201000509 六、發明說明： 【發明所屬之技術領域】 本發明有關聚異氰酸酯組成物及使用其之二液型塗料 組成物。 【先前技術】 使用聚異氰酸酯作爲一成分之二液型胺基甲酸酯塗料 由於可獲得耐候性或耐摩耗性優異之塗膜，故以往已使用 於建築物、土木建築物等之屋外基材之塗裝、汽車之修補 、塑膠塗裝等。 此塗料中，由於聚異氰酸酯之極性高，一般使用甲苯 或二甲苯等之芳香族烴溶劑或乙酸丁酯等之酯系溶劑等之 強溶劑，亦即溶解力強的溶劑。 此強溶劑由於臭味強，近幾年來基於作業環境之改善 或減低對地球環境之負荷觀點而言有敬而遠之之傾向。再 者’於舊塗膜上塗裝新的塗裝進行修補或重新粉刷之際， 於修補用塗料中含有具有高溶解力之強溶劑時，有發生使 舊塗膜彭潤及溶解而甚至連舊塗膜都有修補的必要。其結 果，有發生塗裝作業擴大化及繁雜化、塗裝費用增加、工 期延長等問題。 鑑於上述幾點，近年來持續開發易溶解於低極性有機 溶劑中之聚異氰酸酯。 例如，於專利文獻1 (特開平8 - 1 9 8 9 2 8號公報）中 ’揭示由脂環式二異氰酸酯與低極性有機溶劑之稀釋性爲 -5- 201000509 1 00%以上之多元醇反應所得之聚異氰酸酯作爲低極性溶 劑之稀釋性優異之聚異氰酸酯。又，此專利文獻中，亦揭 示以此聚異氰酸酯作爲硬化劑所得之塗膜其伸展性優異。 又，於專利文獻2(特開2 00 8-2 4 828號公報）中， 揭示使脂肪族及/或脂環式二異氰酸酯與碳數1〜20之單元 醇所得之具有特定脲基甲酸酯基（allophanate) /異尿氰 酸酯基莫耳比及特定分子量分布之聚異氰酸酯化合物作爲 對低極性有機溶劑之溶解性及與矽酸酯化合物之相溶性優 異之聚異氰酸酯。 上述專利文獻1之聚異氰酸酯雖然對低極性有機溶劑 之溶解性優異，但所得塗膜之破裂伸長度爲50%左右，其 伸展性方面尙有改良餘地。 另一方面，使用專利文獻1之聚異氰酸酯化合物所得 之塗膜之伸展性亦不充分。 又’任一種聚異氰酸酯就與作爲主劑之多元醇化合物 之相溶性方面亦要求進一步改善。 專利文獻1 :特開平8 - 1 98928號公報 專利文獻2:特開2008-24828號公報 【發明內容】 [發明欲解決之問題] 本發明係鑑於上述事情所成者，目的在於提供於低極 性有機溶劑中可溶且與多元醇化合物之相溶性優異 '可獲 得伸展性優異之塗膜之聚異氰酸酯組成物以及使用其之二 -6- 201000509 液型塗料組成物。 [用以解決問題之手段] 本發明人等爲達上述目的重複進行刻意檢討之結果， 發現於以基礎聚異氰酸酯與聚醚多元醇進行胺基甲酸酯化 反應所得之聚異氰酸酯組成物中，使用脲基甲酸酯基/異 尿氰酸酯基莫耳比在特定範圍者作爲基礎聚異氰酸酯，可 提高對於低極性有機溶劑之溶解性且由含有此聚異氰酸酯 組成物與多元醇之塗料所得之塗膜之柔軟性、伸展性及強 度獲得提高，因而完成本發明。 亦即，本發明提供： 1. 一種聚異氰酸酯組成物，其係使基礎聚異氰酸酯 與聚醚多元醇進行胺基甲酸酯化反應而得之聚異氰酸酯組 成物，其特徵爲上述基礎聚異氰酸酯係以脲基甲酸酯基/ 異尿氰酸酯基二9 0/10〜10 0/0 (莫耳比）含有脲基甲酸酯基 及異尿氰酸酯基。 2. 如上述1之聚異氰酸酯組成物，其中上述基礎聚 異氰酸酯係使脂肪族或脂環式二異氰酸酯與碳數1〜2 0之 單元醇，在脲基甲酸酯觸媒存在下反應而得者。 3·如上述1之聚異氰酸酯組成物，其中上述基礎聚 異氰酸酯係由使脂肪族或脂環式二異氰酸酯與碳數1〜20 之單元醇在脲基甲酸酯觸媒存在下反應而得之脲基甲酸酯 改質之聚異氰酸酯、以及脂肪族或脂環式二異氰酸酯之聚 異尿氰酸酯之混合物所構成。 201000509 4. 一種聚異氰酸酯組成物，其係使基 與聚醚多元醇進行胺基甲酸酯化反應而得之 成物，其特徵爲以脲基甲酸酯基/異 = 90/10〜1〇〇/〇(莫耳比）含有脲基甲酸酯基 基， 上述基礎聚異氰酸酯係由使脂肪族或脂 酯與碳數1〜20之單元醇在脲基甲酸酯觸媒 得之脲基甲酸酯改質之聚異氰酸酯、以及脂 二異氰酸酯之聚異尿氰酸酯之混合物所構成 5. 如上述1至4中任一者之聚異氰酸 中上述聚醚多元醇之數平均分子量爲1，000〜 6 · —種二液型塗料組成物，其含有上交 一者之聚異氰酸酯組成物以及多元醇化合物 7.如上述6之二液型塗料組成物，其 1 〇 ~ 8 0 °C之低極性有機溶劑或混合苯胺點爲 性有機溶劑。 [發明效果] 本發明之聚異氰酸酯組成物對於低極性 溶劑）之溶解性優異且與使用於二液型塗料 酸系之聚合物之相溶性良好。 由使用此聚異氰酸酯組成物之二異型塗 之塗膜之柔軟性優異，且拉伸強度以及拉伸 強韌者。 礎聚異氰酸酯 聚異氰酸酯組 尿氰酸酯基 及異尿氰酸酯 環式二異氰酸 存在下反應而 肪族或脂環式 〇 酯組成物，其 10,000° g 1至4中任 〇 含有苯胺點爲 5〜50°C之低極 有機溶劑（弱 之氟系或丙烯 料組成物所得 伸長度大而爲 -8 - 201000509 又’本發明之二液型塗料組成物由於在低極性有機溶 劑（弱溶劑）中爲可溶，且由於重複塗佈時不會侵蝕底層 ’故再塗佈性優異。 【實施方式】 &下，就本發明更詳細加以說明。 本發明之聚異氰酸酯組成物爲以脲基甲酸酯基/異尿 氰酸酯基= 90/10〜100/0(莫耳比）含有脲基甲酸酯基及異 尿氰酸酯基之基礎聚異氰酸酯與聚醚多元醇經胺基甲酸酯 化反應而得者。 本發明中，若脲基甲酸酯基/異尿氰酸酯基（莫耳比 )在上述範圍之外，則所得聚異氰酸酯對於低極性有機溶 劑之溶解性低且使用該組成物所得之塗膜之伸展性降低。 更好的是，脲基甲酸酯基/異尿氰酸酯基=92/8〜100/0 (莫耳比），又更好是92/8〜9 9/1。 又，此莫耳比可由1H-NMR測定而算出。 作爲上述基礎聚異氰酸酯，可使用例如聚異氰酸酯與 醇經脲基甲酸酯化者。 此情況下，作爲聚異氰酸酯，可自以往已知之各種聚 異氰酸酯適當選擇而使用，可使用例如六亞甲基二異氰酸 酯、1，4-四亞甲基二異氰酸酯、2 -甲基戊烷-1，5 -二異氰酸 酯、離胺酸二異氰酸酯等之脂肪族二異氰酸酯；異佛爾酮 二異氰酸酯、降冰片烷二異氰酸酯、氫化甲苯二異氰酸酯 、氫化二甲苯二異氰酸酯、氫化二苯基甲烷二異氰酸酯、 -9- 201000509 氫化四甲基二甲苯二異氰酸酯等之脂環式二異氰酸酯； 2,4 -甲苯二異氰酸酯、2,6 -甲苯二異氰酸酯、4,4'_二苯基 甲烷二異氰酸酯、2,4'·二苯基甲烷二異氰酸酯、2,2，_二苯 基甲院二異氰酸醋、4，V -二苯基酸二異氰酸醋、2 -硝基二 苯基-4，4'-二異氰酸酯、2，2’ -二苯基丙烷_4,4，-二異氰酸酯 、3,3·-二甲基二苯基甲烷-4,4、二異氰酸酯、4,4,_二苯基 丙烷二異氰酸酯、間-伸苯基二異氰酸酯、對-伸苯基二異 氰酸醋、萘-1,4-二異氰酸醋、萘-i，5_二異氰酸酯、3,3，_ 二甲氧基二苯基-4, V -二異氰酸酯等之芳香族二異氰酸酯 •’二甲苯-1，4 -二異氰酸酯、二甲苯-丨，3_二異氰酸酯等之 芳香脂肪族二異氰酸酯等。該等可單獨使用亦可2種以上 混合使用。 該等中’若考慮使所得塗膜之耐候性更高，以脂肪族 一異氰酸醋、脂環式一異氰酸酯較佳，尤其較好爲六亞甲 基二異氰酸酯、異佛爾酮二異氰酸酯、氫化二甲苯二異氰 酸酯、氫化二苯基甲烷二異氰酸酯、降冰片雜二異氰酸醋 〇 另一方面’作爲醇亦無特別限制，而可舉例爲例如正 丙醇、異丙醇、正丁醇、異丁醇、正戊醇、異戊醇、正己 醇、正庚醇、正辛醇、2 -乙基己醇、乙基二甲基_丨_己醇 、甲基-1-壬醇、二甲基-1-辛醇、十甲基-1-己醇、3_乙基-4,5,6 -三甲基辛醇、4,5,6,7_四甲基壬醇、4,5,8_三甲基癸 醇、4,7,8-三甲基癸醇、十三烷醇、十四烷醇、2_己基癸 醇、2-辛基癸醇、2-十二烷基癸醇、2_十六烷基十八烷醇 -10- 201000509 等之碳數1~2〇之單元醇類；乙二醇、1,2-p 二醇、1,2-丁 二醇、1,3-丁 二醇、1,4-丁二留 、2-甲基-1,5-戊二醇、3-甲基-1，5-戊二醇、 新戊二醇、1，8-辛二醇' 1，9-壬二醇、2,2-二醇、2-正丁基-2-乙基-1,3-丙二醇、2,2,4-二醇、2·乙基-1,3-己二醇、2-正十六烷基-1 正二十烷基-1,2-乙二醇、2-正二十八烷基-1 乙二醇、二丙二醇、1，4-環己烷二甲醇、雙j 烷或環氧丙烷加成物、氫化雙酚A、3-羥基 基-3-羥基-2,2-二甲基丙酸酯等之二醇類； 、丙三醇等之三醇類。該等可單獨使用亦可 使用。 該等醇類中，若考慮所得聚異氰酸酯組 性有機溶劑之溶解性更高而言，則較好爲碳 元醇，碳數3~20之單元醇更佳，碳數3~18 宜。 脲基甲酸酯化反應可使如上述之聚異氰 機溶劑存在下或不存在下，於50〜150 °C左 〇 脲基甲酸酯化亦可與胺基甲酸酯化同時 胺基甲酸酯化後進行。胺基甲酸酯化與脲基 進行時，在脲基甲酸酯化觸媒存在下進行即 酸酯化後進行脲基甲酸酯化時，在無脲基甲 在下，進行特定時間之胺基甲酸酯化反應後 Ϊ 二醇、1,3-丙 p、1，5-戊二醇 1,6-己二醇、 二甲基-1 ,3-丙 三甲基-1,3-戊 ,2-乙二醇、2-，2-乙二醇、二 盼A之環氧乙 -2,2-二甲基丙 三羥甲基丙烷 組合兩種以上 成物對於低極 數 1~20之單 之單元醇最適 酸酯與醇在有 右加熱而進行 進行，亦可於 甲酸酯化同時 可，於胺基甲 酸酯化觸媒存 ，添加脈基甲 -11 - 201000509 酸酯化觸媒進行脲基甲酸酯化即可。 作爲脲基甲酸酯化觸媒，可自已知觸媒適當選擇使用 ，例如可使用羧酸之鉻鹽。至於上述羧酸，舉例有例如乙 酸、丙酸、丁酸、己酸、辛酸、月桂酸、肉蔻蔻酸、棕櫚 酸、硬脂酸、2-乙基己酸等之飽和脂肪族羧酸、環己烷羧 酸、環戊烷羧酸等之飽和單環羧酸、雙環（4.4.0)癸烷-2-羧酸等之飽和雜環羧酸、環烷酸等之上述羧酸之混合物 ，油酸、亞油酸、亞油酸、大豆油脂肪酸、妥爾油脂肪酸 等之不飽和脂肪族羧酸、二苯基乙酸等之芳香脂肪族羧酸 、苯甲酸、甲苯酸等之芳香族羧酸等之單羧酸類；鄰苯二 甲酸、間苯二甲酸、對苯二甲酸、萘二甲酸、琥珀酸、酒 石酸、草酸、丙二酸、戊二酸、己二酸、庚二酸、辛二酸 、戊烯二酸、壬二酸、癸二酸、I，4-環己基二羧酸、α-氫 黏康酸、/3 -氫黏康酸、〇：-丁基-α-乙基穀胺酸、α,/3-二乙基琥珀酸、馬來酸、富馬酸、苯偏三甲酸、均苯四甲 酸等之聚羧酸類。該等羧酸鉻鹽可單獨使用亦可組合兩種 以上使用。尤其更好使用辛酸锆、2 -乙基己酸锆等之碳數 1 0以下之單羧酸锆鹽。 又’脲基甲酸酯化觸媒之使用量，相對於聚異氰酸酯 與醇之合計質量，較好爲0.0005-1質量％，更好爲 0 · 0 0 1 ~ 0.1 質量 ％。 在有機溶劑存再下進行反應時，可使用不影響反應之 各種有機溶劑，其具體例舉例有例如正己烷、辛烷等之脂 肪族烴類；環己烷、甲基環己烷等之脂環族烴類；丙酮、 -12- 201000509 甲基乙基酮、甲基異丁基嗣、環己酮等之酮類；乙酸甲酯 、乙酸乙酯、乙酸丁酯、乙酸異丁醋等之醋類；乙二醇乙 酸乙酸酯、丙二醇甲醚乙酸醋、3 -甲基-3 -甲氧基丁基乙 酸酯、3 -乙氧基丙酸乙酯等之二醇醚酯類；二乙醚、四氫 呋喃、二噁烷等之醚類；甲基氯、二氯甲烷、氯仿、四氯 化碳、甲基溴、二碘甲烷、二氯乙烷等之鹵化烴類；N—甲 基吡咯啶酮、二甲基甲醯胺、二甲基乙醯胺、二甲基亞颯 、六甲基磺醯基醯胺等之極性非質子溶劑等。該等溶劑可 單獨或組合兩種以上使用。 反應結束後，於反應系統內添加磷酸或磷酸酯等之反 應停止劑，於30〜100°C進行停止反應1〜2小時，使脲基 甲酸酯化反應停止。 反應停止後，藉由薄膜蒸餾等之已知方法除去未反應 成分，可獲得目的之脲基甲酸酯改性之聚異氰酸酯。 所得之脲基甲酸酯改性之聚異氰酸酯爲（滿足上述之 脲基甲酸酯基/異尿氰酸酯基之範圍之情況），其可直接 作爲基礎聚異氰酸酯。 又，以上所得之脲基甲酸酯改性之聚異氰酸酯可爲具 有脲基甲酸酯基爲主者，但於異氰酸酯基過量存在之條件 下進行反應會產生副反應，生成異尿氰酸酯。 因此，於脲基甲酸酯化中藉適宜調整[NCO]/[OH]之比 等之各種條件，可使所得之聚異氰酸酯中脲基甲酸酯基與 異尿氰酸酯基之莫耳比適當調整在100: 0〜70 : 30左右之 範圍。 -13- 201000509 又’以上述方法可調整脲基甲酸酯化聚異氰酸酯，進 而異尿氰酸酯化之脲基甲酸酯基/異尿氰酸酯基之莫耳比 〇 至於異尿氰酸酯化反應，舉例有在異尿氰酸酯化觸媒 存在下’使聚異氰酸酯改性（三聚化）之方法。至於該等 改性方法，可使用例如日本特許3371480號公報、特開 2002-24 1 458號公報中記載之方法。 異尿氰酸酯化觸媒可使用例如脂肪族羧酸之鹼金屬鹽 、酚鉀等之酚鹽、2,4,6 -三（二甲胺基甲基）酚、2,4 -雙 (二甲胺基甲基）酚、2,6-二第三丁基-4-二甲胺基三甲基 矽烷酚、三乙胺、Ν,Ν’，Ν”-三（二甲胺基丙基）六氫-S-三 嗪、二氮雜雙環十一碳烯等之胺系化合物。其中，較好爲 脂肪族之鹼金屬鹽，例如乙酸、丙酸、十一碳酸、己酸、 辛酸、肉宣蔻酸等之羧酸之鈉鹽、鉀鹽等。又，作爲市售 品，可使用 2-羥基丙基三甲銨.辛酸鹽（DABCO TMR， 三共 AIR PRODUCTS (股）製）、辛酸鉀（DABCO K-1 5 ，三共 AIRPRODUCTS (股）製）。 又，本發明之基礎聚異氰酸酯亦可爲調配脲基甲酸酯 改性之聚異氰酸酯、聚異氰酸酯之聚異尿氰酸酯者。 此時，脲基甲酸酯改性之聚異尿氰酸酯與聚異氰酸酯 可以滿足上述之脈基甲酸醋基/異尿氯酸醋基之莫耳比之 比例混合，而考慮脲基甲酸酯改性之聚異氰酸酯中存在之 異尿氰酸酯基，於與後述之聚醚多元醇之反應生成物（聚 異氰酸酯組成物）中之脲基甲酸酯基與異尿氰酸酯基滿足 -14 - 201000509 脲基甲酸酯基/異尿氰酸酯基= 90/10-100/0 (莫耳比）亦可 〇 作爲脲基甲酸酯改性之聚異氰酸酯與聚異尿氰酸酯之 原料聚異氰酸酯，可舉例與上述相同者，但此時亦較好爲 脂肪族或脂環族聚異氰酸酯。 又，於脲基甲酸酯改性時所用之醇，亦可舉例與上述 相同者，但此時亦較佳爲碳數1〜20之單元醇。 又，異尿氰酸酯化之原料聚異氰酸酯中，亦可含有其 一部分之聚異氰酸酯與多元醇反應所得之具異氰酸酯末端 之胺基甲酸酯預聚物。 以上說明之基礎聚異氰酸酯與聚醚多元醇在溶劑存在 下或不存在下反應，可獲得本發明之聚異氰酸酯組成物。 基礎聚異氰酸酯與聚醚多元醇之反應條件並無特別限 制，舉例爲例如依據需要在胺基甲酸酯化觸媒存在下，於 2 0~ 150 °C下使過量之基礎聚異氰酸酯與聚醚多元醇反應之 方法。 基礎聚異氰酸酯與聚醚多元醇之反應，可在無溶劑下 亦可在溶劑存在下進行。作爲溶劑可舉例與上述相同者。 此時，基礎聚異氰酸酯之[NCO]與聚醚多元醇之[OH] 之莫耳比，只要是[NCO]過量則無特別限制’但若考慮使 所得聚異氰酸酯組成物與多元醇化合物相溶性增高且提高 交聯密度及提高塗膜性能’則較好[NCOKtOHP1·2 ’更好 爲1 . 5以上’又更好爲1 _ 7以上。 又，依據需要所用之胺基甲酸酯化觸媒可自已知者適 -15- 201000509 當選擇，例如可使用二丁基錫月桂酸鹽、二辛基錫月桂酸 鹽等。 至於上述聚醚多元醇爲以低分子聚合物、低分子聚胺 、低分子胺醇作爲起始劑，使環氧乙烷、環氧丙烷、四氫 呋喃開環聚合而獲得之聚乙二醇、聚丙二醇、聚四亞甲基 二醇以及其等之共聚物等。 又，該等多元醇可單獨或組合兩種以上使用，但若考 慮提高對於低極性溶劑之溶解性及提高所得之塗膜之伸展 性，較好至少含有聚丙二醇。 本發明中，聚醚多元醇之平均官能基數並無特別限定 ，但若考慮抑制與基礎聚異氰酸酯反應時之膠凝化或使所 得聚異氰酸酯組成物與多元醇化合物之相溶性良好，較好 爲2〜4 ° 又，其數平均分子量亦無特別限制，但若考慮改性之 聚異氰酸酯之黏度或對低極性溶劑之溶解度或溶解後之黏 度’較好數平均分子量爲1,000〜1〇,〇〇〇’更好爲丨，000〜 8,000 〇 又，數平均分子量爲藉由示差折射率計檢測出之凝膠 滲透層析儀（以下簡稱G P C )所測定之測定値（聚苯乙嫌 換算値）。 至於聚醚多元醇之市售品’舉例有SUNNIX PP-10G0 ' PP-2000、 PP-3000 ' GP-1000 ' GP-3000(以上爲三洋化 成工業（股）製）、EKOSENOL- 823、828、83 0、8 3 7、 840 ' 850 、 851B 、 1020 、 2020 、 3020 、 510 、 1030 、 4030 -16- 201000509 、5030 (以上爲旭硝子胺基甲酸醋（股）製）、 POREMINOL-3 0 05、4 002、500 1、700 1 (以上爲旭硝子胺 基甲酸酯（股）製）等。 本發明之聚異氰酸酯組成物之黏度，於25t時爲 2,000 mPa. s以下，較好爲1，5〇〇 mpa· s以下，更好爲 1，000 mPa. s以下。聚異氰酸酯組成物之黏度若超過 2，0 0 0 m P a . s，則塗料組成物之黏度變高，有難以處理之 情況。另一方面，黏度之下限値雖無特別限制，但由操作 性觀點觀之，較好爲50 mPa· s以上。 本發明之塗料組成物，由於上述聚異氰酸酯組成物所 具有之特徵，作爲使其反應硬化之一之成分，自該用途一 般所用之多元醇化合物中適當選擇即可。 作爲具體例，舉例有丙烯酸系多元醇、氟系多元醇等 ，該等中，若考慮耐候性，則以氟系多元醇較適宜，若考 慮耐候性與成本方面之平衡，則較好爲丙烯酸系多元醇。 又，本發明中，基於本發明之聚異氰酸酯組成物之對 低極性有機溶劑之溶解性良好之特性，多元醇化合物亦較 好爲於低極性有機溶劑中可溶者。 作爲於低極性有機溶劑中可溶之丙烯酸系多元醇並無 特別限制，可使用已知之弱溶劑可溶型丙烯酸系多元醇。 