TW201800495A

TW201800495A - Compound and color filter

Info

Publication number: TW201800495A
Application number: TW106103466A
Authority: TW
Inventors: 野口祐貴; 清都育郎
Original assignee: 迪愛生股份有限公司
Priority date: 2016-02-25
Filing date: 2017-02-02
Publication date: 2018-01-01
Also published as: JP6255634B1; JPWO2017145627A1; WO2017145627A1

Abstract

It becomes possible to provide a coloring material which undergoes little change in hue even under temperature history of 200 DEG C or higher which is required for color filter production processes. Provided are, for example: a triarylmethane compound which, when used in the preparation of blue color pixel parts in a color filter, can make it possible to provide a liquid crystal display device capable of excellent liquid crystal display with little change in hue and others; and a color filter containing the triarylmethane compound. It is found that, when a triarylmethane compound composed of a basic polymerized triarylmethane dye cation having a specific structure and a specific counter anion is used as a coloring material for a color filter, little change in hue is observed even under temperature history in the production of a color filter. This finding leads to the accomplishment of the present invention.

Description

化合物及濾色器 Compounds and color filters

本發明關於三芳基甲烷化合物及含有該化合物而成之濾色器，該三芳基甲烷化合物例如於用作著色劑時，可提供即便持續長時間經受高溫下之熱歷程，色相變化亦較小之著色物。 The present invention relates to a triarylmethane compound and a color filter containing the compound. When the triarylmethane compound is used as a colorant, for example, it can provide a small change in hue even if it is subjected to a high temperature thermal history for a long time. Coloring matter.

液晶顯示裝置等之濾色器具有紅色像素部(R)、綠色像素部(G)及藍色像素部(B)。該等各像素部均為於基板上設置有分散有機顏料而成之合成樹脂之薄膜的結構，作為有機顏料，使用有紅、綠及藍各種顏色之有機顏料。 A color filter such as a liquid crystal display device includes a red pixel portion (R), a green pixel portion (G), and a blue pixel portion (B). Each of these pixel portions has a structure in which a thin film of a synthetic resin in which an organic pigment is dispersed is provided on a substrate. As the organic pigment, organic pigments of various colors of red, green, and blue are used.

作為用以形成該等像素部中之藍色像素部之藍色有機顏料，一般而言，使用ε型酞菁銅顏料(C.I.顏料藍15：6)，為了調色，視需要向其中少量併用紫色有機顏料之二

紫顏料(C.I.顏料紫23)。 As the blue organic pigment used to form the blue pixel portion of these pixel portions, generally, an ε-type copper phthalocyanine pigment (CI Pigment Blue 15: 6) is used, and a small amount thereof is used in combination as needed for color adjustment. Purple Organic Pigment 2

Violet pigment (CI Pigment Violet 23).

製作濾色器時之有機顏料具有與習知之通用用途完全不同之特性，具體而言，具有使液晶顯示裝置等之顯示畫面變得更明亮(高亮度化)等要求。然而，若與ε型酞菁銅顏料併用二

紫顏料，則無法達成高亮度，故而特別是對於用於藍色像素部(B)之有機顏料尤其要求高亮度化。 The organic pigments used in the production of color filters have completely different characteristics from conventional general-purpose applications, and specifically, have requirements such as making a display screen of a liquid crystal display device or the like brighter (higher brightness). However, if used in combination with ε-type copper phthalocyanine pigment

Since a purple pigment cannot achieve high brightness, the organic pigment used for the blue pixel portion (B) is particularly required to have high brightness.

為了應對此種高亮度化，最近正研究將於亮度之方面較ε型酞菁銅顏料優異之C.I.顏料藍1之類的三芳基甲烷顏料用於濾色器之藍色像素部(專利文獻1~3)。 In order to cope with such high brightness, research is currently underway to use a triarylmethane pigment such as CI Pigment Blue 1 which is superior in brightness to ε-type copper phthalocyanine pigments for the blue pixel portion of a color filter (Patent Document 1) ~ 3).

作為該C.I.顏料藍1，著名的是以下化學結構之BASF公司之Fanal Color(FANAL BLUE D6340、FANAL BLUE D6390)，C.I.顏料藍1係將作為鹼性三芳基甲烷染料之維多利亞純藍BO利用磷鉬酸或磷鎢鉬酸之類的雜多酸進行色澱化而獲得。關於以此方式獲得之C.I.顏料藍1，陽離子之相對離子A^-為科金型(Keggin type)PMo_xW_12-xO₄₀。 As the CI Pigment Blue 1, the well-known Fanal Color (FANAL BLUE D6340, FANAL BLUE D6390) of the following chemical structure of BASF Company, CI Pigment Blue 1 series will be used as the basic triaryl methane dye of Victoria Pure Blue BO using phosphorus molybdenum Heteropolyacids such as acids or phosphotungstic molybdic acids are obtained by lake formation. Obtained on CI Pigment Blue 1 of this embodiment, the cationic counterions A ^- is Cocking type _{_{(Keggin type) PMo x W 12}} -x O 40.

[其中，通式(IX)中，A^n-為科金型磷鎢鉬酸根陰離子或磷鉬酸根陰離子；n表示任意之自然數] [Wherein, in the general formula (IX), A ^n- is a Coking-type phosphotungstate molybdate anion or a phosphomolybdate anion; n represents an arbitrary natural number]

又，最近亦研究將並非是上述三芳基甲烷顏料之三芳基甲烷染料用於濾色器之藍色像素部(專利文獻4~5)。關於該等三芳基甲烷染料，作為陰離子，認為可使用鹵化物陰離子、四苯基硼之類的硼陰離子、有機羧酸根陰離子、無機硫酸根陰離子、無機磷酸根陰離子、脂肪族磺酸陰離子、芳香族磺酸陰離子、與蒽醌色素或酞菁色素或靛藍色素對應之磺酸陰離子等。 In addition, recently, it has been studied to use a triarylmethane dye other than the triarylmethane pigment for a blue pixel portion of a color filter (Patent Documents 4 to 5). Regarding these triarylmethane dyes, as anions, it is thought that a halide anion, a boron anion such as tetraphenylboron, an organic carboxylate anion, an inorganic sulfate anion, an inorganic phosphate anion, an aliphatic sulfonic acid anion, and an aromatic can be used. Sulfonic acid anion, sulfonic acid corresponding to anthraquinone pigment or phthalocyanine pigment or indigo pigment Acid anions, etc.

進而，亦正研究將由金屬酞菁磺酸與三芳基甲烷陽離子之鹽所構成之染料作為三芳基甲烷染料，而用於濾色器之藍色像素部(專利文獻6)。 Furthermore, the use of a dye composed of a metal phthalocyanine sulfonic acid and a salt of a triarylmethane cation as a triarylmethane dye is also being studied for a blue pixel portion of a color filter (Patent Document 6).

又，亦正研究將由藉由特定結構之三芳基甲烷與特定結構之雜多金屬氧酸根陰離子(hetero polyoxometalate anion)形成之鹽所構成之化合物用於濾色器之藍色像素部(專利文獻7、8)。 Also, a blue pixel portion of a color filter is being studied using a compound composed of a salt formed by a triarylmethane with a specific structure and a hetero polyoxometalate anion with a specific structure (Patent Document 7) ,8).

進而，亦正研究將由藉由經二聚化之三芳基甲烷與陰離子形成之鹽所構成之化合物亦同樣地用於濾色器藍色像素部(專利文獻9)。 Furthermore, a compound composed of a salt formed by dimerized triarylmethane and an anion is also being studied for a blue filter portion of a color filter in the same manner (Patent Document 9).

然而，實際情況為：於將該等習知之三芳基甲烷顏料或三芳基甲烷染料用於濾色器之藍色像素部之製備之情形時，會因持續長時間地經受光線時或製作濾色器時的熱歷程，而使像素之色相顯著降低，仍然無法持續長時間維持令人滿意之亮度，就耐光性、耐熱性之方面而言不充分。 However, the actual situation is that when the conventional triarylmethane pigment or triarylmethane dye is used in the preparation of the blue pixel portion of a color filter, it will be subjected to light for a long period of time or a color filter will be produced. The thermal history of the device significantly reduces the hue of the pixel, and still cannot maintain satisfactory brightness for a long time, which is insufficient in terms of light resistance and heat resistance.

[專利文獻1]日本特開2001-81348號公報 [Patent Document 1] Japanese Patent Laid-Open No. 2001-81348

[專利文獻2]日本特開2010-83912號公報 [Patent Document 2] Japanese Patent Laid-Open No. 2010-83912

[專利文獻3]日本特開2010-85444號公報 [Patent Document 3] Japanese Patent Laid-Open No. 2010-85444

[專利文獻4]日本特開2011-68866號公報 [Patent Document 4] Japanese Patent Laid-Open No. 2011-68866

[專利文獻5]日本特開2011-70171號公報 [Patent Document 5] Japanese Patent Laid-Open No. 2011-70171

[專利文獻6]日本特開2011-70172號公報 [Patent Document 6] Japanese Patent Laid-Open No. 2011-70172

[專利文獻7]WO/2012/039416號 [Patent Document 7] WO / 2012/039416

[專利文獻8]WO/2012/039417號 [Patent Document 8] WO / 2012/039417

[專利文獻9]日本特開2013-057054號公報 [Patent Document 9] Japanese Patent Laid-Open No. 2013-057054

本發明所欲解決之課題在於可提供一種著色材料，其即便經受製作濾色器時之製造步驟所要求之200度以上之熱歷程，色相變化亦較少。例如，本發明之課題在於提供：當用於濾色器之藍色像素部之製備時，可提供色相變化較少之能夠進行優異之液晶顯示之液晶顯示裝置等的三芳基甲烷化合物及含有其而成之濾色器。 The problem to be solved by the present invention is to provide a coloring material that has less change in hue even after being subjected to a thermal history of 200 degrees or more required by the manufacturing steps when making a color filter. For example, an object of the present invention is to provide a triarylmethane compound and the like containing a liquid crystal display device capable of performing an excellent liquid crystal display with less change in hue when preparing a blue pixel portion for a color filter, and a triarylmethane compound containing the same. Made of color filters.

本發明人等鑒於上述實際情況進行了努力研究，結果發現：藉由將由具有特定之結構之鹼性多聚化三芳基甲烷染料陽離子與特定之相對陰離子(counter-anion)所構成之三芳基甲烷化合物用作濾色器之著色材料，即便經受製作濾色器時之熱歷程，色相變化亦較少，從而完成本發明。 The present inventors conducted diligent research in view of the above-mentioned actual situation, and as a result, found that by using a triarylmethane composed of a basic polymerized triarylmethane dye cation having a specific structure and a specific counter-anion The compound is used as a coloring material for a color filter, and even if it is subjected to a thermal history when the color filter is manufactured, the hue changes are small, thereby completing the present invention.

即，本發明提供一種下述通式(I)所表示之化合物。 That is, the present invention provides a compound represented by the following general formula (I).

(通式(I)中，Z表示可具有取代基之a價之脂肪族系或芳香族系的烴基；B^c-表示c價之陰離子；R¹~R³分別獨立地表示氫原子、可具有取代基之烷基或可具有取代基之芳基，R¹與R²可鍵結而形成環結構；A表示可具有取代基之芳香族基或可具有取代基之雜環基；多個R¹~R³及A分別可相同亦可不同；a表示2以上之整數，b、c、d表示1以上之整數；Y分別獨立表示氫原子、或任意之取代基)。 (In the general formula (I), Z represents an a-valent aliphatic or aromatic hydrocarbon group which may have a substituent; B ^c- represents a c-valent anion; R ¹ to R ³ each independently represent a hydrogen atom, and may An alkyl group having a substituent or an aryl group which may have a substituent, R ¹ and R ² may be bonded to form a ring structure; A represents an aromatic group which may have a substituent or a heterocyclic group which may have a substituent; multiple R ¹ to R ³ and A may be the same or different, respectively; a represents an integer of 2 or more, b, c, and d represent an integer of 1 or more; Y each independently represents a hydrogen atom or an arbitrary substituent).

一種化合物，其中，上述通式(I)中之陰離子(B^c-)為雜多金屬氧酸根陰離子。 A compound in which the anion (B ^c- ) in the general formula (I) is a heteropolyoxometalate anion.

一種化合物，其中，上述通式(I)中之陰離子(B^c-)由下述通式(II)表示。 A compound in which the anion (B ^c- ) in the general formula (I) is represented by the following general formula (II).

(通式(II)中，R⁶及R⁷分別獨立地表示可具有取代基之碳數1~8之烷基、可具有取代基之碳數2~6之烯基、或可具有取代基之碳數3~8之環烷基；再者，R⁶及R⁷可相互連結形成環，該環可具有取代基)。 (In the general formula (II), R ⁶ and R ⁷ each independently represent an alkyl group having 1 to 8 carbons which may have a substituent, an alkenyl group having 2 to 6 carbons which may have a substituent, or may have a substituent A cycloalkyl group having 3 to 8 carbon atoms; furthermore, R ⁶ and R ⁷ may be connected to each other to form a ring, and the ring may have a substituent).

一種化合物，其中，上述通式(I)中之陰離子(B^c-)由下述通式(III)表示。 A compound in which the anion (B ^c- ) in the general formula (I) is represented by the following general formula (III).

(通式(III)中，R⁸~R¹⁰分別獨立地表示可具有取代基之碳數1~8之烷基、可具有取代基之碳數2~6之烯基、或可具有取代基之碳數3~8之環烷基；再者，R⁸~R¹⁰可相互連結形成環，該環可具有取代基)。 (In the general formula (III), R ⁸ to R ¹⁰ each independently represent an alkyl group having 1 to 8 carbons which may have a substituent, an alkenyl group having 2 to 6 carbons which may have a substituent, or may have a substituent. A cycloalkyl group having 3 to 8 carbon atoms; furthermore, R ⁸ to R ¹⁰ may be connected to each other to form a ring, and the ring may have a substituent).

一種化合物，其中，上述通式(I)中之陰離子(B^c-)為磺酸陰離子(sulfonic acid anion)。 A compound in which the anion (B ^c- ) in the general formula (I) is a sulfonic acid anion.

本發明提供一種濾色器，其含有選自上述記載之化合物中之至少一種。 The present invention provides a color filter containing at least one selected from the compounds described above.

本發明之三芳基甲烷化合物由於為特定之如通式(I)所表示之三芳基甲烷化合物，故而發揮如下特別顯著之技術效果：即便經受高溫下之熱歷程，著色物之色相變化亦較小，可大幅改善耐熱性，尤其是可大幅改善液晶顯示裝置等之濾色器之耐熱性。 Since the triarylmethane compound of the present invention is a specific triarylmethane compound represented by the general formula (I), it exerts a particularly significant technical effect as follows: even if it undergoes a thermal history at high temperature, the hue change of the coloring matter is small , Can greatly improve the heat resistance, especially the heat resistance of color filters such as liquid crystal display devices.

進而，本發明之濾色器由於在藍色像素部含有特定之如通式(I)所表示之三芳基甲烷化合物，故而發揮如下特別顯著之技術效果：可提供即便經受高溫下之熱歷程，色相變化亦較少之能夠持續長時間進行更明亮之圖像顯示之液晶顯示裝置等。 Furthermore, since the color filter of the present invention contains a specific triarylmethane compound represented by the general formula (I) in the blue pixel portion, it exhibits a particularly significant technical effect that it can provide a thermal history even under high temperature, Liquid crystal display devices, etc., which have less hue changes and can display brighter images for a long time.

本發明之三芳基甲烷化合物為下述通式(I)所表示之化合物。 The triarylmethane compound of the present invention is a compound represented by the following general formula (I).

(通式(I)中，Z表示可具有取代基之a價之脂肪族系或芳香族系的烴基；B^c-表示c價之陰離子；R¹~R³分別獨立表示氫原子、可具有取代基之烷基或可具有取代基之芳基，R¹與R²可鍵結而形成環結構；A表示可具有取代基之芳香族基或可具有取代基之雜環基；多個R¹~R³及A分別可相同亦可不同；a表示2以上之整數，b、c、d表示1以上之整數；Y分別獨立表示氫原子、或任意之取代基)。 (In the general formula (I), Z represents an a-valent aliphatic or aromatic hydrocarbon group which may have a substituent; B ^c- represents a c-valent anion; R ¹ to R ³ each independently represent a hydrogen atom and may have An alkyl group of a substituent or an aryl group which may have a substituent, R ¹ and R ² may be bonded to form a ring structure; A represents an aromatic group which may have a substituent or a heterocyclic group which may have a substituent; a plurality of R ¹ to R ³ and A may be the same or different; a represents an integer of 2 or more, b, c, and d represent an integer of 1 or more; Y independently represents a hydrogen atom or an arbitrary substituent).

本發明之通式(I)之化合物為水不溶性之色料，由三芳基甲烷陽離子部分與陰離子所構成。 The compound of the general formula (I) of the present invention is a water-insoluble colorant, and is composed of a triarylmethane cation portion and an anion.

於通式(I)中，R¹~R³可相同亦可不同。因此，-NR¹R²基可為左右對稱，亦可為左右非對稱。 In the general formula (I), R ¹ to R ³ may be the same or different. Therefore, the -NR ¹ R ² group may be bilaterally symmetric or bilaterally asymmetric.

於鄰接之R¹與R²鍵結而形成環之情形時，該等可為經雜原子交聯之環。作為該環之具體例，例如可列舉以下者。該等環可具有取代基。 In the case where adjacent R ¹ and R ^{2 are} bonded to form a ring, these may be heterocyclic cross-linked rings. Specific examples of the ring include the following. The rings may have a substituent.

又，關於R¹~R³，就化學穩定性之方面而言，較佳為分別獨立為氫原子、可具有取代基之烷基、或可具有取代基之芳基。 In addition, as for R ¹ to R ³ , in terms of chemical stability, an alkyl group which may be a hydrogen atom independently, a substituent which may have a substituent, or an aryl group which may have a substituent are preferred.

Y較佳為分別獨立為氫原子、或任意之取代基。 Y is preferably each independently a hydrogen atom or an arbitrary substituent.

其中，R¹~R³更佳為分別獨立為氫原子；甲基、乙基、丙基、異丙基、環丙基、丁基、異丁基、第二丁基、第三丁基、戊基、環戊基、己基、環己基、庚基、辛基、2-乙基己基、壬基、癸基等烷基；苯基、萘基、噻吩基、呋喃基、噻唑基等芳基之任一者。 Among them, R ¹ to R ^{3 are more} preferably each independently a hydrogen atom; methyl, ethyl, propyl, isopropyl, cyclopropyl, butyl, isobutyl, second butyl, third butyl, Alkyl groups such as pentyl, cyclopentyl, hexyl, cyclohexyl, heptyl, octyl, 2-ethylhexyl, nonyl, decyl; aryl groups such as phenyl, naphthyl, thienyl, furyl, and thiazolyl Either.

於R¹~R³及Y表示烷基或芳基之情形時，該烷基或芳基可進而具有任意之取代基。作為該烷基或芳基可進而具有之任意之取代基，例如可列舉下述[取代基群R]。 When R ¹ to R ³ and Y represent an alkyl group or an aryl group, the alkyl group or the aryl group may further have an arbitrary substituent. As an arbitrary substituent which this alkyl group or an aryl group may have further, the following [substituent group R] is mentioned, for example.

