201219406 六、發明說明： 【發明所屬之技術領域】 本發明係關於聚乳酸樹脂或聚烯烴系樹脂等之樹脂用 晶核劑及樹脂組成物。 【先前技術】 就保護自然環境之觀點而言，有關在自然環境中能生 物分解之脂肪族聚醋之硏究正大量地進行。之中又以聚乳 酸樹脂，因融點爲160~ 18 0 °C及透明性大大地優異，故被 期待作爲容器、薄膜等之包裝材料、衣料、纖維材料、電 氣、電子製品之成形材料。 然而’聚乳酸樹脂具有所謂結晶化速度慢之問題。若 結晶化速度慢時，因結晶化度會變低，耐熱性會變差。例 如，將聚乳酸樹脂藉由無法進行拉伸之射出成形等進行成 形時’成形物之結晶化度變低，在超過6 0。(：前後之玻璃 轉移溫度時’變得具有所謂容易變形之缺點。因此，爲了 提高結晶化度，雖然已嘗試著升高射出成形時模具之溫度 ’並加長於模具內冷卻時間之方法，但以此方法時因爲成 形時間會變長，生產性具有課題。 又’作爲提高聚乳酸樹脂或聚丙烯樹脂之結晶化速度 之方法’例如’已知有添加晶核劑之方法，其中該晶核劑 係成爲結晶性局分子之樹脂的一次（primary)晶核，並 促進結晶成長，及提局結晶化速度。 作爲聚乳酸樹脂之晶核劑，雖已有由特定粒徑以下之 -5- 201219406 滑石及/或氮化硼所成的無機粒子（參考專利文獻1 )、以 特定式所示醯胺化合物（參考專利文獻2)、以特定式所 示山梨糖醇衍生物（參考專利文獻3)、磷酸酯金屬鹽及 鹼性無機鋁化合物（參考專利文獻4)、苯膦酸之金屬鹽 (參考專利文獻5)等被揭示，但期望著更有效的樹脂用 晶核劑之開發。又，爲了縮短成形時間，亦期望提高結晶 化溫度。 [先前技術文獻] [專利文獻] [專利文獻1]特開平8-343 2號公報（申請專利範圍） [專利文獻2]特開平1 0-87975號公報（申請專利範圍 ) [專利文獻3]特開平1 0- 1 5 8 3 69號公報（申請專利範 圍） [專利文獻4]特開2003 - 1 92 8 8 3號公報（申請專利範 圍） [專利文獻5]國際公開第2005-97894號說明書（申請 專利範圍） 【發明內容】 [發明所欲解決的課題] 本發明之課題係以解決上述以往技術之問題點，以提 供可提高樹脂之結晶化速度及結晶化溫度之新穎樹脂用晶 -6- 201219406 核劑及樹脂組成物。 [解決課題之手段] 解決上述課題之本發明樹脂用晶核劑，其特徵係含有 鹼性三聚氰酸鋅粒子。 又，可爲聚乳酸樹脂用晶核劑或聚烯烴系樹脂用晶核 劑。 其中，前述鹼性三聚氰酸鋅粒子，可爲藉由雷射繞射 法所測定平均粒子徑D5Q爲80〜900nm，比表面積爲 20〜1 00m2/g。 又’前述鹼性三聚氰酸綷粒子，可將由氧化鋅及鹼性 碳酸鋅所選出之至少一種、三聚氰酸及水，以相對於水使 三聚氰酸濃度成爲0.1〜10.0質量％般，將已調合之混合漿 料藉由使用5〜5 5 °c溫度範圍之分散介質進行濕式分散而 製造者》 又，可含有苯膦酸之金屬鹽，前述苯膦酸之金屬鹽可 由苯膦酸鋅、苯膦酸鋰、苯膦酸鈉、苯膦酸鉀、苯膦酸鈣 、苯膦酸鎂及苯膦酸錳所選出之至少一種。 本發明之樹脂組成物，其特徵係含有樹脂及鹼性三聚 氰酸鋅粒子。 其中’前述樹脂係聚乳酸樹脂，相對於該聚乳酸樹脂 100質量份’較佳爲含有前述鹼性三聚氰酸鋅粒子 0.01-10.0 質量份。 又’前述樹脂係聚烯烴系樹脂，相對於該聚烯烴系樹 201219406 脂100質量份，較佳爲含有前述鹼性三聚氰酸鋅粒子 0.01〜10.0質量份。 又’前述聚烯烴系樹脂可由聚丙烯樹脂、聚乙烯樹脂 及聚醯胺樹脂所選出之至少一種。 其中，可含有苯膦酸之金屬鹽。 [發明之效果] 依照本發明，藉由使用鹼性三聚氰酸鋅粒子，可提供 新穎的樹脂用晶核劑提供。其中，含有此晶核劑與樹脂之 樹脂組成物，結晶化速度高，且，結晶化溫度成爲高者。 因而，可於短時間內得到結晶化度高，緻密、高剛性之透 明性亦爲優異之成形物。然後，藉由將以雷射繞射法所測 定平均粒子徑D5G爲80〜900nm、比表面積爲20〜100m2/g 之鹼性三聚氰酸鉢粒子作爲晶核劑，可使成形物之透明性 更提昇。又，藉由使同時含有鹼性三聚氰酸鋅粒子與苯膦 酸之金屬鹽，以成爲更優異之樹脂用晶核劑。 [實施發明的最佳型態] 本發明之樹脂用晶核劑爲含有鹼性三聚氰酸鋅粒子者 。鹼性三聚氰酸鋅，係已知作爲鐵系金屬表面之腐蝕防止 劑之物質，以往並未使用來作爲樹脂用之晶核劑，因本發 明團隊之發現，而成爲結晶性高分子之樹脂的一次晶核， 並促進結晶成長，及提高結晶化速度，又，因爲具有提高 結晶化溫度之機能，故可作爲晶核劑使用。 201219406 藉由將此鹼性三聚氰酸鋅粒子作爲晶核劑使用’因樹 脂之結晶化速度會變高，故樹脂之結晶化度會變高’可使 樹脂之成形物耐熱性提昇。又’藉由結晶化速度之變高’ 因結晶化所需要之時間變短’可在短時間內得到樹脂之成 形物，而提昇生產性。其中’藉由在短時間內進行結晶化 ，球晶尺寸變小，可得到緻密、具有高剛性之透明性優異 之成形物。又，因爲樹脂之結晶化溫度亦變高，在將樹脂 使用射出成形等之模具進行成形時，由於可將模具之冷卻 溫度提高，故可在短時間內得到樹脂之成形物，而提昇生 產性。 鹼性三聚氰酸鋅粒子之大小無特別限制，例如，藉由 使用以雷射繞射法所測定之平均粒子徑D5Q爲80〜900nm 、比表面積爲20〜100m2/g之細微的三聚氰酸鋅粒子，可 成爲透明性高的樹脂用晶核劑。 鹼性三聚氰酸鋅粒子，例如，可藉由將由氧化鋅及鹼 性碳酸鋅所選出之至少一種與三聚氰酸，視所需地進行加 熱等使產生反應而製造。因爲氧化鋅、鹼性碳酸鋅及三聚 氰酸爲廉價，故可提供廉價的樹脂用晶核劑。對於使由氧 化鋅及鹼性碳酸鋅所選出之至少一種與三聚氰酸產生反應 來製造鹼性三聚氰酸鋅之方法，未特別限定，例如，舉例 如使氧化鋅與三聚氰酸在沸騰水中產生反應之製造方法、 或將混合有氧化鋅與三聚氰酸之糊料，藉由一邊以 50〜250°C進行加熱，一邊以棒盤粉碎機（pin disc mill) 或翼式粉碎機，以外加剪切作用來進行製造之方法。 201219406 又，亦可使用將由氧化鋅及鹼性碳酸鋅所選出之 一種、三聚氰酸及水’以相對於水使三聚氰酸濃度 0.1〜10.0質量％般，將已調合之混合漿料藉由使用5~ 溫度範圍之分散介質進行濕式分散來製造鹼性三聚氰 粒子。藉由此製造方法，可製造以雷射繞射法所測定 均粒子徑D5〇爲80〜900nm、比表面積爲20〜l〇〇m2/g 微驗性三聚氰酸鋅粒子。以下對於此製造方法予以詳 具體爲，首先，將由氧化鋅及鹼性碳酸鋅所選出 少一種、三聚氰酸及水’以相對於水使三聚氰酸濃度 0 · I ~ 1 0 · 0質量％、較佳爲〇 . 1〜5 . 〇質量％般進行調合以 成混合漿料。相對於水之三聚氰酸濃度若高於1〇質 時’因爲漿料黏度變高會成爲糊狀，在後段使用分散 進行濕式分散之際，分散介質會變得無法移動。另一 ，相對於水之三聚氰酸濃度若較〇. 1質量％低時，生 變差，故不宜。 又，由氧化鋅及鹼性碳酸鋅所選出之至少一種與 氰酸之比例，未特別限定，以莫耳比，氧化鋅及驗性 鋅之氧化鋅換算量之合計/三聚氰酸，較佳爲1.0〜5.0 佳爲2.0〜3.0。氧化鋅換算量之合計/三聚氰酸若較5. 高、或較1.0爲低時，因爲未貢獻於反應之氧化鋅、 碳酸鋅或三聚氰酸會有大量殘留傾向之故。 接著，將所得到的混合漿料藉由使用5〜5 5。(：溫 圍之分散介質進行濕式分散’使由氧化鋅及鹼性碳酸 選出之至少一種與三聚氰酸產生反應，而製造鹼性三 至少 成爲 -5 5〇C 酸鋅 之平 之細 述。 之至 成爲 調整 量％ 介質 方面 產性 三聚 碳酸 、更 0爲 鹼性 度範 鋅所 聚氰 -10- 201219406 酸鋅粒子。 濕式分散係使用分散介質來進行。藉由使用分散介質 所進行之濕式分散，憑藉因分散介質之衝擊所產生的機械 能，可使由氧化鋅及鹼性碳酸鋅所選出之至少一種與三聚 氰酸產生機械化學磨光反應。所謂的機械化學磨光反應， 指爲藉由分散介質之衝擊，將機械能由多方面賦予給氧化 鋅、鹼性碳酸鋅或三聚氰酸，使產生化學反應者。 作爲分散介質，例如，舉例如安定化锆製珠粒、石英 玻璃製珠粒、鹼石灰玻璃製珠粒、氧化鋁珠粒、或此等之 混合物。若考量因分散介質彼此衝擊而使分散介質破碎產 生之污染時，作爲分散介質，較佳爲使用.安定化锆製珠粒 。然後，分散介質之大小，例如直徑0.1〜10mm、較佳爲 直徑0.5~2.0mm。分散介質之直徑若未滿0.1mm時，粉碎 介質彼此之衝擊能小，機械化學磨光反應性有變弱之傾向 。又’分散介質之直徑若較1 Omm大時，分散介質彼此之 衝擊能過大，因分散介質破碎而產生污染會變多，故不宜 〇 使用分散介質進行濕式分散之裝置，只要是能將混合 漿料添加於已投入有分散介質之容器中後，予以攪拌，藉 由使分散介質與氧化鋅、鹼性碳酸鋅或三聚氰酸產生衝擊 ，而使氧化鋅或鹼性碳酸鋅與三聚氰酸產生機械化學磨光 反應者即可’未特別限定’例如，舉例如砂磨機（sand grinder)、橫式珠粒硏磨機、磨碎機、珠磨機（Ashizawa Finetech (股）製）等。尙，用於攪拌分散介質之裝置之 -11 - 201219406 回轉數或反應時間等，配合所希望之粒子徑等予以適當地 調整即可。 又，濕式分散，以5〜55 °C來進行爲必要的，較佳爲 5〜4 5 °C。在較55 °C爲高之溫度下進行濕式分散時，三聚 氰酸會溶解於水中，此溶解的三聚氰酸會快速地與氧化鋅 或鹼性碳酸鋅產生反應，因而促進晶粒成長、或如後述合 成例所示般，而製造的鹼性三聚氰酸鋅會成爲粒徑大者。 其中，藉由在45 °C以下之低溫進行濕式分散時，特別會 成爲粒子小者，可製造出例如藉由雷射繞射法所測定平均 粒子徑D5G爲500nm以下之微粒子。尙，因爲可在如此般 之低溫進行製造，故可使用對於熱爲弱之樹脂等之裝置來 進行製造。 在此，非如上述般使用分散介質之濕式分散，而以棒 盤粉碎機或翼式粉碎機來外加剪切作用之方法時，或因爲 相對於氧化鋅、鹼性碳酸鋅或三聚氰酸，進行剪切之構件 僅只一方向能產生衝擊，而無法產生機械化學磨光反應， 無法得到粒子徑小的鹼性三聚氰酸鋅粒子。 如此般地，將由氧化鋅及鹼性碳酸鋅所選出之至少一 種、三聚氰酸及水，以相對於水使三聚氰酸濃度成爲 0.1〜10.0質量％般，將已調合之混合漿料藉由使用5〜5 5 °C 溫度範圍之分散介質進行濕式分散之製造方法所得到的鹼 性三聚氰酸鋅微粒子，藉由雷射繞射法所測定平均粒子徑 D50爲 80〜900nm、較佳爲 100〜500nm，比表面積爲 20~l〇〇m2/g'較佳爲 30~80m2/g。即，爲粒子徑小、比表 -12- 201219406 面積大者。尙，即使是將如此般之三聚氰酸鋅微粒子與粒 子徑相對爲大之鹼性三聚氰酸鋅，使用反噴硏磨機等之粉 碎機進行粉碎時，亦無法使成爲如藉由雷射繞射法所測定 平均粒子徑D5G爲80~900nm之細微者。 又，使用上述製造方法所得到的鹼性三聚氰酸鋅微粒 子，非球狀，而是如後述合成例所示般，爲針狀或板狀者 ，即，可使成爲細長之微粒子。如此般之鹼性三聚氰酸鋅 微粒，例如，以藉由穿透電子顯微鏡觀察之一次粒子徑， 長軸爲100〜800nm、短軸爲10〜60nm。 尙，可將含有所得到的鹼性三聚氰酸鋅微粒子之鹼性 三聚氰酸鋅漿料，以原樣地作爲樹脂用晶核劑使用，.又， 可將此漿料乾燥製成粉末狀者作爲樹脂用晶核劑。 又，本發明之樹脂用晶核劑，可同時含有鹼性三聚氰 酸鋅粒子與苯膦酸之金屬鹽。藉由含有苯膦酸之金屬鹽， 相較於僅僅由鹼性三聚氰酸鋅粒子所成的樹脂用晶核劑， 可進而提高樹脂之結晶化速度及結晶化溫度。 在此，苯膦酸之金屬鹽雖爲樹脂用晶核劑，但具有所 謂高成本之問題。在本發明中，藉由同時使用較苯膦酸之 金屬鹽爲低成本之鹼性三聚氰酸鋅粒子與苯膦酸之金屬鹽 ，可兼具所謂提高樹脂之結晶化速度及結晶化溫度之效果 ，與所謂低成本化之效果。 作爲苯膦酸之金屬鹽，舉例如苯膦酸鋅、苯膦酸鋰、 苯膦酸鈉、苯膦酸鉀、苯膦酸鈣、苯膦酸鎂、苯膦酸錳等 -13- 201219406 含有鹼性三聚氰酸鋅粒子及苯膦酸之金屬鹽之樹脂用 晶核劑’各成分之含有比例未特別限定，例如，只要使三 聚氰酸爲20〜40質量％、使苯膦酸爲1〇〜30質量％即可。 晶核劑組成物之三聚氰酸成分若未滿2 0質量％時，鹼性 三聚氰酸鋅含有量變少、而苯隣酸鋅含有量變高，除了苯 膦酸爲高價格外’即使是再提高此等以上之苯膦酸之濃度 ，晶核劑性能亦無法提昇。相反地，若晶核劑組成物之三 聚氰酸成分濃度較4〇質量％多時，因鹼性三聚氰酸鋅之 含有量變多、而苯膦酸鋅之含有量變得過少，晶核劑性能 會降低，故不宜。尙，三聚氰酸係以分子式C3N3 03H3所 不’且可由CHN元素分析所測定之氮量來予以定量。苯 膦酸係以分子式C6H7〇3P所示，且可藉由螢光X射線分 析所測定之磷量予以定量。 又，含有鹼性三聚氰酸鋅粒子及苯膦酸之金屬鹽之樹 脂用晶核劑所含有的鋅與苯膦酸鋅之比之鋅/苯膦酸鋅， 以質量比較佳爲較1大而未滿4。即使是使成爲1以下， 並提高高價格的苯膦酸濃度，晶核劑性能亦無法提昇，又 ，4以上時，因爲晶核劑性能會有降低傾向之故。 尙，樹脂用晶核劑，可含有氫氧化鎂、氧化鎂等。 含有如此般之本發明之鹼性三聚氰酸鋅粒子及苯膦酸 之金屬鹽之樹脂用晶核劑之製造方法，未特別限定，例如 ，可藉由將鹼性三聚氰酸鋅粒子與苯膦酸之金屬鹽以混合 機等予以混合而製造。 又，含有鹼性三聚氰酸鋅粒子及苯膦酸之金屬鹽之樹 -14- 201219406 鋰 氧 所 樹 鋰 氧 以 調 、 反 進 如 表 製 水 鎂 解 0.3 pH 乳 脂用晶核劑，亦可藉由將作爲原料之苯膦酸鎂、苯膦酸 、苯膦酸鈉、苯膦酸鉀等苯膦酸之金屬鹽之水溶液、由 化鋅及鹼性碳酸鋅所選出之至少一種、及三聚氰酸，視 需地進行加熱等使產生反應而製造。 又，含有鹼性三聚氰酸鋅粒子及苯膦酸之金屬鹽之 脂用晶核劑，亦可藉由將作爲原料之苯膦酸鎂、苯膦酸 、苯膦酸鈉、苯膦酸鉀等苯膦酸之金屬鹽之水溶液、由 化鋅及鹼性碳酸鋅所選出之至少一種、三聚氰酸及水， 相對於水使三聚氰酸濃度成爲0.1~10.0質量％般，將已 合之混合漿料在5〜5 5 °c溫度範圍，使用分散型攪拌翼 或分散介質之濕式分散使強力攪拌分散，使各原料產生 應而製造。將依此製造方法所得到的漿料藉由以U 0°C 行乾燥，可製造含有細微的鹼性三聚氰酸鋅、苯膦酸鋅 及構成原料之上述苯膦酸之金屬鹽之金屬氫氧化物（例 ，氫氧化鎂等）之樹脂用晶核劑。此樹脂用晶核劑，比 面積爲15〜100m2/g、較佳爲20〜100m2/g。以下對於此 造方法予以詳述。 首先，藉由將碳酸鹽或金屬氫氧化物與苯膦酸溶解 中，來調整作爲原料之苯膦酸之金屬鹽之水溶液。例如 可將碳酸鎂或氫氧化鎂與苯膦酸’使鎂與苯膦酸之比之 /苯膦酸，以莫耳比，使成爲例如〇 · 3〜〇 · 6之比例般地溶 於水中而調製。在此，鎂/苯膦酸（莫耳比）若未滿 時，而製造混合漿料之PH會成爲7以下。然後，將此 爲7以下之漿料乾燥所得到的樹脂用晶核劑，混練於聚 -15- 201219406 酸樹脂時，因聚乳酸之一部份會溶解，故結晶化速度高， 且結晶化溫度高，因而變得所謂晶核劑性能小，又，生成 的苯膦酸鋅會成爲粗大粒子，而聚乳酸樹脂之晶核劑性能 降低。其中，聚乳酸樹脂之溶解部分因爲會以非晶質之原 樣進行固化，該部分會變脆，機械特性會降低。又，鎂/ 苯膦酸（莫耳比）若較0.6大時，苯膦酸鎂粒子會析出。 因此，鎂/苯膦酸（莫耳比），以〇·3〜0.6之範圍內爲宜。 接著，將由氧化鋅及鹼性碳酸鋅所選出之至少一種、 三聚氰酸及水，相對於此水，使三聚氰酸濃度成爲 0.1〜10.0質量％、較佳爲1.0〜5.0質量％般地進行添加，然 後混合上述苯膦酸之金屬鹽之水溶液。例如作爲苯膦酸之 金屬鹽之水溶液爲使用苯膦酸鎂之水溶液時，苯膦酸鎂之 水溶液之濃度較佳以成爲1.0〜3.0質量％般地進行調合， 來調整混合漿料。尙，相對於水之三聚氰酸濃度若較10 質量％高時，因漿料黏度會變高而成爲糊狀，在以後段之 分散型攪拌翼、或使用分散介質之濕式分散時，會變得不 易強力攪拌分散。另一方面，相對於水之三聚氰酸濃度若 較0.1質量％低時，生產性差，故不宜。 又，由氧化鋅及鹼性碳酸鋅所選出之至少一種與三聚 氰酸之比例，未特別限定，以莫耳比，氧化鋅及鹼性碳酸 鋅之氧化鋅換算量之合計/三聚氰酸較佳爲1.〇〜5.0、更佳 爲2.5 ~3.0。氧化鋅換算量之合計/三聚氰酸若較5.0爲高 、或較1.0爲低時，因爲未貢獻於反應之氧化鋅、鹼性碳 酸鋅或三聚氰酸會有大量殘留傾向之故。 •16- 201219406 又，相對於水之，苯膦酸之金屬鹽中所含有苯膦酸之 調合比例，未特別限定，苯膦酸之金屬鹽中所含有苯膦酸 之濃度，較佳爲1.5〜3.0質量％。是因爲即使是較3.0質 量％爲高時，聚乳酸樹脂之晶核劑性能亦無法大大地提昇 ，又，若較1 · 5質量％爲低時，聚乳酸樹脂之晶核劑性能 會降低之故。 其次，將所得到的混合漿料，在例如5〜55 t溫度範 圍，以分散型攪拌翼、或使用分散介質之濕式分散等予以 強列攪拌分散。因此，在使由氧化鋅及鹼性碳酸鋅所選出 之至少一種與三聚氰酸產生反應生成鹼性三聚氰酸鋅之同 時，使氧化鋅或鹼性碳酸鋅與苯膦酸之金屬鹽產生反應而 生成苯膦酸鋅。 尙，強力攪拌分散，若在較55 °C爲高的溫度下進行 濕式分散時，所生成的鹼性三聚氰酸鋅及苯膦酸鋅會變成 粗大粒子，因聚乳酸樹脂之晶核劑性能會降低，故較佳爲 在未滿55 t下進行。又，若使用分散介質進行濕式分散 而予以製造時，可製造出含有藉由穿透電子顯微鏡觀察之 —次粒子之長軸爲100〜1 200nm、短軸爲10~100nm、藉由 雷射繞射法所測定平均粒子徑D5G爲80~900nm之鹼性三 聚氰酸鋅粒子、長軸及短軸爲50~800nm之苯膦酸鋅粒子 之樹脂用晶核劑。 含有如此般所得到的鹼性三聚氰酸鋅、苯膦酸鋅、或 構成原料之苯膦酸之金屬鹽之金屬氫氧化物（例如，氫氧 化鎂）之晶核劑組成物，可將含有此等之漿料，以原樣地 -17- 201219406 作爲樹脂用晶核劑來使用，又，可使此漿料乾燥，並將使 用棒盤或噴射硏磨機等製成微粉末狀者用來作爲樹脂用晶 核劑。 如此般樹脂用晶核劑之大小無特別限制，藉由使用比 表面積爲20〜100m2/g之細微的粒子，可成爲透明性高的 樹脂用晶核劑。 然後，本發明之樹脂組成物，係含有上述樹脂用晶核 劑之鹼性三聚氰酸辞粒子及樹脂者、或含有上述樹脂用晶 核劑之鹼性三聚氰酸鋅粒子、苯膦酸之金屬鹽及樹脂者。 作爲樹脂，例如，舉例如聚乳酸、或聚烯烴系樹脂。 又’可使用2種以上之樹脂。作爲聚乳酸樹脂，舉例如乳 酸之均聚物或共聚物、或將此等乳酸之均聚物或共聚物作 爲主體而混合有其他樹脂之共混聚合物。作爲混合之其他 樹脂，舉例如聚乳酸以外的生物分解性樹脂、泛用合成樹 脂、泛用合成工業用塑膠等。聚乳酸樹脂若爲共聚物時， 排列樣式可任意爲無規共聚物、交替共聚物、嵌段共聚物 、接枝共聚物。又，可將利用熱、光、放射線等以交聯劑 使上述聚乳酸樹脂交聯者’來作爲聚乳酸樹脂使用。當然 ，此等聚乳酸樹脂可使用2種以上。其中，聚乳酸之分子 量未特別限定，例如’數平均分子量爲10, 〇〇〇〜500,〇〇〇 左右。又’聚乳酸樹脂之製造方法未特別限定，例如，使 乳酸交酯開環聚合、或使乳酸之D體、L體、外消旋體等 直接縮聚合，可予以製造。 又’作爲聚烯烴系樹脂，舉例如聚乙烯樹脂、聚丙烯 -18- 201219406 樹脂、聚醯胺樹脂等。其中，作爲聚丙烯樹脂，舉例如聚 丙烯、乙烯-丙烯共聚物等、或以不飽和殘酸或該酸酐所 變性的聚丙烯。以不飽和羧酸或該酸酐所變性的聚丙烯方 面’例如，舉例如丙烯單獨聚合物或乙烯-丙烯共聚物等 之聚丙烯與、具有丙烯酸、甲基丙烯酸、馬來酸'伊康酸 、福馬酸、馬來酸酐、伊康酸酐等之酸或酸酐單位之不飽 和羧酸或該酸酐之共聚物、或接枝共聚物等。特佳爲丙烯 與丙烯酸或馬來酸酐之共聚物、或接枝共聚物。當然，此 等聚烯烴系樹脂可使用2種以上。其中，聚烯烴系樹脂之 分子量未特別限定，例如，數平均分子量爲10,00 0〜 500,000 左右 。 鹼性三聚氰酸鋅粒子與樹脂之調合比例未特別限定， 若作爲樹脂爲使用聚乳酸樹脂時，相對於聚乳酸樹脂1 〇〇 質量份’較佳爲使鹼性三聚氰酸鋅粒子成爲〇.〇1~1〇.〇質 量份。又’若作爲樹脂爲使用聚烯烴系樹脂時，相對於聚 烯烴系樹脂10Q質量份，較佳爲使鹼性三聚氰酸鋅粒子成 爲0.01〜10_0質量份。鹼性三聚氰酸鋅粒子之量，相對於 樹脂100質量份若未滿0.01質量份時，因爲提高樹脂之 結晶化速度或結晶化溫度之效果會有不明顯之故。又，相 對於樹脂100質量份，若鹼性三聚氰酸鋅粒子之量較10.0 質量份爲多時，樹脂組成物之比重會變得過重之故。 又’同樣地，使用含有鹼性三聚氰酸鋅粒子及苯膦酸 之金屬鹽之樹脂用晶核劑時，調合比例亦未特別限定，作 爲樹脂若爲使用聚乳酸樹脂時，相對於聚乳酸樹脂1 〇 〇質 -19- 201219406 量份’較佳爲使含有鹼性三聚氰酸鋅粒子及苯膦酸之金屬 鹽之樹脂用晶核劑成爲0 · 0 1〜1 0.0質量份。又，作爲樹脂 若爲使用聚烯烴系樹脂時’相對於聚烯烴系樹脂100質量 份’亦較佳爲使含有鹼性三聚氰酸鋅粒子及苯膦酸之金屬 鹽之樹脂用晶核劑成爲0·01〜10.0質量份。 本發明之樹脂組成物’可含有無機塡充劑。作爲無機 塡充劑’例如’舉例如玻璃纖維、碳纖維、滑石、雲母、 矽石、高嶺土、黏土、矽灰石、玻璃珠粒、玻璃片、鈦酸 鉀、碳酸鈣、硫酸鎂、氧化鈦等。此等無機塡充劑之形狀 ’可任意爲纖維狀、粒狀、板狀、針狀、球狀、粉末。此 等無機塡充劑之調合量，例如，相對於樹脂100質量份， 可使成爲3 00質量份以下。 又’本發明之樹脂組成物.，可含有難燃劑。作爲難燃 劑’例如，舉例如溴系或氯系等之鹵素系難燃劑、三氧化 銻、五氧化銻等之銻系難燃劑、氫氧化鋁或氫氧化鎂、聚 矽氧系化合物等之無機系難燃劑、紅磷、磷酸酯類、聚磷 酸銨、磷腈等之磷系難燃劑、三聚氰胺、蜜白胺、蜜勒胺 、三聚二氰胺（mellon)、三聚氰酸三聚氰胺鹽、磷酸三 聚氰胺、焦磷酸三聚氰胺、聚磷酸三聚氰胺、聚磷酸三聚 氰胺·蜜白胺.蜜勒胺複鹽、烷基膦酸三聚氰胺、苯膦酸 三聚氰胺' 硫酸三聚氰胺、甲磺酸蜜白胺等之三聚氰胺系 難燃劑、PTFE等之氟樹脂等。此等難燃劑之調合量，例 如，相對於樹脂1 00質量份，可使成爲200質量份以下。 又，樹脂組成物，除了上述成分以外，可含有熱安定 -20- 201219406 劑、光安定劑、紫外線吸収劑、防氧化劑、衝撃改良劑、 防靜電劑、顏料、著色劑、脫模劑、潤滑劑、可塑劑、相 溶化劑、發泡劑、香料、抗菌抗黴劑、矽烷系、鈦系、鋁 系等之各種偶合劑、其他的各種塡充劑、或三聚氰酸鋅粒 子以外之晶核劑等，於一般之合成樹脂製造時通常所使用 之各種添加劑。 使用樹脂與鹼性三聚氰酸鋅、或、鹼性三聚氰酸鋅及 苯膦酸之金屬鹽，與視所需所添加之各種添加劑，製造樹 脂組成物之方法未特別限定，可使用與含有習知晶核劑之 樹脂組成物爲相同之方法來製造。例如，將樹脂與鹼性三 聚氰酸鋅、或、鹼性三聚氰酸鋅及苯膦酸之金屬鹽，與視 所需所添加之添加劑以各種混合機進行混合，使用單軸或 二軸擠壓機等，藉由例如150〜220 °C左右之溫度進行混練 ’可製造樹脂組成物。又，生成含有高濃度的鹼性三聚氰 酸鋅、或、鹼性三聚氰酸鋅及苯膦酸之金屬鹽、視所需所 添加的添加劑之母體混合物，將此添加於樹脂中之方法亦 爲可能的。其中，亦可爲在樹脂之聚合階段，添加鹼性三 聚氰酸鋅、或、鹼性三聚氰酸鋅及苯膦酸之金屬鹽之方法 〇 如此般之本發明之樹脂組成物，藉由射出成形、吹氣 成形、真空成形、壓縮成形等一般之成形法，可容易地製 造各種成形物。成形物，可例如作爲容器、薄膜等之包裝 材料 '衣料、纖維材料、電氣、電子製品等予以使用。 接著’本發明之樹脂組成物，因爲含有晶核劑之鹼性 -21 - 201219406 三聚氰酸鋅粒子、或、鹼性三聚氰酸鋅粒子及苯膦酸之金 屬鹽，樹脂之結晶化速度高。因此，樹脂之結晶化度變高 ，可得到耐熱性良好的成形物。又，藉由結晶化速度之變 高，因結晶化所需要之時間變短，可在短時間內製造樹脂 之成形物。然後，藉由在短時間內進行結晶化，球晶尺寸 變小，可得到緻密、具有高剛性之透明性優異的成形物。 又，藉由含有鹼性三聚氰酸鋅粒子、或、鹼性三聚氰酸鋅 粒子及苯膦酸之金屬鹽，因樹脂之結晶化溫度亦變高，在 將樹脂使用射出成形等之模具進行成形時，由於可將模具 之冷卻溫度提高，故可在短時間內製造樹脂之成形物。 【實施方式】 [實施例] 以下，依據實施例及比較例更進一步予以詳述，惟， 本發明並非受限於此等實施例者。 (測定裝置） 關於實施例及比較例之分析，係使用以下之裝置·條 件所進行。 穿透型電子顯微鏡觀察：JEM-1010型（日本電子（股） 製）外加電壓100KV。 雷射繞射法粒子徑測定：S A L D - 7 0 0 0型（（股）島津製作 所製），將試樣1 g以純水稀釋2 0 0倍來測定。 比表面積測定：氮吸著法表面積測定裝置Monosorb機（ -22- 201219406 yuasa-ionics (股）製）。 重量分析：將約2g的試樣置入磁器製坩堝中精秤後，以 1 1 〇 °C乾燥後之質量算出固形分。 X射線粉末繞射分析：粉末X射線繞射裝置RINT Ultima 型（（股）Rigaku 製）。 元素分析：全自動元素分析裝置CHNS/OAnalyzer 2400 ( PerkinElmer 公司製）。 (合成例1 ) 在容積1升之內壁爲胺甲酸乙酯樹脂之分批式砂磨機 (sand grinder )容器中，置入 Φ 1mm之安定化銷製粉 碎珠粒1140g與純水300g，將砂磨機容器以-5°C之冷凝 器一邊進行冷卻，一邊使用攪拌盤以500rpm進行回轉， 並投入三聚氰酸粉末（日產化學工業（股）製）5.9g。持 續將砂磨機容器以-5 °C之冷凝器一邊進行冷卻，一邊使用 攪拌盤以500rpm進行回轉，並投入氧化鋅粉末（堺化學 (股）製的2種氧化鋅）9.3g。氧化鋅/三聚氰酸之莫耳 比爲2.5，相對於水之三聚氰酸濃度爲2.0質量％。投入 氧化鋅粉末後，以1 2小時將砂磨機容器以-5 °C之冷凝器 一邊進行冷卻，一邊使用攪拌盤以500rPm進行回轉使分 散。此時的漿料溫度爲9°C。因此’得到PH7.1、導電度 84 y S/cm、110。(：乾燥時之固形分爲4.8質量％之白色漿料 3 1 0g。將所得到的白色漿料之1 1 〇°C乾燥粉進行元素分析 ，結果爲碳10.37質量％、氫1.35質量％、氮12.05質量 -23- 201219406 %、氧2 8.2 0質量％。又，將此1 1 0 °C乾燥粉以1 0 0 0 °C使 熱分解成爲氧化鋅後’進行質量測定，求得11 〇 °c乾燥粉 之Zn之有效成分量’結果爲48.03質量％。又，對於110 °C乾燥粉進行x射線粉末繞射分析，結果如圖1所示般 ，未觀察到歸屬於原料之三聚氰酸及氧化鋅之繞射峰，有 觀察到鹼性三聚氰酸鋅之繞射峰。由此等結果，可決定 ll〇°C乾燥粉爲Zn5(C3N303)2(0H)3.3H20之鹼性三聚氰 酸鋅。所得到的白色漿料中所含有的微粒子，以穿透型電 子顯微鏡觀察時’係長軸爲1〇〇〜200nm、短軸爲1〇〜I5nm ，藉由雷射繞射法粒子徑測定之平均粒子徑D5〇爲l〇3nm ，70°C乾燥後之比表面積Sw爲59m2/g之鹼性三聚氰酸鋅 。結果如表1所示°又，穿透型電子顯微鏡所觀察之照片 如圖2所示。 (合成例2) 在容積1升之內壁爲胺甲酸乙酯樹脂之分批式砂磨機 容器中，置入 φ 1mm之安定化錐製粉碎珠粒114〇g與純 水3 OOg，將砂磨機容器以-5 °C之冷凝器一邊進行冷卻， 一邊使用攪拌盤以1 5 00rPm進行回轉，並投入三聚氰酸粉 末（日產化學工業（股）製）5_9g。持續將砂磨機容器 以-5 °C之冷凝器一邊進行冷卻’一邊使用攪拌盤以 1500rpm進行回轉，並投入氧化鋅粉末（裙化學（股）製 的2種氧化鋅）9.3g。氧化鋅/三聚氰酸之莫耳比爲2.5, 相對於水之三聚氰酸濃度爲2.0質量％。投入氧化鋅粉末 -24- 201219406 後，以8小時將砂磨機容器以〇 °c之冷凝器一邊進行冷卻 ，一邊使用攪拌盤以1 5 0 0 rp m進行回轉使分散。此時的漿 料溫度爲1 6°C。因此’得到pH7.1、導電度1 〇9仁S/cm、 110 °C乾燥時之固形分爲4.8質量％之白色漿料311g。又 ，對於所得到白色漿料之11 0 °c乾燥粉進行X射線粉末繞 射分析，結果與合成例1爲同樣之繞射圖型。所得到的白 色漿料中所含有的微粒子，以穿透型電子顯微鏡觀察時， 係長軸爲1〇〇〜3 00nm、短軸爲10〜20nm’藉由雷射繞射法 粒子徑測定之平均粒子徑D5((爲155nm，70°C乾燥後之比 表面積Sw爲49m2/g之鹼性三聚氰酸鋅。結果如表1所示 (合成例3 ) 在容積1升之內壁爲胺甲酸乙酯樹脂之分批式砂磨機 容器中，置入 Φ lmm之安定化鉻製粉碎珠粒1 140g與純 水3 00g，將砂磨機容器以-5°C之冷凝器一邊進行冷卻， —邊使用攪拌盤以2 00 Orpm進行回轉，並投入三聚氰酸粉 末（日產化學工業（股）製）5.9g。持續將砂磨機容器 以-5 °C之冷凝器一邊進行冷卻，一邊使用攪拌盤以 2000 rpm進行回轉，並投入氧化鋅粉末（堺化學（股）製 的2種氧化鋅）9.3g。氧化鋅/三聚氰酸之莫耳比爲2.5， 相對於水之三聚氰酸濃度爲2.〇質量％。投入氧化鋅粉末 後，以8小時將砂磨機容器以-5 t之冷凝器一邊進行冷卻 ，一邊使用攪拌盤以2000rpm進行回轉使分散。此時的漿 -25- 201219406 料溫度爲23°C。因此，得到ΡΗ7·0、導電度120 S/cm、 ll〇°C乾燥時之固形分爲4·8質量％之白色漿料305g。又 ，對於所得到白色漿料之110°c乾燥粉進行X射線粉末繞 射分析，結果與合成例1爲同樣之繞射圖型。所得到的白 色漿料中所含有的微粒子’以穿透型電子顯微鏡觀察時， 係長軸爲100~400nm、短軸爲20〜30nm’藉由雷射繞射法 粒子徑測定之平均粒子徑D5G爲175nm，70°C乾燥後之比 表面積Sw爲32m2/g之鹼性三聚氰酸鋅。結果如表1所示 。又，穿透型電子顯微鏡所觀察之照片如圖3所示。 (合成例4) 在容積1升之內壁爲胺甲酸乙酯樹脂之分批式砂磨機 容器中，置入 Φ 1mm之安定化锆製粉碎珠粒114 0g與純 水2 9 0 g，將砂磨機容器以2 0 °C之自來水一邊進行冷卻， 一邊使用攪拌盤以1 5 00rpm進行回轉，並投入三聚氰酸粉 末（日產化學工業（股）製）9.2g。持續將砂磨機容器以 20°C之自來水一邊進行冷卻，一邊使用攪拌盤以150〇rpm 進行回轉，並投入氧化鋅粉末（堺化學（股）製的2種氧 化鋅）14.5g。氧化鋅/三聚氰酸之莫耳比爲2.5，相對於 水之三聚氰酸濃度爲3.2質量％。投入氧化鋅粉末後，以 10小時將砂磨機容器以20°C之自來水一邊進行冷卻，一 邊使用攪拌盤以1 500rpm進行回轉使分散。此時的漿料溫 度爲40°C。因此，得到ρΗ6·8、導電度 148yS/cm、ll〇 t乾燥時之固形分爲7.5質量％之白色漿料300g。又，對 -26- 201219406 於所得到白色漿料之1 i 〇°C乾燥粉進行x射線粉末繞射分 析，結果與合成例1爲同樣之繞射圖型。所得到的白色漿 料中所含有的微粒子，以穿透型電子顯微鏡觀察時，係長 軸爲100~300nm、短軸爲20〜30nm，藉由雷射繞射法粒子 徑測定之平均粒子徑D5G爲188nm，70°C乾燥後之比表面 積Sw爲26mz/g之鹼性三聚氰酸鋅。 (合成例5) 在容積1升之內壁爲胺甲酸乙酯樹脂之分批式砂磨機 容器中，置入 Φ 1mm之安定化锆製粉碎珠粒1 I40g與純 水290g ’將攪拌盤以150〇rpm進行回轉，並投入三聚氰 酸粉末（日產化學工業（股）製）5.9g。持續將攪拌盤以 1500rpm進行回轉，並投入氧化鋅粉末（堺化學（股）製 的2種氧化鋅）9.3g。氧化鋅/三聚氰酸之莫耳比爲2 5, 相對於水之三聚氰酸濃度爲2_0質量％。投入氧化鋅粉末 後，以5小時將攪拌盤以1500rpm進行回轉使分散。此時 的漿料溫度爲50°C。因此，得到PH8,2、導電度176/z S/cm、110C乾燥時之固形分爲4.8質量％之白色發料 3 0 0 g。又’對於所得到白色獎料之1 1 〇它乾燥粉進行X射 線粉末繞射分析’結果與合成例1爲同樣之繞射圖型。所 得到的白色漿料中所含有的微粒子，以穿透型電子顯微鏡 觀察時，係長軸爲100〜200nm、短軸爲20〜4〇nm，藉由雷 射繞射法粒子徑測定之平均粒子徑爲623nm，7(rc乾 燥後之比表面積Sw爲25m2/g之鹼性三聚氰酸辞。結果如 -27- 201219406 表1所示。 (合成例6) 在容積1升之內壁爲胺甲酸乙酯樹脂之分批式砂磨機 容器中，置入 Φ lmm之安定化锆製粉碎珠粒1140g與純 水298g，將砂磨機容器以10 °C之冷凝器一邊進行冷卻， —邊使用攪拌盤以2000rpm進行回轉，並投入三聚氰酸粉 末（日產化學工業（股）製）4.3g。持續將砂磨機容器以 l〇°C之冷凝器一邊進行冷卻，一邊使用攪拌盤以1 500rptn 進行回轉，並投入鹼性碳酸鋅粉末（氧化鋅成分74.8質 量％，堺化學（股）製）9.0g。氧化鋅換算量/三聚氰酸之 莫耳比爲2.5，相對於水之三聚氰酸濃度爲1.4質量％。 投入氧化鋅粉末後，以8小時將砂磨機容器以10°C之冷 凝器一邊進行冷卻，一邊使用攪拌盤以1 500rpm進行回轉 使分散。此時的漿料溫度爲3 0°C。因此，得到pH6.3、導 電度556yS/cm、黏度198mPa.s、110°C乾燥時之固形 分爲3.5質量％之白色漿料3 10g。又，對於所得到白色漿 料之1 1 〇°C乾燥粉進行X射線粉末繞射分析，結果與合成 例1爲同樣之繞射圖型。所得到的白色漿料中所含有的微 粒子’以穿透型電子顯微鏡觀察時，係長軸爲1〇〇〜300nm 、短軸爲20~4 0nm ’藉由雷射繞射法粒子徑測定之平均粒 子徑Dn爲303nm’ 70°C乾燥後之比表面積Sw爲30m2/g 之鹼性三聚氰酸鋅。結果如表1所示。 -28- 201219406 (合成例7) 將純水24kg與氧化鋅粉末（堺化學（股）製的2種 氧化鋅）1.88kg投入於容積2 00升之混合用槽中，以分散 進行攪拌混合後，調製氧化鋅換算濃度爲7.69質量％之漿 料2 6kg。接著，將 Φ 1mm之安定化銷製粉碎珠粒66kg 置入於有效容積爲10.66升之內壁爲胺甲酸乙酯樹脂之橫 式珠粒硏磨機（Ashizawa Finetech (股）製珠磨機 PM25TEX-H )中。將純水 144kg置入於裝置有冷凝器之 循環槽後，將珠磨機之盤以周速1 0m/秒鐘進行回轉，以 供給速度爲5kg/分鐘將純水一邊供給於珠磨機，一邊使純 水循環。循環開始後投入三聚氰酸粉末（日產化學工業（ 股）製）1.19kg。投入三聚氰酸粉末後，以冷凝器使循環 漿料之溫度成爲3 2 °C般地予以調節後，將氧化鋅換算濃 度爲7.69質量％之氧化鋅漿料24.5 kg，分5次、花費1〇 分鐘進行添加。氧化鋅/三聚氰酸之莫耳比爲2.5，相對於 水之三聚氰酸濃度爲〇. 7質量％。氧化鋅漿料之添加後， 亦將珠磨機之盤一邊以周速l〇m/秒鐘進行回轉，一邊以 供給速度5kg/分鐘將漿料循環15小時，使分散。又，之 間亦以冷凝器使循環漿料溫度成爲3 2 °C般地進行調節。 因此，得到PH6.8、導電度67//S/cm、黏度51mPa.s、 ll〇t乾燥時之固形分爲1.8質量％之白色漿料166kg。對 於所得到白色漿料之11 〇°C乾燥粉進行X射線粉末繞射分 析，結果與合成例1爲同樣之繞射圖型。所得到的白色漿 料中所含有的微粒子，以穿透型電子顯微鏡觀察時，係長[Technical Field] The present invention relates to a resin nucleating agent and a resin composition such as a polylactic acid resin or a polyolefin resin. [Prior Art] As far as the protection of the natural environment is concerned, the research on the aliphatic polyester which can decompose the biomass in the natural environment is being carried out in a large amount. Among them, polylactic acid resin is widely used as a packaging material for packaging materials, clothing materials, fiber materials, electric materials, and electronic products because it has a melting point of 160 to 180 ° C and excellent transparency. However, polylactic acid resin has a problem that the so-called crystallization rate is slow. When the crystallization rate is slow, the degree of crystallization becomes low, and heat resistance is deteriorated. For example, when the polylactic acid resin is formed by injection molding or the like which cannot be stretched, the degree of crystallization of the molded article is lowered to more than 60%. (The glass transition temperature before and after the 'has a disadvantage of being so easily deformed. Therefore, in order to increase the degree of crystallization, although an attempt has been made to increase the temperature of the mold at the time of injection molding and to lengthen the cooling time in the mold, In this method, since the molding time becomes long, productivity is a problem. Further, as a method of increasing the crystallization rate of a polylactic acid resin or a polypropylene resin, for example, a method of adding a crystal nucleus is known, wherein the crystal nucleus is known. The agent is a primary nucleus of the resin of the crystalline local molecule, and promotes crystal growth and speed of crystallization. As a nucleating agent of the polylactic acid resin, it has been 5-5 below the specific particle diameter. 201219406 Inorganic particles of talc and/or boron nitride (refer to Patent Document 1), a guanamine compound represented by a specific formula (refer to Patent Document 2), and a sorbitol derivative represented by a specific formula (refer to Patent Document 3) ), a phosphate metal salt and a basic inorganic aluminum compound (refer to Patent Document 4), a metal salt of phenylphosphonic acid (refer to Patent Document 5), etc., but a more effective resin is desired. In order to shorten the forming time, it is also desired to increase the crystallization temperature. [Prior Art Document] [Patent Document] [Patent Document 1] JP-A-8-343 No. 2 (Application Patent Area) [Patent Literature [Patent Document 3] Japanese Laid-Open Patent Publication No. Hei No. Hei. No. Hei No. Hei. [Patent Document 5] International Publication No. 2005-97894 (Application Patent Scope) [Disclosure] [Problems to be Solved by the Invention] The object of the present invention is to solve the above problems of the prior art. In order to provide a nucleating agent and a resin composition for a novel resin which can increase the crystallization rate and the crystallization temperature of the resin, the present invention provides a nucleating agent for a resin of the present invention which solves the above problems. The characteristic system contains basic zinc cyanuric acid particles. Further, it may be a nucleating agent for a polylactic acid resin or a nucleating agent for a polyolefin resin. The above-mentioned basic zinc cyanurate particles may be used by a ray. Diffraction method The average particle diameter D5Q is 80 to 900 nm, and the specific surface area is 20 to 100 m 2 /g. Further, the aforementioned alkaline cyanuric acid cyanide particles can be at least one selected from zinc oxide and basic zinc carbonate, and cyanide. Acid and water, the concentration of cyanuric acid is 0 with respect to water. 