JP2019038958A - Chlorinated brominated zinc phthalocyanine pigment and color filter containing the same - Google Patents

Abstract

To provide a green pigment for color filters that has high contrast and can achieve an NTSC ratio of 90% or more with a practical thickness, and has a wide color reproduction range, and a color filter containing the pigment.SOLUTION: The present invention provides a chlorinated brominated zinc phthalocyanine pigment, wherein, at least one H of two H on a 6 membered aromatic ring C atom directly bonded to a 5 membered heterocycle is substituted with Cl, and at least one of remaining H on a phthalocyanine skeleton is substituted with Br, and a color filter containing the same in a pixel unit.SELECTED DRAWING: Figure 1

Description

  The present invention relates to a chlorinated brominated zinc phthalocyanine pigment and a color filter containing the same.

  A color filter used in a liquid crystal display is a member that realizes color display of a display by transmitting white light of a backlight. As a display standard for liquid crystal displays, sRGB is the mainstream, but in recent years, DCI-P3 and BT2020 standards showing high color reproducibility have attracted attention as displays capable of displaying more realistic images. A DCI-P3 or BT2020 standard display requires a color filter with a wide color reproduction range, and in recent years, especially for a green colorant for a green color filter, an expansion of the color reproduction range is required.

  Up to now, pigment green 36 and pigment green 58 that can efficiently transmit white light of a backlight have been used as green colorants for color filters for the purpose of saving energy and reducing manufacturing costs of displays. On the other hand, in order to expand the color reproduction range using these pigments, it is necessary to increase the pigment concentration in the coating film or to increase the thickness of the coating film. It is impossible to achieve more than%. Therefore, Pigment Green 7 and Pigment Green 59 having high coloring power are selected as main pigments for expanding the color reproduction range. This is because when the pigment green 7 or the pigment green 59 is used, a thin film with a specific chromaticity can be obtained. For example, it has been proposed to form a green pixel using a green photosensitive resin composition containing Pigment Green 7 and Pigment Yellow 185, and achieve high color reproduction with a thin film of 2.2 μm or less. However, Pigment Green 7 and Pigment Green 59 have a problem in that the contrast, which is one of important performances as a color filter, is reduced due to the formation of coarse particles. In view of the above, there is a demand for color materials for color filters that have high color reproducibility and good contrast.

  As means for solving the above-mentioned problem, in order to provide a green pigment with strong yellowness and high brightness, it is obtained by first chlorinating the phthalocyanine skeleton and secondly brominating the chlorinated phthalocyanine skeleton. A composition of a chlorinated brominated phthalocyanine skeleton-containing compound has been proposed (Cited document 1). However, even in the compound described in the cited document 1, color reproducibility and contrast are not sufficient, and further improvement is desired.

JP2007-291232A

  An object of the present invention is to provide a color filter pigment having a high contrast and a wide color reproduction range, and a color filter comprising the same.

In order to create a color filter pigment having a high contrast and a wide color reproduction range, the present inventors have focused on the number of chlorine atoms substituting at the α-positions of four aromatic rings in the phthalocyanine skeleton. As a result of the synthesis, the inventors have found that a specific chlorinated brominated zinc phthalocyanine pigment described later can solve the above-mentioned problems, and have completed the present invention.
That is, the present invention provides the following general formula (1):

(In the general formula (1), Z ^{1 to} Z ¹⁶ each independently represent a chlorine atom, a bromine atom or a hydrogen atom,
At least one of Z ¹ and Z ⁴ is a chlorine atom,
At least one of Z ⁵ and Z ⁸ is a chlorine atom,
At least one of Z ⁹ and Z ¹² is a chlorine atom,
(At least one of Z ¹³ and Z ¹⁶ is a chlorine atom, and at least one of Z ^{1 to} Z ¹⁶ is a bromine atom)
And a chlorinated brominated zinc phthalocyanine pigment represented by the formula (hereinafter sometimes referred to as the chlorinated brominated zinc phthalocyanine pigment of the present invention).
The present invention also relates to a color filter having the above-described chlorinated brominated zinc phthalocyanine pigment of the present invention in a pixel portion.
Moreover, this invention relates to the chlorinated brominated zinc phthalocyanine compound represented by the said General formula (1).

Here, the difference in expression between “chlorinated brominated zinc phthalocyanine pigment” and “chlorinated brominated zinc phthalocyanine compound” in the present specification will be described.
“Chlorinated brominated zinc phthalocyanine pigments” are those specially designed for coloring applications, and those that have been surface-treated by solvent salt milling, etc., and “chlorinated brominated zinc phthalocyanine compounds” are physical properties. In order to express the chemical structure itself regardless of the expression, it is described separately.

  According to the present invention, a color filter with high contrast can be provided.

It is a figure which shows the xy chromaticity coordinate area | region which can express the pigment of this invention in the XYZ color system of CIE.

The chlorinated brominated zinc phthalocyanine pigment of the present invention is a pigment represented by the general formula (1).
In the above description of the substituent, “at least one of Z ¹ and Z ⁴ is a chlorine atom”, “at least one of Z ⁵ and Z ⁸ is a chlorine atom”, “at least one of Z ⁹ and Z ¹² is chlorine” “Atom” and “At least one of Z ¹³ and Z ¹⁶ is a chlorine atom” means that there are four aromatic rings in the formula, but at least one chlorine atom is introduced at the α-position of each aromatic ring. The chlorinated brominated zinc phthalocyanine pigment.

  Here, if further explained, it goes without saying to those skilled in the art, but there are two α positions per aromatic ring in the formula, and there are a total of eight positions in the phthalocyanine skeleton. The expression “introduced at least one chlorine atom at the α-position of each aromatic ring” as used herein refers to a structure having the following structure, for example.

  The chlorinated brominated zinc phthalocyanine pigment in the present invention is a pigment obtained as a result of bromination using the chlorinated zinc phthalocyanine as a raw material. At this time, at least one of hydrogen atoms on the aromatic ring is a bromine atom. Is replaced.

  In addition, the chlorinated brominated zinc phthalocyanine pigment in the present invention is different from the pigment described in Reference 1 in terms of the number of chlorine atoms substituted on the aromatic ring in the phthalocyanine skeleton and the total halogenation rate. is there.

Among the chlorinated brominated zinc phthalocyanine pigments of the present invention, in the present invention, a coating film composed of 1.25 parts of resin per 1 part of pigment is converted into a film thickness of 1.2 μm to 2.5 μm. When formed,
In the XYZ color system of CIE when color measurement is performed using a C light source alone,
Being a pigment capable of displaying the xy chromaticity coordinate region surrounded by the following formulas (2) to (5),
It is preferable from the viewpoint of showing high contrast.
Formula (2)
y = 2.874x + 0.025
(However, in the formula, x is 0.12 <x <0.20.)
Formula (3)
y = −0.6667x + 0.45
(In the formula, x is 0.12 <x <0.18.)
Formula (4)
y = 2x-0.03
(However, in the formula, x is 0.18 <x <0.24.)
Formula (5)
y = -3.75x + 1.35
(In the formula, x is 0.20 <x <0.24.)

