前驅體之硬化而可容易的調製粒子徑極小之胺樹 脂交聯粒子，而易獲得平均粒徑爲〇 · 1至5 μηι，且粒徑8 μηι以上之粒子之比例爲個數基準0.05%以下之胺樹脂交 聯粒子。 又，第2種製造方法中所使用之胺系化合物以能滿足 下述之水混合性之程度，而其種類及組成比適當設定者爲 佳，但以與甲醛反應可生成水溶性胺樹脂前驅體爲必須者 更佳。又，樹脂化步驟所得之胺樹脂前驅體以水溶性者爲 -33- (31) (31)200401786 佳。 第2種製造方法中所使用之介面活性劑係爲了使胺樹 脂前驅體於水性介質中獲得水親合性而使用者，而不包含 第1種製造方法中所使用之乳化劑。 上述水親合性之程度係依據於1 5 t下，測定於初期 縮合物胺樹脂前驅體中滴加水至產生白濁時所滴加之水 量’其對初期縮合物之重量％ (下文，簡稱爲水混合 度）’而第2種製造方法中較佳之胺樹脂前驅體之水混合 度爲1 0 0 %以上。水混合度小於1 〇 〇 %之胺樹脂前驅體，於 含介面活性劑之水性液中，不管如何分散亦只能形成粒徑 較大之不均勻懸濁液，而最終所得之球狀微粒子難以成爲 均勻之粒徑。 於混合步驟中，係將樹脂化步驟所得之胺樹脂前驅體 於水性介質中藉由攪拌等與介面活性劑混合而獲得混合 液。 上述介面活性劑可使用例如陰離子性介面活性劑、陽 離子性介面活性劑、非離子性介面活性劑、兩性介面活性 劑等所有介面活性劑，特別以陰離子性介面活性劑或非離 子性介面活性劑或者該等之混合物爲佳。陰離子性介面活 性劑可使用十二烷基硫酸鈉、十二烷基硫酸鉀等烷基硫酸 鹼金屬鹽；十二烷基硫酸銨等烷基硫酸銨鹽；十二烷基聚 乙二醇醚硫酸鈉；硫蓖麻油_鈉；磺化石蠛之鹼金屬鹽、 磺化石蠟之銨鹽等烷基磺酸鹽；月桂酸鈉、三乙醇胺油酸 鹽、三乙醇胺松香酸鹽等脂肪酸鹽；十二烷基苯磺酸鈉、 -34- (32) (32)200401786 鹼性酚羥基乙烯之鹼金屬硫酸鹽等烷基芳基磺酸鹽；高烷 基萘磺酸鹽；萘磺酸嗎啉縮合物；二烷基磺琥珀酸鹽；聚 氧化乙烯烷基硫酸鹽；聚氧化乙烯烷基芳基硫酸鹽等，非 離子性介面活性劑可使用聚氧化乙烯烷基醚，聚氧化乙燏 烷基芳基醚；山梨糖醇酐脂肪酸酯；聚氧化乙烯山梨糖醇 酐脂肪酸酯；甘油之單月桂酸酯等之脂肪酸單甘油酯；聚 氧化乙烯氧化丙烯共聚物環氧乙烷與脂族胺、醯胺或酸之 縮合生成物等。介面活性劑之使用量，對上述樹脂化步驟 所得之胺樹脂前驅體1 ο 〇重量份以ο. 〇 1至1 〇重量份之範 圍較佳。若爲小於0.0 1重量份之少量則可能不能獲得胺 樹脂交聯粒子之安定懸濁液，又若爲超過1 0重量份之多 量則於上述懸濁液中會產生不必要之泡沫而對最終所得胺 樹脂交聯粒子之物性有不良影響。 混合步驟例如係將胺樹脂前驅體之濃度（即固形物濃 度）成爲3-25重量％範圍內之上述樹脂化步驟所得之反應 液，添加至介面活性劑之水溶液後，進行混合爲佳。此種 情況，介面活性劑水溶液之濃度並無特別限定，只要爲可 將胺樹脂前驅體之濃度調節於上述範圍內之濃度即可。上 述胺樹脂前驅體之濃度若小於3重量％，則胺樹脂交聯粒 子之生產性可能降低，若超過2 5重量％，則所得胺樹脂 交聯粒子可能肥大化，且粒子間亦可能凝集，由於不能控 制胺樹脂突聯粒子之粒徑，而可能成爲粒度分布廣之胺樹 脂交聯粒子。 混合步驟中之攪拌方法，可採用一般方法，例如以使 -35- (33) (33)200401786 用盤形渦輪機、風扇渦輪機、法厄德拉形攪拌機、螺旋槳 型及多段翼等攪拌翼之攪拌方法爲佳° 第2種製造方法中，爲更進一步防止最終所得之胺樹 脂交聯粒子牢固凝集，必要時可於混合步驟後，於所得之 混合液中添加無機粒子。有關無機粒子及其添加方法等， 可依據前述第1種製造方法所說明者同樣使用。 硬化•粒子化步驟係於上述混合步驟所得之混合液中 添加觸媒（詳言之爲硬化觸媒），藉由胺樹脂前驅體之硬 化反應及其粒子化而獲得胺樹脂交聯粒子（詳言之爲胺樹 脂交聯粒子之懸濁液）。 上述觸媒（硬化觸媒）以酸觸媒爲佳。酸觸媒可適當 使用第1種製造方法中所例舉之相同者。第2種製造方法 中，特別以使用具有碳數1 〇至1 8烷基之烷基苯磺酸爲 佳。 具有碳數1 0至1 8烷基之烷基苯磺酸係於前述作爲初 期縮合物|女樹脂則驅體之水性液中，發揮特異之介面活性 機能，而生成硬化樹脂之安定懸濁液所必須之成分，可例 舉如癸基苯磺酸、十二烷基苯磺酸、十四烷基苯磺酸、十 六院基苯磺酸、十八院基苯擴酸等。此等可僅使用一種， 亦可2種以上倂用。 上述觸媒之使用量，對上述混合步驟所得之混合液中 月女树β日則驅體1 〇 〇重量份以〇 · 1 · 2 〇重量份爲佳，〇 · 5 · 1 〇 重夏份更佳，1 0重量份又更佳。特別是使用上述具有 碳數1 〇至]8烷基之烷基苯磺酸時，對混合液中胺樹脂前 -36 - (34) (34)200401786 驅體1 0 0重量份以0 ·] - 2 0重量份爲佳，〇 · 5 - 1 〇重量份更 佳。上述觸媒之使用量若較上述範園少量則縮合硬化所需 時間長’且不能獲得胺樹脂交聯粒子之安定懸濁液，而最 終可能只獲得含多量凝集粗大化粒子之狀態。又，較上述 範圍多量則所生成懸濁液中之胺樹脂交聯粒子中，必定分 配有超過需要之上述烷基苯磺酸等觸媒，結果胺樹脂交聯 粒子爲可塑化而於縮合硬化中粒子間易產生凝集或融著， 而最終可能無法獲得具有均一粒子徑之胺樹脂交聯粒子。 同樣的，上述觸媒之使用量，對作爲原料化合物用之胺系 化合物1莫耳以0.0005莫耳以上爲佳，0.002莫耳以上更 佳，0.005 -0.05莫耳又更佳。觸媒之使用量對胺系化合物 1莫耳小於〇 . 〇 〇 〇 5莫耳時，需要長時間反應，且硬化可能 不足。 硬化·粒子化步驟中之硬化反應及粒子化，可於胺樹 脂交聯粒子之混合液中添加上述觸媒，而於0 °c之低溫至 加壓下1 〇 〇 °c以上之高溫於攪拌下保持。上述觸媒之添加 方法並無特別限制可適當加以選擇。 硬化反應之終點可依據取樣或目視判斷。又，硬化反 應之反應時間並無特別限定。硬化反應一般係昇溫至於 9 0 °C或以上之溫度並保持一定時間使完成，不一定需要高 溫下硬化，即使低溫下短時間，只要所得懸濁液中之胺樹 脂交聯粒子達到以甲醇或丙酮不會膨潤之程度之硬化程度 即足夠。 硬化•粒子化步驟中之攪拌方法以使用週知之攪拌裝 (35) (35)200401786 置等進行攪拌爲佳。 硬化·粒子化步驟中，使上述混合液中之胺樹脂前驅 體硬化同時粒子化所得之胺樹脂交聯粒子之平均粒徑成爲 0 1至2 0 μ m爲佳，〇 ]至1 〇 μ m更佳，〇】至5 μ m又更 佳。 第2種製造方法中，可包含將染料溶解於水所得之水 溶液添加至胺樹脂前驅體與介面活性劑之混合液或胺樹脂 交聯粒子之懸濁液的著色步驟。染料之種類或其使用量係 與第1種製造方法所說明者相同。 第2種製造方法中，視需要亦可於上述樹脂化步驟所 得之反應液中，另添加染料作爲前段著色步驟。有關該前 段著色步驟所使用染料之種類或其使用量，以及添加將油 溶性染料分散於水而得之分散液時之pH調整之詳細情 形，係與第1種製造方法所說明者相同。 第2種製造方法中，可包含將含上述硬化步驟所得胺 樹脂交聯粒子之懸濁液加以中和之中和步驟。有關中和步 驟中pH之範圍或中和劑之詳細情形，係與第1種製造方 法所說明者相同。 第2種製造方法中，亦可包含自硬化步驟後或中和步 驟後所得胺樹脂交聯粒子之懸濁液取出該胺樹脂交聯粒子 之分離步驟。又，第2種製造方法中，自懸濁液中分離並 取出胺樹脂交聯粒子係指將硬化所得这胺樹脂交聯粒子於 混合步驟中自水系介質分離而取出者。 自懸濁液中分離並取出胺樹脂交聯粒子之方法（分離 -38- (36) (36)200401786 方法）’係與第]種製造方法所說明者相同。又，第2種 製造方法中，將胺樹脂父聯粒子自懸濁液分離取出，係指 經硬化•粒子化而得之胺樹脂交聯粒子自混合步驟或硬化 •粒子化步驟時之水系介質分離而取出者。 第2種製造方法中，較好將經分離步驟取出之胺樹脂 交聯粒子，進行於1 3 0至1 9 0。(：加熱之加熱步驟。有關加 熱步驟之詳細情形，係與第1種製造方法所說明者相同。 又，第2種胺樹脂交聯粒子之製造方法中，將胺系化 合物與甲醒反應所得之胺樹脂前驅體於水系介質中與介面 活性劑混合，於該混合液中添加觸媒使上述胺樹脂前驅體 於水系介質中粒子化，而獲得胺樹脂交聯粒子之方法中， 更好將硬化及粒子化所得之胺樹脂交聯粒子自懸濁液分離 取出，並將乾燥（加熱）、粉碎而得之胺樹脂交聯粒子粉 體’進一步進行分級步驟之形態爲佳。更具體言之，第2 種胺樹脂交聯粒子之製造方法，係將胺系化合物與甲醛反 應所得之胺樹脂前驅體於水系介質中與介面活性劑混合， 於該混合液中添加觸媒使上述胺樹脂前驅體於上述水系介 質中粒子化，而獲得胺樹脂交聯粒子之方法中，更好將硬 化及粒子化所得之胺樹脂交聯粒子自懸濁液分離取出，並 將乾燥（加熱）、粉碎而得之胺樹脂交聯粒子粉體，進一 步分級成爲平均粒徑0.1至20 μΐΏ，且粒徑40 μηι以上之 粗大粒子爲個數基準0.05%以下之胺樹脂交聯粒子之實施 形態爲佳，更好可獲得平均粒徑〇 · 1至5 pm，且粒徑8 μηι以上之粒子爲個數基準0 05 %以下之胺樹脂交聯粒 -39- (37) (37)200401786 子。 第2種製造方法中，與第】種製造方法同樣係以使用 白至爲主成分之觸媒將前述加熱步驟所產生之含甲醒之排 出氣體進行燃燒處理之實施形態爲佳。 第2種製造方法中，有關前述粉碎及或分級以後各步 驟之各種手段及方法或各種條件之詳細情形，均完全與第 1種製造方法所說明者相同。 第2種製造方法與第〗種製造方法同樣爲可容易獲得 本發明上述胺樹脂交聯粒子之方法因而甚佳，其中以可獲 得平均粒徑0 · 1至5 μηι，且粒徑8 μιη以上之粒子之比例 爲個數基準0 · 0 5 %以下之胺樹脂交聯粒子之方法爲佳。 又’以上說明之第1及第2種胺樹脂交聯粒子之製造 方法’係將所含特定粒徑以上之粗大粒子（或粒子）以個 數基準之比例降低至規定標準以下之上述本發明之胺樹脂 交聯粒子之製造方法，但同時由另一方面而言掌握本發明 之技術思想，如上述說明之方法，於製造胺樹脂交聯粒子 之際，可認爲係將上述粗大粒子（或粒子）以個數基準之 含有比例調製至規定標準以下之調整方法，或者可認爲係 將上述粗大粒子（或粒子）以個數基準之含有比例管理至 規定標準以下之管理方法，或者製造管理方法。 實施例 ， 下文以實施例及比較例更具體說明本發明，但本發明 並非限定於此。下文爲方便起見，將「重量份」簡稱爲 -40- (38) (38)200401786 「份」，「公升」簡稱爲「L」。 又’下述實施例1 -4對應於本發明之第1種製造方 法，實施例5 - 7對應於本發明之第2種製造方法。 [實施例1] 於裝設攪拌機、回流冷卻機、溫度計、振動式黏度劑 (MIVI ITS JAPAN 公司製，機種名·· MI VI 600 1 )等之 容量1 〇 L反應釜中，置入作爲胺系化合物之苯并胍胺 3000g(]6莫耳）與濃度37重量％之甲醒水溶液2600g (甲醛3 2莫耳）與碳酸鈉1 0重量％之水溶液1 〇 g (碳酸 鈉0.0 1莫耳），於攪拌下昇溫並於9 5 t下反應。 反應液黏度成爲4·5χ1 · s ( 45cP )之時點（自 反應開始5小時後）將該反應液冷卻使反應步驟終止。據 此而獲得含苯并胍胺與甲醛初期縮合物胺樹脂前驅體之反 應液。 繼之，於裝設回流冷卻機、均質機（攪拌機、特殊機 化工業股份公司製）、溫度計等之容量10L反應釜中，置 入將作爲乳化劑之聚乙稀醇（庫雷拉股份公司製，商品 名：P V A 2 0 5 ) 1 2 0 g溶解於2 0 5 0 g水而得之水溶液，將液溫 昇溫至7 5 °C。然後於該反應釜中添加上述反應液後，使 液溫昇溫至7 7 °C ，並於維持在7 7 °C下’以回轉速度 7 〇 〇 〇 rp m激烈攪拌內容物，使胺樹脂前驅體乳濁而得該胺 樹脂前驅體濃度爲5 2.5重量％之乳濁液。以庫耳特多尺寸 計-11型（庫耳特公司製，測定粒子個數：3 0 0 0 0 )測定該 -41 - 454 (39) (39)200401786 乳濁液，該乳濁液中胺樹脂前驅體之平均粒徑（d 5 〇 )爲 2.4 μηα ’標準偏差爲〇.7 μη]。繼之，於反應釜中添加作爲 無機物氧化砂水分散體之固形物濃度爲1 〇重量％之阿耶 洛凝膠（Aelogel ) 2 00 (日本阿耶洛凝膠股份公司製） 3 2 5 6 g後’維持在7 7 °C下並同時於均質機以回轉速度 4 0 00rpm激烈攪拌內容物5分鐘。將所得乳濁液冷卻至3〇 C。又’將胺樹脂前驅體與乳化劑水溶液混合後至下一步 驟之觸媒添加爲止之時間爲3小時。 繼之，將作爲觸媒之硫酸4 0 g ( 〇 · 4莫耳）溶於！ 2 〇 〇 g 純水而得之水溶液添加至上述乳濁液（內容物之溫度爲 3〇°C )中，於攪拌下以I〇°C /小時昇溫至90°C。然後於達 到90°C後，於該溫度下維持1小時，使胺樹脂前驅體縮 合•硬化。反應時間共計爲7小時。 硬化步驟終了後，將含胺樹脂交聯粒子之懸濁液冷卻 至3 0 °C後，使用5重量％之氫氧化鈉水溶液，將該懸濁液 的pH調成7.5。於中和步驟後藉由過濾自懸濁液取出胺 樹脂交聯粒子。將取出之胺樹脂交聯粒子於1 5 (TC下加熱 處理3小時乾燥之。將加熱處理後之乾燥物以噴射粉碎分 級機（附有分級機能）（機器名：LABO .TET (日本新馬 其工業（股）製））粉碎（鬆碎）同時將粉碎物分級（運 轉條件爲粉體供料量：〇.5kg/h，粉碎機供應空氣 壓：C 4Mpa，2次空氣（通風口）：小，調節環：3片 (24mm )，隔離環：10mm )。此時上述粉碎及分級之步驟 係於空氣水分含量控制在3 g/m3之室內進行’同時粉碎部 (40) (40)200401786 所供應之空氣（發自超音速噴嘴之衝突粉碎用空氣）及分 級部使用之2次空氣係使用水分含量爲3 g/m3之空氣。據 此可獲得粗大粒子少之白色粉末狀胺樹脂交聯粒子 (1 )。該胺樹脂交聯粒子（])之粒徑以庫耳特多尺寸 計-I 1型（庫耳特公司製’測定粒子個數：3 〇 〇 〇 〇 )測定之 結果’平均粒徑（d5 0 )爲2 · 5 μ】Ή，而粒徑40 μ1Ώ以上之 粗大粒子之個數基準之比例爲0 · 〇 1 %以了。 加熱處理步驟產生之含甲醛之排出氣體以使用載持白 金之觸媒（日本觸媒製’製品名；C - 7 0 2 3 )進行燃燒處 理，結果燃燒氣體之出口附近無甲醛臭味。 使用水分含量爲3 g/m3之空氣作爲運送胺樹脂交聯粒 子（1 )粉體之空氣，充塡至數個容器中分別密封，並保 存於2 5 °C。將裝有該胺樹脂交聯粒子（1 )之粉體之容 器，各於1週、〗個月、6個月後開封，該胺樹脂交聯粒 子（1 )之粉體狀態係以庫耳特多尺寸計-11型（庫耳特 公司製，測定粒子個數：3〇〇〇〇 )測定其平均粒徑及粗大粒 子之比例。結果，1週後之平均粒徑（d 5 0 )爲2.5 μ m， 而粒徑4 0 μηι以上之粗大粒子之個數基準比例爲〇 . 〇 1 %， 1個月後之平均粒徑（d 5 0)爲2 ·4 μm，而粒徑4 0 μm以 上之粗大粒子之個數基準比例爲0.01 %，6個月後之平均 粒徑（d 5 0 )爲2 · 5 μ m，而粒徑4 0 μ m以上之粗大粒子之 個數基準比例爲0 · 01 % ’與剛製造時之狀態並無變化’可 確知經本發明之製造方法所得之胺樹脂交聯粒子（1 )之 保存安定性及貯藏安定性均非常優越。此外’由上述測定 >43- (41) (41)200401786 結果與前述之式（A )可評估胺樹脂交聯粒子（1 )之保 存安定性於保存1個月時爲0%，保存6個月時亦爲〇%。 使用作爲黏合劑樹脂之聚酯樹脂75 g (東洋紡股份有 限公司製，派龍2 0 0 )、稀釋用溶劑甲苯]2 0 g與甲基乙 基酮3 0 g，與上述胺樹脂交聯粒子（])混合而得塗覆用 組成物。使用厚度1 〇 0 μηι之聚酯薄膜作爲基材薄膜（東 縲股份有限公司製，璐米菝#〗〇〇Τ56，切割爲 Α4大 小），以輥塗法將前述塗覆用組成物塗覆於該薄膜之單面 上，於]2 0 °C下熱風乾燥]分鐘，形成厚度3 0 // m之光擴 散層，而製作作爲光擴散片的薄膜。觀察該薄膜可確認係 獲得薄膜上無斑點爲良好狀態之光擴散片。 使用胺樹脂交聯粒子（1 )作爲去光劑時，確認具有 良好去光效果。 [實施例2] 於裝設攪拌機、回流冷卻機、溫度計、振動式黏度劑 (MIVI ITS JAPAN公司製，機種名：ΜIV I 6 0 0 1 )等之 容量1 〇L反應釜中，置入作爲胺系化合物之苯并胍胺 3 0 00 g ( 1 6莫耳）與濃度37重量％之甲醛水溶液2 6 00g (甲醛32莫耳）與碳酸鈉10重量％之水溶液10g (碳酸 鈉0.01莫耳），於攪拌下昇溫並於95 °C下反應。 反ΙΓ液黏度成爲4.5x](T2Pa · s ( 45cP )之時點（自 反應開始5小時後）將該反應液冷卻而終止反應步驟。據 此而獲得含苯并胍胺與甲醛初期縮合物胺樹脂前驅體之反 -44- (42) (42)200401786 應液。 繼之，於裝設回流冷卻機、均質機（攪拌機、特殊機 化工業股份公司製）、溫度計等之容量1 0L反應釜中，置 入將作爲乳化劑之聚乙烯醇（庫雷拉股份公司製，商品 名：P V A 2 0 5 ) 1 2 0 g溶解於2 0 5 0 g水而得之水溶液，於攪拌 下昇溫至7 5 °C。然後於該反應釜中添加上述反應液後， 使液溫昇溫至 7 7 °C ，並於維持在 7 7 °C下，以回轉速度 70 OOrpm激烈攪拌內容物，使胺樹脂前驅體乳濁而得該胺 樹脂前驅體濃度爲5 2 · 5重量％之乳濁液。以庫耳特多尺寸 計-Π型（庫耳特公司製，測定粒子個數：3 00 00 )測定該 乳濁液，該乳濁液中胺樹脂前驅體之平均粒徑（d 5 0 ) _ 2.4 μ m，標準偏差爲 0.7 μ m。將所得乳濁液冷卻至3 〇 °C。又，將胺樹脂前驅體與乳化劑水溶液混合後至下一步 驟之觸媒添加爲止之時間爲3小時。 繼之，將作爲觸媒之硫酸40g ( 0.4莫耳）溶於120〇g 純水而得之水溶液添加至上述乳濁液（內容物之溫度；^ 3〇°C )中，於攪拌下以l〇°C /小時昇溫至90°C。然後於達 到9 0 °C後，於該溫度下維持]小時，使胺樹脂前驅體縮 合•硬化。反應時間共計爲7小時。 硬化步驟終了後，將含胺樹脂交聯粒子之懸濁液冷卻 至3 0 t：後，使用5重量％之氫氧化鈉水溶液，將該懸濁液 的p Η調成7 · 5。於中和步驟_由過濾自懸濁液取出胺樹 脂交聯粒子。將取出之胺樹脂交聯粒子於1 5 0 r下加熱處 理3小時乾燥之。將加熱處理後之乾燥物以粉碎機（機器 -45 - (43) 200401786 名：梵它姆磨AP-B，細川微米（股）製）粉碎（ (運轉條件爲篩網徑：〇 3 m m )。將自粉碎機排出 (粉碎物）以暴露於室內空氣之狀態運送至氣流 (機器名克莅歇爾N - 5，精心企業（股）製）， 用氣流分級機進行分級（運轉條件爲粉體供料量： 回轉數：4〇〇〇rpm，回轉閥：1 〇度，2次空氣開度：；[ 次空氣開度·0%，空氣流量：9.lm3/h，2次： 壓：0.20mmAq)。上述粉碎及分級之操作係於將空 含量控制在4g/m3之室內進行，同時粉碎機與分級 成流用之氣體均係使用水分含量控制在4 g / m 3之 據此可獲得粗大粒子少之白色粉末狀胺樹脂交 (2 )。該胺樹脂交聯粒子（2 )之粒徑以庫耳特 計-II型（庫耳特公司製，測定粒子個數：3 0000 ) 結果，平均粒徑（d50 )爲2·6 μηι，而粒徑40 μηι 粗大粒子之個數基準比例爲〇 . 〇 ] %。 加熱處理步驟產生之含甲醛之排出氣體以使用 金之觸媒（日本觸媒製，製品名；C- 7 023 )進行 理’結果燃燒氣體之出口附近無甲醛臭味。 除使用水分含量爲4g/m3之空氣運送胺樹脂交 (2 )以外，於實施例1之相同條件下，充塡至容 封之’並保存於2 5 °C。充塡後將裝有該胺樹脂交 (2 )之粉體之容器，各於丨週、1個月、6個月後 該胺樹脂交聯粒子（2 )之粉體狀態係以庫耳特多」 Π型（庫耳特公司製，測定粒子個數：3 0 0 〇 〇 )測 鬆碎） 之粉體 分級機 然後使 1 k g / h， 0 0%，3 空氣差 氣水分 機中形 空氣。 聯粒子 多尺寸 測定之 以上之 載持白 燃燒處 聯粒子 器中密 聯粒子 開封， 3寸計-定其平 -46- (44) (44)200401786 均粒徑及粗大粒子之比例。結果，]週後之平均粒徑 (d50 )爲2.6m，而粒徑40 以上之粗大粒子之個數基 準比例爲 〇 . 〇 1 %，1個月後之平均粒徑（d 5 0 )爲 2 · 6 pm ’而粒徑 40 μηι以上之粗大粒子之個數基準比例爲 〇 . 〇 ] %，6個月後之平均粒徑（d 5 〇 )爲2 · 6 μηι，而粒徑 4 0 μ m以上之粗大粒子之個數基準比例爲〇 . 〇 1 %，與剛製 造時之狀態並無變化，而可確知經本發明之製造方法所得 之胺樹脂交聯粒子（2 )之保存安定性及貯藏安定性均非 常優越。此外，由上述測定結果與前述之式（A )可評估 胺樹脂交聯粒子（2 )之保存安定性於保存1個月時爲 〇%，保存6個月時亦爲〇%。 使用胺樹脂交聯粒子（2 )，與實施例1同樣操作而 製作作爲光擴散片的薄膜。觀察該薄膜可確認係獲得薄膜 上無斑點爲良好狀態之光擴散片。 [實施例3] 將實施例1所得含樹脂前軀體之乳濁液冷卻至3 0 °C 後，於反應釜中添加作爲無機物氧化矽水分散體之固形物 濃度爲1 〇重量％之阿耶洛凝膠2 0 0 (日本阿耶洛凝膠股份 公司製）3 2 5 6g後，於均質機中以回轉速度4 00 Orpm激烈 攪祥內容物5分鐘。繼之至添加觸媒爲止進行著色步驟。 具體言之，係使用將著色劑水溶性染料「酸性紅（Acid Red 52 )」7g溶於純水3 5 0 g而調製之水溶液。該染料濃 度爲2重量。/。。然後，將所調製之水溶液添加至上述乳濁 -47 - (45) (45)200401786 液中並激烈擅梓5分鐘。繼之，與實施例1同樣將觸媒添 加至乳濁液中’硬化步驟後之步驟係與實施例I同樣進 行’取終獲得著色之胺樹脂交聯粒子（3 )。該胺樹脂交 聯k子（3 )之粒度分布以庫耳特多尺寸計_ n型（庫耳 特公司製’測定粒子個數3 〇 〇 〇 〇 )測定之結果，平均粒徑 (d50)爲2·8 μηι，而粒徑4〇 μΐΏ以上之粗大粒子之個數 基準比例爲〇 . 〇 ] %。 有關胺樹脂交聯粒子（3 )，以與實施例1之相同條 件充塡至谷器中密封之，並保存於2 5 °C。充塡後將裝有 該胺fet脂交聯粒子（3 )之粉體之容器，各於1週、]個 月、6個月後開封，該胺樹脂交聯粒子（3 )之粉體狀態 係以庫耳特多尺寸計_ Π型（庫耳特公司製，測定粒子個 數：3〇〇〇〇 )測定其平均粒徑及粗大粒子之比例。結果，1 週後之平均粒徑（d50 )爲2.8m，而粒徑40 μηι以上之粗 大粒子之個數基準比例爲〇. 0 1 %，1個月後之平均粒徑 (d 5 0 )爲2.8 pm，而粒徑4 0 μηι以上之粗大粒子之個數 基準比例爲〇 . 〇 1 %，6個月後之平均粒徑（d 5 0 )爲2.8 μηι，而粒徑4〇 μηι以上之粗大粒子之個數基準比例爲 0.0 1 %，與剛製造時之狀態並無變化，而可確知經本發明 之製造方法所得之胺樹脂交聯粒子（3 )之保存安定性及 貯藏安定性均非常優越。此外，由上述測定結果與前述之 式（A )可評估齡樹脂交聯粒子（3 )之保存安定性於保 存1個月時爲0%，保存6個月時亦爲〇%。 對作爲聚烯烴透明基材之聚氯乙烯樹脂]0 0份，係配 -48 - (46) 200401786 合1 〇份上述著色之胺樹脂交聯粒子（3 )進行熔融混練， 使用所得之著色樹脂組成物製作厚度5 0 μηι之薄膜。所得 之著色薄膜無斑點、退色等，呈良好著色狀態。 [實施例4 ] 除了將胺樹脂前驅體與乳化劑水溶液混合後至下一步 驟之觸媒添加爲止之時間改爲6小時以外，與實施例1同 樣操作獲得白色粉末狀胺樹脂交聯粒子（4 )。該胺樹脂 交聯粒子（4 )之粒度分布以庫耳特多尺寸計-11型（庫 耳特公司製，測定粒子個數：3 000 0 )測定之結果，平均粒 徑（d50 )爲2·8 μηι，而粒徑40 μ1Ώ以上之粗大粒子個數 基準之比例爲〇. 〇 3 %。又，與實施例1相較，.由於胺樹脂 前驅體與乳化劑水溶液混合後至下一步驟之觸媒添加爲止 之時間增長，一部分發生乳化粒子之粗大化，而於硬化後 之胺樹脂交聯粒子中生成多量粒徑4 0 μ1Ώ以上之粗大粒 子。因此，雖其後以與實施例]之相同條件進行粉碎及分 級，胺樹脂交聯粒子（4 )與胺樹脂交聯粒子（1 )相較， 粒徑40 μηι以上之粗大粒子之個數基準比例有若干增加。 胺樹脂交聯粒子（4 )以與實施例1之相同條件充塡 至容器中密封之，並保存於2 5 °C。充塡後將裝有該胺樹 脂交聯粒子（4 )之粉體之容器，各於1週、]個月、6個 月後開封，該胺樹脂交聯粒子（4 )之粉體狀態係以庫耳 特多尺寸計-II型（庫耳特公司製，測定粒子個 數：3 0 000 )測定其平均粒徑及粗大粒子之比例。結果，1 -49- (47) (47)200401786 週後之平均粒徑（d 5 0 )爲2.8 m，而粒徑4 〇 μ 以上之粗 大粒子之個數基準比例爲0.03%，1個月後之平均粒徑 (d 5 0 )爲2 · 8 μηι，而粒徑4 0 μ m以上之粗大粒子之個數 基準比例爲〇 . 〇 3 %，6個月後之平均粒徑（d 5 0 )爲2 8 μ m，而粒徑4 0 μ m以上之粗大粒子之個數基準比例爲 0.0 3 %，與剛製造時之狀態並無變化，而可確知經本發明 之製造方法所得之胺樹脂交聯粒子（4 )之保存安定性及 貯藏安定性均非常優越。此外，由上述測定結果與前述之 式（A )可評估胺樹脂交聯粒子（3 )之保存安定性於保 存1個月時爲〇%，保存6個月時亦爲0%。 使用胺樹脂交聯粒子（4 )與實施例1同樣製作作爲 光擴散片之薄膜。觀察該薄膜可確認係獲得薄膜上無斑點 爲良好狀態之光擴散片。 [比較例1 ] 除了將胺樹脂前驅體與乳化劑水溶液混合後至下一步 驟之觸媒添加爲止之時間爲1 〇小時’以及粉碎後不進行 分級以外，與實施例2同樣操作獲得比較胺樹脂交聯粒子 (1 )。該比較胺樹脂交聯粒子（1 )之粒徑、粒度分布以 庫耳特多尺寸計-Π型（庫耳特公司製，測定粒子個 數：3 00 00 )測定之結果，平均粒徑（d50 )爲4.5 μηι，而 粒徑40 μηι以上之粗六粒子之個數基準比例爲1 .丨％。 使用比較胺樹脂交聯粒子（1 )與實施例1同樣製作 作爲光擴散片之薄膜，觀察該薄膜見到薄膜上2處有斑 -50^ (48) (48)200401786 點，不適於實際使用作爲光擴散片。 [比較例2 ] 除了粉碎後不進行分級以外，與實施例2同樣操作獲 得比較胺樹脂交聯粒子（2 )。該比較胺樹脂交聯粒子 (2 )之粒徑、粒度分布以庫耳特多尺寸計_n型（庫耳 特公司製，測定粒子個數：3 0000 )測定之結果，平均粒徑 (d50 )爲4.0 μηι，而粒徑40 μηι以上之粗大粒子個數基 準之比例爲0.8 0 %。 使用比較胺樹脂交聯粒子（2 )與實施例1同樣製作 作爲光擴散片之薄膜，觀察該薄膜見到薄膜上 2處有斑 點，不適於實際使用作爲光擴散片。 [實施例5] 於裝設攪拌機、回流冷卻機、溫度計之四口燒瓶中’ 置入3 0 0 0份三聚氰胺、濃度3 7 %之甲醛水溶液5 8 0 0份及 濃度2 8 %之氨水溶液3 0份作成混合物，將反應系之PH 調整至8.0。於攪拌下將該混合物昇溫至7 5 °C，於同溫度 下反應6 0分鐘，獲得含水混合度爲3 0 0 %之初期縮合物胺 樹脂前驅體之反應液。 另外，將陰離子系介面活性劑新佩雷斯 (reopeleks) 05粉末（花王石驗（股）製一丨兀基本 磺酸鈉）200份溶解於44 80 0份水中’將該介面活性劑水 溶液昇溫至8 0 t：並攪拌之。於攪拌狀態下將上述含胺樹 -51 - (49) (49)200401786 脂前驅體之反應液投入該介面活性劑水溶液中，繼之添加 1 0 %十二烷基苯磺酸鈉水溶液9 0 0份，徐徐昇溫至至9 0 °C 並保持2小時使縮合•硬化同時粒子化，而獲得胺樹脂交 聯粒子之懸濁液。該懸濁液以光學顯微鏡（倍率8 0 0倍） 觀察時，可知係含粒徑爲約1 .5 μ1Ώ之球狀微粒子，且各 微粒子進形激烈布朗運動。 將上述懸濁液冷卻至3 0 °C，於其中添加1 %硫酸鋁水 溶液400份後，以吸引過濾分離固體與液體。分離而得之 胺樹脂交聯粒子以1 3 0。(：熱風乾燥機乾燥2小時，獲得 3 6 〇 〇份胺樹脂交聯粒子之乾燥物。然後與實施例2同樣 操作’將該乾燥物粉碎（鬆碎），再進行分級而獲得胺樹 脂交聯粒子（5 )。 該胺樹脂交聯粒子（5 )之粒徑以庫耳特多尺寸計_ j 1 型（庫耳特公司製，測定粒子個數：3 〇 〇 〇 〇 )測定之結果， 平均粒徑（d50 )爲1 ·5 μη]，而粒徑8 μηι以上之粒子之 個數基準比例爲〇 · 〇 1 %。分級後之胺樹脂交聯粒子（5 ) 以ί市描式電子顯微鏡檢視時，粒徑8 m以上之粒子之個 數爲〇 (測定個數：3 0 0 0 ) 除使用水分含量爲4g/m3之空氣運送胺樹脂交聯粒子 (5 )以外，於實施例1之相同條件下，充塡至容器中密 树之’並保存於2 5 t。充塡後將裝有該胺樹脂交聯粒子 (5 )之粉體之容器，各於1週、]個月、6個月後開封， ^ fe樹交聯粒士（ 5 )之粉體狀態係以庫耳特多尺寸計_ U型（庫耳特公司製，測定粒子個數：30〇〇〇 )測定其平 -52 - (50) 200401786 均粒徑及粒徑8 μηι以上之粒子之比例， 均粒徑（d50 )爲].5 μηι，而粒徑8 μη] 數基準比例爲〇 . 〇 1 %，]個月後之平均粒 μ m，而粒徑8 μ m以上之粒子之個數基準 個月後之平均粒徑（d 5 0 )爲1 .5 μιη，而 之粒子之個數基準比例爲0.0 1 %，與剛製 變化，而可確知經本發明之製造方法所得 子（5 )之保存安定性及貯藏安定性均非 由上述測定結果與前述 7之式（A )可評 子（5 )之保存安定性於保存1個月時爲 時亦爲0 %。 除了使用胺樹脂交聯粒子（5 )，經 光擴散層厚度爲1 0 μηι以外，與實施例i 作爲光擴散片的薄膜，觀察該薄膜可確S忍 斑點爲良好狀態之光擴散片。 [實施例6] 於實施例1所使用之四口燒瓶中，個 胺、8 0份苯并胍胺、濃度3 7 %之甲醛水丨 度1〇%之碳酸鈉水溶液1.16份作成混合 pH調整至8 · 0。於攪拌下將該混合物昇之 溫度下吱應4 0分鐘，獲得含水混合度爲 物胺樹脂前驅體之反應液。另外，將陰離 愛瑪露膠（Em a] gel ) 4 3 0 (花王石鹼（股 結果]週後之平 以上之粒子之個 徑（d 5 0 )爲].5 比例爲〇 〇 ] %，6 粒徑8 μπι以上 :造時之狀態並無 之胺樹脂交聯粒 常優越。此外， :估胺樹脂交聯粒 〇 %，保存6個月 熱風乾燥作成之 同樣操作而製作 係獲得薄膜上無 [入7 0份三聚氰 容液2 90份及濃 物，將反應系之 昆至7 (TC，於同 3〇〇°/。之初期縮合 子系介面活性劑 )製，聚氧化乙 (51) (51)200401786 烯油基醚）7.5份溶解於2C5份水中，將該介面活性劑水 溶液昇溫至7 0 °C並攪拌之。於攪拌狀態下將上述含胺樹 脂前驅體之反應液投入該介面活性劑水溶液中，獲得胺樹 脂前驅體與介面活性劑之混合液，混合液暫時成爲透明 後，於其中添加 5 %十二烷基苯磺酸鈉水溶液 9 0份，於 7 〇 °C溫度下保持2小時使縮合硬化，而獲得胺樹脂交聯粒 子之懸濁液。該懸濁液再於攪拌下昇溫至9 0 °C，於同溫 度下保持1小時使完全硬化，而獲得充分硬化之胺樹脂交 聯粒子之懸濁液。自該懸濁液以離心分離沉降胺樹脂交聯 粒子，並以1 4 0 °c熱風乾燥機乾燥4小時，獲得1 2 0份胺 樹脂交聯粒子之乾燥物。然後與實施例]同樣操作，將該 乾燥物粉碎並進行分級而獲得胺樹脂交聯粒子（6 )。 該胺樹脂交聯粒子（6 )之粒徑以庫耳特多尺寸計—π 型（庫耳特公司製，測定粒子個數：3 0 0 0 0 )測定之結 果，平均粒徑（d50 )爲2·5 μηι，而粒徑8 μηι以上之粒 子之個數基準比例爲〇· 〇 1 %。分級後之胺樹脂交聯粒子 (6 )以掃描式電子顯微鏡檢視時，粒徑8 μηι以上之粒子 之個數爲〇 (測定個數：3 0 0 0 )。 胺樹脂交聯粒子（6 )於實施例1之相同條件下，充 續至谷窃中密封之’並保存於2 5 °C。充塡後將裝有該胺 樹脂交聯粒子（6 )之粉體之容器，各於1週、1個月、6 個月後開封’該胺樹脂交聯粒子（6 )之粉體狀態係以庫 耳特多尺寸計-II型（庫耳特公司製，測定粒子個 數：3 0000 )測定其平均粒徑及粒徑S μηι以上之粒子之比 -54 - (52) (52)200401786 例，結果1週後之平均粒徑（d 5 〇 )爲2.5 m，而粒徑8 μηι 以上之粒子之個數基準比例爲〇 . 〇 1 %，]個月後之平均粒 徑（d 5 0 )爲2 5 μηι，而粒徑8 μ】Ό以上之粒子之個數基 準比例爲 0 . 〇 1 %，6個月後之平均粒徑（d 5 0 )爲 2.5 μηι，而粒徑8 μο以上之粒子之個數基準比例爲0.0 1 %， 與剛製造時之狀態並無變化，而可確知經本發明之製造方 法所得之胺樹脂交聯粒子（6 )之保存安定性及貯藏安定 性均非常優越。此外，由上述測定結果與前述之式（A ) 可評估胺樹脂交聯粒子（6 )之保存安定性於保存1個月 時爲0 %，保存6個月時亦爲0 %。 除了使用胺樹脂交聯粒子（6 )，經熱風乾燥作成之 光擴散層厚度爲1 〇 μηι以外，與實施例1同樣操作而製作 作爲光擴散片的薄膜，觀察該薄膜可確認係獲得薄膜上無 斑點爲良好狀態之光擴散片。 [實施例7] 除了粉碎及分級操作係於空氣之水分含量控制在 〗〇g/m3以下之室內進行，以及粉碎機及分級機中形成氣流 所使用之氣體係使用水分含量控制在1 Og/m3以下之空氣 以外’與實施例5同樣操作而獲得白色粉末狀之胺樹脂交 聯粒子（7 )。 胺樹脂交聯粒子（7 )之粒徑、粒度分布以庫耳特多 尺寸計-11型（庫耳特公司製，測定粒子個數：3 0 0 0 0 )測 定’其平均粒徑（d50 )爲].5 μηι，而粒徑8 μη以上之 -55 - cU Μ ^ (53) 200401786 粒子之個數基準比例爲0.03%。分級後之胺樹脂交 (7 )以掃描式電子顯微鏡檢視時，粒徑8 μηι以上 之個數爲〗個（測定個數：3 0 0 0 )，其係凝集粒子。 有關胺樹脂交聯粒子（7 )除了使用水分_ 1 〇g/m3之空氣作爲運送空氣外，於實施例1之相 下，充塡至容器中密封之，並保存於2 5 °C。充塡 有該胺樹脂交聯粒子（7 )之粉體之容器，各於j 個月、6個月後開封，該胺樹脂交聯粒子（7 )之 態係以庫耳特多尺寸計-11型（庫耳特公司製，測 個數：3 0 0 0 0 )測定其平均粒徑及粒徑8 μηι以上之 比例，結果1週後之平均粒徑（d50 )爲1 .5 μηι， 8 μ m以上之粒子之個數基準比例爲〇 . 〇 3 %，]個月 均粒徑（d 5 0 )爲1 .5 μηι，而粒徑8 μηι以上之粒 數基準比例爲0.0 5 %，6個月後之平均粒徑（d 5 0 ) μηι，而粒徑8 μηι以上之粒子之個數基準比例爲0 與剛製造時之狀態並無變化，而可確知經本發明之 法所得之胺樹脂交聯粒子（6 )之保存安定性及貯 性均非常優越。此外，由上述測定結果與前述之式 可評估胺樹脂交聯粒子（7 )之保存安定性於保存 時爲〇%，保存6個月時亦爲〇%。 〔發明之效果〕 依據本發明可提供前述不會產生斑點亦不會發 等品質不良問題之胺樹脂交聯粒子與適於製造此種 聯粒子 之粒子 含量爲 同條件 後將裝 週、1 粉體狀 定粒子 粒子之 而粒徑 後之平 子之個 爲1.6 • 0 7%， 製造方 藏安定 (A ) 1個月 生退色 胺樹脂 -56 - (54) 200401786 交聯粒子之方法。又，本發明之胺樹脂交聯粒子作爲去光 劑可發揮良好的去光效果。 -57--23- (21) (21) 200401786 The pH of the turbid solution is preferably adjusted to 5 or more, and the pH is preferably adjusted to 5 to 9. If the pH of the suspension is less than 5, the amine resin crosslinked particles will be discolored in the heating step and the like described later due to the acid catalyst remaining. By adjusting the pH of the suspension to the above range by neutralization, amine resin crosslinked particles having high hardness, excellent solvent resistance and heat resistance, and no change in color can be obtained. The neutralizing agent used in the neutralization step is preferably a basic substance, for example. The basic substance is, for example, sodium carbonate, sodium hydroxide, potassium hydroxide, ammonia, etc. Among them, sodium hydroxide is preferred in terms of ease of handling, and an aqueous sodium hydroxide solution is preferred. These can be used alone or in combination of two or more. The first manufacturing method may further include a step of separating the amine resin crosslinked particles from the suspension of the amine resin crosslinked particles obtained after the hardening step or the neutralization step. In the first production method, the amine resin crosslinked particles are separated from the suspension and taken out are those obtained when the amine resin crosslinked particles obtained by curing are emulsified (in the emulsification step) and separated from the aqueous medium. The method (separation method) for separating and taking out the amine resin cross-linked particles from the suspension may be a simple method such as a filtration method or a separator such as a centrifuge, and is not particularly limited, and a generally known method can be used. Further, the amine resin crosslinked particles taken out from the suspension may be washed with water or the like if necessary. In the first manufacturing method, it is preferred to perform a heating step of heating the amine resin crosslinked particles taken out through the separation step at I 30 to 190 ° C. The heating step can remove the moisture attached to the amine resin crosslinked particles and the residual free formaldehyde, and can further promote the combination (crosslinking) of the amine resin crosslinked particles. When the above heating temperature is lower than I 3 (TC, the condensation (parent linkage) in the amine resin crosslinked particles cannot be fully promoted, and the hardness and resistance of the amine resin crosslinked particles may not be improved.) 24- (22) (22) 200401786 Solvent and heat resistance, if it exceeds 90 ° C, the resulting amine resin crosslinked particles may be discolored. Even if the above neutralization step is performed, it is also affected by the same effect when the heating temperature is outside the above range. The neutralization step is performed, and the heating temperature of the amine resin crosslinked particles is within the above range, and amine resin crosslinked particles having high hardness, excellent solvent resistance and heat resistance, and no color change can be obtained. There is no heating method in the heating step. It is particularly limited, and a generally known heating method can be used. The heating step can be terminated, for example, at a stage where the moisture content of the amine resin crosslinked particles is 3% by weight or less. The heating time is not particularly limited. In the first production method, more Good amine resin crosslinked particles are taken out of the suspension, and dried (heated), pulverized to obtain the amine resin crosslinked particle powder, and further classified into an average particle diameter of 0. 1 to 20 μηι, and coarse particles with a particle size of 40 μηι or more are counted as 0. Amine resin crosslinked particles below 05%. In the method for producing amine resin crosslinked particles, the harmful formaldehyde contained in the exhaust gas generated during the heating step has always been a problem. So far, it has generally been treated with water absorption or combustion. However, it is not economical because it requires a large amount of water for absorption and it takes a long time for absorption. Therefore, it is preferable that the formaldehyde-containing exhaust gas generated in this step is combusted using a platinum-based catalyst. In the first manufacturing method, the amine resin crosslinked particles obtained through the hardening reaction step are separated from the aqueous medium during emulsification and dried as described above, the obtained dried product is pulverized, and finally the obtained pulverized product is pulverized. Grading. -25- (23) (23) 200401786 The pulverization step for performing the aforementioned pulverization refers to a step of loosening aggregated amine resin crosslinked particles in the steps of hardening, separating, and drying (heating). In addition, the classification step of performing the aforementioned classification refers to a step of reducing fine particles generated in the emulsification step, coarse particles or particles larger than a specific particle size, and aggregated coarse particles or aggregated particles that have not been loosened in the aforementioned pulverizing step, and may be The step of performing only classification 'may be a step of performing classification and pulverization at the same time. When the aforementioned pulverization and classification are performed simultaneously, the pulverization and classification may be performed after pulverization, or the pulverization and classification may be performed simultaneously. In the first manufacturing method, the pulverizing step and the grading step may use separate devices of the pulverizer and the grading device, or a device having both functions of pulverizing and grading (pulverizing and classifying machine). The pulverizer may be exemplified by a Bantam υ mill, a Parubei honing machine (P a) be 1 aizer, Hosokawa micron (shares), a sample mill (Samplemill, not 2 powder (strand) system), jet mill, etc. The classifier can be exemplified by a micro-separator (made by Hosokawa Micron Co., Ltd.), a micro-classifier (made by Sesin Corporation), a soil wave classifier (TURBO CLASSIFIER, manufactured by Nissei Engineering Co., Ltd.) Wait. Examples of the crushing and classifying machine include LABO JET (Newmatch Industrial Co., Ltd., Japan) and jet crushing and classifying machine S T J-2 0 0 (manufactured by Elite Corporation). The pulverizer and classifier is in a better form because of its compact device for economic reasons. The conditions for pulverization and / or classification are not particularly limited, for example, at least one treatment (the steps of pulverization and / or classification and at least one of the steps therebetween or the subsequent steps after the above-mentioned pulverization treatment). The same applies below. -26 -(24) 200401786 'The gas used to form the gas flow is best controlled with a moisture content of 6g / m3 or less, and a gas with a moisture content of 5g / m3 or less is better' The moisture content is controlled at 4g / m3 or less The gas is even better, and the gas whose moisture content is controlled below 3 g / m3 is even better, especially the gas whose moisture content is controlled below 2 g / m3, preferably the gas whose moisture content is controlled below lg / ni3. The gas system used to form the gas stream refers to the gas used in the pulverization or classification step, and also includes the gas used for particle transport (particle transport) between steps. The reason for controlling the moisture content is as described above, in the step of crushing and / or classifying the powder obtained in the foregoing hardening, or in the step of transferring (transporting) between the steps, the gas used to form the air flow, if the moisture content is used When the gas is more than 6g / m3, for example, when using general air (atmospheric), some particles that have been crushed and / or classified may be aggregated into coarse particles again. In addition, the lower limit of the moisture content is not particularly limited. Ideally, it is 0, but it is, for example, 0. 