JPWO2020045198A1 - Color filter - Google Patents

Abstract

One aspect of the present invention is C.I. I. At least one selected from the group consisting of a red pixel portion containing Pigment Red 269 and a yellow color material having an average transmittance of 6% or less at 440 to 470 nm, and a zinc halide phthalocyanine pigment and an aluminum phthalocyanine halogenated pigment. It is a color filter including a green pixel portion including.

Description

The present invention relates to color filters.

As a display color standard, in addition to the conventional sRGB standard, the red pixel part and the green pixel part of the color filter are set with more vivid chromaticity coordinates than the sRGB standard, and DCI-P3 can realize higher color reproducibility. Standards (Digital Cinema Initiative) are attracting attention. In order to satisfy such a standard, as disclosed in Patent Document 1, it is necessary to transmit only a specific wavelength in a color filter to obtain a vivid color.

Japanese Unexamined Patent Publication No. 8-240708

However, conventional color filters do not necessarily have sufficient characteristics to realize high color reproducibility as described above in the DCI-P3 standard, and there is a demand for improving the color reproducibility of color filters. It still exists.

Therefore, an object of the present invention is to improve the color reproducibility of the color filter.

According to the study by the present inventors, it is effective to increase the chromaticity x of the red pixel portion in order to improve the color reproducibility of the color filter. Small C.I. I. By using Pigment Red 269 in combination with a specific yellow color material, the chromaticity x of the red pixel portion can be significantly increased, and in addition, by using a specific green pigment in the green pixel portion, the color of the color filter It turned out that the reproducibility can be improved.

That is, one aspect of the present invention is C.I. I. At least one selected from the group consisting of a red pixel portion containing Pigment Red 269 and a yellow color material having an average transmittance of 6% or less at 440 to 470 nm, and a zinc halide zinc phthalocyanine pigment and a halogenated aluminum phthalocyanine pigment. It is a color filter including a green pixel portion including.

The yellow color material is C.I. I. Pigment Yellow 129, C.I. I. Pigment Yellow 138, C.I. I. Pigment Yellow 139, C.I. I. Pigment Yellow 150, C.I. I. Pigment Yellow 151, C.I. I. Pigment Yellow 185 and C.I. I. It may be at least one selected from the group consisting of sulfonated derivatives of Pigment Yellow 12.

The green pixel part is C.I. I. Pigment Green 58 and C.I. I. It may contain at least one zinc halide phthalocyanine pigment selected from the group consisting of Pigment Green 59.

式（１）中、Ｘ^１〜Ｘ^１６は各々独立に水素原子又はハロゲン原子であり、Ｙ^１及びＹ^２は各々独立に水素原子又はハロゲン原子であり、Ｚは炭素数１〜３のアルキレン基である。The green pixel portion may further contain a compound represented by the following formula (1).

In formula (1), X ^{1 to} X ¹⁶ are independently hydrogen atoms or halogen atoms, Y ¹ and Y ² are independently hydrogen atoms or halogen atoms, and Z is an alkylene group having 1 to 3 carbon atoms. Is.

According to the present invention, the color reproducibility of the color filter can be improved.

It is a schematic cross-sectional view which shows the liquid crystal display device which is one Embodiment of a display device.

The color filter according to one embodiment is used in a display device such as a liquid crystal display device. In explaining the color filter according to the present embodiment, first, the embodiment of the display device will be described.

FIG. 1 is a schematic cross-sectional view showing a liquid crystal display device according to an embodiment of the display device. As shown in FIG. 1, the liquid crystal display device 1 according to the embodiment includes a light source 2, a first polarizing layer 3, a first substrate 4, a first electrode 5, a liquid crystal layer 6, and a third. The second electrode 7, the second polarizing layer 8, the color filter 9, and the second substrate 10 are provided in this order.

The light source 2 may be, for example, a white LED (light emitting diode) light source, a white organic EL light source, a white inorganic EL light source, a white quantum dot light source, or the like. When the light source 2 is a white LED light source, the white LED light source includes, for example, a white LED light source that obtains white light by mixing colors by combining a red LED, a green LED, and a blue LED, and a blue LED, a red LED, and a green phosphor. A white LED light source that obtains white light by mixing colors, a white LED light source that obtains white light by mixing colors by combining a blue LED, a red light emitting phosphor, and a green light emitting phosphor, and a mixture of blue LEDs and a YAG-based phosphor White LED light source that obtains white light, white LED light source that obtains white light by mixing colors by combining ultraviolet LED, red light emitting phosphor, green light emitting phosphor, and blue light emitting phosphor, white LED light source that combines red laser, quantum dot It may be a white LED light source or the like using technology.

As the phosphor, a phosphor used in this field can be appropriately selected. For example, as a phosphor that can be excited by a blue LED or an ultraviolet LED, an yttrium-aluminum-garnet-based phosphor (YAG: Ce) activated by cerium and a lutethium-aluminum-garnet-based phosphor (LAG) activated by cerium are used. : Ce), europium and / or chromium-activated nitrogen-containing calcium aluminosilicate-based phosphor (for example, CaO-Al ₂ O _3- SiO ₂ : Eu), europium-activated silicate-based phosphor ((Sr, Ba)). ) 2SiO ₄ : Eu), Sialon-based phosphor, CASN-based phosphor (CaAlSiN ₃ : Eu), SCASN-based phosphor ((Sr, Ca) AlSiN ₃ : Eu) and other nitride-based phosphors, KSF-based phosphor (K ₂ SiF ₆ : Mn), sulfide-based phosphors, quantum dot phosphors and the like can be mentioned.

More specifically, for example, the sialone-based phosphor may be an α-type sialon phosphor. The α-type sialon phosphor is prepared by mixing, for example, silicon nitride (Si ₃ N ₄ ), aluminum nitride (AlN), calcium carbonate (CaCO ₃ ), and europium oxide (Eu ₂ O ₃ ) at a predetermined molar ratio, and 1 atm. It may be an α-type sialone phosphor in which Eu ions are solid-dissolved, which is produced by holding in nitrogen at (0.1 MPa) at a temperature of 1700 ° C. for 1 hour and firing by a hot press method. This α-type sialone phosphor is a phosphor that is excited by blue light of 450 to 500 nm and emits yellow light of 550 to 600 nm. Sialon phosphor, for example, be a beta-SiAlON phosphor having a β-Si ₃ N ₄ structure. This β-type sialone fluorescent substance is a fluorescent substance that emits green to orange light of 500 to 600 nm when excited by near-ultraviolet to blue light.

Further, for example, the phosphor may be an oxynitride phosphor composed of the JEM phase. This oxynitride phosphor is excited by near-ultraviolet to blue light to emit light having an emission wavelength peak at 460 to 510 nm.

The first polarizing layer 3 and the second polarizing layer 8 may be known polarizing layers (polarizing plates), for example, a dichroic organic dye polarizing plate, a coating type polarizing layer, a wire grid type polarizing plate, and a cholesteric. It may be a liquid crystal type polarizing plate or the like. The first substrate 4 and the second substrate 10 may be made of, for example, glass, or may be made of a flexible material such as plastic.

One of the first electrode 5 and the second electrode 7 is a pixel electrode, and the other is a common electrode. For example, the first electrode 5 may be a pixel electrode and the second electrode 7 may be a common electrode. The first electrode 5 and the second electrode 7 may be made of a transparent material such as ITO. The liquid crystal layer 6 may be composed of a known liquid crystal composition. An alignment film may be further provided between the first electrode 5 and the liquid crystal layer 6 and between the second electrode 7 and the liquid crystal layer 6.

The light L from the light source 2 is incident on the first polarizing layer 3 through, for example, a light guide plate (not shown) formed of acrylic resin, glass, or the like. The light source 2 may be arranged on the side surface of the light guide plate (edge backlight structure) or may be arranged on the main surface of the light guide plate (directly below backlight structure). After the light L from the light source 2 is incident on the first polarizing layer 3, the first substrate 4, the first electrode 5, the liquid crystal layer 6, the second electrode 7, the second polarizing layer 8, and the color filter After passing through 9 and the second substrate 10 in this order, the light is emitted to the outside of the liquid crystal display device 1. At this time, the color of the light L from the light source 2 is converted by the color filter 9.

Subsequently, an embodiment of the color filter will be described in detail. The color filter 9 according to the embodiment includes a red pixel portion (red color filter) 9a, a green pixel portion (green color filter) 9b, a blue pixel portion (blue color filter) 9c, and a light-shielding portion (black matrix) 9d. And have. The red pixel portion 9a, the green pixel portion 9b, and the blue pixel portion 9c are repeatedly arranged in this order, and the color pixel portions are separated from each other by the light-shielding portion 9d.

The red pixel portion 9a includes C.I. I. Pigment Red 269 and a yellow color material having an average transmittance of 6% or less at 440 to 470 nm are included. C. I. Pigment Red 269 is, for example, C.I., manufactured by Clariant AG. I. It is available as Pigment Red 269.

