JPWO2020045199A1 - Halogenated zinc phthalocyanine pigments, coloring compositions and color filters - Google Patents

Abstract

［式（１）中、Ｘ^１〜Ｘ^１６は、各々独立に、水素原子又はハロゲン原子を示す。］
A zinc halide phthalocyanine pigment composed of a compound represented by the following formula (1), wherein the number of halogen atoms in one molecule of the compound is 8 or more and 13 or less on average, and bromine atoms in one molecule of the compound. Zinc phthalocyanine halide, which has an average number of 11 or less and an average number of chlorine atoms in one molecule of the compound is less than 2.
[Chemical 1]

[In formula (1), X ^{1 to} X ¹⁶ each independently represent a hydrogen atom or a halogen atom. ]

Description

The present invention relates to zinc halide phthalocyanine pigments, coloring compositions and color filters.

A color filter is a member that realizes a color display on a display by transmitting white light from a backlight. There is a demand for high brightness and high color reproduction for the green pixel part of the color filter, and it is possible to comply with the standards for high color reproduction displays (Adobe RGB, DCI-P3, etc.) that are expected to become widespread. Color filters are being considered.

As a method of achieving high color reproduction, for example, there is a method of increasing the film thickness of the color filter. However, C.I., which is mainly used in display applications that require high brightness. I. Since halogenated zinc phthalocyanine pigments such as Pigment Green 58 do not have sufficient coloring power, when these pigments are used for the green pixel portion, the thickness required for the pixel portion is large at the design chromaticity required by the above standard. Tends to be too much. Therefore, with the above pigments, it is difficult to form pixel portions that are sufficiently cured by exposure, and a method of increasing the film thickness of the color filter cannot be said to be an effective method for reproducing high colors. For this reason, in display applications where high color reproducibility is required, there is a demand for a green pigment having a high coloring power, which is thin and can form a sufficiently cured pixel portion.

As a result of the research by the present inventors, the halogenated zinc phthalocyanine pigment having a low halogenation rate has a high chromaticity, and by using such a pigment, the standard of a high color reproduction display (AdobeRGB, DCI-) It has been clarified that a green pixel portion having a sufficiently thin thickness can be formed even with the design chromaticity in (P3, etc.). For example, Patent Document 1 describes zinc halide phthalate cyanine having an average of 10 to 14 halogen atoms, an average of 8 to 12 bromine atoms, and an average of 2 to 5 chlorine atoms in one molecule. It is disclosed that by using it, it is possible to provide a color filter having high brightness and a wide color reproduction range.

International Publication 2015/118720 Pamphlet

However, there is room for further improvement in the above-mentioned prior art in terms of increasing the brightness.

Therefore, an object of the present invention is to provide a halogenated zinc phthalocyanine pigment which is excellent in brightness and coloring power and is suitably used for a color filter for high color reproduction, and a coloring composition and a color filter using the pigment. To do.

［式（１）中、Ｘ^１〜Ｘ^１６は、各々独立に、水素原子又はハロゲン原子を示す。］One aspect of the present invention is a zinc halide phthalocyanine pigment composed of a compound represented by the following formula (1), wherein the number of halogen atoms in one molecule of the compound is 8 or more and 13 or less on average. The present invention relates to a zinc halide phthalocyanine pigment having an average number of bromine atoms in one molecule of a compound of 11 or less and an average number of chlorine atoms in one molecule of a compound of less than two.

[In formula (1), X ^{1 to} X ¹⁶ each independently represent a hydrogen atom or a halogen atom. ]

Until now, in the design of color filters, the mass of the pigment used has often been fixed, and the larger the number of moles of the pigment in the color filter, in other words, the smaller the average molecular weight of the pigment, the more the color of the pigment develops. It has been considered excellent. Therefore, for example, the halogenated zinc phthalocyanine pigment described in Patent Document 1 has been designed so that the average number of chlorine atoms having an atomic weight smaller than that of the bromine atom is two or more for the purpose of lowering the average molecular weight. However, as a result of the studies by the present inventors, surprisingly, when the number of bromine atoms is 11 or less on average, excellent brightness can be obtained by reducing the number of chlorine atoms to less than 2. Became clear.

That is, the zinc halide phthalocyanine pigment according to one aspect of the present invention is excellent not only in coloring power but also in brightness. Therefore, according to the above-mentioned zinc halide phthalocyanine pigment, even if it has a design chromaticity according to a high color reproduction display standard (AdobeRGB, DCI-P3, etc.), it is sufficiently thin and exhibits high brightness at the design chromaticity. A green pixel portion can be formed.

Another aspect of the present invention relates to a coloring composition containing a zinc halide phthalocyanine pigment and a solvent.

Another aspect of the present invention relates to a color filter having a pixel portion containing the above-mentioned zinc halide phthalocyanine pigment.

According to the present invention, it is possible to provide a halogenated zinc phthalocyanine pigment which is excellent in brightness and coloring power and is suitably used for a color filter for high color reproduction, and a coloring composition and a color filter using the pigment.

FIG. 1 is a diagram showing a region where the pigments of Examples and Comparative Examples are monochromatic and color-reproducible with a C light source.

［式（１）中、Ｘ^１〜Ｘ^１６は、各々独立に、水素原子又はハロゲン原子を示す。］<Pigments and pigment compositions>
The zinc halide phthalocyanine pigment of one embodiment is composed of one kind or a plurality of kinds of halogenated zinc phthalocyanine compounds having different numbers of halogen atoms. The halogenated zinc phthalocyanine compound has a structure represented by the following formula (1).

[In formula (1), X ^{1 to} X ¹⁶ each independently represent a hydrogen atom or a halogen atom. ]

In the halogenated zinc phthalocyanine pigment, the average number of halogen atoms in one molecule of the compound represented by the formula (1) is 8 or more and 13 or less. That is, the ratio of the total number of halogen atoms contained in the compound to the number of molecules of the compound represented by the formula (1) constituting the halogenated zinc phthalocyanine pigment is 8 or more and 13 or less. Further, in the halogenated zinc phthalocyanine pigment, the average number of bromine atoms in one molecule of the compound represented by the formula (1) is 11 or less, and the average number of chlorine atoms is less than 2.

Since the halogenated zinc phthalocyanine pigment of the present embodiment has the halogen atomic composition as described above, it has excellent coloring power as a green pigment and also has excellent brightness. Therefore, according to the zinc halide phthalocyanine pigment of the present embodiment, the thickness is sufficiently thin at the design chromaticity in the standard of high color reproduction display (Adobe RGB, DCI-P3, etc.), and the green color showing high brightness at the design chromaticity. A pixel portion can be formed. The design chromaticity required by the standard for high-color reproduction displays is, for example, (x, y) = (0.210, 0.670) when a C light source is used (Japanese Patent Laid-Open No. 2017-16132, etc.). reference.).