05g / m3 or more. When using the aforementioned pulverizer and classifier, it is particularly good to use a gas controlled to the above-mentioned moisture content, and it is possible to easily and surely and effectively obtain particles with a specific particle size or larger (coarse particles with a diameter of 40 μηΐ or more) below a specific standard. The amine resin crosslinked particles of the present invention described above. The conditions for the pulverization and / or classification are all the processing steps after the pulverization (the pulverization step, the grading step, the step between them, or all subsequent steps. The same applies below). The conditions under which the gas is used are preferably such that the moisture content is controlled within the above range. The conditions for the pulverization and / or classification are that after the above pulverization, it is preferable to use a gas controlled to the above-mentioned moisture content for atmospheric management. The above-mentioned atmospheric management may be -27- (25) (25) 200401786. Specifically, for example, the above-mentioned gas is used to manage the moisture content in the room where various treatment operations of the amine resin crosslinked particles such as pulverization or classification are performed. According to the above-mentioned atmospheric management, for example, when the pulverized material discharged from the pulverizing device is transferred to the input port of the next classification device in a state of being exposed to the surrounding atmosphere, by controlling the moisture content of the gas between the particle transfer (transport) between each step, Even if it is briefly exposed to the surrounding atmosphere, it can effectively prevent some particles from re-aggregating into coarse particles. In the step after pulverization and / or classification, the gas controlled by the above-mentioned moisture content is used, or in the step after the pulverization, the atmospheric management is by using the gas controlled by the above-mentioned moisture content, and it can be easily achieved according to the present invention. The coarse particles or the proportion of the particles having the specific particle size or more are below a specific standard. When the above-mentioned classification is stored and stored in a sealed container, the sealed container is filled with a gas controlled to the above-mentioned moisture content, and superior storage stability and storage stability effects can be obtained. That is, a method of storing in a sealed container using a gas controlled to the above-mentioned moisture content is a preferred form of the present invention. The amine resin cross-linked particles stored and stored by this preservation method can become the ratio of coarse particles or particles whose specific average particle size and the above-specified particle size are below the specified standard, not only before or after storage and storage. The particle size distribution characteristics of the amine resin crosslinked particles of the present invention have very significant storage stability and storage stability as described below. Regarding storage stability and storage stability, the resin crosslinked particles obtained after classification are stored in a sealed container using a gas that meets the above-mentioned moisture content conditions] for a month, and coarse particles or particles larger than a specific size are evaluated> 28- (26) (26) 200401786 Degree of change in proportion. Specifically, when "the ratio of coarse particles or particles (%) larger than a specific particle size before storage" is a, and "the ratio of coarse particles or particles (%) larger than a specific particle size after storage" is b, the following Formula (A) (| ab | / a) X10 0 (%) (A) Assessed from the evaluation, the value is preferably 30% or less, more preferably 20% or less, and 0% or less is better, 5 % Is even better, especially below 1%. It is also preferable that the evaluations stored in the sealed container during the 1 month and the evaluations stored in the sealed container during the 6 month period satisfy the above range. In the above steps of pulverization and / or classification, the conditions for forming the gas used in the airflow during pulverization and / or classification are due to the danger of dust explosion. It is better to use an inert gas with a low oxygen concentration. Specifically, The oxygen concentration is preferably less than 10%, more preferably less than 5%, and more preferably less than 3%. Examples of such inert gases include rare gases such as nitrogen, helium, and argon, and nitrogen is preferred in terms of economy. The oxygen concentration conditions may be controlled in combination with the above-mentioned conditions of the moisture content, and may be controlled separately from the above-mentioned conditions of the moisture content, but the former is preferred. The classification method can be roughly divided into dry type and wet type. In the case of the wet type, a drying step must be applied afterwards. Because the particles will aggregate into coarse particles during drying, the dry classification must be applied again. The steps are complicated and unfavorable. This can be simplified to dry classification. The dry classification method can be roughly divided into air flow classification method and sieve method. When the sieve method is used, the amine resin crosslinked particles are hardened due to the cross-linking of the particles. 'The sieve openings are difficult to remove when the particles are clogged. For continuous production, airflow classification is preferred. When the classification step is performed by the above-mentioned air classification method, the supply speed of the amine resin crosslinked particle powder is controlled to 0. 15 to 〖〇 Qkg / h is more preferable, and 0 1 to 50 gram g / h is more preferable. If the supply rate is controlled so as to satisfy the above range, the aforementioned amine resin crosslinked particles of the present invention can be easily obtained. Similarly, when the classification step is performed by the airflow classification method, the total air volume of the airflow is controlled to be 0: 5 to 30 m3 / m i η, preferably 0. 5 to 25 m3 / m i η is more preferable. If the total air volume is controlled so as to satisfy the above range, the aforementioned amine resin crosslinked particles of the present invention can be easily obtained. The above-mentioned total air volume refers to the total amount of gas used to form the airflow for classifying the airflow. Generally, in order to form the airflow, a fan or the like is used to exhaust the gas in the classifier and the gas flowing into (through) the classifier. In this case, the total exhaust volume is the total air volume. When the classification step is performed by the air flow classification method, it is preferable to control the supply speed and the total air volume so that both of the conditions are satisfied. When the classification step is performed by the airflow classification method, the ratio of the supply speed and the total air volume "total air volume / supply speed" is controlled so that 01-5 0 is satisfied, 0 · 1 to 3 0 is more preferable, and 0. 5 to 10 is even better. When the above ratio is less than 0.1, the yield of amine resin crosslinked particles may decrease, and if it exceeds 50, coarse particles having a specific particle size or larger may increase. As described above, the amine resin cross-linked particles obtained from the suspension are separated and hardened, dried, pulverized, and classified into 'grades', and the content ratio of the number of coarse particles (or particles) based on the specific particle size or more can be reduced to a specific standard The following amine resin crosslinked particles. -30- (28) (28) 200401786 In the first manufacturing method, airflow pulverization classification or airflow classification method is used as described above, and a gas that reduces the moisture content to a specific standard is used as the transmission gas (air for transportation, etc.), Then, the remaining moisture and the like are not mixed in a continuous series of steps, and the amine resin crosslinked particles can be stably produced and sealed in a container. In the first manufacturing method, the hardening may be performed by adding a catalyst to the emulsion obtained by emulsification, and the addition of the catalyst is preferably performed within 5 hours after the start of the emulsification. In this way, the time from the beginning of emulsification (when the amine resin precursor and the emulsifier (emulsifier aqueous solution) starts to be mixed) to the start of hardening (when the catalyst is added) is controlled within 5 hours, that is, It is easy to obtain amine resin crosslinked particles whose content ratio is reduced to a predetermined standard or less. The above emulsification time is preferably within 4 hours, more preferably within 3 hours, even more preferably within 2 hours, and most preferably within 1 hour. If the above time exceeds 5 hours, the amount of coarse particles (or particles) larger than a specific size is generated. Will increase. The operation from the start of the emulsification time to the end is as described above, starting with the start of emulsification and ending with the start of hardening, and is not particularly