The yellow color material having an average transmission rate of 6% or less at 440 to 470 nm is 440 when an evaluation colored film having a thickness of 1 μm having a mass ratio of yellow color material: resin of 3: 5 is formed. It is a yellow color material having an average transmittance of 6% or less at ~ 470 nm. The average value of the transmittance of the yellow color material was measured using a spectrophotometer (for example, U3900 manufactured by Hitachi High-Tech Science Co., Ltd.) under the conditions of measurement area: 380 to 780 nm and measurement interval: 1 nm for the above evaluation. It is calculated as the average value of the transmittance at 440 to 470 nm from the transmittance spectrum of the colored film. The resin contained in the evaluation coloring film includes a binder resin and a dispersant for suitably dispersing the yellow color material in the binder resin. Further, as the resin, a resin having an average transmittance of 99% or more at 440 to 470 nm when a 1 μm resin film is formed is used.

The evaluation colored film is produced, for example, by the following procedure.
0.55 g of yellow color material, 0.83 g of dispersant (BYK-LPN21116 manufactured by Big Chemie, solid content: 40% by mass), 3.20 g of propylene glycol monomethyl ether acetate, and 0.3 to 0.4 mm zircon beads. Using, disperse with a shaker (paint shaker manufactured by Toyo Seiki Co., Ltd.) for 2 hours to obtain a dispersion liquid. To this dispersion, 1.46 g of a binder resin (Unidic ZL-295 manufactured by DIC Corporation, solid content: 40% by mass) and 0.84 g of propylene glycol monomethyl ether acetate are added and mixed with a shaker to form a yellow composition. Get things. This yellow composition is spin-coated on a soda glass substrate and then dried at 90 ° C. for 3 minutes to prepare a measurement sample in which a colored film for evaluation is formed on the glass substrate. By adjusting the spin rotation speed at the time of spin coating, the thickness of the evaluation colored film after heating at 90 ° C. for 3 minutes is set to 1 μm.

The average value of the transmittance of the yellow color material at 440 to 470 nm is preferably as small as possible from the viewpoint that the chromaticity x of the red pixel portion 9a can be further increased, and specifically, preferably 5% or less and 4% or less. 3% or less, 2.5% or less, or 2% or less.

The yellow color material may be any yellow color material having the above-mentioned transmittance, but is preferably a yellow pigment, and more preferably C.I. I. Pigment Yellow 129, C.I. I. Pigment Yellow 138, C.I. I. Pigment Yellow 139, C.I. I. Pigment Yellow 150, C.I. I. Pigment Yellow 151, C.I. I. Pigment Yellow 185 and C.I. I. Pigment Yellow 12 is at least one selected from the group consisting of sulfonated derivatives. C. I. As the sulfonated derivative of Pigment Yellow 12, known ones can be used, and for example, those described as "disazo compound C2" in "Example 2" of JP-A-2014-228682 can be used. The yellow color material is more preferably C.I. from the viewpoint that the chromaticity x of the red pixel portion 9a can be further increased and the color reproducibility can be further enhanced. I. Pigment Yellow 129, C.I. I. Pigment Yellow 139, C.I. I. Pigment Yellow 150 and C.I. I. Pigment Yellow At least one selected from the group consisting of 185, and particularly preferably C.I. I. Pigment Yellow 129, C.I. I. Pigment Yellow 139 and C.I. I. Pigment Yellow At least one selected from the group consisting of 185.

The yellow color material may be a yellow dye. The yellow dye may be, for example, a quinoline dye, an azo dye, a quinophthalone dye, a methine dye, a coumarin dye, an isoindoline dye, or the like, and specifically, C.I. I. Acid Yellow 1, 3, 23, 29, 36, C.I. I. Solvent Yellow 2, 4, 7, 33, 56, 93, 98, C.I. I. Disperse Yellow 5, 42, 49, 50, 54, 56, 64, 71, 104, 114, 149, 201 and the like may be used.

C.I. in the red pixel portion 9a. I. The blending ratio of Pigment Red 269 and the yellow color material is determined according to the type of the yellow color material and the desired chromaticity. For example, C.I. I. Pigment Red 269 / Yellow color material was mixed in 7/3 (mass ratio), and C.I. I. When a coating film with a film thickness of 3 μm, in which the total amount of Pigment Red 269 and the yellow color material / the compounding ratio of the resin is 3/5 (mass ratio), the chromaticity x measured by the C light source is 0.68 or more. Become.

When the color filter 9 is used as a color filter satisfying the DCI-P3 standard and the sRGB standard, the red pixel portion 9a in the red pixel portion 9a can be preferably obtained from the viewpoint of obtaining a red pixel portion 9a having a high brightness and a thin film thickness. I. The content of Pigment Red 269 is C.I. I. The total amount of Pigment Red 269 and the yellow color material is preferably 10 parts by mass or more, 15 parts by mass or more, 20 parts by mass or more, or 25 parts by mass or more, preferably 90 parts by mass with respect to 100 parts by mass. Hereinafter, it is 80 parts by mass or less, 70 parts by mass or less, 60 parts by mass or less, 50 parts by mass or less, 40 parts by mass or less, or 30 parts by mass or less.

The red pixel portion 9a may further contain other components other than the above. Other components may be, for example, organic pigments other than the above, organic dyes, organic pigment derivatives and the like.

Examples of organic pigments other than the above include azo pigments, disazo pigments, azomethine pigments, anthraquinone pigments, quinophthalone pigments, quinacridone pigments, diketopyrrolopyrrole pigments, dioxazine pigments, and benzimidazolone pigments. , Phtalocyanin pigments, isoindolin pigments, isoindolinone pigments, perylene pigments and the like (excluding CI Pigment Red 269 and the above yellow colorant). The organic pigment is preferably an azo pigment, a disazo pigment, an anthraquinone pigment, a quinophthalone pigment, a quinacridone pigment, a diketopyrrolopyrrole pigment, or a perylene pigment (however, CI Pigment Red). 269 and the above yellow color material are excluded).

Examples of organic dyes include xanthene dyes, azo dyes, disazo dyes, anthraquinone dyes, quinophthalone dyes, triarylmethane dyes, methine dyes, phthalocyanine dyes, rhodamine dyes, cyanine dyes and the like. Can be mentioned. The organic dye is preferably a xanthene dye, an azo dye, a disazo dye, an anthraquinone dye, a quinophthalone dye, a rhodamine dye, or a cyanine dye.

The organic pigment derivative may be, for example, a derivative in which a part of a known organic pigment is modified (substituted) with a sulfonic acid group, a carboxyl group, an amino group, a phthalimide methyl group or the like. Specifically, for example, Solspace (registered trademark name) 5000, 12000, 22000 (manufactured by Ruble Sol Co., Ltd.) and the like can be mentioned. The content of the organic pigment derivative may be 1 part by mass or more and 40 parts by mass or less with respect to 100 parts by mass of the total amount of the pigment.

The red pixel portion 9a may further contain a resin such as a photosensitive resin, a dispersant, a rosin, a surfactant, and the like. These components may or may not be treated on the pigment surface (so-called surface treatment). As a method for treating the pigment surface, known methods such as rosin treatment, surfactant treatment, solvent treatment, and resin treatment may be used.

Examples of the photosensitive resin include thermoplastic resins such as urethane resin, acrylic resin, polyamic acid resin, polyimide resin, styrene maleic acid resin, and styrene anhydride maleic acid resin, and for example, 1,6-. Bifunctional monomers such as hexanediol diacrylate, ethylene glycol diacrylate, neopentyl glycol diacrylate, triethylene glycol diacrylate, bis (acryloxyethoxy) bisphenol A, 3-methylpentanediol diacrylate, etc., trimethyl propantri Examples thereof include photopolymerizable monomers such as polyfunctional monomers such as acrylate, pentaerythritol triacrylate, tris (2-hydroxyethyl) isocyanate, dipentaerythritol hexaacrylate, and dipentaerythritol pentaacrylate.

Examples of the dispersant include ANTI-TERRA (registered trademark name) U / U100, 204, DISPERBYK (registered trademark name) 106, 108, 109, 112, 130, 140, 142, and 145. , 161 、 162 、 163 、 164 、 167 、 168 、 180 、 182 、 183 、 184 、 185 、 2000 、 2001 、 2008 、 2009 、 2013 2022, 2025, 2026, 2050, 2055, 2150, 2155, 2163, 2164, 9076, 9077, BYK LPN-6919, 21116, 21324, 22102 (manufactured by Big Chemie Co., Ltd.) ), EFKA (registered trademark name) 46, 47, 4010, 4020, 4320, 4300, 4330, 4401, 4570, 5054, 7461, 7462, 7476, 7477 (BASF). (Manufactured by Ajinomoto Co., Ltd.), Ajispar PB (registered trademark name) 814, 821, 822, 881 (manufactured by Ajinomoto Fine Techno Co., Ltd.), Solspace (registered trademark name) 24000, 28000, 37500, 76500 (Lubrisole) (Made by Co., Ltd.), etc. The content of the dispersant may be 10 parts by mass or more and 120 parts by mass or less with respect to 100 parts by mass of the total amount of the pigment.

