Polyhalogenated zinc phthalocyanine, polyhalogenated zinc phthalocyanine pigment, and color filter having the same in pixel portion

Abstract

Provided is a polyhalogenated zinc phthalocyanine having excellent tinting power and capable of achieving higher brightness when used as a pixel portion of a color filter. The above technical problems are solved by providing a polyhalogenated zinc phthalocyanine characterized in that it is a polyhalogenated zinc phthalocyanine represented by the following general formula 1 (in the following general formula 1, X1 to X 16 Each of the atoms is independently a chlorine atom, a bromine atom or a hydrogen atom), and the value obtained by dividing the maximum ion intensity in the range of m / z 1780 to less than 1820 by the maximum ion intensity in the range of m / z 1820 to 1860 during mass analysis is 1.00 or less. #imgabs0#

Description

Technical Field

[0001] The present invention relates to a polyhalogenated zinc phthalocyanine pigment having a specific halogen distribution, and a color filter having the polyhalogenated zinc phthalocyanine pigment in a pixel portion. Background Art

[0002] A color filter used in a liquid crystal display is a member that enables color display of the display by transmitting white light from a backlight.

[0003] As a required characteristic of such a liquid crystal display, the high-definition screen can be cited. In order to achieve high-definition, the pixel density needs to be increased, but since the aperture ratio of the screen is reduced, the problem of reduced brightness will arise. The reduction in brightness can also be compensated by increasing the amount of light from the backlight source, but a new problem of increased power consumption will arise. Therefore, the color filter is being improved by using pigments with high transmittance to the backlight source light, such as Pigment Green 58.

[0004] In addition, as other required characteristics, there is also an expansion of the color reproduction range. As a representative indicator of the color reproduction range, the NTSC ratio can be cited. It is an indicator that represents the color gamut that can be covered as a ratio when the color range that can be expressed by the NTSC method, which is a standard specification for analog television broadcasting, is set to 100% on the CIE chromaticity diagram. In recent years, the pursuit of NTSC coverage of more than 90% has begun, but in order to achieve such coverage, it is particularly important to improve the coloring power of green pixels. The improvement of coloring power can be achieved by thickening the pixel film, but for the aforementioned pigment green 58, it is difficult to achieve an NTSC ratio of more than 90% with the actual film thickness used. On the other hand, when using pigments that can be thin-filmed at a specific chromaticity, such as pigment green 7 and pigment green 59, the transmittance is lower than that of pigment green 58, so the brightness of the resulting display is reduced.

[0005] Under such circumstances, it is desired to create a pigment that has a high transmittance with respect to a backlight source and has both high brightness and high coloring power.

[0006] In order to solve such a problem, a pigment composition containing polyhalogenated zinc phthalocyanine with a specified halogen ratio has been proposed (Patent Document 1). However, the pigment composition of Patent Document 1 cannot be said to fully meet the market demand that has been increasing in recent years, that is, the demand for a higher balance between brightness and tinting power.

[0007] Patent Document 1: Japanese Patent Application Publication No. 2007-284589 Summary of the invention

[0008] Technical problem to be solved by the invention

[0009] The technical problem to be solved by the present invention is to provide a polyhalogenated zinc phthalocyanine pigment which has excellent tinting power (high tinting power) and can achieve higher brightness (high brightness) when used as a pixel portion of a color filter.

[0010] Solutions to technical problems

[0011] The present inventors have conducted intensive studies and found that polyhalogenated zinc phthalocyanine having a specific halogen distribution described below can solve the above-mentioned technical problems, thereby completing the present invention.

[0012] That is, the present invention relates to a polyhalogenated zinc phthalocyanine (sometimes referred to as "the polyhalogenated zinc phthalocyanine of the present invention") characterized by being a polyhalogenated zinc phthalocyanine represented by the following general formula 1:

[0013]

[0014] (In the above general formula 1, X1 to X 16 The value obtained by dividing the maximum ion intensity in the range of m / z of 1780 to less than 1820 in mass analysis by the maximum ion intensity in the range of m / z of 1820 to 1860 in mass analysis is 1.00 or less.

[0015] Effects of the Invention

[0016] The polyhalogenated zinc phthalocyanine pigment of the present invention achieves a remarkable effect of being able to achieve both high tinting strength and high brightness at a higher level. BRIEF DESCRIPTION OF THE DRAWINGS

[0017] Figure 1 The mass analysis results of the pigment composition of Synthesis Example 2 are shown in FIG. 1 , wherein the vertical axis represents ion intensity and the horizontal axis represents m / z.

[0018] Figure 2 : This is the mass analysis result of the pigment composition of Comparative Example 1, where the vertical axis represents ion intensity and the horizontal axis represents m / z. DETAILED DESCRIPTION

[0019] Polyhalogenated zinc phthalocyanine is a substance having a structure in which a total of chlorine atoms and / or bromine atoms are bonded to a maximum of 16 atoms per phthalocyanine molecule (structure). As the number of chlorine atoms and / or bromine atoms bonded to the molecule increases, the hue of the polyhalogenated zinc phthalocyanine changes from blue to green.

[0020] As described above, the polyhalogenated zinc phthalocyanine of the present invention has excellent characteristics such as high brightness and high tinting power compared with the conventional polyhalogenated zinc phthalocyanine. Here, it is speculated that the characteristic of high brightness is because the crystallinity of the pigment is reduced by increasing the presence ratio of zinc bromide phthalocyanine (hereinafter, in this specification, expressed as 16-brominated zinc phthalocyanine) in which 16 bromine atoms are combined in each phthalocyanine molecule (structure), and the growth of the pigment particles is inhibited in the firing process when making the color filter, resulting in a reduction in scattered light. In addition, it is speculated that the characteristic of high tinting power is because the purity of the compound is increased by increasing the presence ratio of 16-brominated zinc phthalocyanine, and the absorption spectrum becomes steep.

[0021] Here, the above-mentioned "increasing the abundance ratio of 16-bromozinc phthalocyanine" means that the abundance ratio of 16-bromozinc phthalocyanine is the same as the abundance ratio of zinc phthalocyanine to which 15 bromine atoms and 1 chlorine atom are bonded (hereinafter referred to as 15-bromo-1-chlorozinc phthalocyanine in this specification), or the abundance ratio of 16-bromozinc phthalocyanine exceeds the abundance ratio of 15-bromo-1-chlorozinc phthalocyanine.

