JPWO2010061830A1 - Pigment composition for color filter, method for producing the same, and color filter - Google Patents

Abstract

A polyhalogenated zinc phthalocyanine pigment composition capable of obtaining a color filter excellent in heat resistance of contrast, a photosensitive composition containing the same, and a liquid crystal display for a long time at a high temperature containing the same in a green pixel portion A color filter capable of obtaining an image with little reduction in contrast. C. I. Pigment green 58 and / or C.I. I. Pigment Green 36 (A) and polyurethane resin (B), and C.I. I. Pigment green 58 and / or C.I. I. Pigment Green 36 (A) per 100 parts of the polyurethane resin (B) non-volatile content 0.1 to 10 parts, the color filter pigment composition, the green pixel part containing the pigment composition Color filter.

Description

  The present invention relates to a polyhalogenated zinc phthalocyanine pigment composition from which a color filter excellent in heat resistance of contrast can be obtained, a photosensitive composition containing the same, and a green pixel portion containing the same in a green pixel portion for a long period of time. The present invention relates to a color filter capable of obtaining an image with little reduction in contrast even when liquid crystal display is performed.

  Examples of the polyhalogenated metal phthalocyanine pigment include C.I. I. In addition to polyhalogenated copper phthalocyanine pigments such as CI Pigment Green 36, other polyhalogenated dissimilar metal phthalocyanine pigments are known. Among them, C.I. I. Polyhalogenated zinc phthalocyanine pigments such as CI Pigment Green 58 exhibit unique properties not found in other polyhalogenated dissimilar metal phthalocyanine pigments such as polyhalogenated aluminum phthalocyanine dimer pigments.

  Specifically, application of this polyhalogenated zinc phthalocyanine pigment to a green pixel portion of a color filter of a liquid crystal display device is known. The green pixel part containing this polyhalogenated zinc phthalocyanine pigment has high color purity because Tmax is on the higher wavelength side compared to the conventional green pixel part containing polyhalogenated copper phthalocyanine pigment. Can also be used suitably for high color purity color filters (Patent Document 1).

  Even this excellent polyhalogenated zinc phthalocyanine pigment has insufficient saturation and the color gamut is still unsatisfactory, so conventionally, a betaine-type amphoteric surfactant has been incorporated into the polyhalogenated zinc phthalocyanine pigment. By using the pigment composition, a wider color gamut was ensured with better saturation, and near ideal RGB color reproducibility was achieved in image display on liquid crystal display devices (Patent Literature). 2).

JP 2003-161827 A JP 2007-284592 A

  However, C.I. I. Pigment Green 36 and C.I. I. Since polyhalogenated metal phthalocyanine pigments such as CI Pigment Green 58 are finer than those used in conventional inks and paints, the color filter obtained by using them has a liquid crystal display device with a high temperature history. The problem that the contrast of the image display is reduced when received has not been solved.

The problem to be solved by the present invention is to provide a polyhalogenated metal phthalocyanine pigment composition suitable for forming a green pixel portion of a color filter excellent in heat resistance, the hue of which does not change even when subjected to a thermal history at a high temperature. It is to provide.
Further, the problem to be solved by the present invention is to provide a suitable method for producing the pigment composition, and to provide a contrast even when image display is performed at a high temperature for a long time, containing the pigment composition in a green pixel portion. The object is to provide a color filter with little deterioration.

  The present inventors evaluated the change in hue when a thermal history was applied after adding various surface treatment agents to the polyhalogenated metal phthalocyanine pigment.By using a polyurethane resin, the color filter and A polyhalogenated metal phthalocyanine pigment composition excellent in heat resistance of the contrast when obtained, and a color filter containing such a polyhalogenated metal phthalocyanine pigment composition in a green pixel portion at a high temperature for a long period of time. The present inventors have found that even when the image display is performed, the contrast is less reduced than in the prior art, and the present invention has been completed.

