JP4992321B2 - Polyhalogenated zinc phthalocyanine, photosensitive composition and color filter - Google Patents

Description

  The present invention relates to a polyhalogenated zinc phthalocyanine suitable for use in a color filter of a liquid crystal display device, a photosensitive composition containing the same, and a color filter using the same.

  Conventionally used color filters are highly transparent, and pigments that can transmit colors well through the bright lines of the backlight are considered excellent. This technology is still advantageous for devices such as mobile phones, mobile game machines, PDAs, and the like that require a limited amount of electricity, such as secondary batteries and dry batteries, and where the backlight source needs to reduce the electric capacity.

  However, color filters used in equipment that is always connected to a power source, such as a personal computer liquid crystal display monitor or a liquid crystal television, have a power source that is always supplied with a backlight light source. A highly pure and highly transparent colorant is required.

  A color filter used in a liquid crystal display device that requires high color purity is obtained by forming a three-color pattern of red, green, and blue on a transparent substrate such as glass, and forms a green coloring pattern. For this purpose, a colorant composed of a green pigment such as chlorinated copper phthalocyanine pigment (CI PIGMENT Green 7) or chlorinated brominated copper phthalocyanine (CI PIGMENT Green 36) is generally used.

  Copper phthalocyanine is a cyclic compound having four isoindoles around a copper atom, and has four aromatic rings in one molecule. Each of the aromatic rings has 4 hydrogen atoms, and a total of 16 hydrogen atoms can be substituted with halogen atoms such as bromine and chlorine.

  Therefore, the colorant used in the green pattern of the color filter used in a liquid crystal display device that requires high color purity usually has some or all of these 16 hydrogen atoms formed by chlorine or bromine. Green pigment compositions containing substituted polyhalogenated copper phthalocyanine pigments have been used.

  Separately from this, as disclosed in Patent Documents 1 to 3, the green pixel portion of the color filter is a polyhalogenated zinc phthalocyanine that has a wider color reproduction range and higher coloring power than a polyhalogenated copper phthalocyanine pigment. Is known to be used as a green pigment.

JP 2003-176424 A JP 2004-70342 A JP 2004-70343 A

  However, known polyhalogenated zinc phthalocyanines obtained according to these patent documents have a maximum diffraction peak at a Bragg angle (2θ ± 0.2 °) of 25.0 ° with respect to the Cu—Kα ray in the X-ray diffraction spectrum. , 16.8 °, 23.1 °, and 32.4 °, polyhalogenated zinc phthalocyanine.

  Although such a crystal type polyhalogenated zinc phthalocyanine produces a green color with strong yellowness and high brightness, there are cases where it is difficult to maintain high brightness, high contrast and high brightness.

  The present invention has been made in view of the above circumstances, and develops a green color with a strong yellowishness and high brightness, and as a result, for example, to form a green pixel portion of a color filter with high brightness, high contrast, and high brightness. It is an object of the present invention to provide a suitable crystal type polyhalogenated zinc phthalocyanine. Further, it is an object of the present invention to stably provide a color filter that can be used in combination with a smaller amount of yellow pigment and that has a smaller decrease in lightness due to the toning.

  In the present invention, by newly devising a known method for producing a polyhalogenated zinc phthalocyanine, a new crystal form different from the conventional one appears, and it has higher brightness, higher contrast and higher brightness. It has been found that the present invention is suitable for forming a green pixel portion of a filter, and the present invention has been achieved.

That is, in order to solve the above-mentioned problems, the present invention has an X-ray diffraction spectrum having a maximum diffraction peak at a Bragg angle (2θ ± 0.2 °) = 25.5 ° with respect to the Cu-Kα ray. A featured polyhalogenated zinc phthalocyanine is provided.
The present invention also provides a photosensitive composition for a color filter green pixel portion comprising a photosensitive resin and the above as an essential component of a zinc halide phthalocyanine.
Furthermore, the present invention provides a color filter containing the polyhalogenated zinc phthalocyanine in a green pixel portion.