Furthermore, in the present invention, among the chlorinated brominated zinc phthalocyanine pigments satisfying the above relationship, in the XYZ color system of CIE described above, the xy chromaticity coordinate region surrounded by the following formulas (6) to (9) Is more preferable from the viewpoint of achieving both high color reproducibility and high contrast as color filter characteristics.
Formula (6)
y = 3.2x-0.058
(However, in the formula, x is 0.14 <x <0.19.)
Formula (7)
y = −0.6667x + 0.4833
(However, in the formula, x is 0.14 <x <0.185.)
Formula (8)
y = 2x-0.01
(Where x is 0.185 <x <0.22).
Formula (9)
y = -4x + 1.31
(However, in the formula, x is 0.19 <x <0.22.)
In order to display the xy chromaticity coordinate region, for example, a method of adjusting the average halogenation ratio z of the chlorinated brominated zinc phthalocyanine compound can be mentioned. At this time, the average halogenation rate is an average of the total number of chlorine atoms and bromine atoms substituted per molecule of the chlorinated brominated zinc phthalocyanine compound. For example, a range of 5 ≦ z ≦ 16 There is a method of making chlorinated brominated zinc phthalocyanine. In the present invention, it is preferable to adjust to the range of 10.3 ≦ z ≦ 13.7 from the viewpoint of showing high contrast, and further, adjusting to the range of 11.0 ≦ z ≦ 13.0 is preferable. It is more preferable from the viewpoint of achieving both reproducibility and high contrast.

  The crystallinity of chlorinated brominated zinc phthalocyanine pigments having various halogen substitution numbers and halogen substitution positions was confirmed by XRD measurement. As a result, the chlorination rate at the α-position was high as in the chlorinated brominated zinc phthalocyanine pigment of the present invention. It was found that the spectrum of the pigment becomes broader (the crystallinity becomes lower), while the spectrum of the pigment having a high β-position chlorination rate becomes sharper (the crystallinity becomes higher). Therefore, it is speculated that as the number of chlorine introduced at the α-position increases, the growth of pigment particles is suppressed, the pigment particles become amorphous, and such fine pigment particles can improve the contrast. .

  The method for producing the chlorinated brominated zinc phthalocyanine compound of the present invention is not particularly limited. For example, the following method can easily control the number of chlorine atoms and bromine atoms substituted on the aromatic ring. It is suitable.

The chlorinated brominated zinc phthalocyanine compound of the present invention is obtained by preparing chlorinated zinc phthalocyanine in which at least one α-position of each aromatic ring is chlorinated in advance and brominating it by a known and conventional method. Can do.
This is a method for controlling the halogen substitution position and the number of substitutions utilizing the fact that chlorine is not eliminated even after a bromination step in halogenation of a phthalocyanine compound, which is relatively difficult to control. Therefore, the position and number of substituted chlorine atoms depend on chlorinated zinc phthalocyanine prepared in advance (hereinafter sometimes referred to as raw material phthalocyanine), and can be easily changed by changing the amount of bromine atom added in the bromination step. Can be adjusted. In order to obtain the object of the present invention, as a matter of course from the description of the structure and substituent of the above formula (1), the raw material phthalocyanine is chlorinated at one or more α positions of each aromatic ring, As is clear from the definition of (1), it is possible to use one that leaves room for substitution of one or more bromine atoms. Such raw material phthalocyanine can be easily obtained from chlorinated phthalic anhydride in accordance with the target product.

  Here, the substitution positions and the number of chlorine atoms and bromine atoms in the obtained chlorinated brominated zinc phthalocyanine of the present invention are described in, for example, JP-A-2007-291232 (described above Patent Document 1) and JP-A-2010-189527. It can be obtained by this method. Specific examples include a mass spectrometry method, a fluorescent X-ray method, a method of specifying from the composition of the raw material, a method of specifying from the composition of the decomposition product, and the like.

  Regardless of which method is used, the obtained chlorinated brominated zinc phthalocyanine compound of the present invention is produced by introducing the resulting mixture into an aqueous acidic solution such as water or hydrochloric acid after completion of the reaction. Brominated zinc phthalocyanine precipitates. The precipitated chlorinated brominated zinc phthalocyanine may be used as it is, but is then filtered, washed with water or sodium hydrogensulfate water, sodium hydrogen carbonate water, sodium hydroxide water, acetone, toluene, methyl as necessary. It is preferably used after washing with an organic solvent such as alcohol, ethyl alcohol, dimethylformamide, and after-treatment such as drying.

  The chlorinated brominated zinc phthalocyanine compound of the present invention is dry-ground in a pulverizer such as an attritor, ball mill, vibration mill, vibration ball mill, etc., if necessary, and then pigmented by a solvent salt milling method or a solvent boiling method. By doing so, a pigment which is excellent in dispersibility and coloring power and has a high lightness before the pigmentation can be obtained.

  There is no particular limitation on the method of pigmenting the chlorinated brominated zinc phthalocyanine compound of the present invention. For example, the chlorinated brominated zinc phthalocyanine compound before pigmentation may be dispersed in a dispersion medium and pigmented at the same time. Adopts solvent salt milling treatment because it can easily suppress crystal growth and obtain pigment particles with a large specific surface area compared to solvent treatment in which a chlorinated brominated zinc phthalocyanine compound is heated and stirred in a large amount of organic solvent. It is preferable to do this.

  This solvent salt milling means kneading and grinding a crude pigment, which is chlorinated brominated zinc phthalocyanine that has not undergone pigmentation, ground immediately after synthesis, or after that, an inorganic salt, and an organic solvent. To do. In this case, it is preferable to use the latter crude pigment. Specifically, a crude pigment, an inorganic salt, and an organic solvent that does not dissolve it are charged into a kneader and kneaded and ground therein. As a kneader at this time, for example, a kneader, a mix muller, or the like can be used.

  As the inorganic salt, a water-soluble inorganic salt can be preferably used. For example, an inorganic salt such as sodium chloride, potassium chloride, sodium sulfate is preferably used. Moreover, it is more preferable to use an inorganic salt having an average particle size of 0.5 to 50 μm. Such an inorganic salt can be easily obtained by pulverizing a normal inorganic salt.