The green pixel portion 9b contains at least one selected from the group consisting of a zinc halide phthalocyanine pigment and an aluminum halogenated aluminum phthalocyanine pigment (hereinafter, also referred to as “specific halogenated phthalocyanine pigment”).

The halogenated zinc phthalocyanine pigment is preferably used from the viewpoint of further enhancing the color reproducibility of the color filter and preferably obtaining the green pixel portion 9b having high brightness and thin film thickness. I. Pigment Green 58 and C.I. I. At least one selected from the group consisting of Pigment Green 59, more preferably C.I. I. Pigment Green 59. The halogenated aluminum phthalocyanine pigment is preferably used from the viewpoint of further improving the color reproducibility of the color filter and preferably obtaining the green pixel portion 9b having high brightness and thin film thickness. I. Pigment Green 63.

The green pixel portion 9b may further contain a yellow color material. The blending ratio of the specific halogenated phthalocyanine pigment and the yellow color material is determined according to the type of each pigment or color material and the desired chromaticity.

The yellow color material is, in one embodiment, C.I. I. Pigment Yellow 138, 129, 139, 150, 185, 231 and the like may be yellow pigments, preferably C.I. I. Pigment Yellow 138 and C.I. I. Pigment Yellow At least one kind of yellow pigment selected from the group consisting of 185.

式（１）中、Ｘ^１〜Ｘ^１６は各々独立に水素原子又はハロゲン原子であり、Ｙ^１及びＹ^２は各々独立に水素原子又はハロゲン原子であり、Ｚは炭素数１〜３のアルキレン基である。The yellow color material is a yellow pigment (quinophthalone pigment) composed of a compound (quinophthalone compound) represented by the following formula (1) in another preferable embodiment from the viewpoint of further enhancing the color reproducibility of the color filter. is there.

In formula (1), X ^{1 to} X ¹⁶ are independently hydrogen atoms or halogen atoms, Y ¹ and Y ² are independently hydrogen atoms or halogen atoms, and Z is an alkylene group having 1 to 3 carbon atoms. Is.

The quinophthalone compound exhibits selective absorption and permeation due to the dimerization of the quinophthalone skeleton. In addition, the quinophthalone compound dimerizes the quinophthalone skeleton using the linking group Z as a spacer, whereby the conjugation is cleaved and excessive redness is suppressed. Further, in the above quinophthalone compound, the dispersibility is improved by introducing the imide structure. From these facts, according to the above-mentioned quinophthalone compound, a pigment exhibiting excellent brightness and coloring power can be obtained.

The halogen atom in the 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.

Specific examples of the alkylene group having 1 to 3 carbon atoms in the formula (1) include a methylene group, an ethylene group (1,1-ethanediyl group or 1,2-ethanediyl group), and a propylene group (1,1-). Propanediyl group, 2,2-propanediyl group, 1,2-propanediyl group or 1,3-propanediyl group) is preferable, methylene group, 1,1-ethanediyl group, 1,1-propanediyl group, 2 , 2-Propanediyl group is more preferable, and methylene group is more preferable.

In the quinophthalone compound, it is preferable that at least one of X ^{1 to} X ¹⁶ is a halogen atom, and more preferably two or more are halogen atoms. By introducing a halogen atom into X ^{1 to} X ¹⁶ , the dispersibility of the quinophthalone compound is further improved, and the above-mentioned effect tends to be obtained more remarkably.

Of X ^{1 to} X ⁴ , at least one is preferably a halogen atom, two or more are more preferably halogen atoms, and all may be halogen atoms. Preferably at least one of X ² and X ³ is a halogen atom, more preferably X ² and X ³ are each a halogen atom.

Of X ^{5 to} X ⁸ , at least one is preferably a halogen atom, two or more are more preferably halogen atoms, and all may be halogen atoms. It is preferred that at least one is a halogen atom of X ⁶ and X ^7, and more preferably X ⁶ and X ⁷ are each a halogen atom.

Of X ^{9 to} X ¹² , at least one is preferably a halogen atom, two or more are more preferably halogen atoms, and all may be halogen atoms. It is preferred that at least one is a halogen atom of X ¹⁰ and ^{X 11,} and more preferably ^{X 10} and ^{X 11} are each a halogen atom.

Of X ^{13 to} X ¹⁶ , at least one is preferably a halogen atom, two or more are more preferably halogen atoms, and all may be halogen atoms. It is preferred that at least one is a halogen atom of X ¹⁴ and ^{X 15,} and more preferably ^{X 14} and ^{X 15} are each a halogen atom.

Y ¹ and Y ² may be the same or different from each other, but are preferably the same from the viewpoint of facilitating the synthesis of the quinophthalone compound.

式（１−ｉ）及び式（１−ｉｉ）中、Ｘ^１〜Ｘ^１６、Ｙ^１、Ｙ^２及びＺは上述のとおりである。The structure of the formula (1) includes tautomers having the following formulas (1-i) and formula (1-ii), and the quinophthalone compound has any of these structures. You may.

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

Specific examples of the quinophthalone compound are given below, but the quinophthalone compound is not limited thereto.

As the quinophthalone compound, one kind may be used alone, or two or more kinds of compounds may be appropriately selected and used in combination.

The method for producing the quinophthalone compound is not particularly limited, and a conventionally known method can be appropriately used for production. Hereinafter, one aspect of the method for producing a quinophthalone compound will be described, but the production method is not limited thereto.

The quinophthalone compound can be obtained, for example, by a method including the following steps I, II, III and IV.

式（Ａ−１）中、Ｙ^１、Ｙ^２及びＺは上述のとおりである。<Step I>
First, J. By the method described in Heterocyclic, Chem, 30, 17 (1993) or the like, 2-3 equivalents of crotonaldehyde are added to 1 equivalent of bisanilins and reacted in a strong acid in the presence of an oxidizing agent, and the following formula (A) -1) Synthesize the compound.

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

Examples of the strong acid include hydrochloric acid, sulfuric acid, nitric acid and the like. Examples of the oxidizing agent include sodium iodide, p-chloranil, nitrobenzene and the like.

With respect to step I, the reaction temperature may be 80 ° C. to 100 ° C., preferably 90 ° C. to 100 ° C., and the reaction time may be 1 hour to 6 hours, preferably 3 hours to 6 hours.

式（Ａ−２）中、Ｙ^１、Ｙ^２及びＺは上述のとおりである。<Step II>
Further, the compound of the formula (A-2) can be obtained by reacting the obtained compound of the 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.

With respect to Step II, the reaction temperature may be −20 ° C. to 70 ° C., preferably 0 ° C. to 50 ° C., and the reaction time may be 1 hour to 4 hours, preferably 1 hour to 3 hours.

式（Ａ−３）中、Ｙ^１、Ｙ^２及びＺは上述のとおりである。<Step III>
Further, the compound of the formula (A-3) can be obtained by adding 6 to 8 equivalents of reduced iron to 1 equivalent of the obtained compound of the formula (A-2) and reacting them.

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

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

<Process IV>
Further, at least selected from the group consisting of phthalic anhydride and halogen-substituted phthalic anhydride with respect to 1 equivalent of the compound of the formula (A-3) obtained by the method described in JP2013-61622. The compound of formula (1) can be obtained by reacting one kind in the presence of an acid catalyst in an amount of 4 to 6 equivalents. Examples of the acid catalyst include benzoic acid and zinc chloride.

With respect to step IV, the reaction temperature may be 180 ° C. to 250 ° C., preferably 210 ° C. to 250 ° C., and the reaction time may be 1 hour to 8 hours, preferably 3 hours to 8 hours.

The green pixel portion 9b may further contain other components other than the above. Specifically, the other components are the same as the other components described in the red pixel portion 9a.

The blue pixel portion 9c contains, for example, a blue pigment and a dye. The blue pigment may be a known pigment used for the blue pixel portion. The blue pigment is C.I. I. Pigment Blue 15, 15: 1, 15: 2, 15: 3, 15: 4, 15: 5, 15: 6, etc., preferably C.I. I. Pigment Blue 15: 6.

The dye may be a known dye used for the blue pixel portion. The dyes include, for example, xanthene dyes, azo dyes, disazo dyes, anthraquinone dyes, quinophthalone dyes, triarylmethane dyes, methine dyes, phthalocyanine dyes, rhodamine dyes, cyanine dyes and the like. Good. When the blue pixel portion 9c contains a blue pigment and a dye, the blending ratio of the blue pigment and the dye is determined according to these types and a desired chromaticity.

The blue pixel portion 9c may further contain other components other than the above. Specifically, the other components are the same as the other components described in the red pixel portion 9a.

