WO2020045199A1

WO2020045199A1 - Halogenated zinc phthalocyanine pigment, color composition and color filter

Info

Publication number: WO2020045199A1
Application number: PCT/JP2019/032704
Authority: WO
Inventors: 圭亮坂本; 健太郎大石; 英生海地; 望嶋田; 木村　亮
Original assignee: Dic株式会社
Priority date: 2018-08-31
Filing date: 2019-08-21
Publication date: 2020-03-05
Also published as: CN112601790A; JPWO2020045199A1; TWI828743B; JP6809649B2; CN112601790B; KR20210053893A; TW202016222A

Abstract

This halogenated zinc phthalocyanine pigment is composed of a compound represented by formula (1), wherein the number of halogen atoms in one molecule of the compound is 8 to 13 on average, the number of bromine atoms in one molecule of the compound is 11 or less on average, and the number of chlorine atoms in one molecule of the compound is less than 2 on average. [Chemical formula 1] [In formula (1), X¹-X¹⁶ each independently represent a hydrogen atom or a halogen atom.]

Description

Halogenated zinc phthalocyanine pigment, coloring composition and color filter

<< The present invention relates to a halogenated zinc phthalocyanine pigment, a coloring composition and a color filter.

A color filter is a member that realizes color display of a display by transmitting white light from a backlight. There is a demand for higher luminance and higher color reproduction for the green pixel portion of the color filter, and it is possible to conform to the standards of high color reproduction displays (Adobe RGB, DCI-P3, etc.) which are expected to spread. Color filters are being studied.

方法 As a method of realizing high color reproduction, for example, there is a method of increasing the thickness of a color filter. However, C.I. which is mainly used for display applications requiring high brightness is preferred. I. Pigment Green 58 and other halogenated zinc phthalocyanine pigments do not have sufficient tinting strength. Therefore, when these pigments are used in the green pixel portion, the thickness required for the pixel portion is large at the design chromaticity required by the above standard. It tends to be too much. For this reason, it is difficult to form a pixel portion sufficiently cured by exposure with the pigment, and a method of increasing the thickness of the color filter is not an effective method for achieving high color reproduction. For these reasons, for display applications that require high color reproducibility, a green pigment having a high tinting strength and a small thickness and capable of forming a sufficiently cured pixel portion is required.

As a result of the study of the present inventors, a halogenated zinc phthalocyanine pigment having a low halogenation rate has a high coloring power, and by using such a pigment, the standard of high color reproduction display (Adobe RGB, DCI- It has been clarified that a green pixel portion having a sufficiently small thickness can be formed even with the design chromaticity at P3 or the like. For example, Patent Document 1 discloses a halogenated zinc phthalocyanine 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 a color filter having high luminance and a wide color reproduction range can be provided by using the color filter.

WO 2015/118720 pamphlet

However, the above prior art has room for further improvement in terms of higher brightness.

Accordingly, an object of the present invention is to provide a zinc phthalocyanine halide pigment which is excellent in luminance and coloring power and is preferably used for a color filter for high color reproduction, and a colored composition and a color filter using the pigment. I do.

One aspect of the present invention is a halogenated zinc phthalocyanine pigment composed of a compound represented by the following formula (1), wherein the average number of halogen atoms in one molecule of the compound is 8 or more and 13 or less, The present invention relates to a zinc phthalocyanine pigment in which the number of bromine atoms in one molecule of the compound is 11 or less on average, and the number of chlorine atoms in one molecule of the compound is less than 2 on average.

[In the 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 as the number of moles of the pigment in the color filter increases, in other words, as the average molecular weight of the pigment decreases, the color development of the pigment increases. It has been considered excellent. Therefore, for example, the halogenated zinc phthalocyanine pigment described in Patent Literature 1 has been designed so that the average number of chlorine atoms having an atomic weight smaller than that of bromine atoms is two or more in order to reduce the average molecular weight. However, as a result of the study of the present inventors, surprisingly, when the number of bromine atoms is 11 or less on average, excellent brightness can be obtained by setting the number of chlorine atoms to less than 2 Was revealed.

That is, the halogenated zinc phthalocyanine pigment according to one aspect of the present invention has excellent coloring power and excellent brightness. Therefore, according to the above-mentioned halogenated zinc phthalocyanine pigment, the thickness is sufficiently thin even at the design chromaticity in the standard of high color reproduction display (Adobe RGB, DCI-P3, etc.), and high luminance is exhibited in the design chromaticity. A green pixel portion can be formed.

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

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

According to the present invention, it is possible to provide a halogenated zinc phthalocyanine pigment which is excellent in luminance and coloring power and is preferably 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 an area of a C light source in which the pigments of the examples and the comparative examples can reproduce color in a single color.

<Pigment and pigment composition>
In one embodiment, the halogenated zinc phthalocyanine pigment 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).

において 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 of the compound represented by the formula (1) to the number of molecules of the compound constituting the halogenated zinc phthalocyanine pigment is 8 or more and 13 or less. 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.