The present inventors infer the reason why the above effect can be obtained by the halogenated zinc phthalocyanine pigment of the present embodiment as follows. That is, in the halogenated zinc phthalocyanine pigment having a high halogenation rate, the presence of halogen atoms causes the periphery of the molecule to become congested, which greatly affects the absorption characteristics. Therefore, among the halogen atoms, the influence on the transmission spectrum of the bromine atom having an atomic radius larger than that of the chlorine atom is larger than the influence on the transmission spectrum of the chlorine atom. On the other hand, in the halogenated zinc phthalocyanine pigment having a low halogenation rate, the influence of the three-dimensional effect on the absorption characteristics is weakened, and the influence on the absorption characteristics of the chlorine atom, which has stronger electron attraction than the bromine atom, is the bromine atom. It has a greater effect on the absorption characteristics of. Therefore, when the number of bromine atoms is 11 or less on average and the number of chlorine atoms is 2 or more on average, a variety of compounds having different numbers of substitutions and substitution positions of chlorine atoms exist, and the spectrum is broadened. Occurs. As a result, it is presumed that the brightness of the zinc halide phthalocyanine pigment is lowered and the coloring power is lowered. On the other hand, in the halogenated zinc phthalocyanine pigment of the present embodiment, it is presumed that when the number of chlorine atoms is less than 2, the broadening of the spectrum as described above is suppressed, and excellent brightness and coloring power can be obtained. ..

Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom. The halogenated zinc phthalocyanine pigment preferably has at least one of a bromine atom and a chlorine atom as a halogen atom, and preferably has a bromine atom. The halogenated zinc phthalocyanine pigment may have only one or both of a chlorine atom and a bromine atom as a halogen atom. That is, X ^{1 to} X ¹⁶ in the above formula (1) may be a chlorine atom or a bromine atom.

In the halogenated zinc phthalocyanine pigment, the average number of halogen atoms in one molecule of the compound represented by the formula (1) is preferably 12.5 or less, more preferably 12 from the viewpoint of further enhancing the coloring power. Less than or equal to. The average number of halogen atoms is preferably 9 or more, and more preferably 10 or more, from the viewpoint of obtaining even better brightness. The above upper limit value and lower limit value can be arbitrarily combined. For example, the average number of halogen atoms may be 9 to 12.5 or 10 to 12. In the same description below, the upper limit value and the lower limit value described individually can be arbitrarily combined.

The average number of bromine atoms in one molecule of the compound represented by the formula (1) in the zinc halide phthalocyanine pigment is preferably 10.6 or less from the viewpoint of obtaining more excellent brightness and coloring power. , More preferably 10.2 or less. The average number of bromine atoms is preferably 8 or more, and more preferably 9 or more, from the viewpoint of obtaining even better brightness. The average number of bromine atoms may be 9.3 or more.

In the halogenated zinc phthalocyanine pigment, the average number of chlorine atoms in one molecule of the compound represented by the formula (1) is preferably 1.9 or less from the viewpoint of obtaining more excellent brightness and coloring power. , More preferably 1.5 or less, still more preferably 1.3 or less. The average number of chlorine atoms is preferably 0.1 or more, more preferably 0.3 or more, still more preferably 0.6 or more, from the viewpoint of obtaining more excellent brightness. Particularly preferably, the number is 0.8 or more, extremely preferably 1 or more, and even more preferably 1.3 or more.

From the above viewpoint, it is preferable that the average number of bromine atoms is 8 or more and 11 or less, and the average number of chlorine atoms is 0.1 or more and less than 2.

The number of halogen atoms (for example, the number of bromine atoms and the number of chlorine atoms) can be measured by fluorescent 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 the zinc atom and each halogen atom in the halogenated zinc phthalocyanine pigment.

The zinc halide phthalocyanine pigment is composed of one or more particles. The average particle size (average primary particle size) 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 size is an average value of the major axis of the primary particle, and can be obtained by measuring the major axis of the primary particle 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 1.0 or more, 1.2 or more, 1.3 or more, 1.4 or more or 1.5 or more from the viewpoint of obtaining better contrast. You may. The average aspect ratio of the primary particles of the zinc halide phthalocyanine pigment is 3.0 or less, less than 2.0, 1.8 or less, 1.6 or less, or 1.4 or less from the viewpoint of obtaining better contrast. You may.

The zinc halide phthalocyanine pigment having an average aspect ratio of the 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 contains primary particles having an aspect ratio of 4 or more. It is more preferable that there is no primary particle, and it is further preferable that the primary particle having an aspect ratio of more than 3 is not contained.

The aspect ratio and average aspect ratio of the primary particles can be measured by the following methods. First, the particles in the field of view are photographed with a transmission electron microscope (for example, JEM-2010 manufactured by JEOL 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 defined as the aspect ratio of the primary particles. Further, the average values of the major axis and the minor axis are obtained for 40 primary particles, and the ratio of the major axis to the minor axis is calculated using these values, and this is used as the average aspect ratio. At this time, the halogenated zinc phthalocyanine pigment, which is a sample, is ultrasonically dispersed in a solvent (for example, cyclohexane) and then photographed with a microscope. Further, a scanning electron microscope may be used instead of the transmission electron microscope.

The halogenated zinc phthalocyanine pigment of the present embodiment includes, for example, a step of forming a crude pigment composed of a halogenated zinc phthalocyanine compound (hereinafter referred to as a halogenated zinc phthalocyanine crude pigment) and a step of pigmentating the crude pigment. Obtained by a method comprising.

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

Examples of the chlorosulfonic acid method include a method in which zinc phthalocyanine is dissolved in a sulfur oxide-based solvent such as chlorosulfonic acid, and chlorine gas and bromine are charged therein for halogenation. The reaction at this time is carried out, for example, at a temperature of 20 to 120 ° C. and in the range of 3 to 20 hours.

As the halogenated phthalonitrile method, for example, in addition to bromine, phthalic acid or phthalocyanine in which some or all of the hydrogen atoms of the aromatic ring are substituted with halogen atoms such as chlorine, and a metal or metal salt of zinc are appropriately used. A method of synthesizing the corresponding zinc halide phthalocyanine compound using it as a starting material can be mentioned. In this case, a catalyst such as ammonium molybdate may be used if necessary. The reaction at this time is carried out, for example, at a temperature of 100 to 300 ° C. and in the range of 7 to 35 hours.

Examples of the melting method include aluminum halides such as aluminum chloride and aluminum bromide, titanium halides such as titanium tetrachloride, alkali metal halides such as sodium chloride and sodium bromide, or alkaline earth metal halides (hereinafter referred to as alkali (hereinafter referred to as alkali (hereinafter, alkali)). Halogenation of zinc phthalocyanine in a melt at about 10 to 170 ° C consisting of one or a mixture of two or more compounds that serve as solvents during various halogenations, such as earth) metal halides) and thionyl chloride. Examples thereof include a method of halogenating with an agent.

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

Aluminum halide may be used alone, but when an alkali (earth) metal halide is used in combination with aluminum halide, the melting temperature can be further lowered, which is advantageous in terms of operation. A suitable alkaline (earth) metal halide is sodium chloride. The amount of the alkali (earth) metal halide to be added is preferably 5 to 15 parts by mass of the alkali (earth) metal halide with respect to 10 parts by mass of aluminum halide within the range of producing a molten salt.

Examples of the halogenating agent include chlorine gas, sulfuryl chloride, bromine and the like.

