TW202020061A - Pigment composition, coloring composition and color filter - Google Patents

Abstract

An aspect of the present invention relates a pigment composition containing: a quinophtalone compound represented by formula (1); and at least one aluminum phthalocyanine compound selected from the group consisting of compounds represented by formula (2A) and the like. X1-X16 are each independently a hydrogen atom or a halogen atom, Y1 and Y2 are each independently a hydrogen atom or a halogen atom, and Z is an alkylene group having 1-3 carbon atoms. X51-X54 are an alkyl group and the like, which may have a substituent, Y51 -Y54 are a halogen atom and the like, L1 is a hydroxyl group and the like, and m1-m4 and n1-n4 are integers of 0-4.

Description

Pigment composition, coloring composition and color filter

The invention relates to a pigment composition, a coloring composition and a color filter.

Today, coloring compositions are used in various fields. As specific uses of the coloring compositions, printing inks, paints, colorants for resins, colorants for fibers, colored materials for IT information recording (color filters, colorants, Inkjet) etc. The coloring matter used in the coloring composition requires color characteristics (coloring power, vividness), resistance (weather resistance, light resistance, heat resistance, solvent resistance), etc. Pigments are roughly divided into pigments and dyes. Unlike dyes that develop color in a molecular state, pigments develop color in the state of particles (aggregates of primary particles). Therefore, in general, although pigments are more resistant than dyes, they have poor coloring power or chroma (brightness).

From this background, the search for a pigment with high tinting strength and high chroma, especially organic pigments with advantages in terms of tinting strength, has attracted much attention. For example, Patent Document 1 discloses that a green coloring composition containing a specific quinoline yellow compound and an aluminum phthalocyanine pigment can achieve excellent color rendering power and dispersibility, and can obtain high brightness when used in a color filter Brightness, high contrast ratio. Prior technical literature Patent Literature

Patent Document 1: Japanese Patent Laid-Open No. 2012-247587

[Problems to be solved by the invention]

However, the pigments assumed to be used for color filters are required to have different characteristics from general-purpose uses. Specifically, for example, "high brightness" for reducing power consumption of a backlight, "high coloring power" for thinning of color filters and high color reproduction, etc. are required. However, in the coloring composition disclosed in Patent Document 1, when the use of the color filter is assumed, sufficient brightness and coloring power may not be obtained. That is, for the coloring composition disclosed in Patent Document 1, there is room for further improvement in terms of improving the brightness and obtaining higher color reproducibility even if it is a thin film.

Therefore, an object of the present invention is to provide a pigment composition and a coloring composition excellent in brightness and color rendering power, and a color filter using the same. [Technical means to solve the problem]

The present inventors have made intensive studies to solve the above problems, and as a result, they have found that by combining a compound that dimerizes the quinoline yellow skeleton with a compound having a phthalocyanine aluminum skeleton, the brightness and the color rendering power are improved.

式（1）中，X¹ ～X¹⁶ 各自獨立地為氫原子或鹵素原子，Y¹ 及Y² 各自獨立地為氫原子或鹵素原子，Z為碳數1～3之伸烷基。

式（2A）中， X⁵¹ ～X⁵⁴ 各自獨立地為可具有取代基之烷基、可具有取代基之芳基、可具有取代基之環烷基、可具有取代基之雜環基、可具有取代基之烷氧基、可具有取代基之芳氧基、可具有取代基之烷硫基、或可具有取代基之芳硫基， Y⁵¹ ～Y⁵⁴ 各自獨立地為鹵素原子、硝基、可具有取代基之鄰苯二甲醯亞胺甲基、或可具有取代基之胺磺醯基， L¹ 為羥基、氯原子、-OP(=O)R¹ R² 、或-O-SiR³ R⁴ R⁵ （R¹ ～R⁵ 各自獨立地為氫原子、羥基、可具有取代基之烷基、可具有取代基之芳基、可具有取代基之烷氧基、或可具有取代基之芳氧基，且R¹ 及R² 可相互鍵結而形成環，R³ 、R⁴ 及R⁵ 中之兩個亦可相互鍵結而形成環）， m1～m4及n1～n4各自獨立地為0～4之整數，m1＋n1、m2＋n2、m3＋n3及m4＋n4各自獨立地為0～4之整數。

式（2B）中， X⁵⁵ ～X⁶² 各自獨立地為可具有取代基之烷基、可具有取代基之芳基、可具有取代基之環烷基、可具有取代基之雜環基、可具有取代基之烷氧基、可具有取代基之芳氧基、可具有取代基之烷硫基、或可具有取代基之芳硫基， Y⁵⁵ ～Y⁶² 各自獨立地為鹵素原子、硝基、可具有取代基之鄰苯二甲醯亞胺甲基、或可具有取代基之胺磺醯基， L² 為-O-SiR⁶ R⁷ -O-、-O-SiR⁸ R⁹ -O-SiR¹⁰ R¹¹ -O-、或-O-P(=O)R¹² -O-（R⁶ ～R¹² 各自獨立地為氫原子、羥基、可具有取代基之烷基、可具有取代基之芳基、可具有取代基之烷氧基、或可具有取代基之芳氧基）， m5～m12及n5～n12各自獨立地為0～4之整數，m5＋n5、m6＋n6、m7＋n7、m8＋n8、m9＋n9、m10＋n10、m11＋n11及m12＋n12各自獨立地為0～4之整數。One aspect of the present invention is a pigment composition comprising: a quinoline yellow compound represented by the following formula (1), and selected from a compound represented by the following formula (2A) and represented by the following formula (2B) At least one phthalocyanine aluminum compound in the group of compounds.

In formula (1), X ¹ to X ¹⁶ are each independently a hydrogen atom or a halogen atom, Y ¹ and Y ² are each independently a hydrogen atom or a halogen atom, and Z is an alkylene group having 1 to 3 carbon atoms.

In the formula (2A), X ⁵¹ to X ⁵⁴ are each independently an optionally substituted alkyl group, an optionally substituted aryl group, a substituted cycloalkyl group, a substituted heterocyclic group, or An alkoxy group having a substituent, an aryloxy group having a substituent, an alkylthio group having a substituent, or an arylthio group having a substituent, Y ⁵¹ to Y ⁵⁴ are each independently a halogen atom, a nitro group , Phthalimidomethyl which may have a substituent, or sulfamoyl which may have a substituent, L ¹ is a hydroxyl group, a chlorine atom, -OP(=O)R ¹ R ² , or -O- SiR ³ R ⁴ R ⁵ (R ¹ to R ⁵ are each independently a hydrogen atom, a hydroxyl group, an optionally substituted alkyl group, an optionally substituted aryl group, an optionally substituted alkoxy group, or may be substituted Aryloxy group, and R ¹ and R ² can be bonded to each other to form a ring, two of R ³ , R ⁴ and R ⁵ can also be bonded to each other to form a ring), m1～m4 and n1～n4 each Independently is an integer of 0 to 4, m1 + n1, m2 + n2, m3 + n3 and m4 + n4 are each independently an integer of 0 to 4.

In the formula (2B), X ⁵⁵ to X ⁶² are each independently an optionally substituted alkyl group, an optionally substituted aryl group, a substituted cycloalkyl group, a substituted heterocyclic group, or An alkoxy group having a substituent, an aryloxy group having a substituent, an alkylthio group having a substituent, or an arylthio group having a substituent, Y ⁵⁵ to Y ⁶² are each independently a halogen atom, a nitro group , Phthalimidomethyl which may have a substituent, or sulfamoyl which may have a substituent, L ² is -O-SiR ⁶ R ⁷ -O-, -O-SiR ⁸ R ⁹ -O -SiR ¹⁰ R ¹¹ -O-, or -OP(=O)R ¹² -O-(R ⁶ to R ¹² are each independently a hydrogen atom, a hydroxyl group, an alkyl group which may have a substituent, an aromatic group which may have a substituent) Group, alkoxy group which may have a substituent, or aryloxy group which may have a substituent), m5 to m12 and n5 to n12 are each independently an integer of 0 to 4, m5 + n5, m6 + n6, m7 + n7, m8 + n8, m9 + n9, m10 + n10 , M11+n11 and m12+n12 are each independently an integer from 0 to 4.

Another aspect of the present invention is a coloring composition comprising: the quinoline yellow compound represented by the above formula (1), selected from the compound represented by the above formula (2A) and the compound represented by the above formula (2B) At least one phthalocyanine aluminum compound in the group and the solvent.

Another aspect of the present invention is a color filter having a pixel portion including: a quinoline yellow compound represented by the above formula (1), and a compound selected from the compound represented by the above formula (2A) and the above formula (2B) At least one phthalocyanine aluminum compound in the group consisting of the compounds represented. [Effect of invention]

According to the present invention, it is possible to provide a pigment composition and a coloring composition excellent in brightness and color rendering power, and a color filter using the same.

(Pigment composition) The pigment composition of one embodiment contains a quinoline yellow compound and an aluminum phthalocyanine compound.

式（1）中，X¹ ～X¹⁶ 各自獨立地為氫原子或鹵素原子，Y¹ 及Y² 各自獨立地為氫原子或鹵素原子，Z為碳數1～3之伸烷基。The quinoline yellow compound is represented by the following formula (1).

In formula (1), X ¹ to X ¹⁶ are each independently a hydrogen atom or a halogen atom, Y ¹ and Y ² are each independently a hydrogen atom or a halogen atom, and Z is an alkylene group having 1 to 3 carbon atoms.

