Zinc phthalocyanine polyhalide, coloring composition, color filter, and method for producing zinc phthalocyanine polyhalide.

Abstract

This invention provides zinc phthalocyanine polyhalogenate, which contributes to improving the brightness of color filters. [Solution] A zinc phthalocyanine polyhalide comprising a compound represented by the following general formula (i), wherein, in the mass spectrum obtained by matrix-assisted laser desorption / ionization time-of-flight mass spectrometry, when the maximum ionic intensity in the range of m / z 1820 to 1860 is denoted as I1 and the maximum ionic intensity in the range of m / z 1740 to less than 1780 is denoted as I2, the ratio I2 / I1 is 0.50 or less. TIFF2026086779000008.tif68149

Description

[Technical Field]

[0001] This disclosure relates to polyhalogenated zinc phthalocyanine, a coloring composition, a color filter, and a method for producing polyhalogenated zinc phthalocyanine. [Background technology]

[0002] Green pigments containing zinc phthalocyanine polyhalide are sometimes used in color filters for liquid crystal displays. Examples of pigments containing zinc phthalocyanine polyhalide include Pigment Green 58.

[0003] In recent years, with the increasing resolution of liquid crystal displays, there has been a demand for higher brightness in color filters. In response to this, for example, Patent Document 1 proposes improving the brightness of color filters by changing the halogen ratio of zinc phthalocyanine polyhalide. [Prior art documents] [Patent Documents]

[0004] [Patent Document 1] Japanese Patent Publication No. 2007-284589 [Overview of the Initiative] [Problems that the invention aims to solve]

[0005] The brightness-enhancing effect of zinc phthalocyanine polyhalogenate described in Patent Document 1 above is still not considered sufficient.

[0006] The purpose of this disclosure is to provide zinc phthalocyanine polyhalogenate that contributes to improving the brightness of color filters. [Means for solving the problem]

[0007] Some aspects of this disclosure relate to the following [1] to

[14] .

[0008] [1] The following general formula (i) [Chemical formula] (In general formula (i), X , , ,

[0011] ~X 16 each independently represents a hydrogen atom or a halogen atom. However, at least two of X 1 ~X 16 are halogen atoms.) and includes a compound represented by In the mass spectrum obtained by matrix-assisted laser desorption ionization time-of-flight mass spectrometry, when the maximum ion intensity in the range of m / z 1820 or more and 1860 or less is defined as I1, and the maximum ion intensity in the range of m / z 1740 or more and less than 1780 is defined as I2, a polyhalogenated zinc phthalocyanine in which I2 / I1 is 0.50 or less.

[0009] [2] In the mass spectrum obtained by matrix-assisted laser desorption ionization time-of-flight mass spectrometry, when the maximum ion intensity in the range of m / z 1820 or more and 1860 or less is defined as I1, and the maximum ion intensity in the range of m / z 1780 or more and less than 1820 is defined as I3, the polyhalogenated zinc phthalocyanine according to [1], in which I3 / I1 is 1.00 or less.

[0010] [3] In the mass spectrum obtained by matrix-assisted laser desorption ionization time-of-flight mass spectrometry, when the maximum ion intensity in the range of m / z 1820 or more and 1860 or less is defined as I1, and the maximum ion intensity in the range of m / z 1650 or more and less than 1740 is defined as I4, the polyhalogenated zinc phthalocyanine according to [1] or [2], in which I4 / I1 is 0.45 or less.

[0011] [4] A zinc phthalocyanine polyhalogenate as described in any of [1] to [3], wherein, in the mass spectrum obtained by matrix-assisted laser desorption / ionization time-of-flight mass spectrometry, I1 is defined as the maximum ionic intensity in the range of m / z 1820 to 1860, and I5 is defined as the maximum ionic intensity in the range of m / z 900 to less than 1650, and I5 / I1 is 0.50 or less.

[0012] [5] A zinc phthalocyanine polyhalogenate according to any one of [1] to [4], wherein the zinc content determined by ICP emission spectrometry is 2.5 to 5.0% by mass.

[0013] [6] A zinc phthalocyanine polyhalogenate according to any one of [1] to [5], wherein the bromine content determined by combustion ion chromatography is 30 to 80% by mass.

[0014] [7] A zinc phthalocyanine polyhalogenate according to any one of [1] to [6], wherein the chlorine content determined by combustion ion chromatography is 0.1 to 10% by mass.

[0015] [8] A zinc phthalocyanine polyhalogenate as described in any of [1] to [7], having an average primary particle size of 5 to 100 nm.

[0016] [9] A coloring composition comprising polyhalogenated zinc phthalocyanine as described in any of [1] to [8].

[0017]

[10] A color filter comprising a pixel portion containing zinc phthalocyanine polyhalogenate as described in any of [1] to [8].

[0018]

[11] The first step involves preparing a first reaction solution containing a metal salt and a halogenating agent, A second step involves mixing zinc phthalocyanine with the first reaction solution to obtain a second reaction solution, A third step involves mixing a halogenating agent with the second reaction solution to obtain a third reaction solution, A fourth step involves heating the third reaction solution. It includes at least, A method for producing zinc phthalocyanine polyhalide, wherein the heating rate of the third reaction solution in the fourth step is 2.5°C / hour or less.

[0019]

[12] The method for producing zinc phthalocyanine polyhalogenate according to

[11] , wherein the starting temperature for heating in the fourth step is 5 to 50°C.

[0020]

[13] A method for producing zinc phthalocyanine polyhalogenate according to

[11] or

[12] , wherein the temperature at which the heating is completed in the fourth step is 75 to 170°C.

[0021]

[14] A method for producing zinc phthalocyanine polyhalogenate according to any one of

[11] to

[13] , wherein the first step is to mix a second halogenating agent into a reaction solution containing a first halogenating agent and the metal salt. [Effects of the Invention]

[0022] According to this disclosure, it is possible to provide zinc phthalocyanine polyhalogenate that contributes to improving the brightness of color filters. [Brief explanation of the drawing]

[0023] [Figure 1] The mass spectrum of Example 13 obtained by matrix-assisted laser desorption / ionization time-of-flight mass spectrometry is shown. [Modes for carrying out the invention]

[0024] Hereinafter, exemplary embodiments of the present disclosure will be described. However, the present disclosure is not limited to the following embodiments in any way.

[0025] <Zinc polyhalogenated phthalocyanine> One embodiment of the present disclosure is a zinc polyhalogenated phthalocyanine containing a compound represented by the following general formula (i). [Chemical formula]

[0026] In the general formula (i), X 1 ~X 16 each independently represents a hydrogen atom or a halogen atom. However, at least two of X 1 ~X 16 are halogen atoms. Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.

[0027] In the present disclosure, "zinc polyhalogenated phthalocyanine" can be a composition containing one or more compounds represented by the above formula (i). Therefore, "zinc polyhalogenated phthalocyanine" of the present disclosure can also be read as "zinc polyhalogenated phthalocyanine composition".

[0028] (First Embodiment) The zinc polyhalogenated phthalocyanine of the first embodiment (hereinafter referred to as "zinc polyhalogenated phthalocyanine A1") has the following characteristics in the mass spectrum obtained by matrix-assisted laser desorption ionization time-of-flight mass spectrometry (MALDI-TOF MS). When the maximum ion intensity in the range of m / z 1820 or more and 1860 or less is I1, and the maximum ion intensity in the range of m / z 1740 or more and less than 1780 is I2, I2 / I1 (the ratio of the maximum ion intensity I2 to the maximum ion intensity I1) is 0.50 or less. Here, the maximum ion intensity refers to the intensity of the peak with the highest intensity in each of the above ranges. The maximum ion intensity I1 is 16-brominated zinc phthalocyanine (X 1 ~X16 This is the peak intensity corresponding to a compound in which all atoms are bromine atoms. The maximum ionic intensity I2 corresponds to 15 zinc brominated phthalocyanine (X in formula (i)). 1 ~X 16 (A compound in which 15 of the atoms are bromine atoms and 1 is a hydrogen atom) and / or 14 bromine dichloride zinc phthalocyanine (X in formula (i)) 1 ~X 16 This represents the peak intensity corresponding to a compound in which 14 of the atoms are bromine atoms and 2 are chlorine atoms.

