以下詳細地對本發明之實施形態進行說明。再者，本發明並不限定於以下之實施形態，可於其主旨之範圍內進行各種變化而實施。首先，對上述通式(1)所表示之二苯并哌喃系染料進行說明。 通式(1)中，作為R1
～R4
所表示之「可具有取代基之碳原子數1～20之直鏈狀或支鏈狀之烷基」，具體而言可列舉：甲基、乙基、丙基、丁基、戊基、己基、庚基、辛基、壬基、癸基等直鏈狀之烷基；異丙基、異丁基、第二丁基、第三丁基、異辛基等支鏈狀之烷基。 通式(1)中，作為R1
～R4
所表示之「可具有取代基之碳原子數3～20之環烷基」，具體而言可列舉：環丙基、環戊基、環己基、環庚基、環辛基、環壬基、環癸基等環烷基。 通式(1)中，作為R1
～R4
所表示之「可具有取代基之碳原子數6～20之芳香族烴基」或「可具有取代基之碳原子數2～20之雜環基」，具體而言可列舉：苯基、萘基、蒽基、菲基、芘基、聯三苯基、苝基、茚基、茀基、吡啶基、嘧啶基、三基、吡咯基、咪唑基、吡唑基、三唑基、喹啉基、異喹啉基、萘啶基、吲哚基、苯并咪唑基、咔唑基、咔啉基、吖啶基、啡啉基、呋喃基、苯并呋喃基、二苯并呋喃基、噻吩基、苯并噻吩基、二苯并噻吩基、㗁唑基、苯并㗁唑基、噻唑基、苯并噻唑基等，較佳為苯基。此處，於本發明中，「芳香族烴基」係指表示包含單環之芳香族烴基或複數環之縮合多環芳香族基之基。進而，於本發明中，「雜環基」係指表示單環或複數環之雜環基，表示含氮、含氧或含硫之雜環，可為具有芳香族性者，亦可為不具有芳香族性者。 通式(1)中，作為R1
～R4
所表示之「具有取代基之碳原子數1～20之直鏈狀或支鏈狀之烷基」中之「取代基」，具體而言可列舉 氟原子、氯原子、溴原子、碘原子等鹵素原子；-SO3 -
；環丙基、環丁基、環戊基、環己基、環辛基等碳原子數3～19之環烷基； 甲氧基、乙氧基、丙氧基、丁氧基、戊氧基、己氧基、庚氧基、辛氧基、壬氧基、癸氧基等碳原子數1～19之直鏈狀之烷氧基； 異丙氧基、異丁氧基、第二丁氧基、第三丁氧基、異辛氧基等碳原子數3～19之支鏈狀之烷氧基； 環丙氧基、環丁氧基、環戊氧基、環己氧基等碳原子數3～19之環烷氧基； 苯基、萘基、聯苯基、蒽基、菲基、芘基、聯三苯基、茚基、茀基等碳原子數6～19之芳香族烴基或縮合多環芳香族基； 吡啶基、嘧啶基、三基、吡咯基、咪唑基、吡唑基、三唑基、喹啉基、異喹啉基、萘啶基、吲哚基、苯并咪唑基、咔唑基、咔啉基、吖啶基、啡啉基、呋喃基、苯并呋喃基、二苯并呋喃基、噻吩基、苯并噻吩基、二苯并噻吩基、㗁唑基、苯并㗁唑基、噻唑基、苯并噻唑基等碳原子數2～19之雜環基等。 該等「取代基」可僅包含1個，亦可包含複數個，於包含複數個之情形時可相互相同亦可不同。又，該等「取代基」亦可進而具有上述例示之取代基。 通式(1)中，作為R1
～R4
所表示之「具有取代基之碳原子數3～20之環烷基」、「具有取代基之碳原子數6～20之芳香族烴基」或「具有取代基之碳原子數2～20之雜環基」中之「取代基」，具體而言可列舉：氟原子、氯原子、溴原子、碘原子等鹵素原子；-SO3 -
； 甲基、乙基、丙基、丁基、戊基、己基、庚基、辛基、壬基、癸基等碳原子數1～14之直鏈狀之烷基； 異丙基、異丁基、第二丁基、第三丁基、異辛基等碳原子數3～14之支鏈狀之烷基； 環丙基、環丁基、環戊基、環己基、環辛基等碳原子數3～14之環烷基； 甲氧基、乙氧基、丙氧基、丁氧基、戊氧基、己氧基、庚氧基、辛氧基、壬氧基、癸氧基等碳原子數1～14之直鏈狀之烷氧基； 異丙氧基、異丁氧基、第二丁氧基、第三丁氧基、異辛氧基等碳原子數3～14之支鏈狀之烷氧基； 環丙氧基、環丁氧基、環戊氧基、環己氧基等碳原子數3～14之環烷氧基； 苯基、萘基、聯苯基、蒽基、菲基、茚基、茀基等碳原子數6～14之芳香族烴基或縮合多環芳香族基； 吡啶基、嘧啶基、三基、吡咯基、咪唑基、吡唑基、三唑基、喹啉基、異喹啉基、萘啶基、吲哚基、苯并咪唑基、咔唑基、咔啉基、吖啶基、啡啉基、呋喃基、苯并呋喃基、二苯并呋喃基、噻吩基、苯并噻吩基、二苯并噻吩基、㗁唑基、苯并㗁唑基、噻唑基、苯并噻唑基等碳原子數2～14之雜環基等。 該等「取代基」可僅包含1個，亦可包含複數個，於包含複數個之情形時可相互相同亦可不同。又，該等「取代基」亦可進而具有上述例示之取代基。 通式(1)中，作為R5
～R8
所表示之「鹵素原子」，可列舉：氟原子、氯原子、溴原子、碘原子等。作為「鹵素原子」，較佳為氟原子或氯原子。 通式(1)中，作為R5
～R8
所表示之「可具有取代基之碳原子數1～20之直鏈狀或支鏈狀之烷基」、「可具有取代基之碳原子數3～20之環烷基」、「可具有取代基之碳原子數1～20之直鏈狀或支鏈狀之烷氧基」、「可具有取代基之碳原子數3～20之環烷氧基」或「可具有取代基之碳原子數2～20之直鏈狀或支鏈狀之烯基」中之「碳原子數1～20之直鏈狀或支鏈狀之烷基」、「碳原子數3～20之環烷基」、「碳原子數1～20之直鏈狀或支鏈狀之烷氧基」、「碳原子數3～20之環烷氧基」或「碳原子數2～20之直鏈狀或支鏈狀之烯基」，具體而言可列舉： 甲基、乙基、丙基、丁基、戊基、己基、庚基、辛基、壬基、癸基等直鏈狀之烷基； 異丙基、異丁基、第二丁基、第三丁基、異辛基等支鏈狀之烷基； 環丙基、環戊基、環己基、環庚基、環辛基、環壬基、環癸基等環烷基； 甲氧基、乙氧基、丙氧基、丁氧基、戊氧基、己氧基、庚氧基、辛氧基、壬氧基、癸氧基等直鏈狀之烷氧基； 異丙氧基、異丁氧基、第二丁氧基、第三丁氧基、異辛氧基等支鏈狀之烷氧基； 環丙氧基、環丁氧基、環戊氧基、環己氧基等環烷氧基； 乙烯基、1-丙烯基、烯丙基、1-丁烯基、2-丁烯基、1-戊烯基、1-己烯基、異丙烯基、異丁烯基、或該等烯基鍵結複數個而成之直鏈狀或支鏈狀之烯基等。 通式(1)中，作為R5
～R8
所表示之「具有取代基之碳原子數1～20之直鏈狀或支鏈狀之烷基」、「具有取代基之碳原子數3～20之環烷基」、「具有取代基之碳原子數1～20之直鏈狀或支鏈狀之烷氧基」、「具有取代基之碳原子數3～20之環烷氧基」或「具有取代基之碳原子數2～20之直鏈狀或支鏈狀之烯基」中之「取代基」，具體而言可列舉： 氟原子、氯原子、溴原子、碘原子等鹵素原子；-SO3 -
； 環丙基、環戊基、環己基、環辛基等碳原子數3～17之環烷基； 甲氧基、乙氧基、丙氧基、丁氧基、戊氧基、己氧基、庚氧基、辛氧基、壬氧基、癸氧基等碳原子數1～17之直鏈狀之烷氧基； 異丙氧基、異丁氧基、第二丁氧基、第三丁氧基、異辛氧基等碳原子數1～17之支鏈狀之烷氧基； 環丙氧基、環丁氧基、環戊氧基、環己氧基等碳原子數3～17之環烷氧基； 苯基、萘基、聯苯基、蒽基等碳原子數6～18之芳香族烴基或碳原子數6～17之縮合多環芳香族基等。該等「取代基」可僅包含1個，亦可包含複數個，於包含複數個之情形時可相互相同亦可不同。又，該等「取代基」亦可進而具有上述例示之取代基。 通式(1)中，作為R1
～R4
，較佳為氫原子、可具有取代基之碳原子數1～10之直鏈狀或支鏈狀之烷基、可具有取代基之碳原子數5～12之環烷基或可具有取代基之碳原子數6～12之芳香族烴基。通式(1)中，R1
與R2
之組合與R3
與R4
之組合可相互相同亦可不同。 通式(1)中，R1
與R2
彼此、或R3
與R4
彼此亦可相互鍵結而形成環，作為於該情形時所形成之環，較佳為5員環或6員環，更佳為5員環。R1
與R2
彼此、及R3
與R4
彼此可兩組形成環，亦可任一組形成環。 通式(1)中，作為R5
～R8
，較佳為氫原子、鹵素原子、-SO3 -
、可具有取代基之碳原子數1～20之直鏈狀或支鏈狀之烷基、或可具有取代基之碳原子數1～20之直鏈狀或支鏈狀之烷氧基，更佳為氫原子或-SO3 -
。又，於R5
～R8
之任一者為-SO3 -
之情形時，R7
更佳為-SO3 -
。 通式(1)中，於R5
～R8
中，亦可以相鄰基彼此相互鍵結而形成環，作為於該情形時所形成之環，較佳為5員環或6員環，更佳為6員環。 通式(1)中，「M」表示鹼金屬原子，較佳為鋰原子、鈉原子或鉀原子，更佳為鋰原子或鈉原子，尤佳為鈉原子。 通式(1)中，x表示「M」之數量，為0或1之整數，又，通式(1)所表示之化合物整體為電中性。其中，通式(1)中，-SO3 -
之數量設為1個或2個，於僅包含1個-SO3 -
之情形時成為x=0(不存在M)，又，於包含2個-SO3 -
之情形時成為x=1(存在1個M)。 通式(1)所表示之二苯并哌喃系染料可藉由公知之方法(參照非專利文獻1等)例如按照以下之方式合成。使苯甲醛-2-磺酸鈉等具有等效之取代基之磺醯基醛衍生物與二乙基胺基苯酚等具有等效之取代基之羥基苯胺衍生物於硫酸等酸水溶液中以適當之加熱條件進行縮合反應，而獲得下述通式(2)所表示之中間物。其次，藉由對下述通式(2)進行脫水而獲得由下述通式(3)所表示之中間物。進而，使下述通式(3)於酸水溶液中在適當之加熱條件下與氯化鐵(III)(FeCl3
)進行反應而氧化，並利用氫氧化鈉(NaOH)等鹼性水溶液中和後，使用氯化鈉(NaCl)等氯化合物進行鹽析，藉此獲得含有通式(1)所表示之化合物之產物。 [化4][化5][化6]又，通式(1)所表示之化合物例如亦可藉由如下方法合成：使作為起始原料之下述通式(4)所表示之3,6-二氯螺[9H-二苯并哌喃-9,3'-[3H][2,1]苯并㗁硫醇]1',1'-二氧化物(或二氯磺基熒烷)衍生物與含氮原子之胺化合物、雜環式化合物等於N-甲基吡咯啶酮(NMP)等溶解原料之任意之溶劑中在適當之溫度條件下進行反應(例如參照專利文獻6等)。 [化7]上述通式(2)～(4)中，R1
～R8
意指與通式(1)中之定義相同之定義。 於通式(1)所表示之二苯并哌喃系染料之合成法中，於所析出之二苯并哌喃系染料牢固地附著而妨礙攪拌之情形時，為了消除或緩解該情況，亦可混合有機溶劑。作為所混合之有機溶劑，只要與所對應之二苯并哌喃系染料具有充分之溶解性則無特別限制，可單獨或混合使用甲苯、二甲苯等芳香族烴；丙酮、2-丁酮、2-戊酮、3-戊酮等酮類；乙酸乙酯、乙酸丁酯等酯類；甲醇、乙醇、丙醇、異丙醇、丁醇、戊醇、己醇等醇類等。通式(1)所表示之二苯并哌喃系染料可藉由視需要對利用上述合成方法所獲得之產物進行利用管柱層析法之精製；利用矽膠、活性碳、活性白土等之吸附精製；利用溶劑之分散洗淨或再結晶、晶析、鹽析等公知之精製而獲得。用於該等精製方法之溶劑無特別限定，可單獨或混合使用水、甲醇、乙醇等醇類；二氯甲烷、氯仿等鹵甲烷類；甲苯等。作為通式(1)所表示之本發明之二苯并哌喃系染料，可使用市售品。具體而言，市售有C.I.酸性紅52、C.I.酸性紅289等二苯并哌喃系染料、或含有該等染料作為主成分之組合物。該等亦可直接使用而製備本發明之著色組合物，又，可使用以與上述之二苯并哌喃系染料之精製方法相同之方法精製而成者製備本發明之著色組合物。 將作為通式(1)所表示之本發明之二苯并哌喃系染料之較佳之化合物之具體例示於以下之式(A-1)～(A-37)，但本發明並不限定於該等化合物。再者，於下述結構式中省略記載一部分氫原子。又，即便於存在立體異構物之情形時，亦記載其平面結構式。 [化8][化9][化10][化11][化12][化13][化14][化15][化16][化17][化18][化19][化20][化21][化22][化23][化24][化25][化26][化27][化28][化29][化30][化31][化32][化33][化34][化35][化36][化37][化38][化39][化40][化41][化42][化43][化44][化45][化46][化47][化48][化49][化50][化51][化52][化53][化54][化55]本發明之二苯并哌喃系染料於熱重量測定-示差熱分析(TG-DTA)中之分解開始溫度較佳為250℃以上，更佳為300℃以上，尤佳為360℃以上。於考慮應用於彩色濾光器之情形時，該分解開始溫度越高越佳。 以下詳細地對本發明之含有通式(1)所表示之二苯并哌喃系染料之著色組合物進行說明。本發明之著色組合物設為如下者，即，於其固形物成分中之成分中，含有通式(1)所表示之二苯并哌喃系染料作為主成分，亦可含有一定濃度範圍之水分。藉由存在該著色組合物中之水分，可提高二苯并哌喃系染料於PGME等有機溶劑中之溶解性。具體而言，藉由於含二苯并哌喃系染料之著色組合物整體中，將含水率設為3～18重量%，可維持耐熱性並且獲得對於PGME等有機溶劑之溶解性較高之著色組合物。此處本發明中之「含水率」表示著色組合物整體之重量中之水分之重量比率，單位以「重量%」表示。 本發明之含二苯并哌喃系染料之著色組合物於其製造步驟中藉由形成水分子-二苯并哌喃分子複合體，可使於PGME等有機溶劑中之溶解性提高。此種含有水分子與二苯并哌喃分子之著色組合物可於固體(粉末等)之狀態下，藉由分子間之牢固之氫鍵保持其固體狀態，且於溶解於溶劑時，水分子容易溶解，與水分子溶解之同時二苯并哌喃分子可以分子單位容易地溶解於溶劑中。又，由於亦可不使用多餘之界面活性劑等，故而分散液亦不發生變質(固相-液相之分離等)，可於無損其他彩色濾光器製造用材料之溶解性等之情況下容易地操作。對本發明之含二苯并哌喃系染料之著色組合物中之二苯并哌喃分子與水分子之組成比進行說明。若將二苯并哌喃分子之氧原子、氮原子、-SO3 -
基或金屬原子之極性部分視作形成與水分子之氫鍵，則可認為1個二苯并哌喃分子能夠與至多大約6～8個左右之水分子形成穩定之錯合物狀(或水合物)結構。例如，於包含作為代表性二苯并哌喃系染料之式(II)與水分子之著色組合物中，二苯并哌喃分子與水分子形成穩定結構之莫耳比為1：1～1：7之情形時，於著色組合物整體中，含水率成為3～18重量%。於無任何水分子之狀態(含水率未達3重量%)下，附近之二苯并哌喃分子彼此產生凝聚，另一方面，於水分子之比率較高(含水率大於18重量%)之情形時，相鄰之水分子彼此凝聚，固體狀態之粉末變為液狀，導致製造步驟產生不便。如此，本發明之著色組合物兼具溶解性與作為粉末之易操作性兩者。根據以上內容，本發明之含二苯并哌喃系染料之著色組合物之含水率於著色組合物整體中較佳為3～18重量%，更佳為4～18重量%，尤佳為10～14重量%。 於本發明之含二苯并哌喃系染料之著色組合物中，具有目標含水率之著色組合物可利用以下方法獲得。再者，該方法不限定於一定之含水率之著色組合物之製備方法，亦可用作相同之著色組合物之精製方法。首先，於適當尺寸之容器中放入含有二苯并哌喃系染料作為主成分之粉末、活性碳、及溶劑並進行混合、加熱，然後攪拌一定時間。攪拌後進行熱過濾而獲得濾液。將該濾液一面於大氣壓下或進行減壓一面進行濃縮，而獲得濃縮物。自容器中以濃縮物之形式取出含有溶劑之著色組合物，利用另一容器進行乾燥(一次乾燥)。進而，於一定溫度下進行減壓乾燥而去除溶劑。如此，獲得含有通式(1)所表示之二苯并哌喃系染料且具有一定含水率之著色組合物。此處，作為攪拌用容器之材質，可選擇適當者使用，例如，可使用燒瓶等玻璃製容器、金屬製容器、樹脂製容器、經玻璃襯裡之容器等。 攪拌用容器之大小可為各種大小，對於粉末100 g較佳為1～5 L之大小。但不限定於該範圍，可藉由溶解所使用之二苯并哌喃系染料所需之溶劑量而任意決定。 為了提高活性碳之吸附能力，於溶劑中混合時所使用之活性碳較佳為粉狀或微粉狀。 溶劑較佳為醇，於醇之情形時，較佳為甲醇、乙醇、丙醇、異丙醇、丁醇，更佳為甲醇。 溶劑可使用市售之通用品。就調整著色組合物之含水率之目的而言，較佳為未進行脫水處理者。於使用經脫水處理者之情形時，於溶劑中可添加亦可不添加水等水分。於溶劑為醇之情形時，「醇中所含之水分含有率」(以下，與著色組合物之含水率區別)較佳為0.01～10重量%，更佳為0.1～5重量%。於混合時添加水亦可調整著色組合物之含水率。於使用醇作為溶劑之情形時，為了使「醇中所含之水分含有率」成為0.01～10重量%，可藉由添加水進行調整。作為添加水，可列舉蒸餾水、自來水、工業用水、離子交換水等。該等之中，較佳為離子交換水。 於溶劑中之混合時之二苯并哌喃系染料與溶劑之重量比相對於二苯并哌喃系染料之重量，溶劑較佳為3～10倍之重量比。但並不限定於該範圍，可任意決定將所使用之二苯并哌喃系染料溶解所需之量。 作為其他成分，為了提高本發明之著色組合物作為彩色濾光器用著色劑之性能，可添加界面活性劑、分散劑、消泡劑、調平劑、其他彩色濾光器用著色劑之製造時混合之添加劑等有機化合物等。其中，著色組合物中之該等添加劑之含有率較佳為適量，較佳為不使本發明之著色組合物於溶劑中之溶解性降低、或不使其過度提高，又，不影響彩色濾光器製造時所使用之其他同類添加劑之效果之範圍之含有率。該等添加物可於著色組合物之製備之任意時機投入。 混合或攪拌過程中之容器中之氣體可列舉空氣、氮氣、其他惰性氣體等，並無特別限定。考慮製造時對於靜電所致之引燃之安全性，較佳為於容器中利用氮氣等惰性氣體進行置換。 含有著色組合物之液之濃縮方法並無特別限定，將去除活性碳之濾液於大氣壓下或減壓下蒸餾去除溶劑而進行。減壓蒸餾去除裝置亦可使用蒸發器等。若過度地進行濃縮，則濃縮物之回收困難等影響含水率之調整，又，於濃縮不充分之情形時，於下一步驟之乾燥需要時間，而影響製造成本。因此，濃縮度較佳為於所使用之粉末之體積之2～5倍之範圍內進行。 濃縮物之乾燥係移入如盤或槽之類的容器中實施乾燥而進行。為了使含水率成為平衡狀態，於大氣壓下靜置1～96小時後進行乾燥(一次乾燥)。乾燥時之溫度較佳為20℃～100℃之範圍。此處，較佳為於暫時乾燥中，不使其完全乾燥，而預留某種程度之水分。 經一次乾燥之含二苯并哌喃系染料之著色組合物使用具有真空乾燥機等排氣裝置之乾燥機等進而進行乾燥(二次乾燥)。亦可代替真空乾燥機，於底面積較大之槽狀容器上進行風乾。乾燥時之溫度較佳為40～100℃之範圍。乾燥時間較佳為4～48小時之範圍，為了獲得設為目標含水率之著色組合物，可以任意時間進行設定，並無特別限定。於使用醇作為溶劑之情形時，可將儘可能去除醇之時間點設為乾燥終點。