其具體例舉例有市售品之 ACRYDIC A-801、HU-596 (以 上爲DIC (股）製）' EKOSEROL 410 (亞細亞工業（股 )製）、HITAROID 6500(曰立化成工業（股）製）等。 至於於低極性有機溶劑中可溶之氟系多元醇並未特別 -17- 201000509 限定’但可使用已知之弱溶劑可溶型氟系多元醇。其具體 例，舉例有氟乙烯-乙烯醚（乙烯酯）共聚物等。作爲市 售品，舉例有LUMIFLON LF8 00 (旭硝子（股）製）等。 上述多元醇之羥基價與酸價並無特別限制，但本發明 之塗料組成物較好爲經基價爲1~300 mgKOH/g,更好爲 1〜250 mgKOH/g。經基價未達1 mgKOH/g時，塗膜交聯 不充分，有塗膜強度等之物性降低之傾向，若超過3 00 mgKOH/g，貝fj塗膜之交聯密度過高而變硬，有對基材之追 隨性及柔軟性降低之情況。 本發明之塗料組成物中，聚異氰酸酯組成物與多元醇 化合物之調配比例爲，對於多元醇化合物1 〇〇質量份，較 好聚異氰酸酯組成物爲1〜150質量份，更好爲1~130質量 份，又更好爲1〜1 〇 〇質量份。 本發明之塗料組成物依據需要可含有苯胺點爲1 〇〜80 °C之低極性有機溶劑或混合苯胺點爲5〜50 °C之低極性有 機溶劑。此等低極性有機溶劑可於聚異氰酸酯組成物及/ 或多元醇之調製時分別添加’亦可於聚異氰酸酯組成物與 多元醇混合時添加用以調整黏度。 此處，所謂「苯胺點」爲等體積之苯胺與試料（有機 溶劑）成爲均一混合溶液存在時之最低溫度。又’所§胃「 混合苯胺點」爲苯胺2體積與試料1體積以及1 —戊院1 體積成爲均一混合物存在時之最低溫度。苯胺點及混合苯 胺點可依據JI s κ 2 2 5 6中記載之苯胺點及混合苯胺點試 驗方法予以測定。 -18- 201000509 又’苯胺由於凝固點爲-6。(：，故在該溫度以下紐 聲 /»vv 定苯胺點。因此，爲了於較廣範圍測定於苯胺中混合 之有機溶劑之溶解力’則使用混合苯胺點。 上述苯胺點較好爲10〜80 °c，更好爲1〇〜70¾ , 好爲1 〇 ~ 5 〇 °C。又’混合苯胺點時較好爲5〜5 0。(：。苯 未達10 °C或混合苯胺點未達5 °C時亦侵餓底層，苯胺 過8 0 °C或混合苯胺點超過5 0 °C時，聚異氰酸酯難以 〇 至於此等有機溶劑’舉例有例如甲基環己烷（苯 •_40°C)、乙基環己烷（苯胺點：44°C)、礦油精（ 點：5 6 °C )、萜烯油（苯胺點：4 4。(：），又，作爲石 烴而市售之商品名，舉例有芳族松香水（High Aren White Spirit) (HAWS)(日本蜆殻化學品公司製， 點：1 7 °C )、低芳族松香水（L A W S )(日本蜆殼化 公司製，苯胺點：44°C ) 、ESSONAPHA No· 6 (埃索 公司製，苯胺點：43 °C ) 、BEGAZOL 3040 (埃索美 司製，苯胺點：55°C ) 、A溶劑（新日本石油公司製 胺點：45t： ) 、CRENZORU (新日本石油公司製，苯 :64°C )、礦油精A (新日本石油公司製，苯胺點： )、HIAROM 2S (新日本石油公司製，苯胺點：44°C SOLUBESSO 1〇〇 (埃索美孚公司製，混合苯胺點： )、SOLUBESSO 150 (埃索美孚公司製，混合苯胺 18.3°C ) 、SUWAZOL 100 (九善石油化學公司製，混 胺點：24.6°C ) 、SUWAZOL 200 (九善石油化學公司 法測 戊院 又更 胺點 點超 溶解 胺點 苯胺 油系 n atic 苯胺 學品 美孚 孚公 ，苯 胺點 4 3。。 )' 1代 點： 合苯 製， -19- 201000509 混合苯胺點：23.8°C ) 、SUWAZOL 1 000 (九201000509 VI. Description of the Invention: [Technical Field] The present invention relates to a polyisocyanate composition and a two-component paint composition using the same. [Prior Art] A two-liquid urethane coating material using a polyisocyanate as a component is used in an exterior substrate such as a building or a civil engineering building because it can obtain a coating film excellent in weather resistance or abrasion resistance. Painting, car repair, plastic coating, etc. In the coating material, since the polyisocyanate has a high polarity, a strong solvent such as an aromatic hydrocarbon solvent such as toluene or xylene or an ester solvent such as butyl acetate is used, that is, a solvent having a strong dissolving power. This strong solvent has a tendency to be respected in recent years based on the improvement of the working environment or the reduction of the load on the earth's environment. In addition, when a new coating is applied to the old coating film for repairing or repainting, when the coating material contains a strong solvent having a high dissolving power, the old coating film may be flooded and dissolved, and even Old coatings are necessary for repair. As a result, problems such as enlargement and complication of painting operations, increase in coating cost, and extension of construction period have occurred. In view of the above points, in recent years, polyisocyanates which are easily dissolved in a low polar organic solvent have been continuously developed. For example, it is disclosed in the patent document 1 (Japanese Laid-Open Patent Publication No. Hei No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. 8-9 9 9 8). The obtained polyisocyanate is a polyisocyanate excellent in dilutableness of a low polar solvent. Further, this patent document also discloses that the coating film obtained by using the polyisocyanate as a curing agent is excellent in stretchability. Further, in Patent Document 2 (Japanese Patent Publication No. 2 00 8-2 4 828), it is disclosed that a specific ureido formic acid obtained by using an aliphatic and/or alicyclic diisocyanate and a monohydric alcohol having 1 to 20 carbon atoms is disclosed. The allocyanate/isocyanate-based molar ratio and the polyisocyanate compound having a specific molecular weight distribution are polyisocyanates excellent in solubility to a low-polar organic solvent and compatibility with a phthalate compound. The polyisocyanate of Patent Document 1 is excellent in solubility in a low-polarity organic solvent, but the obtained coating film has a crack elongation of about 50%, and there is room for improvement in stretchability. On the other hand, the stretchability of the coating film obtained by using the polyisocyanate compound of Patent Document 1 is also insufficient. Further, any one of the polyisocyanates is required to be further improved in compatibility with the polyol compound as a main component. [Problem to be Solved by the Invention] The present invention has been made in view of the above, and aims to provide low polarity. It is soluble in an organic solvent and is excellent in compatibility with a polyol compound. A polyisocyanate composition of a coating film excellent in stretchability and a liquid coating composition using the same can be obtained. [Means for Solving the Problem] The present inventors have repeatedly conducted a deliberate review for the above purpose, and found that in the polyisocyanate composition obtained by subjecting a base polyisocyanate to a polyether polyol to undergo a urethanization reaction, The use of an allophanate/isocyanate-based molar ratio as a base polyisocyanate in a specific range can improve the solubility in a low-polar organic solvent and is obtained from a coating containing the polyisocyanate composition and a polyol. The softness, stretchability and strength of the coating film are improved, and thus the present invention has been completed. That is, the present invention provides: 1. A polyisocyanate composition which is a polyisocyanate composition obtained by subjecting a base polyisocyanate to a polyether polyol to undergo a urethanization reaction, which is characterized by the above-mentioned basic polyisocyanate system. The allophanate group/isocyanate group 209 0/10~10 0/0 (mole ratio) contains an allophanate group and an isocyanurate group. 2. The polyisocyanate composition according to the above 1, wherein the basic polyisocyanate is obtained by reacting an aliphatic or alicyclic diisocyanate with a monohydric alcohol having 1 to 20 carbon atoms in the presence of an allophanate catalyst. By. 3. The polyisocyanate composition according to the above 1, wherein the basic polyisocyanate is obtained by reacting an aliphatic or alicyclic diisocyanate with a monohydric alcohol having 1 to 20 carbon atoms in the presence of an allophanate catalyst. A mixture of an allophanate-modified polyisocyanate and a polyisocyanurate of an aliphatic or alicyclic diisocyanate. 201000509 4. A polyisocyanate composition obtained by subjecting a polyether polyol to a urethanization reaction, which is characterized by having an allophanate group/iso = 90/10~1 〇〇/〇 (Morbi) contains an allophanate group, and the above-mentioned basic polyisocyanate is a urea obtained by reacting an aliphatic or aliphatic ester with a monohydric alcohol having 1 to 20 carbon atoms in an allophanate catalyst. a mixture of a polyisocyanate modified with a carbamic acid ester and a polyisocyanurate of a diester diisocyanate. 