[0029] MALDI-TOF MS can be performed using, for example, the JMS-S3000 manufactured by JEOL Ltd. In MALDI-TOF MS, when mass spectrometry is performed on a compound whose molecular weight is known to be Q, the measurement parameters are set so that m / z=Q is detected.

[0030] Because of the above-mentioned characteristics, polyzinc phthalocyanine A1 can improve the brightness of color filters, specifically the brightness in the green pixel area. Furthermore, using polyzinc phthalocyanine A1 as a pigment for color filters tends to improve the contrast of the color filter.

[0031] The reason for the above effect is not clear, but it can be inferred as follows. First, the brightness of the green pixel portion of a color filter depends on the transmittance of light in the 480-580 nm wavelength range, which is recognized as green. The higher the transmittance of light in this wavelength range, the higher the brightness of the green pixel portion. Therefore, in order to increase the brightness of the green pixel portion, it is important to use a compound as a pigment that does not absorb light in the above wavelength range. In this regard, zinc phthalocyanine polyhalide exhibits greater molecular distortion as the number of bromine atoms on the phthalocyanine ring increases, resulting in absorption on the longer wavelength side. Therefore, the higher the proportion of zinc 16-brominated phthalocyanine, the more the absorption peak will be on the longer wavelength side than the above wavelength range, making it difficult to absorb light in the above wavelength range (especially around 580 nm). In contrast, polyzinc phthalocyanine polyhalide A1 has an I2 / I1 ratio of 0.50 or less, meaning that compared to conventional polyzinc phthalocyanine polyhalide, the ratio of zinc phthalocyanine 15-brominated and zinc phthalocyanine 14-bromine-dichloride to zinc phthalocyanine 16-brominated is smaller (i.e., the ratio of zinc phthalocyanine 16-brominated is larger). In other words, polyzinc phthalocyanine polyhalide A1 is less likely to absorb light in the above wavelength range (especially around 580 nm) than conventional materials. Therefore, it is presumed that using polyzinc phthalocyanine polyhalide A1 can increase the transmittance of light in the 480-580 nm wavelength range, thereby improving the brightness of the color filter.

[0032] I2 / I1 may be 0.45 or less or 0.30 or less, from the viewpoint of further improving the brightness and contrast of the color filter. I2 / I1 may be 0.01 or more, for example, 0.01 to 0.50, 0.01 to 0.45, or 0.01 to 0.30.

[0033] In addition to the peaks corresponding to 16-zinc brominated phthalocyanine, 15-zinc brominated phthalocyanine, and 14-zinc bromine dichloride phthalocyanine, several peaks corresponding to the compound represented by formula (i) can be observed on the mass spectrum described above.

[0034] In the range of m / z 1780 to less than 1820, 15 brominated monochlorinated zinc phthalocyanine (X in formula (i)) 1 ~X 16 A peak corresponding to a compound in which 15 atoms are bromine and 1 atom is chlorine may be observed. When the maximum ionic intensity in the above range (m / z 1780 to less than 1820) is denoted as I3, I3 / I1 (the ratio of the maximum ionic intensity I3 to the maximum ionic intensity I1) may be 1.00 or less. When I3 / I1 is 1.00 or less, the brightness and contrast of the color filter tend to improve further. From a similar viewpoint, I3 / I1 may be 0.70 or less, less than 0.50, or 0.45 or less. I3 / I1 may be 0.01 or greater, 0.05 or greater, 0.15 or greater, 0.30 or greater, 0.45 or greater, or 0.60 or greater, and may be between 0.01 and 1.00, 0.05 and 0.70, 0.15 and less than 0.5, 0.15 and 0.45, 0.30 and 1.00, 0.45 and 1.00, or 0.60 and 1.00.

[0035] In the range of m / z 1650 to less than 1740, 13 bromine dichloride zinc phthalocyanine (X in formula (i)) 1 ~X 16 (A compound in which 13 of the atoms are bromine atoms, 2 are chlorine atoms, and 1 is hydrogen atom), 14 zinc brominated phthalocyanine (X in formula (i)) 1 ~X 16 Peaks corresponding to compounds (of which 14 are bromine atoms and 2 are hydrogen atoms) may be observed. When the maximum ionic intensity in the above range (m / z 1650 to less than 1740) is I4, I4 / I1 (the ratio of the maximum ionic intensity I4 to the maximum ionic intensity I1) may be 0.45 or less. When I4 / I1 is 0.45 or less, the brightness and contrast of the color filter tend to improve further. From a similar viewpoint, I4 / I1 may be 0.40 or less, 0.35 or less, 0.30 or less, or 0.25 or less. I4 / I1 may be 0.01 or more, 0.05 or more, 0.10 or more, or 0.35 or more, and may be 0.01 to 0.45, 0.01 to 0.40, 0.05 to 0.35, 0.10 to 0.30, 0.10 to 0.25, or 0.35 to 0.45.

[0036] In the range of m / z 900 to less than 1650, 13 bromine monochloride zinc phthalocyanine (X in formula (i)) 1 ~X 16 (A compound in which 13 of the atoms are bromine atoms, 1 is a chlorine atom, and 2 are hydrogen atoms), 13 zinc brominated phthalocyanine (X in formula (i)) 1 ~X 16 Peaks corresponding to compounds (such as those in which 13 atoms are bromine and 3 atoms are hydrogen) may be observed. When the maximum ionic intensity in the above range (m / z 900 to less than 1650) is I5, I5 / I1 (the ratio of the maximum ionic intensity I5 to the maximum ionic intensity I1) may be 0.50 or less. When I5 / I1 is 0.50 or less, the brightness and contrast of the color filter tend to improve further. From a similar viewpoint, I5 / I1 may be 0.30 or less, 0.24 or less, or 0.20 or less. I4 / I1 may be 0.01 or more, for example, 0.01 to 0.50, 0.01 to 0.30, 0.01 to 0.24, or 0.01 to 0.20.

[0037] The ratio of I5 to I2 (the ratio of the maximum ionic intensity I5 to the maximum ionic intensity I2) may be 1.30 or less, 1.00 or less, 0.70 or less, 0.60 or less, 0.50 or less, or 0.25 or less, from the viewpoint of achieving both high brightness and high contrast. I5 / I2 may be 0.05 or more, 0.10 or more, 0.15 or more, 0.20 or more, or 0.40 or more, and may be between 0.05 and 1.30, 0.10 and 1.00, 0.15 and 0.70, 0.20 and 0.60, 0.40 and 0.50, or 0.10 and 0.25.

[0038] The above maximum ionic intensity I1 may be the maximum among the peak intensities corresponding to the compound represented by equation (i).

[0039] The sum of the above maximum ionic intensities I1 to I5 (I1 + I2 + I3 + I4 + I5) is I T Therefore, I1 / I TFrom the viewpoint of achieving both high brightness and high contrast, the value may be 0.35 or higher, 0.45 or higher, or 0.55 or higher, and may be 0.75 or lower, 0.70 or lower, or 0.65 or lower, and may be 0.35 to 0.75, 0.45 to 0.70, or 0.55 to 0.65.

[0040] I2 / I T From the viewpoint of achieving both high brightness and high contrast, the value may be 0.01 or higher, 0.05 or higher, or 0.07 or higher, and may be 0.30 or lower, 0.20 or lower, or 0.10 or lower, and may be 0.01 to 0.30, 0.05 to 0.20, or 0.07 to 0.10.

[0041] I3 / I T From the viewpoint of achieving both high brightness and high contrast, the value may be 0.05 or higher, 0.10 or higher, or 0.20 or higher, and may be 0.50 or lower, 0.40 or lower, or 0.30 or lower, and may be 0.05 to 0.50, 0.10 to 0.40, or 0.20 to 0.30.

[0042] I4 / I T From the viewpoint of achieving both high brightness and high contrast, the value may be 0.01 or higher, 0.05 or higher, or 0.07 or higher, and may be 0.30 or lower, 0.15 or lower, or 0.10 or lower, and may be 0.01 to 0.30, 0.05 to 0.15, or 0.07 to 0.10.

[0043] I5 / I T From the viewpoint of achieving both high brightness and high contrast, the value may be 0.01 or higher, 0.03 or higher, or 0.05 or higher, and may be 0.15 or lower, 0.10 or lower, or 0.08 or lower, and may be 0.01 to 0.15, 0.03 to 0.10, or 0.05 to 0.08.