Since the novel crystal-type polyhalogenated zinc phthalocyanine of the present invention has a peak at a specific Bragg angle in the X-ray diffraction spectrum, the brightness, contrast, and contrast are higher than those of the conventional crystal-type polyhalogenated zinc phthalocyanine. The light transmittance has an especially remarkable effect that it is superior in performance in any case. Therefore, the polyhalogenated zinc phthalocyanine of the present invention is optimal for forming a pattern of a green pixel portion of a color filter for a large screen such as a display.
Further, since the photosensitive composition of the present invention contains polyhalogenated zinc phthalocyanine having a peak at a specific Bragg angle in the above-mentioned X-ray diffraction spectrum, it is easy in terms of performance in any of brightness, contrast and light transmittance. There is an especially remarkable effect that an excellent color filter can be manufactured.
Furthermore, since the color filter of the present invention contains polyhalogenated zinc phthalocyanine having a peak at a specific Bragg angle in the above X-ray diffraction spectrum, it is superior in performance in terms of luminance, contrast and light transmittance. There is a particularly remarkable effect.

  Since zinc phthalocyanine has 16 hydrogen atoms in the phthalocyanine ring, up to 16 of these hydrogen atoms can be substituted with bromine atoms and / or chlorine atoms. These halogen atoms may all be the same or different. When the number of substituents is constant, green becomes darker in the order of bromine atom> chlorine atom. When these hydrogen atoms are substituted with bromine atoms, for example, chlorine atoms, the number of bromine atoms is 0 to 16, the number of chlorine atoms is 0 to 16, and the number of hydrogen atoms is 0 to 16, in theory. A total of 136 types of substitution products can be produced.

  Such a polyhalogenated zinc phthalocyanine is specifically represented by the following general formula.

(In General Formula 1, all of X _{1 to} X ₁₆ are independently a chlorine atom, a bromine atom, or a hydrogen atom. However, at least eight of all Xs are a chlorine atom or a bromine.)

  Here, polyhalogenated zinc phthalocyanine is optimal because it contains 8 or more bromine atoms, which produces a yellowish, light green color and is optimal for use in the color filter green pixel pattern. It is. In the present invention, polyhalogenated zinc phthalocyanine containing 8 or more bromine atoms is referred to as polybrominated zinc phthalocyanine.

  The average composition of the polyhalogenated zinc phthalocyanine can be easily obtained from mass spectrometry based on mass spectroscopy and halogen content analysis by flask combustion ion chromatography.

  Further, the polyhalogenated zinc phthalocyanine of the present invention is characterized by having a maximum diffraction peak at a Bragg angle (2θ ± 0.2 °) = 25.5 ° with respect to the Cu—Kα ray in the X-ray diffraction spectrum. In the polyhalogenated zinc phthalocyanine of the present invention, this peak at 25.5 ° is the largest, but the other peaks have peaks at 9.6 °, 13.4 ° and 26.6 °. .

  The polyhalogenated zinc phthalocyanine can be produced by a known production method such as a chlorosulfonic acid method, a halogenated phthalonitrile method, or a melting method.

  Examples of the chlorosulfonic acid method include a method in which zinc phthalocyanine is dissolved in a sulfur oxide-based solvent such as chlorosulfonic acid, and chlorine gas and bromine are added thereto to halogenate. The reaction at this time is carried out at a temperature of 20 to 120 ° C. and in a range of 1 to 10 hours.

  As the halogenated phthalonitrile method, for example, phthalic acid or phthalodinitrile in which some or all of the hydrogen atoms in the aromatic ring are substituted with halogen atoms such as chlorine in addition to bromine, and a metal or metal salt of zinc are appropriately used. A method of synthesizing a corresponding metal halide phthalocyanine using as a starting material can be mentioned. In this case, a catalyst such as ammonium molybdate may be used as necessary. The reaction at this time is carried out at a temperature of 100 to 300 ° C. and in the range of 1 to 30 hours.