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

The present inventors presume the reason why the above effects can be obtained by the halogenated zinc phthalocyanine pigment of the present embodiment as follows. That is, in a halogenated zinc phthalocyanine pigment having a high halogenation rate, the presence of a halogen atom causes the surroundings of the molecule to be crowded, so that a three-dimensional effect greatly affects the absorption characteristics. Therefore, among the halogen atoms, the effect on the transmission spectrum of bromine atoms having a larger atomic radius than the chlorine atom is greater than the effect on the transmission spectrum of chlorine atoms. On the other hand, in the halogenated zinc phthalocyanine pigment having a low halogenation rate, the effect of the steric effect on the absorption characteristics is weakened, and the effect on the absorption characteristics of chlorine atoms, which has a higher electron-withdrawing property than bromine atoms, is reduced. Than the effect on the absorption characteristics of Therefore, if the number of bromine atoms is 11 or less on average and the number of chlorine atoms is 2 or more on average, there will be various compounds having different numbers and positions of substitution of chlorine atoms, resulting in a broad spectrum. Happens. As a result, it is presumed that the luminance of the halogenated zinc phthalocyanine pigment decreases and the tinting strength decreases. On the other hand, in the halogenated zinc phthalocyanine pigment of the present embodiment, since the number of chlorine atoms is less than 2, broadening of the spectrum as described above is suppressed, and it is presumed that excellent luminance and coloring power are 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, and more preferably 12 or less, from the viewpoint of further increasing the coloring power. Not more than The average of the number of halogen atoms is preferably 9 or more, more preferably 10 or more, from the viewpoint of obtaining more excellent luminance. The above upper limit and lower limit can be arbitrarily combined. For example, the average number of halogen atoms may be between 9 and 12.5 or between 10 and 12. In the following description, the upper limit and the lower limit individually described can be arbitrarily combined.

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

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

数 The number of the halogen atoms (for example, the number of bromine atoms and the number of chlorine atoms) can be measured by X-ray fluorescence 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 to each halogen atom in the halogenated zinc phthalocyanine pigment.

The halogenated zinc phthalocyanine pigment is composed of one or more particles. The average particle diameter (average primary particle diameter) of the primary particles of the halogenated zinc 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 halogenated zinc 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 an average value of the long diameters of the primary particles, and can be determined by measuring the long 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 halogenated zinc phthalocyanine pigment is 1.0 or more, 1.2 or more, 1.3 or more, 1.4 or 1.5 or 1.5 or more from the viewpoint of obtaining more excellent contrast. You may. The average aspect ratio of the primary particles of the halogenated zinc 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 primary particle aspect ratio 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. More preferably, it does not include primary particles having an aspect ratio of more than 3.

アスペクト The aspect ratio and average aspect ratio of the primary particles can be measured by the following method. First, particles in a visual field 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 present 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 value of the major axis and the minor axis for 40 primary particles is determined, and the ratio of the major axis to the minor axis is calculated using these values, and this is defined as the average aspect ratio. At this time, the sample zinc halide phthalocyanine pigment is ultrasonically dispersed in a solvent (for example, cyclohexane) and 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. And a method comprising:

(4) The step of forming a halogenated zinc phthalocyanine pigment may include a step of synthesizing a halogenated zinc phthalocyanine compound by a known production method such as a chlorosulfonic acid method, a halogenated phthalonitrile method, and a melting method.

As the chlorosulfonic acid method, there is 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 and halogenated. The reaction at this time is carried out, for example, at a temperature of 20 to 120 ° C. for 3 to 20 hours.

As the halogenated phthalonitrile method, for example, in addition to bromine, part or all of the hydrogen atoms of the aromatic ring, phthalic acid or phthalodinitrile substituted with a halogen atom such as chlorine, and a metal or metal salt of zinc are appropriately used. A method of synthesizing a corresponding zinc phthalocyanine compound using as a starting material can be mentioned. In this case, a catalyst such as ammonium molybdate may be used as necessary. The reaction at this time is performed, for example, at a temperature of 100 to 300 ° C. for 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, and alkaline earth metal halides (hereinafter referred to as alkali ( Halogenation of zinc phthalocyanine in a melt of about 10 to 170 ° C. consisting of one or a mixture of two or more kinds of compounds serving as solvents during various halogenations such as earth) metal halides) and thionyl chloride. And halogenation with an agent.

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

アルミニウム Alluminum 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 reduced, which is advantageous in operation. A preferred alkali (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 the aluminum halide within a range in which a molten salt is formed.

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

Halogenation temperature is preferably from 10 to 170 ° C, more preferably from 30 to 140 ° C. Further, pressurization can be performed to increase the reaction rate. The reaction time may be from 5 to 100 hours, preferably from 30 to 45 hours.