The quinoline yellow compound exhibits selective absorption and penetration through dimerization of the quinoline yellow skeleton. In addition, the quinoline yellow compound dimerizes the quinoline yellow skeleton using the linking group Z as a spacer, thereby cutting off the conjugation and suppressing excessive redness. Furthermore, in the above-mentioned quinoline yellow compound, the dispersibility is improved by the introduction of the amide imine structure. Under these circumstances, by using the above-mentioned quinoline yellow compound, a pigment exhibiting excellent brightness and color rendering power when combined with an aluminum phthalocyanine compound (pigment) can be obtained. Specifically, for example, when a pigment composed of the above-mentioned quinoline yellow compound is combined with a pigment composed of a phthalocyanine aluminum compound, the pigment composed of the prescribed quinoline yellow compound described in the above Patent Document 1 , Showing good brightness, and showing superior color rendering power.

The halogen atom in formula (1) may be a fluorine atom, a chlorine atom, a bromine atom or an iodine atom, preferably a fluorine atom, a chlorine atom or a bromine atom, and more preferably a chlorine atom.

As specific examples of the alkylene group having 1 to 3 carbon atoms in formula (1), for example, methylene, ethylidene (1,1-ethanediyl or 1,2-ethanediyl), Propyl (1,1-propanediyl, 2,2-propanediyl, 1,2-propanediyl or 1,3-propanediyl), more preferably methylene, 1,1-ethanediyl , 1,1-propanediyl, 2,2-propanediyl, and more preferably methylene.

In the above-mentioned quinoline yellow compound, preferably at least one of X ¹ to X ¹⁶ is a halogen atom, and more preferably two or more are halogen atoms. ~ X ^{1 6} by introducing a halogen atom to X ^1, dispersibility of the above quinoline yellow compound further increased, there is a tendency can be obtained more significantly the above effect.

Preferably, at least one of X ¹ to X ⁴ is a halogen atom, more preferably two or more are halogen atoms, or all of them may be halogen atoms. It is preferred that at least one of X ² and X ³ is a halogen atom, and it is more preferred that both X ² and X ³ are halogen atoms.

Preferably, at least one of X ⁵ to X ⁸ is a halogen atom, more preferably two or more are halogen atoms, or all of them may be halogen atoms. Preferably, at least one of X ⁶ and X ⁷ is a halogen atom, and more preferably X ⁶ and X ⁷ are both halogen atoms.

Preferably, at least one of X ⁹ to X ¹² is a halogen atom, more preferably two or more are halogen atoms, or all of them may be halogen atoms. It is preferred that at least one of X ¹⁰ and X ¹¹ is a halogen atom, and it is more preferred that both X ¹⁰ and X ¹¹ are halogen atoms.

Preferably, at least one of X ¹³ to X ¹⁶ is a halogen atom, more preferably two or more are halogen atoms, or all of them may be halogen atoms. It is preferred that at least one of X ¹⁴ and X ¹⁵ is a halogen atom, and it is more preferred that both X ¹⁴ and X ¹⁵ are halogen atoms.

Y ¹ and Y ² may be the same as or different from each other. From the viewpoint of easy synthesis of the quinoline yellow compound, it is preferably the same as each other.

式（1-i）及式（1-ii）中，X¹ ～X¹⁶ 、Y¹ 、Y² 及Z如上所述。In addition, tautomers of structures such as the following formula (1-i) and formula (1-ii) exist in the structure of formula (1), and the quinoline yellow compound may be any of these structures.

In formula (1-i) and formula (1-ii), X ¹ to X ¹⁶ , Y ¹ , Y ² and Z are as described above.

Hereinafter, specific examples of the above-mentioned quinoline yellow compound are given, but the above-mentioned quinoline yellow compound is not limited to these.

The quinoline yellow compound may be used alone, or two or more compounds may be appropriately selected and used in combination.

The production method of the above-mentioned quinoline yellow compound is not particularly limited, and can be suitably produced by a previously known method. Hereinafter, one aspect of the method for producing the quinoline yellow compound is described, but the method of production is not limited thereto.

The above-mentioned quinoline yellow compound can be obtained, for example, by a method including the following step I, step II, step III, and step IV.

式（A-1）中，Y¹ 、Y² 及Z如上所述。<Step I> First, by the method described in J. Heterocyclic, Chem, 30, 17 (1993), etc., add 2 to 3 equivalents of crotonaldehyde relative to the addition of 1 equivalent of bisaniline (Bisaniline), in In the presence of an oxidizing agent, the compound of formula (A-1) is synthesized by reacting it in a strong acid.

In formula (A-1), Y ¹ , Y ² and Z are as described above.

Examples of strong acids include hydrochloric acid, sulfuric acid, and nitric acid. Examples of the oxidizing agent include sodium iodide, tetrachloro-p-benzoquinone, and nitrobenzene.

Regarding Step I, the reaction temperature may be 80°C to 100°C, preferably 90°C to 100°C; the reaction time may be 1 hour to 6 hours, preferably 3 hours to 6 hours.

式（A-2）中，Y¹ 、Y² 及Z如上所述。<Step II> Furthermore, the compound of formula (A-2) can be obtained by reacting the obtained compound of formula (A-1) with nitric acid or fuming nitric acid in the presence of concentrated sulfuric acid.

In formula (A-2), Y ¹ , Y ² and Z are as described above.

Regarding step II, the reaction temperature may be -20°C to 70°C, preferably 0°C to 50°C; the reaction time may be 1 hour to 4 hours, preferably 1 hour to 3 hours.

式（A-3）中，Y¹ 、Y² 及Z如上所述。<Step III> Furthermore, the compound of formula (A-3) can be obtained by adding 6 to 8 equivalents of reduced iron to 1 equivalent of the obtained compound of formula (A-2) and allowing it to react. .

In formula (A-3), Y ¹ , Y ² and Z are as described above.

Regarding step III, the reaction temperature may be 60°C to 80°C, preferably 70°C to 80°C; the reaction time may be 1 hour to 3 hours, preferably 2 hours to 3 hours.

<Step IV> Furthermore, by the method described in Japanese Patent Laid-Open No. 2013-61622, etc., 4 to 6 equivalents of a compound selected from the group consisting of phthalic anhydride and halogen are added with respect to 1 equivalent of the obtained compound of formula (A-3) Substituting at least one of the group consisting of phthalic anhydride and reacting in the presence of an acid catalyst, the compound of formula (1) can be obtained. Examples of acid catalysts include benzoic acid and zinc chloride.

Regarding Step IV, the reaction temperature may be 180°C to 250°C, preferably 210°C to 250°C; the reaction time may be 1 hour to 8 hours, preferably 3 hours to 8 hours.

The phthalocyanine aluminum compound is at least one selected from the group consisting of a compound represented by the following formula (2A) and a compound represented by the following formula (2B).

In the formula (2A), X ⁵¹ to X ⁵⁴ are each independently an optionally substituted alkyl group, an optionally substituted aryl group, a substituted cycloalkyl group, a substituted heterocyclic group, or An alkoxy group having a substituent, an aryloxy group having a substituent, an alkylthio group having a substituent, or an arylthio group having a substituent. Examples of the "substituent" in these groups include halogen atoms, amine groups, hydroxyl groups, and nitro groups.

Examples of the "alkyl group" of the alkyl group which may have a substituent include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tertiary butyl, neopentyl, n-hexyl, and n Linear or branched alkyl groups such as octyl, stearyl, 2-ethylhexyl. Examples of the "alkyl group having a substituent" include trichloromethyl, trifluoromethyl, 2,2,2-trifluoroethyl, 2,2-dibromoethyl, 2,2,3,3 -Tetrafluoropropyl, 2-ethoxyethyl, 2-butoxyethyl, 2-nitropropyl, benzyl, 4-methylbenzyl, 4-tert-butylbenzyl, 4- Methoxybenzyl, 4-nitrobenzyl, 2,4-dichlorobenzyl, etc.

Examples of the "aryl group" of the aryl group which may have a substituent include phenyl, naphthyl, and anthracenyl. Examples of the "aryl group having a substituent" include p-methylphenyl, p-bromophenyl, p-nitrophenyl, p-methoxyphenyl, 2,4-dichlorophenyl, and pentafluorophenyl , 2-aminophenyl, 2-methyl-4-chlorophenyl, 4-hydroxy-1-naphthyl, 6-methyl-2-naphthyl, 4,5,8-trichloro-2-naphthalene Group, anthraquinone group, 2-amino anthraquinone group, etc.

Examples of the "cycloalkyl group" of the cycloalkyl group which may have a substituent include cyclopentyl group, cyclohexyl group, and adamantyl group. Examples of "cycloalkyl having a substituent" include 2,5-dimethylcyclopentyl and 4-tertiary butylcyclohexyl.

啉基、吖啶基等。作為「具有取代基之雜環基」，可列舉：3-甲基吡啶基、N-甲基哌啶基、N-甲基吡咯基等。Examples of the "heterocyclic group" of the heterocyclic group which may have a substituent include pyridyl, pyrazyl, piperidinyl, piperanyl, and N-

Porphyrinyl, acridinyl, etc. Examples of the "heterocyclic group having a substituent" include 3-methylpyridyl, N-methylpiperidyl, and N-methylpyrrolyl.