[取代基群R] [Substituent Group R]

可列舉：甲基、乙基、丙基、異丙基、環丙基、丁基、異丁基、第二丁基、第三丁基、戊基、環戊基、己基、環己基、庚基、辛基、2-乙基己基、壬基、癸基等烷基；苯基、萘基、噻吩基、呋喃基、噻唑基等芳基；氟原子、氯原子、溴原子、碘原子等鹵素原子；氰基；羥基；甲氧基、乙氧基、丙氧基、丁氧基等碳原子數1~8之烷氧基；氯甲基、三氟甲基等鹵烷基；胺基、二乙胺基、二丁胺基、乙醯胺基等可具有取代基之胺基；乙醯基、苯甲醯基等醯基；乙醯氧基、苯甲醯氧基等醯氧基等。 Examples include: methyl, ethyl, propyl, isopropyl, cyclopropyl, butyl, isobutyl, second butyl, third butyl, pentyl, cyclopentyl, hexyl, cyclohexyl, heptyl Alkyl groups such as alkyl, octyl, 2-ethylhexyl, nonyl, decyl; aryl groups such as phenyl, naphthyl, thienyl, furyl, and thiazolyl; fluorine atom, chlorine atom, bromine atom, iodine atom, etc. Halogen atom; cyano; hydroxyl; methoxy, ethyl Alkoxy groups having 1 to 8 carbon atoms such as oxy, propoxy, and butoxy; haloalkyl groups such as chloromethyl and trifluoromethyl; amine, diethylamino, dibutylamino, and acetamidine Amino groups, such as an amine group, which may have a substituent; fluorenyl groups, such as an ethyl fluorenyl group and a benzyl fluorenyl group;

作為R¹~R³，進而較佳為可具有取代基之碳原子數1~8之烷基，更具體而言，可列舉：甲基、乙基、丙基、異丙基、丁基、異丁基、第二丁基、戊基、己基、2-乙基己基等未經取代之烷基；2-甲氧基乙基、2-乙氧基乙基等烷氧基烷基；2-乙醯氧基乙基等醯氧基；2-氰乙基等氰基烷基；2,2,2-三氟乙基、4,4,4-三氟丁基等氟烷基等。 As R ¹ to R ³ , an alkyl group having 1 to 8 carbon atoms which may have a substituent is further preferred. More specifically, methyl, ethyl, propyl, isopropyl, butyl, Unsubstituted alkyl such as isobutyl, second butyl, pentyl, hexyl, 2-ethylhexyl; alkoxyalkyl such as 2-methoxyethyl, 2-ethoxyethyl; 2 -Ethoxy groups such as ethoxyethyl; cyanoalkyl groups such as 2-cyanoethyl; fluoroalkyl groups such as 2,2,2-trifluoroethyl and 4,4,4-trifluorobutyl.

又，作為Y，只要無損本發明之效果，則可分別獨立為任意之基，例如可列舉：氫原子；甲基、乙基、丙基、異丙基、環丙基、丁基、異丁基、第二丁基、第三丁基、戊基、環戊基、己基、環己基、庚基、辛基、2-乙基己基等碳原子數1~8之烷基；甲氧基、乙氧基、丙氧基、丁氧基等碳原子數1~8之烷氧基；氟原子、氯原子、溴原子、碘原子等鹵素原子；苯基、萘基、噻吩基、呋喃基、噻唑基等芳基；氰基等。 In addition, as Y, as long as the effect of the present invention is not impaired, each group may be independently any group, and examples thereof include a hydrogen atom; a methyl group, an ethyl group, a propyl group, an isopropyl group, a cyclopropyl group, a butyl group, and an isobutyl group. Alkyl groups having 1 to 8 carbon atoms such as alkyl, second butyl, third butyl, pentyl, cyclopentyl, hexyl, cyclohexyl, heptyl, octyl, 2-ethylhexyl; methoxy, Alkoxy groups having 1 to 8 carbon atoms, such as ethoxy, propoxy, and butoxy; halogen atoms such as fluorine, chlorine, bromine, and iodine; phenyl, naphthyl, thienyl, furanyl, Aryl groups such as thiazolyl; cyano and the like.

又，於上述烷基、烷氧基及芳基中，可進而具有其他任意取代基。作為上述烷基、烷氧基及芳基可進而具有的任意之取代基，例如可列舉上述[取代基群R]之段落所記載者。再者，鄰接之Y可鍵結而進一步形成環結構。關於本發明中之Y，就色純度較高之方面而言，最佳為氫原子。 The alkyl group, alkoxy group, and aryl group may further have other arbitrary substituents. Examples of the optional substituent that the alkyl group, alkoxy group, and aryl group may further have include those described in the paragraph of the above-mentioned [Substituent Group R]. Furthermore, adjacent Y may be bonded to further form a ring structure. Regarding Y in the present invention, in terms of high color purity, a hydrogen atom is most preferred.

A中之芳香族基或雜環基並無特別限定。作為芳香族基中之芳香族，可列舉：苯環；以及萘環、四氫萘環、茚環、茀環、蒽環、菲環等縮合多環芳香族烴；聯苯、聯三苯、二苯甲烷、三苯甲烷、茋等鏈狀多環式烴。於該鏈狀多環式烴中，可如二苯醚等般於鏈狀骨架中具有O、S等雜原子。另一方面，作為雜環基中之雜環，可列舉：呋喃、噻吩、吡咯、

唑、噻唑、咪唑、吡唑等5元雜環；吡喃、哌哢、吡啶、嗒

、嘧啶、吡

等6元雜環；苯并呋喃、苯并噻吩、吲哚、咔唑、香豆素、苯并哌哢、喹啉、異喹啉、吖啶、酞

、喹唑啉、喹

啉等縮合多環式雜環。該等芳香族基或雜環基可具有取代基。作為該取代基，例如可列舉上述[取代基群R]之段落記載者。 The aromatic group or heterocyclic group in A is not particularly limited. Examples of the aromatic group in the aromatic group include benzene rings; condensed polycyclic aromatic hydrocarbons such as naphthalene ring, tetrahydronaphthalene ring, indene ring, fluorene ring, anthracene ring, and phenanthrene ring; biphenyl, bitriphenyl, Diphenylmethane, triphenylmethane, pyrene and other chain polycyclic hydrocarbons. The chain polycyclic hydrocarbon may have heteroatoms such as O and S in the chain skeleton, such as diphenyl ether. On the other hand, as the hetero ring in the heterocyclic group, furan, thiophene, pyrrole,

5-membered heterocycles such as azole, thiazole, imidazole, pyrazole; pyran, piperidine, pyridine, da

, Pyrimidine, pyridine

And other 6-membered heterocyclic rings; benzofuran, benzothiophene, indole, carbazole, coumarin, benzopiperidine, quinoline, isoquinoline, acridine, phthaloline

, Quinazoline, quinine

Condensed polycyclic heterocycles, such as phthaloline. The aromatic group or heterocyclic group may have a substituent. Examples of the substituent include those described in the paragraph [Substituent Group R].

其中，就耐熱性之方面而言，作為A中之芳香族基或雜環基，較佳為下述通式(IV)、下述通式(V)或下述通式(VI)所表示之基。 Among them, in terms of heat resistance, the aromatic group or heterocyclic group in A is preferably represented by the following general formula (IV), the following general formula (V), or the following general formula (VI) The base.

(通式(IV)中，R¹¹及R¹²分別獨立表示氫原子、可具有取代基之烷基或可具有取代基之芳基，R¹¹與R¹²可鍵結而形成環結構；E¹分別獨立地表示氫原子、或任意之取代基；*表示與碳原子之鍵結鍵)。 (In the general formula (IV), R ¹¹ and R ¹² each independently represent a hydrogen atom, an alkyl group which may have a substituent, or an aryl group which may have a substituent, and R ¹¹ and R ¹² may be bonded to form a ring structure; E ¹ Each independently represents a hydrogen atom or an arbitrary substituent; * represents a bond to a carbon atom).

(通式(V)中，R¹³及R¹⁴分別獨立表示氫原子、可具有取代基之烷基或可具有取代基之芳基，R¹³與R¹⁴可鍵結而形成環結構；E²分別獨立地表示氫原子、或任意之取代基；*表示與碳原子之鍵結鍵)。 (In the general formula (V), R ¹³ and R ¹⁴ each independently represent a hydrogen atom, an alkyl group which may have a substituent, or an aryl group which may have a substituent, and R ¹³ and R ¹⁴ may be bonded to form a ring structure; E ² Each independently represents a hydrogen atom or an arbitrary substituent; * represents a bond to a carbon atom).

(通式(VI)中，R¹⁵表示氫原子、碳數1~20之烷基、或可具有取代基之芳基；X表示氧原子、氮原子或硫原子；R¹⁶及R¹⁷分別獨立地表示氫原子、可具有取代基之烷基或可具有取代基之芳基，R¹⁶與R¹⁷可鍵結而形成環結構；*表示與碳原子之鍵結鍵)。 (In the general formula (VI), R ¹⁵ represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, or an aryl group which may have a substituent; X represents an oxygen atom, a nitrogen atom, or a sulfur atom; R ¹⁶ and R ¹⁷ are each independently Ground represents a hydrogen atom, an alkyl group which may have a substituent, or an aryl group which may have a substituent. R ¹⁶ and R ¹⁷ may be bonded to form a ring structure; * represents a bond to a carbon atom).

<關於通式(IV)> <About General Formula (IV)>

於通式(IV)中，R¹¹與R¹²可相同亦可不同。因此，-NR¹¹R¹²基可為左右對稱，亦可為左右非對稱。 In the general formula (IV), R ¹¹ and R ¹² may be the same or different. Therefore, the -NR ¹¹ R ¹² group may be bilaterally symmetric or bilaterally asymmetric.

於鄰接之R¹¹與R¹²鍵結而形成環之情形時，該等可為經雜原子交聯之環。該等環可具有取代基。 In the case where adjacent R ¹¹ and R ^{12 are} bonded to form a ring, these may be a heteroatom-crosslinked ring. The rings may have a substituent.

又，關於R¹¹及R¹²，就化學穩定性之方面而言，較佳為分別獨立為氫原子、可具有取代基之烷基、或可具有取代基之芳基。其中，R¹¹及R¹²更佳為分別獨立為氫原子；甲基、乙基、丙基、異丙基、環丙基、丁基、異丁基、第二丁基、第三丁基、戊基、環戊基、己基、環己基、庚基、辛基、2-乙基己基、壬基、癸基等烷基；苯基、萘基、噻吩基、呋喃基、噻唑基等芳基之任一者。 Further, in terms of chemical stability, R ¹¹ and R ¹² are each preferably a hydrogen atom, an alkyl group which may have a substituent, or an aryl group which may have a substituent. Among them, R ¹¹ and R ^{12 are more} preferably each independently a hydrogen atom; methyl, ethyl, propyl, isopropyl, cyclopropyl, butyl, isobutyl, second butyl, third butyl, Alkyl groups such as pentyl, cyclopentyl, hexyl, cyclohexyl, heptyl, octyl, 2-ethylhexyl, nonyl, decyl; aryl groups such as phenyl, naphthyl, thienyl, furyl, and thiazolyl Either.

於R¹¹及R¹²表示烷基或芳基之情形時，該烷基或芳基可進而具有任意之取代基。作為該烷基或芳基可進而具有的任意之取代基，例如可列舉上述[取代基群R]之段落記載者。 When R ¹¹ and R ¹² represent an alkyl group or an aryl group, the alkyl group or the aryl group may further have an arbitrary substituent. Examples of the optional substituent that the alkyl group or the aryl group may further have include those described in the paragraph of the above-mentioned [Substituent Group R].

作為R¹¹及R¹²，進而較佳為分別獨立為氫原子或可具有取代基之碳原子數1~8之烷基，更具體而言，可列舉：甲基、乙基、丙基、異丙基、丁基、異丁基、第二丁基、戊基、己基、2-乙基己基等未經取代之烷基；2-甲氧基乙基、2-乙氧基乙基等烷氧基烷基；2-乙醯氧基乙基等醯氧基；2-氰乙基等氰基烷基；2,2,2-三氟乙基、4,4,4-三氟丁基等氟烷基等。 As R ¹¹ and R ¹² , an alkyl group having 1 to 8 carbon atoms which is independently a hydrogen atom or a substituent may be further preferred, and more specifically, methyl, ethyl, propyl, iso Unsubstituted alkyl groups such as propyl, butyl, isobutyl, second butyl, pentyl, hexyl, 2-ethylhexyl; alkanes such as 2-methoxyethyl, 2-ethoxyethyl Oxyalkyl; fluorenyloxy such as 2-ethoxyethyl; cyanoalkyl such as 2-cyanoethyl; 2,2,2-trifluoroethyl, 4,4,4-trifluorobutyl And so on.

又，作為E¹，只要無損本發明之效果，則可分別獨立為任意之基，例如可列舉：氫原子；甲基、乙基、丙基、異丙基、環丙基、丁基、異丁基、第二丁基、第三丁基、戊基、環戊基、己基、環己基、庚基、辛基、2-乙基己基等碳原子數1~8之烷基；甲氧基、乙氧基、丙氧基、丁氧基等碳原子數1~8之烷氧基；氟原子、氯原子、溴原子、碘原子等鹵素原子；苯基、萘基、噻吩基、呋喃基、噻唑基等芳基；氰基等。 In addition, as E ¹ , as long as the effect of the present invention is not impaired, each group may be independently any group, and examples thereof include a hydrogen atom; methyl, ethyl, propyl, isopropyl, cyclopropyl, butyl, and iso. C1-C8 alkyl groups such as butyl, second butyl, third butyl, pentyl, cyclopentyl, hexyl, cyclohexyl, heptyl, octyl, 2-ethylhexyl; methoxy Alkoxy groups having 1 to 8 carbon atoms such as ethoxy, propoxy, butoxy; halogen atoms such as fluorine, chlorine, bromine, and iodine; phenyl, naphthyl, thienyl, and furanyl , Aryl groups such as thiazolyl; cyano and the like.

又，於上述烷基、烷氧基及芳基中，可進而具有其他任意取代基。作為上述烷基、烷氧基及芳基可進而具有的任意之取代基，例如可列舉上述[取代基群R]之段落記載者。再者，鄰接之E¹可鍵結而進一步形成環結構。關於本發明中之E¹，就色純度較高之方面而言，最佳為氫原子。 The alkyl group, alkoxy group, and aryl group may further have other arbitrary substituents. Examples of the optional substituent that the alkyl group, alkoxy group, and aryl group may further have include those described in the paragraph of the above-mentioned [Substituent Group R]. Furthermore, adjacent E ¹ may be bonded to further form a ring structure. Regarding E ¹ in the present invention, in terms of higher color purity, a hydrogen atom is preferred.

<關於通式(V)> <About General Formula (V)>

於通式(V)中，R¹³及R¹⁴分別獨立地表示氫原子、可具有取代基之烷基、或可具有取代基之芳基。作為R¹³及R¹⁴中之烷基，可列舉為直鏈狀、支鏈狀或環狀之烷基且其碳數通常為1以上、且通常為8以下、較佳為5以下者。作為具體例，可列舉：甲基、乙基、正丙基、2-丙基、正丁基、異丁基、第三丁基、環己基等。 In the general formula (V), R ¹³ and R ¹⁴ each independently represent a hydrogen atom, an alkyl group which may have a substituent, or an aryl group which may have a substituent. Examples of the alkyl group in R ¹³ and R ¹⁴ include a linear, branched, or cyclic alkyl group, and the number of carbon atoms is usually 1 or more, usually 8 or less, and preferably 5 or less. Specific examples include methyl, ethyl, n-propyl, 2-propyl, n-butyl, isobutyl, third butyl, and cyclohexyl.

作為R¹³及R¹⁴中之芳基，可列舉芳香族烴環基及芳香族雜環基。 Examples of the aryl group in R ¹³ and R ¹⁴ include an aromatic hydrocarbon ring group and an aromatic heterocyclic group.

作為芳香族烴環基，可為單環，亦可為縮合環，且形成環之碳數只要為5~18則並無特別限制，例如可列舉具有1個自由價之苯環、萘環、蒽環、菲環、苝環、稠四苯環、芘環、苯并芘環、苯并菲(chrysene)環、聯三伸苯環、乙烷合萘環、螢蒽(fluoranthene)環、茀環等之基。 The aromatic hydrocarbon ring group may be a monocyclic ring or a condensed ring, and the number of carbon atoms forming the ring is not particularly limited as long as it is 5 to 18. For example, a benzene ring, a naphthalene ring, Anthracene ring, phenanthrene ring, fluorene ring, fused tetraphenyl ring, fluorene ring, benzofluorene ring, chrysene ring, bitriphenylene ring, ethane naphthalene ring, fluoranthene ring, fluorene Ring and other bases.

又，作為芳香族雜環基，可為單環亦可為縮合環，且形成環之碳數只要為3~10則並無特別限制，例如可列舉具有1個自由價之呋喃環、苯并呋喃環、噻吩環、苯并噻吩環、吡咯環、吡唑環、咪唑環、

二唑環、吲哚環、咔唑環、吡咯并咪唑環、吡咯并吡唑環、吡咯并吡咯環、噻吩并吡咯環、噻吩并噻吩環、呋喃并吡咯(furopyrrole)環、呋喃并呋喃(furofuran)環、噻吩并呋喃環、苯并異

唑環、苯并異噻唑環、苯并咪唑環、吡啶環、吡

環、嗒

環、嘧啶環、三

環、喹啉環、異喹啉環、

啉(shinorine)環、喹

啉環、啡啶環、苯并咪唑環、呸啶環、喹唑啉環、喹唑啉酮環、薁環等之基。 The aromatic heterocyclic group may be a monocyclic ring or a condensed ring, and the number of carbon atoms forming the ring is not particularly limited, and examples thereof include a furan ring and a benzo group having one free valence. Furan ring, thiophene ring, benzothiophene ring, pyrrole ring, pyrazole ring, imidazole ring,

Diazole ring, indole ring, carbazole ring, pyrroloimidazole ring, pyrrolopyrazole ring, pyrrolopyrrole ring, thienopyrrole ring, thienothiophene ring, furopyrrole ring, furanofuran ( furofuran) ring, thienofuran ring, benzoiso

Azole ring, benzoisothiazole ring, benzimidazole ring, pyridine ring, pyridine

Ring

Ring, pyrimidine ring, three

Ring, quinoline ring, isoquinoline ring,

Shinorine ring, quinine

Phylline ring, morphine ring, benzimidazole ring, pyrimidine ring, quinazoline ring, quinazolinone ring, fluorene ring and the like.

於鄰接之R¹³與R¹⁴鍵結而形成環之情形時，該等可為經雜原子交聯之環。該等環可具有取代基。 In the case where adjacent R ¹³ and R ^{14 are} bonded to form a ring, these may be a heteroatom-crosslinked ring. The rings may have a substituent.

就化學穩定性之方面而言，作為R¹³及R¹⁴，較佳為分別獨立為氫原子、可具有取代基之碳數1~8之烷基或可具有取代基之苯基。 In terms of chemical stability, R ¹³ and R ¹⁴ are each preferably a hydrogen atom, an alkyl group having 1 to 8 carbon atoms which may have a substituent, or a phenyl group which may have a substituent.

作為R¹³及R¹⁴中之烷基、芳基及相互連結而形成之環可具有之取代基，例如可列舉下述[取代基群Q]。 Examples of the substituent which the alkyl group, aryl group, and ring formed by connecting to each other in R ¹³ and R ¹⁴ may have include the following [Substituent Group Q].

[取代基群Q] [Substituent Group Q]

氟原子、氯原子、碳數1~8之烷基、碳數2~8之烯基、碳數1~8之烷氧基、苯基、2,4,6-三甲苯基、甲苯基、萘基、氰基、乙醯氧基、碳數2~9之烷基羰氧基、磺醯胺基、碳數2~9之碸烷基醯胺基、碳數2~9之烷基羰基、苯乙基、羥乙基、乙醯胺基、碳數1~4之烷基鍵結而成之二烷基胺基乙基、三氟甲基、碳數1~8之三烷基矽基、硝基、碳數1~8之烷硫基。 Fluorine atom, chlorine atom, alkyl group having 1 to 8 carbon atoms, alkenyl group having 2 to 8 carbon atoms, alkoxy group having 1 to 8 carbon atoms, phenyl group, 2,4,6-trimethylphenyl group, tolyl group, Naphthyl, cyano, ethoxyl, alkylcarbonyloxy with 2-9 carbons, sulfonamido, fluorenylalkylfluorenyl with 2-9 carbons, alkylcarbonyl with 2-9 carbons , Phenethyl, hydroxyethyl, acetamido, and dialkylaminoethyl with 1 to 4 carbon atoms, trifluoromethyl, and trialkylsilyl with 1 to 8 carbon atoms Alkyl, nitro, alkylthio having 1 to 8 carbon atoms.

其中，作為R¹³及R¹⁴中之烷基、芳基及相互連結而形成之環可具有之取代基，較佳為碳數1~8之烷基、碳數2~8之烷氧基、氰基、乙醯氧基、碳數2~8之烷基羧基、磺醯胺基、碳數2~8之碸烷基醯胺基及氟原子。 Among them, as the substituents which the alkyl group, aryl group, and ring formed by mutual connection in R ¹³ and R ¹⁴ may have, an alkyl group having 1 to 8 carbon atoms, an alkoxy group having 2 to 8 carbon atoms, A cyano group, an ethoxy group, an alkyl carboxyl group having 2 to 8 carbon atoms, a sulfonamido group, a fluorenyl alkyl amine group having 2 to 8 carbon atoms, and a fluorine atom.