That is, the present invention relates to C.I. I. Pigment green 58 and / or C.I. I. Pigment Green 36 (A) and polyurethane resin (B), and C.I. I. Pigment green 58 and / or C.I. I. Provided is a pigment composition for a color filter, characterized in that the polyurethane resin (B) has a nonvolatile content of 0.1 to 10 parts per 100 parts of Pigment Green 36 (A).
The present invention also relates to C.I. I. Pigment green 58 and / or C.I. I. Pigment Green 36 (A) and an aqueous polyurethane resin dispersion were obtained on a C.I. I. Pigment green 58 and / or C.I. I. Provided is a method for producing a pigment composition for a color filter, wherein the liquid medium is removed after mixing so that the polyurethane resin (B) is 0.1 to 10 parts per 100 parts of Pigment Green 36 (A). .
Furthermore, this invention provides the color filter formed by containing the pigment composition for color filters mentioned above or the pigment composition for color filters obtained by the said manufacturing method in a green pixel part.

Since the polyhalogenated metal phthalocyanine pigment composition of the present invention contains a polyurethane resin, the hue does not change even when subjected to a heat history at high temperature, and has a particularly remarkable heat resistance.
The color filter containing the polyhalogenated metal phthalocyanine pigment composition of the present invention has a conventional color filter, even when displaying images for a long time at a higher temperature than the color filter containing a conventional polyhalogenated metal phthalocyanine pigment composition. Compared to the above, there is an especially remarkable effect that there is less contrast reduction.

Hereinafter, the present invention will be described in detail. Hereinafter, C.I. I. Pigment green 58 and / or C.I. I. Pigment Green 36 (A) may be abbreviated as pigment (A) or former pigment (A). Similarly, the polyurethane resin (B) may be abbreviated as the resin (B) or the latter resin (B).
The pigment composition for a color filter in the present invention includes C.I. I. Pigment green 58 and / or C.I. I. Pigment Green 36 (A) and polyurethane resin (B) are contained, and 0.1 to 10 parts of the latter resin (B) per 100 parts of the former pigment (A) on a mass basis.

  As a result of trial and error, the inventors of the present invention incorporated various surfactants and polymers into the pigment (A) and compared the heat resistance of the photosensitive composition for color filters. As a result, a small amount of polyurethane resin (B) was used. Only the pigment composition obtained by inclusion was found to have a small change in hue, a small decrease in contrast, and excellent heat resistance even when used for a long time at a specific high temperature when used as a color filter.

  The pigment (A) in the present invention is C.I. which is a polyhalogenated zinc phthalocyanine pigment. I. Pigment Green 58, C.I. which is a polyhalogenated copper phthalocyanine pigment. I. Pigment Green 36 and a mixture thereof. Hereinafter, the polyhalogenated zinc phthalocyanine pigment and the polyhalogenated copper phthalocyanine pigment are collectively referred to as a polyhalogenated metal phthalocyanine pigment.

  In the present invention, the pigment (A) is preferably a polyhalogenated metal phthalocyanine pigment having an average primary particle size of 0.01 to 0.30 μm.

  In addition, the average particle diameter of the primary particles in the present invention refers to a pigment that forms 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.). For 50 primary particles of A) or the pigment composition of the present invention, the longer diameter (major diameter) is determined and averaged. At this time, the pigment (A) as a sample or the pigment composition of the present invention 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.

  Examples of the polybrominated zinc phthalocyanine pigment include C.I. I. Pigment Green 58, for example, FASTOGEN (registered trademark) GREEN KTY-CF manufactured by DIC Corporation, FASTOGEN (registered trademark) GREEN A-110, and the like. Examples of the polybrominated copper phthalocyanine pigment include C.I. I. CI Pigment Green 36, for example, FASTOGEN (registered trademark) GREEN 2YK-50, FASTOGEN (registered trademark) GREEN 2YK-53, FASTOGEN (registered trademark) GREEN 2YK-CF manufactured by DIC Corporation.

  Especially, C.I. I. Pigment Green 58 is a C.I. I. Compared to Pigment Green 36, when a color filter is used, it is more preferable because it has high color purity and can achieve a higher level of luminance and more ideal RGB color reproducibility.

  In the present invention, it is preferable to use a polybrominated zinc phthalocyanine pigment having an average primary particle diameter of 0.01 to 0.10 μm for color filter applications.

  The polyurethane resin (B) in the present invention contains two or more urethane bonds as essential in one molecule. The polyurethane resin (B) includes not only a urethane bond but also a polyurethane polyurea resin containing a urea bond.