作為乾燥終點之測定方法，可列舉基於粉末狀態觀察、重量測定、核磁共振分析(NMR)、氣相層析分析(GC)等之溶劑成分之濃度測定之方法。 作為藉由以上方式製備之著色組合物之含水率之測定方法，可列舉：使用電量滴定法或容量滴定法之卡氏(KF)法；使用熱重量測定-示差熱分析(TG-DTA)裝置之熱分析法；使用加熱乾燥式水分計等之加熱乾燥法；氣相層析(GC)法、紅外線或近紅外線吸收法；核磁共振吸收法；電阻法；介電常數法；蒸餾法等方法，就精度之方面而言較佳為卡氏法，就可確認水分蒸發時之吸熱反應之方面而言較佳為熱分析法、或加熱乾燥法。 藉由以上所說明之方法，可獲得含有通式(1)所表示之二苯并哌喃系染料之本發明之著色組合物，其以成為任意之含水率之方式進行過調整。 本發明之著色組合物通常以具有結晶狀、微晶狀、微粉末狀、薄片狀、針晶狀、顆粒狀等形狀之固體粉末之狀態使用，並無特別限定。 本發明之著色組合物之固體粉末之狀態可使用光學顯微鏡、掃描式電子顯微鏡(SEM)等觀察。又，可根據所觀察之圖像獲得粉末之粒徑分佈，具體而言，可使用求出轉換為規則形狀(球、立方體等)之情形之等效直徑之圖像解析法、基於分散有粉末之電解液之電阻測定之庫爾特法、藉由粉末分散液之吸光度測定求出史托克(stokes)有效直徑之離心沈澱法、利用粉末分散液之繞射散射圖案解析之雷射繞射、散射法等進行測定。又，利用該等測定方法所獲得之粒徑使用粒徑分佈之平均值或中央值等，較佳為使用中央值。本發明之著色組合物較佳為處於0.1 μm～數mm之粒徑之範圍，但因製造條件或乾燥後之粉末之回收方法而使粒子之形狀發生變化，故而不限定於特定之粒徑，為了實現較高之溶解性，較佳為粒徑更小者，粒徑分佈之中央值較佳為處於0.1～100 μm之範圍。 本發明中之著色組合物之溶解性係以溶解度表示，溶解度表示粉末狀之著色組合物可溶解於特定之溶劑中之最大量於著色組合物中之比率，例如以「重量%(溶劑名，溫度)」等單位表示。溶解度例如藉由將試樣混合於特定之溶劑中，於一定溫度下將溶劑攪拌一定時間，並測定所製備之飽和溶液之濃度而獲得，亦可藉由基於溶解部之液相層析(LC)或吸光度測定等之濃度測定而獲得。 彩色濾光器用著色劑中所含有之著色組合物由於在彩色濾光器用著色劑及彩色濾光器之製造步驟中必須良好地溶解或分散於含有樹脂等之有機溶劑中，故而較佳為對於有機溶劑之溶解度較高。有機溶劑並無特別限定，具體而言可列舉：乙酸乙酯、乙酸正丁酯等酯類；二乙醚、丙二醇單甲醚(PGME)等醚類；丙二醇單甲醚乙酸酯(PGMEA)等醚酯類；丙酮、環己酮等酮類；甲醇、乙醇等醇類；二丙酮醇(DAA)等；苯、甲苯、二甲苯等芳香族烴類；N,N-二甲基甲醯胺(DMF)、N-甲基吡咯啶酮(NMP)等醯胺類；二甲基亞碸(DMSO)等。該等溶劑可單獨使用，亦可混合使用2種以上。該等之中，較佳為使用PGME。本發明之含二苯并哌喃系染料之著色組合物於有機溶劑中之溶解性、尤其是於PGME中之溶解性優異，例如，於25±2℃下對PGME之溶解度(溶劑PGME，25±2℃)較佳為0.5重量%以上，更佳為1重量%以上，尤佳為2重量%以上。 本發明之彩色濾光器用著色劑含有含通式(1)所表示之二苯并哌喃系染料之著色組合物與通常用於製造彩色濾光器之成分。一般之彩色濾光器例如於利用光微影法步驟之方法之情形時，藉由如下方式獲得：將使染料或顏料等色素與樹脂成分(包含單體、低聚物)或溶劑進行混合所製備之液體塗佈於玻璃或樹脂等基板上，使用光罩使其光聚合，製作可溶/不溶於溶劑之色素-樹脂複合膜之著色圖案，洗淨後進行加熱。又，即便於電沈積法或印刷法中，亦使用將色素與樹脂或其他成分混合而成者製作著色圖案。因此，作為本發明之彩色濾光器用著色劑中之具體成分，可列舉通式(1)所表示之二苯并哌喃系染料、其他染料或顏料等色素、樹脂成分、有機溶劑、及光聚合起始劑等其他添加劑。又，亦可自該等成分加以取捨選擇，或視需要追加其他成分。 於使用本發明之含二苯并哌喃系染料之著色組合物作為彩色濾光器用著色劑之情形時，亦可用於各色用彩色濾光器，較佳為用作藍色或紅色彩色濾光器用著色劑。 本發明之含二苯并哌喃系染料之彩色濾光器用著色劑可單獨使用二苯并哌喃系染料，為了調整色調，亦可混合其他染料或顏料等公知之色素。於用於紅色彩色濾光器用著色劑之情形時無特別限定，可列舉：C.I.顏料紅177、C.I.顏料紅209、C.I.顏料紅242、C.I.顏料紅254等紅色顏料；C.I.酸性紅88、C.I.鹼性紫10等紅色染料等。於用於藍色彩色濾光器用著色劑之情形時無特別限定，可列舉：C.I.鹼性藍3、7、9、54、65、75、77、99、129等鹼性染料；C.I.酸性藍9、74等酸性染料；分散藍3、7、377等分散染料；Spilon染料；花青系、靛藍系、酞菁系、蒽醌系、次甲基系、三芳基甲烷系、陰丹士林系、㗁 系、二㗁 系、偶氮系、不屬於本發明之二苯并哌喃系等藍色系染料或顏料等。 本發明之含二苯并哌喃系染料之彩色濾光器用著色劑中之其他色素之混合比相對於二苯并哌喃系染料較佳為5～2000重量%，更佳為設為10～1000重量%。液狀之彩色濾光器用著色劑中之染料等色素成分之混合比相對於著色劑整體較佳為0.5～70重量%，更佳為1～50重量%。 作為本發明之彩色濾光器用著色劑中之樹脂成分，只要為具有使用該等所形成之彩色濾光器樹脂膜之製造方式或使用時所需之性質者，則可使用公知者。例如可列舉：丙烯酸系樹脂、烯烴樹脂、苯乙烯樹脂、聚醯亞胺樹脂、聚胺酯樹脂、聚酯樹脂、環氧樹脂、乙烯醚樹脂、酚系(酚醛)樹脂、其他透明樹脂、光硬化性樹脂或熱硬化性樹脂，可適當組合該等單體或低聚物成分使用。又，亦可組合該等樹脂之共聚物使用。關於該等彩色濾光器用著色劑中之樹脂含量，於液狀著色劑之情形時，較佳為5～95重量%，更佳為10～50重量%。 作為本發明之彩色濾光器用著色劑中之其他添加劑，可列舉光聚合起始劑或交聯劑等樹脂之聚合或硬化所需之成分，又，可列舉為了使液狀之彩色濾光器用著色劑中之成分之性質穩定所需之界面活性劑或分散劑等。該等均可使用彩色濾光器製造用之公知者，並無特別限定。彩色濾光器用著色劑之固形物成分整體中之該等添加劑之總量之混合比較佳為5～60重量%，更佳為10～40重量%。 [實施例] 以下，藉由實施例具體地對本發明之實施形態進行說明，但本發明並不僅限定於以下之實施例。再者，實施例中所獲得之化合物之鑑定係藉由1
H-NMR分析(日本電子股份有限公司製造之核磁共振裝置，JNM-ECA-600)進行。[合成實施例1]化合物(A-20)之合成 向反應容器中添加下述式(5)所表示之苯甲醛-2,4-二磺酸鈉(79.9 g、258 mmol)、下述式(6)所表示之N,N-二乙基-3-胺基苯酚(85.1 g、515 mmol)、30重量%硫酸(0.799 L)，並於90℃下攪拌23小時。將反應液倒至水2.55 L中，於室溫下攪拌30分鐘後濾取出固體。向所獲得之固體中添加水0.51 L，於80℃下攪拌30分鐘後濾取出固體。向所獲得之固體中添加甲醇0.51 L，加熱並攪拌30分鐘直至回流，然後冷卻至室溫，並濾取出固體。於60℃下對所獲得之固體進行減壓乾燥，藉此獲得以下述式(7)所表示之中間物為主成分之粉末138.7 g。 [化56][化57][化58]向反應容器中添加包含上述式(7)所表示之中間物之粉末138.7 g，並添加90重量%硫酸0.828 L，於100℃下攪拌3小時後，升溫至120℃，進而攪拌3小時。冷卻至室溫後，倒至2.5 L之冰水中，濾取出所析出之固體。向所獲得之固體中添加水2.5 L並於室溫下攪拌後濾取出固體。對所獲得之固體進行乾燥，藉此獲得以下述式(8)所表示之中間物為主成分之粉末146.7 g。 [化59]向反應容器中添加包含上述式(8)所表示之中間物之粉末146.7 g，並添加10重量%硫酸1.61 L進行攪拌後，添加氯化鐵(III)(FeCl3
)291 g，於80℃下攪拌22小時。冷卻至室溫後，添加24重量%氫氧化鈉水溶液直至pH變為7。於添加氯化鈉174 g進行鹽析後，濾取出具有黏性之粗產物。將所獲得之粗產物添加至甲醇2.6 L中並於50℃下進行加熱攪拌後，過濾分離出不溶解成分。使濾液濃縮乾燥，其後利用矽膠管柱層析法(載體：矽膠、溶離液：氯仿→氯仿：甲醇＝95：5(體積比))對所獲得之深紫色產物進行精製。回收目標物組分並濃縮乾燥後，添加甲苯進行分散洗淨並濾取出固體。於70℃下對所獲得之固體進行減壓乾燥，藉此獲得作為目標化合物之含有下述式(A-20)作為主成分之紫紅色粉末(121.7 g、產率80%)。 [化60][合成實施例2]化合物(A-12)～(A-17)之合成 化合物(A-12)～(A-17)係利用與專利文獻6中記載之方法相同之方法獲得。以下例示化合物(A-13)之合成實施例。向反應容器中添加二氯磺基熒烷1.93 g、1,2,3,4,4a,9a-六氫-9H-咔唑3.30 g、NMP 40 mL並於80℃下攪拌8小時。放冷後將反應液倒至水400 mL中，添加1 M鹽酸直至pH變為2，並濾取出所析出之固體。利用矽膠管柱層析法(載體：矽膠、溶離液：氯仿/甲醇＝8/1(體積比))對所獲得之粗產物進行精製，藉此獲得紫紅色粉末(0.901 g、產率28%)。 [實施例1] 向10 L之反應容器中添加含有上述式之化合物(A-20)作為主成分之組合物700 g、活性碳40 g、甲醇6 L，並於55℃下攪拌1小時後，於50℃下進行過濾。於減壓下將該濾液濃縮至1/3，倒至不鏽鋼製之槽中，於25±2℃下風乾4天，於80℃下減壓乾燥5天。於重量減少按每天成為0.4重量%時結束乾燥，而獲得紫紅色粉末之含二苯并哌喃系染料(A-20)之著色組合物(715 g)。對該著色組合物進行NMR分析，確認未觀測到甲醇等有機溶劑之成分。 關於藉由上述方式獲得之含二苯并哌喃系染料(A-20)之著色組合物，使用水分計(平沼產業股份有限公司製造，自動水分測定裝置AQV-5S型)並藉由卡氏(KF)法而測定含水率。又，使用熱重量測定-示差熱分析裝置(MAC Science股份有限公司製造，TG-DTA 2000S型)於氮氣氣流下進行TG-DTA測定(試樣重量：5±1.5 mg，升溫速度：20℃/分)，從而測定分解開始溫度。其次，測定於室溫下在PGME溶劑中之溶解度(PGME，25±2℃)。將該等測定結果示於表1。 [實施例2～實施例5] 變更實施例1之風乾時間及減壓乾燥時間，除此以外進行相同之操作，而以紫紅色粉末之形式獲得實施例2～實施例5之含二苯并哌喃系染料(A-20)之著色組合物。關於該等著色組合物，與實施例1同樣地測定含水率、分解開始溫度及溶解度(PGME，25±2℃)。將測定結果與表1之實施例1之結果一併顯示。 [比較例1] 為了進行比較，變更實施例1之添加水之量或比率、風乾時間或減壓乾燥時間，除此以外進行與實施例1相同之操作，而製備將含水率調整為比實施例低之含二苯并哌喃系染料(A-20)之著色組合物。關於該著色組合物，與實施例1～實施例5同樣地測定含水率、分解開始溫度及溶解度(PGME，25±2℃)。將測定結果與表1之實施例之結果一併顯示。 [表1]
如表1所示，可知實施例1～實施例5之含二苯并哌喃系染料(A-20)之著色組合物由於分解開始溫度為360℃以上，具有充分之耐熱性，故而作為彩色濾光器用著色劑於實用方面不存在問題。又，關於該等實施例之著色組合物於PGME中之溶解性，可知於將比較例1之溶解度設為1之情形時，顯示自2.5倍至10倍以上之溶解度，作為彩色濾光器用著色劑較為有用。 另一方面，可知比較例1之含水率較低之未達3重量%之著色組合物雖為與實施例1～實施例5同等之分解開始溫度，但於PGME中之溶解度較低。 [實施例6～實施例11] 含有包含上述化合物(A-13)～(A-17)之二苯并哌喃系染料之著色組合物係利用與實施例1相同之方法分別於各種乾燥條件下將甲醇等有機溶劑乾燥去除而獲得。與實施例1同樣地測定該等之含水率、分解開始溫度及溶解度(PGME，25±2℃)。又，關於上述式(A-27)所表示之市售之二苯并哌喃系染料C.I.酸性紅289(中外化成股份有限公司製造)亦利用相同之方法進行測定。將測定結果彙總示於表2。[比較例2] 為了與實施例6～實施例11進行比較，變更該等實施例之乾燥條件，除此以外進行相同之操作，而製備將含水率調整為比實施例低之含上述二苯并哌喃系染料(A-12)之著色組合物，並測定含水率、分解開始溫度及溶解度(PGME，25±2℃)。將測定結果彙總示於表2。[比較例3及比較例4] 為了與實施例6～實施例11進行比較，針對下述式(B-1)所表示之C.I.鹼性藍1及下述式(B-2)所表示之C.I.鹼性藍7(均為東京化成工業股份有限公司製造)，以與實施例相同之方式測定含水率、分解開始溫度及溶解度(PGME，25±2℃)。將測定結果彙總示於表2。[化61][化62][表2]
如表2所示，可知實施例6～實施例11之各種含二苯并哌喃系染料之著色組合物由於分解開始溫度為300℃以上，具有充分之耐熱性，故而作為彩色濾光器用著色劑於實用方面不存在問題。又，關於該等實施例之著色組合物於PGME中之溶解性，可知於將比較例2之溶解度設為1之情形時，顯示10倍以上之溶解度，作為彩色濾光器用著色劑較為有用。 另一方面，可知比較例2之含水率未達3重量%之著色組合物雖具有與實施例同等之分解開始溫度，但於PGME中之溶解度較低。又，可知分別含比較例3之染料(B-1)及比較例4之染料(B-2)之著色組合物雖含水率為3重量%以上，於室溫下在PGME中之溶解度與實施例為相同程度，但不具有二苯并哌喃骨架，又，分解開始溫度較低，為220℃以下，耐熱性不充分。 [實施例12] 圖1表示觀察實施例4中所獲得之著色組合物之粉末而得之SEM圖像(標度長＝10 μm)。圖像中觀察到長度數μm～20 μm×寬度2～10 μm之針狀結晶，根據圖像所解析之粒徑分佈之中央值為3～4 μm。根據該結果，可知本發明之著色組合物作為彩色濾光器用著色劑而保持適於操作之粉末狀態。 如上所述，本發明之含二苯并哌喃系染料且含水率處於本發明所示之含水率之範圍之著色組合物具有較高之耐熱性，且具有於PGME等有機溶劑中之較高之溶解性，故而作為彩色濾光器用著色劑較為有用。 [產業上之可利用性] 本發明之含二苯并哌喃系染料之著色組合物之耐熱性及於有機溶劑(PGME等)中之溶解性優異，作為彩色濾光器用著色劑較為有用。Hereinafter, embodiments of the present invention will be described in detail. The present invention is not limited to the following embodiments, and can be implemented with various changes within the scope of the gist thereof. First, a dibenzopiperan-based dye represented by the general formula (1) will be described. In the general formula (1), as R1
~ R4
What is meant by "a linear or branched alkyl group having 1 to 20 carbon atoms which may have a substituent", specifically, methyl, ethyl, propyl, butyl, pentyl, and hexyl , Heptyl, octyl, nonyl, decyl and other linear alkyl groups; isopropyl, isobutyl, second butyl, third butyl, isooctyl and other branched alkyl groups. In the general formula (1), as R1
~ R4
Specific examples of the "cycloalkyl group having 3 to 20 carbon atoms which may have a substituent" include cyclopropyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl, Cycloalkyl such as cyclodecyl. In the general formula (1), as R1
~ R4