又，作為E²，只要無損本發明之效果，則可分別獨立為任意之基，例如可列舉：氫原子；甲基、乙基、丙基、異丙基、環丙基、丁基、異丁基、第二丁基、第三丁基、戊基、環戊基、己基、環己基、庚基、辛基、2-乙基己基等碳原子數1~8之烷基；甲氧基、乙氧基、丙氧基、丁氧基等碳原子數1~8之烷氧基；氟原子、氯原子、溴原子、碘原子等鹵素原子；苯基、萘基、噻吩基、呋喃基、噻唑基等芳基；氰基等。 In addition, as E ² , as long as the effect of the present invention is not impaired, each group may be independently any group. Examples include hydrogen atom; methyl, ethyl, propyl, isopropyl, cyclopropyl, butyl, and iso. C1-C8 alkyl groups such as butyl, second butyl, third butyl, pentyl, cyclopentyl, hexyl, cyclohexyl, heptyl, octyl, 2-ethylhexyl; methoxy Alkoxy groups having 1 to 8 carbon atoms such as ethoxy, propoxy, butoxy; halogen atoms such as fluorine, chlorine, bromine, and iodine; phenyl, naphthyl, thienyl, and furanyl , Aryl groups such as thiazolyl; cyano and the like.

又，於上述烷基、烷氧基及芳基中，可進而具有其他任意取代基。作為上述烷基、烷氧基及芳基可進而具有的任意之取代基，例如可列舉上述[取代基群R]之段落記載者。再者，鄰接之E²可鍵結而形成環結構。關於本發明中之E²，就色純度較高之方面而言，最佳為氫原子。 The alkyl group, alkoxy group, and aryl group may further have other arbitrary substituents. Examples of the optional substituent that the alkyl group, alkoxy group, and aryl group may further have include those described in the paragraph of the above-mentioned [Substituent Group R]. Furthermore, adjacent E ² may be bonded to form a ring structure. Regarding E ² in the present invention, in terms of high color purity, a hydrogen atom is preferred.

<關於通式(VI)> <About General Formula (VI)>

作為通式(VI)中之R¹⁵所表示之碳數1~20之烷基，可列舉：甲基、乙基、正丙基、正丁基、正戊基、正己基、正庚基、正辛基等直鏈狀烷基；異丙基、第二丁基、第三丁基、異戊基、1-甲基戊基、2-甲基戊基、1-乙基丁基、2-乙基丁基、1-甲基己基、2-甲基己基、3-甲基己基、4-甲基己基、1-乙基戊基、2-乙基戊基、3-乙基戊基、1-丙基丁基、1-(1-甲基乙基)丁基等支鏈狀之烷基；環丙基、環丁基、環戊基、環己基、金剛烷基等環狀烷基；其中，較佳為碳數1~8之烷基，更佳為碳數1~6之烷基，進而較佳為碳數1~4之烷基。 Examples of the alkyl group having 1 to 20 carbon atoms represented by R ¹⁵ in the general formula (VI) include methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl, n-heptyl, Linear alkyl groups such as n-octyl; isopropyl, second butyl, third butyl, isopentyl, 1-methylpentyl, 2-methylpentyl, 1-ethylbutyl, 2 -Ethylbutyl, 1-methylhexyl, 2-methylhexyl, 3-methylhexyl, 4-methylhexyl, 1-ethylpentyl, 2-ethylpentyl, 3-ethylpentyl Branched alkyl groups such as 1,1-propylbutyl, 1- (1-methylethyl) butyl; cyclic alkanes such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, adamantyl, etc. Among them, an alkyl group having 1 to 8 carbon atoms is preferred, an alkyl group having 1 to 6 carbon atoms is more preferred, and an alkyl group having 1 to 4 carbon atoms is more preferred.

作為通式(VI)中之R¹⁵所表示之芳基，可列舉苯基、萘基、苄基等碳數6~14之芳基。 Examples of the aryl group represented by R ¹⁵ in the general formula (VI) include an aryl group having 6 to 14 carbon atoms such as a phenyl group, a naphthyl group, and a benzyl group.

作為通式(VI)中之R¹⁵所表示之可具有取代基之芳基中之取代基，可列舉：氟原子、氯原子、溴原子、碘原子等鹵素原子；甲基、乙基等碳數1~6之烷基；氯甲基、三氟甲基等碳數1~6之鹵烷基；甲氧基、乙氧基等碳數1~6之烷氧基；羥基；胺磺醯基；甲磺醯基等碳數1~6之烷基磺醯基等；-SO^3-。 Examples of the substituent in the aryl group which may have a substituent represented by R ¹⁵ in the general formula (VI) include halogen atoms such as a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom; carbons such as a methyl group and an ethyl group; Alkyl groups of 1 to 6; haloalkyl groups of 1 to 6 carbons such as chloromethyl and trifluoromethyl; alkoxy groups of 1 to 6 carbons such as methoxy and ethoxy groups; hydroxyl groups; Groups; alkylsulfonyl groups having 1 to 6 carbons such as methanesulfonyl; -SO ^3- .

於通式(VI)中，X表示氧原子、氮原子或硫原子。就合成之容易度之觀點而言，較佳為硫原子。 In the general formula (VI), X represents an oxygen atom, a nitrogen atom, or a sulfur atom. From the viewpoint of ease of synthesis, a sulfur atom is preferred.

於通式(VI)中，R¹⁶與R¹⁷可相同亦可不同。因此，-NR¹⁶R¹⁷基可為左右對稱，亦可為左右非對稱。 In the general formula (VI), R ¹⁶ and R ¹⁷ may be the same or different. Therefore, the -NR ¹⁶ R ¹⁷ group may be left-right symmetric or left-right asymmetric.

於鄰接之R¹⁶與R¹⁷鍵結而形成環之情形時，該等可為經雜原子交聯之環。該等環可具有取代基。 In the case where adjacent R ¹⁶ and R ^{17 are} bonded to form a ring, these may be a heteroatom-crosslinked ring. The rings may have a substituent.

又，關於R¹⁶及R¹⁷，就化學穩定性之方面而言，較佳為分別獨立為氫原子、可具有取代基之烷基、或可具有取代基之芳基。其中，R¹⁶及R¹⁷更佳為分別獨立為氫原子；甲基、乙基、丙基、異丙基、環丙基、丁基、異丁基、第二丁基、第三丁基、戊基、環戊基、己基、環己基、庚基、辛基、2-乙基己基、壬基、癸基等烷基；苯基、萘基、噻吩基、呋喃基、噻唑基等芳基之任一者。 Regarding R ¹⁶ and R ¹⁷ , in terms of chemical stability, an alkyl group which may independently be a hydrogen atom, which may have a substituent, or an aryl group which may have a substituent, is preferred. Among them, R ¹⁶ and R ^{17 are more} preferably each independently a hydrogen atom; methyl, ethyl, propyl, isopropyl, cyclopropyl, butyl, isobutyl, second butyl, third butyl, Alkyl groups such as pentyl, cyclopentyl, hexyl, cyclohexyl, heptyl, octyl, 2-ethylhexyl, nonyl, decyl; aryl groups such as phenyl, naphthyl, thienyl, furyl, and thiazolyl Either.

於R¹⁶及R¹⁷表示烷基或芳基之情形時，該烷基或芳基可進而具有任意之取代基。作為該烷基或芳基可進而具有之任意之取代基，例如可列舉上述[取代基群R]之段落記載者。 When R ¹⁶ and R ¹⁷ represent an alkyl group or an aryl group, the alkyl group or the aryl group may further have an arbitrary substituent. As the arbitrary substituent which this alkyl group or aryl group may have further, the thing described in the paragraph of the said [substituent group R] is mentioned, for example.

作為通式(VI)所表示之基，較佳為下述式所表示之基。*表示與碳原子之鍵結鍵。 The group represented by the general formula (VI) is preferably a group represented by the following formula. * Indicates a bond with a carbon atom.

上述通式(I)中之Z為可具有取代基之a價之脂肪族系或芳香族系的烴基。脂肪族系之烴基為直鏈、分支或環狀之任一者即可，可具有不飽和鍵，可具有取代基，可於碳鏈中含有O、S、N。例如，可含有羰基、羧基、氧羰基、醯胺基等，氫原子可進而被鹵素原子等取代。芳香族系之烴基可列舉單環或多環芳香族基，可具有取代基，可為含有O、S、 N之雜環。例如可列舉含有下述化學鍵之基：苯環；以及萘環、四氫萘環、茚環、茀環、蒽環、菲環等縮合多環芳香族烴；聯苯、聯三苯等鏈狀多環式芳香族烴；呋喃、噻吩、吡咯、

唑、噻唑、咪唑、吡唑等5元雜環；吡喃、哌哢、吡啶、哌哢、嗒

、嘧啶、吡

、喹唑啉、喹

啉等縮合多環式雜環。 Z in the general formula (I) is an a-valent aliphatic or aromatic hydrocarbon group which may have a substituent. The aliphatic hydrocarbon group may be any of linear, branched, or cyclic, and may have an unsaturated bond, may have a substituent, and may contain O, S, and N in the carbon chain. For example, it may contain a carbonyl group, a carboxyl group, an oxycarbonyl group, a fluorenyl group, and the like, and a hydrogen atom may be further substituted with a halogen atom or the like. Examples of the aromatic hydrocarbon group include a monocyclic or polycyclic aromatic group, which may have a substituent, and may be a heterocyclic ring containing O, S, and N. Examples include groups containing the following chemical bonds: benzene rings; and condensed polycyclic aromatic hydrocarbons such as naphthalene ring, tetrahydronaphthalene ring, indene ring, fluorene ring, anthracene ring, and phenanthrene ring; chain forms such as biphenyl and bitriphenyl Polycyclic aromatic hydrocarbons; furan, thiophene, pyrrole,

5-membered heterocycles such as azole, thiazole, imidazole, pyrazole; pyran, piperidine, pyridine, piperidine,

, Pyrimidine, pyridine

, Quinazoline, quinine

Condensed polycyclic heterocycles, such as phthaloline.

其中，上述通式(I)中之Z為與N(氮原子)直接鍵結之碳原子不具有π鍵的a價之有機基，且該有機基表示至少於與N直接鍵結之末端具有飽和脂肪族烴基之脂肪族烴基、或具有該脂肪族烴基之芳香族基，較佳為於碳鏈中可含有O(氧原子)、S(硫原子)、N(氮原子)之基。由於與N直接鍵結之碳原子不具有π鍵，故而陽離子性之顯色部位所具有之色調或透過率等色特性並不受連結基Z或其他顯色部位之影響，可保持與單體相同之顏色。 Wherein, Z in the above general formula (I) is an organic group of a valence having no π bond in a carbon atom directly bonded to N (nitrogen atom), and the organic group has at least The aliphatic hydrocarbon group of the saturated aliphatic hydrocarbon group or the aromatic group having the aliphatic hydrocarbon group is preferably a group which may contain O (oxygen atom), S (sulfur atom), and N (nitrogen atom) in the carbon chain. Since the carbon atom directly bonded to N does not have a π bond, the color characteristics such as hue or transmittance of the cationic color-developing site are not affected by the linking group Z or other color-developing sites, and can be maintained with the monomer. Same color.

關於Z中至少於與N直接鍵結之末端具有飽和脂肪族烴基之脂肪族烴基，只要與N直接鍵結之末端之碳原子不具有π鍵即可，可為直鏈、分支或環狀之任一者，可使末端以外之碳原子具有不飽和鍵，亦可具有取代基，亦可於碳鏈中含有O、S、N。例如，可含有羰基、羧基、氧羰基、醯胺基等，氫原子可進而被鹵素原子等取代。 Regarding the aliphatic hydrocarbon group having a saturated aliphatic hydrocarbon group at least at the terminal directly bonded to N in Z, as long as the carbon atom at the terminal directly bonded to N does not have a π bond, it may be a straight chain, branched or cyclic one. Either carbon atoms other than the terminal may have an unsaturated bond, may have a substituent, and may contain O, S, and N in the carbon chain. For example, it may contain a carbonyl group, a carboxyl group, an oxycarbonyl group, a fluorenyl group, and the like, and a hydrogen atom may be further substituted with a halogen atom or the like.

又，關於Z中具有上述脂肪族烴基之芳香族基，可列舉具有脂肪族烴基的單環或多環芳香族基，該脂肪族烴基至少於與N直接鍵結之末端具有飽和脂肪族烴基，亦可具有取代基，亦可為含有O、S、N之雜環。 The aromatic group having the above-mentioned aliphatic hydrocarbon group in Z includes a monocyclic or polycyclic aromatic group having an aliphatic hydrocarbon group, and the aliphatic hydrocarbon group has a saturated aliphatic hydrocarbon group at least at a terminal directly bonded to N. It may have a substituent or a heterocyclic ring containing O, S, and N.

其中，就骨架之堅牢度之方面而言，Z較佳為包含環狀之脂肪族烴基或芳香族基。 Among these, in terms of the fastness of the skeleton, Z is preferably a cyclic aliphatic hydrocarbon group or an aromatic group.

作為環狀之脂肪族烴基，尤其是橋接脂環式烴基就骨架之堅牢度之方面而言較佳。所謂橋接脂環式烴基，意指於脂肪族環內具有橋接結構且具有多環結構之多環狀脂肪族烴基，例如可列舉降莰烷、二環[2,2,2]辛烷、金剛烷等。橋接脂環式烴基之中，較佳為降莰烷。又，作為芳香族基，例如可列舉含有苯環、萘環之基，其中，較佳為含有苯環之基。 As the cyclic aliphatic hydrocarbon group, especially the bridged alicyclic hydrocarbon group is preferable in terms of the fastness of the skeleton. The so-called bridged alicyclic hydrocarbon group means a polycyclic aliphatic hydrocarbon group having a bridge structure and a polycyclic structure in an aliphatic ring, and examples thereof include norbornane, bicyclo [2,2,2] octane, and diamond Alkanes, etc. Among the bridged alicyclic hydrocarbon groups, norbornane is preferred. Examples of the aromatic group include a group containing a benzene ring and a naphthalene ring. Among them, a group containing a benzene ring is preferred.

就取得原料之容易度之觀點而言，Z較佳為2價。例如，於Z為2價之有機基之情形時，可列舉碳數1~20之直鏈、分支、或環狀之伸烷基、或苯二甲基等2個碳數1~20之伸烷基經取代而成之芳香族基等。 From the viewpoint of easiness of obtaining raw materials, Z is preferably divalent. For example, when Z is a divalent organic group, linear, branched, or cyclic alkylene groups having 1 to 20 carbon atoms, or two carbon atoms having 1 to 20 carbon atoms, such as xylylene, may be mentioned. An aromatic group in which an alkyl group is substituted.

作為Z之具體例，可列舉如下者，但並不限定於該等。*表示與氮原子之鍵結鍵。 Specific examples of Z include the following, but are not limited thereto. * Indicates a bond with a nitrogen atom.

1分子內之多個R¹~R³及A可相同亦可不同。於多個R¹~ R³及A分別相同之情形時，由於顯色部位呈相同之顯色，故而可再現與單獨之顯色部位相同之顏色，就色純度之方面而言較佳。另一方面，於R¹~R³及A之中至少1者採用不同之取代基之情形時，可再現混合多種單體之顏色，從而可調整為所需顏色。 A plurality of R ¹ to R ³ and A in one molecule may be the same or different. In the case where a plurality of R ¹ to R ³ and A are respectively the same, since the color-developed parts show the same color development, the same color as the individual color-developed parts can be reproduced, which is preferable in terms of color purity. On the other hand, in the case where at least one of R ¹ to R ³ and A uses different substituents, the colors of a plurality of monomers can be reproduced and mixed so that the desired color can be adjusted.

繼而，針對陰離子部分詳細地說明。[B^c-]為1價以上之陰離子。[B^c-]只要為1價以上之陰離子，則並無特別限制，就耐熱性之方而而言較佳之陰離子可列舉雜多金屬氧酸根陰離子、下述通式(II)所表示之陰離子、下述通式(III)所表示之陰離子、及磺酸陰離子。 Next, the anion portion will be described in detail. [B ^c- ] is an anion having a valence of 1 or more. [B ^c- ] is not particularly limited as long as it is an anion having a valence of 1 or more. Examples of the preferred anion in terms of heat resistance include a heteropolyoxometalate anion and an anion represented by the following general formula (II). , An anion represented by the following general formula (III), and a sulfonic acid anion.

本發明中，將雜多酸根陰離子稱為雜多金屬氧酸根陰離子。 In the present invention, the heteropolyacid anion is referred to as a heteropolyoxometalate anion.

雜多酸係不包含有機結構之相對較大之分子量的無機酸，可表現出鹽酸或硫酸之類的低分子之無機酸或有機酸所不具有之特異性質。第一，因陽離子之藉由雜多酸之色澱化而生成水不溶之三芳基甲烷化合物。第二，藉由選擇用於色澱化之雜多酸，有可使所獲得之三芳基甲烷化合物之耐熱性或耐光性提昇之餘地。雜多酸不含有機結構或由於含有金屬故而分子量亦能夠相對較大，因此，藉由適當地選擇雜多酸，即便於暴露於高溫或光線之情形時，亦能夠大幅抑制由陰離子結構導致之三芳基甲烷化合物之變質。 Heteropoly acid is a relatively large molecular weight inorganic acid that does not contain an organic structure, and can exhibit specific properties not possessed by low molecular inorganic or organic acids such as hydrochloric acid or sulfuric acid. First, water-insoluble triarylmethane compounds are formed due to the cation precipitation of heteropolyacids. Secondly, there is room for improving the heat resistance or light resistance of the triarylmethane compound obtained by selecting the heteropoly acid used for the lake formation. Heteropoly acids do not contain organic structures or have relatively large molecular weights because they contain metals. Therefore, by properly selecting heteropoly acids, even when exposed to high temperature or light, it can greatly suppress the effects caused by anionic structures. Modification of triarylmethane compounds.

本發明中，於欲獲得具有更高之耐熱性之三芳基甲烷化合物之情形時，例如較佳為將[B^c-]設為以W(鎢)、O(氧)作為必需元素，且含有P(磷)及Si(矽)之至少一種的雜多金屬氧酸根陰離子。進而，就使耐光性提昇之方面而言，更佳設為以W(鎢)、Mo(鉬)、O(氧)作為必需元素，且含有P(磷)及Si(矽)之至少一種之雜多金屬氧酸根陰離子。作為該等之例，可列舉科金型磷鎢酸根離子α-(PW₁₂O₄₀)^3-、道森型(Dawson type)磷鎢酸根離子α-(P₂W₁₈O₆₂)^6-、β-(P₂W₁₈O₆₂)^6-、科金型矽鎢酸根離子α-(SiW₁₂O₄₀)^4-、β-(SiW₁₂O₄₀)^4-、γ-(SiW₁₂O₄₀)^4-，進而，作為其他例，可列舉(P₂W₁₇O₆₁)^10-、(P₂W₁₅O₅₆)^12-、(H₂P₂W₁₂O₄₈)^12-、(NaP₅W₃₀O₁₁₀)^14-、α-(SiW₉O₃₄)^10-、γ-(SiW₁₀O₃₆)^8-、α-(SiW₁₁O₃₉)^8-、β-(SiW₁₁O₃₉)^8-等。 In the present invention, when a triarylmethane compound having higher heat resistance is to be obtained, for example, it is preferable to set [B ^c- ] with W (tungsten) and O (oxygen) as essential elements, and contain A heteropolyoxometalate anion of at least one of P (phosphorus) and Si (silicon). Furthermore, in terms of improving light resistance, it is more preferable to use W (tungsten), Mo (molybdenum), and O (oxygen) as essential elements and to contain at least one of P (phosphorus) and Si (silicon). Heteropolyoxoanions. Examples of these include a Cotin type phosphotungstate ion α- (PW ₁₂ O ₄₀ ) ^3- , a Dawson type phosphotungstate ion α- (P ₂ W ₁₈ O ₆₂ ) ^6- , β- (P ₂ W ₁₈ O ₆₂ ) ^6- , Kejin type tungstosilicate ion α- (SiW ₁₂ O ₄₀ ) ^4- , β- (SiW ₁₂ O ₄₀ ) ^4- , γ- (SiW ₁₂ O ₄₀ ) ^4- , Furthermore, as other examples, (P ₂ W ₁₇ O ₆₁ ) ^10- , (P ₂ W ₁₅ O ₅₆ ) ^12- , (H ₂ P ₂ W ₁₂ O ₄₈ ) ^12- , (NaP ₅ W ₃₀ O ₁₁₀ ) ^14- , α- (SiW ₉ O ₃₄ ) ^10- , γ- (SiW ₁₀ O ₃₆ ) ^8- , α- (SiW ₁₁ O ₃₉ ) ^8- , β- (SiW ₁₁ O ₃₉ ) ^8- Wait.