5. The average number of the above polyether polyols in the polyisocyanate according to any one of the above 1 to 4 a molecular weight of 1,000 to 6 · a two-liquid type coating composition containing a polyisocyanate composition and a polyol compound which are superior to one. 7. The above-mentioned 6 bis liquid type coating composition, 1 〇 8 Low polar organic solvent or mixed aniline point at 0 °C is an organic solvent. [Effect of the Invention] The polyisocyanate composition of the present invention is excellent in solubility in a low-polarity solvent and has good compatibility with a polymer used in a two-component type acid-based polymer. The coating film which is coated with the dihedral type using the polyisocyanate composition is excellent in flexibility, and has tensile strength and tensile strength. a poly-isocyanate polyisocyanate group urethane cyanate group and an isocyanate cyclic diisocyanate reacted in the presence of an aliphatic or alicyclic oxime ester composition, which has an aniline content of 10,000 ° g 1 to 4 a low-polar organic solvent having a point of 5 to 50 ° C (a weak fluorine-based or propylene-based composition has a large elongation of -8 - 201000509 and a 'two-liquid type coating composition of the present invention due to a low-polar organic solvent ( In the weak solvent), it is soluble, and since the undercoat layer is not eroded, the recoatability is excellent. [Embodiment] The present invention will be described in more detail. The polyisocyanate composition of the present invention is Polyisocyanate and polyether polyol based on allophanate groups and isocyanurate groups with allophanate groups/isocyanate groups = 90/10~100/0 (mole ratio) Obtained by a urethanation reaction. In the present invention, if the allophanate group/isocyanate group (mole ratio) is outside the above range, the obtained polyisocyanate is used for a low polar organic solvent. The solubility is low and the stretchability of the coating film obtained by using the composition is lowered. More preferably, the allophanate group/isocyanate group = 92/8 to 100/0 (mole ratio), and more preferably 92/8 to 9 9/1. The ear ratio can be calculated by 1H-NMR. As the above-mentioned base polyisocyanate, for example, a polyisocyanate and an alcohol can be used for the urea group. In this case, as the polyisocyanate, various polyisocyanates known from the prior art can be appropriately selected. For use, for example, an aliphatic diisocyanate such as hexamethylene diisocyanate, 1,4-tetramethylene diisocyanate, 2-methylpentane-1,5-diisocyanate, diazonic acid diisocyanate or the like can be used; Isophorone diisocyanate, norbornane diisocyanate, hydrogenated toluene diisocyanate, hydrogenated xylene diisocyanate, hydrogenated diphenylmethane diisocyanate, -9-201000509 hydrogenated tetramethyl xylene diisocyanate, etc. Isocyanate; 2,4-toluene diisocyanate, 2,6-toluene diisocyanate, 4,4'-diphenylmethane diisocyanate, 2,4'-diphenylmethane diisocyanate, 2,2,-diphenyl A hospital diisocyanate, 4,V-diphenyl acid Diisocyanate, 2-nitrodiphenyl-4,4'-diisocyanate, 2,2'-diphenylpropane-4,4,-diisocyanate, 3,3·-dimethyldiphenyl Methane-4,4,diisocyanate, 4,4,diphenylpropane diisocyanate, m-phenylene diisocyanate, p-phenylene diisocyanate, naphthalene-1,4-diisocyanate Aromatic diisocyanate such as acid vinegar, naphthalene-i,5-diisocyanate, 3,3,-dimethoxydiphenyl-4,V-diisocyanate, 'xylene-1,4-diisocyanate, two An aromatic aliphatic diisocyanate such as toluene-oxime or 3-diisocyanate. These may be used alone or in combination of two or more. In the case of considering the weather resistance of the obtained coating film to be higher, aliphatic isocyanuric acid or alicyclic monoisocyanate is preferred, and hexamethylene diisocyanate and isophorone diisocyanate are particularly preferred. And hydrogenated xylene diisocyanate, hydrogenated diphenylmethane diisocyanate, norbornane diisocyanate, and on the other hand, as the alcohol, there is no particular limitation, and for example, n-propanol, isopropanol, and n-butyl are exemplified. Alcohol, isobutanol, n-pentanol, isoamyl alcohol, n-hexanol, n-heptanol, n-octanol, 2-ethylhexanol, ethyl dimethyl hydrazine-hexanol, methyl-1-nonanol , dimethyl-1-octanol, decamethyl-1-hexanol, 3-ethyl-4,5,6-trimethyloctanol, 4,5,6,7-tetramethylnonanol, 4,5,8-trimethylnonanol, 4,7,8-trimethylnonanol, tridecyl alcohol, tetradecanol, 2-hexyl decyl alcohol, 2-octyl decyl alcohol, 2-ten a dialkyl decyl alcohol, a 2-hexadecyl octadecyl alcohol-10-201000509, etc., a hydrocarbon having 1 to 2 carbon atoms; ethylene glycol, 1,2-p diol, 1,2-butyl Glycol, 1,3-butanediol, 1,4-butane, 2-methyl-1,5-pentanediol, 3-methyl-1,5-pentanediol, neopentyl Alcohol, 1,8-octanediol ' 1,9-nonanediol, 2,2-diol, 2-n-butyl-2-ethyl-1,3-propanediol, 2,2,4-diol , 2·ethyl-1,3-hexanediol, 2-n-hexadecyl-1 n-icosyl-1,2-ethanediol, 2-n-octadecyl-1 ethylene glycol , dipropylene glycol, 1,4-cyclohexanedimethanol, di-j- or propylene oxide adduct, hydrogenated bisphenol A, 3-hydroxy-3-hydroxy-2,2-dimethylpropionate, etc. Glycols; triols such as glycerol. These can be used alone or in combination. Among these alcohols, in view of the higher solubility of the obtained polyisocyanate group organic solvent, it is preferably a carbon alcohol, preferably a hydrocarbon having 3 to 20 carbon atoms, and preferably having a carbon number of 3 to 18. The allophanation reaction can be carried out at the temperature of 50 to 150 ° C in the presence or absence of the above polyisocyanic acid solvent, and can be esterified with the urethane at the same time as the amine group. It is carried out after formic acidification. When the urethanization is carried out with a ureido group, in the presence of an allophanate catalyst, that is, after the acidification of the ureido-formation, the amine is subjected to the urea-formation, and the amine at a specific time is carried out without the urea-based group. After the esterification reaction, decanediol, 1,3-propane p, 1,5-pentanediol 1,6-hexanediol, dimethyl-1,3-propanetrimethyl-1,3- Ethylene, 2-ethylene glycol, 2-, 2-ethanediol, and di-A-epoxy ethylene-2,2-dimethylpropane trimethylolpropane are combined into two or more kinds of products for low-pole number 1~ The monol base acid ester and the alcohol of 20 are carried out by heating right, or may be acidified, and may be added to the urethane catalyst to add a thiol-11 - 201000509 acid ester. The catalyst can be subjected to allophanation. As the allophanate catalyst, it can be appropriately selected from known catalysts, and for example, a chromium salt of a carboxylic acid can be used. As the above carboxylic acid, for example, a saturated aliphatic carboxylic acid such as acetic acid, propionic acid, butyric acid, caproic acid, caprylic acid, lauric acid, myristic acid, palmitic acid, stearic acid or 2-ethylhexanoic acid, a mixture of a saturated monocyclic carboxylic acid such as cyclohexanecarboxylic acid or cyclopentanecarboxylic acid, a saturated heterocyclic carboxylic acid such as bicyclo (4.4.0) nonane-2-carboxylic acid or the like, or a naphthoic acid or the like , aromatic acids such as oleic acid, linoleic acid, linoleic acid, soybean oil fatty acid, tall oil fatty acid, aromatic aliphatic carboxylic acid such as diphenylacetic acid, aromatic acid such as benzoic acid, and toluic acid a monocarboxylic acid such as a carboxylic acid; phthalic acid, isophthalic acid, terephthalic acid, naphthalene dicarboxylic acid, succinic acid, tartaric acid, oxalic acid, malonic acid, glutaric acid, adipic acid, pimelic acid, Suberic acid, glutaconic acid, azelaic acid, sebacic acid, I,4-cyclohexyl dicarboxylic acid, α-hydromuconic acid, /3 -hydrogenconic acid, hydrazine: -butyl-α- A polycarboxylic acid such as ethyl glutamic