The light-shielding portion (black matrix) may have a known composition, and is formed, for example, by dispersing a black pigment in a cured product of a photosensitive resin composition.

The color filter 9 described above is preferably used even when high color reproducibility is required as in the DCI-P3 standard. Specifically, by using this color filter, the area of the triangle formed by connecting the three points of the red, green, and blue chromaticity coordinates in the xy chromaticity diagram with straight lines is increased. The reason will be described in more detail below.

First, in the red pixel portion 9a, the chromaticity x can be increased. Specifically, C.I. I. Pigment Red 269 alone can display only a small chromaticity x, but by using a yellow color material having a specific transmittance in combination, the chromaticity x as the red pixel portion 9a becomes remarkably large. Such an effect is, for example, C.I. I. It is not found in Pigment Red 254 (that is, CI Pigment Red 254 alone or in combination with CI Pigment Red 254 and a yellow color material having a specific transmittance, in the red pixel portion. The chromaticity x is about the same), C.I. I. It is a surprising effect peculiar to Pigment Red 269. C. I. In the combination of Pigment Red 254 and the yellow color material, absorption overlaps around 480 nm, but C.I. I. Pigment Red 269 is C.I. I. Since it has steeper absorption on the longer wavelength side than Pigment Red 254, the overlap of absorption with the yellow color material is small, and the reason is that the red pixel portion efficiently exhibits the necessary absorption in a wider wavelength range. it is conceivable that. In addition, C.I. I. According to the combination of Pigment Red 269 and certain yellow colors, C.I. I. It is also possible to reduce the chromaticity y of the red pixel portion 9a as compared with the combination of Pigment Red 254 and the specific yellow color material.

Further, by using a specific halogenated phthalocyanine pigment in the green pixel portion 9b, for example, a general green pigment, C.I. I. Compared with the halogenated copper phthalocyanine pigment such as Pigment Green 36, the green pixel portion 9b can display a region having a small chromaticity x and a large chromaticity y. Such an effect is exhibited in the green pixel portion 9b with a specific halogenated phthalocyanine pigment and C.I. I. It is remarkably obtained when used in combination with a yellow color material such as Pigment Yellow 138. Then, by combining the red pixel portion 9a and the green pixel portion 9b, the chromaticity of the red pixel portion 9a and the chromaticity of the green pixel portion 9b are reproduced in high colors in opposite directions in the xy chromaticity diagram. The area of the above triangle can be increased because it moves away from the chromaticity coordinates of white. In particular, in the green pixel portion 9b, C.I. I. By using Pigment Green 59 and the above-mentioned quinophthalone pigment in combination, the area of the triangle measured by the C light source is made larger than the area of the triangle (= 0.1582) specified by NTSC (National Television System Committee). It becomes possible. Therefore, according to the color filter 9 of the present embodiment, the color reproducibility can be improved.

Hereinafter, the present invention will be described in more detail based on Examples, but the present invention is not limited to the following Examples.

[Production Example 1: Composition for Evaluation of Pigment Red 269]
Clariant C.I. I. Pigment Red 269 0.55 g, along with 0.83 g of BYK-LPN21116 (solid content: 40% by mass) manufactured by Big Chemie and 3.20 g of propylene glycol monomethyl ether acetate, using 0.3 to 0.4 mm zircon beads. Dispersion 1 was obtained by dispersing with a paint shaker manufactured by Toyo Seiki Co., Ltd. for 2 hours. To this dispersion 1, 1.46 g of Unidic ZL-295 (solid content: 40% by mass) manufactured by DIC Corporation and 0.84 g of propylene glycol monomethyl ether acetate are added and mixed with a paint shaker to make an evaluation composition. Got

[Production Example 2: Evaluation Composition of Pigment Red 254]
C. I. Instead of Pigment Red 269, BASF's C.I. I. An evaluation composition was obtained in the same manner as in Production Example 1 except that Pigment Red 254 was used.

(Measurement of transmittance of red pigment)
The evaluation composition obtained in Production Examples 1 and 2 was spin-coated on a soda glass substrate and then dried at 90 ° C. for 3 minutes to prepare a transmittance measurement sample in which a colored film was formed on the substrate. By adjusting the spin rotation speed at the time of spin coating, the thickness of the colored film after heating at 90 ° C. for 3 minutes was adjusted to 1 μm. Using a spectrophotometer (U3900 manufactured by Hitachi High-Tech Science Corporation), the transmission spectrum of the transmittance measurement sample was measured under the conditions of a measurement area: 380 to 780 nm and a measurement interval of 1 nm. From the obtained transmittance spectrum, the average value of the transmittance at 440 to 470 nm and the average value of the transmittance at 530 to 590 nm were calculated. The results are shown in Table 1.

[Production Example 3: Evaluation Composition of Pigment Yellow 139]
C. I. Instead of Pigment Red 269, BASF's C.I. I. An evaluation composition was obtained in the same manner as in Production Example 1 except that Pigment Yellow 139 was used.

[Production Example 4: Evaluation Composition of Pigment Yellow 138]
C. I. Instead of Pigment Red 269, C.I. I. An evaluation composition was obtained in the same manner as in Production Example 1 except that Pigment Yellow 138 was used.

[Production Example 5: Composition for Evaluation of Pigment Yellow 185]
C. I. Instead of Pigment Red 269, BASF's C.I. I. An evaluation composition was obtained in the same manner as in Production Example 1 except that Pigment Yellow 185 was used.

[Production Example 6: Evaluation Composition of Pigment Yellow 129]
C. I. Instead of Pigment Red 269, BASF's C.I. I. An evaluation composition was obtained in the same manner as in Production Example 1 except that Pigment Yellow 129 was used.

[Production Example 7: Composition for Evaluation of Pigment Yellow 150]
C. I. Instead of Pigment Red 269, LANXESS C.I. I. An evaluation composition was obtained in the same manner as in Production Example 1 except that Pigment Yellow 150 was used.

[Production Example 8: Composition for Evaluation of Pigment Yellow 151]
C. I. Instead of Pigment Red 269, DIC Corporation C.I. I. An evaluation composition was obtained in the same manner as in Production Example 1 except that Pigment Yellow 151 was used.

[Production Example 9: Composition for Evaluation of Sulfonized Derivative of Pigment Yellow 12]
According to "Example 2" of JP2014-228682, C.I., in the same manner as "disazo compound C2". I. A sulfonated derivative of Pigment Yellow 12 (hereinafter, also referred to as “Pigment Yellow 12 derivative”) was obtained. C. I. Instead of Pigment Red 269, the obtained C.I. I. An evaluation composition was obtained in the same manner as in Production Example 1 except that the sulfonated derivative of Pigment Yellow 12 was used.

[Production Example 10: Composition for Evaluation of Pigment Yellow 109]
C. I. Instead of Pigment Red 269, BASF's C.I. I. An evaluation composition was obtained in the same manner as in Production Example 1 except that Pigment Yellow 109 was used.

[Production Example 11: Composition for Evaluation of Pigment Yellow 110]
C. I. Instead of Pigment Red 269, DIC Corporation C.I. I. An evaluation composition was obtained in the same manner as in Production Example 1 except that Pigment Yellow 110 was used.

(Measurement of yellow pigment transmittance)
Measurement of the permeability of the red pigment except that the evaluation composition of the yellow color material obtained in Production Examples 3 to 11 was used instead of the evaluation composition of the red pigment obtained in Production Examples 1 and 2. In the same manner as above, the transmittance of each yellow color material was measured, and the average value of the transmittance at 440 to 470 nm and the average value of the transmittance at 530 to 590 nm were calculated. The results are shown in Table 2.

[Evaluation Examples 1 to 7]
A colored composition was obtained by mixing 3.5 g of the evaluation composition of Production Example 1 and 1.5 g of the evaluation composition of any of Production Examples 3 to 9 with a paint shaker. Each of the obtained colored compositions was spin-coated on a soda glass substrate and then dried at 90 ° C. for 3 minutes to prepare an evaluation sample in which a colored film was formed on the substrate. By adjusting the spin rotation speed at the time of spin coating, the thickness of the colored film after drying at 90 ° C. for 3 minutes was adjusted to 3 μm. Using a spectrophotometer (U3900 manufactured by Hitachi High-Tech Science Corporation), the chromaticity of the evaluation sample when the C light source was used was measured.

[Comparative evaluation example 1]
The same as in Evaluation Example 1 except that only the evaluation composition of Production Example 1 was used instead of the mixture of the evaluation composition of Production Example 1 and the evaluation composition of any one of Production Examples 3 to 9. The evaluation sample was prepared and the chromaticity was measured.

[Comparative Evaluation Examples 2-3]
Preparation of evaluation sample and measurement of chromaticity in the same manner as in Evaluation Example 1 except that the evaluation composition of Production Example 10 or 11 was used instead of the evaluation composition of any of Production Examples 3 to 9. Was done.

Table 3 shows the combinations of the red pigment and the yellow color material in each evaluation example and the comparative evaluation example, and the measurement results of the chromaticity.