The "aromatic hydrocarbon group having 6 to 20 carbon atoms which may have a substituent" or "heterocyclic group having 2 to 20 carbon atoms which may have a substituent", specifically, phenyl, naphthyl , Anthryl, phenanthryl, fluorenyl, bitriphenyl, fluorenyl, indenyl, fluorenyl, pyridyl, pyrimidinyl, triyl, pyrrolyl, imidazolyl, pyrazolyl, triazolyl, quinolinyl , Isoquinolinyl, naphthyridinyl, indolyl, benzimidazolyl, carbazolyl, carbolinyl, acridinyl, morpholinyl, furanyl, benzofuranyl, dibenzofuranyl, thiophene Group, benzothienyl, dibenzothienyl, oxazolyl, benzoxazolyl, thiazolyl, benzothiazolyl, etc., and preferably phenyl. Here, in the present invention, the "aromatic hydrocarbon group" means a group containing a monocyclic aromatic hydrocarbon group or a condensed polycyclic aromatic group having a plurality of rings. Furthermore, in the present invention, "heterocyclic group" means a heterocyclic group representing a single ring or a plurality of rings, and represents a heterocyclic ring containing nitrogen, oxygen, or sulfur, and may be either aromatic or non-aromatic. Aromatic. In the general formula (1), as R1
~ R4
Specific examples of the "substituent" in the "linear or branched alkyl group having 1 to 20 carbon atoms having a substituent" include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. Halogen atom; -SO3 -
; Cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cyclooctyl and other cycloalkyl groups having 3 to 19 carbon atoms; methoxy, ethoxy, propoxy, butoxy, pentoxy Linear alkoxy groups having 1 to 19 carbon atoms such as hexyloxy, heptyloxy, octyloxy, nonyloxy and decyloxy; isopropoxy, isobutoxy, second butoxy Branched alkoxy groups having 3 to 19 carbon atoms, such as alkyl, third butoxy, and isooctyloxy; carbon atoms such as cyclopropoxy, cyclobutoxy, cyclopentyloxy, and cyclohexyloxy 3 to 19 cycloalkoxy groups; phenyl, naphthyl, biphenyl, anthracenyl, phenanthryl, fluorenyl, bitriphenyl, indenyl, and fluorenyl aromatic hydrocarbon groups having 6 to 19 carbon atoms Or condensed polycyclic aromatic groups; pyridyl, pyrimidyl, triyl, pyrrolyl, imidazolyl, pyrazolyl, triazolyl, quinolinyl, isoquinolinyl, naphthyridinyl, indolyl, benzo Imidazolyl, carbazolyl, carbolinyl, acridinyl, morpholinyl, furyl, benzofuryl, dibenzofuryl, thienyl, benzothienyl, dibenzothienyl, oxazolyl , Benzoxazolyl, thiazolyl, benzothia A heterocyclic group having 2 to 19 carbon atoms such as an azole group and the like. These "substituents" may include only one or a plurality of them, and when they include a plurality of them, they may be the same as or different from each other. These "substituents" may further have the substituents exemplified above. In the general formula (1), as R1
~ R4
"Cycloalkyl having 3 to 20 carbon atoms having a substituent", "Aromatic hydrocarbon group having 6 to 20 carbon atoms having a substituent" or "Hybrid having 2 to 20 carbon atoms having a substituent" Specific examples of the "substituent" in the "cyclic group" include halogen atoms such as a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom; -SO3 -
; Methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl and other linear alkyl groups having 1 to 14 carbon atoms; isopropyl, isobutyl Branched alkyl groups having 3 to 14 carbon atoms such as alkyl, second butyl, third butyl, and isooctyl; carbons such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, and cyclooctyl Cycloalkyl with 3 to 14 atoms; methoxy, ethoxy, propoxy, butoxy, pentoxy, hexyloxy, heptyloxy, octyloxy, nonyloxy, decoxy, etc. Linear alkoxy groups having 1 to 14 carbon atoms; branches having 3 to 14 carbon atoms such as isopropoxy, isobutoxy, second butoxy, third butoxy, and isooctyloxy Chain alkoxy; cycloalkoxy having 3 to 14 carbon atoms such as cyclopropoxy, cyclobutoxy, cyclopentyloxy, and cyclohexyloxy; phenyl, naphthyl, biphenyl, and anthracene Aromatic hydrocarbon groups or condensed polycyclic aromatic groups having 6 to 14 carbon atoms such as phenyl, phenanthryl, indenyl, and fluorenyl; pyridyl, pyrimidyl, triyl, pyrrolyl, imidazolyl, pyrazolyl, and triazole Quinolyl, isoquinolyl, naphthyridinyl, indolyl , Benzimidazolyl, carbazolyl, carbolinyl, acridinyl, morpholinyl, furyl, benzofuryl, dibenzofuryl, thienyl, benzothienyl, dibenzothienyl, A heterocyclic group having 2 to 14 carbon atoms, such as oxazolyl, benzoxazolyl, thiazolyl, and benzothiazolyl, and the like. These "substituents" may include only one or a plurality of them, and when they include a plurality of them, they may be the same as or different from each other. These "substituents" may further have the substituents exemplified above. In the general formula (1), as R5
~ R8
Examples of the "halogen atom" include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. The "halogen atom" is preferably a fluorine atom or a chlorine atom. In the general formula (1), as R5
~ R8
"A linear or branched alkyl group having 1 to 20 carbon atoms which may have a substituent", a "cycloalkyl group having 3 to 20 carbon atoms which may have a substituent", A linear or branched alkoxy group having 1 to 20 carbon atoms in the radical group ", a" cycloalkoxy group having 3 to 20 carbon atoms which may have a substituent group "or a" carbon atom number which may have a substituent group " "Linear or branched alkenyl groups of 2 to 20" "Linear or branched alkyl groups of 1 to 20 carbon atoms", "Cycloalkyl groups of 3 to 20 carbon atoms", "Straight or branched alkoxy group with 1 to 20 carbon atoms", "Cycloalkoxy group with 3 to 20 carbon atoms" or "Straight or branched chain with 2 to 20 carbon atoms" "Alkenyl" specifically includes: linear alkyl groups such as methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, and decyl; isopropyl , Isobutyl, second butyl, third butyl, isooctyl and other branched alkyl groups; cyclopropyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl, cyclo Cycloalkyl such as decyl; methoxy, ethoxy, Linear alkoxy groups such as oxy, butoxy, pentoxy, hexyloxy, heptyloxy, octyloxy, nonyloxy, and decoxy; isopropoxy, isobutoxy, and Branched alkoxy groups such as dibutoxy, third butoxy, and isooctyloxy; cycloalkoxy groups such as cyclopropoxy, cyclobutoxy, cyclopentyloxy, and cyclohexyloxy; ethylene Group, 1-propenyl, allyl, 1-butenyl, 2-butenyl, 1-pentenyl, 1-hexenyl, isopropenyl, isobutenyl, or plural such alkenyl bonds Alkenyl groups such as linear or branched. In the general formula (1), as R5
~ R8
"A linear or branched alkyl group having 1 to 20 carbon atoms having a substituent", a "cycloalkyl group having 3 to 20 carbon atoms having a substituent", "a carbon having a substituent Linear or branched alkoxy group having 1 to 20 atoms "," Cycloalkoxy group having 3 to 20 carbon atoms having substituents "or" Straight or branched alkoxy group having 2 to 20 carbon atoms having substituents " Specific examples of the "substituent" in the "chain or branched alkenyl group" include: halogen atoms such as fluorine atom, chlorine atom, bromine atom, and iodine atom; -SO3 -
Cycloalkyl groups having 3 to 17 carbon atoms, such as cyclopropyl, cyclopentyl, cyclohexyl, and cyclooctyl; methoxy, ethoxy, propoxy, butoxy, pentoxy, and hexyloxy Linear alkoxy groups having 1 to 17 carbon atoms such as heptyloxy, octyloxy, nonyloxy, and decyloxy; isopropoxy, isobutoxy, second butoxy, third Branched alkoxy groups having 1 to 17 carbon atoms, such as butoxy and isooctyloxy; 3 to 17 carbon atoms such as cyclopropoxy, cyclobutoxy, cyclopentyloxy, and cyclohexyloxy Cycloalkoxy; phenyl, naphthyl, biphenyl, anthracenyl, and the like; aromatic hydrocarbon groups having 6 to 18 carbon atoms; or condensed polycyclic aromatic groups having 6 to 17 carbon atoms. These "substituents" may include only one or a plurality of them, and when they include a plurality of them, they may be the same as or different from each other. These "substituents" may further have the substituents exemplified above. In the general formula (1), as R1
~ R4