Examples of the "alkoxy" of the alkoxy group which may have a substituent include methoxy, ethoxy, propoxy, isopropoxy, n-butoxy, isobutoxy, tertiary butoxy Straight-chain or branched-chain alkoxy groups such as alkyl, neopentyloxy, 2,3-dimethyl-3-pentyloxy, n-hexyloxy, n-octyloxy, stearyloxy, 2-ethylhexyloxy base. Examples of the "alkoxy group having a substituent" include trichloromethoxy, trifluoromethoxy, 2,2,2-trifluoroethoxy, 2,2,3,3-tetrafluoropropoxy Group, 2,2-ditrifluoromethylpropoxy, 2-ethoxyethoxy, 2-butoxyethoxy, 2-nitropropoxy, benzyloxy, etc.

Examples of the "aryloxy group" of the aryloxy group which may have a substituent include phenoxy group, naphthyloxy group and anthraceneoxy group. Examples of "aryloxy groups having substituents" include p-methylphenoxy, p-nitrophenoxy, p-methoxyphenoxy, 2,4-dichlorophenoxy, and pentafluorophenoxy Group, 2-methyl-4-chlorophenoxy, etc.

Examples of the "alkylthio group" of the alkylthio group which may have a substituent include methylthio, ethylthio, propylthio, butylthio, pentylthio, hexylthio, octylthio, and decylthio , Dodecanethio, octadecylthio, etc. Examples of "alkylthio having a substituent" include methoxyethylthio, aminoethylthio, benzylaminoethylthio, methylcarbonylaminoethylthio, and phenylcarbonylaminoethyl Sulfur-based.

Examples of the "arylthio group" of the arylthio group which may have a substituent include phenylthio, 1-naphthylthio, 2-naphthylthio, 9-anthracenethio and the like. Examples of the "arylthio group having a substituent" include chlorophenylthio, trifluoromethylphenylthio, cyanophenylthio, nitrophenylthio, 2-aminophenylthio, and 2-hydroxy Phenylthio etc.

In formula (2A), Y ⁵¹ to Y ⁵⁴ are each independently a halogen atom, a nitro group, or a phthalimide methyl group which may have a substituent (C ₆ H ₄ (CO) ₂ N-CH ₂ -) , Or may have a substituent sulfamoyl group (H ₂ NSO ₂ -). The phthalimide methyl group having a substituent is a group obtained by substituting the hydrogen atom in the phthalimide methyl group by a substituent. A sulfamoyl group having a substituent is a group obtained by replacing a hydrogen atom in the sulfamoyl group with a substituent. The "substituent" in each of these groups is the same as the substituent described for X ⁵¹ to X ⁵⁴ .

Y ⁵¹ to Y ^{54 are} preferably halogen atoms. The halogen atom is selected from a fluorine atom, a chlorine atom, a bromine atom and an iodine atom, preferably a chlorine atom or a bromine atom, more preferably a bromine atom.

In formula (2A), L ¹ is a hydroxyl group, a chlorine atom, -OP(=O)R ¹ R ² , or -O-SiR ³ R ⁴ R ⁵ . R ¹ to R ⁵ are each independently a hydrogen atom, a hydroxyl group, an alkyl group that may have a substituent, an aryl group that may have a substituent, an alkoxy group that may have a substituent, or an aryloxy group that may have a substituent. R ¹ and R ² may be bonded to each other to form a ring, and two of R ³ , R ⁴ and R ⁵ may also be bonded to each other to form a ring.

Examples of the alkyl group in R ¹ to R ⁵ include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tertiary butyl, neopentyl, n-hexyl, n-octyl, Linear or branched alkyl groups such as stearyl and 2-ethylhexyl. Examples of the substituted alkyl group in R ¹ to R ⁵ include trichloromethyl, trifluoromethyl, 2,2,2-trifluoroethyl, 2,2-dibromoethyl, and 2- Ethoxyethyl, 2-butoxyethyl, 2-nitropropyl, benzyl, 4-methylbenzyl, 4-tert-butylbenzyl, 4-methoxybenzyl, 4- Nitrobenzyl, 2,4-dichlorobenzyl, etc.

Examples of the aryl group in R ¹ to R ⁵ include phenyl, naphthyl, and anthracenyl. Examples of the substituted aryl group in R ¹ to R ⁵ include p-tolyl, p-bromophenyl, p-nitrophenyl, p-methoxyphenyl, 2,4-dichlorophenyl, and penta Fluorophenyl, 2-dimethylaminophenyl, 2-methyl-4-chlorophenyl, 4-methoxy-1-naphthyl, 6-methyl-2-naphthyl, 4,5, 8-Trichloro-2-naphthyl, anthraquinone, etc.

Examples of the alkoxy group in R ¹ to R ⁵ include methoxy, ethoxy, propoxy, isopropoxy, n-butoxy, isobutoxy, tertiary butoxy, and neopentyl Straight-chain or branched-chain alkoxy groups such as oxy, 2,3-dimethyl-3-pentyloxy, n-hexyloxy, n-octyloxy, stearyloxy, 2-ethylhexyloxy and the like. Examples of the substituted alkoxy group in R ¹ and R ² include trichloromethoxy, trifluoromethoxy, 2,2,2-trifluoroethoxy, 2,2,3, 3-tetrafluoropropoxy, 2,2-ditrifluoromethylpropoxy, 2-ethoxyethoxy, 2-butoxyethoxy, 2-nitropropoxy, benzyloxy Wait.

Examples of the aryloxy group in R ¹ to R ⁵ include phenoxy group, naphthyloxy group, and anthracenyloxy group. Examples of the aryloxy group having a substituent in R ¹ to R ⁵ include p-methylphenoxy, p-nitrophenoxy, p-methoxyphenoxy, and 2,4-dichlorophenoxy , Pentafluorophenoxy, 2-methyl-4-chlorophenoxy, etc.

From the viewpoint of excellent heat resistance and light resistance, L ^{1 is} preferably -OP(=O)R ¹ R ² . In this case, R ¹ and R ² are each independently preferably an aryl group which may have a substituent or an aryloxy group which may have a substituent, more preferably an aryl group or an aryloxy group, and further preferably a phenyl group or Phenoxy. It is preferred that both R ¹ and R ² are an aryl group which may have a substituent or an aryloxy group which may have a substituent, and it is more preferred that both R ¹ and R ² are an aryl group or an aryloxy group. Preferably, both R ¹ and R ² are phenyl or phenoxy.

In formula (2A), m1 to m4 and n1 to n4 are each independently an integer of 0 to 4, and m1+n1, m2+n2, m3+n3, and m4+n4 are each independently an integer of 0 to 4. In one embodiment, the total of m1 to m4 may be 5 or more, 7 or more, or 9 or more, and may be 15 or less, 13 or less, or 11 or less. In another embodiment, m1 to m4 may all be 0. Preferably, all n1 to n4 are 0.

In formula (2B), X ⁵⁵ to X ⁶² are each independently an optionally substituted alkyl group, an optionally substituted aryl group, a optionally substituted cycloalkyl group, a optionally substituted heterocyclic group, or An alkoxy group having a substituent, an aryloxy group having a substituent, an alkylthio group having a substituent, or an arylthio group having a substituent. The "substituent" in each of these groups is the same as the substituent described for X ⁵¹ to X ⁵⁴ . The specific examples of these bases are the same as the specific examples of the bases described with respect to X ⁵¹ to X ⁵⁴ .

In formula (2B), Y ⁵⁵ to Y ⁶² are each independently a halogen atom, a nitro group, or a phthalimide methyl group which may have a substituent (C ₆ H ₄ (CO) ₂ N-CH ₂ -) , Or may have a substituent sulfamoyl group (H ₂ NSO ₂ -). The "substituent" in each of these groups is the same as the substituent described for X ⁵¹ to X ⁵⁴ . The specific examples of these bases are the same as the specific examples of the bases described with respect to Y ⁵¹ to Y ⁵⁴ .

In formula (2B), L ² is -O-SiR ⁶ R ⁷ -O-, -O-SiR ⁸ R ⁹ -O-SiR ¹⁰ R ¹¹ -O-, or -OP(=O)R ¹² -O- . R ⁶ to R ¹² are each independently a hydrogen atom, a hydroxyl group, an alkyl group that may have a substituent, an aryl group that may have a substituent, an alkoxy group that may have a substituent, or an aryloxy group that may have a substituent. Specific examples of the groups in R ⁶ to R ¹² are the same as the specific examples of the groups described for R ¹ to R ⁵ .

In formula (2B), m5 to m12 and n5 to n12 are each independently an integer of 0 to 4, and m5 + n5, m6 + n6, m7 + n7, m8 + n8, m9 + n9, m10 + n10, m11 + n11, and m12 + n12 are each independently an integer of 0 to 4. In one embodiment, the total of m5 to m12 may be 9 or more, 14 or more, or 19 or more, and may be 31 or less, 26 or less, or 21 or less. In another embodiment, m5 to m12 may all be 0. Preferably, all n5 to n12 are 0.

The above-mentioned quinoline yellow compounds can exhibit properties as organic pigments. Quinoline yellow compounds can be pigmented and blended. Similarly, the above-mentioned phthalocyanine aluminum compound can exhibit the properties as an organic pigment, and can be blended by pigmentation. As an example of such a phthalocyanine aluminum pigment, C.I. Pigment Green 63 can be cited. That is, the pigment composition of the present embodiment may contain a pigment composed of the quinoline yellow compound (quinoline yellow pigment) and a pigment composed of the phthalocyanine aluminum compound (phthalocyanine aluminum pigment).

The pigmentation of each of the quinoline yellow compound and the aluminum phthalocyanine compound may be carried out by a well-known method. The quinoline yellow pigment and the phthalocyanine aluminum pigment can be miniaturized by, for example, salt milling treatment or the like, and surface treatments such as rosin treatment, surfactant treatment, solvent treatment, and resin treatment can also be performed.

