KR20230085148A - Pigments for color filters, coloring compositions, and color filters - Google Patents

Abstract

The pigment for color filters of the present invention is a pigment for forming a coating film in a green pixel portion of a color filter,
When the film thickness of the coating film is 1.5 μm to 2.4 μm and the composition is 1.25 parts of resin per 1 part of the pigment in terms of mass, in the XYZ color system of CIE when colorimetry is performed using a C light source alone, the formulas (A) to ( D) can indicate the xy chromaticity coordinate area surrounded by
The pigment contains a zinc halide phthalocyanine pigment which is a compound represented by formula (1), the number of halogen atoms in one molecule of the compound is 0.2 or more and 10 or less on average, and the number of bromine atoms in one molecule of the compound is 0.1 on average. 10 or more, and the number of chlorine atoms in one molecule of the compound is 0.1 or more and less than 2 on average.
In addition, formulas (A) to (D) and formula (1) are as described herein.

Description

Pigments for color filters, coloring compositions, and color filters

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

BACKGROUND ART In a display device such as a liquid crystal display device, the color of light from a light source is converted by a color filter having red, green, and blue color pixel portions, and an image is displayed. For such a display device, various standards regarding color reproducibility exist, and it is required to be able to display colors with a predetermined chromaticity according to each standard. Therefore, a color filter used in a display device also needs to convert light from a light source into light having a chromaticity conforming to a standard.

Regarding the colorant of the green pixel part in the color filter, there is a demand for (1) high luminance and (2) high color reproduction.

(1) To achieve high luminance, it is important to select a pigment having high transmittance to the backlight, and Pigment Green 58 is used as the main pigment. Current displays are designed to have high luminance in accordance with the sRGB standard (green pixels are (x, y) = (0.300, 0.600)), and LED-YAG is widely used as a backlight. (2) In order to achieve high color reproduction, a pigment capable of displaying vivid colors is required. A proposal has been made to achieve high color reproduction by forming green pixels using a green photosensitive resin composition containing Pigment Green 7 and Pigment Yellow 185, but since Pigment Green 7 has a low transmittance, the brightness of the resulting display is low There is Pigment Green 59 as a novel high color reproduction pigment, and compared with the case where color filters of the same film thickness are produced, the use of Pigment Green 59 rather than Pigment Green 7 results in higher luminance. In order to cover the standard of high color reproduction display (AdobeRGB, DCI-P3, etc.), there is a design to increase the film thickness of the color filter, but problems such as insufficient hardening of the color filter in the exposure process occur. It is preferable to use a pigment capable of color display. For the above reasons, Pigment Green 58 is used in high brightness displays, and Pigment Green 59 is used in high color reproduction displays. About the above color filters, it is described, for example in Patent Documents 1 to 3 below.

Japanese Unexamined Patent Publication No. 2012-123302 Japanese Unexamined Patent Publication No. 2006-045399 International Publication No. 2015/118720 Pamphlet

In recent years, BT2020 has attracted attention as a color standard that is more vivid than the conventional AdobeRGB or DCI-P3. In the BT2020, a green pixel is designed with (x, y) = (0.170, 0.797) corresponding to 532 nm color light, but it was found difficult to achieve this with a color filter using Pigment Green 58 or 59 and a general light source. The green pixel portion of the color filter needs to transmit light around 532 nm and absorb other light. Recent development of light sources has progressed in the direction of adjusting the maximum wavelength to around 532 nm, but since unnecessary light is included on the shorter wavelength side and longer wavelength side than 532 nm, it is necessary to combine an appropriate color filter.

As described above, the problem is how to achieve chromaticity coordinates close to (x, y) = (0.170, 0.797) with a thin film in order to make a green color filter compatible with the new color standard BT2020. In addition, from the viewpoint of suppressing the power consumption of the display, it is also an issue how to design high luminance with chromaticity coordinates close to (x, y) = (0.170, 0.797).

Therefore, the subject of this invention is to provide the pigment which can be used as a color filter excellent in brightness|luminance with thin film thickness of a green pixel part in BT2020 which is a new color standard.

In the light source corresponding to BT2020, the present inventors use a pigment containing a zinc halide phthalocyanine pigment having a specific number of halogen atoms having a bluish color (cyan color), in the XYZ color system of CIE, (x, It has been found that a chromaticity coordinate area close to y) = (0.170, 0.797) can be displayed, and the above problems can be solved.

That is, this invention is as follows.

Item 1. As a pigment for forming a coating film in the green pixel portion of the color filter,

When the film thickness of the coating film is 1.5 μm to 2.4 μm and the composition is 1.25 parts of resin per 1 part of the pigment in terms of mass, in the XYZ color system of CIE when colorimetry is performed using a C light source alone, the following formula It is possible to display the xy chromaticity coordinate area surrounded by (A) to (D),

Formula (A)

y=-1.766x+0.618

(In the formula, x is 0.10≤x≤0.17.)

Formula (B)

y=5.889x-0.683

(In the formula, x is 0.15≤x≤0.17.)

Formula (C)

y=0.125x+0.181

(In the formula, x is 0.07≤x≤0.15.)

Formula (D)

y=8.380x-0.397

(In the formula, x is 0.07≤x≤0.10.)

The pigment contains a zinc halide phthalocyanine pigment which is a compound represented by the following formula (1), the number of halogen atoms in one molecule of the compound is from 0.2 to 10 on average, and the number of bromine atoms in one molecule of the compound is on average. 0.1 or more and 10 or less, and the number of chlorine atoms in 1 molecule of the said compound is 0.1 or more and less than 2 on average, The pigment for color filters.

[In Formula (1), X ¹ to X ¹⁶ each independently represents a hydrogen atom or a halogen atom. ]

Claim|item 2. The coloring composition containing the pigment for color filters of claim|item 1, and a solvent.

Claim|item 3. A color filter which has a green pixel part with the coating film formed with the pigment for color filters of claim|item 1.

According to the pigment of the present invention, when used as a color filter, the film thickness of the green pixel portion is thin and the pigment excellent in luminance can be provided.

1 shows a color gamut close to BT2020 in an xy chromaticity diagram.
2 shows an example of a spectrum of light from a light source.
Fig. 3 shows the pigments in the reference example in a monochromatic chromaticity plot (x-axis: chromaticity x, y-axis: chromaticity y).

[Pigments for color filters]

The pigment of the present invention is a pigment for forming a coating film in a green pixel portion of a color filter, and the pigment contains a zinc halide phthalocyanine pigment that is a compound represented by the following formula (1), and in one molecule of the compound The average number of halogen atoms is 0.2 or more and 10 or less, the average number of bromine atoms in one molecule of the compound is 0.1 or more and 10 or less, and the average number of chlorine atoms in one molecule of the compound is 0.1 or more and less than 2.

[In Formula (1), X ¹ to X ¹⁶ each independently represents a hydrogen atom or a halogen atom. ]

A fluorine atom, a chlorine atom, a bromine atom, and an iodine atom are mentioned as a halogen atom in the halogenated zinc phthalocyanine pigment which is a compound represented by Formula (1). The average number of halogen atoms in one molecule is as described above, and the average number of bromine atoms and chlorine atoms in the zinc halide phthalocyanine pigment is as described above.

The average number of halogen atoms in one molecule of the compound represented by formula (1) in the zinc halide phthalocyanine pigment is preferably 0.5 to 9.0, more preferably 1.0 to 7.0, from the viewpoint of further increasing the coloring power. It is a dog. The average number of halogen atoms is preferably 2.0 to 9.0, and more preferably 3.5 to 8.0, from the viewpoint of obtaining higher luminance.

The average number of bromine atoms in one molecule of the compound represented by formula (1) in the zinc halide phthalocyanine pigment is preferably 9.0 or less, more preferably 6.5, from the viewpoint of obtaining more excellent luminance and coloring power. less than a dog The average number of bromine atoms is 0.1 or more, preferably 1.0 or more, and more preferably 2.0 or more, from the viewpoint of obtaining more excellent luminance.

The average number of chlorine atoms in one molecule of the compound represented by formula (1) in the zinc halide phthalocyanine pigment is preferably 1.9 or less, more preferably 1.6 from the viewpoint of obtaining more excellent luminance and coloring power. It is one or less, More preferably, it is 1.3 or less. The average number of chlorine atoms is 0.1 or more, preferably 0.12 or more, more preferably 0.15 or more, still more preferably 0.2 or more, from the viewpoint of obtaining more excellent luminance.

The number of halogen atoms (for example, the number of bromine atoms and the number of chlorine atoms) can be measured by fluorescence X-ray analysis. Specifically, the number of each halogen atom can be calculated as a relative value per zinc atom from the mass ratio of zinc atoms and each halogen atom in the zinc halide phthalocyanine pigment.