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

In the melting method in which two or more of the above compounds are used in combination, the ratio of chloride, bromide and iodide in the molten salt is adjusted, and the amount of chlorine gas, bromine, iodine, etc. introduced and the reaction time are changed. Therefore, the content ratio of the halogenated zinc phthalocyanine compound having a specific halogen atomic composition in the halogenated zinc phthalocyanine compound to be produced can be arbitrarily controlled, which is preferable. Further, according to the melting method, the decomposition of the raw material during the reaction is small, the yield from the raw material is more excellent, and the reaction can be carried out by an inexpensive apparatus without using a strong acid.

In the present embodiment, a halogenated zinc phthalocyanine compound having a halogen atomic composition different from that of the existing halogenated zinc phthalocyanine compound can be obtained by optimizing the raw material charging method, the catalyst species and the amount used thereof, the reaction temperature and the reaction time. ..

In any of the above methods, after the reaction is completed, the obtained mixture is put into an acidic aqueous solution such as water or hydrochloric acid to precipitate the produced zinc halide phthalocyanine compound, thereby producing a halogenated zinc phthalocyanine crude pigment. Obtainable. As the halogenated zinc phthalocyanine crude pigment, this may be used as it is, but after that, filtration, water or sodium hydrogen sulfate water, sodium hydrogen carbonate water, sodium hydroxide water washing, and acetone, toluene, methyl alcohol as necessary. , Ethyl alcohol, dimethylformamide and the like, and after performing post-treatment such as drying, it is preferable to use the product. If necessary, the halogenated zinc phthalocyanine crude pigment may be dry-ground in a crusher such as an attritor, a ball mill, a vibration mill, or a vibration ball mill before use.

The crude zinc halide phthalocyanine pigment obtained in the above step has the same composition as the zinc halogenated zinc phthalocyanine pigment.

In the step of pigmentating the halogenated zinc phthalocyanine crude pigment, for example, the halogenated zinc phthalocyanine crude pigment is kneaded and ground to obtain a halogenated zinc phthalocyanine pigment. The step of pigmentating the halogenated zinc phthalocyanine crude pigment may be a step of kneading the halogenated zinc phthalocyanine crude pigment together with an inorganic salt and an organic solvent. Kneading can be performed using, for example, a kneader, a mix mahler, or the like.

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 size of the inorganic salt is preferably 0.5 to 50 μm. Such an inorganic salt can be easily obtained by finely pulverizing an ordinary inorganic salt.

It is preferable to increase the amount of the inorganic salt used relative to the amount of the crude pigment used, because a pigment having an average primary particle size in the above range can be easily obtained. Specifically, the amount of the 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.

As the organic solvent, one that does not dissolve the crude pigment and the inorganic salt 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 preferably used. Examples of the organic solvent include diethylene glycol, glycerin, ethylene glycol, propylene glycol, liquid polyethylene glycol, liquid polypropylene glycol, 2- (methoxymethoxy) ethanol, 2-butoxyethanol, 2- (isopentyloxy) ethanol, and 2- (hexyl). Oxy) 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 and the like can be used. The amount of the organic solvent (for example, a water-soluble organic solvent) used is not particularly limited, but is preferably 0.01 to 5 parts by mass with respect to 1 part by mass of the crude pigment.

When an inorganic salt and an organic solvent are used, a mixture containing a zinc halide phthalocyanine pigment, an inorganic salt and an organic solvent can be obtained. The organic solvent and the inorganic salt are removed from this mixture, and zinc halide is required. Operations such as washing, filtering, drying, and pulverizing may be performed on a solid substance mainly composed of a phthalocyanine pigment.

As the washing, either water washing or hot water washing can be adopted. The washing may be repeated in the range of 1 to 5 times. When a water-soluble inorganic salt and a water-soluble organic solvent are used, the organic solvent and the inorganic salt can be easily removed by washing with water. If necessary, acid cleaning, alkaline cleaning, and organic solvent cleaning may be performed.

Examples of the drying after the washing and filtration include batch type or continuous type drying in which the pigment is dehydrated and / or the solvent is removed by heating at 80 to 120 ° C. by a heating source installed in a dryer. .. Examples of the dryer generally include a box-type dryer, a band dryer, a spray dryer, and the like. In particular, spray-dry drying using a spray dryer is preferable because it is easily dispersed during paste preparation. Further, pulverization after drying is not an operation for increasing the specific surface area or decreasing the average particle size of the primary particles, as in the case of drying using, for example, a box dryer or a band dryer. This is performed to dissolve the pigment and pulverize it when the pigment becomes lamp-shaped or the like. For example, crushing with a mortar, a hammer mill, a disc mill, a pin mill, a jet mill or the like can be mentioned.

In the above method, the resin may coexist when the crude pigment is pigmented. By coexisting the resin at the time of pigmentation, the active surface (active growth surface) of the particles is stabilized by the resin. As a result, the bias in the direction of particle growth is alleviated, so that a pigment having a small average aspect ratio can be easily obtained. By using such a pigment, the contrast of the pixel portion can be improved. In this method, the zinc halide phthalocyanine pigment is obtained as a mixture with a resin for coating the halogenated zinc phthalocyanine pigment (hereinafter, also referred to as a coating resin). Therefore, this method can be rephrased as a method for producing a pigment composition containing a halogenated zinc phthalocyanine pigment and a coating resin.

In the method in which the resin coexists, the step of pigmentating the halogenated zinc phthalocyanine crude pigment may be a step of kneading the halogenated zinc phthalocyanine crude pigment together with the resin, and the halogenated zinc phthalocyanine crude pigment may be mixed with the resin, the inorganic salt and the resin. It may be a step of kneading with an organic solvent.

When an inorganic salt and an organic solvent are used, similarly to the above, after removing the organic solvent and the inorganic salt from the mixture containing the halogenated zinc phthalocyanine pigment, the resin, the inorganic salt and the organic solvent, if necessary. The solid substance mainly composed of the halogenated zinc phthalocyanine pigment and the resin may be washed, filtered, dried, pulverized and the like.

As the 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 expresses an interaction with the active surface (active growth surface), the resin has an acidic group, so that a pigment having a small average aspect ratio of the primary particles can be easily obtained. Examples of the acidic group include a carboxyl group, a sulfonic acid group, a phosphoric acid group, and an ammonium base thereof. Among these, a carboxyl group is preferable from the viewpoint that more excellent contrast can be easily obtained.

The resin contains one or more polymers. Examples of the polymer include vinyl-based polymers. The vinyl-based polymer contains a monomer having a vinyl group (vinyl-based monomer) as a monomer unit. The vinyl-based polymer preferably has an acidic group, and more preferably has a carboxyl group, from the viewpoint of facilitating the acquisition of better contrast.

Examples of the vinyl-based monomer include (meth) acrylate-based monomer, styrene-based monomer, vinyl ether-based monomer, nitrogen-containing monomer, (halogen-substituted) hydrocarbon-based monomer, and the like. In addition, in this specification, "(meth) acrylate" means at least one of acrylate and corresponding methacrylate. Among the vinyl-based monomers, the vinyl-based polymer preferably contains a (meth) acrylate-based monomer as a monomer unit. That is, the vinyl-based polymer is preferably a (meth) acrylate-based polymer.