[0022] In the present invention, the relationship of the existence ratio is defined as follows based on the measurement results of mass analysis. That is, the present invention is characterized in that the value obtained by dividing the maximum ion intensity in the range of m / z of 1780 or more and less than 1820 in mass analysis (i.e., the maximum ion intensity representing 15-bromo-1-chlorozinc phthalocyanine) by the maximum ion intensity in the range of m / z of 1820 or more and 1860 or less in mass analysis (i.e., the maximum ion intensity representing 16-bromozinc phthalocyanine) is 1.00 or less.

[0023] Polyhalogenated zinc phthalocyanines having such characteristics have not been known so far.

[0024] In order to more significantly obtain the effect of the present invention, it is preferred that the value obtained by dividing the maximum ion intensity in the range of m / z of 1780 to less than 1820 during mass analysis by the maximum ion intensity in the range of m / z of 1820 to 1860 during mass analysis is less than 1.00, preferably less than 0.90, more preferably less than 0.85, and further preferably in the range of 0.85 to 0.50.

[0025] Mass analysis was performed using a matrix-assisted laser desorption ionization time-of-flight mass spectrometer (JMS-S3000 manufactured by JEOL Ltd.), and when performing mass analysis of a known compound with a molecular weight of Q, each measurement parameter was set so that m / z = Q was detected. In the present invention, when performing mass analysis of a known compound with a molecular weight of 1840, the settings of JMS-S3000 were adjusted so that m / z = 1840 was detected.

[0026] The polyhalogenated zinc phthalocyanine of the present invention may contain zinc phthalocyanine bromide to which 1 to 16 bromine atoms are bonded in any proportion as long as the relationship between the abundance ratios of 16-bromozinc phthalocyanine and 15-bromo-1-chlorozinc phthalocyanine satisfies the above relationship, but preferably contains 14% or more of 16-bromozinc phthalocyanine.

[0027] The polyhalogenated zinc phthalocyanine in the present invention has a structure represented by the above-mentioned general formula 1. In the present invention, the polyhalogenated zinc phthalocyanine having an average primary particle diameter of 0.01 to 0.30 μm is referred to as a polyhalogenated zinc phthalocyanine pigment.

[0028] It should be noted that the average particle size of the primary particles in the present invention refers to the value obtained by averaging the longer diameter (long diameter) of each 50 halogenated zinc phthalocyanine primary particles constituting the agglomerate on the two-dimensional image, using a transmission electron microscope JEM-2010 (manufactured by JEOL Ltd.) to photograph the particles in the field of view. At this time, the polyhalogenated zinc phthalocyanine as a sample is ultrasonically dispersed in a solvent and then photographed with a microscope. In addition, a scanning electron microscope can be used instead of a transmission electron microscope.

[0029] Next, one embodiment of the method for producing polyhalogenated zinc phthalocyanine of the present invention will be described. However, the method for producing polyhalogenated zinc phthalocyanine of the present invention should not be limited or interpreted by these embodiments.

[0030] Polyhalogenated zinc phthalocyanine can be obtained as follows: In a known melting method, a halogenating agent such as sulfuryl chloride or bromine is preliminarily added and mixed in a melt at about 10 to 170° C. consisting of one or a mixture of two or more compounds serving as a solvent during halogenation, and then zinc phthalocyanine is added to cause halogenation.

[0031] The melting method is generally a method in which zinc phthalocyanine is halogenated with a halogenating agent in a melt at about 10 to 170°C consisting of one or a mixture of two or more compounds that serve as solvents during halogenation, such as alkali metal halides such as sodium chloride, alkaline earth metal halides, aluminum chloride, titanium tetrachloride, thionyl chloride, etc. The conventional method is generally a method in which a chlorinating agent is added to the melt in advance, a brominating agent is added thereto, and the bromination rate is adjusted. However, with this method, it is difficult to sufficiently increase the presence ratio of "16-brominated zinc phthalocyanine" in the above description of polyhalogenated zinc phthalocyanine.

[0032] Therefore, in order to obtain the polyhalogenated zinc phthalocyanine used in the present invention, it is preferred to preliminarily mix not only the chlorinating agent but also the brominating agent before adding zinc phthalocyanine to the melt as described above.

[0033] Generally, in the melting method, the content ratio of the polyhalogenated zinc phthalocyanine of a specific halogen atom composition in the obtained polyhalogenated zinc phthalocyanine can be arbitrarily controlled by adjusting the ratio of chloride to bromide in the molten salt, or changing the amount of chlorine gas or bromine introduced, or the reaction time. This is also true in the present invention. As mentioned above, by further adding a halogenating agent to the halogenated zinc phthalocyanine, the content ratio of the polyhalogenated zinc phthalocyanine of a desired halogen atom composition can be achieved.

[0034] As mentioned above, the halogenation temperature is preferably 10 to 170° C., more preferably 30 to 140° C. Furthermore, in order to increase the reaction rate, the reaction may be carried out under pressure. The reaction time may be, for example, 1 to 100 hours, preferably 5 to 48 hours.

[0035] The amount of bromine used in the halogenation is preferably 15 to 40 equivalents, more preferably 18 to 28 equivalents, based on zinc phthalocyanine.

[0036] In the present invention, by optimizing the raw material feeding method, usage amount, reaction temperature and reaction time, polyhalogenated zinc phthalocyanine having a halogen atom composition different from that of the existing polyhalogenated zinc phthalocyanine can be obtained.

[0037] Regardless of the above-mentioned production method, if the obtained mixture is put into water or an acidic aqueous solution such as hydrochloric acid after the reaction, the generated polyhalogenated zinc phthalocyanine will precipitate. As the polyhalogenated zinc phthalocyanine, it can be used directly, preferably filtered, washed with water or an aqueous sodium bisulfate solution, an aqueous sodium bicarbonate solution, or an aqueous sodium hydroxide solution, and washed with an organic solvent such as acetone, toluene, methanol, ethanol, or dimethylformamide as needed, and used after post-treatment such as drying.