acid, α,/3-diethyl succinic acid, maleic acid, fumaric acid, trimellitic acid or pyromellitic acid. These chromium carboxylate salts may be used singly or in combination of two or more. Particularly, a zirconium monocarboxylate having a carbon number of 10 or less such as zirconium octylate or zirconium 2-ethylhexanoate is preferably used. Further, the amount of the allophanate-catalyzed catalyst used is preferably 0.0005 to 1 mass%, more preferably 0.00 to 0.1 mass%, based on the total mass of the polyisocyanate and the alcohol. When the reaction is carried out in the presence of an organic solvent, various organic solvents which do not affect the reaction can be used. Specific examples thereof include aliphatic hydrocarbons such as n-hexane and octane; and fats such as cyclohexane and methylcyclohexane. Cyclic hydrocarbons; acetone, -12-201000509 methyl ketone, methyl isobutyl hydrazine, cyclohexanone and other ketones; methyl acetate, ethyl acetate, butyl acetate, isobutyl vinegar, etc. a glycol ether ester of ethylene glycol acetate, propylene glycol methyl ether acetate, 3-methyl-3-methoxybutyl acetate, ethyl 3-ethoxypropionate; An ether such as diethyl ether, tetrahydrofuran or dioxane; a halogenated hydrocarbon such as methyl chloride, dichloromethane, chloroform, carbon tetrachloride, methyl bromide, diiodomethane or dichloroethane; N-methylpyrrole A polar aprotic solvent such as ketone, dimethylformamide, dimethylacetamide, dimethylhydrazine or hexamethylsulfonylguanamine. These solvents may be used singly or in combination of two or more. After completion of the reaction, a reaction stopper such as phosphoric acid or phosphate is added to the reaction system, and the reaction is stopped at 30 to 100 ° C for 1 to 2 hours to stop the allophanation reaction. After the reaction is stopped, the unreacted component is removed by a known method such as thin film distillation to obtain the desired allophanate-modified polyisocyanate. The resulting allophanate-modified polyisocyanate is (in the case of satisfying the above-mentioned range of allophanate groups/isocyanate groups), and it can be directly used as a base polyisocyanate. Further, the allophanate-modified polyisocyanate obtained above may have an allophanate group as a main component, but a reaction may occur in the presence of an excess of an isocyanate group to cause a side reaction to form an isocyanurate. . Therefore, in the allophanatization, the allophanate group and the isocyanurate group in the obtained polyisocyanate can be obtained by various conditions such as adjusting the ratio of [NCO]/[OH]. More than the appropriate adjustment in the range of 100: 0~70: 30 or so. -13- 201000509 Further, the allophanate polyisocyanate can be adjusted by the above method, and the allosocyanate-based allophanate-based/isocyanate-based molybdenum oxime The acidification reaction is exemplified by a method of modifying (trimerization) a polyisocyanate in the presence of an isocyanurating catalyst. For the above-mentioned modification methods, for example, the methods described in Japanese Patent No. 3371480 and JP-A-2002-24 1 458 can be used. As the urethane cyanation catalyst, for example, an alkali metal salt of an aliphatic carboxylic acid, a phenate of potassium phenate or the like, 2,4,6-tris(dimethylaminomethyl)phenol, 2,4-bis ( Dimethylaminomethyl)phenol, 2,6-di-t-butyl-4-dimethylaminotrimethyldecanephenol, triethylamine, hydrazine, Ν', Ν"-tris(dimethylaminopropyl An amine compound such as hexahydro-S-triazine or diazabicycloundecene. Among them, an alkali metal salt of an aliphatic group such as acetic acid, propionic acid, undecanoic acid, caproic acid or octanoic acid is preferred. A sodium salt or a potassium salt of a carboxylic acid such as a meat, and a commercially available product, 2-hydroxypropyltrimethylammonium octoate (DABCO TMR, manufactured by Sankyo AIR PRODUCTS), octanoic acid can be used. Potassium (DABCO K-1 5 , manufactured by AIRPRODUCTS Co., Ltd.) Further, the base polyisocyanate of the present invention may be a polyisocyanate modified with an allophanate or a polyisocyanate of a polyisocyanate. At this time, the allophanate-modified polyisocyanurate and the polyisocyanate may satisfy the above ratio of the molar ratio of the thioglycolic acid/isouric acid vinegar group, and the urea is considered. An allo-urethane group and an isocyanurate in a reaction product (polyisocyanate composition) of a polyether polyol to be described later, an isocyanate group present in a formate modified polyisocyanate Base satisfies -14 - 201000509 Urea-based/isocyanate group = 90/10-100/0 (Morby) can also be used as an allophanate-modified polyisocyanate and polyisoprene The polyisocyanate of the cyanate ester is exemplified by the same as the above, but in this case, it is preferably an aliphatic or alicyclic polyisocyanate. Further, the alcohol used in the modification of the allophanate may be exemplified by The same as the above, but in this case, it is preferably a monohydric alcohol having a carbon number of 1 to 20. Further, the isocyanate esterified raw material polyisocyanate may further contain an isocyanate obtained by reacting a part of the polyisocyanate with a polyhydric alcohol. The terminal urethane prepolymer. The polyisocyanate composition of the present invention can be obtained by reacting the above-mentioned base polyisocyanate with a polyether polyol in the presence or absence of a solvent. Basic polyisocyanate and polyether polyol The reaction conditions are not limited The method is, for example, a method of reacting an excess of a base polyisocyanate with a polyether polyol at a temperature of from 20 to 150 ° C in the presence of a urethane catalyst as needed. Basic polyisocyanate and polyether polyol The reaction can be carried out in the absence of a solvent or in the presence of a solvent. The solvent can be exemplified by the same as above. At this time, the molar ratio of [NCO] of the base polyisocyanate to [OH] of the polyether polyol is as long as When the [NCO] is excessive, there is no particular limitation. However, it is preferable to increase the compatibility between the obtained polyisocyanate composition and the polyol compound, and to increase the crosslinking density and improve the coating film performance. [NCOKtOHP1·2' is preferably 1. 5 or more 'is better than 1 _ 7 or more. Further, the urethane-based catalyst to be used may be selected from known sources, for example, dibutyltin laurate, dioctyltin laurate or the like. The polyether polyol is a polyethylene glycol obtained by ring-opening polymerization of ethylene oxide, propylene oxide or tetrahydrofuran with a low molecular weight polymer, a low molecular weight polyamine, and a low molecular weight amine alcohol as a starting agent. Propylene glycol, polytetramethylene glycol, copolymers thereof, and the like. Further, these polyols may be used singly or in combination of two or more. However, it is preferred to contain at least polypropylene glycol in consideration of improvement in solubility in a low polar solvent and improvement in stretchability of the obtained coating film. In the present invention, the average functional group number of the polyether polyol is not particularly limited. However, it is preferred to suppress gelation upon reaction with the base polyisocyanate or to improve compatibility between the obtained polyisocyanate composition and the polyol compound. 