The content ratio of the quinoline yellow compound (quinoline yellow pigment) and the phthalocyanine aluminum compound (phthalocyanine aluminum pigment) in the pigment composition is appropriately determined according to the type of phthalocyanine aluminum compound or the desired hue (chroma). The content of the quinoline yellow compound (quinoline yellow pigment) is 100 parts by mass relative to the total amount of the quinoline yellow compound (quinoline yellow pigment) and the phthalocyanine aluminum compound (phthalocyanine aluminum pigment), for example, it may be 1 part by mass or more. It may be 95 parts by mass or less. From the viewpoint of being particularly suitable for use in green color filters with high color reproducibility, it is preferably 5 parts by mass or more, more preferably 10 parts by mass or more, and preferably It is 90 parts by mass or less, more preferably 85 parts by mass or less.

The pigment composition may further contain components other than the above. For example, the pigment composition may further contain organic pigments, organic dyes, organic pigment derivatives, etc. other than the above.

Examples of organic pigments other than the above include azo pigments, disazo pigments, methine azo pigments, anthraquinone pigments, and quinoline yellow pigments other than the above quinoline yellow pigments. Quinacridone pigments, diketopyrrolopyrrole pigments, dioxopyrrolopyrrole pigments, benzimide pigments, benzimidazolone pigments, phthalocyanine pigments other than the above phthalocyanine aluminum pigments, isoindoline pigments, Isoindolinone pigments, perylene pigments, etc. The organic pigment is preferably an azo pigment, a methine azo pigment, a quinoline yellow pigment other than the quinoline yellow pigment, a phthalocyanine pigment other than the phthalocyanine aluminum pigment, and isoindolin Pigments, etc., specifically CI Pigment Yellow 129, CI Pigment Yellow 138, CI Pigment Yellow 139, CI Pigment Yellow 150, CI Pigment Yellow 185, CI Pigment Yellow 231, CI Pigment Green 7, CI Pigment Green 36, CI Pigment Green 58, CI Pigment Green 59, CI Pigment Green 62, etc.

系染料、偶氮系染料、雙偶氮染料、蒽醌系染料、喹啉黃系染料、三芳基甲烷系染料、次甲基系染料、酞青系染料、玫瑰紅系染料等。有機染料較佳為酞青系染料。Examples of organic dyes include: 𠮿

Dye, azo dye, disazo dye, anthraquinone dye, quinoline yellow dye, triarylmethane dye, methine dye, phthalocyanine dye, rose red dye, etc. The organic dye is preferably a phthalocyanine dye.

The organic pigment derivative may be, for example, a derivative in which a part of a known organic pigment is modified (substituted) by a sulfonic acid group, a carboxyl group, an amine group, orthophthalimide methyl group, or the like. Specifically, for example, Solsperse (registered trademark name) 5000, Solsperse 12000, Solsperse 22000 (manufactured by Lubrizol Co., Ltd.), etc. may be mentioned. The content of the organic pigment derivative may be 1 part by mass or more and 20 parts by mass or less relative to 100 parts by mass of the total pigment.

The pigment composition may further contain resins such as photosensitive resins and curable resins, rosin, surfactants, dispersants, and the like. These ingredients can be used to treat the surface of the pigment (so-called surface treatment) or not. As a method of treating the surface of the pigment, there may be a method of temporarily dissolving the components in the solvent and depositing them on the surface of the pigment, or a method of adding the components to the kneader and mixing with the pigment, or a solvent A well-known method such as a method of adsorbing these components on the surface of the pigment.

The pigment composition may be in powder form. By dispersing the pigment composition in a solvent, a colored composition as a pigment dispersion can be formed.

(Coloring composition) The coloring composition of one embodiment contains the quinoline yellow compound, the phthalocyanine aluminum compound, and a solvent.

The aspect or the ratio of the quinoline yellow compound and the aluminum phthalocyanine compound in the coloring composition may be the same as the aspect or the ratio of the quinoline yellow compound and the aluminum phthalocyanine compound in the pigment composition, respectively.

The solvent is preferably an organic solvent. Examples of the organic solvent include aromatic solvents such as toluene, xylene, and methoxybenzene; acetates such as ethyl acetate or butyl acetate, propylene glycol monomethyl ether acetate, and propylene glycol monoethyl ether acetate. Solvents; Propionate solvents such as ethoxyethyl propionate; Alcohol solvents such as methanol and ethanol; Ethers such as butylcellulose, propylene glycol monomethyl ether, diethylene glycol ether, diethylene glycol dimethyl ether, etc. Solvents; methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone and other ketone solvents; hexane and other aliphatic hydrocarbon solvents; N,N-dimethylformamide, γ-butyramidine , N-methyl-2-pyrrolidone, aniline, pyridine and other nitrogen compound solvents; γ-butyrolactone and other lactone solvents; such as a 48:52 mixture of methyl carbamate and ethyl carbamate amine Formate, etc. The organic solvent is preferably a polar and water-soluble solvent, and more preferably a propionate-based solvent, an alcohol-based solvent, an ether-based solvent, a ketone-based solvent, a nitrogen compound-based solvent, or a lactone-based solvent.

The content of the solvent can be 300 parts by mass relative to 100 parts by mass of the above-mentioned quinoline yellow compound (quinoline yellow pigment) and phthalocyanine aluminum compound (phthalocyanine aluminum pigment) (hereinafter, referred to as "total amount of pigment") More than 2000 parts by mass.

From the viewpoint of preferably dispersing the quinoline yellow pigment and the aluminum phthalocyanine pigment in the solvent, the coloring composition may further contain a dispersant and/or an organic pigment derivative.

Examples of the dispersant include: ANTI-TERRA (registered trademark name) U/U100, ANTI-TERRA 204, DISPERBYK (registered trademark name) 106, DISPERBYK 108, DISPERBYK 109, DISPERBYK 112, DISPERBYK 130, DISPERBYK 140, DISPERBYK 142 , DISPERBYK 145, DISPERBYK 161, DISPERBYK 162, DISPERBYK 163, DISPERBYK 164, DISPERBYK 167, DISPERBYK 168, DISPERBYK 180, DISPERBYK 182, DISPERBYK 183, DISPERBYK 184, DISPERBYK 185, DISPERBYK 2000, DISPERBYK 2001, PERPERK 2001DIS, 2013, DISPERBYK 2022, DISPERBYK 2025, DISPERBYK 2026, DISPERBYK 2050, DISPERBYK 2055, DISPERBYK 2150, DISPERBYK 2155, DISPERBYK 2163, DISPERBYK 2164, DISPERBYK 9076, DISPERBYK 9077, BYK LPN-6919, BYK LPN-21116, BYK L-21-21, BYK L-21-21 BYK LPN-22102 (made by BYK-Chemie Co., Ltd.), EFKA (registered trademark name) 46, EFKA 47, EFKA 4010, EFKA 4020, EFKA 4320, EFKA 4300, EFKA 4330, EFKA 4401, EFKA 4570, EFKA 5054, EFKA 7461, EFKA 7462, EFKA 7476, EFKA 7477 (manufactured by BASF Corporation), Ajisper (registered trademark name) PB814, Ajisper 821, Ajisper 822, Ajisper 881 (manufactured by Ajinomoto Fine-Techno.Co. Inc.), Solsperse (registered Brand name) 24000, Solsperse 28000, Solsperse 37500, Solsperse 76500 (manufactured by Lubrizol Co., Ltd.), etc. The content of the dispersant may be 10 parts by mass or more and 120 parts by mass or less relative to 100 parts by mass of the total pigment.

The coloring composition may further contain a photosensitive resin. The coloring composition containing the photosensitive resin may also be called a photosensitive coloring composition. Examples of the photosensitive resin include urethane resins, acrylic resins, polyamic acid resins, polyimide resins, styrene maleic resins, and styrene maleic anhydride resins. And other thermoplastic resins; or for example: such as 1,6-hexanediol diacrylate, ethylene glycol diacrylate, neopentyl glycol diacrylate, triethylene glycol diacrylate, bis (acryloyloxyethoxy) Group) Bifunctional monomers such as bisphenol A, 3-methylpentanediol diacrylate; such as trimethylolpropane triacrylate, neopentyl tetraacrylate, isocyanuric acid ginseng (2-propene Photopolymerizable monomers such as polyfunctional monomers such as acetyloxyethyl ester, dipentaerythritol hexaacrylate, dipentaerythritol pentaacrylate, etc.

、1,3-雙(4'-疊氮基苯亞甲基)-2-丙烷、1,3-雙(4'-疊氮基苯亞甲基)-2-丙烷-2'-磺酸、4,4'-二疊氮茋-2,2'-二磺酸等。The photosensitive coloring composition may further contain a photopolymerization initiator. Examples of the photopolymerization initiator include acetophenone, benzophenone, benzyl dimethyl katal, benzyl peroxide, and 2-chloro-9-oxysulfur.

, 1,3-bis(4'-azidobenzylidene)-2-propane, 1,3-bis(4'-azidobenzylidene)-2-propane-2'-sulfonic acid , 4,4'-Diazide-2,2'-disulfonic acid, etc.

When the coloring composition contains a photosensitive resin (further containing a photopolymerization initiator), the coloring composition can be obtained, for example, by the following method. First, if necessary, the quinoline yellow pigment and the aluminum phthalocyanine pigment are dispersed in a solvent together with a dispersant and/or an organic pigment derivative to obtain a dispersion liquid. Next, a photosensitive resin (further addition of a photopolymerization initiator) was added to this dispersion liquid, and after further adding a solvent as necessary, it was stirred uniformly, thereby obtaining a colored composition.