Examples of the (meth) acrylate-based monomer include methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, iso-propyl (meth) acrylate, n-butyl (meth) acrylate, and sec-butyl. (Meta) acrylate, iso-butyl (meth) acrylate, tert-butyl (meth) acrylate, n-pentyl (meth) acrylate, neopentyl (meth) acrylate, iso-pentyl (meth) acrylate, sec-pentyl (meth) acrylate , 3-Pentyl (meth) acrylate, tert-pentyl (meth) acrylate, hexyl (meth) acrylate, heptyl (meth) acrylate, octyl (meth) acrylate, nonyl (meth) acrylate, decyl (meth) acrylate, 2-ethylhexyl (Meta) acrylate, n-lauryl (meth) acrylate, n-stearyl (meth) acrylate, cetyl (meth) acrylate, behenyl (meth) acrylate, cyclohexyl (meth) acrylate, isobornyl (meth) acrylate, adamantyl (meth) Acrylate, dicyclopentanyl (meth) acrylate, tert-butylcyclohexyl (meth) acrylate, ethylcyclohexyl (meth) acrylate, isopropylcyclohexyl (meth) acrylate, isobutylcyclohexyl (meth) acrylate, methylcyclohexyl (meth) acrylate, cyclopentyl ( Meta) acrylate, cycloheptyl (meth) acrylate, cyclooctyl (meth) acrylate, cyclononyl (meth) acrylate, isodecyl (meth) acrylate, cyclodecyl (meth) acrylate, benzyl (meth) acrylate, phenyl (meth) acrylate, phenoxyethyl (Meta) acrylate, hydroxypropyl (meth) acrylate, nonylphenoxypolyethylene glycol (meth) acrylate, neopentyl glycol benzoate (meth) acrylate, paracumylphenoxyethylene glycol (meth) acrylate, 2-hydroxyethyl (meth) acrylate, hydroxy Propyl (meth) acrylate, 3-phenoxy-2-hydroxypropyl (meth) acrylate, neopentyl glycol benzoate (meth) acrylate, phenylphenol (meth) acrylate, phenoxydiechi Lenglycol (meth) acrylate, nonylphenoxyethyl (meth) acrylate, naphthyl (meth) acrylate, glycidyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate glycidyl ether, 3,4-epoxycyclohexylmethyl (meth) acrylate, Examples thereof include 3,4-epoxybutyl (meth) acrylate, 4,5-epoxypentyl (meth) acrylate, 6,7-epoxypentyl (meth) acrylate, and β-methylglycidyl (meth) acrylate.

The monomer contained in the polymer as a monomer unit may be one kind or a plurality of kinds. For example, the polymer may contain a (meth) acrylate-based monomer and another vinyl-based monomer different from the (meth) acrylate-based monomer as a monomer unit. That is, the polymer may be a copolymer of a (meth) acrylate-based monomer and another vinyl-based monomer. The other vinyl-based monomer may be a monomer having an acidic group, for example, (meth) acrylic acid. Other vinyl-based monomers include, for example, nitro group-containing vinyl-based monomers such as (meth) acrylonitrile, vinyl-based aromatic monomers such as styrene and α-methylstyrene, (meth) acrylamide, N, N-dimethylacrylamide, and the like. Amido group-containing vinyl monomers such as N-isopropylacrylamide, N-methylol (meth) acrylamide, dimethylol (meth) acrylamide or diacetoneacrylamide, N-methoxymethyl (meth) acrylamide, or N-butoxymethyl (meth) acrylamide. Ekoxymethyl group-containing vinyl-based monomers such as, olefins such as ethylene, propylene, or isoprene, dienes such as chloroprene, or butadiene, methyl vinyl ether, ethyl vinyl ether, n-propyl vinyl ether, isopropyl vinyl ether, n-butyl vinyl ether, etc. Or vinyl ethers such as isobutyl vinyl ether, vinyl acetate, or fatty acid vinyls such as vinyl propionate, 3- (meth) allyloxy-2-hydroxypropanesulfonic acid, 2- (meth) allyloxyethylenesulfonic acid, 2-acrylamide- 2-Methylpropane sulfonic acid, p-styrene sulfonic acid, α-methyl-p-styrene sulfonic acid, vinyl sulfonic acid, vinyl sulfamic acid, (meth) allyl sulfonic acid, isoprene sulfonic acid, 4- (allyloxy) benzene sulfonic acid , 1-Methyl-2-propen-1-sulfonic acid, 1,1-dimethyl-2-propen-1-sulfonic acid, 3-butene-1-sulfonic acid, 1-buten-3-sulfonic acid, 2-acrylamide -1-Methylpropanesulfonic acid, 2-acrylamidepropanesulfonic acid, 2-acrylamide-n-butanesulfonic acid, 2-acrylamide-2-phenylpropanesulfonic acid, 2-((meth) acryloyloxy) ethanesulfonic acid, etc. It may be unsaturated sulfonic acid or the like.

The content of the (meth) acrylate-based monomer in the vinyl-based polymer is a vinyl-based weight from the viewpoint of exhibiting high transparency, which is an advantage of the (meth) acrylate-based polymer, to the extent that the brightness of the color filter is not reduced. Based on the mass of all the monomer units contained in the coalescence, it is preferably 90% by mass or more, and may be 92% by mass or more or 94% by mass or more. The content of the (meth) acrylate-based monomer in the vinyl-based polymer is the total monomer contained in the vinyl-based polymer from the viewpoint of supplementing the heat resistance, which is a disadvantage of the (meth) acrylate-based polymer, with other vinyl-based monomers. It may be 99% by mass or less, 97% by mass or less, or 95% by mass or less based on the mass of the unit.

The content of the vinyl-based polymer in the resin may be 90% by mass or more, or 100% by mass, based on the total mass of the resin. The content of the (meth) acrylate-based polymer in the resin may be 90% by mass or more, or 100% by mass, based on the total mass of the resin.

The acid value of the resin is preferably 50 mgKOH / g or more, more preferably 70 mgKOH / g or more, still more preferably 90 mgKOH / g or more, from the viewpoint of facilitating the acquisition of more excellent contrast. The acid value of the resin may be 150 mgKOH / g or less, 170 mgKOH / g or less, or 200 mgKOH / g or less from the viewpoint of ensuring developability. When the resin contains a vinyl-based polymer, the acid value of the vinyl-based polymer may be in the above range, and the acid value of the (meth) acrylate-based polymer may be in the above range.

For the above acid value, a sample solution prepared by dissolving 1 ml of resin pg and phenolphthalein test solution in 50 ml of a mixed solution of toluene and ethanol mixed at a volume ratio of 1: 1 was prepared, and 0.1 mol / L ethanol-made hydroxide was prepared. Titrate with a potassium solution (7.0 g of potassium hydroxide dissolved in 5.0 ml of distilled water and adjusted to 1000 ml by adding 95 vol% ethanol) until the sample solution turns pink, and calculated by the following formula. it can.
Acid value = q × r × 5.611 / p
In the formula, q indicates the titration amount (ml) of the 0.1 mol / L ethanol potassium hydroxide solution required for titration, and r indicates the titer of the 0.1 mol / L ethanol potassium hydroxide solution required for titration. Shown, p indicates the mass (g) of the resin.