[0038] The polyhalogenated zinc phthalocyanine can be dry-ground in a pulverizer such as an attritor, a ball mill, a vibration mill, or a vibration ball mill as needed, and then pigmented by a solvent salt milling method, a solvent boiling method, or the like, thereby obtaining a green pigment having excellent dispersibility and tinting power as compared to before pigmentation and exhibiting a yellowish and high-brightness color.

[0039] The pigmentation method of the polyhalogenated zinc phthalocyanine is not particularly limited. For example, the pigmentation can be carried out while dispersing the polyhalogenated zinc phthalocyanine before pigmentation in a dispersion medium. However, compared with a solvent treatment in which a halogenated metal phthalocyanine is heated and stirred in a large amount of an organic solvent, a solvent salt milling treatment is preferably used because it can easily suppress crystal growth and obtain pigment particles with a large specific surface area.

[0040] The solvent salt milling means that the crude pigment as polyhalogenated zinc phthalocyanine, which has just been synthesized or has been milled after synthesis, and which has not been pigmented, an inorganic salt, and an organic solvent are mixed and milled. In this case, the latter crude pigment is preferably used. Specifically, the crude pigment, the inorganic salt, and the organic solvent that does not dissolve them are put into a mixer and mixed and milled therein. As the mixer at this time, for example, a kneader, a mixing rolling mill (Mix Muller) etc. can be used.

[0041] In the present invention, it is preferred that the polyhalogenated metal phthalocyanine pigment composition having an average primary particle size of 0.01 to 0.10 μm is used for color filter applications. When obtaining the aforementioned preferred polyhalogenated zinc phthalocyanine in the present invention, it is preferred to increase the amount of inorganic salt used in the solvent salt mill relative to the amount of crude pigment used. 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, relative to 1 part by mass of the crude pigment.

[0042] As the inorganic salt, a water-soluble inorganic salt can be suitably used, for example, an inorganic salt such as sodium chloride, potassium chloride, sodium sulfate, etc. is preferably used. In addition, an inorganic salt having an average particle size of 0.5 to 50 μm is more preferably used. Such an inorganic salt can be easily obtained by finely pulverizing a common inorganic salt.

[0043] As the organic solvent, it is preferred to use an organic solvent that can inhibit crystal growth. As such an organic solvent, a water-soluble organic solvent can be suitably used, for example, diethylene glycol, glycerol, 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, triethylene glycol, triethylene glycol monomethyl ether, 1-methoxy-2-propanol, 1-ethoxy-2-propanol, dipropylene glycol, dipropylene glycol monomethyl ether, etc. can be used. The amount of the water-soluble organic solvent used is not particularly limited, and is preferably 0.01 to 5 parts by mass relative to 1 part by mass of the crude pigment.

[0044] In the method for producing the pigment containing polyhalogenated zinc phthalocyanine of the present invention, only the crude pigment may be subjected to solvent salt milling, or polyhalogenated zinc phthalocyanine and phthalocyanine derivatives may be used together and subjected to solvent salt milling. In addition, the phthalocyanine derivative may be added during the synthesis of the crude pigment or after pigmentation, but is more preferably added before the pigmentation process such as solvent salt milling. By adding the phthalocyanine derivative, the viscosity characteristics of the resist ink for color filter and the dispersion stability can be improved.

[0045] As such phthalocyanine derivatives, any known and commonly used substances can be used, preferably phthalocyanine pigment derivatives of the following formula (1) or formula (2). It should be noted that the phthalocyanine derivative is preferably a polyhalogenated zinc phthalocyanine or a phthalocyanine derivative corresponding to the zinc phthalocyanine as its raw material, but even when used in combination, it is a small amount, so a polyhalogenated copper phthalocyanine derivative or a copper phthalocyanine derivative can also be used.

[0046] P-(Y) n ···(1)

[0047] P-(AZ) n ···(2)

[0048] (In the formula, P represents a residue having no central metal or having a central metal, which is not substituted or has n hydrogen atoms removed from a halogenated phthalocyanine ring. Y represents a primary or secondary tertiary amino group, a carboxylic acid group, a sulfonic acid group, or a salt thereof with an alkali or a metal. A represents a divalent linking group, and Z represents a residue having at least one hydrogen atom removed from a nitrogen atom of a primary or secondary amino group, or a residue having at least one hydrogen atom removed from a nitrogen-containing heterocyclic ring. Furthermore, m represents 1 to 4, and n represents 1 to 4.)

[0049] The central metal is Zn (zinc), and the primary and secondary amino groups include, for example, monomethylamino, dimethylamino, and diethylamino. In addition, the base or metal that forms a salt with the carboxylic acid group or sulfonic acid group includes, for example, organic bases such as ammonia, dimethylamine, diethylamine, and triethylamine, and metals such as potassium, sodium, calcium, strontium, and aluminum. The divalent linking group of A includes, for example, an alkylene group having 1 to 3 carbon atoms, -CO2-, -SO2-, and -SO2NH(CH2). m - and the like. Also, examples of Z include a phthalimide group, a monoalkylamino group, and a dialkylamino group.

[0050] The phthalocyanine derivative that can be contained in the crude pigment when preparing the crude pigment and / or when the solvent salt is milled is usually 0.01 to 0.3 parts by mass relative to 1 part by mass of the crude pigment. It should be noted that when the phthalocyanine derivative is used when preparing the crude pigment and / or when the solvent salt is milled, the total amount of the crude pigment and the phthalocyanine derivative is regarded as the amount of the crude pigment used, and the amount of the inorganic salt used, etc. is selected from the above range.

[0051] The temperature during the solvent salt milling is preferably 30 to 150° C., more preferably 80 to 100° C. The time for the solvent salt milling is preferably 5 to 20 hours, more preferably 8 to 18 hours.

[0052] Thus, a mixture containing a halogenated zinc phthalocyanine pigment having an average primary particle size of 0.01 to 0.10 μm, an inorganic salt, and an organic solvent as main components can be obtained. The organic solvent and the inorganic salt are removed from the mixture, and the solid matter containing the polyhalogenated zinc phthalocyanine pigment as the main component is washed, filtered, dried, pulverized, etc. as needed, thereby obtaining a powder of the polyhalogenated zinc phthalocyanine pigment.

