Polyhalogenated zinc phthalocyanine, coloring composition, color filter, and production method for 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

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

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

[0002] A green pigment containing polyhalogenated zinc phthalocyanine is sometimes used in color filters used in 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 color filters with higher brightness. 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.

[0004] Japanese Patent Application Laid-Open No. 2007-284589

[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.

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

[14] .

[0008] [1] The following general formula (i): (In general formula (i), X １ ~X １６ each independently represents a hydrogen atom or a halogen atom. １ ~X １６ 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 I １The maximum ion intensity in the range of m / z 1740 or more and less than 1780 is I ２ When I ２ / I １ A polyhalogenated zinc phthalocyanine having a ρ of 0.50 or less.

[0009] [2] 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 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 The polyhalogenated zinc phthalocyanine according to [1], wherein

[0010] [3] 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 determined as I １ The maximum ion intensity in the range of m / z 1650 or more and less than 1740 is I ４ When I ４ / I １ The polyhalogenated zinc phthalocyanine according to [1] or [2], wherein

[0011] [4] 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 determined as I １ The maximum ion intensity in the range of m / z 900 or more and less than 1650 is defined as I ５ When I ５ / I １ [4] The polyhalogenated zinc phthalocyanine according to any one of [1] to [3], wherein

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

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

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

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

[0016] [9] A coloring composition containing 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 method for producing a polyhalogenated zinc phthalocyanine, comprising at least: a first step of preparing a first reaction liquid containing a metal salt and a halogenating agent; a second step of mixing zinc phthalocyanine with the first reaction liquid to obtain a second reaction liquid; a third step of mixing a halogenating agent with the second reaction liquid to obtain a third reaction liquid; and a fourth step of heating the third reaction liquid, wherein the heating rate of the third reaction liquid 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.

[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.

[0023] 1 shows the mass spectrum of Example 13 obtained by matrix-assisted laser desorption ionization time-of-flight mass spectrometry.

[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).

[0026] In general formula (i), X １ ~X １６ each independently represents a hydrogen atom or a halogen atom. 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") has a maximum ion intensity of I in the range of m / z 1820 to 1860 in a mass spectrum obtained by matrix-assisted laser desorption / ionization time-of-flight mass spectrometry (MALDI-TOF MS). 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 (Maximum ionic strength I １ Maximum ionic strength I ２The maximum ionic intensity I is the intensity of the peak with the greatest intensity in each of the above ranges. １ is 16-brominated zinc phthalocyanine (X in formula (i) １ ~X １６ The maximum ion intensity I is the intensity of the peak corresponding to the compound where all ions are bromine atoms. ２ is 15-brominated zinc phthalocyanine (X in formula (i) １ ~X １６ wherein 15 are bromine atoms and 1 is a hydrogen atom) and / or 14 bromine dichloride zinc phthalocyanine (wherein X in formula (i) １ ~X １６ The intensities of the peaks corresponding to a compound in which 14 atoms are bromine atoms and 2 atoms are chlorine atoms are shown.

[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 whose molecular weight is known to be Q, measurement parameters are set so that m / z=Q is detected.

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

[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 tendency that the more bromine atoms present on the phthalocyanine ring, the greater the molecular distortion and the more absorption occurs on the long wavelength side. Therefore, the greater the proportion of 16-brominated zinc phthalocyanine, the more the absorption peak will be on the long wavelength side of the above wavelength region, making it more difficult to absorb light in the above wavelength region (particularly near 580 nm). In contrast, polyhalogenated zinc phthalocyanine A1 has a characteristic that the I ２ / I １ Since the value is 0.50 or less, the abundance ratio of 15-brominated zinc phthalocyanine and 14-bromodichlorozinc phthalocyanine to 16-brominated zinc phthalocyanine is small compared to conventional polyhalogenated zinc phthalocyanines (i.e., the abundance ratio of 16-brominated zinc phthalocyanine is high). In other words, polyhalogenated zinc phthalocyanine A1 is less likely to absorb light in the above wavelength region (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 region of 480 to 580 nm, thereby improving the brightness of the color filter.