The weight average molecular weight of the resin is preferably 4000 or more, and may be 8000 or more, 10000 or more, or 15000 or more from the viewpoint of preventing volatilization when heated at around 200 ° C. in the display manufacturing process. The weight average molecular weight of the resin may be 20000 or less, 18000 or less, or 17000 or less from the viewpoint of efficiently coating the pigment surface. When the resin contains a vinyl-based polymer, the weight average molecular weight of the vinyl-based polymer may be in the above range, and the weight average molecular weight of the (meth) acrylate-based polymer may be in the above range. The weight average molecular weight is a polystyrene-equivalent weight average molecular weight obtained by a gel permeation chromatograph.

The glass transition temperature (Tg) of the resin is preferably 40 ° C. or higher, and may be 45 ° C. or higher or 50 ° C. or higher from the viewpoint of ensuring stability during storage. The glass transition temperature (Tg) of the resin may be 200 ° C. or lower, 95 ° C. or lower, or 65 ° C. or lower from the viewpoint of ensuring developability and easily obtaining an industrial raw material. When the resin contains a vinyl polymer, the glass transition temperature (Tg) of the vinyl polymer may be in the above range, and the glass transition temperature (Tg) of the (meth) acrylate polymer is in the above range. May be good. The glass transition temperature (Tg) can be measured by thermal differential analysis (DSC).

From these viewpoints, a resin containing a vinyl-based polymer having a carboxyl group and having an acid value of 50 mgKOH / g or more is preferable. Further, a gel permeation chromatograph containing a (meth) acrylate-based polymer containing 90% by mass or more based on the mass of all monomer units contained in the vinyl-based polymer and having an acidic group. A resin having a polystyrene-equivalent weight average molecular weight of 4000 or more and a glass transition temperature of 40 ° C. or more is preferable.

The amount of the resin used is preferably 0.1 part by mass or more, and 0.5 part by mass with respect to 100 parts by mass of the crude pigment, from the viewpoint that the pigment can be sufficiently coated and the contrast can be further improved. It may be 10 parts or more, 1.0 part by mass or more, or 1.5 parts by mass or more. The amount of the resin used is preferably 10 parts by mass or less with respect to 100 parts by mass of the crude pigment, from the viewpoint of easily obtaining a pigment having more excellent coloring power and further improving the contrast. It may be 0 parts by mass or less, 5.0 parts by mass or less, 3.5 parts by mass or less, or 3.0 parts by mass or less. The amount of the resin used is, for example, 0.1 to 10 parts by mass, 0.5 to 7.0 parts by mass, 1.0 to 5.0 parts by mass, and 1.0 to 3 parts with respect to 100 parts by mass of the crude pigment. .5 parts by mass or 1.5 to 3.0 parts by mass. In the present embodiment, the amount of the polymer having an acidic group used is preferably in the above range.

Next, the pigment composition of one embodiment will be described.

The pigment composition of one embodiment contains at least the above-mentioned zinc halide phthalocyanine pigment. The content of the halogenated zinc phthalocyanine pigment in the pigment composition may be 85% by mass or more, 90% by mass or more, or 95% by mass or more based on the total mass of the pigment composition. The content of the halogenated zinc phthalocyanine pigment in the pigment composition may be 99% by mass or less, 98% by mass or less, or 96% by mass or less based on the total mass of the pigment composition.

The pigment composition may further contain a resin (coating resin) for coating the zinc halide phthalocyanine pigment. In this case, the halogenated zinc phthalocyanine pigment is preferably completely coated with the resin, but a part of the pigment may not be coated with the resin. That is, when the halogenated zinc phthalocyanine pigment is coated with a resin, the halogenated zinc phthalocyanine pigment may contain particles that are at least partially coated with the resin, and only from the particles completely coated with the resin. It may be composed of only particles which are partially covered with a resin and partially exposed, or may be a mixture thereof. Further, the halogenated zinc phthalocyanine pigment may contain particles that are not completely coated with the resin.

The coating resin may be the above-mentioned resin used for producing a zinc halide phthalocyanine pigment. The content of the coating resin in the pigment composition is preferably 0.1 part by mass or more, and 0.5 part by mass with respect to 100 parts by mass of the halogenated zinc phthalocyanine pigment, from the viewpoint of making it easier to improve the contrast. As mentioned above, it may be 1.0 part by mass or more or 1.5 parts by mass or more. The content of the coating resin in the pigment composition is preferably 10 parts by mass or less with respect to 100 parts by mass of the halogenated zinc phthalocyanine pigment from the viewpoint of being more excellent in coloring power and more easily improving the contrast. It may be 0.0 parts by mass or less, 5.0 parts by mass or less, 3.5 parts by mass or less, or 3.0 parts by mass or less. The content of the coating resin in the pigment composition is, for example, 0.1 to 10 parts by mass, 0.5 to 7.0 parts by mass, and 1.0 to 5. parts by mass with respect to 100 parts by mass of the zinc halide phthalocyanine pigment. It is 0 parts by mass, 1.0 to 3.5 parts by mass, or 1.5 to 3.0 parts by mass. In the present embodiment, the content of the polymer having an acidic group is preferably in the above range.

The pigment composition may further contain components other than the above-mentioned zinc halide phthalocyanine pigment and coating resin. Examples of other components include known phthalocyanine derivatives and the like. Other components may be added, for example, in the step of pigmentating the crude pigment together with the resin, or may be added after obtaining the halogenated zinc phthalocyanine pigment.

The pigment composition is substantially free of solvents and is, for example, in solid form (eg, powder form). The content of the solvent in the pigment composition is, for example, 0% by mass or more and 1.0% by mass or less. By dispersing the pigment composition in a solvent, a coloring composition which is a pigment dispersion can be formed.

The above-described zinc halide phthalocyanine pigment and the pigment composition containing the same are not as specific as the conventional highly halogenated zinc phthalocyanine pigment, but are more specific to the bluish hue than the conventional highly halogenated zinc phthalocyanine pigment. Highly halogenated zinc phthalocyanine pigments can express hues that could not be achieved. For example, the zinc halide phthalocyanine pigment has the following formula (in the XYZ color system of CIE when the color is measured by itself using a C light source when the coating film has a thickness of 1.5 μm to 2.4 μm. It is possible to display the xy chromaticity coordinate area surrounded by 1) to (4), and more preferably the xy chromaticity coordinate area surrounded by the following equations (1) and (5) to (7). Yes, and more preferably, the xy chromaticity coordinate region surrounded by the following equations (1) and (8) to (10) can be displayed. Specifically, the coating film can be formed by the following method. First, 2.48 g of the zinc halide phthalocyanine pigment (when the halogenated zinc phthalocyanine pigment is coated with the above coating resin, the total amount of the halogenated zinc phthalocyanine pigment and the coating resin 2.48 g) is added to BYK-LPN6919 (DIC Corporation). , Trade name, solid content: 60% by mass) 1.24g, Unidic ZL-295 (manufactured by DIC Corporation, trade name, solid content: 40% by mass) 1.86g and propylene glycol monomethyl ether acetate 10.92g Disperse for 2 hours using 0.3 to 0.4 mm zircon beads to obtain a pigment dispersion. To 4.0 g of the obtained pigment dispersion, 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 the paint shaker was used. Mix to make a coating solution. Next, the coating liquid is spin-coated on a soda glass substrate, dried at 90 ° C. for 3 minutes, and then heated at 230 ° C. for 1 hour to form a coating film. The chromaticity is, for example, a value measured using a spectrophotometer (U-3900) manufactured by Hitachi High-Tech Science Corporation.

