JP5210286B2 - Red coloring composition for color filter and color filter - Google Patents

Description

  The present invention relates to a red coloring composition for a color filter used for a color liquid crystal display device or a solid-state imaging device, and a color filter formed using the red coloring composition.

  A color filter has two or more kinds of fine band (striped) filter segments arranged in parallel or intersecting with each other on the surface of a transparent substrate such as glass, or the fine filter segments are arranged vertically and horizontally. It is made up of those arranged in The filter segments are as fine as several microns to several hundreds of microns, and are regularly arranged in a predetermined arrangement for each hue.

On the color filter used in the color liquid crystal display device, a transparent electrode for driving the liquid crystal is generally formed by vapor deposition or sputtering, and an alignment film for aligning the liquid crystal in a certain direction is formed thereon. . In order to sufficiently obtain the performance of these transparent electrodes and alignment films, it is necessary to perform the formation process at a high temperature of generally 200 ° C. or higher, preferably 230 ° C. or higher.
Therefore, at present, as a method for producing a color filter, a pigment dispersion method using a pigment having excellent light resistance and heat resistance as a colorant is mainly used.

In general color filters, blue, green, and red filter segments, which are the three primary colors of light, are arranged on a transparent substrate, but each of them obtains a spectral spectrum as a target color filter with only a single pigment. In many cases, it is difficult to adjust the spectrum using two or more pigments. (For example, see Patent Documents 1 and 2.)
Further, in the color filter in which the filter segments of the three primary colors of light are arranged, in recent years, there is an increasing demand for improvement of color characteristics such as transmittance, that is, lightness and color purity. Regarding the color characteristics, there is a request corresponding to each application not only for each single color but also for white obtained by lighting three colors, and is managed by chromaticity, color temperature (K), and color difference (Δuv). The management of the color characteristics is performed by using the XYZ (Yxy) color system (CIE standard color system) and expressing the color with three values of Yxy using a chromaticity diagram, where Y corresponds to the lightness, xy Corresponds to chromaticity.

Japanese Patent Laid-Open No. 11-14824 Japanese Patent Laid-Open No. 11-14825

Since the color characteristics of white are defined by the chromaticity and brightness of each color, conventionally, it is necessary to change the chromaticity of the three colors in order to adjust the color temperature (K) and color difference (Δuv) of white. there were. As a result, since white is set to the target color temperature (K) and color difference (Δuv), the target of the chromaticity of each color cannot be achieved.
Therefore, the present invention adjusts the lightness of red so that white can be adjusted to the target color temperature (K) and color difference (Δuv) without changing the chromaticity of the three colors. An object of the present invention is to provide a colored composition and a color filter formed using the composition.

For color filters red coloring composition in the invention, a red pigment, a green color element, necessary to adjust the brightness of the red filter segment by including a yellow dye in a specific ratio, a 3-color chromaticity It is possible to adjust white to the target color temperature (K) and color difference (Δuv) without changing.
Chi words, color filter red colored composition of the present invention comprises a transparent resin, a coloring matter carrier comprising a precursor thereof or a mixture thereof, the red dye and a green dye dispersed in the dye carrier, the green pigment Content is 0.01 to 15 weight% on the basis of the whole quantity of a pigment | dye, It is characterized by the above-mentioned.
The red coloring composition of the present invention can further contain a yellow pigment.

  In addition, the color filter in the present invention includes at least one red filter segment, at least one green filter segment, and at least one blue filter segment, and the at least one red filter segment is formed from the above-described red coloring composition. It is characterized by that.

  A color filter having a red filter segment formed by using the red coloring composition of the present invention can give a good value for white balance of a color liquid crystal display device, and is a transmissive / reflective color liquid crystal. It is suitable as a color filter for color separation of a display device and a solid-state image sensor.