[0044] (Second embodiment) The polyhalogenated zinc phthalocyanine of the second embodiment (hereinafter referred to as "polyhalogenated zinc phthalocyanine A2") is characterized in that the above I3 / I1 ratio is 0.60 to 1.00 and the above I5 / I2 ratio is 1.00 or less.

[0045] Because of the above-mentioned characteristics, polyzinc phthalocyanine A2 can improve the brightness of color filters, specifically the brightness in the green pixel area. Furthermore, using polyzinc phthalocyanine A2 as a pigment for color filters tends to improve the contrast of the color filter.

[0046] Although the reason for the above effect is not clear, it is presumed that polyzinc halide phthalocyanine A2 has an absorption peak shifted to the longer wavelength side due to I3 / I1 and I5 / I2 being within the above range, making it less likely to absorb light in the 480-580 nm wavelength range than conventional materials. Therefore, it is presumed that using polyzinc halide phthalocyanine A2 can increase the transmittance of light in the 480-580 nm wavelength range, thereby improving the brightness of the color filter.

[0047] The following description will focus only on features specific to the second embodiment, and will omit any descriptions that overlap with those of the first embodiment.

[0048] In the second embodiment, I2 / I1 may be 0.50 or less, or greater than 0.50. From the viewpoint of further improving the brightness and contrast of the color filter, I2 / I1 may be 0.50 or less, 0.45 or less, or 0.30 or less. I2 / I1 may be 0.01 or more, for example, 0.01 to 0.50, 0.01 to 0.45, or 0.01 to 0.30.

[0049] In the second embodiment, I3 / I1 may be 0.70 to 1.00 or 0.80 to 1.00.

[0050] In the second embodiment, I5 / I2 may be 0.80 or less or 0.70 or less from the viewpoint of further improving the brightness and contrast of the color filter. I5 / I2 may be 0.05 or more or 0.10 or more, for example, 0.05 to 1.00, 0.10 to 1.00, 0.10 to 0.80, or 0.10 to 0.70. I5 / I2 may be 0.15 or more, 0.20 or more, or 0.40 or more, for example, 0.15 to 0.70, 0.20 to 0.70, or 0.40 to 0.70.

[0051] (Third embodiment) The polyhalogenated zinc phthalocyanine of the third embodiment (hereinafter referred to as "polyhalogenated zinc phthalocyanine A3") is characterized in that the I4 / I1 ratio is 0.45 or less and the I5 / I2 ratio is 1.00 or less.

[0052] Because of the above-mentioned characteristics, polyzinc phthalocyanine A3 can improve the brightness of color filters, specifically the brightness in the green pixel area. Furthermore, using polyzinc phthalocyanine A3 as a pigment for color filters tends to improve the contrast of the color filters.

[0053] Although the reason for the above effect is not clear, it is presumed that polyzinc halide phthalocyanine A3 has an absorption peak shifted to the longer wavelength side due to I4 / I1 and I5 / I2 being within the above range, making it less likely to absorb light in the 480-580 nm wavelength range than conventional materials. Therefore, it is presumed that using polyzinc halide phthalocyanine A3 can increase the transmittance of light in the 480-580 nm wavelength range, thereby improving the brightness of the color filter.

[0054] The following description will focus only on features specific to the third embodiment, and will omit any descriptions that overlap with those of the first embodiment.

[0055] In the third embodiment, I2 / I1 may be 0.50 or less, or greater than 0.50. From the viewpoint of further improving the brightness and contrast of the color filter, I2 / I1 may be 0.50 or less, 0.45 or less, or 0.30 or less. I2 / I1 may be 0.01 or more, for example, 0.01 to 0.50, 0.01 to 0.45, or 0.01 to 0.30.

[0056] In the third embodiment, I4 / I1 may be 0.10 or higher, 0.20 or higher, or 0.35 or higher, from the viewpoint of further improving the brightness and contrast of the color filter, for example, 0.10 to 0.45, 0.20 to 0.45, or 0.35 to 0.45. I4 / I1 may also be 0.40 or lower, 0.35 or lower, 0.30 or lower, or 0.25 or lower, and may be 0.10 to 0.40, 0.10 to 0.35, 0.10 to 0.30, or 0.10 to 0.25.

[0057] In the third embodiment, I5 / I2 may be 0.80 or less or 0.70 or less from the viewpoint of further improving the brightness and contrast of the color filter. I5 / I2 may be 0.05 or more or 0.10 or more, for example, 0.05 to 1.00, 0.10 to 1.00, 0.10 to 0.80, or 0.10 to 0.70. I5 / I2 may be 0.15 or more, 0.20 or more, or 0.40 or more, for example, 0.15 to 0.70, 0.20 to 0.70, or 0.40 to 0.70.

[0058] (Fourth embodiment) The polyhalogenated zinc phthalocyanine of the fourth embodiment (hereinafter referred to as "polyhalogenated zinc phthalocyanine A4") is characterized in that the above I5 / I1 is 0.20 or less and the above I5 / I2 is 1.00 or less.

[0059] Because of the above-mentioned characteristics, polyzinc phthalocyanine A4 can improve the brightness of color filters, specifically the brightness in the green pixel area. Furthermore, using polyzinc phthalocyanine A4 as a pigment for color filters tends to improve the contrast of the color filter.

[0060] Although the reason for the above effect is not clear, it is presumed that polyzinc halide phthalocyanine A4 has an absorption peak shifted to the longer wavelength side due to I5 / I1 and I5 / I2 being within the above range, making it less likely to absorb light in the 480-580 nm wavelength range than conventional materials. Therefore, it is presumed that using polyzinc halide phthalocyanine A4 can increase the transmittance of light in the 480-580 nm wavelength range, thereby improving the brightness of the color filter.

[0061] The following description will focus only on the features specific to the fourth embodiment, and will omit any explanations that overlap with those of the first embodiment.

[0062] In the fourth embodiment, I2 / I1 may be 0.50 or less, or greater than 0.50. From the viewpoint of further improving the brightness and contrast of the color filter, I2 / I1 may be 0.50 or less, 0.45 or less, or 0.30 or less. I2 / I1 may be 0.01 or more, for example, 0.01 to 0.50, 0.01 to 0.45, or 0.01 to 0.30.

[0063] In the fourth embodiment, I5 / I1 may be 0.01 or greater, for example, 0.01 to 0.20, from the viewpoint of further improving the brightness and contrast of the color filter. I5 / I1 may be 0.15 or less or 0.10 or less, and may be 0.01 to 0.15 or 0.01 to 0.10.

[0064] In the fourth embodiment, I5 / I2 may be 0.80 or less or 0.70 or less from the viewpoint of further improving the brightness and contrast of the color filter. I5 / I2 may be 0.05 or more or 0.10 or more, for example, 0.05 to 1.00, 0.10 to 1.00, 0.10 to 0.80, or 0.10 to 0.70. I5 / I2 may be 0.15 or more, 0.20 or more, or 0.40 or more, for example, 0.15 to 0.70, 0.20 to 0.70, or 0.40 to 0.70.

[0065] As described above, the zinc phthalocyanine polyhalides A1 to A4 of the first to fourth embodiments (hereinafter collectively referred to as "zinc phthalocyanine polyhalides A") are used to further improve the brightness and contrast of the color filter, and the X in formula (i) 1 ~X 16 However, each may independently consist of a compound that is a hydrogen atom, a chlorine atom, or a bromine atom. That is, polyhalogenated zinc phthalocyanine A is X in formula (i). 1 ~X 16 The compound does not need to contain at least one halogen atom other than a chlorine atom or a bromine atom.

[0066] The zinc content of polyhalogenated zinc phthalocyanine A may be 2.5 to 5.0 mass% from the viewpoint of further improving the brightness and contrast of the color filter. The above zinc content may be 3.0 mass% or more, 3.2 mass% or more, or 3.5 mass% or more from the same viewpoint as above, or 4.5 mass% or less, 4.2 mass% or less, or 4.0 mass% or less, or 3.0 to 4.5 mass%, 3.2 to 4.2 mass%, or 3.5 to 4.0 mass%.