  Examples of the polyurethane resin (B) include polyether-based polyurethane resins, polyether ester-based polyurethane resins, polyester-based polyurethane resins, and the like, but the polyester-based polyurethane resin has high heat resistance when used as a color filter described later. It is preferable at an excellent point.

  The polyurethane resin (B) is a linear thermoplastic polyurethane resin obtained by reacting only an organic diisocyanate, a diol, and, if necessary, a bifunctional chain extender, because it has excellent film properties and is easy to handle. preferable.

  The polyurethane resin (B) has excellent dispersion when the binder resin or monomer used in the preparation of the photosensitive composition to be described later is a (meth) acrylate resin or a (meth) acrylate ester. A polyurethane resin containing a linear aromatic unit having an aromatic ring in the main chain and an anionic group is preferable in terms of stability, and is preferable in terms of excellent film properties such as adhesion and durability. However, the polyester-based polyurethane resin obtained by using an aliphatic or alicyclic diisocyanate containing a linear aromatic unit having an aromatic ring in the main chain and an anionic group is further excellent in heat resistance and has a long period of time. This is particularly preferable in that the decrease in contrast of an image when liquid crystal display is performed is small. Here, the anionic group means, for example, an acid group such as a carboxyl group or a sulfonic acid group or a salt obtained by neutralizing these acid groups with a base. This excellent heat resistance is discovered for the first time by conducting a heat resistance test described in detail later, and cannot be known from observation in a normal state without performing the heat resistance test.

  As this particularly preferred polyurethane resin, it contains a linear aromatic unit containing the above-mentioned linear aromatic polyester unit and containing an aromatic ring in the main chain, and an anionic group. The organic diisocyanate is aliphatic diisocyanate or fatty acid. The polyurethane resin obtained using cyclic diisocyanate is mentioned. As will be described later, the pigment used when forming the pixel portion of the color filter is generally smaller in luminance when some surface treatment is performed than in the luminance when only it is used (no treatment). But C.I. I. When the pigment green 58 is treated with the particularly preferable polyurethane resin, there is a specificity that the luminance is higher than that in the case of no treatment.

  The polyurethane resin (B) may be used as the pigment composition of the present invention by mixing its non-volatile content with the pigment (A) as it is, but the pigment (A) and the resin (B) are dissolved in a liquid medium or After mixing the dispersed solution or dispersion, the liquid medium is removed to prepare a pigment composition in which the pigment (A) and the resin (B) are more uniformly mixed. This mixing is preferably performed with stirring. Among them, the pigment (A) and a solution or dispersion in which the resin (B) is dissolved or dispersed in a liquid medium are mixed and stirred and heated, so that the resin (B) is compared with the case where heating is not performed. The surface of the pigment (A) can be coated more uniformly and reliably. Further, by applying pressure and heating, not only the coating of the resin (B) on the surface of the pigment (A) particles in the case of simple heating, but also the resin in the voids such as the pores of the pigment (A) particles. The penetration of (B) can be promoted, and the effect of coating is further increased.

At this time, when a liquid medium containing only a water or a water-soluble organic solvent mainly containing water (referred to as an aqueous medium) is used as the liquid medium, the mixing heating is performed using only the organic solvent as the liquid medium. In comparison, the change in the crystal shape and the like of the pigment (A) itself is small and the hue change is small, which is preferable.
A dispersion in which the polyurethane resin (B) is dispersed in an aqueous medium is referred to as a polyurethane resin aqueous dispersion.

  Examples of the polyurethane resin used in the present invention include Hydran (registered trademark) AP-40F, AP-30F, AP-20 (above, manufactured by DIC Corporation), Superflex 460, 460S, and 126. Examples thereof include aqueous polyurethane resin dispersions (manufactured by Daiichi Kogyo Seiyaku Co., Ltd.).

  In the present invention, the pigment (A) and the resin (B) aqueous dispersion are 0.1 to 10 parts of the latter resin (B) per 100 parts of the former pigment (A) on a mass basis of the nonvolatile content. Especially, after mixing so that it may become 0.5-5 parts, especially 1-3 parts, it is preferable to remove a liquid medium and to manufacture a pigment composition. The latter resin (B) charged in this way does not flow out even if the treatment described later is performed, and at least 70% of its nonvolatile content remains in the pigment (A) on a mass basis.