First, the red coloring composition for color filters of the present invention will be described.
The coloring composition of the present invention contains a dye carrier composed of a transparent resin, a precursor thereof, or a mixture thereof, and a red dye and a green dye, or a red dye and a black dye dispersed in the dye carrier. The red coloring composition for a color filter can further contain a yellow pigment in order to achieve a desired spectral spectrum.
The dye carrier provides a resinous binder in the red filter segment that is formed.

  Examples of red pigments include C.I. I. Pigment Red 7, 9, 14, 41, 48: 1, 48: 2, 48: 3, 48: 4, 81: 1, 81: 2, 81: 3, 97, 122, 123, 144, 146, 149, 168, 169, 177, 178, 180, 181, 184, 185, 187, 192, 200, 202, 208, 210, 215, 216, 217, 220, 223, 224, 226, 227, 228, 240, 246, 254, 255, 264, 272, C.I. I. Red pigments such as Pigment Orange 36, 43, 51, 55, 59, 61, 71, 73, and orange pigments can be used. In particular, from the viewpoint of the balance between hue and lightness, C.I. I. It is preferable to use at least one red pigment selected from the group consisting of Pigment Red 48: 1, 81: 2, 81: 3, 122, 177, 179, 202, 207, 209, 224, 254, 255, 264. .

  Examples of yellow pigments include C.I. I. Pigment Yellow 1, 2, 3, 4, 5, 6, 10, 12, 13, 14, 15, 16, 17, 18, 20, 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, 86, 93, 94, 95, 97, 98, 100, 101, 104, 106, 108, 109, 110, 113, 114, 115, 116, 117, 118, 119, 120, 123, 125, 126, 127, 128, 129, 137, 138, 139, 147, 148, 150, 151, 152, 153, 154, 155, 156, 161, 162, 164, 166, 167, 168, 169, 170, 171, 172, 173, 174, 1 It can be used yellow pigments such 5,176,177,179,180,181,182,185,187,188,193,194,199,213,214. In particular, from the viewpoint of the balance between hue and lightness, C.I. I. It is preferable to use at least one yellow pigment selected from the group consisting of Pigment Yellow 13, 138, 139, 150, and 185.

Examples of the green pigment include C.I. I. Green pigments such as Pigment Green 7, 10, 36, and 37 can be used.
When the red coloring composition for a color filter contains a red pigment and a green pigment, the content of the green pigment is 0.01 to 20% by weight and 0.5 to 15% by weight based on the total amount of the pigment. Is preferred. When the content of the green pigment exceeds 20% by weight, the lightness becomes too small and the x value becomes small, making it difficult to match the target red hue. If it is less than 0.01% by weight, the change in brightness is too small to reach the desired brightness.

  Moreover, when the red coloring composition for color filters contains a yellow pigment | dye further, it is red pigment | dye 32-99.98 weight%, yellow pigment | dye 0.01-48 weight%, and green pigment | dye 0.01-20 weight%. It is preferable that there are 37 to 99.49% by weight of a red dye, 0.01 to 48% by weight of a yellow dye, and 0.5 to 15% by weight of a green dye. If the yellow pigment content exceeds 48% by weight, the y value becomes too large to match the desired red hue, and if it is less than 0.01% by weight, the hue change is too small. It becomes difficult to match the target red hue.

Examples of the black pigment include carbon black, titanium black, aniline black, anthraquinone black pigment, perylene black pigment, specifically C.I. I. Pigment Black 6, 7, 12, 20, 31, 32, etc., among which carbon black is preferable. Carbon black may be surface-treated with a resin or the like.
When the red coloring composition for a color filter contains a red pigment and a black pigment, the content of the black pigment is 0.01 to 10% by weight and 0.01 to 5% by weight based on the total amount of the pigment. Is preferred. When the content of the black pigment exceeds 10% by weight, the lightness becomes too small, and when it is less than 0.01% by weight, the change in lightness is too small to reach the target lightness.