  Melting methods include aluminum halides such as aluminum chloride and aluminum bromide, titanium halides such as titanium tetrachloride, alkali metal halides or alkaline earth metal halides such as sodium chloride and sodium bromide [ Hereinafter referred to as an alkali (earth) metal halide), thionyl chloride, etc., in a melt of about 10 to 170 ° C. composed of one kind or a mixture of two or more kinds of compounds which become solvents in the case of various halogenations. A method of halogenating phthalocyanine with a halogenating agent is mentioned.

  The preferred aluminum halide is aluminum chloride. In the above method using an aluminum halide, the addition amount of the aluminum halide is usually 3 times or more, preferably 10 to 20 times the mol of the metal phthalocyanine.

  The aluminum halide may be used alone, but when an alkali (earth) metal halide is used in combination with the aluminum halide, the melting temperature can be further lowered, which is advantageous in operation. A preferred alkali (earth) metal halide is sodium chloride. The amount of the alkali (earth) metal halide to be added is preferably 0 to 10 parts by mass of the alkali (earth) metal halide with respect to 10 parts by mass of the aluminum halide within the range in which the molten salt is formed.

  When aluminum chloride is used as the aluminum halide, thionyl chloride or titanium tetrachloride is preferably used as the solvent. The amount of thionyl chloride or titanium tetrachloride is 1 part by mass or more, preferably 2 to 10 parts by mass with respect to 1 part by mass of metal phthalocyanine.

Examples of the halogenating agent include chlorine gas, sulfuryl chloride, bromine and the like.
The halogenation temperature is preferably 10 to 170 ° C, more preferably 30 to 140 ° C. Furthermore, pressurization is possible to increase the reaction rate. The reaction time is 5 to 100 hours, preferably 10 to 30 hours.

  The melting method using two or more of the above-mentioned compounds in combination is possible by adjusting the ratio of chloride, bromide and iodide in the molten salt, or by changing the introduction amount and reaction time of chlorine gas, bromine and iodine. The ratio of various polyhalogenated zinc phthalocyanines in the resulting polyhalogenated zinc phthalocyanine can be arbitrarily controlled, which is preferable.

  In order to obtain the polyhalogenated zinc phthalocyanine of the present invention, the melting method is preferable because the decomposition of the raw material during the reaction is less, the yield from the raw material is better, and the reaction can be performed with an inexpensive apparatus without using a strong acid. .

  In any of the above production methods, after completion of the reaction, when the obtained mixture is put into an acidic aqueous solution such as water or hydrochloric acid, polyhalogenated zinc phthalocyanine is precipitated. Thereafter, filtration, washing with water or sodium hydrogen sulfate aqueous solution, sodium hydrogen carbonate aqueous solution, sodium hydroxide aqueous solution, and organic solvent washing such as acetone, toluene, methyl alcohol, ethyl alcohol, dimethylformamide as necessary are performed. It is preferably used as a raw material for zinc halide phthalocyanine.

  The polyhalogenated zinc phthalocyanine is obtained by subjecting the wet cake obtained by washing as described above or the dried product obtained by drying the crystal to crystal transformation to obtain a novel crystalline form of the polyhalogenated zinc phthalocyanine of the present invention. I can do it.

  In this crystal transformation, the above-mentioned polyhalogenated zinc phthalocyanine is dry-ground in a pulverizer such as an attritor, ball mill, vibration mill, vibration ball mill or the like as necessary, and then in the presence of alkali, a solvent salt milling method. Or the like by a solvent method or the like, a polyhalogenated zinc phthalocyanine having an average primary particle diameter of 0.01 to 0.1 μm can be obtained. By performing such an operation, it is possible to obtain a polyhalogenated zinc phthalocyanine that is superior in dispersibility and coloring power, has a yellowish lightness, and has a high contrast green color than before pigmentation. I can do it.

  In addition, the average particle diameter of the primary particle in the present invention is a polyhalogen constituting an aggregate on a two-dimensional image obtained by photographing particles in the field of view with a transmission electron microscope JEM-2010 (manufactured by JEOL Ltd.). This is a value obtained by obtaining the longer diameter (major diameter) of 50 primary zinc phthalocyanine particles and averaging them. At this time, the sample polyhalogenated zinc phthalocyanine is ultrasonically dispersed in a solvent and then photographed with a microscope. A scanning electron microscope may be used instead of the transmission electron microscope.