  Heating of the pigment (A) and the resin (B) can be carried out in a range of 30 minutes to 5 hours in a closed system with stirring at a temperature of 100 to 150 ° C. after mixing them. By heating in a closed system in this way, a pressurized state is formed, and as described above, the polyurethane resin (B) penetrates into the voids of the pigment particles, so that only the particle surface is covered. Compared with this, a more excellent effect is exhibited.

  The mixture thus heated is cooled, for example, and the liquid medium is removed therefrom. If necessary, the solid is washed, filtered, dried, pulverized, etc., so that the pigment (A) and the polyurethane resin (B ) Containing the pigment composition of the present invention.

  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. By washing, the resin (B) not adsorbed on the pigment (A) can be easily removed. If necessary, acid cleaning, alkali cleaning, and solvent cleaning may be performed so as not to change the crystal state. The amount of resin (B) non-volatile content (so-called yield), which is an active ingredient, contained in the pigment composition for color filters is, for example, from the amount of resin extracted by solvent extraction of the pigment composition or from the charged resin (B) It can obtain | require from the outflow amount in the filtrate with respect to.

  Examples of the drying after filtration and washing described above include batch-type or continuous drying in which the pigment is dehydrated and / or desolvated by heating at 80 to 120 ° C. with a heating source installed in a dryer. Examples of the dryer generally include a box dryer, a band dryer, and a spray dryer. In particular, spray dry drying is preferable because it is easily dispersed during paste preparation. In addition, the pulverization after drying is not an operation for increasing the specific surface area or reducing the average particle diameter of the primary particles, but for example, the pigment is a lamp as in the case of drying using a box dryer or a band dryer. When it becomes a shape, etc., 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 dry powder containing a color filter pigment composition containing the pigment (A) and the resin (B) as a main component is obtained.

  The pigment composition for a color filter of the present invention can be used for any known and commonly used applications. However, when the average particle diameter of primary particles is 0.01 to 0.10 μm, pigment aggregation is relatively weak and coloring is performed. Dispersibility into power synthetic resin and the like becomes better.

  When the color filter pigment composition of the present invention is used for a color filter green pixel portion, the pigment dispersion in the color filter photosensitive composition is easy, and the color filter photosensitive composition is cured. The light-shielding property at 365 nm, which is frequently used in the film, is reduced, the photocuring sensitivity of the resist is not lowered, and film edge and pattern flow during development are less likely to occur. A color filter green pixel portion having both high sharpness and high brightness demanded in recent years can be obtained more easily.

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

  The color filter of the present invention can be obtained by containing the pigment composition for a color filter of the present invention at least in the green pixel portion of the color filter. In the field of color filters, unlike conventional printing inks and paints such as general-purpose applications, the saturation value handling is very strict, and it is difficult to improve the saturation value very slightly. By using this pigment composition for the preparation of a color filter, the color purity is improved and a liquid crystal display device having a wider RGB color reproduction range can be obtained.

  C. I. The pigment composition for a color filter suitable for use in the present invention, which contains CI Pigment Green 58, is used in combination with or without a yellow pigment in particular for color matching when obtaining a green pixel portion of a color filter. Therefore, a decrease in light transmittance in the entire region of 380 to 780 nm can be prevented to a minimum. In particular, since it has a more yellowish color and higher coloring power, if the color density is the same, the yellow pigment may be used in a smaller amount, which is advantageous because the transmittance can be further increased.

  In addition, C.I. I. As described above, the preferred color filter pigment composition of the present invention containing CI Pigment Green 58 has a wavelength (Tmax) at which the transmittance of the spectral transmission spectrum at 380 to 780 nm is maximum, and is 510 to 520 nm. The half-value width of the transmission curve is as sharp as 110 nm or less. (This wavelength is not affected by the photosensitive resin as described later.)

  The spectral transmission spectrum in the present invention is obtained according to the first-class spectrophotometer of Japanese Industrial Standard JIS Z 8722 (color measurement method-reflective and transmissive object color). The resin film containing the pigment composition 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 pigment composition for a color filter of the present invention can be used as it is for the production of a green pixel portion of a color filter, but if necessary, in consideration of economy, a known conventional green or yellow pigment or A pigment derivative may be used in combination.