  Moreover, when the red coloring composition for color filters contains a yellow pigment | dye further, red pigment | dye 36-99.98 weight%, yellow pigment | dye 0.01-54 weight%, black pigment | dye 0.01-10 weight% It is preferable that the red pigment is 41 wt% to 99.89 wt%, the yellow pigment 0.01 wt% to 54 wt%, and the black pigment 0.01 wt% to 5 wt%. If the yellow pigment content exceeds 54% by weight, the y value becomes too large to match the target red hue, and if it is less than 0.01% by weight, the hue change is too small. It becomes difficult to match the desired green hue.

The dye carrier for dispersing the dye is composed of a transparent resin, a precursor thereof, or a mixture thereof as described above. The transparent resin is a resin having a transmittance of preferably 80% or more, more preferably 95% or more in the entire wavelength region of 400 to 700 nm in the visible light region. Transparent resins include thermoplastic resins, thermosetting resins, and active energy ray curable resins, and precursors thereof include monomers or oligomers that are cured by irradiation with active energy rays to form transparent resins. These can be used alone or in admixture of two or more.
When the composition is cured by ultraviolet irradiation, a photopolymerization initiator or the like is added to the red coloring composition for the color filter.

  Examples of the thermoplastic resin include butyral resin, styrene-maleic acid copolymer, chlorinated polyethylene, chlorinated polypropylene, polyvinyl chloride, vinyl chloride-vinyl acetate copolymer, polyvinyl acetate, polyurethane resin, and polyester resin. Acrylic resins, alkyd resins, polystyrene resins, polyamide resins, rubber resins, cyclized rubber resins, celluloses, polyethylene (HDPE, LDPE), polybutadiene, polyimide resins, and the like. Examples of the thermosetting resin include epoxy resins, benzoguanamine resins, rosin-modified maleic acid resins, rosin-modified fumaric acid resins, melamine resins, urea resins, and phenol resins.

  As the active energy ray-curable resin, a (meth) acryl having a reactive substituent such as an isocyanate group, an aldehyde group or an epoxy group on a linear polymer having a reactive substituent such as a hydroxyl group, a carboxyl group or an amino group. A resin in which a photocrosslinkable group such as a (meth) acryloyl group or a styryl group is introduced into the linear polymer by reacting a compound or cinnamic acid is used. Further, a linear polymer containing an acid anhydride such as a styrene-maleic anhydride copolymer or an α-olefin-maleic anhydride copolymer is converted into a (meth) acrylic compound having a hydroxyl group such as hydroxyalkyl (meth) acrylate. Half-esterified products are also used.

  Monomers and oligomers include methyl (meth) acrylate, ethyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, cyclohexyl (meth) acrylate, β-carboxyethyl (meth) acrylate , Polyethylene glycol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, triethylene glycol di (meth) acrylate, tripropylene glycol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol Tri (meth) acrylate, 1,6-hexanediol diglycidyl ether di (meth) acrylate, bisphenol A diglycidyl ether di (meth) acrylate, neo Pentyl glycol diglycidyl ether di (meth) acrylate, dipentaerythritol hexa (meth) acrylate, tricyclodecanyl (meth) acrylate, ester acrylate, methylolated melamine (meth) acrylate, epoxy (meth) acrylate, urethane Various acrylates and methacrylates such as acrylates, (meth) acrylic acid, styrene, vinyl acetate, hydroxyethyl vinyl ether, ethylene glycol divinyl ether, pentaerythritol trivinyl ether, (meth) acrylamide, N-hydroxymethyl (meth) acrylamide , N-vinylformamide, acrylonitrile and the like, and these can be used alone or in admixture of two or more.