A zinc halide phthalocyanine pigment is comprised by one or several particle|grains. The average particle diameter (average primary particle diameter) of the primary particles of the zinc halide phthalocyanine pigment may be 0.01 μm or more, 0.015 μm or more, or 0.02 μm or more. The average primary particle size of the zinc halide phthalocyanine pigment may be 0.20 μm or less, 0.10 μm or less, or 0.07 μm or less. Here, the average primary particle diameter is the average value of the major diameters of the primary particles, and can be obtained by measuring the major diameters of the primary particles in the same manner as the measurement of the average aspect ratio described later.

The average aspect ratio of the primary particles of the zinc halide phthalocyanine pigment is, for example, 1.2 or more, 1.3 or more, 1.4 or more, or 1.5 or more. The average aspect ratio of the primary particles of the zinc halide phthalocyanine pigment is, for example, less than 2.0, less than 1.8, less than 1.6, or less than 1.4. According to a zinc halide phthalocyanine pigment having such an average aspect ratio, more excellent contrast can be obtained.

The zinc halide phthalocyanine pigment having an average aspect ratio of primary particles in the range of 1.0 to 3.0 preferably does not contain primary particles having an aspect ratio of 5 or more, and more preferably does not contain primary particles having an aspect ratio of 4 or more , it is more preferable not to include primary particles whose aspect ratio exceeds 3.

The aspect ratio and average aspect ratio of the primary particles can be measured by the following method. First, the particles in the field of view are photographed with a transmission electron microscope (for example, JEM-2010 manufactured by Nippon Electronics Co., Ltd.). Then, the longer diameter (major axis) and the shorter diameter (minor axis) of the primary particles existing on the two-dimensional image are measured, and the ratio of the major axis to the minor axis is taken as the aspect ratio of the primary particles. Further, the average values of the major axis and the minor axis per 40 primary particles are obtained, and the ratio of the major axis to the minor axis is calculated using these values, and this is taken as the average aspect ratio. At this time, the zinc halide phthalocyanine pigment as a sample is ultrasonically dispersed in a solvent (for example, cyclohexane) and then photographed under a microscope. Moreover, you may use a scanning electron microscope instead of a transmission electron microscope.

The zinc halide phthalocyanine pigment of the present invention is obtained through a step of synthesizing a crude pigment composed of at least a zinc halide phthalocyanine compound. You may further include the process of pigmentizing the said crude pigment as needed.

The step of synthesizing the zinc halide phthalocyanine crude pigment may include a step of synthesizing the zinc halide phthalocyanine compound by a known production method such as a chlorosulfonic acid method, a halogenated phthalonitrile method, or a melting method.

Examples of the chlorosulfonic acid method include a method of dissolving zinc phthalocyanine in a sulfur oxide solvent such as chlorosulfonic acid and injecting chlorine gas and bromine into this to halogenate. The reaction at this time is performed at a temperature of 20 to 120° C. and for 3 to 20 hours, for example.

In the halogenated phthalonitrile method, for example, phthalic acid or phthalodinitrile in which some or all of the hydrogen atoms of the aromatic ring are substituted with halogen atoms such as chlorine in addition to bromine, and a metal or metal salt of zinc are appropriately used as starting materials, , a method of synthesizing a corresponding zinc halide phthalocyanine compound. In this case, you may use a catalyst, such as ammonium molybdate, as needed. The reaction at this time is performed at a temperature of 100 to 300°C and in the range of 7 to 35 hours, for example.

As the melting method, aluminum halides such as aluminum chloride and aluminum bromide, titanium halides such as titanium tetrachloride, alkali metal halides or alkaline earth metal halides such as sodium chloride and sodium bromide (hereinafter referred to as alkali (earth) metal halides) In a melt at about 10 to 170 ° C. composed of one or a mixture of two or more compounds that become solvents during halogenation, such as thionyl chloride, etc., zinc phthalocyanine is halogenated with a halogenating agent.

A suitable aluminum halide is aluminum chloride. In the above method using an aluminum halide, the added amount of the aluminum halide is usually 3 times mole or more, and preferably 10 to 20 times mole relative to zinc phthalocyanine.

The aluminum halide may be used alone, but when an alkali (earth) metal halide is used in combination with the aluminum halide, the melting temperature can be further lowered, which is advantageous in terms of operation. A suitable alkali (earth) metal halide is sodium chloride. The amount of the alkali (earth) metal halide to be added is preferably 1 to 15 parts by mass of the alkali (earth) metal halide with respect to 10 parts by mass of the aluminum halide within the range of generating a molten salt.

As a halogenating agent, chlorine gas, sulfuryl chloride, bromine, etc. are mentioned.

The halogenation temperature is preferably 10 to 170°C, more preferably 30 to 140°C. Further, in order to speed up the reaction rate, it is also possible to pressurize. The reaction time may be 5 to 100 hours, preferably 30 to 45 hours.

The melting method in which two or more of the above compounds are used in combination is a zinc halide phthalocyanine compound produced by adjusting the ratio of chloride, bromide, and iodide in the molten salt, or by changing the introduction amount and reaction time of chlorine gas, bromine, iodine, etc. Since the content ratio of the zinc halide phthalocyanine compound of a specific halogen atom composition in inside can be controlled arbitrarily, it is preferable. In addition, according to the melting method, the yield from the raw material is more excellent because there is little decomposition of the raw material during the reaction, and the reaction can be performed with an inexpensive apparatus without using a strong acid.

A zinc halide phthalocyanine compound having a different halogen atom composition from conventional zinc halide phthalocyanine compounds can be obtained by optimizing the raw material injection method, catalyst type and amount thereof, reaction temperature and reaction time.

In any of the above methods, after completion of the reaction, the obtained mixture is introduced into water or an acidic aqueous solution such as hydrochloric acid to precipitate the resulting zinc halide phthalocyanine compound, whereby a zinc halide phthalocyanine crude pigment can be obtained. As a zinc halide phthalocyanine crude pigment, this may be used as it is, but after that, filtration, washing with water or sodium hydrogen sulfate water, sodium hydrogen carbonate water, sodium hydroxide water, if necessary, acetone, toluene, methyl alcohol, ethyl alcohol, dimethyl It is preferable to use after washing with an organic solvent such as formamide and post-processing such as drying. You may use a zinc halide phthalocyanine crude pigment after dry grinding within grinders, such as an art liter, a ball mill, a vibration mill, and a vibration ball mill, as needed.

The zinc halide phthalocyanine crude pigment obtained in the above process has the same composition as that of the zinc halide phthalocyanine pigment. The zinc halide phthalocyanine crude pigment obtained at the said process may be used as a pigment as it is, or it may be further pigmented as follows and it is good also as a pigment.

In the step of pigmenting the zinc halide phthalocyanine crude pigment, the zinc halide phthalocyanine crude pigment is ground by kneading, for example, to obtain a zinc halide phthalocyanine pigment. The step of converting the zinc halide phthalocyanine crude pigment into a pigment may be a step of kneading the zinc halide phthalocyanine crude pigment with an inorganic salt and an organic solvent. Kneading can be performed using, for example, a kneader, a mixmaler or the like. Moreover, in this invention, you may include the process (miniaturization process) of grinding a zinc halide phthalocyanine crude pigment together with the organic solvent of a liquid state, cooling to -50--10 degreeC, for example.

As the inorganic salt, a water-soluble inorganic salt is preferably used. For example, inorganic salts such as sodium chloride, potassium chloride and sodium sulfate are preferably used. The average particle diameter of the inorganic salt is preferably 0.5 to 50 µm. Such an inorganic salt can be easily obtained by pulverizing a normal inorganic salt.

From the viewpoint of easy obtaining of a pigment having an average primary particle size within the above-mentioned range, it is preferable to increase the amount of inorganic salt used relative to the amount of crude pigment used. Specifically, the amount of inorganic salt used is preferably 5 to 20 parts by mass, more preferably 7 to 15 parts by mass with respect to 1 part by mass of the crude pigment.

Organic solvents that do not dissolve crude pigments and inorganic salts can be used. As the organic solvent, it is preferable to use an organic solvent capable of suppressing crystal growth. As such an organic solvent, a water-soluble organic solvent can be suitably used. Examples of organic solvents include diethylene glycol, glycerin, ethylene glycol, propylene glycol, liquid polyethylene glycol, liquid polypropylene glycol, 2-(methoxyethoxy)ethanol, 2-butoxyethanol, 2-(isopentyl Oxy)ethanol, 2-(hexyloxy)ethanol, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, triethylene glycol, triethylene glycol monomethyl ether, 1-methoxy- 2-propanol, 1-ethoxy-2-propanol, dipropylene glycol, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, trimethyl phosphate, 4-butyrolactone, propylene carbonate, N-methyl-2-p Rolidone, methanol, ethylene cyanohydrin, 1,2,4-butanetriol, 1,2,5-pentanetriol, 1,3-butanediol and the like can be used. The amount of the organic solvent (for example, water-soluble organic solvent) used is not particularly limited, but is preferably 0.01 to 5 parts by mass per 1 part by mass of the crude pigment.