, Preferably a hydrogen atom, a linear or branched alkyl group having 1 to 10 carbon atoms which may have a substituent, a cycloalkyl group having 5 to 12 carbon atoms which may have a substituent, or a substituent An aromatic hydrocarbon group having 6 to 12 carbon atoms. In the general formula (1), R1
With R2
Combination with R3
With R4
The combinations may be the same as or different from each other. In the general formula (1), R1
With R2
Each other, or R3
With R4
The rings may be bonded to each other to form a ring. The ring formed in this case is preferably a 5-membered ring or a 6-membered ring, and more preferably a 5-membered ring. R1
With R2
Each other and R3
With R4
Two groups may form a ring with each other, or any group may form a ring. In the general formula (1), as R5
~ R8
, Preferably hydrogen atom, halogen atom, -SO3 -
, A linear or branched alkyl group having 1 to 20 carbon atoms which may have a substituent, or a linear or branched alkoxy group having 1 to 20 carbon atoms which may have a substituent, more Preferably a hydrogen atom or -SO3 -
. Again, in R5
~ R8
Either -SO3 -
In the case of R7
More preferably -SO3 -
. In general formula (1), in R5
~ R8
In addition, adjacent groups may be bonded to each other to form a ring. As the ring formed in this case, a 5-membered ring or a 6-membered ring is preferable, and a 6-membered ring is more preferable. In the general formula (1), "M" represents an alkali metal atom, preferably a lithium atom, a sodium atom, or a potassium atom, more preferably a lithium atom or a sodium atom, and even more preferably a sodium atom. In the general formula (1), x represents the number of "M" and is an integer of 0 or 1, and the compound represented by the general formula (1) is electrically neutral as a whole. In the general formula (1), -SO3 -
The number is set to 1 or 2 and contains only 1 -SO3 -
In this case, it becomes x = 0 (there is no M).3 -
In this case, x = 1 (1 M exists). The dibenzopiperan-based dye represented by the general formula (1) can be synthesized by a known method (see Non-Patent Document 1, etc.), for example, in the following manner. Sulfurylaldehyde derivatives having equivalent substituents such as sodium benzaldehyde-2-sulfonate and hydroxyaniline derivatives having equivalent substituents such as diethylaminophenol are suitably used in an acid aqueous solution such as sulfuric acid. The condensation reaction is performed under heating conditions to obtain an intermediate represented by the following general formula (2). Next, the intermediate represented by the following general formula (3) is obtained by dehydrating the following general formula (2). Furthermore, the following general formula (3) was mixed with iron (III) chloride (FeCl) in an acid aqueous solution under appropriate heating conditions.3
) Is reacted and oxidized, and neutralized with an alkaline aqueous solution such as sodium hydroxide (NaOH), and then salted out using a chlorine compound such as sodium chloride (NaCl), thereby obtaining a compound containing the compound represented by the general formula (1). product. [Chemical 4][Chemical 5][Chemical 6]The compound represented by the general formula (1) can be synthesized, for example, by using 3,6-dichlorospiro [9H-dibenzopipere] represented by the following general formula (4) as a starting material. Nan-9,3 '-[3H] [2,1] benzopyrenethiol] 1', 1'-dioxide (or dichlorosulfofluorane) derivatives and amine compounds containing nitrogen atoms, The cyclic compound is equivalent to N-methylpyrrolidone (NMP) and the like, and the reaction is performed under an appropriate temperature condition in an arbitrary solvent (for example, refer to Patent Document 6). [Chemical 7]In the general formulae (2) to (4), R1
~ R8
It means the same definition as that in the general formula (1). In the method for synthesizing a dibenzopiperan-based dye represented by the general formula (1), in the case where the precipitated dibenzopiperan-based dye adheres strongly and prevents stirring, in order to eliminate or alleviate the situation, Can mix organic solvents. The organic solvent to be mixed is not particularly limited as long as it has sufficient solubility with the corresponding dibenzopiperan dyes, and aromatic hydrocarbons such as toluene and xylene may be used alone or in combination; acetone, 2-butanone, Ketones such as 2-pentanone and 3-pentanone; esters such as ethyl acetate and butyl acetate; alcohols such as methanol, ethanol, propanol, isopropanol, butanol, pentanol, and hexanol. The dibenzopiperan-based dye represented by the general formula (1) can be purified by column chromatography if necessary, using a product obtained by the above-mentioned synthesis method; by adsorption of silica gel, activated carbon, activated clay, etc. Refining: Obtained by means of well-known refining such as dispersion washing of the solvent or recrystallization, crystallization, and salting out. The solvent used for these refining methods is not particularly limited, and alcohols such as water, methanol, ethanol, etc .; methylene chlorides such as dichloromethane, chloroform, and toluene; As the dibenzopiperan dye of the present invention represented by the general formula (1), a commercially available product can be used. Specifically, dibenzopiperan-based dyes such as C.I. Acid Red 52 and C.I. Acid Red 289, or a composition containing these dyes as a main component are commercially available. These can also be used directly to prepare the coloring composition of the present invention, and the coloring composition of the present invention can be prepared by purifying the coloring composition of the present invention by the same method as that of the dibenzopiperan-based dye. Specific examples of the preferred compound of the dibenzopiperan dye of the present invention represented by the general formula (1) are shown in the following formulae (A-1) to (A-37), but the present invention is not limited to these Such compounds. In addition, a part of hydrogen atoms is omitted in the following structural formula. In addition, even when stereoisomers exist, the planar structural formula is described. [Chemical 8][Chemical 9][Chemical 10][Chemical 11][Chemical 12][Chemical 13][Chemical 14][Chemical 15][Chemical 16][Chemical 17][Chemical 18][Chemical 19][Chemical 20][Chemical 21][Chemical 22][Chemical 23][Chemical 24][Chemical 25][Chemical 26][Chemical 27][Chemical 28][Chemical 29][Chemical 30][Chemical 31][Chemical 32][Chemical 33][Chem 34][Chemical 35][Chemical 36][Chemical 37][Chemical 38][Chemical 39][Chemical 40][Chemical 41][Chemical 42][Chemical 43][Chemical 44][Chemical 45][Chemical 46][Chemical 47][Chemical 48][Chemical 49][Chemical 50][Chemical 51][Chemical 52][Chem 53][Chemical 54][Chem 55]The decomposition initiation temperature of the dibenzopiperan dye of the present invention in thermogravimetric-differential thermal analysis (TG-DTA) is preferably 250 ° C or higher, more preferably 300 ° C or higher, and even more preferably 360 ° C or higher. When considering the application to a color filter, the higher the decomposition start temperature, the better. Hereinafter, the coloring composition containing the dibenzopiperan dye represented by General formula (1) of this invention is demonstrated in detail. The coloring composition of the present invention is such that, among the components of the solid component, the dibenzopiperan dye represented by the general formula (1) is contained as a main component, and a certain concentration range may be contained. Moisture. The presence of water in the coloring composition can improve the solubility of dibenzopiperan-based dyes in organic solvents such