於本發明中，關於具有更高之耐熱性之三芳基甲烷化合物，例如為[B^c-]為選自以(P₂Mo_yW_18-yO₆₂)^6-表示且y=0、1、2或3之整數的雜多金屬氧酸根陰離子、或以(SiMo_zW_12-zO₄₀)^4-表示且z=0、1、2或3之整數的雜多金屬氧酸根陰離子、或空位道森型磷鎢酸雜多金屬氧酸根陰離子中之至少一種陰離子之三芳基甲烷化合物。 In the present invention, for a triarylmethane compound having higher heat resistance, for example, [B ^c- ] is selected from (P ₂ Mo _y W _18-y O ₆₂ ) ^6- and y = 0, 1 , A heteropolyoxometalate anion having an integer of 2 or 3, or a heteropolyoxometalate anion having an integer of (SiMo _z W _12-z O ₄₀ ) ^4- and z = 0, 1, 2 or 3, or Triarylmethane compound of at least one of the vacant Dawson type phosphotungstate heteropolyoxometalate anions.

再者，所謂空位道森型磷鎢酸雜多金屬氧酸根陰離子，為(P₂W₁₇O₆₁)^10-。 The vacant Dawson type phosphotungstate heteropolyoxometalate anion is (P ₂ W ₁₇ O ₆₁ ) ^10- .

作為雜多酸或其鹼金屬鹽，例如可使用H₆(P₂Mo_yW_18-yO₆₂)、Na₆(P₂Mo_yW_18-yO₆₂)、H₄(SiMo_zW_12-zO₄₀)、Na₄(SiMo_zW_12-zO₄₀)、H₁₀(P₂W₁₇O₆₁)及Na₁₀(P₂W₁₇O₆₁)等。 Examples of the heteropoly acid or an alkali metal salt thereof include H ₆ (P ₂ Mo _y W _18-y O ₆₂ ), Na ₆ (P ₂ Mo _y W _18-y O ₆₂ ), and H ₄ (SiMo _z W _{12 -z} O ₄₀ ), Na ₄ (SiMo _z W _12-z O ₄₀ ), H ₁₀ (P ₂ W ₁₇ O ₆₁ ), Na ₁₀ (P ₂ W ₁₇ O ₆₁ ), and the like.

H₆(P₂Mo_yW_18-yO₆₂)等雜多酸例如可根據Inorganic Chemistry,vol47,p3679記載之方法容易地獲得。具體而言，可藉由使鎢酸鹼金屬鹽及鉬酸鹼金屬鹽溶解於水，並向其中添加磷酸，一面進行加熱攪拌一面進行加熱回流5~10小時而獲得。 Heteropoly acids such as H ₆ (P ₂ Mo _y W _18-y O ₆₂ ) can be easily obtained, for example, according to the method described in Inorganic Chemistry, vol47, p3679. Specifically, it can be obtained by dissolving alkali metal tungstate and alkali metal molybdate in water, adding phosphoric acid thereto, and heating and refluxing for 5 to 10 hours while heating and stirring.

以此方式所獲得之雜多酸可藉由使其與鹼金屬氯化物進行反應，而以與上述相同之方式製成作為道森型雜多金屬氧酸鹼金屬鹽之Na₆(P₂Mo_yW_18-yO₆₂)。 The heteropolyacid obtained in this way can be made into Na ₆ (P ₂ Mo) as a Dawson-type heteropolyoxometallic alkali salt by reacting it with an alkali metal chloride in the same manner as described above. _y W _18-y O ₆₂ ).

藉由改變鉬(Mo)與鎢(W)之添加莫耳比，即調整鎢酸鹼金屬鹽與鉬酸鹼金屬鹽之莫耳比，可將上述雜多金屬氧酸根陰離子中之鉬數y調整至0~3之範圍。 By changing the molar ratio of molybdenum (Mo) and tungsten (W), that is, adjusting the molar ratio of alkali metal tungstate and alkali metal molybdate, the molybdenum number y in the heteropolyoxometalate anion can be changed. Adjust to the range of 0 ~ 3.

作為其他方法，可藉由使鉬酸鹼金屬鹽溶解於水，並向其中添加鹽酸，繼而，添加K₁₀(α 2型P₂W₁₇O₆₁)之類的α 2型之空位道森型磷鎢酸鹼金屬鹽，於10~30℃攪拌30分鐘~2小時而獲得。以此方式所獲得之雜多酸可藉由使其與鹼金屬氯化物進行反應，而以與上述相同之方式製成道森型雜多金屬氧酸鹼金屬鹽。 As another method, an alkali metal molybdate is dissolved in water, hydrochloric acid is added thereto, and then a vacant Dawson type such as K ₁₀ (α 2 type P ₂ W ₁₇ O ₆₁ ) is added. An alkali metal phosphotungstate is obtained by stirring at 10 to 30 ° C for 30 minutes to 2 hours. The heteropolyacid obtained in this way can be made into a Dawson type heteropolyoxometallic alkali metal salt by reacting it with an alkali metal chloride in the same manner as described above.

例如，亦可藉由利用水解反應自P₂W₁₈O₆₂製備α 2型P₂W₁₇O₆₁，並使其與Mo進行反應而僅獲得P₂MoW₁₇O₆₂。藉由如此，可獲得於y之數值無分佈之上述雜多酸或其鹼金屬鹽。 For example, it is also possible to obtain only P ₂ MoW ₁₇ O _{62 by} preparing α 2 -type P ₂ W ₁₇ O ₆₁ from P ₂ W ₁₈ O ₆₂ by using a hydrolysis reaction and reacting it with Mo. By doing so, the heteropoly acid or its alkali metal salt having no distribution in the value of y can be obtained.

H₄(SiMoW₁₁O₄₀)等雜多酸、雜多金屬氧酸鹼金屬鹽例如可根據Journal of American Chemical Society,104(1982),p3194記載之方法容易地獲得。具體而言，可藉由將硝酸水溶液與鉬酸鹼金屬鹽水溶液進行混合攪拌，並向其中添加K₈(α型SiW₁₁O₃₉)攪拌2~6小時而獲得。以此方式所獲得之雜多酸可藉由使其與鹼金屬氯化物進行反應，而以與上述相同之方式製成科金型雜多金屬氧酸鹼金屬鹽。 Heteropoly acids such as H ₄ (SiMoW ₁₁ O ₄₀ ) and alkali metal salts of heteropolyoxometals can be easily obtained, for example, according to the method described in the Journal of American Chemical Society, 104 (1982), p3194. Specifically, it can be obtained by mixing and stirring an aqueous nitric acid solution and an aqueous solution of an alkali metal molybdate, and adding K ₈ (α-type SiW ₁₁ O ₃₉ ) thereto, and stirring for 2 to 6 hours. The heteropolyacid obtained in this way can be converted into an alkali metal salt of a heteropolyoxometallic acid in the same manner as described above by reacting it with an alkali metal chloride.

H₆(P₂W₁₈O₆₂)或H₁₀(P₂W₁₇O₆₁)等雜多酸例如可根據Inorganic Chemistry,vol47,p3679記載之方法容易地獲得。具體而言，可藉由使鎢酸鹼金屬鹽溶解水，並向其中添加鹽酸及磷酸，一面進行加熱攪拌一面進行加熱回流10~50小時而獲得。 Heteropoly acids such as H ₆ (P ₂ W ₁₈ O ₆₂ ) or H ₁₀ (P ₂ W ₁₇ O ₆₁ ) can be easily obtained, for example, according to the method described in Inorganic Chemistry, vol47, p3679. Specifically, it can be obtained by dissolving an alkali metal tungstate salt in water, adding hydrochloric acid and phosphoric acid thereto, and heating and refluxing for 10 to 50 hours while heating and stirring.

雜多酸可藉由使其與鹼金屬氯化物進行反應而製成道森型雜多金屬氧酸鹼金屬鹽。 Heteropolyacid can be made into a Dawson type heteropolyoxometalate by reacting it with an alkali metal chloride.

空位道森型雜多金屬氧酸鹼金屬鹽能以前者之道森型磷鎢酸雜多金屬氧酸鹼金屬鹽作為原料，例如根據Inorganic Synthesis,vol27,p104記載之方法而容易地獲得。具體而言，可藉由使道森型磷鎢酸雜多金屬氧酸鹼金屬鹽溶解於水，並向其中添加鹼金屬碳酸氫化物，視需要一面加熱一面攪拌而獲得。 The vacant Dawson type heteropolyoxo acid alkali metal salt can be easily obtained from the former Dawson type phosphotungstic heteropolyoxo acid alkali metal salt as a raw material, for example, according to the method described in Inorganic Synthesis, vol27, p104. Specifically, it can be obtained by dissolving a Dawson type phosphotungstic heteropolyoxo acid alkali metal salt in water, adding an alkali metal hydrogen carbonate to it, and stirring while heating it as necessary.

上述通式(II)中之R⁶及R⁷表示可具有取代基之碳數1~8之烷基、可具有取代基之碳數2~6之烯基、可具有取代基之碳數3~8之環烷基。 R ⁶ and R ⁷ in the general formula (II) represent an alkyl group having 1 to 8 carbon atoms which may have a substituent, an alkenyl group having 2 to 6 carbon atoms which may have a substituent, and 3 carbon atoms which may have a substituent. ~ 8 cycloalkyl.

作為該取代基，可列舉上述[取代基群R]之段落記載者。 Examples of the substituent include those described in the paragraph [Substituent Group R].

該等之中，作為R⁶及R⁷中之烷基、烯基或環烷基所具有之取代基，就陰離子之電荷更加非局域化、色料之耐熱性提昇之方面而言，尤佳為具有氟原子作為取代基。 Among these, as the substituents of the alkyl, alkenyl or cycloalkyl group in R ⁶ and R ⁷ , the anion charge is more delocalized, and the heat resistance of the colorant is particularly improved. Preferably, it has a fluorine atom as a substituent.

即，就分散陰離子之電荷、使陰離子穩定化之方面而言，R⁶及R⁷較佳為碳數1~8之全氟烷基。 That is, in terms of dispersing the charge of the anion and stabilizing the anion, R ⁶ and R ^{7 are} preferably a perfluoroalkyl group having 1 to 8 carbon atoms.

另一方面，R⁶及R⁷亦可相互連結而形成環。於形成環之情形時，R⁶及R⁷連結而形成之基尤佳為碳數2~12之氟伸烷基。 On the other hand, R ⁶ and R ⁷ may be connected to each other to form a ring. When a ring is formed, the group formed by R ⁶ and R ^{7 being} bonded is particularly preferably a fluoroalkylene group having 2 to 12 carbon atoms.

上述通式(III)中之R⁸~R¹⁰表示可具有取代基之碳數1~8之烷基、可具有取代基之碳數2~6之烯基、可具有取代基之碳數3~8之環烷基。 R ⁸ to R ¹⁰ in the general formula (III) represent an alkyl group having 1 to 8 carbons which may have a substituent, an alkenyl group having 2 to 6 carbons which may have a substituent, and 3 carbon atoms which may have a substituent. ~ 8 cycloalkyl.

該等之中，作為R⁸~R¹⁰中之烷基、烯基或環烷基所具有之取代基，就陰離子之電荷更加非局域化、色料之耐熱性提昇之方面而言，尤佳為具有氟原子作為取代基。 Among these, as the substituents of the alkyl, alkenyl or cycloalkyl group in R ⁸ to R ¹⁰ , the anion charge is more delocalized, and the heat resistance of the colorant is particularly improved. Preferably, it has a fluorine atom as a substituent.

即，就分散陰離子之電荷、使陰離子穩定化之方面而言，R⁸~R¹⁰較佳為碳數1~8之全氟烷基。 That is, in terms of dispersing the charge of the anion and stabilizing the anion, R ⁸ to R ^{10 are} preferably a perfluoroalkyl group having 1 to 8 carbon atoms.

另一方面，R⁸~R¹⁰亦可相互連結而形成環。於形成環之情形時，R⁸~R¹⁰連結而形成之基尤佳為碳數2~12之氟伸烷基。 On the other hand, R ⁸ to R ¹⁰ may be connected to each other to form a ring. In the case of forming a ring, the group formed by R ⁸ to R ^{10 being} connected is particularly preferably a fluoroalkylene group having 2 to 12 carbon atoms.

作為磺酸陰離子，例如可列舉：三氟甲磺酸、甲磺酸、戊磺酸、己磺酸、庚磺酸、十二烷磺酸、樟腦磺酸等可具有取代基之脂肪族磺酸陰離子；苯磺酸、對甲苯磺酸、1-萘磺酸、2-萘磺酸、2,6-萘二磺酸、1,3,6-萘三磺酸等可具有取代基之芳香族磺酸陰離子；酸性藍80(C.I.61585)、酸性綠25(C.I.61570)、酸性藍45(C.I.63010)、酸性藍43(C.I.63000)、酸性藍25(C.I.62055)、酸性藍40(C.I.65125)等具有磺酸鹽基之蒽醌系色素之陰離子；直接藍86(C.I.74810)、直接藍199(C.I.14190)等具有磺酸鹽基之酞菁系色素之陰離子；酸性藍74(C.I.73015)等具有磺酸鹽基之靛藍系色素之陰離子等。 Examples of the sulfonic acid anion include aliphatic sulfones which may have a substituent such as trifluoromethanesulfonic acid, methanesulfonic acid, pentanesulfonic acid, hexanesulfonic acid, heptanesulfonic acid, dodecanesulfonic acid, and camphorsulfonic acid. Acid anions; benzenesulfonic acid, p-toluenesulfonic acid, 1-naphthalenesulfonic acid, 2-naphthalenesulfonic acid, 2,6-naphthalenedisulfonic acid, 1,3,6-naphthalenetrisulfonic acid, and the like may have aromatic groups having substituents Group sulfonic acid anion; Acid Blue 80 (CI61585), Acid Green 25 (CI61570), Acid Blue 45 (CI63010), Acid Blue 43 (CI63000), Acid Blue 25 (CI62055), Acid Blue 40 (CI 65125), such as anions of anthraquinone pigments with sulfonate groups; anions of phthalocyanine pigments with sulfonate groups, such as Direct Blue 86 (CI74810), direct blue 199 (CI14190); Acid Blue 74 (CI 73015) and other anions such as indigo pigments having a sulfonate group.

上述通式(I)中之a為構成陽離子之顯色性陽離子部位之數。a為2以上之整數。a之上限並無特別限定，就製造之容易性之方面而言，a較佳為4以下，更佳為3以下。 A in the general formula (I) is the number of color-developing cation sites constituting a cation. a is an integer of 2 or more. The upper limit of a is not particularly limited. In terms of ease of production, a is preferably 4 or less, and more preferably 3 or less.

又，上述通式(I)中之b表示分子聚集體中陽離子之分子數，d表示分子聚集體中陰離子之分子數，且b及d表示1以上之整數。關於本發明之色料，其結晶或凝集體不限於b及d分別為1之情形，亦可分別採用2以上之任何自然數如2、3、4…。本發明之色料就耐熱性之方面而言，較佳為至少一部分形成b≧2之分子聚集體。又，本發明之色料就耐熱性之方面而言，較佳為至少一部分形成d≧2之分子聚集體。 In addition, b in the general formula (I) represents the number of molecules of cations in the molecular aggregates, d represents the number of molecules of anions in the molecular aggregates, and b and d represent integers of 1 or more. Regarding the colorant of the present invention, the crystals or agglomerates thereof are not limited to the case where b and d are 1, respectively, and any natural number of 2 or more such as 2, 3, 4, etc. may also be used. In terms of heat resistance, the colorant of the present invention preferably forms molecular aggregates having b ≧ 2 at least in part. In addition, in terms of heat resistance, the colorant of the present invention preferably forms at least a part of molecular aggregates having d ≧ 2.

於b為2以上之情形時，分子聚集體中之多個陽離子可為單獨1種，亦可組合2種以上。又，於d為2以上之情形時，分子聚集體中之多個陰離子可為單獨1種，亦可組合2種以上。 When b is 2 or more, the plurality of cations in the molecular aggregate may be one kind alone, or two or more kinds may be combined. When d is 2 or more, the plurality of anions in the molecular aggregate may be used alone or in combination of two or more.

本發明之三芳基甲烷化合物例如可藉由使上述對應之陽離子部之氯化物與上述對應之雜多酸或雜多金屬氧酸鹼金屬鹽進行反應而容易地製造。於使用上述對應之陽離子部之氯化物且使用雜多酸之情形時，可藉由利用脫氯化氫反應進行鹽置換而製造，又，於使用上述對應之陽離子部之氯化物且使用雜多金屬氧酸鹼金屬鹽之情形時，可藉由利用脫鹼金屬氯化物反應進行鹽置換而製造。 The triarylmethane compound of the present invention can be easily produced, for example, by reacting the chloride of the corresponding cationic moiety with the corresponding heteropolyacid or heteropolyoxometalate. When using the corresponding chloride of the cationic moiety and using a heteropoly acid, It can be produced by salt replacement using a dehydrochlorination reaction. In the case where a chloride of the corresponding cationic moiety is used and an alkali metal salt of a heteropolyoxo acid is used, it can be performed by using a dealkali chloride reaction. Made by salt replacement.

與上述使用雜多酸之脫氯化氫反應相比，將雜多酸暫且製成雜多金屬氧酸鹼金屬鹽後進行脫鹼金屬氯化物反應不僅可確實地進行鹽置換而能夠以更高產率獲得本發明之三芳基甲烷化合物，而且可獲得副產物更少之純度較高之本發明之三芳基甲烷化合物，因而較佳。當然，雜多金屬氧酸鹼金屬鹽亦可藉由再結晶等進行精製後使用。 Compared with the above-mentioned dehydrochlorination reaction using heteropolyacid, the heteropolyacid is temporarily converted into an alkali metal salt of heteropolyoxometalate and then the alkali metal chloride reaction is performed, which can not only reliably perform salt replacement, but also obtain it in a higher yield. The triarylmethane compound of the present invention is also preferable because it can obtain a triarylmethane compound of the present invention with higher purity and fewer by-products. Of course, the heteropolyoxo acid alkali metal salt can also be used after being purified by recrystallization or the like.

於難以自反應液獲得沈澱之情形時，可藉由將該反應液進行冷卻等，使溶解度降低，而以更高產率獲得對應之雜多金屬氧酸鹼金屬鹽。 When it is difficult to obtain a precipitate from the reaction solution, the reaction solution may be cooled to reduce the solubility, and a corresponding heteropolyoxometalate may be obtained in a higher yield.

由於本發明之陽離子為2價以上，故而作為陰離子源之雜多酸或雜多金屬氧酸鹼金屬鹽之使用量較佳為根據該等之離子價，以成為等莫耳數之方式添加，進行上述反應。 Since the cation of the present invention is divalent or more, the amount of the heteropoly acid or heteropolyoxo acid alkali metal salt used as an anion source is preferably added in such a way that it has an equal mole number according to the ion valence. The above reaction is performed.

本發明之三芳基甲烷化合物由於包含利用雜多酸進行色澱化(水不溶化)之步驟(或利用雜多酸而受到色澱化(水不溶化))，故而於製造步驟中或製造後之某些步驟中使用水之情形時，或為了進行更確實之反應或使所獲得之化合物之色澱結構不受破壞，例如較佳為使用純化水、離子交換水、純水等之類之金屬離子或鹵素離子之含有率極少之水。 Since the triarylmethane compound of the present invention includes a step of performing lake sedimentation (water insolubilization) by using a heteropoly acid (or undergoing lake sedimentation (water insolubilization) by using a heteropoly acid), the When water is used in these steps, or in order to perform a more accurate reaction or to prevent the lake structure of the obtained compound from being damaged, for example, metal ions such as purified water, ion-exchanged water, and pure water are preferably used. Or water with very low halogen ion content.