2 to 4 ° Further, the number average molecular weight thereof is not particularly limited, but considering the viscosity of the modified polyisocyanate or the solubility to a low-polar solvent or the viscosity after dissolution, the number average molecular weight is 1,000 to 1 Torr, 〇 〇〇 'Better 丨, 000~ 8,000 〇 In addition, the number average molecular weight is determined by a gel permeation chromatograph (hereinafter referred to as GPC) detected by a differential refractometer (polyphenyl benzene) ). As for the commercial products of polyether polyols, there are examples of SUNNIX PP-10G0 'PP-2000, PP-3000 ' GP-1000 ' GP-3000 (above is Sanyo Chemical Industry Co., Ltd.), EKOSENOL- 823, 828, 83 0, 8 3 7, 840 ' 850 , 851B , 1020 , 2020 , 3020 , 510 , 1030 , 4030 -16- 201000509 , 5030 (above is Asahi Nitrate vinegar (shares)), POREMINOL-3 0 05, 4 002, 500 1, 700 1 (The above is manufactured by Asahi Nitrate). The viscosity of the polyisocyanate composition of the present invention is 2,000 mPa·s or less at 25 t, preferably 1,5 〇〇 mpa·s or less, more preferably 1,000 mPa·s or less. If the viscosity of the polyisocyanate composition exceeds 2,0 0 m P a .s, the viscosity of the coating composition becomes high and it is difficult to handle. On the other hand, the lower limit of the viscosity is not particularly limited, but is preferably 50 mPa·s or more from the viewpoint of operability. The coating composition of the present invention may be appropriately selected from the polyol compounds generally used for the purpose of the above-mentioned polyisocyanate composition, as a component which is one of the reaction hardening. Specific examples include acrylic polyols and fluorine-based polyols. Among them, fluorine-based polyols are preferable in view of weather resistance, and acrylic acid is preferred in consideration of balance between weather resistance and cost. Is a polyol. Further, in the present invention, the polyisocyanate composition of the present invention is excellent in solubility to a low-polar organic solvent, and the polyol compound is preferably soluble in a low-polar organic solvent. The acrylic polyol which is soluble in the low polar organic solvent is not particularly limited, and a known weak solvent-soluble acrylic polyol can be used. Specific examples thereof include ACRYDIC A-801 and HU-596 (manufactured by DIC Co., Ltd.) of the commercial products, EKOSEROL 410 (made by Asia Industrial Co., Ltd.), and HITAROID 6500 (made by Yuli Chemical Industry Co., Ltd.). Wait. The fluorine-based polyol which is soluble in the low-polar organic solvent is not particularly limited to -17-201000509, but a known weak solvent-soluble fluorine-based polyol can be used. Specific examples thereof include a vinyl fluoride-vinyl ether (vinyl ester) copolymer and the like. As a commercial item, LUMIFLON LF8 00 (made by Asahi Glass Co., Ltd.), etc. are mentioned. The hydroxyl value and acid value of the above polyol are not particularly limited, but the coating composition of the present invention preferably has a base value of from 1 to 300 mgKOH/g, more preferably from 1 to 250 mgKOH/g. When the base price is less than 1 mgKOH/g, the crosslinking of the coating film is insufficient, and the physical properties such as the film strength tend to decrease. If it exceeds 300 mgKOH/g, the crosslinking density of the shell coating film becomes too high and becomes hard. There is a case where the followability and softness of the substrate are lowered. In the coating composition of the present invention, the ratio of the polyisocyanate composition to the polyol compound is preferably from 1 to 150 parts by mass, more preferably from 1 to 130, based on 1 part by mass of the polyol compound. The mass fraction is preferably 1 to 1 part by mass. The coating composition of the present invention may contain a low polar organic solvent having an aniline point of from 1 Torr to 80 °C or a low polarity organic solvent having a mixed aniline point of from 5 to 50 °C, as needed. These low-polarity organic solvents may be added separately in the preparation of the polyisocyanate composition and/or the polyol. Alternatively, the polyisocyanate composition may be added to adjust the viscosity when mixed with the polyol. Here, the "aniline point" is the lowest temperature at which an equal volume of aniline and a sample (organic solvent) are in the presence of a homogeneous mixed solution. Further, the "mixed aniline point" of the stomach is the lowest temperature at which the volume of the aniline 2 is 1 volume of the sample and the volume of the 1st chamber is a uniform mixture. The aniline point and the mixed aniline point can be determined in accordance with the aniline point and mixed aniline point test method described in JI s κ 2 2 5 6 . -18- 201000509 And aniline has a freezing point of -6. (:, therefore, below the temperature, the sound / νv aniline point. Therefore, in order to measure the solubility of the organic solvent mixed in the aniline in a wide range, the mixed aniline point is used. The aniline point is preferably 10~ 80 °c, more preferably 1〇~703⁄4, preferably 1 〇~ 5 〇 ° C. Also 'mixed aniline point is preferably 5~5 0. (: benzene is not up to 10 ° C or mixed aniline point is not When the temperature reaches 5 °C, the bottom layer is also invaded. When the aniline is over 80 °C or the mixed aniline point exceeds 50 °C, the polyisocyanate is difficult to get into such an organic solvent. For example, methylcyclohexane (benzene•_40°) C), ethylcyclohexane (aniline point: 44 ° C), mineral spirits (point: 5 6 ° C), terpene oil (aniline point: 4 4 (:), again, as a hydrocarbon For sale, for example, High Aren White Spirit (HAWS) (made by Japan Shell Chemical Co., Ltd., point: 17 °C), Low Aromatic Pine Perfume (LAWS) (Japan Shell Company) , aniline point: 44 ° C), ESSONAPHA No. 6 (made by Esso, aniline point: 43 ° C), BEGAZOL 3040 (made by Esso Messi, aniline point: 55 ° C), A solvent Nippon Oil Corporation's amine-making point: 45t: ), CRENZORU (Nippon Oil Co., Ltd., benzene: 64 ° C), mineral spirit A (Nippon Oil Company, aniline point: ), HIAROM 2S (New Japan Oil Company) Benzene point: 44 ° C SOLUBESSO 1 〇〇 (made by Esso Mobil, mixed aniline point: ), SOLUBESO 150 (made by Esso Mobil, mixed aniline 18.3 ° C), SUWAZOL 100 (made by Jiushan Petrochemical Co., Ltd.) , mixed amine point: 24.6 ° C), SUWAZOL 200 (Jiushan Petrochemical Company Law to measure the Affiliated Hospital and a more amine point super soluble amine point aniline oil system n atic aniline products Mobil Fugong, aniline point 4 3 ..) '1 generation point: benzene system, -19- 201000509 mixed aniline point: 23.8 ° C), SUWAZOL 1 000 (nine