[0032] I ２ / I １ From the viewpoint of further improving the brightness and contrast of the color filter, I may be 0.45 or less or 0.30 or less. ２ / I １ 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 chlorine atom can be observed. The maximum ion intensity in the above range (m / z range of 1780 or more and less than 1820) is expressed as I ３ When I ３ / I １ (Maximum ionic strength I １ Maximum ionic strength I ３ The ratio of I to I may be 1.00 or less. ３ / I １ When I is 1.00 or less, the brightness and contrast of the color filter tend to be further improved. ３ / I １ may be 0.70 or less, less than 0.50, or 0.45 or less. ３ / I １ 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, and 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-dichlorozinc phthalocyanine (X in formula (i)) １ ~X １６ 13 of which are bromine atoms, 2 of which are chlorine atoms, and 1 of which is hydrogen atom), 14. brominated zinc phthalocyanine (X in formula (i) １ ~X １６ Peaks corresponding to compounds in which 14 bromine atoms and 2 hydrogen atoms are observed can be observed. The maximum ion intensity in the above range (m / z range of 1650 or more and less than 1740) is expressed as I ４ When I４ / I １ (Maximum ionic strength I １ Maximum ionic strength I ４ The ratio of I to I may be 0.45 or less. ４ / I １ When I is 0.45 or less, the brightness and contrast of the color filter tend to be further improved. ４ / I １ may be 0.40 or less, 0.35 or less, 0.30 or less, or 0.25 or less. ４ / I １ 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) is brominated zinc phthalocyanine; １ ~X １６ Peaks corresponding to compounds in which 13 of the m / z atoms are bromine atoms and 3 are hydrogen atoms can be observed. The maximum ion intensity in the above range (m / z range of 900 or more and less than 1650) is expressed as I ５ When I ５ / I １ (Maximum ionic strength I １ Maximum ionic strength I ５ The ratio of I to I may be 0.50 or less. ５ / I １ When I is 0.50 or less, the brightness and contrast of the color filter tend to be further improved. ５ / I １ may be 0.30 or less, 0.24 or less, or 0.20 or less. ４ / I １ 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] I ５ / I ２ (Maximum ionic strength I ２ Maximum ionic strength I ５ From the viewpoint of achieving both high brightness and high contrast, the ratio of I to I 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. ５ / I ２ may be 0.05 or more, 0.10 or more, 0.15 or more, 0.20 or more, 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 ionic strength I １ may be the maximum intensity of the peak corresponding to the compound represented by formula (i).

[0039] The maximum ionic strength I １ ~I ５ The sum of (I １ +I ２ +I ３ +I ４ +I ５ ) to I Ｔ Then, I １ / I Ｔ From 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] I ２ / 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] I ３ / I ＴFrom 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] I ４ / 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] I ５ / 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 the same as the above-mentioned I ３ / I １ is 0.60 to 1.00, and the above I ５ / I ２ is 1.00 or less.

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

[0046] The reason why the above effect is obtained is not clear, but polyhalogenated zinc phthalocyanine A2 has the following properties: ３ / I １ and I ５ / I ２It is presumed that, since the absorption peak is shifted to the long wavelength side by being in the above range, it is difficult to absorb light in the wavelength region of 480 to 580 nm compared to 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 above I ２ / I １ may be less than or equal to 0.50 or greater than 0.50. ２ / I １ From the viewpoint of further improving the brightness and contrast of the color filter, I may be 0.50 or less, 0.45 or less, or 0.30 or less. ２ / I １ 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 above I ３ / I １ may be 0.70 to 1.00 or 0.80 to 1.00.

[0050] In the second embodiment, the above I ５ / I ２ From the viewpoint of further improving the brightness and contrast of the color filter, I may be 0.80 or less or 0.70 or less. ５ / I ２ 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. ５ / I ２ may be 0.15 or more, 0.20 or more, or 0.40 or more, or may be 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 the same as the above-mentioned I. ４ / I １ is 0.45 or less, and ５ / I ２ is 1.00 or less.

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

[0053] The reason why the above effect is obtained is not clear, but polyhalogenated zinc phthalocyanine A3 has the following properties: ４ / I １ and I ５ / I ２ It is presumed that, since the absorption peak is shifted to the long wavelength side by being in the above range, it is difficult to absorb light in the wavelength region of 480 to 580 nm compared to 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 above I ２ / I １ may be less than or equal to 0.50 or greater than 0.50. ２ / I １ From the viewpoint of further improving the brightness and contrast of the color filter, I may be 0.50 or less, 0.45 or less, or 0.30 or less. ２ / I １ 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, the above I４ / I １ From the viewpoint of further improving the brightness and contrast of the color filter, I 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. ４ / I １ 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, the above I ５ / I ２ From the viewpoint of further improving the brightness and contrast of the color filter, I may be 0.80 or less or 0.70 or less. ５ / I ２ 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. ５ / I ２ may be 0.15 or more, 0.20 or more, or 0.40 or more, or may be 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 the same as the polyhalogenated zinc phthalocyanine A4 described above. ５ / I １ is 0.20 or less, and ５ / I ２ is 1.00 or less.