1~10. 0% by mass, the mixed slurry is prepared by wet dispersion using a dispersion medium having a temperature range of 5 to 5 5 ° C. Further, a metal salt of phenylphosphonic acid may be contained, and the phenylphosphonic acid may be used. The metal salt may be at least one selected from the group consisting of zinc phenylphosphonate, lithium phenylphosphonate, sodium phenylphosphonate, potassium phenylphosphonate, calcium phenylphosphonate, magnesium phenylphosphonate and manganese phenylphosphonate. The resin composition of the present invention is characterized by containing a resin and basic zinc cyanurate particles. The above-mentioned resin-based polylactic acid resin preferably contains the above-mentioned basic zinc cyanurate particles with respect to 100 parts by mass of the polylactic acid resin. 01-10. 0 parts by mass. Further, the resin-based polyolefin resin preferably contains the above-mentioned basic zinc cyanurate particles in an amount of 100 parts by mass based on 100 parts by mass of the polyolefin tree 201219406. 01~10. 0 parts by mass. Further, the polyolefin resin may be at least one selected from the group consisting of a polypropylene resin, a polyethylene resin, and a polyamide resin. Among them, a metal salt of phenylphosphonic acid may be contained. [Effect of the Invention] According to the present invention, a novel nucleating agent for a resin can be provided by using basic zinc cyanurate particles. Among them, the resin composition containing the crystal nucleating agent and the resin has a high crystallization rate and a high crystallization temperature. Therefore, a molded article having high crystallinity and compactness and high rigidity can be obtained in a short period of time. Then, by using a rare earth cetyanate particle having an average particle diameter D5G of 80 to 900 nm and a specific surface area of 20 to 100 m 2 /g as a crystal nucleating agent by a laser diffraction method, the molded article can be made transparent. Sexuality is improved. Further, by further containing a metal salt of basic zinc cyanurate particles and phenylphosphonic acid, it is more excellent as a nucleating agent for a resin. [Best Mode for Carrying Out the Invention] The crystal nucleating agent for a resin of the present invention is one containing basic zinc cyanuric acid particles. Basic zinc cyanurate, which is known as a corrosion inhibitor for iron-based metal surfaces, has not been used as a nucleating agent for resins, and has been discovered as a crystalline polymer by the team of the present invention. The primary nucleus of the resin promotes crystal growth and increases the crystallization rate. Moreover, since it has a function of increasing the crystallization temperature, it can be used as a crystal nucleating agent. 201219406 By using the basic zinc cyanurate particles as a nucleating agent, the crystallization rate of the resin is increased, so that the degree of crystallization of the resin is increased, and the heat resistance of the molded product of the resin is improved. Further, by the fact that the crystallization rate is high, the time required for crystallization becomes short, and the resin can be obtained in a short time, thereby improving productivity. In the case where crystallization is performed in a short period of time, the spherulite size is reduced, and a molded article having excellent transparency and high rigidity can be obtained. In addition, since the crystallization temperature of the resin is also increased, when the resin is molded by using a mold such as injection molding, the cooling temperature of the mold can be increased, so that a molded product of the resin can be obtained in a short time, and productivity can be improved. . The size of the basic zinc cyanuric acid particles is not particularly limited, for example, by using a fine trimeric having an average particle diameter D5Q of 80 to 900 nm and a specific surface area of 20 to 100 m 2 /g as measured by a laser diffraction method. The cyanic acid cyanide particles can be used as a nucleating agent for a resin having high transparency. The basic zinc cyanurate particles can be produced, for example, by reacting at least one selected from zinc oxide and basic zinc carbonate with cyanuric acid, if necessary, by heating or the like. Since zinc oxide, basic zinc carbonate, and cyanuric acid are inexpensive, an inexpensive nucleating agent for a resin can be provided. The method for producing basic zinc cyanurate by reacting at least one selected from zinc oxide and basic zinc carbonate with cyanuric acid is not particularly limited, and for example, zinc oxide and cyanuric acid are used, for example. A method for producing a reaction in boiling water or a paste in which zinc oxide and cyanuric acid are mixed, and heating at 50 to 250 ° C, using a pin disc mill or a wing type The pulverizer is a method of manufacturing by adding a shearing action. 201219406 Further, a kind of cyanuric acid and water selected from zinc oxide and basic zinc carbonate can also be used to make the concentration of cyanuric acid relative to water. 1~10. The mixed pulverized slurry was wet-dispersed by using a dispersion medium having a temperature range of 5 to 0% by mass to produce basic melamine particles. By this production method, microscopic zinc cyanuric acid particles having a uniform particle diameter D5 〇 of 80 to 900 nm and a specific surface area of 20 to 1 μm 2 /g can be produced by a laser diffraction method. The following is a detailed description of the manufacturing method. First, one less one selected from zinc oxide and alkaline zinc carbonate, cyanuric acid and water' is made to have a concentration of cyanuric acid relative to water of 0 · I ~ 1 0 · 0 % by mass, preferably 〇. 1~5. 〇The mass% is blended to form a mixed slurry. When the concentration of cyanuric acid in water is higher than 1 〇, the paste becomes a paste because the viscosity of the slurry becomes high, and the dispersion medium becomes unmovable when it is dispersed by wet dispersion in the subsequent stage. 4. The concentration of cyanuric acid relative to water is relatively low. When 1% by mass is low, the growth is poor, so it is not suitable. Further, the ratio of at least one selected from zinc oxide and basic zinc carbonate to cyanic acid is not particularly limited, and is a total of the molar ratio of the molar ratio of zinc oxide to zinc oxide and zinc for examination/cyanuric acid. Good for 1. 0~5. 0 is 2. 0~3. 0. The total amount of zinc oxide converted / cyanuric acid is more than 5. High, or more than 1. When 0 is low, since zinc oxide, zinc carbonate or cyanuric acid which does not contribute to the reaction has a large tendency to remain. Next, the obtained mixed slurry was used by using 5 to 5 5 . (: Wet dispersion of the dispersion medium of the temperature range) causes at least one selected from zinc oxide and alkaline carbonic acid to react with cyanuric acid to produce a basic thinness of at least -5 5 〇C acid zinc As described above, the amount of adjustment is medium. The production of trimeric carbonic acid, and the more basic is the basicity of zinc, polycyanide-10-201219406 zinc acid particles. The wet dispersion is carried out using a dispersion medium. The wet dispersion carried out, by means of the mechanical energy generated by the impact of the dispersion medium, at least one selected from zinc oxide and basic zinc carbonate can be subjected to mechanochemical polishing reaction with cyanuric acid. So-called mechanical chemistry The buffing reaction is a process in which mechanical energy is imparted to zinc oxide, alkaline zinc carbonate or cyanuric acid in a multitude of ways by the impact of a dispersion medium to cause a chemical reaction. As a dispersion medium, for example, stabilization is carried out. Zirconium beads, quartz glass beads, soda lime glass beads, alumina beads, or a mixture of these. If the dispersion medium is impacted by the dispersion medium, the dispersion medium is broken. When contaminated, as a dispersion medium, it is preferably used. Stabilized zirconium beads. Then, the size of the dispersion medium, such as a diameter of 0. 1 to 10 mm, preferably 0. 5~2. 0mm. The diameter of the dispersion medium is less than 0. At 1 mm, the impact energy of the pulverized medium is small, and the mechanochemical polishing reactivity tends to be weak. Moreover, if the diameter of the dispersion medium is larger than 1 Omm, the impact energy of the dispersion medium is too large, and the contamination due to the dispersion of the dispersion medium is increased, so it is not suitable to use a dispersion medium for wet dispersion, as long as it can be mixed. After the slurry is added to the container into which the dispersion medium has been charged, it is stirred, and the zinc oxide or the basic zinc carbonate is trimeric by causing the dispersion medium to be impacted with zinc oxide, alkaline zinc carbonate or cyanuric acid. The cyanic acid generating mechanochemical polishing reaction can be 'unspecially limited', for example, a sand grinder, a horizontal bead honing machine, an attritor, a bead mill (Ashizawa Finetech Co., Ltd.) )Wait.尙, the device for agitating the dispersion medium -11 - 201219406 The number of revolutions, the reaction time, etc., can be appropriately adjusted in accordance with the desired particle diameter. Further, it is necessary to carry out wet dispersion at 5 to 55 ° C, preferably 5 to 4 5 °C. When wet dispersion is carried out at a temperature higher than 55 ° C, cyanuric acid is dissolved in water, and the dissolved cyanuric acid reacts rapidly with zinc oxide or basic zinc carbonate, thereby promoting grain growth. The growth or the basic zinc cyanurate produced as shown in the synthesis example described later becomes a large particle size. In the case where the wet dispersion is carried out at a low temperature of 45 ° C or lower, the particles are particularly small, and fine particles having an average particle diameter D5G of 500 nm or less can be produced, for example, by a laser diffraction method. That is, since it can be manufactured at such a low temperature, it can be manufactured using a device such as a resin having a weak heat. Here, the wet dispersion of the dispersion medium is not used as described above, and the shearing action is applied by a bar mill or a wing mill, or because it is relative to zinc oxide, alkaline zinc carbonate or melamine. The acid, the shearing member can generate an impact in only one direction, and cannot produce a mechanochemical polishing reaction, and it is impossible to obtain an alkaline zinc cyanurate particle having a small particle diameter. Thus, at least one selected from the group consisting of zinc oxide and basic zinc carbonate, cyanuric acid and water are brought to a concentration of cyanuric acid relative to water. 1~10. The basic zinc cyanuric acid microparticles obtained by the wet dispersion method using a dispersion medium having a temperature range of 5 to 5 5 ° C, by a laser mass ratio of 0% by mass, by a laser The average particle diameter D50 measured by the shooting method is 80 to 900 nm, preferably 100 to 500 nm, and the specific surface area is 20 to 10 m2/g', preferably 30 to 80 m2/g. That is, the particle diameter is small and the area is larger than Table -12-201219406.尙 即使 碱性 碱性 碱性 碱性 碱性 碱性 碱性 碱性 碱性 碱性 碱性 碱性 碱性 碱性 碱性 碱性 碱性 碱性 碱性 碱性 碱性 碱性 碱性 碱性 碱性 碱性 碱性 碱性 碱性 碱性 碱性 碱性 碱性 碱性 碱性 碱性 碱性 碱性 碱性 碱性 碱性 碱性 碱性 碱性 碱性 碱性The average particle diameter D5G measured by the laser diffraction method is as small as 80 to 900 nm. Further, the basic zinc cyanuric acid microparticles obtained by the above-described production method are non-spherical, and are acicular or plate-like as shown in the synthesis example described later, that is, they can be elongated microparticles. Such basic zinc cyanuric acid microparticles, for example, have a primary particle diameter as observed by a transmission electron microscope, and have a major axis of 100 to 800 nm and a minor axis of 10 to 60 nm.尙, the alkaline zinc cyanurate slurry containing the obtained basic zinc cyanuric acid microparticles can be used as a nucleating agent for the resin as it is. Further, the slurry may be dried to form a powder as a nucleating agent for a resin. Further, the crystal nucleating agent for a resin of the present invention may contain a metal salt of a basic zinc cyanide particle and a phenylphosphonic acid. By containing a metal salt of phenylphosphonic acid, the crystallization rate of the resin and the crystallization temperature can be further increased as compared with the nucleating agent for the resin formed only from the basic zinc cyanurate particles. Here, although the metal salt of phenylphosphonic acid is a crystal nucleating agent for a resin, it has a problem of high cost. In the present invention, by simultaneously using a metal salt of phenylphosphonic acid as a low-cost metal salt of basic zinc cyanurate particles and phenylphosphonic acid, it is possible to simultaneously increase the crystallization rate and crystallization temperature of the resin. The effect is the result of the so-called cost reduction. The metal salt of phenylphosphonic acid, for example, zinc phenylphosphonate, lithium phenylphosphonate, sodium phenylphosphonate, potassium phenylphosphonate, calcium phenylphosphonate, magnesium phenylphosphonate, manganese phenylphosphonate, etc.-13-201219406 The content ratio of each component of the nucleating agent for the resin of the basic zinc cyanurate particles and the metal salt of phenylphosphonic acid is not particularly limited. For example, if the cyanuric acid is 20 to 40% by mass, the phenylphosphonic acid is used. It can be 1 〇 to 30% by mass. When the cyanuric acid component of the crystal nucleating agent composition is less than 20% by mass, the content of the basic zinc cyanurate is decreased, and the content of the zinc phthalate is increased, except that the phenylphosphonic acid is high in price. It is to increase the concentration of these above phenylphosphonic acids, and the performance of the nucleating agent cannot be improved. On the other hand, when the concentration of the cyanuric acid component of the crystal nucleating agent composition is more than 4% by mass, the content of the basic zinc cyanurate increases, and the content of the zinc phenylphosphonate becomes too small, and the crystal nucleus The performance of the agent will be reduced, so it is not suitable. Further, the cyanuric acid is quantified by the molecular formula C3N3 03H3 and can be quantified by the amount of nitrogen measured by CHN elemental analysis. The phenylphosphonic acid is represented by the molecular formula C6H7〇3P and can be quantified by the amount of phosphorus measured by fluorescent X-ray analysis. Further, the zinc/phenyl phenylphosphonate ratio of zinc and zinc phenylphosphonate contained in the nucleating agent for the resin containing the basic zinc cyanurate particles and the metal salt of phenylphosphonic acid is preferably 1 in quality. Big but less than 4. Even if the concentration of phenylphosphonic acid is 1 or less and the price is increased, the performance of the crystal nucleating agent cannot be improved, and when it is 4 or more, the performance of the crystal nucleating agent tends to decrease. Niobium, a crystal nucleating agent for a resin, may contain magnesium hydroxide, magnesium oxide, or the like. The method for producing a nucleating agent for a resin containing the basic zinc cyanuric acid particles of the present invention and the metal salt of phenylphosphonic acid is not particularly limited. For example, the basic zinc cyanurate particles can be used. It is produced by mixing a metal salt of phenylphosphonic acid with a mixer or the like. In addition, the tree containing basic zinc cyanurate particles and phenylphosphonic acid metal salt -14-201219406 lithium oxygen tree lithium oxygen to adjust, reverse, such as the table water magnesium solution. 3 pH nucleating agent for milk fat, or by using an aqueous solution of a metal salt of phenylphosphonic acid such as magnesium phenylphosphonate, phenylphosphonic acid, sodium phenylphosphonate or potassium phenylphosphonate as raw materials, zinc and alkali At least one selected from the group consisting of zinc carbonate and cyanuric acid are produced by heating or the like as needed to cause a reaction. Further, a nucleating agent for a lipid containing basic zinc cyanurate particles and a metal salt of phenylphosphonic acid may also be used as a raw material of magnesium phenylphosphonate, phenylphosphonic acid, sodium phenylphosphonate or phenylphosphonic acid. An aqueous solution of a metal salt of phenylphosphonic acid such as potassium, at least one selected from zinc and alkaline zinc carbonate, cyanuric acid and water, and the concentration of cyanuric acid is 0 with respect to water. 