  Examples of the photopolymerization initiator include 4-phenoxydichloroacetophenone, 4-t-butyl-dichloroacetophenone, diethoxyacetophenone, 1- (4-isopropylphenyl) -2-hydroxy-2-methylpropan-1-one, 1- Acetophenone-based photopolymerization initiators such as hydroxycyclohexyl phenyl ketone, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butan-1-one c, benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin Benzoin photopolymerization initiators such as isopropyl ether and benzyldimethyl ketal, benzophenone, benzoylbenzoic acid, methyl benzoylbenzoate, 4-phenylbenzophenone, hydroxybenzophenone, acrylated benzophenone, 4- Benzophenone photopolymerization initiators such as nzoyl-4′-methyldiphenyl sulfide, thioxanthone light such as thioxanthone, 2-chlorothioxanthone, 2-methylthioxanthone, isopropylthioxanthone, 2,4-diisopropylthioxanthone Polymerization initiator, 2,4,6-trichloro-s-triazine, 2-phenyl-4,6-bis (trichloromethyl) -s-triazine, 2- (p-methoxyphenyl) -4,6-bis (trichloro) Methyl) -s-triazine, 2- (p-tolyl) -4,6-bis (trichloromethyl) -s-triazine, 2-piperonyl-4,6-bis (trichloromethyl) -s-triazine, 2,4 -Bis (trichloromethyl) -6-styryl-s-triazine, 2- (naphth-1-yl) -4,6-bis Trichloromethyl) -s-triazine, 2- (4-methoxy-naphth-1-yl) -4,6-bis (trichloromethyl) -s-triazine, 2,4-trichloromethyl- (piperonyl) -6-triazine , 2,4-trichloromethyl (4′-methoxystyryl) -6-triazine and other triazine photopolymerization initiators, borate photopolymerization initiators, carbazole photopolymerization initiators, imidazole photopolymerization initiators and the like are used. It is done.

  The above photopolymerization initiators are used alone or in admixture of two or more. As sensitizers, α-acyloxy ester, acylphosphine oxide, methylphenylglyoxylate, benzyl, 9,10-phenanthrene. Compounds such as quinone, camphorquinone, ethylanthraquinone, 4,4′-diethylisophthalophenone, 3,3 ′, 4,4′-tetra (t-butylperoxycarbonyl) benzophenone, 4,4′-diethylaminobenzophenone Can also be used together.

  A red coloring composition for a color filter comprises a three-roll mill, two dyes in a dye carrier, together with a red dye, a green dye or a black dye, and a yellow dye as necessary, and further with the photopolymerization initiator as necessary. It can be produced by finely dispersing using various dispersing means such as a roll mill, a sand mill, a kneader, and an attritor. The red coloring composition for a color filter can also be produced by mixing finely dispersed pigments in a pigment carrier. When the dye is dispersed in the dye carrier, a dispersion aid such as a resin-type pigment dispersant, a surfactant, or a dye derivative can be appropriately contained. Since the dispersion aid is excellent in pigment dispersion and has a great effect of preventing re-aggregation of the pigment after dispersion, a red coloring composition in which the pigment is dispersed in the dye carrier using the dispersion aid is used. In this case, a color filter having excellent transparency can be obtained.

  The resin-type pigment dispersant has a pigment affinity part that has the property of adsorbing to the pigment and a part that is compatible with the dye carrier, and acts to stabilize the dispersion of the pigment on the dye carrier by adsorbing to the pigment. It is something to do. Specific examples of resin-type pigment dispersants include polycarboxylic acid esters such as polyurethane and polyacrylate, unsaturated polyamides, polycarboxylic acids, polycarboxylic acid (partial) amine salts, polycarboxylic acid ammonium salts, and polycarboxylic acid alkylamines. Salts, polysiloxanes, long-chain polyaminoamide phosphates, hydroxyl group-containing polycarboxylic acid esters, their modified products, amides formed by the reaction of poly (lower alkyleneimines) with polyesters having free carboxyl groups, and the like Water-based dispersants such as oily dispersants such as salts, (meth) acrylic acid-styrene copolymers, (meth) acrylic acid- (meth) acrylic acid ester copolymers, styrene-maleic acid copolymers, polyvinyl alcohol, polyvinylpyrrolidone Resin, water-soluble polymer, polyester Modified polyacrylate, ethylene oxide / propylene oxide addition compound, phosphate ester-based and the like are used, they can be used alone or in admixture of two or more.