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

[0060] The reason why the above effect is obtained is not clear, but polyhalogenated zinc phthalocyanine A4 has the following properties:５ / I １ and I ５ / I ２ It is presumed that, since the absorption peak is shifted to the long wavelength side by being in the above range, it is difficult to absorb light in the wavelength region of 480 to 580 nm compared to 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 region 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 above I ２ / I １ may be less than or equal to 0.50 or greater than 0.50. ２ / I １ From the viewpoint of further improving the brightness and contrast of the color filter, I may be 0.50 or less, 0.45 or less, or 0.30 or less. ２ / I １ 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, the above I ５ / I １ From the viewpoint of further improving the brightness and contrast of the color filter, I may be 0.01 or more, for example, 0.01 to 0.20. ５ / I １ 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, the above I ５ / I ２ From the viewpoint of further improving the brightness and contrast of the color filter, I may be 0.80 or less or 0.70 or less. ５ / I ２may 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. ５ / I ２ may be 0.15 or more, 0.20 or more, or 0.40 or more, or may be 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. 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% by mass, 3.2 to 4.2% by mass, 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% by mass, 35 to 70% by mass, 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 may 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 may 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-mentioned spectral transmittance Tb is the maximum spectral transmittance.

[0074] The spectral transmittance Tc of polyhalogenated zinc phthalocyanine A at 480 nm may 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 first 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 (e.g., 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 a color filter.

[0084] Examples of dispersants include DISPERBYK (Disperbyk) manufactured by BYK-Chemie. ＴＭ ) 130, 161, 162, 163, 170, LPN-6919, LPN-21116, BASF 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 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 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 alkali-soluble resins 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 a solid content, from the viewpoint of colorant dispersibility and dispersion stability.

[0088] The content of the resin in 100% by mass of the coloring 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 C.I. 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, 110, 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, and 231. These may 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 for Producing 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 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] As a method for producing polyhalogenated zinc phthalocyanine, known methods such as a chlorosulfonic acid method, a halogenated phthalonitrile method, and a melting method are known, 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 obtaining a 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, but in the production method of this embodiment, a step of mixing zinc phthalocyanine with the first reaction solution, then mixing a halogenating agent, and heating at a predetermined temperature rise rate is carried out. By carrying out such a step, 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, 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 (AlCl ３ ), aluminum bromide (AlBr ３ ) and the like), alkali (earth) metal halides (sodium chloride (NaCl) and the like), 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 relative to 1 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 relative to 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 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] Brominating agents include bromine (Br ２ ), 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. From the viewpoint of improving the purity of the product, bromine may be used.

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

[0111] From the viewpoint of increasing the bromination rate, 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. 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 Step) In the second step, the 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 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 or 1.0°C / hour, or may be 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 rise rate is determined by dividing the difference between the temperature of the third reaction solution at the end of the temperature rise (hereinafter referred to as the "temperature rise end temperature") and the temperature of the third reaction solution at the start of the temperature rise (hereinafter referred to as the "temperature rise start temperature") by the time from the start of the temperature rise (start of heating) to the end of the temperature rise (hereinafter referred to as the "temperature rise time"). Therefore, as long as the temperature rise rate calculated by the above method is 2.5°C / hour or less, the temperature rise rate does not need to be 2.5°C / hour or less throughout the temperature rise time. There may be a time period in which the temperature rise rate exceeds 2.5°C / hour, and there may be a time period in which the third reaction solution is maintained at a constant temperature without being heated. However, if the temperature rise rate is 2.5°C / hour or less throughout the temperature rise time (i.e., there is no time period in which the temperature rise rate exceeds 2.5°C / hour), halogenation tends to proceed more smoothly. From the same perspective, the temperature rise rate may be constant throughout the temperature rise time (e.g., the temperature rise rate fluctuates by ±0.1°C / h 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] The temperature at which the temperature rise is completed may be 75° C. or higher from the viewpoint of improving the halogenation rate. From the same viewpoint, the temperature at which the temperature rise is completed 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 rise is completed means the final temperature reached in the fourth step.

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

[0129] The fourth step may include a step of continuing heating after completion of the temperature increase and maintaining the temperature at the temperature at the end of the temperature increase. The maintenance 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.

[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 Phthalocyanine First, 270 parts by mass of sulfuryl chloride (Wako Pure Chemical Industries, Ltd., product code: 190-04815, "SulCl" in Table 1), 270 parts by mass of anhydrous aluminum chloride (Kanto Chemical Co., Ltd., product code: 01156-00, "AlCl" in Table 1) ３ 315 parts by mass of sodium chloride (Tokyo Chemical Industry Co., Ltd., product code: S0572, "NaCl" 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 liquid containing a melt of metal salts (molten salt) (first half of the first step). Next, bromine ("Br ２ A first reaction solution was obtained by mixing 43 parts by mass of the above-mentioned ester (1)) (the latter half of the first step).