as PGME. Specifically, by setting the moisture content of the entire dibenzopiperan-based dyeing composition to 3 to 18% by weight, heat resistance can be maintained and a coloring agent having high solubility in organic solvents such as PGME can be obtained. combination. Herein, the "water content" in the present invention means a weight ratio of moisture in the weight of the entire coloring composition, and the unit is expressed as "wt%". The dibenzopiperan-based dye-containing coloring composition of the present invention can improve the solubility in an organic solvent such as PGME by forming a water molecule-dibenzopiperan molecular complex in its manufacturing step. Such a coloring composition containing water molecules and dibenzopiperan molecules can be maintained in a solid state (powder, etc.) by a strong hydrogen bond between molecules to maintain its solid state, and when dissolved in a solvent, water molecules It is easy to dissolve, and the dibenzopiperan molecule can be easily dissolved in a solvent in a molecular unit at the same time as the water molecule is dissolved. In addition, since unnecessary surfactants and the like are not used, the dispersion liquid is not deteriorated (solid-liquid phase separation, etc.), and it is easy to be used without compromising the solubility of other color filter manufacturing materials.地 OPERATION. The composition ratio of the dibenzopiperan molecule to the water molecule in the dibenzopiperan dye-containing coloring composition of the present invention will be described. If the oxygen atom, nitrogen atom, -SO of the dibenzopiperan molecule3 -
The polar part of the base or metal atom is considered to form a hydrogen bond with water molecules. It can be considered that one dibenzopiperan molecule can form a stable complex (or hydration) with up to about 6 to 8 water molecules.物) 结构。 Structure). For example, in a coloring composition containing Formula (II) and water molecules as a representative dibenzopiperan-based dye, the molar ratio of the dibenzopiperan molecules to the water molecules to form a stable structure is 1: 1 to 1: 1. : In the case of 7, the water content in the entire coloring composition is 3 to 18% by weight. In the state without any water molecules (the water content is less than 3% by weight), nearby dibenzopiperan molecules are agglomerated with each other. On the other hand, the ratio of water molecules is higher (water content is greater than 18% by weight) In this case, adjacent water molecules condense with each other, and the powder in the solid state becomes liquid, which causes inconvenience in the manufacturing steps. As such, the coloring composition of the present invention has both solubility and ease of handling as a powder. Based on the above, the moisture content of the dibenzopiperan-based dyeing coloring composition of the present invention is preferably 3 to 18% by weight, more preferably 4 to 18% by weight, and even more preferably 10% in the entire coloring composition. ~ 14% by weight. In the coloring composition containing a dibenzopiperan-based dye of the present invention, the coloring composition having a target moisture content can be obtained by the following method. Furthermore, this method is not limited to a method for preparing a coloring composition having a certain water content, and can also be used as a method for refining the same coloring composition. First, a powder containing a dibenzopiperan dye as a main component, activated carbon, and a solvent are put into a container of an appropriate size, mixed, heated, and then stirred for a certain time. After stirring, hot filtration was performed to obtain a filtrate. The filtrate was concentrated while being at atmospheric pressure or under reduced pressure to obtain a concentrate. The colored composition containing the solvent was taken out from the container as a concentrate, and dried in another container (primary drying). Furthermore, the solvent was removed by drying under reduced pressure at a constant temperature. In this way, a colored composition containing a dibenzopiperan-based dye represented by the general formula (1) and having a certain water content is obtained. Here, as a material of the stirring container, an appropriate one can be selected and used. For example, glass containers such as flasks, metal containers, resin containers, and glass-lined containers can be used. The size of the stirring container may be various sizes, and it is preferably 1 to 5 L for 100 g of powder. However, it is not limited to this range, and can be arbitrarily determined by the amount of the solvent required to dissolve the dibenzopiperan-based dye used. In order to improve the adsorption capacity of activated carbon, the activated carbon used when mixed in a solvent is preferably powdery or finely powdered. The solvent is preferably an alcohol. In the case of an alcohol, methanol, ethanol, propanol, isopropanol, and butanol are preferred, and methanol is more preferred. As the solvent, a commercially available general article can be used. For the purpose of adjusting the moisture content of the coloring composition, it is preferably one that has not been subjected to a dehydration treatment. When a dehydrated person is used, water may be added to the solvent or not. When the solvent is an alcohol, the "moisture content rate contained in the alcohol" (hereinafter, different from the moisture content of the coloring composition) is preferably 0.01 to 10% by weight, and more preferably 0.1 to 5% by weight. The water content of the coloring composition can also be adjusted by adding water during mixing. When using alcohol as a solvent, in order to make "the water content rate contained in alcohol" 0.01 to 10 weight%, it can be adjusted by adding water. Examples of the added water include distilled water, tap water, industrial water, and ion-exchanged water. Among these, ion-exchanged water is preferred. The weight ratio of the dibenzopiperan-based dye to the solvent when mixed in a solvent is preferably 3 to 10 times the weight ratio of the solvent relative to the weight of the dibenzopiperan-based dye. However, it is not limited to this range, and the amount required for dissolving the dibenzopiperan-based dye used can be arbitrarily determined. As other ingredients, in order to improve the performance of the coloring composition of the present invention as a colorant for color filters, surfactants, dispersants, defoamers, leveling agents, and other colorants for color filters can be added for mixing. Additives and other organic compounds. Among them, the content of these additives in the coloring composition is preferably an appropriate amount, and it is preferable not to reduce the solubility of the coloring composition of the present invention in a solvent or to increase it excessively without affecting the color filter. The content rate of the range of effects of other similar additives used in the manufacture of optical devices. These additives can be put in at any time when the coloring composition is prepared. The gas in the container during the mixing or stirring process can be exemplified by air, nitrogen, and other inert gases, and is not particularly limited. Considering the safety of ignition caused by static electricity during manufacturing, it is preferable to replace the container with an inert gas such as nitrogen. The method for concentrating the liquid containing the coloring composition is not particularly limited, and the filtrate from which the activated