  Surfactants include sodium lauryl sulfate, polyoxyethylene alkyl ether sulfate, sodium dodecylbenzene sulfonate, alkali salt of styrene-acrylic acid copolymer, sodium stearate, sodium alkyl naphthalene sulfonate, sodium alkyl diphenyl ether disulfonate. , Lauryl sulfate monoethanolamine, lauryl sulfate triethanolamine, ammonium lauryl sulfate, monoethanolamine stearate, sodium stearate, sodium lauryl sulfate, monoethanolamine of styrene-acrylic acid copolymer, polyoxyethylene alkyl ether phosphate Anionic surfactants such as: polyoxyethylene oleyl ether, polyoxyethylene lauryl ether, polyoxyethylene Nonionic surfactants such as nylphenyl ether, polyoxyethylene alkyl ether phosphate ester, polyoxyethylene sorbitan monostearate, polyethylene glycol monolaurate; chaotic properties such as alkyl quaternary ammonium salts and their ethylene oxide adducts Surfactants: Examples include amphoteric surfactants such as alkylbetaines such as alkyldimethylaminoacetic acid betaine and alkylimidazolines, and these can be used alone or in admixture of two or more.

  The dye derivative is a compound in which a substituent is introduced into an organic dye, and the dye derivative used in the present invention is preferably red or yellow because of the hue, but if the addition amount is small, a blue one may be used. good. Organic dyes also include light yellow aromatic polycyclic compounds such as naphthalene and anthraquinone that are not generally called dyes. Examples of the dye derivatives are described in JP-A-63-305173, JP-B-57-15620, JP-B-59-40172, JP-B-63-17102, JP-B-5-9469, and the like. These can be used alone or in combination of two or more.

  Further, in the red coloring composition for a color filter, a dye is sufficiently dispersed in a dye carrier, and applied to a transparent substrate such as a glass substrate so that a dry film thickness is 0.2 to 5 μm. In order to make it easier to form, a solvent can be included. Examples of the solvent include cyclohexanone, ethyl cellosolve acetate, butyl cellosolve acetate, 1-methoxy-2-propyl acetate, diethylene glycol dimethyl ether, ethylbenzene, ethylene glycol diethyl ether, xylene, ethyl cellosolve, methyl-n amyl ketone, propylene glycol monomethyl ether toluene, methyl ethyl ketone. , Ethyl acetate, methanol, ethanol, isopropyl alcohol, butanol, isobutyl ketone, petroleum solvent and the like, and these are used alone or in combination.

  Moreover, the red coloring composition for color filters can contain a storage stabilizer in order to stabilize the viscosity with time of the composition. Examples of storage stabilizers include quaternary ammonium chlorides such as benzyltrimethyl chloride and diethylhydroxyamine, organic acids such as lactic acid and oxalic acid, and organic acids such as methyl ether, t-butylpyrocatechol, tetraethylphosphine, and tetraphenylphosphine. Examples thereof include phosphine and phosphite.

  The red coloring composition for the color filter can be prepared in the form of gravure offset printing ink, waterless offset printing ink, silk screen printing ink, solvent development type or alkali development type colored resist material. The colored resist material is obtained by dispersing a dye in a composition containing a thermoplastic resin, a thermosetting resin or a photosensitive resin, a monomer, and a photopolymerization initiator.

  The red pigment, the green pigment or the black pigment, and the yellow pigment used as necessary are 1.5 to 7 in total in the red coloring composition when the red filter segment is formed by a photolithographic method. It is preferable to contain it in the ratio of weight%. Moreover, when forming a red filter segment by a printing method, it is preferable to contain in a ratio of 1.5 to 40 weight% in total in a red coloring composition. In any case, the dye is preferably contained in the final red filter segment in a proportion of 10-40% by weight, the remainder consisting essentially of the resinous binder provided by the dye carrier.

  Red colored composition for color filter is not less than 5 μm coarse particles, preferably 1 μm coarse particles, more preferably 0.5 μm coarse particles and mixed by means of centrifugation, sintered filter, membrane filter, etc. It is preferable to remove the dust.