[0053] As the cleaning, any one of water washing and hot water washing can be adopted. As for the number of times of cleaning, it can also be repeated within the range of 1 to 5 times. In the case of using the aforementioned mixture of a water-soluble inorganic salt and a water-soluble organic solvent, the organic solvent and the inorganic salt can be easily removed by water washing. If necessary, acid cleaning, alkali cleaning, or solvent cleaning can also be performed in a manner that does not change the crystal state.

[0054] As the drying after the above-mentioned filtration and washing, for example, intermittent or continuous drying of the dehydration and / or desolvation of the pigment by heating at 80 to 120° C. using a heating source provided in the dryer can be cited. As dryers, there are usually box dryers, belt dryers, spray dryers, etc. In particular, spray drying is preferred because it is easy to disperse when making a paste. In addition, the pulverization after drying is not an operation for increasing the specific surface area or reducing the average particle size of the primary particles, but an operation for dispersing and powdering the pigment when the pigment becomes agglomerate, such as when drying using a box dryer or a belt dryer. For example, pulverization using a mortar, a hammer mill, a disc mill, a pin mill, a jet mill, etc. can be cited. Thus, a dry powder containing the polyhalogenated zinc phthalocyanine pigment of the present invention as the main component can be obtained.

[0055] It should be noted that the polyhalogenated zinc phthalocyanine pigment of the present invention has a property that the primary particles have weak cohesion and are more easily dispersed compared to the conventional copper phthalocyanine pigment. Through electron microscope photographs, it is possible to observe the primary particles of the pigment constituting the aggregates which cannot be observed in conventional pigments.

[0056] The polyhalogenated zinc phthalocyanine pigment of the present invention can be used for all known and conventional purposes. In particular, since the average primary particle size is 0.01 to 0.10 μm, the pigment is less likely to aggregate, and its dispersibility in synthetic resins to be colored is further improved.

[0057] In addition, when the polyhalogenated zinc phthalocyanine pigment of the present invention is used in the green pixel portion of the color filter, the pigment is easily dispersed in the photosensitive composition for the color filter, the light shielding property at 365nm commonly used when the photosensitive composition for the color filter is cured is reduced, the photocuring sensitivity is not reduced, and the film loss and pattern flow during development are unlikely to occur, so it is preferred. The green pixel portion of the color filter with high clarity and brightness required in recent years can be obtained more easily.

[0058] Regarding the primary particles of the polyhalogenated zinc phthalocyanine pigment of the present invention, if the aspect ratio of the vertical and horizontal is 1 to 3, the viscosity characteristics are improved in various application fields, and the fluidity becomes higher. When calculating the aspect ratio, first, in the same way as the case of calculating the average particle size of the primary particles, the particles in the field of view are photographed with a transmission electron microscope or a scanning electron microscope. Then, for every 50 primary particles constituting the agglomerate on the two-dimensional image, the average value of the longer diameter (long diameter) and the shorter diameter (short diameter) is calculated, and these values ​​are used for calculation.

[0059] The color filter of the present invention can be obtained by containing the polyhalogenated zinc phthalocyanine pigment of the present invention in at least the green pixel portion of the color filter.

[0060] As with conventional polyhalogenated zinc phthalocyanine pigments, the polyhalogenated zinc phthalocyanine pigment of the present invention does not need to be used in combination with a yellow pigment for color matching, or even if used in combination, a small amount is sufficient, so that the decrease in light transmittance in the entire region of 380 to 780 nm can be minimized. In particular, the polyhalogenated zinc phthalocyanine pigment of the present invention has more yellow and higher tinting power, so that if the color concentration is the same, the yellow pigment can be used in a smaller amount, so that the transmittance can be further improved, which is advantageous.

[0061] The spectral transmission spectrum in the present invention is obtained by using the first type spectrophotometer in accordance with Japanese Industrial Standard JIS Z 8722 (Method for Determination of Color - Color of Reflected and Transmitted Objects), and is obtained by scanning and irradiating a resin film containing a pigment composition having the aforementioned predetermined dry film thickness on a glass substrate, etc. with light in a predetermined wavelength region, and plotting the transmittance values ​​at each wavelength.

[0062] The color filter of the present invention containing a polyhalogenated zinc phthalocyanine pigment in the green pixel portion can transmit the green bright line of the light source well when using white light, F10 or other light sources, and the polyhalogenated zinc phthalocyanine pigment has a sharp spectral transmission spectrum, so it can maximize the color purity and coloring power of green.

[0063] The polyhalogenated zinc phthalocyanine pigment of the present invention can be used directly to produce the green pixel portion of the color filter, but can also be used in combination with a green halogenated metal phthalocyanine pigment such as a known green halogenated copper phthalocyanine or other green halogenated heterometallic phthalocyanine pigment as needed and in consideration of economic efficiency.

[0064] The polyhalogenated zinc phthalocyanine pigment in the present invention: the known and commonly used green halogenated metal phthalocyanine pigment (mass ratio) = 100:0 to 80:20, preferably 100:0 to 90:10.

[0065] In addition to green pigments, yellow pigments are sometimes used for coloring in order to show characteristics. Examples of yellow pigments that can be used together include CI Pigment Yellow (PY) 1, 2, 3, 4, 5, 6, 10, 12, 13, 14, 15, 16, 17, 18, 24, 31, 32, 34, 35, 35:1, 36, 36:1, 37, 37:1, 40, 42, 43, 53, 55, 60, 61, 62, 63, 65, 73, 74, 77, 81, 83, 93, 94, 95, 97, 98, 100, 101, 104, 106, 108, 109, 110, 113, 114, 115, 116, 117, 118, 119, 120, 121, 122, 123, 124, 125 26, 127, 128, 129, 138, 139, 150, 151, 152, 153, 154, 155, 156, 161, 162, 164, 166, 167, 168, 169, 170, 171, 172, 173, 174, 175, 176, 177, 179, 180, 181, 182, 185, 187, 199, 231, etc., from the viewpoint of high brightness or being suitable for thin film formation with a small amount of pigment used, PY83, 138, 139, 150, 185 or 231 is preferred, and PY138, 150, 185 or 231 is particularly preferred. These can be used alone or in combination of two or more. The combined use ratio of the polyhalogenated zinc phthalocyanine pigment and the yellow pigment in the present invention is 10 to 100 parts by mass of the yellow pigment relative to 100 parts by mass of the polyhalogenated zinc phthalocyanine pigment.