[0067] The "zinc content" mentioned above is the content based on the total mass of polyhalogenated zinc phthalocyanine A, as determined by ICP emission spectrometry. Specifically, it can be determined by the measurement method described in the examples.

[0068] The bromine content of polyhalogenated zinc phthalocyanine A may be 30 to 80% by mass from the viewpoint of further improving the brightness and contrast of the color filter. The above bromine content may be 35% by mass or more, 40% by mass or more, 75% by mass or less, 70% by mass or less, or 60% by mass or less, or 30 to 75% by mass, 35 to 70% by mass, or 40 to 60% by mass, from the same viewpoint as above.

[0069] The "bromine content" mentioned above is the content based on the total mass of polyhalide zinc phthalocyanine A, determined by combustion ion chromatography. Specifically, it can be determined by the measurement method described in the examples.

[0070] The chlorine content of polyhalogenated zinc phthalocyanine A may be 0.1 to 10% by mass from the viewpoint of further improving the brightness and contrast of the color filter. The above chlorine content may be 0.3% by mass or more or 0.5% by mass or more, 5% by mass or less or 3% by mass or less, or 0.3 to 5% by mass or 0.5 to 3% by mass from the same viewpoint as above.

[0071] The "chlorine content" mentioned above is the content based on the total mass of polyhalide zinc phthalocyanine A, as determined by combustion ion chromatography. Specifically, it can be determined by the measurement method described in the examples.

[0072] The spectral transmittance Ta of zinc phthalocyanine polyhalide A at 580 nm may be 34.0% or higher (e.g., 34.0-90.0%). The spectral transmittance Ta may also be 34.5-90.0% or 35.0-50.0%.

[0073] The spectral transmittance Tb of polyzinc halide phthalocyanine A at 510-530 nm may be 85.0% or higher (for example, 85.0-99.9%). The spectral transmittance Tb may also be 87.0-99.9% or 90.0-95.0%. Note that the above spectral transmittance Tb is the maximum spectral transmittance.

[0074] The spectral transmittance Tc of zinc phthalocyanine polyhalide A at 480 nm may be 35.0% or higher (e.g., 35.0-90.0%). The spectral transmittance Tc may also be 35.5-90.0% or 36.0-50.0%.

[0075] The above-mentioned spectral transmittance measurements of Ta, Tb, and Tc are performed in accordance with the Type 1 spectrophotometer specified in Japanese Industrial Standard JIS Z 8722 (Methods for measuring color - Reflected and transmitted object color). Specifically, first, a colored composition containing polyhalide zinc phthalocyanine A, a dispersant, an alkali-soluble resin, and an organic solvent is prepared. Next, a sample for measurement is prepared using this colored composition. Then, this sample for measurement is spin-coated onto soda glass to form a film with a film thickness of 0.2 to 5 μm after deposition. Next, the obtained laminate is dried at 70 to 100°C for 2 to 5 minutes, and then fired at 200 to 250°C for 30 minutes to 2 hours to obtain an evaluation glass substrate. Then, using the obtained evaluation glass substrate, the monochromatic spectral transmission spectrum is measured using a Hitachi High-Tech Science U-3900, and the transmittance values ​​at each wavelength are plotted.

[0076] Polyzinc phthalocyanine A may consist solely of the compound represented by formula (i) above, and may also contain compounds other than the compound represented by formula (i) above (e.g., raw materials, by-products, etc.). However, the main component of polyzinc phthalocyanine A may be the compound represented by formula (i) above. The content of the compound represented by formula (i) above may be 60% by mass or more, 80% by mass or more, or 95% by mass or more, based on the total mass of polyzinc phthalocyanine A.

[0077] Polyzinc phthalocyanine A is a particulate solid at room temperature (e.g., 15-35°C). The average particle size of the primary particles of polyzinc phthalocyanine A (hereinafter referred to as "average primary particles") may be 100 nm or less, 70 nm or less, 60 nm or less, or 50 nm or less, or 5 nm or more, or 10 nm or more, or 15 nm or more, or 5-100 nm, 5-70 nm, 10-60 nm, or 15-50 nm, from the viewpoint of further improving the brightness of the color filter. In this specification, polyzinc phthalocyanine with an average primary particle size of 5-100 nm is sometimes referred to as polyzinc phthalocyanine pigment.

[0078] The above-mentioned "average primary particle diameter" can be determined using a transmission electron microscope or a scanning electron microscope by the method described in the examples.

[0079] Polyhalogenated zinc phthalocyanine A can be synthesized, for example, according to the "Method for Producing Polyhalogenated Zinc Phthalocyanine" described in the embodiments below.

[0080] <Coloring composition> Another embodiment of the present disclosure is a colored composition comprising the above-described zinc polyhalogenate phthalocyanine A.

[0081] The coloring composition can be used to form the pixel portion (particularly the green pixel portion) of a color filter. According to the above coloring composition, the brightness of the pixel portion of the color filter can be improved.

[0082] The zinc halide phthalocyanine A contained in the coloring composition may be a zinc halide phthalocyanine pigment. The content of zinc halide phthalocyanine A in 100% by mass of the coloring composition may be 5 to 90% by mass, 5 to 50% by mass, or 5 to 40% by mass, from the viewpoint of colorant dispersibility and dispersion stability.

[0083] The coloring composition may optionally contain dispersants, resins, organic solvents, etc. These materials may be those commonly used as components of coloring compositions for forming the pixel portion (especially the green pixel portion) of a color filter.

[0084] Examples of dispersants include Disperbyk from Bic Chemie. TM Examples include 130, 161, 162, 163, 170, LPN-6919, LPN-21116, BASF's F-C46, F-C47, etc. Leveling agents, coupling agents, cationic surfactants, etc. may also be used in combination.

[0085] Examples of resins used include photosensitive resins and / or alkali-soluble resins. Examples of photosensitive resins include thermoplastic resins such as urethane resins, acrylic resins, polyamic acid resins, polyimide resins, styrene maleic acid resins, and styrene maleic anhydride resins, as well as photopolymerizable monomers such as difunctional monomers like 1,6-hexanediol diacrylate, ethylene glycol diacrylate, neopentyl glycol diacrylate, triethylene glycol diacrylate, bis(acryloxyethoxy)bisphenol A, and 3-methylpentanediol diacrylate, and polyfunctional monomers like trimethylolpropane triacrylate, pentaerythritol triacrylate, tris(2-hydroxyethyl) isocyanate, dipentaerythritol hexaacrylate, and dipentaerythritol pentaacrylate. Examples of alkali-soluble resins include acrylic copolymers having carboxyl groups and epoxy (meth)acrylate resins having carboxyl groups. When using a photosensitive resin, a known and conventional photopolymerization initiator may be used in combination.

[0086] Examples of organic solvents that can be used include aromatic solvents such as toluene, xylene, and methoxybenzene; acetic acid ester solvents such as ethyl acetate, butyl acetate, propylene glycol monomethyl ether acetate, and propylene glycol monoethyl ether acetate; propionate solvents such as ethoxyethyl propionate; alcohol solvents such as methanol and ethanol; ether solvents such as butyl cellosolve, propylene glycol monomethyl ether, diethylene glycol ethyl ether, and diethylene glycol dimethyl ether; ketone solvents such as methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone; aliphatic hydrocarbon solvents such as hexane; nitrogen compound solvents such as N,N-dimethylformamide, γ-butyrolactam, N-methyl-2-pyrrolidone, aniline, and pyridine; lactone solvents such as γ-butyrolactone; carbamic acid esters such as a 48:52 mixture of methyl carbamate and ethyl carbamate; and water.

[0087] The content of the dispersant in 100% by mass of the colored composition may be 1 to 90% by mass, or 3 to 50% by mass, as solid content, from the viewpoint of colorant dispersibility and dispersion stability.

[0088] The content of the resin coloring composition in 100% by mass may be 1 to 90% by mass, or 3 to 50% by mass, as solid content, from the viewpoint of colorant dispersibility and dispersion stability.

[0089] The content of the organic solvent in 100% by mass of the colored composition may be 10 to 95% by mass, or 40 to 90% by mass, from the viewpoint of the solubility and dispersion stability of the other components.