Next, the color filter of the present invention will be described.
The color filter of the present invention comprises at least one red filter segment, at least one green filter segment and at least one blue filter segment, wherein the red filter segment is formed using the red coloring composition of the present invention. The The green filter segment can be formed using a normal green coloring composition, and the blue filter segment can be formed using a normal blue coloring composition.
The green coloring composition is a composition obtained by using, for example, the above-illustrated green pigment and the above-illustrated yellow pigment for toning as required, instead of the red pigment.

Further, the blue coloring composition may be, for example, C.I. I. Pigment Blue 15, 15: 1, 15: 2, 15: 3, 15: 4, 15: 6, 16, 22, 60, 64, and other blue pigments and, if necessary, purple dyes for toning It is a composition obtained.
Examples of purple pigments include C.I. I. Pigment Violet 1, 19, 23, 27, 29, 30, 32, 37, 40, 42, 50, etc. Purple pigments can be used.

For the formation of the green filter segment, a green coloring composition whose brightness is adjusted by adding a specific amount of purple, red or black pigment can be used. By using a combination of a red filter segment formed using the red composition of the present invention and a green coloring composition with adjusted brightness, only the color temperature (K) of white can be obtained without changing the color difference (Δuv). Can be controlled.
For the formation of the blue filter segment, a blue coloring composition whose brightness is adjusted by adding a specific amount of yellow, orange, green or black pigment or red pigment can be used. By using a combination of a red filter segment formed using the red composition of the present invention and a blue coloring composition with adjusted brightness, only the color difference (Δuv) is obtained without changing the color temperature (K) of white. Can be controlled.

The green coloring composition with adjusted lightness includes a transparent carrier, a dye carrier made of a precursor thereof or a mixture thereof, and a green pigment and a purple pigment dispersed in the pigment carrier, and the content of the purple pigment is A composition comprising 0.005 to 10% by weight based on the total amount of the dye, or a dye carrier comprising a transparent resin, a precursor thereof or a mixture thereof, and a green dye and a red dye dispersed in the dye carrier; A composition in which the content of the red pigment is 0.01 to 20% by weight based on the total amount of the pigment, or a pigment carrier comprising a transparent resin, a precursor thereof or a mixture thereof, and dispersed in the pigment carrier A composition containing a green pigment and a black pigment and having a black pigment content of 0.01 to 10% by weight based on the total amount of the pigment can be used. The green coloring composition with adjusted lightness may further contain a yellow pigment, and the content thereof may be 0.01 to 54% by weight based on the total amount of the pigment contained in the green coloring composition. preferable.
The violet, red, or black pigment exemplified above can be used as the lightness adjusting dye contained in the green coloring composition.

The blue coloring composition with adjusted lightness includes a transparent carrier, a dye carrier made of a precursor thereof or a mixture thereof, a blue pigment dispersed in the pigment carrier, and a yellow, orange, green or black pigment, A composition containing 0.01 to 10% by weight of an orange, green or black pigment based on the total amount of the pigment, or a pigment carrier comprising a transparent resin, a precursor thereof or a mixture thereof, and the pigment carrier A composition containing a blue pigment and a red pigment dispersed in the composition, and the content of the red pigment is 0.01 to 30% by weight based on the total amount of the pigment. The blue colored composition with adjusted lightness may further contain a purple pigment, and the content thereof is 0.01 to 15% by weight based on the total amount of the pigment contained in the blue colored composition. preferable.
As the lightness-adjusting dye contained in the blue coloring composition, the yellow, orange, green or black pigment exemplified above, or the red pigment can be used.

The color filter of this invention can be manufactured by forming the filter segment of each color on a transparent substrate using the coloring composition of this invention by the printing method or the photolithographic method.
As the transparent substrate, a glass plate or a resin plate such as polycarbonate, polymethyl methacrylate, or polyethylene terephthalate is used.