[0066] In addition, when the polyhalogenated zinc phthalocyanine pigment of the present invention is used, even when a yellow pigment is used in combination for color matching, a brighter green pixel portion of a color filter can be produced with less turbidity, excellent color purity and coloring power, compared to the conventional case where two or more pigments of different colors are mixed for color matching.

[0067] For example, compared with the case of using a mixed pigment in which the above-mentioned yellow pigment is used in combination with a green pigment such as the conventional CI Pigment Green 7 or CI Pigment Green 36, when a yellow pigment is used in combination with the polyhalogenated zinc phthalocyanine pigment of the present invention, the color purity and tinting strength are high, so the reduction in brightness becomes less and the light transmittance in the green region becomes larger.

[0068] The polyhalogenated zinc phthalocyanine pigment of the present invention can be used to form a pattern of a green pixel portion of a color filter by a known method. Typically, a photosensitive composition for a green pixel portion of a color filter can be obtained that contains the polyhalogenated zinc phthalocyanine pigment of the present invention and a photosensitive resin as essential components.

[0069] As a method for manufacturing a color filter, for example, a method called photolithography can be cited, that is, after dispersing the polyhalogenated zinc phthalocyanine pigment in a dispersion medium composed of a photosensitive resin, it is coated on a transparent substrate such as glass by spin coating, roll coating, inkjet coating, etc., and then the coated film is exposed to pattern by ultraviolet light through a photomask, and the unexposed portion is cleaned with a solvent or the like to obtain a green pattern.

[0070] In addition, the pattern of the green pixel portion can also be formed by electrodeposition, transfer, micellar electrolysis, and photoelectrodeposition (PVED) to manufacture a color filter. It should be noted that the pattern of the red pixel portion and the pattern of the blue pixel portion can also be formed by the same method using known pigments.

[0071] When the photosensitive composition for the green pixel portion of the color filter is modulated, for example, the polyhalogenated zinc phthalocyanine pigment of the present invention, a photosensitive resin, a photopolymerization initiator, and an organic solvent for dissolving the resin are mixed as essential components. The production method is generally the following method: after a dispersion is prepared using a polyhalogenated zinc phthalocyanine pigment, an organic solvent, and a dispersant as required, a photosensitive resin is added thereto for modulation.

[0072] As the polyhalogenated zinc phthalocyanine pigment here, a polyhalogenated zinc phthalocyanine pigment which may or may not contain the above-mentioned phthalocyanine derivative and, if necessary, a yellow pigment can be used.

[0073] Examples of the dispersant used as necessary include DISPERBYK (registered trademark) 130, DISPERBYK 161, DISPERBYK 162, DISPERBYK 163, DISPERBYK 170 from BYK Chemicals, and EFKA 46 and EFKA 47 from BASF. In addition, a leveling agent, a coupling agent, a cationic surfactant, and the like may be used simultaneously.

[0074] Examples of the organic solvent include aromatic solvents such as toluene, xylene, and methoxybenzene; acetate solvents such as ethyl acetate, butyl acetate, propylene glycol monomethyl ether acetate, and propylene glycol monoethyl ether acetate; propionate solvents such as ethoxyethyl propionate; alcohol solvents such as methanol and ethanol; ether solvents such as butyl cellosolve, propylene glycol monomethyl ether, diethylene glycol ethyl ether, and diethylene glycol dimethyl ether; ketone solvents such as methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone; aliphatic hydrocarbon solvents such as hexane; nitrogen compound solvents such as N,N-dimethylformamide, γ-butyrolactam, N-methyl-2-pyrrolidone, aniline, and pyridine; lactone solvents such as γ-butyrolactone; carbamates such as a 48:52 mixture of methyl carbamate and ethyl carbamate, water, and the like. As the organic solvent, particularly suitable ones are those which are soluble in water among polar solvents such as propionate-based solvents, alcohol-based solvents, ether-based solvents, ketone-based solvents, nitrogen compound-based solvents, lactone-based solvents, and water.

[0075] 300 to 1000 parts by mass of an organic solvent relative to 100 parts by mass of the polyhalogenated zinc phthalocyanine pigment of the present invention, and 0 to 100 parts by mass of a dispersant and / or 0 to 20 parts by mass of a phthalocyanine derivative as required are stirred and dispersed uniformly to obtain a dispersion. Next, 3 to 20 parts by mass of a photosensitive resin relative to 100 parts by mass of the polyhalogenated zinc phthalocyanine pigment and 0.05 to 3 parts by mass of a photopolymerization initiator relative to 1 part by mass of the photosensitive resin are added to the dispersion, and an organic solvent is further added as required, and the mixture is stirred and dispersed uniformly to obtain a photosensitive composition for a green pixel portion of a color filter.

[0076] Examples of the photosensitive resin that can be used at this time include thermoplastic resins such as urethane resins, acrylic resins, polyamic acid resins, polyimide resins, styrene maleic acid resins, and styrene maleic anhydride resins; bifunctional monomers such as 1,6-hexanediol diacrylate, ethylene glycol diacrylate, neopentyl glycol diacrylate, triethylene glycol diacrylate, bis(acryloyloxyethoxy)bisphenol A, and 3-methylpentanediol diacrylate; and photopolymerizable monomers such as trimethylolpropane triacrylate, pentaerythritol triacrylate, tris(2-hydroxyethyl)isocyanate, dipentaerythritol hexaacrylate, and dipentaerythritol pentaacrylate.

[0077] Examples of the photopolymerization initiator include acetophenone, benzophenone, benzyl dimethyl ketal, benzoyl peroxide, 2-chlorothioxanthone, 1,3-bis(4'-azidobenzylidene)-2-propane, 1,3-bis(4'-azidobenzylidene)-2-propane-2'-sulfonic acid, and 4,4'-diazidine stilbene-2,2'-disulfonic acid.