公司製，混合苯胺點：12.7°C ) 、SUWAZOL 石油化學公司製，混合苯胺點：1 6 · 5 °C ) 1 8 0 0 (九善石油化學公司製，混合苯胺點：1 光IBUZOL 100 (出光興產公司製，混合苯肢 )、出光IBUZ〇L150(出光興產公司製，混 15.2°C ) 、BEGAZOL ARO-80 (埃索美孚公司 胺點：25°C ) 、BEGAZOL R-100 (埃索美孚公 苯胺點：14°C )、昭石特HAIZOL (日本蜆殻 製，混合苯胺點：12.6°C)、日石HAIZ〇L( 公司製，混合苯胺點：1 7 °C以下）等。該等有 獨使用一種亦可混合兩種以上使用。 苯胺點爲1 0 °C以上或混合苯胺點爲5 °C以 劑有臭味較少之特徵。因此，含有該等低極f生 本發明塗料組成物，由耐環境性之觀點觀之亦 又’如上述之低極性有機溶劑由於溶解力 底層’故塗料組成物之重新塗佈變得可能，亦 修補用塗料。 又’上述塗料組成物亦可含有一般塗料所 加劑。作爲添加劑，舉例有例如可塑劑、防腐 、防藻劑、消泡劑、勻化劑、顏料分散劑、行 垂流防止劑、觸媒、硬化促進劑、脫水劑、莽 線吸收劑、抗氧化劑、顏料、界面活性劑等。 由本發明之塗料組成物製作塗膜時，藉目 善石油化學 1500 (九善 、SUWAZOL 5.7〇C )、出 :點：1 3.5 °C 合苯胺點： 製，混合苯 司製，混合 化學品公司 新曰本石油 機溶劑可單 上之有機溶 有機溶劑之 爲優異者。 低難以侵蝕 可使用作爲 用之各種添 劑、防黴劑 ，降防止劑、 '艷劑、紫外 :於水泥、灰 -20- 201000509 漿、側板、押出成型板、瓷器瓷碍、金屬、玻璃、木材、 塑膠等之適宜基材上’以刷塗、輕塗、吹塑塗裝等方法予 以塗佈，以適當方法乾燥、硬化即可。 又’於乾式建材上進行塗裝時，由吹塑塗佈器或輥塗 佈器於施工場所預先塗佈亦可。 又，亦可於基材上直接塗佈塗料組成物，亦可塗佈於 塡孔、電鍍或底塗（電漿塗佈）、中間塗（著色等）上。 又’基材爲金屬時’亦可塗佈於施以磷酸鐵處理或磷酸鋅 處理等之表面處理上。 實施例 以下列舉合成例、實施例及比較例，對本發明更具體 加以說明’但本發明不限定於以下實施例。又，以下之黏 度係由B型旋轉黏度計之測定値。 Π ]改性聚異氰酸酯之製造 [合成例1]脲基甲酸酯改性之聚異氰酸酯之合成 於配置有攪拌機、溫度計、冷卻管及氮氣導入管之體 積1升之四頸燒瓶中，裝入95 0克六亞甲基二異氰酸酯（ 曰本聚胺基甲酸酯工業（股）製，NCO含量：49.9質量％ ’以下稱爲HDI)及50克異丙醇，邊攪拌邊加熱至85 °C ’進行3小時之胺基甲酸酯化反應。 隨後’於該反應液中添加0.1克脲基甲酸酯化觸媒之 辛酸銷（第—稀土元素化學工業（股）製），於1101：反 -21 - 201000509 應3小時後，添加0.1克之反應停止劑酸性磷酸酯（JP-5 0 8，城北化學工業（股）製），於5 0 °C進行停止反應1 小時。 自此反應生成物，藉薄膜蒸餾（條件：14(TC，0.04 kPa)移除過剩之HDI，獲得310克之NCO含量19.3質 量％、黏度（25 °C ) 100 mPa · s、游離HDI含量0.1質量 %之改性聚異氰酸酯B- 1。改性聚異氰酸酯B- 1完成紅外 線吸收分析（IR )後，確認脲基甲酸酯基之強吸收且確認 異尿氰酸酯基之弱吸收。改性聚異氰酸酯B-1完成NMR 測定後，確認脲基甲酸酯基及少量異尿氰酸酯基。 [合成例2]HDI之聚異尿氰酸酯之合成 於配置有攪拌機、溫度計、冷卻管及氮氣導入管之體 積1升之四頸燒瓶中，裝入997克HDI、2克1,3-丙二醇 以及1克苯酚，進而裝入0.2克之異尿氰酸酯化觸媒之己 酸鉀，在5 (TC反應1 .5小時。隨後，立即升溫至6 5。(：反 應1小時，於NCO含量達44.8質量％時，添加0.1克反 應停止劑之磷酸，進行停止反應1小時。 自此反應生成物，藉薄膜蒸餾（條件：130 °C，0.04 kPa )移除過剩之HDI，獲得1 30克之NCO含量23.2質 量％、黏度（25。(：）1，180 mPa· s、游離 HDI 含量 0.2 質 ® %之改性聚異氰酸酯B - 2。改性聚異氰酸酯B - 2完成紅 #線吸收分析（IR )後，確認異尿氰酸酯基之強吸收且確 認、脲基甲酸酯基之弱吸收。改性聚異氰酸酯 B-2完成 -22- 201000509 NMR測定後’確認異尿氰酸酯基及少量脲基甲酸_基。 [2]聚異氰酸酯組成物之製造 [實施例1] 於配置有攪拌機、溫度計、冷卻管及氮氣導入管之體 積1升之四頸燒瓶中，裝入210克於合成例1中所得之改 性聚異氰酸酯B-1作爲基礎聚異氰酸酯及90克聚醚多元 醇（EKOSENOL 851B，數平均分子量6,700，旭硝子胺基 甲酸酯（股）製），加熱至8 5 °C，進行4小時胺基甲酸 酯化反應’獲得300克之NCO含量12.9質量％、黏度（ 25°C ) 720mPa. s之聚異氰酸酯組成物S-1。 [實施例2] 於配置有攪拌機、溫度計、冷卻管及氮氣導入管之體 積1升之四頸燒瓶中，裝入1 8 9克於合成例1中所得之改 性聚異氰酸酯B -1及2 1克於合成例2中所得之改性聚異 氰酸酯B-2作爲基礎聚異氰酸酯及90克聚醚多元醇（ EKOSENOL 851B，數平均分子量6,700，旭硝子胺基甲酸 酯（股）製），加熱至85°C，進行4小時胺基甲酸酯化 反應，獲得300克之NCO含量13.2質量％、黏度（25 °C )830 mPa· s之聚異氰酸酯組成物S-2。 [比較例1 ] 於配置有攪拌機、溫度計、冷卻管及氮氣導入管之體 -23- 201000509 積1升之四頸燒瓶中，裝入I68克於合成例1中所得之改 性聚異氰酸酯B -1及4 2克於合成例2中所得之改性聚異 氰酸酯B-2作爲基礎聚異氰酸酯及90克聚醚多元醇（ EKOSENOL 851B，數平均分子量6,700，旭硝子胺基甲酸 酯（股）製），加熱至8 5 °C，進行4小時胺基甲酸酯化 反應，獲得300克之NCO含量13.5質量％、黏度（25 °C )l，000 mPa· s之聚異氰酸酯組成物S-3。 [比較例2 ] 於配置有攪拌機、溫度計、冷卻管及氮氣導入管之體 積1升之四頸燒瓶中，裝入910克HDI及90克2-乙基已 醇，立即加熱至8 0°C反應1小時，進行2小時胺基甲酸 酯化反應。 隨後，於該反應液中，添加〇.〇5克異尿氰酸酯之2-羥基丙基三甲基銨辛酸鹽（DABCO TMR，三共 AIR PRODUCTS (股）製），於60°C反應2小時後，添加0.2 克之反應停止劑之磷酸，進行停止反應1小時。 自此反應生成物，藉薄膜蒸餾（條件：1 3 0 °C，0.04 kPa)移除過剩之HDI，獲得460克之NCO含量17.3質 量％、黏度（25°C) 470 mPa· s、游離HDI含量0_2質量 %之改性聚異氰酸酯B-3 (基礎聚異氰酸酯）。改性聚異 氰酸酯B-3完成紅外線吸收分析（IR )後，確認異尿氰酸 酯基之強吸收且確認脲基甲酸酯基之弱吸收。改性聚異氰 酸酯B-3完成NMR測定後，確認了脲基甲酸酯基及異尿 -24- 201000509 氰酸酯基。 接著’於配置有攪拌機、溫度計、冷卻管及氮氣導入 管之體積1升之四頸燒瓶中，裝入216克於上述所得之改 性聚異氰酸酯B_3作爲基礎聚異氰酸酯及84克聚醚多元 醇（EKOSENOL 851B，數平均分子量6,700，旭硝子胺基 甲酸酯（股）製），加熱至8 5 °C，進行4小時胺基甲酸 酯化反應，獲得300克之NCO含量12.1質量％、黏度（ 25 °C ) 1,500 mPa. s之聚異氰酸酯組成物S-4。 於上述實施例1、2及比較例1、2所得之聚異氰酸酯 組成物S -1、S - 2、S - 3、S -4以下述方法分別測定脲基甲 酸酯基與異尿氰酸酯基之（生成）莫耳比。結果示於表1 〇 又，於S-1及S-3之脲基甲酸酯基與異尿氰酸酯基之 (生成）莫耳比與使用之各基礎聚異氰酸酯B-1及B-3之 莫耳比相同。 [測定法] 使用 W-NMR ( ECX400M，日本電子製），由在 8.55ppm附近之鍵結至脲基甲酸酯基之氮原子的氫原子之 訊號與在3. 8 5 ppm附近之鄰接於異尿氰酸酯基之氮原子之 亞甲基的氫原子之訊號面積比求得°具體測定條件如下。 測定溫度：23°C 試料濃度0 · 1克Π毫升 -25- 201000509 積分次數：1 6次 緩和時間：5秒 溶劑：氘化氯仿 化學位移基準：CDC13中CHCh之氫原子訊號（7.24ppm)Company system, mixed aniline point: 12.7 ° C), manufactured by SUWAZOL Petrochemical Co., Ltd., mixed aniline point: 1 6 · 5 °C) 1 8 0 0 (made by Jiushan Petrochemical Co., Ltd., mixed aniline point: 1 light IBUZOL 100 ( Idemitsu Kosan Co., Ltd., mixed benzene limbs, IBUZ〇L150 (produced by Idemitsu Kosan Co., Ltd., mixed 15.2 °C), BEGAZOL ARO-80 (Esso Mobil's amine point: 25 ° C), BEGAZOL R-100 ( Esso mate male aniline point: 14 ° C), Zhao Shite HAIZOL (Japanese oyster shell, mixed aniline point: 12.6 ° C), Japanese stone HAIZ 〇 L (company, mixed aniline point: 1 7 ° C or less) The above may be used alone or in combination of two or more. The aniline point is above 10 ° C or the mixed aniline point is 5 ° C. The agent has less odor. Therefore, the low-level f is contained. The coating composition of the present invention is also made from the viewpoint of environmental resistance, and the re-coating of the coating composition is made possible by the low-polarity organic solvent as described above due to the solubility of the underlying layer. The coating composition may also contain a general coating additive. As an additive, for example, plasticity is exemplified. , antiseptic, anti-algae agent, antifoaming agent, homogenizing agent, pigment dispersing agent, anti-flowing agent, catalyst, hardening accelerator, dehydrating agent, sputum absorbent, antioxidant, pigment, surfactant, and the like. When making a coating film from the coating composition of the present invention, borrowing from the Good Petrochemical 1500 (Jiushan, SUWAZOL 5.7〇C), out: Point: 1 3.5 °C aniline point: system, mixed styrene system, mixed chemical company The solvent of the new sputum oil machine can be excellent in organic solvent-soluble organic solvents. It is difficult to erode and can be used as various additives, anti-fungal agents, anti-fouling agents, scent agents, ultraviolet rays: in cement, ash. 20- 201000509 Pulp, side panel, extruded molding board, porcelain porcelain, metal, glass, wood, plastic, etc., coated on the appropriate substrate by brushing, light coating, blow molding, etc., dried by appropriate methods When it is applied to dry building materials, it may be pre-coated by a blow coater or a roll coater at the construction site. Alternatively, the coating composition may be directly applied to the substrate. Can also be applied to the pupil, plating Or primer (plasma coating), intermediate coating (coloring, etc.). When the substrate is made of metal, it may be applied to a surface treatment such as iron phosphate treatment or zinc phosphate treatment. The present invention will be more specifically described by way of Synthesis Examples, Examples and Comparative Examples. However, the present invention is not limited to the following examples. Further, the following viscosity is measured by a B-type rotational viscometer. Π ] Manufacture of modified polyisocyanate [Synthesis Example 1] Synthesis of allophanate-modified polyisocyanate in a one-liter four-necked flask equipped with a stirrer, a thermometer, a cooling tube, and a nitrogen introduction tube, and charged with 95 g of hexamethylenediene Isocyanate (manufactured by Sigma Polyurethane Industry Co., Ltd., NCO content: 49.9% by mass 'hereinafter referred to as HDI) and 50 g of isopropyl alcohol, heated to 85 ° C with stirring for 3 hours of amine group Formatylation reaction. Subsequently, adding 0.1 g of the octanoate catalyst of the allophanate catalyst (manufactured by the Rare Earth Element Chemical Industry Co., Ltd.) to the reaction solution, and adding 0.1 g after 3 hours at 1101: anti-21 - 201000509 The reaction stopper acid phosphate (JP-5 0 8, manufactured by Seongbuk Chemical Industry Co., Ltd.) was stopped at 50 ° C for 1 hour. From the reaction product, the excess HDI was removed by thin film distillation (condition: 14 (TC, 0.04 kPa), and the NCO content of 310 g was 19.3 mass%, the viscosity (25 °C) was 100 mPa · s, and the free HDI content was 0.1 mass. % modified polyisocyanate B-1. After the modified polyisocyanate B-1 was subjected to infrared absorption analysis (IR), the strong absorption of the allophanate group was confirmed and the weak absorption of the isocyanate group was confirmed. After completion of the NMR measurement of the polyisocyanate B-1, the allophanate group and a small amount of the isocyanurate group were confirmed. [Synthesis Example 2] The polyisocyanate of HDI was synthesized in a mixer, a thermometer, and a cooling tube. And a nitrogen gas introduction tube in a one-liter four-necked flask, which was charged with 997 g of HDI, 2 g of 1,3-propanediol, and 1 g of phenol, and further