Polyhalogenated zinc phthalocyanine, colored composition, color filter, and method for producing polyhalogenated zinc phthalocyanine

Abstract

A polyhalogenated zinc phthalocyanine according to the present invention includes a compound represented by general formula (i). When I1 is the maximum ion intensity within an m / z range of at least 1820 but no more than 1860 on a mass spectrum obtained by matrix-assisted laser desorption / ionization time-of-flight mass spectrometry and I2 is the maximum ion intensity within an m / z range of at least 1740 but less than 1780, I2 / I1 is no more than 0.50. (In general formula (i), X1–X16 each independently represent a hydrogen atom or a halogen atom, provided that at least two of X1–X16 are halogen atoms.)

Description

[Technical Field]

[0001] The present disclosure relates to polyhalogenated zinc phthalocyanines, colored compositions, color filters, and methods for producing polyhalogenated zinc phthalocyanines. [Background technology]

[0002] Green pigments containing polyhalogenated zinc phthalocyanine are often used in color filters for liquid crystal displays. Known examples of pigments containing polyhalogenated zinc phthalocyanine include Pigment Green 58.

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

[0004] [Patent Document 1] Japanese Patent Application Laid-Open No. 2007-284589 Summary of the Invention [Problem to be solved by the invention]

[0005] The effect of improving brightness by the polyhalogenated zinc phthalocyanine described in Patent Document 1 is still not sufficient.

[0006] An object of the present disclosure is to provide a polyhalogenated zinc phthalocyanine that contributes to improving the brightness of color filters. [Means for solving the problem]

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

[14] .

[0008] [1] The following general formula (i) [ka] (In general formula (i), X 1 ~X 16 each independently represents a hydrogen atom or a halogen atom, provided that X 1 ~X 16 At least two of the are halogen atoms.) The compound includes a compound represented by A polyhalogenated zinc phthalocyanine in which, in a 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 I1, and the maximum ion intensity in the range of m / z 1740 to less than 1780 is defined as I2, with I2 / I1 being 0.50 or less.

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

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

[0011] [4] The polyhalogenated zinc phthalocyanine according to any one of [1] to [3], wherein, in a 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 900 or more and less than 1650 is defined as I5, I5 / I1 is 0.50 or less.

[0012] [5] The polyhalogenated zinc phthalocyanine according to any one of [1] to [4], which has a zinc content of 2.5 to 5.0 mass % as determined by ICP emission spectroscopy.

[0013] [6] The polyhalogenated zinc phthalocyanine according to any one of [1] to [5], which has a bromine content of 30 to 80 mass % as determined by combustion ion chromatography.

[0014] [7] The polyhalogenated zinc phthalocyanine according to any one of [1] to [6], which has a chlorine content of 0.1 to 10 mass % as determined by combustion ion chromatography.

[0015] [8] The polyhalogenated zinc phthalocyanine according to any one of [1] to [7], which has an average primary particle size of 5 to 100 nm.

[0016] [9] A coloring composition comprising the polyhalogenated zinc phthalocyanine according to any one of [1] to [8].

[0017]

[10] A color filter having a pixel portion containing the polyhalogenated zinc phthalocyanine according to any one of [1] to [8].

[0018]

[11] a first step of preparing a first reaction solution containing a metal salt and a halogenating agent; a second step of mixing zinc phthalocyanine with the first reaction solution to obtain a second reaction solution; a third step of mixing a halogenating agent with the second reaction solution to obtain a third reaction solution; a fourth step of heating the third reaction liquid; At least A method for producing a polyhalogenated zinc phthalocyanine, wherein the temperature increase rate of the third reaction solution in the fourth step is 2.5°C / hour or less.

[0019]

[12] The method for producing a polyhalogenated zinc phthalocyanine according to

[11] , wherein the temperature increase start temperature in the fourth step is 5 to 50°C.

[0020]

[13] The method for producing a polyhalogenated zinc phthalocyanine according to

[11] or

[12] , wherein the temperature increase end temperature in the fourth step is 75 to 170°C.

[0021]

[14] The method for producing a polyhalogenated zinc phthalocyanine according to any one of

[11] to

[13] , wherein the first step comprises a step of mixing a second halogenating agent with a reaction liquid containing a first halogenating agent and the metal salt. [Effects of the Invention]

[0022] According to the present disclosure, it is possible to provide a polyhalogenated zinc phthalocyanine that contributes to improving the brightness of a color filter. [Brief explanation of the drawings]

[0023] [Figure 1] 1 shows the mass spectrum of Example 13 obtained by matrix-assisted laser desorption ionization time-of-flight mass spectrometry. DETAILED DESCRIPTION OF THE INVENTION

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

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

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

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

[0028] (First embodiment) The polyhalogenated zinc phthalocyanine of the first embodiment (hereinafter referred to as "polyhalogenated zinc phthalocyanine A1") is characterized in that, in a 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 greatest intensity in each of the above ranges. The maximum ion intensity I1 is determined by the ratio of the 16-brominated zinc phthalocyanine (X in formula (i)) to the 16-brominated zinc phthalocyanine (X in formula (i)). 1 ~X16 The maximum ion intensity I2 is the intensity of the peak corresponding to 15 bromide zinc phthalocyanine (a compound in which X in formula (i) are all bromine atoms). 1 ~X 16 wherein 15 are bromine atoms and 1 is hydrogen atom) and / or 14 bromine dichloride zinc phthalocyanine (X in formula (i) 1 ~X 16 The intensities of the peaks corresponding to a compound in which 14 are bromine atoms and 2 are chlorine atoms.