本發明之三芳基甲烷化合物為水不溶性之色料。以此方式所獲得之本發明之三芳基甲烷化合物可直接用作合成樹脂等之著色劑，若有需要可藉由利用公知慣用之粉碎或造粒調整粒徑而製成最適合各種用途之著色劑。關於著色劑，於乾燥粉體中，若一次粒子之平均粒徑為100nm以下，則容易獲得更鮮明之藍色之著色物，因而較佳。 The triarylmethane compound of the present invention is a water-insoluble colorant. The triarylmethane compound of the present invention obtained in this way can be directly used as a coloring agent for synthetic resins, etc. If necessary, it can be made into a coloring that is most suitable for various uses by adjusting the particle size by using the commonly used pulverization or granulation. Agent. As for the colorant, in the dry powder, if the average particle diameter of the primary particles is 100 nm or more, In this case, it is easy to obtain a more vivid blue coloring matter, so it is better.

於本發明中，一次粒子之平均粒徑可如下般進行測定。首先，利用穿透式電子顯微鏡或掃描式電子顯微鏡拍攝視野內之粒子。繼而，對二維圖像上之50個構成凝集體之一次粒子求出各粒子之內徑之最長之長度(最大長度)。將各粒子之最大長度之平均值設為一次粒子之平均粒徑。 In this invention, the average particle diameter of a primary particle can be measured as follows. First, use a transmission electron microscope or a scanning electron microscope to capture particles in the field of view. Then, the longest length (maximum length) of the inner diameter of each particle was calculated for 50 primary particles constituting the aggregate on the two-dimensional image. The average value of the maximum length of each particle is taken as the average particle diameter of a primary particle.

本發明之三芳基甲烷化合物由於在公知慣用之各種用途中，即便歷經高溫下之熱歷程，色相變化亦較小，具有優異之耐熱性，故而於用於濾色器像素部之製造之情形時，可獲得色相變化較少之能夠進行優異之圖像顯示之液晶顯示裝置之濾色器。 The triarylmethane compound of the present invention is used in the manufacture of a color filter pixel portion because it has a small hue change and excellent heat resistance even in a variety of well-known and commonly used applications, even after undergoing a thermal history at high temperatures. A color filter of a liquid crystal display device capable of performing excellent image display with less change in hue can be obtained.

於本發明之濾色器中，作為背光光源，習知之冷陰極管(CCFL光源)、白色LED(LED；Light Emitting Diode，發光二極體)光源、3色獨立LED光源、白色有機EL(EL；Electro Luminescence，電致發光)光源等均可使用。 In the color filter of the present invention, as a backlight light source, a conventional cold cathode tube (CCFL light source), a white LED (LED; Light Emitting Diode) light source, a 3-color independent LED light source, and a white organic EL (EL (Electro Luminescence) can be used.

於本發明之三芳基甲烷化合物中，可視需要含有ε型酞菁銅顏料、二

顏料(C.I.顏料紫23、C.I.顏料紫37、C.I.顏料藍80等)等、或無金屬或金屬酞菁之磺酸衍生物、無金屬或金屬酞菁之N-(二烷基胺基)甲基衍生物、無金屬或金屬酞菁之N-(二烷基胺基烷基)磺醯胺衍生物、二

紫之磺酸衍生物、陰丹士林藍之磺酸衍生物、酞菁磺酸等有機顏料衍生物等；或BYK-Chemie公司之DISPERBYK 130、DISPERBYK 161、DISPERBYK 162、DISPERBYK 163、DISPERBYK 170、DISPERBYK 171、DISPERBYK 174、DISPERBYK 180、DISPERBYK 182、DISPERBYK 183、DISPERBYK 184、DISPERBYK 185、DISPERBYK 2000、DISPERBYK 2001、 DISPERBYK 2020、DISPERBYK 2050、DISPERBYK 2070、DISPERBYK 2096、DISPERBYK 2150、DISPERBYK LPN21116、DISPERBYK LPN6919、EFKA公司之Efka 46、Efka 47、Efka 452、Efka LP4008、Efka 4009、Efka LP4010、Efka LP4050、Efka LP4055、Efka 400、Efka 401、Efka 402、Efka 403、Efka 450、Efka 451、Efka 453、Efka 4540、Efka 4550、Efka LP4560、Efka 120、Efka 150、Efka 1501、Efka 1502、Efka 1503、Lubrizol公司之Solsperse 3000、Solsperse 9000、Solsperse 13240、Solsperse 13650、Solsperse 13940、Solsperse 17000、Solsperse 18000、Solsperse 20000、Solsperse 21000、Solsperse 24000、Solsperse 26000、Solsperse 27000、Solsperse 28000、Solsperse 32000、Solsperse 36000、Solsperse 37000、Solsperse 38000、Solsperse 41000、Solsperse 42000、Solsperse 43000、Solsperse 46000、Solsperse 54000、Solsperse 71000、Ajinomoto股份有限公司之Ajisper PB711、Ajisper PB821、Ajisper PB822、Ajisper PB814、Ajisper PN411、Ajisper PA111等分散劑；或丙烯酸系樹脂、胺酯(urethane)系樹脂、醇酸系樹脂、木松香、松脂膠(gum rosin)、妥爾油松香等天然松香、聚合松香、歧化松香、氫化松香、氧化松香、順丁烯二醯化松香等改質松香、松香胺、石灰松香(lime rosin)、松香環氧烷加成物、松香醇酸加成物、松香改質苯酚等松香衍生物等室溫下為液狀且為水不溶性之合成樹脂。該等分散劑或樹脂之添加亦有助於絮凝(flocculation)之減輕、分散穩定性之提昇、分散體之黏度特性之提昇。 In the triarylmethane compound of the present invention, an ε-type copper phthalocyanine pigment,

Pigments (CI Pigment Violet 23, CI Pigment Violet 37, CI Pigment Blue 80, etc.), or sulfonic acid derivatives without metal or metal phthalocyanine, N- (dialkylamino) formaldehyde without metal or metal phthalocyanine N- (dialkylaminoalkyl) sulfonamide derivatives without metal or metal phthalocyanine,

Purple sulfonic acid derivatives, indanthrene blue sulfonic acid derivatives, organic pigment derivatives such as phthalocyanine sulfonic acid; or DISPERBYK 130, DISPERBYK 161, DISPERBYK 162, DISPERBYK 163, DISPERBYK 170, BYK-Chemie DISPERBYK 171, DISPERBYK 174, DISPERBYK 180, DISPERBYK 182, DISPERBYK 183, DISPERBYK 184, DISPERBYK 185, DISPERBYK 2000, DISPERBYK 2001, DISPERBYK 2020, DISPERBYK 2050, DISPERBYK 2070, DISPERBYK 2096, DISPERBYK 1950, DISPERBYK 2150, 116 Efka 46, Efka 47, Efka 452, Efka LP4008, Efka 4009, Efka LP4010, Efka LP4050, Efka LP4055, Efka 400, Efka 401, Efka 402, Efka 403, Efka 450, Efka 451, Efka 453, Efka 453, Efka 4550, Efka LP4560, Efka 120, Efka 150, Efka 1501, Efka 1502, Efka 1503, Solsperse 3000, Solsperse 9000, Solsperse 13240, Solsperse 13650, Solsperse 13940, Solsperse 17000, Solsperse 20000, Solsperse 20000 Solsperse 24000, Solsperse 26000, Solsperse 27000, Solsper se 28000, Solsperse 32000, Solsperse 36000, Solsperse 37000, Solsperse 38000, Solsperse 41000, Solsperse 42000, Solsperse 43000, Solsperse 46000, Solsperse 54000, Solsperse 71000, Ajisper PB711, Ajispers PB82A8221, AjisperAPB81418221 Ajisper PN411, Ajisper PA111 and other dispersants; or acrylic resin, urethane resin, alkyd resin, wood rosin, gum rosin, tall oil rosin and other natural rosin, polymerized rosin, disproportionated rosin Modified hydrogenated rosin, hydrogenated rosin, oxidized rosin, cis-butene difluorinated rosin, rosin amine, lime rosin, rosin alkylene oxide adduct, rosin alkyd adduct, rosin modified phenol, etc. Derivatives such as synthetic resins that are liquid at room temperature and are water-insoluble. The addition of these dispersants or resins also helps to reduce floculation, improve dispersion stability, and improve the viscosity characteristics of the dispersion.

本發明之三芳基甲烷化合物其本身具有適合於濾色器藍色像素部之製備之色相，若有需要，可藉由相對於其質量換算每100份併用ε型酞菁銅顏料(C.I.顏料藍15：6)0.1~30份進行色相之最佳化。 The triarylmethane compound of the present invention itself has a hue suitable for the preparation of the blue pixel portion of the color filter. If necessary, it can be converted to 100 parts by using ε-type copper phthalocyanine pigment (CI pigment blue) 15: 6) The hue is optimized from 0.1 to 30 parts.

本發明之三芳基甲烷化合物其本身具有適合於濾色器藍色像素部之製備之耐熱性或耐光性，若有需要，可相對於三芳基甲烷化合物每100份使用0.1~10份、尤其是0.5~8份抗氧化劑不揮發成分。此處所謂抗氧化劑，係防止氧化劣化之添加劑之總稱，包含防止因熱引起之氧化劣化者(狹義之抗氧化劑)、及防止因光(主要為紫外線)引起之氧化劣化者(狹義稱為光穩定劑)。 The triarylmethane compound of the present invention has heat resistance or light resistance suitable for the preparation of the blue pixel portion of a color filter. If necessary, it can be used in an amount of 0.1 to 10 parts per 100 parts of the triarylmethane compound, especially 0.5 ~ 8 parts of antioxidant non-volatile components. The term "antioxidant" used herein refers to a general term for additives that prevent oxidative degradation, including those that prevent oxidative degradation due to heat (antioxidants in the narrow sense) and those that prevent oxidative degradation due to light (mainly ultraviolet rays) (the narrow sense is light stabilizer).

此種抗氧化劑有具有捕捉自由基而防止自動氧化之作用(自由基鏈防止作用)者、及具有將過氧化氫(過氧化物)分解成無害者之作用(過氧化物分解作用)者，前者稱為一次抗氧化劑，後者稱為二次抗氧化劑。亦已知有兼備該等兩者之作用之一次二次兩用抗氧化劑。作為一次抗氧化劑，例如典型者為酚系(包含受阻酚系)或胺系(包含受阻胺系)之各抗氧化劑，作為二次抗氧化劑，例如典型者為硫系或磷系之各抗氧化劑。 Such antioxidants have the effect of trapping free radicals and preventing auto-oxidation (free radical chain prevention effect), and the effect of decomposing hydrogen peroxide (peroxide) into harmless ones (peroxide decomposition effect), The former is called primary antioxidant and the latter is called secondary antioxidant. It is also known to have one-time dual-use antioxidants that have the effects of both. As the primary antioxidant, for example, each of phenol-based (including hindered phenol-based) or amine-based (including hindered amine-based) antioxidants is typical, and as the secondary antioxidant, for example, sulfur-based or phosphorus-based antioxidants are typical. .

本發明之三芳基甲烷化合物其本身具有適合於濾色器藍色像素部之製備之耐熱性，若有需要，可藉由併用陽離子性樹脂而更進一步提高耐熱性或耐光性。 The triarylmethane compound of the present invention has heat resistance suitable for the preparation of a blue pixel portion of a color filter. If necessary, heat resistance or light resistance can be further improved by using a cationic resin in combination.

作為此種陽離子性樹脂，例如較佳為使用丙烯酸樹脂、聚胺酯樹脂、環氧樹脂、聚醯胺樹脂等，其原因在於：即便於熱歷程下，色相變化亦較小，可大幅改善濾色器之耐熱性。 As such a cationic resin, for example, an acrylic resin, a polyurethane resin, an epoxy resin, or a polyamide resin is preferably used, because the hue change is small even in the thermal history, and the color filter can be greatly improved. Of heat resistance.

本發明中，三芳基甲烷化合物與陽離子性樹脂之不揮發成分之以質量基準計之比例並無特別限制，較佳為設為相對於前者化合物每100份，後者樹脂之不揮發成分為0.1份以上且未達10份、其中較佳為0.5~5 份、尤佳為1~3份。 In the present invention, the ratio of the triarylmethane compound and the nonvolatile content of the cationic resin on a mass basis is not particularly limited, and it is preferably set to be 100 parts per 100 parts of the former compound and 0.1 part of the nonvolatile matter of the latter resin. Above and less than 10 parts, preferably 0.5 ~ 5 Serving, especially preferred, is 1-3.

於製備含有三芳基甲烷化合物及陽離子性樹脂之著色組成物時，於對上述化合物及樹脂進行加熱之情形時，可將兩者進行混合，其後，利用密閉系統，於化合物本身不產生不良情況之溫度的攪拌下，於30分鐘~5小時間之範圍內進行。藉由以此方式形成加壓狀態，如上所述，陽離子性樹脂滲透至化合物粒子之空隙，表現出與僅被覆粒子表面相比更優異之效果。 When preparing a coloring composition containing a triarylmethane compound and a cationic resin, when the above compounds and resins are heated, the two can be mixed, and then a closed system is used to prevent the compound itself from causing problems. Under stirring at a temperature of 30 minutes to 5 hours. By forming the pressurized state in this way, as described above, the cationic resin penetrates into the voids of the compound particles, and exhibits a more excellent effect than covering only the particle surfaces.

本發明之三芳基甲烷化合物可利用習知公知之方法來用於濾色器像素部之形成。本發明之三芳基甲烷化合物之分散方法中，作為代表性之方法，為光微影法，其為如下方法：將後文所述之光硬化性組成物塗佈於濾色器用之透明基板之設置有黑矩陣側之面進行加熱乾燥(預烘烤)，其後，藉由介隔光罩照射紫外線而進行圖案曝光，使與像素部對應之部位之光硬化性化合物硬化，其後，使未曝光部分利用顯影液進行顯影，將非像素部去除，使像素部固著於透明基板。該方法中，於透明基板上形成由光硬化性組成物之硬化著色皮膜所構成之像素部。 The triarylmethane compound of the present invention can be used for forming a pixel portion of a color filter by a conventional method. In the method for dispersing the triarylmethane compound of the present invention, as a representative method, a photolithography method is a method in which a photocurable composition described later is applied to a transparent substrate for a color filter. The surface provided with the black matrix side is heat-dried (pre-baked), and thereafter, pattern exposure is performed by irradiating ultraviolet rays through a reticle to harden the photocurable compound at a portion corresponding to the pixel portion, and thereafter, The exposed portion is developed with a developing solution to remove the non-pixel portion and fix the pixel portion to the transparent substrate. In this method, a pixel portion composed of a cured colored film of a photocurable composition is formed on a transparent substrate.

對紅色、綠色、藍色每色製備後文所述之光硬化性組成物，反覆進行上述操作，藉此可製造於特定之位置具有紅色、綠色、藍色之著色像素部之濾色器。可由本發明之三芳基甲烷化合物形成藍色像素部。再者，於製備用以形成紅色像素部及綠色像素部之光硬化性組成物時，可使用公知慣用之紅色顏料及綠色顏料。 For each color of red, green, and blue, a photo-hardenable composition described later is prepared, and the above-mentioned operations are repeated, whereby a color filter having red, green, and blue colored pixel portions at specific positions can be manufactured. The blue pixel portion can be formed from the triarylmethane compound of the present invention. When preparing a photocurable composition for forming a red pixel portion and a green pixel portion, a known and commonly used red pigment and green pigment can be used.

作為用以形成紅色像素部之顏料，例如可列舉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，作為用以形成綠色像素部之顏料，例如可列舉C.I.顏料綠7、C.I.顏料綠10、C.I.顏料綠36、C.I.顏料綠47、C.I.顏料綠58等。於該等紅色像素部及綠色像素部之形成時，亦可併用黃色顏料。其後，亦可視需要為了使未反應之光硬化性化合物熱硬化而對濾色器整體進行加熱處理(後烘烤)。 Examples of the pigment used to form the red pixel portion include C.I. Pigment Red 177, C.I. Pigment Red 209, C.I. Pigment Red 242, C.I. Pigment Red 254, and the like, which are used to form green. Examples of the pigment of the pixel portion include C.I. Pigment Green 7, C.I. Pigment Green 10, C.I. Pigment Green 36, C.I. Pigment Green 47, and C.I. Pigment Green 58. When forming the red pixel portion and the green pixel portion, a yellow pigment may be used in combination. Thereafter, if necessary, the entire color filter may be subjected to a heat treatment (post-baking) in order to thermally harden the unreacted photocurable compound.

作為將後文所述之光硬化性組成物塗佈於玻璃等透明基板上之方法，例如可列舉旋轉塗佈法、輥式塗佈法、噴墨法等。 Examples of a method for applying a photocurable composition described later on a transparent substrate such as glass include a spin coating method, a roll coating method, and an inkjet method.

塗佈於透明基板之光硬化性組成物之塗膜之乾燥條件視各成分之種類、調配比例等而不同，通常為於50~150℃下1~15分鐘左右。又，作為用於光硬化性組成物之光硬化的光，較佳為使用200~500nm之波長區域之光線。可使用發出該波長範圍之光之各種光源。 The drying conditions of the coating film of the photocurable composition applied to the transparent substrate vary depending on the type of each component, the blending ratio, and the like, and it is usually about 1 to 15 minutes at 50 to 150 ° C. In addition, as the light for light curing of the photocurable composition, it is preferable to use light in a wavelength range of 200 to 500 nm. Various light sources that emit light in this wavelength range can be used.

作為顯影方法，例如可列舉溢液法、浸漬法、噴霧法等。於光硬化性組成物之曝光、顯影之後，對已形成需要之顏色之像素部之透明基板進行水洗並使其乾燥。藉由對以此方式所獲得之濾色器藉由加熱板、烘箱等加熱裝置以90~280℃進行特定時間加熱處理(後烘烤)，而將著色塗膜中之揮發性成分去除，同時，使光硬化性組成物之硬化著色皮膜中殘存之未反應之光硬化性化合物熱硬化，完成濾色器。 Examples of the development method include an overflow method, a dipping method, and a spray method. After the photocurable composition is exposed and developed, the transparent substrate of the pixel portion where the desired color has been formed is washed with water and dried. The color filter obtained in this way is subjected to a specific time heating treatment (post-baking) at a temperature of 90 to 280 ° C by a heating device such as a hot plate and an oven to remove volatile components in the colored coating film, and at the same time , The non-reacted photocurable compound remaining in the hardened colored film of the photocurable composition is thermally cured to complete the color filter.

用以形成濾色器之藍色像素部之光硬化性組成物可藉由如下方式製備：將本發明之三芳基甲烷化合物、分散劑、光硬化性化合物、及有機溶劑作為必需成分，並視需要使用熱塑性樹脂，將該等進行混合。於對形成藍色像素部之著色樹脂皮膜要求可耐濾色器之實際生產中所進行之烘烤等的強韌性等之情形時，於製備上述光硬化性組成物時，不僅需光硬化性化合物，而且還必須併用其熱塑性樹脂。於併用熱塑性樹脂之情形時，作為有機溶劑，較佳為使用使其溶解者。 The photocurable composition for forming the blue pixel portion of the color filter can be prepared by using the triarylmethane compound, dispersant, photocurable compound, and organic solvent of the present invention as essential components, and It is necessary to use a thermoplastic resin and mix these. When the colored resin film forming the blue pixel portion is required to withstand toughness such as baking in actual production of a color filter, etc., not only the photocuring property is required when preparing the photocurable composition. Compounds, and must also be used in combination with their thermoplastic resins. When using thermoplastic resin In this case, as the organic solvent, it is preferred to use one that dissolves it.

作為上述光硬化性組成物之製造方法，一般為如下方法：使用本發明之三芳基甲烷化合物、有機溶劑及分散劑作為必需成分，以將該等進行混合變得均勻之方式進行攪拌分散而首先製備用以形成濾色器之像素部之分散液之後，向其中添加光硬化性化合物、及視需要之熱塑性樹脂或光聚合起始劑等，而製成上述光硬化性組成物。 As a method for producing the photocurable composition, the following method is generally used: the triarylmethane compound, the organic solvent, and the dispersant of the present invention are used as essential components, and the components are stirred and dispersed in such a manner that they are uniformly mixed. After the dispersion liquid for forming the pixel portion of the color filter is prepared, a photocurable compound, and optionally a thermoplastic resin or a photopolymerization initiator are added thereto to prepare the above-mentioned photocurable composition.

此處，分散劑、有機溶劑可使用上述者。 Here, as the dispersant and the organic solvent, the above can be used.

作為光硬化性組成物之製備所使用之熱塑性樹脂，例如可列舉：胺酯系樹脂、丙烯酸系樹脂、聚醯胺系樹脂、聚醯亞胺系樹脂、苯乙烯順丁烯二酸系樹脂、苯乙烯順丁烯二酸酐系樹脂等。 Examples of the thermoplastic resin used in the production of the photocurable composition include amine ester resins, acrylic resins, polyamido resins, polyamido resins, styrene maleic acid resins, Styrene maleic anhydride resin and the like.