limited. However, for example, ① the reaction solution of the amine resin precursor and the emulsifier can be stirred and mixed to make the amine resin precursor into an opacified state, stop stirring and leave to cool to a predetermined temperature, or ② can be performed after the above cooling The other steps of adding the specified inorganic particles, etc. ③ can be continued until the specified opacifying state is 31-(29) (29) 200401786, and then continue to stir before adding the catalyst ( (It is better to stir gently than at the beginning.) While cooling, there is no particular limitation. In general, for example, when performing the above-mentioned operation ③, if the emulsification time is long, the time for applying shearing force to the opacified particles increases due to its sufficient stirring, so that coarse particles are reduced. For example, if the above-mentioned ① or During the operation of ②, once the particles become opaque, each particle is in a stable, individually dispersed state by standing to cool, and coarse particles will not increase. However, it is surprising that in any of the cases ① to ③, it was confirmed that if the emulsification time exceeds 5 hours, the amount of coarse particles tends to increase. Although the cause is not determined, for example, due to continued application of a shear force for more than a certain period of time or a state of standing for more than a certain period of time, the emulsion film on the surface of the particles in the emulsion is destroyed, and aggregation is liable to occur. The above-mentioned] production method is a method in which the amine resin crosslinked particles of the present invention can be easily obtained, that is, because the average particle diameter can be easily obtained. ] To 20 μη ′ and a ratio of coarse particles having a particle size of 40 or more is preferably a number of amine resin cross-linked particles of 0. 05% or less. -The second manufacturing method-The second manufacturing method of the amine resin crosslinked particles (hereinafter also referred to as "the second manufacturing method") of the present invention is characterized by an amine resin gallery obtained by reacting an amine compound with formaldehyde The driving body is mixed with the surface active agent in the water-based medium, and a catalyst is added to the mixed liquid to precipitate and precipitate the amine resin precursor from the water-based medium, and then the amine resin cross-linked particles are from front-32- (30) (30) 200401786 The aqueous medium during the emulsification is separated, dried, the obtained dried product is pulverized, and the obtained pulverized product is classified. The second manufacturing method 'Although it is also based on the resinization step described in the first method', that is, the amine resin precursor is obtained by the step of reacting an amine compound with formaldehyde, but the second manufacturing method is the resin The amine resin precursor obtained in the chemical conversion step is obtained by applying a mixing step of mixing with a surface-active agent in an aqueous medium, and adding a catalyst to the mixture to granulate and precipitate the amine resin precursor through hardening. The amine resin crosslinked particles are different from the first manufacturing method in the point of the curing and granulation steps. The amine resin crosslinked particles of the present invention have an average particle diameter of 0.1. 1 to 20 μηι, and the proportion of coarse particles with a particle size of 40 μηι or more is preferably a number basis of 0.50% or less. Among the particles in this range, the average particle diameter is 0 as described above. 1 to 5 μηι, and the ratio of particles with a particle size of 8 μηι or more is the number basis 0. Below 05% is preferred. In the first or second production method, the amine resin crosslinked particles of the present invention having the preferable average particle diameter and the like are preferably obtained by the second production method. The preferred state of the second manufacturing method is that amine resin crosslinked particles with extremely small particle diameters can be easily prepared by starting the hardening of the amine resin precursor in an aqueous solution state, and easy to obtain an average particle diameter of 0.1 to 5 μm , And the ratio of particles with a particle size of 8 μηι or more is the number reference 0. Amine resin crosslinked particles below 05%. In addition, the amine compound used in the second production method can satisfy the following water miscibility, and its type and composition ratio are preferably set appropriately, but it can form a water-soluble amine resin precursor by reacting with formaldehyde. Those who need it are better. In addition, the amine resin precursor obtained in the resinization step is preferably -33- (31) (31) 200401786 in terms of water solubility. The surfactant used in the second manufacturing method is for the purpose of obtaining water affinity of the amine resin precursor in an aqueous medium, and does not include the emulsifier used in the first manufacturing method. The degree of the above-mentioned water affinity is based on the measurement of the amount of water added to the initial condensate amine resin precursor dropwise to white turbidity at 15 t, and its weight% to the initial condensate (hereinafter, simply referred to as water Mixing degree) and the water mixing degree of the preferred amine resin precursor in the second manufacturing method is 100% or more. For amine resin precursors with a water mixing degree of less than 100%, in an aqueous solution containing a surfactant, no matter how they are dispersed, it can only form a non-uniform suspension with a large particle size, and it is difficult to obtain spherical fine particles. It has a uniform particle size. In the mixing step, the amine resin precursor obtained in the resinization step is mixed with a surfactant in an aqueous medium by stirring or the like to obtain a mixed solution. The surface active agent can be any surface active agent such as an anionic surface active agent, a cationic surface active agent, a nonionic surface active agent, an amphoteric surface active agent, and particularly an anionic surface active agent or a nonionic surface active agent. Or a mixture of these is preferred. For anionic surfactants, alkali metal salts of alkyl sulfates such as sodium dodecyl sulfate and potassium dodecyl sulfate; alkyl ammonium sulfates such as ammonium dodecyl sulfate; dodecyl polyethylene glycol ether Sodium sulphate; sulfur castor oil_sodium; alkyl sulfonates such as alkali metal salts of sulfonated petrolatum and ammonium salts of sulfonated paraffin; fatty acid salts such as sodium laurate, triethanolamine oleate, triethanolamine rosinate; ten Alkyl aryl sulfonates such as sodium dialkylbenzenesulfonate, -34- (32) (32) 200401786, alkali metal sulfates of basic phenolic hydroxyethylene; higher alkyl naphthalenesulfonates; morpholine naphthalenesulfonate Condensate; Dialkyl sulfosuccinate; Polyoxyethylene alkyl sulfate; Polyoxyethylene alkylaryl sulfate, etc. Non-ionic surfactants can use polyoxyethylene alkyl ether, polyoxyethylene oxane Aryl ethers; sorbitan fatty acid esters; polyoxyethylene sorbitan fatty acid esters; fatty acid monoglycerides such as glycerol monolaurate; polyethylene oxide propylene oxide copolymers of ethylene oxide and grease Condensation products of family amines, amidines, or acids. The amount of the surface active agent is 1 ο 〇 by weight to the amine resin precursor obtained in the resinization step described above. A range of 0.001 to 10 parts by weight is preferred. If it is less than 0. A small amount of 0 parts by weight may fail to obtain a stable suspension of amine resin crosslinked particles, and if it exceeds a large amount of 10 parts by weight, unnecessary foam may be generated in the above suspension and the resulting amine resin The physical properties of the crosslinked particles have an adverse effect. The mixing step is, for example, adding the reaction solution obtained in the resinization step in which the concentration of the amine resin precursor (i.e., the solid content) is in the range of 3 to 25% by weight, and adding the reaction solution to the aqueous solution of the surfactant, followed by mixing. In this case, the concentration of the aqueous surfactant solution is not particularly limited, as long as the concentration of the amine resin precursor can be adjusted within the above range. If the concentration of the amine resin precursor is less than 3% by weight, the productivity of the amine resin crosslinked particles may be reduced. If it exceeds 25% by weight, the obtained amine resin crosslinked particles may be enlarged and the particles may be aggregated. Because the particle diameter of the amine resin burst particles cannot be controlled, it may become amine resin crosslinked particles with a wide particle size distribution. For the stirring method in the mixing step, a general method can be adopted, for example, to use -35- (33) (33) 200401786 to stir using a disc turbine, a fan turbine, a Faedera mixer, a propeller type, and a multi-stage wing. The method is better. In the second manufacturing method, in order to further prevent the amine resin crosslinked particles finally obtained from agglutinating firmly, if necessary, inorganic particles may be added to the obtained mixed solution after the mixing step. Regarding the inorganic particles and the method of adding them, the same methods as those described in the first manufacturing method can be used. The hardening and granulating step is to add a catalyst (specifically, a hardening catalyst) to the mixed liquid obtained in the above mixing step, and obtain amine resin crosslinked particles through the hardening reaction of the amine resin precursor and its granulation (detailed This is a suspension of amine resin crosslinked particles). The catalyst (hardening catalyst) is preferably an acid catalyst. As the acid catalyst, the same ones as exemplified in the first production method can be appropriately used. In the second manufacturing method, it is particularly preferable to use an alkylbenzenesulfonic acid having an alkyl group having 10 to 18 carbon atoms. The alkylbenzene sulfonic acid having a carbon number of 10 to 18 is based on the aforementioned initial condensate. The aqueous solution of the female resin is used to exert a specific interfacial active function to form a stable suspension of a hardened resin. The necessary components can be exemplified by decylbenzenesulfonic acid, dodecylbenzenesulfonic acid, tetradecylbenzenesulfonic acid, hexadecylbenzenesulfonic acid, octadecylbenzenesulfonic acid, and the like. These may be used alone or in combination of two or more. The amount of the catalyst used is preferably 1,000 parts by weight of 0.1 parts by weight, and 0.5 parts by weight of summer parts, for the β-day driver of the moonflower tree in the mixed solution obtained in the above mixing step. More preferred is 10 parts by weight. Especially when using the above-mentioned alkylbenzenesulfonic acid having a carbon number of 10 to 8 alkyl groups, the amine resin in the mixed solution is -36-(34) (34) 200401786. -20 parts by weight is preferable, and 0.5-10 parts by weight is more preferable. If the amount of the catalyst used is smaller than that of the above-mentioned Fan Yuan, the time required for condensation and hardening is long ', and a stable suspension of amine resin crosslinked particles cannot be obtained, and a state containing only a large amount of aggregated coarse particles may be obtained in the end. In addition, if the amount is larger than the above range, the amine resin crosslinked particles in the resulting suspension must be allocated with more than the catalysts such as alkylbenzenesulfonic acid, etc., as a result, the amine resin crosslinked particles are plasticized and hardened by condensation. Aggregation or fusion between intermediate particles is easy to occur, and eventually amine resin crosslinked particles with a uniform particle diameter may not be obtained. Similarly, the amount of the catalyst used is 0 to 1 mol of the amine compound used as the raw material compound. Above 0005 moles is preferred, 0. More than 002 moles is preferred, 0. 