The melting point of the organic solvent is preferably -10°C or lower, more preferably -15°C or lower, still more preferably -20°C or lower, from the viewpoint of preventing solidification by cooling. The melting point of the organic solvent may be -60°C or higher. When the organic solvent contains a plurality of types of organic solvents, it is preferable that the melting point of at least one type of organic solvent is within the above range, and it is more preferable that the melting point of the entire organic solvent is within the above range.

It is preferable that the organic solvent contains an organic solvent having a Ra value of 5 or more with zinc phthalocyanine from the viewpoint of making it difficult for the halogenated zinc phthalocyanine crude pigment to dissolve and making it easier to obtain finer pigment particles. The Ra value represents the distance between the HSPs of two substances, which is obtained from the dispersal force term (δd), polarity term (δp), and hydrogen bond term (δh) in Hansen Solubility Parameters (HSP). The dispersion force term (δd), polar term (δp), and hydrogen bond term (δh) of zinc phthalocyanine are 16.0, 7.7, and 9.5, respectively. When the hydrogen bond term is δh1, the distance (Ra value) between the HSP of the organic solvent and the HSP of zinc phthalocyanine is obtained from the following formula (I).

(Ra) ² = 4(δd1-16.0) ² +(δp1-7.7) ² +(δh1-9.5) ² ...(I)

Hansen solubility parameter values for various organic solvents are described, for example, in "Hansen Solubility Parameters: A Users Handbook" by Charles M. Hansen, etc., and Hansen solubility parameter values for organic solvents not described are computer software (Hansen Solubility Parameters in Practice).

It is more preferable that the organic solvent has a Ra value of 10 or more with zinc phthalocyanine from the viewpoint of making it more difficult to dissolve the crude zinc phthalocyanine pigment. The Ra value of the organic solvent with zinc phthalocyanine is preferably 40 or less, more preferably 30 or less, and still more preferably 25 or less, from the viewpoint of easy wettability of the pigment.

When the organic solvent contains plural types of organic solvents, the distance between the HSP of all organic solvents and the HSP of zinc halide phthalocyanine calculated from the dispersibility term, polar term, and hydrogen bond term of each organic solvent and the mixing ratio of each organic solvent (Ra value) is preferably within the above range.

In the miniaturization process, it is preferable not to use water. The amount of water used is, for example, 20 parts by mass or less, 10 parts by mass or less, or 5 parts by mass or less with respect to 100 parts by mass of the zinc halide phthalocyanine crude pigment.

For cooling, you may use a cooling device, such as a chiller (cooling water circulation device), for example. When using a chiller, the zinc halide phthalocyanine crude pigment can be cooled to about -50°C to -10°C by setting the temperature of the refrigerant in the chiller to, for example, -50°C to -10°C. The cooling temperature is preferably -20°C or lower, more preferably -30°C or lower, from the viewpoint of obtaining finer pigment particles. The cooling temperature may be over -50°C from the viewpoint of preventing an increase in the load on the grinding device due to increase in viscosity.

Grinding in the miniaturization step can be performed using, for example, a kneader, a mixmaler, or the like. The grinding time (for example, kneading time) may be 1 to 60 hours.

In the miniaturization process, when using an inorganic salt and an organic solvent, a mixture containing a zinc halide phthalocyanine pigment, an inorganic salt, and an organic solvent can be obtained. You may perform operations, such as washing|cleaning, filtration, drying, grinding, etc., with respect to the solid material which has a zinc halide phthalocyanine pigment as a main body.

As washing, both water washing and hot water washing are employable. You may perform washing repeatedly in the range of 1-5 times. When water-soluble inorganic salt and water-soluble organic solvent are used, the organic solvent and inorganic salt can be easily removed by washing with water. If necessary, you may perform acid washing, alkali washing, and organic solvent washing.

Drying after washing and filtration may include, for example, batch-type or continuous-type drying in which pigments are dehydrated and/or desolvated by heating at 80 to 120° C. with a heating source installed in a dryer. . As a dryer, generally, a box type dryer, a band dryer, a spray dryer, etc. are mentioned. In particular, spray drying using a spray dryer is preferable because it is easily dispersed at the time of paste production. Further, pulverization after drying is not an operation for increasing the specific surface area or reducing the average particle diameter of the primary particles, but when the pigment becomes a lamp shape, for example, in the case of drying using a box dryer or a band dryer. This is done to dissolve and powder the pigment. For example, pulverization by a mortar, hammer mill, disk mill, pin mill, jet mill, etc., etc. are mentioned.

In the said method, when pigmenting a crude pigment, you may make a coating resin coexist. By coexisting the resin at the time of pigmentation, the active side (active growth side) of the particles is stabilized by the coated resin. As a result, since the deviation in the direction of particle growth is mitigated, a pigment having a small average aspect ratio can be easily obtained. By using such a pigment, the contrast of the pixel part can be improved.

As the coating resin, a resin having an acidic group, for example, a resin containing a polymer having an acidic group is preferably used. Since the acidic group develops interaction with the active surface (active growth surface), when the resin has an acidic group, a pigment having a small average aspect ratio of the primary particles can be easily obtained. As an acidic group, a carboxyl group, a sulfonic acid group, a phosphoric acid group, and its ammonium salt group etc. are mentioned. Among these, a carboxyl group is preferable from the viewpoint of making it easier to obtain more excellent contrast.

The pigment may further contain other components other than the zinc halide phthalocyanine pigment and coating resin described above. As another component, a well-known phthalocyanine derivative etc. are mentioned, for example.

The zinc halide phthalocyanine pigment of the present invention has a unique cyan color, and has a specificity in blue color rather than yellowish color as much as conventional high halogenated zinc phthalocyanine pigments. In conventional high halogenated zinc phthalocyanine pigments, It is possible to express colors that could not be achieved.

In addition, the zinc halide phthalocyanine pigment of the present invention has a composition of 1.25 parts of resin per 1 part of the pigment and a coating film with a film thickness of 1.5 μm to 2.4 μm in terms of mass, CIE XYZ color system when colorimetry is performed using a C light source alone In , the xy chromaticity coordinate area surrounded by the following formulas (A) to (D) can be displayed.

Formula (A)

y=-1.766x+0.618

(In the formula, x is 0.10≤x≤0.17.)

Formula (B)

y=5.889x-0.683

(In the formula, x is 0.15≤x≤0.17.)

Formula (C)

y=0.125x+0.181

(In the formula, x is 0.07≤x≤0.15.)

Formula (D)

y=8.380x-0.397

(In the formula, x is 0.07≤x≤0.10.)

When the above equations (A), (B), (C), and (D) are expressed in a chromaticity plot (x-axis: chromaticity x, y-axis: chromaticity y), the equations A, B, C, and D in FIG. 3 are obtained. The area surrounded by the expressions A, B, C, and D is the chromaticity coordinate area A.

In addition, since the zinc halide phthalocyanine pigment of the present invention is excellent in luminance when used as a color filter, the xy chromaticity coordinate region surrounded by the following formulas (C), (E), (F), and (G) can be displayed. It is desirable to have When this is represented by a chromaticity plot, it follows the formulas C, E, F, and G in FIG. 3 . The area surrounded by the expressions C, E, F, and G is the chromaticity coordinate area B.

Formula (C)

y=0.125x+0.181

(In the formula, x is 0.07≤x≤0.15.)

Formula (E)：y=-1.333x+0.503

(In the formula, x is 0.10≤x≤0.16.)

Equation (F): y=9.000x-1.150

(In the formula, x is 0.15≤x≤0.16.)

Formula (G)：y=6.000x-0.230

(In the formula, x is 0.07≤x≤0.10.)

In addition, since the pigment of the present invention is excellent in luminance when used as a color filter, it is preferable that the xy chromaticity coordinate region surrounded by the following formulas (E), (H), (I), and (J) can be displayed do. When this is shown on the chromaticity plot, it follows the equations E, H, I, and J in FIG. 3 . The area surrounded by the expressions E, H, I, and J is the chromaticity coordinate area C.

Formula (E)：y=-1.333x+0.503

(In the formula, x is 0.10≤x≤0.16.)

Formula (H)：y=7.000x-0.830

(In the formula, x is 0.15≤x≤0.16.)

Formula (I)：y=-0.286x+0.263

(In the formula, x is 0.08≤x≤0.15.)

Formula (J)：y=6.500x-0.280

(In the formula, x is 0.08≤x≤0.10.)