[0078] The photosensitive composition for green pixel portion of a color filter prepared in this way is subjected to pattern exposure with ultraviolet rays through a photomask, and then the unexposed portion is washed with an organic solvent, alkaline water or the like, thereby producing a color filter.

[0079] The polyhalogenated zinc phthalocyanine pigment obtained by the present invention is a green color with more yellow and has high tinting power, showing a bright green color with high contrast at high color purity. Therefore, in addition to the color filter application described in detail, it is also suitable for coloring coatings, plastics, printing inks, rubber, leather, printing, electronic toners, inkjet inks, thermal transfer inks, etc.

[0080] Example

[0081] Hereinafter, the present invention will be described based on Examples, but the present invention is not limited thereto. In Examples and Comparative Examples, "parts" and "%" are based on mass unless otherwise specified.

[0082] Reference Example (Manufacturing Example of Zinc Phthalocyanine Used Below)

[0083] Zinc phthalocyanine is produced from phthalonitrile, ammonia and zinc chloride. The 1-chloronaphthalene solution after the reaction has light absorption at 750-850nm.

[0084] Synthesis example 1

[0085] 270 parts of sulfuryl chloride (Wako Pure Chemical Industries, Ltd., product code: 190-04815), 315 parts of anhydrous aluminum chloride (Kanto Chemical Industry, Ltd., product code: 01156-00), 43 parts of sodium chloride (Tokyo Chemical Industry, Ltd., product code: S0572), and 43 parts of bromine were mixed, and 65 parts of zinc phthalocyanine obtained in the above reference example was added to the obtained mixture. 407 parts of bromine (Wako Pure Chemical Industries, Ltd., product code: 026-02405) was added dropwise thereto, and the temperature was raised to 80°C over 22 hours, and 72 parts of bromine was added dropwise. Thereafter, the temperature was raised to 130°C over 3 hours, and the reaction mixture was taken out into water to precipitate a crude polyhalogenated zinc phthalocyanine pigment. The aqueous slurry was filtered, washed with hot water at 60°C, and then peptized in water. The obtained slurry was filtered again, washed with hot water at 60°C, and dried at 90°C to obtain 173 parts of polyhalogenated zinc phthalocyanine crude pigment. 3 parts of the polyhalogenated zinc phthalocyanine crude pigment, 30 parts of crushed sodium chloride, and 3 parts of diethylene glycol were put into a double-arm kneader and kneaded at 100°C for 8 hours. After kneading, it was taken out into 300 parts of water at 80°C, stirred for 1 hour, filtered, washed with hot water, dried, and crushed to obtain a polyhalogenated zinc phthalocyanine pigment. The polyhalogenated zinc phthalocyanine pigment was subjected to mass analysis (JEOL Ltd., JMS-S3000). As a result, the value obtained by dividing the maximum ion intensity in the range of m / z from 1780 to 1820 by the maximum ion intensity in the range of m / z from 1820 to 1860 was 0.71. In addition, the delay time (Delaytime) at this time was 310ns, and the resolution value (Resolving Power Value) of the peak with m / z of 1820 or more and 1860 or less was 42004.

[0086] Synthesis example 2

[0087] 270 parts of sulfuryl chloride (Wako Pure Chemical Industries, Ltd., product code: 190-04815), 315 parts of anhydrous aluminum chloride (Kanto Chemical Industry, Ltd., product code: 01156-00), 43 parts of sodium chloride (Tokyo Chemical Industry, Ltd., product code: S0572), and 43 parts of bromine were mixed, and 65 parts of zinc phthalocyanine obtained in the above reference example was added to the obtained mixture. 407 parts of bromine (Wako Pure Chemical Industries, Ltd., product code: 026-02405) was added dropwise thereto, and the temperature was raised to 80°C over 22 hours, and 72 parts of bromine was added dropwise. Thereafter, the temperature was raised to 100°C over 3 hours, and the reaction mixture was taken out into water to precipitate a crude polyhalogenated zinc phthalocyanine pigment. The aqueous slurry was filtered, washed with hot water at 60°C, and then peptized in water. The obtained slurry was filtered again, washed with hot water at 60°C, and dried at 90°C to obtain 173 parts of a crude polyhalogenated zinc phthalocyanine pigment. 3 parts of the crude polyhalogenated zinc phthalocyanine pigment, 30 parts of ground sodium chloride, and 3 parts of diethylene glycol were placed in a double-arm kneader and kneaded at 100°C for 8 hours.

[0088] After kneading, the mixture was taken out into 300 parts of water at 80°C, stirred for 1 hour, filtered, washed with hot water, dried and crushed to obtain a polyhalogenated zinc phthalocyanine pigment. The polyhalogenated zinc phthalocyanine pigment was subjected to mass analysis (JEOL Ltd., JMS-S3000). As a result, the maximum ion intensity in the range of m / z of 1780 to 1820 divided by the maximum ion intensity in the range of m / z of 1820 to 1860 was 0.57. In addition, the delay time at this time was 285ns, and the resolution value of the peak of m / z of 1820 to 1860 was 42672.

[0089] Synthesis example 3

[0090] 270 parts of sulfuryl chloride (Wako Pure Chemical Industries, Ltd., product code: 190-04815), 315 parts of anhydrous aluminum chloride (Kanto Chemical Industry, Ltd., product code: 01156-00), 43 parts of sodium chloride (Tokyo Chemical Industry, Ltd., product code: S0572), and 43 parts of bromine were mixed, and 65 parts of zinc phthalocyanine obtained in the above reference example was added to the obtained mixture. 407 parts of bromine (Wako Pure Chemical Industries, Ltd., product code: 026-02405) was added dropwise thereto, and the temperature was raised to 80°C over 22 hours, and 72 parts of bromine was added dropwise. Thereafter, the temperature was raised to 90°C over 3 hours, and the reaction mixture was taken out into water to precipitate a polyhalogenated zinc phthalocyanine crude pigment. The aqueous slurry was filtered, washed with hot water at 60°C, and then peptized in water. The obtained slurry was filtered again, washed with hot water at 60°C, and dried at 90°C to obtain 173 parts of polyhalogenated zinc phthalocyanine crude pigment. 3 parts of the polyhalogenated zinc phthalocyanine crude pigment, 30 parts of crushed sodium chloride, and 3 parts of diethylene glycol were put into a double-arm kneader and kneaded at 100°C for 8 hours. After kneading, it was taken out into 300 parts of water at 80°C, stirred for 1 hour, filtered, washed with hot water, dried, and crushed to obtain a polyhalogenated zinc phthalocyanine pigment. The polyhalogenated zinc phthalocyanine pigment was mass analyzed (JEOL Ltd., JMS-S3000). As a result, the maximum ion intensity in the range of m / z greater than 1780 and less than 1820 divided by the maximum ion intensity in the range of m / z greater than 1820 and less than 1860 was 0.56. In addition, the delay time at this time was 285ns, and the resolution value of the peak with m / z greater than 1820 and less than 1860 was 37665.