  The above-mentioned pigmentation method is not particularly limited. For example, pigment particles that can suppress crystal growth more easily and have a relatively small average particle diameter than solvent treatment in which a metal halide phthalocyanine is heated and stirred in a large amount of an organic solvent. Therefore, it is preferable to employ a solvent salt milling treatment.

  The solvent salt milling means kneading and grinding polyhalogenated zinc phthalocyanine, an inorganic salt, and an organic solvent. Of course, as described above, the polyhalogenated zinc phthalocyanine having a large particle diameter may be subjected to solvent salt milling after dry grinding. Specifically, polyhalogenated zinc phthalocyanine, an inorganic salt, and an organic solvent that does not dissolve it are charged into a kneader, and kneading and grinding are performed therein. As a kneader at this time, for example, a kneader, a mix muller, or the like can be used.

  As described above, the preferred production method in the present invention is a method of solvent salt milling the raw material in the presence of alkali. As the alkali used in this case, either inorganic alkali or organic alkali can be used, but it is easy to handle semi-solid or solid at room temperature, hardly emits odor due to volatilization when heated, and is washed with polyhalogenated zinc halide. A water-soluble inorganic alkali can be preferably used because it can be easily removed from phthalocyanine.

  The water-soluble inorganic alkali includes an inorganic compound that exhibits basicity when dissolved in water. For example, an inorganic alkali such as sodium hydroxide or potassium hydroxide is preferably used. The amount of alkali used is not particularly limited, but is preferably 0.3 to 5 parts, more preferably 0.75 to 2 parts, per 1 part of polyhalogenated zinc phthalocyanine used as a raw material in terms of mass. .

  As said inorganic salt, the water-soluble inorganic salt different from the said inorganic alkali can be used conveniently, For example, it is preferable to use inorganic salts, such as sodium chloride, potassium chloride, sodium sulfate. 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, it is preferable to use polyhalogenated zinc phthalocyanine having an average primary particle diameter of 0.01 to 0.1 μm for forming a green pixel portion of a color filter. In obtaining such a polyhalogenated zinc phthalocyanine having a suitable average particle size, it is preferable to increase the amount of inorganic salt used relative to the amount of polyhalogenated zinc phthalocyanine used in solvent salt milling. That is, the amount of the inorganic salt used is preferably 5 to 20 parts, more preferably 7 to 15 parts per 1 part of polyhalogenated zinc phthalocyanine in terms of mass.

  As described above, it is preferable to use an organic solvent capable of suppressing crystal growth, as described above, and a water-soluble organic solvent can be suitably used as such an organic solvent, 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, triethylene glycol, triethylene glycol monomethyl ether, 1-methoxy-2-propanol, 1-ethoxy-2-propano Le, dipropylene glycol, dipropylene glycol monomethyl ether, dipropylene glycol monomethyl ether, can be used dipropylene glycol.

  Although the usage-amount of the water-soluble organic solvent in this case is not specifically limited, 0.01-5 parts and 0.8-2 parts are preferable with respect to 1 part of polyhalogenated zinc phthalocyanines in mass conversion.

  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 to 20 hours, and more preferably 8 to 18 hours.

  Thus, a mixture containing polyhalogenated zinc phthalocyanine, alkali, inorganic salt, and organic solvent as main components is obtained. The organic solvent, alkali, and inorganic salt are removed from this mixture, and if necessary, polyhalogenated zinc phthalocyanine is obtained. A fine polyhalogenated zinc phthalocyanine powder can be obtained by washing, filtering, drying, pulverizing, etc., a solid mainly composed of.

  As washing, 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 alkali, a water-soluble inorganic salt, and a water-soluble organic solvent, they can be easily removed by washing with water. The washing can be performed until the pH of the washing solution becomes neutral.

  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 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. For example, as in the case of drying using a box-type dryer or a band dryer, When it becomes a shape or the like, it is performed in order to break the pigment into powder, and examples thereof include mortar, hammer mill, disc mill, pin mill, jet mill and the like.