carbon is removed is distilled under atmospheric pressure or under reduced pressure to remove the solvent. An evaporator or the like may be used as the vacuum distillation removal device. If the concentration is excessively carried out, difficulty in recovery of the concentrate affects adjustment of the moisture content, and when the concentration is insufficient, drying in the next step requires time, which affects manufacturing costs. Therefore, the degree of concentration is preferably performed within a range of 2 to 5 times the volume of the powder used. The concentrate is dried by moving it into a container such as a pan or a tank and drying it. In order to bring the moisture content into an equilibrium state, it is left to stand at atmospheric pressure for 1 to 96 hours and then dried (primary drying). The temperature during drying is preferably in the range of 20 ° C to 100 ° C. Here, it is preferable to leave the water to some extent during the temporary drying without completely drying it. The coloring composition containing a dibenzopiperan-based dye which has been dried once is dried (secondary drying) using a dryer having a venting device such as a vacuum dryer. It can also replace the vacuum dryer and air-dry on a trough-shaped container with a large bottom area. The temperature during drying is preferably in the range of 40 to 100 ° C. The drying time is preferably in the range of 4 to 48 hours. In order to obtain a coloring composition with a target moisture content, it can be set at any time and is not particularly limited. In the case where an alcohol is used as a solvent, the point at which the alcohol is removed as much as possible can be set as the end point of drying. Examples of the method for measuring the end point of drying include a method for measuring the concentration of a solvent component based on observation of powder state, weight measurement, nuclear magnetic resonance analysis (NMR), gas chromatography analysis (GC), and the like. Examples of the method for measuring the moisture content of the coloring composition prepared by the above method include: the Karl Fischer (KF) method using an electric titration method or a volumetric titration method; using a thermogravimetric-differential thermal analysis (TG-DTA) device Thermal analysis method; heating and drying method using heating and drying type moisture meter; gas chromatography (GC) method, infrared or near-infrared absorption method; nuclear magnetic resonance absorption method; resistance method; dielectric constant method; distillation method, etc. In terms of accuracy, the Karst method is preferable, and in terms of confirming the endothermic reaction when water is evaporated, the thermal analysis method or the heat-drying method is preferable. By the method described above, the coloring composition of the present invention containing a dibenzopiperan-based dye represented by the general formula (1) can be obtained, and the coloring composition is adjusted to have an arbitrary moisture content. The coloring composition of the present invention is generally used in the state of a solid powder having a shape such as a crystalline shape, a microcrystalline shape, a micropowder shape, a flake shape, a needle crystal shape, or a granular shape, and is not particularly limited. The state of the solid powder of the coloring composition of the present invention can be observed using an optical microscope, a scanning electron microscope (SEM), or the like. In addition, the particle size distribution of the powder can be obtained from the observed image. Specifically, an image analysis method for obtaining an equivalent diameter when converted into a regular shape (ball, cube, etc.) can be used. Coulter method for measuring the resistance of electrolytic solution, centrifugal precipitation method to determine the effective diameter of stokes by measuring the absorbance of powder dispersion, and laser diffraction using diffraction pattern analysis of powder dispersion And scattering methods. In addition, as the particle diameter obtained by these measurement methods, an average value or a median value of the particle size distribution is used, and a median value is preferably used. The coloring composition of the present invention is preferably in a particle size range of 0.1 μm to several mm, but the shape of the particles is changed due to manufacturing conditions or a method for recovering the powder after drying, so it is not limited to a specific particle size. In order to achieve higher solubility, the particle size is preferably smaller, and the central value of the particle size distribution is preferably in the range of 0.1 to 100 μm. The solubility of the coloring composition in the present invention is expressed in terms of solubility, and the solubility refers to the ratio of the maximum amount of the powdery coloring composition that can be dissolved in a specific solvent to the coloring composition. For example, "weight% (solvent name, Temperature). The solubility is obtained, for example, by mixing a sample in a specific solvent, stirring the solvent at a certain temperature for a certain time, and measuring the concentration of the prepared saturated solution, or by liquid chromatography (LC ) Or concentration measurement such as absorbance measurement. The coloring composition contained in the colorant for a color filter is preferably dissolved or dispersed in an organic solvent containing a resin or the like in the production steps of the colorant for the color filter and the color filter. The solubility of organic solvents is high. The organic solvent is not particularly limited, and specific examples include esters such as ethyl acetate and n-butyl acetate; ethers such as diethyl ether and propylene glycol monomethyl ether (PGME); propylene glycol monomethyl ether acetate (PGMEA) and the like Ether esters; ketones such as acetone and cyclohexanone; alcohols such as methanol and ethanol; diacetone alcohol (DAA) and the like; aromatic hydrocarbons such as benzene, toluene, and xylene; N, N-dimethylformamide (DMF), N-methylpyrrolidone (NMP), and other amines; dimethylsulfinium (DMSO) and the like. These solvents may be used alone or in combination of two or more. Among these, PGME is preferably used. The dibenzopiperan dye-containing coloring composition of the present invention has excellent solubility in organic solvents, especially in PGME, for example, solubility in PGME at 25 ± 2 ° C (solvent PGME, 25 ± 2 ° C) is preferably 0.5% by weight or more, more preferably 1% by weight or more, and even more preferably 2% by weight or more. The colorant for a color filter of the present invention contains a coloring composition containing a dibenzopiperan-based dye represented by the general formula (1) and components generally used for producing a color filter. A general color filter is obtained by, for example, a method using a photolithography method in which a pigment such as a dye or a pigment is mixed with a resin component (including a monomer and an oligomer) or a solvent. The prepared liquid is coated on a substrate such as glass or resin, and photo-polymerized using a photomask to produce a coloring pattern of a soluble / insoluble pigment-resin composite film. After washing, it is heated. Moreover, even in an electrodeposition method or a printing method, a coloring pattern is produced using a mixture of a pigment and a resin or other components. Therefore, specific components in the colorant for color filters of the present