  In the present invention, a chlorinated brominated zinc phthalocyanine pigment having an average primary particle size of 0.01 to 0.10 μm is preferably used for color filter applications. In obtaining the above-mentioned preferable chlorinated brominated zinc phthalocyanine pigment in the present invention, it is preferable to increase the amount of inorganic salt used relative to the amount of crude pigment used in solvent salt milling. That is, 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, it is preferable to use an organic solvent capable of suppressing crystal growth, and as such an organic solvent, a water-soluble organic solvent can be suitably used. For example, diethylene glycol, glycerin, ethylene glycol, propylene glycol, liquid polyethylene Glycol, liquid polypropylene glycol, 2- (methoxymethoxy) ethanol, 2-butoxyethanol, 2- (isopentyloxy) ethanol, 2- (hexyloxy) ethanol, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, tri Ethylene glycol, triethylene glycol monomethyl ether, 1-methoxy-2-propanol, 1-ethoxy-2-propanol, dipropylene glycol Calls, can be used dipropylene glycol monomethyl ether. Although the usage-amount of the said water-soluble organic solvent is not specifically limited, 0.01-5 mass parts is preferable with respect to 1 mass part of crude pigments.

  In the method for producing a chlorinated brominated zinc phthalocyanine pigment of the present invention, only the crude pigment may be subjected to solvent salt milling, but the solvent salt milling is performed by using chlorinated brominated zinc phthalocyanine in combination with a phthalocyanine derivative or a quinophthalone derivative. You can also The phthalocyanine derivative may be added at the time of synthesizing the crude pigment or after pigmentation, but is more preferably added before the pigmentation step such as solvent salt milling. By adding a phthalocyanine derivative, it is possible to improve the viscosity characteristics and the dispersion stability of the color filter resist ink.

  As such a phthalocyanine derivative, any known and commonly used phthalocyanine derivative can be used, but a phthalocyanine pigment derivative represented by the following general formula (10) or (11) is preferable. The phthalocyanine derivative is preferably a halogenated zinc phthalocyanine or a phthalocyanine derivative corresponding to the raw material zinc phthalocyanine, but when used in combination, it is a small amount, so a halogenated copper phthalocyanine derivative or a copper phthalocyanine derivative should be used. You can also.

Formula (10) P- (Y) m

Formula (11) P- (AZ) n

(In the formula, P represents a residue obtained by removing n hydrogens of an unsubstituted or halogenated phthalocyanine ring having no central metal or having a central metal. Y represents a primary to tertiary amino group or a carboxylic acid group. Represents a sulfonic acid group or a salt thereof with a base or a metal, A is a divalent linking group, Z is a residue obtained by removing at least one hydrogen on the nitrogen atom of the primary or secondary amino group, or (Represents a residue obtained by removing at least one hydrogen on a nitrogen atom of a heterocyclic ring containing nitrogen, and m represents 1 to 4 and n represents 1 to 4).

The central metal is Zn, and examples of the primary and secondary amino groups include a monomethylamino group, a dimethylamino group, and a diethylamino group. Examples of the base or metal that forms a salt with the carboxylic acid group or sulfonic acid group include ammonia, organic bases such as dimethylamine, diethylamine, and triethylamine, and metals such as potassium, sodium, calcium, strontium, and aluminum. As the divalent linking group for A, for example, a divalent linking group such as an alkylene group having 1 to 3 carbon atoms, —CO ₂ —, —SO ₂ —, —SO ₂ NH (CH ₂ ) a—, etc. Groups. Examples of Z include a phthalimide group, a monoalkylamino group, and a dialkylamino group. a represents the length of the alkyl chain and is an integer of 1 to 3.

The phthalocyanine derivative that can be included in the crude pigment during the preparation of the crude pigment and / or during solvent salt milling is usually 0.01 to 0.3 parts by mass per 1 part by mass of the crude pigment. In addition, when using a phthalocyanine derivative at the time of crude pigment preparation and / or solvent salt milling, the total amount of the crude pigment and the phthalocyanine derivative is regarded as the usage amount of the crude pigment, and the usage amount of the inorganic salt is as described above. Select from a range.
30-150 degreeC is preferable and the temperature at the time of solvent salt milling has more preferable 80-100 degreeC. The solvent salt milling time is preferably 5 hours to 20 hours, more preferably 8 to 18 hours.

  Thus, a mixture containing a chlorinated brominated zinc phthalocyanine pigment, an inorganic salt, and an organic solvent as a main component having an average primary particle diameter of 0.01 to 0.10 μm is obtained. From this mixture, an organic solvent and an inorganic salt are mixed. The powder of the chlorinated brominated zinc phthalocyanine pigment can be obtained by removing, if necessary, and washing, filtering, drying, pulverizing, etc. the solid material mainly composed of the chlorinated brominated zinc phthalocyanine pigment.

  As washing described above, either water washing or hot water washing can be employed. The number of washings can be repeated in the range of 1 to 5 times. In the case of the mixture using a water-soluble inorganic salt and a water-soluble organic solvent, the organic solvent and the inorganic salt can be easily removed by washing with water. If necessary, acid cleaning, alkali cleaning, and organic solvent cleaning may be performed so as not to change the crystal state.

  Examples of the drying after filtration and washing described above include batch-type or continuous drying in which the pigment is dehydrated and / or desolvated by heating at 80 to 120 ° C. with a heating source installed in a dryer. Examples of the dryer generally include a box dryer, a band dryer, and a spray dryer. In particular, spray dry drying is preferable because it is easily dispersed during paste preparation. In addition, the pulverization after drying is not an operation for increasing the specific surface area or reducing the average particle diameter of the primary particles, but for example, the pigment is a lamp as in the case of drying using a box dryer or a band dryer. When it becomes a shape or the like, it is performed to break the pigment into powder, and examples thereof include mortar, hammer mill, disk mill, pin mill, jet mill and the like. Thus, a dry powder containing the chlorinated brominated zinc phthalocyanine pigment of the present invention as a main component is obtained.

  The chlorinated brominated zinc phthalocyanine pigment of the present invention can be used for any known and commonly used applications, but since the average particle diameter of primary particles is 0.01 to 0.10 μm, pigment aggregation is relatively weak, Dispersibility in a synthetic resin to be colored becomes better.

  In addition, when the chlorinated brominated zinc phthalocyanine pigment of the present invention is used in a color filter green pixel portion, the pigment dispersion in the color filter photosensitive composition is easy, and the color filter photosensitive composition is used. The 365 nm photocuring sensitivity frequently used for curing does not decrease, and film edge and pattern flow during development are less likely to occur. A color filter green pixel portion having both high contrast and color reproducibility required in recent years can be obtained more easily.

  When the primary and horizontal aspect ratios of the chlorinated brominated zinc phthalocyanine pigment of the present invention are 1 to 3, the viscosity characteristics are improved in each application field and the fluidity is higher. In order to obtain the aspect ratio, first, as in the case of obtaining the average particle diameter of the primary particles, the particles in the field of view are photographed with a transmission electron microscope or a scanning electron microscope. Then, an average value of the longer diameter (major axis) and the shorter diameter (minor axis) is obtained for 50 primary particles constituting the aggregate on the two-dimensional image, and the average value is calculated using these values. .