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

[0030] Because of the above-mentioned characteristics, polyhalogenated zinc phthalocyanine A1 can improve the brightness of a color filter, specifically the brightness of a green pixel portion. Furthermore, the use of polyhalogenated zinc phthalocyanine A1 as a pigment for a color filter tends to improve the contrast of the color filter.

[0031] The reason why the above effect is obtained is not clear, but is presumed to be as follows. First, the brightness of the green pixel portion of the color filter depends on the transmittance of light in the wavelength region of 480 to 580 nm, which is recognized as green. The higher the transmittance of light in this wavelength region, 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 that does not absorb light in the above wavelength region as a pigment. In this regard, polyhalogenated zinc phthalocyanine has a larger number of bromine atoms present on the phthalocyanine ring, which increases molecular distortion and leads to absorption on the longer wavelength side. Therefore, the higher the proportion of 16-brominated zinc phthalocyanine present, the longer the absorption peak will be on the wavelength side than the above wavelength region, making it more difficult to absorb light in the above wavelength region (especially around 580 nm). In contrast, since polyhalogenated zinc phthalocyanine A1 has an I2 / I1 ratio of 0.50 or less, the abundance ratio of 15-brominated zinc phthalocyanine and 14-bromo-dichloro-zinc phthalocyanine relative to 16-brominated zinc phthalocyanine is smaller than that of conventional polyhalogenated zinc phthalocyanines (i.e., the abundance ratio of 16-brominated zinc phthalocyanine is higher). In other words, polyhalogenated zinc phthalocyanine A1 is less likely to absorb light in the above wavelength range (especially near 580 nm) than conventional polyhalogenated zinc phthalocyanine. For this reason, it is presumed that the use of polyhalogenated zinc phthalocyanine A1 can increase the transmittance of light in the wavelength range of 480 to 580 nm, thereby improving the brightness of the color filter.

[0032] From the viewpoint of further improving the brightness and contrast of the color filter, I2 / I1 may be 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.

[0033] In the mass spectrum, in addition to peaks corresponding to 16-brominated zinc phthalocyanine, 15-brominated zinc phthalocyanine, and 14-bromodichlorozinc phthalocyanine, multiple peaks corresponding to the compound represented by formula (i) can be observed.

[0034] In the range of m / z 1780 or more and less than 1820, 15-brominated 1-chlorinated zinc phthalocyanine (X in formula (i)) 1 ~X 16 A peak corresponding to a compound in which 15 of the m / z atoms are bromine atoms and one is a chlorine atom may be observed. When the maximum ionic intensity in the above range (m / z range of 1780 or more and less than 1820) is 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 be further improved. From the same 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 more, 0.05 or more, 0.15 or more, 0.30 or more, 0.45 or more, or 0.60 or more, or may be 0.01 to 1.00, 0.05 to 0.70, 0.15 to less than 0.5, 0.15 to 0.45, 0.30 to 1.00, 0.45 to 1.00, or 0.60 to 1.00.

[0035] In the range of m / z 1650 or more and less than 1740, 13-bromo-2-chlorinated zinc phthalocyanine (X in formula (i)) 1 ~X 16 13 are bromine atoms, 2 are chlorine atoms, and 1 is a hydrogen atom), 14. brominated zinc phthalocyanine (X in formula (i) 1 ~X 16 Peaks corresponding to compounds such as those in which 14 of the ionic atoms are bromine atoms and 2 are hydrogen atoms may be observed. When the maximum ionic intensity in the above range (m / z range of 1650 or more and 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 be further improved. From the same 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 or more and less than 1650, 13-bromo-1-chlorinated zinc phthalocyanine (X in formula (i)) 1 ~X 16 13) a compound in which 13 are bromine atoms, 1 is chlorine atom, and 2 are hydrogen atoms; 13) a compound in which X in formula (i) 1 ~X 16 Peaks corresponding to compounds such as a compound in which 13 of the ions are bromine atoms and 3 are hydrogen atoms may be observed. When the maximum ionic intensity in the above range (m / z range of 900 or more and less than 1650) is I5, I5 / I1 (the ratio of maximum ionic intensity I5 to 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 be further improved. From the same 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] From the viewpoint of achieving both high brightness and high contrast, I5 / I2 (the ratio of maximum ionic intensity I5 to 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. 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 0.05 to 1.30, 0.10 to 1.00, 0.15 to 0.70, 0.20 to 0.60, 0.40 to 0.50, or 0.10 to 0.25.

[0038] The maximum ion intensity I1 may be the maximum among the intensities of the peaks corresponding to the compound represented by formula (i).

[0039] The sum of the above maximum ion intensities I1 to I5 (I1 + I2 + I3 + I4 + I5) is I T Then, I1 / I TFrom the viewpoint of achieving both high brightness and high contrast, may be 0.35 or more, 0.45 or more, or 0.55 or more, and may be 0.75 or less, 0.70 or less, or 0.65 or less, or 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, may be 0.01 or more, 0.05 or more, or 0.07 or more, and may be 0.30 or less, 0.20 or less, or 0.10 or less, or 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, may be 0.05 or more, 0.10 or more, or 0.20 or more, and may be 0.50 or less, 0.40 or less, or 0.30 or less, or 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, may be 0.01 or more, 0.05 or more, or 0.07 or more, and may be 0.30 or less, 0.15 or less, or 0.10 or less, or 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, may be 0.01 or more, 0.03 or more, or 0.05 or more, and may be 0.15 or less, 0.10 or less, or 0.08 or less, or 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 I3 / I1 is 0.60 to 1.00, and the I5 / I2 is 1.00 or less.