  In this way, a powder of polyhalogenated zinc phthalocyanine is obtained. The polyhalogenated zinc phthalocyanine of the present invention is a pigment, and has a property that the cohesion of primary particles is weaker than that of a conventional copper halide phthalocyanine, and it is easier to unravel. Therefore, any of the polyhalogenated zinc phthalocyanines of the present invention can be used for coloring known and commonly used media to be colored. Among them, the above-described preferred primary halogen particles having a mean particle diameter of polyhalogenated zinc phthalocyanine are preferable as a colorant because dispersibility in a synthetic resin to be colored becomes better.

  Further, in the case of using a polyhalogenated zinc phthalocyanine having a preferable average particle size of primary particles as described above for forming a pixel portion of a color filter, at 365 nm, which is frequently used for curing a photosensitive composition. It is preferable because the light-shielding property does not decrease, the photocuring sensitivity does not decrease, and film edge and pattern flow hardly occur during development.

  When the primary and horizontal aspect ratios of the polyhalogenated zinc phthalocyanine of the present invention are 1 to 3, the viscosity characteristics are improved in each application field and the fluidity is further increased. In order to obtain the aspect ratio, as in the case of obtaining the average particle diameter of the primary particles as described above, 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. .

  Various phthalocyanine derivatives can be contained in any step of producing the novel crystalline polyhalogenated zinc phthalocyanine of the present invention. By using a phthalocyanine derivative in combination with the novel crystalline polyhalogenated zinc phthalocyanine, it may be possible to improve the viscosity characteristics and the dispersion stability of the photosensitive composition for the color filter green pixel portion.

  The wavelength at which the transmittance of the spectral transmission spectrum is maximized is on the longer wavelength side, and the maximum transmittance value is also large, so it combines yellowish green and superior lightness compared to conventional polyhalogenated copper phthalocyanine A color filter having a green portion is obtained. That is, the wavelength (Tmax) at which the transmittance of the spectral transmission spectrum at 380 to 780 nm is maximum, which could not be achieved with the conventional polyhalogenated copper phthalocyanine, is 520 to 590 nm, and the transmittance at Tmax is 70% or more, and For the first time, a color filter having a green pixel portion having a transmittance of 20% or less at a wavelength of 650 to 700 nm using the polyhalogenated zinc phthalocyanine of the present invention is simpler and less expensive. Obtainable.

  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 polyhalogenated zinc phthalocyanine 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 transmittance as a color filter can be determined with higher accuracy by correcting (baseline correction or the like), for example, with a spectral transmission spectrum similarly determined for a film having the same dry film thickness only with a resin.

  The color filter of the present invention has the above-mentioned characteristics, but more preferably, the wavelength (Tmax) at which the transmittance of the spectral transmission spectrum at 380 to 780 nm is maximum is 520 to 590 nm, and the transmission at Tmax is performed. The transmittance is 70 to 99%, and the transmittance of the spectral transmission spectrum at a wavelength of 650 to 700 nm is 0 to 20%.

  In the present invention, it is preferable that various yellow pigments are used in combination for yellowing in forming the green pixel portion of the color filter. That is, by using a yellow pigment in combination with the polyhalogenated zinc phthalocyanine, it is possible to reduce the transmittance of the same spectral transmission spectrum at a wavelength of 400 to 500 nm, for example, the transmittance in the wavelength range. Can be made 50% or less.

  Examples of yellow pigments that can be used here include C.I. I. Pigment YELLOW 83, 110, 138, 139, 150, 180, 185, and the like. In the present invention, the combined proportion of the polyhalogenated zinc phthalocyanine and the yellow pigment is preferably 10 to 100 parts of the yellow pigment per 100 parts of the polyhalogenated zinc phthalocyanine in terms of mass.

  In the present invention, by using polyhalogenated zinc phthalocyanine for forming the green pixel portion of the color filter, even if a yellow pigment is used for color matching, a smaller amount may be used. A decrease in light transmittance over the entire region can be prevented to a minimum.