005 -0. 05 Mo Er is even better. The amount of catalyst used is less than 1 mole for amine compounds. 〇 〇 〇 5 Moore, it takes a long time to react, and hardening may be insufficient. For the hardening reaction and granulation in the hardening and granulation step, the catalyst can be added to the mixed solution of amine resin crosslinked particles, and stirred at a low temperature of 0 ° c to a high temperature of more than 1000 ° c under pressure. Hold down. The method for adding the catalyst is not particularly limited and may be appropriately selected. The end point of the sclerosis reaction can be determined by sampling or visual inspection. The reaction time of the hardening reaction is not particularly limited. The hardening reaction is generally heated to a temperature of 90 ° C or above and maintained for a certain period of time to complete, it does not necessarily need to be hardened at high temperature, even if short time at low temperature, as long as the amine resin crosslinked particles in the resulting suspension reach methanol or The degree of hardening to the extent that acetone does not swell is sufficient. The stirring method in the hardening / granulation step is preferably performed by using a well-known stirring device (35) (35) 200401786. In the hardening and granulating step, the average particle diameter of the amine resin cross-linked particles obtained by hardening and granulating the amine resin precursor in the above-mentioned mixed solution is preferably 0.1 to 20 μm, and 〇] to 10 μm More preferably, it is even more preferable to 5 μm. The second manufacturing method may include a coloring step of adding a water solution obtained by dissolving a dye in water to a mixed solution of an amine resin precursor and a surfactant or a suspension of amine resin crosslinked particles. The types of dyes or the amounts used are the same as those described in the first manufacturing method. In the second manufacturing method, if necessary, a dye may be added to the reaction solution obtained in the above-mentioned resinization step as a first-stage coloring step. The details of the type of dye used in the previous coloring step or the amount thereof, and the pH adjustment when a dispersion liquid obtained by dispersing an oil-soluble dye in water are added are the same as those described in the first manufacturing method. The second production method may include a neutralization step of neutralizing the suspension containing the amine resin crosslinked particles obtained in the above-mentioned curing step. The details of the pH range or neutralizer in the neutralization step are the same as those described in the first production method. The second manufacturing method may further include a step of separating the amine resin crosslinked particles from the suspension of the amine resin crosslinked particles obtained after the hardening step or the neutralization step. In the second production method, the amine resin crosslinked particles are separated from the suspension and taken out are those obtained by separating the amine resin crosslinked particles obtained by curing from an aqueous medium in a mixing step. The method of separating and taking out the amine resin crosslinked particles from the suspension (the method of separation -38- (36) (36) 200401786) 'is the same as that described in the first method. In the second manufacturing method, the amine resin parent-linked particles are separated and taken out from the suspension, and refer to an aqueous medium in the amine resin cross-linked particles obtained through the hardening and granulating process from the mixing step or the hardening and granulating step. Separated and removed. In the second manufacturing method, the amine resin crosslinked particles taken out through the separation step are preferably performed at 130 to 190. (: Heating step of heating. The details of the heating step are the same as those described in the first production method. In addition, in the second method of producing amine resin crosslinked particles, an amine-based compound is reacted with formazan. The amine resin precursor is mixed with a surfactant in an aqueous medium, and a catalyst is added to the mixed solution to granulate the amine resin precursor in the aqueous medium to obtain amine resin crosslinked particles. The amine resin crosslinked particles obtained by hardening and granulation are separated and taken out from the suspension, and the amine resin crosslinked particle powder obtained by drying (heating) and pulverizing is preferably further subjected to a classification step. More specifically, The second method for producing amine resin crosslinked particles is to mix an amine resin precursor obtained by reacting an amine compound with formaldehyde in an aqueous medium and a surfactant, and add a catalyst to the mixture to make the above amine resin precursor In the method for obtaining amine resin crosslinked particles by granulating in the above-mentioned aqueous medium, it is better to separate the amine resin crosslinked particles obtained by hardening and granulation from the suspension liquid. Removed and dried (heated), pulverized to give an amine resin crosslinked particles of the powder, further classifying the average particle diameter becomes 0. 1 to 20 μΐΏ, and coarse particles with a particle size of 40 μηι or more are counted as 0. The form of amine resin crosslinked particles of less than 05% is preferred, and an average particle diameter of 0.1 to 5 pm can be obtained, and particles with a particle size of 8 μηι or more are based on the number of amine resin crosslinked of 0 05% or less. Granules -39- (37) (37) 200401786. In the second manufacturing method, as in the first manufacturing method, the embodiment in which the catalyst containing white to main component is used to combust the exhaust gas containing the formazan produced in the aforementioned heating step is treated. In the second manufacturing method, the details of the various methods and methods or various conditions of the steps after the aforementioned pulverization and / or classification are exactly the same as those described in the first manufacturing method. The second manufacturing method is the same as the first manufacturing method in that the above-mentioned amine resin crosslinked particles of the present invention can be easily obtained, and among them, an average particle diameter of 0.1 to 5 μηι and a particle diameter of 8 μιη or more can be obtained. A method in which the proportion of the particles is an amine resin crosslinked particle with a number basis of 0.5% or less is preferable. In addition, the "manufacturing method of the first and second types of amine resin crosslinked particles described above" refers to the above-mentioned present invention in which coarse particles (or particles) having a specific particle size or more are reduced to a predetermined number or less based on the number of reference particles. A method for producing amine resin crosslinked particles, but at the same time grasp the technical idea of the present invention from another aspect. As described above, when producing amine resin crosslinked particles, it can be considered that the above coarse particles ( Or particles) The adjustment method of adjusting the content ratio based on the number below the specified standard, or it can be considered as a management method of managing the above-mentioned coarse particles (or particles) based on the content ratio of the number below the specified standard, or manufacturing Management methods. EXAMPLES The present invention will be described in more detail with examples and comparative examples below, but the present invention is not limited thereto. In the following, for convenience, "parts by weight" is abbreviated as -40- (38) (38) 200401786 "parts" and "liters" is abbreviated as "L". Also, the following Examples 1 to 4 correspond to the first manufacturing method of the present invention, and Examples 5 to 7 correspond to the second manufacturing method of the present invention. [Example 1] A 10-L reaction kettle having a capacity of 10 liters was installed in a mixer, a reflux cooler, a thermometer, and a vibratory viscosity agent (manufactured by MIVI ITS JAPAN, model name · MI VI 600 1). 3000 g (6 mol) of benzoguanamine, 2600 g (formaldehyde 32 mol) of a 37% by weight aqueous solution of methyl formate and 10 g of sodium carbonate 10% by weight of an aqueous solution (sodium carbonate 0. 0.01 mol), warmed with stirring and reacted at 95 t. When the viscosity of the reaction solution became 4.5 × 1 · s (45 cP) (5 hours after the start of the reaction), the reaction solution was cooled to terminate the reaction step. Accordingly, a reaction solution containing a precursor of benzoguanamine and an initial formaldehyde condensate amine resin was obtained. Next, a 10-L reaction kettle with a capacity of a reflux cooler, a homogenizer (agitator, manufactured by Special Mechanization and Chemical Industry Co., Ltd.), and a thermometer was placed in polyvinyl alcohol (Cureira Co., Ltd.) as an emulsifier. System, trade name: PVA 2 0 5) 1 20 g of an aqueous solution obtained by dissolving in 2 50 g of water, and the temperature of the liquid was raised to 7 5 ° C. After adding the above reaction liquid to the reaction kettle, the temperature of the liquid was raised to 7 7 ° C, and the contents were vigorously stirred at a rotation speed of 7 000 rp m while maintaining the temperature at 7 7 ° C to make the amine resin precursor The body was opaque to obtain a precursor concentration of 52. 