  In addition to the green pigment, a yellow pigment may be used for toning in order to make the characteristics appear. Examples of yellow pigments that can be used here include C.I. I. And yellow organic pigments such as CI Pigment Yellow 83, 110, 138, 139, 150, 180, and 185.

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

  As a method for producing a color filter, for example, this pigment composition for a color filter is dispersed in a dispersion medium made of a photosensitive resin, and then applied onto a transparent substrate such as glass by a spin coating method, a roll coating method, an ink jet method or the like. There is a method called photolithography in which a coating pattern is applied to the coating film, followed by 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. In addition, the pattern of a red pixel part and the pattern of a blue pixel part can also be formed by the same method using a well-known pigment. The color filter pigment composition of the present invention is extremely useful in, for example, a method for producing a color filter in which baking is included in the process because the hue change is small even when subjected to a thermal history.

  In order to prepare the photosensitive composition for the color filter green pixel portion, for example, the pigment composition for the color filter of the present invention, a photosensitive resin, a photopolymerization initiator, and an organic solvent that dissolves the resin are essential. Mix as an ingredient. As the production method, a method of preparing a dispersion liquid using the pigment composition for a color filter of the present invention, an organic solvent, and a dispersant as required, and adding a photosensitive resin or the like to the dispersion liquid is generally used. Is.

  Dispersants used as necessary include, for example, Big Chemie Dispersic (DisperbyK registered trademark) 130, Dispersic 161, Dispersic 162, Dispersic 163, Dispersic 170, Efka 46, Efka 47, and the like. It is done. In addition, a revenig rigging agent, a coupling agent, a cationic surfactant, and the like can be used together.

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

  300 to 1000 parts by mass of an organic solvent and 100 to 100 parts by mass of a dispersant and / or 0 to 20 parts by mass of a phthalocyanine derivative as required per 100 parts by mass of the pigment composition for a color filter of the present invention, A dispersion can be obtained by stirring and dispersing so as to be uniform. Subsequently, 3 to 20 parts by mass of the photosensitive resin per 1 part by mass of the pigment composition for a color filter of the present invention and 0.05 to 3 parts by mass of a photopolymerization initiator per 1 part by mass of the photosensitive resin are added to the dispersion. Further, if necessary, an organic solvent can be further added and stirred and dispersed so as to be uniform, whereby a photosensitive composition for a color filter green pixel portion can be obtained.

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

  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.

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

  The pigment composition for a color filter of the present invention develops a bright green color with a yellowish green color and high coloring power, high color purity and high contrast. Therefore, it is suitable for coloring paints, plastics, printing inks, rubbers, leathers, textile printing, electronic toners, jet inks, thermal transfer inks and the like in addition to the color filters described in detail.

  Next, examples of the present invention will be shown and described in detail. Hereinafter, unless otherwise indicated,% means mass%, and part means mass part.

FASTOGEN (registered trademark) GREEN A-110 (polybrominated zinc phthalocyanine pigment manufactured by DIC Corporation) 20 g and hydran AP-30F (polyurethane resin aqueous dispersion manufactured by DIC Corporation. Non-volatile content (mass conversion) 50%. A polyether polyurethane resin obtained by using an aliphatic or alicyclic diisocyanate containing a polyether unit consisting of repeating alkylene oxide and a carboxyl group.) 0.4 g and 600 g of ion-exchanged water Was charged into a 1 liter autoclave, heated to 130 ° C. in 2 hours with stirring, and heated and stirred at the same temperature for 5 hours.
Thereafter, the mixture was allowed to cool to room temperature, filtered by suction to obtain a solid content, and the solid matter on the filter paper was washed with 5 l of ion-exchanged water. The wet cake of the pigment composition thus obtained was dried in a dryer at 90 ° C. for 12 hours and pulverized with a lab mill.
From the amount of resin extracted by solvent extraction of the dried pigment composition thus obtained, at least 80% (in terms of mass) of the charged hydran AP-30F adhered to FASTOGEN (registered trademark) GREEN A-110. It was confirmed that The average particle diameter of the primary particles of the pigment composition for a color filter was 0.01 to 0.10 μm, and the aspect ratio was in the range of 1 to 3.