[0045] Because of the above-mentioned characteristics, polyhalogenated zinc phthalocyanine A2 can improve the brightness of a color filter, specifically the brightness of a green pixel portion. Furthermore, the use of polyhalogenated zinc phthalocyanine A2 as a pigment for a color filter tends to improve the contrast of the color filter.

[0046] Although the reason for the above-mentioned effects is not clear, it is presumed that the polyhalogenated zinc phthalocyanine A2 has an absorption peak shifted to the long wavelength side due to the I3 / I1 and I5 / I2 ratios being within the above ranges, and therefore absorbs less light in the wavelength region of 480 to 580 nm than conventional polyhalogenated zinc phthalocyanine A2. Therefore, it is presumed that the use of polyhalogenated zinc phthalocyanine A2 can increase the transmittance of light in the wavelength region of 480 to 580 nm, thereby improving the brightness of the color filter.

[0047] Hereinafter, only the features unique to the second embodiment will be described, and descriptions that overlap with the first embodiment will be omitted.

[0048] In the second embodiment, the ratio I2 / I1 may be 0.50 or less or more 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, the ratio I3 / I1 may be 0.70 to 1.00 or 0.80 to 1.00.

[0050] In the second embodiment, from the viewpoint of further improving the brightness and contrast of the color filter, the ratio I5 / I2 may be 0.80 or less or 0.70 or less. 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 is 0.45 or less and the I5 / I2 is 1.00 or less.

[0052] Because of the above-mentioned characteristics, polyhalogenated zinc phthalocyanine A3 can improve the brightness of a color filter, specifically the brightness of a green pixel portion. Furthermore, the use of polyhalogenated zinc phthalocyanine A3 as a pigment for a color filter tends to improve the contrast of the color filter.

[0053] Although the reason for the above-mentioned effects is not clear, it is presumed that the absorption peak of polyhalogenated zinc phthalocyanine A3 is shifted to the long wavelength side due to the I4 / I1 and I5 / I2 ratios being within the above ranges, and that it is less likely to absorb light in the wavelength region of 480 to 580 nm than conventional polyhalogenated zinc phthalocyanine A3. Therefore, it is presumed that the use of polyhalogenated zinc phthalocyanine A3 can increase the transmittance of light in the wavelength region of 480 to 580 nm, thereby improving the brightness of the color filter.

[0054] Hereinafter, only the features unique to the third embodiment will be described, and descriptions that overlap with the first embodiment will be omitted.

[0055] In the third embodiment, the ratio I2 / I1 may be 0.50 or less or more 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, from the viewpoint of further improving the brightness and contrast of the color filter, I4 / I1 may be 0.10 or more, 0.20 or more, or 0.35 or more, for example, 0.10 to 0.45, 0.20 to 0.45, or 0.35 to 0.45. I4 / I1 may be 0.40 or less, 0.35 or less, 0.30 or less, or 0.25 or less, or 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, from the viewpoint of further improving the brightness and contrast of the color filter, the ratio I5 / I2 may be 0.80 or less or 0.70 or less. 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 I5 / I1 is 0.20 or less and the I5 / I2 is 1.00 or less.

[0059] Because of the above-mentioned characteristics, polyhalogenated zinc phthalocyanine A4 can improve the brightness of a color filter, specifically the brightness of a green pixel portion. Furthermore, the use of polyhalogenated zinc phthalocyanine A4 as a pigment for a color filter tends to improve the contrast of the color filter.

[0060] Although the reason for the above-mentioned effects is not clear, it is presumed that the absorption peak of polyhalogenated zinc phthalocyanine A4 is shifted to the long wavelength side due to the I5 / I1 and I5 / I2 ratios being within the above ranges, and that it is less likely to absorb light in the wavelength range of 480 to 580 nm than conventional polyhalogenated zinc phthalocyanine A4. Therefore, it is presumed that the use of polyhalogenated zinc phthalocyanine A4 can increase the transmittance of light in the wavelength range of 480 to 580 nm, thereby improving the brightness of the color filter.

[0061] Hereinafter, only the features unique to the fourth embodiment will be described, and descriptions that overlap with the first embodiment will be omitted.

[0062] In the fourth embodiment, the ratio I2 / I1 may be 0.50 or less or more than 0.50. From the viewpoint of further improving the brightness and contrast of the color filter, the ratio I2 / I1 may be 0.50 or less, 0.45 or less, or 0.30 or less. The ratio 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, from the viewpoint of further improving the brightness and contrast of the color filter, I5 / I1 may be 0.01 or more, for example, 0.01 to 0.20. I5 / I1 may be 0.15 or less, or 0.10 or less, or may be 0.01 to 0.15, or 0.01 to 0.10.