The said coating film consists of 1.25 parts of resin per 1 part of pigment in mass conversion. The resin is a resin for forming a coating film, and is preferably an acrylic resin, and among these, a benzyl methacrylate-methacrylic acid copolymer and a dimethylaminoethyl methacrylate copolymer are particularly preferred. As the benzyl methacrylate-methacrylic acid copolymer, Unidic ZL-295 (solid content: 40% by mass solution) manufactured by DIC Corporation can be used, for example. The weight average molecular weight Mw of the benzyl methacrylate-methacrylic acid copolymer is, for example, 12000 to 16000. Moreover, as a dimethylaminoethyl methacrylate copolymer, BYK-LPN6919 (solution of 60 mass % of solid content) by the Big Chemie company can be used, for example. The weight average molecular weight Mw of the dimethylaminoethyl methacrylate copolymer is 7000 to 11000, for example. The dimethylaminoethyl methacrylate copolymer is, for example, 30 g of Pigment Green 58 (eg, Fastogen Green A110 manufactured by DIC Corporation) and 40% by mass of the solid content of the benzyl methacrylate-methacrylic acid copolymer. 22.5 g of a resin solution (eg, ZL-295 manufactured by DIC Corporation), 132.5 g of propylene glycol monomethyl ether acetate, and 15 g of a resin solution having a solid content of 60% by mass of a dimethylaminoethyl methacrylate copolymer, 0.3 to 10 g When a pigment dispersion is produced by dispersing in a paint shaker for 2 hours using 460 g of 0.4 mm zircon beads, it is a copolymer that provides a pigment dispersion having a viscosity of 10 mPa·s or less at 25°C. In addition, the said viscosity is a viscosity measured by the cone-flat rotary clay meter (conical plate clay meter) (For example, RE550L of Toki Sangyo Co., Ltd.) according to JIS Z8803.

Although the said coating film is not specifically limited, Specifically, it can form by the following method. First, 2.48 g of zinc halide phthalocyanine pigment, BYK-LPN6919 1.24 g, Unidic ZL-295 1.86 g, and propylene glycol monomethyl ether acetate 10.92 g were dispersed for 2 hours using 0.3 to 0.4 mm zircon beads to disperse the pigment Sieve. 0.98 g of Unidic ZL-295 and 0.22 g of propylene glycol monomethyl ether acetate were added to 4.0 g of the obtained pigment dispersion, and mixed in a paint shaker to obtain a coating solution. Next, a coating film can be formed by spin-coating the coating liquid on a soda glass substrate, drying at 90°C for 3 minutes, and then heating at 230°C for 1 hour. Chromaticity is a value measured using a spectrophotometer (U-3900) manufactured by Hitachi High-Tech Science Co., Ltd., for example.

<Coloring composition>

The coloring composition of this invention contains the above-mentioned zinc halide phthalocyanine pigment and a solvent at least.

The coloring composition may further contain a resin (coating resin) for coating the zinc halide phthalocyanine pigment. The type and content of the coating resin may be the same as those described as the coating resin contained in the above-mentioned pigment composition, and the preferred embodiments are also the same.

As a solvent, an organic solvent is preferable. Examples of the organic solvent include aromatic solvents such as toluene, xylene and methoxybenzene, ethyl acetate and butyl acetate, acetic ester solvents such as propylene glycol monomethyl ether acetate, and propylene glycol monoethyl ether acetate, ethoxyethyl Propionate-based solvents such as propionate, alcohol-based solvents such as methanol and ethanol, ether-based solvents such as butyl cellosolve, propylene glycol monomethyl ether, diethylene glycol ethyl ether, and diethylene glycol dimethyl ether, methyl ethyl Ketone solvents such as ketone, methyl isobutyl ketone and cyclohexanone, aliphatic hydrocarbon solvents such as hexane, N,N-dimethylformamide, γ-butyrolactam, N-methyl-2-pyrrolidone, aniline, nitrogen compound solvents such as pyridine, lactone solvents such as γ-butyrolactone, and carbamate esters such as a 48:52 mixture of methyl carbamate and ethyl carbamate. The organic solvent is preferably a solvent that is polar and soluble in water, more preferably a propionate-based solvent, an alcohol-based solvent, an ether-based solvent, a ketone-based solvent, a nitrogen compound-based solvent, or a lactone-based solvent. am.

The content of the solvent may be 300 parts by mass or more and 1000 parts by mass or less with respect to 100 parts by mass of the total amount of the pigment.

If necessary, the coloring composition may further contain organic pigments other than zinc halide phthalocyanine pigments, organic dyes, organic pigment derivatives, and the like in consideration of economy. As the organic pigment, green halide metal phthalocyanine pigments such as well-known and usual green halide copper phthalocyanine and other green halide dissimilar metal phthalocyanine pigments can be used. Moreover, you may use the yellow pigment for toning. As a yellow pigment, C.I. Yellow organic pigments, such as Pigment Yellow 83, 110, 129, 138, 139, 150, 180, 185, and 231, are mentioned. The combined use ratio of the zinc halide phthalocyanine pigment and the yellow pigment is 1 to 400 parts by mass of the yellow pigment per 100 parts by mass of the zinc halide phthalocyanine pigment, for example. The organic pigment derivative may be, for example, a derivative obtained by modifying (substituting) a part of a known organic pigment with a sulfonic acid group, a carboxyl group, an amino group, or a phthalimidemethyl group. Specifically, Solsperse (registered trademark) 5000, 12000, 22000 (manufactured by Lubrizol Corporation) and the like are exemplified.

The coloring composition may further contain a dispersing agent as a component other than the above. As the dispersant, known and usual dispersants such as resins having an amine value can be used. Dispersants include, for example, ANTI-TERRA (registered trademark) U/U100, 204, DISPERBYK (registered trademark) 106, 108, 109, 112, 130, 140, 142, 145, 161, 162, 163, 164, 167 ,168,180,182,183,184,185,2000,2001,2008,2009,2013,2022,2025,2026,2050,2055,2150,2155,2163,2164,9076, 9077, BYK LPN-6919, 21116, 21324, 22102 (manufactured by Big Chemie Corporation), EFKA (registered trademark) 46, 47, 4010, 4020, 4320, 4300, 4330, 4401, 4570, 5054, 7461, 7462, 7476, 7477 (manufactured by BASF Corporation) , Ajisper (trade name) PB814, 821, 822, 881 (manufactured by Ajinomoto Fine Techno Co., Ltd.), Solsperse (registered trade name) 24000, 28000, 37500, 76500 (manufactured by Lubrizol Co., Ltd.), and the like. The content of the dispersant should just be 5 parts by mass or more and just 120 parts by mass or less with respect to 100 parts by mass of the total amount of the pigment.

The coloring composition may further contain a leveling agent, a coupling agent, a cationic rosin, a surfactant, a binder resin, a photosensitive compound (for example, a photosensitive resin), a curable resin, etc. as components other than the above.

A coloring composition containing a photosensitive compound can also be referred to as a photosensitive coloring composition. Examples of the photosensitive compound include thermoplastic resins such as urethane-based resins, acrylic resins, polyamic acid-based resins, polyimide-based resins, styrene maleic acid-based resins, and styrene maleic anhydride-based resins; Bifunctional monomers such as diacrylate, ethylene glycol diacrylate, neopentyl glycol diacrylate, triethylene glycol diacrylate, bis(acryloxyethoxy)bisphenol A, and 3-methylpentanediol diacrylate, and trimester polyfunctional monomers such as tyrolpropane triacrylate, pentaerythritol triacrylate, tris(2-acryloyloxyethyl) isocyanurate, dipentaerythritol hexaacrylate, dipentaerythritol pentaacrylate, etc. A photopolymerizable monomer etc. are mentioned.

The photosensitive coloring composition may further contain a photoinitiator. As the photopolymerization initiator, for example, acetophenone, benzophenone, benzyldimethylketal, benzoyl peroxide, 2-chlorothioxanthene, 1,3-bis(4'-azidebenzal)-2-propane, 1,3 -bis(4'-azidebenzal)-2-propane-2'-sulfonic acid, 4,4'-diazidostilbene-2,2'-disulfonic acid, etc. are mentioned.

The method for producing the photosensitive coloring composition is not particularly limited, but after preparing a dispersion (coloring composition) using a zinc halide phthalocyanine pigment or a pigment composition containing the same, a solvent, and, if necessary, a dispersing agent, thereto, a photosensitive compound, etc. A method of preparing by adding is common. In this case, the content of the photosensitive resin may be 3 parts by mass or more and 20 parts by mass or less with respect to 100 parts by mass of the above dispersion. The content of the photopolymerization initiator may be 0.05 parts by mass or more and 3 parts by mass or less with respect to 1 part by mass of the photosensitive resin.