1~10. In the case of 0% by mass, the mixed slurry is dispersed in a temperature range of 5 to 5 5 °C using a dispersion type stirring blade or a dispersion medium to be strongly agitated and dispersed, and each raw material is produced. The slurry obtained by the production method can be dried by U 0 ° C to produce a metal containing fine basic zinc cyanurate, zinc phenylphosphonate and a metal salt of the above phenylphosphonic acid constituting the raw material. A nucleating agent for a resin of a hydroxide (for example, magnesium hydroxide or the like). The resin nucleating agent has a specific area of 15 to 100 m 2 /g, preferably 20 to 100 m 2 /g. The following is a detailed description of this method. First, an aqueous solution of a metal salt of phenylphosphonic acid as a raw material is adjusted by dissolving a carbonate or a metal hydroxide with phenylphosphonic acid. For example, magnesium carbonate or magnesium hydroxide and phenylphosphonic acid can be dissolved in water in a ratio of magnesium to phenylphosphonic acid in a molar ratio of, for example, 〇·3 to 〇·6. And modulation. Here, if the magnesium/phenylphosphonic acid (mole ratio) is not full, the pH at which the mixed slurry is produced becomes 7 or less. Then, when the resin nucleating agent obtained by drying the slurry of 7 or less is kneaded in the poly-15-201219406 acid resin, since one part of the polylactic acid is dissolved, the crystallization rate is high and crystallization is performed. The temperature is high, so that the performance of the so-called crystal nucleating agent is small, and the resulting zinc phenylphosphonate becomes coarse particles, and the performance of the nucleating agent of the polylactic acid resin is lowered. Among them, the dissolved portion of the polylactic acid resin is solidified as it is, and the portion becomes brittle and the mechanical properties are lowered. Also, if the magnesium/phenylphosphonic acid (Morby) is more than 0. At 6 o'clock, magnesium phenylphosphonate particles will precipitate. Therefore, magnesium / phenylphosphonic acid (Morby), to 〇 · 3 ~ 0. Within the scope of 6 is appropriate. Next, at least one selected from the group consisting of zinc oxide and basic zinc carbonate, cyanuric acid and water are used to make the concentration of cyanuric acid 0. 1~10. 0% by mass, preferably 1. 0~5. The addition is carried out in an amount of 0% by mass, and then an aqueous solution of the above metal salt of phenylphosphonic acid is mixed. For example, when an aqueous solution of a metal salt of phenylphosphonic acid is an aqueous solution of magnesium phenylphosphonate, the concentration of the aqueous solution of magnesium phenylphosphonate is preferably 1. 0~3. The blending was adjusted to 0% by mass to adjust the mixed slurry. When the concentration of cyanuric acid in water is higher than 10% by mass, the viscosity of the slurry becomes high and becomes a paste, and when the dispersion type stirring blade in the subsequent stage or the wet dispersion using a dispersion medium is used, It will become difficult to stir and disperse strongly. On the other hand, the concentration of cyanuric acid relative to water is more than 0. When 1% by mass is low, productivity is poor, so it is not suitable. Further, the ratio of at least one selected from zinc oxide and basic zinc carbonate to the cyanuric acid is not particularly limited, and the total amount of zinc oxide in terms of molar ratio, zinc oxide and basic zinc carbonate/cyanide is The acid is preferably 1. 〇~5. 0, more preferably 2. 5 ~ 3. 0. The total amount of zinc oxide converted / cyanuric acid is more than 5. 0 is high, or is 1. When 0 is low, since zinc oxide, alkaline zinc carbonate or cyanuric acid which does not contribute to the reaction tends to remain in a large amount. In addition, the blending ratio of phenylphosphonic acid contained in the metal salt of phenylphosphonic acid is not particularly limited, and the concentration of phenylphosphonic acid contained in the metal salt of phenylphosphonic acid is preferably 1 . 5~3. 0% by mass. Because even if it is more than 3. When the mass % is high, the performance of the nucleating agent of the polylactic acid resin cannot be greatly improved, and if it is lower than 1.5% by mass, the performance of the nucleating agent of the polylactic acid resin is lowered. Next, the obtained mixed slurry is stirred and dispersed in a range of, for example, a temperature range of 5 to 55 t by a dispersion type stirring blade or a wet dispersion using a dispersion medium. Therefore, a metal salt of zinc oxide or basic zinc carbonate and phenylphosphonic acid is obtained while reacting at least one selected from zinc oxide and basic zinc carbonate with cyanuric acid to form basic zinc cyanurate. A reaction is produced to form zinc phenylphosphonate.尙, strongly stirred and dispersed, if wet dispersion is carried out at a temperature higher than 55 ° C, the resulting basic zinc cyanurate and zinc phenylphosphonate will become coarse particles, due to the nucleus of polylactic acid resin The performance of the agent will be lowered, so it is preferably carried out at less than 55 t. Further, when it is produced by wet dispersion using a dispersion medium, it can be produced by using a transmission electron microscope to observe that the major axis of the secondary particles is 100 to 1 200 nm and the short axis is 10 to 100 nm by laser. A crystal nucleating agent for a resin having a mean particle diameter D5G of 80 to 900 nm and a zinc phenylphosphonate having a major axis and a minor axis of 50 to 800 nm as measured by a diffraction method. a crystal nucleating agent composition containing a metal hydroxide (for example, magnesium hydroxide) of a basic zinc cyanide, zinc phenylphosphonate or a metal salt of a phenylphosphonic acid constituting a raw material thus obtained The slurry containing the same is used as the nucleating agent for the resin as it is, and the slurry can be dried, and the powder can be made into a fine powder using a bar or a jet honing machine. Used as a crystal nucleating agent for resins. The size of the nucleating agent for a resin is not particularly limited, and a fine nucleating agent for a resin having high transparency can be obtained by using fine particles having a specific surface area of 20 to 100 m 2 /g. Then, the resin composition of the present invention is an alkali cyanuric acid particle and a resin containing the above-mentioned resin nucleating agent, or a basic zinc cyanurate particle or a phenylphosphine containing the above-mentioned resin nucleating agent. Acid metal salts and resins. As the resin, for example, polylactic acid or a polyolefin resin is exemplified. Further, two or more kinds of resins can be used. As the polylactic acid resin, for example, a homopolymer or a copolymer of lactic acid, or a blend polymer in which a homopolymer or a copolymer of such lactic acid is used as a main component and a mixture of other resins is mixed. Other resins to be mixed include, for example, biodegradable resins other than polylactic acid, general synthetic resins, and general-purpose synthetic industrial plastics. When the polylactic acid resin is a copolymer, the arrangement pattern may be any random copolymer, alternating copolymer, block copolymer, or graft copolymer. Further, a polylactic acid resin can be used as a polylactic acid resin by crosslinking the above polylactic acid resin with a crosslinking agent by heat, light, radiation or the like. Of course, two or more kinds of these polylactic acid resins can be used. Here, the molecular weight of the polylactic acid is not particularly limited, and for example, the number average molecular weight is 10, 〇〇〇 500, and 〇〇〇. Further, the method for producing the polylactic acid resin is not particularly limited. For example, it can be produced by subjecting lactide lactide to ring-opening polymerization or direct condensing polymerization of D, L, and racemic lactic acid. Further, the polyolefin resin may, for example, be a polyethylene resin, a polypropylene-18-201219406 resin, or a polyamide resin. Among them, examples of the polypropylene resin include polypropylene, an ethylene-propylene copolymer, and the like, or a polypropylene which is denatured with an unsaturated residual acid or the acid anhydride. For the polypropylene which is denatured with an unsaturated carboxylic acid or the acid anhydride, for example, a polypropylene such as a propylene single polymer or an ethylene-propylene copolymer, or acrylic acid, methacrylic acid, maleic acid 'iconic acid, An unsaturated carboxylic acid such as fumaric acid, maleic anhydride or itaconic acid anhydride or a copolymer of the acid anhydride or a graft copolymer or the like. Particularly preferred is a copolymer of propylene with acrylic acid or maleic anhydride, or a graft copolymer. Of course, two or more kinds of these polyolefin resins can be used. The molecular weight of the polyolefin resin is not particularly limited, and for example, the number average molecular weight is about 10,00 to 500,000. The ratio of the ratio of the basic zinc cyanurate particles to the resin is not particularly limited. When the polylactic acid resin is used as the resin, it is preferred to make the basic zinc cyanurate particles with respect to 1 part by mass of the polylactic acid resin. Become a beggar. 〇1~1〇. 〇 Quality. Further, when the polyolefin resin is used as the resin, it is preferred to make the basic zinc cyanurate particles into 0 parts by mass based on 10 parts by mass of the polyolefin resin. 01 to 10_0 parts by mass. The amount of the basic zinc cyanurate particles is less than 0% relative to 100 parts by mass of the resin. In the case of 01 parts by mass, the effect of increasing the crystallization rate of the resin or the crystallization temperature may be inconspicuous. Further, if the amount of the basic zinc cyanurate particles is 10. When the mass portion is 0, the specific gravity of the resin composition may become too heavy. In the same manner, when a crystal nucleating agent for a resin containing a basic metal salt of zinc cyanurate particles and phenylphosphonic acid is used, the blending ratio is not particularly limited, and when a polylactic acid resin is used as the resin, the polymer is used. The lactic acid resin 1 〇〇 -19 - 201219406 parts 'preferably, the nucleating agent for the resin containing the basic metal cyanurate particles and the metal salt of phenylphosphonic acid becomes 0 · 0 1~1 0. 0 parts by mass. In addition, when a polyolefin resin is used, it is preferable to use a crystal nucleating agent for a resin containing a basic metal salt of zinc cyanurate particles and phenylphosphonic acid, as compared with 100 parts by mass of the polyolefin resin. Become 0·01~10. 0 parts by mass. The resin composition 'of the present invention' may contain an inorganic chelating agent. As the inorganic chelating agent 'for example, for example, glass fiber, carbon fiber, talc, mica, vermiculite, kaolin, clay, ash, glass beads, glass flakes, potassium titanate, calcium carbonate, magnesium sulfate, titanium oxide, etc. . The shape of these inorganic chelating agents can be arbitrarily fibrous, granular, plate-like, acicular, spherical, or powder. The blending amount of the inorganic chelating agent can be, for example, 300 parts by mass or less based on 100 parts by mass of the resin. Further, the resin composition of the present invention. It can contain a flame retardant. Examples of the flame retardant include, for example, a halogen-based flame retardant such as bromine or chlorine, an antimony-based flame retardant such as antimony trioxide or antimony pentoxide, aluminum hydroxide or magnesium hydroxide, or a polyoxon compound. Inorganic flame retardants, red phosphorus, phosphates, ammonium polyphosphate, phosphazene and other phosphorus-based flame retardants, melamine, melam, melem, melamine, trimer Melamine cyanate, melamine phosphate, melamine pyrophosphate, melamine polyphosphate, melamine polyphosphate, melam. A melamine-based flame retardant such as melemamine double salt, alkyl phosphinate melamine, phenylphosphonic acid melamine melamine sulfate, meyl sulfamate, or a fluororesin such as PTFE. The blending amount of the flame retardant can be, for example, 200 parts by mass or less based on 100 parts by mass of the resin. Further, the resin composition may contain, in addition to the above components, a heat stabilizer -20-201219406 agent, a light stabilizer, an ultraviolet absorber, an antioxidant, a rinsing improver, an antistatic agent, a pigment, a colorant, a release agent, and a lubricant. Agents, plasticizers, compatibilizers, foaming agents, perfumes, antibacterial and antifungal agents, decane, titanium, aluminum, etc., other coupling agents, other various chelating agents, or zinc cyanurate particles A crystal nucleating agent or the like, which is generally used in the production of a general synthetic resin. The method for producing a resin composition using a resin and a basic metal salt of zinc cyanurate or basic zinc cyanurate and phenylphosphonic acid, and various additives to be added as needed, is not particularly limited and can be used. It is produced in the same manner as the resin composition containing a conventional crystal nucleating agent. For example, the resin and the basic zinc cyanurate, or the metal salt of basic zinc cyanurate and phenylphosphonic acid, and the additives added as needed are mixed in various mixers, using uniaxial or two A shaft extruder or the like can be produced by kneading at a temperature of, for example, about 150 to 220 °C. Further, a precursor mixture containing a high concentration of basic zinc cyanurate or a metal salt of basic zinc cyanurate and phenylphosphonic acid, and an additive added as needed, is added to the resin. The method is also possible. In addition, a method of adding a basic zinc cyanurate or a basic metal salt of zinc cyanurate and phenylphosphonic acid in the polymerization stage of the resin, such as the resin composition of the present invention, may be used. Various molded articles can be easily produced by a general molding method such as injection molding, air blowing molding, vacuum molding, or compression molding. The molded article can be used, for example, as a packaging material for a container or a film, a clothing material, a fiber material, an electric or electronic product. Next, 'the resin composition of the present invention, because of the nucleating agent-containing basic-21 - 201219406 zinc cyanurate particles, or the basic zinc cyanurate particles and the metal salt of phenylphosphonic acid, the crystallization of the resin High speed. Therefore, the degree of crystallization of the resin becomes high, and a molded article having good heat resistance can be obtained. Further, by increasing the crystallization rate, the time required for crystallization is shortened, and the molded product of the resin can be produced in a short time. Then, by crystallization in a short time, the spherulite size becomes small, and a molded article having excellent transparency and high rigidity can be obtained. In addition, by containing basic zinc cyanurate particles, or basic zinc cyanurate particles and a metal salt of phenylphosphonic acid, the crystallization temperature of the resin is also increased, and the resin is used for injection molding or the like. When the mold is molded, since the cooling temperature of the mold can be increased, the molded product of the resin can be produced in a short time. [Embodiment] [Examples] Hereinafter, the present invention will be further described in detail based on examples and comparative examples, but the present invention is not limited to the examples. (Measuring apparatus) The analysis of the examples and comparative examples was carried out using the following apparatus and conditions. Penetrating electron microscope observation: JEM-1010 (manufactured by JEOL Ltd.) applied a voltage of 100 kV. Laser diffraction method for particle diameter measurement: S A L D - 7000 type (manufactured by Shimadzu Corporation), and 1 g of the sample was diluted with pure water for 20,000 times. Specific surface area measurement: Nisorbent surface area measuring device Monosorb machine (-22-201219406 yuasa-ionics (manufactured by the company). Gravimetric analysis: After about 2 g of the sample was placed in a precision scale of a magnetic system, the solid fraction was calculated by mass after drying at 1 1 〇 °C. X-ray powder diffraction analysis: powder X-ray diffraction device RINT Ultima type (manufactured by Rigaku). Elemental analysis: Fully automatic elemental analysis device CHNS/OAnalyzer 2400 (manufactured by PerkinElmer). (Synthesis Example 1) In a batch grinder container in which the inner wall of the volume of 1 liter is an urethane resin, 1140 g of pulverized beads of Φ 1 mm and 300 g of pure water were placed. The sander container was cooled while being cooled at -5 ° C, and was rotated at 500 rpm using a stir plate, and a cyanuric acid powder (manufactured by Nissan Chemical Industries Co., Ltd.) was charged. 9g. The sander container was continuously cooled at -5 °C while being rotated at 500 rpm using a stir plate, and zinc oxide powder (two types of zinc oxide manufactured by Nippon Chemical Co., Ltd.) was introduced. 3g. The molar ratio of zinc oxide/cyanuric acid is 2. 5, the concentration of cyanuric acid relative to water is 2. 0% by mass. After the zinc oxide powder was charged, the sand mill container was cooled at -5 °C for 12 hours, and was rotated at 500 rPm using a stirring disk to be dispersed. The slurry temperature at this time was 9 °C. So 'get PH7. 1. Conductivity 84 y S/cm, 110. (: The solid shape when dry is divided into 4. 8 mass% of white slurry 3 10 g. The obtained white pulp of 1 1 〇 ° C dry powder was subjected to elemental analysis, and the result was carbon 10. 37% by mass, hydrogen 1. 35 mass%, nitrogen 12. 05 quality -23- 201219406 %, oxygen 2 8. 20% by mass. Further, the dried powder at 110 ° C was thermally decomposed into zinc oxide at 100 ° C, and the mass was measured to obtain an effective component amount of Zn of 11 〇 ° c dry powder. 03% by mass. Further, x-ray powder diffraction analysis was performed on the dried powder at 110 ° C. As a result, as shown in Fig. 1, no diffraction peak of cyanuric acid and zinc oxide belonging to the raw material was observed, and alkaline trimerization was observed. A diffraction peak of zinc cyanate. From this result, it can be determined that the dry powder of ll〇°C is Zn5(C3N303)2(0H)3. 