[0064] In the fourth embodiment, from the viewpoint of further improving the brightness and contrast of the color filter, the ratio I5 / I2 may be 0.80 or less or 0.70 or less. 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] The polyhalogenated zinc phthalocyanines A1 to A4 of the first to fourth embodiments described above (hereinafter collectively referred to as "polyhalogenated zinc phthalocyanine A") are, from the viewpoint of further improving the brightness and contrast of the color filter, 1 ~X 16 are each independently a hydrogen atom, a chlorine atom, or a bromine atom. That is, polyhalogenated zinc phthalocyanine A may be a compound represented by the formula (i), 1 ~X 16 The present invention may not include compounds in which at least one of the above is a 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% by mass from the viewpoint of further improving the brightness and contrast of the color filter. From the same viewpoint as above, the zinc content may be 3.0% by mass or more, 3.2% by mass or more, or 3.5% by mass or more, and may be 4.5% by mass or less, 4.2% by mass or less, or 4.0% by mass or less, or may be 3.0 to 4.5%, 3.2 to 4.2%, or 3.5 to 4.0% by mass.

[0067] The "zinc content" is determined by ICP emission spectroscopy and is the content based on the total mass of polyhalogenated zinc phthalocyanine A. 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. From the same viewpoint as above, the bromine content may be 35% by mass or more, or 40% by mass or more, and may be 75% by mass or less, 70% by mass or less, or 60% by mass or less, or may be 30 to 75%, 35 to 70%, or 40 to 60% by mass.

[0069] The "bromine content" is determined by combustion ion chromatography and is the content based on the total mass of polyhalogenated zinc phthalocyanine A. 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. From the same viewpoint as above, the chlorine content may be 0.3% by mass or more, or 0.5% by mass or more, and may be 5% by mass or less, or 3% by mass or less, or may be 0.3 to 5% by mass or 0.5 to 3% by mass.

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

[0072] The spectral transmittance Ta of polyhalogenated zinc phthalocyanine A at 580 nm can be 34.0% or more (for example, 34.0 to 90.0%). The spectral transmittance Ta may be 34.5 to 90.0% or 35.0 to 50.0%.

[0073] The spectral transmittance Tb of polyhalogenated zinc phthalocyanine A in the range of 510 to 530 nm can be 85.0% or more (for example, 85.0 to 99.9%). The spectral transmittance Tb may be 87.0 to 99.9% or 90.0 to 95.0%. The above spectral transmittance Tb is the maximum spectral transmittance.

[0074] The spectral transmittance Tc of polyhalogenated zinc phthalocyanine A at 480 nm can be 35.0% or more (for example, 35.0 to 90.0%). The spectral transmittance Tc may be 35.5 to 90.0% or 36.0 to 50.0%.

[0075] The spectral transmittances Ta, Tb, and Tc are measured using a Type 1 spectrophotometer in accordance with Japanese Industrial Standard JIS Z 8722 (Method of Measuring Color—Reflected and Transmitted Object Color). Specifically, a coloring composition containing polyhalogenated zinc phthalocyanine A, a dispersant, an alkali-soluble resin, and an organic solvent is prepared. A measurement sample is then prepared using the coloring composition. This measurement sample is then spin-coated onto soda glass to form a film with a thickness of 0.2 to 5 μm after film formation. The resulting laminate is then dried at 70 to 100°C for 2 to 5 minutes and then baked at 200 to 250°C for 30 minutes to 2 hours to obtain a glass substrate for evaluation. The monochromatic spectral transmittance spectrum of the obtained glass substrate for evaluation is then measured using a Hitachi High-Tech Science U-3900, and the transmittance values ​​at each wavelength are plotted.

[0076] The polyhalogenated zinc phthalocyanine A may consist solely of the compound represented by the formula (i) above, or may contain compounds other than the compound represented by the formula (i) above (e.g., raw materials, by-products, etc.). However, the main component of the polyhalogenated zinc phthalocyanine A may be the compound represented by the formula (i) above. The content of the compound represented by the 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 the polyhalogenated zinc phthalocyanine A.

[0077] Polyhalogenated zinc phthalocyanine A is a particulate solid at room temperature (for example, 15 to 35°C). From the viewpoint of further improving the brightness of the color filter, the average particle size of the primary particles of polyhalogenated zinc 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, 10 nm or more, or 15 nm or more, or may be 5 to 100 nm, 5 to 70 nm, 10 to 60 nm, or 15 to 50 nm. In this specification, polyhalogenated zinc phthalocyanine having an average primary particle size of 5 to 100 nm may be referred to as a polyhalogenated zinc phthalocyanine pigment.

[0078] The "average primary particle size" can be determined by the method described in the Examples using a transmission electron microscope or a scanning electron microscope.

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

[0080] <Coloring composition> Another embodiment of the present disclosure is a coloring composition containing the polyhalogenated zinc phthalocyanine A described above.

[0081] The coloring composition can be used to form pixel portions (particularly green pixel portions) of a color filter, and the brightness of the pixel portions of the color filter can be improved by using the coloring composition.

[0082] The polyhalogenated zinc phthalocyanine A contained in the coloring composition may be a polyhalogenated zinc phthalocyanine pigment. The content of the polyhalogenated zinc 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 viewpoints of colorant dispersibility and dispersion stability.

[0083] The coloring composition may contain, as necessary, a dispersant, a resin, an organic solvent, etc. As these materials, known and commonly used materials may be used as components of coloring compositions used to form pixel portions (particularly green pixel portions) of color filters.