[0091] Synthesis example 4

[0092] 270 parts of sulfuryl chloride (Wako Pure Chemical Industries, Ltd., product code: 190-04815), 347 parts of anhydrous aluminum chloride (Kanto Chemical Industry, Ltd., product code: 01156-00), 43 parts of sodium chloride (Tokyo Chemical Industry, Ltd., product code: S0572), and 43 parts of bromine were mixed, and 65 parts of zinc phthalocyanine obtained in the above reference example was added to the obtained mixture. 407 parts of bromine (Wako Pure Chemical Industries, Ltd., product code: 026-02405) was added dropwise thereto, the temperature was raised to 80°C over 22 hours, and 72 parts of bromine was added dropwise. Thereafter, the temperature was raised to 120°C over 3 hours, and the reaction mixture was taken out into water to precipitate a polyhalogenated zinc phthalocyanine crude pigment. The aqueous slurry was filtered, washed with hot water at 60°C, and then peptized in water. The obtained slurry was filtered again, washed with hot water at 60°C, and dried at 90°C to obtain 173 parts of polyhalogenated zinc phthalocyanine crude pigment. 3 parts of the polyhalogenated zinc phthalocyanine crude pigment, 30 parts of crushed sodium chloride, and 3 parts of diethylene glycol were put into a double-arm kneader and kneaded at 100°C for 8 hours. After kneading, it was taken out into 300 parts of water at 80°C, stirred for 1 hour, filtered, washed with hot water, dried, and crushed to obtain a polyhalogenated zinc phthalocyanine pigment. The polyhalogenated zinc phthalocyanine pigment was mass analyzed (JEOL Ltd., JMS-S3000). As a result, the maximum ion intensity in the range of m / z greater than 1780 and less than 1820 divided by the maximum ion intensity in the range of m / z greater than 1820 and less than 1860 was 0.81. In addition, the delay time at this time was 300ns, and the resolution value of the peak with m / z greater than 1820 and less than 1860 was 28832.

[0093] Synthesis example 5

[0094] 270 parts of sulfuryl chloride (Wako Pure Chemical Industries, Ltd., product code: 190-04815), 315 parts of anhydrous aluminum chloride (Kanto Chemical Co., Ltd., product code: 01156-00), 43 parts of sodium chloride (Tokyo Chemical Co., Ltd., product code: S0572), and 461 parts of bromine are mixed, and 67 parts of zinc phthalocyanine obtained in the above reference example are added to the obtained mixture. The temperature is raised to 80°C over 22 hours, and 147 parts of bromine are added dropwise. Thereafter, the temperature is raised to 130°C over 3 hours, and after being maintained for 1 hour, the reaction mixture is taken out into water to precipitate a polyhalogenated zinc phthalocyanine crude pigment. The aqueous slurry is filtered, washed with hot water at 60°C, and then peptized in water. The obtained slurry is filtered again, washed with hot water at 60°C, and then dried at 90°C to obtain 178 parts of a polyhalogenated zinc phthalocyanine crude pigment. 3 parts of the crude polyhalogenated zinc phthalocyanine pigment, 30 parts of crushed sodium chloride, and 3 parts of diethylene glycol were put into a double-arm kneader and kneaded at 100°C for 8 hours. After kneading, it was taken out into 300 parts of water at 80°C, stirred for 1 hour, filtered, washed with hot water, dried, and crushed to obtain a polyhalogenated zinc phthalocyanine pigment. The polyhalogenated zinc phthalocyanine pigment was mass analyzed (JEOL Ltd., JMS-S3000). As a result, the maximum ion intensity in the range of m / z greater than 1780 and less than 1820 divided by the maximum ion intensity in the range of m / z greater than 1820 and less than 1860 was 0.69. In addition, the delay time at this time was 400ns, and the resolution value of the peak with m / z greater than 1820 and less than 1860 was 37637.

[0095] Example 1

[0096] 2.48 g of the polyhalogenated zinc phthalocyanine pigment obtained in Synthesis Example 1, 1.24 g of BYK-LPN6919 manufactured by BYK-Chemie, 1.86 g of UNIDIC ZL-295 manufactured by DIC Corporation, and 10.92 g of propylene glycol monomethyl ether acetate were dispersed together in a pigment mixer manufactured by Toyo Seiki Co., Ltd. for 2 hours using zirconium beads of 0.3 to 0.4 mm to obtain a coloring composition (1). 4.0 g of the coloring composition (1), 0.98 g of UNIDIC ZL-295 manufactured by DIC Corporation, and 0.22 g of propylene glycol monomethyl ether acetate were added and mixed using a pigment mixer to obtain an evaluation composition (1-A) for forming a green pixel portion for a color filter.

[0097] Using zirconium beads of 0.3 to 0.4 mm, 2.48 g of Pigment Yellow 138 (BASF Japan Ltd., Paliotol Yellow D0960), 1.24 g of BYK-LPN6919 manufactured by BYK-Chemie, 1.86 g of UNIDIC ZL-295 manufactured by DIC Corporation, and 10.92 g of propylene glycol monomethyl ether acetate were dispersed together in a pigment mixer manufactured by Toyo Seiki Co., Ltd. for 2 hours to obtain a coloring composition (7). 4.0 g of the coloring composition (7), 0.98 g of UNIDIC ZL-295 manufactured by DIC Corporation, and 0.22 g of propylene glycol monomethyl ether acetate were added and mixed using a pigment mixer to obtain a coloring composition (7-A) for forming a green pixel portion for a color filter.