Equation (1): y = -1.766x + 0.628
(In the formula, x is 0.11 <x <0.17.)
Equation (2): y = 2.477x + 0.161
(In the formula, x is 0.11 <x <0.17.)
Equation (3): y = -3.498x + 1.177
(In the formula, x is 0.17 <x <0.21.)
Equation (4): y = 2.865x-0.159
(In the formula, x is 0.17 <x <0.21.)

Equation (5): y = 2.477x + 0.161
(In the formula, x is 0.11 <x <0.16.)
Equation (6): y = −3.583x + 1.131
(In the formula, x is 0.16 <x <0.20.)
Equation (7): y = 2.865x-0.159
(In the formula, x is 0.17 <x <0.20.)

Equation (8): y = 2.477x + 0.161
(In the formula, x is 0.11 <x <0.15.)
Equation (9): y = -3.680x + 1.085
(In the formula, x is 0.15 <x <0.19.)
Equation (10): y = 2.865x-0.159
(In the formula, x is 0.17 <x <0.19.)

The zinc halide phthalocyanine pigment of the present embodiment and the pigment composition containing the same can be used for known and commonly used applications, such as for color filters, paints, plastics, printing inks, rubber, leather, printing, electronic toners, jets. Suitable for coloring inks, thermal transfer inks, etc. Among these, green pigments and green pigment compositions for color filters, particularly green pigments and green pigment compositions used for green pixel portions of color filters, are preferably used.

As described above, the halogenated zinc phthalocyanine pigment of the present embodiment has an average number of halogen atoms of 8 or more and 13 or less, an average of 11 or less bromine atoms, and an average of 2 chlorine atoms. Since it is less than, it is excellent in coloring power and brightness. Therefore, the zinc halide phthalocyanine pigment of the present embodiment and the pigment composition containing the same can display the xy chromaticity coordinate region as described above, and according to the pigment and the pigment composition, high color reproduction is performed. Even with the design chromaticity according to the display standard (AdobeRGB, DCI-P3, etc.), it is possible to form a green pixel portion that is sufficiently thin and exhibits high brightness.

Further, when the halogenated zinc phthalocyanine pigment of the present embodiment and the pigment composition containing the same are used for forming the green pixel portion of the color filter, it is not necessary to use the yellow pigment in combination for toning. Even so, a smaller amount is required. As a result, a decrease in light transmittance over the entire range of 380 to 780 nm can be prevented to a minimum.

<Coloring composition>
The coloring composition of one embodiment contains at least the above-mentioned zinc halide phthalocyanine pigment and a solvent.

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 the resin described as the coating resin contained in the pigment composition described above, and the preferred embodiment is also the same.

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

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 an organic pigment other than the zinc halide phthalocyanine pigment, an organic dye, an organic pigment derivative, or the like, in consideration of economic efficiency. As the organic pigment, a known and commonly used green metal halide phthalocyanine pigment such as green halogenated copper phthalocyanine and other green halogenated dissimilar metal phthalocyanine pigments can be used. Further, a yellow pigment for toning may be used. Examples of the yellow pigment include C.I. I. Examples thereof include yellow organic pigments such as Pigment Yellow 83, 110, 129, 138, 139, 150, 180, 185, and 231. The combined ratio of the halogenated zinc phthalocyanine pigment and the yellow pigment is, for example, 1 to 400 parts by mass of the yellow pigment per 100 parts by mass of the halogenated zinc phthalocyanine pigment. The organic pigment derivative may be, for example, a derivative in which a part of a known organic pigment is modified (substituted) with a sulfonic acid group, a carboxyl group, an amino group, a phthalimide methyl group or the like. Specifically, for example, Solspace (registered trademark name) 5000, 12000, 22000 (manufactured by Ruble Sol Co., Ltd.) and the like can be mentioned.

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

The coloring composition further contains, as components other than the above, 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 and the like. May be.

The 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 resin, acrylic resin, polyamic acid resin, polyimide resin, styrene maleic acid resin, and styrene anhydride maleic acid resin, and for example, 1,6-hexane. Bifunctional monomers such as diol diacrylate, ethylene glycol diacrylate, neopentyl glycol diacrylate, triethylene glycol diacrylate, bis (acryloxyethoxy) bisphenol A, 3-methylpentanediol diacrylate, trimethyl propantriacrylate, penta Examples thereof include photopolymerizable monomers such as polyfunctional monomers such as erythritol triacrylate, tris- (2-acryloyloxyethyl) isocyanurate, dipentaerythritol hexaacrylate, and dipentaerythritol pentaacrylate.

The photosensitive coloring composition may further contain a photopolymerization initiator. Examples of the photopolymerization initiator include acetophenone, benzophenone, benzyldimethylketanol, benzoyl peroxide, 2-chlorothioxanthone, 1,3-bis (4'-azidobenzal) -2-propane, and 1,3-bis (4'). -Azidobenzal) -2-propane-2'-sulfonic acid, 4,4'-diazidostilbene-2,2'-disulfonic acid and the like can be mentioned.

The method for producing the photosensitive coloring composition is not particularly limited, but a dispersion liquid (coloring composition) using a halogenated zinc phthalocyanine pigment or a pigment composition containing the same, a solvent, and if necessary, a dispersant. Is generally prepared by adding a photosensitive compound or the like to the preparation. 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 liquid. 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.

When a yellow pigment for toning is used, for example, a dispersion liquid is prepared using a yellow pigment, a solvent, and a dispersant if necessary, and then a dispersion liquid containing a zinc halide phthalocyanine pigment is used. A photosensitive coloring composition may be prepared by mixing a dispersion liquid containing a yellow pigment and a photosensitive compound or the like. Further, a photosensitive compound or the like is added to a dispersion containing a zinc halide phthalocyanine pigment to prepare a composition for green toning, and a photosensitive compound or the like is added to a dispersion containing a yellow pigment to prepare a composition for yellow toning. A photosensitive coloring composition may be prepared by preparing a product and mixing the green toning composition and the yellow toning composition.

<Color filter>
The color filter of one embodiment has a pixel portion containing a zinc halide phthalocyanine pigment. The color filter typically has a red pixel portion, a blue pixel portion, and a green pixel portion. The pixel portion containing the halogenated zinc phthalocyanine pigment is preferably a green pixel portion. In this case, the thickness of the green pixel portion is, for example, 3.6 μm or less.

The pixel portion 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 the resin described as the resin contained in the pigment composition described above, and the preferred embodiment is also the same.

The pixel portion containing the halogenated zinc phthalocyanine pigment can be easily formed from the above-mentioned 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, and then the coating film is coated. Then, after performing pattern exposure with ultraviolet rays through a photomask, an unexposed portion is washed with an organic solvent, alkaline water, or the like to obtain a colored pattern, which is a method called photolithography. 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 PVED (photovoltaic electrolysis) method. Good.

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

Hereinafter, the content of the present invention will be described in more detail with reference to Examples and Comparative Examples, but the present invention is not limited to the following Examples.