[0084] Dispersants include, for example, DISPERBYK from BYK-Chemie. TM ) 130, 161, 162, 163, 170, LPN-6919, LPN-21116, BASF's Efka 46 and Efka 47, etc. Furthermore, a leveling agent, a coupling agent, a cationic surfactant, etc. may also be used in combination.

[0085] Examples of the resin include photosensitive resins and / or alkali-soluble resins. Examples of the photosensitive resin 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 bifunctional monomers such as 1,6-hexanediol diacrylate, ethylene glycol diacrylate, neopentyl glycol diacrylate, triethylene glycol diacrylate, bis(acryloxyethoxy)bisphenol A, and 3-methylpentanediol diacrylate, and polyfunctional monomers such as trimethylolpropane triacrylate, pentaerythritol triacrylate, tris(2-hydroxyethyl)isocyanate, dipentaerythritol hexaacrylate, and dipentaerythritol pentaacrylate. Examples of the alkali-soluble resin include acrylic copolymers having carboxyl groups and epoxy (meth)acrylate resins having carboxyl groups. When a photosensitive resin is used, a known and commonly used 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; acetate 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; carbamate 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 in 100% by mass of the colored composition may be 1 to 90% by mass, or 3 to 50% by mass as a 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 may be 40 to 90% by mass, from the viewpoint of the solubility of other components and dispersion stability.

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

[0091] In addition to the green pigment, the coloring composition may contain a yellow pigment for color matching to achieve desired characteristics. 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 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 alone 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 having a pixel portion containing polyhalogenated zinc phthalocyanine A.

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

[0094] The pixel portion containing polyhalogenated zinc phthalocyanine A can be formed using, for example, the coloring composition. Therefore, the pixel portion containing polyhalogenated zinc phthalocyanine A can contain the coloring composition or a cured product thereof. The method for forming the pixel portion varies depending on the type of material contained in the coloring composition, but may be a known or commonly used method such as photolithography, electrodeposition, transfer, micellar electrolysis, or PVED (Photovoltaic Electrodeposition).

[0095] Other configurations of the color filter may be the same as those of known and commonly used color filters. The color filter may further include, for example, a black matrix portion, a pixel portion containing a red pigment, and a pixel portion containing a blue pigment. These can be manufactured using known and commonly used materials by known and commonly used methods (for example, the above-mentioned method for forming pixel portions).

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

[0097] Known methods for producing polyhalogenated zinc phthalocyanine include the chlorosulfonic acid method, the halogenated phthalonitrile method, and the melting method, and the production method of this embodiment (particularly the first and second steps) may be carried out according to these known methods. Among these methods, the melting method can increase the abundance ratio of 16-brominated zinc phthalocyanine, thereby producing polyhalogenated zinc phthalocyanine that contributes to improving the brightness of color filters.

[0098] In a general melting method, a halogenating agent such as sulfuryl chloride or bromine is mixed with a melt (molten salt) of a metal salt that serves as a solvent during halogenation to prepare a first reaction solution, and then zinc phthalocyanine is mixed with the obtained first reaction solution to halogenate the zinc phthalocyanine. However, in the production method of this embodiment, after mixing zinc phthalocyanine with the first reaction solution, a halogenating agent is mixed and the mixture is heated at a predetermined temperature rise rate. By performing such a process, a polyhalogenated zinc phthalocyanine (for example, the above-mentioned polyhalogenated zinc phthalocyanine A) that contributes to improving the brightness of a color filter can be obtained.

[0099] Each step will be described below.

[0100] (first step) In the first step, a first reaction solution containing a metal salt and a halogenating agent is prepared. In order 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 a step of preparing a first reaction solution containing a melt of a metal salt (molten salt) and a halogenating agent.

[0101] The first step may be a step of preparing a first reaction solution prepared in advance, or 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 the metal salt and the first halogenating agent. That is, the first step may include a step of mixing a metal salt and a halogenating agent, or may include a step of mixing a second halogenating agent into a reaction solution containing the metal salt and the first halogenating agent. By mixing the second halogenating agent into a reaction solution containing the metal salt and the first halogenating agent, the halogenation rate can be improved.

[0102] In the melting method, the metal salt may be melted before being mixed with the halogenating agent to form a molten salt, which may then be 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 (AlCl), aluminum bromide (AlBr), etc.), alkali (earth) metal halides (sodium chloride (NaCl), etc.), titanium tetrachloride, etc. In the melting method, aluminum chloride or sodium chloride may be used, or these 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 part by mass of zinc phthalocyanine used in the second step, from the viewpoint of increasing the reactivity as a Friedel-Crafts catalyst in the 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 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 salts used may be, for example, 3 to 6 parts by mass per 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, a brominating agent may be used. A brominating agent may be used in combination with another halogenating agent, and from the viewpoint of increasing brightness, a chlorinating agent may be used in combination. For example, one of a brominating agent and a chlorinating agent may be used as the first halogenating agent, and the other of a brominating agent and a chlorinating 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 hypobromite, dibromoisocyanuric acid, 2,4,4,6-tetrabromocyclohexa-2,5-dienone, hydrogen bromide-dimethyl sulfoxide, N-bromosuccinimide-dimethylformamide, 2,4-diamino-1,3-thiazole hydrotribromide, 1,3-dibromo-5,5-dimethylhydantoin, etc. Bromine may be used from the viewpoint of improving the purity of the product.