In the case of using a yellow pigment for coloring, for example, after preparing a dispersion liquid using a yellow pigment, a solvent, and, if necessary, a dispersant, a dispersion liquid containing a zinc halide phthalocyanine pigment and a dispersion liquid containing a yellow pigment And, you may prepare a photosensitive coloring composition by mixing a photosensitive compound etc. In addition, a photosensitive compound or the like is added to a dispersion containing a zinc halide phthalocyanine pigment to prepare a green coloring composition, and a yellow coloring composition is prepared by adding a photosensitive compound or the like to a dispersion containing a yellow pigment. You may prepare the photosensitive coloring composition by mixing the composition for coloring and the composition for yellow coloring. As a yellow pigment for toning, for example, C.I. Pigment Yellow 138, C.I. Pigment Yellow 185, C.I. Pigment Yellow 150, C.I. Pigment Yellow 129, C.I. Pigment Yellow 231, and C.I. Pigment Yellow 233 is exemplified.

In the green pixel, the ratio of the pigment of the present invention is, for example, 10 to 90% by mass, preferably 20 to 80% by mass, with respect to the total amount of the color material constituting the green pixel. In addition, the ratio of the yellow color material for toning is, for example, 10 to 90% by mass, preferably 20 to 80% by mass, with respect to the total amount of the colorant constituting the green pixel.

＜Color filter＞

The color filter of the present invention has a green pixel portion containing at least a zinc halide phthalocyanine pigment. In the color filter, the green pixel portion has a function of converting the color of light from a light source. Usually, a color filter has a red pixel part, a blue pixel part, and a light-shielding part (black matrix) other than a green pixel part. In the color filter, a red pixel section, a green pixel section, and a blue pixel section are repeatedly arranged in this order, and each color pixel section is separated from each other by a light shielding section.

(light source)

An example of the spectrum of light from the light source is shown in FIG. 2 . 2 shows a spectrum in a wavelength range of 380 to 780 nm. Among the spectra shown in FIG. 2, A. LED+QD or B. LED KSF is an example in the case where the light source is a white LED light source that obtains white light by color mixing by combining a blue LED, a red light emitting phosphor, and a green light emitting phosphor. In addition, the spectrum of the light from the light source can be measured using a microscope MX-50 manufactured by Olympus and a spectrophotometer MCPD-3000 spectrophotometer manufactured by Otsuka Electronics under the conditions of a measurement range: 380 to 780 nm and a measurement interval: 1 nm. there is.

In the light source in the present invention, the maximum wavelength in 480 to 580 nm of light emitted is, for example, 500 to 560 nm, preferably 500 to 540 nm. A light source having a maximum wavelength in this range is preferable for the BT2020 because light of 510 to 532 nm is strong. In the emitted light, the intensity of 480 nm (I480) relative to the intensity of 532 nm (I532) is, for example, 1.1 or less, preferably 1.0 or less. Further, the intensity (I480) of 480 nm with respect to the intensity (I550) of 550 nm is 0.9 or less, preferably 0.8 or less. When the light satisfies this intensity, the luminance of the BT2020 can be improved.

In the present invention, the light from the light source has a maximum wavelength in the range of 480 to 580 nm, for example, 500 to 560 nm, and the intensity (I480) at 480 nm with respect to the intensity (I532) at 532 nm is, for example, 1.1 or less. , and the intensity (I480) of 480 nm with respect to the intensity (I550) of 550 nm is 0.9 or less. Among them, light has a maximum wavelength in the range of 480 to 580 nm in the range of 510 to 550 nm, the intensity of 480 nm (I480) with respect to the intensity of 532 nm (I532) is 0.4 or less, and the intensity of 480 nm with respect to the intensity of 550 nm (I550) (I480) is preferably 0.4 or less. In particular, it is preferable that the intensity (I480) of 480 nm to the intensity (I532) of 532 nm is 0.2 or less, and the intensity (I480) of 480 nm to the intensity (I550) of 550 nm is 0.2 or less.

Other than the above light sources, for example, a white LED (light emitting diode) light source, a white organic EL light source, a white inorganic EL light source, or a white quantum dot light source may be used as the light source for emitting light. When the light source is a white LED light source, the white LED light source is, for example, a white LED light source that obtains white light by color mixing by combining a red LED, a green LED, and a blue LED, or a combination of a blue LED, a red LED, and a green phosphor. A white LED light source that obtains white light by color mixing, a white LED light source that obtains white light by color mixture by combining a blue LED, a red light-emitting phosphor, and a green light-emitting phosphor, a white LED light source that obtains white light by color mixing of a blue LED and a YAG-based phosphor, A white LED light source obtained by mixing an ultraviolet LED, a red light emitting phosphor, a green light emitting phosphor, and a blue light emitting phosphor to obtain white light by color mixing, a white LED light source combining a red laser, and a white LED light source using quantum dot technology.

As a light source, FIG. 2 shows an example of the intensity spectrum of light for each wavelength. As such a light source, a green LED (for example, model number "NSPG336CS" manufactured by Nichia Chemical Industries, Ltd.), LED KSF (for example, model number "NFSW157J-HG" manufactured by Nichia Chemical Industries, Ltd.), LEDYAG1 (for example, Commercially available products such as model number "NSSW410A" manufactured by Nichia Chemical Industry Co., Ltd.) can be used.

The color filter of the present invention, when the color material described later is used and the light source is used for color measurement, in the CIE (International Commission on Illumination) XYZ colorimetric system, chromaticity coordinates close to BT2020, 0.140 ≤ chromaticity x ≤ 0.200; 0.600 ≤ chromaticity y ≤ 0.797 can be displayed. In addition, the XYZ color system is a concept that is usually used when considering the display color gamut in a display device, based on the mixed color amount of the three primary colors of RGB (Red/Green/Blue) color light.

The green pixel portion containing a zinc halide phthalocyanine pigment can be easily formed from the above-described coloring composition (photosensitive coloring composition). As a specific method, for example, a coloring composition (photosensitive coloring composition) is applied onto a transparent substrate such as a glass substrate by a spin coating method, a roll coating method, an inkjet method or the like, A method called photolithography is exemplified in which a pattern exposure by ultraviolet rays is performed through a mask, and then the unexposed portion is washed with an organic solvent, alkaline water, or the like to obtain a colored pattern. The method for forming the pixel portion is not particularly limited, and for example, a color filter may be manufactured by forming a pattern of the pixel portion by a method such as an electrodeposition method, a transfer method, a micelle electrolysis method, or a photovoltaic electrodeposition (PVED) method.

Other pixel portions (for example, a red pixel portion and a blue pixel portion) can also be formed by the same method using known pigments.

[Example]

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

<Synthesis of zinc halide phthalocyanine pigment>

Zinc halide phthalocyanine pigments (RP1) to (RP4) were synthesized by the methods of Synthesis Examples 1 to 4 below. The average number of atoms of halogen atoms of each pigment was as shown in Table 1.

[Synthesis Example 1]

In a 1 L flask, 190 g of sulfuryl chloride (manufactured by Fujifilm Wako Junyaku Co., Ltd.), 315 g of aluminum chloride (manufactured by Kanto Chemical Co., Ltd.), 43 g of sodium chloride (manufactured by Tokyo Chemical Industry Co., Ltd.), 84 g of zinc phthalocyanine (manufactured by DIC Corporation) and bromine (Fuji Film Manufactured by Wako Pure Chemical Co., Ltd.) 185 g was injected. After heating up to 55 degreeC and taking out the obtained mixture in water, it filtered, washed with water, and dried to obtain zinc halide phthalocyanine (R1). 40 g of zinc halide phthalocyanine (R1), 400 g of pulverized sodium chloride, and 63 g of 1,3-butanediol (melting point: -54 ° C) were injected into a twin bowl kneader, and the cooling water circulator was set to -20 ° C. Kneaded for 20 hours. The mixture after kneading was taken out in 2 kg of water at 80°C and stirred for 1 hour. Thereafter, by filtering, washing with hot water, drying, and pulverizing, a halide zinc phthalocyanine pigment (RP1) was obtained as a cyan pigment. The halogenated zinc phthalocyanine pigment (RP1) was subjected to fluorescence X-ray analysis using ZSX100E manufactured by Rigaku Co., Ltd., and from the mass ratio of zinc atoms, chlorine atoms, and bromine atoms, as relative values per zinc atom, the average number of chlorine atoms and The average number of bromine atoms was calculated. In addition, 1 g of zinc halide phthalocyanine pigment was pressure-molded (25 mm φ) as a measurement sample, and measured in a vacuum atmosphere with a measurement diameter of 20 mm φ. As a result, in the zinc halide phthalocyanine pigment (RP1), the number of halogen atoms in one molecule was an average of 8.1, among which the number of bromine atoms was an average of 7.9 and the number of chlorine atoms was an average of 0.2.