3H20 alkaline zinc silicate. The fine particles contained in the obtained white slurry were observed by a transmission electron microscope with a long axis of 1 〇〇 to 200 nm and a short axis of 1 〇 to I5 nm, which were measured by the laser diffraction method. The particle diameter D5 〇 is 10 〇 3 nm, and the basic surface area Sw after drying at 70 ° C is 59 m 2 /g of basic zinc cyanurate. The results are shown in Table 1. Further, a photograph observed by a transmission electron microscope is shown in Fig. 2. (Synthesis Example 2) In a batch-type sand mill container in which the inner wall of the volume of 1 liter is a urethane resin, 114 〇g of φ 1 mm of stabilized cone pulverized beads and 3 OOg of pure water were placed. The sander container was cooled while being cooled at -5 °C, and was rotated at 1,500 rPm using a stir plate, and 5 to 9 g of cyanuric acid powder (manufactured by Nissan Chemical Industries Co., Ltd.) was charged. The sander container was continuously cooled while being cooled at -5 °C. While rotating at 1500 rpm using a stir plate, zinc oxide powder (two types of zinc oxide made by skirt chemical) was introduced. 3g. The molar ratio of zinc oxide/cyanuric acid is 2. 5, the concentration of cyanuric acid relative to water is 2. 0% by mass. After the zinc oxide powder -24-201219406 was charged, the sander container was cooled by a condenser of 〇 °c for 8 hours, and rotated by using a stir plate at 1 500 rpm to be dispersed. The slurry temperature at this time was 16 °C. So 'get pH7. 1. The conductivity is 1 〇9 kernel S/cm, and the solid shape at 110 °C is 4. 8 mass% of a white slurry of 311 g. Further, X-ray powder diffraction analysis was carried out on the dried powder of the obtained white slurry at 110 ° C, and the same diffraction pattern as in Synthesis Example 1 was obtained. When the fine particles contained in the obtained white slurry were observed by a transmission electron microscope, the long axis was 1 〇〇 to 300 nm, and the short axis was 10 to 20 nm. The average of the particle diameters by laser diffraction was measured. The particle diameter D5 ((155 nm, basic dry surface area Sw after drying at 70 ° C is 49 m 2 /g of basic zinc cyanurate. The results are shown in Table 1 (Synthesis Example 3). The inner wall of the volume of 1 liter is an amine. In a batch-type sand mill container of ethyl formate resin, 1 140 g of pulverized beads of Φ 1 mm of condensed chrome and 300 g of pure water were placed, and the container of the sand mill was cooled at a condenser side of -5 ° C. - While using a stir plate to rotate at 200 rpm, and putting cyanuric acid powder (manufactured by Nissan Chemical Industry Co., Ltd.). 9g. The sander container was continuously cooled while being cooled at -5 °C, and rotated at 2000 rpm using a stir plate, and zinc oxide powder (two types of zinc oxide manufactured by Nippon Chemical Co., Ltd.) was introduced. 3g. The molar ratio of zinc oxide/cyanuric acid is 2. 5, the concentration of cyanuric acid relative to water is 2. 〇% by mass. After the zinc oxide powder was charged, the sand mill container was cooled with a condenser of -5 t for 8 hours, and the mixture was rotated at 2000 rpm using a stirring disk to disperse. At this time, the temperature of the slurry -25-201219406 was 23 °C. Therefore, 305 g of a white slurry having a solid content of ΡΗ7·0, a conductivity of 120 S/cm, and a solid content of 4.4°% by weight was obtained. Further, X-ray powder diffraction analysis was carried out on the dried powder of 110 ° C of the obtained white slurry, and as a result, the same diffraction pattern as in Synthesis Example 1 was obtained. When the fine particles contained in the obtained white slurry were observed by a transmission electron microscope, the long axis was 100 to 400 nm, and the short axis was 20 to 30 nm. The average particle diameter D5G measured by the laser diffraction method. It is 175 nm, and the specific surface area Sw after drying at 70 ° C is 32 m 2 /g of basic zinc cyanurate. The results are shown in Table 1. Further, a photograph observed by a transmission electron microscope is shown in Fig. 3. (Synthesis Example 4) In a batch-type sand mill container in which the inner wall of the volume of 1 liter is a urethane resin, 114 g of zirconia pulverized beads of Φ 1 mm and 290 g of pure water were placed. The sander container was cooled while being tap water at 20 °C, and rotated at 1 500 rpm using a stir plate, and a cyanuric acid powder (manufactured by Nissan Chemical Industries Co., Ltd.) was introduced. 2g. The sander container was continuously cooled with tap water of 20 ° C, and the mixture was rotated at 150 rpm using a stir plate, and zinc oxide powder (two types of zinc oxide manufactured by Nippon Chemical Co., Ltd.) was introduced. 5g. The molar ratio of zinc oxide/cyanuric acid is 2. 5, the concentration of cyanuric acid relative to water is 3. 2% by mass. After the zinc oxide powder was charged, the sand mill container was cooled with tap water at 20 ° C for 10 hours, and then rotated at 1,500 rpm using a stir plate to disperse. The slurry temperature at this time was 40 °C. Therefore, the solid form when ρΗ6·8, conductivity 148yS/cm, ll〇 t is dry is obtained. 5 mass% of white pulp 300 g. Further, the dried powder of 1 i 〇 °C of the obtained white slurry was subjected to x-ray powder diffraction analysis on -26 to 201219406, and as a result, the same diffraction pattern as in Synthesis Example 1 was obtained. When the fine particles contained in the obtained white slurry were observed by a transmission electron microscope, the long axis was 100 to 300 nm, the short axis was 20 to 30 nm, and the average particle diameter D5G measured by the laser diffraction method was used. It is 188 nm, and the specific surface area Sw after drying at 70 ° C is 26 mz / g of basic zinc cyanurate. (Synthesis Example 5) In a batch-type sand mill container in which the inner wall of the volume of 1 liter is a urethane resin, a pulverized bead of Φ 1 mm of stabilized zirconium 1 I 40 g and pure water of 290 g were placed. Rotating at 150 rpm and putting in cyanuric acid powder (manufactured by Nissan Chemical Industry Co., Ltd.). 9g. The stirring disc was continuously rotated at 1500 rpm, and zinc oxide powder (two kinds of zinc oxide made by 堺Chemical Co., Ltd.) was introduced. 3g. The molar ratio of zinc oxide/cyanuric acid is 25, and the concentration of cyanuric acid relative to water is 2_0% by mass. After the zinc oxide powder was charged, the stir plate was rotated at 1,500 rpm for 5 hours to be dispersed. The slurry temperature at this time was 50 °C. Therefore, PH8, 2, conductivity 176 / z S / cm, 110C dry solidification is divided into 4. 8% by mass of white hair 3 0 0 g. Further, the results of the X-ray powder diffraction analysis of the dried white powder of 1 1 of the obtained white prizes were the same as those of Synthesis Example 1. When the fine particles contained in the obtained white slurry were observed by a transmission electron microscope, the long axis was 100 to 200 nm, and the short axis was 20 to 4 nm. The average particle diameter by the laser diffraction method was measured. The diameter is 623 nm, and 7 (the specific surface area Sw after rc drying is 25 m 2 /g of basic cyanuric acid. The results are shown in Table 1 of -27-201219406. (Synthesis Example 6) The inner wall of the volume of 1 liter is In a batch-type sand mill container of urethane resin, 1140 g of pulverized beads of zirconia Φ 1 mm and 298 g of pure water were placed, and the sand mill vessel was cooled by a condenser at 10 ° C, Rotating at 2000 rpm using a stir plate, and putting in a cyanuric acid powder (manufactured by Nissan Chemical Industries Co., Ltd.). 3g. Continue to cool the sander container to the condenser of l〇°C, and use a stir plate to rotate at 1 500rptn, and put in alkaline zinc carbonate powder (zinc oxide composition 74. 8% by mass, 堺Chemical (share) system) 9. 0g. The amount of zinc oxide converted / the cyan ratio of cyanuric acid is 2. 5, the concentration of cyanuric acid relative to water is 1. 4% by mass. After the zinc oxide powder was charged, the sand mill container was cooled by a condenser at 10 ° C for 8 hours, and the mixture was rotated at 1,500 rpm using a stirring disk to disperse. The slurry temperature at this time was 30 °C. Therefore, a pH of 6. 3. Conductivity is 556yS/cm and viscosity is 198mPa. s, solid state at 110 ° C when dry is divided into 3. 5 mass% of white pulp 3 10 g. Further, X-ray powder diffraction analysis was carried out on the dried powder of 1 〇 °C of the obtained white slurry, and as a result, the same diffraction pattern as in Synthesis Example 1 was obtained. When the fine particles contained in the obtained white slurry were observed by a transmission electron microscope, the long axis was 1 〇〇 300 300 nm, and the short axis was 20 ～ 40 nm 'the average of the particle diameters measured by the laser diffraction method. The particle diameter Dn was 303 nm', and the specific surface area Sw after drying at 70 ° C was 30 m 2 /g of basic zinc cyanurate. The results are shown in Table 1. -28- 201219406 (Synthesis Example 7) 24 kg of pure water and zinc oxide powder (two kinds of zinc oxide made by 堺Chemical Co., Ltd.) were 1. 88 kg was placed in a mixing tank having a volume of 200 liters, and the mixture was stirred and mixed by dispersion, and then the concentration of zinc oxide was adjusted to 7. 69% by mass of slurry 2 6 kg. Next, 66 kg of pulverized bead pellets of Φ 1 mm was placed in an effective volume of 10. The inner wall of 66 liters was a horizontal bead honing machine (Ashizawa Finetech bead mill PM25TEX-H) of urethane resin. 144 kg of pure water was placed in a circulation tank equipped with a condenser, and the disk of the bead mill was rotated at a peripheral speed of 10 m/sec, and pure water was supplied to the bead mill at a supply speed of 5 kg/min. While circulating pure water. After the start of the cycle, the cyanuric acid powder (manufactured by Nissan Chemical Industries Co., Ltd.) was introduced. 19kg. After the cyanuric acid powder was charged, the temperature of the circulating slurry was adjusted to 32 ° C with a condenser, and the conversion of zinc oxide was 7. 69% by mass of zinc oxide slurry 24. 5 kg, divided into 5 times, took 1 minute to add. The molar ratio of zinc oxide/cyanuric acid is 2. 5. The concentration of cyanuric acid relative to water is 〇. 7% by mass. After the addition of the zinc oxide slurry, the disk of the bead mill was also rotated at a peripheral speed of 1 〇 m/sec, and the slurry was circulated at a supply rate of 5 kg/min for 15 hours to be dispersed. Further, the temperature of the circulating slurry was adjusted to 32 °C by a condenser. Therefore, get PH6. 8, conductivity 67 / / S / cm, viscosity 51mPa. s, ll〇t when dry, the solid shape is divided into 1. 8 mass% of white pulp 166 kg. The dried powder of 11 〇 ° C of the obtained white slurry was subjected to X-ray powder diffraction analysis, and as a result, the same diffraction pattern as in Synthesis Example 1 was obtained. The microparticles contained in the obtained white slurry were observed by a transmission electron microscope.
S -29- 201219406 軸爲100〜600nm、短軸爲25〜50nm，藉由雷射繞射法 徑測定之平均粒子徑D 5 〇爲3 1 Onm，7 0 °C乾燥後之比 積Sw爲5 1m2/g之鹼性三聚氰酸鋅。結果如表1所示 ，穿透型電子顯微鏡所觀察之照片如圖4所示。 (合成例8) 在容積1升之內壁爲胺甲酸乙酯樹脂之分批式砂 容器中，置入Φ 1mm之安定化锆製粉碎珠粒i140g 水290g，將攪拌盤以1500rpm進行回轉，並投入三 酸粉末（日產化學工業（股）製）5.9g。持續將攪拌 1 5 00rPm進行回轉，並投入氧化鋅粉末（堺化學（股 的2種氧化鋅）1 1.2g。氧化鋅/三聚氰酸之莫耳比爲 ，相對於水之三聚氰酸濃度爲2.0質量％。投入氧化 末後，以5小時將攪拌盤以1 5 00rpm進行回轉使分散 時的漿料溫度爲23°C。因此，得到PH7.8、導電度 S/cm' 110°C乾燥時之固形分爲 5.6質量％之白色 3 00g。對於所得到白色漿料之1 10°C乾燥粉進行X射 末繞射分析，結果與合成例1爲同樣之繞射圖型。所 的白色漿料中所含有的微粒子，以穿透型電子顯微鏡 時，係長軸爲100〜3 00nm、短軸爲15〜20nm，藉由雷 射法粒子徑測定之平均粒子徑D5G爲152nm，70°C乾 之比表面積Sw爲40m2/g之鹼性三聚氰酸鋅。結果如 所示。 粒子 表面 。又 磨機 與純 聚氰 盤以 )製 3.0 鋅粉 。此 98 // 駿料 線粉 得到 觀察 射繞 燥後 表1 -30· 201219406 (合成例9) 將已置入有純水900g之1升燒杯，放置於附有磁攪 拌器之加熱板上’以攪拌子一邊進行攪拌’ 一邊投入三聚 氰酸粉末（日產化學工業（股）製）18.9g。接著，投入 氧化鋅粉末（堺化學（股）製的2種氧化鋅）30.0g後， 使用攪拌子將混合漿料—邊攪拌，一邊使用加熱板加熱至 煮沸爲止。氧化鋅/三聚氰酸之莫耳比爲2.5,相對於水之 三聚氰酸濃度爲2.1質量％。於100 °C煮沸下攪袢8小時 後，得到PH7.1、導電度46/zS/cm、黏度500mPa. s、以 11(TC乾燥時之固形分爲6.8質量％之白色漿料716g。對 於所得到白色漿料之1 1 〇°C乾燥粉進行X射線粉末繞射分 析，結果與合成例1爲同樣之繞射圖型。所得到的白色漿 料中所含有的微粒子，以穿透型電子顯微鏡觀察時，係長 軸爲2000~20000nm、短軸爲200~500nm，藉由雷射繞射 法粒子徑測定之平均粒子徑D5Q爲2620nm，70°C乾燥後 之比表面積Sw爲5m2/g之鹼性三聚氰酸鋅。結果如表1 所示。又，穿透型電子顯微鏡所觀察之照片如圖5所示。 (合成例1 〇 ) 使用有效容積10.66升之內壁爲胺甲酸乙酯樹脂之橫 式珠粒硏磨機（Ashizawa Finetech (股）製 system zeta LMZ25 )取代珠磨機，以與合成例7之原料比爲相同地進 行同樣之操作，結果得到PH7.9、導電度2〇6#S/cm、黏 度76mPa . s、1 10。(：乾燥時之固形分爲1.8質量％之白色 -31 - 201219406 绩料168kg。對於所得到白色漿料之U(rc乾燥粉進行χ 射線粉末繞射分析’結果與合成例1爲同樣之繞射圖型。 所得到的白色獎料中所含有的微粒子，以穿透型電子顯微 鏡觀察時’係長軸爲100〜800nm、短軸爲10〜60nm，藉由 雷射繞射法粒子徑測定之平均粒子徑D5G爲3 97nm, 70。(： 乾燥後之比表面積Sw爲54m2/g之鹼性三聚氰酸鋅。結果 如表】所示。 (實施例1 ) 將合成例9所得到的鹼性三聚氰酸鋅之no乞乾燥粉 40mg’及聚乳酸樹脂（NW3001D、數平均分子量72,000 、融點164°C、natureworks製）4.0g置入於已加熱至185 °C之混練機（LABO PLASTOMILL東洋.精機（股）製）中 5分鐘，以50rpm進行混練而製造樹脂組成物。冷卻後， 將樹脂組成物取出，以鐵氟龍（登記商標）薄片與黃銅板 挾持，置於已加熱至上部185°C、下部185°C之熱壓製機 中，使薄膜之厚度成爲〇.4mm般地以0.5 kgf進行加壓， 製成薄膜。將此薄膜狀樣本切取成小片，以100°C/分鐘昇 溫至200°c並原樣地保持5分鐘，之後，以5°c /分鐘予以 冷卻來進行DSC測定（Seiko電子（股）製DSC-200 )。 由冷卻時所觀測到來自於聚乳酸之結晶化之發熱峰頂點來 測定結晶化溫度Tc。 又，將此薄膜狀樣本切取成小片’以i〇〇°c/分鐘昇溫 至20(TC並原樣地保持5分鐘，之後，以200°C /分鐘冷卻 -32- 201219406 至13(TC後，進行以130°C保持10分鐘之DSC Seiko電子（股）製DSC-200 )。由保持於130°C 測到來自於聚乳酸之結晶化之發熱峰頂點之時間， 結晶化速度。結果如表2所示。尙，在表2中，將 濃度，以作爲相對於樹脂1 00質量份之鹼性三聚氰 質量份予以記載。 又’將所得到薄膜之可見光透過率，使用色差 京電色TC- 1 8 00MK型），霧度以使用SPECTRAL METER (東京電色TC-H3DPK-MK型）所求得，結 見光透過率爲24%、霧度爲70。 (實施例2) 除了使用合成例7所得到的鹼性三聚氰酸鋅之 乾燥粉取代合成例9所得到的鹼性三聚氰酸鋅之！ 燥粉以外’與實施例1進行同樣之操作，測定聚乳 晶化溫度T c及結晶化速度。結果如表2所示。又 實施例1同樣之方法，求得所得到得薄膜之可見光 及霧度’結果爲可見光透過率爲52%、霧度爲50。 (實施例3 ) 除了使用合成例1 0所得到的鹼性三聚氰酸鋅 C乾燥粉取代合成例9所得到的鹼性三聚氰酸鋅之 乾燥粉以外，與實施例i進行同樣之操作，測定聚 結晶化溫度T c及結晶化速度。結果如表2所示。 測定（ 時所觀 來測定 成核劑 酸鋅之 計（東 HAZE 果之可 1 1 o°c 10〇C 乾 酸之結 ，以與 透過率 之110 1 1 o°c 乳酸之 又，以 -33- 201219406 與實施例I同樣之方法，求得所得到得薄膜之可見光透過 率及霧度，結果爲可見光透過率爲44%、霧度爲57» (實施例4 ) 除了將合成例1 〇所得到的鹼性三聚氰酸鋅之1 1 〇 乾燥粉之使用量設定爲8mg以外，與實施例3進行同樣 之操作，測定聚乳酸之結晶化溫度T c及結晶化速度。結 果如表2所示。又，以與實施例1同樣之方法，求得所得 到得薄膜之可見光透過率及霧度，結果爲可見光透過率爲 78%、霧度爲21。 (實施例5) 除了將合成例1 〇所得到的鹼性三聚氰酸鋅之1 1 0 °C 乾燥粉之使用量設定爲80mg以外，與實施例3進行同樣 之操作，測定聚乳酸之結晶化溫度T c及結晶化速度。結 果如表2所示。又，以與實施例1同樣之方法，求得所得 到得薄膜之可見光透過率及霧度，結果爲可見光透過率爲 22%、霧度爲80。 (實施例6) 將合成例9所得到的鹼性三聚氰酸鋅之Π 0°C乾燥粉 36mg，及聚丙嫌樹脂（novatec PP MA3、數平均分子量 111，000、融點 165°C、Japan Polychem (股）製）3.6g 置 入於已加熱至1 85°C之混練機（LABO PLASTOMILL東洋 -34- 201219406 精機（股）製）中5分鐘，以5 Orpm進行混練而製造樹脂 組成物。冷卻後，將樹脂組成物取出，以鐵氟龍薄片與黃 銅板挾持，置於已加熱至上部185°C、下部185°C之熱壓 製機中，使薄膜之厚度成爲0.4mm般地以〇.5kgf進行加 壓，製成薄膜。將此薄膜狀樣本切取成小片，以100 °C /分 鐘昇溫至20 0°C並原樣地保持5分鐘，之後，以5°C /分鐘 予以冷卻來進行DSC測定（Seiko電子（股）製DSC-200 )，由冷卻時所觀測到來自於聚丙烯之結晶化之發熱峰頂 點來測定結晶化溫度Tc。 又，將此薄膜狀樣本切取成小片，以1 00 °C /分鐘昇溫 至200°C並原樣地保持5分鐘，之後，以20(TC /分鐘冷卻 至130°C後，進行以130°C保持10分鐘之DSC測定（ Seiko電子（股）製DSC-200 )。由保持於13(TC時所觀 測到來自於聚丙烯之結晶化之發熱峰頂點之時間，來測定 結晶化速度。結果如表2所示。又，以與實施例1同樣之 方法’求得所得到得薄膜之可見光透過率及霧度，結果爲 可見光透過率爲3 0%、霧度爲85。 (實施例7) 除了使用合成例7所得到的鹼性三聚氰酸鋅之1 1 0 °C 乾燥粉取代合成例9所得到的鹼性三聚氰酸鋅之1 1 0 °C乾 燥粉以外’與實施例6進行同樣之操作，測定聚丙烯之結 晶化溫度T c及結晶化速度。結果如表2所示。又，以與 實施例1同樣之方法，求得所得到得薄膜之可見光透過率 -35- 201219406 及霧度，結果爲可見光透過率爲40%、霧度爲71。 (實施例8) 除了使用合成例10所得到的鹼性三聚氰酸鋅之110 °C乾燥粉取代合成例9所得到的鹼性三聚氰酸鋅之1 1 〇 °c 乾燥粉以外，與實施例6進行同樣之操作，測定聚丙烯之 結晶化溫度T c及結晶化速度。結果如表2所示。又，以 與實施例1同樣之方法，求得所得到得薄膜之可見光透過 率及霧度，結果爲可見光透過率爲38%、霧度爲78。 (比較例1 ) 除了未將鹼性三聚氰酸鋅添加於聚乳酸樹脂以外，與 實施例1進行同樣之操作。又，以與實施例1同樣之方法 ’求得所得到得薄膜之可見光透過率及霧度，結果爲可見 光透過率爲74%、霧度爲22。 (比較例2) 除了未將鹼性三聚氰酸鋅添加於聚丙烯樹脂以外，與 實施例6進行同樣之操作。又，以與實施例1同樣之方法 ’求得所得到得薄膜之可見光透過率及霧度，結果爲可見 光透過率爲57%、霧度爲31» 此結果如表2所示般，藉由添加鹼性三聚氰酸鋅，樹 脂之結晶化溫度及結晶化速度會變高，可知鹼性三聚氰酸 鋅能作爲樹脂之晶核劑使用。如此般地，因爲樹脂之結晶 -36- 201219406 化速度高，故樹脂之結晶化度會變高，可得到耐熱性良好 之成形物。又，藉由結晶化速度之變高，因結晶化所需要 之時間變短，可在短時間內製造樹脂之成形物。其中，藉 由在短時間內進行結晶化，球晶尺寸變小，可得到緻密、 即使未添加玻璃纖維等亦具有高剛性之透明性優異的成形 物。又，因爲樹脂之結晶化溫度亦高，由於可將模具之冷 卻溫度提高，故可在短時間內製造樹脂之成形物。 又，合成例7或合成例10之鹼性三聚氰酸鋅粒子， 因爲較合成例9之鹼性三聚氰酸鋅粒子爲顯著小之粒子， 故使用合成例7之鹼性三聚氰酸鋅粒子之實施例2及實施 例7、或使用合成例10之鹼性三聚氰酸鋅之實施例3及 實施例8，相較於使用合成例9之鹼性三聚氰酸鋅粒子之 實施例1及實施例6，可見光透過率高而霧度低，透明性 優異。 -37- 201219406 【1®S -29- 201219406 The axis is 100~600nm, the short axis is 25~50nm, the average particle diameter D 5 〇 measured by the laser diffraction method is 3 1 Onm, and the specific product Sw after drying at 70 °C is 5 1 m 2 /g of basic zinc cyanurate. The results are shown in Table 1, and the photographs observed by the transmission electron microscope are shown in Fig. 4. (Synthesis Example 8) In a batch type sand container in which the inner wall of the volume of 1 liter was an urethane resin, 290 g of pulverized bead granules i140 g of Φ 1 mm was placed, and the stirring disk was rotated at 1,500 rpm. In addition, 3.9 g of triacid powder (manufactured by Nissan Chemical Industries Co., Ltd.) was charged. Continue to stir 1 500 00 rPm for rotation, and put in zinc oxide powder (堺2 (2 kinds of zinc oxide) 1 1.2g. The molar ratio of zinc oxide / cyanuric acid is relative to water cyanuric acid The concentration was 2.0% by mass. After the oxidation was completed, the stirring disk was rotated at 1,500 rpm for 5 hours to set the slurry temperature at the time of dispersion to 23 ° C. Thus, pH 7.8 and conductivity S/cm '110 ° C were obtained. The solid shape at the time of drying was 5.6 mass% of white 30,000 g. The X-ray diffraction analysis of the dried powder of 10 ° C of the obtained white slurry was carried out, and the same diffraction pattern as in Synthesis Example 1 was obtained. The fine particles contained in the white slurry have a long axis of 100 to 300 nm and a short axis of 15 to 20 nm in a transmission electron microscope, and the average particle diameter D5G measured by the particle diameter of the laser is 152 nm, 70°. The basic dry surface area Sw of C is 40 m 2 /g of basic zinc cyanurate. The results are as shown. Particle surface, and mill and pure polycyanate disk to make 3.0 zinc powder. This 98 // Jun powder line is observed and shot after drying. Table 1 -30· 201219406 (Synthesis Example 9) Place a 1 liter beaker with 900 g of pure water and place it on a hot plate with a magnetic stirrer. 