  The color filter of the present invention can be obtained by incorporating the chlorinated brominated zinc phthalocyanine pigment of the present invention into at least the green pixel portion of the color filter.

  The spectral transmission spectrum in the present invention is obtained according to the first-class spectrophotometer of Japanese Industrial Standard JIS Z 8722 (color measurement method-reflective and transmissive object color). The resin film containing the pigment formed into a dry film thickness is obtained by plotting each transmittance value at each wavelength by scanning and irradiating light in a predetermined wavelength region.

  The color filter containing the chlorinated brominated zinc phthalocyanine pigment of the present invention in the green pixel portion can transmit the green bright line of the light source well when using a light source such as white light or F10, and is chlorinated. Since the spectral transmission spectrum of the brominated zinc phthalocyanine pigment is sharp, green color purity and coloring power can be expressed to the maximum.

  The chlorinated brominated zinc phthalocyanine pigment of the present invention can be used as it is for the production of the green pixel portion of the color filter. However, if necessary, in consideration of economy, a known and commonly used green halogenated copper phthalocyanine or Other green halogenated metal phthalocyanine pigments such as green halogenated different metal phthalocyanine pigments may be used in combination.

  Examples of the green halogenated metal phthalocyanine that can be used in combination with the chlorinated brominated zinc phthalocyanine pigment of the present invention include C.I. I. Pigment Green 7, 36, 58, 59, 62, 63 and the like.

  Chlorinated brominated zinc phthalocyanine pigment in the present invention: known and commonly used green halogenated metal phthalocyanine pigment (mass ratio) = 100: 0 to 80:20, preferably 100: 0 to 90:10.

  In addition to the green pigment, a yellow pigment may be used for toning to develop characteristics. Examples of yellow pigments that can be used here include C.I. I. And yellow organic pigments such as CI Pigment Yellow 83, 110, 129, 138, 139, 150, 180, 185, and 231. The combined ratio of the chlorinated brominated zinc phthalocyanine pigment and the yellow pigment of the present invention is 10 to 200 parts by mass of the yellow pigment per 100 parts by mass of the chlorinated brominated zinc phthalocyanine pigment.

  In addition, when the chlorinated brominated zinc phthalocyanine pigment of the present invention is used, even when a yellow pigment is used together for toning, compared to the conventional case where two or more different color pigments are mixed for toning. Thus, the color filter green pixel portion can be obtained with little turbidity, excellent color purity and coloring power, and a bright color filter.

  For example, conventional C.I. I. In the case of using a yellow pigment in combination with the chlorinated brominated zinc phthalocyanine pigment of the present invention, compared to the case of using a mixed pigment in which the above-mentioned yellow pigment is used in combination with a green pigment such as CI Pigment Green 7 or 36, Since the color purity and coloring power are high, the decrease in brightness is smaller and the amount of light transmitted in the green region is larger.

  The chlorinated brominated zinc phthalocyanine pigment of the present invention can be used for forming a pattern of a green pixel portion of a color filter by a known method. Typically, a photosensitive composition for a color filter green pixel portion containing the chlorinated brominated zinc phthalocyanine pigment of the present invention and a photosensitive resin as essential components can be obtained.

  As a method for producing a color filter, for example, after dispersing this chlorinated brominated zinc phthalocyanine pigment in a dispersion medium made of a photosensitive resin, glass or the like by a spin coating method, a roll coating method, a slit coating method, an ink jet method or the like. A method called photolithography, in which a green pattern is obtained by applying an ultraviolet ray through a photomask to the coated film and then washing the unexposed portion with a solvent or the like. Is mentioned.

  In addition, a color filter may be manufactured by forming a pattern of the green pixel portion by a method such as an electrodeposition method, a transfer method, a micellar electrolysis method, or a PVED (Photovoltaic Electrodeposition) method.

  To prepare a photosensitive composition for a color filter green pixel portion, for example, the chlorinated brominated zinc phthalocyanine pigment of the present invention, a photosensitive resin, a photopolymerization initiator, and an organic solvent that dissolves the resin. Mix as an essential ingredient. As a production method thereof, a method is generally used in which a dispersion is prepared using a chlorinated brominated zinc phthalocyanine pigment, an organic solvent and a dispersant as required, and then a photosensitive resin is added thereto. is there.

  As the chlorinated brominated zinc phthalocyanine pigment here, a chlorinated brominated zinc phthalocyanine pigment which may or may not contain the phthalocyanine derivative, and a yellow pigment as necessary can be used.

  Examples of the dispersant used as needed include Disperbyk (DISPERBYK®) 130, 161, 162, 163, 170, 170, LPN-6919, LPN-21116, etc. manufactured by Big Chemie. In addition, a leveling agent, a coupling agent, a cationic surfactant, and the like can be used together.

  Examples of the organic solvent include aromatic solvents such as toluene, xylene, and methoxybenzene, acetate solvents such as ethyl acetate and butyl acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, and ethoxyethyl propionate. Propionate solvents such as alcohol solvents such as methanol and ethanol, ether solvents such as butyl cellosolve, propylene glycol monomethyl ether, diethylene glycol ethyl ether and diethylene glycol dimethyl ether, ketone solvents such as methyl ethyl ketone, methyl isobutyl ketone and cyclohexanone, and fats such as hexane Group hydrocarbon solvents, N, N-dimethylformamide, γ-butyrolactam, N-methyl-2-pyrrolidone, ani 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, there is water. As the organic solvent, polar solvents such as propionate-based, alcohol-based, ether-based, ketone-based, nitrogen compound-based, lactone-based, water and the like that are water-soluble are particularly suitable.

  300 to 1000 parts by mass of an organic solvent, and optionally 0 to 100 parts by mass of a dispersant and / or 0 to 20 parts by mass of a phthalocyanine derivative per 100 parts by mass of the chlorinated brominated zinc phthalocyanine pigment of the present invention. The dispersion can be obtained by stirring and dispersing so as to be uniform. Next, 3 to 20 parts by weight of the photosensitive resin per 100 parts by weight of the chlorinated brominated zinc phthalocyanine pigment, 0.05 to 3 parts by weight of a photopolymerization initiator per 1 part by weight of the photosensitive resin are necessary for this dispersion. In accordance with the above, an organic solvent is further added, and the mixture is stirred and dispersed to be uniform, whereby a photosensitive composition for a color filter green pixel portion can be obtained.