<Preparation of composition for color filter green pixel part>
2.48 parts by weight of the dried pigment composition for color filter obtained in Example 1 above, 1.86 parts by weight of the cationic polymer Ajisper PB-814 (solid content 40%) manufactured by Ajinomoto Fine Techno Co., Propylene To a mixture of 12.16 parts by mass of glycol monomethyl ether acetate, 0.3 to 0.4 mmφ zircon beads were added, and dispersed for 80 minutes with a paint conditioner manufactured by Toyo Seiki Co., Ltd. to obtain a colored composition (I). 4.0 parts by weight of the obtained colored composition (I), 1.63 parts by weight of propylene glycol monomethyl ether acetate, 2.55 parts by weight of acrylic resin solution Unidic (registered trademark) ZL-295 manufactured by DIC Corporation The mixture was stirred with a dispersion stirrer (Mazerustar, Kurashiki Boseki Co., Ltd.) to obtain a composition for forming a color filter green pixel portion.

<Production of glass substrate for CF test>
Subsequently, the above composition was applied onto a glass substrate by a spin coater. The number of rotations of the spin coater was 600, 800, 1000, and 1200 rpm, and four types of glass plates having different coating film thicknesses of the composition were prepared. Each glass plate coated with the composition thus obtained was heated at 90 ° C. for 3 minutes to obtain a color filter green pixel portion.

<Evaluation of color filter green pixel part>
Various color filter characteristics were evaluated using the obtained glass substrate.
Hue (x, y) and luminance (Y value) were determined using a microspectrophotometer MCPD-3000 manufactured by Otsuka Electronics Co., Ltd. First, the chromaticity coordinate x value and y value in C light source colorimetry and the Y value in CIE color development chromaticity were measured for each of four types of glass plates having different film thicknesses. Based on this, an x-Y graph consisting of four points was created, and the Y value at y = 0.42 on the approximate line was taken as the luminance. Higher brightness means higher visual brightness.

For initial contrast, the color filter green pixel part is installed between two polarizing plates, a light source is installed on the outside of the polarizing plate, and a color luminance meter BM-5A made by Topcon Technohouse is installed on the other side. Thus, the luminance was measured when the polarization axes of the two polarizing plates were parallel and perpendicular. A graph of chromaticity coordinates y and contrast is created by measuring the ratio of the luminance at the time of parallel and vertical and the contrast of each glass plate, and measuring four glass plates, and y = 0.48 on the approximate line. The value at is taken as the contrast of the green pixel portion.
For heat resistance, the glass substrate provided with the color filter green pixel portion for which the initial contrast was measured was placed in a dryer at 250 ° C. for 1 hour, taken out and allowed to cool, and then the contrast was measured in the same manner, and the heat for the initial contrast was measured. The change in contrast after receiving the history was obtained, and the attenuation rate was expressed in%.

In place of Hydran AP-30F, Hydran AP-40F (polyurethane resin aqueous dispersion manufactured by DIC Corporation. Nonvolatile content (mass conversion) 50%. A linear aromatic unit containing an aromatic ring in the main chain and an anionic group. Except that the same amount of an aliphatic or alicyclic diisocyanate-containing polyester-based polyurethane resin) is used, and the same operation as in Example 1 is carried out, followed by drying to obtain a pigment composition for a color filter. It was.
From the amount of resin extracted by solvent extraction of the dried pigment composition thus obtained, at least 80% (in terms of mass) of the charged hydran AP-40F adhered to FASTOGEN (registered trademark) GREEN A-110. It was confirmed that The average particle diameter of the primary particles of the pigment composition for a color filter was 0.01 to 0.10 μm, and the aspect ratio was in the range of 1 to 3.

  Using the dried color filter pigment composition thus obtained, in the same manner as in Example 1, <Preparation of color filter green pixel part composition>, <CF test glass substrate preparation>, and <Color filter green color> Evaluation of pixel portion> was performed.

[Comparative Example 1]
In the same manner as in Example 1, except that neither Hydran AP-30F nor Hydran AP-40F is used, and 2.48 parts by mass of Fastogen (registered trademark) Green A-110 is used, <color filter green pixel unit Preparation of composition for glass>, <preparation of glass substrate for CF test>, and <evaluation of color filter green pixel portion>. The average particle diameter of the primary particles of this pigment composition was in the range of 0.01 to 0.10 μm.