作為光硬化性化合物，例如可列舉1,6-己二醇二丙烯酸酯、乙二醇二丙烯酸酯、新戊二醇二丙烯酸酯、三乙二醇二丙烯酸酯、雙(丙烯醯氧基乙氧基)雙酚A、3-甲基戊二醇二丙烯酸酯等之類的2官能單體，三羥甲基丙烷三丙烯酸酯、新戊四醇三丙烯酸酯、異氰尿酸三[2-(甲基)丙烯醯氧基乙基]酯、二新戊四醇六丙烯酸酯、二新戊四醇五丙烯酸酯等分子量相對較小之多官能單體，聚酯丙烯酸酯、聚丙烯酸胺酯、聚醚丙烯酸酯等之類的分子量相對較大之多官能單體。 Examples of the photocurable compound include 1,6-hexanediol diacrylate, ethylene glycol diacrylate, neopentyl glycol diacrylate, triethylene glycol diacrylate, and bis (acryloxyethyl). (Oxy) Bifunctional monomers such as bisphenol A, 3-methylpentanediol diacrylate, etc., trimethylolpropane triacrylate, neopentaerythritol triacrylate, isocyanuric acid tri [2- Poly (meth) acryloxyethyl] ester, dipentaerythritol hexaacrylate, dipentaerythritol pentaacrylate, and other polyfunctional monomers with relatively small molecular weight, polyester acrylate, polyacrylate Polyfunctional monomers, such as polyether acrylates, etc., with relatively large molecular weight.

作為光聚合起始劑，例如可列舉：苯乙酮、二苯甲酮、苯偶醯二甲基縮酮、過氧化苯甲醯、2-氯9-氧硫

、1,3-雙(4'-疊氮苯亞甲基)-2-丙烷、1,3-雙(4'-疊氮苯亞甲基)-2-丙烷-2'-磺酸、4,4'-二疊氮茋-2,2'-二磺酸等。作為市售之光聚合起始劑，例如有：Ciba Specialty Chemicals公司製造之「Irgacure(商標名)-184」、「Irgacure(商標名)-369」、「Darocure(商標名)-1173」、BASF公司製造之「Lucirin-TPO」、日本化藥公司製造之「kayacure(商標名)DETX」、「kayacure(商標名)OA」、Stauffer公司製造之「Vicure 10」、「Vicure 55」、Akzo公司製造之「Trigonal PI」、SANDOZ公司製造之「Sandoray 1000」、Upjohn公司製造之「Deap」、黑金化成公司製造之「Biimidazole」等。 Examples of the photopolymerization initiator include acetophenone, benzophenone, benzophenone dimethyl ketal, benzophenone peroxide, and 2-chloro9-oxosulfur.

, 1,3-bis (4'-azidobenzylidene) -2-propane, 1,3-bis (4'-azidobenzylidene) -2-propane-2'-sulfonic acid, 4 , 4'-Diazide-2,2'-disulfonic acid and so on. Examples of commercially available photopolymerization initiators include "Irgacure (trade name) -184", "Irgacure (trade name) -369", "Darocure (trade name) -1173", and BASF manufactured by Ciba Specialty Chemicals). "Lucirin-TPO" manufactured by the company, "kayacure (trade name) DETX" manufactured by Nippon Kayaku Co., "kayacure (trade name) OA", "Vicure 10" manufactured by Stauffer, "Vicure 55", manufactured by Akzo "Trigonal PI", "Sandoray 1000" manufactured by SANDOZ company, "Deap" manufactured by Upjohn company, "Biimidazole" manufactured by Kurojin Kasei Corporation, etc.

又，亦可與上述光聚合起始劑併用公知慣用之光敏劑。作為光敏劑，例如可列舉：胺類、脲類、具有硫原子之化合物、具有磷原子之化合物、具有氯原子之化合物或腈類或者其他具有氮原子之化合物等。該等可單獨使用，亦可將2種以上組合使用。 A known and commonly used photosensitizer may be used in combination with the photopolymerization initiator. Examples of the photosensitizer include amines, ureas, compounds having a sulfur atom, compounds having a phosphorus atom, compounds having a chlorine atom, nitriles, or other compounds having a nitrogen atom. These can be used alone or in combination of two or more.

光聚合起始劑之調配率並無特別限定，較佳為以質量基準計，相對於具有光聚合性或光硬化性官能基之化合物為0.1~30%之範圍。若未達0.1%，則存在光硬化時之感光度降低之傾向，若超過30%，則存在使抗蝕劑之塗膜乾燥時，光聚合起始劑之結晶析出而引起塗膜物性之劣化之情況。 The blending ratio of the photopolymerization initiator is not particularly limited, but it is preferably in the range of 0.1 to 30% by mass based on the compound having a photopolymerizable or photocurable functional group. If it is less than 0.1%, the photosensitivity tends to decrease during photocuring. If it exceeds 30%, the photoresist of the photopolymerization initiator will precipitate when the coating film of the resist is dried, resulting in deterioration of the physical properties of the coating film. Situation.

使用如以上所述之各材料，以質量基準計，相對於本發明之三芳基甲烷化合物每100份，將300~1000份之有機溶劑、及1~100份之分散劑以變得均勻之方式進行攪拌分散，可獲得上述分散液。繼而，於該分散液中，相對於本發明之三芳基甲烷化合物每1份添加合計為3~20份之熱塑性樹脂與光硬化性化合物，相對於每1份光硬化性化合物添加0.05~3份之光聚合起始劑，並視需要進而添加有機溶劑，以變得均勻之方式進行攪拌分散，可獲得用以形成濾色器像素部之光硬化性組成物。 Using each of the materials described above, on a mass basis, 300 to 1,000 parts of an organic solvent and 1 to 100 parts of a dispersant per 100 parts of the triarylmethane compound of the present invention are made uniform. The dispersion is obtained by stirring and dispersing. Then, in the dispersion, 3 to 20 parts of the thermoplastic resin and the photocurable compound are added per 1 part of the triarylmethane compound of the present invention, and 0.05 to 3 parts are added per 1 part of the photocurable compound. A photopolymerization initiator, and if necessary, an organic solvent is further added, and the mixture is stirred and dispersed in a uniform manner to obtain a photocurable composition for forming a pixel portion of a color filter.

作為顯影液，可使用公知慣用之有機溶劑或鹼水溶液。尤其是於上述光硬化性組成物中包含熱塑性樹脂或光硬化性化合物，且該等之至少一者具有酸值、呈鹼可溶性之情形時，藉由鹼水溶液進行洗淨對形成濾色器像素部有效。 As the developing solution, a known and commonly used organic solvent or an alkaline aqueous solution can be used. especially When a thermoplastic resin or a photocurable compound is contained in the photocurable composition, and at least one of them has an acid value and is alkali-soluble, the color filter pixel portion is formed by washing with an alkaline aqueous solution. effective.

針對藉由本發明之三芳基甲烷化合物之分散方法中之光微影法製造濾色器像素部之方法進行了詳細記載，但使用本發明之三芳基甲烷化合物所製備之濾色器像素部亦可利用其他電沈積法、轉印法、微胞電解法、PVED(Photovoltaic Electrodeposition，光伏電沈積)法、噴墨法、反轉印刷法、熱硬化法等方法形成藍色像素部，而製造濾色器。 The method for manufacturing the color filter pixel portion by the photolithography method in the method for dispersing the triarylmethane compound of the present invention is described in detail, but the color filter pixel portion prepared by using the triarylmethane compound of the present invention may be used. The blue pixel portion is formed by other methods such as an electrodeposition method, a transfer method, a cell electrolytic method, a PVED (Photovoltaic Electrodeposition) method, an inkjet method, a reverse printing method, and a thermosetting method to produce a color filter Device.

濾色器可利用如下方法獲得：使用紅色顏料、綠色顏料、使用本發明之三芳基甲烷化合物而獲得之各種顏色之光硬化性組成物作為有機顏料，藉由於平行之一對透明電極間封入液晶材料，將透明電極分割成非連續之微細區間，並且於該透明電極上之由黑矩陣格子狀地劃分而成之微細區間之各者交替且圖案狀地設置選自紅、綠及藍之任一種顏色之濾色器著色像素部的方法獲得；或藉由於基板上形成濾色器著色像素部之後設置透明電極而獲得。 The color filter can be obtained by using a red pigment, a green pigment, and a light-curable composition of various colors obtained by using the triarylmethane compound of the present invention as an organic pigment. The liquid crystal is sealed between a pair of parallel transparent electrodes. Material, the transparent electrode is divided into non-continuous fine sections, and each of the fine sections divided by a black matrix in a grid pattern on the transparent electrode is alternately and patterned to be selected from any of red, green, and blue Obtained by a method of coloring a pixel portion of a color filter; or by providing a transparent electrode after forming a color filter colored pixel portion on a substrate.

本發明之三芳基甲烷化合物可提供鮮明性及明度優異之分散體，除濾色器用途以外，亦可應用於塗料、塑膠(樹脂成型品)、印刷墨水、橡膠、皮革、印染、靜電圖像顯影用碳粉(toner)、噴墨記錄用墨水、熱轉印油墨等之著色。 The triarylmethane compound of the present invention can provide a dispersion with excellent sharpness and lightness. In addition to the use of color filters, it can also be used in coatings, plastics (resin molding), printing inks, rubber, leather, printing and dyeing, and electrostatic images Coloring of toner for development, ink for inkjet recording, thermal transfer ink, and the like.

以下，藉由實施例對本發明詳細地進行說明，當然，本發明並不限定於該等實施例之範圍。再者，只要無特別申明，則「份」、「%」及「ppm」均為質量基準。 Hereinafter, the present invention will be described in detail through examples. However, the present invention is not limited to the scope of these examples. In addition, as long as there is no special statement, "part", "%" and "ppm" are all quality standards.

<中間體1之合成> <Synthesis of Intermediate 1>

以下反應係於氮氣環境下進行。使N-乙基苯胺(東京化成工業股份有限公司製造之試劑)15.5份溶解於N,N-二甲基甲醯胺(和光純藥工業股份有限公司製造之試劑)300ml中，並添加α,α'-二溴對二甲苯(東京化成工業股份有限公司製造之試劑)16份，於室溫攪拌30分鐘。繼而，添加碳酸鉀(和光純藥工業股份有限公司製造之試劑)18.5份，於50℃攪拌3小時。將反應液冷卻至室溫，並利用乙酸乙酯250ml進行稀釋。利用水及飽和鹽水進行洗淨後，添加無水硫酸鈉進行乾燥。於減壓下將溶劑蒸餾去除，於殘渣中添加乙酸乙酯進行加熱溶解，並於冰箱中進行冷卻。過濾所產生之結晶，以己烷/乙酸乙酯=4/1進行洗淨。將所獲得之結晶於減壓下進行加熱乾燥而獲得中間物(1)(16.1份、產率77%)。 The following reactions were performed under a nitrogen atmosphere. 15.5 parts of N-ethylaniline (reagent manufactured by Tokyo Chemical Industry Co., Ltd.) was dissolved in 300 ml of N, N-dimethylformamide (reagent manufactured by Wako Pure Chemical Industries, Ltd.), and α was added, 16 parts of α'-dibromo-p-xylene (reagent manufactured by Tokyo Chemical Industry Co., Ltd.) were stirred at room temperature for 30 minutes. Then, 18.5 parts of potassium carbonate (reagent manufactured by Wako Pure Chemical Industries, Ltd.) was added, and it stirred at 50 degreeC for 3 hours. The reaction solution was cooled to room temperature, and diluted with 250 ml of ethyl acetate. After washing with water and saturated saline, anhydrous sodium sulfate was added and dried. The solvent was distilled off under reduced pressure, and ethyl acetate was added to the residue to dissolve it by heating, and then cooled in a refrigerator. The resulting crystals were filtered and washed with hexane / ethyl acetate = 4/1. The obtained crystal was heated and dried under reduced pressure to obtain an intermediate (1) (16.1 parts, yield 77%).

於4-二乙胺基苯甲酸(東京化成工業股份有限公司製造之試劑)20.2份與甲苯100ml之混合物中添加亞硫醯氯(和光純藥工業股份有限公司製造之試劑)18.7份，於80℃攪拌3小時，其後，進行減壓濃縮，而獲得4-二乙胺基苯甲醯氯。 Add 18.7 parts of thionyl chloride (reagent manufactured by Wako Pure Chemical Industries, Ltd.) to a mixture of 20.2 parts of 4-diethylaminobenzoic acid (reagent manufactured by Tokyo Chemical Industry Co., Ltd.) and 100 ml of toluene, at 80 After stirring at 3 ° C for 3 hours, the solution was concentrated under reduced pressure to obtain 4-diethylaminobenzidine chloride.

將無水氯化鋁(和光純藥工業股份有限公司製造之試劑)23.4份與1,2-二氯乙烷(和光純藥工業股份有限公司製造之試劑)120ml之混合物利用冰浴進行冷卻，並歷時50分鐘滴加下述之溶液，即，將上述4-二乙胺基苯甲醯氯溶解於1,2-二氯乙烷50ml中而得之溶液。一面利用冰浴進行冷卻，一面攪拌1小時，其後，歷時50分鐘滴加下述之溶液，即，將中間物(1)15份溶解於1,2-二氯乙烷60ml中而得之溶液。一面利用冰浴進行冷卻，一面攪拌1小時，其後，於室溫攪拌一晚。將反應液注入至冰水，利用15%氫氧化鈉水溶液而使其為pH10以上，並利用氯仿進行萃取。將氯仿層利用5%氫氧化鈉水溶液及飽和鹽水進行洗淨，並利用無水硫酸鈉進行乾燥。進行減壓濃縮，並利用矽膠管柱層析法(氯仿/乙酸乙酯=20/1至5/1)進行精製，而獲得中間體1(6.5份、產率20%)。 The mixture of 23.4 parts of anhydrous aluminum chloride (reagent manufactured by Wako Pure Chemical Industries, Ltd.) and 120 ml of 1,2-dichloroethane (reagent manufactured by Wako Pure Chemical Industries, Ltd.) was cooled with an ice bath, and The following solution was added dropwise over 50 minutes, that is, a solution obtained by dissolving the aforementioned 4-diethylaminobenzidine chloride in 50 ml of 1,2-dichloroethane. While cooling with an ice bath, the mixture was stirred for 1 hour, and then the following solution was added dropwise over 50 minutes, that is, 15 parts of the intermediate (1) was dissolved in 60 ml of 1,2-dichloroethane Solution. While cooling with an ice bath, the mixture was stirred for 1 hour, and then stirred at room temperature overnight. Pour the reaction solution into ice water, A 15% sodium hydroxide aqueous solution was used to adjust the pH to 10 or higher, and extraction was performed with chloroform. The chloroform layer was washed with a 5% sodium hydroxide aqueous solution and saturated saline, and dried over anhydrous sodium sulfate. The mixture was concentrated under reduced pressure and purified by silica gel column chromatography (chloroform / ethyl acetate = 20/1 to 5/1) to obtain Intermediate 1 (6.5 parts, yield 20%).

<中間體2之合成> <Synthesis of Intermediate 2>

以下反應係於氮氣環境下進行。使N-乙基苯胺(東京化成工業股份有限公司製造之試劑)28.3份溶解於N,N-二甲基甲醯胺(和光純藥工業股份有限公司製造之試劑)500ml，並添加1,4-雙(溴甲基)環己烷(順式-反式混合物，利用Journal of Organic Chemistry,vol60,p7865(1995)記載之方法進行合成)30份，於室溫攪拌30分鐘。繼而，添加碳酸鉀(和光純藥工業股份有限公司製造之試劑)33.8份並於50℃攪拌4小時。將反應液冷卻至室溫，並利用乙酸乙酯500ml進行稀釋。利用水及飽和鹽水進行洗淨後，添加無水硫酸鈉進行乾燥。於減壓下將溶劑蒸餾去除，於殘渣中添加乙酸乙酯進行加熱溶解，並於冰箱中進行冷卻。過濾所產生之結晶，以己烷/乙酸乙酯=4/1進行洗淨。將所獲得之結晶於減壓下進行加熱乾燥而獲得中間物(2)(20份、產率51%)。 The following reactions were performed under a nitrogen atmosphere. 28.3 parts of N-ethylaniline (reagent manufactured by Tokyo Chemical Industry Co., Ltd.) was dissolved in 500 ml of N, N-dimethylformamide (reagent manufactured by Wako Pure Chemical Industries, Ltd.), and 1,4 -30 parts of bis (bromomethyl) cyclohexane (cis-trans mixture, synthesized by the method described in Journal of Organic Chemistry, vol60, p7865 (1995)), and stirred at room temperature for 30 minutes. Then, 33.8 parts of potassium carbonate (reagent manufactured by Wako Pure Chemical Industries, Ltd.) was added, and it stirred at 50 degreeC for 4 hours. The reaction solution was cooled to room temperature, and diluted with 500 ml of ethyl acetate. After washing with water and saturated saline, anhydrous sodium sulfate was added and dried. The solvent was distilled off under reduced pressure, and ethyl acetate was added to the residue to dissolve it by heating, and then cooled in a refrigerator. The resulting crystals were filtered and washed with hexane / ethyl acetate = 4/1. The obtained crystal was heated and dried under reduced pressure to obtain an intermediate (2) (20 parts, yield 51%).

於4-二乙胺基苯甲酸(東京化成工業股份有限公司製造之試劑)26.4份與甲苯150ml之混合物中添加亞硫醯氯(和光純藥工業股份有限公司製造之試劑)24.4份，並於80℃攪拌3小時，其後，進行減壓濃縮，而獲得4 -二乙胺基苯甲醯氯。 To 26.4 parts of 4-diethylaminobenzoic acid (reagent manufactured by Tokyo Chemical Industry Co., Ltd.) and 150 ml of toluene were added 24.4 parts of thionyl chloride (reagent manufactured by Wako Pure Chemical Industries, Ltd.), and Stir at 80 ° C for 3 hours, and then concentrate under reduced pressure to obtain 4 -Diethylamino benzamidine chloride.

將無水氯化鋁(和光純藥工業股份有限公司製造之試劑)30.5份與1,2-二氯乙烷(和光純藥工業股份有限公司製造之試劑)150ml之混合物利用冰浴進行冷卻，並歷時50分鐘滴加下述之溶液，即，將上述4-二乙胺基苯甲醯氯溶解於1,2-二氯乙烷70ml中而得之溶液。一面利用冰浴進行冷卻，一面攪拌1小時，其後，歷時50分鐘滴加下述之溶液，即，將中間物(2)20份溶解於1,2-二氯乙烷80ml中而得之溶液。一面利用冰浴進行冷卻，一面攪拌1小時，其後，於室溫攪拌一晚。將反應液注入至冰水，利用15%氫氧化鈉水溶液使其為pH10以上，並利用氯仿進行萃取。將氯仿層利用5%氫氧化鈉水溶液及飽和鹽水進行洗淨，並利用無水硫酸鈉進行乾燥。進行減壓濃縮，並利用矽膠管柱層析法(氯仿/乙酸乙酯=20/1至5/1)進行精製，而獲得中間體2(6.0份、產率15%)。 The mixture of 30.5 parts of anhydrous aluminum chloride (reagent manufactured by Wako Pure Chemical Industries, Ltd.) and 150 ml of 1,2-dichloroethane (reagent manufactured by Wako Pure Chemical Industries, Ltd.) was cooled with an ice bath, The following solution was added dropwise over 50 minutes, that is, a solution obtained by dissolving the 4-diethylaminobenzidine chloride in 70 ml of 1,2-dichloroethane. While cooling with an ice bath, the mixture was stirred for 1 hour, and then the following solution was added dropwise over 50 minutes, that is, 20 parts of the intermediate (2) was dissolved in 80 ml of 1,2-dichloroethane Solution. While cooling with an ice bath, the mixture was stirred for 1 hour, and then stirred at room temperature overnight. The reaction solution was poured into ice water, and the pH was 10 or more with a 15% sodium hydroxide aqueous solution, and extraction was performed with chloroform. The chloroform layer was washed with a 5% sodium hydroxide aqueous solution and saturated saline, and dried over anhydrous sodium sulfate. The mixture was concentrated under reduced pressure, and purified by silica gel column chromatography (chloroform / ethyl acetate = 20/1 to 5/1) to obtain Intermediate 2 (6.0 parts, yield 15%).