5% by weight of the emulsion. The Coulter multi-size meter -11 (manufactured by Coulter Co., Ltd., measuring the number of particles: 3 0 0 0 0) was used to measure the -41-454 (39) (39) 200401786 emulsion. The average particle diameter (d 50) of the amine resin precursor was 2. 4 μηα ′ standard deviation is 0. 7 μη]. Next, Aelogel 2 00 (manufactured by Ayerelo Gel Co., Ltd., Japan) with a solid concentration of 10% by weight as an aqueous dispersion of inorganic oxide sand was added to the reaction kettle 3 2 5 6 After g ', maintain the content at 7 7 ° C while stirring the contents vigorously for 5 minutes in a homogenizer at a revolution speed of 4,000 rpm. The resulting emulsion was cooled to 30 ° C. The time from the mixing of the amine resin precursor and the emulsifier aqueous solution to the addition of the catalyst in the next step was 3 hours. Then, 40 g (0.4 mole) of sulfuric acid as a catalyst was dissolved! An aqueous solution of 2000 g of pure water was added to the above emulsion (the temperature of the content was 30 ° C), and the temperature was raised to 90 ° C at 100 ° C / hour with stirring. After reaching 90 ° C, it is maintained at this temperature for 1 hour to condense and harden the amine resin precursor. The total reaction time was 7 hours. After the end of the hardening step, the suspension of the amine resin-containing crosslinked particles was cooled to 30 ° C, and then the pH of the suspension was adjusted to 7 using a 5% by weight aqueous sodium hydroxide solution. 5. After the neutralization step, the amine resin crosslinked particles were removed from the suspension by filtration. The removed amine resin crosslinked particles were dried by heating at 15 ° C for 3 hours. The dried material after heating treatment was sprayed and crushed with a classification machine (with classification function) (machine name: LABO. TET (Singapore Industrial Co., Ltd.)) pulverized (loose) and classified the pulverized material at the same time (the operating conditions are the powder supply amount: 0. 5kg / h, air pressure supplied by the crusher: C 4Mpa, secondary air (ventilation): small, adjustment ring: 3 pieces (24mm), isolation ring: 10mm). At this time, the above steps of pulverization and classification are performed in a room where the moisture content of the air is controlled within 3 g / m3. The air supplied by the simultaneous pulverizing section (40) (40) 200401786 (the air for conflict pulverization from the supersonic nozzle) The secondary air used by the classification section is air with a moisture content of 3 g / m3. Thereby, white powdery amine resin crosslinked particles (1) having few coarse particles can be obtained. The particle diameter of the amine resin cross-linked particles (]) was measured as a Coulter size-I 1 type ("Number of measurement particles: 3,000" manufactured by Coulter Corporation), and the average particle size (d5 0) is 2 · 5 μ] Ή, and the ratio of the number of coarse particles with a particle size of 40 μ1Ώ or more is 0 · 〇1%. The formaldehyde-containing exhaust gas generated in the heat treatment step was subjected to combustion treatment using a platinum-supported catalyst (product name of Japan Catalyst Corporation; C-7 0 2 3). As a result, there was no formaldehyde odor near the outlet of the combustion gas. Use air with a moisture content of 3 g / m3 as the air to transport the amine resin cross-linked particles (1) powder, fill it into several containers, and seal them separately, and keep them at 25 ° C. The container containing the powder of the amine resin crosslinked particles (1) was opened after one week, one month, and six months, respectively. The powder state of the amine resin crosslinked particles (1) was Coule The Tedo size meter -11 (manufactured by Coulter Co., Ltd., measuring the number of particles: 3000) was used to measure the average particle diameter and the ratio of coarse particles. As a result, the average particle diameter (d 5 0) after 1 week was 2. 5 μm, and the reference ratio of the number of coarse particles with a particle size of 40 μηι or more is 0. 〇 1%, the average particle size (d 50) after 1 month is 2.4 μm, and the reference ratio of the number of coarse particles with a particle size of 40 μm or more is 0. 01%, the average particle size (d 50 0) after 6 months is 2.5 μm, and the reference ratio of the number of coarse particles with a particle size of 40 μ m or more is 0. 01% There is no change in state ', it can be confirmed that the stability and storage stability of the amine resin cross-linked particles (1) obtained by the production method of the present invention are both excellent. In addition, from the above measurement > 43- (41) (41) 200401786 results and the aforementioned formula (A), the storage stability of the amine resin crosslinked particles (1) can be evaluated as 0% when stored for 1 month, and stored for 6 months. It is also 0% at the month. 75 g of polyester resin (Toyobo Co., Ltd., Pylon 2 0 0) as a binder resin, toluene for dilution] 2 g and methyl ethyl ketone 30 g were used to cross-link the particles with the amine resin. (]) Mixing to obtain a coating composition. A polyester film having a thickness of 100 μm was used as a base film (Lumitsu # 171, manufactured by Toyo Corporation, cut to A4 size), and the aforementioned coating composition was coated by a roll coating method. On one side of the film, it was dried in hot air at 20 ° C for one minute to form a light diffusion layer having a thickness of 30 / m, and a film was prepared as a light diffusion sheet. By observing this film, it was confirmed that a light-diffusing sheet having no spots on the film was in a good state. When an amine resin crosslinked particle (1) was used as a delustering agent, a good delustering effect was confirmed. [Example 2] A 10-L reaction kettle having a capacity of 10 L was installed in a mixer, a reflux cooler, a thermometer, and a vibration viscosity agent (manufactured by MIVI ITS JAPAN, model name: MIV I 6 0 0 1). Benzoguanamine 3 00 g (16 mol) of an amine compound and 2 600 g (formaldehyde 32 mol) of 37% by weight aqueous formaldehyde solution and 10 g of sodium carbonate 10% (sodium carbonate 0. 01 mol), warmed with stirring and reacted at 95 ° C. The inverse Γ liquid viscosity becomes 4. 5x] (T2Pa · s (45cP) (5 hours after the start of the reaction) The reaction solution was cooled to terminate the reaction step. Based on this, the anti-antibody containing benzoguanamine and formaldehyde initial condensate amine resin precursor was obtained. 44- (42) (42) 200401786 should be applied. Next, in a 10L reactor equipped with a reflux cooler, homogenizer (mixer, manufactured by Special Mechanized Chemical Industry Co., Ltd.), thermometer, etc., it will be placed as An emulsifier of polyvinyl alcohol (manufactured by Kurella Co., Ltd., trade name: PVA 2 0 5) 1 20 g of an aqueous solution obtained by dissolving in 2 50 g of water, and the temperature was raised to 7 5 ° C with stirring. After the reaction solution was added to the reaction kettle, the temperature of the solution was raised to 7 7 ° C, and the contents were vigorously stirred at a rotation speed of 70 rpm at a temperature of 7 7 ° C to make the amine resin precursor opaque. This amine resin precursor has a concentration of 5 2 · 5% by weight. The emulsion is measured by Coulter multi-size-II type (manufactured by Coulter Co., Ltd., the number of measured particles: 3 00 00), Average particle diameter of amine resin precursor in the emulsion (d 50) _ 2. 4 μm with standard deviation of 0. 7 μm. The resulting emulsion was cooled to 30 ° C. The time from mixing the amine resin precursor and the emulsifier aqueous solution to the catalyst addition in the next step was 3 hours. Next, 40 g of sulfuric acid (0. 4 mol) An aqueous solution obtained by dissolving in 120 g of pure water was added to the above emulsion (the temperature of the contents; ^ 30 ° C), and the temperature was raised to 90 ° C at 10 ° C / hour under stirring. . After reaching 90 ° C, the temperature was maintained at this temperature for [hours] to condense and harden the amine resin precursor. The total reaction time was 7 hours. After the end of the hardening step, the suspension of the amine resin-containing crosslinked particles was cooled to 30 t: After that, the pΗ of the suspension was adjusted to 7.5 using a 5% by weight aqueous sodium hydroxide solution. In the neutralization step_ The amine resin crosslinked particles were removed from the suspension by filtration. The removed amine resin crosslinked particles were dried by heating at 150 ° C for 3 hours. The dried material after the heat treatment was pulverized by a pulverizer (machine-45-(43) 200401786): Vantam mill AP-B, manufactured by Hosokawa Micron Co., Ltd. ((the operating conditions are sieve diameter: 0 3 mm) Discharge (pulverized material) from the pulverizer and convey it to the airflow in a state exposed to the indoor air (machine name: N-5, carefully manufactured by the company), and classify with an airflow classifier (the operating conditions are powder) Volume of material supply: Number of revolutions: 4,000 rpm, rotary valve: 10 degrees, secondary air opening: [secondary air opening, 0%, air flow: 9. lm3 / h, 2 times: pressure: 0. 20mmAq). The above-mentioned crushing and classification operations are performed in a room where the air content is controlled at 4g / m3, and at the same time, both the grinder and the gas used for classifying the flow are controlled by the moisture content at 4g / m3, so that less coarse particles can be obtained White powdery amine resin (2). The particle diameter of the amine resin crosslinked particles (2) was measured in Coulter-II type (manufactured by Coulter Corporation, and the number of measured particles: 30,000). As a result, the average particle diameter (d50) was 2.6 μηι, and The reference ratio of the number of coarse particles with a particle size of 40 μη is 0. 〇]%. The formaldehyde-containing exhaust gas generated in the heat treatment step was processed using a gold catalyst (manufactured by Japan Catalysts, product name; C- 7 023). As a result, there was no formaldehyde odor near the outlet of the combustion gas. Except that the amine resin (2) was transported by air with a moisture content of 4 g / m3, under the same conditions as in Example 1, it was filled to a sealed 'and stored at 25 ° C. After filling, the container containing the powder of the amine resin cross-linking (2), the powder state of the amine resin cross-linking particles (2) after each week, 1 month, and 6 months is based on Coulter Multi ”type Π (made by Coulter Corporation, measuring the number of particles: 3 000 〇) to measure loose particles, and then make 1 kg / h, 0 0%, 3 air differential air moisture machine shape air. Multi-particle measurement Multi-size measurement of the above carried white burning place Close-coupled particles in the container Unsealed, 3-inch meter-set its flat -46- (44) (44) 200401786 Average particle size and ratio of coarse particles. As a result,] the average particle diameter (d50) after 2 weeks was 2. 