[Comparative Evaluation Examples 4 to 13]
Preparation of evaluation samples and evaluation samples were made in the same manner as in Evaluation Examples 1 to 7 and Comparative Evaluation Examples 1 to 3, except that the evaluation composition of Production Example 2 was used instead of the evaluation composition of Production Example 1. The chromaticity was measured. Table 4 shows the combinations of the red pigment and the yellow color material and the measurement results of the chromaticity in each comparative evaluation example.

As described above, C.I. I. The chromaticity x can be increased by using Pigment Red 269 in combination with a yellow color material having an average transmittance of 6% or less at 440 to 470 nm.

[Production Example 12: Composition for Evaluation of Pigment Green 58]
C. I. Instead of Pigment Red 269, DIC Corporation C.I. I. An evaluation composition was obtained in the same manner as in Production Example 1 except that Pigment Green 58 (zinc halogenated phthalocyanine pigment) was used.

[Production Example 13: Composition for Evaluation of Pigment Green 59]
C. I. Instead of Pigment Red 269, DIC Corporation C.I. I. An evaluation composition was obtained in the same manner as in Production Example 1 except that Pigment Green 59 (zinc halogenated phthalocyanine pigment) was used.

[Production Example 14: Composition for Evaluation of Pigment Green 36]
C. I. Instead of Pigment Red 269, DIC Corporation C.I. I. An evaluation composition was obtained in the same manner as in Production Example 1 except that Pigment Green 36 (copper halide phthalocyanine pigment) was used.

^１Ｈ−ＮＭＲ（ＣＤＣｌ_３）δｐｐｍ：２．８１（ｓ，６Ｈ），４．２４（ｓ，２Ｈ），７．３４（ｄ，Ｊ＝８．０Ｈｚ，２Ｈ），７．４９（ｓ，２Ｈ），７．６７（ｓ，２Ｈ），７．９９（ｄ，Ｊ＝８．８Ｈｚ，２Ｈ）
^１３Ｃ−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＋[Production Example 15: Composition for Evaluation of Kinoftalone Pigment A]
(Synthesis of quinophthalone compounds)
First, a quinophthalone compound was synthesized according to the following procedure.
To a flask, 5.0 g (56.1 mmol) of 4,4'-methylenebis (2-chloroaniline), 27.6 g (112 mmol) of p-chloranil, 150 ml of water, 150 ml of concentrated hydrochloric acid, and 100 ml of n-butanol were added. The mixture was stirred at ° C. for 30 minutes. To this mixture was added dropwise 11.8 g (168 mmol) of crotonaldehyde dissolved in 12 ml of n-butanol, and the mixture was further stirred for 1 hour. The temperature was lowered to 80 ° C., 15.3 g (112 mmol) of zinc chloride was added little by little, 200 ml of THF was added, and the mixture was stirred for 1 hour while maintaining 80 ° C. After allowing to cool to room temperature, the ocher powder was recovered by vacuum filtration. The obtained ocher powder was washed with 200 ml of THF, and the ocher powder was recovered by vacuum filtration again. Further, the obtained ocher powder was transferred to a flask, 200 ml of water and 40 ml of 28% aqueous ammonia were added, and the mixture was stirred at room temperature for 2 hours. The powder was recovered by vacuum filtration to obtain 20.3 g of a crude product. The obtained crude product was dissolved in toluene, the insoluble material was removed by filtration, and then recrystallized to obtain 12.6 g of the intermediate (4) (yield: 61%).

^{1 1} H-NMR (CDCl ₃ ) δppm: 2.81 (s, 6H), 4.24 (s, 2H), 7.34 (d, J = 8.0Hz, 2H), 7.49 (s, 2H) ), 7.67 (s, 2H), 7.99 (d, J = 8.8Hz, 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 +

^１Ｈ−ＮＭＲ（ＣＤＣｌ_３）δｐｐｍ：２．８６（ｓ，６Ｈ），４．２７（ｓ，２Ｈ），７．５６（ｄ，Ｊ＝８．８Ｈｚ，２Ｈ），７．６２（ｓ，２Ｈ），８．０８（ｄ，Ｊ＝８．８Ｈｚ，２Ｈ）
^１３Ｃ−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^−１：３４６５，１６０４，１５３０，１４８７，１３６２Subsequently, 4.15 g (11.3 mmol) of the intermediate (4) and 7.55 mL of concentrated sulfuric acid were added to the flask, and the mixture was stirred at 45 ° C. for 20 minutes. Then, 1.62 mL of fuming nitric acid was added dropwise, the temperature was maintained, and stirring was continued for 1 hour. After allowing to cool, 250 mL of ice water was slowly poured into the system. Further, the pH was adjusted to 8 to 9 using a 10 wt% sodium hydroxide aqueous solution. The precipitated powder was collected by vacuum filtration and washed with 200 mL of distilled water and 100 mL of ethanol to obtain 4.86 g (10.6 mmol) of the intermediate (5) (yield: 94%).

^{1 1} H-NMR (CDCl ₃ ) δppm: 2.86 (s, 6H), 4.27 (s, 2H), 7.56 (d, J = 8.8Hz, 2H), 7.62 (s, 2H) ), 8.08 (d, J = 8.8Hz, 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

^１Ｈ−ＮＭＲ（ＣＤＣｌ_３）δｐｐｍ：２．６５（ｓ，６Ｈ），３．９７（ｓ，２Ｈ），５．９２（ｓ，４Ｈ），７．３２（ｓ，２Ｈ），７．３８（ｄ，Ｊ＝８．８Ｈｚ，２Ｈ），８．５９（ｄ，Ｊ＝８．８Ｈｚ，２Ｈ）
^１３Ｃ−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^−１：３４７６，３３７３，１６２７，１６０５，１４０９，１３５９，１２５０Subsequently, 5.00 g (10.9 mmol) of Intermediate (5) and 23.3 mL of ethanol were added to the flask, and the mixture was stirred at room temperature for 10 minutes. Then, 4.88 g (87.4 mmol) of reduced iron was added to the system, and the mixture was further stirred at room temperature for 10 minutes. Subsequently, 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 allowing to cool, the pH was adjusted to 9 by pouring into 150 mL of distilled water and using a 10% aqueous sodium hydroxide solution. The precipitated powder was collected by vacuum filtration. Further, the recovered powder was sufficiently stirred in 700 mL of ethyl acetate and filtered under reduced pressure. By distilling off the solvent of the obtained filtrate under reduced pressure, 3.64 g (9.16 mmol) of the intermediate (6), which is an ocher powder, was obtained (yield: 84%).

^{1 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 = 8.8Hz, 2H), 8.59 (d, J = 8.8Hz, 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＋Subsequently, 14.1 g (116 mmol) of benzoic acid was weighed in a flask under a nitrogen atmosphere and melted at 140 ° C. To this, 1.44 g (3.62 mmol) of the intermediate (6) and 5.53 g (19.3 mmol) of tetrachlorphthalic anhydride were added, and the mixture was stirred at 220 ° C. for 4 hours. After allowing to cool, 300 mL of acetone was added to the reaction solution, and the mixture was stirred for 1 hour, and then 4.52 g (3.08 mmol) of the target product (7) as a yellow powder was obtained by vacuum filtration (yield: 85%).

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

(Pigmentation of quinophthalone compounds)
5 parts by mass of the obtained quinophthalone dimer (7), 50 parts by mass of pulverized sodium chloride, and 8 parts by mass of diethylene glycol were charged into a dual-arm kneader and kneaded at 80 ° C. for 8 hours. After kneading, the mixture was taken out to 6000 parts by mass of water at 80 ° C., stirred for 1 hour, filtered, washed with hot water, dried and pulverized to obtain quinophthalone pigment A which is a yellow pigment. The quinophthalone pigment A obtained with a transmission electron microscope JEM-2010 manufactured by JEOL Ltd. was photographed. The average aspect ratio is calculated from the average value of the longer diameter (major diameter) and the shorter diameter (minor diameter) of the 40 primary particles that make up the aggregate on the secondary image, and the average value of the major diameter is the average primary particle. The diameter was set. The average aspect ratio was less than 3.00. The average primary particle size was 100 nm or less.

(Preparation of composition for evaluation)
C. I. An evaluation composition was obtained in the same manner as in Production Example 1 except that the obtained quinophthalone pigment A was used instead of Pigment Red 269.