invention include dibenzopiperan dyes represented by the general formula (1), pigments such as other dyes and pigments, resin components, organic solvents, and light. Polymerization initiators and other additives. In addition, these components may be selected or selected, or other components may be added as necessary. When the dibenzopiperan dye-containing coloring composition of the present invention is used as a colorant for a color filter, it can also be used as a color filter for each color, and is preferably used as a blue or red color filter. Coloring agent. The colorant for a color filter containing a dibenzopiperan-based dye of the present invention may be a dibenzopiperan-based dye alone. In order to adjust the color tone, other known dyes and pigments may be mixed. It is not particularly limited when it is used as a colorant for red color filters. Examples include red pigments such as CI Pigment Red 177, CI Pigment Red 209, CI Pigment Red 242, and CI Pigment Red 254; CI Acid Red 88, CI Base Violet 10 and other red dyes. It is not particularly limited when it is used as a colorant for blue color filters. Examples include: CI basic blue 3, 7, 9, 54, 65, 75, 77, 99, 129 and other basic dyes; CI acid blue Acid dyes such as 9, 74; disperse dyes such as disperse blue 3, 7, 377; Spilon dyes; cyanine, indigo, phthalocyanine, anthraquinone, methine, triarylmethane, indandan Blue dyes, pigments, and the like, which are not based on the present invention, such as dibenzopiperan, and the like. The mixing ratio of other pigments in the colorant for color filters containing dibenzopiperan-based dyes of the present invention is preferably 5 to 2000% by weight, and more preferably 10 to 2,000% by weight relative to the dibenzopiperan-based dyes. 1000% by weight. The mixing ratio of the pigment components such as the dye in the liquid color filter colorant is preferably 0.5 to 70% by weight, and more preferably 1 to 50% by weight, based on the entire colorant. As the resin component in the colorant for a color filter of the present invention, a known one can be used as long as it has properties required for the production method or use of the formed color filter resin film. Examples include acrylic resins, olefin resins, styrene resins, polyimide resins, polyurethane resins, polyester resins, epoxy resins, vinyl ether resins, phenolic (phenolic) resins, other transparent resins, and photocuring properties. A resin or a thermosetting resin can be used in appropriate combination of these monomer or oligomer components. A copolymer of these resins may be used in combination. Regarding the content of the resin in these color filters, in the case of a liquid colorant, it is preferably 5 to 95% by weight, and more preferably 10 to 50% by weight. Examples of the other additives in the colorant for color filters of the present invention include components necessary for polymerizing or curing resins such as a photopolymerization initiator and a cross-linking agent, and for liquid color filters. A surfactant or dispersant, etc. required for the properties of the ingredients in the colorant to stabilize. These are all known to be used for manufacturing color filters, and are not particularly limited. The total amount of these additives in the solid matter component of the color filter for color filters is preferably 5 to 60% by weight, and more preferably 10 to 40% by weight. [Examples] Hereinafter, embodiments of the present invention will be specifically described using examples, but the present invention is not limited to the following examples. Furthermore, the compounds obtained in the examples were identified by1
H-NMR analysis (a nuclear magnetic resonance apparatus manufactured by Japan Electronics Co., Ltd., JNM-ECA-600) was performed. [Synthesis Example 1] Synthesis of Compound (A-20) To a reaction vessel, sodium benzaldehyde-2,4-disulfonate (79.9 g, 258 mmol) represented by the following formula (5) and the following formula were added (6) N, N-diethyl-3-aminophenol (85.1 g, 515 mmol), 30% by weight sulfuric acid (0.799 L), and stirred at 90 ° C for 23 hours. The reaction solution was poured into 2.55 L of water, and the mixture was stirred at room temperature for 30 minutes, and then the solid was filtered off. 0.51 L of water was added to the obtained solid, and the mixture was stirred at 80 ° C for 30 minutes, and then the solid was removed by filtration. 0.51 L of methanol was added to the obtained solid, and the mixture was heated and stirred for 30 minutes until reflux, then cooled to room temperature, and the solid was removed by filtration. The obtained solid was dried under reduced pressure at 60 ° C to obtain 138.7 g of a powder containing the intermediate represented by the following formula (7) as a main component. [Chemical 56][Chemical 57][Chem 58]138.7 g of the powder containing the intermediate represented by the above formula (7) was added to the reaction vessel, and 0.828 L of 90% by weight sulfuric acid was added. After stirring at 100 ° C for 3 hours, the temperature was raised to 120 ° C, followed by stirring for 3 hours. After cooling to room temperature, it was poured into 2.5 L of ice water, and the precipitated solid was filtered off. 2.5 L of water was added to the obtained solid, and after stirring at room temperature, the solid was removed by filtration. The obtained solid was dried to obtain 146.7 g of a powder whose main component was an intermediate represented by the following formula (8). [Chemical 59]146.7 g of powder containing the intermediate represented by the above formula (8) was added to the reaction vessel, and 1.61 L of 10% by weight sulfuric acid was added and stirred, and then iron (III) chloride (FeCl) was added.3
291 g, and stirred at 80 ° C for 22 hours. After cooling to room temperature, a 24% by weight aqueous sodium hydroxide solution was added until the pH became 7. After adding 174 g of sodium chloride for salting out, the crude product with viscosity was filtered out. The obtained crude product was added to 2.6 L of methanol and heated and stirred at 50 ° C, and then the insoluble component was separated by filtration. The filtrate was concentrated to dryness, and then the obtained dark purple product was purified by silica gel column chromatography (carrier: silica gel, eluent: chloroform → chloroform: methanol = 95: 5 (volume ratio)). After the target component was recovered and concentrated to dryness, toluene was added for dispersion and washing, and the solid was removed by filtration. The obtained solid was dried under reduced pressure at 70 ° C, thereby obtaining a magenta powder (121.7 g, yield 80%) containing the following formula (A-20) as a main component as a target compound. [Chemical 60][Synthesis Example 2] Synthesis of compounds (A-12) to (A-17) Compounds (A-12) to (A-17) were obtained by the same method as described in Patent Document 6. Examples of the synthesis of compound (A-13) are shown below. To the reaction vessel were added 1.93 g of dichlorosulfofluorane, 1,2,3,4,4a, 9a-hexahydro-9H-carbazole 3.30 g, and 40 mL of NMP, followed by stirring at 80 ° C for 8 hours. After allowing to cool, the reaction solution was poured into 400 mL of water, 1 M hydrochloric acid was added until the pH became 2, and the precipitated solid was filtered out. The crude product obtained was purified by silica gel column chromatography (carrier: silica gel, eluent: chloroform / methanol = 8/1 (volume ratio)) to obtain a purple-red powder (0.901 g, yield 28%). ). [Example 1] A 10 L