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

[0137] Next, bromine (Wako Pure Chemical Industries, Ltd., product code: 026-02405, "Br ２ A third reaction solution was obtained by adding 479 parts by mass of the compound (2) dropwise (third step).

[0138] Next, the third reaction solution was heated for 30 hours at a temperature increase rate of 2.3°C / hour (variation of the temperature increase rate: ±0.1°C / hour or less) (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 water at 60°C, and re-peptized 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 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 water at 80°C, stirred for 1 hour, filtered, and washed with water at 60°C. 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 Analysis) 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), and a mass spectrum was obtained. Specifically, 0.5 mg of polyhalogenated zinc phthalocyanine was first ultrasonically dispersed in 1 mL of THF for 30 minutes using an ultrasonic cleaner Bransonic (EMERSON, CPX2800H-J) to obtain a dispersion. Next, 1 μL of the dispersion was dropped onto a target plate to serve as a measurement sample, and measurement was performed in Spiral POS mode. Note that the measurement parameters of the instrument were set so that m / Z = 1840 was detected 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 of the peak between m / z=1820 and 1860 was 42805. As an example, the mass spectrum of Example 13 is shown in FIG.

[0143] From the obtained mass spectrum, the maximum ion intensity I in the range of m / z 1820 to 1860 １ , the maximum ion intensity I in the range of m / z 1740 or more and less than 1780 ２ , the maximum ion intensity in the range of m / z 1780 or more and less than 1820 is I ３ , the maximum ion intensity I in the range of m / z 1650 or more and less than 1740 ４ and the maximum ion intensity I in the range of m / z 900 or more and less than 1650 ５ I ２ / I １ , I ３ / I １ , I ４ / I １ , I ５ / I １ and I ５ / I ２ The results are shown in Table 2. For reference, the maximum ionic strength I １ ~I ５ The sum of (I １ +I ２ +I ３ +I ４ +I５ ) to I Ｔ When I １ / I Ｔ , I ２ / I Ｔ , I ３ / I Ｔ , I ４ / I Ｔ and I ５ / I Ｔ is shown in Table 3.

[0144] (Measurement of Average Primary Particle Diameter) 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 defined 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 defined as the average primary particle diameter of the polyhalogenated zinc phthalocyanine pigment.

[0145] (ICP Analysis) The zinc (Zn) content of the polyhalogenated zinc phthalocyanine constituting the 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, or 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 amount of 25 g to prepare standard samples. These were then measured using an ICP atomic 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 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 obtain 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 Corporation) 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. These were then measured using an ion chromatograph (ICS-6000 manufactured by Thermo Corporation) to create a calibration curve for measuring the chlorine content.

[0149] On the other hand, 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 obtain a measurement solution. This measurement solution was measured using the ion chromatograph, and the bromine content and chlorine content were determined using the calibration curve.

[0150] <Evaluation> (Measurement of Spectral Transmittance and Contrast) [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 together with 1.24 parts by mass of BYK-LPN6919 (manufactured by BYK Corporation, 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 to prepare a green colored composition for forming a green pixel portion for a color filter.

[0151] [Preparation of Green Spin Coating Liquid] 4.0 parts by mass of the green colored 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 Seisaku-sho, Ltd., test disperser), to prepare a green spin coating liquid.

[0152] [Preparation of Glass Substrate for Evaluation] The above 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 the baking was carried out so that the film thickness after deposition would be 2 μm.

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

[0154] [Measurement of Contrast] 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 location for installing a green pixel portion of a 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 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] (Measurement of Brightness) [Preparation of Yellow Coloring Composition] 2.48 parts by mass of Pigment Yellow 138 (Paliotol Yellow D0960 manufactured by Sun Chemical Corporation) (pigment) was dispersed together with 1.24 parts by mass of BYK-LPN6919 (manufactured by BYK Corporation, 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 to prepare a yellow coloring composition for forming a green pixel portion for a color filter.

[0156] [Preparation of Yellow Spin Coating Liquid] 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 Seisaku-sho, Ltd., test disperser), thereby preparing 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] [Measurement of Brightness] Using the above-mentioned evaluation glass substrate, the brightness was measured with a U-3900 manufactured by Hitachi High-Tech Science Corporation. Specifically, the brightness 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]

[0161]

[0162]

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. 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 and the maximum ionic intensity in the range of m / z 1780 or more and less than 1820 is I 3 , the I 3 / I 1 ratio is 0.01 or more and less than 0.

50.

2. The polyhalogenated zinc phthalocyanine according to claim 1, 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 I1 and the maximum ion intensity in the range of m / z 1740 or more and less than 1780 is I2, I2 / I1 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 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 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 a second halogenating agent with a reaction liquid containing a first halogenating agent and the metal salt.

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