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

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

In any of the above methods, after completion of the reaction, the obtained mixture is poured into an acidic aqueous solution such as water or hydrochloric acid, and the generated zinc phthalocyanine halide compound is precipitated to obtain a crude zinc phthalocyanine pigment. Obtainable. As the crude halogenated zinc phthalocyanine pigment, it may be used as it is, but thereafter, filtered, washed with water or aqueous sodium hydrogen sulfate, aqueous sodium hydrogen carbonate, aqueous sodium hydroxide, and optionally acetone, toluene, methyl alcohol. It is preferable to use after washing with an organic solvent such as ethyl alcohol, dimethylformamide and the like, and performing post-treatments such as drying. The crude halogenated zinc phthalocyanine pigment may be used after dry grinding in a pulverizer such as an attritor, a ball mill, a vibration mill, a vibration ball mill, if necessary.

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

(4) In the step of converting the halogenated zinc phthalocyanine pigment into a pigment, for example, the crude halogenated zinc phthalocyanine pigment is kneaded and ground to obtain a halogenated zinc phthalocyanine pigment. The step of pigmentizing the halogenated zinc phthalocyanine pigment may be a step of kneading the crude zinc phthalocyanine pigment together with an inorganic salt and an organic solvent. The kneading can be performed using, for example, a kneader, a mix muller or the like.

水溶 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 pulverizing a usual inorganic salt.

(4) From the viewpoint that a pigment having an average primary particle diameter in the above-described range is easily obtained, it is preferable to increase the amount of the inorganic salt used relative to the amount of the crude pigment. Specifically, the amount of the inorganic salt used is preferably 5 to 20 parts by mass, more preferably 7 to 15 parts by mass, per 1 part by mass of the crude pigment.

An organic solvent 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 that can suppress crystal growth. As such an organic solvent, a water-soluble organic solvent can be suitably 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, etc. can be used. . The amount of the organic solvent (for example, water-soluble organic solvent) is not particularly limited, but is preferably 0.01 to 5 parts by mass relative to 1 part by mass of the crude pigment.

When an inorganic salt and an organic solvent are used, a mixture containing a halogenated zinc phthalocyanine pigment, an inorganic salt, and an organic solvent is obtained.The organic solvent and the inorganic salt are removed from the mixture, and if necessary, a zinc halide is used. Operations such as washing, filtration, drying, and pulverization may be performed on a solid material mainly containing a phthalocyanine pigment.

Washing or hot water washing can be used. The washing may be repeated 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 washing, alkali washing, and organic solvent washing may be performed.

Examples of the drying after the washing and filtration include batch or continuous drying in which the pigment is dehydrated and / or desolvated by heating at 80 to 120 ° C. using a heating source installed in a dryer. . The dryer generally includes a box dryer, a band dryer, a spray dryer, and the like. In particular, spray-drying using a spray drier is preferable because it can be easily dispersed at the time of preparing the paste. In addition, pulverization after drying is not an operation for increasing the specific surface area or reducing the average particle diameter of primary particles, for example, as in the case of drying using a box-type dryer or a band dryer. This is performed to dissolve the pigment and turn it into a powder when the pigment becomes a lamp shape or the like. For example, pulverization by a mortar, a hammer mill, a disc mill, a pin mill, a jet mill or the like can be mentioned.

では In the above method, when the crude pigment is converted into a pigment, a resin may coexist. By coexisting the resin during pigmentation, the active surface (active growth surface) of the particles is stabilized by the resin. As a result, the deviation in the direction of particle growth is reduced, and 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 halogenated zinc phthalocyanine pigment is obtained as a mixture with a resin 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 of coexisting the resin, the step of pigmenting the crude halogenated zinc phthalocyanine pigment may be a step of kneading the crude halogenated zinc phthalocyanine pigment with the resin. It may be a step of kneading with an organic solvent.

When using an inorganic salt and an organic solvent, as described 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, Then, operations such as washing, filtration, drying, and pulverization may be performed on a solid material mainly composed of a halogenated zinc phthalocyanine pigment and a resin.

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), when the resin has the acidic group, a pigment having a small average aspect ratio of 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 a better contrast is easily obtained.

The resin contains one or more kinds of polymers. Examples of the polymer include a vinyl polymer. The vinyl polymer contains a monomer having a vinyl group (vinyl monomer) as a monomer unit. The vinyl polymer preferably has an acidic group, and more preferably has a carboxyl group, from the viewpoint of more easily obtaining excellent contrast.

Examples of vinyl monomers include (meth) acrylate monomers, styrene monomers, vinyl ether monomers, nitrogen-containing monomers, (halogen-substituted) hydrocarbon monomers, and the like. In the present specification, “(meth) acrylate” means at least one of acrylate and methacrylate corresponding thereto. The vinyl polymer preferably contains a (meth) acrylate monomer as a monomer unit among vinyl monomers. That is, the vinyl polymer is preferably a (meth) acrylate polymer.