18.9 g of cyanuric acid powder (manufactured by Nissan Chemical Industries Co., Ltd.) was charged while stirring with a stirrer. Then, 30.0 g of zinc oxide powder (two types of zinc oxide manufactured by Seiko Chemical Co., Ltd.) was charged, and the mixed slurry was stirred with a stirrer, and heated to a boil using a hot plate. The molar ratio of zinc oxide/cyanuric acid was 2.5, and the concentration of cyanuric acid relative to water was 2.1% by mass. After stirring at 100 ° C for 8 hours, a pH of 7.1, a conductivity of 46/zS/cm, a viscosity of 500 mPa·s, and a white paste of 6.8 mass% of 6.8 mass% at a solid state of TC of 716 g were obtained. The dried powder of 1 〇 ° C obtained in the white slurry was subjected to X-ray powder diffraction analysis, and the same diffraction pattern as in Synthesis Example 1 was obtained. The fine particles contained in the obtained white slurry were penetrating type. When observed by electron microscopy, the long axis is 2000 to 20000 nm and the short axis is 200 to 500 nm. The average particle diameter D5Q measured by the laser diffraction method is 2620 nm, and the specific surface area Sw after drying at 70 ° C is 5 m 2 /g. The basic zinc cyanurate was obtained as shown in Table 1. Further, a photograph observed by a transmission electron microscope is shown in Fig. 5. (Synthesis Example 1 〇) Using an effective volume of 10.66 liters of the inner wall is a uric acid A horizontal bead honing machine (system zeta LMZ25 manufactured by Ashizawa Finetech Co., Ltd.) was used in place of the bead mill, and the same operation as in the raw material ratio of Synthesis Example 7 was carried out, and as a result, pH 7.9 and conductivity were obtained. Degree 2〇6#S/cm, viscosity 76mPa. s, 1 10. (: solid content when dry is 1.8% by mass White-31 - 201219406 Performance 168 kg. The result of the U (rc dry powder ray diffraction powder diffraction analysis) of the obtained white slurry was the same as that of Synthesis Example 1. The obtained white prize was used. The fine particles contained were observed by a transmission electron microscope with a long axis of 100 to 800 nm and a short axis of 10 to 60 nm, and the average particle diameter D5G measured by the laser diffraction method was 3 97 nm, 70. The dry specific surface area Sw was 54 m 2 /g of basic zinc cyanurate. The results are shown in the table. (Example 1) The alkaline dry zinc cyanide no 乞 dry powder obtained in Synthesis Example 9 40 mg' and polylactic acid resin (NW3001D, number average molecular weight 72,000, melting point 164 ° C, manufactured by Natureworks) 4.0 g were placed in a kneading machine (LABO PLASTOMILL Toyo Seiki Co., Ltd.) heated to 185 °C. In a minute, the resin composition was kneaded at 50 rpm. After cooling, the resin composition was taken out, and the Teflon (registered trademark) sheet was held with a brass plate, and placed in a heated upper portion at 185 ° C and a lower portion at 185 ° C. In the hot press, the thickness of the film is 〇.4mm 0.5 kgf was pressed to form a film. The film sample was cut into small pieces, heated to 200 ° C at 100 ° C / min and kept for 5 minutes as it was, and then cooled at 5 ° C / min for DSC. Measurement (Seiko Electronics Co., Ltd. DSC-200). The crystallization temperature Tc was measured from the apex of the exothermic peak from the crystallization of polylactic acid observed at the time of cooling. Further, the film-like sample was cut into small pieces 'heated to 20 (i and kept for 5 minutes as it was, and then cooled at 200 ° C / min -32 - 201219406 to 13 (after TC, DSC-200 (manufactured by DSC Seiko Electronics Co., Ltd.) which was kept at 130 ° C for 10 minutes, and the crystallization rate from the apex of the crystallization peak of the crystallization of polylactic acid was measured at 130 ° C. The results are shown in the table. 2, 尙, in Table 2, the concentration is described as a mass fraction of alkaline melamine relative to 100 parts by mass of the resin. Further, the visible light transmittance of the obtained film is used, and the color difference is used. TC- 1 8 00MK type), the haze was obtained by using SPECTRAL METER (Tokyo Electric Color TC-H3DPK-MK type), and the light transmittance was 24% and the haze was 70. (Example 2) The basic zinc cyanurate obtained in Synthesis Example 9 was replaced with the dry powder of basic zinc cyanurate obtained in Synthesis Example 7! The same procedure as in Example 1 was carried out except for the dry powder, and the polycrystallization temperature T c and the crystallization rate were measured. The results are shown in Table 2. Further, in the same manner as in Example 1, the visible light and haze of the obtained film were found to have a visible light transmittance of 52% and a haze of 50. (Example 3) The same procedure as in Example i was carried out except that the dry powder of basic zinc cyanurate C obtained in Synthesis Example 10 was used instead of the dry powder of basic zinc cyanurate obtained in Synthesis Example 9. The operation was carried out to measure the polycrystallization temperature T c and the crystallization rate. The results are shown in Table 2. Determination (when measuring the nucleating agent zinc acid (East HAZE can be 1 1 o ° c 10 〇 C dry acid knot, with the transmittance of 110 1 1 o ° c lactic acid again, to - 33-201219406 The visible light transmittance and haze of the obtained film were determined in the same manner as in Example I, and the visible light transmittance was 44%, and the haze was 57» (Example 4) except that Synthesis Example 1 The crystallization temperature T c and the crystallization rate of the polylactic acid were measured in the same manner as in Example 3 except that the amount of the dry powder of the obtained basic zinc cyanurate was set to 8 mg. Further, in the same manner as in Example 1, the visible light transmittance and haze of the obtained film were determined, and as a result, the visible light transmittance was 78% and the haze was 21. (Example 5) Synthesis Example 1 The same procedure as in Example 3 was carried out except that the amount of the dry powder used in the alkaline zinc cyanide obtained was set to 80 mg, and the crystallization temperature T c and crystal of the polylactic acid were measured. The results were as shown in Table 2. Further, in the same manner as in Example 1, the solution was obtained. The visible light transmittance and the haze of the film were as follows, and the visible light transmittance was 22%, and the haze was 80. (Example 6) The basic zinc cyanurate obtained in Synthesis Example 9 was dried at 0 ° C. Powder 36mg, and polypropylene propylene resin (novatec PP MA3, number average molecular weight 111,000, melting point 165 ° C, manufactured by Japan Polychem Co., Ltd.) 3.6g placed in a kneading machine that has been heated to 1 85 ° C (LABO PLASTOMILL) In the Toyo-34-201219406 Seiki Co., Ltd., the resin composition was kneaded at 5 O rpm for 5 minutes. After cooling, the resin composition was taken out, and the Teflon sheet and the brass plate were held and heated. The film was pressed into a film at a temperature of 0.45 ° C and a lower portion of 185 ° C at a temperature of 185 ° C and a lower portion of 185 ° C to form a film. The film sample was cut into small pieces at 100 ° C. /min was heated to 20,000 ° C and kept for 5 minutes as it was, and then cooled at 5 ° C /min to carry out DSC measurement (Seiko Electronics Co., Ltd. DSC-200), which was observed from the time of cooling. The apex peak of the crystallization of propylene is measured to determine the crystallization temperature Tc. The film sample was cut into small pieces, and the temperature was raised to 200 ° C at 100 ° C /min and kept for 5 minutes as it was. Thereafter, after cooling to 130 ° C at 20 (TC / min, it was kept at 130 ° C for 10 minutes. DSC measurement (DSC-200 manufactured by Seiko Electronics Co., Ltd.) The crystallization rate was measured from the time when the peak of the exothermic peak derived from the crystallization of polypropylene was observed at 13 (TC). The results are shown in Table 2. Further, the visible light transmittance and haze of the obtained film were determined in the same manner as in Example 1. As a result, the visible light transmittance was 30% and the haze was 85. (Example 7) The dry powder of 1 30 ° C of the basic zinc cyanurate obtained in the synthesis example 9 was replaced by the dry powder of 1 0 ° C of the basic zinc cyanurate obtained in Synthesis Example 7. The same procedure as in Example 6 was carried out, and the crystallization temperature T c and the crystallization rate of the polypropylene were measured. The results are shown in Table 2. Further, in the same manner as in Example 1, the visible light transmittance of -35 - 201219406 and the haze of the obtained film were determined, and as a result, the visible light transmittance was 40% and the haze was 71. (Example 8) In addition to the dry powder of 110 ° C of the basic zinc cyanurate obtained in Synthesis Example 10, in place of the dry powder of the basic zinc cyanurate obtained in Synthesis Example 9, The same procedure as in Example 6 was carried out, and the crystallization temperature T c and the crystallization rate of the polypropylene were measured. The results are shown in Table 2. Further, the visible light transmittance and haze of the obtained film were determined in the same manner as in Example 1. As a result, the visible light transmittance was 38% and the haze was 78. (Comparative Example 1) The same operation as in Example 1 was carried out except that basic zinc cyanuric acid was not added to the polylactic acid resin. Further, the visible light transmittance and haze of the obtained film were determined in the same manner as in Example 1. As a result, the visible light transmittance was 74% and the haze was 22. (Comparative Example 2) The same operation as in Example 6 was carried out except that the basic zinc cyanurate was not added to the polypropylene resin. Further, the visible light transmittance and the haze of the obtained film were determined in the same manner as in Example 1, and as a result, the visible light transmittance was 57%, and the haze was 31». When the basic zinc cyanurate is added, the crystallization temperature and the crystallization rate of the resin become high, and it is understood that the basic zinc cyanurate can be used as a crystal nucleating agent for the resin. In this way, since the resin crystals have a high rate of crystallization -36 - 201219406, the degree of crystallization of the resin is increased, and a molded article having good heat resistance can be obtained. Further, by increasing the crystallization rate, the time required for crystallization is shortened, and the molded article of the resin can be produced in a short time. In addition, by crystallization in a short period of time, the spherulite size is reduced, and a molded article having high transparency and high rigidity even without adding glass fibers can be obtained. Further, since the crystallization temperature of the resin is also high, since the cooling temperature of the mold can be increased, the molded product of the resin can be produced in a short time. Further, in the basic zinc cyanurate particles of Synthesis Example 7 or Synthesis Example 10, since the basic zinc cyanuric acid particles of Synthesis Example 9 are remarkably small particles, the basic melamine of Synthesis Example 7 was used. Example 2 and Example 7 of the zinc silicate particle, or Example 3 and Example 8 using the basic zinc cyanurate of Synthesis Example 10, compared to the basic zinc cyanurate particle of Synthesis Example 9. In Example 1 and Example 6, the visible light transmittance was high, the haze was low, and the transparency was excellent. -37- 201219406 【1®
電導度 (uS/cm) CO 0¾ ο ο oo 2 CO c— ς〇 Ln ΙΑ ε 〇〇 CO CO ο c-a 9 ο eo cd csa oo CO CO 〇〇 C£3 〇〇 <η ν·^ 短軸 (nm) ΙΛ 7 〇 〇 c*o ο 20 〜30 芑 l s § l s 25 〜50 S i LT3 i c=> ο ο 〇 LO e-o 10 〜60 1 長軸 (nm) 100 〜200 100〜300 L___ 100 〜400 100〜300 100〜200 100 〜300 100〜600 100〜300 2, 〇〇〇〜！ 20, 000 100〜800 平均粒子徑 Ds〇 (nm) CO 〇 L/9 LO ΙΛ c—· oo oo c〇 c>a CO s eo 〇 CO c-a Ln 2.620 s CO 比表面積 Sw (m2/g) LO e*Q CO CO c*o LT» c-a LT9 § ι/d i/a 分散触 «〇 CO C*»3 导 s CV3 CO CO c«a g eo CA/水 (質量％) 〇 c-i o oa 〇 c-i Cs3 C0 o e-i C— 〇 ο CN3 c— o ZnO/CA (莫耳比） LO C4 L/9 LT9 c-j ΙΛ c^a LO CN3 tra CO LT9 C^3 Ο c*a Lf> urt 分散介質 安定化ZrO: 安定化Zr0: 安定化ZrOj 安定化Zr02 安定化ZrO^q 安定化ZrO: ' 安定化ZrOi 安定化ZrO: 磁攪拌器 安定化ZrO: 分散機 批式砂磨機 批式砂磨機 批式砂磨機 批式砂磨機 批式砂磨機 批式砂磨機 珠磨機 批式砂磨機 燒杯 system zeta Zn源 〇 5 Ο N Ο N Ο N ο 5 鹼性1 碳酸鋅 〇 Q Ο t〇3 〇 «3 合成例1 合成例2 合成例3 1合成例4 1 1合成例5 . 合成例6 合成例7 合成例8 合成例9 合成例10 长«趙霞III3U -38- 201219406 [表2] 晶核劑 樹脂 核劑濃度 (重量份） 結晶化溫度Tc CC) 結晶化速度 (分） 實施例1 合成例9 聚乳酸樹脂 1.0 116 3.50 實施例2 合成例7 聚乳酸樹脂 1.0 117 3.45 實施例3 合成例10 聚乳酸樹脂 .1.0 118 3.00 實施例4 合成例10 聚乳酸樹脂 0.2 116 3. 60 實施例5 合成例10 聚乳酸樹脂 2.0 121 2. 33 比較例1 無添加 卜聚乳酸樹脂 0 113 4.68 實施例6 合成例9 聚丙烯樹脂 1.0 125 2. 02 實施例7 合成例7 聚丙烯樹脂 1.0 125 2. 00 實施例8 合成例10 聚丙烯樹脂 1.0 126 1.95 比較例2 無添加 聚丙烯樹脂 0 122 3. 00 (合成例1 1 ) 於2升之高分子容器中投入純水I501g及苯膦酸（（ 曰產化學工業（股）製），以下亦稱爲「PPA」）79.7g， 一邊攪拌一邊添加碳酸鎂（關東化學製試劑，以MgO爲 4 2wt% ) 19.3g後，攪拌1小時50分鐘將碳酸鎂溶解，調 製以莫耳比爲 Mg/PPA = 0.40 、 pH = 2.4 、 導電度 = 11.7 8mS/cm之苯膦酸鎂水溶液。在另一個2升之高分子 容器中加入純水l〇77g與所得到的苯膦酸鎂水溶液313g 後，浸漬於溫浴槽中，並加溫使混合水溶液成爲30°C爲 止。當混合水溶液到達3(TC後，使用分散翼（EYELA製 NZ-1000 )以3 3 00rpm —邊予以強力攪拌，一邊投入三聚 氰酸粉末（日產化學工業（股）製）36.4g，更一邊進行 加溫一邊予以強力攪拌40分鐘。接著，以分散翼一邊強 力攪拌一邊投入氧化鋅粉末（堺化學（股）製的2種氧化 -39- 201219406 鋅）57.4g，製成白色漿料1483g。此時的漿料溫度爲38 °C ’使漿料溫度維持在3 8 °C般地，於溫浴槽一邊進行加 溫一邊以分散翼強力攪拌8小時。因此，得到pH7.2、導 電度608//S/cm、黏度40〇1^3.5、11〇1乾燥時之固形 分爲7.2質量％之白色漿料I 483 g。將此漿料使用濾紙（ 5C ’東洋濾紙（股）製）進行Nutsche過濾，將所得到的 濕據餅以1 1 0 t乾燥後，使用家庭用混合機將乾燥濾餅粉 碎’得到比表面積爲28m2/g之粉末（11〇。(：之乾燥粉） 1 〇3g。對於此粉末進行X射線粉末繞射分析，結果如圖6 所示般’觀察到鹼性三聚氰酸鋅、苯膦酸鋅及氫氧化鎂之 繞射峰’爲由3種化合物之混合物所成的粉末。由此可知 ’苯膦酸鎂因強酸性的苯膦酸與氧化鋅之反應而成爲苯膦 酸鋅’鎂則成爲氫氧化鎂，殘餘的氧化鉢與三聚氰酸反應 而生成鹼性三聚氰酸鋅。此粉末爲含有三聚氰酸方面爲 29質量％、鋅方面爲43質量％、苯膦酸方面爲1 6質量％ 、及鎂方面爲1.3質量％。尙，三聚氰酸c3N303H3，係在 CHN元素分析’由所測定樹脂用晶核劑中之氮量所算出 ’且苯膦酸CeHvC^P ’係在螢光X射線分析，由所測定樹 脂用晶核劑中之磷量所算出。然後，將此粉末以純水分散 後’以穿透型電子顯微鏡觀察之結果，係長軸爲 200〜800nm、短軸爲20〜60nm之鹼性三聚氰酸鋅之針狀粒 子' 長軸及短軸爲1〇〇〜500nm之苯膦酸鋅、及氫氧化鎂 之粒狀粒子均一地分散著。結果如表3所示。 -40- 201219406 (合成例1 2 ) 除了將三聚氰酸粉末（日產化學工業（股）製）設定 爲33. lg以外，與合成例1 1進行同樣之操作，得到ρΗ7· 2 、導電度 196 S/cm、黏度500mPa.s、ii〇°c乾燥時之 固形分爲7.2質量％之白色漿料1 483g »將此漿料使用濾 紙（5C，東洋濾紙（股）製）進行Nutsche過濾，將所得 到的濕濾餅以Π 0 °C乾燥後，使用家庭用混合機將乾燥濾 餅粉碎，得到比表面積爲49m2/g之粉末l〇2g。對於此粉 末進行X射線粉末繞射分析之結果，觀察到鹼性三聚氰 酸鋅、苯膦酸鋅及氫氧化鎂之繞射峰。此粉末爲含有三聚 氰酸方面爲32質量％、鋅方面爲42質量％、苯膦酸方面 爲1 6質量％、及鎂方面爲1 · 3質量％。然後，將此粉末以 純水分散後，以穿透型電子顯微鏡觀察之結果，係長軸爲 200〜800nm、短軸爲20〜60nm之鹼性三聚氰酸鋅之針狀粒 子、長軸及短軸爲1〇〇〜500nm之苯膦酸鋅、及氫氧化鎂 之粒狀粒子均一地分散著。結果如表3所示。又，穿透型 電子顯微鏡所觀察之照片如圖7所示。 (合成例1 3 ) 於2升之高分子容器中將合成例11所製成的苯膦酸 鎂水溶液3 13g與純水1160g混合後，浸漬於溫浴槽中， 並加溫使混合水溶液成爲3 0 °C爲止。當混合水溶液到達 3〇°C後，使用分散翼以3 300rpm —邊予以強力攪拌，一邊 投入三聚氰酸粉末（日產化學工業（股）製）30.3g，更 -41 - 201219406 一邊進行加溫一邊予以強力攪拌40分鐘。接著，以分散 翼一邊強力攪拌一邊投入氧化鋅粉末（堺化學（股）製的 2種氧化鋅）57.4g’製成白色漿料1560g。此時的槳料溫 度爲3 8 °C，使漿料溫度維持在3 8 °C般地，於溫浴槽一邊 進行加溫一邊以分散翼強力攪拌8小時。因此，得到 pH8.6、導電度 133#5/〇111、黏度 700111?&.3.、110。(：乾燥 時之固形分爲6.6質量％之白色漿料1 560g。將此漿料使 用濾紙（5C，東洋濾紙（股）製）進行Nutsche過濾，將 所得到的濕濾餅以11 0 °C乾燥後，使用家庭用混合機將乾 燥濾餅粉碎，得到比表面積爲56m2/g之粉末100g。對於 此粉末進行X射線粉末繞射分析之結果，觀察到鹼性三 聚氰酸鋅、苯膦酸鋅及氫氧化鎂之繞射峰。此粉末爲含有 三聚氰酸方面爲35質量％、鋅方面爲40質量％、苯膦酸 方面爲1 5質量％、及鎂方面爲1 .2質量％。然後，將此粉 末以純水分散後，以穿透型電子顯微鏡觀察之結果，觀察 到長軸爲200〜800nm、短軸爲20〜60nm之鹼性三聚氰酸 鋅之針狀粒子、長軸及短軸爲100〜5 00nm之苯膦酸鋅、 及氫氧化鎂之粒狀粒子。結果如表3所示。 (合成例Μ ) 於2升之高分子容器中加入純水99 7g與合成例1 1所 得到的苯膦酸鎂水溶液3 1 3 g。對於此混合水溶液使用分 散翼以3 300rpm —邊予以強力攪拌，一邊投入三聚氰酸粉 末（日產化學工業（股）製）33.lg’接著’以分散翼一 -42- 201219406 邊強力擾拌一邊投入氧化鋅粉末（搏化學（股）製的2種 氧化辞）57.4g，製成白色發料1400g。此時的漿料溫度爲 26°C ’接著以分散翼強力攪拌8小時後之漿料溫度爲28 °C 。因此，得到 ΡΗ8·0、導電度 275 μ S/cm、黏度 1040mPa· s、110°C乾燥時之固形分爲7.6質量％之白色 漿料1 400g。將此漿料使用濾紙（5C，東洋濾紙（股）製 )進行Nutsche過濾，將所得到的濕濾餅以1 1 〇°C乾燥後 ’使用家庭用混合機將乾燥濾餅粉碎，得到比表面積爲 6 2m2/g之粉末l〇5g。對於此粉末進行X射線粉末繞射分 析之結果，觀察到鹼性三聚氰酸鋅、苯膦酸鋅及氫氧化鎂 之繞射峰。此粉末爲含有三聚氰酸方面爲32質量％、鋅 方面爲42質量％、苯膦酸方面爲16質量％、及鎂方面爲 1.3質量％。然後，將此粉末以純水分散後，以穿透型電 子顯微鏡觀察之結果，觀察到長軸爲100~3 00nm、短軸爲 1 0〜3 Onm之鹼性三聚氰酸鋅之針狀粒子、長軸及短軸爲 50〜200nm之苯膦酸鋅，及氫氧化鎂之粒狀粒子。結果如 表3所示。 (合成例1 5 ) 除了將漿料溫度設定爲5 0 t以外，與合成例1 2進行 同樣之操作，得到ρΗ7·7、導電度213 # S/cm、黏度 720mPa · s、1 1 〇°c乾燥時之固形分爲7_6質量％之白色漿 料14 8 0 g。將此漿料使用濾紙（5 C，東洋濾紙（股）製） 進行Nutsche過濾，將所得到的濕濾餅以1 1 0°C乾燥後’ -43- 201219406 使用家庭用混合機將乾燥濾餅粉碎，得到比表面積爲 3 5m2/g之粉末102g。對於此粉末進行X射線粉末繞射分 析之結果，觀察到鹼性三聚氰酸鋅、苯膦酸鋅及氫氧化鎂 之繞射峰。此粉末爲含有三聚氰酸方面爲32質量％、鋅 方面爲42質量％、苯膦酸方面爲16質量％、及鎂方面爲 1 .3質量％。然後，將此粉末以純水分散後，以穿透型電 子顯微鏡觀察之結果，觀察到長軸爲2 0 0~ 1 000nm、短軸 爲40~80nm之鹼性三聚氰酸鋅之針狀粒子、長軸及短軸 爲200〜600nm之苯膦酸鋅、及氫氧化鎂之粒狀粒子。結 果如表3所示》 (合成例1 6 ) 除了將漿料溫度設定爲6 0 °C以外，與合成例12進行 同樣之操作，得到 pH7.6、導電度 183yS/cm、黏度 640mPa · s、1 1 0 °C乾燥時之固形分爲7.6質量％之白色漿 料1480g。將此漿料使用濾紙（5C，東洋濾紙（股）製） 進行Nutsche過濾，將所得到的濕濾餅以11(TC乾燥後， 使用家庭用混合機將乾燥濾餅粉碎，得到比表面積爲 2 6m2/g之粉末102g。對於此粉末進行X射線粉末繞射分 析之結果，觀察到鹼性三聚氰酸鋅、苯膦酸鋅及氫氧化鎂 之繞射峰。此粉末爲含有三聚氰酸方面爲32質量％、鋅 方面爲42質量％、苯膦酸方面爲16質量％、及鎂方面爲 1 .3質量％。然後，將此粉末以純水分散後，以穿透型電 子顯微鏡觀察之結果，係長軸爲300~1000nm、短軸爲 44 - 201219406 40~100nm之鹼性三聚氰酸鋅之針狀粒子、長軸及短軸爲 3 0 0〜8 OOnm之苯膦酸鋅、及氫氧化鎂之粒狀粒子均—地分 散著。結果如表3所示。 (合成例1 7 ) 於2升之高分子容器中將合成例11所製成的苯膦酸 鎂水溶液195g與純水1194g混合後，浸漬於溫浴槽中， 並加溫使混合水溶液成爲3 0 °C爲止。當混合水溶液到達 3〇°C後，使用分散翼以3 3 00rPm —邊予以強力攪拌，一邊 投入三聚氰酸粉末（日產化學工業（股）製）33.lg，更 一邊進行加溫一邊予以強力攪拌40分鐘。接著，以分散 翼一邊強力攪拌一邊投入氧化鋅粉末（堺化學（股）製的 2種氧化鋅）57.4g，製成白色漿料1483g。此時的漿料溫 度爲3 8 °C，使漿料溫度維持在3 8 °C般地，於溫浴槽一邊 進行加溫一邊以分散翼強力攪拌8小時，得到pH8.1、導 電度 142/zS/cm、黏度 540mPa. s、110°C乾燥時之固形 分爲7.2質量％之白色漿料1 483 g。將此漿料使用濾紙（ 5C，東洋濾紙（股）製）進行Nutsche過濾，將所得到的 濕濾餅以1 1 0 °C乾燥後，使用家庭用混合機將乾燥濾餅粉 碎，得到比表面積爲52m2/g之粉末l〇4g。對於此粉末進 行X射線粉末繞射分析之結果，觀察到鹼性三聚氰酸鋅 、苯膦酸鋅及氫氧化鎂之繞射峰。此粉末爲含有三聚氰酸 方面爲33質量％、鋅方面爲46質量％、苯膦酸方面爲10 質量％、及鎂方面爲0.8質量％。然後，將此粉末以純水 -45- 201219406 分散後’以穿透型電子顯微鏡觀察之結果，觀察到長軸爲 20 0〜80 0nm、短軸爲20〜60nm之鹼性三聚氰酸鋅之針狀粒 子、長軸及短軸爲100〜500nm之苯膦酸鋅、及氫氧化鎂 之粒狀粒子。結果如表3所示。 (合成例1 8 ) 將純水3 68kg置入於容積700升之附有夾套（jacket )之SUS製容器中，使用安裝有直徑300inrn之分散翼之 攪拌機 Hyper(Ashizawa Finetech (股）製 Hyper)，以 分散翼500rpm —邊進行分散，—邊投入氧化鋅粉末（堺 化學（股）製的2種氧化鋅）20.3kg。爲了使此氧化鋅漿 料之溫度提高至49°C，將夾套水加溫。在途中氧化鋅漿 料到達40°C時，將分散翼之回轉數提高至800rpm —邊進 行強力分散，一邊將三聚氰酸粉末（日產化學工業（股） 製）1 1.7kg分3次、間隔30分鐘投入。三聚氰酸粉末投 入後，漿料之溫度成爲49°C，調節夾套水之溫度使保持 於此溫度。氧化鋅/三聚氰酸之莫耳比爲2.75，相對於水 之三聚氰酸濃度爲2.9質量％。將此漿料以分散翼之回轉 數爲800rpm之原樣強力分散9小時。因此，得到PH7.5 、導電度29/zS/cm、黏度866mPa.s、110°C乾燥時之固 形分爲8.3質量％之白色漿料3 9 5kg。對於所得到的白色 漿料之1 1 0°C乾燥粉進行X射線粉末繞射分析之結果，觀 察到鹼性三聚氰酸鋅之繞射峰。所得到的白色漿料中所含 有的微粒子，以穿透型電子顯微鏡觀察時，係長軸爲 -46 - 201219406 200~800nm、短軸爲 20~50nm，110°C 乾 Sw爲3 5m2/g之鹼性三聚氰酸鋅。 將所得到的鹼性三聚氰酸鋅換算濃度 色漿料589g置入於1升之高分子瓶-30mm之分散翼以3 200rpm —邊進行強力 合成例1 1所製成的苯膦酸鎂水溶液1 68g 6小時。因此，得到 pH8.5、導電度 1 840mPa . s之漿料，並使用濾紙（5C，東 )進行N u t s c h e過濾，將所得到的濕爐餅 ，使用家庭用混合機將乾燥濾餅粉碎， 3 5m2/g之粉末56g。對於此粉末進行X射 之結果，觀察到鹼性三聚氰酸鋅、苯膦酸 繞射峰。此粉末爲含有三聚氰酸方面爲 面爲42質量％、苯膦酸方面爲1 6質量％ 質量％。然後，將此粉末以純水分散後， 微鏡觀察之結果，觀察到長軸爲 20(l· 20〜60nm之鹼性三聚氰酸鋅之針狀粒子 100〜5 00nm之苯膦酸鋅、及氫氧化鎂之| 表3所示。 (合成例1 9 ) 將純水24kg與氧化鋅粉末（堺化學 氧化鋅）1.88kg投入於容積200升之混合 散翼攪拌混合後，調製氧化鋅換算濃度爲 燥後之比表面積 8.3質量％之白 ί中，使用直徑 '分散，一邊投入 後，更強力分散 88 μ S/cm、黏度 :洋濾紙（股）製 〖以1 l〇°C乾燥後 得到比表面積爲 線粉末繞射分析 鋅及氫氧化鎂之 3 2質量％、鋅方 、及鎂方面爲1.3 以穿透型電子顯 -800nm、短軸爲 、長軸及短軸爲 :狀粒子。結果如 (股）製的2種 用槽中，使用分 7.62質量％之漿 -47- 201219406 料26kg。接著，在有效容積10.66升之內壁爲胺甲酸乙酯 樹脂之橫式珠粒硏磨機（Ashizawa Finetech (股）製 system zetaLMZ25)中，置入 Φ 1mm之安定化锆製粉碎 珠粒66kg。於將水溫爲13 °C之井水作爲夾套水之循環槽 中置入純水144kg後，使橫式珠粒硏磨機之盤以周速 9 · 5 m/秒鐘一邊進行回轉，一邊以供給速度2 2 · 1 kg/分鐘將 純水供給予橫式珠粒硏磨機，使純水循環。循環開始後投 入三聚氰酸粉末（日產化學工業（股）製）1.19kg。將三 聚氰酸粉末投入後，使循環漿料之溫度成爲42 °C般地予 以調節後，將氧化鋅換算濃度爲7.69質量％之氧化鋅漿料 24.6kg分5次、花費1〇分鐘進行添加。添加後，亦將橫 式珠粒硏磨機之盤一邊以周速9.5m/秒鐘進行回轉，一邊 以供給速度22. lkg/分鐘將漿料循環7小時，使分散。又 ’之間亦使循環漿料溫度成爲4 2 °C般地進行調節。因此 ，得到ρΗ7·9、導電度206"S/cm、黏度86riiPa. s、鹼性 三聚氰酸鋅換算濃度1·8質量％之白色漿料167kg。對於 所得到白色漿料之1 1 0 °C乾燥粉進行X射線粉末繞射分析 之結果’未觀察到歸屬於原料之三聚氰酸及氧化鋅之繞射 峰’但觀察到鹼性三聚氰酸鋅之繞射峰。此粉末爲含有三 聚氰酸方面爲39質量％，及鋅方面爲49質量％。