[0110] The chlorinating agent includes sulfuryl chloride, thionyl chloride, and the like.

[0111] The amount of the brominating agent used may be 0.01 to 5.0 parts by mass relative to 1 part by mass of the zinc phthalocyanine used in the second step, from the viewpoint of increasing the bromination rate. When a chlorinating agent is used in combination, the chlorination rate can be suppressed by setting the amount of the brominating agent used within the above range. From the same viewpoint, the amount of the 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 relative to 1 part by mass of the zinc phthalocyanine used in the second step.

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

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

[0114] (Second process) In the second step, the first reaction solution is mixed with zinc phthalocyanine to obtain a second 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 sufficiently dissolving the raw materials.

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

[0117] The halogenating agent may be any of those that can be used in the first step described above. 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-brominated zinc phthalocyanine," the amount of the brominating agent used may be 3.0 to 10.0 parts by mass or 5.0 to 8.0 parts by mass per part by mass of zinc phthalocyanine. In this embodiment, the total amount of the 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 abundance ratio of "16-brominated zinc phthalocyanine."

[0120] The total amount of the brominating agent used in the first step and the third step (the total amount of the brominating agent used in the first step and the 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 part by mass of zinc phthalocyanine, from the viewpoint of increasing the abundance ratio of "16-brominated zinc 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 to 50°C, 10 to 45°C, or 10 to 30°C, from the viewpoint of sufficiently dissolving the raw materials.

[0123] (Fourth step) In the fourth step, the third reaction solution is heated. At this time, by setting the temperature rising rate of the third reaction solution to 2.5° C. / hour or less, halogenation proceeds well.

[0124] From the viewpoint of more smoothly progressing the halogenation, the temperature increase rate may be 0.5°C / hour, 1.0°C / hour, or 2.4°C / hour, or may be 0.5 to 2.5°C / hour, or 1.0 to 2.4°C / hour.

[0125] The temperature increase rate is determined by dividing the difference between the temperature of the third reaction solution at the end of the temperature increase (hereinafter referred to as the "temperature increase end temperature") and the temperature of the third reaction solution at the start of the temperature increase (hereinafter referred to as the "temperature increase start temperature") by the time from the start of the temperature increase (start of heating) to the end of the temperature increase (hereinafter referred to as the "temperature increase time"). Therefore, as long as the temperature increase rate calculated by the above method is 2.5°C / hour or less, the temperature increase rate does not need to be 2.5°C / hour or less throughout the temperature increase time. There may be periods during which the temperature increase rate exceeds 2.5°C / hour, and there may be periods during which the third reaction solution is maintained at a constant temperature without being heated. However, if the temperature increase rate is 2.5°C / hour or less throughout the temperature increase time (i.e., there is no period during which the temperature increase rate exceeds 2.5°C / hour), halogenation tends to proceed more efficiently. From a similar perspective, the temperature increase rate may be constant throughout the temperature increase time (e.g., fluctuations in the temperature increase rate are ±0.1°C / hour or less).

[0126] From the viewpoint of improving the solubility of the raw materials, the temperature increase starting temperature may be 5 to 50° C. From the same viewpoint, the temperature increase starting temperature may be 10° C. or higher, 45° C. or lower, or 40° C. or lower, or may be 10 to 45° C. or 10 to 40° C.

[0127] From the viewpoint of improving the halogenation rate, the temperature at which the temperature is increased may be 75° C. or higher. From the same viewpoint, the temperature at which the temperature is increased may be 80° C. or higher, or may be 170° C. or lower, 150° C. or lower, or 100° C. or lower, or may be 75 to 170° C., 80 to 150° C., or 75 to 125° C. The temperature at which the temperature is increased means the final temperature reached in the fourth step.

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

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

[0130] After the fourth step, if necessary, steps such as a step of precipitating a polyhalogenated zinc phthalocyanine by mixing the reaction solution with water or the like, a step of washing the precipitate, a step of drying the washed precipitate, and a step of pulverizing the dried precipitate by pulverizing, grinding, or the like may be carried out. The step of pulverizing the precipitate is also called a pigmentation step. Since the precipitate after drying is a coarse, dry aggregate called a "crude pigment," by carrying out the pigmentation step, a polyhalogenated zinc phthalocyanine pigment having a small average primary particle size can be obtained. The above steps may be carried out by known, commonly used techniques carried out when producing polyhalogenated zinc phthalocyanine.

[0131] From the viewpoint of easily obtaining a fine pigment, the pigmentation step may include a step of subjecting the dried precipitate to a solvent salt milling treatment. The solvent salt milling treatment is a treatment in which a crude pigment that is a polyhalogenated zinc phthalocyanine that has not been subjected to pigmentation and has been milled immediately after synthesis or thereafter, is kneaded and milled 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 charged into a kneader, and kneading and milling are carried out therein. For example, a kneader or a mixer can be used as the kneader.