[Synthesis Example 2]

A zinc halide phthalocyanine pigment (hereinafter also referred to as "halogenated zinc phthalocyanine pigment (RP2)") was produced in the same manner as in Comparative Example 3 of JP-A-2016-57635. About the zinc halide phthalocyanine pigment (RP2), it carried out similarly to Synthesis Example 1, and calculated the average number of chlorine atoms and the average number of bromine atoms. In the zinc halide phthalocyanine pigment (RP2), the average number of halogen atoms in one molecule was 10.0, among which the average number of bromine atoms was 6.9 and the average number of chlorine atoms was 3.1.

[Synthesis Example 3]

A zinc halide phthalocyanine pigment (hereinafter also referred to as "halogenated zinc phthalocyanine pigment (RP3)") was produced in the same manner as in Pigment 10 of Production Example 10 of Japanese Unexamined Patent Publication No. 2018-36520. About the zinc halide phthalocyanine pigment (RP3), it carried out similarly to Synthesis Example 1, and calculated the average number of chlorine atoms and the average number of bromine atoms. In the zinc halide phthalocyanine pigment (RP3), the number of halogen atoms in one molecule was an average of 7.3, among which the number of bromine atoms was an average of 2.0 and the number of chlorine atoms was an average of 5.3.

[Synthesis Example 4]

In the same manner as RP4 in Example 4 of International Publication No. 2020/045199 (Japanese Patent Application No. 2020-520089), a zinc halide phthalocyanine pigment (hereinafter also referred to as "halogenated zinc phthalocyanine pigment (RP4)") was produced. About the zinc halide phthalocyanine pigment (RP4), it carried out similarly to Synthesis Example 1, and calculated the average number of chlorine atoms and the average number of bromine atoms. In the zinc halide phthalocyanine pigment (RP4), the number of halogen atoms in one molecule was an average of 10.4, among which the number of bromine atoms was an average of 9.3 and the number of chlorine atoms was an average of 1.2.

Next, cyan pigment dispersions (RMG1) to (RMG4), (SMG2) and green pigment dispersions (SMG1) were prepared by the following methods, and further a composition for evaluation (RCG) and a composition for color adjustment (TY) was prepared, and evaluation compositions (RDG), (SDG), (REG), and (SEG) were prepared, and color filter characteristics were evaluated.

<Example 1>

Zinc halogenated phthalocyanine pigment (RP1) 2.48 g, BYK LPN-6919 (product name, solid content: 60 mass%) 1.24 g, Unidic ZL-295 (product name, solid content: 40 mass%) 1.86 g and 10.92 g of propylene glycol monomethyl ether acetate, it was dispersed for 2 hours in a paint shaker manufactured by Toyo Seiki Co., Ltd. using zircon beads of 0.3 to 0.4 mm to obtain a cyan pigment dispersion (RMG1).

<Comparative Examples 1 to 3>

Cyan pigment dispersions (RMG2) to (RMG4) were respectively obtained in the same manner as in Example 1 except that zinc halide phthalocyanine pigments (RP2) to (RP4) were respectively used instead of zinc halide phthalocyanine pigments (RP1).

<Comparative Example 4>

A green pigment dispersion (SMG1) was obtained in the same manner as in Example 1, except that Pigment Green 7 (FASTOGEN Green S manufactured by DIC Corporation; hereinafter also referred to as “SP1”) was used instead of the zinc halide phthalocyanine pigment (RP1). .

<Comparative Example 5>

β-type zinc phthalocyanine (hereinafter also referred to as “SP2”) was produced according to [Production Example 3-6] of Japanese Unexamined Patent Publication No. 2020-38368. A cyan pigment dispersion (SMG2) was obtained in the same manner as in Example 1 except that (SP2) was used instead of the zinc halide phthalocyanine pigment (RP1).

<Evaluation of color filter characteristics>

(Preparation of composition for evaluation (RCG))

To 4.0 g of the cyan pigment dispersion (RMG1), 0.98 g of Unidic ZL-295 (manufactured by DIC Corporation, trade name, solid content: 40% by mass) and 0.22 g of propylene glycol monomethyl ether acetate were added and mixed in a paint shaker, An evaluation composition (RCG1) was obtained for evaluating monochromatic chromaticity as a green pixel portion for a color filter. In addition, the evaluation compositions (RCG2) to (RCG4) and (SCG1) to ( SCG2) were produced respectively.

(Preparation of color-adjusting composition (TY))

C.I. Pigment Yellow 139 (manufactured by BASF Corporation, Paliotol Yellow D1819) 1.65 g, DISPERBYK-161 (manufactured by Big Chemie Co., Ltd., solid content: 30% by mass) 3.85 g and propylene glycol monomethyl ether acetate 11.00 g together with 0.3 to 0.4 mm zircon It dispersed for 2 hours in a paint shaker using beads to obtain a yellow pigment dispersion (MY1). To 4.0 g of the yellow pigment dispersion (MY1), 0.98 g of Unidic ZL-295 (manufactured by DIC Corporation, brand name, solid content: 40% by mass) and 0.22 g of propylene glycol monomethyl ether acetate were added and mixed by a paint shaker to adjust the color A composition (TY1) was obtained.

<light source>

The light sources used in Examples and Comparative Examples are as follows. The spectra of light source A and light source B are as described in FIG. 2 . As described above, the color filter of the present invention can display chromaticity coordinates close to BT2020, 0.140 ≤ chromaticity x ≤ 0.200, 0.600 ≤ chromaticity y ≤ 0.797, in the XYZ color system of CIE. In , it is assumed that (x, y) = (0.170, 0.750) is the target chromaticity coordinate in the color gamut.

Light source A. LED+QD ‥ Light source described in Figure 5 (a) of the paper 「Langmuir 2017, 33, 13040-13050」

Light source B. LED KSF .. model number "NFSW157J-HG" manufactured by Nichia Chemical Industry

(for light source A: preparation of evaluation composition (RDG) (SDG))

Composition for evaluation (RDG1) for evaluating the performance as a green pixel part for a color filter by mixing compositions for evaluation (RCG1) to (RCG4) and (SCG1) to (SCG2), respectively, with a composition for toning (TY1) - (RDG4), (SDG1) - (SDG2) were prepared. Compositions for evaluation (RDG1) to (RDG4) and (SDG1) to (SDG2) are respectively spin-coated on a soda glass substrate and dried at 90° C. for 3 minutes to form a colored film on the soda glass substrate. A glass substrate was produced. In addition, the blending ratio of the composition for evaluation (RCG1) to (RCG4) / composition for toning (TY1), the blending ratio of the composition for evaluation (SCG1) to (SCG2) / composition for toning (TY1), and the film thickness of the coating film, When light source A. LED+QD was used, the chromaticity of the coating film (measured using a spectrophotometer U-3900 manufactured by Hitachi High-Tech Science Co., Ltd.) was determined to be (x, y) = (0.170, 0.750). The film thickness of the coated film was adjusted by adjusting the number of spin rotations during spin coating.

(evaluation)

The luminance Y of the coating film was measured with a spectrophotometer (U-3900) manufactured by Hitachi High-Tech Science Co., Ltd. The results are shown in Table 2.

(for light source B: preparation of composition for evaluation (REG) (SEG))

Composition for evaluation (REG1) for evaluating performance as a green pixel part for a color filter by mixing compositions for evaluation (RCG1) to (RCG4) and (SCG1) to (SCG2) with a composition for toning (TY1), respectively. - (REG4), (SEG1) - (SEG2) were prepared. Compositions for evaluation (REG1) to (REG4) and (SEG1) to (SEG2) are respectively spin-coated on a soda glass substrate and dried at 90° C. for 3 minutes to form a colored film on the soda glass substrate for evaluation. A glass substrate was produced. In addition, the blending ratio of the composition for evaluation (RCG1) to (RCG4) / composition for toning (TY1), the blending ratio of the composition for evaluation (SCG1) to (SCG2) / composition for toning (TY1), and the film thickness of the coating film, Light source B. When LED KSF was used, the chromaticity of the coating film (measured using a spectrophotometer U-3900 manufactured by Hitachi High-Tech Science Co., Ltd.) was determined to be (x, y) = (0.170, 0.750). The film thickness of the coated film was adjusted by adjusting the number of spin rotations during spin coating.

(evaluation)

The luminance Y of the coating film was measured with a spectrophotometer (U-3900) manufactured by Hitachi High-Tech Science Co., Ltd. The results are shown in Table 3.

As shown in Tables 2 and 3, even when the light source is changed, Example 1 has higher luminance than Comparative Examples 1 to 5, and zinc halide phthalocyanine pigments (RP2) to (RP4) and (SP1) to (SP2) It was confirmed that the zinc halide phthalocyanine pigment (RP1) was more excellent.

<Synthesis of zinc halide phthalocyanine pigment>

Zinc halide phthalocyanine pigments (RP5) to (RP8) were synthesized by the methods of Synthesis Examples 5 to 8 below. The average number of atoms of halogen atoms of each pigment was as shown in Table 4.