接著， 所得到的白色漿料中所含有的微粒子，以穿透型電子顯微 鏡觀察時，係長軸爲400〜12〇〇nm、短軸爲20~40nm，藉 由雷射繞射法粒子徑測定之平均粒子徑D 5 〇爲3 9 7 nm，7 0 °C乾燥後之比表面積Sw爲5 4m2/g之鹼性三聚氰酸鋅。結 -48- 201219406 果如表3所示。又，穿透型電子顯微鏡所觀察之照片如圖 8所示。 (合成例20) 於2升之高分子容器中將合成例11所製成的苯膦酸 鎂水溶液156g與純水1 23 3 g混合後，浸漬於溫浴槽中， 並加溫使混合水溶液成爲30 °C爲止。當混合水溶液到達 3〇°C後，使用分散翼以3300rpm —邊予以強力攪拌，一邊 投入三聚氰酸粉末（日產化學工業（股）製）36.4g，更 一邊進行加溫一邊予以強力攪拌40分鐘。接著，以分散 翼一邊強力攪拌一邊投入氧化鋅粉末（堺化學（股）製的 2種氧化鋅）57.4g，製成白色漿料1483g。此時的漿料溫 度爲3 8 °C，使漿料溫度維持在3 8 °C般地，於溫浴槽一邊 進行加溫一邊以分散翼強力攪拌8小時，得到pH8.4、導 電度 130//S/cm'黏度 550mPa.s、110°C乾燥時之固形 分爲7.2質量％之白色漿料1 483 g。將此漿料使用濾紙（ 5C，東洋濾紙（股）製）進行Nutsche過濾，將所得到的 濕濾餅以110°C乾燥後，使用家庭用混合機將乾燥濾餅粉 碎，得到比表面積爲60m2/g之粉末103g。對於此粉末進 行X射線粉末繞射分析之結果，觀察到鹼性三聚氰酸鋅 、苯膦酸鋅及氫氧化鎂之繞射峰。此粉末爲含有三聚氰酸 方面爲34質量％、鋅方面爲46質量％、苯膦酸方面爲8 質量％、及鎂方面爲0.6質量％。然後，將此粉末以純水 分散後，以穿透型電子顯微鏡觀察之結果，觀察到長軸爲 •49- 201219406 2 00~8 00nm、短軸爲20〜60nm之鹼性三聚氰酸鋅之針狀粒 子、長軸及短軸爲100〜500nm之苯膦酸鋅、及氫氧化鎂 之粒狀粒子。結果如表3所示。 (合成例2 1 ) 於2升之高分子容器中添加純水13 84g與苯膦酸（曰 產化學工業（股）製）4.7g後，浸漬於溫浴槽中，並加溫 使混合水溶液成爲3 0 °C爲止》當混合水溶液到達3 0 °C後 ，使用分散翼以330〇rpm —邊予以強力攪拌，一邊投入三 聚氰酸粉末（日產化學工業（股）製）36.4g，更一邊進 行加溫一邊予以強力攪拌40分鐘。接著，以分散翼一邊 強力攪拌一邊投入氧化鋅粉末（堺化學（股）製的2種氧 化鋅）57.4g，製成白色漿料1483g。此時的漿料溫度爲 3 8 °C，使漿料溫度維持在3 8 °C般地，於溫浴槽一邊進行 加溫一邊以分散翼強力攪拌8小時。因此，得到p Η 6.3、 導電度151 " S/cm、黏度640mPa. s、110°C乾燥時之固 形分爲7.2質量％之白色漿料1 4 8 3 g。將此漿料使用濾紙 (5C，東洋濾紙（股）製）進行Nutsche過濾，將所得到 的濕濾餅以1 1 〇°C乾燥後，使用家庭用混合機將乾燥濾餅 粉碎，得到比表面積爲15m2/g之粉末98g。對於此粉末 進行X射線粉末繞射分析之結果，觀察到鹼性三聚氰酸 鋅及苯膦酸鋅之繞射峰。此粉末爲含有三聚氰酸方面爲 34質量％ '鋅方面爲46質量％、及苯膦酸方面爲1〇質量 %。然後’將此粉末以純水分散後，以穿透型電子顯微鏡 -50- 201219406 觀察之結果，觀察到長軸爲200〜600nm、短軸爲20〜40nm 之鹼性三聚氰酸鋅之針狀粒子、長軸及短軸爲 2000~3000nm之苯膦酸鋅之粗大粒狀粒子。結果如表3所 示0 〔晶核劑評價-1〕 . (實施例9) 將合成例1 1所得到1 1 〇 °c之乾燥粉（樹脂用晶核劑 )〇.55g及聚乳酸樹脂（NW300 1 D、數平均分子量72,000 、融點164°C、natureworks製）54.5g混合後，置入於已 加熱至1 70°C之小型二軸混練擠壓機（布蘭達（音譯）公 司製）15分鐘，以50 rpm進行混練，製成樹脂組成物。 冷卻後，取出樹脂組成物，以鐵氟龍薄片與黃銅板挾持， 置於已加熱至上部185 °C、下部185 °C之熱壓製機中，使 薄膜之厚度成爲〇.4mm般地以0.5kgf進行加壓，製成薄 膜。將此薄膜狀樣本切取成小片，以200 °C /分鐘昇溫至 200°C並原樣地保持5分鐘，之後，以5°C/分鐘予以冷卻 來進行DSC測定（Seiko電子（股）製DSC-200)。由冷 卻時所觀測到來自於聚乳酸之結晶化之發熱峰頂點來測定 結晶化溫度Tc。 又，將此薄膜狀樣本切取成小片，以1 〇〇°C /分鐘昇溫 至20 0 °C並原樣地保持5分鐘，之後，以100 °C /分鐘冷卻 至110°c後，進行以ll〇°C保持10分鐘之DSC測定（ Seiko電子（股）製DSC-200 )。由保持於U〇°C時所觀 -51 - 201219406 測到來自於聚乳酸之結晶化之發熱峰頂點之時間，來測定 結晶化速度。結果如表4所示。尙，在表4中，將樹脂用 晶核劑之濃度，以相對於樹脂1 〇〇質量份之樹脂用晶核劑 之質量份予以記載。 (實施例1 0 ) 除了使用合成例12所得到的110 °c乾燥粉〇.55g來取 代合成例1 1所得到的1 1 0°C乾燥粉以外，與實施例9進 行同樣之操作，測定聚乳酸之結晶化溫度Tc及結晶化速 度。結果如表4所示。 又’將所得到的薄膜之可見光透過率使用色差計（東 京電色TC- 1 8 00MK型），霧度爲使用SPECTRAL HAZE METER (東京電色TC-H3DPK-MK型）予以求得，結果爲 波長5 50nm之可見光透過率爲44%、霧度爲56。 (實施例1 1 ) 除了使用合成例1 3所得到的1 1 0 °C乾燥粉0 · 5 5 g來取 代合成例1 1所得到的1 1 (TC乾燥粉以外，與實施例9進 行同樣之操作，測定聚乳酸之結晶化溫度Tc及結晶化速 度。結果如表4所示。 (實施例1 2 ) 除了使用合成例1 4所得到的1 1 〇。(：乾燥粉0.5 5 g來取 代合成例Π所得到的n 〇t乾燥粉以外，與實施例9進 -52- 201219406 行同樣之操作，測定聚乳酸之結晶化溫度Tc及結晶化速 度。結果如表4所示。 (實施例1 3 ) 除了使用合成例15所得到的1 1(TC乾燥粉〇.55g來取 代合成例1 1所得到的1 1 (TC乾燥粉以外，與實施例9進 行同樣之操作，測定聚乳酸之結晶化溫度Tc及結晶化速 度。結果如表4所示。 (實施例1 4 ) 除了使用合成例1 2所得到的1 1 Ot乾燥粉0 · 1 1 g來取 代合成例1 1所得到的1 1 乾燥粉以外，與實施例9進 行同樣之操作，測定聚乳酸之結晶化溫度Tc及結晶化速 度。結果如表4所示。 又’將所得到的薄膜之可見光透過率使用色差計（東 京電色TC- 1 800MK型），霧度爲使用SPECTRAL HAZE METER (東京電色TC-H3DPK-MK型）予以求得，結果爲 波長5 5 0nm之可見光透過率爲75%、霧度爲24。 (實施例1 5 ) 除了使用合成例16所得到的1 10°C乾燥粉0.55g來取 代合成例1 1所得到的1 1 0 °C乾燥粉以外，與實施例9進 行同樣之操作’測定聚乳酸之結晶化溫度Tc及結晶化速 度。結果如表4所示。 -53- 201219406 (實施例1 6 ) 除了使用合成例17所得到的ll〇°C乾燥粉〇.55g來取 代合成例1 1所得到的1 1 〇 °C乾燥粉以外，與實施例9進 行同樣之操作，測定聚乳酸之結晶化溫度TC及結晶化速 度。結果如表4所示。 (實施例1 7 ) 除了使用合成例18所得到的1 10°C乾燥粉0.55g來取 代合成例1 1所得到的1 1 0°C乾燥粉以外，與實施例9進 行同樣之操作，測定聚乳酸之結晶化溫度Tc及結晶化速 度。結果如表4所示。 (實施例1 8 ) 以合成例1 9所得到的鹼性三聚氰酸鋅之1 1 〇 °C乾燥 粉7.0g與含有鋅29質量％及苯膦酸71質量％之苯膦酸鋅 (商標ECOPROMOTE日產化學工業（股）製）3.0g來取 代合成例1 1所得到的！ 1 〇 t乾燥粉，使用家庭用粉體混 合機予·以混合製成評價用混合粉。除了使用此混合粉 〇 · 5 5 g來取代合成例u所得到的1 ! (^c乾燥粉以外，與實 施例9進行同樣之操作，測定聚乳酸之結晶化溫度tc及 結晶化速度β結果如表4所示。 $ ’將所得到的薄膜之可見光透過率使用色差計（東 足電色TC-1800MK型），霧度爲使用SPECTRAL HAZE METER (東京電色TC.H3DPK-MK型）予以求得，結果爲 -54 - 201219406 波長550nm之可見光透過率爲40%、霧度爲61。 (實施例1 9 ) 將苯膦酸鋅（商標ECOPROMOTE日產化學X業（股 )製）5.0g，與合成例19所得到的鹼性三聚氰酸鋅之no °C乾燥粉16.9g及氫氧化鎂（關東化學（股）製試劑） 0.4g，使用家庭用粉體混合機進行混合，製成含有三聚氰 酸29質量％、鋅43質量％、苯膦酸16質量％及鎂丨.3質 量％之混合粉。除了使用此混合粉0.55g來取代合成例11 所得到的1 1 〇°C乾燥粉以外，與實施例9進行同樣之操作 ，測定聚乳酸之結晶化溫度Tc及結晶化速度。結果如表 4所示。 (實施例20 ) 除了使用合成例20所得到的1 10°C乾燥粉0.55g來取 代合成例1 1所得到的1 1 〇 °C乾燥粉以外，與實施例9進 行同樣之操作，測定聚乳酸之結晶化溫度Tc及結晶化速 度。結果如表4所示。 (實施例2 1 ) 除了使用合成例21所得到的1 l〇°C乾燥粉0.5 5g來取 代合成例1 1所得到的1 1 〇 °C乾燥粉以外，與實施例9進 行同樣之操作，於測定聚乳酸之結晶化溫度Tc及結晶化 速度時，漿料成爲PH7以下，一部份之聚乳酸溶解於此 -55- 201219406 樹脂用晶核劑中。 (比較例3 ) 除了未添加樹脂用晶核劑以外，與實施例9進行同樣 之操作，測定聚乳酸之結晶化溫度Tc及結晶化速度。結 果如表4所示。 又，將所得到的薄膜之可見光透過率使用色差計（東 京電色 TC- 1 800MK型），霧度爲使用 SPECTRAL HAZE METER (東京電色TC-H3DPK-MK型）予以求得，結果爲 波長55〇nm之可見光透過率爲87%、霧度爲14。 (比較例4) 除了使用苯膦酸鋅（商標ECOPROMOTE日產化學工 業（股）製）〇 · 5 5 g取代合成例1 1所得到的1 1 〇 °c乾燥粉 以外’與實施例9進行同樣之操作，測定聚乳酸之結晶化 溫度T c及結晶化速度。結果如表4所示。又，將上述苯 膦酸鋅以穿透型電子顯微鏡觀察之結果如圖9所示。尙， 上述苯膦酸鋅之比表面積爲12m2/g。 又’將所得到的薄膜之可見光透過率使用色差計（東 京電色TC- 1 800MK型）’霧度爲使用SPECTRAL HAZE METER (東京電色TC-H3DPK-MK型）予以求得，結果爲 波長5 50nm之可見光透過率爲30%、霧度爲70。 (比較例5) -56- 201219406 除了使用苯膦酸鋅（商標ECOPROMOTE日產化學工 業（股）製）〇 · 1 1 g取代合成例1 1所得到的i丨〇乞乾燥粉 以外，與實施例9進行同樣之操作，測定聚乳酸之結晶化 溫度T c及結晶化速度。結果如表4所示。 又’將所得到的薄膜之可見光透過率使用色差計（東 京電色TC- 1 800MK型），霧度爲使用SPECTRAL HAZE METER (東京電色TC-H3DPK-MK型）予以求得，結果爲 波長550nm之可見光透過率爲60%'霧度爲41。 (參考實施例1 ) 除了使用合成例1 9所得到的鹼性三聚氰酸鋅之1 1 0 °C乾燥粉0.55g取代合成例1 1所得到的no〇c乾燥粉以外 ’與實施例9進行同樣之操作，測定聚乳酸之結晶化溫度 Tc及結晶化速度。結果如表4所示。 又’將所得到的薄膜之可見光透過率使用色差計（東 京電色TC- 1 8 00MK型），霧度爲使用SPECTRAL HAZE METER(東京電色TC-H3DPK-MK型）予以求得，結果爲 波長5 5 0nm之可見光透過率爲39%、霧度爲64。 (參考實施例2) 除了使用合成例19所得到的鹼性三聚氰酸鋅之110 °C乾燥粉〇· 1 1 g取代合成例U所得到的1 1 〇°c乾燥粉以外 ’與實施例9進行同樣之操作，測定聚乳酸之結晶化溫度 Tc及結晶化速度。結果如表4所示。 -57- 201219406 又，將所得到的薄膜之可見光透過率使用色差計（東 京電色TC- 1 800MK型），霧度爲使用 SPECTRAL HAZE METER (東京電色TC-H3DPK-MK型）予以求得，結果爲 波長550nm之可見光透過率爲67%、霧度爲29。 此結果如表4所示般，相較於未添加樹脂用晶核劑之 比較例3、或僅含有鹼性三聚氰酸鋅之參考實施例1及2 ’確認到實施例9〜2 1之結晶化溫度顯著地較高，且，結 晶化速度顯著地高、晶核劑性能非常地優異。 又，相較於僅含有高價格的苯膦酸鋅之比較例4及5 ，實施例9〜2 1爲相同程度之結晶化溫度及結晶化速度， 藉由與較苯膦酸之金屬鹽爲低成本的鹼性三聚氰酸鋅微粒 子一起使用苯膦酸之金屬鹽，亦確認到可兼具所謂的提高 樹脂之結晶化速度及結晶化溫度之效果，與所謂的低成本 化之效果。 又’相較於含有成分爲相同之實施例9與實施例19 時’實施例1之結晶化速度及結晶化溫度爲高。因此可得 知’相較於單純地使鹼性三聚氰酸鋅與苯膦酸鋅及氫氧化 鎂混合’以如實施例9般使原料產生反應而製造時，晶核 劑性能爲優異。 〔晶核劑評價-2〕 (實施例22 )Conductivity (uS/cm) CO 03⁄4 ο ο oo 2 CO c— ς〇Ln ΙΑ ε 〇〇CO CO ο ca 9 ο eo cd csa oo CO CO 〇〇C£3 〇〇<η ν·^ Short axis (nm) ΙΛ 7 〇〇c*o ο 20 〜30 芑ls § ls 25 〜50 S i LT3 ic=> ο ο 〇LO eo 10 ～60 1 Long axis (nm) 100 〜200 100~300 L___ 100 ~400 100~300 100~200 100~300 100~600 100~300 2, 〇〇〇~! 20, 000 100~800 Average particle diameter Ds〇(nm) CO 〇L/9 LO ΙΛ c—· oo oo c〇c>a CO s eo 〇CO ca Ln 2.620 s CO Specific surface area Sw (m2/g) LO e*Q CO CO c*o LT» ca LT9 § ι/di/a Dispersion touch «〇CO C*»3 s s CV3 CO CO c«ag eo CA/water (% by mass) 〇ci o oa 〇ci Cs3 C0 o ei C— 〇ο CN3 c— o ZnO/CA (Mo Erbi) LO C4 L/9 LT9 cj ΙΛ c^a LO CN3 tra CO LT9 C^3 Ο c*a Lf> urt Dispersion medium stabilization ZrO : 安定化Zr0: 安定化ZrOj 安定化Zr02 安定化ZrO^q 安定化ZrO: ' 安定化ZrOi 安定化ZrO: Magnetic Stirrizer Stabilized ZrO: Disperser Batch Sander Batch Sander Batch Sand Mill batch sander batch sander batch sander bead mill batch sander beaker system zeta Zn source 〇 5 Ο N Ο N Ο N ο 5 alkaline 1 zinc carbonate 〇 Q Ο t〇 3 〇«3 Synthesis Example 1 Synthesis Example 2 Synthesis Example 3 Synthesis Example 4 1 Synthesis Example 5 Synthesis Example 6 Synthesis Example 7 Synthesis Example 8 Synthesis Example 9 Synthesis Example 10 Length «Zhao Xia III 3U -38- 201219406 [Table 2 Nucleating agent resin nucleating agent concentration (parts by weight) Crystallization temperature Tc CC) Crystallization speed (minutes) Example 1 Synthesis Example 9 Polylactic acid resin 1.0 116 3.50 Example 2 Synthesis Example 7 Polylactic acid resin 1.0 117 3.45 Example 3 Synthesis Example 10 Polylactic acid resin. 1.0 118 3.00 Implementation Example 4 Synthesis Example 10 Polylactic acid resin 0.2 116 3. 60 Example 5 Synthesis Example 10 Polylactic acid resin 2.0 121 2. 33 Comparative Example 1 No added polylactic acid resin 0 113 4.68 Example 6 Synthesis Example 9 Polypropylene resin 1.0 125 2. 02 Example 7 Synthesis Example 7 Polypropylene resin 1.0 125 2. 00 Example 8 Synthesis Example 10 Polypropylene resin 1.0 126 1.95 Comparative Example 2 No added polypropylene resin 0 122 3. 00 (Synthesis Example 1 1 ) 2 In the polymer container, the amount of pure water I501g and phenylphosphonic acid (also known as "PPA"), 79.7g, were added to the polymer container, and magnesium carbonate (Kordon Chemical Co., Ltd.) was added while stirring. After MgO was 42 wt%) 19.3 g, magnesium carbonate was dissolved by stirring for 1 hour and 50 minutes to prepare an aqueous magnesium phenylphosphonate solution having a molar ratio of Mg/PPA = 0.40, pH = 2.4, and conductivity = 11.7 8 mS/cm. In a two-liter polymer container, 173 g of pure water and 313 g of the obtained aqueous magnesium phenylphosphonate solution were added, and the mixture was immersed in a warm bath and heated to make the mixed aqueous solution 30 °C. When the mixed aqueous solution reached 3 (TC), 36.4 g of a cyanuric acid powder (manufactured by Nissan Chemical Industries Co., Ltd.) was added while vigorously stirring using a dispersion wing (NZ-1000 manufactured by EYELA) at 3 3 00 rpm. After heating, the mixture was vigorously stirred for 40 minutes, and 57.4 g of zinc oxide powder (two kinds of oxidation-39-201219406 zinc manufactured by Seiko Chemical Co., Ltd.) was added thereto with vigorous dispersion while stirring, to prepare 1483 g of a white slurry. At this time, the slurry temperature was 38 ° C. The slurry temperature was maintained at 38 ° C, and the mixture was vigorously stirred for 8 hours while being heated in a warm bath. Thus, pH 7.2 and conductivity 608 were obtained. //S/cm, viscosity 40〇1^3.5, 11〇1 The solid form when dry is divided into 7.2% by mass of white slurry I 483 g. This slurry is made of filter paper (5C 'Toyo filter paper) After Nutsche filtration, the obtained wet cake was dried at 110 °, and the dried filter cake was pulverized using a household mixer to obtain a powder having a specific surface area of 28 m 2 /g (11 〇. (: dry powder) 1 〇 3g. X-ray powder diffraction analysis of this powder, the results are shown in Figure 6. It is shown that 'the diffraction peak of basic zinc cyanurate, zinc phenylphosphonate and magnesium hydroxide' is a powder composed of a mixture of three compounds. It can be seen that 'the magnesium phenylphosphonate is strongly acidic. The reaction of phenylphosphonic acid with zinc oxide to form zinc phenylphosphonate becomes magnesium hydroxide, and the residual cerium oxide reacts with cyanuric acid to form basic zinc cyanurate. The powder contains cyanuric acid. The aspect is 29% by mass, the zinc is 43% by mass, the phenylphosphonic acid is 16% by mass, and the magnesium is 1.3% by mass. 尙, cyanuric acid c3N303H3 is used for the CHN elemental analysis. The amount of nitrogen in the crystal nucleating agent was calculated and 'the phenylphosphonic acid CeHvC^P ' was calculated by fluorescent X-ray analysis from the amount of phosphorus in the nucleating agent for the resin to be measured. Then, the powder was dispersed in pure water. After the observation by a transmission electron microscope, the needle-like particles of the basic zinc cyanurate having a major axis of 200 to 800 nm and a short axis of 20 to 60 nm have a long axis and a short axis of 1 to 500 nm. The granular particles of zinc phenylphosphonate and magnesium hydroxide were uniformly dispersed. The results are shown in Table 3. -40-20 1219406 (Synthesis Example 1 2) The same operation as in Synthesis Example 1 was carried out except that the cyanuric acid powder (manufactured by Nissan Chemical Industries Co., Ltd.) was set to 33. lg, and ρΗ7· 2 was obtained, and the conductivity was 196 S/ Cm, viscosity 500mPa.s, ii〇°c solid state when dry is divided into 7.2% by mass of white slurry 1 483g » This slurry is filtered by Nutsche (5C, manufactured by Toyo Filter Paper Co., Ltd.). After the wet cake was dried at Π 0 ° C, the dried cake was pulverized using a household mixer to obtain a powder having a specific surface area of 49 m 2 /g. As a result of X-ray powder diffraction analysis of this powder, diffraction peaks of basic zinc citrate, zinc phenylphosphonate and magnesium hydroxide were observed. The powder was 32% by mass in terms of cyanuric acid, 42% by mass in terms of zinc, 16% by mass in terms of phenylphosphonic acid, and 3% by mass in terms of magnesium. Then, after dispersing the powder in pure water, the results are observed by a transmission electron microscope, and the needle-like particles of the basic zinc cyanurate having a major axis of 200 to 800 nm and a short axis of 20 to 60 nm, and a long axis and The pulverized particles of zinc phenylphosphonate having a short axis of from 1 to 500 nm and magnesium hydroxide are uniformly dispersed. The results are shown in Table 3. Further, a photograph observed by a transmission electron microscope is shown in Fig. 7. (Synthesis Example 1 3) 3 13 g of an aqueous magnesium phenylphosphonate solution prepared in Synthesis Example 11 and 1160 g of pure water were mixed in a 2-liter polymer container, and then immersed in a warm bath, and heated to make the mixed aqueous solution 3 0 °C. After the mixed aqueous solution reached 3 ° C, it was stirred at a concentration of 3 300 rpm using a dispersion wing, and 30.3 g of a cyanuric acid powder (manufactured by Nissan Chemical Industries Co., Ltd.) was added, and heating was carried out while further -41 - 201219406 Stir vigorously for 40 minutes. Then, 50.7 g of a white slurry was prepared by adding 57.4 g of zinc oxide powder (two types of zinc oxide manufactured by Seiko Chemical Co., Ltd.) with vigorous stirring while dispersing the wings. At this time, the temperature of the slurry was 38 ° C, and the slurry temperature was maintained at 38 ° C. The mixture was heated while stirring in a warm bath for 8 hours with a dispersion wing. Therefore, pH 8.6, conductivity 133 #5/〇111, viscosity 700111?&.3., 110 were obtained. (: The solid content at the time of drying was divided into 6.6 mass% of a white slurry of 1 560 g. This slurry was subjected to Nutsche filtration using a filter paper (5C, manufactured by Toyo Filter Co., Ltd.), and the obtained wet cake was subjected to 110 ° C. After drying, the dried filter cake was pulverized using a household mixer to obtain 100 g of a powder having a specific surface area of 56 m 2 /g. As a result of X-ray powder diffraction analysis of the powder, basic zinc cyanurate and phenylphosphine were observed. a diffraction peak of zinc acid and magnesium hydroxide. The powder is 35 mass% in terms of cyanuric acid, 40% by mass in terms of zinc, 15% by mass in terms of phenylphosphonic acid, and 1.2 mass in terms of magnesium. Then, after the powder was dispersed in pure water, the needle-like particles of basic zinc cyanurate having a long axis of 200 to 800 nm and a short axis of 20 to 60 nm were observed by a transmission electron microscope. The long axis and the short axis are 100 to 500 nm of zinc phenylphosphonate and magnesium hydroxide. The results are shown in Table 3. (Synthesis Example) Adding pure water to a 2 liter polymer container 7 g of the aqueous solution of magnesium phenylphosphonate obtained in Synthesis Example 1 3 3 3 g. Using a dispersing wing at 3,300 rpm while vigorously stirring, while putting in a cyanuric acid powder (manufactured by Nissan Chemical Industries Co., Ltd.) 33.lg', then 'distributing the wing-42-201219406 while vigorously interfering with the input of zinc oxide 57.4 g of powder (two types of oxidation) made of pulverization, and 1400 g of white hair was produced. The slurry temperature at this time was 26 ° C. Then, the slurry temperature was 28 after vigorously stirring with the dispersion wing for 8 hours. °C. Therefore, ΡΗ8·0, conductivity 275 μS/cm, viscosity 1040 mPa·s, and solid content of 7.6 mass% of white slurry 1400 g when dried at 110 ° C. The filter paper (5C) was used. , (Noryang filter paper system) was subjected to Nutsche filtration, and the obtained wet cake was dried at 1 1 〇 ° C. The dried filter cake was pulverized using a household mixer to obtain a powder having a specific surface area of 6 2 m 2 /g. 