charged with 0.2 g of an isothiocyanate catalyst potassium hexanoate. At 5 (TC reaction for 1.5 hours. Immediately thereafter, the temperature was raised to 65. (: 1 hour of reaction, when the NCO content reached 44.8 mass%, 0.1 g of phosphoric acid of the reaction stopper was added, and the reaction was stopped for 1 hour. The reaction product was subjected to thin film distillation (condition: 130 ° C, 0.04 kPa) to remove excess HDI. 1 30g of NCO content 23.2% by mass, viscosity (25. (:) 1,180 mPa·s, free HDI content 0.2 quality ® % modified polyisocyanate B-2. Modified polyisocyanate B-2 finished red# After the line absorption analysis (IR), the strong absorption of the isocyanate group was confirmed and the weak absorption of the allophanate group was confirmed. The modified polyisocyanate B-2 was completed after the -22-201000509 NMR measurement. Cyanate group and a small amount of ureido-form. [2] Production of polyisocyanate composition [Example 1] In a 1-liter four-necked flask equipped with a stirrer, a thermometer, a cooling tube and a nitrogen introduction tube, 210 g of the modified polyisocyanate B-1 obtained in Synthesis Example 1 as a base polyisocyanate and 90 g of a polyether polyol (EKOSENOL 851B, number average molecular weight 6,700, manufactured by Asahi Nitrate), heated 4 hours of urethanization reaction to 8 5 ° C, and obtained 300 g of an NCO content of 12.9% by mass and a viscosity (25 ° C) of 720 mPa·s of polyisocyanate composition S-1. [Example 2] Configurable with a mixer, thermometer, cooling tube and nitrogen inlet tube In a 1-liter four-necked flask, 189 g of the modified polyisocyanate B-1 obtained in Synthesis Example 1 and 21 g of the modified polyisocyanate B-2 obtained in Synthesis Example 2 were charged as a base polyisocyanate. And 90 g of polyether polyol (EKOSENOL 851B, number average molecular weight 6,700, Asahi sulphate), heated to 85 ° C, 4 hours of urethanation reaction, to obtain 300 grams of NCO content 13.2% by mass, viscosity (25 ° C) 830 mPa·s of polyisocyanate composition S-2. [Comparative Example 1] I68 g of the modified polyisocyanate B obtained in Synthesis Example 1 was placed in a 4-liter four-necked flask equipped with a stirrer, a thermometer, a cooling tube, and a nitrogen introduction tube. 1 and 4 2 g of the modified polyisocyanate B-2 obtained in Synthesis Example 2 as a base polyisocyanate and 90 g of a polyether polyol (EKOSENOL 851B, number average molecular weight 6,700, manufactured by Asahi Nitrate) The mixture was heated to 85 ° C for 4 hours of urethanation to obtain 300 g of a polyisocyanate composition S-3 having an NCO content of 13.5% by mass and a viscosity (25 ° C) of 1,000 mPa·s. [Comparative Example 2] In a four-necked four-necked flask equipped with a stirrer, a thermometer, a cooling tube, and a nitrogen introduction tube, 910 g of HDI and 90 g of 2-ethylhexanol were charged, and immediately heated to 80 ° C. The reaction was carried out for 1 hour, and a urethanation reaction was carried out for 2 hours. Subsequently, in the reaction mixture, 5 g of an isohydroxycyanate 2-hydroxypropyltrimethylammonium octoate (DABCO TMR, manufactured by Sankyo AIR PRODUCTS Co., Ltd.) was added, and the reaction was carried out at 60 ° C. After the hour, 0.2 g of the phosphoric acid of the reaction stopper was added, and the reaction was stopped for 1 hour. From this reaction product, excess HDI was removed by thin film distillation (condition: 130 ° C, 0.04 kPa) to obtain 460 g of NCO content of 17.3% by mass, viscosity (25 ° C) of 470 mPa·s, free HDI content. 0_2% by mass of modified polyisocyanate B-3 (base polyisocyanate). After the modified polyisocyanate B-3 was subjected to infrared absorption analysis (IR), strong absorption of the isocyanate group was confirmed and weak absorption of the allophanate group was confirmed. After the modified polyisocyanate B-3 was subjected to NMR measurement, the allophanate group and the isocyanine-24-201000509 cyanate group were confirmed. Then, in a four-necked flask equipped with a stirrer, a thermometer, a cooling tube and a nitrogen introduction tube, 216 g of the modified polyisocyanate B_3 obtained above was used as a base polyisocyanate and 84 g of a polyether polyol ( EKOSENOL 851B, number average molecular weight 6,700, Asahi sulphate (manufactured by Asahi Co., Ltd.), heated to 85 ° C, 4 hours of urethanation reaction, obtaining 300 grams of NCO content 12.1% by mass, viscosity (25 °C) Polyisocyanate composition S-4 of 1,500 mPa.s. The polyisocyanate compositions S-1, S-2, S-3, and S-4 obtained in the above Examples 1, 2 and Comparative Examples 1, 2 were respectively tested for allophanate groups and isocyanuric acid by the following methods. The molar ratio of the ester group. The results are shown in Table 1. Further, the molar ratio of allophanate groups and isocyanurate groups at S-1 and S-3 and the base polyisocyanates B-1 and B- used. 3 Moore is the same. [Measurement method] Using W-NMR (ECX400M, manufactured by JEOL Ltd.), the signal of the hydrogen atom bonded to the nitrogen atom of the allophanate group at around 8.55 ppm is adjacent to the vicinity of 3.85 ppm. The signal area ratio of the hydrogen atom of the methylene group of the nitrogen atom of the isocyanate group is determined as follows. The specific measurement conditions are as follows. Measurement temperature: 23 ° C Sample concentration 0 · 1 gram Π ml -25- 201000509 Number of integration points: 1 6 times Relaxation time: 5 seconds Solvent: Deuterated chloroform Chemical shift reference: Hydrogen atomic signal of CHCh in CDC13 (7.24ppm)
又，實施例1、2及比較例1、2所得之聚異氰酸酯組 成物S-l、S-2、S-3、S-4，藉由以下方法測定對礦油精A (新日本石油（股）製造）之於20 °C之溶解性。結果示 於表1。 [測定法] 量取1克聚異氰酸酯組成物，於其中添加礦油精A， 於渾濁後作爲終點，求得此時點之礦油精A添加量（克 )° 使用此添加量’由下式（1)算出容限度。 量（1克） 谷限度=有機溶劑所需量（克）/樣品 表1Further, the polyisocyanate compositions S1, S-2, S-3, and S-4 obtained in Examples 1 and 2 and Comparative Examples 1 and 2 were measured for the mineral spirits A by the following method (Nippon Oil Co., Ltd.) Made) solubility at 20 °C. The results are shown in Table 1. [Measurement method] Measure 1 g of polyisocyanate composition, add mineral spirit A to it, and use turbidity as the end point to obtain the amount of mineral spirit A added at this point (g) ° Use this addition amount 'by the following formula (1) Calculate the tolerance limit. Amount (1 g) Valley limit = amount of organic solvent required (g) / sample Table 1