  Examples of photosensitive resins that can be used in this case include urethane resins, acrylic resins, polyamic acid resins, polyimide resins, styrene maleic acid resins, styrene maleic anhydride resins, and the like, Bifunctional monomers such as 1,6-hexanediol diacrylate, ethylene glycol diacrylate, neopentyl glycol diacrylate, triethylene glycol diacrylate, bis (acryloxyethoxy) bisphenol A, 3-methylpentanediol diacrylate, Such as trimethylolpropane triacrylate, pentaerythritol triacrylate, tris (2-hydroxyethyl) isocyanate, dipentaerythritol hexaacrylate, dipentaerythritol pentaacrylate, etc. Photopolymerizable monomer such as a polyfunctional monomer UNA and the like.

  Examples of the photopolymerization initiator include acetophenone, benzophenone, benzyldimethyl ketal, benzoyl peroxide, 2-chlorothioxanthone, 1,3-bis (4′-azidobenzal) -2-propane, 1,3-bis (4′- Azidobenzal) -2-propane-2′-sulfonic acid, 4,4′-diazidostilbene-2,2′-disulfonic acid, and the like.

  The thus-prepared photosensitive composition for green color pixel portion of the color filter becomes a color filter by performing pattern exposure with ultraviolet rays through a photomask and then washing the unexposed portion with an organic solvent or alkaline water. Can do.

  The chlorinated brominated zinc phthalocyanine pigment of the present invention has a bluish green color and high coloring power, and develops a bright green color with high color purity and high contrast. Therefore, it is suitable for coloring paints, plastics, printing inks, rubber, leather, textile printing, electronic toners, jet inks, thermal transfer inks and the like in addition to the color filters described in detail.

  Furthermore, the chlorinated brominated zinc phthalocyanine compound of the present invention can be applied to uses such as organic semiconductor materials and near infrared absorbers for laser welding utilizing strong near infrared absorption.

  Next, the present invention will be specifically described with reference to examples. Hereinafter, unless otherwise indicated,% means mass%, and part means mass part.

Synthesis Example 1 (Synthesis of α-tetrachlorozinc phthalocyanine)
A 1 L flask was charged with 111 g of 3-chlorophthalic anhydride, 20 g of zinc chloride, 116 g of urea, 600 mg of hexaammonium hexamolybdate tetrahydrate and 250 g of sulfolane, and stirred at 190 ° C. for 5 hours. Thereafter, the heating was stopped, the mixture was allowed to cool, filtered, and washed with 780 g of 2-propanol, 1000 g of 1% aqueous sodium hydroxide, and 1000 g of 1% hydrochloric acid. After washing with water, the obtained wet cake was dried at 90 ° C. for 12 hours to obtain blue solid α-tetrachlorozinc phthalocyanine (38 g).

Synthesis Example 2 (Synthesis of α-Cl ₄ [1])
In a 200 mL flask, 54 g of sulfuryl chloride (Wako Pure Chemical Industries), 63 g of aluminum chloride (Kanto Chemical), 8.6 g of sodium chloride (Tokyo Chemical Industry), α-tetrachlorozinc phthalocyanine obtained in Synthesis Example 1 18.6 g and bromine (Wako Pure Chemical Industries, Ltd.) 33 g were charged. The temperature was raised to 80 ° C., after removal of water, filtered, washed with water and dried, to obtain a chlorinated brominated zinc phthalocyanine _{(α-Cl 4 [1]} ). α-Cl ₄ [1] means “α-” indicates α-position, and chlorine atoms are introduced at α-position (one chlorine atom is introduced at each α-position of each aromatic ring). Zinc phthalocyanine, and the numbers in [] are numbers for convenience. These also have the same meaning in the following synthesis examples and examples.
Mass spectrometry was performed on chlorinated brominated zinc phthalocyanine (α-Cl ₄ [1]) by JMS-S3000 manufactured by JEOL Ltd., and it was confirmed that the average halogenation rate was 10.5. Note that the delay time at the time of mass spectrometry was 300 ns, and the laser intensity was 38%. 40 g of chlorinated brominated zinc phthalocyanine (α-Cl ₄ [1]), 400 g of crushed 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, it was taken out in 2 kg of water at 80 ° C., stirred for 1 hour, filtered, washed with hot water, dried and pulverized to obtain a green pigment composition (G1).

Synthesis Example 3 (Synthesis of α-Cl ₄ [2])
Synthesis was performed in the same manner as in Synthesis Example 2 except that the amount of bromine added was changed to 42 g, to obtain chlorinated brominated zinc phthalocyanine (α-Cl ₄ [2]). Chlorinated brominated zinc phthalocyanine (α-Cl ₄ [2]) was subjected to mass spectrometry using JMS-S3000 manufactured by JEOL Ltd., and it was confirmed that the average halogenation rate was 11.7. In addition, the delay time at the time of mass spectrometry was 275 ns, and the laser intensity was 38%. 40 g of chlorinated brominated zinc phthalocyanine (α-Cl ₄ [2]), 400 g of crushed 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, it was taken out in 2 kg of 80 ° C. water, stirred for 1 hour, filtered, washed with hot water, dried and pulverized to obtain a green pigment composition (G2).

Synthesis Example 4 (Synthesis of α-Cl ₄ [3])
Synthesis was performed in the same manner as in Synthesis Example 2 except that the amount of bromine added was changed to 50 g, to obtain chlorinated brominated zinc phthalocyanine (α-Cl ₄ [3]). Chlorinated brominated zinc phthalocyanine (α-Cl ₄ [3]) was subjected to mass spectrometry using JMS-S3000 manufactured by JEOL Ltd., and it was confirmed that the average halogenation rate was 12.2. In addition, Delaytime at the time of mass spectrometry was 275 ns, and Laser Intensity was 40%. 40 g of chlorinated brominated zinc phthalocyanine (α-Cl ₄ [3]), 400 g of crushed 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, it was taken out in 2 kg of water at 80 ° C., stirred for 1 hour, filtered, washed with hot water, dried and pulverized to obtain a green pigment composition (G3).

Synthesis Example 5 (Synthesis of α-Cl ₄ [4])
Synthesis was performed in the same manner as in Synthesis Example 2 except that the amount of bromine added was changed to 55 g, to obtain chlorinated brominated zinc phthalocyanine (α-Cl ₄ [4]). Chlorinated brominated zinc phthalocyanine (α-Cl ₄ [4]) was subjected to mass spectrometry using JMS-S3000 manufactured by JEOL Ltd., and it was confirmed that the average halogenation rate was 12.0. In addition, Delaytime at the time of mass spectrometry was 200 ns, and Laser Intensity was 38%. 40 g of chlorinated brominated zinc phthalocyanine (α-Cl ₄ [4]), 400 g of crushed 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, it was taken out in 2 kg of 80 ° C. water, stirred for 1 hour, filtered, washed with hot water, dried and pulverized to obtain a green pigment composition (G4).