〇5g. As a result of X-ray powder diffraction analysis of this powder, a diffraction peak of basic zinc cyanurate, zinc phenylphosphonate and magnesium hydroxide was observed. The powder was 32 in terms of containing cyanuric acid. % by mass, 42% by mass for zinc, and 16% by mass for phenylphosphonic acid. And the magnesium content was 1.3% by mass. Then, after dispersing the powder in pure water, the observation was carried out by a transmission electron microscope to observe an alkalinity of a long axis of 100 to 300 nm and a short axis of 10 to 3 Onm. The needle-like particles of zinc cyanuric acid, the zinc phenylphosphonate having a major axis and a minor axis of 50 to 200 nm, and the particulate particles of magnesium hydroxide. The results are shown in Table 3. (Synthesis Example 1 5) The same operation as in Synthesis Example 12 was carried out except that the material temperature was set to 50 t, and ρ Η 7·7, conductivity 213 # S/cm, viscosity 720 mPa · s, and 1 1 〇 ° c were solidified into 7_6 mass. % white slurry 14 80 g. The slurry was subjected to Nutsche filtration using a filter paper (5 C, manufactured by Toyo Filter Co., Ltd.), and the obtained wet cake was dried at 110 ° C. -43-201219406 Using a household mixer to dry the filter cake The powder was pulverized to obtain 102 g of a powder having a specific surface area of 35 m 2 /g. As a result of X-ray powder diffraction analysis of this powder, diffraction peaks of basic zinc cyanurate, zinc phenylphosphonate and magnesium hydroxide were observed. The powder was 32% by mass in terms of cyanuric acid, 42% by mass in terms of zinc, 16% by mass in terms of phenylphosphonic acid, and 1.3% by mass in terms of magnesium. Then, after dispersing the powder in pure water, the results of observation by a transmission electron microscope revealed that needles of alkaline zinc cyanurate having a long axis of 200 to 1000 nm and a short axis of 40 to 80 nm were observed. The particles, the major axis and the minor axis are 200 to 600 nm of zinc phenylphosphonate and particulate particles of magnesium hydroxide. The results are shown in Table 3 (Synthesis Example 16). The same operation as in Synthesis Example 12 was carried out except that the slurry temperature was changed to 60 ° C to obtain pH 7.6, conductivity 183 yS/cm, and viscosity 640 mPa · s. The solid content at the time of drying at 1 10 ° C was divided into 7.6 mass% of a white slurry of 1480 g. The slurry was subjected to Nutsche filtration using a filter paper (5C, manufactured by Toyo Filter Co., Ltd.), and the obtained wet cake was dried at 11 (TC), and the dried cake was pulverized using a household mixer to obtain a specific surface area of 2 A powder of 6 m 2 /g of 102 g. As a result of X-ray powder diffraction analysis of this powder, a diffraction peak of basic zinc cyanurate, zinc phenylphosphonate and magnesium hydroxide was observed. The powder contained melamine. The acid is 32% by mass, the zinc is 42% by mass, the phenylphosphonic acid is 16% by mass, and the magnesium is 1.3% by mass. Then, the powder is dispersed in pure water and then passed through a transmission electron microscope. As a result of observation, the needle-like particles of alkaline zinc cyanurate having a major axis of 300 to 1000 nm and a short axis of 44 - 201219406 40 to 100 nm, and zinc phenylphosphonate having a major axis and a short axis of 300 to 800 nm The granules of the magnesium hydroxide were dispersed in the same manner. The results are shown in Table 3. (Synthesis Example 1 7) 195 g of an aqueous solution of magnesium phenylphosphonate prepared in Synthesis Example 11 was placed in a 2-liter polymer container. After mixing with 1194g of pure water, it is immersed in a warm bath and heated to make the mixed aqueous solution become 30 °C. When the mixed aqueous solution reaches 3 °C, it is stirred at a concentration of 3 3 00 rPm while using a dispersion wing, and 33.lg of cyanuric acid powder (manufactured by Nissan Chemical Industries Co., Ltd.) is added, and heating is performed on the other side. The mixture was vigorously stirred for 40 minutes. Then, 57.4 g of zinc oxide powder (two types of zinc oxide manufactured by Seiko Chemical Co., Ltd.) was placed while stirring vigorously to obtain a white slurry of 1,48 g. The slurry temperature at this time was 3 8 ° C, the slurry temperature was maintained at 3 8 ° C, while heating in the warm bath while vigorously stirring with the dispersion wing for 8 hours, to obtain pH 8.1, conductivity 142 / zS / cm, viscosity 540mPa. s, solidification at 110 ° C was divided into 7.2% by mass of white slurry 1 483 g. This slurry was subjected to Nutsche filtration using filter paper (5C, manufactured by Toyo Filter Paper Co., Ltd.), and the obtained wet cake was After drying at 110 ° C, the dried filter cake was pulverized using a household mixer to obtain a powder having a specific surface area of 52 m 2 /g, 4 g. For the powder, X-ray powder diffraction analysis was carried out, and alkali three was observed. Winding of polycyanide, zinc phenylphosphonate and magnesium hydroxide The powder is 33% by mass in terms of cyanuric acid, 46% by mass in terms of zinc, 10% by mass in terms of phenylphosphonic acid, and 0.8% by mass in terms of magnesium. Then, the powder is pure water- 45- 201219406 After dispersing, as observed by a transmission electron microscope, acicular particles of the basic zinc cyanurate having a major axis of 20 0 to 80 nm and a short axis of 20 to 60 nm were observed, long axis and short The axis is 100 to 500 nm of zinc phenylphosphonate and particulate particles of magnesium hydroxide. The results are shown in Table 3. (Synthesis Example 1 8) 3 68 kg of pure water was placed in a SUS container having a jacket of 700 liters in a volume of 700 liters, and a Mixer (Ashizawa Finetech Co., Ltd.) equipped with a dispersion of 300 inrn diameter was used. 20.3 kg of zinc oxide powder (two types of zinc oxide manufactured by Seiki Chemical Co., Ltd.) was placed at a dispersion of 500 rpm. In order to raise the temperature of the zinc oxide slurry to 49 ° C, the jacket water was warmed. When the zinc oxide slurry reaches 40 ° C on the way, the number of revolutions of the dispersion wings is increased to 800 rpm - while dispersing the mixture, the acetyl cyanide powder (manufactured by Nissan Chemical Industries Co., Ltd.) is divided into three groups of 1.7 kg three times. Put in at intervals of 30 minutes. After the cyanuric acid powder was charged, the temperature of the slurry was changed to 49 ° C, and the temperature of the jacket water was adjusted to maintain the temperature. The molar ratio of zinc oxide/cyanuric acid was 2.75, and the concentration of cyanuric acid relative to water was 2.9% by mass. This slurry was strongly dispersed for 9 hours as it was at a number of revolutions of the dispersed wing of 800 rpm. Therefore, a solid slurry having a pH of 7.5, a conductivity of 29/zS/cm, a viscosity of 866 mPa·s, and a drying temperature of 110 ° C was obtained, and was classified into a white slurry of 8.3 mass% of 395 kg. As a result of X-ray powder diffraction analysis of the dried powder of 110 °C of the obtained white slurry, a diffraction peak of alkaline zinc cyanurate was observed. The fine particles contained in the obtained white slurry were observed by a transmission electron microscope, and the long axis was -46 - 201219406 200 to 800 nm, the short axis was 20 to 50 nm, and the dry Sw was 3 5 m 2 /g at 110 ° C. Basic zinc cyanurate. The obtained basic zinc cyanuric acid conversion concentration paste 589 g was placed in a 1 liter polymer bottle--30 mm dispersion wing at 3 200 rpm while vigorously synthesizing the magnesium phenylphosphonate prepared in Example 11. Aqueous solution 1 68 g for 6 hours. Therefore, a slurry having a pH of 8.5 and a conductivity of 1,840 mPa·s was obtained, and filtered using Nut filter (5C, East), and the obtained wet cake was pulverized using a household mixer. 5 g 2 /g of powder 56g. As a result of X-ray irradiation of this powder, a diffraction peak of basic zinc cyanurate and phenylphosphonic acid was observed. This powder was 42% by mass in terms of cyanuric acid and 16% by mass in terms of phenylphosphonic acid. Then, after dispersing the powder in pure water, as a result of microscopic observation, it was observed that the long axis was 20 (l·20 to 60 nm of zinc citrate needle-like particles of 100 to 500 nm of zinc phenylphosphonate). And magnesium hydroxide | Table 3. (Synthesis Example 1 9) After mixing 24 kg of pure water and 1.88 kg of zinc oxide powder (zinc chemical zinc oxide) into a mixture of 200 liters of volume, the mixture was stirred and mixed to prepare zinc oxide. In the white ί, which has a specific surface area of 8.3% by mass after drying, the diameter is 'dispersed, and after being put in, it is more strongly dispersed at 88 μS/cm. Viscosity: Made from foreign filter paper (sand) The obtained specific surface area is a linear powder diffraction analysis of zinc and magnesium hydroxide of 32% by mass, zinc side, and magnesium for 1.3. The penetrating electron is -800 nm, the short axis is, and the major axis and the minor axis are: The results are as follows: in the two kinds of tanks made of (shares), the slurry of 7.62 mass% is used, and the weight of the slurry is -47-201219406. Then, the inner wall of the effective volume of 10.66 liters is the horizontal beads of the urethane resin. In a honing machine (Ashizawa Finetech (system) system zetaLMZ25), a Φ 1 mm stabilized zirconium is placed. 66 kg of beads were crushed. After 144 kg of pure water was placed in a circulating tank of water having a water temperature of 13 ° C as a jacketed water, the horizontal bead honing machine was driven at a peripheral speed of 9 · 5 m / sec. While rotating the clock, the pure water is supplied to the horizontal bead honing machine at a supply rate of 2 2 · 1 kg/min to circulate the pure water. The cyanuric acid powder is introduced after the start of the cycle (Nissan Chemical Industry Co., Ltd.) 1.19 kg. After the cyanuric acid powder was charged, the temperature of the circulating slurry was adjusted to 42 ° C, and then 24.6 kg of zinc oxide slurry having a zinc oxide equivalent concentration of 7.69 mass% was divided into 5 times. The addition was carried out for 1 hour. After the addition, the slurry of the horizontal bead honing machine was also rotated at a peripheral speed of 9.5 m/sec, and the slurry was circulated for 7 hours at a supply rate of 22. lkg/min. Dispersion, and also adjust the temperature of the circulating slurry to 4 2 °C. Therefore, ρΗ7·9, conductivity 206"S/cm, viscosity 86riiPa.s, basic zinc cyanurate conversion 167 kg of a white slurry having a concentration of 1.8% by mass. X-rays were applied to the dried powder of 1 10 ° C of the obtained white slurry. The result of the powder diffraction analysis was that no diffraction peak of cyanuric acid and zinc oxide belonging to the raw material was observed, but a diffraction peak of basic zinc cyanurate was observed. This powder was in the form of cyanuric acid. 39% by mass, and 49% by mass in terms of zinc. Then, when the fine particles contained in the obtained white slurry were observed by a transmission electron microscope, the long axis was 400 to 12 〇〇 nm, and the short axis was 20 ~40 nm, the average particle diameter D 5 〇 measured by the laser diffraction method is 397 nm, and the specific surface area Sw after drying at 70 ° C is 5 4 m 2 /g of basic zinc cyanurate. Knot -48- 201219406 The results are shown in Table 3. Further, a photograph observed by a transmission electron microscope is shown in Fig. 8. (Synthesis Example 20) 156 g of an aqueous solution of magnesium phenylphosphonate prepared in Synthesis Example 11 and 1 23 3 g of pure water were mixed in a 2-liter polymer container, and then immersed in a warm bath, and heated to make the mixed aqueous solution 30 °C. After the mixed aqueous solution reached 3 ° C, 36.4 g of cyanuric acid powder (manufactured by Nissan Chemical Industries Co., Ltd.) was added to the mixture at a concentration of 3,300 rpm, and the mixture was stirred while being heated. minute. Then, 57.4 g of zinc oxide powder (two kinds of zinc oxides manufactured by Seiko Chemical Co., Ltd.) was placed while vigorously stirring, and a white slurry of 1,48 g was obtained. The slurry temperature at this time was 38 ° C, and the slurry temperature was maintained at 38 ° C. The mixture was stirred while stirring in a warm bath for 8 hours to obtain a pH of 8.4 and a conductivity of 130 /. /S/cm' viscosity 550 mPa.s, solid state at 110 ° C when dry is divided into 7.2% by mass of white slurry 1 483 g. The slurry was subjected to Nutsche filtration using a filter paper (5C, manufactured by Toyo Filter Co., Ltd.), and the obtained wet cake was dried at 110 ° C, and then the dried cake was pulverized using a household mixer to obtain a specific surface area of 60 m 2 . /g powder 103g. As a result of X-ray powder diffraction analysis of this powder, diffraction peaks of basic zinc cyanurate, zinc phenylphosphonate and magnesium hydroxide were observed. The powder was 34% by mass in terms of cyanuric acid, 46% by mass in terms of zinc, 8% by mass in terms of phenylphosphonic acid, and 0.6% by mass in terms of magnesium. Then, the powder was dispersed in pure water, and as a result of observation by a transmission electron microscope, an alkaline zinc cyanurate having a long axis of ?49-201219406 2 00 to 800 nm and a short axis of 20 to 60 nm was observed. The acicular particles, the long axis and the short axis are 100 to 500 nm of zinc phenylphosphonate, and the particulate particles of magnesium hydroxide. The results are shown in Table 3. (Synthesis Example 2 1 ) After adding 184 g of pure water and 4.7 g of phenylphosphonic acid (manufactured by Seiko Chemical Co., Ltd.) to a 2 liter polymer container, the mixture was immersed in a warm bath and heated to make the mixed aqueous solution 30 °C, when the mixed aqueous solution reached 30 °C, the mixture was stirred at 330 rpm using a dispersion wing, and 36.4 g of cyanuric acid powder (manufactured by Nissan Chemical Industries Co., Ltd.) was added. Stir vigorously for 40 minutes while warming. Then, 57.4 g of zinc oxide powder (two types of zinc oxide manufactured by Seiko Chemical Co., Ltd.) was placed while vigorously stirring, and a white slurry of 1,48 g was obtained. At this time, the slurry temperature was 38 ° C, and the slurry temperature was maintained at 38 ° C. The mixture was stirred while stirring in a warm bath for 8 hours with a dispersion wing. Therefore, p Η 6.3, a conductivity of 151 " S/cm, a viscosity of 640 mPa·s, and a solid content of 7.2% by mass of a white slurry of 1 4 8 3 g at 110 ° C were obtained. The slurry was subjected to Nutsche filtration using a filter paper (5C, manufactured by Toyo Filter Co., Ltd.), and the obtained wet cake was dried at 1 1 ° C, and then the dried cake was pulverized using a household mixer to obtain a specific surface area. It was 98 g of a powder of 15 m 2 /g. As a result of X-ray powder diffraction analysis of this powder, diffraction peaks of basic zinc cyanurate and zinc phenylphosphonate were observed. The powder was 34% by mass in terms of cyanuric acid, 46% by mass in terms of zinc, and 1% by mass in terms of phenylphosphonic acid. Then, after dispersing the powder in pure water, the results of observation by a transmission electron microscope -50-201219406, an alkali zinc cyanurate needle having a long axis of 200 to 600 nm and a short axis of 20 to 40 nm was observed. The coarse particles of zinc phenylphosphonate having a shape of a long axis and a short axis of 2000 to 3000 nm. The results are shown in Table 3, 0 [nuclear agent evaluation-1]. (Example 9) The dried powder (resin for resin nucleating agent) obtained in Synthesis Example 1 1 was 5555 g and polylactic acid resin. (NW300 1 D, number average molecular weight 72,000, melting point 164 ° C, manufactured by Natureworks) 54.5 g was mixed and placed in a small two-axis kneading extruder (Blanda) that has been heated to 170 °C The mixture was kneaded at 50 rpm for 15 minutes to prepare a resin composition. After cooling, the resin composition was taken out, and the Teflon sheet was held with a brass plate, and placed in a hot press which had been heated to an upper portion of 185 ° C and a lower portion of 185 ° C so that the thickness of the film became 〇.4 mm. 0.5 kgf was pressed to form a film. The film sample was cut into small pieces, and the temperature was raised to 200 ° C at 200 ° C /min and held for 5 minutes as it was, and then cooled at 5 ° C / min to carry out DSC measurement (Seiko Electronics Co., Ltd. DSC- 200). The crystallization temperature Tc was measured from the apex of the exothermic peak from the crystallization of polylactic acid as observed during cooling. Further, the film sample was cut into small pieces, and the temperature was raised to 20 ° C at 1 ° C / min and held for 5 minutes as it was, and then cooled to 110 ° C at 100 ° C / min. The DSC measurement was carried out for 10 minutes at 〇 ° C (DSC-200 manufactured by Seiko Electronics Co., Ltd.). The crystallization rate was measured by measuring the time from the apex of the crystallization peak of the crystallization of polylactic acid by maintaining the temperature at U 〇 °C -51 - 201219406. The results are shown in Table 4. In Table 4, the concentration of the resin nucleating agent is described as a part by mass of the resin nucleating agent with respect to 1 part by mass of the resin. (Example 10) The same operation as in Example 9 was carried out except that the dry powder of 110 ° C obtained in Synthesis Example 12 was used instead of the dried powder of 110 ° C obtained in Synthesis Example 1 1 . The crystallization temperature Tc of polylactic acid and the crystallization rate. The results are shown in Table 4. Further, 'the visible light transmittance of the obtained film was measured by a color difference meter (Tokyo Electric Color TC-1800 type), and the haze was obtained by using SPECTRAL HAZE METER (Tokyo Electric Color TC-H3DPK-MK type), and the result was The visible light transmittance at a wavelength of 50 nm was 44% and the haze was 56. (Example 1 1) The same procedure as in Example 9 was carried out except that 1 1 0 ° C dry powder 0·5 5 g obtained in Synthesis Example 13 was used instead of the 1 1 (TC dry powder obtained in Synthesis Example 1). The crystallization temperature Tc and the crystallization rate of the polylactic acid were measured. The results are shown in Table 4. (Example 1 2) Except that 1 1 〇 obtained in Synthesis Example 14 was used. (: 0.5 5 g of dry powder) The crystallization temperature Tc and the crystallization rate of the polylactic acid were measured in the same manner as in the above-mentioned Example 9-52-201219406 except that the n 〇t dry powder obtained in the synthesis example was used. The results are shown in Table 4. Example 1 3) The polylactic acid was measured in the same manner as in Example 9 except that 1 1 (TC dry powder 〇. 55 g obtained in Synthesis Example 15 was used instead of 1 1 (TC dry powder obtained in Synthesis Example 1). The crystallization temperature Tc and the crystallization rate are shown in Table 4. (Example 1 4) The same procedure as in Synthesis Example 1 was used except that the 1 1 Ot dry powder obtained in Synthesis Example 1 was used. The same operation as in Example 9 except for the dry powder of 1 1 was carried out, and the crystallization temperature Tc and the crystallization rate of the polylactic acid were measured. The results are shown in Table 4. In addition, the visible light transmittance of the obtained film was measured using a color difference meter (Tokyo Electric Color TC-1800MK type), and the haze was SPECTRAL HAZE METER (Tokyo Electric Color TC-H3DPK-MK) The results were as follows, and the visible light transmittance at a wavelength of 550 nm was 75%, and the haze was 24. (Example 1 5) Instead of using 0.55 g of a dry powder of 10 ° C obtained in Synthesis Example 16 instead of the synthesis The crystallization temperature Tc and the crystallization rate of the polylactic acid were measured in the same manner as in Example 9 except for the dry powder at 110 °C obtained in Example 1. The results are shown in Table 4. -53 - 201219406 (Implementation Example 1 6) The same operation as in Example 9 was carried out except that the dried powder of 〇 〇 ° C obtained in Synthesis Example 17 was used instead of the dry powder of 1 1 〇 ° C obtained in Synthesis Example 1 The crystallization temperature TC of lactic acid and the crystallization rate are shown in Table 4. (Example 1 7) In place of the synthesis example 1 1 obtained