[0132] As described above, in the production method of the above embodiment, the halogenation rate of the polyhalogenated zinc phthalocyanine can be increased by changing the heating conditions, particularly in the fourth step. Therefore, the polyhalogenated zinc phthalocyanine A of the above embodiment can also be obtained by adjusting the heating rate, heating start temperature, heating end temperature, heating time, etc. in the fourth step. [Example]

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

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

[0135] Example 1 (Synthesis of Polyhalogenated Zinc Phthalocyanines) 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, "AlCl" in Table 1), and 43 parts by mass of sodium chloride (Tokyo Chemical Industry Co., Ltd., product code: S0572, "NaCl" in Table 1) were mixed at room temperature (25°C) to obtain a reaction solution containing a melt of metal salts (molten salt) (first half of the first step). Next, 43 parts by mass of bromine ("Br(1)" in Table 1) was mixed with the resulting reaction solution to obtain a first reaction solution (second half of the first step).

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

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

[0139] The reaction liquid (reaction mixture) obtained in the fourth step was extracted into water, and polyhalogenated zinc phthalocyanine was precipitated to obtain a polyhalogenated zinc phthalocyanine slurry. The obtained slurry was then filtered, washed with 60°C water, and re-peptized in water. The obtained slurry was filtered again, washed with 60°C water, and dried at 90°C to obtain 173 parts by mass of a crude pigment consisting of polyhalogenated zinc phthalocyanine (polyhalogenated zinc phthalocyanine crude pigment). 3 parts by mass of this polyhalogenated zinc phthalocyanine crude pigment, 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 extracted into 300 parts by mass of 80°C water, stirred for 1 hour, filtered, and washed with 60°C water. The resulting mixture was then dried and pulverized to obtain a pigment consisting of polyhalogenated zinc phthalocyanine (polyhalogenated zinc phthalocyanine pigment).

[0140] <Examples 2 to 14 and Comparative Examples 1 and 2> Polyhalogenated zinc phthalocyanines (pigments) of Examples 2 to 14 and Comparative Examples 1 and 2 were synthesized in the same manner as in Example 1, except that the formulations were changed as shown in Table 1.

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

[0142] (mass spectrometry) Mass analysis of the polyhalogenated zinc phthalocyanine constituting 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 polyhalogenated zinc phthalocyanine was 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 as a measurement sample and measured in Spiral POS mode. The instrument's measurement parameters were set to detect m / z = 1840 when performing mass analysis of a known compound with a molecular weight of 1840. The delay time during mass analysis was 275 ns, the detector was 68%, the laser intensity was 34%, and the resolving power value for the peak 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 spectrum, the maximum ion intensity I1 in the range of m / z 1820 to 1860, the maximum ion intensity I2 in the range of m / z 1740 to less than 1780, the maximum ion intensity I3 in the range of m / z 1780 to less than 1820, the maximum ion intensity I4 in the range of m / z 1650 to less than 1740, and the maximum ion 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. For reference, the sum of the maximum ion 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 is shown in Table 3.

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

[0145] (ICP analysis) The zinc (Zn) content of the polyhalogenated zinc phthalocyanine pigment was determined by ICP atomic emission spectroscopy. Specifically, a standard solution for atomic absorption spectroscopy (Merck Millipore's ICP Multi-Element Standard IV, zinc concentration: 1000 ppm by mass) was first diluted stepwise with ion-exchanged water (ultrapure water) to prepare diluted solutions 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, and 3000 μg / kg. These diluted solutions and ion-exchanged water (ultrapure water, zinc concentration: 0 μg / kg) were added to 8 mL of nitric acid to a total volume of 25 g to prepare standard samples. These were then measured using an ICP atomic emission spectrometer (Agilent ICP-OES5800, Agilent) to create a calibration curve. Separately, 0.26 g of polyhalogenated zinc phthalocyanine pigment was decomposed in 8 mL of nitric acid using a microwave decomposition system MARS6 manufactured by CEM 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 a measurement solution. This measurement solution was measured using the ICP emission spectrometer, and the zinc content was determined using the calibration curve.

[0146] (Combustion IC analysis) The bromine (Br) content and chlorine (Cl) content of the polyhalogenated zinc phthalocyanine constituting the pigment were determined by combustion ion chromatography.

[0147] Specifically, a bromine standard 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, respectively. These were then measured using an ion chromatograph (ICS-6000 manufactured by Thermo) to create a calibration curve for measuring the bromine content.

[0148] In addition, a chlorine standard solution (chlorine concentration: 10 ppm by mass) was gradually 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 (ICS-6000 manufactured by Thermo) to create a calibration curve for measuring the chlorine content.

[0149] Separately, 2 mg of polyhalogenated phthalocyanine pigment was combusted in an automatic sample combustion apparatus (AQF-2100H manufactured by Mitsubishi Chemical Analytech Co., Ltd.), and the generated gas was absorbed in 15 mL of ultrapure water containing hydrogen peroxide to obtain an absorbent solution. The ultrapure water containing hydrogen peroxide was prepared by diluting 1 g of 30% hydrogen peroxide with 500 mL of ultrapure water. The absorbent solution was then diluted to 1500 mL with ultrapure water to prepare a measurement solution. This measurement solution was measured using the ion chromatograph, and the bromine and chlorine contents were determined using the calibration curve.

[0150] <Evaluation> (Spectral transmittance and contrast measurement) [Preparation of Green Colored Composition] Green colored compositions were prepared using the polyhalogenated zinc phthalocyanine (pigment) obtained in Examples 1 to 14 and Comparative Examples 1 and 2. Specifically, 2.48 parts by mass of the polyhalogenated zinc phthalocyanine (pigment) was dispersed for 2 hours in a paint shaker (a test disperser manufactured by Toyo Seiki Seisaku-sho, Ltd.) together with 1.24 parts by mass of BYK-LPN6919 (manufactured by BYK, dispersant: solids content 60% by mass), 1.86 parts by mass of Unidic 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) using 0.3 to 0.4 mm zircon beads to prepare a green colored composition for forming a green pixel portion for a color filter.