reaction vessel was charged with 700 g of a composition containing the compound (A-20) of the above formula as a main component, 40 g of activated carbon, and 6 L of methanol, and stirred at 55 ° C for 1 hour. , And filtered at 50 ° C. The filtrate was concentrated to 1/3 under reduced pressure, poured into a stainless steel tank, air-dried at 25 ± 2 ° C for 4 days, and dried at 80 ° C for 5 days under reduced pressure. The drying was terminated when the weight reduction became 0.4% by weight per day, and a dibenzopiperan-based dye (A-20) -containing coloring composition (715 g) was obtained as a reddish-red powder. NMR analysis of this coloring composition confirmed that no component of an organic solvent such as methanol was observed. As for the coloring composition containing the dibenzopiperan dye (A-20) obtained in the above manner, a moisture meter (manufactured by Hiranuma Sangyo Co., Ltd., automatic moisture measuring device AQV-5S type) was used, (KF) method. In addition, a TG-DTA measurement was performed using a thermogravimetric-differential thermal analysis device (manufactured by MAC Science Co., Ltd., TG-DTA 2000S type) under a nitrogen gas flow (sample weight: 5 ± 1.5 mg, heating rate: 20 ° C / Minutes) to determine the decomposition start temperature. Next, the solubility in a PGME solvent at room temperature (PGME, 25 ± 2 ° C) was measured. These measurement results are shown in Table 1. [Example 2 to Example 5] Except changing the air-drying time and the reduced-pressure drying time of Example 1, the same operation was performed, and the dibenzo-containing benzoxide of Example 2 to Example 5 was obtained as a purple-red powder. A coloring composition of a piperan dye (A-20). About these coloring compositions, it carried out similarly to Example 1, and measured the water content, decomposition start temperature, and solubility (PGME, 25 ± 2 degreeC). The measurement results are shown together with the results of Example 1 in Table 1. [Comparative Example 1] For comparison, the same operation as in Example 1 was performed except that the amount or ratio of added water, air-drying time, or reduced-pressure drying time in Example 1 was changed, and the water content was adjusted to be lower than A low coloring composition containing a dibenzopiperan dye (A-20). About this coloring composition, it carried out similarly to Example 1-Example 5, and measured the water content, decomposition start temperature, and solubility (PGME, 25 ± 2 degreeC). The measurement results are shown together with the results of the examples in Table 1. [Table 1]
As shown in Table 1, it can be seen that the coloring compositions containing the dibenzopiperan-based dyes (A-20) of Examples 1 to 5 are colored because the decomposition initiation temperature is 360 ° C or higher, and they have sufficient heat resistance. The colorant for a filter has no practical problems. In addition, regarding the solubility of the coloring compositions in these examples in PGME, when the solubility of Comparative Example 1 is set to 1, it shows that the solubility is from 2.5 times to 10 times or more, and it is colored as a color filter. Agents are more useful. On the other hand, it was found that the coloring composition having a relatively low water content of less than 3% by weight in Comparative Example 1 had the same decomposition initiation temperature as in Examples 1 to 5, but had a low solubility in PGME. [Example 6 to Example 11] A coloring composition containing a dibenzopiperan dye containing the above-mentioned compounds (A-13) to (A-17) was subjected to various drying conditions by the same method as in Example 1 It is obtained by drying and removing an organic solvent such as methanol. The water content, the decomposition start temperature, and the solubility (PGME, 25 ± 2 ° C) of these were measured in the same manner as in Example 1. The commercially available dibenzopiperan dye C.I. Acid Red 289 (manufactured by Sinochem Chemical Co., Ltd.) represented by the above formula (A-27) was also measured by the same method. The measurement results are collectively shown in Table 2. [Comparative Example 2] In order to compare with Examples 6 to 11 and change the drying conditions of these examples, the same operations were performed except that the above-mentioned dibenzene containing the above-mentioned diphenyl was adjusted to have a lower water content than the examples. A coloring composition of a piranoid dye (A-12), and the water content, the decomposition start temperature, and the solubility (PGME, 25 ± 2 ° C) were measured. The measurement results are collectively shown in Table 2. [Comparative Example 3 and Comparative Example 4] For comparison with Examples 6 to 11, the CI Basic Blue 1 represented by the following formula (B-1) and the following represented by the following formula (B-2) CI Basic Blue 7 (both manufactured by Tokyo Chemical Industry Co., Ltd.) was measured for water content, decomposition start temperature, and solubility (PGME, 25 ± 2 ° C) in the same manner as in the examples. The measurement results are collectively shown in Table 2. [Chem 61][Chem 62][Table 2]
As shown in Table 2, it can be seen that the coloring compositions containing various dibenzopiperan dyes of Examples 6 to 11 have sufficient heat resistance because the decomposition initiation temperature is 300 ° C or higher, and therefore they are colored as color filters. There is no problem in practical use of the agent. In addition, regarding the solubility of the coloring compositions in these examples in PGME, when the solubility of Comparative Example 2 was set to 1, it was found that the solubility was 10 times or more, and it was useful as a colorant for color filters. On the other hand, it can be seen that the colored composition of Comparative Example 2 having a moisture content of less than 3% by weight had the same decomposition initiation temperature as that of the Example, but had a low solubility in PGME. In addition, it can be seen that the coloring composition containing the dye (B-1) of Comparative Example 3 and the dye (B-2) of Comparative Example 4 had a water content of 3% by weight or more, and its solubility in PGME and its implementation at room temperature. Examples are of the same degree, but do not have a dibenzopiperan skeleton, and the decomposition initiation temperature is low, being 220 ° C or lower, and the heat resistance is insufficient. [Example 12] FIG. 1 shows an SEM image (scale length = 10 μm) obtained by observing the powder of the coloring composition obtained in Example 4. Needle-like crystals with a length of μm to 20 μm × width of 2 to 10 μm were observed in the image, and the central value of the particle size distribution analyzed from the image was 3 to 4 μm. From this result, it is understood that the coloring composition of the present invention maintains a powder state suitable for handling as a colorant for a color filter. As described above, the coloring composition containing the dibenzopiperan-based dye of the present invention and having a water content in the range of the water content shown in the present invention has high heat resistance, and has a higher content in organic solvents such as PGME. Because of its solubility, it is useful as a colorant for color filters. [Industrial Applicability] The dibenzopiperan dye-containing coloring composition of the present invention is excellent in heat resistance and solubility in an organic solvent (PGME, etc.), and is useful as a colorant for a color filter.