Synthesis Example 6 (Synthesis of α-Cl ₄ [5])
Synthesis was performed in the same manner as in Synthesis Example 2 except that the amount of bromine added was changed to 62 g, to obtain chlorinated brominated zinc phthalocyanine (α-Cl ₄ [5]). Chlorinated brominated zinc phthalocyanine (α-Cl ₄ [5]) was subjected to mass spectrometry using JMS-S3000 manufactured by JEOL Ltd., and it was confirmed that the average halogenation rate was 12.7. In addition, Delaytime at the time of mass spectrometry was 260 ns, and Laser Intensity was 38%. 40 g of chlorinated brominated zinc phthalocyanine (α-Cl ₄ [5]), 400 g of crushed 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, it was taken out in 2 kg of 80 ° C. water, stirred for 1 hour, filtered, washed with hot water, dried and pulverized to obtain a green pigment composition (G5).

Synthesis Example 7 (Synthesis of α-Cl ₄ [6])
The synthesis was performed in the same manner as in Synthesis Example 2 except that the amount of bromine added was changed to 104 g to obtain chlorinated brominated zinc phthalocyanine (α-Cl ₄ [6]). Chlorinated brominated zinc phthalocyanine (α-Cl ₄ [6]) was subjected to mass spectrometry using JMS-S3000 manufactured by JEOL Ltd., and it was confirmed that the average halogenation rate was 13.5. In addition, Delaytime at the time of mass spectrometry was 275 ns, and Laser Intensity was 41%. 40 g of chlorinated brominated zinc phthalocyanine (α-Cl ₄ [6]), 400 g of crushed 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, it was taken out in 2 kg of 80 ° C. water, stirred for 1 hour, filtered, washed with hot water, dried and pulverized to obtain a green pigment composition (G6).

Synthesis Example 8 (Synthesis of β-tetrachlorozinc phthalocyanine)
A 1 L flask was charged with 111 g of 4-chlorophthalic anhydride, 20 g of zinc chloride, 116 g of urea, 600 mg of hexaammonium hexamolybdate tetrahydrate and 250 g of sulfolane and stirred at 190 ° C. for 5 hours. Thereafter, the heating was stopped, the mixture was allowed to cool, filtered, and washed with 780 g of 2-propanol, 1000 g of 1% aqueous sodium hydroxide, and 1000 g of 1% hydrochloric acid. After washing with water, the obtained wet cake was dried at 90 ° C. for 12 hours to obtain blue solid β-tetrachlorozinc phthalocyanine (41 g).

Synthesis Example 9 (Synthesis of β-Cl ₄ )
In a 200 mL flask, 54 g of sulfuryl chloride (Wako Pure Chemical Industries, Ltd.), 63 g of aluminum chloride (Kanto Chemical), 8.6 g of sodium chloride (Tokyo Chemical Industry), β-tetrachlorozinc phthalocyanine obtained in Synthesis Example 8 18.6 g and bromine (Wako Pure Chemical Industries, Ltd.) 33 g were charged. The temperature was raised to 80 ° C., after removal of water, filtered, washed with water to obtain a chlorinated brominated zinc phthalocyanine (β-Cl ₄₎ by drying. Chlorinated brominated zinc phthalocyanine (β-Cl ₄ ) was subjected to mass spectrometry using JMS-S3000 manufactured by JEOL Ltd., and it was confirmed that the average halogenation rate was 13.1. In addition, the Delaytime at the time of mass spectrometry was 300 ns, and Laser Intensity was 39%. 40 g of chlorinated brominated zinc phthalocyanine (β-Cl ₄ ), 400 g of crushed 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, it was taken out in 2 kg of 80 ° C. water, stirred for 1 hour, filtered, washed with hot water, dried and pulverized to obtain a green pigment composition (G7).

Synthesis Example 10 (Synthesis of α-dichlorozinc phthalocyanine)
A 1 L flask was charged with 55 g of 3-chlorophthalic anhydride, 45 g of phthalic anhydride, 20 g of zinc chloride, 116 g of urea, 600 mg of hexaammonium hexamolybdate tetrahydrate and 250 g of sulfolane, and stirred at 190 ° C. for 5 hours. Thereafter, the heating was stopped, the mixture was allowed to cool, filtered, and washed with 780 g of 2-propanol, 1000 g of 1% aqueous sodium hydroxide, and 1000 g of 1% hydrochloric acid. After washing with water, the obtained wet cake was dried at 90 ° C. for 12 hours to obtain blue solid α-dichlorozinc phthalocyanine (22 g).

Synthesis Example 11 (Synthesis of α-Cl ₂ )
In a 200 mL flask, 54 g of sulfuryl chloride (Wako Pure Chemical Industries), 63 g of aluminum chloride (Kanto Chemical), 8.6 g of sodium chloride (Tokyo Chemical Industry), α-dichlorozinc phthalocyanine 16 obtained in Synthesis Example 10 above. .8 g and bromine (Wako Pure Chemical Industries, Ltd.) 41 g were charged at different addition amounts. The temperature was raised to 80 ° C., after removal of water, filtered, washed with water to obtain a chlorinated brominated zinc phthalocyanine (α-Cl ₂₎ followed by drying. Mass spectrometry was performed on chlorinated brominated zinc phthalocyanine (α-Cl ₂ ) using JMS-S3000 manufactured by JEOL Ltd., and it was confirmed that the average halogenation rate was 11.7. In addition, Delaytime at the time of mass spectrometry was 280 ns, and Laser Intensity was 41%. 40 g of chlorinated brominated zinc phthalocyanine (α-Cl ₂ ), 400 g of crushed 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, it was taken out in 2 kg of 80 ° C. water, stirred for 1 hour, filtered, washed with hot water, dried and pulverized to obtain a green pigment composition (G8).

Synthesis Example 12 (Synthesis of R1)
In a 300 mL flask, 90 g of sulfuryl chloride (Wako Pure Chemical Industries Reagent), 105 g of aluminum chloride (Kanto Chemical Reagent), 14 g of sodium chloride (Tokyo Chemical Industry Reagent), 27 g of zinc phthalocyanine from DIC Corporation, bromine (Wako Pure Chemical Reagent) 57g was charged. After heating up to 130 degreeC and taking out to water, chlorinated brominated zinc phthalocyanine (R1) was obtained by filtering, washing with water, and drying. The chlorinated brominated zinc phthalocyanine (R1) was subjected to mass spectrometry using JMS-S3000 manufactured by JEOL Ltd., and it was confirmed that the average halogenation rate was 12.0. In addition, the delay time at the time of mass spectrometry was 275 ns, and the laser intensity was 37%. 40 g of chlorinated brominated zinc phthalocyanine (R1), 400 g of crushed 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 mixture was taken out in 2 kg of 80 ° C. water, stirred for 1 hour, filtered, washed with hot water, dried and pulverized to obtain a green pigment composition (G9).