6m, and the reference ratio of the number of coarse particles with a particle size of 40 or more is 0. 〇 1%, the average particle size (d 50) after 1 month is 2 · 6 pm ′ and the reference ratio of the number of coarse particles with a particle size of 40 μηι or more is 〇. 〇]%, the average particle size (d 50) after 6 months is 2.6 μηι, and the reference ratio of the number of coarse particles with a particle size of 40 μm or more is 〇. 〇 1%, there is no change from the state immediately after manufacture, and it is confirmed that the stability and storage stability of the amine resin cross-linked particles (2) obtained by the manufacturing method of the present invention are very excellent. In addition, from the above measurement results and the aforementioned formula (A), the storage stability of the amine resin crosslinked particles (2) can be evaluated as 0% when stored for one month and 0% when stored for 6 months. Using the amine resin crosslinked particles (2), the same procedure as in Example 1 was performed to prepare a thin film as a light diffusion sheet. Observation of this film confirmed that a light-diffusing sheet having no spots on the film was in a good state. [Example 3] After cooling the resin-containing precursor precursor obtained in Example 1 to 30 ° C, Ayer was added to the reaction kettle with a solid content of 10% by weight as a solid aqueous solution of silicon oxide. Luo Gel 2 0 0 (manufactured by Ajello Gel Co., Ltd.) 3 2 5 6 g, stir the contents vigorously in a homogenizer at a rotation speed of 400 Orpm for 5 minutes. The coloring step is performed until the catalyst is added. Specifically, an aqueous solution prepared by dissolving 7 g of a colorant water-soluble dye "Acid Red 52" in pure water 350 g was used. The dye concentration was 2 weight. /. . Then, the prepared aqueous solution was added to the above-mentioned opacifying -47-(45) (45) 200401786 solution, and vigorously cured for 5 minutes. Next, the catalyst was added to the emulsion in the same manner as in Example 1 and the step after the 'hardening step was performed in the same manner as in Example I' to obtain colored amine resin crosslinked particles (3). The particle size distribution of the amine resin crosslinked k (3) was measured by a Coulter size_n type (the number of measurement particles manufactured by Coulter Corporation was 3,000), and the average particle size (d50) It is 2. 8 μηι, and the reference ratio of the number of coarse particles with a particle size of 40 μΐΏ or more is 0. 〇]%. Regarding the amine resin crosslinked particles (3), the same conditions as in Example 1 were charged into a trough and sealed, and stored at 25 ° C. After filling, the container containing the powder of the amine fet lipid-crosslinked particles (3) is opened at 1 week, 6 months, and 6 months, respectively, and the powder state of the amine resin-crosslinked particles (3) is opened. It is a Coulter multi-size meter (type Π (made by Coulter Corporation, number of measured particles: 30,000)), and the average particle diameter and the ratio of coarse particles were measured. As a result, the average particle diameter (d50) after 1 week was 2. 8m, and the reference ratio of the number of coarse particles with a particle diameter of 40 μηι or more is 0. 0 1%, the average particle size (d 50 0) after 1 month is 2. 8 pm, and the number of coarse particles with a particle size of 40 μηι or more is 0. 〇 1%, the average particle size (d 50) after 6 months is 2. 8 μηι, and the reference ratio of the number of coarse particles with a particle size of 40 μηι or more is 0. 0.01%, which is unchanged from the state immediately after manufacture, and it is confirmed that the stability and storage stability of the amine resin cross-linked particles (3) obtained by the manufacturing method of the present invention are very excellent. In addition, from the above measurement results and the aforementioned formula (A), the storage stability of the ageable resin crosslinked particles (3) can be evaluated as 0% when stored for one month and 0% when stored for 6 months. Polyvinyl chloride resin as polyolefin transparent substrate] 0 parts, -48-(46) 200401786 combined 10 parts of the above-mentioned colored amine resin crosslinked particles (3) were melt-kneaded, and the obtained colored resin was used. The composition was made into a film with a thickness of 50 μm. The obtained colored film was spotless, discolored, and the like, and was in a well-colored state. [Example 4] A white powdery amine resin crosslinked particle was obtained in the same manner as in Example 1 except that the time from mixing the amine resin precursor and the emulsifier aqueous solution to the catalyst addition in the next step was changed to 6 hours. 4). The particle size distribution of the amine resin cross-linked particles (4) was determined by Coulter multi-size meter -11 (manufactured by Coulter Co., Ltd., the number of measured particles: 3000), and the average particle diameter (d50) was 2 8 μηι, and the ratio of the number of coarse particles with a particle diameter of 40 μ1Ώ or more is 0. 〇 3%. Also, compared with Example 1, Due to the increase in time between the mixing of the amine resin precursor and the emulsifier aqueous solution and the addition of the catalyst in the next step, coarsening of some of the emulsified particles occurred, and a large number of particle sizes of 40 μ1 were generated in the hardened amine resin crosslinked particles. Above coarse particles. Therefore, although it was pulverized and classified under the same conditions as in the Example], the number of coarse particles with a particle diameter of 40 μηι or more is based on the number of amine resin crosslinked particles (4) and amine resin crosslinked particles (1). There has been a number of increases. The amine resin cross-linked particles (4) were filled in a container with the same conditions as in Example 1 and sealed, and stored at 25 ° C. After filling, the container containing the powder of the amine resin cross-linked particles (4) is unsealed after 1 week, 6 months, and 6 months, respectively. The powder state of the amine resin cross-linked particles (4) is With Coulter multi-size meter-II (manufactured by Coulter Corporation, number of measured particles: 30,000), the average particle diameter and the ratio of coarse particles were measured. As a result, the average particle diameter (d 5 0) after 1 -49- (47) (47) 200401786 weeks was 2. 8 m, and the reference ratio of the number of coarse particles with a particle size of 40 μ or more is 0. 03%, the average particle size (d 50) after 1 month is 2 · 8 μηι, and the number of coarse particles with a particle size of 40 μm or more is the standard ratio of 0. 〇 3%, the average particle size (d 50) after 6 months is 2 8 μ m, and the reference ratio of the number of coarse particles with a particle size of 40 μ m or more is 0. 0.3%, there is no change from the state at the time of manufacture, but it can be confirmed that the stability and storage stability of the amine resin crosslinked particles (4) obtained by the manufacturing method of the present invention are very excellent. In addition, from the above measurement results and the aforementioned formula (A), the storage stability of the amine resin crosslinked particles (3) can be evaluated as 0% when stored for one month and 0% when stored for 6 months. In the same manner as in Example 1 using the amine resin crosslinked particles (4), a film was prepared as a light diffusion sheet. By observing this film, it was confirmed that a light-diffusing sheet having no spots on the film was in a good state. [Comparative Example 1] A comparative amine was obtained in the same manner as in Example 2 except that the time from the mixing of the amine resin precursor and the emulsifier aqueous solution to the addition of the catalyst in the next step was 10 hours' and the classification was not performed after pulverization. Resin crosslinked particles (1). The particle diameter and particle size distribution of the comparative amine resin cross-linked particles (1) are measured by Coulter multi-size meter-type (made by Coulter Corporation, number of measured particles: 3 00 00), and the average particle diameter ( d50) is 4. 5 μηι, and the reference ratio of the number of coarse six particles with a particle size of 40 μηι or more is 1. 丨%. A comparative amine resin crosslinked particle (1) was used to make a film as a light diffusion sheet in the same manner as in Example 1. Observing the film, two spots on the film were observed -50 ^ (48) (48) 200401786 points, which is not suitable for practical use As a light diffusion sheet. [Comparative Example 2] Comparative amine resin crosslinked particles (2) were obtained in the same manner as in Example 2 except that classification was not performed after pulverization. The particle diameter and particle size distribution of the comparative amine resin cross-linked particles (2) are measured by a Coulter size_n type (manufactured by Coulter Corporation, the number of measured particles: 3 0000), and the average particle diameter (d50 ) Is 4. 0 μηι, and the ratio of the number of coarse particles with a particle diameter of 40 μηι or more is 0. 80%. A comparative amine resin crosslinked particle (2) was used in the same manner as in Example 1 to prepare a thin film as a light diffusion sheet. Observation of the film showed two spots on the film, which was not suitable for practical use as a light diffusion sheet. [Example 5] In a four-necked flask equipped with a stirrer, a reflux cooler, and a thermometer, 300 parts of melamine, a formaldehyde aqueous solution with a concentration of 37%, 5800 parts, and an ammonia aqueous solution with a concentration of 28% were placed. 30 parts were made into a mixture, and the pH of the reaction system was adjusted to 8. 0. The mixture was heated to 75 ° C with stirring and reacted at the same temperature for 60 minutes to obtain a reaction solution of an initial condensate amine resin precursor having a water content of 300%. In addition, 200 parts of anionic surfactant reopeleks 05 powder (basic sodium sulfonate manufactured by Kao Shiken Co., Ltd.) was dissolved in 44 80 parts of water. The temperature of the surfactant aqueous solution was raised. To 80 t: and stir. The reaction solution containing the amine tree-51-(49) (49) 200401786 lipid precursor was added to the aqueous surfactant solution under stirring, followed by the addition of 10% sodium dodecylbenzenesulfonate aqueous solution 9 0 At 0 parts, the temperature was gradually raised to 90 ° C, and it was kept for 2 hours to pelletize condensation and hardening, thereby obtaining a suspension of amine resin crosslinked particles. When the suspension was observed with an optical microscope (magnification of 800 times), it was found that the particle size was about 1. 