<Synthesis of zinc halide phthalocyanine (crude pigment)>
[Synthesis Example 1]
Sulfril chloride (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) 90 g, aluminum chloride (manufactured by Kanto Chemical Co., Inc.) 109 g, sodium chloride (manufactured by Tokyo Chemical Industry Co., Ltd.) 15 g, zinc phthalocyanine (manufactured by DIC Co., Ltd.) 30 g in a 300 ml flask. And bromine (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) 69 g was charged. The temperature was raised to 80 ° C., the obtained mixture was taken out into water, filtered, washed with water, and dried to obtain zinc halide phthalocyanine (R1). Halogenated zinc phthalocyanine (R1) was subjected to fluorescent X-ray analysis using ZSX100E manufactured by Rigaku Co., Ltd., and average chlorine was obtained as a relative value per zinc atom from the mass ratio of zinc atom, chlorine atom and bromine atom. The number of atoms and the average number of bromine atoms were calculated. A sample obtained by pressure-molding (25 mmφ) of 1 g of zinc halide phthalocyanine was used as a measurement sample, and the measurement was performed in a vacuum atmosphere with a measurement diameter of 20 mmφ. As a result, in the halogenated zinc phthalocyanine (R1), the average number of halogen atoms in one molecule was 12.4, of which the average number of bromine atoms was 10.6 and the average number of chlorine atoms was 1.9. It was.

[Synthesis Example 2]
In a 300 ml flask, 70 g of sulfril chloride (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.), 105 g of aluminum chloride (manufactured by Kanto Chemical Co., Inc.), 14 g of sodium chloride (manufactured by Tokyo Chemical Industry Co., Ltd.), 27 g of zinc phthalocyanine (manufactured by DIC Co., Ltd.) And 52 g of bromine (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) were charged. The temperature was raised to 110 ° C., and the obtained mixture was taken out into water, filtered, washed with water, and dried to obtain zinc halide phthalocyanine (R2). For zinc phthalocyanine halogenated (R2), the average number of chlorine atoms and the average number of bromine atoms were calculated in the same manner as in Synthesis Example 1. In the halogenated zinc phthalocyanine (R2), the average number of halogen atoms in one molecule was 11.8, of which the average number of bromine atoms was 9.9 and the average number of chlorine atoms was 1.9.

[Synthesis Example 3]
In a 300 ml flask, 70 g of sulfril chloride (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.), 105 g of aluminum chloride (manufactured by Kanto Chemical Co., Inc.), 14 g of sodium chloride (manufactured by Tokyo Chemical Industry Co., Ltd.), 27 g of zinc phthalocyanine (manufactured by DIC Co., Ltd.) And 54 g of bromine (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) were charged. The temperature was raised to 80 ° C., the obtained mixture was taken out into water, filtered, washed with water, and dried to obtain zinc halide phthalocyanine (R3). For zinc halide phthalocyanine (R3), the average number of chlorine atoms and the average number of bromine atoms were calculated in the same manner as in Synthesis Example 1. In the halogenated zinc phthalocyanine (R3), the number of halogen atoms in one molecule was 11.4 on average, of which 10.2 was on average and the number of chlorine atoms was 1.2 on average.

[Synthesis Example 4]
In a 300 ml flask, 70 g of sulfril chloride (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.), 105 g of aluminum chloride (manufactured by Kanto Chemical Co., Inc.), 14 g of sodium chloride (manufactured by Tokyo Chemical Industry Co., Ltd.), 27 g of zinc phthalocyanine (manufactured by DIC Co., Ltd.) And 52 g of bromine (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) were charged. The temperature was raised to 80 ° C., the obtained mixture was taken out into water, filtered, washed with water, and dried to obtain zinc halide phthalocyanine (R4). For zinc halide phthalocyanine (R4), the average number of chlorine atoms and the average number of bromine atoms were calculated in the same manner as in Synthesis Example 1. In the halogenated zinc phthalocyanine (R4), the number of halogen atoms in one molecule was 10.4 on average, of which the average number of bromine atoms was 9.3 and the average number of chlorine atoms was 1.2.

[Synthesis Example 5]
In a 300 ml flask, 91 g of sulfril chloride (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.), 109 g of aluminum chloride (manufactured by Kanto Chemical Co., Inc.), 15 g of sodium chloride (manufactured by Tokyo Chemical Industry Co., Ltd.), 30 g of zinc phthalocyanine (manufactured by DIC Co., Ltd.) And 63 g of bromine (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) were charged. The temperature was raised to 130 ° C., and the obtained mixture was taken out into water, filtered, washed with water, and dried to obtain zinc halide phthalocyanine (R5). For zinc halide phthalocyanine (R5), the average number of chlorine atoms and the average number of bromine atoms were calculated in the same manner as in Synthesis Example 1. In the halogenated zinc phthalocyanine (R5), the average number of halogen atoms in one molecule was 13.0, of which the average number of bromine atoms was 10.3 and the average number of chlorine atoms was 2.7.

[Synthesis Example 6]
Sulfuryl chloride (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) 90 g, aluminum chloride (manufactured by Kanto Chemical Co., Inc.) 105 g, sodium chloride (manufactured by Tokyo Kasei Kogyo Co., Ltd.) 14 g, bromine (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) in a 300 ml flask. (Manufactured) 14 g was charged and mixed. After charging 22 g of zinc phthalocyanine (manufactured by DIC Corporation) and 136 g of bromine (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.), the temperature was raised to 50 ° C. and stirred for 2 hours. The obtained mixture was taken out into water, filtered, washed with water, and dried to obtain zinc halide phthalocyanine (R6). For zinc halide phthalocyanine (R6), the average number of chlorine atoms and the average number of bromine atoms were calculated in the same manner as in Synthesis Example 1. In zinc halide phthalocyanine (R6), the average number of halogen atoms in one molecule was 9.8, of which the average number of bromine atoms was 9.5 and the average number of chlorine atoms was 0.3.

<Example 1>
40 g of zinc halide phthalocyanine (R1), 400 g of pulverized sodium chloride and 63 g of diethylene glycol were charged into a dual-arm kneader and kneaded at 80 ° C. for 8 hours. After kneading, the obtained mixture was taken out into 2 kg of water at 80 ° C. After stirring for 1 hour, the mixture was filtered, washed with hot water, dried and pulverized to obtain a zinc halide phthalocyanine pigment (RP1) as a green pigment.

2.48 g of zinc halide phthalocyanine pigment (RP1), 1.24 g of BYK LPN-6919 (manufactured by BIC Chemie, trade name, solid content: 60% by mass), Unidic ZL-295 (manufactured by DIC Corporation, trade name, Solid content: 40% by mass) 1.86 g and 10.92 g of propylene glycol monomethyl ether acetate, using 0.3 to 0.4 mm zircon beads, dispersed for 2 hours with a paint shaker manufactured by Toyo Seiki Co., Ltd., and green. A pigment dispersion (RMG1) was obtained.

<Examples 2 to 4, Comparative Example 1>
Halogenated zinc phthalocyanine pigments (RP2) to (RP4) and (RP4) in the same manner as in Example 1 except that halogenated zinc phthalocyanines (R2) to (R5) were used instead of halogenated zinc phthalocyanines (R1). RP6) were obtained respectively.

The green pigment dispersion (RMG2) is the same as in Example 1 except that the halogenated zinc phthalocyanine pigments (RP2) to (RP4) and (RP6) are used instead of the halogenated zinc phthalocyanine pigment (RP1). ~ (RMG4) and (RMG6) were obtained, respectively.