  In addition, when the polyhalogenated zinc phthalocyanine of the present invention is used, even if a yellow pigment is used in combination, a smaller amount may be used, so that a color filter having a green pixel portion of the same color as the conventional color filter green pixel portion is obtained. In this case, the same yellow pigment to be used in combination can be reduced by 30% or more and by a maximum of 50% in terms of mass.

  Furthermore, for the same reason, a pixel portion with less turbidity and excellent color purity can be obtained compared to the conventional case of mixing two or more different color pigments for toning. I can do it.

  For example, conventional C.I. I. Compared to the case where a mixed pigment using the above-mentioned yellow pigment in combination with the above-described yellow pigment is used for a green pigment such as Pigment GREEN 36, the case where the polyhalogenated zinc phthalocyanine of the present invention is used in combination with a yellow pigment is used as a liquid crystal display. The lowering of the brightness becomes smaller, and the light transmission amount in the green region also becomes larger.

  The polyhalogenated zinc phthalocyanine of the present invention can be used for forming a green pixel portion of a color filter by a known method. This pixel portion can be typically obtained from a photosensitive composition for a color filter green pixel portion containing a photosensitive resin and the novel crystalline polyhalogenated zinc phthalocyanine of the present invention as essential components.

  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, Trimethylol propaton triacrylate, pentaerythritol triacrylate, tris (2-hydroxyethyl) isocyanate, dipentaerythritol hexaacrylate, dipentaerythritol pentaacrylate It includes photopolymerizable monomers such as polyfunctional monomers such as.

  As a method for producing a color filter, for example, this polyhalogenated zinc phthalocyanine is dispersed in a dispersion medium made of a photosensitive resin, and then applied onto a transparent substrate such as glass by a spin coat method, a roll coat method, an ink jet method or the like. Then, a method called photolithography, in which the coating film is subjected to pattern exposure with ultraviolet rays through a photomask and then an unexposed portion is washed with a solvent or the like to obtain a green pattern.

  In addition, the color filter may be manufactured by forming a pattern of the green pixel portion by an electrodeposition method, a transfer method, a micellar electrolysis method, or a PVED (Photovoltaic Electrodeposition) method. Each pattern of the red pixel portion and the blue pixel portion can also be formed by a similar method using a known pigment.

  To prepare a color filter resist ink, the polyhalogenated zinc phthalocyanine of the present invention, a photosensitive resin, a photopolymerization initiator, and an organic solvent that dissolves the resin are mixed as essential components. As a manufacturing method thereof, a method is generally used in which a dispersion liquid is prepared using polyhalogenated zinc phthalocyanine, an organic solvent, and a dispersant as required, and then a photosensitive resin is added to obtain a resist ink. is there.

  Examples of the photopolymerization initiator include acetophenone, benzophenone, benzyldimethylketanol, 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.

  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, 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, 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.

  Examples of the dispersant used as needed include Big Chemie's Dispersic 130, Dispersic 161, Dispersic 162, Dispersic 163, Dispersic 170, Efka 46, Efka 47, and the like. In addition, a revenig rigging agent, a coupling agent, a cationic surfactant, and the like can be used together.

  First, in terms of mass, per 100 parts of the polyhalogenated zinc phthalocyanine of the present invention, 300 to 1000 parts of an organic solvent, and optionally 0 to 100 parts of a dispersant and / or 0 to 20 parts of a phthalocyanine derivative. Can be dispersed by stirring and dispersing so as to be uniform. Then, to this dispersion, in terms of mass, 3 to 20 parts of photosensitive resin per part of polyhalogenated zinc phthalocyanine, 0.05 to 3 parts of photopolymerization initiator per part of photosensitive resin, and if necessary Further, an organic solvent is further added, and the resist ink described above can be obtained by stirring and dispersing so as to be uniform.

  The resist ink for color filter thus prepared can be made into 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.