by using 0.55 g of a dry powder of 10 ° C obtained in Synthesis Example 18 The same procedure as in Example 9 was carried out except that the dried powder was dried at 10 ° C, and the crystallization temperature of the polylactic acid was measured. Tc and crystallization rate. The results are shown in Table 4. (Example 1 8) 7.0 g of dried zinc cyanide salt of the basic zinc cyanide obtained in Synthesis Example 19 and containing 29% by mass of zinc And zinc phenylphosphonate (trademark ECOPROMOTE, manufactured by Nissan Chemical Industries Co., Ltd.) of 71% by mass of phenylphosphonic acid was replaced by the synthesis example 1 1 ; 1 〇 t dry powder, mixed with a household powder mixer to prepare a mixed powder for evaluation. The crystallization temperature tc and the crystallization rate β of the polylactic acid were measured in the same manner as in Example 9 except that the mixed powder 〇·5 5 g was used instead of the one obtained by the synthesis example u. As shown in Table 4. $ 'The visible light transmittance of the obtained film is measured by a color difference meter (Dongzu Color TC-1800MK type), and the haze is obtained by using SPECTRAL HAZE METER (Tokyo Electric Color TC.H3DPK-MK type) The result was -54 - 201219406. The visible light transmittance at a wavelength of 550 nm was 40%, and the haze was 61. (Example 1 9) 5.0 g of zinc phenylphosphonate (trademark ECOPROMOTE Nissan Chemical X Co., Ltd.) was used. And 16. g of the no-C dry powder of the basic zinc cyanide obtained in Synthesis Example 19 and 0.4 g of magnesium hydroxide (manufactured by Kanto Chemical Co., Ltd.) were mixed using a household powder mixer. A mixed powder containing 29% by mass of cyanuric acid, 43% by mass of zinc, 16% by mass of phenylphosphonic acid, and 3% by mass of magnesium. In addition to using 0.55 g of the mixed powder, the 1 1 〇° obtained in the synthesis example 11 was replaced. The same procedure as in Example 9 was carried out except for the C dry powder, and the crystallization temperature of the polylactic acid was measured. Tc and crystallization rate. The results are shown in Table 4. (Example 20) In place of the 1 1 〇 ° C dry powder obtained in Synthesis Example 1 except that 0.55 g of a dry powder of 10 ° C obtained in Synthesis Example 20 was used. The crystallization temperature Tc and the crystallization rate of the polylactic acid were measured in the same manner as in Example 9. The results are shown in Table 4. (Example 2 1) The l l ° ° C obtained in the synthesis example 21 was used. The same procedure as in Example 9 was carried out except that the dry powder was 0.55 g instead of the dry powder of 1 1 〇 °C obtained in Synthesis Example 1, and the slurry became PH7 when the crystallization temperature Tc and the crystallization rate of the polylactic acid were measured. Hereinafter, a part of the polylactic acid was dissolved in the nucleating agent for -55-201219406 resin. (Comparative Example 3) The same procedure as in Example 9 was carried out except that the nucleating agent for the resin was not added, and the polylactic acid was measured. The crystallization temperature Tc and the crystallization rate are shown in Table 4. The visible light transmittance of the obtained film was measured by a color difference meter (Tokyo Electric Color TC-1800MK type), and the haze was SPECTRAL HAZE METER (Tokyo). Electrochromic TC-H3DPK-MK type) is obtained, and the result The visible light transmittance at a wavelength of 55 〇 nm was 87%, and the haze was 14. (Comparative Example 4) The synthesis example 1 was replaced with zinc phenylphosphonate (trademark ECOPROMOTE, manufactured by Nissan Chemical Industries Co., Ltd.). The same operation as in Example 9 was carried out except that the obtained dry powder of 1 1 〇 ° c was measured, and the crystallization temperature T c and the crystallization rate of the polylactic acid were measured. The results are shown in Table 4. Further, the results of observation of the above zinc phenylphosphonate by a transmission electron microscope are shown in Fig. 9.尙, the above zinc phenylphosphonate has a specific surface area of 12 m 2 /g. In addition, the visible light transmittance of the obtained film was measured using a color difference meter (Tokyo Electric Color TC-1800MK type). The haze was obtained by using SPECTRAL HAZE METER (Tokyo Electric Color TC-H3DPK-MK type), and the result was wavelength. 5 50 nm has a visible light transmittance of 30% and a haze of 70. (Comparative Example 5) -56-201219406 In addition to the use of zinc phenylphosphonate (trademark ECOPROMOTE manufactured by Nissan Chemical Industries Co., Ltd.) 1·1 1 g in place of the dry powder of i丨〇乞 obtained in Synthesis Example 1, 9 The same operation was carried out, and the crystallization temperature T c and the crystallization rate of the polylactic acid were measured. The results are shown in Table 4. Further, 'the visible light transmittance of the obtained film was measured by a color difference meter (Tokyo Electric Color TC-1800MK type), and the haze was obtained by using SPECTRAL HAZE METER (Tokyo Electric Color TC-H3DPK-MK type), and the result was wavelength. The visible light transmittance at 550 nm is 60% and the haze is 41. (Reference Example 1) The same procedure as in Example 1 except that the dry powder of 1 0 ° C of the basic zinc cyanurate obtained in Synthesis Example 19 was used instead of the dry powder of no〇c obtained in Synthesis Example 11. 9 The same operation was carried out, and the crystallization temperature Tc and the crystallization rate of the polylactic acid were measured. The results are shown in Table 4. Further, 'the visible light transmittance of the obtained film was measured by a color difference meter (Tokyo Electric Color TC-1800MK type), and the haze was obtained by using SPECTRAL HAZE METER (Tokyo Electric Color TC-H3DPK-MK type), and the result was The visible light transmittance at a wavelength of 550 nm was 39%, and the haze was 64. (Reference Example 2) Except that the dry powder of 110 ° C of the basic zinc cyanide obtained in Synthesis Example 19 was used instead of the dry powder of 1 1 〇 °c obtained in Synthesis Example U In the same manner as in Example 9, the crystallization temperature Tc and the crystallization rate of the polylactic acid were measured. The results are shown in Table 4. -57- 201219406 Further, the visible light transmittance of the obtained film was measured by a color difference meter (Tokyo Electric Color TC-1800MK type), and the haze was obtained by using SPECTRAL HAZE METER (Tokyo Electric Color TC-H3DPK-MK type). As a result, the visible light transmittance at a wavelength of 550 nm was 67%, and the haze was 29. As a result, as shown in Table 4, it was confirmed that Examples 9 to 2 were compared with Comparative Example 3 in which no crystal nucleating agent was added, or Reference Examples 1 and 2' containing only basic zinc cyanurate. The crystallization temperature is remarkably high, and the crystallization rate is remarkably high, and the nucleating agent performance is extremely excellent. Further, in Comparative Examples 4 and 5, which contained only a high price of zinc phenylphosphonate, Examples 9 to 21 were the same degree of crystallization temperature and crystallization rate, and the metal salt with phenylphosphonic acid was used. When a low-cost alkaline zinc cyanurate fine particle is used together with a metal salt of phenylphosphonic acid, it has been confirmed that the effect of increasing the crystallization rate and the crystallization temperature of the resin can be achieved, and the effect of cost reduction is achieved. Further, the crystallization rate and the crystallization temperature of Example 1 were higher than those of Example 9 and Example 19 in which the components were the same. Therefore, it is known that the performance of the crystal nucleating agent is excellent when the raw material is mixed with zinc phenylphosphonate and magnesium hydroxide in a simple manner to produce a raw material by reacting as in Example 9. [Crystalline Evaluation-2] (Example 22)
將合成例1 1所得到的鹼性三聚氰酸鋅之1 1 〇 °C乾燥 粉（樹脂用晶核劑）36mg，及聚丙嫌樹脂（novatec PP -58- 201219406 MA3、數平均分子量 111，000、融點 165 °C 、Japan Polychem (股）製）3.6g置入於已加熱至185°C之混練機 (LABO PLASTOMILL東洋精機（股）製）中5分鐘，以 5 Orpin進行混練而製造樹脂組成物。冷卻後，將樹脂組成 物取出，以鐵氟龍薄片與黃銅板挾持，置於已加熱至上部 185°C、下部185 t之熱壓製機中，使薄膜之厚度成爲 0.4mm般地以〇.5kgf進行加壓，製成薄膜。將此薄膜狀 樣本切取成小片，以1〇〇°C/分鐘昇溫至20(TC並原樣地保 持5分鐘，之後，以5 t /分鐘予以冷卻來進行D S C測定 (Seiko電子（股）製DSC-200 )，由冷卻時所觀測到來 自於聚丙烯之結晶化之發熱峰頂點來測定結晶化溫度Tc 。之後，以l〇〇°C /分鐘昇溫至200°C並原樣地保持5分鐘 ，之後’以100°C/分鐘冷卻至130°C後，進行以13CTC保 持5分鐘之DSC測定（Seiko電子（股）製DSC-200)。 由保持於1 3 0 °C時所觀測到來自於聚丙烯之結晶化之發熱 峰頂點之時間’來測定結晶化速度。結果如表5所示。 (比較例6 ) 除了未添加樹脂用晶核劑以外，與實施例2 2進行同 樣之操作’測定聚丙烯之結晶化溫度Tc及結晶化速度。 結果如表5所示。 (比較例7 ) 除了使用苯膦酸鲜（商標ECOPROMOTE日產化學工 -59- 201219406 業（股）製）取代合成例！丨所得到的丨〗〇 C乾燥粉以外 ，與實施例2 2進行同樣之操作’測定聚丙烯之結晶化溫 度Tc及結晶化速度。結果如表5所示。 (參考實施例3) 除了使用合成例19所得到的鹼性三聚氰酸鋅之11〇 °C乾燥粉36mg取代合成例u所得到的！ 1〇t：乾燥粉以外 ’與實施例22進行同樣之操作，測定聚丙烯之結晶化溫 度T c及結晶化速度。結果如表5所示。 如表5所示般，相較於未添加樹脂用晶核劑之比較例 ό、或僅含有鹼性三聚氰酸鋅之參考實施例3，確認到實 施例22之結晶化溫度顯著地較高，且，結晶化速度顯著 地高、晶核劑性能非常地優異。 又’相較於僅含有高價格的苯膦酸鋅之比較例7，實 施例22爲相同程度之結晶化溫度及結晶化速度，藉由與 較苯膦酸之金屬鹽爲低成本的鹼性三聚氰酸鋅微粒子一起 使用苯膦酸之金屬鹽，即使是在聚丙烯樹脂中，亦確認到 可兼具所謂的提高樹脂之結晶化速度及結晶化溫度之效果 ，與所謂的低成本化之效果。 -60- 201219406 【8〕 黏度 (inPa-s) ο 导 S 〇 1 卜 CD uo 〇 OO CO oo 〇 ufd LO «Ο 電導度 US/cm) οο CO <0 era CO CO uo C<l CO CO OO cs> 寸 oo oo CO era < « 宏 C-： c^a «〇 oo o oo 卜 1 ^ oo LO OO 0¾ οό CO CO 比表面積 (mVg) oo csa 0¾ ^r CO L〇 CSI CO L/d CO CO c^a C-3 Lf3 eft CO 守 LT7 g CO i M 分散濃度 (質量％) I_ CJO CO CO CO <〇 *>： C<J o： CO oo 〇〇 .:» C^3 CS3 分散溫度 (V) I_ OO CO oo CO OO CO oo e^a S g oo CQ σ> CsJ 切 CO CO OO CO Mg/^隣酸 (質量比） I_ I 0.40 0.40 1_ 0.40 0.40 0.40 0.40 0.40 0.40 I 0.40 o 苯膦酚 鹼性三聚氰酸鋅 (質量％) OO p— 4 OO oo 00 1 < OO OO o F ~H OO G 0¾ LO 减<3 2. 50 L 2.75 3.00 2.75 2.75 2.75 2.75 2. 75 2.50 2. 50 2. 50 合成例11 |合成例12 J |合成例13 1 |合成例14 I 合成例15 合成例16 合成例17 合成例18 合成例19 合成例20 合成例21 -61 - 201219406 【寸揪】 結晶化速度 份） 0. 57 , 0.47 0.53 0.48 0.55 0.66 0. 68 0. 76 0.57 0.65 0.88 0. 90 1. 08 4.85 0. 64 0. 75 2. 20 2. 32 結晶化溫度 CC) 130.0 130.4 129.6 129. 8 127.6 129.2 129. 1 129.6 129.3 127.4 128. 1 123.7 109.7 129.2 127.3 118.8 114.0 樹脂用晶 核劑濃度 (質量份） CD C3 〇 〇 r·^ Ο CO G> Ο Ο Ο Ο Ο Ο 樹脂用結晶核剤 Ζ翁膦酸 (質量比） Π CO csj C— C^3 CO c<i CO c^i CO c>5 CO 〇5 CO c〇 c<i 〇 卜 c^3 卜 Lri CO 1 CD o 8 8 Mg (質量％) CO CO CO CO CO CO oo CD CO o CO 二 CO ¢=5 G Ο 苯膦酸 償量％) c〇 _ < CO ιλ CO ς〇 CO CO a CO τ·Η CO CO oo (〇 f · O t— 卜 〇 ο Zn (質量％) CO •^r 完 写 寸 CO *^r CO rr CD 切 03 守 CO CO CO CO G 0¾ σ·5 CO 0*5 0¾ 三聚氰酸 (質量％) <Ti C^3 CO CO Ln CO CN3 CO C^3 CO C^3 CO CO CO CO CO c^a CO 〇> CO CO CO o o 0¾ CO 0¾ CO 蘅酸 Sg<n 合成例11 合成例12 合成例13 合成例14 合成例15 合成例12 合成例16 合成例17 合成例18 合成例19 1 合成例20 合成例21 娜加 1 1 合成例19 1 實施例9 實施例10 1實施例11 1實施例12 1實施例13 實施例14 1實施例15 1實施例16 1實施例17 1實施例18 |實施例19 丨實施例20 |實施例21 |比較例3 |比較例4 |比較例5 參考實施例1 參考實施例2 -62- 201219406 -揪一 結晶化速度 份） 0.72 3.10 0.90 2. 00 結晶化溫度 CC) 130.2 122.7 130.0 124.8 樹脂用晶 核劑濃度 _(%)„ Ο 樹脂用晶核劑 Ζη/» 酸 (質量比） j 〇 8 Mg (質量％) CO — 〇 Q 〇 苯膦酸 (質量％) co • * 〇 ί= Zn (質量％) CO 呀 0¾ 三聚氰酸 (質量％) 0¾ CSJ 〇 CTi ΓΟ 蘅酸 嚙匡 S<n 蕕·Μ 合成例11 無添加 1 合成例19 實施例22 比較例6 比較例7 cn 辑 K 璐 -63- 201219406 【圖式簡單說明】 [圖1]合成例1之XRD繞射圖 [圖2]合成例1之TEM照片。 [圖3]合成例3之TEM照片。 [圖4]合成例7之TEM照片。 [圖5]合成例9之TEM照片。 [圖6]合成例1 1之XRD繞射圍 [圖7]合成例12之TEM照片。 [圖8]合成例19之TEM照片。 [圖9]於比較例4所使用苯膦画 型。 型。 鋅之TEM照片。 -64 -The dried zinc cyanurate obtained in Synthesis Example 1 1 1 〇 ° C dry powder (resin nucleating agent) 36 mg, and polyacrylic resin (novatec PP -58-201219406 MA3, number average molecular weight 111, 000, 165 °C, 165 °C, Japan Polychem (manufactured by Japan Polychem Co., Ltd.) was placed in a kneading machine (LABO PLASTOMILL manufactured by Toyo Seiki Co., Ltd.) heated to 185 ° C for 5 minutes, and manufactured by mixing with 5 Orpin. Resin composition. After cooling, the resin composition was taken out, and the Teflon sheet and the brass plate were held, and placed in a hot press which was heated to an upper portion of 185 ° C and a lower portion of 185 t so that the thickness of the film became 0.4 mm. .5kgf is pressurized to form a film. The film sample was cut into small pieces, and the temperature was raised to 20 (TC) at 1 ° C/min, and kept for 5 minutes as it was, and then cooled at 5 t /min to carry out DSC measurement (Seiko Electronics Co., Ltd. DSC) -200), the crystallization temperature Tc was measured from the apex of the exothermic peak from the crystallization of polypropylene observed at the time of cooling, and then the temperature was raised to 200 ° C at 10 ° C / min and held as it was for 5 minutes. After that, it was cooled to 130 ° C at 100 ° C / min, and then subjected to DSC measurement (Seiko Electronics Co., Ltd. DSC-200) held at 13 CTC for 5 minutes. Observed from the temperature observed at 130 ° C The crystallization rate was measured by the time of the apex of the crystallization of the polypropylene. The results are shown in Table 5. (Comparative Example 6) The same operation as in Example 2 was carried out except that the nucleating agent for the resin was not added. The crystallization temperature Tc and the crystallization rate of the polypropylene were measured. The results are shown in Table 5. (Comparative Example 7) In place of the synthesis example, phenylphosphonic acid (trademark ECOPROMOTE Nissan Chemical Co., Ltd. - 59-201219406) was used instead of the synthesis example.丨 丨 〇 〇 〇 C dry powder, and examples 2 2 The same operation was carried out 'The crystallization temperature Tc of the polypropylene and the crystallization rate were measured. The results are shown in Table 5. (Reference Example 3) Except that the basic zinc cyanurate obtained in Synthesis Example 19 was used. 〇 ° C dry powder 36 mg was replaced by the synthesis example u! 1 〇 t: dry powder except 'the same operation as in Example 22, the crystallization temperature T c of the polypropylene and the crystallization rate were measured. The results are shown in Table 5. As shown in Table 5, it was confirmed that the crystallization temperature of Example 22 was remarkable as compared with Comparative Example 3 in which no nucleating agent for a resin was added or Reference Example 3 containing only basic zinc cyanurate. The grounding speed is high, and the crystallization rate is remarkably high, and the nucleating agent performance is extremely excellent. Further, in the comparative example 7 which only contains a high price of zinc phenylphosphonate, the embodiment 22 has the same degree of crystallization temperature. And the crystallization rate, by using a metal salt of phenylphosphonic acid together with a metal salt of phenylphosphonic acid as a low-cost basic zinc cyanurate microparticle, even in a polypropylene resin, it is confirmed that both So-called increase in crystallization rate and crystallization temperature of the resin Effect, and the so-called cost reduction effect. -60- 201219406 [8] Viscosity (inPa-s) ο Guide S 〇1 Bu CD uo 〇OO CO oo 〇ufd LO «Ο Conductivity US/cm) οο CO < ;0 era CO CO uo C<l CO CO OO cs> inch oo oo CO era < « macro C-: c^a «〇oo o oo 卜 1 ^ oo LO OO 03⁄4 οό CO CO specific surface area (mVg) oo Csa 03⁄4 ^r CO L〇CSI CO L/d CO CO c^a C-3 Lf3 eft CO LT7 g CO i M Dispersion concentration (% by mass) I_ CJO CO CO CO <〇*>: C<J o: CO oo 〇〇.:» C^3 CS3 Dispersion temperature (V) I_ OO CO oo CO OO CO oo e^a S g oo CQ σ> CsJ cut CO CO OO CO Mg/^ o-acid (mass ratio) I_ I 0.40 0.40 1_ 0.40 0.40 0.40 0.40 0.40 0.40 I 0.40 o Phenylphosphine phenol basic zinc cyanurate (% by mass) OO p— 4 OO oo 00 1 < OO OO o F ~H OO G 03⁄4 LO minus < ;3 2. 50 L 2.75 3.00 2.75 2.75 2.75 2.75 2. 75 2.50 2. 50 2. 50 Synthesis Example 11 | Synthesis Example 12 J | Synthesis Example 13 1 | Synthesis Example 14 I Synthesis Example 15 Synthesis Example 16 Synthesis Example 17 Synthesis Example 18 Synthesis Example 19 Synthesis Example 20 Synthesis Example 21 -61 - 201219406 [Inch 揪] Crystallization speed fraction) 0. 57 , 0.47 0.53 0.48 0.55 0.66 0. 68 0. 76 0.57 0.65 0.88 0. 90 1. 08 4.85 0. 64 0. 75 2. 20 2. 32 Crystallization temperature CC) 130.0 130.4 129.6 129. 8 127.6 129.2 129. 1 129.6 129.3 127.4 128. 1 123.7 109.7 129.2 127.3 118.8 114.0 Crystal nucleating agent concentration (parts by mass) CD C3 〇〇r·^ Ο CO G> Ο Ο Ο Ο Ο 结晶 Crystallization of resin Nuclear phosphonate (mass ratio) Π CO csj C— C^3 CO c<i CO c^i CO c>5 CO 〇5 CO c〇c<i 〇卜c^3 卜 Lri CO 1 CD o 8 8 Mg (% by mass) CO CO CO CO CO CO oo CD CO o CO II CO ¢=5 G Ο phenylphosphonic acid replenishment %) c〇_ < CO ιλ CO ς〇CO CO a CO τ·Η CO CO oo (〇f · O t- 〇 〇 Zn (% by mass) CO • ^r End of writing CO *^r CO rr CD Cut 03 守CO CO CO CO G 03⁄4 σ·5 CO 0*5 03⁄4 Trimerization Cyanic acid (% by mass) <Ti C^3 CO CO Ln CO CN3 CO C^3 CO C^3 CO CO CO CO c^a CO 〇> CO CO CO oo 03⁄4 CO 03⁄4 CO 蘅 acid Sg<n Synthesis Example 11 Synthesis Example 12 Synthesis Example 13 Synthesis Example 14 Synthesis Example 15 Synthesis Example 12 Synthesis Example 16 Example 17 Synthesis Example 18 Synthesis Example 19 Synthesis Example 20 Synthesis Example 21 Nagar 1 1 Synthesis Example 19 1 Example 9 Example 10 1 Example 11 1 Example 12 1 Example 13 Example 14 1 Example 15 1 Example 16 1 Example 17 1 Example 18 | Example 19 Example 20 | Example 21 | Comparative Example 3 | Comparative Example 4 | Comparative Example 5 Reference Example 1 Reference Example 2 -62-201219406 -揪一Crystallization speed fraction) 0.72 3.10 0.90 2. 00 Crystallization temperature CC) 130.2 122.7 130.0 124.8 Crystal nucleating agent concentration _(%) „ 晶 Crystallizing agent for resin Ζη/» Acid (mass ratio) j 〇8 Mg ( Mass %) CO — 〇Q phenylphosphonic acid (% by mass) co • * 〇ί= Zn (% by mass) CO 呀 03⁄4 cyanuric acid (% by mass) 03⁄4 CSJ 〇CTi ΓΟ 蘅 匡 匡 &S<n 莸Μ Synthesis Example 11 No addition 1 Synthesis Example 19 Example 22 Comparative Example 6 Comparative Example 7 cn Series K 璐-63- 201219406 [Simplified description of the drawing] [Fig. 1] XRD diffraction pattern of Synthesis Example 1 [Fig. 2] TEM photograph of Synthesis Example 1. Fig. 3 is a TEM photograph of Synthesis Example 3. Fig. 4 is a TEM photograph of Synthesis Example 7. Fig. 5 is a TEM photograph of Synthesis Example 9. [Fig. 6] XRD diffraction of Synthesis Example 1 [Fig. 7] A TEM photograph of Synthesis Example 12. Fig. 8 is a TEM photograph of Synthesis Example 19. Fig. 9 is a phenylphosphine pattern used in Comparative Example 4. type. TEM photo of zinc. -64 -