<Example 5>
Halogenated zinc phthalocyanine (R3) 40 g, acrylic resin TS-1316 (manufactured by Seikou PMC Co., Ltd., trade name) 1.2 g, crushed sodium chloride 400 g and diethylene glycol 63 g were charged into a dual-arm kneader, and 8 at 80 ° C. Time kneaded. After kneading, the obtained mixture was taken out into 2 kg of water at 80 ° C. After stirring for 1 hour, the mixture is filtered, washed with hot water, dried and pulverized to obtain a green pigment composition (RG5) containing a halogenated zinc phthalocyanine pigment (RP5) coated with an acrylic resin (TS-1316). Got The content of the acrylic resin (TS-1316) was 3.0 parts by mass with respect to 100 parts by mass of the halogenated zinc phthalocyanine pigment (RP5).

A green pigment dispersion (RMG5) was obtained in the same manner as in Example 1 except that 2.48 g of the green pigment composition (RG5) was used instead of 2.48 g of the zinc halide phthalocyanine pigment (RP1).

<Example 6>
A halogenated zinc phthalocyanine pigment (RP7) was obtained in the same manner as in Example 1 except that the halogenated zinc phthalocyanine (R6) was used instead of the halogenated zinc phthalocyanine (R1).

A green pigment dispersion (RMG7) was obtained in the same manner as in Example 1 except that the halogenated zinc phthalocyanine pigment (RP7) was used instead of the halogenated zinc phthalocyanine pigment (RP1).

<Evaluation of color filter characteristics (1)>
(Preparation of evaluation composition (RCG))
To 4.0 g of green 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 are added to a paint shaker. By mixing with, an evaluation composition (RCG1) for evaluating the performance as a green pixel portion for a color filter was obtained. Further, the evaluation compositions (RCG2) to (RCG7) were used in the same manner as described above, except that the green pigment dispersions (RMG2) to (RMG7) were used instead of the green pigment dispersion (RMG1). Made.

(Preparation of evaluation board)
The evaluation compositions (RCG1) to (RCG7) were spin-coated on a soda glass substrate, dried at 90 ° C. for 3 minutes, and then heated at 230 ° C. for 1 hour. As a result, an evaluation glass substrate having a colored film on the soda glass substrate was produced. By adjusting the spin rotation speed at the time of spin coating, the film thickness of the colored film obtained by heating at 230 ° C. for 1 hour is adjusted, and the film thickness of the colored film is 1 for each Example and Comparative Example. An evaluation glass substrate having a thickness of 5.5 μm, an evaluation glass substrate having a colored film thickness of 1.9 μm, and an evaluation glass substrate having a colored film thickness of 2.4 μm were prepared. The film thickness was measured with a white interference microscope (VS1330) manufactured by Hitachi High-Tech Science Corporation.

(Evaluation)
For each evaluation glass substrate, the chromaticity (x, y) of the colored film in the C light source was measured using a spectrophotometer (U-3900) manufactured by Hitachi High-Tech Science Corporation. The results are shown in Table 2. Further, as shown in FIG. 1, the chromaticity (x, y) of the obtained colored film was plotted on the xy chromaticity coordinates in the XYZ color system of CIE. In FIG. 1, the chromaticity coordinate area A surrounded by the following equations (1) to (4), the xy chromaticity coordinate area B surrounded by the following equations (1) and (5) to (7), and the following equation are shown. The xy chromaticity coordinate region C surrounded by (1) and (8) to (10) is shown.
Equation (1): y = -1.766x + 0.628
(In the formula, x is 0.11 <x <0.17.)
Equation (2): y = 2.477x + 0.161
(In the formula, x is 0.11 <x <0.17.)
Equation (3): y = -3.498x + 1.177
(In the formula, x is 0.17 <x <0.21.)
Equation (4): y = 2.865x-0.159
(In the formula, x is 0.17 <x <0.21.)
Equation (5): y = 2.477x + 0.161
(In the formula, x is 0.11 <x <0.16.)
Equation (6): y = −3.583x + 1.131
(In the formula, x is 0.16 <x <0.20.)
Equation (7): y = 2.865x-0.159
(In the formula, x is 0.17 <x <0.20.)
Equation (8): y = 2.477x + 0.161
(In the formula, x is 0.11 <x <0.15.)
Equation (9): y = -3.680x + 1.085
(In the formula, x is 0.15 <x <0.19.)
Equation (10): y = 2.865x-0.159
(In the formula, x is 0.17 <x <0.19.)

<Evaluation of color filter characteristics (2)>
(Preparation of Toning Composition (TY))
C. I. Pigment Yellow 185 (BASF, Inc., Pariotor Yellow D1155) 1.65 g, DISPERBYK-161 (Big Chemie, solid content: 30% by mass) 3.85 g and propylene glycol monomethyl ether acetate 11.00 g Using 0.4 mm zircon beads, the mixture was dispersed in a paint shaker for 2 hours to obtain a yellow pigment dispersion (MY1). Paint by adding 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 to 4.0 g of the yellow pigment dispersion (MY1). The composition for toning (TY1) was obtained by mixing with a shaker.

(Preparation of evaluation composition (RDG))
Evaluation Compositions (RCG1) to (RCG7) are mixed with the toning composition (TY1), respectively, and the evaluation compositions (RDG1) to evaluate the performance as the green pixel portion for the color filter. (RDG7) was prepared. The blending ratio (TY: RCG, mass ratio) of the toning composition (TY) and the evaluation composition (RCG) is such that the chromaticity (x, y) in the C light source is (0.210, 0.670). It was adjusted so that a certain green pixel part could be obtained.

(Preparation of evaluation board)
The evaluation compositions (RDG1) to (RDG7) were spin-coated on a soda glass substrate and dried at 90 ° C. for 3 minutes. As a result, an evaluation glass substrate having a colored film having a chromaticity (x, y) of (0.210, 0.670) in the C light source on the soda glass substrate was produced. The chromaticity (x, y) was measured by a spectrophotometer (U-3900 manufactured by Hitachi High-Tech Science Corporation).

(Evaluation)
The brightness Y was measured with a spectrophotometer (U-3900) manufactured by Hitachi High-Tech Science Corporation, and the film thickness of the colored film was measured with a white interference microscope (VS1330) manufactured by Hitachi High-Tech Science Corporation. It can be said that the thinner the film thickness, the higher the coloring power. The results are shown in Table 3.

Since the zinc halide phthalocyanine pigment according to the present invention is excellent in brightness and coloring power, it can be suitably used for a color filter for high color reproduction.

Claims (3)

A zinc halide phthalocyanine pigment composed of a compound represented by the following formula (1).
The average number of halogen atoms in one molecule of the compound is 8 or more and 13 or less.
The average number of bromine atoms in one molecule of the compound is 11 or less.
A zinc halide phthalocyanine pigment having an average of less than two chlorine atoms in one molecule of the compound.

[In formula (1), X ^{1 to} X ¹⁶ each independently represent a hydrogen atom or a halogen atom. ] A coloring composition containing the zinc halide phthalocyanine pigment according to claim 1 and a solvent. A color filter having a pixel portion containing the zinc halide phthalocyanine pigment according to claim 1.

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