  The polyhalogenated zinc phthalocyanine of the present invention is a compound having a yellowish green color, and besides being applied to the green pixel portion for a color filter described in detail above as a pigment, paint, plastic, printing ink, rubber, leather Suitable for coloring, textile printing, electrophotographic toner, jet ink, thermal transfer ink and the like.

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

[Production Example 1]
Zinc phthalocyanine was produced from phthalic anhydride, urea, and zinc chloride. This 1-chloronaphthalene solution had light absorption at 750 to 850 nm.
Halogenation is performed by mixing 3.2 parts of thionyl chloride, 3.8 parts of anhydrous aluminum chloride and 0.5 parts of sodium chloride at 40 ° C., and adding 2.7 parts of bromine dropwise. 1 part of zinc phthalocyanine is added thereto and reacted at 90 ° C. for 15 hours, after which the reaction mixture is poured into water to precipitate a halogenated zinc phthalocyanine crude pigment. This aqueous slurry was filtered, washed with hot water at 60 ° C., washed with 1% aqueous sodium hydrogen sulfate, washed with hot water at 60 ° C., dried at 90 ° C., and 2.7 parts of purified polybrominated zinc phthalocyanine (crude oil). Pigment) was obtained.

The X-ray diffraction spectrum of this crude pigment is shown in FIG. The crude pigment was amorphous, unlike that defined in the present invention. The coloring power was very poor.
The X-ray diffraction spectrum was measured by using PHRDIPS XRD-XPERT-PRO-MPD, tube: Cu, sampling angle: 0.020 °, scan speed: 4.00 ° / min, operating angle 2θ. The measurement was performed under the condition of / θ.

1 part of polybrominated zinc phthalocyanine A, 1 part of sodium hydroxide, 10 parts of crushed sodium chloride, and 1 part of diethylene glycol were prepared in a double-arm kneader and kneaded at 100 ° C. for 8 hours. . After kneading is completed, the obtained magma cake is taken out in warm water at 60 ° C., stirred for 1 hour, repeatedly filtered and washed with hot water, repeatedly washed until pH 7 and specific conductivity become 0.5 mS / cm or less, dried, By grinding, 0.9 part of polybrominated zinc phthalocyanine B was obtained.
This polyhalogenated zinc phthalocyanine B had an average composition of ZnPcBr _13.9 Cl _1.8 H _0.3 from mass analysis and halogen content analysis by flask combustion ion chromatography.
This X-ray diffraction spectrum has a maximum diffraction peak at a black angle 2θ of 25.5 °, and has diffraction peaks at 9.6 °, 13.4 °, and 26.6 °, and is defined by the present invention. Had a new crystal form. The average particle diameter of the primary particles was 50 nm, and the aspect ratio of the primary particles in the vertical and horizontal directions was in the range of 1-3.

[Comparative Example 1]
The same operation as in Example 1 was carried out except that 1 part of sodium hydroxide was not used, to obtain 0.9 part of polybrominated zinc phthalocyanine C.
The X-ray diffraction spectrum of this polybrominated zinc phthalocyanine C is shown in FIG.
This X-ray diffraction spectrum has a maximum diffraction peak at a black angle 2θ of 25.5 °, and diffraction peaks at 16.8 °, 23.1 °, and 32.4 °. Had. Moreover, the average particle diameter of the primary particles was 60 nm, and the aspect ratio of the vertical and horizontal directions of the primary particles was in the range of 1-3.

Using the polybrominated zinc phthalocyanine B of Example 1 as a green pigment, a color filter green pixel portion was produced by photolithography.
First, 14 parts of polybrominated zinc phthalocyanine C, C.I. I. Pigment Yellow 150 3 parts, N, N′-dimethylformamide 2.5 parts, Dispersic 161 (manufactured by BYK Chemie) 17.0 parts, Euker ester EEP (manufactured by Union Carbide) 63.5 parts 0.5 mmφ Sepul beads And dispersed with a paint conditioner (manufactured by Toyo Seiki Co., Ltd.) for 1 hour to obtain a pigment dispersion.
5. 5.00 parts of this pigment dispersion, 5.50 parts of polyester acrylate resin (Aronix M7100, manufactured by Toa Gosei Chemical Co., Ltd.), dipentaerylate hexaacrylate (KAYARAD DPHA, manufactured by Nippon Kayaku Co., Ltd.) 00 parts, benzophenone (KAYACURE BP-100, manufactured by Nippon Kayaku Co., Ltd.) 1.00 part, and 13.5 parts of Euker ester EFP were stirred with a dispersion stirrer to obtain a color resist as a photosensitive composition. The color resist was applied to 1 mm thick glass so as to have a dry film thickness of 1 μm.
Next, pattern exposure with ultraviolet rays was performed through a photomask, and then the unexposed portion was washed with an organic solvent to obtain a color filter.