[0090] The coloring composition may contain pigments other than polyzinc phthalocyanine A. Examples of pigments other than polyzinc phthalocyanine A include well-known and conventional green pigments used to form green pixel portions (such as green metal halide phthalocyanine pigments). The mass ratio of polyzinc phthalocyanine A to the well-known and conventional green pigment (polyzinc phthalocyanine A: well-known and conventional green pigment) may be, for example, 100:0 to 80:20, or 100:0 to 90:10.

[0091] The coloring composition may contain a yellow pigment for toning in addition to the green pigment to bring out its properties. Examples of yellow pigments that can be used in combination include CI Pigment Yellow (PY) 1, 2, 3, 4, 5, 6, 10, 12, 13, 14, 15, 16, 17, 18, 24, 31, 32, 34, 35, 35:1, 36, 36:1, 37, 37:1, 40, 42, 43, 53, 55, 60, 61, 62, 63, 65, 73, 74, 77, 81, 83, 93, 94, 95, 97, 98, 100, 101, 104, 106, 108, 109, 1 Examples include 10, 113, 114, 115, 116, 117, 118, 119, 120, 126, 127, 128, 129, 138, 139, 150, 151, 152, 153, 154, 155, 156, 161, 162, 164, 166, 167, 168, 169, 170, 171, 172, 173, 174, 175, 176, 177, 179, 180, 181, 182, 185, 187, 199, 215, 231, etc. These can be used individually or in combination of two or more. The content of the yellow pigment may be, for example, 10 to 100 parts by mass per 100 parts by mass of polyhalogenated zinc phthalocyanine A.

[0092] <Color Filter> Another embodiment of the present disclosure is a color filter comprising a pixel portion containing zinc phthalocyanine polyhalide A.

[0093] The above color filter can exhibit excellent brightness by using the pixel portion containing polyhalogenated zinc phthalocyanine A as the green pixel portion.

[0094] Pixel portions containing polyzinc phthalocyanine A can be formed, for example, using the above-mentioned coloring composition. Therefore, pixel portions containing polyzinc phthalocyanine A may include the above-mentioned coloring composition or its cured product. The method for forming the pixel portions varies depending on the type of material contained in the coloring composition, but may be a known and conventional method such as photolithography, electrodeposition, transfer, micelle electrolysis, or PVED (Photovoltaic Electrodeposition).

[0095] Other components of the color filter may be the same as those of known and conventional color filters. The color filter may further include, for example, a black matrix, a pixel containing a red pigment, and a pixel containing a blue pigment. These can be manufactured using known and conventional materials and by known and conventional methods (e.g., the pixel formation method described above).

[0096] <Method for producing polyhalogenated zinc phthalocyanine> Another embodiment of the present disclosure is a method for producing zinc phthalocyanine polyhalogenate comprising a compound represented by the above general formula (i). This method comprises at least a first step of preparing a first reaction solution containing a metal salt and a halogenating agent; a second step of obtaining a second reaction solution by mixing zinc phthalocyanine with the first reaction solution; a third step of obtaining a third reaction solution by mixing a halogenating agent with the second reaction solution; and a fourth step of heating the third reaction solution, characterized in that the heating rate of the third reaction solution in the fourth step is 2.5°C / hour or less.

[0097] While there are known methods for producing polyzinc phthalocyanine polyhalides, such as the chlorosulfonic acid method, the halogenated phthalonitrile method, and the melting method, the production method of this embodiment (especially the first and second steps) may be carried out according to these known methods. Among these methods, the melting method can increase the proportion of zinc 16-brominate phthalocyanine, resulting in polyzinc phthalocyanine that contributes to improving the brightness of color filters.

[0098] In a typical melting method, a halogenating agent such as sulfuryl chloride or bromine is mixed with a molten metal salt (molten salt) that serves as a solvent during halogenation to prepare a first reaction solution. Zinc phthalocyanine is then mixed into the resulting first reaction solution to halogenate it. However, in the manufacturing method of this embodiment, after mixing zinc phthalocyanine into the first reaction solution, a halogenating agent is added, and the mixture is heated at a predetermined heating rate. By performing this process, polyhalogenated zinc phthalocyanine (for example, the polyhalogenated zinc phthalocyanine A described above) that contributes to improving the brightness of color filters can be obtained.

[0099] The following describes each step.

[0100] (First step) In the first step, a first reaction solution containing a metal salt and a halogenating agent is prepared. To increase the halogenation rate, it is important to prepare the first reaction solution before adding zinc phthalocyanine. In the melting method, the metal salt in the first reaction solution is a molten salt. That is, the first step may be the step of preparing a first reaction solution containing a molten metal salt (molten salt) and a halogenating agent.

[0101] The first step may be a step of preparing a pre-prepared first reaction solution, or it may be a step of preparing the first reaction solution. The preparation of the first reaction solution may be carried out, for example, by mixing a metal salt and a halogenating agent, or by mixing a second halogenating agent different from the first halogenating agent into a reaction solution containing a metal salt and a first halogenating agent. That is, the first step may include a step of mixing a metal salt and a halogenating agent, or it may include a step of mixing a second halogenating agent into a reaction solution containing a metal salt and a first halogenating agent. By mixing a second halogenating agent into a reaction solution containing a metal salt and a first halogenating agent, the halogenation rate can be improved.

[0102] In the melting method, the metal salt may be melted to form a molten salt before mixing it with the halogenating agent, and then mixed with the halogenating agent; or the metal salt may be melted in the halogenating agent. The temperature of the molten salt may be, for example, 10 to 170°C or 10 to 60°C.

[0103] Examples of metal salts include aluminum halides (aluminum chloride (AlCl3), aluminum bromide (AlBr3), etc.), alkali (earth) metal halides (sodium chloride (NaCl), etc.), and titanium tetrachloride. In the melting method, aluminum chloride or sodium chloride may be used, or both may be used in combination, from the viewpoint of lowering the melting temperature of the molten salt.

[0104] The amount of aluminum chloride used may be 0.1 to 50 parts by mass, 1 to 20 parts by mass, or 1 to 10 parts by mass per 1 part by mass of zinc phthalocyanine used in the second step, from the viewpoint of enhancing its reactivity as a Friedel-Crafts catalyst in halogenation.

[0105] The amount of sodium chloride used may be 0.01 to 10 parts by mass, 0.1 to 5 parts by mass, or 0.1 to 1 part by mass per 1 part by mass of zinc phthalocyanine used in the second step, from the viewpoint of lowering the melting temperature of the molten salt.

[0106] The mass ratio of sodium chloride to aluminum chloride (sodium chloride / aluminum chloride) may be 0.01 to 1.0, 0.03 to 0.5, or 0.05 to 0.15, from the viewpoint of lowering the melting temperature of the molten salt.

[0107] The total amount of metal salt used may be, for example, 3 to 6 parts by mass per 1 part by mass of zinc phthalocyanine used in the second step.

[0108] Examples of halogenating agents include fluorinating agents, chlorinating agents, brominating agents, and iodinating agents. From the viewpoint of increasing brightness, brominating agents may be used. Brominating agents may be used in combination with other halogenating agents, and from the viewpoint of increasing brightness, they may be used in combination with chlorminating agents. For example, one of the above-mentioned brominating agents or chlorminating agents may be used as the first halogenating agent, and the other of the brominating agent or chlorminating agent may be used as the second halogenating agent.

[0109] Examples of brominating agents include bromine (Br2), N-bromosuccinimide, silver sulfate-bromine, tetramethylammonium tribromide, trifluoroacetyl hypobromide, dibromoisocyanuric acid, 2,4,4,6-tetrabromocyclohexa-2,5-dienone, hydrogen bromide-dimethyl sulfoxide, N-bromosuccinimide-dimethylformamide, 2,4-diamino-1,3-thiazole hydrotribromide, and 1,3-dibromo-5,5-dimethylhydantoin. Bromine may be used to improve the purity of the product.

[0110] Examples of chlorinating agents include sulfuryl chloride and thionyl chloride.

[0111] From the viewpoint of increasing the bromination rate, the amount of brominating agent used may be 0.01 to 5.0 parts by mass per 1 part by mass of zinc phthalocyanine used in the second step. When a chlorinating agent is used in combination, the chlorination rate can be suppressed by setting the amount of brominating agent used within the above range. From a similar viewpoint, the amount of brominating agent used may be 0.05 parts by mass or more, or 0.5 parts by mass or more, or 2.0 parts by mass or less, or 1.5 parts by mass or less, or 0.05 to 2.0 parts by mass or 0.5 to 1.5 parts by mass per 1 part by mass of zinc phthalocyanine used in the second step.