Examples of the (meth) acrylate monomer include methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, iso-propyl (meth) acrylate, n-butyl (meth) acrylate, and sec-butyl. (Meth) 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) A) acrylate, 2-ethylhexyl (meth) 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 (meth) acrylate, cycloheptyl (meth) acrylate, cyclooctyl (meth) acrylate, cyclo Nonyl (meth) acrylate, isodecyl (meth) acrylate, cyclodecyl (meth) acrylate, benzyl (meth) acrylate, phenyl (meth) acrylate, phenoxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, nonylphenoxy polyethylene glycol (meth) ) Acrylate, neopentyl glycol benzoate (meth) acrylate, paracumylphenoxyethylene glycol (meth) acrylate, 2-hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, 3-phenoxy-2-hydroxypropyl (meth) acrylate , Neopentyl glycol benzoate (meth) acrylate, phenylphenol (meth) acrylate, phenoxydiethylene Glycol (meth) acrylate, nonylphenoxyethyl (meth) acrylate, naphthyl (meth) acrylate, glycidyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate glycidyl ether, 3,4-epoxycyclohexylmethyl (meth) acrylate, 3 , 4-epoxybutyl (meth) acrylate, 4,5-epoxypentyl (meth) acrylate, 6,7-epoxypentyl (meth) acrylate, β-methylglycidyl (meth) acrylate and the like.

モノマー The polymer may include one or more monomers as monomer units. For example, the polymer may include a (meth) acrylate-based monomer and another vinyl-based monomer different from the (meth) acrylate-based monomer as monomer units. That is, the polymer may be a copolymer of a (meth) acrylate-based monomer and another vinyl-based monomer. The other vinyl monomer may be a monomer having an acidic group, for example, (meth) acrylic acid. Other vinyl monomers include, for example, nitro group-containing vinyl monomers such as (meth) acrylonitrile, vinyl aromatic monomers such as styrene and α-methylstyrene, (meth) acrylamide, N, N-dimethylacrylamide, Vinyl monomers containing an amide group such as N-isopropylacrylamide, N-methylol (meth) acrylamide, dimethylol (meth) acrylamide or diacetoneacrylamide, N-methoxymethyl (meth) acrylamide, or N-butoxymethyl (meth) acrylamide , Such as ethylene, propylene, or isoprene, diene, such as chloroprene or butadiene, methyl vinyl ether, ethyl vinyl ether, and n-propyl vinyl. Vinyl ethers such as ether, isopropyl vinyl ether, n-butyl vinyl ether or isobutyl vinyl ether; vinyl fatty acids such as vinyl acetate or vinyl propionate; 3- (meth) allyloxy-2-hydroxypropanesulfonic acid; 2- (meth) Allyloxyethylene sulfonic 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 sulfone Acid, 4- (allyloxy) benzenesulfonic acid, 1-methyl-2-propene-1-sulfonic acid, 1,1-dimethyl-2-propene-1-sulfonic acid, 3-butene-1-sulfonic acid, 1- Butene-3-sulfonic acid, 2-acrylic Mido-1-methylpropanesulfonic acid, 2-acrylamidopropanesulfonic acid, 2-acrylamido-n-butanesulfonic acid, 2-acrylamido-2-phenylpropanesulfonic acid, 2-((meth) acryloyloxy) ethanesulfonic acid, etc. May be unsaturated sulfonic acids.

The content of the (meth) acrylate-based monomer in the vinyl-based polymer is selected from the viewpoint of exhibiting high transparency, which is an advantage of the (meth) acrylate-based polymer, to such an extent that the luminance of the color filter is not reduced. It is preferably 90% by mass or more, and may be 92% by mass or more or 94% by mass or more based on the mass of all the monomer units contained in the union. The content of the (meth) acrylate-based monomer in the vinyl-based polymer is determined by considering the disadvantages of the (meth) acrylate-based polymer in that the heat resistance is compensated by another vinyl-based monomer. 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.

含有 The content of the vinyl polymer in the resin may be 90% by mass or more, or may be 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, and may be 100% by mass based on the total mass of the resin.

(4) The acid value of the resin is preferably 50 mgKOH / g or more, more preferably 70 mgKOH / g or more, and still more preferably 90 mgKOH / g or more, from the viewpoint of easily obtaining superior 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 polymer, the acid value of the vinyl polymer may be in the above range, and the acid value of the (meth) acrylate polymer may be in the above range.

The acid value was determined by preparing a sample solution prepared by dissolving pg of resin and 1 ml of phenolphthalein test solution in 50 ml of a mixed solution of toluene and ethanol at a volume ratio of 1: 1. Titration was performed with a potassium solution (a solution prepared by dissolving 7.0 g of potassium hydroxide in 5.0 ml of distilled water and adding 1,000 vol by adding 95 vol% ethanol) until the sample liquid became pink, and calculated by the following equation. it can.
Acid value = q × r × 5.611 / p
In the formula, q indicates the titer (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. And p represents the mass (g) of the resin.