[Synthesis Example 5]

In a 1 L flask, 190 g of sulfuryl chloride (manufactured by Fujifilm Wako Junyaku Co., Ltd.), 315 g of aluminum chloride (manufactured by Kanto Chemical Co., Ltd.), 43 g of sodium chloride (manufactured by Tokyo Chemical Industry Co., Ltd.), 84 g of zinc phthalocyanine (manufactured by DIC Corporation) and bromine (Fuji Film Manufactured by Wako Pure Chemical Co., Ltd.) 116 g was injected. After heating up to 55 degreeC and taking out the obtained mixture in water, it filtered, washed with water, and dried to obtain zinc halide phthalocyanine (R5). 40 g of halogenated zinc phthalocyanine (R5), 400 g of pulverized sodium chloride, and 63 g of 1,3-butanediol (melting point: -54 ° C) were injected into a twin arm type kneader, and the cooling water circulator was set to -20 ° C. Kneaded for 20 hours. The mixture after kneading was taken out in 2 kg of water at 80°C and stirred for 1 hour. Then, by filtering, washing with hot water, drying, and pulverizing, a zinc halide phthalocyanine pigment (RP5) was obtained as a cyan pigment. About the zinc halide phthalocyanine pigment (RP5), it carried out similarly to Synthesis Example 1, and computed the average number of chlorine atoms and the average number of bromine atoms. In the zinc halide phthalocyanine pigment (RP5), the number of halogen atoms in one molecule was an average of 4.7, among which the number of bromine atoms was an average of 4.4 and the number of chlorine atoms was an average of 0.3.

[Synthesis Example 6]

In a 1 L flask, 270 g of sulfuryl chloride (manufactured by Fujifilm Wako Pure Chemical Co., Ltd.), 315 g of aluminum chloride (manufactured by Kanto Chemical Co., Ltd.), 86 g of sodium chloride (manufactured by Tokyo Chemical Industry Co., Ltd.), 84 g of zinc phthalocyanine (manufactured by DIC Corporation) and bromine (Fuji Film Manufactured by Wako Pure Chemical Co., Ltd.) 116 g was injected. After heating up to 70 degreeC and taking out the obtained mixture in water, it filtered, washed with water, and dried to obtain zinc halide phthalocyanine (R6). 40 g of halogenated zinc phthalocyanine (R6), 400 g of pulverized sodium chloride, and 63 g of 1,3-butanediol (melting point: -54 ° C.) were injected into a twin arm type kneader, and the cooling water circulator was set to -20 ° C. Kneaded for 20 hours. The mixture after kneading was taken out in 2 kg of water at 80°C and stirred for 1 hour. Thereafter, by filtering, washing with hot water, drying, and pulverizing, a zinc halide phthalocyanine pigment (RP6) was obtained as a cyan pigment. About the zinc halide phthalocyanine pigment (RP6), it carried out similarly to Synthesis Example 1, and calculated the average number of chlorine atoms and the average number of bromine atoms. In the zinc halide phthalocyanine pigment (RP6), the number of halogen atoms in one molecule was an average of 5.7, among which the number of bromine atoms was an average of 4.2 and the number of chlorine atoms was an average of 1.5.

[Synthesis Example 7]

In a 1 L flask, 216 g of sulfuryl chloride (manufactured by Fujifilm Wako Junyaku Co., Ltd.), 315 g of aluminum chloride (manufactured by Kanto Chemical Co., Ltd.), 64 g of sodium chloride (manufactured by Tokyo Chemical Industry Co., Ltd.), 84 g of zinc phthalocyanine (manufactured by DIC Corporation) and bromine (Fuji Film Manufactured by Wako Pure Chemical Co., Ltd.) 162 g was injected. After heating up to 70 degreeC and taking out the obtained mixture in water, it filtered, washed with water, and dried to obtain zinc halide phthalocyanine (R7). 40 g of zinc halide phthalocyanine (R7), 400 g of pulverized sodium chloride, and 63 g of 1,3-butanediol (melting point: -54 ° C) were injected into a twin bowl kneader, and the cooling water circulator was set to -20 ° C. Kneaded for 20 hours. The mixture after kneading was taken out in 2 kg of water at 80°C and stirred for 1 hour. Thereafter, by filtering, washing with hot water, drying and pulverizing, a zinc halide phthalocyanine pigment (RP7) was obtained as a cyan pigment. About the zinc halide phthalocyanine pigment (RP7), it carried out similarly to Synthesis Example 1, and calculated the average number of chlorine atoms and the average number of bromine atoms. In the zinc halide phthalocyanine pigment (RP7), the number of halogen atoms in one molecule was an average of 6.8, among which the number of bromine atoms was an average of 6.1 and the number of chlorine atoms was an average of 0.7.

[Synthesis Example 8]

In a 1 L flask, 216 g of sulfuryl chloride (manufactured by Fujifilm Wako Junyaku Co., Ltd.), 315 g of aluminum chloride (manufactured by Kanto Chemical Co., Ltd.), 64 g of sodium chloride (manufactured by Tokyo Chemical Industry Co., Ltd.), 84 g of zinc phthalocyanine (manufactured by DIC Corporation) and bromine (Fuji Film 209 g of Wako Pure Chemical Co., Ltd.) was injected. After heating up to 70 degreeC and taking out the obtained mixture in water, it filtered, washed with water, and dried to obtain zinc halide phthalocyanine (R8). 40 g of halogenated zinc phthalocyanine (R8), 400 g of pulverized sodium chloride, and 63 g of 1,3-butanediol (melting point: -54 ° C) were injected into a twin arm type kneader, and the cooling water circulator was set to -20 ° C. Kneaded for 20 hours. The mixture after kneading was taken out in 2 kg of water at 80°C and stirred for 1 hour. Thereafter, by filtering, washing with hot water, drying, and pulverizing, a zinc halide phthalocyanine pigment (RP8) was obtained as a cyan pigment. About the zinc halide phthalocyanine pigment (RP8), it carried out similarly to Synthesis Example 1, and calculated the average number of chlorine atoms and the average number of bromine atoms. In the zinc halide phthalocyanine pigment (RP8), the number of halogen atoms in one molecule was an average of 8.9, among which the number of bromine atoms was an average of 8.4 and the number of chlorine atoms was an average of 0.5.

<Examples 2 to 6>

Cyan pigment dispersions (RMG5) to (RMG8) were respectively obtained in the same manner as in Example 1, except that zinc halide phthalocyanine pigments (RP5) to (RP8) were respectively used instead of zinc halide phthalocyanine pigments (RP1).

<Evaluation of color filter characteristics>

(Preparation of composition for evaluation (RCG))

To 4.0 g of cyan pigment dispersion (RMG5), 0.98 g of Unidic ZL-295 (manufactured by DIC Corporation, brand name, solid content: 40% by mass) and 0.22 g of propylene glycol monomethyl ether acetate were added and mixed in a paint shaker, An evaluation composition (RCG5) for evaluating performance as a green pixel portion for color filters was obtained. In addition, compositions for evaluation (RCG6) to (RCG8) were produced in the same manner as above, except that (RMG6) to (RMG8) were respectively used instead of (RMG5).

(Preparation of color-adjusting composition (TY))

C.I. Pigment Yellow 185 (manufactured by BASF Co., Ltd., Paliotol Yellow D1155) 1.65 g, DISPERBYK-161 (manufactured by Big Chemie Co., Ltd., solid content: 30% by mass) 3.85 g and propylene glycol monomethyl ether acetate 11.00 g zircon of 0.3 to 0.4 mm Using beads, it dispersed in a paint shaker for 2 hours to obtain a yellow pigment dispersion (MY2). To 4.0 g of the yellow pigment dispersion (MY2), 0.98 g of Unidic ZL-295 (manufactured by DIC Corporation, brand name, solid content: 40% by mass) and 0.22 g of propylene glycol monomethyl ether acetate were added, and mixed by a paint shaker to adjust the color A composition for use (TY2) was obtained. Also, C.I. Instead of Pigment Yellow 185, C.I. A composition for evaluation (TY3) was prepared in the same manner as above except that Pigment Yellow 138 (Paliotol Yellow K0961HD, manufactured by BASF Corporation) was used. Also, C.I. Except for using the quinophthalone compound (D) described in the Examples of International Publication No. 2018/159372 (Japanese Patent Application No. 2018-560690) instead of Pigment Yellow 185, the evaluation composition (TY4) was prepared did.