[0112] From the viewpoint of reducing the viscosity of the reaction solution, the amount of chlorinating agent used may be 1 to 10 parts by mass or 2 to 5 parts by mass per 1 part by mass of zinc phthalocyanine used in the second step.

[0113] The total amount of halogenating agent used in the first step may be 3.0 to 5.0 parts by mass per 1 part by mass of zinc phthalocyanine used in the second step.

[0114] (Second process) In the second step, a second reaction solution is obtained by mixing zinc phthalocyanine with the first reaction solution. In the melting method, the metal salt in the second reaction solution is a molten salt.

[0115] The mixing temperature in the second step may be 5 to 50°C, 10 to 45°C, or 10 to 30°C, from the viewpoint of thoroughly dissolving the raw materials.

[0116] (Third step) In the third step, a halogenating agent is mixed with the second reaction solution to obtain the third reaction solution. In the melting method, the metal salt in the second reaction solution is a molten salt.

[0117] As the halogenating agent, any halogenating agent that can be used in the first step described above can be used. From the viewpoint of increasing brightness, a brominating agent may be used, and from the viewpoint of improving the purity of the product, bromine may be used.

[0118] From the viewpoint of improving the yield of "16-zinc phthalocyanine brominated," the amount of brominating agent used may be 3.0 to 10.0 parts by mass or 5.0 to 8.0 parts by mass per 1 part by mass of zinc phthalocyanine. In this embodiment, the total amount of halogenating agent used in the third step may be within the above range.

[0119] The mass ratio of the brominating agent to the total halogenating agent (brominating agent / halogenating agent) may be 0.4 to 1.0 or 0.5 to 0.9, from the viewpoint of increasing the proportion of "16-zinc brominated phthalocyanine".

[0120] The total amount of brominating agent used in the first and third steps (the total amount of brominating agent used in the first step and the total amount of brominating agent used in the third step) may be 4.0 to 10.0 parts by mass or 5.0 to 8.5 parts by mass per 1 part by mass of zinc phthalocyanine, from the viewpoint of increasing the proportion of "16-zinc brominated phthalocyanine".

[0121] The mass ratio of the brominating agent used in the first step to the brominating agent used in the third step (brominating agent used in the first step / brominating agent used in the third step) may be 0.01 to 100, 0.03 to 10, 0.05 to 1, or 0.05 to 0.5, from the viewpoint of improving the bromination rate and suppressing the chlorination rate.

[0122] The mixing temperature in the third step may be 5-50°C, 10-45°C, or 10-30°C, from the viewpoint of ensuring sufficient dissolution of the raw materials.

[0123] (Fourth step) In the fourth step, the third reaction solution is heated. By keeping the heating rate of the third reaction solution at 2.5°C / hour or less, halogenation proceeds smoothly.

[0124] The heating rate may be 0.5°C / hour or 1.0°C / hour, 2.4°C / hour, 0.5 to 2.5°C / hour, or 1.0 to 2.4°C / hour, from the viewpoint of promoting better halogenation.

[0125] The above heating rate is determined by dividing the difference between the temperature of the third reaction solution at the end of heating (hereinafter referred to as the "end heating temperature") and the temperature of the third reaction solution at the start of heating (hereinafter referred to as the "start heating temperature") by the time from the start of heating (start of heating) to the end of heating (hereinafter referred to as the "heating time"). Therefore, as long as the heating rate calculated by the above method is 2.5°C / hour or less, it is not necessary for the heating rate to be 2.5°C / hour or less throughout the entire heating time, and there may be periods when the heating rate exceeds 2.5°C / hour, and there may also be periods when the third reaction solution is held at a constant temperature without heating. However, if the heating rate is 2.5°C / hour or less throughout the entire heating time (i.e., there are no periods when the heating rate exceeds 2.5°C / hour), halogenation tends to proceed even better. From a similar viewpoint, the heating rate may be constant throughout the entire heating time (for example, the fluctuation in the heating rate may be ±0.1°C / h or less).

[0126] The starting temperature for heating may be 5 to 50°C from the viewpoint of improving the solubility of the raw materials. From a similar viewpoint, the starting temperature for heating may be 10°C or higher, 45°C or lower, 40°C or lower, 10 to 45°C or 10 to 40°C.

[0127] The heating termination temperature may be 75°C or higher from the viewpoint of improving the halogenation rate. Similarly, the heating termination temperature may be 80°C or higher, 170°C or lower, 150°C or lower, or 100°C or lower, and may be between 75°C and 170°C, 80°C and 150°C, or 75°C and 125°C. Note that the heating termination temperature refers to the final temperature reached in the fourth step.

[0128] From the viewpoint of improving the halogenation rate, the heating time may be 30 to 100 hours, and from the same viewpoint, the heating time may be 35 hours or more, 70 hours or less, or 35 to 70 hours.

[0129] The fourth step may include continuing heating after the heating is complete and maintaining the temperature at the end of the heating process. The holding time at the end of the heating process may be, for example, 0 to 5 hours.

[0130] After the fourth step, if necessary, steps may be taken to precipitate polyzinc phthalocyanine polyhalide by mixing the reaction solution with water or the like, to wash the precipitate, to dry the washed precipitate, and to finely grind or mill the dried precipitate. The step of finely grinding the precipitate is also called the pigmentation step. Since the dried precipitate is a coarse dried aggregate called a "coarse pigment," a polyzinc phthalocyanine polyhalide pigment with a small average primary particle size can be obtained by performing the pigmentation step. The above steps may be carried out using known and conventional methods used in the production of polyzinc phthalocyanine polyhalide.

[0131] From the perspective of easily obtaining fine pigments, the pigmentation process may include a step of solvent salt milling of the precipitate after drying. Solvent salt milling is a process of kneading and grinding crude pigment, which is polyhalide zinc phthalocyanine that has not undergone pigmentation, either immediately after synthesis or after grinding, with an inorganic salt and an organic solvent. Specifically, the crude pigment, the inorganic salt, and an organic solvent that does not dissolve it are placed in a kneader and kneaded and ground in it. For example, a kneader or a mix maller can be used as the kneader in this case.

[0132] As described above, in the manufacturing method of the above embodiment, the halogenation rate of polyzinc phthalocyanine polyhalide can be increased, in particular, by changing the heating conditions in the fourth step. Therefore, by adjusting the heating rate, heating start temperature, heating end temperature, heating time, etc. in the fourth step, the polyzinc phthalocyanine A of the above embodiment can also be obtained. [Examples]

[0133] The contents of this disclosure will be described in more detail below using examples and comparative examples, but this disclosure is not limited to the following examples.

[0134] <Synthesis Example 1> Zinc phthalocyanine was synthesized using phthalonitrile, ammonia, and zinc chloride as raw materials by a known method.

[0135] <Example 1> (Synthesis of polyhalogenated zinc phthalocyanine) First, 270 parts by mass of sulfuryl chloride (Wako Pure Chemical Industries, Ltd., product code: 190-04815, "SulCl" in Table 1), 315 parts by mass of anhydrous aluminum chloride (Kanto Chemical Co., Ltd., product code: 01156-00, "AlCl3" in Table 1), and 43 parts by mass of sodium chloride (Tokyo Chemical Industries, Ltd., product code: S0572, "NaCl" in Table 1) were mixed at room temperature (25°C) to obtain a reaction solution containing a molten metal salt (molten salt) (first half of the first step). Next, 43 parts by mass of bromine ("Br2(1)" in Table 1) were mixed into the obtained reaction solution to obtain the first reaction solution (second half of the first step).

[0136] Next, at 25°C, 65 parts by mass of zinc phthalocyanine ("Pc-Zn" in Table 1) obtained in Synthesis Example 1 was added to the first reaction solution to obtain a second reaction solution (second step).

[0137] Next, at 25°C, 479 parts by mass of bromine (Wako Pure Chemical Industries, Ltd., product code: 026-02405, "Br2(2)" in Table 1) were added dropwise to the second reaction solution obtained to obtain a third reaction solution (third step).