(4) The weight average molecular weight of the resin is preferably 4000 or more, and may be 8000 or more, 10000 or more, or 15,000 or more from the viewpoint of preventing volatilization during heating at around 200 ° C. in the display manufacturing process. The weight average molecular weight of the resin may be 20,000 or less, 18,000 or less, or 17000 or less from the viewpoint of efficiently covering the pigment surface. When the resin contains a vinyl polymer, the weight average molecular weight of the vinyl polymer may be in the above range, and the weight average molecular weight of the (meth) acrylate polymer may be in the above range. The weight average molecular weight is a weight average molecular weight in terms of polystyrene measured by gel permeation chromatography.

ガラス 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 securing developability and easily obtaining industrial raw materials. 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 may be in the above range. Is also good. The glass transition temperature (Tg) can be measured by thermal differential analysis (DSC).

From these viewpoints, a resin containing a vinyl polymer having a carboxyl group and having an acid value of 50 mgKOH / g or more is preferable. The gel permeation chromatograph contains a (meth) acrylate-based monomer in an amount of 90% by mass or more based on the mass of all monomer units contained in the vinyl-based polymer and a (meth) acrylate-based polymer having an acidic group. A resin having a polystyrene equivalent weight average molecular weight of 4,000 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 with respect to 100 parts by mass of the crude pigment, from the viewpoint that the pigment can be sufficiently coated and the contrast is more easily improved, and 0.5 parts by mass or more. Parts or more, 1.0 parts by weight or more, or 1.5 parts by weight or more. The amount of the resin used is preferably 10 parts by mass or less based on 100 parts by mass of the crude pigment, from the viewpoint of easily obtaining a pigment having better coloring power and improving the contrast more easily. 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, 1.0 to 3 parts by mass with respect to 100 parts by mass of the crude pigment. It is 0.5 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.

顔料 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 halogenated zinc phthalocyanine pigment. In this case, the halogenated zinc phthalocyanine pigment is preferably completely covered with the resin, but a part of the pigment may not be covered with the resin. That is, when the halogenated zinc phthalocyanine pigment is coated with a resin, the halogenated zinc phthalocyanine pigment only needs to include particles at least partially coated with the resin, and only from particles completely coated with the resin. It may be composed of only particles partially covered with a resin and partially exposed, or a mixture thereof. Further, in the halogenated zinc phthalocyanine pigment, there may be particles that are not completely covered with the resin.

The coating resin may be the above-mentioned resin used for producing a halogenated zinc phthalocyanine pigment. The content of the coating resin in the pigment composition is preferably 0.1 parts by mass or more with respect to 100 parts by mass of the halogenated zinc phthalocyanine pigment, from the viewpoint of further improving the contrast, and more preferably 0.5 part by mass. As described above, the amount 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 based on 100 parts by mass of the halogenated zinc phthalocyanine pigment, from the viewpoints of being more excellent in coloring power and facilitating improvement of contrast. It may be 3.0 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 halogenated zinc phthalocyanine pigment. 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 phthalocyanine halide pigment and coating resin. Other components include, for example, known phthalocyanine derivatives. Other components may be added, for example, in the step of forming a crude pigment together with a resin, or may be added after obtaining a zinc phthalocyanine halide pigment.

The pigment composition does not substantially contain a solvent and is, for example, a solid (eg, a powder). 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 colored composition that is a pigment dispersion can be formed.

The halogenated zinc phthalocyanine pigment described above and the pigment composition containing the same have a specificity not in a yellowish hue but in a bluish hue as in the conventional high-halogenated zinc phthalocyanine pigment, Highly halogenated zinc phthalocyanine pigments can express hues that could not be achieved. For example, when a halogenated zinc phthalocyanine pigment is formed into a coating film having a film thickness of 1.5 μm to 2.4 μm, the following formula (XYZ color system) of CIE when colorimetrically measured using a C light source alone is used. An xy chromaticity coordinate area surrounded by 1) to (4) can be displayed. More preferably, an xy chromaticity coordinate area surrounded by the following equations (1) and (5) to (7) can be displayed. Yes, and more preferably, an xy chromaticity coordinate area 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 a halogenated zinc phthalocyanine pigment (when the halogenated zinc phthalocyanine pigment is coated with the coating resin, the total amount of the halogenated zinc phthalocyanine pigment and the coating resin is 2.48 g) was transferred to BYK-LPN6919 (by BYK-Chemie). With 1.24 g of Unidick ZL-295 (manufactured by DIC Corporation, trade name, solid content: 40% by mass) and 10.92 g of propylene glycol monomethyl ether acetate. The dispersion is performed using zircon beads of 0.3 to 0.4 mm for 2 hours to obtain a pigment dispersion. To 4.0 g of the obtained pigment dispersion, 0.98 g of Unidick 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 mixture was added with a paint shaker. A coating liquid is obtained by mixing. 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 a value measured using, for example, a spectrophotometer (U-3900) manufactured by Hitachi High-Tech Science Corporation.