[0151] [Preparation of green spin coating solution] A green spin coating liquid was prepared by adding 4.0 parts by mass of the green coloring composition, 0.98 parts by mass of Unidic 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 with a paint shaker (manufactured by Toyo Seiki Seisakusho, Ltd., test disperser).

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

[0153] [Spectral transmittance measurement] The spectral transmittance of the above-mentioned evaluation glass substrate was measured using a Hitachi High-Tech Science U-3900, 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 (Method of measuring color - Reflected and transmitted object color) using a Type 1 spectrophotometer. The results are shown in Table 2.

[0154] [Contrast Measurement] Using the above 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 set as the reference (100%), and the relative ratio of each Example and Comparative Example was calculated. The above device had a space for installing the green pixel part of the color filter between two polarizing plates, a light source on one side of the polarizing plate, and a color luminance meter on the opposite side. The contrast was calculated from the ratio of the luminance (transmitted light intensity) when the polarization axes were parallel to each other and perpendicular to each other. The results are shown in Table 2.

[0155] (brightness measurement) [Preparation of Yellow Colored Composition] A yellow colored composition for forming a green pixel portion for a color filter was prepared by dispersing 2.48 parts by mass of CI Pigment Yellow 138 (Paliotol Yellow D0960 manufactured by Sun Chemical Co., Ltd.) (pigment) together with 1.24 parts by mass of BYK-LPN6919 (manufactured by BYK, dispersant: solids content 60% by mass), 1.86 parts by mass of Unidic 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) using 0.3 to 0.4 mm zircon beads in a paint shaker (test disperser manufactured by Toyo Seiki Seisaku-sho, Ltd.) for 2 hours.

[0156] [Preparation of yellow spin coating solution] Next, 4.0 parts by mass of the yellow coloring composition, 0.98 parts by mass of Unidic 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, Ltd., test disperser) to prepare a yellow spin coating liquid.

[0157] [Preparation of green spin coating solution] A green spin coating solution was prepared in the same manner as in (Measurement of spectral transmittance and contrast).

[0158] [Preparation of Colored Composition for Evaluation and Fabrication of Glass Substrate for Evaluation] The prepared green spin coating liquid and yellow spin coating liquid were mixed to prepare a colored composition for evaluation. The obtained colored composition for evaluation was spin-coated on a soda glass (glass plate manufactured by Nippon Sheet Glass Co., Ltd.), dried at 90 ° C for 3 minutes, and then baked at 230 ° C for 1 hour to obtain a glass substrate for evaluation with a chromaticity (x, y) = (0.286, 0.575).

[0159] [Luminance measurement] Using the above evaluation glass substrates, the luminance was measured using a U-3900 manufactured by Hitachi High-Tech Science Corporation. Specifically, the luminance of Comparative Example 2 was set as the standard (100%), and the relative ratio between each Example and 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 independently represents a hydrogen atom or a halogen atom such as a chlorine atom or a bromine atom. １ ~X １６ At least two of the are halogen atoms.) The compound includes 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 was determined as I １ The maximum ion intensity in the range of m / z 1780 or more and less than 1820 is defined as I ３ When I ３ / I １ A polyhalogenated zinc phthalocyanine having a ρ of 0.01 or more and less than 0.

50.

2. 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 was determined as I １ The maximum ion intensity in the range of m / z 1740 or more and less than 1780 is I ２ When I ２ / I １ 2. The polyhalogenated zinc phthalocyanine according to claim 1, wherein the ρ is 0.50 or less.

3. 2. The polyhalogenated zinc phthalocyanine according to claim 1, wherein the zinc content determined by ICP emission spectroscopy is 2.5 to 5.0 mass%.

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

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

6. 2. The polyhalogenated zinc phthalocyanine according to claim 1, having an average primary particle size of 5 to 100 nm.

7. A coloring composition comprising the polyhalogenated zinc phthalocyanine according to any one of claims 1 to 6.

8. A color filter comprising a pixel portion containing the polyhalogenated zinc phthalocyanine according to any one of claims 1 to 6.

9. a first step of preparing a first reaction solution containing a metal salt, a chlorinating agent, and a brominating agent; a second step of mixing zinc phthalocyanine with the first reaction solution to obtain a second reaction solution; a third step of mixing a brominating agent with the second reaction solution to obtain a third reaction solution; a fourth step of heating the third reaction liquid; At least a temperature increase rate of the third reaction solution in the fourth step being 2.5° C. / hour or less;

10. 10. The method for producing polyhalogenated zinc phthalocyanine according to claim 9, wherein the temperature increase start temperature in the fourth step is 5 to 50°C.

11. The method for producing a polyhalogenated zinc phthalocyanine according to claim 9 or 10, wherein the temperature increase end temperature in the fourth step is 75 to 170°C.

12. 11. The method for producing a polyhalogenated zinc phthalocyanine according to claim 9 or 10, wherein the first step comprises a step of mixing one of a chlorinating agent and a brominating agent with a reaction liquid containing the other of a chlorinating agent and a brominating agent.

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