^１Ｈ−ＮＭＲ（ＤＭＳＯ−ｄ６）δｐｐｍ：２．７０（ｓ，６Ｈ），４．４２（ｓ，２Ｈ），７．５８（ｄ，Ｊ＝８．８Ｈｚ，２Ｈ），７．６３（ｄ，Ｊ＝８．８Ｈｚ，２Ｈ），８．０９（ｄ，Ｊ＝８．８Ｈｚ，２Ｈ），８．１３（ｄ，Ｊ＝８．８Ｈｚ，２Ｈ）
^１３Ｃ−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[Production Example 16: Composition for Evaluation of Kinoftalone Pigment B]
(Synthesis of quinophthalone compounds)
First, a quinophthalone compound was synthesized according to the following procedure.
Put 55 g of concentrated sulfuric acid in a flask and stir under ice-cooling to obtain 7.0 g of 6,6'-methylenediquinaldin obtained by the method described in the literature (Polymer, volume39, No.20 (1998), p4949). 23.5 mmol) was added. 6.1 g of 60% nitric acid was added dropwise while maintaining 10 ° C. or lower, and stirring was continued at 10 ° C. to 20 ° C. for 1 hour. The reaction solution was poured into 150 ml of ice water, and the pH was adjusted to 3 with a 20 wt% sodium hydroxide aqueous solution. The precipitated powder was collected by vacuum filtration and washed with water to neutrality. The obtained solid was air-dried at 70 ° C., and then the crude product was washed and filtered with 100 ml of hot ethyl acetate and then 60 ml of hot toluene to obtain 6.52 g (16.8 mmol) of the intermediate (8) (yield). : 72%).

^{1 1} H-NMR (DMSO-d6) δppm: 2.70 (s, 6H), 4.42 (s, 2H), 7.58 (d, J = 8.8Hz, 2H), 7.63 (d, J = 8.8Hz, 2H), 8.09 (d, J = 8.8Hz, 2H), 8.13 (d, J = 8.8Hz, 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

^１Ｈ−ＮＭＲ（ＤＭＳＯ−ｄ６）δｐｐｍ：２．５７（ｓ，６Ｈ），３．４５（ｓ，２Ｈ），５．６６（ｓ，４Ｈ），７．０６（ｄ，Ｊ＝８．２Ｈｚ，２Ｈ），７．１６（ｄ，Ｊ＝８．２Ｈｚ，２Ｈ），７．２３（ｄ，Ｊ＝８．２Ｈｚ，２Ｈ），８．４９（ｄ，Ｊ＝８．２Ｈｚ，２Ｈ）
^１３Ｃ−ＮＭＲ（ＤＭＳＯ−ｄ６）δｐｐｍ：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^−１：３４６４，３３６３，３３１５，３１９２，１６４０，１５９１，１５７３，１４１５，１３６５，８０１Subsequently, 5.30 g of reduced iron and 135 ml of acetic acid were charged in the flask and heated to 50 ° C. with stirring. Next, 4.50 g (11.6 mmol) of the intermediate (8) was added so as to keep the temperature below 70 ° C. After completion of the addition, stirring was continued at 60 ° C. for 1 hr, the reaction solution was cooled to 35 ° C. or lower, poured into 500 ml of ice water, and adjusted to pH 9 with 20% NaOH water. The resulting precipitate was filtered under reduced pressure over Celite. The solid was collected, air-dried at 70 ° C., added to a mixed solvent of 100 ml of dimethyl sulfoxide (DMSO) and 100 ml of N, N-dimethylformamide (DMF), and stirred at 90 ° C. for 1 hr. The mixture was filtered under reduced pressure over Celite and the resulting filtrate was added to 1 L of water with stirring. The produced precipitate was collected by vacuum filtration and washed with water to obtain 3.80 g (11.6 mmol) of the intermediate (9) (yield:> 99%).

^{1 1} H-NMR (DMSO-d6) δppm: 2.57 (s, 6H), 3.45 (s, 2H), 5.66 (s, 4H), 7.06 (d, J = 8.2Hz, 2H), 7.16 (d, J = 8.2Hz, 2H), 7.23 (d, J = 8.2Hz, 2H), 8.49 (d, J = 8.2Hz, 2H)
¹³ C-NMR (DMSO-d6) δppm: 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＋Subsequently, 135 g of benzoic acid was weighed in a flask under a nitrogen atmosphere and melted at 140 ° C. To this, 3.80 g (11.6 mmol) of the intermediate (9), 17.99 g (62.9 mmol) of tetrachlorphthalic anhydride, and 0.49 g (3.6 mmol) of anhydrous zinc chloride were added, and the mixture was added at 220 ° C. The mixture was stirred for 6 hours. After cooling the reaction mixture to 120 ° C., 300 mL of chlorobenzene was added and the mixture was stirred for 1 hour, and 10.5 g (7.5 mmol) of the target product (10) as a yellow powder was obtained by vacuum filtration (yield: 65%). ..

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

(Pigmentation of quinophthalone compounds)
Pigmentation was carried out in the same manner as in Production Example 14 except that the quinophthalone dimer (10) was used instead of the quinophthalone dimer (7) to obtain a quinophthalone pigment B. The average aspect ratio of the obtained quinophthalone pigment B was less than 3.00, and the average primary particle size was 100 nm or less.

(Preparation of composition for evaluation)
C. I. An evaluation composition was obtained in the same manner as in Production Example 1 except that the obtained quinophthalone pigment B was used instead of Pigment Red 269.

[Production Example 17: Composition for Evaluation of Pigment Blue 15: 6]
C. I. Instead of Pigment Red 269, DIC Corporation C.I. I. An evaluation composition was obtained in the same manner as in Production Example 1 except that Pigment Blue 15: 6 was used.

[Production Example 18: Composition for Evaluation of Dye A]
Dye A, which is a xanthene dye, was synthesized according to "Synthesis Example 6: Synthesis of Dye A6" in JP-A-2010-254964. C. I. An evaluation composition was obtained in the same manner as in Production Example 1 except that the obtained dye A was used instead of Pigment Red 269.

[Example 1-1]
(Preparation of red colored film)
The composition for evaluation of Pigment Red 269 of Production Example 1 and the composition for evaluation of Pigment Yellow 139 of Production Example 3 are mixed so that the blending ratio (mass ratio) of Pigment Red 269 / Pigment Yellow 139 is 7/3. , A coloring composition was obtained by mixing with a paint shaker. The obtained coloring composition was spin-coated on a soda glass substrate and then dried at 90 ° C. for 3 minutes to prepare an evaluation sample in which a red colored film was formed on the substrate. By adjusting the spin rotation speed at the time of spin coating, the thickness of the colored film after drying at 90 ° C. for 3 minutes was adjusted to 3 μm. Using a spectrophotometer (U3900 manufactured by Hitachi High-Tech Science Corporation), the chromaticity of the evaluation sample when the C light source was used was measured.

(Preparation of green colored film)
Instead of mixing the evaluation composition of Pigment Red 269 of Production Example 1 and the evaluation composition of Pigment Yellow 139 of Production Example 3, the evaluation composition of Pigment Green 59 of Production Example 12 and the pigment of Production Example 4 The substrate in the same manner as the evaluation sample of the red colored film, except that the composition for evaluation of yellow 138 was mixed so that the blending ratio (mass ratio) of pigment green 59 / pigment yellow 138 was 6.4. An evaluation sample having a green colored film formed on it was prepared, and the chromaticity of the evaluation sample was measured.

(Preparation of blue colored film)
Instead of mixing the evaluation composition of Pigment Red 269 of Production Example 1 and the evaluation composition of Pigment Yellow 139 of Production Example 3, the evaluation composition of Pigment Blue 15: 6 of Production Example 17 and Production Example 18 The composition for evaluation of dye A was mixed on the substrate in the same manner as the sample for evaluation of the red colored film, except that the composition for evaluation of dye A was mixed so that the blending ratio of pigment blue 15: 6 / dye A was 4/6. An evaluation sample on which a blue colored film was formed was prepared, and the chromaticity of the evaluation sample was measured.

(Evaluation of color reproducibility)
The three chromaticity coordinates of the obtained red colored film, green colored film, and blue colored film on the xy chromaticity diagram were connected to each other by a straight line, and the area of the triangle formed by the straight line was calculated. The calculated area of the triangle is shown in Table 5. Table 5 also shows the ratio of the area of the obtained triangle to the area of the triangle defined by NTSC (= 0.1582) (NTSC ratio). The larger the area of the triangle and the NTSC ratio, the higher the color reproducibility.

[Examples 1-2 to 1-7 and Comparative Examples 1-1 to 1-2]
In the production of the red colored film, except that the evaluation composition of each yellow color material of Production Examples 4 to 11 was used instead of the evaluation composition of Pigment Yellow 139 of Production Example 3, the same as Example 1-1. In the same manner, an evaluation sample was prepared, the chromaticity was measured, and the color reproducibility was evaluated. The results are shown in Table 5.

[Comparative Example 1-3]
In the preparation of the red colored film, the same procedure as in Example 1-1 was used except that the evaluation composition of Pigment Red 254 of Production Example 2 was used instead of the evaluation composition of Pigment Red 269 of Production Example 1. , A sample for evaluation was prepared, the chromaticity was measured, and the color reproducibility was evaluated. The results are shown in Table 5.