Formula (1): y = -1.766x + 0.628
(Where x is 0.11 <x <0.17.)
Formula (2): y = 2.477x + 0.161
(Where x is 0.11 <x <0.17.)
Formula (3): y = −3.498x + 1.177
(Where x is 0.17 <x <0.21)
Formula (4): y = 2.865x−0.159
(Where x is 0.17 <x <0.21)

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

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

The halogenated zinc phthalocyanine pigment of the present embodiment and the pigment composition containing the same can be used for known and common uses, and for color filters, paints, plastics, printing inks, rubber, leather, textile printing, electronic toner, and jets. Suitable for coloring ink, thermal transfer ink, etc. Among them, it is suitably used as a green pigment and a green pigment composition for a color filter, particularly a green pigment and a green pigment composition used for a green pixel portion of the color filter.

As described above, the halogenated zinc phthalocyanine pigment of this embodiment has an average of 8 to 13 halogen atoms, an average of 11 or less bromine atoms, and an average of 2 chlorine atoms. Since it is less than 1, the coloring power is excellent and the luminance is also excellent. Therefore, the halogenated zinc 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 achieved. Even with a design chromaticity according to the display standard (Adobe RGB, DCI-P3, etc.), a green pixel portion having sufficiently small thickness and high luminance can be formed.

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

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

The coloring composition may further contain a resin (coating resin) for coating the halogenated zinc 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 above-described pigment composition, and the preferred embodiment is also the same.

有機 As the solvent, an organic solvent is preferable. Examples of the organic solvent include aromatic solvents such as toluene, xylene, and methoxybenzene; ethyl acetate, butyl acetate; acetate solvents such as propylene glycol monomethyl ether acetate; propylene glycol monoethyl ether acetate; and ethoxyethyl propionate. Propionate solvents, alcohol solvents such as methanol and ethanol, ether solvents such as butyl cellosolve, propylene glycol monomethyl ether, diethylene glycol ethyl ether, diethylene glycol dimethyl ether, ketone solvents such as methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, and fats such as hexane Group hydrocarbon solvents, N, N-dimethylformamide, γ-butyrolactam, N-methyl-2-pyrrolidone, aniline Emissions, nitrogen compound-based solvent such as pyridine, a lactone-based solvents such as γ- butyrolactone, carbamic acid esters such as a mixture of 48:52 of methyl carbamate and ethyl carbamate acid. 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. is there.

The content of the solvent may be 300 parts by mass or more, or 1000 parts by mass or less, based on 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 halogenated zinc phthalocyanine pigment, an organic dye, an organic pigment derivative, and the like, in consideration of economy. As the organic pigment, a green halogenated metal phthalocyanine pigment such as a known and commonly used green halogenated copper phthalocyanine and other green halogenated different metal phthalocyanine pigments can be used. Further, a yellow pigment for toning may be used. Examples of the yellow pigment include C.I. I. And yellow organic pigments such as CI Pigment Yellow 83, 110, 129, 138, 139, 150, 180, 185, and 231. The combination 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 phthalimidomethyl group, or the like. Specifically, for example, Solsperse (registered trademark) 5000, 12000 and 22000 (manufactured by Lubrizol 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 dispersing agent include 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 Co., Ltd.) , EFKA (registered trademark) 46, 47, 4010, 4020, 4320, 430 4330, 4401, 4570, 5054, 7461, 7462, 7476, 7777 (manufactured by BASF), Azispar (registered trademark) PB814, 821, 822, 881 (Ajinomoto Fine Technos), Solsperse (registered trademark) 24000, 28000, 37500, and 76500 (manufactured by Lubrizol). The content of the dispersant may be 5 parts by mass or more and 120 parts by mass or less based on 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.

着色 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 resin, acrylic resin, polyamic acid resin, polyimide resin, styrene maleic acid resin, and styrene maleic anhydride resin, and 1,6-hexane, for example. Bifunctional monomers such as diol diacrylate, ethylene glycol diacrylate, neopentyl glycol diacrylate, triethylene glycol diacrylate, bis (acryloxyethoxy) bisphenol A, 3-methylpentanediol diacrylate, trimethylolpropane triacrylate, pentane Multifunctional monomers such as erythritol triacrylate, tris- (2-acryloyloxyethyl) isocyanurate, dipentaerythritol hexaacrylate, dipentaerythritol pentaacrylate Such as a photopolymerizable monomer, such as mers and the like.

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.

The method for producing the photosensitive coloring composition is not particularly limited, but a dispersion (coloring composition) using a halogenated zinc phthalocyanine pigment or a pigment composition containing the same, a solvent and, if necessary, a dispersant is used. Is generally prepared by adding a photosensitive compound or the like thereto after 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 based on 100 parts by mass of the dispersion liquid. The content of the photopolymerization initiator may be 0.05 parts by mass or more and 3 parts by mass or less based on 1 part by mass of the photosensitive resin.