如表 1 所可 Φπ，ΛΛΙ 1 ，dr* 氰酸酯組 知貫施例i及2所得之聚異 -26 201000509 成物對於低極性溶劑之礦油精A之溶解性優異。 [3]二液型塗料組成物之製造 [實施例3〜6、比較例3〜5] 實施例1、2及比較例1、2所得之聚異氰酸酯組成物 S-l、S-2、S-3、S-4以表2所不之比例調配含氣多兀醇（ LUMIFLONLF-800，旭硝子胺基甲酸酯（股）製）或丙烯 酸多元醇（ACRYDIC A-801 > HU-596，DIC (股）製）、 氧化鈦（CR-90，石原產業（股）製）、礦油精 A (新曰 本石油（股）公司）以及SOLUBESSO 100 (埃索化學公 司製），調製二液型塗料組成物。 [表2] 實施例 3 實施例 4 實施例 5 實施例 6 比較例 3 比較例 4 比較例 5 聚異氰 酸酯 S-l 2.6 5.8 - 3.5 - 參 - S-2 - • 2.5 • - - S-3 - 一 - 2.4 - S-4 - • - - 2.8 6.2 SOLUBESSO 100 - 2.5 - - - 2.7 礦油精A 1.1 _ 1.1 1.5 1.0 1.2 - NC0含量（％) 9.0 9.2 9.5 9.0 8.4 9.0 8.4 黏度（mPa · s，25°C ) 40 50 50 50 50 50 50 LUMIFLON LF-800 20.0 - 20.0 - 20.0 20.0 - ACRYDIC A-801 - 20.0 _ - - • 20.0 ACRYDIC HU-596 - - - 20.0 - - - SOLUBESSO 100 5.1 • • - - 5.3 礦油精A 7.1 • 7.0 6.7 7.0 7.2 - 氧化鈦CR-90 9.7 10.5 9.7 9.0 9.6 9.8 10.8 於上述實施例3〜6及比較例3〜5所調製之二液型塗料 -27- 201000509 組成物，使用塗佈器以濕膜厚100微米分別塗佈於以甲基 乙基酮脫脂之鋼板（JIS G3141 ’商品名SPCC-SB ’ PF-1077處理’日本試驗板工業（股）製）’於溫度2〇C、 相對溼度6 5 %之環境下進行養生7天’形成乾燥膜厚 4 0〜5 0微米之塗膜。對所得塗膜’評價下述各物性。結果 示於表4。 (1 )塗膜外觀 由目視觀察硬化組成物之外觀。 形成無霧狀或渾濁等之均一塗膜時記爲合格（〇）， 發生霧狀或渾濁等者記爲不合格（X )。又，外觀評價係 對未調配顏料之下述組成物以上述方法對硬化塗膜進行。 [表3] 實施例 3 實施例 4 實施例 5 實施例 6 比較例 3 比較例 4 比較例 5 聚異氰 酸酯 S-1 2.6 5.8 - 3.5 . _ S-2 - - 2.5 - _ 一 _ S-3 - - - - 2.4 . S-4 - - - 一 2.8 6.2 LUMIFLON LF-800 20.0 - 20.0 • 20.0 20.0 ACRYDIC A-801 - 20.0 - — 20.0 ACRYDIC HU-596 - - - 2〇χΡ SOLUBESSO 100 - 1.7 - 0.8 礦油精A 1.7 - 1.6 2.0 1.8 0.5 氧化鈦CR-90 ^ 0 0 0 0 0 0 0 (2 )耐彎折性 使用直徑2毫米之圓筒型心軸’依據JIS K-5 6 00-5 -1 -28- 201000509 之耐彎折試驗，評價由圓筒型心軸彎折時之塗膜裂痕以及 自鋼板剝落之有無。未產生塗膜裂痕、剝落者記爲合格。 (3 )耐吸杯（c u p p i n g )性 使用壓入器，依據JIP K-5600-5-2之耐吸杯試驗，評 價藉由壓入於承受部分變形時之塗膜裂痕以及自鋼板剝落 之有無。藉由壓入器，產生塗膜裂痕、剝落之壓入深度（ 毫米）作爲耐吸杯性。耐吸杯性爲顯示塗膜之基材追隨性 及柔軟性之値，上述壓入深度數値越大則追隨性及柔軟性 越商。 (4 )耐砝碼落下性 使用直徑10.3毫米、質量0.5公斤之砝碼，依據JIS Κ-5600-5-3之耐砝碼洛下試驗，評價藉由砝碼落下於承受 變形時之塗膜之裂痕以及自鋼板剝落之有無。以產生塗膜 裂痕、剝落之最低落下高度（公分）作爲耐砝碼落下性。 (5 )塗膜硬度 塗膜表面硬度係依據JIS Κ-5600-5-4之拉引硬度試驗 (鉛筆法）測定。塗膜表面未產生傷痕痕跡之最硬鉛筆之 硬度作爲塗膜硬度。 (6 )密著性 塗膜密著性係依據Π S Κ - 5 6 0 0 - 5 - 6之棋盤格膠帶剝離 -29- 201000509 試驗，對塗膜切成直角之格子圖形’對於貫通基底時之自 基底剝離評價塗膜耐性。 (7 )塗膜伸展性 將表3所示之各調配液塗佈於貼附有離型紙及標牌（ guide)之玻璃板上，於溫度20°C、相對溼度65%之環境 下養生7天，形成乾燥膜厚200微米之塗膜。使用啞鈴切 割器，自所得塗膜製作試驗片，爲評價塗膜之伸展性而實 施拉伸試驗。 試驗片：4號啞鈴型 拉伸速度：200毫米/分鐘 [表4] 實施例3 實施例4 實施例5 實施例6 比較例3 比較例4 比較例5 外觀 〇 〇 〇 〇 X X 〇 耐彎折性 合格 合格 合格 合格 合格 合格 合格 耐吸杯性 10 (材料破裂) 10 (材料破裂） 10 (材繼裂） 10 (材料破裂） 10 (材料破裂) 10 (材料破裂) 10 (材料破裂） 耐砝碼落下性 100 100 100 100 100 100 100 十字切割 (分類） 0 0 0 0 0 0 0 ; 硬度 4B 3B 4B 3B 4B 4B 2B 伸 展 性 Γϊϊ伸斷裂 伸長度(％) 190 120 140 140 100 100 70 拉伸破裂 強度(MPa) 19 18 17 19 15 15 20 如表4所示可知’由實施例3〜6之塗料組成物所得之 塗膜之伸展性優異且其他諸特性亦良好。 -30-As shown in Table 1, the Φπ, ΛΛΙ 1 , dr* cyanate groups are known to have excellent solubility in mineral spirits A of low-polarity solvents. [3] Production of two-liquid type coating composition [Examples 3 to 6, Comparative Examples 3 to 5] The polyisocyanate compositions S1, S-2, and S-3 obtained in Examples 1, 2 and Comparative Examples 1 and 2. , S-4 is formulated with a gas-containing polyterpene alcohol (LUMIFLONLF-800, manufactured by Asahi Nitrate) or acrylic polyol (ACRYDIC A-801 > HU-596, DIC (not shown in Table 2). Co., Ltd.), titanium oxide (CR-90, Ishihara Sangyo Co., Ltd.), mineral spirits A (New Okamoto Oil Co., Ltd.), and SOLUBSSO 100 (made by Esso Chemical Co., Ltd.) to prepare two-component coatings Composition. [Table 2] Example 3 Example 4 Example 5 Example 6 Comparative Example 3 Comparative Example 4 Comparative Example 5 Polyisocyanate Sl 2.6 5.8 - 3.5 - gins - S-2 - • 2.5 • - - S-3 - one - 2.4 - S-4 - • - - 2.8 6.2 SOLUBESSO 100 - 2.5 - - - 2.7 Mineral spirit A 1.1 _ 1.1 1.5 1.0 1.2 - NC0 content (%) 9.0 9.2 9.5 9.0 8.4 9.0 8.4 Viscosity (mPa · s, 25° C ) 40 50 50 50 50 50 50 LUMIFLON LF-800 20.0 - 20.0 - 20.0 20.0 - ACRYDIC A-801 - 20.0 _ - - • 20.0 ACRYDIC HU-596 - - - 20.0 - - - SOLUBESSO 100 5.1 • • - - 5.3 Mineral spirit A 7.1 • 7.0 6.7 7.0 7.2 - Titanium oxide CR-90 9.7 10.5 9.7 9.0 9.6 9.8 10.8 The two-component coatings -27-201000509 prepared in the above Examples 3 to 6 and Comparative Examples 3 to 5, It was applied to a steel sheet degreased with methyl ethyl ketone (JIS G3141 'trade name SPCC-SB 'PF-1077 treated 'Japan Test Plate Industry Co., Ltd.) at a temperature of 100 μm in a wet film thickness using an applicator. 2〇C, the relative humidity of 6 5 % of the environment for 7 days to form a dry film thickness of 40 ~ 50 microns coating film. The following physical properties were evaluated for the obtained coating film'. The results are shown in Table 4. (1) Appearance of coating film The appearance of the hardening composition was visually observed. When a uniform coating film such as no fog or turbidity is formed, it is regarded as pass (〇), and when it is foggy or turbid, it is regarded as unacceptable (X). Further, the appearance evaluation was carried out on the cured coating film by the above method for the following composition of the unmixed pigment. [Table 3] Example 3 Example 4 Example 5 Example 6 Comparative Example 3 Comparative Example 4 Comparative Example 5 Polyisocyanate S-1 2.6 5.8 - 3.5 . _ S-2 - - 2.5 - _ I_ S-3 - - - - 2.4 . S-4 - - - One 2.8 6.2 LUMIFLON LF-800 20.0 - 20.0 • 20.0 20.0 ACRYDIC A-801 - 20.0 - — 20.0 ACRYDIC HU-596 - - - 2〇χΡ SOLUBESSO 100 - 1.7 - 0.8 Mine Oil Essence A 1.7 - 1.6 2.0 1.8 0.5 Titanium oxide CR-90 ^ 0 0 0 0 0 0 0 (2) Bending resistance using a cylindrical mandrel with a diameter of 2 mm 'according to JIS K-5 6 00-5 - 1 -28- 201000509 The bending resistance test evaluates the cracks in the coating film when the cylindrical mandrel is bent and the presence or absence of peeling from the steel sheet. No cracks in the coating film and peeling were recorded as qualified. (3) Suction cup (c u p p i n g) The indenter was used, and the evaluation was carried out according to the suction cup test of JIP K-5600-5-2, and the evaluation was carried out by press-fitting the film crack when subjected to partial deformation and the presence or absence of peeling from the steel sheet. By the presser, the penetration depth (mm) of the coating film crack and peeling is generated as the suction resistance. The suction resistance is a measure of the substrate followability and flexibility of the coating film, and the greater the number of the indentation depths, the more satisfactory the followability and the flexibility. (4) The weight-resistance of the weight-resistance code is 10.3 mm and the weight of 0.5 kg is used. According to JIS Κ-5600-5-3, the test is carried out to evaluate the coating film when the weight is dropped by the weight. Cracks and the presence or absence of peeling from the steel plate. The lowest drop height (cm) of the coating film crack and peeling is used as the drop resistance. (5) Film hardness The surface hardness of the film was measured in accordance with the pull hardness test (pencil method) of JIS Κ-5600-5-4. The hardness of the hardest pencil on the surface of the coating film where no scratch marks were formed was taken as the hardness of the coating film. (6) Adhesive film adhesion is based on the Π S Κ - 5 6 0 0 - 5 - 6 checkerboard tape peeling -29- 201000509 test, the film is cut into a right-angled grid pattern 'for the through substrate The film resistance was evaluated from the substrate peeling. (7) Film stretchability Each formulation shown in Table 3 was applied to a glass plate to which a release paper and a guide were attached, and maintained at a temperature of 20 ° C and a relative humidity of 65% for 7 days. A coating film having a dry film thickness of 200 μm was formed. A test piece was prepared from the obtained coating film using a dumbbell cutter, and a tensile test was performed to evaluate the stretchability of the coating film. Test piece: Dumbbell type stretching speed: 200 mm/min [Table 4] Example 3 Example 4 Example 5 Example 6 Comparative Example 3 Comparative Example 4 Comparative Example 5 Appearance 〇〇〇〇 XX 〇 Bending resistance Qualified Qualified Qualified Qualified Qualified Refractory Cupability 10 (Material rupture) 10 (Material rupture) 10 (Material cracking) 10 (Material rupture) 10 (Material rupture) 10 (Material rupture) 10 (Material rupture) Resistance code Dropping 100 100 100 100 100 100 100 Cross cutting (classification) 0 0 0 0 0 0 0 ; Hardness 4B 3B 4B 3B 4B 4B 2B Extensible elongation Elongation (%) 190 120 140 140 100 100 70 Tensile cracking Strength (MPa) 19 18 17 19 15 15 20 As shown in Table 4, it was found that the coating film obtained from the coating compositions of Examples 3 to 6 was excellent in stretchability and other properties were also good. -30-