In this case, the content of the photosensitive resin may be 3 parts by mass or more and 25 parts by mass or less with respect to 100 parts by mass of the dispersion liquid. The content of the photopolymerization initiator may be 0.05 parts by mass or more and 3 parts by mass or less with respect to 1 part by mass of the photosensitive resin.

By using the pigment composition or coloring composition described above, a green color filter (green pixel portion of the color filter) with high brightness and high color reproducibility even if it is a thin film can be obtained. The inventors speculate that the reason is as follows.

In order to obtain a green color filter with high color reproducibility, it is necessary that the yellow pigment is in a blue region where light is not absorbed (transmitted) by the blue pigment or the green pigment used together, preferably in a wider wavelength range To absorb light, in the past, by increasing the content of yellow pigment, the light absorption of yellow pigment in the blue region increased. However, in this case, there is a problem that the brightness decreases and the film thickness becomes thick. On the other hand, the compound represented by the formula (1) has a structure obtained by dimerizing the quinoline yellow skeleton. Therefore, compared with the conventional yellow pigment, the quinoline yellow pigment has a widening in the blue region to Absorption spectrum on the longer wavelength side. Therefore, even without increasing the content of quinoline yellow pigment, it can be toned to a high degree of green for color reproduction. Therefore, in the green color filter, even if it is a thin film, high color reproducibility can be achieved, and higher brightness can also be achieved.

Therefore, the coloring composition is preferable as the coloring composition for the color filter (for forming the color filter), and is particularly preferable as the coloring composition for forming the green color filter (the green pixel portion of the color filter) good.

(Color filter) An embodiment of the present invention is a color filter having a pixel portion formed of the above-mentioned colored composition. In other words, the color filter of one embodiment has a pixel portion containing the quinoline yellow compound and the aluminum phthalocyanine compound. The pixel portion is preferably a green pixel portion.

The pixel portion can be easily formed from the coloring composition (photosensitive coloring composition). As a specific method, for example, there is a method called photoetching method in which a coloring composition (photosensitive coloring composition) is applied to the coloring composition (photosensitive coloring composition) by a spin coating method, a roll coating method, an inkjet method, or the like On a transparent substrate such as glass, the coating film is then exposed to a pattern using ultraviolet rays through a photomask, and the unexposed portion is washed with a solvent or the like to obtain a colored pattern.

The method for forming the pixel portion is not particularly limited. For example, the color filter can be manufactured by forming the pattern of the pixel portion by the electrodeposition method, the transfer method, the cell electrolysis method, or the PVED (Photovoltaic Electrodeposition) method.

In the above embodiment (pigment composition and coloring composition), the quinoline yellow compound and the aluminum phthalocyanine compound are contained in one composition, and in another embodiment, the quinoline yellow compound and the aluminum phthalocyanine compound are included They can be included in different compositions. That is, another embodiment of the present invention is a pigment composition group (coloring composition group) comprising: a first pigment composition (coloring composition) containing the quinoline yellow compound, and an aluminum phthalocyanine compound The second pigment composition (coloring composition). The pigment composition group (coloring composition group) is also preferably used to form a color filter, and is particularly preferably used to form a green color filter (green pixel portion of the color filter). Examples

Hereinafter, the present invention will be further specifically described based on examples, but the present invention is not limited to the following examples.

¹ H-NMR (CDCl₃ ) δppm: 2.81 (s, 6H), 4.24 (s, 2H), 7.34 (d, J=8.0 Hz, 2H), 7.49 (s, 2H), 7.67 (s, 2H), 7.99 (d, J=8.8 Hz, 2H)¹³ C-NMR (CDCl₃ ) δppm: 25.8, 41.1, 123.2, 126.2, 127.8, 130.9, 133.1, 136.3, 137.6, 143.1, 160.0 FT-IR cm^-1 : 3435, 3054, 3030, 2915, 1603, 1487, 1206 FD-MS: 366M+[Synthesis Example 1] 4,4'-methylenebis(2-chloroaniline) 5.0 g (56.1 mmol), tetrachloro-p-benzoquinone 27.6 g (112 mmol), water 150 ml, and concentrated hydrochloric acid 150 were added to the flask ml, n-butanol 100 ml, and stir at 95°C for 30 minutes. To this mixture, 11.8 g (168 mmol) of crotonaldehyde dissolved in 12 ml of n-butanol was added dropwise, followed by stirring for 1 hour. The temperature was lowered to 80°C, and 15.3 g (112 mmol) of zinc chloride was gradually added in small amounts, 200 ml of THF was added, and the mixture was stirred at 80°C for 1 hour. After leaving to cool to room temperature, the yellow ochre powder was recovered by filtration under reduced pressure. The obtained yellow ochre powder was washed with 200 ml of THF, and the yellow ochre powder was recovered by filtration under reduced pressure again. Furthermore, the obtained yellow ochre powder was transferred to a flask, 200 ml of water and 40 ml of 28% ammonia water were added, and it stirred at room temperature for 2 hours. The powder was recovered by filtration under reduced pressure to obtain 20.3 g of crude product. The obtained crude product was dissolved in toluene, and insoluble materials were removed by filtration and then recrystallized to obtain 12.6 g of intermediate (4) (yield: 61%).

¹ H-NMR (CDCl ₃ ) δppm: 2.81 (s, 6H), 4.24 (s, 2H), 7.34 (d, J=8.0 Hz, 2H), 7.49 (s, 2H), 7.67 (s, 2H), 7.99 (d, J=8.8 Hz, 2H) ¹³ C-NMR (CDCl ₃ ) δppm: 25.8, 41.1, 123.2, 126.2, 127.8, 130.9, 133.1, 136.3, 137.6, 143.1, 160.0 FT-IR cm ^-1 : 3435 , 3054, 3030, 2915, 1603, 1487, 1206 FD-MS: 366M+

¹ H-NMR (CDCl₃ ) δppm: 2.86 (s, 6H), 4.27 (s, 2H), 7.56 (d, J=8.8 Hz, 2H), 7.62 (s, 2H), 8.08 (d, J=8.8 Hz, 2H)¹³ C-NMR (CDCl₃ ) δppm: 25.7, 32.4, 119.9, 125.6, 127.5, 130.1, 131.1, 137.3, 143.1, 145.9, 162.2 FT-IR cm^-1 : 3465, 1604, 1530, 1487, 1362Then, 4.15 g (11.3 mmol) of intermediate (4) and 7.55 mL of concentrated sulfuric acid were added to the flask, and stirred at 45° C. for 20 minutes. Thereafter, 1.62 mL of fuming nitric acid was added dropwise, maintaining the temperature and stirring continued for 1 hour. After leaving to cool, slowly inject 250 mL of ice water into the system. Furthermore, the pH was adjusted to 8-9 using 10 wt% sodium hydroxide aqueous solution. The precipitated powder was recovered by filtration under reduced pressure, and washed with 200 mL of distilled water and 100 mL of ethanol, thereby obtaining an intermediate (5) 4.86 g (10.6 mmol) (yield: 94%).

¹ H-NMR (CDCl ₃ ) δppm: 2.86 (s, 6H), 4.27 (s, 2H), 7.56 (d, J=8.8 Hz, 2H), 7.62 (s, 2H), 8.08 (d, J=8.8 Hz, 2H) ¹³ C-NMR (CDCl ₃ ) δppm: 25.7, 32.4, 119.9, 125.6, 127.5, 130.1, 131.1, 137.3, 143.1, 145.9, 162.2 FT-IR cm ^-1 : 3465, 1604, 1530, 1487, 1362

¹ H-NMR (CDCl₃ ) δppm: 2.65 (s, 6H), 3.97 (s, 2H), 5.92 (s, 4H), 7.32 (s, 2H), 7.38 (d, J=8.8 Hz, 2H), 8.59 (d, J=8.8 Hz, 2H)¹³ C-NMR (CDCl₃ ) δppm: 25.4, 31.9, 116.8, 117.7, 117.9, 121.0, 131.8, 132.2, 142.0, 143.1, 158.9 FT-IR cm^-1 : 3476, 3373, 1627, 1605, 1409, 1359, 1250Then, 5.00 g (10.9 mmol) of intermediate (5) and 23.3 mL of ethanol were added to the flask, and stirred at room temperature for 10 minutes. Thereafter, 4.88 g (87.4 mmol) of reduced iron was added to the system, and further stirred at room temperature for 10 minutes. Then, 6.33 mL of concentrated hydrochloric acid was added dropwise, the temperature was raised to 80°C, and stirring was continued for 6 hours. After leaving to cool, it was poured into 150 mL of distilled water, and the pH was adjusted to 9 using a 10% aqueous solution of sodium hydroxide. The precipitated powder was recovered by filtration under reduced pressure. Furthermore, the recovered powder was sufficiently stirred in 700 mL of ethyl acetate, and filtered under reduced pressure. Thus, by distilling off the solvent of the obtained filtrate under reduced pressure, 3.64 g (9.16 mmol) of intermediate (6) as a yellow ochre powder was obtained (yield: 84%).