When using a yellow pigment or the like for toning, for example, a yellow pigment, a solvent, and a dispersant, if necessary, to prepare a dispersion using a dispersion containing a halogenated zinc phthalocyanine pigment, A photosensitive coloring composition may be prepared by mixing a dispersion containing a yellow pigment with a photosensitive compound or the like. In addition, a photosensitive compound or the like is added to a dispersion containing a halogenated zinc 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 phthalocyanine halide pigment. The color filter typically has a red pixel portion, a blue pixel portion, and a green pixel portion. The pixel section containing the halogenated zinc phthalocyanine pigment is preferably a green pixel section. 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 included in the above-described pigment composition, and the preferred embodiment is also the same.

The pixel portion containing the 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 on a transparent substrate such as a glass substrate by a spin coating method, a roll coating method, an ink jet method, or the like, and then the coating film is applied. Then, after performing pattern exposure with ultraviolet rays through a photomask, a method called photolithography, in which an unexposed portion is washed with an organic solvent, alkaline water, or the like to obtain a colored pattern, is used. The method for forming the pixel portion is not particularly limited. For example, a pattern of the pixel portion is formed by a method such as an electrodeposition method, a transfer method, a micelle electrolysis method, a PVED (Photovoltaic Electrodeposition) method, and a color filter is manufactured. Good.

画素 Other pixel portions (for example, a red pixel portion and a blue pixel portion) can be formed by a similar method using a known pigment.

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 halogenated zinc phthalocyanine (crude pigment)>
[Synthesis Example 1]
In a 300 ml flask, 90 g of sulfuryl chloride (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.), 109 g of aluminum chloride (manufactured by Kanto Chemical Co., Ltd.), 15 g of sodium chloride (manufactured by Tokyo Chemical Industry Co., Ltd.), and 30 g of zinc phthalocyanine (manufactured by DIC Corporation) And 69 g of bromine (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.). The temperature was raised to 80 ° C., and the obtained mixture was taken out in water, filtered, washed with water, and dried to obtain a zinc phthalocyanine halide (R1). The halogenated zinc phthalocyanine (R1) was subjected to fluorescent X-ray analysis using ZSX100E manufactured by Rigaku Corporation, and the average chlorine as a relative value per zinc atom was determined from the mass ratio of zinc, chlorine and bromine atoms. The number of atoms and the average number of bromine atoms were calculated. In addition, 1 g of halogenated zinc phthalocyanine was subjected to pressure molding (25 mmφ) as a measurement sample, which was measured under 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. Was.

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

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

[Synthesis Example 4]
In a 300 ml flask, 70 g of sulfuryl chloride (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.), 105 g of aluminum chloride (manufactured by Kanto Chemical Co., Ltd.), 14 g of sodium chloride (manufactured by Tokyo Chemical Industry Co., Ltd.), and 27 g of zinc phthalocyanine (manufactured by DIC Corporation) And 52 g of bromine (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.). The temperature was raised to 80 ° C., and the obtained mixture was taken out in water, filtered, washed with water, and dried to obtain a zinc phthalocyanine halide (R4). About halogenated zinc 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 average number of halogen atoms in one molecule was 10.4, 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 sulfuryl chloride (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.), 109 g of aluminum chloride (manufactured by Kanto Chemical Co., Ltd.), 15 g of sodium chloride (manufactured by Tokyo Chemical Industry Co., Ltd.), and 30 g of zinc phthalocyanine (manufactured by DIC Corporation) And 63 g of bromine (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.). The temperature was raised to 130 ° C., and the obtained mixture was taken out into water, filtered, washed with water and dried to obtain a zinc phthalocyanine halide (R5). About halogenated zinc 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]
In a 300 ml flask, 90 g of sulfuryl chloride (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.), 105 g of aluminum chloride (manufactured by Kanto Chemical Co., Ltd.), 14 g of sodium chloride (manufactured by Tokyo Chemical Industry Co., Ltd.), and bromine (Fujifilm Wako Pure Chemical Industries, Ltd.) Was mixed and charged. 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 the mixture was stirred for 2 hours. The obtained mixture was taken out into water, filtered, washed with water, and dried to obtain a zinc phthalocyanine halide (R6). About halogenated zinc 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. The halogenated zinc phthalocyanine (R6) had an average of 9.8 halogen atoms in one molecule, an average of 9.5 bromine atoms and an average of 0.3 chlorine atoms in one molecule.

<Example 1>
40 g of zinc phthalocyanine halide (R1), 400 g of pulverized sodium chloride and 63 g of diethylene glycol were charged into a double-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 phthalocyanine halide (RP1) as a green pigment.

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

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

A green pigment dispersion (RMG2) was prepared in the same manner as in Example 1 except that the halogenated zinc phthalocyanine pigments (RP1) were replaced by halogenated zinc phthalocyanine pigments (RP2) to (RP4) and (RP6). ~ (RMG4) and (RMG6) were obtained respectively.