[Comparative Example 2]
In place of Hydran AP-30F, the same operation as in Example 1 was performed except that the same amount in terms of nonvolatile content of Amphital (AMPHITL registered trademark) 24B (carboxybetaine surfactant: manufactured by Kao Corporation) was used. And dried to obtain a color filter pigment composition.
Based on the amount of resin extracted by solvent extraction of the dried pigment composition obtained in this way, at least 80% (in terms of mass) of the non-volatile content of charged Amphital 24B is attached to FASTOGEN (registered trademark) GREEN A-110 Was confirmed. The average particle diameter of the primary particles of the color filter pigment composition was in the range of 0.01 to 0.10 μm.

  Using the dried color filter pigment composition thus obtained, in the same manner as in Example 1, <Preparation of color filter green pixel part composition>, <CF test glass substrate preparation>, and <Color filter green color> Evaluation of pixel portion> was performed.

  The evaluation results of Examples 1 and 2 and Comparative Examples 1 and 2 are summarized in Table 1.

Table 1

As is clear from Table 1, the color filter of the example having a green pixel portion made from the pigment composition for a color filter of the present invention has a heat resistance to that of the comparative example from the comparison between the example and the comparative example. Is remarkably superior.
From the comparison between Example 1 and Comparative Example 2, the color filter of Example 1 having a green pixel portion using the pigment composition for a color filter of the present invention containing a polyurethane resin is a conventional betaine-type amphoteric surfactant. Compared to the color filter of Comparative Example 2 obtained in the same manner using a pigment composition containing an agent, the initial contrast is the same, but the heat resistance is good.

  From the comparison between Example 1 and Example 2, the color filter of Example 2 having a green pixel portion using the pigment composition for a color filter of the present invention containing a polyester polyurethane resin contains a polyether polyurethane resin. Compared with the color filter of Example 1 obtained similarly using the pigment composition for color filters of this invention, heat resistance is still more favorable. Further, the color filter of Example 2 shows a higher luminance (Y) than the color filter of Comparative Example 1 obtained in the same manner from a pigment alone containing no polyurethane resin, and the surface treatment of the pigment Etc., there is also a very specific effect that overturns the conventional wisdom of those skilled in the art that the luminance is lower than before processing.

  Moreover, the color filter pigment composition of the present invention containing a polybrominated zinc phthalocyanine pigment has higher chroma and higher color purity than the color filter pigment composition of the present invention containing a polybrominated copper phthalocyanine pigment. It has chromaticity and also exhibits very high coloring power. Therefore, the pigment composition for a color filter of the present invention containing a polybrominated zinc phthalocyanine pigment is most suitable for pattern formation of a green pixel portion of a color filter for a large screen such as a display of a more ideal RGB color reproduction range.

  The present invention relates to a polyhalogenated zinc phthalocyanine pigment composition from which a color filter excellent in heat resistance of contrast can be obtained, a photosensitive composition containing the same, and a green pixel portion containing the same in a green pixel portion for a long period of time. It is possible to provide a color filter that can obtain an image with little reduction in contrast even when liquid crystal display is performed.

Claims (5)

C. I. Pigment green 58 and / or C.I. I. Pigment Green 36 (A) and polyurethane resin (B), and C.I. I. Pigment green 58 and / or C.I. I. A pigment composition for a color filter, wherein the polyurethane resin (B) has a nonvolatile content of 0.1 to 10 parts per 100 parts of Pigment Green 36 (A). The pigment composition for a color filter according to claim 1, wherein the polyurethane resin (B) is a polyester polyurethane resin. C. I. Pigment green 58 and / or C.I. I. Pigment Green 36 (A) and an aqueous polyurethane resin dispersion were obtained on a C.I. I. Pigment green 58 and / or C.I. I. A method for producing a pigment composition for a color filter, wherein the liquid medium is removed after mixing so that the polyurethane resin (B) is 0.1 to 10 parts per 100 parts of Pigment Green 36 (A). The method for producing a pigment composition for a color filter according to claim 3, wherein the polyurethane resin (B) is a polyester polyurethane resin. A color filter comprising the color pixel pigment composition according to claim 1 or 2 in a green pixel portion.