[Examples 2-1 to 2-7 and Comparative Examples 2-1 to 2-2]
In the preparation of the green colored film, instead of mixing the evaluation composition of Pigment Green 59 of Production Example 13 and the evaluation composition of Pigment Yellow 138 of Production Example 4, the evaluation composition of Pigment Green 58 of Production Example 12 Except that the product and the composition for evaluation of quinophthalone pigment A of Production Example 15 were mixed so that the blending ratio (mass ratio) of Pigment Green 58 / quinophthalone pigment A was 8/2, Examples 1-1 to 1 to 1 In the same manner as in 1-7 and Comparative Examples 1-1 to 1-2, an evaluation sample was prepared, the chromaticity was measured, and the color reproducibility was evaluated. The results are shown in Table 6.

[Examples 3-1 to 3-7 and Comparative Examples 3-1 to 3-2]
In the preparation of the green colored film, instead of mixing the evaluation composition of Pigment Green 59 of Production Example 13 and the evaluation composition of Pigment Yellow 138 of Production Example 4, the evaluation composition of Pigment Green 59 of Production Example 13 Examples 1-1 to 1 to 1 to 1 except that the product and the composition for evaluation of quinophthalone pigment A of Production Example 15 were mixed so that the blending ratio (mass ratio) of Pigment Green 58 / quinophthalone pigment A was 7/3. In the same manner as in 1-7 and Comparative Examples 1-1 to 1-2, a sample for evaluation was prepared, the chromaticity was measured, and the color reproducibility was evaluated. The results are shown in Table 7.

[Examples 4-1 to 4-7 and Comparative Examples 4-1 to 4-2]
In the preparation of the green colored film, instead of mixing the evaluation composition of Pigment Green 59 of Production Example 13 and the evaluation composition of Pigment Yellow 138 of Production Example 4, the evaluation composition of Pigment Green 58 of Production Example 12 Except that the product and the composition for evaluation of the quinophthalone pigment B of Production Example 16 were mixed so that the blending ratio (mass ratio) of Pigment Green 58 / quinophthalone pigment B was 8/2, Examples 1-1 to 1 to 1 In the same manner as in 1-7 and Comparative Examples 1-1 to 1-2, an evaluation sample was prepared, the chromaticity was measured, and the color reproducibility was evaluated. The results are shown in Table 8.

[Examples 5-1 to 5-7 and Comparative Examples 5-1 to 5-2]
In the preparation of the green colored film, instead of mixing the evaluation composition of Pigment Green 59 of Production Example 13 and the evaluation composition of Pigment Yellow 138 of Production Example 4, the evaluation composition of Pigment Green 59 of Production Example 13 Except that the product and the composition for evaluation of the quinophthalone pigment B of Production Example 16 were mixed so that the blending ratio (mass ratio) of the pigment green 59 / quinophthalone pigment B was 7/3, Examples 1-1 to 1 to 1 In the same manner as in 1-7 and Comparative Examples 1-1 to 1-2, an evaluation sample was prepared, the chromaticity was measured, and the color reproducibility was evaluated. The results are shown in Table 9.

[Comparative Examples 6-1 to 6-10]
In the preparation of the green colored film, instead of mixing the evaluation composition of the pigment green 59 of the production example 13 and the evaluation composition of the pigment yellow 138 of the production example 4, the evaluation composition of the pigment green 36 of the production example 14 Examples 1-1 to 1 to 1 to 1 except that the product and the composition for evaluation of Pigment Yellow 138 of Production Example 4 were mixed so that the blending ratio (mass ratio) of Pigment Green 36 / Pigment Yellow 138 was 8/2. In the same manner as in 1-7 and Comparative Examples 1-1 to 1-3, a sample for evaluation was prepared, the chromaticity was measured, and the color reproducibility was evaluated. The results are shown in Table 10.

As described above, in the red pixel portion, Pigment Red 269 and a yellow color material having an average transmittance of 6% or less at 440 to 470 nm are used in combination, and in the green pixel portion, a specific halogenated phthalocyanine pigment is used. By using, the area of the triangle in the xy chromaticity diagram can be increased (that is, high color reproducibility can be obtained). Such an effect is particularly remarkable when Pigment Green 59 is used as a specific halogenated phthalocyanine pigment.

[Example 7-1]
<Making color filters>
(Preparation of curable resin composition)
In the polymerization tank, 63 parts by mass of methyl methacrylate (MMA), 12 parts by mass of acrylic acid (AA), 6 parts by mass of -2-hydroxyethyl methacrylate (HEMA), and 88 parts by mass of diethylene glycol dimethyl ether (DMDG). After charging, stirring and dissolving, 7 parts by mass of 2,2'-azobis (2-methylbutyronitrile) was added and dissolved uniformly. Then, the mixture was stirred at 85 ° C. for 2 hours under a nitrogen stream, and reacted at 100 ° C. for another 1 hour. To the obtained solution, 7 parts by mass of glycidyl methacrylate (GMA), 0.4 parts by mass of triethylamine, and 0.2 parts by mass of hydroquinone were further added, and the mixture was stirred at 100 ° C. for 5 hours to obtain a copolymer resin solution ( Solid content: 50% by mass) was obtained.
Next, the following materials were stirred and mixed at room temperature to prepare a curable resin composition.
-The above copolymer resin solution (solid content: 50% by mass): 16 parts by mass-Dipentaerythritol pentaacrylate (Sartmer SR399): 24 parts by mass-Orthocresol novolac type epoxy resin (oiled shell epoxy company Epicoat 180S70): 4 parts by mass ・ 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropane-1-one: 4 parts by mass ・ Diethylene glycol dimethyl ether: 52 parts by mass

(Formation of light-shielding part)
First, each component was mixed with the following composition and sufficiently dispersed with a sand mill to prepare a black pigment dispersion liquid.
・ Black pigment (# 2600 manufactured by Mitsubishi Chemical Co., Ltd.): 20 parts by mass ・ Polymer dispersant (Disperbyk 111 manufactured by Big Chemie Japan Co., Ltd.): 16 parts by mass ・ Solvent (diethylene glycol dimethyl ether): 64 parts by mass Next, with the following composition Each component was sufficiently mixed to obtain a coloring composition for a light-shielding portion.
-The black pigment dispersion: 50 parts by mass-The curable resin composition: 20 parts by mass-Diethylene glycol dimethyl ether: 30 parts by mass The coloring composition for the light-shielding part is applied onto a substrate with a spin coater, and the temperature is 100 ° C. for 3 minutes. It was dried to form a layer. This layer is exposed to a light-shielding pattern using a photomask with an ultra-high pressure mercury lamp, developed with a 0.05 wt% potassium hydroxide aqueous solution, and then heat-treated by leaving the substrate in an atmosphere of 230 ° C. for 30 minutes. To form a light-shielding portion (black matrix).

(Formation of red pixel portion (RCF))
The composition for evaluation of Pigment Red 269 of Production Example 1 and the composition for evaluation of Pigment Yellow 139 of Production Example 3 are mixed so that the blending ratio (mass ratio) of Pigment Red 269 / Pigment Yellow 139 is 21/79. A photosensitive coloring composition was obtained by mixing 10 g of the mixed mixture, 3.19 g of the curable resin composition, and 1.83 g of propylene glycol monomethyl ether acetate with a paint shaker. This photosensitive coloring composition was applied by a spin coating method to form a coating film. Then, the coating film was dried in an oven at 90 ° C. for 3 minutes. Next, a photomask was placed at a distance of 100 μm from the coating film, and only the region corresponding to the region where the light-shielding portion was formed was irradiated with ultraviolet rays for 10 seconds using a 2.0 kW ultra-high pressure mercury lamp with a proximity liner. .. Then, it was immersed in a 0.05 mass% potassium hydroxide aqueous solution (liquid temperature 23 ° C.) for 1 minute and subjected to alkaline development to remove only the uncured portion of the coating film to obtain RCF.

For the blending ratio of Pigment Red 269 / Pigment Yellow 139 and the film thickness of the pixel portion (coating film), a white LED light source (manufactured by Nichia Chemical Industries, Ltd., NSSW304F-HG, hereinafter also referred to as "light source A") is used. At that time, the chromaticity of the pixel part (measured using a microscopic photophotometer) becomes (x, y) = (0.680, 0.320) of the DCI-P3 standard, and the brightness Y of the pixel part is the maximum. It was decided to be. The film thickness of the pixel portion (coating film) was adjusted by adjusting the spin rotation speed at the time of spin coating.

(Formation of green pixel part (GCF))
Instead of mixing the evaluation composition of Pigment Red 269 of Production Example 1 and the evaluation composition of Pigment Yellow 139 of Production Example 3, the evaluation composition of Pigment Green 59 of Production Example 13 and the quinophthalone of Production Example 15 GCF was obtained in the same manner as RCF except that the composition for evaluation of pigment A was mixed so that the blending ratio (mass ratio) of pigment green 59 / quinophthalone pigment A was 56/44. Similar to RCF, the blending ratio of Pigment Green 59 / quinophthalone pigment A and the film thickness of the pixel portion (coating film) are such that the chromaticity of the pixel portion is (x, y) = (when the light source A is used. It was determined to be 0.265, 0.690) and the brightness Y of the pixel portion was maximized.