<Example 5>
40 g of halogenated zinc phthalocyanine (R3), 1.2 g of acrylic resin TS-1316 (trade name, manufactured by Seiko PMC Co., Ltd.), 400 g of pulverized sodium chloride and 63 g of diethylene glycol were charged into a double-arm kneader. Kneaded for 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 green pigment composition (RG5) containing a zinc phthalocyanine pigment (RP5) coated with an acrylic resin (TS-1316). I got The content of the acrylic resin (TS-1316) was 3.0 parts by mass based on 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 phthalocyanine halide 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 (R1) was used instead of the halogenated zinc phthalocyanine (R1).

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

<Evaluation of color filter characteristics (1)>
(Preparation of composition for evaluation (RCG))
0.98 g of Unidick ZL-295 (manufactured by DIC, trade name, solid content: 40% by mass) and 0.22 g of propylene glycol monomethyl ether acetate were added to 4.0 g of a green pigment dispersion (RMG1), and a paint shaker was added. To obtain an evaluation composition (RCG1) for evaluating the performance as a green pixel portion for a color filter. The evaluation compositions (RCG2) to (RCG7) were prepared 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). Produced.

(Preparation of evaluation substrate)
Each of the evaluation compositions (RCG1) to (RCG7) was spin-coated on a soda glass substrate, dried at 90 ° C. for 3 minutes, and then heated at 230 ° C. for 1 hour. Thus, a glass substrate for evaluation having a colored film on a soda glass substrate was produced. In addition, the thickness of the colored film obtained by heating at 230 ° C. for 1 hour was adjusted by adjusting the number of spin rotations at the time of spin coating. An evaluation glass substrate having a thickness of 0.5 μm, an evaluation glass substrate having a color film thickness of 1.9 μm, and an evaluation glass substrate having a color film thickness of 2.4 μm were produced. The film thickness was measured with a white interference microscope (VS1330) manufactured by Hitachi High-Tech Science Corporation.

(Evaluation)
For each glass substrate for evaluation, 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. Table 2 shows the results. Further, as shown in FIG. 1, the chromaticity (x, y) of the obtained colored film was plotted on xy chromaticity coordinates in the CIE XYZ color system. FIG. 1 shows a chromaticity coordinate area A surrounded by the following equations (1) to (4), an xy chromaticity coordinate area B surrounded by the following equations (1) and (5) to (7), The xy chromaticity coordinate area C surrounded by (1) and (8) to (10) is shown.
Formula (1): y = -1.766x + 0.628
(Where x is 0.11 <x <0.17.)
Formula (2): y = 2.477x + 0.161
(Where x is 0.11 <x <0.17.)
Formula (3): y = −3.498x + 1.177
(Where x is 0.17 <x <0.21)
Formula (4): y = 2.865x−0.159
(Where x is 0.17 <x <0.21)
Formula (5): y = 2.477x + 0.161
(In the formula, x is 0.11 <x <0.16.)
Formula (6): y = −3.583x + 1.131
(Where x is 0.16 <x <0.20)
Formula (7): y = 2.865x−0.159
(Where x is 0.17 <x <0.20)
Formula (8): y = 2.477x + 0.161
(In the formula, x is 0.11 <x <0.15.)
Formula (9): y = −3.680x + 1.085
(In the formula, x is 0.15 <x <0.19.)
Formula (10): y = 2.865x−0.159
(Where x is 0.17 <x <0.19.)

<Evaluation of color filter characteristics (2)>
(Preparation of Toning Composition (TY))
C. I. Pigment Yellow 185 (Paliotol Yellow D1155, manufactured by BASF) in an amount of 0.35 g together with 3.85 g of DISPERBYK-161 (manufactured by Big Chemie, solid content: 30% by mass) and 11.00 g of propylene glycol monomethyl ether acetate. Using 0.4 mm zircon beads, the mixture was dispersed with a paint shaker for 2 hours to obtain a yellow pigment dispersion (MY1). To 4.0 g of the yellow pigment dispersion (MY1), 0.98 g of Unidick 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, followed by painting. A toning composition (TY1) was obtained by mixing with a shaker.

(Preparation of composition for evaluation (RDG))
Each of the evaluation compositions (RCG1) to (RCG7) is mixed with the toning composition (TY1) to evaluate the performance as a green pixel portion for a color filter (RDG1) to (RDG7) was prepared. The compounding 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). Adjustments were made to obtain a certain green pixel portion.

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

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

ハロゲン The halogenated zinc phthalocyanine pigment according to the present invention is excellent in luminance and coloring power, and thus can be suitably used for a color filter for high color reproduction.

Claims

A halogenated zinc 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 number of bromine atoms in one molecule of the compound is 11 or less on average;
The halogenated zinc phthalocyanine pigment, wherein the number of chlorine atoms in one molecule of the compound is less than 2 on average.

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