¹ H-NMR (CDCl ₃ ) δppm: 2.65 (s, 6H), 3.97 (s, 2H), 5.92 (s, 4H), 7.32 (s, 2H), 7.38 (d, J=8.8 Hz, 2H), 8.59 (d, J=8.8 Hz, 2H) ¹³ C-NMR (CDCl ₃ ) δppm: 25.4, 31.9, 116.8, 117.7, 117.9, 121.0, 131.8, 132.2, 142.0, 143.1, 158.9 FT-IR cm ^-1 : 3476 , 3373, 1627, 1605, 1409, 1359, 1250

FT-IR cm^-1 : 3449, 1727, 1622, 1536, 1410, 1363, 1308, 1192, 1112, 737 FD-MS: 1467M+Then, under a nitrogen atmosphere, 14.1 g (116 mmol) of benzoic acid was measured in a flask and melted at 140°C. Intermediate (6) 1.44 g (3.62 mmol) and tetrachlorophthalic anhydride 5.53 g (19.3 mmol) were added thereto, and stirred at 220°C for 4 hours. After leaving to cool, 300 mL of acetone was added to the reaction solution, and after stirring for 1 hour, 4.52 g (3.08 mmol) of the target product (7) as a yellow powder was obtained by filtration under reduced pressure (yield: 85%).

FT-IR cm ^-1 : 3449, 1727, 1622, 1536, 1410, 1363, 1308, 1192, 1112, 737 FD-MS: 1467M+

¹ H-NMR (DMSO-d6) δppm: 2.70 (s, 6H), 4.42 (s, 2H), 7.58 (d, J=8.8 Hz, 2H), 7.63 (d, J=8.8 Hz, 2H), 8.09 (d, J=8.8 Hz, 2H), 8.13 (d, J=8.8 Hz, 2H)¹³ C-NMR (DMSO-d6) δppm: 24.5, 32.0, 117.7, 124.8, 127.5, 129.8, 130.5, 131.9, 145.8, 146.2, 160.7 FT-IR (KBr disk) cm^-1 : 3048, 1602, 1520, 1494, 1363[Synthesis Example 2] 55 g of concentrated sulfuric acid was added to the flask, stirred under ice-cooling, and the 6 obtained by the method described in the literature (Polymer, volume 39, No. 20 (1998), p4949) was simultaneously added. 6'-methylene diquinonidine 7.0 g (23.5 mmol). Keep the temperature below 10℃ and add 6.1 g of 60% nitric acid dropwise at the same time, and continue stirring at 10℃ to 20℃ for 1 hour. The reaction solution was poured into 150 ml of ice water, and the pH was adjusted to 3 using a 20 wt% sodium hydroxide aqueous solution. The precipitated powder was recovered by filtration under reduced pressure, and washed to neutrality with water. After the obtained solid was air-dried at 70°C, the crude product was washed and filtered with hot ethyl acetate 100 ml, followed by hot toluene 60 ml, and intermediate (8) 6.52 g (16.8 mmol) was obtained (yield: 72%).

¹ H-NMR (DMSO-d6) δppm: 2.70 (s, 6H), 4.42 (s, 2H), 7.58 (d, J=8.8 Hz, 2H), 7.63 (d, J=8.8 Hz, 2H), 8.09 (d, J=8.8 Hz, 2H), 8.13 (d, J=8.8 Hz, 2H) ¹³ C-NMR (DMSO-d6) δppm: 24.5, 32.0, 117.7, 124.8, 127.5, 129.8, 130.5, 131.9, 145.8 , 146.2, 160.7 FT-IR (KBr disk) cm ^-1 : 3048, 1602, 1520, 1494, 1363

¹ H-NMR (DMSO-d6) δ ppm: 2.57 (s, 6H), 3.45 (s, 2H), 5.66 (s, 4H), 7.06 (d, J=8.2 Hz, 2H), 7.16 (d, J=8.2 Hz, 2H), 7.23 (d, J=8.2 Hz, 2H), 8.49 (d, J=8.2 Hz, 2H)¹³ C-NMR (DMSO-d6) δ ppm: 24.6, 32.1, 115.8, 116.2, 119.5, 130.9, 131.8, 141.5, 147.4, 157.0 FT-IR (KBr disk) cm^-1 : 3464, 3363, 3315, 3192, 1640, 1591, 1573, 1415, 1365, 801Then, 5.30 g of reduced iron and 135 ml of acetic acid were added to the flask, stirred and heated to 50°C at the same time. Subsequently, 4.50 g (11.6 mmol) of the intermediate (8) was added so as to maintain the temperature at 70°C or lower. After the addition was completed, stirring was continued at 60°C for 1 hour, the reaction solution was cooled to below 35°C, poured into 500 ml of ice water, and the pH was adjusted to 9 with 20% NaOH water. The resulting precipitate was filtered on diatomaceous earth under reduced pressure. Collect the solid matter, dry it at 70°C, add it to a mixed solvent of 100 ml of dimethyl sulfite (DMSO) and 100 ml of N,N-dimethylformamide (DMF), and stir at 90°C for 1 hour. The mixture was filtered under diatomaceous earth under reduced pressure, and the obtained filtrate was stirred and simultaneously added to 1 L of water. The resulting precipitate was recovered by filtration under reduced pressure and washed with water to obtain intermediate (9) 3.80 g (11.6 mmol) (yield: >99%).

¹ H-NMR (DMSO-d6) δ ppm: 2.57 (s, 6H), 3.45 (s, 2H), 5.66 (s, 4H), 7.06 (d, J=8.2 Hz, 2H), 7.16 (d, J =8.2 Hz, 2H), 7.23 (d, J=8.2 Hz, 2H), 8.49 (d, J=8.2 Hz, 2H) ¹³ C-NMR (DMSO-d6) δ ppm: 24.6, 32.1, 115.8, 116.2, 119.5, 130.9, 131.8, 141.5, 147.4, 157.0 FT-IR (KBr disk) cm ^-1 : 3464, 3363, 3315, 3192, 1640, 1591, 1573, 1415, 1365, 801

FT-IR cm^-1 : 1788, 1729, 1688, 1638, 1607, 1537, 1420, 1310, 732 FD-MS: 1400M+Then, under a nitrogen atmosphere, 135 g of benzoic acid was measured in a flask and melted at 140°C. Intermediate (9) 3.80 g (11.6 mmol), tetrachlorophthalic anhydride 17.99 g (62.9 mmol) and anhydrous zinc chloride 0.49 g (3.6 mmol) were added thereto, and stirred at 220°C for 6 hours. After the reaction mixture was cooled to 120° C., 300 mL of chlorobenzene was added and stirred for 1 hour, and the target product (10) as a yellow powder (10.5 g (7.5 mmol)) was obtained by filtration under reduced pressure (yield: 65%).

FT-IR cm ^-1 : 1788, 1729, 1688, 1638, 1607, 1537, 1420, 1310, 732 FD-MS: 1400M+

[Synthesis Example 3] 130 mL of concentrated sulfuric acid was added to the flask, stirred and cooled to 10° C. or lower at the same time. 8.00 g (14.4 mmol) of aluminum hydroxyphthalocyanine obtained according to the method described in Japanese Patent Laid-Open No. 2012-247587 was added so as to be kept at 10°C or lower. Then, 21.4 g (74.7 mmol) of dibromoisocyanuric acid was added so as to maintain the temperature at 10°C or lower. Thereafter, it was stirred at room temperature for 7 hours. The reaction solution was added to water, and the precipitated solid was recovered by filtration under reduced pressure. The obtained solid was dispersed in a 2.5% aqueous solution of sodium hydroxide and stirred at 70°C for 1 hour. The solid was recovered by filtration under reduced pressure, and dried at 90° C. for 17 hours to obtain 9.20 g of intermediate (11) (yield: 47%). The average number of bromine substituents is 10.0, and the halogen distribution width is 9 (calculated based on the results of FD-MS).

Then, 6.00 g of intermediate (11), 2.20 g (8.7 mmol) of diphenyl phosphate, and 85 mL of N-methyl-2-pyrrolidone were added to the flask, and stirred at 90°C for 6 hours. The reaction liquid was added to methanol, and the precipitated solid was recovered by filtration under reduced pressure. The obtained solid was dispersed in water/methanol=1/1 and stirred at room temperature for 2 hours. The solid was recovered by filtration under reduced pressure, and dried at 90° C. for 17 hours to obtain 4.60 g of the target product (12) (yield: 65%). The average number of bromine substituents is 10.0, and the halogen distribution width is 9 (calculated based on the results of FD-MS).

¹ H-NMR (CDCl₃ ) δppm: 7.48 - 7.55 (1H), 7.61 (1H), 7.74 (1H), 7.81 - 7.95 (7H), 8.12 (1H), 8.19 - 8.23 (3H), 8.66 (2H), 8.81 (1H), 14,9 (1H) FD-MS: 519M+[Synthesis Example 4] In a nitrogen atmosphere, 24.4 g (200 mmol) of benzoic acid was measured in a flask and melted at 130°C. To this, 1.59 g (10.0 mmol) of 8-aminoquinadine and 1.98 g (10.0 mmol) of 2,3-naphthalenedicarboxylic anhydride were added, and the mixture was stirred at 180°C for 3 hours. Thereafter, 3.31 g of 2,3-naphthalenedicarboxylic anhydride and 1.36 g of zinc chloride were added, and the temperature was raised to 230°C, followed by stirring for 4 hours. After leaving to cool, 700 mL of acetone was added to the reaction solution, and after stirring for 1 hour, the yellow powder was recovered by filtration under reduced pressure. Then, the obtained powder was washed with 300 mL of methanol, and the intermediate (13) 5.00 g (9.64 mmol) as a yellow powder was obtained by filtration under reduced pressure (yield: 96%).