[0138] Next, the third reaction solution was heated for 30 hours at a heating rate of 2.3°C / hour, with a heating rate variation of ±0.1°C / h or less (fourth step). The starting temperature for heating was 25.0°C, and the ending temperature was 95.0°C. The holding time at the ending temperature was 0 hours.

[0139] The reaction solution (reaction mixture) obtained in the fourth step above was taken out and placed in water to precipitate polyzinc phthalocyanine polyhalide, thereby obtaining a slurry of polyzinc phthalocyanine polyhalide. The obtained slurry was filtered, washed with water at 60°C, and then re-dissolved in water. The obtained slurry was filtered again, washed with water at 60°C, and dried at 90°C to obtain 173 parts by mass of crude pigment (polyzinc phthalocyanine crude pigment) consisting of polyzinc phthalocyanine polyhalide. 3 parts by mass of this crude pigment, along with 30 parts by mass of sodium chloride and 3 parts by mass of diethylene glycol, were charged into a double-arm kneader and kneaded at 100°C for 8 hours. After kneading, the mixture was taken out into 300 parts by mass of water at 80°C, stirred for 1 hour, filtered, and washed with water at 60°C. Subsequently, the mixture was dried and pulverized to obtain a pigment (polyzinc phthalocyanine pigment) consisting of polyzinc phthalocyanine polyhalide.

[0140] <Examples 2-14 and Comparative Examples 1-2> Examples 2-14 and Comparative Examples 1-2, each containing zinc phthalocyanine polyhalogenate (pigment), were synthesized in the same manner as in Example 1, except for changes to the formulations shown in Table 1.

[0141] <Analysis> The obtained zinc phthalocyanine polyhalide (pigment) was subjected to mass spectrometry, average particle size measurement, ICP analysis, and combustion IC analysis using the methods described below. The results are shown in Tables 2 and 3.

[0142] (mass spectrometry) Mass spectrometry of zinc phthalocyanine polyhalide, a component of the pigment, was performed using a matrix-assisted laser desorption / ionization time-of-flight mass spectrometer (JEOL Ltd., JMS-S3000) to obtain a mass spectrum. Specifically, 0.5 mg of zinc phthalocyanine polyhalide was first ultrasonically dispersed in 1 mL of THF for 30 minutes using a Bransonic ultrasonic cleaner (EMERSON, CPX2800H-J) to obtain a dispersion. Next, 1 μL of the dispersion was dropped onto a target plate to prepare the sample for measurement, and measured in Spiral POS mode. The instrument's measurement parameters were set so that m / Z = 1840 was detected when mass spectrometry was performed on a known compound with a molecular weight of 1840. The delay time during mass spectrometry was 275 ns, the detector was 68%, the laser intensity was 34%, and the Resolving Power Value for peaks between m / z = 1820 and 1860 was 42805. As an example, the mass spectrum of Example 13 is shown in Figure 1.

[0143] From the obtained mass spectra, the maximum ionic intensity I1 in the range of m / z 1820 to 1860, the maximum ionic intensity I2 in the range of m / z 1740 to less than 1780, the maximum ionic intensity I3 in the range of m / z 1780 to less than 1820, the maximum ionic intensity I4 in the range of m / z 1650 to less than 1740, and the maximum ionic intensity I5 in the range of m / z 900 to less than 1650 were determined, and I2 / I1, I3 / I1, I4 / I1, I5 / I1, and I5 / I2 were calculated. The results are shown in Table 2. Also, for reference, the sum of the maximum ionic intensities I1 to I5 (I1 + I2 + I3 + I4 + I5) was calculated as I T When I1 / I T , I2 / I T I3 / I T , I4 / I T and I5 / I T This is shown in Table 3.

[0144] (Measurement of average primary particle diameter) The average primary particle size of the obtained zinc halide phthalocyanine pigment was measured. Specifically, first, the sample was prepared by ultrasonically dispersing the zinc halide phthalocyanine pigment, which was the sample, in cyclohexane to a concentration of 500 ppm. Next, the sample was observed at a magnification of 30,000x using a transmission electron microscope JEM-2010 (manufactured by JEOL Ltd.), and the zinc halide phthalocyanine pigment within the field of view was photographed. Then, the major and minor axes of 50 primary particles of the zinc halide phthalocyanine pigment on the two-dimensional image were determined. Furthermore, the average value of the determined major and minor axes was taken as the particle size of the primary particle, and this particle size was determined for each of the 50 primary particles. The average value of the particle sizes of the 50 primary particles determined in this way was taken as the average primary particle size of the zinc halide phthalocyanine pigment.

[0145] (ICP analysis) The zinc (Zn) content of the zinc phthalocyanine polyhalide constituting the pigment was determined by ICP emission spectrometry. Specifically, first, atomic absorption spectrometry standard solutions (Merck Millipore ICP Multi-Element Standard IV, zinc concentration: 1000 ppm by mass) were progressively diluted with deionized water (ultrapure water) to prepare dilutions with zinc concentrations of 5 μg / kg, 10 μg / kg, 20 μg / kg, 50 μg / kg, 100 μg / kg, 500 μg / kg, 1000 μg / kg, or 3000 μg / kg. These dilutions and deionized water (ultrapure water, zinc concentration 0 μg / kg) were added to 8 mL of nitric acid in a total volume of 25 g to prepare standard samples. Next, these were measured using an ICP emission spectrometer (Agilent ICP-OES5800, Agilent) and a calibration curve was created. On the other hand, 0.26 g of polyhalogenated zinc phthalocyanine pigment was decomposed in 8 mL of nitric acid using a CEM microwave decomposition system MARS6 to obtain a decomposition solution. The decomposition solution was then diluted 1,000,000 times with ultrapure water, and 8 mL of nitric acid was added to prepare the measurement solution. This measurement solution was measured using the above-mentioned ICP emission spectrometer, and the zinc content was determined using the above-mentioned calibration curve.

[0146] (Combustion IC analysis) The bromine (Br) and chlorine (Cl) content of the zinc phthalocyanine polyhalide that constitutes the pigment was determined by combustion ion chromatography.

[0147] Specifically, a standard bromine solution (bromine concentration: 10 ppm by mass) was first diluted stepwise with ultrapure water to prepare standard solutions with bromine concentrations of 0.5 ppm by mass, 1.0 ppm by mass, and 2.0 ppm by mass. These were then measured using an ion chromatograph (Thermo ICS-6000) to create a calibration curve for measuring bromine content.

[0148] Furthermore, a chlorine standard solution (chlorine concentration: 10 ppm by mass) was progressively diluted with ultrapure water to prepare standard solutions with chlorine concentrations of 0.1 ppm by mass, 0.3 ppm by mass, and 1.0 ppm by mass, respectively. These were then measured using an ion chromatograph (Thermo ICS-6000) to create a calibration curve for measuring chlorine content.

[0149] On the other hand, 2 mg of polyhalogenated phthalocyanine pigment was burned in an automated sample combustion device (AQF-2100H, manufactured by Mitsubishi Chemical Analytec Co., Ltd.), and the resulting gas was absorbed into 15 mL of ultrapure water containing hydrogen peroxide to obtain an absorption solution. The ultrapure water containing hydrogen peroxide was prepared by diluting 1 g of 30% hydrogen peroxide with 500 mL of ultrapure water. Subsequently, the absorption solution was diluted with 1500 mL of ultrapure water to prepare the measurement solution. This measurement solution was measured using the ion chromatograph described above, and the bromine and chlorine content were determined using the calibration curve described above.

[0150] <Rating> (Measurement of spectral transmittance and contrast) [Preparation of green coloring composition] Green colored compositions were prepared using the zinc phthalocyanine polyhalide (pigments) obtained in Examples 1-14 and Comparative Examples 1-2. Specifically, 2.48 parts by mass of zinc phthalocyanine polyhalide (pigment) was dispersed for 2 hours in a paint shaker (Toyo Seiki Seisakusho Co., Ltd., test disperser) using 0.3-0.4 mm zircon beads, along with 1.24 parts by mass of BYK-LPN6919 (manufactured by BYK, dispersant: solids content 60% by mass), 1.86 parts by mass of Unidick ZL-295 (manufactured by DIC Corporation, alkali-soluble resin: solids content 40% by mass), and 10.92 parts by mass of propylene glycol monomethyl ether acetate (manufactured by Kuraray Trading Co., Ltd., organic solvent), to prepare a green colored composition for forming green pixels for color filters.