Synthesis Example 13 (Synthesis of R2)
In a 300 ml flask, 90 g of sulfuryl chloride (Wako Pure Chemical Industries, Ltd.), 105 g of aluminum chloride (Kanto Chemical Reagent), 14 g of sodium chloride (Tokyo Chemical Industry), 27 g of zinc phthalocyanine from DIC Corporation, bromine (Wako Pure Chemical Industries) 58.5 g was charged. After heating up to 130 degreeC and taking out to water, chlorinated brominated zinc phthalocyanine (R2) was obtained by filtering, washing with water, and drying. The chlorobrominated zinc phthalocyanine (R2) was subjected to mass spectrometry using JMS-S3000 manufactured by JEOL Ltd., and it was confirmed that the average halogenation rate was 12.7. In addition, Delaytime at the time of mass spectrometry was 505 ns, and Laser Intensity was 42%. 40 g of chlorinated brominated zinc phthalocyanine (R2), 400 g of crushed 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, it was taken out in 2 kg of 80 ° C. water, stirred for 1 hour, filtered, washed with hot water, dried and pulverized to obtain a green pigment composition (G10).

(Dispersion of Pigment Yellow 138 used for toning)
Pigment Yellow 138 (Chromofine Yellow 6206EC, manufactured by Dainichi Seika Co., Ltd.) 1.65 g, DISPERBYK-161 (manufactured by Big Chemie) 3.85 g, propylene glycol monomethyl ether acetate 11.00 g, 0.3 to 0.4 mm zircon beads Was used and dispersed with a paint shaker manufactured by Toyo Seiki Co., Ltd. for 2 hours to obtain a colored composition (MY1). Coloring composition (MY1) 4.0g, Unidic ZL-295 0.98g, propylene glycol monomethyl ether acetate 0.22g was added, and the composition for toning (TY1) was obtained by mixing with a paint shaker.

Example 1 (Evaluation of α-Cl ₄ [1])
2.48 g of the green pigment composition (G1) is 0.3 to 0.00 together with 1.24 g of BYK-LPN6919 manufactured by Big Chemie Co., 1.86 g of Unidic ZL-295 manufactured by DIC Corporation, and 10.92 g of propylene glycol monomethyl ether acetate. Using 4 mm zircon beads, the mixture was dispersed for 2 hours with a paint shaker manufactured by Toyo Seiki Co., Ltd. to obtain a colored composition (MG1). Coloring composition (MG1) 4.0 g, DIC Corporation Unidic ZL-295 0.98 g, propylene glycol monomethyl ether acetate 0.22 g are added and mixed with a paint shaker to form a green pixel portion for a color filter. An evaluation composition (CG1) was obtained. This evaluation composition (CG1) was spin-coated on soda glass while changing the film thickness, and dried at 230 ° C. for 60 minutes to obtain an evaluation glass substrate. The contrast of the glass substrate for evaluation was measured with a contrast tester CT-1 manufactured by Aisaka Electric Co., Ltd. Furthermore, the spectral transmission spectrum was measured with Hitachi High-Tech Science U-3900, and the film thickness was measured with Hitachi High-Tech Science White Interference Microscope VS 1330 to calculate chromaticity.

Example 2 (Evaluation of α-Cl ₄ [2])
An evaluation composition (CG2) and an evaluation glass substrate were prepared in the same manner except that the green pigment composition (G1) was replaced with the green pigment composition (G2) in Example 1, and the contrast and chromaticity were similarly prepared. Was measured.

Example 3 (Evaluation of α-Cl ₄ [3])
An evaluation composition (CG3) and an evaluation glass substrate were prepared in the same manner except that the green pigment composition (G1) was replaced with the green pigment composition (G3) in Example 1, and the contrast and chromaticity were similarly prepared. Was measured.

Example 4 (Evaluation of α-Cl ₄ [4])
An evaluation composition (CG4) and an evaluation glass substrate were prepared in the same manner except that the green pigment composition (G1) was replaced with the green pigment composition (G4) in Example 1, and the contrast and chromaticity were similarly prepared. Was measured.

Example 5 (Evaluation of α-Cl ₄ [5])
An evaluation composition (CG5) and an evaluation glass substrate were prepared in the same manner except that the green pigment composition (G1) was replaced with the green pigment composition (G5) in Example 1, and the contrast and chromaticity were similarly prepared. Was measured.

Example 6 (Evaluation of α-Cl ₄ [6])
An evaluation composition (CG6) and an evaluation glass substrate were prepared in the same manner except that the green pigment composition (G1) was replaced with the green pigment composition (G6) in Example 1, and the contrast and chromaticity were similarly prepared. Was measured.

Example 7 (Toning of α-Cl ₄ [4] with Y138)
A coating solution obtained by mixing the toning composition (TY1) and the evaluation composition (CG4) at 20:80 is spin-coated on soda glass and dried at 230 ° C. for 60 minutes to obtain a glass substrate for evaluation. It was. The contrast of the glass substrate for evaluation was measured with a contrast tester CT-1 manufactured by Aisaka Electric Co., Ltd. Furthermore, the spectral transmission spectrum was measured with Hitachi High-Tech Science U-3900, and the film thickness was measured with Hitachi High-Tech Science White Interference Microscope VS 1330 to calculate chromaticity.

Comparative Example 1 (Evaluation of β-Cl ₄ )
2.48 g of green pigment composition (G7) 0.3 to 0.00 together with 1.24 g of BYK-LPN6919 manufactured by BYK-Chemie Corporation, 1.86 g of Unidic ZL-295 manufactured by DIC Corporation, and 10.92 g of propylene glycol monomethyl ether acetate. Using 4 mm zircon beads, the mixture was dispersed for 2 hours with a paint shaker manufactured by Toyo Seiki Co., Ltd. to obtain a colored composition (MG7). Coloring composition (MG7) 4.0 g, DIC Corporation Unidic ZL-295 0.98 g, propylene glycol monomethyl ether acetate 0.22 g are added and mixed with a paint shaker to form a green pixel portion for a color filter. An evaluation composition (CG7) was obtained. This evaluation composition (CG7) was spin-coated with soda glass while changing the film thickness, and dried at 230 ° C. for 60 minutes to obtain an evaluation glass substrate. The contrast of the glass substrate for evaluation was measured with a contrast tester CT-1 manufactured by Aisaka Electric Co., Ltd. Furthermore, the spectral transmission spectrum was measured with Hitachi High-Tech Science U-3900, and the film thickness was measured with Hitachi High-Tech Science White Interference Microscope VS 1330 to calculate chromaticity.

Comparative Example 2 (Evaluation of α-Cl ₂ )
An evaluation composition (CG8) and an evaluation glass substrate were prepared in the same manner except that the green pigment composition (G7) was replaced with the green pigment composition (G8) in Comparative Example 1, and the contrast and chromaticity were similarly prepared. Was measured.