¹ H-NMR (CDCl ₃ ) δppm: 7.48-7.55 (1H), 7.61 (1H), 7.74 (1H), 7.81-7.95 (7H), 8.12 (1H), 8.19-8.23 (3H), 8.66 (2H) , 8.81 (1H), 14,9 (1H) FD-MS: 519M+

FD-MS: 338M+Then, 1.03 g (1.99 mmol) of intermediate (13) and 39 mL of ethanol were added to the flask, and stirred at room temperature for 3 minutes. Thereafter, 1.03 g (39.7 mmol) of hydrazine monohydrate was added to the system, which was heated to reflux for 23 hours while stirring. After leaving to cool, the powder was recovered by filtration under reduced pressure, and the filtrate was washed with 250 mL of acetone. Furthermore, it heated and refluxed in 50 mL of 10% sodium hydroxide aqueous solution, and it stirred at the same time for 1 hour. After that, it was filtered while heating at a stage where the temperature was lowered to around 40 to 50° C. to obtain 0.633 g (1.87 mmol) of intermediate (14) as a yellow powder (yield: 94%).

FD-MS: 338M+

Then, 4.13 g (12.2 mmol) of intermediate (14), 3.80 g (13.3 mmol) of tetrachlorophthalic anhydride, and 37.4 mL of trichlorobenzene were added to the flask, followed by heating and stirring at 200° C. for 5 hours. After leaving to cool, it was washed with 300 mL of acetone, and the target substance (15) as a yellow powder (5.92 g (9.76 mmol)) was obtained by filtration under reduced pressure (yield: 80%). FD-MS: 604M+

[Pigment Example 1] 5 parts by mass of quinoline yellow dimer (7) obtained in Synthesis Example 1, 50 parts by mass of crushed sodium chloride, and 8 parts by mass of diethylene glycol were added to a double-arm type kneader, and kneaded at 80°C. 8 hour. After kneading, the mixture was taken out to 6,000 parts by mass of water at 80° C. After stirring for 1 hour, it was filtered, washed with hot water, dried, and pulverized to obtain a quinoline yellow pigment as a yellow pigment. The quinoline yellow pigment obtained by using the transmission electron microscope JEM-2010 manufactured by Japan Electronics Corporation. For the 40 primary particles constituting the aggregate on the secondary image, the average aspect ratio is calculated from the average of the diameter of the longer side (long axis) and the diameter of the shorter side (short axis), and the average value of the long axis As the average primary particle size. The average aspect ratio is less than 3.00. The average primary particle size is below 100 nm.

[Pigmentation Example 2] The quinoline yellow dimer (10) obtained in Synthesis Example 2 was used instead of the quinoline yellow dimer (7) obtained in Synthesis Example 1, except that the pigmentation was carried out in the same manner as in Pigmentation Example 1 to obtain Quinoline yellow pigment. The average aspect ratio of the obtained pigment particles is less than 3.00, and the average primary particle size is 100 nm or less.

[Pigment Example 3] The quinoline yellow monomer (15) obtained in Synthesis Example 4 was used instead of the quinoline yellow dimer (7) obtained in Synthesis Example 1, except that the pigmentation was carried out in the same manner as in Pigmentation Example 1, The quinoline yellow pigment was obtained. The average aspect ratio of the obtained pigment particles is less than 3.00, and the average primary particle size is 100 nm or less.

之SEPR beads 22.0質量份，利用塗料振盪機（東洋精機股份有限公司製造）分散2個半小時，獲得顏料分散體。

[Manufacturing Example 1] 0.660 parts by mass of the quinoline yellow pigment obtained in Pigmentation Example 1 was put in a glass bottle, and the sulfur of CI Pigment Yellow 138 synthesized by the method described in Japanese Patent Laid-Open No. 2013-54200 was added. Acid derivative (16) 0.040 parts by mass, propylene glycol monomethyl ether acetate 12.60 parts by mass, BYK LPN-21116 (manufactured by BYK-Chemie Co., Ltd.) 1.400 parts by mass, 0.3 to 0.4 mm

22.0 parts by mass of SEPR beads were dispersed for 2 and a half hours using a paint shaker (manufactured by Toyo Seiki Co., Ltd.) to obtain a pigment dispersion.

Furthermore, 4.00 parts by mass of the obtained pigment dispersion, 0.600 parts by mass of acrylic resin solution UNIDIC (registered trademark) ZL-295 (manufactured by DIC Corporation), and 0.220 parts by mass of propylene glycol monomethyl ether acetate were charged into a glass bottle In the middle, shaking is performed to prepare a yellow toning composition.

[Production Example 2] The quinoline yellow pigment obtained in Pigmentation Example 2 was used instead of the quinoline yellow pigment obtained in Pigmentation Example 1, except that the composition for yellow toning was obtained in the same manner as in Production Example 1.

[Production Example 3] According to the method described in Japanese Patent Laid-Open No. 2013-87251, a blue-toning composition containing an aluminum phthalocyanine pigment containing unsubstituted phthalocyanine aluminum (17) was prepared.

[Production Example 4] Instead of unsubstituted phthalocyanine aluminum (17), the brominated phthalocyanine aluminum (12) obtained in Synthesis Example 3 was used, in the same manner as in Production Example 3, in accordance with Japanese Patent Laid-Open No. 2013-87251 The method described in the bulletin obtains a composition for green toning.

之SEPR beads 22.0質量份，利用塗料振盪機（東洋精機股份有限公司製造）分散2個半小時，獲得顏料分散體。進而，將所獲得之顏料分散體2.00質量份、ZL-295 0.490質量份、丙二醇單甲醚乙酸酯0.110質量份裝入至玻璃瓶中進行振盪，藉此製作黃色調色用組成物。[Production Example 5] 0.700 parts by mass of the quinoline yellow pigment obtained in Pigmentation Example 3 was put in a glass bottle, 6.42 parts by mass of propylene glycol monomethyl ether acetate, BYK LPN-6919 (BYK-Chemie Co., Ltd. limited 0.467 parts by mass, acrylic resin solution UNIDIC (registered trademark) ZL-295 (made by DIC Corporation) 0.700 parts by mass, 0.3～0.4 mm

22.0 parts by mass of SEPR beads were dispersed for 2 and a half hours using a paint shaker (manufactured by Toyo Seiki Co., Ltd.) to obtain a pigment dispersion. Furthermore, 2.00 parts by mass of the obtained pigment dispersion, 0.490 parts by mass of ZL-295, and 0.110 parts by mass of propylene glycol monomethyl ether acetate were charged into a glass bottle and shaken, thereby preparing a composition for yellow toning.

[Example 1] The yellow toning composition obtained in Production Example 1 and the blue toning composition obtained in Production Example 3 were added in such a manner that they became quinoline yellow pigment: aluminum phthalocyanine pigment (mass ratio) = 49:51. Mix to obtain a colored composition.

[Example 2] The yellow coloring composition obtained in Production Example 2 was used instead of the yellow coloring composition obtained in Production Example 1, except that the coloring composition was obtained in the same manner as in Example 1.

[Comparative Example 1] The yellow toning composition obtained in Production Example 5 was used in place of the yellow toning composition obtained in Production Example 1, so that the quinoline yellow pigment: phthalocyanine aluminum pigment (mass ratio) = 63:37. A coloring composition was obtained in the same manner as in Example 1 except that the coloring composition and the blue coloring composition were mixed.

<Evaluation of color filter characteristics> Each coloring composition obtained was coated on a glass substrate with a spin coater, dried, and heated at 230° C. for 1 hour to prepare a sample for evaluation that showed a predetermined green chromaticity when using C light source. In addition, as the green chromaticity, the green chromaticity (0.260, 0.650) in the color standard for high color reproduction used in Japanese Patent Laid-Open No. 2010-2550 is used. Chromaticity is a value measured by a spectrophotometer (U3900/3900H model manufactured by Hitachi High-Tech Science Corporation). The brightness Y of the obtained sample for evaluation was measured by a spectrophotometer (U3900/3900H model manufactured by Hitachi High-Tech Science Corporation). Furthermore, for the obtained evaluation sample, the thickness of the coloring film formed on the glass substrate was measured with a film thickness meter (VS1330 scanning white interference microscope manufactured by Hitachi High-Tech Science Corporation). Furthermore, it can be said that the thinner the film thickness, the higher the coloring power. The results are shown in Table 1.

[Table 1]

It can be seen that the quinoline yellow compound represented by formula (1) is used in comparison with Comparative Example 1 in which a conventional quinoline yellow compound (quinoline yellow monomer (15)) is used instead of the quinoline yellow compound represented by formula (1) Examples 1 and 2 of the combination of (quinoline yellow dimer (7) or (10)) and phthalocyanine aluminum compound (unsubstituted phthalocyanine aluminum (17)) are high brightness and high coloring power (can be thinner The film thickness is adjusted for high color reproduction greenness).

[Example 3] The green toning composition obtained in Manufacturing Example 4 was used instead of the blue toning composition obtained in Manufacturing Example 3 so as to become a quinoline yellow pigment: phthalocyanine aluminum pigment (mass ratio) = 27:73 A coloring composition was obtained in the same manner as in Example 1 except that the yellow toning composition and the blue toning composition were mixed.

[Example 4] The yellow coloring composition obtained in Production Example 2 was used instead of the yellow coloring composition obtained in Production Example 1, except that the coloring composition was obtained in the same manner as in Example 3.

[Comparative Example 2] The yellow toning composition obtained in Production Example 5 was used in place of the yellow toning composition obtained in Production Example 1 so as to become a quinoline yellow pigment: phthalocyanine aluminum pigment (mass ratio) = 39:61 A coloring composition was obtained in the same manner as in Example 3 except that the yellow toning composition and the blue toning composition were mixed.