[0151] [Preparation of green spin-coat solution] A green spin-coat solution was prepared by adding 4.0 parts by mass of a green coloring composition, 0.98 parts by mass of Unidick ZL-295 (manufactured by DIC Corporation, alkali-soluble resin: solid content 40% by mass), and 0.22 parts by mass of propylene glycol monomethyl ether acetate (manufactured by Kuraray Trading Co., Ltd., organic solvent), and mixing them in a paint shaker (manufactured by Toyo Seiki Seisakusho Co., Ltd., test disperser).

[0152] [Fabrication of glass substrates for evaluation] The above green spin-coating solution was spin-coated onto soda glass (manufactured by Nippon Sheet Glass Co., Ltd., glass plate), dried at 90°C for 3 minutes, and then fired at 230°C for 1 hour to obtain an evaluation glass substrate. The firing was performed so that the film thickness after deposition was 2 μm.

[0153] [Measurement of spectral transmittance] The spectral transmittance was measured using the above-mentioned evaluation glass substrate with a Hitachi High-Tech Science U-3900 spectrophotometer, and the spectral transmittance values ​​at each wavelength were plotted. The spectral transmittance was determined in accordance with the Japanese Industrial Standard JIS Z 8722 (Methods for measuring color - Reflected and transmitted object color) for a Class 1 spectrophotometer. The results are shown in Table 2.

[0154] [Contrast measurement] Using the above-mentioned evaluation glass substrate, the contrast was measured using a contrast tester (CT-1, manufactured by Tsubosaka Electric Co., Ltd.), and the relative ratio was calculated. Specifically, the contrast of Comparative Example 2 was used as the baseline (100%), and the relative ratio of each example to the comparative example was calculated. The above apparatus has a space for the green pixel portion of the color filter between two polarizing plates, with a light source on one polarizing plate and a colorimeter on the opposite side. The contrast was calculated from the ratio of luminance (transmitted light intensity) when the polarization axes are parallel and perpendicular. The results are shown in Table 2.

[0155] (Brightness measurement) [Preparation of yellow colored composition] A yellow coloring composition for forming green pixels for a color filter was prepared by dispersing 2.48 parts by mass of Pigment Yellow 138 (Paliotol Yellow D0960, manufactured by Sun Chemical) (pigment) with 1.24 parts by mass of BYK-LPN6919 (manufactured by BYK, dispersant: solid content 60% by mass), 1.86 parts by mass of Unidick ZL-295 (manufactured by DIC Corporation, alkali-soluble resin: solid content 40% by mass), and 10.92 parts by mass of propylene glycol monomethyl ether acetate (manufactured by Kuraray Trading Co., Ltd., organic solvent) using 0.3-0.4 mm zircon beads in a paint shaker (test disperser, manufactured by Toyo Seiki Seisakusho Co., Ltd.) for 2 hours.

[0156] [Preparation of yellow spin coat solution] Next, 4.0 parts by mass of yellow coloring composition, 0.98 parts by mass of Unidick ZL-295 (manufactured by DIC Corporation, alkali-soluble resin: solid content 40% by mass), and 0.22 parts by mass of propylene glycol monomethyl ether acetate (manufactured by Kuraray Trading Co., Ltd., organic solvent) were added and mixed using a paint shaker (manufactured by Toyo Seiki Seisakusho Co., Ltd., test disperser) to prepare a yellow spin coat solution.

[0157] [Preparation of green spin-coat solution] A green spin-coated solution was prepared using the same method as that used for (measurement of spectral transmittance and contrast).

[0158] [Preparation of colored compositions for evaluation and fabrication of glass substrates for evaluation] A colored composition for evaluation was prepared by mixing the prepared green spin-coating solution and the yellow spin-coating solution. The obtained colored composition for evaluation was spin-coated onto soda glass (manufactured by Nippon Sheet Glass Co., Ltd., glass plate), dried at 90°C for 3 minutes, and then fired at 230°C for 1 hour to obtain an evaluation glass substrate with a chromaticity (x,y) = (0.286, 0.575).

[0159] [Brightness measurement] The brightness was measured using the above-mentioned evaluation glass substrate with a Hitachi High-Tech Science U-3900. Specifically, the brightness of Comparative Example 2 was used as the baseline (100%), and the relative ratio of each example to the comparative example was calculated. The results are shown in Table 2.

[0160] [Table 1]

[0161] [Table 2]

[0162] [Table 3]

Claims

1. The following general formula (i) 【Chemistry 1】 (In general formula (i), X １ ~X １６ Each of these independently represents either a hydrogen atom or a halogen atom. However, X １ ~X １６ At least two of them are halogen atoms. It contains a compound represented by, In the mass spectrum obtained by matrix-assisted laser desorption / ionization time-of-flight mass spectrometry, the maximum ion intensity in the range of m / z 1820 to 1860 is defined as I １ The maximum ionic intensity in the range of m / z 1740 to less than 1780 is defined as I ２ In that case, I ２ / I １ Polyhalogenated zinc phthalocyanine with a value of 0.50 or less.

2. In the mass spectrum obtained by matrix-assisted laser desorption ionization time-of-flight mass spectrometry, let the maximum ion intensity in the range of m / z 1820 or more and 1860 or less be I １ and let the maximum ion intensity in the range of m / z 1780 or more and less than 1820 be I ３ When this is done, I ３ / I １ is 1.00 or less, the zinc polyhalophthalocyanine according to claim 1.

3. In the mass spectrum obtained by matrix-assisted laser desorption / ionization time-of-flight mass spectrometry, the maximum ion intensity in the range of m / z 1820 to 1860 is defined as I １ The maximum ionic intensity in the range of m / z 1650 or more and less than 1740 is defined as I ４ In that case, I ４ / I １ The zinc phthalocyanine polyhalogenate according to claim 1, wherein the ratio is 0.45 or less.

4. In the mass spectrum obtained by matrix-assisted laser desorption / ionization time-of-flight mass spectrometry, the maximum ion intensity in the range of m / z 1820 to 1860 is defined as I １ The maximum ionic intensity in the range of m / z 900 to less than 1650 is defined as I ５ In that case, I ５ / I １ The zinc phthalocyanine polyhalogenate according to claim 1, wherein the ratio is 0.50 or less.

5. The zinc phthalocyanine polyhalogenate according to claim 1, wherein the zinc content determined by ICP emission spectrometry is 2.5 to 5.0% by mass.

6. The zinc phthalocyanine polyhalogenate according to claim 1, wherein the bromine content determined by combustion ion chromatography is 30 to 80% by mass.

7. The zinc phthalocyanine polyhalogenate according to claim 1, wherein the chlorine content determined by combustion ion chromatography is 0.1 to 10% by mass.

8. The zinc phthalocyanine polyhalogenate according to claim 1, wherein the average primary particle size is 5 to 100 nm.

9. A coloring composition comprising zinc phthalocyanine polyhalogenate according to any one of claims 1 to 8.

10. A color filter comprising a pixel portion containing zinc phthalocyanine polyhalide as described in any one of claims 1 to 8.

11. The first step involves preparing a first reaction solution containing a metal salt and a halogenating agent, A second step involves mixing zinc phthalocyanine with the first reaction solution to obtain a second reaction solution, A third step involves mixing a halogenating agent with the second reaction solution to obtain a third reaction solution, A fourth step involves heating the third reaction solution. It includes at least, A method for producing zinc phthalocyanine polyhalide, wherein the heating rate of the third reaction solution in the fourth step is 2.5°C / hour or less.

12. The method for producing zinc phthalocyanine polyhalogenate according to claim 11, wherein the starting temperature for heating in the fourth step is 5 to 50°C.

13. A method for producing zinc phthalocyanine polyhalogenate according to claim 11 or 12, wherein the temperature at which the heating process ends in the fourth step is 75 to 170°C.

14. The method for producing zinc phthalocyanine polyhalogenate according to claim 11 or 12, wherein the first step includes a step of mixing a second halogenating agent into a reaction solution containing a first halogenating agent and the metal salt.

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