  The formation of each color filter segment by the printing method can be patterned simply by repeating the printing and drying of the colored composition prepared as the above various printing inks. Therefore, the color filter manufacturing method is low-cost and excellent in mass productivity. ing. Furthermore, it is possible to print a fine pattern having high dimensional accuracy and smoothness by the development of printing technology. In order to perform printing, it is preferable that the ink does not dry and solidify on the printing plate or on the blanket. Control of ink fluidity on a printing press is also important, and ink viscosity can be adjusted with a dispersant or extender pigment.

  When forming each color filter segment by a photolithography method, the colored composition prepared as the solvent developing type or alkali developing type colored resist material is applied on a transparent substrate, such as spray coating, spin coating, slit coating, roll coating, etc. By a coating method, coating is performed so that the dry film thickness is 0.2 to 5 μm. If necessary, the dried film is exposed to ultraviolet light through a mask having a predetermined pattern provided in contact with or non-contact with the film. Then, after immersing in a solvent or alkali developer or spraying the developer by spraying or the like to remove the uncured portion to form a desired pattern, the same operation is repeated for other colors to produce a color filter. be able to. Furthermore, in order to accelerate the polymerization of the colored resist material, heating can be performed as necessary. According to the photolithography method, a color filter with higher accuracy than the above printing method can be manufactured.

In development, an aqueous solution such as sodium carbonate or sodium hydroxide is used as an alkali developer, and an organic alkali such as dimethylbenzylamine or triethanolamine can also be used. Moreover, an antifoamer and surfactant can also be added to a developing solution.
In order to increase the UV exposure sensitivity, after coating and drying the colored resist material, a water-soluble or alkaline water-soluble resin such as polyvinyl alcohol or water-soluble acrylic resin is applied and dried to form a film that prevents polymerization inhibition by oxygen. Then, ultraviolet exposure can be performed.

  The color filter of the present invention can be produced by an electrodeposition method, a transfer method, or the like in addition to the above method, but the colored composition of the present invention can be used in any method. The electrodeposition method is a method for producing a color filter by using a transparent conductive film formed on a transparent substrate and forming each color filter segment on the transparent conductive film by electrophoresis of colloidal particles. is there. The transfer method is a method in which a color filter layer is formed in advance on the surface of a peelable transfer base sheet, and this color filter layer is transferred to a desired transparent substrate.

Hereinafter, the present invention will be described based on examples, but the present invention is not limited thereto. In the examples and comparative examples, “parts” means “parts by weight”.
First, adjustment of acrylic resin solutions and resins having phosphoric acid groups used in Examples and Comparative Examples will be described. The molecular weight of the resin is a weight average molecular weight in terms of polystyrene measured by GPC (gel permeation chromatography).

(Preparation of acrylic resin solution)
370 parts of cyclohexanone was placed in a reaction vessel, heated to 80 ° C. while injecting nitrogen gas into the vessel, and a mixture of the following monomer and thermal polymerization initiator was added dropwise at the same temperature over 1 hour to carry out a polymerization reaction.
Methacrylic acid 20.0 parts Methyl methacrylate 10.0 parts n-Butyl methacrylate 55.0 parts 2-Hydroxyethyl methacrylate 15.0 parts 2,2′-azobisisobutyronitrile 4.0 parts After the reaction at 3 ° C. for 3 hours, 1.0 part of azobisisobutyronitrile dissolved in 50 parts of cyclohexanone was added, and the reaction was further continued at 80 ° C. for 1 hour to obtain an acrylic resin solution. . The weight average molecular weight of the acrylic resin was about 40,000.
After cooling to room temperature, about 2 g of the resin solution was sampled, heated and dried at 180 ° C. for 20 minutes to measure the nonvolatile content, and cyclohexanone was added to the previously synthesized resin solution so that the nonvolatile content was 20% by weight. To prepare an acrylic resin solution.