<中間體3之合成> <Synthesis of Intermediate 3>

以下反應係於氮氣環境下進行。將硫氰酸鉀(和光純藥工業股份有限公司製造之試劑)18.2份投入至丙酮110ml，其後，於室溫攪拌30分鐘。繼而，歷時10分鐘滴加苯甲醯氯(和光純藥工業股份有限公司製造之試劑)25份。滴加結束後，進而於室溫下攪拌2小時。一面利用冰浴進行冷卻一面歷時15分鐘滴加N-乙基鄰甲苯胺(東京化成工業股份有限公司製造之試劑)22.9份。滴加結束後，進而於室溫攪拌30分鐘。一面利用冰浴進行冷卻一面歷時15分鐘滴加30%氫氧化鈉水溶液17.1份。於室溫攪拌30分鐘後，少量逐步地添加氯乙酸(和光純藥工業股份有限公司製造之試劑)17.7份，加熱回流7小時。冷卻至室溫之後，將反應液注入至水中，利用甲苯進行萃取。以1N鹽酸、水、飽和鹽水之順序將有機層洗淨並利用無水硫酸鈉進行乾燥。於減壓下將溶劑蒸餾去除，於殘渣中添加12%氫氧化鈉水溶液135份及氯乙酸20.7份。加熱回流一晚之後，冷卻至室溫並利用甲苯進行萃取。以1N鹽酸、水、飽和鹽水之順序將有機層洗淨並利用無水硫酸鈉進行乾燥。進行減壓濃縮，並利用矽膠管柱層析法(己烷/丙酮=6/1)進行精製，而獲得中間體3(18.2份、產率35%)。 The following reactions were performed under a nitrogen atmosphere. 18.2 parts of potassium thiocyanate (reagent manufactured by Wako Pure Chemical Industries, Ltd.) was put into 110 ml of acetone, and then stirred at room temperature for 30 minutes. Then, 25 parts of benzamidine chloride (a reagent manufactured by Wako Pure Chemical Industries, Ltd.) was added dropwise over 10 minutes. After completion of the dropwise addition, the mixture was further stirred at room temperature for 2 hours. While cooling in an ice bath, N-ethyl-o-toluidine (manufactured by Tokyo Chemical Industry Co., Ltd.) was added dropwise over 15 minutes. Reagent) 22.9 parts. After the dropwise addition was completed, the mixture was further stirred at room temperature for 30 minutes. While cooling with an ice bath, 17.1 parts of a 30% sodium hydroxide aqueous solution was added dropwise over 15 minutes. After stirring at room temperature for 30 minutes, 17.7 parts of chloroacetic acid (a reagent manufactured by Wako Pure Chemical Industries, Ltd.) was gradually added in small amounts, and heated under reflux for 7 hours. After cooling to room temperature, the reaction solution was poured into water and extracted with toluene. The organic layer was washed in the order of 1N hydrochloric acid, water, and saturated saline, and dried over anhydrous sodium sulfate. The solvent was distilled off under reduced pressure, and 135 parts of a 12% sodium hydroxide aqueous solution and 20.7 parts of chloroacetic acid were added to the residue. After heating under reflux overnight, it was cooled to room temperature and extracted with toluene. The organic layer was washed in the order of 1N hydrochloric acid, water, and saturated saline, and dried over anhydrous sodium sulfate. The solution was concentrated under reduced pressure, and purified by silica gel column chromatography (hexane / acetone = 6/1) to obtain Intermediate 3 (18.2 parts, yield 35%).

<化合物1之合成> <Synthesis of Compound 1>

將6.0份中間體1、及N-乙基-1-萘基胺(東京化成工業股份有限公司製造之試劑)3.0份混合於甲苯40ml，其後，添加磷醯氯(關東化學股份有限公司製造之試劑)3.3份，進行回流5小時。冷卻至室溫後，添加1N鹽酸攪拌15分鐘，並利用氯仿進行萃取。將氯仿層利用飽和鹽水進行洗淨，並利用無水硫酸鈉進行乾燥。進行減壓濃縮，並利用矽膠管柱層析法(氯仿/甲醇=15/1至5/1)進行精製，而獲得化合物1(5.1份、產率55%)。 6.0 parts of Intermediate 1 and 3.0 parts of N-ethyl-1-naphthylamine (reagent manufactured by Tokyo Chemical Industry Co., Ltd.) were mixed in 40 ml of toluene, and then phosphoric acid chloride (manufactured by Kanto Chemical Co., Ltd.) was added. Reagent) 3.3 parts, and refluxed for 5 hours. After cooling to room temperature, 1N hydrochloric acid was added and stirred for 15 minutes, and extraction was performed with chloroform. The chloroform layer was washed with saturated saline, and dried over anhydrous sodium sulfate. The mixture was concentrated under reduced pressure, and purified by silica gel column chromatography (chloroform / methanol = 15/1 to 5/1) to obtain compound 1 (5.1 parts, yield 55%).

<化合物2之合成> <Synthesis of Compound 2>

將6.3份中間體1、及1-甲基-2-苯基吲哚(東京化成工業股份有限公司製造之試劑)3.8份混合於甲苯40ml，其後，添加磷醯氯(關東化學股份有限公司製造之試劑)3.5份，進行回流5小時。冷卻至室溫後，添加1N鹽酸攪拌15分鐘，並利用氯仿進行萃取。將氯仿層利用飽和鹽水進行洗淨，並利用無水硫酸鈉進行乾燥。進行減壓濃縮，並利用矽膠管柱層析法(氯仿/甲醇=15/1至5/1)進行精製，而獲得化合物2(4.8份、產率46%)。 6.3 parts of Intermediate 1 and 3.8 parts of 1-methyl-2-phenylindole (reagent manufactured by Tokyo Chemical Industry Co., Ltd.) were mixed in 40 ml of toluene, and then phosphoric acid chloride (Kanto Chemical Co., Ltd.) was added. 3.5 parts of manufactured reagent), and refluxed for 5 hours. After cooling to room temperature, 1N hydrochloric acid was added and stirred for 15 minutes, and extraction was performed with chloroform. The chloroform layer was washed with saturated saline, and dried over anhydrous sodium sulfate. The mixture was concentrated under reduced pressure, and purified by silica gel column chromatography (chloroform / methanol = 15/1 to 5/1) to obtain compound 2 (4.8 parts, yield 46%).

<化合物3之合成> <Synthesis of Compound 3>

將5.8份中間體1、及4.9份中間體3混合於甲苯40ml，其後，添加磷醯氯(關東化學股份有限公司製造之試劑)3.2份，進行回流5小時。冷卻至室溫後，添加1N鹽酸攪拌15分鐘，並利用氯仿進行萃取。將氯仿層利用飽和鹽水進行洗淨，並利用無水硫酸鈉進行乾燥。進行減壓濃縮，並利用矽膠管柱層析法(氯仿/甲醇=15/1至5/1)進行精製，而獲得化合物3(6.4份、產率58%)。 5.8 parts of Intermediate 1 and 4.9 parts of Intermediate 3 were mixed in 40 ml of toluene, and then 3.2 parts of phosphorochlorine (a reagent manufactured by Kanto Chemical Co., Ltd.) was added and refluxed for 5 hours. After cooling to room temperature, 1N hydrochloric acid was added and stirred for 15 minutes, and extraction was performed with chloroform. The chloroform layer was washed with saturated saline, and dried over anhydrous sodium sulfate. The mixture was concentrated under reduced pressure, and purified by silica gel column chromatography (chloroform / methanol = 15/1 to 5/1) to obtain compound 3 (6.4 parts, yield 58%).

<化合物4之合成> <Synthesis of Compound 4>

將6.0份中間體2、及N-乙基-1-萘基胺(東京化成工業股份有限公司製造之試劑)2.9份混合於甲苯40ml，其後，添加磷醯氯(關東化學股份有限公司製造之試劑)3.3份，進行回流5小時。冷卻至室溫後，添加1N鹽酸攪拌15分鐘，並利用氯仿進行萃取。將氯仿層利用飽和鹽水進行洗淨，並利用無水硫酸鈉進行乾燥。進行減壓濃縮，並利用矽膠管柱層析法(氯仿/甲醇=15/1至5/1)進行精製，而獲得化合物4(4.5份、產率48%)。 6.0 parts of Intermediate 2 and 2.9 parts of N-ethyl-1-naphthylamine (reagent manufactured by Tokyo Chemical Industry Co., Ltd.) were mixed in 40 ml of toluene, and then phosphoric acid chloride (manufactured by Kanto Chemical Co., Ltd.) was added. Reagent) 3.3 parts, and refluxed for 5 hours. After cooling to room temperature, 1N hydrochloric acid was added and stirred for 15 minutes, and extraction was performed with chloroform. The chloroform layer was washed with saturated saline, and dried over anhydrous sodium sulfate. The mixture was concentrated under reduced pressure, and purified by silica gel column chromatography (chloroform / methanol = 15/1 to 5/1) to obtain compound 4 (4.5 parts, yield 48%).

<化合物5之合成> <Synthesis of Compound 5>

參考日本特開2013-057054號公報之段落編號[0087]，而獲得化合物5(7.5份、產率60%)。 Referring to paragraph number [0087] of Japanese Patent Application Laid-Open No. 2013-057054, Compound 5 (7.5 parts, yield 60%) was obtained.

<陰離子K₆(P₂MoW₁₇O₆₂)之合成> <Synthesis of anion K ₆ (P ₂ MoW ₁₇ O ₆₂ )>

將Na₂WO₄‧2H₂O(和光純藥工業股份有限公司製造之試劑)44.0份、Na₂MoO₄‧2H₂O(關東化學股份有限公司製造之試劑)1.90份溶解於純化水230份。對該溶液一面進行攪拌一面使用滴液漏斗添加85%磷酸64.9份。將所獲得之溶液加熱回流8小時。將反應液冷卻至室溫，並添加1滴溴水，一面攪拌一面添加氯化鉀45.0份，藉此獲得K₆(P₂MoW₁₇O₆₂)。進而攪拌1小時後，過濾分離所產生之黃色之沈澱K₆(P₂MoW₁₇O₆₂)，並以90℃進行乾燥，而獲得產量29.4份之乾燥物。 44.0 parts of Na ₂ WO ₄ ‧ 2H ₂ O (reagent manufactured by Wako Pure Chemical Industries, Ltd.) and 1.90 parts of Na ₂ MoO ₄ ‧ 2H ₂ O (reagent manufactured by Kanto Chemical Co., Ltd.) were dissolved in 230 parts of purified water . While stirring this solution, 64.9 parts of 85% phosphoric acid was added using a dropping funnel. The obtained solution was heated under reflux for 8 hours. The reaction solution was cooled to room temperature, 1 drop of bromine water was added, and 45.0 parts of potassium chloride was added while stirring, thereby obtaining K ₆ (P ₂ MoW ₁₇ O ₆₂ ). After further stirring for 1 hour, the yellow precipitate K ₆ (P ₂ MoW ₁₇ O ₆₂ ) produced was separated by filtration and dried at 90 ° C. to obtain 29.4 parts of a dried product.

<陰離子K₄(SiMoW₁₂O₄₀)之合成> <Synthesis of anion K ₄ (SiMoW ₁₂ O ₄₀ )>

於13mol/L之HNO₃水溶液9.8份中添加1mol/L之Na₂MoO₄水溶液16.4份進行攪拌。於該溶液中少量逐步地添加16.4份利用下述文獻1記載之方法所製備之K₈(SiW₁₁O₃₉)‧13H₂O。於室溫下攪拌4小時後，添加飽和KCl水溶液26份，藉此獲得K₄(SiMoW₁₁O₄₀)之沈澱物。將該沈澱物進行過濾分離，並利用飽和KCl水溶液進行洗淨。將所獲得之固體於室溫且減壓下進行乾燥。獲得產量12.2份之乾燥物。(參照文獻1：Inorganic Synthesis vol.27 p85) To 9.8 parts of a 13 mol / L HNO ₃ aqueous solution, 16.4 parts of a 1 mol / L Na ₂ MoO ₄ aqueous solution was added and stirred. To this solution, 16.4 parts of K ₈ (SiW ₁₁ O ₃₉ ) · 13H ₂ O prepared by the method described in Document 1 below was gradually added in small amounts. After stirring at room temperature for 4 hours, 26 parts of a saturated KCl aqueous solution was added to obtain a precipitate of K ₄ (SiMoW ₁₁ O ₄₀ ). This precipitate was separated by filtration and washed with a saturated KCl aqueous solution. The obtained solid was dried at room temperature under reduced pressure. A yield of 12.2 parts of a dried product was obtained. (Reference 1: Inorganic Synthesis vol. 27 p85)

<化合物6之合成> <Synthesis of Compound 6>

將2.0份化合物1投入於水/甲醇=1/1混合液500ml，並於50℃攪拌30分鐘使其溶解。繼而，將K₆(P₂MoW₁₇O₆₂)2.9份溶解於溫水20ml，其後，緩慢地添加至化合物1之溶液中，並於40℃~45℃攪拌1.5小時。冷卻後進行過濾，並利用水/甲醇=2/1混合液100ml及水150ml進行洗淨。將所獲得之固體進行乾燥，而獲得化合物6(3.4份、產率75%)。 2.0 parts of Compound 1 was put into 500 ml of a water / methanol = 1/1 mixed solution, and stirred at 50 ° C for 30 minutes to dissolve it. Then, 2.9 parts of K ₆ (P ₂ MoW ₁₇ O ₆₂ ) was dissolved in 20 ml of warm water, and then, it was slowly added to the solution of Compound 1 and stirred at 40 ° C to 45 ° C for 1.5 hours. After cooling, it was filtered and washed with 100 ml of water / methanol = 2/1 mixed solution and 150 ml of water. The obtained solid was dried to obtain compound 6 (3.4 parts, yield 75%).

又，化合物6亦可利用如下方法同樣地獲得。於2.0份化合物1中添加乙酸100份並於50℃進行加熱攪拌而進行溶解。將該溶液利用10%KOH水溶液調整至pH2.0，其後，以乙酸濃度成為30%之方式追加水。繼而，將K₆(P₂MoW₁₇O₆₂)3.1份溶解於溫水20ml，其後，緩慢地添加化合物1之溶液，並於50℃攪拌1小時。其後使內溫增高至80℃，進而攪拌1小時。冷卻後進行過濾，並利用100ml之水洗淨2次。於所獲得之固體中添加水200ml，於室溫攪拌1小時並再次進行過濾。利用100ml水進行洗淨3次，其後，將所獲得之固體進行乾燥而獲得化合物6(4.0、產率89%)。 Compound 6 can also be obtained in the same manner as described below. 100 parts of acetic acid was added to 2.0 parts of Compound 1, and the mixture was dissolved by heating and stirring at 50 ° C. This solution was adjusted to pH 2.0 with a 10% KOH aqueous solution, and thereafter, water was added so that the acetic acid concentration became 30%. Next, 3.1 parts of K ₆ (P ₂ MoW ₁₇ O ₆₂ ) was dissolved in 20 ml of warm water, and then a solution of Compound 1 was slowly added and stirred at 50 ° C. for 1 hour. Thereafter, the internal temperature was increased to 80 ° C., and the mixture was further stirred for 1 hour. After cooling, it was filtered and washed twice with 100 ml of water. 200 ml of water was added to the obtained solid, and it stirred at room temperature for 1 hour, and filtered again. After washing with 100 ml of water three times, the obtained solid was dried to obtain compound 6 (4.0, yield 89%).

<化合物7之合成> <Synthesis of Compound 7>

將2.0份化合物1投入至水/甲醇=1/1混合液500ml，並於50℃攪拌30分鐘使其溶解。繼而，將K₄(SiMoW₁₁O₄₀)2.8份溶解於溫水20ml，其後，緩慢地添加至化合物1之溶液，於40℃~45℃攪拌1.5小時。冷卻後進行過濾，並利用水/甲醇=2/1混合液100ml及水150ml進行洗淨。將所獲得之固體進行乾燥，而獲得化合物7(3.6份、產率80%)。 2.0 parts of Compound 1 was put into 500 ml of a water / methanol = 1/1 mixed solution, and the mixture was stirred at 50 ° C. for 30 minutes to be dissolved. Next, 2.8 parts of K ₄ (SiMoW ₁₁ O ₄₀ ) was dissolved in 20 ml of warm water, and then slowly added to the solution of Compound 1 and stirred at 40 ° C to 45 ° C for 1.5 hours. After cooling, it was filtered and washed with 100 ml of water / methanol = 2/1 mixed solution and 150 ml of water. The obtained solid was dried to obtain compound 7 (3.6 parts, yield 80%).

又，化合物7亦可利用如下方法同樣地獲得。於2.0份化合物1中添加乙酸100份並於50℃進行加熱攪拌而進行溶解。將該溶液利用10%KOH水溶液調整至pH2.0，其後，以乙酸濃度成為30%之方式追加水。繼而，將K₄(SiMoW₁₁O₄₀)3.0份溶解於溫水20ml，其後，緩慢地添加至化合物1之溶液，並於50℃下攪拌1小時。其後，使內溫增高至80℃，進而攪拌1小時。冷卻後進行過濾，並利用100ml之水洗淨3次。於所獲得之固體中添加水200ml，於室溫下攪拌1小時並再次進行過濾。利用100ml水洗淨5次，其後，將所獲得之固體進行乾燥而獲得化合物7(3.7、產率82%)。 Compound 7 can also be obtained in the same manner as described below. 100 parts of acetic acid was added to 2.0 parts of Compound 1, and the mixture was dissolved by heating and stirring at 50 ° C. This solution was adjusted to pH 2.0 with a 10% KOH aqueous solution, and thereafter, water was added so that the acetic acid concentration became 30%. Next, 3.0 parts of K ₄ (SiMoW ₁₁ O ₄₀ ) was dissolved in 20 ml of warm water, and thereafter, it was slowly added to the solution of Compound 1 and stirred at 50 ° C. for 1 hour. Thereafter, the internal temperature was increased to 80 ° C., and the mixture was further stirred for 1 hour. After cooling, it was filtered and washed three times with 100 ml of water. 200 ml of water was added to the obtained solid, and it stirred at room temperature for 1 hour, and filtered again. After washing with 100 ml of water five times, the obtained solid was dried to obtain compound 7 (3.7, yield 82%).

<化合物8之合成> <Synthesis of Compound 8>

於3.0份化合物1中添加甲醇90ml並於50℃進行加熱攪拌而進行溶解。向該溶液中滴加溶解於甲醇30ml之雙(三氟甲磺醯)亞胺鉀(potassium bis(trifluoromethanesulfonyl)imide，和光純藥工業股份有限公司製造之試劑) 1.8份。於50℃攪拌1小時後，將反應液進行過濾並利用蒸發器進行濃縮。於所獲得之殘渣中添加水/甲醇=2/1混合液90ml並攪拌30分鐘。過濾固形物成分並進行乾燥，而獲得化合物8(3.0份、產率68%)。 90 ml of methanol was added to 3.0 parts of Compound 1, and the mixture was dissolved by heating and stirring at 50 ° C. To this solution, potassium bis (trifluoromethanesulfonyl) imide dissolved in 30 ml of methanol (a reagent manufactured by Wako Pure Chemical Industries, Ltd.) was added dropwise. 1.8 servings. After stirring at 50 ° C for 1 hour, the reaction solution was filtered and concentrated by an evaporator. To the obtained residue, 90 ml of a water / methanol = 2/1 mixed solution was added and stirred for 30 minutes. The solid component was filtered and dried to obtain compound 8 (3.0 parts, yield 68%).

<化合物9之合成> <Synthesis of Compound 9>

於3.0份化合物1中添加甲醇90ml並於50℃進行加熱攪拌而進行溶解。向該溶液中滴加溶解於甲醇30ml之三(三氟甲磺醯基)甲基化絕(cesium tris(trifluoromethanesulfonyl)methide，Central Glass股份有限公司製造之試劑)3.1份。於50℃攪拌1小時後，將反應液進行過濾並利用蒸發器進行濃縮。於所獲得之殘渣中添加水/甲醇=2/1混合液90ml並攪拌30分鐘。過濾固形物成分並進行乾燥，而獲得化合物9(3.6份、產率71%)。 90 ml of methanol was added to 3.0 parts of Compound 1, and the mixture was dissolved by heating and stirring at 50 ° C. To this solution, 3.1 parts of a cesium tris (trifluoromethanesulfonyl) method (a reagent manufactured by Central Glass Co., Ltd.) dissolved in 30 ml of methanol was added dropwise. After stirring at 50 ° C for 1 hour, the reaction solution was filtered and concentrated by an evaporator. To the obtained residue, 90 ml of a water / methanol = 2/1 mixed solution was added and stirred for 30 minutes. The solid component was filtered and dried to obtain Compound 9 (3.6 parts, yield 71%).