(Formation of blue pixel portion (BCF))
Instead of mixing the evaluation composition of Pigment Red 269 of Production Example 1 and the evaluation composition of Pigment Yellow 139 of Production Example 3, the evaluation composition of Pigment Blue 15: 6 of Production Example 17 and Production Example 18 BCF was obtained in the same manner as RCF, except that the composition for evaluation of Dye A was mixed so that the blending ratio (mass ratio) of Pigment Blue 15: 6 / Dye A was 94/6. As with RCF, the blending ratio of Pigment Blue 15: 6 / Dye A and the film thickness of the pixel portion (coating film) are such that the chromaticity of the pixel portion is DCI-P3 standard when the light source A is used. It was determined that x, y) = (0.150, 0.060) and the brightness Y of the pixel portion was maximized.

As described above, a color filter having red, green, and blue color pixel portions was obtained. The area of each color pixel portion is measured so that the chromaticity calculated by the additive color mixing of each color pixel portion using the light source A is (x, y) = (0.3140, 0.3510) of the DCI-P3 standard. Was fine-tuned.

<Measurement of pixel film thickness>
The thickness of each color pixel portion obtained was measured with a white interference microscope VS1330 manufactured by Hitachi High-Tech Science Corporation. The results are shown in Table 11.

<Assembly of display device and calculation of white brightness Y>
An alignment film was formed on each of the pair of substrates, and a liquid crystal composition was dropped and bonded between the pair of substrates to form a liquid crystal layer between the substrates. The color filter obtained above was further bonded to one of the substrates to obtain a display unit. Further, a plurality of light sources A were attached to a housing provided with a drive board to obtain a backlight portion. An evaluation display device was obtained by arranging the side opposite to the color filter of the display unit and the light emitting side of the backlight so as to face each other. In this evaluation display device, the brightness Y of white was calculated by the additive color mixing of the brightness Y of each color pixel portion. The results are shown in Table 11.

[Example 7-2 and Comparative Examples 7-1 to 7-2]
In the formation of RC F, the evaluation composition of Pigment Red 269 of Production Example 1 and the evaluation composition of the yellow color material (yellow pigment) shown in Table 11 (the preparation method is as described in the above production example) are shown in Table. The composition (preparation) for evaluation of the green color material (green pigment) shown in Table 11 in the formation of GCF by mixing so as to have the blending ratio (pigment red 269 / yellow color material (mass ratio)) shown in 11. The method is as described in the above production example) and the composition for evaluation of pigment yellow 185 of production example 5 are mixed so as to have a blending ratio (green color material / pigment yellow 185 (mass ratio)) shown in Table 11. Except for the above, the color filter was produced, the film thickness of the pixel portion was measured, the display device was assembled, and the white brightness Y was calculated in the same manner as in Example 7-1. The results are shown in Table 11.

[Example 8-1 and Comparative Examples 8-1 to 8-3]
A composition for evaluation of Pigment Red 269 or Pigment Red 254 of Production Example 1 or 2 in the formation of RCF using a white LED light source (manufactured by Nikka Kagaku Kogyo Co., Ltd., NSSW157F, hereinafter also referred to as “light source B”). And the composition for evaluation of the yellow color material (yellow pigment) shown in Table 12 (the preparation method is as described in the above production example), and the blending ratio (Pigment Red 269 or 254 / yellow color material (mass) shown in Table 12). In addition, in the formation of GCF, the composition for evaluation of the green color material (green pigment) shown in Table 12 (the preparation method is as described in the above production example) and Production Example 5 are mixed so as to have a ratio)). The color for evaluation of Pigment Yellow 185 was mixed in the same manner as in Example 7-1 except that the composition was mixed so as to have the blending ratio (green color material / Pigment Yellow 185 (mass ratio)) shown in Table 12. The filter was manufactured, the thickness of the pixel portion was measured, the display device was assembled, and the white brightness Y was calculated. The results are shown in Table 12. In Table 12, when the color cannot be adjusted to the desired chromaticity, "color adjustment is not possible" is described in the columns of the blending ratio and the film thickness.

[Examples 9-1 to 9-10 and Comparative Example 9-1]
The chromaticity and white chromaticity of each color pixel portion are designed to be sRGB standard, and in the formation of RCF, the composition for evaluation of Pigment Red 269 of Production Example 1 and the yellow color material (yellow pigment) shown in Table 13 are used. The composition for evaluation (preparation method is as described in the above production example) is mixed so as to have the blending ratio (pigment red 269 / yellow color material (mass ratio)) shown in Table 13, and the GCF In the formation, the composition for evaluation of the green color material (green pigment) shown in Table 13 (the preparation method is as described in the above production example) and the composition for evaluation of the yellow color material (yellow pigment) shown in Table 13 (preparation). The method is the same as in Example 7-1 except that the mixture (as described in the above production example) is mixed so as to have the blending ratio (green color material / yellow color material (mass ratio)) shown in Table 13. , Fabrication of a color filter, measurement of the film thickness of the pixel portion, assembly of a display device, and calculation of white brightness Y. The results are shown in Table 13. The chromaticity and white chromaticity of each color pixel portion according to the sRGB standard are as follows.
Red (x, y) = (0.640, 0.330)
Green (x, y) = (0.300, 0.600)
Blue (x, y) = (0.150, 0.060)
White (x, y) = (0.3127, 0.3290)

[Examples 10-1 to 10-3 and Comparative Examples 10-1 to 10-3]
A light source B is used as a light source, and the chromaticity and white chromaticity of each color pixel portion are designed to be sRGB standard, and in the formation of RCF, the composition for evaluation of Pigment Red 269 or Pigment Red 254 of Production Example 1 or 2. The material and the composition for evaluation of the yellow color material (yellow pigment) shown in Table 14 (the preparation method is as described in the above production example) are mixed with the compounding ratio (Pigment Red 269 or 254 / yellow color material (Pigment Red 269 or 254 / yellow color material) shown in Table 14. In addition, in the formation of GCF, the composition for evaluation of the green color material (green pigment) shown in Table 14 (the preparation method is as described in the above production example) and Production Example 4 are mixed so as to have a mass ratio)). In the same manner as in Example 7-1, except that the composition for evaluation of Pigment Yellow 138 was mixed so as to have a blending ratio (green color material / Pigment Yellow 138 (mass ratio)) shown in Table 14. The color filter was manufactured, the film thickness of the pixel portion was measured, the display device was assembled, and the white brightness Y was calculated. The results are shown in Table 14. In Table 14, when the color cannot be adjusted to the desired chromaticity, "color adjustment is not possible" is described in the columns of the blending ratio and the film thickness.

As described above, in the red pixel portion, Pigment Red 269 and a yellow color material having an average transmission rate of 6% or less at 440 to 470 nm are used in combination, and in the green pixel portion, a specific halogenated phthalocyanine pigment is used. By using the above, the thickness of the red pixel portion and the green pixel portion can be reduced even when the brightness is designed to be high in the DCI-P3 standard and the sRGB standard. Such an effect is particularly remarkable when Pigment Green 59 is used as a specific halogenated phthalocyanine pigment.

1 ... Liquid crystal display device (display device), 2 ... Light source, 3 ... First polarizing layer, 4 ... First substrate, 5 ... First electrode, 6 ... Liquid crystal layer, 7 ... Second electrode, 8 ... Second polarizing layer, 9 ... color filter, 10 ... second substrate, L ... light from a light source.

Claims (4)

C. I. A red pixel portion including Pigment Red 269 and a yellow color material having an average transmittance of 6% or less at 440 to 470 nm.
A color filter comprising a green pixel portion containing at least one selected from the group consisting of a halogenated zinc phthalocyanine pigment and a halogenated aluminum phthalocyanine pigment. The yellow color material is C.I. I. Pigment Yellow 129, C.I. I. Pigment Yellow 138, C.I. I. Pigment Yellow 139, C.I. I. Pigment Yellow 150, C.I. I. Pigment Yellow 151, C.I. I. Pigment Yellow 185 and C.I. I. The color filter according to claim 1, which is at least one selected from the group consisting of sulfonated derivatives of Pigment Yellow 12. The green pixel portion is C.I. I. Pigment Green 58 and C.I. I. The color filter according to claim 1 or 2, which comprises at least one zinc halide phthalocyanine pigment selected from the group consisting of Pigment Green 59. The color filter according to any one of claims 1 to 3, wherein the green pixel portion further contains a compound represented by the following formula (1).

[In formula (1), X ^{1 to} X ¹⁶ are independently hydrogen atoms or halogen atoms, Y ¹ and Y ² are independently hydrogen atoms or halogen atoms, and Z is an alkylene having 1 to 3 carbon atoms. It is the basis. ]

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