5 μ1Ώ spherical particles, and each particle enters into intense Brownian motion. The suspension was cooled to 30 ° C, and 400 parts of a 1% aluminum sulfate aqueous solution was added thereto, and then the solid and liquid were separated by suction filtration. The isolated amine resin crosslinked particles were 1 3 0. (: Drying by hot air dryer for 2 hours to obtain 36,000 parts of amine resin crosslinked particles dried. Then the same operation as in Example 2 'the dried product was crushed (loose), and then classified to obtain amine resin crosslinked The cross-linked particles (5). The particle size of the amine resin cross-linked particles (5) is measured in terms of Coulter size_j 1 type (manufactured by Coulter Co., Ltd., the number of measured particles: 30,000). , The average particle diameter (d50) is 1.5 μηι], and the reference ratio of the number of particles with a particle diameter of 8 μηι or more is 0.001%. The classified amine resin cross-linked particles (5) are represented by 市When viewed with an electron microscope, the number of particles with a particle size of 8 m or more was 0 (the number of measurements: 3 0 0). Except for the use of air to transport the amine resin crosslinked particles (5) with a moisture content of 4 g / m3, Under the same conditions as in Example 1, it was filled into the dense tree in the container and stored at 25 t. After filling, the containers containing the powder of the amine resin cross-linked particles (5) were each one week,] Kaifeng after 6 months and 6 months, the powder state of ^ fe tree cross-linked tablets (5) is based on Coulter multi-size_ U type (Coulter company System, measuring the number of particles: 30,000)) measuring its average -52-(50) 200401786 average particle diameter and the ratio of particles with a particle size of 8 μηι or more, the average particle diameter (d50) is]. 5 μηι, and the particle size 8 μη] number reference ratio is 0. 〇 1%,] the average particle size after a month μm, and the number of particles with a particle size of 8 μm or more after a reference month, the average particle size (d 50) is 1. 5 μιη, and the reference ratio of the number of particles is 0. 0 1%, and the rigidity is changed, and it can be confirmed that neither the storage stability nor the storage stability of the seed (5) obtained by the manufacturing method of the present invention can be evaluated from the above measurement results and the formula (A) of the aforementioned 7 (5). The storage stability is also 0% when stored for one month. Except that the amine resin cross-linked particles (5) were used and the thickness of the light diffusion layer was 10 μm, the film was the same as that in Example i as a light diffusion sheet. Observation of the film confirmed that the S spot was a light diffusion sheet in a good state. [Example 6] In the four-necked flask used in Example 1, an amine, 80 parts of benzoguanamine, a 37% formaldehyde solution, a 10% sodium carbonate aqueous solution 1. 16 parts were prepared and the pH was adjusted to 8 · 0. The mixture was squeezed at a temperature of 40 minutes under stirring to obtain a reaction solution having a water-containing mixing degree as a precursor of the amine resin. In addition, the anion gel (Em a) gel) 4 3 0 (the diameter of the particles (d 5 0) above the level of Kao alkaloid (share result) weeks later is]. 5 ratio is 〇 〇]%, 6 particle size is 8 μm or more: amine resin crosslinked particles that are not in the state of manufacture are often superior. In addition, it is estimated that the crosslinked particles of amine resin are 0% and stored for 6 months in the same way as hot air drying. The same operation is performed to obtain the film without [into 70 parts of cyanuric solution 2 90 parts and concentrated matter, and the reaction system is Kunzhi 7 (TC, the same initial condensing system surfactant as 300 ° /), polyethylene oxide (51) (51) 200401786 oleyl ether) 7. 5 parts were dissolved in 2C5 parts of water, and the aqueous surfactant solution was warmed to 70 ° C and stirred. Add the reaction solution of the amine resin precursor into the aqueous surfactant solution under stirring to obtain a mixed solution of the amine resin precursor and the surfactant. After the mixed solution becomes transparent temporarily, add 5% dodecane 90 parts of an aqueous solution of sodium benzenesulfonate were kept at 70 ° C. for 2 hours to harden the condensation to obtain a suspension of amine resin crosslinked particles. This suspension was further heated to 90 ° C with stirring and kept at the same temperature for 1 hour to completely harden to obtain a suspension of sufficiently hardened amine resin crosslinked particles. From this suspension, the amine resin crosslinked particles were precipitated by centrifugation and dried with a hot air drier at 140 ° C for 4 hours to obtain 120 parts of a dried product of the amine resin crosslinked particles. Then, the dried product was pulverized and classified in the same manner as in Example] to obtain amine resin crosslinked particles (6). The particle diameter of the amine resin crosslinked particles (6) is based on the Coulter size—π type (manufactured by Coulter Corporation, the number of measured particles: 3 0 0 0 0). The average particle size (d50) It is 2.5 μηι, and the reference ratio of the number of particles having a particle diameter of 8 μηι or more is 0.001%. When the classified amine resin crosslinked particles (6) were examined with a scanning electron microscope, the number of particles having a particle size of 8 μm or more was 0 (the number of measurements: 3 00 0). Under the same conditions as in Example 1, the amine resin cross-linked particles (6) were continued until they were sealed in gluten and stored at 25 ° C. After filling, the container containing the powder of the amine resin crosslinked particles (6) will be unsealed after 1 week, 1 month, and 6 months, respectively. Coulter multi-size meter-Type II (manufactured by Coulter Co., Ltd., measuring the number of particles: 3 0000) Measure the average particle size and the ratio of particles with particle size S μm or more -54-(52) (52) 200401786 For example, the average particle size (d 5 〇) after 1 week was 2. 5 m, and the reference ratio of the number of particles with a particle size of 8 μηι or more is 0. 〇 1%,] the average particle diameter (d 50 0) after 2 months is 25 μηι, and the standard ratio of the number of particles with a particle diameter of 8 μ or more is 0. 〇 1%, the average particle size (d 50) after 6 months is 2. 5 μηι, and the reference ratio of the number of particles with a particle size of 8 μο or more is 0. 0.01%, which is unchanged from the state at the time of manufacture, but it can be confirmed that the stability and storage stability of the amine resin crosslinked particles (6) obtained by the manufacturing method of the present invention are excellent. In addition, from the above measurement results and the aforementioned formula (A), the storage stability of the amine resin crosslinked particles (6) can be evaluated as 0% when stored for 1 month, and also 0% when stored for 6 months. A thin film was prepared as a light diffusion sheet in the same manner as in Example 1 except that the thickness of the light diffusion layer made of the amine resin cross-linked particles (6) and dried by hot air was 10 μm. Observation of this film confirmed that the film was obtained on the film. A light-diffusion sheet with no spots is a good condition. [Example 7] Except that the pulverization and classification operations are performed in a room where the moisture content of the air is controlled below 0 g / m3, and the gas system used to form the air flow in the pulverizer and the classifier is controlled to a moisture content of 1 Og / Except for air below m3 ', the same operation as in Example 5 was performed to obtain white powdery amine resin crosslinked particles (7). The particle size and particle size distribution of the amine resin cross-linked particles (7) are based on Coulter multi-size meter-11 (manufactured by Coulter Co., Ltd., the number of measured particles: 3 0 0 0 0). The average particle size (d50 )for]. 5 μηι, and -55-cU Μ ^ (53) 200401786 with a particle size of 8 μηη or more, the reference ratio of the number of particles is 0. 03%. When the classified amine resin (7) was examined with a scanning electron microscope, the number of particles having a particle size of 8 μm or more was 〖(measured number: 3 00 0), which are agglomerated particles. The amine resin cross-linked particles (7) were filled with air in a container and sealed at 25 ° C in the same manner as in Example 1 except that air containing moisture_10 g / m3 was used as the transport air. The container filled with the powder of the amine resin crosslinked particles (7) is opened after j months and 6 months, respectively. The state of the amine resin crosslinked particles (7) is based on Coulter multi-size- Type 11 (made by Coulter Co., Ltd., number of measurements: 3 0 0 0 0) was measured for the average particle diameter and the ratio of the particle diameter above 8 μηι, and the average particle diameter (d50) after 1 week was 1. The reference ratio of the number of particles of 5 μηι and 8 μm is 0. 〇 3%,] the monthly average particle diameter (d 50) is 1. 5 μηι, and the reference ratio of the number of particles with a particle size of 8 μηι or more is 0. 0 5%, the average particle diameter (d 50 0) μηι after 6 months, and the reference ratio of the number of particles with a particle diameter of 8 μηι or more is 0 and there is no change in the state at the time of manufacturing, but it can be confirmed that The amine resin crosslinked particles (6) obtained by the method have excellent storage stability and storage properties. In addition, the storage stability of the amine resin crosslinked particles (7) can be evaluated from the above measurement results and the aforementioned formulas. The storage stability at the time of storage is 0%, and the storage stability at 6 months is also 0%. [Effects of the Invention] According to the present invention, it is possible to provide the above-mentioned amine resin cross-linked particles that do not cause spots or problems such as poor quality and the particle content suitable for producing such linked particles. The size of the solid particles is 1. 6 • 0 7%, manufacturer Zangan Ding (A) 1 month Fading amine resin -56-(54) 200401786 Method for cross-linking particles. Further, the amine resin crosslinked particles of the present invention can exhibit a good delustering effect as a delustering agent. -57-