<Evaluation of color filter characteristics> For each coloring composition obtained, the color filter characteristics were evaluated in the same manner as in Examples 1 to 2 and Comparative Example 1. The results are shown in Table 2.

[Table 2]

It can be seen that the quinoline yellow compound represented by formula (1) is used in comparison with Comparative Example 2 in which a conventional quinoline yellow compound (quinoline yellow monomer (15)) is used instead of the quinoline yellow compound represented by formula (1) Examples 3 and 4 of the combination of (quinoline yellow dimer (7) or (10)) and aluminum phthalocyanine compound (aluminum bromide phthalocyanine (12)) are high brightness and high tinting strength (thin film can be used) Thick toning is high color reproduction green).

no

no

Claims (3)

A pigment composition comprising: a quinoline yellow compound represented by the following formula (1), and a group selected from a compound represented by the following formula (2A) and a compound represented by the following formula (2B) At least one of the phthalocyanine aluminum compounds,

[In formula (1), X ¹ to X ¹⁶ are each independently a hydrogen atom or a halogen atom, Y ¹ and Y ² are each independently a hydrogen atom or a halogen atom, and Z is a C 1-3 alkylene group],

[In formula (2A), X ⁵¹ to X ⁵⁴ are each independently an optionally substituted alkyl group, an optionally substituted aryl group, a optionally substituted cycloalkyl group, and optionally substituted heterocyclic group, An alkoxy group which may have a substituent, an aryloxy group which may have a substituent, an alkylthio group which may have a substituent, or an arylthio group which may have a substituent, Y ⁵¹ to Y ⁵⁴ are each independently a halogen atom, nitrate Group, phthalimidomethyl group which may have a substituent, or sulfamoyl group which may have a substituent, L ¹ is a hydroxyl group, a chlorine atom, -OP(=O)R ¹ R ² , or -O -SiR ³ R ⁴ R ⁵ (R ¹ to R ⁵ are each independently a hydrogen atom, a hydroxyl group, an alkyl group which may have a substituent, an aryl group which may have a substituent, an alkoxy group which may have a substituent, or may have Aryloxy group of the substituent, and R ¹ and R ² may be bonded to each other to form a ring, and two of R ³ , R ⁴ and R ⁵ may also be bonded to each other to form a ring), m1～m4 and n1～n4 Each independently is an integer of 0 to 4, m1+n1, m2+n2, m3+n3 and m4+n4 are each independently an integer of 0-4],

[In the formula (2B), X ⁵⁵ to X ⁶² are each independently an optionally substituted alkyl group, an optionally substituted aryl group, a optionally substituted cycloalkyl group, and optionally substituted heterocyclic group, The alkoxy group which may have a substituent, the aryloxy group which may have a substituent, the alkylthio group which may have a substituent, or the arylthio group which may have a substituent, Y ⁵⁵ to Y ⁶² are each independently a halogen atom, nitrate Group, phthalimide methyl group which may have a substituent, or sulfamoyl group which may have a substituent, L ² is -O-SiR ⁶ R ⁷ -O-, -O-SiR ⁸ R ^9- O-SiR ¹⁰ R ¹¹ -O-, or -OP(=O)R ¹² -O-(R ⁶ to R ¹² are each independently a hydrogen atom, a hydroxyl group, an alkyl group that may have a substituent, and a substituent that may have a substituent Aryl, alkoxy which may have a substituent, or aryloxy which may have a substituent), m5 to m12 and n5 to n12 are each independently an integer of 0 to 4, m5 + n5, m6 + n6, m7 + n7, m8 + n8, m9 + n9, m10+n10, m11+n11 and m12+n12 are each independently an integer of 0 to 4]. A coloring composition comprising: a quinoline yellow compound represented by the following formula (1), selected from the group consisting of a compound represented by the following formula (2A) and a compound represented by the following formula (2B) At least one phthalocyanine aluminum compound, and a solvent,

[In formula (1), X ¹ to X ¹⁶ are each independently a hydrogen atom or a halogen atom, Y ¹ and Y ² are each independently a hydrogen atom or a halogen atom, and Z is a C 1-3 alkylene group],

[In formula (2A), X ⁵¹ to X ⁵⁴ are each independently an optionally substituted alkyl group, an optionally substituted aryl group, a optionally substituted cycloalkyl group, and optionally substituted heterocyclic group, An alkoxy group which may have a substituent, an aryloxy group which may have a substituent, an alkylthio group which may have a substituent, or an arylthio group which may have a substituent, Y ⁵¹ to Y ⁵⁴ are each independently a halogen atom, nitrate Group, phthalimidomethyl group which may have a substituent, or sulfamoyl group which may have a substituent, L ¹ is a hydroxyl group, a chlorine atom, -OP(=O)R ¹ R ² , or -O -SiR ³ R ⁴ R ⁵ (R ¹ to R ⁵ are each independently a hydrogen atom, a hydroxyl group, an alkyl group which may have a substituent, an aryl group which may have a substituent, an alkoxy group which may have a substituent, or may have Aryloxy group of the substituent, and R ¹ and R ² may be bonded to each other to form a ring, and two of R ³ , R ⁴ and R ⁵ may also be bonded to each other to form a ring), m1～m4 and n1～n4 Each independently is an integer of 0 to 4, m1+n1, m2+n2, m3+n3 and m4+n4 are each independently an integer of 0-4],

[In the formula (2B), X ⁵⁵ to X ⁶² are each independently an optionally substituted alkyl group, an optionally substituted aryl group, a optionally substituted cycloalkyl group, and optionally substituted heterocyclic group, The alkoxy group which may have a substituent, the aryloxy group which may have a substituent, the alkylthio group which may have a substituent, or the arylthio group which may have a substituent, Y ⁵⁵ to Y ⁶² are each independently a halogen atom, nitrate Group, phthalimide methyl group which may have a substituent, or sulfamoyl group which may have a substituent, L ² is -O-SiR ⁶ R ⁷ -O-, -O-SiR ⁸ R ^9- O-SiR ¹⁰ R ¹¹ -O-, or -OP(=O)R ¹² -O-(R ⁶ to R ¹² are each independently a hydrogen atom, a hydroxyl group, an alkyl group that may have a substituent, and a substituent that may have a substituent Aryl, alkoxy which may have a substituent, or aryloxy which may have a substituent), m5 to m12 and n5 to n12 are each independently an integer of 0 to 4, m5 + n5, m6 + n6, m7 + n7, m8 + n8, m9 + n9, m10+n10, m11+n11 and m12+n12 are each independently an integer of 0 to 4]. A color filter having a pixel portion including: a quinoline yellow compound represented by the following formula (1), and a compound selected from the compound represented by the following formula (2A) and the following formula (2B) At least one phthalocyanine aluminum compound in the group consisting of the represented compounds,

[In formula (1), X ¹ to X ¹⁶ are each independently a hydrogen atom or a halogen atom, Y ¹ and Y ² are each independently a hydrogen atom or a halogen atom, and Z is a C 1-3 alkylene group],

[In formula (2A), X ⁵¹ to X ⁵⁴ are each independently an optionally substituted alkyl group, an optionally substituted aryl group, a optionally substituted cycloalkyl group, and optionally substituted heterocyclic group, An alkoxy group which may have a substituent, an aryloxy group which may have a substituent, an alkylthio group which may have a substituent, or an arylthio group which may have a substituent, Y ⁵¹ to Y ⁵⁴ are each independently a halogen atom, nitrate Group, phthalimidomethyl group which may have a substituent, or sulfamoyl group which may have a substituent, L ¹ is a hydroxyl group, a chlorine atom, -OP(=O)R ¹ R ² , or -O -SiR ³ R ⁴ R ⁵ (R ¹ to R ⁵ are each independently a hydrogen atom, a hydroxyl group, an alkyl group which may have a substituent, an aryl group which may have a substituent, an alkoxy group which may have a substituent, or may have Aryloxy group of the substituent, and R ¹ and R ² may be bonded to each other to form a ring, and two of R ³ , R ⁴ and R ⁵ may also be bonded to each other to form a ring), m1～m4 and n1～n4 Each independently is an integer of 0 to 4, m1+n1, m2+n2, m3+n3 and m4+n4 are each independently an integer of 0-4],

[In the formula (2B), X ⁵⁵ to X ⁶² are each independently an optionally substituted alkyl group, an optionally substituted aryl group, a optionally substituted cycloalkyl group, and optionally substituted heterocyclic group, The alkoxy group which may have a substituent, the aryloxy group which may have a substituent, the alkylthio group which may have a substituent, or the arylthio group which may have a substituent, Y ⁵⁵ to Y ⁶² are each independently a halogen atom, nitrate Group, phthalimide methyl group which may have a substituent, or sulfamoyl group which may have a substituent, L ² is -O-SiR ⁶ R ⁷ -O-, -O-SiR ⁸ R ^9- O-SiR ¹⁰ R ¹¹ -O-, or -OP(=O)R ¹² -O-(R ⁶ to R ¹² are each independently a hydrogen atom, a hydroxyl group, an alkyl group that may have a substituent, and a substituent that may have a substituent Aryl, alkoxy which may have a substituent, or aryloxy which may have a substituent), m5 to m12 and n5 to n12 are each independently an integer of 0 to 4, m5 + n5, m6 + n6, m7 + n7, m8 + n8, m9 + n9, m10+n10, m11+n11 and m12+n12 are each independently an integer of 0 to 4].