[0098] The toning composition (7-A) and the evaluation composition (1-A) were mixed so as to achieve chromaticity (x, y) = (0.286, 0.575), and a film was formed and dried to obtain a glass substrate (1-B) for evaluation.

[0099] Embodiments 2 to 5

[0100] By the same procedure as in Example 1, colored compositions (2) to (5), evaluation compositions (2-A) to (5-A), and evaluation glass substrates (2-B) to (5-B) were obtained from the polyhalogenated zinc phthalocyanine pigments obtained in Synthesis Examples 2 to 5.

[0101] Comparative Example 1

[0102] (1) 270 parts of sulfuryl chloride (Wako Pure Chemical Industries, Ltd., product code: 190-04815), 315 parts of anhydrous aluminum chloride (Kanto Chemical Industry, Ltd., product code: 01156-00), and 43 parts of sodium chloride (Tokyo Chemical Industry, Ltd., product code: S0572) were mixed, and 63 parts of zinc phthalocyanine obtained in the above reference example was added to the resulting mixture. 367 parts of bromine (Wako Pure Chemical Industries, Ltd., product code: 026-02405) was added dropwise thereto, and the temperature was raised to 80°C over 22 hours, and 69 parts of bromine was added dropwise. Thereafter, the temperature was raised to 130°C over 3 hours, and after being maintained for 1 hour, the reaction mixture was taken out into water to precipitate a polyhalogenated zinc phthalocyanine crude pigment. The aqueous slurry was filtered, washed with hot water at 60°C, and then peptized in water. The obtained slurry was filtered again, washed with hot water at 60°C, and dried at 90°C to obtain 169 parts of polyhalogenated zinc phthalocyanine crude pigment. 3 parts of the polyhalogenated zinc phthalocyanine crude pigment, 30 parts of crushed sodium chloride, and 3 parts of diethylene glycol were put into a double-arm kneader and kneaded at 100°C for 8 hours. After kneading, it was taken out into 300 parts of water at 80°C, stirred for 1 hour, filtered, washed with hot water, dried, and crushed to obtain a polyhalogenated zinc phthalocyanine pigment. The polyhalogenated zinc phthalocyanine pigment was mass analyzed (JEOL Ltd., JMS-S3000). As a result, the maximum ion intensity in the range of m / z greater than 1780 and less than 1820 divided by the maximum ion intensity in the range of m / z greater than 1820 and less than 1860 was 1.24. In addition, the delay time at this time was 495ns, and the resolution value of the peak with m / z greater than 1820 and less than 1860 was 36553.

[0103] (2) Using zirconium beads of 0.3 to 0.4 mm, 2.48 g of the polyhalogenated zinc phthalocyanine pigment obtained in (1) above, 1.24 g of BYK-LPN6919 manufactured by BYK-Chemie, 1.86 g of UNIDIC ZL-295 manufactured by DIC Corporation, and 10.92 g of propylene glycol monomethyl ether acetate were dispersed in a pigment mixer manufactured by Toyo Seiki Co., Ltd. for 2 hours to obtain a coloring composition (6). 4.0 g of the coloring composition (6), 0.98 g of UNIDIC ZL-295 manufactured by DIC Corporation, and 0.22 g of propylene glycol monomethyl ether acetate were added and mixed in a pigment mixer to obtain a comparative composition (6-A) for forming a green pixel portion for a color filter.

[0104] (3) The coloring composition (7-A) and the comparative composition (6-A) obtained in the above (2) were mixed so that the chromaticity (x, y) = (0.286, 0.575), and a film was formed and dried to obtain a comparative glass substrate (6-B).

[0105] Test example

[0106] The brightness of the evaluation glass substrates (1-B) to (5-B) and the comparison glass substrate (6-B) was measured using a spectrophotometer U3900 manufactured by Hitachi High-Technologies Corporation. In addition, the film thickness of the evaluation glass substrates (1-B) to (5-B) and the comparison glass substrate (6-B) was measured using a scanning white interference microscope VS1330 manufactured by Hitachi High-Technologies Corporation. The results of the brightness and film thickness measurements are shown in the table below (the values ​​when the comparison glass substrates were used were set to 100.0% for evaluation).

[0107] [Table 1]

[0108]

[0109] The values ​​obtained by dividing the maximum ion intensity in the range of m / z of 1780 to less than 1820 of the polyhalogenated zinc phthalocyanine pigments obtained in Synthesis Examples 1 to 5 and Comparative Example 1(1) by the maximum ion intensity in the range of m / z of 1820 to 1860 are shown in the table below.

[0110] [Table 2]

[0111] Comparative Example 1 Synthesis example 1 Synthesis example 2 Synthesis example 3 Synthesis example 4 Synthesis example 5 1.24 0.71 0.57 0.56 0.81 0.69

[0112] As described above, it was confirmed that the brightness and film thickness after adjusting the color to chromaticity (x, y) = (0.286, 0.575) (Japanese Patent Application Laid-Open No. 2016-80919) using the transmission spectrum of the polyhalogenated zinc phthalocyanine obtained in the present invention and the transmission spectrum of Pigment Yellow 138 were better than those using the transmission spectrum of the existing polyhalogenated zinc phthalocyanine.

Claims

1. A polyhalogenated zinc phthalocyanine, characterized in that: is a polyhalogenated zinc phthalocyanine represented by the following general formula 1, [Chemistry 1] Formula 1 In the above general formula 1, X1 to X 16 are independently a chlorine atom, a bromine atom or a hydrogen atom, The value obtained by dividing the maximum ion intensity in the range of m / z from 1780 to less than 1820 by the maximum ion intensity in the range of m / z from 1820 to 1860 in mass analysis is 0.85 to 0.

50.

2. A pigment dispersion comprising at least the polyhalogenated zinc phthalocyanine according to claim 1 and an organic solvent. 3 . A color filter comprising the polyhalogenated zinc phthalocyanine according to claim 1 in a pixel portion.

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