<化合物10之合成> <Synthesis of Compound 10>

將2,6-萘二磺酸二鈉(東京化成工業股份有限公司製造之試劑)1.0份投入至水/甲醇=1/2混合液60ml，並於50℃進行攪拌。向其中添加3.2份化合物1，並於50℃下攪拌1小時後，利用蒸發器進行濃縮。於所獲得之殘渣中添加水100ml並進行過濾，利用水進行洗淨。將所獲得之固體進行乾燥，而獲得化合物10(3.1份、產率80%)。 1.0 part of disodium 2,6-naphthalene disulfonate (reagent manufactured by Tokyo Chemical Industry Co., Ltd.) was put into 60 ml of a water / methanol = 1/2 mixed solution, and stirred at 50 ° C. 3.2 parts of Compound 1 was added thereto, and the mixture was stirred at 50 ° C. for 1 hour, and then concentrated by an evaporator. Obtained 100 ml of water was added to the obtained residue, and it was filtered and washed with water. The obtained solid was dried to obtain compound 10 (3.1 parts, yield 80%).

<化合物11之合成> <Synthesis of Compound 11>

將2.5份化合物2投入至水/甲醇=1/1混合液500ml，並於50℃攪拌30分鐘使其溶解。繼而，將K₆(P₂MoW₁₇O₆₂)3.4份溶解於溫水20ml，其後，緩慢地添加至化合物2之溶液，並於40℃~45℃攪拌1.5小時。冷卻後進行過濾，並利用水/甲醇=2/1混合液100ml及水150ml進行洗淨。將所獲得之固體進行乾燥，而獲得化合物11(4.2份、產率77%)。 2.5 parts of compound 2 was added to 500 ml of a water / methanol = 1/1 mixed solution, and the mixture was stirred at 50 ° C. for 30 minutes to be dissolved. Next, 3.4 parts of K ₆ (P ₂ MoW ₁₇ O ₆₂ ) was dissolved in 20 ml of warm water, and then, it was slowly added to the solution of Compound 2 and stirred at 40 ° C to 45 ° C for 1.5 hours. After cooling, it was filtered and washed with 100 ml of water / methanol = 2/1 mixed solution and 150 ml of water. The obtained solid was dried to obtain compound 11 (4.2 parts, yield 77%).

<化合物12之合成> <Synthesis of Compound 12>

將2.5份化合物3投入至水/甲醇=1/1混合液500ml，並於50℃攪拌30分鐘使其溶解。繼而，將K₆(P₂MoW₁₇O₆₂)3.0份溶解於溫水20ml，其後，緩慢地添加至化合物3之溶液，並於40℃~45℃下攪拌1.5小時。冷卻後進行過濾，並利用水/甲醇=2/1混合液100ml及水150ml進行洗淨。將所獲得之固體進行乾燥，而獲得化合物12(4.4份、產率86%)。 2.5 parts of Compound 3 was added to 500 ml of a water / methanol = 1/1 mixed solution, and the mixture was stirred at 50 ° C. for 30 minutes to be dissolved. Next, 3.0 parts of K ₆ (P ₂ MoW ₁₇ O ₆₂ ) was dissolved in 20 ml of warm water, and then, it was slowly added to the solution of Compound 3, and stirred at 40 ° C to 45 ° C for 1.5 hours. After cooling, it was filtered and washed with 100 ml of water / methanol = 2/1 mixed solution and 150 ml of water. The obtained solid was dried to obtain compound 12 (4.4 parts, yield 86%).

<化合物13之合成> <Synthesis of Compound 13>

將2.5份化合物4投入至水/甲醇=1/1混合液500ml，並於50℃攪拌30分鐘使其溶解。繼而，將K₆(P₂MoW₁₇O₆₂)3.6份溶解於溫水20ml，其後，緩慢地添加至化合物4之溶液，並於40℃~45℃攪拌1.5小時。冷卻後進行過濾，並利用水/甲醇=2/1混合液100ml及水150ml進行洗淨。將所獲得之固體進行乾燥，而獲得化合物13(4.0份、產率71%)。 2.5 parts of compound 4 was added to 500 ml of a water / methanol = 1/1 mixed solution, and the mixture was stirred at 50 ° C. for 30 minutes to be dissolved. Next, 3.6 parts of K ₆ (P ₂ MoW ₁₇ O ₆₂ ) was dissolved in 20 ml of warm water, and then, it was slowly added to the solution of Compound 4 and stirred at 40 ° C to 45 ° C for 1.5 hours. After cooling, it was filtered and washed with 100 ml of water / methanol = 2/1 mixed solution and 150 ml of water. The obtained solid was dried to obtain compound 13 (4.0 parts, yield 71%).

<化合物14之合成> <Synthesis of Compound 14>

將2.0份化合物5投入至水/甲醇=1/1混合液500ml，並於50℃攪拌30分鐘使其溶解。繼而，將K₆(P₂MoW₁₇O₆₂)2.9份溶解於溫水20ml，其後，緩慢地添加至化合物5之溶液，並於40℃~45℃攪拌1.5小時。冷卻後進行過濾，並利用水/甲醇=2/1混合液100ml及水150ml進行洗淨。將所獲得之固體進行乾燥，而獲得化合物14(3.6份、產率79%)。 2.0 parts of compound 5 was added to 500 ml of a water / methanol = 1/1 mixed solution, and the mixture was stirred at 50 ° C. for 30 minutes to be dissolved. Next, 2.9 parts of K ₆ (P ₂ MoW ₁₇ O ₆₂ ) was dissolved in 20 ml of warm water, and then, it was slowly added to the solution of Compound 5 and stirred at 40 ° C to 45 ° C for 1.5 hours. After cooling, it was filtered and washed with 100 ml of water / methanol = 2/1 mixed solution and 150 ml of water. The obtained solid was dried to obtain compound 14 (3.6 parts, yield 79%).

<化合物15之合成> <Synthesis of Compound 15>

將鹼性藍7(東京化成工業股份有限公司製造之試劑)5.0份投入至水350ml，並於40℃攪拌30分鐘使其溶解。繼而，將K₆(P₂MoW₁₇O₆₂)7.6份溶解於溫水50ml，其後，緩慢地添加至鹼性藍7之溶液，並於40℃攪拌1小時。繼而，使內溫增高至80℃，進而於該溫度攪拌1小時。冷卻後進行過濾，並利用300ml水洗淨3次。將所獲得之固體進行乾燥，而獲得化合物15(10.1份、產率87%)。 5.0 parts of Basic Blue 7 (a reagent manufactured by Tokyo Chemical Industry Co., Ltd.) was put into 350 ml of water, and it was stirred at 40 ° C for 30 minutes to dissolve. Next, 7.6 parts of K ₆ (P ₂ MoW ₁₇ O ₆₂ ) was dissolved in 50 ml of warm water, and thereafter, it was slowly added to a solution of Basic Blue 7 and stirred at 40 ° C. for 1 hour. Then, the internal temperature was increased to 80 ° C, and the mixture was further stirred at this temperature for 1 hour. After cooling, it was filtered and washed three times with 300 ml of water. The obtained solid was dried to obtain compound 15 (10.1 parts, yield 87%).

<化合物16之合成> <Synthesis of Compound 16>

將2.5份化合物2投入至水/甲醇=1/1混合液500ml，並於50℃攪拌30分鐘使其溶解。繼而，將K₄(SiMoW₁₁O₄₀)3.3份溶解於溫水20ml，其後，緩慢地添加至化合物2之溶液，並於40℃~45℃攪拌1.5小時。冷卻後進行過濾，並利用水/甲醇=2/1混合液100ml及水150ml進行洗淨。將所獲得之固體進行乾燥，而獲得化合物16(4.3份、產率80%)。 2.5 parts of compound 2 was added to 500 ml of a water / methanol = 1/1 mixed solution, and the mixture was stirred at 50 ° C. for 30 minutes to be dissolved. Next, 3.3 parts of K ₄ (SiMoW ₁₁ O ₄₀ ) was dissolved in 20 ml of warm water, and then, it was slowly added to the solution of Compound 2 and stirred at 40 ° C to 45 ° C for 1.5 hours. After cooling, it was filtered and washed with 100 ml of water / methanol = 2/1 mixed solution and 150 ml of water. The obtained solid was dried to obtain compound 16 (4.3 parts, yield 80%).

<化合物17之合成> <Synthesis of Compound 17>

將2.5份化合物3投入至水/甲醇=1/1混合液500ml，並於50℃攪拌30分鐘使其溶解。繼而，將K₄(SiMoW₁₁O₄₀)2.9份溶解於溫水20ml，其後，緩慢地添加至化合物3之溶液，並於40℃~45℃攪拌1.5小時。冷卻後進行過濾，並利用水/甲醇=2/1混合液100ml及水150ml進行洗淨。將所獲得之固體進行乾燥，而獲得化合物17(3.9份、產率78%)。 2.5 parts of Compound 3 was added to 500 ml of a water / methanol = 1/1 mixed solution, and the mixture was stirred at 50 ° C. for 30 minutes to be dissolved. Next, 2.9 parts of K ₄ (SiMoW ₁₁ O ₄₀ ) was dissolved in 20 ml of warm water, and then, it was slowly added to the solution of Compound 3, and stirred at 40 ° C to 45 ° C for 1.5 hours. After cooling, it was filtered and washed with 100 ml of water / methanol = 2/1 mixed solution and 150 ml of water. The obtained solid was dried to obtain compound 17 (3.9 parts, yield 78%).

[實施例1] [Example 1]

將1.80份經市售之榨汁器粉碎之化合物6、BYK-2164(BYK-Chemie公司製造之分散劑)2.10份、丙二醇單甲醚乙酸酯11.10份、0.3-0.4mmΦ之SEPR顆粒添加至聚乙烯瓶，並利用塗料調節器(東洋精機股份有限公司製造)分散2小時，而獲得色料分散液。 Add 1.80 parts of compound 6, crushed by a commercially available juicer, 2.10 parts of BYK-2164 (a dispersant manufactured by BYK-Chemie), 11.10 parts of propylene glycol monomethyl ether acetate, and 0.3-0.4 mmΦ of SEPR particles The polyethylene bottle was dispersed for 2 hours using a paint conditioner (manufactured by Toyo Seiki Co., Ltd.) to obtain a pigment dispersion liquid.

於該色料分散液3.00份中添加UNIDIC ZL-295(DIC股份有限公司製造之丙烯酸系樹脂)1.85份、丙二醇單甲醚乙酸酯0.80份，並利用塗料調節器進行混合，藉此獲得用以形成濾色器用藍色像素部之評價用組成物。 To this pigment dispersion liquid 3.00 parts, 1.85 parts of UNIDIC ZL-295 (acrylic resin manufactured by DIC Corporation) and 0.80 parts of propylene glycol monomethyl ether acetate were added, and mixed with a paint conditioner to obtain The composition for evaluation which forms the blue pixel part for color filters is formed.

向鈉玻璃將該評價用組成物以內插色度y=0.110之方式改變轉數進行4種旋轉塗佈。將以此方式獲得之轉數不同之玻璃板以90℃乾燥3分鐘而獲得評價用玻璃基板。 This evaluation composition was subjected to four types of spin coating by changing the number of revolutions to the soda glass by interpolating the color y = 0.110. Glass plates having different rotation numbers obtained in this way were dried at 90 ° C. for 3 minutes to obtain a glass substrate for evaluation.

[實施例2] [Example 2]

使用化合物7代替化合物6，除此以外，進行與上述實施例1相同之操作，獲得評價用玻璃基板。 A glass substrate for evaluation was obtained in the same manner as in Example 1 except that Compound 7 was used instead of Compound 6.

[實施例3] [Example 3]

使用化合物8代替化合物6，除此以外，進行與上述實施例1相同之操作，獲得評價用玻璃基板。 A glass substrate for evaluation was obtained in the same manner as in Example 1 except that Compound 8 was used instead of Compound 6.

[實施例4] [Example 4]

使用化合物9代替化合物6，除此以外，進行與上述實施例1相同之操作，獲得評價用玻璃基板。 A glass substrate for evaluation was obtained in the same manner as in Example 1 except that Compound 9 was used instead of Compound 6.

[實施例5] [Example 5]

使用化合物10代替化合物6，除此以外，進行與上述實施例1相同之操作，獲得評價用玻璃基板。 Except for using Compound 10 instead of Compound 6, the same procedure as in Example 1 was performed. Operation was performed to obtain a glass substrate for evaluation.

[實施例6] [Example 6]

使用化合物11代替化合物6，除此以外，進行與上述實施例1相同之操作，獲得評價用玻璃基板。 A glass substrate for evaluation was obtained in the same manner as in Example 1 except that Compound 11 was used instead of Compound 6.

[實施例7] [Example 7]

使用化合物12代替化合物6，除此以外，進行與上述實施例1相同之操作，獲得評價用玻璃基板。 A glass substrate for evaluation was obtained in the same manner as in Example 1 except that Compound 12 was used instead of Compound 6.

[實施例8] [Example 8]

使用化合物13代替化合物6，除此以外，進行與上述實施例1相同之操作，獲得評價用玻璃基板。 A glass substrate for evaluation was obtained in the same manner as in Example 1 except that Compound 13 was used instead of Compound 6.

[實施例9] [Example 9]

使用化合物16代替化合物6，除此以外，進行與上述實施例1相同之操作，獲得評價用玻璃基板。 A glass substrate for evaluation was obtained in the same manner as in Example 1 except that Compound 16 was used instead of Compound 6.

[實施例10] [Example 10]

使用化合物17代替化合物6，除此以外，進行與上述實施例1相同之操作，獲得評價用玻璃基板。 A glass substrate for evaluation was obtained in the same manner as in Example 1 except that Compound 17 was used instead of Compound 6.

<比較例1> <Comparative example 1>

使用化合物14代替化合物6，除此以外，進行與上述實施例1相同之操作，獲得評價用玻璃基板。 A glass substrate for evaluation was obtained in the same manner as in Example 1 except that Compound 14 was used instead of Compound 6.

<比較例2> <Comparative example 2>

使用化合物15代替化合物6，除此以外，進行與上述實施例1相同之操作，獲得評價用玻璃基板。 A glass substrate for evaluation was obtained in the same manner as in Example 1 except that Compound 15 was used instead of Compound 6.

<耐熱性試驗評價方法> <Evaluation method of heat resistance test>

將上述實施例1~10及比較例1、2所獲得之評價用玻璃基板以230℃加熱1小時，對加熱前後之色差△E^*ab使用分光光度計U-3900(Hitachi High-Tech Science股份有限公司製造)進行測定。關於色差△E^*ab，其值越小，表示其為具有越高之耐熱性之材料。再者，色差△E^*ab係設為各轉數之玻璃板之色差△E^*ab之平均值。將其結果示於表1。 The glass substrates for evaluation obtained in Examples 1 to 10 and Comparative Examples 1 and 2 were heated at 230 ° C for 1 hour, and the color difference ΔE ^* ab before and after heating was measured using a spectrophotometer U-3900 (Hitachi High-Tech Science Co., Ltd. Co., Ltd.). Regarding the color difference ΔE ^* ab, a smaller value indicates that it is a material having higher heat resistance. Further, the color difference △ E ^* ab color system is set to the number of revolutions of each of the glass sheets △ E ^* ab of the average value. The results are shown in Table 1.

根據表1可知，若將本發明之實施例1~10與比較例1~2進行比較，則色差△E^*ab較小，即便歷經230℃之高溫之熱歷程色差亦較小，本發明之化合物之熱穩定性非常高。 According to Table 1, it can be seen that if Examples 1 to 10 of the present invention are compared with Comparative Examples 1 to 2, the color difference ΔE ^* ab is small, and the color difference is small even after a thermal history of 230 ° C. The thermal stability of the compound is very high.

又，本發明於如下方面優異：可如上述通式(I)般藉由使連結基Z連結於特定之部位而自由地變更對耐熱性有效果之A部而進行合成，從而可進一步提昇耐熱性。例如，若合成上述中間體1或上述中間體2，則可容易地變更A部。進而，藉由變更A部，顏色會變化，因此可調整成所需顏色。 In addition, the present invention is excellent in that it can be synthesized by freely changing the A part having an effect on heat resistance by connecting the linking group Z to a specific portion as in the above-mentioned general formula (I), so that the heat resistance can be further improved. Sex. For example, if the intermediate 1 or the intermediate 2 is synthesized, the A part can be easily changed. Furthermore, since the color is changed by changing part A, it can be adjusted to a desired color.

Claims

一種化合物，其由下述通式(I)表示：

(通式(1)中，Z表示可具有取代基之a價的脂肪族系或芳香族系之烴基；B^c-表示c價之陰離子；R¹~R³分別獨立地表示氫原子、可具有取代基之烷基或可具有取代基之芳基，R¹與R²可鍵結而形成環結構；A表示可具有取代基之芳香族基或可具有取代基之雜環基；多個R¹~R³及A分別可相同亦可不同；a表示2以上之整數，b、c、d表示1以上之整數；Y分別獨立地表示氫原子、或任意之取代基)。 A compound represented by the following general formula (I):

(In the general formula (1), Z represents an a-valent aliphatic or aromatic hydrocarbon group which may have a substituent; B ^c- represents a c-valent anion; R ¹ to R ³ each independently represent a hydrogen atom, and An alkyl group having a substituent or an aryl group which may have a substituent, R ¹ and R ² may be bonded to form a ring structure; A represents an aromatic group which may have a substituent or a heterocyclic group which may have a substituent; multiple R ¹ to R ³ and A may be the same or different, respectively; a represents an integer of 2 or more, b, c, and d represent an integer of 1 or more; Y each independently represents a hydrogen atom or an arbitrary substituent).

如申請專利範圍第1項之化合物，其中，上述通式(I)中之陰離子(B^c-)為雜多金屬氧酸根陰離子(heteropolyoxometalate anion)。 For example, the compound according to item 1 of the patent application scope, wherein the anion (B ^c- ) in the general formula (I) is a heteropolyoxometalate anion.

如申請專利範圍第1項之化合物，其中，上述通式(I)中之陰離子(B^c-)係由下述通式(II)表示：

(通式(II)中，R⁶及R⁷分別獨立地表示可具有取代基之碳數1~8之烷基、可具有取代基之碳數2~6之烯基、或可具有取代基之碳數3~8之環烷基；再者，R⁶及R⁷可相互連結形成環，該環可具有取代基)。 For example, the compound in the first scope of the patent application, wherein the anion (B ^c- ) in the general formula (I) is represented by the following general formula (II):

(In the general formula (II), R ⁶ and R ⁷ each independently represent an alkyl group having 1 to 8 carbons which may have a substituent, an alkenyl group having 2 to 6 carbons which may have a substituent, or may have a substituent A cycloalkyl group having 3 to 8 carbon atoms; furthermore, R ⁶ and R ⁷ may be connected to each other to form a ring, and the ring may have a substituent).

如申請專利範圍第1項之化合物，其中，上述通式(I)中之陰離子(B^c-)係由下述通式(III)表示：

(通式(III)中，R⁸~R¹⁰分別獨立地表示可具有取代基之碳數1~8之烷基、可具有取代基之碳數2~6之烯基、或可具有取代基之碳數3~8之環烷基；再者，R⁸~R¹⁰可相互連結形成環，該環可具有取代基)。 For example, the compound in the first scope of the application for a patent, wherein the anion (B ^c- ) in the general formula (I) is represented by the following general formula (III):

(In the general formula (III), R ⁸ to R ¹⁰ each independently represent an alkyl group having 1 to 8 carbons which may have a substituent, an alkenyl group having 2 to 6 carbons which may have a substituent, or may have a substituent. A cycloalkyl group having 3 to 8 carbon atoms; furthermore, R ⁸ to R ¹⁰ may be connected to each other to form a ring, and the ring may have a substituent).

如申請專利範圍第1項之化合物，其中，上述通式(I)中之陰離子(B^c-)為磺酸陰離子(sulfonic acid anion)。 For example, the compound according to item 1 of the patent application scope, wherein the anion (B ^c- ) in the general formula (I) is a sulfonic acid anion.

一種濾色器，其含有選自申請專利範圍第1至5項之化合物中之至少一種。 A color filter containing at least one selected from the compounds of claims 1 to 5 of the patent application scope.