Comparative Example 3 (R1 evaluation)
An evaluation composition (CG9) and an evaluation glass substrate were prepared in the same manner except that the green pigment composition (G7) was replaced with the green pigment composition (G9) in Comparative Example 1, and the contrast and chromaticity were similarly prepared. Was measured.

Comparative Example 4 (R2 evaluation)
An evaluation composition (CG10) and an evaluation glass substrate were produced in the same manner except that the green pigment composition (G7) was replaced with the green pigment composition (G10) in Comparative Example 1, and the contrast and chromaticity were similarly produced. Was measured.

Comparative Example 5 (Toning of β-Cl ₄ with Pigment Yellow 138)
A coating solution obtained by mixing the toning composition (TY1) and the evaluation composition (CG7) at 20:80 is spin-coated on soda glass and dried at 230 ° C. for 60 minutes to obtain an evaluation glass substrate. It was. The contrast of the glass substrate for evaluation was measured with a contrast tester CT-1 manufactured by Aisaka Electric Co., Ltd. Furthermore, the spectral transmission spectrum was measured with Hitachi High-Tech Science U-3900, and the film thickness was measured with Hitachi High-Tech Science White Interference Microscope VS 1330 to calculate chromaticity.

Comparative Example 6 (R1 Toning with Pigment Yellow 138)
An evaluation composition (CG10) and an evaluation glass substrate were prepared in the same manner except that the evaluation composition (CG7) was replaced with the evaluation composition (CG9) in Comparative Example 5, and the contrast and chromaticity were similarly prepared. Was measured.

The results of these examples and comparative examples are shown in the table below.
X in the table indicates chromaticity x when normalized by a straight line of y = 3.5x−0.15.
Further, CR (contrast) in the table is a value at a film thickness of 1 μm.

In Examples 1 to 6, since α-tetrachlorozinc phthalocyanine is used as a raw material, at least one chlorine atom is introduced at the α-position of each aromatic ring of the obtained chlorinated brominated zinc phthalocyanine. The number of chlorine atoms in the molecule is 4 or more. On the other hand, although the average chlorination rate of the chlorinated brominated zinc phthalocyanine (β-Cl ₄ ) used in Comparative Example 1 is 5.7, it is obtained because β-tetrachlorozinc phthalocyanine is used as a raw material. The maximum number of chlorine atoms introduced at the α-position of the pigment is 1.7. Similarly, in Comparative Examples 2 to 4, the number of chlorine atoms introduced at the α-position of the obtained pigment was determined from the number of chlorine atoms of chlorinated zinc phthalocyanine or zinc phthalocyanine used as a raw material. Both are lower than the example and less than 4.

As can be seen from Table 1, the contrast of Example 3 using a pigment having a chlorine atom preferentially introduced at the α-position was the same hue, and a pigment having a chlorine atom preferentially introduced at the β-position was used. The value is higher than the contrast of Comparative Example 1. Further, Comparative Example 2 having a small number of α-position chlorine atoms has a lower value than the contrast of Example 5 having the same hue and a large number of α-position chlorine atoms. Further, Comparative Examples 3 and 4 in which the chlorine atom substitution position is not particularly controlled are lower than Examples 5 and 6 having the same hue. Further, in Examples 1 to 5, when the film thickness is 1.2 μm to 2.5 μm, in the XYZ color system of CIE when color measurement is performed using a C light source alone, the following formula (2 ) To (5) can display the xy chromaticity coordinate area. It can be seen that this hue shows a particularly high contrast as compared with the case of using a chlorinated brominated zinc phthalocyanine pigment in which no chlorine atom is preferentially introduced at the α-position.
Formula (2)
y = 2.874x + 0.025
(However, in the formula, x is 0.12 <x <0.20.)
Formula (3)
y = −0.6667x + 0.45
(In the formula, x is 0.12 <x <0.18.)
Formula (4)
y = 2x-0.03
(However, in the formula, x is 0.18 <x <0.24.)
Formula (5)
y = -3.75x + 1.35
(In the formula, x is 0.20 <x <0.24.)

  Furthermore, it can be seen from Table 2 that when the toning yellow pigment is used in combination with the green pigment of the present invention, the same high contrast is exhibited.

Claims (5)

The following general formula (1):

(In the general formula (1), Z ^{1 to} Z ¹⁶ each independently represent a chlorine atom, a bromine atom or a hydrogen atom,
At least one of Z ¹ and Z ⁴ is a chlorine atom,
At least one of Z ⁵ and Z ⁸ is a chlorine atom,
At least one of Z ⁹ and Z ¹² is a chlorine atom,
A chlorinated brominated zinc phthalocyanine pigment represented by: at least one of Z ¹³ and Z ¹⁶ is a chlorine atom, and at least one of Z ^{1 to} Z ¹⁶ is a bromine atom. When a coating film consisting of 1.25 parts of resin per part of pigment in terms of mass was formed so that the film thickness was 1.2 μm to 2.5 μm,
In the XYZ color system of CIE when color measurement is performed using a C light source alone,
The xy chromaticity coordinate area surrounded by the following formulas (2) to (5) can be displayed,
The chlorinated brominated zinc phthalocyanine pigment according to claim 1.
Formula (2)
y = 2.874x + 0.025
(However, in the formula, x is 0.12 <x <0.20.)
Formula (3)
y = −0.6667x + 0.45
(In the formula, x is 0.12 <x <0.18.)
Formula (4)
y = 2x-0.03
(However, in the formula, x is 0.18 <x <0.24.)
Formula (5)
y = -3.75x + 1.35
(In the formula, x is 0.20 <x <0.24.) The pigment for a color filter according to claim 2, wherein an xy chromaticity coordinate region surrounded by the following formulas (6) to (9) can be displayed.
Formula (6)
y = 3.2x-0.058
(However, in the formula, x is 0.14 <x <0.19.)
Formula (7)
y = −0.6667x + 0.4833
(However, in the formula, x is 0.14 <x <0.185.)
Formula (8)
y = 2x-0.01
(Where x is 0.185 <x <0.22).
Formula (9)
y = -4x + 1.31
(However, in the formula, x is 0.19 <x <0.22.) The color filter which has a chlorinated brominated zinc phthalocyanine pigment as described in any one of Claims 1-3 in a pixel part. The following general formula (1):

(In the general formula (1), Z ^{1 to} Z ¹⁶ each independently represent a chlorine atom, a bromine atom or a hydrogen atom,
At least one of Z ¹ and Z ⁴ is a chlorine atom,
At least one of Z ⁵ and Z ⁸ is a chlorine atom,
At least one of Z ⁹ and Z ¹² is a chlorine atom,
A chlorinated brominated zinc phthalocyanine compound represented by: at least one of Z ¹³ and Z ¹⁶ is a chlorine atom, and at least one of Z ^{1 to} Z ¹⁶ is a bromine atom.

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