The color and brightness of the pattern of the color filter green pixel portion produced from polybrominated zinc phthalocyanine C were visually evaluated.
Luminance (Y value) is calculated by using a micro-spectrophotometer MCPD-3000 manufactured by Otsuka Electronics Co., Ltd. to calculate chromaticity coordinate x value and y value by F10 light source colorimetry. The Y value in CIE color development system chromaticity was measured by combining the values. Here, it was evaluated that the visual brightness was higher as the luminance (Y value) was higher.
For contrast, the color filter red pixel portion was installed between two polarizing plates, a light source was installed on one side, and a CCD camera was installed on the opposite side, and luminance was measured. It was calculated from the ratio of luminance (transmitted light intensity) between when the polarization axis was parallel and when it was vertical.
Further, when measured using a first-type spectrophotometer (spectrophotometer) defined in JIS Z 8722, the wavelength (Tmax) at which the transmittance of the spectral transmission spectrum at 380 to 780 nm is maximum is 525 nm, and the wavelength is 650. The maximum transmittance at 700 nm was 6.0%.
The luminance, contrast, and light transmittance at Tmax are shown in Table 1, respectively.

[Comparative Example 2]
A color filter green pixel portion was produced in the same manner as in Example 2 except that the polybrominated zinc phthalocyanine C of Comparative Example 1 was used instead of the polybrominated zinc phthalocyanine B of Example 2.
The obtained color filter green pixel portion was measured in the same manner as in Example 2. The results are shown in Table 1.

  As can be seen from Table 1, the color filter of Example 2 having a green pixel portion containing the novel crystalline polyhalogenated zinc phthalocyanine of the present invention is the same as the conventional crystalline polyhalogenated zinc phthalocyanine of Comparative Example 1. Compared to that of Comparative Example 2 having a green pixel portion to be contained, not only the light transmittance at Tmax was high, but also the luminance and contrast were very high.

2 is an X-ray diffraction spectrum of a raw material (crude pigment) of polybrominated zinc phthalocyanine of the present invention. 2 is an X-ray diffraction spectrum of the novel crystalline polybrominated zinc phthalocyanine of the present invention. 2 is an X-ray diffraction spectrum of a conventional crystal type polybrominated zinc phthalocyanine.

Claims (6)

In X-ray diffraction spectrum, it has a Bragg angle (2 [Theta] ± 0.2 °) 25.5 ° maximum diffraction peak for Cu-K [alpha line, 9.6 °, 13.4 °, a diffraction peak at 26.6 ° polyhalogenated zinc phthalocyanine, characterized by have a. The compound according to claim 1, wherein the polyhalogenated zinc phthalocyanine is polybrominated zinc phthalocyanine. The compound according to claim 1 or 2, wherein the primary particles have an average particle diameter of 0.01 to 0.1 µm. The photosensitive composition for color filter green pixel parts which contains photosensitive resin and the compound as described in any one of Claims 1-3 as an essential component. The color filter which contains the compound as described in any one of Claims 1-3 in a green pixel part. The wavelength (Tmax) which contains the compound as described in any one of Claims 1-3 in a green pixel part, and the transmittance | permeability of the spectral transmission spectrum in 380-780 nm becomes the maximum is 520-590 nm, The said wavelength ( A color filter having a transmittance at Tmax) of 70% or more and a transmittance of the spectral transmission spectrum at a wavelength of 650 to 700 nm of 20% or less.

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