[Reference Example 1]
A mixture having the following composition was uniformly dispersed, stirred and mixed, and then filtered through a 1 μm filter to prepare an alkali developing type red colored composition.
Red pigment: C.I. I. Pigment Red 254 4.47 parts
("Irga Four Red B-CF" manufactured by Ciba Geigy)
Blue pigment: C.I. I. Pigment Blue 15: 6 0.03 part ("Rionol Blue ES" manufactured by Toyo Ink Manufacturing Co., Ltd.)
Dispersant (“Solspers 20000” manufactured by Zeneca) 1.00 parts acrylic resin solution 24.00 parts trimethylolpropane triacrylate 5.40 parts (“NK Ester ATMPT” manufactured by Shin-Nakamura Chemical Co., Ltd.)
Photopolymerization initiator ("Irgacure 907" manufactured by Ciba Geigy Co., Ltd.) 0.30 parts Sensitizer ("EAB-F" manufactured by Hodogaya Chemical Co., Ltd.) 0.20 parts Cyclohexanone 64.60 parts

[Examples 3 and 4 and Comparative Examples 1 and 2]
An alkali developing type colored composition was obtained in the same manner as in Reference Example 1 except that the pigment and the blending amount thereof were changed as shown in Table 1.

  The green colored composition 1 produced in the same manner as in Reference Example 1 except that the red colored compositions obtained in Examples 3 and 4 and Comparative Examples 1 and 2, and the pigment and the blending amount thereof were changed as shown in Table 1. And a blue coloring composition 1 on a glass substrate having a thickness of 100 mm × 100 mm and a thickness of 1.1 mm using a spin coater, drying at 70 ° C. for 20 minutes, and using an ultrahigh pressure mercury lamp, an integrated light amount of 150 mJ Stripe pattern UV exposure was performed, followed by development with an alkali developer for 90 seconds to form stripe-shaped color filter segments. The alkali developer is composed of sodium carbonate 1.5% by weight, sodium hydrogen carbonate 0.5% by weight, an anionic surfactant (“Perilex NBL” manufactured by Kao Corporation) 8.0% by weight and water 90% by weight. . The coated substrate was heated at 230 ° C. for 1 hour and allowed to cool, and then the chromaticity (Y, x, y) of the obtained coating film with a C light source was measured with a microspectrophotometer (“OSP-SP100” manufactured by Olympus Optics) And measured. Table 2 shows the chromaticity measurement results for each color filter, and Table 3 shows the chromaticity measurement results for white when the three color filters are combined.

As shown in Tables 2 and 3, when it is desired to increase the values of the white color temperature (K) and color difference (Δuv), the red coloring composition of the present invention (Examples 3 and 4) is used. The target white chromaticity, color temperature (K), and color difference (Δuv) can be achieved without adjusting the brightness of the film and the green coating film.
Moreover, when a red filter segment was formed using the red coloring composition obtained in Comparative Example 2, the desired chromaticity was not obtained.
Moreover, the external appearance of the red coating film formed using the red coloring composition of this invention was favorable.

Claims (5)

A pigment carrier comprising a transparent resin, a precursor thereof or a mixture thereof, and a red pigment and a green pigment dispersed in the pigment carrier, and the content of the green pigment is 0.01 to 15 weight based on the total amount of the pigment % Red coloring composition for color filter,   Furthermore, the red coloring composition for color filters of Claim 1 containing a yellow pigment | dye.   The yellow pigment is C.I. I. The red coloring composition for a color filter according to claim 2, wherein the red coloring composition is at least one yellow pigment selected from the group consisting of Pigment Yellow 13, 138, 139, 150, and 185.   The red pigment is C.I. I. Pigment Red 48: 1, 81: 2, 81: 3, 122, 177, 179, 202, 207, 209, 224, 254, 255, 264, and at least one red pigment selected from the group consisting of The red coloring composition for color filters according to any one of claims 1 to 3.   5. A at least one red filter segment, at least one green filter segment, and at least one blue filter segment, wherein the at least one red filter segment is formed from a red colored composition according to any one of claims 1-4. The color filter characterized by being made.