(for light source A: preparation of composition for evaluation (RFG))

Composition for evaluation (RFG1) for evaluating the performance as a green pixel part for a color filter by mixing the compositions for evaluation (RCG1) to (RCG2) and (RCG5) to (RCG8), respectively, with the composition for toning (TY2) - (RFG2), (RFG5) - (RFG8) were prepared. Compositions for evaluation (RFG1) to (RFG2) and (RFG5) to (RFG8) are respectively spin-coated on a soda glass substrate and dried at 90° C. for 3 minutes to form a colored film on the soda glass substrate for evaluation. A glass substrate was produced. In addition, the blending ratio of the composition for evaluation (RFG1) to (RFG2) / composition for toning (TY2), the blending ratio of the composition for evaluation (RFG5) to (RFG8) / composition for toning (TY2), and the film thickness of the coating film, When light source A. LED+QD was used, the chromaticity of the coating film (measured using a spectrophotometer U-3900 manufactured by Hitachi High-Tech Science Co., Ltd.) was determined to be (x, y) = (0.170, 0.750). The film thickness of the coated film was adjusted by adjusting the number of spin rotations during spin coating.

(evaluation)

The luminance Y of the coating film was measured with a spectrophotometer (U-3900) manufactured by Hitachi High-Tech Science Co., Ltd. The results are shown in Table 5.

(for light source A: preparation of composition for evaluation (RGG))

Composition for evaluation (RGG1) for evaluating performance as a green pixel part for a color filter by mixing compositions for evaluation (RCG1) to (RCG2) and (RCG5) to (RCG8), respectively, with a composition for toning (TY3) - (RGG2), (RGG5) - (RGG8) were prepared. Compositions for evaluation (RGG1) to (RGG2) and (RGG5) to (RGG8) are respectively spin-coated on a soda glass substrate and dried at 90° C. for 3 minutes to form a colored film on the soda glass substrate for evaluation. A glass substrate was produced. In addition, the blending ratio of evaluation compositions (RGG1) to (RGG2) / color toning composition (TY3), the blending ratio of evaluation compositions (RGG5) to (RGG8) / color toning composition (TY3), and the film thickness of the coating film, When light source A. LED+QD was used, the chromaticity of the coating film (measured using a spectrophotometer U-3900 manufactured by Hitachi High-Tech Science Co., Ltd.) was determined to be (x, y) = (0.170, 0.750). The film thickness of the coated film was adjusted by adjusting the number of spin rotations during spin coating.

(evaluation)

The luminance Y of the coating film was measured with a spectrophotometer (U-3900) manufactured by Hitachi High-Tech Science Co., Ltd. The results are shown in Table 6.

(for light source A: preparation of composition for evaluation (RHG))

Composition for evaluation (RHG1) for evaluating the performance as a green pixel part for a color filter by mixing the compositions for evaluation (RCG1) to (RCG2) and (RCG5) to (RCG8), respectively, with the composition for toning (TY4) - (RHG2), (RHG5) - (RHG8) were prepared. Compositions for evaluation (RHG1) to (RHG2) and (RHG5) to (RHG8) are respectively spin-coated on a soda glass substrate and dried at 90° C. for 3 minutes to form a colored film on the soda glass substrate. A glass substrate was produced. In addition, the blending ratio of the composition for evaluation (RHG1) to (RHG2) / composition for toning (TY4), the blending ratio of the composition for evaluation (RHG5) to (RHG8) / composition for toning (TY4), and the film thickness of the coating film, When light source A. LED+QD was used, the chromaticity of the coating film (measured using a spectrophotometer U-3900 manufactured by Hitachi High-Tech Science Co., Ltd.) was determined to be (x, y) = (0.170, 0.750). The film thickness of the coated film was adjusted by adjusting the number of spin rotations during spin coating.

(evaluation)

The luminance Y of the coating film was measured with a spectrophotometer (U-3900) manufactured by Hitachi High-Tech Science Co., Ltd. The results are shown in Table 7.

As shown in Tables 5 to 7, even when the yellow pigment used for color toning is changed, Examples 2 to 6 have higher luminance than Comparative Example 6, and zinc halide phthalocyanine pigment (RP1) than zinc halide phthalocyanine pigment (RP2). ) and (RP5) to (RP8) were confirmed to be excellent.

<Reference Examples 1 to 8>

<Evaluation of the color of the color filter>

(Production of board for evaluation)

Each of the compositions for evaluation (RCG1) to (RCG8) and (SCG2) was spin-coated on a soda glass substrate, dried at 90°C for 3 minutes, and then heated at 230°C for 1 hour. In this way, a glass substrate for evaluation having a colored film on the soda glass substrate was produced. In addition, by adjusting the number of spin rotations during spin coating, the film thickness of the colored film obtained by heating at 230 ° C. for 1 hour was adjusted, and for each reference example, the film thickness of the colored film was 1.5 μm. A glass substrate for evaluation having a film thickness of 1.9 µm and a glass substrate for evaluation having a film thickness of the colored film of 2.4 µm were produced, respectively. The film thickness was measured with a white interferometric microscope (VS1330) manufactured by Hitachi High-Tech Science Co., Ltd.

(evaluation)

About each glass substrate for evaluation, the chromaticity (x, y) in C light source of a colored film was measured using the spectrophotometer (U-3900) by Hitachi High-Tech Science Co., Ltd. product. The results are shown in Table 8. Moreover, as shown in FIG. 3, the chromaticity (x, y) of the obtained colored film was plotted on the xy chromaticity coordinates in the XYZ colorimetric system of CIE. 3, the chromaticity coordinate area A surrounded by the following formulas (A) to (D), the xy chromaticity coordinate area B surrounded by the following formulas (C) and (E) to (G), and the following formula (E) and an xy chromaticity coordinate region C surrounded by (H)-(J). Three markers each of RCG1, 5 to 8, RCG2 to 4, and SCG2 in FIG. 3 indicate coordinates when the film thickness is 1.5, 1.9, and 2.4 μm, respectively.

Equation (A)：y=-1.766x+0.618

(In the formula, x is 0.10≤x≤0.17.)

Equation (B): y=5.889x-0.683

(In the formula, x is 0.15≤x≤0.17.)

Equation (C): y=0.125x+0.181

(In the formula, x is 0.07≤x≤0.15.)

Equation (D): y=8.380x-0.397

(In the formula, x is 0.07≤x≤0.10.)

Formula (E)：y=-1.333x+0.503

(In the formula, x is 0.10≤x≤0.16.)

Equation (F): y=9.000x-1.150

(In the formula, x is 0.15≤x≤0.16.)

Formula (G)：y=6.000x-0.230

(In the formula, x is 0.07≤x≤0.10.)

Formula (H)：y=7.000x-0.830

(In the formula, x is 0.15≤x≤0.16.)

Formula (I)：y=-0.286x+0.263

(In the formula, x is 0.08≤x≤0.15.)

Formula (J)：y=6.500x-0.280

(In the formula, x is 0.08≤x≤0.10.)

In Table 8, (RP1) and (RP5) to (RP8) used in Reference Examples 1 and 5 to 8 are the pigments (Examples) of the present invention. On the other hand, (RP4) and (SP2) used in Reference Examples 4 and 9 are pigments outside the scope of the present invention (comparative examples). As can be seen from FIG. 3, (RCG1) and (RCG5) to (RCG8) are colorimetric using a C light source alone when the film thickness is 1.5 μm to 2.4 μm and the composition is 1.25 parts of resin per 1 part of pigment in terms of mass. In the XYZ colorimetric system of CIE when From the above results, the number of halogen atoms in one molecule is 0.2 or more and 10 or less on average, the number of bromine atoms is 0.1 or more and 10 or less on average, the number of chlorine atoms is 0.1 or more and less than 2 on average, and the color is (A) It was confirmed that the luminance of the zinc halide phthalocyanine pigment falling in the range surrounded by (D) was high.

Claims (3)

As a pigment for forming a coating film in the green pixel portion of the color filter,
When the film thickness of the coating film is 1.5 μm to 2.4 μm and the composition is 1.25 parts of resin per 1 part of the pigment in terms of mass, in the XYZ color system of CIE when colorimetry is performed using a C light source alone, the following formula It is possible to display the xy chromaticity coordinate area surrounded by (A) to (D),
Formula (A)
y=-1.766x+0.618
(In the formula, x is 0.10≤x≤0.17.)
Formula (B)
y=5.889x-0.683
(In the formula, x is 0.15≤x≤0.17.)
Formula (C)
y=0.125x+0.181
(In the formula, x is 0.07≤x≤0.15.)
Formula (D)
y=8.380x-0.397
(In the formula, x is 0.07≤x≤0.10.)
The pigment contains a zinc halide phthalocyanine pigment which is a compound represented by the following formula (1), the number of halogen atoms in one molecule of the compound is from 0.2 to 10 on average, and the number of bromine atoms in one molecule of the compound is on average. 0.1 or more and 10 or less, and the number of chlorine atoms in 1 molecule of the said compound is 0.1 or more and less than 2 on average, The pigment for color filters.

[In Formula (1), X ¹ to X ¹⁶ each independently represent a hydrogen atom or a halogen atom.] A coloring composition containing the pigment for color filters according to claim 1 and a solvent. The color filter which has a green pixel part with the coating film formed with the pigment for color filters of Claim 1.

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